Emergent and robust ferromagnetic-insulating state in highly strained ferroelastic LaCoO3 thin films

Dong Li; Hongguang Wang; Kaifeng Li; Bonan Zhu; Kai Jiang; Dirk Backes; Larissa S.I. Veiga; Jueli Shi; Pinku Roy; Ming Xiao; Aiping Chen; Quanxi Jia; Tien Lin Lee; Sarnjeet S. Dhesi; David O. Scanlon; Judith L. MacManus-Driscoll; Peter A. van Aken; Kelvin H.L. Zhang; Weiwei Li

doi:10.1038/s41467-023-39369-6

Emergent and robust ferromagnetic-insulating state in highly strained ferroelastic LaCoO₃ thin films

Dong Li, Hongguang Wang^*, Kaifeng Li, Bonan Zhu^*, Kai Jiang^*, Dirk Backes, Larissa S.I. Veiga, Jueli Shi, Pinku Roy, Ming Xiao, Aiping Chen, Quanxi Jia, Tien Lin Lee, Sarnjeet S. Dhesi, David O. Scanlon, Judith L. MacManus-Driscoll, Peter A. van Aken, Kelvin H.L. Zhang^*, Weiwei Li^*

^*Corresponding author for this work

Chemistry

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Abstract

Transition metal oxides are promising candidates for the next generation of spintronic devices due to their fascinating properties that can be effectively engineered by strain, defects, and microstructure. An excellent example can be found in ferroelastic LaCoO₃ with paramagnetism in bulk. In contrast, unexpected ferromagnetism is observed in tensile-strained LaCoO₃ films, however, its origin remains controversial. Here we simultaneously reveal the formation of ordered oxygen vacancies and previously unreported long-range suppression of CoO₆ octahedral rotations throughout LaCoO₃ films. Supported by density functional theory calculations, we find that the strong modification of Co 3d-O 2p hybridization associated with the increase of both Co-O-Co bond angle and Co-O bond length weakens the crystal-field splitting and facilitates an ordered high-spin state of Co ions, inducing an emergent ferromagnetic-insulating state. Our work provides unique insights into underlying mechanisms driving the ferromagnetic-insulating state in tensile-strained ferroelastic LaCoO₃ films while suggesting potential applications toward low-power spintronic devices.

Original language	English
Article number	3638
Number of pages	9
Journal	Nature Communications
Volume	14
Issue number	1
Early online date	19 Jun 2023
DOIs	https://doi.org/10.1038/s41467-023-39369-6
Publication status	Published - Dec 2023

Bibliographical note

Funding Information:
W.-W.L. and K.H.L.Z. acknowledge support from the National Natural Science Foundation of China (Grant No. 52102177, Grant No. 21872116, and No. 22075232). W.-W.L. is grateful for funding support from the National Natural Science Foundation of Jiangsu Province (Grant No. BK20210313), the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions (TAPP), and the Jiangsu Specially-Appointed Professor Program. The research work is supported by the supporting funds for the talents of Nanjing University of Aeronautics and Astronautics. We thank the Diamond Light Source for the time on beamline I06 (proposal MM25425, MM26901, and MM29616) and beamline I09 (proposal SI31069). J.L.M.-D. and M.X. thank the Royal Academy of Engineering, grant CIET1819_24, for funding. Via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/R029431), this work used the ARCHER2 UK National Supercomputing Service ( http://www.archer2.ac.uk ), the UK Materials and Molecular Modelling Hub for computational resources, MMM Hub, which is partially funded by EPSRC (EP/P020194). The authors also acknowledge the use of the UCL Myriad and Kathleen High Performance Computing Facility (Myriad@UCL, Kathleen@UCL), and associated support services, in the completion of this work. The work at Los Alamos National Laboratory was supported by the NNSA’s Laboratory Directed Research and Development Program and was performed, in part, at the Center for Integrated Nanotechnologies (CINT), an Office of Science User Facility operated for the U.S. Department of Energy Office of Science. Los Alamos National Laboratory, an affirmative action equal opportunity employer, is managed by Triad National Security, LLC for the U.S. Department of Energy’s NNSA, under contract 89233218CNA000001. The work at the University at Buffalo was partially supported by the U.S. National Science Foundation under award number ECCS-1902623. Q.X.J. also acknowledges the CINT Users Program. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under Grant Agreement No. 823717-ESTEEM3.

Publisher Copyright:
© 2023, The Author(s).

ASJC Scopus subject areas

General Chemistry
General Biochemistry,Genetics and Molecular Biology
General Physics and Astronomy

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Cite this

Li, D., Wang, H., Li, K., Zhu, B., Jiang, K., Backes, D., Veiga, L. S. I., Shi, J., Roy, P., Xiao, M., Chen, A., Jia, Q., Lee, T. L., Dhesi, S. S., Scanlon, D. O., MacManus-Driscoll, J. L., van Aken, P. A., Zhang, K. H. L., & Li, W. (2023). Emergent and robust ferromagnetic-insulating state in highly strained ferroelastic LaCoO₃ thin films. Nature Communications, 14(1), Article 3638. https://doi.org/10.1038/s41467-023-39369-6

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title = "Emergent and robust ferromagnetic-insulating state in highly strained ferroelastic LaCoO3 thin films",

abstract = "Transition metal oxides are promising candidates for the next generation of spintronic devices due to their fascinating properties that can be effectively engineered by strain, defects, and microstructure. An excellent example can be found in ferroelastic LaCoO3 with paramagnetism in bulk. In contrast, unexpected ferromagnetism is observed in tensile-strained LaCoO3 films, however, its origin remains controversial. Here we simultaneously reveal the formation of ordered oxygen vacancies and previously unreported long-range suppression of CoO6 octahedral rotations throughout LaCoO3 films. Supported by density functional theory calculations, we find that the strong modification of Co 3d-O 2p hybridization associated with the increase of both Co-O-Co bond angle and Co-O bond length weakens the crystal-field splitting and facilitates an ordered high-spin state of Co ions, inducing an emergent ferromagnetic-insulating state. Our work provides unique insights into underlying mechanisms driving the ferromagnetic-insulating state in tensile-strained ferroelastic LaCoO3 films while suggesting potential applications toward low-power spintronic devices.",

author = "Dong Li and Hongguang Wang and Kaifeng Li and Bonan Zhu and Kai Jiang and Dirk Backes and Veiga, {Larissa S.I.} and Jueli Shi and Pinku Roy and Ming Xiao and Aiping Chen and Quanxi Jia and Lee, {Tien Lin} and Dhesi, {Sarnjeet S.} and Scanlon, {David O.} and MacManus-Driscoll, {Judith L.} and {van Aken}, {Peter A.} and Zhang, {Kelvin H.L.} and Weiwei Li",

note = "Funding Information: W.-W.L. and K.H.L.Z. acknowledge support from the National Natural Science Foundation of China (Grant No. 52102177, Grant No. 21872116, and No. 22075232). W.-W.L. is grateful for funding support from the National Natural Science Foundation of Jiangsu Province (Grant No. BK20210313), the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions (TAPP), and the Jiangsu Specially-Appointed Professor Program. The research work is supported by the supporting funds for the talents of Nanjing University of Aeronautics and Astronautics. We thank the Diamond Light Source for the time on beamline I06 (proposal MM25425, MM26901, and MM29616) and beamline I09 (proposal SI31069). J.L.M.-D. and M.X. thank the Royal Academy of Engineering, grant CIET1819_24, for funding. Via our membership of the UK{\textquoteright}s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/R029431), this work used the ARCHER2 UK National Supercomputing Service ( http://www.archer2.ac.uk ), the UK Materials and Molecular Modelling Hub for computational resources, MMM Hub, which is partially funded by EPSRC (EP/P020194). The authors also acknowledge the use of the UCL Myriad and Kathleen High Performance Computing Facility (Myriad@UCL, Kathleen@UCL), and associated support services, in the completion of this work. The work at Los Alamos National Laboratory was supported by the NNSA{\textquoteright}s Laboratory Directed Research and Development Program and was performed, in part, at the Center for Integrated Nanotechnologies (CINT), an Office of Science User Facility operated for the U.S. Department of Energy Office of Science. Los Alamos National Laboratory, an affirmative action equal opportunity employer, is managed by Triad National Security, LLC for the U.S. Department of Energy{\textquoteright}s NNSA, under contract 89233218CNA000001. The work at the University at Buffalo was partially supported by the U.S. National Science Foundation under award number ECCS-1902623. Q.X.J. also acknowledges the CINT Users Program. This project has received funding from the European Union{\textquoteright}s Horizon 2020 research and innovation programme under Grant Agreement No. 823717-ESTEEM3. Publisher Copyright: {\textcopyright} 2023, The Author(s).",

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doi = "10.1038/s41467-023-39369-6",

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Li, D, Wang, H, Li, K, Zhu, B, Jiang, K, Backes, D, Veiga, LSI, Shi, J, Roy, P, Xiao, M, Chen, A, Jia, Q, Lee, TL, Dhesi, SS, Scanlon, DO, MacManus-Driscoll, JL, van Aken, PA, Zhang, KHL & Li, W 2023, 'Emergent and robust ferromagnetic-insulating state in highly strained ferroelastic LaCoO₃ thin films', Nature Communications, vol. 14, no. 1, 3638. https://doi.org/10.1038/s41467-023-39369-6

TY - JOUR

T1 - Emergent and robust ferromagnetic-insulating state in highly strained ferroelastic LaCoO3 thin films

AU - Li, Dong

AU - Wang, Hongguang

AU - Li, Kaifeng

AU - Zhu, Bonan

AU - Jiang, Kai

AU - Backes, Dirk

AU - Veiga, Larissa S.I.

AU - Shi, Jueli

AU - Roy, Pinku

AU - Xiao, Ming

AU - Chen, Aiping

AU - Jia, Quanxi

AU - Lee, Tien Lin

AU - Dhesi, Sarnjeet S.

AU - Scanlon, David O.

AU - MacManus-Driscoll, Judith L.

AU - van Aken, Peter A.

AU - Zhang, Kelvin H.L.

AU - Li, Weiwei

N1 - Funding Information: W.-W.L. and K.H.L.Z. acknowledge support from the National Natural Science Foundation of China (Grant No. 52102177, Grant No. 21872116, and No. 22075232). W.-W.L. is grateful for funding support from the National Natural Science Foundation of Jiangsu Province (Grant No. BK20210313), the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions (TAPP), and the Jiangsu Specially-Appointed Professor Program. The research work is supported by the supporting funds for the talents of Nanjing University of Aeronautics and Astronautics. We thank the Diamond Light Source for the time on beamline I06 (proposal MM25425, MM26901, and MM29616) and beamline I09 (proposal SI31069). J.L.M.-D. and M.X. thank the Royal Academy of Engineering, grant CIET1819_24, for funding. Via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/R029431), this work used the ARCHER2 UK National Supercomputing Service ( http://www.archer2.ac.uk ), the UK Materials and Molecular Modelling Hub for computational resources, MMM Hub, which is partially funded by EPSRC (EP/P020194). The authors also acknowledge the use of the UCL Myriad and Kathleen High Performance Computing Facility (Myriad@UCL, Kathleen@UCL), and associated support services, in the completion of this work. The work at Los Alamos National Laboratory was supported by the NNSA’s Laboratory Directed Research and Development Program and was performed, in part, at the Center for Integrated Nanotechnologies (CINT), an Office of Science User Facility operated for the U.S. Department of Energy Office of Science. Los Alamos National Laboratory, an affirmative action equal opportunity employer, is managed by Triad National Security, LLC for the U.S. Department of Energy’s NNSA, under contract 89233218CNA000001. The work at the University at Buffalo was partially supported by the U.S. National Science Foundation under award number ECCS-1902623. Q.X.J. also acknowledges the CINT Users Program. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under Grant Agreement No. 823717-ESTEEM3. Publisher Copyright: © 2023, The Author(s).

PY - 2023/12

Y1 - 2023/12

N2 - Transition metal oxides are promising candidates for the next generation of spintronic devices due to their fascinating properties that can be effectively engineered by strain, defects, and microstructure. An excellent example can be found in ferroelastic LaCoO3 with paramagnetism in bulk. In contrast, unexpected ferromagnetism is observed in tensile-strained LaCoO3 films, however, its origin remains controversial. Here we simultaneously reveal the formation of ordered oxygen vacancies and previously unreported long-range suppression of CoO6 octahedral rotations throughout LaCoO3 films. Supported by density functional theory calculations, we find that the strong modification of Co 3d-O 2p hybridization associated with the increase of both Co-O-Co bond angle and Co-O bond length weakens the crystal-field splitting and facilitates an ordered high-spin state of Co ions, inducing an emergent ferromagnetic-insulating state. Our work provides unique insights into underlying mechanisms driving the ferromagnetic-insulating state in tensile-strained ferroelastic LaCoO3 films while suggesting potential applications toward low-power spintronic devices.

AB - Transition metal oxides are promising candidates for the next generation of spintronic devices due to their fascinating properties that can be effectively engineered by strain, defects, and microstructure. An excellent example can be found in ferroelastic LaCoO3 with paramagnetism in bulk. In contrast, unexpected ferromagnetism is observed in tensile-strained LaCoO3 films, however, its origin remains controversial. Here we simultaneously reveal the formation of ordered oxygen vacancies and previously unreported long-range suppression of CoO6 octahedral rotations throughout LaCoO3 films. Supported by density functional theory calculations, we find that the strong modification of Co 3d-O 2p hybridization associated with the increase of both Co-O-Co bond angle and Co-O bond length weakens the crystal-field splitting and facilitates an ordered high-spin state of Co ions, inducing an emergent ferromagnetic-insulating state. Our work provides unique insights into underlying mechanisms driving the ferromagnetic-insulating state in tensile-strained ferroelastic LaCoO3 films while suggesting potential applications toward low-power spintronic devices.

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