Exsolution of Ni nanoparticles in A-site excess STO films

Abstract

Exsolution is a technique to create metal nanoparticles embedded within a matrix. The phenomenon has previously predominantly been studied in A-site deficient and stoichiometric perovskite powders. Here, we present a systematic study of an A-site excess perovskite oxide based on SrTiO₃ thin films, doped with nickel and exsolved under different conditions. The study aims to shed light on particle formation in these novel systems, including the effects of (i) the thin film thickness, (ii) pre-exsolution annealing in an oxidative atmosphere, (iii) a reductive atmosphere during the exsolution step, and (iv) exsolution time on the particle size and particle density. Our results indicate that exsolution occurs quickly, forming nanoparticles both on the surface and in the bulk of the host perovskite. The findings indicate that pre-annealing in an ambient atmosphere leads to fewer but larger exsolved particles compared to samples without pre-annealing. Consequently, while crystallization of the thin film occurs in both atmospheres, the simultaneous crystallization of the thin film and formation of the nanoparticles leads to a smaller apparent average radius. Moreover, we present evidence that metal particles can be found beyond the originally doped region. These findings are a step towards realizing tunable functional materials using exsolution to create metallic nanostructures within a thin film in a predictable manner.