Site‐Specific Placement of Au Nanoparticles on Chemical Nanopatterns Prepared by Molecular Transfer Printing Using Block‐Copolymer Films

Inexpensive, large area patterning of ex‐situ synthesized metallic nanoparticles (NPs) at the nanoscale may enable many technologies including plasmonics, nanowire growth, and catalysis. Here, site‐specific localization of Au NPs onto nanoscale chemical patterns of polymer brushes is investigated. In this approach, patterns of hydroxyl‐terminated poly(styrene) brushes are transferred from poly(styrene‐block‐methyl methacrylate) (PS‐b‐PMMA) block copolymer films onto a replica substrate via molecular transfer printing, and the remaining areas are filled with hydroxyl‐terminated poly(2‐vinyl pyridine) (P2VP‐OH) brushes. Citrate‐stabilized Au NPs (13 nm) selectively bind to P2VP‐OH functionalized regions and the quality of the resulting assemblies depends on high chemical contrast in the patterned brushes. Minimization of the interpenetration of P2VP‐OH chains into PS brushes during processing is the key for achieving high chemical contrast. Large area hexagonal arrays of single Au NPs with a placement accuracy of 3.4 nm were obtained on patterns (～20 nm spots, ～40 nm pitch) derived from self‐assembled cylinder‐forming PS‐b‐PMMA films. Linear arrays of Au NPs were generated on patterns (40 nm lines, 80nm pitch) derived from lamellae‐forming PS‐b‐PMMA that had been directed to assemble on lithographically defined masters.