Stabilizing hexagonally close-packed phase in single-component block copolymers through rational symmetry breaking

Despite being predicted to be a thermodynamically equilibrium structure, the absence of direct experimental evidence of hexagonally close-packed spherical phase in single-component block copolymers raises uncomfortable concerns regarding the existing fundamental phase principles. This work presents a robust approach to regulate the phase behavior of linear block copolymers by deliberately breaking molecular symmetry, and the hexagonally close-packed lattice is captured in a rigorous single-component system. A collection of discrete A₁BA₂ triblock copolymers is designed and prepared through an iterative growth method. The precise chemical composition and uniform chain length eliminates inherent size distribution and other molecular defects. Simply by tuning the relative chain length of two end A blocks, a rich array of ordered nanostructures, including Frank-Kasper A15 and σ phases, are fabricated without changing the overall chemistry or composition. More interestingly, hexagonally close-packed spherical phase becomes thermodynamically stable and experimentally accessible attributed to the synergistic contribution of the two end blocks. The shorter A blocks are pulled out from the core domain into the matrix to release packing frustration, while the longer ones stabilize the ordered spherical phase against composition fluctuation that tends to disrupt the lattice. This study adds a missing puzzle piece to the block copolymer phase diagram and provides a robust approach for rational structural engineering.