Study of coupling efficiency of molecules to surface plasmon polaritons in surface-enhanced Raman scattering (SERS)

Studying the interaction between molecules and surface plasmon polaritons (SPPs) is of great important in understanding surface-enhanced Raman scattering (SERS). While it is known that SERS consists of excitation and emission enhancements, each of them is manifested by several sub-steps which individually also deserve attention. For example, for emission enhancement, the energy from the excited molecules is first coupled to SPPs, which then radiatively scatter to far-field. To understand these two sequential processes completely, differentiating them one by one is necessary. Here, we decouple them and determine the coupling efficiency of molecules to SPPs by using a phenomenological rate equation model. We find the coupling efficiency, defined as the ratio of the coupling rate from molecules to SPPs to the direct Raman decay rate, can be expressed as the SERS intensity ratio and the SPP absorption and radiative decay rates, which all can be determined by polarization- and angle-dependent Raman and reflectivity spectroscopy. As a demonstration, the coupling efficiencies of 6-mercaptopurine to SPPs propagating in Gamma-X direction on Ag nanohole array are measured for several Raman emission wavelengths. (C)2013 Optical Society of America