Specificity of electrophysical and gas-sensitive properties of nanocomposite ZnO–TiO2 films formed by solid-phase pyrolysis

ZnO–TiO2 thin films containing 0.5, 1.0, and 5.0 mol.% ZnO were synthesized by oxidative solid-phase pyrolysis. The materials contained anatase and rutile phases with particle size of 6–13 nm, as confirmed using X-ray phase analysis and scanning electron microscopy. When a certain number of ZnO crystallites appeared in the TiO2 film structure in the temperature range of room temperature to 220°C, a two-level response of the film resistance was observed, differing by approximately 10%, as obtained by electrophysical measurements. The two-level response correlates with the formation of two donor energy levels of 0.28 and 0.33 eV in the band structure of the ZnO–TiO2 films. The donor level with a higher activation energy corresponded to the Ti vacancy (V−Ti), and that with a lower activation energy corresponded to the Zn vacancy (V−Zn). Two levels of gas-sensitive properties were noted for 0.5ZnO–TiO2, 1ZnO–TiO2, and 5ZnO–TiO2 under the influence of 50 ppm NO2 at 250°C. Such two-level responses can be ascribed to the pinning of the Fermi level on ZnO and TiO2 nanocrystallites. The mechanism of the beak-shaped and two-level responses of sensors based on composite nanomaterials when exposed to various gases was elucidated.