Bronze Electroplating: Stability, Nucleation and Growth Study of a New Green Formulation

Abstract

Bronze electroplating is a widely used process in the electronics and costume jewelry industrial sectors as an anti-corrosion coating and barrier layer against intermetallic diffusion. The study of this alloy is also essential for the realization of copper-zinc-tin sulfide (CZTS) compounds, a quaternary semiconductor with a growing interest for the realization of thin film photovoltaic devices. The galvanic baths currently on the market are alkaline with a high amount of sodium or potassium cyanide to complex the metal ions. Cyanide salts are extremely dangerous for their toxicity, blocking cellular respiration. For this reason, cyanides are considered a danger both for the environment as well as for the workers with whom it comes in contact. In this study, a new eco-friendly, acidic and cyanide-free formulation was developed for the deposition of the Cu-Sn alloy.To achieve this goal, methanesulfonic acid (MSA) was chosen as electrolyte, which is biodegradable as part of the natural sulfur cycle. Various recipes have been evaluated to obtain a solution that was stable over time and that did not lead to the precipitation or oxidation of its components. Copper sulphate, copper methanesulfonate and tin methanesulfonate solutions were used as precursors of the metals [1]. As stabilizing additives nitrilotriacetic acid (NTA) and 2-picolinic acid (2PA), complex agents for copper, and hydroquinone (HYD), antioxidant agent for tin, were evaluated. The composition of the films, obtained both by potentiostatic and galvanostatic deposition, were analyzed by scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS) and, to investigate the structural phases of the deposits, XRD measurements were carried out. Finally, nucleation and growth as a function of the concentration of thiourea (TU) and potassium and sodium tartrate (PST), regulating additives for the deposition of copper and tin, respectively, were studied by chronoamperometric methods, in order to achieve progressive growth and therefore a lucid deposit. The present study funded by the PRIN Project (“Progetti di Ricerca di Rilevante Interesse Nazionale”), “Novel Multilayered and Micro-Machined Electrode Nano-Architectures for Electrocatalytic Applications (Fuel Cells and Electrolyzers)”, grant number 2017YH9MRK.