Beyond the Surface: Interconnection of Viscosity, Crystal Growth, and Diffusion in GeSe Glass-Former.

The knowledge of viscosity behavior, crystal growth phenomenon, and diffusion is important in producing, processing, and practical applications of amorphous solids prepared in different forms (bulk glasses and thin films). This work uses microscopy to study volume crystal growth in GeSe bulk glasses and thermally evaporated thin films. The collected growth data measured over a wide temperature range show a significant increase in crystal growth rates in thin films. The crystal growth is analyzed using near-surface viscosities obtained in bulks and thin films using nanoindentation and melt viscosities measured by a pressure-assisted melt filling technique. The crystal growth analysis provides information on the size of the structural units incorporated into the growing crystals, essential for estimating the diffusion coefficients and explaining the difference in crystal growth rates in bulk and thin films. The crystal growth analysis also reveals the decoupling between diffusion and viscous flow described by the Stokes-Einstein-Eyring relation. Moreover, to the authors' best knowledge, the manuscript provides the first evaluation estimation of the effective self-diffusion coefficient directly from growth data in chalcogenide glass-formers. The present data show a similar relation between diffusion coefficients () and crystal growth rates (): ≈ , which is found in several molecular glasses.