Shape Alloys of Nanorods and Nanospheres from Self-Assembly

Mixtures of anisotropic nanocrystals promise a great diversity of superlattices and phase behaviors beyond those of single-component systems. However, obtaining a colloidal shape alloy in which two different shapes are thermodynamically co-assembled into a crystalline superlattice has remained a challenge. Here we present a joint experimental-computational investigation of two geometrically ubiquitous nanocrystalline building blocks---nanorods and nanospheres---that overcome their natural entropic tendency towards macroscopic phase separation and co-assemble into three intriguing phases over centimeter scales, including an AB2-type binary superlattice. Monte Carlo simulations reveal that although this shape alloy is entropically stable at high packing fraction, demixing is favored at experimental densities. Simulations with short-ranged attractive interactions demonstrate that the alloy is stabilized by interactions induced by ligand stabilizers and/or depletion effects. An asymmetry in the relative interaction strength between rods and spheres improves the robustness of the self-assembly process. Reference: Ye, Millan, Engel, Chen, Diroll, Glotzer, Murray, Nano Letters 13, 4980 (2013).