Shining Light on The Phase Transitions of Vanadium Dioxide

The salient feature of the familiar structural transition accompanying the thermally-driven metal-insulator transition in bulk vanadium dioxide (VO2) is a pairing of all the vanadium ions in the monoclinic M¬1 insulating phase. Whether this pairing (unit cell doubling) alone is sufficient to open the energy gap has been the central question of a classic debate which has continued for almost sixty years. Interestingly, there are two less familiar insulating states, monoclinic M2 and triclinic, which are accessible via strain or chemical doping. These phases are noteworthy in that they exhibit distinctly different V-V pairing. With infrared and optical photon spectroscopy, we investigate how the changes in crystal structure affect the electronic structure. We find that the energy gap and optical inter-band transitions are insensitive to changes in the vanadium-vanadium pairing. This result is confirmed by DFT+U and HSE calculations. Hence, our work conclusively establishes that intra-atomic Coulomb repulsion between electrons provides the dominant contribution to the energy gap in all insulating phases of VO2. VO2 is a candidate material for novel technologies, including ultrafast data storage, memristors, photonic switches, smart windows, and transistors which move beyond the limitations of silicon. The attractiveness of correlated materials for technological application is due to their novel properties that can be tuned by external factors such as strain, chemical doping, and applied fields. For advances in fundamental physics and applications, it is imperative that these properties be measured over a wide range of regimes. Towards this end, we study a single domain VO2 crystal with polarized light to characterize the anisotropy of the optical properties. In addition, we study the effects of compressive strain in a VO2 thin film in which we observe remarkable changes in electronic structure and transition temperature. Furthermore, we find evidence that electronic correlations are active in the metallic rutile phase as well. VO2 films exhibit phase coexistence in the vicinity of the metal-insulator transition. Using scanning near-field infrared microscopy, we have studied the patterns of phase coexistence in the same area on repeated heating and cooling cycles. We find that the pattern formation is reproducible each time. This is an unexpected result from the viewpoint of classical nucleation theory that anticipates some degree of randomness. The completely deterministic nature of nucleation and growth of domains in a VO2 film with imperfections is a fundamental finding. This result also holds promise for producing reliable nanoscale VO2 devices