Solution-Processed Small-

Molecule Solar Cells with 7%

Efficiency
Alan J. Heeger
Professor of Physics & Materials, UC Santa Barbara
Acknowledgements

Gui Bazan
Greg Welch

Yanming Sun and Weilin Leong
(device fabrication and analysis)

Chris Takacs
(High resolution phase contrast TEM)

Loren Kaake (Ultrafast spectroscopy)

This is a CEEM project
with partial support from AFOSR
Why Organic Photovoltaics (OPV)?

- Thin, flexible, light weight and rugged products

- High throughput, roll-to-roll manufacturing

- Potential for low cost and low carbon footprint

- Unique semi-transparent modules with tunable colors

- Remarkably interesting and challenging science ---
nanoscale photovoltaics!

Roll-to-Roll Manufacturing
Bulk Heterojunction Solar
Cells Fabricated from Small
Molecules (Not Polymers)
New Direction
With polymers --- batch-to-batch variations in solubility,
molecular weight, polydisperity and purity provide
materials with considerably different processing properties.

Difficult, therefore, to evaluate the fundamental
structure-performance relationships.
New Direction:
Solution-Processed Small-Molecule Solar Cells
with 6.7% Efficiency
e
V
ITO/MoO
x
/TTPSiBT:PC
70
BM/Al
-5.4 eV
-4.7 eV
-3.6 eV
-5.2 eV
-4.3 eV
-6.1 eV
-4.3 eV
-3.0
-4.0
-5.0
-6.0
-7.0
DTS(PTTh
2
)
2 PC
70
BM
a
b c
OMe
O
N
S
N
N
S
N
S
S
Si
S
S
S
N
S
N
300 400 500 600 700 800 900 1000
0.0
0.2
0.4
0.6
0.8
1.0
1.2


N
o
r
m
a
l
i
z
e
d

A
b
s
o
r
p
t
i
o
n
Wavelength (nm)
Solution
Film
Design and synthesis:
G. Bazan and G. Welch
Dynamics and Time Scales
Mobile carrier
sweep out by the
internal voltage
(built-in electric
field)
Ground state
Interfacial traps
and
Interfacial
excitons
Excited state
and
charge
transfer
h
Recombination
t < 100 fs
t < 100 fs
Energy out
ns - s
HOMO
LUMO
HOMO
LUMO
Electron Acceptor
Electron Donor
The Initial Discovery (1992):
Ultrafast Photo-induced electron transfer
Photo-induced charge transfer < 10
-12
s
*
*
n

hv
e-
+
Ultrafast charge separation with quantum efficiency approaching Unity !
50 fs
Brabec et al Chem Phys Lett 2001
-60 -50 -40 -30 -20 -10 0 10
10
-11
10
-10
10
-9
10
-8
10
-7
10
-6
10
-5
10
-4

I
d
s

1
/
2

(
m
A
1
/
2
)

I
d
s

V
gs
(V)

14.0


0.0
2.0
4.0
6.0
8.0
10.0

12.0

0 -10 -20 -30 -40 -50 -60


I
d
s

(

A
)
V
ds
(V)
-20 V
-30 V
-40 V
-50 V

-60 V
0.0
-20.0
-40.0
-60.0
-80.0
-100.0 a b
OFET data obtained from pristine DTS(PTTh
2
)
2
.
a) Output curves
b) transfer curves (V
ds
=-60 V).

Hole mobility (saturation regime) ~ 0.12 cm
2
/Vs

on/off ratio of ~ 10
7
.


-0.2 0.0 0.2 0.4 0.6 0.8 1.0
-14
-12
-10
-8
-6
-4
-2
0
2


C
u
r
r
e
n
t

d
e
n
s
i
t
y

(
m
A
/
c
m
2
)
Voltage (V)
80:20
70:30
60:40
50:50
Relatively small amount of fullerene is required ---
Optimum Donor-to-fullerene ratio is 7:3
Device science:
Yanming Sun and Wei Lin Leong

Summary of device parameters of SM-BHJ solar cells with
active layers cast from solutions with different blend ratios .


DTS(PTTh
2
)
2
/PC
70
BM
(weight ratios)
a

V
oc
(V) J
sc
(mA/cm
2
) FF (%) PCE (%)
80:20
70:30
60:40
50:50
0.80
0.80
0.83
0.84
11.4
12.5
7.2
4.4
39.4
45.2
35.4
28.6
3.60
4.52
2.12
1.06
a
Active layer thin films cast from 4% w/v CB solutions with varying weight
ratio of the DTS(PTTh2)
2
:PC70BM components
7:3 G24:PC
70
BM (=6.7%)
Top View
SideView
100 nm
7:3 G24:PC
70
BM (=6.7%)
James Rogers, Ed Kramer and Gui Bazan
300 400 500 600 700 800 900
0
10
20
30
40
50
60


I
P
C
E

(
%
)
wavelength (nm)
80:20
70:30
60:40
50:50
IPCE spectra of SM-BHJ solar cells based on DTS(PTTh
2
)
2
/PC
70
BM
active layer with different blend ratios.
-0.2 0.0 0.2 0.4 0.6 0.8
-14
-12
-10
-8
-6
-4
-2
0
2


C
u
r
r
e
n
t

d
e
n
s
i
t
y

(
m
A
/
c
m
2
)
Voltage (V)
300 400 500 600 700 800 900
0
10
20
30
40
50
60
70


I
P
C
E

(
%
)
Wavelength (nm)
0%
0.2%
0.6%
1.0%
Performance of solar cells with a DTS(PTTh
2
)
2
:PC
70
BM active layer
as a function of DIO content (as processing additive).

(a) Current-voltage curves (b) IPCE spectra.
Processing with 0.25% DIO (as additive) optimum:
PCE = 6.7%
FF = 0.59
V
oc
= 0.78V
J
sc
= 14.4 mA/cm
2

Each of these values sets a new record for small molecule OPV!
-60 -40 -20 0 20 40 60
10
-10
10
-9
10
-8
10
-7
10
-6
10
-5
10
-10
10
-9
10
-8
10
-7
10
-6
10
-5
n-type mode
with 0.25% DIO
w/o DIO


I
d
s

(
V
)
V
gs
(V)
p-type mode
Transfer characteristics of bipolar field-effect transistors based on
DTS(PTTh
2
)
2
/PC
70
BM blended films processed with and without DIO additives.

Hole mobility ~ 610
-3
cm
2
/Vs
Electron mobility ~ 210
-3
cm
2
/Vs

Nearly balanced.

1 2 3 4 5 6
40
45
50
55
60


F
F

(
%
)
Process run
1 2 3 4 5 6
4.0
4.5
5.0
5.5
6.0
6.5
7.0


P
C
E

(
%
)
Process run
1 2 3 4 5 6
10
11
12
13
14
15


J
s
c

(
m
A
/
c
m
2
)
Process run
1 2 3 4 5 6
0.70
0.72
0.74
0.76
0.78
0.80


V
o
c

(
V
)
Process run
Performance distribution of SM-BHJ solar cells based on
DTS(PTTh
2
)
2
/PC
70
BM active layers with 0.25% DIO (v/v).

Independent 6 batches of device fabrication were made
and for each batch at least 2 cells were tested (totally 14 cells).

The average PCE is ~ 6.2%.

DTS(PTTh
2
)
2
BHJ on MoOx (no DIO )
(163 nm per side)
(50 nm scale bar)
False Color
Raw Image
TEM:
Chris Takacs
In-plane stacking of DTS(PTTh
2
)
2
at 0.31
-1
.
(approx. 2 nm d-spacing)

Regions of solid color indicate the spatial extent
and direction of the crystal lattice planes.

Defocused --- Phase Contrast TEM


AZ = defocus length
u = spatial frequency
= e-wavelength (2.5 pm)
) sin( 2 ) ( ) ( ) (
2
u Z u E u A u CTF tA =

Phase Contrast TEM
E-beam undergoes many small angle
deflections proportional to the density
of carbon nuclei
PCBM has higher density of carbon
nuclei
E-beam velocity is slower in PCBM than
in Polymer

Result: Phase Contrast
Morphology of the BHJ Materials
Defocused (Phase Contrast) TEM imaging
of the lattice planes
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
0
0.2
0.4
0.6
0.8
1
1.2
x 10
-9
P
o
w
e
r

S
p
e
c
t
r
u
m

(
A
r
b
.
)
q (
-1
)
Azimuthally integrated power spectrum from BHJ raw images:
Blue is from no DIO device (pristine),
Red is 0.25% DIO device (optimal) device,
Green is 0.60% DIO device.
The dashed line represents the theoretical |CTF|
2
for a defocus
of -1000 nm.

DTS(PTTh
2
)
2
BHJ on MoOx (no DIO )
(163 nm per side)
(50 nm scale bar)
False Color
Raw Image
TEM:
Chris Takacs
In-plane stacking of DTS(PTTh
2
)
2
at 0.31
-1
.
(approx. 2 nm d-spacing)

Regions of solid color indicate the spatial extent
and direction of the crystal lattice fringes.

DTS(PTTh
2
)
2
BHJ on MoOx (0.25% DIO)
(163 nm per side)
False Color
Raw Image
TEM:
Chris Takacs
In-plane stacking of DTS(PTTh
2
)
2
at 0.31
-1
.
(approx. 2 nm d-spacing)

Regions of solid color indicate the spatial extent
and direction of the crystal lattice fringes.


50 nm scale bar
Caution: Generation of impurity
during synthesis

- Remove impurity via extraction with hexanes and
column chromatography
- Can avoid methyl transfer by lowering reaction temperature
Typically less than 1% impurity

Device V
oc
(V) J
sc
(mA/cm
2
) FF (%) PCE (%)
G24:PC
70
BM 0.78 14.4 59.3 6.70
G24 (impurity):PC
70
BM 0.74 10.2 39.6 3.00
300 400 500 600 700 800
0
10
20
30
40
50
60
70


I
P
C
E

(
%
)
Wavelength (nm)
G24
G24 with impurity


0.0 0.2 0.4 0.6 0.8
-16
-14
-12
-10
-8
-6
-4
-2
0
2
G24
G24 with impurity


I
(
m
A
/
c
m
^
2
)
Voltage(v)
PC
84
BM Traps in PCDTBT:PC
84
BM
Introduce first-order (monomolecular) recombination
and decrease V
OC

Reduce mobility

Reduce j
SC
and prevent fast sweep out


Result: All parameters adversely affected:
V
OC
j
SC
FF

-0.5 0.0 0.5 1.0
-8
-6
-4
-2
0
2
m
84
:m
60
= 1:100
m
84
:m
60
= 0:1


C
u
r
r
e
n
t

d
e
n
s
i
t
y

(
m
A
/
c
m
2
)
Voltage (V)
m
84
:m
60
= 1:1,000
a.

0.0
10
-4
10
-3
10
-2
10
-1
10
0
0.5
0.6
0.7
0.8
0.9
m
84
:m
60
= 0:1
m
84
:m
60
= 1:10,000
m
84
:m
60
= 1:1,000
m
84
:m
60
= 1:100
m
84
:m
60
= 1:0
(estimated)


O
p
e
n

c
i
r
c
u
i
t

v
o
l
t
a
g
e

(
V
)
PC
84
BM Concentration
d.
S
S
N
C
8
H
17 C
8
H
17
n
N
N
S
a
OMe
O
Dynamics and Time Scales
Mobile carrier
sweep out by the
internal voltage
(built-in electric
field)
Ground state
Interfacial traps
and
Interfacial
excitons
Excited state
and
charge
transfer
h
Recombination
t < 100 fs
t < 100 fs
Energy out
ns - s
80
60
40
20
0
t
C
T

(
f
s
)
0.6 0.4 0.2 0.0
DIO (%v/v)
-1.0
-0.5
0.0
0.5
1.0

A

(
a
u
)
1.5 1.0 0.5 0.0 -0.5
time (ps)
DIO (%v/v)
0.25
0.16
0.08
0.00
( a )
( b )
Ultrafast charge separation is enhanced by DiO additive
Continuum of interface states can enable
the ultrafast charge transfer
e
-
center of mass
donor acceptor
e/h pair
exciton
CT states
CT continuum
CT exciton
CS state
E
Looking for a model
General properties of an attractive
potential in a continuum
Bound states
Scattering states
Loss of carriers at early times due to bimolecular
recombination at very high carrier densities
Still lower pump power ------
approx. 2.7x10
17
electrons per cm
COMPETITION between
SWEEPOUT and RECOMBINATION
Mobile carrier
sweep out by the
internal voltage
(built-in electric
field)
Ground state
Interfacial traps
and
Interfacial
excitons
Recombination
Time scale ???
Energy out
ns - s
0 5 10 15 20
10
-3
10
-2
10
-1
10
0
Time (s)
J

/

V
i
n
t

(
m
O
-
1

c
m
-
2
)


0.7V
0.6V
0.5V
0.4V
0.2V
0.0V
-0.5V
-1.0V
PCDTBT:PC70BM
T = 300K
OMe
O
PCDTBT
PC
70
BM
V
int
= V
BI
V
Photoconductance =
Current / Internal
voltage
Transient photocurrent in operating solar cell:
Competition between Sweep-out and Recombination
When sweep-out is faster than recombination
--- high efficiency.
Device J
sc
(mA cm
-2
) V
oc
(V) FF (%) PCE (%)
70:30 13.39 0.78 62.7 6.50
80:20 9.81 0.78 54.1 4.12
85:15 5.51 0.77 39.6 1.68
90:10 3.55 0.76 37.2 1.0
95:05 0.20 0.73 26.1 0.04
100:0 / 0.50 26.3 /
-0.2 0.0 0.2 0.4 0.6 0.8
-14
-12
-10
-8
-6
-4
-2
0
2


C
u
r
r
e
n
t

d
e
n
s
i
t
y

(
m
A
/
c
m
2
)
Voltage (V)
70:30
80:20
85:15
90:10
95:05
300 400 500 600 700 800
10
20
30
40
50
60
70


I
P
C
E

(
%
)
Wavelength (nm)
70:30
80:20
85:15
90:10
95:05
Solution-Processed Small-Molecule Solar Cells with 6.7% Efficiency

A Promising New Direction !

Nature Materials (submitted)

G. Bazan, G. Welch, Y. Sun, W-L Leong, C.J. Takacs and AJH

Plastic Solar Cells
E
f
f
i
c
i
e
n
c
y

(
%
)

2000 1995
NREL
NREL
NREL
NREL
United Solar
United Solar
12
8
4
0
16
20
2005
UCSB
Cambridge

NREL
U. Linz
Siemens
Konarka
Konarka
Siemens
2010
12
8
4
0
16
20
OPV single junction
Year
Konarka
Plextronics
UCSB
Solarmer
Efficiency
Konarka
Time evolution of
efficiency of plastic
solar cells

9.3 % Japan;9.2% SCUT
(inverted structure)
Plastic Solar Cells
Low $ cost manufacturing

Low energy cost manufacturing

Low carbon footprint manufacturing
Technology
Energy for
production
(MJ.Wp
-1
)
CO
2

footprint
(gr.CO
2
-eq.Wp
-1
)
Energy
payback time
(years)
mc-Si 24.9 1293 1.95
CdTe 9.5 542 0.75
CIS 34.6 2231 2.71
Flex OPV 2.4 132 0.19
A. L. Roes et al, Progress in Photovoltaics 17, 372 (2009)
Semi-transparent BIPV based on OPV
BIPV for new constructions
BAPV for retro-fit existing buildings

Power Plastic: Blending Functionality with Aesthetics
Questions ???