Annealing-induced formation of Sn₂P₂S₆ crystallites in As₂S₃-based glass matrix
Sn–As–P–S glasses were obtained using co-melting of pre-synthesized As₂S₃ and Sn₂P₂S₆. Their structure and composition were confirmed by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and micro-Raman scattering. Crystallization of Sn₂P₂S₆ crystallites from the...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2015
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| Цитувати: | Annealing-induced formation of Sn₂P₂S₆ crystallites in As₂S₃-based glass matrix / Yu.M. Azhniuk, A.V. Gomonnai, O.O. Gomonnai, S.M. Hasynets, F. Kováč, V.V. Lopushansky, I. Petryshynets, V.M. Rubish, D.R.T. Zahn // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2015. — Т. 18, № 3. — С. 248-254. — Бібліогр.: 41 назв. — англ. |
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irk-123456789-1212062017-06-14T03:07:24Z Annealing-induced formation of Sn₂P₂S₆ crystallites in As₂S₃-based glass matrix Azhniuk, Yu.M. Gomonnai, A.V. Gomonnai, O.O. Hasynets, S.M. Kováč, F. Lopushansky, V.V. Petryshynets, I. Rubish, V.M. Zahn, D.R.T. Sn–As–P–S glasses were obtained using co-melting of pre-synthesized As₂S₃ and Sn₂P₂S₆. Their structure and composition were confirmed by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and micro-Raman scattering. Crystallization of Sn₂P₂S₆ crystallites from the glass matrix is observed at annealing under relatively low temperatures (410…580 K). 2015 Article Annealing-induced formation of Sn₂P₂S₆ crystallites in As₂S₃-based glass matrix / Yu.M. Azhniuk, A.V. Gomonnai, O.O. Gomonnai, S.M. Hasynets, F. Kováč, V.V. Lopushansky, I. Petryshynets, V.M. Rubish, D.R.T. Zahn // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2015. — Т. 18, № 3. — С. 248-254. — Бібліогр.: 41 назв. — англ. 1560-8034 DOI: 10.15407/spqeo18.03.248 PACS 64.70.pn, 78.67.-n, 82.80.Gk http://dspace.nbuv.gov.ua/handle/123456789/121206 en Semiconductor Physics Quantum Electronics & Optoelectronics Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine |
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English |
| description |
Sn–As–P–S glasses were obtained using co-melting of pre-synthesized As₂S₃ and Sn₂P₂S₆. Their structure and composition were confirmed by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and micro-Raman scattering. Crystallization of Sn₂P₂S₆ crystallites from the glass matrix is observed at annealing under relatively low temperatures (410…580 K). |
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Article |
| author |
Azhniuk, Yu.M. Gomonnai, A.V. Gomonnai, O.O. Hasynets, S.M. Kováč, F. Lopushansky, V.V. Petryshynets, I. Rubish, V.M. Zahn, D.R.T. |
| spellingShingle |
Azhniuk, Yu.M. Gomonnai, A.V. Gomonnai, O.O. Hasynets, S.M. Kováč, F. Lopushansky, V.V. Petryshynets, I. Rubish, V.M. Zahn, D.R.T. Annealing-induced formation of Sn₂P₂S₆ crystallites in As₂S₃-based glass matrix Semiconductor Physics Quantum Electronics & Optoelectronics |
| author_facet |
Azhniuk, Yu.M. Gomonnai, A.V. Gomonnai, O.O. Hasynets, S.M. Kováč, F. Lopushansky, V.V. Petryshynets, I. Rubish, V.M. Zahn, D.R.T. |
| author_sort |
Azhniuk, Yu.M. |
| title |
Annealing-induced formation of Sn₂P₂S₆ crystallites in As₂S₃-based glass matrix |
| title_short |
Annealing-induced formation of Sn₂P₂S₆ crystallites in As₂S₃-based glass matrix |
| title_full |
Annealing-induced formation of Sn₂P₂S₆ crystallites in As₂S₃-based glass matrix |
| title_fullStr |
Annealing-induced formation of Sn₂P₂S₆ crystallites in As₂S₃-based glass matrix |
| title_full_unstemmed |
Annealing-induced formation of Sn₂P₂S₆ crystallites in As₂S₃-based glass matrix |
| title_sort |
annealing-induced formation of sn₂p₂s₆ crystallites in as₂s₃-based glass matrix |
| publisher |
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| publishDate |
2015 |
| url |
http://dspace.nbuv.gov.ua/handle/123456789/121206 |
| citation_txt |
Annealing-induced formation of Sn₂P₂S₆ crystallites in As₂S₃-based glass matrix / Yu.M. Azhniuk, A.V. Gomonnai, O.O. Gomonnai, S.M. Hasynets, F. Kováč, V.V. Lopushansky, I. Petryshynets, V.M. Rubish, D.R.T. Zahn // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2015. — Т. 18, № 3. — С. 248-254. — Бібліогр.: 41 назв. — англ. |
| series |
Semiconductor Physics Quantum Electronics & Optoelectronics |
| work_keys_str_mv |
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2025-07-08T19:23:52Z |
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2025-07-08T19:23:52Z |
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| fulltext |
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2015. V. 18, N 3. P. 248-254.
doi: 10.15407/spqeo18.03.248
© 2015, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
248
PACS 64.70.pn, 78.67.-n, 82.80.Gk
Annealing-induced formation of Sn2P2S6 crystallites
in As2S3-based glass matrix
Yu.M. Azhniuk1, A.V. Gomonnai1, O.O. Gomonnai2, S.M. Hasynets3, F. Kováč4, V.V. Lopushansky1,
I. Petryshynets4, V.M. Rubish3, D.R.T. Zahn5
1Institute of Electron Physics, National Academy of Sciences of Ukraine,
21, Universytetska str., 88017 Uzhhorod, Ukraine
2Uzhhorod National University,
46, Pidhirna str., 88000 Uzhhorod, Ukraine
3Uzhhorod Scientific and Technology Center, Institute for Information Recording,
National Academy of Sciences of Ukraine,
4, Zamkovi Skhody, 88000 Uzhhorod, Ukraine
4Institute of Materials Science, Slovak Academy of Sciences,
Watsonova 47, Košice 04001, Slovakia
5Chemnitz University of Technology, D-09107 Chemnitz, Germany
Phone +38(0312)-643822; fax +38(0312)-643650; e-mail: yu.azhniuk@gmail.com
Abstract. Sn–As–P–S glasses were obtained using co-melting of pre-synthesized As2S3
and Sn2P2S6. Their structure and composition were confirmed by X-ray diffraction,
scanning electron microscopy, energy dispersive X-ray spectroscopy, and micro-Raman
scattering. Crystallization of Sn2P2S6 crystallites from the glass matrix is observed at
annealing under relatively low temperatures (410…580 K).
Keywords: glass, nanostructures, electron microscopy, Raman spectroscopy.
Manuscript received 02.03.15; revised version received 14.05.15; accepted for
publication 03.09.15; published online 30.09.15.
1. Introduction
Sn2P2S6 (ditin hexathiodiphosphate) is a well-known
ferroelectric material that has become an object of
extensive theoretical and experimental interest in view
of phase transitions and polycritical phenomena
observed under variation of temperature and pressure as
well as possible applications, in particular for piezo- and
pyroelectric gauges and as photorefractive materials [1–
4 and references therein]. At ambient pressure, the
Sn2P2S6 crystal undergoes a second-order structural
transition from the ferroelectric phase (Pn) to the
paraelectric (P21/n) one at 337 K, which was thoroughly
investigated by X-ray diffraction [5], dielectric studies
[6], Raman scattering [7-9], inelastic neutron scattering
[10], ultrasonic measurements [11], optical spectroscopy
[12], birefringence measurements [13], Mössbauer
spectroscopy [14, 15], X-ray photoelectron spectroscopy
[16, 17], soft X-ray fluorescence spectroscopy [16], and
thermal expansion studies [18]. In most cases, these
studies were carried out for good quality bulk single
crystals.
Much less studied are micro- and nanocrystalline
Sn2P2S6-based materials. In Sn2P2S6 ceramics with grain
sizes below 1 μm a decrease of the phase transition
temperature by 12 K with respect to the bulk sample was
observed in dielectric measurements [19]. Nano-
crystalline Sn2P2S6 powders with average crystallite
sizes down to 20 nm were obtained earlier using soft
chemistry (exchange reaction in an aqueous medium)
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2015. V. 18, N 3. P. 248-254.
doi: 10.15407/spqeo18.03.248
© 2015, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
249
[20, 21], ball milling from single crystals [22], and ball
milling from elemental components with subsequent
microwave treatment [23]. Fabrication and investigation
of nanoscale ferroelectric materials are important in
view of both fundamental and practical aspects. The
experience of obtaining nanocrystals in amorphous
matrices, especially well known for II-VI chalcogenides
(see e.g. [24, 25] and references therein), inspired to use
such an approach for glass-embedded nanoscale
ferroelectric chalcogenide-based materials in order to
study size-related effects and possible applications of
such systems. In our recent studies, we reported on laser
beam annealing-induced formation of SbSI ferroelectric
nanocrystals in As2S3-based glass matrix [26, 27].
Here, we present scanning electron microscopy
(SEM), energy-dispersive X-ray fluorescence spectro-
scopy (EDX), and Raman scattering studies of Sn–As–
P–S system revealing evidence for the formation of
Sn2P2S6 nanocrystals in the glass matrix upon annealing
at relatively low temperatures (below 580 K).
2. Experimental
Sn–As–P–S glasses were prepared by vacuum
(~0.01 Pa) co-melting of a mixture of As2S3 and Sn2P2S6
components both synthesized from high-purity elemental
substances. Polycrystalline Sn2P2S6 was obtained by
cooling a homogenized (for 72 h) melt from 900 K to
room temperature. As2S3 glass was obtained by cooling a
homogenized (for 24 h) melt from 780 K in air. As2S3
and Sn2P2S6 were co-melted and homogenized at 850–
870 K for 24 h with occasional stirring and subsequently
hardened in air. Variation of the component ratio
enabled a series of (1–x)As2S3⋅xSn2P2S6 materials with x
ranging from 0.1 to 0.43 to be obtained.
Scanning electron microscopy studies combined
with energy dispersive X-ray spectroscopy were
performed using a SEM JEOL 7000F setup. Micro-
Raman measurements were carried out using a Dilor
XY800 triple monochromator with a CCD camera and a
Kr+ laser (λexc = 647.1 nm). Macro-Raman measure-
ments were performed using a LOMO DFS-24 double
monochromator with a FEU-136 phototube and a He-Ne
laser (λexc = 632.8 nm). The instrumental resolution was
better than 2 cm−1. All the measurements were carried
out at room temperature.
3. Results and discussion
Fig. 1 shows SEM scans of the 0.8As2S3⋅0.2Sn2P2S6
sample surface before and after annealing at 442 K. As
one can see, the patterns for the annealed samples
exhibit higher roughness probably related to some
annealing-induced transformation in the material, which
can involve phase separation and/or chemical reactions
on the surface. The typical size of the inclusions shown
in Fig. 1 is below 1 μm.
Fig. 1. SEM patterns of 0.8As2S3⋅0.2Sn2P2S6 glass before and
after annealing at 442 K for 1 h.
The EDX measurements performed together with
SEM (Fig. 2) enabled us to estimate the chemical
composition of the samples. It should be mentioned that
the EDX data in Fig. 2 differ somewhat from the
intended chemical composition (for this sample the
chemical formula corresponds to a relative atomic
composition of 6.66% Sn, 6.66% P, 26.66% As, and
60.02% S). The EDX data noticeably underestimate the
phosphorus content and overestimate that of tin:
according to the initial glass composition their values
should be equal while the EDX measurements reveal a
significant difference. While the sulphur content
determined from EDX in the initial glass is close to that
in the initial mixture, it somewhat decreases after
annealing. A similar trend is observed for other samples
(see, for instance, Fig. 3), and this loss of sulphur can be
explained by its volatility due to the high vapour pressure.
Raman spectra of as-synthesized
(1–x)As2S3⋅xSn2P2S6 glasses are shown in Fig. 4. The ex-
tensively studied Raman spectrum of glassy As2S3 [28-37]
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2015. V. 18, N 3. P. 248-254.
doi: 10.15407/spqeo18.03.248
© 2015, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
250
Fig. 2. EDX spectra of 0.8As2S3·0.2Sn2P2S6 glass before and
after annealing at 442 K for 1 h and the estimated element
content in the samples.
is known to be dominated by a broad band in the range
of 300−400 cm−1, which is related to symmetric
stretching vibrational modes of AsS3/2 pyramids (AsS3
pyramids are linked together by As–S–As bonds) [31,
33]. A weak band at 490 cm−1 is attributed to S–S
stretching vibrations in S8 rings indicating the presence
of excessive sulphur [33]. Low-intensity bands centered
near 185 and 230 cm−1 are ascribed to bending modes of
AsS3/2 pyramids as well as S8 and As4S4 structural
groups that are known to be present in As2S3 glass [33–
35 and references therein].
With a gradual increase of Sn2P2S6 content, the
Raman spectra of (1–x)As2S3⋅xSn2P2S6 glasses are
characterized not only by broad features typical for
amorphous materials, but also by somewhat narrower
bands that can be related to the vibrations of new
structural groups. At x = 0.1, a shoulder at 408 cm−1
appears, it already at x = 0.2 becomes a rather narrow
peak and with further increase in x develops into the
dominant one in the Raman spectrum (Fig. 4). This band
is most likely related with formation of new structural
groups in the Sn–As–P–S glass structure. Note that for
As–P–S glasses similar behaviour was observed: with
increasing phosphorus content, a rather narrow band
emerged at 418 cm−1, rapidly growing in its intensity
[38]. Such a sharp Raman band observed for glassy
material is, according to Ref. [38 and references therein],
characteristic of an intermediate range order in glasses,
usually of a breathing vibration of ring structures. It was
assumed that in As–P–S glasses eight-membered As2P2S4
rings are formed by sulphur bridges joining AsS3/2
pyramids and S=PS3/2 tetrahedra in the glass structure.
The breathing mode of these rings corresponds to the
band at 418 cm−1 [38]. In our case, the rather close
frequency and similar dependence on composition of the
band at 408 cm−1 suggest the same explanation. The
slight difference in frequency can evidently be explained
by the different long-range environment somewhat
distorting the rings under consideration. It should also be
mentioned that in our earlier study of Sn2P2S6
nanocrystals obtained by ball milling we observed the
weak band centred at 406 cm−1, assumed to stem from
partial S→O substitution in PS3 pyramids due to
oxidation at the nanocrystal surface [22]. The band of
similar frequency at 411 cm−1 was observed in the
Raman spectra of Sn2P2S6 crystals recovered after high-
pressure treatment, where it was possibly related to
pressure-induced defects [39]. Still, in the present case,
based on the above speculations, we consider the
breathing mode of As2P2S4 rings in the glass structure to
be the most appropriate explanation of the Raman peak
in question.
Fig. 3. EDX spectra of 0.8As2S3·0.2Sn2P2S6 glass before and
after annealing at 410 K and the estimated element content in
the samples.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2015. V. 18, N 3. P. 248-254.
doi: 10.15407/spqeo18.03.248
© 2015, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
251
Fig. 4. Raman spectra of unannealed (1–x)As2S3·xSn2P2S6
glasses.
Simultaneously, the increase of x results in more
pronounced features near 185 and 225 cm−1 indicating
the increasing concentration of S8 and As4S4 structural
groups in the glass. Besides, new features near 140, 247,
and 272 cm−1 appear as evidence for formation of new
bonds in the glass. In As–P–S glasses, the increasing
phosphorus content also resulted in new Raman bands in
the spectra, namely peaks near 150, 230, and 268 cm−1.
These were attributed to the vibrational modes of S8,
S=PS3/2 (as well as P4S7), and P4S10 groups, respectively
[38]. With increasing Sn2P2S6 content, some structure
gradually emerges in the region of the main broad As2S3-
related band. Similar transformations were observed for
As–P–S glasses, where a clear splitting of the band was
recorded for x ≥ 0.4 [38]. There the band emerging at
368 cm−1 was ascribed to vibrations of S=PS3/2
tetrahedra. In our case, the maximum emerging near
374 cm−1 (for x ≈ 0.4) might be also related to P–P bond
vibration, the frequency of which in Sn2P2S6 is near
380 cm−1 at room temperature [7, 8]. Slightly above
550 cm−1, a rather broad band is observed, which can be
related to vibrations of P2S6 structural groups present in
the basically amorphous network, since it is known that
the Raman spectrum of Sn2P2S6 contains five bands
assigned to internal vibrations of (P2S6)4– anions [3]. The
splitting related to a crystal environment as well as two-
fold Davydov splitting of these bands reported in [3]
cannot be resolved in the unpolarized spectra of glass-
based composites shown in Fig. 4. In general, the overall
appearance of the Raman spectra of the as-synthesized
(1–x)As2S3⋅xSn2P2S6 samples is consistent with their
amorphous structure and the presence of some
pronounced structural groups.
Note that the Raman spectrum of the
(1–x)As2S3⋅xSn2P2S6 glasses does not change with the
measurement time indicating the glass stability, contrary
to the case of As–Sb–S–I and Tl–In–As–Se glasses,
where we recently observed rapid laser beam-induced
crystallization of SbSI [26, 27] and TlInSe2 [40]
crystallites, respectively.
The changes in the Raman spectra after annealing
(Fig. 5) noticeably depend on the glass composition. For
the glasses with lower Sn2P2S6 content, only slight
changes are observed (sharpening of some features and a
slight increase of their intensity). Meanwhile, the
samples with higher Sn2P2S6 content exhibit rather
dramatic changes. An intense narrow band emerges at
380 cm−1, its position practically coinciding with the
most intense Raman band of a Sn2P2S6 crystal. There it
corresponds to the stretching vibration of the P–P bond
connecting two PS3 pyramids in the Sn2P2S6 structure
[7]. Besides, the maxima at 142, 183, and 244 cm−1
become more intense and sharper, as well as new
features appear at 65, 84, 110, 244, and 295 cm−1. Note
that the frequency positions of all these bands correlate
with the known Sn2P2S6 phonon spectrum [9] as well as
with our earlier measurements for Sn2P2S6 micro- and
nanopowders and ceramics where features near 85, 140,
185, 245, 260, and 290 cm−1 were observed [22]. The
observed features clearly confirm Sn2P2S6 crystallite
formation in the glass matrix under annealing.
Three distinct peaks at 340, 349, and 359 cm–1
appear on the background of the intense broad As2S3
glass-related maximum. Three bands with similar
frequencies in this spectral range are characteristic for
As4S4 structural groups [32]. Moreover, As4S4 structural
groups can contribute to the weaker maxima observed
near 140, 185, and 220 cm−1, since features with similar
frequencies are present in the realgar (As4S4) phonon
spectrum [32]. Note that a similar effect of distinct
relatively narrow As4S4-related peaks emerging on the
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2015. V. 18, N 3. P. 248-254.
doi: 10.15407/spqeo18.03.248
© 2015, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
252
background of the broad maximum near 350 cm−1 was
observed with increasing As/S ratio from slightly
substoichiometric (As-deficient) to slightly super-
stoichiometric (S-deficient) arsenic sulphide glasses
[41]. The authors conclude that even the stoichiometric
glass can be separated into small As-rich (As4S4) and
large S-rich clusters [41]. In our case, this can be
evidence not only for the annealing-induced crystal-
lization of Sn2P2S6 from the Sn–As–P–S glass, but also
the increasing clustering (phase separation) in the As2S3-
based glass itself. Moreover, in view of the above quoted
data of Ref. [39], the observed narrow bands emerging
on the background of the broad maximum at 350 cm−1
correlate well with the decrease of sulphur content in the
material after annealing as determined from the EDX
data (Figs. 2 and 3).
It is also interesting that the relatively narrow band
at 408 cm−1 ascribed to the breathing vibrations of
distorted As2P2S4 rings changes its frequency to the
typical value of 418 cm−1. This could mean that the
annealing (and, possibly, the phase separation) results in
a more stable As–P–S glass-like environment where the
breathing vibrations of the As2P2S4 rings occur with their
usual frequency. Anyway, this is clear evidence for the
fact that not all tin and phosphorus atoms participate in
the Sn2P2S6 crystallization and a considerable part of
them is still kept within the Sn–As–P–S glass network.
4. Conclusions
Sn–As–P–S glasses were obtained by co-melting of
As2S3 and Sn2P2S6 in a broad compositional interval,
their glass structure being clearly confirmed by micro-
Raman spectra. SEM and EDX data show the evidence
for phase transformations in the Sn–As–P–S samples
annealed above 500 K, accompanied by a decrease of
sulphur content with respect to the initial glass.
Annealing-induced formation of Sn2P2S6 crystallites is
confirmed by Raman scattering data where sharp
features, characteristic for Sn2P2S6, are observed for the
annealed samples with Sn2P2S6 concentration x > 0.4.
Sample heating induced by laser beam irradiation does
not result in Sn2P2S6 crystallization in the glass.
Acknowledgements
Yu.M. Azhniuk is grateful to Deutscher Akademischer
Austauschdienst (DAAD) for the support of his research
at Chemnitz University of Technology.
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© 2015, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
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