Confinement-induced ordering of grafted nanoparticles aided by diblock copolymers

Self-assembly behavior of polymer grafted nanoparticles in ordered phases of geometrically confined diblock copolymers is studied using self-consistent field theory. Entropy loss and structural frustration introduced by physical confinement significantly alter the morphology of ordered phases from the bulk behavior. In particular, a rich variety of three-dimensional microstructures, for example, helical structures, are obtained under confinement. In the present study, we demonstrate that ordered microstructures of diblock copolymers can be employed as promising structural scaffolds to host and self-assemble nanoparticles within the selective domain. Templated self-assembly of nanoparticles offers a potential route to fabricate advanced nanomaterials with superior properties. Analysis reveals various stable equilibrium phases of block copolymers embedded with nanoparticles with a high degree of nanoscale ordering. The arrangement of nanoparticles is controlled by tuning various parameters such as block fraction in diblock copolymers, particle loading, size and number of grafted chains, and degree of confinement. At a low volume fraction, nanoparticles self-organize into chiral microstructures, such as single and double helices, even though the system contains only achiral species. Upon enhancing particle loading, the helical structure becomes less favorable and various other three-dimensional phases such as ring and disk morphologies are obtained. The regions of helical, ring, disk, and concentric lamellar phases are identified in terms of parameters related to grafted particles. Understanding the factors affecting localization of nanoparticles enables us to control the particulate self-assembly behavior of nanoparticles to design novel and advanced nanocomposites with desirable properties.Self-assembly behavior of polymer grafted nanoparticles in ordered phases of geometrically confined diblock copolymers is studied using self-consistent field theory. Entropy loss and structural frustration introduced by physical confinement significantly alter the morphology of ordered phases from the bulk behavior. In particular, a rich variety of three-dimensional microstructures, for example, helical structures, are obtained under confinement. In the present study, we demonstrate that ordered microstructures of diblock copolymers can be employed as promising structural scaffolds to host and self-assemble nanoparticles within the selective domain. Templated self-assembly of nanoparticles offers a potential route to fabricate advanced nanomaterials with superior properties. Analysis reveals various stable equilibrium phases of block copolymers embedded with nanoparticles with a high degree of nanoscale ordering. The arrangement of nanoparticles is controlled by tuning various parameters such as block fra...