Effect of concentration gradient on the anodic behavior of tungsten

Potentiodynamic and potentiostatic polarization experiments, the electrochemical impedance spectroscopy, the rotating disk electrode technique, and surface pH measurements were used to study the effect of tungstate ions on the anodic behavior of tungsten (W). Deliberately added tungstate ions, which are also tungsten dissolution products, were found to decrease the anodic currents at around the point of zero charge, increase the anodic currents in the neutral to weakly basic range and have no effect on the anodic currents in the strongly basic conditions. This variable effect was attributed to the competition between the stabilization of the tungsten oxide due to higher concentration of the dissolution products next to the metal surface and the stabilization of the local pH as a result of the enhanced polymerization reactions of the tungstate species. The surface pH measurements showed that the polymerization reactions kept the W surface pH higher (i.e. closer to the bulk pH) in the absence of a pH buffer in the neutral and weakly basic solutions. The tungstate ion was considered as a potentially useful additive in W chemical mechanical polishing (CMP) slurries, since this ion could increase the stability of the oxide phase to be removed by polishing and serve as a pH buffering agent.