Journal of Alloys and Compounds 466 (2008) 447450

The effects of zinc nitrate, zinc acetate and zinc chloride precursors on investigation of structural and optical properties of ZnO thin lms
elik a , M. Karakz d , M. Altunbas E. Bacaksiz a, , M. Parlak b , M. Tomakin c , A. Ozc a
a

Department of Physics, Faculty of Arts and Sciences, Karadeniz Technical University, 61080 Trabzon, Turkey b Department of Physics, Middle East Technical University, 06531 Ankara, Turkey c Department of Physics, Rize Universitiy, Rize, Turkey d Department of Physics, Faculty of Arts and Sciences, Krkkale University, Krkkale, Turkey Received 5 June 2007; received in revised form 15 November 2007; accepted 16 November 2007 Available online 22 November 2007

Abstract ZnO thin lms were prepared using zinc chloride, zinc acetate and zinc nitrate precursors by spray pyrolysis technique on glass substrates at 550 C. Structural and optical properties of ZnO lms were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM) and optical transmittance spectra. Regardless of precursors, ZnO thin lms are all in hexagonal crystallographic phase and have (0 0 2) preferred orientation. SEM images show completely different surface morphologies for each precursor in ZnO thin lms. ZnO rod was observed only for zinc chloride precursor. The optical measurements reveal that lms have a low transmittance and a direct band gap approximately 3.30 eV, which is very close to band gap of intrinsic ZnO. 2007 Elsevier B.V. All rights reserved.
Keywords: Zinc oxide; Microrods; Spray pyrolysis; Transmittance

1. Introduction Considering the ever-decreasing dimensions of electronic devices, producing self-assembled micro- and nanostructured materials systems is becoming increasingly commercially important. There is also signicant academic interest in these systems, as their properties can be remarkably different from those of the bulk materials due to quantum-size effects. Much attention recently has been paid to the nanostructured materials such as ZnO and GaN, which radiate ultraviolet (UV) emission. Especially, since ZnO has a wide direct band gap of 3.4 eV at room temperature, high mechanical and thermal stabilities and much larger free exciton binding energy (60 meV) than that of GaN (26 meV) ensuring an efciency excitonic emission up to room temperature. Zinc oxide represents an important basic material due to its low cost as well as its electrical, optoelectronic and luminescent properties. Overall, ZnO is of importance for fundamental research, and also relevant for various elds of industrial and high technological applications such as gas sen-

Corresponding author. Tel.: +90 462 377 2545; fax: +90 462 325 3195. E-mail address: eminb@ktu.edu.tr (E. Bacaksiz).

sors, varistors, piezoelectric transducers, UV light detector and Schottky diodes [13]. Various ZnO nanostructures, such as nanobelts, nanoribbons, nanowires and nanorods have been fabricated by thermal evaporation, chemical vapor deposition, solgel method, electrochemically deposition, ion beam assisted deposition, rf magnetron sputtering deposition, spray pyrolysis aqueous solution method and metalorganic chemical vapor deposition [411]. Among these methods, spray pyrolysis is especially suitable and particularly useful for large area applications, since it has proved to be a simple and inexpensive method. Many authors have described the preparation and characterization of ZnO thin lms by spray pyrolysis with high c-axis preferred orientation. Nevertheless, little attention has been paid to the nature of the precursors. Romero et al. [12] studied the effects of zinc acetate and zinc chloride precursors on the preferred crystalline orientation of ZnO thin lms produced by spray pyrolysis. In the study, ZnO lm, which is produced by using zinc chloride precursor, was grown in better preferred orientation than the lm grown using zinc acetate precursor. Htay et al. and Alver et al. have obtained ZnO microrod by spray pyrolysis using zinc acetate precursor and zinc chloride precursor, respectively [13,14].

0925-8388/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jallcom.2007.11.061

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E. Bacaksiz et al. / Journal of Alloys and Compounds 466 (2008) 447450

In this work, we report the effects of different precursors such as zinc chloride, zinc acetate and zinc nitrate on the ZnO thin lms, which were deposited by spray pyrolysis method. The structural, optical and electrical properties were also investigated.
2. Experimental details
ZnO thin lms were obtained by the spray pyrolysis technique in air atmosphere. The experimental setup and the other experimental details are explained elsewhere [14]. The initial solutions are prepared from zinc chloride (ZnCl2 ), zinc acetate (Zn(CH3 COO)2 2H2 O) and zinc nitrate (Zn(NO3 )2 4H2 O) at 0.1 M concentration in deionized water. The growth was performed with a spray rate of about 5 ml/min and growth rate of 50 nm/min on the glass substrates cleaned with ethanol and dried in vacuum. During the growth process, the substrates were rotated with a speed of 10 rpm at a temperature of 550 C in order to produce homogenous lms. The obtained lms had good adhesion to the substrate surfaces. The X-ray diffraction (XRD) data of lms were taken using a Rigaku D/MaxIIIC diffractometer with Cu K radiation over the range 2 = 3 70 at room temperature. The transmittance spectra of the lms were measured by Shimadzu UV-1601 spectrophotometer in the spectral range of 1901100 nm at room temperature. The surface morphology was studied by using JEOL JST-6400 scanning electron microscopy. The resistivity of ZnO lms was determined by van der Pauw measurements at room temperature. The carrier concentration was determined by means of Hall effect measurements.

3. Results and discussion Fig. 1 shows the XRD spectra of ZnO thin lms grown on glass substrate at 550 C using zinc nitrate (Fig. 1a), zinc acetate (Fig. 1b) and zinc chloride (Fig. 1c) as ZnO precursors. The ZnO thin lms are all in hexagonal crystallographic phase and has predominantly (0 0 2) preferred orientation. ZnO lm obtained by using zinc chloride precursor had a high degree of preferential orientation with the c-axis perpendicular to the substrate; however the small peaks of (1 0 1) and (1 0 2) planes were also observed. It is known that the preferential orientation is caused by the minimization of internal stress and surface energy [15]. The ZnO lm grown by using zinc acetate precursor is shown in Fig. 1b. As it can be seen, the relative intensity of (0 0 2) peak decreased in this lm with the appearance of new peaks of (1 0 0) and (1 1 0). These results are in agreement with Romero et al. [12]. When ZnO thin lms were grown using zinc nitrate precursor, relative intensity of (0 0 2) peak is increased as shown in Fig. 1a. The widely admitted theory [16] about the mechanism for the formation of textured thin lms assumes that there are differences in the crystal growth rates on the substrate surface depending on the nature of the precursor. In accordance with this theory, many authors have reported different preferred orientations such as (0 0 2) and (1 0 1) [17,18]. The calculated c parameters were found to be 0.518, 0.518 and 0.520 nm, for zinc nitrate, zinc acetate and zinc chloride as ZnO precursors, respectively. The calculated values are found to be in good agreement with ASTM data for ZnO powder. The values of the lattice parameter for all ZnO precursors grown lms are less than that of ZnO [19], which is 0.5206 nm for a powder sample, suggesting that our lms are subjected to tensile stresses in the plane of the substrate surface. The origin of the stress may be the difference in the linear thermal expansion coefcients of ZnO

Fig. 1. XRD patterns of ZnO thin lms for (a) zinc nitrate, (b) zinc acetate and (c) zinc chloride precursors.

lm ( = 7 106 / C) and soda-lime glass ( = 9 106 / C). No diffraction peaks of other impurity phases are found in these samples. These results are in agreement with the SEM data as will be discussed later. Fig. 2ac shows the SEM micrographs of ZnO thin lms obtained using zinc nitrate, zinc acetate and zinc chloride as precursors respectively. As shown in Fig. 2, completely different surface morphologies were observed for ZnO thin lms. The reason for this diversity is probably the presence of the enough energy available for the thermal decomposition on the substrate surface; solvent evaporated before the droplets reach the substrate where thermal decomposition occurs. It is also known that the growth processes depend on the initial substrate conditions; a continuous lm can be evolved with stronger interaction between particleparticle, however particulate coating can be obtained with stronger interaction between particle and substrate. The former would result in a compact c-textured lm, but the latter would results in a less compact and randomly oriented structure [12]. Fig. 2a shows the SEM image of the lm obtained by using zinc nitrate as the precursor. A nonuniform surface morphology and indenite grain boundaries were clearly observable from the image. However, the SEM image

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around 1 m. According to the XRD pattern, the hexagonal column rods are regular and almost perpendicular to the substrate, indicating that ZnO rods preferentially grow along the [0 0 2] direction. The room temperature resistivity values of ZnO thin lms measured by van der Pauw techniques were found to be as 5.7 103 , 7.1 103 and 1.3 104 cm for zinc nitrate, zinc acetate and zinc chloride precursors, respectively. The carrier concentrations were determined as 1.1 1014 , 1.0 1014 and 9.3 1013 cm3 for the three successive precursors, respectively. The resistivity values are relatively high when compared with the reported values (43 cm) in the literature [1]. The reasons for this change in resistivity range may be due to the larger density of extrinsic traps at the grain boundaries due to oxygen chemisorptions as well as the differences in surface morphologies [20]. Corresponding mobility values were determined as 5.1, 8.6 and 10.4 cm2 /V s. Fig. 3ac shows the optical spectra for ZnO thin lms obtained by using different precursors such as zinc nitrate (Fig. 3a), zinc acetate (Fig. 3b) and zinc chloride (Fig. 3c). The optical transmission spectra of the ZnO thin lms using the above mentioned precursors were not found to be highly transparent. Since ZnO thin lms were produced at relatively high temperatures in our work, the decreased optical transmittance of the samples might be due to the scattering at the grain boundaries, which is also reported in the study of Krunks on the ZnO thin lms [21]. However the high optical transmittance was observed in ZnO thin lms prepared by spray pyrolysis at substrate temperatures lower than 500 C [17]. The smoother surface morphology and less grain boundary the lm has, the higher the transmittance is [22]. The optical band gap values of the ZnO lms were obtained from the transmission measurements by plotting (h)2 vs. h graphs. The absorption spectra of ZnO lms are shown in Fig. 4. The extrapolated values of the optical band gaps, Eg , are 3.30, 3.27 and 3.26 eV for ZnO lms produced using precursors of zinc nitrate (Fig. 4a), zinc acetate (Fig. 4b) and zinc chloride (Fig. 4c); these are very close

Fig. 2. SEM images of ZnO thin lms for (a) zinc nitrate, (b) zinc acetate and (c) zinc chloride precursors.

of the sample using zinc acetate precursor, Fig. 2b, shows the appearance of the partially protruded hexagonal crystal islands on the relatively at seeding layer. Because of their hexagonal appearance, these islands can be interpreted as the ZnO crystal seeds [13]. Therefore, it can be conrmed from this result that the seeding layer and seed crystals are composed of randomly oriented ZnO crystals; this is also conrmed by Fig. 1b. The surface morphology of ZnO thin lm grown using zinc chloride as precursor is shown in Fig. 2c. This SEM image indicates that the aligned hexagonal ZnO rods grow nearly uniform in large scale, and the diameter of the ordered ZnO rods is approximately

Fig. 3. Optical transmissions spectra of ZnO thin lms for (a) zinc nitrate, (b) zinc acetate and (c) zinc chloride precursors.

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Fig. 4. Absorption spectra of ZnO lms for (a) zinc nitrate, (b) zinc acetate and (c) zinc chloride precursors.

to band gap of intrinsic ZnO [23]. The difference in these values is within the experimental error of the used method. 4. Conclusion ZnO thin lms were prepared using zinc nitrate, zinc acetate and zinc chloride precursors by spray pyrolysis technique on glass substrates at 550 C. Regardless of precursors, ZnO thin lms are all in hexagonal structure. The lm grown using zinc chloride precursor had a well-preferred orientation of (0 0 2) while the other two are randomly oriented. SEM images show completely different surface morphologies for the ZnO thin lms using different precursors. It is interesting to note that the clear appearance of ZnO rods in the samples was obtained only for the zinc chloride precursor. The optical measurements reveal that lms have a low transmittance and the calculated optical band gap values of 3.30, 3.27 and 3.26 eV for ZnO using different precursors of zinc nitrate, zinc acetate and zinc chloride, respectively, are very close to the band gap values of intrinsic ZnO crystal. References
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