Eight19 Limited

Advanced Electron Transport Materials

for Application in Organic
Photovoltaics (OPV)
Alan Sellinger
GCEP Research Symposium 2011
October 5, 2011

1
 Why Solar?
1 % of land with solar cells could meet our electricity needs
6 Boxes at 3.3 TW Each

Amount of solar energy in hours, received each day on an optimally tilted surface during
the worst month of the year.
 Germany 50% 3
Total PV installation:
USA 9%!
Types of Solar Technologies

Lowest cost
$/W

4
 Why Organic Semiconductors?

CuPc
Attractive properties: Copper Phthalocyanine
Abundant: ~100,000 tons/year
Mature industry/markets
Low materials cost: ~$1/g 15/m2
Low-cost processing: printing
Excellent stability
Non-toxic 5
Organic LEDs for Displays
Organic LEDs for Lighting
New Applications for Organic Solar Cells
 Chemistry Nobel Prize Day!
Organic Electronics: Combination of 3 Nobel Prizes!
1996 Nobel Prize in Chemistry - Robert F. Curl Jr., Sir Harold Kroto,
Richard E. Smalley for their discovery of fullerenes (C60)

C60 C70

2000 Nobel Prize in Chemistry - Alan Heeger, Alan G. MacDiarmid,

Hideki Shirakawa for their discovery and development of conductive
polymers S
n
PEDOT
O O

2010 Nobel Prize in Chemistry - Richard F. Heck, Ei-ichi Negishi, Akira

Suzuki for palladium-catalyzed cross couplings in organic synthesis
C-C bond formation
S C6H13 C6H13
O N N O
S S
N N
S S
9
n/4
O O
C6H13 C6H13
 Motivation for Organic-Based PV

Lower production cost

Roll-to-roll coating
Inexpensive active materials
Inexpensive processing
Lower capital cost

Inhabitat.com

Lower environmental impact - $/W

Energy Payback CO2 Emission in
Time (yrs) Production (g)

Crystalline silicon 2.3 1560

Thin film (CIGS, CdTe, etc.) 1.2-3.2 900-2560
Polymer PV (Glass substrate) 1.3 820
Polymer PV (Plastic substrate) 0.2 130
Roes et al., Prog. Photovoltaics. 2009 (17) 372-393 10
Cost Analysis for Solar Cell Technologies
Thin Film

Crystalline Si

near term/today

Organic/Hybrid
Efficiency

today

$/W basis competitive

future

Paint Material and Manufacturing Cost Ingot

 What is an Organic Photovoltaic?

Simplified Working Principle

Recombination

+ +
Photon - -
Exciton

Cathode
Hole Charge Separation
Electron
Anode

+ + +
+- - - -

+- Drift/Diffusion
+
+ + -
Photon - -
Diffusion
Generation

Donor Material Acceptor Material

50-200 nm

Kietzke, T., Adv. OptoElect., 2007, Article ID 40285.

 Progress in Organic Solar Cells
10%? Mitsubishi 2011

Solution processes (Polymer, PCBM) ?

Vacuum processed 9% Solarmer 2011

8.3% Heliatek 2010

2005 2010

Similar development for organic solar cells as for amorphous silicon 20 years ago
Both approaches are reaching nearly similar efficiencies
Improvements are largely materials discovery based
 Estimated lifetimes of OPVs

Burn-in Lifetime in linear

loss Burn-in time regime*
P3HT:PCBM 16% 55 days 3.5 years
PCDTBT:PC70BM 27% 38 days 6.7 years

*Lifetime assumes 5.5 hrs/day of one-sun intensity1

Heliatek (BASF and Bosch) has achieved 30 year lifetimes

with tandem OPVs2

1. C. Peters, M. McGehee, Adv. Energy Mater. in press, 2011

2. www.heliatek.com
 Bulk heterojunction (BHJ) Polymer Solar Cell

Current world record:

8-10%
Extrapolated lifetimes >6 years
Advantages:
Solution processing (roll-to-roll), increased contact area between
active phases,
Disadvantages:
Difficult to achieve optimum morphology, polymers generally less
pure than molecules, solvent dependence
http://www.solarmer.com/
 High-efficiency BHJ solar cells
PCDTBT:PC70BM
PBT7:PC70BM O 6.1% PCE
7.4% PCE O

PCPC70BM
70BM
Liang et al., Adv. Mat. 2010 (22) E135-E138
Park et al., Nat. Phot. 2009 (3) 297-303

P3HT:ICBA*
6.5% PCE

* ICBA: Indene-C60 Bisadduct

Zhao et al., Adv. Mat. 2010 (22) 4355-4358

PC60BM

Record OPV cells ALL use fullerene derivatives

16
Recent development based on donor materials discovery
 Drawbacks for fullerenes

5
x 10
2.5
Absorption Coefficient (M-1 cm-1)

New Acceptor
PC60BM -3.1 eV -3.1 eV
2
PC70BM -3.4 eV
-3.7 eV
1.5 -3.9 eV
P3HT P3HT
-4.3 eV
1
New
PCBM Acceptor
0.5 -5.1 eV -5.1 eV
-5.6 eV
-5.9 eV
0 -6.1 eV
300 400 500 600 700 800 -6.1 eV
Wavelength (nm)

Reduced solar spectrum

absorption Lower VOC

Difficult synthesis and purification = Higher cost

PC60BM: $50/g
CuPc: $1-5/g

Fullerene acceptor up to 10% of total PV system cost

17
Roes et al., Prog. Photovoltaics. 2009 (17) 372-393
 Effect of Production Steps on Cost

O
O
O
O

PC60BM PC70BM

Significant increases (2X) for higher purification

PC71BM approximately 3.4X more expensive than PC61BM
18
Anctil et al., Environ. Sci. Technol. 45, (2011) 2353-9
 Non-fullerene acceptors
P3HT:99BF
~2% PCE

POPT:CN-PPV
O 2% PCE
O
CN

O NC
O n
O O
Holcombe et al., J. Am. Chem. Soc. 2009 131 (40) Brunetti et al., Ang. Chem. Int. Ed. 2010 49 (3) 532-536
14160-14161
SubPc:FSubPc dimer
2.5% PCE (vacuum) N
S
N
F F

F
F F
F NC CN POPT:EV-BT
N N
Cl 1.4% PCE
F N N F
N N CN
N N NC
N B N N B N
N N
F N N F
Cl
F F
F F
F F
Verreet et al., Adv. Ener. Mat. . 2011 (1) 565-568 Woo et al., Chem. Mater. 2010 22 (5) 1673-1679

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Lower efficiencies due to lower JSC and lower FF
 New Acceptors based on Vinazene
Original applications as high nitrogen containing materials for
reduced flammability. Without vinyl groups has been used in
the agriculture sector (fertilizers)

Their highly electron deficient properties make them

candidates as acceptor materials in organic electronic
applications

R R

HN N HN N HN N

NC CN NC CN
NC CN
Vinazene
2-vinyl-4,5-dicyanoimidazole 4,5-dicyanoimidazole

Commercially available
Alkylation of 2-Vinyl-4,5-dicyanoimidazole

Acetone, K2CO3
N N
I
Reflux
NC CN
1-Butylvinazene (90%)

Acetone, K2CO3
N NH
N N
I

NC CN Reflux
NC CN
Vinazene
1-Hexylvinazene (90%)

DMF, K2CO3, 70oC

N N
Br

NC CN
1-Ethylhexylvinazene (56%)
 Tunable Synthesis: Heck Chemistry

Shin R.Y.C., Sonar, P., Siew, P.S., Chen, Z.C., Sellinger, A., J. Org. Chem., 2009, 74 (9), 32933298.
Optical properties of selected vinazene derivatives
S S
N N N N
S
S
(1) (4) (5)
(10) (13)

1 1
1.0 1.0
4 4
5 5
10
Normalised Intensity (a.u.)

Normalised Intensity (a.u.)

10
0.8 0.8
13 13

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
300 350 400 450 500 550 600 650 350 400 450 500 550 600 650 700 750
Wavelength (nm) Wavelength (nm)

UV spectra of the PL spectra of the

molecules in toluene molecules in toluene

Significant absorption in visible spectrum

 Vinazenes used for OPVs

Solubilizing groups for

solution processing

Conjugated
chemical links
HV-BT
S
N N

NC CN
N N

NC N N
CN

Electron accepting sites

EV-BT
Better solubility
Can be thermally sublimed as well
 Preparation of OPV Devices

POPT donor polymer

New Electron Acceptor

Solution processed active layer

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 POPT with HV-BT

POPT

Voc = 0.62 V, FF = 0.40, PCE = 1.41%

Kietzke, T., Shin R.Y.C., Egbe, D.A.M., Chen, Z.K., and Sellinger, A., Macromolecules, 2007, 40, 4424-4428.
Shin R.Y.C., Kietzke, T., Sudhakar, S., Dodabalapur A., Chen, Z.K., and Sellinger, A., Chem. Mater., 2007, 19(8), 1892-
1894.
Woo, C.W., Holcombe, T.W., Tam, T.L., Sellinger, A., Frechet, J.M.J., Chem. Mater. 2010, 22 (5), 16731679
 Can we make better acceptors?

Solubilizing groups for

solution processing

Conjugated
chemical links

S
N N

NC CN
N N

NC N N
CN

Electron accepting sites

Corresponding electron donor has charge mobility (cm2/V sec) in 10-4

range. Is charge transport mis-match a problem?
Improving Organic Acceptor Materials
Improved Acceptor Materials?

S
O N N O

N N

O O
Acceptor Materials: Computational Studies

Ground-state geometries

LUMO

HOMO
 Synthetic Scheme for PI-BT/NI-BT
PI-BT

PI-BT

NI-BT

NI-BT
31
 New Acceptor Properties
-3.1 eV -3.1 eV
PI-BT
Normalized Absorption (arb. units.)

NI-BT -3.69 eV
1 -3.84 eV

P3HT
0.8 Thin Film P3HT

0.6
PI-BT NI-BT
-5.1 eV -5.1 eV
0.4

-6.05 eV -5.99 eV
0.2

0 ELUMO ~ 0.6 eV ELUMO ~ 0.7 eV

200 300 400 500 600 700 800 900
Wavelength (nm) EHOMO ~ 0.9 eV EHOMO ~ 0.9 eV

Peak acceptor absorption is in visible spectrum

Larger ELUMO,Acc EHOMO,Don than for P3HT:PC60BM

Tunable LUMO expected higher Voc than fullerenes

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 J-V Curve Optimal Devices
8
PI-BT P3HT:PI-BT P3HT:NI-BT
6 NI-BT Solvent Chlorobenzene Chloroform
Current Density (mA cm-2)

4 Thickness (nm) ~ 90 ~ 120

2 Cathode LiF(1nm)/Al Ca(7nm)/Al

Anneal Pre/Post Post Pre
0
Ann. Temp/Time 110 C/3min 110 C/10min
-2 Jsc (mA/cm2) 4.7 1.2
-4 Voc (V) 0.96 0.51
FF 0.56 0.35
-6
PCE (%) 2.54 0.22
-8
-1 -0.5 0 0.5 1 1.5
Voltage (V)

Believed highest efficiency BHJ with non-fullerene acceptor

and commercially available P3HT donor

High voltage as expected with higher-lying LUMO

Why is the efficiency for NI-BT 10X lower? 33

 EQE Spectra of P3HT:PI-BT Device

0.5
P3HT:PI-BT EQE

EQE (%) or Absorption (arb. units)

P3HT Absorption
0.4 PI-BT Absorption

0.3

0.2

0.1

0
300 400 500 600 700 800 900
Wavelength (nm)

Significant photocurrent generation from acceptor absorption

34
 Molecular Simulation Ground State Geometry

27.3 2.06

2.06

PI-BT NI-BT

Twisting of NI-BT molecule due to steric interactions may

prevent crystallization in films

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 GIXS Acceptor Crystallization

P3HT:PI-BT (CB) P3HT:NI-BT (CF)

P3HT Only - CB P3HT Only - CF

More acceptor peaks in PI-BT sample than NI-BT

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 OPV Conclusions

Very promising new acceptor materials as potential

replacement for fullerene derivatives
Synthesized in minimal step/moderate yield reactions
Tunable energy levels
Anticipated to be much less expensive than fullerenes

Initial device performance very promising

From initial PCE of 0.1% >2.54% PCEmax, 5 years of R&D, (5-7
total researchers)
Close interaction between chemists and device
engineers/physicists
 Acknowledgements

Co-PI - Prof. Michael McGehee

Synthesis Dr. Xu Han (now at DuPont R&D Shanghai), Dr. Andrew
Higgs
Device Fabrication/Characterization Jason Bloking, Jack Kastrop
Quantum Calculations Dr. Chad Risko, Dr. Joe Norton, Laxman
Pandey, Dr. Jean-Luc Bredas (Georgia Tech)

Funding Sources:

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