Enhancement of p-Type Dye-Sensitized Solar Cell Performance by
Supramolecular Assembly of Electron Donor and Acceptor
Haining Tian †, #, Johan Oscarsson ‡, Erik Gabrielsson†, Susanna K. Eriksson §, Rebecka
Lindblad ‡, Bo Xu †, Yan Hao §, #, Gerrit Boschloo §, Erik M. J. Johansson §, James M.
Gardner ¶, Anders Hagfeldt §, Håkan Rensmo ‡,*, Licheng Sun †,‖*
†
Organic Chemistry, Centre of Molecular Devices, Department of Chemistry, School of Chemical
Science and Engineering, KTH Royal Institute of Technology, SE-10044, Stockholm, Sweden.
‡
Division of Molecular and Condensed Matter Physics, Department of Physics and Astronomy,
Uppsala University, SE-751 20 Uppsala, Sweden.
§
Physical Chemistry, Centre of Molecular Devices, Department of Chemistry-Ångström, Uppsala
University, SE-751 20 Uppsala, Sweden.
‖
State Key Laboratory of Fine Chemicals, DUT-KTH Joint Research Centre on Molecular Devices,
Dalian University of Technology (DUT), 116024 Dalian, China
¶
Applied Physical Chemistry, Centre of Molecular Devices, Department of Chemistry, School of
Chemical Science and Engineering, KTH Royal Institute of Technology, SE-10044, Stockholm,
Sweden.
#
Current address: Physical Chemistry, Uppsala University, SE-751 20 Uppsala, Sweden
Figure S1. The H1-NMR spectrum of ZnTCPP
Figure S2. The H1-NMR spectrum of C60PPy
Absorbance
C60PPy in toluene
400
500
600
700
800
Wavelength [nm]
Figure S3. UV-Vis spectrum of C60PPy in toluene
Figure S4. Absorbance spectrum of C60PPy on NiO (NiO as background).
Figure S5. Absorbance spectra of NiO sensitized by ZnTCPP(a) and TCPP(b).
40
NiO
NiO/C60PPy
NiO/ZnTCPP
NiO/(ZnTCPP/C60PPy)
35
IPCE [%]
30
25
20
15
10
5
0
400
500
600
Wavelength [nm]
700
800
Figure S6. IPCE spectra of NiO, NiO/C60PPy, ZnTCPP and ZnTCPP/C60PPy-based p-type DSCs
TCPP
TCPP/C60PPy
-2
Photocurrent Density [mA.cm ]
1.2
0.8
0.4
0.0
0.00
0.03
0.06
0.09
Photovoltage [V]
0.12
0.15
Figure S7. J-V curves of TCPP and TCPP/C60PPy-based p-type DSCs
30
TCPP
TCPP/C60PPy
25
IPCE %
20
15
10
5
0
400
500
600
Wavelength [nm]
700
800
Figure S8. IPCE spectra of TCPP and TCPP/C60PPy-based p-type DSCs
1.2
ZnTCPP
ZnTCPP+C60PPy
Absorbance
1.0
0.8
0.6
0.4
0.2
415
420
425
430
435
440
445
Wavelength [nm]
Figure S9. The absorption spectra of ZnTCPP with/without C60PPy in Tol:EtOH (10:1)
Table S1. Reproducibility of photovoltaic performance of ZnTCPP devices.
JSC
VOC
η
ff
1
2
3
4
[mA·cm−2]
[mV]
0.5
0.4
0.5
0.5
118
122
120
120
[%]
0.40
0.40
0.40
0.40
0.02
0.02
0.02
0.02
All values are obtianed under 100 mW·cm-2 light illumination using E1 electrolyte
Table S2. Reproducibility of photovoltaic performance of ZnTCPP-C60PPy devices.
JSC
VOC
η
ff
1
2
3
4
[mA·cm−2]
[mV]
1.3
1.4
1.5
1.6
154
146
158
150
[%]
0.38
0.40
0.38
0.37
0.08
0.08
0.09
0.09
All values are obtained under 100 mW·cm-2 light illumination using E1 electrolyte
Table S3. Calculated energy levels of the dye, fullerene and dye-fullerene complex.
ZnTCPP
C60PPy
ZnTCPP-C60PPy
HOMO /V vs
NHE
0.963832
0.935805
0.547232
All values are given vs NHE
LUMO /V vs
NHE
-1.91808
-0.93441
-0.79128
LUMO+4 / V vs
NHE
-2.17087
E0-0 / V vs
NHE
2.881917
1.870212
1.338509
-1
-2
E /eV
-3
-4
-5
-6
-7
Figure S10. Energy level diagram showing 20 frontier levels of the dye-fullerene complex. Red lines represent
virtual orbitals and black occupied. NHE is marked with a dashed line at -4.44 eV.
HOMO-1 (ZnTCPP)
HOMO (ZnTCPP)
LUMO (ZnTCPP)
HOMO-1 (C60PPy)
LUMO (C60PPy)
LUMO+1 (ZnTCPP)
HOMO (C60PPy)
LUMO+1 (C60PPy)
HOMO-1 (ZnTCPP/C60PPy)
HOMO (ZnTCPP/C60PPy)
LUMO (ZnTCPP/C60PPy)
LUMO+1 (ZnTCPP/C60PPy)
LUMO+2 (ZnTCPP/C60PPy)
LUMO+3 (ZnTCPP/C60PPy)
LUMO+4 (ZnTCPP/C60PPy)
Figure S11. Molecular frontier orbitals of ZnTCPP, C60PPy and ZnTCPP/C60PPy
Table S4. Photovoltaic properties of ZnTCPP/C60PPy-based DSCs with different electrolytes. [a]
JSC
Electrolytes
η [b]
VOC
ff
[mA·cm−2]
[mV]
E2
1.5
260
0.35
0.13
E3
1.6
155
0.32
0.08
[a]
[%]
3 µm NiO electrode; [b] Light intensity of 100 mW·cm−2
0
10
E2
E3
-1
QOC [mC]
10
-2
10
-3
10
-4
10
0.00
0.05
0.10
0.15
0.20
0.25
Voc [V]
Figure S12. Extracted charge Qoc as a function of Voc from ZnTCPP/C60PPy-based devices using E2
and E3 electrolytes
Figure S13. FT-IR spectra of pure ZnTCPP and ZnTCPP on NiO.
Pure ZnTCPP and ZnTCPP on NiO were tested by infrared spectroscopy in order to
get insights into the interfacial structure of ZnTCPP on NiO surface. The IR spectrum
of pure ZnTCPP in KBr showed a peak at 1700 cm-1, which belongs to C=O
stretching of the protonated carboxylic acids. When ZnTCPP was sensitized on NiO,
the carbonyl peak is disappeared. The absence of the carbonyl peak indicates a full
conversion of the carboxylic acids into carboxylates, which suggests all carboxyl acid
groups have been anchored on NiO surface via bidentate or/and unidentate (from the
broad 1600 cm-1 peak) to the NiO and also means the sensitized ZnTCPP is lying on
NiO surface.