This paper develops a parametric method for determining the core radius and shell thickness in small silver–silver-oxide core–shell nanoparticles (Nps) based on single particle optical extinction spectroscopy. The method is based on the study of the relationship between plasmon peak wavelength, full width at half maximum (FWHM) and contrast of the extinction spectra as a function of core radius and shell thickness. This study reveals that plasmon peak wavelength is strongly dependent on shell thickness, whereas FWHM and contrast depend on both variables. These characteristics may be used for establishing an easy and fast stepwise procedure to size core–shell NPs from single particle absorption spectrum. The importance of the method lies in the possibility of monitoring the growth of the silver-oxide layer around small spherical silver Nps in real time. Using the electrostatic approximation of Mie theory, core–shell single particle extinction spectra were calculated for a silver particle's core size smaller than about 20 nm and different thicknesses of silver oxide around it. Analysis of the obtained curves shows a very particular characteristic of the plasmon peak of small silver–silver-oxide Nps, expressed in the fact that its position is strongly dependent on oxide thickness and weakly dependent on the core radius. Even a very thin oxide layer shifts the plasmon peak noticeably, enabling plasmon tuning with appropriate shell thickness. This characteristic, together with the behaviour of FWHM and contrast of the extinction spectra can be combined into a parametric method for sizing both core and shell of single silver Nps in a medium using only optical information. In turn, shell thickness can be related to oxygen content in the Np's surrounding media. The method proposed is applied to size silver Nps from single particle extinction spectrum. The results are compared with full optical spectrum fitting using the electrostatic approximation in Mie theory. The method may be the basis for developing a plasmonic sensor for O2 concentration based on Ag single NP spectroscopy.

We report on the analysis of structure, configuration, and sizing of Cu and Cu oxide nanoparticles (Nps) produced by femtosecond (fs) laser ablation of solid copper target in liquids. Laser pulse energy ranged between 500 lJ and 50 lJ. Water and acetone were used to produce the colloidal suspensions. The study was performed through optical extinction spectroscopy using Mie theory to fit the full experimental spectra, considering free and bound electrons size dependent contributions to the metal dielectric function. Raman spectroscopy and AFM technique were also used to characterize the sample. Considering the possible oxidation of copper during the fabrication process, two species (Cu and Cu 2 O) arranged in two structures (bare core or core-shell) and in two configuration types (Cu-Cu 2 O or Cu 2 O-Cu) were considered for the fitting depending on the laser pulse energy and the surrounding media. For water at high energy, it can be observed that a CuCu 2 O configuration fits the experimental spectra of the colloidal suspension, while for decreasing energy and below a certain threshold, a Cu 2 O-Cu configuration needs to be included for the optimum fit. Both species coexist for energies below 170 lJ for water. On the other hand, for acetone at high energy, optimum fit of the full spectrum suggests the presence a bimodal Cu-Cu 2 O core-shell Nps distribution while for decreasing energy and below a 70 lJ threshold energy value, Cu 2 O-Cu core-shell Nps must be included, together with the former configuration, for the fit of the full spectrum. We discuss possible reasons for the changes in the structural configuration of the core-shell Nps. V C 2013 American Institute of Physics. [http://dx

Synthesis of nickel (Ni) nanoparticles (NPs) suspensions was performed using a 120 femtosecond (fs) pulse laser to ablate a Ni solid target in n-heptane and water.Analysis of structure, configuration and sizing was carried out using different independent techniques such as Optical Extinction Spectroscopy (OES), Atomic Force Microscopy (AFM), Transmission Electron Microscopy (TEM) and Electron Diffraction (ED), which yield interrelated information.AFM microscopy allows determining the spherical shape and size distribution of the NPs in the obtained colloids while TEM provides knowledge about shape, structure and size distribution. ED allows identification of the different metal and metal oxide composition as well as their crystallographic phase. On the other hand, OES gives information related to size distribution, structure, configuration and composition.Interpretation of these spectra is based on Mie theory which, in turn, depends on Ni dielectric function. For NPs radii smaller than 3 nm, size-dependent free and bound electron contributions to the dielectric function must be considered. To account for the full size span, complete Mie expansion was used for optical extinction cross-section calculations. A theoretical analysis of the dependence of plasmon resonance of bare core and core-shell Ni NPs with core size and shell thickness provide insight about their spectroscopic features.For n-heptane, species like bare core Ni and hollow Ni NPs are found in the colloid, being the latter reported for the first time in this work. Instead, for water, the colloid contains hollow nickel NPs and nickel oxide in different core-shell configurations: Ni-NiO and NiO-Ni, being the latter also reported for the first time in this paper. In both cases, size distribution agrees with that derived from TEM and AFM analysis. The formation of the oxide species is discussed in terms of oxidation-reduction processes during ablation. Possible mechanisms for the formation of hollow species are proposed.