Plastic Solar Cells

Thuc-Quyen Nguyen
Department of Chemistry and Biochemistry
Center for Polymers and Organic Solids (CPOS)
University of California, Santa Barbara

Bulk Heterojunction Polymer Solar Cells

1) Light absorption 
create the excited
state named “exciton”
(electron-hole pair)
ITO
2) Exciton diffusion
3) Charge separation
or electron transfer at
donor-acceptor
interfaces
4) Charge transport
5) Charge Collection
Aluminum
Exciton Fullerene 
Polymer (Donor)
(Acceptor)
 Organic Solar Cell Fabrication

Challenges
- Material Design and Synthesis: Need strategy, theory to
guide synthesis, take a long time to optimize new materials,
material reproducibility
- Material Characterization: nanoscale morphology of blended
materials, interfaces, charge generation, charge transport,
charge recombination, defects, etc.
- Device Physics

- Degradation, Lifetime
- Modeling/Calculation: materials and devices
 Issues with Conjugated Polymers
1) Batch to batch variation Mn ~ 7K kg/mol
η% ~ 1.2%
- Molecular weight (MW)
- Polydispersity
Mn ~14K kg/mol
- Chain end variation
2) Impurity
3) Difficult to purify Mn ~ 34K kg/mol
η% ~ 5.9%
4) Weak molecular packing

Gui Bazan (UCSB), Nature Chemistry, in press

Advantages of Molecular Donors

SiEt3
C6H13O

S S C6H13O OC6H13

OC6H13
PCE = 1.1%
PCE = 1% S
SiET3

S
S S
S S

S S
N

S S S
S S
S S S
O
PCE = 0.8% PCE = 0.8%
O

G. Malliaras, Mater. Today 2007, 10, 34.

Molecular Donors: No batch to batch variation, easy to

purify and to functionalize
 New Materials
Strong Absorbing
Chromophore

Strong Molecular Thermal/Photo/

Order Electrochemical
Stability
Donor Materials

High Charge Solution

Carrier Mobility Processable

Low Band Gap

Building Blocks
Sexithiophene Diketopyrrolopyrrole
(DPP)
S S S
S S S
R3
vacuum deposited on SiO2
O N R2

R1 N O
R4
h ~ 0.2 cm2/V.s Wallquist, Olof; Lenz, R. “20 years of
DPP pigments - future perspectives.”
Muccini, et al., Nature Materials Macromolecular Symposia (2002), 187,
4, 81-85 (2005) 617-629
Applications of DPP: Paint Pigments

Diketopyrrolopyrrole (DPP)
High thermal stability

Incorporate the Best of Both Worlds

+ S
S
S
S
S
S

Oligothiophene
High charge mobility unit
Diketopyrrolopyrrole
Strong absorbing unit
Strong Intermolecular
Interactions

Functionalization  Solution Process

 Effect of the End Unit

O N O
S
S
O N O

DPP(TBFu)2

T.-Q. Nguyen et al. Adv. Funct. Mater. 2009, 19, 3063.

Optical Properties
1.6 DPP(TBFu)2 Solution
DPP(TBFu)2 Film
1.2
Intensity (a.u.)

PC71BM Film

0.8

0.4

0.0
400 500 600 700
Wavelength (nm)

N O 30:70
O 0.5
50:50
Absorbance (a.u.)

S
S 0.4 60:40
O N O 70:30
0.3

0.2

0.1

400 500 600 700

Wavelength (nm)
 Effect of Blend Ratio on Annealed Film
Morphology
70:30 50:50 30:70

rms ~ 2.1 nm rms ~ 2.2 nm rms ~ 2.4 nm

Annealed at 100 °C for 10 min

Image size: 5 μm  5 μm

Effect of Different Blend Ratios

4
30:70 as-cast 30:70 Annealed
50:50 as-cast 50:50 Annealed
2 60:40 as-cast 60:40 Annealed 0.5
30:70
70:30 as-cast 70:30 Annealed 50:50
0
IPCE (electrons / photon)

60:40
0.4 70:30
-2
J (mA/cm )
2

-4
0.3

-6
0.2
-8
0.1
-10

-12 0.0
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 300 400 500 600 700 800
Potential (V) Wavelength (nm)

As-cast Annealed
30-70 50-50 60-40 70-30 30-70 50-50 60-40 70-30
JSC
6.64 4.13 1.45 0.68 5.70 8.38 10.7 9.01
(mA/cm2)
VOC (V) 0.87 0.93 0.96 0.81 0.89 0.89 0.92 0.92
FF 0.32 0.29 0.24 0.23 0.33 0.38 0.37 0.43
η% 1.85 1.12 0.33 0.12 1.67 2.87 4.33 3.54
 Film Morphology of Annealed Blend
As-cast 90 °C 100 °C

rms ~ 0.5 nm rms ~ 1.1 nm rms ~ 2.3 nm

Image Size: 2 μm  2 μm Blend Ratio: 70:30

Effect of Thermal Annealing on Device

Performance (60:40 blend ratio)
IP C E (e le c tro n s / p h o to n )

2 0.6 As-cast
0 0.5 80 ºC
Current Density (mA/cm )
2

90 °C 100 ºC
-2 100 °C 0.4
110 °C 110 ºC
-4 120 °C 0.3 150 ºC
130 °C
-6 140 °C 0.2 P3HT
-8 0.1
-10 0.0
-12 300 400 500 600 700 800 900
Wavelength (nm)
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
Potential (V)

Temp (°C) 90 100 110 120 130 140

Jsc 10.9 10.7 11.9 10.5 9.2 8.0
Voc 0.92 0.92 0.92 0.92 0.92 0.92
FF 0.34 0.37 0.37 0.39 0.41 0.40
η 3.97 4.33 4.79 4.42 4.12 3.43
 Adv. Funct. Mater. 2009, 19, 3063

Acknowledgements
Students: Postdocs: Undergraduates:
Bright Walker Dr. Arnold Tamayo Peter Zalar
Mark Dante Dr. Chunki Kim Tyler Kent
Jason Lin Dr. Junghwa Seo Ngoc Luu
Mananya Tantiwiwat Dr. Xuan-Dung Dang Duc Duong
Jessica Sherman Dr. Karolina Siskova Janine Boucher
Corey Hoven Dr. Jihua Yang Calvin Peng
Chi-Yen Lin Dr. Peng Wang Alexandra Polosukhina
Michele Guide Dr. Mungsoo Lee Alissa Walker Bell
Daniel Kamkar Dr. Andres Garcia Jaime Salazar
Armando Lagunas
Dorian Mattrey
Victoria Crockett
Collaborators: Jeff Peet, Gui Bazan, Fred
Manuel Schnabel
Wudl, Alan Heeger, Ed Kramer, Harold Ade,
Lynn Loo, Darryl Smith Jennifer Swift
Frank Proa
 Funding
- Office of Naval Research Young Investigator Award
- Camille Dreyfus Teacher Scholar Award
- Alfred Sloan Research Award
- DOE: BES, Energy Frontier Research Centers (EFRCs)
- NSF-MRSEC
- California NanoSystem Institute at UCSB
- Army Office of Research/Institute for Collaborative
Biotechnologies