Crosslinking Modulated Hierarchical Self-Assembly of Rod–Coil Diblock Copolymer Patchy Nanoparticles

Stepwise self-assembly of block copolymers offers a convenient route to structuring complex materials over multiple length scales. Still, the controllability and adjustability of such approaches need to be further improved. We proposed a crosslinking strategy and presented a computational study on the stepwise self-assembly of rod–coil diblock copolymers modulated by crosslinking. The computation results showed that the crosslinking number and rod block length determine the structure of transient patchy particles, which affect the morphology of hierarchical aggregates formed eventually. We discovered that the packing parameter of temporary patchy particles can effectively predict the geometry of hierarchical aggregates. In particular, we found that the stepwise self-assembly modulated by crosslinking can help build supracolloidal networks with hierarchy.