Phase coexistence and pressure-temperature phase evolution of VO2(A) nanorods near the semiconductor-semiconductor transition

A comprehensive understanding of the physical origins of the phase transition behaviors of transition metal oxides is still complex due to the interplay among competing interactions of comparable strengths tuning their nature. Widespread interest in such phase transitions has motivated explorations of nanocrystalline vanadium dioxide (VO2) in various forms and a long-running debate persists over the roles played by electron-electron correlation with lattice distortion. External stimuli like pressure and temperature have strong effects on the appearance, stability, and spacial distribution of the high-resistive (HR) and low-resistive (LR) phases accompanying their structural modification. Our comprehensive experiments establish the pressure-induced and thermally driven evolution of phase coexistence in VO2(A) nanorods. Our experimental evidence supports coexisting HR and LR phases, where compression suppressed coexistence at ∼7 GPa, followed by a semiconductor-semiconductor transition at around ∼10 GPa with the absence of pressure-induced metallization. X-ray diffraction revealed lattice distortion with local microscopic strain inhomogeneity in the nanorods, without any discontinuity in the pressure-volume data. We further investigated the vibrational modes and relaxations of the samples related to their thermal expansions. We also found that the pressure-dependent hierarchy of microstructural densification contributed significantly to the resulting transport properties.