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Influence of Cu dopant on the optical and electrical properties of spray

deposited tin sulphide thin films

Article in Vacuum · June 2016

DOI: 10.1016/j.vacuum.2016.04.003

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Short communication

Influence of Cu dopant on the optical and electrical properties of spray

deposited tin sulphide thin films
K. Santhosh Kumar a, A. Gowri Manohari b, *, Chaogang Lou a, T. Mahalingam c,
S. Dhanapandian d
a
School of Electronic Science & Engineering, Southeast University, Nanjing 210096, Jiangsu Province, People's Republic of China
b
School of Biological Sciences & Medical Engineering, Southeast University, Nanjing 210096, Jiangsu Province, People's Republic of China
c
School of Physics, Alagappa University, Karaikudi 630004, India
d
Department of Physics, Annamalai University, Annamalainagar 608002, India

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

Article history: Copper doped tin sulphide (SnS: Cu) thin films have been prepared by the spray pyrolysis technique at
Received 25 January 2016 the substrate temperature of 350
C. The optical and electrical properties of the films were studied as a
Received in revised form function of copper dopant concentration (up to 10 at.%). The optical measurements showed the energy
29 March 2016
band gap, refractive index and extinction co-efficient values varied with increase in Cu concentration and
Accepted 4 April 2016
Available online 5 April 2016
the PL spectra showed the strong emission peak around at 765 nm. The film has the lowest resistivity
while higher carrier concentration and mobility were obtained at 8 at.% of Cu.
© 2016 Elsevier Ltd. All rights reserved.
Keywords:
Copper doped SnS
Spray pyrolysis
Optical constants
Electrical properties

Optical investigation of solid constituents is very much essential
to estimate its suitability for various applications. To enhance the
economic feasibility of thin coatings a study is made of potentially
low cost coatings. Thin films are used to create optical coatings like
anti reflective coatings on the glasses, reflective baffler on car head
lights high precision optical filters and mirrors. The optical proper-
ties of semiconductor materials are tunable varying their shapes and
sizes [1,2]. The recent investigations are directed towards the
development of cost effective and non toxic optical materials that
can be synthesized by a simple and robust technology. In this di-
rection, attention has been focused on new materials, which are
abundant in nature and can be easily processed without posing any
environmental issues. The semiconducting chalcogenide thin films
like SnS have received much attention due to its novel property [3,4].
It has direct band gap (1.2e1.6 eV) [5,6] and high optical absorption
co-efficient (>104 cm1) for photons with energies greater than the
band gap such that only a few microns of SnS are needed to absorb
most of the incident light [7]. In addition, the elemental constituents
of this material are cheap, non toxic and abundant in nature.
* Corresponding author.
E-mail address: gowrimanohari1987@gmail.com (A. Gowri Manohari).
SnS thin films have been prepared using different techniques
such as chemical bath deposition [8,9], vacuum evaporation [10], rf
sputtering [11], dip deposition [12], chemical spray pyrolysis
[13,14], etc. Among these, spray pyrolysis technique is very ad-
vantageous for large scale production of thin films with lower cost
and also for preparing pin hole free, homogeneous deposits of the
required thickness [15]. Doping in semiconductor material can
improve its optical and electrical properties. Therefore it is neces-
sary to study doped tin sulphide thin films for different applica-
tions. In this aspect Copper is identified as suitable dopant for
optical and electrical properties, so we have tried to prepare Cu
doped SnS thin films by spray pyrolysis technique.
Cu doped tin sulphide thin films (SnS: Cu) were deposited onto
75  25 mm2 microscopic glass substrates by the spray pyrolysis
technique. A detailed description of optimized parameters, pre-
cursor concentration for formation of single-phase tin sulphide thin
films and automated spray-coating unit has been discussed before
[16,17]. Copper was doped with SnS thin films using CuSO4 as the
dopant source in the ratio of [Cu/Sn] ¼ 2e10% added to starting
solution.
Optical measurements were carried out using a JASCO V-670
UVeViseNIR double-beam spectrophotometer in the wavelength
range of 400e1200 nm. The photoluminescence (PL) spectra were

http://dx.doi.org/10.1016/j.vacuum.2016.04.003
0042-207X/© 2016 Elsevier Ltd. All rights reserved.
 K. Santhosh Kumar et al. / Vacuum 128 (2016) 226e229
recorded at room temperature using a FluoroLog spectrofluorom-
eter with an excitation wavelength of 650 nm. The electrical re-
sistivity, carrier concentration and mobility were measured by
automated Hall Effect system (ECOPIA HMS-3000) measured at
room temperature.
The spectra of transmission for SnS thin films obtained at
various doping concentrations of Cu are shown in Fig. 1(a). This
figure exhibits a cut off region on transmittance spectrum at shorter
wavelengths indicating the onset of the intrinsic inter-band ab-
sorption in SnS: Cu thin films and possessed high absorption co-
efficient (>105 cm1) which means that the films were good for
absorbing sunlight from the visible to near-infrared band. The ab-
sorption edge shifted to higher wavelength region with increase in
doping concentration which indicated the decrease of optical band
gap. The decrease of transmittance at higher doping concentration
may be due to the increased scattering of photons by crystal de-
fects. The similar behavior of Cu doping in SnS thin films was
observed and reported by Manoj et al. (2007) [18].
Fig. 1 (b) illustrates the variation of (ahn)2 with hn for copper
doped tin sulphide thin films. It can be seen that the band gap value
was found to decrease from 1.55 eV to 1.37 eV for doped films upto
Fig. 1. (a) Transmittance spectra and (b) Plots of (ahn)2 versus photon energy (hn) for
Cu doped SnS thin films prepared at various doping concentrations.
227
8 at.% of copper; this value was nearly equal to the optimum value
(1.40 eV) of efficient light absorption; and then the energy band gap
increased slightly for further increase of doping concentration. The
decrease in optical band gap might be attributed to the band
shrinkage effect because of increasing carrier concentration [19].
Also, the unsaturated bonds that might be present in the layers are
responsible for the formation of some defects, while produce
localized states in the band structure reducing the optical band gap
[20]. By increasing the doping concentration above 6 at.%, the band
gap value increased and it was due to an effective incorporation of
dopant into the SnS lattice, since more copper atoms were placed at
the substitutional sites, therefore the occupied states and the band
gap were incremented [21]. These results clearly suggested that the
optical properties of SnS thin films were affected by copper doping
[22].
Fig. 2(a) depicts the variation of refractive index with different
wavelength and it was interesting to note that the nmax was shifted
to higher wavelength region (lower photon energy) with increasing
doping concentration upto 8 at.% and then shifted to lower
Fig. 2. (a) Variation of refractive index (n) and (b) Variation of extinction coefficient (k)
with wavelength for Cu doped SnS thin films prepared at various doping
concentrations.
228 K. Santhosh Kumar et al. / Vacuum 128 (2016) 226e229
Fig. 3. PL spectra for Cu doped SnS thin films prepared at various doping
concentrations.
wavelength region for further increase of doping concentration.
This shift corresponds to the doping of copper and dependence of
energy band gap. At higher transmission range the value of
refractive index could be decreased from 2.60 to 1.70 in a gradual
manner. The plot of extinction coefficient as a function of wave-
length for copper doped SnS thin films is shown in Fig. 2(b). It can
be identified that the extinction coefficient value varied in the
range of 0.30e0.43 with increasing doping concentration. The
observed low extinction coefficient value indicated the low surface
roughness of the films.
Fig. 3 shows the PL spectra of copper doped SnS thin films taken
at room temperature with an excitation wavelength of 650 nm. It
exhibits an emission peak of about 765 nm attributed to carrier
recombination at surface states. With an increase of Cu concen-
tration, the intensity of emission peak significantly increased and
its peak position was shifted to longer region upto 8 at.% of copper.
Beyond 8 at.% of Cu doping, quenching phenomenon occurred in
the system. Concentration quenching has been mainly attributed to
the migration of excitation energy between Cu2þ ion pairs in the
case of beyond the doping concentration of 8 at.%. Thus the exis-
tence of Cu2þ pairs was important for the occurrence of concen-
tration quenching effect. During the concentration quenching
process, the excitation energy is transferred from one Cu2þ ion by
nonradiative transition and a number of transfer steps take place
finally to reach the quenching site. Such behavior of decrease in
intensity with increasing copper concentration was also reported
by Wang et al. (2000) [23]. From the PL spectra it was also noted
that the red shift on doping which may be due to the indirect
recombination of electrons moving from trap level formed by Cu
atoms to holes in valence band. These trap levels were present in
energy band gap and shifted towards the valence band upon
Table 1
Electrical resistivity, carrier concentration and mobility for Cu doped SnS thin films prepared at various doping concentrations.
Cu (at.%) Resistivity (U-cm)
2 1.25  102
4 8.74  101
6 2.05  101
8 5.94  100
10 9.85  100
Fig. 4. SEM image for 8 at.% of Cu doped SnS thin films.
doping [24]. Furthermore, the localized energy level of exciton
states of Cu2þ differs from that of Sn2þ, which leads to a shift of PL
peak.
The electrical resistivity, carrier concentration and Hall mobility
for Cu doped SnS thin films were measured at room temperature
and the results have been listed in Table 1. From this table it can be
seen that the resistivity of SnS: Cu thin films decreased with an
increase in doping concentration upto 8 at.% and further increased
for increasing the doping concentration of 10 at.%. The decrease in
resistivity of the films may be due to incorporation of copper im-
purities into Sn sites, which increase the acceptor states. It helps to
increase the hole carrier concentration in the valence band and
leads to low resistivity at room temperatures [25]. When increasing
the doping concentration above 8 at.%, the resistivity of the films
increased whereas the carrier concentration and mobility values
decreased and it can be attributed to the decrease in crystallite size
which will increase the grain boundary [26]. These results were in
good agreement with the previously reported results that doping
was found to change the electrical properties of the films [27,28].
The increase in carrier concentration and mobility with an increase
of doping concentration was attributed to improvement of charge
density. Due to doping effect, the inter-grain boundary area de-
creases i.e. there is a decreasing trend in the electron scattering.
This in turn increases the conductivity.
Fig. 4 depicts the scanning electron microscopic image of SnS:
Cu (8 at.%) thin film. Spherical grains with dense structure and well
surface coverage were observed. Also, the fairly porous nature of
the film was noticed and there was a significant change in the
incorporation of Cu into SnS thin films. Moreover, the particle size
of SnS: 8 at.%Cu films (1.4 mm) was increased as compared to that of
undoped SnS thin films (1.2 mm) [17]. In addition, there were some
hard white regions observed on the surface of the films. This un-
desired formation may be the result of high stress in the film or
Carrier concentration (cm3) Hall mobility (cm2/Vs)
8.72  1015 266.5
7.25  1016 354.4
2.37  1017 432.3
3.05  1017 449.6
9.75  1016 401.8
 K. Santhosh Kumar et al. / Vacuum 128 (2016) 226e229
thermal difference between the film and the substrate [29].
In summary, copper doped SnS thin films were deposited on
microscopic glass substrates by spray pyrolysis technique at the
substrate temperature of 350
C. From this study, it was observed
that the properties of SnS thin films were improved by copper
doping. The PL measurement showed a substantial red-shift of the
band gap, which can be interpreted in terms of band gap modu-
lation and a minimum resistivity of 5.94 U cm due to doping. From
these results we have demonstrated that the properties of SnS can
be well modified by copper doping, which may used in opto-
electronics devices.
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