Tunable Subnanometer Gaps in Self-Assembled Monolayer Gold Nanoparticle Superlattices Enabling Strong Plasmonic Field Confinement

[Image: see text] Nanoparticle superlattices produced with controllable interparticle gap distances down to the subnanometer range are of superior significance for applications in electronic and plasmonic devices as well as in optical metasurfaces. In this work, a method to fabricate large-area (∼1 cm(2)) gold nanoparticle (GNP) superlattices with a typical size of single domains at several micrometers and high-density nanogaps of tunable distances (from 2.3 to 0.1 nm) as well as variable constituents (from organothiols to inorganic S(2–)) is demonstrated. Our approach is based on the combination of interfacial nanoparticle self-assembly, subphase exchange, and free-floating ligand exchange. Electrical transport measurements on our GNP superlattices reveal variations in the nanogap conductance of more than 6 orders of magnitude. Meanwhile, nanoscopic modifications in the surface potential landscape of active GNP devices have been observed following engineered nanogaps. In situ optical reflectance measurements during free-floating ligand exchange show a gradual enhancement of plasmonic capacitive coupling with a diminishing average interparticle gap distance down to 0.1 nm, as continuously red-shifted localized surface plasmon resonances with increasing intensity have been observed. Optical metasurfaces consisting of such GNP superlattices exhibit tunable effective refractive index over a broad wavelength range. Maximal real part of the effective refractive index, n(max), reaching 5.4 is obtained as a result of the extreme field confinement in the high-density subnanometer plasmonic gaps.