Alexandre Merlen

Surface enhanced Raman spectroscopy of organic molecules deposited on gold sputtered substrates

Aggregates of Au nanoparticles have been extremely easily obtained on glass substrates by physical sputtering under primary vacuum. With such a protocol, we demonstrate that it is possible to control the surface plasmon band absorption. Surface enhanced Raman spectroscopy (SERS) experiments were performed with methylene blue, zinc octacarboxyphthalocyanine, 4-aminothiophenol and cysteamine. The correlation between the absorption band and the wavelength giving the highest SERS intensity is clearly observed for methylene blue, in accordance with the electromagnetic enhancement theory. For the other molecules, effects of the chemical enhancement are also observed. In addition, we noticed a strong influence of the nature of the adsorbed molecule on the enhancement factor for a given wavelength. The origin of this feature is discussed in terms of resonant effects or multipolar surface plasmon modes.

Imaging the Optical near Field in Plasmonic Nanostructures

Over the past five years, new developments in the field of plasmonics have emerged with the goal of finely tuning a variety of metallic nanostructures to enable a desired function. The use of plasmonics in spectroscopy is of course of great interest, due to large local enhancements in the optical near field confined in the vicinity of a metal nanostructure. For a given metal, such enhancements are dependent on the shape of the structure as well as the optical properties (wavelength, phase, polarization) of the impinging light, offering a large degree of control over the optical and spatial localization of the plasmon resonance. In this focal point, we highlight recent work that aims at revealing the spatial position of the localized plasmon resonances using a variety of optical and non-optical methods.

A Surface Enhanced Raman Spectroscopy study of aminothiophenol and aminothiophenol-C60 self-assembled monolayers: evolution of Raman modes with experimental parameters

P-aminothiophenol (PATP) is a well-known molecule for the preparation of self-assembled monolayers on gold via its thiol functional group. After adsorption, it has been demonstrated that this molecule is anchored to gold through its thiol group, and standing nearly upright at the surface with the amino functional group on top. This molecule has been extensively studied by surface enhanced Raman spectroscopy but its exact SERS spectrum remains unclear. Here, we demonstrate that it can be strongly affected by at least two experimental parameters: laser power and layer density. Those features are discussed in terms of a dimerization of the PATP molecules. The free amino group affords the adsorption of other molecules such as C(60). In this case, a complex multilayer system is formed and the question of its precise characterisation remains a key point. In this article, we demonstrate that surface enhanced Raman spectroscopy combined with x ray photoelectron spectroscopy can bring very important information about the organization of such a self-assembled multilayer on gold. In our study, the strong evolution of Raman modes after C(60) adsorption suggests a change in the organization of aminothiophenol molecules during C(60) adsorption. These changes, also observed when the aminothiophenol layer is annealed in toluene, do not prevent the adsorption of C(60) molecules.

Optical near-field mapping of plasmonic nanostructures prepared by nanosphere lithography

We introduce a simple, fast, efficient and non-destructive method to study the optical near-field properties of plasmonic nanotriangles prepared by nanosphere lithography. Using a rectangular Fourier filter on the blurred signal together with filtering of the lower spatial frequencies to remove the far-field contribution, the pure near-field contributions of the optical images were extracted. We performed measurements using two excitation wavelengths (532.1 nm and 632.8 nm) and two different polarizations. After the processing of the optical images, the distribution of hot spots can be correlated with the topography of the structures, as indicated by the presence of brighter spots at the apexes of the nanostructures. This technique is validated by comparison of the results to numerical simulations, where agreement is obtained, thereby confirming the near-field nature of the images. Our approach does not require any advanced equipment and we suggest that it could be applied to any type of sample, while keeping the measurement times reasonably short.

Optical and luminescent properties of CdSe/ZnS and TiO2 semiconductor quantum dots embedded into PMMA layers

Optical quality PMMA thin film layers including different concentrations of 3nm CdSe/ZnS and 5 nm TiO2 semiconductor quantum dots have been made by spin coating method. Their optical properties show evident consequences of the confinement effects with wavelength bandgap shifting for both types of QDs. The confinement effects are more pronounced for CdSe/ZnS QDs than for TiO2 QDs. Layers including CdSe/ZnS QDs exhibit a strong luminescent behavior centred on 560nm with a stock-shift in front of the first exciton absorption peak.

Self-Assembly and Raman Spectroscopy of Additive Coated Nanocrystals

Copper oxalate 1 μm-sized nanocrystalline assemblies with several shapes (cushions, lenses, drilled cushions, and square rods) have been obtained by aqueous precipitation without additive, with glycerol, with PEG and with HPMC. Respective influences of these additives on the nanocrystals self-assembly are suggested from the obtained particles morphologies to provide a better understanding of this assembly process. Raman spectroscopy is used to highlight fluorescence occurring on the copper oxalate samples synthesized with additives. This additive induced fluorescence is suggested to result from specific interactions between the nanocrystals and the adsorbed additives.