한국미래기술교육연구원

태양전지세미나
2010. 9. 2.

유기 태양전지 핵심재료 개발 동향
-광활성층/
광활성층/ 유연기판/ 투명전극-
투명전극

2010. 9. 2

Ch h Lee
Changhee L
School of Electrical Engineering and Computer Science
Seoul National Univ.
chlee7@snu.ac.kr

Organic Semiconductor Lab 1/35 Changhee Lee, SNU

한국미래기술교육연구원
Contents 태양전지세미나
2010. 9. 2.

• A brief history of
organic
i solar
l cells
ll
• Active materials
• Electrodes
• Substrates
• Summary

Organic Semiconductor Lab 2/35 Changhee Lee, SNU

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 한국미래기술교육연구원
Solar Cells: Cost-performance, Loss processes 태양전지세미나
2010. 9. 2.

Loss processes in a standard solar cell:

(1) nonabsorption of belowbandgap photons;
(2) lattice thermalization loss;
(3) and (4) junction and contact voltage losses;
(5) recombination loss

Gavin Conibeer, Materials Today 10, 42 (2007) Gavin Conibeer, Materials Today 10, 42 (2007)

Organic Semiconductor Lab 3/35 Changhee Lee, SNU

Why Organic Photovoltaics (OPV)?

한국미래기술교육연구원
태양전지세미나
2010. 9. 2.

Conventional PV OPV

Expensive Lower cost (simple

device structure, Spin Coating
(3~4 $/Wp, 50 process, production
cents/kWh) facilities) Solvent Saturated
Atmosphere
High module prices, Low unit costs enable Spinner
high spec. (long life use even for shorter Cover
time) lifecycles Spun Film
Materials New applications
characteristics limit
application field (rigid, (Light, Flexible,
Semi-transparency) ITO substrate
heavy) Spinner
Bowl Spinner Base
Spinner
Motion

Si Solar cell Organic Solar cell

Organic Semiconductor Lab 4/35 Changhee Lee, SNU

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 한국미래기술교육연구원
Applications of Flexible Organic Solar Cells 태양전지세미나
2010. 9. 2.

참고: 실리콘 태양전지

http://www.konarka.com/

태양전지로 구동되는 노트북PC

대만 IT전시회
(타이베이시 세계무역센터, 2006. 5. 11. )
New Applications of Flexible Solar Cells
Organic Semiconductor Lab 5/35 Changhee Lee, SNU

한국미래기술교육연구원
Mimic “Photosynthesis” 태양전지세미나
2010. 9. 2.
Very low-efficiency: ~0.001 %!

“The power conversion efficiency for these cells is on the

order of 10-3 % which is among the highest in photovoltaic
cells using organic materials.”
Metal 2
Chlorophyll a
Chlorophyll-a
Chlorophyll a Metal 1
quartz

Plants convert light into chemical energy with a

maximum photosynthetic efficiency of ~ 6%. Light

http://en.wikipedia.org/wiki/Photosynthesis
C. W. Tang and A. C. Albrecht, J. Chem. Phys. 62, 2139 (1975)
Organic Semiconductor Lab 6/35 Changhee Lee, SNU

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 한국미래기술교육연구원
Low probability of exciton dissociation 태양전지세미나
2010. 9. 2.

Large exciton (Coulombically bound e-h pair) binding energy : 0.1 ~ 1 eV

Onsager theory of geminate recombination

Carrier generation efficiency that excitons are
separated by an external electric field,
field E,
E as a
function of the initial separation of the carriers,
r0, and orientation of the field, assuming that
the carrier motion is described by hopping
transport.
b 2 b3 b 4
E
3 − kTB
kD (E) = kR e [1 + b + + + + ...],
4πro
3
3 18 180
e3 E
where b = ,
8πε 0ε r k 2T 2
eμ
kD (E) = (Langgevin recombination rate),
ε0 εr
and E B = e-h binding energy
C. L. Braun, J. Chem. Phys. 80, 4157 (1984) P. Peumans and S. R. Forrest, Chem. Phys. Lett., 398, 27 (2004).

Organic Semiconductor Lab 7/35 Changhee Lee, SNU

한국미래기술교육연구원
1st big improvement: p/n heterojunction (“Tang cell”) 태양전지세미나
2010. 9. 2.

Au
PV (n-type)

CuPC (p-type)
ITO
Glass

Light

• p-n heterojunction
• ηp= 1 % under AM2 illumination
C. W. Tang, Appl. Phys. Lett. 48, 183 (1986)

Organic Semiconductor Lab 8/35 Changhee Lee, SNU

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 한국미래기술교육연구원
Small exciton diffusion lengths 태양전지세미나
2010. 9. 2.

Charge transfer condition :

Diffusion coefficient D ≈ 10-3 cm 2 / s
Diffusion length L = Dτ ≈ 10 nm
Eexciton < ΔI P , ΔE A
L

Exciton diffusion quencher

p-type
Exciton
V. I. Arkhipov and H. Bässler, phys. stat. sol. (a) 201, 1152 (2004) n-type

L
Only small portion of the organic layer is utilized for the carrier generation!

L ~ 10nm << α −1 ~ 100nm

Organic Semiconductor Lab 9/35 Changhee Lee, SNU

한국미래기술교육연구원
Organic solar cell with a codeposited active layer 태양전지세미나
2010. 9. 2.

Mixed Interlayer
ZnPc mixed with C60

ηp= 0.7 %

M. Hiramoto, H. Fujiwara, and M. Yokoyama, Appl. Phys. Lett. 58, 1062 (1991) D. Meissner, Y. Shirota et al, Solar Energy Materials and Solar Cells 61, 87 (2000)

Organic Semiconductor Lab 10/35 Changhee Lee, SNU

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 한국미래기술교육연구원
2nd big improvement: bulk D/A heterojunctions 태양전지세미나
2010. 9. 2.

Bulk heterojunction Ultrafast process (~100fs) & Very efficient PICT

Light

e-

Donor
Acceptor
G. Zerza, C. J. Brabec, G. Cerullo, S. De Silvestri,
N. S. Sariciftci et al., Science 258, 1474 (1992). and N. S. Sariciftci, Synth. Metals 119, 637 (2001)

Highly efficient carrier generation at bulk D/A heterojunctions PC onset at ~17 mol% PCBM, (percolation threshold)

Courtesy: Prof. Niyazi Serdar Sariciftci, Linz Institute for Organic

C. H. Lee et al, Phys. Rev. B 48, 15425 (1993) Solar Cells (LIOS), Johannes Kepler University Linz, Austria

Organic Semiconductor Lab 11/35 Changhee Lee, SNU

한국미래기술교육연구원
Dependence of IQE on morphology 태양전지세미나
2010. 9. 2.

Dynamical Monte Carlo Modelling of Organic Solar

Cells Charge
collection exciton
• IQE is found to be strongly sensitive to the scale of phase dissociation
efficiency
separation in the morphology, with a peak at 20 nm for the efficiency
PFB/F8BT system studied.
• An ordered, checkered morphology exhibits a peak IQE 1.5 times
higher than a disordered blend.
internal
quantum
efficiency

P. K. Watkins, A. B. Walker, and G. L. B. Verschoor, Nano Lett. 5, 1814 (2005)

Organic Semiconductor Lab 12/35 Changhee Lee, SNU

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 한국미래기술교육연구원
Methods for improving morphology of polymer blends 태양전지세미나
2010. 9. 2.

• Molecular structure
- eg. regioregularity of P3HT
H. Sirringhaus et al. Nature 401, 685 - 688 (1999)
Xiaoniu Yang, Nano Lett. 5, 579 (2005).

• Donor-acceptor blend ratio Good for high

g mobilityy Not ggood

T. J. Savenije, J. E. Kroeze, M. M. Wienk, J. M. Kroon, and J. M. Warman, Phys. Rev. B 69, 155205 (2004)
J. K. J. van Duren, X. Yang, J. Loos, C. W. T. Bulle-Lieuwma, A. B. Sieval, J. C. Hummelen, R. A. J. Janssen, Adv. Funct.
Mater. 14, 425 (2004).
V. Mihailetchi, et al., Adv. Funct. Mater, 15, 795 (2005)

• Solvent controls
- kind of solvents
J. C. Hummelen et al. Chem. Commun., 2116 (2003)
- solvent
l evaporation
i speedd
- mixture of solvents

• Thermal annealing

• Addition of alkanethiols
Organic Semiconductor Lab 13/35 Changhee Lee, SNU

한국미래기술교육연구원
Bulk heterojunction polymer Solar Cells 태양전지세미나
2010. 9. 2.

Light
e–
Nanoparticles dispersed in LUMO
polymers e– LUMO

HOMO h+

HOMO

Anode Electron Electron Cathode

acceptor donor
Interpenetrating network of
internal p-n heterojunctions
Æ efficient charge generation

CDT
Konarka Nanosys

Organic Semiconductor Lab 14/35 Changhee Lee, SNU

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 한국미래기술교육연구원
Progress of OPV device structure 태양전지세미나
2010. 9. 2.

1. New materials
- Low bandgap donor
- High LUMO acceptor

2. Improved morphology:
Ordered bulk heterojunction
Top electrode

Transparent electrode

3. Multijunction (tandem) structure

Single-layer PV cell
very low efficiency: ηp= 0.001 %
C. W. Tang and A. C. Albrecht,
J. Chem. Phys. 62, 2139 (1975)
Top electrode
Disordered Top cell
Bilayer PV cell bulk heterojunction Eg1
Transparent inter-electrode
ηp= 1 % under AM2 illumination ηp= 7.9 % cell efficiency (0.1 cm2)
C. W. Tang, ηp= 3.9 % module efficiency Bottom
B tt
Appl. Phys. Lett. 48, 183 Solamer (2009. 12. 2; http://www.pvt- cell Eg2
(1986).
ech.org/news/_a/solarmer_breaks_organic_solar_pv_cell_conversion_
efficiency_record_hits_nre/) Transparent electrode
• N. S. Sariciftci et al., Science 258, 1474 (1992).
• C. H. Lee et al., Phys. Rev. B 48, 15425 (1993). 4. Organic/inorganic hybrid cells
• G. Yu et al., Science 270, 1789 (1995).
• J. J. M. Halls et al., Nature 376, 498 (1995).
(QD, Nanorod, Nanowire, etc.)
Current status Future directions
ηp ~8% ηp> 10 % Æ ηp> 15 %
AM1.5 100 mW/cm2 at 25 oC AM1.5 100 mW/cm2 at 25 oC

Organic Semiconductor Lab 15/35 Changhee Lee, SNU

한국미래기술교육연구원
Progress of the performance of OPVs 태양전지세미나
2010. 9. 2.
Lawrence L. Kazmerski, Journal of Electron Spectroscopy and Related Phenomena 150, 105 (2006)

Konarka (USA)
- 6.4% NREL (2009.5)

Plextronics (USA)
- 5.98% PCE (0.043cm2, 2008.
8)

Solarmer Energy (USA)

- 7.9% PCE (2009. 12)

Heliatek GmbH (Germany)

- 5.9% NREL (2 cm2, 2009. 4)

7.9 %
Solarmer
>10 %

6.4% (Konarka)
5.15% (Konarka)
Cambridge
Kodak UCSB 5.4% (Plextronix)

2007 2009 2012

Prof. Alan J. Heeger
(Nobel Laureate
Chemistry 2001) Prof. N. Serdar Sariciftci
Dr. Ching W. Tang UCSB Johannes Kepler
Eastman Kodak Sir Richard Friend,
Universität Linz
Univ. of Cambridge
Organic Semiconductor Lab 16/35 Changhee Lee, SNU

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 한국미래기술교육연구원
Design rules for polymer solar cell 태양전지세미나
2010. 9. 2.

Single Cell Tandem Cell

M. C. Scharber, D. Muhlbacher, M. Koppe, P. Denk, C. Waldauf,
A. J. Heeger, and C. J. Brabec, Adv. Mater. 18, 789 (2006).
Organic Semiconductor Lab
Optimization condition
- Bottom cell condition: Donor ELUMO=-4eV, Gap of
bottom cell=~1.6eV, ηMAX>4%
- Top cell condition: Gap of Top cell=~1.3eV, ηMAX>4 %
Æ ~15% tandem organic solar cells
G. Dennler, M. C. Scharber, T. Ameri, P. Denk, K. Forberich, C. Waldauf,
and C. J. Brabec, Adv. Mater. 20, 579 (2008)
17/35 Changhee Lee, SNU

한국미래기술교육연구원
Organic Solar Cells: Active materials 태양전지세미나
2010. 9. 2.

- Low bandgap donors

- high LUMO acceptors
- Semiconductor Nanocrystals

Organic Semiconductor Lab 18/35 Changhee Lee, SNU

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 한국미래기술교육연구원
Donor materials 태양전지세미나
2010. 9. 2.

9 Toward low bandgap & low HOMO donor Æ Maximizing Voc in a low-bandgap polymer solar cell

Donor
V oc
Acceptor

PCPDTBT (Eg=1.46eV)

P3HT

PCPDTBT

J. Peet, J. Y. Kim, N. E. Coates, W. L. Ma, D. Moses, A. J. Heeger, N. Blouin, A. Michaud, D. Gendron, S. Wakim, E. Blair, R. Neagu-Plesu, M. Belletête, G.
Durocher, Y. Tao, M. Leclerc, J. Am. Chem. Soc., 2008, 130 (2), pp 732–742
and G. C. Bazan, Nature Mater., 6, 497 (2007)
Organic Semiconductor Lab 19/35 Changhee Lee, SNU

한국미래기술교육연구원
Internal quantum efficiency approaching 100% 태양전지세미나
2010. 9. 2.

S. H. Park, A. Roy, S. Beaupré, S. Cho, N. Coates, J. S. Moon, D. Moses, M. Leclerc, K. Lee, and A. J. Heeger, Nature Photon. 3, 297 (2009).

Organic Semiconductor Lab 20/35 Changhee Lee, SNU

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Donor materials 태양전지세미나
2010. 9. 2.

Poly[4,8-bis-substituted-benzo [1,2-b:4,5-b']dithiophene-2,6-diyl-alt-4-
substituted-thieno[3, 4-b]thiophene-2,6-diyl] (PBDTTT)-derived polymers

Bandgap : 1.77eV

HOMO VOC JSC FF PCE (%)

(eV) (V) (mA cm-2) (%) Best Avg.
PBDTTT-
-5.01 0.62 -13.2 63 5.15 4.8
E
PBDTTT-
-5.12 0.7 -14.7 64.1 6.58 6.3
C
PBDTTT-
-5.22 0.76 -15.2 66.9 7.73 7.4
CF

H.-Y. Chen, J. Hou, S. Zhang, Y. Liang, G. Yang, Y. Yang, L. Yu, Y. Wu & G. Li, Nature Photon, 3, 649, (2009)
Organic Semiconductor Lab 21/35 Changhee Lee, SNU

한국미래기술교육연구원
Bandgap & band position tunability of semiconductor NCs 태양전지세미나
2010. 9. 2.

VIS IR

ƒ Band gap & band position tunability

9 1.1 eV < Eg < 3 eV
9 dot, rods, tetrapods, dendritic shape
Æ Wide Absorption Range (VIS ~ IR)
ƒ Solution process capability
9 Assembly into superlattices
9 Spin, dip, drop casting
Æ Large area with cheap price
ƒ Multiple exction generation
Æ 1 photon to multiple excitons
Organic Semiconductor Lab 22/35 Changhee Lee, SNU

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NC-polymer hybrid p-n bulk heterojunction (BH) photovoltaics 태양전지세미나
2010. 9. 2.

Device characteristics (PCE~1.7 %)

A. P. Alivisatos Science 295, 2425 (2002)

Organic Semiconductor Lab 23/35 Changhee Lee, SNU

한국미래기술교육연구원
State-of-the-Art: NC-polymer BH photovoltaics 태양전지세미나
2010. 9. 2.

Material & device structure IV characteristic of device (EQE ~ 3.19 %)

PCPDTBT (low bandgap polymer)

TEM image & UV-vis spectra

S. Dayal, Nano Lett. 10, 239 (2010)

Organic Semiconductor Lab 24/35 Changhee Lee, SNU

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 한국미래기술교육연구원
TiO2 Nanotube Array−P3HT Based Heterojunction Solar Cells 태양전지세미나
2010. 9. 2.

Solar cell consisting TiO2 nanotube arrays

vertically oriented from the FTO-coated
glass substrate, sensitized with
unsymmetrical squaraine dye (SQ-1) (that
absorbs in the red and NIR portion of solar
spectrum), and which are uniformly
infiltrated with p-type regioregular poly(3-
hexylthiophene-2,5-diyl) (P3HT) (that
absorbs higher energy photons).

Efficiency ~3.2% under UV filtered AM

1.5G of 90 mW/cm2 intensity
G. K. Mor, S. Kim, M. Paulose, O. K. Varghese, K. Shankar, J. Basham, C. A. Grimes, Nano Lett., 2009, 9 (12), pp 4250–4257
Organic Semiconductor Lab 25/35 Changhee Lee, SNU

한국미래기술교육연구원
Organic Solar Cells: Transparent electrodes 태양전지세미나
2010. 9. 2.

- Transparent electrodes
- Optical spacers
C. J. Brabec (SIEMENS), 2004

Organic Semiconductor Lab 26/35 Changhee Lee, SNU

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Transparent Electrodes: Graphene Electrode 태양전지세미나
2010. 9. 2.

Curling, rolling and stacking can turn graphene

into buckyballs, nanotubes - and graphite

Graphite flakes of different thicknesses rubbed from bulk

graphite onto the surface of an oxidised silicon wafer
http://www.rsc.org/chemistryworld/restricted/2008/April/TheGrapheneChallenge.asp
Organic Semiconductor Lab 27/35 Changhee Lee, SNU

한국미래기술교육연구원
Flexible and Transparent CVD Graphene Electrode 태양전지세미나
2010. 9. 2.

CVD graphene transfer process

onto PET substrates

CVD graphene

Performance Details of OPV Cells Built on PET

JSC (mA cm-2) VOC (V) FF (%) PCE (%)

CVD graphene 4.73 0.48 0.52 1.18

ITO 4.69 0.48 0.57 1.27

Chongwu Zhou, ACS Nano 4, 2865 (2010)

Organic Semiconductor Lab 28/35 Changhee Lee, SNU

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Optical Spacer 태양전지세미나
2010. 9. 2.

Organic Semiconductor Lab 29/35 Changhee Lee, SNU

한국미래기술교육연구원
Optical Spacer 태양전지세미나
2010. 9. 2.
9 ZnO NP layers as an optical spacer

René A. J. Janssen, Appl. Phys. Lett. 91, 113520 (2007)

9 TiOx sol-gel films

~80 nm ~10 nm

Kwanghee Lee & Alan J. Heeger, et al., Nature Photon. 3, 297, (2009)

Organic Semiconductor Lab 30/35 Changhee Lee, SNU

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Tandem solar cell 태양전지세미나
2010. 9. 2.

9TiOx Sol-gel film/PEDOT:PSS inter-electrode 9TiO2 nanoparticle/PEDOT:PSS inter-electrode

Ziruo Hong & Yang Yang, Adv. Mater. 22, 380 (2010)
9ZnO nanoparticle/PEDOT:PSS inter-electrode

VOC JSC FF PCE

(V) (mA cm-2) (%) (%)

P3HT:PC70BM 0.63 10.8 69 4.7

PCPDTBT:PCBM 0.66 9.2 50 3.0

Tandem 1.24 7.8 67 6.5

Jin Young Kim, Kwanghee Lee, Nelson E. Coates, Daniel Moses, Thuc-Quyen
Nguyen, Mark Dante, Alan J. Heeger, Science 317, 222 (2007). René A. J. Janssen, Appl. Phys. Lett. 90, 143512 (2007)

Organic Semiconductor Lab 31/35 Changhee Lee, SNU

IRTG 2010 Meeting

Flexible Substrates for Organic Solar Cells 2010. 6. 21
Mainz

L. Jay Guo, Adv. Mater. (in press)

Organic Semiconductor Lab 32/35 Changhee Lee, SNU

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Flexible Substrates for Organic Solar Cells 태양전지세미나
2010. 9. 2.

Organic Semiconductor Lab 33/35 Changhee Lee, SNU

한국미래기술교육연구원
Flexible Substrates : Barrier Performance 태양전지세미나
2010. 9. 2.

Organic Semiconductor Lab 34/35 Changhee Lee, SNU

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Summary 태양전지세미나
2010. 9. 2.

• Organic solar cells attract a great interest as a potential clean energy source.

• Bulk heterojunction (BHJ) of electron donor (D) and acceptor (A) materials:
phase-separated on the ~ 10 nm scale (comparable to the exciton diffusion length).
Æ The excitons photogenerated in the device are split into free electrons and holes by
the difference in HOMO-LUMO levels of the two materials.
Æ High charge dissociation efficiency.

• But their power conversion efficiency is still low: ~ 7.9 % (Solarmer)

• Breakthroughs are required:

- Design and synthesis of new active materials: low-bandgap polymers, new
acceptors etc
acceptors, etc.
- Device optimization: Optimum band alignment; Good organic/electrode interfaces;
Optical spacers, tandem structures, etc.
- Cost-effective, large-area deposition and patterning technique
- Flexible substrates; Thin film encapsulation

Organic Semiconductor Lab 35/35 Changhee Lee, SNU

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