Massively Parallel Arrays of Size-Controlled Metallic Nanogaps with Gap-Widths Down to the Sub-3-nm Level

Metallic nanogaps (MNGs) are fundamental components of nanoscale photonic and electronic devices. However, the lack of reproducible, high-yield fabrication methods with nanometric control over the gap-size has hindered practical applications. A patterning technique based on molecular self-assembly and physical peeling is reported here that allows the gap-width to be tuned from more than 30 nm to less than 3 nm. The ability of the technique to define sub-3-nm gaps between dissimilar metals permits the easy fabrication of molecular rectifiers, in which conductive molecules bridge metals with differing work functions. A method is further described for fabricating massively parallel nanogap arrays containing hundreds of millions of ring-shaped nanogaps, in which nanometric size control is maintained over large patterning areas of up to a square centimeter. The arrays exhibit strong plasmonic resonances under visible light illumination and act as high-performance substrates for surface-enhanced Raman spectroscopy, with high enhancement factors of up to 3 × 10⁸ relative to thin gold films. The methods described here extend the range of metallic nanostructures that can be fabricated over large areas, and are likely to find many applications in molecular electronics, plasmonics, and biosensing.