Thin Solid Films, 248 (1994) 131- 139

137

Letter
Preparation and properties antimony trisulphide films
C. H. Bhosale, M. D. Uplane, C. D. Lockhande
(Received January 17, 1994; acceped

of sprayed

P. S. Patil and
004, India

Department of Physics, Shivaji University, Kolhapur-416 May 11, 1994)

We report here, for the first time, the deposition of Sb2S3 thin films by spray pyrolysis. Oxalic acid is added as a complexing agent and thioacetamide is used as a sulphide ion source. The deposited films have been characterised by X-ray diffraction (XRD) scanning electron microscopy (SEM), optical and electrical measurements.

2. Experimental details Abstract

Semiconducting Sb2S3 thin films have been prepared on glass substrates by spray pyrolysis. The films were deposited at optimised conditions of substrate temperature and solution concentration and have been characterised for their structural, optical and electrical properties. The films are semiconducting and amorphous. From the optical absorption study, the (indirect) bandgap is estimated to be 1.55 eV.

1. Introduction
Recently considerable attention has been given to the preparation of thin metal chalcogenide films by various techniques [l-3]. Among various metal sulphides, antimony trisulphide finds some special applications in the target material for television cameras [4], microwave devices [5], switching devices [6], and various optoelectronic devices [ 7-91. Savadago and Mandal [lo] and Lockhande [ll] have deposited Sb2S, thin films by chemical bath deposition. Pawar et al. [ 121have prepared the films using the solution gas interface technique, while George and Radhakrisshnan [ 91prepared them by a three temperature method. Badachhape and Goswami [ 131 obtained Sb2S3 films by vacuum evaporation. Many bindary and ternary semiconductors on a variety of substrates have been prepared by the spray pyrolysis technique; the more important examples being CdS, CdSe, CdTe, CuInS,, CuInSe,, Bi,CdS, [ 141, CdSb,S [ 151, etc. However, no reports are available in the literature on the preparation of Sb,S, thin films by spray pyrolysis. Merely spraying mixed solutions of antimony trichloride and thiourea in an appropriate volume onto hot substrates does not form thin films of Sb,& on the substrates. Further, it it difficult to change the pH of the solution from acidic to alkaline simply by adding NaOH or NH,OH solution.

The films prepared by taking equimolar solutions of antimony trichloride and thioacetamide in appropriate volumes to obtain a Sb:S ratio of 2:3. Oxalic acid was used as the complexing agent. 20 cm3 of 2 M oxalic acid was mixed with 100 cm3 of 0.1 M antimony trichloride. This retards sulphide precipitate formation between antimony trichloride and thioacetamide. 150 cm3 of 0.1 M thioacetamide solution was mixed with the compelxed antimony trichloride solution. The mixed solution was immediately sprayed onto hot glass substrates (300 C). The spray rate was 14 cm3 min- and air was used to atomise the solution. The structural characterisation of the Sb,S, films was carried out by analysing the X-ray diffraction pattern obtained using a Philips X-ray diffractometer model PW-1710 (1 = 1.5405 A for Cu Ka). The surface morphology was studied using SEM. The thickness of the films were determined by weight difference. Optical absorption spectra of the film were recorded by using a UV-VIS-NIR spectrophotometer model Hitachi-330 (Japan). Resistivity was measured by a two probe method in the temperature range 300-500 K.

3. Results and discussion Spray pyrolysis is a simple and inexpensive method for preparing thin film semiconductors. The starting materials required to form the desired compound are in the form of solutions which are sprayed onto preheated substrates, resulting in the formation of thin films on the substrates. The direct mixing of antimony trichloride and thioacetamide solutions results in a yellowish turbidity which prohibits the spraying process. Oxalic acid forms a strong complex with antimony, and therefore the addition of thioacetamide solution does not cause this turbidity. This mixed solution remains stable for about

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10 min. When fine droplets of spray solution reach the hot substrates, owing to pyrolytic decomposition of the solution, uniform, well adherent and dark grey colored films of Sb,S, are formed on the substrates. The preparative parameters were optimised as substrate temperature 300 C and solution concentration 0.1 M. The film thickness was between 2 and 3 urn. The X-ray diffraction pattern of the as-deposited Sb,S, film is studied. The appearance of the broad X-ray spectrum suggests that the films are amorphous. A similar amorphous nature was reported for chemi-

tally deposited Sb*S, film by Savadogo and Mandal [lo] and for vacuum evaporated films by Ghosh and Varma [ 161. SEM has been used for studying the surface morphology of the films. Figures l(a) - l(c) show SEM micrographs at three different magnifications. The micrographs show voids and holes at relatively higher magnification. The film clearly demonstrates an uneven surface morphology devoid of any irregular crystalline growth. The optical absorption spectrum of the Sb,S3 films is shown in Fig. 2. The optical absorption coefficient a is of the order of lo4 cm-. The indirect bandgap was estimated by plotting (c&v)I* versus hv (Fig. 3). The extrapolation of the straight portion to the
5.6 _

4.6

0 I 5 3.4

(4

0 2 B k3 m 4 2.2

1.0 I 300 450 600 WAVELENGTH 750 900

(nm

)
a versus wavelength 1.

Fig. 2. Plot of optical

absorption

coefficient

(b)

0.0

1.5 hu(eV

3.0 1

Fig. 1. SEM micrographs (b) 500x, (c) 3000x.

of Sb,S,

films at magnifications:

(a) 100 x ,

Fig. 3. Plot of (ah~)~ versus hv.

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films are amorphous. The room temperature electrical resistivity was of the order of 10 Q cm. The Sb,S, was found to have an indirect bandgap of Eg = 1.55 eV.

References
J. R. Lince, J. Mat. Res., 5(1990) 218. K. C. Mandal and 0. Savadogo, J. Mater. Chem., 1 (1991) 301. C. D. Lockhande, Mat. Chem. Phys., 27 (1991) I. D. Cope, US Patent No. 2,875,359 (1959). J. Grigas, J. Meshkanskas and Orlimas, Phys. Stat. Solidi (A), 37 (1976) 10. M. S. Ablowa, A. A. Andreev, T. T. Deb Akaev, B. T. Melekh, A. B. Peutsow, N. S. Sheridel and L. N. Shivilona, Sou. Phys. Semicond., 10 (1976) 629. M. J. Chokahngam, K. Nagarajo Rao, R. Rangarajan and C. V. Suryanarayana, J. Phys. D., 3 (1970) 1641. E. Montrimass and A. Pazera, Thin Solid Films, 34 (1976) 65. J. George and M. K. Radhakrishnan, Solid State Commun., 33 (1980) 987. 0. Savadogo and K. C. Mandal, Sol. Energy Mater. Solar Cells, 26(1992) 117. C. D. Lokhande, Ind. J. Pure Appl. Phys., 29 (1991) 300. S. H. Pawar, Shobha Tamhankar, P. N. Bhosale and M. D. Uplane, Ind. J. Pure Appl. Phys., 21 (1983) 665. S. B. Badachhape and Goswami, Ind. J. Pure Appl. Phys., 5 ( 1967) 477. R. Krishnakumar, V. Subramanian, Y. Ramprakash and A. S. Lakshimanan, Mat. Chem. Phys., I5 (1987) 385. S. H. Pawar, C. H. Bhosale and A. J. Pawar, Ind. J. Pure Appl. Phys., 26 (1988) 323. C. Ghosh and B. P. Varma, Solid State Commun., 31 (1979) 683.

2.5 1 2.0 2.2 2.4 2.6 ( f 1x103 28 3.0

Fig. 4. Plot of log p versus

l/T.

7 8

energy axis gives a bandgap of 1.55 eV. This value agrees with values reported by other workers [ 10, Ill. The two probe method was used to measure the electrical resistivity of the films in the temperature range 300-500 K. Figure 4 show the plot of log p versus l/T. The activation energy was estimated to be 0.28 eV. The variation of resistivity with temperature reveals that the films are semiconducting in nature.

9 10 11 12 13 14

4. Conclusions Thin films of Sb2S, have been deposited from an oxalate bath using spray pyrolysis. The deposited

15 16