Effect of Thiourea on Oxidation of Hypophosphite Ions on Ni Surface Investigated by Raman Spectroscopy and DFT Calculation

Thiourea is well known and widely used additive for controlling the rate of electroless Ni deposition, and it is known to show complicated behavior in acidic/alkaline electroless deposition baths. To understand this, several experiments and theoretical calculations were performed. In the experiments, the adsorption of thiourea and the reducing agent (i.e., hypophosphite ions) on a Ni surface was characterized with a high-selectivity component at a right angle down to the sub-monolayer level using surface-enhanced Raman spectroscopy. By comparing the results with those obtained from the theoretical calculation, co-adsorption of thiourea and hypophosphite ions on the Ni surface was confirmed. Moreover, the acceleration or suppression effects of thiourea on the oxidation of hypophosphite ions on a Ni surface in acidic/alkaline bath were analyzed from the experimental and computational perspectives. Accordingly, an explanation that unifies both the acceleration and suppression mechanisms of thiourea in terms of its own fundamental characteristics is proposed; this will be one of the most important processes for industrial applications of electroless Ni deposition. (C) 2013 The Electrochemical Society. All rights reserved.