Structural stability and electronic properties of XTO2 (X= Cu, Ag; T=Al, Cr): An ab initio study including X vacancies and Mg doping

Abstract Ab initio density functional theory-based calculations are used to study the structural and electronic properties of CuAlO 2 , AgAlO 2 , CuCrO 2 , and AgCrO 2 transparent conducting oxides (TCOs). The hexagonal 2H delafossite polymorph is determined here to be one of the most stable polymorphs, by comparing total energies for different structural phases. The simple antiferromagnetic configuration is chosen to model magnetic effects in CuCrO 2 and AgCrO 2 due to it having one of the lowest ground state total energies and containing the most semiconductor like behavior of the magnetic configurations considered. Electronic structures of 2H CuAlO 2 and AgAlO 2 obtained from different approximations for the exchange-correlation functional, GGA (PBE), PBE + U, PBE + mBJ, PBE + mBJ + U, and the Hybrid HSE06 are compared. Supercells are employed to model 6.25% Cu and Ag vacancies, 3.13% O vacancies, and 6.25% Mg doping replacing Al and Cr, from which structural and electronic properties are obtained and used to predict on the effectiveness of these native defects and dopant on increasing the conductivity in all TCOs studied in this work. The obtained partial density of states for the pristine systems supports a model of hole conduction in the a – b plane, perpendicular to the O – X – O dumbbells of the delafossite structure. Additionally, the partial density of states of the defective and doped systems suggest a growth environment deficient in X and saturated in O may increase conductivity in these materials.