Study of the solid-phase equilibria in the GeTe-Bi2Te3-Te system and thermodynamic properties of GeTe-rich germanium bismuth tellurides

A set of self-consistent thermodynamic parameters of the GeTe-rich germanium-bismuth tellurides were determined using an electromotive force (EMF) method with a glycerol electrolyte in a temperature range from 300 to 450 K. The solid-phase equilibrium diagram of the GeTe-Bi₂Te₃-Te system at 400 K was constructed using X-ray diffraction (XRD) and scanning electron miscroscope (SEM) techniques of synthesized electrode alloys, as well as available literature data. It is found that all telluride phases in GeTe-Bi₂Te₃ pseudo-binary section have a tie-line connection with elemental tellurium. The relative partial thermodynamic functions of GeTe in alloys were calculated using data from EMF measurements of concentration cells relative to the GeTe electrode. These findings together with the corresponding thermodynamic functions of GeTe and Bi₂Te₃ were used to calculate the relative partial molar functions of germanium in alloys, and also the standard thermodynamic functions of formation and standard entropies of the ternary compounds, namely Ge₂Bi₂Te₅, Ge₃Bi₂Te₆ and Ge₄Bi₂Te₇.