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arXiv · 2503.10960

Exploration of metastable A-site-ordered perovskites (Ca,Ba)FeO3-δ by computationally-guided multi-step synthesis

Masaho Onose·Hidefumi Takahashi·Hajime Sagayama·Yuichi Yamasaki·Shintaro Ishiwata
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Abstract

Perovskite-type iron oxides with Fe4+ ions have attracted much attention for their versatile helimagnetic phases. While the introduction of a layered A-site ordered structure to AFeO3 with Fe4+ ions potentially lead to novel helimagnetic phases, the synthetic pathway spanning high pressure range is apparently difficult to elucidate. Here, we explored new A-site ordered perovskite-type iron oxides (Ca,Ba)FeO3-δ with Fe4+ ions with the support of first-principles calculations evaluating thermodynamic stability at selected pressures and chemical compositions. Among the six types of putative A-site ordered perovskites with and without oxygen vacancy, only two types of oxygen-deficient perovskites CaBaFe2O6-δ and Ca(Ba0.9Ca0.1)2Fe3O9-δ (δ~1) were successfully obtained by high-pressure synthesis, being consistent with the DFT-based convex-hull calculations. Considering the evaluated stability of the putative perovskites at selected pressures, we adopted low-temperature topotactic oxidation using ozone at ambient pressure and obtained the oxidized perovskites CaBaFe2O6-δ (δ~0.4) and Ca(Ba0.9Ca0.1)2Fe3O9-δ (δ~0.6), potentially showing novel helimagnetic phases. This study demonstrates that computational visualization of multi-step synthetic pathways involving high pressure can accelerate the search for new metastable perovskites with rich magnetic phases.

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Masaho Onose, Hidefumi Takahashi, Hajime Sagayama, Yuichi Yamasaki, Shintaro Ishiwata. 2025-03-14. Exploration of metastable A-site-ordered perovskites (Ca,Ba)FeO3-δ by computationally-guided multi-step synthesis. https://doi.org/10.1021/jacs.4c15392

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