Evidence of Local Structural Variations and Their Influence on Magnetic Properties in Mn- and Cr-Containing High-Entropy Oxide Thin Films Using Electron Microscopy

Alloying is an age-old strategy for synthesizing materials with enhanced properties. Recently, multicomponent systems such as high-entropy oxides have garnered widespread attention due to their tunable and often superior properties compared to their constituent oxides. Here, we study the local structural and chemical nuances of six-component (Mg0.167Co0.167Ni0.167Cu0.167Zn0.167Mn0.167)O and (Mg0.167Co0.167Ni0.167Cu0.167Zn0.167Cr0.167)O thin films. The Mn-alloyed thin film exhibits a higher exchange bias and greater magnetic frustration compared with the Cr-containing thin film. Scanning/transmission electron microscopy investigations reveal that the Mn-alloyed thin film exhibits the coexistence of rock salt and spinel-like regions, unlike the single-phase rock salt structure observed in the Cr-alloyed thin film. Electron energy loss spectroscopy indicates changes in Co and Mn valences within the Mn-containing thin film, suggesting the presence of mixed-valence states, which are further confirmed by X-ray absorption spectroscopy measurements. These observations are further validated by cation-site-preference energy calculations using density functional theory. Our results demonstrate how the chemistry, site occupations, and cation valences result in pronounced changes in the overall properties of high-entropy oxides.