How UV light lowers the conductivity of SrTiO3 by photochemical water splitting at elevated temperature

Abstract

Nominally undoped SrTiO₃ single crystals were illuminated by UV light at 350 °C in oxidizing as well as reducing atmospheres. In N₂/O₂ atmospheres, UV irradiation enhances the conductivity of SrTiO₃ by several orders of magnitude. In dry H₂ atmosphere UV exposure leads to the opposite conductivity effect, i.e., above band gap energy illumination surprisingly lowers the conductivity. This is discussed in the framework of a defect chemical model. We show that a shift in defect concentrations due to UV-driven oxygen incorporation from the gas phase into the oxide is the main cause of the measured conductivity changes. A model is introduced to illustrate the thermodynamic and kinetic drivers of the processes under UV irradiation. Noteably, in reducing H₂/H₂O atmospheres, the incorporation of oxygen into the investigated oxide under UV light takes place via water splitting. Owing to the predominant electron conduction of SrTiO₃ in equilibrium with H₂, oxygen incorporation upon UV and thus an increase of the oxygen chemical potential leads to a decrease of the majority electronic charge carrier, here electrons, which lowers the conductivity under UV irradiation.