Electrochemical characterization of copper deposited on plasma and thermally modified titanium surfaces
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INTRODUCTION
Titanium has been used successfully as a cathode substrate in a variety of electrochemical operations.[1] One of the main reasons titanium is adopted is the excellent corrosion resistance provided by the oxide film formed on its surface. Most applications employ the titanium with a naturally formed oxide. The primary objective of this research was to determine if thermally produced films would modify the electrochemical behavior of the surface. A variety of methods have been used to form titanium dioxide thin films, including anodization (1 M pure sulfuric acid),[2] furnace oxidation,[3] evaporation or sputtering of TiO2,[4,5] metallo-organic chemical vapor deposition,[6] and chemical vapor deposition.[7] Among these, furnace oxidation is the least complicated in generating reproducible oxide thin films. Although the high-temperature properties of titanium have been extensively evaluated, few studies have been made on the effect of the oxide phase on electrocrystallization. This is particularly true for research conducted on generating films below 800 7C, as the surface titanium dioxide films are often too thin to be characterized using X-ray diffraction (XRD) techniques. Over the past decade, a variety of applications relating to the area of surface coating using plasma treatment techniques have been identified. For example, high dielectric constant titanium dioxide thin films have been formed on silicon substrates by plasma oxidation of titanium.[8] Plasma oxidation of silicon has been used in integrated circuits to form high quality insulating oxide layers. Scheider et al.[9] reported that aluminum samples oxidized in plasma showed significant increases in oxygen diffusion. Plasma-treated K.S. TENG, formerly graduate student with the Materials Research Center at the University of Missouri-Rolla, is now Integration Engineer with Winbond Electronics Corp., Taipei, Taiwan. J.-L. DELPLANCKE, Lecturer, Department of Metallurgie-Electrochimie, is with the Universite Libre de Bruxelles, B-1050 Bruxelles, Belgium. J. ZHANG, formerly graduate student with the Materials Research Center at the University of Missouri-Rolla, is currently with Caterpillar, Peoria, IL 61656. T.J. O’KEEFE, Professor, is with Department of Metallurgical Engineering and the Materials Research Center, University of Missouri-Rolla, Rolla, MO 65409-1170. Manuscript submitted June 27, 1995. METALLURGICAL AND MATERIALS TRANSACTIONS B
Cu-Al alloy also enhanced the reaction rate and caused selective oxidation. Thus, a thermally or plasma-modified surface has been shown to cause a variety of changes in behavior of the metal substrate. In this study, the oxide films were grown on titanium by plasma and thermal oxidation at various temperatures (ambient temperature to 800 7C) and oxygen partial pressures (air or 80 mtorr O2). Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Auger electron spectroscopy (AES), and XRD were used to characterize the thin films. Particular attention was given to the electrochemical be
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