J. Am. Ceram. Soc.

, 95 [4] 13201325 (2012)

DOI: 10.1111/j.1551-2916.2012.05117.x
2012 The American Ceramic Society

Journal

Mechanical Properties and Crystallization Behavior of

GeS2Sb2S3In2S3 Chalcogenide Glass

Lei Ying, Changgui Lin,, Qiuhua Nie, Zhuobin Li, Yinsheng Xu, Feifei Chen, and Shixun Dai,

The School of Information Science and Engineering, Ningbo University, Ningbo 315211, China

The School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China

54GeS236Sb2S310In2S3 glass-ceramics were prepared by

heat-treating the base glass above Tg for dierent durations.
The results of Raman spectra and XRD patterns show that the
rst precipitated crystals during the heat treatment are In2S3
and the crystallization of the Sb2S3 and GeS2 subsequently
occurs. Bulk samples heat-treated at 295C for dierent heating rates and durations are used to study the crystallization
mechanism and evolution of the three crystallization peaks
(CPs). It is found that three CPs partly overlap with each
other and then separate with increasing heat-treating durations.

I.

bility. In this case, metallic halide is substituted by a similar

large-metallic sulde In2S3,which plays a role in the formation of the glassy framework other than modier. Meanwhile, the element In located at the same main group and
the next period of the elemental period table as Ga, In-contained chalcogenide glasses should have similar superior
properties, such as high solubility of rare earth ions. Furthermore, the substitution of Ga for heavier metal In would
increase the refractive index, leading to high quantum eciencies for rare earth ions transition in chalcogenide glass.12
In this work, we focus on the crystallization behavior of
glasses based on the GeS2In2S3Sb2S3 system which has
been well-investigated in our previous research.13 As crystallization of a chalcogenide glass is a highly exothermic process,
dierential scanning calorimetry (DSC) is a very suitable
technique for obtaining the parameters of crystallization. The
results on the precipitated crystal phases, physical properties,
and crystallization behavior of GeS2In2S3Sb2S3 glassceramics are presented and discussed. Based on the DSC, XRay diraction (XRD), and Raman results, the crystallization mechanism for three crystal phases of In2S3, Sb2S3, and
GeS2 is elucidated in detail.

Introduction

HALCOGENIDE glasses have received considerable interest

in the development of pertinent materials operating in
mid-infrared (IR) spectral region of 210 lm wavelength
range for various applications such as thermal imaging, optical bers for chemical and biological sensing, optical modulator and optical communications.13 In addition, their
advantages over currently used single crystalline germanium
are associated with the relatively low-cost of raw materials
and the possibility of producing complex optics by molding.4,5 However, the excellent IR transmitting material has
not been fully exploited due to their intrinsic weakness such
as poor resistance to crack propagation and thermal shocks.
Fortunately, the generation of crystals inside a glass matrix
is a proven technique for improving the mechanical properties of glasses to balance shock sensitivity and inhibit crack
propagation.6,7 As far as optical properties are concerned,
the formation of grains inside glass matrix can be a source of
optical loss due to light scattering. Consequently, main challenge in glass-ceramic science is to discover glassy systems
exhibiting soft balance in glass to crystal transformation and
keeping good transparency.
In the past several years, crystallization behavior of some
chalcogenide glasses, e.g., GeS2Ga2S3CsCl,8 GeSe2Sb2Se3
RbI9 and GeS2Sb2S3CsCl10 have been systematically
investigated. These relatively suitable systems are based on
glasses of the GeS2Sb2S3 or GeS2Ga2S3, combined with
metallic halide in which the size of the metallic ion is large
enough to be used as the compatible modier cations. Previous studies have been conducted in using CsCl, CsBr, CsI,
RbI, CuI, PbI2.911 Unfortunately, controllable and reproducible crystals growth in the above mentioned chalcogenide
glassesstill suer from the diculty to control the nucleation
of nanometer size and species. In addition, the introduction
of relatively high-halide content leads to poor chemical dura-

II.

Experimental

Bulk glass with a composition of 54GeS236Sb2S310In2S3

was synthesized using polycrystalline germanium, indium,
antimony, and sulfur (all of 5 N) as starting materials.
Appropriate quantity (10 g) of each component was weighed
according to the stoichiometric glass composition and introduced into a silica tube, which was sealed under a vacuum of
~10
3 Pa and then it was reacted at 950C for 13 h in a
rocking furnace. Tube containing the melt was moved out
and subsequently quenched in cold water. The reference
polycrystalline In2S3 sample was also prepared with very
slow cooling rate in a vacuum silica tube. The obtained glass
rod was annealed below glass transition temperature (Tg) for
5 h to minimize inner stress. Specimens were cut into disks
of ~10 mm in diameter and 1.5 mm in thickness, and polished both sides for optical measurements. The crystallization
of the as-prepared glass was conducted by heating at 2C/
min to a designed temperature (THT), holding for various
durations, and then cooling slowly to room temperature.
The glass transition temperatures (Tg) and crystallization
temperatures (Tx) of as-prepared glasses were determined by
DSC at a heating rate of 10C/min with a temperature accuracy of 1C (TA Q2000). To study the crystallization
behavior, bulk samples heat-treated at THT (Tg + 20C) for
dierent durations were placed in hermetic aluminum pans
and heated from room temperature until crystallization completed. The densities were measured, according to Archimedes principle using de-ionized water as an immersion liquid.
Transmission spectra were obtained with a Lambda 950 UVVIS-NIR spectrophotometer (Perkin-Elmer, Inc., Waltham,
MA) in visible and near-IR spectral region and Nicolet 381

J. Heocontributing editor

Manuscript No. 30209. Received August 21, 2011; approved January 18, 2012.

Authors to whom correspondence should be addressed. e-mails: linchanggui@nbu.

edu.cn and daishixun@nbu.edu.cn

1320

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GeS2-Sb2S3-In2S3 Chalcogenide Glass and Glass Ceramics

Fourier Infrared spectrophotometer (Thermo Nicolet Corporation, Madison, WI) in the mid-IR region ranging from
2.5 to 16 lm, respectively. Crystals in glassy matrix were
observed by a scanning electric microscope (SEM) and the
marks and cracks made by indentation were observed with
optical microscope (VHX-1000E; Keyence Corporation,
Osaka, Japan). XRD data were collected using a D8
Advance X-Ray diractometer (Voltage 36 kV, current
20 mA, Cu Ka; Bruker AXS, Madison, WI). Raman spectra
were conducted at room temperature using back (180) scattering conguration by Laser Co-focal Raman Spectrometer
(Renishaw, inVia) with excitation wavelength of 488 nm. The
resolution in the frequencies is 0.5 cm
1. Vickers microindenter (Everone MH-3, Everone Enterprises. Ltd., Shanghai,
China) was used to obtain hardness with a charge of 100 g
for 5 s. All the characteristics were averaged over measurement on 10 indentations per sample.

III.

(a)

(b)

(c)

(d)

Results and Discussion

The DSC curve of the 54GeS236Sb2S310In2S3 glass at a

heating rate of 10C/min is shown in Fig. 1. An obvious exothermic peak can be observed, and the characteristic temperatures of Tg and Tx are also listed in Fig. 1. Evidently, the
exothermic peak is overlapped by several peaks as shown in
the inset. The exothermic peak can be decomposed by Gaussian functions with three peaks ranging from 370C to 415C,
suggesting dierent kinds of crystallization. With the knowledge of thermal results and previous study,14,15 a fairly low
THT of 295C (Tg + 20C) was chosen as heat-treated temperature for crystallization process. The base glasses were
placed in a ventilated furnace at 295C for dierent durations ranging from 20 to 120 h. It should be pointed out that
the shape and parallelism of the studied samples were not
changed after the heat-treatment. To investigate whether
mechanical properties would be improved after ceramization
process, Vickers indentations were performed on the wellpolished samples. As shown in Fig. 2, the marks and cracks
made by indentation were observed with an optical microscope. The propagation of cracks is greatly inhibited with
increasing heat-treatment durations, indicating a progressive
strengthening of the samples by generating crystals inside
glassy matrix. Some physical and mechanical properties are
listed in Table I.
Furthermore, the Vis-NIR transmission spectra, which are
very sensitive to the presence of crystals, are shown in
Fig. 3(a) for the base and crystallized glasses. As indicated in
Table I, it can be clearly seen that the cut-o edge of short

Fig. 1. DSC curve for bulk glass of 54GeS236Sb2S310In2S3 at a

heating rate of 10C/min. The exothermic peak is tted by Gaussian
Functions in the inset.

Fig. 2. Optical microscope pictures of the dierent samples after

Vickers indentation (a) Base glass, glasses crystallized at 295C for
(b) 20 h, (c) 40 h, and (d) 60 h, respectively.

Table I. Some Physical and Mechanical Properties of the

54GeS236Sb2S310In2S3 Glass and Glass-Ceramics
Samples

Cut-o
edge (1 nm)

Base
20 h
40 h
60 h
90 h
120 h

637
643
825
1027
1273
1608

Density,
(0.002 gcm3)

3.595
3.671
3.794
3.790
3.732
3.867

Hardness, Hv
(2 Kgmm2)

177
175
180
186
194
193

wavelength is red-shifted as a function of heat-treatment

durations. It is well known that the change depends largely
on the size and concentration of the crystals, and that the
optical attenuation decreases rapidly when the wavelength
increase.16 Surprisingly, as shown in Fig. 3(b), the transmittance is not impaired strongly in the mid-IR spectral region
from 2 to 10 lm. It can be concluded that the presence of
small crystals in the glassy matrix does not impair the transparency in the application window located at mid-IR spectral
region. Then, SEM images shown in Fig. 4 indicate that the
inner crystals are of size about 60 nm, which cause Mie diffusion to shift the cut-o edge of short wavelength, and no
notable change of size is observed in the range of 60 h. However, samples heat-treated for 120 h at 295C show a distinctly decrease in the maximum of transmission from 65%
to 50%. This phenomenon shows the presence of large crystals that deteriorate the transparency of the material rapidly,
leading progressively to its whole opacity in the IR range.
To identify the species of the precipitated crystal, X-ray
diraction is carried out on the polycrystalline In2S3 and the
54GeS236Sb2S310In2S3 base glass heat-treated for dierent
durations. Figure 5 presents the XRD patterns collected at
295C during 120 h on powder samples. A three-step crystallization mechanism can be clearly recognized from these
XRD patterns. During the rst step, which ends after ~ 20 h
of annealing at 295C, no obvious diusion signature is
observed and the matrix remains mostly amorphous. However, after about 40 h, several peaks (2h = 27, 33, 43 and
47) appear and then grow slowly and continuously. The

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Journal of the American Ceramic SocietyYing et al.

Vol. 95, No. 4

(a)

Fig. 5. XRD patterns of In2S3 polycrystalline, 54GeS236Sb2S3

10In2S3 base glass and glass ceramics obtained by heat-treatment at
295C for dierent durations, respectively.

(b)

Fig. 3. Transmission curves of 54GeS236Sb2S310In2S3 glass and

glasses ceramics heat-treated at 295C for dierent durations: (a)
near-infrared transmitting spectral region, and (b) the whole
transmitting spectral region. The inset of (b) is the photograph of
the base glass and glasses ceramics.

(a)

(b)

Fig. 4. SEM images for samples crystallized at 295C for dierent

durations: (a) 40 h9100 000, and (b) 60 h9100 000, respectively.

Fig. 6. Raman spectra of In2S3 polycrystalline, 54GeS236Sb2S3

10In2S3 glass and glasses ceramics heat-treated at 295C for dierent
durations.

positions of these peaks are in good agreement with the

In2S3 indexation (JCPDS card no. 25-0390) and their broadness conrms the nanosize of the particles. The third step,
starting from about 50 h, corresponds to the appearance of
new sharp ones (2h = 22, 41), related to new crystal phase
Sb2S3 (JCPDS card no. 42-1393). In addition, the GeS2 phase
(2h = 30, 31) is also present in the 60 h heat-treated sample. Therefore, the species of crystal phases are roughly
revealed by the XRD patterns.
In addition, normalized Raman spectra of the glass ceramics and In2S3 polycrystalline are presented in Fig. 6, further
conrming that the crystals of In2S3 and Sb2S3 were precipitated. With the increasing of the heat-treatment durations,
the bands around 140 and 310 cm
1 which is attributed to
the vibrations of [S3InInS3] ethane-like units and [InS4] tetrahedra17 are gradually enhanced at the beginning of 20 h.
More importantly, the little prominence at 140 cm
1 become
sharp with the elongation of heat-treatment whereas the
band at 310 cm
1 has almost no change. It can be ascribed
that the vibration of the homopolar bond of InIn in the
In2S3 crystal gradually dominates in the crystallized samples.
In addition, the main Raman peak at 300 cm
1 corresponding

April 2012

1323

GeS2-Sb2S3-In2S3 Chalcogenide Glass and Glass Ceramics

to the vibration of the [Sb2S3] pyramid unit is also sharpened

after 60 h heat-treatment, suggesting the Sb2S3 crystals have
appeared during the crystallization process. Regretfully, we
did not observe the characteristic vibration band of GeS2
crystals in Fig. 6, which may be due to the Raman spectra of
a small amount of GeS2 crystals undistinguishable from that
of GeS2 glass.18 Based on the above-mentioned analysis, the
species and sequence of crystallization are coincident to the
XRD results.
IR-transmitting 54GeS236Sb2S310In2S3 glass-ceramics
with improved mechanical properties have been fabricated
through a reproducible and controllable crystallization.
Meanwhile, the species, size, and sequence of precipitated
crystals were determined. Hence, in the following, the main
purpose is to study the crystallization mechanism of this
glass. The presence of three CPs in Fig. 1 may be due to the
presence of dierent crystallization mechanism. Furthermore,
as shown in Figs. 5 and 6, three crystal phases were precipitated in the glass matrix, successively. Therefore, it can be
supposed that these three CPs are originated from the precipitation of In2S3, Sb2S3, and GeS2 crystals, respectively.
Despite the good knowledge on the distinct phase transformation for the three CPs achieved, the reasons mainly for
the crystallization of In2S3 crystals in 54GeS236Sb2S3
10In2S3 glass at 295C are still ambiguous. As shown in
Fig. 7, a variable heating rate DSC method was employed to
evaluate the kinetic parameters for crystallization of the studied glass. In Table II are listed the characteristic temperatures of the studied chalcogenide glass at an increased
heating rate, b = 1, 5, 10, 15 and 20C/min. The crystallization behavior of the three glass phases can be understood by
the following kinetic parameters: the activation energy for
the crystallization Ec, the frequency factor K0, and the crys-

tallization rate constant K. To obtain the kinetic parameters,

the kinetic model of Bansal and Hyatt19 is used and
expressed as follows:

ln

b
T2c





Ec
RK0
ln
RTc
Ec

(1)

Where R is the ideal gas constant (8.314 Jmol
1K
1), and

Tc is the characteristic temperature in Kelvin, respectively.
Plots of lnb=T2c against 1000/Tc for the chalcogenide glass
give a linear behavior as shown in Fig. 8. Consequently, the
Ec and K0 values are calculated from the slopes of these lines
corresponding to Ec/R, listed in Table III. Nevertheless, the
parameters of Ec and K0 are still not sucient to understand
why the In2S3 crystal phase is much easier to be fully crystal-

Fig. 8.

Plots of lnb=T2c vs (1000/Tc).

Table III. Crystallization Kinetics Parameters for

54GeS236Sb2S310In2S3 Glass
Crystallization peaks

First (In2S3)
Second (Sb2S3)
Third (GeS2)

Ec (kJmol
1)

K0 (s
1)

K295C (s
1)

152.30
155.34
160.84

6.8 9 1012
1.1 9 1012
0.5 9 1012

3.49 9 10
3
2.68 9 10
3
2.63 9 10
3

Fig. 7. DSC curves of the 54GeS236Sb2S310In2S3 glasses heattreated at 295C for dierent heating rates from 1C/min to 20C/
min.

Table II.

Characteristic Temperatures of Tg, Tx and Tp for

54GeS236Sb2S310In2S3 Glass

Heating rates, b (oC/min)

Tg ( 1C)

Tx ( 1C)

1
5
10
15
20

265
281
283
284
286

339
370
377
384
389

Fig. 9. DSC curves of the 54GeS236Sb2S310In2S3 glasses heattreated at 295C for dierent durations.

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Vol. 95, No. 4

Journal of the American Ceramic SocietyYing et al.

(a)

(b)

(c)

Fig. 10. Schematic illustration of In2S3, Sb2S3,and GeS2 crystallization processes in a glass matrix: (a) precursor glass, (b) In2S3 nuclei
formation, and (c) glass ceramics.

lized than Sb2S3 and GeS2 at 295C. Hence, the crystallization rate constant K should be considered. In general, the
crystallization rate constant K increases exponentially with
temperature indicating that the crystallization is a thermally
activated process. It can be computed with Ec and K0, and
mathematically expressed as:


Ec
K K0 exp

RT

nally grow into In2S3 crystals. Similar crystallization process

for the formation of Ga2S3 nanocrystals in the GeS2Ga2S3
glass has been reported by Lin et al.22 With the increasing of
heat-treatment durations, the Sb2S3 and GeS2 crystal is precipitated subsequently.

IV.
(2)

These K values for the In2S3, Sb2S3, and GeS2 phases

listed in Table III were analyzed using the above equation.
Where T corresponding to the annealing temperature
(568.15 K), and the values of Ec and K0 are used from
Table III, respectively. The K value for the In2S3 phase is
about two times larger than that of the Sb2S3 and GeS2
phase, suggesting a much easier crystallization mechanism of
In2S3 phase. Thus, it is not surprising that the In2S3 crystals
are easily precipitated by the heat treatments at 295C.
To study the crystallization behavior of these three phases,
DSC curves of base glass and glass ceramics which were
heat-treated at 295C for dierent durations were recorded
as shown in Fig. 9. After heat-treatment at 295C for 20 h,
the main broad peak beginning split up into three exotherm
peaks gradually. By increasing the heat-treatment durations,
the three CPs shifts towards lower temperature. It is possibly
due to the increasing number of nuclei in the glass matrix
after heat-treatment, subsequently leading to an easy crystallization. Meanwhile, the height of the rst CP obviously
decreases with the elongation of heat-treatment durations
and vanishes after 40 h heat-treatment indicating the total
crystallization of associated phase. During this period, the
second and the third CPs dissociated by degrees as well as
the increasing height of the CPs. After 60 h heat-treatment,
the second CP almost disappeared, indicating the total crystallization of the related phase. Moreover, the third CP
behaves in a similar way by further increasing the heat-treatment time. Combined with the results on the XRD patterns
and Raman spectra, the precipitation of In2S3 is completed
at the rst ~ 40 h, corresponding to the evolution of rst CP.
Consequently, the crystal phase of In2S3 is responsible for
the rst CP in the present glass. In addition, the XRD spectra recorded that the crystal phase of Sb2S3 which precipitated prior to GeS2 are in agreement with the sequence of
phase transformation in GeSbS glass ceramics.20,21 Therefore, the Sb2S3 crystal phase is related to the second CP
whereas the GeS2 crystal phase is corresponding to the transformation of the third CP.
Based on the above analysis, the crystallization of In2S3,
Sb2S3, and GeS2 phase in the glass matrix is schematically
illustrated in Fig. 10. For the 54GeS236Sb2S310In2S3 glass,
the glass network mainly consists of [SbS3] pyramids, [GeS4],
and [InS4] tetrahedra in a stochastic manner. According to
the cognition of the rst crystallization of In2S3 crystals and
the nanophase containing InIn bonds in the glass network,
[S3InSInS3] units are specied to present the possible conguration of In-related units to form In2S3 nuclei, which

Conclusion

In this work, we demonstrate that reproducible glass ceramics were obtained from 54GeS236Sb2S310In2S3 chalcogenide glass. The obtained glass-ceramics are highly transparent
in the mid-IR region. In addition, the crystallization behaviors of the In2S3, Sb2S3, and GeS2 phase have been systematically investigated by XRD, Raman, and DSC analysis. Based
on the results, the evolution of the three CPs for the crystallized bulk indicates that the precipitation of In2S3 and Sb2S3
crystal phase are responsible for the rst and the second CP,
and that of GeS2 phase for the third one in DSC curves. The
lower value of activation energy Ec and higher value of crystallization rate constant K for the rst CP illustrates the
much easier crystallization mechanism of In2S3. These results
allowed us to deduce that the [S3InSInS3] units are specied to possible nearest-neighbor conguration of In-related
units, which are demixed from the network backbone.

Acknowledgments
This work is partially supported by Natural Science Foundation of China
(Grant No. 61108057), Zhejiang Provincial Natural Science Foundation of
China (Grant Nos. R1101263 and Y4110322), Program for Innovative
Research Team in Ningbo City (Grant No. 2009B21007), Natural Science
Foundation of Ningbo City (Grant No. 2011A610091), Program for New Century Excellent Talents in University (Grant No. NCET-10-0976), and the outstanding Dissertation Engagement Foundation of Graduate School of Ningbo
University (Grant No. PY20100010).In addition, it was also sponsored by K.
C. Wong Magna Fund in Ningbo University.

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