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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.

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