Crystallization-dictated assembly of block copolymers and nanoparticles under three-dimensional confinement.

Crystallization-dictated self-assembly of crystalline block copolymers (BCPs) in solution has been utilized to produce many impressive nanostructures. However, when the assembly of crystalline BCPs happens in a three-dimensional (3D) confined space, predicting the self-assembly structure of BCPs becomes challenging due to the competition between crystallization and microphase separation. In this feature article, we summarize the recent progress in the self-assembly of crystalline BCPs under confinement, emphasizing the impact of crystallization behavior on the assembly structure. Furthermore, we highlight the crystallization-directed assembly of inorganic nanoparticles (NPs), either by pre-assembling crystalline polymers as templates or using crystalline polymer chain segments as ligands. By exploring the impact of crystallization behavior on the assembled structure of BCPs and NPs, it is helpful to predict and manipulate the properties of polymer/nanoparticle composites, thereby enabling the precise design of polymer metamaterials.