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G398
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
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G399
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.
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G400
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-
12.
13.
14.
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