Room-temperature valence transition in a strain-tuned perovskite oxide

Vipul Chaturvedi; Supriya Ghosh; Dominique Gautreau; William M. Postiglione; John E. Dewey; Patrick Quarterman; Purnima P. Balakrishnan; Brian J. Kirby; Hua Zhou; Huikai Cheng; Amanda Huon; Timothy Charlton; Michael R. Fitzsimmons; Caroline Korostynski; Andrew Jacobson; Lucca Figari; Javier Garcia Barriocanal; Turan Birol; K. Andre Mkhoyan; Chris Leighton

doi:10.1038/s41467-022-35024-8

Room-temperature valence transition in a strain-tuned perovskite oxide

Vipul Chaturvedi, Supriya Ghosh, Dominique Gautreau, William M. Postiglione, John E. Dewey, Patrick Quarterman, Purnima P. Balakrishnan, Brian J. Kirby, Hua Zhou, Huikai Cheng, Amanda Huon, Timothy Charlton, Michael R. Fitzsimmons, Caroline Korostynski, Andrew Jacobson, Lucca Figari, Javier Garcia Barriocanal, Turan Birol, K. Andre Mkhoyan, Chris Leighton

Reflectometry

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

Cobalt oxides have long been understood to display intriguing phenomena known as spin-state crossovers, where the cobalt ion spin changes vs. temperature, pressure, etc. A very different situation was recently uncovered in praseodymium-containing cobalt oxides, where a first-order coupled spin-state/structural/metal-insulator transition occurs, driven by a remarkable praseodymium valence transition. Such valence transitions, particularly when triggering spin-state and metal-insulator transitions, offer highly appealing functionality, but have thus far been confined to cryogenic temperatures in bulk materials (e.g., 90 K in Pr_1-xCa_xCoO₃). Here, we show that in thin films of the complex perovskite (Pr_1-yY_y)_1-xCa_xCoO_3-δ, heteroepitaxial strain tuning enables stabilization of valence-driven spin-state/structural/metal-insulator transitions to at least 291 K, i.e., around room temperature. The technological implications of this result are accompanied by fundamental prospects, as complete strain control of the electronic ground state is demonstrated, from ferromagnetic metal under tension to nonmagnetic insulator under compression, thereby exposing a potential novel quantum critical point.

Original language	English
Article number	7774
Journal	Nature Communications
Volume	13
Issue number	1
DOIs	https://doi.org/10.1038/s41467-022-35024-8
State	Published - Dec 2022

Funding

We gratefully acknowledge helpful comments and input from R. Fernandes. Work at the University of Minnesota (UMN) was primarily funded by the Department of Energy (DOE) through the UMN Center for Quantum Materials under Grant Number DE-SC0016371 (CL). Electron microscopy by SG and KAM was supported by the National Science Foundation (NSF) through the UMN MRSEC under DMR-2011401 (KAM). Parts of the work were performed in the Characterization Facility, UMN, which receives partial support from the NSF through the MRSEC and NNCI programs. Part of this work also used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Aspects of this work additionally used resources of the Advanced Photon Source, a DOE Office of Science User Facility operated by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Certain commercial equipment, instruments, or materials are identified in this paper to foster understanding. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology, nor does it imply that the materials or equipment identified are necessarily the best available for the purpose. We gratefully acknowledge helpful comments and input from R. Fernandes. Work at the University of Minnesota (UMN) was primarily funded by the Department of Energy (DOE) through the UMN Center for Quantum Materials under Grant Number DE-SC0016371 (CL). Electron microscopy by SG and KAM was supported by the National Science Foundation (NSF) through the UMN MRSEC under DMR-2011401 (KAM). Parts of the work were performed in the Characterization Facility, UMN, which receives partial support from the NSF through the MRSEC and NNCI programs. Part of this work also used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Aspects of this work additionally used resources of the Advanced Photon Source, a DOE Office of Science User Facility operated by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Certain commercial equipment, instruments, or materials are identified in this paper to foster understanding. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology, nor does it imply that the materials or equipment identified are necessarily the best available for the purpose.

Funders	Funder number
NNCI
UMN Center for Quantum Materials	DE-SC0016371
UMN MRSEC	DMR-2011401
National Science Foundation
U.S. Department of Energy
National Institute of Standards and Technology
Office of Science
Argonne National Laboratory	DE-AC02-06CH11357
Oak Ridge National Laboratory
University of Minnesota
Materials Research Science and Engineering Center, Harvard University

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10.1038/s41467-022-35024-8

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Chaturvedi, V., Ghosh, S., Gautreau, D., Postiglione, W. M., Dewey, J. E., Quarterman, P., Balakrishnan, P. P., Kirby, B. J., Zhou, H., Cheng, H., Huon, A., Charlton, T., Fitzsimmons, M. R., Korostynski, C., Jacobson, A., Figari, L., Barriocanal, J. G., Birol, T., Mkhoyan, K. A., & Leighton, C. (2022). Room-temperature valence transition in a strain-tuned perovskite oxide. Nature Communications, 13(1), Article 7774. https://doi.org/10.1038/s41467-022-35024-8

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title = "Room-temperature valence transition in a strain-tuned perovskite oxide",

abstract = "Cobalt oxides have long been understood to display intriguing phenomena known as spin-state crossovers, where the cobalt ion spin changes vs. temperature, pressure, etc. A very different situation was recently uncovered in praseodymium-containing cobalt oxides, where a first-order coupled spin-state/structural/metal-insulator transition occurs, driven by a remarkable praseodymium valence transition. Such valence transitions, particularly when triggering spin-state and metal-insulator transitions, offer highly appealing functionality, but have thus far been confined to cryogenic temperatures in bulk materials (e.g., 90 K in Pr1-xCaxCoO3). Here, we show that in thin films of the complex perovskite (Pr1-yYy)1-xCaxCoO3-δ, heteroepitaxial strain tuning enables stabilization of valence-driven spin-state/structural/metal-insulator transitions to at least 291 K, i.e., around room temperature. The technological implications of this result are accompanied by fundamental prospects, as complete strain control of the electronic ground state is demonstrated, from ferromagnetic metal under tension to nonmagnetic insulator under compression, thereby exposing a potential novel quantum critical point.",

author = "Vipul Chaturvedi and Supriya Ghosh and Dominique Gautreau and Postiglione, {William M.} and Dewey, {John E.} and Patrick Quarterman and Balakrishnan, {Purnima P.} and Kirby, {Brian J.} and Hua Zhou and Huikai Cheng and Amanda Huon and Timothy Charlton and Fitzsimmons, {Michael R.} and Caroline Korostynski and Andrew Jacobson and Lucca Figari and Barriocanal, {Javier Garcia} and Turan Birol and Mkhoyan, {K. Andre} and Chris Leighton",

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year = "2022",

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doi = "10.1038/s41467-022-35024-8",

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Chaturvedi, V, Ghosh, S, Gautreau, D, Postiglione, WM, Dewey, JE, Quarterman, P, Balakrishnan, PP, Kirby, BJ, Zhou, H, Cheng, H, Huon, A, Charlton, T, Fitzsimmons, MR, Korostynski, C, Jacobson, A, Figari, L, Barriocanal, JG, Birol, T, Mkhoyan, KA & Leighton, C 2022, 'Room-temperature valence transition in a strain-tuned perovskite oxide', Nature Communications, vol. 13, no. 1, 7774. https://doi.org/10.1038/s41467-022-35024-8

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T1 - Room-temperature valence transition in a strain-tuned perovskite oxide

AU - Chaturvedi, Vipul

AU - Ghosh, Supriya

AU - Gautreau, Dominique

AU - Postiglione, William M.

AU - Dewey, John E.

AU - Quarterman, Patrick

AU - Balakrishnan, Purnima P.

AU - Kirby, Brian J.

AU - Zhou, Hua

AU - Cheng, Huikai

AU - Huon, Amanda

AU - Charlton, Timothy

AU - Fitzsimmons, Michael R.

AU - Korostynski, Caroline

AU - Jacobson, Andrew

AU - Figari, Lucca

AU - Barriocanal, Javier Garcia

AU - Birol, Turan

AU - Mkhoyan, K. Andre

AU - Leighton, Chris

PY - 2022/12

Y1 - 2022/12

N2 - Cobalt oxides have long been understood to display intriguing phenomena known as spin-state crossovers, where the cobalt ion spin changes vs. temperature, pressure, etc. A very different situation was recently uncovered in praseodymium-containing cobalt oxides, where a first-order coupled spin-state/structural/metal-insulator transition occurs, driven by a remarkable praseodymium valence transition. Such valence transitions, particularly when triggering spin-state and metal-insulator transitions, offer highly appealing functionality, but have thus far been confined to cryogenic temperatures in bulk materials (e.g., 90 K in Pr1-xCaxCoO3). Here, we show that in thin films of the complex perovskite (Pr1-yYy)1-xCaxCoO3-δ, heteroepitaxial strain tuning enables stabilization of valence-driven spin-state/structural/metal-insulator transitions to at least 291 K, i.e., around room temperature. The technological implications of this result are accompanied by fundamental prospects, as complete strain control of the electronic ground state is demonstrated, from ferromagnetic metal under tension to nonmagnetic insulator under compression, thereby exposing a potential novel quantum critical point.

AB - Cobalt oxides have long been understood to display intriguing phenomena known as spin-state crossovers, where the cobalt ion spin changes vs. temperature, pressure, etc. A very different situation was recently uncovered in praseodymium-containing cobalt oxides, where a first-order coupled spin-state/structural/metal-insulator transition occurs, driven by a remarkable praseodymium valence transition. Such valence transitions, particularly when triggering spin-state and metal-insulator transitions, offer highly appealing functionality, but have thus far been confined to cryogenic temperatures in bulk materials (e.g., 90 K in Pr1-xCaxCoO3). Here, we show that in thin films of the complex perovskite (Pr1-yYy)1-xCaxCoO3-δ, heteroepitaxial strain tuning enables stabilization of valence-driven spin-state/structural/metal-insulator transitions to at least 291 K, i.e., around room temperature. The technological implications of this result are accompanied by fundamental prospects, as complete strain control of the electronic ground state is demonstrated, from ferromagnetic metal under tension to nonmagnetic insulator under compression, thereby exposing a potential novel quantum critical point.

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DO - 10.1038/s41467-022-35024-8

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AN - SCOPUS:85144143914

SN - 2041-1723

VL - 13

JO - Nature Communications

JF - Nature Communications

IS - 1

M1 - 7774

ER -

Room-temperature valence transition in a strain-tuned perovskite oxide

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