Stress state of silver nanoparticles embedded in a silicate glass matrix investigated by HREM and EXAFS spectroscopy

Ag particles of 3.9 and 5.1 nm mean size in silicate glasses were produced by ion exchange and subsequent annealing at 480 and 600 ^°C. These thermal treatments may induce stresses in matrix and particles in addition to the well known effect of surface atoms because of the thermal expansion mismatch of both materials. Structural characterisation of the particles by high-resolution electron microscopy revealed a size-dependent lattice dilatation quite opposite to the so far observed lattice contraction of similar metal/glass composites. This result, confirmed by X-ray absorption spectroscopy at the Ag K-edge, is discussed in terms of an Ag-Ag bond length increase near the particle surface. The temperature-dependent EXAFS spectra (10-300 K) indicate an increased thermal expansion coefficient of the particles with an increased mean particle size calculated on the basis of an anharmonic Einstein model. With that the bond length increase can be explained. The results can be interpreted by a combination of both the particle size effects and the influence of the surrounding matrix. Received 30 November 2000     

From anisotropic dots to smooth RFe 2 (110) single crystal layers (R = rare earth)

Single crystal RFe₂(110) films were grown by molecular beam epitaxy to a total thickness of 1000 ? at different substrate temperatures ranging from 450 ^° C to 660 ^° C. The first stages of growth and the surface morphology of the deposited layers have been studied using Reflection High Energy Electron Diffraction (RHEED) and Atomic Force Microscopy (AFM). The growth is first strained but further deposit induces the formation of three-dimensional fully relaxed islands. Subsequently, the morphology of the RFe₂(110) nanosystems evolves from anisotropic dots to a smooth surface, as a function of the preparation parameters, i.e. nominal thickness and substrate temperature. It also depends on the rare earth involved in the compound. Received 29 June 2000     

Coalescence process of monodispersed Co cluster assemblies

Cluster-cluster coalescence process of monodispersed Co clusters with mean diameter d = 8.5 and 13 nm deposited a plasma-gas-condensation-type cluster beam deposition system was investigated by in situ electrical conductivity measurements and ex situ scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and analyzed by percolation concept. The electrical conductivity measurement and TEM observation indicated that, below temperature T≈ 100^°C, the Co clusters in the assemblies maintain their original structure as deposited at room temperature, while that the inter-cluster coalescence takes place at T > 100^°C, although the size distribution and the interface morphology of the clusters showed no marked change at substrate temperatures T _s≤200^°C. Received 29 November 2000     

Fabrication of bismuth telluride nanotubes via a simple solvothermal process

The unique Bi₂Te₃ tubes were obtained via a simple solvothermal reaction in the presence of ethylenediaminetetraacetic acid disodium salt. The product was characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Bi₂Te₃ nanosheets are vertically grown off the tube wall to form Bi₂Te₃ tubes. A possible formation mechanism is proposed.     

Growth of tellurium clusters in presence of metal impurities

The growth of small tellurium clusters in helium and the influence of a metal impurity (dysprosium atoms) on the cluster size distribution are investigated in a double laser vaporization source. A model describing the role of the carrier gas as collision partner is presented, emphasizing the crucial influence of the gas pressure on cluster formation. Changes in cluster reactivity due to dysprosium addition are discussed in terms of ionic structures Dy ^{3 +}(Te _N)^{3 -} containing a radical electron. Received 28 November 2000     

Effect of montmorillonite filler on structural and electrical properties of polymer nanocomposite electrolytes

Polymer–clay nanocomposites consisting of polymer (polyethylene oxide) and NaI as salt with different concentration of organically modified Na⁺-montmorillonite (DMMT) have been fabricated and characterized. X-ray diffraction analysis shows that the polymer–salt complexes have been intercalated into the nanometric silicate layers of DMMT. Fourier transform infrared analysis shows that the polymer structure in the clay interlayer is similar to that of the polymer–salt complexes, and there is a strong interaction between the polymer–salt complexes and clay layers. A study of surface morphology using scanning electron microscopy reveals that microstructure of composites is affected by clay addition. Complex impedance analysis was used to calculate the bulk resistance of the composites. An enhancement in the conductivity of about one order of magnitude has been observed on 5% clay addition compared to that of the polymer–salt complexes, and it decreases monotonically for higher clay concentration. The effect of clay concentration on the structural and physical properties of polymer nanocomposites is well correlated.     

Phase transitions in Co nanoclusters grown by pulsed laser deposition

The crystalline structure of Co clusters embedded in an amorphous Al₂O₃ matrix was studied by transmission electron microscopy (TEM) and electron diffraction (TED). In the first stage of the growth a metastable structure (body-centred-cubic) is observed. A face-centred-cubic phase (fcc) is found when the size of the clusters increases ( diameter > 4 nm). The hexagonal-close-packed phase arises in the fcc phase by a succession of stacking faults at the largest sizes. The mechanisms of phase transformation have been determined by using high resolution electron microscopy (HREM). The chemical nature of the clusters, in particular the existence of Co-O bonds, was investigated by using electron energy loss spectroscopy (EELS). Received 03 July 2000 and Received in final form 22 December 2000     

The effect of oxidation on the structure of nickel nanoparticles

The structural properties of nickel nanoparticles which are prepared by means of DC sputtering in argon and subsequently oxidized in ambient air are reported. Ex situ structural and chemical investigations utilizing (high resolution) transmission electron microscopy and electron energy loss spectroscopy reveal that the particles consist of a metallic core surrounded by an oxide shell. The lattice constant of the nickel core is found to increase significantly with decreasing particle size. This widening of the nickel lattice is attributed to an interfacial stress that originates from the lattice mismatch between nickel and nickel oxide. Received 21 December 2000     

Branched crystal morphology of linear polyethylene crystallized in a two-dimensional diffusion-controlled growth field

The branched crystal morphology of linear polyethylene formed at various temperatures from thin films has been studied by atomic-force microscopy (AFM), transmission electron microscopy (TEM), electron diffraction (ED) pattern and polymer decoration technique. Two types of branched patterns, i.e. dendrite and seaweed patterns, have been visualized. The fractal dimension d _f = 1.65 of both dendrite and some of seaweed patterns was obtained by using the box-counting method, although most of the seaweed patterns are compact. Selected-area ED patterns indicate that the fold stems tilt about 34.5^° around the b-axis and polymer decoration patterns show that the chain folding direction and regularity in two (200) regions are quite different from each other. Because of chain tilting, branched crystals show three striking features: 1) the lamella-like branches show two (200) regions with different thickness; 2) the crystals usually bend towards the thin region; 3) the thick region grows faster by developing branches, thus branches usually occur outside the thick region. The branched patterns show a characteristic width w, which gives a linear relationship with the crystallization temperature on a semilogarithmic plot. Received 15 March 2002 and Received in final form 29 April 2002     

Nanoparticles superficial density of charge in electric double-layered magnetic fluid: A conductimetric and potentiometric approach

We analyze potentiometric and conductimetric measurements simultaneously performed on Electric Double-Layer Magnetic Fluid based on cobalt ferrite nanoparticles, in order to obtain the pH-dependence of the particle surface charge density. We propose a mechanism for the charging of the particle surface. This model considers the ferrofluid solution as a mixture of strong and weak diprotic acids. We show how an exact analytical treatment involving proton transfer between the particle surface and the bulk solution allows the construction of a speciation diagram of the charged superficial sites. The saturation value of the superficial density of charge is found to be equal to 0.326 ± 0.065 C m^-2. Received 9 May 2001 and Received in final form 17 July 2001     

Dielectric resonances in disordered media

Binary disordered systems are usually obtained by mixing two ingredients in variable proportions: conductor and insulator, or conductor and super-conductor. They present very specific properties, in particular the second-order percolation phase transition, with its fractal geometry and the multi-fractal properties of the current moments. These systems are naturally modeled by regular bi-dimensional or tri-dimensional lattices, on which sites or bonds are chosen randomly with given probabilities. The two significant parameters are the ratio h = σ ₁/σ of the complex conductances, σ and σ ₁, of the two components, and their relative abundances p (or, respectively, 1 - p). In this article, we calculate the impedance of the composite by two independent methods: the so-called spectral method, which diagonalises Kirchhoff's Laws via a Green function formalism, and the Exact Numerical Renormalization method (ENR). These methods are applied to mixtures of resistors and capacitors (R-C systems), simulating e.g. ionic conductor-insulator systems, and to composites constituted of resistive inductances and capacitors (LR-C systems), representing metal inclusions in a dielectric bulk. The frequency dependent impedances of the latter composites present very intricate structures in the vicinity of the percolation threshold. In this paper, we analyse the LR-C behavior of compounds formed by the inclusion of small conducting clusters (“n-legged animals”) in a dielectric medium. We investigate in particular their absorption spectra who present a pattern of sharp lines at very specific frequencies of the incident electromagnetic field, the goal being to identify the signature of each animal. This enables us to make suggestions of how to build compounds with specific absorption or transmission properties in a given frequency domain. Received 16 August 2002 Published online 14 February 2003 RID="a" ID="a"e-mail: laurent.raymond@l2mp.fr RID="b" ID="b"e-mail: steffen.schaefer@l2mp.fr RID="c" ID="c"UMR CNRS 6137     

Coherent transport through intramolecular junction of single-wall carbon nanotubes

We have constructed four types single-wall carbon nanotube intramolecular junctions (IMJs) of (5,5)/(8,0), (5,5)/(10,0), (5,5)/(9,0)A, and (5,5)/(9,0)B along a common axis, and calculated their electronic and transport properties using a tight binding-based Green's function approach that is particular suitable for realistic calculation of electronic transport property in extended system. Our results show that quasi-localized states can appear in the metal/semiconductor heterojunctions ((5,5)/(8,0) and (5,5)/(10,0)junctions), which is desirable for the design of a quantum device; and the conductance of M-M IMJs is very sensitive to the connectivity of the matching tubes, certain configurations of connection completely stop the flow of electron, while others permit the transmission of the current through the interface. These results may have implications for the device assembly and manipulation process of all carbon nanotubes-based microelectronic elements. Received 14 January 2003 / Received in final form 25 February 2003 Published online 4 June 2003 RID="a" ID="a"e-mail: lfyzz@yahoo.com.cn     

Spin-polarized tunneling in ferromagnetic double barrier junctions

Spin-polarized tunneling in FMS/M/FMS double tunnel junctions where FMSs are ferromagnetic semiconductor layers and M is a metal spacer is studied theoretically within the single-site coherent potential approximation (CPA). The exchange interaction between a conduction electron and localized moment of the magnetic ion is treated in the framework of the s-f model. The spin polarization in the FMS layers is observed to oscillates as a function of the number of atomic planes in the spacer layer. Amplitude of these oscillations decreases with increasing the exchange interaction in FMS layers. Received 9 June 2001 and Received in final form 20 August 2001     

Modeling of recognition sites of nucleic acid bases aaand amide side chains of amino acids. Combination of experimental and theoretical approaches

A combined experimental-theoretical approach to modeling of building blocks of recognition complexes formed by nucleic acid bases and the amino-acids side-chain amino group is reviewed. The approach includes the temperature dependent field-ionization mass spectrometry and ab initio quantum chemical calculations. The mass spectrometric technique allows determination of interaction enthalpies of biomolecules in the gas phase, and the results it produces are directly comparable to the results obtained through theoretical modeling. In our works we have analyzed both thermodynamic and structural aspects of the recognition complexes of four canonical nucleic acid bases and acrylamide, which models the side chain of asparagine and glutamine. It has been shown that all bases can interact with amide group of the amino acids via their Watson-Crick sites when being incorporated into a single strand DNA or RNA. Stability of the complexes studied, expressed as - ΔH (kJ mole^-1) decreases as: m⁹Gua (- 59.5) > m ¹Cyt (- 57.0) > m ⁹Ade (- 52.0) ≫m ¹Ura (- 40.6). We have determined that in the double stranded DNA only purine bases can be recognized. Received 5 February 2002 and Received in final form 14 March 2002 Published online 13 September 2002     

Growth velocity and the topography of Ni-Zn binary alloy electrodeposits

We show that the electrodeposition of Ni-Zn alloys at the lowest growth velocities, v < 0.5μm/s, exclusively proceeds from an abnormal co-deposition phenomenon. The growth process in this v region greatly depends on the initial [Co²⁺] concentration of the film deposition bath. A theoretical approach of this process including the role of the saturation surface roughness of the alloy, , leads to an estimation of the transport properties of the ad-atoms involved during the deposit formation. Their surface diffusion coefficient varying between 1.76×10^-10 and 2.40×10^-8 cm^-2/s exhibits a minimal value, D _s = 2.10×10^-10 cm^-2/s located between v = 0.17 and 0.35μm/s. The spatial scaling analysis of the local roughness, σ, examined according to the power-law σ≈L ^α reveals that the resulting roughness exponents concurs with the Kardar-Parisi-Zhang dynamics including the restricted surface diffusion. Two main v regions leads to different fractal textural features of the alloy film surface. Below 0.10 μm/s, the roughness exponent obtained is α≈ 0.6, depicting a limited ad-atom mobility. Over v = 0.30μm/s, this exponent stabilises at α≈ 0.82, indicating an increase of the surface diffusion. Received 16 August 2000 and Received in final form 20 June 2001     

Stabilisation of fcc cobalt layers by 0.4 nm thick manganese layers in Co/Mn superlattices

Epitaxial Co/Mn multilayers (0.75 to 6 nm Co, 0.4 nm Mn layer thickness) have been grown on mica substrates covered by a (0002) Ru buffer layer. The structural properties of these layers have been studied using X-ray diffraction, nuclear magnetic resonance (NMR), and high resolution transmission electron microscopy (HRTEM). The Co layers, grown as face centred cubic (fcc), were found to be stabilised by the very thin Mn layers. Data obtained using X-ray diffraction and NMR were analysed and found to be in good agreement, while Monte-Carlo simulations were used to interpret the data and calculate the expected diffracted intensity and NMR spectra. The HRTEM data show that the Mn layers give rise to a large strain contrast extending, in the growth direction, over a distance which exceeds the thickness of the Mn layers. The superlattices could be described as having an fcc structure containing randomly located stacking faults with varying densities. The results verify the presence of a dominant, almost perfect phase of fcc stacking, and of a faulted hcp phase, while the number of defects increases with the Co layer thickness. Received 27 October 1999 and Received in final form 29 May 2000     

Nanostructures of gold coated iron core-shell nanoparticles and the nanobands assembled under magnetic field

Pure metal iron nanoparticles are unstable in the air. By a coating iron on nanoparticle surface with a stable noble metal, these air-stable nanoparticles are protected from the oxidation and retain most of the favorable magnetic properties, which possess the potential application in high density memory device by forming self-assembling nanoarrays. Gold-coated iron core-shell structure nanoparticles (Fe/Au) synthesized using reverse micelles were characterized by transmission electron microscopy (TEM). The average nanoparticle size of the core-shell structure is about 8 nm, with about 6 nm diameter core and 1∼2 nm shell. Since the gold shell is not epitaxial growth related to the iron core, the morié pattern can be seen from the overlapping of iron core and gold shell. However, the gold shell lattice can be seen by changing the defocus of TEM. An energy dispersive X-ray spectrum (EDS) also shows the nanoparticles are air-stable. The magnetic measurement of the nanoparticles also proved successful synthesis of gold coated iron core-shell structure. The nanoparticles were then assembled under 0.5 T magnetic field and formed parallel nanobands with about 10 μm long. Assembling two dimensional ordered nanoarrays are still under going. Received 29 November 2000     

Barrier-free intermolecular proton transfer in the uracil-glycine complex induced by excess electron attachment

The photoelectron spectra (PES) of anions of uracil-glycine and uracil-phenylalanine complexes reveal broad features with maxima at 1.8 and 2.0 eV. The results of ab initio density functional B3LYP and second order M?ller-Plesset theory calculations indicate that the excess electron occupies a π^* orbital localized on uracil. The excess electron attachment to the complex can induce a barrier-free proton transfer (BFPT) from the carboxylic group of glycine to the O8 atom of uracil. As a result, the four most stable structures of the anion of uracil-glycine complex can be characterized as the neutral radical of hydrogenated uracil solvated by the anion of deprotonated glycine. The similarity between the PES spectra for the uracil complexes with glycine and phenylalanine suggests that the BFPT is also operative in the case of the latter anionic species. The BFPT to the O8 atom of uracil may be related to the damage of nucleic acid bases by low energy electrons because the O8 atom is involved in a hydrogen bond with adenine in the standard Watson-Crick pairing scheme. Received 6 April 2002 Published online 13 September 2002     

Low energy electron attachment to formic acid

Using a high resolution electron energy monochromator low energy electron attachment to formic acid is studied for the first time by means of mass spectrometric detection of the product anions. The largest dissociative electron attachment (DA) cross-section produces HCOO ^-+H with weaker channels for OH^- and O^- becoming apparent at higher incident energies. Received 23 January 2002 and Received in final form 9 February 2002 Published online 13 September 2002     

Microphase separation in weakly charged hydrophobic polyelectrolytes

Aqueous solutions of a well-defined poly(N-isopropylacrylamide-co-sodium 2-acrylamido-methylpropanesulfonate) (NIPAM/NaAMPS in a 95/5 molar ratio) have been investigated by means of small-angle neutron scattering (SANS) and rheological experiments as a function of temperature ( 25^° C T 60^° C) and polymer concentration ( 0.5wt% C 12wt%). The solutions remain optically transparent and isotropic over the whole temperature range, in contrast with the homopolyNIPAM which precipitates above its lower critical solution temperature (LCST = 32^° C). Upon addition of salt, the systems undergo a micro-macrophase separation. At temperatures above 45^° C, the SANS spectra exhibit a sharp peak at a scattering wave vector, q _max, which increases slightly with temperature. At high temperature ( T∼ 60^° C), the scattered intensity follows a power law I(q) ∼q ^-4 in the asymptotic regime, characteristic of two-density media with sharp interfaces, and q _max is found to vary with polymer concentration as q _max∼C ^0.22. Estimates of the typical sizes give values between 40 ? and 200 ?. These results provide a strong evidence of a thermally induced microphase separation, which is corroborated by the very sharp increases of the viscosity (over 2 decades) and of the stress relaxation time of the solutions, occurring in the temperature range where the scattering peak is observed. The results are discussed and compared with the theoretical models proposed for weakly charged polyelectrolytes in a poor solvent. Received 1 October 2001