One-Step Synthesis and Self-Assembly of Metal Oxide Nanoparticles into 3D Superlattices

A simple one-pot approach based on the “benzyl alcohol route” is introduced for the fabrication of highly ordered supercrystals composed of highly uniform 3–4 nm zirconia and rare-earth stabilized zirconia nanoparticles. The as-fabricated supercrystals reach sizes larger than 10 μm and present well-defined 3D morphologies such as flower-like, rhombic dodecahedron, and bipyramids. This system is unique in that the supercrystals are formed in one-step directly in the reaction medium where the nanoparticles are synthesized. The uniformity in nanocrystal shape and size is attributed to the in situ formation of benzoate species that directs the nanoparticle growth and assembly. The low colloidal stabilization of the benzoate-capped nanoparticles in benzyl alcohol promotes the formation of supercrystals in solution by π–π interaction between the in situ formed benzoate ligands attached to neighboring particles. By varying the reaction temperature and the nature of the doping the way the nanobulding blocks assemble in the supercrystals could be controlled. Standard FCC superlattice packings were found together with more unusual ones with P6/mmm and R3̅m symmetries.