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Defects in the surface region of a reducible oxide, as TiO2, have a profoundeffect on applications, while their nature is very much influenced by thepossibility of small polaron formation. Here, we probe rutile (110) and anatase(101) single crystals via high-resolution ultraviolet photoelectronspectroscopy and resolve multiple components of the well-known defect state inthe band gap. In rutile, we find two at VBM+2.1 eV and VBM+1.4 eV, which weassign to subsurface polaron traps and vacancy-bound states, respectively,confirming the predicted partial suppression of polaron formation at highvacancy concentration. New defects are created in situ on the anatase surfaceby the synchrotron beam. We assign a component at VBM+2.3 eV, which can beremoved by annealing, to polaron states associated with surface oxygenvacancies. We also identify a second component at VBM+1.6 eV, which can not beremoved by annealing, and is too deep to be associated with oxygen vacancies.

Observation of vacancy-related polaron states at the surface of anatase and rutile TiO2 by high-resolution photoelectron spectroscopy