QUASIBINARY SYSTEM Ag7PSe6– Ag2Se

Abstract

Semiconductor binary and ternary argentum selenides are of considerable practical interest, particularly as promising thermoelectric materials. These include Ag2Se, a narrow-band semiconductor, and Ag7PSe6, with a disordered cationic sublattice and a rigid anionic framework that causes efficient phonon scattering. Doping of Ag7PSe6 with the narrow bandgap semiconductor Ag2Se should increase its conductivity and Ag2Se with a more disordered Ag7PSe6 argyrodite phase to a decrease in thermal conductivity. In both cases, this should increase the thermoelectric figure of merit of the respective phases. At the same time, establishing the conditions for obtaining doped phases requires studying the conditions of their existence in the Ag7PSe6-Ag2Se system. Present work studies phase equilibria in the Ag7PSe6-Ag2Se system in the entire concentration range. A corresponding phase diagram was constructed based on the X-ray phase and differential thermal analysis results. It was found that the Ag7PSe6-Ag2Se system is quasi-binary. It is characterized by four processes: two eutectoid processes at 405 K and 433 K, caused by the presence of two polymorphic modifications in Ag2Se and Ag7PSe6, respectively; eutectic process at 893 K (the coordinates of the eutectic point are 893 K and ~8 mol% Ag2Se) and monotectic process at 977 K. Above this temperature, in the concentration range of ~9 - ~87 mol%, a region of immiscibility in the liquid is observed. The homogeneity regions of the initial components are less than 5 mol%. Keywords: quasibinary system; selenides; phase equilibria; phase diagram.