Dynamics of mobile ions in single- and mixed-cation glasses

To study the ion dynamics of several inorganic glasses, including single- and mixed-cation glasses, we have determined conductivity spectra over wide ranges in frequency. In the case of the single-cation glasses, these spectra extend from a few hertz up to the terahertz regime. The spectra show a transition from their dc values to a dispersive regime where the conductivity increases continuously with frequency, tending towards a linear frequency dependence at sufficiently low temperatures. At high frequencies the dynamic conductivity is governed by vibrational contributions, whereas ionic hopping sequences determine the low-frequency part of the spectra. In an intermediate-frequency regime, both hopping and vibrational contributions contribute to the dynamic conductivity. The shape of the high-frequency conductivity spectra is discussed for various glasses. The low-frequency spectra are discussed in the framework of the concept of mismatch and relaxation.

For the mixed-cation glasses where spectra have been taken by impedance spectroscopy, we report on a new kind of mixed-alkali effect. In contrast to conductivity spectra of single-cation glasses which follow the time–temperature superposition principle, featuring a temperature-invariant shape, the shapes of the conductivity spectra of the mixed-alkali glasses studied here are found to change with temperature. To explain this effect, we suggest differently activated mobilities of the two different ionic species.