The Initial Stages of Copper Deposition on Bare and Chemically Modified Gold Electrodes

Schneeweiss, Marie Anne; Kolb, Dieter M.

doi:10.1002/(sici)1521-396x(199905)173:1<51::aid-pssa51>3.0.co;2-o

Cited by 66 publications

(62 citation statements)

References 105 publications

(78 reference statements)

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“…These results are consistent with those reported previously. 10,12,35 As described above, cupric ions codeposited with MAA molecules formed corrugated stripes on the MAA adlayer (Fig. 6), rather than nucleated near pits.…”

Section: Resultsmentioning

confidence: 59%

In Situ Scanning Tunneling Microscopy Imaging Self-Assembled Monolayers of Mercaptoacetic Acid and Cupric Ion on Au(111) Electrode

Lai¹,

Chen²,

Yau³

et al. 2014

J. Electrochem. Soc.

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We employed voltammetry and scanning tunneling microscopy (STM) to study the coadsorption of mercaptoacetic acid (MAA) and cupric ions (Cu 2+ ) on Au(111) electrode from 0.5 M sulfuric acid + 0.8 M CuSO 4 + 0.03 mM MAA. Irreversibly adsorbed Cu 2+ ions were reduced at 0.27 V first then at −0.2 V (vs. Ag/AgCl), ascribed to the underpotential and overpotential deposition processes, respectively. Counting the amount of charge involved in the stripping peak of the Cu deposit rendered quantification of Cu 2+ ions codeposited with MAA on the Au(111) electrode, which yielded roughly 7.7 × 10 14 Cu 2+ ions/cm 2 . MAA alone and MAA + Cu 2+ were adsorbed in Au(111) -(3 × √ 13) and (p × √ 3) structures, respectively. Cu 2+ could be imaged by the STM, but their high mobility made it difficult to obtain high -quality STM results needed to quantify the amount of adsorbed Cu 2+ . Spatial structures of MAA molecules segregated onto the Cu deposit were found to vary with potential. They returned to the Au(111) electrode once the Cu deposit was oxidized at E > 0.4 V, yielding MAA + Cu 2+ structures different from those seen at the pristine sample.Organosulfur compounds (OSCs) have found wide applications in electroanalysis and electrodeposition. 1-4 In developing glucose biosensor, for example, gold electrode modified with mercaptopropanic acid (MPA) is able to trap protein molecules in the presence of cationic polymeric molecules, which enables charge transfer and detection of biomolecules using current as the gauge to quantify analyte. 1 In addition, gold electrodes coated with MPA and MAA (mercaptoacetic acid) are used to pre-concentrate copper ions, making it possible to quantify Cu 2+ by cathodic stripping analysis. 5 Of close relevance to this study is the role of OSCs in electrodeposition, as many of them are essential ingredients in electroplating baths. For example, bis-3-sodiumsulfopropyl-disulfide (SPS) and mercaptopropanic sulfonic acid (MPS), are used as accelerators to implement Cu superfilling in recess on silicon chips. [6][7][8][9] In addition, OSCs with carboxylic acid end groups such as MPA can yield bright Cu deposit. 10 The devise of scanning tunneling microscopy (STM) greatly helps our understanding of these OSCs involved in Cu electroplating. STM has revealed MPA, 10 and a number of OSCs, 11-14 adsorbed on copper and gold electrodes. Furthermore, in situ STM has shed insights into electrodeposition of Cu on bare and modified metallic electrodes of gold, platinum, rhodium, etc. [15][16][17] In this study we employed in situ STM to examine spatial structures of MAA and MAA + Cu 2+ adlayers deposited on Au(111) from acidic aqueous dosing solutions. Not only strongly adsorbed MAA molecules but also Cu 2+ ions were imaged by molecular -resolution STM. Results obtained show that MAA molecules rearranged to accommodate coadsorbed Cu 2+ ions. We substantiated this study by looking at the reduction processes of surface bound Cu 2+ on Au(111). STM revealed organized MAA molecules segregated from the gold substrate ont...

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Section: Resultsmentioning

confidence: 59%

In Situ Scanning Tunneling Microscopy Imaging Self-Assembled Monolayers of Mercaptoacetic Acid and Cupric Ion on Au(111) Electrode

Lai¹,

Chen²,

Yau³

et al. 2014

J. Electrochem. Soc.

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“…However, to date reported SPM results do not support this conclusion and thus contribute to the pre-existing controversy. Both STM [26,34,35] and AFM [9,27] studies report on the 'bare' atomic structure of the completed Cu adlayer with an atomic spacing of the underlying Au(1 1 1) which is attributed to Cu-(1 · 1) layer. Actually, there are not that many studies of the Cu upd process focusing on this aspect of monolayer formation in contrast to the numerous reports and analysis of the low-density structure that is so easily observable.…”

Section: Phase Transition Betweenmentioning

confidence: 99%

High resolution electrochemical STM: New structural results for underpotentially deposited Cu on Au(111) in acid sulfate solution

Vasiljević¹,

Viyannalage²,

Dimitrov³

et al. 2008

Journal of Electroanalytical Chemistry

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“…The study of initial electrocrystalization of metals is an important area of study [7][8][9][10]. A number of studies have been reported for the investigation of the initial nucleation of cobalt [32], copper [14,22,25,27,29,33], palladium [7, 13, 16-19, 21, 23, 34, 36], platinum [20,28] and silver [31] on various substrates. Initial electro-nucleation studies are important as it provides a mechanistic study with simple approach that can be used to approximate the actual initial nucleation without the help of expensive instruments such as atomic force microscopy and other nano-imaging tools.…”

Section: Introductionmentioning

confidence: 99%

Tuning the Initial Electronucleation Mechanism of Palladium on Glassy Carbon Electrode

Alemu¹,

Assresahegn²,

Soreta³

2014

Port. Electrochim. Acta

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Electrochemical metal nucleation is the method for the formation of metal nanoparticles on the electrode surface. Studying the early stage of electronucleation is simpler than other methods as the driving force for nucleation is achieved by changing deposition potentials and concentration of metal ions. In this work, the potential step electrochemical deposition of palladium was studied from its chloride solution at room temperature on glassy carbon electrode surface. The nucleation mechanism was studied by analysis of the resulting current transients. Accordingly, the initial electro-nucleation mechanism of palladium nanoparticles was found to be varying depending on deposition conditions such as deposition potential and palladium concentration. It can be changed from 3D instantaneous (for all deposition potentials studied and in higher electrolytic concentration) to 3D progressive nucleation mechanism (for lower deposition potential and lower electrolytic concentration). In addition, the nucleation rate for each deposition potential as well as the concentration has been determined. The nucleation rate in this research is used to calculate the nuclei density and found to decrease from more negative deposition potential to more positive deposition potential in agreement with the observed shift in electronucleation mechanism.

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The Initial Stages of Copper Deposition on Bare and Chemically Modified Gold Electrodes

Cited by 66 publications

References 105 publications

In Situ Scanning Tunneling Microscopy Imaging Self-Assembled Monolayers of Mercaptoacetic Acid and Cupric Ion on Au(111) Electrode

In Situ Scanning Tunneling Microscopy Imaging Self-Assembled Monolayers of Mercaptoacetic Acid and Cupric Ion on Au(111) Electrode

High resolution electrochemical STM: New structural results for underpotentially deposited Cu on Au(111) in acid sulfate solution

Tuning the Initial Electronucleation Mechanism of Palladium on Glassy Carbon Electrode

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