Low Cost “Plastic” Solar Cells

Solar cells --- Power from the Sun --- must be and will be ---

a significant contribution to our energy needs.

Two problems that must be solved with solar:

1. Cost
2. Area
 Semiconducting and Metallic Polymers

“inks” ---- with

electronic functionality!

Plastic Substrate

Solar Cells
The Dream → →
Functional
Ink
 “Plastic” Solar Cells

Ultrafast charge separation with quantum

efficiency approaching Unity !

1992
ħω RO OR

RO OR

RO OR
e-

RO OR

50 femtoseconds!!
 Ultrafast electron transfer is important ---

Charge transfer is 1000 times faster than any competing

process,
and
Back charge transfer is inhibited

Therefore,
Quantum efficiency for charge separation approaches unity!

Every photon absorbed yields one pair of separated charges!

(Route to photovoltaics and photodetectors)
Ultrafast photo-induced charge separation ----

But how do we create a material with

charge-separating junctions everywhere??

ħω RO OR

RO OR
50 fs
RO OR
e-

RO OR

All must be accomplished at nanometer length scale!

 OMe

S n
Bulk Heterojunction Material
P3HT PCBM Bicontinuous interpenetrating network

Self-assembled nanoscale material with

charge-separating junctions everywhere!
 “Bulk” D-A Heterojunction Material

A self-assembled nanomaterial

Electrical Contact

Electrical Contact

Must break the symmetry --- use two different metals with
different work functions.
Electrons will automatically go toward lower work function
contact and holes toward higher work function contact
 Origin of Voc --- when irradiated with high light intensity,
Fermi levels must be equal (holes in the π-band and electrons in PCBM LUMO):

Voc ≈ EPCBM LUMO - Epolymer homo

π*-band
π*-band

PCBM LUMO PCBM LUMO

Voc --- small Voc --- larger

π-band
PCBM HOMO π-band PCBM HOMO
PCBM PCBM

semiconducting
polymer semiconducting
Polymer
(deeper HOMO)
 Solar Cell Performance

Device structure: ITO/PEDOT/P3HT:PCBM/Al.

Eff = 5.0%
w/o anneal
VOC = 0.625 V
FF = 68%

70oC, 30 min

150oC, 30 min

Series resistance decreased from 113 Ω to 7.9 Ω

“Bulk” Heterojunction Material --- Optimize Nanomorphology

Before 150oC 150oC anneal 150oC anneal

anneal 30 min 2 hours

OMe

S n

P3HT PCBM

TEM images of the P3HT/PCBM

interpenetrating network
After annealing for 10 minutes at 150oC Spatial Fourier Transform

10min annealing
30min annealing
2hour annealing

P.S.D.(a.u.)
0.01 0.1 1
Spatial Frequency(1/nm)
High temperature annealing --- 150o C
1. Stable for long times at High-T
2. 10 minutes sufficient to lock in the nano-scale morphology

Quasi-periodic with “periodicity” of 16-20 nm

 80 nm

|”Period” 160 -200 Å|

Distance from any point in the material to a

charge separating interface ≈ 40-50 Å

Less than the mean exciton diffusion length ---

High efficiency for charge separation.
 New Device Architecture: Optical Spacer

Conventional Device
Glass ITO PEDOT Active Layer Al

Light intensity in

Dead zone
 New Device Architecture: Optical Spacer

Conventional Device Device with Optical Spacer

Glass ITO PEDOT Active Layer Al Glass ITO PEDOT Active Layer Al

Light intensity in

Dead zone Optical spacer

Device architecture: Optical spacer
OR

OR Ti OR

+ H2O

OH

OH Ti OH

OH
Al
P3HT um
PED :PCB
inu O
OT:P M
TiOX m Ti
SS O
Glas ITO Ti
s O
O
Ti
O O Ti

TiOX

Charge separation layer

Optical Spacer can improve the Power Conversion Efficiency

Green light (532 nm)

Efficiency
ηe = 8.1% → 12.6%

25 % - 50% increase in efficiency

AM1.5 (solar spectrum)
Efficiency
Optical spacer important for low mobility
= 2.3% → where
ηe materials 5.0% simply making the active
layer thicker is not an option
 What can we expect to achieve??
Single layer with efficiency > 5% demonstrated with P3HT

Band gap too large ---Missing more than half the solar spectrum

Opportunity: Potential for factor of 2 improvement using

polymer with smaller band gap.
 Semiconducting polymers with smaller band gap?
(a)
Zhengguo Zhu
S

(ZZ50) N N

(c)
( )n
S S

OCH3
O
(b)

S n

Photocurrent (arb.u.)
1E-4

1E-5

1E-6

Absorption and photoresponse 1E-7

ZZ50/ZZ50:PCBM
out to 900 nm in the IR. 1E-8

Photocurrent (arb.u.)
1E-4

1E-5
Should be capable of 7% in single cell 1E-6
and >10% in a Tandem Cell with P3HT
1E-7
P3HT/P3HT:PCBM
1E-8
300 400 500 600 700 800 900 1000

Energy (eV)
 With ZZ50 ---

Progress --- but still missing all incident power in the IR beyond 900 nm.
Need smaller gap materials
 Morphology Control withAlkane-dithiols as Processing Additives
(Nature Materials, Published online May 27. 2007)

Add 2.5% alkanedithiol into solvent (chlorobenzene)

1,3-propanedithiol (blue), 1,4-butanedithiol (green),

1,6-hexanedithiol (orange) and 1,8-octanedithiol (red)

Spectra sharpen and red-shift Higher jsc --- higher efficiency

Processing Additives for Morphology control

Zhengguo
(a)
(a Zhu
S
(ZZ50)
N N

((c)
( )n
S S

OCH3
O
b

Factor of 2 Improvement
η =2.8% by using octane-dithiol
as processing additive
η =5.5% Nature Materials
Published online May 27. 2007

Best performance for a single cell architecture

 Processing Additives for Morphology Control
of Bulk Heterojunction Materials

Mechanism:
(i) Selective (differential) solubility of the fullerene component
(ii) Higher boiling point than the host solvent.
 Absorption Spectra

PCPDTBT film (green)

PCPDTBT:C71-PCBM films processed with 1,8-octanedithiol ---

Before removal of C71-PCBM with alkanedithiol (black),
After removal of C71-PCBM with alkanedithiol (red)

The PCBM is completely removed by the alkane-dithiol!

 Multi-layer Tandem Cell
(equivalent to two solar cells in series)

Al

TiOx

P3HT:PC70BM

OR
PEDOT:PSS
TiOx O Ti O
R R

←
Al
+
TiOx HO
OH 2
Back cell P3HT:PC70BM
PEDOT:PSS
TiOx O Ti OH
H
Front cell PCPDTBT:PCBM
OH
PEDOT:PSS
ITO
O
T
Glass O
T i
i O O
T
i O O Ti

Ti
OX
 Tandem Cell
(Multilayer architecture equivalent to two solar cells in series)

Current Density (mA/cm )

0

2
-2

-4

-6

-8
PCPDTBT single cell
-10 P3HT single cell
Tandem cell
-12
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Bias (V)

Open circuit voltage doubled --- Efficiency 6.5%

 We can do even better ----

Increased performance of
each of the two subcells ---

Already demonstrated
(using the Processing Additive).

Goal for coming months: 8-10 %

In the Tandem Cell, the TiOx layers serve six separate functions:

1. Optical spacer that redistributes the light intensity

to optimize the efficiency of the back cell.

2. With TiOx layer between the charge separating layer and

the aluminum cathode --- much improved air stability

3. The TiOx functions as a low resistance electron transport layer

4. TiOx layer breaks the symmetry and thereby creates

the open circuit voltage.

5. TiOx functions as a hole blocking layer

(top of the valence band at - 8.1 eV)

6. TiOx layer enables the fabrication of tandem cells. The transparent

TiOx layer is used to separate and connect
the front cell and the back cell.
Polymer Solar cells: Present status --- 5 - 6 % with P3HT
(and with several other materials with similar spectra)
What can we expect (hope) to achieve??

New Architecture --- optical spacer --- 25-50% improvement

New Polymers with energy gap well matched to the

solar spectrum
Opportunity for x2 improvement

Better charge collection efficiency (optimize morphology)

Opportunity for 25% improvement

Increased open circuit voltage (deeper HOMO for semiconducting polymer)

Opportunity: Potential for > 50% improvement

Tandem Cell ---

Opportunity: Potential for > 50% improvement
Reality of each of these has been demonstrated.

Goal: Achieve all these advances in the same system

(1.25 x 2 x 1.25 x 1.5 x 1.5 = 7)

Clear vision of technology pathway to BHJ

solar cells with efficiencies exceeding 20%
 New materials are the key to progress

Examples:

LeClerc and colleagues (JACS published on the web 12/21/07)

S
N N

With X = acceptor such as

*
*
S
X S

N n
N N

3.6% with PCBM

C8H17 C8H17

Yong Cao and colleagues (in press)

5.4% with PCBM

Note: Both have high Voc --- 0.9 V Deeper HOMO

 Air-stable polymer electronic devices

Thin layer of amorphous TiOx (x<2) improves performance

and

Enhances Lifetime

Polymer Based Solar Cells

Polymer LEDs
Polymer FETs

Adv Mater. 2007

 Bulk Heterojunction Solar Cells
Single TiOx passivation layer signficantly enhances the lifetime
Factor of 100 !

Efficiency (%)
1 with TiOx

0.1

Conventional

0.01
0 50 100 150
Time (Hours)

Goal: Simple inexpensive barrier materials will be

sufficient for achieving long lifetime.
 Background scientific information

a b

O1s Intensity (C1s- Normalized)

1.0 Glass/PF 0.6
PL Intensity (Normalized)

Glass/TiOx/PF
Glass/PF/TiOx
0.5 Glass/TiOx/PF/TiOx without TiOx layer
Fresh Film with TiOx layer 0.4

0.0

1.0 o
15 hours at 150 C 0.2

0.5

0.0
0.0
400 500 600 700 530 525 520
Wavelength (nm) Binding Energy (eV)

TiOx prevents oxidation XPS of the O1s/C1s ratio

of polyfluorene (PF) in the PF after
48 hrs at 150oC in air
 Similar enhancement in lifetime for LEDs and FETs

FETs
LEDs
Luminous Efficiency (cd/A)

-1
10 with TiOx

-2
10 Conventional

0 5 10 15 20
Time (Hours)
Rooftop testing of BHJ solar cells at KONARKA
 Lifetime: Rooftop and Accelerated Degradation
Flexible devices packaged with commercial, low cost barrier films
(Konarka)

Active layers
Barrier Film
Metal Metal
Transparent Electrode
PET
Barrier Film
UV-Filter

Illumination

Flexible Organic P3HT:PCBM Bulk-Heterojunction Modules with more than 1 Year Outdoor Lifetime
Jens A. Hauch, Pavel Schilinsky, Stelios A. Choulis, Richard Childers, Markus Biele and Christoph J. Brabec

Long-Lived Flexible Organic Solar Cells

Jens A. Hauch, Pavel Schilinsky, Stelios C. Choulis, Sambatra Rajoelson and Christoph J. Brabec
 Outdoor rooftop lifetime (Konarka)
1.6 60
Sep. 20th 2006 Nov. 7th 2007

1.4 50

Normalized Power output [a.u.]

1.2 40

Temperature [°C]
1.0 30

0.8 20

0.6 10

0.4 0

0.2 Efficiency -10

Temperature
0.0 -20
S O N D J F M A M J J A S O N D
Month

15.00%
10.86%
10.00%

Efficiency actually increased --- 5.00% 3.31%

0.14%
Drop in power output after 1 year 0.00%
due to small shift in the maximum Efficiency Voc Jsc FF
power point (from 0.87V to 0.8V). -5.00%

-6.80%
-10.00%

Rel. Change
-15.00%
 Accelerated Degradation ---
Flexible devices packaged with commercial, low cost barrier films
(Konarka)

110%
105%
100%

Normalized Jsc [a.u.]

Normalized Voc [a.u.]

100%
90%

95% 80%

70%
65°C/85%rh 65°C/85%rh
90%
65°C 60% 65°C
65°C/1sun 65°C/1sun
85% 50%
0 250 500 750 1000 1250 0 250 500 750 1000 1250
Time [hrs] Time [hrs]
105% 110%

Normalized Efficiency [a.u.]

100%
Normalized FF [a.u.]

100%
95% 90%

90% 80%

85% 70%
65°C/85%rh 65°C/85%rh
80% 65°C 60% 65°C
65°C/1sun 65°C/1sun
75% 50%
0 250 500 750 1000 1250 0 250 500 750 1000 1250
Time [hrs] Time [hrs]
Goal: Efficiency > 10 - 15% with polymer
“bulk heterojunction” nano-materials

Low Cost Roll-to-Roll manufacturing by

printing and coating technologies
Acknowledgement

Professor Kwanghee Lee ---UCSB and GIST (Korea)

Dr. Jin Young Kim
Prof G. Bazan, D. Moses, J.Peet
Christoph Brabec and colleagues at Konarka