Thin Solid Films 311 1997.

114118

Effect of the substrate temperature on the properties of spray deposited

SbSe thin films from non-aqueous medium
K.Y. Rajpure
b

a,)

, C.D. Lokhande b, C.H. Bhosale

a
Thin film Physics Laboratory, Department of Physics, Shiaji Uniersity, Kolhapur-416004, India
Hahn-Meitner Institute, Bereich Strahlem Chemie, Glienicker Str 100, Postfach 390128, Berlin 14091, Germany

Received 22 January 1997; accepted 25 June 1997

Abstract
Semiconducting SbSe thin films are prepared on glass substrates from a non-aqueous medium using a spray pyrolysis technique. The
films are deposited at a fixed solution concentration of 0.1 M and at various substrate temperatures. The film thickness is of the order of
0.5 m m and is found to be relatively higher for the film deposited at 1758C substrate temperature. X-ray diffraction studies reveal that the
as deposited films are amorphous in nature, while after annealing in the N2 atmosphere at 3258C for 2 h, the films deposited at 2008C turn
into polycrystalline ones. The analysis of the absorption coefficient data reveals that as the substrate temperature increases, the optical
bandgap value of the material increases. It has also been found, for the film deposited at 2008C and annealed in N2 atmosphere, that the
polycrystalline material follows the direct optical transition with energy gap Eg opt equal to 2.14 eV. The electrical resistivity at room
temperature 300 K. is of the order of 10 6 10 7 V cm, which changes slightly after annealing. q 1997 Elsevier Science S.A.
Keywords: Deposition process; Optical properties; Resistivity; X-ray diffraction

1. Introduction

2. Experimental details

In the last few years the studies of amorphous films of

the SbSe system are attracting wide attention, due to its
good photovoltaic properties and high thermoelectric
power, which allow possible applications for optical and
thermoelectric cooling devices.
A few reports on the transport and optical properties of
Sb X Se1yX w13x, SbSe w4x and Sb 2 Se 3 w58x thin films
deposited chemically from an aqueous medium are available in the literature but no reports are available on the
preparation of SbSe thin films from a non-aqueous
medium by a spray pyrolysis technique.
We report here, for the first time, the deposition of
SbSe thin films by a spray pyrolysis technique from a
non-aqueous medium. The films so prepared are characterised by X-ray diffraction XRD., optical absorption and
electrical resistivity measurement techniques and the results have been discussed.

2.1. Preparation of thin films

Corresponding author.

0040-6090r97r$17.00 q 1997 Elsevier Science S.A. All rights reserved.

PII S 0 0 4 0 - 6 0 9 0 9 7 . 0 0 4 1 5 - X

0.1 M solutions of antimony trichloride SbCl 3 . and

selenium dioxide SeO 2 . were prepared by dissolving the
appropriate amount of the salts AR grade. in acetic acid
glacial. and formaldehyde, respectively. These equimolar
solutions were mixed together in the appropriate volumes
to obtain the Sb:Se ratio as 2:3. The whitish turbidity
resulted due to direct mixing of SbCl 3 and SeO 2 can be
redissolved by the addition of excess acetic acid glacial..
The films were prepared by spraying the clear solution
onto the preheated glass substrates. The spray rate was
kept constant at 14 cc miny1 and air was used to atomise
the solution. The films were deposited at various substrate
temperatures varying from 150 in 258C steps to 2508C.
2.2. Characterisation
The structural characterisation of SbSe films was carried out by analysing the X-ray diffraction pattern obtained
using an X-ray diffractometer model PW-1710 l s 1.5405

K.Y. Rajpure et al.r Thin Solid Films 311 (1997) 114118

115

for CuK a .. The thickness of the film was determined by

A
the weight-difference method. Optical absorption spectra
of the films were recorded using an UV-VIS-NIR spectrophotometer model Hitachi-330 Japan.. Resistivity was
measured by a two-probe method in the temperature range
300500 K. Silver paste was applied to provide good
ohmic contacts with the films.
3. Results and discussion
In the spray pyrolysis method, the starting material
required to form the desired compound are in the form of
solutions, which are then sprayed onto preheated substrates, resulting in the formation of thin films on the
substrates. When the droplets of the sprayed solution reach
the hot substrates, owing to the pyrolytic decomposition of
the solution, uniform, pinhole-free and orange colored
films of SbSe are formed that adher well to the substrates. The film thickness was measured by a weight
difference method and was found to be between 0.5 and 2
m m thick. Fig. 1 shows the thickness variation of SbSe
thin films with substrate temperature. From the plot, initially, it appears that the thickness of the SbSe thin films
increases, attaining a terminal thickness of 1.78 m m when
the substrate temperature was 1758C and then decreases
for higher substrate temperatures. This can be explained as
follows: Initially, at lower substrate temperatures e.g.,
1508C., the temperature may not be sufficient to decompose the sprayed droplets of Sb 3q and Se 2y ions from the
solution and this therefore, results in a low thickness. At a
particular substrate temperature 1758C., decomposition

Fig. 1. Variation of thickness of SbSe thin films as a function of

substrate temperature.

Fig. 2. XRD patterns of SbSe thin films deposited at: a. 1508C b.

1758C c. 2008C d. 2258C and e. 2508C.

occurs at the optimum rate resulting in the terminal thickness 1.78 m m. being attained. The decrease in film
thickness at higher substrate temperatures may be due to a
higher evaporation rate of the initial ingredients of the
solution.
The SbSe compound formation was analysed with the
help of XRD patterns of the films deposited at different
substrate temperatures in the range of 150 to 2508C. It was
found that all the films were amorphous in nature w2,3x
Fig. 2.. The XRD patterns of all the films were taken after
annealing them in a N2 atmosphere at 3258C for 2 h Fig.
3.. Comparison of American Standards for Testing Materials ASTM. data w9x of Sb 2 Se 3 with the films deposited at
2008C and annealed at 3258C for 2 h reveals that the
observed d values match with the standard d values. This
confirms the formation of Sb 2 Se 3 material at 2008C substrate temperature only. Table 1 shows a comparison of the
observed d values with ASTM data.
Fig. 4 shows the variation of relative absorptance a t .,
t being the film thickness, with wavelength l. for as-deposited films. It shows that the optical absorption coefficient a , is a function of photon energy. Also a increases
up to 1758C substrate temperature and beyond this, it
decreases. This increase in a may be attributed to the
increase in film thickness. For amorphous semiconductors,
the lack of long range order produces strong scattering

K.Y. Rajpure et al.r Thin Solid Films 311 (1997) 114118

116

Fig. 4. Variation of relative absorptance a t . with wavelength l. of

SbSe thin films deposited at: a. 1508C b. 1758C c. 2008C d. 2258C
and e. 2508C.

Fig. 3. XRD patterns of SbSe thin films, annealed at 3258C in N2

atmosphere for 2 h deposited at: a. 1508C b. 1758C c. 2008C d. 2258C
and e. 2508C.

such that k is not well defined quantum number to describe the electron quantum state w10x. For amorphous
SbSe thin films, being studied, it is observed that the
absorption coefficient near the fundamental edge follows a
power law w11,12x in the form
2

a s B E y Eg . rE,

towards low photon energies. The exponential form of the

tail may be due to disorder and defects e.g., gap states. in
the amorphous materials. The observed values of the optical energy gaps Eg opt of SbSe films are found to increase
from 0.45 to 1.55 eV with increase in substrate temperature. The increase of the bandgap with substrate temperature may be due to the change in the density of states in
the gap and in the band tails. The data for the energy gaps
obtained from optical measurements is given in Table 2.

1.

where E is the photon energy, Eg is defined as the

bandage energy and B is a function of the density of states
near the conduction and valence band edges. Fig. 5 shows
a hn .1r2 vs. hn plots for as-deposited SbSe thin films.
The relation is found to be identical in character for all the
films and indicate tailing of the absorption coefficient
Table 1
Comparison of the observed d values of Sb 2 Se 3 thin films with standard
ASTM data
Standard d
.
values A

IrIo %.

hkl . Planes

.
values A

Observed d
3.437
3.033
2.646
2.229
1.858
1.699

3.416
3.03
2.629
2.238
1.861
1.698

39.43
100.00
23.85
19.52
28.61
26.18

220.Se
100.Se
240.
331.
212.
322.

Fig. 5. Plot of a hn .1r 2 vs. hn for as-deposited SbSe thin films

deposited at: a. 1508C b. 1758C c. 2008C d. 2258C and e. 2508C.

K.Y. Rajpure et al.r Thin Solid Films 311 (1997) 114118

117

Table 2
The data of energy gaps obtained from optical measurements for SbSe
thin films deposited at different substrate temperatures
Substrate temperature 8C.

Eg opt eV.

150
175
200
225
250

0.45
0.75
0.86
1.00
1.55

The nature of the optical transition involved, for the polycrystalline film, can be determined by considering the
dependence of a on hn :

a A hn y Eg .

2.
.2

In the present case, the plot of a hn vs. hn Fig. 6. is

linear, indicating that the transition is a direct band edge
transition. The extrapolation of the linear portion of such a
plot to a s 0 yields the optical bandgap Eg opt s 2.14 eV
due to direct transition. However, for the film deposited at
2008C amorphous., the optical bandgap has been found to
be 0.86 eV. This change in the nature and value of optical
gap after annealing the film at specific temperature may be
due to i. The change in atomic order in the amorphous
phase after annealing and ii. Occurrence of wrong bonds
due to presence of 5-fold ring in amorphous structure w13x.
The two-point DC probe method for measuring the dark
resistivity shows that the films prepared are semiconducting in nature and have dark resistivities of the order of 10 6
to 10 7 V cm which is similar to the results reported by
Pramanik and Bhattacharya w8x. The higher resistivity of
the film may be due to large grain boundaries and discontinuities in the film. The variation of log r with 1000rT
for the tested films is shown in Fig. 7. The observed
activation energy, irrespective of the substrate temperature,

Fig. 6. Plot of a hn . 2 vs. hn for SbSe thin film deposited at 2008C

and annealed in N2 atmosphere at 3258C for 2 h.

Fig. 7. Plot of log r . vs. 1000rT for as-deposited SbSe thin films
deposited at: a. 1508C b. 1758C c. 2008C d. 2258C and e. 2508C.

is 0.77 eV. This uniform nature of the thermal activation

energy may be attributed to the stoichiometric uniformity
in the films prepared at this range of substrate temperatures w14x.
The dark resistivity for the polycrystalline film is found
to be of the order of 10 6 10 7 V cm, same as that of
amorphous film, deposited at the same substrate temperature. The plot of log r vs. 1000rT for annealed film is
shown in Fig. 8. It is seen that there are two regions
corresponding to low and high temperatures and electrical
conduction in these films can take place via two parallel
mechanisms: a. Intrinsic conduction mechanism which
occurs at high temperature above 435 K. and b. The

Fig. 8. Plot of log r . vs. 1000rT for SbSe thin film deposited at 2008C
and annealed in N2 atmosphere at 3258C for 2 h.

118

K.Y. Rajpure et al.r Thin Solid Films 311 (1997) 114118

hopping conduction in localized states at low temperatures

below 435 K. w1x. The activation energies corresponding
to the low and high temperature regions are 0.52 eV and
1.01 eV, respectively. The activation energy in high temperature region is nearly similar to the reported value w1x.
The difference in the estimated activation energy for polycrystalline film and reported value may be due to different
mechanism of film formation and compositional differences. However, the decrease in activation energy in low
temperature region below 435 K. for polycrystalline film
indicates that the deep trapping levels have been removed
by annealing the sample w15x.

4. Conclusions
SbSe thin film deposition using non-aqueous solvents
by a spray pyrolysis method is possible. The as deposited
films are amorphous in nature, while the films deposited at
specific substrate temperature and heat treated in a N2
atmosphere at moderate temperature are polycrystalline.
The optical bandgap of amorphous SbSe thin film increases with increase in substrate temperature. It can also
be concluded that the optical band edge of the amorphous
SbSe changes into direct transition band edge when it
turns into polycrystalline after annealing. The electrical
resistivity of the films is of the order of 10 6 10 7 V-cm.

Acknowledgements
One of the authors, KYR is indebted to the Department
of Science and Technology, New Delhi, for the award of
Junior Research Fellowship.
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