Locally Favored Two-Dimensional Structures of Block Copolymer Melts on Nonneutral Surfaces

Self-assembly of block copolymers (BCPs) into arrays of well-defined nanoscopic structures has attracted extensive academic and industrial interests over the past several decades. In contrast to the bulk where phase behavior is controlled by the segmental interaction parameter, the total number of segments in BCPs and volume fraction, the morphologies and orientations of BCP thin films can also be strongly influenced by the substrate surface energy/chemistry effect (considered as a “substrate field”). Here, we report the formation of locally favored structures where all constituent blocks coexist side-by-side on nonneutral solid surfaces irrespective of their chain architectures, microdomain structures, and interfacial energetics. The experimental results using a suite of surface-sensitive techniques intriguingly demonstrate that individual preferred blocks and nonpreferred blocks lie flat on the substrate surface and form a two-dimensional percolating network structure as a whole. The large numbers of solid-segment contacts, which overcome a loss in the conformational entropy of the polymer chains, prevent the structure relaxing to its equilibrium state (i.e., forming microdomain structures) even in a (good) solvent atmosphere. Our results provide direct experimental evidence of the long-lived, nonequilibrium structures of BCPs and may point to a new perspective on the self-assembly of BCP melts in contact with impenetrable solids.