Correlation of the glass transition temperature and average energetic connectivity in network chalcogenide glasses

: pp. 32-37
Lviv Polytechnic National University
Vlokh Institute of Physical Optics; R&D Enterprise “Electron-Carat"; Jan Długosz University in Częstochowa

A correlation ratio between a glass transition temperature Tg and average bond energy E (obtained for chalcogenide glasses in L. Tichý & H. Tichá [J. Non-Cryst. Solids, 189, 1995]) was critically analyzed in this paper. As a result, this ratio was shown to have been obtained using incorrect calculations of the average bond energy E through inappropriate application of different averaging procedures for different terms of this parameter and, therefore, it cannot be used in practice. A mathematical algorithm for calculating the average energy bonding was adjusted by the atom-averaging procedure for the both energy of the “network part of a matrix” Ec (energy of heteropolar bonds) and energy of a "residual matrix" Erm (energy of homopolar bonds), as well as considering the impossibility of forming covalent chemical bonds between cations of different type. It was stated that the linear ratio between the glass transition temperature Tg and energy bonding E can be obtained by the ratio Tg ≅ 326∙(E – 0.94)  and this claim was proved for 145 typical representatives of the covalent-bonded network chalcogenide glasses (Ge-As-S/Se-type systems).

  1. C.A. Angell, et al., "Relaxation in glassforming liquids and amorphous solids", J. Appl. Phys., vol. 88, pp. 3113-3157, 2000.
  2. D. Cangialosi, "Dynamics and thermodynamics of polymer glasses", J. Phys.: Condens. Matter., vol. 26, pp. 153101-1-19, 2014.
  3. K. Tanaka and K. Shimakawa, Amorphous Chalcogenide Semiconductors and Related Materials, New York-Dordrecht-Heidelberg-London: Springer, 2011.
  4. A. Feltz, Amorphous Inorganic Materials and Glasses, Weinheim-New York-Basel-Cambridge-Tokyo: VCH Publ., Inc., 1993.
  5. J-L. Adam and X. Zhang (Eds.), Chalcogenide Glasses: Preparation, Properties and Application, Philadelphia-New Delhi: Woodhead Publ. ser. in Electronic and Optical Mater., 2013.
  6. J. Bicerano and S.R. Ovshinsky, "Chemical bond approach to the structures of chalcogenide glasses with reversible switching properties", J. Non-Cryst. Solids, vol. 74, pp. 75-84, 1985.
  7. K. Tanaka, "Glass transition of covalent glasses", Solid State Commun., vol. 54, pp. 867-869, 1985.
  8. A. Feltz, H. Aust, and A. Blayer, "Glass formation and properties of chalcogenide systems XXVI: permittivity and the structure of glasses AsxSel-x and GexSel-x", J. Non-Cryst. Solids, vol. 55, pp. 179-190, 1983.
  9. P. Chen, P. Boolchand, and D.G. Georgiev, "Long term aging of selenide glasses: evidence of sub-Tg endotherms and pre-Tg exotherms", J. Phys.: Condens. Matter., vol. 22, pp. 065104-1-16, 2010.
  10. G. Yang, et al., "Correlation between structure and physical properties of chalcogenide glasses in the AsxSe1−x system", Phys. Rev. B, vol. 82, pp. 195206-1-8, 2010.
  11. M. Shpotyuk, et al., "On the glass transition temperature Tg against molar volume Vm plotting in arsenoselenide glasses", J. Non-Cryst. Solids, vol. 528, pp. 119758-1-6, 2020.
  12. E. Zhu, et al., "Correlation between thermo-mechanical properties and network structure in GexS100–x chalcogenide glasses", J. Non-Cryst. Solids: X, vol. 1, pp. 100015-1-7, 2019.
  13. P. Boolchand, X. Feng, and W.J. Bresser, "Rigidity transitions in binary Ge–Se glasses and the intermediate phase", J. Non-Cryst. Solids, vol. 293-295, pp. 348-356, 2001.
  14.  L. Tichý and H. Tichá, "Covalent bond approach to the glass-transition temperature of chalcogenide glasses", J. Non-Cryst. Solids, vol. 189, pp. 141-146, 1995.
  15. A.V. Nidhi, V. Modgil, and V.S. Rangra, "The effect of compositional variation on physical properties of Te9Se72Ge19-xSbx (x = 8, 9, 10, 11, 12) glassy material", New J. Glass Ceram., vol. 3, pp. 91-98, 2013.
  16. A.V. Nidhi, V. Modgil, and V.S. Rangra, "Structural characterization of Te9Se72Ge19-xSbx (8£x£12) glass using far-infrared spectra", Chalcogen. Lett., vol. 11, pp. 365-372, 2014.
  17. J. Lonergan, et al., "Modeling and experimental determination of physical properties of GexGaySe1-x-y chalcogenide glasses I: Structure and mechanical properties", J. Non-Cryst. Solids, vol. 510, pp. 192-199, 2019.
  18. J. Lonergan, et al., "Modeling and experimental determination of physical properties of GexGaySe1-x-y chalcogenide glasses II: Optical and thermal properties", J. Non-Cryst. Solids, vol. 511, pp. 115-124, 2019.
  19. N. Chandel, and N. Mehta, "Analysis of physicochemical properties in covalent network chalcogenide glasses (ChGs): critical review of theoretical modeling of chemical bond approach", SN Appl. Sci., vol. 1, pp. 657-1-14, 2019.
  20. A.I. Isayev, et al., "Structure and optical properties of chalcogenide glassy semiconductors of the As-Ge-Se system", Semiconductors, vol. 53, pp. 1500-1506, 2019.
  21. R.W. Fawcett, C.N.J.Wagner, and G.S.Cargill III, "Radial distribution studies of amorphous GexSe1-x alloy films", J. Non-Cryst. Solids, vol. 8-10, pp. 369-375, 1972.
  22. G.A.N. Connel, and G. Lucovsky, "Structural models for amorphous semiconductors and insulators", J. Non-Cryst. Solids, vol. 31, pp. 123-155, 1978.
  23. L. Pauling, The Nature of the Chemical Bond, New York: Cornell Univ. Press, 1960.
  24. T. Qu, and P. Boolchand, "Shift in elastic phase boundaries due to nanoscale phase separation in network glasses: the case of GexAsxS1-2x", Phil. Mag., vol. 85, pp. 875-884, 2005.
  25. R.P. Wang, et al., "Raman spectra of GexAsySe1-x-y glasses", J. Appl. Phys., vol. 106, pp. 043520-1-4, 2009.
  26. Y. Wang, P. Boolchand, and M. Micoulaut, "Glass structure, rigidity transitions and the intermediate phase in Ge-As-Se ternary", Europhys. Lett., vol. 52, no. 6, pp. 633-639, 2000.
  27. J.Z. Liu, and P.C. Taylor, "The formal valence shell model for structure of amorphous semiconductors", J. Non-Cryst. Solids, vol. 114, pp. 25-30, 1989.