Indium oxide is widely used as a transparent electrode in optoelectronic devices and as a photocatalyst with activity for reduction of CO 2 . 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 5s 2 orbitals have been identified on vacuum-annealed In 2 O 3 (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 In 2 O 3 (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 5s 2 lone pairs confer Lewis basicity on the surface In sites and may have a pronounced impact on the catalytic or photocatalytic activity of reduced In 2 O 3 .
Bibliographical noteFunding Information:
D.W.D. thanks the Engineering and Physical Sciences Research Council (EPSRC) for support via the Centre for Doctoral Training in Sustainable Chemical Technologies (EPL016354/ 1). Calculations were carried out on the Balena HPC cluster at the University of Bath, which is maintained by Bath University Coomputing Services. V.R.D. thanks EPSRC for support (EP/ NO15800/1). K.H.L.Z gratefully acknowledges the funding support of a Clarendon Scholarship at the University of Oxford and the Thousand Youth Talents Program at Xiamen University. K.P. thanks the Academy of Finland (grant 277829) and the CSC-Finnish IT Centre for Science for support.
© 2018 American Chemical Society.