Self-organized nanocrack networks: a pathway to enlarge catalytic surface area in sputtered ceramic thin films, showcased for photocatalytic TiO2

Sputter deposited photocatalytic thin films offer high adherence and mechanical stability, but typically are outperformed in their photocatalytic properties by colloidal TiO2 nanostructures, which in turn typically suffer from problematic removal. Here we report on thermally controlled nanocrack formation as a feasible and batch applicable approach to enhance the photocatalytic performance of well adhering, reactively sputtered TiO2 thin films. Networks of nanoscopic cracks were induced into tailored columnar TiO2 thin films by thermal annealing. These deep trenches are separating small bundles of TiO2 columns, adding their flanks to the overall catalytically active surface area. The variation of thin film thickness reveals a critical layer thickness for initial nanocrack network formation, which was found to be about 400 nm in case of TiO2. The columnar morphology of the as deposited TiO2 layer with weak bonds between respective columns and with strong bonds to the substrate is of crucial importance for the formation of nanocrack networks. A beneficial effect of nanocracking on the photocatalytic performance was experimentally observed. It was correlated by a simple geometric model for explaining the positive impact of the crack induced enlargement of active surface area on photocatalytic efficiency. The presented method of nanocrack network formation is principally not limited to TiO2 and is therefore seen as a promising candidate for utilizing increased surface area by controlled crack formation in ceramic thin films in general.