X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and density study of ternary chalcogenide glasses based on Ge-Se and Ge-S

Abstract

Glasses of the systems Ge-Se-X (X = Ga, Sn, Bi, Sb), Ge-S-Y (Y = Ag, Ga, Sn, Bi) and Se-S have been examined using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), density and differential scanning calorimetry (DSC). Two of the compositions, GeSe2 and (GeSe2)92Ga8, have also been examined by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES). The emphasis of the XPS measurements was on the changes in the binding energies with composition of the core peaks of the glasses, and on the plasmon energy losses from the L3M4,5M4,5 Auger lines of Se and Ge. It was found that there were small shifts in the binding energies of the core peaks on substitution but the plasmon energy changed markedly with composition. For the XRD measurements, the focus was on two features : (a) to ensure that the samples prepared were truely amorphous and (b) to confirm the presence of the first sharp diffraction peak (FSDP) on the interference functions. The density measurements showed that the addition of the third element (X or Y) to the binary resulted in an increase in the relative density except for one system, Ge-Se-Sn, which showed the opposite behaviour. The DSC measurements showed that the addition of the third element to the binary resulted in a decrease in the glass transition temperatures. The EXAFS and XANES measurements of GeSe2 and (GeSe2)92Ga8 glasses showed that there was very little change in the local order around the Ge atom in GeSe2 glass with increase in temperature and that the local order around the Ge atom changes on alloying GeSe2 with Ga. Correlations between parameters and measured properties of the ternary alloys have been investigated. It has been found that the parameter <m>, the average coordination number, correlates well with certain structural properties but badly with others. Suggestions are made for an alternative to <m>.