Patterned polyfluorene surfaces by functionalization of nanoimprinted polymeric features

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A new procedure is described for surface grafting polymer brushes by step-growth polymerization from initiator-embedded polymeric thin films and micron- and nanometer-scale patterns. An imprint lithographic process, nanocontact molding, was used to prepare thin patterned cross-linked polyacrylate network films on silicon wafers that incorporated 4-bromostyrene in the networks. These networks present reactive 4-bromophenyl functionality at the surface that act as attachment sites for the subsequent Ni(0)- mediated step-growth condensation polymerization of 2,7-dibromo-9,9-dihexylfluorene The step-growth polymerization medium consisted of 2,7-dibromo-9,9-dihexylfluorene, Ni(0)-catalyst, and bipyridine in a toluene/dimethylformamide solvent mixture. The resulting growth of polydihexylfluorene brushes from the patterned surface was monitored by contact angle, optical spectrometry, surface profilometry and AFM. Brush growth was conducted from patterned features ranging from 100 μm to 100 nm in width and 50 nm in height. The optical and fluorescence behavior of the polyfluorene brushes was similar to that of thin polyfluorene films made by spin coating. © 2006 American Chemical Society.