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Journal of The Electrochemical Society, 148 7 G398-G400 2001

G398

0013-4651/2001/1487/G398/3/$7.00 The Electrochemical Society, Inc.

Electrochemical Fabrication of Single-Crystalline Anatase TiO2


Nanowire Arrays
Xinyi Zhang,a, z Baodian Yao,a Lixia Zhao,a Changhao Liang,a Lide Zhang,a and
Yongqiang Maob
a

Institute of Solid State Physics, Chinese Academy of Sciences, Heifei 230031, China
Nanjing Institute of Geology and Paleontology, Chinese Academy of Sciences, Nanjing 210008, China

Well-aligned TiO2 nanowire arrays have been synthesized by anodic oxidative hydrolysis of TiCl3 within a hexagonal closepacked nanochannel alumina on an Au substrate. X-ray diffraction spectrum, Raman scattering spectrum, scanning electron
microscopy, and transmission electron microscopy analysis show that the single-crystalline anatase TiO2 nanowires, 15 nm in
diam, are uniformly assembled into highly ordered pores of the anodic alumina. Finally, the growth mechanism of the TiO2
nanowires is discussed. The well-aligned TiO2 nanowire arrays will be useful for study of the photoelectrochemical properties of
TiO2 nanowires and application in photoelectrochemistry.
2001 The Electrochemical Society. DOI: 10.1149/1.1378293 All rights reserved.
Manuscript submitted August 16, 2000; revised manuscript received March 8, 2001. Available electronically June 8, 2001.

In recent years, there has been increasing interest in the fabrication of one-dimensional nanostructures because of their potential
utilization in electronic, magnetic, optical, and micromechanical devices. To obtain scaled-up functional devices highly ordered nanowire or nanotube arrays are essential. The most common technique
used to fabricate such a structure is so-called template synthesis.1-4
This method has been used to prepare tubules and fibrils composed
of conductive polymers, metals, semiconductors, and other materials
such as carbon nanotubes. TiO2 is one of the most important transition metal oxides, widely used as a catalyst support,5 as a semiconductor photocatalyst,6 and in solar cell,7 and sensors.8,9 TiO2 nanowire arrays have been synthesized using sol-gel template method.10
However, the sol-gel method has some disadvantages in preparing
such structures, for example, impurities are often brought in and the
organic precursors are often hydrolyzed quickly and easily to form
an unstable gel.
Electrochemical synthesis is cheap and fast in comparison with
the sol-gel method. Electrodeposition of TiO2 anatase films was
previously reported by anodic oxidative hydrolysis of TiCl3. 11 We
have used this method to prepare well-aligned single-crystalline
TiO2 nanowire arrays within a hexagonal close-packed nanochannel
alumina NCA. This report focuses on the fabrication process and
characterization of the single-crystalline anatase TiO2 nanowire arrays.
Experimental
NCA templates were prepared by a two-step anodization process
as described in a previous report.12 Briefly, high purity 99.999%
aluminum foils were used as the starting material. Prior to anodizing, the aluminum was annealed at 500C in order to obtain homogeneous conditions for pore growth over large areas. Subsequently,
the foils were electropolished in a 1:9 by volume mixture of HClO4
and C2H5OH. Anodization was carried under a constant cell voltage
of 40 V in a 0.3 M oxalic acid solution at 12C for 10 h. The formed
alumina was then removed by a mixture of phosphoric acid and
chromic acid, and the Al sheet was anodized again under the same
conditions as above for 2 h. After the anodization, the remaining
aluminum was removed in a saturated HgCl2 solution. Subsequently, the pore bottoms were opened by chemical etching in 5 wt
% aqueous phosphoric acid. In order to fabricate an array of TiO2
nanowires, a layer of Au film was deposited as an electrode on one
side of the anodic porous alumina template using a vacuum evaporation apparatus. Arrays of TiO2 nanowires were prepared by anodic
oxidative hydrolysis of acidic aqueous TiCl3 solutions using the

E-mail: zxyxlh@mail.hf.ah.cn

potentiostatic method with a three-electrode arrangement with a


saturated calomel reference electrode SCE and a Pt counter electrode. Preparation of TiO2 nanowires was performed from a 0.25 M
TiCl3 solution at 25C under an Ar atmosphere, pH 2.5. The anode
potential was kept at 0.1 V vs. SCE. Then, the sample was annealed
at 500C in order to obtain anatase TiO2 nanowires. The structure
and morphology of the ordered TiO2 nanowire arrays were investigated using a transmission electron microscope TEM, JEM200CX, a scanning electron microscope SEM, JEOL JSM-6300,
and an X-ray diffractometer Pw 1700. The Raman spectrum was
measured at room temperature with a laser Raman scattering spectrometer Spex 1403. A 200 mW output power was chosen as the
incident light source.
Results and Discussion
Figure 1 shows the SEM images of hexagonal close-packed
NCA template formed by the two-step anodization process. The
cross sections of the parallel cylindrical pores are clearly seen after
a slight etching. The channel diameter and length were 45 nm and 6
m, respectively. The SEM images of the TiO2 nanowire arrays are
shown in Fig. 2, which resulted from etching away the aluminum
oxide using a mixture of 6 wt % phosphoric acid and 1.8 wt %
chromic acid followed by cleaning in an ultrasonic bath. It can be
clearly seen that TiO2 nanowires are of an equal height and have a
highly ordered tip array. Most of the nanowire tips are crooked,
which could be caused by the etching process. Figure 3a shows the
TEM image of a bundle of TiO2 nanowires obtained after dissolving
away the alumina template. The TiO2 nanowires are straight and
have uniform diameters about 15 nm. It is interesting that the diameter of TiO2 nanowires is much less than the pore size of alumina.
Figure 3b shows the TEM image of a TiO2 nanowire. A selected
area diffraction pattern recorded perpendicular to the nanowires
along the axis near the tip Fig. 3b, inset could be indexed for the
110 zone axis of the nanowires.10 It can be concluded from the
observation that the nanowires are single anatase-phase crystals.
Figure 3c shows the TEM image of a TiO2 nanowire located at the
center of the cylindrical alumina pore. The X-ray diffraction XRD
spectrum of the TiO2 nanowire arrays is displayed in Fig. 4. The
broad feature in the spectrum arises from the amorphous alumina
substrate. Only 101, 004, 211 peaks of anatase can be observed.
Nanowires in the template are perpendicular to the surface of the
template; only crystal planes in which the nanowire axis lies are
possible to satisfy the Bragg condition for XRD. Figure 5 shows the
Raman scattering spectrum of the TiO2 nanowire arrays. The Raman
peaks are located around 148, 399, 516, and 640 cm1, corresponding to the typical Raman peaks of anatase TiO2. The prominently
intense, low-frequency mode at 148 cm1 corresponds to one of the

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Journal of The Electrochemical Society, 148 7 G398-G400 2001

G399

Figure 1. SEM images of the highly ordered NCA template prepared by a


two-step anodization method: a top view and b cross-sectional view.

Figure 3. TEM images of the TiO2 nanowires: a, top the TEM image of a
bundle of TiO2 nanowires. b, center The TEM image of a TiO2 nanowire.
The inset shows the electron diffraction pattern of the nanowire recorded
near the tip along the 110 zone axis perpendicular to the nanowire axis. c,
bottom The TEM image of a TiO2 nanowire located at the center of the
cylindrical alumina pore.

Figure 2. SEM images of the resulting ordered array of TiO2 nanowires: a


low magnification image and b high magnification image.

Eg modes, which has been assigned to the O-Ti-O bending vibration.


This result is consistent with SEM and TEM observations.
The mechanism of preparation of TiO2 anatase films by anodic
oxidative hydrolysis of TiCl3 has been postulated by Kavan and
co-workers.13 In the process of anodic oxidative hydrolysis of TiCl3,
the rate of anodic Ti3aq oxidation is controlled, analogous to the
chemical oxidation with O2, by a rapid hydrolytic pre-equilibrium,
followed by the oxidation of the thus formed TiOH2 monohydroxy
intermediate to TiIV oxo species. This consists probably of partly
dehydrated cross-linked polymeric TiIV hydroxide, containing
both terminal and bridged OH groups. This material is converted
finally into TiO2 by annealing. At this stage, the situation is quite

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G400

Journal of The Electrochemical Society, 148 7 G398-G400 2001


cause the reduced ion is a positively charged ion. The transport of
TiOH2 acts contrary to the action of the applied electric field. So
the migration of TiOH2 from the bulk electrolyte to the anode/
solution interface only caused by the concentration difference between the bulk electrolyte and the interface. Considering the high
resistance of the solution in the pores, we used a 0.25 M TiCl3
solution, the concentration is much higher than that for preparing
TiO2 films.11 The nonannealed TiO2 film prepared by anodic oxidative hydrolysis is composed of extremely small crystalline particles
with 1-2 nm in diameter. After annealing, the particles grow and
aggregate to form a polycrystalline film,13 in this case, the formation
of anatase TiO2 nanowires are limited within the template including
electrodeposition and annealing process, which should account for
the formation of single-crystalline anatase TiO2 nanowires.

Figure 4. XRD spectrum of the TiO2 nanowire arrays.

Conclusion
different because of the presence of the alumina template. An explanation of the nanowire growth mechanism within the alumina
template must remain speculative. According to the observations of
SEM and TEM, the nanowires nucleate and grow at the center of the
alumina pore. As we know, there are many oxygen vacancies on the
pore walls, so the pore walls of the alumina template are positively
charged.14 From this point it can be inferred that TiOH2 particles
are repelled by the electric field of the pore walls when they enter
the pores. Thus it is not surprising that the nanowires nucleate at the
center of the alumina pores. The process of anodic oxidative hydrolysis is different from the usual anodic reaction processes, be-

The well-aligned TiO2 nanowire arrays with diameters about 15


nm have been synthesized by anodic oxidative hydrolysis of TiCl3
within a hexagonal close-packed NCA template on a Au substrate.
Characterization by means of SEM, TEM, XRD spectrum, and Raman scattering spectrum shows that the single-crystalline anatase
TiO2 nanowires are uniformly assembled into the highly ordered
pores of the anodic alumina. The gentle electrochemical nanofabrication method presented is fast and inexpensive. The well-aligned
TiO2 nanowire arrays would be useful for studying the photoelectrochemical properties of TiO2 nanowires and their application in
photoelectrochemistry.
Acknowledgments
The authors thank Professor S. Y. Zhang and Professor G. H. Li
for valuable discussions. The financial support of this work by the
Key Project of National Fundamental Research of China is acknowledged.
References
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Figure 5. Raman scattering spectrum of the TiO2 nanowire arrays, showing


the anatase Eg modes at 148 and 639 cm1, a double of A1g and B1g modes
at 516 cm1, and the B1g mode at 399 cm1.

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