Physica B: Condensed Matter 534 (2018) 145–149

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Physica B: Condensed Matter

journal homepage: www.elsevier.com/locate/physb

Thermoluminescent properties of nanocrystalline ZnTe thin films: Structural

and morphological studies
Shashikant Rajpal *, S.R. Kumar
Department of Applied Sciences and Humanities, National Institute of Foundry and Forge Technology, Ranchi 834003, India

A R T I C L E I N F O A B S T R A C T

Keywords: Zinc Telluride (ZnTe) is a binary II-VI direct band gap semiconducting material with cubic structure and having
Zinc telluride potential applications in different opto-electronic devices. Here we investigated the effects of annealing on the
Thin film thermoluminescence (TL) of ZnTe thin films. A nanocrystalline ZnTe thin film was successfully electrodeposited
Theromoluminiscent on nickel substrate and the effect of annealing on structural, morphological, and optical properties were studied.
Annealing The TL emission spectrum of as deposited sample is weakly emissive in UV region at ~328 nm. The variation in
XRD
the annealing temperature results into sharp increase in emission intensity at ~328 nm along with appearance of
a new peak at ~437 nm in visible region. Thus, the deposited nanocrystalline ZnTe thin films exhibited excellent
thermoluminescent properties upon annealing. Furthermore, the influence of annealing (annealed at 400
C) on
the solid state of ZnTe were also studied by XRD, SEM, EDS, AFM. It is observed that ZnTe thin film annealed at
400
C after deposition provide a smooth and flat texture suited for optoelectronic applications.

1. Introduction Te and Zn stacked layers from aqueous electrolytes. On the basis of

Zinc telluride is one of the important semiconductor materials of II–VI
group because of its extensive potential applications in different opto-
electronic devices [1]. Zinc telluride (ZnTe) is a compound semi-
conductor with p-type conductivity due to its nonstoichiometry (Zn va-
cancy) characteristic [2]. It has a direct band gap semiconductor having
band gap 2.26 eV at 300 K [3]. This material is now a day investigated in
thin film form due to its potential towards various viable applications. It
is suitable material for several applications like solar cell, photodetector,
light emitting diodes [4]. ZnTe is one of the most attractive semi-
conductors for photovoltaics and photo-electrochemical solar cells
because of its optimum energy gap [5] and low affinity [6].
ZnTe can be developed by various physical and chemical methods
which includes RF sputtering [7], chemical vapor deposition [8], Hot
wall evaporation [9], thermal evaporation [10], molecular beam epitaxy
[11], electrodeposition [12–15]. Out of these techniques the electrode-
position is a cost-effective method for producing good quality of film.
Electrodeposition technique has diverse advantages viz., low tempera-
ture growth, ability of bandgap engineering and the ability to control the
film thickness by varying the deposition time and potential [16]. Elec-
trochemical preparation of thin films of ZnTe was first reported by Basal
and Kapur [17] using a two-stage process involving electrodeposition of
photocurrent in cyclic voltammetry of solutions containing TeO2 and
Zn2þ salts Misra and Rajeshwar postulates the formation of ZnTe but they
don't develop ZnTe thin film [15]. Again Michael Neumann-Spallart
developed the ZnTe film by using ZnSO4 and TeO2 and three electrode
geometry in aqueous medium [12]. In aqueous medium hydrogen evo-
lution and lower working temperature are major problem. Little work has
been performed in non-aqueous medium for the deposition of ZnTe thin
films. Thus, it is of interest to explore the possibility of using a different
molten salt bath for ZnTe electrodeposition.
In present study we developed ZnTe film by electro deposition tech-
nique in non-aqueous medium. The non-aqueous bath has the flexibility
of conducting electro deposition at higher temperature [18]. Non
aqueous bath offers great flexibility in choosing deposition sources,
higher working temperature (even above 100
C), and also free from
hydrogen evolution reaction. The ZnTe thin films have been electro-
deposited on nickel substrate using a three-electrode system in
non-aqueous solution. Zinc Chloride and Tellurium tetrachloride have
been used as precursors for deposition of ZnTe thin films. Using the
electro deposition technique, we report the solid state and optical
properties of as deposited and annealed ZnTe thin films. The optical and
thermal properties of nanocrystalline materials are of great interest
because these may find wide applications in a number of optical devices.

* Corresponding author.
E-mail address: sraj1162@gmail.com (S. Rajpal).

https://doi.org/10.1016/j.physb.2018.01.046
Received 29 December 2017; Received in revised form 19 January 2018; Accepted 20 January 2018

0921-4526/© 2018 Elsevier B.V. All rights reserved.

S. Rajpal, S.R. Kumar
Fig. 1. Cathodic Polarization curve of ZnTe.
Fig. 2. XRD spectra of as deposited and annealed (400
C) ZnTe film.
The results of photo physical studies revealed that the deposited nano-
crystalline ZnTe thin films exhibited excellent thermoluminescent
properties upon annealing.
2. Materials and methods
ZnTe thin films were electrodeposited on nickel substrate having di-
mensions 1.5  1 cm2 using potentiostat/galvanostat (CH Instruments,
Model 680, USA). Substrate (nickel) was cleaned in soap solution fol-
lowed by rinsing in distilled water. Then substrate was cleaned in ul-
trasonic acetone bath for 10 min, rinsed with distilled water and finally
dried in air. The deposition of ZnTe thin films was carried out cathodi-
cally from a non-aqueous electrolyte containing AR grade 0.1 M con-
centration of ZnCl2 and AR grade 0.001 M concentration TeCl4 at a
Table 1
2θ, miller planes and average crystalline size of the as deposited and annealed ZnTe thin films.
Compound As deposited ZnTe Film
2θ in degree Miller indices
ZnTe 25.26 (111)
Physica B: Condensed Matter 534 (2018) 145–149
deposition potential of 0.85 V. To balance the reaction 0.16 M of KI was
introduced in electrolyte. Electrodeposition was performed in a con-
ventional three-electrode cell with nickel substrates as cathode and
graphite rod as anode and a platinum wire as reference electrode. The
temperature of the non-aqueous electrolyte was maintained at 160
C.
The deposition was carried out at a potential of 0.85 V for 15 min
duration. When the deposition is completed the substrate was removed
from the electrolyte and washed with distilled water. The as deposited
ZnTe thin film was annealed at 400
C in air. The structural character-
ization of as deposited and annealed ZnTe thin films was performed by
high resolution Rigaku miniflex model 600 diffractometer with Cu K
alpha radiation of wave length λ ¼ 1.5418 Å. Surface morphology and
compositional analysis of films was studied by scanning electron micro-
scope and EDS (Jeol-JSM6390LV) operating with an electron beam en-
ergy of 10 KeV. The roughness measurement of electrodeposited ZnTe
thin films was carried out by Atomic Force Microscopy (NT-MDT, Solver
Pro-47)). Optical properties of film were carried out by UV–Visible
Spectroscopy (Perkin Elmer Lambda 25) and Fluorescence Spectropho-
tometer (RF-5301PC, Shimadzu) on conducting glass plate.
3. Results and discussion
3.1. Electrodeposition of ZnTe thin film
The developed ZnTe films on nickel substrate are physically stable
and show good adhesion. The films were electrodeposited in non-
aqueous medium with varying potential range from 0.75 V to 1.0 V.
The best film were deposited at 0.85 V. Electrodeposition of ZnTe can
occur over a large range of potentials between the two limits of redox
potential of Te and Zn. The steady state current voltage characteristics of
the electrodeposition matrix provide valuable information of the onset of
cathodic process and the existence of any diffusion hindrance during
growth mechanism [19]. Fig. 1 shows the typical cathodic polarization
curve obtained at 160
C. The voltage recorded in the cathodic polari-
zation with respect to the Pt reference electrode. In this figure the first
cathodic onset from 0.44 V to 0.54 V corresponds to the deposition of
Te ions whereas at higher voltage second cathodic onset from 0.76 V to
1.00 V corresponds to the deposition of ZnTe ions. The codeposition of
ZnTe compound takes place between potential range 0.8 V to 1.0 V.
3.2. Structural and morphological studies
XRD patterns of ZnTe films before and after annealing are presented
in Fig. 2. The pattern is carried out in the range of 20–80
. It is observed
that the electrodeposited ZnTe thin film indicates that the exhibited
peaks located at 2θ ¼ 25.26, 41.92 and 49.52 arises on the spectra and
the peaks are identified as (111), (220) and (311) diffraction planes of
the crystalline cubic structure. The plane observed at 45.62
(111) and
52.92
(200) are due to the nickel substrate. When ZnTe thin film was
annealed at 400Ί C in air crystallinity improves as the intensity of peaks
increases. The full width at half maxima also decreases resulting the
bigger crystalline size.
The average crystallite size of the as deposited and annealed ZnTe
thin films was measured using scherrers relation, D ¼ 0.94λ/βCosθ;
Where, λ is Wavelength of incident X-ray (¼1.54 Å) β is Full width at half
maxima in radian and θ is diffracted angle [20].
The calculated crystallite size of the as deposited and annealed ZnTe
thin films was 18 nm and 32 nm respectively. The increase in average
Annealed ZnTe Film at 400
C
Average Crystalline Size 2θ in degree Miller indices Average Crystalline Size
18 nm 25.25 (111) 32 nm
146
S. Rajpal, S.R. Kumar Physica B: Condensed Matter 534 (2018) 145–149

Fig. 3. (a) SEM photograph of as deposited ZnTe; (b)

SEM photograph of annealed ZnTe.

Fig. 4. a. EDS spectra of as deposited ZnTe b. EDS

spectra of annealed deposited ZnTe.

evinced from Fig. 3(b) fusion process occurred. The distributions of

Table 2
Atomic % of as deposited and annealed ZnTe films developed on nickel substrate.
grains on the film surface was more compact, and are dense in cluster
forms which indicates the improved crystalline quality of the ZnTe film
Elements As deposited ZnTe Film Annealed ZnTe Film
after annealing. These results are also substantiated from XRD studies.
Atomic % Atomic % Fig. 4(a) and (b) shows the compositional analysis of as deposited and
Ni 49.16 28.61 annealed ZnTe film. The peaks of the spectra are quite distinct and show
Zn 15.75 29.95 the presence of zinc and tellurium. The ratio of atomic percentage of Zn
Te 35.08 41.44 and Te of as deposited and annealed ZnTe films are observed to be 0.44
100% 100%
and 0.71 respectively. Table 2 shows the atomic percentage ratio of as
deposited and annealed ZnTe films. Here, due to annealing the Zn % is
increased and film move towards more stoichiometric. The stoichiometry
grain size due to annealing clearly indicates the crystallinity improves. can be further minimizing by optimizing the growth conditions.
The increase in average grain size decreases the grain boundaries and Fig. 5 (a) and (b) shows AFM photographs of as deposited ZnTe and
thus reduces the recombination center at the grain boundaries. The annealed ZnTe films in three dimension. The variation of the surface
calculated 2θ, miller planes and average crystalline size of the as roughness was observed at room temperature and at 400
C. The root
deposited and annealed ZnTe thin films are shown in Table 1. mean square (RMS) roughness, grain size and surface morphology of the
Surface morphology of the films has been studied by scanning elec- films are studied. The as deposited ZnTe films are observed to have small
tron microscope. The deposited samples were viewed under scanning grains, uniform grain size and number of voids which indicates that the
electron microscope at an accelerating voltage of 20 kV under high characteristics of the film is less crystalline. The RMS roughness is esti-
vacuum. SEM photograph of as deposited and annealed ZnTe film is mated to be 60 nm and 56 nm in as deposited and annealed case
shown in Fig. 3 (a) and (b) respectively. The grains are spherical, well respectively. The RMS roughness represents the standard deviation be-
connected and uniformly distributed. The grains are densely packed, free tween the height of topographic feature and the mean feature height. But
from pin holes pits and voids as is evidence from the contrast of the film. annealed at 400
C, the films are smooth, crystallinity increases and
After annealing the film at 400
C surface morphology was changed. As roughness decreases to 56 nm.

Fig. 5. (a) AFM image of as deposited ZnTe (b) AFM image of annealed ZnTe.

147
S. Rajpal, S.R. Kumar
Fig. 6. (αhν)2 vs energy (eV) plot of as deposited and annealed ZnTe films.
Fig. 7. Effect of annealing on the Emission profile of as deposited ZnTe
thin film.
3.3. Thermoluminiscent studies
The optical absorption spectra of ZnTe films deposited onto a con-
ducting glass plate were studied at room temperature in the wavelength
range of 200–900 nm. UV–visible absorption spectroscopy is an efficient
technique to monitor the optical properties of quantum-sized particles.
Band gap of the film is determined by Tauc formula, (αhν)1/n ¼ A(hνEg)
[21] Where, α, h, ν, A, Eg are absorption coefficient, plank constant,
frequency of vibration, proportionality constant and band gap
respectively.
Fig. 6 shows optical absorption spectra of ZnTe thin film which is plot
of (αhν)2 vs energy (eV) and the band gap, Eg of ZnTe is obtained by
extrapolation of the curve for (αhν)2 ¼ 0. The energy band gap is found to
be 2.22 eV in as deposited case and 2.18 eV in annealed case. The band
gap shift depends on the intrinsic defects in the ZnTe films, quantam size
effect, large density of dislocations etc due to annealing. In both the cases
the measurement of band gap indicates the semiconductor behavior.
Furthermore, thermoluminescence measurements of as deposited and
annealed ZnTe film are carried out by fluorescence spectrophotometer.
Fig. 7 shows the stimulated spectra of ZnTe under different temperatures.
The TL emission spectrum of as deposited sample is weakly emissive
in UV region at ~328 nm. The variation in the annealing temperature
results into sharp increase in emission intensity at ~328 nm along with
appearance of a new peak at ~437 nm in visible region. Thus, the
148
Physica B: Condensed Matter 534 (2018) 145–149
deposited nanocrystalline ZnTe thin films exhibited excellent thermolu-
minescent properties upon annealing. The increase in thermolumines-
cent properties upon annealing could be a consequence of decrease in
particle size. Smaller particles have larger surface/volume ratio and more
surface states, therefore, contain more accessible carrier for TL. The TL
spectra of ZnTe have broad emission due to size effect in bulk ZnTe
system. From the spectrum, the lower wavelengths are attributed to
similar size ZnTe quantum dots and higher wavelengths are attributed to
bulk ZnTe crystals.
4. Conclusions
The cubic shaped ZnTe thins film were prepared successfully on
nickel substrate using electrodeposition technique in non-aqueous me-
dium. The solid state and optical properties of annealed films were
studies by different techniques. Cubic phase ZnTe is observed by XRD
analysis. Crystallinity and average crystalline size improves after
annealing. The SEM images show uniform, compact, void-free surfaces,
and varying orientation of film after annealing. EDS spectra shows the
peaks of Zn and Te. AFM shows the roughness of the surface nearly equal
to 60 nm which slightly reduces after annealing. Band gap of the semi-
conducting film is also reduced and found to be 2.18 eV in annealed case.
ZnTe film presented have good characteristic to be used as for photo
electrochemical cell, sensor applications and photovoltaic. Moreover,
The thermoluminiscent properties of these thin film may provide useful
informations about the surface states that may explain the size depen-
dence of the surface fluorescence.
Acknowledgements
The authors are thankful for the fund provided by Ministry of HRD,
Govt. of India and Central Instrumentation Facility Lab., Birla Institute of
Technology Mesra, Ranchi for various Characterizations.
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