Chemical Cross-Linking of Anatase Nanoparticle Thin Films for Enhanced Mechanical Properties

Titania nanoparticle-based thin films are highly attractive for a vast range of commercial applications. Although their application on polymer-based substrates is particularly appealing, the requirement of low process temperatures results in low mechanical stability. Highly crystalline anatase nanoparticles were used as the building blocks for coatings through a two-stage process. The main benefits of this method, over the more common sol-gel ones, are the relatively low temperature required for the production of metal oxide coatings, allowing the use of polymer-based substrates, and the defined crystallinity of the resulting thin films. Although in several cases moderate temperatures can be utilized for drying the films, the mechanical stability of the respective coatings remains a critical issue. In this contribution, we present a strategy to achieve network formation between TiO₂ nanoparticles in a preformed thin film on the basis of the cross-linking of the functionalized nanoparticles. In the first stage, the nanoparticles were functionalized by dicarboxylic acids, concurrently leading to a stable colloidal dispersion that could be utilized for dip-coating to obtain TiO₂ thin films with high homogeneity and optical transparence. During the second stage, the films were immersed in a solution of a diamine as the linker molecule, to achieve cross-linking between the nanoparticles within the film. It is demonstrated that indeed covalent bonding was realized and functional coatings with significantly enhanced mechanical properties were obtained by our strategy.