Plasmonic Nanoparticle Arrays with Nanometer Separation for High-Performance SERS Substrates

We demonstrate a method for fabricating arrays of plasmonic nanoparticles with separations on the order of 1 nm using an angle evaporation technique. Samples fabricated on thin SiN membranes are imaged with high-resolution transmission electron microscopy (HRTEM) to resolve the small separations achieved between nanoparticles. When irradiated with laser light, these nearly touching metal nanoparticles produce extremely high electric field intensities, which result in surface-enhanced Raman spectroscopy (SERS) signals. We quantify these enhancements by depositing a p-aminothiophenol dye molecule on the nanoparticle arrays and spatially mapping their Raman intensities using confocal micro-Raman spectroscopy. Our results show significant enhancement when the incident laser is polarized parallel to the axis of the nanoparticle pairs, whereas no enhancement is observed for the perpendicular polarization. These results demonstrate proof-of-principle of this fabrication technique. Finite difference time domain simulations based on HRTEM images predict an electric field intensity enhancement of 82400 at the center of the nanoparticle pair and an electromagnetic SERS enhancement factor of 10(9)-10(10).