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.     

A Mössbauer and Electrochemical Characterization of the Corrosion Products Formed from Marine and Marine-Antartic Environments

Hyperfine Interactions - Corrosion products formed on low alloy steel under two marine environments are characterised. Both environments are classified as C4 according to the ISO 9223 Standard. The...     

A transparent solid-state ion gel for supercapacitor device applications

Journal of Solid State Electrochemistry - A feasibility study of the synthesis of gel polymer electrolytes based in methyl methacrylate (MMA) and 1-vinyl-2-pyrrolidone (VP) using [HEMIm][BF4] as...     

Crystallographically-oriented single-crystalline copper nanowire arrays electrochemically grown into nanoporous anodic alumina templates

Highly crystallographically-oriented single-crystalline copper nanowire arrays were electrochemically deposited into nanoporous commercial alumina templates. A gold/copper backward contact was needed in the template, while the nanowires were grown from a 0.5 M CuSO₄·5H₂O solution adjusted to pH=1. The kinetics of the growing process is studied by means of current vs. time curves. The pore filling is between 80 to 90%. The structure and morphology of the wires are studied by XRD, SEM and TEM. The wires have an average diameter of 150 nm corresponding to the pore diameter of the template, with the cubic face-centered copper structure. This structure is highly oriented along the [100] direction parallel to the wire axis. The preferential growing along this direction was not previously found in the literature, which may have interesting applications when such direction is required. PACS 81.05.Bx; 82.45.Qr; 81.07.-b     

Seed layer effect on morphological,structural, and optical properties of electrochemically grown ZnO nanowires over different SnO2:F/glass substrates

Journal of Solid State Electrochemistry - Transparent conductive oxide electrodes and specifically SnO2:F/glass are widely employed substrates in the preparation of optoelectronic devices. This...