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High resolution electrochemical STM: New structural results for underpotentially deposited Cu on Au(1 1 1) in acid sulfate solution

Journal of Electroanalytical Chemistry

Vasiljevic, Natasa V.; Viyannalage, Lasantha T.; Dimitrov, Nikolay; Sieradzki, Karl

Adsorption of sulfate assists Cu monolayer underpotential deposition (upd) on Au(1 1 1) in a unique way, rendering two distinct structural stages: (i) formation of a low-density Cu phase at coverage of 2/3 ML known as the fenced(sqrt(3) × sqrt(3)) R 30 ° or honeycomb phase; (ii) formation of a complete monolayer, i.e., Cu-(1 × 1) phase pseudomorphic with respect to underlying Au(1 1 1) substrate. In this paper we present new structural in situ scanning tunneling microscopy (STM) results for this system. We show and discuss the STM imaging of the copper honeycomb superstructure probed underneath the co-adsorbed fenced(sqrt(3) × sqrt(3)) R 30 ° sulfate adlayer in the low-density phase. High resolution imaging during the phase transition from the low to high density copper phase unambiguously shows the existence of an ordered sulfate structure p(2 × 2) on the pseudomorphic Cu-(1 × 1) layer. The new structure is seen during the co-existence of two copper phases as well as upon completion of the Cu-(1 × 1) monolayer. While supported by earlier chronocoulometric measurements in the same system, the new structural results raise questions that need to be addressed in a future work. © 2007 Elsevier B.V. All rights reserved.

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Anion adsorption induced reversal of coherency strain

Proposed for publication in Physical Review Letters.

Floro, Jerrold A.; Seel, S.C.; Vasiljevic, Natasa V.

Experimental results are presented for stress evolution, in vacuum and electrolyte, for the first monolayer of Cu on Au(111). In electrolyte the monolayer is pseudomorphic and the stress-thickness change is -0.60 N/m, while conventional epitaxy theory predicts a value of +7.76 N/m. In vacuum, the monolayer is incoherent with the underlying gold. Using a combination of first-principles based calculations and molecular dynamic simulations we analyzed these results and demonstrate that in electrolyte, overlayer coherency is maintained owing to anion adsorption.

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5 Results
5 Results