Intensity Modulated Photocurrent Spectroscopy (IMPS) Used to Detect Photoactive Intermediates during Ni-W Electrodeposition
The attached figure shows a typical response during cathodic deposition of a Ni-W alloy at -1 V vs AglAgCl (42 wt % W) during IMPS compared to a potential where open circuit conditions are achieved and when clearly the alloy is treated anodically. A three electrode, single compartment cell with a flat quartz window was used with the following electrolyte: 0.375 M sodium citrate, 1.0 M boric acid, 0.075 M sodium tungstate, and 0.1 M nickel sulfate at a pH of 7. The response during deposition is significantly larger than that which occurs when a surface oxide is purposely generated; helping to valid that the deposition intermediate contributes to the observed impedance results. A simple model that includes the generated photocurrent contributing to an electrochemical reaction at the electrode/electrolyte interface or being lost to recombination was used to interpret the IMPS results. The dominate process occurring during IMPS is electron-hole pair recombination and thus, the modulated light does not significantly change the deposit composition, which was experimentally confirmed.