Charge carrier concentration and mobility in alkali silicates

Abstract

The respective contributions of the charge carrier concentration and mobility to the ionic conductivity in glasses remain an open question. In the present work we calculate these two parameters from conductivity data as a function of temperature below and above the glass transition temperature, Tg. The basic hypothesis assumes that ionic displacement results from the migration of cationic pairs formed by a partial dissociation, which is a temperature-activated process. Below Tg their migration would follow a temperature-activated mechanism, while a free volume mechanism prevails above this temperature, leading to a deviation from the Arrhenius behavior. Expressions are formulated for the variation in ionic conductivity as a function of temperature in the supercooled and glassy states. Fitting the experimental data with the proposed expressions allows for the determination of characteristic parameters such as the charge carrier formation and migration enthalpies. Based on these values, it is then possible to calculate the charge carrier concentration and mobility in the entire temperature range. At room temperature, the mobility of effective charge carriers is estimated close to 104 cm2s-1V-1 for alkali disilicates glasses under study, while the ratio between the number of effective charge carriers and the total number of alkali cations is estimated to be 10-8 to 10-10, comparable to the concentration of intrinsic defects in an ionic crystal or dissociated species from a weak electrolyte solution