LaTiOxNy oxynitride thin films are employed to study the surface modifications at the solid- liquid interface that occur during photoelectrocatalytic water splitting. Neutron reflectometry and grazing incidence x-ray absorption spectroscopy were utilised to distinguish between the surface and bulk signals, with a surface sensitivity of 3 nm.
Mixed oxides derived from the perovskite structure by combination of A- and B-site elements and by partial substitution of oxygen provide an immense playground of physico-chemical properties. Here, we give an account of our own research conducted at the Paul Scherrer Institute on perovskite-type oxides and oxynitrides used in electrochemical, photo(electro)chemical and catalytic processes aimed at facing energy relevant issues.
SrTiO3 thin films were grown on 18O-exchanged SrTiO3 single crystalline substrates by pulsed-laser deposition, rf sputtering, and oxide molecular-beam epitaxy to study their oxygen diffusion depth profiles using secondary ion mass spectrometry and elastic recoil detection analysis depth profiling. The oxygen depth profiling shows that SrTiO3 films prepared with the three different deposition techniques will take oxygen from the substrate, even at room temperature. This confirms that the substrate is one possible oxygen source for the growth of oxide thin films independent of the physical vapor deposition technique employed. It was also found that a reactive oxygen environment changes the oxygen composition of the substrate during the growth of a film and partly replaces 18O with 16O up to a depth of several tens of nm. These findings imply that SrTiO3 and therefore other ion conducting oxide substrates, which are commonly used as platforms for thin film growth, can be considered capricious in nature with respect to oxygen chemistry and lattice constants.