Investigation of the Atomic Structure of Ge-Sb-Se Chalcogenide Glasses

Abstract

Glasses with composition of GexSb40-xSe60 (x= 40, 35, 32, 27, 20, 15 at. %) have been synthesized. Neutron and X-ray diffraction techniques were used to study the atomic glassy structure, and Reverse Monte Carlo (RMC) simulations were applied to model the 3-dimensional atomic configurations and thorough mapping of the atomic parameters, such as first and second neighbour distances, coordination numbers, and bond-angle distributions. The results are explained with formation of GeSe4 and SbSe3 structural units, which correlate with the Ge/Sb ratio. For all the studied compositions, the Ge-Se, Sb-Se, Ge-Ge, and Se-Se bonds are significant. RMC simulations reveal the presence of Ge-Sb and Sb-Sb bonds, being dependent on Ge/Sb ratio. All atomic compositions satisfy formal valence requirements, i.e., Ge is fourfold coordinated, Sb is threefold coordinated, and Se is twofold coordinated. By increasing the Sb content, both the Se-Ge-Se bonds angle of 107±3° and Se-Sb-Se bonds angle of 118±3° decrease, respectively, indicating distortion of the structural units. Far infrared Fourier Transform spectroscopic measurements conducted in the range of 50-450 cm-1 at oblique (75°) incidence radiation have revealed clear dependences of the IR band's shift and intensity on the glassy composition, showing features around x=27 at.% supporting the topological phase transition to a stable rigid network consisting mainly of SbSe3 pyramidal and GeSe4 tetrahedral clusters. These results are in agreement with the Reverse Monte Carlo models, which define the Ge and Sb environment.