Photochemical activity of nitrogen-doped rutile TiO2(111) in visible light

TiO2 (110) single crystals, doped with nitrogen via an NH3 treatment at 870 K, have been found to exhibit photoactivity at photon energies down to 2.4 eV, which is 0.6 eV below the band-gap energy for rutile TiO2. The active dopant state of the interstitial nitrogen that is responsible for this effect exhibits an N (Is) binding energy of 399.6 eV and is due to a form of nitrogen that is probably bound to hydrogen, which differs from the substitutional nitride state with an N (Is) binding energy of 396.7 eV. Optical absorption measurements also show enhanced absorption down to 2.4 eV for the NH3-treated TiO2 (110). A co-doping effect between nitrogen and hydrogen is postulated to be responsible for the enhanced photoactivity of nitrogen-doped TiO2 materials in the range of visible light.