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In situ stress and nanogravimetric measurements during underpotential deposition of bismuth on (111)-textured Au.

The surface stress associated with the underpotential deposition (upd) of bismuth on (111)-textured Au is examined, using the wafer curvature method, in acidic perchlorate and nitrate supporting electrolyte. The surface stress is correlated to Bi coverage by independent nanogravimetric measurements using an electrochemical quartz crystal nanobalance. The mass increase measured in the presence of perchlorate is consistent with the (2 x 2) and (p x square root 3)-2Bi adlayers reported in the literature. ClO(4)(-) does not play a significant role in the upd process. The complete Bi monolayer causes an overall surface stress change of about -1.4 N m(-1). We attribute this compressive stress to the formation of Bi-Au bonds which partially satisfy the bonding requirements of the Au surface atoms, thereby reducing the tensile surface stress inherent to the clean Au surface. At higher Bi coverage, an additional contribution to the compressive stress is due to the electrocompression of the (p x square root 3)-2Bi adlayer. In nitric acid electrolyte, NO(3)(-) coadsorbs with Bi over the entire upd region but has little fundamental impact on adlayer structure and stress.