Raman spectra and electron microscopic investigations of the sections of modified As₂S₃ glasses
Chalcogenide vitreous semiconductors (ChVS) are used as memory elements, elements of fiber, integral and power optics [1–6]. The change of the synthesis conditions results in the change of structure and, as a consequence, physical parameters of ChVS [1]. It means that it is possible to find solution...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2004
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| Цитувати: | Raman spectra and electron microscopic investigations of the sections of modified As₂S₃ glasses / N. Mateleshko, V. Mitsa, E. Borkach // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2004. — Т. 7, № 3. — С. 243-246. — Бібліогр.: 15 назв. — англ. |
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irk-123456789-1191182017-06-05T03:02:33Z Raman spectra and electron microscopic investigations of the sections of modified As₂S₃ glasses Mateleshko, N. Mitsa, V. Borkach, E. Chalcogenide vitreous semiconductors (ChVS) are used as memory elements, elements of fiber, integral and power optics [1–6]. The change of the synthesis conditions results in the change of structure and, as a consequence, physical parameters of ChVS [1]. It means that it is possible to find solution of the fabrication of glasses with high optical strength by using modification of ChVS structure [2]. The objective of the present work is to investigate the influence of the temperature-temporal conditions of the fabrication on the structure of As₂S₃ glasses by the method of the Raman scattering spectroscopy and electron microscopy and also to choose the conditions of fabrication of As₂S₃ glasses with the continuously bonded matrix of the structure suitable for power optics using this basis. 2004 Article Raman spectra and electron microscopic investigations of the sections of modified As₂S₃ glasses / N. Mateleshko, V. Mitsa, E. Borkach // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2004. — Т. 7, № 3. — С. 243-246. — Бібліогр.: 15 назв. — англ. 1560-8034 PACS: 61.43.Fs, 78.30.-j, 78.30.g http://dspace.nbuv.gov.ua/handle/123456789/119118 en Semiconductor Physics Quantum Electronics & Optoelectronics Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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Chalcogenide vitreous semiconductors (ChVS) are used as memory elements, elements of fiber, integral and power optics [1–6]. The change of the synthesis conditions results in the change of structure and, as a consequence, physical parameters of ChVS [1]. It means that it is possible to find solution of the fabrication of glasses with high optical strength by using modification of ChVS structure [2]. The objective of the present work is to investigate the influence of the temperature-temporal conditions of the fabrication on the structure of As₂S₃ glasses by the method of the Raman scattering spectroscopy and electron microscopy and also to choose the conditions of fabrication of As₂S₃ glasses with the continuously bonded matrix of the structure suitable for power optics using this basis. |
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Mateleshko, N. Mitsa, V. Borkach, E. |
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Mateleshko, N. Mitsa, V. Borkach, E. Raman spectra and electron microscopic investigations of the sections of modified As₂S₃ glasses Semiconductor Physics Quantum Electronics & Optoelectronics |
| author_facet |
Mateleshko, N. Mitsa, V. Borkach, E. |
| author_sort |
Mateleshko, N. |
| title |
Raman spectra and electron microscopic investigations of the sections of modified As₂S₃ glasses |
| title_short |
Raman spectra and electron microscopic investigations of the sections of modified As₂S₃ glasses |
| title_full |
Raman spectra and electron microscopic investigations of the sections of modified As₂S₃ glasses |
| title_fullStr |
Raman spectra and electron microscopic investigations of the sections of modified As₂S₃ glasses |
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Raman spectra and electron microscopic investigations of the sections of modified As₂S₃ glasses |
| title_sort |
raman spectra and electron microscopic investigations of the sections of modified as₂s₃ glasses |
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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2004 |
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http://dspace.nbuv.gov.ua/handle/123456789/119118 |
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Raman spectra and electron microscopic investigations of the sections of modified As₂S₃ glasses / N. Mateleshko, V. Mitsa, E. Borkach // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2004. — Т. 7, № 3. — С. 243-246. — Бібліогр.: 15 назв. — англ. |
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Semiconductor Physics Quantum Electronics & Optoelectronics |
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| first_indexed |
2025-07-08T15:15:13Z |
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2025-07-08T15:15:13Z |
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243© 2004, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
Semiconductor Physics, Quantum Electronics & Optoelectronics. 2004. V. 7, N 3. P. 243-246.
PACS: 61.43.Fs, 78.30.-j, 78.30.g
Raman spectra and electron microscopic investigations
of the sections of modified As2S3 glasses
N. Mateleshko, V. Mitsa, E. Borkach
Uzhgorod National University, 32, Voloshin str., 88000 Uzhgorod, Ukraine
E-mail: mitsa@univ.uzhgorod.ua
Abstract. Chalcogenide vitreous semiconductors (ChVS) are used as memory elements, ele-
ments of fiber, integral and power optics [1�6]. The change of the synthesis conditions results
in the change of structure and, as a consequence, physical parameters of ChVS [1]. It means that
it is possible to find solution of the fabrication of glasses with high optical strength by using
modification of ChVS structure [2]. The objective of the present work is to investigate the
influence of the temperature-temporal conditions of the fabrication on the structure of As2S3
glasses by the method of the Raman scattering spectroscopy and electron microscopy and
also to choose the conditions of fabrication of As2S3 glasses with the continuously bonded
matrix of the structure suitable for power optics using this basis.
Keywords: chalcogenide glasses, arsenicum trisulfide, Raman scattering spectroscopy.
Paper received 03.03.04; accepted for publication 21.10.04.
1. Introduction
The investigation of the non-crystalline semiconductors
is one of the important objectives of the solid state phy-
sics. The problem to modify properties of these materials
up to date still remains actual. The technological modifi-
cation is among the effective methods directed towards
the solution of this problem. The change of the synthesis
temperature and cooling rate results in the changing
structure, which causes changes in materials properties.
2. Experimental technique
During fabrication of g-As2S3, the temperature-temporal
conditions of the annealing were modified. The aim was
to choose fabrication conditions, which enable to avoid
dissociation of the structural units (s.u.) in the melt. As
the technological modification of the g-As2S3 fabrication
we will imply the change of the melt temperature (Òi,
i = 1,2,3), from which the cooling started (T1 = 870 K;
T2 = 1170 K; T3 = 1370 K) and change of the melt cool-
ing rate (V1 = 10�2, V2 = 1,5; V3 = 1.5×102 K/s). Investi-
gations of the Raman spectra was carried out using
DFS-24 spectrophotometer. He-Ne laser (λ = 632.8 nm)
was used to excite Raman scattering.
Electron-microscopic investigations of modified
g-As2S3 were carried out using sections g-As2S3, which
were obtained using UMTP-4 ultramicrotome, the thick-
ness of the samples 50-70 nm was small enough for trans-
mitting the electron beams [7].
3. Results and discussion
Within the frames of the molecular approach (model) [8]
most intensive band in the Raman spectra of g-As2S3 near
340 cm�1 (Fig. 1, 2) in the first approximation can be
interpreted stemming from the frequencies of free mol-
ecule analogs and related to the symmetric vibrations of
ÀsS3 pyramid with C3v symmetry [9].
In the Raman spectra of g-As2S3 in the wide band the
high- and lowfrequency shoulders are observed at 380
and 316 cm�1, respectively (Fig.1). The fixation of the
shoulder near 380 cm�1 in the Raman spectra of g-As2S3
testify on the presence of the interaction between pyra-
mids and creation of the �waterlike� bonds As-S-As [9].
Thus, in Raman spectra of g-As2S3 it is possible to sepa-
rate at least three bands. If the most intensive maximum
can be related to the valence vibrations of AsS3 pyra-
mids, then interpretation of the bands in Raman spectra
is difficult, that points to the limitations of the use of
�molecular� approach for the structural interpretation
of the vibrational spectra of g-As2S3.
Despite the moderate melt cooling rates from 870 K,
in Raman spectra of g-As2S3 (T1V1) (Fig. 1) the band near
244
SQO, 7(3), 2004
N. Mateleshko et al.: Raman spectra and electron microscopic investigations of ...
230 cm�1 appears, which is characteristic for the atoms
vibrations in à-As [9] and low-intensity band near
190 cm�1, characteristic for the vibrations of the atoms in
As4S4 �molecules� [10]. In the 450�480 cm�1 range, weak
bands are pronounced, which are characteristic for S�S
bonds [11]. The presence of the homopolar As-As bands
testify on the partial dissociation of the pyramidal AsS3/2
s.u., which is reflected in their physical characteristics
[2]. Chemical analysis of As�As bonds content in g-As2S3
glasses shows that their general fraction consists 0.5 wt %
[9], and As4S4 content in this case is ~0.015 mol. %, if
rigid cooling conditions are used it is increased up to
0.15 mol.% [12].
According to the cluster topological approach [13],
generalized in [9], the intensive vibrational band in the
low-frequency (LF) Raman spectrum of g-As2S3 (synthe-
sized from 870 K with the 1.5 K/s cooling rate) with the
maximum near 26 cm�1 coincides with the frequency of
the rigid-layer vibrations in the Raman spectrum of
c-As2S3 crystal [2] and indicates presence in the glass
matrix of the fragments, which are characteristic to the
chain-layer ordered phase. The existence of the layer-
like blocs in the structure of g-As2S3 is supported by the
presence of the first sharp diffraction peak (FSDP), ob-
served in diffraction studies of the binary ChVS [4]. The
simplest model of g-As2S3 structure is randomly oriented
spiral chains of ÀsS3 pyramids [4]. In [14], it is shown
that for formation of a layered fragment, it is sufficient
that the chains will be parallel to each other.
Let us consider the position change of the low-fre-
quency boson maximum B in the Raman spectrum of the
technologically modified g-As2S3 (Figs 1, 2). The analy-
sis of the position change of the low-frequency boson
maximum B shows that the low-frequency maximum is
shifted from 26 cm�1 (T1V1) up to 20 cm�1 (T3V3), T1 =
= 870 K; T2 = 1170 K; T3 = 1370 K with the growth of
the cooling rate (Vi) from Ti temperatures. Anomalous
shift is observed at low-temperature synthesis T1V1 in
comparison with its position at T1V2. Here, B is shifted
from 26 cm�1 (T1V1) up to 27 cm�1 (T1V2). The lowering of
the frequency position of the boson maximum with the
increase of cooling rate of the glasses was also observed
in [9], but at temperatures close to the glass transition
temperature of the arsenic trisulfide (Òg = 473 K). It is
essential to note that with the change of the cooling rate
we observed the increase of the ratio of the intensity of
the boson maximum (IB) to the (I342) intensity of the va-
lence vibrations of the As�S bonds in the Raman spectra
near 342 cm�1,
340I
IB
, which is distinctly observable for
the melt temperature Ò3, where this ratio sharply in-
creases from 0.96 (T3V1) up to 1.27 (T3V2), and further at
T3V3 is practically unchanged. The increase of
340I
IB
ra-
tio points to the essential disordering of the structure of
the matrix and agrees with the conclusions, which were
obtained by means of the structural interpretation of the
valence vibrations in the vibrational spectra of the modi-
fied g-As2S3 [2]. According to the data of the electron-
microscopic studies in the matrix of such glass, the
microcrystals with the sizes from 20.0 up to 50.0 nm are
observed, so the shift of the boson maximum towards the
low-frequency region at T3V3 conditions is logically to
connect the destruction of the intactness of the matrix of
the structure, which arises as a result of the emergence of
the crystalline phase.
The results of the direct electron-microscopic investi-
gations of the structure of g-As2S3 (T1V2) show the high
glass uniformity, absence of inclusions and uniform
evaporation under the electron beam.
It is considered that the slow melt cooling with the
soaking at T1 = 870 Ê (minimal temperature when the
synthesis process undergoes within the real time scale)
facilitates fabrication of the glass with the low defects
number [4].
In the image of cleavage of g-As2S3 (T1V1), inclu-
sions are clearly observed (see Fig. 3), which are seen as
dark dots on the uniform background. The theoretical
calculations allow the possibility of the presence of 20
different s.u. in As�S system [9].
At the transition from moderate up to rigid conditions
of the cooling, the content of As�As bonds in g-As2S3
increases from 0.5 to 2.5 wt.% [9]. Thus. it is logically to
Fig. 1. Raman spectra of As2S3 glasses obtained by melt (Tm1 =
= 870 K) cooling at different cooing rates Vj: 1 � V1 = 10�2 K/s;
2 � V2 = 1.5 K/s; 3 � V3 = 1.5⋅102 K/s.
Fig. 2. Raman spectra of glasses, obtained with the constant
cooling rate (V1 = 10�2 K/s) from melts with different tempera-
tures Tmi: 1 � Tm1 = 870 K; 2 � Tm2 = 1170 K; 3 � Tm3 = 1370 K.
Dv, cm�1
0 100 200 300 400 500
0
10
20
30
40
50
60
70
80
90
3
2
1
I
,
r
e
l.
u
n
1
Dv, cm�1
2
0 100 200 300 400
3
I
,
r
e
l.
u
n
N. Mateleshko et al.: Raman spectra and electron microscopic investigations of ...
245SQO, 7(3), 2004
suppose that the dark dots of g-As2S3 (T1V1) observed in
the microscope are related to the associates of arsenic,
the existence of which is supported by the analysis of the
vibrational spectra (Fig. 1, curve 1).
In the conditions of the rigid cooling of the melt T1V3
on the cleavage of the glass the voids are observed, filled
by the pseudogranules of amorphous structure. These
voids can be represented as bubbles of vapor, which are
created in the glass volume during melt cooling. The domi-
nating constituents of the vapor phase of à-As2S3 in the
wide temperature range are spherically symmetrical As4S4
molecules [11]. Absorption edge of the molecular crys-
tals α, β-As4S4 (the basic structural element of them are
As4S4 molecules) is shifted with reference to absorption
edge of g-As2S3 towards high-energy side [9]. Indeed, the
absorption edge of g-As2S3 which were obtained in differ-
ent cooling conditions (T1V3, T2V3, T3V3), is shifted to
the high-energy side as compared with T1V2 conditions.
When cooling the melt from Ò2, Ò3, let us take into
account that the melting temperature Òmelt(As2S3) =
= 583 K and boiling temperature Òboil(As2S3) = 996 K
are taken at the pressure 1 atmosphere [9]. With taking
into account the value of Òboil, the cooling process from
Ò2, Ò3 of the dissociation products of this overheated melt
placed in the evacuated quartz ampoule must be similar
to the process of the films fabrication [9]. If we suppose
preferable influence of the structural factor on the opti-
cal damage threshold, then ²13 of g-As2S3 (T1V3) coin-
cides in its value with ² = 30 MW/cm2 value of the a-
As2S3 film, which was obtained by the common crucible
evaporation of the glass with the consequent vapor con-
densation on the unheated substrate [9]. The vapor phase
of à-As2S3 mainly consists of the complexes of AsnSm
(n, m = 1...4 type), and, what's more, the fraction of the
As4S4 fragments in the vapor is maximal [15]. It is known
that the most stable component of the cluster flux �cools�
on the substrate and in the condensed phase, as a rule, it
is labile. The question arises on the character of the dis-
tribution of the dissociation products of the melt in the
glass volume. Under T2V3 condition (Fig. 4) the glass
has non-uniform wavy structure. At the cleavage, also
observed are the chaotically placed electron-amorphous
regions with widths up to 1000 Å. In the amorphous field
of the diffraction pattern of the sample cooled from T3V3
the reflexes are observed, which testify on the presence of
the crystalline inclusions of sulfur in the sample. The
evaluation of their sizes has shown that it is varied from
200 up to 500 Å. The ascent of the �plateau� in the low-
energy part of the absorption α curve is similar to that
observed in ChVS with the presence of microscopic in-
clusions [4].
The vitreous g-As2S3 practically does not crystallize
[4], the appearance of the microcrystalline inclusions in
the glasses of As-S system is observed at deviations of
composition from As40S60 only on 1 at. % towards the
side of arsenic enrichment [9].
1 2 3
Fig. 3. Electron-microscopic images of the g-As2S3, obtained in different physico-technological conditions [7]: 1 � T1V1; 2 � T1V2; 3 � T1V3.
Fig. 4. Electron-microscopic images of g-As2S3, obtained in different physico-technological conditions [7]: 1 � T2V1; 2 � T2V2; 3 � T2V3.
1 2 3
246
SQO, 7(3), 2004
N. Mateleshko et al.: Raman spectra and electron microscopic investigations of ...
Thus, it is possible to suppose that non-equilibrium of
the glasses fabrication conditions at T1V3, T2V3 results
in local deviations from As40S60 composition, causes ap-
pearance of As4S4 in micropores, which leads to the in-
fringements of the connectivity of the glass matrix struc-
ture. The consequent increase of the temperature up to Ò3
(Fig. 5) increases the melt dissociation degree, and rigid
cooling in the non-equilibrium conditions leads to more
pronounced local deviations in the composition, which
facilitates the microscopic inclusions appearance. The
best conditions of g-As2S3 fabrication are realized at Ò1 =
= 870 K and V2 = 1.5 K/s.
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Fig. 5. Electron-microscopic images of g-As2S3, obtained in different physico-technological conditions [7]: 1 � T3V1; 2 � T3V2; 3 � T3V3.
1 2 3
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