Vacancy-induced magnetic states in TiO2 surfaces.

We present a combined experimental and theoretical study of surface-related magnetic states in TiO 2. Our experiments on nano-sized thin films of pure TiO 2 have suggested that the observed room-temperature magnetism originates from defects, in particular, from the surface of thin films as well as from point defects, such as oxygen vacancies located mainly at the surface. Clarifying this phenomenon is very important for harnessing magnetic properties of pristine TiO 2 films in future spintronic applications but a detailed experimental investigation is very demanding. Therefore, quantum-mechanical density functional theory calculations were performed for (i) bulk anatase TiO 2 , (ii) bulk-like TiO 2 -terminated vacancy-free (001) surfaces, (iii) vacancy-containing TiO-terminated (001) surfaces, (iv) TiO 0.75 -terminated (001) surfaces with additional 25% surface oxygen vacancies, as well as (v) oxygen-terminated (001)-surfaces. Our fixed-spin-moment calculations identified both the bulk and the bulk-like terminated vacancy-free TiO 2 -terminated (001) surfaces as non-magnetic. In contrast, oxygen vacancies in the case of TiO-terminated and TiO 0.75 -terminated (001) surfaces lead to ferromagnetic and rather complex ferrimagnetic states, respectively. The spin-polarized atoms are the Ti atoms (due to the d -states) located in the surface and sub-surface atomic planes. Last, the O-terminated surfaces are also magnetic due to the surface and sub-surface oxygen atoms and sub-surface Ti atoms (but their surface energy is high). [ABSTRACT FROM AUTHOR]