Controlled self-organization of polymer nanopatterns over large areas

Self-assembly methods allow to obtain ordered patterns on surfaces with exquisite precision, but often lack in effectiveness over large areas. Here we report on the realization of hierarchically ordered polymethylmethacrylate (PMMA) nanofibres and nanodots over large areas from solution via a fast, easy and low-cost method named ASB-SANS, based on a ternary solution that is cast on the substrate. Simple changes to the ternary solution composition allow to control the transition from nanofibres to nanodots, via a wide range of intermediate topologies. The ternary solution includes the material to be patterned, a liquid solvent and a solid substance able to sublimate. The analysis of the fibres/dots width and inter-pattern distance variations with respect to the ratio between the solution components suggests that the macromolecular chains mobility in the solidified sublimating substance follows Zimm-like models (mobility of macromolecules in diluted liquid solutions). A qualitative explanation of the self-assembly phenomena originating the observed nanopatterns is given. Finally, ASB-SANS-generated PMMA nanodots arrays have been used as lithographic masks for a silicon substrate and submitted to Inductively Coupled Plasma-Reactive Ion Etching (ICP-RIE). As a result, nanopillars with remarkably high aspect ratios have been achieved over areas as large as several millimeters square, highlighting an interesting potential of ASB-SANS in practical applications like photon trapping in photovoltaic cells, surface-enhanced sensors, plasmonics.