Search

Several technologies have attempted to deliver the analytical capabilities of Raman and fluorescence spectroscopies to developing nanotechnologies. They have, however, two limitations when applied to nanoscale structures: (i) diffraction limit and (ii) weak signal due to a small sampling volume. To overcome the first obstacle, researchers traditionally use aperture-limited near-field optics based on optical fibers with extremely small apertures (down to ~50 nm). Low transmission through the apertures exacerbates the second limitation by strongly decreasing the measured optical signal. An alternative method based on plasmon optics, strong and very local enhancement of the electric field of light in the vicinity of plasmon nanoparticles (usually Ag or Au), helps to overcome both problems. We overview developments in apertureless near-field optics that are based on a combination of optical spectroscopy and scanning probe microscopy (SPM), with SPM tips modified to have plasmon resonance at the apex. Apertureless near-field microscopy enables traditional confocal optical imaging, scanning probe microscopy (SPM), and a combination of optical and SPM imaging with spatial resolution ~10-20nm, unprecedented for optical techniques. We demonstrate simultaneous Raman and SPM imaging of semiconductor structures and also discuss the challenges facing widespread applicability of this emerging technology, for areas as far ranging as biomedical, semiconductor, and composite materials research.

In contrast with aperture-limited Scanning Near-field Optical Microscopy, where the focusing of light is achieved only with very high attenuation, in apertureless near-field optics light is both focused and strongly amplified by the surface plasmons of the probe. Although the general feasibility of this idea and the unprecedented in optics lateral resolution of ~ 15-30 nm have already been demonstrated, the actual field enhancement has so far been well below theoretical expectations, and the useful optical signals have been weak. To bridge the gap between the "proof-of-concept" experiments and reliable optical microscopy with molecular-scale resolution, one needs to unify accurate simulation with effective measurements of the optical properties of the tips and with fabrication. We use dark-field microscopy with side collecting optics for measurements of the optical properties of the tip. The side view allows us to observe the radiation of the tip and hence to analyze its optical properties at the apex. In addition, the measured Raman signal provides an estimate of the electric field enhancement by the tip. Our simulation protocol consists of two parts: electrostatics and wave analysis. Electrostatic simulations give good qualitative predictions, are very fast and therefore conducive to multiparametric optimization. Full wave analysis is needed to evaluate the dephasing effects and far-field signals. The Finite Element Method is used for all simulations. Various tip designs with the field enhancement ranging from ~ 50 to over 250 (depending on various parameters), with the commensurate enhancement of the Raman signal by ~ 454 (for gold coating) and ~ 2704 (for silver coating), are presented and analyzed.© (2006) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.

The local electric field enhancement in the vicinity of a metal-coated or metal tip is a significant factor in the performance of apertureless near-field optical microscopy and spectroscopy techniques. Enhancement, which is related to the generation of localized surface plasmons in the metal tip, can be maximized when the plasmons resonate at the probing wavelength. Thus the resonance frequencies of the tip apex are crucial to near-field optics. However, it remains a challenge to measure the optical properties of the apex of a tip with a radius much smaller than the wavelength of light. A dark-field scattering spectroscopy method is presented in combination with a side-illumination nano-Raman spectrometer to experimentally determine the optical properties of the tip. The dependence of the optical resonance on the metal deposited is shown for silver- and gold-coated tungsten tips as well as gold-coated silicon nitride tips. The enhancement for Si using gold-coated silicon nitride tips is somewhat larger for a wavelength of 647 nm than for a wavelength of 514.5 nm. The former is closer to the plasmon resonance observed for this tip at ~680 nm.

Tip-enhanced Raman spectroscopy (TERS) is emerging as a promising spectroscopic tool fo r nanoscale characterization of chemical composition, structure, stresses and conformational states. However, its widespread application requires optimization of the technique to reproduci bly achieve sufficiently high contrast be tween near-field and far-field signals. We present a TERS spectrometer, based on side illumination geometry, which demonstrates reproducible enhancements of the Raman signal of the order of 10 3 -10 4 for a variety of molecular, polymeric and semi-conducting samples using both silver- and gold-coated tips. We estimate the localization of the Raman signal enhancement to be ~20 nm. For thick samples, the contrast is limited by a strong far-field signal (from the laser illuminated spot) that overpowers the near-field signal (enhanced in the vicinity of the tip). Optimizing the polarization geometry and the incident angle, we have achieved a contrast between near-field and far-field signal of 12 times on (100) Si – a level that makes this technique attractive for characterization of silicon nanostructures. Keywords: Tip-enhanced Raman spectroscopy (TERS), side- illumination geometry, contrast, (100) silicon, polarization of light.