NANO LETTERS

Electrochemically Induced SolGel Preparation of Single-Crystalline TiO2 Nanowires

Zheng Miao, Dongsheng Xu,* Jianhua Ouyang, Guolin Guo,* Xinsheng Zhao, and Youqi Tang
State Key Laboratory for Structural Chemistry of Unstable and Stable Species, College of Chemistry and Molecular Engineering, Peking UniVersity, Beijing 100871, P. R. China
Received March 4, 2002; Revised Manuscript Received April 29, 2002

2002 Vol. 2, No. 7 717-720

ABSTRACT
Highly ordered TiO2 single-crystalline nanowire arrays have been fabricated within the pores of anodic aluminum oxide (AAO) template by a cathodically induced solgel method. Raman spectra confirmed that the nanowires are composed of pure anatase TiO2. TEM investigations indicated that these nanowires have a uniform tetragonal single-crystal structure. Finally, a possible growth mechanism of the TiO2 nanowires is discussed.

Over the past decade, the synthesis and functionalization of one-dimensional nanostructural materials has become one of the most highly energized research areas.1-11 Among the many methods that have been used to prepare such materials, the sol-gel template synthesis method is one of the most common techniques used, especially in the synthesis of semiconductor oxide nanowires. Nanostructures (nanowires and nanotubules) of TiO2,12-14 CdS,15 SiO2,12,16 In2O3,17 Ga2O3,17 V2O5,12 MnO2,12 WO3,12 and many other semiconductor materials have been synthesized using such a solgel template synthesis strategy. However, as was mentioned in a recent report18 by Limmer et al., there are some potential limitations to this technique. For example, since the only driving force of this technique is capillary action, for the sol with higher concentration, filling the pores is difficult (at the same time destabilization of the sol remains a big problem), but low concentration leads to nanomaterials with serious shrinkage and cracking. Electrophoretic growth of nanorods throws some light on how to overcome the limitations of the direct sol filling method.18 While using this sol-gel electrophoresis in the templateassisted growth of nanorods, an electric field was applied to draw the charged sol nanoclusters into the template pores. This procedure failed to synthesize nanorodes of <50 nm in diameter, and we noticed that reports on the sol-gel preparation of nanowires in the pores of template with small diameters, especially less than 20 nm, are still scarce. This can be explained by the difficulty clusters have diffusing in
* Corresponding authors. E-mail: dsxu@chem.pku.edu.cn. Fax: 86-1062753937. 10.1021/nl025541w CCC: $22.00 Published on Web 05/08/2002 2002 American Chemical Society

the nanosized pores. Here we report an electrochemically induced sol-gel method to prepare TiO2 single-crystalline nanowire arrays. At first, the hydroxyl ion is generated due to the cathodic reduction, and then the generation of OHions increases the local pH at the electrode surface, resulting in the titanium oxyhydroxide gel formation in the pores of the template. Finally, subsequent heat-treatment and the removal of the AAO template results in the formation of TiO2 single-crystalline nanowire arrays. During this electrochemically induced sol-gel process, both the formation of sol particles and the gelation process take place in the AAO pores. Therefore, the sol-gel preparation of nanowires within templates that have very small pores (less than 20 nm or even small) would be readily achievable by using this technique. The electrolyte solution was prepared according to the work of C. Natarajan and G. Nogami.19 First, the Ti powder was dissolved in H2O2 and ammonia solution, then the excess H2O2 and ammonia were decomposed by heating the solution on a hot plate and, consequently, a yellow-colored gel was obtained. By dissolving the yellow gel in 4 M H2SO4, we got a red-colored solution. The red-colored solution was used as the stock solution for further electrodeposition. At last, certain amount of KNO3 was dissolved in the stock solution (about 145 mM), the PH of the solutions was adjusted to 2-3 by using an ammonia solution, and this resulting solution is used as electrolyte in the following electrodeposition. Electrodeposition was carried out at room temperature (20-25 C), using a three-electrode potentiostatic system with a saturated calomel electrode (SCE) as a reference elec-

Figure 1. (A) SEM image of the TiO2 nanowires grown in a 50 nm diameter membrane. (B) Raman spectra of the untreated and annealed bulk nanowire samples. All of the AAO template were removed.

Figure 2. TEM images of nanowires and SEM images of AAO template that we used in our experiment. (A) TEM images of 20 nm TiO2 nanowires. (B) TEM images of 10 nm TiO2 nanowires. (C) TEM image of a single TiO2 nanowire with a diameter of about 40 nm and the corresponding selected area diffraction pattern of this nanowire (inset). (D) SEM images of 50 nm AAO template. (E) SEM images of 22 nm AAO template. (F) SEM images of 12 nm AAO template. The scare bars in D, E, and F are 500 nm.

trode and a 2 cm 1.5 cm platinum plate as a counter electrode. A small piece of AAO template with Au substrate was used as the working electrode, with the porous side being exposed to the electrolyte. Templates with pore diameters of about 50 nm (Figure 2D), 22 nm (Figure 2E), and 12 nm (Figure 2F) were used in our experiment. The fabrication of porous AAO membrane templates with different pore diameters has been reported in previous works.9,20 The deposition
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was carried out under potentiostatic conditions with the potential range between -0.9 to -1.2 V. Then, the sample was annealed at 450 C for 24 h in order to obtain anatase TiO2 nanowires. For further analysis, the sample was attached to a small piece of silicon plate using epoxy resin and then the AAO template was dissolved in 1 M NaOH at 25C for 1 h and washed several times with double distilled water. For TEM observations, a transmission electron microscope, JEM-200CX, operated at 200 kV, was used. Scanning electron microscopy (SEM) was carried out on AMARY 1910FE. Raman spectra were measured using 514.5 nm laser light from a He:Ne laser and a Renishaw System 1000 Raman microscope. Figure 1(A) shows the SEM images of a large quantity of TiO2 nanowires obtained by this electrochemically induced sol-gel method in a 50 nm diameter membrane. It can be seen that the nanowires are continuous and arranged roughly parallel to one another, all of them have uniform diameter of about 40 nm, which is slightly less than the pore size of the template used. This would be well explained by the shrinkage due to densification and the removal of water from the gel. Unlike the synthesis of nanomaterials by other solgel methods,18 no broken nanowire has been observed in our samples. This may be explained by the higher packing density of nanomaterials prepared by this electrochemically induced sol-gel method. The lengths of the nanowires can range from 2 to 10 m according to the deposition time from 0.5 to 3 h. Figure 1(B) shows the Raman spectra of the untreated and annealed bulk samples (AAO template removed) with diameters of about 40 nm. While the untreated sample gave out a spectrum of noncrystalline materials, the spectrum of the sample after annealing shows the typical Raman shifts analogous to those of pure crystalline anatase TiO2 with five well resolved Raman peaks located at around 144 cm-1 (Eg), 195 cm-1 (Eg), 399 cm-1 (B1g), 516 cm-1 (A1g and B1g), and 638 cm-1 (Eg). The TEM images of the nanowires with diameters of about 20 nm (Figure 2A) and 10 nm (Figure 2B) indicate that these wires have uniform diffraction contrast, relatively straight morphologies, and smooth surfaces. Figure 2(C) shows the sharp selected area diffraction pattern of a 40 nm TiO2 nanowire, and the diffraction spots were indexed as 004, 200, and 103 of tetragonal anatase TiO2. The same electron diffraction patterns were obtained from different areas throughout the entire length of the nanowire. Both the diffraction contrast and the diffraction patterns demonstrated that these nanowires have a single-crystal structure. Figure 3 presents the cyclic voltammogram for a working electrode (a small piece of AAO template with Au substrate) in the electrolyte solution. The only cathodic peak can be assigned to the electroreduction of nitrate ions:19 NO3- + 6H2O + 8 e- f NH3 + 9OHFigure 4 is a schematic drawing of the electrochemically induced sol-gel process. First, at potentials more negative
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Figure 3. Cyclic voltammogram (10 mV s-1) for the Au/AAO working electrode in the electrolyte solution.

network courses the expansion of gel in the AAO pores and aging of the gel that has already formed. The AAO template with pores of nanoscale size can restrict the diffusion of OHin solution, so it is easy to construct higher local pH and longer diffusion depth in the AAO pores than on the thin film. As we know, both the hydrolysis and the gelation may be strongly dependent on the pH of the solution during the sol-gel process. The high local pH may lead to complete hydrolysis and condensation and result in more compact and highly branched structures. Because the pH gradient at the bottom of the pore increases with decreasing of the pore size, the gels formed in small pores are more compact than in big pores. The compact structure of the gel in turn obstructs the transport of ions in the pores; this may account the fact that the current decays steadily during the potential-static electrodeposition and higher current density was observed while using templates with bigger pores. Compared with the direct sol filling method,12,14,15 this method offers many advantages for the formation of nanowires. First, although sol-gel preparation of TiO2 nanowires with small diameters has been reported,12,14 to fill small pores with the sol is still difficult work. However, using our technique, templates with very small pores (20 nm or even small) can be used in the preparation. Second, the length of the nanowires can be well controlled by varying the deposition time and potential of the working electrode. Third, as we know, the catalyst plays an important role in the hydrolyzation, gelation, and aging processes;, the high pH gradient constructed at the bottom of the pores makes higher packing density achievable, hence less shrinkage and cracking will happen during the heat treatment of nanowires. In summary, highly ordered TiO2 single-crystal nanowire arrays with diameters of about 40 nm, 20 nm, and 10 nm were prepared by cathodically induced sol-gel method from an aqueous solution containing a Ti precursor. By doing this, we also attempt to find a general method for the growth of 1D nanostructures of a variety of inorganic oxides (single or complex) materials, such as SiO2, ZrO2, YBCO etc. Acknowledgment. This work was supported by the Major State Basic Research Development Program (Grant No. 2000077503). References
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Figure 4. Schematic demonstrating the progress of the electrochemically induced sol-gel process. We see that both the formation of sol particles and the gelatin process take place in the AAO pores; last, the pores are filled with homogeneous titanium oxyhydroxide gel.

than -0.9 V, the nitrate ions are reduced to produce hydroxyl ions, which increase the local pH in the AAO pores, resulting in the hydrolyzation of Ti precursor and form a dispersion of colloidal particles in the AAO pores: TiO2+ + 2OH- f TiO(OH)2 (sol) Further electrochemical reaction in the pores causes bonds formation between sol particles, resulting in a network of titanium oxyhydroxide gel in the pore of AAO template: TiO(OH)2 (sol) - xH2O f TiO1+x(OH)2-2x (gel) The transport of ions through the voids of packed sol particles and the tiny pores in the titanium oxyhydroxide gel
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