Asymmetric Interfacet Adatom Migration as a Mode of Anisotropic Nanocrystal Growth

Crystals are known to grow nonclassically or via four classical modes (the layer-by-layer, dislocation-driven, dendritic, and normal modes, which generally involve minimal interfacet surface diffusion). The field of nanoscience considers this framework to interpret how nanocrystals grow; yet, the growth of many anisotropic nanocrystals remains enigmatic, suggesting that the framework may be incomplete. Here, we study the solution-phase growth of pentatwinned Au nanorods without Br, Ag, or surfactants. Lower supersaturation conditions favored anisotropic growth, which appeared at variance with the known modes. Temporal electron microscopy revealed kinetically limited adatom funneling, as adatoms diffused asymmetrically along the vicinal facets (situated inbetween the {100} side-facets and {111} end-facets) of our nanorods. These vicinal facets were perpetuated throughout the synthesis and, especially at lower supersaturation, facilitated {100}-to-vicinal-to-{111} adatom diffusion. We derived a growth model from classical theory in view of our findings, which showed that our experimental growth kinetics were consistent with nanorods growing via two modes simultaneously: radial growth occurred via the layer-by-layer mode on {100} side-facets, whereas the asymmetric interfacet diffusion of adatoms to {111} end-facets mediated longitudinal growth. Thus, shape anisotropy was not driven by modulating the relative rates of monomer deposition on different facets, as conventionally thought, but rather by modulating the relative rates of monomer integration via interfacet diffusion. This work shows how controlling supersaturation, a thermodynamic parameter, can uncover distinct kinetic phenomena on nanocrystals, such as asymmetric interfacet surface diffusion and a fundamental growth mode for which monomer deposition and integration occur on different facets.