Universal A-Cation Splitting in LiNbO3-Type Structure Driven by Intrapositional Multivalent Coupling
Understanding the electric dipole switching in multiferroic materials requires deep insight of the atomic-scale local structure evolution to reveal the ferroelectric mechanism, which remains unclear and lacks a solid experimental indicator in high-pressure prepared LiNbO3-type polar magnets. Here, we report the discovery of Zn-ion splitting in LiNbO3-type Zn2FeNbO6 established by multiple diffraction techniques. The coexistence of a high-temperature paraelectric-like phase in the polar Zn2FeNbO6 lattice motivated us to revisit other high-pressure prepared LiNbO3-type A2BB'O6 compounds. The A-site atomic splitting (∼1.0-1.2 Å between the split-atom pair) in B/B'-mixed Zn2FeTaO6 and O/N-mixed ZnTaO2N is verified by both powder X-ray diffraction structural refinements and high angle annular dark field scanning transmission electron microscopy images, but is absent in single-B-site ZnSnO3. Theoretical calculations are in good agreement with experimental results and suggest that this kind of A-site splitting also exists in the B-site mixed Mn-analogues, Mn2FeMO6 (M = Nb, Ta) and anion-mixed MnTaO2N, where the smaller A-site splitting (∼0.2 Å atomic displacement) is attributed to magnetic interactions and bonding between A and B cations. These findings reveal universal A-site splitting in LiNbO3-type structures with mixed multivalent B/B', or anionic sites, and the splitting-atomic displacement can be strongly suppressed by magnetic interactions and/or hybridization of valence bands between d electrons of the A- and B-site cations.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2020 |
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| Erschienen: |
2020 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:142 |
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| Enthalten in: |
Journal of the American Chemical Society - 142(2020), 15 vom: 15. Apr., Seite 7168-7178 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Han, Yifeng [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Revised 15.04.2020 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/jacs.0c01814 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM308021606 |
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| 520 | |a Understanding the electric dipole switching in multiferroic materials requires deep insight of the atomic-scale local structure evolution to reveal the ferroelectric mechanism, which remains unclear and lacks a solid experimental indicator in high-pressure prepared LiNbO3-type polar magnets. Here, we report the discovery of Zn-ion splitting in LiNbO3-type Zn2FeNbO6 established by multiple diffraction techniques. The coexistence of a high-temperature paraelectric-like phase in the polar Zn2FeNbO6 lattice motivated us to revisit other high-pressure prepared LiNbO3-type A2BB'O6 compounds. The A-site atomic splitting (∼1.0-1.2 Å between the split-atom pair) in B/B'-mixed Zn2FeTaO6 and O/N-mixed ZnTaO2N is verified by both powder X-ray diffraction structural refinements and high angle annular dark field scanning transmission electron microscopy images, but is absent in single-B-site ZnSnO3. Theoretical calculations are in good agreement with experimental results and suggest that this kind of A-site splitting also exists in the B-site mixed Mn-analogues, Mn2FeMO6 (M = Nb, Ta) and anion-mixed MnTaO2N, where the smaller A-site splitting (∼0.2 Å atomic displacement) is attributed to magnetic interactions and bonding between A and B cations. These findings reveal universal A-site splitting in LiNbO3-type structures with mixed multivalent B/B', or anionic sites, and the splitting-atomic displacement can be strongly suppressed by magnetic interactions and/or hybridization of valence bands between d electrons of the A- and B-site cations | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Zeng, Yijie |e verfasserin |4 aut | |
| 700 | 1 | |a Hendrickx, Mylène |e verfasserin |4 aut | |
| 700 | 1 | |a Hadermann, Joke |e verfasserin |4 aut | |
| 700 | 1 | |a Stephens, Peter W |e verfasserin |4 aut | |
| 700 | 1 | |a Zhu, Chuanhui |e verfasserin |4 aut | |
| 700 | 1 | |a Grams, Christoph P |e verfasserin |4 aut | |
| 700 | 1 | |a Hemberger, Joachim |e verfasserin |4 aut | |
| 700 | 1 | |a Frank, Corey |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Shufang |e verfasserin |4 aut | |
| 700 | 1 | |a Wu, MeiXia |e verfasserin |4 aut | |
| 700 | 1 | |a Retuerto, Maria |e verfasserin |4 aut | |
| 700 | 1 | |a Croft, Mark |e verfasserin |4 aut | |
| 700 | 1 | |a Walker, David |e verfasserin |4 aut | |
| 700 | 1 | |a Yao, Dao-Xin |e verfasserin |4 aut | |
| 700 | 1 | |a Greenblatt, Martha |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Man-Rong |e verfasserin |4 aut | |
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