Free-standing sub-10 nm nanostencils for the definition of gaps in plasmonic antennas.

Nanogaps between metal nanostructures are useful in localizing optical energy in plasmonic antennas, but are challenging to directly pattern. Patterning with the positive-tone polymethyl methacrylate (PMMA) resist causes an undesirable spread in nanogap dimensions. On the other hand, the negative-tone hydrogen silsesquioxane (HSQ) resist possesses the high resolution suited for the definition of nanogaps. However, it requires a hydrofluoric acid solution for liftoff, making it incompatible with the quartz or glass substrates used in optical devices. In this work, we created free-standing nanostencils in HSQ with sub-10 nm dimensions onto PMMA supports, which allow liftoff in organic solvents, thus extending this method to a broad range of substrate materials. The cross-sectional profiles of the nanogaps formed between the gold nanostructures were imaged in a transmission electron microscope and measured to be similar to 8 nm. We demonstrated the utility of this process in fabricating entire arrays of dimer nanostructures with sub-10 nm gaps. Using a surface enhanced Raman scattering setup, an order of magnitude increase in peak intensity was observed when the fields in the gap were resonantly excited compared to when the fields were localized at the corners of the nanostructures.