Deep‐UV tip‐enhanced Raman scattering

We report for the first time the tip‐enhancement of resonance Raman scattering using deep ultraviolet (DUV) excitation wavelength. The tip‐enhancement was successfully demonstrated with an aluminum‐coated silicon tip that acts as a plasmonic material in DUV wavelengths. Both the crystal violet and adenine molecules, which were used as test samples, show electronic resonance at the 266‐nm excitation used in the experiments. With results demonstrated here, molecular analysis and imaging with nanoscale spatial resolution in DUV resonance Raman spectroscopy can be realized using the tip‐enhancement effect. Copyright © 2009 John Wiley & Sons, Ltd.     

Frequency shifts of cantilever in AFM

The frequency shift and frequency shift image of cantilever in AFM have been studied by numerical integration of the equation of motion of cantilever for silicon tip with rutile TiO₂(0 0 1) surface in UHV conditions and by the Hamaker summation method for the tip-surface interaction forces. The effects of the excitation frequency at the cantilever base and the equilibrium position of the tip on the frequency shift have been calculated and the results showed the same phenomena as those measured, e.g., the frequency shift increased dramatically or rapidly before the contact point and was then almost level off after the contact point. The effects of scanning speed and the initial closest distance of tip to the contact point have been calculated at different excitation frequencies at the cantilever base and the results showed that proper frequency shift image could be obtained either by noncontact mode at the excitation frequency slightly less than the resonance frequency of free cantilever, or by tapping mode at the excitation frequency a few times smaller than the resonance frequency of free cantilever.     

Surface‐enhanced Raman spectroscopy on novel black silicon‐based nanostructured surfaces

Two different black silicon nanostructured surfaces modified with thin gold layers were tested for analytical signal enhancement with Surface‐Enhanced Raman Spectroscopy (SERS). The relationship between the thicknesses of the gold layers and the analytical signal enhancement was studied. Also, effects of Ti and Ti/Pt adhesion layers underneath the gold layers on the analytical signal enhancement were tested. An enhancement factor of 7.6 × 10⁷ with the excitation laser 785 nm was achieved for the tested analyte, Rhodamine 6G, and non‐resonance SER spectra were recorded in a 5 s acquisition mode. Such an enhancement enables to achieve a detection limit down to 2.4 pg of Rhodamine 6G on a black silicon‐based nanosurface coated with a 400‐nm‐thin layer of gold. Copyright © 2009 John Wiley & Sons, Ltd.     

Gold‐coated zinc oxide nanowire‐based substrate for surface‐enhanced Raman spectroscopy

Zinc oxide nanowires with two distinct morphologies were synthesized on silicon substrates using a simple thermal evaporation and vapor transport method in an oxidizing environment. The as‐synthesized nanowires were coated with gold to allow excitation of surface plasmons over a broad frequency range. SERS studies with near‐IR excitation at 785 nm showed significant enhancement (average enhancement > 10⁶) with excellent reproducibility to detect monolayer concentrations of 4‐methylbenzenethiol (4‐MBT) and 1,2‐benzendithiol (1,2‐BDT) probe molecules. The Raman enhancement showed a strong dependence on the gold film thickness, and the peak enhancement was observed for a ∼40‐nm‐thick film. The Raman enhancement was stronger for randomly oriented nanowires compared to aligned ones suggesting the importance of contributions from the junctions of nanowires. Copyright © 2009 John Wiley & Sons, Ltd.     

SERS active Ag nanoparticles in mesoporous silicon: detection of organic molecules and peptide–antibody assays

Ag nanoparticles synthesized on porous silicon samples were studied and applied as substrates for surface‐enhanced Raman scattering (SERS). The metallic nanostructures prepared by immersion plating were characterized by UV–Vis reflectance spectroscopy and scanning electron microscopy. SERS activity of the substrates was tested using Cyanine dye 1,3,3,1′,3′,3′‐esamethyl‐5,5′‐dimethoxyindodicarbocyanine iodide (Cy5‐OCH₃) as a probe molecule. The Raman spectra obtained for different excitation wavelengths indicate amplifications ascribed to plasmonic resonances with an enhancement factor up to 10⁷. CGIYRLRS peptides were chemisorbed on the Ag nanoparticles with the plasmonic resonance tuned at the excitation energy. Such oligopeptides were used as baits for a specific polyclonal antibody. The overall Raman enhancement allowed to evidence a good selectivity to the target analyte as required by most of the SERS applications on biological assays. Copyright © 2011 John Wiley & Sons, Ltd.     

Effects of sample topography and thermal features in scanning thermal conductivity microscopy

This article analyses the operation of an atomic force microscope whose cantilever, which is heated at its free end, is used to map topography and thermal features across a sample surface. The analysis takes into account the thermal flow along the cantilever, between the cantilever and sample via air, and through the constriction formed at the tip-sample contact area. The thermal flow through the constriction is analysed in terms of Maxwell and Sharvin components as given by Wexler. Examples using silicon tips and samples with a rectangular grid consisting of (a) silicon and silicon oxide features and (b) silicon oxide steps of 100 nm height, show that long tips are more sensitive to the thermal features of the sample while short once are more sensitive to its topography.     

Electrochemical fabrication of silver tips for tip‐enhanced Raman spectroscopy assisted by a machine vision system

Both tip‐enhanced Raman spectroscopy and scanning tunneling microscopy require the use of sharp tips. Electrochemical etching appears to be the most widely used method for preparing tips. To address the over‐etching problem associated with the silver tips by either using voltage or current as a feedback, we developed here an optical method‐based machine vision to achieve a quick cutoff of the circuit once the tip forms. It is a fully automated method with a response time of about 40 ms and is tolerated with any existing electrochemical etching method. We can significantly decrease the time of over‐etching of the silver tip when short rectangular pulses with a duty cycle of 28.6% were used. The mean radius of curvature was ca. 58 nm, as measured from over 50 tips. The capacities of silver tips for high‐resolution scanning tunneling microscopy imaging and high‐sensitivity tip‐enhanced Raman studies have been demonstrated. Copyright © 2016 John Wiley & Sons, Ltd.     

Nanoscale probing of adsorbed species by tip-enhanced Raman spectroscopy

Tip-enhanced Raman spectroscopy (TERS) is based on the optical excitation of localized surface plasmons in the tip-substrate cavity, which provides a large but local field enhancement near the tip apex. We report on TERS with smooth single crystalline surfaces as substrates. The adsorbates were CN- ions at Au(111) and malachite green isothiocyanate (MGITC) molecules at Au(111) and Pt(110) using either Au or Ir tips. The data analysis yields Raman enhancements of about 4 x 10(5) for CN- and up to 10(6) for MGITC at Au(111) with a Au tip, probing an area of less than 100 nm radius.     

Virtual photon scattering at subwavelength sized tips

Silicon AFM tips can profitably be used as optical sensors for near field optical microscopy. In particular they are able to convert evanescent waves (also called virtual photons) into propagating ones which are conveniently guided in the tip and transferred to the air at the back of the cantilever. In this paper it is shown that virtual photons scattered at the tip end are also converted into real ones which are observed in the far field. Contrary to the previous observations of similar conversion at STM metal tips the scattered emission at dielectric silicon tips does not have a dependence with distance of a full exponential decay but rather follows the more complex dependence of the dielectric capture. This observation is consistent with Mie's theory of scattering of real photons by small particles. Experiments are performed with boths andp polarizations showing a regular dependence of the scattered intensity with the incidence angle. The same experiment is also performed with metallized silicon tips showing a metal scattering behaviour. This results can help to achieve a better control of the tip position in the close range of distances in a Photon Scanning Tunneling Microscopy (PSTM) experiment.     

Magnetic contrast from domain walls in BaFe12O19 by tunneling stabilized magnetic force microscopy

The magnetic structure of BaFe₁₂O₁₉ is imaged with a scanning tunneling microscope having a flexible, magnetic tip. We find that Fe thin films evaporated on a silicon tip, integrated with a cantilever, behave as magnetically soft tips. Therefore, we are able to image domain walls with high lateral resolution. A different contrast along the domain wall due to surface magnetic charges is observed. We explain the data using previously established models for wavy domain walls. The obtained images are the first experimental evidence of magnetic charges induced on the wavy domain walls in BaFe₁₂O₁₉.     

Mesoscopic temporary devices: a multiple tip experiment on a silicon surface

A cantilever device with two gold coated silicon tips has been used to create two point contacts on a silicon surface. The lateral distance between the tips is 10 μm. The tips are independently movable in vertical direction and the contact force is defined. While the contacts are closed, a complete set of electrical characteristics of the system is measured. An Ohmic current and a field dependent current are found, so the system behaves like a FET. The measured set of curves was fit with a MESFET model. A weak coupling between the bulk material and the current carried through surface states is found.     

Nanosphere Templated Metallic Grating Assisted Enhanced Fluorescence

In this paper, enhanced fluorescence from a silver film coated nanosphere templated grating is presented. Initially, numerical simulation was performed to determine the plasmon resonance wavelength by varying the thickness of the silver film on top of a monolayer of 400 nm nanospheres. The simulation results are verified experimentally and tested for enhancing fluorescence from fluorescein isothiocyanate whose excitation wavelength closely matches with the plasmon resonance wavelength of the substrate with 100 nm silver film over nanosphere. The 12 times enhancement in the intensity is attributed to the local field enhancement in addition to the excitation of surface plasmon polaritons along the surface.     

Effect of tip mass on frequency response and sensitivity of AFM cantilever in liquid

The effect of tip mass on the frequency response and sensitivity of atomic force microscope (AFM) cantilever in the liquid environment is investigated. For this purpose, using Euler–Bernoulli beam theory and considering tip mass and hydrodynamic functions in a liquid environment, an expression for the resonance frequencies of AFM cantilever in liquid is derived. Then, based on this expression, the effect of the surface contact stiffness on the flexural mode of a rectangular AFM cantilever in fluid is investigated and compared with the case where the AFM cantilever operates in the air. The results show that in contrast with an air environment, the tip mass has no significant impact on the resonance frequency and sensitivity of the AFM cantilever in the liquid. Hence, analysis of AFM behaviour in liquid environment by neglecting the tip mass is logical.     

Study for noise reduction in synchrotron radiation based scanning tunneling microscopy by developing insulator-coat tip

To solve difficulties of instability and inaccuracy in synchrotron radiation based scanning tunneling microscopy, a method to reduce noise was investigated. New insulator-coat tips were developed to shut out electrons coming from a wide area that damage the spatial resolution. By changing the exposed conductive area at the end of the insulator-coat tips, the effect of noise reduction was estimated. The tip with an exposure area of 50 nm in diameter was found to reduce noise effectively. Also a key discriminating condition was found to obtain the local signal, which is based on the modulation of the X-ray-induced tip current caused by excitation of the specific element.     

Surface‐enhanced Raman scattering from gold‐coated germanium oxide nanowires

We utilized bulk‐synthesized nanowires (NWs) of germanium dioxide as nanoscale structures that can be coated with noble metals to allow the excitation of surface plasmons over a broad frequency range. The NWs were synthesized on substrates of silicon using gold‐catalyst‐assisted vapor–liquid–solid (VLS) growth mechanism in a simple quartz tube furnace setup. The resulting NWs have diameters of ∼100–200 nm, with lengths averaging ∼10–40 µm and randomly distributed on the substrate. The NWs are subsequently coated with thin films of gold, which provide a surface‐plasmon‐active surface. Surface‐enhanced Raman scattering (SERS) studies with near‐infrared (NIR) excitation at 785 nm show significant enhancement (average enhancement > 10⁶) with good uniformity to detect submonolayer concentrations of 4‐methylbenzenethiol (4‐MBT), trans‐1,2‐bis(4‐pyridyl)ethylene (BPE), and 1,2‐benzendithiol (1,2‐BDT) probe molecules. We also observed an intense, broad continuum in the Raman spectrum of NWs after metal coating, which tended to diminish with the analyte monolayer formation. Copyright © 2008 John Wiley & Sons, Ltd.     

Effect of shape and interstice on surface enhanced Raman scattering (SERS) of molecules adsorbed on gold nanoparticles in the near‐dipole and quadrupole regions

Surface enhanced Raman scattering (SERS) of adsorbed molecule on colloidal gold nanoparticles of different shapes, namely nanospheres (NSs), nanorods (NRs), and nanoprisms (NPs) as well as the three NPs arrays of different interstice prepared by NS lithography, are studied with incident wavenumbers in the near‐dipole and near‐quadrpole regions of the nanoparticles. In the colloidal gold nanoparticles, the SERS enhancement is the largest for the sharp tip followed by the truncated tip NPs, then the NRs and least enhancement for the NSs. This decreasing order of enhancement occurs although the incident wavenumber was near the dipole resonance of NSs and the quadrupole resonance for the NPs. These varied enhancements are explained in part as due to the binding energies of the nanocrystal facets, but the larger contribution results from the plasmon electromagnetic fields. A parallel finite difference time domain (FDTD) calculations were carried out, which corporate the experimental results and show agreement with ratios of the SERS enhancement for the different shapes. The normalized SERS intensity for NPs of different interstice distances show a sharp rise with the decrease of the interstice distances because of interparticle dipolar and quadrupolar coupling as evidenced also by FDTD calculations. Furthermore, these calculations show that the enhancement is polarization independent for an incident wavelength near quadrupole resonance but polarization dependent for an incident wavelength near the plasmon dipole transition. In the last case, the enhancement is larger by an order of magnitude for a polarization parallel to the NPs bisector than for polarization normal to the bisector with no hot spots for the relatively large interstice dimensions used. Copyright © 2012 John Wiley & Sons, Ltd.     

Detection of biologically active diterpenoic acids by Raman Spectroscopy

Three poorly detectable, biologically active diterpenoic acids, kaurenoic, abietic, and gibberellic acid, were studied by using different modes of Raman spectroscopy. Because of their structural similarities, in the absence of strongly polarizable groups, conventional Raman spectroscopy is not suitable for their unambiguous identification, especially not in solution. We attempted to increase the sensitivity by applying UV‐resonance Raman spectroscopy and surface‐enhanced Raman spectroscopy (SERS) techniques. The UV‐Raman spectra of the three compounds in ethanol/water 50:50 showed only very few enhanced Raman lines. SERS spectra with 514‐nm excitation with Ag colloids were also relatively weak. The best SERS spectra were obtained with 785‐nm excitation on a novel nanostructured substrate, ‘black silicon’ coated with a 400‐nm gold layer. The spectra showed clear differences, and these ‘fingerprints’ would be suitable for the unambiguous identification of these diterpenoic acids. Copyright © 2009 John Wiley & Sons, Ltd.     

Tip-enhanced fluorescence microscopy at 10 nanometer resolution

We demonstrate unambiguously that the field enhancement near the apex of a laser-illuminated silicon tip decays according to a power law that is moderated by a single parameter characterizing the tip sharpness. Oscillating the probe in intermittent contact with a semiconductor nanocrystal strongly modulates the fluorescence excitation rate, providing robust optical contrast and enabling excellent background rejection. Laterally encoded demodulation yields images with <10 nm spatial resolution, consistent with independent measurements of tip sharpness.     

Field emission properties of nano-structured phosphorus-doped diamond

Nano-structured phosphorus-doped diamonds were fabricated for field emitters and their field emission properties were characterized. Two kinds of nano-structures were prepared; tip array structures and whiskers on tip structures. The tips, which have 100 nm radius and 10 μm height, are used in tip array structures; whiskers have tip radii of 5 nm and height of 500 nm. Following nano-structure formation, a reduction of threshold fields is observed compared to non-patterned flat surfaces. This is ascribed to field concentration at the tips. However, at higher electric fields, a saturation of the emission current is observed due to non-negligible bulk resistances in tips and whiskers.