Self-brushing for nanopatterning: Achieving perpendicular domain orientation in block copolymer thin films

The self-assembly of thin films of block copolymers (BCPs) with perpendicular domain orientation offers a promising approach for nanopatterning on a variety of substrates, which is required by advanced applications such as ultrasmall transistors in integrated circuits, nanopatterned materials for tissue engineering, and electrocatalysts for fuel cell applications. In this study, we created BCPs with an A-b-(B-r-C) architecture that have blocks with equal surface energy (γ_air) and that can bind to the substrate, effectively creating a non-preferential substrate coating via self-brushing that enables the formation of through-film perpendicular domains in thin films of BCPs. We employed a thiol–epoxy click reaction to functionalize polystyrene-block-poly(glycidyl methacrylate) with a pair of thiols to generate an A-b-(B-r-C) BCP and tune γ_air of the B-r-C block. The secondary hydroxyl and thiol ether functionality generated by the click reaction was utilized to bind the BCP to the substrates. Scanning electron microscopy revealed that perpendicular orientation was achieved by simply annealing a thin film of the BCP on the bare substrate without the usual extra step of coating a random copolymer brush on the substrate. The self-brushing capability of the BCP was also examined on gold, platinum, titanium, aluminum nitride, and silicon nitride surfaces. These results demonstrate that self-brushing is a promising approach for achieving perpendicular domain orientation in thin films of BCP for nanopatterning on a variety of useful surfaces.