Evidence of network demixing in GeS{sub 2}-Ga{sub 2}S{sub 3} 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 GeS{sub 2}-Ga{sub 2}S{sub 3} glasses. The turning point of phase transformation behavior is demonstrated to be glasses containing 14-15 mol% Ga{sub 2}S{sub 3}. 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) GeS{sub 2}.14.3 mol% (1/7) Ga{sub 2}S{sub 3}, six-coordinated [S{sub 3}Ga-X-GaS{sub 3}] units (X=S or None) are well isolated by the [GeS{sub 4}] structures, which contributes to the decreasing of precipitation of Ga{sub 2}S{sub 3} crystals in (100-x)GeS{sub 2}-xGa{sub 2}S{sub 3} (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. -- Graphical abstract: Synopsis: network demixing in GeS{sub 2}-Ga{sub 2}S{sub 3} chalcogenide glasses. Display Omitted Highlights: {yields} Phase transformation in GeS{sub 2}-Ga{sub 2}S{sub 3} glasses. {yields} Turning point of the phase transformation behavior. {yields} Medium-range order structure of chalcogenide glasses. {yields} Network demixing model for GeS{sub 2}-Ga{sub 2}S{sub 3} glasses.