Vanadium dioxide (VO2) is a promising material for developing energy-saving “smart windows,” owing to its infrared thermochromism induced by metal-insulator transition (MIT). However, its practical application is greatly limited by its relatively high critical temperature (~68°C), low luminous transmittance (<60%), and poor solar energy regulation ability (<15%). Here, we developed a reversible and nonvolatile electric field control of the MIT of a monoclinic VO2 film. With a solid electrolyte layer assisting gating treatment, we modulated the insertion/extraction of hydrogen into/from the VO2 lattice at room temperature, causing tristate phase transitions that enable control of light transmittance. The dramatic increase in visible/infrared transmittance due to the phase transition from the metallic (lightly H-doped) to the insulating (heavily H-doped) phase results in an increased solar energy regulation ability up to 26.5%, while maintaining 70.8% visible luminous transmittance. These results break all previous records and exceed the theoretical limit for traditional VO2 smart windows, making them ready for energy-saving utilization.

Hydrogenation is an effective way to tune the property of metal oxides. It can conventionally be performed by doping hydrogen into solid materials with noble-metal catalysis, high-temperature/pressure annealing treatment, or high-energy proton implantation in vacuum condition. Acid solution naturally provides a rich proton source, but it should cause corrosion rather than hydrogenation to metal oxides. Here we report a facile approach to hydrogenate monoclinic vanadium dioxide (VO2) in acid solution at ambient condition by placing a small piece of low workfunction metal (Al, Cu, Ag, Zn, or Fe) on VO2 surface. It is found that the attachment of a tiny metal particle (~1.0 mm) can lead to the complete hydrogenation of an entire wafer-size VO2 (>2 inch). Moreover, with the right choice of the metal a two-step insulator–metal–insulator phase modulation can even be achieved. An electron–proton co-doping mechanism has been proposed and verified by the first-principles calculations.

VO2 epitaxial film with large size has been prepared by oxide-molecular beam epitaxy method on Al2O3 (0001) substrate. The VO2 film shows a perfect crystal orientation, uniformity, and distinct metal-insulator phase transition (MIT) characteristics. It is observed that the MIT character is closely associated with the crystal defects such as oxygen vacancies. By controlling the growth condition, the MIT temperature can be tuned through modifying the content of oxygen vacancies. The role of the oxygen vacancies on the phase transition behavior of this VO2 film is discussed in the framework of the hybridization theory and the valence state of vanadium.