Thermodynamic Design of Electrolyte for CuO/Cu2O Bilayer by Anodic Electrodeposition

Electrodeposition of multilayered semiconductors requires a bath design to electrodeposit the upper layer(s) without dissolving the base layer(s) below. We present herein a reliable approach to bath design based on thermodynamics from the viewpoint of complexation with ligands. A CuO/Cu2O bilayer film was targeted as an example. We searched a thermodynamic database of complexation constants for ligands that could form a complex with Cu(II) but not with Cu(I), and identified monoethanolamine as one of the best candidates. Using a Cu(II)-monoethanolamine alkaline aqueous bath, we experimentally confirmed that a CuO upper layer could be deposited without dissolving the Cu2O base layer. We believe that this design is applicable to other bilayer films produced by electrochemical techniques.