Thermodynamic modeling of phase equilibria and defect chemistry in the Zn-S system

Abstract Though important and fundamental, a satisfactory theoretical framework of modeling multiple point defects in the context of phase equilibria is still lacking. In this work, a methodology that models point defects, electrons, holes and the underlying phase equilibria simultaneously is developed and applied to the Zn-S system. It overcomes some issues in previous works, such as inconsistency in the reference state for electrons. The model parameters are directly related to the Gibbs energy of formation of point defects computed from first-principles phonon calculations. A double exponential function is proposed to parameterize the entropy of formation of point defects as a function of temperature. Using this approach, phase diagrams, concentrations of point defects and free carriers, the majority carrier, and defect-related properties exemplified by the electrical conductivity are obtained under various conditions, in agreement with experimental data. The present methodology provides a way to integrate first-principles calculations and experimental data into the CALPHAD model, enabling description of multi-component semiconductor systems.