Title

Sulfur on TiO2(110) studied with resonant photoemission

Document Type

Article

Publication Date

9-15-2001

Abstract

Adsorption of sulfur on TiO2(110) at room temperature (RT) and 350 °C has been studied with ultraviolet photoelectron spectroscopy. A TiO2(110) (1 ×1) surface with a small amount of oxygen vacancies was prepared by sputtering and annealing in ultrahigh vacuum. Oxygen vacancies induce a defect state that pins the Fermi level just below the conduction-band minimum. Sulfur adsorption at room temperature leads to the disappearance of this vacancy-related band-gap state, indicating that the surface oxygen vacancies are filled by sulfur. Sulfur-induced valence-band features are identified at binding energies of 3.4 and 8 eV. Adsorption of S at 350 °C forms a (4 ×1) superstructure at high coverages [≅0.9 monolayer (ML)] that is visible with low-energy electron diffraction. In a previously proposed model for this superstructure, sulfur replaces half of the in-plane oxygen atoms and all the bridging oxygen atoms are removed. In agreement with this model, the oxygen 2s peak is decreased significantly and the defect state is increased. Two additional valence features are observed: one at 2.7 eV and one at 3.9 eV. Due to those features the band gap vanishes. In resonant photoemission, these features show a similar, but weaker, resonance profile than the vacancy-related defect state. Hybridized Ti-derived states extend across the whole valence-band region. Generally, a higher resonant photon energy is found for valence-band states with lower binding energies, indicating mainly 3p-4s transitions in the upper valence band. Adsorption of sulfur reduces the strength of the resonances.

Publication Source (Journal or Book title)

Physical Review B - Condensed Matter and Materials Physics

First Page

1154181

Last Page

11541811

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