Spectrochimica Acta Part A 77 (2010) 330333

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Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

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Short communication

Effect of sintering on optical, structural and photoluminescence properties of ZnO thin lms prepared by solgel process
M. Vishwas a, , K. Narasimha Rao b , K.V. Arjuna Gowda c , R.P.S. Chakradhar d,
a

Department of Physics, M.V.J. College of Engineering, Bangalore 560067, India Department of Instrumentation, Indian Institute of Science, Bangalore 560012, India c Department of Physics, Government First Grade College, K.R. Pura, Bangalore 560036, India d Glass Technology Laboratory, Central Glass and Ceramic Research Institute (CSIR), Kolkata 700032, India
b

a r t i c l e

i n f o

a b s t r a c t
Zinc oxide (ZnO) thin lms have been deposited on glass substrates via solgel technique using zinc acetate dihydrate as precursor by spin coating of the sol at 2000 rpm. Effects of annealing temperature on optical, structural and photo luminescence properties of the deposited ZnO lms have been investigated. The phase transition from amorphous to polycrystalline hexagonal wurtzite structure was observed at an annealing temperature of 400 C. An average transmittance of 87% in the visible region has been obtained at room temperature. The optical transmittance has slightly increased with increase of annealing temperature. The band gap energy was estimated by Taucs method and found to be 3.22 eV at room temperature. The optical band gap energy has decreased with increasing annealing temperature. The photoluminescence (PL) intensity increased with annealing temperature up to 200 C and decreased at 300 C. 2010 Elsevier B.V. All rights reserved.

Article history: Received 8 January 2010 Received in revised form 23 April 2010 Accepted 28 April 2010 PACS: 42.79 Wc 78.66 Li 61.05 Cp Keywords: ZnO lms Optical properties XRD PL Solgel

1. Introduction The ZnO lm is one of the transparent conducting oxide thin lms with wide band gap of 3.37 eV and high excitonic binding energy of 60 meV, which has received increased demand for various applications including opto-electronic devices [1], transparent electrodes [2], photo catalyst [3], gas sensor [4] and MEMS gas sensors [5]. However, the main disadvantage of this material is numerous problems often exist in ZnO, which affect the electrical and optical properties [6]. In general, electrical and optical properties of ZnO transparent conducting oxide lms can be improved by oxygen partial pressure [7], doping ions [8,9], substrate temperature [10] and others. Inspire of many experimental studies there is still controversy in understanding this material in depth.

Corresponding author. Present address: CSIR-NAL, Bangalore 560017, India. Tel.: +91 80 2508 6498. Corresponding author. Present address: Department of Physics, Government Science College, Bangalore 560001, India. Tel: +91 80 2221 2924. E-mail addresses: vishu 792005@yahoo.co.in (M. Vishwas), sreechakra72@yahoo.com (R.P.S. Chakradhar). 1386-1425/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.saa.2010.04.032

Recently, Liu et al. [11] have prepared porous ZnO thin lms by solgel dip-coating method and reported the optical, structural and morphological investigations of ZnO thin lms. Nunes et al. [12] reported the comparison of optical, structural and electrical properties of pure ZnO lms and ZnO doped with indium and aluminum prepared by spray pyrolysis. They studied the effect of annealing temperature and atmosphere (air/forming gas) on these properties. They have shown the increase and decrease of resistivity with annealing temperature in presence of air and forming gas respectively. The decrease of resistivity by doping with metals also has been reported. Kaur et al. [13] have reported the effect of yttrium doping and annealing temperature on the optical, structural and electrical properties of ZnO thin lms deposited by sol gel method. They have studied the effect of annealing temperature on FWHM, lattice constant, resistivity and hall mobility. Fujihara et al. [14] have reported the effect of lithium doping and annealing temperature on optical, structural and morphological properties of ZnO thin lms deposited by solgel method. Xue et al. [15] and Zi-qiang et al. [16] have reported the effect of Al doping concentration on optical, structural, electrical and photoluminescence (PL) properties of ZnO thin lms prepared by sol gel method. Very recently, Musat et al. [17] have presented the optical, structural and electrical properties of ZnO/SiO2 nano composite thin lms prepared by sol gel method

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using different ways of sol preparation. In this work, the inuence of annealing temperature on optical, structural and photoluminescence properties were investigated on ZnO lms giving attention to the temperature range 100400 C. 2. Experimental The precursor solution of ZnO was prepared using zinc acetate dihydrate (0.5 M) {Zn (CH3 CO2 )2 2H2 O} as starting material and dissolved in isopropyl alcohol. Few drops (0.5 ml) of diethanolamine were used as stabilizer. The clear solution obtained was ltered with lter paper. The sol was warmed at 60 C with constant stirring using a magnetic stirrer for 1 h. The resultant sol was very clear and transparent and was kept in an air tight beaker for 4 h before lm deposition. The glass slides were used as substrates and they were rst cleaned with detergent, ultrasonic bath and then with isopropyl alcohol and acetone. The substrates were dried at 50 C for 2 h. A few drops of the sol was spin coated on pre-cleaned glass slides at spinning speed of 2000 rpm and spinning time of 40 s in ambient condition. The lms were annealed in steps of 100 C in the temperature range 100300 C for 1 h in air. The lms were characterized with UVVIS-NIR spectrophotometer (Ocean optics, USA). The structural investigations were performed with Philips diffractometer by using Cu K radiation. The photoluminescence spectrum of ZnO thin lms was investigated by PerkinElmer (LS 55) Fluorescence spectrometer. 3. Results and discussion 3.1. Structural studies Fig. 1 shows the XRD pattern of ZnO lm on the glass substrate annealed at 300 and 400 C for 1 h in air. It is clear from the gure that the lm annealed at 300 C was amorphous and the same lm annealed at 400 C has been converted from amorphous to polycrystalline which showed several diffraction peaks at 2 = 31.95 , 34.8 , and 36.3 ranging 2 from 20 to 65 angle with the inter-planner spacing of 2.798, 2.575, 2.47 , respectively. The relative intensities of the peaks coincide with the JCPDS data of ZnO which crystallizes in the hexagonal wurtzite structure. The relative peak intensity of these diffraction peaks also increases with the annealing temperature and resulted in better crystallinity [18], corresponds to the polycrystalline phase. The grain size was calculated for the peak (1 0 0) of ZnO at 2 = 31.95 using the Scherrers 3.2.1. Transmittance and reectance measurements The optical transmittance spectra of zinc oxide lms annealed at different temperatures is shown in Fig. 2. The transmittance has increased with annealing temperature up to 200 C and decreased with further increase of temperature. The initial increase may be due to solvent evaporation and the decrease at high temperature may be due to densication. The lm thickness has decreased from 192 to 161 nm with increase of annealing temperature from room temperature (RT) to 300 C. Fig. 3 shows the reectance spectra of ZnO thin lms annealed at different temperatures. It can be seen that the reectance increases with increasing the annealing temperature. This is explained on the basis of increase of density of the lm with annealing temperature. As the density of the lm increases, the refractive index of the lm also increases and in turn the reectance increases. The variation of refractive index and lm thickness with annealing temperature was estimated from reectance spectra at 550 nm and is reported in Table 1. The lm thickness decreases with annealing temperature and this is due

Fig. 2. Optical transmittance spectra of ZnO lms annealed at different temperatures on glass substrate.

relation [19] and was found to be 53.41 nm. The grain size increases with increasing annealing temperature [20] and hence the crystal structure of the lm is strongly depends on the annealing temperature. 3.2. Optical properties

Fig. 1. Typical X-ray diffraction (XRD) pattern of ZnO lm annealed (a) at 300 C and (b) at 400 C on glass substrate for 1 h.

Fig. 3. Reectance spectra of ZnO lms annealed at different temperatures on glass substrate.

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Table 1 Refractive index and thickness as estimated from reectance spectra for different annealing temperatures. Film annealing temperature ( C) As deposited 100 200 300 R 0.1080 0.1093 0.1230 0.1385 n 1.743 1.766 1.789 1.895 Thickness t (nm) 192 173 179 161

to the solvent evaporation and the densication of the lm. The refractive index (n) was estimated using the relation [21] n = (no ns )1/2 1 + (R )1/2 1 (R )1/2
1/2

(1)

where no and ns represent refractive indices of the surrounding medium and the substrate, respectively. R represents the value of reectance maxima in the reectance spectra.

Fig. 5. Photoluminescence spectra of ZnO lm at different annealing temperatures.

3.2.2. Optical band gap energy estimation The optical band gap energy of zinc oxide thin lms was estimated using the Taucs method [22]. The absorption coefcient was calculated using the relation = 1 t 1 T (2)

3.3. Photoluminescence studies The effect of annealing temperature on the PL properties of ZnO thin lms was investigated. The PL spectra obtained at room temperature for ZnO thin lms annealed in steps of 100 C on glass substrate are shown in Fig. 5. The PL spectra in all samples exhibit one prominent emission peak (3.2 eV) in the UV position [24] and a weak red luminescence band (in the range 1.61.75 eV). The PL intensity has enhanced with increase of annealing temperature up to 200 C then decreased at 300 C. It is to be noted that, the band emission is not related to the defects or impurities in the lm and is due to exitonic emission. The intensity of emission peak increased with decrease of band gap energy of ZnO lm. The band emission energy is slightly shifted from 3.22 to 3.30 eV with the increase of annealing temperature up to 200 C. When the annealing temperature increases, the oxygen and zinc atoms move from interstitial to lattice sites. Therefore the red emission at about 730 nm is due to the oxygen and zinc anti-sites [25]. 4. Conclusions Pure zinc oxide thin lms were prepared by solgel process and the effect of annealing on optical, structural and photoluminescence properties was investigated. The phase transition from amorphous to polycrystalline hexagonal wurtzite structure was observed at an annealing temperature of 400 C. The optical transmittance and refractive index of ZnO lms were slightly increased with increasing annealing temperature. The optical band gap decreased with the annealing temperature. The enhancement of PL intensity of band gap emission and red emission with annealing temperature at 200 C suggests that these lms can be used for photoluminescence applications at low temperatures. References
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ln

where t and T are the lm thickness and transmittance respectively. The absorbance values (h )2 versus h or energy has been plotted in the UVvisible region and is shown in Fig. 4. The linear part of the plot has been extrapolated towards energy axis. The intercept value on the energy axis has been found to be 3.23 and 3.16 eV for RT and annealing temperature of 100 C, respectively. The indirect band gap energy was decreased with annealing temperature due to the decrease of gap between conduction band edge and valance band edge (semi conducting property) of the zinc oxide lm. Liu et al. [11] have reported the band gap energy of 3.22 eV for the as deposited ZnO thin lms on glass substrates by sol gel dip-coating method using emulsion of polystyrene. Jun-Liang Zhao et al. [23] have estimated the band gap of ZnO lms in the range 3.253.27 eV at different substrate temperatures and oxygen pressures prepared by pulsed laser deposition.

Fig. 4. Optical band gap energy estimation of ZnO lm at RT and annealed at 100 C.

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