Modular super-assembly of hierarchical superstructures from monomicelle building blocks

Manipulating the super-assembly of polymeric building blocks still remains a great challenge due to their thermodynamic instability. Here, we report on a type of three-dimensional hierarchical core-satellite SiO₂@monomicelle spherical superstructures via a previously unexplored monomicelle interfacial super-assembly route. Notably, in this superstructure, an ultrathin single layer of monomicelle subunits (~18 nm) appears in a typically hexagon-like regular discontinuous distribution (adjacent micelle distance of ~30 nm) on solid spherical interfaces (SiO₂), which is difficult to achieve by conventional super-assembled methods. Besides, the number of the monomicelles on colloidal SiO₂ interfaces can be quantitatively controlled (from 76 to 180). This quantitative control can be precisely manipulated by tuning the interparticle electrostatic interactions (the intermicellar electrostatic repulsion and electrostatic attractions between the monomicelle units and the SiO₂ substrate). This monomicelle interfacial super-assembly strategy will enable a controllable way for building multiscale hierarchical regular micro- and/or macroscale materials and devices.