Silver Nanocube Epitaxy via Nanogap‐Induced Electrostatics

Abstract Silver nanostructures are highly valued in nanophotonic devices due to their appealing plasmonic properties and affordability relative to gold. Yet, fabricating high‐quality, monocrystalline silver nanostructures, with full control over the shape, is challenging. A mild, liquid‐phase method for the epitaxial welding of adjacent monocrystalline silver nanocubes in reductant‐free conditions is introduced to prevent the formation of detrimental nuclei on the surface that can degrade the nanostructures' optical qualities. The mechanism is thoroughly investigated and it is found that the nanocubes themselves can act as reducing agents, promoting growth preferentially into the gap as a result of electrostatic interactions. By controlling experimental parameters such as temperature, pH, and the introduction of capping agents, a balance between nanocube epitaxy and shape retention is achieved. Finally, by applying this procedure to nanoparticle assembled in predefined meta‐atoms, the feasibility of creating intricate silver nanostructures, that are monocrystalline as verified by transmission electron microscopy (TEM), is demonstrated. This advancement paves the way for bottom‐up fabrication of optical metasurfaces that can be swiftly integrated in devices.