Fabrication of Ag2SeTe thin films by thermal

evaporation
C. Vijayan1, M. Pandiaraman2, N. Soundararajan3, R. Chandramohan*4 and
S. Ramaswamy1
Semiconducting silver selenide telluride (Ag2SeTe) ternary thin films of different thicknesses were
synthesised employing thermal evaporation. The variation in structure of the films with thickness
was estimated using X-ray diffraction studies. The thin films of lower thickness were amorphous,
and at higher thickness, they were polycrystalline in nature with orthorhombic structure. The film
crystallinity increased with increase in thickness. Increase in thickness beyond 320 nm caused
the appearance of new peaks with increased intensity. The structural studies on typical
Ag2Se0?2Te0?8 system revealed that the stoichiometry of the bulk corresponded to that of the thin
films. Micro-Raman spectra of the Ag2Se0?2Te0?8 thin films were recorded and analysed. The
optical image of Ag2Se0?2Te0?8 thin films was also studied. The topography of the thin film was
studied using atomic force microscopy. The results are presented.
Keywords: Ag2SeTe, Thin films, Thermal evaporation, XRD, AFM, Micro-Raman, Spectroscopy

Introduction However, the AgSe bond formation is reported at

Ag2SeTe are interesting semiconducting ternary system
having potential application in energy storage devices,
photosensitisers, magneto-optic sensing devices, etc.1,2
Synthesis, characterisation, optimisation and designing
a manufacturing process of such systems in nanothin
film form are of paramount interest recently owing to
the need for storage and sensing devices. Several authors
have reported on the manufacturing of thin films for
various applications.311 They are suitable for photo-
voltaic industry and storage memory devices.1214 Se, Te
based metal alloys do have a non-stoichiometry
associated with them due to the difference in nobility
and reactivity of metals and chalcogenides. Few
attempts are reported for the mass production of this
interesting system.1517 The spectroscopic investigation
on such systems are carried out by several authors, and
the results obtained are quiet interesting. Samal and
Pradeep18 reported using the surface enhanced Raman
scattering study on dispersed Ag2Te nanowires and their
spectral sensitivity. They have also reported results on
Te and Ag2Te nanowires. The former show peaks at 149,
267 and 479 cm21 respectively, and the latter had a
single peak at 481 cm21, which is associated to AgTe
bond. Cao et al.19 reported the results of Fourier
transform infrared for as synthesised sample Ag2Se.
1 study on the Ag2SeTe ternary system are absent in the
Department of Physics, N.M.S.S. Vellaichamy Nadar College, Madurai,
India
2
Department of Physics, Nehru Memorial College, Puthanampatti, Trichy,
India
3
Thin film Laboratory, Madurai Kamaraj University, Madurai, India
4
Department of Physics, Sree Sevugan Annamalai College, Devakottai,
India
*Corresponding author, email rathinam.chandramohan@gmail.com
132 cm21. Qin et al.20 observed the change in the spectra
of Ag2Te nanotubes with different exposure times. The
Raman spectra of Ag2Te samples were weak. The
intensity of the Raman spectra improved, with the
increase in exposure time. They observed less intense
peaks at 119, 145 and 641 cm21 respectively. With
increased exposure time additional peaks were observed
at 675 and 814 cm21 respectively. The additional peaks
are due to the occurrence of redox reaction on these
films and the formation of TeO bond.
Ge et al.21 observed the Fourier transform Raman
spectra of the as prepared Ag2Se, Cu5Se4, Ni3Se4 and
PbSe nanoparticles. The peak at 141, 128 and 511 cm21
are the characteristic vibrations of the AgSe, CuSe
and NiSe bonds respectively. Mendoza-Galvan et al.22
reported the results of Raman studies on amorphous
SexTe(12x) alloys (x50?321). They have reported that
Se line, observed near 250 cm21, shifted towards
240 cm21 with the decrease in the Se content. The peak
near 200 cm21, at x50?93, becomes intense with
increase in Te content. This line has been associated
with the SeTe vibrations. In addition, the Raman line
corresponding amorphous tellurium, near 173 cm21 for
x550?78, became intense and exhibited blue shift with
increase in Te. For x50?32, they have reported the Te
Te vibrations near 155 cm21.
Careful literature survey indicated that systematic
literature. In the present investigation, the thin films of
ternary compound, Ag2Se0?2Te0?8, has been synthesised
by thermal evaporation technique. The X-ray diffraction
(XRD) pattern and Raman spectrum of the synthesised
thin films were obtained. An attempt has been made to
estimate the structure and vibration properties of the

2016 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 23 January 2014; accepted 14 August 2014
DOI 10.1179/1743294414Y.0000000353 Surface Engineering 2016 VOL 0 NO 0 1
Vijayan et al. Fabrication of Ag 2 SeTe thin films by thermal evaporation
1
thin films with film thicknesses using the obtained XRD
pattern and Raman spectrum respectively. Thermal
evaporation route is an industrially viable reproducible
technique provided that the thickness of the films is
controlled to enable industrial production.
Experimental
The silver selenide telluride (Ag2Se0?2Te0?8) thin films of
thicknesses were prepared. Films of typical thicknesses of
50, 95, 150,230 and 320 nm were prepared by thermal
evaporation on to precleaned glass substrates (0?016
0?0360?001 m) using a deposition rate of 0?2 nm s21 in
high vacuum ,1025 mbar by the evaporation of chemi-
cally synthesised Ag2Se0?2Te0?8 powder. Spectroscopically
pure Ag (99?999%), Se (99?999%) and Te (99?999%) were
used for the preparation of Ag2Se0?2Te0?8 ternary alloy
bulk in powder form in a sealed and fused quartz ampule
kept in a furnace at 1300 K for 24 h for homogenising.
The samples were then annealed at 1000 K for 24 h
followed by slow cooling to room temperature for 2 days.2
The glass slides used for preparing thin films were
precleaned by immersing in hot chromic acid for 45 min
and then rinsed with triple distilled water and cleaned with
acetone and again with triple distilled water. Thickness of
films were measured by quartz crystal thickness monitor
(Hindhivac thickness monitor model DTM-101) and
confirmed in a profilometer (Mitutoyo-SJ 301) after
deposition. The thickness was estimated with an accuracy
of 1 nm. The XRD patterns of these films were recorded
2 the DebyeScherrers formula, the average grain size of
2 Surface Engineering 2016 VOL 0 NO 0
3
using powder X-ray diffractometer (XPert PRO
PANalytical, The Netherlands) with Cu Ka radiation
(l50?1540 nm) to determine the structure of prepared
Ag2Se0?2Te0?8 thin films. Raman spectra for the bulk
material and of the prepared thin films were recorded with
the excitation wavelength of 632 nm using HeNe laser
source. The morphology was studied using atomic force
microscopy (AFM) (model DSR-XE-100TM).
Results and discussion
Structural analysis
The formation of the bulk Ag2Se0?2Te0?8 compound at
room temperature has been confirmed by X-ray powder
diffraction analysis and reported.1 Figures 13 show the
typical XRD patterns of thermally evaporated
Ag2Se0?2Te0?8 films of thicknesses of 50, 95 and
230 nm respectively. In this paper, the Pearsons XRD
standard for bulk is taken as reference for the XRD
analysis of ternary thin films.23 It is observed that the
films had peaks at two theta values of 29?86, 31?66,
35?36, 38?82, 42?32 and 43?16 respectively. They are
prominent and intense. They are corresponding to [102],
[120], [013], [122], [201] and [032] planes respectively.
For films grown with thickness ,50 nm, the XRD
shows that the films are amorphous. However, at 90 nm
thickness, the characteristic peaks tend to appear
distinctly. The [120] peak reported for the standard at
two theta values at 31?66u (Ref. 23) appears shifted
slightly to 31?42. The most intense peak at 33?58 is
absent in 90 nm. This shows that the films tend to grow
without any specific preferential orientation. The [102]
peak is also present with reduced intensity. The most
intense peak reported is at 42?32u. However, the peak
obtained at 42?42u is slightly shifted with reduced
intensity corresponding to [201] plane. The peak at
38?82u is also present at the same point with reduced
intensity. The most intense peak for 90 nm thick film
appears in 35?18, which is nothing but [013] peak, which
is one of the peaks reported for Ag2Se.3Te.7 system.23
These studies revealed that the films are ternary in
nature with selenium ,0?2 and tellurium ,0?8. This
property is supplemented using Raman studies. The
XRD studies reveal amorphous state of films at low
thickness ,50 nm, and when the thickness is increased,
the films showed crystalline orthorhombic phase. Using

4 at 154 cm21 for all the films irrespective of their
Ag2Se0?2Te0?8 has been calculated, and it is found to be
,40 nm. From the AFM studies, the average grain size
of these films is found to be ,40 nm.
Raman spectral studies
The spectral dependence of Raman intensity with
incidence frequencies are shown in Fig. 4 for both bulk
and nanothin films.
In the spectra of thin film of thickness of 50 nm, no
peak is observed because of its amorphous nature and
hence not included here. However, in the films of
thicknesses of 90, 150, 230 and 320 nm, a peak is
observed at 154 cm21. The bulk also indicates a strong
and wide peak closure to 153 cm21. Furthermore, the
intensity of these peaks is found to increase with the
decrease in thickness of the films. There is no appro-
priate shift in the position of Raman peak, and no other
peaks are found. Some noises present in bulk are also
not present in the nanothin films. The increase in full
width at half maximum is an indication of the presence
of nanograins. According to our knowledge, the
vibrational modes of ternary compound Ag2SeTe have
not been studied and reported earlier. In the present
study, an attempt is made to identify the vibrational
modes of Ag2Se0?2Te0?8 thin films. From the literature,
the vibration mode of Ag2Te is found to be observed
,152 cm21, and Ag2Se is found to be ,230 cm21.24 For
5 ac confocal micrographs of Ag2SeTe thin lms of thickness of 90, 150 and 240 nm respectively
Vijayan et al. Fabrication of Ag 2 SeTe thin films by thermal evaporation
the symmetry point group C2v, the three normal
vibrational modes are the bending vibration (A1),
symmetric stretching vibration (A1) and asymmetric
stretching vibration (B2); among these, the symmetric
stretching vibration (A1) is highly Raman active when
compared with the other two modes of vibrations.
Theoretical investigations obtained using Gaussian
mode reveal three modes for Ag2Se. The A1 modes are
obtained at 45 and 132 cm21, and the B2 mode is
obtained at 159 cm21. Usually, it is adjudged that A1
mode at 132 cm21 is highly Raman active; for Ag2Te,
the A1 modes are obtained at 25 and 153 cm21. The B2
mode is obtained at 179 cm21. Usually, it is adjudged
that A1 mode at 153 cm21 is highly Raman active, and
for SeTe, the A1 mode is obtained at 279 cm21. In the
present investigation, the micro-Raman spectra of the
sample under study of Ag2Se0?2Te0?8 shows a sharp peak
thicknesses. By comparing the micro-Raman experi-
mental results with the Gaussian theoretical investiga-
tions for Ag2Se and Ag2Te, it is found that the
proportion of Te in Ag2Se0?2Te0?8 is prominent rather
than Se.
In the present sample preparation, the proportionate
of tellurium in the Ag2Se0?2Te0?8 compound is higher
than the proportion of selenium. The structural studies
revealed by XRD have indicated a composition with
selenium composition less and is in conformity with the
results of micro-Raman. The formation of Te bonds is
higher, and the modes of vibrations are occurring
dominantly due to the Te atoms than the Se atoms. In
this investigation, the high intense peak observed ,154
cm21 is very close to the peak observed in the micro-
Raman spectra of Ag2Te films.24
The occurrence of peak ,154 cm21 in the spectra is
mainly due to the formation of TeTe bonds.25
Generally, the silver chalcogenides are very sensitive to
laser beams and cause a redox reaction in it. The
exposure time of laser on these films was very short, and
the possibilities for the occurrence of redox reaction on
these films are negligible, and hence, there are no TeO
bonds in the recorded spectra. The intensity of Raman
lines in the present investigation increases with decrease
in thicknesses of thin films. In Raman studies, increasing
number of scattering molecules enhances the intensity of
Raman bands. The increase in intensity is a measure of
Surface Engineering 2016 VOL 0 NO 0 3
Vijayan et al. Fabrication of Ag 2 SeTe thin films by thermal evaporation
6 ac Two-dimensional images (AFM) obtained for ther-
mal evaporated Ag2SeTe lms of various thicknesses
cross-sectional increase in scattering, which may be
attributed to chemical nature of the reactions, surface
roughness or optical property. Hence, the increase in
surface roughness and the change in chemical reaction
may contribute significantly to the intensity variations.
Micro-Raman optical image
The optical image obtained for Ag2Se0?2Te0?8 thin films
of thicknesses of 50, 95 and 230 nm using micro-Raman
microscope is shown in Fig. 5. These micrographs reveal
that the films are formed due to the clusters of
agglomerated grains of Ag2Se0?2Te0?8 particulates of
submicrometre dimensions to form discrete islands of a
few micrometres, and the thermal energy was sufficient
to carry these domains to the surface of the substrate.
Alternatively, the evaporated particulates of few nano-
metres first reach the substrate and become centres of
nuclei for attracting more vapours, and this grain gets
agglomerated and spreads throughout the substrate. At
lower thickness, the distribution seems to be quite
uniform. For higher thicknesses, the films have some
grains and grain boundaries. It is, as if, the particulates
agglomerated form individual grains and are separated
to provide some grain boundaries. As the thickness is
4 Surface Engineering 2016 VOL 0 NO 0
increased, the boundaries are also filled with smaller
particles and the films found to have a layer composed
of both grains and grain boundaries embedded with very
small uniform aggregates and bigger ones covering the
entire substrate. The uniform distributions revealed by
the micrographs testify to the higher quality of films at
higher thicknesses. A closer look at some samples with
higher thickness supports our assumption by revealing
larger aggregates that are resulting from the melting of a
few bigger grains and annexing neighbouring grains,
forming small island-like structures.
Figure 6 shows the typical AFM spectra obtained for
film of thickness of 90, 150 and 240 nm. The micro-
graphs indicate the modification of morphology and
grain size during increase in thickness of this system. The
typical grain size ,40 nm is measured for a film of
thickness of 150 nm.
Conclusions
The fabrication of thin films of ternary system of
Ag2SeTe using thermal evaporation has been envisaged.
X-ray diffraction pattern of these films confirmed the
formation of polycrystalline orthorhombic phase at
higher thicknesses. However, the films were amorphous
at lower thickness. The ternary Ag2Se0?2Te0?8 thin films
composition was estimated from the XRD studies.
Optical image of Ag2Se0?2Te0?8 thin films were recorded
and presented. Micro-Raman spectral results of
Ag2Se0?2Te0?8 thin films with different thicknesses
between 50 and 320 nm were analysed. Raman active
peaks are attributed to AgTe vibration modes. The
AFM images indicate the modification of morphology
and grain size during increase in thickness of this system
associated with filling of grain boundaries or voids
during addition of layers.
References
1. C. Vijayan, N. Soundararajan, R.Chandramohan, V. Dhanasekeran,
K. Sundaram, K. Neivasagam and T. Mahalingam: J. Microsc.,
2011, 243, 261.
2. C. Vijayan, M. Pandiaraman, N. Soundararajan, R.Chandramohan,
V. Dhanasekeran, K. Sundaram, T. Mahalingam and A. John Peter:
J. Mater. Sci. Mater. Electron., 2010, 22, 545.
3. P. D. Tall, S. Ndiaye, A. C. Beye, Z. Zong, W. O. Soboyejo, H.-J.
Lee, A. G. Ramirez and K. Rajan: Mater. Manuf. Processes, 2007,
22, 175.
4. T. Otiti, Y. Cao, S. M. Allameh, Z. Zong, O. Akogwu and W. O.
Soboyejo: Mater. Manuf. Processes, 2007, 22, 195.
5. D. S. Sofronov, Y. A. Zagoruiko, N. O. Kovalenko, A. S.
Gerasimenko, V. N. Baumer, P. V. Mateychenko, A. G. Mamalis
and S. N. Lavrynenko: Mater. Manuf. Processes, 2013, 28, 944.
6. Y.u Bai, F. L. Yu, S. W. Lee, H. Chen and J. F. Yang: Mater.
Manuf. Processes, 2012, 27, 58.
7. K. G. Prashanth and B. S. Murty: Mater. Manuf. Processes, 2010,
25, 592.
8. K. F. Tamrin, Y. Nukman and S. S. Zakariyah: Mater. Manuf.
Processes, 2013, 28, 857.
9. W. Soboyejo: Special issue materials and manufacturing
processes on multifunctional micro- and nano-structures, Mater.
Manuf. Processes, 2007, 22, 139.
10. T. Mahalingam, S. Thanikaikarasan, V. Dhanasekaran, A.
Kathalingam, S. Velumani and J.-K. Rhee: Mater. Sci. Eng. B,
2010, B174, 257262.
11. T. Mahalingam, V. Dhanasekaran, G. Ravi, S. Lee, J. P. Chu and
H.-J. Lim: J. Optoelectron. Adv. Mater., 2010, 12, 13271332.
12. V. M. Dzhagan, M. Ya Valakh, A. E. Raevskaya, A. L. Stroyuk,
S. Ya Kuchmiy and D. R. T. Zahn: Nanotechnology, 2008, 19,
305707.
13. P. Lakshmi and K. S. Raghavan: Mater. Manuf. Processes, 1992, 7,
(1).
 Vijayan et al. Fabrication of Ag 2 SeTe thin films by thermal evaporation

14. D. Sharma and S. K. Thakur: Mater. Manuf. Processes, 2011, 91,
(6), 899907.
15. V. S. Vinogradov, G. Karczewski, I. V. Kucherenko, N. N. Melnik
and P. Fernandez: Phys. Solid State, 2008, 50, 1, 164.
16. M. G. Sridharan, M. Mekaladevi, S. K. Narayandass, D. Mangalaraj
and H. Chul Lee: J. Optoelectron. Adv. Mater., 2005, 7, 3, 1479.
17. K. Neyvasagam, V. Ramakrishnan, C. Sanjeevaraja and N.
Soundararajan: Optoelectron. Adv. Mater. Rapid Commun., 2007,
1, 7, 319.
18. A. K. Samal and T. Pradeep: J. Phys. Chem. C, 2009, 113C, 13539.
19. H. Cao, Y. Xiao, Y. Lu, J. Yin, B. Li, S. Wu and X. Wu: Nano
Res., 2010, 3, 12, 863.
20. A. Qin, Y. Fang, P. Tao, J. Zhang and C. Su: Inorg. Chem., 2007,
46, 18, 7403.
21. J.-P. Ge and Y.-D. Li: J. Mater. Chem., 2003, 13, 911.
22. A. Mendoza-Galvan, E. Garcia-Garcia, Y. V. Vorobiev,
J. Gonzalez-Hernandez: Microelectron. Eng., 2000, 5152,
677.
23. Pearsons crystal data, Powder pattern no. 310733 for
Ag2Se0?3Te0?7.
24. M. Pandiaraman and N. Soundararajan: J. Theor. Appl. Phys.,
2012, 6, 7.
25. M. Pandiaraman, N. Soundararajan, C. Vijayan, C. Kumar and
R. Ganesan: J. Ovonic Res., 2010, 6, (6), 285.

Surface Engineering 2016 VOL 0 NO 0 5