ABSTRACT
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.
ABSTRACT
Experimental results of the thermal conductivity (k(T)) of nanostructured g-As2S3 during cooling and heating processes within the temperature range from 2.5 to 100 K have been analysed. The paper has considered thermal conductivity is weakly temperature k(T) dependent from 2.5 to 100 K showing a plateau in region from 3.6 to 10.7 K during both cooling and heating regimes. This paper is the first attempt to consider the k(T) hysteresis above plateau while heating in the range of temperature from 11 to 60 K. The results obtained have not been reported yet in the scientific literature. Differential curve Δk(T) of k(T) (heating k(T) curve minus cooling k(T) curve) possesses a complex asymmetric peak in the energy range from 1 to 10 meV. Δk(T) reproduces the density of states in a g(ω)/ω 2 representation estimated from a boson peak experimentally obtained by Raman measurement within the range of low and room temperatures. Theoretical and experimental spectroscopic studies have confirmed a glassy structure of g-As2S3 in cluster approximation. The origin of the low-frequency excitations resulted from a rich variety of vibrational properties. The nanocluster vibrations can be created by disorder on atomic scale.
ABSTRACT
As x S100-x (x = 40, 45, 50) thin films top surface nanolayers affected by green (532 nm) diode laser illumination have been studied by high-resolution X-ray photoelectron spectroscopy, Raman spectroscopy, optical spectroscopy, and surface profilometry. It is shown that the composition of obtained films depends not only on the composition of the source material but as well on the composition of the vapor during the evaporation process. Near-bandgap laser light decreases both As-As and S-S homopolar bonds in films, obtained from thermal evaporation of the As40S60 and As50S50 glasses. Although As45S55 composition demonstrates increasing of As-As bonds despite to the partial disappearance of S-S bonds, for explanation of this phenomenon Raman investigations has also been performed. It is shown that As4S3 structural units (s.u.) responsible for the observed effect. Laser light induced surface topology of the As45S55 film has been recorded by 2D profilometer.
ABSTRACT
The depth dependence of Raman spectra of a-GeS(2)-type films having a different optical thickness (lambda/4 and lambda/2) and their refractive index profile have been investigated. The model of a layered-inhomogeneous structure of films has been proposed. There have been distinguished three regions: near-surface region (up to 50 A), central part and transition film-substrate region (up to 300 A).
