Structural hierarchy in blends of amphiphilic block copolymers self-assembled at the air-water interface

We present a concurrent self-assembly strategy for patterning hierarchical polymeric surface features by depositing variable-composition blends of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) and polybutadiene-block-poly(ethylene oxide) (PB-b-PEO) block copolymers at the air-water interface. Hierarchical strand networks of hydrophobic PS/PB blocks anchored via PEO blocks to the water surface, with an internal phase-separation structure consisting of periodic domains of PS blocks surrounded and connected by a matrix of PB blocks, are generated by the interplay of interfacial amphiphilic block copolymer aggregation and polymer/polymer phase separation. In contrast to the cylinder-in-strand structures previously formed by our group in which interfacial microphase separation between PS and PB blocks was constrained by chemical connectivity between the blocks, in the current system phase separation between PS and PB is not constrained by chemical connectivity and yet is confined laterally within surface features at the air-water interface. Investigations of multi-component polymer systems with different connectivities constraining repulsive and attractive interactions provides routes to new hierarchical surface patterns for a variety of applications, including photolithography masks, display technology, surface-guided cell growth and tissue engineering.