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, Cu0.9Sb1S2 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.