Mechanisms of oscillations and formation of nano-scale layered structures in induced co-deposition of some iron-group alloys (Ni-P, Ni-W, and Co-W), studied by an in situ electrochemical quartz crystal microbalance technique.

We have investigated mechanisms of oscillations and formation of nano-scale layered structures in induced co-deposition of some iron-group alloys (Ni-P, Ni-W, and Co-W) that have unique properties and are widely used in industries. Detailed in situ electrochemical quartz crystal microbalance (EQCM) experiments have revealed that the electrodeposition (induced co-deposition) of the alloys has negative differential resistances (NDRs), from which the oscillations and the layer-structure formation arise. The NDRs, however, cannot necessarily be seen in current-potential curves owing to overlap of hydrogen evolution current, indicating that the oscillations are of a hidden-NDR (H-NDR) type. The EQCM experiments have also shown that electrolyte components (such as H2PO2- and WO4(2-)) or related species are adsorbed at the electrode (deposit) surface and act as a promoter for the co-deposition reaction and that the NDRs arise from desorption of the adsorbed promoter. Interestingly, the adsorbed promoter is drawn into the deposition reaction itself, thus resulting in the alloy deposits. This mechanism was supported by in situ EQCM investigations of the oscillation as well as Auger electron spectroscopic (AES) analyses of deposits formed during the oscillation. The present work has for the first time clarified a general mechanism for the induced co-deposition reactions of some industrially important iron-group alloys (Ni-P, Ni-W, and Co-W).