Thermally Induced Superhydrophilicity in TiO₂ Films Prepared by Supersonic Aerosol Deposition

Superhydrophilic and superhydrophobic surfaces enable self-cleaning phenomena, either forming a continuous water film or forming droplets that roll off the surface, respectively. TiO₂ films are well-known for their extreme hydrophilicity and photocatalytic characteristics. Here, we describe nanostructured TiO₂ thin films prepared by supersonic aerosol deposition, including a thorough study of the effects of the annealing temperature on the crystal structure, surface morphology, surface roughness, and wetting properties. Powder X-ray diffraction showed that supersonic deposition resulted in fragmentation and amorphization of the micrometer-size anatase (60%)–rutile (40%) precursor powder and that, upon annealing, a substantial fraction of the film (∼30%) crystallized in the highly hydrophilic but metastable brookite phase. The film morphology was also somewhat modified after annealing. Scanning electron microscopy and atomic force microscopy revealed rough granular films with high surface roughness. The as-deposited TiO₂ films were moderately hydrophilic with a water contact angle (θ) of ∼45°, whereas TiO₂ films annealed at 500 °C became superhydrophilic (θ ∼ 0°) without UV illumination. This thermally induced superhydrophilicity of the TiO₂ films can be explained on the basis of the combined effects of the change in the crystal structure, surface microstructure, and surface roughness. Supersonic aerosol deposition followed by annealing is uniquely able to produce these nanostructured films containing a mixture of all three TiO₂ phases (anatase, rutile, and brookite) and exhibiting superhydrophilicity without UV illumination