Transport and Recombination in

Polymer:Fullerene Solar Cells

Paul Blom
Max Planck Institut fr Polymer Forschung, Mainz
Outline
1. Charge transport in Organic Semiconductors
-Hole Transport, Electron Transport

2. Photocurrent Generation in Organic Solar Cells
-Space Charge, Recombination

3. Recombination in organic solar cells
-Bimolecular Recombination, Trap-assisted`Recombination

4. Origin of the Recombination in Organic Solar Cells
-CT electroluminescence, ideality factor, Exciton Diffusion


< 2
Vbias (V)
0.1 1 10
10
-4
10
-3
10
-2
10
-1
10
0
0.13 m
0.3 m
0.7 m

J

(
A
/
m


2

)

J
V
L
=
9
8
2
3
c
APL 68, 3308 (1996)
Current-Voltage characteristic of a PPV Hole-Only Device
PPV
Au ITO
Hole Current is Space Charge (Bulk) Limited !!
Vs
cm
2
7
10 5

=
< 3
< 4
SCLC: PLED acts as a Capacitor
ITO Au
PPV
V=0
ITO
Au
PPV
V>
+
+ +
+
+
+
+
+
ITO
Au
PPV
+
+
+
+
+
+
+
+
V>>
+
+
+
+
+
+
+
+
J=charge velocity
CV V/L
Charge density and Electric field ~ V
10
19
10
20
10
21
10
22
10
23
10
24
10
25
10
26
10
-10
10
-9
10
-8
10
-7
FET

h
,

F
E
T

(
m
2
/
V
s
)
p (m
-3
)


LED
OC
1
C
10
-PPV
T=295 K
Mobility is Density Dependent !
Phys. Rev. Lett. 91, 216601 (2003)
< 5
0
Transport
level
Equilibrium
level
0
E
f
Low carrier density Higher carrier density
E
f
2
1
ln
T

T
1
ln
Effect of Carrier Density?
< 6
1 10 100
10
-7
10
-6
10
-5
10
-4
10
-3
10
-2
10
-1
10
0
10
1
T=298 K
T=272 K
T=252 K
T=233 K
V (V)
J

(
A
/
m
2
)


Theoretical model for (p,T,E) developed
Phys. Rev. Lett. 94, 206601 (2005)
< 7
Electron Transport in PPV
Low Electron Current, Steep J-V: Traps ?
Ca Ca
Holes
Electrons
0.34 um
0.22 um 0.37 um
0.3 um
APL 68, 3308 (1996)
< 8

10
-5
10
-4
10
-3
10
-2
10
-5
10
-4
10
-3
10
-2
10
-1
10
0
10
1
2 3 4 5 6 7 8 910 20 30
10
-5
10
-4
10
-3
295 K
275 K
255 K
235 K
215 K
195 K

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
A
/
m

)
(a)
(c)
NRS-PPV
L = 320 nm
MEH-PPV
L = 270 nm
295 K
273 K
251 K
230 K
211 K


C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
A
/
m

)
OC
1
C
10
-PPV
L = 300 nm
(b)
290 K
275 K
255 K
235 K
215 K

C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
A
/
m

)
V-V
bi
(V)
Gaussian LUMO and Gaussian Traps?
Trap-limited Electron currents in
PPV derivatives also described
by Gaussian trap distribution



N
t
~ 210
17
cm
-3

t
= 0.10 eV

E
t
~ 0.6-0.7 eV
Phys. Rev. B 83, 183301 (2011)
< 9
Slope vs LUMO position
2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2
0
1
2
3
4
5
6
7
8


S
l
o
p
e
LUMO (eV)
NRS-PPV
OC
1
C
10
-PPV
P3HT
F8BT
PF10TBT
PCPDTBT
PCBM
P(NDI2OD-T2)
PF1CVTP
PCNEPV
Trap-free
Explained by change of Gaussian Trap Depth!!!
< 10

-3.8
-3.6
-3.4
-3.2
-3.0
-2.8
-2.6
-2.4
-2.2
Trap

NRS-PPV
OC
1
C
10
-PPV
F8BT
PF10TBT
PCPDTBT
P3HT
LUMO
Electron Trapping in OLEDs:
One kind of trap responsible for trapping in all OLEDs!!!
N
t
~ 2-310
17
cm
-3

t
= 0.10 eV
Electron current can be predicted when LUMO is known
< 11
Nature Materials 11 , p.882 (2012)
Origin of Trap?
Photo-oxidation?


Water-polymer complexes?





Hydrated-oxygen complexes O
2
(H2O)
2
Trap-depth 0.1-0.2 eV
Potential Deep Trap
Peter Ho et al., Adv. Mat. 21, 4747 (2009)
C. Campbell, C. Risko, J. L. Brdas, Georgia Tech
< 12
Outline
1. Charge transport in Organic Semiconductors
-Hole Transport, Electron Transport

2. Photocurrent Generation in Organic Solar Cells
-Space Charge, Recombination

3. Recombination in organic solar cells
-Bimolecular Recombination, Trap-assisted`Recombination

4. Origin of the Recombination in Organic Solar Cells
-CT electroluminescence, ideality factor, Eciton Diffusion


< 13
Goodman and Rose: J. Appl. Phys. 42, 1971, 2823
E
n
e
r
g
y

x
L
E
C

E
V

Before light excitation
field: E=V/L
mean carrier drift lengths:
w
n
=
n
t
n
E
w
p
=
p
t
p
E
Assumptions:
uniform generation of e-h pairs throughout the volume of the active layer
non injection contacts for both electrons and holes
one dimensional case
diffusion ignored
Photocurrent in a semiconductor:
< 14
Built-in Voltage:
V=0
V=V
bi
LiF PEDOT
V
bi
LiF
V
bi
PEDOT
V=0
Goodman and Rose:
BHJ Solar Cell:
V
eff
=V-V
bi
< 15
main carrier drift length w
n
=
n
t
n
E and w
p
=
p
t
p
E <<L ,
E=V/L=constant.

+
_
hv
V=V
OC
-V
bias
L
J-V characteristic (Ohmic regime):

After light excitation
( )
L
V
eG J
p p n n
t t + =
J
V
V
Small applied voltage:
< 16

n
t
n
>
p
t
p ,
w
n
>> L, w
p
< L


Recombination (t)

Limited regime:

( )
2 / 1 2 / 1
2 / 1
; GV J V eG J
n n
= t
J
V
V
V
1/2

+
_
hv
L
1

V=V
OC
-bias
Intermediate voltage:
< 17
saturation regime:
w
n
> L, w
p
> L,

E=V/L=constant
equal electron and hole current.
J-V characteristic is:

eGL J =
+
_
hv
V=V
OC
-bias
L
J
V
V
V
1/2

Constant
High Voltage Regime:
< 18
SCL Photocurrent:

J
V
V
1/2

+
_
hv
L
1

V=V
OC
-bias
Space-Charge Limited Photocurrent:
2 / 1 4 / 3 2 / 1 4 / 3
4 / 1
;
8
9
V G J V G
q
q J
p

|
|
.
|

\
|
=
c
3
1
2
1
1
1
1
8
9
d
V
j j
h SCLC ph
c = s
Maximum electrostatically allowed current:

n
t
n
>
p
t
p ,

p
<<,

t
p
>>

< 19
LUMO PPV
LUMO PCBM
HOMO PPV
HOMO PCBM
Exciton
diffusion
Donor
Acceptor
Anode
ITO/PEDOT
5.2 ev

Cathode
LiF/Al
3.8 ev
Light
Electron transport
Hole transport
Charge transfer
CT-state
CT-state:
If r
0
=1 nm and c
r
=3, then
binding energy is 0.5 eV !!
Photocurrent in a Polymer:Fullerene Solar Cell
< 20
G. Yu, J. Gao, J. C. Hummelen, F.
Wudl, A. J. Heeger, Science 1995,
270, 1789.
Apply GR Model to BHJ Solar Cell:
HOMO
PPV
HOMO C
60

LUMO C
60

2.9 eV
3.7 eV
5.1 eV
6.1 eV
PEDOT:PSS

M
~5.2 eV
LUMO
PPV
LiF/Al

M
~3.0 eV
LUMO=LUMO
PCBM
HOMO=HOMO
PPV
Effective Medium:
< 21
0.01 0.1 1 10
1
10
J
p
h
=
J
L
-
J
D

[
A
/
m
2
]
V
0
-V [V]
drift diffusion
Photocurrent in PPV:PCBM (1:4 wt.%) solar cells
deviation at high (reverse) voltages due to field-dependence of G?
0.0 0.2 0.4 0.6 0.8 1.0
-30
-20
-10
0
10
20
V
OC
V
0
J
D
J
L
J
ph
=J
L
-J
D


J

[
A
/
m
2
]
V [V]
J o V
J=qGL
L=120 nm
T=295 K
< 22
Saturation Regime:
MDMO-PPV:PCBM
Saturated regime: photocurrent J=e G(E,T) L due to dissociation of
bound electron-hole pairs
Braun: J . Chem. Phys. 80, 1984, 4157
0.1 1 10
1
10
295 K
270 K
250 K
230 K
210 K


J
p
h

[
A
/
m
2
]
V
OC
-V [V]
Phys. Rev. Lett., 93, 216601 (2004)
60%
J
sc
At J
sc
only 60% of bound
e-h pairs is dissociated !!
eG
MAX
L
< 23
Solar Cell Device Model
Inclusion of (Langevin) recombination and G(E,T) requires numerical
modeling
10
-2
10
-1
10
0
10
1
10
0
10
1
data 295 K
data 250 K
q G(V) L 295 K
q G(V) L 250 K
simulation 295 K
simulation 250 K

J
l
i
g
h
t
-
J
d
a
r
k

[
A
/
m
2
]
Voc-V [V]
Phys. Rev. B 72, 085205 (2005)
MDMO-PPV:PCBM
< 24
3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8
10
-11
10
-10
10
-9
10
-8
10
-7
O
O
*
O
O
*
1
3
ran
O
O
*
O
O
*
1
3
ran
L
1
L
V
1
G
L
1
L
V
1
G

[
m
2
/
V
s
]

1000/T [K
-1
]


Electrons
Holes
At T=210 K factor 10
3
difference in e/h mobilities
Transport in a BEH-BMB PPV/ PCBM blend
1:4 wt. %
< 25
0.01 0.1 1 10
10
0
10
1
295 K
270 K
250 K
230 K
210 K


J
p
h
=
J
L
-
J
D

[
A
/
m
2
]
V
0
-V [V]
J
ph
o V
1/2
Light-intensity (G) dependence ?
Photocurrent in the BEH-BMB PPV/ PCBM blend
Observation of SCL photocurrent
0.01 0.1 1 10
0.1
1
10


J
p
h

[
A
/
m
2
]
V
0
-V [V]
L=275 nm
T=210 K
V
sat
10
1
10
10 100
1
2
3
4
J
ph
@ V
0
-V=10 V
S = 0.76
J
p
h

[
A
/
m
2
]
S = 0.95
J
ph
@ V
0
-V=0.1 V


S = 0.51


V
s
a
t

[
V
]
Incident Light Power [mW/cm
2
]
Light-intensity dependence:
80 mW/cm
2
6 mW/cm
2
At J
sc
losses due to bimolecular recombination weak (4%)

Phys. Rev. Lett. 94, 126602 (2005)
< 27
|
28
Low Bandgap Polymer PCPDTBT (Konarka)
V
oc
= 0.65 V
J
sc
= 90 A/m
2
(PC
61
BM)
= 110 A/m
2
(PC
71
BM)
FF 47%
PCE = 2.67 % (PC
61
BM)
= 3.16 % (PC
71
BM)
Mhlbacher et al, Adv. Mater., 18, 28842889 (2006)
Poly [2,6-(4,4-bis-(2-ethylhexyl)-4H-
cyclopenta[2,1-b;3,4-b]dithiophene)-alt-4,7-
(2,1,3-benzothiadiazole)]
(PCPDTBT)
??
< 28
PCPDTBT:PCBM Solar Cells
-0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
-60
-50
-40
-30
-20
-10
0
10


295
270
250
230
210
J
L
[
A
/
m
2
]
V [V]
Low Fill Factor (~40-45%) combined with
square root regime in photocurrent:
Space-Charge Limited???
0.1 1
10
100
T [K]
295
270
250
230
210


J
p
h
[
A
/
m
2
]
V
0
-V [V]
< 29
|
30
Single Carrier Devices
0.0 0.4 0.8 1.2 1.6 2.0
10
100
1000
10000


J

[
A
/
m
2
]
V-V
res
-V
bi
[V]

e
=7x10
-8
m
2
/Vs
0.0 0.7 1.4
1
10
100
1000


J

[
A
/
m
2
]
V-V
bi
-V
rs

h
=3x10
-8
m
2
/Vs
LUMO
HOMO
LUMO
HOMO

Hole/Electron mobility almost balanced: SC Limit Unlikely!!!
Polymer:Fullerene Blend
< 30
Intensity dependence of Photocurrent:
0.1 1 10
10
100


J
p
h

[
A
/
m
2
]
V
0
-V [V]
J
ph
V
1/2
J
ph
G

V
sat
= constant
V
sat

Fingerprint of recombination limited current!!!
Adv. Funct. Mater. 2009, 19, 11061111
< 31
|
32
Square Root Dependence; vs sc limited
Two different origins for a square root dependence of J
ph

Space Charge Limited:
e
>>
h

V qG J
h r ph

|
.
|

\
|
s
25 . 0
0
75 . 0
8
9
) ( c c
J
ph
V
1/2
J
ph
G
3/4
V
sat
G
1/2
V. D. Mihailetchi et al., Phys. Rev. Lett. 94, 126602 (2005)
A. M. Goodman and A. Rose, J. Appl. Phys. 42, 2823 (1971)
-limited: w
n,p
= tE < L ;
p
t
p
<
n
t
n
V qG J
h h ph
t s
0.1 1 10
10
100


J
p
h

[
A
/
m
2
]
V
0
-V [V]
J
ph
V
1/2
J
ph
G

V
sat
= constant
V
sat

L
1

L
V
1

G
< 32
Outline
1. Charge transport in Organic Semiconductors
-Hole Transport, Electron Transport

2. Photocurrent Generation in Organic Solar Cells
-Space Charge, Recombination

3. Recombination in organic solar cells
-Bimolecular Recombination, Trap-assisted`Recombination

4. Origin of the Recombination in Organic Solar Cells
-CT electroluminescence, ideality factor


< 33
< 34
Limited by Diffusion of Electrons and Holes towards each other

Critical Coulomb Radius: binding energy hole-electron = kT
q
2
/4tckT (20 nm) >> mean free path in PPV (1-3 nm)
20nm
1-3 nm
Bimolecular Langevin recombination
U. Albrecht and H. Bssler, Phys. Status Solidi B 191, 455 (1995)
P. Langevin, Ann. Chem. Phys. 28, 289 (1903)
Study Recombination at V
oc
!!

Measure V
oc
~ Light Intensity!!
Solar cell with bimolecular recombination:
( )
|
|
.
|

\
|

=
PG
N P
q
kT
q
E
V
c
gap
oc
2
1
ln

APL 86, 123509 (2005)
E. A. Schiff, Sol. Eng. Mater. Sol. Cells 2003, 78, 567.
How to characterize recombination?

< 35
Light intensity dependence of V
oc
Linear dependence of V
oc
on ln(I) with slope kT/q, n=1 !
1 2 3 4 5
0.65
0.70
0.75
0.80
0.85
0.90


V
o
c

[
V
]
Ln (intensity) [a.u.]
295 K
250 K
210 K
APL 86, 123509 (2005)
MDMO-PPV:PCBM
Only bimolecular Recombination!!!!!
< 36
All-polymer solar cells: Electron traps
Recombination
1. Langevin
2. Shockley-Read-Hall
-
+
-
+
- - -
+ + +
-
-
-
-
1
2
Parameters:
Nt, Tt, Cn, Cp
( ) ( ) ( ) | |
1 1 1 1
/ p p C n n C n p pn N C C R
p n t p n
SRH + + + =
) (
2
i
Langevin n np R =
) (
0
p n
r
q

c c
+ =
< 37
V
oc
light intensity dependence
10 100 1000
1.25
1.30
1.35
1.40
1.45
1.50

Light intensity (W/m
2
)


V
o
c

(
V
)
Only Langevin recombination included
S[kT/q]=1
At V
oc
only losses via Recombination!!!!!
MDMO-PPV:PCNEPV
< 38
All-polymer: SRH recombination effects on Voc
10 100 1000
1.25
1.30
1.35
1.40
1.45
1.50

Light intensity (W/m
2
)


V
o
c

(
V
) C
n,p
= 1.410
-18
m
3
s
-1


5.010
-17
m
3
s
-1

5.010
-20
m
3
s
-1


< 39
Photocurrent of MDMO-PPV:PCNEPV
-10 -8 -6 -4 -2 0 2
-50
-40
-30
-20
-10
0
10
20

Voltage (V)


J

(
A
/
m
2
)
J
D
J
L
G
max
= 9.410
27
m
-3
s
-1
K
f
= 6.710
2
s
-1

a = 0.62 nm
<
r
> = 2.6
N
t
= 9.6 10
22
m
-3

T
t
= 2500 K

C
n,p
= 1.810
-18
m
3
s
-1
Both Langevin and SRH recombination included
Adv. Funct. Mat. 17, 2167 (2007)
What does it mean?
< 40
Measure PLED as a solar cell:
MEH-PPV
C
n
=C
p
=110
-18
m
3
/s
kT/q
M.M. Mandoc et al. App. Phys. Lett. 91, 263505 (2007)
M.M. Mandoc et al. Adv. Funct. Mater. 17, 2167-2173 (2007)
< 41
Origin of SRH Capture Coefficient:
3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8
10
-21
10
-20
10
-19
10
-18

p
q

c
C = solar cell
C = - hole-only device


C
a
p
t
u
r
e

C
o
e
f
f
i
c
i
e
n
t
s

(
m
3
/
s
)
T
-1
(10
-3
K)
p N
q
p N C k
t p t p SRH

c
= =
N
t
=electron trap
Phys. Rev. Lett. 107, 256805 (2011)
< 42
Origin of SRH Capture Coefficient:
20nm
1-3 nm
p N k r
t S R H
=
) 0 (
p S R H
q
k
c
+ =
Trapping
Idem as Langevin with immobile electron!
< 43
< 44
V=0
Ca ITO
Vbi
V=Vbi
Ca
Vbi
ITO
V>Vbi
Ca
V
ITO
Diffusion Current V<Vbi
Drift Diffusion
Drift
Diffusion
Diffusion
dx
dp
eD E ep J =
) / exp( ~ nkT qV J
v=E
OLED Current-voltage characteristics:

Three regimes:
1. Leakage current



2. Diffusion regime



3. Drift regime



1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
10
-6
10
-5
10
-4
10
-3
10
-2
10
-1
10
0
10
1
10
2
10
3


J

[
A
/
m
2
]
V [V]
1.
2.
3.
V
bi
(

|
|
.
|

\
|
= 1 exp
0
kT
qV
J J
q
3
2
8
9
L
V
J c =
leakage
R
V
I =

Ideality Factor

< 45
Origin of Ideality Factor?



Ideality factor equals 2 in the case of trap-assisted
recombination in a classical p-n junction
(

|
.
|

\
|
= 1
2
exp
0
kT
qV
J J
C. T. Sah et al., Proc. IRE 45, 1228 (1957)
< 46
Super Yellow PPV LED

The ideality factor for a Super
Yellow LED was determined
to have a value of 2 at room
temperature.

This corresponds to SRH
recombination from trapping
sites:
(

|
.
|

\
|
= 1
2
exp
0
kT
qV
J J
1
ln

|
|
.
|

\
|
c
c
=
V
J
q
kT
q
< 47
White OLEDs: Emissive SRH recombination?

Trap-assisted recombination in conventional polymers
appears to be non-radiative.

In a white emitting polymer, red dyes in the blue backbone
function as emissive traps.
HOMO
LUMO
< 48
Langevin & SRH recombination!
-0.2 -0.1 0.0 0.1
1
2
3
4
Current
Light 550 nm Longpass Filter
Light Blue Dichroic Filter


(
k
T
/
q

c
l
n
J
/
c
V
)
-
1
V-V
bi
[V]
2.0 2.5 3.0 3.5
10
-13
10
-12
10
-11
10
-10
10
-9
10
-8
10
-7
10
-6
400 500 600 700
0
20
40
60
80
100


E
L

I
n
t
e
n
s
i
t
y

[
a
.
u
.
]
Wavelength [nm]
550 nm Longpass Filter
Blue Dichroic Filter


L
u
m
i
n
a
n
c
e

[
a
.
u
.
]
V [V]

Luminance of red dyes follows SRH recombination,
whereas the blue light follows Langevin recombination.
< 49
Outline
1. Charge transport in Organic Semiconductors
-Hole Transport, Electron Transport

2. Photocurrent Generation in Organic Solar Cells
-Space Charge, Recombination

3. Recombination in organic solar cells
-Bimolecular Recombination, Trap-assisted Recombination

4. Origin of the Recombination in Organic Solar Cells
-CT electroluminescence, ideality factor


< 50
Charge transport in BJH Solar Cell
0.1 1
10
0
10
1
10
2
10
3
10
4
T = 294 K
170 nm
90 nm
J

[
A
/
m
2
]
V-V
Rs
-V
bi
[V]
3
2
0
8
9
L
V
J
e r
c c =

e
=2.0x10
-7
m
2
/Vs
Adv. Funct. Mater. 2003, 13,
Electron transport in PCBM and Hole transport in Donor
Polymers are trap-free: No SRH recombination
expected
< 51
Slope=kT/q: Only Bimolecular Recombination




Other Polymer:fullerene solar cells:

< 52
CT state electroluminescence in OPV
Weak electroluminescence from the charge-transfer state
is observed in organic solar cells
Cathode
Anode
Acceptor
Donor
< 53
EL Ideality factor?


Ideality factor of 1 is
measured for the CT
electroluminescence

Emission originates from a
free-carrier bimolecular
recombination process!
< 54
V
oc
vs Light intensity
A contribution of trap-assisted recombination is observed for
P3HT:PCBM










Recombination is bimolecular for other solar cells
< 55
Nonradiative SRH recombination?
Can be exposed by looking at the voltage dependence of
the EL quantum efficiency
P3HT:PCBM
Competition
SRH and
Bimolecular!
< 56
P3HT:PCBM solar cells
P
t
< 210
15
cm
-3
? SRH small
Hole traps in P3HT?
< 57
P3HT:PCBM solar cells
In P3HT:PCBM solar cells the Langevin recombination
is strongly reduced ~10
3
(CELIV)

Pivrikas, Osterbacka, Juska et al., Phys. Rev. Lett. 94, 176806 (2005)
Two dimensional Langevin recombination in the
lamellar structure of RR-P3HT
Juska, Osterbacka et al., Appl. Phys. Lett. 95, 013303 (2009)
< 58
P3HT:PCBM solar cells
10
2
10
3
0.50
0.52
0.54
0.56
0.58
0.60
Reduced Langevin + SRH


V
o
c

[
V
]
Light Intensity [W/m
2
]
Langevin + SRH
kT/q
Advanced Energy Materials, accepted
< 59
Exciton Transport?

Photo-excitation
Langevin Recombination, Trap-assisted Recombination
Ca
ITO
< 61
Neat Polymer PL decay:
0 200 400 600 800
10
-1
10
0
exp.
calc.
MEH-PPV t=300ps


L
u
m
i
n
e
s
c
e
n
c
e

(
a
.
u
.
)
Time (ps)
Intrinsic Exciton Lifetime ~ 300 ps?
Exciton diffusion
Change Energetic disorder in PPV derivatives
Reduced energetic disorder enhances exciton diffusion!!
7
Polymer , meV D, cm
2
/s (300K), m
2
/Vs
NRS-
PPV
125 3 10
-4
1.5 10
-12

MEH-
PPV
105 1.1 10
-3
5 10
-11

BEH-
PPV
92 2 10
-3
2 10
-9

O
O
n

O


O
O
0.5
0.5
O
O
n

NRS-PPV
MEH-PPV
BEH-PPV
E
D
E
D
PHYSICAL REVIEW B 72, 045217 2005
< 63
Neat Polymer PL decay:
0 200 400 600 800
10
-1
10
0
exp.
calc.
NRS-PPV t=800ps


L
u
m
i
n
e
s
c
e
n
c
e

(
a
.
u
.
)
Time (ps)
0 200 400 600 800
10
-1
10
0
exp.
calc.
MEH-PPV t=300ps


L
u
m
i
n
e
s
c
e
n
c
e

(
a
.
u
.
)
Time (ps)
0 200 400 600 800
10
-2
10
-1
10
0


exp.
calc.
L
u
m
i
n
e
s
c
e
n
c
e

(
a
.
u
.
)
Time (ps)
BEH-PPV t=200ps
-Less disorder, shorter
PL decay
-Less disorder, mono-
exponential decay
D=310
-4
cm
2
/s

D=110
-3
cm
2
/s

D=210
-3
cm
2
/s

Exciton diffusion
Energetic disorder in PPV derivatives
Exciton diffusion length 5-7 nm is independent on the
amount of energetic disorder!!!!
8
0 20 40 60
0.0
0.2
0.4
0.6
0.8
1.0


NRS-PPV; L
D
=5 nm
Q
u
e
n
c
h
i
n
g

e
f
f
i
c
i
e
n
c
y
Polymer film thickness [nm]
MEH-PPV; L
D
=6.3 nm
BEH-PPV; L
D
=6 nm
const L
D L
D
D
D
~
=
+ | +
t
t o and
- quenching
centers?
< 65
Are electron traps also exciton quenchers?
Universal electron trap density ~ 510
17
cm
-3

Distance between traps 1/(510
17
)
1/3
= 12.6 nm

Exciton has to travel 6 nm to reach a trap


Measure electron transport and exciton diffusion
independently in a model system with single
exponential PL decay!!
< 66
Model System PCPDTBT
poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-
4,7-(2,1,3-benzothiadiazole)] (PCPDTBT)
Hole Transport:
Electron Transport:

h
= 610
-8
m
2
/Vs
= 0.075 eV
N
t
=510
17
cm
-3
E
t
=0.3 eV
< 67
PL decay PCPDTBT
All Single exponential!!
< 68
PL decay Analysis (exp. decay)
1 1
4
f
rDc t
t t
= +
Stern-Volmer formula:
= PL decay time of blend with PCBM concentration c

f
= PL decay time of pristine PCPDTBT
r = Sum of the exciton radii
D = Exciton diffusion coefficient.
r~ 1 nm
D=310
-3
cm
2
/s

< 69
0
q c c = +
0
1 1
4 4
f
rDc rDq t t
t t
= +
0
0
1 1
4
f
rDc t
t t
=
q=0: Intrinsic Exciton Lifetime
0

Background Quenchers
PCBM
Background Quenchers
+Stern Volmer:

f
= PL decay time of pristine PCPDTBT

0
= PL decay time of solution
< 70
Graphical Representation c
0
c
0
=610
17
cm
-3
, equal to N
trap
electrons !!!!!
< 71
What about PL efficiency?
t
f
=
1
+ k
nr
+ k
diff
t
0
=
1
+ k
nr
k
diff
=
1
t
f

1
t
0
= 4p rDc
0
g =

+ k
nr
+ k
diff
=

1
t
0
+ 4p rDc
0
=
1 t
0
k
nr
1+ 4p rDc
0
t
0
Measured lifetime in film
Measured lifetime in solution
Stern-Volmer
PL Yield
< 72
PL from integrating sphere

0
k
nr
=0.72
Conclusions
Imbalanced transport and strong recombination lead to a
square-root dependence of the photocurrent, FF~0.4

Nature of recombination can be identified from charge-
transfer state electroluminescence
CT-state emission is of bimolecular origin
Weak trap-assisted recombination is present in
P3HT:PCBM solar cells

The amount of exciton quenchers is equal to the amount of
electron traps. The exciton diffusion length and liftetime
are not intrinsic but are determined by extrinsic defects



< 73
RuG
Cristina Tanase
Denis Markov
Jan Anton Koster
Magda Mandoc
Irina Craciun
Yuan Zhang
Herman Nicolai
Gert-Jan Wetzelaer
Paul de Bruyn
Niels van der Kaap
Bert de Boer


Dago de Leeuw
Acknowledgement:
UCSB
Alex Miknenko
Martijn Kuik
Jason Lin
Quyen Nguyen

GeorgiaTech
Jean-Luc Bredas
Chad Risko
Casey Campbell

Thank you for your attention!!!
< 75
< 76
Injection: Barrier Height
Transport: Mobility, Traps, Space Charge
Recombination
2.1 eV
Ca
ITO
O
H
3
C O
n
Burroughes et al., Nature 347, p. 539 (1990)
Transport and Recombination in a PLED
Exponential Trap Distribution: Modified Model
Exp. Trap model:
r=T
t
/T
) (
1 2
1
) (
0
r C
L
V
eN
e N J
r
r
r
eff t
r
n c
+
+
|
|
.
|

\
|
=
c c

E
) exp( ~ ) (
t
t
t
kT
E E
E N

N
trap
=5*10
17
cm
-3

T
t
=1500 K
MDMO-PPV:
(

=
t
tc
t eff t
T
kT E
N N
) 2 /(
exp
2
) (
o
t
T T
c
t t
N
n
N n
/
|
|
.
|

\
|
=
< 77
LUMO PPV
How can we determine
e
, N
t
, and E
tc
??

Trap-limited Electron Transport?
Deep Traps
Shallow Traps
Hopping in
modified DOS
E
tc
v. Mensfoort et al., PRB
80, 033202 (2009)
< 78
n-type doping:
A. Kahn et al., Org. Electr. 9, 575 (2008)
< 79
After n-doping:
Electron current equal to hole current
Temperature dependence equal to temperature dependence of hole
current

e
=
h

Traps located > 0.4 eV below the LUMO

Phys. Rev. B. 81, 085201 (2010)
n-type doping:
< 80
Gaussian LUMO and Exponential Traps?
Use Approximation in Intermediate Voltage Regime:
G. Paasch and S. Scheinert, J. Appl. Phys. 107, 104501 (2010).
10
14
10
16
10
18
10
20
10
22
10
24
10
26
10
18
10
19
10
20
10
21
10
22
10
23
10
24
10
25

LUMO
E

Single level
Exponential
Gaussian


n
t

(
m
-
3
)
n (m
-3
)
< 81
Polymer:PCBM bulk heterojunction solar cells have an
ideality factor of ~1.3




Ideality factor solar cells: Dark Current
(

|
|
.
|

\
|
= 1 exp
kT
qV
J J
s D
q
n>1: Evidence for trap-assisted recombination?
< 82
Single Carrier Dark-Current (no rec!!)

Ideality factor single-carrier
devices of separate materials
match ideality factors of the
blend





=> Ideality factor is determined by transport-dominating
constituent of the solar cell blend.
Appl. Phys. Lett. 99, 153506 (2011)
Other conjugated polymers?
0.1 1 10
10
-3
10
-2
10
-1
10
0
10
1
10
2
10
3
10
4
148 nm PCPDTBT
85 nm PF10TBT
173 nm F8BT
300 nm OC
1
C
10
-PPV


C
u
r
r
e
n
t

D
e
n
s
i
t
y

(
A
/
m

)
V (V)
Slope of Trap-limited Electron Current varies for different polymers
< 84
PLED Operation:
Trap-Free SCL Hole Transport
Trap-limited Electron Transport
Langevin Recombination, Shockley-Read-Hall Recombination
Ca
ITO
< 85
L
J-V characteristic is:

No recombination losses:
+
_
hv
V=V
OC
-bias
|
|
.
|

\
|

+
= + =
eV
kT
kT eV
kT eV
eGL J J J
p n
2
1 ) / exp(
1 ) / exp(
Hughes and Sokel: J. Appl. Phys. 52, 1981, 6743
J
V
V
diffusion drift
Assumption: Diffusion neglected
< 86
Recap:
|
|
.
|

\
|

+
=
eV
kT
kT eV
kT eV
eGL J
2
1 ) / exp(
1 ) / exp(
( )
L
V
eG J
p p n n
t t + =

8
9
2 / 1 4 / 3
4 / 1
V G
q
q J
p
|
|
.
|

\
|
=
c
Low voltage: Ohmic behaviour:
( )
2 / 1
2 / 1
V eG J
n n
t =
eGL J =
Intermediate voltage: Square root behaviour:
Saturation regime: Voltage independent
or
??
Drift vs diffusion
or ??
< 87
Poly(F2D) allows formation of a completely
immobilized well-defined heterostructure
L
D
=5-7 nm
N
O
O
C
4
H
9
C
4
H
9
F2D

0 40
0.0
0.2
0.4
0.6
0.8
1.0


P
L

q
u
e
n
c
h
i
n
g

[
a
.
u
.
]
NRS-PPV film thickness [nm]
NRS-PPV/poly(F2D)
L
D
= 5 nm
Time-independent!!
Photovoltaic response: 7 nm
J.J.M.Halls et.al., Appl. Phys. Lett., 1996, 68, 3120
Exciton Diffusion Length
J. Phys. Chem. A 2005, 109, 5266-5274
) , ( ) , ( ) (
) , (
) (
) , ( ) , (
2
2
t x g t x n x S
x
t x n
D
t
t x n
t
t x n
+
c
c
+ =
c
c
t
0 200 400 600 800
0.0
0.2
0.4
0.6
0.8
1.0


P
L

i
n
t
e
n
s
i
t
y

[
a
.
u
.
]
Time [ps]
Neat NRS-PPV
Film thickness
15.5 nm
8 nm
4 nm
s
cm
D
NRS
2
4
10 3

=
Photo-induced defect quenching:
D=2 10
-4
cm
2
/s
M. Yan et. al.,
Phys. Rev. Let., 1994, 73, 744
Exciton Diffusion Coefficient
Neat Polymer used as reference
PHYSICAL REVIEW B 72, 045216 2005
< 90
Exciton Diffusion Coefficient
Bulk Quencher
PCBM
C-PCPDTBT
< 91
Exciton Diffusion Coefficient
Relative quenching efficiency
}
}
=
dt PL
dt PL
Q
pristine
blend
1
Intimate
mixture:
no clusters!
MC simulation:
D=310
-3
cm
2
/s
L
D
=10 nm

Energy Environ. Sci., 2012, 5, 6960
< 92
Neat Polymer PL decay
PL decay is not single exponential.
-relaxation of excitons in Gaussian DOS

J. Phys. Chem. B 2008, 112, 1160111604 11601
Movaghar, B.; Grnewald, M.; Ries, B.; Bssler, H.; Wrtz, D.
Phys. Rev. B 1986, 33, 55455554.
< 93
Recap:
Reduction of disorder leads to increase of
exciton diffusion coefficient

For exciton diffusion coefficient >10
-3
cm
2
/Vs
the PL decay is single exponential

The exciton diffusion length ~5-7 nm is
independent on disorder.
0.01 0.1 1 10
0.1
1
constant G
Jo V
MDMO-PPV:PCBM
Si p/n cell


J
/
J
m
a
x
Voc-V [V]
field dependent G
The generation rate in blends of MDMO-PPV:PCBM is field dependent!

Organic BHJ vs. Si-based Solar cell
< 94
Introduction of TCNQ electron traps:
Can we prove that recombination with trapped electrons is
responsible for the enhanced dependence of Voc on light
intensity?
LUMO MDMO-PPV
LUMO PCBM
HOMO MDMO-PPV
HOMO PCBM
Exciton
diffusion
N
N
N
N
H H
H H
4.5 eV
TCNQ
< 95
10 100 1000
0.2
0.4
0.6
0.8
1.0
S[kT/q]=3
Light intensity (W/m
2
)


V
o
c

(
V
)
No Traps
S[kT/q]=1
TCNQ Traps
V
oc
light intensity dependence
Appl. Phys. Lett. 91, 263505 2007
< 96
< 97
PL decay PCPDTBT

0
=212 ps

f
= 146 ps
+
3-D Transport by hopping
between conjugated parts
of the chain
Disorder dominated charge transport
Low mobility:~
Vs
cm
2
7
10 5

=
Bssler, Phys. Stat. Sol. (b) 175, 15 (1993)
< 98