Self-organization of a 4-miktoarm star block copolymer induced by cylindrical confinement.

Self-consistent field calculations have been carried out to reveal the self-assembly behavior of a melt of the ABCD star tetrablock copolymer confined within a cylindrical nanopore. The miktoarm star block copolymer exhibits a rich self-assembly behavior with a myriad of interesting three-dimensional ordered phases with the potential to produce advanced nanomaterials. The broad array of ordered mesophases includes helical microstructures, stack of rings/doughnuts, honeycomb structure, and perforated lamella with beads, depending on the individual block fractions and the size of the cylindrical nanopore. Such chiral motifs generated from achiral polymeric molecules are fascinating due to their superior performance in sophisticated opto-electronic devices. The study also demonstrates an interesting morphology, viz. a honeycomb structure, obtained from the self-organization of ABCD star block copolymer molecules with equal block fractions. The system exhibits order-order phase transition covering a range of ordered morphologies by changing either the block fraction or the nanopore radius. A representative phase diagram in terms of block fractions is constructed. These novel ordered microstructures, arising mainly out of structural frustration and confinement-induced entropy loss, can serve as structural scaffolds to host the spatial distribution of nanoparticles resulting into novel nanocomposites with significantly enhanced as well as controllable properties.