Surface mobility in amorphous selenium and comparison with organic molecular glasses.

Surface diffusion is important for a broad range of chemical and physical processes that take place at the surfaces of amorphous solids, including surface crystallization. In this work, the temporal evolution of nanoholes is monitored with atomic force microscopy to quantify the surface dynamics of amorphous selenium. In molecular glasses, the surface diffusion coefficient has been shown to scale with the surface crystal growth rate (us) according to the power relation us ≈ Ds 0.87. In this study, we observe that the same power law applies to surface crystallization of amorphous selenium, a representative inorganic polymer glass. Our study shows that the surface diffusion coefficient can be used to quantitatively predict surface crystallization rates in a chemically diverse range of materials.

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 (EG = 294 ± 6 kJ/mol for bulk glass and EG = 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.

Pressure-Induced Phase Transitions in GeTe-Rich Ge-Sb-Te Alloys across the Rhombohedral-to-Cubic Transitions.

We demonstrate that pressure-induced amorphization in Ge-Sb-Te alloys across the ferroelectric-paraelectric transition can be represented as a mixture of coherently distorted rhombohedral Ge8Sb2Te11 and randomly distorted cubic Ge4Sb2Te7 and high-temperature Ge8Sb2Te11 phases. While coherent distortion in Ge8Sb2Te11 does not prevent the crystalline state from collapsing into its amorphous counterpart in a similar manner to pure GeTe, the pressure-amorphized Ge8Sb2Te11 phase begins to revert to the crystalline cubic phase at ∼9 GPa in contrast to Ge4Sb2Te7, which remains amorphous under ambient conditions when gradually decompressed from 40 GPa. Moreover, experimentally, it was observed that pressure-induced amorphization in Ge8Sb2Te11 is a temperature-dependent process. Ge8Sb2Te11 transforms into the amorphous phase at ∼27.5 and 25.2 GPa at room temperature and 408 K, respectively, and completely amorphizes at 32 GPa at 408 K, while some crystalline texture could be seen until 38 GPa (the last measurement point) at room temperature. To understand the origins of the temperature dependence of the pressure-induced amorphization process, density functional theory calculations were performed for compositions along the (GeTe)x - (Sb2Te3)1-x tie line under large hydrostatic pressures. The calculated results agreed well with the experimental data.

Crystal Growth Kinetics and Viscous Behavior in Ge2Sb2Se5 Undercooled Melt.

Crystal growth, viscosity, and melting were studied in Ge2Sb2Se5 bulk samples. The crystals formed a compact layer on the surface of the sample and then continued to grow from the surface to the central part of the sample. The formed crystalline layer grew linearly with time, which suggests that the crystal growth is controlled by liquid-crystal interface kinetics. Combining the growth data with the measured viscosities and melting data, crystal growth could be described on the basis of standard crystal growth models. The screw dislocation growth model seems to be operative in describing the temperature dependence of the crystal growth rate in the studied material in a wide temperature range. A detailed discussion on the relation between the kinetic coefficient of crystal growth and viscosity (ukin ∝ η(-ξ)) is presented. The activation energy of crystal growth was found to be higher than the activation energy of crystallization obtained from differential scanning calorimetry, which covers the whole nucleation-growth process. This difference is considered and explained under the experimental conditions.