Yann Battie

Chemical Growth and Photochromism of Silver Nanoparticles into a Mesoporous Titania Template

Elaboration of mesoporous titanium oxide film supporting silver nanoparticles is described. Mesoporous titanium oxide films are characterized by TEM analysis. Titania films are infiltrated with a silver salt solution and chemical reduction treatments are performed using either a NaBH(4) or a formaldehyde solution. Infiltrated films are then characterized by TEM, SEM, AFM, UV-visible spectroscopy, X-ray diffraction, and Rutherford Backscattering Spectrometry (RBS). The utilization of a mesoporous titania substrate allows to control the nanoparticle size and the interparticle distance. RBS experiments provide the evidence that NaBH(4) treatment induces a strong accumulation of silver nanoparticles in the subsurface of the layer, while formaldehyde treatment induces the formation of silver nanoparticles embedded into almost the whole depth of the titania film. Large silver nanocrystals are also formed at the film surface whatever the reducer used. A broad visible absorption band related to the surface plasmon resonance (SPR) is obtained in both cases and is strongly red-shifted compared to the SPR obtained for silver nanoparticles inside a silica matrix. Moreover, irradiation with visible light causes the photooxidation of silver nanoparticles by titania and a complete discoloration of the material. The photooxidation is related to a drastic decrease in the silver nanoparticle size and is found to be reversible, particularly in the case of the material obtained by the formaldehyde reduction.

Extended Maxwell-Garnett-Mie formulation applied to size dispersion of metallic nanoparticles embedded in host liquid matrix

The optical properties of metallic spherical nanoparticles embedded in host liquid matrix are studied. Extended Maxwell-Garnett-Mie formulation which accounts for size dispersion, the intrinsic confinement, and extrinsic size effect, is proposed for the calculation of the effective dielectric function and absorption coefficient of size dispersion of colloidal solution of Au and Ag nanoparticles in water. We demonstrate that the size distribution induces an inhomogeneous broadening and an increase of the amplitude of the plasmon band. A large redshift of the plasmon band is also observed for silver nanoparticles. Compared to the conventional Maxwell Garnett theory, we demonstrated that this model gives better description of the measured absorption spectra of colloidal gold solutions.

GoldHelix: Gold Nanoparticles Forming 3D Helical Superstructures with Controlled Morphology and Strong Chiroptical Property

Plasmonic nanoparticles, particularly gold nanoparticles (GNPs) hold a great potential as structural and functional building blocks for three-dimensional (3D) nanoarchitectures with specific optical applications. However, a rational control of their assembly into nanoscale superstructures with defined positioning and overall arrangement still remains challenging. Herein, we propose a solution to this challenge by using as building blocks: (1) nanometric silica helices with tunable handedness and sizes as a matrix and (2) GNPs with diameter varying from 4 to 10 nm to prepare a collection of helical GNPs superstructures (called Goldhelices hereafter). These nanomaterials exhibit well-defined arrangement of GNPs following the helicity of the silica template. Strong chiroptical activity is evidenced by circular dichroism (CD) spectroscopy at the wavelength of the surface plasmon resonance (SPR) of the GNPs with a anisotropy factor (g-factor) of the order of 1 × 10-4, i.e., 10-fold larger than what is typically reported in the literature. Such CD signals were simulated using a coupled dipole method which fit very well the experimental data. The measured signals are 1-2 orders of magnitude lower than the simulated signals, which is explained by the disordered GNPs grafting, the polydispersity of the GNPs, and the dimension of the nanohelices. These Goldhelices based on inorganic templates are much more robust than previously reported organic-based chiroptical nanostructures, making them good candidates for complex hierarchical organization, providing a promising approach for light management and benefits in applications such as circular polarizers, chiral metamaterials, or chiral sensing in the visible range.

Photo-directed organization of silver nanoparticles in mesostructured silica and titania films

This paper quantifies the migration of silver contained within mesostructured hybrid silica films and mesoporous titania films under exposure to modulated light. This quantization allows to demonstrate that all of the initial silver salt can be concentrated and reduced in domains accumulating the higher photonic energy. Entirely reduced in the form of nanoparticles of few nanometers size embedded in the silica matrix, silver is then quite stable even under subsequent homogeneous exposures. It is also shown that thanks to the relatively slow nanoparticle growth, successive multiple exposures can be used to create complex 3D microstructures within silica films using a simple dual beam interferometer. In mesoporous titania films, the UV photo-growth of silver nanoparticles remains limited to the vicinity of the film interface because of the matrix absorption and cannot provide deep 3D patterns of silver nanoparticles. However, 2D refractive index patterns can be obtained under UV exposure, erased with visible light and updated thanks to a reversible photochromic behavior. In such films, opposite migration flows of silver species are proven under UV intensity gradient and homogeneous visible exposure.

Experimental and theoretical determination of the plasmonic responses and shape distribution of colloidal metallic nanoparticles

The optical properties of gold and silver nanoparticles (NPs) dispersed in water and distributed in shape are investigated by introducing a shape distributed effective medium theory (SDEMT). This model takes into account the variation of depolarization parameter induced by a NP shape distribution. Simulations show that the shape distribution induces an inhomogeneous broadening and a decrease of the amplitude of the plasmon band. The number of plasmon bands and their positions depend on both the mean value of depolarization parameter and the NP material. By fitting the measured absorption spectra with the SDEMT, we unambiguously demonstrate that the depolarization parameter distribution, i.e., the shape distribution of nanoparticles can be deduced from absorption spectra.

How to determine the morphology of plasmonic nanocrystals without transmission electron microscopy

This paper reports the complete ellipsometric characterization of gold nanoparticles (NPs) embedded in a photoresist films. The effective dielectric function of nanocomposite films as well as the shape distribution and the volume fraction of NPs are extracted from ellipsometric measurements by introducing an effective medium theory which takes into account the NP shape distribution and the intrinsic confinement effect. This theory remains valid as long as the nanoparticle interaction is negligible. We show that the magnitude of the confinement depends on the nanoparticle shape and the environment through chemical damping. This suggests that the NP shape distribution can be directly estimated by ellipsometry, while the determination of absolute radius distribution requires transmission electron microscopy measurements. The imaginary part of the effective dielectric function exhibits a strong asymmetric surface plasmon band, while a large variation of the real part occurs close to the resonance. The redshift and the broadening of the plasmon band as the gold volume fraction increases are correlated to the evolution of NP shape distribution. This evolution is attributed to a competition between the nucleation and the coalescence of NPs. This unambiguously demonstrates that ellipsometry combined with a shape-distributed effective medium theory is a powerful alternative tool to transmission electron microscopy for the NP shape analysis.

Influence of the laser light absorption by the colloid on the properties of silver nanoparticles produced by laser ablation in stirred and stationary liquid

Silver nanoparticles were produced by nanosecond pulsed-laser ablation at 1064 nm of Ag in pure water. These experiments were performed using an alternative ablation cell design where a cylindrical shaped Ag target was horizontally irradiated, while the liquid was stirred by a stir rod coaxially arranged to the target. The repeatability of the generated colloids properties (extinction and size distribution) is assessed by statistical tools. The colloids properties prepared under stationary liquid are found to be unpredictable, while they are highly repeatable at high stirring speed. At the same time, electronic microscopy examinations of the irradiated Ag targets revealed that the width of the laser-machined grooves exponentially decays in stationary liquid and almost linearly under high stirring speed as the ablation proceeds. In the latter case, the decay rate was found to be constant from one experiment to the other, while it was not repeatable stationary liquid. We show that the decay of the groove width is due to an attenuation of the laser energy reaching the target surface due to the formation of a more or less dense NPs layer in front of the target as the ablation proceeds. Using the ablation time-dependence of the groove width, we can quantify the attenuation factor of the laser energy with exposure time. Finally, the relationship between the laser energy attenuation, stirring speed, and repeatability of the colloids properties is interpreted and discussed in terms of mass transfer.

Determination of morphological characteristics of metallic nanoparticles based on modified Maxwell-Garnett fitting of optical responses

A modified effective medium theory (MEMT) is introduced to determine morphological characteristics and the volume fraction of colloidal metallic nanoparticles. By analyzing the optical absorption spectra of gold nanoparticles (NPs), this model is used to determine the distribution of prolate and oblate NPs and to demonstrate the presence of spherical NPs. In addition to interband transition, the model takes into account the longitudinal and transversal surface plasmon resonances. The results predicted by the MEMT theory were found to be in very good agreement with the shape distributions obtained by transmission electron microscopy. We found that fitting optical absorption spectra using MEMT provides a robust tool for measuring the shape and concentration of metallic NPs.

Chirality distribution in single walled carbon nanotube films by spectroscopic ellipsometry

We report an experimental technique that determines the chirality distribution in single wall carbon nanotube (SWCNT) films. Films of CoMoCat SWCNTs and SWCNTs enriched in (6,5) chirality are considered. Classical methods like photoluminescence spectroscopy frequently give incomplete distribution. In this way, spectroscopic ellipsometry is used to determine the dielectric function of SWCNT film. The chirality abundance obtained by analysing the ellipsometric data with a tight binding model is compared with that deduced from photoluminescence excitation spectroscopy. We demonstrate that ellipsometry is an efficient tool for a complete and quantitative determination of the chirality distribution and the metallic/semiconducting ratio.

Determination of optical properties of percolated nanostructures using an optical resonator system

In this work, methods are introduced to the determination of optical properties of thin silver films and nanostructures. We present an optical resonant system consisting of a mirror, a transparent layer and a thin silver film. The layer sequences and the nanostructure of the thin films are investigated by optical methods consist of reflectance measurements. The structures are analyzed by atomic force microscopy and scanning electron microscopy. The optical properties are determined by modeling the reflectance data. We have found that the growth mechanisms of the silver layer are correlated to its optical properties. It also found that temperature treatments produce isolated particles with a narrow plasmon resonance.