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.