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DNA-coated colloids can self-assemble into an incredible diversity of crystal structures, but their applications have been limited by poor understanding and control over the crystallization dynamics. To address this challenge, we use microfluidics to quantify the kinetics of DNA-programmed self-assembly along the entire crystallization pathway, from thermally activated nucleation through reaction-limited and diffusion-limited phases of crystal growth. Our detailed measurements of the temperature and concentration dependence of the kinetics at all stages of crystallization provide a stringent test of classical theories of nucleation and growth. After accounting for the finite rolling and sliding rates of micrometer-sized DNA-coated colloids, we show that modified versions of these classical theories predict the absolute nucleation and growth rates with quantitative accuracy. We conclude by applying our model to design and demonstrate protocols for assembling large single crystals with pronounced structural coloration, an essential step in creating next-generation optical metamaterials from colloids.

Coating colloidal particles with DNA is a promising strategy to make functional nanoscale materials because the particles can be programmed to spontaneously self-assemble into complex, ordered structures. In this Article, we explore the phase behavior and types of structures that can be formed when interactions between DNA-coated colloids are specified by linker DNA strands dispersed in solution. We show that linker-mediated interactions direct the self-assembly of colloids into equilibrium crystal structures. Furthermore, we demonstrate how different linker sequences and concentrations produce different crystal lattices, whose symmetry and compositional order are encoded exclusively by the linker-mediated interactions. These results illustrate how linkers can be used to separate the assembly instructions, encoded in the linkers, from the colloids themselves. We also examine the phase behavior of asymmetric linkers, which bind more strongly to one colloidal species than the other. We find that asymmetry strongly influences the concentration dependence of the colloidal interactions, which we explain using a mean-field model. We also find evidence that asymmetric linkers might help to reduce kinetic bottlenecks to colloidal crystallization. Together, our findings expand the design rules of linker-mediated self-assembly and make connections between the various schemes for programming assembly of DNA-coated colloids reported in the literature.

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