Nanocube Epitaxy for the Realization of Printable Monocrystalline Nanophotonic Surfaces

Abstract Plasmonic nanoparticles of the highest quality can be obtained via colloidal synthesis at low‐cost. Despite the strong potential for integration in nanophotonic devices, the geometry of colloidal plasmonic nanoparticles is mostly limited to that of platonic solids. This is in stark contrast to nanostructures obtained by top‐down methods that offer unlimited capability for plasmon resonance engineering, but present poor material quality and have doubtful perspectives for scalability. Here, an approach that combines the best of the two worlds by transforming assemblies of single‐crystal gold nanocube building blocks into continuous monocrystalline plasmonic nanostructures with an arbitrary shape, via epitaxy in solution at near ambient temperature, is introduced. Nanocube dimers are used as a nanoreactor model system to investigate the mechanism in operando, revealing competitive redox processes of oxidative etching at the nanocube corners and simultaneous heterogeneous nucleation at their surface, that ensure filling of the sub‐nanometer gap in a self‐limited manner. Applying this procedure to nanocube arrays assembled in a patterned poly(dimethylsiloxane) (PDMS) substrate, it is able to obtain printable monocrystalline nanoantenna arrays that can be swiftly integrated in devices. This may lead to the implementation of low‐cost nanophotonic surfaces of the highest quality in industrial products.