Super-radiant plasmon mode is more efficient for SERS than the sub-radiant mode in highly packed 2D gold nanocube arrays.

Abstract

The field coupling in highly packed plasmonic nanoparticle arrays is not localized due to the energy transport via the sub-radiant plasmon modes, which is formed in addition to the regular super-radiant plasmon mode. Unlike the sub-radiant mode, the plasmon field of the super-radiant mode cannot extend over long distances since it decays radiatively with a shorter lifetime. The coupling of the plasmon fields of gold nanocubes (AuNCs) when organized into highly packed 2D arrays was examined experimentally. Multiple plasmon resonance optical peaks are observed for the AuNC arrays and are compared to those calculated using the discrete dipole approximation. The calculated electromagnetic plasmon fields of the arrays displayed high field intensity for the nanocubes located in the center of the arrays for the lower energy super-radiant mode, while the higher energy sub-radiant plasmon mode displayed high field intensity at the edges of the arrays. The Raman signal enhancement by the super-radiant plasmon mode was found to be one hundred fold greater than that by sub-radiant plasmon mode because the super-radiant mode has higher scattering and stronger plasmon field intensity relative to the sub-radiant mode.