Phys. Status Solidi A 206, No. 11, 2551–2554 (2009) / DOI 10.1002/pssa.
200925197
Unique structure of ZnO films
deposited by chemical bath deposition
Dewei Chu* ,1 , Yoshitake Masuda1 , Kazumi Kato1 , and Takahiro Hamada2
1
National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimoshidami, Moriyama-ku, Nagoya
463-8560, Japan
2
Nanotechnology Research Laboratory, Advanced Technology Research Laboratories, Panasonic Corporation, 3-4 Hikaridai,
Seika-cho, Soraku-gun, Kyoto 619-0237, Japan
Received 21 April 2009, revised 18 May 2009, accepted 2 June 2009
Published online 30 June 2009
PACS 61.05.cp, 68.37.Hk, 73.61.Ga, 74.25.Fy, 81.15.Lm
∗
Corresponding author: e-mail dewei-chu@aist.go.jp, Phone: +81 52-736-7238, Fax: +81 52-736-7234
The unique structure of ZnO films obtained from aqueous solu-
tion method was investigated. Scanning electron microscopy
(SEM) and X-ray powder diffraction (XRD) analyses indicate
that unique morphology and structure of the region where
1 Introduction As a soft solution route alternative to
conventional deposition approaches thin films, the chemical
bath deposition (CBD) method has been widely used to
deposit semiconductor and ceramic thin films in recent
years [1]. CBD processes usually involve deposition of
material onto an existing template via hydrolysis and
condensation reactions of metal ions and complexes from
aqueous solution [2]. Control of crystal size and shape
of the films is the fundamental topic for its practical
applications, and the conditions of the solutions are
controllable by adjusting the concentration of precursors,
pH value, and additives. For example, controlled growth of
ZnO films with different morphology and optical properties
from solution have been reported [3–11]. However, the
relationship between the structures and electrical properties
of ZnO film grown from CBD method was seldom
investigated. It is known that the electrical properties
of ZnO film are very important parameters for practical
applications such as transparent conducting films [12, 13].
Unfortunately, ZnO films grown by this method usually show
poor conductivity [14–16]. Hence, it is still a significant
challenge to obtain ZnO thin films with controllable
conductivity.
In this work, ZnO films were prepared on glass substrates
with a two-step CBD method under mild conditions.
Combined effects on the structural and electrical properties of
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precipitation on the substrate may occur in parallel with other
regions. This is accompanied by a decrease of the electrical
resistivity in the absorbed region. A possible mechanism for
the resistivity transformation was discussed.
© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ZnO films were investigated, and a relatively low resistivity
of 6 × 10–3
cm in the special region was realized. The
influence mechanisms of different conditions and electrical
properties of the films have been discussed.
2 Experimental procedure ZnO films were grown
using a simple two-step process: spin-coating ZnO seeds on
the substrate and growth of films on the seeded substrate.
All chemicals (Wako Pure Chemical Industries, Ltd., Japan)
were used as received without further purification, and glass
slide (size: 76 mm × 26 mm) was used as substrates.
First, a ZnO seed was prepared by a modified sol–gel
method. Basically, 0.09 g Zn(CH3 COOH)2 and 0.12 g KOH
were dissolved into 50 ml methanol, respectively. They were
mixed rapidly, with stirring at 60 ◦ C for 5 min, then cooled
to room temperature. The resultant solution was transparent
with ZnO nanoparticles. The solution was then spin-coated
on the substrate at 500 rpm for 5 s, and 3000 rpm for 30 s.
After processing, the substrate was heated at 300 ◦ C for
30 min to remove the solvent.
Secondly, ZnO growth was carried out by suspending the
substrate in a 40-ml beaker filled with an aqueous solution
of 0.1 M zinc nitrate hexahydrate [Zn(NO3 )2 · 6H2 O] and
0.1 M methenamine (C6 H12 N4 ) at 70 ◦ C. The initial pH value
of the solution was tuned to 6.16 by adding CH3 COOH.
The substrate was inserted into the channel of a Teflon
© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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2552 D. Chu et al.: Unique structure of ZnO films deposited by chemical bath deposition

Figure 1 (online color at: www.pss-a.com)

Schematic illustration of the CBD system
(a) and substrate (b). X represents different
vertical positions of the substrate.

Figure 2 Surface SEM images of ZnO films, taken

from different vertical positions. The edge of the
glass that was contacted with Teflon was marked as
0 mm. (a) 32 mm; (b) 16 mm; (c) 9 mm; (d) 8 mm;
(e) 7 mm; (f) 6 mm; (g) 5 mm; (h) 4 mm.

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Phys. Status Solidi A 206, No. 11 (2009)
support, and the angle between the substrate and beaker
bottom was about 70◦ , as shown in Fig. 1. The coated side
of the substrate was face down, and it was found that after
heating at 70 ◦ C for 5 min white precipitation occurred in
the solution. After 16 h, the substrate was removed from the
solution, rinsed with deionized water and dried in air at 60 ◦ C.
The phase composition of the samples was characterized
by X-ray powder diffraction (XRD, RINT-2100V, Rigaku,
Cu Kα). The morphologies of the samples were observed
by field emission scanning electron microscopy (FESEM;
JSM-6335FM, JEOL, with an accelerating voltage of 5 kV).
Electrical resistivity of the films was measured by a four-
point method (K-705RS, Kyowariken).
3 Results and discussion Figure 2 shows the
evolution of the morphology of ZnO film as a function of
the different vertical positions from the bottom. It is clear
that the morphology evolution can be divided into two parts.
In the first part (x < 9 mm), dense film structure, with an
average grain size of 700 nm was observed. Besides, the
crystals were hexagonal with well-defined shape. In the
second part (x < 9 mm), the morphology transforms from
hexagonal microrod to nanorod structure, and the average
grain size and density dramatically decreased at x = 8 mm.
Figure 4 (online color at: www.pss-a.com) XRD patterns of the
ZnO films, measured at different vertical positions (x).
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Original
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2553
On further decreasing the value of x, the average grain size
gradually increased again.
Figure 3 shows the cross-sectional SEM images of the
ZnO film measured at vertical positions of 6 and 16 mm,
respectively. In both cases, the films are composed of rod-
like crystals. It is noticeable that the diameter and length
of the crystals at x = 6 mm are less than that observed at
x = 16 mm. The crystal structure of the two areas, x = 4–6 and
10–12 mm, is studied by XRD, which is shown in Fig. 4. Both
of the patterns reveal a strong diffraction derived from the
(002) plane of the hexagonal ZnO structure, indicating that
the films grow along the c-axis orientation. Meanwhile, an
obvious peak shift of (002) is found in the area of x = 4–6 mm.
The variation of resistivity in different areas is shown in
Fig. 5. For x > 9 mm, the resistivity is stable at around 5
cm.
However, for x = 5 mm, the value dramatically decreases to
6 × 10–3
cm, and this value is comparable to the doped ZnO
films prepared by other methods [17]. On further decreasing
x, the resistivity increases again.
The change of morphology, structure and electrical
property of ZnO film in different regions may result from
combined effects, such as concentration and temperature
gradient. In order to eliminate the effect of temperature gra-
dient, two heating methods, water-bath and oven have been
Figure 3 Cross-sectional SEM images of the
ZnO film, taken at different vertical positions:
(a) x = 6 mm; (b) 16 mm.
Figure 5 Resistivity of the ZnO film, measured at different vertical
positions (x).
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2554 D. Chu et al.: Unique structure of ZnO films deposited by chemical bath deposition

compared, and similar results were found. As to the of conductive ZnO films at low temperature for future
concentration gradient, a higher concentration usually results applications like gas sensing.
in a more dense structure and fewer grain boundaries.
However, from Fig. 3, it can be observed that the region of
x = 16 mm is more dense compared to that of x = 6 mm.
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