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Ceramics International: K. Priya, V.K. Ashith, Gowrish K. Rao, Ganesh Sanjeev
Ceramics International: K. Priya, V.K. Ashith, Gowrish K. Rao, Ganesh Sanjeev
Ceramics International
journal homepage: www.elsevier.com/locate/ceramint
A R T I C L E I N F O A BS T RAC T
Keywords: The paper compares structural, optical and electrical properties of ZnS thin films prepared by thermal
Thermal evaporation evaporation and SILAR techniques. Both techniques produced well-adherent films with uniform substrate
SILAR coverage. Films were found to be polycrystalline in both the cases. Crystallite size of the films was found to
Lattice parameter improve with thickness. Thermal evaporated films were found to possess comparatively better electrical
Quantum size effect
properties owing to their superior crystallanity. However optical absorption characteristics of both the films
were found to be similar. Detailed structural, optical and electrical studies reveal that the SILAR technique can
be an effective and economical alternative to thermal evaporation for optoelectronic applications.
⁎
Corresponding author.
E-mail address: [email protected] (G.K. Rao).
http://dx.doi.org/10.1016/j.ceramint.2017.05.094
Received 7 April 2017; Received in revised form 12 May 2017; Accepted 12 May 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Please cite this article as: K., P., Ceramics International (2017), http://dx.doi.org/10.1016/j.ceramint.2017.05.094
K. Priya et al. Ceramics International xxx (xxxx) xxx–xxx
2. Experimental procedure
2.2. SILAR
λ1λ 2
Zn2+ (In solution)+S2− (In solution)→ZnS (Adsorbed) (2) t=
2(λ1n 2 − λ 2n1) (5)
The ZnS films obtained from thermal evaporation and SILAR were
where n1 and n 2 are the refractive indices at two adjacent maxima at
then subjected to structural, optical and electrical characterization. X-
wavelengths λ1 and λ 2 . The thickness of the films was calculated using
ray diffraction patterns of the films were obtained by Rigaku Minflex X-
the Eq. (5). The thickness measured from the above two techniques
ray diffractometer (CuKα radiation, λ=1.54 Å). Zeiss scanning electron
were reconfirmed by the cross sectional SEM images of the films
microscope was used to study the surface features of the films.
(Fig. 2).
Elemental analysis was done using EDAX. Optical properties were
obtained from Shimadzu UV 1800 spectrophotometer. Electrical
properties of the films were studied by Hall Effect measurements at
room temperature.
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Table 1
Structural properties of ZnS films deposited by thermal evaporation and SILAR.
2dsinθ = nλ (6)
a = d h2 + k 2 + l 2 (7)
Fig. 3. Typical ZnS thin films deposited by (a) thermal evaporation, (b) SILAR. where h, k, l are the Miller indices.
The values of a calculated for thermal evaporated and SILAR
3.2. Structural properties deposited films are tabulated in Table 1. The lattice parameter obtained
for thermal evaporated ZnS films was close to 5.3 Å and that for SILAR
The photographs of the ZnS films obtained by thermal evaporation deposited films was about 5.5 Å, which agrees with earlier reported
and SILAR techniques are shown in Fig. 3. The thermal evaporated values [9,27].
films were almost violet and SILAR deposited films were bluish white The position of prominent XRD peaks was found to shift as
in color. The visible color of the films indicates that the absorption edge thickness of the films increased. In the case of thermal evaporated
is in the ultraviolet region. films, the 2θ value of (111) peak shifted from 29.24° to 28.94° with
The XRD patterns of thermal evaporated and SILAR deposited ZnS increase in thickness. The same was from 27.4° to 27.62° for SILAR
films are shown in Fig. 4. In both the cases, the films were found to be deposited films. The XRD unit (Rigaku Minflex) used for this XRD
polycrystalline with dominant cubic phase. Many other authors have studies has an accuracy of 0.02° (in 2θ values). Since the observed shift
reported similar result [14,21]. The XRD patterns of thermal evapo- in 2θ values is more than 0.02° it can be safely concluded that the shift
rated films show a strong, single peak corresponding to (111) plane. On arises from the changes in crystal structure of the films and not because
the other hand, the XRD patterns of SILAR deposited films show three of the instrumental error. As a result of the shift in 2θ values, the lattice
peaks corresponding to (111), (220) and (311) planes. constant also changed correspondingly. Maximum deviation in lattice
The interplanar spacing, d, was calculated using Bragg's equation constant (from the standard value of 5.41 Å for bulk ZnS) was observed
[26], in the films with least thickness. As the thickness increased, the lattice
Fig. 4. The XRD patterns of ZnS films (with different thickness) deposited by thermal evaporation (a to c) and SILAR (d to f).
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K. Priya et al. Ceramics International xxx (xxxx) xxx–xxx
where ao and a are the lattice parameters in bulk and thin film form of
ZnS. Y is the Young's modulus=8.64×1010 N m−2 and σ is the Poisson's
ratio=0.428 for ZnS, respectively.
In the case of thermal evaporated films, the stress increased with
increase in film thickness (Table 1). This is in good agreement with
earlier reports [32,33] which claim that during vacuum deposition of
high melting point materials, the stress increases with film thickness.
On the contrary, stress in SILAR deposited films decreased with
increase in film thickness (Table 1) [34]. It should be noted that the
thermal evaporation process involves high temperatures. The vapour
atoms impinging on the substrates have high thermal energy. Besides,
once a thin layer of film is formed by thermal evaporation, the
continuation of deposition process (to increase the thickness) exposes
the already deposited bottom layer of the film to the heat radiated from
the evaporation boat. Therefore prolonged thermal deposition process
increases the stress. On the other hand, SILAR deposition takes place
at room temperature. Due to slow rate of SILAR deposition, both
substrate and the ions are almost at the same temperature. The low
thickness SILAR deposited films may have some stress arising because
of the formation of polycrystalline grains on amorphous substrates. But
as the thickness increases, the subsequent layers of film material will be
formed on the film layers which are already deposited on glass. Hence
the stress decreases.
The crystallite size D was calculated from the XRD patterns using
the Scherer formula:
0. 9λ
D=
βcosθ (9)
Fig. 6. The SEM image of ZnS films of thickness 550 nm deposited by (a) thermal
The variation of crystallite size with thickness is shown in Fig. 5. evaporation (b) SILAR.
It can be seen that, irrespective of the method with which the films
were grown, there was a significant increase in the crystallite size of the interaction between substrate and subsequent impinging atoms re-
films when the thickness is increased. This behavior is in accordance duces as the thickness increases which results in better crystallinity
with earlier reports [13,34,35,36]. When the film thickness is very low, [22].
there will be a strong interaction between impinging atoms and the It can also be seen that thermally evaporated films possess better
substrate. But as the film thickness increases, the impinging atoms face crystallinity than SILAR deposited films, for a given thickness. This can
the previously settled layer of polycrystalline ZnS. Therefore, the be attributed to higher surface mobility of the impinging atoms in the
case of thermal evaporation. The vapour atoms possess high thermal
energy and hence they have higher surface mobility upon impinging on
the substrate [22]. Since the SILAR deposition takes place at room
temperature the surface mobility of the adatoms is comparatively less.
The SEM images (Fig. 6) of the ZnS films revealed that all these
films have good substrate coverage. The films were pin hole free and
the grains were continuous unlike the work reported by Qi Liu et al.
[37] and Dhanya et al. [38]. The SEM images of the SILAR deposited
films show that the films are made up of nano-sized grains. However,
no such grains are visible in the same magnification (50 K) SEM image
of the thermal evaporated films. As mentioned earlier, the crystallite
size of SILAR deposited films (calculated from XRD) is less than that of
the thermal evaporated films. Hence the grains visible in the SEM
image of SILAR deposited must be composed of several smaller
crystallites. Such type of granular structure is common in films
obtained by chemical methods. The limited surface mobility of adatoms
in SILAR deposition results in the formation of localized groups of
small crystallites.
The chemical composition of the ZnS films was determined by
Fig. 5. Variation of crystallite size of thermal evaporated and SILAR deposited ZnS thin EDAX. A typical EDAX spectrum of the films is shown in Fig. 7. Both
films with thickness. thermal evaporated and SILAR deposited films were found to have
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K. Priya et al. Ceramics International xxx (xxxx) xxx–xxx
Fig. 8. The absorbance spectra of (a) thermal evaporated and (c) SILAR deposited films with corresponding Tauc plots (b and d).
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