Rapid ellipsometric imaging characterization of nanocomposite films with an artificial neural network.

Imaging ellipsometry is an optical characterization tool that is widely used to investigate the spatial variations of the opto-geometrical properties of thin films. As ellipsometry is an indirect method, an ellipsometric map analysis requires a modeling step. Classical methods such as the Levenberg-Marquardt algorithm (LM) are generally too time consuming to be applied on a large data set. In this way, an artificial neural network (ANN) approach was introduced for the analysis of an ellipsometric map. As a proof of concept this method was applied for the characterization of silver nanoparticles embedded in a poly-(vinyl alcohol) film. We demonstrate that the LM and ANN give similar results. However, the time required for the ellipsometric map analysis decreases from 15 days for the LM to 1 s for the ANN. This suggests that the ANN is a powerful tool for fast spectroscopic-ellipsometric-imaging analysis.

In situmonitoring the productivity of ultra-small gold nanoparticles generated by pulsed-laser ablation of a high-speed rotating gold target in pure water.

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 byin situmonitoring 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.

In situ monitoring of the shape distribution of metallic colloids from extinction spectroscopy measurements.

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.

Determination of the Size Distribution of Metallic Colloids from Extinction Spectroscopy.

In this paper, we explore the ability of extinction spectroscopy to characterize colloidal suspensions of gold nanoparticles (Au NPs). We demonstrate that the Au NPs' size distribution can be deduced by analyzing their extinction spectra using Mie theory. Our procedure, based on the non-negative least square algorithm, takes advantage of the high sensitivity of the plasmon band to the Au NP size. In addition, this procedure does not require any a priori information on the Au NP size distribution. The Au NPs' size distribution of monomodal or bimodal suspensions can be satisfactorily determined from their extinction spectra. Finally, we show that this characterization tool is compatible with in situ measurement and allows following the change in NPs' radii during laser exposure.

Monitoring the aspect ratio distribution of colloidal gold nanoparticles under pulsed-laser exposure.

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.

Mechanisms and advanced photothermal modelling of laser-induced shape transformations of colloidal gold nanorods by nanosecond laser pulses.

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.

Ellipsometry of Colloidal Solutions: New Experimental Setup and Application to Metallic Colloids.

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.

Interaction of a converging laser beam with a Ag colloidal solution during the ablation of a Ag target in water.

We studied the nanosecond laser-induced shape modifications of Ag colloids exposed to a converging laser beam during the ablation of a Ag target in water. To this end, we performed a series of laser ablation experiments in which the laser energy was varied while all other parameters were kept constant. In addition to transmission electron microscopy (TEM), the shape distribution of the Ag nanoparticles was determined by modelling the extinction spectra of the final colloidal solutions using theoretical calculations based on shape distributed effective medium theory (SDEMT). From these calculations, two physical parameters named sphericity and dispersity were introduced and used to gauge the evolution of the shape distribution of the particles. As the laser energy on the target was increased from 5 to 20 mJ/pulse, an apparently abrupt modification of the shape distribution of the particles was evidenced by both TEM and SDEMT calculations. This change is explained in terms of competitive fragmentation, growth and reshaping processes. On the basis the heating-melting-vaporization model, we demonstrate how the competition between these processes, occurring at different locations of the converging beam, determines the shape distribution of the final product. We highlight the relevance of the fluence gradient along the beam path and the laser interaction volume on the laser-induced modifications of the suspended particles during the ablation process.

Effect of SiN x diffusion barrier thickness on the structural properties and photocatalytic activity of TiO2 films obtained by sol-gel dip coating and reactive magnetron sputtering.

We investigate the effect of the thickness of the silicon nitride (SiN x ) diffusion barrier on the structural and photocatalytic efficiency of TiO2 films obtained with different processes. We show that the structural and photocatalytic efficiency of TiO2 films produced using soft chemistry (sol-gel) and physical methods (reactive sputtering) are affected differentially by the intercalating SiN x diffusion barrier. Increasing the thickness of the SiN x diffusion barrier induced a gradual decrease of the crystallite size of TiO2 films obtained by the sol-gel process. However, TiO2 obtained using the reactive sputtering method showed no dependence on the thickness of the SiN x barrier diffusion. The SiN x barrier diffusion showed a beneficial effect on the photocatalytic efficiency of TiO2 films regardless of the synthesis method used. The proposed mechanism leading to the improvement in the photocatalytic efficiency of the TiO2 films obtained by each process was discussed.