Viscosity dependence of electrochemical etching for gold tip fabrication

We suggest an electrochemical etching method with viscous etchant to enhance the sharpness of tip of scanning probe microscope. The viscosity of the etchant mixed with HCl solution and glycerol was used as a control parameter in addition to the voltage applied to the tip. In order to improve the sharpness of the tip, a nano-scale meniscus formed between the end of the tip and the liquid level was used. The shapes, aspect ratios, and radii of tips were measured depending on the concentration of the etchant. It was found that the tip etched with the mixed liquid with glycerol was sharper than the tip with the pure HCl solution. This can be explained by the fact that the meniscus formed by viscous liquid is maintained with a thinner diameter and causes final etching until the meniscus bridge is ruptured.     

Towards chemical analysis of nanostructures in biofilms II: tip-enhanced Raman spectroscopy of alginates

This study examines the feasibility of using tip-enhanced Raman spectroscopy (TERS) for label-free chemical characterization of nanostructures in biological systems. For this purpose, a well-defined model system consisting of calcium alginate fibers is studied. In a companion paper, calcium alginate fibers and their network structures were shown to be a good model for the extracellular polysaccharides of biofilms at the nanoscale. TERS analysis of biological macromolecules, such as alginates, is complicated by heterogeneity in their sequence, molecular weight, and conformations, their small Raman cross-section, and the large number of functional groups, which can chemically interact with the silver surface of the tip and cause significant band shifts. Due to these effects, Raman frequencies in TERS spectra of biopolymers do not necessarily resemble band positions in the normal Raman spectrum of the bulk material, as is the case for less complex samples (e.g., dye molecules) studied so far. Additionally, analyte decomposition due to laser heating can have a significant influence, and carbon contamination signals can sometimes even overwhelm the weak analyte signals. Based on the investigation of alginates, strategies for spectra correction, choice of appropriate reference samples, and data interpretation are presented. With this approach, characteristic frequency ranges and specific marker bands can be found for biological macromolecules that can be employed for their identification in complex environments. Figure TERS spectrum of a calcium alginate fiber bundle     

High-Resolution Tip-Enhanced Raman Mapping

Tip-enhanced Raman mapping (TERM) can be used to obtain chemical analysis of a sample with a topographical resolution down to 15 nm. A short review of this technique is given. Among other samples (e.g. carbon nanotubes and graphene), we recently measured a high resolution tip-enhanced Raman map of a polymer for the first time. Using TERM, the phase separation behaviour of a polymer blend (PMMA/SAN) was monitored. In the early, incomplete state of phase separation an interface width of ∼200 nm was measured. A spatial resolution in the tens of nm range could be achieved.     

Nanoprobes for intracellular and single cell surface‐enhanced Raman spectroscopy (SERS)

Surface‐enhanced Raman spectroscopy (SERS) is a promising and powerful label free technique for high resolution analysis of single cells. For intracellular analysis, there is a need for SERS‐active nanoprobes that are minimally invasive to cells, do not affect cell viability, and provide reproducible signals. This work reviews the state‐of‐the‐art tools currently available for intracellular SERS. Various types of SERS probes are considered, including colloidal gold and silver nanoparticles, metallized optical fibers, and tip‐enhanced Raman probes. We also discuss recently developed SERS‐active nanopipettes implemented on the basis of pulled glass microcapillaries. Finally, the critical aspects of selecting an optimal SERS nanoprobe for single‐cell analysis depending on a particular application are summarized. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and attachment of silver nanowires on atomic force microscopy cantilevers for tip‐enhanced Raman spectroscopy

Surface‐enhanced Raman spectroscopy is based on the absorption of light by nanometer‐sized metal particles, resulting in large enhancement of the Raman signal. By replacing the metal particles by a metallic nanotip, the enhancement can be localized. The resulting tip‐enhanced Raman spectroscopy is capable of measuring Raman spectra with high spatial resolution, effectively overcoming the diffraction limit. A successful tip‐enhanced Raman spectroscopy experiment depends heavily on the ability to fabricate tips of a definite metal with the appropriate shape and size, which is still a challenging process. We have prepared silver nanowires with a diameter of 200–300 nm by templated electrochemical deposition and attached them onto atomic force microscope cantilevers by focused electron beam induced deposition. We found that they produce a reproducible enhancement of the Raman signal intensity. Other metals and smaller nanostructures might also be produced, suggesting an interesting development potential for these novel nanoprobes. Copyright © 2011 John Wiley & Sons, Ltd.     

A matter of scale: from far‐field microscopy to near‐field nanoscopy

Vibrational spectroscopy is a powerful analytical tool which provides chemical information about a sample without a priori knowledge. By combining vibrational spectroscopy with different microscopic techniques, scientists can visualize and characterize the chemical composition of a sample on length scales which cover many orders of magnitude; from far‐field radiation used in microwave astronomy and Fourier transform infrared microscopy, to near‐field scattering used in tip‐enhanced Raman spectroscopy and scanning near‐field optical or infrared microscopy. Here, various modern chemical mapping techniques are reviewed and their advantages and disadvantages are discussed. Also, a basic theoretical background is provided for each technique along with several illustrative examples.     

High Resolution Tip Enhanced Raman Mapping on Polymer Thin Films

Advanced tip enhanced Raman mapping (TERM) was applied to high resolution chemical identification on nanoscale. Thin poly(methyl methacrylate)/poly(styrene acrylonitrile) (SAN28/PMMA) blend films were measured at different stages of phase separation. New insights into the phase evolution behavior of the thin films were obtained, when the TERM images were compared. An unexpected morphology transition was observed after a few minutes annealing at 250 °C. No surface enrichment of PMMA was observed, differing from the previous reports on a similar well-studied system of SAN33/PMMA. The glass transition temperature, the surface and interfacial tension were found to be the main factors responsible for the phase evolution behavior of SAN28/PMMA films.     

Tip‐enhanced Raman spectroscopy using single‐crystalline Ag nanowire as tip

We report the surface‐enhanced Raman scattering (SERS) effect from the apex of single‐crystalline Ag nanowires (NWs). We also fabricated tip‐enhanced Raman spectroscopy (TERS) tips by attaching individual Ag NWs to W wires by using the alternating current dielectrophoresis (AC‐DEP) method. The single‐crystalline Ag NW tips could overcome many of the shortcomings of conventional TERS tips. Most importantly, the results obtained from TERS using single‐crystalline metal NWs are very reproducible, and the tips are also reusable. This development represents a significant progress in making TERS a reliable optical characterization technique with nanometer spatial resolution. Copyright © 2010 John Wiley & Sons, Ltd.