Kinetics of electrochemically controlled surface reactions on bulk and thin film metals studied with Fourier transform impedance spectroscopy and surface plasmon resonance techniques.

摘要

In the work presented in this thesis, the surface sensitive electrochemical techniques of cyclic voltametry (CV), potential step (PS) and Fourier transform impedance spectroscopy (FT-EIS), as well as the optical technique of surface plasmon resonance (SPR), were used to probe a wide variety of surface processes at various metal/liquid interface. Three polycrystalline metals (Au, Ta and Cu) and a Cr-coated gold film were used for these studies in different aqueous environments.; A combination of CV with FT-EIS and PS was used to investigate electronic and structural proprieties of a modified bulk electrode of Au. This experimental system involved under potential deposition (UPD) of Bi3+ on Au in a supporting aqueous electrolyte containing ClO-4 . UPD range of Bi3+ was determined, and adsorption kinetics of Bi3+ in the presence of coadsorbing anion, ClO-4 were quantified.; Potentiodynamic growth of oxide films of Ta in the following electrolytes NaNO3, NaNO3 + 5wt% H2O2, NaOH and NaOH + 5wt% H2O2 had been investigated. The oxide films were grown in the range -0.1 → +0.4V (high electric field) at a scan rate of 10 mV/s. Time resolved A.C. impedance spectroscopy measurements in the frequency range (0.1--20 KHz) were performed to characterize the surface reactions of oxide formation. The results are interpreted in terms of charge conductivity O2- through the oxide film, and disintegration of H2O2 into OH-. In a high pH medium (pH 12), dissociation of H2O2 was catalytically enhanced. This led to destabilization of the electrogenerated tantalum oxide surface film in the form of a soluble hexatantalate species.; In contrast with the electrolytes, NaNO3, NaNO3 + 5wt% H2O2, NaOH, where only the oxide growth was observed, the A.C. impedance spectroscopy measurements in NaOH + 5wt% H 2O2 showed competition between oxide formation and its removal. These results are relevant for chemical slurry design in chemical mechanical polishing (CMP) of Ta. Further investigations were performed by studying potential galvanic corrosion effects that are susceptible to occur during planarization process in CMP technology. A combination of FT-EIS with potentiodynamic polarization and galvanic current measurements showed evidence of these effects when Cu (interconnected material in integrated circuits) and Ta (barrier material) were brought into electrical contact via abrasive-free polishing solutions. Quantitative analyses of kinetics of these effects were performed.; Catalytic activity of a thin film Au (∼40 nm) toward methanol oxidation in alkaline medium for direct methanol fuel cell (DMFC) was carried out in this part of the work. A relatively unique combined technique of FT-EIS and SPR was used to perform this study. The FT-EIS data provided detailed kinetic parameters that characterize electro-oxidation of methanol. This led to a quantitative understanding of the mechanism of the probed surface reactions. At the same time, the SPR data provided with high accuracy the optical parameters and electronic characteristics of the thin film Au. The combined technique provided a complete understanding of the observed surface reactions, and showed consistency in data.