Diblock copolymer templated self-assembly of grafted nanoparticles under circular pore confinement

Abstract

Geometrical confinement plays an important role in generating novel molecular organization arising out of structural frustration and confinement-induced entropy loss. In the present study, we perform self-consistent mean-field theoretical calculations to examine a mixture of a diblock copolymer and polymer grafted nanoparticles confined in a cylindrical nanopore. The two-dimensional analysis is aimed at constructing the equilibrium nanostructures decorated with particles in an ordered manner. The rich variety of ordered mesophases of the diblock copolymer under confinement provide a template to achieve the self-assembly of nanoparticles in a selective domain. The localization behavior of nanoparticles under confinement is found to be qualitatively different from that in a bulk system. In particular, for the concentric lamellar phase the particles tend to localize predominantly in the region of greater curvature within the curved lamella. The incorporation of grafted nanoparticles also results in a transition in ordered phases. Various equilibrium morphologies are observed depending upon the degree of confinement, particle loading, density of grafted segments and selectivity of the particle core to the polymeric species. The ordering of particles and the ensuing equilibrium nanostructures are analyzed. The comprehensive understanding of the self-assembly behavior of particles enables one to design novel nanomaterials with desirable material properties.