Assembly by solvent evaporation: equilibrium structures and relaxation times

We present a study describing the dynamics and equilibrium of the assembly of nanostructures by solvent evaporation. We first consider N nanocrystals stabilized by capping ligands in a spherical droplet of liquid solvent coexisting with its gas and show that, as the liquid solvent evaporates slowly, NCs crystallize into clusters of high symmetry based on tetrahedral and octahedral units: tetrahedron (N = 4), octahedron (N = 6), icosahedron (N = 13), Archimedean truncated tetrahedron (N = 16) and Z₂₀ (N = 21). We derive explicit formulas for the process and rigorously compute relaxation times, which drastically increase when the packing parameter reaches the hard-sphere liquid-solid transition η = 0.49. This result shows that contrary to what occurs in an evaporation of a single component system, the relaxation times are not determined by the diffusion constant of the vapor, but rather, are dominated by the residence time of solvent molecules trapped within the capping ligands. Our theory provides a number of predictions that enable the design of new structures while improving the control and quality of their assembly.