Thermodynamic Assessment of the Ag-Se System Aided by First-Principles Calculations

The substitution of Ag for Cu in CuIn_xGa_1?xSe₂-based photovoltaic absorber layers can be used to adjust the bandgap energy to better optimize the overall cell efficiency. Based on available thermochemical, equilibrium, and structural data, the Ag-Se system has been assessed and modeled. Given the order-disorder structure transition Ag₂Se, the 2- and 3-sublattice models were used to represent the low- and high-temperature phases of the intermetallic compound respectively. Density functional theory based first-principles calculations were used to calculate the Gibbs energy of formation of the end-member compounds. A set of modeling parameters was obtained by the CALculation of PHAse Diagram approach and reasonable agreement was obtained between the experimental thermodynamic properties of the stable phases and the phase relationships in the Ag-Se system.