A study of structure, electrical and optical properties of some vanadate glasses
Studies of semiconducting glasses have become of great interest in recent years because of their importance in the theory of solid state physics and in their applicability to electronic devices. Of these classes of materials the transition metal oxide glasses are much the most thoroughly studied. In these glasses the transition metal oxide e. g. V205-TiO2-MoO39 WO3, Cu0 is a major constituent i.e > 50 mol%. We start this work with a discussion about a critical review of the history, formation and modern theory of non-crystalline semiconductors in general and glassy state in particular. The aim of the experimental work in present study is to check the validity of the theories and models proposed so far to explain the origin and the nature of the charge carriers, structure, electrical and optical properties of some transition metal oxide glasses based on vanadium pentoxide. For this purpose series of binary V205-P205 glass samples containing 50 to 90 mol% V205 as well as ternary V2015-P205-Te02 glasses containing 60 mol% V2051 (40-x) mol% P205 and x mol% Te02 in which x varies from 5 to 35 were prepared by normal cooling from the melt. It was found that the glass forming region of the system under consideration is fairly large and in binary V205-P205 systems, glass with up to 95 moll V205 could be prepared. Density measurements indicate that in binary V205 - P205 glasses the density increases linearly with increasing V205 content and in ternary V205 - P205 - TeO2 systems density increases with increasing Te02 content. It was also found that the density of both systems are affected by annealing temperature. Electron spin resonance (E.S.R.) studies show that in vanadate glasses, the vanadium exists in more than one valency state mainly V5+ and V4+ of which V4+ is paramagnetic and detectable by E. S. R. This could be taken as some evidence of a hopping conduction mechanism in vanadate glasses and conduction is due to transfer of charge form V4+ to V5+ ions and this is discussed in the terms of small polaron. It is found that the conduction in these glasses is Ohmic up to a field of the order of 4x 105 Vcm-1 with an activation energy range from 0.31 to 0.48 e.V depending on composition and independent of temperatures in our range of temperature (above room temperature). Above this field conduction becomes non-Ohmic which is found to be due to lowering the potential barrier of the carriers at high electric field as was predicted by Poole and Frenkel. Memory switching is observed in thin blown film samples of both binary and ternary glass systems, which is associated with field-induced crystallization of a localized region and formation of conductive channel in the switched area due to self heating effect. In other words the conducting zone consists of VO2 crystals which possess more metal-like conductivity. Infra-red absorption spectra of these glasses revealed that some of the absorption bands of glasses and crystalline V205 are similar which is some evidence that the vanadium ions exists in six-fold co-ordination in disordered glassy systems as well as ordered crystalline V205. The fundamental absorption edge of these glasses occurs in the short wave length region of the visible and is dependent on composition, and the fundamental absorption arises form direct forbidden transitions and occurs at a photon energy of about 1.9-2.6 e.V depending on composition. The absorption edge in these glasses is found to be of the same order of magnitude as that in crystalline V205.