Amplified and localized photoswitching of TiO2 by micro- and nanostructuring

Fast photoswitching of wetting properties is important for the development of micro/nanofluidic systems and lab-on-a-chip devices. Here, we show how structuring the surface amplifies photoswitching properties. Atomic layer-deposited titanium dioxide (TiO2) has phototunable hydrophilic properties due to its surface chemistry, but microscale overhang pillars and additional nanoscale topography can override the chemistry and make the surface superhydrophobic. Three switching processes are achieved simply by controlling the UV exposure time: from (1) rolling superhydrophobic to sticky superhydrophobic (Cassie-Baxter to Wenzel), (2) superhydrophobic to hydrophilic, and (3) superhydrophobic to superhydrophilic after 1, 5, and 10 min of UV exposure, respectively. We report the fastest reversible switching to date: 1 min of UV exposure is enough to promote a rolling-to-sticky transition, and mild heating (30 min at 60 °C) is sufficient for recovery. This performance is caused by a combination of the photoswitching properties of TiO2, the micropillar overhang geometry, and surface nanostructuring. We demonstrate that the switching also can be performed locally by introducing microwriting under a water droplet.