Voltammetric Study of Tin Electrodeposition on Polycrystalline Gold from Sulfuric and Methanesulfonic Acid

Abstract

In this work, we have studied tin electrodeposition on polycrystalline gold electrodes from two different supporting electrolytes: sulfuric acid (SA) and methanesulfonic acid (MSA), both of them commonly used in the industry. This work aims to understand the effect of the different electrolyte anions on the deposition process. We show at least three different tin deposition mechanisms on gold: irreversible adsorption, underpotential deposition, and overpotential (bulk) deposition. Underpotential deposition leads to the formation of a layer of tin in SA and MSA with a coverage around ML (monolayer) and ML, respectively. The UPD Sn layer is however somewhat uncharacteristic as it is associated with island formation and surface alloying. Cyclic voltammograms in an extended potential range showed five distinct peaks: two cathodic peaks associated with tin underpotential and overpotential deposition, and three main anodic peaks, corresponding to the oxidation of the bulk Sn, of the AuSn intermetallic layer, and of the adsorbed Sn(II) to Sn(IV). Both voltammetric and rotating disk electrode measurements show that the kinetics of tin electrodeposition in MSA is slower than in SA, which we ascribe to Sn-MSA complex formation in solution. Slow Sn deposition in MSA promotes AuSn formation, in contrast to SA in which bulk tin deposition is more prominent. Complete Levich-type mass transport control of tin deposition in SA and MSA was only reached at low scan rate due to concurrent HER on the uncovered gold surface during the deposition process at higher scan rates. An unexpected surface-confined passivation process is observed in both electrolytes.