The Open-Circuit Voltage

in Organic Solar Cells

Carsten Deibel, Andreas Baumann, Alexander Förtig,
Markus Mingebach, Daniel Rauh, Thomas Strobel,
Alexander Wagenpfahl, Vladimir Dyakonov
Julius-Maximilians-University of Würzburg, Germany

8th April 2010, MRS Spring Meeting in San Francisco

Outline
introduction
definition of Voc
generation
photocurrent
polaron pair dissociation

recombination
bulk recombination
surface recombination

open-circuit voltage
temperature dependence
carrier concentration

conclusions 2
 Definition
Open-Circuit Voltage

‣ current jn and jp usually non-zero!

derivatives usually non-zero

‣ continuity equations (here for holes with density p)

3
 Definition
Open-Circuit Voltage

‣ current jn and jp usually non-zero!

derivatives usually non-zero

‣ continuity equations (here for holes with density p)

‣ from electron and hole continuity with current derivatives:

for free charge carriers

3
 Definition
Open-Circuit Voltage

‣ current jn and jp usually non-zero!

derivatives usually non-zero

‣ continuity equations (here for holes with density p)

‣ from electron and hole continuity with current derivatives:

for free charge carriers

geminate dissociation & recombination nongeminate recombination3

 Models
Koster et al., APL 86, 123509 (2005)
Cheyns et al., PRB 77, 165332 (2008)

‣ Eg effective bandgap, determined by CT complexes

‣ Neff effective density of states
‣ n, p electron and hole concentration

4
 Models
Koster et al., APL 86, 123509 (2005)
Cheyns et al., PRB 77, 165332 (2008)

‣ Eg effective bandgap, determined by CT complexes

‣ Neff effective density of states
‣ n, p electron and hole concentration

High steady state carrier concentration means higher Voc

needed: high generation combined with low recombination
4
Outline
introduction
definition of Voc
generation
photocurrent
polaron pair dissociation

recombination
bulk recombination
surface recombination and S shape

open-circuit voltage
temperature dependence
carrier concentration

conclusions 5
 Generation: Photocurrent
Photocurrent = Current(illumination) - Current(dark)

POS =
0
voltage-independent
point of optimal symmetry
photocurrent density JPh [mA/cm!]

Ooi et al, J. Mater. Chem., 18, 1644 (2008)

offset

-2
photocurrent symmetric
with respect to POS
POS
-4 voltage independent
offset
-6

-8
-1.0 0.0 1.0

applied voltage [V]

6
 Generation: Photocurrent
Photocurrent = Current(illumination) - Current(dark)

POS =
0
voltage-independent
point of optimal symmetry
photocurrent density JPh [mA/cm!]

Ooi et al, J. Mater. Chem., 18, 1644 (2008)

offset

-2
photocurrent symmetric
with respect to POS
POS
-4 voltage independent
offset
-6

-8 open circuit voltage

-1.0 0.0 1.0 slightly above POS
applied voltage [V]

6
 Point of Optimal Symmetry
What is the origin of POS?
flat band in bulk?
0
voltage-independent
photocurrent density JPh [mA/cm!]

offset

-2

POS
-4

-6

-8
-1.0 0.0 1.0 built-in potential?
applied voltage [V]

7
 Point of Optimal Symmetry
What is the origin of POS?

0
voltage-independent
photocurrent density JPh [mA/cm!]

offset

-2

POS
-4

-6

-8
-1.0 0.0 1.0

applied voltage [V]

POS is
Quasi Flat Band in the bulk,
not built-in potential
Voltage-independent offset
(in part) due to finite field at
PRB 81, 085203 (2010)
electrodes 7
Generation: Photocurrent
Voc is close to quasi flatband case

finite field at electrodes

promotes polaron pair dissociation
free charge generation at Voc!

field in bulk almost zero at Voc

is there still free charge generation?

8
 Photocurrent Fit => Polaron Pair Dissociation
Photocurrent = Current(illumination) - Current(dark)

6 1
5
4
9
has two contributions
|JPh - JPh(VPOS)| [mA/cm ]

8
relative to POS!
2

7 Mihailetchi et al, PRL 93, 216601 (2004)

2

1
• charge extraction
Sokel-Hughes, JAP 53, 7414 (1982)
8 5
7
6
5
experiment
4
• polaron pair dissociation
Braun-Onsager, JCP 80, 4157 (1984)
4 Onsager-Braun
3 Sokel-Hughes
combination
2 3
0.01 0.1 1 10

|V - VPOS| [V]

PRB 81, 085203 (2010) 9

 Photocurrent Fit => Polaron Pair Dissociation
Photocurrent = Current(illumination) - Current(dark)

6 1
5
4
9
has two contributions
|JPh - JPh(VPOS)| [mA/cm ]

8
relative to POS!
2

7 Mihailetchi et al, PRL 93, 216601 (2004)

2

1
• charge extraction
Sokel-Hughes, JAP 53, 7414 (1982)
8 5
7
6
5
experiment
4
• polaron pair dissociation
Braun-Onsager, JCP 80, 4157 (1984)
4 Onsager-Braun
3 Sokel-Hughes
combination
2 3
0.01 0.1 1 10

|V - VPOS| [V]

PRB 81, 085203 (2010) 9

 Generation: Polaron Pair Dissociation
Kinetic Monte Carlo

‣ Hopping transport
E-Field

‣ Gaussian density of states

‣ Coulomb interaction
+
!

Donor

Acceptor
10
 Generation: Polaron Pair Dissociation
Kinetic Monte Carlo Experiment Simulation
1
‣ Hopping transport

Polaron Pair Dissociation Yield

6
5
E-Field 4
3
CL
2 ····· 1

0.1
6 !f
5 100ns
4
10µs
3

+ 2

fit to experiment
! 0.01
6 7 8 9
10 10 10 10
Electric Field [V/m]

Donor
‣ simulation does not reach
experimental yield at short circuit
Acceptor exp: PRB 81, 085203 (2010) 10
 Generation: Polaron Pair Dissociation
Kinetic Monte Carlo

‣ Hopping transport
E-Field

+
!

Donor

Acceptor
10
 Polaron Pair Dissociation: Extended Chains
Kinetic Monte Carlo

‣ Hopping transport
E-Field

+
!

Donor

Acceptor
11
 Polaron Pair Dissociation: Extended Chains
Kinetic Monte Carlo Experiment Simulation
1
‣ Hopping transport

Polaron Pair Dissociation Yield

6
5
E-Field 4
3
CL
2 ····· 1
–·– 4
– – 10
0.1
6 !f
5 100ns
4
3

+ 2

fit to experiment
! 0.01
6 7 8 9
10 10 10 10
Electric Field [V/m]
finite polaron pair dissociation
Donor at low fields
Acceptor
‣ considerable generation 11
 Generation: Polaron Pair Dissociation

PP diss simulated polaron pair

dissociation

P rec ‣ high yield similar to

experiment due to
bulk rec delocalisation along
polymer chains

‣ significant bulk generation

even at zero field

internal ‣ thus, also at Voc

‣ generation@oc ~4/5th of sc
‣ almost no loss in Voc
12
Outline
introduction
definition of Voc
generation
photocurrent
polaron pair dissociation

recombination
bulk recombination
surface recombination

open-circuit voltage
temperature dependence
carrier concentration

conclusions 13
 Bulk Recombination
P3HT:PCBM (annealed) measured by photo-CELIV

125 K

22
10
‣ Langevin recombination
prefactor
n [m ]
-3

21 300 K
10

P3HT:PCBM 1:0.8 ‣ temperature dependence

20
10
annealed typical for Langevin
recombination
-7 -6 -5 -4 -3 -2
10 10 10 10 10 10
tdelay [s]
Andreas Baumann APL 93, 163303 (2008) 14
 Bulk Recombination
P3HT:PCBM (annealed) measured by TPV@Voc

27 P3HT:PCBM
10 (annealed)
‣ recombination rate higher
recombination rate [m s ]
-3 -1

T [K]
200 at higher temperature
26
10 225 (proportional to the
250
275 charge carrier mobility)
300
25
10

‣ temperature dependence
24
10 typical for Langevin
recombination
2 4 6 8 2 4 6 8
21 22 23
10 10 10
-3
Alexander Förtig charge carrier density [m ] APL 95, 052104 (2009) 15
 Bulk Recombination
P3HT:PCBM (annealed) measured by photo-CELIV

Order of Decay Reduced Recombination Rate

3.4 -17
P3HT:PCBM 1:0.8 10
3.2
pristine
recombination order

3.0 annealed -18

10

kBR [m /s]
2.8

3
2.6 -19
10
2.4 P3HT:PCBM 1:0.8
annealed
-20 fit Langevin
2.2 10
125 K
BR 175 K
2.0
300 K
150 200 250 300 20 21 22
10 10 10
T [K] -3
n [m ]
Andreas Baumann PRB 80, 075203 (2009); Hilczer&Tachiya, JPCC (2010) 16
Bulk Recombination: Summary
Recombination of Free Charges
‣ bimolecular recombination
‣ Langevin type: depending on mobility
‣ reduced recombination rate
‣ order larger than two: due to trapping

Open Circuit Voltage

‣ at room temperature, bimolecular recombination is
significant
‣ limits Voc

17
Surface „Recombination“
Better: look at it as extraction rate!
Charge Extraction Pathways

Alexander Wagenpfahl 18
Surface „Recombination“
Better: look at it as extraction rate!
Simulated IV Curve Charge Extraction Pathways

Alexander Wagenpfahl 18
 Simulation

Reduced surface recombination

of holes at anode
Alexander Wagenpfahl 19
Energetic Structure at Voc

Charge carrier densities

20
Energetic Structure at Voc

21
Energetic Structure at Voc

22
Energetic Structure at Voc

At open circuit conditions:

Surface recombination:

22
Surface Recombination: Summary
S-shaped IV-characteristics
calculated by reduced surface recombination

Interpretation
surface „recombination“ is actually extraction rate
accumulation of surface space charge
‣ reduces Voc (and fill factor)
‣ transition from ohmic to space charge limited current

23
Outline
introduction
definition of Voc
generation
photocurrent
polaron pair dissociation

recombination
bulk recombination
surface recombination

open-circuit voltage
temperature dependence
carrier concentration

conclusions 24
 Voc(T) and n(T): annealed
ITO/PEDOT/blend/Ca/Al

Voc

0.7

0.6
Voc [V]

0.5 increasing PL

P3HT:PCBM 1:0.8
0.4 annealed

100 150 200 250 300

temperature [K]
 Voc(T) and n(T): annealed
ITO/PEDOT/blend/Ca/Al

Voc charge extraction

15
100x10
P3HT:PCBM 1:0.8
0.7 annealed
80
increasing PL
0.6
60

n [cm ]
Voc [V]

0.5 -3
increasing PL 40

P3HT:PCBM 1:0.8
0.4 annealed 20

100 150 200 250 300 100 150 200 250 300
temperature [K] temperature [K]
 Voc Models
Koster et al., APL 86, 123509 (2005)
Cheyns et al., PRB 77, 165332 (2008)

fit parameters:

‣ Eg effective bandgap, determined by CT complexes

‣ Neff effective density of states

measured
‣ n, p electron and hole concentration
26
 Voc: Modelling the experiment

annealed pristine

0.70 P3HT:PCBM 1:0.8 P3HT:PCBM 1:0.8

annealed as cast
0.75
0.65

0.70
0.60
Voc [V]

Voc [V]
0.55 0.65

0.50
0.60

0.45 measurement measurend

fit in linear Voc(T) range 0.55 fit in linear Voc(T) range
0.40
100 150 200 250 300 100 150 200 250 300

temperature [K] temperature [K]

• model fits well in linear Voc(T) range at T > 150 K

• from carrier concentration at T < 150 K, higher Voc is expected
Daniel Rauh
 Voc: Injection Barriers by Simulation

Voc charge extraction

1.0
1.1 24
Eg = 1.1 eV 10

Charge carrier densities [m ]

-3
Open circuit voltage [V]

0.8
1.1-(0.1+0.2)
23
10
0.6
Sim !n / !p Model
0.0 / 0.0 eV
0.1 / 0.2 eV
0.4 0.1 / 0.7 eV
22
10
electron !n / !p hole
0.0 / 0.0 eV
1.1-(0.1+0.7) 0.1 / 0.2 eV
0.2
0.1 / 0.7 eV
21
10
100 150 200 250 300 350 400 100 150 200 250 300 350 400

Temperature [K] Temperature [K]

Alexander Wagenpfahl
• ohmic contacts: Voc extrapolates to effective bandgap
• Voc is usually contact limited at low T
• model predictions due to carrier concentration yield ohmic case
 Voc: Light Intensity
Experiment Again!

0.7
Open Circuit Voltage [V]

0.6

0.5
‣ low light intensity:
monomol. recombination

0.4 100K
200K ‣ 1 sun: bimolecular
300K

0.3 P3HT:PCBM 1:0.8 MR ‣ 100K: contact limited

annealed BR
(as seen in Voc(T) plot)
0.001 0.01 0.1 1
Illumination Density [suns]
Daniel Rauh
 Voc: Light Intensity
Experiment Again!

0.7
Open Circuit Voltage [V]

0.6 ‣ 130mV

0.5
‣ low light intensity:
monomol. recombination

0.4 ‣ 1 sun: bimolecular

300K

0.3 P3HT:PCBM 1:0.8 ‣ 100K: contact limited

annealed
(as seen in Voc(T) plot)
0.001 0.01 0.1 1
Illumination Density [suns]
Daniel Rauh
Voc: Conclusions
high T
Voc determined by blend properties (CT complex energy)
bimolecular recombination is limiting Voc @ 1 sun
if only monomolecular: 130mV higher Voc @ RT

low T
generation rate lower
‣ recombination rate lower
‣ steady state carrier concentration higher
‣ Voc higher
for non-ohmic contacts usually contact limited
Conclusions

significant generation even at low fields

dissociation due to band bending at electrodes
delocalisation along effective conjugation length

recombination
bulk recombination limits at room T
S shape due to low extraction rates

open-circuit voltage
low T: usually contact limit
RT: bimolecular recombination

31
 Acknowledgments

BMBF GREKOS

deibel@physik.uni-wuerzburg.de
www.disorderedmatter.eu Bavarian Academy of Sciences and Humanities

EP VI

32
 Acknowledgments
Thanks to EP VI
Thank You

BMBF GREKOS

deibel@physik.uni-wuerzburg.de
www.disorderedmatter.eu Bavarian Academy of Sciences and Humanities

EP VI

32