Basic aspects of the metal–insulator transition in vanadium dioxide VO$_{2}$: a critical review

Jean-Paul Pouget

doi:10.5802/crphys.74

Article de recherche

Basic aspects of the metal–insulator transition in vanadium dioxide VO

_{2}

: a critical review
[Aspects principaux de la transition métal–isolant du dioxyde de vanadium VO

_{2}

: une revue critique]

Jean-Paul Pouget ¹

¹ Laboratoire de physique des solides, CNRS UMR 8502, Université Paris-Sud, Université Paris-Saclay, 91405 Orsay, France

Comptes Rendus. Physique, Volume 22 (2021) no. 1, pp. 37-87.

Résumé
Abstract

Le dioxyde de vanadium présente une transition métal–isolant (TMI) du premier ordre à 340 K ( $= T_{MI}$ ) d’une structure rutile (R) à une structure monoclinique ( $M_{1}$ ). Le mécanisme de cette transition interprétée comme étant due soit à une instabilité de Peierls soit à une instabilité de Mott–Hubbard reste très controversé depuis près d’un demi-siècle. Cependant depuis une vingtaine d’années l’étude des propriétés chimiques et physiques de ${VO}_{2}$ et de ses alliages suscite un renouveau d’intérêt par la possibilité d’applications provenant de l’obtention de dispositifs s’appuyant sur la réalisation de films minces. Nous décrivons dans cette revue les propriétés structurales, électroniques et magnétiques des différentes phases métallique (R) et isolantes ( $M_{1}$ , T et $M_{2}$ ) de ${VO}_{2}$ , de ses solutions solides et des modifications sous contrainte. Nous présentons de façon synthétique les divers diagrammes de phase et leur analyse par symétrie. Ce travail conduit à relativiser certaines interprétations du passé et à souligner en particulier le rôle particulièrement important des interactions électron–électron dans les différentes phases de ${VO}_{2}$ et des fluctuations structurales dans le mécanisme de la TMI. Dans ce cadre nous montrons que la transition de phase est annoncée de façon surprenante par des corrélations structurales d’anisotropie unidimensionnelle (1D) révélant un ordre local en chaine du V issu d’une instabilité sous-jacente de la structure rutile. A celles-ci correspond une dynamique critique inattendue de type relaxation (ou ordre-désordre). Nous décrivons comment le couplage bidimensionnel (2D) de ces fluctuations 1D forme localement des chaines zig-zag de $V^{4 +}$ et des paires V–V, conduisant aux phases isolantes $M_{2}$ et $M_{1}$ . Ces phases présentent une forte anisotropie électronique avec de substantielles corrélations électron–électron conduisant à un découplage spin–charge. Le fondamental de type spin-Peierls de la phase $M_{1}$ est analysé à partir d’un mécanisme de dimérisation, en phase T, des chaines d’Heisenberg de spin 1/2 formées par les zig-zags de $V^{4 +}$ dans la phase $M_{2}$ . Cette revue résume de façon critique les résultats principaux de l’abondante littérature concernant les aspects fondamentaux de la TMI de ${VO}_{2}$ . Elle est complétée par d’anciens résultats jamais publiés. Les interprétations proposées se placent dans un cadre conceptuel relativement large se révélant pertinent pour l’interprétation des propriétés physiques d’autres classes de matériaux.

Vanadium dioxide exhibits a first order metal to insulator transition (MIT) at 340 K ( $T_{MI}$ ) from a rutile (R) structure to a monoclinic ( $M_{1}$ ) structure. The mechanism of this transition interpreted as due either to a Peierls instability or to a Mott–Hubbard instability is controversial since half a century. However, in the last twenty years the study of chemical and physical properties of ${VO}_{2}$ and of its alloys, benefits of a renewed interest due to possible applications coming from the realization of devices made of thin films. We describe in this review the structural, electronic and magnetic properties of the different metallic (R) and insulating ( $M_{1}$ , T, $M_{2}$ ) phases of ${VO}_{2}$ , of its solid solutions and under constraint. We present in a synthetic manner the various phase diagrams and their symmetry analysis. This work allows us to revisit older interpretation and to emphasize in particular the combined role of electron–electron interactions in the various phase of ${VO}_{2}$ and of structural fluctuations in the MIT mechanism. In this framework we show that the phase transition is surprisingly announced by anisotropic one-dimensional (1D) structural fluctuations revealing chain like correlations between the V due to an incipient instability of the rutile structure. This leads to an unexpected critical dynamics of the order–disorder (or relaxation) type. We describe how the two-dimensional (2D) coupling between these 1D fluctuations, locally forming uniform $V^{4 +}$ zig-zag chains and V–V pairs, stabilizes the $M_{2}$ and $M_{1}$ insulating phases. These phases exhibit a 1D electronic anisotropy where substantial electron–electron correlations conduct to a spin–charge decoupling. The spin-Peierls ground state of $M_{1}$ is analyzed via a mechanism of dimerization, in the T phase, of the spin 1/2 $V^{4 +}$ zig-zag Heisenberg chains formed in the $M_{2}$ phase. This review summarizes in a critical manner the main results of the large literature on fundamental aspects of the MIT of ${VO}_{2}$ . It is completed by unpublished old results. Interpretations are also placed in a large conceptual frame which is also relevant to interpret physical properties of other classes of materials.

Reçu le : 2020-11-28
Révisé le : 2021-02-25
Accepté le : 2021-04-20
Publié le : 2021-06-11

DOI : 10.5802/crphys.74

Keywords: Vanadium dioxide, Metal–insulator transition, Mott–Hubbard charge localization, Spin-Peierls and Peierls transitions, Chain-like structural instability, Electron–phonon coupling
Mot clés : Dioxyde de vanadium, Transition métal–isolant, Localisation de charge de Mott–Hubbard, Transitions de Peierls et de spin-Peierls, Instabilités structurales corrélées à une dimension, Couplage électron–phonon

Affiliations des auteurs :

Jean-Paul Pouget ¹

¹ Laboratoire de physique des solides, CNRS UMR 8502, Université Paris-Sud, Université Paris-Saclay, 91405 Orsay, France

Licence :

CC-BY 4.0

Droits d'auteur : Les auteurs conservent leurs droits

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Jean-Paul Pouget. Basic aspects of the metal–insulator transition in vanadium dioxide VO$_{2}$: a critical review. Comptes Rendus. Physique, Volume 22 (2021) no. 1, pp. 37-87. doi : 10.5802/crphys.74. https://comptes-rendus.academie-sciences.fr/physique/articles/10.5802/crphys.74/

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