Vanadium dioxide (VO2) films have attracted extensive attention for their pronounced metal–insulator transition (MIT) and multifunctional responses, holding great promise for smart windows, infrared stealth, memristive devices, and advanced sensors. However, conventional approaches for tuning the transition temperature, such as elemental doping or heterostructure engineering, often suffer from complicated processing, impurity phases, and poor device uniformity. Here, we use a dopant-free, high-vacuum annealing (9 × 10−4 Pa, ≈9 × 10−6 mbar) strategy to regulate the intrinsic structural evolution of VO2 films via oxygen-vacancy engineering and to clarify its influence on electrical switching contrast and infrared emissivity modulation. As the annealing temperature increases under low oxygen partial pressure, oxygen vacancies gradually accumulate, converting V4+ to V3+ and driving the films through three distinct structural stages: low-temperature lattice expansion with preserved M1 framework, critical structural collapse at 550 °C, and high-temperature defect rearrangement with local recrystallization. Consequently, the electrical MIT temperature continuously decreases, but the switching ratio collapses at the critical point and only partially recovers after high-temperature reorganization, while the infrared emissivity response transitions from abrupt, phase-transition-dominated switching to a continuous, tunable modulation at elevated temperatures. Notably, the infrared response begins continuous tuning earlier (≈450 °C) than the collapse of electrical MIT, reflecting the different sensitivities of optical and electronic responses to local lattice defects. These results reveal the coupling among oxygen-vacancy evolution, structural stability, electrical contrast, and infrared modulation in compositionally simple VO2 films. Compared with conventional doping, this high-vacuum annealing strategy avoids impurity phases, preserves compositional simplicity, and provides a scalable defect-engineering route to design VO2-based devices with reconfigurable electrical and infrared response modes.
Liu et al. (Fri,) studied this question.