Surface-Enhanced Infrared Absorption of Self-Aligned Nanogap Structures

Plasmonic nanostructures are often used in surface-enhanced infrared absorption (SEIRA) spectroscopy to probe surface assembled molecules or the dielectric environment surrounding the metallic nanostructures. Here we fabricate metallic nanogap structures using self-aligned techniques on an intrinsic silicon substrate and correlate resulting SEIRA spectra with the choice of metal nanostructure geometry. A motivation is to compare the enhancement from hybridization of bright plasmon modes with the effect of hybridization between bright and dark plasmon modes. These structures provide a gap size below 10 nm and support strong field enhancements. The structures demonstrate their sensitivity through the enhanced absorption signature of the Si-O stretch in the native silicon oxide layer of nanometer thickness beneath the metal. Simulations reveal this thin layer plays a critical role in determining the plasmon modes of the nanostructures. Numerical simulations of the optical properties are consistent with the observations that stronger Si-O stretch signals are detected on self-aligned nanogap structures than nanorod arrays, highlighting the enhanced electromagnetic fields in the underlying native oxide.