Electronic structure and optical properties of SrCu2O2

Abstract

The electronic structure of SrCu2O2, a wide gap (∼3.3 eV) p-type oxide semiconductor, was examined by photoelectron and optical spectroscopy. The spectroscopy results were compared with the energy band structure calculated by the local density approximation method to clarify the origins of p-type conductivity in this material. Despite the significant difference in band gap energy, the basic electronic structure around the band gap region was found to be quite similar to that of Cu2O. Thus, the 3d−4sp orbital of Cu+ ion is hybridized with the 2p orbital of ligand O2− ions due to the covalency of Cu–O bonds, to form states near the valence band maximum; the conduction band minimum is predominantly composed of the hybridized orbital of Cu 4sp and O 2p, forming the direct band gap at Γ point. A sharp absorption band observed near the fundamental absorption edge is likely attributable to an exciton. Although the corresponding exciton emission was not observed near the absorption edge, a blue-green emission band (Stokes shift of ∼1 eV) was observed at ∼2.47 eV. The emission is presumably attributable to intra-atomic transitions of Cu+, partially allowed by p-orbital mixing into s and d orbitals.