Ordered Surface Structuring of Spherical Colloids with Binary Nanoparticle Superlattices

Surface-patterning colloidal matter in the sub-10 nm regime generates exceptional functionality in biology and photonic and electronic materials. Techniques of artificially generating functional patterns in the small nanoscale advanced in a fascinating manner in the last several years. However, they remain often restricted to planar and noncolloidal substrates. Patterning colloidal matter in solution via bottom-up assembly of smaller subunits on larger core particles is highly challenging because it is necessary to force the subunits onto randomly moving objects. Consequently, the nonequilibrium conditions present during nanoparticle self-assembly are difficult to control to eventually achieve the desired material structures. Here, we describe the formation of surface patterns with intrinsic periodic repeats of 8.9 +/- 0.9 nm and less on hard, amorphous colloidal core particles by assembling binary nanoparticle superlattices on the curved particle surface. The colloidal environment is preserved during the entire bottom-up crystallization of variable building blocks (here, monodispersed 5 nm Au and 2.4 inn Pd nanopartides (NPs) and 230 nm SiO2 core particles) into AB(13)-like, binary, and isotropic superlattice domains on the amorphous cores. The three-dimensional, bottom-up assembly technique is a new tool for patterning colloidal matter in the sub-10 nm surface regime for gaining access to multicomponent metamaterials for bionanoscience, photonics, and electronics.