Precise Control of Two-Dimensional Hexagonal Platelets via Scalable, One-Pot Assembly Pathways Using Block Copolymers with Crystalline Side Chains

Crystallization-driven self-assembly (CDSA) of block copolymers (BCPs) in selective solvents provides a promising route for direct access to two-dimensional (2D) platelet micelles with excellent uniformity, although significant limitations also exist for this robust approach, such as tedious, multistep procedures, and low yield of assembled materials. Herein, we report a facile strategy for massively preparing 2D, highly symmetric hexagonal platelets with precise control over their dimensions based on BCPs with crystalline side chains. Mechanistic studies unveiled that the formation of hexagonal platelets was subjected to a hierarchical self-assembly process, involving an initial stage of formation of kinetically trapped spheres upon cooling driven by solvophobic interactions, and a second stage of fusion of such spheres to the 2D nuclei to initiate the lateral growth of hexagonal platelets via sequential particle attachments driven by thermodynamically ordered reorganization of the BCP upon aging. Moreover, the size of the developed 2D hexagonal platelets could be finely regulated by altering the copolymer concentration over a broad concentration range, enabling scale-up to a total solids concentration of at least 6% w/w. Our work reveals a new mechanism to create uniform 2D core-shell nanoparticles dictated by crystallization and particle fusion, while it also provides an alternative facile strategy for the design of soft materials with precise control of their dimensions, as well as for the scalability of the derived nanostructures.