The thermally reversing window in ternary GexPxS1−2x glasses

Gex Px S1−2x glasses in the compositional range 0.05 x 0.19 have been synthesized and examined in temperature modulated differential scanning calorimetry (MDSC) and Raman scattering experiments. Trends in the nonreversing enthalpy Hnr(x) near Tg show the term to almost vanish in the 0.090(5) < x < 0.135(5) range, and to increase by an order of magnitude at x < 0.09, and at x > 0.135. In analogy to previous results on chalcogenide glasses, we identify compositions at x < 0.09 to be elastically floppy, those in the 0.090 < x < 0.135 range to be in the intermediate phase, and those at x > 0.135 to be stressed rigid. MDSC results also show that the Hnr term ages in the stressed-rigid and floppy phases but not in the intermediate phase. The intermediate phase is viewed to be a self-organized phase of a disordered network. It consists of at least four isostatically rigid local structures: cornersharing GeS4, edge-sharing GeS2, pyramidal P(S1/2)3 and quasi-tetrahedral S=P(S1/2)3 units for which evidence comes from Raman scattering. The latter method also shows the existence of P4S7 and P4S10 molecules in the glasses segregated from the backbone. These aspects of structure contribute to an intermediate phase that is significantly narrower in width than in the corresponding selenide glasses. (Some figures in this article are in colour only in the electronic version)