Marc Lamy de la Chapelle

Optical Nanoantennas for Multiband Surface-Enhanced Infrared and Raman Spectroscopy

In this article we show that linear nanoantennas can be used as shared substrates for surface-enhanced Raman and infrared spectroscopy (SERS and SEIRS, respectively). This is done by engineering the plasmonic properties of the nanoantennas, so to make them resonant in both the visible (transversal resonance) and the infrared (longitudinal resonance), and by rotating the excitation field polarization to selectively take advantage of each resonance and achieve SERS and SEIRS on the same nanoantennas. As a proof of concept, we have fabricated gold nanoantennas by electron beam lithography on calcium difluoride (1-2 μm long, 60 nm wide, 60 nm high) that exhibit a transverse plasmonic resonance in the visible (640 nm) and a particularly strong longitudinal dipolar resonance in the infrared (tunable in the 1280-3100 cm(-1) energy range as a function of the length). SERS and SEIRS detection of methylene blue molecules adsorbed on the nanoantennas surface is accomplished, with signal enhancement factors of 5×10(2) for SERS (electromagnetic enhancement) and up to 10(5) for SEIRS. Notably, we find that the field enhancement provided by the transverse resonance is sufficient to achieve SERS from single nanoantennas. Furthermore, we show that by properly tuning the nanoantenna length the signals of a multitude of vibrational modes can be enhanced with SEIRS. This simple concept of plasmonic nanosensor is highly suitable for integration on lab-on-a-chip schemes for label-free chemical and biomolecular identification with optimized performances.

SERS detection of biomolecules using lithographed nanoparticles towards a reproducible SERS biosensor.

In this paper we highlight the accurate spectral detection of bovine serum albumin and ribonuclease-A using a surface-enhanced Raman scattering (SERS) substrate based on gold nanocylinders obtained by electron-beam lithography (EBL). The nanocylinders have diameters from 100 to 180 nm with a gap of 200 nm. We demonstrate that optimizing the size and the shape of the lithographed gold nanocylinders, we can obtain SERS spectra of proteins at low concentration. This SERS study enabled us to estimate high enhancement factors (10(5) for BSA and 10(7) for RNase-A) of important bands in the protein Raman spectrum measured for 1 mM concentration. We demonstrate that, to reach the highest enhancement, it is necessary to optimize the SERS signal and that the main parameter of optimization is the LSPR position. The LSPR have to be suitably located between the laser excitation wavelength, which is 632.8 nm, and the position of the considered Raman band. Our study underlines the efficiency of gold nanocylinder arrays in the spectral detection of proteins.

Diameter control of single-walled carbon nanotubes using argon–helium mixture gases

A method is reported for controlling the diameter of single-walled carbon nanotubes (SWCNTs) during the electric-arc-discharge process. Using argon as inert atmosphere provides smaller diameters as compared with those when pure helium is used. Varying the gas mixture from argon to helium changes the diameter distribution to higher values. A linear fit of the average diameter shows a 0.2 A diam decrease per 10% increase in the argon–helium ratio.

Lithographied nanostructures as nanosensors

Major improvements in fabrication techniques at the nanoscale during the last two decades enable us to exploit and control nanoscale phenomena such as the localized surface plasmons (LSP) provided by metallic nanoparticles (MNP). The large enhancement of the electromagnetic field due to plasmonic effects increases drastically the response of any analyte located close to or adsorbed on MNPs, which opens ways for detection of very low concentration of analytes and sensor miniaturization. However, the efficiency of such nanosensors requires a precise control of the optical properties of the MNPs since it strongly depends on their geometrical properties. Such precision can be reached by nanolithography techniques. The parameters that govern the near field enhancement include the geometrical parameters of the MNPs (size, shape, and gap), the LSP characteristics (near field decay length and resonance position) and the excitation parameters (excitation wavelength and associated electric field polarization). Nanolithography techniques used for surface nanostructuring include optical, focused electron and ion beams, nanoimprint and nanosphere lithographies. Nanosensor fabricated lithographically exploit localized surface plasmon resonance, surface enhanced Raman scattering, and surface enhanced fluorescence.

Soft UV nanoimprint lithography-designed highly sensitive substrates for SERS detection

AbstractWe report on the use of soft UV nanoimprint lithography (UV-NIL) for the development of reproducible, millimeter-sized, and sensitive substrates for SERS detection. The used geometry for plasmonic nanostructures is the cylinder. Gold nanocylinders (GNCs) showed to be very sensitive and specific sensing surfaces. Indeed, we demonstrated that less than 4 ×106 avidin molecules were detected and contributed to the surface-enhanced Raman scattering (SERS) signal. Thus, the soft UV-NIL technique allows to obtain quickly very sensitive substrates for SERS biosensing on surfaces of 1 mm 2.

Biological and chemical gold nanosensors based on localized surface plasmon resonance

In this paper, we discuss the performances of gold nanosensors based on Localized Surface Plasmon Resonance (LSPR) designed by Electron Beam Lithography (EBL) in the context of biological and chemical sensing. We demonstrate the sensitivity of our gold nanosensors by studying the influence of the concentration of 11-mercaptoundecanoic acid (MUA) on the shift of LSPR wavelength. Additionally, to study the selectivity of our nanosensors, the system Biotin/Streptavidin was used to detect very weak concentration of biomolecules. These results represent new steps for applications in chemical research and medical diagnostics.

Nanoshells for photothermal therapy: a Monte-Carlo based numerical study of their design tolerance.

The optimization of the coated metallic nanoparticles and nanoshells is a current challenge for biological applications, especially for cancer photothermal therapy, considering both the continuous improvement of their fabrication and the increasing requirement of efficiency. The efficiency of the coupling between illumination with such nanostructures for burning purposes depends unevenly on their geometrical parameters (radius, thickness of the shell) and material parameters (permittivities which depend on the illumination wavelength). Through a Monte-Carlo method, we propose a numerical study of such nanodevice, to evaluate tolerances (or uncertainty) on these parameters, given a threshold of efficiency, to facilitate the design of nanoparticles. The results could help to focus on the relevant parameters of the engineering process for which the absorbed energy is the most dependant. The Monte-Carlo method confirms that the best burning efficiency are obtained for hollow nanospheres and exhibit the sensitivity of the absorbed electromagnetic energy as a function of each parameter. The proposed method is general and could be applied in design and development of new embedded coated nanomaterials used in biomedicine applications.

Direct Visualization of the Two-step Nucleation Model by Fluorescence Color Changes during Evaporative Crystallization from Solution.

The two-step nucleation model for crystal nuclei formation explains several experimental and theoretical results better than the classical nucleation theory. We report here direct visualization of the two-step nucleation model for organic molecular crystallization. Evaporative crystallization from a solution of a dibenzoylmethane boron complex that displays mechanofluorochromism, a fluorescence color change induced by mechanical perturbation, was probed by fluorescence change. The dependence of fluorescence change on dispersion concentration of the complex in a polymer matrix was also investigated. We detected transitional emission from the amorphous cluster state prior to crystallization. This is the first demonstration of the two-step nucleation model based on fluorescence color changes.

Localized surface plasmon resonance in arrays of nano-gold cylinders: inverse problem and propagation of uncertainties

The plasmonic nanostructures are widely used to design sensors with improved capabilities. The position of the localized surface plasmon resonance (LSPR) is part of their characteristics and deserves to be specifically studied, according to its importance in sensor tuning, especially for spectroscopic applications. In the visible and near infra-red domain, the LSPR of an array of nano-gold-cylinders is considered as a function of the diameter, height of cylinders and the thickness of chromium adhesion layer and roughness. A numerical experience plan is used to calculate heuristic laws governing the inverse problem and the propagation of uncertainties. Simple linear formulae are deduced from fitting of discrete dipole approximation (DDA) calculations of spectra and a good agreement with various experimental results is found. The size of cylinders can be deduced from a target position of the LSPR and conversely, the approximate position of the LSPR can be simply deduced from the height and diameter of cylinders. The sensitivity coefficients and the propagation of uncertainties on these parameters are evaluated from the fitting of 15500 computations of the DDA model. The case of a grating of nanodisks and of homothetic cylinders is presented and expected trends in the improvement of the fabrication process are proposed.

Optimized plasmonic nanostructures for improved sensing activities.

The paper outlines the optimization of plasmonic nanostructures in order to improve their sensing properties such as their sensitivity and their ease of manipulation. The key point in this study is the optimization of the localized surface plasmon resonance (LSPR) properties essential to the sensor characteristics, and more especially for surface-enhanced Raman scattering (SERS). Two aspects were considered in order to optimize the sensing performance: apolar plasmonic nanostructures for non polarization dependent detection and improvements of SERS sensitivity by using a molecular adhesion layer between gold nanostructures and glass. Both issues could be generalized to all plasmon-resonance-based sensing applications.