Surface Functionalization of Porous Nanostructured Metal Oxide Thin Films Fabricated by Glancing Angle Deposition

We report the application of solution- and vapor-phase siloxane-based methods for tailoring the surface chemistry/properties of highly porous, nanostructured thin films fabricated using glancing angle deposition (GLAD). The GLAD technique produces high surface area films consisting of isolated columns and provides complete control over the film/column morphology. In the present study, the chemical tunability of a variety of metal oxide GLAD films was investigated using solution-based and vapor-phase surface functionalization methodologies. The surface properties and structures of the treated and untreated films were investigated using scanning electron microscopy (SEM), advancing aqueous contact angle measurements, cyclic voltammetry, and X-ray photoelectron spectroscopy (XPS). Results indicate that the surface chemistry of metal oxide GLAD films could be tailored by either method; however, chemical reactivity depends strongly on the metal oxide film material. Chemical tunability is demonstrated through the covalent tethering of numerous chemical moieties onto the exposed and interior surfaces of metal oxide GLAD films of varied structural motifs. Through careful choice of surface modifier, the present derivatization methods afford a full range of aqueous wettability from hydrophilic to superhydrophobic without compromising film structure. These functionalized, nanoconstructed films demonstrate a high degree of tunability over both structural and surface properties, making them well suited for diverse applications such as optical filters or sensors.