Deviatoric stress-driven fusion of nanoparticle superlattices.

We model the mechanical response of alkanethiol-passivated gold nanoparticle superlattice (supercrystal) at ambient and elevated pressures using large-scale molecular dynamics simulation. Because of the important roles of soft organic ligands in mechanical response, the supercrystals exhibit entropic viscoelasticity during compression at ambient pressure. Applying a hydrostatic pressure of several hundred megapascals on the superlattice, combined with a critical deviatoric stress of the same order along the [110] direction of the face-centered-cubic supercrystal, can drive the room-temperature sintering ("fusion") of gold nanoparticles into ordered gold nanowire arrays. We discuss the molecular-level mechanism of such phenomena and map out a nonequilibrium stress-driven processing diagram, which reveals a region in stress space where fusion of nanoparticles can occur, instead of other competing plasticity or phase transformation processes in the supercrystal. We further demonstrate that, for silver-gold (Ag-Au) binary nanoparticle superlattices in sodium chloride-type superstructure, stress-driven fusion along the [100] direction leads to the ordered formation of Ag-Au multijunction nanowire arrays.