Obtaining and optical properties of the glasses of the GeS₂–HgS system
The glassy alloys of the GeS₂–HgS system in the range of 0–50 mol. % HgS were obtained by the melt quenching technique. Their Raman spectra were investigated. The dependence of the particularities of the light scattering bands on the chemical composition was analyzed.
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2007
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irk-123456789-1181252017-05-29T03:04:52Z Obtaining and optical properties of the glasses of the GeS₂–HgS system Nechyporuk, B.D. Olekseyuk, I.D. Yukhymchuk, V.O. Filonenko, V.V. Mazurets, I.I. Parasyuk, O.V. The glassy alloys of the GeS₂–HgS system in the range of 0–50 mol. % HgS were obtained by the melt quenching technique. Their Raman spectra were investigated. The dependence of the particularities of the light scattering bands on the chemical composition was analyzed. 2007 Article Obtaining and optical properties of the glasses of the GeS₂–HgS system / B.D. Nechyporuk, I.D. Olekseyuk, V.O. Yukhymchuk, V.V. Filonenko, I.I. Mazurets, O.V. Parasyuk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2007. — Т. 10, № 3. — С. 65-69. — Бібліогр.: 11 назв. — англ. 1560-8034 PACS 33.20.Fb, 71.23.Cq http://dspace.nbuv.gov.ua/handle/123456789/118125 en Semiconductor Physics Quantum Electronics & Optoelectronics Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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The glassy alloys of the GeS₂–HgS system in the range of 0–50 mol. % HgS
were obtained by the melt quenching technique. Their Raman spectra were investigated.
The dependence of the particularities of the light scattering bands on the chemical
composition was analyzed. |
| format |
Article |
| author |
Nechyporuk, B.D. Olekseyuk, I.D. Yukhymchuk, V.O. Filonenko, V.V. Mazurets, I.I. Parasyuk, O.V. |
| spellingShingle |
Nechyporuk, B.D. Olekseyuk, I.D. Yukhymchuk, V.O. Filonenko, V.V. Mazurets, I.I. Parasyuk, O.V. Obtaining and optical properties of the glasses of the GeS₂–HgS system Semiconductor Physics Quantum Electronics & Optoelectronics |
| author_facet |
Nechyporuk, B.D. Olekseyuk, I.D. Yukhymchuk, V.O. Filonenko, V.V. Mazurets, I.I. Parasyuk, O.V. |
| author_sort |
Nechyporuk, B.D. |
| title |
Obtaining and optical properties of the glasses of the GeS₂–HgS system |
| title_short |
Obtaining and optical properties of the glasses of the GeS₂–HgS system |
| title_full |
Obtaining and optical properties of the glasses of the GeS₂–HgS system |
| title_fullStr |
Obtaining and optical properties of the glasses of the GeS₂–HgS system |
| title_full_unstemmed |
Obtaining and optical properties of the glasses of the GeS₂–HgS system |
| title_sort |
obtaining and optical properties of the glasses of the ges₂–hgs system |
| publisher |
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| publishDate |
2007 |
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http://dspace.nbuv.gov.ua/handle/123456789/118125 |
| citation_txt |
Obtaining and optical properties of the glasses of the GeS₂–HgS system / B.D. Nechyporuk, I.D. Olekseyuk, V.O. Yukhymchuk, V.V. Filonenko, I.I. Mazurets, O.V. Parasyuk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2007. — Т. 10, № 3. — С. 65-69. — Бібліогр.: 11 назв. — англ. |
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Semiconductor Physics Quantum Electronics & Optoelectronics |
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Semiconductor Physics, Quantum Electronics & Optoelectronics, 2007. V. 10, N 3. P. 65-69.
© 2007, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
65
PACS 33.20.Fb, 71.23.Cq
Obtaining and optical properties
of the glasses of the GeS2–HgS system
B.D. Nechyporuk1, I.D. Olekseyuk2, V.O. Yukhymchuk3, V.V. Filonenko1,
I.I. Mazurets2, O.V. Parasyuk2
1Rivne State University for the Humanities, Department of Physics and Technology,
31 Ostafov str., 33300 Rivne, Ukraine
2Department of General and Inorganic Chemistry, Volyn State University, 13, Voli Ave., 43025 Lutsk, Ukraine
3V. Lashkaryov Institute for Semiconductor Physics, NAS of Ukraine, 45, prospect Nauky, 03028 Kyiv, Ukraine
Abstract. The glassy alloys of the GeS2–HgS system in the range of 0–50 mol. % HgS
were obtained by the melt quenching technique. Their Raman spectra were investigated.
The dependence of the particularities of the light scattering bands on the chemical
composition was analyzed.
Keywords: chalcogenide glasses, Raman spectra, structure of glasses.
Manuscript received 07.02.07; accepted for publication 27.09.07; published online 31.10.07.
1. Introduction
Chalcogenide glassy semiconductors (CGS), with their
unique properties, belong to an important class of
materials that are perspective for optical devices due to
high transparency in the visible and near- and mid-IR
spectral regions. In particular, CGSs are heavily used for
the production of optical elements for IR devices, high-
resolution, silver-free photographic media, xerography
materials, photosensitive layers for vidicon tubes. CGSs
are characterized by inexpensive material costs which is
a decisive factor in the mass production [1-3].
The subject of this investigation is a systematic
study of the dependence of the physical and the
structural properties of the GeS2–HgS glasses on the
chemical composition, namely the investigation of its
effect on the Raman spectra of the glasses.
2. Experimental
The glasses were synthesized from very high-purity
germanium (99.9999 wt. %), sulfur (99.999 wt. %) and
previously synthesized mercury sulfide (99.999 wt. %).
The proportionally weighed substances (total mass 4 g)
were placed into a specially designed container made of
thin-wall (0.7 mm) quartz, from which the air was
evacuated to the remaining pressure of 10−2 Pa. To
decrease the loss of material to the melt sputtering and to
the condensation of the gaseous phase on the container
walls during quenching, top part of the container was
isolated by the asbestos cord. The glasses were synthe-
sized in two stages. At the first stage the ampoules with
the charge were heated in the oxygas burner flame to
complete bonding of the elemental sulfur. Then the
ampoules were placed in a single-temperature furnace
and heated to the temperature of 250–300 К above the
melting point of the alloy on the stable part of the phase
diagram. After the exposure to the maximum tempe-
rature for 8-10 hours with periodic vibration the alloys
were quenched into 25 % aqueous NaCl at the room
temperature. The use of this quenching routine allowed
us to obtain alloys with 0–50 mol. % HgS in the glassy
state. The glassy state was examined by X-ray and
microstructure analysis. Obtained glasses are transparent
in the visible light (GeS2-rich compositions) and vary
from yellow (GeS2) to black (50 mol. % HgS) color.
Raman spectra of the glasses were investigated using an
automated set-up based on a DFS-24 spectrometer. The
Raman spectra were excited by the argon laser radiation
(λ = 514.5 nm). The spectra were recorded by a cooled
FEP-136 photoelectron multiplier working in the photon
count mode. The experiment geometry was set to the
reflection mode. Optical resolution was 1.9 cm–1.
3. Results
It was proved in [4-6] that the 3D structural network of
the glassy GeS2, like the crystalline α-GeS2 which is
presented in Fig. 1, consists of the tetrahedral structural
units [GeS4] that are connected by the corners and the
edges to form a quasi-3D network.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2007. V. 10, N 3. P. 65-69.
© 2007, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
66
Fig. 1. Section of a α-GeS2 layer where the equal numbers of
the GeS4 tetrahedra are linked by four corners or by two
corners and one edge (double circles represent the common
edges perpendicular to the figure plane) [7].
The sulfur atoms bridge the tetrahedra; their mean
coordination number equals 2. As a result of the
described structuring of the components, four bands can
be singled out in the Raman spectrum of the glassy GeS2
sample in the wavelength range 250–550 cm–1 [4]:
1. ν = 340 cm–1 – strongly polarization-sensitive,
caused by the symmetrical vibration mode ν1 (А1,
molecular mode) of the tetrahedral groups [GeS4].
2. ν = 370 cm–1 – caused by the vibrations of the
edge-linked [GeS4] tetrahedra (companion c
1A mode).
3. ν = 400 cm–1 – caused by the antisymmetrical
vibration mode ν3 (F2). This band is absent from the
Raman spectrum of the crystalline GeS2. One can see its
presence in the graph as a high-frequency shoulder that
distorts a symmetrical band at ν = 340 cm–1. This band
appears in the Raman spectra due to the interaction of
the structural units GeS4 between themselves.
4. ν = 435 cm–1 – caused by the vibrations of the
S3Ge–S–GeS3 unit.
The analysis of the parameters of the scattering
spectra of the glassy alloys of the HgS–GeS2 system
shows that the frequency position and the half-width of
the scattering bands typical of the glass of GeS2
composition are practically unchanged but their intensity
decreases with the decrease of the GeS2 content (Fig. 2).
Also, an additional scattering band at ν = 312…331 cm–1
appears upon the introduction of HgS to the alloy
composition. The intensity of this band increases with x,
its position shifts to lower frequencies. A possible
assumption that this band is caused by the groupings
typical of the crystalline HgS phase is invalidated by the
known fact that the scattering bands of various HgS
modifications lie in the frequency range of 150–270 cm–1
[2]. When the HgS content increases to x = 0.5, the
Raman spectrum is split into six bands with the
appearance of a new scattering band at ν = 460 cm–1.
100 200 300 400 500 600
1
8
7
6
5
4
3
2
In
te
ns
ity
, a
.u
.
Raman shift, cm-1
Fig. 2. The Raman spectra of the glasses of the (GeS)1-x –
(HgS)x system: 1 – x = 0; 2 – x = 0.05; 3 – x = 0.10; 4 –
x = 0.15; 5 – x = 0.25; 6 – x = 0.30; 7 – x = 0.40; 8 – x = 0.50.
The increase of x from 0 to 0.50 leads to only minor
changes in the Raman spectra displayed as a shift of the
scattering band to lower frequencies (some 30 cm–1). This
is because the contributions of the different modes to the
Raman spectra are very difficult to separate (the
vibration frequencies are close, whereas the bands are
quite wide).
The intensity of the bands that correspond to the
scattering by the groupings of the glassy GeS2 decreases
with the x increase; the intensity of these bands is
proportional to the number of the tetrahedra, i.e. to the
amount of the Ge atoms. This amount decreases with x
which leads to the decrease of the scattering intensity.
A detailed analysis of the experimentally obtained
Raman spectra in the frequency range of 250–500 cm–1
required their split into separate scattering bands as
shown, for instance, in Fig. 3. It is shown in Fig. 3а that
the spectrum of the glass of GeS2 composition (x = 0)
consists of four bands. At the same time, the spectra of
the glasses of the (GeS2)1–x–(HgS)x system at x > 0
reveal five bands as shown in Fig. 4а, for x = 0.15. This
means that an additional scattering band not typical of
the GeS2 glass appears in the Raman spectra at x > 0.
Indeed, the fact that the Raman spectrum of glass
of GeS2 composition consists of four Gaussian
components is confirmed by the results of double
differentiation of the original spectrum that produces
four negative minima shown in Fig. 3b. Meanwhile, the
Raman spectra of the glasses of the (GeS2)1–x–(HgS)x
composition at 0 < x ≤ 0.4 split into five Gaussian
components as confirmed by five negative minima of the
second derivative of the experimental spectrum
(Fig. 4b).
The spectrum of the (GeS2)1-x–(HgS)x glass at
х = 0.5 can be split into six bands as shown in Fig. 5а;
this is confirmed by six negative minima of the second
derivative of the experimental spectrum (Fig. 5b).
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2007. V. 10, N 3. P. 65-69.
© 2007, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
67
250 300 350 400 450 500
In
te
ns
ity
, a
.u
.
Raman shift, cm-1
a
2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0
- 1 0 0
- 8 0
- 6 0
- 4 0
- 2 0
0
2 0
4 0
6 0
R a m a n s h i f t , c m - 1
D
o
u
b
le
D
if
fe
re
n
ti
a
ti
o
n
b
Fig. 3. The Raman spectrum of the GeS2 glass and its split into
the Gaussian components (а) and the second derivative of the
spectrum (b).
The results of the analysis of the experimental
Raman spectra are given in Table where the scattering
band frequencies, their half-width and the integral
intensities in arbitrary units are listed.
The analysis of the parameters of separate
scattering bands shows that their frequency position and
the half-width are typical of the glass of the GeS2
composition and are practically unchanged with the
composition variation. In its turn, as x increases, the
intensity of the scattering band caused by the symmetric
vibration mode ν1 (350 cm–1) decreases. In addition, the
increase of x leads to an appearance of an additional
separate scattering band with frequency ν = 320 cm–1.
The intensity of this band increases with x, and its
position shifts to lower-frequency region. This fact is
clearly related to the increase of the Hg atom concen-
tration with x.
It could be assumed that the existence of HgS
clusters is responsible for this band; however, this
contradicts the known fact that the scattering bands of
various HgS modifications lie in the frequency range of
150–270 cm–1 [4].
250 300 350 400 450 500
In
te
ns
ity
, a
.u
.
Raman shift, cm-1
a
b
Fig. 4. The Raman spectra of the (GeS2)1–x– (HgS)x glass
(x = 0.15) and its split into the Gaussian components (а) and
the second derivative of the spectrum (b).
To elucidate the rules that govern the changes in
the Raman spectra with x, we turn to the stable phase
diagram of the HgS–GeS2 which is the most objective
way to determine interrelationship composition–
structure–properties. According to the phase diagram,
the glass-formation region in this system (0 < x < 0.52)
corresponds to two liquidus sections, the crystallization
of HT-GeS2 and Hg4GeS6, separated by the eutectic at
x = 0.42 [8].
According to the pseudo-phase concept introduced
by E.A. Porai-Koshits [9] and to the quasi-eutectic
theory of V.A. Funtikov [10], the structure of multi-
component glasses is constructed with the fragments
(structural units) of the stable and the metastable
compounds existing in the system. That is, the glassy
alloys reflect, to a degree, the character of the compo-
nent interaction present in the stable phase diagram.
However, this “reflection” is accompanied by the loss of
the long-range ordering which is typical of the
crystalline substances due to the formation of a large
number of the nucleation centers and their inability to
the consolidation caused by the too-fast increase of the
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2007. V. 10, N 3. P. 65-69.
© 2007, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
68
а b
Fig. 5. The Raman spectrum of the (GeS)1–x – (HgS)x glass (x = 0.50) and its split into the Gaussian components (а) and the
second derivative of the spectrum (b).
melt viscosity. The structural units of other phases are
reflected, probably, only at the level of the preservation
of the coordination (hybrid state) of the atoms that form
these phases.
Considering the obtained results from this
viewpoint, we assume that the appearance of the new
scattering band at ν ≈ 462.2 cm–1 is probably cause by
the vibration of the structural units [HgS4]S that form the
structure of the Hg4GeS6 phase. Presented in Fig. 6, such
unit consists of a [HgS4] tetrahedron that is strongly
polarized by the presence of another sulfur atom at a
distance of 0.34 nm. As a result of the polarization and
the shift of the cation to the fifth anion, the symmetry of
such an atomic grouping is far from Td. Due to the
ability to strong deformation, the [HgS4]S unit is more
likely to appear in the glasses as a distorted trigonal
bipyramid than a tetrahedron.
The band at ν ≈ 462.2 cm–1 recorded for the sample
with x = 0.5 is probably caused by the evolution of the
structure of the Hg4GeS6 pseudo-phase and by the
appearance of the S[S3Hg]–S–Hg[S3]S bonding in the
beyond-eutectic compositions; however, there was an
attempt [11] to explain the band at ν ≈ 462.2 cm–1 as a
result of the existence of the sulfur rings S8.
Hg
S
Fig. 6. A general appearance of the structural unit [HgS4]S.
Table. Parameters of the scattering bands obtained by the split of the Raman spectra of the glasses of the (GeS2)1–x–(HgS)x
system for various х values.
Scattering band parameters
1 2 3 4 5 6
x ν1,
cm–1
Г1,
cm–1
І1
ν2,
cm–1
Г2,
cm–1
І2
ν3,
cm–1
Г3,
cm–1 І3
ν4,
cm–1
Г4,
cm–1 І4
ν5,
cm–1
Г5,
cm–1 І5
ν6,
cm–1
Г6,
cm–1 І6
0.00 340.7 28.1 564070 372.7 20.4 147056 400.2 43.3 250764 435.6 22.1 102391
0.05 344.1 22.4 314455 370.9 24.0 194026 403.4 43.4 243497 436.5 21.7 87454 328.0 26.7 229744
0.10 344.9 20.5 207679 370.9 25.6 256735 404.6 39.2 263154 436.2 22.7 112501 331.2 32.1 468307
0.15 344.2 16.6 97962 371.0 35.3 278454 409.9 28.3 109526 435.2 22.6 88272 328.0 34.2 413138
0.25 343.8 20.0 204833 368.4 35.0 384992 411.6 38.1 256344 435.7 19.8 64674 320.6 33.5 660379
0.30 343.3 18.7 181153 368.4 34.7 297341 410.2 37.8 207792 434.0 20.5 48394 316.5 34.4 630523
0.40 343.7 19.2 171389 371.0 34.9 278130 402.9 25.1 88918 426.8 27.8 126655 312.1 37.7 765099
0.50 339.1 13.7 15913 372.5 32.5 34279 406.2 29.5 27223 428.6 21.1 9484 322.0 54.8 154733 462.2 35.8 9173
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2007. V. 10, N 3. P. 65-69.
© 2007, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
69
4. Conclusions
As a result of the performed investigation, it
was established that the Raman spectra of the
(GeS2)1–x(HgS)x glasses depend substantially on their
chemical composition. The analysis of the obtained
results shows that the spectrum of the GeS2 glass
consists of four components, the spectra of the glasses of
the GeS2–HgS system with 0 < х < 0.4 consist of five
components, the spectrum with х = 0.5 consists of six
components. The appearance of the additional scattering
bands is related to the crystal chemical parameters of the
phases the primary crystallization of which form the
liquidus curve on the stable phase diagram of the GeS2–
HgS system in the region of the existence of the glasses.
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