Architecture Effects in Complex Spherical Assemblies of (AB)-Type Block Copolymers

Molecular architecture plays a key role in the self-assembly of block copolymers, but few studies have systematically examined the influence of chain connectivity on tetrahedrally close-packed (TCP) sphere phases. Here, we report a versatile material platform comprising two blocks with substantial conformational asymmetry, A = poly(trifluoroethyl acrylate) and B = poly(dodecyl acrylate), and use it to compare the phase behavior of AB diblocks, ABA triblocks, and (AB) radial star copolymers with n = 3 or 4. Each architecture forms TCP sphere phases at minority A block compositions (f_A < 0.5), namely, σ and A15, but with differences in the location of order-order phase boundaries that are not anticipated by mean-field self-consistent field theory simulations. These results expand the palette of polymer architectures that readily self-assemble into complex TCP structures and suggest important design considerations when targeting specific phases of interest.