Copper electrodeposition onto zinc for the synthesis of kesterite Cu2ZnSnS4 from a Mo/Zn/Cu/Sn precursor stack

A chloride-free solution based on ethylene glycol was shown to be suitable for the electrodeposition of copper onto zinc, allowing the fabrication of a Mo/Zn/Cu/Sn metallic precursor stack. The addition of diethanolamine (DEA) played an essential role in minimizing displacement reactions by shifting copper reduction towards a more negative potential. The electrochemical behavior of copper species with and without DEA was studied by cyclic voltammetry, and subsequently confirmed by displacement reaction assessment (OCV and ICP-OES measurements). The metallic stack was characterized by SEM and AFM, showing the effectiveness of the copper plating solution. Reactive annealing was carried out in a tubular furnace to obtain the CZTS kesterite semiconductor, as confirmed by XRD and Raman spectroscopy.