CIS/CIGS Solar Cells

Mark-Daniel Gerngro, Julia Reverey

02/04/2008 12:00 - 12:45
A. 241
Mawi Seminar WS 07/08 Prof. Dr. H. Fll

Motivation

solution: solar cells, especially CIS/ CIGS solar cells

problem:
short running
resources
andclimate
raising power
demand
problem:
global oil
warming
and
change
http://world.honda.com/environment/2006report/05010000_12.jpg
http://www.smh.com.au/ffximage/2005/10/07/arctic_wideweb__430x308.jpg
http://blog.kir.com/archives/oil%20and%20gas%20well%20at%20sunset3.jpg
http://www.photon-magazine.com/news/news_2004-03%20ap%20sn%20Honda_big.jpg
http://www.elenatour.uz/photo/uzb/images/Uzbekistan.%20Desert%20Kizil%20Kum.%20Takir.jpg
http://cache.eb.com/eb/image?id=91641&rendTypeId=4

Contents

Introduction
Material Properties
Growth Methods for Thin Films
Development of CIGS Thin Film Solar Cells
Fabrication Technology
Conclusion & Prospect

Introduction
CIS = CuInSe2 (copper indium diselenide)
CIGS = CuInxGa1-xSe2 (copper indium gallium diselenide)
compound semiconductor ( I-III-VI)
heterojunction solar cells
high efficiency (19% in small area, 13% in large area modules)
very good stability in outdoor tests
applications:

solar power plants

power supply in aerospace
decentralized power supply
power supply for portable purposes

http://www.copper.org/innovations/2007/05/images/civilian_flex_panel.jpg
http://www.rgp.ufl.edu/publications/explore/v12n2/images/thin-film.jpg
http://www.baulinks.de/webplugin/2007/i/0732-wuerthsolar1.jpg
http://www.esa.int/images/ISS_2004_web400.jpg

Contents
Introduction
Material Properties
Phase diagram
Impurities & Defects

Growth Methods for Thin Films

Development of CIGS Thin Film Solar Cells
Fabrication Technology
Conclusion & Prospect

Material Properties I
crystal structure:
tetragonal chalcopyrite structure
derived from cubic zinc blende structure
tetrahedrally coordinated

direct gap semiconductor

band gap: 1.04eV 1.68eV
exceedingly high adsorptivity
adsorption length: >1m
minority-carrier lifetime: several ns
electron diffusion length: few m
electron mobility: 1000 cm2 V -1 s-1 (single crystal)
ShiyouHamakawa,
Chen and X.
Yoshihiro:
G. Gong:Thin
Physical
Film Solar
Review
Cells,
B 75,
Springer,
2052092004.
2007

Material Properties II

simplified version of the ternary phase diagram

reduced to pseudo-binary phase diagram along the red dashed line
bold black line: photovoltaic-quality material
4 relevant phases: -, -, -phase and Cu2Se

Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Material Properties III

-phase (CuInSe2):
range @RT: 24-24.5 at%
optimal range for efficient thin film solar cells: 22-24 at %
possible at growth temp.: 500-550C, @RT: phase separation into +

-phase (CuIn3Se5)
built by ordered arrays of defect pairs
( VCu, InCu anti sites)

-phase (high-temperature phase)

built by disordering Cu & In sub-lattice

Cu2Se
built from chalcopyrite structure by
Cu interstitials Cui & CuIn anti sites
Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Impurities & Defects I

problem: a-phase highly narrowed @RT
solution: widening -phase region by impurities
partial replacement of In with Ga
20-30% of In replaced
Ga/(Ga+In) 0.3

band gap adjustment

incorporation of Na
0.1 at % Na by precursors

better film morphology

passivation of grain-boundaries
higher p-type conductivity
reduced defect concentration

Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Impurities & Defects II

doping of CIGS with native defects:
p-type:
Cu-poor material, annealed under high Se vapor pressure
dominant acceptor: VCu
problem: VSe compensating donor

n-type:
Cu-rich material, Se deficiency
dominant donor: VSe

electrical tolerance to large-off stoichiometries

nonstoichiometry accommodated in secondary phase
off-stoichiometry related defects electronically inactive

Impurities & Defects III

electrically neutral nature of structural defects
Efdefect complexes < Efsingle defect
formation of defect complexes out of certain defects
VCu, InCu, CuIn, InCu and 2Cui, InCu
no energy levels within the band gap

grain-boundaries electronically nearly inactive

Contents
Introduction
Material Properties
Growth Methods for Thin Films
Coevaporation process
Sequential process
Roll to roll deposition

Development of CIGS Thin Film Solar Cells

Fabrication Technology
Conclusion & Prospect

Growth Methods for Thin Films I

coevaporation process:
evaporation of Cu, In, Ga and Se from elemental sources
precise control of evaporation rate by EIES & AAS or mass spectrometer
required substrate temperature between 300-550C
inverted three stage process:
evaporation of In, Ga, Se
deposition of (In,Ga)2Se3
on substrate @ 300C
evaporation of Cu and Se
deposition at elevated T
evaporation of In, Ga, Se
smoother film morphology
highest efficiency
Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Growth Methods for Thin Films II

sequential process:
annealing
of from
stacked
elemental layers
selenization
vapor:
substrate: soda lime glass coated with Mo
deposition of Cu and In, Ga layers
bysputtering
sputtering
films by
deposition
Se layer
by atmosphere
evaporation
selenizationofunder
H2Se
rapid
thermal
process
thermal
process
for conversion into CIGS
advantage: large-area deposition
avoidance
of toxic
H2(H
Se 2Se)
disadvantage:
use of toxic
gases

Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Growth Methods for Thin Films III

roll to roll deposition:
substrate: polyimide/ stainless steel foil coated with Mo
ion beam supported low temperature deposition of Cu, In, Ga & Se

Mo

Cu,Ga,In,Se

CdS

ZnO

advantages: low cost production method

flexible modules and high power per weight ratio
disadvantages: lower efficiency

http://www.solarion.net/images/uebersicht_technologie.jpg

Contents
Introduction
Material Properties
Growth Methods for Thin Films
Development of CIGS Thin Film Solar Cells

Cross section of a CIGS thin film

Buffer layer
Window layer
Band-gap structure

Fabrication Technology
Conclusion & Prospect

Development of CIGS Solar Cells I

Zn0 front contact 0.5m

CdS buffer 50nm
CIGS absorber 1.6 m

Mo back contact 1m
soda lime glass
substrate 2mm

www.kolloquium-erneuerbare-energien.uni-stuttgart.de/downloads/Kolloq_2006/Dimmler_EEKolloq-290606.pdf

Development of CIGS Solar Cells II

Buffer layer: CdS
deposited by chemical bath deposition (CBD)
layer thickness: 50 nm

properties:
band gap: 2.5 eV
high specific resistance
n-type conductivity
diffusion of Cd 2+ into the CIGS-absorber (20nm)
formation of CdCu- donors, decrease of recombination at CdS/CIGS
interface

function:
misfit reduction between CIGS and ZnO layer
protection of CIGS layer
Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Development of CIGS Solar Cells III

Window layer: ZnO
band gap: 3.3 eV
bilayer high- / low-resistivity ZnO deposited by RF-sputtering / atomic
layer deposition (ALD)
resistivity depending on deposition rate (RF-sputtering)/flow rate (ALD)
high-resistivity layer:
- layer thickness 0.5m
- intrinsic conductivity
low-resistivity layer:
- highly doped with Al (1020 cm-3)
- n-type conductivity

function:
transparent front contact
R.Menner, M.Powalla: Transparente ZnO:Al2O3 Kontaktschichten fr CIGS Dnnschichtsolarzellen

Development of CIGS Solar Cells IV

band gap structure:
i-ZnO inside space-charge region
discontinuities in conduction band structure
i-ZnO/CdS: 0.4eV
CdS/CIGS: - 0.4eV 0.3eV
depends on concentration of Ga
positive space-charge at CdS/CIGS
huge band discontinuities of
valance-band edge
electrons overcome heterojunction
exclusively

heterojunction: n+ip
Meyer, Thorsten: Relaxationsphnomene im elektrischen Transport von Cu(In,Ga)Se2, 1999.

Contents
Introduction
Material Properties
Growth Methods for Thin Films
Development of CIGS Thin Film Solar Cells
Fabrication Technology
Cell processing
Module processing

Conclusion & Prospect

Fabrication Technology I
cell processing:
monolithical
integration:
of
buffer
layer grid
deposition
Ni/Al
substrate wash
#1collector

during cell #2
processing
patterning
deposition
of
antireflection
coating
metal base electrode
fabricationof
of complete modules
deposition
patterning #1n-type window layer
patterning#3
formation of p-type CIGS absorber

substrate
Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Fabrication Technology II
module processing:
packaging technology nearly identical to crystalline-Si solar cells
tempered glass as cover glass

ethylene vinyl acetate (EVA) as pottant

soda-lime glass as substrate

Al frame
junction box with leads

CIGS-based circuit
Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Contents
Introduction
Material Properties
Growth Methods for Thin Films
Development of CIGS Thin Film Solar Cells
Fabrication Technology
Conclusion & Prospect

Conclusion & Prospects

prospects:

conclusion:

increasing utilization (solar parks, aerospace etc.)

optimization of fabrication processes
gain in efficiency for large area solar cells
possible short run of indium and gallium resources

high reliability
high efficiency (19% in small area, 13% in large area modules)
less consumption of materials and energy
monolithical integration
high level of automation

http://img.stern.de/_content/56/28/562815/solar1_500.jpg
www.kolloquium-erneuerbare-energien.uni-stuttgart.de/downloads/Kolloq_2006/Dimmler_EEKolloq-290606.pdf

Thank you for your attention!

sources:
Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.
Meyer, Thorsten: Relaxationsphnomene im elektrischen Transport von
Cu(In,Ga)Se2, 1999.
Dimmler, Bernhard: CIS-Dnnschicht-Solarzellen Vortrag, 2006.