Additive Monitoring And Interactions During Copper Electroprocessing

Several organic and inorganic substances are widely used to control deposit structure and morphology during the electroprocessing of copper. Methods for monitoring the levels of thiourea, glue and guar gum during electrorefining and electrowinning have been successfully developed under the trade names of Reatrol and CollaMat. Other instrumental methods have been developed for additives and decomposition products associated with the electroplating of copper and other metals. Generally, these methods have been found to be either insufficiently sensitive or lacking in the desired selectivity for some or all of the additives. These procedures have mostly employed DC techniques; i.e., cyclic voltammetry, Tafel analysis, etc. In this work, chronopotentiometry (CP) and AC voltammetry were used to examine the interaction of glue, guar gum, thiourea and chloride during the electroplating of copper onto a platinum electrode. In addition, the interactions between the additives have been explored. It was found that glue in pure electrolyte (H2S04 and CuS04 only) had no effect on the chronopotentiogram. Glue was only active if chloride ions were present. The addition of thiourea resulted in several different chronopotentiograms depending on the presence of either chloride or chloride and glue. Thiourea used in conjunction with glue and chloride showed a significant increase in the polarization during copper deposition when compared to the electrolyte containing only glue and chloride. The use of a modified channel electrode further increased the sensitivity of CP. The use of AC voltammetry was explored as a technique to monitor some of the additives. AC voltammograms have more spectral detail then their DC counterparts and it is possible to monitor some of the additives at very low concentrations with AC techniques.