..

THE
PHYSICSOF
PHYSICS OF

SOLAR
SOLAR CELLS

Jenny Nelson
College, UK
Imperial College, UK

~ .. Imperial College Press

 '!if
'I ..

Published by
Imperial
Imperial College Press
College Press
57 Shelton Street
Covent Garden
London WC2H 9HE

Distributed by
World Scientific Publishing Co. Pte. Ltd.
Preface
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Over the last ten years, photovoltaics has emerged to become become an an application
Library Cataloguing-in-Publication
British Library Cataloguing-in-Publication Data of recognised potential and has
recognised potential has attracted
attracted the interest
interest ofof increasing
increasing numbers
numbers
A catalogue record
record for
for this
this book
book isis available
availablefrom
fromthe
theBritish
BritishLibrary.
Librar. of students and researchers. The purpose of this book is to provide an intro-
duction to, and and overview
overview of, of, the physics
physics of of the
the photovoltaic
photovoltaic cell.
cell. It
It should
should
be suitable for undergraduate
undergraduate physicists
physicists and engineers who who areare interested in
this application of senconductor
semiconductor physics, physics,and andtoto non-specialist
non-specialistgraduates
graduates
First published 2003
Reprinted 2004, 2005
and others who require a background in in the physical principles
principles of of solar
solar cells.
cells.
The focus
focus is on the basic basic semiconductor physics physics relevant
relevant to to photovoltaics,
physical models
models of photovoltaic devices devices andand how how these
these relate
relate to the design
design
and function of of practical
practical devices.
devices. It It should
should enable
enable the reader
reader to understand
THE PHYSiCS
PHYSICS OF SOLAR
SOLAR CELLS
CELLS how solar cells
how solar cells work,
work, to to understand the conceptsconcepts and and models
models of of solar
solar cell
cell
Imperial College
2003 by Imperial
Copyright ig College Press
Press device physics, and
device physics, and to to formulate and solve relevant physical
solve relevant physical problems.
problems. Al-
All rights reserved. This book,
book, or parts
parts thereof,
thereof, may
may not
not be reprodu~edin
be reproduced inany
anyform
form or
orby
byany m~ans,
any m~ans, though practical materials and device device designs
designs are are used
used as examples,
examples, the
electronic or
electronic or mechanical,
mechanical, including
including photocopying,
photocopying, recording
recording or
or any
any information
mformallon storage
storage and
and retrieval
retrieval book is not not intended
intended as as aa comprehensive
comprehensive review review of of photovoltaic materials
materials
known or
system now known or to
to be invented,
invented, without wrillen permission from the Publisher.
and devices,
devices, nor of the latest latest developments
developments in in photovoltaics
photovoltaics research.
research.
Chapter i1 introduces
introduces the the solar
solar cell
cell as
as aa simple
simple current
current generator
generator andand
defines
defines the performance characteristics which are used to describe and com- com-
pare solar cells.cells. Chapter 2 describesdescribes in in general
general terms
terms howhow light energy
energy is is
For photocopying
For photocopying of of material
material in
in this
this volume,
volume, please
please pay
pay aa copying
copying fee
fee tlu0ugh
through thethe Copyright
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Clearance Center,
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Inc., 222
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Rosewood Drive,
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01923, USA.
USA. In thIS case
In this case permission
permISSIOn to
to converted
converted into electricity,
into electricity, comparing comparing
the photo the photo voltaic converter
voltaic converter with other
photocopy is not
not required
required from
from the
the publisher.
publisher. systems and evaluating the limits to effciency. efficiency. Chapters 3 and 44 cover cover the
basic physics of
basic physics of the
the semiconductor,
semiconductor, the the semiconductor
semiconductor transport
transport equations
equations
and thethe processes
processes of light light absorption and carrier recombination. Chapter 55
ISBN
ISBN 1-86094-340-3
1-86094-340-3 focuses
focuses on on the
the concept
concept of of the asymmetric
asymmetric junction,junction, andand details the dif- dif-
ISBN
ISBN 1-86094-349-7
1-86094-349-7 (pbk)
(pbk) ferent
ferent types of of junction
junction which which are exploited
exploited in photovoltaics.
photovoltaics. Chapter 66
applies
applies the the theory
theory of of earlier
earlierchapters
chapterstotoaap-n p- junction,
junction,the theclassical
classical model
model
of aa solar
solar cell.
cell. Chapters
Chapters 7 and and 88 areare concerned
concerned with with the range
range of photo-
photo-
voltaic
voltaic materials
materials anddesigns.
and device device designs.
Chapter 7 deals Chapter
with mono 7 deals with monocrystallne
crystalline
book isis printed
This book printed on
on acid-free
acid-free paper.
paper. rn junctiondevices,
]rnjunction devices, relating
relatingthethemodel
modelof ofChapter
Chapter66totopractical
practicaldevices,
devices,
Pririted in
Printed in Singapore
Singapore by
by Mainland
Mainland Press
Press
v
r r
I
I
vi Preface
Preface
vi

using crystalline silicon and gallium arsenide cells as examples. Chapter 8

using crystallne silcon and gallum arsenide cells as examples. Chapter 8
deals with thin film photovoltaic materials, discussing physical processes
deals with thin film photovoltaic materials, discussing physical processes
anddesign
and designissues
issues relevant
relevant toto thin
thinfilms
films and
andfocusing
focusing ononthe
theways
waysininwhich
which
the standard model must be adapted for thin film devices.
the standard model must be adapted for thin film devices. Chapter 9 deals Chapter 9 deals
with various techniques for managing light in order
with various techniques for managing light in order to maximise perfor- to maximise perfor-
mance, and Chapter 10 covers a range of approaches, mainly theoretical,
mance, and Chapter 10 covers a range of approaches, mainly theoretical,
toto increasing the efficiency of solar cells above the limit for a single band
increasing the effciency of solar cells above the limit for a single band Contents
Contents
gap photoconverter.
gap photoconverter.
I
I amam grateful
grateful totoall
allof
ofthe
thepeople
people whowho have
have helped
helped me
me prepare
prepare this
this book.
book.
In particular, to Keith Barnham for passing the original proposal from Im-
In particular, to Keith Barnham for passing the original proposal from Im-
perial College
perial College Press
Press inin my
my direction;
direction; toto Leon
Leon Freris
Freris and
and David
David Infield
Infield for
for
giving me the opportunity to teach the physics of solar cells to MSc stu-
giving me the opportunity to teach the physics of solar cells to MSc stu-
dents at Loughborough, and so establish the basic course from which this Preface
Preface vv
dents at Loughborough, and so establish the basic course from which this
book developed; to all the research students in photovoltaics at Imperial
book developed; to all the research students in photovoltaics at Imperial
College for raising so many interesting questions, especially Jenny Barnes,
College for raising so many interesting questions, especially Jenny Barnes, Chapter
Chapter 11 Introduction
Introduction 1
1
James Connolly and Benjamin Kluftinger; to Ralph Gottshalg, Tom Mark-
James Connolly and Benjamin Kluftinger; to Ralph Gottshalg, Tom Mark- 1.1.
1.1. Photons
PhotonsIn,
In,Electrons
Electrons Out:
Out: The
ThePhotovoltaic
PhotovoltaicEffect
Effect 1
vart and Peter Wuerfel for help with questions related to material in this 1
vart and Peter Wuerfel for help with questions related to material in this 1.2. Brief
1.2. BriefHistory theSolar
Historyofofthe SolarCell
Cell. .. .. .. .. .. .. .. . .. .. .. 2
book; to Ned Ekins-Daukes and Jane Nelson for their helpful comments 2
book; to Ned Ekins-Daukes and Jane Nelson for their helpful comments 1.3. Photovoltaic
1.3. PhotovoltaicCells
Cells and
and Power Generation. .. . .. .. ..
Power Generation 4
on the text; to Clare Nelson for the cover illustration and to all other col- 4
on the text; to Clare Nelson for the cover ilustration and to all other col- 1.3.1.
1.3.1. Photovoltaic cells, modules
Photovoltaic cells, modules and and systems
systems 4
leagues who have helped in my endeavours to understand how these things 4
leagues who have helped in my endeavours to understand how these things 1.3.2.
1.3.2. Some
Some important definitions . . . .. .. . .. .. .. .
important definitions. . 6
work, 6
work, in in particular
particular toto Richard
Richard Corkish,
Corkish, James
James Durrant,
Durrant, Michael
Michael Gratzel,
Griitzel,
1.4. Characteristics
1.4. Characteristicsof ofthe
the Photovoltaic
Photovoltaic Cell: Cell: AA Summary
Summary 7
Martin Green, Christiana Honsberg, Stefan Kettemann and Ellen Moons. 7
Martin Green, Christiana Honsberg, Stefan Kettemann and Ellen Moons. 1.4.1. Photocurrent and quantum efficiency ..
1.4.1. Photocurrent and quantum effciency 7
II am
am grateful
grateful toto the
the Greenpeace
Greenpeace Environmental
Environmental 'Irust for funding
funding meme to to 7
'Iust for 1.4.2. Dark
1.4.2. Darkcurrent
currentand andopen
open circuit
circuit voltage
voltage .. 9
study solar cells before they were popular, and to the UK Engineering and 9
study solar cells before they were popular, and to the UK Engineering and 1.4.3. Efficiency..........
1.4.3. Effciency.......... 11
Physical Sciences Research Council and for an Advanced Research Fellow- 11
Physical Sciences Research Council and for an Advanced Research Fellow- 1.4.4. Parasitic
ship which allowed me to spend my Saturday afternoons writing chapters 1.4.4. Parasitic resistances
resistances . . .. .. .. 13
13
ship which allowed me to spend my Saturday afternoons writing chapters 1.45. Non-ideal 15
instead of lectures. Finally I am grateful to John Navas for his encourage- 1.4.5. Non-ideal diode
diode behaviour
behaviour 15
instead of lectures. Finally I am grateful to John Navas for his encourage- 1.5. Summary.
1.5. Summary. 15
ment to
ment to start on this
start on project and
this project and to
to Laurent
Laurent Chaminade
Chaminade and and his
his staff
staff at
at IC
IC 15
References .
References 16
Press
Press and to Lakshmi Narayan and colleagues at World Scientific, for their
and to Lakshmi Narayan and colleagues at World Scientific, for their 16
help in seeing it through.
help in seeing it through. Chapter22 Photons
Chapter Photons In, In, Electrons
Electrons Out: Out: Basic
Basic
This
This book
book isis dedicated
dedicated to to the memory of
the memory Stephen Robinson
of Stephen Robinson and and M.V.
M.V.
McCaughan.
Principles
Principles of PV of PV 17
17
McCaughan. Introduction
2.1. Introduction
2.1. . .. .. .. .. .
. .. .. ....... .. 17
17
Jenny Nelson TheSolar
2.2. The
2.2. SolarResource
Resource . ...... .. .. .
. . .. 17
17
Jenny Nelson 2.3. Types 22
London, April 2002 2.3. Types of
of Solar
SolarEnergy
Energy Converter
Converter 22
London, April 2002 2.4. Detailed
Detailed Balance 24
2.4. Balance . .......
... . 24
2.4.1. In
2.4.1. In equilbrium
equilibrium . . .. .. 24
24
2.4.2. Under
2.4.2. Under illumination
ilumination 26
26
2.5. Work Available from aa Photovoltaic
2.5. Work Available from Photovoltaic DeviceDevice 28
28
2.5.1.
2.5.1. Photocurrent....
Photocurrent . . .. 28
28
vii
vii
 r~
viii Contents
viii Contents Contents ix
ix

2.5.2.
2.5.2. Dark
Dark current . . . . current . . . . 30
30 3.7.3. Current
3.7.3. Currentequations
equationsfor
fornon-crystallne
non-crystalline solids.
solids. 76
76
2.5.3.
2.5.3. Limiting
Limiting efficiency . effciency. 31
31 3.8. Summary.........................
3.8. Summary ................... . 77
77
2.5.4.
2.5.4. Effect of band gap. 3334
Effect of band gap. 33
2.5.5. Effect of spectrum on effciency 34
2.5.5. Effect of spectrum on efficiency Chapter 44 Generation
Chapter Generation and
and Recombination 79
79

2.7.
2.6.
Summary.
References . 38
2.6. Requirements
Requirements for the for
2.7. Summary.
References . 39
Idealthe Ideal Photoconverter
Photoconverter 35
35
38
39
4.1. Introduction:
4.1.
4.2.
Introduction: Semiconductor
4.2. Generation
4.3.
Semiconductor Transport
andRecombination
Generation and Recombination
'Iansport Equations.
Equations.
. .... .. .. .
Quantum Mechanical Description of 'Ian
4.3. Quantum Mechanical Description of
. ......... ..
sit ion Rates
Transition
79
79
81
81
83
4.3.1.
4.3.1. Fermi's
Fermi's Golden RuleRule
Golden ... ...... .
.......... 83
Chapter
Chapter 3 3 Electrons
Electrons and
and Holes
Holes in Semiconductors 41
in Semiconductors 41 4.3.2. Optical
4.3.2. Opticalprocesses
processesinin aa two
two level
level system
system 85
3.1. Introduction..............
3.1. Introduction . . ....... . ... . 41 41 4.4. Photogeneration........
4.4. 87
3.2. Basic Concepts ............... 42
3.2. Basic Concepts . . . . . . . . . . . . . . . 42 4.4.1.
4.4.1. Photogeneration rate. .. .. ........... ..
Photogeneration rate 88
3.2.1. Bonds
3.2.1. Bonds and bands
and in crystalsin.. crystals
bands . . . . 42 42 4.4.2. Thermalisation.....
4.4.2. Thermalisation............. . . . . . . .. 89
3.2.2. Electrons, holes and conductivity 44
3.2.2. Electrons, holes and conductivity 44 4.4.3.
4.4.3. Microscopic description of absorption
Microscopic description of absorption 90
3.3. Electron States in Semiconductors. 46
3.3. Electron States in Semiconductors. 46 4.4.4. Direct
4.4.4. Direct gap
gap semiconductors
semiconductors .. 93
3.3.1. Band structure. . 46
3.3.1. Band structure .. 46 4.4.5. Indirect
4.4.5. Indirect gap
gap semiconductors 94
3.3.2.
3.3.2. Conduction
Conduction band . . . . . band .... . 48 48 4.4.6.
4.4.6. Other types of
Other types of behaviour 96
3.3.3. Valence band. . . . . . . . 49
3.3.3. Valence band. . . . . . . . 49 4.4.7. Examples
4.4.7. Examples and anddatadata .. . .. 98
3.3.4. Direct and indirect band gaps 50
3.3.4. Direct and indirect band gaps 50 4.5. Recombination
4.5. Recombination .......... 99
3.3.5. Density of states. . . . . . . . 51
3.3.5. Density of states. . . . . . . . 51 4.5.1. Typesof
4.5.1. Types of recombination.
recombination. 99
3.3.6. Electron distribution function 54
3.3.6. Electron distribution function 54 4.5.2. Radiative recombination
4.5.2. Radiative recombination 99
3.3.7. Electron and hole currents 55
3.3.7. Electron and hole currents 55 4.5.3. Simplifiedexpressions
4.5.3. Simplified expressions for for radiative
radiative recombination
recombination 102
3A. Semiconductor in Equilibrium .
3A. Semiconductor in Equilbrium . . . . . 56. . . . 56 4.5.4. Auger
4.5.4. recombination
Auger recombination . .. .. .. . .. .. . . . .. .. . .. 105
3.4.1. Fermi Dirac statistics . . . . . 56
3.4.1. Fermi Dirac statistics . . . . . 56 4.5.5. Shockley
4.5.5. Shockley Read
Read HallHall recombination
recombination. . ...... .. 106
3.4.2. Electron
3.4.2. Electron andand holehole densities
densities in equilbrium. 57
in equilibrium. 57 4.5.6. Surface and
4.5.6. Surface and grain
grain boundary
boundary recombination 110
3.4.3.Boltzmann
3.4.3. Boltzmann approximation
approximation . . . . . . . . . . . . . . . 58 58 4.5.7. Trapsversus
4.5.7. 'Iaps versus recombination
recombination centres
centres .. 111
3.4.4. Electron and hole currents in equilbrium 60
3.4.4. Electron and hole currents in equilibrium 60 4.6. Formulation
4.6. of the
Formulation of theTransport
'Iansport Problem
Problem .. .. . .. 112
3.5. Impurities and Doping . . . . . . 61
3.5. Impurities and Doping . . . . . . 61 4.6.1. Commentsononthe
4.6.1. Comments thetransport
transport problem
problem 113
3.5.1. Intrinsic semiconductors 61
3.5.1. Intrinsic semiconductors 61 4.6.2. Transportequations
equationsininaa crystal
crystal 114
3.5.2. n type doping . . . . . 62
3.5.2. n type doping . . . . . 62 4.7.
4.6.2. 'Iansport
4.7. Summary.
Summary. 115
3.5.3. p type doping . . . . . . 63
3.5.3. p type doping . . . . . . 63 References . 117
3.5.4.
3.5.4. Effects
Effects of heavy dopingof . heavy doping . 65 65
3.5.5.
3.5.5.Imperfect
Imperfectand amorphous crystals
and amorphous crystals 65 65 Chapter 55 Junctions
Junctions 119
119
3.6. Semiconductor under Bias . . . . . . . . . 66
3.6. Semiconductor under Bias . . . . . . . . . 66 5.1.
5.1. Introduction .............. .
Introduction............... 119
119
3.6.1. Quasi thermal equilbrium . . . . 66
3.6.1. Quasi thermal equilibrium . . . . 66 5.2. Origin
5.2. Origin of
of Photovoltaic Action........ .
Photovoltaic Action 120
120
3.6.2. Electron
3.6.2. Electron andand hole densities
hole densities under bias.under bias. 68 68 5.3. WorkFunction
5.3. Work Function and
and Tyes
Typesofof Junction
Junction 124
124
3.6.3. Current densities under bias . . . . . . 69
3.6.3. Current densities under bias . . . . . . 69 5.4. Metal-Semiconductor Junction
5.4. Metal-Semiconductor Junction 125
125
3.7. Drift and Diffusion . . . . . . . . . . . . . . . . 72
3.7. Drift and Diffusion . . . . . . . . . . . . . . . . 72 5.4.1. Establishing
5.4.1. Establishing aafield
field ..
.. 125
125
3.7.1. Current equations
3.7.1. Current equationsinin terms
terms of drift and diffusion.
of drift and diffsion. 72 72 5.4.2. Behaviour
5.4.2. Behaviour in
in the
the light . 126
126
3.7.2. Validity of
3.7.2. Validity ofthe
thedrift-diffusion
drift-diffsion equations . . .. ... . . . . . 75
equations 75 5.4.3. Behaviour in
5.4.3. Behaviour in the
the dark.
dark. 127
127
xx Contents
Contents
r Contents
Contents xi
xi

I
I
i
6.8.4.
6.8.4. Other
Otherdevice
device structures
structures .. .. .
. ..
i
174
5.4.4. Ohmic contacts
5.4.4. Ohmic contacts. .. .. .. .. .. .. . . . .. .. .. .. .. .. .. . . 129
129
130
I
I
6.8.5. Validity
Validityof
of the
the approximations
174
174
5.4.5. Limitations ofofthe
5.4.5. Limitations theSchottky
Schottkybarrier
barrier junction
junction 174
130 6.8.5. approximations
5.5. Semiconductor-Semiconductor
Semiconductor-SemiconductorJunctions Junctions 131
131 6.9. Summary.
6.9. Summary. 175
175
5.5.
5.5.1. p- p-njunction
junction .. .. .. .. 131 References
References .. 176
176
5.5.1. 131
5.5.2. p--n
5.5.2. junction .... ..
p-i-njunction 132
132
133 Chapter
Chapter 7 Monocrystalline
MonocrystallineSolar
SolarCells
Cells 177
177
5.5.3 . p-n heterojunction
5.5.3. p-n heterojunction 133
7.1. Introduction:
7.1. Introduction:Principles
Principles of
of Cell
Cell Design
Design 177
177
5.6. Electrochemical
5.6. Electrochemical Junction.
Junction .. . 133
133
5.7. Junctions in Organic Materials 137
137 7.2.
7.2. Material
Materialand
and Design Issues.
Design Issues . .. .. .. .. 178
178
5.7. Junctions in Organic Materials
7.2.1. Material
7.2.1. Materialdependent
dependentfactors
factors . ..
. 178
178
5.8. Surface
5.8. Surfaceand
andInterface
Interface States
States . .. .
139
139
5.8.1. Surface states onfreefree surfaces
surfaces 139
139 7.2.2.
7.2.2. Design factors............ .. .. ..
Design factors 179
179
5.8.1. Surface states on
7.2.3. General
7.2.3. General design
design featuresofofp-n
features junctioncells
p-njunction cells 180
180
5.8.2 . Effect
5.8.2. Effectofofinterface
interface states
states on junctions
on junctions 141
141
5.9. Summary. 143
143 7.3.
7.3. Silcon
Silicon Material Properties.
Material Properties . . .. .
. .. ........... .. .. 180
180
5.9. Summary. 180
References .. 144 7.3.1.
7.3.1. Band
Bandstructure
structureand
andoptical
opticalabsorption
absorption 180
References
7.3.2.
7.3.2. Doping......
Doping ..... . 181
181
Chapter 66 Analysis
Analysis of of the
the p-n Junction
p-n Junction 145 7.3.3. Recombination..
7.3.3. Recombination .. 182
182
Chapter
6.1. Introduction . . . . . . . . . . . . . 145 7.3.4. Carrier
7.3.4. Carrier transport
transport 185
185
6.1. Introduction.............
6.2. The
The p-n 146 7.4. Silcon
SiliconSolar
Solar Cell
Cell Design 186
6.2. p-n Junction
Junction. . ............ .. .. .. 7.4. Design . 186
6.2.1. Formation
6.2.1. Formation of ofp-n junction
p-n junction 146 7.4.1.
7.4.1. Basic
Basicsilcon
siliconsolar
solar cell
cell .. 186
186
6.2.2. 147 7.4.2. Cell fabrication
fabrication .... ... 186
6.2.2. Outline of approach.. .. .. ..
Outline of approach 7.4.2. Cell 186
6.3. Depletion Approximation. 149 7.4.3. Optimisation
7.4.3. Optimisationofofsilcon
siliconsolar
solarcellcelldesign
design 188
6.3. Depletion Approximation. .. .. .. .. .. " ;;( .. 188
6.3.1. Calculationofof depletion
depletion width 150 7.4.4. Strategies to enhance absorption. . . .. .. 190
width .. 190
7.4.4. Strategies to enhance absorption.
6.3.1. Calculation
6.4. Calculationof of Carrier
Carrier and Current Densities
Densities . 152 7.4.5. Strategies to
7.4.5. Strategies to reduce
reduce surface
surface recombination
recombination 191
191
6.4. Calculation and Current
6.4.1. Currents and carrier densities in the
the neutral
neutral 7.4.6. Strategiestotoreduce
7.4.6. Strategies reduceseries
series resistance.
resistance. .. 194
194
6.4.1. Currents and carrier densities in
regions 152 7.4.7. Evolution
Evolutionofofsilcon
siliconsolar
solar cell design. . 194
regions . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . ... .. 7.4.7. cell design. 194
6.4.2. Currentsand andcarrier
carrierdensities
densities in in the
the space
space 7.4.8.
7.4.8. Future directions in silicon cell design
Future directions in silcon ell design.. 197
197
6.4.2. Currents
charge region. .
charge region. . . . . . . . 154
154 7.4.9. Alternatives
7.4.9. Alternatives toto silcon.
silicon ... . .. ........... .. 198
198
6.4.3. Total current
current density
density 156
156 7.5. III-V Semiconductor
7.5. I11-V SemiconductorMaterial
MaterialProperties.
Properties ... .. .. 198
198
6.4.3. Total
6.5. General Solution
6.5. General Solution forfor J(V)
J(V) 156
156 7.5.1. III-V semiconductor
7.5.1. I11-V semiconductorband bandstructure
structure and and optical
optical
6.6. p-n Junction in the Dark...
6.6. p-n Junction in the Dark . 160
160 absorption
absorption . . . . . . . . 0' 198
198
6.6.1. At equilibrium.
equilibrium . .. .. 160
160 7.5.2. Galliumarsenide
7.5.2. Gallum arsenide 200
200
6.6.1. At
6.6.2. Underapplied
6.6.2. Under applied bias
bias 160
160 7.5.3. Doping......
7.5.3. Doping . . . . . . 201
201
Junction under 165 7.5.4.
7.5.4. Recombination .. 202
under Illumination.
6.7. p-n Junction
6.7. p-n Ilumination. 165 Recombination.. 202
6.7.1. 165 7.5.5. Carrier transport
transport 203
6.7.1. Short circuit. .. . . . .. .. .. ..
Short circuit 165 7.5.5. Carrier 203
6.7.2. Photocurrentand
6.7.2. Photocurrent andQE QEininspecial
special casescases 167
167 7.5.6. Reflectivity
7.5.6. Reflectivity....
.... 203
203
6.7.3. p-n junction as a photovoltaic cell ..
6.7.3. p-n junction as a photovoltaic cell 169
169 7.6. GaAs
7.6. GaAs Solar
Solar Cell Design....
Cell Design 204
204
6.8. Effects on Junction Characteristics.
Characteristics. 172
172 7.6.1. Basic
7.6.1. BasicGaAs
GaAs solar
solar cell
cell 204
6.8. Effects on p-n
p-n Junction 204
6.8.1.
6.8.1. Effects of parasitic resistances
Effects of parasitic resistances 172
172 7.6.2. Optimisation
7.6.2. OptimisationofofGaAs GaAssolar
solar cell
cell design
design 204
204
6.8.2. Effect ofof irradiation
irradiation .. 172
172 7.6.3. Strategies to
7.6.3. Strategies to reduce frontfront surface
surfacerecombination
recombination 205
205
6.8.2. Effect
6.8.3. Effect of
6.8.3. Effect of temperature
temperature... ....... 173
173 7.6.4.
7.6.4. Strategies
Strategies to reduce series resistance . . .. .. .. ... ..
to reduce series resistance. 207
207
 xii Contents
xii Contents
r-
Contents xiii
Contents xiii

7.7. Summary.
7.6.5.
7.6.5.
208
Strategies
Strategies

References. 210
7.7. Summary.
to reduce
to reduce substrate
substrate cost . cost. 208
208
208
8.9.
8.8.1.
8.8.1. Materials
Materials

Summary. 251
8.8.2.
249
properties. . . . . . . . . . . . 248
properties.
8.8.2. Microcrystallne silcon
Microcrystalline silicon solar
solar cell cell
design.
248
design. 248
248
References .

Chapter 8Film
Chapter 8 Thin Thin
SolarFilm
Cells Solar Cells 211
211
210
References.
8.9. Summary.
References .
249
251

8.1. Introduction..................
8.1. Introduction... . . 211
211 Chapter 9 Light
Chapter 9 Managing Managing Light 253
253
8.2. ThinFilm
8.2. Thin Film Photovoltaic
Photovoltaic Materials Materials
.. . . . . . . 213
213 9.1. Introduction............................
9.1. Introduction... . . 253
253
8.2.1.
8.2.1. Requirements
Requirements for materials
for suitable suitable materials 213 213 PhotonFlux:
9.2. Photon
9.2. Flux: AAReview
Reviewand
andOverview
Overviewofof Light
Light
8.3. Amorphous
8.3. Amorphous Silicon Silcon. . . . . . . . . . . . . . 213
213 Management
Management . . . . . . . .. . . . . . . . . . . . 255
255
8.3.1.
8.3.1. Materials
Materials properties. . . . . . . 213
properties. 213 9.2.1.
9.2.1. Routes
Routes to higher
to higher photon flux. . . . . 257
photon flux. 257
9.3. Minimising Reflection. . . . . . . . . . . . . . 258
8.3.3.
8.3.2.

8.3.4. Absorption.
8.3.2 . Defects
Defects
217
in amorphous

Doping... 217
8.3.3. Absorption .
material .
in amorphous 215
material . 215
217
9.3. Minimising
9.3.1.
9.3.1.
9.3.2.
Reflection..
Optical
Optical
..
properties
properties
Antireflection
of semiconductors 258
of semiconductors
coatings 260
258
258

8.3.5.
8.3.4.
8.3.5.
8.3.6.
'Iansport
Doping
Transport
Stability
219
8.3.6. Stabilty.. 220
217
219
220
9.4.
9.3.2. Antireflection
9.4. Concentration
9.4.1.
coatings
Concentration..........
. . . . . .
Limits
260
263
to concentration 263
263

8.3.7. Related alloys 221

8.3.7. Related alloys
8.4. Amorphous Silcon Solar Cell Design 221
8.4. Amorphous Silicon Solar Cell Design
221
221
9.4.1.
9.4.2.
9.4.2.
Limits to concentration
Practical
Practical
263
concentratorsconcentrators 264
264
9.5. Effects
9.5. of Concentration
Effects of Concentration on Device on Device Physics. 266
Physics. 266
8.4.1.Amorphous
8.4.1. Amorphous silcon
silicon p-i-n ri-n structures 221
structures 221 9.5.1.
9.5.1. LowLow injection
injection .. ............ 266 266
8.4.2.p-i-
8.4.2. p-i-n solar
n solar cellphysics
cell device device physics . . . 222 222
9.5.2. High injection . . . . . . . . . . . . 267
9.5.2. High injection .. 267
8.4.3. Fabrication of a-Si solar cells . . . . 227
8.4.3. Fabrication of a-Si solar cells . 227
9.5.3. Limits-to
9.5.3. effciency
Limits-to efficiency underunder concentration. 269
concentration. 269
8.4.4. Strategies
8.4.4.
8.5. Defects
Strategies to to
Defects in in
improve
improve
Polycrystalline
a-Siperformance
a-Si cell
Thin
cell performance 227
Film Materials
227
. . 229
9.5.4. Temperature....... 270
9.5.4. Temperature . . . . . 270
8.5.
8.5.1.Grain
8.5.1.
Polycrystalline
Grain
Thin Film
boundaries
boundaries ..
Materials .
. . . . . . . . . . . . . 230
229
230
9.5.5. Series resistance . . . . . . 270
9.5.5. Series resistance 270

8.5.2. Effects of grain boundaries on transport 233

8.5.2. Effects of grain boundaries on transport 233
9.5.6. Concentrator cell design . 270
9.5.6. Concentrator cell design . . 270
8.5.3. Depletion approximation
8.5.3. Depletion approximationmodelmodelfor for grain
grain
9.5.7. Concentrator cell materials 271
9.5.7. Concentrator cell materials. 271
boundary . . . . . . . . . . 234
boundary . . .. .. 234
9.6.
9.6. LightLight Confinement
Confinement .. .. ......... 272 272
9.6.1. Light paths and ray tracing 272
8.5.4. Majority carrier transport 236
8.5.4. Majority carrier transport
8.5.5. Effect of ilumination . . . 239
8.5.5. Effect of illumination
236
239
9.6.2. Mirrors........ 274
9.6.1. Light paths and ray tracing
9.6.2. Mirrors.
9.6.3. Randomising surfaces 275
272
274
8.5.6. Minority carrier transport 240
8.5.6. Minority carrier transport 240 9.6.3.
9.6.4.
Randomising surfaces
9.6.4. Textured surfaces . . 276
Textured surfaces
275
276
8.5.7. Effects of
8.5.7. Effects of grain
grain boundary
cell performance .
recombination on
boundary recombination
cell performance . . . . 242
on solar
solar
242 9.6.5. Practical schemes . . 278
9.6.5. Practical schemes .. 278
8.6. CulnSe2
8.6. CuInSe2 Thin Thin
FilmFilm
Solar Solar
Cells. Cells. . .. .. . . . . . . . . . 243 243 9.6.6. Lightconfining
9.6.6. Light confiningstructures:
structures: restricted
restricted acceptance
acceptance

8.6.1. Materials
8.6.1. Materials properties.
properties . . . . . . . . . . . . . . . . . . . . 243
243 areasandand
areas external
external cavities cavities . . . . . . . . . 280
280
8.6.2. Heterojunctions
8.6.2. Heterojunctions in thinin thin
film film
solar solar cell design 244
cell design 244 9.6.7.
9.6.7. Effects of light trapping on device
Effects of light trapping on device physics physics 281
281
8.6.3. CulnGaSe2 solar cell design 245
8.6.3. CuInGaSe2 solar cell design 245 9.7. Photon Recycling . . . . . . . . . . . 282
9.7. Photon Recycling 282
8.7. CdTe Thin Film Solar Cells . . 246
8.7. CdTe Thin Film Solar Cells 246 9.7.1. Theory of photon recycling. 282
9.7.1. Theory of photon recycling . 282
9,7.2. Practical schemes 285
8.7.1. Materials properties. . 246
8.7.1.
8.7.2.
Materials properties.
8.7.2. CdTe solar cell design. 247
CdTe solar cell design.
8.8. Thin Film Silcon Solar Cells. . 248
8.8. Thin Film Silicon Solar Cells.
246
247
248
9.8. Summary. 286
9,7.2.
9.8. Summary.
Practical schemes

References. . . . . . . . . . . . . 288
References. . .
285
286
288
i:
:
.F
I !
 xiv
xiv Contents
Contents Contents
Contents xv
xv

Chapter 10
Chapter Over the
10 Over the Limit:
Limit:Strategies
Strategies for High Efficiency
for High Effciency 289
289 Fundamental
Fundamental constants
constants
10.1. Introduction. .. . . . . . . . . . . . . . . . . . . . . . . . . .. 289
10.l. Introduction 289
I'li hh Planck's
Planck'sconstant
constant
10.2. How
10.2. How Much
Much is
is Out
Out There?
There? Thermodynamic
Thermodynamic Limits to
Limits to
1;11
'il Ii Planck's
Ii Planck'sconstantj211
constant/21T
p Effciency
Efficiency ..................... 291 291
O
eo dielectric
dielectricpermittivity
permittivityofoffree
freespace
space
,.j'
j<;,<
10.3. Detailed Balance Limit to Effciency, Reviewed 292
10.3. Detailed Balance Limit to Efficiency, Reviewed 292
O'B
O'B Stefan's
Stefan'sconstant
constant
;~
Multiple Band Gaps
10.4. Multiple Band Gaps ........ 297
10.4. 297
cc speed
speed
of of light in
light in vacuum
vacuum
.:!.
10.5. Tandem Cells . . . . . . . . . . . . 298
10.5 . Tandem Cells 298
kB
kB Boltzmann's
Boltzmann'sconstant
constant
10.5.l. Principles
10.5.1. of tandem cells
Principles of. tandem cells. 298 298
mo
mo free
freeelectron
electronmass
mass
10.5.2. Analysis .. . . . . . . . . 300
10.5.2. Analysis 300
qq charge
charge
on on theelectron
the electron
10.5.3. Practical tandem systems. 301
10.5.3. Practical tandem systems . 301
10.6. Intermediate
10.6. Intermediate Band
Band and andBand
Multiple Multiple
Cells Band Cells 302 302
Symbols used in
in the
the text
1O.6.l. Principles
Principles of Symbols used
"
10.6.1. ofintermediate
intermediate and multiple
and band
multiple cellscells 302
band 302
10.6.2. Conditions
10.6.2. Conditions................... 303 303 a absorption coeffcient
coefficient
10.6.3. Practical
10.6.3. Practical strategies . . . . . . . . . . . . . . 306
strategies 306
10.7. Increasing
10.7. Increasing thethe
Work
WorkPer Photon using 'Hot'
Per Photon usingCarriers
'Hot' Carriers 309 309 [
X
spectral photon
photon flux
electron affinity
electron affnity
flux density per unitunit solid
solid angle
angle

10.7.1. Principles
10.7. I. Principles of cooling
of cooling and 'hot'and 'hot'
carriers . carriers. 309 309
10.7.2.Analysis
10.7.2. Analysisof the of
hot the hot
carrier carrier
solar cell solar cell 311 311 I !:lL

quasi Fermi level
emissivity
separation or chemical
level separation
emissivity i.i. e.e. probability
probabilty of
chemical potential of light
of photon
photon emission
emission
10.7.3. Practical strategies . . . . . . . . . . . 316
10.7.3. Practical strategies 316 s dielectric permittivity
permittivity of of semiconductor
semiconductor
10.8.Impact
10.8. Impact lonisation
Ionisation Solar
Solar Cells . Cells. . . . . . . . . . . 318 318 polarisation vector of light

10.9. Summary.
10.8.l.
10.9. Summary.
References
References .
323
10.8.1.Analysis
. 324
Analysis of impact
of impact ionisationionisation
solar cell solar cell 320 320
323
324
<P
cP

t.
<I>
electrostatic potential
work function

Exercises 327
Exercises 327
<Po
cPo
1]
r

"'s
/'i,s
neutrality level
neutrality level
power conversion efficiency
imaginary part of
effciency
of refractive
refractive index
index of
of semiconductor
Solutions to the Exercises 337
Index 355
Solutions to the Exercises

Index
337

355
A

J,L
lL
J,Ln;
lLn; J,Lp
1/
1/

Be
lLp
wavelength of light
chemical potential
chemical
electron
potential
mobilty;
electron mobility; hole
frequency of light
frequency
critical angle
critical
hole mobility
mobilty

angle at optical interface

Bsun
f)sun angular width
angular width of the the sun
P charge density
charge density or resistivity
0'
0' conductivity
rT lifetime
lifetime
Tn;Tp electron lifetime;
electron lifetime; holehole lifetime
lifetime
W angular frequency
angular frequency of light
n solid angle
solid angle
'l wavefunction
wavefunction
V, Vr grad operator
grad operator with with respect
respect to position
position
Vk grad
grad operator
operator with with respect
respect toto wavevector
wavevector
 ~r

xvi Contents Contents xvii

a probability of
probabilty of photon absorption
photon absorption jn; jp electron current density;
spectral electron density; spectral hole
hole current density
A cell area
cell k crystal wavevector
wavevector
b spectral photon flux density normal to surface surface L diffsion length
diffusion length or or length
length of
of crystal
crystal sample
sample
Bn; Bp coeffcient for
coefficient for bimolecular
bimolecular capture
capture by trap
trap ofof electrons;
electrons; Ln; Lp diffusion length of
diffsion length of electron;
electron; diffusion length of
diffsion length of hole
hole
holes m diode ideality factor
Brad
Brad coeffcient of bimolecular
coefficient bimolecular radiative recombination m~ conduction band
band effective
effective mass
D diffusion coefficient
diffsion coeffcient m~ valence band effective
effective mass
Dn; Dp diffusion coefficient of
diffsion coeffcient of electron;
electron; diffusion
diffusion coefficient of hole
coeffcient of hole M
M dipole matrix element
dipole element
EE energy n density of electrons
electrons per per unit
unit volume
volume
Eo electromagnetic field
electromagnetic field strength no equilbrium electron
equilibrium electron density
EF Fermi energy or Fermi level level n intrinsic carrier density
Ii
EFn; EFp electron quasi-Fermi energy level; level; hole quasi-Fermi level ns refractive index of semiconductor
Eg band gap
band Na density of acceptor
acceptor impurity atoms
Ett
E energy of
energy of trap state Nd density of donor
donor impurity atoms
Ev energy of valence
valence band edge Ne effective conduction band density of
effective of states
states
Ee
Ec conduction band edge
energy of conduction Nv effective valence
valence bandband density of of states
states
Ei
E intrinsic energy level
level N charged background doping in intrinsic layer
Evae
Evac vacuum energy level Nt density of
density of trap
trap states
F electrostatic field Ns density of interface states
states per
per unit area
area
F force P density of holes
holes perper unit volume
volume
1 (k, r)
f(k, r) probabilty
probability occupation
occupation function
function for electronic
electronic state at k,
stateat k, r P momemtum
fo
10 Fermi Dirac probabilty
Fermi Dirac probability occupation
occupation function
function P power density
Fa; Fe; Fs;
Fs; Fx
Fx geometrical factor
geometrical factor relating
relating normal
normal to to angular photon
photon flux
flux Po equilbrium hole
equilibrium hole density
density for emission from: ambient;
emission from: ambient; cell;
cell; sun;
sun; concentrated Q
Q charge
light source QE
QE quantum effciency
efficiency
FF fill factor
fill rr position
g
g photogeneration rate
spectral photogeneration rate per
per unit volume
volume T transition rate
C
G generation rate
generation rate per
per unit volume
volume R reflectivity
G
Cnn electron generation
electron generation raterate per
per unit volume
volume Rs series resistance
G
Cpp hole generation
hole generation rate
rate per
per unit volume
volume Rsh shunt or parallel
parallel resistance
resistance
g(E)
g(E) density of
density of electronic
electronicstates
states per
per unit
unit energy
energy perper unit crystal S vector defining
defiing aa point
point onon surface
surface
volume 3n
Sn electron surface recombination velocityvelocity
H
H Hamiltonian operator 3p
Sp hole surface recombination velocity
/
I current tt time
10
/0 incident light intensity TT temperature
JJ current
current density
density Ts temperature of of sun
sun
JJse
sc short circuit current density
density UE energy density
energy density of of radiation
radiation per
per unit volume
volume
Jdark
Jdark dark current density
dark current density U recombination rate
recombination rate per
per unit volume
volume
IIn;
n ; JJp
p electron current density;
electron density; hole current density Un electron recombination
electron recombination rate rate per
per unit volume
volume
xviii Contents Contents xix

Up hole
hole recombination
recombination rate
rate per
per unit volume
volume CIGS copper indium gallium
gallum diselenide
diselenide
UAug Auger recombination rate AR antireflection
Urad radiative recombination
recombination rate
rate. PERL passivated emitter, rear locally diffused
passivated emitter, diffused solar cell
USRH Shockley Read
Shockley Read Hall
Hall recombination
recombination rate PESC passivated emitter solar cell
passivated emitter
V volume TCO transparent
transparent conducting oxide
conducting oxide
v velocity PR photon recycling
V voltage or bias
voltage or bias QD
QD quantum dot
Vbi built in
built in bias
bias QW
QW quantum well
Vce open circuit voltage LO longitudinal optical (of
(of phonons)
Vn donor ionisation energy
Vp acceptor ionisation energy
Wn;Wp thickness of
thickness of depletion
depletion region
regioninin nn layer;
layer; in
in player
player
X concentration factor

Acronyms
e.m.f. electromotive force
electromotive force
ac alternating current
dc direct current
AM air mass
AM1.5 air mass 1.5 spectrum
mass 1.5 spectrum-- standard
standardfor forsolar
solar cell
cell calibration
calibration
STC standard test conditions
CB conduction band
VB valence
valence band
FGR Fermi's golden rule
PV photovoltaics
a-Si amorphous silicon
amorphous silcon
c-Si crystallne silcon
crystalline silicon
p.-Si
i-Si microcrystallne silicon
microcrystalline silcon
a-Si:H hydrogenated amorphous
hydrogenated amorphous silicon
silcon
a-SiC amorphous silicon-carbon
amorphous silcon-carbon alloy
amorphous silicon-germanium
a-SiGe amorphous silcon-germanium alloy
DOS density of states
JDOS joint density
joint density ofof states
states
ii region intrinsic or
region intrinsic or undoped
undoped region
regionofofa ap-i-n
p--n junction
SCR space charge region
space charge region
QE
QE effciency
quantum efficiency
SRH Shockley-Read-Hall
GaAs gallum arsenide
gallium arsenide
CdTe cadmium telluride
r
r
i

Chapter
Chapter 11

Introd uction
Introd

1.1. Photons
1.1. Photons In,
In,Electrons
Electrons Out:
Out: The
The Photovoltaic
Photovoltaic Effect
Effect

Solar photovoltaic
photovoltaic energy
energy conversion
conversion is one~step conversion process which
is a one~step
generates electrical energy from light energy.energy. The
The explanation
explanation relies on ideas
quantum theory.
from quantum theory. Light
Light isis made
made up up ofofpackets
packets ofof energy, called photons,
whose energy
whose energy depends
depends only
only upon
upon the frequency,
frequency, oror colour,
colour, of
of the
the light.
light. The
visible photons
energy of visible photons isis sufficient
suffcient to excite electrons,
electrons, bound into solids,
solids,
up to higher
higher energy
energy levels where they are more free
levels where free to move.
move. An extreme
extreme
example of
example of this
this is the photoelectric effect, the celebrated
celebrated experiment which
was explained
was explained byby Einstein in 1905, where blue
1905, where blue or
or ultraviolet light provides
provides
enough energy
enough energy forfor electrons
electrons to to escape completely from
escape completely from the
the surface
surface ofof a
metal. Normally, when light
Normally, when light isis absorbed
absorbed by by matter,
matter, photons are given up to
electrons to
excite electrons to higher
higher energy
energystatesstates within
within the
the material,
material, but
but the excited
quickly relax
electrons quickly relax back
back to to their
their ground
ground state. In aa photovoltaic
photovoltaic device,
device,

p n
metal

Current

Fig. 1.1.
Fig. 1.1. Comparison
Comparisonofofthe thephotoelectric
photoelectriceffect
effect (left),
(left), where
where uvuv light liberates electrons
from the surface
from of aa metal,
surface of metal, with
with the photovoltaic
photovoltaic effecteffect in
in aa solar
solar cell
cell (right).
(right). The
The
photovoltaic cell needs
photovoltaic cell needs toto have some spatial
have some spatial asymmetry,
asymmetry, such such asas contacts with different
different
electronic properties,
electronic properties, to
to drive
drive the excited electrons through
excited electrons through the external circuit.

11
 ., ~ .....

22 The Physics
The Physics of
of Solar
Solar Cells
Cells Introduction
Introduction 33

however, there
however, there is
is some
some built-in
built-in asymmetry
asymmetry which
which pulls
pulls the
the excited
excited electrons
electrons However, it was
However, it was not
not the
the photovoltaic
photovoltaic properties
properties of
of materials
materialslike
like sele-
sele-
away before
away before they
they can
can relax,
relax, and
and feeds
feeds them
them to
to an
an external
external circuit. The extra
circuit. The extra nium
nium which excited researchers, but the photoconductivity. The fact that
which excited researchers, but the photoconductivity. The fact that
energy of
energy of the
the excited
excited electrons
electrons generates
generates a potential difference,
a potential difference, or
or electro-
electro- the
the current
currentproduced
produced was
was proportional
proportional to
to the
the intensity
intensity of
of the
the incident
incident light,
light,
motive force (e.m.f.). This force drives the electrons through
motive force (e.m.f.). This force drives the electrons through a load in a load in the
the and
and related
related toto the
the wavelength
wavelength in in a definite way
a definite way meant
meant that
that photoconductive
photoconductive
external circuit
external circuit to
to dodo electrical
electrical work.
work. materials
materials were
were ideal for photographic
ideal for photographic light light meters.
meters. The The photovoltaic
photovoltaic effect effect
The effectiveness
The effectiveness of of aa photovoltaic
photovoltaic device
device depends
depends upon the choice
upon the choice ofof in barrier structures was an added benefit, meaning
in barrier structures was an added benefit, meaning that the light meter that the light meter
light absorbing materials and the way in which they are
light absorbing materials and the way in which they are connected to theconnected to the could
could operate
operate without
without aa power
power supply.
supply. It It was
was notnot until
until the
the 1950s,
1950s, withwith the the
external circuit.
external circuit. The
The following
following chapters
chapters will deal with
wil deal with the
the underlying
underlying phys-
phys- development
development of good quality
of good quality silicon
silcon wafers
wafers for for applications
applications in in the
the new
new solid
solid
ical ideas, the device physics of solar cells, the properties of
ical ideas, the device physics of solar cells, the properties of photovoltaic photovoltaic state
state electronics,
electronics, thatthatpotentially
potentiallyusefuluseful quantities
quantitiesof ofpower
power were were produced
produced
materials and
materials and solar
solar cell
cell design.
design. InIn this
this chapter
chapter wewe will summarise the
wil summarise the main
main by photovoltaic
by photovoltaic devices
devices in in crystallne
crystalline silcon.
silicon.
characteristics of
characteristics of aa photovoltaic
photovoltaic cell
cell without discussing its
without discussing its physical
physical function
function In
In the
the 1950s,
1950s, thethe development
development of of silicon
silicon electronics
electronics followed
followed the the discov-
discov-
in detaiL.
in detail. ery of a way to manufacture p-n junctions in silcon.
ery of a way to manufacture p-n junctions in silicon. Naturally n type siliconNaturally n type silcon
wafers developed aa pp type
wafers developed type skin
skin when
when exposed
exposed to to the
the gas
gas boron
boron trichloride.
trichloride.
Part
Part of of the
the skin
skin could
could be be etched
etched awayaway to to give access to
give access to the
the nn type
type layer
layer
1.2. Brief
1.2. BriefHistory
Historyof
of the
the Solar
Solar Cell
Cell
beneath. These p-n junction structures produced
beneath. These p-n junction structures produced much better rectifying much better rectifying
The photovoltaic
The photovoltaic effect
effect was
was first reported by
first reported by Edmund
Edmund Bequerel
Bequerel in
in 1839
1839 action
action than
than Schottky
Schottky barriers,
barriers, and better photovoltaic
and better photovoltaic behaviour.
behaviour. The The first
first
when he
when he observed
observed that the action
that the action of
of light
light on
on aa silver
silver coated
coated platinum
platinum elec-
elec- silcon
silicon solar
solar cell
cell was
was reported
reported by by Chapin,
Chapin, Fuller Fuller andand Pearson
Pearson in in 1954
1954 and and
trode immersed
trode immersed in
in electrolyte
electrolyte produced
produced an electric current.
an electric current. Forty
Forty years
years converted sunlight with
converted sunlight with an an effciency
efficiency of of 6%,
6%, sixsix times
times higher
higher than than the the best
best
later the first
later the first solid
solidstate
statephotovoltaic
photovoltaicdevices
devices were
were constructed
constructed by by work-
work- previous attempt. That
previous attempt. That figure
figure waswas toto rise
rise significantly
significantly over over thethe following
following
ers investigating the
ers investigating the recently
recently discovered
discovered photoconductivity
photoconductivity of of selenium.
selenium. In In years and decades but, at an estimated production cost of some $200
years and decades but, at an estimated production cost of some $200 per per
1876
1876 William
Wiliam Adams
Adams and Richard Day
and Richard Day found
found that
that aa photocurrent
photocurrent could could Watt, these
Watt, these cells
cells were
were not
not seriously
seriously considered
considered for for power generation for
power generation for sev-
sev-
be produced
be produced in in aa sample
sample of selenium when
of selenium when contacted
contacted by by two heated plat-
two heated plat- eral decades.
eral Nevertheless, the
decades. Nevertheless, the early
early silicon
silcon solar
solar cell
cell did
did introduce
introduce the the pos-
pos-
inum
inum contacts. The photovoltaic action of the selenium differed from
contacts. The photovoltaic action of the selenium differed from its
its sibilty of power generation in remote locations where
sibility of power generation in remote locations where fuel could not easily fuel could not easily
photoconductive
photoconductive action action inin that
that aa current
current waswas produced
produced spontaneously
spontaneously by by be delivered.
be delivered. The The obvious
obvious application
application was was to to satellites
satellites where
where the the require-
require-
the action of
the action of light.
light. No
No external power supply
external power supply waswas needed.
needed. In In this early pho-
this early pho- ment of
ment reliabilty and
of reliability and lowlow weight
weight mademade the the cost
cost of the cells
of the unimportant
cells unimportant
tovoltaic
tovoltaic device,
device, aa rectifying
rectifying junction
junction had been formed
had been formed between
between the the semi-
semi- and during
and during thethe 1950s
1950s and
and 60s, silcon solar
60s, silicon solar cellscells were widely developed
were widely developed for for
conductor and the metal contact. In 1894, Charles
conductor and the metal contact. In 1894, Charles Fritts prepared what Fritts prepared what applications in in space.
was
was probably
probably the first large
the first large area
area solar
solar cell
cell by
by pressing
pressing aa layer
layer ofof selenium
selenium Also in
Also in 1954,
1954, aa cadmium
cadmium sulphidesulphidep-n p-n junction
junction was produced with
was produced with an an
between
between gold
gold andand another
another metal.
metal. InIn the following years
the following years photovoltaic effects
photovoltaic effects effciency of
efficiency of 6%,
6%, and
and inin the
the following
following years years studies
studies of of p-n
rn junction
junction pho- pho-
were observed in copper-copper oxide thin film structures,
were observed in copper-copper oxide thin film structures, in lead sulphide in lead sulphide tovoltaic devices
tovoltaic devicesinin gallium
gallum arsenide, indium phosphide
arsenide, indium phosphide and and cadmium
cadmium tel- tel-
and
and thallium sulphide. These
thallum sulphide. These early
early cells
cells were
werethinthin film Schottky barrier
film Schottky barrier luride were stimulated by theoretical work indicating that these materials
luride were stimulated by theoretical work indicating that these materials
devices,
devices, where a semitransparent layer of metal deposited on top of
where a semitransparent layer of metal deposited on top of the
the would offer
would offer aa higher
higher efficiency.
effciency. However,
However, siliconsilcon remained
remained and and remains
remains the the
semiconductor
semiconductor provided
provided bothboth the asymmetric electronic
the asymmetric electronic junction,
junction, whichwhich is is foremost photovoltaic
foremost photovoltaic material,
material, benefiting
benefiting from from thethe advances
advances of ofsilicon
silcon tech-
tech-
necessary for photovoltaic action, and access to the junction
necessary for photovoltaic action, and access to the junction for the inci- for the inci- nology for
nology for the
the microelectronics
microelectronics industry.
industry. Short
Short histories
histories of of the
the solar cell are
solar cell are
dent
dent light.
light. The photovoltaic effect
The photovoltaic effect ofofstructures
structures like
likethis
this was
wasrelated
related toto the
the given
given elsewhere [Shive, 1959;
elsewhere Shive, 1959; Wolf,
Wolf, 1972;
1972; Green,
Green, 1990].
1990J.
existence of a barrier to current flow at one of the semiconductor-metal
existence of a barrier to current flow at one of the semiconductor-metal In the
In the 1970s
1970s thethe crisis
crisis inin energy
energysupply
supplyexperienced
experienced by bythethe oil-dependent
oil-dependent
interfaces (i.e.,
interfaces (i.e., rectifying
rectifying action)
action) byby Goldman
Goldman and and Brodsky
Brodsky in 1914. Later,
in 1914. Later, western world led to a sudden growth of interest in alternative sources
western world led to a sudden growth of interest in alternative sources of of
during
during the 1930s, the theory of metal-semiconductor barrier layers was
the 1930s, the theory of metal-semiconductor barrier layers was energy,and
energy, and funding
funding for for research
researchand and development
developmentinin those those areas.
areas. Photo-
Photo-
developed
developedby byWalter
WalterSchottky,
Schottky,Neville
NevileMott Mott and
and others.
others. voltaics was
voltaics wasaasubject
subject ofofintense
intenseinterest
interestduring
duringthis thisperiod,
period, and and aa range
range of of
 4 The Physics
The Physics of
ofSolar
Sola.rCells
Cells Introduction
Introduction 5
4 5

strategies for
for producing
producing photovoltaic
photovoltaic devices
devices and
and materials
materialsmore
morecheaply
cheaply
([000000000
000000000
~
strategies
and for improving device efficiency were explored. Routes to lower
and for improving device effciency were explored. Routes to lower cost costin-
in-
000000000
000000000
cluded photoelectrochemical
cluded photoelectrochemical junctions,
polycrystalline silicon, amorphous
junctions, and and alternative
silicon,
alternative materials
other 'thin
polycrystallne silcon, amorphous silcon, other 'thin film' materials and
materialssuch
film'
suchas
materials
as
and
~11111I1II111111II1I111b.
000000000
( 000000000
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organic conductors.
organic
other
conductors. Strategies
multiple band
Strategies for
gap designs.
for higher
higher effciency
Although
efficiency included
none of
included tandem
these led to
tandem andand
widespread
000000000
other multiple band gap designs. Although none of these led to widespread
commercial development,
development, our our understanding
understanding of ofthe
thescience
science ofof photovoltaics
photovoltaics
commercial
is mainly rooted in this period. OV-.r--~~~~~~~~h
~ ~ /-1 /-1 /-1 /-1 /-1 ~ h

~
OV
is mainly rooted in this period.
During the
During the 1990s,
1990s, interest
interest in in photovoltaics
photovoltaics expanded,
expanded, alongalong with
withgrow-
grow- rlrl r--1
r- r--1
r- f-1
r- f-1
r- r-
r--1 r- r--1r-f-1rl~
r--1r-
ing awareness of the need to secure sources of electricity
ing awareness of the need to secure sources of electricity alternative to alternative to
1"""1111111111111""1 ~~~~~~~~~h
~ /-1/-1/-1/-1/-1/-1/-1 f-l h
fossil fuels. The trend coincides with the widespread
fossil fuels. The trend coincides with the widespread deregulation of the
electricity markets
electricity markets andand growing
growing recognition
recognition of of the
deregulation
the viability
viabilty of
of the
of decentralised
decentralised qu""""'I"""""" +12V Y
+ 12V Y r- r- r- r- r- r- r- r- rl
r--1 r--1 f-1 f-1 r--1 r--1 r--1 f-1 ~
(a)
(a) (b)
(b)
power. During this period, the economics of photovoltaics improved pri-
power. During this period, the economics of photovoltaics improved pri-
marily
duction
through economies
marily through
expanded
economies of
at a rate
of scale.
of
scale. In
15-25%
In the
per
late 1990s
the late 1990s the
annum,
duction expanded at a rate of 15-25% per annum, driving a reduction in
the photovoltaic
driving
photovoltaic pro-
a reduction
pro-
in I r----,--~ +V
+V

I
cost. Photovoltaics first became competitive in contexts
cost. Photovoltaics first became competitive in contexts where conventionalwhere conventional
electricity supply
electricity supply isis most
most expensive,
expensive, for for instance,
instance, forfor remote
remote lowlow power
power ap-
ap-
plications such
plications such as navigation, telecommunications,
as navigation, telecommunications, and rural electrification
and rural electrification
and for enhancement of supply in grid-connected
and for enhancement of supply in grid-connected loads at peak use loads at peak use An-
[An-
I . Power
Power
derson, 2001]. As prices fall, new markets are opened
derson, 2001J. As prices fall, new markets are opened up. An important up. An important I
.
II
II
';..
.
';:
PV generator
PV generator
conditioning
conditioning
Load
Load
example
example is
the
is building
building integrated
photovoltaic system
integrated photovoltaic
system is is offset
photovoltaic applications,
offset by
applications, wherewhere the cost of
the cost of
,i
the photovoltaic by the savings in
the savings building materials.
in building materials. I

Storage
Storage
00 (Battery (de)
(Battery (dc)
1.3. Photovoltaic Cells
1.3. Photovoltaic Cellsand
andPower
Power Generation
Generation or Grid
or Grid (ae
(ac))

1.3.1. Photovoltaic cells, modules and systems (c)

(c) (d)
(d)
1.3.1. Photovoltaic cells, modules and systems
Fig. 1.2. (a) Photovoltaic cell showing surface contact patterns (b) In a module cells
Fig. 1.2. (a) Photovoltaic cell showing surface contact patterns (b) In a module cells
The solar cell
The solar cell isis the
the basic
basicbuilding
building block
block of
of solar
solar photovoltaics.
photovoltaics. The The cell
cell can
can are.usually
are. usuallyconnected
connectedininseries
seriestotogive
giveaastandard
standard dcdc voltage
voltage of
of 12
12 VV (c)
(c) For
For any
any ~ppli-
~ppli
be cat~on,modules
modulesare
areconnected
connectedininseries
seriesinto
intostrings
stringsand
andthen
theninin parallel
parallel into
into an
an array,
array,
be considered as a two terminal device which conducts like a diode in
considered as a two terminal device which conducts like a diode in the the cat~on,
dark which produc~ sufficient current and voltage to meet the demand. (d) In most cases
which produc~ suffcient current and voltage to meet the demand. (d) In most cases
dark andand generates
generates aa photovoltage
photovoltage when when charged
chargedbybythe
the
2
sun.
sun. Usually
Usually itit isis aa the photovoltalc
the photovoltaic array
array should
should be be integrated
integrated with
with components
components for
for charge
charge regulation
regulation and
and
thin
thin slice
slice of ofsemiconductor
semiconductormaterial material ofof around
around 100
100 cm
cm2ininarea.
area. The
The surface
surface storage.
storage.
isis treated
treated to reflect as little visible light as possible and appears dark blue
to reflect as little visible light as possible and appears dark blue
or
or black.
black. AApattern
pattern of of metal
metal contacts
contacts isis imprinted
imprinted onon the
the surface
surface to
to make
make
electrical
electricalcontact
contact (Fig.(Fig. 1.2(a)).
1.2(a)). 28 to
28 to 36
36 cells
cellsininseries,
series,totogenerate
generateaadc de output
output voltage
voltageof
of 12
12VV inin stan-
stan-
When
When chargedby
charged bythe
thesun,
sun, this
this basic
basic unit
unit generates
generates aa dc
dc photovoltage
photovoltage of of dard ilumination conditions (Fig. 1.2(b)). The 12 V modules
dard illumination conditions (Fig. 1.2(b)). The 12 V modules can be used can be used
0.5 to 1 volt and, in short circuit,
0.5 to 1 volt and, in short circuit, a photo
a photo current
current of
of some
some tens
tens of
ofmilliamps
miliamps singly, or connected in parallel and series into an array with a larger
singly, or connected in parallel and series into an array with a larger current current
2 . Although the current is reasonable, the voltage is too small for an~voltage
voltageoutput,
output, according
accordingto to the
the power
power demanded
demandedby bythe
the application
application
per
per cmcm2. Although the current is reasonable, the voltage is too small for an~
most
mostapplications.
applications. To To produce
produce useful
usefulde dcvoltages,
voltages,the
thecells
cellsare
areconnected
connectedto- to- (~lg.
(~ig.l.?(c)).
1.?(c)). Cells
Cellswithin
withinaamodule
moduleare areintegrated
integratedwith
with bypass
bypassand
and blocking
blocking
gether
gether in series and encapsulated into modules. A module typicallycontains
in series and encapsulated into modules. A module typically contains dIOdes ill order to avoid the complete loss of power which would result ifif one
diodes II order to avoid the cmplete loss of power which would result one
 6 The Physics of Solar Cells
The Physics Cells Introduction 7

cell
cell in
in the series failed.
the series failed. Modules
Modules within
within arrays
arrays are
are similarly
similarly protected. The
protected. The that ilumination.
illumination. Thus
Thus both II and
and VV areare determined
determined by the ilumination
illumination
array, which is
array, which is also
also called photovoltaic generator,
called aa photovoltaic generator, isis designed
designed to generate
to generate as well
as well asas the
the load.
load. Since
Sincethe
the current
current isis roughly
roughlyproportional
proportionalto to the
the illumi-
ilumi-
power at
power a certain
at a certain current
current and
and aa voltage
voltage which
which is
is some
some multiple
multiple of 12 V,
of 12 V, nated area,
nated area, the
the short
short circuit current
current density
density JseJ sc isis the
the useful
useful quantity
quantity for
under standard illumination. For almost all applications, the
under standard ilumination. For almost all applications, the ilumination is illumination is comparison. These quantities are defined
comparison. defined forfor a simple,
simple, ideal diode model of
too variable for efficient operation all the time and the photovoltaic
too variable for effcient operation all the time and the photovoltaic gener- gener- a solar cell
cell in
in Sec.
Sec. 1.4
1.4 below.
below.
ator must be
ator must be integrated
integrated with
with aa charge
charge storage
storage system
system (a (a battery) and with
battery) and with
components
components for for power
powerregulation
regulation (Fig.
(Fig. 1.2(d)).
1.2(d)). The battery isis used
The battery used toto store
store Box 1.1. Solar
Solar cell
cell compared
compared with conventional battery
charge
charge generated
generated during
during sunny periods and
sunny periods the power
and the conditioning ensures
power conditioning ensures
that The photovoltaic cell differs from
cell differs fromaa simple
simpledc dc battery
battery in these respects:
respects:
that the power supply is regular and less sensitive to the solar
the power supply is regular and less sensitive to the solar irradiation.
irradiation.
For the e.mJ.
e.mJ. of the battery
battery is is due
due to
to the
the permanent
permanent electrochemical
electrochemical potential
For ac
ac electrical
electrical power,
power, toto power
power ac ac designed
designed appliances
appliances andand for
for integration
integration
with an electricity grid, the dc current supplied by the photovoltaic modules difference between
difference betweentwo twophases
phasesinin the
the cell,
cell, while
while thethe solar cell derives
derives its
is
is converted
converted to ac power
to ac power of appropriate frequency
frequency using
using an an inverter.
e.m.f. from
e.m.f. from aa temporary change in electrochemical potential potential caused by light.
The The power delivered
delivered by by the
the battery
battery to aa constant load resistance
resistance isisrelatively
relatively
The design and engineering of photovoltaic systems is beyond
design and engineering of photovoltaic systems is beyond the scope
the scope
of this book. A more detailed
detailed introduction given by
by Markvart [Markvart, constant, while
constant, while delivered by
the power delivered
the power by the
the solar cell
cell depends
depends on on the
the incident
2000j and
2000] Lorenzo Lorenzo,
and Lorenzo
pends to aa large
cells.
large degree
introduction is given
[Lorenzo, 1994j.
1994]. Photovoltaic systems
degree upon the electrical
Markvart Markvart,
systems engineering
electrical characteristics of the
engineering de-de-
the individual
light intensity,
intensity, and and not
completely discharged when
although its output
although
since it can be
since
not primarily

output varies
primarily on the load
when itit reaches
varies with
be continually
with intensity,
continually recharged
intensity, is
load (Fig.
reaches the end of its
is in
recharged with light.
, ,
(Fig. 1.4).
1.4). The
its life,
The battery is
life while the solar
in principle
principle never
solar cell
never exhausted,
exhausted,
is
cell,

The battery
battery isis modelled
modelled electrically
electrically as a voltage
voltage generator and is char-
1.3.2. Some
1.3.2. Some important
important definitions
definitions acterised by
acterised by its e.mJ. (which,
(which, in practice,
practice, depends
depends upon the the degree
degree of of dis-
dis-
The solar cell
The solar cell can
can take
take the
the place
place ofof aa battery
battery in aa simple
simple electric
electric circuit charge), its charge capacity,
charge), capacity, and by by aa polarisation
polarisation curvecurve which
which describes
describes
(Fig. 1.3). In the dark the cell in circuit A does nothing. When it is
is switched
switched how the e.mJ.
how e.mJ. varies
varies with current
current Vincent
[Vincent 1997j.
1997]. The solar solar cell,
cell, in
in con-
con-
(Fig. 1.3). In the dark the cell in circuit A does nothing. When it
on develops aa voltage,
on by light it develops voltage, oror e.mJ.,
e.mJ., analogous
analogousto to the
the e.mJ.
e.mJ. of the trast, isis better
better modelled
modelled as as a current generator,
generator, sincesince forfor all
all but the largest
largest
battery in
battery in circuit
circuit B.
B. The
The voltage
voltage developed
developed when
when the
the terminals
terminals are isolated loads the current drawn
loads drawn is independent of load. load. But its characteristics
characteristics de- de-
(infinite load resistance)
resistance) isis called
called the open circuit
the open circuit voltage
voltage Voe'
Voc. The current pend entirely
pend entirely on on the
the nature
nature ofof the
the illuminating source, and
iluminating source, and so Isc and
so Ise Vac
and 'Ve
(infinite load The current
drawn when the terminals
drawn when the terminals are connected together
connected together is theis the short circuit cur-
circuit cur- must be quoted
quoted for for aa known
known spectrum,
spectrum, usually
usually for for standard test conditions
Isc. For any intermediate
rent Ise. intermediate loadload resistance
resistance RL the
the cell
cell develops
develops a voltage (defined below).
(defined below).
V between 00 and
V between andVoeVoc and
anddelivers current I I such
delivers aa current suchthat thatVV = = II RL
RL and
and
I(V) isis determined
determined by by the current-voltage characteristic
the current-voltage characteristic of the cell cell under
1.4. Characteristics
1.4. Characteristics of
of the
the Photovoltaic
Photovoltaic Cell:
Cell: A Summary
Summary

solar cell battery 1.4.1.

1.4.1. Photocurrent and
and quantum efficiency
quantum effciency

The photo current generated by a solar cell

The photo cell under
under illumination
ilumination: at
at short cir-
cir-
cuit is dependent on the incdent
incident light.
light. To
To relate
relate the
the photocurrent
photocurrentdensity,
density,
JJse,
sc , to the incident
incident spectrum wewe need the cell's quantum
quantum effciency,
efficiency, (QE).
(QE).
QE(E) is the probability that an incident photon of energy
QE(E) is the probabilty that an incident photon of energy E wil deliverE will deliver
one electron
one electron to
to the external circuit. Then
I,
Fig. 1.3.
Fig. 1.3.
(a)
(a)
The solar cell
cell may
may replace
replace aa battery
(b)
(b)
simple circuit.
battery in a simple JJse J
= qq J bs(E)QE(E)dE
sc = (1.1)
(1.1)

I,
Ii
88 Physics of
The Physics of Solar
Solar Cells
Cells Introduction
Introduction 99

~ " -OEo!
.-OEof gallium arsenide
gallium arsenide cell
cell
Voltage
-~
c --Solar photon
- Solar flux
photon dens~y
flux densny

ii
c ::.
Gl .
Battery e.m.l
Ballery e.mf 'C II
)( W
-
~a
c
go
.c
D.

200
200 400
400 600
600 800
8001000
10001200
1200 1400
1400 1600
1600 1800
1800

Wavelength I nm

Current Fig. 1.5. Quantum

Quantumeffciency
efficiencyofofGaAs
GaAscell
cell compared
compared to the solar
solar spectrum. The
The vertical
vertical
scale is in
scale is in arbitrary units,
units, for
for comparison.
comparison. The short circuit
circuit photocurrent
photocurrent is
is obtained
obtained
Fig. 1.4.
Fig. Voltage-currentcurves
1.4. Voltage-urrent curvesofofa aconventional
conventionalbattery
battery(grey)
(grey)and
anda asolar
solar cell
cell under
under by integrating the product
product of of the
the photon
photon flux
flux density.and
density -and QE
QE over
over photon energy.
energy. It is
is
different levels
different levelsof
ofillumination.
ilumination. A A battery normally delivers
battery normally delivers aa constant
constant e.m.f.
e.m.f. at
at different
different desirable to have
desirable to have aa high
high QE at wavelengths where the
wavelengths where the solar
solar flux
flux density is high.
levels of
levels of current
current drain except for
drain except for very
very low
low resistance
resistance loads,'
loads, when
when the e.m.f. begins
the e.m.f. begins to
to
fall . The
fall. The battery e.m .f. wil
battery e.m.f. will also
also deteriorate
deteriorate when
when the battery
batteryisisheavily
heavily discharged.
discharged. The
solar
solar cell
cell delivers
delivers aa constant
constantcurrent
current for
for any
any given
given illumination level while
ilumination level while the the voltage
voltage 1.4.2. Dark
1.4.2. Darkcurrent
currentand
andopen
opencircuit
circuitvoltage
voltage
is
is determined
determined largely
largely by
by the resistance of
the resistance of the load. For
the load. For photovoltaic
photovoltaic cells
cells itit is
is usual
usual to
to
plot the
plot the data
data in
in the
theopposite
opposite sense,
sense, with
with current
current on
on the
the vertical
vertical axis
axis and
and voltage
voltage on on the
the
When a load
load isis present,
present, a potential
potential difference
difference develops between the
develops between the termi-
horizontal axis. This
horizontal axis. is because
This is because the
the photovoltaic
photovoltaic cell
cell is
is essentially
essentially aa current source, while
current source, while
the battery isis aa voltage source. nals of the celL.
nals This potential difference
cell. This generatesaacurrent
difference generates current which
which acts
acts in
the battery voltage source.
opposite direction
the opposite direction to
to the photocurrent,
photocurrent, and and the net current
current is
is reduced
reduced
from its short circuit value.
from value. This reverse current is usually
reverse current usually called
called the
the dark
where bs(E)
where bs(E) isis the incident spectral
the incident spectral photon
photon flux density,
density, the number of
the number current inin analogy
analogy with the current Idark(V) which flows across
which flows across the device
photons of energy in the range
energy in the range E E to E +
+ dE which are incident on unit
which are incident on unit area under an applied voltage,
under voltage, oror bias,
bias, VV in the
the dark.
dark. Most
Most solar
solar cells
cells behave
behave
in unit time and q is the electronic charge. QE depends
is the electronic charge. QE depends upon the upon the absorption
like aa diode
like diode inin the dark,
dark, admitting
admitting aa much
much larger
larger current
current under
under forward
forward
coefficient
coeffcient of the solar cellcell material,
material, the effciency
efficiency of charge
charge separation
separation and bias (V
bias (V ?> 0)
0) than
than under
under reverse (V <
bias (V
reverse bias .. 0). This rectifying
rectifying behaviour
behaviour is
the efficiency of
the effciency of charge
charge collection
collection in the
the device
device but does
does not depend
depend on
aa feature ofof photovoltaic
photovoltaic devices, since an
devices, since an asymmetric
asymmetric junction is needed needed
the incident spectrum. It is therefore a key quantity in
the incident spectrum. It is therefore a key quantity in describing solardescribing solar
to achieve charge separation. For an ideal diode the dark current density
to achieve charge separation. For an ideal diode the dark current density
cell performance under different conditions. Figure 1.5 shows
cell performance under different conditions. Figure 1.5 shows a typical QE a typical
Jdark(V) varies
Jdark(V) varies like
spectrum in comparison
comparison with with the spectrum of solar photons.
QE
QE and spectrum can be
and spectrum can be given
given asas functions
functions of
of either
either photon energy or
photon energy or Jdark(V) = Jo(eqV/kBT - 1) (1.3)
wavelength, A.
wavelength, . Energy
Energy isis aa more
more convenient
convenientparameter
parameterfor for the
the physics
physics ofof
where JJo
where o isis aa constant,
constant, kB kB isis Boltzmann's
Boltzmann's constantconstant andand TT is temperature
solar cells and it will
solar cells and it wil be used in this book. The relationship between
between E E and
in degrees Kelvin.
in
A
isis defined
definedby by
overall current
The overall current voltage
voltage response
response of ofthe
the cell,
cell,its
its current-voltage
current-voltage char-
E= he (1.2) acteristic,
acteristic, cancan be approximated
be approximated as the sum of as
thethe
shortsum ofphoto
circuit the short circuit photo current
(1.2)
and the dark current
and current (Fig.
(Fig. 1.6).
1.6). This stepstep is is known
known as the superposition ap-
superposition ap-
where hh is
where Planck's constant
is Planck's constant and cc the
the speed
speed of
of light
light in
in vacuum.
vacuum. A
A con-
con- proximation. Although the the reverse
reverse current
current whichwhich flows
flows inin reponse
reponse to
to voltage
voltage
venient
venient rule
rule for
for converting
converting between
between photon energies,
energies, in
in electron-Volts,
electron-Volts, and
and in an
an illuminated
iluminated cell cell is
is not formally
formally equal
equal to the current which flows in the
flows in
wavelengths,
wavelengths,ininnm,
nm,isisE/eV
EjeV== 1240/(A/nm).
1240j(jnm). dark, the approximation is reasonable for
dark, for many
many photovoltaic
photovoltaic materials
materials and
and
r-

The
The Physics
Physics of
of Solar
Solar Cells Introduction
Introduction 11
11
10
10

JJsc
+
sc
.,
i-
v

cQ)
Light current
Light current J dark
't..
C
....
Q)
Dark
Dark current Fig. 1.
Fig. 1.7.7. Equivalent
Equivalentcircuit
circuitofofideal
idealsolar
solarcelL.
cell.
:J
(, Voc

photocurrent
photocurrent which which is is light
light dependent
dependent but bias independent.
but bias independent. At At VV :;> Voe,
Voe,
voltage, V
Bias voltage, the device
device again consumes
consumes power.power. ThisThis isis the
the regime where light
regime where light emitting
diodes.
diodes.operate.
operate.We We will see later
wil see later that
that in
insome
some materials
materials the
the dark current is
dark current is
Fig.
Fig. 1.6. Current-voltagecharacteristic
1.6. Current-voltage characteristic of
of ideal
ideal diode
diode in
in the
the light
lightand
and the
the dark.
dark. To
To
a first approximation,
approximation, the current is
is obtained
obtained byby shifting
shifting the bias
bias dependent d~rk
dependent d~rk
accompanied
accompanied by by the emission
emission of of light.
the net current
current up by
current up by aa constant
constant amount,
amount, equal
equal to short circuit
to the short circuit photocurrent.
photocurrent. The
The sign
sIgn Electrically, the
the solar
solar cell is equivalent
equivalent to to aa current generator
generator in
in parallel
convention isis such
convention such that
that the short circuit
circuit photocurrent
photocurrent isis positive.
positive. with an an asymmetric,
asymmetric, non linear resistive resistive ele~ent,
ele~ent, i.e.,
i.e., a
a diode
diode (Fig. 1.7).
1.7).
When illuminated,
When iluminated, theproduces
the ideal cell ideala cell
photo produces a photo current
current proportional to
will be used
wil be used for
for the
the present
present discussion.
discussion. The sign
sign convention for
for current
current and the light intensity. That That photocurrent
photocurrentisis divided
divided between
between the
the variable
variable resis-
resis-
voltage in
voltage photovoltaics isis such
in photovoltaics such that photocurrent is
that the photocurrent is positive.
positive. This isis tance of the diode and the load, load, in a ratio
ratio which
which depends on the resistance
resistance
the opposite
opposite to the
the usual
usual convention
convention for electronic
electronic devices. With
devices. With this sign
sign of the load and the level ilumination. For
level of illumination. For higher
higher resistances, more of the
convention the
convention the net
net current density in the cell
cell is
is photo current flows
photo flows through the diode, diode, resulting
resulting in aa higher
higher potential
potential differ-
ence between the
ence between the cell
cell terminals
terminals but but aa smaller
smaller current
current though
though the load. The
J(V) = Jse - Jdark(V), (1.4)
(1.4) diode thus provides photovoltage. Without
provides the photovoltage. Without the diode,
diode, there is
is nothing
to drive
drive the photocurrent through through the the load.
load.
which becomes, for an ideal diode,
becomes, for diode,

se -
J == Jse Jo(e qV /kBT
J - Jo(eav 1) ..
/kaT -- 1) (1.5)
(1.5)
1.4.3. Effciency
1.4.3. Efficiency
This result
result is
is derived
derived in Chapter 6.
6. operating regime
The operating regime of
of the
the solar
solar cell
cell is
is the
the range
range of
of bias, from
from 00 to Voe, in
to Voe,
When the
When the contacts
contacts are isolated, the potential difference has
potential difference has its
its maximum which the cell
cell delivers
delivers power. The cellcell power
power density
density is given
given by
by
value, the open circuitcircuit voltage Voe. This
voltage Voe' This is equivalent
equivalent to the condition
condition when
when
the dark current and short circuit photo current exactly cancel out. For the
the dark current and short circuit photo
P=JV. (1.7)
(1. 7)
ideal diode, from
from Eq. 1.5,
1.5,
kT
q (Jse
kT (Jse ))
Voe == q In
Voe J ++11 ..
In Jo (1.6)
(1.6)
P reaches
reaches aa maximum
point.
point. This
maximum at the
This occurs
occurs at
at some
the cell's
some voltage
cell's operating
voltage Vm
operating point
point or
or maximum
maximum power
power
with aa corresponding current density
Vm with
o
Jm,
J m , shown in Fig. 1.8. 1.8. The optimum
optimum loadload thus
thus has
has sheet
sheet resistance
resistance given
given
Equation 1.6
Equation 1.6 shows
shows that Voe increases
thatVoe increases logarithmically with light intensity.
intensity. by Vm/
Vm / JJm. The fill
m . The fill factor
factor isis defined
defined asas the ratio
Note that
thatvoltage
voltageisis defined
defined so that the photovoltage occurs in forward bias,
that the photovoltage occurs in forward bias,
where
where V V :;>O.
O. FF = JmVm (1.8)
Figure 1.6 shows
shows that current-voltage product is
is positive,
positive, and the
the (1.8)
Figure that the current-voltage Jse Vce
cell
cell generates power,
power, when the voltage is between 0 and Voe'
voltage is between and Voe' At V < 0, the
V -: 0, the and
and describes
describes the 'squareness'
'squareness' of
of the
the J-V
J-Vcurve.
curve.
illuminated device acts as a photodetector
iluminated device acts as a photo detector , consuming power to
to generate
generate aa
12
12 The Physics
The Physics of
of Solar
Solar Cells Introduction
Introduction 13
13

Max
Maxirmun Table 1.1.
Table 1.. Performance of
Performance of some
sometypes
types of
of PV
PV cell Green
[Green et
et al.,
al., 2001j.
2001] .
power point 2) 2)
Current density
Current Cell Type
Cell Type Area
Area (cm
(cm2) V oc (V)
V oc (V) J.
Jsc (mA/cm2)
c (mA/cm FF Efficiency
Effciency (%)
(%)
Jsc
crystalline Si
crystallne Si 4.0 0.706 42.2 82.8 24.7
Jm crystallne GaAs
crystalline GaAs 3.9 1.022 28.2 87.1 25.1
.. poly-Si 1.
1.1 0.654 38.1 79.5 19.8
to a-Si 1.0 0.887 19.4 74.1 12.7
ii CulnGaSe2
CulnGaSB2 1.0 0.669 35.7 77.0 18.4
i:
Q)
"C
CdTe 1.
1.1 0.848 25.9 74.5 16.4
..i: Power
density ,;
....
Q)
;f'''-fI'
~ ,/
o 80
"' /?
;/'" 70

Vm ! Voc rr N
N
60

Bias voltage, V , rI 'E

'E
u 50 c-Si

Fig. 1.8.
Fig. 1.8. TheThecurrent
currentvoltage
voltage(black)
(black) and
andpower-voltage
power-voltage (grey)
(grey) characteristics
characteristics of an
~
~
-<
-..,
-E
E 40 poly-Si
.....
poly-Si .

.
Power density reaches
ideal cell. Power reaches aa maximum
maximum at a bias Vm , close
bias Vm, to V
close to oc . The
Voc. The maximum
u CdTa GaAs
()
CIGS CdTe
power density 1m
power density Jm xX VmVm is given by the area area of the inner
inner rectangle.
rectangle. The outer
outer rectangle
rectangle II ..'"II 30

.
S'
has area lsc
has area oc . If
Jscxx VVoc. If the
the fill factor
factor were
were equal
equal to 1,I, the
the current
current voltage
voltage curve
curve would
would i

a-S'iI
a-
f
20
follow the outer
follow outer rectangle.
rectangle. r
i
!I 10
i
i

The effciency
efficiency r
1] of the cell
cell is
is the
the power
power density
density delivered
delivered at
at operating
operating [
r 0
0.5 0.6 0.7 0.8 0.9 1.1
1.1 1.2
Ps ,
I
point as
point as aa fraction
fraction of
of the
the incident light power
incident light density, Ps,
power density,

Voc N
VocN
r=-.
JmVrn
1]= - - .
P
JmVm
Pss
(1.9)
(1.9) I
l[
it Fig. 1.9.
Fig. 1.9. Plot J sc against
Plot ofof Jsc against Voc
V ocfor
for the
thecells
cells listed
listed in
in Table
Table 1.1.
1.1. Materials
Materials with
with high
high
Voc
V oc tend to
to have
have lower
lower Jsc.
J sc . This is
is due
due toto the
the band
band gap
gap of
ofthe
thesemiconductor
semiconductor materiaL.
material.
Efficiencyis
Effciency is related to JJse
related to se and Voe using
and Vce F F,
using F F, The grey
grey line
line shows
shows the relationship expectedexpected in the theoretical
theoretical limit.
limit.
Jse
JseVoe FF
VceF F
(1.10)
r
1]== (1.10)
Ps
Ps the band
band gap of the semiconductor.
semiconductor. In In Chapter 2 we
we will
wil see
see that there
there is is aa
These four
four quantities: J se , Voe,
quantities: Jse, Voe , F FF and
and r1] are
are the
thekeykeyperformance
performancechar- char- fundamental compromise between photocurrent and voltage
compromise between voltage in photovoltaic
acteristics of a solar
solar cell.
cell. All
All of
of these
these should
should be be defined
defined for particular il-
particular il- energy conversion. Figure
energy conversion. Figure 1.9
1.9 illustrates
ilustrates the
the correlation
correlation between J-s e and
between J"e and
lumination conditions.
conditions. The Standard
Standard TestTest Condition
Condition (STC)
(STC) for
for solar
solar cells
cells Voe for the
Voe for the cells in Table
cells in Table 1.1,
1.1, together
together with
with the relationship
relationship for
for a cell
cell ofof
is the
the Air
Air Mass
Mass 1.51.5 spectrum,
spectrum, an anincident
incidentpowerpower density
density of
of1000
1000 W Wm m -2,
- 2, maximum
maximum effciency.
efficiency.
and aa temperature
temperatureof of25C.
25C. (Standard
(Standardand andother
othersolar
solarspectra
spectraare
arediscussed
discussed
in Chapter
in Chapter 2.)2.) The
Theperformance
performance characteristics
characteristics for for the
the most
most common
common solar
solar 1.4.4. Parasitic
1.4.4. Parasitic resistances
resistances
cell
cell materials
materials are listed in Table
are listed in Table 1.1. 1. 1.
Table
Table 1.1
1.1 shows
shows that solarsolar cell
cell materials
materials with higher J sc tend to
higher Jse to have
have In
In real
real cells
cells power
power is
is dissipated
dissipated through
through the
the resistance
resistance of
of the
the contacts
contacts and
and
Voc. This
lower Voe'
lower This isis aa consequence
consequence of of the
the material
material used,
used, and
andparticularly
particularly of of ti.'.. through
through leakage
leakage currents around
around the
the sides
sides of
of the
the device.
device. These
These effects
effects are
are

!
rl

14 The
The Physics
Physics of Solar Cells
Cells Introduction 15

1.4.5. Non-ideal diode

1.4.5. Non-ideal diode behaviour
F\
+ The 'ideal'
'ideal' diode
diode behaviour
behaviour of
ofEq.
Eq. 1.5
1.5 isis seldom
seldom seen.
seen. ItIt isis common
common for
for the
the
dark current toto depend
depend more
more weakly
weakly onon bias.
bias. The actual dependence on V V
F\h v is quantified
is quantified by an
an ideality factor,
factor, m and the current-voltage characteristic
given
given by the non-ideal
by the non-ideal diode
diode equation,
equation,

J = Jse - Jo(eqV/mkBT - 1) (1.12)

(1.12)
Fig. 1.10. Equivalent
Fig. 1.10. Equivalentcircuit
circuitincluding
including series
series and
and shunt
shunt resistances.
resistances.

m typically lies
m between 11 and
lies between and 2. The reasons
2. for non-ideal
reasons for non-ideal behaviour
behaviour will
wil
be discussed
discussed in later chapters.

~c:
l!
~

I!
..
:i
rr 1.5. Summary
1.5. Summary
o (. Rsh decreasing
decreasing
Rs increasing
Rs increasing
r
L
A photovoltaic cell consists consists of aa light
light absorbing
absorbing material which is connected

Bias Bias !
!
to an external circuit
ated
ated in
towards one
the
circuit in
material by
in an
an asymmetric
the
asymmetric manner.
absorption
material by the absorption
one or or other
other ofof the
the contacts
contacts byby the
manner. Charge
of photons
photons
the built-in
Charge carriers are
of light, and
are gener-
are
built-in spatial asymmetry. This
gener-
driven
and are driven

(a)
(a) (b)
(b) light driven charge
light separation establishes
charge separation establishes aa photovoltage
photovoltage at at open circuit,
circuit,
Fig. and a photoa photo current at short
generates short circuit.
circuit. When
When aa loadload is
is connected to
Fig. 1.11. Effect of
1.11. Effect of (a)
(a) increasing
increasing series
series and (b) reducing
and (b) reducing parallel
parallel resistances.
resistances. In In each
each and generates

case
case the
the outer curve has
outer curve has R.Rs == 00 and R.h==00.
and R.h 00.InIneach
eachcase
casethe
theeffect
effect ofof the
the resistances
resistances the external circuit, the cell cell produces
produces both current and voltage and can do
reduce the area
is to reduce area of the maximum
maximum powerpower rectangle
rectangle compared
compared to J se xx Voc.
to Jsc Voe.
electrical work.
The sizesize ofof the current generated
generated by by the cell
cell in short circuit
circuit depends
depends
equivalent
equivalent electrically
electrically toto two
two parasitic
parasitic resistances
resistances in series (Rs)
in series (Rs) and in par- upon the intensity and the energy energy spectrum of the the incident
incident light.
light. Photocur-
(Rsh)
allel (Rsh)
allel with the cell (Fig. 1.10).
cell (Fig. 1.10). rent is related to incidentincident spectrum
spectrum by the quantum effciency efficiency of the
the cell,
cell,
The series
series resistance
resistance arises
arises from
from the
the resistance
resistance of of the cell material
the cell material to which isis the
which the probability
probabilty of of generating an electron incident photon as a
electron per incident
current flow, particularly
current flow, particularly through
through the
the front
front surface
surface to to the contacts,
contacts, and function of of photon
photon energy.
energy. When aa load load isis present,
present, a potential
potential difference
difference is.
is.
from
from resistive
resistive contacts.
contacts. Series
Series resistance
resistanceisisaa particular
particular problem
problem at high high created between terminals of the
between the terminals the cell
cell and
and this drives
drives aa current, usually
current densities, for
current densities, instance under
for instance concentrated light.
under concentrated light. The parallel
parallel or called the
called the dark
dark current,
current, in the opposite direction to the photocurrent.
opposite direction photocurrent. As As
shunt resistance arises
shunt resistance arises from
from leakage
leakage ofof current
current through
through the cell,
cell, around
around the load
load resistance
resistance is is increased,
increased, the potential
potential difference increases and
difference increases and the
the edges
edges of the device
device and between
between contacts
contacts of of different
different polarity.
polarity. ItIt is
is a net current
net current decreases
decreases until theuntil
photo the photo current
current and dark current
and dark current exactly
exactly cancel
cancel

poorly rectifying
problem in poorly rectifying devices.
devices. out. The potential
potential difference
difference at this point point isis called
called the open circuit
circuit voltage.
voltage.
Series andand parallel resistances reduce the the fill
fill factor asas shown
shown in Fig. 1.11.
1.11. At some point before before Voe Voc isis reached,
reached,the the current-voltage
current-voltage product is max- max-
For an efficient cell we want Rs to be as
For effcient cell we want Rs to be small and Rsh to assmall and Rsh to be as large as
as imum. This
imum. This is is the maximum
maximum power power point
point and
and the cell should
should be operated
possible. with a load
load resistance
resistance which corresponds to
which corresponds to this point.
When parasitic resistances
resistances are included,
included, the diode
diode equation
equation becomes
becomes The solar cell cell can
can bebe modelled
modelled as as aa current
current generator
generator in in parallel with an
diode, and
ideal diode, and thethe current-voltage characteristic given by the ideal diode diode
J = Jse _ Jo(eq(V+JARs)/kT _ 1) _ V +l:ARs. (1.11)
(1.11) equation, Eq. 1.5. In real
equation, real cells,
cells, the behaviour
behaviour is degraded by the presence presence
sh series and parallel resistances.
of series resistances.
1 16 The
The Physics
Physics of Solar Cells
Cells

References
D.
D. Anderson, Clean Electricity
Anderson, Clean Electricity from
from Photovoltaics,
Photovoltaics, eds.
eds. M.D.
M.D. Archer
Archer and R.D.
and R.D.
Hill (London: Imperial
Hil (London: Imperial College
College Press,
Press, 2001).
2001).
M.A. Green, "Photovoltaics:
M.A. Green, "Photovoltaics: Coming
Coming of of age", Conf. Record
age", Conf. Record 21st
21st IEEE Photo-
Photo- Chapter
Chapter 2
voltaic Specialists Conf.,
voltaic Specialists Conf., 1-7 (1990).
(1990).
E. Lorenzo, Solar Electricity:
Lorenzo, Solar Electricity: Engineering
Engineering ofof Photovoltaic
Photovoltaic Systems
Systems (Progensa,
(Progensa,
1994).
T. Markvart, SolarElectricity
Markvart, Solar Electricity(Wiley,
(Wiley, 2000).
2000).
Photons In, Electrons Out: Basic
Photons Basic
J.N. Shive, Semiconductor Devices
Shive, Semiconductor
C.A. Vincent, Modern
C.A.
Devices (Van Nostrand, 1959).
Modern Batteries (Arnold,
(Arnold, 1997).
1997).
1959). Principles of PV
M.
M. Wolf,
Wolf, "Historical development
development of solar
solar cells", Proc. 25th Power
cells", Proc. Power Sources
Sources Sym-
Sym-
posium, 1972. In
posium, 1972. In Solar Cells, ed. C.E.
Cells, ed. C.E. Backus (IEEE Press,
Press, 1976).
1976).

2.1. Introduction

I
I
In Chapter
Chapter 11 the
istics, in
istics,
we address
we
thesolar
in response
solarcell
response to
address some
some of
cellwas
to applied
was introduced
applied bias
introducedand"

of the thermodynamic
and" its performance
bias and light, were
performance character-
defined. In
were defined.
thermodynamic aspects of photovoltaic
character-
In this
this chapter
photovoltaic solar en-
conversion. The
ergy conversion. The chapter is organised as follows:
follows:first
first the
the radiant
radiant power
from the sun is defined;
available from defined; the photovoltaic cell is is distinguished from
other types
types of
of solar
solar energy
energy converter and the question
question ofof how
how much
much elec-
elec-
trical work can be extracted is is addressed;
addressed; the principle
principle of detailed balance
is introduced andand used
used to calculate
calculate the
the performance
performance characteristics
characteristics of an
photovoltaic energy
ideal photovoltaic energy converter.
converter. We shall see that effciency
see that efficiency depends
depends on
the band gapgap of
of the absorbing
absorbing material and the incident
incident spectrum. Finally,
Finally,
the properties
properties which
which are desirable
desirable for high effciency
efficiency in real
real photovoltaic
photovoltaic
t:
materials andand devices
devices are
are discussed.
discussed.

2.2. The Solar

2.2. The Solar Resource

The sun emits

emits light
light with
with aa range
range of
of wavelengths, spanning the ultraviolet,
wavelengths, spanning
visible and
visible and infrared sections
sections of the electromagnetic
electromagnetic spectrum. Figure Figure 2.12.1
showsthe
shows the amount
amount of of radiant
radiant energy receivedfrom
energy received from the
the sun
sun per
per unit area
area
per unit
per unit time
time -- thethe solar
solar irradiance
irradiance -- as as aa function
function of wavelength
wavelength at at a
point outside the Earth's
Earth's atmosphere.
atmosphere. Solar
Solar irradiance
irradiance is
is greatest
greatest at
at visible
visible
wavelengths,
wavelengths, 300-800
300-800 ur,nm, peaking
peakingin in the
the blue-green.
blue-green.
This extraterrestrial
extraterrestrialspectrum
spectrumresembles
resembles the spectrum
spectrum of ofaa black
black body
body
at 5760 K.
at 5760 K. A black body
A black body emits
emits quanta
quanta of of radiation
radiation - - photons
photons - - with a
distribution of energies determined by
energies determined by its characteristic
characteristic temperature,
temperature, Ts' Ts.
At a point
point ss on
on the
the surface
surface ofof the black
black body the number
number of photons with
energy in
energy in the
the range
range EE to to E ++ dE emitted
emitted through unit area area per
per unit
unit solid
solid

17
!
rr

16 The
The Physics
Physics of Solar Cells
Cells

References
D.
D. Anderson, Clean Electricity from
Anderson, Clean from Photovoltaics,
Photovoltaics, eds.
eds. M.D.
M.D. Archer
Archer and R.D.
R.D.
Hill (London: Imperial
Hil (London: Imperial College
College Press,
Press, 2001).
2001).
M.A. Green, "Photovoltaics:
M.A. Green, "Photovoltaics: Coming
Coming of of age", Conf. Record
age", Conf. Record 21st
21st IEEE Photo-
Photo- Chapter
Chapter 2
voltaic Specialists Conf.,
voltaic Specialists Con/. , 1-7 (1990).
(1990).
E. Lorenzo, Solar Electricity:
Lorenzo, Solar Electricity: Engineering
Engineering ofof Photovoltaic
Photovoltaic Systems
Systems (Progensa,
(Progensa,
1994).
T. Markvart, SolarElectricity
Markvart, Solar Electricity(Wiley,
(Wiley, 2000).
2000).
Photons In, Electrons Out: Basic
Photons Basic
J.N. Shive,
C.A.
Semiconductor Devices
Shive, Semiconductor Devices (Van Nostrand, 1959).
Modern Batteries (Arnold,
1959). Principles of PV
C.A. Vincent, Modern (Arnold, 1997).
1997).
M. Wolf, "Historical development
M. Wolf, development of solar
solar cells", 25th Power
cells", Proc. 25th Power Sources
Sources Sym-
Sym-
posium, 1972.
posium, In Solar
1972. In Cells, ed.
Solar Cells, ed. C.E.
C.E. Backus (IEEE Press,
Press, 1976).
1976).

2.1. Introduction

I
I
In Chapter 11 the
istics, in
istics,
we address
we
the solar
in response
solar cell
response to
address some
some of
cell was
to applied
was introduced and
applied bias
of the thermodynamic
its performance
and'its
bias and light, were
performance character-
defined. In
were defined.
thermodynamic aspects of photovoltaic
In this
this chapter
photovoltaic solar en-
conversion. The
ergy conversion. The chapter is organised as follows:
follows:first
firstthe
the radiant
radiant power
available from
available from the
the sun is defined;
defined; the photovoltaic cell is is distinguished from
other types
types of
of solar
solar energy
energy converter and the question
question ofof how
how much
much elec-
elec-
trical work can be extracted is is addressed;
addressed; the principle
principle of detailed balance
is introduced andand used
used to calculate
calculate the
the performance
performance characteristics of an an
photovoltaic energy
ideal photovoltaic energy converter.
converter. We shall see that effciency
see that efficiency depends
depends on
the band gap of the absorbing material and the incident incident spectrum. Finally,
Finally,
the properties
properties which
which are desirable
desirable for high effciency
efficiency in real
real photovoltaic
photovoltaic
materials andand devices
devices are
are discussed.
discussed.

2.2. The Solar

2.2. The Solar Resource

The sun emits lightlight with

with aa range
range of
of wavelengths, spanning the ultraviolet,
wavelengths, spanning
visible and
visible and infrared sections
sections of the electromagnetic
electromagnetic spectrum. Figure Figure 2.12.1
showsthe
shows the amount
amount of of radiant
radiant energy receivedfrom
energy received fromthe
the sun
sun per
per unit area
area
per unit
per unit time
time -- the the solar
solar irradiance
irradiance -- as as aa function
function of
of wavelength
wavelength at at aa
point outside the Earth's
Earth'satmosphere.
atmosphere. Solar
Solar irradiance
irradiance is
is greatest
greatest atat visible
visible
wavelengths, 300-800
wavelengths, 300-800 nm, nm, peaking
peaking inin the blue-green.
This extraterrestrial
extraterrestrialspectrum
spectrumresembles
resembles the spectrum
spectrum of of aa black
black body
body
at 5760 K.
at 5760 K. A A black
black bodybody emits
emits quanta
quanta of of radiation
radiation - - photons
photons - - with a
distribution of energies
distribution determined by
energies determined by its characteristic temperature, Ts. Ts.
At aa point
point ss on
on the
the surface
surface of the black body the number
number of photons
photons with
energy in
energy in the
the range
range EE to E + + dE emitted
emitted through
through unit area
area per
per unit
unit solid
solid

I
I
17
r

I
I
18
18 Physics of
The Physics of Solar
Solar Cells
Cells photons
Photons In, Electrons
Electrons Out: Basic
Basic Principles of PV
PV 19
19
I
I
angle per
angle per unit
unittime,
time,the
thespectral
spectralphoton
photonflux f3s(E,s, s,B,B,cP),
fluxs(E, ), is
is given
given by
by
II
.
f3s(E, s,
s, B,B,)dO.dSdE = =h3h3c2
2(
2 ( E2
E2 )) dO.dSdE (2.1)
s(E, cP)dn.dSdE E / kBT _ _1 1 dn.dSdE
c2 eeE/kBT. (2.1)

where dS
where element of surface
dS the element surface area around s and
area around and dO.
dO the unit
unit of
of solid
solid
angle around the direction
angle direction of ofemission
emission of
of the
the light
light(B,(B,cP).
). The flux
flux issued
issued
normal to the surface is given
normal to the surface is given by the by the component of /3s
s integrated over solid
resolved along dS,
angle and resolved dS,
Box 2.1.
2.1. The angular
angular resolved photonflux
resolved photon density,/3,, isis the
flux density, the number
number of
s)dSdE ==~ s(E,
bs(E, s)dSdE In
/3s(E, ) . cos
B,B,cP)
s, s, BdO.dSdE
cosBdn.dSdE photons of
photons of given
given energy
energy passing
passing through
throughunit
unit area
area in
in unit
unit time,
time, per
per unit
unit
solid angle. It is defined
solid angle. defined onon an element
element of surface area, and its direction
surface area, direction
= 2Fs
= 2Fs( ( E2
E2 ) )dSdE
dSdE (2.2) is defined by the angle to the
defined by the surface
surface normal,
normal, B,
B, and an azimuthal
azimuthal angle,
angle,
h 3 c2 eE/kBT. 1 (2.2)
h3c2 eE/kBTs -- 1 , projected
cP, projectedononthe
theplane
planeof ofthe
the surface
surfaceelement.
element.InInstructures
structures with
with planar
Fs is aa geometricaL,
where Fs geometricat factor symmetry it is
is suffcient
sufficient to
to know
know the
the photon
photon flux
flux density
density resolved
resolved along the
where factorwhich
which arises
arisesfrom
from integrating over the
integrating over
relevant angular normal to the
the surface,
surface, b. is obtained by integrating the components of /3
b. b is
relevant angular range.
range. Just
Just at the surface
at the surface of the black
black body this
this range
range I
is a hemisphere
hemisphere and Fs = Away from the surface, the angular range is normal to the
the surface
surface over
over solid
solid angle.
angle.
and Fs = 1r.
1r. the surface, angular range is
reduced and
The emitted energy flux density
energy flux densityor
or irradiance,
irradiance,L(E),
L(E), isis related
related to
to the
Fs = 1f sin2 Bsun (2.3)
(2.3) photon flux density through
where BsunBsun
where is theishalf
theangle
half tended by
sub angle sub tended by the
the radiating body to the point
radiating body point
L(E) == Ebs(E)
Ebs(E) .. (2.4)
where the flux flux isis measured.
measured. For For the
the sun
sun asas seen
seen from
from the earth,
earth, Bs Bs == 0.26
0.26 so
so
4 5
that
that FsFs is
is reduced
reduced by by aa factor of
of 4.6
4.6 x 10104 to
to 2.16
2.16xx1O- 1r. IfIfthe
10-51f. thetemperature
temperature Integrating
Integrating Eq.
Eq. 2.4 over E
2.4 over gives the total
E gives total emitted
emitted power density, asTs,
power density, asTs,
at all points
at all points ss on on the
the surface
surface ofof the
the black
black body
body isis the
the same,
same, then
then the
the where as
where as is Stefan's constant,
argument s can be dropped from bs, bs , and Eq. 2.2 can
and Eq. 2.2 can be be written
21f55 kk44
21T
as = 15c2h3 .
bs(E) =
2Fs( ( E2
2Fs E2 )) (2.2) as = 15c2 h 3
bs(E) = h 3 c2 .
h3c2. eE/kBT. _ 1 .
eE/kBTs _ 1 . (2.2)
At the sun's
sun's surface
surface this is is aa power
power density
density of 62 MW m- 2 . At a point
m -2. point
In the remaining
remaining sections
sections of
of this
this chapter we
we will bs and Fs
wil use bs Fs to repre- just outside the Earth'sEarth'satmosphere
atmospherethe thesolar
solarflux
flux isis reduced
reduced (on
(on account
account ofof
sent
sent the spectral photon
photon flux
flux and geometrical
geometrical factor
factor for
for the sun. the reduced angular range of the sun) sun) and the solar power density is reduced
2
to 1353
1353 W W m-m-2. In Fig. 2.1 the extraterrestrial solar spectrum is compared
2.1 the
with the spectrum
spectrum of of aa 5760
5760 K black body, reduced by the factor factor 4.6 10 4
4.6 xx 104.
The higher
The higher Ts, Ts, thethe higher
higher the average
average energy
energy of of the
the emitted radiation.
radiation.
A black
black body
body at the the temperature
temperature of of the
the Earth,
Earth, Ts Ts == 300
300 K, emits
emits most
most
strongly in
strongly in the
the farfar infrared
infrared andand itsits radiation cannot
cannot be seen. For the sun,
seen. For
with TsTs == 5760
5760 K K the emission
emission isis strongest
strongest atat visible
visible wavelengths.
wavelengths. AA hotter
hotter
sun would
sun would emitthatlight
emit light that
appears blue appears blue to to us,
us, with
with a spectrum shiftedshifted to
shorter wavelengths
shorter wavelengths on on Fig.
Fig. 2.1,
2.1, and
and aa cooler
cooler sun
sun would
would appear
appear red.
On passing
On passing through
through the the atmosphere,
atmosphere, light light isis absorbed
absorbed andand scattered
scattered by by
various atmospheric
various atmosphericconstituents,
constituents,so sothat
that the
the spectrum
spectrum reaching
reaching thethe Earth's
Earth's

I
I
20
20 The Physics
The Physics of
of Solar
Solar Cells
Cells Photons
Photons In, Electrons
Electrons Out: Basic
Basic Principles of
of PV
PV 21
21

'7'7
EcE
c
C)I
22 ~--~-----------------------------------.
-AM)
-AM)
."M-5960K
"'~- 5960Kblack
black body spetrum
body spectrum
-e-
/ \\
-e-
/
ci
E -AM1.5
--AM 1.5

-
E
::
-
::
CI)
CI
() datm
()
c datm
c
.!!!
.!!
"t
'C AMI.S
AMI.S
.....
as
CI
.!::
.=
o o o o o o o
8
'"
8 8 8'" 8.. 8IX 8ai o8 oo o
o
'"
o'" g o
.. 16 ai 8'"
Fig. 2.2.
Fig. If the
2.2. If the atmosphere has thickness
atmosphere has thickness datm,
datm, then
then when the sun
when the sun isis at
at an
an angle
angle of
of
-l '" ~ ~ ~ ~ ~ elevation 'Yo,
iS' light
light from
from the sun
sun has
has to
to travel
travelthrough
throughaadistance
distancedatm
d atmxxcosec
cosecIS
'Y. through
through
the atmosphere
atmosphere to an an observer
observer on the Earth's
Earth's surface.
surface. The
The optical
optical depth
depth of
of the
the atmo-
atmo-
Wavelength I nm

I
sphereisisincreased
sphere increased
by aby a factor
factor nAirMa
nAirMass = cosec iS compared to when the sun is
= cosec'Y. is directly
directly
overhead.
overhead .
Fig. 2.1.
Fig. 2.1. Extra-terrestrial
Extra-terrestrial(Air
(AirMass
Mass0)0)solar
solarspectrum
spectrum (black
(black line)
line) compared
compared with
with the
the
5760 K
5760 K black
black body
body spectrum
spectrum reduced
reduced by
by the factor 4.6
the factor 104 (thick
4.6 xx 104 (thick grey
grey line)
line) and with
and with I
the standard
the standard terrestrial (Air Mass
terrestrial (Air Mass 1.5)
1.5) spectrum
spectrum (thin grey line).
(thin grey line).

surface
surface isis both attenuated
attenuated andand changed
changed in in shape.
shape. Light
Lightofofwavelengths
wavelengths less
less
than
than 300300 nm
run is
is filtered
filtered out
out by
by atomic
atomic and
andmolecular
molecular oxygen,
oxygen, ozone,
ozone, and
nitrogen.
nitrogen. Water
Water andand CO2
CO 2 absorb
absorb mainly
mainly in in the infrared and
the infrared and are
are responsible
responsible
for
for the dips in
the dips in the
the absorption
absorption spectrum
spectrum at at900,
900, 1100,
1100, 1400
1400 and
and 1900
1900 nm
run
(H 2
(H20) 0) and at 1800 and 2600 nm
and at 1800 and 2600 nm (C02), (C0 ), Attenuation by the atmosphere
2 Attenuation by the atmosphere is is
quantified
quantified by the 'Air
by the 'Air Mass' factor, nAirMass
Mass' factor, defined as
nAirMass defined as follows
follows
optical path
optical path length to Sun
nAirMass = optical path length if Sun directly overhead
nAirMass = optical path length if Sun directly overhead
cosec "Is
= cosec "Is . (2.5)
(2.5)
where "Isisisthe
where "Is theangle
angleof ofelevation
elevationofofthe
thesun,
sun, as
as shown
shown in in Fig.
Fig. 2.2.
2.2. The
The Air
Mass nAirMassspectrum
Mass nAirMass spectrumisisan anextraterrestrial
extraterrestrial solar
solar spectrum
spectrum attenuated
by nAirMass
nAirMass thicknesses
thicknessesofofan anEarth
Earth atmosphere
atmosphereof of standard
standard thickness
thickness and
Fig.
Fig. 2.3. Globaldistribution
2.3. Global distribution of
of annual average solar
annual average solar irradiance.
irradiance. The values on
The values on the
the irra-
irra-
composition.
composition. 2.
diance contours
diance contours are given
given in
in W
W m-m -2.
The
The standard
standard spectrum
spectrum for for temperature
temperature latitudes Air Mass
latitudes isis Air Mass 1.5,
1.5, or
or
AM1.5,
AM1.5, corresponding
correspondingtoto the the sun
sun being
being at an
an angle
angle of
of elevation
elevation ofof 420.
42.
This atmospheric thickness
This atmospheric thickness should
should attenuate
attenuate the
the solar
solar spectrum
spectrum to a mean
to a mean and orientation of
and orientation of the
the Earth
Earth and
and condition of of the
the sky.
sky. Averaged global
Averaged global
irradiance of around 900 W m- 2 However, for convenience, the standard 2
irradiance of around 900 W m-2. However, for convenience, the standard irradiances vary
irradiances vary from
fromless
lessthan
than 100
100WWm-m-2 atat high
high latitudes to over 300
300 WW
terrestrial
terrestrial solar spectrum is defined
defined asas the
the AM1.5 spectrum normalised
normalised so so m-22 in the sunniest
m- sunniest places
places (usually, desert area
(usually, desert area in
in continental
continental interiors),
interiors), as
as
that integrated irradiance
that the integrated irradiance is 1000 W
is 1000 W m -2.-2. Actual irradiances
irradiances clearly
clearly shown in
shown in Fig.
Fig. 2.3.
2.3. (Solar
(Solarradiation
radiation and
and spectral variations are discussed
discussed byby
vary
vary on
on account
account of of seasonal
seasonalandand daily
dailyvariations
variationsinin the
the position
position of
of the
the sun
sun [Gottschalg,
lGottschalg, 2001].)
2001).)

I
I
"T
I
22
22 The Physics
Physics of
of Solar
Solar Cells
Cells Photons
Photons In, Electrons Out: Basic
Electrons Out: Basic Principles
Principles of PV
PV 23
23
I
efficient solar
For effcient solar collection,
collection, the
the solar
solar collector
collector should be
be directly
directly facing
facing be extracted, the
the excited
excited state should
should be separated from
from the ground state
However, variations
the sun. However, variations in
in the
the position
position of the sun
sun mean
mean that
that any flat by an
an energy
energy gap
gap which
which isis large compared to
to kBT,
kBT, where
where kB
kB is Boltzmann's
Boltzmann's
plate collector in aa fixed
collector in position will
fixed position wil face
face the
the sun
sun only part of
of the
the time.
time. constant. Therefore
Therefore the
the material
materialshould
should contain
containtwo
two or
ormore
moreenergy
energylevels,
levels,
Tracking systems
systems can be used to follow
follow the
the sun
sun but these increase
increase the cost.
cost. or bands,
bands, which are separated
which are separated by
by more
more than
than kBT.
kBT. In
In Chapter
Chapter 3 we
we wil
will
Scattering light by
Scattering of light by the atmosphere
atmosphere means
means a fraction
fraction of the light
light is
is see that aa semiconductor
see that semiconductor is is a veryvery good
good example
example of such such aa system.
system. TheThe
diffuse, i.e.,
diffuse, i.e., incident
incident from angles rather
from all angles rather than
than direct from the
the sun.
sun. This
This separation
separation of of the energy
energy bands, or or band
band gap, serves to
gap, serves to maintain the excitedexcited
fraction
fraction is around 15% 15% on on average,
average, but
but larger
larger at
at higher
higher latitudes, and in in electrons at at the
the higher
higher energy
energy for a long long time
time compared
compared to to the
the thermal relax-
regions where there
regions where there isis aa significant
significant amount
amount of cloud
cloud cover.
cover. Diffuse
Diffuse light ation time,
time, so so that
thatthey
theymay maybe be collected.
collected. Electrons
Electrons in in each
each of the different
presents different
presents different challenges for photovoltaic conversion. Since Since the
the light rays bands relax to form a local thermal equilibrium, equilbrium, calledcalled aa quasi
quasi thermal
thermal equi-
equi-
are not parallel,
are parallel, they
they cannot
cannot be
be refracted
refracted or concentrated.
concentrated. Materials
Materials with librium, with
librium, with aa different
different chemical potential, or,
chemical potential, or, quasi
quasi Fermi level. In
Fermi leveL. In aa two
two
rough surfaces are relatively
surfaces are relatively better suited
suited for
for diffuse
diffuse light than
than perfectly
perfectly band system,
system, the increase increase in in electrochemical potential energy
electrochemical potential energy is given by by
flat surfaces and areare less
less sensitive to movements
movements of the sun. the Gibbs
Gibbs free free energy, D.t., where
energy, N D./l-, where NN is the number of electrons promoted
and D.t.
!:!./l- the difference
difference in the chemical potentials between between the excited popu-

2.3. Types
2.3. Types of
of Solar
Solar Energy

The photovoltaic
Energy Converter

photovoltaic device
Converter

should be
device should be distinguished
distinguished from
from both
both solar thermal
I
I
lationandand
lation

from
from the absorption
radiation. In
radiation.
energy from
the ground
the ground

absorption of
In equilibrium,
of light
equilbrium, D.t.
population. The difference in D.t.
state The
state population.

light is is sometimes
sometimes called
D./l- == o.
from light in this way is most effective
O. Extraction
difference
called the chemical
Extraction of
which results
D./l- which
chemical potential of
of electrochemical potential
electrochemical potential
when the
effective when the ground
ground state is is full
and photochemical energy converters.converters. Solar energy conversion
Solar thermal energy conversion re-
sults from thethe heat
heat exchange
exchange between
between aa hot hot body (the sun) sun) andand aa cool
cool one
one initially and the excited
initially excited statestate is is empty.
empty.
(the solar thermal device). Photochemical conversion is,
(the solar thermal device). Photochemical conversion is, like photovoltaic like photovoltaic Unlike the
Unlike the solar
solar thermal converter,
converter, the photovoltaic converter converter extracts
conversion,
conversion, aa quantum conversion process
quantum energy conversion process but
but one which
which results in a solar energy
solar energy only only from
from those
those photons
photons with with energy
energy sufficient
suffcient to to bridge
bridge the
permanent increase
increase in in chemical
chemicalpotential
potential rather than electric
electric power.
power. To dis- band
band gap. gap. Since
Since these
these mainly increase increase the electrochemical
electrochemical potential en- en-
tinguish these different types of solar energy converter, we need to consider ergy the increase
ergy increase in internal
internal energy
energy is much much less.
less. InIn practice,
practice, increased
increased
the different modes of energy energy transfer from
from the sun. temperature can decrease decrease the the efficiency
effciency of photovoltaic conversion conversion and so so
The radiant
radiant energy
energy absorbed by by a device
device can either increase the kinetic photovoltaic
photovoltaic cells cells are designed
are usually usually designed
to be to be in good thermal contact
in good thermal contact with
with
energy of
energy of the
the atoms
atoms andand electrons
electrons inin the
the absorbing material (the internal
absorbing material the ambient.
ambient.

energy), or
energy), or it can increase
increase the potential
potential energy
energy of the electrons.
electrons. Which of To complete
To complete the photovoltaic
photovoltaic conversion process, the
conversion process, the excited electrons
these happens
these happens depends
depends uponupon the
the material
material andand howhow itit is
is connected
connected to to the must be extracted
extracted and and collected.
collected. This This requires
requires aa mechanism
mechanism for for charge
charge sep-
outside world.
outside world. In In aa solar
solar thermal converter
converter thethe radiant energy
energy absorbed is aration. Some
aration. intrinsic asymmetry
Some intrinsic asymmetry is is needed
needed to to drive
drive the excited electrons
converted
converted mainly
mainly into energy and
into internal energy and raises
raises the
the temperature
temperature of the away from
away from theirtheir point of of creation.
creation. (In (In general,
general, charge
charge separation
separation involves
involves
cell.
cell. The difference
difference in in temperature
temperature relative
relative to
to the ambient means means that
that the positive holes
positive holes and/or
and/or ions as well well as electrons.
electrons. We We describe
describe the process in
solar converter
solar converter cancan operate
operate asas aa heat engine
engine and do work, work, for instance by terms of electrons for for simplicity.)
simplicity.) This This can
can bebe provided by selective
selective contacts
contacts
driving aa steam
driving steam turbine to generate
generate electric
electric power.
power. Solar
Solar thermal converters such that
such that carriers with raised raised /l- t. (excited state) are collected
(excited state) collected at at one
one contact
utilise
utilse the
the full
full range
range ofof solar
solarwavelengths,
wavelengths, including
including thethe infrared,
infrared, and
and are
are and those
and those with with low /l- t. (ground
(ground state) at the the other.
other. The
The difference
difference in chemi-
chemi-
designed to
designed to heat
heat up easily. They are
easily. They are thermally
thermally insulated
insulated fromfrom the ambient cal potential between
cal contacts, D./l-,
between the contacts, D.t., then
then provides
provides aa potential
potential difference
to working temperature
to make the working difference as large as possible.
temperature difference possible. between the
between the terminals
terminals of of the
the cell.
cell. Once separated, the charges
Once separated, charges should
should be
A photovoltaic converter,
A photovoltaic converter, on the other hand, is designed to
on the other hand, is designed to convert
convert allowed to
allowed to travel
travel without
without lossloss to to an
an external
external circuit
circuit and do electrical work. work.
the incident solar
the incident solar energy mainly into
energy mainly into electrochemical
electrochemical potential
potential energy.
energy. Photovoltaic conversion
Photovoltaic conversion isis similar
similar to photochemical
photochemical energy conversion conversion
Absorption of
Absorption of aa photon
photon in in matter
matter causes
causes thethe promotion
promotion of of anan electron
electron to
to aa (e.g. in
(e.g. photosynthesis), in
in photosynthesis), in that radiant energy
that radiant energy produces
produces an an increase
increase in in
state
state of higher energy
energy (an state). For
excited state).
(an excited For the
the extra
extra electronic energy
energy toto electronic potential energy,
electronic potential energy, rather than heat. rather than heat. In the case
case of photosynthesis
 l'
I
24 of Solar
The Physics of Solar Cells
Cells Photons In, Electrons
Electrons Out:
Out: Basic
Basic Principles
Principles of PV 25
25

stale
Excited state
~
Means of
Integrating over
normal to
over directions,
to the
directions, we
the surface
obtain the incident flux of thermal photons
we obtain
surface of a flat plate
plate solar
solar cell
cell
2Fa ( E2 )
charge
separation ba(E) = h3c2 eE/kBTa-l (2.6)

slale
where
where the geometrical factor Fa
geometrical factor Fa == 1f, assuming that
7r, assuming that ambient radiation is
is
Ground state
received over aa hemisphere.
received over hemisphere. The
The equivalent
equivalent current density
density absorbed from
from
Fig. 2.4.
Fig. Excitation and
2.4. Excitation and charge
chargeseparation.
separation. After
After an
an electron
electron is
is promoted to aa higher
promoted to higher the ambient
ambient is
is
energy level
level by
by absorption
absorption ofof aa photon
photon of
of sufficient
sufcient energy,
energy, it must
must bebe pulled
pulled away
away from
from
point of
the point of promotion
promotion byby some
some mechanism
mechanism for
for charge separation. The
The driving
driving force
force for
for jabs(E) = q(1
I jabs(E) q(1 -- R(E))a(E)ba(E) (2.7)
:1
charge separation prevents
charge separation prevents the
the relaxation
relaxation of
of the
the system
system to
to its initial state.
I
where a(E) is the probabilty
where a(E) probability ofof absorption
absorption of a photon
photon of energy
energy E E and
I
population drives
drives aa chemical
chemical reaction, the
the conversion
conversion of
R(E) isis the
the probabilty
probabilityofofphoton
photonreflection.
reflection. jabs(E) is
is the electron current
i the excited electron population
CO 2 and
density equivalent to
density equivalent to the absorbed
absorbed photon
photon flux
flux if
if each
each photon
photon ofof energy
energy

i CO2 and water
water into
into carbohydrate,
carbohydrate, rather
rather than
than driving anan electric
electric current.
current.
.1. E generates
generates one electron. a(E) is
one electron. is known
known as as the absorbance or
the absorbance or absorptivity,
:1 But in
But in either
either case
case the
the solar
solar energy results in a net flux of electronic
electronic potential
potential
energy constituting
constituting work. I and is determined
determined by by the
the absorption
absorption coefficient
coeffcient of of the
the material and by the
II
energy work. The different modes
The different of solar
modes of solar energy conversion
energy conversion
optical path
optical path length
length through
through the the device.
device.
II are explained
are in detail
explained in detail by
by de
de Vos [de Vos,
Vos de Vos, 1992).
1992].
the following
following sections
To
To obtain the total total equivalent
equivalent current
current forfor photon
photon absorption,
absorption, Eq. 2.7 2.7
1I
In the sections we
we will amount of
wil calculate the amount of work
work available
available
jm should
should be be integrated
integrated over over the
the surface
surface of of the
the solar
solar collector.
collector. The result
result
photovoltaic device.
from a photovoltaic device.
:~
depends on
depends on the interface
interface at at the rear
rear surface.
surface. If the the rearrear surface
surface contacts
contacts
:~
:f~ the air,
the air, then
then both sides contribute
both sides equally, and
contribute equally, and thethe equivalent
equivalent current
current is
is
II 2.4. Detailed Balance
2.4. Detailed 2qA(1-- R(E))a(E)ba(E)
2qA(1 R(E))a(E)ba(E) for for a collector
collector of of area
area A. A. If the the rear
rear surface
surface
is
is in
in contact
contact withwith aa material
material of of higher
higher refractive
refractive index,
index, n s , the rate
ns, rate of
of
.11
;H
1

i1;
One
One of of
the the fundamental
fundamental

voltaic cell arises from

physical physical limitations on the performance of a photo- photon absorption isis enhanced
photon absorption enhancedby n;
by n; over
over that
that surface,
surface, and and the result is is
from the principle of detailed balance. As well as
the as absorbing q(1 + n;)A(1 - R(E))a(E)ba(E). In the case of a perfect
perfect reflector (which
q(1 + n;)A(1 - R(E))a(E)ba(E). In the case of a
Ii solar radiation the the solar
solar energy exchanges thermal
energy converter exchanges
:Ii
i.~ thermal radiation
radiation with is capable
is capable of of reflecting
reflecting thermal
thermal photons) at the the rear
rear surface,
surface, the equivalent
" its surroundings.
surroundings. Both the the cell
cell and
and the
the surrounding
surrounding environment
environment radiate
radiate current for
current for absorbed
absorbed thermal
thermal photons
photonsisisonlyonlyqA(1 qA(1- - R(E))a(E)ba(E).
R(E))a(E)ba(E). In
i
long
long wavelength,
wavelength, thermal,thermal, photons
photons on on account
account of
of their
their finite
finite temperature. this case the areas for for thermal photon and solar photon photon absorption are the
II
I'li

Iii
The rate of of emission
emission of of photons
photons by by the
the cell
cell must
must be
be matched
matched by by the
the rate of same, and
same, and the
the device
device efficiency
effciency is is the
the greatest.
greatest. In In the following
following analysis
analysis we
we
photon absorption, so that in in the
the steady
steady state the concentration
concentration of of electrons
electrons assume that
assume that this is is the
the case.
case.
, ,I in the material remains remains constant. As well
As well asas absorbing
absorbing thermal
thermal photons,
photons, the the cell
cell emits
emits thermal photons
'Ii
II,
by spontaneous
by spontaneous emission. Spontaneous emission
emission. Spontaneous emissionisis the the conversion
conversion intointo a
2.4.1. In equilibrium
2.4.1. In equilibrium photon of the potential
potential energy
energy released when an excited electron relaxes
released when relaxes to
its ground state
state (Fig.
(Fig. 2.5).
2.5). (Stimulated
(Stimulated emission,
emission, discussed in Chapter Chapter 4, can
First we consider
consider the
the cell
cellininthe
thedark,
dark, in
inthermal
thermal equilibrium
equilbrium with the ambi- be neglected
neglected sincesince thethe solar
solar cell
celloperates
operates in in aa limit
limit where
where the the excited
excited state
ent.
ent. Assuming
Assuming that
that the ambient radiates like aa black body at a temperature is almost empty.) This This emission
emission is necessary
necessary to to maintain
maintain a steady state.
T a , then,
Ta, then, according
according toto Eq.
Eq. 2.1,
2.1, itit produces
produces aa spectral
spectral photon
photon flux
flux at
at a point A cell
A in thermal equilbrium
cell in equilibrium with with its
its surroundings,
surroundings, i.e., i.e., receiving
receiving no
ss on
on the surface
surface of
of the
the solar
solar cell
cell of radiation other than from from the ambient, has temperature Ta and emits ther-

f3a(E, s, (), )dn.dSdE = =h3h3c2

2 ( ( E2
2
c2 eE/kBTa E2 )) mal radiation characteristic
mal characteristic of of that
that temperature.
temperature. If If EO is
is the emissivity
emissivity (or
a(E,s,B,cP)dn.dSdE eE/kBTa_ _1 1 dn.dSdE.
dn.dSdE. probability
probabilty of of emission of of aa photon
photon of of energy E) E) the
the equivalent
equivalent current
current
T
Ii
I; 26
26 Physics of
The Physics of Solar
Solar Cells
Cells Photons
Photons In,
In, Electrons
Electrons Out:
Out: Basic
Basic Principles
Principles of
of PV 27
27

l the
the rate
rateof
ofemission
emission depends
depends upon
upon 6i..
6.f.l. This
Thismakes
makessense
sensesince
since when
whenmore
more
hv
hv electrons are at raised
raised energy,
energy, relaxation events are more
events are more frequent.
frequent. Accord-
J hv
hv
iJ ~> >
~ ing to a generalised
generalised form of Planck's
Planck's radiation law, the spectral
spectral photon
photonflux flux
,I emitted from
from aa body
body ofof temperature
temperature Tc andand chemical
chemical potential 6i.
6.f.l into
into aa
medium of of refractive
refractive index
index ns
ns is
is given
given by
by
il 2n2 E2
2n 2 E2
absorption spontaneous emission
spontaneous emission (E,
(3(E,s,s,B,
B, cP)
) == h3;2 e(E-~JL)/kBTa __ 11
h3;2 e(E-;ltt)/kBTa (2.11)
Fig. 2.5.
Fig. Absorption and
2.5. Absorption and spontaneous
spontaneousemission.
emission. In
In spontaneous emission, also
spontaneous emission, also known
known
as radiative recombination, the electron
electron relaxes
relaxes from
per unit
per unit surface
surface area
area and
and solid
solid angle
angle Wuerfel,
[Wuerfel, 1982;
1982; de
de Vos,
Vos, 1992).
1992]. Inte-
Inte-
as from excited
excited state
state to ground state giving
its extra
out its extra potential
potential energy
energy as
as aa photon
photon of
of light.
light. grating over
over the range
range of
of solid
solid angle
angle through
through which
which photons
photons can
can escape
escape
::; BB ::
(0 :: ::; Be)
Be) we
we obtain
obtain the
the photon flux emitted normal
normal to
to the
the surface
surface
photon emission
density for photon emission through the
the surface
surface of the cell is given by 2n2 E2
be(E,6i.) = Fe h3;2 e(E-;ltt)/kBTa _ 1 (2.12)
jrad(E) = q(1
jrad(E) q(1 -- R(E))(E)ba(E).
state, the
In order to maintain a steady state,
jrad (Eq. 2.8) must balance and therefore
jrad (Eq. 2.8) must balance and therefore
R(E))e:(E)ba(E).
the current
currentdensities
densities jabs (Eq. 2.7)
jabs (Eq. 2.7) and
(2.8)
(2.8)
I
I where
. Be
Fe = 1fsin 2 =n~
1f2 (2.13)
ns
e:(E) a(E) ..
(E) = a(E) (2.9)
(2.9)
and
This is a result of
of detailed balance: In
detailed balance: In quantum
quantum mechanical
mechanical terms,
terms, it results
from
from the fact that
the fact that the
the matrix
matrixelement
element for
for optical
optical transitions
transitions from
from ground
ground
11
B
Ue . .-1
e = =SInSln (no)
-1 (no)
ns
ns
to excited state and
and from excited
excited to
to ground
ground state
state must
must be
be identicaL.
identical.
by Snell's law, where
Snell's law, no
where no isis the
the refractive
refractive index of the surrounding medium.
2.4.2. Under illumination
2.4.2. Under illumination
At a surface
surface with air, no 1, Fe
with air, no = Fe XX n~
n; == Fa
Fa ==1f
1r and

Under
Under illumination by aa solar
ilumination by solar photon
photon flux
flux bs(E) (Eq.
(Eq. 2.2),
2.2), the cell
cell absorbs
2Fa E2
be(E,6i.) = h3c2 e(E-;ltt)/kBTa _ 1 . (2.14)
solar photons of energy E at
solar photons of energy E at a a rate
Note that this
Note that this result
result isis the
thesame
same whether the integration
whether the integration is
is taken
taken over
(1
(1 -- R(E))a(E)bs(l?)'
R(E))a(E)bs(E) . internal or external
internal external solidsolid angle: internally, ns
angle: internally, ns must
must be
be retained
retained but
but the
The equivalent angular range
angular rangeisislimited
limited toto Be,
Be,while
whileexternally
externallynsns== 11 but the
the angular
angular
equivalent current
current density
density for includes aa contribu-
for photon absorption includes
tion from
from thermal photons, hence
hence range is a hemisphere.
range
Now ifif e isis the probabilty
Now probability of of photon
photon emission,
emission, the equivalent
equivalent current
jabs(E)
jabs(E) == q(1-
q(1 -R(E))a(E) (bs(E)++
R(E))a(E) (bs(E) (1- ~:) ba(E))
(1 - ~:) ba(E)) (2.10)
(2.10)
for photon emission
density for emission is

jrad(E) q(l -- R(E))(E)be(E,

jrad(E) == q(1 R(E))e:(E)be(E, 6i.).
6.f.l). (2.15)
where
where the
the coefficient
coeffcient ofof bba
a is
is introduced
introduced to to allow
allow for
for the fraction of
the fraction of the
incident
incident ambient flux flux which
which hashas been
been replaced
replaced byby solar
solar radiation.
radiation. It is easy to see
see that Eq.
Eq. 2.15
2.15 reduces to Eq.
reduces to Eq. 2.8
2.8 for
for the
the cell
cell in
in equilibrium,
equilbrium,
As
As aa result
result of of illumination,
ilumination, part
part of
of the
the electron
electron population
population has raised
has raised where aa = e and
where 6.f.l ==O.
and 6i. O. It
It isis not
notimmediately
immediately obvious
obvious howhow a(E) relates
relates
electrochemical
electrochemicalpotential
potential energy,
energy,andand the develops a chemical
the system develops chemical po- to (E)
to e(E) for
for the
thecell
cellwith
with6i.
6.f.l~>O.O.However,
However, itithas
hasbeen
beenshown
shownelsewhere
elsewhere
6.f.l ~> O.
tential 6i. O. In these
these conditions
conditions spontaneous
spontaneous emission
emission is increased and Araujo, 1994)
[Araujo, from a generalised
1994] from detailed balance
generalised detailed balanceargument
argument thatthat Eq.
Eq. 2.9
2.9
7

28 The
The Physics
Physics of Solar Cells
Cells Photons
Photons In, Electrons
Electrons Out: Basic Principles
Principles of PV 29
I
still holds, provided
stil holds, f}.J-L isis constant
provided that /:/- constant through
through the
the device.
device. That result
result

~~
will
wil bebe used
used below
below without
without proof.
proof.
The net
net equivalent
equivalent current
current density,
density, from
from Eqs. 2.10
2.10 and 2.15
2.15 is, (

excited state
jabs(E) -- jrad(E)
jabs(E) jrad(E)

=
= q(l-- R(E))a(E)
q(1 (bs(E) ++ (1 +
R(E))a(E) (bs(E) (1
+ ~:) ba(E) - be(E,
~:) ba(E) be(E,f}.J-L)). (2.16)
/:/-)). (2.16)
'v -lAS
-!A Eg

This may be divided

divided into contributions
contributions from
from net absorption (in
(in excess
excess to
that at equilbrium),
equilibrium), U ground state
0o 0
!!ts
jabs(net)(E) = =q(l
jabs(net)(E) q(1- -R(E))a(E)
R(E))a(E)(bs(E) ~: ba(E))
(bs(E)-- ~: (2.17)
(2.17) o

net emission,
and the net

jabs(net)(E) ==q(l
jabs(net)(E)
recombination current density
emission, or radiative recombination

q(1- - R(E))a(E)(be(E,
R(E))a(E)(be(E, f}.J-L)
/:/-) -- be(E,
be(E, 0)),
0)), (2.18)
(2.18)
I
I
Fig. 2.6.
Fig.

excess
2.6. Two
an electron
Two band
electron to
excess energy
photon with E;;;;
band photoconverter.
to the
energy isisquickly
E Eg
it is the incident
quicklylost
lostasasheat
Eg achieves
incident photon
photon flux
heatas
the same
achieves the
flux and not
Photons with
photoconverter. Photons
the excited
excited state.
state. Photons
Photonswith
asthe

not the
with EE ~ Eg
the carriers
carriers relax
same result
result as
the photon
energyEE <.. Eg
with energy
Eg can
relax to
as aa photon
photon energy
can raise
to the
Eg cannot

the band edges.

photon with
energy density
cannot promote
raise the electron
promote
electron but any
edges. An absorbed
with EE == Eg.
E g For
density which
any

For this reason

which determines
reason
determines the
photogeneration.
photogeneration. Once Once excited
excited the
the electrons
electrons remain
remain in in the
the excited
excited state
state for a relatively
relatively
noting
noting that ba(E) == be(E,
that ba(E) be(E, 0).
0). This
This radiative
radiative recombination is an
recombination is an unavoid-
unavoid- long time.
able loss which means that absorbed solar
able loss which means that absorbed solar radiant energy
energy can never be
never be
fully utilised
fully utilsed by
in Chapter 4.
by the
the solar
solar cell.
cell. Radiative
Radiative recombination
recombination is discussed further
i at short
short circuit
circuit by
by integrating
integratingjabs
jabs over
over photon
photon energies
energies

I
4.

2.5. Work
2.5. WorkAvailable
Availablefrom
fromaaPhotovoltaic
Photovoltaic Device
Device
I
sc =
JJse 100

= q 100 'T/c(E)(l
7/e(E)(1- -R(E))a(E)bs(E)dE.
R(E))a(E)bs(E)dE. (2.19)
(2.19)

Now
Now wewe have
have enough
enough information
information to to calculate
calculate thethe absolute limiting
limiting eff-
effi- This is identical
identical to Eq.
Eq. 1.1
1.1 with the
the quantum effciency QE(E) given
quantum efficiency given by
ciency of
ciency of aa photovoltaic converter. We
photovoltaic converter. Wewillwil consider
consider aa two band band system
system
the product of
of the
the collection
collection and
and absorption
absorption effciencies.
efficiencies.
for which
for which thethe ground
ground state (lower band) is
(lower band) is initially
initially full
full and the the excited
excited
state (upper
(upper band)
band) empty. The bands
empty. The bands are separated
separated by by aa band gap, gap, Eg,
Eg ,
so light with E ..<Eg
so that light Egisisnot
notabsorbed
absorbed(see(see Fig.
Fig. 2.6).
2.6). We
We wilwill assume
assume Jse = q 100 QE(E)bs(E)dE (1.1)
(1. 1)
that electrons
that electrons in each
each band are inin quasi
quasi thermal
thermal equilibrium
equilbrium at the ambient
temperature Ta and the chemical potential for
chemical potential for that band,
band, /-i.
J-Li. For the case of the most effcient
For efficient solar cell
cell we
we will
wil suppose
suppose that we we have a
perfectly absorbing,
perfectly non-reflecting material
absorbing, non-reflecting material so
so that all incident
that all
that that incident pho-
pho-

2.5.1.
2.5.1. Photocurrent
energy EE >
tons of energy :; Eg
Eg are
are absorbed to promote exactly one electron
electron to the
upper band. We We further suppose
suppose perfect charge that all
charge separation so that all elec-
elec-
Photocurrent
Photocurrent is is due to the
due to the net
net absorbed
absorbed flux
flux due
due to
to the
the sun,
sun, Eq.
Eq. 2.17.
2.17. trons which survive
survive radiative recombination
recombination areare collected by the negative
collected by negative
Since the
Since the angular
angular range
range of
of the
the sun
sun is so
so small compared
compared to the ambient,
ambient, terminal of the cell
terminal cell and delivered
delivered toto the
the external circuit (i.e. 7/e(E)
'T/c(E) == 1).
1).
the second
second term in in Eq.
Eq. 2.17
2.17 is
is usually
usually neglected.
neglected. If each
each electron has a
electron has This gives
This gives the maximum
the maximum photo current for
photo current for that band
band gap,
gap, assuming
assuming that
'T/c(E), of being collected,
probability, 7/e(E), we obtain
collected, we obtain the photocurrent density
density multiple carrier
multiple carrier generation
generation-- the thepromotion
promotion ofof more
more than
than one
one electron
electron by

I
I
r

30 The
The Physics
Physics of Solar Cells
Cells Photons
Photons In,
In, Electrons
Electrons Out:
Out: Basic
Basic Principles
Principles of PV 31

an
an absorbed
absorbed photon
photon -- does
does not
not happen.
happen. Then
Then For the special case of the step-like absorption function (Eq. 2.20),
2.20),

QE(E) = a(E)
QE(E) a(E) == {i ~ ~ E;: Eg
E-:Eg
(2.20)
(2.20) J(V) roo
J(V) == qqroo ~bs(E)
{bs(E) -_ (be(E,
lEg
lEg
(be(E, qV)
qV) -- be(E,
be(E, O))}dE
O)HdE ,, (2.24)
(2.24)

and J(V) isis strongly

strongly bias
bias dependent
dependent through the
the exponential
exponential term in
in Eq.
Eq. 2.12
2.12
has the
and has the approximate form
JJse roo
sc == qq roo bs(E)dE
lEg
bs(E)dE .. (2.21)
(2.21)
=
J(V) = Jse
Jsc -- Jo(eqV/kBT 1)
Jo(eqV/kBT -- 1)
lEg J(V)

Photocurrent
Photocurrent isis then then aa function
function only
only of the
the band
band gap
gap and and the the incident
incident where JJo
where o isis aa (temperature
(temperature dependent)
dependent) constant
constant for
for the
the particular
particular materiaL.
material.
spectrum.
spectrum. Clearly, the lower lower E g , the
Eg, the greater
greater will
wil be J sc . It
be Jse' It isis also
also clear from This resembles
resembles the the ideal diode Eq. 1.4.
1.4.
Eq. 2.21
Eq. 2.21 that itit isis necessary
necessary to define
define the spectrum for for any statement of The net electron
electron current is is thus
thus due
due to
to the
the difference
difference between
between the two
efficiency.
effciency. photon flux
flux densities:
densities: the absorbed flux, which is
flux, which is distributed over a wide wide
range of photon
range photon energies abovethe
energies above the threshold
threshold EEg, g , and
and the emitted
emitted flux,
flux,
2.5.2. Dark current
2.5.2. Dark current
which isis concentrated
which concentrated on on photon
photon energies
energiesnearnear EEg. g As
As V
V increases,
increases, the
emitted flux
emitted increases and
flux increases and the
the net current decreases.
decreases. At At the open
open circuit
Dark current
current is
is the current that
that flows
flows through
through the
the photovoltaic
photovoltaicdevice
device when voltage Voc
voltage Voe the the total
total emitted
emitted flux
flux exactly
exactly balances
balances the the total
total absorbed flux
absorbed flux
a bias is applied
applied in in the dark. WeWe will suppose that in
wil suppose in the
the ideal
ideal cell
cell mate-
mate- and the net
and net current
current is is zero.
zero. If V V is
is increased stil further,
increased still further, thethe emitted
emitted
rial no
no carriers
carriers are
are lost
lost through
through non-radiative
non-radiative recombination,
recombination, for for example
example flux exceeds
flux exceedsthe the absorbed
absorbed and and the
the cell
cell begins
begins toto act
act like
like aa light emitting
emitting
at
at defects
defects within
within thethe material.
materiaL. The only loss
The only loss process
process considered
considered is is the
the un-
un- device, giving
device, giving out out light
light in
in return for the applied
applied electrical potential
potential energy.
energy.
avoidable
avoidable radiative spontaneous emission,
radiative relaxation of electrons through spontaneous emission, Note that
that Voe Voc must always
always be be less ~g.
less than Egoq
The
The spectral fluxes
fluxes leading to
described
described above.
above. The The dark
dark current density
density due to thisthis process
process is
is given
given by these regimes
these regimes are areillustrated
ilustrated in Fig. 2.7(a), while Fig.
2.7(a), while Fig. 2.7(b)
2.7(b)illustrates
ilustrates the
integrating jrad over photon energy and,
integrating jrad over photon energy and, for a flat for a flat plate cell with perfect
cell with perfect resulting J(V)
resulting curves.
J(V) curves.
rear reflector, is given by

J
Jrad(1::..)= =q q J(1(1- -R(E))a(E)(be(E,
Jrad(Ap,) D..)- - be(E,
R(E))a(E)(be(E, Ap,) be(E,O))dE, (2.22)
O))dE, (2.22)
2.5.3. Limiting effciency
2.5.3. Limiting

To calculate
To
efficiency

calculate the power

power conversion effciency we
conversion efficiency weneed
need to
to calculate
calculate the in-
in-
assuming that
assuming Ap, is
that D.. is constant over
over the surface
surface of the cell
cell and
and using
using the
the cident and
cident and extracted
extracted power from the photon
power from photon fluxes.
fluxes. The incident
incident power
power
detailed balance result, a(E) == (E).
balance result, e(E).InInideal
idealmaterial
materialwith
withlossless
lossless carrier
carrier density is
density is obtained simply by integrating
simply by integrating the incident irradiance (Eq.
(Eq. 2.4)
2.4)
transport
transport D.. Ap, can be
be further
further assumed
assumed constant
constant everywhere equal to
everywhere and equal to qq over
over photon energy,
photon energy,
times the applied bias V Araujo,
[Araujo, 1994).
1994]. Then, assuming
assuming that
that dark current
current
and photocurrent
and photocurrent can can be added,
added, as
as in Eq. 1.3
1.3 Ps = 100 Ebs(Es)dE. (2.25)
(2.25)

J(V) = Jse - Jdark(V) ,

For the output
output power
power we need to
we need to know
know the
the electrical
electrical potential
potential energy of
the extracted
the extracted photo-electrons.
photo-electrons. converter it is
For the ideal photo converter
For the ideal photo is assumed
assumed
we
we obtain for
for the net
net cell
cell current
current density,
density,
that no
that no potential
potential isis lost
lost through
through resistances
resistances anywhere in the circuit. There-

J(V) 1 00

J(V) == qq 100 (1
(1 - - R(E))a(E){bs(E)
R(E))a(EHbs(E) -- (be(E,
(be(E, qV)
qV) -- be(E,
be(E, O))}dE. (2.23)
O)HdE. (2.23)
fore all collected electrons should have
Ap, of work to the
deliver D.. the external
have Ap,
external circuit.
D.. of
of electrical
electrical potential
circuit.Since
potential energy
Ap, == qV
Since D.. qVwe
energy and
wehave
have for
and
for the
the
rI
j 32
32 Physics of
The Physics of Solar
Solar Cells
Cells Photons
Photons In,
In, Electrons
Electrons Out:
Out: Basic
Basic Principles
Principles of
of PV 33
33

1.E+22
1.E+22 extracted power
extracted power density
density from
from Eq.
Eq. 1.6
1.6
I
\
\
\ Pp=
= VVJ(V)
J(V)
\
I
.. \ with
with J(V)
J(V)given
givenby
byEq.
Eq.2.24
2.24above.
above. The
Thepower
powerconversion
conversion effciency
efficiency is
is
::CI \ \
r-h. VJ(V)
('
'E : '{X Ps
r
7=]V
= J(V)
Ps .
--. (2.26)

--
.......'(I)
-
, (I

o
(I)
(I
c
r;:
g
O.E+OO
O.E+OO
o
O..0
0 !0.8' 1.00 1.20 1.40

""''""''<~ Absorbed solar

-,~",,,',,,"'Absorbed flux
solar flux
1. o
1. 0
Maximum effciency
efficiency is
is achieved
achieved when
when
d
dV (J(V)V)
dV (J(V)V) = o.
= o. (2.27)
o
.s::.
.c - -- -- -- Emitted
- Emitted (V <Voc)
N.cVoc) The
The bias
bias at
at which
which thisthis occurs
occurs is
is the
the maximum
maximum power
power bias,
bias, Vrn
Vm introduced
introduced
c..
D. --+- in
-- NetNet flux N.cVoc)
flux (V<Voc) in Chapter
Chapter 1.1. In
In Fig.
Fig. 2.7(b)
2.7(b) the
the output
output power
power density
density for
for aa 0.7
0.7 eV
eV band
band gap
gap
--Emitted
- (V>Voc)
Emitted N.;"voc) photoconverter
photoconverter in in aa black body sun
black body sun isis plotted
plotted as
as aa function
function of bias. At
of bias. At the
the
__ Net flux
---Net fluxN::"voc)
(V>Voc) maximum, VrnVm == 0.45
0.45 V, the
the power
power conversion effciency is
conversion efficiency is around
around 20%.
20%.
-1.E+22

Photon Energy leV 2.5.4. Effect of band

2.5.4. Effect band gap
(a)
(a)
Given
Given all all of assumptions
of the the assumptions made
made above, the powerabove, the
conversion power conversion efficiency of
effciency

1000 0.3 the ideal two band photoconverter is

the ideal two band photoconverter is a function only a function only of
of Eg
Eg and
and the
the incident
incident
800 .. spectrum. If .the incident spectrum is fixed, then 7] depends only on
spectrum. If. the incident spectrum is fied, then r depends only on the
the
0.2 band gap. Intuitively we can see
we can see that
that very small and and very large band gaps
('
N
c:-ci 600
'E
'e E e will lead to
wil lead to poor
poor photoconverters:
photoconverters: in in the
the first
first case
casebecause
because the
the working
working

--.- ~
400 0.1
c(
cr value of
value of V is is too
too small,
small, (Vrn,
(Vm, like
like Voc, is always
Voe, is always less
lessthan
than Eg)
Eg) and
and in
in the
the
3:
3=
~
200 >- second because the photo current current is too smalL. For any spectrum
small. For any spectrum there is
~-
second because the photo
~
.- -
~ 0 CJ
c:
C an optimum band
(I) .-
c(/
.- 0 an band gap
gap at
at which
which r7] has
has aa maximum.
maximum. Figure
Figure 2.8
2.8 shows
shows the
the
c: (/
(I)
06 .u
Q)
Q)
'u variation of r 7] with Eg
Eg calculated
calculated in this this way
way for the
the standard
standard AM1.5
AM1.5 solar
-... ...
Q) c:
Q) C -200 solar
"C
"C Q) Q) -0.1 ==
_ "C "C
c: ..
C -400 LIJ
LI ==
.. 0~~
~
~ -600 -Oment density
-Q.ient density -0.2 0.40. 4 0 , - - - - - - - - - - - - - - - ,
0
:i 0
:J __ Power
Power density
00 a.
D. -800 density
A"-Bficiency
~~ 8ficiency
-0.3
-0.3 >-
:0 0.30
0.30
-1000 U
U
-1000 cc
-1200 -0.4
-0.4 ~
.~ 0.20
0.20
-1200

Bias/V
Bias I V
ffi=W 0.10
0.10

(b)
(b) 0.00 +---+---+---+----1
0.00
0.50
0.50 1.00
1.00 1.50
1.50 . 2.00
2.00 2.50
2.50
Fig.
Fig. 2.7. (a)Absorbed
2.7. (a) (bs(E,emitted
Absorbed(bs(E)), (be(E, qV))
emitted(be(E, qV andand net (=bs
net (= bs - be)
be) spectral
spectral photon
photon
flux
flux for a biased
for a biasedcell
cellof Eg== 0.7
ofEg 0.7VV at
at 300
300KK illuminated
iluminated byby aa black
black body sun 5760 K.
sun at 5760 K. Band Gap/eV
Band Gap I eV
(b)
(b) Current density, power
Current density, power density
density and
and efficiency
effciency of
of the
the device
device in
in (a)
(a) as
as aa function
function of
of V.
V.
The
The current
current isis calculated
calculated from
from qq times
times the
the integrated
integrated net
net photon
photon flux
flux.. Fig.
Fig. 2.8.
2.8. Calculated limiting
Calculated limiting efficiency
effciency for
for aa single
single band
band gap
gap solar
solar cell
cell in
in AM
AM 1.5.
1.5.
34 The
The Physics
Physics of Solar Cells
Cells photons In, Electrons
Photons In, Out: Basic
Electrons Out: Principles of
Basic Principles of PV
PV 35

800.------------------r==================~
800 effciency.In
efficiency. In the
the limit
limit where
where Ta Ta ~-l 0,
0, the
the radiative
radiative current
current vanishes
vanishes and
-- Black
Blackbody
bodysun
sun at
at 5760K
5760K
~
:: bias has no effect
bias has effect onon the
the net photocurrent.
photocurrent. Then the optimum
optimum operating
operating
~ J 600
~GJ 600 -Optimum band
-Optimum bandgap
gapcell
cell
bias is V
bias is Edqq(anything
V == Ed (anythinghigher
higherisisphysically
physically unreasonable)
unreasonable) and if all
E
carriers are collected
collected with D.J.
D../.L == qV
qV then the maximum
maximum effciency
efficiency is
is given
given
::-- 400
GJ
J
400 by
U

-Eg J:
U
c::
i:
II
III
:g
:s 200
200 g
J: bs(E)dE
g
r - Jooc Ebs(E)dE
~~
O~-+--~~--~--r_~~~~
o
0.00 0.50
0.00 0.50 1.00
1.00 1.50 2.00
1.50 2.00 2.50
2.50 3.00
3.00 3.50
3.50 4.00
4.00 This hashas aa maximum of around 44% 44% at a band gap gap of 2.2
2.2 eV for aa 6000
6000 K
Photon Energy leV black body sun, increasing
increasing to to higher
higher values
values and and higher
higher band
band gaps
gaps for
for hotter
hotter
suns.
suns. This
This limit
limit was was reported
reported by by Shockley
Shockley and and Queisser
Queisser Shockley,
[Shockley, 1961)
1961]
Fig. 2.9.
Fig. 2.9. Power
Power spectrum
spectrum of
of aa black
black body
body sun
sun at
at5760
5760 K,
K, and
and power
power available
available to the
as the
as the ultimate
ultimate effciency
efficiency of the solar solar cell.
cell. In practice
practice the cooling
cooling of thethe
optimum band
band gap
gap cell.
cell.
cell below
cell below the the ambient
ambient requires
requires an an input of energy which reduces
energy which reduces thethe net
efficiency.
effciency.
spectrum.
spectrum. ItIt has
has a a maximum
maximum of about 33% 33% at an Eg Eg of of around
around 1.4
1.4 eV.
eV. Another way
Another way of improving
improving the the effciency through the
efficiency through the spectrum
spectrum is is to
Optimising the performance of the ideal single band gap photoconverter is alter the angular width of of the
the sun.
sun. Recall from Eq.
Recall from Eq. 2.2
2.2 that
that the solar flux
therefore
therefore aa matter
matter ofof choosing
choosing thethe right
right materiaL.
material. contains a factor Fs Ps which represents
represents the solid solid angle
angle subtended
subtended by the sun.
In Fig. 2.9 the available power spectrum for
In Fig. 2.9 the available power spectrum for an optimum
optimum band gap gap If thisangle
If this angle is increased
is increased by concentrating
by concentrating the light, the net the
photo light, the net photo current

cell
cell at maximum power power point compared with
point is compared with the incident
incident power
power from
from a wil increase
will increase and the first first term
term (absorbed
(absorbed flux)flux) in the integrand
integrand inin Eq.
Eq. 2.24
2.24
black body
black body sun. Clearly, no
sun. Clearly, no photons
photons withwith energy
energy less
less than
than Eg contribute wil increase
will increase relative to the second (emitted flux). flux). One way way oflooking
oflooking at at this
to the
the available
available power.
power. Photons
Photonsof of EE ~> Eg
Eg are
are absorbed
absorbed but deliver only is to consider
is that while the cell
consider that emits radiation in all directions,
cell emits directions, it absorbs
D../.L(=
D.J.(= qVrn) of electrical energy to the load, so only D../.L/E
qVrn) of electrical energy to the load, so only D.J./E of their power
power sunlight
sunlight only only from
from a a small
small angular
angular range.
range. Increasing
Increasing the the angular
angular range
is available. The
is available. figure shows
The figure shows how how this
this fraction
fraction falls as E increases.
falls as increases. Even

qVrn .: Eg. .
improves the
improves the balance,
balance, as as does
does restricting
restricting the angularangular range
range for
for emission.
emission.
at EE ==Eg Egonly
onlya afraction D../.L/Eg
fractionD.J./ Eg of
of the
theincident
incidentpower
power isis available,
available, since
since This wilwill be
be considered
considered in more detail in Chapter 9. 9. Optimising
Optimising the powerpower
qVrn < E g . density then yieldsyields a new new r(Eg) curve with a higher maximum at
Tf(Eg) curve at aa smaller
smaller
band
band gap.gap. For
For light
light which is concentrated
concentrated by by aa factor
factor of 1000,
1000, aa limiting
limiting
2.5.5. Effect of
2.5.5. Effect of spectrum
spectrum on efficiency
on effciency efficiency
effciency of of about
about 37% 37% at Eg == 1.1
at Eg 1.1eV eVisis predicted
predicted Henry,
[Henry, 1980J.
1980]. For
For aa
concentration factor of 4
of 4.6
4.6 xx 104
10 (the
(the maximum)
maximum)rTfisisover over40%.
40%. However,
However,
To model the influences
influences of of spectrum
spectrum on limiting effciency, efficiency, it is
is convenient
convenient these estimates ignore
these ignore the practical effect effect that under under high
high concentrations
concentrations
to use a black body spectrum at Ts as the illuminating
black body spectrum at Ts as the iluminating source. source. The spectrum the cell will
wil bebe heated,
heated, and and emit
emit more
more strongly.
strongly.
of aa 5760
5760 KK black
black body
body with
with the
the angular width of the sun is a good model of
the extra-terrestrial
extra-terrestrial(Air (Air Mass
Mass 0) spectrum
spectrum and predictspredicts aa limiting
limiting effciency
efficiency
of around
around 31 31 %% atat a band
band gapgapof of1.3
1.3 eeV
V [Araujo, 1994], somewhat
Araujo, 1994), somewhat lower than than 2.6. Requirements
2.6. Requirements for
for the
the Ideal
Ideal Photoconverter
Photoconverter
the maximum efficiencyeffciency in AM1.5.
In the
the above
above we
we made
made the following
following assumptions:
assumptions:
If the spectrum
If the spectrum is shifted to the the red,
red, by reducing the temperature of the
source,
source, the optimum band gap and the limiting limiting effciency
efficiency are both
both reduced.
reduced. that our
. that our photovoltaic
photovoltaic material has
has an
an energy
energy gap which separates
gap which separates states
states
Clearly,
Clearly, in in the
the limit where Ts
limit where Ts == TaTa the
the cell
cell isisin
inequilibrium
equilbrium with the source which are normally full
which from states which are normally empty;
full from
and there
and there is noisnet
nophoto
net photo conversion.
conversion. On On the
the other
other hand,
hand, ifif the temperature . that
thatall
allincident
incidentlight
light with
with E
E ~>Eg
Eg isisabsorbed;
absorbed;
of the source is increased relative to the
of the source is increased relative to the cell, so is the photocell, so is the photo conversion that each
. that each absorbed
absorbedphoton
photongenerates
generatesexactly
exactlyone
oneelectron-hole
electron-hole pair;
pair;
36
36 Physics of
The Physics of Solar
Solar Cells
Cells Photons
Photons In,
In, Electrons
Electrons Out:
Out: Basic
Basic Principles
Principles of
of PV 37
37

. that
that excited
excited charges
charges do
do not
not recombine
recombineexcept
exceptradiatively,
radiatively, as
as required
required by
by This
This asymmetry
asymmetry cancan be provided by preparing aa junction at at or
or beneath
beneath
detailed balance;
detailed balance; the
the surface.
surface. The
The junction
junctionmay
maybe be an
aninterface
interfacebetween
between two
two electronically
electronically dif-
dif-
that
. that excited
excited charges
charges are
are completely separated;
completely separated; ferent materials or between
between layers of the
layers of the same
same material
material treated
treated inin different
different
that
. that charge
chargeisis transported
transportedtotothe
theexternal
externalcircuit
circuit without
withoutloss.
loss. ways.
ways. ItIt is
is normally
normally large
large in
in area
area toto maximise
maximise thethe amount
amount of of solar
solar en-
en-
ergy intercepted. For effcient photovoltaic conversion
For efficient photovoltaic conversion the junction quality
examine what
Let's examine what these
these assumptions
assumptions mean
meanfor
for real
realphysical
physicalsystems.
systems.
is
is of centralimportance
of central importancesincesince electrons
electrons should
should loselose as little
as little as possif
as possihle--of
their
their electrical
electrical potential
potentialenergy
energy while
while being
being pulled away.
away. InIn practice prepar-
Energy gap
Energy gap ing this large area junction successfully
successfully andand without
without detriment
detriment to to material
quality is a challenge
challenge and limits the number
number ofof suitable materials.
Many solid
Many solid state and molecular materials satisfy the condition
condition of of the
the energy
energy
band gap.
or band gap. The need
need for conductivity
conductivity make
make semiconductors
semiconductors particularly
particularly
suitable. With
With band
band gaps
gaps in
in the
the range 0.5-3 eV
range 0.5-3 eV semiconductors
semiconductors can absorb Lossless transport
visible photons
visible photons to excite electrons across
electrons across thethe band gap, where they may be
collected. The compound semiconductors
semiconductors gallium arsenide (GaAs)
(GaAs) To
To conduct the charge
conduct the to the
charge to the external
external circuit the material
circuit the material should be aa
should be
collected. The III-V compound gallum arsenide
have band
band gaps
gaps close
close to the optimum
optimum (1.42(1.42 eV
eV good electrical conductor. PerfectPerfect conduction meansmeansthatthat carriers must not
and indium phosphide (InP) have
and 1.35 eV, respectively, at 300 K) and are favoured for high efficiency recombine
recombine withwith defects
defects oror impurities,
impurities, and should not give up energy energy to the
and 1.35 eV, respectively, at 300 K) are favoured for effciency
cells. The most popular
popular solar
solar cell
cell material,
material, silcon,
silicon, has
has aa less
less favourable
favourable medium.
medium. There should be no resistive loss
loss (no series resistance) or current
series resistance)
cells. The most
(1.1 eV, leakage (parallel resistance). The material around the junction should be
leakage (parallel resistance). The material around
band gap (1.1 eV, maximum
maximum effciency of 29%)
efficiency of 29%) but but is cheap and abun-
is cheap abun-
dant compared
compared to these III-VIII-V materials.
materials. Other
Othercompound
compound semiconductors,
semiconductors, highly conducting and
highly conducting and make
make good
good Ohmic
Ohmic contacts
contacts to to the external circuit.
in particlular cadmium telluride
telluride (CdTe)
(CdTe) and copper indium indium gallum
gallium dise-
dise- Mechanisms for
Mechanisms for excitation,
excitation, charge separation and
charge separation and transport
transport can
can be pro-
lenide (CuInGaSe2) are being developed for thin film photovoltaics. Recent vided by
vided by the
the semiconductor
semiconductorp-n p- junction,
junction,which
which isis the
the classical
classical model
model of a
lenide (CuInGaSe2) for
developments solar cell.
celL.InIn this
this system charge
charge separation
separation isis achieved
achievedby by aacharged
chargedjunction
junction
developmentsin in semiconducting
semiconductingmolecular
molecularmaterials
materialsindicate
indicate that organic
that organic
semiconductors between layers of
between layers of semiconductor
semiconductor of of different
differentelectronic
electronicproperties:
properties: i.i.e.,
e., the
semiconductors are promising materials for for photovoltaic energy
energy conversion
conversion
driving force
driving force which
whichseparates
separatesthe
the charges
chargesisiselectrostatic.
electrostatic.TheThep-n
p-n junction
in the
in the future.
future.
wil be
will be treated
treated in in detail
detail in
in Chapter
Chapter 6.6.

Light
Light absorption
Optimum load
Optimum load resistance
High
High absorption
absorptionofoflight withEE :;> Eg
lightwith Eg isisstraightforward
straightforward to to achieve
achieve in
principle.
principle. Increasing
Increasing the
the thickness of the absorbing layer increases
increases its opti- Finally, the
Finally, the load
load resistance
resistance should
should bebe chosen
chosentoto match
match the
the operating point
cal
cal depth, for most
depth, and for most semiconductors
semiconductors almost
almost perfect
perfect absorption
absorption cancan be of the cell.
of cell. As
As we
we have
have seen
seen above,
above, individual solar cells
individual solar tends to offer
cells tends offer
achieved with a layer a few tens or hundreds of microns thick.
achieved with a layer a few tens or hundreds of microns thick. However, However, photovoltages
photovoltages of of less
less than
than one volt which
one volt are often
which are often too
too small
small to
to be
be usefuL.
useful.
the requirements of high
high optical depth andand perfect
perfect charge
charge collection,
collection, make For most
For most applications,
applications, voltage
voltage isis increased
increased by connecting several
several cells in
cells in
very high demands
demands of of material
material quality. series into a module,
series into a module, and sometimes
sometimes by connecting modules in
connecting modules in seriesseries and
parallel into aa larger array.
array. In
In practice
practice the
the load resistance
resistance should
should bebe matched
matched
Charge with the
the maximum
maximum powerpower point of the array,array, rather than the cell.
cell.
Charge separation
As aa consequence
As consequence of ofthe
the demands
demands on on the
the material,
material, only
only aa very
very small
small
For
For a current to
a current to be delivered, the
be delivered, the material
material should
should be
be contacted
contacted in
in such
such number
number of materials,
materials, all of them inorganic semiconductors,
inorganic semiconductors, have have been de-
way that the
aa way the promoted
promoted electrons
electrons experience
experience aa spatial asymmetry, which
spatial asymmetry, which veloped for photovoltaics. Only a few of the many potentially
veloped for photovoltaics. Only a few of the many potentially useful ma- useful ma-
drives
drives them
them away
away from
from the
the point
point of promotion.
promotion. This can be an electric
electric field,
field, terials have
terials have the necessary technologicalhistory.
necessary technological history. The
The favourites
favourites are those
or
or aa gradient in electron
gradient in electron density.
density. developed
developed for for the
the microelectronics
microelectronics industry
industry '-'- silicon,
silcon, gallium arsenide,
gallum arsenide,
 38
38 The Physics
The Physics of
ofSolar
Solar Cells
Cells Photons
Photons In,
In, Electrons
Electrons Out:
Out: Basic
Basic Principles
Principles of
of PV
PV 39
39

amorphous silcon,
amorphous silicon, some
some II-VI
II-VI and
and other
otherIII-
III-V compounds. It
V compounds. It isis only
only re-
re- to
to the
thedifference
difference between
between the flux
flux ofofphotons
photons absorbed
absorbed from
from the
the sun
sun and
and the
the
cently that materials have been developed primarily for their application
cently that materials have been developed primarily for their application flux
flux of photons
photons emitted by the excited device, while
by the excited device, while the voltage
voltage due to
is due to
in photovoltaics.
in photovoltaics. the
the electrochemical
electrochemical potential
potential energy
energy of
of the
the excited
excited electrons.
electrons. From
From this
thiswewe
In terms
In terms of
ofthe
theabove
abovediscussion,
discussion, the
the main
mainreasons
reasons why
why real
realsolar
solarcells
cells calculate
calculate the
the current-voltage
current-voltagecharacteristic
characteristicofofananideal
idealsolar
solarcelL.
cell. The
The maxi-
maxi-
do not achieve ideal performance are
do not achieve ideal performance are these:these: mum
mum effciency
efficiencydepends
depends upon the incident
incident spectrum
spectrum and
and the
the band
band gap,
gap, and
and
for a standard solar spectrum it is around 33% at a band gap of
for a standard solar spectrum it is around 33% at a band gap of 1.4 eV. For 1.4 eV. For
. Incomplete
Incomplete absorption
absorption of ofthe
the incident
incident light.
light.Photons
Photonsare are reflected
reflected from
from
aa real
the front surface or from the contacts or pass through the cell without real device
device to approach thethe limiting
limiting effciency,
efficiency, it should have an optimum
optimum
the front surface or from the contacts or pass through the cell without energy gap, strong light
being absorbed.
absorbed. This
This reduces
reduces thethe photocurrent.
photocurrent. light absorption,
absorption, effcient
efficient charge
charge separation and and charge
charge
being transport, and
transport, and the
the load
load resistance
resistance should
should bebe optimised.
optimised.
. Non-radiative
Non-radiativerecombination
recombinationof ofphotogenerated
photogenerated carriers. carriers. Excited
Excited charges
charges
are trapped at defect sites and subsequently recombine
are trapped at defect sites and subsequently recombine before being col- before being col-
lected. This can occur at the surfaces where the defect density
lected. This can occur at the surfaces where the defect density is higher, is higher, References
or near
or near interfaces
interfaces with another material,
with another material, oror near
near the the junction.
junction. Recombi-
Recombi-
G.L. Araujo and
and A.
A. Marti,
Marti,"Absolute
"Absolutelimiting
limitingeffciencies
effciencies for
for photovoltaic
photovoltaic energy
energy
nation reduces
nation reduces both
both the photocurrent, through
the photocurrent, through the probability of
the probabilty of carrier
carrier conversion",
conversion", Solar Energy
Energy Materials and
and Solar
Solar Cells
Cells 33,
33, 213
213 (1994).
(1994).
collection, and
collection, and the
the voltage,
voltage, by by increasing
increasing the
the dark current.
dark current. A. de Vos,
Vos, Endoreversible
Endoreversible Thermodynamics
Thermodynamics of Solar Energy Conversion
Conversion (Oxford
(Oxford
Voltage
. Voltage drop
drop due
duetotoseries
series resistance
resistance between
between the point of
the point of photogen-
photogen- University Press,
University 1992).
Press, 1992).
eration and the external circuit. This reduces the available power,
eration and the external circuit. This reduces the available power, as as R. Gottschalg,
Gottschalg, The
The Solar
Solar Resource
Resource and the
the Fundamentals
Fundamentals of Radiation
Radiation for Re-
Re-
discussed in
discussed in Chapter
Chapter 1.1. It also means
It also means that f:l./-Li=i=qqV.
that t:i V. newable Energy Systems
newable Energy (Sci-Notes, Oxford, 2001).
Systems (Sci-Notes, 2001).
C.H. Henry,
Henry, "Limiting effciencies of ideal
efficiencies of ideal single
single and
and multiple
multiple energy
energy gap terres-
In following chapters
In following chapters we
we shall
shall see
see how
howfar
far different
different designs
designsand
and materials
materials trial solar
solar cells",
cells", J.
J. Appl.
Appl. Phys.
Phys. 51,
51,4494-4499
4494-4499 (1980).
(1980).
meet
meet the demands of
the demands of the ideal photovoltaic
the ideal photovoltaic converter.
converter. W. Shockleyand
W. Shockley andH.J.
H.J.Queisser,
Queisser, "Detailed
"Detailed balance
balancelimit
limit of
of efficiency
effciency of
ofp-n junc-
p- junc-
tion solar cells",
cells", J. Appl.
Appl. Phys.
Phys. 32,
32, 510-519
510-519 (1961).
(1961).
P. Wuerfel,
P. Wuerfel, "The
"The chemical
chemical potential
potential of
of radiation",
radiation", J. Phys.
Phys. C15,
C15, 3697
3697 (1982).
(1982).
2.7.
2.7. Summary
Summary
The
The sunsun emits
emits radiant
radiant energy
energy over
over aa range
range of of wavelengths,
wavelengths, peaking
peaking in in the
the
visible. Its spectrum is similar to that of a black body at 5760
visible. Its spectrum is similar to that of a black body at 5760 K, although K, although
it is influenced
it is influenced by atmospheric absorption
by atmospheric absorptionand and the
the position
position of of the sun.
the sun.
The standard solar
The standard solar spectrum
spectrum for for photovoltaic
photovoltaic calibration
calibration isis the AM 1.5
the AM 1.5
spectrum.
spectrum.
AA photovoltaic
photovoltaic solar
solar energy
energy converter
converter absorbs
absorbs photons
photons of of radiant en-
radiant en-
ergy to
ergy to excite
excite electrons
electrons toto aa higher
higher energy
energy level,
level, where
where they
they have
have increased
increased
electrochemical
electrochemical potential
potential energy.
energy.In In order
order for these excited
for these excited electrons
electrons to be
to be
extracted
extracted as electrical power, the material must possess an energy gap or
as electrical power, the material must possess an energy gap or
band
band gap.
gap. To To calculate
calculatethe the absolute
absolutelimiting
limiting efficiency
effciency of a photovoltaic
of a photovoltaic
energy
energy converter,
converter, wewe use
use the
the principle
principle of of detailed
detailed balance.
balance. This allows for
This allows for
the
the fact
fact that any body
that any body which
which absorbs
absorbs light
light must
must also
alsoemit
emitlight.
light. A pho-
A pho-
tovoltaic
tovoltaic device
devicewill
wil emit
emit more
more light
light when
when optically
optically excited
excited onon account
account of of
the
the extra electrochemical potential energy of the electrons. This radiative
extra electrochemical potential energy of the electrons. This radiative
recombination
recombinationisisthe the mechanism
mechanismwhich whichultimately
ultimatelylimits
limitsthe
the efficiency
effciency of of aa
photovoltaic
photovoltaic cell.
celL.The
Thecurrent
current delivered
deliveredby by the
the ideal
ideal photoconverter
photoconverter is is due
due
 Chapter
Chapter 33

.
Electrons and
Electrons and Holes
Holes in
in
Semicond
Semicond uctors
uctors

3.1.
3.1. Introduction

In Chapter 22 we
we considered
considered the requirements
requirements for photovoltaic
photovoltaic energy con-
version.
version. WeWe concluded
concludedthat that aa suitable
suitable photovoltaic
photovoltaic material should should absorb
absorb
visible light, possess a band gap between the initial, occupied states and
visible light, possess a band gap between the initial, occupied states
the final, unoccupied
unoccupied states states which are are involved
involved in in photon absorption and be be
able to transport
transport charges
charges effciently.
efficiently. The gap is necessary in order to make make
the potential energy
the extra potential energy which
which electrons
electrons gain photon absorption
gain from photon absorption
available as electrical energy. energy. All semiconducting
All semiconducting and and insulating solids pos-
solids
sess
sess an energy gap but but only
only semiconductors
semiconductors are suitable for for photovoltaics,
photovoltaics,
because
because the the band gap of of insulators
insulators is is too large
large to permit
permit absorption
absorption of of
visiblelight.
visible light.
Most Most solids possess solids possess an energy gap, but with the
molecularmolecular
an energy gap, but with the
exception of of some
some conjugated
conjugated molecular
molecular materials,
materials, the charge
charge transport
transport is is
too
too ineffcient
inefficient totobebeuseful
usefulforforsolar
solarcells.
cells.
The band
The band gapgap isis important
importantbecausebecause ititenables
enables excited
excited electrons
electrons to to remain
remain
in
in higher
higher energy
energy levels
levels forfor long
long enough to be exploited. IfIfelectrons
be exploited. electrons were
were
simply promoted through a continuum
simply promoted through a continuum of energy levels as of energy levels as in a metal,
metal, forfor
example, they would
example, would very very quickly
quickly decay
decay backback down
down to their
their ground
ground state
state
through
through aaseries
series ofof intermediate
intermediate levels.
levels. The
The abundance
abundance of of empty
empty levels
levels at at
intermediate energy
intermediate energy meansmeans thatthat the
the probabilty
probabilityofofan anexcited
excitedelectron
electronbeing
being
scattered
scattered to toaalower
lower energy
energy state
state within
within thethethermal
thermalenergy
energyof ofthe
theoriginal
original
level,
level, is
is high.
high. AtAt room
room temperature
temperature this this 'thermalisation'
'thermalisation'ofofcarriers
carriers totothe
the
band
band edge
edge occurs
occurs in infemtoseconds.
femtoseconds . When an an electron
electron isis excited
excited across
across aa
band
band gap,
gap, ititquickly
quickly decays
decays to to the
thelowest
lowest available
available energy
energy state in in the
the
conduction
conduction band band (the(the conduction
conduction band band edge)
edge) but but the
the next stage
stage -- decay
decay
across the band
across band gap
gap to to aa vacant
vacant site in the the valence
valence band - isisslow,slow,asasshown
shown
inFig.
in Fig.3.1.
3.1.

4141
42
42 Physics of
The Physics oJ Solar
Solar Cells
Cells Electrons
Electrons and
and Holes
Holes in
in Semiconductors
Semiconductors 43
43

metal
metal semiconductor
semiconductoror
orInsulator
Inlulator

----....IIL..Io---- conduction band

band
- - -- conduction
conduction band
band
photon
~> 1 ! -il s l ::>-
~
ei
GI
GI
c
c: + 4-
i
-
w
w +-4j...

---_1-..-. .---- band

valence band
4-
4-
++-' .
-4j...-4!-

- 1s
- f8 ll I I
22 N
N Crystal
"*" 22 N Crystal
valence
valence band
band

N Crystal

Fig. 3.1.
Fig. Promotion of
3.1. Promotion of an
an electron
electron from
from valence
valence band
band to
to conduction
conduction band by aa pho-
band by pho- Fig. 3.2. As
Fig. 3.2. Asthe
thenumber
numberofofatoms
atomsininaamolecule
molecule or
or cluster
cluster increases,
increases, the
the atomic
atomic orbitals
orbitals
ton , thermalisation
ton, thermalisation to
to the
theband
bandedges,
edges, and
and recombination.
recombination. Although thermalisation
thermalisation is
is split
split into
into multiple
multiple levels, eventually coming
levels, eventually comingtogether
together to
to form
form bands
bands in
in the
the limit
limit of
of many
many
and occurs
very fast and occurs in
in femtoseconds,
femtoseconds, relaxation
relaxation across
across the
the band is many
band gap is many orders
orders of atoms. Overlapping (left)
atoms. Overlapping (left) and
and non
non overlapping (right) bands
overlapping (right) bands represent
represent aa metal
metal and
and aa
magnitude slower.
magnitude slower. semiconductor, respectively.
respectively.

practice, the great

In practice, great majority
majority of
ofexperience
experience with photovoltaic
photovoltaic materi-
materi- Bands are occupied
Bands are occupied or
or not
not depending
depending upon
upon whether
whether the
the original
original molec-
molec-
als is based on a small number of semiconductor
semiconductor materials.
materials. In
In this chapter ular orbitals were occupied. The
were occupied. The highest
highest occupied
occupied band,
band, which contains the
which contains the
and the
the next
next we
we wil
willexamine
examinesomesomeofofthe
thebasic
basicphysical
physical principles
principles of
of semi-
semi- valence electrons, is
valence electrons, is normally
normally called
called the
the valence band (VB).
valence band (VB). The
The lowest
lowest un-
un-
conductors. We will
conductors. We wil focus focus on the electronic
electronic and optical properties of crys-
optical properties of crys- occupied band
occupied band isis called
called the
the conduction band (CB).
conduction band (CB). If the
the valence band is
valence band is
talline materials. We
talline materials. We will show how
wil show how the optical
optical and
and electronic
electronic properties
properties partly full, or if it overlaps in energy with the lowest unoccupied
partly full, or if it overlaps in energy with the lowest unoccupied band, the band, the
result from
from the crystal structure. In In this
this chapter
chapter we
we introduce
introduce the concepts
concepts solid isis aa metal.
solid metal. InIn aa metal,
metal, the
the avalabilty
availability of
of empty
empty states
states at
atsimilar
similarener-
ener-
of density
density of states, electron
electron distribution function, doping,
function, doping, quasi thermal gies makes
gies makes itit easy
easy forfor aa valence electron to
valence electron to be
be excited,
excited, or
or scattered, into aa
scattered, into
equilibrium
equilbrium and and the
the definition
definition of electron
electron and
and hole
hole currents.
currents. In
In Chapter 4 neighbouring state.
state. These
These electrons
electrons can
canreadily
readily act
act as
as transporters
transporters of
of heat
heat
we
we will treat the
wil treat theprocesses
processes ofof charge
charge carrier
carrier generation
generation and
and recombination
recombination or charge,
charge, andand soso the solid conducts
conducts heat and electric current.
in semiconductors
semiconductors and
and show
show how
how toto set
set up the semiconductor
up the semiconductor transport If the
If the valence
valence bandband is is completely
completely full
full and separated from
and separated from the
the next
next band
band
equations, which are key
key to the
the physics
physics of
of photovoltaic
photovoltaic devices.
devices. by an
by an energy
energy gap,gap, then
then the
the solid
solid is
is aa semiconductor
semiconductor or or an
an insulator.
insulator. The
The
electrons in the valence band are all completely involved in bonding and
electrons in the valence band are all completely involved in bonding and
cannot be
cannot be easily
easily removed.
removed. TheyThey require
require an an energy
energy equivalent
equivalent toto the
the band
band
3.2. Basic Concepts
3.2. Basic Concepts gap to
gap to be
be removed
removed to to the
the nearest available unoccupied
nearest available unoccupied leveL. Thesematerials
level. These materials
therefore do
therefore do not
not conduct heat or electricity
electricity easily.
easily.
3.2.1. Bonds
3.2.1. Bonds and
andbands
bands in
in crystals
crystals
Semiconductorsare
Semiconductors aredistinguished,
distinguished,roughly,
roughly,asasthe
the group
group ofof materials
materials
When
When aa pair of of atoms
atoms are brought together together into a molecule,
molecule, their atomic with a band gap in the range 0.5 to 3 eV. Semiconductors have aa small
with a band gap in the range 0.5 to 3 eV. Semiconductors have small con-
con-
orbitals combine
combine to form pairs of molecular molecular orbitals arranged slightly
orbitals arranged slightly higher ductivity in
ductivity in the
the dark
dark because
because only
only aa small
small number
number of valence electrons
of valence electrons will
wil
and slightly lower in energy than
and slightly lower in energy than each original each original level.
leveL. We say that the
We say that the energy have enough
have enoughkinetic
kinetic energy
energyat at room
room temperature
temperature to to be
be excited
excited across the
across the
levels have split.
levels have split. When
When aa veryvery large
large number
number of of atoms come together
atoms come together in band gap
band gap atat room
room temperature.
temperature. This
This intrinsic
intrinsic conductivity
conductivity decreases with
decreases with
aa solid,
solid, each
each atomic
atomic orbital splits into aa very
orbital splits very large
large number
number ofof levels,
levels, so increasing band gap. Insulators are wider band gap materials
increasing band gap. Insulators are wider band gap materials whose con-whose con-
close
closetogether
togetherin energythat
in energy that they
they effectively
effectively form band, of
form aa continuum, or band, of ductivity is
ductivity is negligible
negligibleatat room
room temperature.
temperature. Materials
Materials of
of band
band gap
gap 0(
< 0.5 eV
0.5 eV
allowed levels. The bands due to different molecular orbitals
allowed levels. The bands due to different molecular orbitals mayor may-not mayor ma:ynot have aa reasonably
have reasonably high
high conductivity
conductivity and
and are
are usually
usually known
known asas semimetals.
semimetals.
overlap.
overlap. The The energy
energy distribution
distribution of of the
the bands
bands depends
depends upon the electronic When the solid forms a regular crystal, then the energies of the bands, or
When the solid forms a regular crystal, then the energies of the bands, or
properties
properties of of the
the atoms
atoms andand the strength of of the bonding
bonding between
between them. the band structure can be predicted exactly. Exactly which crystal structure
the band structure can be predicted exactly. Exactly which crystal structure
44
44 The Physics
The Physics of
of Solar
Solar Cells
Cells

r Electrons
Electrons and

of the

or energy.
or
to
Holes in
and Holes

energy. Meanwhile,
move, and
to move,
Semic.onductors
in Semiconductors

the lattice and some are able to break free.

excited
excited into
into the conduction band and are
Meanwhile,the
and can
can also
the vacancies
vacancieswhich
also conduct
conduct (see
free. The freed electrons have been
are able
ableto
whichthey
(see Box
Box 3.1)
to travel
travel and
theyhave
3.1).. The
The higher
and transport
haveleft
transport charge
left behind
higher the
behind are
are able
the temperature,
45
45

the greater the number

number of electrons
electrons and
and holes
holes which
whicharearemobilised,
mobilsed, and
and the
higher
higher the
the conductivity.

Box
Box 3.1. holes
3.1. Electrons and holes
Fig.
Fig, 3.3. Structure of
3.3, Structure of crystalline
crystallne silicon.
silcon. Each
Each silicon
silcon atom is bonded
atom is to four
bonded to four others
others in
in When an electron is removed from aa bond
removed from bond between atoms, a positively
between atoms,
aa tetrahedral
tetrahedral arrangement.
arrangement.
charged vacancy
charged vacancy remains.
remains. This
This vacancy
vacancy can
can be
be filled by another electron,
filled by electron,
most easily by electrons which
which are involved in neighbouring
involved in bonds. If
neighbouring bonds. If this
aa solid will
wil adopt
adopt depends
depends upon
upon the
thenumber
number of ofvalence
valence electrons and and other
factors. It
factors. It wil
will prefer
prefer aa configuration
configuration thatthat minimises
minimises the the total
total energy.
energy. A A
band gap is is likely to
to arise in a crystal
crystal structure
structurewherewhere all
all valence
valence electrons
electrons
are
are used
used in in bonding.
bonding. ForFor example,
example, thethe silcon
silicon atom
atompossesses
possesses fourfour valence
valence
electrons in
electrons in its
its outermost
outermost 3s 3s and
and 3p
3p atomic
atomic orbitals.
orbitals. If
If the
the atom
atom could
could form
form
bonds with four four neighbours, each contributing
electrons would be occupiedoccupied in
contributing one
in bonding.
one electron, then
bonding. In crystalline
crystallne silicon
then all
silicon this
this is
all valence
valence
is achieved
achieved
.............

by the hybridisation
hybridisation of the the 3s and 3p 3p orbitals
orbitals into
into aa set
set of
of four
four degenerate
degenerate
Sp3 orbitals, which
Sp3 orbitals, which areare directed
directed inin space
space with
with tetrahedral
tetrahedral symmetry,
symmetry, and and
allow the formation of four four identical silicon-silicon
silcon-silcon bondsbonds with
with neighbouring
neighbouring
atoms (Fig. 3.3). When the crystallne
to
crystallinesolid
solidisis formed,
formed, thethe Sp3 orbitals split
Sp3 orbitals
II
II
to form
form aa pair
pairofofbands.
bands. TheThe lower,
lower, bonding
bonding band band isis completely
completely filledfilled by
by
the
the valence electrons and
valence electrons and the
the upper,
upper, antibonding
antibonding or or conduction
conduction band, band, is is
completely
completely empty
exist
exist in
empty in
in different
in aa perfect
different phases.
perfect crystal
phases. For
crystal at
For instance,
at absolute
instance, carbon
insulating, wide band gap, diamond crystal
absolute zero.
carbon can
zero. Some
can form
crystal structure
Some solids
form either
structurewhere
either the
whereall
solids can
can
the highly
all four
highly
four valence
valence
.....
.......
Cl

:: <
electrons
electrons are are tied
tied up
up inin covalent
covalent bonds
bonds with
with neighbouring carbon atoms,
neighbouring carbon atoms, or or ~
the
the semimetallc
semimetallic graphite
graphite structure
structurewhere
whereonlyonly three
threevalence
valence electrons
electrons are are
involved
involved in in directed
directed bonds with neighbouring
neighbouring atoms while while the remaining
remaining Valence and
Valence and conduction
conduction electrons
electrons Valenos band
Valence band holes
holes and conduction
conduction electrons
electrons

electron
electron is is loosely involved in
loosely involved in bonding
bonding withwith another
another plane
plane ofof carbon
carbon atomsatoms Fig,
Fig. 3.4
3.4. The
Thevalence
valenceband
bandisisrepresented,
represented, very
very crudely,
crudely, by
by marbles
marbles in aa tray.
tray. When
When
and
and isis relatively
relatively mobile.
mobile. the
the valence
valence band
band is
is filled
filled (top)
(top) nono net
net electron
electron motion
motion can
can occur,
occur, despite
despite an
an applied
applied
force, because there
force, because there are
are no
no vacant
vaant orbitals
orbitals for
for the
the electrons
electrons to be
be scattered
scattered into.
into. Motion
Motion
becomes
becomes possible when
when an electron is removed
removed (bottom),
(bottom), freeing
freeing up some vacant orbitals.
orbitals.
3.2.2. Electrons,
3.2.2. Electrons, holes
holes and
and conductivity
conductivity The
The nearly
nearly filled
filled valence band is most easily characterised in terms of those orbitals
orbitals which
which
are
are not filled, called
called 'holes'.
'holes'. The
Thedynamics
dynamics of
ofthe
the hole
hole are
are equivalent
equivalent to
to those.of
t hose .o f aa particle
particle
with
with the
the opposite
opposite charge,
charge, wavevector and energy
wavevector and to the missing
energy to electron, It responds
missing electron. responds to
to
At absolute
At absolute zero
zero temperature, a pure
temperature, a pure semiconductor
semiconductor is
is unable to conduct
unable to conduct
an
an applied
applied field
field by moving in the opposite
moving in opposite sense
sense to an
an electron,
electron. The
The two
two situations
situations
heat or electricity since all of its electrons are involved in bonding. As the
heat or electricity since all of its electrons are involved in bonding. As the depicted
depicted on the
the right
right are
areequivalent
equivalent to
to those
those on
on the
the left,
left ,using
using holes
holes to
to represent
represent missing
missing
temperature
temperatureisisraised,
raised ,the
theelectrons
electronsgain
gainsome
some kinetic
kinetic energy
energy from
from vibrations
vibrations electrons.
electrons .
46 The Physics
The Physics of Solar Cells
Celts Electrons and Holes
Electrons Holes in Semiconductors
Semiconductors 47

happens, the the vacancy

vacancy moves to the neighbouring bond. The creation creation of
of holes the probability distribution of of the electrons must also be periodic.
periodic. There is
in the valence
valence band creates a means whereby whereby charge
charge can
can be
be transferred.
transferred. In no physical
no reason why
physical reason why anan electron
electron should
should occupy
occupyaa particular
particular site within
the presence of an electric field,
field, aa bonding, or valence,
valence, electron
electron can
can respond one unit
one unit cell
cell rather than withinwithin anyany other.
other. Because
Because the lattice
lattice isis infinite,
infinite,
to the
the field
field by
by moving
moving into the hole.hole. The
The vacancy
vacancy which
which it leaves
leaves behind
behind the electrons should
should form delocalisedstates
form delocalised states which
whichextend
extend throughout
throughout the
can be filled
filled by another valence electron, and
valence electron, and so
so on.
on. The net movement
movement of crystal, just like
like an
an electron
electron in in free
free space.
space. The
The sort
sortof
ofwavefunction
wavefunction which which
the valence electrons against
valence electrons against the field
field is
is equivalent
equivalent toto the movement
movement of a satisfies theseconditions
satisfies these conditions is the
is the BlochBloch function. It
wave wavefunction, It is the
the product of a
small number of positive
small positive holes
holes inin the
the direction
direction of the field. Since there are
field. Since periodic part
periodic part uik(r), which
which possesses
possesses thethe periodicity
periodicityofofthe the lattice,
lattice, and
and a
many fewer
fewer valence
valence holes
holesthan
than electrons
electrons itit is
is much
much more
more convenient
convenient toto think
think wave part.
plane wave part. The
The periodic
periodic partpart is related to one of the atomic orbitals
in
in terms
terms of of the
the motion of holes
motion of holes through
through the
the valence
valence band.
band. These positive
These positive involved in
involved in the
the crystal
crystal structure
structure and inherits its its symmetry.
symmetry, The The plane
plane wave
wave
holes can
holes can be characterised
characterised with
with a mobilty
mobility and
and an
aneffective
effective mass, just
just like
like modulates the wavefunction
modulates wavefunction and and isis analogous
analogous to to the wavefunction
wavefunction of an
conduction electrons.
electrons. electron in free
electron free space. Each Bloch
space, Each Bloch state
state is
is tthus
hus characterised
characterised by by aa crystal
band i and
band and aa wavevector
wavevector kk,,
semiconductor can
A semiconductor can be made to conduct in other ways:
be made ways: if thethe material
7,b(k,
'l(k, r) uik(r)e ik .r . .
r} == uik(r)eik,r (3,1)
(3.1)
is exposed to
is exposed to light of energy
light of energy greater
greater than band gap,
than the band gap, a photon
photon can
can bebe
absorbed by a valence electron to
valence electron to free
freeitit from
fromthe
the lattice
lattice and
and promote it into In quantum
quantum mechanical terms, kk is aa 'good
mechanical terms, 'good quantum
quantum number'.
number', For For each
each
the conduction
conduction band. ThisThis creates
creates aa vacancy
vacancy in the the valence
valence band. The free free original atomic
original atomic orbital i therethere is
is aa continuous
continuous setset of
of solutions with different
different
electron and
electron and hole
hole created
created inin this way
way are
are available
available to conduct
conduct electricity.
electricity. k which make up
which make up the
the wave
wavefunctions
functions ininthetheith
ithcrystal
crystal band,
band. The
The uik(r)
uik(r) and
This is called photoconductivity,
photoconductivity, the the phenomenon
phenomenon which whichfirst
firstdrew
drewattention
attention eigenenergiesE(k)
eigenenergies E(k) are, in in general,
general, found
found by
by solving the Schrdinger
Schrodinger equa-
to photovoltaic materials (see Chapter 1). 1). tion for each band i, for for each k. The The map
map of
of energies
energies E against
against wavevector
wavevector
Alternatively, impurities with different
Alternatively, different numbers of valence electrons or k is called the crystal
crystal band
band structure (see Box Box 3.2).
3.2). The
The uik(r) are usually
usually
bond strengths
different bond strengths can
can be
be added
added to to the
the materiaL.
material. Electrons
Electrons oror holes
holes rapidly varying with distance and weakly
varying with dependent on
weakly dependent on kk., In aa commonly
commonly
may be freed
freed more
more easily
easily from
from these
these impurities
impurities than
than from
from thethe native atoms, used approximation, called the effective mass approximation,
effective mass approximation, the the k depen-
thereby increasing the number
number of carriers
carriers normally available for conduction dence
dence ofof the
the uik(r}
uik(r) is
is neglected.
neglected. Then Then all
all of the
the dynamic
dynamic information is is
compared
compared to the pure pure semiconductor.
semiconductor. Deliberate addition of impurities to contained
contained in in the plane wave
wave part of the wavefunction,
wavefunction, and and the
the ui(r) come
come
increase conductivity in this way way is is called
called doping.
doping. Both of of these
these processes
processes in through
through effective
effective parameters.
- photoconductivity
photoconductivity and and doping
doping -- wil willbebediscussed
discussed later.
later.
next section
In the next section we
we will consider what controls
wil consider controls the energetic arrange-
Box 3.2.
Box 3.2, Band structure diagrams
Band structure diagrams
ment and thethe dynamics
dynamics of of the
the electrons
electrons and and holes
holes in
in aa semiconductor.
semiconductor.
E(k) isis usually
usually plotted against Ikl for
against Ikl for the two or three most important
two or
directions
directions inin the crystal.
crystaL Directions
Directions are labelled with Miler
labelled with Miller indices
indices (hkl)
(hkl)
3.3. Electron
3.3. Electron States
States in
in Semiconductors
Semiconductors where (h,k,l) is a vector parallel
parallel to k, measured in unit cell widths along the
3.3.1. Band
3.3.1. Bandstructure
structure natural axes
axes ofof the crystal.
crystal. For
For instance,
instance, the direction
direction (100)
(100) represents the
set of k parallel
parallel to the first
first of
of the natural axes,
axes, say
say the x axis.
axis. In
In aa cubic
cubic
To locate the energy
energy levels of an atom
levels of atom or
or aamolecule,
molecule, we
we need
need to
to solve
solve system, (100)
system, (100) also
also represents
represents the
the directions
directions parallel
parallel to
to the
the yy and
and zz axes,
axes,
Schrdinger's equation.In
Schrodinger's equation. In aa solid
solid we
we do
do the
the same
same thing,
thing, except
except that now
now because these three directions
directions are
are indistinguishable
indistinguishable in cubic
cubic symmetry.
symmetry,
weneed
we need
to to
taketake account
account of of an
an infiite
infinite array
array of
of atomic potentials, and
atomic potentials, and not
not k isis varied
varied from
from 0 to to n'TrIa
I a along
along the chosen direction, where
chosen direction, where aa isis the
just
just the
the few
few which
which make
make up our
our molecule.
molecule. In a crystallne
crystalline material
materialw~w~,are
are spacing
spacing of of the
the planes
planesof ofatoms
atomsininthat
that direction. Forkk>? 'TrIa,
direction.For nla, the
the energy
energy
able to
able to take
take advantage
advantage ofof the
the fact
fact that the atomic
that the potentials are
atomic potentials are arraiged
arranged spectrum repeats itself.
itself. This is because inin aa periodic
periodic structure with period
on anan infinite
infinite periodic
periodic lattice.
lattice. The periodicity of the
periodicity of the lattice
lattice means
means that a,
a, wavevectors which differ
wavevectors which differ by multiples
multiples of
of2n I a cannot be
211'1 be distinguished.
distinguished.
48 The
The Physics
Physics of Solar Cells
Cells Electrons
Electrons and Holes
Holes in Semiconductors
Semiconductors 49

" This is the parabolic

parabolic band approximation. The The effective
effective mass m~ is analogous
to the mass
mass of
of a free
free electron mo, but differs from mo
differs from mo through
through the different
different
Conducrion
Conduction band forces experienced
forces experienced by byan
an electron
electron within
withinaa crystal
crystal lattice.
lattice. m~
m~ can be greater
or less
less than moj
mo; large
large values
values of m~
m~ imply
imply that thethe conduction
conduction electrons
electrons
are strongly
are strongly influenced
influenced by by the
the atomic
atomic potentials.
potentials. m~m~ describes
describes how
how the
momentum PP conduction
momentum conduction electron responds
responds to an applied force,
force, FF

Valenceband
Valence bad F=m~~~ ..
F=m~~~ (3.4)
(3.4)

The value of m~ m~ isis determined

determined by by the atomic potentials. The The effective
effective mass
dl0,. ,,000,. dOO,. Wave
Wave vector, k is one
is way in
one way in which
which thethe ui(r)
u(r) enter
enter into
into the
the electron
electron dynamics
dynamics in this
this ap-
ap-
proximation. In
proximation. generalm~
In general m~ should
should be
be aatensor- dependenton
tensor- dependent onthe
the direction
direction
Fig.
Fig, 3.5. Schematic band
3,5. Schematic bandstructure
structure diagram
diagramofof aa direct
direct gap
gap semiconductor.
semiconductor. of
of the
the applied
applied force
force and the directions
and the directions of
of the
the crystal
crystal axes.
axes. However, close
However, close
to the band
band minimum the the band
band structure
structure isis often
often isotropic
isotropic and
and m~m~ can
can be
be
For
For most
most crystals, for kk <.( 00 the
crystals, for function E(k)
the function E(k) is identical
identical to E( -k)
to E( since
-k) since approximated by a constant.
states with
with positive
positive and
and negative
negative kk are
are degenerate.
degenerate. Therefore,
Therefore, all the infor-
infor- The two terms in Eq. Eq. 3.2
3.2 represent the potential
represent the potential and kinetic energy
energy of
mation about E(k)
mation about E(k) isis contained
contained in the range 00 <.( kk .(
the range 7r/a, and
< 'TIa, and only this
this aa conduction band electron
electron with wavevector
wavevector k. k. It
It can
can be
be used
used to derive the
section
section needs
need to be plotted.
to be plotted. The The point k = = 'TIa is called
7r/ a is called the Brillouinzone
the Brillouin zone electron velocity,
boundary. At
boundary. these points,
At these points, the wave function
the wave function is a standing
standing wave
wave and
and the
gradient E(k)
gradient of E(k) vanishes. Whether the energy reaches a maximum or
of vanishes. Whether the energy reaches a maximum or aa v = VkE(k) = !i(k - koc) (3.5)
(3.5)
m*c
minimum
minimum depends
depends onon the symmetry of the band.
and momentum

We minimum and maximum

We are interested in the minimum maximum energies of the
the crystal m~v = !i(k
p = m~v Ii(k -- koc)
ko c) .. (3.6)
(3.6)
bands, since
bands, since these
these determine
determinethe
the band
band gap,
gap, and
and in
in the
the form of E(k)
form of E(k) near
to
to these
these stationary points.
stationary points. 3.3.3. Valence band
3.3.3. Valence

In the valence
valence band, we
we require
require an expression for the energy of the hole
expression for hole
3.3.2.
3.3.2. Conduction band
near to the valence band maximum.
valence band maxium. Since
Sinceaahole
hole represents
represents the
the absence
absence of
For
For the conduction band,
the conduction band, the minimum of
the minimum of the energy E(k)
the energy occur at
E(k) may occur an electron,
electron, and electrons prefer to
electrons prefer to have
have as
as little energy
energy as possible,
possible, the
kk =
= 00 or
or another
another value
value of
of k
k corresponding
corresponding to to an
an important direction in
important direction in the
the most stable situation
situation for
for aa hole
hole is
is where
where the electron energy
energy is a maximum.
crystal.
crystal. Near to a minimum
minimum of energy
energy at at k == koc,
k oc , it
it is
is often
often convenient
convenient to Therefore holes
Therefore holes are
are most
most likely
likely to
to exist
exist near to aa valence
valence band maximum,
maximum,
expand
expand thethe E(k) in powers
E(k) in powers of
of (k
(k -- koc) and approximate
k oc ) and approximate E(k) by
E(k) by and have kinetic energy which
which increases
increasesasasE(k)
E(k) is reduced.
reduced. For a hole near
2 a VB maximum at
VB maximum at k = kvo,
kyo, the energy
energy can be approximated
approximated by
+ /i,2Ik-
E(k) = Eco
E(k) = E + kocl
!i21k - kocl2 (3.2)
(3.2)
2m6
2m:;cO
E(k) = Evo _ !i21k - kvol2 (3.7)
(3.7)
2m~
where Eco
where Eco == Ec(ko), m~ is
Ec(ko), m~ with the
is a parameter with the dimensions
dimensions of mass and
is defined
defined from
from the
the band
band structure by where Evo
where Evo == Ev(kvo),
Ev(kvo), resulting in a hole
hole velocity
velocity of
i _ i fPEc(k) !i(k -- kvo)
Ii(k kyo)
(3.3) v=
V=- (3.8)
m:; - !i2~ (3.3)
m*v
(3.8)
50
50 The Physics
The Physics of
ofSolar
Solar Cells
Cells Electrons
Electrons and
andHoles
Holes in
inSemiconductors
Semiconductors 51
51

and momentum
and momentum
EE
-!ilk-- kvo)
pp == -(k kyo) (3.9)
(3.9)
Eo
where the
where the VB
VB effective
effective mass, m~ is
mass, m~ is defined
defined through
through

i
m*v -2~i fj2 Ev(k) (3.10)
(3.10)
Evr-----------~~------------~~~~---
E
v
so that
so that the
themass
massisisnormally
normallypositive.
positive. In
Ingeneral,
general, the
theeffective
effective masses
masses of
of
electrons and
electrons and holes
holes in
in the
the same
same semiconductor
semiconductor areare different,
different, because
because the
the
curvature of
curvature of the
the conduction
conduction andand valence
valence bands
bands are
aredifferent.
different.
kk

3.3.4. Direct
Direct and
and indirect
indirect band gaps Fig.
Fig. 3.6.
3.6. Band
Bandstructure
structurediagram
diagramshowing
showingindirect
indirectband
band gap,
gap. The
The maximum
maximum energy
energy of
of
3.3.4. band gaps
the
the valence band occurs
valence band occurs at
at aa different
different wavevector to the
wavevector to the minimum
minimum of
of the
the conduction
conduction
The minimum
minimum amount
amount of of energy
energy which band,
band. Excitation
Excitation of
of an
an electron
electron across
across the
the fundamental
fundamental bandband gap
gap requires
requires aa change
change in
in
The which will promote an
wil promote an electron
electron from
from the
the
electron momentum,
momentum. This
This may
may be
be supplied
supplied by
by aa phonon.
phonon.
valence band
valence band into
into the conduction band
the conduction band isis called
called the
the fundamental
fundamental bandband gap,
gap,
E g . If
Eg. If the
the CB
CB minimum
minimum and and VBVB maximum
maximum occur occur at the same
at the same value
value of
of k,
k,
then a photon of energy Eg is sufficient to create an electron-hole
then a photon of energy Eg is suffcient to create an electron-hole pair. This pair. This
type of semiconductor
semiconductor is is called
called aa direct
direct band
bandgap materiaL
gap materiaL. E
type of
Now, if
Now, if the CB minimum
the CB minimum and and VBVB maximum
maximum occur occur atat different values
different values conduction band
conduction band
of k, a photon with energy Eg is not on its own sufficient
of k, a photon with energy Eg is not on its own suffcient to create an to create an Ec
Ec'--
electron-hole pair. Promoting an electron from the
electron-hole pair. Promoting an electron from the VB maximum to theVB maximum to the
CB minimum would
CB minimum would cause change in
cause aa change in its momentum, of
its momentum, 1)(kco -- kvo),
of '1(kco kyo). Eg
Momentum
Momentum has has to
to be conserved in
be conserved in aa crystal,
crystal, but
but since
since photons
photons possess
possess
virtually
virtually no momentum, that
no momentum, extra momentum
that extra momentum must must be be supplied
supplied by by some-
some- Ev
Ev

thing
thing else.
else.Usually
Usually ititisis
supplied
supplied bybya aphonon
phonon- - a a lattice
lattice vibration
vibration - - of
of the
the
correct
correct momentum.
momentum. The The phonon
phonon givesgivesup upits
its momentum
momentumto to the
the electron
electron atat
the
the moment
moment of of photon
photon absorption
absorption so so that both energy
that both energy and
and momentum
momentum ,are .are
conserved.
conserved. This
This type
type ofof semiconductor
semiconductor isis called
called an an indirect
indirect band gap mate-
band gap mate- distance
distance
rial.
riaL Clearly,
Clearly,photon
photon absorption
absorption can can only
only happen
happen in in indirect
indirect gapgap materials
materials
Fig,3.7.
Fig. 3.7. Energy--clistance
Energy-cistance band
band diagram
diagram of semiconductor.
of semiconductor.
if
if there are enough
there are enough phonons
phonons available
availablewith with the
the required
required value
value of k. This
of k. This
means
means that optical absorption is generally weaker for indirect than direct
that optical absorption is generally weaker for indirect than direct
gap
gap materials,
materials, andand that
that itit is
is more
more heavily
heavily dependent
dependent on on temperature.
temperature. The The 3.3.5. Density of
3.3.5. Density of states
states
dependence
dependenceof ofabsorption
absorptionon onphoton
photon energy
energyisisalso
alsomore
moregradual,
gradual,asaswill
wil be
be
discussed
discussedin in Chapter
Chapter 4. 4. According to
According to the Pauli exclusion principle, each
exclusion principle, quantum state
each quantum state can
can support
support
For
For device
device physics
physicspurposes,
purposes,usually
usuallyonlyonlythe the CB
CB minimum
minimum and VB
and VB only two electrons
only electrons ofof different
different spin.
spin. Since
Sinceeach
eachquantum
quantumstate
statein
in aa crystal
crystal
maximum
maximum energy
energyarearerepresented,
represented,ininan anenergy-distance
energy-distance band band diagram
diagram such
such isis defined
definedby byaa unique
uniquevalue
valueofofkk (k
(k is
is a
a 'good
'good quantum
quantum number'),
number'), there
there
as
as Fig.
Fig. 3.7.
3.7. This
This gives
gives us us no
no information
information on on the
the kk dependence
dependence of of the b~nd
the bind shouldbe
should be two
twoelectrons
electronsperperkk value.
value.AAcrystal
crystalofofvolume
volumeLLxxLL xx LL can can
structure,
structure, and
and does
doesnotnottell
tell us
us whether
whether the the band
bandgap gapisisdirect
direct oror indirect.
indirect. support (Lj21f)3
support different values
(L/211:)3 different valuesofofk,k,and
and hence
hence there
there are
are (1/21f)3 different
(1/211:)3 different
52 The Physics of
The of Solar Cells
CelI. Electrons and
and Holes
Holes in
in Semiconductors
Semiconductors 53

states per
k states per unit
unit crystal
crystal volume.
volume. This
This follows
follows from
from the
the requirement
requirement that The parabolic
parabolic band
band approximation
approximation has only
only limited
limited validity
validity for real
real ma-
ma-
must be
kLj27r must
kL/27r be an an integer
integer for aa wavefunction
wavefunction confined
confined in region of width
in a region terials.
terials. At
At energies far from
energies far from the principal band
band minimum
minimum (or
(or maximum)
maximum)
degeneracy, the
L. Including spin degeneracy, the density
density of
of electron
electron states
states per
per unit crystal electron states at other
electron states other symmetry points in
symmetry points in the
the band structure must
must be
be
volume, g(k) , is
volume, g(k), is included,
included, distorting the DOS
DOS from
from the form
form in
in Eqs.
Eqs. 3.16
3.16 and
and 3.17.
3.17. Where
Where
2 3 the parabolic
parabolic band
band approximation
approximation is
is really
really inappropriate
inappropriate we
we should use the
()323
g(k)d
9
3
(27r)3 dd k.
k d kk == (27r)3 k. (3.11)
(3.11) form
form of E(k) in
in Eq.
Eq. 3.14.
3.14.

It isisassumed
It assumed that
that the
theelectron
electronlevels
levels are
are close
close enough
enough for
for the integral
integral over
over
be aa good
good approximation
approximation to the sum sum of k states.
Excztons
E:z:citons
k to be
is generally
It is generally much more
more useful
useful to
to know
know the
the density
density of states
states (DOS) in So have treated
So far we have treated the electron and hole hole states independently.
independently. We We have
have
terms of energy,
energy, rather
rather than wavevector.
wavevector. We Weuseusethe
the band structure E(k)
band structure not considered
considered interactions between
between charge carriers which may
charge carriers may influence
influence
to convert
convert the
the integral
integral over
over wavevector space in
wavevector space in Eq.
Eq. 3.11
3.11 into an integral
integral the density
the density of states. An
of states. important effect
An important effect is
is the
the Coulombic interaction
Coulombic interaction
over energy.
over energy.IfIf the
the band
band structure
structure is isotropic
isotropic about the
the band
band minimum,
minimum, between electrons and
between electrons and holes,
holes, which
which gives
givesrise
rise to
to bound states
states called
called ex-
ex-
assumed here
assumed here to
to be
be at k == 0,
0, we
we can
can write
write citons.
citons. Excitonic states are
are built
built up
up from
from combinations
combinations of of electron and
and hole
hole
states of the same k. Physically they may
Physically they may be be stationary
stationary (k = 0) 0) or
or mobile
mobile
g(k)d3k = g(k) x 4n:k2dk (3.12)
(3.12) within the crystal.
crystal. The
The exciton
exciton energies
energies maymay bebe calculated
calculated byby considering
considering
whence the Coulombic interaction as
Coulombic interaction as aa perturbation of the the independent
independent particle
particle
crystal potential. A basis state ofof the form
form
dk
g(E)dE =
g(E)dE = g(k) 47rk 2 xx dE
g(k) xx 47rk2 dE .
dEdE. (3.13)
(3.13)
\lex = iPe(k,r)iPh(k,r')
(H the band
(If the band minimum
minimum is is at
at ko
ko '"
# 00 we
we simply
simply expand
expandabout
about(k
(k -- ko).
ko). The
The
for geE)
result for g(k) , then satisfies
satisfies a hydrogenic effective
effective mass
mass equation
geE) is the same.)
same.) Substituting for g(k),

geE)
2 2 2 dk
(27r)3 xx 47rk
geE) == (27r)3
2 dk
47rk x dE
dE .. (3.14)
(3.14)
r22 q2_
. n:ss r - r
--2 0 V \lex - 4 I " - Eex\lex

In the parabolic approximation, E(k)

parabolic band approximation, E(k) for
for an
an electron in the CB
electron in CB is
is where .0
where J.L* is the
the reduced
reduced effective mass of the electron-hole
effective mass electron-hole pair, Ss
e. the
the
given
given by Eq. 3.2. k2
3.2. From this we obtain k2 permittivity of the semiconductor and - Eex
dielectric permittivity Eex is the binding energy
of the excitonic state.
state. This
This has
has solutions
solutions for Eex
Eex
2 2m~
1i2 c .
kk2 == 2m~ (E -- EEea)
1l.2 (E 0) . (3.15)
(3.15)
Eex
_ J.L*
Eex -= -
e5Ryd
l:2~-Ryd
mo 1 where II = 1,2,3,
where 1, 2, 3,....
..
Differentiating Eq. 3.15 to
Eq. 3.15 find ;~
to find and substituting
:~ and substitutingin
in3.14
3.14we
we find
find the DOS
DOS 7no e.s; 12
2

for the CB, where Ryd is

where is the Rydberg energy:
energy: The electron and hole densities of states states

gc(E)
1 (2 me*)3/2
fi2
gc(E)= =27r-.2 (2m~)3/2 3/2
(E - Eca) . (3.16)
(3.16)
are thus modified by the presence of aa series
tonic states are
are not relevant for electrons
series of
electrons or
of bound
or holes
bound states.
holesin
states. Although exci-
in isolation,
isolation, the excitonic
27r2 -- (E - Eco)3/2 . levels are
levels are usually drawn on band
band diagrams
diagrams asas aa series
series of
of levels
levels below the con-
In a similar way we
we obtain
obtain the valence
valence band
band density
density of states
states duction band edge.
duction edge. The binding
binding energies are greatly reduced compared to
energies are
the hydrogen atom on account of of the screening effect of the semiconductor.
screening effect

gv
= _1_
(E) = 27[2 (2m~)3/2 (E
1l.2 3/2
_ E)3/2 (3.17)
(3.17)
In a typical
typical semiconductor,
semiconductor, the binding
binding energy is a few few meV,
meV, so the exci-
exci-
gv(E)
2n:2"V (EvovO- E)3/ .
-. (2m~)
tons are
tons are likely
likely to be ionised at room temperature.
ionised at temperature. Excitonic states at band
 54 The Physics
Physics of
ofSolar
SolarCells
Cells Electrons
Electrons and
andHoles
HolesininSemiconductors
Semiconductors 55
54 The 55

minima and
minima and maxima
maxima are
are important
importantininthc
thcoptical
opticalproperties
propertiesfor
forsemicon-
semicon- volume d3 k around
volume d3k around kk isisgiven
givenby
by
ductors , particularly in low dimensional structures. In molecular materials,
ductors, particularly in low dimensional structures. In molecular materials,
excitonic states
states are
are very
very important
important and
and dominate
dominate over
over band
band states,
states, so
so that
that
n(r)d3k = g(k)f(k, r)d3k
excitonic
this perturbation
perturbationapproach
approachisis not
notappropriate.
appropriate. and
this and the
the total
totalelectron
electron density
density in
in the
the conduction
conduction band
band by
by the
the sum
sum over
over kk
states
states
Box 3.3.
Box Low dimensional
3.3. Low

The above
The
dimensional systems

above treatment
systems

treatment of ofdensity
density ofof states
states is
is based
based on
on aa material
material system
system
n(r)
n(r) =1
=1 gc(k)f(k,r)d3k.
ge(k)f(k,r)d 3 k .
conduction
conduction band
band kk
(3.20)
(3.20)

with isotropic symmetry and would be invalid for highly non-isotropic

with isotropic symmetry and would be invalid for highly non-isotropic sys- sys- Since
Since a hole is an unoccupied electron
electron state,
state, the probability
probability ofof a hole
hole state
state
tems. One
tems. One important
importantsuchsuchclass
classare low dimensional
are low dimensional structures
structures where
where carri-
carri- being
being occupied is simply
simply 1-
1 - f(k,
f(k, r).
r). Thus
Thusthe
thedensity
densityof
ofholes
holes in
in the
thevalence
valence
ers are
ers are confined
confined inin one,
one, two or three
two or three dimensions
dimensions by by the
the presence
presence of of quantum
quantum band
band is
is given
given by
by
heterostructures such as quantum wells, quantum wires and quantum dots.
heterostructures such as quantum wells, quantum wires and quantum dots.
In these
In these cases
rections,
cases the
the electron
increasing
electron motion
the
motion is
minimum
is strongly
strongly quantised
energy above
quantised in
the
in the
minimum
rections, increasing the minimum energy above the minimum which applies
theconfined
confined di-
which
di-
applies
p(r) 1
p(r) = = r 9y(k)(1
9v(k)(1
J valence
- f(k,rd 3 k.
~ f(k,r))d3k.
band kk
valence band
(3.21)
(3.21)

in the bulk. Propagating k states can only exist in the unconfined direc-
in the bulk. Propagating k states can only exist in the unconfined direc-
tions, and
and so
so the
the sum
sum over
over kk states
states in
in Eq.
Eq. 3.14
3.14 must
must bebe taken
taken in in two,
two, one
one 3.3.7. Electron
3.3.7. Electron and
and hole
hole currents
currents
tions,
or zero
or zero directions
directions rather
rather than three. The
than three. The result
result isis that the form
that the form of 9(E) is
of 9(E) is In the
the effective
effective mass approximation, used so far, electron and hole densities
changed. For two dimensional systems, the DOS, now per
changed. For two dimensional systems, the DOS, now per unit area, is the unit area, is the
are represented
are by probability
represented by probabilitydistributions
distributions of
of plane waves. To
plane waves. Tofind
find the
the elec-
elec-
step
step function tron and
function and hole
hole currents,
currents, we
we need to weight
need to each probability
weight each probabilty carrier
carrier density
density
by its group velocity. Now, by
by analogy
analogywith
with the
the result for free electrons,
electrons, the
(In')
velocity. Now, for free
92D(E)
g2D(E) == (~n
h; B(E
8(E-- Ec)
Ee) (3.18)
(3.18) group velocity
group velocity of
of an
an electron
electronofofeffective
effectivemass m~m~
mass in in k kis is~.
state
state me~. The net
me
electron current
electron current density in the conduction
conduction band should
should therefore
therefore be be given
given
by the sum of contributions over
by over kk states,
where 8(E)
where B(E) isis the Heaviside function
the Heaviside and Ee
function and represents the
Ec represents the new,
new, shifted,
shifted,
minimum
minimum energy
energy state.
state. In one dimensional
In one dimensional systems
systems we
we have
have the
the DOS per
DOS per In(r) = - q~ 1 k9c(k)f(k,r)d3k (3.22)
unit length me conduction band k
unit length
and the
and the hole
hole current
current density
density in
in the conduction band
band by
E) - 2- (2m~)1/2 (E _ E )-1/2
1D (
991O(E) - = 271" h2
2- (2m~)1/2 e' (3.19)
(3.19) qh
27r -- (E - Ec)-1/2. Jp(r) = -- k9y(k)(1 - f(k,r))d3k (3.23)
(3.23)
mv valence band k
These
Theseconfigurations
configurations are
arerelevant
relevant to
to some
someof ofthe
the novel
novel photovoltaic
photovoltaic mate- wherewe wemake
makeuse useofofthe
thefact
fact that
that current
mate- where current is
is parallel to hole
parallel to hole flow, and
flow, and
rials and device designs, which will be discussed in Chapter
rials and device designs, which wil be discussed in Chapter 10. 10.
anti
anti parallel
parallel to
to electron
electron flow
flow..
So, in
So, in order
order to to calculate
calculate thethe densities and dynamics
densities and dynamics of of electrons
electrons and
and
holes
holes ininour
oursemiconductor
semiconductor we we need
need toto know the distribution
know the function f(k,
distribution function f(k, r)
r)
3.3.6. Electron distribution function
3.3.6. Electron distribution function as well
as wellasas the
the DOS.
DOS. In In general,
general,ff is is position
position dependent
dependent andand relies upon
relies upon
To calculate the densities of electrons
To calculate the densities of electronsandand holes
holesfrom
fromthethedensity
density of
ofstates,
states, (external)
(external) factors
factors which
which may
may vary
vary within
within the
the material.
materiaL.For
Forthe
the special
special case
case
we need to know how the states are filled. Let's define a distribution
we need to know how the states are filled. Let's define a distribution fuiic- fuIlc- of aa system
of systemininthermal
thermalequilibrium,
equilbrium, however,
however,thisthisdistribution
distribution isis spatially
spatially
tion,f(k,
tion, f(k,r),
r), such thatff is
suchthat is the
the probability
probabilty that
that at
at aa point
point rr the
the electron
electron invariantand
invariant anddescribed
describedbybyFermi FermiDimcDimcstatistics.
statistics.This
Thisisistreated
treatedinin the
the
state
stateofof wavevector
wavevectorkk isisoccupied.
occupied.Then
Thenthethedensity
densityof of electrons
electronsinin aa small
small
next section.
next section.
56
56 The Physics
The Physics of
of Solar
Solar Cells
Cells Electrons
Electrons and
a.nd Holes
Holes in
in Semiconductors
Semicondu.ctors 57
57

3.4. Semiconductor
3.4. Semiconductor in
in Equilibrium
Equilbrium and the total
total density
densityof
ofelectrons
electrons in
in aa conduction
conduction band
band of
of minimum
minimum energy
energy
Ee by
Ee by
3.4.1. Fermi
3.4.1. FermiDirac
Dirac statistics
statistics
At absolute
At absolute zero
zero the
the electrons
electrons have
have no
no kinetic
kinetic energy
energy and
and always
always occupy
occupy the
the n roo
n = roo ge(E)fo(E,
9c(E)/o(E, EEF,
F , T)dE
T)dE (3.27)
lowest available
lowest available levels,
levels,filling
fillng up
up the available
available states in order of
in order of increasing
increasing JEo
JE,
energy. The energy up to which
energy. which states
states are
are filled
filled is
is called
called the Fermi energy,
the Fermi ener9Y, where the upper
where the upper limit
limit of
ofintegration
integrationhas
has been
been extended
extended to infinity.
EF. At
EF. At finite
finite temperatures the electrons
temperatures the electrons have
have some kinetic energy,
some kinetic energy, and
and The density
density of
of holes
holes in aa valence band of maximum energy
valence band energy EyEv is
is given
given
some of
some of them are excited
them are excited into
into states
states above EF, leaving
above EF, leaving some
some states
states below
below by
EF unoccupied.
unoccupied.
Ev
equilibrium means
means that are no netexchanges
no net exchanges ofof particles
part icles
Thermal equilibrium
energy between
or energy between different
semiconductor and
semiconductor
that there are
different points
points in
and its surroundings.
surroundings. Every
semiconductor or between
in the semiconductor
Every point in the
between the
the semiconductor
semiconductor is is
l
P = J rEv
-00 gy(E)(1-- fo(E,
-00 gv(E)(1 EF,, TdE
/o(E, EF T))dE.. (3.28)

the ambient
ambient temperature,
temperature, T, T ,so
so that
thatall
allcarriers
carriershave
have the
the same
same average
average ., Figure 3.8 illustrates
Figure 3.8 ilustrates the
the Fermi
Fermi Dirac distribution function
function and
and its
its effect
effect
at the
internal energy
kinetic or internal energy of ~kBT where
of ~kBT kB is Boltzmann's constant. The
where kB The on the energy
energy distribution
distribution of
of electrons
electrons and holes in a semiconductor
semiconductor with
distribution ofof particles
particles has
has settled
settled soso that
that that there
there are
are no net particle
particle roughly parabolic
roughly parabolic bands.
flows and EF
flows and EF isisthe
the same
sameatat all
all points.
points. In
In these
these equilibrium conditions, Fermi
equilbrium conditions,
Dirac statistics describe
Dirac statistics describe the
the most stable energetic
most stable energetic distribution
distribution of
of electrons
electrons
which
which isis consistent
consistent with
potential energy (EF).
For
with their

special case,
For this special
through the electron
electron energy,
their internal

case, If is
is dependent
energy (kBT)
internal energy

dependent upon
energy, and is
(kBT) and
and their statistical

upon wavevector
is independent
independent of
wavevector only
of position.
position.
only implicitly
implicitly
~l 1\
~E)r r .1' r---l,
~ ~ E

o ~r
I(k,r) 10(E(k) ,EF,
f(k, r) == fo(E(k), EF,T)
T) (3.24)
(3.24)
fIE) r 1 t: ) ,
.E'i:
where 10(E,
where fo(E, E F, T)
EF, Fermi Dirac distribution function,
T) is the Fermi function, giving the av- T:>O
erage
erage probability
probabilitythat
that an
an electron
electronstate
state at energy EE wil
at energy will be
be occupied
occupied at
at ~ E
some temperature T,
some temperature T,
~

fo(E,EF,T)
10(E, EF, T) == e(E-EF)~kBT
.~ ~ ,1, _ + 1 . (3.25)
(3.25)
~~ r
n(E) r

(T=O)
IT=O)
3.4.2. Electron and
andhole
hole densities
densities in
in equilibrium E
E
3.4.2. Electron equilibrium

The electron
10.
electron and hole densities
Provided that the
densities can
density of
can be
be derived
states
derived from Eqs.
can be expressed
Eqs. 3.21-3.22
in
3.21- 3.22 using
terms of energy,
_(E) r
nlE) r
fa. Provided that the density of states can be expressed in terms of energy, (T>O)
(T"O)
it is usually more convenient
convenient to
to do
do the calculations
calculations over
over electron
electron states
states in E
E
terms
terms of energy.
energy.Then
Then the
the number densityn(E)
numberdensity nee) of
f electrons
electrons with
with energy
energy inin
the range EE to E +
the range in aa system
+ dE in system with
with density
density of
ofstates
states geE)
g(E) is given-by
given"1:>Y Fig, 3,8.
Fig. 3.8. Density
De nsityof
ofstates
statesfunction
function g(E)
g(E)ofofaa semiconductor
semiconductor with parabolic
p';"abolic bands, Fermi
Dirac
Dirac distribution function, f(E)
distribution function, , and
f(E), and energy dist ribution, neE),
energy distribution, n(E), of
of electrons
electrons (shaded
(shaded

n(E)dE =
= g(E)fo(E,
g(E)/o(E ,EF, T)dE
EF, T)dE (3.26) area) at
area) at TT = a0 and finite temperature.
temperature,
(3.26)
58 The
The Physics
Physics of Solar Cells
Cells Electrons
Electrons and Holes
Holes in
in Semiconductors
Semiconductors 59

3.4.3.
3.4.3. Boltzmann approximation
Boltzmann approximation This relationship is used
relationship is used to
to define
define aa constant
constant property
property of
of the
the material,
material, the
intrinsic
intrinsic carrier density ni
carrer density n
For a semiconductor at absolute
absolute zero,
zero, the valence
valence band
band is
is completely
completely filled
and the conduction
and the conduction band completely empty.
band completely empty. This
This means that the
means that the Fermi
Fermi n~ = np = NcNve-Eg/kBT (3.36)
(3.36)
level
level must lie somewhere
must lie somewhere inin the
the band gap. Now,
Now, if EF is
is far
far enough
enough from
from
band edges,
both band edges, fo can be
fo can be well
well approximated by the Maxwell-Boltzmann
Maxwell-Boltzmann n
ni is equal to the
the density
density of
of electrons
electrons which
which are thermally excited into the the
form.
form. InIn the
the conduction
conduction band when EE
band when EF ,
).). EF, CB of aa pure semiconductor
CB semiconductor inin thermal equilibrium,
equilbrium, and
and isis necessarily
necessarily also
also
equal
equal to the number
number of
of holes
holes which have
have been
been left behind.
fo(E, EF. T) ~ e(EF-E)/kBT (3.29)
(3.29) It is sometimes convenient
convenient to
to write
write nand
nand p in terms of ni
n and an intrinsic
intrinsic
potential energy
potential Ei,
energy Ei,
and in
in the
thevalence
valence band whereEE
bandwhere 0(0( E
EF,
F,
n=
= n
nj exp((EF - E)/kBT)
Ej)/kBT) (3.37)
(3.37)
1 - fo(E,EF,T) ~ e(E-EF)/kBT. E 0(0( EF (3.30)
(3.30)
p = nj exp((Ei
= n exp((E - - EF
EF )/kBT)
)/kBT) (3.38)
(3.38)
These
These approximations simplifythe
approximations simplify theintegrals
integralsininthe
the expressions
expressionsfor
fornand
nand where
(Eqs. 3.27
p above (Eqs. 3.27 and 3.28).
3.28). In the parabolic
parabolic band approximation,
approximation, using
using
Eqs.
Eqs. 3.16
3.16 and
and 3.17 forg(E),
3.17for nand ppcan
g(E), nand can be
be evaluated
evaluated exactly.
exactly. We
We find
find for i 1 ( Nc )
gi= -(E
2 +c E)v- -kTln
2 Nv-
the electron density,
the electron density,
i 3 ~kBTln
n = Nc exp((EF - Ec)/kBT) (3.31)
(3.31) 2 4 (m*)
~(Ec
= -(Ec +
m~
+ Ev) (:D .
Ev)- - -kBTln -- . (3.39)
(3.39)

where
where the
the constant Nc is called
constant Nc called the
the effective
effective conduction
conduction band
band density
density of E
Ei is an
an energy
energy close
close to to the
the centre
centre of the band
band gap,
gap, and is equal
equal to the
the
states
states and is given by Fermi level
level of the pure semiconductor
semiconductor in in equilibrium.
Another physically
Another physicallyimportant
importantquantity
quantityisis the
the electron
electron affinity
affnity of the
Nc = 2 (m~kBT)3/2 (3.32)
(3.32) semiconductor, X.
semiconductor, X. XX is
is the least amount of of energy
energy required to remove
remove an
2rr!i2 electron from
electron from thethe solid.
solid. It is measured from the conduction
measured from conduction band edge
edge to
the vacuum
vacuum level
level Evac. Evacisisthe
Evac. Evac the energy
energyto to which
which anan electron
electron must be be
Similarly for the
Similarly for the hole density,
hole density,
raised to be
be free
free of
of all
all forces
forces from
from the solid. Any spatial variations
variations in Evac
in Evac
p = Nvexp((Ev - EF)/ksT) (3.33)
(3.33) are due to electrostatic
electrostatic fields.
fields. The conduction and valence
valence band edges and

where
where the effective valence
valence band
band density of
of states
states is
~ac vacuum level

X
X
Nv = 2 (m~kBT) 3/2 (3.34)
(3.34)
2rr!i2
i;
~ conduction band
kTlnNc
kTlnNc
Equations 3.31 and
Equations 3.31 and 3.33 say,
say, very
very simply,
simply,that
that the
the electron and hole densities ~
Ei Fermi level
vary
vary exponentially
exponentially with with the
the position
position of
of the Fermi level
the Fermi level in
in the band
band gap.
gap.
kTin Nv
kTln N
Moreover, they
Moreover, they tell tell for any
us that for
us that any given
given material
material at
at a given
given temperature v
valence band
the product np np is
is a constant,
constant, ~
E.

np = NcNve-Eg/kBT . (3.35)
(3.35) Fig, 3.9.
Fig. 3,9, Position
PositionofofFermi
Fermilevel
level and
and vacuum
vacuum level
level on the energy
energy band diagram.
diagram.
60 The Physics of
The Physics of Solar
Solar Cells
CeUs Ele.ctron5 and Holes
Ele.ctrons and Holes in
in Semiconductors
Semiconductors 61

the Fermi level

level can
can be related to Eva.c as
to Eva. as follows:
follows: From the
From the above argument we
above argument wecan
canalso
alsosee
seethat
that f(k,
f(k, r) must be
be asym-
asym-
metric in k if
metric if the electron
electron and hole currents are not to
to vanish.
vanish.
Ee
Ec = Evae -- X
Evac X

Ev =
Ev = Evac -- X
Evac X -- Eg
Eg (3.40)
(3.40) 3.5. Impurities and
3.5. Impurities and Doping
Doping

EF = Evac - X - kBTlnNc = Evac - X - Eg + kBTlnNv. 3.5.1. Intrinsic semiconductors

3.5.1. Intrinsic semiconductors

The semiconductor
The describedsosofarfaris isintrinsic
semiconductor described intrinsic- - it is
is aa perfect
perfect crystal
crystal
Validity of
Validity of Boltzmann
Boltzmann approximation impurities. The only energy levels
containing no impurities. levels permitted
permitted are the levels
levels of
The above approximations
approximations for
for nand
nand pp hold
hold so
so long
long as well defined
defined kk which arise
arise from
from the
the overlap
overlap of of the
the atomic
atomic orbitals
orbitals into crys-
crys-
tal bands,
bands, as described
described above.
above. The properties of those those bands
bands determine the
~:;:;1,
Ee
Ec -EF
- EF
~1,
position of the Fermi level
which have
level in
in equilibrium,
equilbrium, E,
enough thermal energy to cross
have enough
E j , and
and the
thedensity
densityofofcarriers,
cross the band gap and conduct
carriers,n,
nj,

conduct elec-
elec-
and
tricity. They also determine conductivity since the intrinsic semiconductor
tricity. semiconductor
has nj
has n electrons
electrons and nj
n holes available for conduction
holes available conduction andand conductivity
conductivity(T(Tisis
EF - Ev :;:; 1 given by
kBT
(T = qllnn + qllpP (3.41)
(3.41)
which are
conditions which are usually
usually true
true for
for aa semiconductor
semiconductor inin equilibrium.
equilbrium. If the
parabolic band
band approximation is is not appropriate, then the form of Nc
appropriate, then Ne and
and where {.tn,
where lIn, and
and /Lp
llp are
are the mobilties
mobilities ofof the
the electrons
electrons and
and holes,
holes, respectively,
respectively,
NNv wil be different,
v will but the energy
different, but energy dependence
dependenceof ofnand
nand pp will
wil be the same and q is is the electronic charge.In
electronic charge. Inequilibrium,
equilbrium, nand nand pp are
arereplaced
replaced with
with n
nj

as
as above.
above.nand diverge from the simple exponential
nand p diverge exponential form conditions
form in conditions in
in Eq. 3.41.
Eq. 3.41.
where
where the Fermi levellevel approaches
approaches the the lowest
lowest CB
CB or highest VB VB leveL.
level. This At room temperature the the conductivity
conductivity of of an
an intrinsic
intrinsic semiconductor
semiconductor is
can
can happen
happen if semiconductor is
if the semiconductor is highly doped
doped (see
(see below)
below) or
or if there is generally very smalL.
small. ForForexample
examplefor forintrinsic
intrinsic silicon,
silcon, n
nj =
= 1.02
1.02xx1010 cm- 3
1010 cm-3
aa high density
density of
of defect
defect states
states in the
the band
band gap.
gap. Then
Then the
the semiconductor
semiconductor and (J(J == 3 xX 10-6
and 6
10- Ohm-I I
Ohm- cm-1, I
cm- ,atat300 300K.K.Conductivity
Conductivityincreases
increases with
is said to be
is be degenerate,
degenerate, and the full full form
form of the Fermi Dirac distribution, increasing temperature,
increasing temperature, and and with decreasing
decreasing band gap gap since
since n
nj varies
varies as
as
Eq. 3.24, must be
3.24, must used to
be used to evaluate
evaluate nand
nand p. e-Egl2kBT. For
e-Eg/2kBT. For example,
example, germanium
germanium with a band gap of
band gap of 0.74
0.74 eV has aa
eV has
conductivity of
conductivity of22xx10-10-22
Ohm-II cm-
Ohm- cm-II while
while gallum
gallium arsenide
arsenide with a band
8 Ohm- I em-I, many orders
gap of 1.42
gap 1.42 eVeV has
has aa conductivity
conductivityofof10- 10-8 Ohm-I cm-I, many orders of
3.4.4. Electron and
3.4.4. Electron and hole
hole currnts
currents in
in equilibrium
equilibrium
magnitude smaller.
smaller.
To find IInn and
To find Jp in
and Jp in equilibrium,
equilbrium, we we need
need toto evaluate
evaluate Eqs.
Eqs. 3.22
3.22 and 3.23
and 3.23 Now supposethat
Now suppose that the crystal is is altered
altered byby introducing
introducing an an impurity
impurity atom
with f(k,r) fo(E(k),EF,T). Here
f(k,r) = fo(E(k),EF,T). Herethe the integral
integral must
must be done over over kk or a structural
structural defect.
defect. The
The impurity
impurityor ordefect
defect introduces
introduces bonds
bonds ofof different
different
states since
since k occurs
occurs explicitly
explicitly in the
the integrand.
integrand. However
However we can take ad-
we can strength to to those
those which
which make up the perfect crystal, and and therefore
therefore changes
changes
vantage of
vantage of what
what we
we know
know about
about the
the dependence
dependenceofofEE on on k.
k. Since, in the
Since, in the local
local distribution
distribution of of electronic
electronic energy
energy levels.
levels. The altered energy
energy levels
levels
parabolic band
parabolic approximation, EE is
band approximation, is an
an even function of
even function k, g(E(k))
of k, g(E(k)) and and (unless the density of defects
are localised (unless defects isis very
very high),
high), unlike
unlike the
the extended
fo(E(k),
fo(E(k), EF,E F, T) are also
T) are also even
even functions
functionsof of k.
k. That means that
That means the inte-
that the inte- k states
states which
which make up the intrinsicintrinsic conduction and valence valence band states.
grand, kg(E(k))fo(E(k),
grand, kg(E(k))fo(E(k),EF,T) EF, T) wilwillbe
bean anodd
odd function
function of k,k, and so the If the impurity energyenergy levels occur within
levels occur within the
the band gap they can can affect
affect
integral
integral when taken over
when taken over all
all kk states
states will
wil vanish. Therefore IIn
vanish. Therefore J p :;
= Jp
n = 0;
:;;: 0; the electronic properties of the semiconductor. Introducing occupied impu-
i.e., no
i.e., no net current flows
flows in the semiconductor
semiconductor in in equilibrium.
equilibrium. That is is ex-
ex- rity levels
levels above
above E E j increases the Fermi
Fermi level,
level, which increases the densitydensity
actly what
what wewe would
would expect. electrons relative
of electrons relative toto holes
holes inin equilibrium
equilbrium (as is is clear
clear from Eqs. 3.37 and
62 The Physics
The Physics of
of Solar
Solar Cells
Cells Electrons
Electrons and
a.nd Holes
Holes in
inSemiconductors
SemiconductDrs 63
63
62

3.38}. In
3.38).
and
In the

nature of
nature
thesame
and increase
ofthe
sameway,
increase the
way, unoccupied
the density
the carriers
carriers in
unoccupiedlevels
density of
of holes
inthe
levels below
holes relative
relative to
the semiconductor
E j reduce
below E reducethe
electrons. The
to electrons.
semiconductor can
can thus
thus be
theFermi
Fermilevel
The density
density and
be controlled
level
and the
controlled by
the
by adding
adding =0=0=0=
II
II IIII IIII
0=0=0= EC
E
definite amounts
dcfinite
valence
amounts of
band
of impurities
edge.
impurities with
This is
with energy
called
energy levels
doping.
valence band edge. This is called doping.
levels close
close to the conduction
to the conduction or
or
AI, III
_IIIIAk\
o~e-;o=
-0-+0-;---0=
-t--~-------~
~--~------_. E EFF

3.5.2. nn type
3.5.2. type doping
doping I "11"/ I
0=0=0=
0=0=0=
II '~lle"/ II
E
A semiconductor
A semiconductor whichwhich has been doped
has been doped to to increase
increase the
the density
density ofofelec-
elec- v
trons relative
trons relative to
to holes
negative.) Occupied
negative.)
holes is
Occupied levels
is called n type.
called n
between E
levels between
type. (The
(The principal
principal charge
Ec are
and Ee
Ej and
charge carriers
are introduced
introduced by
carriers are
byreplacing
are
replacing I III III
II
some of
some of the atoms in
the atoms in the
the crystal
crystal lattice
lattice with
with impurity
impurityatoms
atomswhich
which possess
possess Fig,
Fig. 3.10.
3.10. Schematic
Schematic ilustration
illustration of an nn type
type impurity
impurity in
in the
the bond
bond (left)
(left) and
and band
band
too many
one too many valence
valence electrons
electrons for
for the
the number
number of of crystal
crystal bonds.
bonds. Such
Such im-
im- (right) picture,
(right) picture. The
The extra
extraelectron
electron is
is loosely
loo.sely bound
bound to the donor
to the donor atom.
atom. When
When the
the ionisa-
ionisa-
one tion
tion energy
energy of VnVn is supplied,
supplied, the extra electron
electron is freed
freed from the donor,
donor, andand the
t he donor
donor
purities are
purities are called donor atoms
called donor atoms because
because they
they donate
donate an extra electron
an extra electron toto atom becomes positively charged.
becomes positively charged, InIn the
the band
band picture, the electron
electron is
is raised
raised through
through VnVn
the lattice. An example would be an atom of phosphorus,
the lattice. An example would be an atom of phosphorus, which has five which has five into the
the conduction
conduction band,
band.
valence electrons,
valence electrons, in
in the
the tetravalent
tetravalent silicon lattice. The
silcon lattice. The extra
extra electron
electron is
is not
not
needed in
needed the strong
in the strong directional
directional covalent
covalent bonds
bonds which
which hold
hold each
each atom
atom to to
temperature, then
temperature,
its four
its four neighbours.
neighbours. Therefore
Therefore itit isis much
much less
less well
well bound
bound than the other
than the other
valence electrons,
valence electrons, and
and is
is instead held rather
instead held rather loosely
loosely inin aa Coulombic
Coulombic bound
bound n;:Nd (3.42)
state with the
state with the phosphorus
phosphorus atom.
atom. TheThe donor
donor can
can be
be ionised
ionised relatively
relatively easily,
easily,
leaving and
leaving the
the extra
extra electron
electron free
free to
to move
moveandandthe
the fixed donor atom
fied donor atom positively
positively
charged. For typical
charged. For typical donors,
donors, the
the ionisation
ionisation energy, Vn , is
energy, Vn, is some
some meV
meV oror tens
tens p=n?INd, (3.43)
of meV. Assuming
of meV. Assuming a a hydrogenic
hydrogenic bound
bound state,
state, the
the ionisation
ionisation energy
energy isis ap-
ap-
proximated by
proximated by since np
since nr
np == n? at
at equilibrium.
equilibrium. The
The electron
electron density
density is
is now
now greatly increased
. 2
over its
over its equilbrium
equilibrium value,
value, while
while the hole
hole density
density isis greatly reduced.
reduced. The
Vn = meo Ryd here called
electrons are here called the
the majority
majority carriers
carriers and
and the holes
holes the
the minority car-
mo~
riers. Relat
riers. Relative
ive to the intrinsic case,
case, the total
total density
density ofof carriers is
is increased,
where
where s sisisthe
the relative
relative dielectric
dielectric constant
constantof ofthe
the material and Ryd
material and Ryd isis the
the and so
and so therefore
therefore isis the conductivity. Conduction in
conductivity. Conduction in nn type semiconductors
semiconductors
Rydberg
Rydberg energy, 13.6 eV. For typical crystallne semiconductors s is of the
energy, 13.6 eV. For typical crystalline semiconductors s is of the is mainly by electrons.
is
order
order ofof 10
10 and
and m~m~ lessless than
than one, meaning Vn
one, meaning Vnwill
wil be
be reduced
reduced by by aa factor
factor
of
of 100
100 compared
comparedto to the
the Rydberg.
Rydberg. Provided
Provided that the impurity
that the impurity isis chosen
chosen soso 3.5.3. P type doping
3.5.3. doping
that Vn is
that Vn small enough,
is small enough,virtually
virtuallyall allthe
the donor
donor atoms
atoms will
wil be ionised at
be ionised at
room
room temperature.
temperature. A semiconductor
A semiconductor which
which isis doped
doped to to increase
increase the
the density of positive charge
In the band
In the band picture,
picture, the the donor
donor electrons
electrons have
have been
been promoted
promoted from from aa carriers relative to negative is is calledp
calledp type. It is produced by replacing some
level
level inin the
the band
band gap,gap, Vn below EEe,
Vn below e , into
into the conduction band.
the conduction Since the
band. Since the the atoms
of the atoms in in the
the crystal
crystal with
with acceptor impurity atoms,
acceptor impurity atoms, which
which contribute
contribute
donor
donor states
statesare areallallfilled
filled at
at TT = 0, the
= 0, the Fermi
Fermi level
level must
must now
now lie
lie between
between too few
too few valence
valenceelectrons
electronsfor
forthe
thebonds
bonds they
they need
need to
to form.
form. An
An example
example would
would
the
the donor and Ec.
level and
donor level Ee. be the trivalent element
be element boron in silicon.
silicon. The acceptor becomes
becomes ionised byby
The
The density
density of carriers can
of carriers can be
be controlled
controlled by by varying
varying thethe density
density of of removingaa valence
removing valenceelectron
electronfromfromanother
anotherbond
bond toto complete
complete the
the bonding
dopants,NNd.
dopants, d . IfIf Nd
Nd ~ : nnjand
andthethedonors
donors areare fully
fully ionised
ionised atat room
room between itit and
between and its four
four neighbours.
neighbours. This This releases
releases aa hole
hole into
into the valence
valence
64
64 The Physics
The Physics of
of Solar
Solar Cells
Cells Electrons and
Electrons and Holes
Holes in Semiconductors
Semiconductors 65
65

III III \II

----CB
CB ~""~~ CB ----CB
CB
=0=0=0=
= 0=0=0= E
c
EF
-- E F
donor level

=~=~ . ~~=
=~=~,,~=
'_ I
acceptor
acceptor level
level
-----E-F
EF
VB
II II II
=0=0=0=
=0=0=0=
\I \I \I
---v;t-----;-
---v;t------. E F
Ev
EF
intrinsic
VB

n type
VB VB
VB

I\I III III

v ptype
p type
Fig. 3,12,
Fig. 3.12. Position
Position of
ofFermi
Fermi level
level and
and impurity
impurity levels
levels relative
relative to the
the conduction
conduction and
and
valence band
valence band edges.
edges. Shaded regions
regions indicate
indicate levels
levels filled
filled by electrons.
Fig. 3.11. Schematic
Fig. 3.11. Schematic ilustration
illustrationoforaa pp type
type impurity
impurity in
in the
the bond
bond (left)
(Iert) and
and band
band (right)
The acceptor
picture. The acceptor atom
atomhas has one
one too
too few
rew electrons,
electrons, and
and becomes
becomes ionised
ionised by grabhing
grabbing
another electron from a neighbouring bond. The grabbed electron is more
neighbouring bond. more tightly bound
to the
the impurity
impurity than
than toto aanormal
normalcrystal
crystal atom.
atom. The
Thehole
hole created
created isis relatively
relatively free
free to 3.5.4. Effects of heavy
3.5.4. Effects heavy doping
doping
travel from
travel from site to site,
site. In
In the
the band
band picture,
picture, the
the hole
hole isis lowered
lowered through
through Vp Vp into the
the
valence band.
valence Heavy doping
Heavy doping causes
causes imperfections
imperfectionsininthe
the crystal
crystal structure
structure which
which appear
as states in the band
band gap
gap close
close to the
the CB
CB and
and VB
VB edges.
edges. These states havehave
the effect of adding
effect of adding aa tail to the
the CB
CB and
and VB
VB density
density ofof states
states functions,
functions,
band. The energy
band. The of this
energy of this ionised state is
ionised state is higher,
higher, by
by a
a small amount
amount of
energy V
and so effectively reducingthe
effectively reducing the band
band gap.
gap. The
The intrinsic
intrinsic carrier
carrier density
density will
wil
energy p , than the highest
Vp, highest energy
energy of
of aa valence
valence band
band electron, and so so the
increase, because thermal
increase, because thermal excitation
excitation across
across the
the band gap is is easier,
easier, and this
acceptor energy level
acceptor energy levelappears
appears in
in the
the band gap close
close to thethe valence
valence band
band
edge.
edge. The Fermi level now lies
level now lies between
between thethe acceptor level
level and Ev.
has consequences
consequences for for solar cell
cell performance.
performance. Heavy
Heavy doping
doping is also
also likely
likely
These pp type semiconductors contain
contain anan excess
excess of to increase the density
increase the density of defect
defect states
states which
which act as as centres
centres for carrier
carrier
of positive carriers, holes.
.l0sitive carriers, holes.
recombination or or trapping.
doping density of Na ~~nnjionisable
recombination trappin.
For a doping ionisableacceptors, we find
acceptors-;-we find

p",Na (3.44)
(3.44) 3.5.5. Imperfect
3.5.5. Imperfect and
and amorphous
amorphouscrystals
crystals
and As well as extrinsic impurities,
as extrinsic impurities, semiconductors intrinsic defects
semiconductors may contain intrinsic defects
n = nriNa. (3.45) which introduce levels
levels into the band
band gap and modify the the electronic
electronic prop-
prop-
(3.45)
erties.
erties. Even
Even in aa perfect
perfect monocrystallne
monocrystallinesemiconductor,
semiconductor, configurational
configurational
Again the
the total
total carrier
carrier density
density and
and hence the conductivity is greatly
hence the greatly in-
in- defects
defects arise from broken
arise from broken bonds
bonds and
and structural rearrangement
rearrangement at at surfaces.
surfaces.
creased,
creased, but now
now conduction
conduction is mainly
mainly by holes,
holes, which are the majority
which are majority In a polycrystallne
polycrystalline semiconductor,
semiconductor, made up of of grains
grain of
of the same crystal at
carriers in
carriers in this
this case.
case. various orientations, defects occur at grain boundaries.
defects occur boundaries. These
These defects
defects may
Notice from Eqs.
Notice from Eqs. 3.37,
3.37, 3.38
3.38 and
and 3.42-3.45
3.42-3.45how howthe the changes
changesininnandnand cause an otherwise intrinsic material to become become slightly nn or p type, by by self
self
pp are
are consistent
consistent with
with thethe changes
changes in the
the Fermi
Fermi leveL.
level. InIn an intrinsic(i.(i.e.,
an intrinsic e., doping.
doping. They can also also be
be responsible
responsible for
for charged
charged boundary layers near to
pure) semiconductor
semiconductor EF EF lies
lies roughly
roughly inin the
the middle
middle of of the
the band gap. The
bandgap. The surface or grain boundaries
boundaries in in deliberately
deliberately doped
doped materials,
materials, which
which impede
impede
effect of
effect of doping is to shift
shift the
the Fermi
Fermilevel
level away
away from
from thethe centre
centre of
of the
the band
band carrier
carrier transport.
transport.
gap, towards Ec in
gap, i'n nn type
type material,
material,and
andtowards
towardsEv Ev ininPPtype
typemateriaL.
material. There is
There is another
another important
important group
group ofof semiconductor
semiconductor materials,
materials, amor-
amor-
Note
Note also
also that, unlike
unlike heating
heating and
and ilumination,
illumination,doping
dopingisisaaway
wayof. of..in-
in- phous
phous semiconductors. These have
semiconductors. These haveaa similar
similarstructure
structure to
to the crystal on the
creasing the conductivity of the semiconductor
semiconductor at at equilbrium
equilibrium without
without re- re- short
short range,
range, but
but have
have nono long
long range
range order. For instance, in amorphous sil- sili-
quiring aa constant
quiring constant input
input of
of energy.
energy. con, while each
each silicon
silcon atom is bonded to four neighbours with approximate
approximate
 The
The Physics
Physics of Solar Cells
Cells Electrons
Electrons and Holes
Holes in Semiconductors
Semiconductors 67
66

tetrahedral all points

all points in the semiconductor
semiconductor are are no
no longer
longer inin equilibrium,
equilbrium, andand also
also kk
tetrahedral symmetry (just as
symmetry (just as in crystalline silcon)
in crystallne silicon) the
thearrangement
arrangement of of sil-
sil-
icon dependent because
dependent because thethe applied bias may
applied bias may be directional
directional and maymay favour
favour
icon atoms four or
atoms four or five
five bond lengths away
bond lengths away appears almost random.
appears almost random. These
These
small occupation of some
some kk states
states rather than others of the same same E.
small deviations
deviations in in bond
bond length
length and orientation give
and orientation give rise
rise to
to aa spread
spread inin
energy levels so that the density of states near the conduction band mini- Now
Now -- and
andhere
herecomes
comesone
oneofofthe
the great
great simplifications
simplifications of semiconductor
energy levels so that the density of states near the conduction band mini-
mum physics -- ifif the
the disturbance
disturbance isis not too great,
great, oror not
not changing too quickly,
quickly,
mum and valence band
band maximum
maximum tendstends to decay with
with energy
energy into
into the band physics not too changing too
and valence to decay the band
gap, the populations of of electrons and holes each relax to achieve
achieve aa state of
of quasi
quasi
gap, in
in an
an Urbach
Urbach tail, rather than
tail, rather than cutting
cuttingoff
offabruptly.
abruptly.Amorphous
Amorphous semi-semi-
conductors thermal equilibrium.
thermal eqilibrium. What that that means
means is is that
that thethepopulation
population ofofelectrons
electrons
conductors are also very
are also likely to
very likely to contain
contain defects
defects due
due to voids and
to voids and broken
broken
bonds. Intrinsic
Intrinsic defects
defects and amorphous semiconductors
semiconductors will be discussed
discussed in
in within the conduction band distribute themselves
within themselves as as though
though they
they were
were at
bonds. and amorphous wil be
Chapter 8. 8. equilbrium, with aa common
equilibrium, common Fermi level and
Fermi level and temperature,
temperature, and thethe holes
holes
A within the valence themselves as
valence band arrange themselves as though
though they
they shared another,
A very
very high
high density
density of of defects
defects in
in the
the band gap is
band gap is undesirable,
undesirable, as as these
these
tend to act
act as
as centres
centres for
for charge
charge recombination
recombination (see
(see Chapter 4). It
It also
also gives
gives different Fermi level andand possibly
possibly aa different
different temperature.
temperature. In In quasi
quasi thermal
tend to Chapter 4).
rise equilibrium,
rise to an effect
to an effect called
called Fermi
Fermi level
level pinning,
pinning, where
where the
the density
density ofof intra band
intra band
gap states is too high for all the states to be ionised at room
gap states is too high for all the states to be ionised at room temperature, temperature,
and
and soso the
the Fermi
Fermi level
levelisisfixed
fied amongst
amongst them.
them. This
This makes
makes itit difficult
diffcult to to dope
dope fc(k,r) ~ fo(E,EFn,Tn)
the semiconductor in
the semiconductor the usual
in the usual way.
way. Fermi
Fermi level
level pinning can be
pinning can be aa problem
problem
and
at interfaces
interfaces andand is
is mentioned
mentioned in Chapter 5. 5.
fv(k, r) ~ fo(E, EFp, Tp).
3.6. Semiconductor under
3.6. Semiconductor under Bias
Bias
The new apparent
apparent FermiFermi levels
levels for
for electrons
electrons and holes holes are called
called the
the electron
So far we
So far we have
have considered
considered the the semiconductor
semiconductor at at equilibrium.
equilbrium. One feature
One feature and hole quasi
quasi Fermi
Fermi levels, EFn and
levels, EFn EFp, respectively.
and EFp, respectively.
of the
of the material
material at equilibrium is
at equilbrium is that
thatno
no current
currentflows.
flows. To
To understand
understand the the The approximation
approximation is possible because relaxation
possible because relaxation within each band is
within each is
operation of a solar cell, we need to understand what happens
operation of a solar cell, we need to understand what happens to the semi-to the semi- so much
so much faster
faster than relaxation
relaxation between
between the the bands.
bands. (Carriers relax within
conductor when it
conductor when is displaced
it is displaced from
from equilibrium
equilbrium by by exposure
exposure to
to light.
light. Since
Since the bands mainly by scattering from from the lattice, with the emission emission and ab-
current flows in
current flows in the operating solar
the operating solar cell,
cell, by
by definition
definition the device cannot
the device be
cannot be sorption ofphonons.
ofphonons. This This occurs
occurs on on aa time
time scale
scale of 10- 12 _10- 15 s. Between
of 10-12_10-15
at equilibrium.
equilbrium. bands,
bands, the carriers relax only only by by interacting
interacting with with another
another carrier,
carrier, with
with the
emission
emission of of aa photon
photon or or with a deep trap. Relaxation
Relaxation over over these
these energies
energies isis
much less
less likely because of
likely because of the
the scarcity
scarcity of of high energy phonons and photons
3.6.1. Quasi thermal
3.6.1. Quasi thermal equilibrium
equilibrium 6
under normal conditions, and time scales scales areare longer,
longer,typically
typically10- -10- 9 s.)
10-6-10-9
Suppose
Suppose the semiconductor is
the semiconductor is disturbed
disturbed fromfrom equilbrium
equilibriumby bysome
some influence
influence It is
It is possible
possible forfor aadisturbance
disturbance- - such such as asoptical
opticalgeneration
generation- - to to be
be fast
fast on
which
which changes
changes the
the population
population ofof electrons
electrons and and holes.
holes. This could be
This could be exposure
exposure the timescale relaxation between
timescale of relaxation between bands,
bands, so so that
that it continuously
continuously disturbs
to light of
to light energy EE ?>Eg
of energy Eg which
which increases
increases the the density
density ofof both electrons and
both electrons and system from
the system from equilibrium,
equilbrium, but but slow
slow on the timescale
timescale of ofrelaxation
relaxation within
within
holes
holes above
above their equilibrium values,
their equilibrium values, or or itit could
could be the electrical
be the electrical injection
injection bands.
of electrons and
of electrons and holes
holesthrough
through anan applied
applied electric
electric bias.
bias. InIn either case, nand
either case, nand Considering only
Considering onlythethe conduction
conductionband band forfor thethe moment,
moment, fe(k,
fc(k, r)r) cannot
p have been disturbed so that they are no longer
p have been disturbed so that they are no longer described by the described by the Fermi
Fermi be completely describedby
completely described bythethequasi
quasithermal
thermalequilibrium
equilbrium distribution
distribution how-how-
Dirac
Dirac equilibrium distribution function
equilbrium distribution function and and np nr
np == nr isis no
no longer
longer true.
true. ever;
ever; since,
since,asaswe wehave
have seen
seenabove,
above, fofoisissymmetric
sy=etric in in k,
k, implying
implying thatthat
The electron distribution
The electron distribution isis now
now governed
governed by the general
by the distribution
general distribution no current flows.
no flows. To To deal
deal with
with this,
this, a small additional term, fA, fA, which
which isis
function r) introduced
f(k, r)
function f(k, introducedininEq.Eq.3.20
3.20above.
above. Moreover,
Moreover, different dist~ibu
different distribu- antisymmetric in
antisymmetric in k,
k, is
is added
added to fo. 10. The approximation
approximation is written,
tion functions, fc(k,
tion functions, fe(k, r)
r) and Iv(k,r),
and fv(k, r), should
should applyapply for
for electrons
electrons inin conduc-
conduc-
tion
tion and
and valence
valence bands. fe and
bands. fe and fvfv should
should be be position
position dependent,
dependent, because
because fe(k, r) = fo(E, EFn, Tn) + h(k,r) (3.46)
(3.46)
 The
The Physics
Physics of
of Sola.r Celts
Solar Cells Electrons (md Holes
Electrns and Holes in
in SemiconductO'T'S
Semiconductors 69
68

Equilibrium Under bias

where

10(E,EFn,Tn)
1
e(E-EFn)/kBTn +1'
fo(E,EFn,Tn) = e(E-EFnl/kBTn +1' (3.47)
(3.47)
no
no electrons
electrons
".~
;os;
~'~~J_"'
fl O electrons
_ ~);no electrons
_

EFn ".EF
fA can be
fA can be found
found by
by setting
setting upup and
and solving
solving aa book-keeping
book-keeping equation
equation for
for ff EF

called the
called the Boltzmann
Boltzmann Transport equation (see (see Box
Box 3.4).
3.4). Note
Note that
that because Ec,'E, .
of the
the well
well defined
definedparity of10
parity of and fA,
foand only 10
fA, only fo contributes
contributes to
to the expressions . Po Po holes ;:;:Po holes

for nnand
for and p,p, while only fA
while only fA contributes to ln
contributes to In and Jp.
lp.

3.6.2. Electron and

3.6.2. Electron andhole
hole densities
densities under bias
under bias Fig.
Fig, 3.13. Fermi levels
3,13. Fermi levels at
at and
and away
away from
from equilibrium
equilbrium..

Assuming
Assuming quasi
quasi thermal
thermal equilibrium,
equilbrium, the electron
electron and hole densities
and hole densities in
in a
semiconductor under bias are given, using Eqs. 3.37 and 3.38,
3.38, by is the difference
is difference inin chemical
chellcal potentials
potentials referred to in Chapter
referred to Chapter 2, and and the
the
size of
size of the
the splitting,
splitting, b.i
D.f.1., depends
depends upon
upon the
the intensity
intensity of
of the
the disturbance.
disturbance.
n = nie(EFn-El/kBTn (3.48)
(3.48) The electron hole
hole product is now given by

and np
np = nt e Ll.l'/k B T .
= nteI'/kBT (3.53)
(3.53)
p = nie(E;-EFPl/kBTp (3.49)
(3.49) In general, nand EFp
general, EF nand EFp are functions
functions ofof position.
position. At
At any point within
within
the semiconductor we wil suppose there is
we will is aa local
localquasi
quasithermal
thermalequilibrium
equilbrium
or,
or, in
in terms
terms of
of the
the conduction
conduction and valence band
and valence band energies
energies using
using Eqs.
Eqs. 3.31
3.31 and we can define local
local quasi Fermi
Fermi levels.
levels.
and 3.34, by

n = Nee-(Ec-EFnl/kBTn (3.50)
(3.50) 3.6.3. Current
3.6.3. Currentdensities
densities under
under bias
bias

and To find
find ln
In and
and Jp
lp we
we need
need to find
find an approximation
approximation for the antisymmetric
antisymmetric
part of
part I.
of f. This is done
This is by considering
done by consideringthe
the different
different influences
influences on
on f. I.
p = Nve-(EFp-Evl/kBTp , (3.51)
(3.51)

Tn and Tp
where Tn Tp are
are the electron and hole effective
effective temperatures. princi-
temperatures. In princi- Box 3.4.
3.4. Boltzmann Transport equation and the relaxation time approxima-
approxima-
Tn and
ple, Tn Tp may
and Tp may bebe different
different from
from the
the ambient temperature T. Electrons
ambient temperature tion
Tn >
with Tn :; T are
are called
called 'hot'
'hot'electrons
electrons and
andcancanarise
ariseininsituations
situationswhere
wherethe the
In this
this box
box we
we derive
derive a form
form for I A based
for fA based on
on aa consideration
consideration of
of' the
excess kinetic energy from strong
carriers gain excess strong electric
electric fields.
fields. However,
However, the
processes by
processes by which carriers are
which carriers areremoved
removed from any particular
from any particular kstate.
kstate.
conditions giving
conditions giving rise
rise to
to hot carriers dodo not usually apply in photovoltaic
photovoltaic
Since Ie
Since Ie isis aa function
function of
ofk,
k, rrand
and t,t, the
the rate
rate of
ofchange of I isis given
change of given by
devices, and
devices, and henceforth
henceforthwewill
wewil assume
assume thatthat Tn
Tn == Tp
Tp == T. (We(We wil
will come
come
electrons in Chapter 10.)
back to hot electrons 10.) It is
is assumed
assumed in Eqs.Eqs. 3.48-3.51
3.48-3.51 that
It
dfe dr dk fe ( )
dIe dr dk 8Ie
= dt . \lrie + dt . \lkle + at (3.54)
Ee -- EFn
Be kBT
EF" ?? kBT and E Fp -- Ev
and EFp kBT,
Ev ?? kBT, soso that Boltzmann statistics
that Boltzmann statistics apply.
apply. di = dt . Vrfe + dt . Vkfe + at. 3.54
Equations 3.48 and 3.49 3.49 are the same as Eqs. 3.37 and 3.38 3.38 except
except that
that The terms
terms in
in this
this equation
equation represent
represent the
the various
various ways
ways in which Ie can
which fe can
EFn =I
EFn EFp l =I
l EFp EF.EF.
WeWesay
saythat thethe
that Fermi
Fermilevels
levelsare
aresplit
split(see
(seeFig.
Fig. 3.13).
3.13). change. In
change. In the
the following
following we will use
we wil use the
the de!nitions
de!initionsof
of velocity
velocity
difference in quasi
The difference quasi Fermi
Fermi levels,
levels, ""
dr
b.tt = EF n - EFp (3.52)
(3.52)
vv == dt'
dt' (3.55)
(3.55)
70
70 The
The Physics of
of Solar Cells
Cells Electrons
Electrons and
and iales
H ale.s in
inSemiconductors
Semiconductors 71

force
and force Two,
Two, the distribution
distribution relaxes
relaxes exponentially
exponentially towards the quasi
quasi equilibrium
equilibrium
function
function with a characteristic time constant T so that
T so

F fidkdtdt ..
F == 1idk (3.56)
(3.56) le I (Ie -- fa)
10)
8fe I (Ie
(3.61)
derivativesofofI I with respect
To find the derivatives respect toto rand
rand k we wil approximate
we will approximate Ie
fe
at
at collisions
collisions T

by la
fo and
and refer
refer the
the electron
electron energy
energy to
to the
the conduction
conduction band
band edge,
edge, This is the Telaxation time approximation.
reLaxation time appmximation.Then
Thenwewecan
cansolve
solve Eq~Q in
Eq~Q in
the steady state
state to obtain
Ee +E(k,
E = Ec+ E(k, r)r) .. (3.57)
(3.57)
Ie =/a (1- ~'; ''VrEFn) (3.62)
(Here we
(Here we have
have assumed,
assumed, for clarity, that
for clarity, the conduction
that the conduction band
band minimum
minimum is
is
whence
at ka
ko =
= O. The result
O. The result is
is the
the same
same for ka :f.l 0.)
for ko 0.) Then
Then
TV
IA == --/akBT'
fA 'ilrEFn .
fa kBT .'VrEFn. (3.63)
'Vr/e ~ - tt'Vr(Ee - EFJ (3.58)
(3.58)
feinto
Substituting for Ie into Eq.
Eq. 3.22 for IInnwe
3.22 for we find

{-_kBT
q_ r T (fi~)2 9C(k)fo(E(k))d3k}
and
In(r) =
In(r)=fkaT r, T(1i~)2ge(k)/a(E(k))d3kL
'Vk/e ~ la- 'V
kTE k= kBT
_ 1ila v (3.59)
1. B )conduction band k me f
)conduct ion band k me
(3.59)
X'ilrEFn'VrEFn
X . . (3.64) (3.64)
where we have used the definition
definition of
of group
group velocity.
velocity. (We have also assumed Finally, replacing
Finally, replacing the
the term
term in brackets
brackets by tJnn,
/Lon, where Pn is the electron
where /Ln electron
that there
that there isis no
no gradient
gradient inin temperature,
temperature, asas discussed
discussed above.
above. In the most
most mobility, and
mobility, and nn defined from 10
defined from la as
as above,
above, (Eq.
(Eq. 3.21)
3.21) we
we have
general case
general case 'ilT'VT ofl 00and
andthe
theresulting
resultingexpression
expression forfor current
current contains
contains aa
term driven by temperature
temperature gradients.)
gradients.) Substituting
Substituting back
back into
into Eq.
Eq. 3.54
3.54 we
we (3.65)
(3.65)
I In(r) = PnnVrEFn .
obtai
obtain
So, the
So, the electron
electron current
current is
is proportional
proportional to the gradient in the electron quasi
die la Fermi leveL.
Fermi level.
similar treatment for
A similar for the valence band distribution
valence band distribution function
function Iv
fv pro-
pro-
at
di = - kBT(v' 'Vr(Ee - EFJ + F. v) + ale
duces the hole current density
duces
=Av.'VE +
ale
(3.60)
kBT r F" 7f . (3.60)
I Jp(r) = tJppVrEFn I.
(3.66)

where we
where we have related 'il
have related 'VrEe
rEetotothe
the force
forceon
on the
the electron
electron to
to cancel out the
cancel out Henceforth we will use 'il tomean
Henceforth we wil use V to mean 'V'il r'
first and third terms.
first terms.
To solve
To solve this for Ie
this for Ie we need to make two
we need assumptions about
two assumptions about the pro-
pro- Using the
Using the Boltzmann Transportequation
Boltzmann Transport equationtoto solve
solve for
for the non-
non-
cesses which
cesses changeIe.
whichchange Ie. One,
One,relaxation
relaxation events
eventswithin
within aa band
band within
within aa band equilbrium distribution
equilibrium distribution function
function (see
(see Box 3.4),
3.4), we
we obtain the
the following
following
are much more frequent than than exchanges
exchanges of carriers
carriers between
between bands.
bands. AB
A?, men- relations for
relations for the electron and hole current densities in a semiconductor un-
tioned above, events within
above, relaxation events within aa band
band are usually
usually collisions
collsions with the der bias:
lattice and are
are fast
fast because
because of
of the
the abundance
abundance of of phonons.
phonons. Therefore
Therefore
In(r) = PnnVEFn (Eq.3.65)
(Eq. 3.65)
ale ~ ale
Ofe afe I I
7f ~~at7ft
7ft collsions
co llisions Jp(r) = PppVEFp, (Eq.3.66)
(Eq. 3.66)
72

that is, the

that is,
carrier
the
the current
current density
density and
carrier density
current is
the current
density at
and the
is driven
at any
the gradient
driven by
gradient of
by the
point is
any point
of the
the gradient
the relevant
gradient in
relevant quasi
in the
the quasi
The
The Physics

is proportional
Physics of Solar Cells

proportional to
quasi Fermi
quasi Fermi
to the
Fermi level.
leveL.We
Cells

the relevant
relevant
We say
say
level. InIn aa more
Fermi leveL. more
T
T
Electrons
Electrons and Holes

and
Holes in
in Semiconductors
Semiconductors

Jp(r) = -qDp \lp + .pp(qF - \lX - \lEg + kBT\l InNv)' (3.74)

73

general
general case,
case, Eqs.
Eqs. 3.65
3.65 and
and 3.66
3.66would
wouldcontain termsinin'ilTn
containterms and 'ilTp
\lTn and \lTp and Thus the gradients
Thus gradients in the
the electron
electron affnity,
affinity, band
band gap
gap and
and effective
effective band
the currents would
would be driven also
also by
by temperature gradients. densities of
densities of states
states provide
provide an
an additional
additional effective electric field
effective electric field to the
the elec-
elec-
At any point
At any point rr the
the net
net current
current is
is given
given byby the
the sum of the
sum of the electron
electron and
and trostatic field F.
hole currents at that point:
hole currents at that point: In compositionally invariant material,
compositionally invariant material, only
only the
the electrostatic
electrostatic field
field FF is
present and
present so
and so
J(r) = In(r) + Jp(r), (3.67)
(3.67)
In(r) = qDn \In + q.nFn (3.75)
(3.75)

3.7. Drift and

3.7. Drift Diffusion
and Diffusion and

3.7.1. Cu.rrent equations

equ.ations in
in terms
terms of
of drift
drift and diffusion Jp(r) = -qDn \lp + ql!pFp. (3.76)
(3.76)
3.7.1. Ou:rrent and diffusion
Above we
Above we have
have used
used the
the 'Einstein'
'Einstein' relations which relate
relations which relate mobility
mobilty to
to the
the
Equations 3.65
3.65 and
and 3.66
3.66 are
are the most compact
compact forms for IInn and Jp.
forms for J p How-
How-
diffusion constant for either carrier, and are valid under low field conditions
ever, the physical interpretation of a quasi Fermi level gradient
ever, the physical interpretation of a quasi Fermi level gradient may be may be
somewhat clearer if we
we use
use the
the results,
results, valid
valid within
within the Boltzmann approx- qDn qDp.
l!n= !.T' (3.77)
(3.77)
imation, that
imation, that .p = kBT
kBT Now,
Now, IInn and Jp
J p each
each resolve
resolve into two contributions: aa drift current (some-
two contributions: (some-
\lEFn = (\lEe - kT\llnNe) + -\In (3.68)
(3.68)
n times called migration) where
called migration) carriers are driven
where carriers driven by an electric field,
field, and
and a
diffusion current where are driven
where they are driven by
by aa concentration
concentration gradient.
gradient. In
In the
and
first case
first case the carriers
carriers move
move soso as
as to minimise their electrostatic potential
minimise their
kBT energy, and
energy, and in
in the second
second toto minimise
rnnimise their statistical
statistical potential
potential energy.
energy.
'ilEF
\lEFp = =
p
('ilEv
(\lEv +
+ kT'illnNv ) - --'ilp.
kT\llnNv) p-\lp.
(3.69)
(3.69)
p
II Field
(These
(These can
can be
be obtained
obtained by by differentiating
differentiating Eqs. 3.31 and
Eqs. 3.31 and 3.33.)
3.33.) The
The gradient
gradient
in the conduction
conduction oror valence
valence band edge is is provided
provided by
by the electrostatic
electrostatic field
field
F and
and the
the gradients
gradients in
in the
the electron
electron affnity
affinity X and band
X and band gap, Eg
gap, Eg

'il
\lEeEc == qF - 'ilX
qF - \lX (3.70)
(3.70)
conduction band
band

and
+
\lEv=qF-\lX-\lEg (3.71)
'ilEv=qF-'ilX-'ilEg (3.71)

where we have used Eq. 3.40 and the defiition of electrostatic field I valence band
where we have used Eq. 3.40 and the definition of electrostatic field valence band

1 1
F= -\lEvac. (3.72)
F= -'ilEvac.
qq
(3.72) II Current

Substituting for \l'ilEF

Substituting for nand \l'ilEF
EF nand EF n
n into Eqs. 3.65 and 3.66
3.66 we
we have Fig, 3.14.
Fig. 3.14. Drift.
Drift.Carriers
Carriersflow
flow under
under anan electric
electric field
field in order
order to reduce
reduce their
their electri-
electri-
cal potential energy.
cal energy. Notice
Noticethat
that electrons
electrons and
and holes
holes drift
drift in opposite directions,
directions, both
In(r) == qDn'iln
In(r) qDn \In + J.tnn(qF
+ .nn(qF - \lx
- 'ilx - kBT\l InNe).
- kBT'illnNc). (3.73)
(3.73) producing currents
currents in
in the direction of
of the field.
field.
74 The Physics
The Physics of Solar Cells
Cells Electrons
Electrons and Holes
Holes in Semiconductors
Semicondu.ctors 75

dominated by
dominated by minority
minority carrier
carrier diffusion.
diffsion. This wil
will be
be discussed
discussed in detail in
Chapter 6.
6.
n

e-. . . .e-. . e- 3.7.2. Validity of

3.7.2. Validity of the

The drift-diffusion
the drift-diffusion
drift-diffusion equations

current equations
equations

equations inin the

the form
form 3.75 and 3.76
3.76 are very
~
. drift-diffusion current 3.75 and very
:~.......-
, ........-
~.....-. ~,:.........................
_". .....h...............
Conduction band
commonly usedused for
for the electron and hole currents in
ever, they depend upon
ever, upon several
several assumptions.
assumptions. It is
in device
device physics.
is worth
physics. How-
worth reviewing
reviewing these
these
electron current here,
here, and
and considering
considering some exceptions.
some exceptions.

hole current
Assumptions used:
,;........~.~ .. 'O'=:;:
., .......... ............ ......
=:. ............ ... Valence band
If;;.....o_ Electron and
. Electron hole populations
and hole populations each
each form
form aa quasi
quasi thermal
thermal equilibrium
equilbrium
0-. with a characteristic Fermi level and temperature
level and

This is one of the

the fundamental tenets of semiconductor physics. It would
tenets of would
not be valid if for
for instance,
instance, the bands were too narrow, too close together, or
pp if there was
was too high a density of intra
intra band
band gap
gap states.
states. In those
those conditions
if there
we might not really
we really have
have aa semiconductor!
semiconductor!
Fig. 3.15. InIndiffusion,
Fig. 3.15. diffusion, the
theelectron
electron and
and hole
hole populations
populations spread
spread out
out under
under aa concen-
concen-
. Electron
Electron and
and hole
hole temperatures are always
temperatures are the same
always the same as
as the lattice
lattice
tration gradient
gradient to reduce
reduce their
their statistical
statistical potential
potential energy.
energy. The grey
grey and dotted
dotted lines
lines
indicate how
indicate how the electron
electron and hole
hole density
density may
may develop after generation
develop after generation close to the
close to temperature
left hand
hand surface.
surface. Note that
that the
the currents
currents produced
produced byby electron
electron and
and hole
hole diffusion
diffusion have
have
opposite signs.
signs, Unless
Unless the
the electron
electron and
and hole
hole mobilities
mobilties are different,
different, the
the net
net current may
may This fails
fails in conditions
conditions where electrons or
where electrons or holes
holes gain
gain extra kinetic en-en-
be zero. ergy; for
ergy; for example,
example, through acceleration through large large electric
electric fields.
fields. Then
the hot
hot electrons
electrons and
and holes
holes need to be be described
described by spatially varying
varying tem-
In the presence
presence of a drift field
field only,
only, the
the total current is peratures TnTn and
and TTp, and aa term
p , and term proportional
proportional to
to the temperature gradient
appears in
appears in the electron andand hole currents. Such
hole currents. Such high
high fields
fields are
are not usually
J = In + Jp = q('nn + .pp)F (3.78)
(3.78) encountered in photovoltaic
encountered photovoltaic devices.
devices. However,
However, itit is theoretically
theoretically possible
possible
where the coeffcient
where the of F
coefficient of is the
F is the conductivity
conductivity ofof the
the semiconductor, as
semiconductor, as
that hot
hot carrier
carriereffects
effects may
may arise
arise through quantum confinement
confinement in in low di-
given
given in
in Eq.
Eq. 3.41.
3.41. Note
Note that the
the field
field drives
drives electrons and holes in opposite mensional structures. This
mensional structures. This will
wil bebe raised
raised in
in Chapter 10.
Chapter 10.

directions. . Changes
Changes in in state
stateoccupancy
occupancy are
are much
much more
more likely to be
likely to be due
due to scattering
In the presence
presence of a concentration
concentration gradients
gradients only
only we
we have, collisions
collsions within
within aa band
band than to generation,
than to generation, recombination
recombination or or trapping
trapping

In = q(Dn 'in - Dp 'ip) (3.79)

(3.79) which remove
events which removeaacarrier
carrierfrom
fromthat
that band.
band. This
This is
is the
the relaxation time
approximation.
If the electron
electron and hole
hole gradients
gradients are similar, as
are similar, as may
may be the case
be the case under
under
illumination, the electron
ilumination, the electron and
and hole
hole diffusion
diffusion currents
currents tend
tend to
to cancel
cancel each
each
This may fail
fail in materials containin aahigh
materials containing highdensity
density of
ofdefects,
defects, where
where
other out. A
A net diffusion current usually arises only when
netdiffusion when the electron and trapping, detrappiiig
trapping, detrappillg and recombination events are
recombination events are common.
common. ThenThen the
hole gradients are
hole carrier gradients are very different. This can
very different. can bebe achieved
achieved in certain
in certin relaxation time approximation
approximation is not valid.
valid. Another special case arises
arises at an
device configurations, such
device configurations, such as
as aa p-n junction. In
p- junction. In that
that case,
case, currents
currents are
are abrupt boundary
boundary between
between two different semiconductors
semiconductors (a(a heterojunction).
heterojunction).
76 The Physics of Solar Cells
The Physics Cells Electrons and
and Hole.s in Semiconductors
Hole.s in Semicondu.ctors 77

. Electron
Electronand
and hole
hole states
states can
can be
be described
described by a quantum number kk localised states
localised states in the band
band gap,
gap,

fails
This
This is
fails for
is used
used in
in the
the definition
for non-crystalline
definition of
of the
materials, with
non-crystallne materials,
electron and
the electron
with the
hole currents
and hole
the consequence
consequence that
above. It
currents above. It
carrier mobil-
that carrier mobil-
J = In + Jp +
L
localised states
localised states i
JJ.i (3.80)
(3.80)

ities cannot be rigorously defined from the expectation value of the scatter- This localised
This state current
localised state current can
can be
be described
described withwith the
the aid of
of an
an energy
energy
ing
ing time. Nevertheless, analogous
time. Nevertheless, analogous expressions
expressions for
for electron
electron and
and hole
hole currents
currents dependent
dependent mobility, i(E)JL(E),, in analogy
mobility, analogy to
to the
the definition
definition of current
current in aa crystal
can
can be be used
used in
in amorphous
amorphous andand defective
defective materials,
materials, but
but with
with empirical
empirical ex-
ex- above
pressions for
pressions for the
the mobilities.
mobilties.
LJi== L.(E)f(E)g(E)
LJ LJL(Edf(Ei)g(Ei) (3.81)
(3.81)
. Boltzmann
Boltzmannapproximation (Ec -- EFD
approximation (Ec kBT; EFp
EFc ;:;: EFp -- Ey kBT)
Ev ;:;:
This was made
This was made in obtaining the
in obtaining drift diffsion
the drift diffusion forms
forms from
from the
the quasi
quasi where g(Ei) is
where g(E) is the
the density
density oflocalised
oflocalised states
statesandand f(E)
f(E) is
isthe
the(usually
(usuallyFermi-
Fermi-

Fermi
Fermi level
level gradients.
gradients. In
In degenerate
degenerate semiconductors
semiconductors (where
(where the
the Boltzmann
Boltzmann Dirac) distribution
distribution function.
function. The
The form
form of JL(E)depends
of .(E) depends on the mecanism
mechanism
approximation
approximation fails)
fails) the definitions in
the definitions terms of
in terms of Fermi
Fermi level
level gradients
gradients are
are of transfer between
between localised states. For example,
localised states. example, for
for thermally
thermally assisted
assisted
still valid and should be used.
stil valid and should be used. hopping it should be thermally activated.
hopping
Delocalised
Delocalised conduction
conduction oror valence
valence band states can
band states can be
be distinguished
distinguished from
from
. Compositional
Compositional invariance
invariance localised, intra
localised, intra band
band gap
gap states by a mobility edge. In
mobility edge. In practice,
practice, this
this is the
energy at
energy at which
which the
the mobility
mobilty becomes temperature activated.
becomes temperature activated. These
These will
wil be
This was made
This was made in replacing the
in replacing band edge
the band edge gradient
gradient with F. For
with F. For aa com-
com-
discussed in
discussed in more
more detail
detail in Chapter 8.8.
positionally varying material, contributions to the current will also
positionally varying material, contributions to the current wil also arise arise
from any variation
from any variation in
in the
the electron
electron affinity,
affity, band gap, and
band gap, andeffective
effective mass,
mass,
and can
can be
be included
included by
by using
using Eqs.
Eqs. 3.73
3.73 and
and 3.74.
3.74. 3.8.
3.8. Summary
Summary
Semiconductors are
Semiconductors are suitable
suitable materials
materials forfor photovoltaics
photovoltaics on on account
account of the
3.7.3. Currentequations
3.7.3. Current equationsfor
fornon-crystalline
non-crystalline solids
solids band gap between occupied and
between occupied and unoccupied
unoccupied bands
bands which
which can
can be bridged
by a visible photon, and
visible photon, and the ease
ease ofof charge
charge transport
transport through
through the crystal
The drift difsion
The drift diffusionpicture
pictureisisclearly
clearlynot
notvalid
validininthe
thecase
caseofofdefective
defective crys-
crys-
bands. In crystallne
crystallinesemiconductors,
semiconductors, electrons promoted to the conduction
talline or amorphous
tallne or amorphous materials,
materials, when
when the density of
the density of states
states in
in the band gap
the band gap
can be
band can be treated
treated like nearly freefree particles with
with aa well-defined
well-defined wavevector
wavevector
is
is high. Then thethe following
following effects
effects may apply:
and an effective mass which
effective mass which reflects
reflectsthe
the effect
effectof
ofthe
the lattice
lattice atoms. Absent
thenumber
. the numberdensity
densityofofelectrons
electrons and
and holes
holes may be differently sensitive
sensitive to electrons in
electrons in the valence band are
valence band are known
known as as holes and can
holes and can be treated asas
temperature, electric
electric field
field and
and illumination;
ilumination; positively charged particles
positively charged particles with
with an effective mass determined
effective mass determined by by the va-
va-
. the
themobilty
mobilitymay
maybebetemperature,
temperature,field
fieldand
andcarrier
carrierdensity
density dependent;
dependent; lence band
lence band structure. Electrons and holes can be
holes can be treated approximately as
. there
theremay
maybe
be aa contribution
contributiontotothe
thecurrent
currentwhich
whichcomes
comes from conduction
conduction independent particles.
independent particles. The
The band
band structure is the relationship
relationship between the
between
between localised
localised states
states in
in the band gap.
gap. energy of
energy of the
the electron
electron and
and its wavevector.
wavevector. The The most
most important
important points are
the valence
valence band maximum
maximum and conduction
conduction bandband minimum.
minimum. The form of
There are aa number of different ways of describing
describing the currents in defective
defective the band structure is is determined
determined by by the
the crystal
crystal structure but it isis approx-
approx-
materials.
materials. AA thorough
thorough description
description isis beyond
beyond thethe scope
scope of
of this
this chapter.
chapter. It
It imately parabolic near to these these critical points.
points.
is
is often assumed
assumed that the. currents
that the currents due
due toto electrons
electrons and
and holes
holes moving
moving in In equilibrium, states
states are
are filled
filled by electrons according to to the Fermi Dirac
delocalised
delocalised states conduction and
states in the conduction and valence
valence bands can be describ~d by
be describ~d distribution function.
distribution function. In aIn a pure
pure semiconductor
semiconductor lies within
the Fermi level lies
the Fermi level

the Boltzmann transport

the Boltzmann theory, i.e.,
transport theory, i.e., drift
drift diffsion
diffusion equations
equations apply.
apply. There
There the band
the band gap gap and
and the
the electron
electron and and hole
hole densities
densities depend
depend exponentially
exponentially
may
may bebe an
an additional
additional current
current due
due toto electron
electron (or
(or hole)
hole) motion
motion between
between upon EF.
E F . Doping
Doping with
with impurities
impurities of of different
different valence increases the density
valence increases
78 The Physics
The Physics of Solar Cells
Cells

of electrons
electrons or or holes
holes in the semiconductor
semiconductor at equilibrium
equilibrium and movesmoves EF
towards the bands. Heavy
towards doping fixes
Heavy doping fies the
the density
density of the dominant
dominant carrier.
At equilibrium, electron
At equilibrium, electron and
and holes
holes currents
currents are
are always
always zero.
zero.
The semiconductor
semiconductor can can be
be disturbed
disturbed from
from equilibrium
equilbrium by by the action of
light or
or an
an applied
applied electric
electric bias.
bias. Away
Away from
from equilibrium
equilibrium the the distribution
Chapter
Chapter 4
function changed but
function is changed can be
but can be approximated
approximated by by aa Fermi
Fermi Dirac
Dirac function
with separate,
separate, spatially
spatiallyvarying
varying Fermi
Fermi levels,
levels, called
called quasi
quasi Fermi
Fermi levels,
levels, for
for Generation and Recombination
the electron and hole.
hole. In general,
general, different electron and hole
different electron hole temperatures
may apply but in
may in practical
practical conditions
conditions the ambient
ambient temperature is is usually
usually
valid.
Application of
Application of bias
bias produces
produces electron
electron and
and hole
hole currents. In conditions
conditions
where scattering events
where events within
within bands being
being faster
faster than
than transitions between
between
bands (the
bands (the relaxation
relaxation time approximation), the currents currents are proportional 4.1. Introduction: Semiconductor
4.1. Introduction: Semiconductor Transport Equations
Equations
to
to the gradients in
the gradients in the
the respective
respective quasi
quasi Fermi levels and
Fermi levels to the
and to the respective
respective
The essential function of aa solar
solar cell
cell isis the
the generation
generation of of photocurrent.
photocurrent. The
mobilties. The quasi
mobilities. quasi Fermi
Fermi level
level gradient
gradient may
may be considered
considered asas a driv-
driv-
output isis determined
determined by by aa balance
balance between
between light absorption, current gen- gen-
ing force
ing for conduction.
force for conduction. By resolving the quasi Fermi level
resolving the level gradient into
eration and charge
charge recombination. Currents due
recombination. Currents due to electrons hol~s in
electrons and hol~s
electrostatic potential and carrier density gradients, the current can can be ex-
semiconductors
semiconductors were were discussed
discussed inin Chapter
Chapter 3, 3, and
and Chapter
Chapter 5 5 will deal with
wil deal with
pressed
pressed as as a sum of a field
field driven
driven 'drift' current
current and
and aastatistically
statisticallydriven
driven
the mechanisms
mechanisms of of charge
charge separation
separation whichwhich drive
drive the
the photocurrent.
photocurrent. This
'diffsion' current.
'diffusion' current.InInnon-crystallne
non-crystallinematerials
materialsthethesame
sameconcepts
conceptsofofquasi
quasi
chapter is concerned
chapter concerned with the processes
processes of chargecharge carrier generation
generation and
Fermi
Fermi level
level and
and mobility can be applied,
mobilty can applied, but the effective
effective mobility may be
mobilty may be
recombination. We
recombination. We introduce
introduce the theoretical formalism
formalism for for electronic
electronic tran-
energy dependent.
sitions in semiconductors
sitions in semiconductors andthis
and use usetothis to derive
derive theofrates of photogene
the rates photogene ration
and the principal
principal recombination
recombination mechanisms.
mechanisms. We We will
wil derive
derive some
some of the
co=only used
commonly usedformulae
formulaeforforrecombination
recombination rates, rates, and
and attempt
attemptto toshow
show how
how
the rates are
are dependent upon the electronic
electronic structure, materials properties
and operating conditions. The detailed
conditions. The detailed derivations
derivationswillwil not
not be relevant
relevant to
all readers, but are included
included to suggest
suggest how how the formalisms
formalisms can can bebe adapted
adapted
to
to deal
deal with
with other,
other, novel
novel photovoltaic
photovoltaic materials
materials and structures.
and structures.
The basic
basic equations
equations of device
device physics,
physics, the semiconductor
semiconductor transport
equations, are
equations, are based
based on twotwo simple principles:that
simple principles: that the number of of carri-
carri-
ers of each
ers eac typetypemust
mustbebeconserved;
conserved; and and that the the electrostatic
electrostatic potential
potential
due to the
due the carriers
carriers charges
charges obeys
obeys Poisson's
Poisson's equation.
equation. ForFor aa semiconductor
semiconductor
containing electrons
containing electrons and holes,
holes, conservation
conservation of electron number requires requires
that
{)n 1
an = ~V'.Jn + Gn - Un
-() = -Y'.J n + G n - Un (4.1)
(4.1)
at
t qq
for electrons
for electrons and
ap = -~V'.Jp + Gp - Up
(4.2)
(4.2)
at q
79
 The
The Physics Cells
Physics of Solar Cells Generation
Generation and
and Recombination
Recombination 81
80

parameters,
parameters, we we have
have aa set
set aa set
set of coupled
coupled differential
differential equations
equations which
which
/ / can be solved for the
solved for the three
three unknowns.
unknowns.The Theparticular formofofJ,J, G
particularform G and U
area dA

--
~
J(x)
--
~
J(x+dx)
J(X+dx)
depends on
depends
J and
on the material and
and nn are
aredefined
look at the
look
defined for
the mechanisms
mechanisms which
and environment.
environment. In Chapter
for a crystallne
determine U
which determine
Chapter 33 we
crystalline semicoriductor.
U and G.
we looked
In this
semiconductor. In
looked at how
this chapter we
how
we will
wil

/ 1/ 4.2. Generation and Recombination

4.2. Generation Recombination

( dx ))
(
dx
Generation is
Generation
of free
is an electronic
free carriers
electronic excitation event which
carriers available
available to carry charge.
which increases
charge. Recombination
increases the number
Recombination is
number
is an electronic
electronic
Fig. 4.1. Illustration of the continuity equations. On passing thro~gh a small volume, relaxation event which reduces the
which reduces the number of free carriers. Generation re-
free carriers.
Fig. 4,1. Ilustration of the continuity equations. On passing through a small volume,
the charge changes
the charge changes byby (l(x + dx)
(l(x + J(x))
dx) -- l(x dA. This
ii xxdA. Thishas
hasto
tobebesupplied
supphed by
bythe
thedifference
dIfference quires an input of
quires of energy
energy wilie
while recombination
recombination releases
releases energy.
energy. The energy
between the
between the carrier
carrier generation
generation and
and recombination
recombinationrates,
rates, (G U) x
(G-- U) x dx dA.
dx xX dA. input can
can be
be provided
provided by by the
the vibrational
vibrational energy
energy of the lattice (phonons),
(phonons),
light
light (photons)
(photons) oror the kinetic energy
the kinetic energy ofof another carrier. The
another carrier. released en-
The released en-
for ergy is taken up up by
by these
these same
same mechanisms.
mechanisms. For For every
every generation
generation process
process
for holes,
holes, where
where G /
Gn/p is the volume rate of generation of electrons (holes)
n p is the volume rate of generation of electrons (holes)
and U / p is
is the
the volume
volume rate
rate of
of recombination.
recombination. Poisson's
Poisson's equation
equation in
in the
the there
there isis an
an equivalent
equivalent recombination process. This
recombination process. This isis due
due to
to microscopic
microscopic
and Un/p
n reversibilty, and is an
reversibility, an important
important principle
principle in in understanding
understanding the functionfunction
differential form is
of
of photovoltaic devices.
photovoltaic devices.
V 2
v2clcp == 1-( -pfixed +
.i( -pfixed p)
+ nn -- p) (4.3)
(4.3) Generation may
Generation may be the promotion
promotion of of an
an electron
electron fromfrom valence
valence to con-
con-
es
s
duction band,
band, which
which creates an an electron-hole pair, or from valence band band into
where cpcl isisthe
where the electrostatic
electrostatic potential,
potential, s es is
is the
the dielectric
dielectric permittivity
permittivity ofof the
the a localised state in the band
localised state band gap,
gap, which
which generates
generates onlyonly aa hole,
hole, or from
from a
semiconductor
semiconductor and pfixed isisthe
and pfixed thelocal
localdensity
densityof offixed charge.
fied charge. localised state
localised state into the conduction
conduction band, which which generates only an electron.electron.
The continuity Eqs.
The continuity Eqs. 4.14.1 and 4.2 can
and 4.2 can bebe understood
understood by by considering
considering aa For the solar cell,
cell, the most important form form of generation is is optical,
optical, i.e., by
small volume fJ1/ = fJA x fJx within the semiconductor
small volume b1/ = bA x bx withi the semiconductor (Fig. 4.1). (Fig. 4.1). the absorption of a photon.
In unit time,
In unit fJ1/ xx Gn
time, b1/ G n electrons
electrons are
are generated
generated within
within thethe volume
volume and
and Recombination
Recombination isis the the loss
loss ofof an
an electron
electron or or hole
hole through
through the decaydecay of
fJ1/
b1/ xx UnUn electrons
electrons are removed. Electrons
are removed. Electrons may may also
also be introduced or
be introduced or re-
re- an electron to a lower energy state.
lower energy state. Again
Again this
this may
may be be from
from band
band to band,
moved
moved by by currents
currents flowing
flowing into
into and
and out
out ofof the
the volume.
volume. Consider
Consider only the xx
only the destroying an
destroying an electron-hole
electron-holepair, pair,ororitit may
may be be from
from conduction
conduction band band to
component
component of
of the current. In
the current. In unit
unit time ~Jn(x+fJx)xxbA
time ~Jn(x+bx) fJA electrons
electrons leave
leave the
the trap
trap state
state oror from
from trap
trap state
state toto valence
valenceband,
band, removing only an
removing only an electron
electron
volume through the right hand boundary while ~Jn(x)
volume through the right hand boundary while ~Jn(x) x bA enter from the x fJA enter from the or aa hole,
hole, respectively.
respectively. The energy
energy released
released can can be be given
given upup as
as aa photon
left, causing a net change of ~ ~ x fJv in the number
left, causing a net change of ~ ~ x bv in the number of electrons. Addingof electrons. Addi.ng (radiative recombination), as
(radiative recombination), as heat
heat through phonon emission
through phonon emission (non-radiative
(non-radiative
the three contributions
contributions we we have
have for
for the
the rate
rate of
ofchange
change ofof electron
electron density
density recombination) or as
recombination) as kinetic energy
energy to another
another freefree carrier (Auger
(Auger recom-
recom-
the three
per unit
bination).
per unit volume,
volume,

an =_ ~~aJ
an aJn+ G
C _U n
Un .
at-qax+
at q ax n n. n
-
Thermal generation and
and recombination
recombination

In three dimensions
dimensions this
this generalises
generalises quite readily to
to the
the form
form given
given in
in (4.1)
(4.1) At absolute zero in the absence
absence of any external bias, electrons occupy all of
In three quite readily the energy
energy levels available up
levels available up to
to the Fermi level,
level, and no recombination or
above.
Equations (4.1) and
and (4.2)
(4.2) are
are completely
completely general.
general. Once
Once we
we know
know how
how generation processes
generation processesoccur.
occur.As
Asthe
the temperature
temperature isis raised,
raised, the
the lattice gains
Equations (4.1)
the J, G
G and
and UU depend
depend on
on n, cp, and
and cl,
n, pp and and other
other material
material or
or environment
environment vibrational kinetic energy and some
some of of this
this may
may bebe given
given up
up to an electron
the J,
82 The Physics
The Physics of
of Solar
Solar Cells
Cells Generation and
Generation and Recombination
Recombination 83
83
82

to promote
to promoteitittotoaahigher
higherenergy
energyleveL.
level. The
The promotion
promotion of
of an
an electron
electron across
across and
and surface
surface recombination, and
and show
show how the
the recombination
recombination rates
rates are
are re-
re-
the band
the band gap
gap is
is is
is called
called thermal
thermal generation.
generation. At At the
thesame
same time,
time, electrons
electrons in in lated
lated to
to the
thematerial
materialproperties.
properties.Section
Section4.6
4.6addresses
addresses the
thesemiconductor
semiconductor
excited states can
excited states can relax
relax down
down to
to vacant
vacant lower
lower energy
energy states
states and
and give
give upup the
the transport
transportequations
equationsagain
againand
andindicates
indicatessome
somesimplified
simplifiedcases.
cases.
energy difference
energy difference as as vibrational
vibrational energy
energy to the lattice.
to the lattice. The
Theloss
loss of
of aa mobile
mobile
carrier in this way is thermal 7"ecombination. Like any
carrier in this way is thermal recombination. Like any other generation- other generation-
recombination processes,
processes, these
these thermal
thermal processes
processes cancan involve
involve band
4.3.
4.3. Quantum
QuantumMechanical
MechanicalDescription
Description of
ofTransition
Transition Rates
Rates
recombination band to band
to band
transitions and
transitions and localised
localised state to band
state to band transitions.
transitions. At At finite
finite temperatures
temperatures 4.3.1. Fermi's
4.3.1. Fermi's Golden
Golden Rule
Rule
these processes
these processes occur
occur continually
continually atat aa rate
ratewhich
which increases
increases withwith increasing
increasing
temperature. In In thermal
thermal equilbrium,
equilibrium,the therate
rate of
of every In
In many
many cases
cases electronic
electronic transitions can can bebe described
described byby Fermi's
Fermi's Golden
Golden
temperature. every thermal generation
thermal generation
process is matched exactly
is matched exactly by
by the
the rate
rate ofofthe
the equivalent
equivalent thermal
thermalrecombi-
recombi- Rule.
Rule. This is an an approximation,
approximation, basedbased on first
first order perturbation theory,
theory,
process
nation events. Thus the thermal generation G~~p is balanced by the equi- of
of the full quantum
quantum mechanical transition rate.
mechanical transition rate. According
According toto Fermi's
Fermi's Golden
Golden
nation events. Thus the thermal generation G~~p is balanced by the equi-
Rule, the transition
transition probability per unit time from an initial
probability per initial filled
filled state
state Ii)
Ii)
librium recombination
librium U~?p'
rate U~?p'
recombination rate
of energy Ei
of energy E toto aa final
fial empty
empty state If) of
state in of energy
energy ErEc which
whichdiffers
differs inin energy
energy
~h == U~h
~h U~h by E under
under thethe action
action of
of some perturbing Hamiltonian
some perturbing Hamiltonian H' H' isis given
given byby
2: j(iIHllnI2(Er - E Of E).
and
and (4.6)
G~h = U~h
G~h U~h..
The term
term in in brackets 101 2 isis aa matrix element
brackets 1012 couplinginitial
element coupling initial and final
Since we
Since we are
are interested
interested in
in the distu7"bance of
the disturbance of the
the populations
populations from
from equilib-
equilb- states. It describes
states. It describes the size
size of the interaction between
between the two states
states un-
un-
rium, we need consider only the excess recombination and generation
rium, we need consider only the excess recombination and generation rates rates der the given perturbation. H'
given perturbation. H' may may represent the effect
represent the effect of
of aa light
light field,
field, of
in Eq. (4.1), i.e.,
in Eq. (4.1), i.e., phonon interactions, or carrier-carrier interactions.
phonon interactions, interactions. The delta function
function en-en-
sures conservation of energy.
energy. A A negative
negative sign
sign applies
applies for
for excitation events,
(4.4)
(4.4)
Un = uotal - Uh such as
such as absorption where
where Er Er > :; E,
Ei, and
and aa quantum
quantum ofofenergy
energy EE isisremoved
removed
and from the perturbing
from perturbing field,
field, and aa positive
positive sign
sign for relaxation events, such as
and
recombination, where
recombination, where EfEr <0(Ei
Ei and
and aa quantum
quantum E E is emitted.
Gn = G~otal - G~h .
Thus thermal generation
Thus thermal generation is not included
is not included explicitly
explicitly as
as aa contribution
contribution to G.
to G. Box 4.1. Derivation
Box 4.1. Derivation 01
oL Fermi's
Fermi's Golden
Golden Rule
Rule
For
For band-ta-band generation and
band-to-band generation and recombination
recombination processes,
processes, the
the rates
rates are
are To obtain
To obtain the
the transition
transition rate we need to
we need to multiply
multiply by by the
the probabilities
probabilties
equal
equal for
for electrons
electrons and holes and
and holes and occupied,IiIi== f(Ei(k
that the initial state is occupied, I(E(k)) and that
i )) and that the final
fial state
stateisis
Un = Up = U (4.5)
(4.5) available,
available,1-1- ff (1- f(Ef(kr))),
If == (1- I(Ef(k))), where I(E) is
where I(E) is the
the electronic
electronicoccupation
occupation
function.Then
function. Then the
the rate
rate of
of transitions -- I isis given
transitionsi i -> given by
and
and
271 22
271"
ri_f
ri~r == nlHicl
--IHirl o(E
(Erf -- Ei E)Ii(l - - fr)
Ei -- E)fi(l fr (4.7)
Gn = Gp = G.

In
In this
this chapter we will
chapter we first consider
wil first consider how
how electronic
electronic transition
transition rates
rates may
may bebe where Hif
where H is
is shorthand
shorthand for for the matrix
matrix element.
element. (In
(In Eq.
Eq. 4.7
4.7an anelectron
electron
treated microscopically using Fermi's Golden Rule, in Sec. 4.3. In
treated microscopically using Fermi's Golden Rule, in Sec. 4.3. In Sec. 4.4 Sec. 4.4 promotion event
promotion (Er >
event (Ec :; Ej,
Ei, is
is assumed.
assumed. The analysis applies equally
analysis applies equally toto the
the
we
we will address the
wil address the process
process ofof photogeneration,
photogeneration, and
and show
show how
how thethe ab,sorp-
ab,sorp- case Er <
case Ec 0( Ei,
Ei, in
in which
which case
case EE takes
takes the opposite sign.)
tion coefficient of Provided that the
the transition -- II is
transition i i -> is energy
energy conserving,
conserving, thenthen the
tion coeffcient of aa semiconductor
semiconductor is derived. In
is derived. Sec. 4.5
In Sec. 4.5 we
we consider
consider the
the Provided that the
different same perturbingfield
field can
can induce
inducethe
theT"everse transition II ->
reverse transition . (Stimulated
-- ii.
different types
types of
of recombination:
recombination: radiative,
radiative, Auger,
Auger, nonradiative
nonradiative viavia traps,
traps, same perturbing (Stimulated
84
84 The Physics
The of Solar
Physics of Solar Cells
Cells Generation and
Generation a.nd Recombination
Recombination 85
85

emission in
emission in aa solid
solid isis an
an example
example of ofthis.)
this.) As
As soon
soonasasstatestate fI is
is partially
partially Optical transitions
transitions may
may involve
involve additional
additional photons,
photons, or phonons.
phonons. In such
such
occupied and
occupied and state is partially
state ii is partially empty,
empty, there
there isis aa finite probability that
fiite probability that cases
cases thethe first
first order
order approximation
approximation given given by Fermi's
Fermi's Golden
Golden Rule
Rule fails,
fails,
this reverse
this reverse transition
transition wil willoccur.
occur. By
By the
thesymmetry
symmetryof ofquantum
quantummechanics
mechanics and itit isis necessary
necessary to
to expand
expand the the quantum
quantum mechanical transition rate to
mechanical transition to
the transition ff -4
the transition -+i iisisgoverned
governed byby the
the same
same matrix
matrix element
element Hif,Hir, and
and it
it higher order. An important example example is the case of optical
optical transitions in an
has rate indirect
indirectband band gap
gap semiconductor,
semiconductor, whichwhich involve
involve aa photon
photon and
and a phonon. The
higher order terms resultresult in
in aa different
different energy dependence of the the absorption
21l 2 (4.8)
Tf-4i = -iIHill i5(Ef - E - E)fil - f (4.8) coeffcient
coefficient for indirect and and direct
direct gap
gap materials,
materials,which
which isisdiscussed
discussed below.
below.
The higher
higher orderorder approximations
approximations are beyondbeyond the scope
scope of this book.
book.
The net
The net rate
rate of
of transitions -+f fisistherefore
transitions ii -4 thereforegiven
givenby
bythe
thedifference
difference between
between
two rates
the two
4.3.2. Optical
4.3.2. Optical processes
processes in
in aa two
two level
level system
system
21l 2
Tif = Ti-4f - Tf-4 = -iIHifl 8(Ef - E - E)(J - fr. (4.9)
Here wewe consider
consider the
the simple
simple case
caseofofaasteady
steadystate
state light
light field
field interacting
interacting with
For all
all such
such transitions
transitions involving
involving aa quantum
quantum of of energy
energy E E we
we should
should sum
sum a two level system. The two level
level system. model allows
level model allowsusustoto derive
derive the
the distribution
distribution
For
over all function for photons,
function for photons, which
which will
wil be used
used later. The photon energy energy isis equal
over all pairs
pairs of initial and final
of initial final states which
which differ
differ by
by E. crystal,
E. For a crystal,
to the
the difference
difference in energies
energies E Ev and Ec'
y and Ec. Since
Since the light
light biases
biases thethe system
system
where states
states are
are distinguished by wavevector,
wavevector, we can can convert the sum sum over
over
discrete states T(E)
r(E) = 2:i,1
= ,I ril, into
into an
anintegral
integralover
over all
all initial
initial states k iand
statesk and the two
two levels wil not
levels will not be in thermal
thermal equilibrium,
equilbrium, but we wil assume
we will assume that
Tif,
final kr which they are each in quasi
each in quasi thermal equilbrium
equilibriumwith
withquasi
quasiFermi
Fermilevels
levelsofofEF p
EFp
final states
states kf which differ
differ in
in energy
energy by by E, by introducing
E, by introducing the the density
density of
of
9r(kt} and
states functions gf(ki) 9i(k;) for
and g(k.) for the
therelevant
relevant crystal
crystal bands
bands(Eq.(Eq.3.11).
3.11). and respectively de
EFnrespectively
and EFn [de Vos,
Vos, 19921.
1992J.
Then we we have The following
following events can occur:
haveforfor the
the transition
transition rate per unit crystal
crystal volume,
volume,

r(E) 2; JJ
IH ir128(Er -- Ei
= 2; J J IHi1128(Ef
T(E) = E -- E)(f(Ei(k i )) -- f(Ef(kf)))
E)(J(E(k)) f(Ei(k)))
. aa photon
. an
anelectron
can be
photon can
electroncan
be absorbed
absorbed to
can relax
relax to
to Ev
to promote
Ev from
promote an
from Ec
an electron
Ec while
electron from Ev
while emitting
emittingaa photon
Ec;
to Ee;
Ev to
photon(spontaneous
(spontaneous
emission);
X 9i(ki)9f(kr)d3kid3kl
x g (ki)gi (kl)d3kid3kl ((4.10)
4.10) . aa photon
photon cancan stimulate
stimu.late the
the relaxation of an
relaxation of an electron
electron from
from to
to Ev
Ev from
Ec together with
Ee together with the
the emission of aa second
second photon (stimulated emission)
photon (stimulated emission)
The form of
The form of Hir
Hf depends
depends upon
upon the nature of
the nature of the
the interaction.
interaction. For
For instance,
instance,
(Fig. 4.2).
(Fig. 4.2).
for
for optical
optical transitions
transitions the
the matrix
matrix element
element delivers
deliversthethecondition thatkk == k',
conditionthat k',
and the matrix
and the matrix element
element then
then depends only on
depends only E.
on E. The first and third
third of
of these
these processes
processes are closely related. They
closely related. They can
can be
If the kk dependence
If the dependence isis not
not needed
needed explicitly
explicitly (for instance, ifif the
(for instance, band
the band distinguished only by
distinguished by the
the relative occupation
occupation probabilities
probabilties of
of the
the two
two levels,
levels,
structure
structure isis isotropic)
isotropic) then
then the integral can
the integral expressed in
can be expressed terms of
in terms and not by
and not by the
the strength
strength ofof the
the photon field: any
photon field: any photon can cause
photon can cause either
either
energies, event. Therefore
type of event. Therefore wewewill
wil combine
combinethem
theminto
intothe
the net
net absorption
absorption with

r(E)
T(E) = 2; J
= 2; J IHiI12(J(E) f(Ei ++ E))gi(Ei)gf(E
IHiI12(f(Ei) -- f(Ei i ++
E))g(Ei)gf(E E)dE
E)dEi (4.11)
i (4.11)
aa rate given
given by
21l1 2 (
Tabs = -i Hevl f. fv - Ie) ((4.13)
4.13)
To
To find
find the
the total
total rate of band to band transitions,
transitions, T(E)
r(E) should be summed
over
over the
the transition energy E, weighted
transition energy weighted by the density
density of
of available
available photon where fv
where Iv isis the
the (Fermi Dirac) probability
(Fermi Dirac) probabilitythat
that there
there isis an electron is the
electron is
states gph(E) of
states 9ph(E) of the
the perturbing
perturbing field
field state E
state Ev,
y ,

G J
r(E)gph(E)dE
G == J r(E)gph(E)dE (4.12)
(4.12) fv
11
Iv == e(Ev-EFp)/kBT
/L" '0_ \JI._1"
+ _,
1'
(4.14)
(4.14)
86
86 The Physics
The Physics of
of Solar
Solar Cells
Cells Generation and
Generation and Recombination
Recombination 87
87

initial
initial final
final The same
same matrix
matrix element
element controls
controls absorption
absorption and
andspontaneous
spontaneousemission
emission
because of microscopic
microscopicreversibility:
reversibilty: although
although the
the initial and final
final states in
in
Fermi's Golden
Fermi's Rule have
Golden Rule have been
been exchanged,
exchanged, the
the value
value of H;v
of H;v remains
remains the
the
same.
In
In the
thesteady
steady state,
state, the
therates
rates of
ofall
allthree
threeprocesses
processes must balance. Setting
Setting

:; Tabs 0,
.p == 0,
r abs -- rTsp (4.17)
(4.17)

(a) we find that
we find
(al
11
inital
initial final
final I
t = e(E-~I')/kBT
= e(E-6.J)/ _ 1 (4.18)

where we
we have
have used
used the definition of l:.
f:.J1.

l:. = EFn - EFp.

i :; It is
is clear
clear from Eq.
Eq. 4.19
4.19 that aa more
more intense light field
field will
(4.19)

wil cause a greater

I1 . separation in quasi
quasi Fermi
Fermi levels.
levels. For this reason,
reason, l:.
f:.J.l isissometimes
sometimes referred
referred
to as
to as the
the 'chemical potential of
'chemical potential of radiation'
radiation' [Wuerfel, 1982] .
Wuerfel, 1982J.
(b)
(bl It is
is the
the quasi-equilibrium
quasi-equilbrium occupation funct ion for
occupation function for photons.
photons. Thus, the
Thus, the
energy E
number density of photons of energy E in quasi tthermal
hermal equilibrium is
is given
initial finnl
linnl by

. nph(E) = t(E)gph(E) (4.20)

-7 :.
-7
-7 where
wil be
will
gph(E)
where gph(E) is the
is the

be determined
density
density

determined by by the
of

the strength
strengthof
states. Away
of photon states.
ofthe
fromequilibrium
Away from
theelectromagnetic
equilbrium nnph(E)
electromagnetic field.
field.
ph(E)

Equation 4.17 also gives

4.17 also gives usus the
the useful
useful result
result that:
that:
(c)
(cl
lle(1 tv) == I
e(l -- Iv) i. (Iv
(Iv - te)
Ie).. (4.21)
(4.21 )
Fig.
Fig, 4. 2. (al
4.2. (a) Absorption
Absorption ofof aa photon t o promote
photon to promote ananelectron.
electron. (b)
(b) Relaxation
Relaxation ofof an
an
electron
electron accompanied
accompanied byby spontaneous
spontaneous photon
photon emission.
emission,(e)
(c) Absorpt ion of
Absorption of aa photon
photon ttoo
result
result in relaxation and stimulated
stimulated photon
photon emission.
emission.
4.4.
4.4. Photogeneration

Ie the probability
probability that there is
is an
an electron
electron in E e, Photogeneration
Photogenerat ion isis by
by far
far the most important generation
generation process
process in pho-
Ie the that there in state
state Ee, tovoltaic devices.
tovoltaic devices. By By photogeneration
photogeneration we wemean
mean thethe generation of mobile
mobile
11 electrons
electrons and
and holes
holes through the absorption
through the absorption ofof light
light inin the
the semiconductor.
semiconductor.
te =
Ie e (Ec-EPn) / koT +
= e(Ec-Epn)/kBT +11 '' (4.15)
(4.15)
Other generation processes
processes of of relevance
relevancetoto photovoltaics
photovoltaicsare are trap
trap assisted
It the
the probability that there
probabilty that there is
is aa photon,
photon, and H ev isis the
and Hev the optical
optical matrix
matrix and Auger
and Auger generation,
generation,whichwhichwill
wil be
be mentioned
ment ioned in Chapters
Chapters 88 andand 10,
10,
element. respectively.
Spontaneous
Spontaneous emission
emission proceeds
proceedsat at aa rate
rate Though most
Though most relevant
relevant for
for photovoltaics,
photovoltaics,this
thisisis not
not the
the only optical
optical
27r
271" 22 process which
process which occurs
occurs in in semiconductors. Photons may
semiconductors. Photons may alternatively
alternatively be
Tsp == /iIHev
rsp -,IHevl l te. (1-
I e' (1 I v).
- tv). (4.16)
(4.16) absorbed to
absorbed to increase
increase thethe kinetic
kinetic energy
energy of mobile
mobile carriers
carriers (free
(free carrier
88 The Physics
The PhysicsofofSolar
SolarCells
Cel ls Generation
Generation and
andReombination
Recombination 89
89
88

absorption) or to generate phonons, or to promote electrons between lo-

absorption) or to generate phonons, or to promote electrons between 10-
calised states, or they may be scattered. The first two of these are usu-
calised states, or they may be scattered. The first two of these are usu-
ally important only at photon energies much smaller than the band gap
ally important only at photon energies much smaller than the band gap I1=
= (l-R)
100 meV) and the first only at high carrier densities. Near to the band Is (l-R) IsIs exp(-ax)
exp(-ax)
C,,:: 100 meV) and the first only at high carrier densities, Near to the band
gap, band
gap, band to
to band
bandand
and localised
localised state
state to
to band
band transitions
transitionsare
are dominant.
dominant.
Scattering, particularly by interfaces and by inhomogeneities
Scattering, particularly by interfaces and by inhomogeneities in in non
non
uniform media, removes light from the incident beam without generating (l-R) Is
uniform media, removes light from the incident beam without generating
carriers, and so is undesirable for photovoltaics. However, it may be ex-
carriers, and so is undesirable for photovoltaics. However, it may be ex-
ploited in solar cell structures which are designed to trap the light and so
ploited in solar cell structures which are designed to trap the light and so
amplify the photon field . This will be discussed in Chapter 9. x
amplify the photon field. This wil be discussed in Chapter 9.
Fig.
Fig. 4,3.
4. 3. Attenuation
Attenuationofoflight
lightintensity
intensity in
in aaslab
slab ofofabsorption
absorption i:c:t and
and thickness
thickness x,
x. A
A
4.4.1. Photogeneration rate fraction
fraction (l-R)
(l-R) of
of the
the light
light incident
incident from
from the
the sun,
s un, Is,
Is, isis reflected
reflected at
at the
thefront
frontsurface,
surface.
4.4.1. Photogeneration rate The
The remaining
remaining intensity
intensity attenuates
attenuates exponentially
exponentially with
with distance
distance inin aa uniform
uniform material,
material
as
as shown
shown by
by the
the thin
thin black
black line.
line. Photon
Photon flux
flux density
density attenuates
attenuates in
in the
thesame
sameway,
way. '
The macroscopic absorption coefficient a describes how the light intensity
The macroscopic absorption coeffcient a describes how the light intensity
is attenuated on passing through the material. a:(E) may be considered as
is attenuated on passing through the materiaL. a(E) may be considered as
the sum of the absorption cross sections per unit volume of material for
the sum of the absorption cross sections per unit volume of material for where
where bb is
is the
the photon
photon flux
flux at
at x.
x. Notice
Notice that
that it
it is
is the
the number and not
number and not the
the
the various
the various optical
optical processes.
processes. Suppose
Suppose aa beam
beam ofof photons
photons of energy EE and
of energy and energy
energy ofof the
the photons
photons which
which determines
determines thethe photogenera
photogeneration rate. To
tion rate. To relate
relate
intensity [0 is normally incident on a slab of absorbing material. A fraction
intensity 10 is normally incident on a slab of absorbing materiaL. A fraction 9 to
9 to the incidentflux
theincident fluxwe we need
need to allow
to allow for reflection
for reflection of of photons
photons at
at the
the surface
surface
alE)
a(E) .. dx
dx of
of the photons of energy E entering a slab of thickness dx will
the photons of energy E entering a slab of thickness dx wil and attenuation within
and attenuation within thethe material.
materiaL. Thus
Thus
be absorbed and the light intensity [(x ) will be attenuated by a factor
be absorbed and the light intensity I(x) wil be attenuated by a factor g(E,
g(E, x) (1 -- R(E))a(E)bs(E)
x) == (1 J; goCE,x')dx'
R(E))a(E)bs(E)e- e- a(E,x')dx' (4.25)
e - o(E)dx . Hence (4.25)
e-oCE)dx. Hence
d[ = -aI. where bs(E)
where b.(E) isis the
the incident
incident flux and R
flux and R(E)
(E) is
is the
the reflectivity
reflectivity of
of the
the surface
surface
-dI =-c;[. (4.22)
(4.22)
dx
dx to normally incident light of energy E. This is the spectral photogeneration
to normally incident light of energy E. This is the spectral photogeneration
Integrating Eq. 4.22 for a material of non-uniform a the intensity at a depth rate. To
rate. find the
To find the total
total generation
generat ion rate
ra te at
at xx we
we sum
sum over
over photon
photon energies
energies
Integrating Eq. 4.22 for a material of non-uniform a the intensity at a depth
x, [(x), is given by
x, I(x), is given by
[(x) = [(O)e- g a(E,x') dx'
I(x) = I(O)e- J; oCE,x')dx'
(4.23)
(4.23)
G(x) ==
G(x) JJ g(E, x)dE.
g(E, x)dE. (4.26)
(4.26)

where 1(0) is the intensity just inside the surface (i.e., after accounting for The integral
The integral should
should be
be extended
extended only
only over
overenergies
energieswhere
wherephoton
photonabsorption
absorption
where 1(0) is the intensity just inside the surface (i.e., after accounting for primarily results
primarily results in
in free
free carrier generation.
generation.
reflection). For uniform a, this reduces to the simple Beer-Lambert law,
reflection). For uniform a, this reduces to the simple Beer-Lambert law,
I(x) = [(Ole- OX (Fig. 4.3). It can be shown that a is related to the imagi-
I(x) = I(O)e-OX (Fig. 4.3). It can be shown that a is related to the imagi-
nary part of the refractive index Im(ns ) through a = 41rI~(n. ) where>. is the 4.4.2.
4.4.2. Thermali.mtion
Thermalisation
nary part of the refractive index Im(ns) through a = 47T~(n") where is the
wavelength of light. a defined this way may also contain contributions from
wavelength of light. a defined this way may also contain contributions from Photogeneration
Photogenera doesnot
tion does not depend
dependupon
upon the
the energy
energy of
of the
the aabsorbed pho-
bsorbed pho-
scattering; however, these are not considered in the microscopic derivation
scattering; however, these are not considered in the microscopic derivation ton, except
ton, except in
in that
that the
the energy
energy exceed the band
exceed the band gap.
gap. When
When higher
higher energy
energy
below.
below. photons are
are absorbed,
absorbed, they
they generate
generate carriers
carriers with
with higher
IfIfwe photons higher kinetic
kinetic energy,
energy,
wecan
canassume
assumethat
thatall
allphotons
photonsare
are absorbed
absorbed to
to generate
generate free
free carriers
carriers but that
that energy
then the rate of carrier generation, per unit volume, at a depth x below the but energy is is quickly lost and
qUickly lost and only Eg of
only Eg of potential
potent ial energy remains
energy remains
then the rate of carrier generation, per unit volume, at a depth x below the to be
be collected,
collected,asasshown
shownininFig.
Fig.4.4.
4.4.The
Theimportant
importantquantity
quantityisisthe
the num-
num-
surface is given by to
surface is given by berofofexcitation
excitationevents
eventsand
andnot
notthe
the amount
amount ofof energy
energyabsorbed.
absorbed.ThisThis isis
ber
g(E , x) = b(E, x)a(E, x) (4.24)
(4.24) oneofofthe
one themost
mostimportant
important concepts
concepts in
in understanding
understanding photovoltaic
photovoltaic devices.
devices.
g(E, x) = b(E, x)a(E, x)
90 The Physics
The Phy.ics of
ofSolar
SolarCells
Cells Generation and
Generation and Recombination
Recombination 91
90 91

From
From Eq.Eq. 4.10,
4.10, the
the net
net rate
rate of
of transitions
transitions from
from an
an initial
initial state
state in
in the
the
conduction band
conduction band valence
valence bandband Ii)
Ii) =
= Iv,
lv, kv)
kv) to
to aa final
final state
state in
in the
theconduction
conduction band
band If)
If)
Ic, kc) through
Ic,ke) t hrough anan interval
interval E Ec (kc) -- Ev(kv)
E == Ee(ke) Ev (kv)isisgiven
givenby
by
photon
photon
~:> 2; 11
IHcv125(Ec -- Ev
r(E) == 2; J J IHevl2l(Ee
r(E) Ev -- E)(Jv(Ev(kv))
E)(Jv(Ey(kv)) -- fe(Ee(ke)))
fc(Ec(k ))) c

x gv(kv )ge(ke)d3kvd3ke . (4.27)

(4.27)
valence band
valence band Now,
Now, for
for an
an electromagnetic
electromagnetic field
field of
of strength
strength Eo,
Eo, polarisation
polarisation vector
vector g and
and
angular
angular frequency
frequency w,
w, where
where the
the wavelength
wavelength ofof light
light is
is long
long compared
compared to to
interatomic
interatomic distances,
distances, the
the perturbation
perturbation H'H'isisgiven
givenininthe
thedipole
dipoleapproxi-
approxi-
Fig. 4.4. Photogeneration of an electron-hole pair and loss of excess electron and hole mation by
mation by
Fig. 4.4. Photogeneration of an electron-hole pair and loss of excess electron and hole
kinetic energy by thermalisation to the respective band edges.
kinetic energy hy thermalisation to the respective band edges,
Hi =-.p
H' iqEo
iqEo
= 2mo we . p
2mow (4.28)
(4.28)
It isis also
It also the
theessential
essentialdifference
difference between
between photovoltaic
photovoltaic and solar thermal
and solar thermal where
where pp is
is the
the quantum
quantum mechanical
mechanical momentum
momentum operator.
operator. Then
Then
action.
action.
The photogenerated
The photogenerated carriers
carriers lose
lose any
any extra
extra kinetic
kinetic energy
energy by
by thermali-
thermali-
r(E)
2rr 4m~E2 jrj r Mcv 5(Ec - Ev - E)(Jy(Ev(kv))
2rrq2E5n2
T
q2Eg2 r r 22
r(E) = -- 4mE2 J MeAEe - Ev - E)
= (kv)) -- fe(Ee(ke))
(Jv fc(Ec(kc)))
(Ev
or cooling.
sation, or
sation, Microscopically, this
cooling. Microscopically, means that
this means they undergo
that they undergo repeated
repeated
collisions with the
collsions with the lattice,
lattice, giving
giving upup some
some of
of their
their kinetic
kinetic energy
energy to to produce
produce X ge (k')gv (k)d3kd3k' (4.29)
aa phonon
phonon while
while they
they decay into a lower energy state, until they are in
decay into a lower energy state, until they are ther-
in ther-
mal equilibrium with the ambient. Phonons are the means by which energy where
mal equilbrium with the ambient. Phonons are the means by which energy
is
is carried
carried away
away toto the outside world.
the outside world. This cooling happens
This cooling happens very
very fast,
fast, on
on the
the Mev == I(v,
Mev kl. pic,
I(v, kle pic,k/)1
k')1 (4.30)
order
order of
of picoseconds,
picoseconds, partly because of
partly because of the
the high
high density of final
density of final states which
states which
are
are available
available at
at lower
lowerkinetic energy. Cooling
kietic energy. Cooling isisfaster
fasterthan
than all
all but
but the most
the most is called
is called the dipole matrix element.
element.
intense generation processes. In exceptional circumstances, for
intense generation processes. In exceptional circumstances, for example for example for Sincer(E)
Since r(E) represents the net
represents the net rate
rate of photon absorption,
of photon absorption, the
the electromag-
electromag-
very
very high
high optical
optical intensities
intensities oror for
for electronic
electronic structures with reduced
structures with reduced den-den- netic field
netic field is giving up energy to the semiconductor
energy to semiconductor at
at aa net
net rate
sity
sity of
of available
availablestates,
states, then
then the
the carriers
carriers may
may not
not bebe able
able toto lose
lose energy
energy 8UE = -E x r(E)
fast enough and consequently are 'hot'. This will be discussed in detail in aUE = -E x r(E) (4.31)
(4.31)
fast enough and consequently are 'hot'. This wil be discussed in detail in
Chapter 10.
at
Chapter 10. per unit
unit time,
per time, where
where UEUE isis the
the energy
energy density
density of
of the
the radiation.
radiation. Now,
Now, we use
we use
the fact
the fact that,
that, for
for aa plane
plane wave, the cycle-averaged
wave, the rate at
cycle-averaged rate at which
which the
the beam
beam
4.4.3. Microscopic description of absorption
4.4.3. Microscopic description of absorption losesenergy
loses energywith
withtime
timeisisequal
equaltotothe
therate
rateat
at which
which the
the beam
beam loses
loses intensity
intensity
with distance,
with distance,
Since
Sincephotogeneration
photogenerationisisthethe promotion
promotionof ofan
an electron
electron from
from aa valence
valencetoto aa
conduction 81 UE
conduction band
band energy
energy level,
level,the
theenergy
energydependence
dependenceofofaamust
must be
be strongly
strongly (4.32)
(4.32)
related x - --
to
related to the density of valence and conduction band states and therefore
the density of valence and conduction band states and therefore
to
to the
the band
band structure of the
structure of the materiaL.
material. Here
Here we
wewill see how
wil see how using
using Fermi's
Fermi's ififxxisisthe
thedirection
directionof
ofpropagation.
propagation.From
FromEq.
Eq.4.22
4.22the
theabsorption
absorption coefficient
coeffcient
Golden
GoldenRule.
Rule.Further
FUrther details
details of
of the
the microscopic
microscopic optical properties of
optical properties of Semi-
Semi- isisgiven
given by
by
conductors are given elsewhere [Bassani, 1975; Stern, 1963; Wuerfel,
conductors are given elsewhere Bassani, 1975; Stern, 1963; Wuerfel, 1982; 1982; 1 d1
dI .
-1dx
a = -1
Bastard, 1986].
Bastard, 1986J. a = dx'
 Physics of Solar
The Physics Solar Cells
Cells Generation
Generation and Reombination
Recombination 93
92

Now, since
Now, since the
the intensity of radiation
intensity of in aa medium
radiation in medium of
of refractive
refractive index
index ns
n. T 4.4.4. Direct
4.4.4. Direct gap semiconductors
UE through
is related to UE i In aa crystal,
crystal, electron
electron and hole
hole states can be
be written,
written, using
using the
the Bloch
Bloch the-
the-
(4.33) orem, as the
orem, as the product of aa plane
plane wave and aa rapidly
wave and rapidly varying atomic part.
I = UEC (4.33)
ns Thus
and, from
and, from basic
basic electromagnetic
electromagnetic theory,
theory, Ie, k')
Ic, ue(r)eik'.r
k') == ue(r)eik'.r (4.41))
(4.41
2E2
UE =
UE n. a0
= ns (4.34)
(4.34) and
871"
871

we finally
we finally obtain for a: lv, k)
lv, k) = Uy(r)e ik .r ..
= uv(r)eik.r

nsE E )
a == --U
a Tab. (E)..
n. U Tabs(E (4.35)
(4.35) Now, acting on
Now, acting Ic, k')
on Ie, k') with
with the differential operator -ilie
differential operator -i .. V,
V, where
where the
the
C EE momentum operatorhas
momentum operator hasbeen
beenwritten
writtenasas-i1iV,
-inV, and
and writing
writing the matrix
matrix
Substituting for
Substituting Tab.(E), from
for Tabs(E), from Eq.
Eq. 4.29,
4.29, we
we obtain
obtain element in integral
element in integral notation we for the matrix element
we obtain for element

alE) = ~: J J M;vi5(Ee - Ev - E)(fv(Ev(kv)) - fcEe(ke)))

Mev == -ihE
Mev f[ei(k'-k).ru~(r)Vue(r)+ +ik'ei(k'-k)'ru~(r)ue(r)ld3r.
-i. fej(k'-k)'ru~(r)VUe(r) ik'ei(k'-k).ru~(r)ue(r)ld3r.(4.42)
(4.42)

x ge(k')gv (k)d3kd3k' (4.36)

(4.36) First, the integral
integral is non zero
mentum must be
zero only
be conserved.
when k'k' -- kk == o.o.InInother
only when otherwords,
conserved. This is the usual selection rule for
words,mo-
mo-
for optical
optical tran-
where sitions. It is the reason
sitions. reason for the distinction
distinction between direct and indirect gap gap
A,,=-.
A" = 47r2q2
2
n
471"2q /i
nscmaE
nscmo E
. (4.37)
(4.37)
materials. Second,
must vanish
Second, thethe contribution from
since the
vanish since the different
different bands
from the
the second
bands e,c, and
second term
and v,
term in
in the
the intergrand
v, must be orthoghonal. This
is a consequence
is consequence of of quantum
quantum mechanics.
mechanics.ThenThen the
the dipole
dipole matrix element is
For low enough
For low enough excitation levels, the
excitation levels, valence band
the valence band isis effectively
effectively full (f yv ~
full (f ~
simply given
by by (clcplv). Mev is a property of the material and, in
in general,
general,
(fe ~
simply given (cle.plv). Mev is a property of
1)
1) and
and the conduction band
the conduction empty (fe
band empty 0), so,
~ 0), so, to
to aa good
good approximation
approximation
of the electric field
field direction.
direction. For
For isotropic
isotropicmaterials M;v== !1(cJplv)l2.
materialsM;v ~ l(clplvjl.
(4.38)
(4.38) Now a can
Now can be
be evaluated
evaluated simply
simply from the densities of states.
states. When these
alE) = ~: J J M;vi5(Ee - Ev - E)ge(k')gv(k)d3kd3k' .
depend only on energy
energy wewe have
have
The
sum
macroscopic absorption
The macroscopic
of
absorption coefficient
contributions from all
coeffcient may
valence
may alternatively
(i) to conduction
be considered
alternatively be
(f)
considered as
band
as aa
transitions
sum of contributions from all valence (i) to conduction (I) band transitions aalE) -Mev
mo
f
ge(k(Ei +
A" M;v2 f ge(k(E
(E) = A" + E))gv(k(Ed)dEi.
E))gAk(Ei))dE. (4.43)
( 4.43)
which differ in energy by E
energy by
The quantity given
given by the integral
integral is known
known asas the joint density of states
alE) ==
a(E) LL aif(E)
alf(E) (4.39)
( 4.39) (JDOS).
(JDOS). In the case
In the case of the parabolic
of the parabolic band
band approximation
approximation (introduced
(introduced in in
l,f
i,f Chapter 3),
Chapter 3), where
where gy(E)
gv(E) varies
varies like
like (Evo
(Eva -- E)1/2
E)1/2 and
and ge(E)
gc(E) varies
varies like
like
where (E
(E -- Eea)1/2,
Eeo)1 /2, it
it is
is straightforward
straightforward to to show
show that
that
(4.40)
air(E) = A" MM(Er - Ei - E) (4.40)
aif(E) = A" MM(Ef - Ei - E)
ma
mo
alE) = aa(E - Eg)1/2 (4.44)

In this representation,
representation, the the density
density of
of kk states
states is
is included
included through the sum-
sum- where ao
where aa is
is a material dependent
dependent constant,
constant, and
and Eg == Eeo
Eco -- Eva. Thus, the
Evo. Thus,
In this through the
mation over different transitions. "" absorption coeffcient
coefficient reflects the shape of the individual densities of states.
mation over different transitions.
Our expression for In general the
In general the JDOS
JDOS of of aa direct
direct gap
gap material
material will
wil look like
like the
the product of
Our expression for aa wil
will simplify
simplify when
when wewe evaluate
evaluate the
the matrix element.
matrix element.
At this stage
stage it
it is
is worth
worth distinguishing
distinguishing direct
direct and
and indirect
indirect gap
gap materials.
materials. the conduction band and and valence band density
valence band density of
of states
states (DOS)
(DOS) functions.
At this
94
94 The Physics
The Physics of
of Solar
Solar Cells
CeUs Generation and
Generation and Recombination
Recombination 95
95

4.4.5. Indirect gap

4.4.5. Indirect gap semiconductors
semiconductors depends
depends upon the
the availability
availability of a phonon
phonon of
of suitable
suitable energy,
energy, the density
density
of
of occupied
occupied valence band states
valence band states and
and of unoccupied
unoccupied conduction
conduction band
band states.
states.
In indirect
In indirect gap
gap materials,
materials, this
this is
is not
not the
thecase.
case. Equation
Equation 4.424.42 showed
showed that
that
According
According to to Bose-Einstein
Bose-Einstein statistics
statistics the
the probability
probability of
of finding
fiding aa phonon
phonon of
of
optical transitions
optical transitions cannot
cannot occur
occur unless
unless k/kl -- kk == o.O.Therefore
Therefore an an electron
electron
energy Ep
energy Episis given
given by eEp/k~T -1'
by eEp/k~T -i. If
If the
thevarious
variousmatrix
matrix elements
elements are energy
energy
cannot be
cannot be excited
excited from
from the
the valence
valence band
band maximum
maximum to the conduction
to the conduction band
band
independent,
independent, the conduction
conduction band is initially empty and the the valence
valence band
band
minimum in
minimum in an
an indirect
indirect gap
gap material
material simply
simply by by the
the absorption
absorption ofof aa photon.
photon.
full, then the
the transition
transition rate
ratevaries
varies like
like
What can
What can happen,
happen, however,
however, is is that the
the electron
electron can
can be
be excited
excited simulta-
simulta-
neously with
neously absorption or emission
with the absorption emission of phonon. In
of aa phonon. In the first case
case the rOC ~ " 1m J 9c(Ei + E + Ep)9v(E)dEi (4.46)
ground state
ground is aa composite
state is composite state of of electron
electron in the
the valence
valence band plus
plus a
phonon, and the final state
state is
is aa composite
composite of an electron in the conduction
conduction where the integral
where the can be taken
integral can taken over
over energies, rather than
energies, rather than k, since
since the
the
band and
band and no
no phonon:
phonon: phonon distribution isis isotropic
phonon distribution isotropic inin k.
k. Using
Using the densities
densities of states for
for
Ii} == Iv,kjWp,kp
Iv, kjwp , kp} parabolic bands
parabolic bands such
such that gv(E) oc
that 9v(E) (Evo -- E)I/2
DC (Eva E)I/2 and gc(E) exDC (E
and 9c(E) (E -- Eca)I/2,
EcO)1 /2,
li
the integral can
can be
be evaluated
evaluated to find
If)
lf =
= le,k/jO)
Ic,k'jO
(Eg - E - Ep)2
up_ ex eEp/kBT _ 1
where the
where the phonon
phonon has
has energy Ep == liw
energy Ep and momentum
1ipp and momentum hkp.
likp . Conservation
Conservation
requires that
of energy requires
A second type of indirect transition,
second type t ransition, where
where the photon
photon absorption
absorption causes
causes
Ep = Ec(kl) - Ev(k) - 1i . (4.45)
(4.45) the generation
generation of aa phonon,
phonon, should
should be
be included.
included.In
In this
this case
case the
the transition
rate isis proportional
rate proportionaltotothetheprobability
probabilityofofphonon
phonon emission,
emission, 1-. .1
J eln_
ks 1, and
and
Evaluation of the matrix element
element delivers
delivers the condition due due to momentum the contribution to to ua varies
varies like
like
conservation
conservation that
that k/
kl -- kp
kp -- kk == O.
O.'Transitions
Transitionsfrom from the
thevalence
valenceband
band max-
max-
imum ttoo the conduction
conduction band
band minimum
minimum are are allowed
allowed if a phonon of suitable up+ ex(Eg
1 _ -e-Ep/kBT
E - Ep)2
.
k is available
available (Fig. 4.5)
4.5).. The sum over over all
all initial
initial and final
final states must
must now
now
involve
involve the
the probability density of
probabilty density of phonons
phonons of of energy Ep and and wavevector kp ,
wavevector kp, The net absorption
a bsorption coeffcient
coefficient is the sum
sum of
of contributions
contributions from
from each type
np(Ep), as well
well as the JDOS
JDOS of of conduction
conduction andand valence
valence bands. event. At
of event. At photon energies
energies which
whichare
aresuch
suchthat
that EE - Eg kBT
Eg ).). kBT,, Ep
Ep can be
We
We will estimate the
wil estimate the absorption
absorption coeffcient
coefficient forfor an
an indirect
indirect transition
transition neglected in
neglected in tthe numerator and
he numerator and the
the absorption
absorption coefficient
coeffcient has
has the
the quadratic
with absorption. See
with phonon absorption. See also
also (Pankove,
([Pankove, 19711).
1971]). TheThe transition rate
transition rate form

u oc (E - Eg)2 . (4.47)
(4.4 7)
conduction
conduction band
band

x
The absorption
The coeffcient of
absorption coefficient of an
an indirect material
material has
has very different
different be-
be-
haviour to
haviour to aa direct
direct gap material and does
material and not reflect
does not the JDOS
reflect the JDOS at pho- pho-
ton energies closetoto the
energies close the band
band edge.
edge. atE)
u(E) is
is generally
generally smaller
smaller and
and rises
rises
more smoothly
more smoothly from
from the
the band
band edge than in direct
edge than direct gap
gap materials.
materials. Simi-
Simi-
lar behaviour is observed
observed in highly
highly doped
doped semiconductors
semiconductors where electron
valence band
valence band scattering, rather than
scattering, than phonon
phonon emission and absorption,
emission and absorption, assists
assists the
the optical
optical
direct
direct gap
gap transitions.
indirect
indirect gap
gap
At higher
At higher photon energies,
energies, direct
direct optical
optical transitions
transitions are allowed
allowed inin the
the
Fig.
Fig. 4.5. Absorption in
4,5. Absorption in aa direct
direct and
and indirect
indirect gap
gap band
band structure.
structure. In
In the
the indirect
indirect gap
gap indirect gap materiaL.The
gap material. The contribution
contribution of these direct transitions should
these direct should
material,
material, aa phonon
phonon of
of momentum
momentum kp is needed
kp is needed to conserve momentum.
to conserve momentum. reflect the
reflect the JDOS
JDOS without
without any phonon
phonon contributions
contributions and so rise
rise more
more rapidly
rapidly
96 The Physics
The Physics of Solar Cells
Cells Generation and
and Recombination
Recombination 97

with energy
energy than the indirect
indirect contributions.
contributions. The direct
direct contributions
contributions usu-
usu- The important point for
The for application
application toto photovoltaics
photovoltaics is is that excitonic
excitonic
ally appear as a change
ally change in curvature in atE).
in o:(E). absorption does
absorption does not
not automatically generate mobile carriers.
generate mobile carriers. The exciton
exciton
needs to dissociate
needs dissociate first,
first, and it may recombine beforethat
recombine before that happens. There-
4.4.6. Other types
4.4.6. Other types of
of behaviour fore in
fore in modelling
modellng device behaviour
behaviour we we should
should use
use for
for G
G the
the net generation
rate of free
free carriers from exciton generation and and dissociation,
dissociation, and and not sim-
In
In practice, the (E
practice, the (E -- Eg)1/2
Eg)1/2 behaviour predicted by
behaviour predicted by Eq.
Eq. 4.44
4.44 is
is seldom seen.
seldom seen. ply the optical excitation rate.
above Eg
At energies above Eg the DOS functions
functions diverge
diverge from
from the
the parabolic approx- Sensitisers are
Sensitisers are analogous
analogous to to excitons
excitons and
and are usually
usually deliberately
deliberately in-
in-
imation, while at energies
energies just belowbelow Eg excitons
excitons influence
influence the absorption. troduced as optical
troduced optical absorbers.
absorbers. The The sensitiser
sensitiser may
may be be aamolecular
molecular species
species
The parabolic band approximation is only only good
good close
close to the
the band
band ex-
ex- such as
such as a dye
dye molecule,
molecule, or or aa small
small solid
solidstate
state particle
particle in in contact
contact with
with a
trema, typically
typically within 100 100 meV. values of
meV. At values of kk far
far from
from the
the band
band extrema semiconductor surface.
semiconductor surface. Such
Such systems
systems are
are widely
widely used
used inin photography.
photography. The
the E(k)
E(k) curve
curve begins
begins to flatten out, and and becomes
becomes stationary at other high photon creates an excited state, which which may then dissociate
dissociate into a charged
charged
symmetry values
symmetry values of of k.k. This
This leads
leads to local
local maxima
maxima and and other features
features in pair, following
following the sequence
sequence
in the DOS,
in DOS, which
which can often often bebe identified
identified from peaks in
from peaks in the absorption
absorption
spectrum.
to atE)
s+ hv -+
S + hv -- S .t S+
S. {c} S+ + e-
e-+
As
As aa better
better approximation
approximation to than (E
o:(E) than (E -- Eg)1/2,
Eg)1/2, parametric
parametric forms
forms
may be derived for for groups of semiconductors
semiconductors sharing
sharing aa similar
similar crystal
crystal struc-
ture. These wil
will depend
depend typically
typically upon
upon thethe energies
energies of the important
important sym-
sym- where S,
where S, S*
S* and S+ represent
represent the ground
ground state, excited
excited state, and
and ionised
ionised
metry points, band
metry points, gaps and
band gaps and dipole
dipole matrix
matrix elements.
elements. Various
Various models
models have
have state of the sensitiser. The final stage
sensitiser. The involves injection
stage involves injection of the free
free carrier
beendeveloped
been developed for III-V
for the the III-V andfamiles
and II-VI II-VI of
families of semiconductors [Adachi,
semiconductors Adachi, into the semiconductor. Sensitisers at heterojunctions may inject charges of
Sensitisers at
1992].
1992j. opposite sign
opposite sign into
into the two different media forming the junction
junction Hagfeldt,
[Hagfeldt,
2000].
2000J.
absorption by excitons
In the case of absorption excitons or
or sensitisers
sensitisers the
the optical
optical generation
Multiple
Multiple step photogeneration
rate should bebe replaced by
As well
As well as
as direct
direct band
band to band photogeneration, free free charge carriers may be
generated indirectly, where
where the
the photon is is absorbed
absorbed toto create
create an excited statestate g(E, x)
g(E, (1 -- R(E))TJdiss(E)o:(E)bs(E)e-
x) == (1 R(E))7]diss(E)a(E)bs(E)e-;1;a(E,x')dx'
a(E,x')dx'
which subsequently
which subsequently dissociates
dissociates to release one or more free
release one free carriers. Exam-
ples are absorption by excitons and by sensitisers.
ples are sensitisers. Excitons are Coulombic
where 7]diss(E)
TJdiss(E)isisthe
thequantum
quantumefficiency
effciencyfor dissociation,i.i.e.,e.,the
fordissociation, theprobability
probabilty
bound states of of electron-hole pairs, and were
electron-hole pairs, were introduced
introduced in in Chapter 3. An
exciton can
can bebe created
created byby aa photon
photon of energy than E
smaller than Eg.
that one
that one absorbed
absorbed photon
photon of
of energy
energy E wil
will generate
generate aa free
free charge.
charge.
exciton energy smaller g The dif-
ference between
ference between the the exciton
exciton energy
energy and and the
the band gap, called
called the exciton
exciton
binding energy, isis usually
binding energy, usually less
less than
than kBT
kaT and
and so
so most
most excitons
excitons dissociate
dissociate
A morphous
morphous materials
materials
at room
room temperature.
temperature. However,
However, the the binding energy will
binding energy wil be strong in in cases
cases
where the photogenerated
where photogenerated electron
electron and and hole
holewavefunctons
wavefunctions are arelocalised,
localised, In amorphous (non-crystallne)
(non-crystalline) material,
material,the
thelack
lackofoflong-range
long-range order means
as in
in the
the case
case of
of low
low dimensional
dimensional semiconductor
semiconductor structures
structures and and molecu- that crystal
that crystal momentum
momentum needneed not bebe conserved
conserved inin an
an optical
optical transition.
transition. The
lar semiconductors.
semiconductors. In In those
those cases
cases the
the excitons
excitons are
are important features
features of band
band gap
gap is always
always 'direct'. Absorption
Absorption events
events are
are therefore
therefore more likely
likely
the room temperature
temperature absorption.
absorption. The The magnitude
magnitude of of the
the excitonic
excitonic absorp-
absorp- than in the
than in the equivalent
equivalent crystallne
crystalline material;
material; for
for example,
example, the
the absorption
absorption
tion, its
tion, its oscilator
oscillatorstrength,
strength, isisgenerally
generally larger
larger for
for more
more strongly
strongly bound
bound coeffcient is
coefficient is larger
larger in amorphous
amorphous thanthan in
in crystalline
crystalline silicon.
silicon. The
The form
form of
excitons.
excitons. NoteNote that
that only
only stationary
stationary (k 0) excitons
(k == 0) excitons can can be generated
generated a(E) isis dominated
a(E) dominated by by the
the JDOS
JDOS without
without kk conservation
conservation restrictions.
restrictions. This
optically. wil be
will be discussed
discussed for the case
case of amorphous
amorphous silicon
silcon in Chapter 8. 8.
98 The
The Physics
Physics of Solar Cells
Cells Generation
Generation and
and Recombination
Recombination 99

1.0E+
1.0E+06
4.5.
4.5. Recombination

1.0E-+S
1.0E~5 4.5.1. Types of
4.5.1. Types of recombination
reombination
';"

-.
'eE
-U
U
C
C
0o
:
:;::I
1.QE..
1.0E..04

1.0E-t3
1.0Et-03
By recombination we
a number of
we refer
refer to
to the loss of mobile
of removal mechanisms. Unlike
is dominant, several different
mobile electrons
electrons or
Unlike generation,
different recombination
or holes
holes by any of
generation, where one mechanism
recombination mechanisms
mechanisms are are important
important for
~
Co
.. the
the photovoltaic device .
photovoltaic device.
0o
II
1/1 1.0E-t2
1.0E+02
We should distinguish two
We two categories:
categories: unavoidable
unavoidable recombination pro- pro-
.c Al 0,33 Ga O,67As
ci
c(
cesses which
cesses which areare due
due to the essential physical processes
processes in in the
the intrinsic ma-
1.0E+01
1.0E+01
terial, and
and avoidable
avoidable processes
processes which are largely due to to imperfect
imperfect materiaL.
material.
1.OE+
1.0E+OO
Amongst the unavoidable
Amongst unavoidable recombination
recombination processes
processes are are the processes
processes
0.5 1,5
1.5 2.5 which result
which result from generation, spontaneous
from optical generation, spontaneous and stimulated emission emission
Photon Energy
Energy I eV
eV (see Sec. 4.3).
(see Sec. 4.3). For
Forphotovoltaics,
photovoltaics, the the
mostmost important
important of of these is spontaneous
emission, which
emission, which is is also
also known
known as as radiative recombination.
Fig.
Fig. 4.6.
4.6. Absorption spectra of
Absorption spectra ofsome
some common photovoltaic semiconductors.
common photovoltaic semiconductors, Notice
Notice how
how
the band edge semiconductors, GaAs,
edge of the direct semiconductors, GaAs,InPInP and
and AlxGal_xAs
AlxGai_xAs is
is sharper
sharper than The other important
important unavoidable
unavoidable process
process is the interaction
interaction of of an
an elec-
elec-
for the indirect
for indirect semiconductors silcon and germanium,
semiconductors silicon germanium. The sharp edges
edges of the GaAs
GaAs tron or hole
hole with
with aa second
second similar
similar carrier, resulting
resulting in in the decay
decay ofof one
one
and InP absorption
and absorption are
are influenced
influenced. by
by excitonic
excitoniceffects.
effects. carrier across
carrier across the the band
band gap and the increase
increase in the kinetic
kinetic energy
energy of the
other carrier
other carrier by an an amount
amount equalequal to the bandband gap.
gap. This is is called
called Auger
Auger
4.4.7. Examples and
4.4.7. Examples and data
data recombination. It is the reverse
recombination. reverse of a rare generation process where a carrier
with kinetic
with energy greater
kinetic energy greater than
than the band gap is able able toto give
give up
up some
some of
Figure 4.6 shows
Figure 4.6 the absorption
shows the absorption spectra
spectra of of aa number
number of of semiconductors
semiconductors its kinetic energy to excite an electron electron across
across the gap (discussed
(discussed in Chap-
which are important for
which for photovoltaics.
photovoltaics. Notice
Notice how the absorption edge edge for for ter 10).
10). Auger recombination
recombination is is important
important in low band gap materials with
low band
the direct band
band gap
gap semiconductors
semiconductors GaAs GaAs andand InP,
InP, isis sharper
sharper than for the high carrier densities,
high densities, where
where carrier-carrier
carrier-carrier interactions are stronger.
indirect band gap materials, silcon silicon and
and germanium.
germanium. Notice Notice how the shape Avoidable recombination processes
Avoidable recombination processes usually
usually involve
involve relaxation
relaxation by way of
curves for
of the curves for GaAs,
GaAs, InP InP and AlxGal_xAs
AlxGai_xAs are similar;similar; this
this is
is due
due to their a localised trap state.
localised trap state. These
These trap states are due to impurities in the crystal
similar crystal structure.
similar crystal structure. or defects
defects inin the crystal structure. These These are
are often
often known
known as non-radiative
non-radiative
The absorption
absorption length
length of a photovoltaic
photovoltaic material is aa useful useful quantity.
quantity. recombination processes (although
recombination processes (although Auger is also also non-radiative)
non-radiative) and and are
are usu-
This is defined
defined asas the distance light of a particular
particular wavelength
wavelength must travel ally the dominant
dominant mechanisms.
mechanisms. Recombination
Recombination in in semiconductors
semiconductors is is well
well
before the
before the intensity isis attenuated
attenuated by by aa factor
factor e,e, and is
is given by ~. ~. At
At visible
visible covered by
covered by Landsberg Landsberg,
[Landsberg, 1990J and many semiconductor
1990] and semiconductor text- text-
wavelengths
wavelengths the the direct
direct band
band gap
gap materials GaAs and InP have
materials GaAs have absorption books such
books such asas Shur
ShurShur,
[Shur, 1990J
1990] or or Tyagi [Tyagi, 19911.
Tyagi Tyagi, 1991].
lengths
lengths ofof less
less than
than one
one micron.
micron. This
This means
meansthat that only
only a few few microns
microns of
material are
material are needed
needed to to absorb
absorb virtually
virtually all all of
of the
the light.
light. InIn contrast,
contrast, the
indirect gap
indirect gap material
material Si Si has anan absorption
absorption length
length ofof tens
tens ofof microns,
microns, so so 4.5.2. Radiative recombination
4.5.2. Radiative
that
that wafers
wafers tens
tens or
or hundreds
hundreds of of Il-ll
im thick
thick are
are needed
needed forfor good
good absorption.
absorption.
Box 4.2.
Box 4.2. Derivation of the radiative
radiative recombination
recombination rate
Reflectivity has not been
has not treated explicitly
been treated explicitly in this section.
section. ForFor typical
semiconductorsR(E)
semiconductors R(E) isis ~ ~ 30-40%
30-40% at visible
visible wavelengths,
wavelengths, and and so
so itit is
is an Here we
Here we are
are going
going toto derive
derive an
an expression
expression forfor the
the rate of radiative re-re-
important factor.
factor. The
The netnet reflectivity
reflectivity ofof aa semiconductor
semiconductor surface surface can be be using our results
combination using results for absorption coeffcient.
coefficient.
reduced
reduced using
using anti-reflection
anti-reflection coatings or surface
surface texturing; these are treated
texturing; these From Sec. 4.3 above
Sec. 4.3 above we weknow
knowthatthat the rate ofof spontaneous
spontaneous relaxation
in Chapter 9. 9. events from
events from an
an initial state If) == Ic,
initial state Ie, kke) of energy
e ) of energy EeEe to
to aa final
final state Ii) =
state Ii)
 The
The Physics
Physics of Solar
Sola.r Cells
Cells Generation and Recombination 101
100

Now
Now we we can
can relate
relate the
the spontaneous
spontaneous emission
emissionrate
rate to
to the absorption coeff-
coeffi-
cient,
cient, using
using Eq.
Eq. 4.35 to relate
4.35 to relate Tabs
rabs to
to a,
a,

l-
~..'."""'.'""y;",,',
l

_._......;..:_.:~.:..', _.,.n_.._..,..,,,,,.:

I"'."",
~ . .. .
. ,," _. . "~
Substituting

This is the
This is
Tsp =-
rsp =

Substituting for
for gph

the volume
-U
TabsE C
rabsE

volume rate
E ns
Ux x9phfeq
E
9phfeq =

gph and feq

feq we

T =-
c
= -a(E)gph(E)feq(E).
-a(E)gph(E)feq(E).
we have

81m; a(E)E2
sp =h3c2
rsp

rate of
8'1m;
n.

a(E)E2
h3c2e(E-Ll.)lkBT
e(E Ll./L)/kBT __

of radiative
radiative recombination,
11..

taken over
recombination, taken over all
(4.52)
(4.52)

(4.53)
(4.53)

all angles
radiative non-radiative Auger
band-Io-band
band-to-band via trap state
stale of emission. For applications
emission. For applications in devices we are
devices we are most
most often
often interested
interested in
the recombination resolvedalong
recombination resolved alongaaparticular
particulardirection.
direction.InIn that
that case,
case, the
Fig.
Fig, 4.7.
4.7. Radiative band-to-band, non-radiative
Raiative band-to-band, non-radiative and
and Auger recombination.
Auger recombination, geometric factor
geometric factor isis given
given byby 1fir rather
rather than 4ir
41f and
and the
the recombination
recombination rate
is reduced
is reduced by
by a factor 1/4:
lv,
lv, kv)
kv) of energy Ev
of energy is given
Ev is given by
by 2irn; a(E)E2
Tsp = h3c2 e(E-Ll.)lkBT _ 1 . (4.54)
(4.54)
2ir 22
21f )
Tsp==THevfe
rsp THevfe'.(1
(1 - fv)
fv
This ratecan
This rate canbe be expressed
expressed in terms
in terms of of the photon flux from a (biased) black
(Eq. 4.13) while
(Eq. 4.13) while the net rate
the net rate of
of absorption
absorption is
is b(E, Llj.i,)
body, beE, t:.)

Tabs= =
rabs 2: H~vf
2ir 2
THevf . (fv
(Iv -- fe)
fe) Top = be(E, t:.)a(E) (4.55)
(4.55)
where
(Eq.
(Eq. 4.16) wheref f isis the
4.16) where the probability that there
probabilty that there is
is aa photon
photon of energy E
of energy E ==
(Ee - Ev). At quasi thermal equilibrium the two rates match and
(Ee - Ev)' At quasi thermal equilbrium the two rates match and we obtain
Eq.
we obtain
be(E, t:.)
be(E, Llj.i,) == Fa
2 E2
2
Fa h3c2
h3c2 e(E
E2
e(E-Ll.)lkBT
Ll./L)/kBT __ 1
1
Eq. 4.18
4.18 for We will
for f. We call this
wil call this feq(E). Away from
feq(E). Away from equilibrium
equilbrium
feq (4.48) as shown
shown in Eq. 2.14,
2.14, where Fa = = 7r for emission
7r for emission normal
normal to
to the cell
cell surface
Tsp T basXX feq
Tsp == Tabs T.
f' (4.48)
and ns
and ns == 1.
i.
Now, under
Now, under an
an incident
incident field
fieldthe
theprobability that there
probabilty that there isis aa photon
photon of
of energy We obtain
We obtain the total
total radiative
radiative recombination
recombination rate
rate by
by integrating
integrating 4.55
4.55
E is
is related
related to
to the
the (non-equilbrium)
(non-equilibrium) number
number density
density of of photons
photons nph
nph by over photon energies:
energies:

ff gph= nph (4.49)

= nph
gph
(4.49) U:~dal [.e,
U:~dal == 1"'" a(E)be(E,Llj.i,)dE.
a(E)be(E, t:.)dE.

where 9phisisthe
where gph thedensity
densityof
ofphoton
photonstates
statesininthe
the energy
energyrange to E +
rangeEE to + dE. AB explainedin
As explained in Sec.
Sec. 4.1,
4.1, to
to obtain
obtain the net
net recombination
recombination rate we
we must
must
In an optically
optically isotropic
isotropic medium
medium of
of refractive index ns subtract the
subtract the rate
rate at
at thermal equilibrium,
equilbrium, which
which is the rate when t:. == 0,
when Llj.i, 0,
8irn33 E
81fn
h3~3
gph(E) == h3~3
gph(E)
E22
(4.50)
(4.50) Urad =
Urad [~
= 1".0 a(E)b.(E,
a(E)be(E, Llj.i,)dE l""
t:.)dE- - l"" a(E)be(E,
a(E)be(E, O)dE.
O)dE. (4.56)
(4.56)

nph is
nph is related
related to energy density
the field energy density through Spatial variations in the recombination rate enter
enter through
through spatial variations
in t:.(x)
Llj.i,(x)(see
(seealso
alsoWuerfel
WuerfelWuerfel,
[Wuerfel,1982)
1982) and
andStern
SternStern,
[Stern,1963J).
1963]).
nph =UE
nph=E E (4.51)
(4.51)
102
102 The Physics
The Physics of
of Solar
Solar Cells
Cells Generation and
Generation and Recombination
R ecombin ation 103
103

4.5.3. Simplified
4.5.3. Simplified expressions lor radiative
expressions for radiative recombination
recombination
1.2
12 r-------------~==;===~
In order
In order to
to use
use the
the recombination
recombination rate into the
rate into transport equations,
the transport equations, itit would
would
:::i
be useful
be useful to
to be
be able
able toto express
express Urad
Urad in
in terms
terms ofof the carrier densities.
the carrier densities. InIn aa m:::im
i
.... 0 .6
.. i 0,8
semiconductor, EE -- L!tl??
non-degenerate semiconductor, kBT for
t::.J.1 kBT for all
all energies
energies E at
at which
which GI ..
U
2! i:C
the rate,
rate, Eq.
Eq. 4.55,
4.55, is
is non-negligible.
non-negligible. Then, to aa good approximation, i .2 0,6
.2 0.6
.a
E2 :::::: e-(E-~I') / kBTE2
E2 ~ e-(E-L'I')/kBT E2 . 0-
.Q
..
~ E
Ul
411
Ul
.. Ul
411
E 0.4 0.4
e(E-L'I')/knT
1
e(E-~I')/kBT --i~. ~ W
.aW
0.2
Using the relation
Using relation for
for aa semiconductor
semiconductor under
under bias,
bias, Eq.
Eq. 3.53,
3.53,
o
np = eL'l'/kBTni,
2 1,3
1.3 1.35
1.35 1,4 1.45 1.5
1.5 1.55
1.55 1.6
1.6

we can write Eq.

we Eq. 4.56
4.56 as band gap Energy
Energy IleV
eV

Urad = Brad(np - nt) (4.57)

(4.57) Fig. 4.8.
Fig, Absorptionand
4,8, Absorption andcalculated
calculated emission
emission spectrum
spectrumfor
for aa slab
slab of
of GaAs with aa small
GaAs with
density of
of defect levels below the
levels below the band
band edge.
edge, The
The emission spectrum
spectrum is
is strongly
strongly influenced
influenced
where t he shape
by the of the
t he absorption near the
the band
ba nd edge.
edge. Notice
Noticehow
howa asmall
smalldensity of impurity
densityof

1
by shape of absorption near
00 states
stat es below
below the band edge,
edge, which is
is barely
barely visible
visiblein
inthe
theaabsorption spectrum, is
bsorption spectrum, strongly
i. st rongly
_
_ i
1 271
27f '"2 2 -E/kBT
-E/ kBT 2
2 visible in tthe
he emission spectrum.
Brad-Zh32
Brad - 2h 3 2
ni C
n c a0
nsa(E)e
n.a(E)e EdE.
E dE . (4.58)
(4.58) visib!e spectrum .
i

The radiative recombination

The radiative recombination coeffcient
coefficient Brad is carrier
Brad is density independent
carrier density independent with
and is aa property
and is of the
property of the materiaL.
material. 1i
The expression
expression simplifies
simplifiesfurther
further for
for doped material. If
doped material. If the density of Tp,rad== BradNd
Tp,rad
.
BradNd .
(4.62)
photogenerated electrons
photogenerated electrons and
and holes
holes is
is each
each equal to t::.n,
equal to L!n, then in pp type
then in type
The radiative
radiative lifetime can be measured from the time resolved spontaneous
material
material with
with a
a doping
doping density
density N a,
Na,
emission follOWing
emission followinginstantaneous
instantaneousoptical
optical excitation
excitation of the semiconductor
semiconductor
(np
(np -- nt) (no ++L!n)(po
n~) == (no t::.n)(po + t::.n) -- nopo
+ L!n) "" AnNa
nopo :::::: nNa (called photoluminescence or
(called photoluminescence fluorescence). Brad
or fluorescence). Brad cancan be be determined exper-
determined exper-
imentally from the
imentally from the variation
variation ofof Trad
Trad with
with doping.
doping.
where
where nono and
and Po
Po are
are the electron and hole
hole densities
densities in equilibrium, given
in equilbrium, given
by nr/
Na and
by nt / Na a , respectively.
and NNa, respectively.This
This means
meansthat Urad is
that Urad isproportional
proportional to
to the
Equation 4.58 shows
shows that
that Brad
Brad is
coeffcient, and therefore radiative
tion coefficient,
is larger
larger forfor mat
materials
recombination is
radiat ive recombination
erials with a high absorp-
is more
more important
important in
excess
excess minority
minority carrier density, direct band
direct band gap
gap materials.
materials. The exponential
exponential term term means
means that, that, relative to
relative to
Urad =
Urad
n-no
n-
---
no
(4.59) absorption, contributions
absorption, contributions fromfrom energy
energy levels
levelscloser
closertotothe the band edges
edges are
= Tn1rad (4.59)
Tn, rad much more
much more important.
important. It also
also means that that radiative
radiative recombination
recombination from from ei-
where ther band to impurity
ther impurity states inside
inside the band gap can be very very important,
and can dominate over band-to-band events.
11
Tn,rad
Tn ,rad== BradNa
BradNa (4.60)
(4.60) In cases
In cases where
where the
the chemical
chemical potential
potential is is uniform,
uniform, the radiative recombi- recombi-
nation rate can be directly
nation directly related to bias.bias. IfIf L!tl(x) "" qV
t::.J.1(x) :::::: qV throughout
throughout the
is
is the minority rome.
the minority lifetime. AA similar
radiative lifetime.
carrer radiative similar analysis
analysis shows
shows that in
that in material
material tthen,
hen, using Eq. 4.57,
using Eq. 4.57,
nn type material of doping density Nd,Nd ,
Urad ==Urad QV
Urad Urad ,0
,0 (e
(eQV /kB T -- 1)
/kBT 1) (4.63)
Urad = p - PO (4.61)
(4.61)
Tp,rad where Urad
where Urad,o
,O isisaamaterial
material dependent
dependent constant.
 Cells
Physics of Solar Cells
The Physics
The Generatio
Generation and Recombin
n and ation
Recombination 105
104

cells at operatin g of localised

density of statesand
localised states the probabil
ft the
and It that the
ity that
practicall cells the density
Ntisis the
tant forfor practica where
where Nt probabilty the
Radiativ recombi nation is
Radiativee recombination is unimpor
unimportant at operating
themechanism
material ititisisthe
perfect material limits
which limits
mechani sm which localised state is occupied.
is occupied.
point but in the
but in ofperfect
limit of
the limit
Relationships
Relation ships between rates and
between rates complica ted
and carrier densities are more complicated
efficiency.
effciency. when
when the initial
when the initial to
to final
final state transition step process
transitio n is a multi step process and
a multi and when
the transition depends on the
the availabilty
availabil ity of
of aa third
third entity.
entity. Shockley
Shockley Read
Read
the transitio n depends
B ox 4.3. Bimolecular
Box recombination
Bimolecu lar recombination Hall recombination via a
a trap state
state in the
the band
band gap
gap is
is an
an example
example of aa
of
Hall recombi nation via
multi-step consider ed next, is a three
The detailed
detailed treatment ofradiative
treatmen t of above shows
recombi nation above
radiativerecombination how
shows how multi-ste p process
process andand Auger
Auger recombination,
recombination, considered next, is a three
types of carrier process.
recombi nation is
the rate of recombination is proporti
proportional the densities
to the
onal to of both
densities of both types of
usual for
fact, itit isis usual band-to- bandrecombination
for band-to-band which
recombi nation processess which
processe
carrier. In fact,
do not depend on the presence
do presence of a third quantity to vary like
of a third quantity to vary like 4.5.4. Auger
4.5.4. recomb ination
Auger recombination
U = Bnp
U=Bnp In between two similar carriers
two similar in
results in
In Auger
Auger recombination,
recombination, aa collsion
collision between carriers results
the energy,
kinetic energy, and t he recombin a-
where and process
where B is a material and depende nt constant.
process dependent We show
constant . We here that
show here that the excitation
excitation of
of one carrier to aa higher
higher kinetic the recombina-
tion carrier ofof opposite polarity.
opposite polarity.
is consistent
this is consiste nt with
with Fermi's Rule.
Golden Rule.
Fermi's Golden tion of
of the
the other
other across
across the band gap with a carrier
band gap
we may replace
may replace The energy which
which is
is released
released through recombi nation
recombination is given
given up
up as
as kinetic
kinetic
For transitions
For transitio ns from valence to
from valence to conduction band, we
conducti on band, The energy
conditio ns the energy to the
the other
other carrier.
carrier. Ultimate
Ultimately that extra energy will
ly that wil be as heat
lost as
be lost heat
(1 - Iv). Ie in Eq. 4.27. Since under normal energy to
(fy -- Ie)
(Iv fe) with
with (1 - fv). fe in Eq. 4.27. Since under normal conditions the as edge.
band edge.
mainly empty while the valence band is mainly full, as the
the excited
excited carrier relaxes to the band
conduction
conducti band isis mainly empty while the valence band is mainly full,
on band
vary exponentially
functions vary with energy
exponen tially with over the
energy over the relevant For
For band-to-band electron and two holes
recombination, an electron
band-to- band Auger recombination, or aa
holes or
the Fermi Dirac functions relevant t to that used
the hole and two
two electrons
electrons areare involved
involved.. By similar argumen
By aa similar argument to that used
ranges
ranges of of Ev and Ee
Ev and factors Ie
The factors
Ee.. The and Iv
fe and fv are therefore likely
are therefore likely to be the
to be hole and
If the matrix element is only weakly
factors. If the matrix element is only weakly depen- depen- above, the
above, the rate
rate is proporti onal to the densities of all
is proportional all three carriers, so that
carriers, so that
most rapidly varying factors.
outside the
taken outside
be taken integral
the integral the net rate
rate varies
varies like
dent on initial and finalfinal state energies , it
state energies, it can
can be
in and
rate in the integrations
and the the con-
over the
integrati ons over
expression for
in the expression transitionn rate
the transitio
for the con- U Aug = Ap(n2p - n6Po)
e
duction bands separate
valence bands
duction and valence In the
separate.. In the case where the
case where band structur
the band structure
isotropic,
is isotropic , for
for two-electron collisions and
two-electron collisions
21T fEv,o (Ev)dEv
roo
U = -iIH~yI2 -00 (1 - fv lEeo fe(Ec)gc(Ec)dEe. (4.64)
(Ev))gy
UAug = An(np2 - nOP5) (4.66)
(4.66)

for processe s are most importa

aremost carrier
where carrier
nt where
The two integrals in Eq. 4.64 4.64 are in fact
are in the density
fact the of holes
density of the valence
in the
holes in valence for two-hole
two-hole collsions.
collisions. Auger
Auger processes important
is pro- densities are high, for instance in
in low band gap
gap and
and doped
doped material s,
materials, or at
or at
band and electrons in the conducti on band. Thus, the transitio
conduction band. Thus, the transition rate n rate is pro- densities are high, for instance
densities,UUDC()( np. (Remem ber
np. (Remember high temperature.
ture. The
The dependence
depende nce on doping
doping density
density is
is strong. In
In p-type
p-type
to the
portionall to
portiona productofofthe
theproduct carrierdensities,
freecarrier
thefree high tempera
ed to the net
obtain the doped material the electron lifetime for band-to-band
doped material recombi nation
band-to- band Auger recombination
that the
the thermal recombination rate
thermal recombination must be
rate must be subtract
subtracted to obtain net
is given by
recombi nation rate!)
recombination
For transitio ns from
transitions band to
conducti on band
from conduction site, or
localised site,
toaa localised localised
from localised
or from
11
band, we
valence band, we replace the conducti on (or valence)
replace the conduction (or valence) band DOS band DOS Tn,Aug == A
Tn,Aug N2 ..
AnNi (4.67)
(4.67)
site to valence
site n ..
the DOS for the localised state, and n (or p) with the density
function with
function DOS for the localised state, and n (or p) with the density
band to
on band localised
to localised Similarly,
Similarly, the hole is
hole lifetime in n-type material is
of electrons (or holes)
of For conducti
state. For
holes) in the localised state. conduction
have
we have
t ransition s we
state transitions
Tp,Aug - --1 .
Tp ,Aug =- ANd
1
AN2 .
U = BnNt(l - ft) ((4.65)
4.65) d
 The
The Physics
Physics of Solar Cells
Cells Genemtion and
and Recombination
Recombination 107
106

then the trap

trap has
has been
been emptied
emptied again
again and the two two carriers
carriers have
have in effect
effect
recombined. This
recombined. This isis illustrated
ilustrated inin Fig.
Fig. 4.11.
4.11. Localised
Localised states
states which
which serve
serve
mainly to capture and
mainly and release
release only one type of of carrier
carrier are
are usually
usually called
called
traps. Those
traps. which capture
Those which capture both types
types of carrier
carrier are
are called
called recombination
recombination
centres. Usually
centres. Usually recombination
recombination centres
centreslie lie deeper
deeperinto
into the
the band
band gap
gap than
traps.

Box 4.4.
Box 4.4. Derivation of
of the
the Shockley Read Hall
Shockley Read Hall (SRH)
(SRH) recombination
recombination rate

Consider aa semiconductor
semiconductor containing
containing aa density
density NtNt trap
trap states
states atat an
an
Fig.
Fig, 4.9. Energy-momentumrepresentation
4.9, Energy-momentum representationof ofAuger
Auger recombination
recombination inin direct
direct (left)
(left) and
and
indirect (right) band
indirect (right) band gap
gap materials.
materials. A A collsion
collision between
between twotwo electrons
electrons neaJ
near to the mini-
to the mini- energy EEit in the band
energy band gap.
gap. Empty
Empty traps
traps can
can capture
capture electrons
electrons from
from the
mum
mum of of the conduction band
the conduction results in
band results in the
the promotion
promotion of of one
one electron
electron to
to aa higher
higher energy
energy conduction band, and filled
filled traps can capture
capture holes
holes from the valence
valence band.
state and recombination
state and recombination ofof the other with
the other with aa hole.
hole. Both
Both energy
energy and
and momentum
momentum must must bebe The rate
rate at
at which
which electrons
electrons are
are captured
capturedinin this
this bimolecular
bimolecular process
process is
is given
given
conserved.
conserved, TheThe right-hand figure shows
right-hand figure shows that Auger events
that Auger events may
may occur
occur between
between conduc-
conduc-
tion band minimum
minimum andand valence
valence band
band maximum
maximum in in indirect
indirect band
band gap
gap materials,
materials, since
since
by Eq.
by Eq. 4.65
4.65
tion band
the difference
difference in
in momentum can can bebe taken
taken up by the the promoted
promoted electron.
electron.
Une = BnnNt(l - ft)

Auger
Auger recombination
recombination can can also
alsooccur
occurvia
viaaatrap
trap state. An electron
state. An electron collding
colliding where ftft is the probability that
where that the
the trap
trapisis occupied.
occupied. The coeffcient
coefficient can be
with an occupied
with an occupied trap state close
trap state close to the conduction
to the conduction band band can
can stimulate the
stimulate the expressed as
recombination of the electron in the trap state with a valence
recombination of the electron in the trap state with a valence band hole, band hole,
Bn = 'VnO"n (4.68)
(4.68)
whilst energy. Similarly
whilst gaining kinetic energy. Similarly aa hole
holecolliding with an empty
collding with empty trap
trap
close
close to
to the
the valence
valence band
band can
can stimulate Auger recombination.
stimulate Auger recombination. In In these
these cases
cases where Vn
where 'Unisisthe
themean
meanthermal
thermal velocity ofof the
the electron,
electron, and
and0"(J' nn the
the capture
the minority carrier
the minority carrier lifetimes
lifetimes vary
vary like
like N;N
N;Ntt
and Nd1Nt'
and Nd1Nt' cross section
cross sectionofofthe
thetrap
trap for
for electrons.
electrons.ItItwill
wil also
alsobe
be useful
usefultotodefine
defie a
Auger
Auger events
events conserve
conserve momentum
momentum as well as
as well energy. An
as energy. An electron
electron with lifetime for electron capture by the
electron capture the trap
energy E
energy and momentum
E and momentum k k can
can recombine
recombine with with aa hole
hole of energy EE -.
of energy -, E'
E'
1
1
and momentum k',
and momentum provided that
k', provided there is
that there is anan electron
electron state
state available
available at
at Tn,SRH == BnN
Tn,SRH BnNt .. (4.69)
(4.69)
(E + E'), k + k' (see Fig. 4.9). This means that Auger
(E + E'), k + k' (see Fig. 4.9). This mean that Auger recombination canrecombination can t

occur
occur in indirect band
band gapgap materials, unlike radiative recombination
recombination which The rate at
The at which
which electrons
electrons are released from the
released from the trap depends on the
depends on
is suppressed. Auger
is suppressed. Auger recombination
recombination isis therefore
therefore muchmuch more
more important
important in in occupation of
occupation of the
the traps and can
can be
be written
written
indirect than direct band gap materials, and is the dominant
indirect than direct band gap materials, and is the dominant loss mechanismloss mechanism
germanium.
in very pure silicon and germanium. Gne = Ntft (4.70)
(4.70)
7esc

where the release

release time Tese
Tese isisdetermined
determined by
by the
the condition
condition that
that Une
Une = Gne
C ne
4.5.5. Shockley Read
4.5.5. Shockley Hall recombination
Read Hall recombination in equilbrium.
equilibrium. Then
Then itit follows
follows that
By far the
By far the most
most important
importantrecombination
recombination processes
processes inin real
real semiconductors
semiconductors
Gne = Bn1lNtft (4.71)
(4.71)
are those which involve defect or trap states
are those which involve defect or trap states in in the band gap. Since aa trap
gap. Since
state
state is
is spatially
spatially localised
localised whilst
whilst the
the free
free electron
electron or
or hole
hole is
is delocalised,
delocalised, we
we where nt
where nt is the value
value of
of the
the electron
electron density when the electron Fermi level
level
can think of
can think of the free carrier
the free carrier as
as being
being captured
captured byby the
the trap. The carrier
trap. The carrier can
can is equal
is equal to
to the trap
trap level,
level,
subsequently be
subsequently be released
released byby thermal
thermal activation.
activation. Alternatively,
Alternatively, ifif the
the trap
trap
captures
captures aa carrier
carrier of
of the
the opposite
opposite polarity
polarity before
before the
the first
first carrier
carrier is
is released,
released, nt = nie(Et-E1)/kBT (4.72)
(4.72)
108 The Physics
The Physics of
of Solar
Solar CelL.
Cell. Generation and
and Recombination
Recombination 109

In
In a
a similar
similar way,
way, holes
holes are
are captured at aa rate
captured at rate In n
In n type
type material
material

Upc = BppNdt (4.73)

(4.73) ~ (p-po)
U
USRH
SRH~ --
;: (p -.
- po) (4.81)
(4.81)
Tp,SRH .
Tp,SRH
where
However, when
However, when nt and and Pt,
Pt,ororwhen
whenTn,SRH
Tn,SRH and Tp,SRH differ by
Tp,SRH differ by orders
orders of
Bp = vpO"p (4.74)
(4.74) magnitude, these
magnitude, these limiting forms may
limiting forms may notnot apply.
apply. Then the the full
full expression
expression
and must be used.
used.
recombination isis strongest
SRH recombination strongest when
when nandnand pP are
are ofof similar magnitude.
11
Tp,SRH == BpNt
Tp,SRH BpN '' (4.75)
(4.75) examining Eq.
By examining Eq. 4.79
4.79can
can see
seethat
that for
for aa mid
mid gap
gap trap
trap with equal capture
t
times,U has
times,U has its
its maximum
maximum when when n = p. p. (See
(See Fig. 4.10.) This means
4.10.) This means thatthat in
and released at aa rate
released at undoped regions, where where nand
nand pPmay
may be be similar,
similar, SRH recombination is more
important relative
relative to radiative
radiative recombination.
recombination. (Equation 4.57 shows that
4.57 shows that
Gpc = BpptNt(l - it) (4.76)
(4.76) radiative recombination depends only
recombination depends only onon the
the np
np product, which is is constant
where Pt
where Pt is
is the value of the hole density when
hole density when EFp
EFp == E
Et,
t,
for uniform
for 6./1.) This
uniform 6,/1.) This dependence
dependenceon onthethe nip
nip ratio
ratio influences
influences the bias bias
dependence
dependence of of the
the SRH recombinationrate.
SRH recombination rate. We willsee
We wil see in
in Chapter
Chapter 66 that that
Pt =
Pt nje(E;-E.j/kBT..
= ne(E;-E.)!kaT (4.77)
(4.77) SRH recombination varies like eqV!kaT e qV /kBT inin doped
doped material but but like e qV /2kBT
likeeqV!2kaT
in the
the 'depleted'
'depleted' layer
layer between
between two differently
differently doped
doped materials.
materials.
In general, the
In general, the rates
rates of
of capture
capture and release for
and release for electrons
electrons and will be
holes will
and holes be
In real semiconductors, there may be several several trap
trap levels in the
levels in the band gap
different, depending
different, dependingon onthe the affinity
affnity of the trap for for electrons
electrons or
or holes
holes and
and carriers may recombine
and recombine by more more than one one step.
step. However,
However, the largest
largest
its position
position in
in the
the band
band gap.
gap. However,
However, in the steady state, the
steady state, the net
net rate of
contribution is from from traps which are located close close to
to the
the centre of the band
electron capture
electron capture byby the
the traps
traps U Unc
ne - - Gnc must be
G ne must be equal
equaltoto the
the net
net rate of
gap, for
gap, for nn ;:
~ p.
p. So,
So, for bulk
bulk material
material with
with aa uniform
uniform density
density ofof traps,
traps, the
the
hole capture
hole Upe -- Gpc,
capture Upc G pe , since
since charges
charges cannot be allowed
cannot be allowed to
to build
build up
up on the
on the
approximation is
approximation is usually made that recombination
made that recombination through one one particular
traps. This condition fies the
condition fixes value of It,
the value ft,
trap level
trap level is dominant. Multi-level
Multi-level recombination is discussed by Landsberg
f Bnn- Bppt Landsberg, 1990J.
[Landsberg, 1990].
fff =--Bnn
Bn(n++-
Bn(n nt)Bppt
nt) ++Bp(p
Bp(p++Pt)
Pt) ..
(4.78)
(4.78)

it
it can
can then
then be eliminated from
be eliminated
for the net recombination
for
from the
recombination rate
the expressions for U
expressions for U -- G.
G. Finally
Finally we find
we find
--...
GI
Gl
aCls
.. I 3E+20

U np - n
U
SRH
=
SRH =
Tn,SRH(p +
Tn,SRH(p
np-nj
+ Pt) +
2

Tp,sRH(n +
+ Tp,SRH(n nt)
+ nt)
(4.79)
(4.79)
C
C
00
;:
:
as --:-
c~ -:
:s.c :i:Jm
,- .
where we have used the definitions
Read Hall expression
Read
definitionsofofTn,SRH
for recombination
expression for
Tn,SRH and Tp,SRH.
recombination through
Tp,SRH. This
through a
This isis the
single trap
a single
the Shockley
trap state.
Shockley e00 ~
u
u
1!1
1!
--
:t
:t:
For doped semiconductors,
semiconductors, USRH simplifies.InInPptype
USRH simplifies. typematerial,
material, provided II
II:
that TnNa
that TnNa ?? Tpnt
Tpnt and Na Pt,
Na ?? Pt, USRH becomesproportional
USRH becomes proportional to the excess
excess
en 0.00000001
en 0.00000001 0.00001
0,00001 0.01 v 10 10000 10000000

carrier
carrier density,
density,
nIp
(n- no) .
(n - no)
U
USRH;: Tn,SRH
SRH~--- (4.80)
(4.80) Fig.
Fig. 4.10. SRHrecombination
4.10. SRH recombination rate
rate as
as aa function
function of
of the
the ratio
ratio nip
nip for
for aa trap
trap at
at mid-gap,
mid-gap.
Tn,SRH
no The Physics of
of Solar Cells
Cells Genemtion
Generation and
and Recombination
Recombination ni
111

Surface and
4.5.6. Surface
4.5.6. and grain
grain boundary recombination
boundary recombination the electron
electron current
current density
density has
has changed
changed by
by

2
1) 2( ",-.5"
According to Eq. 4.79,
According 4.79, spatial
spatial variations
variations in
inUSRH
USRH can by varia-
can be caused by varia-
tions
tions in nand
nandp,p,or
orby
byspatial
spatialvariations
variations in
in the
the nature
nature or
ornumber
number density
density l:J=J
I::.J=J xxs+-x
s +-8x -J
(
1) 1"'+0"
( i)2 ( 1) 21"'+.5"
-J Xs--QX
Xs--x=q
=q Udx=qSn(ns-no).
Udx=qSn(n.-no).
x,-OX
of the dominant trap. AA higher
higher density of trap states shortens
shortens the
the electron
electron
and hole capture times. In real
capture times. real materials,
materials, defects
defects are
are much
much more
more likely to If the
the interface
interface is aa surface,
surface, then
then this
this condition
condition determines
determines the current
current
occur at surfaces
surfaces and
and at the
the interfaces
interfaces between
between different
different crystal regions
regions in density at
density the surface
at the surface
a multi
a multicrystallne
crystalline oror heterostructured
heterost ructuredmateriaL.
material. Localised
Localisedstates
states at
at surfaces
surfaces
and interfaces
and interfaces include
include both crystal
crystal defects
defects due broken bonds,
due to broken bonds, and
and ex-
ex- In(xs) = -qSn(ns - no) . (4.85)
trinsic impurities
trinsic impurities which
which are deposited from the external
deposited from external environment,
environment, or
which concentrated at interfaces
which are concentrated during growth.
interfaces during growth. InIn such
such cases
cases the
the trap Similarly, the
the change in hole
change in hole current
current density
density at
at an
an interface
interface in
in n type ma-
ma-
responsible for recombination are concentrated in
states responsible in aa two-dimensional
two-dimensional terial is
is given
given by
than three-dimensional
rather than three-dimensional spacespace and
and it is
is much
much more meaningful to ex- ex-
press the
press the recombination
recombination in in terms
terms ofof the
the trap
trap density
density per
per unit
unit area
area of
of the
the
l:Jp = -q Udx = -qSp(Ps - Po),
surface
surface or or interface,
interface, than
than per
per unit volume.
volume. The The relevant
relevant quantity
quantity will
wil be a 1"'+.5"
xs-DX
recombination
recombination flux flux-- the
thenumber
numberofofcarriers
carriers recombining
recombining at the the interface
interface
per unit
unit area
area per unit
unit time,
time, rather
ratherthan
thanaavolume
volume recombination
recombination rate.
rate. and the
and the current
current density
density at
at the
the surface
surface by
by

If a surface
surface contains density N.
contains aa density Ns traps
traps per unit area, then within
within aa very
very
layer x
thin layer Qx around
around the
the surface,
surface, the
the surface
surface recombination
recombinationflux fluxwill
wil be
be Jp(xs) = qSp(Ps - po) . (4.86)
2
sX-
U.r
S;;(P.
Usvx- _ n.ps
_
in.p.-nj
1 -1n
+ pd + (n. + 1lJ1 )
Sp (ns + 'i)
Sn (ys + Pt) + Sp
(4.82)
(4.82) 4.5.7. Trapsversus
4.5.7. Trps versusrecombination
recombination centres
centres

n., Ps When a carrier isis captured

captured by
by aa trap, it may
may then be
be released
released or it may be
per unit area,
area, where
where n.. P. are the
the electron
electron and hole
hole densities at the
the surface.
surface.
annihilated by the capture of the opposite
annihilated type of carrier. When
opposite type When the time
Sn is
Sn is the surface electrons, defined
surface recombination velocity for electrons, defined by,
by,
for electron release
for by thermal activation
release by
Sn = BnN. (4.83)
(4.83) 1
_1_= =Bnne(Et-E;)/kBT
_ Bnnje(Et-E;)/kBT
and Sp
Sp the surface
surface recombination velocity for
for holes,
holes, Tesc
Tesc

Sp = BpNs. (4.84)
(4.84) much shorter
is much shorter than the time
time for
for capture
capture of
of aa hole
hole

In this definition, both Sn and Sp are directed towards the surface

surface from the ~ = Bpp,
bulk. Tcp
In
In pp type material, Eq.
type material, Eq. 4.82
4.82 reduces to
reduces to
the
the state can be considered
considered an an electron
electrontraptmp rather
rather than aa recombination
recombination
Usx r: Sn(ns - no). centre.
centre. This may happen
This may happen if state is close
if the state close in energy to the conduction
in energy conduction
band edge,
edge, or if the cross
cross section for electron
section for electron capture
capture is
is much
much larger
larger than
This leakage
leakage of
of minority
minority carriers
carriers to
to the surface
surface results in
in aa surface
surface recom-
recom- for hole capture, as,
as, for
for instance,
instance, for
for aa positively
positively polarised defect.
defect. Similarly,
Similarly,
bination current.
bination currnt. The
The magnitude
magnitude of of the
the current
current can
can be
be obtained
obtained from
from the localised states
localised states which
which are close
close to
to the valence
valence band or which have a higher
electron
electron continuity
continuity equation. In the
equation. In the dark,
dark, at
at steady state, Eq.
steady state, 4.1 requires
Eq. 4.1 requires cross
cross section
section for
for hole capture act as
hole capture as hole
hole traps. serve to
tmps. Traps serve to slow down
that V ..I In
that 'i n == qUn. Integrating this
qUn. Integrating this across
across the
the interface
interface layer,
layer, wewe find
find that
that the transport
transport of
of carriers
carriers but they
they do
do not
not remove
remove them.
112
112 The Physics
The Ph.ysics of
of Solar
Sola.r Cells
Cells Generation and
Generation and Recombination
Recombination 113
113

.
j
Jl j , For the
For
profile
profile
the fied
fixed charge
charge density
density in
in Poisson's
Poisson's equation
equation we
we need the doping
need the doping

~ TtU
VI
v

v 7.Z
Pfixed(X) = (-N.(x) + Nd(X)) (4.90)
(4.90)
A
where
where Na
No and Nd
Nd represent
represent the
thedensities
densities of
of ionised
ionised acceptors
acceptors and
and donors.
donors.
In
I n and
and Jp
Jp are
are derived for aa crystalline
crystallne material
material in
in Chapter
Chapter 3.
3. According
According
1:7
to
to Eqs.
Eqs. 3.65
3.65 and 3.66, the currents
currents can
can be
be expressed
expressed in terms of
of the electron
electron
(a)
(a) (b)
(b) (c)
(c) and hole
and hole quasi
quasi Fermi
Fermi levels,
levels, in
in one
one dimension,
dimension,
Fig. 4,11.
Fig. 4.11. (a) Electron trapping
(a) Electron trapping and
anddetrapping;
detrapping; (b)
(b)electron-hole
electron-hole recombination;
recombination;
dEFn
(c) hole trapping and detrapping.
(c) hole trapping and detrapping, In = .nn~
dEFp
4.6. Formulation
4.6. Formulation of
of the
the Transport
Transport Problem
Problem Jp = .pp~.
Finally we
Finally we can
can proceed
proceed to solve
solve the
the set
set of
of equations for n,
equationsfor and ~
n, p and set
set out
introduction to
to this
this chapter.
chapter.In
Inone
onedimension,
dimension,
For
For a crystallne
crystalline material, these can
material, these can be
be expressed
expressedininterms
termsofofnand
nand p
in the introduction using the definitions of EF n , EFp
of EFn, EFp (Eqs.
(Eqs. 3.31 and 3.34).
3.31 and 3.34). For
For non-crystalline
non-crystallne
an __ ~~ aJn
an aJn + G
Gn _ U
Un
(4.87) materials we must substitute
we must substitute alternative appropriate
appropriate expressions
expressions forfor IInn and
at -
at - q ax +
q ax n n (4.87)
J p such as
Jp as Eq. 3.81.
3.81.
When InI n and
and Jp
Jp are
aresubstituted
substitutedinto
intoEqs.
Eqs.4.87
4.87 and
and 4.88,
4.88, we
we have
have a set
ap _~8Jp
ap =_ _~ aJp +
+GGp _
-UUp
(4.88) rp as a function of
at q8x .
at- qax p p (4.88) of three equations which can be solved deliver n,
solved to deliver n, pp and rf
assuming that all
x and t assuming all material
materialparameters
parameters are
are known. Boundary
Boundary condi-
condi-
and
and tions are provided by the external
external electrical conditions and by the surface
conditions and surface
d2~
d2 qq conditions, and by the time dependence of the electrical and
recombination conditions,
-d2 = -(-Pfi".d(X) +n-p). (4 .89)
(4.89) optical conditions
optical conditions for
forthe
the transient
tranient problem.
problem.
x = e.
dx2 ~(-Pfixed(X) +n-p).
For
For G Gn and Gp
n and G p we
we provide
provide the
the photogeneration
photogenerationrate rateatat that point . For
that point. For
band-to-band generation,GG == Gn
band-to-band generation, Gn = = Gp
Gp isis given
given by by Eqs.
Eqs. 4.25
4.25 and
and 4.26.
4.26. 4.6.1.
4.6.1. Comments
Comments on
onthe
the transport
transport problem
problem
Photogeneration is the only only generation
generation process
process normally considered explic-
normally considered
itly for solar cells;
cells; thermal Steady
Steady state
state solutions
itly for thermal generation
generation of of carriers
carriers isis taken
taken into
into account
account in in
each
each of of the expressions for
the expressions for recombination.
recombination.To evaluateG(x)
To evaluate G(x) wewe need
need to
to Since solar
Since solarcells
cellsoperate
operateinin the
the steady
steadystate
state we
weare
areusually
usually interested
interested in
in the
know
know the the absorption coeffcienta(E,x),
absorptioncoefficient a(E,x), the reflectivity R(E),
the reflectivity R(E), andand thethe in-
in- case where
case
cident
cident photon flux density
photon flux bs(E) .
density bs(E).
For Un
For or Up
Un or Up we
we should,
should, in
in general,
general, provide
provide the the sum
sum ofof all
all the recom-
recom-
an=ap=o
8n=Op=o
bination
bination processes
processes -- radiative,
radiative, Auger,
Auger, and trap assisted
and trap assisted - - as
as aa function
function
at at
at at
of
of n, , ~ and
n, pp, x. For
and x. For radiative
radiativerecombination
recombinationwe we also
alsoneed
needto toknow
know the
the and solve
and solvethethe transport
transport equations
equations forfor aa steady
steady state
state illumination
ilumination and
and elec-
elec-
coefficient Brad (Eqs.
coeffcient Brad (Eqs. 4.57
4.57 and
and 4.58).
4.58). For Auger
Auger recombination
recombination we we need
need the
the conditions. In
trical conditions. In the steady state, the
the electron
electron and hole
hole densities in each
each
Auger
Auger coefficients
coeffcients (Eq.
(Eq. 4.66).
4.66). For
For SRH
SRH recombination
recombination in in the
the bulk we we need
need band and
band and in localised states must
localised states must be
be constant.
constant. This
This means
means that
that the gen-
gen-
the
the density
density and
and position
position ofof the
the dominant
dominant traptrap state
state andand the lifetimes for
the lifetimes for eration and capture terms
eration terms for
for the
the exchange carriers between
exchange of carriers between band
band and
and
electron
electron and and hole
hole capture (Eq. 4.79);
capture (Eq. 4.79); at the
the surface
surface wewe need the recombi-
recombi- trap states
trap states (as opposed
opposed to recombination centres) must
recombination centres) must cancel
cancel out,
out, and so
nation velocities (Eqs.
nation velocities (Eqs. 4.83
4.83 and 4.84).
4.84). trapping
trapping can
can bebe left
left out
out of
of the
the continuity
continuityequations.
equations.TheThe consequence
consequence isis
114
114 The
The Physics
Physics of
of Solar
Solar Cells
CeUs Generation and
Generation and Recombination
Recombination 115
115

that the
that thegeneration
generationand andrecombination
recombinationprocesses
processes areare all effectively
effectively band-
band- (i) one
(i) one carrier
carrier type
type greatly
greatly exceeds
exceeds the other and
the other and the
the recombination
recombination rate
rate
to-band: Gn
to-band: Gn = G p and
= Gp Un =
and Un Up. The
= Up, The trapped
trapped charge
charge density
density will influence
wil influence simplifies to the monomolecular
simplifies to monomolecular form form UU ~~ (n - nO)lTn
nO)/7n (Eq. 4.80),
4.80), and
the solution
the solution through the fied
through the fixed charge
charge term
terminin Poisson's
Poisson's equation.
equation. (ii) the
(ii) the electric field F
electric field F isis zero
zero or
or constant,
constant, the
the transport
transportequations
equations for
for
the transient
In the transient case
case where
where traps
traps are
are being
being filled
filled or emptied,
emptied, then the
the minority carriers
carriers simplify
simplify to thethe analytically
analyticallysoluble
soluble form:
form:
terms for
for capture andand release
release from
from traps must
must bebe included
included and netnet genera-
genera-
ratefor
for holes
holes and
and electrons
electrons are
are nonzero.
nonzero.
d2n
d?n + qF
qF dn
dn _(n(n-- no) G(x)
no) + G(x) = 0
tion rate (4.93)
dx 2 +kBT
dx2 kBTdx dx -L~-- + Dn
Dn = 0

Photon continuity for electrons in the p region,

region, and

Until now,
Until now, we
we have
have assumed
assumed that
that the
the density
density of photons
photons at a point is
at a is de-
de- d2p
2 + qF
d p + qF dp
dp __ (p
(p -- Po)
Po) +
+ G(x)
G(x) == 00
(4.94)
termined solely
termined solely by
by the absorption
absorption within the the materiaL.
material. That is, is, we
we have
have dx2
dx 2 kBT
kBT dx dxL~
L~ Dp
Dp
assumed that
assumed that the
the density of photons
photons resulting
resulting from
from radiative
radiative recombina-
recombina- and for holes the nn region.
holes in the region.
is negligible
tion is negligible compared
compared to to the incident flux density.
density. In materials with
efficiency, or under high illumination
a high radiative effciency, conditions, these
ilumination conditions, these 're-
're- Here we
Here we have
have used
used the
the Einstein relation !-i.= =
Einstein relation i!!T (Eq. 3.77) for !-i and
~ (Eq. 3.77) for . and
cycled' photons
cycled' photons may
may be be significant.
significant. Then
Then aa further continuity
continuity equation
equation is is have diffusion length
have introduced the diffusion length for
for electrons
electrons
for photons, and a further unknown
required, for unknown needs
needs to be found,
found, the photon Ln = VTnDn (4.95)
flux density b(x).
flux density b(x). The case of photon recycling isis treated
photon recycling treated in Chapter 9. 9.
and holes
4.6.2. Transportequations
4.6.2. Transport equationsin
in aa crystal
crystal Lp = VTpDp. (4.96)
The most
The most relevant
relevant context
context for
for conventional
conventional photovoltaics
photovoltaics isis aa one- one- The diffusion length isis aa measure
diffusion length of the average
measure of distance a minority car-
average distance car-
dimensionally
dimensionally varying crystallne material in
varying crystalline in the
the steady st ate. The
state. The quantity
quantity rier
rier will
wil diffuse
diffse before
before recombining.
recombining. In
In steady state, the
steady state, the one-dimensional
one-dimensional
of interest
interest isis the terminals, IInn +
the net current at either of the terminals, J p , and its
+ Jp, its de-
de-
diffsion equation
diffusion equation becomes
becomes
pendence
pendence on on applied
applied bias
bias and
and illumination.
ilumination. To To find this we firstfirst need
need to set
up the transport
transportequations
equationsand
andsolve
solvefor n,ppand
for n, r/!, as
andrP, as described
described above.
above. (n -- no)
(n
-- no) __ D
- n D d?n
d?n
dx2 (4.97)
( 4.97)
- - 7 -- - n dx 2
We
We proceed
proceed by by combining
combining thethe current equations for
current equations a compositionally
for a n
invariant crystal (Eqs. 3.75 3.75 and
and 3.76)
3.76) with
with thethe steady
steady state continuity equa- which has
which has solutions
solutions for
for the
the excess minoritycarrier
excess minority carrierconcentrations
concentrations(n (n-- no)
tions to obtain
obtain aa pair
pair of
ofsecond
second order
order differential
differential equations
equations governing
governingnandnand of the
of the form
formex/...rrs:r.
e~x/Vf. This
This makes
makes L L= =JI5T
.J a anatural
naturalunit
unitofoflength
length to
pp.. In one dimension characterise diffusion.
characterise diffsion. Minority
Minority carrier concentration
concentration and current
current profiles
profiles
d?n dn dF
d?n
Dndx2
Dn dx 2 +.nF
dn
+ !-in F dx
dx +
+.nn
dF
dx - -UU++G
!-inn dx G == 00 (4.91)
(4.91)
different behaviour
have different behaviour depending on
to the layer width,
width, and to the
on whether L is large or
the absorption
absorption length.
length.
or small compared

Finally,
Finally, we
we solve
solve the
the transport
transport equations for (n-no),
equations for (p -- po)
(n-no), (p Po) subject
subject toto
and
and appropriate boundary conditions.
conditions. In the next chapters, we wil meet several
we will
d2p dp dF
Dp dx2 + .pF dx + .pP dx - U + G = o. (4.92)
(4.92)
examples where
examples where thethe simplified approach of
simplified approach of Eqs.
Eqs. 4.93
4.93 and
and 4.94
4.94 can
can be used.

While G
While G is usually aa function.
function of
of position only, U
position only, U generally
generally depends
depends upon 4.7.
4.7. Summary
Summary
both densities. This
both carrier densities. couples the
This couples equations for
the transport equations for electrons
electroI+s
and holes.
holes. In however, U
In certain situations, however, U depends
depends onon nn or
or pp only
only and
and the
the Photocurrent generation
Photocurrent generation by
by a solar cell
cell is
is linked
linked to charge
charge carrier gener-
equations
equations can
can be solved independently. In
solved independently. In particular, when
particular, when ation and recombination
ation recombination by conservation
conservation ofof the
the numbers
numbers of
of electrons
electrons and
116
116 The Physics
The Physics of
of Solar
Solar Cells
Cells Generation and
Generation and Recombination
Recombination 117
117

holes. Photogeneration is the primary

primary carrier
carrier generation
generation process
process in
in photo-
photo- References
cells. For
voltaic cells. semiconductors, the absorption coeffcient
For direct gap semiconductors, coefficient can
Physical Properties
Adachi, Physical
S. Adachi, Properties ofofIII-
III-VV Semiconductor
Semiconductor Compounds
Compounds (Chichester:
(Chichester:
be described
described mathematically
mathematically by by Fermi's
Fermi's Golden
Golden Rule, and near to the the band
band
1992).
Wiley, 1992).
Wiley,
edge it
edge it depends
depends on on photon
photon energy
energy approximately
approximately as as (E - Eg)1/2.
Eg)1/2. ForFor indi-
indi- Bassani and
F. Bassani and G,G. Pastori Parravicini, Electronic States
Parravicini, Electronic States and Optical
Optical Transitions
Transitions
materials, light
rect gap materials, light absorption
absorptionrequires
requires phonon
phonon absorption
absorptionor oremission,
emission, in Solids
Solids (Oxford:
(Oxford: Pergamon, 1975).
Pergamon, 1975).
the absorption coeffcient
coefficientisis generally
generallysmaller
smaller and and rises
rises more gradually, like like Bastard, Wave
G. Bastard, Wave Mechanics
Mechanics Applied
Applied to to Semiconductor
Semiconductor Heterostructures
Heterostructures (Edi-
(Edi-
(E - E )2, near the band edge. Photogeneration formally requires the dis- tions de
tions de Physique, 1986)
Physique, 1986)
(E - Eg)2, near the band edge. Photogeneration formally requires the dis-
g
Endoreversible Thermodynamics
Vas, Endoreversible
A. de Vos, Thermodynamics of Solar Energy ConversionConversion (Oxford
(Oxford
sociation of an an excited
excited state and is is not identical
identical to lightlight absorption
absorption in in some
some
University Press,
University 1992).
Press, 1992).
compound or organic materials where where this dissociation
dissociation is is incomplete.
incomplete. Fonash, Solar Cell Device
S.J. Fonash, Device Physics
Physics (New York, London:
London: Academic, 1980).
Academic, 1980).
S.J.
The mainmain recombination
recombination mechanisms
mechanisms are are radiative, Auger,
Auger, and trap as- as- Silicon Solar Cells:
M.A. Green, Silicon
M,A. Cells: Advanced
Advanced Principles
Principles and Practice (Sydney:
(Sydney: Cen-
Cen-
sisted recombination in the bulk or at the the surface.
surface. Radiative
Radiative recombination
recombination tre
tre for
for Photovoltaic
Photovoltaic Engineering,
Engineering, 1995).
1995).
relaxation of
is the relaxation ofan
an electron
electron across
across thethe band gap gap together
together with the emis-
with the emis- A. Hagfeldt
A. Hagfeldt and M, M. Grtzel,
Gratzel, "Molecular
''Molecular photovoltaics", Acc. Chem.
photovoltaics" , Acc. Chem. Res,
Res. 33,
33 ,
sion of aa photon. (2000).
269-277 (2000).
photon. It is unavoidable in aa light absorbing absorbing material and is most
P.T. Landsberg, Recombination in Semiconductors
Landsberg, Recombination Semiconductors (New(New York: Cambridge Uni-
York: Cambridge
important when when absorption
absorption is strong, strong, in in direct
direct gap
gap semiconductors.
semiconductors. The The
versity Press, 1991).
versity Press, 1991).
recombination rate is
radiative recombination is described
described by by aa generalised
generalised PlanckPlanck formula
formula J.l. Pankove,
J.L Optical Processes
Pankove, Optical Processes in Semiconductors
Semiconductors (Englewood
(Englewood Cliffs: Prentice
Cliffs: Prentice
and varies
varies approximately as np. Auger recombination is the relaxation of
np. Auger of a Hall, 1971).
Hall, 1971).
charge carrier to excite a second second carrier
carrier to to a higher
higher energy
energy state
state within the M. Shur, Physics of
Shur, Physics ofSemiconductor
Semiconductor Devices
Devices (Englewood
(EnglewoodCliffs: Prentice Hall,
Clifs: Prentice
band. The rate rate depends
depends on carrier densities densities to third order and is is strongest 1990).
1990).
F. Stern,
Stern, "Elementary
"Elementary theory
theory of of the
the optical
optical properties
properties of
of solids", Solid State
solids" , Solid State
when
when the charge carrier densities are high. Trap Trap assisted
assisted recombination
recombination is is
15, 300
Physics 15,
Physics (1963)
300 (1963)
a multiple
mUltiple step relaxation
relaxation process,
process, usually involving involving intermediate
intermediate states in M.S. Introduction to
Tyagi, Introduction to Semiconductor
Semiconductor Materials
Materials and
and Devices
Devices (Chichester:
(Chichester:
M.S. Tyagi,
the band gap. gap. The energyenergy lost lost by relaxation is given up as as heat.
heat. The rate Wiley, 1991).
1991).
depends
depends upon the density and position of these these intermediate
intermediate states states and on 011 P.
P. Wuerfel,
Wuerfel, "The chemical potential
"The chemical potential of radiation",1.J.Phys.
of radiation", Phys.CC -- Solid
Solid State
State
the relative
relative densities
densities of electrons
electrons and and holes.
holes. ItIt isis strongest
strongest for for deep
deep traps Physics 15, 3967-3985 (1982).
Physics (1982).
when
when nandnand pp are are similar.
similar. In In doped
doped material
material itit becomes
becomes linear
linear and can be
characterised by a single recombinationrecombination time. time. Trap assisted recombination
recombination
is
is particularly important at at aa surface
surface on on account
account of of surface
surface states. Surface
Surface
recombination
recombination becomes becomeslinear linearinin doped
doped material
material and and can be characterised
by a surface recombination velocity which which depends
depends on the density of surface
defects. In
defects. In real
real materials
materials trap assistedassisted recombination
recombination is is dominant.
dominant. In In the
limit
limit of perfect
perfect material, recombination is
material, radiative recombination is dominant
dominant and Auger Auger
becomes
becomes important
important for for low
low band
band gap gap and
and indirect
indirect gap materials.
Formulae
Formulae for for the generation and
the generation recombination rates
and recombination rates cancan be used to
be used
set
set up equations for each
up transport equations each of the charge charge carriers.
carriers. Together
Together withwith
Poisson's equation, these form form a set set of
of coupled
coupled differential
differential equations
equations which
which
can
can be
be solved
solvedfor for the
the charge
chargecarrier
carrier densities,
densities,currents
currents andand thethe electrostatic
electrostatic
potential.
potentiaL. In In general,
general,the the problem
problem isis complex
complex but but can
can be be greatly
greatly simplified
through assuming
assuming aa linear linear recombination rate and neglecting neglecting electric field,field,
conditions
conditions whichwhich are are valid
valid inin many
many device
device structures.
structures.
 Chapter 55
Chapter

Junctions

5.1. Introduction
5.1. Introduction

Photovoltaic energy
energy conversion results from charge generation, charge
charge sep-
sep-
aration and
aration charge transport.
and charge transport. In
In Chapters
Chapters 33 and
and 4,
4, the
the processes
processes of
of pho-
pho-
togeneration and charge transport
transport in
in aasemiconductor
semiconductor were
were discussed.
discussed. The
remaining stage, charge
remaining stage, charge separation,
separation, requires
requires some
some kind of
of driving
driving force.
force.
This driving force is absolutely key for
for photovoltaic energy conversion and
must be built in
must in to
to our
our device.
device. In the
the language
language of Chapter 3, the
the driving
driving
force can
force can bebe equated
equated to to aa light-induced
light-induced gradient
gradient in the
the quasi
quasi Fermi
Fermi levels
levels
for electrons
for electrons andand holes.
holes. InIn an
an alternative,
alternative, electrical
electrical picture,
picture, the light ab-
a b-
sorbing material
sorbing material isis connected
connected to to the
the external circuit by paths
paths of
of different
different
resistance: one
resistance: one which
which has
has much
much lower
lower resistance
resistance for
for negative
negative than
than positive
charge,and
charge, and the
the other
other which has has much
much lower
lower resistance
resistance forfor positive
positive than
negative (Fig.
negative (Fig. 5.1).
In principle, there are many ways of providing
providing aa charge
charge separating
separating mech-
anism. It
anism. It is normally provided
provided by spatial variations in the the electronic
electronic envi-
ronment. In In aa crystallne
crystalline semiconductor
semiconductor device,
device, aa junction
junction between
between twotwo

~ ~
Fig.
Fig.5.1.
5.1, Schematic
Schematic of charge
tact provides
tact provides aa low
low resistance
:I
resistancepath
:r-
o 0oo. 0-
charge separation
separationmechanism
pathfor
mechanism in
for electrons
electronsbut
-7(~
in aa photovoltaic
but blocks
photovoltaicdevice.
blocks hole
hole flow
flow,
device,One
Onecon-
while the
, while
con-
the other
other
providesan
provides aneasy
easypath
path for
for holes
holesbut
but aa barrier
barrier to electrons.
electrons. Such asymmetry can
Such asymmetry can be
be
achievedby
achieved byusing
usingdifferent
differentelectronic
electronicmaterials
materialsononeither
either side.
side.

119
119
120
120 The Physics
The Physics of
of Solar
Solar Cells
Cells Junctions
Junctions 121
121

materials provides
electronically different materials provides an electrostatic force,
force. In photo-
photo- illumination, nn ;:>no
Under ilumination, noandandpp;:>Po, Po .Then,
Then,ififthetheelectric
electricfield
field is
is non
non
synthesis -- where
synthesis wherecharge
charge separation
separation is
is also
also aa requisite
requisite-- excited
excitedelectrons
electrons zero,
zero, aa net
netdrift
drif current
current wil
willresult.
result.Alternatively,
Alternatively,ififthere
thereisisno no electric
electric field,
field,
are driven across photosynthetic membrane
across the photosynthetic membrane by differences
differences in the
the free
free but there
there are
are gradients in the carrier densities, densities,then then aa net
net diffusion
diffsion current
current
energy of molecular acceptors. In bothboth cases
cases the
the force
force arises
arises from
from aa compo-
compo- may result.
result.
gradient.
sitional gradient. An electric
electric field which
which exists
exists inin equilibrium
equilbrium is is called aa 'built-in'
'built-in'field
fieldandand
this chapter
In this chapter we
we wil
willdiscuss,
discuss, without
without mathematical
mathematical detail,
detail, various
various is due to to compositional
compositional factors.
factors. We We shall
shall see
see below
below howhow a built-in
built-in electro-
electro-
types of
types of junction
junction used
used in
in photovoltaic
photovoltaic devices. Chapter 66 completes
devices. Chapter completes the the field isis established
static field established at thethe interface
interface between
between two materials of different
description of photovoltaic
photovoltaic action
action with
with a detailed analysis of the most most im-im- work function.
function. As As shown
shown in in Chapter
Chapter 3, 3, an
an effective
effective electric
electric field
field may
may alsoalso
portant example,
portant rrn junction.
example, the p-n junction. result from
from gradients in the electron electron affnity,
affinity, band
band gap,
gap, and
and effective
effective band
density of states.
states. An An electric
electric field
field isis effective
effective forfor charge
charge separation
separation since it
always drives pp and
always drives and n carriers
carriers in opposite
opposite directions.
directions.
5.2. Origin
5.2, Origin of
of Photovoltaic
PhotovoltaIc Action
Action Carrer
Carrierdensitydensity gradients
gradients result
result from
from gradients
gradients in the the generation
generation or or re-
re-
In a photovoltaic device, light produces a separation of charges.
charges. That charge
That charge moval rate. In an
moval rate. an otherwise
otherwise isotropic environment aa gradient
isotropic environment gradient in the gen- gen-
separation then
separationthen gives
gives riserise tophoto
to a current (in short circuit) or aa photo-
a photocurrent photo- eration rate
eration rate of of electron-hole
electron-hole pairs
pairs can result in
can result in aa net
net current
current onlyonly if if the
the
voltage (in open
voltage open circuit). The
The photovoltaic
photovoltaic action
action arises
arises from
from the
the driving diffusion constants
diffusion constants for electrons and
for electrons holes are
and holes different. If
are different. If they
they are
are the

force
force separating
separating charges.
charges. Here
Here we wewill
wil ana lyse this
analyse this in contri-
in terms of the contri- same, then
same, then the the electron
electron andand hole
hole diffusion
diffsion currents
currents cancel
cancel outout exactly.
exactly.
butions to
butions to the
the photocurrent 1. (It
photocurrent, , J. (It can
can equally
equally well
well be
be analysed in terms
analysed in of
terms of
The potential difference created by
difference created byasymmetry
asymmetryinindiffusion
diffsion constants,
constants, the
contributions to
contributions to the
the photovoltage [Fonash, 19801,)
photovoltage Fonash, 19801.) Dember potential,
Dember potential, is not not usually
usually largelarge enough
enough for for effective
effective photovoltaic
photovoltaic
Now, from Chapter 33 (Eqs.
(Eqs. 3.65-3.67) we we have
havefor
for the
the current
current at
at aa point action in crystallne
action crystalline materials,
materials, although
although it it may
may be be large
large in inmolecular
molecular
materials.
J = In + Jp = inn'VEFn + ipp'VEFp' (5.1)
(5.1) Large diffusive
Large diffusive currents
currents can be be achieved, however, in
achieved, however, in an asymmetric
asymmetric
environment where
environment where there is some some additional
additional mechanism
mechanism which selectivelyselectively
By definition, for
By definition, for aa semiconductor
semiconductor inin equilibrium,
equilbrium, EFnEFn and EFp
EFp are equal
remove electrons
remove electrons or or holes.
holes. This
This could
could be be aa contact which has low low resistance
and constant and J1 == 00everywhere.
and everywhere. So,
So, to achieve
achieve photovoltaic action, we we
for electrons
for electrons and and high for holes,
holes. Such
Such a contact or or charged
charged region
region prefer-
prefer-
must have a situation where light
light produces
produces aa gradient
gradient in
in at least one of the entially removes electronsfrom
removes electrons from the the light absorbing
absorbing region
region andand creates
creates a
quasi levels.
quasi Fermi levels. gradient in the electron
gradient electron density,
density. It may may be be considered
considered as an electronelectron sink.
sink.
How
How could
could that
that happen? Using the
happen? Using diffusion forms
the drift diffusion forIIn
formsfor n and Jp
and Jp That density gradient drives drives an an electron
electrondiffusion
diffsion current.
current, In this situation
from
from Chapter 3 (Eqs. 3.75-3.76)
3.75-3.76) we
we have
have that
that there
there is is no
no hole
hole current
current toto cancel
cancel the electron currents
the electron currents sincesince holes
holes were
were

n = qDn'V(n
IIn no)++J1.n(n
qDn V'(n - -no) in(n- -no)(qF
no)(qF- -V'x
'Vx- -kTV' In N c) (5.2)
kT'VlnNc) (5.2) not collected.
collected. There may be a second second contact
contact which
which preferentially
preferentially removes
holes, and
holes, and thisthis creates
creates aa hole
hole diffusion
diffsion current which which addsadds to the electron
electron
and current.
In the following,
following, we we consider
consider the the contributions
contributions to the the charge
charge separating
p=
JJp -qDp V'(p -- Po)
= -qDp'V(p +ip(p
Po) + po)(qF -- 'Vx
J1.p(p - po)(qF Eg ++kT'V
V'x- -'VV'Eg kTV'In N v ) (5.3)
In Nv) (5.3)
field.
where no,
where Po represent
no, Po represent the
the carrier
carrier densities
densities inin equilibrium
equilbrium andarid we
we have
have
made use of
made use of the
the fact
fact that n =
that IIn J p == 00 in
= Jp in equilbrium.
equilibrium. In
In either
either equation,
equation, Box 5.1.
Box 5.1. Contributions
Contributions to the
the charge
charge separating
sepamting field
field
the first term represents diffusion
diffusion and
and the second
second represents
represents drift
drift under
under the
Figure 5.2
Figure 5.2 shows
shows aa band profile representation of the various
profile representation various possible
possible
net electric
electric field,
field, which
which isis due
due to compositional
compositional gradients,
gradients, as well
well as ~ny
!lny
contributions to the electric field
contributions experienced by
field experienced by electrons
electrons in
in the
the conduction
conduction
electrostatic
electrostatic field
field (as
(as shown Fig. 5.2).
showninin Fig. 5.2). When
When the
the equations
equations areare written
written band. (Note that
that each
band. each of
of these configurations results in
configurations results in an
an electron
electron current
current
in
in this form, both terms
terms are identically zerozero in
in equilibrium.
122
122 Physics of
The Physics of Solar
Sola.r Cells
Cells Junctions
Junctions 123
123

E vac

5 Energy
Energy vacuum
vacuum level
leve!

conducton
conduction band
band
Ene'9Y ;
Energy

Evac X
Eyac----J

E C quasi Fennllevels

--
----r
EEoc ---""-:!;~
E
ECe kTln(Nc In)
E
EFF -------
E
EFF ------"<-,_
Fermi Ie.... ,
EFn I kTln(Ny Ip)I.veI.
Ee = = : : = = : r k T l n ( N e / n I

: Fn I quasi Fennl
E Fp
(a)
kTln(N/PO ) Fp ~kTJn(NY/P I
(a) valence band
band

'. -~--l- E vac

E
Eyy E
Eyy

Ne1 ;: Ne2 - - - -- - - -- -7) D~~

Distance ---------7) Distance
DlsJance

E" E" (a) (b)

E Fig.
Fig. 5.3.
5.3. Built
Builtininelectric
electricfield
field and
and charge
charge separation
separation in
in aa general
general material,
material, (a)
(a) in
in equi-
equi-
E
E FF- - - - - - - - - E FF - - - - - - -
librium (b) under ilumination,
librium (b) illumination.
(b)
(b) (c)
(c)
Fig. 5,2,
Fig, 5.2. Contributions
Contribut ions to
to aa built-in
built-in effective
effective field
field for
for electrons.
elect rons. (See
(See text
text for
for
a uniform
a uniform excess
excess carrier
carrier density
density of of em
-n is
ispresent
presentsosothat
thatno no +
-. no
no -> + Ll.n
-n
explanation.
explanation,))
and Po
and Po -> Po +
-. Po + -n, Now, the
Ll.n. Now, the quasi
quasi Fermi
Fermi levels
levelsare
aresplit
split and
and have
have both
both
developed aa positive
developed positive gradient.
gradient. Electrons
Electronswill wil be
be driven
driven to the left and holes
holes
from
from right to left.
right to left. The
The sign
sign of of the net current
the net current also
also depends
depends upon upon the
the sense
sense to the right
right by
by the
thebuilt-in
built-infield,
field, thus
thus effecting
effecting charge
charge separation.
of
of the driving force for holes
the driving holes in valence band.)
in the valence In summary, the various
various conditions which
which can give rise to charge sepa-
give rise
In (a) aa difference
In (a) difference in the work
in the work function
function has
has given
given riserise to
to aa gradient
gradient in
in ration in
in our
our semiconductor
semiconductor are:are:
the vacuum
vacuum level
level and
andhence
hence an an electrostatic
electrostaticfield, ~ 'IlEvac.
field,~ V' Evac.
In (b) aa difference
In (b) difference in in the
the electron
electron affinity due to
affnity due to aa compositional
compositional gradient
gradient (i) gradient in
(i) gradient in the
the vacuum
vacuum level
levelororwork fuction ~
workfunction electrostatic field
~ electrostatic field
creates
creates anan effective field, -~'Ilx,
effective field, -i V'X, seen
seen asas aa gradient
gradient in in the
the conduction
conduction bandband (ii) gradient in
(ii) gradient in the
the electron
electron affinity ~effective
affnity ~ effective field
field
edge. (iii) gradient in
(iii) gradient in the
the band
band gap
gap ~~ effective
effective field
field
In (c) aa field
In (c) field due
due toto aa gradient
gradient in in the
the effective
effective conduction
conduction band band density
density (iv) gradient in
(iv) gradient the band
inthe band densities
densities of states ~
of states effective field
~ effective field
of
of states, k;
states, -- k; In InV'
'Il N c, isis driving
Ne, driving electrons
electronsto to the
the right. This term
right, This term cannot
cannot
The first three
three ofthese
ofthese are
are exploited in in photovoltaic
photovoltaicdevices.
devices. Changes
Changes inin (i),
be depicted on
be depicted this diagram
on this diagram as as it
it represents
represents aa gradient
gradient in in the
the free energy
free energy
rather than potential
potential energy:
energy: carriers
carriers are (ii)
(ii) and (iii) can
and (iii) be achieved
can be achieved at at the interface between
the interface between twotwo different
different materials
materials
rather than are driven
driven thermodynamically
thermodynamically in the
in the
direction -- aa 'heterojunction'
'heterojunction' -- or or through
through gradual
gradual changes
changes inin the
the composition
composition of of an
an
direction of of increasing
increasing availability
availabilty of of states.
states.
alloy.
alloy.However,
However, thethe fields
fields available
availablethrough
through variations
variations inin the
the electron
electron affinity
affnity
or band
or band gap
gap can
can be
befairly
fairly limited,
limited, at least
least in crystalline
crystalline semiconductors.
semiconductors. A A
Figure
Figure 5.3
5.3 shows
shows the
the various
various factors
factors which
which contribute
contribute toto the net elec-
the net elec- further problem
further problem withwith heterojunctions
heterojunctionsisisthat that defects
defects at at the interface
interface can
tric field within
tric field within some
some general,
general, compositionally
compositionally varying semiconductor
semiconductor in enhance recombination losses, losses.
equilibrium. Neglecting gradients
equilbrium. Neglecting gradients inin the
the band densities of
band densities of states, an elec-
states, an elec- Changes in
Changes in the vacuum level or work
level or work function
function (i),
(i), can also be achieved
achieved
tron
tron in theconduction
in the conduction band
band experiences
experiences an electric field
an electric of ~~ V'
field of Ee ==
'Il Ec without using different materials,
using different materials,simply
simplyby by varying
vaying the doping level in
doping level in aa
~('IlEvac
~ (\7 Evae \7 X)and
- -'Ilx) anda ahole
hole in the valence
in the valence band
band experiences
experiences the field
the field single semiconductor.
single semiconductor. The fields fields establisherl
established this way can he be large
large and
and avoid
i \7 Ev = i(\7 Evae - V'x - \7 Eg). .
~'IlEv = ~('IlEvac - 'IlX - 'IlEg ).
In Fig.
Fig. 5.3(a)
5.3(a) the
the carrier
carrierdensities
densities have
have their equilibrium
equilibrium profiles
,
'no,
profiles 'no,
the material problems due
the
means of
means of establishing
establishing the
due toto heterojunctions.
the charge
heterojunctions. This is the most widely used
charge separating
separating field
field in solar cells.
used

Po,, which
Po which are
are spatially
spatially varying,
varying, and
and the
the Fermi
Fermi level
level isis flat.
flat. In Fig. 5.3(b)
In Fig. 5.3(b) The most common types of junction are described
The described below.
below.
124 The Physics
The Physics of
ofSolar
Solar Cells
Cells Junctions
Junctions 125
125
124

5.3. Work
5.3, WorkFunction
Functionand
andTypes
Typesofof Junction
Junction 5.4. Metal-Semiconductor
5.4. Metal-Semiconductor Junction
Junction

The work
The work function
fWlCtion of
of aa material
material is is the
the potential
potential required
required to
to remove
remove the
the 0) Perhaps the simplest
Perhaps the type of
simplest type of charge
charge separating junction is
separating junction is the
the
least tightly
least tightly bound
bound electron.
electron. ItItisisisisdefined
defined by
by semiconductor-metal junction. We
semiconductor-metal junction. We will
wil use
use this asas a model
model to explain
explain in in
qualitative
qualitative terms
termshow
how the
theelectrostatic
electrostaticfield
field is
is established
established and
and how
how itit causes
causes
-Pw = (Evae
Pw (Evac -- EF)
EF) (5.4)
(5.4) photovoltaic
photovoltaic action.
action.

In metals
In -Pw isis always
metals Pw always equal
equal to
to the
the electron
electron affiuty,
affinity. In
In semiconductors
semiconductors itit
can be
be controlled
controlled by by doping.
doping. Since
Since the
the position
position of
of the
the Fermi
Fermi level
level within
within 5.4.1. Establishing
5.4,1. Establishingaafield
field
can
the band
the band gapgap ofof aa semiconductor
semiconductor depends
depends upon
upon doping,
doping, aa particular
particular semi-
semi- Suppose we have aa uniform
we have uniform nn type semiconductor of work function -Pn
work function Pn and
and
conductor will
conductor have aa smaller
wil have smaller work
work function
function when
when it is doped
it is doped n n type
type than
than -Pm, such
a metal of work function Pm, > Pn.
<Pm ?
that Pm
such that -Pn. When
When the
the two
two materials
materials
when it
when it is
is doped
doped pp type,
type. are isolated
isolated from each other,
from each other, the Fermi
Fermi levels wil be
levels will be independent,
independent, as in
in
Since EF
Since EF isis constant
constant in in equilbrium,
equilibrium, an an electrostatic
electrostatic field
field must
must be be es-
es- 5.4(a) . When they
Fig. 5.4(a). they are
are brought
brought into
into electronic
electronic contact
contact the
the Fermi
Fermi levels
levels
tablished at
tablished at the
the junction
junctionbetween
between any
any two
two regions
regions of different Pw,
of different -P w , due
due to
to must
must line
line up, as as in
in Fig.
Fig. 5.4(b),
5.4(b), with
with the
theconsequence
consequence that the the vacuum
vacuum
the gradient
the gradient in E v",,' This
in Evo.' Thiscould
could be heterojunctionbetween
beatataaheterojunction betweenaasemicon-
semicon- level changes by
level changes by (.pm
(Pm -- ifn)cl>n) between
between thethe semiconductor
semiconductor and and the metal.
metal.
ductor and
ductor and aa metal
metal or or two
two semiconductors
semiconductors of different -P
of different w , or
Pw, or it could be
it could be at
at Physically
Physically thisthis is achieved
achieved by by the exchange
exchange of charge carriers across the tbe
homojunction between
aa homojundion between two two layers
layers of
of the same semiconductor
the same semiconductor which which havehave junction.Electrons
junction. Electrons flow
flow from
from the the semiconductor
semiconductor to the to the metal leaving
metal leaving aa layer
layer
been doped
been doped differently.
differently. of positive
positive fixed
fied charge
charge behind,
behind, andand aa negative
negative image
image charge on the metal,
For any
For any ofof these junctions, the
these junctions, the electric
electric field is evaluated
field is evaluated in in the
the following
following until the charge
charge gradient which builds up
which builds up isis suffcient
sufficient to prevent
prevent further
further
way:
way: flow. At this
flow. this point
point the
the two
two layers are in
layers are in thermal
thermal equilibrium.
equilbrium, The The energy
energy at
The electrostatic potential
The electrostatic potential energy
energy difference
difference across
across thethe junction
junction is is equal
equal the conduction
conduction bandband edgeedge in in the
the bulk of of the
the semiconductor
semiconductor is lowerlower than
to the difference
to the difference in in the
the work
work functions.
functions. Therefore
Therefore the field F
the field established
F established at the
the interface
interface with the the metal,
metal, and
and anan electrostatic
electrostatic field
field exists close
close to the
across
across aa junction
junction in the xx direction
in the direction must
must obey
obey junction,
junction. The variation
variation in in electrostatic
electrostatic potential energyenergy is represented
represented by
x+ the change
change in EvacEVaG in in Fig.
Fig. 5.4
5.4 and
and the field
field by
by the gradient
gradient of of Evo.'
Evac. The
The
(5.5)
(5.5) potential difference
difference isis shared
shared between
between thethe two
two materials
materials according
according to to their
q x_ Fdx = Pw(x+) - ifw(x-) = liPw
where x_
where x_ and x+ represent
and x+ represent positions
positions fa
farr from the junction
from the on either
junction on either side
side
where
where the electric field
the electric field is
is zero.
zero. Poisson's
Poisson's equation
equation requires
requires that
that E vac --~---
Evac
d ntype
n typesemiconductor
semiconductor metal
metal cp i
-(csF) = qp(x)
dx
dx (csF) = qp(x)
(5.6)
(5.6) Evac-- -r Ec
n

EF

"~,, "
where
where c,Csisisthe
the local
localdielectric
dielectricpermittivity
permittivity and
and the
the local charge density
density p
includes
includescontributions
contributionsfrom fromall
all charges
chargesininthethejunctions
junctionsregion
region- - trapped
trapped E,
E, _ _ _ _ _ ~~

charges
charges asas well
wellas asfixed space charge
fied space charge and
and free
free electrons
electrons and holes. The
and holes. The free
free
carrier
carrier distributions
distributions themselves
themselves depend
depend on on the local value
the local value ofof EF relative
EF relative E, v - - - - - - x=o
E
to the band
to the band edges,
edges, soso the
the problem has to
problem has be solved
to be solved self
self consistently.
consistently. Thus,
Thus,
accommodating (a)
(a) (b)
(b)
accommodating aa difference
difference in in work
work functions
functions effectively
effectivelymeans
means aa redistri-
redistri-
bution
bution of charge around
of charge around thethe junction.
junction, This
This will
wil be
be seen
seen for
for the
the examples
examples Fig.
Fig. 5.4. (a) Band
5.4, (a) profiles of
Band profiles ofn-type
n-type semiconductor
semiconductor and metal in
and metal in isolation,
isolation. (b)
(b)Band
Band
below.
below. profileofofthe
profile thesemiconductor-metal
semiconductor-metaljunction
junctionininequilibrium.
equilbrium.
 126 ThePhysics
The PhysicsoJ
ofSolar
Solar Cells
Cells Junctions
Junctions 127
127
126

dielectricpermittivities.
dielectric

either
toto zero.
permittivities, Because
than semiconductors (much lower
than
isis dropped
dropped in
either side,
zero.This

typically
materials
in the
side, the
This distance
typicallyaround
materials carry
space charge
distance is
aroundaamicron
carry a
chargelayer
a net
Becausemetals

the semiconductor.
semiconductor.At
the potential
potential difference
isvanishingly
metalsare
lower cs),
At some
difference stops
vanishingly short
micron- - in
net charge.
layerof
in the
charge. This
ofthe
aremuch
is.),virtually

short in
muchpoorer
virtually all

inthe

the semiconductor,
all of
somedistance
poorerat
ofthe
distancefrom
stopsvarying
varyingand
themetal
metal but

semiconductor. Within
region is
This region
the junction.
junction. It
is called
at storing
thepotential
fromthe
and the
but is
Within these
the space
called the
It corresponds to the
storing charge

thejunction
the electric
charge
potential difference
difference
junction on
electric field
issignificant
significant
these regions
space charge
regions the
charge region
on
field falls
falls
- -
the
region oror
vV -l
T
E~
c m
E vac

Ev .-
F

space the region

region where
where Evac
EvlJ,C i
++
isis changing.
changing.Because
Becausethetheelectron
electronaffinity
affnityandand band
band gapgap are
are invariant
invariant in
in the
the
semiconductor, the
semiconductor, the conduction
conduction and and valence
valence band
band energies
energies must
must change
change in in
parallel with
with Eva<:'
Eva.. This
This is x=o
x=o
parallel is usually referred to
usually referred to as
as band
band bending.
bending. TheThe total
total
amount by which the
amount the bands
bands bend
bend in in the
the semiconductor
semiconductor is is given
given by
by qVbi
qVbi Fig.
Fig. 5.5.
5,5. Band profile of the
Band profie thesemiconductor-metal
semiconductor-metal junction
junction under
under illumination
ilumination at
at open
open
where V
Vbiisiscalled
calledthe
the built-in
built-in bias. circuit. The accumulation of photogenerated
circuit. photogenerated electrons
electrons in
in the
the n-type
n-type semiconductor raises
where bi bias. the electron Fermi level and generates
level and generates a photovoltage, V.
photovoltage, V.
The charge
The distribution across
charge distribution the junction
across the junction can
can be
be inferred
inferred from
from the
the
band bending.
band bending.Far Far from
fromthethejunction,
junction,nandnand pp wil h~ve
will have
2
their
their equilb-
equilib-
rium values
rium valuesfor forthat
that doping
dopinglevel,
level,n n"'""'Nd
Nd, andpp """' E
, and N;;(Eqs.
(Eqs.3.42
3.42and
and region through
region through the diffusive current resulting from preferentialpreferential hole extrac-
3.43) aand
3.43) nd the
the material
material isis electrically
electrically neutral.
neutral. Now
Now since
since from
from Eq.Eq. 3.31
3.31 tion atat the
theinterface,
interface. The
Thesemiconductor
semiconductor wil willbecome
become negatively
negatively charged
charged
n == Nce-(Ec-EFl/kBT,
Nce-(Ec-EF)/kBT , we we can
can see
seethat
that as
as x approaches
approaches the junction and Ec and the
the potential
potential difference across the
difference across the junction
junction will wil be
be reduced.
reduced. The
The elec-
elec-
increases,
increases, nn willwil decrease belowits
decrease below itsequilibrium
equilbrium valuevaluesosothatthat nn <
.: Nd
Nd and
and tron quasi
quasi Fermi level far
Fermi level far from
fromthethejunction
junctionwill wil be
be higher than it was
higher than was in
the material
material becomes
becomes positively charged,
charged. At the the same
same time, the the mobile
mobile hole
hole the dark, andand higher
higher than
than the
the Fermi
Fermi level
level in
in the
the metal,
metal, as
as shown
shown in Fig.
Fig. 5.5.
5.5.
concentration
concentration increases, sinceEv
increases, since Evisis increasing
increasingand andpp = = Nve-(EF-Ev)/kT.
Nve-(EF-Ev l/ kT. The light has has caused
caused thethe Fermi
Fermi level
level to split. It It has
hascreated
createdaaphotovoltage,
photovoltage,
However, p is is still
still very
very small
small and
and the
the positive
positive charge
charge acquired is due mainly V, equal
equal to to the
the difference
difference inin the
the Fermi
Fermi levels
liwels ofof semiconductor
semiconductor and metal
metal
to
to the
the fied
fixedionised
ioniseddonor
donoratoms
atomswhich
whichhave
have lost
lost their
their electrons.
electrons. The
The space
space far from
far from thethe junction.
junction. This
This abilty
ability to
to sustain
sustain aa difference
difference in
in quasi
quasi Fermi
Fermi

charge region is
charge region is depleted
depleted of carriers and is is often
often called
called aa depletion
depletion region
region levels under
levels under illumination
ilumination is is the
the key requirement for
key requirement for photovoltaic
photovoltaic energy
energy
or
or exhaustion
exhaustion layer.
layer. conversion.
conversion.
Thus, by
Thus, by joining an nn type
joining an type semiconductor
semiconductor to
to aa metal
metal of
of larger
larger work
work
function,
function, we
we set
set upup an
an electric
electric field
field in
in aa layer
layer close to the
close to the interface.
interface. It
It isis 5.4.3. Behaviour
5.4.3. Behaviourin
in the
the dark
dark
evident
evident that
that this
this field
field wil
willdrive
drive electrons
electrons toto the
the left
left and
and holes
holes to the
the right,
right,
so
so effecting charge separation.
charge sepa ration. The
The contact
contact presents
presents aa lower
lower resistance
resistance path
path The
The presence
presence of
of the barrier
barrier also
also governs
governs the current-voltage
current-voltage characteristic
characteristic
for
for holes
holes than
than electrons,
electrons, from
from semiconductor
semiconductor toto metal.
metal. This
This type
type of
ofjunction
junction in the
in the dark.
dark, Conduction in nn type
Conduction in type semiconductors
semiconductorsisis normally
normally by
byelectron
electron
is
is an
an example
example ofof aa Schottky
Schottky barner.
barnel'. flow,
flow, and the
the interface
interface presents
presents aa barrier
barrier to
to electron
electron flow.
flow. At equilbrium,
equilibrium,
aa small
small current
current due
due to
tothe
thethermal
thermalactivation
activationof ofelectrons
electrons over
over the
the bar-
bar-
rier
rier isis balanced
balanced by aa small 'leakge'
'leakage' current
current due
due to
to the
the drift
driftofofholes
holesfrom
from
5,4,2,
5.4.2. Behaviour
Behaviour in
inthe
the light
light semiconductor
semiconductor to
to metal.
metal. When
When aaforward
forward bias
biasisisapplied
applied(the
(thesemiconduc-
semiconduc-
Now
Now suppose that that the
the semiconductor
semiconductor is is iluminated
illuminatedwith
withphotons
photonsofofenergy
energy tor
tor isisheld
held atata amore
morenegative
negative bias
bias than
than the
themetal)
metal) the
thebarrier
barrierheight
height isis
greater
greaterthan
thanEg.
E g The
. Thespace
spacecharge
chargelayer
layerwil
willcause
causeelectron-hole
electron-holepairs
pairsgener-
gener- reduced
reduced and
and electrons
electrons pass
pass more
more easily over the barrier
barrierfrom
fromsemiconduc-
semieonduc-
ated
atedininthethesemiconductor
semiconductorto tobe
beseparated
separatedso sothat
thatthe
theelectrons
electronsaccumulate
accumulate tor
tortotometal.
metal.This
Thisforward
forwardcurrent
currentincreases
increasesapproximately
approximatelyexponentially
exponentiallyas as
inin the
thesemiconductor
semiconductor and and the
theholes
holes in
inthethemetal
metal(i.e.,
(i.e.,electrons
electronsremoved
removed the
thebarrier
barrierheight
heightisisreduced,
reduced.In
Inreverse
reversebias,
bias,the
thebarrier
barrierheight
heightisisincreased,
increased,
from
from the
themetal).
metal) .This
Thisapplies
appliestotopairs
pairsgenerated
generatedfar farfrom
fromthe thefield
fieldbearing
bearing suppressingthe
suppressing theactivated
activated current,
current, and
andthe
the only
onlycontribution
contributionisis the
the small
small
 The
The Physics
Physics of
of Solar CeUs
Solar Cells Junctions
Ju.nctions 129
129

E,a~n
128
128

P:i
Evac Evac
Evac

~
4>
4>
cD
p
E, E,

E, ""I
E
F Ey
1 . -1-v
- EF T

~
(a)
+
c.
e!e~\' I
A. B.
B, C. (a)
(a) (b)
(b)
---'J> J~ 0 l
J"-O
J<O
)J >
"u0 Fig.
Fig. 5.7. Bandprofile
5,7, Band profile of
of tthe
he p-type
p-type semiconductor-metal junction (a)
semiconductor-metal junction (a) at
at equilibrium
equilibri
eft'CffOlljlow and (b) under
and (b) illumination at
under ilumination at open
open circuit.
circuit. urn
~

" ___
:~Ev J~'
+1--+
Ev
-- ::==1
"-="-Ev
'~'J-
-- + ~,
--7 _
hole.fow liolefloi.
hu/f! flow Iwle fiow holeflow
semic~nductor ~a~ds
semiconductor
a barrier
semiconductor
bands bend down
barner to majority
majorItycarriers
negatively charged
semiconductor is negatively
The forward
acceptor impurities. The
towards the
down towards
carrierswhich
which are
are now
charged due
forward current
the interface (Fig.
now holes.

current is
(Fig, 5.7), presenting
holes. The depleted layer of the
space charge
due to the space
is provided
charge ofof the ionised
provided by hole activation over over
(b)
the barrier, and the
the reverse
reverse current by electron leakage.
leakage. Under
Under illumination
ilumination,
Fig. 5.6.
Fig. (a)Schematic
5.6. (a) Schematiccurrent-voltage
current-voltagecharacteristic
characteristic of
of aa Schottky
Schottky barrier
barrier junction
junction in
in electrons are driven
electrons are driven into
into the metal and holes
holes into the semiconductor,
semiconductor and
the dark.
the dark. A,
A, B
equilibrium and
B and
and CCmark
andforward
markpoints
forwardbias
pointson
bi",,; (b)
(b) A:
onthe
thecurve
A: band
curvewhere
band profile
where the
profile of
thedevice
device is
is at
atreverse
reverse bias,
bias,
the semiconductor develops
develops aa photovoltage whichwhich isis positive relative t~
positive relative to the
equilbrium of an
an n-type
n-type semicond uctor-metal
semiconductor-metal
Schottky barrier
Schottky barrier at
at reverse
reverse bias.
bias. The
The only
only current
current is
is due
due to minority carrier
to minority carrier (hole)
(hole) drift
drift metal. In the dark,
dark, the
the junction
junction exhibits
exhibits the
the same
same type
type of
of asymmetric
asymmetric cur-cur-
acrOSS the
across the depleted
depleted barrier region. B:
barrier region. B: band
band profile
profileatat equilibrium. The currents
equilbrium. The due to
currents due to rent voltage behaviour as
voltage behaviour as the
the nn type Schottky
Schottky barrier, but with with opposite
opposite
electron diffusion
electron diffusion and
and ho le drift
hole cancel out.
drift cancel out. C:
C: band
band profile at forward
profie at forward bias.
bias. The
The current
current polarity.
due to
due electron diffusion
to electron diffusion is
is greatly
great ly increased
increased as
as the
the barrier height is
barrier height is reduced,
reduced, and
and the
the net
net
current changes sign.
current sign.

5.4.4. Ohmic
5.4,4, Ohmic contacts
contacts
leakage current
leakage current in the reverse
in the reverse direction,
direction, which
which is limited by
is limited by the
the low
low den-
den- The situation is is different if we
different if we have
have an
an nn type-metal junction such
type-metal junction such that
sity of
sity of mobile
mobile holes.
holes. So, the junction
So, the junction passes
passes current
current preferentially
preferent ially in
in the
the
<Pm <
'Pm ~ Wn, or aa pp type
<P n, or type metal
metal junction
junction with
withWmiI>m ?> 'Pp.
iI>p . Now,
Now, when
when the
the mate-
mate-
forward direction,
forward direction, and
and exhibits
exhibits 'rectifying'
' rectifying' characteristics
characteristics(Fig.
(Fig.5.5).
5.5).(This
(This
rials are brought into contact,
contact, the
the semiconductor
semiconductor bands
hands bend
bend in
in such
such aa way
way
was the
was the special
special property
property of of the
the early
early metal-semiconductor
metal-semiconductor junctions
junctions men-
men-
that
that they
.they encourage
.encourage the the ttransport
ransport ofof majority
majoritycarriers
carriersacross
across the junction,
junction,
tioned in
tioned in Chapter
Chapter 1,1, to
to which
which photovoltaic
photovoltaic behaviour
behaviour was was attributed.) This
attributed.) This andinhibit
and mhlbltonly
onlythethe How of minority carriers (Fig. 5.8). Majority
flow Majority carriers
carriers
asymmetric current-voltage
asymmetric behaviour in
current-voltage behaviour in the
the dark
dark isis aaconsequence
consequence of of the
the
must accumulate
accumulate nearnear the
the interface
interface to
to establish
establish thethe necessary
necessary potential
potential dif-
dif-
charge separating
separating junction
junction and
andisis aa feature
feature of
of most
most photovoltaic
photovoltaic devices,
devices.
charge ference,
ference, and the junction regionregion is rich
rich with
with carriers.
carriers. This means it can pass
The greater
The greater the
the difference
difference in work functions,
in work functions, the
the stronger
stronger the
the band
band bending
bending
current
current easily
easily in either
either direction,
direction,andandsosowewe have a low resistance contact
contact for
for
and the
and the greater
greater the
theasymmetry
asymmetrybetween
between the
theforward
forward and
and reverse
reversecurrents.
currents.
majority
majority carriers,
carriers, usually
usually called an Ohmic
called an contact. Under
Ohmic contact. Under illumination
ilumination, the
charges
charges separated at the the junction
junction pass
pass back
back across
across the
the junction
junction relatively
relatively
nandpptype
nand typemetal-semiconductor
metal-semiconductor junction
junction easily, so that
easily, so that the
~he resultant
resultant photovoltage
photovoltage at at the
theterminals
terminalsisisnegligible.
negligible. The
The
A completely
completely analogous
analogous situation
situation applies
applies to
to aa pp type
type semiconductor
semiconductor in in con-
con- mechanism
mechamsm whIchwhichgives
givesrise
risetotothe
thephotovoltage
photovoltageinina abarrier
barrierjunction
junction- - the
the
A
tact with
withaametal
metalofoflower
lowerwork
work function, iI>m ~<'Pp.
i.e., 'Pm
function, i.e., Inthis
iI>p. In thiscase
casethe
the selective removal
selective removal of of minority carriers -- isis absent.
minority carriers absent .
tact
130 The Physics
The Physics of Solar
Solar Cells Junctions 131

vac-----...-----....'-----
Evac
E E,ac
Evac '( ~ --
~'-----?I;;- 5.5. Semiconductor-Semiconductor Junctions
5.5, Semiconductor-Semiconductor Junctions

T~
5.5.1.
5.5.1. p-n junction
p-n junction
<Il
cI
p
P
Eo p-n junction
The p-n junctionisis the
theclassical
classical model
model ofof a solar cell.
cell. This
This type of junction
junction is
Eo <Il
cIm

1
EF Ec
EF .~ created
created by regions of the
by doping different regions the same
same semiconductor
semiconductor differently,
E,
Ey------------~
E so
so we have
have anan interface
interface between
between pp typetype and
and n type layers
n type layers ofof the
the same
same
E, F
F
Ev material.
materiaL. Since
Since thethe work function of
work function of the
the p type material
p type material is is larger
larger than
than
the n type,
type, the
the electrostatic
electrostatic potential must must bebe smaller
smaller on on the
the n side
side than
the p, and
the and anan electric
electric field
field isis established
established atat the junction
junction (see
(see Fig,
Fig. 5,9)
5.9)
(al
(a) (bl
(b) which drives photogenerated electrons towards the n side side and holes towards
Fig.
Fig, 5.8.
5.8. Ohmic metal- semiconductorcontacts
Ohmic metal-semiconductor cont8l:ts for
for (a)
(a) an
an n-type
n-type semiconductor
semiconductor and
and the
the p.
p, The junction region
The junction region is is depleted
depleted of of both
both electrons
electrons and and holes
holes, and
and
(b) a p-type semiconductor. In each case the difference in work functions is supplied
(b) a p-type semiconductor. In each case the difference in work functions is supplied always presents
always presents aa barrier
barrier to to majority
majority carriers, and a low
carriers, and low resistance
reSistance' path
by the build
by the build up
up ofof majority
majority carriers
carriers in
in an
an accumulation
accumulation layerlayer near
near the
the interface.
interface. An
An
accumulation
to minority carriers. It It drives
drives the the collection
collection of minority carriers which are
accumulation layer
layer is generally narrow
is generally narrow compared
compared to to aa depletion
depletion layer
layer because
because of the
higher density ofof charges
charges and
and stronger electric field,
field. photogenerated throughout the
photogenerated throughout the pp and
and n layers,
layers, and reach
reach the junction by
diffsion.
diffusion.
We draw the
We can draw the following
following conclusions from
from the above
above discussion:
discussion:

. aacharge
charge separating field isis established
separating field
terials of different work function
established at thethe interface
interface between
between two ma-
E,ac~ E,ac-;
p type semiconductor
p type semiconductor n type semiconductor

. the
thejunction

. the
junctionwil
willdevelop
rier to majority
develop aaphotovoltage
ma jority carrier
thephotovoltage
carrier currents
photovoltage provided
currents
photovoltage isis related
related to to the
provided that it presents

the difference
difference in work
presents a bar-

work functions
functions
bar-
Ec EC~EF
EF
Ev E
Ev - - - - - - - -
5.4.5. Limitations
5.4,5, Limitations of
of the
the Schottky
Schottky barrier junction
barrer junction
(al
(a)
The metal-semiconductor
metal- semiconductor barrier
barrier is
is aa simple
simple way to prepare a photovoltaic
photovoltaic

:~ tJ~~:
However, it
junction. However, it does
does not produce the highest photovoltages; (i) When
the barrier
barrier height
height is
is larger
larger than ~ ~ Eg/2,
E g /2, the
theminority
minority carriers
carriers outnumber
outnumber Evac
majority carriers
the majority carriers in the
the region
region close
close to the interface
interface and an
an inversion
inversion
layer is formed. In these conditions
is formed, conditions the the the junction
junction becomes
becomes carrier
carrier rich
rich
cannot sustain
and cannot sustain aa photovoltage.
photovoltage. This limits the useful barrier height, and

~
photovoltage; (ii) In
hence limits the photovoltage;(ii) Inthethecase
caseof
ofhighly
highly doped
doped semiconduc-
semiconduc-
very thin barrier
tors, very barrier layers
layers may
may result which allow allow tunnelling
tunnellng of majority E,
carriers through the
the junction,
junction,reducing
reducing the
the effectiveness
effectiveness of of the
the barrier;
barrier; (iii)
material interface
The material interface between
between the semiconductor
semiconductor and and tthe
he metal leads to
interface states which
which may
may trap charge
charge and limit
limit the
the photovoltage,
photovoltage, as as dis-
dis-
(b)
(b)
cussed below.
cussed below.
The problems
The problems of of the
the Schottky
Schottky barrier
barrier can can bebe avoided
avoided withwith Fig. 5:9.
Fig, (al Band
5,9. (a) profiles of
Band profies of p-type
p-type and
and n-type
n-type semiconductor
semiconductorininisolation.
isolation. (b)
(b) Band
Band

semiconductor-semiconductor junctions. profile ofthe

profile of thep--n
p- junction
junction in
in equilbrium.
equilibrium.
 The Phy.ica
The Physics of
of Solar
Solar Cells Junctions 133
133
132
132

The p-n junction has the advantages

advantages over the Schottky
over the Schottky barrier
barrier that
that (i)
(i) minority carrier
minority carrier diffusion
diffusionlengths
lengthsare
areshort,
short, and
and carriers
carriers photogenerated in
there is no
there is need for
no need for aa metallurgical
metallurgical interface
interface with
with its
its associated
associated defects,
defects. p or nn layers
layers areareunlikely
unlikely to
to contribute
contribute toto the photocurrent. Carriers which
The junction can
The can be
be created
created by continuously varying the
continuously varying the doping
doping of a sin- are photogenerated
are photogenerated in in the i region
region are driven towards the contactscontacts by by the
the
gle crystal
gle crystal wafer
waferduring
duringororafter
afer growth; (ii) A
growth; (ii) A large
large built
built in
in bias can be
bias can electric field
electric field and
and survive
survive for aa greater
greater distance
distance than
than inin doped
doped materiaL.
material.
establishedwithout
established without populating the junction
junction region
region (no
(no inversion
inversion layer),
layer). Lifetimes of carriers in the i region
region are usually extended
extended relative to those in
The
T he p-n junction
junction isis the
the most
most widely
widely used
used structure
structure for
for solar
solar cells
cells and the doped regions.
regions. Some
Somedisadvantages
disadvantagesofofthe thep-i-n
p-i-n design
designare arethat
that (i)
(i) the
the ii
wil be
will be analysed
analysed in detail in Chapter 6. 6.
region has
region has poorer
poorer conductivity
conductivity than doped layers, and may introduce series
resistance; (ii)
resistance; (ii) the likelihood
likelihood ofof recombination
recombination within
within the
the ii layer
layer at forward
bias conditions,
bias conditions, where
where electron
electron and hole populations becomes similar; and
becomes similar;
5.5.2.
5.5,2. p-i-n junction
p-i--"11- junction (iii)
(iii) charged
charged impurities
impurities may
may cause
cause the
the electric
electric field
field toto fall
fall to zero within
to zero within
the intrinsic region. p-i-np--n junctions
junctions inin amorphous
amorphous silcon
silicon wil
willbe
bediscussed
discussed
variation on
A variation on the
the p-n theme is is the p--n
p-i-njunction,
junction. This
This is
is aa p-n
p-njunction
junction
in Chapter 8. 8.
where aa layer of semiconductor between
between pp andand nn has been left
has been left undoped,
undoped, or
intrinsic (i). The same built-in bias is
intrinsic is established
established as as with
with the
the p-n
p-n junction
with the same
with same doping
doping levels,
levels, but the
the electric
electric field
field extends
extends over
over aa wider
wider 5.5.3.
5.5,3, p-n heterojunction
p--"11- heterojunction
region,, as shown in Fig.
region Fig, 5.10.
5.10. This
This design
design isis preferred
preferred inin materials
materials where the
p-n and
p-n and p--n
p-i-njunctions
junctionscan
canalso
also be
be prepared
prepared as
as heterojunctions
heterojunctions using two
two
different materials of different band band gap,
gap . This might
might bebe aa design
design feature to
improve carrier collection
improve carrier collection (discussed
(discussedinin Chapt
Chapter 7) or aa necessity
er 7) necessity because
because
Evac~ Evac~ Evac--
pptype
type intrinsic "type
"type

Evac
Ec
Ec EC~EF Ec
of the doping

change in
fields
doping properties
be a discontinuity
change in the
properties of available

the band gap,

for electrons
fields for electrons and
availablematerials.
discontinuity in the conuction
gap . This potential
and holes
materials,At
concuction and valence
potential step
which usually
holes which
Atthe
the junction

step introduces
junction there
band edges
valence band
introduces different
usually assist
there will
wil
due to the
edges due the
different effective
assist the electrostatic
effective
electrostatic field
field for
EF one
one carrier
carrier andand oppose
oppose itit for
for the other. In the the example
example in in Fig.
Fig. 5.11,
5.11, the
the
EF
EF heterojunction enhances
enhances thethe field
field driving electrons towards the
electrons towards the n side but
Ev Ev
Ev - - - - - - Ev
Ev ------
Ev ------ opposes the field for holes
field for holes by
by introducing
introducing aa barrier
barrier in the valence band. Such
(al
(a) barriers are common
barriers are common- - though
though not not unavoidable
unavoidable- - in in p-n
p- heterojunctions,
heterojunctions,
and can
can lead
lead toto enhanced
enhanced recombination
recombination in the junction region. region. The exact
exact
p "n band line-up
line- up wil
will depend
depend upon
upon thethe difference
difference inin the electron affinities
affnities and
Evae the
the work
work functions.
functions.

E'~ n~~qv, 5.6. Electrochemical

5.6. Electrochemical Junction
Junction

E.~ ~E, A surface barrier junction similar to the Schottky barrier can
at
at the

and
theinterface
trolyte
and from
interface between
trolyte which
from the
between aa semiconductor
which contains
semiconductor and
contains aa redox
the semiconductor
redox couple
semiconductor surface,
and aa liquid
is capable
couple is
surface. The
can be
be established
established
liquid electrolyte.
electrolyte. An
capable of transporting charge
The redox
redox couple
couple contains
An elec-
elec-
charge to
contains two
two ionic
to
ionic
(b)
(b) species different state
species of different state of charge, or oxidation
charge, or oxidation state. These
These may
may bebe ions
ions
of
of the
the same
same material
material in
in different
different states
states of
of charge,
charge, for
for instance Fe 2 + and
instance Fe2+ and
Fig. 5.10.
Fig. (a) Band
5,10. (a) Bandprofies
profilesofof p,
p, ii and
and n-type
n-type semiconductors
semiconductorsininisolation,
isolation . (b)
(b) Band
Band
profile of the
profile of the p-i-n
p--n junction
junction in
in equilbrium.
equilibrium. F+.
Fe3+.The
Theone
onewith
witha amore
morepositive
positivecharge
chargeisisthe
theoxidised
oxidisedspecies,
species, while
while
 r'

134 The Physics

The Physics of
of Solar
Solar Cells
Gells Junctions
Junctions 135
135
4

Evac~ Evac--
p-type semiconductor
p-type semiconductor n-type semiconductor
n-type semiconductor where E~.dox
where E~.doxisisthe
thestandard
standardredox
redoxpotential
potential of
work function of the standard. The final term
depends upon
depends upon the relative
relative concentrations
of the
the electrolyte
term shows
concentrations of
electrolyte and
shows how
of reduced
how the
and 'Prof
the work
reduced species,
<Prof is the
work function
function
species, Redj,
[Red), andand

Eo
~
Eo ~EF oxidised
oxidised species,
species, [OxJ.
concentrations.
concentrations. )
Oxl.(The
(The standard redox potential
standard redox potential is is defined
defined for
for equal
equal

The type of
The type of junction
junction which
which isis formed
formed at at aa perfect
perfect interface
interface depends
depends
EF upon the difference
upon difference in in the work functions
functions of of the
the semiconductor
semiconductor and and the
Ev Ev
E ------
E v ------ v electrolyte. Just
electrolyte. Just as with the semiconductor-metal
semiconductor-metal junction, a surface bar-
(a) rier will
rier wil be
be formed
formed at the the interface
interface between
between an n type type semiconductor
semiconductor with
work function
work function <Pn
'Poandandan an electrolyte
electrolytewith
with<p.q,. >;: 'Po. This is
<Pn . This is ilustrated
illustrated inin

Evac ----r-~Vbi
Fig. 5.12(b).
Fig. 5.12(b). Upon
Upon contact,
contact, electrons
electrons flow
flow from
from semiconductor
semiconductor into into elec-
elec-

~1
~ trolyte until
until the
the Fermi
Fermi levels
levels equalise,
equalise, establishing a positive space charge
layer in the semiconductor and an electric field field at the interface which drives

::
Eo
't ~I E
~i~=tq~;
Ev ~ EF Evac-;
-r
type semiconductor
n type redox electrolyte

Ev ~
F

-r.-
ig. 5.11.
Fig, (al Band
5.11, (a) Bandprofiles
profiles of
of pp and
(bl
(b)

n-type semiconductors
and n-type semiconductors of
of different
different band gap in
band gap in
EC~EF
E v v------
E :: ~
--.~--. <E'ax>

<~e<?

!L
isolation; (b) Band
.elation; (b) Band profile
profileof
ofthe
thep-n
p- heterojunction
heterojWlction in equilbrium.
equilibrium.
(al
(a)

~
the
he more
more negative
negative one is the
the reduced
reduced species.
species. The species
species are capable
capable of i

xchanging charge
exchanging charge with
with each other by transferring an electron. The relative
each other E

Eva3:dIJL ~
vac
concentrations
oncentrations are are fixed
fied onon preparation
preparation (like
(likedoping
dopingaa semiconductor)
semiconductor) and and i
cio
the
he overall
overall charge
charge is balanced with counter
balanced with counter ions.
ions. E n I <Eo :>
Like a metal
metal or
or semiconductor,
semiconductor, the redoxredox couple
couple has aa Fermi
Fermi level,
level, or
or Eco I ' EF
! I. ~Eo,'
..,./ij'''-
chemical potential, which
hemical potential, which isis constant
constantat at equilibrium.
equilbrium. To predict the the nature
nature
.- j "-- -",ERe6'
-- - <E :;-
of,f the
the junction,
junction, wewe needneed toto know
know the
the effective
effective work
work function
function of ofthe
theelec-
elec- Rec

rolyte, 'Po,
trolyte, which isis the
<Po , which the difference
difference between
between the chemical
chemical potential and and the
the
E
E
v v---- !
I
'acuum leveL.
vacuum level. Redox
Redoxpotentials
potentials are
areusually
usually given
given relative
relative to a standard ref-ref-
:rence level,
level, such If the I
erence such as the redox
redox potential
potential ofof hydrogen,
hydrogen. If the work
work function
function
reference is known,
of,f the reference known, then the work work function of the electrolyte
electrolyte can
can be
be (b)
(b)
lefined from
defined from the
the redox
redox potential
potential Fonash,
[Fonash, 1980j
1980J Fig,
Fig. 5.12.
5.12. (a)
(a)Band
Bandprofies
profilesofof
n-type
n-typesemiconductor
semiconductorand
andredox
redox electrolyte
electrolyte in
in isolation;
isolation;
(b) Band
(b) ofthe
profile of
Band profie the semiconductor-electrolyte
semiconductor-electrolyte heterojunction
heterojunction in
in equilbrium.
equilibrium.AAdeple-deple-
'Po o
Eredox ++<Prof
<Pe == E~odox 'Prof- -kBTln ([Re~)
kBTln (RedJ)
[OxJ (5.7)
(5.7)
tion
tion layer
the
layer is
is formed
formed at the
the reorganisation
reorganjsationenergy.
the semiconductor
energy.
semiconductor surface,
surface, as in a Schottky barrier.
barrier . ...\represents
represents
Oxj
136 The Physics
The Physics of Solar Cells
Cells Junctions 137

charge
charge separation.
separation. A balancing charged layer layer is formed
formed in the electrolyte.
electrolyte. electrolyte.
electrolyte. For
For current
current to flows
flows through
through the external circuit, the
the oxidised
oxidised
This charged
charged layer usually taken
layer isis usually taken up up within the first
within the first few
few monolayers
monolayers of species must
species must be
be able
able to recover
recover an electron from a counter electrode and
electron from
solvent molecules,
molecules, in in aa region called the
region called the Helmholtz
Helmholtz layer
layer which
which may
may sustain regenerate
regenerate the
the reduced
reduced form.
large
large electric
electric field.
field. The ionic concentrations
concentrations may may continue
continue to be disturbed The electrochemical junctionisisaa poor
electrochemical junction poor man's
man's Schottky
Schottky barrier.
barrier. It has
has
from
from equilibrium through aa region
equilbrium through region beyond
beyond the
the Helmholtz
Helmholtz layer
layer called the the advantage
advantage that field is
that the field established spontaneously
is established spontaneously upon
upon wetting
wetting the
diffuse layer. Because
diffse layer. Because the the permittivites
permittivitesof ofelectrolytes,
electrolytes, like
like metals, are small, semiconductor surface,
semiconductor surface,but
but the
the disadvantage
disadvantage that,
that, in many
many materials
materials sys-
sys-
the difference
difference in in work
work functions
functions isis taken
taken up almost entirely by the the semicon-
semicon- tems, the semiconductor
semiconductor surface is prone to reactreact chemically
chemically with the
the elec-
elec-
ductor,
ductor, i.e" the potential
i.e., the potential drop
drop within
withinthe theHelmholtz
Helmholtz layerlayer of
of the
the solution,
solution, trolyte
trolyte under
under illumination.
ilullnation. These problems can
These problems can be
be avoided
avoidedwith
withsensitised
sensitised
V
VH, is small and
H , is electrochemical junctions (Grtzel,
electrochemical junctions [Gratzel, 2001J.
2001].
11
-6,cp =
-6.<I>
qq
= Vbi + VH
Vbi + VH ""
"" Vbi.
V bi .
5.7. Junctions in
5,7. Junctions in Organic
Organic Materials
The energy levels
levels of
of the oxidised species
the reduced and oxidised species in
in the electrolyte Junctions in in molecular
molecular photovoltaic
photovoltaic materials
materials require
require different
different consider-
consider-
are
are slightly different. The
The mean
mean energy of the the oxidised
oxidised state,
state, (Eox)
(Eox) is higher
ations.
ations. InIn aa molecular
molecular semiconductor
semiconductor light light generates
generates excitons
excitons which are
which are
and mean energy
and the mean energy of the reduced
reduced state, (ERed) isis lower
state, (ERed) lower than
than the redox
redox
strongly bound,
relatively strongly bound, depending
depending on on the
the strength
strength of the intra-molecular
potentialbyby an amount known as
potential as the reorganisation energy. This difference
difference
forces compared
forces compared to to those
those binding
binding the molecules together, In some
molecules together. some crys-
crys-
is
is due to the
due to the reorgnisation
reorgnisation of of solvent
solvent molecules
molecules toto stabilse
stabilise the
the electron
electron
tallne organic
talline organic solids,
solids, intermolecular
intermolecular forces forces are
are strong
strong and
and carriers may be
on the reduced
reduced ion,
ion, like
like aa polaronic
polaronic effect
effect in a solid.
solid. Because
Because of thermal
considered to
considered to occupy
occupy bands much much like inorganic crystals.
like inorganic crystals. InIn such materi-
fluctuations, the
the energies
energies of the reduced
reduced andand oxidised
oxidised states
states are
are distributed
distributed als, excitons
als, excitons may be split spontaneously and devices devices can be designed using
around the mean
mean values.
values. These
These distributions influence the charge
distributions influence charge transfer
principles as
similar principles as for
for inorganic
inorganic metal-semiconductor
metal-semiconductor junctions. junctions. In
In other
processes at
processes semiconductor-electrolyte interface,
at the semiconductor-electrolyte interface. For
For electron transfer materials, such
materials, such asas amorphous
amorphous organic organc solids
solids oror polymers,
polymers, intra-molecular
to the
the semiconductor
semiconductor surface,
surface, forces dominate
forces dominate and and the excitons
excitons are are very
very tightly
tightly bound. In such cases the
Red ->
Red -' Ox
Ox++ e~ ,
e~, electrostatic fields
electrostatic available from
fields available from the the difference
difference in in work
work functions
functions ofof the
junction materials
junction materials is is not
not usually
usually suffcient
sufficient to to split
split the exciton. Instead,
the exciton, Instead,
the levels
levels of the reduced
reduced species
species should
should overlap
overlap with
with vacant levels in
vacant levels in the the excitons drift, and only split
excitons drift, split when
when they they approach
approach the the junction with
with a
semiconductor.
semiconductor. For
For transfer from the semiconductor,
semiconductor, contact material
material of of different
different work function. Charge
work function. Charge separation
separation thus occurs
occurs
only at the junction,
junction. The problemproblem is is that
that aa tightly
tightly bound
bound exciton is likely
Ox+e~->Red,
Ox + e~ -' Red,
to recombine
recombine before it it reaches
reaches the junction.
junction. In typical molecular materials
the levels
levels of the
the oxidised
oxidised species
species should
should overlap with filled
overlap with filled levels in the
levels in the exciton diffsion length
exciton diffusion length is is aa few
few tens of of nanometres.
nanometres. This This means
means that
semiconductor. for a Schottky
for Schottky barrier type structure, only only the 10 10 nm
nm ofof material
material closest
closest
Under illumination,
Under ilumination, electrons wil be
electrons will be transferred
transferred to oror from
from the
the semi-
semi- to the junction can contribute to the the photocurrent.
photocurrent. Hundreds
Hundreds of nm of the
conductor according
conductor according to to the
the type of doping. For the
doping. For the n-type semiconductor- material wil
will be
be needed
needed forfor aa good
good optical depth.
electrolyte junction
electrolyte junction illustrated
ilustrated in Fig.
Fig. 5,12,
5.12, electrons wil be
electrons will be transferred
transferred A solution
solution to this problem
problem is to use use aa distributed
distributed interface,
interface, where
where two
two
to
to the semiconductor surface,
the semiconductor surface, resulting
resulting inin the
the semiconductor
semiconductor gaining
gaining aa materials
materials of different electronic
electronic structure are combined into
are combined into aa blend,
blend. The
negative charge
negative charge andand the electrolyte
electrolyte a positive
positive charge,
charge, so providing
providing a materials should be chosenchosen so so that their
their energy
energy levels
levels line up to encourage
encourage
photovoltage. excitons to
excitons to split atat the
theinterface,
interface, as as shown
shown in Fig. Fig. 5.13.
5.13. The
The difference
difference in
The currentdensity
The current densityininthe
theelectrolyte
electrolyte is
is due
due to
to the
the net
net flux
flux of
of reduceCl
reduceq electron affinities
electron afities leads
leadstotostrong
stronglocallocalelectric
electricfields.
fields. Then
Then when
when anan exciton
exciton
species
species (in
(in this example) towards and oxidised
towards and oxidised species
species away
away from
from the semi- diffuses to
diffuses to the
the interface
interface itit is
is likely
likelyto to be
besplit
split and
and the
the resulting charge
charge states
states
surface. This provides
conductor surface. provides aa current directed from
from semiconductor to (which
(which are
are polarons
polaronsin in molecular
molecularmaterials)
materials)are arefree
freetotodiffuse towards the
difse towards the
138 The PhysiC3
The Physics of
of Solar
Solar Cells
Cells Junctions
Junctions 139
139
138

the
the sensitiser-semiconductor
sensitiser-semiconductor interface wherewhere the
the difference
differenceininelectron
electron affini-
affni-
ties splits the
ties splits the exciton.
exciton. Nanocrystalline
Nanocrystallne porous
porous semiconductor
semiconductor substrates
substrates al-
al-
e-
low
low blending
blending of of the materials on a a 1-100 nm scale.
scale. The physics
physics ofof organic
organic
photovoltaic
photovoltaic devices
devices isis described
described by Halls
Halls and Friend Halls,
[Halls, 2001J,
2001], 8Jld
and the
HOMO principles
principles of dyedye sensitised
sensitised junctions
junctions by [Gratzel, 2001;
by Gratzel Gratzel, 2001; Hagfeldt
Hagfeldt
h+
and Gratzel, 2000J.
and Gratzel, 2000].
HOMO
HOMO

"/I contact
contact ..nsllls.r p contact
5.8. Surface and
5.8, Surface and Interface
Interface States
States
electron hol.
electron
nn contact
contact acceptor donor
acceptor donor p pcontact
contact transportr transporter
Iransportor transporter
In discussing
discussing thethe various
various types
types of
of interface
interface (metal-semiconductor,
(metal-semiconductor, semicon-
(a) (b)
ductor heterojunction,
ductor heterojunction, semiconductor-electrolyte)
semiconductor-electrolyte) we we have
have supposed
supposed the
semiconductorinterfaces
semiconductor interfacesare areperfect.
perfect.In In fact
fact,, solid
solid surfaces
surfaces are
are likely
likely to
contain defects
contain defects and
and impurities,
impurities, both
both intrinsic
intrinsic defects
defectsdue
due to
to the
the interrup-
tion of the
tion of the crystal
crystal structure
structure atat the surface, and
the surface, extrinsic defects
and extrinsic defects due,
due, e.g.
e.g.
to adsorbed
adsorbed impurity
impurity atoms,
atoms. These
These defects tend to introduce
defects tend introduce extra
extra elec-
elec-
tronic states
states with
with energies
energies in thethe band
band gap.
gap. These
These 'surface'
'surface' or 'interface'
'interface'
states
states are
are (spatially) localised
localised near to the interface and are capablecapable of of trap-
trap-
ping charge,
charge, and
and so
so they
they will
wil influence
influence the the potential
potential distribution across the
interface through
interface through Eq. 5.6.5.6. When
When interface
interface states
states are present,
present, the poten-
poten-
tial difference necessaryto
difference necessary to match
match work
work functions
functionsacross
acrossaajunction
junction will
wil be
distributed differently,
differently.
anode cathode

Electric field 5.8.1. Surface

5.8,1. Surface states
states on
on free surfaces
fre surfaces
(c)
Intra-band
Intra-b8Jld gapgap states
states near to the the valence
valence b8Jldband tend to trap trap electrons
electrons (ac-
(ac-
Fig. 5,13.
5.13. (a)
(a)Band
Bandprofiie
profileofofjunction
junctionbetween
betweenan
anelectron
electron accepting
accepting and
and electron
electron do-
do- ceptor states) while near to the conduction
while states near conduction band band tend to trap trap holes
holes
nating molecular
molecular semiconductor under illumination.
semiconductor under ilumination" Photon
Photon absorption
absorption (1)
(1) isis followed
followed
(donor states).
(donor states). InIn general,
general, interface
interface states
states may may bebe distributed
distributed in in energy
energy
by
by recombination
recombination (2)
(2) or
or exciton
exciton dissociation
dissociation (3),
(3). Separated
Separated charges
charges may
may recombine
recombine (5),
(5).
Band profile
(b) Band profile for
for aa donor-acceptor junction with
with aa sensitising
sensitising molecule
molecule to the
to absorb the throughout
throughout the band band gap
gap region,
region, andand whether
whether they they actact like
like acceptors
acceptors or or
light;
light; (c)
(c)Schematic
Schematic of
of charge
charge separation and transport through
separation and through aa donor-acceptor
donor- acceptor blend.
blend . donors
donors depends
depends uponupon the occupancy
occupancy of of the
the states and the the Fermi
Fermi level
level of
of
the semiconductor.
semiconductor. It isis useful
useful toto define
define aa neutrality
neutralitylevel 1>0 as the
level ,po the level
level
collecting contacts. Charge
collecting contacts. Charge separation
separation will
wil be effcient
efficient if the materials
materials areare up toto which
which thethe states
states are
are filled
filled when
when thethe surface
surface (or interface)
interface) is is neutral.
neutral.
blended
blended on aa scale whi~h is
scale whi~h is similar
similar to the exciton
exciton diffusion
diffusion length, i.e.,
i.e., on
on This isis like
like aa Fermi
Fermi level
level for
for the surface in isolation. When the surface surface ad-
ad-
the
the nanometre
nanometre scale.
scale. By By using
using aa distributed
distributed junction,
junction, charge
charge separation
separation joins
joins aa layer
layer ofofsemiconductor,
semiconductor, ,po is in general
rPo is general at a different
different energy
energy than
than
CRn
CRn bebe achieved
achievedthroughout
throughout aa layerlayer of
of high
high optical
optical depth.
depth, AsAi; in all
all photo-
photo- the
the semiconductor
semiconductor Fermi level level and so charge
charge must be be exchanged
exchanged to bring bring
voltaic
voltaic structures,
structures, itit isis necessary
necessary to use
use asymmetric contacts to the the blended
blended the
the surface
surface andand semiconductor
semiconductor into equilbrium.
equilibrium. If 1>0 -(
If ,po < EF the the surface
surface isis
materials,
materials, so
so as
as to
to collect
collectelectrons
electronsand
andholes
holesselectively.
selectively. acceptor
acceptor like
like and traps
trapselectrons,
electrons, while rPo >
while ifif ,po :; EF the
the surface
surface isis donor
donor like
like
AA similar
similar principle
principle isis exploited
exploited inin dye
dye sensitised
sensitised devices,
devices, where mole~
where aa molec- and
and traps
traps holes.
holes. Figure
Figure5,14
5.14 shows
shows how a depletion region region isis established
established at at
ular
ular sensitiser
sensitiser is
is anchored at the the interface
interface between an electron transporting
transporting the
the surface
surface of an n type type semiconductor
semiconductor for which rPo <
which ,po -( EF.
E F . Upon
Upon contact,
contact,
semiconductor
semiconductor and a hole hole trarispNting
traI\spmting medium.
medium. In this
this case
case the
the junction
junctionisis electrons
electrons flow from semiconductor
semiconductor into into surface
surface states, leaving a positively
positively
140
140 The
Th e Physics
Physics of Solar Cells
Cells Junctions 141
141

surlace
surface n type semiconductor
semiconductor less far
would extend much less far into the
the semiconductor
semiconductor and the band
band bending
bending
smaller.
would be smaller.
Ec
Ec
------EEF 5.8.2. Effect
5,8.2, Effect of
of interface
interface states
states on
on junctions
junctions
F

% above we
From the above we see
see that surface
surface or interface
interface states
states can
can introduce aa
Ev Ev
potential difference, and an electric field
difference, and into an otherwise
field into otherwise neutral
neutral semi-
semi-
conductor structure. At a junction,
conductor structure. junction, interface states may
interface states may trap charge
charge and
(a)
(a) influence the potential and electric
influence the electric field
field distribution.
distribution. Although
Although interface
interface
states cannot
states cannot alter
alter the net potential
potential difference
difference across
across the
the junction (which
junction (which
+ ++
+
must always
always equal the difference in work
difference in work functions),
functions), they influence the way
way
n type semiconductor in which
which that potential
potential isis divided
divided between
between the two two materials.
materials.

-------Ec
Ec Interface states at
Interface states at a p-n
p-n junction
junction
- EF
EF Suppose
Suppose we we have
have an
an acceptor
acceptor like likeinterface
interfaceatataa p-n
p-n junction.
junction. When the
%
junctionisis formed,
junction formed ,some
some electrons
electrons fromfrom tthe
he n-type layer
layer become
become trapped
trapped at
the interface, so that
that aa smaller
smaller negative
negative space
space charge
charge needs
needs to bebe developed
developed
-------EE v in the pp side
side toto compensate
compensate the the positive
positive space charge on
space charge on the
the nn side. The
(b)
(b)
consequenceisisthat
consequence that more
more of of the
the potential difference
difference isis dropped
dropped on on the
the nn
side, and the
side, the electric
electric field,
field, which
which is is discontinuous
discontinuous atat the charged
charged interface,
interface,
5.14,
Fig. 5. 14. (a)
(a)Band
B andprofies
profilesoforsurface
surraceand
andn-type
n-typesemiconductors
sem iconductors in
in isolation;
isolation; (b) Band
profile of the
profile of the surface
surface in
in equilibrium.
equilbrium.
is now
now higher
higher onon the
the nn side.
side. To
Tosupport
support the
the larger potential difference on the
potential difference
n side an inversion layer
layer of mobile
mobile holes
holes (minority
(minority carriers)
carriers) may accumulate
beside
beside the interface.
charged depleted
charged depletedlayer
layerbehind
behinduntil
until the potential
potential barrier
barrierestablished,
established, Vbi,
Vbi, Figure 5.15
Figure showshow
5.15 shows howthethe band
band profile
profie may
may change. Notice that
change. Notice that the
is big enough to prevent
is prevent further
further flow.
flow. The
The surface
surface charge
charge accumulated
accumulated isis effect of
effect of the
the interface
interface layer
layer isis to Eo closer
to pull Eo to EF
closer to EF at the
the interface.
interface.
negative and is given by identifY two extreme
We should identify extreme situations:
. IfIfthe
thedensity
densityof ofinterface
interface states
states isis large
large enough,
enough, then the Fermi
Fermi level at
-Q, = LEo-Vn-Vbi
-q g,(E)dE (5.8)
(5.8) the interface wil be
interface will be pinned
pinned at 1>0, irrespective
at o, irrespectiveofof the
thework
work functions
functionsofof
.po
the materials on either side. side. The high density
density of trapped charge
charge at the
where Vn
where Vn isis the
the donor
donor ionisation energy,g.(E
ionisation energy, g,(E)) is
is the
the density
density of
of surface
surface interface screens
interface screens the two materials from from each other.
other.
states and
states and Vbi is determined by simultaneously solving
Vbi is solving Poisson's
Poisson's equation. . If,
If,ininaddition,
addition,o 4>0 isis low enough (comparable
low enough (comparablewith with the
the acceptor
acceptor ionisation
ionisation
This must
must be
be matched
mat ched by aa positive
positive charge +Q. inside
charge +Qs inside the
the semiconductor.
semiconductor. energy Vp)
energy Vp),, then
then the
the entire potential difference
difference can
can bebe dropped
dropped on the n
on the
negative depletion
A negative depletion layer
layer is
is similarly
similarly established
established nearnear the surface of aa side.
side.
p-type semiconductor
semiconductor with 1>0 <-( EF.
with o EF. See Bardeen (Bardeen,
See Bardeen [Bardeen, 1947J, foran
1947], for an
early discussion
discussion of the effects surface states.
effects of surface states,
Interface states
Interface states at a metal-semiconductor junction
metal-semiconductor junction
If instead
If instead we had aa surface
we had with 1>0
surfacewith o>? EF
EF on
on anan n-type semiconductor,
semiconductor,
or 1>0
or o -(< EF
EF on on aa p-type
p-type semiconductor,
semiconductor, then then the
the semiconductor
semiconductor would
would layer immediately
An interface layer immediately next
next to.
to the metal at a metal-
metal-semiconductor
semiconductor
accumulate carriers to compensate the surface charge, charge, but the charged layer junction has
junction has no effect
effect on
on the electrostatics of the junction
electrostatics of junction because
because the
142
142

E~~~ - --- -----r---- -~

The Physics
The Physics of
of Solar
Solar Cells Junctions

of the
the insulating
insulating layer.
layer, Note
Note that
that the presence of the
the insulating
insulating layer
143
143

layer will
wil

?
of presence of

'1 -Eq~
Evac
always
alwaysmean meanthat that the built-in
built-in bias
bias in in the
the semiconductor,
semiconductor, Vbi, Vbh isis less
less than

Eo'f ,ain ~.6.<I>w.

~tiq,w. The
The role
role of
of interface
interface states
states isis to
to influence
influence the the sharing
sharing ofof the
the poten-

Ev ~ , F
tial difference
tial
an
field
betweenthe
difference between
an n-type
n- type semiconductor,
the interface
field at the interface so
the semiconductor
semiconductor,acceptor
semiconductorand
acceptorlike likestates
and the
statestend
the insulating
insulating layer.
tend to
less of the potential difference
so that less
layer. With
reduce the
to reduce
difference is
the electric
is dropped
dropped in

~"---
the insulator
the insulator and and more
more inin the
the n-type
n-type material,
material, just just as
as in
in the case
case of the
heterojunction (i.e.,
heterojunction (i.e., Vbi
Vbi isis increased
increased relative
relativeto to the
the case
case with no interface
states).
states). Donor like statesstates increase
increase the
the field
field at thethe interface
interface and
and reduce
reduce Vbi.
Vb i .
(a) For an extremely
For extremely high high density
density of ofinterface
interfacestates, states,EF EFwill
wil be
be pinned
pinned at o,cPo,
the interface charge wil screen
charge will screen the metalmeta l from
from the the semiconductor
semiconductor and and Vbi
Vbi
wil be
will be independent
independent of the work work function
function of of the
the metal.
metal. This is called
called the
Bardeen limitlimit for
for metal semiconductor
semiconductor junctions.junctions. In In the
the opposite
opposite limit,
limit, of
a perfect junction
junction with
with no
no interface
interfacestates,
states, anyany change
changeininthe thework
workfunction
fuction

Ev ~
:~ 'l-~?~Ee of the metal

Just
J
metalcauses

Interface states
causes anan equal
equal change
change in Vbi.

states at aa semiconductor-electrolyte

listasasatat the
the semiconductor-metal junction,
Vbi .

junction
semiconductor-electrolyte junction

junction, interface
interface states
states at a
at a
semiconductor-electrolyte junction can
can accommodate part
part of
of the
the difference
difference
Fig. 5.15.
Fig. (a) Band
5.15. (a) profiles of
Band profiles of aa p-n junction in
p- junction in equilbrIum (a.) in
equilibrium (a) in the
the absence
absence of
of in work functions
functions between the semiconductor and redox
redox couple.
couple. Including
interface
interface states (b)
(b) with
with acceptor
acceptor like
like interface
interface states, which
which change
change the division
division of the the interface
interface state
state charge
charge we
we have
have
built-in
built-in bias
bias between
between the
the two
two semiconductors.
semiconductors.
'w = Vbi + Vint + VH .
interface chargewill
interface charge wil be
be screened by the
screened by the infinitely mobile
mobile charge
charge of the
the Again, for aa very high
high density
density of
of interface states, EF
interface states, EF is
is pinned at cPo
pinned at oatat the
the
metal.
metal. If, however, the interface
however, the layer isis separated
interface layer separated from
from the
the metal by anan interface and Vbi
Vbi is independent of the redox
redox couple.
couple.
insulating
insulating layer then charge
layer then can be stored
charge can stored at either
either side
side of
of this
this insulator,
insulator,
like aa parallel
parallel plate
plate capacitor,
capacitor, causing
causing a Vint. This
a potential drop, Vint. This is
is aa real-
real-
istic situation since
since a thin
thin layer
layer of
of oxide
oxide may form
form between
between the metal and 5.9. Summary
5,9. Summary
the
the semiconductor.
semiconductor. VintVint contributes to the
the change
change in
in work
work functions
functions across
across For a light
light absorbing
absorbing device
device to work
work as
as aa solar
solar cell,
cell, some
some kind
kind of
of asym-
asym-
the
the junction
junction through
through metryneeds
metry needstotobebebuilt
built in
in to
to the system whichdrives
system which drives electrons
electrons and holes
and holes
i1 in different
different directions.
directions. This
This asymmetry
asymmetry may
may be introduced through spatial
spatial
-'w Vbi++Vint
-.6.cPw==Vbi Vint (5.9)
(5.9) variations in the
the electronic
electronic properties. Spatial variation inin electron
electron affnity,
affinity,
qq
band
band gap,
gap, work
work function
function or
or density
density of
of states
states can
can drive
drive charge
charge separation.
separation.
and
and must
must be
be given
given by
by Variations in work
work function can generate
generate large electric
electric fields
fields and are most
most
Vint = c:Qd
Vint cQd commonly
commonly used.
used.
At
At the
the interface
interface between
between two
two different
different electronic materials, a potential
electronic materials, potential
where
where Q here
here represents
represents the total
total charge
charge developed
developed in the the semiconductbr,
semiconductbr, step
step equal to the
the difference
difference in work
work function
functionisisestablished
established by
byexchange
exchange of
of
dd the
the thickness
thickness of
of the
the interface
interface layer
layer and
and c:c is
is the
the dielectric
dielectric permittivity
permittivity charge
charge carriers.
carriers. The potential is taken
taken up
up in
in the
the semiconductor(s)
semiconductor(s) and
and is
is
144 The
The Physics
Physics of Solar Cells

11
represented
represented by by bending
bending the the bands.
bands. TheThe junction
junction isis effective
effective for
for charge
charge sep-
sep- ,i
1
aration if the
the semiconductor
semiconductor is depleted of carriers and blocks blocks the flowflow of 11,...1

majority carriers across the junction. If If the

the semiconductor
semiconductor is is enriched with :'1
,11
charge
charge the junction is is Ohmic,
Ohmic. A blocking
blocking contact can be be formed
formed between
between "I
Chapter
Chapter 6
aa metal and
and semiconductor
semiconductor (a (a Schottky
Schottky barrier),
barrier), between
betweenan annand
nand p-type
semiconductor
semiconductor (a (a Jrn
p-n junction) or or between
between a semiconductor
semiconductor and an an elec-
elec-
trolyte. When
When the device
device isis illuminated, electrons and holes
iluminated, electrons holes are separated Analysis of
Analysis of the
the p-n
p-n Junction
by the field
by field at the
the junction,
junction, andand accumulate
accumulate on on opposite
opposite sides.
sides. The pho- pho-
tovoltage is
tovoltage is determined
determined by by the
the maximum
maxmum chargecharge separation and is is related
the height
to the height of the the potential
potential step
step and
and the rectifying
rectifying action of the the junc-
junc-
tion. At
tion. At aa Schottky barrier the
Schottky barrier the photovoltage
photovoltage is is limited
limited byby the
the formation
formation
of an
of an inversion
inversionlayerlayerandandby tunnellng.Jrn
bytunnelling. junctions perform
p- junctions perform better.
better. De-
De-
6.1. Introduction
6,1. Introduction
fects at the interface introduce states in the
fects the semiconductor
semiconductor band gap which
can trap charges
charges and influence
influencethe the potential
potential distribution
distribution atat the junction. A p- homojunction
The Jrn homojunctionisisthe themost
mostwidely
widelyuseduseddevice
device structure
structure ii in photo-
photo-
high density
density of interface
interface states reduces the photovoltage
states reduces photovoltage and degrades
degrades the voltaics.
voltaics. Selective doping of
Selective doping of the different sides of a semiconductor wafer
different sides wafer p
photovoltaic
photo voltaic performance of the device. device. type and n type leads leads to a potential
potential barrier
barrier between
between the regions. This This junc-
tion acts as
as aa selective
selective barrier to charge
charge carrier flow,
flow, soso that
that there is is aa low
low
resistance path for electrons to
for electrons to the n contact and for holes to the p contact,
References
thus providing
providing the asymmetry
asymmetry in in resistance
resistance which
which isis necessary
necessary for photo-photo-
J. Bardeen,
J. Bardeen, "Surface states", Phys.
"Surfac states", Phys. Rev.
Rev. 71,717 (1947) .
71,717 (1947). voltaic conversion.
conversion. By By control of the the doping
doping levels, large potential barriers
levels, large barriers
S.J. Fonash, Solar
S.J. Fonash, Solar Cell Device
Device Physics (New York:York : Academic,
Academic, 1980).
1980). can be established which ma make possible to
ke it possible to generate
generate large photovoltages. It
Gratzel, "Photoelectrochemical
M. Grtzel, "Photoelectrochemical cells", Nature 414,
cells" , Nature 414, 338-344
338-344 (2001).
(2001).
A. Hagfeldt
Hagfeldt and M.M. Grtzel,
Gratzel, "Molecular
"Molecular photovoltaics", Ace. Chern.
photovoltaics", Ace. Chern. Res.
Res. 33,
33, has the practical advantage that that the
the junction
junction can can be
be prepared
preparedfrom from aa single
single
A.
269-277 (2000).
(2000) . crystal semiconductor wafer wafer without the need for a metallurgical interface, interface,
Halls and
J.J.M. Halls and R.H. Friend, "Organic
"Organic photovoltaic
photovoltaic devices" Clean Electricity
devices" in Clean and the associated
associated problems of of interface
interface states.
states.
from Photovoltaics,
from Photovoltaics, eds.
eds. M.D.
M.D. Archer
Archer and
and R.D.
R.D. Hill (Imperial College
Hil (Imperial College Press,
Press, The photovoltaic function of
photovoltaic function of aa Jrn
p-n junction can be analysed
analysed using the
2001).
2001) . theoretical apparatus
apparatus introduced
introduced in in Chapters
Chapters 33 and 4. 4. In general,
general, the prob-prob-
lem
lem consists
consists of of solving
solving aa set
set of coupled diferential equations for
coupled differential for the
the elec-
elec-
tron density,
density, hole
hole density
density and
and thethe electrostatic
electrostatic potential,
potential, given
given specified
specified
forms for the photogeneration,
photogeneration, the recombination
recombination and and the
the electron
electron andand hole
hole
currents,
currents. It is is in
in general
general aa complex
complex problem
problem but, but, with the benefit
benefit of of two
two
approximations, analytic solutions
approximations, analytic solutions for for the
the JJ(V)
(V) characteristic
characteristic under
under differ-
ent conditions
conditions can can bebe found.
found . These
These two approximations are the depletion depletion
approximation, and the
approximation, the approximation
approximation that that recombination in in the
the doped
doped
material isis linear,
linear. This
This allows
allows the differential
differential equations
equations to be be uncoupled
uncoupled
and linearised.
linearised. In the next next sections
sections we we first outline the approach
approach to to solving
solving
the p-n
Jrn junction,
junction,before
before presenting
presentingthe thesolutions
solutions and
and discussing
discussing some
some of the
implications for
implications for junction design.
junction design.

145
145
146 The Physics of Solar Cells
146 The Physics of Solar Cells Analysis of the
Analysis the p-n Junction
p-n Junction 147
147

6.2. The
6.2. p-nJunction
The p- Junction pp nn

6.2.1. Formation
6.2.1. Formationof
of p-n
p-n junction
junction

As explained
As explained in
in Chapter 5, aa p-n
Chapter 5, junction isis established
p-n junction established when
when aa layer
layer of
of i~
Ik. IIII II
=~=g=g=~- g e=o=o=e=o=
.=0=0=.=0=
II IIII IIII
semiconductor and a layer of n-type material are brought
p-type semiconductor
diffuse across
across the junction leaving
leaving behind
behind aa layer
brought together.
layer of
offixed
together.
fixed charge,
charge,
II II II II~ ~-
=~=~=~-
=0=0=0=0
II + IIII II
ii~ 11+
~=~+
0 .=0=0=0=0=
II~=~=~=
II IIII
II
Carriers diffuse
due to the
the now
now ionised impurity atoms,
atoms, on
on either
either side.
side. This
This space
space charge
charge sets
jd
II II 11_ II 11- o=e=o=o=o=
=0=0=~=0=~ II 11+ II II II
=O=O==O~ 0=.=0=0=0=
up an electrostatic field which
Equilibrium isis established
Equilbrium
which opposes
established when
opposes further
when diffusion
further diffusion across
across thethe junction.
diffusion of majority carriers across
junction.
across the
F
II
II II
II II
II II
II II
II IIII IIII IIII IIII IIII
junction is
junction is balanced
balanced by by the
the drift
drift of
of minority carriers back across the junction
in the built
built in
in electrostatic
electrostatic field.
field. At this
this point
point the
theFermi
Fermi levels
levels of the p and
(a)
type layers are equal, the difference
n type layers are equal, the difference
n in the work functions is
work functions is taken up byby
a step
step in thethe conduction
conduction and and valence
valence band
band edges,
edges, called
called the
the built-in bias,

I
a built-in bias,
the junction
and the junction region
Thebuilt-in
The
region is
built-in bias
bias in
is depleted
depleted of
in equilibrium,
equilbrium, Vbi,
of carriers.
carriers.
is determined
Vb;' is determined byby the
the difference
difference in
in
E- vac I -- "-
- - -..- -
Evac - - -.11'.- - -- " v.
work functions of the nand p type materials, Pn and Pp.
work functions of the nand p type materials, iPn and iPp' The difference The difference cI>
tV
"~ '-
'- _- -;;,_
___ q bi
_T_ . .qVbi
in work functions
functions is is equal
equal to the difference
difference in of the
in the shift of the Fermi
Fermi levels
levels
from
from the intrinsic potential
potential energy
energy of the semiconductor, since Ei is parallel Ec (fn
<I>

~
to Evac.
Evac. Hence

1 1
q q (6.1)
Vbi = -(iPn - iPp) = -((Ei - EF)lp side - (Ei - EF)ln side)' (6.1)
Ev
______~------~----~-------EE F

Far from
from the
the junction, Nd on the n side and p
junction, nn == Nd p = Na on
= Na on the
the pp side.
side. The
shifts
shifts Ei - EF can then be expressed in terms of the doping levels using
Ei - EF can then be expressed in terms of the doping levels using (b)
Eqs.
Eqs. 3.37
3.37 and
and 3.38
3.38for
for nand
nand p. This gives
p. This Vbh
gives for Vbi,
Fig.
Fig. 6.1. (a) Schematic
6.1. (a) Schematicofofcrystal
crystal structure
structure close toa ap-n
close to p- junction.
junction. Close
Close to
to the
the junction
junction
free carriers
free carriers are
are removed,
removed, so
so that
that acceptor impurities on the pp side
side (grey
(grey circles) become
Vbi = ksT In (NdNa) (6.2) negatively charged,
negatively charged, and
and donor
donor impurities
impurities on
on the n side
side become
become positively
positively charged;
charged; (b)
q nr (6.2)
Energy band
Energy band profile
profie across junction in
across the junction in equilibrium.
equilbrium,
relating V bi to
Vbi tothe
the doping
doping levels.
levels.Figure
Figure6.16.1illustrates
ilustrates the space charge and
band
band bending
bending inin aa p-n
p-n junction
junction at equilbrium.
equilibrium.
bias
bias of Vbiwill
of Vbi completely cancel
wil completely cancel the potential
potentialstep
step and
and remove
remove the asymme-
If
If an external electrical
electrical bias
bias is applied, it raises
is applied, raises the Fermi
Fermi level on one
try which drives
drives the
the photovoltaic
photovoltaic effect.
effect.Illumination
Ilumination of the semiconductor
side with respect to the other
side with respect to the other andand the potential dropped across the junction,
causes photogenerated
causes photogenerated holes
holestoto build
buildup
up in
in the
the pp side
side and
and electrons
electrons on
on the
Vj
Vj becomes
becomes nn side, shifting the Fermi levels in the
levels in the same sense
sense asas aa positive applied bias.

Vj = Vbi - V (6.3)
(6.3) ~

6.2.2. Outline of approach

6.2.2. Outline approach
where VV is
where is the bias
bias applied
applied to the
the pp side.
side. A negative
negative applied
applied bias
bias with-
draws carriers from the junction region, increasing the depletion while
draws carriers from the junction region, increasing the depletion while aa In the analysis of the p-n
In p-n junction
junction which
which follows, we assume
follows, we assume that
that we have
positive
positive applied
applied bias
bias injects
injects carriers
carriers and
and reduces
reduces the depletion.
depletion. A positive high quality,
high quality, crystalline
crystallne semiconductor
semiconductorlayers,
layers,that
that the
the junction
junction is
is free
free of
 148
148
The Physics
The Physics of
ofSolar
SolarCells
Cells Analysis
Analysis of
of the
the p-"
p-n Junction
Junction 149
149

interfacestates.
interface states.We
We assume
assume that
thatthe
thebuilt
builtininbias
biascan
canbe
betaken
takenup
upcompletely
completely minority
minority carrier
carrier currents
currents under
under ilumination
illuminationand
andapplied
appliedbias.
bias.We
Weinclude
include
within the
within the nand
nandp players.layers.This Thisisistrue
truefor fortypical
typicaldoping
dopinglevelslevelsand andlayerlayer termsfor
terms for the
the dark
dark and
andphoto-currents
photo-currentswithin
withinthe
thedepletion
depletion region.
region. Before
Before
thicknesses. Then the junction consists of three
thicknesses. Then the junction consists of three regions: a neutral p type regions: a neutral p type the
the depletion
depletion region
region current
current isis included,
included, the
the current
current voltage
voltage characteristic
characteristic
region, aa charged
region, charged region
region around
around the the junction
junction and neutral nn type
and aa neutral typeregion.
region. has the
has the ideal
ideal diode
diode form (Eq. 1.5)
form (Eq. 1.5) and the superposition
and the superposition approximation
approximation
We want
We want to calculate the current which passes through the device inin
to calculate the current which passes through the device (Eq. 1.4)
(Eq. 1.4) isisobeyed.
obeyed.
steady
steady statestate under
under given
given illumination
ilumination and andfor foraagivengivenpotential
potentialdifference
difference We look at solutions for special cases to show how the photocurrent
We look at solutions for special cases to show how the photo current isis
between the terminals. In general, this may
between the terminals. In general, this may be done by solving the be done by solving thesemi-
semi- influenced
influenced by the minority
minority carrier
carrier transport
transportparameters
parameters and
and how
how the
the dark
dark
conductor transport
conductor transportequations
equationsand andPoisson's
Poisson's equationequation (Eqs. 4.87-4.89) self
(Eqs. 4.87-4.89) self current
current is influenced by the recombination mechanism. Series resistance can
is influenced by the recombination mechanism. Series resistance can
consistently together with appropriate boundary conditions at the p and nn
consistently together with appropriate boundary conditions at the p and be
be accommodated
accommodated by by adjusting the junction
junction potential
potential to
toallow
allow for
for potential
potential
terminals and appropriate forms for the photogeneration
terminals and appropriate forms for the photogene
ration and recombina-
and recombina- drops
drops in
in the
the doped
doped regions,
regions, and the effects of
of temperature
temperature and light intensity
intensity
tion rates and the electron and hole currents. The problem is, iningeneral,
tion rates and the electron and hole currents. The problem is, general, are studied.
are studied.
complicated because
complicated because of of the
the coupling
coupling of of electron
electron and hole densities
and hole densities through
through
Poisson's equation and non-linear recombination
Poisson's equation and non-linear recombination terms. terms.
The problem
The problem is is simplified
simplified by by making
making two two approximations.
approximations. First, First, we we as- as- 6.3. Depletion
6.3. Depletion Approximation
Approximation
sume that the charged region around the junction
sume that the charged region around the junction contains no free carriers contains no free carriers
so that the potential
potentialstep step isis taken
taken upup completely
completely by We define our
We define our junction
junction asas aa layer of pp type
layer of type material
material of
of doping
doping N
Naa for
for xx <
.. 00
so that the by the
the fixed space charge
fied space charge of of
the doped materials near the junction. This is the depletion approximation. which adjoins a layer of n type material of doping Nd for x > 0, with aa
which adjoins a layer of n type material of doping Nd for x :; 0, with
the doped materials near the junction. This is the depletion approximation.
In this
this approximation,
approximation, the the electric
electric field
field vanishes
vanishes at perfect interface in
in the
the plane x = O. The pp layer
O. The layer has
has thickness
thickness xp
xp and
and the
the n
In at aa fixed distance from
fied distance from ei- ei-
ther side of the junction, leaving neutral p and n type regions. Within these layer has
layer has thickness
thickness xxn. The junction is completely free
n . The free of
of majority
majority carriers
ther side of the junction, leaving neutral p and n type regions. Within these
neutral regions, the for a depth wp
for wp into the
the pp layer
layer and
and Wn into the n layer, as shown in Fig. 6.2.
Wn into
neutral regions, the majority carriers have
majority carriers have their
their equilibrium
equilbrium value value andand onlyonly
variations Then the depleted layers in the two materials are charged
charged by the ionised im-
in
variations in the minority carrier density determine the current. Across the
the minority carrier density determine the current. Across the
depleted purity atoms. The regions beyond these boundaries
purity atoms. The regions beyond these boundaries are are completely
completely neutral.
neutral.
depleted regionregion the the quasi
quasi Fermi
Fermi levels
levels areare separated
separated by by the applied bias,
the applied bias,
q Vj and this provides a boundary condition on the minority carrier density Note that an
Note that an n-p
n-p junction
junction can
can be
be treated
treated exactly
exactly the
the same
same way:
way: only
only
q Vj and this provides a boundary condition on the minority carrier density of xx changes.
the direction of changes.
at the edge
at the edge of of each
each neutral
neutral region,
region, so sothe
the minority carrier density
minority carrier density can can be be
solved within that region alone. Finally, the absence
solved within that region alone. Finally, the absence of electric field means of electric field means
that the minority carrier currents are driven by diffusion
that the minority carrier currents are driven by diffsion onlyonly and the cur-
and the cur- pp region
region nn region substrate
substrate
rent
rent equations are simplified. Thus the depletion approximation allows the
equations are simplified. Thus the depletion approximation allows the
solutions in the neutral p and n regions to be decoupled.
solutions in the neutral p and n regions to be decoupled.
The
The second
second approximation
approximationisisthat that the
the recombination
recombinationrates rates in in the neu-
the neu-
tral regions are linear in the minority carrier density.
tral regions are linear in the minority carrier density. This is reasonable,
This is reasonable,
according
accordingtoto Eqs. Eqs. 4.80-4.81,
4.80-4.81,since sincethethe majority
majority carriercarrier densities
densities are are large
large
and constant. This allows analytic solutions to
and constant. This allows analytic solutions to be found. This linearisa- be found. This linearisa-
tion
tion decouples
decouplesthe theeffect
effectofofbias biasfrom
fromthe theeffect
effectofofillumination,
ilumination,sosothat that
the
the solutions under bias and under light may be added to
solutions under bias and under light may be added to give
give the solu-
the solu-
tion under both light and bias. This is sometimes called the superposition
tion under both light and bias. This is sometimes called the superposition
approximation.
approximation. -Xn -Wn Wn Xn
In
In the
the following,
following,we wewill
wilfirst
firstestablish
establishthe the width
width of of the
the depleted
depleted region,
region,
o
or space charge region (SCR). Then we set up the equations forthe
or space charge region (SCR). Then we set up the equations for theminority
minority Fig.
Fig.6.2.
6.2. Schematic
Schematic layer
layer structure
structureofofp-n
p- junction,
junction,showing
showing charged
charged region
region near
near
carrier
carrierdensities
densitiesininthe theneutral
neutral regions,
regions,and andfind findthethegeneral
generalsolution
solutionfor forthethe junction.
junction.
 The
The Physics
Physics of Solar Cells
Cells Analysis the p-n
Analysis of the p-n Junction
Junction 151
150

6.3.1. Calculation of
of depletion
depletion width
Requiring that and
Requiring that Fare. continuous
and Fare at xx =
continuous at = 0 we
we obtain
obtain the
the individual
individual
6.3.1. Calculation width
depleted widths
According to Poisson's
According to Poisson's equation
equation the
the electrostatic potential
electrostatic potential must obey
must obey
1 2es Vbi
d2 _ !LNa
dx2 - es
<0
for xx -:
for (6.4)
(6.4)
wp = Na
(i-)'
q Na + Nd
(6.10)
(6.10)

2es Vbi

(i-)'
1
and Wn = Nd (6.11)
(6.11)
q Na + Nd
d? q
d?== --Nd
- -!!..Nd for > 00
x )0 (6.5)
(6.5)
dx2 eses
dx2
for x
and the total
and the total width of the
width of the space
space charge
charge region,
region, Wscr

where
where eses isis the
the permittivity
permittivity ofof the semiconductor and
the semiconductor and isis related
related to the
to the 2es (~ + ~)
2es ( 1 1 )
intrinsic potential energy Ei through Ei = -q+C where C is
intrinsic potential energy Ei through Ei = -q+C where C is any constant any constant Wscr== wp
Wscr wp + Wn =
Wn = - -+-
qq Na
Vbi.
Na Nd
Nd
Vbi . (6.12a)
(6.12a)
and can be
and can be setset to
to O. Since can
O. Since can vary
vary only
only within
within the
the space
space charge
charge region
region
it must change
it must change by Vbiby V across the width of that region. This
bi across the width of that region. This gives gives us the
us the Notice
Notice that that the depleted
depleted width increasesasas either
width increases either the
the pp doping
doping oror the
the nn
boundary conditions
doping isis reduced.
doping reduced. This
This means
meansthatthat it is not feasible to have
feasible to have aa p-n
p-n junction
with bothboth aa wide
wide depleted
depleted region,
region, which
which aids carrier
carrier collection,
collection, and high
=O x =
at x -wp
-wp doping levels, which aid cell voltage.
levels, which aid cell voltage. This is one of several compromises in
cell design.
and Notice also that the
Notice also the division
division of of Vbi
Vbi between
between the two two layers
layers depends
depends
upon the relative doping:
doping: more of Vbi Vbi is
is dropped
dropped in the layer which has has the
=Vbi at
at x
x = w n .
= Wn
lower doping and the wider depleted width. In most crystallne solar cells
lower doping and the wider depleted width. In most crystalline solar cells
Integrating Poisson's equation
Integrating Poisson's equation then
then yields
yields expressions
expressions for
for the
the electric
electric it isis usual
it usual toto dope
dope the
the top
top layer
layer (known
(known ininelectronics
electronics terminology
terminology asas the
field,FF == -- ::::'' emitter) heavily
emitter) heavily but
but the lower layer (known
lower layer (known as as the
the base) lightly, so
base) lightly, so that
field,
almost all of the space
almost space charge region lies within
region lies within the base. The reasons
reasons for
for
d qNa (x + wp)
d _ _ qNa (6.6) this wilwill be
be explained
explained in Chapter 7. Then, for a p on n
7. Then, for a p on n structure,
-- = --(x+wp) for -- Wn
for < xX -:
Wn -: <0 (6.6)
- dx
dx - eses
2es Vbi.
Wscr ~ Wn = (6.12b)
(6.12b)
and qNd
d=qNd
_ d qNd (x _ w n ) for 0 <
for < wp
-: x -: wp (6.7)
(6.7) The potential and electric field
and electric field profile
profilefor
for aatypical
typicaljunction
junction are
areillustrated
ilustrated
--dx= es
dx
-(x-wn)
es in
in Fig. 6.3.
Fig. 6.3.

using If bias V is
If aa forward bias the pp side relative to the n side, then the
is applied to the
using the boundary conditions
the boundary conditions that the field
that the field must vanish at
must vanish the edges
at the edges of
of
the depleted layers. A further integration, using the boundary condition on bias across
across thethe depleted
depleted region reducedtotoltjij = (Vbi
regionisisreduced (Vbi - - V).
V). The boundary
the depleted layers. A further integration, using the boundary condition on
yields
condition at
condition at Wn
Wnbecomes
becomes(w (wn)
n ) = = ij,
ltj, and
and Wn
Wn and
and wp
wp wil be
will be reduced
reduced
in proportion to vlVbiJVbi -- V. Similarly,
Similarly, ifif the junction is reverse biased,
biased, the
qNa 2
-(x+wp)p )2
qNa
=-(x+w
= for -- Wn
for < xX -:
Wn -: <0 (6.8)
(6.8) ~ potential
potential drop
drop increases
increases and the depleted
depleted layers
layers become thicker.
thicker. The applied
2es
2es ~ bias
bias shifts
shifts the relative
relative position
position of the quasiquasi Fermi
Fermi levels of the majority
levels of majority

q.
).L

carriers inin the neutral regions,

regions, soso that
that
and
1
qNa
qN
== ---
-
a(
-x-wn)
( 2)2 +Vbi
x - Wn + VIbi for
for 0 < xx -:
0 -: < wp.
wp . (6.9)
(6.9)
V = -(EFn(Wn) - EFp(-Wp)). (6.13)
(6.13)
2es
152 The Physics
The Physics of Solar Cells
Cells Analysis the p-n
Analysis of the p-n Junction
Junction 153

pp
through
p
p n pp n n

+
Nd
Vbi
In(x) J
In(x) == J jn(E,x)dE
jn(E,x)dE (6.14a)
(6.14a)

Jp(x) =J
Jp(x) = J jp(E,
jp(E, x)dE (6.14b)
(6.14b)

provided
provided that thethe differential
differential equations governing nand
equations governing nand pp are
are linear.
-Na
- t- In the electrically neutral
neutral pp and nn layers,
layers, the
the electric
electric field is zero
zero and
and the
space electric field potential majority carrier
majority carrier concentration
concentration isis constant
constant atat the
the doping
doping leveL.
level. The minor-
space charge
charge
ity carrier concentration
concentration is is controlled
controlled byby the
the transport equations
equations 4.91
4.91 for
for
Fig. 6.3.
Fig. 6.3. Doping
Doping profie,
profile, electric fieldand
electric field and potential
potentialvariation
vaiation across
acrossaap-n
p- junction.
junction. electrons
electrons in
in the
the neutral
neutral pp region
region and 4.92 for
and 4.92 for holes
holes in
in the
the neutral region.
neutral n region.
The electric field varies linearly
field varies linearly and
and the
the electrostatic
electrostatic potential quadratically across
across each
each If recombination
recombination isis linear
linear then,
then, in
in the neutral pp region,
region, n(x) satisfies
satisfies
depleted region.
depleted region. In
In this example, the pp layer
example, the layer is
is doped
doped more
more heavily
heavily than
than the n and
and so
so
the depletion
depletion width is larger
larger in the n.
dd2n
2
n __ (n
(n- -no)
no) g(E,x)
g(E,x) __ 00
dx2 2
dx 2
n +nD -.
2n + D n -. x -: -wp (6.15)
(6.15)

Because
Because all
all potential
potential isis dropped within the depleted
depleted layer, the quasi
quasi Fermi
Fermi from Eq.
from Eq. 4.93 forFF = 0,
4.93for 0, where g(E, x)
where g(E, x) is
is the
the pair generation rate at x,
generation rate
levels of
levels of majority
majority carriers
carriers remain
remain constant
constant throughout the neutral
neutral regions.
regions. given by
A further requirement
A requirement of depletion is that the
depletion is the difference
difference in electron
electron and
g(E, x) == (1
g(E, x) (1 - - R(E))a(E)bs(E)e-a(E)x
R(E))a(E)bs(E)e-O!(E)x (6.16)
(6.16)
hole quasi
hole quasi Fermi
Fermi levels
levelsmust
must remain
remainconstant
constantand
and equal
equal to
to V
V across
across the
depleted layer, e.,
layer, i.i.e., from Eq. 4.25
from Eq. 4.25 for
for aa uniform
uniform materiaL. Ln is
material. Ln is the
the electron
electron diffusion
diffsion length
length
given
given by Ln =
by Ln = ....;:r;:IJ;.
where where Tn the
Tn is is the electronlifetime.
electron lifetime. At
At the
the boundary
boundary
pn = n?eav /kBT for
for -- < < wp ..
Wn-: xX -: Wp
Wn with the depletion
depletion region
region n(x) satisfies
satisfies
1

nn22
This has the
the consequence
nn -- no
no =
= -i(eav /kBT --1)
_ i (eQV/kBT 1) x = -wp (6.17)
(6.17)
that EF
consequence that nand EF
EF nand EF pp are
are both constant across the Na
depleted region.
where no == nr INa
where no jNa is the equilibrium
equilibrium electron density in
electron density in the pp region.
region. This
boundary
boundary condition follows
follows from the
the requirement
requirement that
that EF
EFn - EFEFpp ==qqVj
Vj
6.4. Calculation of
6.4. Calculation of Carrier and
and Current Densities
Current Densities throughout the
throughout the space
space charge
charge region (SCR). second boundary condition
(SCR). The second
provided by
is provided by the surface recombination at
surface recombination at the outer surface
surface
6.4.1. Currents
6.4.1. Currentsand
andcarrier
carrierdensities
densities in
inthe
theneutral
neutralregions
regions
dn
Dn dx = Sn(n - no) at x -xp'p
x = -x (6.18)
(6.18)
To calculate
To the carrier
calculate the carrier densities we will
densities we wil use
use the
the semiconductor
semiconductor trans-
trans-
port
port equations
equations derived
derived in in Chapter
Chapter 4.4. These
These simplify for each
simplify for each of the
the We have
We have used
used Eq.
Eq. 4.85
4.85 and
and the
the fact
fact that the
the electron
electron current
current is
is purely
purely
three regions of the p-n junction, which we will consider
three regions of the p- junction, which we wil consider separately. We separately. We diffusive
diffsive when F == 0,
when F 0, hence
will consider aa junction
wil consider junction illuminated
iluminated by by aa flux density bs(E)
flux density bs(E) of
of photons
photons ~

of energy
energy E, E, and
and subject to an applied bias V.
V. We
We will
wil use
use jn(E,x), qDn ~:
.-1""
of subject to applied bias jn(E, x) == qDn ~: . (6.19)
(6.19)
jp(E, x)
jp(E, x) to
to denote
denote thethe solutions
solutions for
for the
the electron
electron and hole current
and hole current den-
den-
sities, respectively, at depth under monochromatic ilumination. The
sities, respectively, at depth x under monochromatic illumination. The For a
For a p region which is
region which is thick compared with Ln the
compared with the boundary
boundary condition
condition
current densities
current densities for
for the panchromatic
panchromatic spectrum
spectrum are are easily
easily constructed,
constructed, -xp) == no
n( -xp) no is
is adequate.
adequate.
- - _. __._
. --

154 ThePhysics
The Physicsof
ofSolar
Solar Cells
Cells Analysisof
Analysis ofthe
thep-n
p-n Junction
Junction 155
155
154

In
In the
the neutral
neutral nn region
region the
the hole
hole population
population follows
follows an
an analogous
analogous set
set of
of pp region
region space
space charge
charge nn region
region
equations.
equations. I region
region
!
2
dd2p
dx2
p __ (P
(p- -po)+
Po) g(E,
qL~ + Dp
x) =
geE, x) _ 00 x > Wn (6.20)
(6.20) I II
Dp - x ~ Wn

~P------~I->--~~~~~I
dx 2
~n
Fpn
with the
with the boundary
boundary conditions
conditions Fpp r- '"""Iil
I!
p-po=
n2
Nd
Nd
2
p - Po =-n --(eqV/kBT
i (e QV jkBT at xx == Wn
- -1) 1) at Wn (6.21)
(6.21)
p=N
p=N I
I
~!-----------~Ei
i n=N
n=N dd
dp )
aa
and
and pp varying
np =
2 varing
nn varying
varing np = nnI2 exp( qV/kT)
exp(qVIkT)
-Dp-dp= =Sp(p
-Dp- - Po at
at xx == Wn
Wn (6.22)
(6.22) i
dx Sp(P - Po)
dx
Fig. 6.4.
Fig. 6.4. Fermi
Fermilevels
levels and depletion approximation.
and intrinsic potential in the depletion approximation.Within Within the
nn22 spacecharge
space chargeregion
regionnand
nand pp are
are determined
determined by EFEFnn-- E
E j and
and E EFp'
E j -- EF ' respectively,
respectively, and
and
where Po = it
where Po = it.
vary continuously
vary continuously from
from the
the majority carrier (doping)" densityatatone
(doping)" density
p
oneside
sideto to the
the minority
The hole current density
density obeys
The hole current
. dp
obeys

Jp(E, x) = -qDp
jp(E, x) -qDp dx
dp
dx .. (6.23)
carrier density
carrier density on
on the other.

From Eqs. 3.37 and

Eqs. 3.37 and 3.38
3.38nand
nand p are
are given by
The majority carrier
carrier concentrations
concentrations are
are simply
simply
p=Nd xx -(
< -wp
-wp (6.24) n = ne(EFn -E)/kBT

in
in the
the pp region
region and
and
and
n=Nd x>
x ~ Wn
Wn (6.25) p = ne(E1-EFp)/kBT

in the n
in the n region.
region. Ei is
E is found
found from Ei ==-qcp
from E -q<jJwhere
wherecp
<jJ is
is the
thesolution
solutiontotoPoisson's
Poisson'sequation,
equation,
given by
by Eqs.
Eqs. 6.8
6.8 and
and 6.9.
6.9. Knowledge
Knowledge of EFn,EFn, EFp
EFp and
and E
Ei determines
determines nn
6.4.2.
6.4.2. Currents
C urrents and
andcarrier
carrierdensities
densities in
inthe
thespace
space charge
charge and p completely within
within the
the SCR
SCR and
and ensures that nand
ensures that nand pp are
are continuous
continuous
region
region across the
across the boundaries
boundaries atat xx == -Wn andx x= =wp'
-Wn and Figure6.4
wp.Figure 6.4shows
showshowhowEFEF
n n,,
EF pp and
EF and Ei
E vary across the region
region within the
the depletion
depletion approximation.
approximation.
The
The space
space charge
charge region
region isis assumed
assumed free
free of carriers for
for the
the purpose
purpose of
of cal-
cal- The
The depletion
depletion region
region current
current can
can be
be determined
determined from
from carrier
carrier continuity.
continuity.
culating
culating thethe electrostatic
electrostatic potentiaL. One approach
potential. One approach isis to ignore
ignore the S~R
the SCR Integrating
Integrating Eq.
Eq. 4.87
4.87 across
across the
theSCR
SCRwe we find
find
completely
completely in the calculation
calculation of current. A A better,
better, though
thoughnotnotself con~ls
selfconsis-
withi~the wn
tent,
tent , approximation
from
from the
approximation is
theFermi
Fermilevels
is to
levels and
to calculate
calculate nand
and the
nandppwithin
theelectrostatic
electrostaticpotentiaL.
potentlal.
thespace
spacecharge
chargeregion
reglOn
j
Jscr == qqJ rWn
Jser -Wp (U -- G)dx
-W (U
p
G)dx (6.27)
(6.27)
The
The depletion
depletion approximation
approximation requires
requires that
that EF
EF nand
nandEF
EFpp are
are constant
constant
across ~." where
where JJser isequal
scr is equaltotoboth
both the
the net
net electron
electron current generated between -wp
-w p
across the
the region,
region, thus
thus ,I" and Wn and to the net hole current generated between Wn and -wp' Jser
iPO'_ and Wn and to the net hole current generated between Wn and -w p . Jscr
EFn(X)
EFn(X) == EFn(Wn)
EFn(wn) can
can be
be broken
broken down into spectral
spectral contributions,
contributions, jser(E),
jscr(E), such
such that Jscr ==
that Jser
EFp(X)
EFp(X) == EFp(-Wp)
EFp(-W p )
(6.26)
(6.26) J jscr(E)dE. U is known from nand p given the form of the recombination
J jser(E)dE. U is known from nand p given the form of the recombination
qV rate,
rate,and
andGGisisknown
knownfrom
from the
theincident
incident spectrum
spectrumandandEq.
Eq.6.16.
6.16.
qV ==EFn
EFn (x)
(x) -- EFp(X)
EFp(X) -- wp < <
Wp-( x x-( Wn
w n.
156 The Physics
The Physics of Solar Cells
Cells Analysis of the
Analysis of thep--n
p-- Junction
Junction
157

6.4.3. current density

Total current
6.4.3. Total density and

The net current

The net
constant
current is
constant through
is given
through the
givenbyby the
device in
the device
sumofofIIn
the sum
insteady
steadystate.
and JJpp at
n and at any
any point
EvaluatingJJ at
state. Evaluating
point and
at -wp
-wp we
and is
we find
is
find
Dn Ln Ln Dn
')ne-a(xp-wp)(n cosh (xp-wp) + sinh (xp-wp)) _ (n + aLn)J

Bn =
- no
L coshDn
(eqV/kBT -1)rn Ln
(xp-wp) + sinh Ln
(xp-wp)J
JJ = - In ( -w
= -In( p) -
-wp) J p ( -w
- Jp( p)
-wp) Dn Ln Ln
SnLn sinh (xp-wp) + cosh (xp-wp)

(6.32)
(6.32)
= -In(-wp)- - Jp(wn)
= -In(-wp) Jp(w n )-- Jscr
Jscr
From the
the definition
definition of jn,
jn, Eq.
Eq. 6.19,
6.19, we
we have
= - Jjn(E, -wp)dE - Jjp(E,wn)dE -
= - J jn(E, -wp)dE - J jp(E,wn)dE - J jscr(E)dE
J jscr(E)dE (6.28)
(6.28)
From

jn(E, -wp) = qDn ( - ~: - a')ne-a(Xp-Wp)) . (6.33)

(6.33)
using the
using the result,
result, from Eq. 4.87,
4.87, that
that
Hence,
rn
Jp(-wp) = Jp(wn) - Lwp (U - G)dx.
In(-Wp) = J jn(E, -wp)dE
jn(E, -w
jn(E, p) and
-wp) jp(E, wn)
andjp(E, wn) are
are found
found by
by evaluating
evaluating Eqs.
Eqs. 6.19
6.19 and
and 6.23
6.23 at
at
the edges
edges ofof the
the SCRSCR using
using the
the solutions forn(x)
solutions for and p(x).
n(x) and for
p(x). The result for with
J is
is identical we evaluate
identical ififwe evaluate the
the current
current at
atWn.
Wn
We havechosen
We have chosenthe thesign
signconvention
conventionhereheresuch
suchthat
thattotal current JJ is
total current is jn(E, -w p)
-wp)
positive when
when flowing
flowing from
from pp to circuit. This
to nn through the external circuit. Thismeans
means q(1
q(1 -- R)bsaLn
R)bsaLn
that photocurrent
photocurrent is positive.
positive. This isis opposite
opposite to the
the normal
normalengineering
engineering (a 2 L; -1)
(a2L~ -1)
convention,
convention, and is responsible for for the minus
minus signs in Eq.
Eq. 6.28.
6.28.

6.5. General Solution for J(V)

Solution for
x Dn Dn
LnLnLnLnDn SnLn sinh (xp-wp) + cosh (xp-wp)
f e-a(xp-wp) (SnLn cosh (xp-wp) + sinh (xp-wp)) - (. + aLn)
6.5. General J(V)

Equation 6.15 for n has

has the
the general
general solution + aLne-a(xp-wp) J

n(E, x) =
= An (-x -
cosh ( -x Ln
An cosh
Wp )
z. wp ) ++ Bn sinh ( -x z.
Bn sinh
(-x -
Lnwp )
Wp )

+ Dn LnDnLn (6 34)
qDnno(eqV/kBT - 1) f n cosh (xp-wp) + sinh (xp-wp) J
+ ')ne-a(x+xp)
(6.29)
(6.29) Ln SnLn sinh (xp-wp) + cosh (xp-wp)(6.34)
Ln Ln .
where For holes
For holes in
in the
the nn region
region Eq.
Eq. 6.20 for pp has
6.20 for has the
the general
general solution
solution

a(1 -- R)bsL~
')n =
'Yn
a(1
= Dn(a2
R)bsL~
L~ -- 1)
Dn(a2 L; 1) ..
(6.30)
(6.30) p(E, x) =
p(E, x) = Ap cosh (x
Ap cosh ~pWn +
(x ~pWn )) + Bp sinh (x
Bp sinh ~pWn
(x 1pwn)) __ ')pe-a(x+xp) (6.35)
'Ype-<>(x+xp ) (6.35)
..
-<>
l"where ')p is given by Eq. 6.30 with Ln, Dn replaced by Lp, Dp and Ap and
The boundary
boundary conditions,
conditions, Eqs.
Eqs. 6.17
6.17 and 6.18, determine the coeffcients An
coefficients An jI"where 'Yp is given by Eq. 6.30 with Ln, Dn replaced by Lp, Dp and Ap and
and Bn: Bp are obtained
Bp are obtained from
from the
the boundary
boundary conditions
conditions 6.21
6.21 and
and 6.22
6.22 as
as

An = no( eqV /kT) - ')ne-a(xp-wp) (6.31)

(6.31) Ap = Po
(eqV/kT -1) - ')pe-a(xp+wn) (6.36)
(6.36)
158 The Physics
The Physics of
of Solar
Solar Cells
Cells Analysis of
Analysis of the
thep-n
p-n Junction
Junction 159
159
158

and and generation,

and generation, due
due to
to the light,
and

'Y'Y p Dp Lp Lp Dp p
e-a(xp+wn)[(~cosh("'n-wn) +sinh("'n-wn) )-(~-QL )e-a(xn-wn)j
P e-,,(xp+Wn)((~cosh
_po(eqV/kBT
Dp (Xn-Wn)
L Dp Lp Lp
-l)[~cosh
Lp +sinh (Xn-Wn)
Lp
("'n- Wn ) + sinh
)-(~-aL
Dp
sinh (%n-wn)j
(xn-wn)J
)e-,,(xn-wn)J
P gen =
JJgen J
= J jgen(E)dE
jgen(E)dE
(6.41)
_po(eaV/kBT -l)r~cosh (xn-wn)
Dp + Lp Lp wn (6.41)
Bp=--------------~~--~--~~----~~~-------------
Bp ~
~Dp . h . (Xn-Wn)
h (%n -Wn) ++ h h(Xn-Wn)
DpSillsm Lp Lp cos (%n -Wn)
cos Lp Lp
(6.37)
(6.37)
Jgen(E)== -q
Jgen(E) fWn
-q Lwp
-w j p
geE,
g(E, x)dx.

The bias dependent

The dependent and light dependent
dependent currents are, again, independent
This gives the solution for
This gives for the
the hole
hole current
current at n,
at WWn, and opposite in sign. If the dominant recombination
recombination process is SRH recom-
bination through trap
trap states
states then,
then, using
using Eq. 4.79 for U,
4.79 for
(6.38)

hence
jp(E, Wn) = -qDp (~: - a'Ype-a(Xp+wn)) (6.38)
Jreewn
j
J rec = np - n~
=-q
+ +
_q1 +dx
wn

-W
-Wpp
np-n~

'Tn(P + Pt)
Tn(p
1

Tp(n + nt)
Pt) + 'Tp(n Ti)
dx (6.42)
(6.42)
hence
nand PPdetermined
with nand determinedfrom
from EFn,
EF n , EFp
EFp and
and EEi as
as explained
explained above, and nt nt
Jp(Wn) = J jp(E,wn)dE and Pt given by Eqs. 4.72
4.72 and
and 4.77.
4.77. The
The full
full form
form of
of the
the SRH
SRH recombination
recombination
rate is used, rather than the
used, rather the linear
linear approximation,
approximation, because
because in in this region
region
where
where both nand
nandPP vary
vary strongly. InIn the
the depletion
depletion approximation
approximationEF EFnand
nand EFEF pare
constant across the SCR
across the and Ei
SCR and E is
is aa known
known function of x, given
of x, given by
byEqs.
Eqs. 6.8
6.8
jp(E, Wn) and 6.9.
6.9. If we
we make
make the approximation
approximation that that EEi varies
varies linearly
linearly across
across the
the
depletion region
depletion region then Eq. 6.42
6.42 can be evaluated analytically to yield yield .
_ _ q(1 - R)bsaLp -a(xp+wn)
- (a2 L~ _ 1) e J (V) _ qni(w n + wp ) 2sinh(qV/2kT)
~
Jree(V) -= qn(wn + wp) 2sinh(qV/2kT) ~E
TnTp
v''Tn'Tp q(Vb
q(Vbi - V)/kT
V)/kT
(6.43)
(6.43)
sinh (Xn-Wn))_(SpLp_aL )e-a(xn-Wn)
x Dp Lp
SpLp . h Lp
(Xn-wn) +Dp
Dp sin Lp cos Lp
+
P
h (Xn-wn)
aLp 1
factor ~Etends
where the factor tends to
to7r /2 at suffciently
7r /2 sufficiently large
large forward
forward bias
bias Sah
[Sah et
etal.,
al.,
\ (SpLp cosh (Xn-Wn) 1957].
1957J.

+ p Dp Lp Lp
qD po(eqV/kBT - 1) \ SpLp cosh (Xn-Wn) + sinh (Xn-wn) 1
(6.39)
The spectral contributions to the
by integrating geE,
g(E, x) across
the photocurrent,
across the SCR
photocurrent, jgen
SCR (Eq.
(Eq. 6.41).
6.41). Thus
jgen are
are found simply
simply

Dp Lp Lp
Lp ~ sinh (Xn-wn) + cosh (Xn-Wn) .
jgen(E) = qbs(1 - R)e-a(xp-wp)(1 _ e-a(wp+wn)), (6.44)
(6.44)
For each of Eqs.
Eqs. 6.34
6.34 and
and 6.39,
6.39, the
the first
first term is proportional bs and
to bs
proportional to and is
is due
due
expressing the fact
expressing the fact the
the number
number of
of carriers
carriers generated
generated isis simply
simply given
given by
by
to the
the light,
light, and
and the
the second
second term
term is
is due
due to
to the
the electric
electric bias.
bias. The
The light
light and
and
the number
number of of photons
photons absorbed.
absorbed. It is
is reasonable
reasonable that carriers
carriers should
should be
be
currents are
bias induced currents are independent.
independent. This
Thisisis aa consequence
consequence of the linearity
linearity
collected efficiently
effciently in the SCR
SCR on
on account
account ofof the
the built
built in
infield.
field.
of the differential
differential equations for nand
equations for nand p.p.Note
Notealsoalsothe thedifference
difference ininsigns:
signs:
Taking
Taking Eqs.
Eqs. 6.43
6.43 and 6.44 into 6.27,
6.27, and
and integrating
integrating Eq.
Eq. 6.44
6.44 over photon
photon
the
the light
light generated
generated and
and bias
bias driven
driven currents
currents act
actin inopposite
opposite directions.
directions.
energy
energy we
we obtain,
obtain,
The
The third
thirdcontribution,
contribution,Jsell
JSCf!given
givenby
byEq.
Eq. 6.27,
6.27, isis sometimes
sometimes referred
referred to
to
..
.~
as
as the
the recombination-generation current. It can
recombination-generation current. can be be split
split into
into contributions
contributions t~ qni (w n++wp)
J (V) == qn(wn
Jser(V)
sinh( qV /2kT) ~
w p )22sinh(qV/2kT) 7r
scr
from
from recombination, due to the the applied
applied bias
bias TnTp
v''Tn'Tp q(Vbq(Vbi -- V)/kT
V)/kT22

Jree
f
jwn
wn
J rec == qq -w Udx
-Wp
p
Udx (6.40)
(6.40) - q J (1 - R)bse-a(xp-w p)(1 -:- e-c:r(wp+wn)dE .
- q J (1 - R)bse-a(xp-wp) (1 -: e-a(wp+wn))dE .
(6.45)
(6.45)
 160 ThePhysics
The PhysicsofofSolar
SolarCells
Cells Analysis
Analysis ofofthe
the p-n
p-nJunction
Junction
160 161
161

Equations 6.28, 6.34, 6.39 and 6.45 give us the full solution for the current- 1.5 , - -_ _ _ _ _ _ _ _ _ _ _ _ _-.
1.5
Equations 6.28, 6.34, 6.39 and 6.45 give us the full solution for the current-
voltage characteristic of the junction in the depletion approximation.
voltage characteristic of the junction in the depletion approximation. Ec
Below we consider how the solution simplifies in various special cases.
Below we consider how the solution simplifies in various special cases. Vb;

-~~......>>-
0.5
0.5
CD
CI
6.6. [rn Junction in the Dark EFn EFp
6.6. rn Junction in the Dark
00
6.6.1. At equilibrium
6.6.1. At equilibrium
C)
..
CD
CI
e 0.5 1.5 22 2.5
2.5
i:c
In equilibrium there is no illumination (b s = 0) and no applied bias (V = 0), W -0.5
W -0.5
In equilbrium there is no ilumination (bs = 0) and no applied bias (V = 0),
so all contributions to the current density J are zero. The carrier popula-
so all contributions to the current density J are zero. The carrier popula- -1
-1
tions obey Ev
tions obey
-1.5
-1.5
p(x) = Na ,
p(x) = Na,
n(x)
n(x)
= no
= no for < -Wp
for xx .( -w p (6.46)
(6.46)
Distance
DistanceIIlLm
JLm
p(x} = Po, p(x) = Nd
p(x) = Po, p(x) = Nd
for x
for > -Wn
x ;: -Wn (6.47)
(6.47) (a)
(a)
and
and 1.0&17
1.06+17
pn=nj 2
wp .(<xx .(<wn
for -- Wp Wn ..
1.0&15
1.06+15
pn = nf for '"
n
'1 1.06+13
1.0&13 pP n
'eE
Clearly there will be no minority carrier diffusion currents in either neutral
Clearly there wil be no minority carrier diffusion currents in either neutral
region and the fact that pn = nr
in the space charge region means that
region and the fact that pn = nt in the space charge region means that
-.a-~
()
() 1.06+11
1.0& 11
......
1.0E+09
1.06+09
there is no net recombination. The bands and carrier profiles are illustrated
there is no net recombination. The bands and carrier profiles are ilustrated eniiCi: 1.0&07
1.06+07
in Fig. 6.5. CD 1.0&05
Q) 1.06+05
in Fig. 6.5. 'C
'C
..
~ 1.0&03
1.06+03
CD
Q)

6.6.2. Under applied bias

6.6.2. Under applied bias
.:
'a..
o
:::: 1.06+01
~
C'C'
1.0&01
\
\1.5
CS 1.0&01
1.0E-01
0 0.5
0.5 1.5 22 2.5
2.5
If a bias is applied to the junction in the dark, the built in potential barrier 1,0&03
1.0E-03 J
If a bias is applied to the junction in the dark, the built in potential barrier
is reduced and more majority carriers are able to diffuse across the junction, 1.0&05
1.0E-05
is reduced and more majority carriers are able to diffse across the junction,
so that there is now a net current of electrons from n to p and holes from
so that there is now a net current of electrons from n to p and holes from Distance II lLm
Distance J.l.m
p to n. This is sometimes referred to as the injection of majority carriers.
p to n. This is sometimes referred to as the injection of majority carriers.
Because the quasi Fermi levels in the SCR are split by the applied bias, (b)
(b)
Because the quasi Fermi levels in the SCR are split by the applied bias,
there is net recombination in that region which adds to the current. The Fig,6.5.
~ig: 6.5. (a)
(a) Band
Band profiles and (b)
(b) carrier
carrier densities
densitiesfor
fora aGaAs
GaAsp-n
p- junction
junction inin equi-
there is net recombination in that region which adds to the current. The librium.The
profiles and
Theparameters
parametersused used were xp = 1 .m, Xn=== 22 .m, Na =- 1017
equi-
cm-3,
band profile is illustrated in Fig. 6.6. lIbrIum. were xp == 1 Hm x Hm N 1017 -3
band profile is ilustrated in Fig. 6.6. N. _ 16 -3 ,.. , n ,.., a -
Nd = 1016 cm-3. Ln = Lp = 1 .m and Sn = Sp = O. Calculated using PC1D Basore,
cm,
In the dark bs(E) = 0 for all E and only the second term of each of d - 10 cm . Ln == Lp == 1 I-'m and Sn == Sp == O. Calculated using PC1D [Basore
In the dark bs(E) = 0 for all E and only the second term of each of 1991J as are
19911 as are Figs.
Figs. 6.6,
6.6,6.8
6.8and
and 6.11.
6.11. '
Eqs. 6.34, 6.39 and 6.45 will be non zero. Because all of these contributions
Eqs. 6.34, 6.39 and 6.45 wil be non zero. Because all of these contributions
represent a current which flows in the direction of the bias, and in the
represent a current which flows in the direction of the bias, and in the
opposite sense to the photo current current itit isis convenient
convenienttotodefine
defineaadark
darkcurrent
current FromEqs.
;" From Eqs.6.34
6.34and
and6.39
6.39ititisisclear
clearthat
thatboth
boththetheminority
minorityhole
holeand
andminority
minority
opposite sense to the photo
Jdark(V) which is positive,
Jdark(V) which is positive,
electroncurrents
electron currentsare
areproportional
proportionalto to(eqV/kBT
(eqV/kBT - - I).
1).InInthe
thelimit
limitwhere
where the
the
neutral p layer is thick compared to Ln and the n layer
neutral p layer is thick compared to Ln and the n layer thick compared thick compared
(6.48)
Jdark = In (-wp) + Jp( wn) + Jser (6.48) toto Lp,
Lp, surface
surface recombination
recombinationbecomes becomesirrelevant
irrelevantandandI Inand
n
andJJp have
p
havethethe
162 The Physics
The Physics of
of Solar
Solar Cells
Cells Analysis of
Analysis of the
thep-n
p-n Junction
Junction 163
163
162

1.5
1.5 In this
In this limit, p(x) and n(x) have
limit, p(x) have the
the simple
simple forms
forms
~
Ec P - Po = Po (e qV /KBT _ 1)e-(x-wn )/Lp (6.51)
Ec Vbi- V
Vbi- V P - Po = Po (eqV/KBT - 1)e-(x-wn)/Lp (6.51)
for xx >
for ? Wn
Wn and
>::
--
C
G)
CI)

>;:-
~
2'
G)
CI)
0.5
0.5

00
E
EFn
Fn

EFp
EFp
II.

V
for xx <
for -( -w
-wpp which
n - no = no(eqV/kBT _ 1)e(x+wp)/Ln

which express the factfact that the

the mobile
mobile minority carrier density
(6.52)
(6.52)

C 2.5
W
W U." 1.5
1.5 22 2.5 is significant
is significantonly
onlywithin
withinaadiffusion
diffsion length of the depleted region.
region. Further
-0.5
-0.5
away, minority
away, minority carriers
carriers are
are more
more likely
likely to
to be
be lost by recombination before
E they reach the junction.
Ev
-1
Since both
Since both IInn and Jp
Jp result from minority carrier
from minority carrierdiffusion
diffsion they can be
-1
grouped together
grouped together asas aa diffusion
diffusion current, Jdiff
i.m
Distance I J.1m
Jdiff(V) = In(-wp) + Jp(wn) = Jdiff,o(eqV/kBT -1) (6.53)
(6.53)
(a)
where
1.0E+18
1.0E<-1S
'? 1.0&16
.., 1.0E<-16
r Jdiff,O 2( (NaLn
2
=qniqni Dn++Dp
Dn
NaLn Dp )) .
NdLp (6.54)
p l n Jdiff ,O = NdLp . (6.54)

--
'E
~
U

en
:g
C
1.0E<-14 I
5 1.0E+14

~1.0E+12
1.0E+12
1.0E+10
1.0E+10
Including
changes
the finite
Including the finite layer
layer thickness
changes the value of Jdiff,
thickness and
Jdiff, but
and surface
but not the bias
The recombination current fromfrom the
surface recombination
bias dependence.
dependence.
the depletion
depletion region
region given
velocity
recombination velocity

given by 6.43
6.43 has
~ 1.0E+08
~ 1.0E<-OS
..... the approximate form
CI) 11.0E+06
..
.9! .OE+06
...
"C
1.0E+04
1.0E+04
J Jscr(V) =
Jscr(V) Jscr,o(V/2kBT -1)
= Jscr,o(eqV/2kBT -1) (6.55)
0
CIS
0 11.0E<-02
.OE+02
(6.55)

1.0E+O
where
1.0E+OO
2.5 33
qni(wn + wp)
oo 0.5
0.5

Distance
Distance I i.m
J.1m
1.5
1.5 22 2.5
J. -_ qni(wn
J.scr,O
ser 0 -
, JTnTp
yTnTp
-+ wp)
~ .(656)
..(6.56)
(b) Note that
that Jscr
J ser has
has aa different
different dependence on both ni
dependence on ni and
and V
V to
toJdiff.
J diff .

Fig. 6,6.
6.6. (a)
(a)Band
Bandprofie
profileand
and(b)(b)carrier
carrierdensities
densities for biased~
for biased p- junction
junction in
inthe
the dark.
dark.
Combining termsterms we
we have
have
Parameters are
are the
the same
same as
as for
for Fig.
Fig. 6,5
6.5 and
and VV == 0.5
0.5 V,
V. =
Jdiff,o(eqV/kBT -1)
Jdark(V) = Jdiff,o(eqV/kBT +
Jscr,o(eqV/2kBT -1)
Jdark(V) -1) + Jscr,o(eqV/2kBT -1)

+ Jrad,o(eqV/kBT
+ Jrad,O(eqV -1) /kBT - 1) (6.57)
(6.57)
simple
simple approximate
approximate forms
forms
where
where we have included
we have included aa termterm for thethe radiative
radiative recombination
recombination current,
current,
J (_
In(-wp)) = qn? Dn (eqV /kBT _-1)
= a;:Z:(eqV/kBT 1) (6.49)
(6.49) Jrad.
Jrad . From Eq.
Eq. 4.57
4.57 itit is
is clear
clear that
that the radiative
radiative current has has the
the same
same bias
bias
n wp NaLn
?'dependence
i" dependence as the diffsion current. Jrad
diffusion current. J radmay be significant in high quality,
may be significant in high quality,
and
and direct
direct band
band gap
gap materials.
materials. The The relative
relative importance
importance of of the
the terms
terms depends
depends on on

p n NdLp .
J (w ) = qnt Dp (eqV /kBT - 1) (6.50)
(6.50)
the
the importance
importance of
silcon,
silicon, diffsion
of recombination
recombination in the
diffusionlengths
lengthsare arelong
the SCR.
longcompared
SCR. In indirect
compared to to the
indirect gap
the depletion
gap materials
materials like
depletion width
width and
like
and very
very
164 ThePhysics
The PhysicsofofSolar
SolarCells
Cells Analysis
Analysisofofthe p-nJunction
thep-n Junction 165
165
164

little recombination
little recombinationoccurs
occursininthe
the depleted
depleted region,
region, so
so JJser can be
ser can be ignored.
ignored. In heterojunctions,
In heterojunctions,tunnelling
tunnellng through
through barriers
barriers may
may givegive rise
rise to
to m
m values
values
In that case we have
greater than 2. The effect of an ideality factor greater than 1 is to reduce
greater than 2. The effect of an ideality factor greater than 1 is to reduce
In that case we have
the fill
the fillfactor
factor of
ofthe
the solar
solar cell.
cell. For
For ideal
ideal diodes
diodes the
the fill
fill factor
factor is
is 86%.
86%.
(6.58)
Jdark:: Jdiff,o(eaV/kBT -1). (6.58)

This is
This is the
the Shockley
Shockleyor or 'ideal'
'ideal' diode
diode equation
equation and
and isis often
often quoted
quoted for
for the
the 6.7. :n Junction under
6.7. p-n under Illumination
Illumination
dark current of a solar cell.
dark current of a solar cell. 6.7.1. Short
6.7.1. circuit
Short circuit
In direct
In direct band
band gap
gap materials where absorption
materials where absorption isis strong
strong or
or where
where the
the
SCR is wide, recombination within the depleted region may
SCR is wide, recombination within the depleted region may be dominant. be dominant. When the
When the junction
junction isis illuminated,
iluminated, light light creates
creates electron-hole pairs in
electron-hole pairs in all
all
Then three regions.
three regions.nand nand p are are then
then enhanced
enhanced above abovetheir
their equilibrium
equilbrium values,
values,
Then
and the electron and hole quasi Fermi
and levels are
Fermi levels are split.
split. The
The electric
electric field
field at
at
~ (qV /kBT - 1)
:: JJser,O(eaV/kBT (6.59)
(6.59)
1Jdark
dark ~ ser,O e - 1) the
the junction
junction actsacts toto separate
separate the the pairs
pairs byby driving
driving minority carriers across
minority carriers across

If more
If more than
than one
one process
process isis important
important then
then Jdark may appear
Jdark may appear to vary like the junction.
the junction. We
We wil will
first firstexpressions
obtain obtain for expressions
the photo for the photo current generated
current generated
at short circuit, Jsc.
at In these
Jse . In these conditions
conditionsVV== 00 so so that,
that, within the depletion
~ TJo(eaV/mkBT
1Jdark::
qV 1) .
(e /mkBT - -1). (6.60)
(6.60) approximation, EF
approximation, EFnandnand EFpp are are equal
equal across
acrossthe theSCR
SCR andand there
there is
is no
dark ~ "0

where JJo isis aa constant

where and m
constant and m is
is the
the ideality
ideality factor.
factor. An
An ideal
ideal diode
diode has
has
net recombination
net recombination there. there. Figure
Figure 6.8 6.8illustrates
ilustrates the band profile
profile and carrier
o densities.
m = 1. m can be inferred
m = 1. m can be inferred fromfrom
Now
Now only
only thethe first
first term in each of Eqs. 6.34 and 6.39 is is non-zero
non-zero and all
11 kT dIn
kT dIn Jdark
Jdark (6.61) are negative,
negative, representing positivecontributions
representing positive contributionstoto the the photocurrent.
photocurrent. For
-
m=-
m q q dV
dV the minority
minority carrier currents
currents from from thethe neutral
neutral regions
regions wewe have
have .
In
In real
real cells
cells we
we often
often see
see aa change
change in
in slope
slope from
from Jser
J ser dominating
dominating atat low
low
bias jn(E, w p)
bias (m
(m == 2),
2), to
to Jdiff
Jdiff or
or Jrad
Jrad at
at high
high bias
bias (m
(m ==1)
1)asasshown
shown in
in Fig.
Fig. 6.7.
6.7 . jn(E, wp)

= [qb s(1 - R)aLn]

1.E+06 -----..----...
(a2L~
= (abs(1
(a2 L~ -1)
- R)aLn)
- 1)
1.E+08

..'e
..
'E 1.E+04
() 1.E+04
()
cl 1.E+02
1.E+02
1.E+06
1.E+06
X Dn DnDnLn+Ln
X
{
(~
n
Ln
Ln
+ aLn) - e-a(xp-wp ) (nf.n.

SnLn sinh
SnLn
Dn
sinh (xp-wp)
f (SnLn + aLn) - e-a(xp-wp) Ln
(SnLn
Dn
cosh
cosh (xp-wp)
(xp wp) + cosh (xp-wp )
(xp-w
Ln
p) + sinh

Ln + sinh (XP-WP))
cosh (xp-wp)
(xp-w p
Ln
)

~'-e"
E 1.E+OO
1.E+OO
1.E-02
~ 1.E-02
ii
cQlIIIc
l.E-04
l.E-04
- aLne-a(xp-Wp)
- aLne-a(xp-w p) } 1 (6.62)
(6.62)

..
C ..
't"CGI 1.E-06
1.E-06
c 1.E-OB
~ 1.E-OB
and
and
::~ 1.E-l0
1.E-l0
CJ:::s
U 1.E-12
1.E-12 jp(E, wn)
l.E-14
l.E-14
o0 0.5 1.5
1.5
0.5
Bias
BiasIV
IV ( a2 L~ - 1) 1 P
= (abs(1 - R)aLp) e-a(xp+wn) f aL

Fig. 6.7.
Fig, 6.7. Dark
Dark current
current ofof
a anon-ideal
non-idealdiode,
diode,resolved
resolvedinto
intocontributions
contributionsfrom
fromdiffusion
diffusion Dp Lp . +Lp+ coshP(Xn-Wn) .
SpLp (cosh (Xn-Wn) - e-a(xn-.w n)).+ sinh (Xn-Wn) + aL e-a(xn-Wn) 1

SpLp sinh (Xn-Wn)

and
andSCR
SCRrecombination.
bination
current
recombination.As
binationcurrent
currentand
currentdepends
andthe
dependsupon
AsVVincreases
theslope
uponthe
slopeof
thecarrier
increasesthe
oflog
thediffusion
log JJagainst
carrierlifetimes:
diffusioncurrent
againstVVchanges.
lifetimes:for
currentovertakes
changes.The
forshorter
overtakesthe
Theimportance
shorterlifetimes,
theSCR
importanceof
lifetimes, the
SCRrecom-

thetransition
ofthe
recom-
theSCRSCR
transitiontotodiffu-
diffu-
Dp Lp Lp
SpLp sinh (Xn-Wn)
Dp Lp
cosh (Xn-Wn)
Lp
(6.63)
.

(6.63)
sive
sivebehaviour
behaviouroccurs
occursat
athigher
higherVVthanthanforforlonger
longerlifetimes,
lifetimes.Plots
Plotsare
areshown
shownforforthethecases
cases
where
whereelectron
electron and
andhole
holelifetimes
lifetimes are
are both
bothequal
equaltoto11ms,ms,and
andboth
bothequal
equaltoto1 1.s.
J.Ls.
The
Thegeneration
generationcurrent
currentininthe
theSCR,
SCR,jgen,
jgen,isisgiven
givenby
byEq.
Eq.6.44.
6.44.
 :1

166 ThePhysics
The Physicsof
ofSolar
Solar Cells
Cells Analysis
Analysisofofthe p-n Junction
thep--n Junction 167
166 167

1.5
1.5
The quantum
The quantum efficiency
effciency of
of the
the cell
cellat
at different
differentphoton energiesE,
photon energies E, defined
defined in
in
~ Chapter
Chapter 1,
1, isis for
for some
some purposes
purposesofofmore
moreinterest than JJse
interestthan sc since
sinceit
it does
does not
not

~~
Vb!
Vtj, dependon
depend onthe
theincident
incidentspectrum.
spectrum.We obtainQE(E)
Weobtain QE(E) easily
easilyfrom
fromthe
thespectral
spectral
EFn
E Fn photo
photo current since
current sinceeach
eachcomponent
componentofofj(E) j(E) isis proportional
proportional toto bs(E):
bs(E):
>CD::CD
-:: 0.5

->ei-
~
0.5

0
0 2.5
QE(E) = -jn(E, -wp) - jp(E, wn) - jgen(E) .
qbs (E)
(6.66)
(6.66)

\
CD 0.5
0.5 . 1.5
1.5 22 2.5
c
CD
C
u. -0.5
u.I -0.5 EFP
" EFP
6.7.2. Photocurrent
6.7.2. Photocurrent and
and QE
QE in
in special
special cases
cases
-1
-1
~f\. E.
Ev Let's consider
Let's consider the the form
form of of the
the photocurrent
photocurrent and and the QE
QE inin some
some special
special
-1.5
-1 .5
cases.
cases.
Distance II lJm In thecasecase
In the of a of a p-n
thick thick
cell p-n cellthewhere
where both neutral both the neutral layers are much
layers are much
Distance ~m
thicker
thicker than
than thethe diffusion
diffsion length
length the the electron
electron and
and hole
hole currents
currents can
can be
be
(a)
approximated
approximated by by

..,C' 1.0&16
1.06+-16
1.0&18
1.0&18 -r---------------'l
n
n
jn(E, -w
jn(E, p) ~
-wp) ~ qb s (l- R)e-Ct(xp-w
qbs(1- R)e-a(xp-wp)p
) C:~~n)
:~~n) C (6.67)
(6.67)
1.0&14 i P
-~ 1.0&12
E 1.06+-14
'5
U
'i 1.0&12
P and

.; ) ~ qb (1 _ R)e-a(xp+w n ) ( aLp )
J.p (E , wwn) (6.68)
1.0&10
cC 1.06+-10 jp(E, n ~~ qbs(1
s aLp ..
- R)e-a(xp+wn) 1C :;Lp) + (6.68)
~CD 1.0E+08
1.0E+08
".!!!

~ 1.0E+06
1.0E+06
Here only electrons
electrons generated
region are collected.
generated within
within one
one diffusion
diffsion length
collected. In the other extreme, where
length of
Ln and
where Ln
of the
and Lp
the space
Lp are
space charge
are much
charge
much longer
longer
'E 11.0&04
~
~
.0Et
as
as
o 1.0E+2 than the
than andnnregions,
the pp and regions, respectively,
respectively, we
we have
have
0 1.0E+02
1.0E+OO
1.0EtOO
o0 0.5 1.5
1.5 22 2.5
2.5 33 jn(E, -wp) ~ qbs(1- R) (1 + ~) (1- e-a(xp-wp)) (6.69)
0.5 aDn (6.69)
Distance
Distance II l-m
~m and
and
(b)
(b)
~
jp(E, w n ) ~ qbs(1-
jp(E,wn) R)e-a(xp+w ) (1-
qbs (1 - R)e-a(xp+wn) (1- a~p) (1- a~p)
(1 -e-a(xn-Wn)).
n (6.70)
e-a(xn-W )). (6.70) n
Fig.
F ' 6.8.
68 (a) (a)Band
Bandprofie
profileand
and(b)
(b)carrier
carrier densities iluminated ~
for illuminated
densities for p- junction
junctionat sho~t
at short
ci~r;;ui~. Parameters
circuit. 'Parameters are the
the same
same as
as for
for Fig.
Fig. 6.5
6.5 and
and b.b. ;:>0,O.The horizont~larrows
Thehorizontal arrows inIn
(a) show
(a) show the
the direction
directionof
ofelectron
electronand
and hole
hole transport
transportfollowing
followingphotogeneration.
photogeneratlOn. In
In this
this limit,
limit, ififno
nocarriers
carriers are
are lost
lostthrough
throughrecombination
recombination at
atthe
thesurfaces,
surfaces,
(So= 0=or0Spor= 0)Spthe=electron
(So 0) theandelectron
hole photo and hole photocurrents
currents are
are simply
simply qq times
times
Combining
Combining terms we have for
for the short circuit spectral
spectral photocurrent
photocurrent the
the flux
fluxofofphotons
photonsabsorbed
absorbed in in that
thatlayer.
layer.
The
The QE QEspectrum
spectrumreflects
reflects the the cell
cell design
design and
and the
the material
materialquality.
quality. For
For
jse(E) = -jn(E, -wp) - jp(E, wn) - jgen(E). (6.64)
(6.64) a.a p-n
p-n cell
cell the
the short
shortwavelength
wavelength response
response is is provided
provided mainly
mainly by by the
the pp re-
re-
i'gion,
i'gion,since
sincehighhighenergy
energyphotons
photonsare areabsorbed
absorbed at atthe
thefront
frontofofthe
thecelL.
cell.Since
Since
For
For aa panchromatic
panchromatic spectrum
spectrum the
the net
net photocurrent
photocurrentisis carriers
carriers generated
generated near near thethe front
frontsurface
surfacearearesusceptible
susceptibletotosurface
surfacerecom-
recom-
bination,
bination, the theshort
shortwavelength
wavelength QE QE isis particularly
particularlysensitive
sensitive to to the
thesurface
surface
Jse = 100 jse(E)dE. (6.65)
(6.65) recombination
recombination velocity.velocity. Sn may
So may be reduced by be reduced by introducing
introducingaawindow
windowlayerlayer
 168 The Physics
The Physics of
ofSolar
SolarCells
Cells Analysis
Analysis of
ofthe
the p-n
p-nJunction
Junction
168 169
169

or passivating
or passivating the
the surface.
surface. Long
Long wavelength
wavelength QE QE is
is affected
affected by
by the
the back
back 6.7.3.
6.7.3. p-n junction as a photo
voltaic cell
p-n junction as a photovoltaic cell
surface quality and by the thickness of the cell. The abruptness
surface quality and by the thickness of the cell. The abruptness of the QE of the QE
edge refiects the form of the absorption. At intermediate wavelengths car- IfIfaaresistive
resistive load
load. isis connected
connected between the terminals
between the terminals of
of the
the iluminated
illuminated
edge reflects the form of the absorption. At intermediate wavelengths car- cell, the cell experiences both electrical and optical bias. The bias splits the
riers are
riers are generated
generated in
in the
the SCR.
SCR. The
The various
various contributions
contributions to to the
the QE
QE areare cell, ~he cell experIences both electrical and optical bias. The bias splits the
shown inin Fig.
Fig. 6.9. The overall
6.9. The overall magnitude
magnitude of
of the
the QE
QE isis affected
affected byby the
the eff-
effi- Fermi
FermI levels
levels throughout
throughout the
the device,
device as
as shown
shown in
in Fig.
FI'g 6.11.
611 Notice
N t' howh the h
shown ' . . . 0 Ice ow t e
ciency of
ciency of light
light absorption.
absorption. ItItmay
maybebeincreased
increasedbybyreducing
reducingreflection
refiectionlosses,
losses,
by increasing the width of the cell or by light trapping techniques.
by increasing the width of the cell or by light trapping techniques. Effect
Effect of
ofjunction
junction depth
depth
Figure6.10
Figure 6.10 shows
shows the effect of
the effect varying some
of varying some ofof the
the junction parameters.
junction parameters.
1
In Fig. 6.1O(a) shows how the QE changes with emitter
In Fig. 6.10(a) shows how the QE changes with emitter thickness. When thickness. When
0.9
0.9
xp exceeds L n , part of the emitter becomes a 'dead' layer which absorbs

0.6 ~ Xp=O.21J.Ill
xp exceeds Ln, part of the emitter becomes a 'dead' layer which absorbs 0.8
0.8
light but
light
is
but generates
generates no
straightforward to
no photocurrent,
photocurrent, and
show that in
and degrades
the
degrades the
optimum
the cell
design
cell performance.
the
performance. It
emitter
It
should
0.7 Xp=O.5. /
0.7
is straightforward to show that in the optimum design the emitter should 0.6
be asas thin
thin asas possible
possible andand certainly
certainly thinner
thinner than Ln.Practical
thanLn' Practicalsolar
solarcells
cellsare
are ~
a 0.5 ~ Xp=l.
W
be
usually designed to have a thin, highly doped emitter
usually designed to have a thin, highly doped emitter and a thick, lightly and a thick, lightly 0.4 __
0.5
0.4
0.3 ___
doped base. In these conditions the photocurrent current from the thin
from the thin pp region
region 0.3
doped base. In these conditions the photo
is likely to be limited by surface recombination velocity, while the current 0.2m.. Xp=2.
0.2
is likely to be limited by surface recombination velocity, while the current 0.1
from the
from thick nn region
the thick region maymay be be limited
limited byby either
either minority
minority carrier
carrier diffusion
diffsion o0
length or by rear surface recombination. The effect
length or by rear surface recombination. The effect of Sn on such of Sn on such aa device
device 400 500 600 700
500 600 700 800
800 900
900
is shown in Fig. 6.10(b) and the effects of Lp and Sp
is shown in Fig. 6.10(b) and the effects of Lp and Sp in Fig. 6.10(c). in Fig. 6.10(c).
Wavelength II nm
Wavelength nm
(a)
Layer
Layer contnbutions
contrbutions
Effect of Sn
Effect of Sn

1 _.. - .... -._. - - .... .. _....... ... _. - .... -. --........, Q9

0.9
1

-F-..._-----.. . .---_____
T::
0.9
~9 \ QB
O.B
0.8 5
~8 Q7
0.7 So=10 ~-
0.7
~7 Q6
W 0.6
~ So=O, 103
0.6
~6 ---player
-p layer OM .So=106
0.5
Q4
0.4

W
W 0.5
M -nlayer
aa -n layer ~3
0.3
0.4
~4 ----SCR
----SCFI
Q2 So=108
0.3
~3
-totalQE
---lolalQE
abs. flux
0.2
Q1
0.1
.
.. . . ... abs, flux o
0.2 O~--_+----+_--_+----+_--~
~2 400
400 50 600 700
0.1 500 600 700 BOO
BOO 900
900
~1
O~~~~------+------+------+---~~
o
"' Wavelength II nm
Wavelength nm
400
~O SOD
500 600
600 700
700 800
800 900
900 ~
/",
(b)
(b)
Wavelength II nm
Wavelength nm Fig, 6.10. Calculated quantum effciency of a p- junction showing the effect of (a) the
Fi~. 6.lD. Calc~lated quantum efficiency of a p-n junction showing the effect of (a) the
emitter layer thickness (b) the front surface recombination velocity for a thin emitter
Fig. 6.9. Schematic quantum efficiency curve showing contributions from p, n, and
:~lltterdlar)r t~hlckness (b) the front surface recombination velOCity for a thin emitter
cell, and (c) the transport parameters in the base for a thin emitter cell with low Sn'
Fig. 6.9, Schematic quantum effciency curve showing contributions from p, n, and S c b~ tr~nsport parameters in the base for a thin emitter cell with low S
f: an recombination
SCR. Surface
ur ace recom velocitiesare
matlon velocities aregiven
givenininmm5s-1.
- i. . n
SCR.
 The Physics
The Physics of
of Solar
Solar Cells
Cells Analysisof
Analysis ofthe
thep-n
p~ Junction
Junction 171
171
170
170

1.5
1.5
Effect
Effect of Lp
Lp and Sp
Ec ~
Lp=5
Lp=5 Vbi - V
Vb;- V
1

--..
>::
0.9
0.9 EEFn
Fn
i
0.8 CI)
CI
0.8 0.5
0.5
0.7
0.7
0.6
~
>C)
C)
-
UJ
0.6 ..
CI)
Ul 0.5
aa 0.5
0.4
0.4
C
C
W
W
CI
0 'U.5
"- 1.5 2 2.5
2 2.5
0.3
0.3 EFp
0.2 -0.5
-0.5
0.2
0.1
0.1 Ev
00 -1
-1
400 500
500 600
600 700 800 900
400

Wavelength I nm Distance I111m

Distance p.m
(a)
(a)
(c)

6.10. (( Continued).
Fig. 6.lD. Continue). 1.0&18
C')
l1 1.06+16

Fermi levels
levels slope
did in the
negative,
slope towards
the case
case of
towards the band edge
the short circuit
edge at
cell,
of the short circuit cell, indicating
i.e., a photocurrent.
negative, i.e.,
Now both terms in
Now in Eqs.
Eqs. 6.34
6.34 and
and6.39
6.39 are
edges of
at the edges
indicating that

arenon-zero.
of the SCR, as
the net

non-zero. However,
as they
current
the net current is

However, because
because
is -
's()E() 1.0&14
- 1.0&14
~ 1.06+12
a- 1.06+12
en 1.06+10
ii
cC
1.06+10

~ 1.06l
~ 1.0&08
-
p
p

~~
n
n

solutions for
the solutions for bias
bias and light
light induced
induced currents
currents are independent in
are independent in the G; 1.06+06
G; 1.0E+
depletion approximation, the solution for the current J in this
depletion approximation, the solution for the current J in this regime is regime is "E 1.0EH
"E 1.06+04
given by the algebraic
algebraic sum of the integrated short-circuit photocurrent
sum of the integrated short-circuit photocurrent and and
ocaca
1.06+02
o 1,OE+2
the dark
the dark current
current atat that
that bias
bias (Eq.
(Eq. 1.4)
1.4)
1.06+
1.06+00
J(V)
J(V) ==Jsc
J sc -- Jdark(V)
Jdark(V) .. o 0.5
0.5 1.5
1.5 22 2.5
2,5 33

DistanceII p.m
Distance 11m
This superposition
superposition of currents is
is valid
valid within the depletion
depletion approximation
approximation
when minority
minority carrier
carrier recombination linear. IfIfseries
recombination isis linear. series resistance
resistance isis impor=
impor!" (b)
(b)
tant, the
tant, the addition of terms
addition of changesslightly,
terms changes slightly, as
as explained
explained below.
below. Fig.
Fig: 6.11,
~.11 .. (a)
(a)Band
B~nd profile
profile and (b) carrier densitiesininananilluminated
carrier densities iluminatedp-n
p- junction
junction at
at
If the
If the dark
dark current
current isis dominated
dominated by
by diffusion
diffusion currents (Eq.
(Eq. 6.58)
6.58) then positive
PO~ltlve bias. Notice that the carrier
bias. ~o~lce carrier densities aresimilar
densities are similar to
to the
the values
vaues at short circuit
circuit
(Fig. 6.8) . This
(Fig. 6,8), This is because the
IS because the bias
bias chosen
chosen is
is much
much less
less than V. aand
than Voc d the
th currentt is.
qV (6.71) dominated by by the
the photocurrent,
photocurrent. oc n e curren IS
J(V) =
J(V)= Jsc
J sc-- Jdiff,o(eqV/kBT 1)
Jdiff,o(e /kBT -- 1) (6.71) dominated

withthe
with thedark
darksaturation
saturationcurrent
currentJdiff,O given by Eq.
Jdiff,O given Eq. 6.54.
6.54. This is
is identical
identical
4~
to the
to the ideal
ideal diode
diode equation,
equation, Eq.
Eq. 1.5,
1.5, and
and isis the
the most
most commonly
commonly used
used form
form "where Jm,o isisthe
/"where. Jrn,o the saturation
saturation current
current in the
the dark.
dark. When
When recombination
recombinationcur-
cur-
for the
for the current-voltage
current-voltage characteristic
characteristic ofof aa solar
solar cell.
cell. More
Moregenerally,
generally, thethe rents
rents in
ill the
theSCR
SCRarearedominant,
dominant ,m m==22andandJm,o
J m,O=-- Jscr,o.
J.ser,O-
J(V) can sometimes be expressed by the non-ideal
J(V) can sometimes be expressed by the non-ideal diode form diode form . Equation
E~uation 6.72 6.72 can be be rearranged
rearranged to
to find
find anan expression
expression for
for the
the open
open
J(V) == Jsc
J(V) Jm,O(eqV/mkBT -1)
J sc -- Jrn,O(eqV/rnkBT -1) (6.72)
(6.72) circuit
ClfCUlt voltage, Vac, the
voltage, v;c, thevoltage
voltage which
which develops
develops between
between the terminals
terminals ofof
172
172 The Physics
The Physics of
ofSolar
Solar Cells
Cells Analysis
Analysis of
of the
the p-n
p-n Junction
Junction 173
173

the iluminated
the illuminatedcell
cellwhen
when no
no current
current isis drawn
drawn increasing
increasing

Im,O 1)
- nnI (Jsc
V;oc --- mkBT J ++1)..
intensity
intensity maximum
maximum
oc mkBT
V;
q
q J
(Jsc
m,O
(6.73)
(6.73) power
powerline
line
, ,'"\
Equation 6.71,
Equation 6.71, or
or 6.72
6.72 in
voltage characteristic
voltage
in the
characteristic of
the more
more general
the p-n
of the
general case,
case, describes
junctionsolar
p- junction
describes the
solarcell.
cell. The
the current-
current-
relationship be-
The relationship be-
-i:
GI
....
::
o
-...
-cc
..l!!
l!
::::s
tween the J(V)
tween the J(V)characteristic
characteristicand
andthethecell
cellperformance
performancecharacteristics
characteristics is
is oo
discussed in Chapter 1. We can now calculate the J(V) for any rrn device
.....
discussed in Chapter 1. We can now calculate the J(V) for any rn device ~

structure in
structure in aa given
given spectrum
spectrum byby calculating
calculating the
the QE
QE spectrum
spectrum and
and the
the dark
dark
--
current characteristic as described above. Then the solar cell performance
current characteristic as described above. Then the solar cell performance
characteristics can
can be
be extracted
extracted as
as described
described in Chapter 1.
1. Voltage
Voltage Voltage
characteristics in Chapter Voltage
(a) (b)

6.8. Effects
Effects on
on p-n Junction Characteristics
p-n Junction Characteristics Fig. 6.12, Effects
Fig. ~.1? Effects of
of (a) concentrationand
~a) .concentration and(b)
(b)temperature
temperatureon onp-n
p- junction
junction J(V)
J(V) char-
char-
6.8. acteristic.
acteristic. The
The arrow
arrow indicates
mdlcates the
the direction
direction of
of increasing intensity or
increasing intensity or temperature.
temperature.
6.8.1. Effects
6.8.1. Effects of
ofparasitic
parasitic resistances
resistances

So far
So we have
far we have considered
considered aa lossless
lossless material
material without parasitic resistances.
without parasitic resistances.
Series resistance is, however, a prevalent problem in practical
Series resistance is, however, a prevalent problem in practical solar solar cells.
cells. concentration factor up
concentration factor up to
to high
high irradiation
irradiation levels.
levels. Equation
Equation 6.73
6.73 indicates
indicates
As
As mentioned
mentioned in Chapter 1,
in Chapter 1, series
series resistance
resistance arises
arises from
from the resistance of
the resistance of that
that Vac should also increase, logarithmically, with irradiation. Therefore,
Vce should also increase, logarithmically, with irradiation. Therefore,
the p and n layers to majority carrier flow, as well as from the
the p and n layers to majority carrier flow, as well as from the resistanceresistance we expect
we expect light
light concentration
concentration to to increase cell efficiency.
increase cell effciency. The
The effect
effect of
of light
light
of the electrical
of the electrical contacts
contacts to
to the
the cell.
cell. The effect is
The effect is to introduce a
to introduce a potential
potential intensity on
intensity on J(V)
J(V) is
is ilustrated
illustrated ininFig,
Fig. 6.12.
6.12.
drop JARs
drop of JAR. between the junction and the applied potential difference at
of between the junction and the applied potential difference at In practice, concentration also increases
In practice, concentration also increases series series resistance
resistance and
and raises
raises the
the
the Vapp ,
terminals, Vapp,
the terminals,
temperature of the celL. These effects tend to degrade cell
temperature of the cell. These effects tend to degrade cell performance, performance,
with the
with the result
result that
that the
thecell
cell has
has an
an optimum
optimum effciency
efficiency atat some
some finite
finite con-
con-
Vapp == VV -- JARs.
Vapp centration, usually
usually aa few
few hundred
hundred suns.
suns. This
This will
wil be
JARs'
centration, be discussed further in
discussed further in
Chapter 9.
Thus,
Thus, when
whenaa photocurrent
photocurrentflows flows(J(J>:; 0),
0), the
the-bias
bias at
at the
the terminals
terminals isis
smaller than that at the junction, and when a dark current flows
smaller than that at the junction, and when a dark current flows the bias the bias
at the terminals
at the terminals isis larger.
larger. In
In the
the formulae
formulae derived above, VV refers
derived above, refers to the
to the
applied If J J dark 6.8.3. Effect of
6.8.3. Effect of temperature
temperature
applied bias at the junction. If J and J dark are both expressed in terms of the
bias at the junction. and are both expressed in terms of the
measurable Vapp , then
bias Vapp, then the
the additivity
additivity condition
conditionshould
should be
be changed
changed to As temperature
temperature is
measurable bias to As is increased, the equilbrium
increased, the equilibrium population
population of of electrons
electrons nnj

J(Vapp++JARs)
J(Vapp J sc - Jdark(Vapp
JAR.) == Jse Jdark(Vapp -- JdarkAR.)
JdarkARs) increases exponentially, increasing the dark saturation current density.
increases exponentially, increasing the dark saturation current density.
Note that
Note that this
this effect wil be
effect will be stronger for the
stronger for the diffsion
diffusion component
component of of the
the
to
to take account of
take account of series
series resistance
resistance losses.
losses. The effect of
The effect of series
series resistance
resistance on
on dark current
dark current than
than for
for the
the recombination-generation
recombination-generationcomponent,
component, because
because
J(V) characteristics is illustrated in Fig. 1.10.
J(V) characteristics is ilustrated in Fig. 1.10. of the stronger dependence on n (Eqs. 6.54 and 6.56).
of the stronger dependence on nj (Eqs. 6.54 and 6.56). The increased The increased
~ark
cjark current reduces Vac.
current reduces Voe.At At the same time,
the same incre ased temperature
time, increased temperature re- re-
O" duces the band gap and increases the photocurrent, since lower energy
O" duces the band gap and increases the photocurrent, since lower energy
6.8.2. Effect of
6.8.2. Effect of irradiation
irradiation photons can
photons can now
now bebe absorbed.
absorbed. The
The net
net effect
effect isis aa reduction
reduction inin effciency
efficiency
For
For linear photogeneration and
linear photogeneration recombination, increasing
and recombination, increasing the intensity
the intensity because the
because the loss in Voc
loss in Voe outweighs
outweighs the
the gain
gain in
in Jse. This is
J sc . This ilustrated in
is illustrated in
of the incident light increases
of the incident light increases the photo
the photo current.
current. J
Jse
sc varies
varies linearly
linearly with
with Fig.6.12(b).
Fig.6.12(b).
 174 The Physics
The Physicsof
of Solar
Solar Cells
Cells Analysis
Analysisof
ofthe p-n Junction
thep-n Junction 175
175
174

6.8.4. Other
6.8.4. Other device
device structures
structures minority
minority carrier
carrier density
density because
because of
of the
the effects
effects of
oftraps.
traps. In
In such conditions,
conditions,
light and
light and dark
dark currents
currents may
may not
not be
be added,
added, and
and the light
light current may even
even
The techniques described
The techniques described inin this
this chapter
chapter can can be applied to
be applied to other
other de-de- vary nonlinearly
vary nonlinearly with
with light intensity.
intensity.
vice structures,
vice structures, provided
providedthat
that the
the depletion
depletion approximation
approximation isis valid.
valid. More
More
complicated structures
complicated structures may include 'window' layers placed in front of of the
the
emitter; highly doped
emitter; doped back surface field
back surface field layers;
layers;graded
gradedpporor nn layers;
layers; p- p-
i-- structures
i-n structures andandheterojunctions.
heterojunctions. A A wide
wide band
band gapgap window
window is is used
used toto 6.9.
6.9. Summary
Summary
reduce
reduce thethe surface
surface recombination
recombination velocity
velocity andand toto modify light admission
modify light admission
At
At a p-n junction
a p-n junction between
between aa p p type
type and
and n type layer
n type layer of of the
thesamesame semicon-
semicon-
through reflection
through and absorption
reflection and absorption of of short wavelength
wavelength light.
light. These
These ef- ef-
ductor, aa potential
ductor, potential barrier
barrier is is formed whichacts
formed which actsas as aa barrier
barrier to majority
majority
fects are
fects are easily
easily incorporated
incorporated in in the model
model as as changes
changes to to Sn bs(E).
Sn and bs(E).
carrier flow.
carrier flow. This
This barrier
barrier provides
provides the asymmetric
asymmetric resistances
resistances needed
needed for for
Modellng aa back
Modelling back surface
surface field layer, such
field layer, such asas nn++ back
back surface
surface layer
layer be-
be-
photovoltaicaction.
photovoltaic action. Good
Goodquality
qualityp-n p-n junctions
junctions can can be made easily easily and
neath an
neath an nn type
type base,
base, means solvingfor
means solving for the n-n ++ junction
the n-n junction andand find-
find-
they are are the
the most
most widely
widelyused useddesign
design ofofsolar
solarcelL.
cell.
ing
ing minority carrier diffusion
minority carrier diffsion currents
currents in in both
both regions.
regions.AA compositionally
compositionally
The current-voltage
The current-voltage characteristic
characteristic for for aa p-n
p-n junction solar cell cell can be
gradedpp or
graded or nn layer
layer can
can be
be used
used to to assist
assist thethe minority
minority carrier
carrier flow
flow to-
calculated analytically
calculated analytically by making two approximations. These are that
approximations. These are that the
wards the
wards the junction
junction and cancan bebe treated
treated by by including
including the electric
electric field
field term potential is dropped
dropped entirely
entirely across
across aa junction
junction region
region which
which is is free of carriers
potential is
in the
in the current
current equations.
equations. AA p-i-n structure is
p--n structure is straightforward,
straightforward, and and can
can
(the depletion approximation), and that the minority
(the depletion approximation), and that the minority carrier recombination carrier recombination
be treated by extending the depletion
be depletion region
region to include
include an
an undoped
undoped layer.
layer.
rates are linear in the carrier density. density. ThenThen the the junction
junction may may be be treated in
This is
This is discussed
discussed in in Chapter
Chapter 88 for for amorphous
amorphoussilicon. silcon.AAp-np- heterojunc-
heterojunc-
three layers,
three neutral nand
layers, neutral nand pptype typelayers
layers andand aacharged
charged spacespace charge
charge re-re-
tion may
tion may bebe treated
treated just
just as
as the
the p-n junction, once
p-n junction, once the
the heterojunction
heterojunction po- po-
gion. The
gion. current is
The current is due
due to to contributions
contributions from each of
from each of the
the layers,
layers, which
which
tential profile
profile is worked out, and the
worked out, the difference
difference in absorption
absorption coeffcient
coefficient
are calculated
are calculated separately.
separately. In In each
each of
of the
the neutral
neutral layers
layers thethe current
current is is due
due
included.
included. to minority
minority carriers
carriers and can be be found
found by by solving
solving the current
current and and conti-
conti-
nuity equations.
equations. TheseThese equations
equations are are simplified
simplified when when the electric
electric field
field is
is
zero
zero and recombination
recombination linear.linear. InIn the space
space charge
charge region
region the current is is
6.8.5. Validity
6.8.5. Validity of
of the
the approximations
approximations
due to generation
generation and and recombination
recombination between between both both types of carrier. The The
approximation is
The depletion approximation is best
best for highly
highly doped
doped junctions
junctions at at low
low bias.
bias. net current
current voltage
voltage characteristic
characteristic is is the
the sum
sum of contributions
contributions due due to thethe
Then the the rectangular
rectangular form form assumed
assumed for for the
the space
space charge
charge profile
profile isis most
most light(the(the
light photophotocurrent)
current) andand duedue to the the applied
applied bias bias (the
(the darkdark current).
current).
accurate,
accurate, and and thethe volume
volume takentaken up up byby the junction is is the
the smallest.
smallest. ForFor The dark dark currents
currents from
from thethe neutral
neutrallayers
layers and andspace
space charge
charge layers
layers have
have
weakly
weakly dopeddoped junctions
junctions or or at highhigh forward
forward bias, freefree carriers populate the different dependence. J(V)
different bias dependence. J(V) cancan bebeexpressed
expressed in in the
the form
form of of the
the Shock-
Shock-
junction
junction region
region andand contribute to the the potential
potential distribution.
distribution. TheTheeffect
effect is
is ley diode
diode equation
equation with
with an an ideality
ideality factor
factor which
which expresses
expresses the dominantdominant
generally to
generally to increase
increase recombination,
recombination, since the electron electron and
and hole
hole densities areare type of of dark
dark current.
current. The
The photocurrent
photocurrent can can be related
related to the the quantum
quantum
more
more likely
likely to be be similar,
similar, andand the the Shockley
Shockley Read Read Hall
Hall recombination
recombination rate rate effciency
efficiency spectrum,
spectrum, and is is influenced
influenced by by the junction
junction design
design and and mate-
mate-
larger.
larger. Thus the the depletion
depletion approximation
approximation underestimates the dark dark current
current rial parameters.
rial parameters. Photocurrent
Photocurrent isis highest
highest whenwhen the greatest amount of light light
at
at low
low doping
doping or or high
high forward
forward bias.bias. results
results in in carriers
carriers crossing
crossing the the junction.
junction. This This isis true
true for
for a thinthin emitter,
emitter,
Linear
Linear recombination
recombination resultsresults for for either Shockley
Shockley Read Hall or or radia-
radia- low front
low front surface
surface recombination
recombinationvelocity,velocity, long
long diffusion length in
diffsion length in the
the base
base
tive
tive recombination
recombination in the limit limit where
where the the majority
majority carrier
carrier density
density greatly
greatly Jl.nd low reflectivity. Dark current is least when
ind low reflectivity. Dark current is least when carrier lifetimes are thecarrier lifetimes are the
outnumbers
outnumbers the the minority
minority carrier.
carrier. This
This wilwillbebeuntrue
untruefor
forlightly
lightlydoped
doped ma-ma- ;" longest.
;'~ longest.
terials
terials or or ininthe
thelimit
limitofofhighhighlightlightintensity.
intensity.Some
Someother
otherrecombination
recombination The formulation
The formulationcan canbe beused
used toto simulate
simulatethe theeffects
effects ofof junction
junctiondesign,
design,
processes
processes are are not
not linear,
linear, even
even in in the
thelimit
limitof oflow
low minority
minority carrier
carrier density.
density. InIn materials properties,
materials properties, irradiance
irradiance and and other
otherparameters
parameters on on solar
solar cell
cell perfor-
perfor-
some
some defective
defective materials
materials the recombination
the recombination
linearly with
rate may rise super rate may rise super linearly with mance,
mance, and and isis easily
easily modified
modified to modelmodel other varieties
varieties of p-np-n junction.
junction.
176
176 The Physics
The Physics of
of Solar
Solar Cells

References
References
C.-T.
C.-T. Sah, R.N. Noyce
Noyce and W. Shockley,
Shockley, "Carrier
"Carrier generation
generation and recombination
in
in p-n junctions and
p- junctions andp-
p-n junction
junction Proc. Institute
characteristics", Proc.
characteristics", Institute of
01 Radio
Radio
Engineers, 1228 (1957). I
Engineers, 1228 (1957). Chapter 7
P.A. Basore, "PC1D version 3: improved speed and convergence", ConI. Record. Chapter 7
P.A. Basore, "PC1D version 3: improved speed and convergence", Conf Record.
22nd IEEE Photovoltaic
22nd Photovoltaic Specialists
Specialists Conf., 299-302 (1991).
ConI, 299-302 (1991). PC1D software
software
wasdeveloped
was developed
by Sandiaby Sandia
National National
Laboratories, NM, USA; Laboratories,
and is dis- NM, USA; andMonocrystalline
is dis- I M t II" Solar
S Cells
tributed by Centre for Photovoltaic Engineering, University of New South onocrys a ine olar Cells
tributed by Centre for Photovoltaic Engineering, University of New South
Wales.

7.1. Introduction: Principles

7.1. Introduction: Principles of
of Cell
Cell Design
Design

The most common solar cell

common solar celldesign monocrystallne;rn
designisisaamonocrystalline ;rn
rn junction. rn
homojunctions have
homojunctions have the significant
significant advantage over over heterojunction designs
designs
that there is
that there is no material interface
no material interface at at the
the junction,
junction, andand so losses due
so losses to
due to
interface states
interface states can
can be
be avoided.
avoided. In In this
this chapter
chapter we we will
wil discuss
discuss the de-
de-
sign of rrn
sign rn junction
junctionsolar
solarcells
cells ininthe
thetwotwobest
bestperforming
performingphotovoltaic
photovoltaic
materials, monocrystallne silicon
materials, monocrystalline silcon andand gallium
gallum arsenide, ilustrating the
arsenide, illustrating the is-
is-
sues relevant to PV in
sues relevant in weakly
weakly absorbing and strongly absorbing materials.
We wil look
We will look at
at the
thetechniques
techniques which
which are are used
used toto improve
improve performance
performance in
practice.
Effcient
Efficient photovoltaic
photovoltaic energy
energy conversion requires efficient
conversion requires effcient light absorp-
absorp-
tion, effcient
efficient charge separation and efficient
effcient charge
charge transport. FromFrom Chap-
Chap-
ter 66 we can
can translate these requirements into demands on the
demands on the material and
design parametersof
design parameters ofaarrn
p- junction
junctionsolarsolarcelL.
cell.
. For
Forgood
good optical
optical absorption,
absorption, the optical depth depth of the
the device, a(E)(xp +
device,a(E)(xp +
xn)
x n ) should be high for energies
energies EE above
above thethe band
band gap,
gap, and the reflectivity
reflectivity
of the surface, R(E),
R(E), should
should be be small.
small.
. For
Forgoodgood charge
charge separation,
separation, the the built ininbiasbias Vbi
Vbi should
should bebe large,
large, de-de-
manding
manding a high high doping
doping gradient across the
gradient across the junction
junction (a large Na Na xx Nd Nd
product).
product). Charge
Charge recombination
recombination in in the
the junction
junctionregion
region should
should bebe as
as slow
slow
as possible. And, as we
possible. And, have seen
we have seen inin Chapter 6, 6, the junction
junction should
should be be
located close
close to the
the surface
surface forfor effective
effective charge
charge separation over a range range
of
of wavelengths.
. For
For effcient
efficient minority
minoritycarrier
carrier transport
transport the the minority
minoritycarrier
carrierlifetimes
lifetimes
((Tn,
Tn,Tp) and
T p) anddiffusion lengths (Ln,
diffsion lengths (Ln, Lp) should be
Lp) should be long
long and
and surface
surface re- re-
combination velocities (8
combination velocities (8n,8p)
n ,8p ) should
should be be small.
small. Good
Good majority carrier
carrier
transport
transportrequires
requiressmall
smallseries
series resistance
resistance Rs, RSI and
and the
the shunt
shunt resistance
resistanceRsh Rsh

177
177
 The Physics
The Physics of
of Solar
Solar Cells
Cells Monocrystalline
Monocrystalline Solar
Solar Cells
Cells 179
179
178
178

should be
should be as
as high
high as
as possible
possible to
to avoid
avoid leakage
leakage of
of carriers
carriers back
back across
across the
the These
These requirements
requirements limit limit the range
range ofof materials
materials which
which can
can bebe used,
used.
junction. Figure
Figure 7.17.1 shows
shows the
the band
band gaps
gaps ofof some
some common semiconductor materials materials
junction,
. The
Theband
bandgap
gapshould
should be
be close
close toto the
the optimum
optimum for
for the
theintended
intended solar
solar compared
compared to the limitinglimiting effciency
efficiency in in a standard solar solar spectrum,
spectrum. Of Of the
the
bs(E).
spectrum, bs(E), elemental
elemental semiconductors,
semiconductors, only only silicon
silcon has
has a suitable band gap, gap. Germanium
Germanium
spectrum,
and
and selenium
selenium werewere usedused inin early
early photovoltaic cells cells but thethe band
band gaps
gaps are
are
Some of
Some of these
these demands
demands are
are contradictory and aa compromise
contradictory and compromise mustmust be
be found,
found. too
too small,
small. Of Of the
the compound
compound semiconductors,
semiconductors, III-V III-V crystallne
crystalline materials
materials
For instance, high doping levels needed for a large built in bias are
For instance, high doping levels needed for a large built in bias are likely likely have
have been
been best
best developed.
developed. GallumGallium arsenide
arsenide andand indium
indium phosphide
phosphide havehave
to reduce minority carrier lifetimes, and strong optical absorption will
to reduce minority carrier lifetimes, and strong optical absorption wil gen- gen- suitable band
suitable gaps. Several
band gaps, Several II-VI
II-VI and and I-III-V semiconductors
semiconductors are are strong
strong
erally mean
erally mean strong
strong recombination,
recombination. optical absorbers
absorbers with with suitable
suitable band gaps and some, some, notably CdTe CdTe andand
CuInSe2,
Cu1nSe2, havehave been
been developed
developed for for photovoltaics.
photovoltaics, TheseThese materials cannot
cannot
always
always be be doped
dopedbothboth nand
nand pp type,
type, soso that
that p-n
p-nhomojunctions
homojunctions cannot
cannot be be
7.2. Material
7.2. Material and
and Design
Design Issues
Issues made, Amorphous silicon
made. Amorphous silcon and
and related
related alloys
alloys have
have suitable bandband gaps,
gaps, but
7.2.1. Material
Material dependent
dependent factors
factors diffsion
diffusion lengths
lengths areare too
too short
short compared
compared to the absorption
absorption depth, and and soso
7.2.1.
again they cannot be used for p-n
used for p-n homojunction
homojunction cells,cells.
There are
There are certain
certain basic
basic materials
materials requirements,
requirements. For high theoretical
For high theoretical con-
con- Materials
Materials can can be prepared
prepared as singlesingle crystals
crystals (monocrystallne)
(monocrystalline) or as as
version efficiencies in AM1.5 (? 30%) the band gap should lie
version effciencies in AM1.S (2= 30%) the band gap should lie in the range in the range polycrystallne
polycrystalline or or multicrystallne
multicrystallinewafers,wafers. IfIfgrain
grain sizes
sizes are smaller than
than de-
de-
1-1.6 eV; or
1-1.6 eV; or in
in the
the range
range 0,7
0.7 to
to 22eV
eV for
for effciencies
efficiencies over
over 20%
20% (see
(see Fig,
Fig. 7,1),
7.1). vice thickness, grain
vice thickness, grain boundary
boundary effects
effectsareare likely
likelytotodominate
dominatetransport
transport and
and n
pp and type varieties
n type varieties of
of the
the semiconductor
semiconductor material
material must
must be
be available,
available, and
and diffsion
diffusion lengths
lengths are
are likely
likely to
to be
be short.
short. In
Insuch
such cases,
cases, much
much of the analysis
analysis
we need to be able to produce a junction of good quality.
we need to be able to produce a junction of good quality, For acceptable For acceptable of Chapter 6 is not valid, valid. We wil distinguish 'multicrystallne'
We will 'multicrystalline'as asmaterial
material
photocurrent levels
photocurrent levels the
the quantum efficiency should
quantum effciency should be
be high over aa broad
high over broad where the
where the crystal grain size is comparable
size is comparable with with oror larger
larger than thethe device
device
range of wavelengths. That means that the diffusion lengths
range of wavelengths. That means that the diffsion lengths must be long
must be long thickness, and
thickness, and 'polycrystallne'
'polycrystalline' or or 'microcrystallne'
'microcrystalline'asasmaterial
materialwhere
wherethethe
compared
compared to to the absorption depth,
the absorption depth, andand this
this places
places high
high demands
demands on the
on the grain size is much
size is much smaller.
smaller. Devices
Devicesmade madefrom
frommulticrystalline
multicrystallne material
material can
crystal quality.
crystal quality, be considered
considered in in same
same wayway as as single
single crystal
crystal devices,
devices, treated
treated below,
below. Junc-
tions in
tions in polycrystalline
polycrystallne materials will wil be
be considered
considered in in the
the Chapter 8.
Intrinsic
Intrinsic materials
materials variables
variables are are the optical properties,
the optical properties, the available
the available
0.40
0.40
dopants, the carrier mobilties,
dopants, mobilities, andand thethe dominant
dominantrecombination
recombination processes,
processes,
all of
all of which
which areare related
related to to the crystal structure,
structure. Process
Process variables are the
variables are
0.30
0"30 means of wafer
means wafer and
and junction fabrication.
>-
u:0
c()
c
Q)
0.20
!
:
()
0.20 7.2.2. Design factors
7.2.2. Design factors
ffiff
The requirement
The requirement of of aa good
good quality
quality junction
junction generally favours the
generally favours the p-n
p-n ho-
0.10
0.10
mojunction for
mojunction for the
the design, Once the
design. Once the material
material is chosen,
chosen, aa limited
limited number
of design
of design factors
factors remain
remain which
which can
can be
be controlled.
controlled, These
These include
include junction
junction
0.00
0.00 polarity; junction depth; doping
polarity; doping levels; cell thickness;
levels; doping gradients; cell thickness; sur-
sur-
0.50 1.00
1"00 1.50
1"50 2.00
2.00 2.50
2.50
0.50 face treatments;
face treatments; andand contact
contact design.
design. The
The simple
simplep-n
p-n junction
junction can
can also
also bebe
Band Gap (eV)
Band Gap (eV) modified in
modified in aa number
number of waysways to improve performance, Strategies include
improve performance. include
Fig. compositional variations
compositional variations such
such as
as windows
windowsandandgraded
gradedlayers,
layers,andandlight
light trap-
trap-
Fig"7.1. Limiting efficiency
7"1. Limiting effciency asas aa function
function of
of band
band gap
gap for
for the air mass
the air mass 1.5
1.5 solar
solar spec-
spec-
trum, and the band gaps of some common photovoltaic materials.
trum, and the band gaps of some common photovoltaic materials" ping structures.
ping structures,
180
180 of Solar
The Physics of Solar Cells
Cells Monocrystalline
Monocrystalline Solar Cells
Cells 181
181

The main
The main focus
focus of cell
cell design
design depends
depends upon
upon the optical properties
properties ofof the
material. In a weakly absorbing material like silicon,
materiaL. In a weakly absorbing material strategies to
silcon, strategies to maximise
maximise
the optical
optical absorption are important,
important, and and recombination
recombination at at the
the rear
rear surface
surface
needs to be avoided. In a highly absorbing
needs to be avoided. In a highly absorbing material material like gallium arsenide,
like gallum arsenide,
absorption is
good optical absorption is achieved
achieved easily
easily but
but more
more attention
attention must be be paid
to minimising recombination near the front surface and around the junction, junction.
Strategies for for these
these two
two groups
groups of of materials
materials are
arediscussed
discussed below,
below.

7.2.3. General
7.2.3. Generaldesign
designfeatures
features of
of p-n
p-njunction
junctioncells
cells

A number of general design

design features
features apply
apply to p-n homojunctioncells
rn homojunction cellsinde-
inde-
of the
pendent of the materiaL.
material. These
These are
are that: L r X U,K rr
k
(i) the
(i) the thickness
thickness should
should exceed
exceed the absorption length,
the absorption length, for
for effcient
efficient light
light
(a) (b)
absorption;
(ii) the
the junction
junction should
should be
be shallow
shallow compared Fig" 7.2" (a)
Fig. 7.2. (a) Tetrahedral
Tetrahedral crystal structure of
crystal structure of crystalline
crystallne silicon;
silcon; (b) Band
Band structure of
(ii) comparedtotoboth
both the
the diffusion length
diffsion length silcon,
silicon, showing
showing energy
energy levels
levels as function of wavevector,
wavevector, k. Levels
Levels are normally filled
filled up
in the
in the emitter
emitter and the absorption
and the absorptionlength,
length, to
to avoid
avoid having
having aa 'dead
'dead layer'
layer' to the
the energy
energy EE == 0,0,which
which marks
marks the
the top
topof
ofthe
thevalence
valence band"
band. Notice
Notice that the
the valence
valence
at the
the front
front of
of the
the cell
cell where light is absorbed unproductively, as noted band maximum isis at
band maximum the rr point,
at the where k ==0,0,while
point, where whilethe
theconduction
conduction band
band minimum
minimum
in Chapter
Chapter 6; 6; is near the X
is X point,
point, where
where kk isis directed
directed along
along (100).
(100). The
The fundamental
fundamental band gap
gap lies
lies
between these extrema
between these extrema and is marked as Eg. Eg .
(iii) the emitter
(iii) the emitter should
should be
be doped
doped heavily,
heavily, to to improve
improve conductivity
conductivity to the
to the
fine
fine metallic contacts on
metallc contacts on the front of of the
the cell,
cell. Heavy
Heavy emitter
emitter doping
doping
also
also allows
allows the
the base
baseto to be
be doped
doped lightly,
lightly, which improves
improves collection
collection in - the
thefundamental
fundamental band band gap
gap -- areareseparated
separated by by only
only1.1
1.1 eeV at room
room
the neutral base
base region
region without limiting
limiting thethe open-circuit
open-circuit voltage.
voltage. temperature, these
temperature, points occur
these points occur at
at different values
values of the crystal
crystal momen-
momen-
(iv) Reflection of light should be minimised. All crystalline
(iv) Reflection of light should be minimised. All crystallne semiconduc- semiconduc- tum and
and aa phonon
phonon is is needed
needed asas well
well as
as aa photon
photon in in order
order for an
an electron
electron
tor cells
cells are
are treated with an anti-reflection
anti-reflection (AR)
(AR) coat.
coat, This
This isis aa thin to be
be promoted,
promoted. This
This reduces
reduces the optical
optical absorption
absorption compared
compared to direct
direct
layer
layer of material of refractive index between between that of the semiconductor
that of gap semiconductors,
gap Directoptical
semiconductors. Direct opticaltransitions
transitionsoccur
occurininsilicon
silcon at
at photon
and the air which
which couples
couples light of preferred
light of preferred wavelengths
wavelengths into the the semi-
semi- energies above
energies above 33 eeV though these
V though these are not useful
useful for photovoltaics,
photovoltaics.
conductor by matching the optical impedance.
conductor by matching the optical impedance, The AR coat The AR coat material The band gapgap is
is fairly
fairly close to the optimum
optimum for for solar
solar energy
energy conversion.
and thickness
thickness are chosen
chosen to to maximise
maximise photocurrent
photocurrent generation for for the At 1.1
At 1.1 eV,
eV, the
the theoretical
theoretical limiting
limiting effciency
efficiency inin AM1.5
AM1.5 is is a few
few percent
percent
relevant
relevant incident
incident spectrum.
spectrum, (This
(This isis discussed
discussed further
further in
in Chapter 9.) smaller than the maximum,
smaller maximum.
Silcon has
Silicon has aa refractive index of
refractive index of around
around 3.43.4 and
and aa natural
natural reflectivity
of about 40%
40% over visible wavelengths. Introducing
visible wavelengths. Introducing aa single
single or multilayer
7.3. Material Properties
Silicon Material
7.3. Silcon Properties anti-reflection coat reduces this to less
reduces this less than 5%,
5%.
7.3.1. Band
7.3.1. Bandstructure
structure and
and optical
optical absorption
absorption
7.3.2.
7.3.2. Doping
Doping
Silicon
Silcon is is a group
group IV element
element which
which adoptsadopts the
the tetrahedral crystal struc-
ture at room
room temperature
temperature and and pressure.
pressure. In In this
this arrangement
arrangement every
every valence
valence Another criterion
Another criterion for
for electronic
electronicmaterials
materialsisis whether
whether they
they can
can be easily
easily
electron
electron isis involved
involvedininbonding
bondingand and thethe material
material is a semiconductor,
semiconductor. As dis- doped. Silicon can be readily doped n type, usually by the addition of
doped. Silcon can be readily doped n type, usually by the addition
cussed in Chapter
cussed in Chapter 3, gap
3, the band theis band gap
indirect, Thatisis,
indirect. That is, although the lowest
although the lowest pentavalent phosphorus
pentavalent phosphorus impurity
impurity atoms,
atoms, which
which introduce
introduce an
an extra loosely
loosely
point
point in the conduction band and the highest point in the valence band
in the conduction band and the highest point in the valence band bound electron
bound electronwhen
whensubstituted
substitutedfor
foraa tetravalent
tetravalentsilicon
silcon atom.
atom, pp type
 The Cells
Physics of Solar Cells
The Physics Monocrystalline
Monocry stallin e Solar Cells
Cells 183
1S3
1S2

The
The net
net recombination
recombination rate, U, wil
will be
be the
thesum
sumof
ofall processes,
all processes,
1"&07
IR Visible uv
.. I U = Urad
+ U Aug++UAug
U = Urad U SRH . + USRH, (7,1)
(7.1)
1.E-K6
'e
--
U

C
1 "E-K5
From Eq, 4.59
From Eq.
to follow
to follow
4,59 we
weexpect
expectthe
the radiativ
radiative recombination
e recomb ination rate materiall
type materia
in pp type
rate in

Q)
'
n-no
n-no
1.E-K4 Urad ---
Urad = Tn,rad (7.2)
(7,2)
=
Q)
Tn ,rad
0U where silcon is
Sincesilicon indi-
is an indi-
1" E-K3 where the
the radiative
radiativ e lifetime
lifetime Tn,rad varieslike
Tn ,rad varies like11N
1/Na,
a . Since
C rect
rect band
band gap
gap semiconductor,
semiconductor, radiative
radiativ e recombination slowand
recombinationisisslow andTn,rad
T is
0 t . 11 off theh order of millseconds, n ,rad
le.
: 1 "E-K2 typically
yplca y 0 t e order of milliseconds, so
so this contribution
contrib ution is
is negligib
negligible,
ci
.. density
0en . Auger recombination
~uger recomb canbe
ination can be import
important
ant inin silicon,
silcon, if the carrier
carrier density
.c 1,E-K1 is
IS high,
hIgh. For
For electrons
electrons in pp type material,
materia l, from
from Eq, 4.67
Eq. 4,67
c(
1.E-KO UAuger no)
AnN;(nn -- no)
UAuger == AnN;( (7.3)
(7,3)
1 1"5 2 2"5 3
2 2.5 3 3.5
3"5 4
so
so that the
the lifetime
lifetime varies
varies like
Energyy IleV
Energ eV

Fig. Silcon absorpti

7.3. Silicon
Fig. 7.3. absorptionon spectrum
spectrum". The absorpti on spectrum
The absorption
of gallium arsenide
spectrum of gallum arsenide
Tn,AugooN;:2.
N-
Ton,Aug OO (7.4)
a
2
(7.4) .

to its indirect (over

densities (over
is shown for compari
shown for comparison, to emphasi
son, to se the
emphasise low absorpti
the low absorption silicon due
in silicon
on in due to its indirect
ate
Auger processes
Auger process are most
es are most import
important silcon at
ant in silicon at high doping densities
high doping
gap. The
band gap" linesdenote the wavelengths SOO nm and 300 nm, the approxim
verticallines
The vertical denote the wavelen gths 800 nm and 300 nm, the
approximate 17
1017 3 and can be the dominant recombination pathway
cm-3) nt recomb ination pathwa y mechan ism.
mechanism.
visible part spectrum .
the spectrum.
of the 10 cm- ) and can be the domina
limits of the visible
limits part of sil-
but the purest sil-
. Trap
Trap assisted
assisted nonradiative processes
nonrad iative process dominate
es domina in all
te in all but
icon, h a single trap state we
state we
ICon. For
For Shockley Read Hall
Shockley Read Hall recomb
recombination through
ination throug
trivalen t boron,
with trivalent introdu ced
which introduced
boron, which expect, from Eq,
Eq. 4,80,
4.80,
silcon
silicon may
may bebe produced doping with
by doping
produc ed by
an electron
electro n vacancy, or hole,
vacancy, or the lattice
into the
hole, into when substit
lattice when uted for
substituted silicon.
for silcon. n-no
USRH = - (7,5)
n-no
(7.5)
generally degrades the material quality..
atoms generally degrad es the materia l quality US RH = - -
Addition impuri ty atoms
Additio n of these impurity Tn,SRH
Tn,SRH
to reduce
However relative
However relatively high doping levels
ly high are needed
levels are the emitter
neededinin the emitter to reduce where carrier lifetime
minori tycarrier Tn,SRHdepend s upon of trap
density of
the density
es Voc. In silicon the where the
the minority lifetimeTn,SRH depends upon the trap
series resistan
series and increas
ce and Vbi, which
e Vbi. turn increas
in turn states, Eq. 4,69 we
4.69 we
resistance increase which in increases Voc' In silcon the
the band
of the
shrinkage of due
gap, due
band gap, states, as
as well
well as
as their
their position
positio n within
within the band
band gap,
gap. From
From Eq,
influence of doping on Voc
influence Voc isis limited
limited by the shrinkage
by the know
know that
states, atathigh doping levels. This means
high doping levels, This means that that
to the
the introduction
introdu ction of tail states, 1
Vac cannot in fact exceed 81% of Eg at room
Vcc cannot in fact exceed 81% of Eg at temper ature.
room temperature, Tn,SRH = BnNt (7,6)
(7.6)

and there e that Tn,SRH decreas es as doping increases, sugges ting

and there is evidence
is evidenc that Tn,SRH decreases doping increases, suggesting
binati on that doping,. Lifetim es vary from
7.3.3. Recom
7.3.3. Recombination that the
the number
numbe r ofof active
active traps
traps increases with doping
increases with Lifetimes
ms for very pure material
ms for very pure materia l to
to aa fraction
fractionof
ofaalLS
J-lS for
for high
high defect
defect densities.
densities,
We
We will that nearly all
below that
wil see below of the
all of volumeof
the volume typicalcrystal
ofaatypical line silicon
crystallne silcon
depleti on Combining the bulk recombination
. Combining the bulk recombination process processes es in
in Eq.
Eq. 7,1
7.1 and
and noting that
noting that
is provide
cell is provided d by type silicon.
by pp type silcon, The of recomb
effect of
The effect recombination in the
ination in the depletion in the neutral are linear in the excess
because ofof the levels of
low levels
the low photo- m the neutralpp region
region all
all recombination
recomb ination mechanisms
mechanisms the excess
region and
region layer is
emitter layer
and emitter rather low
is rather low because of photo- such that
leaves
This leaves electron density,
electro n density , (n
(n -- no),
no), we
we obtain
obtain the
the net
net electron
electro n lifetime
lifetime Tn
Tn such
generation
genera layers, and
in those thin layers,
tion in usually be
can usually
and can neglected. This
be neglected,
n recomb ination in thethe pp region as the domina nt volume recomb
region as the dominant volume recombina- ina- n-no
electron
electro recombination U= =
U n-nO
-- (7.7)
trap-as sisted
and trap-assisted
Auger and mechan isms. (7,7)
tion process, includes radiativ
process. This includes radiative,e, Auger mechanisms, Tn
Tn
184 The
The Physics
Physics of Solar Cells
Cells Monocrystalline
Monocrystalline Solar Cells
Cells 185

"~
"~ \
\-2 (al
\-N;.2 (a) . (bl
(b)
As we
As we saw
saw in
recombination is
recombination
in Chapter
Chapter 6,
is low,
6, surface
surface recombination
low, i.i,e.,e"when
recombination isis important
whenminority
minoritycarrier
important when bulk
carrierdiffusion
diffsion lengths are
are long,
long.

10-
10-44 ~
\\
\ \
"\ 10-
10-44
\\.
\\.
For electrons in
For electrons in pp type
type silicon,
silcon, the the surface
surface recombination velocity at
recombination velocity at un-
un-

"\
"\. '.\ '.
treated surfaces, and at interfaces
surfaces, and with metallic
interfaces with metallc contacts, is in the range
range of
~ xx"\ \.\. 10 3 -10 5 cm S-1 [Hovel, 1975]. When the surface is passivated with a layer
103-105 cm S-1 Hovel, 1975J, When the surface is passivated with a layer
10- 5
10-5 ~
x : .:.
x \
\ \..
.\
\"
\1\1
~ x
x I I ""'.
\
\
10-55
10-
)( )( x \.'\\
x x
silcon dioxide,
of silicon dioxide, the oxide
oxide shields minority carriers
shields minority carriers from
from defects
defects atat the
i~\ \ surface
surface andand reduces Sn to to less
less than
than 100
100 cm s-1 Green,
[Green, 1995J,
1995].
~i~\ \
reduces Sn cm s-1

'\\\ "\
\\. \ \\ .
\\
x..~
x~
, \.\.\
x,
x x6i

~
10- 6
10-61
\\ \. 10-66
10- xxxx x.x
x.x \ \ \

x .x\
lx\ "\ .. ,A~ ~ \.\
". ~ ~
7.3.4. Carriertransport
transport
Alx\ "Cp
1:p
"\ x\ \\ 7.3.4. Carrer

\
"C
1:.n
\\ , \Ii
10- 7
10-7 ~ ~\
~I
X" I I
10-
10-7
7 .x ,\
x ~\ x \
In practice,
practice, thethe electron
electron mobility
mobilty in in pp type
type silicon
silcon tends
tends to be higher than
X'

x~\ ~A
~A x\ the hole mobilty in n type
hole mobility type silcon
silicon doped
doped to to the
the same
same level,
level, and the the mi-
mi-

10- 8
\x\
t\
\x \

t\ 10- 8
x x\
~
\\ XX

\+~\x
\
XX \\

\+~\x \\
nority electron
impurities in
impurities
diffsion length
electron diffusion
in silicon
silcon are are of
length isis longer.
of acceptor
longer. This is because
acceptor type type and
and so
because the fundamental
so are
are more
fundamental
more important
important in in nn
.i 10-8
\\ \
10-8 ~ \ II
\. I
\.. \\\\ ~~
\ type than pp typetype materiaL.
material. It It means
means that that carrier collection is is more
more efficient
effcient
~~ Xx
10- 9
\ \\ \ 10- 9
in p type material than in
thickness, and so cells cells are
in an
an nn type
are generally
type layer
layer of
generallydesigned
of the
the same
designedasasn-p
same doping
n-p cells
doping density and
cellswith
withaathin
thin nn type
10-9 ~
i I
10-9
\"W22
\W thickness,
\ 0\
0\ 0
0 emitter on top of of a thick
thick p type base,base.
10
\ Electron and hole
Electron mobilties are
hole mobilities are determined
determined by the the frequency
frequency of scat-
10- '0 , . , , I 10-
10-10 I , , , , ,
10-101
10'4
1014 10 '6
1016 10'8
1018 10 20
1020 10
1014'4 10 '6
1016 10'8
1018 10 20
1020 tering events within the
events within the conduction
conduction or or valence band. At low
valence band. low doping
doping levels
levels
NA (cm-
NA
3
(cm-3i) No (cm- )
No (cm-3
3 scattering is
scattering is dominated
dominated by by the
the silicon
silcon lattice. At high doping mobilty de-
doping mobility de-
creases because
creases because the the impurity
impurity atomsatoms generate
generate scattering
scattering centres,
centres. ToTo a first
Fig.
Fig. 7.4. Lifetime as
7.4. Lifetime as aa function
function ofof doping density in
doping density in pp type (left panel)
type (left and nn type
panel)and type approximation the mobility mobilty does does not
not depend
depend on whether doping is is nn type or
(right panel) silicon. At high doping densities the lifetime varies like the inverse square 2
(right panel) silcon" At high doping densities the lifetime vaies like the inverse square
of
p type,
type. In silcon,
silicon, electrons have aa mobility
electrons have mobilty of of around
around 1500
1500cm cm2V-I V-I s-1
s-1 at
of the
the doping density,
density, indicating
indicating that Auger processes
that Auger processes are dominant. Lifetimes
Lifetimes for
for other
other 2 V-I s-1
recombination
recombination processes are are expected vary like
expected to vary like the simple
simple inverse
inverse of the
the doping. From low doping,
low doping,falling
fallng toto around
around 70 70cm cm2 V-I s-1 at impurity concentrations of
van Overstraeten andand Mertens
Mertensvan[vanOverstraeten,
Overstraeten,1986).
1986). over
over 10 19 cm-
1019 cm-3,3 , while holes have a low-doping mobility of 500 cm 2 V-I s-l,
while holes have a low-doping mobilty of 500 cm2 V-I s-l,
2 V-I s-l. The corresponding diffusion constants in
fallng
falling to around 50 cm2
50 cm V-I s-I, The corresponding diffsion
lightly doped
lightly doped material are 30-40 cm2 cm 2 s-1 forfor electrons
electrons and around
around 10 cm 2
10 cm2
and S-1 for holes
holes [Shur,
Shur, 1990;
1990; Green, 1995].
-=-+-+-,
1 1 1 1
-
1
=TSRH
--+
Tn TSRH
Tn
- +TAug
Trad
-.
Trad TAug
1 1 1
(7.8)
(7,8)
S-1 for

where
Minoritycarrier
Minority carrierdiffusion
refers to
where TT refers the net
to the
Green, 1995j,
diffsionlengths
lengthsare
net recombination
aredefined
recombination and
defiedfrom
and do
fromL L= =VTi5Vi (Eq,
not distinguish
do not
(Eq. 4,95)
distinguish between
4.95)
between
processes,
processes. For For aa commercial
commercial siliconsilcon cell,
cell, Tn
Tn isis several
several J-LS
l-Sandand Ln
Ln is is around
Different
Different processes
processeswill
wil have
have different
different temperature
temperature and doping doping dependence,
dependence.
100 l-m.
J-Lm.
In lightly doped p-type silicon at room
silcon at room temperature,
temperature,SRH SRHprocesses
processes domi-
domi-
The resistivity of any semiconductor
semiconductor material,
material, p,p, depends upon the level level
nate, giving
giving rise to aa T value of about 1010 l-S.
J-LS. Lifetime
Lifetimein inlightly
lightly doped
doped nn type ,, <J
~of ofdoping.
doping.From Fromthe the definition
definition of of conductivity
conductivity (Eq, (Eq. 3.41),
material is rather
rather shorter, around 11 l-S,
shorter, around J-LS. In
In more
more heavily
heavily doped
doped silicon
silcon or at
higher temperatures
of TT on
on Na shown
Auger dominates,
temperatures Auger
shown in Fig.
dominates. This is evident from the dependence
Fig. 7.4,
7.4. Radiative lifetimes
lifetimes in in silicon extremely
silcon are extremely 1 1 (7.9)
(7,9)
long and never
never dominate the recombination
recombination in in aa practical
practicalsolar
solarcelL.
cell. p = -; = q(l-nn + l-pp) .
 'f,1

186
186 Physics of
The Physics of Solar
Solar Cells
Cells Monocrystalline
Monocrystalline Solar
Solar Cells
Cells 187
187

doped material, resistivity

In doped resistivity will therefore be dominated by the majority
wil therefore majority Energy
Energy
carrier density
density and mobilty,
mobility. ppvaries
varies roughly
roughly like (10 16 INa) Ohm-em
like (1016/Na) Ohm-cm in pp
type silcon,
type silicon, and
and is
is aa factor
factor of
of three
three smaller in n type,
smaller in type. With
With an
an acceptor
acceptor
concentrationof
concentration 10 16 cm-
of1016 em -3,3 , a p region several hundred f..tm thick has a sheet
a p region several hundred .m thick has a sheet
~
<E<::----- 300J.
300JUTl ~:>
O,3Im
resistance of around 10-1 1 Ohm-cm2 which
10- Ohm-cm2 which isis unimportant
unimportant for for the current
current
(-)/
--
densities
densities under standard solar illumination. However, series
standard solar ilumination, However, series resistance ef-, resistance ef- Ef
fects
fects can be more serious
more serious in in the emitter, where
where the funnelling of current
funnellng of current
from a large semiconductor
semiconductor area into a very small contact area creates high high
current densities,
current densities. This
This is
is one reason why the emitteremitter is is highly doped relative emitter base
base
to the
the base,
base. When
When the the contact
contactresistance
resistance isis included
included the theequivalent
equivalentseries
series nntype
type pptype
type
sheet resistance
resistance for
for aa commercial
commercial silconsilicon cell
cell is
is typically
typically 20-50 Ohm-cm 2
20-50 Ohm-cm2.
Silicon materials
Silcon materialsproperties
propertiesare arediscussed
discussedinindetail
detailby byGreen,
[Green,1995;
1995; Bube
Bube ----------------~)
~ Distance
1998;
1998; van
van Overstraeten, 1986J;
1986J; andand many semiconductor texbooks.
Fig. 7,5"
Fig. 7.5. Energy band diagram
Energy band diagram of aa nIJ
nJ junction
junctionininsilcon"
silicon.

7.4. Silcon
7.4. Silicon Solar
Solar Cell
Cell Design
Design doping density elecric
electric field
field

7.4.1. Basic
7.4.1. Basic silicon
silicon solar
solar cell
cell

A typical silicon
A typical solar cells
silcon solar cells isis an
an n-p junction made
n-p junction made in aa wafer
wafer of pp type
type
silicon
silcon aa few
wafer
wafer forms

as much
few hundred microns thick and around
forms
the base

light as possible, and lightly

around 100

doped
100 cm2
theof base of the cell and is thick (300-500 .m)
(rv
as much light as possible, and lightly doped ("" 1016 cm-3) improve
cm in

10 16
2
in area.

cm-
area, The pp type
f..tm) in order to absorb
absorb
3 ) to improve
g +
distae
distance

n p n+ p
diffusion lengths. The nn type emitter is created
diffsion lengths, created by
by dopant
dopant diffusion
diffsion and is
heavily (rv 10 19 3
heavily doped
doped ("" 1019cm-cm-3) ) to reduce sheet series
to reduce series resistance,
resistance. This layer
Fig. 7"6,
Fig. 7.6. Doping
Dopingprofies
profilesfor
foran
anabrupt
abrupt(black
(blackline)
line)and
and diffused
diffused (grey
(grey line) junction"
junction.
should be thin to allow as much much lightlight as
as possible
possibleto
to pass
pass through
through toto the base,
but thick
thick enough
enough to to keep
keep series resistance reasonably low, low. Carrier collection
from
from the emitter is is negligible
negligible because of high high recombination
recombination in in this heavily The junction
The junctionisisprepared
preparedbybydiffusing
diffsingthe thenntype
typedopant
dopant- - usually
usually
doped layer, The
doped layer. The front surface isis anti-reflection
front surface anti-reflection coated
coatedand and both
both front
front and phosphorus -- on
phosphorus ontotothe
thepptype
typewafer.
wafer. Phosphorus
Phosphorus may may be deposited either
back surfaces
surfaces are are contacted
contacted before
before encapsulation in aa glass glass covering,
covering. from the
from the vapour
vapour phase by exposure exposure to nitrogen gas bearing POC!s; POCI3 ; from
from
phase, for
solid phase, for example by chemical
chemical vapour
vapour deposition of phosphorus oxide;
7.4.2. Cell fabrication
fabrication or directly
or directly by by ion
ion implantation,
implantation. The latter method method allows
allows greater control
7.4.2. Cell
the doping
of the doping profile
profile but is is more
more costly.
costly.Note
Notethat
that the
the dopant
dopant profile
profile in
in the
Single
Single crystal
crystal silicon
silcon may be grown by by aa number
number ofof methods.
methods, In
In the
the common diffused
diffsed n layer will
n layer wil not
not bebe uniform
uniform and the junction
and the junction not
not abrupt, unlike the
abrupt, unlike the
Czochralski
Czochralskiprocess
processaasingle
singlecrystal
crystalisisdrawn
drawn slowly
slowlyout
outof
ofaamelt.
melt,In the float
In the float ideal
ideal p-n junction in
p- junction in Chapter
Chapter6. 6. This
This has
has the
the consequence
consequencethat
thatthe
theelectric
electric
zone
zone process
processaa single
singlecrystal
crystal isisgradually
graduallyformed
formedfrom
fromaapolycrystalline
polycrystallne rod .,., fields
fieldsextend
extendfurther
furtherfromfromthethejunction
junction (and
(and the
the depletion
depletion approximation is
by
by passing
passing aa molten
molten zone
zonethrough
through it.it, This is
is more
more costly
costly but
but produces
produces higher
higher /'/' lesslessaccurate),
accurate). The Thediffsed
diffuseddoping
dopingprofile
profile may
may bebe modelled
modelled with
with an
an error
error
purity material. In either case the dopant (usually boron)
purity materiaL. In either case the dopant (usually boron) introduced is introduced function.
function.
during
during growth to produce
produce aa pp type crystal. The solid crystal is sliced
type crystal. sliced into
into Multicrystallne silcon,
Multicrystalline silicon, which
which is used
used in most
most commercial silcon cells,
commercial silicon cells,
wafers
wafers and
and etched
etched toto smooth the roughrough surfaces,
surfaces. is made
is made by a by a variety
variety of methodsof methods
such as casting such as casting and ribbon growth. (For
and ribbon growth, (For
188 The Physics
The Physics of
of Solar
Solar Cells Monocrystalline Solar Cells
Monocrystalline 189
189
188

textured surface

l textured surface
......
.!!
.! )C
)C
--~
Silcon cell 100 nm light
..
.! )C 0.8
Silicon cell, 500
Silcon cell 500 nm light
run light

I!f! ..
:J f! ..
I AR coat ai c-
41)0;::
.>
_ ..
ai
:. -- 0.8

front
~
.!:i ,-i:
.. II :i C
~:g :i -
.! -: 0.'
EJg
contact :i l:--
:
(J
CJ
E
:i
CJ
l:- 0.2

50 100
50 100 150
150 20 250
~
250 30
300 50 100
50 100 150 20020 25
150 250 30
300

DepUi 111m Depth/11m

Depth 111m

Fig" 7.8.
Fig. 7"8" Simulated cumulative absorption
Simulated cumulative absorption andand recombination
recombinationrates rates for
for aa silicon
silcon solar
solar
cell with
cell with the
the parameters
parameters in Table
Table 7"1 under monochromatic
7.1 under monochromatic lightlight at two
two different
different wave-
wave-
lengths at
lengths at a bias
bias close to open
close to open circuit. In In each
each graph
graph the
the cumulative
cumulative absorption
absorption and and
recombination, normalised
recombination, normalisedtotothe
the total
total incident
incident flux,
flux,are
are plotted
plotted against
against depth
depth through
the celL. For aa good
cell. For good cell
cell at short
short circuit,
circuit, recombination
recombination should
should be zero
zero andand cumula-
cumula-
Fig" 7.7.
Fig. 7"7" Layer
Layerstructure
structureofofbasic
basic silcon
siliconcelL.
cell.
tive absorption
tive should be
absorption should be close
close to
to one.
one"At At open
opencircuit
circuit (illustrated)
(ilustrated) the
the final
final values
values of
recombination and absorption are equal.
recombination equal.
details see Green Green,
[Green, 1995),)
1995].) The relatively large sizes of the
the grains (0,1-
(0.1-
10
10 cm)
em) mean
mean that moderately
moderately effcient
efficient devices
devices can be prepared
prepared from
from mul-
mul-
ticrystalline material using
using techniques
techniques similar to those
those used
used for
for monocrys-
monocrys-
Table
Table 7.1.
7.1. Typical
Typical silicon
silicon material
material and
and cell
cell parameters,
parameters, used
used for the
the calculations
calculations in
talline silcon,
tallne silicon. Fig. 7"8"
Fig. 7.8.
The front surface is
is usually
usually textured to reduce
reduce reflectivity
reflectivity and an anti-
coating is
reflection coating is deposited from liquid
liquid or or vapour
vapour phase
phase added.
added, For
For silicon
silcon .. EMITTER (N
EMITTER (N TYPE)
TYPE) BASE
BASE (P TYPE)
TYPE)
the AR
AR coating
coating should
should have
have a refractive
refractive index of around 22 and and thickness
thickness thickness/
thickness/.m
JLm 0.5 300
80-100 nm.
of 80-100 Suitable materials
nm, Suitable materials forfor silicon
silcon areare tantalum
tantalum oxide (Ta 20 5),
oxide (Ta205), doping/cm- 3
doping/cm-3 1019
1 xx 1019
1 11 x 10
X 16
1016
titania (Ti02)
titania and silcon
(Ti02) and silicon nitride
nitride (Sb Ni4)'
(SbNi4), minority
minority carrier
carrier diffusion constant/cm 2 s-1
diffusion constant/cm2 2 40
rear surface
The rear surface is doped
doped more heavily to to create
create aa back
back surface
surface field,
field, minority carrier lifetime/s
lifetime/s 1x 10- 6
X 10-6 5X 10- 6
X 10-6

which helps
helps to
to reduce
reduce thethe loss
loss of
of carriers
carriers through
through surface
surface recombination,
recombination. minority
minority carrier
carrierdiffusion
diffusion length/
length/.m
JLm 14
14 140
surface recombination velocity/em s-1
recombination velocity/em 10000
10000 10000
This is
This is discussed below.
below,
back contacts are added, added. In the early
early silcon
siliconcells,
cells, reflectivity 0.05
0"05
Finally the front and back
absorption:
absorption: at 500 nm/cm-11
500 nm/cm- 15000
15000
aluminium was used as the rear contact, contact. In In large
large scale production, AR coat, JLm/cm- 1
at 11 .m/cm-1 35
35
front and
and back
back contacts
contacts areare usually
usually deposited
deposited by screen
screen printing and then
Screen printing of
fired. Screen of contacts
contacts is is cheap
cheap butbut obscures
obscures a a relatively large
large
area of the cell
cell and
and degrades
degrades conductivity.

7.4.3.
7.4.3. Optimisation
Optimisationofofsilicon
siliconsolar
solarcell
celldesign
design
. bulk
bulkrecombination
recombination in
in the
theppregion
region is
is the
the most
most important
important recombination
recombination
7.8 ilustrates
Figure 7,8 illustrates the
the absorption
absorption and
and recombination
recombination profiles
profiles in
in a typi- .,4 process
process
silicon cell,
cal silcon cell, calculated
calculated using
using the
the p-n junction theory
p-n junction theory of
ofChapter
Chapter 66 and
and ;~
i " . rear
rearsurface
surfacerecombination
recombination is is important,
important, particularly
particularly for
for photogeneration
photogeneration
the
the materials
materials parameters
parameters in in Table
Table 7,1.
7.1. From
From the graphs
graphs we
we can
can make
make the
the by
by red
red and
and infrared light
light
following observations:
following observations: . front
frontsurface
surfacerecombination
recombination and and recombination
recombination in in the
the junction
junction region
region are
are
. absorption
absorptionofoflight
light close
close to
to the
the band gap (near
band gap (near infrared)
infrared) is
is poor
poor
relatively
relatively unimportant
unimportant forfor photogeneration
photogenerationby bylong
long wavelengths
wavelengths
 .~

190 ThePhysics
The Physicsof
ofSolar
Solar Cells
Cells MonocrystallineSolar
Monocrystalline Solar Cells
Cells 191
191
190

n contacts
n Icontacts
______
I
~WII~~~--oxide
oxide layer
layer
(g(g(g (g nn nn

(g(g(g (g
(g(g(g (g Fig"7.10.
Fig. 7.10. Buried
resistance.
resistance.
Buried contacts"
contacts. Differential n+ doping in the contact
Differential n+ contact grooves
grooves reduces series
series
(a)
(a) (b)
(b)

Fig. 7.9.
Fig. 7"9" Surface texturing: (a)
Surface texturing: (a) shows how the
shows how the refraction
refraction ofofincident
incidentlight
lightrays
raysatat the
the
textured surface
textured increases the
surface increases the optical
optical path
path length relative
relative to light normally incident
incident on
the resistance
the resistance either
either inin the
the emitter,
emitter, ifif the
the contacts
contacts are
are too
too sparse,
sparse, or or in
aa plane
plane surface;
surface; (b)
(b) shows
shows aa plan
plan view
view of
of regular
regular pyramids"
pyramids. the metal, if the fingers are too
fingers are too narrow.
narrow, TheThe optimum
optimum arrangement
arrangement is is aa
grid narrow, dense, highly conducting fingers. One solution is to use
grid of narrow, dense, highly conducting fingers. One solution is to
narrow, deep
narrow, deep contacts
contacts partly
partly buried
buried in
in the surface of the cell.
surface of cell. This may
To improve
To improve the
the performance
performanceof of the
the cell
cell itit is necessary
necessary to maximise
maximise the
reduce shading
reduce shadingtoto aa fraction
fraction of a percent of the the surface,
surface. By
By embedding
embedding
absorption of
absorption of red
red light,
light, minimise recombinationatat the
minimise recombination the rear surface,
surface, and
the contacts in the semiconductor,
semiconductor, a larger contact area can can be
be achieved
achieved
minimise series
minimise series resistance.
resistance. Bulk
Bulk recombination
recombination isis determined
determined mainly
mainly byby the
without increasing the surface shading.
shading. The grooves are created by laser
grooves are
method of wafer
wafer growth,
growth, and
and for
for good
good quality
quality silicon
silcon it is already as
as low
low as
mechanical etching,
or mechanical etching, and
and are
are doped
doped more
moreheavily
heavilythan
than the
the main
main emitter
emitter
can be
can be expected,
expected. to improve
improve conductivity, However,the
conductivity. However, the large
large scale
scale preparation of such such
Thus the main
main challenges in crystalline
challenges in crystallne silcon
silicon cell
cell design
design are to:
contacts is
contacts is more
more costly than screen
screen printing.
printing,
.
Maximise
Maximise absorption
absorption
.
Minimise
Minimise rear
rear surface recombination
surface recombination
. Minimise
Minimise series
series resistance
resistance 7.4.5. Strategies
7.4.5. to reduce
Strategies to reduce surface
surface recombination
recombination

These
These are
are discussed
discussed below.
below. Back
Backsurface
surface field,
field. A
A more
more heavily
heavily doped
doped layer
layer is
is formed
formed at
at the
theback
back
surface of the
surface of the p type
type base
base by
by alloying with aluminium
alloying with aluminium or or by
by diffsion,
diffusion.
This introduces
This introduces aa p+
p+-p junction and
-p junction andpresents
presents aa potential
potential barrier
barrier to
to the
the
7.4.4. Strategies to
7.4.4. Strategies to enhance absorption
enhance absorption
minority
minority electrons.
electrons. This
This back
back surface
surface field
field reflects electrons and reduces
reduces
. Texturing
Texturing of
offront
front surface,
surface. This
This reduces
reduces the
the net
net reflection
reflection of
of light
light and
and the
the effective
effective rear surface recombination velocity,
velocity, to less than
than 100
100 cm
cm S-1.
S-l.
increases the optical
increases the optical depth ofof the
the cell,
cell. Texturing
Texturing cancan bebe achieved
achieved by by (See Box
(See Box 7.1).
7,1), The
The extra
extra p+-p junction also
p+-p junction also adds
adds to the built
to the built in
in bias
bias
treating
treatingwith
withanananisotropic
anisotropicchemical
chemicaletc,
etc. which
which acts
acts preferentially
preferentially along
along of the
of thecell,
cell,and
andmay
mayenhance
enhanceVcc [Hovel, 1975),
Voe Hovel, 1975] . Front
Fl'ontsurface
surfacefields
fieldshave
have
the
the (111)
(111) crystal
crystal planes
planes and
and leaves
leaves a pattern
patternofofpyramids
pyramids onon the
thesurface.
surface. also
also been
been used
used in
in some
some cell
cell designs,
designs, but are
are less
less effective
effective since
since the ratio
ratio
Regular pyramids can be produced on a monocrystallne
Regular pyramids can be produced on a mono crystalline surface by pho-
surface by pho- of
of doping
doping levels
levels wil
will be
be smaller,
smaller.
tolithographic
tolithographic definition,
definition. Light trapping
trapping is is improved
improved by by using
using inverted
inverted
pyramids,
pyramids, which
which improve
improve the total
total internal
internalreflection
reflection of
oflight
lightreflected
reflected
from
from the
the back
back surface,
surface, by
by asymmetric pyramids, or by texturing the the rear
rear "I"~ ~Box 7.1, Calculation of
'Box 7.1. ofeffective
effective surface recombination
recombination velocity
velocity with
with aaback
back
surface,
surface. Light
Light trapping
trapping strategies
strategies are
are discussed
discussed further in in Chapter
Chapter9,9. surface
surfacefield
field
. Optimisation
Optimisationofofcontacts,
contacts. Shading
Shadingofofthe thefront
front surface
surface by
by metal
metal contacts
contacts
reduces
reduces the
thesurface
surfacearea
areaavailable
availabletotothe
theincident
incidentlight
lightby
byasasmuch
muchasas10%,
10%. Whenaa back
When back surface
surface field layer
layer is present in pp type
is present type material,
material,the
thechange
change
Reduced
Reduced contact
contact area
areaincreases
increases the
theavailable
available surface
surface area
area but
butincreases
increases in
in doping
doping introduces
introduces aa step
step in
in the
the conduction
conduction band
band edge
edge of
of height
height 6.Ec
flEe =
=
 192 ThePhysics
The Physicsoj
ofSolar
Solar Cells
Cells MonocrystallineSolar
Monocrystalline Solar Cells
Cells 193
193
192

o~f c.b.
c"b" isislinear
solve
linearininthat
solvefor
that layer
thethe
for
layer and
ratio F~xJ+~
ratio
and characterised
dn (x )
characterisedby
~ andand
....An(xHJ
n Xj+
find 'inin the
find,
byaadiffusion
diffsion length
the dark,
dark , that
that
length Ln+
Ln+ we
we can
can

E F
E F
~~~~",=~,,,,,,,,,"'''''-~''=~''rl,;'~0~''U' ~~AA ~"~~.o
v"b,
v.b. S
D=
SeffDLn+
ff -
NNf~Sn+Ln+
n+
-- ~ + cosh
Dn+
cos
a . + sm
Bn+Ln+
Ln+
D
n sinh .1
Ln+,
h~
L
n+
. h~}
L
n+ (7.10)
e - N + { asinh + cosh
Bn1;Ln+
Dn+
n+
~
Ln+ Na+ Sn+Ln+ sinh . + cosh . .
Ln+
n+ Ln+
Ln+
X
...!b....L (7,10)
+
pp p
If the
If the highly doped layer
highly doped layer isis thin
thin enough,
enough, Eq.
Eq, 7.10
7,10 shows
showsthat
that Seff
S..ffwill
wil be
be
Fig"7.11.
Fig. 7"11" Back surface
surface field
field in
in pp type
type material.
materiaL.Electrons
Electrons are
are reflected
reflected from
fromthe
the doping
doping reduced
reducedby by the
the ratio of
of doping
doping levels.
levels. '.
barrier, effectively
barrier, effectively reducing
reducing the
the surface recombination velocity
surface recombination velocity".

kBT In(
kBT In(Nat).
~~), Electron
Electron concentration
concentration is is reduced on the
reduced on the p+ side the low-
side of the Passivation
Passivation of of front
front surface
surface withwith thinthin oxide
oxide coating.
coating. TheThe high
highsurface
surface
high jun~tion
high junction (xH)(xj+) relative
relative to to the mainmain pp side (Xj_) by
side (Xj_) by the
the ratio
ratio of the recombination velocity
recombination velocity at at a a free
free silcon
silicon surface
surface tends
tends to create
create aa dead
dead
doping levels,
doping levels, N a/
Na/Na+, Nfollows
This a+. This
from follows
continuity from
of
the Fermi
continuity of the Fermi level across
level across
layer, where
layer, where photogenerated
photogeneratedcarriers carriersare are not
not collected,
collected,at at the surface of
the junction.
junction, If If xx == Xj the ~+
Xjatat the p-+ junction an unpassivated cell. Oxidising
Oxidising the the surface c~eates
creates a thin layer of the wide
the junctionwe we have
have
band gap
gap insulator,
insulator, silicon dioxide, which
silcon dioxide, which prevents
prevents carriers from reaching
reaching
~n(xj_) == ~n(xj+)
.6.n(xj-) .6.n(xH) xx eD-Ee/kaT
et..Ecl
kBT
= =.6.n(xH)
~n(xj+)~: ~: the surface and
and hence reduces the
The interface between
the effective
silcon and silcon
between silicon silicondioxide
recombination velocity.
effective surface recombination
dioxide isis much
much less
less defective
defective
for
for the excess
excesselectron
electronconcentration
concentration.6.n.
~n, Current
Current continuity
continuity at the junction than aa free
free silcon
silicon surface.
surface. This reducesreduces the loss of carriers
carriers in
in the
the emitter
provides through surface
surface recombination,
recombination, and improves improves the response to blue blue light,
light.
provides aa second
second boundary
boundary condition,
condition,
Use
Use ofofpoint
pointcontacts
contacts at atrear,
rear.Since
Since thethe silcon-metal
silicon-metalinterface
interfaceisismore
more
D dn(xj_)
D dn(xj_) __ D
D dn(xj+)
dn(xH) defective than
defective the silcon-silcon
than the silicon-silicondioxidedioxide interface,
interface, rear
rear surface
surface recombi-
recombi-
n-
n-
dx
dx -- n+ n+
dx
dx nation can be be reduced
reduced by contacting
contacting only only part
part of the rear
rear pp layer
layer with
with
where Dn-
Dn- and
and Dn+
Dn+ are
are the
the diffsion
diffusionconstants
constantsininthe
theppand
andp+p+layers,
layers.Now,
Now, metal, using
using 'point' contacts,
contacts. The The restrest of
ofthe
thesurface
surface can
can then
thenbe bepas-
pas-
if
if we define
define an effective
effective surface
surface recombination
recombination velocity
velocity atat the
the junction,
junction,Seff,
Seff, sivated with
sivated with oxide,
oxide, andand thethe overall
overall surface
surface recombination losses greatly
recombination losses greatly
in analogy with Eq, 4,85, reduced,
reduced. In order
order toto avoid
avoid problems
problems with with series
series resistance,
resistance, thethe region
region
in analogy with Eq. 4.85,
of
of semiconductor
semiconductor closeclose to to the point
point contacts
contacts isis differentially
differentially doped
doped p+,p+.
Seff_- Dn-
- dn(xj_)
~n(xj_) dx
This
This innovation
innovationfollowed
followed fromfrom thethe rear
rear point
pointcontact
contactsolar
solarcell,
cell,described
described
below.
below,
itit follows
follows that
that
Seff Dn+ NaNadn(xj+)
dn(xH)
Seff = =- ~n(xj+)
Dn+ d
Na+ dx
.6.n(xH) N a + x
The
The electron
electron density
density in the highly
highly doped layer isis fixed
doped layer fied by
by the
theboundary
boundary
condition
conditionatat the
the rear
rear surface
surface oxidelayer
oxide layer
..

dx =+ Sn+(~n(xj
dn(xj + Xb) /""
-Dn+
-Dn+ dn(xj Xb)
= Sn+(.6.n+XjXb))
( ) ),
+ Xb ,
dx ppcontact
contact ppcontact
contact
where
where XbXb is
is the
the thickness
thickness of
of the
the highly
highlydoped
doped layer
layer and
and Sn+
Sn+ isisthe
therear
rearsur-
sur-
Fig. 7"12"
Fig. 7.12. Rear
Rearpoint
pointcontacts
contactsininp ptype
typemateriaL.
material.
face
face recombination
recombinationvelocity
velocity within
withinthe
thehighly
highlydoped
dopedlayer.
layer.IfIfrecombination
recombination
 194 ThePhysics
The Physicsof
ofSolar
Solar Cells
Cells MonocrystallineSolar
Monocrystalline Solar Cells
Cells 195
195
194

7.4.6. Strategies to
7.4.6. Strategies to reduce series resistance
reduce series resistance

. Optimisation the nn region

of the regiondoping.
doping,Reduced
Reduced doping improves collection
collection
~.. ~
Optimisation of doping improves :a ;.
o
fromthe
from the nn region,
doping increases
doping increases Vbi
givingaa better
region, giving
Vbiandandreduces
better response
reducesseries
response to to blue
seriesresistance,
light, Increased
blue light.
resistance,although
Increased nn
althoughveryveryhigh
high nn
":
..
en
Z
I
..o d:~:~~~
C\ C" C" N ~ C"
doping isis unhelpful
unhelpful forfor increasing ::
~ ..~
doping increasing Vac because of
Voc because of Auger
Auger recombination
recombination ~
..
and band
and band gap
gap narrowing.
narrowing. ~ I

Differential doping of
. Differential doping ofthe
the area
area around
around thethe contacts.
contacts. This
This is
is achieved
achieved by by en
i: ~ '! "" ......
o ~
exposing the areas
exposing the areas toto be
be contacted
contacted to to dopant rich gases
dopant rich gases before
before deposition
deposition ~ ~ M o
00 i- i-
ao
00

of the
of the contacts.
contacts, For
For point
point and
and grid
grid contacts,
contacts, the
the current
current density
density through
through ;g --
8 C'
the material close
close toto the contacted area will wil be
be high,
high. Doping
Doping this volume ::
heavily reduces
heavily reduces the
the losses
losses toto series resistance.
series resistance.
i
+- ..o o C' co
C'
'" -: N c 00
o
co
. Narrow
Narrow butbutdeep
deep fingers
fingers in front contact, as above. The high
above. The high aspect
aspect ratio ;i 6 -. M C'

reduces surface
reduces surface area
area blocked
blocked by by contacts
contacts without reducing
reducing finger
finger cross
cross +- u
en ..(J
sectional area,
sectional area, and
and the
the relatively
relatively high
highcontact
contact area
area between
betweenfingers
figers and ..
Cl
'0
semiconductor reduces
semiconductor reducesthe the current
current density
density atat the contact,
contact. i:
:: ~
~ '! 00 C'

o
C)
U '! '!
'" C' C'
~
Ql
., ci ci ..
en >
:;
7.4.7. Evolution -:cd
7.4.7. Evolutionojofsilicon
siliconsolar
solarcell
celldesign
design --
o C'
+-
Let's look
look at
at how
how these
these strategies
strategies have
have been
been incorporated
incorporated into
into the
the design
design '" ::
.iCl
S ,.1"~-4S~
C' 0 0 0 0..
of silicon
silcon solar cells. A summary
cells. A summary of of crystalline
crystallne silicon
silcon cell
cell performance
performance data ..+-Cl -:
I
is
is given
given in
in Table
Table 7,2,
7.2. -g
0:
cd -:
-en_
"
Ql ""
., ~ Cl
Black
Black cells i: I
cells o ....
., i:
i:
o.. Cl
Typical 'black
'black cell'
cell' designs
designs (so
(so called
called because
because ofoftheir
theiralmost
almostzero
zeroreflec-
reflec- :3
en .. I
;i

tivity)
tivity) were
were developed
developed in the the early
early 1980s
1980s and
and exhibited
exhibited effciencies
efficiencies of
of up
up gi 0 :; en
o
,-o ...- I
Cl
..
::
to
to 17%.
17%. Black cells
cells incorporated the innovation of the surface texturing as as
well
well as the
the features
features ofof the
thebasic
basiccell
cell described
described above,
above.
~~
.. ..
I
0:
I
.. ..
~~.s~~
'" I
i:
tS ~ 0000 i:oooo
. ~
::
~
zZ2ZZ
;: ;: 00 ;: ;:
"8.
o
~
g i:
Passivated
Passivated emitter
emittercells
cells "~
., .. ~
a3 0 "" en

Passivated
Passivated emitter
emitter solar
solar cells
cells (PESC)
(PESC) arearesoso called
calledbecause
because of of the
the innova-
innova-
Cl --
'0 __ "~~"_
~ +- 0 ~
tion
tion of
of the
the passivation
passivation ofof the
the non-contacted
non-contacted front
front surface
surface with aa thin
thinlayer
layer ~ ' Z Q, ~ 00 0)
~ +- i: Cl "_ i:
0: S o
of
of silcon
silicondioxide,
dioxide. Improvements
Improvements such such asas these
these make
make ititworthwhile
worthwhile using
using .G
~ t: ::
d ~t=..
8 "5 ==~~
00 :3
more
more expensive float zone
expensive float zone produced
produced silicon,
silcon, which
which isis better quality
quality than
than
/ "0
C'
i- 00
i:
Ci
~1: 0U ~
" ~.-
en ~~;;
Czochralski
Czochralski and has has aa longer
longer diffsion
diffusionlength,
length.TheThePESC
PESCcell cellwas
wasdesigned
designed Cl .. o00 "Olo...i:Clt;
atatthe
theUniversity
UniversityofofNew
NewSouth
SouthWales
Walesandandachieved
achievedananeffciency
efficiencyofof20%
20% in
in
~ o~
E-d:;
I
Cl
CI~~loO
g 00 "- .. i: ~ g
; i:a:a:i: a.., S
1985,
1985.
196 The Physics
The Physics of
ofSolar
SolarCells
Cells Monocrystalline
Monocrystalline Solar
SolarCells
Cells
196 197
197

"inverted"
"inverted" pyramids
pyramids

back ontact rear contact oxide

oxide
Fig. 7.13. Passivated emitter solar cell (PESC) [Green, 1995] . Fig,
Fig. 7"13. Passivated emitter solar cell (PESC) (Green, 19951" Fig. 7.15"
7.15. PERL
PERLcell
cellGreen,
[Green,19951,
1995].

1 light
l light
develop at the
develop at
than
than at
at the
contacts of
contacts
the rear
rear of
thefront,
of the
the cell
front. Another
of opposite
cell between
Another diffculty
opposite polarity
contacts of
between contacts
difficulty is
polarity on
on aa single
is the
of opposite
opposite polarity
the risk
risk of
single surface,
surface.
polarity rather
ofshorting
rather
shorting out
out between
between

PERL cell
cell
n n
oxide
oxide layer
layer The passivated
The emitter, rear
passivated emitter, rear locally diffsed (PERL)
locally diffused (PERL) solar
solar cell
cell was
was devel-
devel-
oped at UNSW, with an efficiency of 24% in 1994 [Zhao, 1994). This design
oped at UNSW, with an effciency of 24% in 1994 Zhao, 1994J. This design
ncontact pcontact
p contact ncontact
n contact exploits the
exploits the advantage
advantage of of point
point contacts
contacts inin reducing
reducing recombination
recombination at at the
the
n contact
rear
rear surface.
surface, It
It has
has the
the following
following features:
features:
Fig.
Fig" 7.14. Schematic cross
7"14" Schematic cross section
section of
of rear point contact
rea point contact celL.
cell.
Rear
Rearpoint
pointcontacts
contactsreduce
reducethe
thearea
areaof
ofthe
thesemiconductor-metal
semiconductor-metalinterface,
interface,
where recombination is high, so that most
where recombination is high, so that most of of the
the rear
rear surface may be
surface may be
Rear
Rear point
point contact
contact cell
cell contacted with oxide.
contacted with oxide.

By Grooved
Grooved front
front contacts
contacts as
as with
with the
the passivated
passivated emitter
emittersolar
solarcell,
cell.
By placing
placingboth boththe
thenand contacts on
nand pp contacts on the
the rear
rear of
of the
the cell,
cell, this
this design
design
eliminates Differential
Differential heavy
heavy doping
doping of
of nn layer
layer near
near contacts
contacts
eliminates shading losses entirely, This cell was introduced at Stanford in
shading losses entirely. This cell was introduced at Stanford in
1992, Surface
Surface texturing
texturing using
using inverted
inverted pyramids
pyramids
1992,withwith an
an efficiency
effciency ofof 22%.
22%, The
The original
original design
design was
was intended
intended for for use
use
in
in concentrators [Sinton, 1986).
concentrators Sinton, 1986J,TheThe cel!
cel!isismade
madefrom
fromlightly doped nn type
lightlydoped type
silicon with heavily doped n
silcon with heavily doped nand p type regions close to point contacts on
and p type regions close to point contacts on 7.4.8. Future
7.4.8. Future directions in s-liconcell
directions in s#iconcell design
design
the
the rear
rear surface.
surface. The
The front
front surface
surface isis passivated
passivated andand textured
textured as as usuaL.
usual. The
The ..
cell
cellisisthin
thin (100
(100pm)
/-m)andandisisintended
intendedto to operate
operate at high injection
at high injection levels,
levels, so
so "'he performance of silcon
i"The performance of silicon solarsolarcells
cellsisisnow
nowfairly
fairly close
closetotothe
the theoretical
theoretical
light trapping is important.
light trapping is important, maximum of 29%. Continuing refinements to the design,
maximum of 29%. Continuing refinements to the design, mainly aimed mainly aimedatat
Extremely
Extremelyhigh highpurity
purity material
material isis needed,
needed, because
becausephotogenerated
photogenerated car- car- reducing shading and series resistance losses, may increase effciencies
reducing shading and series resistance losses, may increase efficiencies of lab of lab
riers havetoto diffuse
riershave diffusetoto the
the rear
rear of the celL.
of the cell. Small
Small space
spacecharge
chargeregions
regionswill
wil cellstoto26%
cells 26%or or 27%
27%ininAM1.5.
AM1.S,The Themain
main challenges
challengesare arenow
nowin in improving
improving
 198 ThePhysics
The PhysicsofofSolar
SolarCells
Cells Monocrystalline
MonocrystallineSolar
SolarCells
Cells
198 199
199

cell production techniques in order to mass-produce efficient cells more

cell production techniques in order to mass-produce effcient cells more
cheaply. For example, with the buried contact cell, efforts have focused on
cheaply. For example, with the buried contact cell, efforts have focused on
producing grooves more cheaply, for example by mechanical etching.
producing grooves more cheaply, for example by mechanical etching.
AAquite
quite different direction is the thin film microcrystalline silicon cell.
different direction is the thin film microcrystallne silcon cell,
Here the objective is to reduce bulk recombination losses without losing
Here the objective is to reduce bulk recombination losses without losing
absorption and effective light trapping is required. This design works in the
absorption and effective light trapping is required. This design works in the
'high injection' limit where different physics applies. It is considered briefly
'high injection' limit where different physics applies, It is considered briefly
in Chapter 8.
in Chapter 8.

7.4.9. Alternatives to silicon

7.4.9. Alternatives to silicon
Silicon is not an ideal solar cell material, for two main reasons. One is that
Silcon is not an ideal solar cell material, for two main reasons. One is that l rr X U,K rr
its band gap (1.1 eV) is smaller than the optimum (1.4 eV) for terrestrial X U,K
its band gap (1.1 eV) is smaller than the optimum (1.4 eV) for terrestrial k
k
solar energy conversion. The other is that since its absorption coefficient
solar energy conversion, The other is that since its absorption coeffcient (a)
(a) (b)
(b)
is low, a relatively thick layer of silicon is needed (in conventional silicon
is low, a relatively thick layer of silcon is needed (in conventional silcon Fig.
designs) to absorb sunlight effectively. The significant requirement for high Fig. 7"16"
7.16. GaAs
GaAs crystal
crystal structure
structure and
and band
band structure.
structure. Notice
Notice that
that the
the conduction
conduction band
band
designs) to absorb sunlight effectively. The significant requirement for high maximum occurs at
maximum occurs at the
the same point as
same point as the
the valence band minimum
valence band minimum (the(the rr point,
point, where
where
purity silicon increases the cost, as well as the weight, of the cell. Another kk =
= 0,
0, giving
giving aa direct
direct band
band gap).
purity silcon increases the cost, as well as the weight, of the cell. Another gap).
consideration is the temperature dependence of efficiency which makes sil-
consideration is the temperature dependence of effciency which makes sil-
icon less suitable for applications under concentrated light and in space.
icon less suitable for applications under concentrated light and in space.
Therefore a number of alternative semiconductor materials have been de- there is
Therefore a number of alternative semiconductor materials have been de- there is a
a band
band gap
gap between the (normally
between the (normally empty)
empty) conduction
conduction band
band and
and
veloped for photovoltaic applications. Cell designs aimed at reducing costs the (normally filled) valence band,
the (normally filled) valence band.
veloped for photovoltaic applications. Cell designs aimed at reducing costs
by using less or less pure semiconductor material are considered in Chap- Relative to
by using less or less pure semiconductor material are considered in Chap- Relative to silcon,
silicon,111- V's have
111-V's have several
several advantages
advantages as as electronic
electronic mate-
mate-
ter 8. In the next section we will briefly consider materials, from the III-V
ter 8. In the next section we wil briefly consider materials, from the III-V rials. One is the possibility of varying the crystal composition by
rials, One is the possibilty of varying the crystal composition by replacing
replacing
group of compound semiconductors, with more favourable materials prop- some of of the
the group
group IIIIII atoms
atoms with
with another
another groupgroup III
III element in order
order to
to
group of compound semiconductors, with more favourable materials prop- some element in
erties for high efficiency single crystal cells.
cells. vary the band gap in a controlled way, Another is that for many composi-
erties for high effciency single crystal vary the band gap in a controlled way. Another is that for many composi-
tions these
tions materials are
these materials are direct
direct gap semiconductors, and
gap semiconductors, and so
so are
are much
much more
more
effective optical absorbers (see
effective optical absorbers (see Fig. 7.3). Fig. 7,3),
7.5. III-V Semiconductor Material Properties
7.5. IIi-V Semiconductor Material Properties III-Vshave been
III-Vshave been widely
widely developed
developed for for applications
applications inin optoelectron-
optoelectron-
7.5.1. III- V semiconductor band structure and optical ics, They
ics. They are are grown
grown by by aa number
number of of epitaxial
epitaxial techniques
techniques suchsuch as as liquid
liquid
7.5.1. III- V semiconductor band structure and optical
absorption phase epitaxy (LPE), molecular beam epitaxy (MBE),
phase epitaxy (LPE), molecular beam epitaxy (MBE), metal-organic chem- metal-organic chem-
absorption ical vapour
vapour deposition
deposition (MOCVD)
(MOCVD) and and metal-organic vapour phase
phase epi-
ical metal-organic vapour epi-
A III-V semiconductor is an alloy containing equal numbers of atoms
atoms from
from taxy (MOVPE) which allow minute control of the composition and layer
layer
A III-V semiconductor is an alloy containing equal numbers of taxy (MOVPE) which allow minute control of the composition and
groups III and V in the periodic table. The group III atom contributes developedininparticular
particularsosothat
that het-
het-
groups III and V in the periodic table. The group III atom contributes thickness, Epitaxial growth has been
thickness. Epitaxial growth has been developed
three valence electrons to bonding and the group V element contributes erostructures - layered structures of materials of different band gap which
three valence electrons to bonding and the group V element contributes erostructures - layered structures of materials of different band gap which
five. For many compounds the atoms arrange themselves into the zincblende e:iablespatial
spatialconfinement
confinementofofcarriers
carriersforforapplications
applicationssuch
suchasaslasers
lasers- - may
may
five, For many compounds the atoms arrange themselves into the zincblende e~able
crystal structure - two interlocking face centred cubic lattices - where .'be fabricated, The best understood and most widely used of these III-V
crystal structure - two interlockig face centred cubic lattices - where 'lbe fabricated. The best understood and most widely used of these III-V
each atom forms four bonds to neighbouring atoms of the other type. All of semiconductorsisisgallium galliumarsenide
arsenide(GaAs).
(GaAs),ItItisisalso
alsothe
themost
mostsuitable
suitable for
for
each atom forms four bonds to neighbouring atoms of the other type, All of semiconductors
the valence electrons are used up in bonding, and, as in the case of silicon, solarenergy
energyconversion.
conversion,Other Otherrelevant
relevantmaterials
materialsarearethe
the binary
binary alloys
alloys in-
in-
the valence electrons are used up in bonding, and, as in the case of silcon, solar
the lowest energy configuration for the crystal is a semiconductor where dium phosphide (InP), gallum antimonide (GaSb) and ternary alloys such
the lowest energy configuration for the crystal is a semiconductor where dium phosphide (InP), gallium antimonide (GaSb) and ternary alloys such
200 The Physics
The Physics of
ofSolar
SolarCells
Cells Monocrystalline
Monocrystalline Solar
SolarCells
Cells 201
200 201

as aluminium gallium arsenide (AlxGal_xAs), where a fraction x ofthe thegal-

gal- GaAs
GaAs enjoys
enjoys other
other advantages
advantages forfor solar
solar cell
cell applications,
applications. One
One isis aa better
better
as aluminium gallum arsenide (AlxGai_xAs), where a fraction x of
lium atoms in GaAs have been replaced by aluminium atoms, indium gal- temperature coeffcient than silcon, Solar cell effciency tends to
temperature coefficient than silicon. Solar cell efficiency tends to decreasedecrease
lium atoms in GaAs have been replaced by aluminium atoms, indium gal-
lium phosphide (InxGal_xP) and indium gallium arsenide (InxGal_xAs). as
as temperature
temperatureincreases,
increases, because
because ofofincreasing
increasing carrier
carrier recombination
recombination and and
lium phosphide (InxGai-xP) and indium gallum arsenide (InxGai-xAs),
Indiumphosphide
phosphidehas
has aa suitable
suitable band
bandgap
gap for
forphotovoltaic
photovoltaicconversion
conversionand
and aa decreasing
decreasing band gap. The first effect is more pronounced in
band gap, The first effect is more pronounced in silcon
siliconwhere
where
Indium
is particularly attractive for space applications on account of its resistance recombination
recombination depends
depends upon
upon the
the availabilty
availabilityofofphonons,
phonons,which
whichincreases
increases
is particularly attractive for space applications on account of its resistance
to degradation
degradationunder
underradiation,
radiation,oror'radiation
'radiationhardness'.
hardness'.Properties
PropertiesofofGaAs
GaAs with
with temperature,
temperature. This
This means
means that
that GaAs
GaAs performs
performs better
better in
in situations
situations
to
are covered elsewhere [Lush, 1986; Adachi, 1992; Bube, 1998]. where
where the
the cell
cell operates
operates at
at high
high temperature,
temperature, under
under concentration
concentration and
and in
in
are covered elsewhere Lush, 1986; Adachi, 1992; Bube, 1998J.
space,
space.
Another
Another factor
factor relevant
relevant toto space
space is
is the
the radiation
radiation resistance
resistance ofof the
the mate-
mate-
7.5.2. Gallium arsenide
7.5.2. Gallium arsenide riaL. Exposure to
rial. Exposure to extraterrestrial
extraterrestrial radiation
radiationdegrades
degrades the
the effciency
efficiency of ofaa solar
solar
GaAs hashas aa band
band gap gap ofof 1.42
1.42 eV at room
room temperature,
temperature. This This isis close
close to
to cell over its lifetime. GaAs has a better radiation hardness
cell over its lifetime. GaAs has a better radiation hardness than silicon , than silcon,
GaAs eV at
the optimum for the standard solar spectrum and means
the optimum for the standard solar spectrum and means a conversion ef- a conversion ef- although
although indium
indium phosphide
phosphide isis better
better still.
stil.
ficiency of
ficiency 31% is
of 31% theoreti~ally possible,
is theoretically possible. ItIt is
is aa direct
direct gapgap material
material andand High purity GaAs is much
High purity GaAs is much more costly more costly than
than pure
pure silcon,
silicon, and
and GaAs
GaAs
absorbs strongly above its band gap. Over visible wavelengths
absorbs strongly above its band gap, Over visible wavelengths the absorp- the absorp- cells are some
cells are some 5 5 to
to 10
10 times
times asas expensive
expensive in in spite
spite of
of reduced
reduced cellcell thickness,
thickness.
tion coeffcient
tion coefficient of
of GaAs
GaAs isis about
about ten times that
ten times that of of silcon
silicon (see
(see Fig.
Fig. 7,3),
7.3), However,
However, GaAs GaAs production
productiontechnology
technologyisisstill stil maturing,
maturing, and and production
production
and only a few f.J.m rather than hundreds of f.J.m are needed
and only a few lLm rather than hundreds of lLm are needed for the active for the active costs
costs are decreasing as the scale of manufacture of GaAs based devices
are decreasing as the scale of manufacture of GaAs based devices for
for
region of
region of the solar cell,
the solar cell. This
This most
most important
important for for space
space applications
applications where
where applications in optoelectronics
applications in optoelectronics expands. expands,
the priority is to reduce the cell weight.
the priority is to reduce the cell weight,
These
These factors
factors mean
mean that
that GaAs
GaAs cells
cells have
have been
been developed
developed primarily
primarily forfor
use in space, The most likely terrestrial application is
use in space. The most likely terrestrial application is for power genera-for power genera-
1.6+00 ~---------------------,
tion under
tion under concentrated
concentrated light.light. (Concentration
(Concentration is is discussed
discussed in in Chapter
Chapter 9.) 9.)
1"EK6
Although most of the design features mentioned below are general, some
Although most of the design features mentioned below are general, some

----
"':"s
":e
U were developed
were developed with with concentration
concentration in in mind,
mind.
u
C
c:
CP 1.Et05
uQ)
'u
1.EK5

~;:Q)
oo
7.5.3.
7.5.3. Doping
Doping
uu
c III- V semiconductors
III-V semiconductorscan can be
be doped
doped byby replacing
replacing one
one ofof the
the elements
elements withwith
oc:o 1.Et04
1"Et Ai 0.33Ga
Ai 0.33 0.67 As
Ga 0,67 As one of
one of different
differentvalence.
valence,InInGaAs,
GaAs,nn type
type doping
doping may
may be be achieved
achieved by by intro-
intro-
~
:
c.
o..
ducing controlled amounts of silcon during growth. The tetravalent
ducing controlled amounts of silicon during growth. The tetravalent silicon silcon
eno
en
atoms normally
atoms normallyreplace
replacesome
someofofthe
thetrivalent
trivalentgallium
gallumatoms
atoms in in the
the lattice,
lattice,
.Q
.c
c: 1.Et03+-----L~--~-_r----_+----~
1"EK3
introducing a donor state associated with the extra valence
introducing a donor state associated with the extra valence electron. Tin, electron, Tin,
1.5
1"5 22 2.5
2"5 33 whichisisalso
which alsotetravalent,
tetravalent, has
has also
alsobeen
beenused
usedas
asaadonor
donorimpurity.
impurity, For Forpptype
type
1
doping, carbon is the most commonly used impurity. Carbon,
doping, carbon is the most commonly used impurity. Carbon, like silicon, like silicon,
Energy/eV
Energy I eV
isis tetravalent
tetravalentbut but under
under certain
certain growth
growth conditions
conditionsitit prefers
prefers to to substitute
substitute
Fig. 7.17. Absorption coefficient of GaAs and Alo.33Gao.67As. Note the strong absorp- Jor arsenic
Jor arsenic atoms
atoms in in the
the lattice,
lattice, and
and so
so introduces
introduces aa deficiency
deficiency of of valence
valence
Fig. 7.17" Absorption coeffcient of GaAs and Alo"33Gao"67As. Note the strong absorp-
tion at energies just above the band gap, and the similar shape of the spectra. As the
tion at energies just above the band gap, and the similar shape of the spectra" As the rt".electrons
electronsand andhence
henceacceptor
acceptorstates.
states.Alternatively
Alternativelythethegroup
group IIII element
element
aluminium fraction x is increased, the AlxGal_xAs band edge moves to higher energies.
aluminium fraction x is increased, the AlxGai_xAs band edge moves to higher energies.
At compositions above x = 0.4 the band gap becomes indirect and AlxGal_xAs is too
beryllum can
beryllium can be
be used,
used, which
which introduces
introducesan anacceptor
acceptorstate
state byby substitut-
substitut-
At compositions above x = 0.4 the band gap becomes indirect and AlxGai-xAs is too ing for gallum atoms, Dopants may be introduced by diffsion or directly
poor an absorber to be useful for photogeneration. However, high aluminium content
poor an absorber to be useful for photogeneration, However, high aluminium content ing for gallium atoms. Dopants may be introduced by diffusion or directly
material is used as a 'window', much as oxide is used in silicon cells.
material is used as a 'window', much as oxide is used in silcon cells. during growth by epitaxial
during growth by epitaxial techniques.techniques, .
202 The Physics
The Physicsof
of Solar
Solar Cells
Cells MonocrystallineSolar
Monocrystalline Solar Cells
Cells 203
203
202

Table7.3.
Table 7"3" Tyical
TypicalGaAs
GaAsmaterial
materialand
andcell
cellpaxameters,
parameters, used
used in
in calculations
calculations in
in Fig.
Fig. 7,19"
7.19.
7.5.4. Recombination
7.5.4. Recombination
EMITTER (P
EMITTER (P TYPE) BASE (N
TYPE) BASE (N TYPE)
TYPE)
Radiative recombination is
Radiative is faster
faster in in GaAs
GaAsthan than inin silicon,
silcon, and may may dominate
dominate
in very pure materiaL.
in material. The The direct
direct band
band gap gap means
meansthat that direct
direct transitions
transitions Thickness // /.Lm
Thickness im 0.5
0"5 44
Doping/cm-33
Doping/cm- 11 xx 10 18 11 XX 10 17
1018
from conduction
from conduction to to valence
valence bandband are more more likely
likelyandand thethe radiative lifetime is is Minority carrier
Minority carrier diffusion
diffusionconstant/cm
constant/cm2 2 s-l
s-1 25
1017
10
16 cm -3, 25 10
aa factor
factor of 104 shorter, For example, at
10 4 shorter. at acceptor
acceptor doping
doping levels
levels of of1016
10 em -3, Minority caxrier lifetime/s
Minority carrier lifetime/s 10-99
11 xx 10- 1- 8
1-8
Tradisisaround
Trad around11J.LS.sininpure
purepptype typeGaAs,
GaAs,compared
comparedto to around
around 10 10 msms in in silicon
silcon Minority carrier diffusion
Minority diffusion length/
length/im
/.Lm 1.5
1.5 33
Lush, 1986;
1986;Green,
Green, 1995].
1995J,The The large
large difference
differenceisis due due to to the difference Surface recombination
Surface recombination velocity/em
velocity/em s-l
s-1 1000000
1000000 1000000
1000000
[Lush, difference in in
the absorption coeffcients
coefficients at energies
energies justjust above the respective absorption Reflectivity
Reflectivity 0.05
0,05
Absorption: at
Absorption: at 500 nm/cm-11
500 nm/cm- 110000
110000
edges, We
edges. We know
knowfrom fromSec.Sec,4.5.1
4,5.1that thatthe
therecombination
recombinationrate rate isis proportional
proportional at 800
at nm/cm-11
800 nm/cm- 13000
13000
to the value of a within kBT
within kBT of of the absorption
absorption edge. edge,
Auger recombination,
Auger recombination,on onthethe other
other hand,
hand, is is much
much slower
slowerthan than in in silicon
silcon
6 cm
due
due toto the much smallerintrinsic
much smaller intrinsic carrier concentration
concentration (n (nj = 22 x 10 106 em -3 in
GaAs, compared to 1 x 10 101010 cm-
cm-3 3 ininsilicon)
silcon) and is negligible
negligible in in photovoltaic
photovoltaic Like bulk recombination,
recombination, surface recombination isis higher
surface recombination higher in
in GaAs
GaAs than
devices.
devices. silcon, At
in silicon. At untreated
untreated surfaces
surfaces the
the minority
minority carrier
carrier surface
surface recombination
In practical mate~ials, nonradiative Shockley
practical mate~ials, Shockley Read Hall recombination is
is of the order of 106 cm
of 106 cm s-l [Hovel, 1975J
s-l Hovel, 1975] but this
this can
can bebe reduced
reduced to under
under
4 cm S-l using window layers, discussed below [Bube, 1998].
through defect
defect states dominates,
dominates. SRH SRH lifetimes
lifetimes depend
depend on on the
the nature and 104
10 cm s-l using window layers, discussed below Bube, 1998J.
concentration of
concentration of impurities
impurities and and the the growth
growth conditions.
conditions, Electron
Electron lifetime
lifetime in
good quality p type type GaAs
GaAs varies
varies fromfrom around
around 11 .s J.Ls at
atlow
lowdoping
doping levelslevels toto
7.5.5. Carrier transport
7.5.5. Carrier transport
approximately (1019/Na) 19
(10 INa) ns at higher higher doping,
doping. For For holes
holes in nn type type GaAs
GaAs Tp Tp
18 3
varies from
varies from 10-100
10-100 ns ns at
at low
low doping
doping to to aa few
few nsns at
at Nd Nd :;> 1018
10 cm-3,
cm- . Tp Tp isis As in silicon,
silcon, electrons
electrons have aa higher
higher mobility
mobilty than
than holes
holes in GaAs,
GaAs. Minority
up to one
one order of magnitude shorter than Tn Tn in p type GaAs GaAs doped to the electrons have
have aa mobility
mobilty of around
around 5000
5000cm
cm22 V-I s-l at low doping which
y-1 s-l at low doping which
same 2 V-I S-l at doping levels of 10 18 cm- 3 The mi-
same leveL.
level. falls to around
falls around 1000
1000 cm cm2 y-1 S-l at doping levels of 1018 cm-3,
In p-n devices, SRH recombinationininthe the space
space charge
charge region
region dominates 2
In p- devices, SRH recombination dominates nority hole
nority hole mobility
mobilty varies
varies from
from 300-400
300-400 cm V-Is-l
cm2 y-1 s-latatlow
lowdoping
dopinglevels
levels
performance,
performance. This is because the SRH recombination rate rate is greatest in this to less
to less than
than 100
100 cm 2
cm2 V-I s-l at
y-1 S-l at doping
doping levels
levels ofof more
more than
than 10
101818 cm-
cm-3,3
.
region where nand
region where nand pp are are similar,
similar, and and because
because the the carrier
carrier densities
densities in the the Together
Together withwith minority carrier lifetimes,
minority carrier lifetimes,these
theselead
leadtoto diffusion
diffsion lengths
lengths ofof
junction
junction region
region of of aa GaAs
GaAs devicedevice are high high because
because of the high high absorption,
absorption. a few .m
J.Lm in moderately
moderately doped GaAs, longer
doped GaAs, longer for
for pp than
than nn type,
type. In
In ternary
ternary
The recombination
recombination rate therefore therefore involves
involves both both carrier types,types, and and is not not the higher
alloys, the higher defect
defect density
density leads
leads to much faster recombination.
recombination. For For ex-
ex-
simply
simply proportional
proportional to to the minority
minority carrier density, density, as as inin silicon,
silcon, nor is is itit ample,
ample, inin nn doped
doped AlxGa1_xAs,
AlxGa1-xAs, Lp Lp may bebe less
less than
than 0.1
0.1 .m
J.Lmand
andlifetimes
lifetimes
possible to
possible to resolve
resolve thethe lifetime
lifetime intointo factors
factors duedue toto different
different processes,
processes, as as inin may be
may be aa few
few tens
tens of
ofps,
ps.
Eq,7,8,
Eq.7.8. The
The doping
doping dependent resistivityofofpp type
dependent resistivity type GaAs
GaAs is is around
around
The
The effect
effect of space charge region recombination isis evident
region recombination evident in in the dark
dark 15
(10 INa)
(1015/ Na)OhmOhmcm. cm.ItIt is
is about
about anan order
order of
of magnitude
magnitude greater
greater forfor n type
n type
current
current characteristics
characteristics of GaAs GaAs solar cells. cells. TheThe dark current tends to vary vary material doped
material dopedtotothe
thesame
sameleveL.
level.
with
with the
the ideality
ideality factor
factor of of 22characteristic
characteristic of of SRH
SRH recombination
recombination at the the
junction, Jdark
junction, Jdark rv eqV /2kaT,
'" eqV j2kBT, at at low
low positive
positive biases,
biases. In In silcon
silicon cells,
cells, for
for com-
com-
parison,
parison, where
where thethe dark
dark current
currentisis dominated
dominated by by recombination
recombination in in the
theneu-
neu-
1.5.6. Reflectivity
1.5.6. Rejlectivity
t"".
tral
tral regions,
regions, thethe ideality
ideality factor
factor isis close
close to to 1.
1. At
Athigher
higherforward
forward biasesbiases in in GaAs
GaAs has
has a refractive
refractive index
index of 3.3
3.3 and
and a natural
natural reflectivity
reflectivity ofof30-40%
30-40%
good
good quality
qualityGaAs
GaAscells cellsJdark
Jdark begins
begins totovary varylike
likeeqVeqV /kaT,
jkBT, as radiative
radiative re- re- over visible
over visible wavelengths.
wavelengths. Suitable
Suitable anti-reflection
anti-reflectioncoatings
coatingscan
canbe
be made
made from
from
combination
combination beginsbegins to to dominate.
dominate. silcon
silicon nitride.
nitride.
204
204 The Physics
The Physics of
of Solar
Solar Cells
Cells Monocrystalline Solar
Monocrystalline Solar Cells
Cells 205
205

GaAs BOO nm
cell, 800
GaA cell light
om light GaAs 500 nm
cell, 500
GaA cell light
om light
front contacts
front contacts
....- ....-
./ AR coat
wnmr@'
~!!~iiiiiiiiiii is 0.8
-m..l..)C
.a)C:i 0.8
0.8
!

./ AR coat .,- l
l s 0.81i

:- !!!!!!~!!!!~!!!!~_ ~ pp AIGaAs
AIGaAs window
window ;>
II = 0.6
>-
~ cC
III
-:!i!
0.6
ca .,~ 0.4
I _Roconil I !
i
i ~~
;> c
ii
0.6
GI ii 0.6
as ., 0.4
-:!i!
.! -8 0.4
.......l-----------1- p GaAs emitter
- p GaAs emitter '3
:> U
()
E
ECC 0.2 ~AbaO'lbn....
'bn E
:> ()
:: i
C 0.2 -RocOnt>ina'ionl

o:i -
E c
:i -
:>- 0.2 i- -~OnDmtbn
Ablorptlon :>- 0.2
I-
nn GaAs
GaAs base
0o oo !7
t I2 I3I I
I J 0
o
o
Absorption

nn type
type buffer Depth/pm
Depth Ipm Depth/pm
Depth Ipm
Fig.
Fig. 7.19.
7.19, Simulated
Simulated cumulative absorption
absorption and recombination rates
and recombination rates for
for aa GaAs so-
GaAs so-
nn type
type substrate
lar cell
lar cell with the parameters
parameters in in Table
Table 7"3
7.3 under
under monochromatic light at two
monochromatic light two different
different
wavelengthsand
wavelengths and at
at aa bias
bias close
closetoto open
open circuit.
circuit.
contact

Fig" 7.18.
Fig. 7"18" Layer
Layer structure
structureof
ofaawindowed
windowed monocrystallne
monocrystallineGaAs
GaAssolar
solarcelL.
cell.
bulk
bulkrecombination
recombination is
is unimportant
unimportant relative
relative to
to junction
junction and
andsurface
surface re-
re-
combination
rear
rearsurface
surface recombination
recombinationisis negligible,
negligible, because
because of the high
high absorption
absorption
7.6. GaAs
7.6. GaAsSolar
Solar Cell
Cell Design
Design
7.6.1. Basic
7.6.1. Basic GaAs
GaAs solar
solar cell
cell Therefore, the objectives in optimising GaAs cell
Therefore, cell design
design should
should be
be to

In GaAs,
GaAs, because diffsion lengths
because diffusion greater than the absorption
lengths greater absorption depth can Minimise
. Minimise front
front surface
surface recombination
recombination
be achieved
be achieved for
for either
either doping
doping type,
type, cells
cellscan
canbe
beprepared
prepared as
as either
eitherp-n or
p- or Minimise
. Minimise junction
junction recombination
n-p
n-p designs,
designs. In either case the emitter
emitter should
should be as thin as
as possible
possible without . Minimise
Minimise series
series resistance
resistance
increasing series
series resistance
resistance too
too much.
much, For
For the
the p-n
p-n design,
design, aa 0,5
0.5 .m
/-lm emitter
emitter
doped
doped to 1018 cm-3
1018 cm is typical;
-3 is typical; for
for the
the n-p
n-p design, the emitter can be as
design, the as We wil
will add
add one
one more
more very
very practical
practical objective:
objective:
thin as
as 0,2
0.2 .m
/-lm because of the higher n type conductivity,
conductivity. In practice p+-n
p+-n
designs seem to perform better
better than
thannn+-p
+ -p designs,
designs. The base is much shorter Minimise
. Minimisesubstrate
substratecost.
cost.
than in
in silcon
siliconcells,
cells, typically
typically 2-4 .m
/-lm and
and comparable with the diffsion
comparable with diffusion
length,
length. This arises because the GaAs layers are extremely thin, and must be
be grown
grown
on a substrate for mechanical stabilty, yet
mechanical stability, yet depositing
depositing GaAs
GaAs cells
cells on
on GaAs
GaAs
7.6.2.
7.6.2. Optimisation
OptimisationofofGaAs
GaAssolar
solarcell
celldesign
design substrates is
substrates is prohibitively
prohibitively expensive.
expensive.
Strategies to
Strategies to address these issues
address these issues are
are discussed
discussed below.
below,
Figure 7,19
7.19 ilustrates
illustrates absorption
absorption and
and recombination profile in
recombination profile in a typical
typical
GaAs p-
p-njunction
junctioncell,
cell,calculated
calculatedasasFig,
Fig. 7,8
7.8 and
and using
using the
the materials
materials pa-
pa-
rameters
rameters in Table
Table 7,3,
7.3. The
The graphs
graphs show
show that forfor GaAs
GaAs thetheinfluences
influences on
on 7.6.3.
7.6.3. Strategies
Strategies to
to reduce frnt surface
reduce front surface reombination
recombination
recombination
recombination are
are rather
ratherdifferent,
different.We
Wecan
can make
make thethe following
followingobservations:
observations: .,
"'
"'l ' Because
Because ofof the
the high absorption
absorption coeffcient,
coefficient, more
more carriers
carriers are
are generated
generated in
in
. absorption
absorptionofoflight
lightisisgood
goodatatall
allwavelengths
wavelengths the emitter in a GaAs than a silicon cell. This means the contribution
the emitter in a GaAs than a silcon celL. This means the contribution of of
. front
front surface
surface recombination is important
recombination is for long
important for long wavelengths
wavelengths the
the emitter
emitter to
to the
thephotocurrent
photocurrentisisnotnotnegligible
negligible and also
also that
that surface
surface and
and
. recombination
recombinationininthe
thejunction
junctionregion
regionisisdominant
dominant bulk
bulk recombination
recombination in this
this region
region are important,
important.
 206
206
The Physics
The Physics of
ofSolar
SolarCells
Cells Monocrystalline
Monocrystalline Solar
SolarCells
Cells 207
207

.Front
Frontsurface
surfacefields.
fields. AAheavily
heavily doped
doped layer
layer is
is introduced
introduced by by diffusion.
diffsion. TheThe window
principle is the same as for the back surface field discussed
principle is the same as for the back surface field discussed for silcon, for silicon.
Windowlayers, Front surface
layers. Front surface recombination
recombination can can be be reduced
reduced by by intro-
intro- Eg
. Window
ducing a front surface window of a higher band gap material to reflect wi"
ducing a front surface window of a higher band gap material to reflect
minority carriers
carriers away
away from
from the
the surface.
surface. TheThe principle
principle is is similar
similar to to the
the
minority
back surface field. The higher band gap of the
back surface field, The higher band gap of the window layer presents
potential barrier
aa potential barrier to toelectrons
electrons generated
generated in
window
the ppregion
in the
layer
region(Fig.
presents
(Fig. 7,20),
7.20).
IE

p
.. n
IE,
The window layer is transparent to most visible light,
The window layer is transparent to most visible light, but the interface but the interface
between thethe window
window and and the
the bulk
bulk GaAs
GaAs isis much
much less less defective
defective than
than un-un- Fig. 7.20.
Fig" 7.20. Band
Band diagram
diagramof
of aa p-n
p- GaAs
GaAscell
cell with
with aa pp type
typeAlGaAs
AlGaAs window
window of band gap
of band gap
between Ewin"
Ewin
treated GaAs. The consequence is that the effective front
treated GaAs. The consequence is that the effective front surface velocity surface velocity
is greatly
is greatly reduced,
reduced. An An analysis
analysis similar
similar to to that
thatgiven
given above
above forfor back
back sur-
sur-
face field shows that, if interface recombination is negligible,
face field shows that, if interface recombination is negligible, the effective the effective graded layer
surface velocity
surface velocity at at aa window
window layer
layer isis given
given by
by

where l::l.E
S _D
Seff-L
eff-
D
_ ~i eSn+Ln+
L~eEg/kT
n+ S~AEg/kT
SL
{
cosh . + sinh .l
LDn+ Ln+ Ln+
n+ ~ sinh . Ln+
Dn+ + cosh
SntLnt
Dnt

Ln+.
cosh 2:.b..
Lnt
sinh 2:.b.. + cosh 2:.b..
Dnt Lnt
+ sinh 2:.b..
Lnt

L nt
}
(7.11)
(7,11)
IEW;' _ _
IE w;:""'ed laye,
""",,--_l
.. IE, Eg
where tiEgg isis the
the difference
difference in
in band
band gaps
gaps between
between GaAs
GaAs and
and the
the win-
win- p nn
dow and n+ denotes the window layer. Typical window
dow and n+ denotes the window layer, Tyical window materials are materials are
AlxGal_xAs and InxGai-xP,
InxGal-xP, both
bothof
ofwhich
which are
are lattice
lattice matched
matched to
to GaAs
GaAs Fig"
Fig: :7"21.
.21. Band
Band diagram
dia~r~m of
of aa GaAs
GaAs cell with an
cell with an AlxGai-xAs
AlxGal_xAs emitter
emitter of
of graded
graded com-
com-
AlxGai-xAs and position" The compositional
and posItIOn. The composItIOnal grade
grade provides
provides an
an effective
effective electric
electric field
field which
which accelerates
accelerates
and so so result
result in good quality
in good quality interfaces
interfaces withwith aa low
low density
density ofof interface
interface electrons towards
electrons towards the
the junction
junction region
region and
and assists
assists charge
charge separation.
separation.
states [Hovel, 1975).
states Hovel, 1975J,
. Heterojunctions
Heterojunctions and and graded
graded emitters.
emitters. OtherOther options
options are
are to fabricate the
to fabricate the
whole of the emitter from a wider gap material than the base, producing the junction,
the junction, as
as shown
shown inin Fig,
Fig. 7,21. This can
7.21. This can be
be done
done inin GaAs
GaAs cells
cells using
using
whole of the emitter from a wider gap material than the base, producing
aa p-n heterojunction cell, AlxGai_xAs of varying aluminium fraction and has resulted
AlxGal_xAs of varying aluminium fraction and has resulted in enhanced in enhanced
rn heterojunction cell, where
wherethe thep-n junction actually
p- junction actually occurs
occurs atat the
the
junction between two materials of different composition. The advantage photo current through
photocurrent through improved
improved minority
minority carrier
carrier collection,
collection. The
The wider
wider gap
gap
junction between two materials of different composition, The advantage
is that the emitter still absorbs short wavelengths but recombination is acts like a window layer, shifting the absorption of longer wavelength
acts like a window layer, shifting the absorption of longer wavelength pho- pho-
is that the emitter stil absorbs short wavelengths but recombination is
suppressed, tons towards
tons towards the
the junction
junction where
where they
they are
are more
more.likely
likelytotobebeutilised.
utilsed. These
These
suppressed, so so improving
improvingresponse
responsetotoblue blue light.
light. The
The wider
wider gap
gap emitter
emitter
also strategies would
strategies would certainly
certainly be
be useful
usefulfor
forsilicon
silconcells,
cells,but
butwith
withsilicon
silcon there
there is
is
also offers the possibilty of increases in Voc (though in practice these are
offers the possibility of increases in Voc (though in practice these are
negligible) no convenient wider band gap semiconductor with a similar lattice
no convenient wider band gap semiconductor with a similar lattice constant constant
negligible)and andflexibility
flexibiltyto to maintain
maintain high high doping
dopingininemitter
emitter without
without thethe
recombination which could
which could be used.
used,
recombination losses
losseswhich
whichwould
wouldresult
result in
in aa homojunction
homojunction cell.cell. However,
However,
the interface is likely to introduce defects, and since
the interface is likely to introduce defects, and since recombination is recombination is
already
already highest
highestinin the
the depleted
depletedregionregionwhere
wherenand nand pp are
are similar,
similar, there
there 7.6.4. to reduce
Strategies to
7.6.4. Strategies series resistance
reduce series resistance
isisaadanger that defects at the heterojunction will assist
danger that defects at the heterojunction wil assist recombination.
recombination.
A Seriesresistance
Series resistanceisisan
an issue
issue with
with all
all solar
solar cell
cell designs
designs because
because ofof the
the need
need
A compromise
compromiseisistotolocatelocatethethehigh
highbandbandgap gap- - low
low band
band gap
gap interface
interface
away from the depleted region in the neutral player. j;o expose
..to exposeasasmuch
muchofofthethe front
front surface
surfaceasas possible
possibletotothethe light,
light, yet
yet make
make
away from the depleted region in the neutral player, i' electrical contact to it to collect the current, In GaAs concentrator cells
i' electrical contact to it to collect the current. In GaAs concentrator cells
Another
Another idea
idea isisto
to grade
grade the
the composition
compositionof ofthe
theplayer,
player, from
from GaAs
GaAs near
near itit is
is aa particularly important issue.
particularly important issue,ForForaa cell
celltoto operate
operate atat optimal
optimal effi-
eff-
to
to the
the junction,
junction, to
to aa high
high band gap alloy
band gap alloy at
at the front surface.
the front surface. The composi-
The composi- ciency under 100 suns, the sheet resistance of the cell should be less that
ciency under 100 suns, the sheet resistance of the cell should be less that
tional
tional grade
grade introduces
introduces an an electric
electric field
field which
whichassists
assistselectron
electronmigration
migrationto
to 10-3 3
Ohm-cm2,2 GaAs cells for use in concentration are therefore designed
10- Ohm-cm . GaAs cells for use in concentration are therefore designed
208 The
The Physics
Physics of Solar Cells
Cells Monocrystalline
Monocrystalline Solar Cells
Cells 209

to have minimal resistance at highhigh injection

injection levels,
levels, and are not
not necessarily
necessarily trapping structures,
structures. Charge
Charge separation
separation isis maximised
maximised by using a good qual-
the optimum design
design for
for one sun. This means special grid patterns with high
one sun. This means special grid patterns ity junction with a high high built-in
built-in bias. bias. Effcient
Efficient charge
charge transport requires requires
metallisation, and very high emitter
metallsation, and very high emitter doping,
doping, which
which can
can be
be achieved
achieved with
with the
the good quality
good quality crystal with low low bulk and and surface
surface recombination
recombination and good good
help of a window
window layer and a front
front surface
surface field,
field. majority carrier
majority carrier conductivity.
conductivity. For For anyany material the ideal Jrn rn structure
structurehas has
a thin heavily
heavily doped emitter on top of of aa thicker,
thicker, heavily
heavily doped base, base. The
7.6.5. Strategies to
7.6.5. Strategies to reduce
reduce substrate
substrate cost
cost remaining priorities
remaining priorities depend
depend upon upon the material
material used,used.
Silcon has aa low
Silicon low absorption coeffcientcoefficient and most photogeneration takes
Because
Because thethe GaAs
GaAs cellcellisissoso thin,
thin, itit must
must be be grown
grown on on aa substrate,
substrate, andand place
place in in the base,
base. p type silcon silicon is is used
used as as the
the base
base because
because the minority
minority
it is
is better
better to
to choose
choose a substrate
substrate of of the
the same
same lattice
lattice constant
constant as as the
the cell
cell carrier transport characteristics
carrier characteristics are are better
better thanthan in nn typetype materiaL.
material. The The
material
material in order not to
in order to introduce
introduce crystal
crystal defects
defects at the the rear
rear interface.
interface. base should be several several hundred lLm thick for
/-Lm thick for good
good light
light absorption, while while
GaAs
GaAs substrates are are ideal,
ideal, but
but prohibitively
prohibitively expensive,
expensive, and for for large
large scale
scale the n type
type emitter
emitterisis typically
typically less less than
than 0.50.5 micron thick. The base base is lightly
production germanium, which has a similar lattice
production germanium, which has a similar lattice constant, used, Ge constant, is used. Ge doped so
doped so that electron
electron diffsion
diffusionlengthslengths are arelonglong enough
enough (several
(several hundred
has same lattice
has the same lattice constant
constant as as GaAs,
GaAs, but but isis rather
rather rare
rare and in the end end /-Lm) for
lLm) for good charge collection,
good charge collection. Because
Because of of the
the low
low absorption,
absorption, the the priorities
priorities
the cost of GaAs
GaAs on Ge Ge solar cells
cells isis likely
likely to to be limited by
be limited by the cost of in silicon solar cell design are to
silcon solar to minimise
minimise light light reflection
reflectionand and shading,
shading, and and to
Ge.
Ge, Growth of of GaAs
GaAs on on Si
Si substrates
substrates suffers
suffers fromfrom the
the difference
difference in in lattice reduce recombination at the rear rear surface,
surface. Reflection is is reduced
reduced by by texturing
texturing
constants, and poor material
material quality
quality inevitably
inevitably results,
results. the front surface
surface with aa pattern
pattern of ofmicron
micron sized sized pyramids
pyramids and by adding adding
One solution isis to re-use the substrate,
substrate. Techniques
Techniques have have been developed
developed an anti-reflection coat,
an coat. Shading
Shading is is reduced
reduced by by using
using thin contact
contact fingers,
fingers,
in which epitaxially grown GaAs GaAs wafers
wafers are are removed
removedfrom fromaa GaAs
GaAssubstrate
substrate and by burying
burying the contacts
contacts into into thethe emitter,
emitter, while
while the the series
series resistance
resistance
by etching or cleaving along an intermediate plane, plane. Cells produced this way which results
results from thin thin contacts
contacts can can bebe reduced
reduced by differential doping. doping. of
are brittle and
and stil
stillrequire
requiremechanical
mechanical support.
support. Another
Another approach
approach to cost cost the semiconductor near near to the the contacts,
contacts. Surface
Surface recombination is is reduced
reduced
reductions
reductions is is to use
use polycrystalline
polycrystalline GaAs,GaAs, in which case case lattice matching
matching by passivating
passivating the the surface
surface with with aa layer
layer of of silicon
silcon dioxide,
dioxide, and and by by the use use
with a substrate
substrate isis less
less important.
important.20% 20% effcient
efficient poly-GaAs
poly-GaAs cells
cells have been of point
of point contacts
contacts at the
at the rear. rear.
The best monoThe best mono crystallinecrystallne silcon
silicon cell
cell isis 24%
24%
grown on Germanium substrates.
substrates. A A long term term objective would be to deposit effcient in AM1.5.
efficient AM1.5.
poly-GaAs cells on silicon,
poly-GaAs cells on silcon, metal or glass.
or glass. GaAs is aa strong absorber and devices devices only only aa few
few mi.::rons
mi.:rons thick
thick absorb
most of the
most the light.
light, Both
Both n-p and rn Jrnstructures
structuresmay maybe beused,
used, with
withtypical
typical
emitter thicknesses
thicknesses of less less than 0,5 0.5 lLm
/-Lm andand base
base thicknesses
thicknesses of of 2-4
2-4 lLm,
/-Lm.
7.7.
7.7. Summary
Summary Significant photogeneration
Significant photogeneration takes takes placeplaceinin thethe emitter
emitter and junction
junction as as well
well
The most effcient
efficient single
single junction
junction photovoltaic
photovoltaiccellscellsare basedononp-n
arebased p- junc- as the base,
as base. This
This means
means that recombination
recombination at at the front
front surface
surface and in
tions
tions in monocrystalline semiconductors, Crystallne silcon is the most
in monocrystalline semiconductors. Crystalline silicon is the most the junction is important.
important. Front Front surface
surface recombination
recombination can be reduced reduced by
important photovoltaic
photovoltaic material
material and
and is widely usedused for appli-
for terrestrial appli- building in
building in doped
doped window
window layerslayers from a wider band gap semiconductor. semiconductor, The
cations. Crystalline GaAs
cations, Crystalline GaAs isis more
more suitable
suitable for applications in
for applications space and
in space window separates
window separatesthe the active
active region
regionfrom fromthe the metallic
metallc contact, and helps helps
under concentration.
concentration. Both materials have have suitable
suitable band gaps leading
band gaps leading toto a to drive
drive minority
minority carriers
carriers towards
towards the junction,junction. Junction
Junction recombination
recombination
high theoretical effciency.
efficiency. is minimised
is minimised mainly mainy by by control
control of the the crystal
crystal quality
quality and and doping
doping levels,
levels.
The objectives in
The objectives solar cell
in solar cell design
design are
are to maxmise
maximise lightlight absorption,
absorption, Reflection
Reflection is is minimised
minimised using using anti-reflection
anti-reflection coats; coats;texturing
texturing is is not suitable
charge G because of the larger size of light trapping structures compared to the device
charge separation
separationand andcharge
chargetransport,
transport,and andtotomaximise
maxise the thephotovolt-
photovolt- G because of the larger size of light trapping structures compared to the device
age.
age. The design
design factors
factors which
which may
may bebe varied
varied inin aa Jrn junctionsolar
rn junction solarcell
cell rI' thickness,
thickness, and and thethe sensitivity
sensitivity of of the
the front
front surface
surface quality,
quality. As As in in silcon,
silicon,
are
are the layer thicknesses, the doping levels, the surface treatments
thicknesses, the doping levels, the surface treatments and the the front surface
surface contact pattern pattern shouldshould be be designed
designed to minimise
minimise shading
shading
front surface
front surface contact pattern. High light absorption is achieved
pattern. High light absorption is achieved by using a without enhancing series resistance. resistance, The best single cell cell efficiency,
effciency, of25.1%,
of25,l%,
high minimising shading
high optical depth, minimising shading and reflection,
reflection, and using light
and by using has been achieved
has been achieved in GaAs.
in GaAs,
210 The Physics
The Physics of Solar Cells
Cells

References
S. Physical Properties
S, Adachi, Physical Properties of ofIII-
III-VV Semiconductor
Semiconductor Compounds
Compounds (Chichester:
(Chichester:
Wiley, 1992).
Wiley, 1992).
R. Photovoltaic Materials
R, Bube, Photovoltaic Materials (Imperial
(Imperial College
College Press, 1998).
Press, 1998), Chapter
Chapter 8
M.A. Silicon Solar
Green, Silicon
M.A" Green, Solar Cells:
Cells: Advanced
Advanced Principles and and Practice
Practice (Sydney:
(Sydney: Cen-
Cen-
tre for
for Photovoltaic
Photovoltaic Engineering, 1995).
Engineering, 1995).
M.A. Green, K.
M,A, Green, Emery, D.L.
K. Emery, D,L, King,
King, S.
Progress in Photovoltaics
tables", Progress
S, Igari
Photovoltaics 9,
Igari and
and W.
W. Warta,
287-293 (2001),
9, 287-293 (2001).
"Solar cell
Wara, "Solar cell effciency
efficiency Thin Film Solar
Solar Cells
Cells
H.J. Hovel,
H.J. Hovel, "Solar
"Solar cells",
cells", in
in Semiconductors
Semiconductors and and Semimetals
Semimetals 11, 11, eds,
eds. R.K,
R.K.
Wilardson and
Willardson and A,C,
A.C. Beer
Beer (1975),
(1975).
G.B. Properties of
G.B. Lush, in Properties of Gallium
Gallium Arsenide
Arsenide (INSPEC, 1986).
(INSPEC, 1986).
M. Physics of
M, Shur, Physics of Semiconductor
Semiconductor Devices
Devices (Prentice Hall International, 1990).
International, 1990),
R.
R. Sinton al., "27.5%
Sinton etet al., silicon concentrator
"27,5% silicon concentrator solar cells", Electron
solar cells", Device Letts.
Electron Device Letts.
EDL-7,
EDL-7, 567 567 (1986),
(1986). 8.1. Introduction
8.1. Introduction
R.J.
R.J. van
van Overstraeten
Overstraeten and and R,R. P. Mertens, Physics
p, Mertens, Physics Technology
Technology and Use of
and Use of Photo-
Photo-
voltaics 1986).
Hilger, 1986),
voltaics (Bristol: Adam Hilger, In Chapter
Chapter 66 we we covered
covered the the theory of idealideal p-n
p-n junction
junction solar
solar cells,
cells, and
J. Zhao and
J, Zhao M.A. Green,
and M,A, "23.5% effcient
Green, "23,5% efficient silicon
silicon solar
solar cell", Prog. Photovoltaics
cell", Prog, Photovoltaics in Chapter
in Chapter 7 applied
7 applied crystallne silcon
it to mono it to mono crystalline silicon and
and GaAs
GaAs devices,
devices. We We
2, 227-230
227-230 (1994).
(1994). seen that,
have seen that, provided
provided that that minority
minority carrier
carrierdiffusion
diffusion lengths exceed typ-
ical absorption
ical absorption depths,depths, junctions
p-nmake
p-n junctions make efficient photo converters with a
effcient photo

high collection
collection effciency,
efficiency, where
where recombination at the the surfaces
surfaces is is the dom-
dom-
inant loss
loss process. However, single
process. However, single crystals
crystals are
are expensive
expensive to to produce and
so there is
so there is aa great
great dealdeal ofof interest
interest inin finding
finding photovoltaic materials of
photovoltaic materials of less
less
demanding material quality which can be grown
demanding grown more cheaply,
cheaply. A number
of materials have have been
been identified
identified of which the best best developed
developed at present
present are
amorphous silicon
amorphous silcon (a-Si),
(a-Si), polycrystallne
polycrystalline cadmium
cadmium telluride (CdTe),
(CdTe), poly-
poly-
crystallne copper
crystalline copper indium
indium diselenide (CuInSe2) and
diselenide (CuInSe2) and microcrystalline
microcrystallne thin
film silicon
film silcon (p-Si),
(p-Si). These 'thin 'thin fim'
film'materials
materialsare areusually
usuallyproduced
producedby byphys-
phys-
ical or chemical
chemical deposition
deposition techniques
techniques which can be applied to to large
large areas
areas
and fast
and fast throughput.
throughput, Note Note that the term 'thin 'thinfilm'
film'refers
refers more
more toto solar
solar cell
cell
technologieswith
technologies with mass-production
mass-productionpossibilities
possibilties rather
rather than the film
film thick-
thick-
ness: GaAs
ness: GaAs p-n p-n junction cells, with an active layer aa few few pm
pm thick,
thick, are thin,
but do not not belong
belong to this this class.
class.
Polycrystallne and
Polycrystalline and amorphous
amorphous semiconductors
semiconductors contain intrinsic defects defects
which increase
increase the the density
density of traps and and recombination
recombination centres,
centres. For solar
solar
cells, this
cells, this has the consequence
consequence that:
. Diffsion
Diffusion lengths
lengths areare shorter,
shorter, soso the
the material
material needs
needs to
to be
be a strong op-
a strong op-
~
'.
"/"
tical absorber.
absorber. Alternatively, multiplejunctions
Alternatively, multiple junctionsmust
must bebe used
used to make
make
the device optically
the device optically thick.
thick. In
In the
the case
case of
of very
very short
short diffusion lengths, it
diffsion lengths, it
may be necessary
may necessary to to use extended
extended built-in
built-in electric fields to
electric fields to aid carrier
collection,This
collection. This isis the
the case
caseinin amorphous
amorphoussilicon,
silcon,where
wherep-i-n
p-i-n structures
are preferred.
are preferred,

211
212 The
The Physics
Physics of Solar Cells
Cells Thin Film Solar Cells
Thin Cells 213

. Losses
Lossesinin the
the layers
layers close
close to
to the
the front
front surface
surface are
are greater,
greater, so
so it
it is
is advan-
advan- 8.2. Thin Film
8.2. Thin FilmPhotovoltaic
Photovoltaic Materials
Materials
tageous to replace the emitter with a wider band gap window
tageous to replace the emitter with a wider band gap window materiaL. material.
8.2.1. Requirementsfor
8.2.1. Requirements forsuitable
suitable materials
materials
. TheThepresence
presence of of defect
defect states in thethe band
band gap
gap can
can make
make the
the materials
materials
difficult to dope,
diffcult to dope, andand can
can limit
limit the
the built-in
built-in bias
bias available
available from a junction Good thin film
Good film materials should should be low cost, non-toxic,
low cost, non-toxic, robust
robust and stable.
through Fermi
Fermi level
level pinning. They should
They absorb light
should absorb light more strongly than
more strongly than silcon.
silicon. Higher
Higher absorption
absorption
. The
Thepresence
presenceof ofgrain
grain boundaries
boundaries andand other
other intrinsic
intrinsic defects
defects increases
increases the reduces the cell thickness
reduces thickness and so relaxes relaxes the requirement for long minority-
resistivity of the films
films particularly low doping densities,
particularly at low densities, and makes the carrier diffusion
carrier lengths, allowing
diffusion lengths, allowingless lesspure
pure polycrystalline
polycrystallne or amorphous
amorphous
conductivity dependent
dependent on carrier density,
density, soso influencing
influencing the electrical
electrical materials to be
materials be used.
used. Figure 8.1 8.1 compares
compares the the absorption
absorption coefficients
coeffcients for
characteristics of devices.
characteristics of devices. several photovoltaic
several photovoltaic materials
materials and and the maximum
maximum photon current which can
. The
Thepresence
presence of defects
defectssimilarly
similarly means
meansthatthatminority
minority carrier
crrier lifetime and be generatedin
be generated in aathin
thin film as aa function
function of its thickness.
thickness. Notice how weakly
diffusion constant are
diffsion constant are carrier
carrier density
density dependent.
dependent. silcon absorbs, in comparison
crystalline silicon comparison with with thethe other materials. Suitable
materials should transport charge
should transport charge effciently,
efficiently, and should be readily readily doped.
doped.
What this means
What this means for for the
the calculation
calculation of of solar cell current-voltage characteris- Materials are
Materials are particularly attractive ifif they can can be be deposited
deposited in in such
such a way
way
tics is that (i) the
that (i) the model
model of p-njunction
of the p-n junctiondeveloped
developed in
in previous
previous chapters that arrays
that arrays of of interconnected
interconnected cells can can bebe produced
produced at at once
once (Fig.
(Fig. 8.2).
8.2). This
must
must bebe modified
modifiedfor forp-i-n
p-i-n structures
structures andandp-n heterojunctions and
p- heterojunctions and (ii) the greatly reduces the module module cost.
solution of the transport equations becomes
transport equations becomes more complicated, because the Of the elemental
elemental semiconductors,
semiconductors, only only silicon
silcon hashas a suitable bandband gap
gap
parameters such as mobilty,mobility, lifetime
lifetime and
and diffusion
diffusion constant are
are functions
functions for photovoltaic energy conversion.
for Compound semiconductors
conversion. Compound semiconductors greatly ex-
density. The differential equations
of carrier density. equations of the form tend the rangerange of of available materials and
available materials and ofof these
these aa number
number of II-VI bi- bi-
nary compounds
compounds and and I-III-VI
I-Ill-VI ternary
ternarycompounds
compounds have have been used for for thin
an
an 11
-- = =-"\. I n ++ Gn
-'\7.In G n -- Un
film photovoltaics.
photovoltaics. Many Many of ofthese
these are direct band band gap semiconductors
semiconductors with with
at
at qq high optical
high optical absorption
absorption relative
relative to silcon. to silicon. The I-III-VI
The I-II 1- VI compounds
compounds (or
chalcogenides)are
chalcogenides) areanalogous
analogoustotoII-VI's II-VI's where
where the the group II element
element hashas
which result from electron continuity, are no longer longer linear
linear in n. In the course
in n. been replaced
replaced by by aa group
group II and a group III species. species. At present the leading leading
of this chapter we will show how
wil show how the simple
simple model
model of the p-n
ofthe p-n junction can compound semiconductors
compound semiconductorsfor for thin
thin film
film photovoltaics
photovoltaicsare are the
the II-VI semi-
semi-
be adapted for other device device structures,
structures, and and indicate how current generation conductor, CdTe,
conductor, CdTe, and the thechalcogenide
chalcogenide alloys,
alloys, CuInGaSe2
CulnGaSe2 and CuInSe2.CulnSe2.
and recombination
recombination are are influenced
influenced by the the presence
presence ofof defects.
defects. Other new materials are continually being being investigated,
investigated, including
including other
other 11-
II-
The chapter
chapter is is organised
organised as as follows:
follows: first wewe discuss the
discuss the general features I-ILL-VIcompounds,
VI and I-III-VI compounds,amorphousamorphouscarboncarbonand and nanocrystalline
nanocrystallne silicon.
silicon.
of thin film
film photovoltaic
photovoltaic materials.
materials. Then we focus focus on amorphous
amorphous silcon,
silicon, Molecular electronic
Molecular electronic materials
materials formform aa new classclass of thin-film
thin-film photovoltaic
photovoltaic
reviewing
reviewing the the materials consequences for
materials properties, the consequences for charge
charge transport
transport materials, but rely rely on different physics,
physics, andand they
they will
wil not
not bebe discussed
discussed here.
and photo current
and photo generation, and
current generation, design of amorphous
and the design amorphous silicon solar
silcon solar
cells. At this stage the analysis of the p-i-n junction
cells. At this stage the analysis of the p-i-n junction is presented. Thenis presented. Then
we
we move
move on on to
to polycrystalline
polycrystallne thin film film materials.
materials. In this
this section
section aa simple
simple 8.3.
8.3. Amorphous Silicon
Amorphous Silcon
model of aa grain
grain boundary is presented. Finally Finally the
thedesign
design ofof CdTe,
CdTe, CuInSe2
CulnSe2 8.3.1. Materials properties
8.3.1. Materials properties
and thin
thin film
film silcon
siliconsolar
solarcells
cells isis discussed.
discussed.
Note that
Note that this
this chapter
chapter is is not
not intended
intended as as aa comprehensive review of
comprehensive review of Amorphous silicon
Amorphous silicon(a-Si)
(a-Si)isisthe thebest
best developed
developedthin
thinfilm
fim material
material and has
the materials science
science and technology
technology of thin film solar cells, but rather
of thin film solar cells, but rather to been
been in commercial production since
commercial production since 1980, initially for
1980, initially for use in.
in hand held
highlight
highlight certain aspects of the device device physics.
physics. Reviews
Reviews of ofthe
the state
state of,thin calculators.
film photovoltaics
photovoltaics for for the
the different
different materials
materials areare found
found in
in Bube
Bube lBube,
[Bube, 1998j
1998] As a material for photovoltaics, it has the advantages of relatively cheap,
and Archer and Hill [Archer,
and Archer and HillArcher, 2001j. 2001]. low temperature
low temperature deposition
(-( 3000) 300C) and deposition and the possibility of growing
the possibilty of growing on a
on a
214 The
The Physics
Physics of Solar Cells
Cells Thin Film Solar Cells
Thin Cells 215

-- 6 back contact
serl'liconductor
"";E
;"E \ \ transparent
\ serliconductor
\ transparent
front front contact
contact

--...
u
..cc
U
CII
CI
5
~,~ ___a""m ...._........._.w......._...,......
.,~_.___u_. "",a"""'"m",a,w"""a~""",,,,G
_________________-
- -glass
- glass

-1~~~~
'U
=CIICI
==
0
0
u 4
cc
:,00c.
:;:::;
GaAs
...0..0
Co
Fig.
Fig. 8.2. Integral interconnections
8.2. Integral interconnectionsinin aa thin
thin film
film cell.
celL.ToTo form
form integrally
integrally interconnected
interconnected
1/
1/1 3 modules the
modules the layers are scribed
layers are scribed between
between stages
stages first
first to
to separate
separate individual cells
cells and
and then
.a to connect them in in series.
series. This removes the need for separate
separate contacting and connecting
~
~
Cl
CI
cells, which
of cells, which is
removes the
is costly in conventional module
need for
module designs.
designs.
connecting

.2
22+-----~--~~~-----~----~------+_----~
0.5 1.5 2 1.5 2 2.5
2.5 3 3.5 variety of substrates, including glass,
variety glass, metal and plastic, with
with diverse
diverse com-
com-
Energy/eV
Energy I eV
mercial applications.
mercial applications. The
The amorphous
amorphous nature has several
several important
important conse-
conse-
quences for
quences for photovoltaics.
photovoltaics. Absorption
Absorption ofof visible
visiblelight
lightisisbetter
better than
than for
for crys-
(a)
(a) silicon, but
talline silicon, but doping
doping and
and charge
charge transport
transport are more difficult.
diffcult. The
The avail-
avail-
abilty of
ability ofalloys
alloys with different band gap enable the design
design of
ofheterostructure
heterostructure
45 and tandem
tandem devices.
devices.
40
.....
'E
'E 35 8.3.2. Defects in
8.3.2. Defects in amorphous material
amorphous material
u
<C
cC 30

-...
-...E..
E
C
C
~
..
25

20
CdTe In amorphous
orientations, as
neighbours of
neighbours
materials, the
amorphous materials,
as well as
of any
anyatom
atom are
the lattice contains

are co-ordinated
contains aa range of bond lengths and
unsatisfied 'dangling'
as unsatisfied 'dangling' bonds.
co-ordinatedalmost
bonds. Although the
almostexactly
exactlyasasininthe
the nearest
nearest
thecrystalline
crystallne
:J
:::J material, the the combined
combined effect of small
effect of small bond
bond distortions means
means thatthat there is
is
U
U 15
.s.s00 10
virtually no correlation between between an an atom
atom and its more distant
distant neighbours.
neighbours.
.c
..c The long rangerange order of the crystal is gone. a-Si, Si
gone. In a-Si, Si atoms
atoms are arranged
ii
D.
5
in anapproximate
in an approximate lattice but with a variation
tetrahedral lattice
tetrahedral variation of up to 100 10 in
0 the bond angles.
angles. As mentioned in
As mentioned in Chapter
Chapter 4, 4, this loss of order
loss of order means
means that
that
0.001 0.01 0.1 11 10 100
100 1000
1000
the selection rules for photon absorption
selection rules absorption are are relaxed,
relaxed, and
and aa semiconductor
semiconductor
iim
Thickness I J.Lm which isis indirect
which indirect in in its
its crystalline
crystallne form
form behaves likelike aa direct
direct gap material in
(b)
(b) its amorphous form. This increased absorption absorption is one reason why amorphous
Fig. 8.1. (a)
(a)Absorption
Absorptioncoeffcients
coefficientsofofaanumber
number ofofdifferent
differentphotovoltaic
photovoltaic materials.
materials.
silcon is
silicon is of
of interest
interest for for photovoltaics.
photovoltaics.
Fig. 8.1.
(A derivative of
of the
the organic
organic semiconductor
semiconductor polyphenylene
polyphenylene vinylene
vinylene (MDMO-PPV)
(MDMO-PPV) is is The variation in Si-Si distance and orientation gives rise to a spreading
gives rise
(A derivative
included [Mitchell, 1977;
included for comparison.) Mitchell, 1977; Tuttle, 1987;
1987; Fritzsche,
Fritzsche, 1985);
1985); (b)
(b) Maximum
Maximum in the
the electron
electron energy levels, levels, relative
relative toto the
the perfect
perfect crystal. This spreading
spreading
photon current available
available from
from each
each material
material under
under AM1.5
AM1.5 illumination, func~ion of
as aa func~ion
ilumination, as
film thickness, assuming
assuming perfect collection
collection of
appears as
appears as aa tail in the the density
density of states at the the top
top of
ofthe
the valence
valence band
band
fim thickness, of all
all photogenerated
photogenerated charges.
charges. The
The saturation
saturation
photocurrent is
photocurrent a function
is a function of
of band
band gap.
gap. The
The maximum
maximum photocurrent
photocurrent supplied
supplied by by the
the and
and thethe bottom
bottom of the conduction band,
of the conduction band, known
known as as an Urbach
Urbach taiL.
tail. Dan-
AM1.5 spectrum
AM1.5 spectrum is is around
around 49
49 mAcm-
mAcm-2. 2. gling bondstates
gling bond states are
are due
due to
to Si
Si atoms
atoms which
which are
are co-ordinated
co-ordinatedonly only to
to three
216 The Physics
The Physics of Solar Cells
Cells Thin Film Solar Cells
Thin Cells 217

The defects
defects in amorphous material differ
amorphous material from those
differ from those in
in polycrystalline
polycrystallne
materials in
materials in that they
they occur
occur uniformly
uniformly throughout
throughout the material and not
. uncoordinated
uncoordinated Si
Si atom
atom
only at grain
only at grain boundaries.
boundaries.

(] dangling bond orbital

tJ dangling bond orbital

8.3.3.
8.3.3. Absorption

The loss
The loss of crystal order means that the absorption
means that absorption coeffcient
coefficient is is higher
higher
than in crystallne
crystalline silcon.
silicon. In
In crystallne
crystalline silcon
silicon the
the band
band gap
gap isis indirect
indirect for
for
most visible wavelengths
wavelengths and and so
so absorption
absorption of of aa photon requires the simul-simul-
Fig.
Fig. 8.3. Danglingbonds
8.3. Dangling bondsininamorphous
amorphoussilicon
siliconininwhich
which some
some silicon
silicon atoms are bonded
bonded taneous absorption of a phonon to conserve crystal momentum.
conserve crystal momentum. Absorption
to
to only
only three
three rather
rather than
than four
four neighbours, leaving an
neighbours, leaving unused valence
an unused valenceorbitaL.
orbital. This defect
This defect
is
thus is limited
limited by the availabilty
availability of
of phonons.
phonons. In amorphous silcon there
amorphous silicon
is known
known asas aa dangling
dangling bond, may be
bond, and it may be neutral,
neutral,positively
positively or
or negatively
negatively charged.
charged.
is no well defined E-k
is no well defined E-k relationship and no requirement conserve crystal
requirement to conserve
momentum. Absorption
momentum. Absorption depends
depends simply
simplyupon upon thethe availability
availabilty of photons
photons
crystalline amorphous and the density
density of states inin valence
valence and conduction bands, much as it does does
in direct
direct gap
gap crystals.
crystals. The absorption coeffcient
coefficient is is about
about anan order
order of of mag-
mag-

Energy
l/ tail

l/ tail ~:':UClion band

I~
l,)
~:':UClion band
nitude greater than
nitude greater
Fig. 8.1).

absorption
than in

absorption coefficient
cally has
cally
in crystallne
crystalline silcon

a-Si with hydrogen

Passivation of a-Si
silicon (c-Si)

coeffcient and the band gap.

has aa band gap of 1.7 eV. eV. This
This is
(c-Si) at

hydrogen (discussed
at visible

(discussed below)
gap. Material used
is higher
higher than
visible wavelengths

used for
wavelengths (see

below) increases
increases both
for solar cells
than the optimum
optimum for
(see

both the
cells typi-
typi-
for solar
Ji"'\ dangling bond defects
l\'d\ dangling bond defects
energy conversion,
energy conversion, butbut material with lowerlower concentrations of hydrogenhydrogen is

r
l,,~: tail states unusable
unusable duedue to
to poor doping
doping andand transport properties.
properties.
--'t".
~"'\

valence band
rL.~.: tail states 8.3.4.
8.3.4. Doping
Doping
16 3
In unpassivated
unpassivated a-Sia-Si the defect density isis so
defect density high (>
so high ()o 10
1016 cm-3)
cm- that the
) that

density of states material cannot

material normally be
cannot normally be doped.
doped. TheThe extra carriers
carriers which would would bebe
introduced into the conduction
introduced conduction or valence
valence bandband by donor or acceptor
acceptor im-im-
Fig.
Fig. 8.4. Schematicdensity
8.4. Schematic densityof
of states
states in
in amorphous
amorphous material,
material, compared
compared to
to the
the crystalline
crystallne purities are captured
captured byby dangling
dangling bond
bond defects.
defects. However,
However, the background
background
form.
density of
density of defect
defect states
states may
may be reduced
reduced by by saturating the'dangling
the- dangling bonds
bonds
with atomic
with atomic hydrogen
hydrogen (Fig.
(Fig. 8.5).
8.5). Hydrogen
Hydrogen formsforms aa bond
bond with
with the unpaired
neighbouring Si atoms, leaving one valence
valence orbital which is not involved
involved in electron in
electron in a neutral (Do)
(Do) defect
defect and removes
removes thethe capacity
capacity of of that defect
defect
bonding. The dangling bond may be positively chargedcharged (D+), neutral
neutral (DO)
(DO) to trap
trap an
anelectron
electron or
oraahole.
hole.Passivation
Passivation with with5-10%
5-10%hydrogen
hydrogenreduces
reduces
or negatively charged (D-). An excess of D- states
negatively charged (D-). An excess of D- states gives gives rise to n type a-Si
a-Si the density ofof dangling bonds
bonds to around
around 101510 15 cm- 3,
cm-3, produces material
and produces material
while excess
excess D+ gives rise
D+ gives rise to p-type materiaL.
to p-type material. More defects
defects can be created from which workable
from which workable p-n junctions can
p--n junctions can bebe made.
made.

by irradiating the material,

material, by
by heating
heating and
and sudden
sudden cooling,
cooling, or
or by extt1nsic
extansic The material may be dopeddoped nn oror pp type
type but the doping effciency
efficiency is low.
doping. The dangling bond states
doping. states give
give rise to energy levels
levels deep
deep in
in the
the band example, doping
For example, doping with
with phosphorus
phosphorus introduces density Nd
introduces aa density Nd of
of neutral
neutral P
gap
gap (Fig. 8.4).
8.4). atoms which
which inin crystalline
crystallne silcon
siliconwould
would normally
normally ionise to add one electron
 The Physics of Solar Cells,
The Physics Cells, Thin Film Solar Cells
Thin Cells 219
218

Density
of states
CB
- -n n-n- donor level
donor level
_....,I;lOL....J;lOL....J;l0L--
CB
----
EF
-----EF
valence band conduction band _ _ _ _ _ defect level
defect level
- - - - - defect level EF
ft n ,. EF
_-"QL....J;IQ.....oQ_ acceptor level
VB VB
VB
n type
ntype ptype
p type
))
Energy Fig.
Fig. 8.6. Fermi levels
8.6. Fermi levels in and nn type
inp pand type amorphous material.
amorphous materiaL.

Fig. 8.5. Schematic

Fig. 8.5. Schematicofofdensity
densityofofstates
statesbefore
before(black)
(black)and
andafter
after(.grey) passivat~on in
(.grey )passivat~on in
amorphous
amorphous silicon. Unpassivated dangling bond defects are responsiblefor.
silicon. Unpassivated dangling bond defects are responsIble for.p~s ~he
m ~he
p~s II 8.3.5. Transport
8.3.5. Transport
density of states deep in the band gap. Before passivation the defect densIty IS so hIgh
density of states deep in the band gap. Before passivation the defect density is so high
that
that the
the material
material cannot
cannot be
be doped.
doped. The defect
The defect states whichwhich remain
remain after
after hydrogen passivation act
hydrogen passivation act both
both as
charge traps
charge traps and recombination centres and
recombination centres and dominate
dominate charge
charge transport
transport in
a-Si.
to the
the conduction
conduction band:
band: The distribution of tail states
states below
below the conduction
conduction and valence
valence band
edges act as traps for
edges for mobile
mobile carriers. Charge carriers in these states move move
pO -4 p+ + e - .
by aa sequence
by sequence of of thermal activation and
thermal activation retrapping events.
and retrapping events. This distribution
This distribution
in energies leadsto
energies leads to aa distribution
distribution in
in the time constants for for any transient
In amorphous silicon,
In amorphous silicon, however,
however, the
the addition of an
addition of an electron
electron upsets
upsets the
the equi-
equi- process,
process, andand aa strong dependence upon the
dependence upon the occupation
occupation ofof the
the states,
states, and
librium between neutral and negatively charged dangling bonds, and drives
librium between neutral and negatively charged dangling bonds, and drives hence carrier
hence carrier density.
density. Consequently
Consequently thethe usual
usual transport
transport parameters of mo-
the following
following reaction
reaction to
to the right: bility, lifetime,
lifetime, and
and diffusion
diffusion constant
constant are
are density
density dependent
dependent andand hard
hard to
determine. Transport characteristics can be modelled
determine. modelled by including transi-
e- + DO ? D- from the
tions to and from the trap states. The density of tail states in the conduction
band, say, is often modelled
modelled as as an exponential of the form
so that the density of D- states increases. This decreases the minority
so that the density of D- states increases. This decreases the minority
carrier
carrier lifetime sinceD-
lifetime since states are
D- states are recombination
recombination centres centres forfor holes.
holes. It can
It can g()
E = Nt
kBTo(E
exp-kBTo
Ec)
be shown that the density of D- increases like ...;Nd
be shown that the density of D- increases like .. and therefore that the
and therefore that the
density of majority carriers increases
majority carriers increases more
more slowly
slowly than Nd The
than Nd. The effect
effect on
on the
the
density of
Fermi level is to pull the Fermi level away from the donor or acceptor level where Nt
where Nt is the
the volume
volume density of tail
density of tail states, and To To isis aa characteristic
characteristic
Fermi level is to pull the Fermi level away from the donor or acceptor level 'temperature' which
'temperature' which describes
describes the
the depth
depthofofthe
thetaiL.
tail.Such
Suchapproaches
approachessuc- suc-
towards
towards the defect levels
the defect levels in
in the
the band gap, as
band gap, as shown
shown in in Fig. 8.6. When
Fig. 8.6. When thethe
density of dangling bonds is very high, the Fermi level is pinned amongst cessfully reproduce
cessfully reproduce the
the features
features of
of transport measurements
measurements in in a-Si.
a-Si. (For
(For
density of dangling bonds is very high, the Fermi level is pinned amongst aa review, see Tiedje Tiedje,
see Tiedje [Tiedje, 1984J.) Charge transport
1984].) Charge transport in in such
such aa defective
defective
the defect states.
the defect states. Low
Low doping
doping efficiency
effciency meansmeansthat the majority
that the majority carrier
carrier
activation energy - which is the difference between Fermi level and band medium is sometimes dispersive transport.
sometimes called dispersive transport.
activation energy - which is the difference between Fermi level and band
edge - is high. (Incrystallne
crystallinematerial
materialthisthisshould
shouldbe beequal
equalto tothe
thedifference
difference The dangling
The bond states
dangling bond states which
which remain
remain after
after passivation
passivation act act as
as
edge - is high. (In recombination centres
recombination centres and
and can
can be
be treated most
most simply
simply by by including
including cap-
cap-
between the impurity level and the band edge.) In p-type
between the impurity level and the band edge.) In p-type a-Si the activation a-Si the activation
ture of
of electrons
electrons and holes
holes by two
two discrete levels in
discrete levels in the
the band gap gap repre-
repre-
energy
energy is is around
around 0.4 0.4 eV.
eV. These
These large
large activation
activation energies
energieslimit
limitthethe size(~f
sizeaf the
the senting the unoccupied
senting unoccupied and singly occupied state
singly occupied state of the defect (Fig.
(Fig. 8.7).
8.7).
built-in bias which can be achieved at a p-n or p-i-n
built-in bias which can be achieved at a p-n or p-i-n junction, increasing junction, increasing
[e.g.
e.g. Spear,
Spear, 1976].
1976j. Rate
Rate equations
equationscancan be
be constructed
constructed for for the capture
capture andand
the difference between
the difference betweenthe the built-in
built-in bias
bias and
and the band gap.
the band gap.
220
220 of Solar
The Physics of Solar Cells
Cells Thin Film
Film Solar
Solar Cells
Cells 221
221

Energy
Energy

1_,.
l~ D-lOo

Ef
-n
DOIO+

pptype
type type nntype
type

Fig. 8.7.
Fig. 8.7. AA trivalent
trivalent defect
defect in
in amorphous material. The
amorphous materiaL. The upper
upperlevel
level represents
represents the
the - - - - - - - - - - - - - - + )) Distance
Distance
D-IDa
D- /Dostate
state (a(a singly
singly occupied
occupied defect
defect as
as seen
seen by
by the
the electron)
electron) and
and the
the lower
lower level
level
represents DO
represents DO /D+ (unoccupied defect).
ID+ (unoccupied defect) .
Fig. 8.8.
8.8. Band
Band profile
profile of p-i--n
p-i-n junction.
junction.

emission of
emission of carriers
carriers from
from that level using
that level using detailed
detailed balance
balance and
and Fermi Dirac
Fermi Dirac
8.3.7. Related
8.3.7. Related alloys
alloys
statistics. a-Si:H may be
a-Si:H may be alloyed
alloyedwith
with carbon
carbon (C)
(C) or
or with
with germanium
germanium (Ge)
(Ge) to produce
hydrogenated amorphous
In undoped hydrogenated amorphous silicon (a-Si:H) the minority
silcon (a-Si:H) minority car-
car-
compound amorphous materials of wider
compound amorphous materials of wider (a-SiC:H)
(a-SiC:H) or
or narrower
narrower (a-SiGe:H)
rier lifetime is
rier lifetime is typically
typically 10-20
10-20 .s and the
J-LS and thediffusion
diffusion length
length around
around0.1
0.1im,
J-Lm,
band gap. These
These allow
allow the design
design ofof multi-junction,
multi-junction, heteroface
heteroface or graded
although
although bothboth areare carrier
carrier density
density dependent.
dependent. Electron
Electron mobility
mobilty is rather
is rather
6 to 10- 4 m 2 V-1s- 1 cf. 10- 7 to 10- 6 m 2
cells. Materials
cells. Materials properties
properties are
are slightly
slightly worse
worse inin the
the alloys; for instance
alloys; for instance a
better than hole mobility (10-
better than hole mobility (10-6 to 10-4 m2 V-1s-1 cf. 10-7 to 10-6 m2 higher density
higher density of valence
valence band
band tail
tail states in
in a-Ge.
a-Ge.
V-1s-l
V-1s-1 for for holes),
holes), probably
probably due
due to an asymmetric
to an asymmetric trap distribution. With
trap distribution. With
doping
doping the defect density
the defect density increases
increases andand diffusion lengths are
diffsion lengths are much
much reduced.
reduced.
This means that
This means carrier collection
that carrier collection in in aa Jrn junction would
p-n junction would be
be extremely
extremely 8.4. Amorphous
8.4. AmorphousSilcon
SiliconSolar
Solar Cell
Cell Design
Design
poor,
poor, and consequently Jri-n structures are
consequently p-i-n structures are used. used.
8.4.1. Amorphous
8.4.1. Amorphous silicon p-i-n structures
silicon p-i-n structures

The basic a-Si

The basic a-Si solar
solar cell is aa Jri-n
cell is junction. Since diffusion
p-i-n junction. diffusion lengths
lengths are
8.3.6. Stability
8.3.6. Stability
so short in doped a-Si,
so a-Si, the central
central undoped
undoped or intrinsic
intrinsic region
region isis needed
needed
Amorphous
Amorphous silicon suffers from
silcon suffers from light-induced
light-induced degradation
degradation known
known as as the
the to extend
extend the the thickness
thickness overover which
which photons
photons may may bebe effectively
effectively absorbed.
absorbed.
Staebler Wronski effect. The defect density in a-Si:H increases
Staebler Wronski effect. The defect density in a-Si:H increases with light with light The built-in
The built-in bias is is dropped across the
dropped across the width
width of the i-region, creating an
i-region, creating
exposure,
exposure, over over aa time scale of
time scale of months,
months, to to cause
cause an increase in
an increase the recom-
in the recom- electric
electric field which drives charge separation (discussed
drives charge separation (discussed in Sec. 5.5). in Sec. 5.5). In
In the
bination current and
bination current and reduction
reduction in in effciency.
efficiency. It is believed
It is believed that light energy
that light energy Jri-n structure
p-i-n structure photo carriers are
photo carriers are collected
collectedprimarily
primarilyby by drift
drift rather
rather than
breaks some Si-H bonds to increase the density of
breaks some Si-H bonds to increase the density of dangling bonds. The dangling bonds. The by diffusion.
system is excited into in a higher energy configuration with
system is excited into in a higher energy configuration with more active de- more active de- thickness of
The thickness of the
the i region should be
region should be optimised
optimised for for maximum
maximum currentcurrent
fects. Annealing at a few hundred degrees Centigrade
fects. Annealing at a few hundred degrees Centigrade allows the structureallows the structure generation. Although
generation. Although more more light
light isis absorbed
absorbed in in a thicker
thicker region,
region, charged
charged
to relax, and
to relax, and the
the dangling
dangling bonds
bonds toto bebe resaturated.
resaturated. For For this
this reason
reason a-Si a-Si defects reduce
defects reduce the the electric
electric field
fieldacross
acrossthe the ii region,
region, and
and at somesome thickness
thickness
solar cells may perform rather better in high temperature
solar cells may perform rather better in high temperature environments. environments. the width
the width of the i region region wil
will exceed
exceed thethe space
space charge
charge width as shown shown in
In
In aa typical
typical a-Si
a-Si solar
solar Gell
cell the
the efficiency
effciency isis reduced
reduced byby upup to
to 30%
30% in in the
the Fig. 8.10
Fig. 8.10 below.
below.The The remaining,
remaining,neutral
neutral part
part of the
the i layer
layer is a 'dead layer'
first
first six
six months
months as as aa result of the
the Staebler Wronski effect, effect, and
and the fill fa:
the fill ctor
factor and does
and does not
not contribute
contribute to to the photocurrent.
falls
falls from
from over 0.7to
over 0.7 to about
about 0.6.
0.6.This
This light
light induced
induced degradation
degradation is is the
the major
major Clearly the
Clearly the cell
cellshould
should be bedesigned
designedsosothatthatthethe depletion
depletion width
width isis greater
greater
disadvantage
disadvantage of of a-Si
a-Si asas aa photovoltaic material.
photovoltaic materiaL. than the
than the thickness
thickness of of the
the ii region
region at at operating
operating bias.
bias. In
In practice
practice this limits
222 The Physics
The Physics of Solar Cells Thin Film
Thin Film Solar Cells
Cells 223

~:t
negligiblecompared
negligible comparedto to the
the recombination occurring in
recombination occurring in the intrinsic layer.
layer.
p n .~
So,
So, toto a first
a first approximation,
approximation, we need
we need only include current and
only include the photo current
the photo

dark current resulting from the

resulting from the intrinsic layer. Then,
intrinsic layer. Then, ifif dark
dark current and
)
) photo
photo current are are independent, we have from
we have

J(V) = Jse - Jdark(V) .

from Eq. 1.4

)) For the
For the p-i-n structure, the
p--n structure, the dark
dark current
current is
is given
givenby
by the
thevolume
volume recombi-
recombi-
nation rate integrated
integrated across the i region,
across the region,
)
)
-x
-x
p
00 x x.1i+ xXnn x 1.dark
_
1dark
(V) - (V)/kTe
2sinh(qV/2kT)
qnjXj
(V)_ -qnixi
--- 2 sinh(qVj2kT)
q(Vbj
J'Tn'Tp q
VTnTp Vbi - - V)jkT
(8.2)
(8.2)

Fig. 8.9.
Fig. 8.9. Layer
Layer widths of p-i~
widths of p--n junction
junction structure.
structure. Provided that the p and
Provided that and nn layer
layer
where the Sah-Noyce-Shockley
where approximation, Eq.
Sah-Noyce-Shockley approximation, Eq. 6.43,
6.43, has
has been used,
used,
doping are high enough,
levels .are
doping levels enough, the depletion
depletion region
region is contained
contained almost entirely within
the
the ii region.
region. and Tn, Tprefer
'Tn, 'Tp refertoto electron
electron and
and hole
hole lifetimes
lifetimes inin the
the undoped
undoped region.
region. (In
fact, this is
fact, is aa far
far better
better approximation
approximation for for p-i-n
p-i-n structures
structures than for p-n's.
The approximation supposes supposes thatthat the energy level varies
the intrinsic energy varies linearly
the i-region
i-region thickness
thickness to
to around
around 0.5
0.5 .m. The following
J.Lm. The followingsection
sectionexplains
explains how
how
across the
across the depleted region, which
depleted region, which isis indeed the case
indeed the case for
for p-i-n structures
p-i-n structures
the current voltage
voltage characteristics of aa p-i-n
characteristics of p-i-n junction
junction may
may bebe calculated.
calculated.
with low background doping.) Because the depletion region is thick, ii region
recombination of
recombination of the
the form
form Eq.
Eq. 8.2
8.2will
wil always dominate and
always dominate and the ideal (n
the ideal (n ==
8.4.2. p-i-n
8.4.2. p-i~ solarcell
solar cell device
device physics
physics 1)
1) behaviour expected for
behaviour expected for diffsion
diffusion currents
currents in in aa p-n junction is
p-n junction is seldom
seldom

To a first
first approximation
approximation the depletion
depletion approximation
approximation can can be used to cal-cal- seen.
seen.
culate the current-voltage
current-voltage characteristics of aa p-i-n
p-i-n junction
junctionsolar
solar cell.
cell. We
We If collection
collection of of photogenerated carriers isis perfect,
photogenerated carriers perfect, the 'short
'shortcircuit'
circuit'
will consider
wil consider aa structure
structure with
with p,
p, ii and n layer
and n layer thicknesses
thicknesses xxp, Xiand
p , Xj Xn and
and Xn and
photocurrent is given given byby the photogenerated current in the ii region,
photogenerated current region, from
from
set xx == 00 at
set at the
the p-i interface. The
p-i interface. The pp and doping densities
n doping
and n are N
densities are N aa and
and
Eq. 6.44,
Eq.6.44,
Nd, respectively,
Nd, and the i region has an unintentional or
respectively, and or background
background dop-
dop-
ing level of Nil
level of Ni, due
due to charged
charged impurities,
impurities, here assumed
assumed n type.
type. Because
Because Jse = f q(l - R)be-axp(l - e-axi)dE. (8.3)
(8.3)
the doping
doping levels in the
levels in the pp and n regions are so much
regions are higher than
much higher than in the
intrinsic region, the
intrinsic region, the depletion
depletion widths
widths within
within the
the pp and n regions
regions are very
very This is the
the case for very
case for very good
good carrier
carrier transport
transport in thethe undoped
undoped region.
region. If,
small and can
can be
be neglected. Then, provided
neglected. Then, provided that the
the background
background doping
doping however, carrier lifetimes are short or mobilties low, then
however, carrier lifetimes are short or mobilities low, then the net
net pho-
pho-
is low
low enough,
enough, the space charge region thickness isis equal
region thickness equal to the
the i-region
i-region tocurrent wil
to will be
be limited
limited by
by the mobilty
mobility and
and the
the electric
electric field.
field. The total
thickness. Following the analysis
Following the analysis of
ofthe
the p-n
p-n junction in Chapter
Chapter 6,
6, we
we have
have photogenerated current, given by Eq. 8.3, may exceed exceed the maximum drift
using Eq. 6.28,
6.28, current which i-region can
which the i-region can support
support at a given applied
applied bias.
bias. In
In that case
case
it can
it canbe be shown
shown that thethat the net photocurrent is
net photo is reduced to
J = -In(O) - Jp(Xi) - Jser (8.1)
(8.1)
where
where JJser is the
scr is the current
current density from the
density from the ii layer
layer and each
each of the three
three
I ( X~)
Jse=Jse 1- 1
W(Vbi - V)
(8.4)
(8.4)
contributions is worked
worked out for
for some given bias
some given bias VV and
and generation rate G.
C.
Because
Because ofof the
the short diffusion lengths in
diffusion lengths in doped
doped amorphous
amorphous silicon
silconthe
the where.T
where is the
J.L'T is the average
average mobility-lifetime
mobility-lifetime product for the
product for the two carrier types
two carrier types

current collection
collection from
from the p and
and nlayers
n .layersisisnegligible.
negligible. Moreover,
Moreover, because
because Merten, 1998j. In
[Merten, 1998]. In deriving Eq. 8.4
8.4 itit isisassumed
assumed that
that electron
electron and
and hole
hole
these layers are
these layers are so
so thin, the
the excess
excess recombination
recombination occurring there
there is
is also
also densities vary linearly
linearly with distance in the i region,
region, and have
have independent,
independent,
 224 ThePhysics
The PhysicsofofSolar
SolarCells
Cells Thin
ThinFilm
FilmSolar
SolarCells
Cells 225
224 225

constant lifetimes and that photogeneration is uniform. It is useful to define Electric

Electricfield
field
constant lifetimes and that photogeneration is uniform. It is useful to define
a drift length for photogenerated carriers, Li
a drift length for photogenerated carriers, Li

Li= . W(Vbi - V)
Xi
pptypety ty
itype nt~e
nt}-p9
Several semi-empirical models for performance of amorphous silicon solar
Several semi-empirical models for performance of amorphous silcon solar
cells have been developed, which include such bias dependence of the pho-
cells have been developed, which include such bias dependence of the pho-
tocurrent [e.g. Hegedus, 1997J.
to current e.g. Hegedus, 1997j. low backgou J ng
la.v backgOlrd d:!pi rg
There are a number of ways in which this treatment may need to be or low bias
There are a number of ways in which this treatment may need to be or la.vbias
modified for a-Si p-i-n structures.
modified for a-Si p-i-n structures.
(i) If the charged background doping in the i region is too high, then at ligh
tigh bagrolT dop
backgrolTd doping
rg
(i) Ifabove
the charged background or
or lighbias
biases some threshold the doping in the i region is too high, then at
i region will not be completely depleted. l"ighbias
biases above some threshold the i region wil not be completely depleted. )) Dist~e
Distarce
This situation occurs when the i region thickness obeys
This situation occurs when the i region thickness obeys
Fig.
Fig. 8.10.
8.10. E~ectric
E!ectricfield
field dropping
dropping across
across an
an ii layer
layer with
with charged
charged background
background impurities.
impurities.
The
!~e dashed
dashed hne
Ime represents
represents the
the electric field distribution
electric field distribution atat the
the point
point where
where the
the ii region
region
x1
?> 2.ss(Vbi - V) (B.5) is just depleted.
x.
1__
(8.5) IS Just depleted.
qNi
where we have used Eq. 6.13 for the thickness of the depletion region at
where we have used Eq. 6.13 for the thickness of the depletion region at
a symmetric junction and assume that Na
~ N As V is increased the
a symmetric junction and assume that Na ?? Ni.i As V is increased the
built-in bias is split between the p-i and i-n interfaces, so that in the case
~~ -------_._.-

~
built-in bias is split between the p-i and i-n interfaces, so that in the case
of n type background doping in the i region, only
of n type background doping in the i region, only EFp -------....
----- . _---- EFn

. - kT In (NaNi)
pi -qnni2
v.v..
pi -- kT 1
q (NaNi)
2
ni
is dropped across the p-i depletion region and the depletion thickness is
~
p tye
ptype itye
type n type
ntype
is dropped across the p-i depletion region and the depletion thickness is Fig. 8.11.
8.11. Band
reduced to Fig. Band profile
profile of p--n junction
of p-i-n junctionunder
underhigh
highinjection
injection conditions.
conditions. The
The electric
electric
reduced to fieldininthe
field the ii region
region isis neutralised
neutralised by
by the
the space
space charge of free
charge of free carriers.
carriers.

Wi=
2.ss(Vbi - V) (B.6)
Wi= (8.6)
qNi and p.p. Free
Freecarriers
carriers arrange
arrange themselves
themselvestotominimise
minimisethe theelectrostatic
electrostatic poten-
poten-
and
Then in Eqs. B.2 and B.4 Vbi should be replaced by V pi and Xi should be tial energy with the result that the electric field, rather than being
tial energy with the result that the electric field, rather than being constant constant
Then in Eqs. 8.2 and 8.4 Vbi should be replaced by Vpi and Xi should be
replaced by Wi from Eq. B.6. The situation is illustrated in Fig. 8.10. acrossthe
across thei iregion,
region,isishigher
higheratatthe
thep-i
p- and
and i-n
i-n interfaces, and smaller
interfaces, and smaller in
in
replaced by Wi from Eq. 8.6. The situation is ilustrated in Fig. 8.10.
In this situation the photo current will be reduced and become bias de- the middle.
the middle. In In very
very high
high injection
injection conditions
conditionsthe the field
fieldvanishes
vanishesthroughout
throughout
In this situation the photocurrent wil be reduced and become bias de-
pendent, decreasing with increasing V. For high Ni levels this effect appears mostofofthe
most thei i region
regionand
andnn~~ pp..
pendent, decreasing with increasing V. For high Ni levels this effect appears
as a slope in the plateau of the J-V curve, and could be confused with shunt Thennand
Then nand p p obey equationsof
obey equations ofthe
the form
form
as a slope in the plateau of the J-V curve, and could be confused with shunt
resistance.
resistance.
(ii) At high injection levels, for instance at high illumination, the free
(ii)densities
carrier At high injection levels,become
in the i region for instance at highand
significant ilumination, the free
the depletio~ ap-
~- + =0
dd2p
dx
p _ (p
dx
2

2
(p -- Po)
DpTp
DpTp
Po)+g(E,
Dp-
x) _ 0
g(E, x)
Dp (8.7)
(B.7)
carrier densities in the i region become significant and the depletio~ ap-
proximation is not valid for calculating the band profile. The band profile
proximation is not valid for calculating the band profile. The band profie
should then be calculated self consistently, including the contributions of n
should then be calculated self consistently, including the contributions of n
--
2
dd2n
dx2
-
dx
++ Dn-
n (n
- DnTn
2
-0
(n -- no)
DnTn
no) g(E,
Dn-
x)
g(E, x)
-0 (8.8)
(B.B)
226 The Physics
The Physics of
of Solar
Solar Cells Thin Film
Thin Film Solar Cells
Cells 227
227
226

where D
where
intrinsic
n, D
Dn, Dp,
p
intrinsic region.
, are the diffusion
diffusion coeffcients
Sincenn== pp and
region. Since
coefficients of electrons
and no Po, these
no == Po,
electrons and
these equations
and holes
equations can
holes in
can be
in the
be added
added to
I light I light
.,t,li9ht

give an
give an ambipolar diffusion equation W transparent conductor W
transparent conductor
glass _ ~ e.g. indium tin tin
oxide
2 n (n(n-- no)
dd2n x) __ 0a
g(E,x)
no) g(E,
glass ~ e.g. indium
oxide-;,==f:
oxide
~-
oxide---_-.:;~--J
dx2
dx 2 - - L~L ++ DaDa --
(8.9)
(8.9) ~ e.g.

..-
.....
a-Si
'VVVVVVVVVV"..

a-Si
e.g. zinc
zinc

a-Si a-Si
I:
where the
where the ambipolar diffusion constant is given by

Da DnDp
Da == DnDp (8.10) ----- oxide
metal
- .-r--~~-------
Tr.n
TCO
metal
Dn + Dp
Dn+Dp
and the
and the ambipolar diffusion
diffusion length by
(8.11) superstrate design substrate design
La = JDaTa (8.11)
Fig. 8.12.
Fig. 8.12. Substrate
Substrateand
andsuperstrate
superstratea-Si
a-Sicell
cell designs.
designs.
where
Dn + Dp
Ta = Dn/Tp + Dp/Tn . (8.12)
Ta = Dn/Tp + Dp/Tn . 8.4.3.
8.4.3. Fabrication
Fabrication of
ofa-Si
a-Si solar
solar cells
cells

Evidently the
Evidently the current
current is now driven
is now driven by diffusion rather
by diffusion rather than
than drift, and
and Amorphous silcon solar cells
Amorphous silicon cells are normally
normally deposited
deposited on glass substrates,
charge
charge separation is driven by the small space charge regions for holes at
small space charge regions for holes which are coated
coated with a transparent
transparent conducting
conducting oxide
oxide (TCO) such
such as tin
tin ox-
ox-
the p-i
the interface and
p-i interface for electrons
and for electrons at
at the i- n interface.
the i-n interface. ide or indium tin oxide.
oxide. TCO coated
coated plastics
plastics are
are also
also being
being developed.
developed. Cells
Cells
conditions the recombination
In these conditions recombination rate becomes becomes linear with nn (the
linear with are
are usually fabricated in
in aa 'superstrate'
'superstrate' design,
design, where
where layers
layers of
of conducting
conducting
SRH recombination rate, Eq. 4.79, 4.79, becomes
becomes approximately
approximately proportional to oxide, p-type, undoped and n-type a-Si
oxide, p-type, a-Si are deposited in
in sequence.
sequence. The a-Si
a-Si
when n =
n when = p)
p) and
and isis constant
constant across
across the
the ii region.
region. Then
Then the the ideality
ideality factor
factor deposited by
is usually deposited by plasma
plasma decomposition of of silane or 'glow
'glow discharge',
discharge',
of the
of the dark
dark J-VJ-Vcharacteristic
characteristic should should become
become equalequal to to one.
one. InIn the
the case
case but aa number
number of of other deposition
deposition methods such as sputtering
sputtering andand 'hot
'hotwire'
wire'
where electron
where electron and and hole
hole lifetimes
lifetimes areare equal,
equal,and andn, n, pp nj, Eq.
// n, Eq.8.9
8.9cancanbebe are being
being investigated.
investigated. For For the rear contact,
contact, zinc
zinc oxide
oxide is deposited on to
solved exactly to give solutions analogous
solved analogous to to those
those for for the
the currents from the the n layer
layer followed
followed by by aa metal,
metal, usually
usually aluminium.
aluminium. Light
Light trapping struc-
struc-
neutral regions
regions of a p-n p-n junction
junction derived
derived in Chapter
Chapter 6. 6. tures may be built-in by texturing the front TCO layer, metallsing or
layer, and metallising or
(iii) The
(iii) The electron
electron andand hole
hole lifetimes
lifetimes in Eq. 8.2
in Eq. 8.2 are,
are, in in general,
general, not
not con-
con- texturing the
the back
back surface
surface in in order
order to
to enhance
enhance light
light absorption.
absorption.
stants for
stants for an
an amorphous
amorphousmateriaL.
material. At low low light intensity charge carriers are An alternative
alternative is is the
the 'substrate'
'substrate'design
designwhere
wherelayers
layersare
aredeposited
depositedon on
likely to
more likely to be trapped in in tail
tail states,
states, which
which extends
extends their their lifetime.
lifetime. The
The a metal
metal substrate,
substrate, suchsuch asas steel,
steel, which
which forms
forms the back contact. Here Here the pp
dark current term term inin Eq.
Eq. 1.3
1.3 is
is therefore intensity dependent.
therefore intensity dependent.The Theeffect
effect for
for layer can be very thin, since
layer can since there is is no
no glass
glass and
and the
the front
front surface
surface does
does
amorphous silicon
amorphous silcon p-i-n cells is
p-i-n cells is that
that performance
performance is is better
better at low light in- in- not need
not need toto bebeflat,
fiat, and
and so so higher
higher effciencies
efficiencies are
are possible.
possible. However, the
However, the
Carrierdensity
tensity. Carrier density dependence
dependence of of lifetime
lifetime is evident through through decreasing
decreasing substrate
substrate design
design is is not
not so
so easy
easy to
toprocess.
process.
efficiencies and fill factor with increasing
collection effciencies increasing light light intensity.
intensity.
(iv) If the electron and hole mobilities are
(iv) If the electron and hole mobilties are low, collection in low, collection in aa wide,
wide, 8.4.4. Strategies
8.4.4. Strategies to improve a-Si cell
improve a-Si cell performance
performance
depleted
depleted ii layerlayer may
may be be limited by by the
the electric
electric field
field due
due to to the
the mobile
mobile
carriers. In
carriers. In these
these conditions
conditions the the current
currentisis said
said to
tobe be 'space
'space charge
charge limi,ted'.
limited'. . Light
Light induced
induced degradation
degradation
If mobility
If mobility is is intensity
intensity dependent,
dependent, collection
collection in this this limit
limit should
should improve
improve The Staebler
The Staebler Wronski
Wronski effect
effect is
is the
the most
most important
important barrier
barrier to
to
with increasing light intensity.
with increasing light intensity. widespread
widespread use of a-Si solar cells.
cells. Light-induced
Light-induced degradation is
is stronger
stronger
 ThePhysics
The PhysicsofofSolar
Solar Cells
Cells ThinFilm
Thin FilmSolar
Solar Cells
Cells 229
229
228
228

Table8.1.
Table 8.1. Evolution
Evolution of
of performance
performance of a-Si solar cells.
a-Si solar cells.
pp nn p
p nn
Date
Date Design
Design Efficiency
Effciency
)
) 1977
1977
1980
1980
Schottky
Schottky diode
a-Si:H
a-Si
diode
p--n
:H p-i-n
6%
6%
6%
10 6%

))
1982
1982 a-SiC:H/a-Si:H
a-SiC:H/a-Si:H p-i-n heterojunction
p--n heterojunction 8%
8%
1982
1982 textured
textured substrates
substrates 10%
10%
1987
1987 gr8.d.ing of p-i
gr8.ing of interface
p- interface 12%
12%
l'tunnel.junction
l' . 1990s
1990s multigap
multigap designs
designs 13%
13%
tunne1lunclion

Fig. 8.13.
Fig. 8.13. Multilayer
Multilayer a-Si
a-Si cell.
cell. the use of multi~ayer
the use multilayer a-Sia-Si cells.
cells. In
In the
the multilayer
multilayer design,
design, two
two oror more
more
p--n cells
p-i-n cellswith
withrelatively
relatively thin
thini-regions
i-regions areare connected
connected in series.
series. The
extra cell
extra cell (or (or cells)
cells) increases
increases overall overall light
light absorption
absorption while
whilethe
the thin
thin ii
in materials with a higher hydrogen
in content, because
hydrogen content, because ofof the
the greater den-
den-
regions avoid
regions avoid the the collection
collectionlosses
lossesdue duetoto background
backgrounddoping
dopingin in the
the ii
sity of
sity of Si-H
Si-H bonds,
bonds, yet aa high
high hydrogen
hydrogen content is needed
needed for suitable
region. Moreover,
region. Moreover,the the higher
higher electric
electric field
fieldwhich
whichapplies
appliesinin thinner
thinner i
doping and
doping and transport properties. If a-Si
properties. If a-Si could be produced
produced with aa lower
lower
layers appears
layers appears to to reduce
reduce the the Staebler Wronski effect.effect.
original dangling
original dangling bond
bond density
density then less
less hydrogen
hydrogen would
would be needed for
passivation and
passivation and so
so the
the Staebler
Staebler Wronski
Wronski effect
effect could.
could be reduced. ~l.t~r
be reduced. Alter- Since the
Since the cells
cells are
are connected
connected inin series,
series,itit isis necessary
necessarytoto match
match the
native deposition techniques
techniques are
are therefore
therefore being
being studied.
studied. OneOne posslblhty
possibilty currents from
currents from the front
front and
and back
back cell.
cell. Since
Since less
less light reaches
reaches the back
back
is the 'hot
is 'hotwire'
wire'technique
technique which
which appears
appears totoproduce
producegood gooda-Si
a-Siwhen
when cell, the
cell, the back
back cell
cell must
must be
be thicker
thicker to
to produce
produce thethe same
same photocurrent.
photocurrent. The
saturated with only
saturated with only 1%
1% hydrogen.
hydrogen. optimum ratio of thicknesses wil depend
thicknesses will depend on on illumination
ilumination cnditions.
conditions. As
As
with two-terminal
two-terminal tandem designs (discussed inin Chapter
designs (discussed Chapter 10),
10), the stack
stack
.
Improvement
Improvementof
of Vae
Voe wil
will operate
operate at
at its
itsoptimum
optimum only
only under
under certain
certain ilumination
illuminationconditions.
conditions.
The open
open circuit
circuit voltage
voltage in a-Si
a-Si solar
solar cells
cells is
is substantially less
less than
the optical band gap (0.89 V compared to 1.7 eV) on account of the
the optical band gap (0.89 V compared to 1.7 eV) on account of the high
high Improvement
Improvementofoflimiting
limitingeffciency
efficiency
activation
activation energies
energies in amorphous material, and and resulting
resulting low
low built-in
built-in bias.
bias. Multi-gap cell designs
designs are possible using a-SiC:H
possible using a-SiC:H as
as the material
material for
for
Vae can be
Voe can be increased
increased byby the
the use
use of
of either
either (i)
(i) a wider
wider band gapgap emitter
emitter aa wider
wider gap
gap cell
cell and
and a-SiGe:H
a-SiGe:H for aa narrower
narrower gap
gap cell.
cell. Two-terminal
Two-terminal
such
such as a-SiC:H
a-SiC:H or (ii)
(ii) a polycrystallne
polycrystalline Si
Si emitter,
emitter, in
inwhich
which degenerate
degenerate cascade designs where
cascade designs where the
the different
differentp-i-n
p--n cells
cells are
are connected
connected in
in series
series
doping
doping isis possible.
possible.
using
using tunnel
tunnel junctions
junctions have
have been studied. To
been studied. To date thethe best
best effciency
efficiency
from
from aa three-cell
three-cell stack
stack slightly
slightly improves
improves on the
the best
best single
single junction
junction a-Si
a-Si
. Improvement
Improvementof
ofJse
J se cell,
cell, but
but substantial
substantialimprovements
improvementsarearepossible.
possible. The
The limiting
limiting effciency
efficiency for
for
There
There are
are two
twoproblems:
problems: three cell
three cell devices
devices is calculated at
at 33%. The main
33%. The mainproblems
problemshave
have been
been the
the
(i) Response
Responsetotoblue
bluelight
lightisispoor
poorininhomogenous
homogenousa-Si:H
a-Si:Hcells
cells on
on account
account
poorer
poorer quality
quality of
of the
the alloy
alloy relative
relative to
to a-Si
a-Si and
and incorporating
incorporating large
large area
area
(i)
of poor collection in'the p layer. This can be resolved by replacing
of poor collection in the p layer. This can be resolved by replacing tunnel
tunnel junctions.
junctions. The
Theevolution
evolutionof ofa-Si
a-Si solar
solar cell
cell performance
performance is
is charted
charted
the
the a-Si
a-Si pp layer
layer with
withaawiderwiderband
bandgap
gapa-SiC:H
a-SiC:H window,
window, like
like the
the in
in Table
Table8.1.
8.1.
heteroface
heterofacedesigns
designs preferred
preferredforfor GaAs,
GaAs, or
orby
byaagraded
gradeda-SiC:H-a-Si:H
a-SiC:H-a-Si:H
layer.
layer. 8.5. Defects
8.5. in Polycrystallne
Defects in Thin Film
Polycrystalline Thin Film Materials
Materials
(ii) Response to
(ii) Response tolong
long wavelengths
wavelengths maymay be
be poor
poor because
because ofof the
the limit
limit.to
to
Thefollowing
The following sections
sections are
are concerned
concerned with
with polycrystallne
polycrystallinethin
thin film
film photo-
photo-
the
thei-region
i-regionthickness
thicknesswhich
whicharises
arisesfrom
from charged
chargedbackground
backgroundd~ping
dQpmg
voltaic
voltaic materials.
materials. We
We first
firstconsider
consider the
the features
features of
of aa grain
grain boundary
boundaryand
and
in
inthe
thei-region.
i-region. This
Thiscan
canbe
beresolved
resolved either
either with
with light
lighttrapping
trappingtech-
tech-
the
theconsequences
consequenceSforfor photovoltaic
photovoltaiCdevices.
devices.
niques
niques to
to increase
increase the
the optical
optical path
path length
length within
within the
thecell,
cell, or
orwith
with
 230 ThePhysics
The Physicsof
ofSolar
Solar Cells
Cells ThinFilm
Thin Film Solar
Solar Cells
Cells 231
231
230

Fig.
Fig. 8.14.
8.14. Grain boundaries in
Grain boundaries in microcrystallne
microcrystalline materiaL.
material.

8.5.1. Grain
8.5.1. Grain boundaries
boundaries Fig. 8.15.
Fig. 8.15. Schematic
Schematic of
of grain
grain boundary
boundary showing distorted lattice
showing distorted lattice between grains of
between grains of
different orientation.
different orientation.
A polycrystalline
A polycrystallne material
material is is composed microcrystalltes
composed of micro crystallites or
or 'grains'
'grains'ofofthe
the
semiconductor arranged
semiconductor arrangedat at random
random orientations
orientations to to each other (Fig. 8.14).
each other 8.14).
The material is
The is crystalline
crystallne over the width of a grain,
over the grain, which
which is is typically
typically the
order of one /-L m . Since
one .m. Since the grains
grains are
are large
large in
in quantum-mechanical
quantum-mechanical terms, terms, band gap may be capable
band capable of trapping either type of of carrier, and and because
because
the band
the band structure,
structure, and and therefore the absorption
therefore the absorption coefficient,
coeffcient, isis virtually
virtually the times for re-release
re-release fromfrom deep
deep traps
traps byby thermal
thermal activation are very long
identical to that
identical that of of the
the single
single crystal
crystal materiaL. Howeverthe
material. However the transport
transport and they tend to to act
actas asrecombination
recombinationcentres. centres. (See
(See Sec.
Sec. 4.5.)
4.5.)
recombination properties are strongly affected by the presence of the inter- Because these
Because these intra
intra band
band gapgap states are able to trap trap charge,
charge, they
they influ-
influ-
faces ence
ence thethe potential distribution close close to the grain boundary. In Chapter Chapter 55 we we
faces or
or grain
grain boundaries.
boundaries.
The different orientations
orientations of
of neighbouring crystal grains
grains give
give rise to dis-
dis- saw
saw howhow defect
defectstates
states atat aa surface
surfacein in doped
dopedmaterial
materialtend tend toto trap
trap majority
locations, misplaced atoms ('interstitials'),
('interstitials'),vacancies,
vacancies, distorted
distortedbond
bondangles
angles carriers
carriers andand establish
establish an an electrostatic
electrostatic field
field opposing
opposing majority
majority carrier flow.flow.
and bond distances
distances at the
the interfaces.
interfaces. In
In compound
compound semiconductors
semiconductors we we may The situation
situation with
with aa grain
grain boundary
boundaryisis similar,
similar, rather
ratherlike like two
two surfaces
surfaces back
find
find atoms occupying
occupying the wrongwrong lattice sites,
sites, and
and vacancies
vacancies of particular to back.
back. We consider the
We consider the case
case of of aa grain
grain boundary
boundary in in nn type material
material in in
atoms
atoms which effectively
effectively dope
dope the materiaL. There may
material. There may bebe a few
few atomic
atomic Fig.8.16.
Fig. 8.16.
The The
defect defect levels within the band
levels within band gap gap are
are usually
usually distributed
distributed so so
layers of imperfect
imperfect crystal
crystal at the
the grain
grain boundaries,
boundaries, while
while the material
material ac-ac- that
that thethelocal
local neutrality
neutralitylevel level (defined
(defined in Chapter
Chapter 55 as as the
the level
level up
up to
to which
which
commodates
commodates the change
change in crystal orientation
orientation (Fig.
(Fig. 8.15).
8.15). Polycrystallne
Polycrystalline the
the states
states are filled when the interface is neutral) lies lies closer
closer to the centre
centre of of
materials
materials are
are also
also likely
likely to contain
contain extrinsic
extrinsic impurities
impurities which
which contaminate
contaminate the
the band
band gapgap than
thanthe theFermi
Fermilevellevel ofof the
the doped
doped semiconductor.
semiconductor. (This wil will
the
the materials
materials during
during growth.
growth. These
These extrinsic
extrinsic impurity
impurity atoms
atoms are
are likely
likely to
to always
always be the case case unless the interface states states are
are concentrated
concentratedvery veryclose
close in
in
concentrate at
concentrate at the
the grain
grain boundaries.
boundaries.
energy
energy to the conduction
conduction band edge.) edge.) Then, the states states wilwillbe beacceptor-like
acceptor-like
The
The various
various types
types of
of defect
defect introduce
introduce extra
extraelectronic
electronicstates.
states. These
These extra
extra and
and trap
trap electrons.
electrons. ThisThis gives
gives rise
rise to aa plane
plane of of fixed
fied negative
negativecharge
charge at at the
the
states
states are
are spatially
spatially localised and because
localised and they do
because they do not need
need to obey
obey thethe interface,
interface, and aa layer layer ofofpositive
positive space
space charge
charge on on either side side where
where the nn
symmetry
symmetry of of the crystal
crystal and
and they
theymay
mayhave
have energies
energies in the
the band
band gap
gap (see
(see type
type material
material hadhad been
been depleted.
depleted. TheThe electrostatic
electrostatic forceforce sets up aa potential
potential
Chapter
Chapter 5),
5), these
these intra band
band gap
gap states
states tend
tend to
to trap
trap carriers
carriers and
and we
we wil
will barrier
barrier which
which opposes further majority majority carrier
carrier migration.
migration. Minority
Minority carriers,
carriers,
refer
refer to
to them
them asas 'intra-band-gap
'intra-band-gap states'
states' or simply
simply 'trap
'trapstates'.
states'.How
Howthey
they however,
however, see see aa potential well well atat the grain boundary
boundary and and are
arepulled
pulled towards
towards
behave
behave depends
depends upon their their energetic
energetic position
position relative
relative to the bands
bands of
of the
the it,
it,where
where thethe probabilty
probabilityofofrecombining
recombining with with aa trapped
trapped majority
majoritycarrier
carrierisis
bulk
bulk crystal:
crystal: shallow
shallow defects
defects close to the conduction
close to conduction band tend tend to ~ct as
toa,ct as high.
high.
electron
electron traps
traps(acceptors)
(acceptors)while
whiledefect
defect levels
levels close
close to the
the valence
valence band
band act
act Figure
Figure8.16 8.16 shows
shows how a depletion
depletion region
region is is established
established aroundaround aa grain
grain
as
as hole
hole traps
traps (donors).
(donors).'Deep'
'Deep'defect
defectlevels
levelsatatenergies
energies near
near the
thecentre
centreofofthe
the boundary
boundary in nn type type material
material for for which
which o CPo -(< EF.
EF. The The grain
grain boundary
boundary
 The Physics
The Physics of Solar
Solar Cells Thin Film
Thin Film Solar Cells
Cells 233
232
..

~ 8.5.2. Effects of
of grain
type semiconductor
semiconductor interface
Interface nn type
type semiconductor
semiconductor 8.5.2. Effects grain boundaries
boundaries on transport
on transport
n type
~
The effect
The of grain
effect of grain boundaries
boundaries on on charge
charge transport
transport depends
depends on whether
whether
Ec Ec they lie
they lie normal
normal toto or parallel
parallel to to the
the direction current flow.
direction of current flow. In
In the
the first
Ec
- - - - - - EEFF - - - - - - EEFF case,
case, when current is
when current flowing across
is flowing across aa grain
grain boundary, the potential
boundary, the potential bar-
bar-
aio
riers slow down the transport majority carriers, limiting the
riers slow down the transport of majority carriers, limiting the majority
<1>0
carrier mobility,
carrier mobilty, while
while the potential
potential wells
wells drive
drive minority carriers towards
towards
Ev Ev Ev recombination centres
recombination centres atat the grain boundary, reducing the
boundary, reducing the minority carrier
diffsion length
diffusion length and
and lifetime.
lifetime. TheThe size
size of
of these
these effects depends upon
effects depends upon the
doping,
doping, the density of interface
of interface states, and the photogenerated carrier den-
n type semiconductor n type semiconductor sity.
sity.AA simple
simple model for aa grain
model for grain boundary
boundary in in nn type
type materials
materials Seto,
[Seto, 1975;
1975;
Card, 1977;
1977; Landsberg,
Landsberg, 1984j
1984] isis discussed
discussed below.
_ _ _ _ _ _ _ Ec The main results are that:
Ec
EF
EF . Increasing
Increasing the
the trap
trap density
density increases
increases the the space
space charge stored at
charge stored at the
the grain
grain
<1>0 boundary, which increases
boundary, which increases the the barrier
barrier height,
height, reduces
reduces conductivity and
increases recombination.
- - - - - - - EEvv . Increasing
Increasing the doping
doping first increases
increases thethe barrier
barrier height,
height, but
but at higher
higher
levels the
doping levels the traps
traps become
become saturated, the the space
space charge
charge region
region begins
begins
++
+ -- ++
+ -- ++ to contract and the the barrier
barrier isis reduced.
reduced.
Fig. 8.16.
Fig. 8.16. Ilustration
Illustrationofofhow
howband
bandbending
bendingresults
results when
when aa layer
layer of
of interface
interface states
states is
is . Increasing
Increasing the density
density of of free
free carriers by ilumination
carriers by illumination reduces
reduces the net
net
sandwiched between two layers. Notice how depletion
two nn type semiconductor layers. depletion results when charge stored at
charge stored at the grain
grain boundary
boundary and hencehence the barrier
barrier height.
height. At
At
neutrality level
the neutrality level of the
the interface states lower than
states is lower Fermi level
than the Fermi level of
of the
the nuetral
nuetral n high ilumination
illumination levels
levels the
the grain
grain boundaries
boundaries have
have the
the minimum
minimum effect:
effect:
type layer.
layer.
conductivity reaches its
conductivity reaches its maximum
maximum level, level, and
and recombination
recombination withwith trap
states saturates.

(negative) sheet charge

accumulates a (negative)
Qgb = -q
charge density of Grain boundaries
boundaries which
which lie parallel to the direction
direction of
of current
current flow
flow prin-
cipally affect minority carriers.
affect minority Majority carriers
carriers. Majority travellng parallel to the
carriers travelling the
Ec-Vn-EB
l (8.13)

~'~
Qgb = LEc-Vn-EB ggb(E)dE
-q ggb(E)dE (8.13)
</>0
cPo

~.~
~'
emitter
where ggb(E) is the density of
ionisation energy,
ionisation
found
either side
and EB
energy, and
found from Poisson's
of interface states per unit
EB isis the
the band bending
Poisson's equation. The
bending due
The depleted
unit area,

depleted layers
layers of
side should each contain a compensating (positive)
Vn is the donor
area, Vn
due to the trapped
trapped charge,
ofsemiconductor
charge,
semiconductor on
(positive) charge
on
charge density of
112m)
Fig. 8.17.
Fig. (a) In
8.17. (a) In aa microcrystallne
base

microcrystalline material,
material, the intended width
width of
~:~
~:~
of the
the emitter
emitter region
region
+~Qgb.
+~Qgb. may comparablewith
may be comparable with the
the grain
grain size.
size.InInsuch
suchcases,
cases,the
the~
p- junction
junction passes
passes through
through
For p type material
material the
the situation
situationisisanalogous.
analogous.Occupied
Occupieddefect
defect levels
levels be-
be- individual
individual grains
grains and the actual position of the junction (grey
(grey line) may
may vary from grain
grain
low cPo
low o trap
trap majority holes until
majority holes until aa barrier
barrier opposing holeflow
opposing hole flow is
is established,
established, to grain; (b) At a point where
where the
the~junction
p- junction (full
(fullline)
line) passes
passes through a grain boundary
(dashed line)
(dashed line) the local potential
the local is affected,
potential is as shown
afected, as shown by by the
the lines
lines of
of constant
constant electrostatic
electrostatic
and aa negatively
negatively charged
charged depleted
depleted region
region appears
appears around
around the positively
positively
potential
potential (curved
(curved lines).
lines).
charged grain boundary.
 234 ThePhysics
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ThinFilm
FilmSolar
SolarCells
Cells 235
234 235

grain boundary are not affected - they see no barrier - but minority Energy
Energy
grain boundary are not affected - they see no barrier - but minority bulk
bulk grain boundary bulk
grain boundary bulk
carriers are still likely to be trapped in the potential well and recombine.
carriers are stil likely to be trapped in the potential well and recombine.
When a grain boundary actually crosses the p-n junction, it reduces the
When a grain boundary actually crosses the p-n junction, it reduces the
efficiency of charge separation by competing with the p-n junction for mi-
-*,1__~_ _ __
effciency of charge separation by competing with the p-n junction for mi- EB
nority carriers. A more serious problem arises when dopant impurity atoms Ec _E_B
Ec
nority carriers. A more serious problem arises when dopant impurity atoms
from the emitter diffuse along the grain boundaries, through the nominal EF
from the emitter diffuse along the grain boundaries, through the nominal
p-n junction, into the base. This creates a shunt path through the p-n
p-n junction, into the base. This creates a shunt path through the p-n oo E1
junction which reduces the rectification of the junction.
junction which reduces the rectification of the junction.
Ev
8.5.3. Depletion approximation model for grain boundary
8.5.3. Depletion approximation model for grain boundary
Here we are going to use the depletion approximation to show how the
Here we are going to use the depletion approximation to show how the
resistivity of a granular material depends upon doping, density of trap x=-L
resistivity of a granular material depends upon doping, density of trap xx=-dl2
= - d/2 x=-L x=O
x=O x=L
x=L x = d/2
x =dl2 Distance
Distance
states and light intensity. The grain boundary is modelled as a plane at
states and light intensity. The grain boundary is modelled as a plane at
x = 0 with sheet density Ns of defects sandwiched between two layers of a Fig. 8.18. Grain
Fig. 8.18. Grain boundary
boundary in
in the
the depletion approximation showing
depletion approximation showing trap
trap energy
energy E
E
x = 0 with sheet density Ns of defects sandwiched between two layers of a barrier
barrier height EBheight EBEFand
and Fermi level . Fermi level
' EF. ' t,t,
homogenous material degenerately doped n type with dopant density N d .
homogenous material degenerately doped n type with dopant density Nd.
Neighbouring grain boundaries are placed at x = d. The defect energy
Neighbouring grain boundaries are placed at x = ::d. The defect energy
levels are located in a narrow band around E t such that E t is less than the In
levels are located in a narrow band around Et such that Et is less than the In the
the first
first case L=
case L = ~~ and
and the
the barrier
barrier height
height is
is given
given by
by
donor level Ec - Vn. In isolation, the neutrality level of the grain boundary
donor level Ec - Vn. In isolation, the neutrality level of the grain boundary
is below the Fermi level of the bulk semiconductor as shown in Fig. 8.16.
is below the Fermi level of the bulk semiconductor as shown in Fig. 8.16. EB = q2 Ndd2 (8.15)
When the three layers are brought together, electrons move from the bulk 8es (8.15)
When the three layers are brought together, electrons move from the bulk
layers into trap states at the grain boundary until equilibrium is reached.
layers into trap states at the grain boundary until equilbrium is reached. In this
Then the plane of the grain boundary will be negatively charged and the In this case,
case, because
because thethe grain
grain isis completely depleted, the
completely depleted, the Fermi
Fermi level has
level has
Then the plane of the grain boundary wil be negatively charged and the been unpinned from the donor level of the bulk materiaL. At the middle of
surrounding bulk layers positively charged, resulting in the potential profile been unpinned from the donor level of the bulk material. At the middle of
surrounding bulk layers positively charged, resulting in the potential profile the grain the Fermi level has been shifted down by an amount and the
shown in Fig. 8.18. The conduction band edge at the grain boundary is the grain the Fermi level has been shifted down by an amount ~ and the
shown in Fig. 8.18. The conduction band edge at the grain boundary is electron density
density reduced
reduced to to N
Nde-6./kT
raised by an amount EB relative to its value at the centre of the grain. electron d e-6./kT relative to the
relative to the undepleted
undepleted material.
materiaL.
raised by an amount EB relative to its value at the centre of the grain. To find
fid the
In the depletion approximation we neglect free carriers and suppose To thenew
new value
value of of EF
EF we need to
we need to consider
consider the
the filling
fillng of
of the
the trap
trap levels.
levels.
In the depletion approximation we neglect free carriers and suppose The sheet
sheet density
density of
of occupied
occupied traptrap states
states isis given
given by
by
that the bulk layers are completely depleted for a thickness L on either The
that the bulk layers are completely depleted for a thickness L on either
side. Then solving Poisson's equation with the boundary condition that the
side. Then solving Poisson's equation with the boundary condition that the
electric field vanishes at x = L field we find that the conduction band
electric field vanishes at x = ::L field we find that the conduction band
dNd L
dNd== L !(Et,
f(EEF, T)ggb(Et)
t , EF, T)ggb(Et )
traps,t
(8.16)
(8.16)
traps,t
edge varies like
edge varies like
q2Nd w~eref(E
w~ere !(Et, EF,T)
t , EF, T~isis the
the Fermi-Dirac
Fermi-Dirac distribution
distribution function
function (Eq.
(Eq. 3.25).
3.25).
(8.14)
(8.14) With a delta function for the distribution of trap states per unit area
Ec(x) = Ec(L) + -2 (L -lxI)2. WIth a delta function for the distribution of trap states per unit area
es
Now we need to distinguish two cases:
Now we need to distinguish two cases: ggb(E) = Ns(E - Et) (8.17)
(8.17)
(i) the grain is completely depleted and the trap states are partly filled.
(i) (dNd
the grain andassuming
assumingaaspin
spindegeneracy
degeneracyofofone
onewe
wefind
find
< N sis) This
completely
occurs depleted and the trap states are partly filled.
at low doping. and
(dNd -( Ns) This occurs at low doping.
(ii) the grain is partly depleted and the trap states are completely filled
(ii) the grain is partly depleted and the trap states are completely filed
(dNd > Ns).This occurs at high doping or at high intensity levels. dNde(E,-EF)/kBT
=Ns + 1 . (8.18)
(8.18)
(dNd :; Ns).This occurs at high doping or at high intensity levels.
236 Physics of
The Physics of Solar
Solar Cells
Cells Thin Film
Film Solar
Solar Cells
Cells 237
237
236

Rearranging, we
we find
find for EF
for EF space
space space
space
I
Rearranging,
charge
charge charge
charge
I
I

rr
EF == Et
E t -- kT
kT In
ln(Ns
(Ns -- 1)
1) (8.19)
(8.19)

1 r
EF
dNd
where EF
where EF and
intrinsic level
E t are
and Et
at x
aremeasured
= O.
measured relative
Thus the
relative to
Fermi
to some
level
some reference,
is
reference, such
unpinned
such as
from the
intrinsic level at x = O. Thus the Fermi level is unpinned from the donor
level, and
level,
In
and fixed
In the
instead to
fied instead
the second
second case,
to the
the trap
case, where
trap energy
where the
energyleveL.
grain is
the grain
level.
is partly
partly depleted,
depleted,
as the
the
donor

electric
field
T IT
electric
electric
field
I w
!

I

Ns
i

L = 2Nd'
2Nd' (8.20)
(8.20)
L = I

barrier height
the barrier height is
is I
band
q2N 2
q2N;
EB=-
EB = __ s_ (8.21)
(8.21)
profile

l
=t
8sNd
8sNd
q,
and the
the conduction
conduction band
band minimum
minimum is
is at
at the
the conduction
conduction band
band edge
edge energy
energy i
and
of the bulk material in equilibrium. In the mid-grain, undepleted regions v.b.
v.b.
of the bulk material in equilbrium. In the mid-grain, undepleted regions
the Fermi level
the Fermi level is
is pinned at the
pinned at donor level
the donor and nn has
level and hasits
its bulk value NNd.
bulk value d
~
The charge distributions, electric field and band profiles are illustrated
The charge distributions, electric field and band profiles are ilustrated for for
(a) (b)
each case in
each case in Fig. 8.19 below.
Fig. 8.19 below.
Fig. 8:19.
Fig. 8:19. Space
Space charge,
charge, electric fieldand
electric field and band
band profile
profie at
at aa grain
grain boundary
boundary in in n-type
n-type
materIal for ~he
material for ~he case
case where the grains
where the grains are
are (a)
(a) totally
totally and (b) partly
and (b) partly depleted.
depleted . In case
In case
8.5.4. Majority carrier
8.5.4. Majority carrier transport
transport ~a) t~eFermi
~a) t~e FermI level,
level, represented
represented by the by
fullthe line in the band
full horizontal line
horizontal band profile
profile diagram
diagram
is shIfted
IS shiftedD'
do~nwar~s
downwards .
r~lativetotothe
relative the donor
donor level
level(dashed
(dashedline)
line)by
byananamoun
amount .
t u.
A In cas~
. I n case'
In studying the
In studying the transport
transport ofof majority
majority carriers
carriers we we are
are interested
interested in
in the
the ef-
ef- (b) h e rerml
(b) tthe level iS
Fermi level IS pinned at the
pinned at the donor
donorleveL.
level.
fective conductivity of
fective conductivity of the medium, which
the medium, which is is the
the current
current crossing
crossing the grain
the grain
boundary per unit applied field, and the effective mobility, which
boundary per unit applied field, and the effective mobility, which is the con- is the con-
ductivity per unit charge. For this we need to calculate the
ductivity per unit charge. For this we need to calculate the mean current mean current
density crossing the
density crossing the grain boundary, (J).
grain boundary, (1).
We
We suppose
supposethatthat aa constant
constant electric field FF is
electric field applied to
is applied the granular
to the granular c:J ;:
medium
higher by
of
Fd
the
on
last
the
section.
right
Then
than the
the electrostatic
left of the grain
potential
medium of the last section. Then the electrostatic potential is on average
boundary
is on
in
average
Fig. 8.20,
electrostatic
potential energy
.
higher by Fd on the right than the left of the grain boundary in Fig. 8.20,

. .. ..;1"
and
and aa net
net current
current of approx:imately
of approximately Es
(8.22)
(8.22)
(J) = q(n)vxe-EB/kBT(eqFd/kBT - 1)
qV
will flow to
wil flow to the
the right. Here (n)
right. Here (n) is
isthe
themean electron density
mean electron density and Vx is the
and Vx is the x
mean
mean electron
electron velocity
velocity in the xx direction,
in the direction, given
given by
by ----------~-----------4'/ x
-d/2
-d/2
o +d/2
+d/2
Vx = ( kBT
Vx =
)1/2 (8.23)
(8.23) Fig.
Fig. 8.20.
8.20. Model of
Model of thermionic
thermionic current
current across
across aagrain
grainboundary
boundary under
under electric
electric field
field V
V /d.
/d.
( 27rm~
21lm~
kBT )1/2
 The
The Physics Cells
Physics of Solar Cells Thin Film
Film Solar
Solar Cells
Cells 239
239
238

statisti cs and
ann statistics isotropic motion,
and isotropic where m~
motion, where m~ is the elec-
assumi ng Boltzm
assuming Boltzmann is the elec- ozr--- ------____________ ~
tivity 0.2
kBT/q,
to kBT
compar ed to the conduc
/ q, the
small compared :i
tron effective
tron Since Pd
effective mass. Since Pd isis small conductivity
8.22 is by
given by
is given > 02
;: 02
-.,
Eq. 8.22
obtaine d from Eq.
obtained ~...
..II
~:J
j.
(J) __ q2
_ (J)
a-p- q2(n)vx d -EB/kBT -EB/kB T (8.24) .
i 0.15
..
0.15 :ien
iiai
a- p - kT
kT ee
_ (n)vxd (8.24) .c
.r:
-!
.! 0.1
0.'
e-
el
i
;
0."
ai 0.05 .2
electro n mobilit
and the electron by
mobiltyy by o
a.BO 2.&21
2.&21 4.&21
" .&21 8.&21
8.&21 8.El1
' .&21 1.&2
1.&22 1.5t19
1,5+19 1.5t 1.5t21
1.5+20 1,5+21 1.~
1,5+22 1.5t23
1,5+23
_ a a qvxd
_ qvxd-EB/kBT O.BOO
-EB/kB T (8.25)
f.n (8.25)
f.Ln -= q(n)
q(n) -= kT
kT ee DopingI1m'
Doping mO' Doping I m"
Doplng/m -3

(a)
(a) (b)
depend s on and Ns
Nd and only throug h
Ns only
Equations 8.24 and
Equati ons 8.24 showthat
8.25 show
and 8.25 that aa depends on Nd through
and .n
EB and (n), and f.Ln only throug h EB'
only through is immed iately clear
E B. ItItis immediately clear that that f.Ln will
EB f.n wil
lowest where
be lowest EB is greates t. To conside r the behavio ur of a we need to
where EB is greatest. To consider the behaviour of a we need to
(n).
density (n). lOS
IOS
carrier density
evaluatee the mean carrier
evaluat
over a grain
In non-degenerate
is, using Eq. 3.31
is, n,
3.31 for n,
conditi
non-de genera te conditions ons the
the carrier average d over
density averaged
carrier density a grain i9-i
9-
10 4
104
IOl3
10

21
Q.
)02
102
d 2 ~
(n) = -21d/2/ Nce-(E c(x)-EF )/kBTd x.
(n) = d_ 00Nce-CEcCx)-EF)/kBT dx.
(8.26)
(8.26)
.~
.;:
>
'C
D
... 1011
10
.~
R 10
u 10
approp riate
forEc(x) with the
Ec(x) with
This can be evaluated
of LL in
values of
values in each
using Eq.
exactly using
evaluat ed exactly
The result
case. The
each case. result has
8.14for
Eq. 8.14
limiting forms
the limiting forms
has the
the appropriate
i'"i
en
10-11
10-
10.2
10-2
(n) : : : : nje(EB+ EF)/kT (8.27)
(8.27) 10-33
10-
(n) ~ neCEB+EF)/kT
,.
10 17
10 IS 10 19
17 101019
~ Nss and
dNd N
for dNd
for ..,
:i DOping (em-3)
a>ncenlralion (em-l)
Doping ooncntiation

(8.28)
(n) :~: : : Nd
(n) Nd (8.28) (c)

and insensitive to Fi~. 8.21.

Fi~. 8.21. Grai~
Grainboundary
boundar y model
model of
of resistivity
resistivi ty in
in polycrystalline
polycrys talline materiaL. . (a) Barrier
material (a) Barrier
~ N
for dNd :;:; Ns'
s . This has the
This has consequence that
the consequence is small
that aa is small and insensitive to , . . .. maximum .occurs
rapidly with Nd height as a function of d~p~n~
of doping density
density, fromfrom
Eqs. Eqs
8.15 815
and and
8.21. 821
The The
maximu m occurs
doping over
doping regime where
the regime
over the wheredNd dNd<-( N s , but
Ns, but then rises rapidly
then rises with Nd heIght as a function
when dNd ~ N . (b) ResIstIVIty for grain boundar y
when dNd ~ N.. (b) Resistivity for grain boundary calculated
calculate d from
from Eqs.
Eqs. 8.24
8.24 and 8.27,
8.27,
s the limit for crystal materia l as
line material =
dNd >:; N
once dNd
once Ns,s , finally tending toward
finally tending towards the limit for crystallne as co~par:.~ with the
co~par~ WIth the case case of
of an
an ideal
ideal crystal
crystal with
with EB
EB =
= O.
o. Parameters
Paramet ers used
used were
were Ns
Ns =
l is therefo re high at low 10 m. ,~. = 1 J.m, . = lOo. (c) Data for the resistivity of polycrystalline and
and
o. 10 m. ,~ . = 1 j.Lm, e. = lOeo. (c) Data for the resistivi
resistiv ity of a polycry stalline materia ty of polycrys talline
EB ~ The
EB -4 O. The resistivity of a polycrystallne material is therefore high at low
levels until crystallm e slhcDn Moller, 1983].
silicon [Moller,
doping levels, falling
doping levels, very rapidly
fallng very rapidly at doping levels
interme diate doping
some intermediate
at some until
crystalline 1983j.

ted in
finally itit compar
finally compares withcrystal
es with crystallne valuesatat high
line values highNd. Thisisisillustra
Nd.This ilustrated in
Fig. 8.2l.
Fig. 8.21. ~ 8.5.5. of illumi
Effect of
8.5.5. Effect nation
illumination
stalline ma-
suggests that we
This suggests should aim
we should aim for doped polycry
highly doped
for highly polycrystallne ma- By analogy with the level
to reduce resistiv e losses. Howeve r, high doping tends to increas e the By analogy with the case of bulk
case of bulk recombination via a
recomb ination via a single
single trap level
terial reduce resistive losses. However, high doping tends to increase the by
given by
is given
occupied is
ries, as will be (Eq. 4.78),
(Eq. 4.78), the fraction of interface are occupied
which are
interface traps which
ofminori
losses of
losses minority carriersvia
ty carriers viarecomb
recombination grain bounda
ination atat grain boundaries, as wil be
line materia the best
ls, the is a comprc)illise
materia l is
best material
seen below.As
seen below. Aswith withcrystal
crystallne materials, a comprmise - SpPt
SnnSnn
it= =Sn(n
it
+- nt)
SpPt
+ Sp(p++ Sp(p
betwee
between n high doping and
high doping and highhigh conduc tivity.
conductivity. Sn(n + nt) pd (8 .29)
+ pi) (8.29)
240
240
The Physics
The Physics of
of Solar
Solar Cells Thin Film
Thin Film Solar Cells
Cells 241

/', 1 simply proportional

simply proportional to to the
the minority carrier density
minority carrier density as
as expected
expected for
for bulk
recombination in
recombination in aa doped
doped material (Eq. 4.80).
4.80). However,
However, itit is convenient
convenient to
to
EBB low lightintensi
low light intensi" ___,_,_",.#~// 'k\.,~__""",_", ,_=~.w:,I~h light intensity
define an
define an effective interfacerecombination
effective interface recombinationvelocity,
velocity,S8gb,
b
g,

8gb==_ _ Jp(L)
Sgb Jp(L) (8.31)
(8.31)
Fig. q(P(L) -- Po)
q(P(L) Po)
Fig. 8.22. Grainboundary
8.22. Grain boundary height
height at
at different
different light
light intensities.
intensities. At high
high light
light intensity,
intensity,
changes in
changes in the
the charge
charge stored
stored in
in the
the interface states reduce
interface states reduce the
the height of the potential
height of
where Jp(L)
where Jp(L) and
and p(L) are p(L) areatevaluated
evaluated the edge of at the edge of the depletion layer
layer and Po
and Po
barrier..
barrier
is the equilbrium hole density.
is the equilibrium hole density. Jp(L) is equal to the interface recombination
current density,
density, whence
whence
where n,
where n, P are the densities
densities of electrons
electrons and and holes
holes at at the grain boundary
boundary
and 8n, Sp are the interface recombination velocities.
Sn, 8p velocities.Illumination increases
Ilumination increases Jgb == Jp(L)
Jgb =
Jp(L) = -qSgb(p(L)
-q8gb(p(L) -- Po).
Po). (8.32)
(8.32)
both nand
nand p, but the
p, but the fractional
fractional increase
increase in in the
the minority
minority carrier population At equilibrium, net grain boundary recombination
recombination is zero. Under increasing
_
_ holes
holes inin this
this case greater. ItItisisclear
case -- isisgreater. clear from
from Eq.Eq. 8.29
8.29 that, for
for aa
illumination,
ilumination, the net charge at the grain
the net charge at the grain boundary decreases so
boundary decreases so that
that the
the
grain boundary in n type material, if nand p
grain boundary in n type material, if nand p are both increased are both increased by the
barrier
barrier height
height decreases, and the enhancement
decreases, and enhancement of of the recombination
recombination rate
same amount, It wil
same amount, willbe bedecreased.
decreased. Physically,
Physically, thisthis is
is due
due aa greater rate of due to the depletion
depletion region
region decreases. The effect
decreases. The effectisisthat,
that, at intensities such
hole
hole capture by the grain grain boundaries,
boundaries, resulting
resulting in a lower
lower net charge. The
that pp :;>Pt,
that Pt, the
theratio
ratioininEq.
Eq.8.31
8.31decreases,
decreases, and
and the
theeffective
effective recombination
reduced
reduced grain boundary charge reduces reduces the barrier height EB, as shown
EB, as shown in
velocity decreases.
Fig. 8.22.
8.22. AtAt first, if the minority carrier Fermi level is stil above the trap
if the minority carrier Fermi level is still above
To
To evaluate
evaluate the overall effect on
overall effect on the
the minority carrier transport char-
minority carrier char-
level (i.e.,
level (i.e., P < Pt) the
p -( the effect
effect is
is negligible
negligible and EB unaffected. Then, as
EB is unaffected. as PP
acteristics
acteristics wewe need
need to to add
add the grain boundary recombination
recombination to to the other
surpasses Pt,
surpasses Pt, the barrier beginsbegins to fall.
fall. As
As EBEB isis reduced
reduced under
under increasing
increasing
principal recombination mechanisms.
mechanisms. We We define
define aa minority carrier lifetime
lifetime
illumination the
ilumination the majority
majority carrier
carrier mobilty,
mobility, andand hence
hence the
the conductivity,
conductivity, are
for
for grain boundary recombination from from the grain boundary recombination
recombination
increased. Intensity
increased. Intensity dependent mobilities
mobilties are commonly observed in practice
are commonly observed (i.e.,
rate per
per grain,
grain, (i. e., a volume
volume recombination rate)
in polycrystalline
in polycrystallne semiconductors.
semiconductors.
~1 _ _ Jgb
Jgb 8gb
_ Sgb
(8.33)
Tgb
Tgb - - qL(p(L) Po)- =L
qL(p(L)- -Po) L' (8.33)
8.5.6. Minority
8.5.6. Minoritycarrier
carrier transport
transport
Then an
an effective
effective minority carrier
carrier lifetime,
lifetime, Teff, can be
Teff, can be defined
defined by adding
The most
most important
important factor
factor controllng
controlling minority carrier transport
minority carrier transport is the
the grain boundary recombination
recombination to the
the other mechanisms ,,
othermechanisms
minority carrier recombination rate. Recombination
analogous to
analogous to surface
surface recombination
Recombination at a grain boundary
recombination and
and can
can be
be treated
boundary is
treated with the
is
the approach
approach 1 1+1
1
-=-+-+-+-.
-=-- -+
1 1 1
- - TAuger
1
+ - . (834)
1 1
(834)
of Sec.
Sec. 4.5.
4.5. The recombination current density,
density, Jgb,
Jgb, can be expressed
be expressed asas qq Teff
TeffTSRH Tgb
TSRH Tgb Trad .TAuger Trad

the area
times the area recombination rate at
at the
the grain
grain boundary,
boundary, using
using Eq.
Eq. 4.82,
4.82, An effective diffusion length Leff
Leff may be derived
derived from
from Teff in the usual
Teff in usual way,
way,
as for Eqs.
Eqs. 4.95
4.95 and
and 4.96
4.96
. np-
np n~
- nr
(8.30)
Jgb =
Jgb = qUgbOX =
qUgb8x =q q1 1
( ( + )) + 111( ( + ))
+ Pt
Sn PP
Sn Pt +Sp n +nt
Sp n nt
(8.30)
Leff = V DeffTeff . (8.35)
(8.35)

where nand are the

nand pPare the electron
electron and
and hole densities
densities at the grain boundary. NowNow In conditions
In conditions where
where grain
grain boundary
boundary recombination dominates
dominates -- that
that is
is,
because
because of the depletion region, the electron density
region, the electron density at at the grain boundary
grain boundary low doping, high
low doping, high grain
grainboundary
boundarydefect
defectdensity
densityand
andlow ilumination~-
lowillumination
will be
wil belower thanits
lower than itsbulk
bulkvalue
valueby byapproximately
approximatelye-EB/kBT
e-EB/kBT and the thehole
hole the
the overall effectivelifetime
overall effective lifetimeand
anddiffusion
diffsion length will
wil be
be bias
bias and
and intensity
intensity
density higher
density than its
higher than itsbulk
bulkvalue
valueby byeEB/kBT, so the
eEB/kBT, so the net recombinationrate
recombination rate dependent,
dependent, through
through the
thebias
biasdependence
dependence ofof8eff.
Seff. At
At higher
higher intensity
intensitylevels
levels
is higher than
is than itit would
would bebe in
in the
the absence
absence of
of the
the depletion
depletion region,
region, and is
is not
not the other mechanisms take over, and Leff increases. towards a
the other mechanisms take over, and Leff increases towards a saturationsaturation
 242 ThePhysics
PhysicsofofSolar
SolarCel13
Cel!.> Thin
Thin Film
Film Solar
SolarCells
Cells 243
243
242 The
i
that
thatsince
sincegrain
grainboundary
boundaryrecombination
recombinationoccurs
occurs in
inspace
spacecharge
chargeregions
regions
""0
""0 where
where nandnandppare arecomparable,
comparable, we we tend
tend to tosee
see the
the dark
dark current
currentcharac-
charac-
8 teristic
teristic typical
typical of of generation-recombination
generation-recombination currents (with (with ideality
ideality factor
factor
of
of 2)
2) ifif the
the grain
grain boundary
boundarydefect defect density
densityisis high
high enough.
enough .
. Because
Because minority
minoritycarrier
carrierlifetimes
lifetimes andand diffsion
diffusionlengths
lengthsare
arecarrier
carrierdensity
density
dependent,
dependent, the reverse
the reverse current
current which which
opposes the short opposes the short circuit photocur-
circuit photo cur-
6
""0
""0
rent
rent may
may be be intensity
intensity dependent
dependent whilst whilst thethe photocurrent
photocurrent may be be bias
bias
dependent,
dependent, and and not wellwell approximated
approximated by by Jsc'
J sc These
These mean
mean that
that simple
simple
diode equation descriptions
descriptions such such as as Eq.
Eq. 1.4 are not appropriate,
appropriate, unless
unless
e~ Silso Ip
type)
Silso Ip type)
grain
grain boundary
boundary effects
effects are
are well
well controlled.
controlled.
-c
s:
CJ
Silso In type)
Silso
HE"
type)
.!
HE" A further influence on J-V characteristics arises from
influence on recombination at
from recombination at the
c:
0 HE interface in
interface in heterojunction cells, discussed
heterojunction cells, discussed below.
below.

::
a:t
2 8.6. CuInSe2
8.6. CuInSe2Thin
ThinFilm
FilmSolar
Solar Cells
Cells

8.6.1. Materials
8.6.1. Materials properties
properties
Control
Control Copper indium diselenide (CuInSe2, or
diselenide (CuInSe2, or CIS)
CIS) isis aa direct gap semiconductor
uI1G-$i
ul1G-Si
with a band
band gap
gap of
of around
around 11 eeV V and
and anan optical
optical absorption which is amongst
50
so 100
100 150
1S0
the highest
the highest known
known for any any semiconductor.
semiconductor. Its Its strong
strong absorption,
absorption, as as well
well
Illumination
Ilumination intensity I%At11'
intensity I%AH1) as its
as its availability
availabilty in bothboth p andand n types, makeitit attractive
types, make attractive for for thin
thin film
photovoltaicsand
photovoltaics and itit has been
been developed
developed for for this
this purpose since the early
purpose since early
Fig.
Fig. 8.23. Increase inin effective
effective diffusion
diffusion length Leff with carrier density
density in
in p-Si.
p-Si. de
[de
Pauw,
8.23. Increase
1984.]
length Leff with carrier 1970s.In
1970s. Inits
itspolycrystalline
polycrystallne form,form,ititconsists
consistsofofgrains
grainsofofsize
sizeapproximately
approxiately
Pauw, 1984.j
11 J.Lm,
.m, which
which tend
tend to grow in a columnar structure so that that grain
grain boundaries
boundaries
are more
are morelikely
likelytotolielienormal
normaltotothe thep-n
p- junction.
junction. CIS CISp-np- homojunction
homojunction
value.
value. In polycrystalline silcon,
In polycrystallne silicon, Leff has been
Leff has been observed
observed to increase with
to increase with
solar cells
solar cellscan
can be
be made,
made, but but have
have an an effciency
efficiency of of only
only 3-4%,
3-4%, and and better
generation rate up to a saturation level (Fig. 8.23). In that material
generation rate up to a saturation level (Fig. 8.23). In that material grain grain
devicescan
devices can be
be made
made with
with aa heterojunction
heterojunctionstructure,
structure, using
using anan n-type
n-type CdS
a -(< 1017
10 17 em 3
boundary effects dominate
boundary effects dominate for
for doping levelsNNa
dopinglevels cm--3. .
emitter on a lightly doped p-type CIS
emitter CIS base.
base. The highly doped CdS layer has has
aa band gap of around 2.5 eV eV and serves
serves (i)
(i) as
as aa window
window layer
layer to to reduce
reduce the
the
8.5.7. Effects of
8.5.7. Effects of grain
grain boundary recombinationon
boundary recombination onsolar
solar cell
cell collectionlosses
collection lossesdue
due to to surface
surface recombination
recombination of of carriers
carriers photogenerated
performance
performance by short
by short wavelength
wavelengthlight, light, and
and (ii)
(ii) to transport
transport electrons
electrons fromfrom junction
to front
to front surface with minimum
minimum series resistance.
resistance. Only a few few .m
J.Lm of
of p-CIS
p-CIS
Grain
Grain boundary effects influence
boundary effects influencethe
the current
current voltage
voltage characteristic
characteristic of
of poly-
poly- base are
base are needed
needed forfor good
good absorption.
absorption.In In most
most photovoltaic
photovoltaicstructures
structures thethe
crystalline solar cells in several important ways.
crystallne solar cells in several important ways. alloy CuInGaSe2
alloy CuInGaSe2(CIGS)(CIGS)isis used
used inin place
place ofof CIS.
CIS. Addition
Addition of Ga improves
improves
. The
The effect
effect of
of grain
grain boundaries
boundariesininreducing
reducingmajority
majoritycarrier
carriermobility
mobilty may
may the photovoltaic
the photovoltaic characteristics,
characteristics,by byraising
raisingthethe band
band gap,
gap, asas well
well as
as the
the
increase series resistance.
increase series resistance. electronic
electronic properties
properties of of the
the rear
rear contact.
contact.
. The
The enhancement
enhancement of of minority carrier recombination
minority carrier recombination at grain boundaries
at grain boundaries The compound
The compound forms forms thethe chalcopyrite
chalcopyritecrystal
crystalstructure.
structure. The conduc-
conduc-
reduces
reduces lifetimes,
lifetimes,asasdiscussed
discussedabove,
above,and
andincreases
increasesdark
dark current.
current. Notice
Notice tivity
tivityofofptype
ptype CIGS
CIGS is is due
due toto native
native defects,
defects,mainly
mainly indium
indium vacancies
vacancies
244
244 The Physics
The Physics of
of Solar
Solar Cells Thin Film
Thin Film Solar Cells 245

and copper
and copper atoms
atoms on
CujIn ratio during
Cu/In
grain boundaries
grain
on indium

boundaries and give

valence band
valence band edge
edge such
indium sites,
during growth.
give rise
such that
sites, and

rise to
and can
growth. These native defects
can bebe controlled
controlled by
defects tend
tend to
to a distribution of trap energies
that the hole
hole activation
activation energy
by varying
varying the
to congregate
congregate at
energies above
energy is around
at the
above the
around 0.3
0.3 eV.
eV.
--_ EF
~E _ F
AR
AR coat

(Note this is smaller than the value for a-Si, indicating that
(Note this is smaller than the value for a-Si, indicating that charge com- charge com-
p - CulnSe
CulnSe22
pensation
pensation isis less
less of
of aa problem.)
problem.) InIn addition,
addition, positively
positivelycharged
charged selenium
selenium 2-51lm p-CulnGaSe
vacanciesconcentrate
vacancies concentrateat at the
the grain
grain boundaries
boundaries and must be passivated,
passivated, for 2

instance by
instance by annealing
annealing in in oxygen,
oxygen, to to reduce
reduce grain
grain boundary
boundary activity. Elec-
Elec- ZnO Mo contact
tron diffsion
diffusion lengths
lengths areare similar
similar toto the
the grain
grain size,
size, giving
giving rise to internal
internal Qlass
Qlass
quantum effciencies
efficiencies which are as as high as 90% at
as 90% at the maximum.
8.24. Band
Fig. 8.24. Bandprofile
profile and
and layer
layer structure of typical eIGS cell.
cell.

8.6.2. Heterojunctions
8.6.2. Heterojunctions in
in thin
thinfilm
filmsolar
solarcell
celldesign
design
effciency of collection.
efficiency collection. AtAt the
the Cu(In,Ga)Se2
Cu(In,Ga)Se2- - CdS CdS junction,
junction, aa step
step
In a heterojunction
heterojunction the the emitter
emitter isis made
made from
from aa different,
different, wider
wider band gap
gap of around
around 0.50.5 eVV in in the
the conduction
conduction band band edge
edge creates
creates aa triangular
triangular
material than the
material than the base.
base. Such
Such designs
designs are
are used
used in
in polycrystallne
polycrystalline thin
thin film
film barrier (Fig.
(Fig. 8.24(a)),
8.24(a)), opposing
opposing collection
collection of photogenerated electrons.
solar cells
solar cells for
for two
two reasons.
reasons.First,
First,the
the short
short diffusion
diffsion lengths
lengths mean
mean that This step
step acts like aa Schottky
acts like barrier, but its
Schottky barrier, its effect
effect onon photocurrent
photocurrent
high energy photons may
energy photons may not be collected effciently. The wider band gap
collected efficiently. collection isis negligible
collection negligibleifif it is
is less than 0.4 eV.
less than eV. ItIt introduces
introduces aa con-
con-
emitter therefore
therefore acts
acts like
like aa window
window (see(see Sec.
Sec. 7.6).
7.6). The second
second reason
reason is
is tribution toto the
the recombination
recombination current from tunnellng of
from tunnelling of electrons
electrons to
that
that CdTe
CdTe and
and CuInSe2
CuInSe2 thin
thin film
film materials cannot easily be doped n-type, interface defects in
interface defects in the
the CdS,
CdS, andand this is manifest as an ideality factor
so alternative materials such as CdS CdS must be be used.
used. greater than 2 in the
greater than the (low
(low temperature)
temperature) darkdark current
current characteristic
characteristic
The material
material interface
interface introduces
introduces several
several problems:
problems: ..~ Rau, 2001].
[Rau, 2001j. The
The problem
problem of of aa barrier
barrier at the heterojunction
heterojunctionisisavoided
avoided
(i) Differences
.. for CdS -- CdTe
for CdS CdTe n-p
n-pstructures.
structures.
(i) Differences between the crystal
between the crystal structure
structure or or lattice
lattice constants
constants of of the
the
two materials
materials generally introduce intra intra band
band gapgap defect
defect states
states at the
the
junction. These states encourage Shockley Read
junction. These states encourage Shockley Read Hall recombination,
recombination,
8.6.3.
8.6.3. CulnGaSe2
CulnGaSe2 solar
solarcell
celldesign
design
increasing
increasing darkdark currents
currents and limiting the open open circuit
circuit voltage.
voltage. They
They
may also assist tunnelling of carriers across the junction, again again increas-
increas- CIGS is deposited
deposited by two
two main
main methods:
methods: vapour
vapour co-deposition
co-deposition of
of copper,
copper,
ing recombination.
recombination. VeryVery large
large densities
densities ofof interface
interface states
states cancan lead to indium, gallum and
indium, gallium and selenium;
selenium; and the
the selenisation
selenisation of CujIn
Cu/In films.
films. After
After
Fermi level pinning at
level pinning at the interface, with the effect that carrier densi-
effect that carrier densi- deposition of the CIGS layer
layer the film
fim is
is annealed
annealed in
in oxygen,
oxygen, to compensate
compensate
ties are
are not
not easily
easily controlled.
controlled. charged
charged graingrain boundary defects and reduce
defects and the density of
reduce the of recombination
recombination
(ii) Differences between
(ii) Differences between the the chemical
chemical composition
composition of of the two materials
the two materials maymay centres. Then the
centres. Then the nn type CdS CdS layer is is deposited
deposited typically
typically by
by chemical
chemical bath
lead to the
lead to the diffsion
diffusion of
of species
species across
across the
the junction,
junction, or or the
the formation
formation deposition, followed by
deposition, followed by aa thin layer
layer of of conducting
conducting oxide
oxide which
which maymay also
also
of new chemical compounds in
chemical compounds in the junction region.
region. For example,
example, the serve
serve asas part
part anti-reflection
anti-reflection coat. Zinc Zinc oxide
oxide is preferred
preferred as its high
high con-
con-
unwanted alloys
unwanted alloys CuSe2
CuSe2 andand CUS2
CUS2 may
may form
form at at the
theCuInSe2
CuInSe2- - CdS CdS ductivity reduces
reduces the thickness
thickness of CdS needed needed to a few
few tens ofof nm.
nm. CIGS
CIGS
hetero junction.
hetero junction. cells
cells are always
always prepared
prepared as as substrate designs
designs onon a molybdenum
molybdenum coatedcoated
(ii) Differences between
(iii) Differences between the
the electron
electron affnity
affinity and
and band
band gapgap ofof the
the two
two ma-
ma- glass
glass substrate, as as Mo
Mo is is needed
needed to make make anan Ohmic
Ohmic contact.
contact. GaGa improves
improves
terials
terials may
may lead
lead to the
the situation
situation where
where there
there is aa narrow
narrow barrier
barrier or
or adhesion
adhesion to to the Mo contact,
contact, butbut isis costly.
costly.
spike
spike in thethe conduction
conduction or or valence band, or
valence band, or both, at at the
theinterface.
interface. The
The effciency
efficiency of of CIGS cells improved
improved substantially
substantially over the last
last 10
10 years
years
Then photogenerated
photogenerated carriers
carriers crossing
crossing thethe junction
junction needneed to tunnel
tunnel andpresently
and presently stands
stands at ata 18.4% for a device
18.4% for device on
on glass
glass substrate
substrate Contreras,
[Contreras,
through
through thethe spike
spike before
before they cancan bebe collected,
collected, and this this reduces
reduces the
the 1999].
1999).
 Physics of
of Solar
Solar Cells
Cells Thin Film
Film Solar
Solar Cells
Cells 247
247
246 The Physics
246

AR coat
ARcoat
The major
The major design
design problems
problems with
with CIGS
CIGS cells
cells are:
are: Teo
TCO
(i) Poor spectral response at long wavelengths, which is due to the poor
(i) Poor spectral response at long wavelengths, which is due to the poor
collection of
collection of carriers photogenerated at
carriers photogenerated at the back of
the back of the
the cell.
cell. Improved
Improved
photo current
photo
current requires
requires aa longer
longer electron
electron diffusion
diffusion length,
length, and
and since
since .LnLn ,~

at about 2 p,m is already similar to the grain size this

at about 2 .m is already similar to the grain size this means reducmg means reducing passivation layer
grain boundary
boundary recombination.
recombination. This may bebe done
done by by passivating
passivating the the metal
grain This may
interfaces or
interfaces, or increasing
increasing thethe crystallite size by
crystallte size by annealing.
annealing.
Fig. 8.25.
8.25. Layer
Layerstructure
structureofofCdTe
CdTe cell.
cell.
(ii) High reco~bination at the heterojunction, and grain boundaries. The
(ii) High recombination at the heterojunction, and grain boundaries. The
dark current
dark current is is about ten times
about ten times that
that of
of crystalline
crystallne silicon
silcon (which
(which hashas
aa similar band gap).
similar band gap). The
The high
high defect
defect density
density atat the
the heterojunction
heterojunction improve material quality.
improve material quality. Grain size
size can
can be
be increased
increased and
and material proper-
~
arises from
arises from thethe mismatch
mismatch of of the
the wurtzite
wurtzite crystal
crystal structure
structure of of CdS
CdS with
with
.:'
ties improved by annealing.
the chalcopyrite
the chalcopyrite structure
structure ofof CIGS,
CIGS, and
and encourages
encourages recombination
recombination by by CdTe can be single
CdTe can crystal or
single crystal or polycrystalline,
polycrystallne, although polycrystallne
polycrystalline
tunnelling via trap
tunnellng via trap states. states. is
is obviously the material
obviously the material of
of interest
interest for
for thin
thin film
film cells
cellsand
and in
in fact
fact it has
has
(iii) Although optical losses losses in
in the CdS can
the CdS can be
be minimised
minimised by keeping that
by keeping that achieved the best performance. AA wide variety of techniques have been used
(iii) Although optical
layer as thin as possible, poor collection in the blue and
layer as thin as possible, poor collection in the blue and green is green is aa prob-
prob- for
for the deposition of CdTe
CdTe in
in solar
solar cells.
cells.The
The best
best results
results to date have been
lem with
with mass-produced
mass-produced cells, cells, because
because ofof poorer
poorer surface
surface processing.
processing. achieved with
achieved with close
close space
space vapour transport, but
vapour transport, other candidates
but other candidates include
include
lem
gas phase
gas evaporation and spray pyrolysis.
phase evaporation

8.7. CdTe Thin

8.7. CdTe ThinFilm
FilmSolar
Solar Cells
Cells
8.7.2.
8.7.2. CdTe
CdTe solar
solarcell
cell design
design
8.7.1. Materials properties
8.7. 1. Materials properties
The preferred design
design isis an-CdS
an-CdS p-CdTe
p-CdTe heterojunction
heterojunctioncell.cell. As
As inin CuInSe2
CuInSe2
Cadmium
Cadmium telluride
telluride (CdTe)
(CdTe) isis the semiconductor from
the semiconductor the II-VI
from the group of
II-VI group of based cells
cells the
the CdS
CdS emitter acts as a window
window to improve collection
collection atat short
materials which is in principle best suited for photovoltaics.
materials which is in principle best suited for photovoltaics. It has a direct It has a direct wavelengths.In
wavelengths. In this
this case,
case, no
no barrier
barrier results
results in the
the conduction
conduction or or valence
valence
band gap of 1.44 eV, close to the optimum for photo conversion, conversion, and aa very band,
band, but lattice
lattice mismatch
mismatch between
between the twotwo materials
materials leads
leads to
to interface
interface
band gap of 1.44 e V, close to the optimum for photo
high optical absorption. It is one of only two
high optical absorption. It is one of only two II-VI compounds II-VI compounds (the other
(the other states. About 3-53-5 .m
p,m of
of CdTe
CdTe are needed for suffcient optical depth. This
for sufficient This
one
one is ZnTe, with
is ZnTe, with aa band
band gapgap of of 2.26 eV) which
2.26 eV) which can
can be
be doped
doped pp type
type asas is
is generally
generally weakly
weakly doped
doped but
but a second
seconddoping
dopingtreatment, e.g. with
treatment, e.g. copper
with copper
well as n type. Historically, CdTe was sought and
well as n type. Historically, CdTe was sought and developed as a p typedeveloped as a p type or lithium is needed
needed to improve
improve thethe conductivity
conductivity of of the
the CdTe
CdTe layer
layer at
at the
replacement
replacement for for the photovoltaic material,
the photovoltaic material, CU2S,
CU2S, which
which was
was used
used inin early
:arly rear contact.
rear contact. The materials
materials may
may be be deposited
deposited in in substrate fashion
fashion on on a
heterojunction designs with n type CdS as the wider
heterojunction designs with n type CdS as the wider band gap emitte.r, band gap emitter, metal substrate, or in in superstrate
superstrate fashion
fashion on
on TCO coated
coated glass.
glass.
but whose performance
but whose performancewas wasinhibited
inhibitedby bydiffusion
diffsion of
of Cu along the
Cu along grain
the gram Problems facing CdTe cell cell design
design are
are as
as follows:
boundaries.
The crystal adopts
adopts thethe wurtzite
wurtzite crystal
crystal structure,
structure, like
like GaAs,
GaAs, but has . The
TheCdS CdS emitter
emitterstil
stillabsorbs
absorbssignificantly
significantly in
in the green and very
very thin
thin (50-
The crystal but has 80 nm)
80 nm) layers
layers are needed
needed forfor good
good response
response toto green
green light.
light. One objective
poorer transport properties. It suffers from a high density of native
poorer transport properties. It suffers from a high density of native defects defects
such in CdTe
CdTe cell development
development is is to reduce the thickness
reduce the thickness ofof the
the CdS
CdS layer
layer in
such as excess Te
as excess Te atoms
atoms at the grain
at the grain boundaries
boundaries which
which give
give rise
rise to
to defect
defect
mass production.
states
states deep in the band gap. p type CdTe must be doped extrinsically but
deep in the band gap. p type CdTe must be doped extrinsically but
the high intra
intra band
band defect
defect density
density leads
leads to
to poor
poor doping
doping effciency,
efficiency, much
much asas . The
Thehigh
highdensity
density of
of trap
trap states
states at
atthe
thegrain
grainboundaries
boundaries give
give rise to a high
the high dar kkcurrent
current (about
(about 20 times
times that
that of the otherwise similar material GaAs)
in amorphous silicon. However, treatments have been developed
in amorphous silcon. However, treatments have been developed to satllrate to satJlrate
the traps and
and effcient (>15%)
efficient (:: 15%)solar
solarcells
cells have
have now
now been
been produced
produced from
from low v;,c
and low Voc(0.2
(0.2VVless
lessthan
than GaAs).
GaAs). The
The low
lowVoc
Vocisispartly
partlyattributed
attributed to
the traps Fermi level
Fermi level pinning
pinning at the trap
trap states.
states.
the
the polycrystallne materiaL. Activation by heating in CdCb is essential to
polycrystalline material. Activation by heating in CdCh is essential to
248
248 of Solar
The Physics of Solar Cells
Cells Thin Film
Film Solar
Solar Cells
Cells 249
249

. Fermi
Fermilevel
level pinning
pinning by
by the
the trap
trap states
statesleads
leadsto
todiffculties
difficultiesdoping
doping CdTe
CdTe harvests less than half of the
harvests less than half of the available
available photons (Fig. 8.1).
8.1). Below
Below we
we mention
mention
heavily p type
heavily Ohmic contact
type and making Ohmic contact to
to the substrate. two basic approaches to to improving
improving performance.
performance. A A 22 .m
/-Lm thick
thick.-Si
/-L-Si silcon
silicon
. Defects
Defects at
at the
theCdS-CdTe
CdS-CdTe heterojunction,
heterojunction, due
due to lattice mismatch
mismatch or to
to solar cell on glass has been reported with
with to
to have
have an
aneffciency
efficiencyof ofover
over 10%10%
the formation
the formation of
of other
other chemical
chemical compounds
compounds (such
(such as
as CdTe03)
CdTe03) enhance
enhance [Yamamoto, 1998j.
Yamamoto, 1998).
junction recombination.
junction recombination.
2
. Light
Lighttrapping
trappingininthin
thinfilm
filmSi
Sisolar
solarcells
cells
The most
The most effcient
efficientCdTe
CdTecell
cell is 16.4% effcient,
is aa 16.4% efficient, 11 cm2
cm CdS/CdTe
CdS/CdTe device
device on
on Relatively
Relatively thin cells can be
cells can be made
made from
from polycrystalline
polycrystallne silicon
silcon ifif light
light
glass, produced
glass, produced by the US US National
National Renewable
Renewable Energy Laboratories. The trapping techniques are used
techniques are used to increase
increase the optical path length
length inside
inside
challenge is
challenge is now
now to improve CdTe solar cell
to improve cell production technology
technology so as
as the cell.
cell. Texturing front and back
back surfaces increases
increases the
the optical depth by by
to increase the efficiency of mass produced cells towards the values
to increase the effciency of mass produced cells towards the values for lab for lab a factor of
of around
around 20,20, which
which means
means that that only
onlyaa few
few tens
tens of
of microns
microns of of.-Si
/-L-Si
cells. are needed to absorb most of the incident light. This relaxes relaxes the need
need forfor
a long
a long diffsion
diffusion length,
length, and allows higher base doping, which
and allows increases
which increases

ThinFilm
8.8. Thin
8.8. FilmSilcon
SiliconSolar
Solar Cells
Cells v;,c' The
Voc' physics of
The physics of light
light trapping
trapping willwil be discussed in in Chapter
Chapter 9. 9.
Parallel
. Parallel multijunction
multijunctionthin thinfilm
film silcon
siliconsolar
solarcells
cells
8.8.1. Materials
8.8.1. Materials properties
properties An alternative concept in thin film silcon is the parallel multijunction
film silicon
solar cell, where the cellcell is composed of consecutive micron-thick layers of
Thin film
Thin film microcrystallne
microcrystalline silcon
silicon isis characterised
characterised by
by grain
grain sizes
sizes of
of around
around
p and n type
type microcrystallne
microcrystallineSi. Si. Layers
Layers of of similar polarity are connected
connected
j.m. It
1 /-Lm. has the optical properties
It has properties of of crystalline silicon, while
crystallne silcon, while its
its electronic
electronic
together to give
give a set
set of
of p-n
p-njunctions
junctions connected
connectedin inparalleL.
parallel. Because the
properties are
properties dominated by
are dominated by the boundaries. Defect
the grain boundaries. Defect states
states atat grain layers are
layers are of
of similar
similarthickness
thicknesstotothe theminority
minoritycarrier
carrierdiffusion
diffsion length, the
include dangling
boundaries include dangling bondsbonds typical
typical ofof amorphous
amorphous silicon
silcon asas well
well as
probabilty is high that a photogenerated
probability is high that a photogenerated minority carrier wil reach and
will
extrinsic impurities introduced during growth. The
extrinsic impurities introduced during growth. The defect states defect states appear to
cross aa p-n
cross p-n junction. Majority carriers
junction. Majority carriers then
then diffuse
diffse laterally
laterally towards the
be distributed through the band band gap gap so that the grain boundaries
that the grain boundaries are are active
contacts. The
contacts. The cells
cells perform
perform better
better than
than single junction .-Si
single junction /-L-Si cell
cell of
of the
the
in
in both nand p ptype
both nand type materiaL.
material. Grain
Grain boundaries
boundaries dominate
dominate thethe transport
transport
3 same thickness
same thickness because
because the the fraction of minority carrier lost by by recombi-
recombi-
properties
properties of of microcrystalline
microcrystallne Si Si for
for doping
doping levels
levels Na -( 10 17 cm-
< 1017 cm-3,, giving nation is smaller.
smaller.
rise
rise to
to intensity
intensity dependent
dependent minority
minority carrier
carrierdiffusion
diffsion lengths
lengths and
and mobilities.
mobilties.
Microcrystalline silicon (/-L-Si) can be prepared by the same
Microcrystallne silcon (.-Si) can be prepared by the same techniques techniques
as multi-crystalline, normally
as multi-crystallne, normally by casting of molten molten silicon into aggregates
silcon into aggregates 8.9. Summar
8.9. Summary
or
or sheets. techniques have been investigated for
sheets. A range of other techniques for thin film
film
polycrystalline material, including liquid phase epitaxy,
polycrystallne material, including liquid phase epitaxy, chemical vapour chemical vapour Thin film
Thin film materials
materials based on on polycrystallne
polycrystalline or oramorphous
amorphous semiconduc-
semiconduc-
deposition
deposition andand the
the crystallisation
crystallsation of of amorphous
amorphous silicon.
silcon. The goal is to fab- tors are being developed
developed for for lower cost photovoltaics. Advantages
Advantages include
ricate cells by depositing the .-Si /-L-Si on
on cheap
cheap ceramic or foil substrates,
substrates, or or on
on the possibilties
the possibilities of of deposition
deposition over large areas
over large areas on on cheap
cheap substrates (such
(such
glass. as glass, plastic or foil) and the
as glass, plastic or foil) and the potential potential for fabricating
fabricating integrally con-
integrally con-
nected modules
nected modules duringduring film
film deposition.
deposition. The
The primary disadvatange is lower lower
8.8.2. Microcrystallinesilicon
siliconsolar
solarcell
cell design
design power conversion effciency
power conversion efficiency resulting
resulting from
from poorer
poorer charge
charge transport
transport proper-
proper-
8.8.2. Microcrystalline ties in the defective materials. Suitable
Suitable materials
materials should
should have
have high
high optical
optical
ties defective materials.
Figure
Figure 8.18.1illustrates
ilustrates the
the basic
basic problem
problemwithwith using
usingsilicon
silcon in in thin
thin film solar absorption. The materials
absorption. The leading amorphoussilicon
leadingarematerials are amorphous silcon (a-Si),
(a-Si), and
and the
cells.
cells. As
As in
in any
any polycrystalline material,the
polycrystallne material, the diffusion
diffusionlength
lengthinin.-Si
/-L-Siisiseffec-
effec- polycrystallne semiconductors
polycrystalline semiconductors cadmiumcadmium telluride
telluride (CdTe)
(CdTe) and
and copper in-
tively
tively limited
limited byby the grain size,
the grain size, and this places
and this places aa limit
limit on on the cell thic~ess
the cell thiclress dium gallium
dium gallum diselenide
diselenide (CIGS).
for
for effective
effective carrier
carrier collection
collection of
of aa few
few microns
microns oror tens of microns. However,
However, Amorphous silicon
Amorphous silcon offers
offersstrong
stronglight
lightabsorption
absorptioncompared
comparedtotocrystalline
crystallne
the
the low absorption coefficient means
coeffcient means that a
a layer of /-L-Si a
.-Si few few microns thick silcon and
silicon and maymay be be deposited
deposited at at lower
lower temperatures.
temperatures. As an an amorphous
amorphous
 250
250 The Physics
The Physics ofofSolar
SolarCellcr
CelliS Thin
Thin Film
Film Solar
SolarCells
Cells 251
251

semiconductor, itit suffers

semiconductor, suffers from
from 'dangling
'danglingbond'
bond'defects
defectswhich
whichmake
makedoping
doping References
References
difficult, and
diffcult, and intra
intraband
bandtail
tailstates
stateswhich
which reduce
reduce mobilty
mobility by
by charge
charge trap-
trap-
ping. Passivation with hydrogen reduces the defect density sufficiently that M.D.
M.D. Archer
Archer and
and R.D.
R.D. Hil
Hill(eds.),
(eds.),Clean
CleanElectricity
Electricityfrom
fromPhotovoltaics
Photovoltaics(London:
(London:
ping. Passivation with hydrogen reduces the defect density suffciently that Imperial College
Imperial CollegePress, 2001).
Press, 2001).
useful devices
useful devices may
may be
be made,
made, but
but the
theeffciency
efficiencyof
ofdoping
dopingisislow
low and
and lifetimes
lifetimes RH.
RH.Bube,
Bube,Photovoltaic
PhotovoltaicMaterials
Materials(London:
(London:Imperial
ImperialCollege
College Press,
Press, 1998).
1998).
in doped
in doped material
material are
are very
very short.
short. Poor
Poor transport
transport in
in doped
doped a-Si
a-Si mean
mean that
that H.C.
H.C. Card
Card and
and E.S.
E.S. Yang,
Yang, "Electronic
"Electronic processes
processes at grain boundaries under
under optical
optical
solar cells
solar cells are
are made
madeininp-i-n rather than
p-i-n rather than p-n structures. In
p-n structures. In p-i-n struc-
p-i-nstruc- IEEETrans.
illumination", IEEE
ilumination", Trans. Electron Devices ED-24,
Electron Devices 397-402(1977).
ED-24, 397-402 (1977).
tures, collection
tures, collection losses
losses maymay result
result from
from either
either neutralisation
neutralisationof ofelectric
electricfield
field M.A.
M.A. Contreras et et al.,
al., "Progress
"Progress toward
toward 20%
20% effciency
efficiency inin Cu(In,Ga)Se
Cu(In,Ga)Se polycrys-
polycrys-
or series resistance in the i-region. Higher efficiencies may be obtained using talline
talline thin-film
thin-film solar
solar cell",
cell", Progr.
Progr. Photovoltaics
Photovoltaics 7, 7, 311-316
311-316 (1999).
(1999).
or series resistance in the i-region. Higher effciencies may be obtained using H.
H. Fritzsche,
Fritzsche, "Density
"Density of states in in noncrystalline
noncrystalline solids",
solids", in
in Physical
Physical Properties
Properties
tandem structures,
tandem structures, which
which reducereduce the the thickness
thickness of of individual
individual ii regions,
regions, or or of Amorphous
Amorphous Materials,
Materials, eds.
eds. D.
D. Adler
Adler et
et al.
al. (New
(New York:
York: Plenum,
Plenum, 1985).
1985).
heterojunctions,which
heterojunctions, which reduce
reduce collection
collection losses
losses inin the
the emitter
emitter by by introducing
introducing M. A. Green, K. Emery, D. L. King, S. Igari and W. Warta,
M. A. Green, K. Emery, D. L. King, S. Igari and W. Wart a, "Solar
"Solar cell
cell effciency
efficiency
a window. The dispersive transport characteristics
a window. The dispersive transport characteristics and series resistance of and series resistance of tables", Progr.
tables", Progr. Photovoltaics
Photovoltaics 9, 9, 287-293 (2001).
287-293 (2001).
a-Si lead to light intensity dependent transport and
a-Si lead to light intensity dependent transport and current voltage charac- current voltage charac- S.S.
S.S. Hegedus,
Hegedus, "Current-voltage analysis analysis of a-Si and a-SiGe
a-SiGe solar
solar cells
cells including
including
teristics. A A long-standing
long-standing problem problem is is light
light induced
induced degradation
degradation or or Staebler-
Staebler- voltage dependent
dependent photocurrent collection",
collection", Prog.
Prog. Photovoltaics
Photovoltaics Res. Res. Appl.
Appl.
teristics. 5, 151-168
Wronski effect,
effect, which 151-168 (1997).
(1997).
Wronski which causes
causes aa 30% 30% reduction
reduction in in cell
cell performance
performance over over the
the
P.T. Landsberg
Landsberg and M.S. Abrahams,Abrahams, "Effects
"Effects ofof surface states and
surface states and of excitation
first months of operation.
first months of operation. on
on barrier
barrier heights
heights inin aa simple
simple model
model of of aa grain
grain boundary",
boundary", J. J. Appl.
Appl. Phys.
Phys.
Polycrystalline semiconductors
Polycrystallne semiconductors are are characterised
characterised by by grain
grain boundary
boundary ef- ef- 55, 4284-4293
4284-4293 (1984).
(1984).
fects. Defects at grain boundaries in doped material
fects. Defects at grain boundaries in doped material introduce space charge introduce space charge J. Merten et et al.,
al., "Improved
"Improved equivalent
equivalent circuit
circuit and
and analytical
analytical model
model forfor amorphous
amorphous
regions where silicon solar cells
cells and
and modules",
modules", IEEE
IEEE Trans.
Trans. Electron
Electron Devices 45,423-429
Devices 45,423-429
regions where majority
majority carrier
carrier mobility
mobilty is is reduced
reduced and and minority
minority carrier
carrier re-
re-
combination is enhanced. Saturation of traps reduce grain boundary recom- (1998).
combination is enhanced. Saturation of traps reduce grain boundary recom- K. Mitchell, A.L. Fahrenbruch
Fahrenbruch and and R.H.
R.H. Bube,
K. Mitchell, A.L. Bube, "Photovoltaic
"Photovoltaic determination of
bination at
bination at high
high light
light intensities.
intensities. The The effect
effect of of grain
grain boundaries
boundaries on on mobility
mobilty optical absorption coeffcient
coefficient in CdTe", J. J. Appl.
Appl. Phys.
Phys. 48,48, 829-830
829-830 (1977).
(1977).
and lifetime can be described with a model based
and lifetime can be described with a model based on the depletion approxi- on the depletion approxi- H.J. Moller, Semiconductors
H.J. Moller, Semiconductors for for Solar
Solar Cells
Cells (Artech
(Artech House, 1983).
House, 1983).
mation. In
mation. the best
In the best polycrystallne
polycrystallinephotovoltaic
photovoltaic materials,
materials, CdTeCdTe and and CIGS,
CIGS, P. de
P. de Pauw
Pauw et al.,al., "On
"On the
theinjection
injectionlevel
leveldependence
dependence of of the
the minority-carrier
minority-carrier
grain boundary activity is minimised during materials
grain boundary activity is minimised during materials growth, and effcient growth, and efficient lifetime inin defected
defected silicon substrates", Solid State Electron. 27,573
State Electron. 27,573 (1984).
(1984).
junction devices U. Rau and
U. and H.W. Schock,
Schock, "Cu(In,Ga)Se2
"Cu(In,Ga)Se2 solar solarcells",
cells", in
in Clean
Clean Electricity
Electricity from
from
p-n
p-n junction devices can can be be made.
made.
For
Photovoltaics,eds.
Photovoltaics, eds.M.D.
M.D.Archer
Archerandand RD.
RD. Hil
Hill (London:
(London: Imperial
Imperial College
College
For both CdTe and CIGS, cells
both CdTe and CIGS, cellsare
areprepared
preparedas n-p heterojunctions
asn-p heterojunctions with with Press, 2001).
Press,
an
an n-type
n-type CdSCdS emitter
emitter in in order
order to to minimise
minimise QE QE losses
losses inin the
the emitter.
emitter. TheThe J.Y.W. Seto,
J.Y.W. Seto, "The electrical properties of
electrical properties of polycrystalline
polycrystalline silicon
siliconfilms",
films", J.
J. Appl.
hetero-interface introduces additional defects which
hetero-interface introduces additional defects which act as recombination act as recombination Phys. 46, 5247-5254 (1975).
Phys. (1975).
centres
centres and
and reduce
reduce the open circuit
the open circuit voltage.
voltage. In CIGS-CdS structures
In CIGS-CdS structures the the W. Spear
W. Spear andand P. P. LeComber,
LeComber, "Electronic
"Electronic properties
properties of of substitutionally
substitutionally doped doped
heterojunction also introduces a barrier in the conduction band impeding amorphous Si
amorphous Si and
and Ge",
Ge", Phil. Mag.
Mag. 33, 935935 (1976).
(1976).
heterojunction also introduces a barrier in the conduction band impeding
electron T. Tiedje,
T. Tiedje, "Time resolved chargetransport
resolved charge transport inin hydrogenated
hydrogenated amorphous
amorphous silicon",
silcon",
collection.The
electron collection. The mainmain challenges
challengesare aretotoimprove
improvetransport
transport properties
properties in Physics
in Physics of of Hydrogenated Amorphous Silicon,
Hydrogenated Amorphous Silicon, eds.
eds. J.D.
J.D. Joannapoulos
Joannapoulos and and
of the bulk materials; improve the quality of the
of the bulk materials; improve the quality of the heterojunction; improve heterojunction; improve G. Lucovsky,
Lucovsky, 261-300
261-300 (Springer,
(Springer, 1984).
G.
contact with substrate and reduce losses due to
contact with substrate and reduce losses due to surface recombination in surface recombination in JJ.R
.R Tuttle,
Tuttle, "The
"Theeffect
effect of
of composition
composition on on the
the optical
optical properties
propertiesof ofCu 2InSe2 thin
Cu2InSe2 thin
the emitter. Efficiencies of over 16% and 18% have
the emitter. Effciencies of over 16% and 18% have been achieved in CdTe been achieved in CdTe films", Conf.
films", Conf. Record.
Record. 19th
19th IEEE
IEEE Photovoltaic Specialists
Specialists Conf., 1494-1495
1494-1495
and
and CIGS,
CIGS, respectively,
respectively,ininn-p n-p structures
structures on on glass.
glass. (1987).
(1987).
Microcrystalline K. Yamamoto
K. Yamamotoetet al., al., "Thin
"Thin film
fim poly-si solar cell
poly-si solar cellononglass
glasssubstrate
substrate fabricated
fabricated at
at
Microcrystallne siliconsilcon is is attractive
attractive for for thin
thin film
film photovoltaics,
photovoltaics, but but suf-
suf- lowtemperature",
temperature", MRS
fers from low optical absorption. Designs incorporating light trapping struc- low MRS Spring Meeting, April, 1998,
Meeting, April, San Francisco.
1998, San Francisco.
fers from low optical absorption. Designs incorporating light trapping struc-
tures
tures offer
offer to
to increase
increase the the QE QE forfor micron-thick
micron-thick films fims and and achieve
achieve improved
improved
transport
transport properties
properties by by oparating
oparating at high carrier
at high carrier density.
density.
 Chapter 99
Chapter

Managing Light

9.1. Introduction
9.1. Introduction

This chapter is
is about
about the
the effect
effect of increasing photon flux
increasing photon flux density
density within the
solar celL.The
solar cell. Themain
main reason
reasonfor fordoing
doingthisthis isis that
that by increasing
increasing the photon
flux per unit volume,
volume, we decrease the volume of cell cell material
material which is needed
to harness
harness a certain
certain amount of light. light. This decreases
decreases the the cost per unit of
cost per
converted, since
energy converted, since the
the volume
volume of ofcell
cellmaterial
materialisisthe the main
main determinant
determinant
of cost.
cost. Another
Another reason
reason isis that
that cells may perform
cells may perform more effciently under
more efficiently under
increased
increased photon
photon flux levels.
levels.
We start by reviewing
We reviewing howhow light
light is
is utilised
utilsed in in aa photovoltaic
photovoltaic cell.
cell. Con-
Con-
sider aa semiconductor
sider semiconductorlayerlayerof ofactive
activewidth
width w, w, supported
supported by aa substrate
substrate of
a similar semiconductor, as
similar semiconductor, as illustrated
ilustrated in in Fig.
Fig. 9.1.9.1. Light
Light normally
normally incident
incident
on the cell passes through encapsulating materials before meeting the cell
on cell
surface, where
surface, where itit may strike semiconductor or cell contacts. Some fraction,
R,
R, of
of the
the light
light will
wil be
be reflected
reflectedfrom from the
the semiconductor surface, contacts
semiconductor surface, contacts
and outer
and outer layers. Of the
layers. Of the remainder,
remainder, some somewill wil be be absorbed
absorbed in in the active
active

,)
bs(E)
b(E, x)
: b(E,

(1-R) bs(E)

o0 x w
Fig. 9.1.
Fig. 9.1. Attenuation,
Attenuation, transmission
transmission and
and reflection
reflection of incident
incident radiation in aa semicon-
semicon-
ductor layer
ductor layer of
of active
activewidth
widthww.. b.(E}
bs(E) isis the
the incident
incident photon
photon flux
flux density
density normal
normal toto the
the
surface, and
surface, and beE,
beE,x}x)isisthe
thetransmitted
transmitted photon flux flux density
density at
at depth x below
below the surface.
surface.

253
253
254 of Solar
The Physics of Solar Cells
Cells Managing Light
Managing 255
255
254

layers and
layers and some
some will
wil pass
pass straight through into
straight through into the substrate. Within
the substrate. Within the
the delivered
delivered byby the cell, JJ (V)
the cell, increases faster
(V) x V, increases fasterthan
than X,
X, so efficiency
so the effciency
cell, the
cell, the flux
flux attenuates
attenuates so
so that at aa depth
that at depth xx the
the flux
flux density
density of
of photons
photons of
of increases under increased
increases under increased photon
photon fluxflux levels.
levels.Note
Notethat
that this is independent
energy E is
energy is given
given by
by of the result that
thatfor
forsome
some defective
defective semiconductors,
semiconductors, current collection
collection can
be improved at higher
higher light
light intensities.
intensities.
b(E, x)
b(E, = (1
x) = (1 -- R(E))bs(E)e-
R(E))bs(E)e-1;1;a(E,x')dx'
a(E,x')dx' (9.1)
(9.1) This chapter
chapter isis organised
organised as as follows: first we
follows: first review the
we review the role of photon
where bs(E) flux in a solar cell and discuss the ways in which light management can im-
which light im-
where is the
bs(E) is incident photon
the incident flux density
photon flux density normal
normal to
to the surface, R(E)
the surface, R(E)
is the reflectivity of the surface, and a(E, x) is the absorption coefficient of
of prove the performance
performance of a solar cell. Then we
cell. Then we treat
treat the
the following
following strategies:
is the reflectivity of the surface, and a(E, x) is the absorption coeffcient
the semiconductor
semiconductor at x. Assuming
Assuming that all absorbed
absorbed photons
photons result
result in
in band
band anti-reflection coatings, concentrator
anti-reflection coatings, concentrator systems,
systems, light
light trapping
trapping structures
structures and
the at x. that all
gap excitation, electron-hole pairs
pairs are
are generated
generated at a rate
rate photon
photon recycling
recycling systems. In In each
each case
case the
the effect
effect on
on device
device physics
physics is
is briefly
briefly
gap excitation, electron-hole at a
discussed.
g(E, x) = a(E, x)b(E, x) = (1 - R(E))a(E, x)bs(E)e- 1; a(E,x')dx' (9.2)
g(E, x) = a(E, x)b(E, x) = (1 - R(E))a(E, x)bs(E)e- 1; a(E,x')dx' (9.2)
per unit
per unit volume,
volume, in
in accordance
accordance with
with Eq.
Eq. 4.25.
4.25. For
For aa cell
cell of
of thickness w, aa
thickness w,
9.2. Photon
9.2. PhotonFlux:
Flux: AA Review
Reviewand
and Overview
Overviewof
of Light
Light
fraction Management
b(E,w)
b(E, w)
fabs
fabs ==11- - R(E)
R(E)-- bs(E)
bs(E) Box 9.1. Understanding
Box 9.1. Understanding photon
photon flux:
flux: some
some definitions
definitions
of incident
of incident photons are absorbed
photons are absorbed while
while aa fraction
fraction The spectral photon
photon flux
flux density (E,
f3(E, r,r,B, ) is the number of photons
B, )
b(E,w)
b(E, w) of energy
energy EE which pass through
which pass through unit
unit area
area per
per unit solid
solid angle
angle per unit
ftrans bs(E)
ftrans == bs (E) time. In
time. general, f3 is
In general, is defined by aa direction
defined by (B, )
direction (B, ) and
and isis position
position as
as well
well as
as
energy
energy dependent.
dependent. Conservation
Conservation of of photons
photons requires
requires that, some volume
that, for some
pass through.
pass through. For
For aa uniform
uniform absorber
absorber the
the absorbed
absorbed and
and unused
unused fractions
fractions
V
V of material with surface
surface S,
S,
are
= (3(E, s, B, )dO dS 1
IsIs (E,
fabs (1 - R(E))(l - e-a(E)w) (9.3)
(9.3)
fabs = (1 - R(E))(l - e-a(E)w) = (gph(E, r) - uph(E, r))dV (9.5)
s, B, )df!. dS = 1 (gph(E, r) - uph(E, r))dV
and
where ss is
where is aa point on the surface, gph(E, r)r) is
surface, gph(E, is the
the photon emission
emission rate
rate and
ftrans== (1
ftrans
(1 -- R(E))e-a(E)w
R(E))e-a(E)w (9.4)
(9.4)
uph(E, r)r) the photon
photon absorption
absorption rate per unit unit volume.
volume. We define uph(E, r)
We define
respectively.
respectively.The The unabsorbed
unabsorbed fraction
fraction isis high whenever aw
high whenever aw is is small,
small, for
for as the net absorption,
as the absorption, that
that is,
is, the
the difference
difference between absorption and
between absorption and stim-
instance,
instance, for wavelengths close
for wavelengths closetoto the
the band
band gapgap and
and for indirect semicon-
for indirect semicon- ulated emission. The left
emission. The left hand integral in Eq. Eq. 9.5
9.5 is
is taken
taken over
over solid angle
ductors suchsuch asas silicon.
silcon. of! and points s on the surface
surface S, while
while the right hand integral is is taken over
over
For
For effcient light
efficient light utilisation,
utilsation, as as much
much light
light as
as possible
possible should
should bebe ab-
ab- all points
all points r within
within the
the volume
volume V. V. Using Gauss's law
Using Gauss's law wewe find
find that
that at any
any
sorbed in the active layers, so R(E) and b(E, w) should
sorbed in the active layers, so R(E) and b(E, w) should be as small as be as small as point within V
point
possible. If
possible. b(E, x)
If b(E, x) could
could bebe increased
increased within
within the
the cell,
cell, the photogeneration
the photogeneration
rate
rate would increase. This means we could achieve the same photogeneration
rate
would
rate with
increase.
with aa smaller
This
smaller volume,
means we
volume, reducing
could achieve the same
materials requirements.
reducing materials requirements.
photogeneration l V . f3(E, r, 8, cp)dO = gph(E, r) - uph(E, r).
l V . (E, r, 8, cp)df! = gph(E, r) - uph(E, r).
(9.6)

The effect of
The effect of increased b(E, x)
increased b(E, x) onon cell
cell effciency
efficiency isis discussed
discussed below
below in
in
Sec.
Sec. 9.4.
9.4. WeWewillwil show
show that if the
that if the flux
flux density
density is
is increased
increased by by aa factor
factor X,
X, The rate
The rate of absorption for photons
absorption for for aa given
photons for given fluxflux direction
direction is propor-
propor-
the cell current should increase, to a first approximation,
the cell current should increase, to a first approximation, in proportion to in proportion to tional to
tional to the magnitude
magnitude ofof the
the photon
photon flux,
flux,(3,, in
in that direction, and the
direction, and
X while the cell voltage increases as 10g(X). This means
X while the cell voltage increases as log(X). This means that the power that the power emission rate
emission rate proportional
proportional to
to the magnitude of emitted flux. flux. Summing up
256
256 The Physics
The Physics of Solar Cells Managing
Managing Light
Light 257

contributions over solid

contributions over solid angle,
angle, we
we find
find 9.2.1.
9.2.1. Routes to higher
Routes to higher photon flux
photon flux

uph(E,r)
uph(E, in
r) == L a(E,r)(E,r,B,)dO
a(E, r)f3(E, r, B, )d0. (9.7)
(9.7)
An
An increased
of
increased photon flux
of the
the light,
light, trapping
flux can be achieved in several ways,
trapping of
of the
the light,
light,or orby
by exploitation
ways, by
exploitation of
by concentration
of photon recycling.
photon recycling.
These are illustrated schematically
These are ilustrated schematically in Fig. 9.2.
9.2.
where aa is
where is the
the absorption
absorption coefficient
coeffcient at
at r,
r, and All of
All of these
these processes
processesaim aimto to improve
improvethe
theefficiency
effciencyofofutilisation
utilsation of pho-

gph(E,r)
9ph(E, in
r) == L (E,r)e(E,r,B,)dO
c:(E, r)f3e(E, r, B, )d0. (9.8)
(9.8)
tons in a given amount of photovoltaic materiaL.
conditions,
conditions, for forinstance
instancelight
lighttrapping
material. They
trapping strategies
They are useful in different
strategies are
are particularly
particularly important
important
for weak absorbers
for weak absorbers and and thin cells, while concentration is important in very
cells, while concentration is important
where c: isis the
where the emission
emissioncoefficient
coeffcient and
and and
and f3e
eisis the
the emitted
emitted flux density.
density. effcient, crystalline
efficient, crystallne cells.
cells.
Note that, in
Note in general,
general, c: and
and a may
may be be direction
direction dependent.
dependent. IfIf they are
are
direction independent,
direction independent, thenthen Uph
Uphandand 9ph
gphareare proportional
proportionaltoto the
the sum of
magnitudes of
magnitudes of the
the fluxes
fluxes from
from different directions.
directions. Combining Eqs. 9.6 to
Eqs. 9.6

--
~
"';g
9.8 and resolving along the direction
9.8 direction (B,
(B, ),
), we
we have
. J --
vv ..{3 == e
c:f3e -- a
af3 if ~
=i
I....'~."......
which can
which can also
also be
be written as
(a)
(a)
d
df3
dI == e
c:f3e -- a
af3 (9.9)
(9.9)

where L
l isis the
the lenth coordinate
dI
coordinate along
along (B,
(B, )
) Chandrasekhar,
[Chandrasekhar,1950j.
1950j.
J'
..

-- ~i
, --
'. bs --
In
In real
real materials the emitted
emitted flux,
flux, which
whicharises
arises from the radiative
radiative recom-
recom- == I......'C".'.".. == +- I
bination of carriers,
carriers, is
is usually
usually negligible.
negligible. That leaves
leaves us with the
the soluble
soluble (b) (d)
(b) (d)
linear equation
d
df3
- + af3 = 0
dl + a = 0
dI
(9.10)
(9.10)
-- --
In the
(B =
the case
0,
case where
=
where the
0), we
the incident
set
incident flux
f3 = b(E,
flux is
x) and
is directed
directed normal
have the
normal to
one
to the
the cell
dimensional
cell surface
(B = 0, = 0), we set = b(E, x) and have the one dimensional equation
db
surface
equation -- -- ~ --~I (e)
(c)
- + ab = 0 (9.11)
(9.11) (c) (e)
dx
dx + ab = 0
Fig. 9.2.
9.2. (a)
(a)InIna non
a nonoptimised
optimisedsolar
solarcell,
cell,light
lightisisincident
incident atatnormal
normal(one(onesun)
sun)concen-
concen-
which has
has the solution
solution tration
tration and
andlight
light isis lost
lost by
by reflection
reflection and transmission. Photogeneration
Photogeneration can can be
be increased
increased
by
by (b) reducing
reducing reflection with an anti-reflection coating; (c) increasing the incident pho- pho-
b(E, x)
b(E, b(E,O)e-
x) ==b(E, O)e-1;J;a(E,x')dx'
o(E ,x')dx' (9.12) ton
ton flux
flux density by concentrating the light. Note that that this
this increases
increases the
the angle
angle subtended
subtended
(9.12) by
by the
the light
light source;
source; (d) (d) confining
confining the light
light by
by means
means of internal reflection
reflection (or light trap-
trap-
ping)
ping) strategies; (e) (e) reabsorption
reabsorption of of photons
photons produced
produced by by radiative
radiative recombination.
recombination. SomeSome
usually
usually known
known as
as the Beer-Lambert
Beer-Lambert law. Henceforth, b(E, x)
law. Henceforth, x) is
is used
used to
to of
of these strategies
strategies wouldwould normally
normally be be used
used together,
together, e.g.,
e.g., an AR
AR coat
coat would
would be be used
used
represent
represent the flux travellng at depth
flux travelling depth xx normal
normal to
to the
the surface
surface of
of aa planar
planar under
under concentration,
concentration, and and light trapping structures
structures wouldwould be usedused toto enhance
enhance photon
photon
structure. recycling.
recycling.
structure.
258 The Physi
The Physics of Solar
cs of Solar Cells Managing
Managing Light
Light 259

In thischapter
In this chapter
we wilwe will look
look at
at the
the basic
basic physics
physics of
of each
each of
of the
the processes,
processes, Table
Table 9.1. Refractiveindices
9.1. Refractive indices of
of se-
se-
lected semiconductors
lected semiconductors and
and AR coat
how they
how they are
are or might be be achieved
achieved inin practice, and how
practice, and how they affect
affect the materials. From various sources
materials. sources in-
physics and
physics and performance
performance of of the
the photovoltaic cell. cluding Pankove
Pankove pankove,
[Pankove, 1971j.
19711.

Refractive
Refractive index
Material (at ca. 1.5
(at ca. 1.5 eV)
eV)
9.3. Minimising Reflection
9.3. Minimising Reflection
Si 3.44
9.3.1. Optical properties
9.3.1. Optical properties of
of semiconductors
semiconductors
~
Ge 4.00
GaAs 3.6
The optical properties of a solid
solid are described
described by the
the dielectric
dielectric constant,
constant, Alo.SG8u.2As
Alo.sG8{).2 As 3.2
~ AlAs 3.0
s.. eg
eg s is
is a complex
complex quantity and
and obeys
obeys
Tl20s 2.1
ZnO 2.02
~ = ns - i/'s (9.13)
(9.13) Sb
Sb N4 1.97
Si02 1.46
where
where nns is the refractive index of the material and the imaginary part /'s
g is the refractive index of the material and the
/';,s
j\'
is related
is related to the absorption coeffcient of the
absorption coefficient the material through
where
a=T' 47l/'s
411'/';,s
a = -,).- . (9.14)
(9.14)
TIs = ns see Os
secBs (9.17)
1/s = ns (9.17)
general, s,
In general, nss and /'s
es, n wavelength dependent,
/';,s are wavelength dependent, and and may
may be
be direction for p polarised light (with the
for the electric
electric field
field vector in the
the plane
plane of
of incidence)
incidence)
dependent. and
Differences in
Differences in refractive index determine the reflection and transmission
of light at the
the interface
interface between
between two
two materials.
materials. For
For thin
thin films,
films, light
light should
should 1/s nscos
TIs == ns cosBs
Os (9.18)
(9.18)
be treated as as coherent,
coherent, and and Maxwell's equations
equations can
can bebe solved
solved toto find the
the
and for s-polarised light (electric field vector
(electric field vector normal
normal to the plane
plane of
of inci-
inci-
relative amplitudes of transmitted
transmitted and andreflected
reflected waves.
waves. In thethe simplest
simplest case,
case,
dence). 00 and
dence). Bo Os are
and Bs are related
related through Snell's law
through Snell's law
that of
that ofaa plane
plane boundary
boundary between
between materials
materials of
of refractive
refractive index
index no n s,
and ns,
no and
interface at normal
light striking the interface normal incidence
incidence isis reflected
reflected with
with probability
probabilty sin Bo
no sin
no nssin
00 = ns Os ..
sinBs

R-
R no - n s
= (no
( - ns) 2 . )2 (9.15)
(9.15)
For unpolarised light, considered
unpolarised light, consideredas as an
an equal
equalmixmixof ofsand
sand pp polarisations,
polarisations,
no +ns
no +ns the
the net
net reflectivity
reflectivity generally
generally increases with angle (for the s polarised
polarised compo-
nent itit increases
increases while for
for the
the pp component
component itit has a minimum), approaching
semiconductor, ns
For aa semiconductor, ns is
is typically 3-4
3-4 at
atvisible
visiblewavelengths
wavelengths (Table
(Table 9.1),
9.1), one at large
large angles.
angles. The
The minimum
minimum reflectivity
reflectivity of
of aa semiconductor
semiconductor surface
surface
so that
that some
some 30-40%
30-40% of of light
light normally
normally incident
incident onon the
the surface
surface from
from free
free to unpolarised
unpolarised light
light occurs
occurs at
at normal
normal incidence
incidence and is is given
given by
by Eq.
Eq. 9.15.
9.15.
space wil be
space will be reflected.
reflected. At 30-40%,
30-40%, this is is unacceptably
unacceptably high
high for
for effcient
efficient photovoltaic
photovoltaic energy
energy con-
con-
At oblique incidence the reflectivity is is angle
angle and
and polarisation dependent. version.
version.
If the
If the incident
incident ray
ray makes
makes an an angle
angle Bo
00 with
with the
the surface
surface normal,
normal, and
and the trans- Snell's law alsoalso means
means thatthat light travellng
travellingwithin
within the
thesemiconductor
semiconductorto- to-
mitted ray an angle Os with the surface normal inside the
mitted ray an angle Bs with the surface normal inside the semiconductor semiconductor wards
wards the the surface
surface at an
at an angle angle
greater than greater than
the critical the
angle, Be, critical
is angle, Oe, is internally
internally
then
then reflected.
reflected. For an air-semiconductor
air-semiconductor interface the critical critical angle
angle is
is given
given by
by
2
R (TIO -- 1/s)2
R == (1/0 TIs) (9.16)
(9.16) 88ee =.=-1
SIn (no)
. sin(no)
-1
ns'
ns' (9.19)
(9.19)
Tlo ++1/s
1/0 TIs
 260 ThePhysics
The Physicsof
of Solar
Solar Cells
Cells ManagingLight
Managing Light 261
261
260

fromthe
from the front
front and
and rear
rear interface
interfaceofofthe
the thin
thin film
film are
are out
out of
of phase
phase and
and
f-
d1

interferedestructively.)
interfere destructively.)RRvanishes
vanisheswhen
whenititisisalso
alsotrue
truethat
that

ni = y'nons . (9.22)
(9.22)
Soby
So bycoating
coatingour oursemiconductor
semiconductorwith with aa thin
thin layer
layer of
of aa medium
medium with
with refrac-
refrac-
tive index.,;n.,
tive index vn, we we can
can reduce
reduce the
the reflectivity
reflectivity to zero
zero at some particular
some particular
wavelength, AO.
wavelength, o.Since
Sincethethesolar
solarspectrum
spectrumisisbroad,
broad,this
this wavelength
wavelength should
should
be chosen
be chosen to to lie
lie towards
towards the middle of the range of wavelengths which which can
can
be usefully
be usefullyabsorbed
absorbedfor forthat
that semiconductor,
semiconductor,and and this
this determines
determines thethe AR
coat thickness.
coat thickness. Close
Close to o,RRincreases
to AO, increaseswith
withwavelength
wavelengthapproximately
approximately like like
no (~;)2,
(~;)2, and at wavelengths where the phase shift becomes a multiple of 7l RR
n 5
n 1
and at wavelengths where the phase shift becomes a multiple of 1l'
the dielectric
reaches its
reaches its maximum
maximum value value equal
equal toto the
the natural
natural reflectivity uncoa~ed
reflectivity of the uncoa~ed
Fig.
Fig. 9.3. Single
9.3. Single layer
layer anti-reflection
anti-reflection coating.
coating. When
When the the of
thickness thickness of the dielectric layer
layer is
is
equal to to one
one quarter
quarter wavelength,
interface. This means that an
interface. This means that an AR coat optimised at one
one visible wavelength
wavelength
equal wavelength, the incident and reflected waves interfere destructively
waves interfere destructively
to cancel
to cancel out
out the
the reflected ray at
reflected ray the outer
at the outer surface.
surface. may be
may be quite
quite highly
highly reflecting
reflectingat at others.
others. ARAR coats
coats on
on silicon
silcon solar cells are
usually optimised
usually optimised for for red
red light,
light, where
where solar
solar irradiance
irradiance isis strong,
strong, and be- be-
come reflective
come reflectivein in the
the blue.
blue. For
For this reason silcon solar
reason silicon solar cells
cells often appear
appear
For the air-silcon
For the interface Be
air-silicon interface Oe == 16.9.
16.9. In
In the
the presence
presence of
of an
an optical
optical coating
coating
viole.toror blue.
viole: blue. Similarly,
Similarly,the the reflectivity
reflectivityof ofthe
the AR
AR coat
coat depends on angle,angle,
no in Eq.
no in Eq. 9.19
9.19 is
is replaced by the
replaced by the refractive
refractive index
index of
of the
the coating
coating and Be is
and Oe is
and increases
Increases at at wide angles. This
wide angles. This means
means that
that AR coats are of of limited use
increased.
increased. This phenomenon of total internal reflection
reflection is exploited in light
in diffuse light or for non-planar
diffuse light non-planar surfaces. Figure 9.4
surfaces. Figure 9.4 shows
shows howhow anan AR
AR
trapping
trapping structures,
structures,which
which are
arediscussed
discussed inin Sec.
Sec. 9.6.
9.6. coat which
which is tuned for for normal
normal incidence
incidence at aa certain
certainwavelength
wavelength becomes
becomes
reflecting
reflecting at other
other wavelengths
wavelengths and and wide
wide angles.
angles.
9.3.2.
9.3.2. Anti-reflection
Anti-reflection coatings
coatings
Reflectivity of the
the air-semiconductor interface can be reduced using an anti- 0.4
0.4
reflection (AR) coating.
reflection (AR) coating.An An AR
AR coat
coat isis aa thin
thin film
film ofof aa dielectric
dielectric with
with 0.35
0.35
refractive 8=00
refractive index ni intermediate
index n1 intermediate between
between those
those of
of the
the semiconductor
semiconductor (ns)(n6) 0.3
and free
free space (no). By considering
(no) . By considering forward and backward travellng waves
travelling waves
~ 0.25
0.3
>
0.25
'S;
:;::::;
:
in
in each
each medium
medium itit can
canbebeshown
shownMacleod,
[Macleod, 2001J that the
2001] that thereflectivity
reflectivityof
ofthe
the (,(,)
Q)
0.2
0.2
Q)
film
film for
for light
light of
of wavelength
wavelength is given
A is by
given by ;;::::
;Q) 0.15
0.15
Q)
2 a:
a: 0.1
0.1
RR __(1/0 "16)2++
("10- -1/s)2 (1)0"16/1)1- -1/1)2
(1/o1/s/rl tan 01(h
"11)2tan2 (9.20)
2 1 (9.20) 0.05
0.05
("10+ +
-- (1/0 "1.)2+ +(1/01/s/1/1
1/s)2 ("I01]6/1J1 ++1/1)
1]1) tan 8
tan2 01
0
where
where 01
81 is
is the
the phase
phase shift
shift in
in the
thefilm,
film, 300 500
500 700
700 900
900

01 (9.21) Wavelength II nm
Wavelength nm
81==27l1/1
21l'1)1d1
d1cos
cos01B11/ A,, (9.21)
F.ig.
F.ig. 9.4.
9.4. Calcula~ed.
Calcula~ed. reflectivity of
of single
single layer
layer ARAR coat
coat as
as function
function of
ofwavelength
wavelength atat
01
B1 is the angle
angle between the light
between the light ray and
and the
the normal
normal within
within the
thefilm,
film , and
and ~ifferent
~J!Ierent an~les
an~les of
of incidence
mCldence (J = 0,
(J = 0 0 , 30
30 0 and
and 60.
60 0 Notice
Noticehow
howthe
theminimum
minimumofofreflectivity
reflectivity
d1
d1 is
is the
the film
filmthickness.
thickness. RRclearly
clearlyhas
hasitsitsminimum
minimumvalue when0181= =:
valuewhen 7l 1l'12.
/2. lifts
hfts and
and shifts
shIfts totoshorter
shorterwavelengths
wavelengths at
atwider
widerangles
angles of
ofincidence.
incidence. Calculated
Calculated for
for aa
For normal incidence,
For normal incidence, this first happens when
first happens when d 1 d1 is equal to a quarter
equal to a quarter 100
100 nm
nm layer
layer of refractive index nl
ni == vl3.3
y'3.3on
ontop
topof
ofaasemiconductor
semiconductorof
ofrefractive
refractiveindex
index
ns
ns == 3.3.
3.3.
wavelength
wavelengthin inthe
thethin
thinfilm
filmmateriaL.
material. (In
(In those
thoseconditions
conditionsthe
thewaves
wavesreflected
reflected
 ThePhysics
The PhysicsofofSolar
SolarCells
Cells ManagingLight
Managing Light 263
262 263
262

In the
In the above
above treatment
treatment of of AR
AR coats,
coats, we
we neglect
neglectthe the absorption
absorption of ofthe
the thicknessand
thickness and
opticalmaterials.
optical materials.This This isis usually
usually aa good
good approximation
approximation since, since, for
for most
most ns (9.23)
semiconductors,the theabsorption
absorption visible
visiblewavelength
wavelengthisissufficiently
suffcientlyweakweakthatthat
semiconductors,
/'s :
I'-s ~ ns.
ns. For
For reflection
reflection from
from an absorbing
absorbing medium,
medium, ns ns should
should properly
properly be
(~:r no (9.23)
This condition
This conditionallowsallowsaalittle
little more
moreflexibility
flexibilty in
in choice
choiceof ofmaterials
materialsthan
than
replacedby
replaced bythe
the complex
complexrefractive
refractiveindex
indexnsns- - il'-s
i/'s in
in Eqs.
Eqs. 9.17-9.20
9.17-9.20 andand R
the single
the single layer
layer case.
case.InIn some
some cellcell designs,
designs,where
whereaawide
wideband
band gap
gap window
window
calculated with complex arithmetic.
calculated with complex arithmetic. The The incident medium should of course
course
layer isis present
layer presentfor for improved
improved carriercarrier collection,
collection,aa double
doublelayer
layer AR
AR coat
coat
be non-absorbing.
be non-absorbing. can be made simply by choosing an optical coating with refractive indexnn
can be made simply by choosing an optical coating with refractive index
AccordingtotoEq.
According
have aa refractive
have refractive index
Eq. 9.22,
9.22,the
index of
the ideal
of around
ideal AR
around 1.84,
AR coat
1.84, and
coat material
and for
material for
for GaAs,
GaAs, 1.90.
for silicon
1.90. Good
silcon should
should
Good materials
materials
satis~ing
satis~ing Eq. Eq. 9.23n2where
9.23 where n2 is the
is the refractive refractive
index of index of the
the window
window layer, an~
layer, an~
are silicon
silcon nitride
nitride which
whichhas hasn1 ni == 1.97 and tantalum
tantalum oxide oxidewithwithn1 ni == 2.1. choosingappropriate
choosmg appropriate thicknesses.
thicknesses.This Thishas
has been
been done
done with
with GaAs devices
devices
are 1.97 and 2.1.
having
having aa high
high aluminium
aluminium content
content AIGaAs
AIGaAs window.
window.
Thesegive
These giverelectivities
relectivitiesof of less than1%
lessthan 1%atatnormal
normalincidence
incidenceatatthe theoptimum
optimum
Regarding solar
. .Regarding solar cell
cell device
device physics,
physics, thethe effect
effect of
of anti-reflection
anti-reflection coatings
coatings
wavelength.
wavelength.
Improved reflectivity
Improved reflectivity over
over aa band
band of wavelengths
wavelengths can can be achieved
achieved with
IS
is sImply
simply to reduce R,
to reduce R, and
and increase
increase the the flux
flux and
and generation
generation rates, as defined
in Eqs.
Eqs. 9.19.1 and 9.2.
two or
two or more
more thin
thin films.
films. The
The greater
greater the
the number
number of of layers,
layers, thethe greater
greater the
range of wavelengths
range wavelengths over over which
which thethe reflectivity
reflectivity cancan be minimised.
minimised. Multi-
ple layers
ple layers are
are not usually practical for for solar
solar cells,
cells, given
given their cost and and ~he~he 9.4.
9.4. Concentration
sensitivity to angle of incidence,
sensitivity incidence, but but double layers
layers are used on some some high
h1gh
effciency cells.
efficiency Layers should
cells. Layers should be be deposited
deposited soso that
that refractive index increases 9.4.1. Limits to
9.4.1. Limits to concentration
concentration
consecutively
consecutively from from air (no) to
air (no) to first coat (n1)
first coat (ni) toto second
second coat (n2) to
coat (n2) to semi-
semi-
In photovoltaic
photovoltaic concentration systems, light
concentration systems, light isis collected
collected over
over aa large
large area
conductor
conductor (ns). Reflectivity
Reflectivity vanishes
vanishes when both films films have
have quarter-wave
quarter-wave
and focused on to a cell cell surface of smaller
smaller area.
area. This increases the incident
incident
flux density
flux density at the cell surface
cell surface by a concentration factor, which is
concentration factor, X, which is ap-
ap-
proximately
proximately the ratio of of the
the collection
collection and cell
cell areas. The mainmain objective
objective
0.4
0.4 of this strategy
strategy isis to
to reduce
reduce the
thecost
costofofthe
thephotovoltaic
photovoltaicconversion
conversion system.
system.
0.35
0.35
Concentrating optics are
Concentrating are much cheaper per unit area area than
thanphotovoltaic
photovoltaiccellscells
0.3
and the
the cells
cells convert
convert the concentrated
concentrated and unconcentrated
unconcentrated lightlight with
with ap-
ap-
0.3
proximately
proximately the samesame effciency. To aa first
efficiency. To first approximation, the concentrator
concentrator
~~ 0.25
'S;0.25
--single
- singlelayer
layer
cell
cell delivers
delivers the power of X identical
identical cells
cells in unconcentrated
unconcentrated light.
light.
-- double
doublelayer
~~
(, 0.2
layer
According
According to geometrical optics, concentrating
geometrical optics, concentrating the the incident
incident light
light isis
()
Q) 0.2
;CI) equivalent
equivalent to expanding
expanding the angularangular range
range subtended
subtended by by the
thesource.
source. Con-
Con-
0.15
==
Q)
a:CI)
a:
0.15 centrating sunlight
centrating sunlight by
by aa factor
factor X using aa spherical
X using spherical concentrator
concentrator increases
increases
0.1
0.1 the
the angular
angular range
range to
toOx
(}xsuch
suchand
andenhances
enhances the
the total
total(angle-integrated)
(angle-integrated)
0.05
incident
incident flux
flux by
by aa factor
factor
0.05
r 27r r 8x dr.
0
0 X = l21r
Jo Jol(JxH dO = .sin
22 (}x
(9.24)
300 500 700 900
900 1100
1100 X = Jo Jo
r r8l(Js
27r H
a dr.
= sin
. 20Ox (9.24)
300 500 700 l21r
Jo Jo HdO .SIn
2 ()
sun
Jo Jo H sin sun
Wavelength
WavelengthIInm
nm where
where Osun is the
(}sun is the half
half angle
angle subtended
subtended by the sun, 0.260.
0.26. It
It isis assumed
assumed that
that
the
theintensity
intensityofofthe
theconcentrated
concentratedlig~t
lig~tisisuniform
uniform over
over the
theangular
angularrange.
range.
Fig.
Fig.9.5.
9.5.Calculated
Calculatedreflectivity
reflectivityofof
double
doublelayer
layerAR
ARcoat,
coat,optimised
optimisedfor
for700
700nm.
nm.The
The
reflectivity
reflectivityofofaasingle
singlelayer
layerisispresented
presentedfor
forcomparison.
comparison.
Because
Because of
of refraction
refraction of
of light,
light, most
most of
of the
the light
light entering
enteringthe
thesemiconductor
semiconductor
264 ThePhysics
The PhysicsofofSolar
SolarCells
Cells Managing
ManagingLight
Light 265
264 265

isis directed
directed close to the normal, and so the flux normal to the surface is
close to the normal, and so the flux normal to the surface is
enhanced approximately by the factor X relative to the unconcentrated
enhanced approximately by the factor X relative to the unconcentrated
case. For normal incidence,
case. For normal incidence,
b(E,x) = (1- R(E))Xbs(E)e-J;a(E.x' )dx'.
b(E, x) = (1 - R(E))Xbs(E)e- 1; a(E,x')dx' . (9.25)
(9.25)
To a first approximation, the generation rate, as given in Eq. 9.2 increases
To a first approximation, the generation rate, as given in Eq. 9.2 increases
by the same factor.
by the same factor.
The geometrical
The geometrical factor Fs, introduced
factor Fs, introduced in Chapter 22 to
in Chapter to relate
relate the
the ab-
ab-
sorbed light to the angular range of the source, changes to
sorbed light to the angular range of the source, changes to Fig.
Fig. 9.7.
9.7. Tracking
Trackingsystem.
system.The
Theconcentrator
concentratormust
mustbe
bemounted
mountedtotofollow
follow the
thedirection
direction
of the
of the sun
sun on
on aa daily
daily and
andseasonal
seasonalcycle.
cycle.
Fx = 7l sin2 Ox = X sin2 Osun . (9.26)
(9.26)
The maximum
The maximum theoretical
theoretical concentration
concentration occurs
occurs when
when Ox ()x =
= 900, e., X
90 , i.i. e., X ==
46050. For a concentrator with cylindrical rather than spherical symmetry
46050. For a concentrator with cylindrical rather than spherical symmetry
the maximum
the maximumconcentration lower:XX==111/sinOsun.
concentrationisislower: sin ()sun '

9.4.2. Practical concentrators

9.4.2. Practical concentrators
In practice, concentration is limited by the quality of the optics, by tracking
In practice, concentration is limited by the quality of the optics, by tracking
errors in working photovoltaic systems, and by the practical difficulty of
errors in working photovoltaic systems, and by the practical diffculty of
coupling
coupling very very highly
highly concentrated
concentrated light, light, with
with its very wide
its very wide angular
angular range,
range,
into the cell. Practical concentration ratios of tens to thousands of suns Fig. 9.8.
Fig. 9.8. Compound
Compound parabolic
parabolic concentrator.
concentrator.
into the cell. Practical concentration ratios of tens to thousands of suns
have been achieved using reflective optics or Fresnel lenses. lenses.
have been achieved using reflective optics or Fresnel
Note
Note that imaging concentration is only possible when
that imaging concentration is only possible when incident
incident light
light AM1.5 spectrum,
AM1.5 spectrum, isis incident
incident onon the
the concentrator
concentrator from
from wide angles and
wide angles and can-
can-
rays
rays are
are parallel
parallel andand thethe concentrator
concentrator isis pointing
pointing at
at the sun. This
the sun. This means
means
not be coupled into the cell. Even in direct sunlight, the concentrator
not be coupled into the cell. Even in direct sunlight, the concentrator must must
that only direct sunlight can be concentrated. Diffuse sunlight, which has
that only direct sunlight can be concentrated. Diffuse sunlight, which has be made
be made to to follow
followthe the sun
sun during
duringitsits daily
daily and
and seasonal
seasonaltrajectories
trajectories and
and
been scattered by the atmosphere and composes some 15% of the standard
been scattered by the atmosphere and composes some 15% of the standard
this is achieved with tracking systems. Concentrator systems are mos~ cost
this is achieved with tracking systems. Concentrator systems are mos~ cost
effectivewith
effective withhigh
high quality
quality cells
cells where
wherethe the saving
saving onon photovoltaic
photovoltaic materi-
materi-
;\ direction of sun direction
directionof
ofsun
sun als is greatest, and in ,finny climates where the direct solar irradiation
als is greatest, and in , tinny climates where the direct solar irradiation is is
;\ direction of sun
largest. 'fracking
Trackingsystsystems areessential
essentialforforhigh
highefficiency
effciencybut
butadd
addtoto the
the
largest.
cost and
cost and complexity
complexity of
ems are
of the
the system.
system.
An alternative
An to imaging
alternative to imaging concentrators
concentrators are
arenon-imaging,
non-imaging, low
low concen-
concen-

lens tration ~ystems

tration ~ystems which
whichdo donot
notrequire
requiretracking.
tracking.An
Anexample
exampleisisthe
thecompound
compound
parabolic concentrator Welford, 1990j. The cell receives light with
parabolic concentrator (Welford, 1990J. The cell receives light with the the an-
an-
gular range
gular range (),
0, where
where ()
0 is the half
is the half angle
angle of
ofthe
the paraboloid,
paraboloid,andand achieves
achieves
parabolic mirror
parabolic mirror concentration ratios of 41 sin2
2 0, or 4n21
2 sin2
2 0 if filled with a medium
concentration ratios of 4/ sin (), or 4n / sin () if filled with a medium of of
(a) (b)
(b) refractiveindex
refractive indexnn..
(a)
Fig. 9.6. Concentrator system based on (a) parabolic reflector (b) Fresnel lens.
lens.The
Thecell
cell Anotherapproach
Another approach toto non-imaging
non-imagingconcentration
concentration isis the
the use
use of
of fluorescent
fluorescent
Fig. 9.6. Concentrator system based on (a) parabolic reflector (b) Fresnel
is placed at the focus in either case.
is placed at the focus in either case. concentrators. AArefractive
concentrators. refractivematerial
material filled
filledwith
withfluorescent
fluorescentparticles
particlesre-emits
re-emits
266 The Physics
The Physics of
ofSolar
SolarCells
Cells Managing
Managing Light
Light 267
266 267

photons on
photons on irradiation.
irradiation. The
The emitted
emitted light
light can
can be
be directed
directed on
on to
to the
thecell
cell increasing
increasing
exploiting total internal reflection, and the spectral range of the re-emitted JI int ens ity
intensity maximum
maximum
exploiting total internal reflection, and the spectral range of the re-emitted power
light can be controlled [Goetzberger, 1977]. powerline
line
light can be controlled Goetzberger, 1977J.

Jsc
lsc
9.5. Effects
9.5. Effects of
of Concentration on Device
Concentration on Device Physics
Physics

We wil
We willdistinguish
distinguishcells
cells which
which operate
operate under
under concentration
concentrationin low injection
inlow injection
conditions, where photogenerated carrier density is smaller than
conditions, where photogenerated carrier density is smaller than the equi- the equi-
librium majority carrier density, from those which operate in high
librium majority carrier density, from those which operate in high injectioninjection
conditions, where
conditions, where the
the photogenerated
photogenerated density
density is
is greater.
greater.
vVoc
oc--.
.
vv
9.5.1. Low
9.5.1. Low injection
injection Fig.
Fig. 9.9.
9.9. Current-voltage
Current-voltagecurve
curveatatdifferent
differentintensities.
intensities.Jsc
J. c increases linearly with
increases linearly with light
light
intensity and Voc increases like the logarithm of intensity. The result is that the maximum
intensity and Voc increases like the logarithm of intensity. The result is that the maximum
In low injection, a rr-n concentrator cell can be treated essentially with power
power point
point moves to higher
moves to higher voltages,
voltages, and
and the
the effciency
efficiency increases.
increases.
In low injection, a ~n concentrator cell can be treated essentially with
the standard theory for a rr-n junction as developed in Chapter 6. In low
the standard theory for a p- junction as developed in Chapter 6. In low
injection conditions, minority
injection conditions, minority carrier
carrier recombination
recombination rates
rates are linear and
are linear the
and the factor
current densities resolve into a dark component Jdark which depends on V
current densities resolve into a dark component Jdark which depends on V
X (1+ q~:(~ InX),
and aa bias
and bias independent,
independent, light
light generated
generated component
component JseJ sc which
which depends
depends on
on X (1 + q~:e(~ InX),
flux
flux density
density and
and acts in the
acts in the opposite
opposite direction.
direction. Thus,
Thus, from
from Eq.
Eq. 1.4
1.4
and the
and the efficiency
effciency by a factor
J(V) = Jse - Jdark(V)

where
where the
the dark
dark current
current typically has the
typically has diode-like form
the diode-like form so
so that
that (1 + q~:(~ lnx).
X) .
(1 + q~:e(~) In

J(V) = Jsc - Jo(eqV/mkBT - 1). (9.27) Figure 9.9

Figure 9.9 shows
showshow
howthe
theoperating
operating point
point of
of the
the cell moves to
cell moves to higher
higher voltage
voltage
J(V) = Jse - Jo(eqV/mkBT - 1). (9.27)
as X
as X increases.
Now
Now if if the
the incident flux bs
bs is is increased
increasedby byaafactor
factorXX through
through concentration In practice,
practice, however,
however, the
the dark
dark current
incident flux concentration In current is
is affected by concentration
affected by concentration
of the light, J will increase to a first
of the light, Jse wil increase to a first approxiation by
sc approximation by the
the same
same factor,
factor, through (i)
(i) increasing carrier densities
densities leading
leading to
to high
high injection
injection conditions,
conditions,
through increasing carrier
i.e., Jsc(Xb
i.e., Jse(Xbs) ) : : : : X Jsc(b s ), but leave the dark current,
s ~ X Jse(bs), but leave the dark current, for a given bias, for a given bias, and (ii)
and (ii) increasing
increasing temperature,
temperature, both
both leading
leading to
to deviations
deviations from
from this
this be-
be-
unaffected. This means that at any given bias
unaffected. This means that at any given bias below Voe the net current below Voc the net current haviour. These
haviour. These effects
effects are
are discussed
discussedininthe
the following
following sections.
sections.
increases
increaseswith with X. X. Moreover,
Moreover, aa higher higher biasbias isis needed
needed to achieve the
to achieve open-
the open-
circuit condition where dark current cancels photocurrent. Replacing J sc
circuit condition where dark current cancels photocurrent. Replacing Jse 9.5.2. High
9.5.2. High injection
injection
with X J sc in Eq. 9.27 we See that for a diode of ideality
with X Jse in Eq. 9.27 we s~e that for a diode of ideality factor m, the open factor m, the open
circuit
circuit voltage
voltage becomes
becomes Concentrator cells
Concentrator cellsmay
may be
be designed
designedtotooperate
operate inin high
high injection
injection conditions.
conditions.
That means
That that the
means that the photogenerated carrier densities
photogenerated carrier densities areare large
large compared
compared
Voe(X)= =m~BT
Voc(X) m~BTIn(X~SC
In(X~Se+1) ~Vce(l)+m~BT
+1):::::::Vc,c(l)+ m~BT InX
InX (9.28)
(9.28) to the doping density in the base, and both carrier types
to the doping density in the base, and both carrier types must be must be included
included
in the transport equations. Generally nand p wil be different and
in the transport equations. Generally nand p will be different and electric electric
fields due to carrier density gradients must be taken into account. In the
the
whereVc,c(l)
where Vce(l)represents
representsthe
theopen
opencircuit
circuitvoltage
voltageunder
underunconcentrated light
unconcentratedlight fields due to carrier density gradients must be taken into account. In
(1 sun). Thus Voc increases logarithmically with X, and if the cell fill factor limit where
limit wherenn == pp we showedininSec.
we showed Sec.8.4,
8.4,forforrr-i-n
~i-n structures,
structures,that
that the
the
(1 sun). Thus Voe increases logarithmically with X, and if the cell fill factor
remains
remainsthe
thesame
samethen
thenthe
thepower
powerdelivered
deliveredbybythe
the cell
cell should
should increase
increaseby by aa
transport equation for either carrier reduces to the diffsion equation-like
transport equation for either carrier reduces to the diffusion equation-like
268
268 The Physics
The Physics of
of Solar
Solar Cells
Cells Managing
Managing Light
Light 269
269

form,
form, The different
The different recombination
recombination regimes
regimesmay maybe
be distinguished
distinguished as
as aa change
change
2 n (n(n-- no)
in the
in Vc,c. If
the intensity dependence of Vce' If the
the separation in electron-hole
electron-hole Fermi
Fermi
dd2n no) g(E,
g(E,x)
x) __ 0 (8.9*)
(8.9*) levelsisisequal
levels equalto andnn== p,
to qqVVand p, then
then from
from the law of mass
mass action we have
have
dx2
dx 2 - - L;L~ ++ DaDa - -
n = nV/2kBT
whereDDaa-- DnDp
where DnDp
-Dn+Dp'
Dn+Dp'L2L2a==Da DTa Ta
and T isTa the
and
a, a, a
ambipolar
is the ambipolarcarrier
carrierlifetime,
lifetime, ~
~
given by
given by Eq.
Eq. 8.12. , and so we
and so expect recombination
we expect recombinationto to vary
vary like",
like", eqVe qV /2kBT
/2kBT for
forSRH process,
SRH process,
.,
like'" qV 3qV
If
If the
the dominant recombination
recombination process is linear with excess carrier den- ~ like '" eeqV/kBT
/kBT for
for radiative
radiative processes
processes and
and like'"
like '" ee3qV/2kBT/2kBT for
for Auger.
sity, then Ln is independent
sity, then
nn and the solution
independent of of n,
n, the
solution can be separated into
the differential equation
equation (8.9)
into independent
(8.9) is
independent light dependent
is linear
linear in
dependent and
-21
,~
;1;
Consequently we expect
Consequently we expect V;
respectively,ininthe
respectively, the three
V tooe q' q 3q'
vary like
oc to vary like 2kB
three cases.
cases. InIn the
2kB

the case
q
In
T In '
T

case of
X
X kBqT
kB

of silicon,
T In X and
and 2kB
2kB
3
silcon, Auger recombination
T
Auger.
TqIn
InXX'

bias dependent
bias dependent terms,
terms, as
asinin the
the treatment
treatment in Sec. 6.5, i.e., superposition is
Sec. 6.5, ;,-=
places aa limit on the cell
places cell performance under concentration.
valid. This is the case
valid. case for
for Shockley
Shockley Read Read Hall
Hall recombination,
recombination, eveneven at high
injection. Letting nn = pp in
injection. Letting in Eq.
Eq. 4.79
4.79 for
for the
the SRH
SRH recombination
recombination rate, and 9.5.3~
9.5.3~ Limits to efficiency
Limits to effciency under concentration
under concentration
assumingn
assuming n // nt,
nt, and pp // Pt,
Pt, we
we find that
find that
n In Sec.
Sec. 2.5 we showed
2.5 we showedhow howtoto calculate
calculatethe the efficiency
effciency of of aa solar
solar cell
cell in
in the
USRH + ~ ~ . (9.29)
USRH ~ - - _ .
Tn + Tp
Tn Tp
(9.29)
radiative limit, where the only loss process process isis radiative
radiative recombination.
recombination. The
net flux absorbed in the cell cell is the difference between an
difference between an incident
incident flux
flux term
term
USRH
USRH is is stil
still proportional
proportional to to nn but
but the
thecarrier
carrier lifetime
lifetime has
has been increased.
been increased.
which isis proportional
proportional to to FFs,
which s , and an emitted flux term which is is proportional
Physically this
Physically this is
is due
due to
to the relative scarcity
scarcity of of majority carriers.
carriers. In low
low to Fe,
Fe, thethe geometrical
geometrical factorfactor for for emitted
emitted light.
light. ForFor aa flat
flat plate
plate cell in a
cell in
injection, thethe capture of aa minority carrier in aa trap
minority carrier trap state
state is immediately fol- standard sun
standard sun Fs/Fe
FslFe == 2.16 10- 5 , because
2.16 x 10-5, because of of the
the small
small angular
angular width
width of
lowed
lowed by by the
the capture
capture of aa majority
majority carrier, simply because of the abundance the sun. Increasing Fs Fs to Fx by by concentrating
concentrating the the light
light (Eq.
(Eq. 9.25)
9.25) increases
increases
of majority carriers, and the rate rate determining
determining step was was the minority
minority carrier the absorbed
absorbed relative to emitted fluxes fluxes at
at any value
value of the the chemical
chemical potential
potential
capture. Now both both hole
hole capture
capture and
and electron
electron capture are rate determining. (see Eq.
(see Eq. 2.16)
2.16).. This
This increases
increases the the product
product ofof net
net flux
flux and
and chemical
chemical potential,
potential,
If SRH recombination is dominant at at all
all injection
injection levels,
levels, superposition
superposition and hence the limiting
limiting effciency
efficiency of the solar solar cell.
cell. Maximum concentration
should hold and and the
the arguments
arguments given
given above
above for the variation Voc and
variationofofVoe and cell
cell is achieved
achieved when acceptance Ox
when the angle of acceptance Ox reaches
reaches90 0
900, and Fx
, and Fx = Fe Fe ==7l7r
power
power with concentration should be valid. valid. Indeed,
Indeed, JseJ sc may
may increase
increase even
even radians,
radians, so so that thethe cell
cell accepts
accepts and and emits
emits light
light over
over the
the same
same angular
angular
faster
faster than X, X, on
on account
account of
of the
the longer
longer carrier lifetime at high high injection.
injection. range.
range. ThisThis leads
leads to to aa maximum effciencyefficiency of over 40% 40% if the temperature
temperature
Radiative
Radiative and and Auger
Auger recombination,
recombination, however,
however, become non linear with n is unaffected. Another way
unaffected. Another way of of achieving
achievingthe thecondition
conditionthat that FeFe == Fs
Fs is to
in high
high injection.
injection. From
From Eq.
Eq. 4.57 it is
4.57 it is clear
clear that
that the
the radiative
radiative recombination
recombination restrict
restrict the
the angular
angularrange
rangefor for emission.
emission. This
This idea
idea isis developed in Chapter
Chapter 10. 10.
rate will
rate vary like
wil vary like In practice,
practice, concentration
concentration systemssystems increase
increase the maximum
maximum effciency
efficiency ofof
Urad Bn 2
= Bn2
Urad =
high quality
quality SiSi and
and GaAs
GaAs cells
cells byby a few
few percent. However,
However, when when the optical
losses
losses in in the
the concentrating
concentrating system system and and the
the wastage
wastage of ofdiffuse
diffse light are taken
when n ==p,p,implying
implyingaalifetime
lifetimewhich
whichvaries
varieslike
likeTT ex
ex n -1.
-1. Similarly,
Similarly, band-
band- into account,
account, concentrator
concentrator modulesmodules actually perform perform no no more
more effciently
efficiently
to-band
to-band Auger
Auger recombination
recombination (Eq.
(Eq. 4.66)
4.66) varies
varies like
like than
than oneone sun
sun modules
modules in in AM1.5.
AM1.5. Concentrators are of interest interest primarily
primarily forfor
the
the reduced
reduced cost through
through reduced
reduced cell area,area, and
and notnot for improved
improved effciency.
efficiency.
An33
UAug = An
UAug
Changing spectral intensity also changes changes thethe optimum band gap. gap. Fig-
Fig-
implying
implying that
that TT ex
ex nn -2.
-2. Therefore
Therefore at
at injection
injection levels
levels where
where radiative
radiative and
and ure
ure 9.10
9.10 shows
shows the limiting effciency
efficiency of an ideal photoconverter, calculated calculated
Auger
Auger processes are dominant, superposition
superposition becomes
becomes invalid, the dark
dark cur-
cur- as
as aa function
function of of band
band gap
gap according
according to to Sec.
Sec. 2.4-2.5, for an AM1.5 spectrum
AM1.5 spectrum
rent
rent term
termincreases
increases with
with generation
generation rate
rate and
and Voe
Voc rises
rises more
more slowly than
than with
with X X == 11and andXX= =1000 1000(Fx (Fx= =1000Fs)'
1000Fs ).ItItisisclear
clearthat
thatthethemaxi-
maxi-
predicted by Eq. 9.28.
predicted by Eq. 9.28. mum
mum effciency
efficiency point shifts
shifts to to lower
lower band
band gap
gap as asconcentration
concentrationincreases.
increases.
270 The Physics
The Physics of Solar Cells Managing Light
Managing Light 271

Note that this

Note that this calculation
calculationdoes
does not
not include
includeAuger
Auger recombination,
recombination, which
which be used for
be used for the
the active
active layers
layers than
than for
for aa one
one sun cell because
sun cell high carrier
because high carrier
is, like radiative recombination,
is, like recombination, an unavoidable
unavoidable process,
process, nor effects of
nor the effects densities mean higher conductivity, and also because lower doping produces
temperature. better quality
quality materiaL. Examples of
material. Examples of concentrator
concentrator cellscells are
are the PERL cell,cell,
developed at
developed at UNSW, (1/ (TJ == 26%
26% in in 20
20 suns)
suns) which
which operates
operates in low injection
conditions, and
conditions, and the
the rear
rear point contact
contact cell,
cell, developed
developed at at Stanford, which
9.5.4.
9.5.4. Temperature
is based
is based on on an
an undoped
undoped substrate
substrate and and operates
operates in in high injection
injection Sinton,
[Sinton,
High
High concentration
concentration raises
raises the temperature of
of the
the cell.
cell.At
Athigher
highertemperature
temperature 1986; Swanson,
1986; Swanson, 1990].
1990j.Buried
Buried contacts
contacts which
which combine
combine low low resistivity
resistivity with
the intrinsic carrier population low shading
low shading offer
offer to
to improve
improve series
series resistance
resistance in in future designs.
designs.
As noted
As noted above,
above, higher
higher emitter
emitter current densities mean that that series
series resis-
resis-
n~1 '" e-Eg/kBT tance minimisation
minimisation through conta,ctcont~ct and and emitter
emitter design
design isis important.
important. Con-
increases,
increases, an effect
effect which
which isis enhanced
enhanced byby the
the shrinkage
shrinkage of of the
the band gap Eg tact grids
grids should
should have
have thicker,
thicker, denser fingers
fingers and often are designed
designed with
with increasing
increasing temperature. Increasing n increases the dark current. The
ni increases The symmetry to match the image image of the concentrated light. They are normally
reduced band gap increases the
increases the photocurrent, but only
but only slightly compared to designed to
designed to give
give maximum
maximum performance
performance underunder certain concentration
concentration levels,
levels,
the effect on Jdark,
Jdark, so
so the
the increasing
increasing dark
dark current dominates. This opposesopposes and do not as
and as aa rule
rule give
give the
the best
best performance
performance underunder one-sun
one-sun conditions.
the effect increasing efficiency
effect of increasing effciencyunder
underconcentration
concentrationwith withthethe result
result that
that The higher
higher degree
degree of metallsation
metallisation needed
needed increases
increases losses
losses byby reflectivity
reflectivity
optimum performanceisis achieved
optimum performance achieved atat some
some intermediate
intermediate concentration
concentrationleveL.
level. and shading (to
and shading (to 10-20%),
10-20%), but but this
this can
can be
be overcome
overcome by by encapsulating
encapsulating the the
GaAs
GaAs hashas aa slightly
slightly better
better temperature coeffcient
coefficient of efficiency
effciency than
than silicon
silcon cell beneath
cell beneath aa prismatic
prismatic lenslens which
which refracts
refracts thethe light
light onto the bare
bare cell
cell
and finds its
and finds its optimum
optimum at at aa higher
higher concentration
concentrationleveL.
level. surface and
surface and away
away from
from the contact
contact fingers.
fingers.

9.5.5. Series
9.5.5. Series resistance
resistance
9.5.7. Concentrator
9.5.7. Concentratorcell
cell materials
By increasing
increasing the current
current density,
density, concentration
concentration increases
increases the potential
potential
drop,
drop, JAR.,
JARs, due
due to
to series
series resistance
resistance in
in the
the cell.
cell. This
This is
is aa problem
problem par-
par- Figure 9.10 shows that
9.10 shows that the optimum band band gap
gap for
for photovoltaic
photovoltaic energy
energy con-
con-
emitter layer
ticularly in the emitter layer where
where lateral current
current densities
densities are
are high.
high. Con-
Con- version is reduced
version is under concentration.
reduced under concentration. This This would suggest
suggest that silicon,
silicon,
centrator cells
centrator cells must therefore
therefore be
be designed
designed differently,
differently, with
with different
different metalli-
metall- with Eg
Eg = 1.11.1 eV,
eV, is
is aa better
better concentrator
concentrator cell cell material than GaAs GaAs with
with
sation patterns
patterns and
and ideally
ideally with
with higher
higher emitter
emitter doping
doping than
thanone-sun
one-sun cells.
cells. Eg
Eg == 1.4
1.4eV.
eV.However,
However, GaAs GaAs hashas two
two important
important advantages:
advantages: (i) (i) GaAs
GaAs
Emitter doping
Emitter doping levels
levels are limited by recombination and cannot be increased enjoys
enjoys aa better temperature
temperature coeffcient
coefficient of of efficiency
effciency than
than silicon
silcon and (ii) (ii)
indefinitely, nor
indefinitely, nor can
can the contacted areaarea become
become too
too large,
large, soso compromises
compromises Auger recombination isis stronger
Auger recombination stronger inin silicon
silcon because
because of of its lower
lower band gap
be found.
must be found. Minimisation
Minimisation of of series resistance losses
losses is
is aa major objective and limits the theoretical
theoretical effciency
efficiency to 36%36% at aa concentration
concentration of of 100
100 suns
suns
in concentrator
concentrator cell
cell design.
design. with perfect
perfect light
light trapping.
trapping. Auger
Auger recombination
recombination is much less less important
in GaAs
GaAs and effciency
efficiency continues
continues to to rise with concentration up to to several
several
hundred
hundred suns.
suns. At 10001000 suns
suns the theoretical
theoretical effciency
efficiency isis 36-37%
36-37%Sinton,
[Sinton,
9.5.6. Concentrator
9.5.6. Concentratorcell
cell design
1995; Klausmeier-Brown, 1995J.
1995; Klausmeier-Brown, 1995].
Concentrator cells should
should be of very high purity, since high effciency efficiency is a No simple direct semiconductors
semiconductors exist exist with
with band gaps
gaps in the range 1.1-
priority,
priority, and because
because the cell
cell is a smaller fraction
smaller fraction of the system cost. The 1.3 eV, where
1.3 eV, where the theoretical effciency
efficiency under concentration
concentration is is high.
high. Some
Some
cell should
concentrator cell should have
have very
very low
low bulk
bulk recombination
recombination losses,
losses, so high
high ternary alloys, such as
alloys, such as InxGal_xAs,
InxGal_xAs, have have suitable
suitable band
band gaps
gaps but
but their ma-
ma-
crystals should
quality crystals should be be used,
used, and
and good
good surfaces.
surfaces. Light trapping
trapping isis helpful
helpful terial quality is inferior. To date, GaAs
inferior. To remains the best material for
GaAs remains for high
high
reducing the cell
in reducing cell thickness
thickness and thereby
thereby reducing
reducing resistive
resistive losses
losses du
due to
to concentration with aa record
record effciency
efficiency ofof 27.6%
27.6% in AM 1.5 under 255 255 suns
carrier diffsion
diffusionininthe
thehigh
highinjection
injectionlimit.
limit. More
More lightly
lightly doped material
material can
can [Vernon, 1991j.
Vernon, 1991]. The best silcon
The best siliconcell
cell is
is 26.8% at 96 suns
26.8% at [Verlinden, 1995J.
suns Verlinden, 1995].
272
272 Solar Cells
The Physics of Solar Cells Managing
Managing Light 273
273

0.40 large
large compared to the coherence
compared to length of
coherence length of the
the light,
light, and light rays
rays with
with

/r~''-,
~=lOOO different history do
different history do not interfere.
interfere. This is a good approximation in
good approximation in silcon
silicon

/I X-j
~, where cells
cells are
are hundreds of microns
microns thick.
thick. In
In micron
micron scale
scale structures,
structures, light

::
u>-
i:
r:::::
CI)

;:
0.20
:=W'uw
.~ 0.20
0.30

i - should be treated
systems,
treated as
systems, classical
as coherent
classical ray
eration rate must be
Light trapping
coherent and
ray tracing
and interference
interference becomes
tracing approaches
approaches are
be found from the gradient of
trapping involves
involves the scattering
scattering and
becomes important. In such
are not
not valid,
of the Poynting
and reflection
such
valid, and the photogen-
photogen-
Poynting vector.
vector.
reflection of light rays within
I
.,-
the cell
the cell so
so that
that they
they travel
travel atat wider
wider angles
angles toto the
the surface
surfacenormal.
normaL. TheThe
problem can be considered in terms of the paths taken by by light
light rays
rays inside
0.10
/ are defined
considered in
the cell. An admitted rayray may
may travel
defined by the cell geometry.
travel in
geometry. At
in one
At some
one of a number of paths,
some point
inside
paths, Pi, which
point within the cell volume,
which
volume, the
0.00 total flux
flux is given
given the sum
sum ofof the
the contributions
contributions alongalong the different
different paths.
0.00 0.50 1.00 1 .50
1.00 1.50 2.00 2.50 The relevant quantity for photogeneration is is the light absorption rate, fromfrom
Gap/eV
Band Gap I eV Eq.9.7,
Fig. 9.10.
Fig. 9.10. Limiting
Limitingeffciency
efficiency versus
versus band gap
gap for
for an
an ideal
ideal solar
solar cell
cell in
in AM
AM 1.5
1.5 with
with
uph(E, r)
uph(E, o:(E,r)
r) == a(E, r) L f3i(E,r,r'(h,
L (E, O, 4) (9.30)
X=lOOOandX=1.
X=1000andX=1.
Pi
PI

where the integral

integral over
over solid angle
angle is converted to a sum over the paths, and
f3i represents the
i represents thephoton
photon flux
flux at from the
at rr from the direction (Oi, <Pi).
direction (Oi, ). Equation 9.30 9.30
provides the
provides the photogeneration
photogeneration raterate at at rr and should replace
and should replace Eq. Eq. 9.2
9.2 in in the
the
calculation of photogeneration. However, because of
However, because of the
the different
different history
history of
the rays it is diffcult
difficult to
to determine
determine the the
f3i at
at aa general
general point,
point, andand ititisis easier
easier
to find the total
total absorbed
absorbed flux
flux by
by considering absorption along
considering absorption along the length
each ray
of each ray path, using
using an approach
approach known
known as 'ray 'ray tracing'.
tracing'.Thus,
Thus,
(a)
(a) (b)
(b)
Fig.
Fig. 9.11.
lens
(a)Contact
9.11. (a) Contactgrid
lens refracts light on to
gridfor
to cell
forconcentrator
concentrator cell
cell surface
surface away
cell with
with circular
away from contacts.
circular symmetry;
symmetry; (b) Prismatic
Prismatic
fabs==(1bs(E)
Jabs
-bs(E)
R(E)) { 1-
1.1 (r
(1 - R(E)) f (r
- R(E) )}
) 1. ~f3i(E,O)exp
R(E) -- r(E, 0) exp -a(E)
-o:(E)jPt
jPI dli f (9.31)
(9.31)

9.6. Light Confinement

9.6. Light Confinement
where lil is
where is a length co-ordinate along the
co-ordinate along the path p,Pi, and
and the
the integration
integrationisis
taken over
taken over thethe ray
ray path, from entry to exit. (E,O)
from entry f3i(E,O) is the flux
flux of the ith
ith
9.6.1. Light paths
9.6.1. Light paths and
and ray
ray tracing
tracing ray at the
ray at the start
start of
of its
its path
path inside
inside the
the cell
cell- - effectively
effectively aa weighting factor
weighting factor
for the
for the path
path -- andandsatisfies
satisfies
In contrast to
to anti-reflection
anti-reflection coats,
coats, which
which increase
increase the fraction of photons
admitted toto the
the cell,
cell, and
and concentration
concentration which
which increases
increases the
the iIi.cident
incident flux, Lf3i(E,O) (1-
Li(E,O) == (1 R(E))bs(E).
- R(E))bs(E). (9.32)
light confinement techniques
light confinement techniques increase
increasethe
the path
path length
length of photons inside the Pi
cell,
cell, once
once admitted.
admitted. Increasing
Increasingthethe path length increases
path length increases the
the probability
probabilty
of
of photogeneration
photogeneration per per incident
incident photon,
photon, particularly
particularly when
when the absorption clarity, we
For clarity, we have
have assumed
assumed aa position
position independent
independent absorption coeffcient.
coefficient.
coefficient
coeffcient is small,
small, increasing
increasing the
the absorbed fraction
fraction.. Light trapping
trapping isis Ilor-
nor- Clearly
Clearly aa longer
longer rayray path
path will lead to
wil lead to aa higher
higher attenuation of the
attenuation of the ray
ray
mally considered
mally considered in in the regime geometrical optics where structures are
regime of geometrical optics where structures and a higher
and a higher Jabs. Different
fabs. Different light trappinglight
schemestrapping schemes can be evaluated by
evaluated by
274
274 Physics of
The Physics of Solar
Solar Cells
Cells Managing
Managing Light
Light 275
275

comparing the average

average path length
length

(l) = r(E,O) ldli/ ri(E,O) (9.33)

(9.33)

width of
with the width of the cell,
cell, w.
geometry and reflection
on geometry
probability of
contain the probability
Note that the
w. Note
reflection and
the path
and transmission
of photon
photon absorption.
absorption.
path length
length isis dependent
transmission probabilities,
dependent only
probabilties, and does
only
does not
not
Fig. 9.13.
wI

9.13. Ideal
Idealrandomising
randomising rearrear surface.
surface. Light
Light rays striking
striking the rear
-
rear surface
surface are
are re-
re-
flected
flected in a
a random direction. On
random direction. On the
the first two reflections,
reflections, thethe illustrated
ilustrated ray
rayisisreflected
reflected
at an
an angle
angle larger
larger than
thanOc.
(}c. On
On the
the third
thirdbounce,
bounce,ititisisreflected with0(}-c<Oc
reflectedwith (}c and
and escapes.
escapes.
9.6.2. Mirrors
9.6.2. Mirrors

The simplest
simplest light
light trapping
trapping scheme
scheme isis to introduce an
to introduce optical mirror
an optical mirror at they wil
willbe
beunable
unableto
toescape
escape from
from the
the cell
cell and be
be reflected
reflected back for
for another
rear surface
the rear surface of the cell,
cell, either by
by metallsing
metallising the
the rear
rear cell
cell surface
surface or
or pass within
double pass thecelL.
within the cell.
growing the
by growing the active
active layers
layers on
on top
top of aa Bragg stack. typically
stack. The mirror typically
reflects over 95%
95% ofof rays
rays striking the rear
striking the rear surface.
surface. Rays
Rays which subsequently
subsequently
9.6.3. Randomising
9.6.3. Randomisingsurfaces
surfaces
reach the front,
front, semiconductor-air,
semiconductor-air, surface are likely likely to pass through
through sincesince
the reflectivity of that interface
interface must be be small for efficient
effcient light capture. So So One approach is to use use aa roughened
roughened surface
surface which
which scatters, or or randomises,
randomises,
the rear mirror effectively doubles
mirror effectively doubles thethe path length of the light. For For an
an ideal
ideal the light
light upon
upon reflection,
reflection, changing
changing the
thevalue
value of
ofOs'
()s' Here we consider a ran- ran-
mirror (with R
mirror (with R = 1) and ideal
1) and ideal front surface (with RR =
surface (with length
0) the path length
= 0) domising rear
domising rear surface
surface although
although inin principle
principleeither
either the
the front
front or
or the
the rear sur-
is 2w. face, or
face, or both, cancan be randomising.
randomising. A A perfectly
perfectly randomising
randomising surface,
surface, called
called
Greater path
path length
length enhancements
enhancements can can bebe achieved
achieved by exploiting
exploiting total a Lambertian
Lambertian surface,
surface, scatters reflected rays with spherical
reflected rays spherical symmetry so so
internal reflection
reflection at surface. This is not possible
at the front surface. possible for a cell
cell with that all
all angles
angles in the
the hemisphere pointing into the
hemisphere pointing the cell
cell are
are equally
equally likely.
likely.
parallel surfaces since,
parallel planar surfaces since, by symmetry,
symmetry, reflected
reflected rays
rays must approach Assuming normal
Assuming normal incidence,
incidence, aa light ray
ray enters
enters and
and crosses the cell
crosses the cell and is
the front surface
surface at the
the same
same angle
angle at which
which they were were admitted, and and con-con- scattered at the rearrear surface.
surface. The mean path length
length forfor the reflected
reflected ray to
sequently
sequently encounter the same reflectivity,
reflectivity, which
which should
should bebe small.
small. For light cross back
cross back toto the front surface
surface is twice the cell
cell width:
trapping, rays should
should approach
approach thethe front
front surface
surface at at a wider
wider angle
angle than
than the w
(l)==(co:O
( 0 )) = (9.34)
angle at which they
at which they were
were admitted.
admitted. This can be achieved
achieved by by tilting
tilting the front (l) cos s = 2w.
2w.
s
or the rear surface,
surface, oror by
by scattering
scatteringthe the light
light within the cell. If
the celL. If light rays
rays
can ()s ;:>Oe
This doubling
This doubling of ofthe
the optical
opticaldepth
depth of ofthe
the cell
cell illustrates
ilustrates the advantage
advantage of
can be
be manipulated so so that
that they
theyapproach
approachthe thesurface
surfaceatatananangle
angleOs ()e
randomising the
randomising the light even
even before
before light confnement
confinement has has occurred.
occurred. Now,
Now,
since
since only
only those
those rays
rays with Os >
with Os Oe can
;: ()e can escape, only ~
escape, only -b
ns of
of the rays
the rays striking
striking
n.
the front
the surface will
front surface wil leave
leave the
the cell;
cell;the
the rest
rest will
wil be reflected to make
reflected to make aa
secondpass,
second pass,ofoflength
length2w,
2w,across
acrossthe thecell
celland
andbe bescattered
scatteredagain
againatat the
the rear
surface. Adding
surface. Addingup up the
the path
path lengths of the the rays
rays according
according to to the
the number of
times they are scattered before
times before leaving
leaving thethe cell
cell we
we find
find
wI
~1 1n;
~ (1) ~.) 1 n;
(1 -n; (~ 1(1n;
_)2
~)
(l)= = -x x2w2w+ + -x x 1 - - xx 6w
(l)
n~ n; n~ n~
6w ++ - xx 1 - - x lOw
n~ n~
2 X + . +....
. lOw
whereitit isis assumed
where assumedthatthat the
the path length
length is ww for
for the first
first pass
pass (normal
(normal
Fig.
Fig. 9.12. Double path
9.12. Double pathlength
length ininmetallsed
metallisedcelL.
cell.
incidence)and
incidence) and the
the final
final pass
pass (only small Os
(only small Oscan
can escape)
escape)butbut 2w
2w for
for all
276 The Physics of
The of Solar
Solar Cells
Cells Managing
Managing Light 277
277

passes. Summing
intermediate passes. Summing the series
series to infinite
infinite order, immediately be stated that

(l) =
(l) (4n: -- 2)w
= (4n; ~ 4n;w.
2)w ~ 4n:w. (9.35)
(9.35) (l) ~~ 2(1
(l) +sec 2B
2(1 + see tilt )w ~
20tiit)W 4w..
~ 4w (9.36)
This ideal
This ideal path
path length enhancement, 4n:,
length enhancement, is around 50 for silicon
4n;, is and GaAs,
silcon and GaAs, Although higher tilt angles
Although higher angles lead
lead to higher
higher path
path length
length enhancements
enhancements for
for
which shows
which showsthethepotential
potentialofof light
light trapping
trapping systems [Lush, 1991J.
systems Lush, 1991]. the shortest
shortest pass,
pass, shallower
shallower angles
angles allow longer textured
allow longer textured faces,
faces, and a higher
If the
If the rear
rear surface is imperfectly
surface is reflecting then
imperfectly reflecting then aa fraction
fraction of
of the
the light
light probabilty
probabilityofofmultiple
multiple passes.
passes.
is lost through
through the the rear
rear surface
surface at
at each
each scattering
scattering event,
event, and the
the mean
mean Texturing the front surface
surface in the same way leads to
way leads to similar
similar path length
path
path length
length isis reduced.
reduced. The
Theeffect
effect can
can be
be considerable
considerable because
because of the large
large enhancements. Normally incident rays striking
enhancements. Normally incident rays striking the the textured surface
surface are re-
re-
number of reflection
reflectionevents (aroundn:)
events(around n;) at that
that surface.
surface. fracted into the cell
cell at an
an angle
angle
Although useful for
Although useful for indicating
indicating the
the potential of light trapping
trapping systems,
systems,
perfectly randomising surfaces
surfaces are
are not easily realised.
realised. Practical techniques
techniques 'Y = .tilt
'Y = OII
-1
utilt -- (sin
sin
sm (sin
.
-Btilt)
-Otit)
-1
-
- (9.37)
ns
depend on
usually depend on the geometrical-optical properties of more regular, tex-
tured surfaces.
tured surfaces. which increases the path
path length
length from
from side
side to
to side
side of
of the
the celL. Ifthe
cell. If the texturing
texturing
is symmetrical, then most
symmetrical, then most of those
those rays
rays will
wil strike the front
front surface
surface again
again
on a face which
which has opposite tilt to
to the
the face
face of
of entry,
entry, and
and leave
leave the
the cell.
cell. So,
So,
9.6.4. Textured
9.6.4. Textured surfaces
surfaces at the
the minimum,
minimum, only
only aa double
double pass
pass isis available
available and
The simplest system isis where
simplest system where oneone surface
surface isis tilted
tilted relative
relative toto the other.
other.
(l) ~~ 2wsec'Y > 2w.
2wsec'Y ;: 2w.
(l) (9.38)
Consider a rear surface tilted
Consider a rear surface tilted at an angle Otit relative to
angle Btilt relative to the planar front
planar front
surface, as
surface, as in
in Fig.
Fig. 9.14. When BOtit
9.14. When tilt > !Bc, normally
;: lOe, incident rays
normally incident rays will
wil be However,
However, ififthe
the texturing
texturing isis asymmetrical,
asymmetrical, thenthen by choosing
choosing thethe tilt angles
angles
reflected from the
reflected from the rear
rear surface
surface atat an angle greater than Oe, Be, and
and be totally carefully, four
carefully, four passes
passes ofof the
the light
light can be achieved,
achieved, as shown in Fig.Fig. 9.15.
9.15.
reflected at
reflected at the front.
front. If a ray
ray strikes
strikes the same
same portion
portion ofof the rear
rear surface
surface As a general trend, the lower
general trend, lower the degree symmetry, the greater the
degree of symmetry,
on the second pass, itit will
second pass, wil be
be reflected
reflected at an an even
even wider angle, and
wider angle, and trapped degree of
degree of light
light trapping.
trapping. If the surface
surface isis textured in two
two directions,
directions, with
again. For uniform
again. cell width,
uniform cell width, both positive
positive and negative
negative tilt angles
angles must pyramids
pyramids rather than grooves,
than grooves, then rays are scattered in
in three dimensions
three dimensions
be present,
be present, so
so that
that trapped rays wil
trapped rays will eventually
eventually be be reflected
reflected at
at narrower
narrower rather than
than two
two andand light
light trapping
trapping isis improved.
improved. Calculation
Calculation of the mean mean
angles and
angles escape. If
and escape. If the
the positive and negative
positive and tilt angles
negative tilt angles are equal,
equal, then path length
path length for
for any texturing
texturing pattern is is complicated
complicated and requires the
and requires the av-
av-
each ray makes
each makes aa multiple
multiple of
of four
four passes
passes across
across the
the celL.
cell. The worst
worst case,
case, erage of
erage of ray
ray paths
paths over the different
over the different points
points of incidence
incidence by rayray tracing.
tracing.
four passes
four passes (a 'double bounce'), is ilustrated
illustratedininFig.
Fig.9.14.
9.14.The
Theoverall
overallmean
mean However,itit is
However, is easy
easy to to see
seethat
that for
for a surface textured with pyramids
surface textured pyramids the the
path length
length depends upon the size
size and
and tilt angles
angles ofofthe
the texture,
texture, but it can probabilty
probability ofof aa light
light ray
ray striking
striking the surface at the same same angle at which it
was admitted
was admitted-- the thecondition
condition forfor escape
escape -- isissmaller
smaller than
than for
for aa surface
surface

wI
wI
~.",,, wI
Fig.
Fig. 9.15. (a) AAsimple
9.15. (a) simplereflection
reflection in
in aa structure
structurewith
with symmetrical surface texture.
symmetrical surface texture. Notice
Notice
Fig. 9.14.
Fig. 9.14. Light
Light trapping
trapping structure
structure with
with aa tilted
tiltedrear
rearsurface,
surface, illustrating
illustrating aa 'double
'double how the
how the surface
surface texture
texture extends
extends the
the path length from front to rear of the cell.
from front cell. (b) A four
bounce' light path.
bounce' path. pass path in
pass in aa cell
cell with asymmetric
asymmetric surface texture.
278
278 The Physics of
The of Solar
Solar Cells
Cells Managing Light 279
279

45 be rough and
and therefore
therefore have
have aa lower
lower reflectivity
reflectivity than single
single crystal. Chem-
Chem-
ical etches have been used in polycrystallne silcon totocreate
ical etches have been used in polycrystalline silicon create'honeycomb'
'honeycomb'
N
N
E and other structures which enhance enhance lightlight trapping.
0E0 40 Textured rear surfacessurfaces can be prepared
prepared by by growing
growing the active active layers
layers of
~E
E the cell
cell on patterened substrates. These These can be be prepared
prepared by by etching;
etching; or by by
....:c epitaxial methods, and the the active
active layers
layers then grown epitaxially on on top. The
~ 35 pyramids (2 sides)
..
"- size features on
size of features on textured surfaces
surfaces are typically
typically in in the
the .m
J.Lm range,
range,which
which
~::::l
00 (random, regular)
(random, regular)
..5
..... is acceptable
acceptable for for silicon
silcon where cells are
where cells are atat least tens of of microns
microns thick, but
'5 problematic for for highly absorbing materials
highly absorbing materials like like GaAs.
GaAs. An An alternative is to
0..~ 30
0
' grow the
grow the active
active layers
layers over
over aa blazed grating [Heine, Heine, 1995J1995J which achieves
which achieves
t:
-e the light
the light scattering
scattering without increasing cell
without increasing cell width.
width.
....c:00 25
en
en
Approximately randomising front front surfaces
surfaces havehave been
beenprepared
prepared on on silicon
silcon
using
using random pyramidalpyramidal surface
surface texture
texture Green,
[Green, 1995J,
1995]' and alternatively
alternatively
with a thin
thin layer
layer of of porous
porous silicon on top of the active
silicon on active layers.
layers. The porousporous
20
1
1 2 5 10 20 50 100200
50 1000 silicon coating can
silicon coating can be produced
produced by by electrochemically
electrochemically etching etching the the silcon
silicon
surface. Nanometre sized
surface. Nanometre sizedcrystallites
crystalltes andand pores
pores in in the
the porous
porous silicon
silcon scatter
Cell thickness, microns
the light
the light toto achieve
achieve wider
wider angles
angles of of entry
entry [Stalmans, 1998J.
Stalmans, 1998J.

J seasasa afunction
9.16. Jsc
Fig. 9.16. functionofofcell
cellthickness,
thickness,for
fordifferent
different light
light trapping
trappingschemes.
schemes.(Swan-
(Swan- Reflective
Reflective rear rear surfaces
surfacesare areprepared
preparedby bymetallising
metallsing the rear of of the cell
cell
son, 1990.1
son, 1990. with aluminium
aluminium or or gold.
gold. Such
Such semiconductor-metal
semiconductor-metal interfaces interfaces have have reflec-
reflec-
tivities of
of over
over 95%. Reflectivity at that
95%. Reflectivity that surface
surface cancan be be improved
improved ifif aa thin
layer of
layer of dielectric
dielectric- - typically
typically Si02Si0 2 -- is isinserted
insertedbetween
betweensemiconductor
semiconductor
textured only
only with
with grooves.
grooves. For aa regular array of
regular array of pyramids,
pyramids, light
light confine-
confine- and metal. Rays incident at wide angles angles are are then reflected
reflected by by total
total internal
ment is better
better ifif the
the pyramids
pyramids are
are offset
offset from each other. Random arrays of reflection. For
reflection. For epitaxially grown crystals, crystals, an an alternative is to grow grow thethe ac-
ac-
pyramids, which
pyramids, which havehave a very low degree
degree of symmetry, trap light
of symmetry, light very
very well
well tive layers
layers onon top of a BraggBragg stack, whichwhich has very very high reflectivity
reflectivity over a
and are comparable
and are comparable with the ideal
with the ideal randomising
randomising surface.
surface. Inverted regular
regular band of of wavelengths.
wavelengths.
pyramids, as
pyramids, as used
used in in the PERL cellcell (Sec.
(Sec. 7.4)
7.4) perform
perform slightly
slightly better
better than Actual path
Actual length
length enhancements
enhancements of of over
over 10,10, rather
rather smaller
smaller thanthan the
1
upright because of
upright ones because of an increased probability
an increased probabilty of of the escaping
escaping light
light re-
re- maximum of '4n~,
maximum 4n~, have
have been
been achieved
achieved in in silicon
silcon cells
cells with roughened
roughened sur-
entering the cell.
cell. Figure 9.16
9.16 compares
compares thethe light trapping performance a
performance of faces and
faces and with
with pyramidal
pyramidal texturing.
texturing. Note
Note that this this isis considerably
considerably smaller
smaller
range of different surfaces. than the
the flux
flux enhancements available through concentration; concentration; unlike unlike concen-
concen-
trators,
trators, light
light trapping cells operate
trapping cells operate inin relatively
relatively low low injection
injection conditions.
conditions.

9.6.5. Practical schemes

We have
We have not
not discussed
discussed the the application of of resonant
resonant cavities
cavities andand photonic
9.6.5. Practical schemes
band gap
band gap to photovoltaics. These These areare useful
useful for for strong confinement
confinement of par-
Front surface texturing
Front surface texturing in monocrystallne
monocrystalline materials
materials may
may be be achieved
achieved by ticular wavelengths
ticular wavelengths or or bands
bands of of wavelengths,
wavelengths,and and maymay be be ofof interest for for
using a selective
selective etch
etch which
which acts
acts in
in preferred
preferred directions
directions to
to expose
expose particular
particular photovoltaic effects
photovoltaic effectswithwithnarrow
narrowband band light
light sources,
sources,but but are
are not expected
crystal planes.
planes. In silicon basic etch can be used on the (100)
silcon a basic (100) surface to to to be beneficial
beneficial for for broad band
band sources.
sources.
expose
expose the (111) crystal faces.
faces. The size
size of surface pyramids can be defined
defined
before etching by using a mask. "
before etching by using a mask. "
Surface texturing is less
Surface texturing is less important for polycrystallne materials. De-
for polycrystalline materials. De-
pending
pending onon the
the method
method of film deposition,
deposition, the surface
surface isis already
already likely
likely to
280 The Physics
The Physics of Solar Cells
Cells Managing
Managing Light 281

9.6.7. Effects of
9.6.7. Effects of light
light trapping
trapping on device physics
on device physics

Incorporating light trapping can be be compared

compared to increasing
increasing the cell
cell thick-
thick-
ness. To
ness. To see
see this,
this, compare
compare aa standard cell of width
width w
w without rear reflector
reflector
with a light trapping cell of width
cell of widthW W== XX and a mean
mean optical path length
length
of (l) =W
(l) = W X. TheThe extended
extended pathpath length
length compensates
compensates for the reduced
reduced cell
cell
thickness so
thickness so that,
that, to aa first
first approximation,
approximation, the fraction
fraction of
of light absorbed is
the same in either
either case.
case.
Now we can make the following
following observations.
observations.

(a)
(a) (b)
(b) . Bulk
Bulkrecombination
recombinationlosses
losses are reduced. The thickness of the the light
light trapping
trapping
cell is
cell is smaller
smaller compared
comparedtoto the the minority
minority carrier
carrierdiffusion
diffsion length, so a
length, so
Fig. 9.17.
Fig. 9.17. (a)
(a) Highly
Highlyconfning
confiningcell
cellstructure
structure with
withmirrored
mirroredsurface;
surface; (b)
(b) AA reflective
reflective
cavity containing
containing arrays
arrays of
of cells (the 'photovoltaic
'photovoltaic eye').
eye').
smaller fraction of thethe photogenerated carriers should be lost by minority
carrier recombination
recombination than than ininthe
thestandard
standardcelL.cell.
. Rear
Rear surface
surface recombination losses may
recombination losses may bebe increased.
increased. The
The point
point generation
generation
rate is made
made up up of contributions from from reflected
reflected and incident rays rays and
and is
is
more uniform
more uniform than
than for
for the
the standard
standard cell.
cell. This
This means
meansthat
that generation
generation will
wil
9.6.6. Lightconfining
9.6.6. Light confining structures:
structures: restricted
restricted acceptance
acceptance be significant near the rear surface,
be surface, andand the
the fraction of
of carriers
carriers available
available
areas and
areas and external cavities
cavities for recombination
for recombination therethere is
is higher.
higher. Very good quality
Very good quality rear surfaces
surfaces are
therefore needed, with low low recombination velocities as well
velocities as as very high
well as
The degree
The degree ofof light
light trapping
trapping can be be increased
increased if the the cell
cell is
is enclosed
enclosed in optical reflectivities.
reflectivities.
a reflective cavity with
reflective cavity with restricted
restricted aperture for for acceptance
acceptance of of light.
light. Two
Two . Bulk
Bulkresistivity
resistivitylosses
losses are
are reduced.
reduced. Because
Because the same same amount
amount of of genera-
genera-
examples
examples are are illustrated
ilustrated in in Fig.
Fig. 9.17.
9.17. In the first,first, the
the entire
entire surface
surface of the tion is occurring in a smaller
smaller volume,