Self-Assembled Nanoparticle Arrays on Chemical Nanopatterns Prepared Using Block Copolymer Lithography

We present a high-throughput and inexpensive fabrication approach that uses self-assembled block copolymer (BCP) films as templates to generate dense nanoscale chemical patterns of polymer brushes for the selective immobilization of Au nanoparticles (NPs). A cross-linked random copolymer mat that contains styrene and methyl methacrylate units serves both as a base layer for perpendicular assembly of nanoscale domains of poly­(styrene-<i>block</i>-methyl methacrylate) (PS-<i>b</i>-PMMA) films and as a nonadsorbing background layer that surrounds the chemical patterns. The selective removal of the PMMA block and the underlying mat via oxygen plasma etching generates binding sites which are then functionalized with poly­(2-vinylpyridine) (P2VP) brushes. Au NPs with a diameter of 13 nm selectively immobilize on the patterned P2VP brushes. An essential aspect in fabricating high quality chemical patterns is the superior behavior of methyl methacrylate containing cross-linked mats in retaining their chemistry during the grafting of P2VP brushes. The use of BCPs with different molecular weights and volume fractions allows for preparation of chemical patterns with different geometries, sizes, and pitches for generating arrays of single particles that hold great promise for applications that range from molecular sensing to optical devices