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Phys. Status Solidi A 206, No. 11, 2551–2554 (2009) / DOI 10.1002/pssa.

200925197

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applications and materials science
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- precipitation on the substrate may occur in parallel with other
tion method was investigated. Scanning electron microscopy regions. This is accompanied by a decrease of the electrical
(SEM) and X-ray powder diffraction (XRD) analyses indicate resistivity in the absorbed region. A possible mechanism for
that unique morphology and structure of the region where the resistivity transformation was discussed.

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1 Introduction As a soft solution route alternative to ZnO films were investigated, and a relatively low resistivity
conventional deposition approaches thin films, the chemical of 6 × 10–3  cm in the special region was realized. The
bath deposition (CBD) method has been widely used to influence mechanisms of different conditions and electrical
deposit semiconductor and ceramic thin films in recent properties of the films have been discussed.
years [1]. CBD processes usually involve deposition of
material onto an existing template via hydrolysis and 2 Experimental procedure ZnO films were grown
condensation reactions of metal ions and complexes from using a simple two-step process: spin-coating ZnO seeds on
aqueous solution [2]. Control of crystal size and shape the substrate and growth of films on the seeded substrate.
of the films is the fundamental topic for its practical All chemicals (Wako Pure Chemical Industries, Ltd., Japan)
applications, and the conditions of the solutions are were used as received without further purification, and glass
controllable by adjusting the concentration of precursors, slide (size: 76 mm × 26 mm) was used as substrates.
pH value, and additives. For example, controlled growth of First, a ZnO seed was prepared by a modified sol–gel
ZnO films with different morphology and optical properties method. Basically, 0.09 g Zn(CH3 COOH)2 and 0.12 g KOH
from solution have been reported [3–11]. However, the were dissolved into 50 ml methanol, respectively. They were
relationship between the structures and electrical properties mixed rapidly, with stirring at 60 ◦ C for 5 min, then cooled
of ZnO film grown from CBD method was seldom to room temperature. The resultant solution was transparent
investigated. It is known that the electrical properties with ZnO nanoparticles. The solution was then spin-coated
of ZnO film are very important parameters for practical on the substrate at 500 rpm for 5 s, and 3000 rpm for 30 s.
applications such as transparent conducting films [12, 13]. After processing, the substrate was heated at 300 ◦ C for
Unfortunately, ZnO films grown by this method usually show 30 min to remove the solvent.
poor conductivity [14–16]. Hence, it is still a significant Secondly, ZnO growth was carried out by suspending the
challenge to obtain ZnO thin films with controllable substrate in a 40-ml beaker filled with an aqueous solution
conductivity. of 0.1 M zinc nitrate hexahydrate [Zn(NO3 )2 · 6H2 O] and
In this work, ZnO films were prepared on glass substrates 0.1 M methenamine (C6 H12 N4 ) at 70 ◦ C. The initial pH value
with a two-step CBD method under mild conditions. of the solution was tuned to 6.16 by adding CH3 COOH.
Combined effects on the structural and electrical properties of The substrate was inserted into the channel of a Teflon

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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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Original
Paper

Phys. Status Solidi A 206, No. 11 (2009) 2553

support, and the angle between the substrate and beaker On further decreasing the value of x, the average grain size
bottom was about 70◦ , as shown in Fig. 1. The coated side gradually increased again.
of the substrate was face down, and it was found that after Figure 3 shows the cross-sectional SEM images of the
heating at 70 ◦ C for 5 min white precipitation occurred in ZnO film measured at vertical positions of 6 and 16 mm,
the solution. After 16 h, the substrate was removed from the respectively. In both cases, the films are composed of rod-
solution, rinsed with deionized water and dried in air at 60 ◦ C. like crystals. It is noticeable that the diameter and length
The phase composition of the samples was characterized of the crystals at x = 6 mm are less than that observed at
by X-ray powder diffraction (XRD, RINT-2100V, Rigaku, x = 16 mm. The crystal structure of the two areas, x = 4–6 and
Cu Kα). The morphologies of the samples were observed 10–12 mm, is studied by XRD, which is shown in Fig. 4. Both
by field emission scanning electron microscopy (FESEM; of the patterns reveal a strong diffraction derived from the
JSM-6335FM, JEOL, with an accelerating voltage of 5 kV). (002) plane of the hexagonal ZnO structure, indicating that
Electrical resistivity of the films was measured by a four- the films grow along the c-axis orientation. Meanwhile, an
point method (K-705RS, Kyowariken). 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
3 Results and discussion Figure 2 shows the Fig. 5. For x > 9 mm, the resistivity is stable at around 5  cm.
evolution of the morphology of ZnO film as a function of However, for x = 5 mm, the value dramatically decreases to
the different vertical positions from the bottom. It is clear 6 × 10–3  cm, and this value is comparable to the doped ZnO
that the morphology evolution can be divided into two parts. films prepared by other methods [17]. On further decreasing
In the first part (x < 9 mm), dense film structure, with an x, the resistivity increases again.
average grain size of 700 nm was observed. Besides, the The change of morphology, structure and electrical
crystals were hexagonal with well-defined shape. In the property of ZnO film in different regions may result from
second part (x < 9 mm), the morphology transforms from combined effects, such as concentration and temperature
hexagonal microrod to nanorod structure, and the average gradient. In order to eliminate the effect of temperature gra-
grain size and density dramatically decreased at x = 8 mm. 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 4 (online color at: www.pss-a.com) XRD patterns of the Figure 5 Resistivity of the ZnO film, measured at different vertical
ZnO films, measured at different vertical positions (x). 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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