Journal of Non-Crystalline Solids 402 (2014) 236–243

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Journal of Non-Crystalline Solids

journal homepage: www.elsevier.com/ locate/ jnoncrysol

Coordination disordering in near-stoichiometric arsenic sulfide glass

O. Shpotyuk a,b,⁎, S. Kozyukhin c, Ya. Shpotyuk d, P. Demchenko d, V. Mitsa e, M. Veres f
a
Lviv Scientific Research Institute of Materials of SRC “Carat”, 202 Stryjska str., Lviv 79031, Ukraine
b
Institute of Physics, Jan Dlugosz University in Czestochowa, 13/15 al. Armii Krajowej, Czestochowa 42200, Poland
c
N.S. Kurnakov Institute of General and Inorganic Chemistry, 31 Leninsky Pr., Moscow 199991, Russia
d
Ivan Franko National University of Lviv, 50 Dragomanova str., 79005 Lviv, Ukraine
e
Uzhgorod National University, 32 Voloshina str., Uzhgorod 88000, Ukraine
f
Wigner Research Centre for Physics, Hungarian Academy of Sciences, H-1121 Budapest, Hungary

a r t i c l e i n f o a b s t r a c t

Article history: Compositionally-dependent deviations in structural metastability of near-stoichiometric glassy arsenic sulfides
Received 3 May 2014 As38S62, As40S60 and As42S58 associated with interbalanced chemical, medium-range and coordination
Received in revised form 18 June 2014 disordering are studied with optical spectrophotometry, micro-Raman scattering and X-ray diffraction measure-
Available online xxxx
ments related to. The glasses quenched from high enough temperatures above boiling point reveal characteristic
chemical disordering with additional amount of molecular products having “wrong” homopolar bonds, this effect
Keywords:
Chalcogenides;
being inhibited in over-stoichiometric As42S58 glass. Optical transmission measurements in the bandgap cut-off
Glasses; region demonstrate increased light scattering losses in high-temperature-quenched As38S62 and As40S60 glasses,
Non-crystalline materials; while no changes are detected in As42S58 glass. The most essential influence expressed in obvious increase in the
X-ray diffraction; effective periodicity and correlation length of the first sharp diffraction peak is registered in g-As40S60 prepared
Optical properties by slow cooling from relatively low temperatures such as 500 °C. Coordination disordering due to double-
bond-based quasi-tetrahedral S3/2As_S units, identified in respect to increased Raman-active stretching
modes near 530–540 cm−1, along with extra homopolar As\As bonds enhances a compositional misbalance
in this stoichiometric specimen, tending towards As-rich glass-forming network approaching g-As42S58. Possible
topological configurations of these structural anomalies are examined using ab-initio quantum chemical calcula-
tions with RHF/6-311G⁎ basis set, testifying in a favor of more distinct spacing arrangement of quasi-tetrahedral
units and S-compensating homopolar As\As bonds.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction justifying their functioning in different spheres. Typically, these disor-

For a long time, the chalcogenide glasses (ChG), e.g. melt-quenched
vitreous alloys of chalcogen atoms (S, Se, Te) with some elements from
IV and V groups of the Periodic table [1,2], have been in a sphere of tight
interests because of a number of important applications [3–6]. Due to
excellent transparency in mid-IR region, the ChG are especially attrac-
tive for modern optoelectronics and photonics, so that emergence of a
new field of materials research called Chalcogenide Photonics has been
declared recently [7].
The ChG of binary As\S system possessing a good network-forming
ability with full saturation of covalent bonding in a wide compositional
range including stoichiometric glassy g-As40S60 serve as model objects
⁎ Corresponding author at: Lviv Scientific Research Institute of Materials of SRC “Carat”,
202 Stryjska str., Lviv 79031, Ukraine. Tel.: +380 032 263 83 03; fax: +380 032 294 97 35.
E-mail addresses: shpotyuk@novas.lviv.ua, olehshpotyuk@yahoo.com (O. Shpotyuk),
sergkoz@igic.ras.ru (S. Kozyukhin), demchenko@franko.lviv.ua (P. Demchenko),
v.mitsa@gmail.com (V. Mitsa), vm@szfki.hu (M. Veres).
dered media can be prepared by conventional melt-quenching route,
when some features of structural disordering proper to a melt occur to
be frozen in a glass [1,2].
Despite the lack of long-range interatomic correlations like in
crystals, the effect of preparation conditions still remains essential
for ChG in view of different levels of chemical (redistribution of co-
valent bonds composing glassy network) and medium-range struc-
tural disordering (topological interlinking between glass-forming
units at more prolonged length scales stretching over a few nm) [8,9].
The medium-range disordering can be eliminated along with frozen me-
chanical stresses in a glassy state due to annealing near glass transition
temperature Tg, while chemical disordering cannot be fully removed in
ChG due to this procedure [8]. So even stoichiometric g-As40S60
quenched from high enough temperatures Tq above boiling point Tb
demonstrates broken chemical ordering, which results in a few percents
of “wrong” homopolar As\As and S\S bonds in addition to heteropolar
As\S ones (such glass synthesis technological route can be conditionally
referred to as high-temperature HT-regime). At the same time, the effect

http://dx.doi.org/10.1016/j.jnoncrysol.2014.06.013
0022-3093/© 2014 Elsevier B.V. All rights reserved.
 O. Shpotyuk et al. / Journal of Non-Crystalline Solids 402 (2014) 236–243
of slow cooling reveals itself as very long physical aging in rapidly
quenched ChG, producing measurable blue shift in the fundamental op-
tical absorption edge [8,10]. Therefore, to avoid the influence of
“wrong” homopolar bonding in g-As\S, the process of glass syn-
thesis should be arranged in a principally other way, exploring
slower cooling rates from lower temperatures T q, which are more
than melting temperature T m but far below boiling point T b (such
glass synthesis route can be conditionally referred to as low-
temperature LT-regime).
In respect to the phase diagram of binary As\S system [1,11,12], the
homogeneous single-phase region of melt corresponding to As40S60 is
stretched down from Tb = 709 °C (determined at 1 atm.) to Tm =
310 °C (a more accurate value of the melting point for hydrothermally
grown As2S3 crystals gives Tm = 327 ± 2 °C [13]). Since S possesses
low Tm = 113 °C and Tb = 445 °C [14], the As (despite its higher melting
point Tm ≈ 615 °C) can react with S even at such relatively low tem-
peratures (450–500 °C). So it seems principally possible to prepare
the g-As40S60 regardless of the temperature from which the melt is
cooled down within 310 b Tq b 709 °C range. Nonetheless, this reaction
is time-exhaust because of limited S solubility in solid As (in respect to
[15,16], only 1.16 at.% of S can be dissolved in solid As at 500 °C). Hence,
it is expected that under insufficient melt homogenization at these
relatively low Tq (e.g. in the LT-regime), the S can be non-uniformly
distributed in a glassy network resulting in specific type of structural
disordering.
So the melt-quenching route to prepare near-stoichiometric g-
As\S can be arranged employing respectively low temperatures,
such as 450–525 °C [17–19]. The prepared ChG are expected to be
free of chemical disordering (as compared with HT-quenched
glassy alloys), but it remains unclear how structural metastability
will be equilibrated with medium-range disordering frozen during
this LT-regime. To our knowledge, this specificity is often ignored
despite some evident controversies between ChG prepared in LT-
and HT-regimes. This concerns, in the first hand, the uniformity in
network connectivity of glassy backbone, since even some room-
temperature stable ESR centers (not proper to g-As\S, which typical-
ly demonstrate a diamagnetic response [1]) were detected in S-rich g-
As30S70 and g-As33S67 [19].
In this work, we try to disclose the nature of structural metastability
in g-As\S caused by insufficient melt homogenization at relatively
low temperatures such as 500 °C. Two batches of near-stoichiometric
g-As40S60 allowing both S-rich and As-rich compositional deviations
will be compared for technological synthesis route arranged in the LT-
and HT- regimes.
2. Experimental
ChG samples of stoichiometric g-As 40 S 60 , S-rich g-As 38 S 62 and
As-rich g-As 42 S 58 were synthesized in evacuated (2 · 10 − 5 Pa,
ILMVAC CDK-180, Germany) and sealed fused quartz ampoules
(8 mm in diameter) by conventional melt-quenching technique in
a rocking furnace as was described elsewhere [17–19]. The elemen-
tal constituents additionally purified with distillation (no worse
than three nines) in a total amount of 6 g were melted at maximal
temperature of 500 °C (the LT-regime) or 850 °C (the HT-regime).
Whole synthesis procedure (lasted nearly 24 h) was carried out in
three steps: (1) the initial heating from room temperature to
200 °C with keeping at this temperature for 2 h, then (2) heating
to 450 °C followed by 2 h keeping at this temperature in a rocking
regime, and finally, (3) heating ampoules to the above maximal
temperature followed by 6-hour keeping at this temperature with
only 2-hour rocking. Finally, the HT-ingots were air-quenched (g-
As40S60-HT, g-As38S62-HT, g-As42S58-HT), and LT-ingots were slow-
ly cooled in a furnace-off regime (g-As 40 S 60 -LT, g-As 38 S 62 -LT, g-
As42S58-LT) to produce a glassy state, which was controlled visually
by characteristic conchoidal fracture and confirmed owing to wide-
237
stretched amorphous halos registered on X-ray diffraction (XRD)
patterns (D8 Advance BRUKER, Cu Kα-radiation, Germany). Before
all experiments, the ChG samples were cut on plane-parallel disks
of 1 mm in thickness and polished to high optical quality.
Atomic densities of the prepared glasses were controlled at room
temperature using the Archimedes method with distilled water, the ac-
curacy being not worse than ±0.005 g/cm3.
UV/VIS/NIR PerkinElmer LAMBDA 950 spectrophotometer (0.5–
1.4 μm) was used to measure optical transmission T of the samples
(± 0.5%) in the fundamental absorption edge region.
Microstructure studies were performed with Raman scattering spec-
troscopy using Renishaw system 1000 micro-Raman spectrometer
(with a typical 1–2 cm−1 resolution) equipped with charge coupling
camera. All measurements were performed at room temperature in
back-scattering geometry. The diode laser beam of 785 nm (1.58 eV) fo-
cused by means of 50× objectives was used for scattering excitation, the
excitation time being ~ 60 s. To avoid photostructural changes in the
studied ChG, the output power was limited by optical filters to the
level of 80 μW.
Structural effects ascribed to medium-range disordering in the
glasses under consideration were studied with powder XRD tech-
nique in a measuring mode of a so-called first sharp diffraction
peak (FSDP). This isolated peak in a reciprocal space is caused by
some quasi-periodicities R (defined by the FSDP position 2Θ) in
real-space interatomic correlations occurred over length D (defined
by the FSDP halfwidth) [20]. An explicit nature of the FSDP has still
remained controversial, despite extensive efforts to give unambigu-
ous interpretation of this phenomenon in last years. The FSDP be-
haves unlikely to other XRD peaks, showing anomalous decrease
and shift towards higher scattering vectors Q with pressure and in-
crease with temperature (while other XRD peaks demonstrate an
opposite tendency in full respect to the Debye–Waller rule)
[21–24]. In a more generalized approach, the FSDP is attributed to
some structural entities forming medium-range ordering in a glass
(stretched through few Å), such as two-dimensional layers
[21–24], atomic clusters [25] or voids [20,26].
The FSDP-related XRD patterns in the ChG were registered in
transmission geometry using STOE STADI P (STOE & Cie GmbH,
Germany) diffractometer with linear position-sensitive detector
(Cu Kα1-radiation, X-rays, curved Ge(111) monochromator on pri-
mary beam), as it was described in [27,28]. The ChG samples of
each composition synthesized in the LT- and HT-regimes were first-
ly powdered. Further, they were used to prepare special probes
sandwiched between amorphous films made of acetate polymer
having negligible absorption and no any XRD peaks in the region
of interest. All such probes were prepared so to keep full sample-
to-sample similarity between separate XRD measurements, the
probe thickness being close to one of standards (Si, Al 2 O 3 ) used
for equipment calibration. Nearly the same pressure of gas mixture
(90% Ar + 10% CH4) was maintained in the measuring chamber of
position-sensitive detector through whole duration of the experi-
ment. The obtained XRD data were treated for profile fitting of the
peaks by WinPLOTR program [29]. To exclude apparatus influences
in different measuring cycles (pressure instabilities in a measuring
camera, deviations in probe thickness, etc.), the XRD patterns
were normalized in respect to the maximal peak. Both the angular
position 2Θ and full width at half maximum (FWHM) were chosen
as principal parameters to describe the FSDP, their numerical values
in a reciprocal space (scattering vector Q and width ΔQ) being
parameterized as:
Q ¼ ð4π=λÞ  sinΘ; ð1Þ
ΔQ ¼ ð4π=λÞ  sinðFWHM=2Þ: ð2Þ
238 O. Shpotyuk et al. / Journal of Non-Crystalline Solids 402 (2014) 236–243

In addition, the effective FSDP-related periodicity R and correlation 70

length L over which these periodicities occur [30] were estimated
using the Ehrenfest equation [31] simplified as: 60

50
As38S62-HT

T, %
R ¼ 2π=Q; ð3Þ
40 As38S62-LT

30
L ¼ 2π=ΔQ : ð4Þ
20
Atomic clusters identified as potential subjects of structural 10
disordering in binary As\S system and their possible structural config- a
urations were examined utilizing the PC-aided simulation procedure 0
600 800 1000 1200 1400
known as CINCA (the cation-interlinking network cluster approach)
[32,33]. The ab-initio quantum chemical modeling was performed Wavelength, nm
using HyperChem Release 7.5 program package based on restricted
Hartree–Fock (RHF) self-consistent field method using split-valence
70
double-zeta basis set with single polarization function 6-311G* [34,35].
The final geometrical optimization and single-point energy calculations 60
for selected molecular precursors of network-forming clusters were per-
formed employing the Fletcher–Reeves conjugate gradient method until 50
As40S60-HT
the root-mean-square gradient of 0.1 kcal/(Ǻ·mol) was reached. The 40

T, %
As40S60-LT
obtained energy of clusters was corrected on added H atoms according
to the procedure well developed elsewhere [36–38]. In such a way, the 30
full energy for each self-closed molecular cluster was obtained. Since
20
these clusters were artificially terminated by H atoms, the half energy
of S atoms bonded to H, energy of all H atoms themselves and corre- 10
sponding S\H bonds was subtracted from this full energy to distinguish
b
the total energy of “pure” network-forming cluster. Then, the corre- 0
600 800 1000 1200 1400
sponding cluster formation energy Ef was calculated as difference be-
tween this cluster energy and overall energy of constituting atoms. Wavelength, nm

3. Results and discussion

70

As it follows from numerous previous research [8,9,39–41], g-As\S 60

synthesized in the HT-regime essentially differ by content of frozen
50 As42S58-HT
“wrong” homopolar covalent chemical bonds, this kind of structural
T, %

disordering (referred to as chemical disordering, in terms of K. Tanaka 40 As42S58-LT

[8]) being simply governed by following disproportionality reaction pre-
sented in terms of main glass-forming structural units: 30

2AsS3=2 ↔As2 S4=2 þ S2=2 ;
which denotes that some part of a glassy matrix composed of heteropolar
As\S bonds within AsS3/2 pyramids is transformed to partially- or fully-
polymerized As-rich (mostly As4S4 molecules involving two interlinked
As2S4/2 units) and S-rich entities (homochain and homocyclic Sn mole-
cules with most probable n attaining 6, 8, 9, 10, 12, 18 and 20 integers
[42,43]). This specificity of heteropolar-to-homopolar bond switching can
be conveniently expressed by modified disproportionality reaction given
in terms of principal covalent bonds (denoted by long lines) and their
nearest surrounding:
2  S2=2 As–S–AsS2=2 ↔S2=2 As–AsS2=2 þ S–S:
Chemical order broken in respect to above reaction (6) modifies the
electronic structure of g-As\S due to the defect states appearing near
band edges, so decreasing the optical bandgap [8].
At high enough temperature from which the quenching began Tq,
the equilibrium in reaction (6) is right-hand shifted, reflecting the ap-
pearance of large content of “wrong” homopolar bonds frozen in a
glass. But at lower Tq, that is not greater than boiling point Tb (for g-
As40S60, this value is close to 709 °C [11,12]), the appearance of
molecular-like products based on homopolar chemical bonds are
blocked by the energetic preference of heteropolar bonding. However,
this network-forming tendency will be disturbed, provided that
20
ð5Þ
10
c
0
600 800 1000 1200 1400
Wavelength, nm
Fig. 1. Optical transmission spectra of g-As38S62 (a), g-As40S60 (b) and g-As42S58
(c) prepared in HT- and LT-regimes.
constituent atoms (S and/or As) are not distributed uniformly in a
glassy backbone, as it can be expected for ChG prepared in the LT-
ð6Þ regime.
The high degree of chemical disordering in the HT-quenched ChG
owing to molecular-like products based on “wrong” homopolar bonds
creates some structural inhomogeneities, affecting light scattering,
these changes being expected in addition to long-wave shift in optical
transmission cut-off produced by reaction (6). Optical transmission
spectra on Fig. 1 clearly confirm this expectation for stoichiometric
g-As40S60 and S-rich g-As38S62. These ChG prepared in the HT-regime
demonstrate an obvious failure in optical transmittance at the funda-
mental absorption edge, enhancing towards lower photon wavelengths
as compared with the same for LT-cooled samples. The Rayleigh scatter-
ing losses seem to be most favorable to explain such behavior [44,45].
Indeed, a practically unchanged saturation is observed for the near-IR
 O. Shpotyuk et al. / Journal of Non-Crystalline Solids 402 (2014) 236–243
Table 1
Atomic densities ρ and the FSDP parameters of the studied As\S glasses prepared in HT- and LT-regimes.
Sample ρ, g/cm3 2Θ, ° FWHM, °
g-As38S62-HT 3.110 (5) 17.457 (14) 5.0 (3)
g-As38S62-LT 3.040 (5) 17.364 (12) 4.5 (3)
g-As40S60-HT 3.170 (5) 17.477 (12) 5.1 (3)
g-As40S60-LT 3.140 (5) 16.757 (11) 4.1 (3)
g-As42S58-HT 3.190 (5) 16.712 (12) 4.1 (4)
g-As42S58-LT 3.160 (5) 16.803 (11) 4.0 (3)
transmittance of these samples (up to 1400 nm), which is a concomi-
tant of wavelength dependence character for the Rayleigh scattering
[45]. However, no difference was detected for g-As42S58 prepared in
the HT- and LT-regimes (see Fig. 1c), testifying in a favor of negligible
effect of chemical disordering on these As-rich samples.
It is noteworthy that ChG of both HT- and LT-batches clearly demon-
strate regular long-wave shift in spectral position of cut-off with As con-
tent in good accordance with known concentration dependence of
optical bandgap in g-As\S system [46]. The saturation level of optical
transmission is close to 70% whichever ChG composition and preparation
regime, corresponding roughly to the refractive index n approaching 2.5,
which is also in good respect to the previously measured value [1,2].
Despite the spectral position of optical cut-off for g-As40S60 and
g-As38S62 prepared in the HT- and LT-regimes seeming to occur to
be interconnected through the blue shift (see Fig. 1a and b), which
is a characteristic feature of physically aged ChG [10], such a compar-
ison is simply inadmissible. Indeed, the physically aged glasses being
affected by atomic shrinkage due to aging typically demonstrate an
increased density ρ (see, for instance [47]), while the ρ data from
Table 1 show evidently an opposite tendency. The densities ρ of all LT-
samples, which in this case can serve as aged ones, are obviously reduced
as compared with HT-samples (which should be expected as non-aged
ChG). Hence this specificity is caused by chemical disordering owing to
difference in molecular-network content of the corresponding glasses
prepared in the HT- and LT-regimes rather than by their physical aging.
Thus, the chemical disordering due to HT-regime does not affect sig-
nificantly the over-stoichiometric g-As42S58, clearly modifying optical
losses in g-As40S60 and g-As38S62 (Fig. 1), this process being not simply
transferred to physical aging like in [10]. Nevertheless, it leaves prob-
lematic to which extend these changes are attributed (if any) to
medium-range disordering in these ChG. To answer this question let's
refer to the FSDP-related correlations in the XRD patterns depicted in
Fig. 2 and parameterized in Table 1.
All XRD patterns of the studied glasses contain three amorphous
halos in the investigated 2Θ region as it follows from Fig. 2. The FSDP
corresponds to the most intensive peak revealed at 2Θ ≈ 16.5–17.5°,
Fig. 2. XRD patterns of g-As38S62 (1,2), g-As40S60 (3,4) and g-As42S58 (5,6) prepared in HT-
(1,3,5) and LT-regimes (2,4,6). Y offset is 12 mm for better presentation of the differences.
239
Q, Å−1 ΔQ, Å−1 R, Å L, Å
1.24 0.36 5.08 17.62
1.23 0.32 5.10 19.49
1.24 0.36 5.07 17.33
1.19 0.29 5.29 21.58
1.19 0.29 5.30 21.36
1.19 0.29 5.27 21.98
while two weaker halos are observed near ~ 6° and ~34°. There is also
a smaller satellite peak located at the right from the FSDP (~ 21.3°),
this peak being attributed to different S allotropes present in the sam-
ples (α-cyclo-S9, cyclo-S20, α-cyclo-S8) [14,27,42,43,48,49]. In respect
to theoretically calculated XRD patterns shown in Fig. 3, there were no
character peaks near scattering angels proper to arsenolite As2O3
(with a most intensive line near 2Θ ≈ 14°), as it was characterized for
γ-irradiated g-As40S60 [27,28]. So parasitic oxidation processes are
quite well inhibited in all studied glasses.
As it follows from Fig. 2, the FSDP position does not depend on the
highest temperature of the melt for g-As38S62 and g-As42S58, demonstrat-
ing respectively strict decrease in 2Θ from 17.5° to 16.7°, respectively.
The peak halfwidth (FWHM) drops slightly in the g-As 38 S62 -LT as
compared with HT-quenched sample, but it remains nearly the
same in g-As42S58-HT. More essential changes occur in the FSDP pa-
rameters of stoichiometric g-As40S60. The HT-quenched sample of
this composition g-As40 S60 -HT behaves similarly to g-As 38S 62 -HT
giving 2Θ = 17.5° and FWHM = 5.1°, while the LT-quenched g-
As38S62-LT is very close to both g-As 42 S58 showing typical for this
glass 2Θ = 16.8° and FWHM = 4.1°. These effects are accompanied
by corresponding changes in the scattering vector Q and width ΔQ,
as well as effective periodicity R and correlation length L gathered
in Table 1.
The observed stability in the FSDP parameters for g-As42S58 testifies
in a favor of unchanged medium-range disordering of this specimen
prepared in different melt-quenching/cooling regimes. In other words,
the inner structural correlations, which determine the FSDP origin in
As-rich g-As42S58, are the same whichever medium-range and/or chem-
ical disordering frozen from a melt. This result permits to suppose that
the FSDP-related medium-range correlations in this glass prepared in
the LT-regime are inter-balanced with ones occurred with respect to re-
action (6) in the HT-regime, or alternatively, both types of structural
disordering are ineffective to parameterize the FSDP. The similar
Fig. 3. Experimental XRD patterns of g-As40S60 prepared in HT- (black curve) and LT-
regimes (blue curve) as compared with theoretically calculated ones for crystalline
arsenolite As2O3 (red curve) and sulfur S α-cyclo-S9 and cyclo-S20 polymorphs (green
and purple curves, respectively). (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)
240 O. Shpotyuk et al. / Journal of Non-Crystalline Solids 402 (2014) 236–243

changes are characterized for S-rich g-As38S62, since no essential shift in
the FSDP position was detected. However, slight drop in the halfwidth of
this peak leading to ~10% rise in the correlation length L (from 17.62 Å
for g-As38S62-HT to 19.49 Å for g-As38S62-LT) can be attributed to the ex-
pansion in real-space region of structural correlations responsible for
the FSDP.
In contrast, the stoichiometric g-As40S60-LT as compared with HT-
modified g-As40S60-HT demonstrates an obvious increase in both effec-
tive periodicity R and correlation length L corresponding to the FSDP
(Table 1). Thus, the XRD patterns of g-As40S60-LT become very similar
to ones registered for LT- and HT-modifications of g-As42S58. So it can
be speculated that intrinsic decomposition in this glass is caused mainly
by demixing of some S atoms from glassy network under these prep-
aration conditions in the LT-regime, ensuring an effective As-rich
glass-forming network for atomic remainder (very similar to one in g-
As42S58). This effect agrees well with the observed long-wave shift of
fundamental optical absorption edge in g-As40S60-LT approaching one
character for both g-As42S58 samples (Fig. 1b and c).
Thus, special kind of structural disordering seems to appear in the
Thus, in full agreement with these predictions, we reasonably expect
from our Raman scattering spectra shown in Fig. 4 that the LT-
synthesized ChG are influenced by abnormal coordination for some
amount of As atoms in QT configurations based on double As_S
bonds, this anomaly being accompanied by the appearance of additional
homopolar As\As bonds. So despite obvious preference of direct
corner-shared linking between AsS3/2 pyramids [32,57], some amount
of S3/2As_S units along with “wrong” As\As bonds have been formed
in the LT-cooled glasses, being a source of structural disordering
owing to insufficient melt homogenization, which in this respect can
be identified as coordination disordering. Accepting a strong difference
in Raman cross sections σ for stretching As_S vibrations in S3/2As_S
units (σ = 21.9) and symmetric As\S vibrations in AsS3/2 pyramids
(σ = 34.0) as it is assumed from the first-principle calculations [50],
the content of such structural anomalies in g-As2S3 estimated roughly
from surface areas under corresponding peaks of Raman spectra on
As38S62-HT x10

490
340
LT-cooled ChG due to insufficient melt homogenization at relatively As38S62-LT

530-540
470
365
low temperatures (500 °C). Deficient S distribution in a glassy network

310
stabilized at the LT-regime ensures looser glass structure with signifi- a

Intensity, a.u.
cantly reduced atomic densities ρ as it follows from the data gathered
in Table 1. It is noteworthy that this feature does not affect optical trans- 450 500 550
mission giving a sharp steepness in optical transmission edge of all LT-

165
180

530-540
prepared glasses (Fig. 1), but obviously enhances chemical misbalance

230

490
shifting ChG towards more As-enriched compositions.

470
265
To shed more light on the possible nature of this phenomenon, we
performed a comparative microstructure study of the glasses prepared
in the LT- and HT-regimes using micro-Raman scattering technique,
150 200 250 300 350 400 450 500 550 600
the normalized spectra being shown in Fig. 4. -1
In respect to these data, the glasses synthesized in the HT- and LT- Raman shift, cm
regimes differ gradually by the content of homopolar bonds. Indeed,
apart from sharp lines corresponding to Raman-active modes of AsS3/2 As40S60-HT x20
340
530-540
pyramids, which are principal glass-forming units in these ChG (the As40S60-LT

490
365

470
umbrella mode at 165 cm− 1 and dominant broad band of stretch
310

symmetric-asymmetric modes at ~ 340 cm− 1 modified by shoulders b

Intensity, a.u.

at ~ 310 and ~ 380 cm−1 [50–52]), the modes assigned to homopolar

bonding can be easily identified. In part, the intense bands at ~ 180, 450 500 550 600
230 and 365 cm− 1 can be attributed to As\As-based units such as
165

220
180

As4S4 molecules [50–54], while slight bands at 220 and 470 cm− 1
530-540
230
210

along with 490 cm−1 are caused by S\S vibrations in ring- and chain-
490
470

like fragments, respectively [50–52,55,56]. Surprisingly, all these

Raman-active modes (see Fig. 4) corresponding to homopolar bonding
(especially, As\As bonds) are more prominent in g-As40S60-LT.
150 200 250 300 350 400 450 500 550 600
From stoichiometry point, it seems that additional channel of S ap-
-1
pearance should be employed in the LT-cooled ChG to equilibrate with Raman shift, cm
these As\As bond extraction. This channel becomes evident from
Raman spectra inspection in 500–550 cm−1 range (as it follows from in- As42S58-HT x20
340

sets to Fig. 4). It is seen that the LT-cooled ChG demonstrate additional
As42S58-LT
365

wide band at ~530–540 cm−1, absent in the HT-quenched glasses. To 530-540

490
470
310

our knowledge, there were no Raman-active modes attributed to own

c
Intensity, a.u.

structural fragments of g-As40S60 in this spectral region, despite careful

inspection of whole g-As\S system previously [50–52,54,56].
180

220

To identify an eventual origin of this anomaly, let's refer to possible 450 500 550
165

theoretical predictions for Raman-active modes in g-As\S, which are

230
210

530-540

anticipated for this spectral region. Thus, in respect to the first-

490
470

principle cluster-modeling calculations based on density-functional

theory [50], the quasi-tetrahedral (QT) S3/2As_S unit can be evidenced
by the mode of double-bond As_S stretch vibrations at 537 cm− 1
(while other umbrella, symmetric-stretch and asymmetric-stretch 150 200 250 300 350 400 450 500 550 600
modes of this QT unit are expected to be neat 146, 335 and 365 cm−1, Raman shift, cm
-1

respectively, contributing mainly to modes of normal AsS3/2 pyramids).

This finding is also concomitant with the earlier ab-initio Hartree–Fock Fig. 4. Micro-Raman spectra of g-As38S62 (a), g-As40S60 (b) and g-As42S58 (c) synthesized
method calculations for different structural configurations in g-As2S3, in HT- and LT-regimes (the inset represents enhanced domain corresponding to symmet-
giving As_S group frequencies in 525–530 cm−1 domain [54]. ric stretching mode of QT S3/2As_S unit).
 O. Shpotyuk et al. / Journal of Non-Crystalline Solids 402 (2014) 236–243
Fig. 4 can be expected at the level of a few percents. So this anomaly can
really be presented only as a specific kind of structural defects due to
non-uniform S distribution in a glassy matrix, resulting from LT-
deviations in conventional glass-preparation technology.
Coordination disordering gives an adequate explanation for the
above FSDP-related correlations in the XRD patterns of the studied
ChG (see Fig. 2), as it can be found within known Gaskel's concept on
crystalline-like ordering in melt-quenched network glasses [58]. In
Wright's extension [59], this concept justifies the model explaining
the FSDP as arising from a periodicity in the distribution of some “pseu-
do-planes” for Bragg diffraction, which represent “walls” separating a
succession of randomly-packed network cages in a glass. Flattened
cage structure produces inner equivalent planes at opposite sides of
these cages, giving necessary contribution to the reciprocal space Fouri-
er component generating the FSDP. The ball-stick diagram of the well
known Zacharaisen's random network for binary glassy compounds
evolving two- and three-coordinated atoms on Fig. 5 [60] gives general
insight on such successive cage “walls” acting as “pseudo-planes” for the
FSDP [59]. Within this diagram, the decrease in the scattering vector Q
corresponding to the FSDP position with the increase in the pnictogen
concentration [61] can be viewed as deviations in distances between
cage “walls” due to enlarged pnictogen–pnictogen or shortened chalco-
gen–chalcogen bonds in a network of mostly heteropolar pnictogen–
chalcogen bonds. The appearance of fourfold-coordinated As atoms ter-
minated by double As_S bonds essentially modifies the remaining ring
structure due to “compensating” As\As bonds pushed in the nearest
atomic environment. As a result, the flattened cage-like network be-
comes enriched on As\As bonds, resulting in the effect similar to the
shift towards As-rich glass compositions. Therefore, the FSDP of stoichio-
metric g-As40S60 prepared in the LT-regime, which contains maximal
content of QT S3/2As_S units, occurs to be parameterized like As-rich
g-As42S58 (see Table 1).
The S-compensating homopolar As\As bonds can be immediately
attached to fourfold-coordinated As atoms, being included directly in
QT unit as _As\[As(S2/2)]_S fragment of As2S3 network-forming clus-
ter, or, alternatively, they can be pushed away from this place in a cage-
like glassy network to create _As\[As(S3/2)]\[As(S2/2)]_S fragment
of As3S4.5 network-forming cluster. The latter is necessary to form uni-
form network topology of ChG enriched on extra As\As bonds.
Fig. 5. Ball-stick representation showing pseudo-planes for “Bragg” diffraction formed by
successive cage “walls” within known Zachariassen's random network diagram [26] con-
tributing to the FSDP in Wright's presentation [24] (red and yellow colors are stand for As
and S atoms, respectively). (For interpretation of the references to color in this figure leg-
end, the reader is referred to the web version of this article.)
241
Fig. 6. Ball-stick representation showing geometrically-optimized configurations of
double-bond-based S_As2S2H4 (a) and S_As3S3.5H4 (b) clusters (red, yellow and gray
colors are used to show As, S and H atoms, respectively). (For interpretation of the refer-
ences to color in this figure legend, the reader is referred to the web version of this article.)
The preferred one of these structural solutions can be justified with
ab-initio quantum chemical simulation using CINCA [32,33]. Let's con-
sider two possible configurations of network-forming clusters based
on QT units, e.g. As2S3 and As3S4.5, both being terminated by four H
atoms to form self-closed molecular S_As2S2H4 and S_As3S3.5H4 pro-
totypes suitable for calculations. The geometrically optimized configu-
rations of these clusters are shown in the ball-stick representation in
Fig. 6 and corresponding parameters are gathered in Table 2. Calculated
distances for single As\S and double As_S bonds occur to be only
slightly scattered in these clusters, being grouped roughly around 2.24
and 2.07 Å, respectively, while As\As bonds are shorten in S_As2S2H4
molecules (2.41 Å against 2.47 Å). Bond angles on fourfold-coordinated
As atoms are smaller from character tetrahedral angle, consisting near
106° and 107° in As2S3 and As3S4.5 clusters, respectively. Bond angle
on S atom linking homopolar As\As bonds to QT unit in As3S4.5 cluster
is close to 100°. Thus, it should be concluded that both clusters reveal
character elements of tetrahedral environment with only slight distor-
tion in As2S3 cluster having As\As bond just in its nearest surrounding.
In cluster formation energy Ef calculations, this As2S3 cluster (with
molecular S_As2S2H4 prototype) yields the second As3S4.5 one (with
molecular S_As3S3.5H4 prototype), which has more distant homopolar
As\As bond, the corresponding energetic balance being rationed
as − 76.48 kcal/mol and − 77.42 kcal/mol. Such great difference tes-
tifies that S-compensating homopolar As\As bonds are rather inserted
deeply in a cage-like glassy network than being directly attached to
As_S double-bond. By accepting remarkable difference in the bond
lengths within the g-As\S system (2.28 Å for As\S and 2.49 Å for
As\As bond [1]), the enhancement in the FSDP-related periodicity R
and correlation length L is anticipated as it follows from random net-
work diagram on Fig. 5, in full respect to the experimentally observed
effect (see Table 1).
The possibility of double-bond linking in glassy arsenic chalcogen-
ides has still remained a subject of hot controversies in scientific litera-
ture as a key giving an unambiguous explanation for some anomalies
observed in compositional dependencies of their physical–chemical
properties. Thus, numerous attempts have been made to explain the
under-margin values observed in the reversing heat flow of DSC pat-
terns in As\S/Se ChG near the mean coordination number (the number
of covalent chemical bonds per atom) Z = 2.286 due to this kind of in-
teratomic bonding, thus proving compositional boundaries for so-called
optimally-constrained intermediate phase in their elastic proper-
ties [50]. Indeed, by assuming covalent bond as Lagrangian constraint
nc, two types of elementary structural units having (in per-atom deter-
mination) the number of these constraints nc approaching the space di-
mensionality (in case of 3D space nc = 3.00) can be expected for binary
g-As\S [50,51]. The first is AsS3/2 pyramids linked through common S
atom (corner-sharing S2/2As\S\AsS2/2 pyramidal units), which corre-
sponds to stoichiometric As2S3 composition (Z = 2.40), while the sec-
ond is S3/2As_S quasi-tetrahedrons, which are proper to more S-rich
ChG (Z = 2.286). As glassy backbone had been composed only from
242 O. Shpotyuk et al. / Journal of Non-Crystalline Solids 402 (2014) 236–243
Table 2
Geometric parameters of optimized network-forming clusters in binary As\S system based on double-covalent bond and their formation energies Ef (kcal/mol).
Network (molecular) cluster Bond distance, 10−4 nm Bond angle, deg
As\S As\As As_S ∠S\As\S
As2S3 2244 2463 2069 97.7
(S_As2S2H4) 2249 2347 101.8
2226
average 2240 2405 2069 99.8
As3S4.5 2247 2470 2063 100.1
(S_As3S3.5H4) 2255 101.6
2245 103.0
2287 102.6
2217 102.6
2217
2217
Average 2241 2470 2063 102.0
these units, all corresponding ChG are expected to be optimally-
constrained with nc = 3.00, giving a reason for so-called reversibility
window in this range of compositions. However, this is not a case of ho-
mogenized glassy networks prepared in conventional melt-quenching/
cooling conditions, neither As\S [18] nor As\Se [62], since reliable
experimental evidences for double-bond-based QT structural units
S(Se)3/2As_S(Se) have not been obtained before. It means that
double-covalent bonding does not govern primary network-forming
tendencies in glassy arsenic chalcogenides, in contrast to phosphorous
chalcogenides, where such possibilities can be evidently realized [1,63].
This is the first time when this type of structural anomaly (coordi-
nation disordering) was found in g-As40S60 as being produced by
inhomogeneities in S distribution originating from technological conditions
of glass preparation. Surprisingly, that double-bond linking was not found
in ChG synthesized at high over-melting temperatures, but, otherwise,
obtained at relatively low temperatures but with insufficient melt ho-
mogenization. This type of structural defects sets the glassy system far
away from thermodynamic equilibrium, because in addition to increased
atomic coordination for As atom in optimally-constrained QT environ-
ment (nc = 3.00), the appearance of homopolar As\As bonds introduces
extra constraints in a glassy matrix making its rigid and stress. Within
constraint counting algorithm developed at the basis of the Phillips–
Thorpe mean-field rigidity percolation theory [64,65], it can be easily
estimated that the _As\[As(S2/2)]_S structural fragment having
an adjacent As\As bond is over-constrained with n c = 3.20,
while _As\[As(S3/2)]\[As(S2/2)]_S unit with a more distinct As\As
bond has nc = 3.13. Thus, the coordination disordering results in
over-constrained glassy network in respect to chemical bond dis-
proportionality given by the following reaction below:
3  S2=2 As–S–AsS2=2 ↔2  S3=2 As ¼ S þ 2  S2=2 As–AsS2=2 :
The left-hand part of this equation represents the network of
corner-shared AsS3/2 pyramids, while the right-hand side corresponds
to QT S3/2As_S units and homopolar As\As bonds within As2S4/2 con-
figuration. Under conventional synthesis conditions, the equilibrium of
this reaction (6) is shifted in the left side, which determines the prefer-
ence of heteropolar covalent bonding in g-As\S. However, under insuffi-
cient melt homogenization, which occurs at relatively low temperatures
Tq (450–500 °C), the bond disproportionality in the quenched glass at-
tains an opposite trend, producing fourfold-coordinated As atoms and
“wrong” homopolar As\As bonds.
Supposedly, the coordination disordering could result in optimally-
constrained glassy network in a sense of global connectivity, provided
As\As bonds were overcompensated by S additions to form the
normally-coordinated covalent network of corner-sharing AsS3/2 pyra-
mids. However, as it follows from Fig. 4, this effect determined in the in-
creased stretching vibrations of QT units (530–540 cm−1) decays with S
addition (in g-As38S62-LT) as compared with stoichiometric g-As2S3,
Ef
∠S\As_S ∠As\As_S ∠S\As\As ∠As\S\As
115.0 111.1 98.0 – −76.48
114.8 97.8
114.9 111.1 97.9 –
116.7 – 105.4 99.7 −77.42
115.3 95.0
114.7 100.7
95.1
115.6 – 99.1 99.7
while S\S vibrations in ring- and chain-like fragments (470 cm−1 and
490 cm−1, respectively) obviously grow. It means that concentration
excess of S in g-As\S system does not facilitate a global network con-
nectivity resulting in nc = 3.00, so that coordination disordering is rath-
er compositionally near-stoichiometric effect.
4. Conclusions
Structural metastability in near-stoichiometric g-As\S is composi-
tionally dependent in view of interbalanced chemical, medium-range
and coordination disordering, the latter being caused by insufficient
melt homogenization at relatively low temperatures such as 500 °C.
Molecular products based on “wrong” homopolar covalent chemical
bonds in HT-prepared glasses appeared in respect to heteropolar-to-
homopolar bond redistribution revealing the essential effect on optical
transmission cut-off due to long-wave shift and increased scattering
losses in this spectral region, this kind of structural disordering being
suppressed in As-rich g-As42S58, which is quite close to the boundary
of glass-forming region.
Medium-range structural disordering in g-As\S is probed with the
FSDP-related XRD. The most essential influence expressed in the in-
creased effective periodicity R and correlation length L corresponding
to the FSDP is characterized for stoichiometric g-As40S60 prepared
in the LT-regime. This specimen obviously demonstrates composition-
al misbalance tending towards As-rich glass-forming network ap-
proaching g-As42S58.
This work gives first experimental evidence for microstructure
changes corresponding to such inhomogeneities in S distribution
using micro-Raman scattering. Owing to slow cooling from relatively
low temperatures and insufficient melt homogenization, the double-
ð7Þ
bond-based S3/2As_S units can be formed in g-As\S as a specific kind
of coordination disordering associated with non-uniform S distribution
in a glassy matrix. Possible topological configurations of these structural
anomalies are examined with ab-initio quantum chemical modeling for
clusters, evolving both double-bond QT unit and neighboring S-
compensating homopolar As\As bond. Effect of coordination dis-
ordering, which is most pronounced in near-stoichiometric g-As40S60,
does not result in optimally-constrained glassy network in a sense of
global connectivity.
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