The chemistry of melting oxynitride phosphate glasses

Abstract

Abstract Oxide glasses are the most commonly studied non-crystalline materials in Science and Technology, though compositions where part of the oxygen is replaced by other anions, e.g. fluoride, sulfide or nitride, have given rise to a good number of works and several key applications, from optics to ionic conductors. Oxynitride silicate or phosphate glasses stand out among all others because of their higher chemical and mechanical stability and their research continues particularly focused onto the development of solid electrolytes. In phosphate glasses, the easiest way of introducing nitrogen is by the remelting of the parent glass under a flow of ammonia, a method that allows the homogeneous nitridation of the bulk glass and which is governed by diffusion through the liquid-gas reaction between NH3 and the PO4 chemical groupings. After nitridation, two new structural units appear, the PO3N and PO2N2 ones, where nitrogen atoms can be bonded to either two or three neighboring phosphorus, thus increasing the bonding density of the glass network and resulting in a quantitative improvement of their properties. This short review will gather all important aspects of the synthesis of oxynitride phosphate glasses with emphasis on the influence of chemical composition and structure.