Two-dimensional assembly and local redox-activity of molecular hybrid structures in an electrochemical environment

The self-assembly and redox-properties of two viologen derivatives, N-hexyl-N-(6-thiohexyl)-4,4-bipyridinium bromide (HS-6V6-H) and N,N-bis(6-thiohexyl)-4,4-bipyridinium bromide (HS-6V6-SH), immobilized on Au(111)-(1x1) macro-electrodes were investigated by cyclic voltammetry, surface enhanced infrared spectroscopy (SEIRAS) and in situ scanning tunneling microscopy (STM). Depending on the assembly conditions one could distinguish three different types of adlayers for both viologens: a low coverage disordered and an ordered striped phase of flat oriented molecules as well as a high coverage monolayer composed of tilted viologen moieties. Both molecules, HS-6V6-H and HS-6V6-SH, were successfully immobilized on Au(poly) nano-electrodes, which gave a well-defined redox-response in the lower pA–current range. An in situ STM configuration was employed to explore electron transport properties of single molecule junctions Au(T)|HS-6V6-SH(HS-6V6-H)|Au(S). The observed sigmoidal potential dependence, measured at variable substrate potential ES and at constant bias voltage (ET–ES), was attributed to electronic structure changes of the viologen moiety during the one-electron reduction/re-oxidation process V2+ V+. Tunneling experiments in asymmetric, STM-based junctions Au(T)-S-6V6-H|Au(S) revealed current (iT)–voltage (ET) curves with a maximum located at the equilibrium potential of the redox-process V2+ V+. The experimental iT–ET characteristics of the HS-6V6-H–modified tunneling junction were tentatively attributed to a sequential two-step electron transfer mechanism.

Adsorption behavior of redox-active suppressor additives: Combined electrochemical and STM studies

The redox chemistry and the related surface phase behavior of Safranine (SAF) and Janus Green B (JGB) have been studied by means of cyclic voltammetry in combination with in situ Scanning Tunneling Microscopy using HOPG (Highly Oriented Pyrolytic Graphite) and single crystalline Cu(1 0 0) as model substrates, both revealing different widths of the accessible potential windows. JGB and SAF serve as prototypical heterocyclic suppressor/leveler additives that are used for the metallization of 3D-TSVs (3D Through Silicon Vias) following a classical "leveling" concept. SAF can be considered as the reductive decomposition product of JGB that is formed at the copper/electrolyte interface upon electroplating. Both additives reveal a pronounced pH-dependent redox-chemistry with redox-transitions lying close to or even beyond the anodic limit of the copper potential window. Affected by these redox-processes are in particular the aromatic cores of those heterocycles that can be (quasi)reversibly reduced by a two electron transfer process within the potential window of copper. Therefore we identify the reduced form of those dyes as the active components for the suppressing/leveling effect in copper plating. STM data clearly shows a dye surface phase behavior that is crucially determined by its potential-dependent redox-chemistry. This will be exemplarily discussed for the SAF dye. On chloride-modified Cu(1 0 0) mono-reduced SAF forms a structurally well-defined monolayer of cationic stacking polymers. However, this coupled anion/cation layer reveals only minor suppressing capabilities with respect to the copper dissolution and deposition processes. Complete reduction of the aromatic heterocycle finally leads to the 3D precipitation of hydrophobic reaction products. 3D clusters of this SAF precipitate are discussed as the active structural motif for the suppressing effect of these dyes. (C) 2011 Elsevier Ltd. All rights reserved.

Structural aspects of redox-mediated electron tunneling (Dedicated to the memory of professor Alexander M. Kuznetsov)

We investigated structural aspects of electron transfer (ET) in tunneling junctions (Au(1 1 1)vertical bar FcN vertical bar solution gap vertical bar Au STM tip) with four different redox-active N-thioalk(ano)ylferrocenes (FcN) embedded. The investigated molecules consist of a redox-active ferrocene (Fc) moiety connected via alkyl spacers with N = 4, 6, 8 and 11 carbon atoms to a thiol anchoring group. We found that for short FcNs (N = 4, 6,8) the redox-mediated ET response increases with the increase of the alkyl chain length, while no enhancement of the ET was observed for Fc1 1. The model of two-step ET with partial vibrational relaxation by Kuznetsov and Ulstrup was used to rationalize these results. The theoretical ET steps were assigned to two processes: (1) electron tunneling from the Fc group to the Au tip through the electrolyte layer and (2) electron transport from the Au(1 1 1) substrate to the Fc group through the organic adlayer. We argue that for the three short FcNs, the first process represents the rate-limiting step. The increase of the length of the alkyl chain leads to an approach of the Fc group to the STM tip, and consequently accelerates the first El' step. In case of the Fcl 1 junctions the rather high thickness of the organic layer leads to a decrease of the rate of the second ET step. In consequence, the contribution of the redox-mediated current enhancement to the total tunneling current appears to be insignificant. Our work demonstrates the importance of combined structural and transport approaches for the understanding of Er processes in electrochemical nanosystems. (C) 2010 Elsevier B.V. All rights reserved.

Layer-by-layer grown scalable redox-active ruthenium-based molecular multilayer thin films for electrochemical applications and beyond

Here we report the first study on the electrochemical energy storage application of a surface-immobilized ruthenium complex multilayer thin film with anion storage capability. We employed a novel dinuclear ruthenium complex with tetrapodal anchoring groups to build well-ordered redox-active multilayer coatings on an indium tin oxide (ITO) surface using a layer-by-layer self-assembly process. Cyclic voltammetry (CV), UV-Visible (UV-Vis) and Raman spectroscopy showed a linear increase of peak current, absorbance and Raman intensities, respectively with the number of layers. These results indicate the formation of well-ordered multilayers of the ruthenium complex on ITO, which is further supported by the X-ray photoelectron spectroscopy analysis. The thickness of the layers can be controlled with nanometer precision. In particular, the thickest layer studied (65 molecular layers and approx. 120 nm thick) demonstrated fast electrochemical oxidation/reduction, indicating a very low attenuation of the charge transfer within the multilayer. In situ-UV-Vis and resonance Raman spectroscopy results demonstrated the reversible electrochromic/redox behavior of the ruthenium complex multilayered films on ITO with respect to the electrode potential, which is an ideal prerequisite for e.g. smart electrochemical energy storage applications. Galvanostatic charge–discharge experiments demonstrated a pseudocapacitor behavior of the multilayer film with a good specific capacitance of 92.2 F g−1 at a current density of 10 μA cm−2 and an excellent cycling stability. As demonstrated in our prototypical experiments, the fine control of physicochemical properties at nanometer scale, relatively good stability of layers under ambient conditions makes the multilayer coatings of this type an excellent material for e.g. electrochemical energy storage, as interlayers in inverted bulk heterojunction solar cell applications and as functional components in molecular electronics applications.