Mechanistic insights into photo-current enhancement in photo-active SrTiO3 heterojunctions under UV illumination

Photo-active heterojunctions were prepared by growing thin La0.9Sr0.1CrO3-δ films on SrTiO3 (STO) single crystals substrates via pulsed laser deposition. The photo-electrochemical characteristics of these heterojunctions under UV illumination were investigated by DC measurements and electrochemical impedance spectroscopy (EIS). Under UV illumination, the photo-current produced by these junctions increases over time by almost an order of magnitude to 1 to 2 mA cm-2 at 350 °C. Two effects governing this increase can be distinguished: A first process, independent of the surrounding atmosphere, is related to a stoichiometry polarization of the STO single crystal upon current flow. A second process is highly sensitive to contaminants in the surrounding atmosphere and is strongly accelerated in pure, synthetic atmospheres. We suggest that it is related to photo-oxidation of the STO single crystal. EIS revealed that both processes result in a decrease of both the electronic transport resistance through the STO single crystal and, to a lesser degree, the space charge resistance of the photo-active junction. Operando EIS under illumination and with DC bias was used to record the cells' photo-power characteristics and identify individual loss processes. Owing to the illumination induced strong increase of the STO single crystal conductivity, the photo-currents of such enhanced cells are limited by the space charge resistance.