Quartz Crystal Microbalance Expanded Capability for Studying CuCl Crystal Formation on Copper Surfaces

Soares, David Mendez; Wasle, Sabine; Doblhofer, Karl; Tenan, M. A.

doi:10.1002/1439-7641(20020916)3:9<817::aid-cphc817>3.0.co;2-u

Cited by 6 publications

(6 citation statements)

References 11 publications

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“…Similar behavior has been observed previously in absence of PEG. [5][6][7] At chloride concentrations c Cl Ͼ 2 mM a deposit of CuCl was found to form reversibly on the electrode surface, in parallel with the electrochemical Cu͑II͒/Cu metal reaction. Clearly, under the conditions of Fig.…”

Section: Resultsmentioning

confidence: 90%

“…5͒ depends nearly linearly on the concentration of chloride, as observed previously in the absence of PEG, indicating that the growth rate of the deposit is limited by transport of Cl Ϫ toward the electrode surface. [5][6][7] In the negative potential range, the CuCl deposit dissolves when the stationary concentration of Cu ϩ falls below the value defined by the solubility product. The Cu ϩ ions may then be reduced to Cu metal while Cl Ϫ undergoes transport into the bulk electrolyte.…”

Section: Discussionmentioning

confidence: 99%

“…In previous publications we studied phenomena resulting from chloride and bromide additions to the H 2 SO 4 ϩ CuSO 4 electrolyte. [5][6][7] In the present work this investigation is extended to study the effects of adding PEG to the electrolyte in the presence and in absence of halide ions.…”

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confidence: 99%

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An EQCM Study of the Electrochemical Copper(II)/Copper(I)/Copper System in the Presence of PEG and Chloride Ions

Doblhofer

Wasle

Soares

et al. 2003

J. Electrochem. Soc.

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The charge-transfer reaction between copper͑II͒ and copper electrodes is studied in electrolytes that are similar to galvanic copper baths, 2.2 M H 2 SO 4 ϩ 0.3 M CuSO 4 ϩ chloride ions (c Cl р 1 ϫ 10 Ϫ2 M͒, and polyethyleneglycol 1500 ͑PEG, c PEG р 4 ϫ 10 Ϫ3 M͒. Electrochemical quartz crystal microbalance ͑EQCM͒ measurements are conducted, mainly under conditions of cyclic voltammetry. The formation and dissolution of CuCl on the electrode surface at c Cl у 2 mM is demonstrated, a notable shift of the pseudo-equilibrium potential associated with CuCl deposition is analyzed, and the inhibition of the charge-transfer reaction by the PEG/Cl Ϫ surface layer is characterized. It is shown that the inhibiting layer forms by reaction between the adsorbate-covered copper electrode and PEG, i.e., neither Cu ϩ nor Cu ϩϩ from the electrolyte are required. Numerical simulations of the processes as well as parallel experiments conducted with electrolytes not containing Cu͑II͒ support the proposed mechanisms, in particular the role of the intermediate Cu ϩ .

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Section: Resultsmentioning

confidence: 90%

Section: Discussionmentioning

confidence: 99%

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An EQCM Study of the Electrochemical Copper(II)/Copper(I)/Copper System in the Presence of PEG and Chloride Ions

Doblhofer

Wasle

Soares

et al. 2003

J. Electrochem. Soc.

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“…micrograph of the copper surface after contact with an electrolyte containing 4 mM KBr for 3 minutes, indicating that the mass increase is due to a crystalline deposit that forms without current flow. The EDAX analysis conducted as described before [10,20] indicates unambiguously that the deposit is CuBr. It has been shown [10] that CuCl forms at open circuit at the rate of transport of chloride towards the electrode surface.…”

Section: Resultsmentioning

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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“…A quartz microbalance is a well established and robust device for recording in situ mass changes due to intake or desorption of reaction products [29,30]. It is compatible with UHV requirements in open beam experiments with synchrotron radiation.…”

Section: Adoption Of a Quartz Microbalance For A Reaction Cell And A ...mentioning

confidence: 99%

Reactions of halogens with surfaces stimulated by VUV light

Ney

Schwentner

2006

J. Phys.: Condens. Matter

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Reactions of halogens (Cl2,XeF2) with metals (Cu) and semiconductors (Si, GaAs) are investigated. The main focus is put on light induced reactions, stimulated by synchrotron radiation in the spectral range from 200 to 50 nm, in comparison with the dark reaction. Growth of reaction products on the surface and the desorption of volatile compounds are studied. A set-up with a quartz microbalance was adopted to determine reaction rates in situ. The rates are very sensitive to sample preparation. In the system Cu/Cl2, oxygen was found to especially slow down the reaction and much higher reaction rates than reported previously were observed for pure samples. Measurements with masks show the possibility of using desorption (also called light induced dry etching) to microstructure materials. Analysis of the irradiations with different wavelengths reveals a high spectral dependence of the reactions, which can therefore be controlled. The efficiency of the light induced non-selective reaction follows the gas phase absorption of the etching gases, whereas selective reactions, which are used to structure the materials, are induced in adsorbed halogens at different wavelengths. High efficiencies of single-photon events, due to chain reactions, with multiplication factors of the order of 105, are observed. The resulting pit size has to be contrasted with the intended spatial resolution.

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Quartz Crystal Microbalance Expanded Capability for Studying CuCl Crystal Formation on Copper Surfaces

Cited by 6 publications

References 11 publications

An EQCM Study of the Electrochemical Copper(II)/Copper(I)/Copper System in the Presence of PEG and Chloride Ions

An EQCM Study of the Electrochemical Copper(II)/Copper(I)/Copper System in the Presence of PEG and Chloride Ions

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

Reactions of halogens with surfaces stimulated by VUV light

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