Nanoparticle Superlattices with Nonequilibrium Crystal Shapes

Nanoparticle assembly is a material synthesis strategy that enables precise control of nanoscale structural features. Concepts from traditional crystal growth research have been tremendously useful in predicting and programming the unit cell symmetries of these assemblies, as their thermodynamically favored structures are often identical to atomic crystal analogues. However, these analogies have not yielded similar levels of influence in programming crystallite shapes, which are a consequence of both the thermodynamics and kinetics of crystal growth. Here, we demonstrate kinetic control of the colloidal crystal shape using nanoparticle building blocks that rapidly assemble over a broad range of concentrations, thereby producing well-defined crystal habits with symmetrically oriented dendritic protrusions and providing insight into the crystals' morphological evolution. Counterintuitively, these nonequilibrium crystal shapes actually become more common for colloidal crystals synthesized closer to equilibrium growth conditions. This deviation from typical crystal growth processes observed in atomic or molecular crystals is shown to be a function of the drastically different time scales of atomic and colloidal mass transport. Moreover, the particles are spherical with isotropic ligand grafts, and these kinetic crystal habits are achieved without the need for specifically shaped particle building blocks or external templating or shape-directing agents. Thus, this work provides generalizable design principles to expand the morphological diversity of nanoparticle superlattice crystal habits beyond the anhedral or equilibrium polyhedral shapes synthesized to date. Finally, we use this insight to synthesize crystallite shapes that have never before been observed, demonstrating the ability to both predict and program kinetically controlled superlattice morphologies.