Fabrication of Thiol-Ene "Clickable" Copolymer-Brush Nanostructures on Polymeric Substrates via Extreme Ultraviolet Interference Lithography.

We demonstrate a new approach to grafting thiol-reactive nanopatterned copolymer-brush structures on polymeric substrates by means of extreme ultraviolet (EUV) interference lithography. The copolymer brushes were designed to contain maleimide functional groups as thiol-reactive centers. Fluoropolymer films were exposed to EUV radiation at the X-ray interference lithography beamline (XIL-II) at the Swiss Light Source, in order to create radical patterns on their surfaces. The radicals served as initiators for the copolymerization of thiol-ene "clickable" brushes, composed of a furan-protected maleimide monomer (FuMaMA) and different methacrylates, namely, methyl methacrylate (MMA), ethylene glycol methyl ether methacrylate (EGMA), or poly(ethylene glycol) methyl ether methacrylate (PEGMA). Copolymerization with ethylene-glycol-containing monomers provides antibiofouling properties to these surfaces. The number of reactive centers on the grafted brush structures can be tailored by varying the monomer ratios in the feed. Grafted copolymers were characterized by using attenuated total reflection infrared (ATR-IR) spectroscopy. The reactive maleimide methacrylate (MaMA) units were utilized to conjugate thiol-containing moieties using the nucleophilic Michael-addition reaction, which proceeds at room temperature without the need for any metal-based catalyst. Using this approach, a variety of functionalities was introduced to yield polyelectrolytes, as well as fluorescent and light-responsive polymer-brush structures. Functionalization of the brush structures was demonstrated via ATR-IR and UV-vis spectroscopy and fluorescence microscopy, and was also indicated by a color switch. Furthermore, grafted surfaces were generated via plasma activation, showing a strongly increased wettability for polyelectrolytes and a reversible switch in static water contact angle (CA) of up to 18° for P(EGMA-co-MaMA-SP) brushes, upon exposure to alternating visible and UV-light irradiation.