A study on selective surface nitridation of TiO2 nanocrystals in the afterglows of N2 and N2-O2 microwave plasmas

Abstract

Surface-selective chemical modification of anatase TiO2 nanocrystals is performed in the post-discharge region of N2 microwave plasma and the chemical bonding states of surface nitrogen species are carefully evaluated using X-ray photoemission spectroscopy (XPS). It is found that the surface treatments in the afterglows induce the formation of stable nitrogen species at or near the surface of TiO2. Interestingly, the detailed bonding structure varies strongly depending on the afterglow condition. In pure N2 afterglows, various N species with a direct TiN bond are formed on the surface, while the use of N2-O2 mixtures induces the formation of additional oxidized species of NO3− on the surface. This is attributed to the high concentrations of O or NO in the afterglows of N2-O2 plasmas. The incorporation of substitutional N species in the subsurface is also achieved after a prolonged exposure in the early afterglow with a high density of N2+ species. Our results show that the exposure condition can be controlled for a selective chemical modification of TiO2 surface for the control of surface properties in various applications.