A novel near-field optical microscope based on a parabolic mirror is used for recording high-resolution tip-enhanced photoluminescence (PL) and Raman images with unprecedented sensitivity and contrast. The measurements reveal small islands on the Au surface with dimensions of only a few nanometres with locally enhanced Au PL. These islands appear as nanometre-sized hot spots in tip-enhanced Raman microscopy when benzotriazole molecules adsorbed on the Au surface serve as local sensors for the optical field. The spectra show that localized plasmons are the cause of both the locally enhanced Au PL and enhanced Raman scattering. This finding suggests that the dispersive background in the surface-enhanced Raman spectra can be explained simply by the enhanced Au PL in the gap. Furthermore, our results show that the surface flatness must be better than 1 nm, to provide an optically homogeneous substrate for near-field enhanced PL and Raman spectroscopy.

Tip-enhanced near-field optical images and correlated topographic images of an organic semiconductor film (diindenoperylene, DIP) on Si have been recorded with high optical contrast and high spatial resolution (17 nm) using a parabolic mirror with a high numerical aperture for tip illumination and signal collection. The DIP molecular domain boundaries being one to four molecular layers (1.5-6 nm) high are resolved topographically by a shear-force scanning tip and optically by simultaneously recording the 6x10{5} times enhanced photoluminescence (PL). The excitation is 4x10{4} times enhanced and the intrinsically weak PL-yield of the DIP-film is 15-fold enhanced by the tip. The Raman spectra indicate an upright orientation of the DIP molecules. The enhanced PL contrast results from the local film morphology via stronger coupling between the tip plasmon and the exciton-polariton in the DIP film.

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Summary Detecting efficiently the plasmon‐enhanced Raman signal of molecules created in the nanometre‐sized gap between a metal nanoparticle or the apex of a sharp tip and a metal surface is the key problem in particle‐ or tip‐enhanced local surface spectroscopy (Pettinger et al., 2004; Roth et al., 2006). The optical excitation field has to be polarized along the gap, and the field emerging from the gap has to be observed from the side. These geometrical restrictions usually limit the numerical aperture of the lens used for exciting the gap and collecting the scattered photons created in the gap. We present a novel method to overcome this problem. The solution is based on a confocal optical microscope with a high numerical aperture parabolic mirror for excitation and detection. Localized plasmons can be efficiently excited parallel to the surface normal by illuminating the parabolic mirror with a radially polarized doughnut mode and the field emerging sidewise from the gap can be efficiently collected by the rim of the parabolic mirror and directed to the detection system. First results on particle‐ and tip‐enhanced Raman spectroscopic measurements of benzotriazole molecules adsorbed on gold films are presented.