Materials Letters 65 (2011) 2639–2641

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Cobalt sulphide thin films: Chemical bath deposition, growth and properties
S.T. Mane a, S.S. Kamble b,⁎, L.P. Deshmukh a
a
Thin Film & Solar Studies Research Laboratory, Department of Physics, Solapur University, Solapur, Solapur-Pune Road, Kegaon, Solapur-413255, (M.S.) India
b
Bharat Ratna Indira Gandhi College of Engineering, Solapur-Pune Road, Kegaon, Solapur-413255, (M.S.) India

a r t i c l e i n f o a b s t r a c t

Article history: In the present report synthesis of CoS thin films was carried out by a modified liquid phase chemical growth process.
Received 21 March 2011 Dark green coloured CoS thin films with hexagonal wurtzite polycrystalline structure and average grain size of
Accepted 31 May 2011 ≈15 nm were deposited. Surface morphology reveals a randomly oriented network of elongated thread like grains.
Available online 13 June 2011
The absorption coefficient of the CoS thin film is high (α≈104–105 cm−1) and a direct band gap of 1.13 eV has been
observed. n-type conduction is found in the deposited films which can be attributed to the lack of stoichiometry.
Keywords:
CoS thin films
© 2011 Elsevier B.V. All rights reserved.
Deposition
Chemical growth
Crystal structure
n-type conduction

1. Introduction
Attempts were made to deposit a variety of metal chalcogenide thin
films employing various deposition techniques individually [1–12].
The different CoS deposition process studied so far are found to be
complicated and time consuming [1–3,10,13–16]. Hence, for the first
time we have deposited CoS thin films using modified liquid phase
chemical growth process [8,9,17–20].
2. Experimental
Synthesis of CoS thin films was carried out in a relatively high
alkaline medium (PH ≈ 11 ± 0.1) on a glass substrates (previously
degreased in concentrated nitric acid for 24 h, washed with detergent
solution, rinsed with double distilled water and dried ultrasonically) of
dimension 75mm× 9mm× 2mm. The growth solution consisted of
10 ml of 1 M CoSO4, 2 ml TEA, 16 ml (AR grade) 25% ammonia, 10 ml of
1 M thiourea and around 115 ml double distilled water, which were
mixed in the above order. The glass slides were mounted on a specially
designed substrate holder attached to a constant speed motor and kept
rotating with at 70± 2 rpm in the reaction mixture for 80 min. For this
synthesis we propose the following reactions;
CoSO4 + ðTEAÞn ↔½CoðTEAÞ2n + + SO2−
4 structure of deposited films and purity is in consistent with the earlier
½CoðTEAÞ2n +
↔Co2 + + ðTEAÞn
ðNH2 Þ2 CS + 2OH − ↔S2− + 2H2 O + CH2 N2
2 + 2−
Co +S →CoS:
⁎ Corresponding author.
E-mail address: Shrishail_kamble@yahoo.co.in (S.S. Kamble).
The samples were taken off the reaction bath, washed with double
distilled water, dried and kept in a dark desiccator. Tightly adherent,
uniform deposits were diffusely reflecting with colour changing from
light green (small thickness) to dark green (terminal layer thickness).
The film composition was determined by using the EDS technique
(KEVEX-7000-77) with an accelerating voltage of 20 kV. Crystal
structure was then revealed by XRD using a Philips PW3710 with
diffractometer with monochromatic CuKα radiation (λ = 1.54247 Å).
Surface morphology was viewed through a SEM, CEMECA–SU–30
(France). The optical absorbance of a good quality sample was measured
in 500 nm–1300 nm wavelength range and energy band gap was
determined. The electrical conductivity and type of conduction
mechanism was determined in the temperature range of 300 K–550 K.
3. Results and discussion
• The terminal layer thickness was measured by an interference
technique and found to be of the order of 537 nm for a double layered
CoS thin film.
• From EDS analysis (Fig. 1) average composition was determined.
The deposits, at our experimental conditions, are Co-rich (Co ≈ 80%
and S ≈ 20%).
• XRD pattern (Fig. 2) revealed hexagonal wurtzite polycrystalline
reports [5,21]. The precise values of ‘d’, intensities of reflections and
lattice parameters (Table 1) were calculated. Average crystallite size
was calculated from the Scherrer formula and it is found to be in the
nano range (≈15 nm).
• From a typical surface micrograph (Fig. 3), it appears that, the film
growth is a randomly oriented network of elongated grains tapered at
both ends which are threaded into each other.

0167-577X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.05.117
2640 S.T. Mane et al. / Materials Letters 65 (2011) 2639–2641

Fig. 1. EDS analysis of a typical CoS thin film.

Fig. 3. SEM micrograph of a typical CoS thin film.

Fig. 4. Variation of (αhν)2 vs. hν.

Fig. 2. XRD pattern for CoS thin film.
• The thermo-probe measurements revealed n-type conduction in
deposited CoS thin films which is in contradiction to the earlier
• The absorption coefficient (α) of deposited films is high (104– observations [5]. This n-type conduction can be attributed to the
105 cm− 1) and it has a broad absorption edge as expected. The optical lack of stoichiometry in CoS as it is revealed by an EDS analysis.
band gap (Eg) was computed from the variation of (αhν)2 versus hν as
shown in Fig. 4. CoS thin films have a direct band gap of 1.13 eV.
• The electrical conductivity and thermoelectric probe measurements
of prepared CoS thin films were carried out in the 300 K–550 K
temperature range (Fig. 5). At room temperature, (300 K) electrical
conductivity is of the order of 5.25 × 10 − 6 (Ω cm) − 1. The activation
energy of an intrinsic conduction is found to be 0.671 eV.

Table 1
X-ray diffraction data of CoS films prepared by LPCBD technique.

d (obs.) A0 d (std.) A0 I/Imax (obs.) I/Imax (std.) CoS (hkl) planes

2.915 2.918 100 62 (100)

2.563 2.538 93 45 (101)
1.927 1.929 76 100 (102)
1.687 1.685 70.7 43 (110)
1.497 1.478 67 5.2 (103)
1.447 1.459 69 4.4 (200)
1.405 1.412 63 10 (112)
1.289 1.285 59 4.2 (004)
1.251 1.268 60 16 (202)
a = 3.37 A0 (std.) 0
a = 3.366 A (obs.)
c = 5.14 A0 (std.) c = 5.156 A0 (obs.)
Fig. 5. Variation of log σ with 1/T for CoS thin film.
 S.T. Mane et al. / Materials Letters 65 (2011) 2639–2641 2641

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