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Solid-state 31p MAS-NMR provides powerful insights into the local order of phosphorus selenide based glasses. Specifically, it allows a quantitative characterization of the melt equilibrium PSe3/2 + Se -> Se=PSe3/2 describing the stability of four-coordinate P atoms. Using this technique, the effect of isovalent substitution by As, and Te, and of other glass constituents Ge and TI on this equilibrium and on the quantitative phosphorus speciation is studied in detail.

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While the utility of solid state NMR to provide structural information in amorphous systems is well established in silicate and borate glasses, the systematic application of modern NMR techniques to non-oxidic systems has just begun. One of the central issues in these types of glasses is the question of the chemical bond distribution and the existence of short range order. The present study utilizes the selective measurement of homonuclear 31p.31P dipole-dipole couplings via spin echo decay to address this issue in the glass systems P-Se, PSe- Ge and CdGeAs2-xPx. The results indicate that the first two systems are characterized by a high degree of chemical ordering. The chemical bond distribution in CdGeAs2-xPx glasses is found to deviate considerably from that in the stoichiometry-analog crystalline materials.