Atomic structures and dynamics of a Cu(100) electrode in dilute hydrobromic acid: An in situ STM study

Broekmann, Peter; Anastasescu, Mihai; Spaenig, A.; Lisowski, Wojciech; Wandelt, K.

doi:10.1016/s0022-0728(00)00340-5

Cited by 52 publications

(40 citation statements)

References 21 publications

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“…The huge differences in the cyclic voltammograms of copper electrodes in iodide containing electrolytes (Figures 1 and 2) and in other acidic electrolytes [11][12][13][14][15][16][17] are due to the intermediate and final products formed upon copper dissolution. In the absence of complexing anions copper dissolution is described by the widely accepted BockrisMattson mechanism [28][29][30].…”

Section: Discussionmentioning

confidence: 99%

“…This can simply be attributed to the higher solubility product of CuBr bulk (K s = 5.9 Â 10 )9 mol 2 l )2 and CuCl bulk (K s = 1.72 Â 10 )7 mol 2 l )2 and the low halide concentrations of 10 mM used in previous experiments [11][12][13]17]. It can be assumed that CuX bulk phases (X = Br ) , Cl ) ) would also appear upon copper dissolution provided higher chloride and bromide concentrations are used.…”

Section: Discussionmentioning

confidence: 99%

“…The on-going trend of miniaturization towards the nanometer scale requires a more sophisticated understanding of the relevant interface properties of those devices containing such reactive materials as copper. An atomic scale understanding of copper corrosion phenomena, corrosion inhibition by organics [3][4][5][6], oxidation and precursor films for oxidation [7][8][9][10], anodic dissolution [11][12][13][14][15][16][17] and the formation of passive films [18,19] is thus of vital interest and has consequently been the focus of numerous fundamental studies. Since modern processing lines of chip fabrication also include ''wet'' chemical deposition processes the mastering of copper-electrolyte interfaces with or without potential control can be regarded as a particular challenge.…”

Section: Introductionmentioning

confidence: 99%

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Copper dissolution in the presence of a binary 2D-compound: CuI on Cu(100)

2006

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Exposing a Cu(100) electrode surface to an acidic and iodide containing electrolyte (5 mM H 2 SO 4 /1 mM KI) leads to the formation of an electro-compressible/electro-decompressible c(p Â 2)-I adsorbate layer at potentials close to the onset of the copper dissolution reaction. An increase of mobile CuI monomers on-top of the iodide modified electrode surface causes the local CuI solubility product to be exceeded thereby giving rise to the nucleation and growth of a laterally well ordered 2D-CuI film at potentials below 3D-CuI bulk phase formation.Step edges serve as sources for the consumption of copper material upon compound formation leading to accelerated copper dissolution at the step edges. The 2D-CuI film exhibits symmetry properties and nearest neighbor spacings that are closely related to the (111) lattice of the crystalline CuI bulk phase. Intriguingly, the 2D-CuI film on Cu(100) does not act as an efficient passive layer. Copper dissolution proceeds at slightly higher potentials even in the presence of this binary 2D-compound via an inverse step flow mechanism. Further dissolution causes the nucleation and growth of 3D-CuI clusters on-top of the 2D-CuI film. This several nanometer thick 3D-CuI bulk phase passivates the electrode against further dissolution. Characteristically, the formation/dissolution of the 3D-CuI bulk phase reveals a significantly larger potential hysteresis of about DE = 320 mV while the appearance/disappearance of the 2D-CuI film is reversible with a potential hysteresis of only DE = 20 mV.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Copper dissolution in the presence of a binary 2D-compound: CuI on Cu(100)

2006

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“…these potentials [11][12][13][14][15][16][17][18]. It is of interest to elucidate the effect of the adsorbed halide ions on the rate of copper(II) reduction.…”

Section: Effect Of the Halides On The Charge-transfer Reaction Ratesmentioning

confidence: 99%

“…The discussion of the mechanism of CuCl and CuBr formation combined with the known adsorption behaviour of chloride [11][12][13][14][15] and bromide [16][17][18] on copper leads to new insight into the role of halides in the kinetics of the copper deposition reaction.…”

Section: Introductionmentioning

confidence: 99%

The Influence of Halide Ions on the Kinetics of Electrochemical Copper(II) Reduction

Doblhofer¹,

Wasle²,

Soares³

et al. 2003

Zeitschrift Für Physikalische Chemie

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Electrochemistry / Copper / Halides / Mechanism / Electroplating / ElectrorefiningThe cathodic reduction of copper(II) in an electrolyte comparable to technical conditions (2.2 M H 2 SO 4 + 0.3 M CuSO 4 ) is markedly affected by the presence of small concentrations of halide ions. Chloride ions accelerate the reaction, while it is slowed down by bromide. Experiments in which cyclic voltammetry is combined with an electrochemical quartz-crystal microbalance reveal the deposition and dissolution of crystalline CuCl or CuBr, respectively, on the copper surface. At the technically relevant more negative electrode potentials bulk CuCl and CuBr are unstable, however halide ions are adsorbed on the copper electrode. Although there is evidence for adsorption of the reacting Cu(II) species at the electrode surface, up to a concentration of 0.3 M CuSO 4 in presence as well as in absence of adsorbed halogenide, there is no evidence for limiation of the reaction rate caused by a limited coverage of the surface with this species.

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Dynamics and Stability of Surface Structures

Giesen

Beltramo

2011

Catalysis in Electrochemistry

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Atomic structures and dynamics of a Cu(100) electrode in dilute hydrobromic acid: An in situ STM study

Cited by 52 publications

References 21 publications

Copper dissolution in the presence of a binary 2D-compound: CuI on Cu(100)

Copper dissolution in the presence of a binary 2D-compound: CuI on Cu(100)

The Influence of Halide Ions on the Kinetics of Electrochemical Copper(II) Reduction

Dynamics and Stability of Surface Structures

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