No abstract

Fast morphological evolution of polymer blend dictated by underlying polymer thin film upon rapid thermal annealing at high temperature.

Strategic electron beam (e-beam) irradiation on the surface of an ultrathin (<100 nm) film of polystyrene–poly(methyl methacrylate) (PS-PMMA) random copolymer followed by solvent annealing stimulates a special variety of dewetting, leading to large-area hierarchical nanoscale patterns. For this purpose, initially, a negative (positive) tone of resist PS (PMMA) under weak e-beam exposure is exploited to produce an array of sites composed of cross-linked PS (chain-scissioned PMMA). Subsequently, annealing with the help of a developer solvent engenders dewetted patterns in the exposed zones where PMMA blocks are confined by the blocks of cross-linked PS. The e-beam dosage was systematically varied from 180 μC cm−2 to 10 000 μC cm−2 to explore the tone reversal behavior of PMMA on the dewetted patterns. Remarkably, at relatively higher e-beam dosing, both PMMA and PS blocks act as negative tones in the exposed zone. In contrast, the chain scission of PMMA in the periphery of the exposed regions due to scattered secondary electrons caused confined dewetting upon solvent annealing. Such occurrences eventually lead to pattern miniaturization an order of magnitude greater than with conventional thermal or solvent vapor annealed dewetting. Selective removal of PMMA blocks of RCP using a suitable solvent provided an additional 50% reduction in the size of the dewetted features.

Dynamic contact line lithography (DCLL) is generally used for the templateless but well-ordered deposition of polymer micro/nanostructures from the solution of homopolymer. DCLL from the blend of several polymers in a common suitable solvent can generate rich morphologies including nanostructured Janus micro threads on a surface which might be challenging to fabricate using any other method. A blend of polystyrene (PS) and poly(methyl methacrylate) (PMMA) in toluene with different compositions and concentrations are used for DCLL at a constant contact line speed of 10 μm/s. Variations of compositions and the overall concentration of polymer, engender Janus micro threads to undulated threads and multi-layered micro/nanodroplets of PS/PMMA. Interestingly, the more soluble PS phase separates first compared to less soluble PMMA near the contact line due to the enhanced local concentration of PS during the convective flow of the solvent toward the contact line. This is also verified by DCLL using PS/PMMA blend in ethyl acetate as well. In that case, more soluble PMMA deposits first near the contact line compared to marginally less soluble PS in the solvent.