ACTA PHYSICO-CHIMICA SINICA

Volume 24, Issue 12, December 2008

Online English edition of the Chinese language journal

Cite this article as: Acta Phys. -Chim. Sin., 2008, 24(12): 2191−2197. ARTICLE

Preparation and Characterization of TiO2 Nanotube Arrays

via Anodization of Titanium Films Deposited on FTO
Conducting Glass at Room Temperature
Yuxin Tang, Jie Tao*, Yanyan Zhang, Tao Wu, Haijun Tao, Zuguo Bao

College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, P. R. China

Abstract: Self-organized TiO2 nanotube arrays with micro-scale length were prepared on fluorine-doped tin oxide (FTO)
conducting glass in NH4F/glycerol electrolyte by electrochemical anodization of pure titanium films deposited by radio frequency
magnetron sputtering (RFMS) at room temperature. The samples were characterized by means of field emission scanning electron
microscopy (FESEM), X-ray diffraction (XRD), and photoelectrochemistry methods. The results showed that Ti films prepared at
the condition of Ar pressure 0.5 Pa, power 150 W, and 0.5 h at room temperature possessed the zone T model structure with good
homogeneity and high denseness. When the anodization time was prolonged from 1 to 3 h at the voltage of 30 V, the pore diameter
of TiO2 nanotubes increased from 50 to 75 nm, and the length increased from 750 to 1100 nm and then gradually decreased to 800
nm, while their wall morphology changed from smooth to rough. Also with increasing the anodization voltage, the pore diameter
became larger, and the remaining oxide layer reduced, which could be easily removed by ultrasonic- chemical cleaning in 0.05% (w,
mass fraction) diluted HF solution. Moreover, the photocurrent response curves and electrochemical impedance spectroscopy (EIS)
results indicated that UV-illumination clearly enhanced the effective separation of the electron-hole pairs and the crystallized
electrodes from the annealing treatment of as-anodized electrodes at 450 °C exhibited a better photoelectrochemical performance.

Key Words: Radio frequency magnetron sputtering; Room temperature; FTO conducting glass; TiO2 nanotube arrays;
NH4F/glycerol

The growth of metal film in vacuum is a deposition process
of massive atoms or atomic groups arriving on the substrate,
which is affected by the deposition parameters, such as sub-
strate temperature, sputtering pressure, and power. The micro-
structure of the films is dominated by the relative substrate
temperature and the energy of deposition atoms[1−4]. Mainly,
there are evaporation method and sputtering method to pre-
pare metal films by vacuum deposition. The former easily
conducted in simple equipment can manufacture the films
with poor compactness and several bubbles. The latter can
produce firm and dense films with good homogeneity and re-
producibility in a large area owing to high-energy bombarding
particles. Therefore sputtering method has become an impor-
tant way that has been used very widely.
Recently, titanium film has drawn extraordinary attention
for its applications in microelectronics, machinery, aerospace,
and medical industry owing to its remarkable photoelectric
performance and corrosion resistance. Mor group[5] has suc-
cessfully developed the technology to grow TiO2 nanotube ar-
rays from titanium thin films deposited on glass substrates at
500 °C by anodization. The well-orderly and perpendicularly-
oriented TiO2 nanotubes possessed not only large specific
surface area and strong absorption capacity, but also superior
electron lifetimes owing to providing excellent pathways for
electron percolation. Thus they exhibited high photoelectric
conversion efficiency[6−8] and good photocatalytic proper-
ties[9,10]. Some other groups[11−16] also used the same way to
deposit Ti films at high temperature on a variety of substrates
(e.g. silicon). However, the length of nanotube arrays prepared
in the electrolytes was less than 700 nm since the increasing of

Received: July 14, 2008; Revised: September 17, 2008.

*Corresponding author. Email: taojie@nuaa.edu.cn; Tel: +8625-52112900.
The project was supported by the Natural Science Foundation of Jiangsu Province (BK2004129) and the Aeronautical Science Foundation of China (04H52059).

Copyright © 2008, Chinese Chemical Society and College of Chemistry and Molecular Engineering, Peking University. Published by Elsevier BV. All rights reserved.
Chinese edition available online at www.whxb.pku.edu.cn
 Yuxin Tang et al. / Acta Physico-Chimica Sinica, 2008, 24(12): 2191−2197
the thickness of Ti-sputtered films resulted in the degradation
of the films′ quality[5,6]. Obviously, it is not appropriate to de-
posit Ti film at high temperature on flexible and temperature-
nonresistant substrates, e.g. polyethylene terephthalate (PET)
or polyethylene naphthalate polymer (PEN). Moreover, to
prepare TiO2 nanotubes on transparent substrates (e.g. con-
ducting glass, PET substrate) can enhance the light-converting
efficiency of optical-electric devices based on the TiO2 nano-
tubes and make these devices microminiaturized and flexible.
Although Eu[17] and Neale[18] et al. have prepared the porous
titania films on the transparent substrate, the distribution of
the pores is not ordered and highly oriented. According to our
previous work[19], the quality (dense, uniform) of the titanium
film and the anodization parameters are critical to the forma-
tion process of titania nanotubes. Therefore, on the basis of
the fabrication of high-qualify Ti films, it is necessary to se-
lect an electrolyte with low chemical dissolution rate to in-
crease the thickness-conversion ratio of Ti film. In this study,
we attempt to deposit compact and uniform Ti films on con-
ducting glass at room temperature, and then fabricate large
aspect ratio TiO2 nanotube layer (1100 nm) in NH4F/glycerol
electrolyte. Additionally, the growth process and photoelec-
trochemical characteristics of the TiO2 nanotubes are investi-
gated, and a method for eliminating the cover layer on the
nanotube surface is also discussed.
1 Experimental
1.1 Deposition of the titanium film at room temperature
on conducting glass
Ti films (ca 1.47 µm) were deposited on fluorine-doped tin
oxide (FTO) conducting glass at room temperature by RFMS
(radio frequency magnetron sputtering) (JPG500, China). A Ti
disk (99.9% purity, TianYuan Co., Ltd., Shenzhen, China)
with 60 mm diameter and 5 mm thickness was used as the
target. The base chamber pressure was below 7.0×10−4 Pa and
the distance between the target and sample was 60 mm. To
remove pinhole defects in the titanium film, the specimen was
cleaned by ultrasonic in acetone, ethanol, and deionized water
for 15 min, respectively. Before deposition, the target was
prior sputtered for 10 min to remove the oxide layer or other
impurities on the titanium target surface. During the deposi-
tion process, the argon gas (99.999% purity) pressure (pAr)
was 0.5 Pa with gas flowing at 10 mL·min−1 and the sputtering
power (Ps) was 150 W at room temperature. After deposition
for 0.5 h, the samples were kept in vacuum for 6 h.
1.2 Preparation of TiO2 nanotubes on FTO glass using an
anodization method
Anodization was carried out using a two-electrode configu-
ration. Titanium film/FTO with an exposed surface area of 1.0
cm2 was used as the working electrode. A platinum sheet (2
cm×1.5 cm) with a copper wire was used as the counter-elec-
trode. The distance between the working and counter-
electrodes was kept at 3 cm. A DC power source (WYK-1502,
Eksi Electronic Co., Ltd., Jiangsu, China) supplied the re-
quired anodization potential (10−40 V) in a single step (with-
out ramping). Anodization was conducted in 0.5% (w)
NH4F/glycerol at room temperature using a digital multimeter
interfaced with a computer. After anodization, the samples
were immediately washed with distilled water and subse-
quently dried in air. Some samples were heat treated for 3 h at
different temperatures ranging from 300 to 550 °C in air at a
heating rate of 5 °C·min−1, and then the samples were cooled
in the furnace.
2 Results and discussion
2.1 Characterization of titanium films deposited at room
temperature
The atom deposition process can be divided into three steps,
namely the gas phase atom′s deposition or adsorption, the sur-
face diffusion, and the bulk self-diffusion. The morphological
features of metal films are given on the basis of the relative
substrate temperature Ts/Tm (Ts is substrate temperature, Tm is
melting point of the deposited material) and the energy of
deposition atoms. The morphological features were named as
zone 1, zone T, zone 2, and zone 3 for high melting point
metal film by taking into account the Ts/Tm and the pres-
sure[1−4]. Based on the titanium film (Tm(Ti)=1660 °C) deposited
at room temperature (Ts(FTO)<150 °C) in this experiment and
hence Ts(FTO)/Tm(Ti)<0.3, the Ti film structure depended on the
sputtering pressure and power will be formed between zone 1
and zone T. Compared with zone 1, the critical nucleus size of
Ti grains is still small and the structure is also consisted of an
array of fibrous grains in the zone T, however, the surface dif-
fusion of the atom is significant, causing the relatively com-
pact structure at grain boundaries without holes and tapered
crystals. Apparently, it is necessary to choose the appropriate
sputtering parameters to promote the appearance of zone T
structure. At suitable low sputtering pressure and high sput-
tering power, the Ti atom will obtain higher energy. Therefore,
the surface diffusion is improved and the substrate tempera-
ture increases, yielding a movement of the structure to zone T
region.
FESEM images, XRD pattern, and EDX spectrum of Ti
film deposited under the conditions of pAr=0.5 Pa, Ps=150 W,
and t=0.5 h at room temperature are shown in Fig.1. In
Fig.1(a−c), it is found that a close-packed hexagonal structure
of α-Ti film with (002) preferred orientation appears when
150 W power is applied. The microstructure of the film is
uniform with the grain size of 100 nm, and a banding distribu-
tion of columnar structure belonged to the typical zone T
structure with high density is seen from the cross-section of
the film. The Ti atom has high energy to migrate and occupy
the equilibrium sites of titanium crystal lattice when the Ti
 Yuxin Tang et al. / Acta Physico-Chimica Sinica, 2008, 24(12): 2191−2197
Fig.1 (a) Top and (b) cross-sectional FESEM images of Ti film and the corresponding (c) XRD pattern and (d) EDX spectrum
film is deposited at appropriate high sputtering power and low
sputtering pressure, which results in the growth of the colum-
nar structure (zone T). Moreover, the result of the chemical
analysis by energy dispersive X-ray (EDX) spectroscopy
(Fig.1(d)) indicates that an almost pure Ti film is formed with
a low oxygen contamination level (below 1%). Fig.2 depicts
FESEM images of TiO2 nanotube arrays via anodization of ti-
tanium films deposited at different conditions in 0.5% (w) HF
solution at 10 V. When Ti film is deposited at 500 °C
(Ts(FTO)/Tm(Ti)> 0.3)[14], the structure of the film belongs to the
zone 2 form. In this condition, the surface and bulk diffusion
of the film are significant and the deposited atoms migrate
adequately, so that the shadowing effect is weakened, leading
to a columnar structure of the film with high denseness.
Therefore, the substrate is frequently heated at high tempera-
ture to create a dense, uniform, and crystal titanium film suit-
able for anodization[5−7,11−16]. In this experiment, the morpho-
logical feature of uniform and organized titania nanotubes
(Fig.2(a)) anodized from Ti films deposited at room tempera-
ture is similar to Fig.2(b), which indicates that the dense and
uniform Ti film obtained directly at room temperature is fa-
vorable for the formation of ordered nanotube arrays.
2.2 Fabrication and characterization of TiO2 nanotube
arrays on FTO glass substrates
Fig.3 depicts the current–time behaviors recorded at 10 V
for 0.5% (w) HF/1 mol·L−1 H3PO4 and 0.5% (w) NH4F/glyc-
erol electrolytes. It can be seen that the behaviors are not dif-
Fig.2 FESEM images of TiO2 nanotube arrays via anodization of
titanium films deposited at different conditions
(a) pAr=0.5 Pa, Ps=150 W, Tsubstrate=room temperature, t=0.5 h;
(b) pAr=0.5 Pa, Ps=150 W, Tsubstrate=500 °C, t=1 h
ferent from that of the Ti films anodized in HF solution[19].
However, this process is relatively slow for NH4F/glycerol
electrolyte owing to its high dielectric constant and coefficient
of viscosity. Also, a low current density is found in the viscous
electrolyte, which is only one-tenth of HF/H3PO4 electrolyte,
indicating that the anodization process is controlled by diffu-
sion. Hence a dependence of the diffusion constant on the
viscosity is in a Stokes-Einstein manner: D=kBT/6πηr, where
D is the diffusion constant, kB is Boltzmann′s constant, T is the
absolute temperature, η is the dynamic viscosity, and r is the
radius of a spherical body. According to this formula, D is in-
versely proportional to η. Therefore, a lower growth and
chemical dissolution rate of the nanotubes is obtained in the
viscous electrolytes. Also, it takes a long time to reach the
stable-state. As the anodization proceeds, the steep rise of
current in HF/H3PO4 electrolyte occurs earlier than in glycerol
electrolyte after going through the stable stage. The current
increase is because the electrolyte interacts with the FTO sur-
face as the last of the Ti film is consumed. Meanwhile, the
sample becomes translucent and should be quickly removed
from the electrolyte; otherwise it would be consumed by the
HF. Moreover, compared with smooth current curve in glyc-
erol electrolytes, occasional fluctuations of the current curve
are found in HF/H3PO4 electrolyte, which is caused by oxygen
bubbles (2H2O−4e→4H++O2↑) produced on the pinholes in Ti
film or any exposed FTO substrate at the condition of high
potentials and low viscosity of the aqueous HF/H3PO4 elec-
trolyte. However, this phenomenon does not appear in the
Fig.3 Current density–anodizing time curves of titanium films at
10 V in different electrolytes
(a) 0.5% (w) NH4F/glycerol, (b) HF/H3PO4
 Yuxin Tang et al. / Acta Physico-Chimica Sinica, 2008, 24(12): 2191−2197

glycerol electrolyte. taneously, the variation of the amount of water in glycerol

The effect of anodization time and voltage on the formation
of TiO2 nanotubes in 0.5% (w) NH4F/glycerol electrolyte is
studied. Fig.4(a−g) shows FESEM images of the samples ano-
dized for different times at the voltage of 30 V. At the initial
stage of anodization (Fig.4(a, b)), the surface of nanotubes is
almost covered with a porous oxide layer. After anodization
for 1 h, the pore diameter of TiO2 nanotubes is about 50 nm,
with the length of 750 nm, which is longer than that of aque-
ous HF/H3PO4 electrolyte for the same time. In this case, the
wall morphology of TiO2 nanotubes is smooth. When the ano-
dization time is 2 h (Fig.4(d, e)), the morphology of the nano-
tube arrays is getting clear owing to the obvious thinning of
the porous structure. The pore diameter and the length of the
nanotubes with roughness and ripples at the bottom of tube
walls increases to 75 nm and 1100 nm, respectively, while the
thickness of Ti film decreases to 200 nm. During the anodiza-
tion process, the glycerol electrolyte keeps absorbing moisture
in the air, leading to the drop of the resistance of the electro-
lyte. As a result, the rise of effective potential on the Ti/FTO
electrode results in the diameter of TiO2 nanotubes to increase
with the increasing amount of water in the electrolyte. Simul-
electrolyte causes the difference in the dissolution and the ox-
ide formation rate of TiO2 nanotubes, bringing about the
change of the wall topography. These phenomena are the
same for the anodization of Ti foil[20,21]. When the anodization
time is prolonged to 3 h, the pore diameter of nanotubes is no
longer changed. And the porous structure is consumed com-
pletely because of the chemical dissolution during the anodi-
zation (Fig.4(f, g)). The length of the nanotubes is shortened
to 800 nm with some collapsed nanotubes on the surface ow-
ing to the serious corrosion of the electrolyte. The whole
formed tubes have rough walls with ripples. Fig.4(h, i, f)
shows FESEM images of samples anodized for 3 h at the
voltages of 10, 20, and 30 V, respectively. Obviously, the po-
tential has a large effect on the tube diameters, ranging from
about 35 nm at 10 V to 75 nm at 30 V. However, the porous
layer existed after 3 h anodization reduces gradually with the
increase of anodizing potential. This indicates that the higher
potential not only increases the electric field intensity of the
oxide layer, but also speeds up the diffusion of ions, leading to
the higher growth rate of nanotube, and accelerating the field-
enhanced dissolution rate of the upper oxide layer. Therefore,

Fig.4 Top and cross-sectional FESEM images of TiO2 nanotubes anodized in 0.5% (w) NH4F/glycerol electrolyte at
different conditions
(a, b) 0.5 h, (c) 1 h, (d, e) 2 h, (f, g) 3 h at 30 V, and top view at 10 V (h), 20 V (i) for 3 h
 Yuxin Tang et al. / Acta Physico-Chimica Sinica, 2008, 24(12): 2191−2197

Fig.5 Top view of the surface of TiO2 nanotubes in Fig.4(d) after ultrasonic cleaning by immersing in
0.05% (w) HF solution for different times
(a) 15 s, (b) 30 s, (c) 60 s

the increase of the potential can promote dissolution of the
cover oxide layer.
In order to remove the porous oxide layer on the surface, a
series of as-prepared samples are cleaned in 0.05% (w) HF
solution by chemical etching with ultrasonic. Fig.5 exhibits
the variation on the surface topography of the Fig.4(d) sam-
ples (1100 nm) cleaned at different times. Clearly, the as-
prepared sample without cleaning is almost covered by a thin
porous oxide layer which is dissolved gradually as time passes.
After 15 s treatment (Fig.5(a)), a small part of the uniform
nanotubes are exposed due to the porous oxide film dissolving
under the combined action of the hydrofluoric acid chemical
dissolution and ultrasonic oscillation, and then clear nanotubes
(Fig.5(b)) appear when the time reaches to 30 s. Furthermore,
the porous layer is removed completely after 60 s treatment
(Fig.5(c)), while the topography and the length of nanotubes
are not influenced. Therefore, the ultrasonic-chemical clean-
ing is an efficient method for the removal of the covered oxide
layer.
The XRD patterns of the nanotubular TiO2/FTO electrodes
before and after heat treatment at different temperatures are
shown in Fig.6. Most of Ti film has been transformed to TiO2
nanotube layer (1100 nm) after anodization. The characteristic
peaks of the as-anodized sample (Fig.6(a)) do not arise from
the TiO2 but from the conducting film (SnO2 and SnO) of
FTO and Ti, contributing to the form of the amorphous sample.
After heat treatment at 300 °C for 3 h (Fig.6(b)), the amor-
phous sample transforms to anatase structures characterized
with (101) preferred orientation. At higher temperature (450
°C, 550 °C), the peaks of anatase in Fig.6(c, d) become
stronger and the (110) characteristic diffraction peak of rutile
phase appears, which indicates that the crystal type of TiO2
nanotubes is a mixed structure of anatase and rutile. Also, the
rutile phase grows at the interface between the barrier layer of
the nanotubes and titanium film where the thermal oxidation
occurs (≥430 °C)[5,14].
2.3 Photoelectrochemical characterization of nanotubular
TiO2/FTO electrodes
Figs.7 and 8 show the photocurrent response curves and
electrochemical impedance spectra (EIS) of nanotubular
TiO2/FTO electrodes annealed at different temperatures under
UV illumination, respectively. All electrochemical measure-
ments are carried out in electrolyte solution of 0.1 mol·L−1
Na2SO4 under ultraviolet lamp (UV, 254 nm, 8 W) illumina-
tion using three-electrode system at room temperature with the
TiO2/FTO electrode, a platinum plate, and a saturated calomel
electrode (SCE) served as the working, counter, and reference
electrodes, respectively. The distance between the working
electrode and the UV lamp is 3 cm. The EIS measurement is

Fig.6 XRD patterns of nanotublar TiO2/FTO electrodes annealed Fig.7 Photocurrent response curves of nanotubular TiO2/FTO
at different temperatures electrodes annealed at different temperatures in 0.1 mol·L−1
(a) as-anodized, (b) 300 °C, (c) 450 °C, (d) 550 °C Na2SO4 solution under UV pulsed-illumination
 Yuxin Tang et al. / Acta Physico-Chimica Sinica, 2008, 24(12): 2191−2197
Fig.8 EIS of nanotubular TiO2/FTO electrodes annealed at different
temperatures in 0.1 mol·L−1 Na2SO4 solution under UV illumination
carried out by applying 100 kHz to 0.01 Hz frequency range
with oscillation amplitude of 5 mV on a CHI660 electro-
chemical workstation. As seen in Fig.7, the photoelectric cur-
rent transiently increases and then tends to be stable when UV
light is turned on, which indicates that the nanotube electrode
has a good photoelectric current stability. However, once UV
light is turned off, the photocurrent intensity quickly decreases
to initial value as dark current. This phenomenon illustrates
that the composite electrodes have the n-type semiconductor
characteristic. It is clear that the photocurrent increases along
with the increasing of heat treatment temperature and the re-
sponsive currents are constant at 0.03, 0.38, 1.55, and 4.88 µA
under dark condition and then drastically increase to 1.74,
6.48, 9.78, and 7.95 µA under UV illumination, respectively.
The increase of photocurrent for TiO2 nanotubes under the UV
illumination is owing to the efficient photo-generated elec-
trons conducting through interfacial region of the nanotubes
under an electric field, and the photocurrent level is affected
by the crystallinity and isomorph type of the titania. When the
heat treatment temperature increases, the crystallinity of TiO2
nanotubes is enhanced obviously, leading to the improvement
of photoelectrochemical performance. It is found that the
sample shows better performance at 450 °C. However, when
the temperature is higher than 550 °C, the performance of the
electrode degrades due to the decreasing of the specific sur-
face area of TiO2 nanotubes which results from the structural
damage and collapse of the nanotubes (not shown here). This
is in line with the heat treatment of TiO2 nanotubes on Ti
foil[22−24]. Fig.8 presents that larger radius of the semicircle is
found in the amorphous electrode corresponding to higher
TiO2 resistance value. At the same frequency, the larger the
radius of semicircle, the smaller will be the capacitance con-
stant, which results in higher value of the impedance of Fara-
day current. Therefore, it is more difficult for the chemical
reaction to take place on the electrode owing to the higher en-
ergy barrier. However, it is found that the radius of the semi-
circle decreases after heat treatment. Moreover, the smallest
radius corresponding to the optimal performance appears at
450 °C. This result is consistent with that of the photocurrent
response test.
3 Conclusions
The Ti films were deposited on FTO by RFMS under 0.5 Pa
Ar pressure and 150 W sputtering power at room temperature
for 0.5 h, which possessed a uniform and dense zone T struc-
ture. Then TiO2 nanotubes of 1100-nm length and 75-nm pore
diameter were successfully prepared by potentiostatic anodi-
zation of the Ti films in 0.5% (w) NH4F/glycerol electrolyte at
the voltage of 30 V for 2 h. With the increasing of the anodi-
zation voltage (from 10 to 30 V for 3 h), the pore diameter
became larger (from 35 to 75 nm), and the remaining oxide
layer reduced, which could be easily removed by ultrasonic-
chemical cleaning in 0.05% (w) diluted HF solution. Further-
more, the photoelectrochemistry measurements indicated that
the crystallized electrodes from the annealing treatment of
as-anodized electrodes at 450 °C exhibited better photoelec-
trochemical performance. Additionally, the UV-illumination
clearly enhanced the effective separation of the electron-hole
pairs, so that the photo-induced electrons transferred quickly
to the conducting glass via external circuit and formed photo-
current.
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