While SOFC perovskite oxide cathodes have been the subject of numerous studies, the critical factors governing their kinetic behavior have remained poorly understood. This has been due to a number of factors including the morphological complexity of the electrode and the electrode- electrolyte interface as well as the evolution of the surface chemistry with varying operating conditions. In this work, the surface chemical composition of dense thin film SrTi_1−xFe_xO_3-δelectrodes, with considerably simplified and well-defined electrode geometry, was investigated by means of XPS, focusing on surface cation segregation. An appreciable degree of Sr-excess was found at the surface of STF specimens over the wide composition range studied. The detailed nature of the Sr-excess is discussed by means of depth and take-off angle dependent XPS spectra, in combination with chemical and thermal treatments. Furthermore, the degree of surface segregation was successfully controlled by etching the films, and/or preparing intentionally Sr deficient films. Electrochemical Impedance Spectroscopy studies, under circumstances where surface chemistry was controlled, were used to examine and characterize the blocking effect of Sr segregation on the surface oxygen exchange rate.

The correlation between the surface chemistry and electronic structure is studied for SrTi_1−xFe_xO₃ (STF), as a model perovskite system, to explain the impact of Sr segregation on the oxygen reduction activity of cathodes in solid oxide fuel cells. Dense thin films of SrTi_0.95Fe_0.05O₃ (STF5), SrTi_0.65Fe_0.35O₃ (STF35) and SrFeO₃ (STF100) were investigated using a coordinated combination of surface probes. Composition, chemical binding, and valence band structure analysis using angle-resolved X-ray photoelectron spectroscopy showed that Sr enrichment increases on the STF film surfaces with increasing Fe content. In situ scanning tunnelling microscopy/spectroscopy results proved the important and detrimental impact of this cation segregation on the surface electronic structure at high temperature and in an oxygen environment. While no apparent band gap was found on the STF5 surface due to defect states at 345 °C and 10⁻³ mbar of oxygen, the surface band gap increased with Fe content, 2.5 ± 0.5 eV for STF35 and 3.6 ± 0.6 eV for STF100, driven by a down-shift in energy of the valence band. This trend is opposite to the dependence of the bulk STF band gap on the Fe fraction, and is attributed to the formation of a Sr-rich surface phase in the form of SrO_x on the basis of the measured surface band structure. The results demonstrate that Sr segregation on STF can deteriorate oxygen reduction kinetics through two mechanisms – inhibition of electron transfer from bulk STF to oxygen species adsorbing onto the surface and the smaller concentration of oxygen vacancies available on the surface for incorporating oxygen into the lattice.