There are needs for both high resolution imaging and high sensitivity detection/analysis of surface chemistry on a
nanometer scale. These needs can be addressed with Raman spectroscopy coupled with schemes that provide
extraordinary enhancement of the Raman signal, namely surface enhanced (SERS) and tip enhanced Raman
spectroscopy (TERS). Advances in applications of high resolution imaging and high sensitivity detection will be
enabled by two specific improvements: increased signal enhancement and increased robustness of the plasmonic
structures needed to achieve enhancement. Robustness and stability are especially important for those plasmonic
structures made of silver that usually provide the best enhancements. Here we focus particularly on TERS, in which a
plasmonic structure is placed on a scanning probe microscope tip in order to achieve high lateral resolution imaging. We
have demonstrated that aluminum oxide protected silver plasmonic structures show significantly increased robustness
against chemical and mechanical degradation when compared to unprotected analogues without loss of enhancement. A
2-3 nm thick coating of aluminum oxide prevents chemical attack of the underlying silver film for three months in a
desiccator, significantly increasing the storage life of current probes. The same protective coating also extends the
scanning life of the probe when the probe is used to image a hard patterned silicon substrate.
High resolution chemical imaging of surfaces can be achieved using Tip Enhanced Raman
Spectroscopy(TERS), an emerging technique that combines scanning probe microscopy with optical spectroscopy and
takes advantage of apertureless near-field optics to obtain lateral resolution dramatically better than that provided by
conventional optics. So far a 20 nm lateral resolution in chemical imaging of a surface has been achieved. The
plasmonic structures on the tip used for imaging could also be used for novel, high sensitivity, local chemical and
biological sensing. However, the silver plasmonic structures suffer from limited lifetimes due to morphological changes
resulting from heating, wear during imaging, and tarnishing.
The lifetimes of silver plasmonic structures on flat surfaces (as model systems) and on silicon nitride TERS tips
have been extended by depositing over the silver an ultrathin (3nm) silicon oxide (SiO<sub>x</sub>) coating. With this thickness
protective coating, the contrast factor for the tip, which is the key parameter controlling one's ability to image with the
tip, is decreased slightly (~10%) initially, but the rate at which the signal enhancement degrades is sharply reduced. The
silver layer on an unprotected tip was mechanically damaged after only three images of a polymer surface, while a silver
layer protected by SiO<sub>x</sub> remained intact after scanning three images.
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 <i>aperture-limited</i> 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 <i>apertureless</i> 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.
Tip-enhanced Raman spectroscopy (TERS) using side illumination is a promising spectroscopic tool for nanoscale characterization of chemical composition, structure, stresses and conformational states of non-transparent samples. Recent progress has shown signal enhancements for a variety of samples, including break-through enhancements of semiconductors. In this work, optimization of the polarization geometry increases contrast between near-field and far-field signals on Si and improves imaging quality. Two-dimensional images of semiconductor nanostructures show reasonable agreement between topographical and TERS images. These recent TERS results using both silver- and gold-coated tips demonstrate localization of the Raman enhancement to within approximately 20 nm of the tip. Also, the enhanced Raman signal of a strained Si layer is separated from an underlying Si substrate, which is encouraging for potential strain distribution analysis of silicon nanostructures.
Tip-enhanced Raman spectroscopy (TERS) is emerging as a promising spectroscopic tool for nanoscale characterization of chemical composition, structure, stresses and conformational states. However, its widespread application requires optimization of the technique to reproducibly achieve sufficiently high contrast between 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<sup>3</sup>-10<sup>4</sup> 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.
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.
The synthesis and characterization of photoactive monolayers is described. Monolayers containing azobenzene were prepared either by direct chemisorption of a trichlorosilane or by covalent attachment to a functionalized self-assembled monolayer (SAM). Preliminary photoisomerization studies show a decrease in wettability upon exposure to ultraviolet light. In addition, a new experimental methodology for measuring protein adsorption to SAMs was developed. Neutron reflectometry measurements show that the protein, Human Serum Albumin (HSA), adsorbs onto both methyl- and ammonium-terminated SAMs. However, more protein was found in the interphase next to the methyl-terminated SAM.