- Electronic properties of reduced (vacuum-annealed) and oxidized (air-annealed) TiO2 films were investigated by in situ conductivity and current–voltage measurements as a function of the ambient oxygen pressure and temperature, and by ex situ surface photovoltage spectroscopy. The films were quite conductive in the reduced state but their resistance drastically increased upon exposure to air at 350 °C. In addition, the surface potential barrier was found to be much larger for the oxidized versus the reduced films. This behavior may be attributed to the formation of surface and grain boundary barriers due to electron trapping at interface states associated with chemisorbed oxygen species. © 2003 American Institute of Physics.