Structural diversity in binary nanoparticle superlattices

The assembly of nanoparticles of two different materials into a binary nanoparticle superlattice is a promising way of synthesizing a large variety of materials (metamaterials) with precisely controlled chemical composition and tight placement of the components. In theory only a few stable binary superlattice structures can assemble from hard spheres, potentially limiting this approach. But all is not lost because at the nanometre scale there are additional forces (electrostatic, van der Waals and dipolar) that can stabilize binary nanoparticulate structures. Shevchenko et al. now report the synthesis of a dozen novel structures from various combinations of metal, semiconductor, magnetic and dielectric nanoparticles. This demonstrates the potential of self-assembly in designing families of novel materials and metamaterials with programmable physical and chemical properties. Assembly of small building blocks such as atoms, molecules and nanoparticles into macroscopic structures—that is, ‘bottom up’ assembly—is a theme that runs through chemistry, biology and material science. Bacteria1, macromolecules2 and nanoparticles3 can self-assemble, generating ordered structures with a precision that challenges current lithographic techniques. The assembly of nanoparticles of two different materials into a binary nanoparticle superlattice (BNSL)3,4,5,6,7 can provide a general and inexpensive path to a large variety of materials (metamaterials) with precisely controlled chemical composition and tight placement of the components. Maximization of the nanoparticle packing density has been proposed as the driving force for BNSL formation3,8,9, and only a few BNSL structures have been predicted to be thermodynamically stable. Recently, colloidal crystals with micrometre-scale lattice spacings have been grown from oppositely charged polymethyl methacrylate spheres10,11. Here we demonstrate formation of more than 15 different BNSL structures, using combinations of semiconducting, metallic and magnetic nanoparticle building blocks. At least ten of these colloidal crystalline structures have not been reported previously. We demonstrate that electrical charges on sterically stabilized nanoparticles determine BNSL stoichiometry; additional contributions from entropic, van der Waals, steric and dipolar forces stabilize the variety of BNSL structures.