Thermodynamic calculation of S−Sb system and Cu−S−Sb system

Sb₂S₃ and CuSbS₂ have been proposed as alternative earth-abundant absorber materials for thin-film solar cells. However, no thermodynamic study of the S−Sb binary system and the Cu−S−Sb ternary system were investigated. In this paper, The S−Sb system and the Cu−S−Sb system are calculated utilizing the so-called CALPHAD (CALculation of PHAse Diagrams) technique. Using TEM-EDS and XRD, Cu_0.9Sb₁S₂ is experimentally confirmed at the Cu₁Sb₁S₂ and Sb₂S₃ two-phases region in the isothermal section at 673 K of the Cu−S−Sb ternary system. Given the asymmetric shape and miscibility gap of the liquidus in the S−Sb phase diagram, the associate solution model for the liquid phase is adopted. The solution phases (liquid, bcc, fcc) are treated with the Redlich–Kister equation. The compounds S₃Sb₂, Cu₃SbS₃, Cu₁₂Sb₄S₁₃, CuSbS₂, and Cu₃SbS₄ are described as a stoichiometric compound. A set of self-consistent thermodynamic parameters of the S−Sb binary system and the Cu−S−Sb ternary system are obtained. The calculated results are in good agreement with the experimental data. This study provides a set of reliable thermodynamic parameters to the Cu−Sb−S thermodynamic database, and a cost-effective tool to design material synthesis experiments and manufacturing processes.