MATERIALS CHEM;STRYiFD

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Materials Chemistry and Physics 55 ( 1998 1 5 1-54

Preparation and characterization

of electrodeposited Bi,Se, thin films

A.P. Torane , C.D. Lokhande b, P.S. Patil b, C.H. Bhosale ,*

Received 25 July 1997; received in revised form 24 November 1997; accepted 23 January 1998

Abstract
Thin films of BizSel have been prepared from an aqueousacidic bath at room temperatureusing selenium dioxide as a seleniumion source by a simple, inexpensiveelectrodepositiontechnique. The electrodepositionpotentials for different bath compositions and concentrationsare estimatedfrom polarization curves.It has beenfound that Bi( NO, j .? and SeO,in the volumetric proportion as7:3 and their equimolar solutions of 0.025 M form good quality films. The films are annealed in a nitrogen atmosphere at 200C for 2 h. The films are characterized by scanning electron microscopy, X-ray diffractionand optical absorption techniques. Studies reveal that aa-deposited andannealed thinfilmsarecontinuous

and polycrystalline in nature. The optical band gap has been found to be 0.55 eV for the above-mentionedcomposition and concentration of the film. 0 1998 Elsevier Science S.A. All rights reserved.
Keylvrds:

Bismuth selenide: Electrodeposition; Polarization curves

1. Introduction Group V-VI binary compounds and their pseudobinary solid solutions are highly anisotropic and crystallize in homologous layered structures parallel to the growth direction [ 11. Over the last two decades, many experimental data have been gathered on electrical, optical and thermoelectric properties of these materials [ 21, owing to their applications such as precise temperature control of laser diodes [ 31, optical recording system [ 41, electromechanical devices [ 51, strain gauges [6] and thermoelectric devices [7-g]. These thin films have great technological importance owing to their potential applications in photoelectrochemical devices, solar selective, optoelectronic devices, thermoelectric coolers and decorative coatings [ lo]. In recent years considerable attention has been focused on glassesof Bi and Se because of thei use in optical and photosensitive devices [ 111. Co-deposited Bi-Se thin films of different composition and thickness were prepared by Nikam and Aher for studying the electrical transport properties [ 121. Pramanik et al. have prepared Bi,Se, thin films by the chemical deposition method [ 131. Among various deposition methods, electrodeposition is a simple and inexpensive method for the preparation of thin films. The growth rate can be easily controlled through electrical quantities such as current density and deposition
* Corresponding author: Tel.: + 91 655 571 5228; Fax: + 91 23 1 656133 0254-0584/98/$19.00
PIlSO254-0584(98)00085-6

potenpotential. In rhe present investigation, we report the electrodeposition of Bi,Se, thin films on the stainless steel and fluorine doped tin oxide (FIO) coated glass substrates as deposition on copper and brass substrates is hard to obtain. The electrodeposition potentials for different bath compositions and concentrations are estimated from polarization curves. It has been found that equimolar (0.025 M) solutions of Bi( No~)~~H~O and SeO, in rhe volumetric proporation 7:3 form good quality films. The films have been studied for their structural and optical properties. An effect of annealing on the properties of the films has also been discussed.

2. Experimental
2.1. Prepnration

qf thir~j2ms

The Bi$e, thin films were prepared on stainless steel substrate and fluorine doped tin oxide (FTO) coated glass substrates (area 4 X 2 cm) by electrodeposition technique. The stainless steel substrate was polished by fine zero number polish paper, then washed by laboline and finally by an ultrasonic cleaner. The back of the substrate was covered with an insulating tape. The FTO coated glass substrate was cleaned by 50% diluted HCI and then by double distilled water. The economical and inert polished graphite plate (4 X 2 X 0.2 cm3) was used as a counter electrode. The dep-

0 1998 Elscvier Science S.A. All rights reserved.

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A, P. Torane et al. / Materids

Chrwist~~ cd Physics 55 (1998) 51-54

osition was carried out from an unstirred solution at room temperature with a potentiostatic mode of conditions. A three electrode system was used and the potentials were measured with respect to saturated calomel electrode (SCE). The distance between anode and cathode was 0.4 cm. Bi(N03)3 .5Hz0 was dissolved in concentrated nitric acid and then diluted by double distilled water to a desired normality. Selenium dioxide (SeO,) was dissolved in double distilled water. The equimolar (0.1 M) solutions of Bi( N03)3. 5H10 and SeO, with bath compositions in the volumetric proportion lO:O, 9:1, 8:2, 7:3, 64, 5:5, 4:6, 3:7, 28, 1:9, 0: 10 were used as electrolytes for determining the deposition potentials. The electrical and optical studies of the films reveal that a good quality film formation occurs at 7:3 composition. By keeping thecomposition fixed the equimolar concentration of the bath of Bi( N03) 3. 5Hz0 and SeOl was varied from 0.005 M, at the interval of 0.025 M, to 0.01 M. The deposition time and deposition potential were kept constant at 30 min and - 0.09 V (SCE) respectively. The as-deposited films were washed with double distilled water. The Bi,Se, thin films deposited on stainless steel substrate were dark grey in colour, well adherent to the substrates and uniform in appearance. They were annealed in a nitrogen atmosphere at 200C for 2 h. The thickness of the deposited film was determined by weight difference method.
2.2. Cizaracterizntion

Volt

(SCE)

22 E

cl

- 0.08

-0.16

- 0.24

Fig. 1. Polarisation curves of Bi$e, on stainless steel substracts for compositions of 3i:Se. (a) Bi, (b) 9:1, (c) 8:2, (d) 7:3, (e) 6:4, (f) 5:5, (g) 3:6, th) 3:7, (i) 2:8, (j) 1:9, (k) Se.
Volt 0 -1 ( SCE)

-2

-3

-4

-5

For microstructure investigation with SEM (Cambridge Stereoscan 250-MK-3 unit) the films were coated with goldpalladium by a polaron sputter coating unit E-2500. The coating thickness was 15 nm. The XRD patterns of the as-deposited and annealed Bi$e, thin films were investigated using a Phillips X-ray diffractometer (PW 1710) with CuKa target. Optical absorption studies were carried out using a UVVIS-NIR spectrophotometer (Hitachi Model 330, Japan) within the wavelength range of 900 to 1500 nm.

Fig. 2. Polarisation curves of Bi,Se, for FPO coated glass substrates for compositions ofBi:Se. (a) 36, (b) 3:7, (c) 2:8, (d) 1:9, (e) O:IO(Se).
Table 1

Estimated deposition potentials of equimolar (0.1 M) B&Se, from the polarisation curves for different compositions for stainless steel and FTO coated glass substrates Deposited film Bath composition 0.1 M (equimolar) PHZ IO:0 9: I 8:2 713 6:4 5:5 4:6 3:7 2:s I:9 0:lO Potentials V vs. (SCE) Stainless steel FTO coated glass

3. Results and discussion The polarization curves were plotted to estimate deposition potentials of B&Se, deposited on to the stainless steel (Fig. 1) and FTO coated glass (Fig. 2) for the baths of various compositions. The estimated deposition potentials for Bi,Se, on stainless steel and FTO coated glass substrates are shown in Table 1, It is seen that the deposition potentials for Bi2Se3 thin films deposited on FTO coated glass substrates are higher than that for deposition on stainless steel substrates. This may be ascribed to the higher resistivity of FTO coated glass substrates than that of the stainless steel substrates. The electrodeposition of Bi,Se, had been carried out from an aqueous acidic solution containing bismuth and selenium ions.

Bi Bi$e, Bi,Se, Bi$e, Bi,Se, Bi,Se, Bi$e; Bi,Se, B&Se, BiSe, Se-

- 0.059 - 0.06 - 0.07 - 0.09 - 0.094 -0.15 -0.12 -0.1-C -0.102 -0.081 - 0.07

No deposition No deposition No deposition No deposition No depoaition No deposition - 0.326 -0.67 - 0.3 -0.9 - 0.802

Se02+Se++20- Se+ is converted into Scads. The electrons react with Serldras 3Se,,,+&--+3SeA complex of Bi3+ reacts with Se- to give

71)

(2)

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Chemistry and Physics 55 (1998) 51-54

in nature and the crystallinity increases after annealing. The optical band gap (direct) energy is 0.55 eV.

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