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Title: Metallization of vanadium dioxide driven by large phonon entropy

Abstract

Phase competition underlies many remarkable and technologically important phenomena in transition-metal oxides. Vanadium dioxide exhibits a first-order metal-insulator transition (MIT) near room temperature, where conductivity is suppressed and the lattice changes from tetragonal to monoclinic on cooling. Ongoing attempts to explain this coupled structural and electronic transition begin with two classic starting points: a Peierls MIT driven by instabilities in electron-lattice dynamics versus a Mott MIT where strong electron-electron correlations drive charge localization1-10. A key-missing piece of the VO2 puzzle is the role of lattice vibrations. Moreover, a comprehensive thermodynamic treatment must integrate both entropic and energetic aspects of the transition. Our measurements establish that the entropy driving the MIT is dominated by strongly anharmonic phonons rather than electronic contributions, and provide a direct determination of phonon dispersions. Our calculations identify softer bonding as the origin of the large vibrational entropy stabilizing the metallic rutile phase. They further reveal how a balance between higher entropy in the metal and orbital-driven lower energy in the insulator fully describes the thermodynamic forces controlling the MIT. This study illustrates the critical role of anharmonic lattice dynamics in metal-oxide phase competition, and provides guidance for the predictive design of new materials.

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [1];  [2];  [2];  [1];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1185416
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature (London)
Additional Journal Information:
Journal Name: Nature (London); Journal Volume: 515; Journal Issue: 7528; Journal ID: ISSN 0028-0836
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Budai, John D., Hong, Jiawang, Manley, Michael E., Specht, Eliot D., Li, Chen, Tischler, Jonathan, Abernathy, Douglas L, Said, Ayman, Leu, Bogdan, Boatner, Lynn A., McQueeney, Robert John, and Delaire, Olivier A. Metallization of vanadium dioxide driven by large phonon entropy. United States: N. p., 2014. Web. doi:10.1038/nature13865.
Budai, John D., Hong, Jiawang, Manley, Michael E., Specht, Eliot D., Li, Chen, Tischler, Jonathan, Abernathy, Douglas L, Said, Ayman, Leu, Bogdan, Boatner, Lynn A., McQueeney, Robert John, & Delaire, Olivier A. Metallization of vanadium dioxide driven by large phonon entropy. United States. doi:10.1038/nature13865.
Budai, John D., Hong, Jiawang, Manley, Michael E., Specht, Eliot D., Li, Chen, Tischler, Jonathan, Abernathy, Douglas L, Said, Ayman, Leu, Bogdan, Boatner, Lynn A., McQueeney, Robert John, and Delaire, Olivier A. Mon . "Metallization of vanadium dioxide driven by large phonon entropy". United States. doi:10.1038/nature13865. https://www.osti.gov/servlets/purl/1185416.
@article{osti_1185416,
title = {Metallization of vanadium dioxide driven by large phonon entropy},
author = {Budai, John D. and Hong, Jiawang and Manley, Michael E. and Specht, Eliot D. and Li, Chen and Tischler, Jonathan and Abernathy, Douglas L and Said, Ayman and Leu, Bogdan and Boatner, Lynn A. and McQueeney, Robert John and Delaire, Olivier A.},
abstractNote = {Phase competition underlies many remarkable and technologically important phenomena in transition-metal oxides. Vanadium dioxide exhibits a first-order metal-insulator transition (MIT) near room temperature, where conductivity is suppressed and the lattice changes from tetragonal to monoclinic on cooling. Ongoing attempts to explain this coupled structural and electronic transition begin with two classic starting points: a Peierls MIT driven by instabilities in electron-lattice dynamics versus a Mott MIT where strong electron-electron correlations drive charge localization1-10. A key-missing piece of the VO2 puzzle is the role of lattice vibrations. Moreover, a comprehensive thermodynamic treatment must integrate both entropic and energetic aspects of the transition. Our measurements establish that the entropy driving the MIT is dominated by strongly anharmonic phonons rather than electronic contributions, and provide a direct determination of phonon dispersions. Our calculations identify softer bonding as the origin of the large vibrational entropy stabilizing the metallic rutile phase. They further reveal how a balance between higher entropy in the metal and orbital-driven lower energy in the insulator fully describes the thermodynamic forces controlling the MIT. This study illustrates the critical role of anharmonic lattice dynamics in metal-oxide phase competition, and provides guidance for the predictive design of new materials.},
doi = {10.1038/nature13865},
journal = {Nature (London)},
number = 7528,
volume = 515,
place = {United States},
year = {Mon Nov 10 00:00:00 EST 2014},
month = {Mon Nov 10 00:00:00 EST 2014}
}

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