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

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.

Photoinduced electronic and ionic effects in strontium titanate.

The interaction of light with solids has been of ever-growing interest for centuries, even more so since the quest for sustainable utilization and storage of solar energy became a major task for industry and research. With SrTiO3 being a model material for an extensive exploration of the defect chemistry of mixed conducting perovskite oxides, it has also been a vanguard in advancing the understanding of the interaction between light and the electronic and ionic structure of solids. In the course of these efforts, many phenomena occurring during or subsequent to the illumination of SrTiO3 have been investigated. Here, we give an overview of the numerous photoinduced effects in SrTiO3 and their inherent connection to electronic structure and defect chemistry. In more detail, advances in the fields of photoconductivity, photoluminescence, photovoltages, photochromism and photocatalysis are summarized and their underlying elemental processes are discussed. In light of recent research, this review also emphasizes the fundamental differences between illuminating SrTiO3 either at low temperatures (200 °C), where in addition to electronic processes, also photoionic interactions become relevant. A survey of the multitude of different processes shows that a profound and comprehensive understanding of the defect chemistry and its alteration under illumination is both vital to optimizing devices and to pushing the boundaries of research and advancing the fundamental understanding of solids.

Cation non-stoichiometry in Fe:SrTiO3 thin films and its effect on the electrical conductivity.

The interplay of structure, composition and electrical conductivity was investigated for Fe-doped SrTiO3 thin films prepared by pulsed laser deposition. Structural information was obtained by reciprocal space mapping while solution-based inductively-coupled plasma optical emission spectroscopy and positron annihilation lifetime spectroscopy were employed to reveal the cation composition and the predominant point defects of the thin films, respectively. A severe cation non-stoichiometry with Sr vacancies was found in films deposited from stoichiometric targets. The across plane electrical conductivity of such epitaxial films was studied in the temperature range of 250-720 °C by impedance spectroscopy. This revealed a pseudo-intrinsic electronic conductivity despite the substantial Fe acceptor doping, i.e. conductivities being several orders of magnitude lower than expected. Variation of PLD deposition parameters causes some changes of the cation stoichiometry, but the films still have conductivities much lower than expected. Targets with significant Sr excess (in the range of several percent) were employed to improve the cation stoichiometry in the films. The use of 7% Sr-excess targets resulted in near-stoichiometric films with conductivities close to the stoichiometric bulk counterpart. The measurements show that a fine-tuning of the film stoichiometry is required in order to obtain acceptor doped SrTiO3 thin films with bulk-like properties. One can conclude that, although reciprocal space maps give a first hint whether or not cation non-stoichiometry is present, conductivity measurements are more appropriate for assessing SrTiO3 film quality in terms of cation stoichiometry.