Metallization of vanadium dioxide driven by large phonon entropy

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.

doi:10.1038/nature13865

Title: Metallization of vanadium dioxide driven by large phonon entropy

Journal Article · Mon Nov 10 00:00:00 EST 2014 · Nature (London)

DOI:https://doi.org/10.1038/nature13865· OSTI ID:1185416

Budai, John D. ^[1]; Hong, Jiawang ^[1]; Manley, Michael E. ^[1]; Specht, Eliot D. ^[1]; Li, Chen ^[1]; Tischler, Jonathan ^[2]; Abernathy, Douglas L ^[1]; Said, Ayman ^[2]; Leu, Bogdan ^[2]; Boatner, Lynn A. ^[1]; McQueeney, Robert John ^[1]; Delaire, Olivier A. ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

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.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: AC05-00OR22725

OSTI ID:: 1185416

Journal Information:: Nature (London), Vol. 515, Issue 7528; ISSN 0028-0836

Publisher:: Nature Publishing Group

Country of Publication:: United States

Language:: English

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