Exploration of metastable A-site-ordered perovskites (Ca,Ba)FeO3-δ by computationally-guided multi-step synthesis
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| Main Authors: | , , , , |
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| Format: | Preprint |
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2025
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| _version_ | 1866916652449267712 |
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| author | Onose, Masaho Takahashi, Hidefumi Sagayama, Hajime Yamasaki, Yuichi Ishiwata, Shintaro |
| author_facet | Onose, Masaho Takahashi, Hidefumi Sagayama, Hajime Yamasaki, Yuichi Ishiwata, Shintaro |
| contents | 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. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2503_10960 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Exploration of metastable A-site-ordered perovskites (Ca,Ba)FeO3-δ by computationally-guided multi-step synthesis Onose, Masaho Takahashi, Hidefumi Sagayama, Hajime Yamasaki, Yuichi Ishiwata, Shintaro Materials Science Strongly Correlated Electrons 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. |
| title | Exploration of metastable A-site-ordered perovskites (Ca,Ba)FeO3-δ by computationally-guided multi-step synthesis |
| topic | Materials Science Strongly Correlated Electrons |
| url | https://arxiv.org/abs/2503.10960 |