Hierarchical Self‐Assembly of 3D‐Printed Lock‐and‐Key Colloids through Shape Recognition

Progress in colloid self-assembly crucially depends on finding preparation methods for anisotropic particles with recognition motifs to facilitate the formation of superstructures. Here, we demonstrate for the first time that direct 3D laser writing can be used to fabricate uniform populations of anisotropic cone-shaped particles that are suitable for self-assembly through shape recognition. The driving force for the self-assembly of the colloidal particles into linear supracolloidal polymers are depletion forces. The resulting supracolloidal fibrils undergo hierarchical ordering and form nematic liquid-crystalline domains. Such a behavior could so far not be observed in the absence of an electric field. The study opens possibilities for using direct laser writing to prepare designed colloids on demand, and to study their self-assembly.