Competition between clustering and dispersion of cobalt atoms on perovskite surfaces: SrTiO3(001) and KTaO3(001)

Abstract

Perovskite oxides are attractive for reactions in photo/electrocatalytic schemes, and extrinsic doping is a common strategy for tuning their properties. It is widely known that extrinsic dopants impact the structure and stability of perovskite surfaces, but an atomic-scale view is missing. Here, noncontact atomic force microscopy (ncAFM) and photoelectron spectroscopy (XPS/PES) are used to combine microscopic and spectroscopic evidence of cobalt adsorption, incorporation, and clustering at surfaces of two prototypical perovskites SrTiO3 and KTaO3. A number of different sub-ML coverages and temperatures of annealing were investigated. Several common features are observed: cobalt shows a strong preference for ionic nature (+2 and +3 charge states), and remains dispersed as single atoms to a certain extent in both perovskites. Two competing mechanisms are observed upon annealing: coalescence into clusters with a mixed metallic/ionic character, and incorporation into the surface and subsurface regions. The latter is more pronounced in SrTiO3, where a cobalt-stabilized surface reconstruction is identified, whereas for KTaO3 cobalt likely incorporates in the near-surface region.