Synthesis and characterization of potassium, rubidium, and cesium thiogermanate glasses

By Oshida, Yoshiki; Sellers, Cory B.; Mirza, Kawther & Farzin-Nia, Farrokh
Published in Journal of Non-Crystalline Solids NULL 2004

Abstract

Glass-forming regions were investigated for the binary xM2S + (1 - x)GeS2 (M=K, Rb, Cs) systems. Glasses were prepared from 0⩽x⩽0.20 mole fraction alkali sulfide using a novel preparation route involving the decomposition of the alkali hydrosulfides in situ. At higher alkali concentrations near x=0.33, the glass-forming regions are limited by the readily formed adamantane-like M4Ge4S10 crystals. Structural characterization of the glasses and polycrystals for x⩽0.33 were performed using Raman scattering and IR absorption. Terminal Ge–S- vibrational modes, observed between 473 and 479 cm-1, increased in intensity and decreased in frequency with increasing alkali modifier content. Glass transition temperatures decreased with increasing alkali modifier, ranging from 250 to 215 °C. Corresponding crystallization onset temperatures were between 340 and 385 °C. DC conductivity values of the glasses ranged from 10-10 to 10-7 (Ω cm)-1 with activation energies between 0.54 and 0.93 eV for the temperature range of ∼100–250 °C. Higher ionic conductivities were observed with increasing alkali concentration and decreasing alkali radii. Additionally, an increase in the activation energy was observed above the glass transition temperature.

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