Topological Origin of Fragility, Network Adaptation, and Rigidity and Stress Transitions in Especially Homogenized Nonstoichiometric Binary GexS100–x Glasses

Abstract

Binary GexS100-x glasses reveal a richness of elastic and chemical phase transitions driven by network topology. With increasing Ge content (x), well-defined rigidity at xc(1) = 19.3(5)% and a stress transition at xc(2) = 24.9(5)% are observed in Raman scattering. In modulated DSC measurements, the nonreversing enthalpy of relaxation at Tg reveals a square-well-like minimum (reversibility window) with window walls that coincide with the two elastic phase transitions. Molar volumes show a trapezoidal-like minimum (volumetric window) with edges that nearly coincide with the reversibility window. These optical, thermal, and volumetric results are consistent with an isostatically rigid elastic phase (intermediate phase, IP) present between the rigidity (xc(1)) and stress (xc(2)) transitions. Complex Cp measurements show melt fragility index, m(x) to also show a global minimum in the reversibility window with m < 20, underscoring that melt dynamics encode the elastic behavior of the glass formed at Tg. The strong nature of melts formed in the IP has an important practical consequence; they lead to slow homogenization (over days not hours) of nonstoichiometric Ge-S batch compositions reacted at high temperatures. Homogenization of chalcogenide melts/glasses over a scale of a few micrometers is a prerequisite to observe the intrinsic physical properties of these materials.