Complex copper-based chalcogenides: a review of phase equilibria and thermodynamic properties

Complex copper-based chalcogenides are among the most important functional materials in modern engineering and technology due to their diverse physical and physicochemical properties, environmental safety and availability. The development of new similar materials and the improvement of the applied characteristics of known compounds is largely associated with the use of approaches based on the physicochemical analysis and, in particular, the “composition-structure-property” relationship. This review summarizes the available data on phase equilibria in ternary systems Cu-Tl(BIV, BV)-X (BIV-Si, Ge, Sn; BV-As, Sb, Bi; X-S, Se, Te) and the thermodynamic properties of their intermediate phases. Similar data are also considered for more complex systems forming solid solutions of various types of substitution based on known ternary copper chalcogenides. A significant part of the presented sets of mutually consistent data on phase equilibria and thermodynamic properties of the considered systems was obtained by our group over the past 10-15 years. Although these data cover only a small part of the systems described above, they provide great possibilities for manipulation of composition and structure, including entropic engineering strategies. The authors consider it extremely important to further develop fundamental research on phase equilibria and thermodynamic properties of complex copper chalcogenides and use their results widely in selecting alloy compositions for physical measurements