Uniform High-Level Block Copolymer Architectures via Hybrid Self-Seeding

Abstract

The construction of hierarchical architectures with precisely controlled dimensions and morphologies remains a key challenge in block copolymer self-assembly. Here we introduce hybrid self-seeding, a streamlined strategy that employs either the coassembly of a crystallizable homopolymer with two block copolymers or the direct self-seeding of mixed one-dimensional (1D) and two-dimensional (2D) seed fragments. By orchestrating sequential nucleation events where the homopolymer nucleates first, followed by block copolymers with decreasing propensity for 1D growth, we achieve precise morphological control in a single process. This method yields uniform scarf-like micelles (up to 34 μm), yucca flaccida-like architectures, and long ribbon-like morphologies. Electron diffraction confirms homoepitaxial growth across morphological domains, linking the structural memory effect to crystal lattice continuity. Our approach establishes a generalizable platform for higher-level soft matter.