The structure of alkali germanophosphate glasses by Raman spectroscopy

Abstract

A series of alkali germanophosphate glasses ((R 2O) x (GeO 2:P 2O 5) 1− x where R=Na, K and Rb) with variable GeO 2:P 2O 5 ratios (8:1, 6:1, 4:1 and 2:1) have been investigated using Raman spectroscopy. The glass network may be treated as being made up of separate germanate and phosphate components. Addition of alkali cations indicates that the alkalis preferentially modify the phosphate part of the network. Network depolymerization occurs by formation of Q 2 and Q 1 PO 4 tetrahedra. At high Ge:P ratios the glasses exhibit a density anomaly. The anomaly is attributed to the formation of small three-membered GeO 4 rings. However, alkali cation size and mass are contributing factors to the shape of the density anomaly in the K 2O and Rb 2O containing glasses. Depolymerization of the 2:1 alkali germanophosphate glasses is predominantly by formation of Q 2 PO 4 tetrahedra. At low Ge:P ratios (2:1) density trends are linear. No ring transition is observed in these glasses. Furthermore, the presence of [5]Ge cannot be ruled out, but if present, does not play a major role in generating a ‘germanate anomaly’.