An AFM, XPS and electrochemical study of molecular electroactive monolayers formed by wet chemistry functionalization of H-terminated Si(1 0 0) with vinylferrocene

Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η⁵-C₅H₅)Fe²⁺(η⁵-C₅H₄)-CH₂-CH₂-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe³⁺ at the expenses of Fe²⁺ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO⁻ groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe³⁺ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing.     

Liquid–gas critical phenomena under confinement: small-angle neutron scattering studies of CO2 in aerogel

Small angle neutron scattering (SANS) is a well-established technique for investigating the behavior of confined binary liquid solutions, as it can probe the correlation length and susceptibility in pores on length scales 1 – 100 nm. We applied SANS to explore the influence of confinement on critical behavior of an individual fluid carbon dioxide (CO₂) in a highly porous aerogel. The results demonstrate that quenched disorder induced by aerogel significantly depresses density fluctuations. Despite the negligible volume occupied by aerogel (< 4%), the macroscopic phase separation of confined CO₂ into coexisting liquid and gaseous phases is suppressed and below the critical temperature of the bulk fluid frozen methastable microdomains are formed. Experimental data show that critical adsorption is as important as the effect of confinement in defining the behavior of confined fluids.     

Stress-Strain State in the Zone of Load Transfer in a Composite Specimen under Uniaxial Tension

The stress-strain state in the zone of load transfer in a uniaxially stretched specimen made of a unidirectional epoxy carbon-fiber-reinforced plastic (CFRP) is investigated. A parametric analysis of the influence of geometric and mechanical characteristics of the specimen on its stress-strain state is performed by means of finite-element modeling. The parameters allowing us to significantly reduce the dangerous concentration of transverse and tangential stresses are revealed. The mechanical tensile characteristics of a high-strength pultruded unidirectional CFRP are determined experimentally, and the size effect of its strength is estimated.     

Energy Spectrum Width and Nonequilibrium Energy of Rayleigh Waves Scattered on a Two-Dimensional Near-Surface Electron Layer

We obtain expressions for the energy spectrum widths of Rayleigh waves corresponding to their deformational coupling to Fermi and Boltzmann electrons in a two-dimensional layer near the surface of a semibounded solid. We evaluate the nonequilibrium energy of Rayleigh waves that depends on these widths and is caused by the same coupling to the corresponding hot electrons. We show that this energy is independent of the degeneracy degree of the electrons and is given by the mean energy of free Rayleigh waves heated up to temperature of the electrons. We find conditions under which the thermodynamics is determined by this nonequilibrium energy of Rayleigh waves in films of a certain thickness with Fermi electrons near the surface and by the equilibrium energy of bulk phonons in thicker samples. All the results are obtained using the Keldysh diagram technique applied to the case of semibounded media.     

An Algebraic Method for the Exact Solution of the Partition Function of the Canonical Ensemble in Nuclear Multifragmentation

We propose a unified method for deducing recursive relations for the canonical partition function of a system of noninteracting particles with charge conservation if the particles follow the Bose–Einstein, Fermi–Dirac, or Maxwell–Boltzmann statistics or parastatistics. For all these types of statistics, we find recursive relations for the partition function of a new statistical model of nuclear multifragmentation with electric charge and baryon number conservation, accounting for the internal degrees of freedom of the nuclear fragments.     

Periodic Optical Pulses in Nonlinear Optical Fibers

We discuss the problem of transmitting polarized pulses along optical fibers with variable dispersion. The dissipation and mean dispersion are assumed to be zero, which allows using the model of the vector nonlinear Schrödinger equation. We consider an optical fiber consisting of arms of equal length, which is assumed to be large. We propose an asymptotic recursive procedure for calculating the amplitude and the phase of an optical pulse propagating along the optical cable with variable dispersion.     

53rd Meeting of the International Society of Electrochemistry

Russian Journal of Electrochemistry -