Effects of Zirconium Ions Doping on the Structural and Thermochromic Properties of VO₂ Thin Films

Abstract

As an inorganic functional material, VO₂ thin films are expected to be used for smart windows. However, these films are not conducive to practical applications when the phase transition temperature (Tc) of the VO₂ is approximately 68°C, which is greater than room temperature. To decrease Tc, the effect of Zr⁴⁺ doping on the structure and properties of VO₂ films were investigated. The films were prepared using a sol–gel process, spin-coating on quartz glasses, and annealing at 525°C in a tube furnace within a nitrogen atmosphere. The results demonstrate that these films have a highly preferential crystalline orientation on the substrate; however, the primary two x-ray diffraction pattern peaks shift slightly toward the small angle, and when 7 at.% Zr⁴⁺ was doped in the VO₂ film, the deviation angle was 0.16°, and the crystallite size was approximately 98 nm. A large number of grains were found on the surface of the pure VO₂ films, but all the Zr⁴⁺ doped films had a layered structure, and the thickness of the films was approximately 200 nm. The Tc of these films was characterized using differential scanning calorimetry, and the luminous and solar transmittance was characterized using a UV–Vis–NIR spectrophotometer, which demonstrated that the effect of Zr⁴⁺ doping decreased Tc by approximately 1°C per 1 at.% on average, and the Tc of the 7 at.% film was slightly greater than that of the 5 at.% film, the phase transition temperature of which was 61.4°C. The transmittance decreased as the doping concentration increased, and 1 at.% Zr⁴⁺ doping increased the luminous regulation efficiency (ΔT _lum) and solar modulation efficiency (ΔT _sol). The ΔT _lum of the pure VO₂ film and the 1 at.% Zr⁴⁺-doped VO₂ films was 10.9% and 11.2%, and ΔT _sol was 14.4 and 15.2%, respectively.