From Au to Pt via Surface Limited Redox Replacement of Pb UPD in One-Cell Configuration

This work is aimed at developing a protocol based on surface limited redox replacement (SLRR) of underpotentially deposited (UPD) Pb layers for the growth of epitaxial and continuous Pt thin films on polycrystalline and single crystalline Au surfaces. Different from previously reported papers using SLIM in multiple immersion or flow cell setups, this work explores the one-cell configuration setup as an alternative to improve the efficiency and quality of the growth. Open circuit chronopotentiometry and quartz-crystal microbalance experiments demonstrate steady displacement kinetics and a yield that is higher than the stoichiometric Pt(II)-Pb exchange ratio (1:1). This high yield is attributed to oxidative adsorption of OH(ad) taking place on Pt along with the displacement process. Also, ex situ scanning tunneling microscopy surface characterization reveals after the first replacement event the formation of a dense Pt cluster network that homogenously covers the Au surface. The Pt films grow homogenously with no significant changes in the cluster distribution and surface roughness observed up to 10 successive replacement events. X-ray diffraction analysis shows distinct (111) crystallographic orientation of thicker Pt films deposited on (111) textured Au thin films. Coarse energy dispersive spectroscopy measurements and finer X-ray photoelectron spectroscopy suggest at least 4 atom % Pb incorporating into the Pt layer compared to 13 atom % alloyed Cu when the growth is carried out by SLRR of Cu UPD.