Abstract:The voltage-induced assembly of mercaptosuccinic acid-stabilized Au nanoparticles of 1.5 ( 0.4 nm diameter is investigated at the polarizable water|1,2-dichloroethane interface. Admittance measurements and quasi-elastic laser scattering (QELS) studies reveal that the surface concentration of the nanoparticle at the liquid|liquid boundary is reversibly controlled by the applied bias potential. The electrochemical and optical measurements provide no evidence of irreversible aggregation or deposition of the particles at the interface. Analysis of the electrocapillary curves constructed from the dependence of the frequency of the capillary waves on the applied potential and bulk particle concentration indicates that the maximum particle surface density is 3.8 × 10 13 cm -2 , which corresponds to 67% of a square closedpack arrangement. This system provides a unique example of reversible assembly of nanostructures at interfaces, in which the density can be effectively tuned by the applied potential bias.

A new method is proposed for the fabrication of a well-defined size and shape distribution of silver nanoparticles in solution; the method employs direct laser irradiation of an aqueous solution containing a silver salt and a surfactant in the absence of reducing agents.

The use of 4.2 nm gold nanoparticles wrapped in an adsorbates shell and embedded in a TiO2 metal oxide matrix gives the opportunity to investigate ultrafast electron-electron scattering dynamics in combination with electronic surface phenomena via the surface plasmon lifetimes. These gold nanoparticles (NPs) exhibit a large nonclassical broadening of the surface plasmon band, which is attributed to a chemical interface damping. The acceleration of the loss of surface plasmon phase coherence indicates that the energy and the momentum of the collective electrons can be dissipated into electronic affinity levels of adsorbates. As a result of the preparation process, gold NPs are wrapped in a shell of sulfate compounds that gives rise to a large density of interfacial molecules confined between Au and TiO2, as revealed by Fourier-transform-infrared spectroscopy. A detailed analysis of the transient absorption spectra obtained by broadband femtosecond transient absorption spectroscopy allows separating electron-electron and electron-phonon interaction. Internal thermalization times (electron-electron scattering) are determined by probing the decay of nascent nonthermal electrons (NNEs) and the build-up of the Fermi-Dirac electron distribution, giving time constants of 540 to 760 fs at 0.42 and 0.34 eV from the Fermi level, respectively. Comparison with literature data reveals that lifetimes of NNEs measured for these small gold NPs are more than four times longer than for silver NPs with similar sizes. The surprisingly long internal thermalization time is attributed to an additional decay mechanism (besides the classical e-e scattering) for the energy loss of NNEs, identified as the ultrafast chemical interface scattering process. NNEs experience an inelastic resonant scattering process into unoccupied electronic states of adsorbates, that directly act as an efficient heat bath, via the excitation of molecular vibrational modes. The two-temperature model is no longer valid for this system because of (i) the temporal overlap between the internal and external thermalization process is very important; (ii) a part of the photonic energy is directly transferred toward the adsorbates (not among "cold" conduction band electrons). These findings have important consequence for femtochemistry on metal surfaces since they show that reactions can be initiated by nascent nonthermal electrons (as photoexcited, out of a Fermi-Dirac distribution) besides of the hot electron gas.

The spectroscopic and electrochemical properties of two-dimensional electrostatic assembly of Au nanocrystals are examined on poly-L-lysine (pLys) modified gold electrodes. The surface preparation for the nanoparticle deposition involved the selfassembly of a monolayer of 11-mercaptoundecanoic acid on the electrode surface, followed by the electrostatic deposition of pLys from aqueous solution. The polyelectrolyte layer acts as the electrostatic anchor for the Au particles. Electrostatically stabilised Au particles were prepared by homogeneous reduction in the presence of citrate, yielding monodispersed colloidal suspension with an average diameter of 18 AE 2 nm. After 4 h of deposition, the citrate-stabilised particles reach a maximum surface density of (8.2 AE 0.1) Â 10 10 particles cm À2 , with an average edge-to-edge distance of 25 nm. The particle surface density was estimated from scanning electron micrographs. Kelvin probe measurements were employed for examining changes in surface dipole introduced by the 2D array of nanocrystals. From simple electrostatic arguments, the apparent static dipole moment per particle was estimated of the order of 2700 D. The strong interaction between the nanocrystals and the pLys layer is responsible for the surface charge displacement, leading to changes in the surface dipole of 0.35 eV. These electrostatic interactions also manifest itself by the red shift of the plasmon resonance of the assembly with respect to the aqueous colloidal suspension. Analysis of the spectral broadening was attempted within the framework of the so-called coherent-potential approximation. Finally, electrochemical studies in 1,2-dichloroethane show a large electronic overlap between the nanocrystals and the metal substrate. Results obtained from electrochemical impedance spectroscopy strongly suggest that the electrostatic assembly of nanocrystal behaves like a 2D array of randomly distributed spherical nanoelectrodes.

The electrostatic layer-by-layer assembly of nanoparticles and polyelectrolytes is regarded as one of the most simple and versatile method for the construction of ultrathin organised multilayers.[1-10] The basic protocol is based on the seminal work by Decher on the formation of polyelectrolyte multilayers via al- [a] Dr.

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The emerging field of spintronics explores the many possibilities offered by the prospect of using the spin of the electrons for fast, nanosized electronic devices. The effect of magnetization acting on a current is the essence of giant or tunnel magnetoresistance. Although such spintronics effects already find technological applications, much of the underlying physics remains to be explored. The aim of this article is to demonstrate the importance of spin mixing in metallic nanostructures. Here we show that magnetic clusters embedded in a metallic matrix exhibit a giant magnetic response of more than 500% at low temperature, using a recently developed thermoelectric measurement. This method eliminates the dominating resistivity component of the magnetic response and thus reveals an intrinsic spin-dependent process: the conduction-electron spin precession about the exchange field as the electron crosses the clusters, giving rise to a spin-mixing mechanism with strong field dependence. This effect appears sensibly only in the smallest clusters, that is, at the level of less than 100 atoms per cluster. Spintronics seeks to exploit the interplay of spin-polarized conduction electrons and magnetization in nanostructures. Spin-dependent scattering leads to giant magnetoresistance [1][2][3][4][5] (GMR) and tunnelling magnetoresistance [6][7][8] , whereas the converse effect of a spin-polarized current on the magnetization 9-11 can be taken advantage of in magnetoresistive memory bits 12 and gigahertz oscillators 13 . GMR as a field sensing measurement of a resistivity ratio R/R is dominated by non-magnetic and spin-independent scattering processes determining R. Instead, the thermoelectric measurement protocol developed in our laboratory 14 depends on the first derivative of R with respect to the temperature and thus suppresses this resistive contribution. This allows us to fully reveal the otherwise negligible spin-mixing processes. In multilayers this mechanism is essentially a spin-dependent Peltier effect that roughly doubles the field sensitivity compared with GMR 14 . Here we have applied this measurement protocol to granular clusterassembled materials 15 , the geometry of which is not appropriate for a Peltier effect. Hence a clearly different microscopic mechanism takes a predominant role here. We invoke the predominance of spin mixing caused by a spin-precession effect 16 that is completely different in nature. Spin mixing was predicted to decrease GMR responses, as it scrambles the two spin channels of conduction. In our measurement scheme, on the contrary, it results in a 100-fold increase of the field response compared with GMR. The combined use of cluster-assembled materials and a novel measurement method thus reveal a different spin transport effect and may open a new route towards possible applications.Samples were prepared (see the 'Methods' section) according to the strategy of 'cluster-assembled materials' (Fig. 1). Briefly, the samples consist of thin films of copper in which well-defined cobalt clu...

The voltage induced assembly and photoreactivity of cadmium selenide (CdSe) nanoparticles protected by mercaptosuccinic acid are studied at the polarisable interface between water and 1,2-dichloroethane electrolyte solutions. Cyclic voltammograms and admittance measurements show an increase of the interface excess charge associated with the adsorption of CdSe nanoparticles as the Galvani potential difference is tuned to negative values with respect to the potential in the organic phase. Within the potential range where the nanoparticles are adsorbed, band-gap illumination leads to heterogeneous electron transfer from CdSe nanoparticles to electron acceptors located in the organic phase. The interfacial Galvani potential difference plays an important role in these phenomena, as it affects the interfacial density of the nanoparticles, as well as the driving force for the electron transfer. The photocurrent efficiency also strongly depends on the formal redox potential of the electron acceptor, indicating that the heterogeneous photoreaction is kinetically controlled. The interfacial electron transfer occurs via depopulation of the deep trap states in the band gap. Analysis of the photocurrent transient responses reveals that the magnitude of the instantaneous photocurrent upon illumination is determined by the kinetics of heterogeneous electron transfer, while photogenerated holes are swiftly captured by species present in the aqueous phase. The photocurrent decay upon constant illumination is associated with the diffusion of the acceptor to the interfacial region. From the phenomenological point of view, the photoelectrochemical behaviour of CdSe nanoparticles can be compared to a self-assembled ultrathin p-type semiconductor photoelectrode.