Effective plasmon coupling in conical cavities for sensitive surface enhanced Raman scattering with quantitative analysis ability.

Conical silver nanocavity arrays are fabricated by directly depositing Ag on porous alumina templates with V-shaped nanopores. By controlling the thickness of deposited Ag, complete and cracked cavity arrays are constructed respectively. The cracked cavity arrays with the cavity wall consisting of Ag nanoparticles are demonstrated to exhibit higher surface enhanced Raman scattering (SERS) activity than the complete one. Numerical simulation reveals that an effective coupling of the cavity modes with the surface plasmons of Ag nanoparticles (NPs) generates a significantly enhanced local electric field on the cavity wall responsible for the high SERS activity. The optimized cavity array presents an enhancement factor (EF) of ∼7.4 × 106 and an excellent uniformity with a relative standard deviation (RSD) as small as ∼5% for rhodamine 6G (R6G) molecules. Moreover, a good linear correlation between the logarithmic Raman intensity and the molecular concentration endows the array with quantitative analysis ability. These cavity arrays therefore are of great potential for qualitative and quantitative chemical and biomedical analysis with high sensitivity and reproducibility.