Identification of Lone-Pair Surface States on Indium Oxide

Indium oxide is widely used as a transparent electrode in optoelectronic devices and as a photocatalyst with activity for reduction of CO₂. However, very little is known about the structural and electronic properties of its surfaces, particularly those prepared under reducing conditions. In this report, directional "lone-pair" surface states associated with filled 5s² orbitals have been identified on vacuum-annealed In₂O₃(111) through a combination of hard and soft X-ray photoemission spectroscopy and density functional theory calculations. The lone pairs reside on indium ad-atoms in a formal +1 oxidation state, each of which traps two electrons into a localized hybrid orbital protruding away from the surface and lying just above the valence band maximum in photoemission spectra. The third electron associated with the ad-atoms is delocalized into the conduction band, thus producing the surface electron accumulation layer identified previously on vacuum-annealed In₂O₃(111) (1 × 1) surfaces. The surface structure is further supported by low-energy electron diffraction, but there is no chemical shift in indium core level X-ray photoelectron spectra between surface In(I) ad-atoms and bulk In(III). The 5s² lone pairs confer Lewis basicity on the surface In sites and may have a pronounced impact on the catalytic or photocatalytic activity of reduced In₂O₃.