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J. Am. Ceram. Soc., 95 [4] 1320–1325 (2012) DOI: 10.1111/j.1551-2916.2012.05117.x © 2012 The American Ceramic Society

Mechanical Properties and Crystallization Behavior of GeS 2 Sb 2 S 3 In 2 S 3 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

54GeS 2 36Sb 2 S 3 10In 2 S 3 glass-ceramics were prepared by heat-treating the base glass above T g for different durations. The results of Raman spectra and XRD patterns show that the first precipitated crystals during the heat treatment are In 2 S 3 and the crystallization of the Sb 2 S 3 and GeS 2 subsequently occurs. Bulk samples heat-treated at 295°C for different heat- ing 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.

Introduction

  • C 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, opti-

cal fibers for chemical and biological sensing, optical modu-

lator and optical communications.

1 3

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 mold- ing. 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 proper- ties 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 chal- lenge 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.,

9

GeS 2 Ga 2 S 3 CsCl, 8 GeSe 2 Sb 2 Se 3

RbI and GeS 2 Sb 2 S 3 CsCl 10 have been systematically investigated. These relatively suitable systems are based on glasses of the GeS 2 Sb 2 S 3 or GeS 2 Ga 2 S 3 , combined with metallic halide in which the size of the metallic ion is large enough to be used as the compatible modifier cations. Previ- ous studies have been conducted in using CsCl, CsBr, CsI,

RbI, CuI, PbI 2 . 9 11 Unfortunately, controllable and repro- ducible crystals growth in the above mentioned chalcogenide glassesstill suffer from the difficulty to control the nucleation of nanometer size and species. In addition, the introduction of relatively high-halide content leads to poor chemical dura-

J. Heo—contributing 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

bility. In this case, metallic halide is substituted by a similar large-metallic sulfide In 2 S 3 ,which plays a role in the forma- tion of the glassy framework other than modifier. Mean- while, the element In located at the same main group and the next period of the elemental period table as Ga, In-con- tained chalcogenide glasses should have similar superior properties, such as high solubility of rare earth ions. Further- more, the substitution of Ga for heavier metal In would increase the refractive index, leading to high quantum effi- ciencies for rare earth ions transition in chalcogenide glass. 12 In this work, we focus on the crystallization behavior of glasses based on the GeS 2 In 2 S 3 Sb 2 S 3 system which has been well-investigated in our previous research. 13 As crystalli- zation of a chalcogenide glass is a highly exothermic process, differential 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 GeS 2 In 2 S 3 Sb 2 S 3 glass- ceramics are presented and discussed. Based on the DSC, X- Ray diffraction (XRD), and Raman results, the crystalliza- tion mechanism for three crystal phases of In 2 S 3 , Sb 2 S 3 , and GeS 2 is elucidated in detail.

II.

Experimental

Bulk glass with a composition of 54GeS 2 36Sb 2 S 3 10In 2 S 3 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 intro- duced into a silica tube, which was sealed under a vacuum of ~10 3 Pa and then it was reacted at 950°C for 13 h in a rocking furnace. Tube containing the melt was moved out and subsequently quenched in cold water. The reference polycrystalline In 2 S 3 sample was also prepared with very slow cooling rate in a vacuum silica tube. The obtained glass rod was annealed below glass transition temperature (T g ) for 5 h to minimize inner stress. Specimens were cut into disks of ~10 mm in diameter and 1.5 mm in thickness, and pol- ished both sides for optical measurements. The crystallization of the as-prepared glass was conducted by heating at 2°C/ min to a designed temperature (T HT ), holding for various durations, and then cooling slowly to room temperature. The glass transition temperatures (T g ) and crystallization temperatures (T x ) of as-prepared glasses were determined by DSC at a heating rate of 10°C/min with a temperature accu- racy of ± 1°C (TA Q2000). To study the crystallization behavior, bulk samples heat-treated at T HT (T g + 20°C) for different durations were placed in hermetic aluminum pans and heated from room temperature until crystallization com- pleted. The densities were measured, according to Archime- des principle using de-ionized water as an immersion liquid. Transmission spectra were obtained with a Lambda 950 UV- VIS-NIR spectrophotometer (Perkin-Elmer, Inc., Waltham, MA) in visible and near-IR spectral region and Nicolet 381

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GeS 2 -Sb 2 S 3 -In 2 S 3 Chalcogenide Glass and Glass Ceramics

1321

Fourier Infrared spectrophotometer (Thermo Nicolet Cor- poration, 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 diffractometer (Voltage 36 kV, current 20 mA, Cu Ka; Bruker AXS, Madison, WI). Raman spectra were conducted at room temperature using back (180°) scat- tering configuration 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 microind- enter (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 measure- ment on 10 indentations per sample.

III.

Results and Discussion

The DSC curve of the 54GeS 2 36Sb 2 S 3 10In 2 S 3 glass at a heating rate of 10°C/min is shown in Fig. 1. An obvious exo- thermic peak can be observed, and the characteristic temper- atures of T g and T x 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 Gauss- ian functions with three peaks ranging from 370°C to 415°C, suggesting different kinds of crystallization. With the knowl-

edge of thermal results and previous

study, 14,15 a fairly low

T HT of 295°C (T g + 20°C) was chosen as heat-treated tem- perature for crystallization process. The base glasses were placed in a ventilated furnace at 295°C for different dura- tions 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 well- polished samples. As shown in Fig. 2, the marks and cracks made by indentation were observed with an optical micro- scope. 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-off edge of short

April 2012 GeS -Sb S -In S Chalcogenide Glass and Glass Ceramics 1321 Fourier Infrared spectrophotometer

Fig. 1. DSC curve for bulk glass of 54GeS 2 36Sb 2 S 3 10In 2 S 3 at a heating rate of 10°C/min. The exothermic peak is fitted by Gaussian Functions in the inset.

(a) (b) (c) (d)
(a)
(b)
(c)
(d)

Fig. 2. Optical microscope pictures of the different samples after Vickers indentation (a) Base glass, glasses crystallized at 295°C for (b) 20 h, (c) 40 h, and (d) 60 h, respectively.

Table I.

Some Physical and Mechanical Properties of the

54GeS 2 36Sb 2 S 3 10In 2 S 3 Glass and Glass-Ceramics

Samples

Cut-off edge (±1 nm)

Density, ρ (±0.002 g·cm 3 )

Hardness, H v (±2 Kg·mm 2 )

Base

637

3.595

177

20

h

643

3.671

175

40

h

825

3.794

180

60

h

1027

3.790

186

90

h

1273

3.732

194

120 h

1608

3.867

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 transmit- tance 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 trans- parency 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 dif- fusion to shift the cut-off edge of short wavelength, and no notable change of size is observed in the range of 60 h. How- ever, samples heat-treated for 120 h at 295°C show a dis- tinctly decrease in the maximum of transmission from 65% to 50%. This phenomenon shows the presence of large crys- tals 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 diffraction is carried out on the polycrystalline In 2 S 3 and the 54GeS 2 36Sb 2 S 3 10In 2 S 3 base glass heat-treated for different durations. Figure 5 presents the XRD patterns collected at 295°C during 120 h on powder samples. A three-step crystal- lization mechanism can be clearly recognized from these XRD patterns. During the first step, which ends after ~ 20 h of annealing at 295°C, no obvious diffusion signature is observed and the matrix remains mostly amorphous. How- ever, after about 40 h, several peaks (2h = 27°, 33°, 43° and 47°) appear and then grow slowly and continuously. The

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Vol. 95, No. 4

(a)
(a)
(b)
(b)

Fig. 3. Transmission curves of 54GeS 2 36Sb 2 S 3 10In 2 S 3 glass and glasses ceramics heat-treated at 295°C for different 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)
(a)
(b)

Fig. 4. SEM images for samples crystallized at 295°C for different durations: (a) 40 h9100 000, and (b) 60 h9100 000, respectively.

1322 Journal of the American Ceramic Society—Ying et al. Vol. 95, No. 4 (a) (b) Fig.

Fig. 5. XRD patterns of In 2 S 3 polycrystalline, 54GeS 2 36Sb 2 S 3 10In 2 S 3 base glass and glass ceramics obtained by heat-treatment at 295°C for different durations, respectively.

1322 Journal of the American Ceramic Society—Ying et al. Vol. 95, No. 4 (a) (b) Fig.

Fig. 6. Raman spectra of In 2 S 3 polycrystalline, 54GeS 2 36Sb 2 S 3 10In 2 S 3 glass and glasses ceramics heat-treated at 295°C for different durations.

positions of these peaks are in good agreement with the In 2 S 3 indexation (JCPDS card no. 25-0390) and their broad- ness confirms 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 Sb 2 S 3 (JCPDS card no. 42-1393). In addition, the GeS 2 phase (2h = 30°, 31°) is also present in the 60 h heat-treated sam- ple. Therefore, the species of crystal phases are roughly

revealed by the XRD patterns. In addition, normalized Raman spectra of the glass ceram-

ics and In 2 S 3 polycrystalline are presented in Fig. 6, further confirming that the crystals of In 2 S 3 and Sb 2 S 3 were precipi- tated. With the increasing of the heat-treatment durations, the bands around 140 and 310 cm 1 which is attributed to the vibrations of [S 3 InInS 3 ] ethane-like units and [InS 4 ] tet- rahedra 17 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 In 2 S 3 crystal gradually dominates in the crystallized samples. In addition, the main Raman peak at 300 cm 1 corresponding

April 2012

GeS 2 -Sb 2 S 3 -In 2 S 3 Chalcogenide Glass and Glass Ceramics

1323

to the vibration of the [Sb 2 S 3 ] pyramid unit is also sharpened after 60 h heat-treatment, suggesting the Sb 2 S 3 crystals have appeared during the crystallization process. Regretfully, we did not observe the characteristic vibration band of GeS 2 crystals in Fig. 6, which may be due to the Raman spectra of a small amount of GeS 2 crystals undistinguishable from that of GeS 2 glass. 18 Based on the above-mentioned analysis, the species and sequence of crystallization are coincident to the XRD results. IR-transmitting 54GeS 2 36Sb 2 S 3 10In 2 S 3 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 different crystallization mechanism. Furthermore, as shown in Figs. 5 and 6, three crystal phases were precipi- tated in the glass matrix, successively. Therefore, it can be supposed that these three CPs are originated from the precip- itation of In 2 S 3 , Sb 2 S 3 , and GeS 2 crystals, respectively. Despite the good knowledge on the distinct phase trans- formation for the three CPs achieved, the reasons mainly for the crystallization of In 2 S 3 crystals in 54GeS 2 36Sb 2 S 3 10In 2 S 3 glass at 295°C 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 stud- ied glass. In Table II are listed the characteristic tempera- tures of the studied chalcogenide glass at an increased heating rate, b = 1, 5, 10, 15 and 20°C/min. The crystalliza- tion behavior of the three glass phases can be understood by the following kinetic parameters: the activation energy for the crystallization E c , the frequency factor K 0 , and the crys-

April 2012 GeS -Sb S -In S Chalcogenide Glass and Glass Ceramics 1323 to the vibration

Fig. 7. DSC curves of the 54GeS 2 36Sb 2 S 3 10In 2 S 3 glasses heat- treated at 295°C for different heating rates from 1°C/min to 20°C/ min.

Table II.

Characteristic Temperatures of T g , T x and T p for 54GeS 2 36Sb 2 S 3 10In 2 S 3 Glass

Heating rates, b ( o C/min)

T g (± 1°C)

T x (± 1°C)

  • 1 265

339

  • 5 281

370

  • 10 283

377

  • 15 284

384

  • 20 286

389

tallization rate constant K. To obtain the kinetic parameters, the kinetic model of Bansal and Hyatt 19 is used and expressed as follows:

ln

b

T 2

c

¼

E c

RT c

þ ln

RK 0

E c

(1)

Where R is the ideal gas constant (8.314 J·mol 1 K 1 ), and T c is the characteristic temperature in Kelvin, respectively. Plots of lnðb=T 2 Þ against 1000/T c for the chalcogenide glass give a linear behavior as shown in Fig. 8. Consequently, the E c and K 0 values are calculated from the slopes of these lines corresponding to E c /R, listed in Table III. Nevertheless, the parameters of E c and K 0 are still not sufficient to understand why the In 2 S 3 crystal phase is much easier to be fully crystal-

c

Fig. 8. Plots of lnðb=T 2 Þ vs (1000/T c ). c
Fig. 8.
Plots of lnðb=T 2 Þ vs (1000/T c ).
c

Table III.

Crystallization Kinetics Parameters for 54GeS 2 36Sb 2 S 3 10In 2 S 3 Glass

Crystallization peaks

E c (kJ·mol 1 )

K 0 (s 1 )

K 295°C (s 1 )

First (In 2 S 3 )

2

152.30

6.8 9 10 12

3.49 9 10 3

Second (Sb S 3

)

155.34

1.1 9 10 12

2.68 9 10 3

Third (GeS 2 )

160.84

0.5 9 10 12

2.63 9 10 3

April 2012 GeS -Sb S -In S Chalcogenide Glass and Glass Ceramics 1323 to the vibration

Fig. 9. DSC curves of the 54GeS 2 36Sb 2 S 3 10In 2 S 3 glasses heat- treated at 295°C for different durations.

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Vol. 95, No. 4

(a) (b) (c)
(a)
(b)
(c)

Fig. 10. Schematic illustration of In 2 S 3 , Sb 2 S 3 ,and GeS 2 crystallization processes in a glass matrix: (a) precursor glass, (b) In 2 S 3 nuclei formation, and (c) glass ceramics.

lized than Sb 2 S 3 and GeS 2 at 295°C. Hence, the crystalliza- tion 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 E c and K 0 , and mathematically expressed as:

finally grow into In 2 S 3 crystals. Similar crystallization process for the formation of Ga 2 S 3 nanocrystals in the GeS 2 Ga 2 S 3 glass has been reported by Lin et al. 22 With the increasing of heat-treatment durations, the Sb 2 S 3 and GeS 2 crystal is pre- cipitated subsequently.

IV.

Conclusion

K ¼ K 0 exp

E c

RT

(2)

In this work, we demonstrate that reproducible glass ceram- ics were obtained from 54GeS 2 36Sb 2 S 3 10In 2 S 3 chalcogen- ide glass. The obtained glass-ceramics are highly transparent in the mid-IR region. In addition, the crystallization behav- iors of the In 2 S 3 , Sb 2 S 3 , and GeS 2 phase have been systemati- cally investigated by XRD, Raman, and DSC analysis. Based on the results, the evolution of the three CPs for the crystal- lized bulk indicates that the precipitation of In 2 S 3 and Sb 2 S 3 crystal phase are responsible for the first and the second CP, and that of GeS 2 phase for the third one in DSC curves. The lower value of activation energy E c and higher value of crys- tallization rate constant K for the first CP illustrates the much easier crystallization mechanism of In 2 S 3 . These results allowed us to deduce that the [S 3 InSInS 3 ] units are speci- fied to possible nearest-neighbor configuration 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 Cen- tury Excellent Talents in University (Grant No. NCET-10-0976), and the out- standing 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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These K values for the In 2 S 3 , Sb 2 S 3 , and GeS 2 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 E c and K 0 are used from Table III, respectively. The K value for the In 2 S 3 phase is about two times larger than that of the Sb 2 S 3 and GeS 2 phase, suggesting a much easier crystallization mechanism of In 2 S 3 phase. Thus, it is not surprising that the In 2 S 3 crystals are easily precipitated by the heat treatments at 295°C. To study the crystallization behavior of these three phases, DSC curves of base glass and glass ceramics which were heat-treated at 295°C for different durations were recorded as shown in Fig. 9. After heat-treatment at 295°C 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 crystal- lization. Meanwhile, the height of the first 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 crys- tallization of the related phase. Moreover, the third CP behaves in a similar way by further increasing the heat-treat- ment time. Combined with the results on the XRD patterns and Raman spectra, the precipitation of In 2 S 3 is completed at the first ~ 40 h, corresponding to the evolution of first CP. Consequently, the crystal phase of In 2 S 3 is responsible for the first CP in the present glass. In addition, the XRD spec- tra recorded that the crystal phase of Sb 2 S 3 which precipi- tated prior to GeS 2 are in agreement with the sequence of

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20,21

fore, the Sb 2 S 3 crystal phase is related to the second CP whereas the GeS 2 crystal phase is corresponding to the trans- formation of the third CP. Based on the above analysis, the crystallization of In 2 S 3 , Sb 2 S 3 , and GeS 2 phase in the glass matrix is schematically illustrated in Fig. 10. For the 54GeS 2 36Sb 2 S 3 10In 2 S 3 glass,

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