Materials Letters 61 (2007) 2632 2637

www.elsevier.com/locate/matlet

Fabrication of TiO2/Au nanorod arrays employing a positive sacrificial

ZnO template and their electrochromic property
J. Zuo a , C.G. Nie a , X. Gu a , Y.K. Lai b , Y. Zong b , L. Sun a , C.J. Lin a,
a

State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen, 361005, China
b
Department of Materials Science and Engineering, Xiamen University, Xiamen, 361005, China
Received 10 June 2006; accepted 9 October 2006
Available online 27 October 2006

Abstract
A novel method to fabricate large scale TiO2/Au nanorod array using a positive sacrificial ZnO template has been developed. This method
includes a two-step process, (1) preparation of ZnO/Au nanorod array by a simple low-temperature hydrothermal process, and (2) preparation of
TiO2/Au nanorod array by electrochemically induced solgel process. The TiO2/Au nanorod array has showed a reversible electrochromism in
lithium-ion-containing organic electrolyte. The coloration and bleaching throughout a visible range can be switched on and off within a few
seconds.
2006 Published by Elsevier B.V.
Keywords: TiO2/Au nanorod array; Positive sacrificial ZnO template; Electrochromism

1. Introduction
In recent years there has been increasing interest in the
synthesis and applications of one-dimensional nanostructure
materials due to a broad range of enhanced mechanical, optical,
magnetic and electronic properties compared to coarser-grained
materials with the same chemical composition [113]. Among
the various techniques that have been developed to prepare such
materials, anodic aluminum oxide (AAO) template method [14]
is one of the most common techniques used, especially in the
synthesis of semiconductor oxide materials. Titanium dioxide
has been well known as a semiconductor with photocatalytic
activities and applied in the fields such as environmental
purification, utilization of solar energy and electrochromic
electrodes. The productions of TiO2 nanowire and nanorod array
using AAO templates have been reported previously, including
solgel [15], electrochemically induced solgel [6], anodic
oxidative hydrolysis [3], and solgel electrophoresis deposition
[7] methods. However, many problems in applications of TiO2
for practical devices, such as the strength of tailored nanomater Corresponding author. Tel./fax: +86 592 2189354.
E-mail address: cjlin@xmu.edu.cn (C.J. Lin).
0167-577X/$ - see front matter 2006 Published by Elsevier B.V.
doi:10.1016/j.matlet.2006.10.010

ials and the assembly for devices, have not been well solved yet
[8]. After the AAO template is removed, the embedded array
with a high aspect ratio normally collapses into an entangled
mess due to the surface tension force exerted on the nanowires
and nanorods during the evaporation of the liquids [1619]. This
makes the template-assisted synthesis greatly limited when vertically aligned nanowire array is desired for devices applications.
Accordingly, in this study, a novel ZnO nanorod array
templating technology is attempted to fabricate TiO2 nanorod
array in a large scale on ITO substrate. The strategy involves two
steps: firstly, the ZnO nanorod array with Au is used as a positive
sacrificial template; secondly, TiO2 nanorod array is prepared by
chemically induced solgel method [6]. This approach is
expected to have a wide potential application in functional
glass for photocatalysis, solar energy, manufacture of practical
devices and etc. Moreover, the phenomenon of electrochromic
properties of the TiO2 nanorod array electrode is investigated in
the paper.
2. Experimental
All the solutions were prepared from analytical grade
reagents and distilled water.

J. Zuo et al. / Materials Letters 61 (2007) 26322637

2.1. Preparation of ZnO/Au nanorod array template

Highly ordered ZnO nanorod array was grown using a simple two-step process. In the first step, a thin ZnO nanocrystals
seeds film (27 nm in diameter) was produced by dip-coating
according to the method reported by Meulenkamp [20]. After
the ITO glass was uniformly coated with ZnO nanocrystal
seeds, a low-temperature hydrothermal process reported by
Greene [2] was adopted to prepare ZnO nanorod array.
Prior to electroplating, a layer of Au (RF, 100 W, 3 min) was
deposited onto ZnO nanorod array as a conductive contact and a
sheath onto ZnO nanorod array.

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and consequently a yellow-colored gel was obtained. By dissolving the yellow gel in 4 M H2SO4, a red-colored solution was
obtained. Then about 1.76 g KNO3 was dissolved in this
solution, the pH of the solutions was adjusted to 2.5 by using an
ammonia solution. The prepared solution was used as an electrolyte in the following electrodeposition. The sample coated
with ZnO/Au nanorod array was cathodically deposited for
30 min under 0.75 V at room temperature, using a threeelectrode system with a saturated calomel electrode (SCE) as a
reference electrode and a 2 cm 1.5 cm platinum plate as a
counterelectrode. The ZnO/Au nanorod array template was used
as the working electrode. In the end, the sample was annealed at
450 C for 24 h in order to obtain anatase TiO2 nanorod array.

2.2. Preparation of TiO2 nanorod array

2.3. Characterization of nanorod array
The TiO2 nanorod array was prepared by using an
electrochemically induced solgel process [6] in the ZnO/Au
nanorod array template. First, the Ti powder was dissolved in
25 ml H2O2 (30%) and 25 ml ammonia solution (25%28%),

The morphology and elemental compositions of samples

were characterized by a scanning electron microscope (SEM,
LEO-1530) and EDX spectrometer. XRD measurement was

Fig. 1. (A) SEM image of the top view and (B) XRD pattern of ZnO nanorod array; (C), (D) SEM images of the top view and side view of ZnO/Au after sputtering a
thin layer of Au, respectively.

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J. Zuo et al. / Materials Letters 61 (2007) 26322637

performed with Rigaku Rotaflex D/max-C system. The Raman

spectra were directly conducted using 514.5 nm laser light from
a He:Ne laser and a Renishaw System 1000 Raman microscope.
2.4. Spectroelectrochemical measurement
A single-compartment cell with two Pt wires as the counter
and quasi-reference electrode respectively in 1 M LiClO4/
acetonitrile solution was used. Optical (Cary 5000 UVVis
NIR spectrophotometer) and electrochemical (AUTOLAB ECO
CHEMIE B.V.) tests were conducted to study the electrochromism properties of the prepared TiO2 nanorod array electrode.
3. Results and discussion
Fig. 1(A) shows the SEM image of ZnO nanorod array in the top
view. It is evident that the entire glass is coated with a uniform and
dense ZnO nanorod array. The diameter of ZnO nanorod is about 40
80 nm. The low-temperature solution method using ZnO seeds was
adopted here because of its simple facility, low cost and large scale

formation on the substrates. In particular, it can generate highly uniform and densely packed ZnO nanoarray almost perpendicularly onto
the substrates with flat hexagonal crystallographic planes [2]. As
confirmed by X-ray diffraction with a remarkably enhanced (002) peak
(Fig. 1(B)) resulting from the vertical orientation of ZnO nanorod, the
ZnO nanorod array is wurtzite type pattern with crystals highly oriented
in (001) plane.
The SEM images of ZnO/Au nanorod array in the top view and the
side view are shown in Fig. 1(C) and (D) respectively. The diameter of
the ZnO/Au nanorods increases to 120180 nm after a thin layer of Au
is coated on the ZnO nanorod array. Compared with the as-prepared
ZnO nanorod array, different structures are observed clearly, which
confirms the presence of Au film on ZnO nanoarray. The sharp edges
on the hexagonal ZnO nanorod are not as clear as those observed in asprepared ZnO nanorod array. It can be seen that Au grains are obvious
on the surface and the side of ZnO nanorods. The diameter of such
grains ranges from 20 to 30 nm in size. The nanorods are robustly
encapsulated in a thin and continuous Au film by radio frequency
magnetron sputtering, different from work by Wu [21] with photosynthesis of Au nanoparticles on the ZnO nanorod which only are
formed on the tip regions of the ZnO nanorods.

Fig. 2. SEM images of (A), (B) top view at different magnifications and (C) side view; (D) Raman spectrum of TiO2/Au nanorod array; (E) SEM image of individual
TiO2 nanorods; all samples were prepared by 30 min deposition time and 24 h heat treatment. (F) EDX spectrum of individual nanorod on Cu grid removed from
nanorod array.

J. Zuo et al. / Materials Letters 61 (2007) 26322637

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Fig. 2 (continued).

Fig. 2 shows SEM images of the top view (A), (B) and side view (C)
of TiO2/Au nanorod array. New nanorod arrays can be observed after
TiO2 is deposited onto the ZnO/Au nanorod arrays by the electrochemically induced solgel method for 30 min followed by heat
treatment. The Raman spectrum (Fig. 2(D)) indicates typical Raman
shifts analogous to pure crystalline of anatase TiO2 [22], with five well
resolved Raman peaks located at around 153 cm 1 (Eg), 202 cm 1
(Eg), 397 cm 1 (B1g), 511 cm 1 (A1g and B1g), and 632 cm 1 (Eg). It is
obvious that the entire glass is coated with a densely packed TiO2/Au
nanorod array with diameter of about 120200 nm. It indicates that all
of these reactions are probably finished in the Au sheath after 30 min
electrodeposition and heat treatment. Compared with the ZnO
nanorods coated with a layer of Au, there are no obvious Au grains
on the top and side surface of TiO2/Au nanorods. The reason might be
that a little amount of Ti gel network can be formed on the outer layer
of the Au sheath. Fig. 2(E) shows the SEM image of individual
nanorods on Cu grid removed from the array. The cluster morphology
of TiO2 nanorods is analogous to that of individual ZnO nanorods [2],
which often grow from a single aggregate of ZnO nanoparticles
attached to the substrate. The elemental composition of the individual
nanorods after heat treatment is confirmed by EDX spectroscopy
(Fig. 2(F)).
As the previous studies reported by Xu et al. and his group [5,6],
electrochemically induced solgel method involves three steps. Firstly,
the nitrate ions in the electrolyte are reduced to produce hydroxyl ions

(Eq. (1)). Secondly, the resulting hydroxyl ions induce hydrolysis of a

precursor solution to form a suspension of colloidal particles (the sol)
and then the sol particles aggregate to become a gel. Finally, subsequent heat treatment results in solid TiO2 nanorod array. Fig. 3

Fig. 3. Cyclic voltammogram (10 mV/s) for the ZnO/Au working electrode.

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J. Zuo et al. / Materials Letters 61 (2007) 26322637

presents the cyclic voltammogram for the ZnO/Au nanorod array

coated on ITO glass in the solution. The only cathodic peak at 0.75 V
can be assigned to the electroreduction of nitrate ions [6,23]:
NO3 6H2 O 8eNH3 9OH

It is well known that ZnO dissolves in acidic solution. When the

ZnO/Au nanorod array on ITO glass is immersed in the acidic solution,
and its pH is adjusted to 2.5, the ZnO nanorods begin to dissolve slowly
because of the protection of Au coating. At the same time, the resulting
hydroxyl ions, which increase the local pH in the Au sheath, may result
in the hydrolyzation of Ti precursor to form a dispersion of colloidal
particles on the Au sheath [6,22]:

TiO
2 OH TiOOH2

Further electrochemical reaction on the Au sheath causes bonds

formation between sol particles, and finally a network of titanium
oxyhydroxide gel on the sheath [6,23]:
TiOOH2 solH2 OTiO1 OH22 gel

The diffusion of generated OH in solution can be restricted by the

Au sheath with a Au top cover so it is easier to form the sol particle and
gel network on the top of the sheath than in the bottom under the
electric field. As shown in Fig. 4(A), the formation of the sol particle

and gel network after 10 min deposition time and subsequent heat
treatment are initially performed on top of the Au sheath and then
extended to the bottom. The EDX analysis (Fig. 4(B)) of this nanorod
shows that it is mostly composed of Au and Ti without any trace of Zn.
Other elemental peaks quite probably arise from the composition of the
ITO glass substrate. This result demonstrates that ZnO nanorods in the
Au sheath have been completely dissolved and replaced after TiO2
electrodeposition for about 10 min.
By combining ZnO positive sacrificial template method and electrochemically induced solgel method, the well-structured TiO2/Au
nanorod array can be fabricated in large scale. However, further study
is needed to understand the mechanism of ZnO nanorod dissolution
and TiO2 nanorod growth process. The condition of sputtering Au and
the deposition time are two important factors in determining the
processing of electrodeposition. A further detailed study is required to
understand the exact nature of the deposition process.
The electrochromic study of the TiO2/Au nanorod array composite
was carried out in 1 M LiClO4 in acetonitrile solution. The optical
absorption (colored and bleached) of the TiO2 nanorod array film in
400 to 800 nm wavelength is shown in Fig. 5. When a potential of
2.5 V is applied, the colored film developed within 30 s. On the other
hand when the potential is changed to 0.5 V, bleaching is observed in
the same time scale. These phenomena have been found for the anatase
powder [24,25] and the anatase films made by reactive evaporation

Fig. 4. (A) SEM image of formation of the sol particle and gel network after 10 min deposition time and (B) EDX spectrum taken from these nanorods.

J. Zuo et al. / Materials Letters 61 (2007) 26322637

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Acknowledgment
The financial support from the National Science Foundation
of China for this project (20021002) is gratefully acknowledged.
References

Fig. 5. UVVis spectral response for colored and bleached TiO2/Au nanorod
array at 2.5 V and 0.5 V each for 30 s, respectively.

[26], the sputtering of Ti [27] and by solgel preparation [28,29]. It

can be proposed that both Li intercalation/deintercalation reaction and
Ti4+ Ti3+ redox reaction lead to coloration/decoloration process of
the film:
TiO2 Li e Li TiO2
Ti4 e Ti3
Further studies on the electochromic properties of the TiO2
nanorods composite are now under investigation.

4. Conclusions
This investigation has clearly established a novel combination technique for fabricating large scale TiO2/Au nanorod
array. A possible formation mechanism is proposed. And the
key factors are the formation of Au film sheath, dissolution of
ZnO nanorods and the electrodeposition of TiO2. From the
viewpoint of ZnO nanorod array as positive sacrificial templates
for nanoarray structure materials, it is expected that such
templates can be applied to other nanoarray materials, such as
SiO2, SiTiO3 which are needed in applications of chemical
sensors, photocatalysis, light energy conversion devices, and
nanoscale electronic and optoelectronic devices. And the
reversible electrochromic properties of the novel TiO2/Au
nanorod array composite are also observed. This study shows
the well-ordered TiO2/Au nanorod array exhibits similar
coloration and decoloration phenomena with TiO2 film and
powder. Future investigation of color switching speed,
efficiency and long-term reversible stability is in progress.

[1] Y.G. Guo, L.J. Wan, C.L. Bai, J. Phys. Chem., B 107 (2003) 5441.
[2] L.E. Greene, M. Law, J. Goldberger, F. Kim, J.C. Johnson, Y.F. Zhang, R.J.
Saykally, P.D. Yang, Angew. Chem., Int. Ed. 42 (2003) 3031.
[3] Y. Lei, L.D. Zhang, J.C. Fan, Chem. Phys. Lett. 338 (2001) 231.
[4] C.H. Liu, J.A. Zapien, Y. Yao, X.M. Meng, C.S. Lee, S.S. Fan, Y. Lifshitz,
S.T. Lee, Adv. Mater. 15 (2003) 838.
[5] D. Xu, Y. Yu, M. Zheng, G.L. Guo, Y.Q. Tang, Electrochem. Commun. 5
(2003) 673.
[6] Z. Miao, D.S Xu, J. Ouyang, G. Guo, X. Zhao, Y. Tang, Nano Lett. 2
(2002) 717.
[7] Y. Lin, G.S. Wu, X.Y. Yuan, T. Xie, L.D. Zhang, J. Phys., Condens. Matter
15 (2003) 2917.
[8] S.Z. Chu, K. Wada, S. Inoue, S.-i. Todoroki, Chem. Mater. 14 (2002) 266.
[9] B.B Lakshmi, P.K. Dorhout, C.R. Martin, Chem. Mater. 9 (1997) 857.
[10] M.J. Zheng, L.D. Zhang, G.H. Li, W.Z. Shen, Chem. Phys. Lett. 363
(2002) 123.
[11] X. Feng, L. Feng, M. Jin, J. Zhai, L. Jiang, D. Zhu, J. Am. Chem. Soc. 126
(2004) 62.
[12] Y. Zhang, H. Jia, R. Wang, C. Chen, X. Luo, D. Yu, Appl. Phys. Lett. 83
(2003) 4631.
[13] C.H. Liu, W.C. Yiu, F.C.K. Au, J.X. Ding, C.S. Lee, S.T. Lee, Appl. Phys.
Lett. 83 (2003) 3168.
[14] Z.L. Wang, Nanowires and NanobeltsMaterials, Properties and Devices
Press Tsinghua University Publisher, 2004, p. 3.
[15] Y. Lei, L.D. Zhang, G.W. Meng, G.H. Li, X.Y. Zhang, C.H. Liang, W.
Chen, S.X. Wang, Appl. Phys. Lett. 78 (2001) 1125.
[16] D. Routkecitch, A.A. Tager, J. Haruyama, D. Almawlawi, M. Moskovits,
J.M. Xu, IEEE Trans. Electron Devices 43 (1996) 1646.
[17] D. Xu, Y. Xu, D. Chen, G. Guo, L. Gui, Y. Tang, Adv. Mater. 12 (2000)
520.
[18] D. Xu, Y. Xu, D. Chen, G. Guo, L. Gui, Y. Tang, Chem. Phys. Lett. 325
(2000) 340.
[19] M. Barbic, J. Mock, D.R. Smith, S.J. Schultz, J. Appl. Phys. 91 (2002)
9341.
[20] Eric A. Meulenkamp, J. Phys. Chem., B 102 (1998) 5566.
[21] J.J. Wu, C.H. Tseng, Appl. Catal., B Environ. 66 (2006) 51.
[22] C. Natarajan, G. Nogami, J. Electrochem. Soc. 143 (1996) 1547.
[23] J.C. Parker, R.W. Siegel, J. Mater. Res. 5 (1990) 1246.
[24] M. Wagemaker, A.P.M. Kentgens, F.M. Mulder, Nature 418 (2002) 397.
[25] M. Ottaviani, S. Panero, S. Morzilli, B. Scrosati, M. Lazzari, Solid State
Ion. 20 (1986) 197.
[26] T. Seike, J. Nagai, Sol. Energy Mater. 22 (1991) 107.
[27] S.F. Cogan, E.J. Anderson, T.D. Plante, R.D. Rauh, Proc. Soc. Photo-Opt.
Instrum. Eng. 562 (1985) 23.
[28] S. Doeuff, C. Sanchez, Compt. Rendues Acad. Sci. Paris, Sir. II 309 (1989)
531.
[29] N. Ozer, Thin Solid Films 214 (1992) 17.