Geometric frustration of Jahn-Teller order in the infinite-layer lattice
© 2023. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply..
The Jahn-Teller effect, in which electronic configurations with energetically degenerate orbitals induce lattice distortions to lift this degeneracy, has a key role in many symmetry-lowering crystal deformations1. Lattices of Jahn-Teller ions can induce a cooperative distortion, as exemplified by LaMnO3 (refs. 2,3). Although many examples occur in octahedrally4 or tetrahedrally5 coordinated transition metal oxides due to their high orbital degeneracy, this effect has yet to be manifested for square-planar anion coordination, as found in infinite-layer copper6,7, nickel8,9, iron10,11 and manganese oxides12. Here we synthesize single-crystal CaCoO2 thin films by topotactic reduction of the brownmillerite CaCoO2.5 phase. We observe a markedly distorted infinite-layer structure, with ångström-scale displacements of the cations from their high-symmetry positions. This can be understood to originate from the Jahn-Teller degeneracy of the dxz and dyz orbitals in the d7 electronic configuration along with substantial ligand-transition metal mixing. A complex pattern of distortions arises in a [Formula: see text] tetragonal supercell, reflecting the competition between an ordered Jahn-Teller effect on the CoO2 sublattice and the geometric frustration of the associated displacements of the Ca sublattice, which are strongly coupled in the absence of apical oxygen. As a result of this competition, the CaCoO2 structure forms an extended two-in-two-out type of Co distortion following 'ice rules'13.
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| Medienart: |
E-Artikel |
| Erscheinungsjahr: |
2023 |
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| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:615 |
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| Enthalten in: |
Nature - 615(2023), 7951 vom: 22. März, Seite 237-243 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Kim, Woo Jin [VerfasserIn] |
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Journal Article |
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Date Completed 11.03.2023 Date Revised 20.07.2023 published: Print-Electronic ErratumIn: Nature. 2023 Aug;620(7972):E12. - PMID 37474799 Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1038/s41586-022-05681-2 |
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| 100 | 1 | |a Kim, Woo Jin |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Geometric frustration of Jahn-Teller order in the infinite-layer lattice |
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| 500 | |a Date Revised 20.07.2023 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a ErratumIn: Nature. 2023 Aug;620(7972):E12. - PMID 37474799 | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a © 2023. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply. | ||
| 520 | |a The Jahn-Teller effect, in which electronic configurations with energetically degenerate orbitals induce lattice distortions to lift this degeneracy, has a key role in many symmetry-lowering crystal deformations1. Lattices of Jahn-Teller ions can induce a cooperative distortion, as exemplified by LaMnO3 (refs. 2,3). Although many examples occur in octahedrally4 or tetrahedrally5 coordinated transition metal oxides due to their high orbital degeneracy, this effect has yet to be manifested for square-planar anion coordination, as found in infinite-layer copper6,7, nickel8,9, iron10,11 and manganese oxides12. Here we synthesize single-crystal CaCoO2 thin films by topotactic reduction of the brownmillerite CaCoO2.5 phase. We observe a markedly distorted infinite-layer structure, with ångström-scale displacements of the cations from their high-symmetry positions. This can be understood to originate from the Jahn-Teller degeneracy of the dxz and dyz orbitals in the d7 electronic configuration along with substantial ligand-transition metal mixing. A complex pattern of distortions arises in a [Formula: see text] tetragonal supercell, reflecting the competition between an ordered Jahn-Teller effect on the CoO2 sublattice and the geometric frustration of the associated displacements of the Ca sublattice, which are strongly coupled in the absence of apical oxygen. As a result of this competition, the CaCoO2 structure forms an extended two-in-two-out type of Co distortion following 'ice rules'13 | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Research Support, U.S. Gov't, Non-P.H.S. | |
| 650 | 4 | |a Research Support, U.S. Gov't, P.H.S. | |
| 650 | 4 | |a Research Support, Non-U.S. Gov't | |
| 700 | 1 | |a Smeaton, Michelle A |e verfasserin |4 aut | |
| 700 | 1 | |a Jia, Chunjing |e verfasserin |4 aut | |
| 700 | 1 | |a Goodge, Berit H |e verfasserin |4 aut | |
| 700 | 1 | |a Cho, Byeong-Gwan |e verfasserin |4 aut | |
| 700 | 1 | |a Lee, Kyuho |e verfasserin |4 aut | |
| 700 | 1 | |a Osada, Motoki |e verfasserin |4 aut | |
| 700 | 1 | |a Jost, Daniel |e verfasserin |4 aut | |
| 700 | 1 | |a Ievlev, Anton V |e verfasserin |4 aut | |
| 700 | 1 | |a Moritz, Brian |e verfasserin |4 aut | |
| 700 | 1 | |a Kourkoutis, Lena F |e verfasserin |4 aut | |
| 700 | 1 | |a Devereaux, Thomas P |e verfasserin |4 aut | |
| 700 | 1 | |a Hwang, Harold Y |e verfasserin |4 aut | |
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