The role of tip plasmons in near‐field Raman microscopy

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Abstract
The enhancement in electric field strength in the vicinity of a metal tip, through the excitation of plasma modes in the tip, is investigated using the finite difference time domain method; such tip enhancement has significant potential for application in scanning near‐field Raman microscopy. To represent an experimentally realistic geometry the near‐field probe is described by a conical metal tip with a spherical apex, with radii 20 nm and 200 nm considered, in close proximity to a glass substrate. Illumination through the substrate is considered, both at normal incidence and close to the critical angle, with the polarization in the plane of incidence. By modelling the frequency dependent dielectric response of the metal tip we are able to highlight the dependence on the scattering geometry of the nature of the electromagnetic excitations in the tip. In particular, the strongest electric field enhancement with the greatest confinement occurs for the excitation of modes localized at the tip apex, excited only for off‐normal incidence. Bulk modes excited in the tip also produce enhancement, although over a larger area and with significantly less enhancement than that of the localized modes; however, the excitation of bulk modes is independent of the angle of incidence.