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Plasmonic Cu nanoparticles were in-situ grown into a Cu$_2$O semiconductor matrix by using reactive magnetron sputtering and adjusting the amount of oxygen available during the synthesis in order to prevent the oxidation of part of copper atoms landed on the film surface. Varying only the oxygen flowrate (OFR) and using a single Cu target it was possible to observe the evolution in the simultaneous formation of metallic Cu and Cu$_2$O phases for oxygen-poor conditions. Suchformation is accompanied by the development of the surface plasmon band (SPB) corresponding to Cu, as evidenced by UV-Vis spectrophotometry and spectroscopic ellipsometry. The bandgap values of the elaborated composites containing embedded Cu plasmonic nanodomains were lower than the bandgap of single-phased Cu$_2$O films, likely due to the higher defect density associated to the nanocrystalline nature of films, promoted by the presence of metallic Cu. The resistivity of the thin films increased with more oxidative deposition conditions and was associated to an increase in Cu$_2$O/Cu ratio and smaller and more isolated Cu particles, as evidenced by high resolution transmission electron microscopy and X-ray diffraction. Photoconversion devices based on the studied nanocomposites were characterized by I-V and spectral photocurrent measurements, showing an increase in the photocurrent density under light illumination as consequence of the plasmonic particles excitation leading to hot carrier's injection in the nearby ZnO and Cu$_2$O semiconductors., Comment: ACS Applied Electronic Materials, American Chemical Society, 2022

International audience; The optical properties of chiral plasmonic metasurfaces depend strongly on their architecture, in particular the orientation and spacing between the individual building blocks assembled into large arrays. However, methods to obtain chiral metamaterials with fully tunable chiroptical properties in the UV, visible and near infrared range are scarce. Here, we show that the chiroptical properties of silver nanowires assembled in helical nanostructures by Grazing Incidence Spraying and Layer-by-Layer assembly can be finely tuned over a broad wavelength range using simple design principles. The angle between the oriented nanowire layers controls the intensity of the circular dichroism, reaching ellipticity values higher than 13° and g-factor values up to 1.6, while the shape of the circular dichroism spectra depends strongly on the spacing between the layers which can be tuned at the nm-scale. The structure-dependent optical properties of the assembly are successfully modeled using a transfer matrix approach.

In this Letter, we propose a new, to the best of our knowledge, approach to determine the shape distribution of gold (Au) nanorods from real-time extinction spectroscopy measurements. This method is based on the linearization of the shape distribution effective medium theory (SDEMT). The aspect ratio distribution of Au colloids is obtained in a few tens of ms without any a priori information on the distribution. Both bimodal and monomodal shape distributions of nanoparticles can be extracted by analyzing their extinction spectra. The proposed method is applied to monitor the change in the nanoparticle shape during their exposure to ns-laser pulses.

Due to their tunable physical and chemical properties, alloys are of fundamental importance in material science. The determination of stoichiometry is crucial for alloy engineering. Classical characterization tools such as energy-dispersive x-ray spectroscopy (EDX) are time consuming and cannot be performed in an ambient atmosphere. In this context, we introduce a new methodology to determine the stoichiometry of alloys from ellipsometric measurements. This approach, based on the analysis of ellipsometric spectra by an artificial neural network (ANN), is applied to electrum alloys. We demonstrate that the accuracy of this approach is of the same order of magnitude as that of EDX. In addition, the ANN analysis is sufficiently robust that it can be used to characterize rough alloys. Finally, we demonstrate that the exploitation of ellipsometric maps with the ANN is a powerful tool to determine composition gradients in alloys.

International audience; The optical properties of a monolayer of nanocomposite film (PMMA/gold nanocubes) were provided by fitting a proposed theoretical model to spectroscopic ellipsometry (SE) measurements. For such a thin film, these features cannot be successfully determined by means of experimental and conventional effective medium theory such as Maxwell-Garnett or Bruggeman. To make it possible, we developed a model of two classical Lorentz oscillators; one for a PMMA layer and the other for GNCs, revealing one homogeneous layer and rapid analysis without the need for large computational resources. Additionally, we tailored both the size and number of GNCs in the PMMA layer by tuning the synthesis parameters as seen in scanning electron microscopy (SEM) images. In parallel, SE measurements clearly highlighted the change in the optical properties of GNCs as a function of their density on the substrate and dimensions. Our findings demonstrate that SE is an alternative method to characterize layered GNCs on opaque substrates efficiently, which has potential implications for designing other morphologies in the future.

We investigate the productivity of ultra-small gold nanoparticles generated by pulsed-laser ablation in liquid of a high-speed rotating gold target as functions of laser ablation time and rotation speed of the target in the range 90–3000 rpm. These experiments were performed by in situ monitoring the extinction spectra of the gold colloidal suspension. The time evolution of the gold volume fraction in the colloidal suspension of the target was determined by modeling the extinction spectra using the shape distribution effective medium theory. The time dependence of the ablation rate, deduced from that of the volume fraction, shows an initial exponential decay followed by a steady-state value at longer ablation time. The influence of the laser-induced roughening of the target surface on the time evolution of the ablation rate is clearly demonstrated. The experimental results also reveal the dependence of the time evolution of the ablation rate of the target on its rotation speed. The effect of the liquid flow on the ablation rate of the target is analyzed and discussed.

Helical and twisted silica nanoribbons, deposited in an in-plane direction and with a random orientation, on a quartz substrate showed chiral optical scattering, and the helical nanoribbons had a g-factor of the order of 10-2 below 250 nm. Their signs depend on the handedness of the nanohelices. The effect of the morphology and the orientation of the helices on the chiral optical scattering were investigated with simulations via the boundary element method.

International audience; CdSe nanocrystals (NCs) were grafted on chiral silica nanoribbons, and the mechanism of resulting chirality induction was investigated. Because of their chiral organization, these NCs show optically active properties that depend strongly on their grafting densities and sizes of the NCs. The effect of the morphology of the chiral silica templates between helical (cylindrical curvature) vs twisted (saddle like curvature) ribbons was investigated. The g-factor of NCs-silica helical ribbons is larger than that of the NCs-silica twisted ribbons. Finally, rod-like NCs (QR) with different lengths were grafted on the twisted silica ribbons. Interestingly, their grafting direction with respect to the helix surface changed from side-grafting for short QR to tip-grafting for long rods and the corresponding CD spectra switched signs.

International audience; Chirality is found at all length scales in nature, and chiral metasurfaces have recently attracted attention due to their exceptional optical properties and their potential applications. Most of these metasurfaces are fabricated by top-down methods or bottom-up approaches that cannot be tuned in terms of structure and composition. By combining grazing incidence spraying of plasmonic nanowires and nanorods and Layer-by-Layer assembly, we show that nonchiral 1D nano-objects can be assembled into scalable chiral Bouligand nanostructures whose mesoscale anisotropy is controlled with simple macroscopic tools. Such multilayer helical assemblies of linearly oriented nanowires and nanorods display very high circular dichroism up to 13 000 mdeg and giant dissymmetry factors up to g ≈ 0.30 over the entire visible and near-infrared range. The chiroptical properties of the chiral multilayer stack are successfully modeled using a transfer matrix formalism based on the experimentally determined properties of each individual layer. The proposed approach can be extended to much more elaborate architectures and gives access to template-free and enantiomerically pure nanocomposites whose structure can be finely tuned through simple design principles.

We report a study of the effect of nitrogen ion bombardment on the optical properties of anatase TiO2 ultrathin films, particularly the band gap energy. The TiO2 films were prepared by a sol-gel method and dip-coating process. The as-prepared TiO2 films were then exposed to a N 2 + low-energy ion beam from a microwave electron cyclotron resonance (ESR) ion source. Raman and spectroscopic ellipsometry (SE) analysis were performed on TiO2 films prepared at different N 2 + exposure times. The Raman measurements reveal the conservation of the anatase TiO2 crystalline structure after the ion beam exposure. From a detailed ellipsometric study, the thickness of layers, the dielectric function, the band gap and the Urbach energies were determined. The obtained results show an increase of the TiO2 band gap with the decrease of thickness of films during N 2 + exposure time. The band gap energy was blue shifted from 20 meV to 140 meV as the exposure time was increased from 5 min to 20 min when the thickness was decreased from 30 nm to 21 nm. This increasing of band gap energy could be explained by the thickness effect. From the band tail, the Urbach energy was also affected by N 2 + ion beam. These results are in good agreement with the observed broadending of the Raman band the O Ti O bending vibration mode, as the exposure time increases.

We propose an advanced in situ extinction spectroscopy set up to investigate the dynamic of the fragmentation and reshaping processes of gold colloids during a ns-laser pulse exposure. The evolution of the aspect ratio distribution of gold nanorods (NRs) during the laser exposure is obtained by analyzing each spectra with the shape distributed effective medium theory. We demonstrate that the kinetics of NR shape transformation can be divided into two fluence regimes. At small fluence, the kinetic is limited by the NRs orientation, while at high fluence, the fragmentation rate is only limited by the probability of NRs to be located in the irradiated volume.

Perovskite nanocrystals (PNCs) exhibit excellent absorption and luminescent properties. Inorganic silica right (or left) handed nanohelices are used as chiral templates to induce optically active properties to CsPbBr

International audience; We apply a kinetic model to simulate the photocatalytic removal of stearic acid (SA) discrete deposits. At the microscopic scale, the SA deposit is modelled as a set of hundreds of squared islands deposited on the TiO2 surface and separated from each other. The input data include the projected areas and heights of the islands both characterized by a Gaussian distribution law with a mean value and various standard deviations. The effects of these parameters are examined, analyzed and put in relation with experimental results from the literature. The dependence of the removal kinetics of the SA deposits on its initial microstructure is clearly demonstrated. Additionally, we show that the removal kinetics of the SA deposit as measured by infrared spectroscopy can be satisfactory predicted from the distributions of the initial projected areas of the islands and their heights as measured by optical microscopy and atomic force microscopy.

Chiral materials appear as excellent candidates to control and manipulate the polarization of light in optical devices. In nanophotonics, the self-assembly of colloidal plasmonic nanoparticles gives rise to strong resonances in the visible range, and when such organizations are chiral, a strong chiroplasmonic effect can be observed. In the present work, we describe the optical properties of chiral artificial nanophotonic materials

International audience; Here, we exercise nanoscale control over the assembly of highly anisotropic silica helices using convective flow by using the physical properties occurring during evaporation-induced self-assembly. Organizing and patterning such chiral elongated objects over large surfaces in a controllable and reproducible fashion are challenging but desirable to optimize the performance of biomimetic structures, nanosensors (mechanical properties of helices), or optical materials (chiral objects have asymmetric interactions with light as absorption is different for left- and right-handed polarization). The coupling of evaporation forces and physicochemical solution properties induce specific helix alignment, and the stick–slip phenomenon produces a periodical deposition of bands with controllable and regular spacing. Helix orientation, packing density, and spacing can then be tuned. We observe the effect of polymer additives, silica helix concentration, and substrate withdrawal speed on the quality and orientation of the helix deposition. Theoretical modeling based on capillary hydrodynamics is developed to describe the relationship between evaporative conditions and pitch distance, the band width of the stick region, and the helix orientation.

Perovskite nanocrystals (PNCs) exhibit excellent absorption and luminescent properties. Inorganic silica right (or left) handed nanohelices are used as chiral templates to induce optically active p...

We study the local density of optical states (LDOS) for lossy dielectric substrates whose electric permittivity has a vanishing real part, approaching zero from the positive side of the real axis. A criterion for evaluating the threshold height above (below) which radiative (non-radiative) processes dominate for a dipole emitter is established. We focus on the case of a vertical dipole above the ϵ -near-zero (ENZ) substrate and show that, in the lossless case, complete LDOS cancellation originates from radiative modes in its near field. We evaluate the performance of commercially available ENZ materials and quantify the limits of such cancellation effects with the intrinsic losses of the substrate.

International audience; Chiral materials appear as excellent candidates to control and manipulate the polarization of light in optical devices. In nano-photonics, the self-assembly of colloidal plasmonic nanoparticles gives rise to strong resonances in the visible range and, when such organizations are chiral, strong chiroplasmonic effect can be observed. In the present work, we describe the optical properties of chiral artificial nano-photonic materials, Goldhelices, which are hierarchically organized by Grazing Incidence Spraying. These Goldhelices are made by plasmonic nanoparticles (gold) grafted onto helical templates made from silica nanohelices. A comparison of oriented vs non-oriented surfaces has been performed by Mueller matrix polarimetry, showing the importance of the organization of the Goldhelices regarding their interaction with light. Moreover, mono-vs multi-layers photonic films are created and the measured optical properties are discussed and compared to simulations.

We report the temperature dependence of the dielectric function, the exciton binding energy and the electronic transitions of crystallized ZnO thin film using spectroscopic ellipsometry (SE) and photoluminescence (PL). ZnO layers were prepared by sol-gel method and deposited on crystalline silicon (Si) by spin coating technique. The ZnO optical properties were determined between 300 K and 620 K. Rigorous study of optical responses was achieved in order to demonstrate the quenching exciton of ZnO as a function of temperature. Numerical technique named constrained cubic splines approximation (CCS), Tauc-Lorentz (TL) and Tanguy dispersion models were selected for the ellipsometry data modeling in order to obtain the dielectric function of ZnO. The results reveals that the exciton bound becomes widely flattening at 470 K on the one hand, and on the other that the Tanguy dispersion law is more appropriate for determining the optical responses of ZnO thin film in the temperature range of 300 K–420 K. The Tauc-Lorentz, for its part, reproduces correctly the ZnO dielectric function in 470 K–620 K temperature range. The temperature dependence of the electronic transition given by SE and PL shows that the exciton quenching was observed in 420 K–∼520 K temperature range. This quenching effect can be explained by the equilibrium between the Coulomb force of exciton and its kinetic energy in the film. The kinetic energy was found to induce three degrees of freedom of the exciton.

An ellipsometric cell is developed to simultaneously determine the shape distribution, the volume fraction, and the complex refractive index of gold and silver colloids. Simulation reveals that this cell drastically improves the detection limit of ellipsometry. Indeed, Ag and Au nanoparticles (NPs) are detected at the ppmv level. We demonstrate that the NPs shape distribution can be estimated from ellipsometric measurements by analyzing them with a shape distributed effective medium theory (SDEMT). The obtained distributions from ellipsometry are in agreement with those deduced from transmission electron microcopy (TEM). Contrary to TEM, ellipsometry probes a large number of NPs estimated at about 1011 NPs. Finally, we show that the complex refractive index of colloids as determined from ellipsometry is sensitive to the optical properties of the solvent and the plasmonic properties of NPs.

International audience; Here, we report for the first time a facile and fast one-step strategy to fabricate monodisperse gold nanocubes (GNCs) by spin-coating a gold precursor-loaded PMMA dispersion on N-doped silicon. A vapor induced phase separation allows PMMA self-assembly into a nanoporous film including the GNCs in its holes. Control of size and shape until obtaining monodisperse GNCs was achieved by tailoring the concentration of the gold precursor. Upon increasing this concentration, the optical properties of the GNCs such as the surface plasmon resonance has been red-shifted from 540 to 650 nm, in relation to the strong interaction between closely separated GNCs, increase in their number and PMMA thickness on the substrate surface. Therefore, the high density of hotspots in the gaps between closely spaced GNCs led to the sensitive detection of pyridine with an unprecedented SERS threshold of detection of 10−12 M. SERS experiments revealed the high chemical enhancement and allowed few molecule detection without any surface modification of the GNCs.

International audience; Nanocomposite films consisting of gold nanoparticles embedded in zinc oxide (ZnO-Au) have been synthesized with different gold loadings by reactive magnetron sputtering at near-room temperature followed by ex situ annealing in air up to 300 °C. Using X-ray diffraction and high resolution transmission microscopy it is shown that during deposition gold substitutes zinc in ZnO as isolated atoms and in nanoparticles still exhibiting the structure of ZnO. Both situations degrade the crystalline quality of the ZnO matrix, but thermal annealing cures it from isolated gold atoms and triggers the formation of gold nanoparticles of size higher than 3 nm, sufficient to observe a strong activation of localized surface plasmon resonance (LSPR). The amplitude of LSPR absorption observed after annealing increases with the gold loading and annealing temperature. Moreover, UV and visible photoluminescence from the ZnO matrix is strongly enhanced upon activation of LSPR showing strong coupling with the gold nanoparticles. Finally, modeling of spectroscopic ellipsometry measurements unambiguously reveals how curing the defects increases the optical bandgap of the ZnO matrix and modifies the optical dielectric functions of the nanocomposite and ZnO matrix.

Ferrofluids are colloidal suspensions generally composed of ferromagnetic or ferrimagnetic nanoparticles (NPs). In the present study, the authors have focused on the ellipsometric characterization of two types of ferrofluids: one constituting maghemite (γ-Fe2O3) NPs and the other cobalt ferrite (CoFe2O4) NPs. The optical properties of the NPs are extracted from the ellipsometric spectra by using the Maxwell–Garnett effective medium approximations. As expected, Mueller matrix measurements reveal that the ferrofluid becomes anisotropic under the influence of a magnetic field. The authors correlate this anisotropy to the preferential orientation of NPs along the magnetic field.Ferrofluids are colloidal suspensions generally composed of ferromagnetic or ferrimagnetic nanoparticles (NPs). In the present study, the authors have focused on the ellipsometric characterization of two types of ferrofluids: one constituting maghemite (γ-Fe2O3) NPs and the other cobalt ferrite (CoFe2O4) NPs. The optical properties of the NPs are extracted from the ellipsometric spectra by using the Maxwell–Garnett effective medium approximations. As expected, Mueller matrix measurements reveal that the ferrofluid becomes anisotropic under the influence of a magnetic field. The authors correlate this anisotropy to the preferential orientation of NPs along the magnetic field.

Transparent nanoscale-film heterojunctions based on Cu2O and ZnO were fabricated by atomic layer deposition and reactive magnetron sputtering. The constitutive layers exhibit high crystalline quali...

International audience; We propose an advanced photothermal model based on a modified Takami model (MTM) to explain the mechanisms of shape changes of colloidal gold nanorods (NRs) induced by nanosecond laser pulses. This model takes into account the orientation of NRs, the radiative and convective losses, and the phase transitions of NRs. It was applied to the determination of the evolution of temperature and the shape and size transformations of NRs during the laser exposure. A series of measurements arising from the interaction between Au NRs and nanosecond laser pulses were analyzed by TEM measurements and the MTM model. We have demonstrated that the fragmentation and reshaping processes govern the nanoparticle (NP) shape. At high laser fluence, the complete fragmentation leads to a population of nearly spherical NPs, while at a moderate laser fluence, the partial fragmentation and reshaping processes generate a bimodal distribution. At low laser fluence, uncommon ϕ-shape NPs were produced as a result of the competition of cooling and reshaping processes. We also demonstrated that it is possible by the MTM model to determine the laser fluence required to suppress some specific NR shapes and to predict the NP size and shape distributions obtained after the laser exposure.

International audience; A new methodology, to the best of our knowledge, is developed to determine the shape distribution profile of gold nanoparticles (NPs) from optical spectroscopic measurements. Indeed, an artificial neural network (ANN) approach was introduced to classify Au NP shape distributions from their normalized absorption spectra. This ANN quantitatively analyzes the absorption spectra and provides the posterior probability to have a bimodal or unimodal shape distribution. Several colloidal suspensions were considered to investigate the robustness of the ANN approach. The comparison between ANN classification and TEM analysis was also given and discussed. We demonstrate that ANN classification is a suitable tool to inspect rapidly Au colloidal suspensions after their synthesis.

In this paper, we explore the ability of ellipsometry to characterize colloidal suspensions composed of gold nanoparticle (NP) chains. The complex effective index of these suspensions is deduced from ellipsometric measurement by using a wavelength-by-wavelength inversion without any dispersion law. We show that the effective refractive index of these colloids is defined by the nature of the solvent, whereas their effective extinction coefficient is mainly sensitive to the plasmonic properties of NP chains. The influence of the NP radius distribution and arrangement on the effective extinction coefficient of NP chain are investigated through simulations based on the coupled point dipole method (CDM). We clearly show that this coefficient is mainly sensitive to the interparticle distance and the number of NPs in the longest segment of chains. We demonstrate that the distribution of the number of NPs in the longest segment of chains and their volume fractions can be directly deduced from the ellipsometry by ...

International audience; Plasmonic Cu nanoparticles (NP) were successfully deposited on ZnO substrates by atomic layer deposition (ALD) owing to the Volmer–Weber island growth mode. An evolution from Cu NP to continuous Cu films was observed with an increasing number of ALD cycles. Real and imaginary parts of the NP dielectric functions, determined by spectroscopic ellipsometry using an effective medium approach, evidence a localized surface plasmon resonance that can be tuned between the visible and near-infrared ranges by controlling the interparticle spacing and size of the NP. The resulting Cu NP/ZnO device shows an enhanced photoresponse under white light illumination with good responsivity values, fast response times, and stability under dark/light cycles. The significant photocurrent detected for this device is related to the hot-electron generation at the NP surface and injection into the conduction band of ZnO. The possibility of tuning the plasmon resonance together with the photoresponsivity of the device is promising in many applications related to photodetection, photonics, and photovoltaics.

We report a comparative study between Forouhi-Bloomer, Tauc-Lorentz and Tanguy dispersion laws for determining the reliable dielectric function of crystallized ZnO. ZnO layers were prepared by sol-gel method and deposited on crystalline silicon (c-Si) by spin coating. Spectroscopic ellipsometry (SE) was performed on ZnO/c-Si and each dispersion law was considered in the physical model for fitting SE experimental data. A best agreement was found between measurements and model. This applies in particular to the Tanguy dispersion. The physical parameters such as excitonic energy, optical gap, damping factor, real and imaginary parts of dielectric function were determined and analyzed. The temperature-dependent photoluminescence spectroscopy (PL) measurements were also used to approve the adequate dispersion law for ZnO material. We found by SE and PL measurements that Tanguy law dispersion can be considered as the most appropriate one for a correct description of ZnO optical dielectric function and for the interpretation of the absorption tail band and for the excitonic band of crystallized ZnO. The band-gap energy, excitonic energy and damping factor parameter are determined and analyzed. Their values (3.37 eV, 48 meV and 39 meV, respectively) extracted from ellipsometry are in good agreement with those obtained by PL measurements.

International audience; 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.....

International audience; A new methodology is developed to determine the shape distribution of gold nanoparticles (NPs) from optical spectroscopic measurements. Indeed, the morphology of Au colloids is deduced by fitting their absorption spectra with an effective medium theory which takes into account the nanoparticle shape distribution. The same procedure is applied to ellipsometric measurements recorded on photoresist films which contain Au NPs. Three spaces (L2, r2, P2) are introduced to interpret the NPs shape distribution. In the P2 space, the sphericity, the prolacity and the oblacity estimators are proposed to quantify the shape of NPs. The r2 space enables the determination of the NP aspect ratio distribution. The distributions determined from optical spectroscopy were found to be in very good agreement with the shape distributions obtained by transmission electron microscopy. We found that fitting absorption or ellipsometric spectra with an adequate effective medium theory, provides a robust tool for measuring the shape and concentration of metallic NPs.

International audience; We present a method to characterize optical properties of liquids by spectroscopic ellipsometry. The experiments use a specific liquid cell that avoids disturbance of waves at air-liquid interface and allows the determination of the real and the imaginary part of the refractive index, with a sensitivity of the latter below 10−4. The method is illustrated by results obtained with a spectroscopic phase modulation ellipsometer on several liquids such as deionised water, microscope oil and protein solution. Comparisons of the method with standard techniques are given.

In this paper, the optical properties and the growth mechanism of Au/SiO2 metal-insulator films (MIFs) are investigated by combining ellipsometry and transmission electron microscopy. The ellipsometric measurements, analyzed by using effective medium theories, show that the growth mechanism involves a Volmer-Weber growth mode while the morphology and the optical properties of Au/SiO2 MIFs are directly related to the percolation of the Au nanostructures. Indeed, below the percolation threshold of Au, the MIFs consist of ellipsoidal Au inclusions embedded in a SiO2 matrix. These insulating films present anisotropic plasmonic properties, attributed to the asymmetric interactions between nanaoparticles (NPs), which can be modeled according to the interacted shape distributed nanoparticle effective medium theory. At the percolation threshold of Au, an insulator-to-metal transition is observed. The MIFs simultaneously exhibit plasmonic and metallic optical properties, which can be described by the Bruggeman theory. The density of free electrons increases and the MIFs become more and more conductive as the Au volume fraction increases. We also demonstrate that for a high Au volume fraction, Bruggeman and Maxwell Garnett theories converge toward the same results, suggesting that the film is composed of isolated SiO2 inclusion embedded in a gold matrix.In this paper, the optical properties and the growth mechanism of Au/SiO2 metal-insulator films (MIFs) are investigated by combining ellipsometry and transmission electron microscopy. The ellipsometric measurements, analyzed by using effective medium theories, show that the growth mechanism involves a Volmer-Weber growth mode while the morphology and the optical properties of Au/SiO2 MIFs are directly related to the percolation of the Au nanostructures. Indeed, below the percolation threshold of Au, the MIFs consist of ellipsoidal Au inclusions embedded in a SiO2 matrix. These insulating films present anisotropic plasmonic properties, attributed to the asymmetric interactions between nanaoparticles (NPs), which can be modeled according to the interacted shape distributed nanoparticle effective medium theory. At the percolation threshold of Au, an insulator-to-metal transition is observed. The MIFs simultaneously exhibit plasmonic and metallic optical properties, which can be described by the Bruggeman the...

International audience; We report an uncommon study of the insertion of distributions of both volume fraction and depolarization factors in the modeling of the plasmonic properties of implanted Ag nanoparticles (Ag-NPs) in a SiO2 layer when using spectroscopic ellipsometry (SE) characterization. The Ag-NPs were embedded in the SiO2 matrix by Ag+ ion implantation at various doses of 0.5 × 1016, 1 × 1016, 2 × 1016, and 5 × 1016 ions cm−2. The formation of the Ag-NPs in a host matrix of SiO2 was controlled by transmission electron microscopy (TEM). The Ag-NPs are self-organized in the layer, and their mean radius ranges between 2 and 20 nm. The optical properties of layers were extracted by modeling the SE parameters by taking into account the depth profile concentration of Ag-NPs. The mixture of SiO2 and Ag-NP inclusions was modeled as an effective medium according to the shape distributed effective medium theory (SDEMT). In addition to the optical responses, it is shown that this model enables the explanation of the impact of NP shape distribution on the plasmon band and provides precious information about the NP shape characteristics. A good agreement was obtained between ellipsometry and TEM results. The distribution of the volume fraction in the film was found to lead to a gradient of effective dielectric function which was determined by the SDEMT model. The effective dielectric function reveals distinct Ag plasmon resonance varying as the Ag+ ions dose is varied. The real part of the dielectric function shows a significant variation around the plasmon resonance in accordance with the Kramers-Kronig equations. All determined optical parameters by SDEMT are provided and discussed. We highlight that SE combined with SDEMT calculations can be considered as a reliable tool for the determination of the NP shape and volume fraction distributions without the need of TEM.

6th International Conference on Spectroscopic Ellipsometry (ICSE), Kyoto, JAPAN, MAY 26-31, 2013; International audience; We describe a spectroscopic ellipsometer in the visible domain (400-800 nm) based on a rotating compensator technology using two detectors. The classical analyzer is replaced by a fixed Rochon birefringent beamsplitter which splits the incidence light wave into two perpendicularly polarized waves, one oriented at +45 degrees and the other one at-45 degrees according to the plane of incidence. Both emergent optical signals are analyzed by two identical CCD detectors which are synchronized by an optical encoder fixed on the shaft of the step-by-step motor of the compensator. The final spectrum is the result of the two averaged. and. spectra acquired by both detectors. We show that. and. spectra are acquired without systematic errors on a spectral range fixed from 400 to 800 nm. The acquisition time can be adjusted down to 25 ms. The setup was validated by monitoring the first steps of bismuth telluride film electrocrystallization. The results exhibit that induced experimental growth parameters, such as film thickness and volumic fraction of deposited material can be extracted with a better trueness.

The optical properties of spherical gold and silver nanoparticles distributed in size are investigated through a new effective medium theory. It is about the modified Maxwell-Garnett-Mie theory (MMGM) that takes into account the intrinsic confinement, dynamic effects and the nanoparticle radius distribution. In the case of monodispersed nanoparticles with a radius in the 1 nm-25 nm range, MMGM is equivalent to the Mie theory. Compared to the conventional effective medium theory, we demonstrate that MGMM gives better description of the measured extinction spectra of colloidal gold and silver solutions. (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

International audience; A new effective medium theory is introduced to describe the optical properties of a two-dimensional array of metallic nanoislands. This model which takes into account both the nanoisland orientation and their shape distribution is successfully used to interpret the ellipsometric measurements performed on gold nanoislands sputtered on a silicon substrate. By coupling ellipsometry to atomic force microscopy measurements, we show that the growth mechanism involves a Volmer-Weber growth mode. The optical anisotropy of uniaxial films was attributed to in-plane preferential self-orientation of gold nanoislands. Finally, we demonstrate that the optical birefringence and dichroism of nanoisland layers can be tuned during the film growth and are due to the splitting of the plasmon resonance into two modes: the transversal and the longitudinal modes of gold nanoislands.

This paper reports recent advances in ellipsometric characterization of silver and gold nanoparticles (NPs). Three systems are investigated: films composed of Au NPs distributed in shape, films with a gradient of concentration of Ag NPs, and colloidal suspensions composed of Au NP chains. The authors show that ellipsometry is highly sensitive to the plasmon resonance of NPs. This later can be used as an efficient probe of the NP morphology. The ellipsometric results are systematically compared to those that are obtained by transmission electron microscopy. The authors demonstrate that quantitative insights such as the shape distribution, the concentration, and the organization of NPs can be extracted from ellipsometric spectra.This paper reports recent advances in ellipsometric characterization of silver and gold nanoparticles (NPs). Three systems are investigated: films composed of Au NPs distributed in shape, films with a gradient of concentration of Ag NPs, and colloidal suspensions composed of Au NP chains. The authors show that ellipsometry is highly sensitive to the plasmon resonance of NPs. This later can be used as an efficient probe of the NP morphology. The ellipsometric results are systematically compared to those that are obtained by transmission electron microscopy. The authors demonstrate that quantitative insights such as the shape distribution, the concentration, and the organization of NPs can be extracted from ellipsometric spectra.

We report on the realization of functional infrared light concentrators based on a thick layer of air-polymer metamaterial with controlled pore size gradients. The design features an optimum gradient index profile leading to light focusing in the Fresnel zone of the structures for two selected operating wavelength domains near 5.6 and 10.4 μm. The metamaterial which consists in a thick polymer containing air holes with diameters ranging from λ/20 to λ/8 is made using a 3D lithography technique based on the two-photon polymerization of a homemade photopolymer. Infrared imaging of the structures reveals a tight focusing for both structures with a maximum local intensity increase by a factor of 2.5 for a concentrator volume of 1.5 λ3, slightly limited by the residual absorption of the selected polymer. Such porous and flat metamaterial structures offer interesting perspectives to increase infrared detector performance at the pixel level for imaging or sensing applications.

International audience; 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.

International audience; We report on structural and optical properties of ZnO thin films deposited on different Si-based substrates presenting different porosities. ZnO layers were prepared by sol gel method and deposited on crystalline silicon (ZnO/Si), mesoporous silicon (ZnO/PS+) and nanoporous silicon (ZnO/PS-) by spin coating. Several techniques such as scanning electron microscope (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence spectroscopy (PL) and spectroscopic ellipsometry (SE) were used to study the influence of the pore size of porous silicon (PS) on physical properties of ZnO films. SEM images revealed the formation of ZnO granular nanoparticles on Si, PS- and PS+ substrates. We show by the XRD analysis that hexagonal crystallized (002) ZnO is mainly obtained for ZnO/PS- system causing by a strong absorption of the capillary effect and high adhesion to PS- surface. An intense PL related to ZnO and PS- was demonstrated for ZnO/PS- in UV and visible ranges. Optical properties of ZnO were determined and analyzed by SE using Tanguy dispersion model. For each sample, a specific optical model was carried out. SE confirms a good physical properties of ZnO/PS- comparing to ZnO/Si and ZnO/PS+. For example, the good crystallinity is characterized by low damping factor value (Gamma). This value was found by SE to be low (29 meV) for the ZnO/PS-, while the damping factors of ZnO/Si and ZnO/PS+ are 47 meV and 70 meV, respectively. The amplitude of dielectric function of ZnO/PS- around 3.4 eV reveals an increase of grain size and crystallinity of ZnO layer.

International audience; By irradiating a cylindrical silver target rotated at a high-speed within the range 300–2400 rpm (lateral speed 0.16–1.25 m/s) in pure water, we prepare ligand-free Ag nanoparticles (NPs) with a size of 4 ± 2 nm which are likely to be primary particles. Usually, the generation of NPs showing such a small size requires either a laser post-treatment and/or chemical additives. As the rotation rate of the target is increased, calculated 3D flow patterns revealed different hydrodynamic regimes which clearly influence the ablation rate and repeatability of the process as well as the colloidal properties. In addition to revealing the importance of fluid dynamics in pulsed-laser ablations in liquids, this study provides a way for producing in one step pure NPs with sizes below 5 nm which are suitable for applications in catalysis.

International audience; Single-walled carbon nanotubes (SWCNT) synthesized using the HiPco (R) process and purified thereafter were submitted to two covalent functionalization processes: i) a mild oxidation in a concentrated HNO3 solution using microwave irradiation and ii) a radical functionalization to graft methoxyphenyl groups. The samples were analyzed by Raman spectroscopy and spectroscopic ellipsometry in the energy window 0.07-4.96 eV. The complex dielectric function was analytically calculated in order to extract the real (epsilon(r)) and imaginary (epsilon(i)) parts of this function vs. the incident energy of the light. The ellipsometric data in the infrared part of the spectrum revealed that process i) mainly affected the amorphous carbon deposited on the surface of SWCNTs while process ii) strongly changed the electronic nature of the film due to a charge transfer between methoxyphenyl groups and SWCNTs. These results demonstrate the richness of information that spectroscopic ellipsometry is able to bring about on an entire carbon nanotube ensemble compared to Raman spectroscopy, while not suffering from limitation on their electronic structure and/or aggregate state/presence of surfactants.

The optical properties of single walled carbon nanotube (SWCNT) films, produced by vacuum filtration, are correlated with their diameter and their in plane preferred orientation by coupling transmission and scanning electron microscopy to conventional ellipsometry. We focused on the optical anisotropy of this material and we demonstrated that it was originated from a breakdown in the selection rules.