Spatially and angularly resolved cathodoluminescence study of single ZnO nanorods

Single ZnO nanorods were studied with cathodoluminescence at high spatial and angular resolution. A newly developed luminescence detector consisting a fiber probe controlled by a nano-manipulator is attached to a scanning electron microscope to carry out the cathodoluminescence measurements. Excitonic emission from the sidewalls and redshifted near band edge emission guided along the nanorod axis are observed as the fiber probe axis is aligned to be perpendicular and parallel to the nanorod axis, respectively, demonstrating the angular resolving power of the experimental setup and waveguiding behavior of the nanorods. High spatial resolution cathodoluminescence measurement shows that the near band edge emission can propagate parallel and perpendicular to the nanorod axis and an increased propagation distance results in more redshift of the guided luminescence. In addition, the high spatial resolution and temperature dependent cathodoluminescence measurements demonstrate the important role of free exciton-longitudinal optical phonon interaction in the waveguiding behavior and the propagation of the near band edge emission in ZnO nanorods.     

The fabrication and optical properties of Nd3+ in silica-based optical fibres

We discuss the fabrication and optical properties of Nd³⁺-doped silica-based optical fibres as a function of core glass composition. The absorption and fluorescence spectra are shown to be very dependent on P₂O₅ concentration. This has resulted in multi-component host glass type optical behaviour from silica-based fibres.     

Spatially resolved analysis of small particles by confocal Raman microscopy: depth profiling and optical trapping

Raman microscopy is a powerful method to provide spatially resolved information about the chemical composition of materials. With confocal collection optics, the method is well suited to the analysis of small particles, either resting on a surface or optically trapped at a laser focus, where the confocal collection volume optimizes the signal from the particle. In this work, the sensitivity and spatial selectivity of detecting Raman scattering from single particles was determined as a function of particle size. An inverted confocal Raman microscope was used to acquire spectra of individual surface-bound and optically trapped polystyrene particles with sizes ranging between 200 nm and 10 microm. The particles are in contact with aqueous solution containing perchlorate ion that served as a solution-phase Raman-active probe to detect interferences from the surrounding medium. The collection volume is scanned through single particles that are attached to the surface of the coverslip, and the sensitivity and selectivity of detection are measured versus particle size. The results compare favorably with a theoretical analysis of the excitation profile and confocal collection efficiency integrated over the volumes of the spherical particles and the surrounding solution. This analysis was also applied to the detection of particles that are optically trapped and levitated above the surface of the coverslip. The results are consistent with the optical trapping of particles at or near the excitation beam focus, which optimizes excitation and selective collection of Raman scattering from the particle.     

Spatially resolved luminescence properties of ZnO tetrapods

ZnO tetrapods were prepared by Zn-vapour deposition at 740 °C in Argon and subsequent oxidation in air for 1–30 min. The photoluminescence (PL) and cathodoluminescence (CL) spectra were measured from ZnO particles collected at various distances from the Zn source representing decreasing dimensions. The ZnO tetrapods showed a green emission centred at 516 nm (2.40 eV) band and the exciton emission at 387 nm (3.20 eV). The measured data suggested that the green emission is strongly increased for particle sizes below 500 nm, whereas the exciton emission is dominant for particle size larger than 500 nm. Spatially resolved CL-measurement on individual tetrapod legs showed, that the green emission increases with decreasing ZnO leg diameter. To our knowledge, the local CL spectroscopic measurements were correlated with the dimensions of the individual ZnO tetrapods for the first time.     

Spatially resolved Raman spectroscopy of single- and few-layer graphene

We present Raman spectroscopy measurements on single- and few-layer graphene flakes. By using a scanning confocal approach, we collect spectral data with spatial resolution, which allows us to directly compare Raman images with scanning force micrographs. Single-layer graphene can be distinguished from double- and few-layer by the width of the D' line: the single peak for single-layer graphene splits into different peaks for the double-layer. These findings are explained using the double-resonant Raman model based on ab initio calculations of the electronic structure and of the phonon dispersion. We investigate the D line intensity and find no defects within the flake. A finite D line response originating from the edges can be attributed either to defects or to the breakdown of translational symmetry.     

Plasmonic modes of annular nanoresonators imaged by spectrally resolved cathodoluminescence

We report the observation of plasmonic modes of annular resonators in nanofabricated Ag and Au surfaces that are imaged by spectrally resolved cathodoluminescence. A highly focused 30 keV electron beam is used to excite localized surface plasmons that couple to collective resonant modes of the nanoresonators. We demonstrate unprecedented resolution of plasmonic mode excitation and by combining these observations with full-field simulations find that cathodoluminescence in plasmonic nanostructures is most efficiently excited at positions corresponding to antinodes in the modal electric field intensity.     

Spatially resolved photoluminescence study of single ZnO tetrapods

ZnO tetrapods and nanowires were fabricated by a simple method of thermal evaporation of pure Zn powder in the air. These nanostructures, formed in different temperature regions of the same apparatus, displayed distinct photoluminescence (PL) characteristics. Spatially resolved PL measurements on legs of individual tetrapods show that the green luminescence (GL) decreases with decreasing leg diameter, and there was no detectable GL from nanowires grown simultaneously. These PL properties suggest that the green luminescence may not come from surface states, but rather from bulk defects.     

Spatially resolved electronic and vibronic properties of single diamondoid molecules

Diamondoids are a unique form of carbon nanostructure best described as hydrogen-terminated diamond molecules. Their diamond-cage structures and tetrahedral sp3 hybrid bonding create new possibilities for tuning electronic bandgaps, optical properties, thermal transport and mechanical strength at the nanoscale. The recently discovered higher diamondoids have thus generated much excitement in regards to their potential versatility as nanoscale devices. Despite this excitement, however, very little is known about the properties of isolated diamondoids on metal surfaces, a very relevant system for molecular electronics. For example, it is unclear how the microscopic characteristics of molecular orbitals and local electron-vibrational coupling affect electron conduction, emission and energy transfer in the diamondoids. Here, we report the first single-molecule study of tetramantane diamondoids on Au(111) using scanning tunnelling microscopy and spectroscopy. We find that the diamondoid electronic structure and electron-vibrational coupling exhibit unique and unexpected spatial correlations characterized by pronounced nodal structure across the molecular surfaces. Ab initio pseudopotential density functional calculations reveal that much of the observed electronic and vibronic properties of diamondoids are determined by surface hydrogen terminations, a feature having important implications for designing future diamondoid-based molecular devices.     

Raman microprobe analysis of preforms and optical fibers

The concentration profile of various dopants (germanium, phosphorus, and fluorine) in preforms and optical fibers has been obtained with a Raman microprobe. A 2-microm spatial resolution was achieved. In the case of germanium and phosphorus, the results agree quite well with those obtained with an electron microprobe. Raman spectroscopy easily detects fluorine. From measurements of various F-doped samples, diffusion of fluorine in undoped and doped silica is suggested.     

Spatially resolved absolute diffuse reflectance measurements for noninvasive determination of the optical scattering and absorption coefficients of biological tissue

The absorption and transport scattering coefficients of biological tissues determine the radial dependence of the diffuse reflectance that is due to a point source. A system is described for making remote measurements of spatially resolved absolute diffuse reflectance and hence noninvasive, noncontact estimates of the tissue optical properties. The system incorporated a laser source and a CCD camera. Deflection of the incident beam into the camera allowed characterization of the source for absolute reflectance measurements. It is shown that an often used solution of the diffusion equation cannot be applied for these measurements. Instead, a neural network, trained on the results of Monte Carlo simulations, was used to estimate the absorption and scattering coefficients from the reflectance data. Tests on tissue-simulating phantoms with transport scattering coefficients between 0.5 and 2.0 mm(-1) and absorption coefficients between 0.002 and 0.1 mm(-1) showed the rms errors of this technique to be 2.6% for the transport scattering coefficient and 14% for the absorption coefficients. The optical properties of bovine muscle, adipose, and liver tissue, as well as chicken muscle (breast), were also measured ex vivo at 633 and 751 nm. For muscle tissue it was found that the Monte Carlo simulation did not agree with experimental measurements of reflectance at distances less than 2 mm from the incident beam.     

Spatially resolved investigations of the excitonic luminescence in GaN

We performed spatially-resolved investigations on thick GaN layers using cathodoluminescence and micro-Raman experiments. Our measurements reveal that the peak position of the excitonic transition lines strongly depends on the distance to the substrate interface. The luminescence is shifted continuously to lower energies with decreasing distance, however, a strong blue shift occurs directly at the interface. We correlate these effects with bandgap renormalization and band filling effects induced by a strong gradient of free-carrier concentration in addition to a strain gradient found by our Raman experiments.     

Spatially resolved phase imaging of a programmable liquid-crystal grating

Phase imaging is used to compare near-field measurements with the corresponding far-field intensity distribution. A liquid-crystal device serves as a phase object that can be programmed as a variable grating. Real-time phase visualization then provides an avenue for direct optimization of complex phase gratings.     

Spatially resolved photoelectric performance of axial GaAs nanowire pn-diodes

The spatially resolved photoelectric response of a single axial GaAs nanowire pn-diode has been investigated with scanning photocurrent and Kelvin probe force microscopy. Optical generation of carriers at the pn-junction has been shown to dominate the photoresponse. A photocurrent of 88 pA, an open circuit voltage of 0.56 V and a fill factor of 69% were obtained under AM 1.5 G conditions. The photocurrent followed the increasing photoexcitation with 0.24 A/W up to an illumination density of at least 90 W/cm², which is important for potential applications in concentrator solar cells.     

Spatially resolved electrochemiluminescence on an array of electrode tips

An array of electrode tips with 6-microm center-to-center spacing, fabricated through chemical etching of an optical fiber bundle, and coated with gold, was used for initiating electrochemiluminescence (ECL) in an aqueous solution of Ru(bpy)3(2+) and tri-n-propylamine (TPrA). ECL generated at the tips of the electrodes in the array was detected with a CCD camera and exhibited both high sensitivity and high resolution. In the case in which the ECL signal could not be distinguished from the background, ECL signals could be obtained by pulsing the array and summing multiple CCD images. The behavior of this array was compared to a second array that consisted of individual electrodes insulated with an electrophoretic paint.     

Spatially resolved self-sensing of strain and damage in carbon fiber cement

Spatially resolved self-sensing of strain and damage has been shown in carbon fiber cement under flexure by three-point bending. This involves measurement of the one-dimensional distribution of the DC electrical resistance by the use of surface electrical contacts on the bottom (tension) and top (compression) surfaces. For a span of 290 mm, a spatial resolution of 5 mm has been attained. The bottom surface resistance, which increases reversibly with strain and increases irreversibly with damage, is a more effective indicator of strain and damage (in combination) than the top surface resistance, the oblique resistance or the through-thickness resistance for spatially resolved self-sensing. For sensing without spatial resolution, the oblique resistance is the most effective indicator. For sensing with distinction between strain and damage, the top surface resistance is the most effective indicator.     

Thermal properties of highly birefringent optical fibers and preforms

Temperature cycling of highly birefringent optical fibers and preforms has been used to investigate the thermal properties of bow-tie and elliptically clad structures. The thermal hysteresis of the birefringence is shown to be a direct consequence of the thermal history of the fiber or preform and has been related to volume changes in the stress-producing borosilicate sections. Annealing increases the axial stress as well as the stress anisotropy and hence the birefringence. Increases of up to a factor of 2 in the birefringence on suitable thermal treatment indicate a new method for further improvement of high birefringence fibers. The implications of the results in the design, fabrication, and use of such fibers are discussed.     

Spatially resolved evolution of adhesion properties of large porcelain tiles

The rising number of failures of porcelain tiles, especially in outdoor applications, is to some extent a consequence of the critical combination of applying tiles of large dimensions and the non-porous nature of these tiles. A special setup allows a reproducible application of large-sized tiles (30 × 30 cm). In analogy to outdoor conditions, samples were stored under dry and wet conditions and have been investigated with different physico-chemical approaches. Under dry storage conditions adhesion strength is significantly lower along the periphery of the tiles compared to their centre. This reduction in adhesion performance is mainly caused by shrinkage of the mortar and substrate (～0.1 mm/m). In situ observations through glass tiles indicate that the stresses induced by shrinkage are highest in the rim regions of the tiles. Under wet storage conditions, water percolates into the rim regions of the mortar, which leads to swelling of mortar and substrate, accelerating the delamination process. The findings of this study confirm observations on the construction site, where initial failures are often found at the periphery of large-sized tiles.     

Spatially resolved characterization of cellulose nanocrystal-polypropylene composite by confocal Raman microscopy

Raman spectroscopy was used to analyze cellulose nanocrystal (CNC) -polypropylene (PP) composites and to investigate the spatial distribution of CNCs in extruded composite filaments. Three composites were made from two forms of nanocellulose (CNCs from wood pulp and the nano-scale fraction of microcrystalline cellulose) and two of the three composites investigated used maleated PP as a coupling agent. Raman maps, based on cellulose and PP bands at 1098 and 1460 cm(-1), respectively, obtained at 1 μm spatial resolution showed that the CNCs were aggregated to various degrees in the PP matrix. Of the three composites analyzed, two showed clear existence of phase-separated regions: Raman images with strong PP and absent/weak cellulose or vice versa. For the third composite, the situation was slightly improved but a clear transition interface between the PP-abundant and CNC-abundant regions was observed, indicating that the CNC remained poorly dispersed. The spectroscopic approach to investigating spatial distribution of the composite components was helpful in evaluating CNC dispersion in the composite at the microscopic level, which helped explain the relatively modest reinforcement of PP by the CNCs.