Formation of 2D and 3D multi-tori mesostructures via crystallization-driven self-assembly

The fabrication of three-dimensional (3D) objects by polymer self-assembly in solution is extremely challenging. Here, multi-tori mesostructures were obtained from the crystallization-driven self-assembly of a coil-crystalline block copolymer (BCP) in mixed solvents. The formation of these structures follows a multistep process. First, the BCP self-assembles into amorphous micrometer-large vesicles. Then, the BCP confined in these mesosized vesicles crystallizes. This second step leads to the formation of objects with shapes ranging from closed 3D multi-tori spherical shells to 2D toroid mesh monolayers, depending on the solvent mixture composition. This approach demonstrates how topological constraints induced by the specific interactions between coil-crystalline BCP and solvents can be used to prepare mesostructures of complex morphologies.