Tuning grain boundary cation segregation with oxygen deficiency and atomic structure in a perovskite compositionally complex oxide thin film

Compositionally complex oxides (CCOs) are an emerging class of materials encompassing high entropy and entropy stabilized oxides (HEOs, ESOs). These promising advanced materials leverage tunable chemical bond structure, lattice distortion, and chemical disorder for unprecedented properties. Grain boundary (GB) and point defect segregation to GBs is relatively understudied in CCOs even though they can govern macroscopic material properties. For example, GB segregation can govern local chemical (dis)order and point defect distribution, playing a critical role in electrochemical reaction kinetics, and charge and mass transport in solid electrolytes. However, compared with conventional oxides, GBs in multi-cation CCO systems are expected to exhibit more complex segregation phenomena and thus prove more difficult to tune through GB design strategies. Here, GB segregation was studied in a model perovskite CCO LaFe0.7Ni0.1Co0.1Cu0.05Pd0.05O3-x textured thin film by (sub-)atomic-resolution scanning transmission electron microscopy imaging and spectroscopy. It is found that GB segregation is correlated with cation reducibility—predicted by an Ellingham diagram—as Pd and Cu segregate to GBs rich in oxygen vacancies (𝑉 𝑂 ∙∙). Furthermore, Pd and Cu segregation is highly sensitive to the concentration and spatial distribution of 𝑉 𝑂 ∙∙ along the GB plane, as well as fluctuations in atomic structure and elastic strain induced by GB local disorder, such as dislocations. This work offers a perspective of controlling segregation concentration of CCO cations to GBs by tuning reducibility of CCO cations and oxygen deficiency, which is expected to guide GB design in CCOs.