高エントロピー酸化物薄膜の酸化選択性とクロムの偏析（When High Entropy Meets Epitaxy: Selective Oxidation and Chromium Segregation in Multicomponent Oxide Thin Films）

2025-09-15 パシフィック・ノースウェスト国立研究所 (PNNL)

Studies reveal that chromium in high-entropy oxides tends to segregate during growth due to oxidation-induced migration of smaller, high-valence Cr cations.
(Image by Nathan Johnson | Pacific Northwest National Laboratory)

＜関連情報＞

• https://www.pnnl.gov/publications/when-high-entropy-meets-epitaxy-selective-oxidation-and-chromium-segregation
• https://pubs.acs.org/doi/10.1021/acs.nanolett.5c03196

高エントロピー酸化物薄膜における選択的酸化とCr偏析 Selective Oxidation and Cr Segregation in High-Entropy Oxide Thin Films

Le Wang,Krishna Prasad Koirala,Shuhang Wu,Jueli Shi,Hsin-Mei Kao,Andrew Ho,Min-Ju Choi,Alexander B. C. Mantilla,Dongchen Qi,Anton Tadich,Mark E. Bowden,Bethany E. Matthews,Hua Zhou,Yang Yang,Chih-hung Chang,Zihua Zhu,Chongmin Wang,and Yingge Du
Nano Letters  Published: August 11, 2025
DOI:https://doi.org/10.1021/acs.nanolett.5c03196

Abstract

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_1–xSr_x(Cr_0.2Mn_0.2Fe_0.2Co_0.2Ni_0.2)O₃ thin films. X-ray spectroscopies reveal that Sr doping preferentially promotes Cr oxidation from Cr³⁺ to Cr⁶⁺, partially oxidizes Co and Ni, while leaving Mn⁴⁺ and Fe³⁺ 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.