Evidence of network demixing in GeS2–Ga2S3 chalcogenide glasses: A phase transformation study

The information of phase transformation is attained by in situ XRD experiments leading to the knowledge of topological threshold in GeS2–Ga2S3 glasses. The turning point of phase transformation behavior is demonstrated to be glasses containing 14–15 mol% Ga2S3. To interpret it a network demixing model is further improved and proposed for the structure of these ternary or quasi-binary chalcogenide glasses. For the nearest-neighbor coordination environment of glass with a transitional composition of 85.7 mol% (6/7) GeS2·14.3 mol% (1/7) Ga2S3, six-coordinated [S3Ga–X–GaS3] units (X=S or None) are well isolated by the [GeS4] structures, which contributes to the decreasing of precipitation of Ga2S3 crystals in (100−x)GeS2–xGa2S3 (x≤14.3) glasses corresponding to the experimental evidence of the phase transformation behavior. This scenario of intermediate-range structural order, firstly, includes the arrangement of structural units which is consistent with and provides an atomistic explanation of the compositional evolution of phase transformation behavior in these glasses.