Materials Letters 62 (2008) 4532–4534

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Chemical bath deposition of textured ZnO thin films in aqueous/ethanolic solution

Mingsong Wang a, Sung Hong Hahn b, Jae Seong Kim a, Soon Ho Hong a, Kee-Kahb Koo c, Eui Jung Kim a,⁎
a
Department of Chemical Engineering, University of Ulsan, Ulsan 680-749, South Korea
b
Department of Physics, University of Ulsan, Ulsan 680-749, South Korea
c
Department of Chemical and Biomolecular Engineering and Interdisciplinary Program of Integrated Biotechnology, Sogang University, Seoul 121-741, South Korea

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

Article history: ZnO thin films have been prepared by chemical bath deposition in aqueous/ethanolic solution. The film
Received 7 May 2008 texture was successfully controlled by varying the volume ratio of water to ethanol. Films consisting of
Accepted 16 August 2008 densely oriented nanorod arrays with the c-axis perpendicular to the substrate were fabricated in aqueous
Available online 22 August 2008
solution. The crystals became increasingly tilted as more ethanol was introduced to the solution, resulting in
the cracked nanocolumns and the smoothed crystals. The crystal size was decreased with increasing ethanol
Keywords:
Crystal growth
content, and granular morphology was obtained in films deposited in ethanolic solution. A gradual evolution
Thin films of the film texture is possibly due to the inhibited crystal growth in solution with higher ethanol content.
ZnO © 2008 Elsevier B.V. All rights reserved.
Semiconducting II–VI materials

1. Introduction
As a direct wide band gap (3.37 eV) II–VI semiconductor with a
large exciton binding energy (60 meV), zinc oxide (ZnO) has
increasingly attracted attention due to its excellent chemical stability
and specific optoelectronic property [1]. Since the properties of ZnO
strongly depend on its morphology and microstructure, it is essential
to precisely control the size, shape and microstructure of ZnO for its
application as optoelectronic materials used in solar cells [2], gas
sensors [3], and light emitting diodes [4].
ZnO films have been prepared by various techniques including
sputtering [5], spray pyrolysis [6], sol–gel process [7], chemical vapor
deposition [8], and chemical bath deposition (CBD) [9]. It is necessary
to prepare high-quality ZnO films via a relatively cheap route for
various applications. CBD has been demonstrated to be a facile
approach to fabricate large-area ZnO thin films. However, the precise
control of ZnO crystal evolution in the CBD process is a formidable
task. Moreover, the mechanism for the formation of CBD ZnO crystals
is hardly understood.
In this work, the heterogeneous growth of CBD ZnO thin films was
carried out in aqueous/ethanolic solution. The preparation method for
textured ZnO films is modified from the solution route synthesis of
ZnO nanorod arrays: a seeded substrate is immersed in an equimolar
aqueous solution of zinc salt and methenamine at 90 °C for a period of
time [10]. By varying the volume ratio of water to ethanol, VW/VE,
we have synthesized ZnO films with a series of controlled textures.
The film deposition rate is found to decrease with increasing ethanol
⁎ Corresponding author. Tel.: +82 52 259 2832; fax: +82 52 259 1689.
E-mail address: ejkim@ulsan.ac.kr (E.J. Kim).
content. A tentative growth mechanism for the CBD ZnO film
deposition has also been described.
2. Experimental
The preparation method for textured ZnO films was modified from
the solution route synthesis of ZnO nanorod arrays, i.e., by immersing
the seeded substrate in equimolar aqueous solution of zinc salt and
methenamine at 90 °C for a period of time [11]. The seed layer was
formed by a single sol–gel dip-coating followed by post-treating at
400 °C for 1 h. Preparation of the sol has been described in detail
elsewhere [12]. Textured ZnO films were deposited from 0.1 M
equimolar aqueous/ethanolic solution of zinc acetate (Zn(Ac)2·2H2O,
extra pure) and methenamine (C6H12N4, extra pure) at 95 °C in a 250-mL
conical flask with a reflux condenser. Typically, films were deposited in
the solution with the VW/VE ratio of 1/0, 3/1, 1/1, and 0/1, for 1, 2, 3, and
4 h, respectively. Finally, the deposited films were thoroughly washed by
deionized water and dried in an oven at 50 °C before characterization.
Film texture was monitored by XRD θ–2θ scan and rocking curve
scan via Philips X'Pert PW-3710 and X'Pert PRO (Cu Kα radiation),
respectively. Sample morphology was examined by field emission
scanning electron microscopy (FESEM) (JEOL, JSM-6500F).
3. Results and discussion
As shown in Fig. 1a, the ZnO film comprising densely oriented nanorod arrays with
the c-axis perpendicular to the substrate is fabricated in aqueous solution. The diameter
of the nanorods is in the range of 200–500 nm. However, the single crystals are less
faceted, which is probably attributed to the rapid growth rate of crystals at high Zn2+
concentration (0.1 M). As reported by Vayssieres et al. [13], only microrods of 1 μm in
diameter were obtained in such a high Zn2+ concentration. When deposited in a mixed
solution with 25% ethanol, however, the columns are cracked and tilted, with only two

0167-577X/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2008.08.024
 M. Wang et al. / Materials Letters 62 (2008) 4532–4534 4533

Fig. 1. SEM images of samples grown on pre-coated glass substrate: (a) in an aqueous solution (VW/VE = 1/0) for 1 h; (b) in a mixed solution (VW/VE = 3/1) for 2 h; (c) in a mixed solution
(VW/VE = 1/1) for 3 h; (d) in an ethanolic solution (VW/VE = 0/1) for 4 h. Scale bars, (a–d) in sequence: 1 μm, 1 μm, 500 nm, 200 nm.

or three edges survived in the hexagonal faces (Fig. 1b). A further increase in ethanol
content to 50% results in decreased crystal size, polished crystal edges and more
randomly oriented crystals, but the basic crystal corners are still retained (Fig. 1c). For the
films deposited in 100% ethanol, the crystal corners disappear completely, thus resulting in
a granular morphology (Fig. 1d). The results of Fig. 1 can be summarized: (i) the oriented
texture decreases with the increase in ethanol content, from perpendicularly aligned
nanorod arrays to randomly oriented particles; (ii) the film deposition rate as well as the
crystal size is decreased correspondingly.
XRD θ–2θ scan measurement of the deposited films reveals a textured film
structure; the strongest reflection for the films deposited in 0%, 25%, 50%, and 100%
ethanol, is (002), (101), (112), and (002), respectively (Fig. 2). The XRD results also show
that the solvent effect plays an important role in the formation of film texture.
Accordingly, by tuning the VW/VE ratio, the films can be deposited with well-controlled
texture and crystal size. A careful look at the XRD rocking curves for the (002) reflection
reveals that the inclination angle of the crystal [001] direction relative to the vertical
direction of the substrate plane is dominantly 0, 42, and 63° for the films deposited in
0%, 25%, and 50% ethanol, respectively (Fig. 3). The signal from the films deposited in
100% ethanol is rather weak (Fig. 3), indicating randomly oriented crystallites in the
film. Consequently, a gradual change of the film texture is achieved by increasing the
ethanol content in the solution.

Fig. 2. XRD θ–2θ scan of the films deposited at various conditions: (a) in an aqueous Fig. 3. XRD rocking curves for (002) reflection of the films deposited at various
solution (VW/VE = 1/0) for 1 h; (b) in a mixed solution (VW/VE = 3/1) for 2 h; (c) in a mixed conditions: (a) in an aqueous solution (VW/VE = 1/0) for 1 h; (b) in a mixed solution (VW/
solution (VW/VE = 1/1) for 3 h; (d) in an ethanolic solution (VW/VE = 0/1) for 4 h. The VE = 3/1) for 2 h; (c) in a mixed solution (VW/VE = 1/1) for 3 h; (d) in an ethanolic solution
asterisk (⁎) indicates the strongest reflections of the films. (VW/VE = 0/1) for 4 h.
4534 M. Wang et al. / Materials Letters 62 (2008) 4532–4534
To better understand the effect of solvent on the film texture, one needs to look into
the reactions taking place in the solution. As proposed by Li et al. [14], the reactions that
lead to the formation of ZnO crystals are as follows:
ðCH2 Þ6 N4 þ 6H2 O→6HCHO þ 4NH3 ð1Þ
NH3 þ H2 O↔NHþ
4 þ OH

ð2Þ
 2þ
2OH þ Zn →ZnO þ H2 O ð3Þ
This reaction mechanism indicates that the amount of water would considerably
affect the crystal growth rate. Inhibited crystal growth after the introduction of ethanol
is attributed to a high solvent viscosity and low solvent polarity of ethanol compared
with water [15]. In fact, the film deposition rate as well as the crystal size is observed to
decrease with decreasing water content in the solution.
4. Conclusion
ZnO thin films with well-controlled texture were prepared by a
CBD method in aqueous/ethanolic solution. The solvent effect on the
film texture has been intensively investigated. Films consisting of
densely oriented nanorod arrays with the c-axis perpendicular to the
substrate are fabricated in aqueous solution. As ethanol is introduced
in the solution, the crystals become randomly oriented in the films,
which is attributed to a decrease in crystal size and aspect ratio. The
crystals become tilted as ethanol is introduced in the solution, leading
to the survival of cracked crystals in the films.
Acknowledgment
This work was supported by the 2008 Research Fund of the
University of Ulsan.
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