Symmetry Relationship and Strain-Induced Transitions between Insulating M1 and M2 and Metallic R phases of Vanadium Dioxide

Abstract

The ability to synthesize VO2 in the form of single-crystalline nanobeams and nano- and microcrystals uncovered a number of previously unknown aspects of the metal-insulator transition (MIT) in this oxide. In particular, several reports demonstrated that the MIT can proceed through competition between two monoclinic (insulating) phases M1 and M2 and the tetragonal (metallic) R phase under influence of strain. The nature of such phase behavior has been not identified. Here we show that the competition between M1 and M2 phases is purely lattice-symmetry-driven. Within the framework of the Ginzburg-Landau formalism, both M phases correspond to different directions of the same four-component structural order parameter, and as a consequence, the M2 phase can appear under a small perturbation of the M1 structure such as doping or stress. We analyze the strain-controlled phase diagram of VO2 in the vicinity of the R-M2-M1 triple point using the Ginzburg-Landau formalism and identify and experimentally verify the pathways for strain-control of the transition. These insights open the door toward more systematic approaches to synthesis of VO2 nanostructures in desired phase states and to use of external fields in the control of the VO2 phase states. Additionally, we report observation of the triclinic T phase at the heterophase domain boundaries in strained quasi-two-dimensional VO2 nanoplatelets, and theoretically predict phases that have not been previously observed.