There are two options for realizing apertureless NSOM-Raman technique: TERS and SERS. TERS is frequently used for apertureless NSOM-Raman and can significantly enhance the spatial resolution. This technique requires a metal tip to enhance the signal of the sample. That is why an AFM metal tip is usually used for enhancing the electric field for molecule excitation. Raman spectroscopy was combined with AFM in 1999. A very narrow aperture of the tip was required to obtain a relatively high spatial resolution; such aperture reduced the signal and was difficult to prepare. In 2000, Stȍckle et al. first designed a setup combining apertureless NSOM, Raman and AFM techniques, in which the tip had a 20 nm thick granular silver film on it. They reported a large gain in the Raman scattering intensity of a dye film (brilliant cresyl blue) deposited on a glass substrate if a metal-coated AFM tip was brought very close to the sample. About 2000-fold enhancement of Raman scattering and a spatial resolution of ~55 nm were achieved.
Similarly, Nieman et al. used an illuminated AFM tip coated with a 100 nm thick film of gold to enhance Raman scattering from polymers samples and achieved a resolution of 100 nm. In the early research of TERS, the most commonly used coating materials for the tip probe were silver and gold. High-resolution spatial maps of Raman signals were obtained with this technique from molecular films of such compounds as brilliant cresyl blue, malachite green isothiocyanate and rhodamine 6G, as well as individual carbon nanotubes.