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Polymer Tandem Solar Cells

Letian Dou, Jingbi You, Gang Li, Yang Yang Materials Science and Engineering, UCLA yangy@ucla.edu
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Morphology (control) in BHJ solar cell


BHJ very high interfacial area Efficient Exciton dissociation Charge transport - major bottleneck Phase separation
X. Yang & J. Loos, Macromolecules 40, 1353 (2007)

Interpenetration Network Both Donor & Acceptor Domain size twice of exciton diffusion length (2 x LD) ~20 nm

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Bulk Heterojunction Polymer Solar Cells


Device Structure

eOC H 2
S S S n/4 S

(1) (2) (3) (4)

Absorption ( A) Exciton Diffusion ( ED) Charge Transfer ( CT) Charge Collection ( CC)
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P3HT
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PCBM

Various Polymers for High Performance Solar Cells


Organic Bulk Heterojunction Solar Cell Polymer P3HT PSBTBT PBDTTBT PBDTTT-C PBDTTT-CF PSiFDBT PBDTTPD PDPPTPT PCPDTBT PTB1 PTB7 Acceptor PC61BM PC71BM PC71BM PC71BM PC71BM PC61BM PC71BM PC71BM PC71BM PC71BM PC71BM Voc [V] 0.61 0.67 0.92 0.7 0.76 0.9 0.85 0.8 0.88 0.56 0.74 Jsc [mA cm-2] 10.6 13.6 10.7 14.7 15.2 9.55 9.81 10.3 10.6 15 14.5 Performance FF [%] 67.4 61.5 57.5 64.1 66.9 50.7 66 65 66 63.3 68.9 PCE [%] 4.37 5.6 5.66 6.58 7.73 5.4 5.5 5.5 6.1 5.3 7.4 Ref. Y. Yang [1] Y. Yang [2] Y. Yang [3] Y. Yang [4] Y. Yang [5] Y. Cao [6] A. K-Y Jen [7] M. Leclerc [8] R. Janssen[9] A. Heeger [10] L. Yu [11] L. Yu [12]

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[1] G. Li, V. Shrotriya, J. Huang, Y. Yao, T. Moriarty, K. Emery, Y. Yang, Nat. Materials 2005, 4, 864 [2] J. Hou, H. Chen, S. Zhang, G. Li, Y. Yang, J. Am. Chem. Soc., 2008, 130 (48), 16144-16145 [3] L. Huo, J. Hou, S. Zhang, H. Chen, Y. Yang, Angew. Chem. Int. Ed. 2010, 49, 1500 1503 [4] J. Hou, H. Chen, S. Zhang, R. Chen, Y. Yang, Y. Wu, G. Li, J. Am. Chem. Soc. 2009, 131, 15586 15587 [5] H. Y.Chen, J. H. Hou, S. Q. Zhang, Y. Y. Liang, G. W. Yang, Y. Yang,L. P. Yu, Y. Wu, G. Li, Nat. Photonics 2009, 3, 649 [6] E. G. Wang, L. Wang, L. F. Lan, C. Luo, W. L. Zhuang, J. B.Peng, Y. Cao, Appl. Phys. Lett. 2008, 92, 033307 [7] Y. Zhang, S. K. Hau, H. Yip, Y. Sun, O. Acton, A. K.-Y. Jen, Chem. Mater. 2010, 22, 2696 2698 [8] Y. Zou, A. Najari, P. Berrouard, S. Beaupre, B. R. Aich, Y. Tao, M. Leclerc, J. Am. Chem. Soc. 2010, 132, 5330 5331 LABs J. C. Bijleveld , V. S. Gevaerts , D. Nuzzo , M. Turbiez , S. Mathijssen , D. Leeuw , M. Wienk , R. Janssen, Adv. Mater. 2010, 22, E242 E246 [9] [10] S. H. Park, A. Roy, S. Beaupre, S. Cho, N. Coates, J. S. Moon, D. Moses, M. Leclerc, K. Lee, A. J. Heeger, Nat. Photonics 2009, 3, 297 [11] Y. Liang, Y. Wu, D. Feng, S. Tsai, H. Son, G. Li, L. Yu, J. Am. Chem. Soc. 2009, 131, 56 57 [12] Y. Liang, Z. Xu, J. Xia, S. Tsai, Y. Wu, G. Li, C. Ray, L. Yu, Adv. Mater. 2010, 22, E135 E138

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Chemical Structures

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Best published OPV efficiencies


* PC60BM ** PC70BM
8.0 7.5 7.0

10.2%, UCLA* 9.2%, SCUT 8.62%, UCLA 8.37%, SCUT

PBDTTT-CF** 7.73% PTB7**

Efficiency (%)

6.5

PBDTTT-C** PCPDTBT**

6.0 5.5 5.0 4.5 4.0 2006 2007 2008 2009 2010 2011

PSBTBT** PSiFDBT*

PBDTTBT** PBDTTPD** PTB1** PDPPTPT**

4.3% P3HT*

Year
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*uncertified,
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Achievements of UCLA polymer solar cell project


UCLA-Solarmer: 8.13%! 8.62%!
Nature Photonics, 3, 649 (2009) 2-Terminal 3-Terminal

2011

Highly Efficient Tandem Cells


Advanced Materials, 21, 1 (2009) Advanced Materials, 21, 4238 (2009)

2010

Vertical Phase Separation


Advanced Functional Materials (2009)

2009

Semi-transparent Solar Cell


Advanced Materials, 20, 415 (2008)

Solvent Mixture Effect


Advanced Materials, 18, 1783 (2008)

Low Bandgap Polymers


J. Am. Chem. Soc., 131, 15586 (2009) 2008 Anisotropy in Single-Crystal Photovoltaic

Solvent Annealing Effect


Advanced Functional Materials (2007)

2007

Advanced Materials, 20, 435 (2008)


Al

Inverted Structure
Applied Physics Letters (2006)

Transition Metal Oxide as Buffer Layer


Applied Physics Letters (2006)
PED OT:PSS

2006 Accurate Measurement and Characterization


Advanced Functional Materials, 16, 2016 (2006) 2005 Controlling of Active Layer Growth Rate (4.4%) Nature Materials, 4, 864 (2005) 2003 (<1%) UCLA YY LABs

Al BCP C60 Crystal PEDOT:PSS ITO Glass


BCP

BCP

C60

C60

Crystal
Crys tal

PEDOT:PSS

ITO ITO

G las s

Glass

Introduce to Solarmer Energy, Inc. a UCLA startup


Founded March, 2006 in Los Angeles, California Developing plastic solar panels for
Smart fabrics Portable electronics Building Integrated PV (including power windows)

Certified world records for plastic solar cells Currently 26 employees www.solarmer.com

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Common Terms
Short Circuit Current V = 0, I = ISC Open Circuit Voltage I = 0, V = VOC Fill Factor I max Vmax FF = I sc Voc Power Conversion Efficiency:

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PMAX FF v I sc v Voc PCE ! ! Plight Plight


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Limitations of Polymers
Narrow absorption range Low carrier mobility (~ 10-5 cm2/ V-s)
5x10
21

Photon Density (Number /m /nm)

Solar Spectrum Green polymer absorption 1.0

Less than 30% of solar spectrum is absorbed

4x10

21

Absorbance

3x10

21

2x10

21

0.5

1x10

21

Solution: Tandem Solar Cell


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0 300

30% of solar spectrum 0.0 1200

600

900

Wavelength (nm)

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Tandem Solar Cells




Tandem Cell:
Stack two solar cells with complementary absorption range on top of each other. Enhances the net absorption range.
Solar Spectrum Green polymer absorption Red polymer absorption

Photon Density (Number /m /nm)

5x10

21

1.0

ITO
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4x10

21

Absorbance (a.u.)

3x10

21

0.5 2x10
21

PV1 n h

p+

PV2

1x10

21

60% of solar spectrum

0 300

600

900

0.0 1200

Wavelength (nm)

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Working Mechanism of Tandem Cell


Light absorption by the two sub-cells Collection of holes from rear cell and electrons from front cell Efficient recombination of electron & holes in the interlayer Collection of carriers to the external circuit
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Front Cell Anode

Cathode Rear Cell

Interconnecting layer

Requirements for interconnecting layer (ICL)


Optically transparent
Cathode

Electrically conductive
Anode

Front Cell

Rear Cell

Physically robust

Interconnecting layer

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2 Terminal Series Connected Polymer Tandem Cells


Regular structure:
+

Inverted structure:
+

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ITO ITO

Traditional Tandem Cell Design


Absorption range from 300nm to 850nm.
Metal Electrode

PSBTBT:PC70BM
TiO2:Cs

P3HT:PC70BM

PEDOT:PSS PEDOT:PSS
TiO2 PEDOT:PSS Glass / ITO Substrate

+
0.60V

1.25V 0.66V

hR

PSBTBT

P3HT

PCE(%) P3HT:PC70BM 3.77 3.94 PSBTBT:PC70BM

Voc (V) 0.60 0.67 1.25

Jsc (mA/cm2) FF(%) 9.27 10.71 7.44 66.6 55.8 63.2


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Tandem 5.90 Sista, S. et al Adv. Mater. 2010, 22, 380 383

Tandem Device
ITO/PEDOT/P3HT:IC60BA/TiO2/m-PEDOT/PSBTBT:PC70BM/Ca/Al
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Current Density (mA/cm )

2 0 -2 -4 -6 -8 -10 -12 -14


P3HT:IC60BA PSBTBT:PC70BM Tandem

-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

J. Yang et al, Adv. Mat., 23, 3465, 2011

Bias (V)

Device P3HT:IC60BA PSBTBT:PC70BM YY LABs Tandem


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VOC (V) 0.82 0.66 1.47

JSC (mA/cm2) 8.5 13.7 7.6

FF (%) 65 54 63

PCE (%) 4.5 4.7 7.0


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Performance Under Various Light Intensity


8.0 7.5

PCE (%)

7.0

6.5

6.0

100

80

60

40

20

Light Intensity (mW/cm2)

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1 sun 0.5 sun 0.35 sun 0.18 sun 0.1 sun

Light Intensity (mW/cm2) 100 50 35 18 10

VOC (V) 1.47 1.40 1.39 1.36 1.32

JSC (mA/cm2) 7.6 4.03 2.83 1.54 0.88

FF (%) 60 62 63 64 67

PCE (%) 6.6 7.0 7.2 7.4 17 7.8

Inter-connecting layer
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Current Density (mA/cm )

10 1 0.1 0.01 1E-3 1E-4 1E-5 -2

Before Illumination After Illumination

Very low dark forward injection current before exposure to light.

Photoconductivity of TiO2

-1

Bias (V)
4

Large interface resistance observed when UV light is cut-off leading to S-shape in the J-V curves under light bias.

Current Density (mA/cm2)

W/O UV activation With UV activation 0

-4

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-8

-0.4

0.0

0.4

0.8

1.2

1.6

Bias (V)
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Working mechanism of interlayer


EC EF TiO 2 PEDOT

Before UV Light exposure

Schottky to Ohmic Transition


Tunne ling

TiO 2

PEDOT

After UV Light exposure

UV Light increases electron concentration in TiO2


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Inverted Polymer Solar Cell and Inverted Polymer Tandem Solar Cell

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Why Inverted Polymer Tandem Solar Cell?


To avoid PEDOT layer; Solution processible metal-oxide ICL is easier to handle and reproducible n-type metal-oxide based cathode for better stability

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Previously reported inverted single layer cells


ITO/Cs2CO3 / BHJ / V2O5 (Au) ITO/ZnO / BHJ / Ag ITO/TiO2 / BHJ/ PEDOT (Au) PTE / TiO2 / BHJ/ PEDOT (Ag) PCE = 2.25% [1] PCE = 2.58% [2] PCE = 3.1% [3] PCE = 3.6% [4] 3.0
Low work function electrode Good interfacial contact

3.7 Cs2CO3 P3HT

2.9 Ca

Regular Structure

4.3 Al

4.7 ITO 5.2 PEDOT

PCBM 4.9 V2O5 6.1

Inverted Structure

1. G. Li, Appl. Phys. Lett. 88, 253503 (2006) 2. M. S. White , Appl. Phys. Lett. 89, 143517 (2006) 3. C. Waldauf, Appl. Phys. Lett. 89, 233517 (2006) 4. R. Steim, Appl. Phys. Lett. 92, 093303 (2008)

Efficient inverted (single layer) solar cell


0 -2 Jsc (mA/cm )
2

-4 -6 -8 -10 -12 0.0

No annealing o 70 C annealing o 120 C annealing o 150 C annealing o 170 C annealing o 210 C annealing

Anneal T (oC) RT 70 120 150 170

Jsc (mA/cm2) 7.61 9.36 10.86 11.63 10.38 10.45

Voc (V) .550 .565 .580 .590 .582 .584

PCE (%) 2.31 2.92 3.69 4.19 4.08 3.73

FF (%) 55.2 55.2 58.6 64.0 62.1 56.0

0.1

0.2 0.3 0.4 Bias (V)

0.5

0.6

210

In 2008, we have demonstrated single layer tandem solar cell with 4.2% efficiency, which is comparable to our previously reported best regular P3HT:PCBM device structure 4.4%
H.H. Liao et al., Appl. Phys. Lett. 92, 173303 (2008)

Unique inter-connecting layer based on all metal oxides ITO/ZnO/PVunit1/MoO3/Al/ZnO/PVunit2/MoO3/Al


Cathode Inter-connnection layer Anode

Negligible optical loss due to absorption; Excellent electrical connection; Excellent Processibility The use of acidic PEDOT:PSS can be avoided

Advanced Materials, 23, 1282 (2011)

Device structure
- illustration & cross-section SEM

+ _

PSBTBT:PC6 0BM rear subcell P3HT:PC6 0BM front subcell


Advanced Materials, 23, 1282 (2011)

Optimized device performance

Devices

Voc (V)

Jsc (mA/cm2)

PCE (%)

FF (%)

Tandem
P3HT:PCBM ref PSBTBT:PCBM ref

1.20
0.58 0.64

7.84
8.6 11.7

5.1
3.2 3.7

54
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Advanced Materials, 23, 1282 (2011)

Optical properties of each layer

Energy diagram

Optical loss of the ICL has been minimized. Ideal band structure for the ICL
Advanced Materials, 23, 1282 (2011)

High performance Inverted tandem solar cell


Using designed LBG polymer PBDTT-DPP Devices structure and band alignment

(a) The structure of inverted tandem solar cell, and (b) band alignment of each layer
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Chemical structure of PBDTT-DPP

PBDTT-DPP

Materials used in inverted tandem solar cells.


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Properties of PBDTT-DPP
Absorption

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Designed low bandgap polymer PBDTT-DPP (Eg=1.44 eV) has complementary absorption with wide bandgap polymer P3HT (Eg=1.9 eV).

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Properties of PBDTT-DPP
C-V
10 9
60
PBDTT-DPP LUMO = -3.63 eV HOMO = -5.30 eV

SCLC
8

J0.5 (mA0.5/cm)

7 6 5 4 3 2

Current/QA

30

-30

1
-1000 -500 0 500 1000 1500

-1500

0 0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

Voltage/mV

Bias (V)

Low HOMO level: -5.30 eV

High hole mobility: 3.110-4 cm2V-1s-1

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High performance of low bandgap polymer (PBDTT-DPP) based single junction solar cell

 Low bandgap polymer (PBDTT-DPP, Eg=1. 44 eV) owns high mobility (3.110-4cm2V-1s-1 ), low HOMO energy (-5.3 eV), the PBDTT-DPP based single junction solar cells showed as high as 6.5% power conversion efficiency (PCE).
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High performance inverted tandem solar cell by using designed new LBG polymer PBDTT-DPP

NREL certified I-V curve

VOC (V) Front cell (P3HT:ICBA) Rear cell (PBDTT-DPP:PC71BM) Tandem (NREL)
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JSC (mA/cm2) 9.56 13.5 8.26

FF (%) 70.2 65.1 66.8

PCE (%) 5.7 6.5 8.6

0.85 0.74 1.56

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L. T. Dou et al, Nat. Photonics, in press

EQE of the tandem device:


a b

Front cell
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Rear cell

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L. T. Dou et al, Nat. Photonics, in press

High stability of our inverted tandem solar cell device

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L. T. Dou et al, Nat. Photonics, in press

UCLA 10.2% tandem solar cell based on new polymer

Voc (V) Earlier Tandem devices


(Measured in NREL)

Jsc (mA/cm2) 8.26 7.2(front cell by EQE) 7.3(Rear cell by EQE) 9.93 8.83(front cell by EQE) 8.85(Rear cell by EQE)

FF (%) 66.8 70(Front cell) 63(Rear cell) 68.63 69(Front cell) 67(Rear cell)

PCE (%) 8.62%

1.56 0.84+0.72 1.503 0.84+0.67

P3HT:ICBA (front cell) LT13:PCBM(rear cell) Present Tandem devices


(Measured in Our Lab)

10.22%

P3HT:ICBA (front cell) New Poly:PCBM(rear cell)

Summary
We have demonstrated high-performance tandem solar cell and investigated the ICL working mechanism. We demonstrated low bandgap polymer (PBDTTDPP) specifically designed for tandem solar cells. The significance of the PBDTT-DPP polymer is clearly demonstrated in the inverted tandem cell with 8.62% PCE measured by NREL. Finally, a new los bandgap polymer pushes our tandem solar cell to reach a record 10% PCE.
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Polarizing Organic Photovoltaics


-----A unique concept combines OPV and LCD-----

Rui Zhu, Ankit Kumar, and Yang Yang Materials Science and Engineering, UCLA California Nanosystem Institute (CNSI), UCLA

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Liquid Crystal Displays

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Basic Principle of LCDs

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Linear Polarizer
Polymer chain orientation

Polymer chain orientation Definition of polarization: using the oriented polymer chain axis as the reference parallel polarized light: optical polarization is parallel to polymer chain, absorbed perpendicular polarized light: optical polarization is perpendicular to polymer chain, transmitted Dichroic ratio DR = Absorption (Parallel) Absorption (Perpendicular)
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Photovoltaic (PV) Polarizer

Functions: 1. Polarizer, the traditional polarizer function 2. PV device, harvesting ambient light, sunlight, or even the backlight energy.
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Requirements for PV Polarizer


High dichroic ratio (DR) Efficient PV performance, especially under low light intensity Electrodes with good transmittance
Commercial Polarizer

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Technology Choice for PV Polarizer


Inorganic v.s. Organic Photovoltaics (OPVs)
low specific-weight mechanical flexibility easy tunability of material property better performance in low light intensity transparent solar-cells

Unique feature: organic molecule alignment gives the anisotropic effect

Polarizing Organic Photovoltaic (ZOPV)


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Achieving ZOPV Devices


Materials:
PC60BM P3HT

Devices:

Steps: 1. Align P3HT molecular chain, for anisotropic effect. 2. Form interpenetrated donar-acceptor networks, for efficient charge separation and transportation. 3. Electrode deposition.
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1. P3HT Alignment



//
R. Zhu , Y. Yang., et. al. Adv. Mater., 2011, 23, 4193 46 G. Derue, et. al., J. Am. Chem. Soc., 2005, 127, 8018

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2: Forming Interpenetrated Networks


A). Coat PCBM on aligned P3HT --- form bilayer structure B). Thermal Annealing --control diffusion of PCBM into P3HT
PC60BM

Forming quasi-bilayer interpenetrated networks


Rubbed P3HT

S. H. Tolbert, et al., J. Phys. Chem. C 2009, 113, 20050 C. J. Hawker, et al., Adv. Energy Mater. 2011, 1, 82

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3. Electrode Deposition

Test condition AM1.5G, 1 Sun, unpolarized light s-mode polarized light, 0.33 Sun, p-mode polarized light, 0.33 Sun, //

Jsc (mA cm-2) 2.74 0.41 1.45

Voc (V) 0.596 0.513 0.568

FF (%) 42.16 53.08 50.27

Eff (%) 0.69 0.34 1.25


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Ratio(Jsc)=3.54

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Future Challenges
Highly transparent electrodes
Front electrode, back electrode

Efficient film orientation process


To achieve higher DR

Novel OPV materials


Easy to align, to achieve the high DR. High PV performance, to achieve high electricity production

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Is OPV a real technology?


Things need to be concerned: Stability, Panel Efficiency, Material Cost (Donor, Acceptor, Charge injection layers, metal oxides, substrates), Manufacture cost, Encapsulation
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OLED Experience
In 1993, OLED have only a few hours of lifetime and efficiency is much less than 10 lm/watt. Currently, OLEDs have more than 50K hours of lifetime, and higher than 50 lm/watt efficiency. In May 2010, Samsung announced in SID that OLED will be the next trend of display technology.
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What are next to come?


The efficiency of OPV has been increased from 6% to 8% in 2010; and we anticipate the efficiency will break the 10% barrier in 1-2 years, and eventually to reach the 15% barrier in a few years. (This will lead to 10-12% panel efficiency.) This is significantly important in renewable energy, since the OPV solar panel can be printed like newspaper. It is time that industrial manufacture to kick-in, to work on new materials, large area coating, stability, and modules; and we welcome opportunities for collaborations.
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Acknowledgement
Dr. Dr. Mr. Mr. Youjun He (ORNL) Seiichiro Murase (Toray) Jun Yang, (Solarmer) Tom Moriarty, Dr. Keith Emery (NREL)

Funding:

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