Profiles of oxygen and titanium point defects in ferromagnetic TiO2 films

Abstract Experimentally it is shown that without any oxygen manipulation for TiO 2 , a strong room temperature ferromagnetism could be expected only in ultra-thin films, with the ideal thickness below 100 nm. Both bulks and nano-powders of TiO 2 are diamagnetic, indicating that the surface and its nano-sublayers play very important roles in tailoring the magnetic properties in this type of compound. To shed a new light on the defect-related magnetism in the typical case of anatase TiO 2 surfaces, we have performed a series of quantum-mechanical calculations for TiO 2 slabs containing Ti or O vacancies in different distances from the (001) surface. The lowest formation energies were obtained for the Ti vacancies in the first sub-surface layer and the O vacancies within the surface. The computed magnetic states reflect complicated structural relaxations of atoms influenced by both the surface and vacant atomic positions. O atoms cannot contribute much to magnetic moment when Ti vacancies are isolated and far from the surface. Ti vacancies in TiO 2 are only metastable. The formation energy of Ti interstitials is lower than for Ti vacancies since high-temperature annealing, especially with a lot of O 2 available that would fill up O-related defects, and as a result, eliminate most of Ti vacancies. Lower temperatures, less O 2 , and shorter exposure times may enable not only partial elimination of Ti vacancies but also can facilitate their diffusion into different states of aggregations. In the ferromagnetic films (i.e. thin films below 100 nm), it looks like that the O atoms are located closer to the Ti vacancies.