Chain topology offers a chemistry-preserving route to tune block copolymer (BCP) self-assembly by modifying intrachain correlations and relaxation pathways without changing monomer interactions. Here, we perform a unit-matched comparison of four lamella-forming AB architectures reconstructed from an identical constitutive diblock unit (N0): a linear diblock (DB), a linear multiblock (MB), a comb-like architecture (CB), and a star-like architecture (SB). Using dynamical density functional theory (DDFT), we quantify topology-dependent bulk ordering thresholds and show that architectural reconfiguration systematically stabilizes the ordered phase, reducing the order–disorder transition relative to DB (MB/CB/SB ≈0.793/0.762/0.752 of the diblock value), in semi-quantitative agreement with random phase approximation (RPA) spinodal trends. We also compare topology-dependent directed self-assembly in a common trench geometry under matched reduced quench depth Δ(χN0)=χN0−(χN0)ODT, thereby isolating kinetic differences at comparable thermodynamic distance from bulk ordering. A Fourier-based alignment order parameter α(t) reveals sigmoidal alignment kinetics over decades in time and is well captured by a logistic form in lnt, enabling compact descriptors (t50, t90, and a steepness parameter k) that separate alignment onset from late-stage defect annihilation, while selective sidewalls robustly template sidewall-parallel lamellae across all topologies, the late-stage kinetics remain strongly connectivity dependent and can exhibit long-tailed completion associated with slow late-stage defect annihilation. These results demonstrate a dual role of topology in DSA: lowering the segregation strength required for bulk ordering while reshaping defect-mediated alignment pathways under confinement.
June Huh (Wed,) studied this question.