We used scanning tunneling microscopy–tip-enhanced Raman spectroscopy (STM-TERS) to study the polarization properties of near-field scattering on a crystalline material as well as on a dye adsorbate. The measurements on a (111)-oriented c-Si sample were found to be well described by a recently proposed model for TERS and allowed for a characterization of the polarization properties of the tips used. The tip enhancement was stronger for excitation radiation having a field component along the tip axis for both types of samples. A non-negligible enhancement was also found for the field component perpendicular to the tip axis.

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