Robust Unusually High Valence Fe5+ State and Large Magnetic Interaction Change in the Double Perovskites La2–xCaxLiFeO6–0.5x

IF 7 2区材料科学 Q2 CHEMISTRY, PHYSICAL Chemistry of Materials Pub Date : 2025-02-20 DOI:10.1021/acs.chemmater.4c03494

Masato Goto, Kazunori Sato, Wei-tin Chen, Wei-Hsiang Huang, Yuichi Shimakawa

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Abstract

We successfully synthesized Ca-substituted B-site-ordered double perovskites La_2–xCa_xLiFeO₆ by using high-pressure techniques and investigated site-substitution effects on the stability of unusually high valence Fe ions and their magnetic properties. Our research revealed the robust Fe⁵⁺ state against the aliovalent substitution at the A site, as seen in the actual composition La_2–xCa_xLiFeO_6–0.5x. Introducing oxygen vacancies is a key factor in this discovery, as it significantly weakens the strong antiferromagnetic interaction for x = 0, transforming it into a weak ferromagnetic one for x > 0.3. This significant interaction change, coupled with the partial randomness of the magnetic interactions, easily releases the geometrical spin frustration of Fe⁵⁺ located on a face-centered-cubic lattice with just 5% Ca substitution. These results deepen our understanding of the site-substitution effects in geometrically frustrated B-site-ordered double perovskites.

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La2-xCaxLiFeO6-0.5x双钙钛矿中异常高价Fe5+态和大磁相互作用的变化

利用高压技术成功合成了钙取代b位有序双钙钛矿La2-xCaxLiFeO6，并研究了位置取代对异常高价铁离子稳定性和磁性能的影响。我们的研究揭示了Fe5+对A位的共价取代的稳健状态，如实际组成La2-xCaxLiFeO6-0.5x所示。引入氧空位是这一发现的关键因素，因为它显著削弱了x = 0的强反铁磁相互作用，将其转变为x >；0.3. 这种显著的相互作用变化，加上磁相互作用的部分随机性，很容易释放位于面心立方晶格上的Fe5+的几何自旋受挫，只需5%的Ca取代。这些结果加深了我们对几何受挫b位有序双钙钛矿中位取代效应的理解。

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.