Extended Study on Crystal Growth and Viscosity in Ge-Sb-Se Bulk Glasses and Thin Films

Crystal growth rates in Ge₁₈Sb₂₈Se₅₄ bulk glass and thin film were measured using optical and scanning electron microscopy under isothermal conditions. The studied temperature region was 255-346 °C and 254-286 °C for bulk glass and thin film, respectively. The compact crystalline layer growing from the surface into the amorphous core was formed in bulk glasses and no bulk crystallization was observed. In the case of thin films, needle-shape crystals were formed. The crystalline layer and needle-shape crystals grew linearly with time that corresponds to a crystal growth controlled by the crystal-liquid interface kinetics. In the narrow temperature range, crystal growth rates exhibit simple exponential behavior, so the activation energies of crystal growth for the studied temperature regions were estimated (E_G = 294 ± 6 kJ/mol for bulk glass and E_G = 224 ± 12 kJ/mol for thin film). Viscosity of Ge₁₈Sb₂₈Se₅₄ material was measured in the region of the undercooled melt and glass. The extrapolation of viscosity data into the immeasurable, but important, temperature range is discussed. The experimental growth data were combined with melting and viscosity data and the appropriate growth models were proposed to describe crystal growth in a wide temperature region. The standard crystal growth models are based on a simple proportionality of the crystal growth rate to the viscosity (u ∝ η^-1). This simple proportionality holds for the bulk material. Nevertheless, in the thin films the decoupling of the crystal growth rate from the inverse viscosity occurs, and the standard kinetic growth models need to be corrected. Such corrections provide better description of experimental data and more realistic value of the parameter describing the mean interatomic distance in the crystal-liquid interface layer, where the crystal growth takes place.