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A study is carried out on the electronic structure of gold nanoparticles embedded in a silica film, both before and after irradiation at 355 nm by a laser. The results show that before irradiation the gold atoms are in metallic states within the nanoparticles.

(C[sub 60]) [sub n] C[sup +][sub q] cationic clusters are produced in a laser vaporization source by quenching the vapors from C[sub 60] and graphite targets. They are analyzed in the gas phase by abundance and photofragmentation time-of-flight mass spectroscopy. Among the large number of expected isomers, the present experiments give evidence for the stability of special arrangements that may result from the attachment of preformed carbon rings to the fullerene cage. The particular case of C[sub 10] will be discussed, considering the results obtained on complexes with one, two or even three C[sub 60] molecules. This study reveals that the incorporation of large molecules into carbon cages could be an essential mechanism during the growth process of larger fullerenes and that the polymerization of C[sub 60] molecules is promoted by carbon links involving a single atom or a dimer. [ABSTRACT FROM AUTHOR]

Investigates the unimolecular decomposition of size selected cluster cations of trivalent metals induced by high fluence laser ionization. Method applied to photoexcited trivalent clusters generated in an evaporative ensemble; Experimental data covering a size range that was not explored in previous pioneering experiments on their dynamics.

An electrostatic quadrupole deviator is used to separate charged from neutral clusters produced by a laser vaporization source. Because of their rather constant velocity, this device which is basically an energy selector also acts as an efficient mass filter. We have simulated and studied its capability to generate beams of size-selected charged clusters. Typical beam currents of a few tens of pA allow the formation of two-dimensional cluster deposits within a few minutes. Platinum and indium clusters are deposited on electron microscopy grids coated with an amorphous carbon film. For low-density assemblies of particles in the nanometer range, size histograms are discussed in relation with the mass selectivity of the apparatus. An upper limit for the dispersion of selected cluster diameters is found to be of the order of ±8% which is at least five times better than the dispersion of neutral species. [ABSTRACT FROM AUTHOR]

(C60)mNan clusters are produced in a tandem laser vaporization source and analyzed by photoionization and photofragmentation time-of-flight mass spectroscopy. At low sodium coverage, the special behavior of (C60)m=1,2Nan clusters (n ≤ 6m) is consistent with a significant electron transfer from the first six adsorbed atoms towards each of the C60 fullerenes and an ionic-like bonding in this size range. However, the stability of the (C60)Na3+ cation is found much more pronounced than the one of (C60)Na7+ predicted to be a magic size under the hypothesis of a full charge transfer from the metal atoms to the C60 molecule. When more sodium atoms are present, metal-metal bonds tend to become preponderant and control the cluster properties. Relative to the number of sodium atoms, an odd-even alternation in their stability is explained by the high dissociation rates for even-numbered clusters. The even clusters evaporate neutral sodium atoms whereas odd ones prefer to evaporate Na2 molecules. The hypotheses for the growth of a sodium droplet that does not wet the fullerene surface or for the formation of a concentric metallic layer are discussed in the light of this study. [ABSTRACT FROM AUTHOR]

The diffusion and aggregation of preformed Agn-clusters ( n = 2-9) deposited onto a highly oriented pyrolytic graphite (HOPG) substrate is studied by two-photon-photoemission (2PPE). The sample is irradiated with ultrashort laser pulse pairs and the kinetic energy of the emitted photoelectrons is analyzed in a magnetic bottle type time-of-flight spectrometer. During annealing of the sample from 100 K up to room temperature, nanoparticles are formed on the surface by diffusion and aggregation of the silver clusters. A steep increase of the total photoelectron yield at a sample temperature of about 150 K is explained by the excitation of plasmons in the silver nanoparticles. From the kinetic energy distribution of the photoelectrons we deduce a strong variation of the work function of the sample during the formation of the nanoparticles, which is attributed to a quantum size effect. [ABSTRACT FROM AUTHOR]

Optical properties of mixed clusters (AuxAg 1 - x ) n and (NixAg 1 - x ) n, produced by laser vaporization and embedded in an alumina matrix, are reported. The size effects are investigated for different concentrations ( x = 0.25, 0.5 and 0.75) in the diameter range 2-4 nm. For alloyed clusters (AuxAg 1 - x ) n of a given size an almost linear evolution of the surface plasmon frequency ω s with the concentration is observed (between those of pure gold and pure silver clusters). Moreover the blue-shift and the damping of the resonance with decreasing size is all the more important as the gold concentration in the particles increases. Such results are in agreement with theoretical calculations carried out in the frame of the time-dependent local-density-approximation (TDLDA) including an inner skin of ineffective screening and the porosity of the matrix. The optical response of (NixAg 1 - x ) n clusters exhibits a surface plasmon resonance in the same spectral range as the one observed for pure silver clusters, but considerably damped and broadened. For a given mean cluster size 3.0 nm, a blue-shift of the resonance is observed when increasing the nickel concentration (between x = 0.25 and x = 0.75). The results are in good qualitative agreement with classical predictions in the dipolar approximation, assuming a core-shell geometry. [ABSTRACT FROM AUTHOR]

We use time resolved two photon photoemission to study the stability of size selected silver clusters deposited onto highly oriented pyrolytic graphite (HOPG) substrates. Size-selected Ag n + clusters ( n=2-9) are deposited at low coverage onto HOPG surfaces at liquid nitrogen temperatures. After deposition, the samples are irradiated by a series of ultrashort laser pulse pairs. Photoelectrons created by two photon photoemission are collected in a magnetic bottle type time-of-flight photoelectron spectrometer. Their kinetic energy distribution is recorded as a function of the delay time between subsequent light pulses. With the exception of Ag3 the size dependence of the photoelectron spectra reveals a pronounced odd/even effect, which is well known for gas phase silver clusters. This indicates that the deposited clusters retain their size and identity on the sample. The lifetime of the photoexcitation rises with cluster size. This is attributed to an increasing electronic density of states for larger clusters. [ABSTRACT FROM AUTHOR]

A new reflectron time-of-flight mass spectrometer with a cylindrical electrostatic mirror instead of the usual plane reflector is described. When it is mounted at right angles to the direction of an incoming molecular beam, this system automatically compensates for the transverse drift of the ions in the spectrometer due to their initial velocity parallel to the molecular beam direction. As a consequence, ions of any mass can be collected onto the detector, whatever their initial transverse velocity is. The mass range accessible in a single scan with our cylindrical reflectron is thus strongly increased as compared to the case of a usual plane reflectron. This article presents the general design of our cylindrical reflectron. A detailed description of the apparatus is given and its performances are illustrated on selected examples. Cluster mass spectra extending over a very wide size range are presented. A mass resolution of about 4000 is achieved in mass spectra of laser photoionized aluminum clusters. Moreover, the cylindrical geometry of the reflector gives rise to focusing properties onto the detector, which could be interesting in view of collection efficiency improvement. [ABSTRACT FROM AUTHOR]

Electronic shell and supershell structures in trivalent-metal clusters exhibit large discrepancies with the results of the conventional jellium model. For gallium the beat location in the supershell pattern is found around Ne=2500 valence electrons, in disagreement with the jellium model prediction Ne=1150. The discrepancies can be explained by a slight softness increase of the effective electronic potential at the surface. Theoretical calculations, taking into account ion pseudopotentials, within both local and nonlocal approaches, show that this softness arises to a large extent from the non-Coulombic short-range electron-ion interaction. [ABSTRACT FROM AUTHOR]

In order to understand laser-induced damage in glass, we subjected engineered SiO[sub 2] thin films containing sub-micron gold inclusions to high fluences, and observed the results using several means of analysis. We found decoupling in time between the emission of gold and that of silicon with samples containing gold spheres of diameter 3 nm. We have analyzed the changes in the silica optical absorption at 1064 nm, using photothermal deflection microscopy. We find, upon exceeding a sharp fluence threshold, a thousand-fold increase in absorption of the silica matrix around the inclusion. We conclude that ions from the inclusion permeate the surrounding silica, and form a highly absorbent mixture. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Several populations of Cu spherical nanoparticles grown in a silicate glass at different temperatures with respect to the glass transition temperature were studied using high-resolution, low-frequency Raman scattering and optical absorption. The analysis of the spectra shows that the annealing of the doped glass at temperatures close to Tg leads to the formation of metallic copper nanoparticles with high crystallinity, whereas lower-temperature and higher-temperature annealings result in the formation of poorer nanoparticle assemblies in terms of size distribution and/or nanocrystallinity. It is also shown that in the case where the optical data do not unambiguously reveal the presence of metallic Cu nanoparticles, the Raman probe enables us to probe their presence as a result of the resonance process. [ABSTRACT FROM AUTHOR]

In this study, the atomic and chemical structure and the optical response of A x B 1- x bimetallic nanoparticles (BNPs) combining gold or silver (A) with aluminium or indium (B) were investigated at various stoichiometries in order to examine if stable alloyed phases could exist and promote the emergence of localized surface plasmon resonance (LSPR) in the UV range. The structure and morphology of BNPs of a few nanometres, produced by laser vaporization, were analysed by transmission electron microscopy (TEM) and optical absorption measurements were performed on matrix-embedded BNPs. Information about the oxidation state of the BNPs can be inferred from a comparison between experimental optical spectra and Mie calculations in the dipolar approximation. The BNPs' internal structures were further investigated by additional characterization techniques. Firstly, in situ X-ray photoelectron spectroscopy provided information about the chemical state of the constituent elements and their evolution with time. Secondly, synchrotron-based X-ray scattering techniques were performed on Ag-Al BNPs in a wide-angle configuration under grazing incidence, giving complementary information about structural and morphological heterogeneities in the BNPs. Finally, the restructuring of the partially oxidized Au 0.33 Al 0.67 BNPs annealed in a reducing atmosphere was also attempted by environmental TEM. The complementary techniques of characterization show that silver-based Ag-In and Ag-Al BNPs form metallic silver-rich alloyed cores surrounded by an indium or aluminium oxide shell. The initial LSPR is in the UV range for both systems, but the difference in the kinetics of oxidation between indium and aluminium involves less blue-shifted LSPR for Ag-Al BNPs. In the case of gold-based BNPs, we show evidence of ordered nanoalloys just after air exposure and the appearance of gold and indium (or aluminium) demixing during oxidation. The initial LSPR of Au-In BNPs is the one the most in the UV range among the four systems, with an LSPR peak centred at 254 nm, which may be a sign of the formation of the Au 0.33 In 0.67 alloy. Nevertheless, strategies to preserve BNPs from oxidation have to be developed.

Using time-resolved ultrafast pump-probe spectroscopy we investigated the electron-lattice energy transfer in small copper nanospheres with diameters ranging from 3.2 to 23 nm, either embedded in a glass or dispersed in a solvent. Electron-lattice scattering rate is shown to increase with size reduction, in agreement with our previous results obtained on gold and silver nanoparticles in the low excitation regime. We attribute this effect to the reduction of the screening efficiency of electron-phonon interactions close to the nanoparticle surface. To understand the discrepancy between the results on the electron-lattice scattering in different metals reported in the literature (reduction, no dependence or increase with nanoparticle size), we discuss the experimental conditions required for the accurate determination of electron-lattice energy transfer time from time-resolved investigations in the weak and strong excitation regimes and present power-dependent experiments on gold nanospheres in solution. Our findings are derived from a theoretical analysis based on the two-temperature model predictions and on a complete modeling of the nanoparticle transient extinction cross-section through the resolution of Boltzmann equation in the presence of hot electrons.

Sensitive, robust and stable sensors are required to bring biosensing techniques from the forefront of research to clinical and commercial settings. To this end, we report on the development of new robust plasmonic sensors consisting of gold nano-bipyramids (BPs) grafted to a glass substrate via silanization, associated with a novel setup based on Spatial Modulation Spectroscopy allowing the measurement of the optical response of individual nano-objects in a liquid environment. We thereby show that changes in the refractive index of the medium around individual silanized BPs can be detected by measuring their plasmonic shift with sensitivities comparable to values reported elsewhere and in good agreement with theoretical calculations. The optical response is furthermore shown to be stable and robust allowing for repeated measurements in different media and storage over many months. This work opens up new perspectives in the field of plasmonic bio-sensing as our setup is readily adaptable to dynamic liquid measurements and a wide range of applications such as the detection of clinically important analytes or pollutants in water.

The acoustic vibrations of single monomers and dimers of gold nanoparticles were investigated by measuring for the first time their ultralow-frequency micro-Raman scattering. This experiment provides access not only to the frequency of the detected vibrational modes but also to their damping rate, which is obscured by inhomogeneous effects in measurements on ensembles of nano-objects. This allows a detailed analysis of the mechanical coupling occurring between two close nanoparticles (mediated by the polymer surrounding them) in the dimer case. Such coupling induces the hybridization of the vibrational modes of each nanoparticle, leading to the appearance in the Raman spectra of two ultralow-frequency modes corresponding to the out-of-phase longitudinal and transverse (with respect to the dimer axis) quasi-translations of the nanoparticles. Additionally, it is also shown to shift the frequency of the quadrupolar modes of the nanoparticles. Experimental results are interpreted using finite-element simulations, which enable the unambiguous identification of the detected modes and despite the simplifications made lead to a reasonable reproduction of their measured frequencies and quality factors. The demonstrated feasibility of low-frequency Raman scattering experiments on single nano-objects opens up new possibilities to improve the understanding of nanoscale vibrations with this technique being complementary with single nano-object time-resolved spectroscopy as it gives access to different vibrational modes.

Multimetallic nano-alloys display a structure and consequently physicochemical properties evolving in a reactive environment. Following and understanding this evolution is therefore crucial for future applications in gas sensing and heterogeneous catalysis. In view hereof, the structural evolution of oxidized Ag 25 In 75 bimetallic nanoparticles under varying H 2 partial pressures (P H 2 ) and substrate temperatures (T s ) has been investigated in real-time through environmental transmission microscopy (E-TEM) while maintaining the atomic resolution. Small Ag 25 In 75 bimetallic nanoparticles, produced by laser vaporization, are found (after air transfer) to contain an indium-oxide shell surrounding a silver-rich alloyed phase. For high P H 2 and T s , the direct reduction of the indium oxide shell, immediately followed by the melting or the diffusion onto the carbon substrate of the reduced indium atoms, is found to be the dominant mechanism. This reduction is concomitant with the growth of the core, indicating a partial diffusion of indium atoms from the shell towards the particle volume. The "surviving" particles therefore consist of a silver-indium alloy, very stable and remarkably resistant against oxidation contrary to native clusters. Interestingly, in the (P H 2 , T s ) space, the transition from "soft" (core-shell particles for low (P H 2 , T s ) values) to "strong" reduction conditions (silver-rich alloys for high (P H 2 , T s ) products) defines an intermediate domain where the preferred formation of Janus structures is detected. These results are discussed in terms of thermodynamic driving forces in relation to alloying and interface energies. This work shows the potential of high-resolution ETEM for unravelling the mechanisms of nanoparticle reorganization in a chemically reactive environment.

Homodimers of noble metal nanocubes form model plasmonic systems where the localized plasmon resonances sustained by each particle not only hybridize but also coexist with excitations of a different nature: surface plasmon polaritons confined within the Fabry-Perot cavity delimited by facing cube surfaces (i.e., gap plasmons). Destructive interference in the strong coupling between one of these highly localized modes and the highly radiating longitudinal dipolar plasmon of the dimer is responsible for the formation of a Fano resonance profile and the opening of a spectral window of anomalous transparency for the exciting light. We report on the clear experimental evidence of this effect in the case of 50 nm silver and 160 nm gold nanocube dimers studied by spatial modulation spectroscopy at the single particle level. A numerical study based on a plasmon mode analysis leads us to unambiguously identify the main cavity mode involved in this process and especially the major role played by its symmetry. The Fano depletion dip is red-shifted when the gap size is decreasing. It is also blue-shifted and all the more pronounced that the cube edge rounding is large. Combining nanopatch antenna and plasmon hybridization descriptions, we quantify the key role of the face-to-face distance and the cube edge morphology on the spectral profile of the transparency dip.

The optical absorption of bimetallic nanoparticles M-Ag involving silver as an active plasmonic compound has been the subject of very extensive experimental studies, both for a large range of sizes and a large variety of associated metals. Considering the most commonly encountered core-shell segregated configuration M@Ag involving a transition metal M, the spectral response is found to be weakly discriminating with regard to the chemical order and composition and is characterized by a large unstructured plasmon resonance in the 2 eV to 4 eV range. The plasmon band is essentially shaped by the scars made in the absorption continuum of metal M by Fano-like induced resonances and is surprisingly little sensitive to the exact nature of this metal, giving birth to a "quasi universal" optical signature for M@Ag systems. In this paper, we show how this generic behaviour arises from the specific plasmonic response of silver and stress the role of interband transitions of both metals through their coupling with the free electron oscillation modes. This theoretical discussion will be illustrated through selected experimental results.