Structural Diversity in Hybrid Binary Superlattices Coassembled From Colloidal Nanocrystals and Submicrometer Colloids

Integrating nanocrystals (NCs) and submicrometer colloids, such as SiO 2 , to construct hybrid superlattices presents significant scientific and practical opportunities, yet their ordered coassembly is challenged by inherent colloidal incompatibility. Here, polystyrene (PS) ligands featuring six terminal amine groups are introduced, which facilitate robust hydrophobization of SiO 2 colloids through multivalent hydrogen bonding. The resulting PS‐grafted SiO 2 particles exhibit exceptional colloidal stability and compatibility with conventional hydrophobic NCs, enabling their ordered coassembly into hybrid binary superlattices with unprecedented structural diversity. In particular, hidden subsurface NCs are revealed at interstitial voids in multiple binary phases, highlighting structural complexities beyond those of conventional binary colloidal crystals. Furthermore, selective etching of SiO 2 colloids produces non‐close‐packed NC superlattices that are challenging to achieve through direct assembly. By addressing colloidal incompatibility through ligand design, this work paves the way for bridging nanoscale and submicroscale building blocks, facilitating the design of hybrid superlattices with wide applications in photonics, sensing, catalysis, and multifunctional metamaterials.