Nanoimprint methods for the fabrication of macroscopic plasmonically active metal nanostructures

In this article, we present a refined nanostructuring method, lift-off nanoimprint lithography (LO-NIL), which allows the deposition of high-quality metal nanostructures due to a bilayer resist process and compare it to nano-transfer printing (nTP), a purely additive metal printing technique. LO-NIL and nTP are used as accurate methods for the fabrication of ordered plasmonic metal nanostructure arrays on semiconducting substrates over large areas using the example of gold nanodisks on silicon. The possibility of feature size adjustment in LO-NIL during the fabrication process is especially useful for tuning plasmonic resonance peaks between the visible and the mid-infrared range as well as fine-tuning of these resonances. In UV-VIS-NIR spectroscopic measurements, a significant blueshift in the plasmonic resonance was found for nTP samples compared to the ones fabricated with the lift-off technique. It was concluded that this shift originates from a metal/substrate interface roughness resulting in a change in the dielectric properties of this layer. This finding was verified with finite difference time-domain simulations where a similar trend was found for a model with an assumed thin air gap in this interface. In cyclic voltammetry measurements under illumination, a reduced overpotential by almost 400 mV for CO₂ reduction and hydrogen evolution was found for LO-NIL samples.