Decanethiol-passivated silver nanocrystals are shown, by small-angle X-ray diffraction, to organize into hexagonal close packed or face centered cubic (fcc) structures depending on the substrate temperature. When the nanocrystals are passivated by dodecanethiols, fcc and body centered cubic lattices as well as disordered arrangements are observed. The different crystalline phases correspond to thermodynamic equilibrium states. The passivant chain length is shown to control the interactions between the nanocrystals and consequently the superlattice structure.
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