Selective Oxidation and Cr Segregation in High-Entropy Oxide Thin Films
High-entropy oxides (HEOs) offer exceptional compositional flexibility and structural stability, making them promising materials for energy and catalytic applications. Here, we investigate Sr doping effects on B-site cation oxidation states, local composition, and structure in epitaxial La<sub>1-<i>x</i></sub>Sr<sub><i>x</i></sub>(Cr<sub>0.2</sub>Mn<sub>0.2</sub>Fe<sub>0.2</sub>Co<sub>0.2</sub>Ni<sub>0.2</sub>)O<sub>3</sub> thin films. X-ray spectroscopies reveal that Sr doping preferentially promotes Cr oxidation from Cr<sup>3+</sup> to Cr<sup>6+</sup>, partially oxidizes Co and Ni, while leaving Mn<sup>4+</sup> and Fe<sup>3+</sup> unchanged. Atomic-resolution scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy shows pronounced Cr segregation, with depletion at the interface and enrichment at the surface, along with partial amorphization in heavily Sr-doped samples. This segregation is likely driven by oxidation-induced migration of smaller, high-valence Cr cations during growth. These findings highlight the critical interplay between charge compensation, local strain, and compositional fluctuations in HEOs, indicating that precise control over growth conditions is critical for tuning their surface composition and electronic structure toward more robust electrocatalyst design.
Authors
- Dongchen Qi (ORCID: https://orcid.org/0000-0001-8466-0257)
- Zihua Zhu (ORCID: https://orcid.org/0000-0001-5770-8462)
- Hua Zhou (ORCID: https://orcid.org/0000-0001-9642-8674)
- Yingge Du (ORCID: https://orcid.org/0000-0001-9680-1950)
- Chih‐Hung Chang (ORCID: https://orcid.org/0000-0003-3429-3940)
- Andrew Ho (ORCID: https://orcid.org/0000-0003-1287-9844)
- Krishna Prasad Koirala (ORCID: https://orcid.org/0000-0002-9137-917X)
- Shuhang Wu (ORCID: https://orcid.org/0000-0002-0311-0788)
- Mark Bowden (ORCID: https://orcid.org/0000-0003-3812-3340)
- Jueli Shi (ORCID: https://orcid.org/0000-0001-9122-8921)
- Bethany E. Matthews (ORCID: https://orcid.org/0000-0001-7193-2583)
- Alexander B. C. Mantilla (ORCID: https://orcid.org/0000-0002-9262-1351)
- Anton Tadich (ORCID: https://orcid.org/0000-0001-9455-5901)
- Min‐Ju Choi (ORCID: https://orcid.org/0000-0003-1876-3228)
- Le Wang (ORCID: https://orcid.org/0000-0002-7730-9482)
- Yang Yang (ORCID: https://orcid.org/0000-0002-6417-3483)
- Chongmin Wang (ORCID: https://orcid.org/0000-0003-3327-0958)
- Hsin-Mei Kao (ORCID: https://orcid.org/0009-0000-3418-6315)
Institutions
- Argonne National Laboratory (US)
- Oregon State University (US)
- Australian Nuclear Science and Technology Organisation (AU)
- Pacific Northwest National Laboratory (US)
- Santa Rosa Junior College (US)
- Queensland University of Technology (AU)
- Brookhaven National Laboratory (US)
- Environmental Molecular Sciences Laboratory (US)
- Australian Synchrotron (AU)
- Centre for Biomedical Engineering and Physics (SE)
- Stanford Synchrotron Radiation Lightsource (US)
- National Synchrotron Light Source II
Publication Details
- Journal
- Nano Letters
- Published
- 2025-08-11
- DOI
- https://doi.org/10.1021/acs.nanolett.5c03196
- Citations
- 1
- Primary Topic
- Electronic and Structural Properties of Oxides
- Type
- article
- Field-Weighted Citation Impact
- 0.52
Funders
- Basic Energy Sciences