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DOI 10.1007/s10854-015-3812-7
Abstract Thin films of copper doped tin sulphide (Cux sputtering [11], electro deposition [12] and successive ionic
Sn1-xSy) with the complexing agent TEA are deposited on layer adsorption and reaction (SILAR) [1316, 18, 22].
glass substrates by SILAR technique for various molar con- SILAR technique is simple, cost effective, able to coat in
centrations (0.010.10 M) at room temperature. The struc- large area, used to prepare metal chalcogenide films, less
tural, surface morphology, topography and optical properties time consuming and making the process feasible for com-
of the films are studied for the varying molar concentrations. mercial application. The wastage of material is avoided as no
XRD studies reveal the amorphous nature of TEA added Cu precipitate is formed during this process. The film properties
doped SnS films. The surface morphology was observed by are well comparable with the properties obtained by other
SEM images. Surface topography of the film is studied by chemical methods [17]. This shows the wide applicability of
AFM. 2D-AFM images reveals that the grain size, surface SILAR method for the deposition of various metal chalco-
roughness and height decreases for the increasing concentra- genides. It is possible to produce uniform and well adherent
tion. FTIR analysis shows the molecular vibrations. The thin films. Ternary compound TEA added CTS are more
optical properties of the deposited films are investigated by promising opto-electronics materials, because their band gap
measuring the optical absorbance of the films in a range of energy matches the solar spectrum, optimum optical
300800 nm with a UVVis spectrophotometer. Other prop- absorption, their abundance and competitive cost. Further, it
erties such as transmittance, refractive index, and energy gap contained more abundant and cheaper elements that are
are calculated. Based on the above characterisations, synthe- environmentally safe to handle [9]. Till date, few works have
sized TEA added copper doped tin sulphide thin film may be been reported on CTS [15, 11, 13, 14, 18]. This work is an
used for small band-gap semiconductors, non-linear materials attempt to prepare CTS with TEA by varying molar con-
and photovoltaic cell materials. centration. Sn(TEA) complex reduces the release of Sn2?
ions into the solution and the presence of TEA promotes the
deposition of uniform and better quality films [12].
1 Introduction
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films are prepared by the SILAR technique at room tem- and rinsing operations facilitates heterogeneous reaction
perature. In this method, concentration, pH, temperature of between the solid phase and the solvated ions in the solu-
precursor solutions and the time duration for the dipping tion (Fig. 1). Thus a SILAR cycle consists of these six
process are the key factors which dictate the adsorption and operations and the same is repeated for 30 SILAR cycles
nucleation of the reacting substances and thus effective for all the ten different (0.010.10 M) molar concentra-
coating on the substrate. Hence, by keeping all these tions. Figure 2 shows the schematic representation of
parameters at the optimum level, the films are coated. The SILAR deposition of TEA added CuxSn1-xSy thin film.
deposition process is carried out at room temperature
(30 C) and the reacting solutions are kept undisturbed and
the deposition process is carried out by the following six 3 Results and discussion
steps per dipping cycle (Table 1).
In this present research work, TEA added CuxSn1-xSy thin
1. A pre-cleaned glass substrate is initially immersed in
films are deposited on glass substrates by SILAR technique
the cationic precursor TEA added tin nitrate
at room temperature using copper nitrate (CuNO3) and tin
(Sn(NO3)27H2O) solution for about 35 s.
nitrate (Sn(NO3)2 as cationic ion source and sodium sulfide
2. Then rinsed in deionised water for 35 s to remove the
(Na2S) as anionic source is reported. The deposited films
loosely bound or unadsorbed tin Sn2? ions.
are characterised using X-Ray Diffractometer (XRD),
3. The cationic precursor adsorbed substrate is subse-
Fourier Transform Infra Red spectroscopy (FTIR), Scan-
quently immersed in the anionic precursor solution
ning Electron Microscopy (SEM), Atomic Force Micro-
sodium sulfide (Na2S) for about 35 s, where the S2-
scopy (AFM) and UVvisible Spectrometer techniques.
ions are reacted with the pre-adsorbed Sn2? ions and a
The work also explores the influence of dopant (Cu2?)
layer of SnS thin film is formed.
molar composition on structural, vibrational, surface mor-
4. It is rinsed with deionised water for 35 s to remove the
phology, topography and optical studies of the TEA added
unbound ions.
CuxSn1-xSy thin films.
5. The pure SnS deposited film is dipped again in cationic
precursor solution of TEA added copper nitrate
3.1 XRD analysis
(Cu(NO3)27H2O) for about 35 s to add the Cu2? ions
on the SnS thin films as dopant and
The X-ray diffraction (XRD) pattern obtained for Cux
6. Finally the substrate is rinsed in deionised water for
Sn1-xSy thin films (Cu) x = 0.04, 0.06 and 0.09. Figure 3
35 s to remove the loosely bound or un adsorbed
exhibit the amorphous nature of Cu doped SnS thin film. The
(Cu2?) ions.
diffraction hump is observed at the 2h value of 27.06 for the
The adsorbed Cu2? ions and Sn2? are reacted with the different molar compositions of Cu doped SnS thin films
S2- ions to form TEA added CuxSn1-xSy compounds as an (Cu) x = 0.04, 0.06 and 0.09 at room temperature. Only one
ultra thin coating on the substrate. Each immersion stage is diffraction peak is observed for (Cu) x = 0.09 M in appre-
consisted with a rinsing step. These alternative immersions ciable height on the hump and the other minor peaks reveal
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Fig. 1 Schematic
representation of SILAR
method
Fig. 2 Schematic
representation of SILAR
deposition of CuxSn1-xSy thin
film
the amorphous nature. CuS and SnS phases are easy to Cu0.01MSn0.09MS0.10M film in 50, 10 and 5 lm is given in
identify in XRD. When it is present in a phase mixture with Fig. 4. The SEM micrograph of the Cu0.02MSn0.08MS0.10M
CuxSn1-xSy its diffraction peaks are not distinct. It may have film of 200 and 5 lm is given in Fig. 5. Both of them are
clear distinct peaks on annealing [1, 2, 13]. exposing the uniform surface with the formation more
irregular structures in the higher magnification.
3.2 SEM analysis The SEM micrograph of Cu0.03MSn0.07MS0.10M film in
200, 50, 20, 10, 5 and 2 lm magnifications is given in
The SEM analysis are carried out for the different compo- Fig. 6. It exposes the even coating on the substrate. To
sitions of Cu0.01MSn0.09MS0.10M, Cu0.02MSn0.08MS0.10M, know further about the surface, it is magnified to closer
Cu0.03MSn0.07MS0.10M, Cu0.04MSn0.06MS0.10M, Cu0.05M- area from 200, 50, 20, 10, 5 and 2 lm. It shows the
Sn0.05MS0.10M, Cu0.06MSn0.04MS0.10M and Cu0.09MSn0.01M improved evenness in the surface. For 200 lm, the surface
S0.10M thin films. The SEM micrograph of is uniform with some different drawing shaped spot. For
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observed in 5 lm magnification. The particles on the uni- composition of SEM micrographs of Cu0.03MSn0.07MS0.10M,
form coating are like tiny flakes in 2 lm. The morpho- Cu0.04MSn0.06MS0.10M, Cu0.06MSn0.04M S0.10M and Cu0.09M
logical property of the thin film surface indicates that the Sn0.01MS0.10M are showing smooth surface with well grown
formation of nano particles are evenly sized and uniformly particles. For the lower and higher copper composition and
distributed over the entire surface. The average sizes of the equal concentration of cations Cu and Sn (Cu0.05MSn0.05M
particles are found to be in the range below 15 nm. S0.10M) the comparative variation in morphology is observed.
Micrograph in 5 and 2 lm magnifications disclose the The particles improve in its size regularly for the high com-
formation of nano crystals in surface. It is like the stars in position of copper for the respective higher magnification.
night sky. The particles appears to be the broken shining
glass pieces in 1 lm and 500 nm. 3.3 AFM analysis
For the SEM micrographs Cu0.01MSn0.09MS0.10M and
Cu0.02MSn0.08MS0.10M, surface is uniform with the formation The surface topography analysis of the thin films is
more irregular structures. The following different examined by AFM studies for the different compositions of
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Cu0.01MSn0.09MS0.10M, Cu0.02MSn0.08MS0.10M, Cu0.03M of them are more or less having equal surface roughness
Sn0.07MS0.10M, Cu0.04MSn0.06MS0.10M, Cu0.05MSn0.05M and height. Coating of these five films are coincides with
S0.10M, Cu0.06MSn0.04MS0.10M and Cu0.09MSn0.01MS0.10M the results of SEM micrograph.
thin films. Figure 11 shows 3D AFM images of CuSnS thin 2D AFM images are shown in the Figs. 12, 13, 14, 15
film of various concentrations. All the 3D AFM images are and 16. In the minimum copper and maximum tin con-
recorded in 3 lm area. For 0.03 and 0.04 M the particles centration (x = 0.03 M and 0.04 M) of CuxSn1-xSy thin
are mostly in equal size. The surface is smooth. But for films of 2D-AFM images reveals that the grain size, surface
0.05 M, the particles are not in equal size. The surface roughness and height decrease for the increasing concen-
height varies and the surface roughness differs. So this film tration. For the equal concentration of cations Cu and Sn,
is not smooth in equal concentration of the cations Cu and the grain size, surface roughness and surface height
Sn. For 0.06 and 0.09 M the particles are grown well. Both increase. In the maximum copper and minimum tin
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concentration (x = 0.06 M) of CuxSn1-xSy thin films of FTIR measurements have been made in the wave number
2D-AFM images reveals that the grain size, surface range 4004000 cm-1. The absorption bands observed at
roughness and surface height increase comparatively with 569.00 and 686.66 cm-1 are possibly due to the stretching
equal concentration of cations Cu and Sn. For x = 0.09 M vibration of SnS. The presence of water is also confirmed
of CuxSn1-xSy thin films, the grain size, surface roughness by its bending vibration observed at 1800 cm-1. Medium
and surface height decrease. These values are tabulated in strong band position at 18001000 cm-1 is possibly due to
the Table 2. stretching vibrations of sulphide group. The absorption
peak appears around 1925 and 2081.25 cm-1 may be due
3.4 FTIR analysis to C=C vibration suggesting the organic contamination
from the source materials [16, 1921]. The weak absorp-
The FTIR spectrum of Cu doped SnS composite thin film tion band at 3495, 3521 and 2911 cm-1 is assigned to OH
for the concentration 0.010.05 M is shown in Fig. 17. stretching vibration of the adsorbed water in the sample.
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Table 2 Surface properties of grain size, surface roughness and surface height
Molar concentration of Grain Surface Surface
TEA added CuxSn1-xSy size (nm) roughness (nm) height (nm)
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Fig. 19 Absorbance versus wavelength for CuxSn1-xSy thin films for 0.010.05 and 0.060.10 M
Fig. 20 Transmittance versus wavelength for CuxSn1-xSy thin films for 0.010.05 and 0.060.10 M
of sulphide group. The weak absorption band at 3520, 3.5 UVVIS spectra analysis
3280 and 2825 cm-1 is assigned to OH stretching
vibration of the adsorbed water in the sample. FTIR 3.5.1 Optical absorbance analysis
spectrum is observed for the different molar concentra-
tions of CuSnS thin film with TEA prepared by SILAR Absorbance and transmittance values are observed for
method. The value of the absorption peak is shifted CuxSn1-xSy thin films in the wavelength range of
according to nature of material and is shifted for the 300900 nm using UVVis spectrometer analysis. Fig-
increasing concentrations. Transmittance % is changes ures 19, 20 shows the plots of absorbance verses wave-
according to the increasing molar composition. length for CuxSn1-xSy thin films. For the decreasing
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wavelength of incident photon, absorbance of CuxSn1-xSy longer wavelength in the near visible region (below
thin films increases. There is a very slow increase of 600 nm) with the increasing molar composition. So, here
absorbance in visible region for the decreasing wave- more number of valence electrons are converted into
length for different compositions. The absorbance conduction electron. The incident photons liberate more
increases with the decreasing wavelength and reaches a number of electrons in the coated material. Photon to
small absorption peak with absorption maxima around electron conversion starts at the wavelength 650700 nm
370 nm. The absorption edge of the films shifted towards for different composition.
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3.5.2 Optical transmittance studies on the doping concentration. For the solar cell fabrication
doping of appropriate materials are advisable to increase its
Transmittance versus wavelength plot for CuxSn1-xSy thin efficiency.
films for different molar concentration is given in Fig. 20.
Transmittance decreases for the minimum concentration of 3.5.3 Refractive index
copper and the maximum concentration of tin in the film
(Cu0.01Sn0.09S, Cu0.02Sn0.08S and Cu0.03Sn0.07S). Trans- The refractive index of the TEA added CuxSn1-xSy thin
mittance increases for the maximum concentration of film can be derived from the transmission spectrum using
copper and the minimum concentration of tin in the film the following Eq. 1
(Cu0.06Sn0.04S, Cu0.07Sn0.03S, Cu0.08Sn0.02S and Cu0.09 p
1 1 Tmax 2
Sn0.01S). For the equal concentration of Copper and Tin, ns 1
Tmax
the transmittance is higher it is slightly constant (Cu0.05
Sn0.05S and Cu0.04Sn0.06S). When tin is having maximum This formula may fit for extremely little circumstances. If
concentration and in the absence of copper, the transmit- the transmittance is higher, there is a meagre chance for
tance is higher and slightly constant. All the absorbed change of medium. In such type of situation, absorption is
photons are transmitted to the next layer of the material in neglected. So the transmission maximum is dominating in
copper maximum region (Cu0.09Sn0.01S). The process of the particular wavelength. The various refractive indices
photons to electron conversion is very slow. This is very (ns) for the increasing molar concentration are recorded in
similar in the case of tin maximum region (Cu0.00Sn0.10S) Table 2.
but the process of photons to electron conversion to some
extent increases moderately to some extent. 3.5.4 Band gap analysis
For the increasing doping concentration, photon to
electron conversion is increasing. But the point of photon Band gap energy of CuxSn1-xSy thin film observes the
to electron conversion is not constant. It may shift to longer graph of the absorption coefficient (Ahm)2 versus photon
(red shift) or shorter (blue shift) wavelength region based energy (hm). Show the Fig. 21, the ternary material
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Table 3 Absorbance, transmittance, refractive indices and the band gap of TEA added CuxSn1-xSy films
Molar concentration Absorbance Transmittance Refractive Band
CuxSn1-xSy (A.U.) (%) Index gap
(y = 0.10 M) (eV)
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