DOI: 10.1002/cphc.
200600664
TiO2 Porous Electrodes with Hierarchical
Branched Inner Channels for Charge Transport
in Viscous Electrolytes**
Yong Zhao,[a, b] Xianliang Sheng,[a, b] Jin Zhai,*[a] Lei Jiang,[a] Chunhe Yang,[a]
Zhongwei Sun,[a] Yongfang Li,[a] and Daoben Zhu[a]
Titanium dioxide (TiO2) photoelectrodes with micro/nano hier-
archical branched inner channels have been prepared by an elec-
trohydrodynamic (EHD) technique and assembled to form dye-
sensitized solar cells (DSSCs). Excellent penetration of ionic-liquid
electrolytes and enhanced light harvesting in the longer wave-
length region are realized within the composite-structure elec-
trode, thus a better fill factor (ff) of 75.3 % and higher conversion
efficiency (h) of 7.1 % are obtained for viscous ionic-liquid electro-
Introduction
Dye-sensitized solar cells (DSSCs) have attracted much atten-
tion as promising low-cost and relatively efficient devices for
the photovoltaic conversion of solar energy.[16] Device perfor-
mance, that is, light-to-electricity conversion efficiency, is deter-
mined by light collection efficiency, which is directly related to
a given systems capability for charge separation and charge
transport. With organic liquid electrolytes, which have high
charge drift mobility, over 10 % conversion efficiency was ob-
tained for DSSCs,[7, 8] whereas the devices sealing and long-
term stability with liquid electrolytes remain an important
issue in view of the practical application. Consequently, nonvo-
latile viscous ionic-liquid/polymer electrolytes, quasi-solid-state
electrolytes, and solid-state electrolytes[917] have been intro-
duced to replace the organic liquid electrolytes. However, su-
perior penetration of these new electrolytes into the nanocrys-
talline network structure and the quick charge transport as in
pure nanostructured films cannot be realized easily. On the
other hand, the photocurrent can be improved by increasing
the light-collection efficiency. Much effort has gone into the
synthesis of various sensitizers to enhance the spectral re-
sponse.[18, 19] While tuning film morphology, such as coupling
the photonic crystal layer to the electrode as a dielectric
mirror,[20] introducing hollow sphere voids[21] and large solid
particles[22, 23] as scattering centers is also an efficient way to
improve light harvesting, and with it, conversion efficiency.
Therefore, with porous photoanodes, where favorable penetra-
tion effects of viscous and solid electrolytes predominate, fast
charge transport and effective light collection are attractive tar-
gets for researchers.
856 @ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
lytes compared to pure nanostructured films. Hierarchical
branched channels in the photoanodes can efficiently improve
the transport properties of redox-active species in viscous electro-
lytes, which is demonstrated by electrical impedance spectrosco-
py (EIS). The incident monochromatic photon-to-electron conver-
sion efficiency (IPCE) shows that enhanced light scattering in the
composite film is of benefit for light harvesting and thus for solar
energy conversion efficiency.
As reported recently, TiO2 photoelectrodes prepared by the
electrospraying method had higher photocurrents than con-
ventional photoelectrodes because of better ionic paths in the
TiO2 layer.[24] In our previous work, micro/nano composite pho-
toanodes fabricated by the electrohydrodynamic technique
showed both better fill factors and better conversion efficiency
for quasi-solid-state DSSCs.[25] However, the essence of this
phenomenon was not clearly understood. Herein, instead of
using the P25 TiO2 that we used as photoanode material in our
previous work, hydrothermal-synthesized anatase TiO2 nano-
particles are employed, for which a higher conversion efficien-
cy of 7.1 % and a fill factor of 75.3 % are attained for hierarchi-
cal thin films containing branched inner channels with viscous
ionic-liquid electrolyte. The influence of charge transport and
light scattering in the micro/nano composite films are investi-
gated and compared to nanostructured films with and without
hollow spherical voids. The EIS measurements indicate that ion
[a] Dr. Y. Zhao, Dr. X. Sheng, Prof. J. Zhai, Prof. L. Jiang, Prof. C. Yang,
Dr. Z. Sun, Prof. Y. Li, Prof. D. Zhu
Center for Molecular Science, Institute of Chemistry
Chinese Academy of Sciences
Fax: (+ 86) 10-8262-7566
E-mail: zhaijin@iccas.ac.cn
[b] Dr. Y. Zhao, Dr. X. Sheng
Graduate School of the Chinese Academy of Science
Chinese Academy of Sciences
Beijing 100080 (P. R. China)
[**] For High-Efficiency Solar Cells.
Supporting information for this article is available on the WWW under
http://www.chemphyschem.org or from the author.
ChemPhysChem 2007, 8, 856 861
TiO2 Porous Electrodes

diffusion within the composite film containing con-

tinuous three-dimensional channels had superior
ionic transport properties. In addition, the measure-
ments of reflectance and IPCE spectra show that
light scattering within the composite films is of ben-
efit for enhancing light harvesting at longer wave-
lengths, which would enhance the solar energy con-
version efficiency. Based on the progress of current
research and the previous data,[25] it can be deduced
that the composite micro/nano porous structure is
of benefit for constructing high-efficiency devices
for viscous electrolytes, such as ionic-liquid and
quasi-solid-state electrolyte.

Results and Discussion

TiO2 Hierarchical Porous Film Prepared by the
EHD Method
The fabrication process of TiO2 hierarchical film is de-
scribed in the Experiment Section. In a continuous-
spraying mode, numerous copies of TiO2polymer
hybrid microspheres were deposited randomly on
the surface of fluorine-doped tin oxide (FTO) con-
ducting glass to form organicinorganic composite
films layer by layer. During the course of TiO2poly- Figure 1. a) SEM image of electrode 1 (prepared by the EHD method). b) Magnified
mer microsphere deposition under strong electric image of electrode 1. c) SEM image of electrode 2 (prepared by the doctor blade
field, lots of sub-microchannels were formed be- method). d) Magnified image of electrode 2. e) SEM image of electrode 3 with hollow
spheres. f) Magnified image of electrode 3.
tween the TiO2 microspheres in the film. After calci-
nation in air, composite thin films incorporating
micro/nano hierarchical branched inner channels
were obtained.
Characterization of As-Prepared TiO2 Films
Three different types of films were initially examined using
scanning electron microscopy (SEM) and the results are given
in Figure 1. Figure 1 a shows the surface morphology of a
micro/nano composite electrode (electrode 1) prepared by the
EHD method. We can see clearly that the films are composed
of microscale and sub-microscale near-spherical clusters with
diameters of 0.51 mm. In addition to the spherical clusters,
lots of nanopores and micropores of size 2 nm1 mm exist in
this film. From the magnified image (Figure 1 b), it can be seen
that the average size of nanopores is about 1020 nm. Fig-
ure 1 c shows the surface structure of pure nanostructured
electrode (electrode 2), prepared by the simple doctor blade
technique. The nanostructured film displays a relatively flat sur-
face with lots of homogeneous nanopores, while the magni-
fied image (Figure 1 d) indicates that the size of nanopores is
about 1020 nm. In Figure 1 e, in addition to the nanopores
(1020 nm), some hollow spheres are introduced by burning
out the polystyrene particles to form a porous electrode (Elec-
trode 3). The enlarged image (Figure 1 f) shows that the aver-
age diameter of microspheres is ca. 400 nm. (The transmission
electron microscopy image and X-ray diffractometry spectros-
copy of the calcined composite film prepared by EHD tech-
nique can be found in the Supporting Information).
In order to learn more about the pore composition of three
different electrodes, the pore distribution of the electrodes
was determined with nitrogen adsorption experiment. The Bar-
rettJoynerHalenda analysis of the desorption isotherms is
shown in Figure 2. The pore size distribution in curve 1 implies
that electrode 1, prepared by the EHD method, has large
porous channels in the mesoporous (240 nm) and macropo-
rous (> 50 nm) regions. The dominant peaks are in the meso-
pore range centered at 17 nm, while there is a broad pore dis-
tribution from 2 nm to hundreds of nanometers, which has
also been confirmed by the SEM measurement described
above. For nanostructured electrode 2, the average pore distri-
bution is centered at 14 nm, and the size distribution is narrow
(240 nm). After hollow spherical voids are incorporated into
electrode 3, the distribution of mesopores is centered at 17 nm
and becomes broader (270 nm) than that of electrode 2 but
remains narrower than that of electrode 1. (It must be men-
tioned that macropores larger than 200 nm in electrode 1 and
hollow spherical voids with diameter of 400 nm in electrode 3
were inevitably destroyed during the course of dislodging the
TiO2 film from the substrate, so these data cannot be observed
in Figure 2). In addition, the BrunauerEmmettTeller (BET) sur-
face areas from nitrogen adsorption experiments for electro-
des 1, 2, and 3 are 76.4, 75.3, and 77.6 m2 g 1, respectively.

ChemPhysChem 2007, 8, 856 861 @ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org 857

Figure 2. BJH pore-size distributions calculated from N2 desorption iso-
therms. Curve 1 &: electrode 1 with micro/nano composite structure (V: pore
volume, D: pore diameter). Curve 2 N: nanostructured electrode 2. Curve 3
*: electrode 3 containing spherical voids.
According to the character of film formation in the EHD pro-
cess, the film morphologies from SEM images, and BJH pore-
size analysis, the idealized schematic depictions of the three
electrodes are drawn in Figure 3 to illustrate their structural
Figure 3. Schematic depiction of the pore structure of electrodes. a) Elec-
trode 1; b) magnified view of a section of electrode 1; c) electrode 2; d) elec-
trode 3 (thick line: microchannel; thin line: nanochannel).
specialties. Figure 3 a shows the micro/nano composite film
formed by the EHD technique. Lots of sub-micropores are
formed among the interstices of TiO2 sub-microspheres, hence
forming the continuous microchannels (thick lines). Figure 3 b
shows a magnified version of a section of Figure 3 a. Micro-
spheres formed by the EHD method are composed of nanopar-
ticles. The nanopores between the nanoparticles form continu-
ous nanochannels (thin lines). The hierarchical branched inner
channels composed of continuous micropores (thick lines) and
nanopores (thin lines) in electrode 1, like the blood circulation
858 www.chemphyschem.org @ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Zhai et al.
system of the human body constructed by main vessels and
capillary vessels, should be capable of facilitating charge trans-
port in viscous electrolytes. But electrode 2 (Figure 3 c), with
only nanochannels (thin lines), which are like single capillary
vessels, may not be suited for charge transport in viscous elec-
trolytes. As for electrode 3, although hollow spherical voids
have been introduced into the nanoporous structure, single
micropores (Figure 3 d) may not match the continuous micro-
pore channels in electrode 1 for charge transport. The hypoth-
esis of ionic diffusion for different electrodes can be proven
from the different device performances discussed below.
Photovoltaic Behavior of Dye-Sensitized Solar Cells
The photovoltaic performances of electrodes 1, 2 and 3 were
evaluated at one condition chosen to simulate sunlight
(AM1.5, 100 mW cm 2). Figure 4 shows the current density
Figure 4. Photocurrentvoltage plots of DSSCs measured with viscous elec-
trolyte A. The sensitizer was N3 (ruthenium dye). The cell active area was
0.2 cm2 and the light intensity was 100 mW cm 2. 1) Electrode 1 with micr
nano-composite structure; 2) nanostructured electrode 2; 3) electrode 3 con-
taining spherical voids.
versus voltage (IV) curves of DSSCs based on different photo-
anodes with viscous electrolyte. Three to four devices for every
type of photoanode were tested. Table 1 summarizes the pho-
toelectrical parameters and the deviation of each average
value. The data in parentheses in Table 1 are the highest
values, which are shown here. The short-circuit photocurrent
density (Jsc), open-circuit photovoltage (Voc) and fill factor (ff) of
composite electrode 1 with viscous electrolyte A (see Experi-
mental Section for composition) are 13.8 mA cm 2, 0.691 V, and
75.3 %, respectively, yielding an overall conversion efficiency of
7.1 %. For electrode 2, based on pure nanostructured channels,
the corresponding device parameters (Jsc, Voc, ff, and h) are
13.0 mA cm 2, 0.636 V, 68.4 %, and 5.7 %, respectively. For elec-
trode 3, containing hollow-sphere structures, the Jsc, Voc and ff
value are 12.5 mA cm 2, 0.645 V, and 72.8 %, respectively, h =
ChemPhysChem 2007, 8, 856 861
TiO2 Porous Electrodes
Table 1. Device performances of DSSCs with electrodes 1, 2 and 3 for vis-
cous electrolyte A.[a]
Device Jsc Voc [V] ff [%] h [%]
[mA cm 2]
electrode 1 13.5  0.3 0.688  0.03 75  0.3 6.9  0.2
(13.8) (0.691) (75.3) (7.1 )
electrode 2 12.6  0.4 0.632  0.04 68.1  0.3 5.4  0.3
(13.0) (0.636) (68.4) (5.7)
electrode 3 12.4  0.3 0.642  0.03 72.4  0.4 5.7  0.2
(12.5) (0.645) (72.8) (5.8)
[a] Three or four devices for every type of photoanodes were tested. The
light intensity was 100 mW cm 2. The values reported here are the aver-
age data of four cells with deviations, while the maximum values are
given parentheses.
5.8 %. Of the three different electrodes, composite electrode 1
gives the highest values for both fill factor and h.
In order to confirm that composite photoelectrodes with hi-
erarchical porous channels can enhance the conversion effi-
ciency indeed, another viscous electrolyte (electrolyte B; see
also the Experimental Section) was also used to fabricate
DSSCs. Similar results are obtained (see the Supporting Infor-
mation), again indicating that composite porous channels in
the film enhance conversion efficiency. The electrode 1, 2, and
3 give similar values of the BET surface area, which confirms
that there is no obvious difference among the amount of ab-
sorbed dye molecules for the three electrodes. Consequently,
these phenomena should be attributed to the increased pene-
tration of the viscous electrolyte and the thus remarkably im-
proved charge-transport properties of micro/nano composite
photoanodes with hierarchical branched channels.
Electrochemical Impedance Measurements for Ion Transport
in Viscous Electrolytes
The transport kinetics of the redox couple in the porous TiO2
film is an important process for cell function. For the organic
liquid electrolytes with high drift mobility of charge, the trans-
port kinetics are fast enough to regenerate (i.e. reduce) the
dye in these three electrodes, and no change is observed with
modification of the film structure. If the electrolytes are vis-
cous, as when using ionic liquids as solvents, their diffusion ki-
netics in the porous channels will become the key and limiting
step in photocurrent generation. Dye molecules are active
under light irradiation, and the transport of I3 /I ions to and
from the counter electrode is not fast enough to fully regener-
ate the dye molecules in nanostructured electrodes; lower
photocurrent and a smaller fill factor are obtained.
It has been pointed out that the properties of ionic diffusion
in the electrolyte films can be ascertained by impedance meas-
urements. The minimum-frequency peak at low-frequency
range can be correlated to the Nernst diffusion-limited process
in the electrolyte. The higher the low-frequency peak is, the
quicker the ion diffuses.[26] Figure 5 shows typical EI spectra.
The inset is an enlarged plot at the low frequency; the figure
ChemPhysChem 2007, 8, 856 861 @ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 5. Electrical impedance spectra of 1) electrode 1 (~ magnitude and ~
phase), 2) electrode 2 (& magnitude and & phase) and 3) electrode 3 (* mag-
nitude and * phase) measured with the viscous electrolyte A with an illumi-
nation of 100 mW cm 2. The inset is an enlarged plot of the low-frequency
section. Film thickness is about 10 mm. The frequencies are average data
with a deviation of  0.03 Hz.
is presented in the forms of Bode plots. Strikingly, the low fre-
quency for electrode 2, shown in Bode phase plots, is 0.12 Hz,
and 0.31 Hz for electrode 3, while for electrode 1 (prepared by
the EHD method), the low frequency increases to 0.49 Hz. The
frequencies showed here are for the average data with a devia-
tion of  0.03 Hz. Obviously, the capability of ionic diffusion in
hierarchical branched inner channels is best for viscous electro-
lytes, leading to the best fill factors for micro/nano composite
photoanodes. It must be mentioned that though electrode 3
incorporates hollow spherical voids on a sub-micrometer scale,
according to EIS measurements, independent micropores in
the film cannot facilitate better ion-diffusion behavior than is
found for electrode 1 with its continuous micro/nano porous
network.
On the other hand, a Voc of 0.691 V for electrode 1, 0.636 V
for electrode 2, and 0.645 V for electrode 3 are obtained with
electrolyte A; thus, electrode 1 with hierarchical branched
micro/nano channels gives the largest value of Voc. As reported,
photovoltage and photocurrent are influenced by the film
thickness in DSSC systems, which can be ascribed to the rapid
concentration increase of the recombination centers (traps) off-
setting that of the injection centers (dye species), that is, the
recombination rate grows faster than the injection rate does
with the increasing film thickness.[2731] Herein, composite
porous structures not only enhance the transportation proper-
ties of redox-active species but also reduces the numbers of
the traps, and thus increases the photovoltage. In addition, the
internal resistance for the composite electrode should be
lower than for the nanostructured electrode, since the ions can
diffuse quickly to the counter electrode; at the same time, the
faster ion transport in the hierarchical structure can decrease
the charge recombination between the electron and the I3
ion, resulting in higher photovoltage and a higher fill factor.
www.chemphyschem.org 859

Influence of the Light-Scattering Effect on the
Photoelectrical Character of DSSCs
Another important factor that is influenced by the composition
of the films is the light-harvesting efficiency. By introducing
large nanoparticles or spherical voids, the light absorption
range can be extended, and the light-harvesting efficiency can
be enhanced through light scattering.[21, 23] Reflectance meas-
urements of three types of sensitized electrodes are shown in
Figure 6. Nanostructured electrode 2 shows the lowest scatter-
Figure 6. Measured diffuse reflectance of sensitized films. 1) electrode 1 with
micro/nano composite structure. 2) nanostructured electrode 2. 3) elec-
trode 3 containing spherical voids.
ing. After micro/nano composite structure is introduced into
electrode 1, the scattering is enhanced clearly, and higher con-
version efficiency is obtained, because light-scattering macro-
pores are incorporated into the TiO2 thin film to extend the
photoresponse to red region. A photocurrent action spectrum
for electrodes 1 and 2 with ionic-liquid electrolyte A is shown
in Figure 7. Electrode 1 shows enhanced red-region absorption
as a result of light scattering. But it cannot be deduced that
the improvement of photocurrent is only decided by the light-
scattering effect; the better ionic diffusion may also decrease
the loss of charge transport, resulting in better photocurrent
generation.
The kinetics of ion transport and light-collection efficiency
influence each other, and there must be a balance to achieve
the best photovoltaic performance. If the pores are too large,
despite easy ion transport for viscous electrolytes and favora-
ble light-scattering, the thin films cannot absorb enough dye
molecules for light harvesting; if the pores are too small, the
transport kinetics of redox species limit the charge-transfer
rate, and the light-scattering effect is lost, even as the amount
of absorbed dye increases.[7, 32] As a result, electrode 3 shows
the strongest scattering effect among the three types of thin
films, but it does not obtain the highest conversion efficiency.
This can be ascribed to the decrease of surface area and light
loss owing to back scattering arising from the presence of
860 www.chemphyschem.org @ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Zhai et al.
Figure 7. Photocurrent action spectra of composite electrode 1 and nano-
structured electrode 2 with electrolyte A.
hollow spheres, which counteract the light scattering effect.
Composite structures with hierarchical channels balance these
two effects of ion transport and light scattering, and thereby
obtain optimal photoelectrical action.
Conclusions
A simple and effective hierarchical structure is introduced into
nanocrystalline thin films to provide a new way to improve
charge transport and light harvesting, while a conversion effi-
ciency h = 7.1 % and a fill factor ff = 75.3 % were attained for
viscous electrolytes. This result means that photoelectrical per-
formance can be tuned by changing the composite porous
structure, which will give a good strategy for the fabrication of
photoelectrodes suited for highly viscous electrolytes. The idea
of film-structure modulation will provide a promising new way
to approach high-efficiency devices.
Experimental Section
Preparation of Dye Sensitized Solar Cells: Two methods were em-
ployed to prepare TiO2 thin films. Method 1: Micro/nano composite
electrode 1 was fabricated by the EHD technique.[25] The TiO2 col-
loidal suspension was composed of ethanol (5 mL), poly(vinyl alco-
hol) (PVA, MW = 22,000) water solution (1 g, 33 wt %), titanium sol
(6.6 mL, 0.1 g mL 1; anatase TiO2 nano-particles were hydrothermal-
ly synthesized according to ref. [33]). The suspension was sprayed
onto the conducting FTO glass slides with block layer (the prepara-
tion method of which is described elsewhere[25]). Then, the TiO2
composite films were calcined at 450 8C for 1 hour in air. The
whole EHD process was operated in air. Method 2: Nanostructured
films (electrode 2) were prepared by the doctor blade technique,
which employed the colloidal TiO2 suspension used above, spread-
ing it evenly onto the conducting glass. The 10-mm thin films were
obtained after repeating the above procedure several times. The
nanostructured electrodes with hollow spheres (electrode 3) were
prepared according to ref. [21]: Monodisperse polystyrene (PS)
spheres with a radius of 200 nm were dispersed in the TiO2 colloi-
dal suspension used as above in a ratio of 1: 20 by weight using
ChemPhysChem 2007, 8, 856 861
TiO2 Porous Electrodes
an ultrasonic bath. the doctor blade method was used to prepare
the thin films with PS spheres. After sintering them at 450 8C, the
PS particles was burned out, thus leaving hollow spheres as scat-
tering centers.[21] Performance of the photoanodes was further im-
proved by depositing TiO2 from 0.2 m TiCl4 aqueous solution. The
TiCl4 treatment covers the impure TiO2 core with a thin layer of
highly pure TiO2, which can improve the injection efficiency and
the blocking character of the semiconductorelectrolyte junction.[8]
The calcined films were soaking in ethanol solution containing 3 M
10 4 m RuACHTUNGRE(dcbpy)2ACHTUNGRE(NCS)2 (N3; dcbpy = 2,2-bipyridine-4,4-dicarbox-
ylic acid) for 24 h. After completion of the dye coating, the electro-
des were rinsed with dry ethanol and dried in a flow of nitrogen.
Then, the internal space of the porous TiO2 electrodes was filled
with viscous electrolytes by a vacuum pump, and Pt counter-elec-
trodes were overlapped onto the photoanodes to produce the de-
vices.[9] The viscous electrolyte (electrolyte A) was composed of
0.5 m iodine and 0.45 m N-methyl-benzimidazole (NMBI) in a mix-
ture of 3-methoxypropionitrile and 1-propyl-3-methylimidazolium
iodide (PMII; volume ratio 7:13). The electrolyte used for compari-
son (electrolyte B) was composed of 0.1 m iodine, 0.05 m LiI and
0.45 m NMBI in a mixture of PMII and 1-hexyl-3-methylimidazolium
iodide (HMII; volume ratio 13:7).
Measurements: The surface morphology and thickness of these
porous films were determined by SEM (JEOL, JSM-6700F). The Bru-
nauerEmmettTeller (BET) surface area of the powder was ob-
tained using nitrogen adsorption in a Micromeritics ASAP 2010 ni-
trogen adsorption apparatus. The UV/Vis spectra were measured
with a spectrophotometer (U-3010, HITACHI). The electrochemical
impedance measurements were carried out on a Zahner IM6e im-
pedance analyzer (Germany) in the frequency range 0.03 Hz100
KHz with illumination of 100 mW cm 2. The IV characteristics of
the devices were measured using an electrochemical analyzer
(CHI630B, Chenhua Instruments Co., Shanghai) under 100 mW cm 2
irradiation of solar-simulator illumination (CMH-250, Aodite Photo-
electronic Technology Ltd., Beijing) at room temperature. The IPCE
curves of the DSSCs were measured by illumination with mono-
chromatic light, which was obtained by passing light through a
series of light filters with different wavelengths. The active area of
the solar cell was 0.20 cm2.
Acknowledgements
This work was supported by Special Research Foundation of the
National Natural Science Foundation of China (50533030,
20573120) and the National Research Fund for Fundamental Key
Projects No. 973 (2006CB806200, 2006CB932100). We thank Prof.
Zhengzhong Yang at the Institute of Chemistry, Chinese Academy
of Sciences, for his help with supporting the monodisperse poly-
styrene sphere.
Keywords: charge transport dyes/pigments
electrochemistry light harvesting nanostructures
[1] B. ORegan, M. GrOtzel, Nature 1991, 353, 737 740.
[2] I. Robel, V. Subramanian, M. Kuno, P. V. Kamat, J. Am. Chem. Soc. 2006,
128, 2385 2393.
[3] P. V. V. Jayaweera, A. G. U. Perera, M. K. I. Senevirathna, P. K. D. D. P. Piti-
gala, K. Tennakone, Appl. Phys. Lett. 2004, 85, 5754 5756.
ChemPhysChem 2007, 8, 856 861 @ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
[4] M. Adachi, Y. Murata, J. Takao, J. T. Jiu, M. Sakamoto, F. M. Wang, J. Am.
Chem. Soc. 2004, 126, 14 943.
[5] M. Y. Song, Y. R. Ahn, S. M. Jo, D. Y. Kim, J. P. Ahn, Appl. Phys. Lett. 2005,
87, 113 113.
[6] S. Hattori, Y. Wada, S. Yanagida, S. Fukuzumi, J. Am. Chem. Soc. 2005,
127, 9648 9654.
[7] C. J. Barbe, F. Arendse, P. Comte, M. Jirousek, F. Lenzmann, V. Shklover,
M. GrOtzel, J. Am. Ceram. Soc. 1997, 80, 3157 3171.
[8] M. K. Nazeeruddin, A. Kay, I. Rodicio, R. H. Baker, E. MPller, P. Liska, N.
Vlachopoulos, M. GrOtzel, J. Am. Chem. Soc. 1993, 115, 6382 6390.
[9] P. Wang, S. M. Zakeeruddin, P. Comte, I. Exnar, M. GrOtzel, J. Am. Chem.
Soc. 2003, 125, 1166 1167.
[10] W. Kubo, S. Kambe, S. Nakade, T. Kitamura, K. Hanabusa, Y. Wada, S. Ya-
nagida, J. Phys. Chem. B 2003, 107, 4374 4381.
[11] Y. Shibata, T. Kato, T. Kado, R. Shiratuchi, W. Takashima, K. Kaneto, S.
Hayase, Chem. Commun. 2003, 21, 2730 2731.
[12] X. T. Zhang, I. Sutanto, T. Taguchi, Q. B. Meng, T. N. Rao, A. Fujishima, H.
Watanabe, T. Nakamori, M. Uragami, Sol. Energy Mater. Sol. Cells 2003,
80, 315 326.
[13] A. F. Nogueira, J. R. Durrant, M. A. De Paoli, Adv. Mater. 2001, 13, 826
830.
[14] E. Stathatos, P. Lianos, U. Lavrencic-Stangar, B. Orel, Adv. Mater. 2002,
14, 354 357.
[15] S. X. Tan, J. Zhai, B. F. Xue, M. X. Wan, Q. B. Meng, Y. L. Li, L. Jiang, D. B.
Zhu, Langmuir 2004, 20, 2934 2937.
[16] G. R. A. Kumara, A. Konno, K. Shiratsuchi, J. Tsukahara, K. Tennakone,
Chem. Mater. 2002, 14, 954 955.
[17] D. Gebeyehu, C. J. Brabec, F. Padinger, T. Fromherz, S. Spiekermann, N.
Vlachopoulos, F. Kienberger, H. Schindler, N. S. Sariciftci, Synth. Met.
2001, 121, 1549 1550.
[18] M. K. Nazeeruddin, P. Pechy, M. GrOtzel, Chem. Commun. 1997, 1705
1706.
[19] S. M. Zakeeruddin, M. K. Nazeeruddin, R. Humphry-Baker, M. GrOtzel, V.
Shklover, Inorg. Chem. 1998, 37, 5251 5259.
[20] S. Nishimura, N. Abrams, B. A. Lewis, L. I. Halaoui, T. E. Mallouk, K. D.
Benkstein, J. van de Lagemaat, A. J. Frank, J. Am. Chem. Soc. 2003, 125,
6306 6310.
[21] S. Hore, P. Nitz, C. Vetter, C. Prahl, M. Niggemann, R. Kern, Chem.
Commun. 2005, 15, 2011 2013.
[22] H. Nusbaumer, S. M. Zakeeruddin, J. E. Moser, M. GrOtzel, Chem. Eur. J.
2003, 9, 3756 3763.
[23] W. E. Vargas, G. A. Niklasson, Sol. Energy Mater. Sol. Cells 2001, 69, 147
163.
[24] M. Fujimoto, T. Kado, W. Takashima, K. Kaneto, S. Hayase, J. Electrochem.
Soc. 2006, 153, 826 829.
[25] Y. Zhao, J. Zhai, S. Tan, L. Wang, L. Jiang, D. B. Zhu, Nanotechnology
2006, 17, 2090 2097.
[26] R. Kern, R. Sastrawan, J. Ferber, R. Stangl, J. Luther, Electrochim. Acta
2002, 47, 4213 4225.
[27] R. Gomez, P. Salvador, Sol. Energy Mater. Sol. Cells 2005, 88, 377 388.
[28] K. Hara, T. Horiguchi, T. Kinoshita, K. Sayama, H. Sugihara, H. Arakawa,
Sol. Energy Mater. Sol. Cells 2000, 64, 115 134.
[29] N. G. Park, J. van de Lagemaat, A. J. Frank, J. Phys. Chem. B 2000, 104,
8989 8994.
[30] S. Ito, T. Kitamura, Y. Wada, S. Yanagida, Sol. Energy Mater. Sol. Cells
2003, 76, 3 13.
[31] M. Zukalova, A. Zukal, L. Kavan, M. K. Nazeeruddin, P. Liska, M. GrOtzel,
Nano. Lett. 2005, 5, 1789 1792.
[32] Z. S. Wang, H. Kawauchi, T. Kashima, H. Arakawa, Coord. Chem. Rev.
2004, 248, 1381 1389.
[33] A. Zaban, S. Ferrere, J. Sprague, B. A. Gregg, J. Phys. Chem. B 1997, 101,
55 57.
Received: October 24, 2006
Published online on March 21, 2007
www.chemphyschem.org 861