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The influence of the electric field and electric current on the behavior ofoxygen vacancies (VOs) in TiO2 anatase was investigated with Scanning TunnelingMicroscopy (STM). At the anatase (101) surface VOs are not stable; they migrateinto the bulk at temperatures above 200 K. Scanning a clean anatase (101)surface at a sample bias greater than +4.3 V results in surface VOs in thescanned area, suggesting that subsurface VOs migrate back to the surface. Totest this hypothesis, surface VOs were first created through bombardment withenergetic electrons. The sample was then mildly annealed, which caused the VOsto move to the subsurface region, where they formed vacancy clusters. These VOclusters have various, distinct shapes. Scanning VO clusters with a high STMbias reproducibly converts them back into groupings of surface VO, with aconfiguration that is characteristic for each type of cluster. The dependenceof the subsurface-to-surface VO migration on the applied STM bias voltage,tunneling current, and sample temperature was investigated systematically. Theresults point towards a key role of energetic, 'hot' electrons in this process.The findings are closely related to the memristive behavior of oxides andoxygen diffusion in solid-oxide membranes.

Aggregation and Electronically-Induced Migration of Oxygen Vacancies in TiO2 Anatase