Nanometer scale polarimetry studies using a near-field scanning optical microscope

We describe a new technique that incorporates polarization modulation into near-field scanning optical microscopy (NSOM) for nanometer scale polarimetry studies. By using this technique, we can quantitatively measure the optical anisotropy of materials with both the high sensitivity of dynamic polarimetry and the high spatial resolution of NSOM. The magnitude and relative orientation of linear birefringence or linear dichroism are obtained simultaneously. To demonstrate the sensitivity and resolution of the microscope, we map out stress-induced birefringence associated with submicrometer defects at the fusion boundaries of SrTiO3 bicrystals. Features as small as 150 nm were imaged with a retardance sensitivity of approximately 3 x 10(-3) rad.     

Stress characterization of Si by near-field Raman microscope using resonant scattering

We have developed a tapping-mode scanning near-field optical Raman microscope (SNORM) with a caved and pyramidical probe, using resonant Raman scattering, and have measured the stress distribution of Si. The peak frequency shifts to a lower frequency by 0-0.5 cm(-1) in the area covered by silicon dioxide, whereas it shifts to a higher frequency by 0-0.3 cm(-1) in the area uncovered by silicon dioxide, showing that the areas covered and uncovered by silicon dioxide are under tensile and compressive stresses, respectively. It has been found that compressive stresses of about 0.69 GPa/cm2 are concentrated on the corner of the area uncovered by silicon dioxide. The comparison of stress distributions measured with and without the cantilever shows that the SNORM we developed has a spatial resolution of at least less than 250 nm.     

Surface-enhanced Raman spectroscopy for bacterial discrimination utilizing a scanning electron microscope with a Raman spectroscopy interface

Surface-enhanced Raman scattering (SERS) utilizing colloidal silver has already been shown to provide a rapid means of generating "whole-organism fingerprints" for use in bacterial identification and discrimination. However, one of the main drawbacks of the technique for the analysis of microbiological samples with optical Raman microspectroscopy has been the inability to acquire pre-emptively a region of the sample matrix where both the SERS substrate and biomass are both present. In this study, we introduce a Raman interface for scanning electron microscopy (SEM) and demonstrate the application of this technology to the reproducible and targeted collection of bacterial SERS spectra. In secondary electron mode, the SEM images clearly reveal regions of the sample matrix where the sodium borohydride-reduced silver colloidal particles are present, Stokes spectra collected from these regions are rich in vibrational bands, whereas spectra taken from other areas of the sample elicit a strong fluorescence response. Replicate SERS spectra were collected from two bacterial strains and show excellent reproducibility both by visual inspection and as demonstrated by principal components analysis on the whole SERS spectra.     

Observation of nanostructure by scanning near-field optical microscope with small sphere probe

Step and terrace structure has been observed in an area of 1 μm×1 μm on the cleaved surface of KCl-KBr solid-solution single crystal by scanning near-field optical microscope (SNOM) with a small sphere probe of 500 nm diameter. Lateral spatial resolution of the SNOM system was estimated to be 20 nm from the observation of step width and the scanning-step interval. Vertical spatial resolution was estimated to be 5-2 nm from the observation of step height and noise level of photomultiplier tube (PMT). With applying a dielectric dipole radiation model to the probe surface, the reason why such a high spatial resolution was obtained in spite of the 500 nm sphere probe, was understood as the effect of the near-field term appeared in the radiation field equations.     

Image resolution in reflection scanning near-field optical microscopy using shear-force feedback: characterization with a spline and Fourier spectrum

Scanning near-field optical microscopes (SNOM's) actually lead to nanometric lateral resolution. A combination with shear-force feedback is sometimes used to keep the SNOM tip at a constant force from the sample. However, resolutions in shear-force and optical data are different. An estimation of both resolutions is important for characterizing the capabilities of such systems. The basic principle of the measurement is to compare a spline-fitted logarithm of the power spectra calculated with the optical image with that of the shear force image in which resolution is determined a priori. Quantitative results are given in the case of periodic or untested sample and simulated data. Moreover the accuracy and the stability of the method are discussed.     

Detection of DNA-hybridization using a near-field scanning microwave microscope

A near-field scanning microwave microscope (NSMM) is used to detect sequence-specific hybridization between surface-immobilized and free DNA single strands. Hybridization between target (free) and capture (immobilized) sequences leads to changes in the reflection coefficient (S11) which are measured by the NSMM. These changes are caused by hybridization-induced modification of the dielectric constant profile of the DNA film. NSMM instrumentation does not require labeling of target sequences with fluorophores or other tagging groups. The physical basis of reflection coefficient changes underpinning the NSMM approach is discussed.     

Subsurface Raman spectroscopy and mapping using a globally illuminated non-confocal fiber-optic array probe in the presence of Raman photon migration

We report the use of a fiber-optic probe with global illumination and an array of 50 collection fibers (PhAT probe, Kaiser Optical Systems, Inc.) to obtain Raman spectra and 50 spatial element maps of polymers through overlayers of other polymers that are highly scattering. Band target entropy minimization (BTEM) is used to recover the spectra of the subsurface components and generate maps of their distributions. This approach to subsurface mapping is tested with model systems consisting of two or three layers of polyethylene, polytetrafluoroethylene (Teflon), and polyoxymethylene (Delrin) arranged in different geometries. Raman spectra and maps were obtained through overlayer thicknesses of up to 13 mm. Subsurface spatial resolution is achieved because each fiber views an asymmetric distribution of Raman scattered light from surface and subsurface components that depends on the position of the fiber relative to the depth and position of a component and the extent of photon diffusion through the system.     

Improved scanning range for coherent anti-stokes Raman spectroscopy using a tunable optical parametric oscillator

Coherent anti-Stokes Raman spectroscopy (CARS) is a well-known form of nonlinear spectroscopy that has been used for a wide range of specialized quantitative applications. From an analytical chemist's point of view, however, conventional CARS is impractical as a tool for qualitative and quantitative analyses because the scan range is too short to produce complete vibrational spectra. This paper introduces a new technique, synchronously scanned optical parametric oscillator (OPO) CARS, that improves the potential for using nonlinear spectroscopy as an analytical technique in both gas- and condensed-phase samples. First, it uses a broadly tunable OPO to increase the scan range. Second, phase matching problems that limit scans in condensed-phase CARS are reduced by using both the signal and the idler beams in a synchronous scanning manner. Finally, this synchronous scanning method generates an output signal that remains fixed at a single wavelength (single-wavelength detection). Advantages of single-wavelength detection include reduction of stray light, simplicity, and elimination of the need for wavelength calibration of the detection optics. Results are presented on neat and mixed samples in gas and condensed phases.     

Raman spectroscopy as a probe of graphene and carbon nanotubes

Progress in the use of Raman spectroscopy to characterize graphene samples for the number of graphene layers and doping level they contain is briefly reviewed. Comparisons to prior studies on graphites and carbon nanotubes are used for inspiration to define future promising directions for Raman spectroscopy research on few layer graphenes.     

Characterization of self-assembled monolayers by using a near-field microwave scanning microprobe

A near-field microwave scanning microprobe (NSMM) technique has been used to investigate the material properties of n-alkanethiol self-assembled monolayers (SAMs) on a gold (Au) surface. We demonstrate that near-field microwave probing technique can achieve the noncontact detection of the thickness of SAMs by measuring the microwave reflection coefficient S₁₁ at an operating frequency near 5.3 GHz. We also directly image the patterned SAMs by NSMM. The thickness (chain length) of SAMs is determined from the visualized microwave reflection coefficient changes on the Au surface with high sensitivity. This nano-scale measurement of SAMs has a great potential for investigating the surface profile with high sensitivity.     

Evaluation of interfacial shear stress between multi-walled carbon nanotubes and epoxy based on strain distribution measurement using Raman spectroscopy

This study investigated the stress recovery of aligned multi-walled carbon nanotubes (MWCNTs) embedded in epoxy using Raman spectroscopy, and evaluated interfacial shear stress between MWCNTs and epoxy using shear-lag analysis. To this end, ultralong aligned MWCNTs (3.8 mm long) were embedded in epoxy to obtain Raman spectra at multiple points along the MWCNTs. Downshift of the G′-band due to tensile strain was measured from the nanotube end to the center, and the strain distribution of embedded MWCNTs was evaluated successfully. Interfacial shear stress was then estimated by minimizing the error between the shear-lag analysis and measured strain distribution. The maximum interfacial shear stress between the embedded MWCNTs and epoxy was 10.3–24.1 MPa at the failure strain of aligned MWCNT-reinforced epoxy composites (0.46% strain). Furthermore, the interfacial shear stress between an individual MWCNT and epoxy was investigated.     

Determination of the resolution of a multichannel Raman spectrometer using Fourier transform Raman spectra

The resolution of a grating polychromator for Raman spectroscopy has been simulated by measuring spectra on a Fourier transform (FT) Raman spectrometer and selecting the FT of the apodization function so that the instrument line shape function mimics the triangular spectral slit function of the polychromator. To this end, FT-Raman spectra measured with a nominal resolution of 0.5 cm-1 were modified through the application of sinc2 apodization functions of various widths to simulate spectra measured on a polychromator at lower resolution. The success of this approach was validated using the 1085 cm-1 band of calcite. When the modified FT-Raman spectra were compared with spectra measured on a grating polychromator equipped with slits of widths 100 and 150 microns, the resolution of the polychromator was estimated to be 6.3 and 7.8 cm-1, respectively. This conclusion was verified experimentally by measuring the separation of two bands in the Raman spectrum of BaSO4 at approximately 460 cm-1.     

Rapid measurement of the diameter of the electron probe of a scanning electron microscope

A quick method of measuring the diameter of the electron probe of a scanning electron microscope is proposed. The error of the method is 3–4 nm. Translated from Izmeritel'naya Tekhnika, No. 7, pp. 27–28, July, 1996.     

Topographical and chemical microanalysis of surfaces with a scanning probe microscope and laser-induced breakdown spectroscopy

Spatially resolved chemical imaging is achieved by combining a fiber-optic scanning probe microscope with laser-induced breakdown spectroscopy in a single instrument, TOPOLIBS. Elemental composition of surfaces can be mapped and correlated with topographical data. The experiment is conducted in air with minimal sample preparation. In a typical experiment, surface topography is analyzed by scanning a sharp fiber-optic probe across the sample using shear force feedback. The probe is then positioned over a feature of interest and pulsed radiation is delivered to the surface using a nitrogen laser. The pulse vaporizes material from the surface and generates a localized plasma plume. Optical emission from the plume is analyzed with a compact UV/visible spectrometer. Ablation crater size is controlled by the amount of laser power coupled into the probe. Sampling areas with submicrometer dimensions are achieved by using reduced laser power.     

Analysing one isolated single walled carbon nanotube in the near-field domain with selective nanovolume Raman spectroscopy

In this paper, we describe a new method to the selective nanovolume analysing of one isolated single walled carbon nanotube (SWNT). This concept is based on actually available imaging micro-spectrometry systems for working in near-field domain combined with a stigmatic solid immersion lens. This combination of different analytical methods, and modified and configured equipment entitles us to expand the functionality toward a three-dimensional (3D) nanovolume Raman mapping and photoluminescence intensity with a possible discrimination in polarization, as well as photoluminescence decaytime constant mapping with their unique combination. Subsequently, selective spectra can be acquired from the same location on the samples. By spectrally selecting a SWNT, we registered the spatial distribution of the emitted photons in x, y, z vectors to determine the position of a SWNT in the near-field domain. For the SWNTs that are localized with an accuracy better than 18 nm in the x, y and <1 nm in the z directions, we demonstrate an analytical sensitivity close to a single nanotube with unity throughput. This near-field capability is applied to resolve local variations unambiguously in the Raman spectrum along one single SWNT. Finally, in this paper, we report what we believe to be the first evidence of Raman mapping and 3D real optical imaging of carbon nanotubes with near-field resolution.     

Readout characteristics of a near-field optical probe as a data-storage readout device: submicrometer scan height and resolution

A photodiode-embedded near-field scanning microscope cantilever (photocantilever) was used to scan in a noncontact, constant-height mode at a range common in hard disk drives to examine its readout capabilities when mounted on a flying-slider head. The intensity ratios of spatial frequencies that compose the obtained near-field image were analyzed by use of the fast Fourier transform. A simplified model was developed as a guiding principle for estimating the readout characteristics of the near-field optical probe in the above-proximity scan-height range.     

Fabrication and characterization of a silicon cantilever probe with an integrated quartz-glass (fused-silica) tip for scanning near-field optical microscopy

A cantilever-based probe is introduced for use in scanning near-field optical microscopy (SNOM) combined with scanning atomic-force microscopy (AFM). The probes consist of silicon cantilevers with integrated 25-mum-high fused-silica tips. The probes are batch fabricated by microfabrication technology. Transmission electron microscopy reveals that the transparent quartz tips are completely covered with an opaque aluminum layer before the SNOM measurement. Static and dynamic AFM imaging was performed. SNOM imaging in transmission mode of single fluorescent molecules shows an optical resolution better than 32 nm.     

Surface and bulk stress/strain measurements in composite laminates with a fibre-optic Raman probe

Fibre stress/strain measurements in unidirectional, as well as, multidirectional aramid/epoxy composites have been conducted with the use of a laser Raman microprobe. The composite was incrementally loaded in tension while Raman measurements were taken. Fibre-optic probes sandwiched between adjacent laminae were employed for channelling the laser excitation light to a specified location within the bulk of the composite. The direction of the fibre-optic was either perpendicular or parallel to the reinforcing fibres. For comparison purposes, the same fibre-optic probe was used to scan the surface of the laminates. The perpendicular configuration was found to reduce the tensile strength of the as-received composite coupon by 10% whereas the parallel second configuration had no effect. In the unidirectional coupons the stress or strain in the principal fibre direction could be measured prior to loading and at every increment of applied tensile load up to fracture. The take-up of fibre strain for both bulk and surface set of measurements was identical with that obtained from the attached electrical resistance strain gauges. In the case of multidirectional coupons the stress or strain in the principal direction could be measured within successive plies situated at angles θ to the loading direction. The results for the 0° plies were in good agreement with those obtained by conventional laminate analysis whereas small deviations from linearity were observed in the angle plies. The proposed methodology paves the way for simultaneous in-service stress/strain measurements on the reinforcing fibres situated on the surface or within the bulk of a composite laminate.     

Imperfection measurement of cylinders using automated scanning with a laser displacement meter

Geometric imperfections, commonly in the form of depressions at the circumferential welds, are present in most metal silo structures and can greatly reduce the structure's buckling strength. These imperfections sure close to axisymmetric in form. This paper describes the measurement system which was developed for an experimental study of this phenomena. Computer controlled steppennotors for both Hie circumferential and longitudinal travel of the measurement carriage provided a precise and repeatable traverse of the specimen. A laser displacement meter, which is capable of high speed, non-contact measurement and has a resolution of 0.5 microns, was controlled synchronously with the steppennotors to provide a very accurate three-dimensional measurement system. Both the initial geometrically imperfect shape and the progressive growth of deformations during loading were accurately measured.     

Raman imaging of carious lesions using a hollow optical fiber probe

Raman spectroscopy using a hollow optical fiber probe with a glass ball lens at the distal end is proposed for detection of early caries lesions. Raman spectroscopy on carious lesions of extracted teeth showed that the probe enables measurement with a high signal-to-noise ratio when combined with a ball lens with a high refractive index. The proposed probe and lens combination detects changes in Raman spectra caused by morphological differences between sound and carious enamel. We also obtained a high-contrast image of an early carious lesion by scanning the tooth surface with the probe.