Nanobubble and nanodroplet template growth of particle nanorings versus nanoholes in drying nanofluids and polymer films

Abstract
Here we demonstrate how confined nanobubbles and nanodroplets, which can either form spontaneously at the suspension/substrate interface, or can more interestingly be purposely introduced in the system, allow assembly of nanoparticles (NPs) into nanoring-like structures with a flexible control of both the size and distribution. As with most wetting-mediated nanopatterning methods, this approach provides an alternative to direct replication from templates. The formation of two-dimensional ring-shaped nanostructures was obtained by drying a nanocolloidal gold (Au) suspension drop confining nanobubbles (or nanodroplets) that are settled at a solid substrate. AFM investigation of the dry nanostructures showed the formation of isolated Au NPs rings having diameters ranging from 200 nm to 500 nm along the dewetting–drying path of the suspension drop. The flexibility of these wetting processes for the variation of the spatial features of the nanoring (size and shape resolution) essentially depends on physical parameters such as the nanobubble/nanodroplet size and concentration, the wettability, and the evaporation rate of the nanofluid drop on the substrate. Furthermore, we show that the underpinning mechanism of this evaporation-assisted assembly of Au NPs into supported functional nanoring patterns is fairly similar to that at work in the spontaneous formation of nanoholes in drying polymer thin films. Finally, the method proves to be a simple and flexible nanofabrication tool to be extended to various nanosize objects, towards specific optical and sensing applications.'