O - NCKU 國立成功大學能源科技與策略研究中心

綠能科技及產業研討會 綠能科技及產業研討會 2010-11-26
成功大學太陽光電科技研究中心
染料敏化太陽能電池
染料敏化太陽能電池
吳春桂
吳春桂
國立中央大學化學系
Jhong-Li, Taiwan, ROC
1

Dye Dye-sensitized Dye sensitized sensitized Solar Solar Cell:
Cell:
A A New New New New New Generation Generation Photovoltaic
Photovoltaic
Photovoltaic
Photovoltaic
Photovoltaic
Professor Michael Grätzel
Artificial photosynthesis or nanotechnology
2

Characteristics
Characteristics
Dye Dye Dye Dye-Sensitized Dye Sensitized Sensitized Solar Solar Cells
Cells
TAIYO YUDEN Co., Ltd. (Japan),2005
Efficiency independent of sunshine angle
Efficiency increases with increasing temp.
Both sides can absorb sun light
Can absorb scattering light
Work at room light
ETRI, Korea, 2004
3

The The Efficiency Efficiency Roadmap Roadmap of of solar solar cells
cells
4

Principle Principle of of Dye Dye-sensitized Dye sensitized Solar Solar Cell
Cell
E vs NHE (V)
Conducting glass TiO 2 /Dye Electrolyte Cathode
hʋ
-1.0
-0.5
0
0.5
1.0
Anode
CB
e -
S*
S 0 /S +
I
Red Ox
- /I -
3
5

The The Photovoltaic Photovoltaic Performance Performance Performance of of N3
N3
and and N719 N719 dyes
dyes
M. K. Nazeeruddin et al. J. Am. Chem.
Soc. 2005, 127, 16835.
M. K. Nazeeruddin et al. J. Am. Chem.
Soc. 1993, 115, 6382.

The The Imperfect Imperfect of of N3 N3 and and N719 N719 dyes
dyes
● How How About About the the Light Light-Absorption Light Light Absorption Property?
Property?
Molar Absorption Coefficient (10 4 M -1 cm -1 Molar Absorption Coefficient
)
5
4
3
2
1
AM 1.5G
N3
0
0.0
300 400 500 600 700 800
Wavelength (nm)
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
Spectral Irradiance W m -2 nm -1
Spectral Irradiance W m
7

Elongating Elongating the the Conjugated Conjugated Length Length of of Ancillary
Ancillary
Ligand Ligand Decreases Decreases the the the Energy Energy of of of the the MLCT MLCT band band
band
HOOC
Heteroleptic
Homoleptic
COOH
Anchoring
ligand
HOOC
N
Ancillary
ligand
N N
N
Ru
N
C
S
COOH
N C S
≡ Conjugated Moiety
π∗ π of Ligand
h ν’
8

Heteroleptic Heteroleptic Sensitizer : Z907 Z907
HOOC
N
SCN
Z907
COOH
N
Ru
sensitizer λmax
(nm)
NCS
N
N
C 9H 19
C C9HH 19
ε
(M -1 cm -1 )
Z907 526 12200
N719 532 14000
Nomaized Nomaized efficiency
Design Design for for high high stability stability
stability
Time(h)
P. Wang, S. M. Zakeeruddin, R. Humphry-Baker, J-E. Moser, M. Grätzel, Adv. Mater. 2003, 15, 2101.
80 o C dark
1000 h.
55 o C, one Sun
1000 h.
P. Wang, S. M. Zakeeruddin, J-E. Moser, M. K. Nazeeruddin, T. Sekiguchi, M. Grätzel, Nat. Mater. 2003, 2, 402.
9

A A Ruthenium Ruthenium Complex Complex with with Super Super-High Super High Light Light- Light Harvesting Harvesting
Harvesting
Capacity Capacity for for Dye Dye-Sensitized Dye Sensitized Solar Solar Cells
Cells
C 8H 17
S
HOOC
S
HOOC
N
N N
N
Ru
CYC CYC-B1 CYC CYC B1
S
N C S
N
C
S
S
C 8H 17
Thiophene can effectively provide
aromatic stability to polyacetylene
while preserving the high charge
transport property.
The facile functionalization of a
thiophene also offers relatively
efficient synthetic solutions to
solubility, polarity, and band-gap
tuning.
Sulfur atom has greater radial
extension, therefore, thiophene is a
more electron-rich moiety, can raise
the energy level of metal center
10

IPCE (%)
PV PV Performance Performance of of CYC CYC-B1 CYC B1 or or N3 N3 Based Based Cells
Cells
80
70
60
50
40
30
20
10
0
CYC-B1
N3
400 500 600 700 800
Wavelength (nm)
Complex
Current Density(mA/cm2 Current Density )
I sc
(mA/cm 2 ) V oc
24
20
16
12
8
4
CYC-B1
N3
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Voltage (V)
(V) FF η (%)
CYC-B1 23.92 0.65 0.55 8.54
N3 21.32 0.66 0.55 7.70
11
C. Y. Chen, S. J. Wu, C. G. Wu, J. G. Chen, K. C. Ho, Angew. Chem. Int. Ed., 2006, 45, 5822 .

CYC-B11
The State-of-the-Art Dyes for DSCs
COO
TBA
S S
HOOC
N
S
N N
S
C
N
Ru
N
N
S
C
S
S
S
ε = 2.42 × 104 M-1 cm-1 ( at 554 nm)
ε
(10 4 M -1 cm -1 )
ε
5
4
3
2
1
-The system with volatile electrolyte-
CYC-B11
CYC-B1
PV Parameters
Jsc (mA/cm 2 ) 20.05
Voc (mV) 743
FF 0.774
η (%) 11.5
11.5
0
300 400 500 600 700 800
Wavelength (nm)
*Thickness: 8 + 5 μm; with DINHOP & Z960.
C. Y. Chen, M. Wang, J. Y. Li, N. Pootrakulchote, L. Alibabaei, C. Ngoc-le, J. D. Decoppet, J. H. Tsai,
C. Grätzel, C. G. Wu*, S. M. Zakeeruddin* & M. Grätzel*, ACS Nano 2009, 3, 3103.

Ru Ru-based Ru based Dyes Dyes Prepared Prepared in in Our Our Lab Lab for for DSC
DSC
HOOC
C C8H 8H 17
HOOC
S
C
N
N
COOH
N
Ru
N
C
S
CYC-B1
S S
N
N
S S
HOOC
N
N N
N
Ru
N C S
N
C
S
S
S
CYC CYC-B5 B5
- :
S
S
C C8H 8H 17
C 8H 17
C 8H 17
X =
S
S
O
S
HOOC
S
N
O
S
C
N
N
COOH
N
Ru
N
C
S
N
N
C C8H 8H 17 CYC-B3
R
C8H17 R
SJW-E1
X
X
R: C 7H 15 ,CYC-B6L
R: t-C 4H 9 ,CYC-B6S
S SC 8H 17 CYC-B11
13

Representative Representative of of Ru Ru-based Ru based Complexes
Complexes
1993
N3
λmax = 530 nm
ε= 14200 M -1 cm -1
COOH
HOOC
N
N
N
COOH
HOOC
N N
N Ru N C S
S
C
Ru
N
N
C
S
N
COOH
ABTOOC
N N
C
S
CYC-B11
Wu Lab
2009
(η= 10 %)
2005
Nazeeruddin, M. K.; Kay, A.; Rodicio, I.; Humpbry-Baker, R.; Miiller, E.; Liska, P.; Vlachopoulos, N.;
Grätzel, M. J. Am. Chem. Soc.,1993, 115, 6382-6390.
M. K. Nazeeruddin et al. J. Am. Chem. Soc. 2005, 127, 16835.
HOOC COOTBA
(η= 11.18 %)
λmax = 554 nm
ε = 24200 M -1 cm -1
(η= 11.5 %)
Chen, C. Y.; Wang, M.; Li, J. Y.; Pootrakulchote, N.; Alibabaei, L.; Ngoc-le, C. h.; Decoppet, J. D.; Tsai, J. H.; Gratzel, C.; Wu, C.G.; Shaik M. Zakeeruddin and
Michael Gratzel. ACS nano, 2009, 3 (10), 3103–3109.
14

Electronic Electronic Absorption Absorption Maxima Maxima of of the
the
sensitizer
Ancillary Ancillary Ligands Ligands and and and Complexes
Complexes
HOOC
X
HOOC
N
ancillary
ligand
λ max
(nm)
complex
peak II peak III (MLCT)
λ max
(nm)
λ max
(nm)
ε
(10 4 M -1 cm -1 )
S
CYC-B3 C8H17 318 338 544 1.57
S C8H 17
N N
N
Ru
X
N
C
S
N C S
X =
SJW-E1 339 363 546 1.87
O O
CYC-B6S 363 399 548 1.61
CYC-B6L 363 400 550 1.62
CYC-B1 S
C8H17 375 403 553 2.12
S
CYC-B11 377 387 554 2.36
S
S CaS
S CaL
S
S SC6H 13
S C8H 17
CYC-B4 S
404 425 543 2.44
15

C 8H 17
The The Importance Importance of of the the HOMO HOMO HOMO and and LUMO
LUMO
Location Location of of Ruthenium Ruthenium Based Based Dye Dye for for DSC
DSC
S
HOOC
S
S
HOOC
N
N N
N
Ru
N
C
S
S
N C S
S
S
CYC CYC-B4 CYC B4
C 8H 17
HOMO
LUMO
16

Reduce Reduce the the energy energy energy of of MLCT MLCT band band by
by
changing changing the the anchoring anchoring ligand
ligand
Elongate Simultaneously the Conjugation
Lengths of Ancillary Ligand & Anchoring Ligand
h ν’
C 8H 17
HOOC
HOOC
S
S
HOOC
HOOC
N
N
N N
Ru
N
C
S
S
N C S
S
CYC-B1
CYC CYC-B5 CYC B5
S.-J. Wu, C.Y. Chen, J.-G.Chen, J.-Y. Li, C.-G. Wu, Y. -L. Tung , K.-C.Ho Dyes and pigments, 2009, 84, 95. 17
C 8H 17

The The Efficiency Efficiency of of CYC CYC-B5, CYC B5, B5, CYC CYC-B1 CYC B1 & & N3
N3
Based Based Based DSCs
C 8H 17
HOOC
Sensitizer
CYC-B5
S S
S S
HOOC
N
N N
N
Ru
N C S
N
C
S
C 8H 17
CYC CYC-B5 CYC CYC-B5 CYC B5
B5
ε [*10 3 M -1 cm -1 ] (λ max [nm])
π-π* π-π* or 4d-π* 4d-π*
34.4 (316)
35.7 (327)
IPCE (%)
80
70
60
50
40
30
20
10
0
HOMO
(ev)
Current Density (mA/cm 2 )
24
21
18
15
12
9
6
3
CYC-B5
CYC-B1
N3
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
V / V
CYC-B5
CYC-B1
N3
400 500 600 700 800
LUMO
(ev)
Wavelength (nm)
Cell performance
Jsc (mA/cm 2 ) Voc (mV) FF η (%)
44.8 (411) 25.1 (562 562) 5.07 3.56 22.3 672 0.636 9.5
CYC-B1 35.8 (312) 46.4 (400) 21.2 (553 553) 5.10 3.52 20.8 655 0.668 9.1
N3 51.1 (311) 15.2 (385) 14.5 (530) 5.20 3.52 18.4 690 0.664 8.4
S.-J. Wu, C.Y. Chen, J.-G.Chen, J.-Y. Li, C.-G. Wu, Y. -L. Tung , K.-C.Ho Dyes and pigments, 2009, 84, 95.
18

The The Integrated Integrated Photon Photon Photon Flux Flux and and Maximum
Maximum
Current Current Density
Density
Current density mA/cm 2
Current density mA/cm
9
8
7
6
5
4
3
2
1
1
5.1
5.1
6.7
7.3
6.9
6.4
0
0
300 400 500 600 700 800 900 1000
Wavelength (nm)
http://rredc.nrel.gov/solar/spectra/am1.5/.
4.4
40
35
30
25
20
15
10
5
Accumulated current density density (mA/cm 2 )

The The Squaraines Squaraines are are are a a Class Class of of Dyes Dyes with with
with
Resonance Resonance Resonance Stabilized Stabilized Stabilized Zwitterionic Zwitterionic Structure
Structure
N
O
O
N
O
N
N 2+
N
1. Good light-absorption in the red-light region
2. ε (molar extinction coefficient) is very large
O
O
O
N
20

The The Highest Highest Efficiency Efficiency Unsymmetrical Unsymmetrical Squaraine
Squaraine
for for for Dye Dye Sensitized Sensitized Solar Solar Cells
Cells
SQ01
N
Dye
O
O
C 8H 17
N
SQ02 O
N
TiO 2
(µm)
COOH
O
C 8H 17
N
COOH
CDCA
(mM)
IPCE
(%)
Jsc (mA/cm 2 )
Voc
(mV)
Dye λmax (nm)
SQ01 647
SQ02 662
Yum, J.-H.; Walter, P. ; Huber, S. ; Rentsch, D.; Geiger, T.; Nuesch, F. ; Angelis,F. D.; Graetzel, M.; Nazeeruddin, M. K.; J. Am. Chem. Soc., 2007, 129, 10320.
Yum, J.-H.; Moon, S.-J.; Humphry-Baker, R.; Walter, p.; Geiger, t.; Nüesch, F. ; Grätzel, M.; Nazeeruddin, M. K.; Nanotechnology, 2008, 19, 424005
Geiger, T.; Kuster, S.; Yum, J.-H.; Moon, S.-J.; Nazeeruddin, M. K.; Grätzel, M.; Nüesch, F. Adv. Funct. Mater. 2009, 19, 2720-2727.
in DMF
FF η (%)
SQ02 7 0 --- 9.00 640 0.72 4.16
SQ02 7 10 --- 9.48 657 0.72 4.47
SQ02 7 30 --- 8.87 679 0.70 4.10
SQ01 10+4 10 85 10.5 603 0.71 4.50
SQ02 9+4 10 78 11.3 667 0.72 5.40
21

Panchromatic Panchromatic Unsymmetrical Unsymmetrical Squaraines Squaraines Squaraines for
for
Dye Dye-Sensitized Dye Sensitized Solar Solar Cell
Cell
N
JK-64
O
O
C8H 17
N
COOH
( in EtOH)
~ 660 nm
Intramolecular energy transfer
C 6H 13
C 6H 13
N
JK-64Hx
O
O
C8H 17
N
COOH
C 6H 13O JK-65
C 6H 13O
Dye Jsc (mA/cm 2 ) Voc (mV) FF η (%)
JK64 / Al 2O 3 13.85 510 70.77 5.00
JK64Hx/ Al 2O 3 12.82 542 74.87 5.20
JK65/ Al 2O 3 7.28 516 79.21 2.98
Choi, H.; Kim, J. J.; Song, K.; Ko, J.; Nazeeruddin, M. K.; Gratzel, M. J. Mater. Chem., 2010, 20,
3280–3286
N
O
O
C8H 17
N
COOH
22

Molecular Molecular Molecular Design Design of of the the the Unsymmetrical
Unsymmetrical
Unsymmetrical
Squaraine Squaraine Squaraine Dyes Dyes Dyes for for Panchromatic Panchromatic DSC
DSC
Hydrophobic group
Donor
group
Conjugated
Moiety
• Absorption in the red and far red region
O
O -
• Increase the molar extinction coefficient of the dye
Heterocyclic
(developing)
COOH
• Retard charge recombination between the injection electron and the
oxidized dye
• Structural modification to suppress the aggregation
• Containing hydrophobic group to prevent water-induced desorption
of the dye from TiO 2 surface.
23

An An Unsymmetrical Unsymmetrical Squaraine Squaraine Dye
C 6H 13
O
C 6H 13
O
N
O
S
O
O
JYL-SQ5
O
N
C4H9 COOH
24

Electronic Electronic Absorption Absorption Spectra Spectra of of JYL JYL-SQ5 JYL SQ5 in
in
Molar Absorption Coefficient (10 4 M -1 cm -1 Molar Absorption Coefficient
)
12
10
8
6
4
2
0
EtOH EtOH EtOH and and Adsorbed Adsorbed on TiO TiO 2
JYL-SQ5
JYL-SQ5 on TiO 2
691 691 nm
nm
400 500 600 700 800 900
Wavelength (nm)
Absorbance (a.u.)

Another Another Unsymmetrical Unsymmetrical Squaraine
Squaraine
C 6H 13
C 6H 13
Dye Dye Design Design Design for for NIR NIR NIR Sensing
Sensing
O
O
N
JYL-SQ6
S S
O
O
COOH
N
C 4H 9
26

The The Localization Localization of of the the Frontier Frontier Orbitals
for for JYL JYL-SQ5 JYL SQ5 and and JYL JYL-SQ6 JYL SQ6 Dyes
Dyes
JYL-SQ5
LUMO+1
LUMO
HOMO
HOMO-1
Molecular orbital calcularions of JYL-SQ5 were performed with the TD-DFT on B3LYP/6-31G* *
JYL-SQ6

Electronic Electronic Absorption Absorption Spectra Spectra of of JYL JYL-SQ5 JYL SQ5
and and and JYL JYL-SQ6 JYL JYL SQ6 SQ6 in in in EtOH EtOH and and Adsorbed Adsorbed on TiO TiO 2
Molar Absorption Coefficient (10 4 M -1 cm -1 Molar Absorption Coefficient (10 )
4 M -1 cm -1 Molar Molar Absorption Coefficient
)
12
10
8
6
4
2
0
JYL-SQ5
JYL-SQ5 on TiO 2
JYL-SQ6
JYL-SQ6 on TiO 2
400 500 600 700 800 900
Wavelength (nm)
Absorbance (a.u.)

Current Density (mA/cm2 Current Density
)
PV PV performance performance of of DSCs DSCs DSCs based based on on JYL JYL-SQ5 JYL SQ5
12
10
8
6
4
2
and and JYL JYL-SQ6 JYL SQ6
JYL-SQ5
JYL-SQ6
0
0 100 200 300 400
Voltage (mV)
IPCE (%)
50
40
30
20
10
JYL-SQ5
JYL-SQ6
0
300 400 500 600 700 800 900
Wavelength (nm)
Dye Jsc (mA/cm 2 ) Voc (mV) ff η (%)
JYL-SQ5 11.2 422 0.557 2.61
JYL-SQ6 9.40 432 0.578 2.34

The The Absorption Absorption Profile Profile of of FF-DOT1
F DOT1 Matches
Matches
Molar Absorption Coefficient (10 4 M -1 cm -1 Absorption coefficiency
Molar Absorption Coefficient
)
12
9x10 4
10
8x10 4
7x10 4
8
6x10 4
6
5x10 4
4x10 4
4
3x10 4
2x10 4
2
1x10 4
0
That That for for for JYL JYL-SQ5 JYL
SQ5
JYL-SQ5
JYL-SQ5 on TiO 2
F-DOT1
400 500 600 700 800 900
Wavelength (nm)
Absorbance (a.u.)

JYL JYL-SQ5 JYL
SQ5 was was Used Used as as a a a Co Co-dye Co dye for for an
an
Jsc (mA/cm 2 )
Organic Organic Dye Dye (F (F-DOT1) (F DOT1)
浸泡順序 浸泡順序 浸泡時間 浸泡時間 Voc (V)
Jsc
(mA/cm 2 )
FF η (%)
F-DOT1 (F) 6 hrs 0.50 9.64 0.62 2.99
JYL-SQ5 (S) 5hrs 0.42 11.86 0.54 2.64
16
14
12
10
8
6
4
2
F → S 2hrs-4hrs 0.42 14.62 0.49 3.04
F → S 2hrs-8hrs 0.42 14.19 0.49 2.96
F → S 6hrs-3hrs 0.43 14.97 0.50 3.26
0.0 0.1 0.2 0.3 0.4 0.5
Voc (V)
F-DOT1_4P1
SQ5_4P1
F-DOT1_SQ5 (2-4)
F-DOT1_SQ5 (2-8)
F-DOT1_SQ5 (6-3)
IPCE (%)
100
80
60
40
20
0
300 400 500 600 700 800 900 1000
Wavelength (nm)
F-DOT1_4P1
SQ5_4P1
F-DOT1_SQ5 (2-4)
F-DOT1_SQ5 (2-8)
F-DOT1_SQ5 (6-3)

國科會有機太陽能電池研究量測實驗室急徵求以下人才
國科會有機太陽能電池研究量測實驗室急徵求以下人才
應徵人員項目 : 1. 研究員及博士後研究員數名
2. 操作員數名
職務說明 :
1. 研究員及博士後研究員--從事有機太陽能電池之相關研究計畫。
2. 操作員--協助有機太陽能電池研究量測實驗室之相關儀器的操作與維護。
條件限制 :
•1. 操作員:凡對儀器操作維護有興趣之大學以上理工科畢業具備良好的溝通
• 能力及積極態度之有志青年,具理工科碩士學位者優先錄取。
2. 研究員及博士後研究員:具有理工科博士學位之人才,具有機太陽能電池
(DSC或OPV)元件組裝之經驗者優先錄取。(應徵此項者請附上一封介紹信)
薪資待遇及任期 : 依國科會之薪資規定給薪(依個人研究表現調整薪資,
可長期聘任)。
上班地點 : 中壢市國立中央大學
可開始上班日 : 即日起
有意應徵者請將個人履歷及相關資料寄到
中壢市中大路
中壢市中大路300
中壢市中大路 300 300號國立中央大學化學系吳春桂教授收
300 號國立中央大學化學系吳春桂教授收

Conclusions
Conclusions
DSC DSC is a potential candidate for next next next generation generation solar
solar
cells
cells
Thiophene Thiophene moiety moiety has has been been been proved proved to to be be a a powerful
powerful
unit unit for for red red-shifting red shifting the the absorption absorption maxima maxima of of the
the
Ru Ru-based Ru Ru-based Ru
Ru based based and and squaraine squaraine dyes.
dyes.
DSCs DSCs based based based JYL JYL-SQ5 JYL
SQ5 and and JLY JLY-SQ6 JLY SQ6 reveal reveal reveal panchromatic
panchromatic
response response with with the the conversion conversion efficiencies efficiencies of of 2.61 2.61 %
%
and and and 2.34 2.34 %, %, respectively.
respectively.
JYL JYL-SQ5 JYL
SQ5 can can be be a a Co Co-dye Co dye for for organic organic dye dye however however the
the
efficiency efficiency need need to to be be be improved improved further.
further.
33

Acknowledgement
Acknowledgement
Mr. Jheng Jheng-Ying Ying Li ( (李政穎 李政穎 李政穎) 李政穎
Dr. Chia Chia-Yuan Yuan Chen ( (陳家原 陳家原 陳家原 陳家原 陳家原) 陳家原 陳家原 陳家原
Miss Jia Jia-Hung Hung Tsai (林祖涵 林祖涵 林祖涵) 林祖涵 林祖涵) 林祖涵
Miss Szu Szu-Chien Chien Chen (陳思蒨 陳思蒨 陳思蒨) 陳思蒨 陳思蒨) 陳思蒨
Prof. Kuo Kuo-Chuan Chuan Ho (何國川 ( 何國川 何國川 何國川 何國川) 何國川 何國川 何國川
Mr. Jian Jian-Ging Ging Chen (陳建清 ( 陳建清 陳建清 陳建清 陳建清) 陳建清 陳建清 陳建清
Department of Chemical Engineering,
National Taiwan University, Taiwan
Thank you for your attention
Professor M. Gr Grätzel tzel Group
Laboratory for Photonics and Interfaces,
Swiss Federal Institute of Technology,
CH 1015, Lausanne, Switzerland
Professor Hui Hui-Hsu Hsu Tsai
Department of Chemistry,
National Central University,
National Science Council
Photovoltaics Technology
Center, ITRI
Department of Chemistry,
National Central University
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