Hydrothermally grown rutile TiO₂ nanowires are intrinsically full of lattice defects, especially oxygen vacancies. These vacancies have a significant influence on the structural and electronic properties of the nanowires. In this study, we report a post-growth heat treatment in different environments that allows control of the distribution of these defects inside the nanowire, and thus gives direct access to tuning of the properties of rutile TiO₂ nanowires. A detailed transmission electron microscopy study is used to analyze the structural changes inside the nanowires which are correlated to the measured optical and electrical properties. The highly defective as-grown nanowire arrays have a white appearance and show typical semiconducting properties with n-type conductivity, which is related to the high density of oxygen vacancies. Heat treatment in air atmosphere leads to a vacancy condensation and results in nanowires which possess insulating properties, whereas heat treatment in N₂ atmosphere leads to nanowire arrays that appear black and show almost metal-like conductivity. We link this high conductivity to a TiO2-x shell which forms during the annealing process due to the slightly reducing N₂ environment.
Keywords: black TiO2; conductivity; defects; electron energy loss spectroscopy; nanowire; oxygen vacancy.