Spatial arrangement of block copolymer nanopatterns using a photoactive homopolymer substrate

Spatial control of the orientation of block copolymers (BCPs) in thin films offers enormous opportunities for practical nanolithography applications. In this study, we demonstrate the use of a substrate comprised of poly(4-acetoxystyrene) to spatially control interfacial interactions and block copolymer orientation over different length scales. Upon UV irradiation poly(4-acetoxystyrene) undergoes a photo-Fries rearrangement yielding phenolic groups available for further functionalization. The wetting behaviour of PS-b-PMMA deposited on the poly(4-acetoxystyrene) films could be precisely controlled through controlling the UV irradiation dose. After exposure, and a mild post-exposure treatment, the substrate switches from asymmetric, to neutral and then to symmetric wetting. Upon exposure through photomasks, a range of high fidelity micro-patterns consisting of perpendicularly oriented lamellar microdomains were generated. Furthermore, the resolution of chemically patterned poly(4-acetoxystyrene) substrate could be further narrowed to submicrometer scale using electron beam lithography. When the BCP was annealed on an e-beam modified poly(4-acetoxystyrene) surface, the interface between domains of parallel and perpendicular orientation of the BCPs was well defined, especially when compared with the substrates patterned using the photomask.