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Ferroelectrics
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Effects of Annealing on Thermally Evaporated SnSe Thin Films


R. Indirajith , M. Rajalakshmi , R. Gopalakrishnan & K. Ramamurthi
a b a a a

Crystal Research Laboratory, Department of Physics, Anna University, Chennai, 600 025, India
b

Crystal Growth and Thin Film Laboratory, School of Physics, Bharathidasan University, Tiruchirappalli, 620 024, India Available online: 30 Jun 2011

To cite this article: R. Indirajith, M. Rajalakshmi, R. Gopalakrishnan & K. Ramamurthi (2011): Effects of Annealing on Thermally Evaporated SnSe Thin Films, Ferroelectrics, 413:1, 108-114 To link to this article: http://dx.doi.org/10.1080/00150193.2011.551090

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Ferroelectrics, 413:108114, 2011 Copyright Taylor & Francis Group, LLC ISSN: 0015-0193 print / 1563-5112 online DOI: 10.1080/00150193.2011.551090

Effects of Annealing on Thermally Evaporated SnSe Thin Films


R. INDIRAJITH,1 M. RAJALAKSHMI,1 R. GOPALAKRISHNAN,1, AND K. RAMAMURTHI2
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Crystal Research Laboratory, Department of Physics, Anna University, Chennai 600 025, India 2 Crystal Growth and Thin Film Laboratory, School of Physics, Bharathidasan University, Tiruchirappalli 620 024, India
SnSe alloy in alkaline medium was synthesized at 100 C using SnCl2 .2H2 O and selenium as source materials. The powder X-ray diffraction patterns recorded for synthesized product conrmed the formation of nanocrystalline SnSe material. The synthesized SnSe was made as pellets and used as the source materials for the deposition of SnSe thin lms on the glass substrate by thermal evaporation method at room temperature (RT) and at various substrate temperatures of 150 C, 250 C, 350 C and 450 C. The deposited lms were annealed at 450 C for 30 min under the vacuum of 105 Torr. The effects of annealing on the structural and optical properties of the as deposited SnSe lms are reported in this article. Scanning Electron Microscopy shows the modication in surface morphology of SnSe thin lms due to annealing. Annealing of the lms reduces the transmittance and enhances optical band gap of SnSe lms. Keywords Thin lms; thermal evaporation; SEM; optical analysis; tin selenide

1. Introduction
Binary IV-VI layered semiconducting compounds have generated a great deal of interest due to their interesting electrical and optical properties. Among these compounds tin monoselenide (SnSe) has been least attended by the researchers compared to lead and Ge chalcogenides. SnSe belongs to the orthorhombic crystal structure with unit cell parameter of a = 11.496 , b = 4.151 and c = 4.444 and has the energy gap of about 1eV. The orthorhombic structure transforms to tetragonal structure at high temperature below its melting point of 860 C [1]. It has great potential in memory switching devices [2], solar cells [3], holographic recording systems [4], radiation detectors [5] and opto-elecronic devices [6]. The electrical resistance of SnSe semiconducting single crystals is pressure dependent [7]. Preparation of SnSe thin lms was reported from various experimental techniques [813]. Ana Cl udia Bernardes-Silva et al. [14] have reported that the phase change of a SnSe bulk material occurs due to annealing. The change in photosensitivity of SnSe thin lms due to annealing was investigated by Zainal et al. [15]. In the present investigation
Received in nal form September 5, 2010. Corresponding author. Tel: +91-44-2235 8710/8707, Fax: +91-44-2235 8700. E-mail: krgkrishnan@annauniv.edu, krgkrishnan@yahoo.com

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we report the effect of annealing on the SnSe thin lms prepared by thermal evaporation method using the source material synthesized from chemical route.

2. Synthesis of SnSe at Low Temperature


Recently Wang et al. [1] have reported a systematic investigation on the synthesis of nano crystalline SnSe powder in various alkaline media. When compared to previous methods reported by various investigators on the preparation of SnSe at high temperature or using toxic reagents, the method reported by Wang et al. [1] is milder/less complicated. Hence the SnSe powder has been prepared by following the simple chemical reaction route reported by Wang et al. [1]. Powder X-ray diffraction (XRD) patterns recorded for the synthesized SnSe powder conrm the formation of nanocrystalline SnSe (Fig. 1). The peaks were compared with JCPDS data (JCPDS Card number: 481224) [16] and indexed. XRD results of the synthesized powder show that the (400) plane emerges as the strongest orientation (Fig. 1) as has also been reported in the earlier works [1719].

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3. Experimental
Pellets of SnSe synthesized material (2 mm thickness and 12 mm diameter) were prepared by applying an external force of 4 tons for 1 min. These prepared pellets were cut into small pieces and used as the source material. The optimized distance of 14 cm between the glass substrate and source was maintained. Thin lms of SnSe were deposited on the well cleaned microscopic glass slides employing a Hind High Vacuum Coating Unit (Model 12-A4D) at different substrate temperatures such as RT, 150 C, 250 C, 350 C and 450 C under vacuum of 5.5 105 Torr. SnSe lms deposited at various substrate temperatures were annealed at 450 C for 30 min under vacuum (105 Torr) and then allowed to cool naturally

Figure 1. XRD pattern of synthesized SnSe powder.

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to room temperature. The annealed lms were characterized for their structural, optical and morphological properties. The results of the as deposited SnSe lms are already reported by the authors [20].

4. Results and Discussion


4.1 X-Ray Diffraction XRD results reveal that annealing of SnSe lms prepared at RT produced relatively stronger (200) peak when compared to that of (400) orientation. Further the process of annealing the lms deposited at various substrate temperatures reduces the intensity of (200) peak and increases the intensity of (400) peak. The peak observed at (300) in the as deposited lm prepared at 450 C vanished due to vacuum annealing at 450 C. The XRD patterns of as deposited and annealed SnSe lms are presented in Fig. 2. The grain size of the as deposited and annealed SnSe lms was estimated by Scherrers equation [21] and presented in Table 1. From the data it can be inferred that annealing reduces crystallite size calculated from the (400) diffraction peak except the one coated at RT. Similar results were obtained for Ba0.5 Sr0.5 TiO3 thin lms [22]. Further XRD pattern of the annealed lms enumerate that the process of vacuum annealing does not change the (400) preferential growth direction from that of the as deposited lms prepared at various substrate temperatures.

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Figure 2. XRD patterns of As deposited and annealed SnSe lms.

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Table 1 Comparison of Crystallite size and peak intensity of as deposited and annealed SnSe lms As Deposited Ts R.T 150 C 250 C (hkl) (200) (400) (200) (400) (200) (400) (200) (400) (200) (300) (400) 2 ( ) 31.381 14.967 31.337 31.394 14.993 31.351 15.386 24.043 31.483 Crystallite size (nm) 17.77 16.31 16.12 28.29 9.24 13.59 8.35 63.02 36.48 Intensity (a.u) 219.73 130.76 192.93 235.69 128.33 165.49 127.96 225.22 419.74 2 ( ) 15.074 32.414 14.802 31.411 15.129 31.326 15.074 31.285 15.312 31.428 Annealed at 450 C for 30 Minutes Crystallite size (nm) 15.8660 34.1388 8.0105 11.9281 9.1311 9.4072 10.7745 11.9927 16.6775 25.7881 Intensity (a.u) 485.84 280.42 116.82 178.08 136.37 166.19 127.62 164.52 132.41 428.26

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350 C 450 C

4.2 Scanning Electron Microscopy HITACHI-S-3000H model Scanning Electron Microscope was employed to study the surface morphology of the as deposited SnSe lms and that of the same lm annealed at 450 C. The recorded micrographs are presented in the Fig. 3. SEM micrographs show that annealing produces appreciable changes in the surface morphology of the as deposited SnSe lm due to the agglomeration of the grains at the surface.

4.3 Optical Analysis The UV-visNIR spectra were recorded for the as deposited and annealed SnSe lms in the range of 2002500 nm. The as deposited SnSe lm at 150 C acquires relatively high transmittance. It is clear that the transmittance of the lm is reduced due to annealing and this reduction may be due to increase in the lm density. The average transmittance calculated in the range of 15002500 nm for SnSe thin lms prepared at R.T, 150 C, 250 C, 350 C and 450 C is 18.4 (13.62), 39.5 (6.89), 17.2 (7.43), 34.4 (22.57) and 9.6 (8.88)% respectively and the corresponding values of annealed lms are given in the parenthesis for comparison. Using the absorption spectra of SnSe thin lms the optical band gap was calculated from the plot of (h)2 versus the photon energy (h). Band gap (Eg ) of the as deposited SnSe lms was found in the range of 1.21.4 eV and that of the annealed lms lies in the range of 3.33.7 eV. Thus the process of annealing increases the optical band gap of the SnSe thin lms prepared at various substrate temperatures. The change in the band gap of the as deposited and the corresponding annealed lms is shown in Fig. 3. The annealing temperature decreases (alter) the amount of defects and disorder in the lms and hence the optical band gap of SnSe lms increases [21, 23].

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Figure 3. SEM Photographs of SnSe lms prepared at various substrate temperatures and annealed at 450 C.

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Figure 4. Plot of substrate temperature vs Eg for as deposited and annealed SnSe thin lms.

5. Conclusion
SnSe material synthesized at a low temperature from chemical route was conrmed with powder XRD and used to deposit SnSe thin lms by thermal evaporation technique at various substrate temperatures. Deposited lms were annealed at 450 C under high vacuum (105) for 30 min. Annealing inuences the intensity of XRD peaks of the as deposited samples. The grain size calculated for the annealed SnSe lms shows appreciable change from that of the as deposited lms. However the crystalline size calculated using (400) peak for the as deposited lm at 350 C showed no change due to annealing at 450 C. The SEM image clearly gives the changes in the surface morphology due to annealing. The process of annealing changed the grain size of the crystallites of (400) peak and the band gap values effectively.

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