Suppression of Sequential Charge Transitions in Ca_{0.5}Bi_{0.5}FeO₃ via B-Site Cobalt Substitution

Fabio Denis Romero; Peng Xiong; Midori Amano Patino; Takashi Saito; Paula Kayser; J. Paul Attfield; Yuichi Shimakawa

doi:10.1021/acs.chemmater.8b02524

journal article·2018-08-14Open access

Suppression of Sequential Charge Transitions in Ca_0.5Bi_0.5FeO₃ via B-Site Cobalt Substitution

Fabio Denis Romero, Peng Xiong, Midori Amano Patino, Takashi Saito, Paula Kayser, J. Paul Attfield, Yuichi Shimakawa

Chemistry of Materials· Volume 30· Issue 15

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Source abstract

Abstract

The perovskite Ca0.5Bi0.5FeO3 containing unusually high-valent Fe3.5+ undergoes sequentially charge disproportionation (CD) of the Fe centers and intersite charge transfer (CT) between Bi and Fe. From structural, magnetic, and transport property characterization, we found that substitution of Co for Fe occurs isovalently to form Ca0.5Bi3+0.5(Fe1–xCox)3.5+O3 and destabilizes the CD state. This results in materials exhibiting only intermetallic charge transfer behavior in the region 0.01 < x < 0.67. The CT transitions for these materials only involve Fe3.5+, whereas Co remains in the 3.5+ oxidation state at all temperatures. The doped Co3.5+ ions give Pauli-paramagnetic like conducting behavior. The Co-substitution effect is very different from that observed in CaFe1–xCoxO3.

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Research context

Metals & alloys Electronic materials

OpenAlex topics: Magnetic and transport properties of perovskites and related materials · Multiferroics and related materials · Thermal Expansion and Ionic Conductivity

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan

Hakubi Center for Advanced Research, Kyoto University, Yoshida-honmachi, Sakyo-ku, Kyoto 606-8501, Japan

Centre for Science at Extreme Conditions and School of Chemistry, The University of Edinburgh, Edinburgh EH9 3JZ, U.K.

Funding

Royal Society · Engineering and Physical Sciences Research Council · Ministry of Education, Culture, Sports, Science and Technology · Japan Society for the Promotion of Science

References (18)

Show source-provided references

1. 10.1016/0025-5408(77)90104-010.1016/0025-5408(77)90104-0 ↗

2. 10.1103/PhysRevB.62.84410.1103/PhysRevB.62.844 ↗

3. 10.1038/nature0781610.1038/nature07816 ↗

4. 10.1088/0022-3727/48/50/50400610.1088/0022-3727/48/50/504006 ↗

5. 10.1021/ja074880u10.1021/ja074880u ↗

6. 10.1002/anie.20170088110.1002/anie.201700881 ↗

7. 10.1103/PhysRevB.96.06443410.1103/PhysRevB.96.064434 ↗

8. 10.1063/1.165753010.1063/1.1657530 ↗

9. 10.1143/JPSJ.67.152910.1143/JPSJ.67.1529 ↗

10. Larson, A. C.; Von Dreele, R. B. General Structure Analysis System (GSAS); Los Alamos National Laboratory Report LAUR 86-748; The Regents of the University of California: Oakland, CA, 2000; pp 86–748.

11. Greenwood N. N. · 2012

12. 10.1107/S010876819001104110.1107/S0108768190011041 ↗

13. 10.1021/acs.inorgchem.7b0278510.1021/acs.inorgchem.7b02785 ↗

14. 10.2497/jjspm.65.26910.2497/jjspm.65.269 ↗

15. 10.1016/0025-5408(71)90075-410.1016/0025-5408(71)90075-4 ↗

16. 10.1134/S002136401014008010.1134/S0021364010140080 ↗

17. 10.1143/JPSJ.72.87310.1143/JPSJ.72.873 ↗

18. Goodenough J. B. · 1963