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The temperature dependence of the thermal conductivity k(T) of the AsxS100-x glass system was studied down to 1.8 K in a wide range of various (x = 20, 28.6, 40, 45, and 50) compositions. Universal glass anomalies in k(T) were revealed. The temperature dependence k(T) ∼ T2 onset at the lowest temperatures and plateau below 15 K were detected. The plateau formation is sample quality sensitive and composition-dependent. It was experimentally found that even with a slow cooling rate, several samples were cracked. Depending on the sample damage, the additional internal scattering process leads to the k(T) plateau suppression. The observed k(T) temperature dependence is similar to the glassy ceramics-like behavior.

The super-bandgap laser irradiation of the in situ prepared As-S chalcogenide films was found to cause drastic structural transformations and unexpected selective diffusion processes, leading to As enrichment on the nanolayer surface. Excitation energy dependent synchrotron radiation photoelectron spectroscopy showed complete reversibility of the molecular transformations and selective laser-driven mass transport during "laser irradiation"-"thermal annealing" cycles. Molecular modeling and density functional theory calculations performed on As-rich cage-like clusters built from basic structural units indicate that the underlying microscopic mechanism of laser induced transformations is connected with the realgar-pararealgar transition in the As-S structure. The detected changes in surface composition as well as the related local and molecular structural transformations are analyzed and a model is proposed and discussed in detail. It is suggested that the formation of a concentration gradient is a result of bond cleavage and molecular reorientation during transformations and anisotropic molecular diffusion.

As-deposited, annealed, and in situ As2S3 nanolayers, illuminated by blue (405 nm) and red (650 nm) laser light, were studied using synchrotron radiation photoelectron spectroscopy and DFT electronic structure calculations. Changes in composition and local atomic coordination occurring in the irradiated region of As2S3 films were monitored by analysis of As 3d and S 2p core levels. These studies show that both the thermal treatment and the red laser illumination of As2S3 nanolayers decrease the concentration of homopolar (As-As and S-S) bonds. From the other hand, an increasing concentration of As-rich structural units (s.u.) with a homopolar As-As bond was observed under in situ blue laser illumination of As2S3 nanolayers. Molecular orbital energies were calculated for different As- and S-centered s.u. and used for the interpretation of the core levels and valence band spectra. The surface local structure of the As2S3 nanolayers and its photoinduced transformation are discussed in detail.