First-principles study of band alignments in the p-type hosts BaM2X2 (M = Cu, Ag; X = S, Se).

The electronic structures of four semiconductor compounds BaCu2S2, BaCu2Se2, BaAg2S2, and BaAg2Se2 are studied by density functional theory using both semi-local and hybrid functionals. The ionization energies and electron affinities were determined by aligning the electronic states with the vacuum level by calculating the electrostatic profile within a supercell slab model. The ionization energy and electron affinity of the compounds were calculated using the Heyd-Scuseria-Ernzerhof functionals and range from 4.5 eV to 5.4 eV and 3.1 eV to 3.4 eV, respectively. The replacement of Cu by Ag slightly increases the ionization energy and electron affinity, while the replacement of S by Se decreases the ionization energy but slightly increases the electron affinity. Overall, the low ionization energies and small electron affinities suggest that these compounds possess good p-type doping propensities. The band gaps are somewhat small to be ideal candidates for transparent semiconducting behavior; however, the replacement of Cu with Ag in the barium sulfide compounds can increase the band gap from 1.62 to 2.01 eV.