The seed-mediated growth of noble metal nanostructures with planar geometries requires the use of seeds lined with parallel stacking faults so as to provide a break in symmetry in an otherwise isotropic metal. Although such seeds are now routinely synthesized using colloidal pathways, equivalent pathways have not yet been reported for the fabrication of substrate-based seeds with the same internal defect structures. The challenge is not merely to form seeds with planar defects but to do so in a deterministic manner so as to have stacking faults that only run parallel to the substrate surface while still allowing for the lithographic processes needed to regulate the placement of seeds. Here, we demonstrate substrate-imposed epitaxy as a viable synthetic control able to induce planar defects in Au seeds while simultaneously dictating nanostructure in-plane alignment and crystallographic orientation. The seeds, which are formed in periodic arrays using nanoimprint lithography in combination with a vapor-phase assembly process, are subjected to a liquid-phase plasmon-mediated synthesis that uses light as an external stimuli to drive a reaction yielding periodic arrays of hexagonal Au nanoplates. These achievements not only represent the first of their kind demonstrations but also advance the possibility of integrating wafer-based technologies with a rich and exciting nanoplate colloidal chemistry.

Galvanic replacement reactions carried out on solid core-shell structures typically yield a noble metal nanorattle geometry in which a mobile core is contained within a hollowed shell. Here, we adapt this colloidal synthesis to substrate-based structures to obtain a fundamentally altered product in which an immobilized core is separated from the shell by a well-defined gap, an architecture unobtainable using colloidal techniques and that offers unique advantages in terms of generating plasmonic near-field effects within the confines of a single structure. In the devised route, Wulff-shaped templates of Au, Pt, or Pd, formed through the dewetting of ultrathin films, are first transformed into core-shell structures through the reduction of Ag(+) ions onto their surface and then further transformed through the galvanic replacement of Ag with Au. Through suitable adjustments to the shell geometry, the epitaxial relationship with the substrate, and the extent to which the shell is replaced, it is possible to generate an entire family of nanostructures in which a Wulff-shaped core is confined within a nanoshell, nanocage, or nanoframe, where, in all cases, bonds formed between the structure and the substrate preclude motion. With the potential to tune the gap width, the geometry of the confining structure, and the composition of the core, shell, and substrate, these structures could find application as catalytic nanoreactors able to drive both single-step and cascade reactions or as plasmon-based sensing elements for biological and chemical detection.

Current best-practice lithographic techniques are unable to meet the functional requirements needed to enable on-chip plasmonic devices capable of fully exploiting nanostructure properties reliant on a tailored nanostructure size, composition, architecture, crystallinity, and placement. As a consequence, numerous nanofabrication methods have emerged that address various weaknesses, but none have, as of yet, demonstrated a large-area processing route capable of defining organized surfaces of nanostructures with the architectural diversity and complexity that is routinely displayed in colloidal syntheses. Here, a hybrid fabrication strategy is demonstrated in which nanoimprint lithography is combined with templated dewetting and liquid-phase syntheses that is able to realize periodic arrays of complex noble metal nanostructures over square centimeter areas. The process is inexpensive, can be carried out on a benchtop, and requires modest levels of instrumentation. Demonstrated are three fabrication schemes yielding arrays of core-shell, core-void-shell, and core-void-nanoframe structures using liquid-phase syntheses involving heteroepitaxial deposition, galvanic replacement, and dealloying. With the field of nanotechnology being increasingly reliant on the engineering of desirable physicochemical responses through architectural control, the fabrication strategy provides a platform for advancing devices reliant on addressable arrays or the collective response from an ensemble of identical nanostructures.