Fabrication of multiscale surface-chemical gradients by means of photocatalytic lithography.

We describe a new method for the fabrication of surface-chemical gradients. A film of titanium dioxide is brought into close proximity to a uniformly monolayer-covered surface and exposed to UV light to produce oxygen radicals. The use of a gradated grayscale mask between the UV source and the TiO2 allows the production of surface-chemical gradients via oxidation of the monolayer. The technique is demonstrated on gold surfaces bearing alkanethiol SAMs. Oxidation and subsequent replacement of the oxidized thiols has been used to produce surface-chemical gradients with lengths on the submillimeter to centimeter scales. The oxidation, removal, and replacement of the thiols during the process have been demonstrated by means of XPS. This oxidative process may be applied to other surface chemistries. Similarly, other shapes and slopes of gradients may be produced, depending on the photomask employed.