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Highly efficient poly(3-hexylthiophene) based monolithic dye-sensitized

solar cells with carbon counter electrode

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DOI: 10.1039/C0EE00821D

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Cite this: DOI: 10.1039/c0ee00821d
www.rsc.org/ees COMMUNICATION
Highly efficient poly(3-hexylthiophene) based monolithic dye-sensitized solar
cells with carbon counter electrode
Heng Wang, Guanghui Liu, Xiong Li, Peng Xiang, Zhiliang Ku, Yaoguang Rong, Mi Xu, Linfeng Liu, Min Hu,
Ying Yang and Hongwei Han*
Downloaded by Huazhong University of Science & Technology on 15 April 2011

Received 26th December 2010, Accepted 22nd March 2011

Published on 15 April 2011 on http://pubs.rsc.org | doi:10.1039/C0EE00821D

DOI: 10.1039/c0ee00821d

A high efficiency of 3.1% was obtained for poly(3-hexylthiophene)
based monolithic solid state dye-sensitized solar cells using graphite/
carbon black counter electrodes under simulated AM 1.5 solar
illumination of 100 mW cm
2.
Renewable energy sources have received increasing attention during
the past decades due to the energy crisis and their environmental
impact. As one of the most promising alternative energy sources,
solar power is in urgent demand in the near future. Dye-sensitized
solar cells (DSSCs), which are easy to fabricate and low in cost, have
been considered as one of the most cost-effective photovoltaic (PV)
devices.1 A high efficiency of up to 11.5% has been achieved with
a liquid electrolyte associated with I3
/I
redox coupling,1c but
DSSCs based on liquid electrolytes have many practical problems
such as the leakage of the solvent and the erosion of electrodes, which
block their rapid commercial application. Replacing the liquid elec-
trolyte with a solid-state medium seems to be a solution to these
problems. Recently, great efforts have been devoted to all-solid-state
DSSCs based on hole-transporting materials (HTMs), including
Michael Gr€ atzel Center for Mesoscopic Solar Cells, Wuhan National
Laboratory for Optoelectronics, Huazhong University of Science and
Technology, Wuhan, Hubei, P. R. China. E-mail: hongwei.han@mail.
hust.edu.cn; Fax: +86 027 877 930 27; Tel: +86 027 877 930 27
organic small-molecules HTM,2 conjugated polymers,3 and inorganic
semiconductors.4
Although an efficiency of over 5% has been achieved with HTMs,
the counter electrodes (CEs) of most HTM based all-solid-state
DSSCs are made by thermally evaporating noble metals such as Au
or Ag.2d Obviously, the fact that this CE uses high-cost metals is still
an issue for its widescale application, and the vacuum deposition
process is also highly energy consumptive. Therefore, the question of
how to fabricate CEs for HTM-based DSSCs with low-cost materials
and simple processes is still a big challenge.
Carbon is an abundantly available and low-cost material, and
could be deposited via simple processes such as the screen-printing
method. Graphite and carbon black are the most common carbon
materials that have been used in DSSCs. In 1996, Kay and Gr€ atzel5
firstly reported a monolithic liquid DSSC with a carbon CE, in which
graphite was used to increase the lateral conductivity and carbon
black acted as a catalyzer. Recently, a monolithic solid-state DSSC
based on a platinized carbon CE was developed by Han et al.6
Unfortunately, these works are still based on an iodine system, which
connotes the possibility of unstabilization.
P3HT, one of the iodine-free HTMs, is of particular interest in
solid-state DSSCs for its high hole-mobility, amorphous property
and good solubility. D102 is a metal free dye and has a high
extinction coefficient. The chemical structures of D102 dye and P3HT
are shown in Fig. 1a. After treatment with Li(CF3SO2)2N, the lowest

Broader context
Dye-sensitized solar cells (DSSCs) have attracted high attention in the past decades for their low cost, simple manufacturing process
and high efficiency. So far, the highest certificated energy conversion efficiency of a DSSC has reached 11.5%. Unfortunately, such
efficiency is based on a liquid electrolyte, which imposes many hurdles for its application, such as instability and complicated
technological fabrication. Replacing the liquid electrolyte with a solid state medium seems to be an effective road for DSSCs’
commercialization. However, the counter electrode of most solid-state DSSCs based on hole-transporting materials (HTMs) is
fabricated by evaporating a noble metal. Obviously, this counter electrode, with its high-cost metals, is still an issue for widescale
application. Here, we demonstrate firstly a simple method to assemble a poly(3-hexylthiophene) (P3HT)-based monolithic DSSC
with a carbon counter electrode. It is gratifying to find that with a graphite/carbon black counter electrode, a high efficiency of 3.1%
was obtained under illumination of 100 mW cm
2, which is even higher than that of corresponding devices with Au counter elec-
trodes. Impedance spectra revealed that carbon black could enhance electron injection from the counter electrode to P3HT, and lead
to a decreased recombination rate between injected electrons and holes in P3HT. This monolithic DSSC with a carbon counter
electrode presents a promising commercial vision.

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Fig. 2 SEM images of the cross sections of: a) a P3HT based DSSC with
Fig. 1 a) The chemical structures of D102 dye and P3HT and the cor-
a carbon CE, and b) its high magnification dye-sensitized TiO2/P3HT
responding energy levels of various materials. b) A schematic structure of
layer.
a graphite based monolithic device.

gradually at 65  C for 40 min, the P3HT based monolithic solid-state

DSSCs were prepared successfully.
unoccupied molecular orbital (LUMO) energy level (3.4 eV) of D102
Figs 2a and b show the SEM cross section of a P3HT-based
is lower than that of P3HT (3.1 eV).3f This facilitates the electron
monolithic solid-state DSSC and its high magnification dye-sensitized
injection from P3HT to D102. Fortunately, the work function of
TiO2/P3HT layer, respectively. In Fig. 2a, it is clear that 2.3 mm TiO2
carbon (5.0 eV)7 is close to the HOMO of P3HT (5.1 eV). These
layer, 1.6 mm ZrO2 layer and around 25 mm carbon layer are ordinally
advantages prompted us to assemble a monolithic solid-state DSSC
deposited on the surface of FTO glass. The film in Fig. 2b shows
with P3HT, D102 and carbon CE.
a sheet structure with very soft features and low contrast within
Fig. 1b shows a schematic structure of P3HT-based monolithic
various small areas, indicating homogeneity and effective pore filling.
devices, where a nanoporous TiO2 layer, a ZrO2 insulating layer and
This indicates that such a monolithic device could be successfully
a carbon CE layer were screen-printed onto one FTO glass substrate
filled with P3HT, although the total thickness of the device is more
layer by layer. P3HT was deposited on the graphite/carbon black
than 28 mm.
layer by drop casting. Dramatically, a high efficiency of 3.1% was
The characteristic parameters of the current–voltage curves of
obtained for the P3HT based monolithic solid state DSSCs
TiO2/D102/Li+/P3HT/C solar devices with different ZrO2 thicknesses
using graphite/carbon black CEs under simulated AM 1.5 solar
were obtained under simulated AM 1.5 sunlight with an intensity of
illumination of 100 mW cm
2, which is even higher than that of
100 mW cm
2 and are presented in Table 1. There, the thickness of
corresponding devices using vacuum deposited Au CE.3f The fluo-
TiO2 film is 1.6 mm and the thickness of carbon CE is around 25 mm.
rine-doped SnO2 substrates were etched with a laser to form two
Generally, the thickness of HTM layer between the dye-sensitized
detached electrode patterns before being cleaned ultrasonically with
TiO2 film and the vacuum deposited noble metal CE layer is
detergent, deionized water and ethanol. After that, the patterned
controlled to be around 100–200 nm.3c It is well known that a thinner
substrates were coated with a 100 nm compact TiO2 layer by aerosol
HTM layer between the TiO2 film and the CE layer corresponds to
spray pyrolysis, and then a 2 mm nanoporous TiO2 layer was
a smaller series resistance; moreover, it also means that more light
deposited by screen printing with a TiO2 slurry. After being sintered
could be reflected by the CE. As a result, the HTM layer should be as
at 450  C for 30 min, the films were soaked in an aqueous solution of
thin as possible, if that does not lead to a short circuit. Herein, the
TiCl4 (0.05 M) for 30 min at 70  C.8 The samples were sintered again
at 450  C for 15 min after rinsing with deionized water and ethanol.
Then, a 4 mm insulating ZrO2 layer was printed on the top of the
nanoporous TiO2 layer using a ZrO2 paste, which also acts as a light- Table 1 The photovoltaic performance of TiO2/D102/Li+/P3HT/C
devices with different ZrO2 layer thicknesses under AM 1.5 conditions of
reflecting spacer layer. Finally, the carbon CE was coated on the top 100 mW cm
2. The CEs were composed of graphite and carbon black.
of ZrO2 layer by printing a carbon slurry and sintering at 400  C for The thickness of TiO2 film was 1.6 mm
30 min. The thickness of the carbon film was around 25 mm. After
dying with D102 solution (0.5 mM in CH3CN : t-BuOH (1 : 1)) at Thickness/mm Jsc/mA cm
2 Voc/V FF h (%)
room temperature for 24 h, the samples were rinsed in dry ethanol 3
0 5.43 0.53 0.70 2.02
times and dried under a flow of air. Then, the samples were immersed 1.1 6.1 0.63 0.68 2.61
in an acetonitrile solution containing Li(CF3SO2)2N (Aldrich, 2.3 6.3 0.63 0.64 2.54
20 mg ml
1) for 5 min, and dried under a flow of air. A 1,2-dichlo- 4.0 6.6 0.65 0.63 2.70
6.3 6.1 0.67 0.60 2.45
robenzene solution containing P3HT (Synwitech. CO, LTD. 9.5 4.5 0.67 0.48 1.45
40 mg ml
1) was dropped onto the carbon layer. After being dried

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optimized ZrO2 film thickness, which determines the distance

between the TiO2 film and the carbon layer, is controlled within
1–6 mm. Compared with devices with ZrO2 insulating layers, devices
without a ZrO2 layer show a lower open-circuit voltage (Voc) of
0.53 V and a lower short-circuit current density (Jsc) of 5.43 mA
cm
2. This was assumed to be due to the insulating ZrO2 layer
preventing the transfer of electrons from the conduction band of
TiO2 to the carbon counter electrode. The highest fill factor (FF)
of 0.7 was obtained for devices without a ZrO2 layer. This may be
attributed to better filling of P3HT and a lower series resistance
for devices without a ZrO2 layer. However, when the thickness of
the ZrO2 film is increased from 1.1 mm to 6.3 mm, all the
parameters of these devices show approximative values, which
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present as 0.63–0.67 V for Voc, 6.1–6.6 mA cm
2 for Jsc, and

Published on 15 April 2011 on http://pubs.rsc.org | doi:10.1039/C0EE00821D

2.5–2.7% for the efficiency. In fact, when the thickness of the

ZrO2 film is further increased to 9.5 mm, the Jsc decreased to
4.5 mA cm
2, the FF decreased to 0.48 and the efficiency
decreased to 1.5%. This could be attributed to the fact that
a ZrO2 film with a thickness above 6 mm leads to poor pore-filling
and a high series resistance. As a result, the optimized ZrO2 film
thickness was in the range 1–6 mm for P3HT based monolithic
solid-state DSSCs when the thickness of TiO2 was 1.6 mm.
For further optimization of P3HT-based monolithic DSSCs with
carbon CEs, the characteristic parameters of the current–voltage
curves of TiO2/D102/Li+/P3HT/C solar devices with different TiO2
thicknesses were obtained under simulated AM 1.5 sunlight with an
intensity of 100 mW cm
2 and are presented in Table 2, where the
thickness of the ZrO2 insulating layer and the carbon CE were kept at
the same values of 4 mm and 25 mm, respectively. It indicated that
with the increase of of the TiO2 film thickness, the Voc remains
around 0.63 V, the Jsc increases from 6.1 mA cm
2 for the device with
a 0.9 mm TiO2 layer to 7.6 mA cm
2 for that with a 2.0 mm TiO2 layer.
This could be attributed to the fact that a thicker TiO2 film could
absorb more dye and then higher photocurrent density would be
obtained. However, when the thickness of the TiO2 film was further
increased to 5.4 mm, the Jsc decreased to 6.1 mA cm
2. This could be
attributed to the fact that a thicker TiO2 film could lead to worse pore
filling and a higher series resistance. Clearly, the highest Jsc could be
obtained when the thickness of TiO2 film is 2 mm. However, the FF of
these devices decreased gradually from 0.67 to 0.41 when the thick-
ness of the TiO2 film was increased from 0.9 mm to 5.4 mm. When the
thicknesses of the TiO2 layer and the ZrO2 layer were 1.6 mm and
9.5 mm respectively, the FF value of the DSSC was 0.48, which was
higher than the 0.41 achieved for the device with 5.4 mm TiO2 and
4 mm ZrO2 layers. This could be attributed to the better filling of
P3HT in the ZrO2 layer than in the TiO2 film, since the size of the
Fig. 3 The photocurrent–photovoltage curves of P3HT based mono-
lithic DSSCs with different CEs: graphite CE (circle), graphite and
carbon black CE (square) under 100 mW cm
2 AM 1.5 illumination.
ZrO2 particles (90 nm) was much larger than that of the TiO2
particles (18 nm). As a result, the overall energy conversion efficiency
increased from 2.65% for the devices with 0.9 mm TiO2 films to 3.11%
for those with 2 mm TiO2 films, and then decreased to 2.7% for 3.3 mm
and 1.45% for 5.4 mm when the thickness of the TiO2 film was further
increased. Therefore, the highest efficiency of 3.11% of P3HT based
monolithic solid-state DSSCs was obtained with a 2 mm TiO2 film
thickness.
In order to investigate the effect of carbon black on the perfor-
mance of P3HT-based monolithic DSSCs with graphite/carbon black
counter electrodes (GCCEs), devices with blank graphite counter
electrodes (GCEs) were fabricated. The current density–voltage
curves of GCCE based and GCE based DSSCs were measured under
irradiation by 100 mW cm
2 AM 1.5 simulated sunlight and are
presented in Fig. 3, where the thicknesses of the TiO2 nanocrystallite
layer and the ZrO2 layer were optimized at 2.0 mm and 4.0 mm,
respectively. The GCCE based devices showed a higher performance
(Jsc ¼ 7.6 mA cm
2, Voc ¼ 0.62 V, and h ¼ 3.1%) than that of the
GCE based devices (Jsc ¼ 5.5 mA cm
2, Voc ¼ 0.52 V, h ¼ 1.8%).
Fig. 4 shows the corresponding incident photo-to-current efficiency
(IPCE) spectra for the devices used in Fig. 3. The IPCE is defined as

Table 2 The photovoltaic performance of TiO2/D102/Li+/P3HT/C

devices with different TiO2 layer thicknesses under AM 1.5 conditions of
100 mW cm
2. The CEs were composed of graphite and carbon black.
The thickness of ZrO2 film was 4.0 mm

Thickness/mm Jsc/mA cm
2 Voc/V FF h (%)

0.9 6.1 0.65 0.67 2.65

1.5 6.8 0.63 0.67 2.87
2.0 7.6 0.62 0.66 3.11
3.3 7.3 0.63 0.59 2.71
Fig. 4 The IPCE spectra of P3HT based monolithic DSSCs with
4.1 6.6 0.63 0.52 2.16
5.4 6.1 0.62 0.41 1.55 different CEs: graphite CE (circle), graphite and carbon black CE
(square).

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Fig. 5 Electrochemical impedance spectra of P3HT-based monolithic
DSSCs with different CEs: graphite CE (circle), graphite and carbon
black CE (square).
the ratio of collected electrons to incident photons, which reflects the
light response of devices and is directly related to the Jsc. Obviously,
the IPCE value of the GCCE based devices is higher than that of the
GCE based devices in the full-scale visible region of the electromag-
netic spectrum. The highest values of these devices are obtained at
470 nm, where the IPCE value of the GCCE based devices is 50%,
which is a factor of 31% more than that of the GCE based devices
(38%). These data indicate that the GCCE based devices collect
electrons more efficiently relative to the GCE based devices. As
a result, the Jsc of the GCCE based devices is higher than that of the
GCE based devices.
Electrochemical impedance spectra (EIS) are widely used to
investigate charge transfer rates at the interface of either dye
sensitized TiO2/HTM or HTM/CE.9 Herein, the EIS of the GCCE
based and GCE based DSSCs were tested at
0.6 V with a PAR-
STAT2273 advanced electrochemical system under dark condi-
tions, as shown in Fig. 5. The high frequency arc (ranging from
1 MHz to 1 kHz) is assigned to the charge exchange process at the
P3HT/CE interface. The low frequency arc (ranging from 500 Hz to
0.4 Hz) corresponds to the recombination between the electrons in
the conduction band of TiO2 and the holes in the P3HT. The results
indicate that the high frequency arc radius of the GCE based
devices is larger than that of the GCCE based devices, but the low
frequency arc radius of the GCE based devices is smaller than that
of the GCCE based devices. This means that the charge transfer
resistance (R1) between GCE and P3HT is larger than between
GCCE and P3HT, while the recombination resistance (R2) at the
TiO2/HTM interface of the GCE based devices is smaller than that
of the GCCE based devices.
The photovoltaic performances and related parameters obtained
by analogizing the impedance spectra10 of the GCE based devices and
the GCCE based devices are summarized in Table 3. Since R1 of the
GCCE based devices (9.7 U cm2) is smaller than that of the GCE
based devices (27.6 U cm2), electron injection at the P3HT/CE
interface is more efficient for the GCCE based devices than for the
GCE based devices, and as a result, a higher Jsc is obtained for the
GCCE based devices than for the GCE based devices. On the other
hand, since electron transfer from the CE to P3HT is more difficult
for GCE based devices than for GCCE based devices, the hole
density in P3HT for the GCE based devices should be higher than
that for the GCCE based devices. This facilitates the recombination
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Table 3 The photovoltaic performance of TiO2/D102/Li+/P3HT/C
devices with graphite CEs (GCE) and graphite and carbon black CEs
(GCCE), and parameters obtained by fitting the impedance spectra using
an equivalent circuit.11
Jsc Voc R1 R2
CE (mA cm
2) (V) FF h (%) (U cm2) (U cm2) s (ms)
GCE 5.5 0.52 0.64 1.8  0.1 27.6 56.0 1.6
GCCE 7.6 0.62 0.66 3.1  0.1 9.7 203.6 3.5
between electrons in the conduction band of TiO2 and holes in P3HT.
The recombination between holes in P3HT and electrons in TiO2
results in a downward shift of the quasi-Fermi level of TiO2. This
explains why a lower Voc is obtained for the GCE based devices than
for the GCCE based devices, since the Voc is decided by the difference
between the quasi-Fermi level in TiO2 and the quasi-Fermi level in
P3HT.12 Moreover, the recombination resistance (R2) of the GCE
based devices (56.0 U cm2) is smaller than that of the GCCE based
devices (203.6 U cm2). Because a small recombination resistance
means a high recombination rate, the GCE based devices have higher
recombination rates than the GCCE based devices. The recombina-
tion lifetime (s) is also used to investigate the TiO2/P3HT interface,
and can be obtained using the equation s ¼ 1/2pfmid;11 here the fmid is
defined as the midfrequency peak of the bode-phase plots in
impedance spectra.10b,12 The GCE based devices and the GCCE based
devices exhibit fmid values of 97 Hz and 45 Hz, respectively. This
represents the fact that the GCCE based devices have a longer
recombination lifetime (3.5 ms) than the GCE based devices (1.6 ms).
These results demonstrate that the use of carbon black in the CE
decreases the charge recombination between the injected electrons in
the conduction band of TiO2 and the holes in P3HT. This could
explain why a larger Voc is obtained for the GCCE based devices than
for the GCE based devices. Therefore, CEs composed of graphite and
carbon black exhibited better performance for the P3HT
based monolithic solid-state DSSCs than those composed of pure
graphite CE.
In conclusion, we have developed highly efficient P3HT based
monolithic DSSCs with low-cost carbon CEs. Compared with blank
graphite CE based devices, the devices with graphite and carbon
black CEs shows a higher efficiency of 3.1%. Impedance spectra
revealed that carbon black could enhance the electron injection from
the CE to P3HT and lead to a decreased recombination rate between
injected electrons and holes in P3HT. This design of HTM-based
monolithic DSSCs with carbon CEs presents a promising substitute
for conventional HTM-based DSSCs with vacuum-deposited metal
CEs, and offers a path to the commercial development of DSSCs
with low cost CEs. Further improvement could be expected from
interface engineering or sensitizer design.
Acknowledgements
The authors acknowledge the financial support of the Nature
Science foundation of Hubei Province (2008CDA042) and the
Wuhan national laboratory for optoelectronics (WNLO). We
thank the Analytical and Testing Center of Huazhong University of
Science and Technology (HUST) for field emission scanning elec-
tron microscopy (FESEM) testing.
This journal is ª The Royal Society of Chemistry 2011

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