Microporous and Mesoporous Materials 119 (2009) 75–81

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Voltage-dependent morphology, wettability and photocurrent response

of anodic porous titanium dioxide films
Hua-Yan Si, Zhen-Hong Sun, Xu Kang, Wei-Wei Zi, Hao-Li Zhang *
State Key Laboratory of Applied Organic Chemistry (SKLAOC), College of Chemistry and Chemical Engineering, Lanzhou University, Tianshui Road 222#, Lanzhou 730000, China

a r t i c l e i n f o a b s t r a c t

Article history: The effects of anodic voltages on the morphology, wettability and photocurrent response of the porous
Received 11 April 2008 titanium dioxide films prepared by electrochemical oxidation in a hydrofluoric acid (HF)/chromic acid
Received in revised form 26 August 2008 electrolyte have been studied. The porous titanium dioxide films showed an increased surface roughness
Accepted 30 September 2008
with the increasing anodizing voltages. By controlling the films morphology and surface chemical com-
Available online 14 October 2008
position, the wettability of the porous titanium dioxide films could be easily adjusted between superhy-
drophilicity and superhydrophobicity. X-ray diffraction (XRD), Raman and UV–vis spectroscopy revealed
Keywords:
that the obtained titanium dioxide films were in anatase phase. The titanium dioxide films showed clear
Titanium dioxide
Morphology
photocurrent response, which decreased dramatically with the increase of the anodizing voltages. This
Superhydrophilicity study demonstrates a straightforward strategy for preparing porous titanium dioxide films with tunable
Superhydrophobicity properties, and especially emphasizes the importance of understanding their morphology/properties
Photocurrent response relationship.
Ó 2008 Elsevier Inc. All rights reserved.

1. Introduction is often considered to be more interesting than the barrier layer

Since Fujishima and Honda reported the photocatalytic split-
ting of water on titanium dioxide electrodes [1], titanium dioxide
has been extensively investigated as a semiconductor photocata-
lyst. Nanoscale titanium dioxide, a wide-band-gap semiconductor
materials, now has found applications in many exciting fields,
like solar energy conversion [2], photocatalysis [3] and self-clean-
ing coating, etc. Various synthetic methods have been developed
for the fabrication of titanium dioxide nanostructures, such as
sol–gel reactions [4], chemical vapor deposition (CVD) [5], hydro-
thermal synthesis [6] and template methods [7]. It is known that
titanium dioxide can also be obtained from oxidation of titanium,
but much less effort has been made to develop synthetic meth-
ods for titanium dioxide materials based on oxidizing titanium,
partly due to the relatively inert properties of the titanium
surface.
Recently, it has been realized that electrochemical oxidation in
fluorine containing solution is a simple and straightforward meth-
od to prepare titanium dioxide coating on titanium substrates
[8,9]. These titanium dioxide films obtained from electrochemical
approaches can be generally described as a porous oxide layer on
a much thinner barrier oxide layer. Under desired condition, the
porous layer consists of regular arrays of vertically aligned nano-
scale titanium dioxide tubes. The porous titanium dioxide layer
* Corresponding author. Tel./fax: +86 931 8912365.
E-mail address: Haoli.zhang@lzu.edu.cn (H.-L. Zhang).
due to its large surface area, which is preferable for most photo
catalysis applications [10].
Compared with the extensive investigation on the other por-
ous oxide materials, especially the anodic aluminium oxide
(AAO) [11,12], the study on the exact formation mechanism of
porous titanium dioxide during electrochemical reaction is still
very limited. Previous works have shown that the structural
parameters of the porous titanium dioxide layers are strongly
dependent on the oxidation condition. Many works [13–16] stud-
ied the effects of electrochemical oxidation condition on thickness
of the titanium dioxide layer. Zwilling et al. [13] suggested that
the thickness of titanium dioxide barrier oxide is independent
of the anodizing time whereas the thickness of the porous tita-
nium dioxide increases. Gaul [14] reported that the thickness of
the titanium dioxide formed is directly proportional to the ap-
plied voltage. However, there are many works suggested that
the thickness of the porous layer was limited to around a few
hundreds of nanometers using fluorine base electrolyte [15–19].
Only very recently, much thicker titanium dioxide nanotube ar-
rays were fabricated by Grimes’ [20,21] group using polar organic
electrolyte. They suggested that the key to achieving very long
nanotube arrays using organic electrolytes appeared to be mini-
mizing the water content to less than 5% [22]. These previous re-
searches have shown that the oxidization condition affects
structural features of the anodic titanium oxide films in a very
complicated way. Therefore more studies are still need to gain
further understanding to the effects of many factors, such as

1387-1811/$ - see front matter Ó 2008 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2008.09.042
76 H.-Y. Si et al. / Microporous and Mesoporous Materials 119 (2009) 75–81
electrolyte, ions strength, temperature and voltages, on the struc-
ture of the porous films.
So far, most effort has been made to improve the order or con-
trol the pore aspect ratio of the porous layers [9], while little atten-
tion has been paid to adjusting the films properties by controlling
the film morphologies, especially the surface roughness. In this
work, we demonstrated that the surface morphologies of the por-
ous titanium dioxide films can be well controlled by varying the
oxidization condition, which consequently bring important prop-
erties changes to the materials.
2. Experimental section
2.1. Specimen preparation
High purity Ti sheets (99.99%, 1 mm thick, 25  10 mm2) were
used in this work. The sheets were firstly degreased in acetone
and subsequently ultrasonicated in de-ionized water for 3 min.
They were then chemically polished in a solution of HNO3:hydro-
fluoric acid (HF) (8:1). For the electrochemical anodization, the Ti
sheet was used as anode and two Al sheets were served as the
cathodes. About 0.5 M chromic acid solution with 1.7 wt% HF
was used as the electrolyte, which was rigorously stirred with
magnetic agitation during the entire anodization process. The reac-
tion was carried out at room temperature (20 °C) with the oxida-
tion voltages varied between 10 and 95 V. To facilitate comparison,
all the samples reported herein were prepared by applying the
same oxidizing time for 1 h unless stated otherwise. All samples
were thoroughly rinsed with distilled water and then dried in ar-
gon flow before further characterization.
2.2. Characterization
Contact angle (CA) measurements were performed according to
the sessile drop method. A small water droplet (ca. 5 ll) was
dropped on the surface with a syringe and the digital images of
the droplet silhouette were captured with a CCD camera (KB-
1380). The contact angle was determined by numerically fitting
to the droplet image.
Raman spectra were obtained by a JY 800 Raman spectrometer
(HR, France) under 532 nm excitation wavelength with a resolu-
tion of 2 cm1. X-ray diffraction (XRD) patterns were recorded
using a Shimadzu D6000 X-ray diffractometer with Cu Ka radiation
(k = 1.540562 Å). UV–vis absorption spectra were measured in
reflection mode on a Lambda 900 UV–vis spectrometer (P.E.,
USA) equipped with an integrate sphere. Scanning electron micros-
copy (SEM) images were acquired by a JEOL JSM-6380LV scanning
electron microscope, which equipped with an energy dispersive
X-ray spectroscopy (EDX) analyzer. Au was sputtered onto the
sample surface before SEM measurement by a JEOL JFC-1600 coat-
er. X-ray photoelectron spectroscopy (XPS) was performed on a
PHI 5702 spectrometer.
Photocurrent measurements were carried out in 0.1 M Na2SO4
utilizing a 500 W mercury light source. The voltage dependence
of the photocurrent was measured under chopped irradiation of
light during a voltage sweep from 1.5 to 0.8 V with the sweep
rate of 10 mV s1. The titanium dioxide films were illuminated
from the front side through a quartz window. A WDS-3 monochro-
mator (Tuopu, China) was employed to obtain the photocurrent ac-
tion spectra. The photocurrents were obtained under short-circuit
conditions, where the titanium dioxide electrode is poised to a
constant potential of 1.2 V. The intensity of the incident monochro-
matic light was typically in the 0.1–0.2 mW/cm2 range. All voltages
were recorded against an aqueous saturated calomel reference
(SCE) electrode.
3. Results and discussion
The Ti sheets showed shining metallic appearance after being
polished. After the electrochemical oxidation, the sample surfaces
were turned into different colors (Fig. 1). It is known that the color
changing is due to change the thickness of titanium dioxide films
through an interference phenomenon between the reflected beam
from the oxide surface and the beam reflected from the interface of
the surface oxide and titanium substrate. Fig. 1 shows that the col-
ors of the anodized samples change from orange to deep blue via
dark purple with the increasing voltages, which suggests that
thicker oxide films were obtained at higher anodizing voltages.
However, the colors of the anodized surfaces are not very vivid; in-
stead they are somehow blurred, indicating rough surfaces were
obtained under the anodization condition.
To evaluate the surface structures, SEM images were taken from
a series of samples fabricated with different anodizing voltages
(Fig. 2). At low voltage, such as 10 V, the pores are relative small
and the overall sample surface is relatively smooth (Fig. 2A). For
the samples anodized at 20 V, regular pores around 120 nm in
diameters can be clearly observed (Fig. 2B). When anodized at
much higher voltages, the morphology of the surface changes dra-
matically (Fig. 2C and D). At 40 V, the pores become near micron
size in diameter. More significantly, there are many rose-like irreg-
ular nodules grown around the pores edges, which consist of sub-
micron titanium dioxide nanoparticles. The sample from 80 V
shows much higher density of pores on the surface, but similar
pore size and irregular nodules around the pores edges as that
from 40 V. Under the same voltage, prolonged anodizing time leads
to slightly bigger pores and more irregular nodules on the surface.
Fig. 3A shows the representative EDX spectrum of the oxidized
samples. The EDX spectra from all the samples show very similar
features, hence, only the spectrum of the 80 V sample is shown
here. The EDX spectrum only shows peaks associated to the Ti
and O elements, and no F element was detected. The surface com-
position of the titanium dioxide films was also determined by XPS
(Fig. 3B). XPS spectrum suggests that the sample surface consisted
primarily Ti, O, which is in agreement with the EDX results. Traces
of F and Cr elements were detected by XPS. Compared with EDX,
which penetrates much more deeply and hence gives bulk compo-
sition, XPS analysis provides the composition information of the
very top surface layer. The fact that neglectable amount of F and
Cr elements are only detected by XPS but not shown on the EDX
indicates that the F and Cr elements are only on the very top sur-
face not incorporated into the titanium dioxide crystalline. It is rea-
sonable to attribute the F and Cr components to the residual
electrolytes that were not completely washed away due to the la-
ger surface area of very porous morphology of the sample surfaces.
C 1s peaks are observed on the spectra of the plain Ti sheet and the
anodized samples with similar intensities, which are not from the
samples but due to the hydrocarbon contamination in the XPS
chamber.
The effect of anodizing voltage on the morphology has been
studied by many groups [15,16,23]. For example, Gong et al. re-
ported that the porous titanium oxide from a HF aqueous solution
exhibited a morphology change from sponge-like to particulate,
then to tube-like, when voltage increased from 3 to 20 V [16].
However, the rose-like irregular nodules structure observed in this
work has not been reported previously. To date, the exact forma-
tion mechanism for the irregular nodules is not fully understood.
It may be attributed to a combination of oxide expansion and etch-
ing speed variation at different positions. At the position close to
the electrolyte/oxide interface, where supply of the O2/OH spe-
cies is abundant, the oxide layer may outgrow those parts further
from the interface. The difference in growth rate should be more
 H.-Y. Si et al. / Microporous and Mesoporous Materials 119 (2009) 75–81 77

Fig. 1. Coloring of the titanium dioxide films prepared by anodic oxidation at (A) 10 V, (B) 20 V, (C) 40 V, (D) 60 V and (E) 80 V.

Fig. 2. SEM images of the surface of the porous titanium dioxide thin films anodized under different voltages: (A) 10 V, (B) 20 V, (C) 40 V and (D) 80 V.
O1s

A B
Cr2p
F1s

Ti2p

C1s
Counts (a.u.)

Counts (a.u.)

Ti3p
Ti3s

80V

30V

Ti
0 2 4 6 1000 800 600 400 200 0
KeV Binding energy (eV )

Fig. 3. (A) The EDX spectrum of the sample anodized at 80 V and (B) XPS survey spectra of untreated Ti sheet and Ti sheets after anodization at 30 and 80 V, respectively.
78 H.-Y. Si et al. / Microporous and Mesoporous Materials 119 (2009) 75–81
significant when the pore separation is large. This is consistent
with our finding in Fig. 2 that the nodules growth is more obvious
on samples with larger pore separation. Meanwhile, the different
growth rate will generate mechanic stress within the oxide films,
which had been extensively discussed in the previous investigation
on ordered AAO films [24]. In the case of the titanium dioxide, the
oxide grown under such mechanic stress may also cause inhomo-
geneous etching by the fluorine containing solution, which induces
a non-flat morphology. Distinguishing the above two effects is dif-
ficult and will require more carefully designed experiments.
As shown in Fig. 2, the surface morphology of the porous tita-
nium dioxide films changes dramatically with the variation of
anodizing voltage. The wettability of the titanium dioxide films
with different morphologies was probed by water contact angle
(CA) measurement. For the as-prepared films, the water CA exhib-
its a clear trend of decrease with the increase of anodizing voltages
(Fig. 4). When the anodizing voltages were higher than 30 V, the
samples became completely wetted by water (Fig. 4D). Due to
the high polar O–Ti–O bonds, it is not very surprising that the tita-
nium dioxide surfaces exhibit low water CA. The CA on a planar
titanium dioxide sample is normally observed between 64° and
74° [25,26]. Much lower CAs are shown in Fig. 4, especially on
the samples from higher anodizing voltages, are attributed to the
increase of roughness.
To assess the contributions from surface chemical composition
and surface morphology, the titanium dioxide surface was modi-
fied by stearic acid. It is known that fatty acid could form self-
assembled monolayers (SAMs) on many oxide surfaces to form a
low polar coating. After the dipping the titanium dioxide films into
ethanol solution of stearic acid for 12 h, the CA became much high-
er than that of the as-prepared samples (Fig. 5), suggesting a stea-
ric acid SAMs are successfully formed on the samples surface. In
contrast to the as-prepared samples, the stearic acid modified sam-
ples show a clear increase of CA with the increase of anodizing
voltage. The CA variation curve indicates that a significant transi-
tion takes place while the anodizing voltages vary between 10
and 30 V (Fig. 5D). When the voltage is above 40 V, the CA reaches
a constant around 154 ± 2°.
The wettability of a solid materials is governed by several
parameters, among which the surface energy and the surface
roughness are dominant [27]. It is clear that the voltage-dependent
wettability transitions of the porous titanium dioxide is due to the
changes of surface roughness, while simple surface modification by
stearic acid could easily switch the surface from hydrophilic to
hydrophobic. In general, surface roughness has been found to am-
plify the intrinsic CA of a given air/solid interface [28]. This fact can
be clearly seen from Figs. 4 and 5. The increase of the surface
hydrophilicity on a rough surfaces can be described by Wenzel’s
law [29]
cos hf ¼ r cos hw
where hf and hw are the water CA on a rough and smooth surface,
respectively, and r is the surface roughness, which is defined as
the ratio of the actual area of the rough surface to the projected area
[27]. For hw < 90°, it can be seen that an increase of r shall result in a
smaller CA. Complete wetting occurs when the hw is small enough
and the pores will be filled with water. However, for hydrophobic
films, such as stearic acid modified titanium dioxide films, the
Fig. 4. Contact angle images of the as-prepared porous titanium dioxide thin films anodized at different voltages: (A) 10 V, (B) 20 V, (C) 30 V and (D) 40 V.
water droplet is suspended above the pores and could not penetrate
into the pores. The apparent CA hf is better described by Cassie’s
equation [30]
cos hf ¼ fs cos hw  fv ð2Þ
where fs and fv are the area fractions of the projecting solid and air
on the surface, respectively (fs + fv = 1). The large fraction of air
trapped in the films forms a cushion at the substrate/water inter-
face that prevents the penetration of the water droplet into the
pores. Eq. (2) suggests that the CA is in fact indirectly linked with
the surface roughness. It is the area fraction of the air trapped at
surface instead of the actually roughness value dominates the
hydrophobicity. Besides increasing the roughness, an optimal sur-
face morphology at both micro- and nano-scale is also required
for achieve high CA.
Highly hydrophilic titanium dioxide coating is of great interest
for the applications like biocompatible implants, anti-fog coating
and self-cleaning surfaces. Herein, highly hydrophilic titanium
dioxide surfaces were obtained without requiring any further
treatment, like hydrophilic coating or UV radiation [31]. Superhy-
drophobic surface with water CA above 150°, are also under great
attention recently for both fundamental and application interests
[25,26,32]. Various methods for reversible switching between
superhydrophilicity and superhydrophobicity have been proposed
previously [26,33–36]. According to our study, the variation from
superhydrophilic surface to superhydrophobic surface was
achieved by a simple monolayer coating while the reversal process
can be achieved by removal the monolayer by using an oxygen
plasma or UV illumination.
Nanostructured titanium dioxide could exist in three crystalline
forms, in which the anatase and rutile phases are more useful than
the brookite phase for photochemical application. The crystalline
form of the titanium dioxide prepared by electrochemical anodiza-
tion under our condition was investigated by XRD and Raman
spectroscopy. The XRD patterns also show strong voltage depen-
dence, which is consistent with the above analysis (Fig. 6). For
the specimen obtained at 40 V or below, the XRD pattern shows
mainly features ascribing to the Ti substrate, which suggests that
the titanium dioxide layer is relatively thin [14]. The sample anod-
ized at 80 V (Fig. 6D) has thicker films and showed much clearer
peaks associated with titanium dioxide crystalline in the XRD
graph. The diffraction peaks at 25.3°, 37.8°, 54.0°, 55.0° and
62.07° are well corresponding to the (1 0 1), (0 0 4), (2 0 0), (1 0 5),
(2 1 1) and (2 0 4) diffraction of the anatase phase [37–39].
The phase of the obtained titanium dioxide films were also eval-
uated by Raman spectroscopy, since different crystalline forms
have distinct Raman characteristics (Fig. 7). All the Raman spectra
of the titanium dioxide thin films show similar features except the
20 V sample, on which no Raman peak was obtained mostly likely
due to the very thin oxide films. On the 40, 60 and 80 V samples, all
ð1Þ
the spectra consist of a strong peak around 147 cm1 and three
bands around 398, 518 and 640 cm1, which are well consistent
with the literature values of the Eg, B1g, A1g or B1g and Eg modes
of anatase phase, respectively [38,40]. For comparison, it is known
that the rutile phase shows Raman bands at 612 and 440 cm1,
while amorphous titanium dioxide gives Raman peaks located
around 158, 410 and 626 cm1, respectively [41]. Fig. 7 does not
show observable band corresponding to either rutile or amorphous
 H.-Y. Si et al. / Microporous and Mesoporous Materials 119 (2009) 75–81 79

AA B

C 160 D

( )
140

Contact Angle (°
120

100

0 20 40 60 80 100
Anodizing voltage (V)

Fig. 5. Contact angle images of the porous titanium dioxide thin films after modified by stearic acid. The anodizing voltages were (A) 20 V, (B) 40 V and (C) 60 V. (D) Shows the
plot of the water contact angles verses anodizing voltages, the dotted lines serves as a guide for the eyes only.

A (004) A (200) A (105)

A (101)
A (211) A (204)
D
Intensity (a.u.)
Intensity (a.u.)

B C

B
A
A

20 40 60 80 0 200 400 600 800 1000

2 θ (degree) Raman shift (cm-1)

Fig. 6. XRD patterns of the titanium dioxide thin films anodized at (A) 20 V, (B) Fig. 7. Raman spectra of the porous titanium dioxide thin films anodized at (A)
40 V, (C) 60 V and (D) 80 V, respectively. The labels show the assignments to the 20 V, (B) 40 V, (C) 60 V and (D) 80 V, respectively.
peaks due to the anatase phase titanium oxide.

possess good long-rang and short-range order. The peaks of the

titanium dioxide, indicating that the obtained titanium dioxide is
anatase phase, which is consistent with the XRD result.
The width and position of the Raman peaks also provide infor-
mation about the crystalline structure of the anatase titanium
dioxide. It has been reported that the occurrence of Eg mode
around 147 cm1 modes indicates long-range order, while the
intensities of the peaks around 398, 518 and 640 cm1 give indica-
tion of the short-range order of the anatase phase. Fig. 7 shows that
all the Eg, B1g, A1g or B1g and Eg modes are clearly observed in the
samples from voltages above 20 V, indicating that the electro-
chemically prepared anatase phase titanium dioxide nanocrystals
80 V sample were observed at 151, 405, 530 and 650 cm1, respec-
tively, which are blue shifted for 4–12 wavenumbers compared
with the corresponding peaks of the other samples. It is well
known that the lowest-frequency Eg mode is closely related to
the grain size of the titanium dioxide nanocrystals. For example,
the decrease in the titanium dioxide particle dimensions to the
nanometer scale is expected to cause in a wavenumber blue shift
and Raman peaks broadening as a result of phonon confinement
[42,43]. In Fig. 7, the spectrum of the 80 V sample shows only peak
shift but no detectable change in the peak full width half maxi-
mum (FWHM). Meanwhile, both the SEM (Fig. 2) and electronic
80
spectra (Fig. 8) suggest a clear tendency that titanium dioxide grain
size increases with the anodizing voltage. Therefore, other reasons
beside the grain size change shall be responsible for the above blue
shift. It is also known that Raman peak of nanoscale particle can be
affected by changes in strain and crystallinity [44,45]. As men-
tioned above, significant mechanic stress is expected for the porous
layer produced by electrochemical oxidation, especially for sam-
ples oxidized at high voltage. Therefore, it is reasonable to attribute
the blue shift observed in the Raman spectrum of the 80 V sample
to the residual compressive stress remaining in the titanium diox-
ide crystals.
Previous studies have suggested that different phase of titanium
dioxide could be obtained under different anodizing condition. Ar-
sov reported the transformation of amorphous titanium dioxide
films to the anatase, brookite, and rutile mineral forms in H2SO4,
KOH and HNO3 electrolyte [15,46]. In HF containing solution, pre-
vious works showed the porous titanium dioxide films mainly exist
in amorphous or poorly ordered crystalline state [16,47]. The crys-
tallographic transformation porous titanium dioxide films are clo-
sely related to the electrical breakdown, which is dependent on the
electrochemical parameters such as the electrolyte concentration
and the current density. It has been found that longer anodizing
time and stronger acid will help crystallization [15,48]. The elec-
trolyte used in this work contains a strong acidic and oxidative
mixture of chromic acid and HF, which shall facilitate the electrical
breakdown and crystallization of the grown titanium dioxide layer.
This may explain the fact that nearly pure crystalline anatase phase
was obtained under our condition.
The UV–vis absorption spectra of porous titanium dioxide thin
films show absorption maximum (Fig. 8) around 330–350 nm.
Intensity(a.u.)
300 400 500 600
Wavelength/nm
Fig. 8. The UV–vis absorption spectra of the porous titanium dioxide thin films
anodized at different voltages.
A B
100µA cm-2
Current density
20V
40V
60V
-0.5 0.0
Fig. 9. (A) Linear-sweep photovoltammograms with chopped irradiation and (B) photoaction spectra of the titanium dioxide films anodized at 20 V, 40 V and 60 V,
respectively.
H.-Y. Si et al. / Microporous and Mesoporous Materials 119 (2009) 75–81
The absorption edges are around 370–390 nm, corresponding to
an electron energy transition around 3.35–3.18 eV [49], which is
consistent with the band gap of anatase phase titanium dioxide
(3.18 eV). With increasing voltages, the absorption bands show
red shifts, indicating an increase of titanium dioxide nanocrystal
size. The broad absorption like bands above 400 nm in the spectra
of the 80 and 95 V samples are due to the interference effect, which
is responsible for the different color of the films.
The photocurrent of the porous titanium dioxide films were re-
corded during switching between dark and irradiated conditions
(Fig. 9A). Significant response to the illumination condition, i.e.
the difference between the light and dark currents, can be seen
from the photocurrent curves of all the samples. Fig. 9A shows that
the photocurrent responses decrease with the increase of the anod-
izing voltage. The response from the 20 V sample is one order of
magnitude higher than that of the 40 and 60 V samples. Mean-
while, the photocurrent response is high at positive bias, revealing
that the device performs better when holes move towards the
oxide/electrolyte interface. Photocurrent action spectra were mea-
sured to evaluate the photo-activity of the samples under different
incoming photo energy (Fig. 9B). The titanium dioxide films give
dominate photocurrents in the range between 330 and 350 nm,
which are in accordance with the absorption spectra as shown in
Fig. 8. The 20 V sample exhibits a much higher photocurrent re-
sponse in the whole spectral range, consistent with the results of
Fig. 9A.
Two reasons may be responsible for the lower photo-response
from the samples prepared at higher anodizing voltage. Firstly, as
shown in Fig. 9B, predominant photocurrent arises from the
absorption below 380 nm. Light in this wavelength range is ex-
pected to be strongly diffused at rough surfaces, especially on the
samples at high voltages, where the nodule sizes are comparable
with the wavelength. The diffusion effect may cause the light
95V
absorption occurs at the very top layer of the titanium dioxide
films, which will dramatically affect the path way for the elec-
90V
tron/hole to reach the bottom electrode. The intensive boundary
scattering for the photo-generated carriers reduce the carrier life
80V and mobility, leading to the decrease of the photo-response [4].
60V
Secondly, the transient photocurrent property of porous titanium
40V dioxide films is dependent on the photo-induced charge generation
20V and electron/hole transport kinetics. Samples from higher anodiz-
ing voltages have thicker titanium dioxide films and large pore
sizes. Thicker titanium dioxide layer is better for absorbing photon
above the band gap energy and generating charge carriers, but the
700 800
electron/hole recombination probability may increases dramati-
cally due to long travel distance toward the interfaces. Tacconi
et al. [50] showed that anodizing conditions have a complicated
relationship with the photo-response quality of the porous oxide
10µA cm-2
Current density
Light on
20V
40V
Light off
60V
0.5 1.0 1.
1.5 300 35
350 400 450
Potential/ V Wavelength/nm
 H.-Y. Si et al. / Microporous and Mesoporous Materials 119 (2009) 75–81
films. Herein, we demonstrated that the anodizing voltage afford-
ing different morphologies do yield significantly different
photo-response, which provides a simple strategy to tailor the
photo-activity of the porous titanium dioxide films.
4. Conclusion
We have shown that porous titanium dioxide layers with
rose-like irregular nodules on the surface can be obtained at high
anodizing voltage using HF/chromic acid mixture as electrolyte.
Different surface morphology could be readily obtained in a well
controlled manner by controlling the anodizing voltage. The wetta-
bility of the obtained titanium dioxide films was easily switchable
between superhydrophilicity and superhydrophobicity. XRD,
Raman and UV–vis results revealed that the as-prepared titanium
dioxide films were in anatase phase. In addition, with the increase
of the anodizing voltages, a decrease in photocurrent response was
observed. This work emphasizes the importance of controlling the
surface morphologies of the electrochemical anodized porous tita-
nium dioxide. It is expected that with further optimization, the
strategy of fabricating porous titanium dioxide films with desired
surfaces morphology will find applications in a wide range of
applications, such as photocatalysis, solar energy conversion and
surgical implants.
Acknowledgments
This work is supported by Program for New Century Excellent
Talents in University (NCET), National Natural Science Foundation
of China (NSFC, 20503011, 20621091), Specialized Research Fund
for the Doctoral Program of Higher Education (SRFDP.
20050730007), Key Project for Science and Technology of the Min-
istry of Education of China (106152).
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