M. Lamy de la Chapelle

Characterization of singlewalled carbon nanotubes-PMMA composites

Thin films of poly(methyl methacrylate)-singlewalled nanotubes (PMMA-SWNTs) composite were produced by spin coating using different nanotubes concentrations. Characterization of these new materials was performed by scanning electron microscopy (SEM) and Raman spectroscopy in order to obtain information on the possible interactions between these two materials and especially, on the modifications of the nanotubes and their organization. It is found that in the composite films, the distance between the nanotubes in bundles increases because of the intercalation of polymer. For low nanotube concentrations, amorphous carbon is dispersed in the polymer matrix giving more uniform thin films.

Optimization of SERS-active substrates for near-field Raman spectroscopy

As a first step towards near-field Raman, we chose to study surface enhanced Raman scattering (SERS)-active substrates to cope with the weakness of Raman scattering (small cross-section and low concentration). We concentrated our work on localized surface plasmon (LSP) since they turned out to play a great part in SERS and we put forward the relation between LSP resonance and Raman enhancement. Roughness of our samples is controlled either by annealing process or electron-beam lithography (EBL); this latter technique proved to best suit to our study. Substrates are characterized by extinction spectroscopy which determines the LSP resonance and then Raman spectrum of a probe molecule, trans-1,2-bis(4-pyridyl)ethylene (BPE) is recorded. We show that maximum of enhancement is obtained when the LSP resonance is red-shifted (50 nm) compared to the excitation laser line (632.8 nm).

Raman characterization of singlewalled carbon nanotubes and PMMA-nanotubes composites

The Raman spectroscopy have allowed us to perform studies on singlewalled nanotubes (SWNTs) produced by following methods: electric arc, laser ablation and solar energy. As this characterization method provides a great deal of informations, we will present a comparison between the nanotubes produced by all these processes and the influence of some synthesis parameters. By using spin casting, we have produced thin films of PMMA-SWNTs for different concentrations. Then, we have characterized these new materials by Raman spectroscopy. The aim of these investigations is to get information on the possible interactions between these two materials. In particular, we have studied the evolution of the composites films spectra as a function of the nanotubes concentration in the polymer.

Light depolarization induced by metallic tips in apertureless near-field optical microscopy and tip-enhanced Raman spectroscopy

We have investigated the depolarization effects of light scattered by sharp tips used for apertureless near-field optical microscopy. Dielectric and metal coated tips have been investigated and depolarization factors between 5 and 30% have been measured, changing as a function of the incident light polarization and of the tip shape. The experimental results are in good agreement with theoretical calculations performed by the finite element method, giving a near-field depolarization factor close to 10%. The effect of depolarization has been investigated in polarized tip-enhanced Raman spectroscopy (TERS) experiments; the depolarization gives rise to forbidden Raman modes in Si crystals.

Resonances of individual lithographic gold nanowires in the infrared

With infrared spectroscopic microscopy using synchrotron radiation, we systematically studied resonant light scattering from electron-beam lithographically produced gold nanowires (nanostripes) with diameters in the 100 nm range and with various lengths below 1 to about 2.5 μm. Similar to electrochemically grown cylindrical wires of high crystalline quality, clear antennalike plasmon resonances were observed for these stripelike and less-perfect wires. The resonance wavelength shifts with length as theoretically predicted for cylindrical gold antennas in the optical range. Surprisingly, also the extinction cross section of the nanostripes is equal to that measured for highly crystalline cylinders.

Defect-induced activation of symmetry forbidden infrared resonances in individual metallic nanorods

We report on the observation of second-order infrared (IR) plasmon resonances in lithographically prepared gold nanorods investigated by means of far-field microscopic IR spectroscopy. In addition to the fundamental antennalike mode, even and odd higher order resonances are observed under normal incidence of light. The activation of even-order modes under normal incidence is surprising since even orders are dipole-forbidden because of their centrosymmetric charge density oscillation. Performing atomic force microscopy and calculations with the boundary element method, we determine that excitation of even modes is enabled by symmetry breaking by structural deviations of the rods from an ideal, straight shape.

Detection in near-field domain of biomolecules adsorbed on a single metallic nanoparticle

In this paper, we study the performances of nanosensors based on Localized Surface Plasmon Resonance in the context of biological sensing. We demonstrate the sensitivity and the selectivity of our designed nanosensors by studying the influence of the concentration of Streptavidin on the shift of Localized Surface Plasmon Resonance wavelength. In addition, to study the detection of biomolecules on a single Au nanoparticle, we used a Scanning Near‐field Optical Microscope. These results represent new steps for applications in biological research and medical diagnostics.

Optical properties of metal nanoparticles as probed by photoemission electron microscopy

Interaction of light with metallic nanostructures exhibit resonances specific to eigenmodes of collective electron motion known as plasmon modes. Both these resonances and effects of electromagnetic singularities lead to local field enhancement. Photoemission electron microscopy (PEEM) was recently used to image the electrons photoemitted from these local effects. Here we report on a full PEEM spectral study of localized surface plasmons excited on nanoparticles. In particular, we show strong spectral similarities between the PEEM signal and optical extinction as a function of the incident wavelength, establishing the photoemission microscopy as a valuable tool for investigating the optical properties of metal nanoparticles.

Error signal artifact in apertureless scanning near-field optical microscopy

Apertureless scanning near-field optical microscopy is a method for obtaining subwavelength optical images of nanostructures. However, great care must be taken to avoid artifactual images. We report on one artifact related to the error signal in cantilever vibration amplitude when operating in tapping mode atomic force microscopy. The artifact is described experimentally and modeled by electromagnetic calculations based on the finite element method. We report specific steps to identify and avoid this artifact with experimental results on gold nanostructures. It is suggested that future apertureless scanning near-field optical microscopy studies verify that optical image does not correlate with error signal.

Effect of temperature on carbon nanotube diameter and bundle arrangement: Microscopic and macroscopic analysis

The diameter distribution of the nanotubes produced by electric-arc discharge are measured using Raman spectroscopy at various wavelengths. These measurements agree with the results provided by two other techniques: high-resolution transmission electron microscopy and x-ray diffraction. The mean tube diameter shifts more than 0.1 nm with the increase of argon in the inert atmosphere. Some argon concentrations favored the synthesis of metallic tubes with specific diameters. Furthermore, the background gas influences the macroscopic characteristics of nanotube yield and bundle size, as determined by Brunauer–Emmett–Teller surface area measurements and x-ray diffraction. The information collected on nanotube diameter and arrangement is correlated with temperatures calculated using a numerical model of the plasma generated between the two electrodes. Indeed, plasma temperature control during the production process is achieved using argon–helium mixtures as buffer gases. The variation of the gas mixture from p...