Exsolution of Embedded Nanoparticles in Defect Engineered Perovskite Layers.

Exsolution phenomena are highly debated as efficient synthesis routes for nanostructured composite electrode materials for the application in solid oxide cells (SOCs) and the development of next-generation electrochemical devices for energy conversion. Utilizing the instability of perovskite oxides, doped with electrocatalytically active elements, highly dispersed nanoparticles can be prepared at the perovskite surface under the influence of a reducing heat treatment. For the systematic study of the mechanistic processes governing metal exsolution, epitaxial SrTi0.9Nb0.05Ni0.05O3-δ thin films of well-defined stoichiometry are synthesized and employed as model systems to investigate the interplay of defect structures and exsolution behavior. Spontaneous phase separation and the formation of dopant-rich features in the as-synthesized thin film material is revealed by high-resolution transmission electron microscopy (HR-TEM) investigations. The resulting nanostructures are enriched by nickel and serve as preformed nuclei for the subsequent exsolution process under reducing conditions, which reflects a so far unconsidered process drastically affecting the understanding of nanoparticle exsolution phenomena. Using an approach of combined morphological, chemical, and structural analysis of the exsolution response, a limitation of the exsolution dynamics for nonstoichiometric thin films is found to be correlated to a distortion of the perovskite host lattice. Consequently, the incorporation of defect structures results in a reduced particle density at the perovskite surface, presumably by trapping of nanoparticles in the oxide bulk.