Modification of Mott phase transition characteristics in VO2@TiO2 core/shell nanostructures by misfit-strained heteroepitaxy.

Vanadium dioxide (VO2) is a key material for thermochromic smart windows that can respond to environmental temperature and modulate near-infrared irradiation by changing from a transparent state at low temperature to a more reflective state at high temperature, while maintaining visible transmittance. Here, we demonstrate for the first time that the Mott phase transition characteristics in VO2 nanoparticles can be remarkably modified by misfit strains occurring at the epitaxial interface between VO2 and the anatase TiO2 of VO2/TiO2 core-shell particles. The heteroepitaxial growth of the as-synthesized particles followed an unprecedented orientation relationship, and an epitaxial growth mechanism is proposed to explain this behavior. A relatively small theoretical coherent misfit (3-11%) and a moderate heating rate (20 °C·min(-1)) in the preparation of the core-shell structure were critically important from the thermodynamic and kinetic perspectives, respectively. The misfit-induced interfacial strain along the uniaxial cR axis increased the transition temperatures, especially on the cooling portion of the heating-cooling cycle, leading to a notably reduced transition hysteresis loop width (from 23.5 to 12.0 °C). Moreover, the optical band gap was also engineered by the interfacial effect. Such a reduced hysteresis showed a benefit for enhancing a rapid response for energy saving thermochromic smart windows.