Properties of GdSF and phase diagram of the GdF3 - Gd2S3 system

Abstract

The objectives of this study were to refine the phase diagram of the GdF3-Gd2S3 system and to calculate their liquidus, and to synthesize GdSF and to study their properties. The GdSF compound (ST PbFCl, P4/nmm, a (Å) 3.83006(17), c (Å) 6.8529(3), has an optical band gap for a direct interband transition of 2.56 ​eV and is characterized by a pronounced increase in the Kubelka-Munk function in the region of this transition. Direct optical bandgap of GdSF is measured to be equal to 2.77 ​eV. Two indirect bandgaps are detected to be 1.54 and 2.4 ​eV. Meta-GGA simulations of band structure predicting 1.481 ​eV direct bandgap of GdSF are in good agreement with these features of the experimental absorption spectrum. To explain this complicated case, we argue that formally direct optical transitions to highly dispersive subbands contribute not to direct but to indirect bandgaps measured by Tauc analysis. The GdSF compound melts incongruently with the formation of a melt and γ-Gd2S3 compound at t ​= ​1280 ​± ​2°С, ΔН ​= ​40.6 ​± ​2.8 ​kJ/mol, ΔS ​= ​26.1 ​± ​1.8 ​J/mol∗K. The eutectic has a composition of 13 ​mol.% Gd2S3 (0.74 GdF3 ​+ ​0.26 GdSF), the melting characteristics of the eutectic are 1182 ​± ​2°С, ΔН ​= ​36.2 ​± ​2.5 ​kJ/mol, ΔS ​= ​24.9 ​± ​1.7 ​J/mol∗K. In the system GdF3 - Gd2S3 the balance equations for five phase transformations recorded by the DSC method were compiled. Convergence was achieved in the liquidus of the system constructed according to DSC data and calculated with the use of the Redlich-Kister equation.