Abstract

Long-term physical ageing of chalcogenide glasses, which occurs over tens of years, ismuch less understood than the short-term ageing. With Se-rich underconstrainedAs30Se70 glass as a modelcomposition (consisting of Sen chains with n≤3 on average), a microscopic model is developed for this phenomenon by combining informationfrom differential scanning calorimetry, extended x-ray absorption fine structure, Raman, and77Se solid state nuclear magnetic resonance spectroscopies. The accompanying changes in theelectronic structure of these glasses are investigated by x-ray photoelectron spectroscopy.The data suggest ageing from cooperative relaxation, presumably involving bond switchingor reconfiguration of As–Se–Se–As fragments.

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