Band structure and phase stability of the copper oxides Cu2O, CuO, and Cu4O3

The p-type semiconductor copper oxide has three distinct phases Cu2O, CuO, and Cu4O3 with different morphologies and oxidation states of the copper ions. We investigate the structural stability and electronic band structure of all three copper oxide compounds using ab initio methods within the framework of density functional theory and consider different exchange correlation functionals. While the local density approximation (LDA) fails to describe the semiconducting states of CuO and Cu4O3, the LDA + U and HSE06 hybrid functional describe both compounds as indirect semiconductors. Using the HSE06 hybrid functional we calculate the electronic band structure in the full Brillouin zone for all three copper oxide compounds. DOI: 10.1103/PhysRevB.87.115111