Confinement-induced self-assembly of a diblock copolymer within a non-uniform cylindrical nanopore.

The self-assembly of a diblock copolymer melt confined within a non-uniform cylindrical nanopore is studied using the self-consistent field theory. The non-uniformity manifests in the form of a converging-diverging cylindrical nanopore. The axial variation in pore diameter presents a range of curvatures within the same confinement pore as opposed to a single curvature in a uniform-diameter cylindrical pore. The introduction of multiple curvatures leads to the formation of novel microstructures not accessible in uniform cylindrical confinement. The well-known equilibrium structures like a single helix, double helices, and concentric lamella under cylindrical confinement transition into new morphologies such as hyperboloidal phases, microstructures containing rings with a bead, rings with spheres, and a squeezed helical phase as the pore diameter varies axially. The converging-diverging geometry of the confining pore renders the helical phases seen in the cylindrical pore less favorable. A phase diagram in the parametric space of the block fraction and the ratio of the smallest and largest pore radii has been constructed to depict the order-order transition of various microstructures. The ratio of radii, a measure of the non-uniformity of the pore, along with the pore length brings out some interesting morphologies. The mechanism of these structural transitions is understood as the interplay between the variation in pore curvature attributed to the non-uniformity, the spontaneous curvature of the block copolymer interface, and the enthalpic interaction between the segregated blocks.