Nevgi Rukma, Dey Subha, Bhattacharya Nandana, Ershadrad Soheil, Dan Tinku, Chakravarty Sujay, Kaushik S D, Klewe Christoph, Sterbinsky George E, Sanyal Biplab, Middey Srimanta
Department of Physics, Indian Institute of Science, Bengaluru, 560012, India.
Department of Physics and Astronomy, Uppsala University, Box-516, 75120, Uppsala, Sweden.
Nat Commun. 2025 Jul 31;16(1):7038. doi: 10.1038/s41467-025-62268-x.
Understanding how local distortions determine the functional properties of high entropy materials, containing five or more elements at the same crystallographic site, is an open challenge. We address this for a compositionally complex spinel oxide (MnCoNiCuZn)CrO (ACrO). By comparatively examining extended X-ray absorption fine structure on ACrO and its parent counterparts, ACrO along with density functional theory calculations for multiple configurations, we find that the element-specific distortions go beyond the first neighbor. Specifically, the strong Jahn-Teller distortion present in CuCrO is found to be completely suppressed in ACrO even locally. Instead, there is a broad distribution of Cu-O and Cu-Cr bond distances, while other A-O distances acquire certain specific values. This study demonstrates the additional flexibility of a cationic sublattice in maintaining a uniform long-range structure, in contrast to previous reports showing only the accommodative anionic sublattice. The mean-field magnetic interactions of ACrO exhibit a striking resemblance to those of NiCrO, despite the presence of multiple magnetic ions and variable bond lengths. This originates from the comparability of bond lengths around Cr in both materials. Our study paves the way for a deeper understanding of the impact of local structural distortions on the physical properties of compositionally complex quantum materials.
理解局部畸变如何决定同一晶体学位置包含五种或更多元素的高熵材料的功能特性,是一项尚未解决的挑战。我们针对一种成分复杂的尖晶石氧化物(MnCoNiCuZn)CrO₂(ACrO₂)来解决这个问题。通过比较研究ACrO₂及其母体对应物的扩展X射线吸收精细结构,以及对多种构型进行密度泛函理论计算,我们发现特定元素的畸变超出了第一近邻范围。具体而言,我们发现CuCrO₂中存在的强 Jahn-Teller 畸变在ACrO₂中甚至局部都被完全抑制。相反,Cu-O和Cu-Cr键长存在广泛分布,而其他A-O键长则获得了某些特定值。与之前仅显示容纳性阴离子亚晶格的报告相反,本研究证明了阳离子亚晶格在维持均匀长程结构方面具有额外的灵活性。尽管存在多种磁性离子和可变键长,但ACrO₂的平均场磁相互作用与NiCrO₂的平均场磁相互作用惊人地相似。这源于两种材料中Cr周围键长的可比性。我们的研究为更深入理解局部结构畸变对成分复杂的量子材料物理性质的影响铺平了道路。