Raman scattering in sulphide glasses
Raman spectra of two ternary glasses of composition Ge₅As₃₇S₅₈ and As₄Ge₃₀S₆₆ have been investigated. An influence of addition of third element on the spectra of binary glasses has been studied by comparison with spectra of two binary glasses of composition Ge₃₃S₆₇ and As₄₀S₆₀. Glass structure an...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
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irk-123456789-1187362017-06-01T03:02:57Z Raman scattering in sulphide glasses Tolmachov, I.D. Stronski, A.V. Pribylova, H. Vlček, M. Raman spectra of two ternary glasses of composition Ge₅As₃₇S₅₈ and As₄Ge₃₀S₆₆ have been investigated. An influence of addition of third element on the spectra of binary glasses has been studied by comparison with spectra of two binary glasses of composition Ge₃₃S₆₇ and As₄₀S₆₀. Glass structure and phase separation effects are discussed. 2010 Article Raman scattering in sulphide glasses / I.D. Tolmachov, A.V. Stronski, H. Pribylova, M. Vlcek // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 4. — С. 432-435. — Бібліогр.: 12 назв. — англ. 1560-8034 PACS 63.50.Lm, 77.84.Bw, 78.30.Ly http://dspace.nbuv.gov.ua/handle/123456789/118736 en Semiconductor Physics Quantum Electronics & Optoelectronics Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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Raman spectra of two ternary glasses of composition Ge₅As₃₇S₅₈ and
As₄Ge₃₀S₆₆ have been investigated. An influence of addition of third element on the
spectra of binary glasses has been studied by comparison with spectra of two binary
glasses of composition Ge₃₃S₆₇ and As₄₀S₆₀. Glass structure and phase separation effects
are discussed. |
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Article |
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Tolmachov, I.D. Stronski, A.V. Pribylova, H. Vlček, M. |
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Tolmachov, I.D. Stronski, A.V. Pribylova, H. Vlček, M. Raman scattering in sulphide glasses Semiconductor Physics Quantum Electronics & Optoelectronics |
| author_facet |
Tolmachov, I.D. Stronski, A.V. Pribylova, H. Vlček, M. |
| author_sort |
Tolmachov, I.D. |
| title |
Raman scattering in sulphide glasses |
| title_short |
Raman scattering in sulphide glasses |
| title_full |
Raman scattering in sulphide glasses |
| title_fullStr |
Raman scattering in sulphide glasses |
| title_full_unstemmed |
Raman scattering in sulphide glasses |
| title_sort |
raman scattering in sulphide glasses |
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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2010 |
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http://dspace.nbuv.gov.ua/handle/123456789/118736 |
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Raman scattering in sulphide glasses / I.D. Tolmachov, A.V. Stronski, H. Pribylova, M. Vlcek // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 4. — С. 432-435. — Бібліогр.: 12 назв. — англ. |
| series |
Semiconductor Physics Quantum Electronics & Optoelectronics |
| work_keys_str_mv |
AT tolmachovid ramanscatteringinsulphideglasses AT stronskiav ramanscatteringinsulphideglasses AT pribylovah ramanscatteringinsulphideglasses AT vlcekm ramanscatteringinsulphideglasses |
| first_indexed |
2025-07-08T14:33:33Z |
| last_indexed |
2025-07-08T14:33:33Z |
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Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 432-435.
PACS 63.50.Lm, 77.84.Bw, 78.30.Ly
Raman scattering in sulphide glasses
I.D. Tolmachov1,*, A.V. Stronski1, H. Pribylova2, M. Vlček2
1V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine,
41, prospect Nauky, 03028 Kyiv, Ukraine
2Faculty of Chemical Technology, University of Pardubice,
Studentská 573, 532 10 Pardubice, Czech Republic, *E-mail: tolmach_igor@mail.ru
Abstract. Raman spectra of two ternary glasses of composition Ge5As37S58 and
As4Ge30S66 have been investigated. An influence of addition of third element on the
spectra of binary glasses has been studied by comparison with spectra of two binary
glasses of composition Ge33S67 and As40S60. Glass structure and phase separation effects
are discussed.
Keywords: Raman scattering, chalcogenide glasses.
Manuscript received 24.09.10; accepted for publication 02.12.10; published online 30.12.10.
1. Introduction
Investigations of non-crystalline solids occupy one of
the leading places in modern solid state physics. High
research interest paid to these materials is caused by a
number of their inherent properties (an opportunity to
tailor continuously the composition and physical
properties, effective production and treatment, stability
in various media, etc.) which provide many
opportunities for their practical applications. Studying of
non-crystalline solid state is also of great importance
from the viewpoint of the fundamental science.
Chalcogenide vitreous semiconductors are very
interesting materials of this class. Beside the mentioned
physical properties inherent to glassy state, they have
also many specific properties such as transparency in the
infrared region of spectrum, a variety of photoinduced
phenomena and high nonlinear optical properties, which
made them very perspective in such practical
applications as telecommunications, sensors, optical data
storage, etc. Investigation of structure of these materials
and it’s relation to the composition and physical
properties is a key for effective application. Raman
scattering is one of the commonly used ways to
investigate the structure of the glassy state. In this paper,
we present the results of Raman spectroscopic studies
concerning two ternary chalcogenide glasses of
composition Ge5As37S58 and As4Ge30S66 and comparison
with binary glasses As40S60 and Ge33S67.
2. Experimental
Glasses of compositions As40S60, Ge5As37S58, Ge33S67
and As4Ge30S66 were synthesized by direct melting of
initial high purity elements in evacuated silica ampoules.
Ge33S67 and As4Ge30S66 glasses were held at 750 °C for
5 h and then melted at 800 – 970 °C for 10 – 12 h.
As40S60 and Ge5As37S58, glasses were melted at 650 –
800 °C for 8 – 24 h. After synthesis, the ampoules with
melts were quenched in cold water. Raman spectra were
investigated using IR Fourier spectrophotometer Bruker
IFS55 Equinox with FRA-106 attachment. Nd-YAG
laser light with the wavelength 1.064 μm was used for
excitation.
3. Results and discussion
Raman spectra of binary glasses As40S60 and Ge33S67
are presented in Figs 1a and 1b, respectively. The
spectrum of As40S60 glass consists of the main band
centered at 344 cm-1 and a broad band in the lower
frequency region (50 – 250 cm-1). There is also a weak
band at 497 cm-1. The spectrum of Ge33S67 glass
contains the main peak at 344 cm-1 with the shoulder at
372 cm-1, which is usually referred to as A1
c
“companion” mode. Also, there is the distinguished
peak at 436 cm-1 and weak band at 488 cm-1. In the
lower frequency region (50 – 250 cm-1), there is a
broad band with features at 85, 117, 154, 208 cm-1.
The Raman spectrum of As4Ge30S66 glass is
presented in Fig. 2a. The higher frequency region (300 –
600 cm-1) contains the broad band with two maxima near
346 and 435 cm-1. This band can be deconvoluted into
four Gaussian bands centered at 346, 375, 403 and
435 cm-1, as shown in Fig. 1. There is also a weak band
at 495 cm-1 in this region.
The lower frequency part of the spectrum (50 –
300 cm-1) also can be deconvoluted into Gaussian bands
centered at 88, 114, 152, 186, 210 and 246 cm-1 (see
Fig. 2).
© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
432
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 432-435.
0 100 200 300 400 500
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
In
te
ns
ity
, a
.u
.
Wavenumber, cm-1
322 359
344
402
384
189
168
236
80
150
118
215
497
a
0 100 200 300 400 500 600
0,00
0,02
0,04
0,06
0,08
0,10
In
te
ns
ity
, a
.u
.
Wavenumber, cm-1
344
372
436
488
208
154
117
85
b
Fig. 1. Raman spectra of binary glasses As40S60 (a) and
Ge33S67 (b).
In Fig. 2b, the Raman spectrum of Ge5As37S58 glass
is presented. There is a broad band centered near
343 cm-1 in the higher frequency region (260 – 500 cm-
1). Deconvolution of this band leads to five Gaussian-
shaped lines (see Fig. 2) with the maxima at 320, 167,
189, 214 and 237 cm-1. There is also a weak band at
496 cm-1.
In the lower frequency region (60 – 260 cm-1) there
is a broad band which has local peculiarities at 150, 167,
189, 214 and 237 cm-1.
The most intensive band in the spectrum of Ge33S67
glass is located at 344 cm-1. In the case of As4Ge30S66
glass, it is shifted towards 346 cm-1. This band has been
previously observed in binary glasses of Ge–S system
either of stoichiometric or non-stoichiometric
composition [1-5]. The peak at 346 cm-1, as usually
accepted, corresponds to the A1 symmetric stretching
vibrations in the main structural units of the glass –
Ge(S1/2)4 tetrahedra, and in the case of ternary
As4Ge30S66 system, it also contains a contribution from
symmetrical vibrations of As(S1/2)3 pyramidal units [6].
Two other bands – A1
c companion mode at 375 cm-1, and
the band near 435 cm-1 have been also observed in
GexS1-x glasses of different compositions, but their origin
still remains controversial.
Authors of the paper [7] associated the band
375 cm-1 with the presence of medium range order
structures in these glasses. A model was assumed,
according to which, glassy Ge(S, Se)2, as opposed to
SiO2, are formed not by a three-dimensional random
network, but have rather layer-like structure consisted of
medium-range order regions. The typical scale of these
structures is about 10 to 20 Å.
100 200 300 400 500 600
0,00
0,05
0,10
0,15
0,20
In
te
ns
ity
, a
.u
.
Wavenumber, cm-1
403
114
246
346
435
375
210
495
152
88
186
a
200 400
0,00
0,05
0,10
0,15
In
te
ns
ity
, a
.u
.
Wavenumber, cm-1
214
189
237
150
342
496
115
81
320
140
391
364
402
167
b
Fig. 2. Raman spectra of ternary glasses Ge30As4S66 (а) and
Ge5As37S58 (b).
Authors of [3] investigated evolution of Raman
spectra with temperature. They observed two stage
crystallization of glassy GeS2. It was found that the A1
c
mode is present in spectra during the rise of temperature
© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
433
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 432-435.
and remains after the transition to 3D-crystalline state (at
~750 ºC), and also it is present at temperatures higher
than 850 ºC as a shoulder (when the transition to the 2D-
crystalline state occurs). After slow cooling down to
room temperature, material retains 2D-crystalline
structure that also has the А1
с mode in its spectrum.
Therefore, by analogy with the 2D-crystalline state, the
А1
с mode in glassy GeS2 was ascribed to symmetrical
vibrations of sulphur bridge atoms in edge-shared
tetrahedra.
Authors of [5] provided comparison of Raman
spectra of glassy GeS2 obtained under different
quenching temperatures and cooling rates. A conclusion
has been drawn that А1
с mode together with 433 cm-1
band can be ascribed to vibrations in edge-shared
tetrahedra. In paper [3], 433 cm-1 band was ascribed to
the stretching vibrations of S–S bonds that were either
present separately in glass matrix or bond together with
tetrahedral elements. This opinion is supported by the
authors of [8]. They stated that the 434 cm-1 band that
was observed by them in germanium sulphide films,
corresponds to the vibrations of S–S bonds
interconnecting Ge(S1/2)4 tetrahedra. Authors of [3]
claims that the presence of such bonds in stoichiometric
glass indicates the presence of homopolar Ge–Ge bonds.
The band at 260 cm-1, the intensity of which was
growing up with the increase of Ge concentration was
ascribed to the presence of these bonds. The authors,
however, didn’t explain why the intensity of 433 cm-1
band (along with A1
c band) decreases with increasing of
the sulphur content.
Authors of [5] don’t support the assumption about
the presence of homopolar bonds in glassy GeS2. The
bands at 200, 237 and 256 cm-1 which were observed in
samples of glassy GeS2 obtained at different synthesis
conditions, were ascribed to the vibrations in three-fold
coordinated structures consisted of Ge and S atoms, for
instance, to the vibrations in crystalline nanophase c-
GeS. As mentioned in [5], c-GeS nanoparticles with
sizes about 7–12 Å may exist in the glass structure, or,
depending on the synthesis conditions, may form larger
c-GeS particles within the matrix of glassy GeS2.
In the paper [4], the band near 440 cm-1 that was
observed in glasses of nearly stoichiometric
compositions GexS1-x, was ascribed to the F2 mode of
tetrahedra Ge(S1/2)4. In paper [9], the structure of
As4Ge30S66 glass was investigated by means of X-ray
diffraction. By comparison of experimental results with
those of numerical simulation, a conclusion was drawn
that the structure of glass is given by inhomogeneous
network with regions expressing a quasi-layer type
stacking interlinked with regions of random network
where the amount of homopolar bonds is kept minimum.
The 495 cm-1 band observed in the spectrum of
As4Ge30S66 is characteristic for the presence of S–S
bonds. Presence of these bonds implies the existence of
edge-shared Ge(S1/2)4 tetrahedra in the structural
backbone of the glass, which must lead to the
appearance of redundant S atoms.
The 246 cm-1 band was observed earlier in the
GexA40-xS60 glass spectra [10]. When x = 0, a weak band
near 231 cm-1 was observed, which was growing and
shifting towards the higher frequencies with increasing x
until 245 cm-1 when x = 36. This feature was related by
authors with increasing amount of homopolar Ge–Ge
bonds compared to As–As. As claimed in [10],
homopolar Ge–Ge bonds are located in Ge–S4-nGen
tetrahedra and/or in Ge2S6/2 ethane-like clusters.
Similar peculiarity was observed in [11] during the
investigation of series of compounds (Ge2S3)x(As2S3)1-x
where 0<x<1. When x>0.5, the broad band centered at
250 cm-1 appeared and began to increase. As stated in
[11], this band corresponds to the vibrations in ethane-like
Ge2S6 nanophase that segregates from GeS2. According to
the results of calculations provided in [5], ethane-like
nanophase possesses the intensive peak at 250 cm-1 and
also several bands near 400 cm-1. In the decomposition of
the main peak in the As4Ge30S66 spectrum (see Fig. 2),
there is a broad band centered at 403 cm-1. Therefore,
bands at 246 and 403 cm-1 can be ascribed to the
vibrations in ethane-like nanophase Ge2S6.
In Fig. 3, the difference between spectra of
As4Ge30S66 and Ge33S67 glasses normalized to the
intensity of the main peak is shown. The difference
spectra clearly reveal the changes made by addition of
arsenic to the Ge33S67 glass. The abrupt transition from
minimum to maximum near 346 cm-1 is due to the red
shift of the main band. The difference spectrum has
maximum near 250 cm-1 corresponding to the
appearance of this band in the spectrum of As4Ge30S66
glass, and minima at 374 and 438 cm-1 due to the
softening of corresponding bonds. The former
peculiarity can be ascribed to the precipitation of ethane-
like nanophase, while the latter to the decrease of the
Ge(S1/2)4 tetrahedra concentration.
The Raman spectrum of Ge5As37S58 glass (see
Fig. 2b) is almost similar to the spectrum of binary
As40S60 glass. The main broad band in the spectra of
As40S60 and Ge5As37S58 glasses at 342 cm-1 corresponds to
the band characteristic for AsxS100-x glasses of different
compositions. The bands at 321, 343 and 361 cm-1 that are
present in the decomposition of main band are typical to
the As42S58 glass enriched by arsenic as compared to the
stoichiometric As40S60 glass. The 342 cm-1 band, as
generally accepted [6, 10, 11], corresponds to the
symmetric ν1 vibrations of pyramidal As(S1/2)3 units. The
band at 361 cm-1 corresponds to the intensive mode of
crystalline As4S4 [6]. The increase in this band intensity is
characteristic of AsxS1-x compositions when x>40, that is
arsenic enriched as compared to the stoichiometric glass
[6, 12]. Numerical calculations provided in [12] allow to
ascribe the band at 361 cm-1 to the presence of As4S4
clusters in material. In the lower frequency region of the
Ge5As37S58 spectrum, we can also see the bands observed
earlier by the authors of [6] in the As42S58 glass, in
particular: the bands at 150 (corresponds to the 147 cm-1
band), 167, 189, 214 and 237 cm-1 (corresponds to the
© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
434
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 432-435.
234 cm-1 band). Bands at 150, 167, 189 and 214 cm-1 can
also be ascribed to the vibrations in As4S4 clusters [6, 11].
The band near 496 сm-1 that is characteristic of S-S
bonds appears in spectra of glass of either stoichiometric
As40S60 or non-stoichiometric Ge5As37S58 glass with Ge
additive. Thus, presence in the spectrum of As40S60 glass
bands at 361, 150, 167, 189 and 214 cm-1 that are
characteristic of As4S4 clusters, and the band at 496 cm-1,
suggests the non-homogeneity and nanophase separation
in stoichiometric glass.
In Fig. 4, the difference between spectra of
Ge5As37S58 and As40S60 glasses normalized to the
intensity of the main peak is shown. As can be seen from
Fig. 4, introduction of Ge additives leads to appearance
of the minima at 310 and 330 cm-1, which corresponds to
the anti-symmetrical and symmetrical vibrations of AsS3
pyramids [6]. The positive peaks near 241, 383 and
408 cm-1 can be ascribed to the vibrations in ethane-like
clusters that can be formed in glass with addition of Ge.
0 100 200 300 400 500
In
te
ns
ity
d
iff
er
en
ce
, a
.u
.
GeS2
Wavenumber, cm-1
In
te
ns
ity
, a
.u
.
As4Ge30S66 -0,04
-0,03
-0,02
-0,01
0,00
0,01
0,02
112
141
250 374
438
346
Fig. 3. Difference between spectra of As4Ge30S66 and Ge33S67
glasses normalized to the intensity of the main peak.
100 200 300 400 500
In
te
ns
ity
d
iff
er
en
ce
, a
.u
.
241
331
310
383
408
Wavenumber, cm-1
In
te
ns
ity
, a
.u
.
As40S60
Ge5As37S58
-0,006
-0,004
-0,002
0,000
0,002
0,004
0,006
Fig. 4. Difference between spectra of Ge5As37S58 and As40S60
glasses normalized to the intensity of the main peak.
4. Conclusions
Raman spectra of two ternary glasses with compositions
Ge5As37S58 and As4Ge30S66 have been investigated. An
influence of third element addition on the spectra of
binary glasses has been studied by comparison with two
binary glasses of composition Ge33S67 and As40S60. The
observed peaks in Raman spectra are characteristic
either to the main elements forming structural backbone
of the glasses (tetrahedral Ge(S1/2)4 units and pyramidal
As(S1/2)3 units) or various inclusions (molecular As4S4
clusters and ethane-like nanophase Ge2S6/2).
Inhomogeneity and nanophase separation can be
observed in glasses of either non-stoichiometric or
stoichiometric composition.
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© 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
436
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