|1

Plastic solar cells

M. A. Loi
Zernike Institute for Advanced Materials
University of Groningen,
The Netherlands
e-mail M.A.Loi@rug.nl
Overview
|2

1st hour
Solar cells in general
 Solar Radiation
 p-n junction
 The organic version

2nd hour
 Improving plastic solar cells
 Low band-gap polymers
 Charge transfer states is detrimental?
 Solar Cells I
|3

› Long duration power supply

• Satellites
• Space vehicles
• Remote locations on earth

› Valid alternative to fossil fuels

› Pollution free
 Solar Cells II
|4

› Photovoltaic effect
• Becquerel (1839)
• Fritts {Selenium} (1883)
• Ohl {semiconductor junction solar cell}(1946)
• Chapin, Fuller, Person {Silicon p-n junction solar
cells} (1954)
 Motivations
|5

› ENERGY Increasing energy need

Exhaustion of fossil fuels
Diversification of energy sources
Energy for all (2 billion people without electricity)

› ECOLOGY Pollution of environment

CO2 Responsible Climate change

› ECONOMY Energetically independent

 Solar Radiation
|6

› Every second in the sun

6 x 1011 kg H2 → He + 4 x 1020 J ☼

› At the average distance of the earth the solar radiation is

1353 W/m2

› The atmosphere attenuates the solar radiation

• Absorption water - IR
Air Mass
• Absorption Ozone – UV
• Scattering
 Air Mass
|7

› Air mass = the path length of the light from a celestial

source relative to that at the zenith at sea level.
› increases as the angle between the source and the zenith
increases (AM38 at the horizon).

AM= sec q q = zenith angle

› Out of the atmosphere AM0
› On earth surface with sun at the zenith AM1
› Average for terrestrial applications - 45˚ from the zenith
AM1.5
Solar spectrum
|8
|9
Solar cells – inorganic case
| 10

› Single bandgap material

• Photons with hn<Eg lost energy

• Photons with hn=Eg used energy
• Photons with hn>Eg (hn-Eg) lost energy

Illuminated p-n junction

P-n junction solar cells
| 11
 Ideal solar cell
| 12

IL current produced by solar radiation

Is diode saturation current
RL load resistance Shockley diode equation

I = I s (e qV / kT
 1)  I L
 1 Dp 1 D  Eg / kT
I s = AqNC NV   n 
e
A device area  ND  p N A  n 
 
 IV characteristics
| 13

I sc = I L Short circuit current

Voc Open circuit voltage

0 = I s (eqVoc / kT  1)  I L
kT  I L  kT  I L 
Voc = ln   1   
q  Is  q  Is 
Ideal solar cell
| 14

P = IV = I sV (eqV / kT  1)  I LV

Pm = I mVm

Pm
=
Pi
 IV characteristics-realistic
| 15

Series resistance
Junction,
impurity
concentration

Shunt resistance – leakage current

I =  I L  I D  I SH
  q(V  IRS )   V  IRS
I =  I L  I s exp    1 
  kT   RSH
 IV characteristics-realistic
| 16

Rs in Si solar cells 0.7-0.4 W

The effect RSH is negligible

I = IL  ID
  q(V  IRS )   V  IRS
I =  I L  I s exp    1 
  kT  RSH
Conversion efficiency
| 17

I mVm
Fill factor FF =
I LVoc

Conversion efficiency
I mVm FF  I LVoc
= =
Pin Pin
› FF; IL; Voc should be maximized for efficient solar cells!

EQE or IQE, quantum efficiency-percentage of photon

converted in carriers (ISC)
Ideal efficiencies
| 18
Real efficiency
| 19
Plastic Solar cells
| 20

2000

2008
Pro & con
| 21

Advantages

› tailoring of opto-electronic properties

› large areas
› low temperatures (RT)
› processing from solution
› roll to roll manufacturing
› light weight
Power paint?
› transparent
› low cost…….maybe…
Pro & con
| 22

Problems

› low ambient stability

› strongly bound excitons (Frenkel like)
› Exciton diffusion length rather short 5-20 nm.
› low mobility of charge carriers
• μn (c-Si) > 1000 cm2/Vs
• μh (polymer) ≈ 0.1 cm2/Vs
› difficult to obtain low band-gap materials
Nevertheless
| 23

http://www.konarka.com

Disposable low-end applications!

 To start - photoexcitations
| 24

Frenkel exciton Charge Transfer exciton

Stronghly bound (0.4 eV in PPV); radius  5 Å

+
-
+ -

Polarons
Molecular semiconductors
• coulomb interaction
+
• elettron-phonon coupling
-
 Intermolecular excitons
| 25
Frenkel excitons
non radiative
states

Non radiative-emission
Triplet excitons
Fluorescence

Phosphorescence

Ground state
 The first examples
| 26

› Early works inspired by nature (photosynthesis)

› Porphyrins, phthalocyanines, perylenes (xerography),
merocyanines
› Organic heterojunction devices: p-type / n-type
organic semiconductors
› – 1970’s until 1995: organic heterojunction bilayers
› – 1985 Tang cell: PTCBI (45 nm) and CuPc (25 nm)
› 1% efficiency
 The Kodak approach
| 27

Tang et al., APL 2005

 The polymer approach!
| 28

› Active layer:
bulk heterojunction - hole conducting material
- electron conducting material

› Operation principle:

• Exciton photoexcitation
• Diffusion of the excitons towards the organic-organic interface
• Charge separation/electron transfer
• Transport of charge carriers towards the electrodes
 Photoinduced Charge Generation
| 29

An ultra-fast e- transfer occurs between Conjugated Polymer / Fullerene

composites upon illumination. The transition time is less than 40 fs.
Back transfer very slow! ms - ms

DONOR ACCEPTOR
exciton

O n

MDMO PPV PCBM

3,7 - dimethyloctyloxy methyloxy
1-(3-methoxycarbonyl) propyl-1-
PPV
phenyl [6,6]C61
N. S. Sariciftci et al., Science 258, 1474 (1992)
The driving force!
| 30

› Electron affinity fullerene derivatives!

-3.5 eV
OMe

O
-4.2 eV

-5.2 eV
-6 eV
PCBM
Polymer
Bulk Heterojunctions
| 31

e-
Al Electrode
Al Electrode
e- e- e-
P+
e-
e-
e-
e-
P+
ITO on Glass / Plastic

PCBM hn MDMO-PPV
 P-Solar Cells - FILM PREPARATION
| 32

Spin Casting is a easy coating

technique for small areas.
Material loss is very high. Doctor Blade Technique
was developed for large
area coating

Doctor Blade
has no material loss
Production - Large Area
| 33

Large Area Thin Film Production using Doctor/Wire Blading

1 2

a)

b)
Plastic Solar Cells - CONTACTING
| 34

The cathode electrode is

applied by evaporation.
Different electrodes are used
for different applications.

Sealing is absolutely necessary for an

increased life time of plastic solar cells.
Characterization under A.M. 1.5
| 35
Bulk Heterojunctions
| 36

e-
Al Electrode
Al Electrode
e- e- e-
P+
e-
e-
e-
e-
P+
ITO on Glass / Plastic

PCBM hn MDMO-PPV
The morphology issue…
| 37

< 1% 2,5%

S. E. Shaheen, Appl. Phys. Lett., 78, 841–843 (2001)

 Now..
| 38

Organic solar cells performances depend on the material

properties and microscopic structure of the bulk heterojunction!

P3HT

4,5-5.0 %

> 60 polymers checked last 5 years!

Optimization
| 39

eff = Isc * Voc * FF / Iinc

Isc Tuning of the Transport Properties - Mobility

Voc Tuning of the Electronic Levels of the Donor Acceptor

Systems

FF Tuning of the Contacts and Morphology

Iinc Tuning of the Spectral Absorbance/Absorbing more

light (low bandgap)
The future?
| 40
 | 41

Intermezzo!
Organic Solar cells
| 42

bulk heterojunction
3D heterostructure

hole conducting material

bulk heterojunction
+
electron conducting material

PCBM
(acceptor)
Polymer
(donor)
Power conversion efficiency ~ 5 - 6%
 Remember-Organic Solar Cells
| 43

› Working mechanism-steps
• Excitons photoexcitation
• Diffusion of the excitons towards the interface
• Charge separation/electron transfer
• Transport of charge carriers towards the electrodes

› Organic solar cells performances depend on

• the material properties
• the microscopic structure of the bulk hetero-junction
The driving force!
| 44

› Donor and acceptor LUMO energy offset!

-3.5 eV
OMe

O
-4.2 eV

-5.2 eV
-6 eV
PCBM
Polymer

Ultrafast phenomena!
Enhancing devices efficiency
| 45

› Optimize the materials properties

• Matching solar spectrum! NIR materials
• Relative position of the energy levels of the donor and acceptor

 optimal offset between LUMO (D) – LUMO(A)

for electron transfer at least 0.3 – 0.5 eV
 P3HT:PCBM: LUMO (D) – LUMO(A) ~1.1 eV

› Optimize the morpholog

• microscopic phase separation
( exciton diffusion length ~ 5 – 7 nm )
• presence of a percolation pathway
 Remember-Solar cells parameters
| 46

› JSC – short-circuit current

› Jph – photocurrent
Vmax  J max
› FF – fill factor: FF =
VOC  J SC

› VOC – open circuit voltage

LUMO (D)
3
LUMO (A)
Donor
Energy (eV)

4 Voc ›   power conversion

Acceptor

5 HOMO (D) efficiency

Pout Pmax VOC  J SC
= = = FF 
6 Pin Plight Plight
 The reduction of the LUMO offset
| 47

Power conversion
P3HT:PCBM efficiency ~ 4.5 % !!!
bisPCBM
3
Donor

4 • LUMO offset ~ 1.0 eV

Energy(eV)

Voc
• Voc~ 0.73 V
Acceptor

5
• power conversion efficiency ~ 3.8 %
• LUMO offset ~ 1.1 eV
6 • Voc~ 0.59 V

M. Lenes et al, Adv. Mater. 2008, 20, 2116

 PL of thermally annealed films
| 48

The devices performance:

P3HT:PCBM – 3%
P3HT:bisPCBM – 3.6%

P3HT:bisPCBM – PL ≈ 60 ps
P3HT:PCBM – PL ≈ 41 ps
 electron transfer is more
efficient for P3HT:PCBM
 PL of solvent annealed films
| 49

The devices performance:

P3HT:PCBM – 3.8%
P3HT:bisPCBM – 4.6%

P3HT:bisPCBM – PL ≈ 38 ps
P3HT:PCBM – PL ≈ 31 ps
 electron transfer is more
efficient for P3HT:PCBM
AFM measurements
| 50

P3HT:PCBM P3HT:bisPCBM

• surfaces is smoother for

samples prepared by
thermal annealing
3.9 nm spin coated 4.6 nm • difference in RMS
roughness between
P3HT:PCBM and
P3HT:bisPCBM

10.7 nm slow dried 12.4 nm 10x10mm

The blend in solution
| 51

P3HT:PCBM &
P3HT:bisPCBM

PL ≈ 156 ps

→ the efficiency of the electron

transfer is the same in both blends
 Conclusion 1
| 52

› Increasing power conversion efficiency by tailoring

the energy levels
• P3HT:bisPCBM – higher Voc
• P3HT:bisPCBM – higher power conversion efficiency
• P3HT:PCBM – faster PL decay in the thin film
• In solution – the same PL decay

› A small reduction of the LUMO offset does not have

a significant influence on the electron transfer

› The P3HT:bisPCBM blend is limited by diffusion -

the morphology can be still optimize
Remember-Photoexcitations
| 53

Frenkel exciton Charge Transfer exciton

Stronghly bound (0.4 eV in PPV); radius  5 Å

+
-
+ -

Polarons
Molecular semiconductors
• coulombic interaction
+
• elettron-phonon coupling
-
Intermediate state?
| 54

CT like intermediate states

are considered for
modelling IV of solar cells

V.D. Mihailetchi et al., PRL (2004)

Recent reports consider the

energy transfer from the polymer
to the PCBM as the first step of
the charge separation *

S OMe
N S
N N
O N
S
*
R *
R R R S
n

M. A. Loi et al.,
*
n
Adv. Funct. Mat. 17, 2111 (2007)
 Energy transfer?
| 55

OMe
*

S
O
2
N N 10

Photocurrent (mA/cm )
2
1
R *
10
R
n
0
10
F8BT PCBM -1
10

-2
10

-3
10

-4
10
-0,4 -0,2 0 0,2 0,4 0,6 0,8 1

Voltage (V)
Very poor PV performances!!
 Energy transfer? P
P
P
| 56 P
P
*
F8BT P
S
N N 0,5% PCBM
33%PCBM 66%PCBM
F8BT

Photoluminescence
R *

Photoluminescence
R
n 0,5% PCBM PCBM

F8BT 20% PCBM

OMe
33%PCBM
O

66%PCBM
PCBM
20% PCBM

PCBM
450 500 550 600 650 700 750 800 850

M. A. Loi et al.,
400 500 Wavelength
600 (nm)
700 800

Adv. Funct. Mat. 17, 2111 (2007) Wavelength (nm)

 Energy transfer?
| 57

F8BT @ 530 nm
66%PCBM @ 520nm
Photoluminescence

PCBM @ 720nm
66%PCBM @ 720nm The polymer PL
decay becomes very
fast upon PCBM
blending

Energy Transfer?

0 500 1000 1500 2000

Time (ps)
 | 58

Photoluminescence
PCBM-TR1 N
laser N
66%F8BT

No clear evidence! -10 0 10 20 30 40 50

Time (ps)
Long rise-time also in
pristine PCBM
Energy transfer to the PCBM singlet
state then transferred to the triplet state.
M. A. Loi et al.,
S. Cook et al., APL (2006)
Adv. Funct. Mat. 17, 2111 (2007)
 Electron transfer
| 59

N S OMe

*
S N
O ~4%
R R S
*
n 2
10
F8DTBT

Photocurrent (mA/cm )
2
PCBM
1
10

0
10

Polyfluorene copolymers -1
10

promising low-band gap -2

10

materials for PV applications -3

10

-4
10
M. Svensson et al., Adv. Mat. 15, 988 (2003); -0,4 -0,2 0 0,2 0,4 0,6 0,8 1
Q. Zhou et al., Appl. Phys. Lett. 84, 1653 (2004);
F. Zhang et al., Adv. Funct. Mater. 16, 667 (2006)
Voltage (V)
 | 60

N S
S N F8DTBT
*

Photoluminescence
R R S
*
n
F8DTBT

OMe

O
0.5% PCBM

10%PCBM
20% PCBM
66% PCBM
PCBM
550 600 650 700 750 800 850

Wavelegth (nm)
 Charge transfer excitons
| 61

PCBM 33%PCBM me4

66%PCBM
En = Eg  2 2 2
Photoluminescence

2  n
F8DTBT
Rydberg-like transitions
5% PCBM
ε(PCBM) ~ 3.9;
20% PCBM
ε(Polymer) ~ 2.5-3.0

Red-shift with the

increasing of the average
dielectric constant
550 600 650 700 750 800 850

Wavelegth (nm)
 | 62

PCBM
F8DTBT @ 630nm
66%PCBM @ 630nm
1 = 350ps; 2 = 1.0 ns
Photoluminescence

F8DTBT @ 730nm
66%PCBM @ 730nm
PCBM @ 820nm
66%PCBM @ 820nm
66%PCBM
1 = 320 ps; 2 = 3.1 ns

0 500 1000 1500 2000

M. A. Loi et al.,
Time (ps) Adv. Funct. Mat. 17, 2111 (2007)
 Ground state interaction?
| 63

Absorption Coefficient (10 cm )

N S 3.5

-1
S N PCBM
*
R R S F8DTBT
* 3.0 66%F8DTBT+33%PCBM

5
n 33%F8DTBT+66%PCBM

F8DTBT 2.5
66%F8DTBT+33%PCBM CALC
33%F8DTBT+66%PCBM CALC

2.0
OMe

O
1.5

1.0

PCBM 0.5

0.0
300 400 500 600 700 800

Wavelength (nm)
 | 64

Absorption Coefficient (10 cm )

3.5

-1
*
PCBM
S
N N F8BT
3.0 66%F8BT+33%PCBM

5
R * 33%F8BT+66%PCBM
R
n
66%F8BT+33%PCBM CALC
2.5 33%F8BT+66%PCBM CALC

F8BT
2.0

OMe

O 1.5

1.0

0.5

PCBM
0.0
300 350 400 450 500 550 600

Wavelength (nm)
Charge separation
| 65

There is an intermediate
state between the
Frenkel exciton and the
free charge!
Is it general?
| 66
Are more systems showing this phenomena?
Typical of narrow band gap polymers?

S
N N

*
S
* S n

PCPDTBT

FIRST narrow band-gap O-semiconductor

Solar cells efficiency: =3.2 %

D. Muehlbacher et al. Adv. Mater. 2006

Narrow band-gap polymer
| 67

PCPDTBT
blend PCBM 1:1
Concentration dependence
| 68

(10,1)
1/11 PCBM (2,1)
1/3 PCBM
(1,1)
1/2 PCBM
Charge Transfer
Exciton
(1,0)
0 PCBM
 Exciton CT Exciton
| 69

1/3 PCBM
 = 510ps
1/2 PCBM
 = 478ps
0 PCBM
 = 100ps

1/11 PCBM
1/2 PCBM 1 = 50ps
 = 5ps 0 PCBM 2 = 1190ps
 = 150ps

New excited state in the blend with long decay time!

(ns)
CTE detrimental for PV?
| 70

PCPDTBT/PCBM 1:1
 Conclusions II
| 71

Evidences of an excited state intermediate between the

exciton and the free carriers in heterojunctions containing
narrow band gap polymers – present also in working devices!

Additives can reduce the CTE component acting on the

microstructure of the blend.

The suppression of the intermediate states in bulk hetero-

junctions is extremely important for the optimization of
organic solar cells.  PCPDTBT/PCBM 3.8% →5.5%