Achieving High Performance Solar

Cells through Innovative Approaches

Yang Yang 楊陽 (yangy@ucla.edu)

Materials Science and Engineering and
California Nano-System Institute
UCLA
 Let’s start from a number:

0.08%!
The ratio Solar energy occupied in
US energy sources.

Why?
2
The answer is:
 Cost,
 Availability
 Installation (counts for 50% of the cost)

We need a disruptive technology or

technologies to solve this problem

3
 Our Goals in PV technology
• Low cost (or very low cost) and high performance
solar cells as future source of energy.

• To reach this goal, solar cell technology must be

simple to manufacture, robust in various
environments, and it must be high performance,
and easy to deploy.

• Solution process is the way to go

Introduction- Organic materials vs Inorganics
 Covalent bonds
 van de Waals force

 With no charge carriers

 With certain amount of charge carriers
Very small amount due to traps or
impurities 1010~1018 cm-3

 Discrete energy levels (however,  Continuous band structure

band structure is currently used)

Remember:
Exciton binding energy
~0.3 eV

* NOTE: Ba nd st ruct ure is used for o rg anic e lect ro nics for

simp licit y
5 09/10/09
Introduction-II Conjugated Polymers

 π – conjugation
π – bonds from pz orbitals

 Alternating single-double bonds

 Delocalized π-electron clouds

6 09/10/09
 7
YY LAB

UCLA Department seminar 09/10/09

 YY LABs

Economic Viability UCLA

1. Can renewable energy supply our energy needs?

• Annual energy consumption (US): 134 quadrillion btu[1]
• Average solar radiation: 6 kWh/m2/day[2]
• Assuming average solar cell efficiency: 10%
• Require area: 70,600 sq-mile ~ 25% of Texas

2. Can it be done economically?

• Current electricity cost: $0.08-0.10/kWh[1]
• Assuming module cost $75 per m2 (FYI, x-Si panel is $400/m2)

8 1. US Dept of Energy - 2007 Annual Energy Outlook

2. http://rredc.nrel.gov/solar/old_data/nsrdb/redbook/atlas/
 YY LABs

Best Research Cell Efficiencies UCLA

Crystalline Si Cells
24 Multicrystalline
Thin Film Technologies
Poly-silicon Cu(In,Ga)Se2
Cu(In,Ga)Se2
20
CdTe
Amorphous Si:H
16 (stabilized)
Efficiency (%)

Emerging PV CdTe
Organic cells
12
Amorphous Si:H

4 Organic cells

0
1975 1980 1985 1990 1995 2000
9
www.nrel.gov/pv/thin_film/docs/kaz_best_research_cells.ppt
 UCLA Polymer Solar Cells (~5%)

Ca 2.9eV
- Metal electrode + LUMO P3HT 3.0eV
3.7eV
LUMO PCBM
Active layer 4.7eV
HOMO P3HT
ITO
5.2eV 4.9eV

PEDOT

HOMO PCBM
6.1eV

Regioregular poly-(3-hexyl-thiophene)
(RR-P3HT)
PCBM

OCH2
O
Glass ITO PEDOT:PSS S S
S S

n/4

YY Lab
Li et al., Nature Materials, 4, 865, (2005) 
UCLA
 Operation Mechanism of OPV Device
 Photovoltaic Effect Under Short Circuit Condition
The production of opposite charges ηED
in semiconductor devices under ηCT

illumination and the subsequent ηCC

2.9 eV
collection of charges at the electrodes ηA
3.0 eV LUMO P3HT
 Steps in the process 3.7 eV LUMO PCBM

 Light absorption (η )
4.7 eV
A
5.2 eV
 Motion of excited species (ηED)
4.9 eV HOMO P3HT
 Charge separation (ηCT)
6.1 eV HOMO PCBM
 Charge collection (ηCC)
ITO PEDOT P3HT PCBM Ca
 Overall Efficiency
η = ηA × ηED × ηCT × ηCC
 YY LABs

Efficiency
UCLA

Vmax ∙Jmax
Efficiency (η) = ∙ 100
Incident Power

12
 However, OPV is not simple device
 What happens in solvent drying process?
 Solvent removing speed is function of:
 solvent, spin-speed, spin-cast time, environment …

Shorten the polymer film drying time

Decrease of the Polymer Crystallinity

Purple phase Transition Yellow phase
Nanoscale Phase Separation
in P3HT:PCBM
Solvent annealed Fast drying

200nm 200nm

PE
(300) (010) DO (010)
T/
PS
(200) S

(100)

0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0
qxy (Å )-1 qxy (Å-1)
Photovoltaic performance
- strong function of cast condition

Fast drying film

-2
Jsc (mA/cm )

-4 ts
2

20 sec
-6 30 sec
40 sec
50 sec
-8
52 sec
55 sec
-10 20 minutes drying time 80 sec

-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Bias (V)
 External Quantum Efficiency
70
20 min drying time Spin-coating time • Changing in both
60 20 sec magnitude & shape
50 sec
55 sec • Note the loss of IPCE
50 80 sec
@ 600 nm
40
• In P3HT absorption,
IPCE (%)

30
600 nm corresponding to
the interchain
20 interaction ( π-π
Fast drying film
stacking)
10

0
300 400 500 600 700 800 •PCE = ~ 4 - 5%
λ (nm)
 Strategies on New Generation OPV
 Basic research is needed to understand the device
operation mechanism: charge transport, defects,
interface property, ..
 Novel materials for smaller Eg, higher carrier
mobility, high optical density are required.
 Stability study
 Hybrid-structure, combing with nano-structure, QD,
and other formats of materials structures

17
 High Gain Photoconductivity (PC)
Device structure and chemical structure of capping ligand

Cathode
Anode
P3HT:PCBM
blend (with or
ITO without CdTe
NPs)
Glass PEDOT:PSS
H
CdTe nanoparticles(NPs) with the N
designed ligand, PMDTC, are C
blended into the P3HT:PCBM film to
achieve high photoconductive gain S
devices. CdTe

Chen et al, Nature Nanotechnology, 3, 543, 2008. 18

J-V charateristics
ITO/PEDOT:PSS/Polymer Blend(P3HT:PCBM/CdTe NPs)/Ca/Al

High photoconductive gain was

observed under reverse bias after
blending with CdTe NPs.

Device A- P3HT:PCBM blend

Device B- P3HT:PCBM blend with CdTe NPs
 EQE measurement

For regular P3HT:PCBM (Device

A) solar cell, only 10% increase in
EQE when applied bias to -5V.

External quantum efficiency (EQE) of device B

(with CdTe NPs) reached 8000% at 350nm under
-4.5V. Higher than 100% EQE implies there is
current injection from external circuit, since
impact ionization is unlikely to happen in
organic/polymer system.
 Mechanism Study
Hole-only devices with MoO3/Al
electrode. From the J-V curve, hole
injection from MoO3/Al electrode is
much higher than from ITO side.
MoO3/Al This implies the vertical distribution
of NPs in the film might not be
uniform, i.e. higher concentration
near the top surface.

CdTe NPs act as electron traps,

and the trapped electrons lower the
hole injection barrier from Ca/Al
electrode to the polymer film.
AFM Images
No PC Gain Minor PC Gain High PC Gain

Phase

P3HT:PCBM P3HT:PCBM P3HT:PCBM

+ solvent annealing + 3.1% CdTe NPs + 3.1% CdTe NPs
+ solvent annealing

The morphology changed significantly after adding CdTe NPs

coupled with solvent annealing, possibly due to the higher
concentration of NPs near the top surface.
Summary for High Gain PC
We demonstrated a high-gain photoconductivity based on nano-particle
blend in P3HT:PCBM blend.

The mechanism is attributed to the interface charge trapping and

subsequently lower the hole injection barrier at low voltage.

Trap-engineering for polymer electronics is an important topic.

23
Radiation Effect of
Polymer Solar Cells

Manuscript accepted by Nanotechnology

Motivation
 Exploring the effect of high dose x-ray radiation
on organic solar cell
 Exploring the possibility of the application of
OPV in space
 Organic vs. Inorganic PV
 Lower efficiency now, but constantly improving
 Light weight
Outer space impact on OPV
 Pros
 No O2 & H2O concerns
 Potentially it improves OPV Lifetime
 Cons
 StrongerSun Light (AM0 is 1360W/m2)
 Much stronger high energy radiation!
 We present the very first set of data on
radiation effect on OPV
Experiment
 Polymer solar cells fabricated, tested (one-sun
condition) & encapsulated in UCLA
 Devices shipped to Air Force Research
Laboratory (AFRL) Kirtland AFB, NM
 ARACOR 4100 X-irradiation system
 Electrical probing - Hewlett Packard 4142
 Light source - halogen lamp (maximum 150 W)
 Device Data - UCLA
0

-2
PCE Jsc Voc FF
2
4.16% 10mA/cm 0.613V 68%
-4
J (mA/cm )
2

Device 1
-6 Device 2
Device 3
Device 4
-8

-10

-12
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Bias (V)
Response of Voc under radiation
Irradiation at 8.33 kRad(SiO2)/min

0.59

0.58
60 min
0.57
500K Rad(SiO2)
Voc (V)

0.56

0.55

0.54

0.53
0 50 100 150 200 250 300
Time (minutes)
Response of Jsc under radiation
Irradiation at 8.33 kRad(SiO2)/min

1.00
Normalized Short Circuit Current

0.95
60 min
0.90
500K Rad(SiO2)
0.85

0.80

0.75

0.70
0 50 100 150 200 250 300
Time (minutes)
Response of PCE under radiation
Irradiation at 8.33 kRad(SiO2)/min
Normalized Power Conversion Efficieny

1.00 4.16%
0.95
0.90
0.85
60 min
0.80
500K Rad(SiO2)
0.75 2.9%
0.70
0.65
0.60
0.55 2.2%
0.50
0 50 100 150 200 250 300
Time (minutes)
Reduced Glass Transmission ~ 7%
i.e. 92% to 85%
100

Air as reference

90
Transmission (%)

80
OPV
response
70
Glass
Glass/PEDOT
Glass/ITO/PEDOT
60
250K Rad Glass
250K Rad Glass/PEDOT
250K Rad Glass/ITO/PEDOT
50
300 400 500 600 700 800 900 1000

λ (nm)
 Minimal polymer absorption loss
- Better than glass?
Fresh Glass_PEDOT as reference
P3HT:PCBM film transmission with various radiation
100
Transmission (%)

80

60 No Rad
M54 50K rad
M71 100k Rad
M88 250k Rad
40
M89 500k Rad

20

300 400 500 600 700 800 900 1000

λ (nm)
Summary
 Polymer solar cell efficiency drops to 54% of
original value after 500K Rad strong x-ray
irradiation

 Significant efficiency recovery phenomenon

observed – recover to 70% after 2 hours

 Take into account of radiation induced

transmission loss from glass, polymer PV cell
can recover to 76% of original efficiency
Conclusion of Part III
 Very interesting radiation damage and recovery
phenomenon effect observed

 Organic solar cells could be sufficiently radiation

tolerant to be useful for space applications
Technology transfer
 One startup “Solarmer Energy Inc.”
established in 2006 to commercialize our
technology.
 Solarmer has licensed 7 UCLA patents
and hire 5 of our students.

36
Acknowledgements:
 Financial support from ONR, AFOSR, Solarmer
Energy on the nano-technology and its
application in polymer opto-electronic devices.
 NSF & NSFC Joint project, starting Oct. 08
 Students involved in the projects:
Gang Li, Vishal Shrotriya, Fishier Chen, Jinsong Huang.

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