Fabrication of stimulus-responsive polymeric nanostructures by proximal probes

The triggered control of interfacial properties on the nanometer scale holds significant promise for actuation in bio-nanotechnology applications where polymeric actuators may manipulate the transport, separation, and detection of biomolecules. To fabricate patterned, stimulus-responsive polymer brushes we have developed several methods that combine surface initiated polymerization (SIP) with dip-pen nanolithography (DPN). Surface-confined, stimulus-responsive polymer brush nanopatterns were fabricated by amplification of DPN patterned, self-assembled monolayers of 16-mercaptohexadecanoic acid on gold surfaces by SIP of N-isopropylacrylamide (NIPAAm). While free radical polymerization yielded only short polymer brushes (DP<50), atom transfer free radical polymerization (ATRP) produced thick, uniform polymer brushes. For free radical polymerization the thickness of the polymer brush layer is a function of the lateral feature size and the initiator density and is maximal at pattern boundaries.