Evolution of glass properties during a substitution of S by Se in Ge28Sb12S60 −xSex glass network

article i nfo In this paper, a detailed study to examine the influence of chalcogen S/Se mole % in the Ge28Sb12S60�xSex glass system, with x=0, 15, 30, 45 and 60, is presented that provides insight into the effect of chalcogen con- tent on the glass network and properties. Specifically, we report results of a systematic study to evaluate the relationship between compositional variation, glass properties and dominant bonding configurations. These materials are important to applications in optics manufacturing where correlation of physical and optical properties is required to predict fabrication behavior and ultimate material performance. It has been found that the dominant bonds in the glass system change upon reaching a specific molar ratio (percentage, %) of chalcogen substitution, between 30bxb45 mol%, changing from Ge―Se to Sb―Se bonds as the dominant bond type. This singularity has been observed using micro-Raman spectroscopy and X-ray photoelectron spectroscopy. This effect of the dominant bond configurational change was also shown to impart changes in important physical properties including micro-hardness, thermal properties, and the glass' viscometric be- havior. Results indicate that the observed dominant bond change was responsible for a constant value in the evolution of both the micro-hardness and calorimetric glass transition temperature. The viscosity was also af- fected by the change in dominant bond type, breaking the monotony of the viscosity evolution during the S substitution, due to the total strength of the vitreous system which does not linearly increase.

[1]  A. Odajima,et al.  X-Ray Photoelectron Spectroscopy of Ag- and Cu-Doped Amorphous As2Se3 and GeSe2 , 1982 .

[2]  Jean-Luc Adam,et al.  Optimization of chalcogenide glass in the As–Se–S system for automotive applications , 2009 .

[3]  P. Němec,et al.  Structure and properties of the pure and Pr3+-doped Ge25Ga5Se70 and Ge30Ga5Se65 glasses , 2000 .

[4]  S. El-Sayed.  Far-infrared studies of the amorphous SbxGe28−xSe72 glassy semiconductor , 2003 .

[5]  Steve W. Martin,et al.  Effect of the substitution of S for Se on the structure of the glasses in the system Ge0.23Sb0.07S0.70−xSex , 2005 .

[6]  D. R. Goyal,et al.  Far-infrared absorption in amorphous Sb15GexSe85 - x glasses , 1995 .

[7]  G. Lucovsky,et al.  Structural interpretation of the infrared and Raman spectra of glasses in the alloy systemGe1−xSx , 1974 .

[8]  S. Mahadevan,et al.  Heat capacities of GeSbSe glasses , 1981 .

[9]  L. Zan,et al.  New chalcohalide glasses from the Sb2S3-MXn system , 1995 .

[10]  S. Mahadevan,et al.  Density and microhardness of GeSbSe glasses , 1981 .

[11]  Tatsuo Shimizu,et al.  Study on local structure in amorphous SbS films by Raman scattering , 1983 .

[12]  A. Singh,et al.  Elastic properties of GeSbSe glasses , 1983 .

[13]  J. Oswald,et al.  Synthesis and optical properties of the Ge–Sb–S:PrCl3 glass system , 1999 .

[14]  Nathan Carlie,et al.  Correlation between the nonlinear refractive index and structure of germanium-based chalcogenide glasses , 2007 .

[15]  J. C. Phillips,et al.  Topology of covalent non-crystalline solids I: Short-range order in chalcogenide alloys , 1979 .

[16]  M. Couzi,et al.  Effect of the substitution of S for Se on the structure and non-linear optical properties of the glasses in the system Ge0.18Ga0.05Sb0.07S0.70- xSex , 2006 .

[17]  E. Černošková,et al.  Thermomechanical and structural characterization of GeSe2–Sb2Se3–ZnSe glasses , 2003 .

[18]  G. Chryssikos,et al.  Structure and Optical Conductivity of Silver Thiogermanate Glasses , 1994 .

[19]  Sugai.  Stochastic random network model in Ge and Si chalcogenide glasses. , 1987, Physical review. B, Condensed matter.