Symmetry-Breaking and Self-Sorting in Block Copolymer-Based Multicomponent Nanocomposites

Co-assembly of inorganic nanoparticles (NPs) and nanostructured polymer matrix represents an intricate interplay of enthalpic or entropic forces. Particle size largely affects the phase behavior of the nanocomposite. Theoretical studies indicate that new morphologies would emerge when the particles become comparable to the soft matrix's size, but this has rarely been supported experimentally. By designing a multicomponent blend composed of NPs, block copolymer-based supramolecules, and small molecules, a 3-D ordered lattice beyond the native BCP's morphology was recently reported when the particle is larger than the microdomain of BCP. The blend can accommodate various formulation variables. In this paper, when the particle size equals the microdomain size, a symmetry-broken phase appears in a narrow range of particle sizes and compositions, which we named the "train track" structure. In this phase, the NPs aligned into a 3-D hexagonal lattice and packed asymmetrically along the c axis, making the projection of the ac and the bc plane resemble train tracks. Computational studies show that the broken symmetry reduces the polymer chain deformation and stabilizes the metastable hexagonally perforated lamellar morphology. Given the mobility of the multicomponent blend, the system shows a self-sorting behavior: segregating into two macroscopic phases with different nanostructures based on only a few nanometers NP size differences. Smaller NPs form "train track" morphology, while larger NPs form a "simple hexagon" structure, where the NPs take a symmetric hexagonal arrangement. Detailed structural evolution and simulation studies confirm the systematic-wide cooperativity across different components, indicating the strong self-regulation of the multicomponent system.