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

Doblhofer, Karl; Wasle, Sabine; Soares, David Mendez; Weil, K. G.; Weinberg, Gisela; Ertl, G.

doi:10.1524/zpch.217.5.479.20457

Cited by 34 publications

(51 citation statements)

References 24 publications

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“…The value of j 0 obtained in this study is somewhat larger than the previously reported values (1.1-1.4 mA cm −2 ), which is most likely due to the difference in the concentrations of Cu 2+ ions in this study (0.85 M) and those in the previous study (0.25 M). The Tafel slope was 124 mV/decade, which is also similar to the literature values [27][28][29]. Substituting the obtained kinetic parameter values of α and j 0 into the Overpotential / V Fig.…”

Section: Methodssupporting

confidence: 86%

Fabrication of high thermal conductivity copper/diamond composites by electrodeposition under potentiostatic conditions

Arai

Ueda

2020

J Appl Electrochem

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High thermal conductivity Cu/diamond composites were fabricated using an electrodeposition technique. The electrodes were oriented horizontally, and the cathode was located at the bottom of the plating bath. Diamond particles (10-230 μm) were first precipitated on the cathode substrate, and then copper was electrodeposited on the substrate to fill the gap between the precipitated diamond particles, which resulted in the formation of a Cu/diamond composite. The deposition behavior of the copper was electrochemically investigated, and the current densities of copper deposition under galvanostatic conditions were estimated. The current densities for the substrate with diamond particle layers were 4-10 times higher than the current density for the substrate without diamond particle layers, which led to undesired hydrogen evolution. Cu/diamond composites were formed under potentiostatic conditions without hydrogen evolution, and the resultant composites had compact morphologies. A specimen containing 49 vol% diamond particles with a mean diameter of 230 μm had the highest thermal conductivity of 600 W m −1 K −1 , which is 1.5 times that of pure copper (ca. 400 W m −1 K −1 ). Graphic AbstractHigh thermal conductivity Cu/diamond composites were fabricated by electrodeposition under a potentiostatic condition without the evolution of hydrogen gas. (-) (+) Diamond particles (-) (+) Potentiogalvanostat Cu plating bath (-) (+) Cu 2+ Cu e -Under potentiostatic condition High thermal conductivity Cu/diamond composite

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Section: Methodssupporting

confidence: 86%

Fabrication of high thermal conductivity copper/diamond composites by electrodeposition under potentiostatic conditions

Arai

Ueda

2020

J Appl Electrochem

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“…Similarly, the possibility of CuCl precipitation should also be considered. 37,38 In any case, the sharp onset of current is suggestive of a classical heterogeneous nucleation triggered process.…”

Section: Resultsmentioning

confidence: 94%

Electrodeposition of Cu on Ru Barrier Layers for Damascene Processing

Moffat

Walker

Chen

et al. 2006

J. Electrochem. Soc.

125

126

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Superfilling of submicrometer trenches by direct copper electrodeposition onto physical vapor deposited and atomic layer deposited Ru barriers is demonstrated. The Cu nucleation and growth mode is found to be sensitive to the oxidation state of the Ru surface as well as the copper deposition parameters. Depending on the processing conditions, Cu deposition may or may not occur competitively with oxide reduction. Failure to remove the air-formed 3D oxide film results in Volmer-Weber ͑island͒ growth and consequently poor trench filling, as well as poor adhesion between Cu and Ru. In the case of thin resistive oxide-covered Ru seed layers, the "terminal effect" further exacerbates the difficulties in obtaining a compact, fully coalesced Cu film because the rate of Ru oxide reduction is decreased along with the density of Cu nuclei. In contrast, Cu deposition on a reduced "oxide-free" Ru surface results in more rapid coalescence involving the formation of a wetting Cu underpotential deposition layer. Electrochemical reduction of the oxidized Ru seed layer in a deaerated sulfuric acid solution, followed by rapid wet transfer to a Cu plating bath, enables robust superfilling of trenches and improved adhesion between Cu and Ru. Early film coalescence is favored by deposition at high ͑ Ϸ-0.25 V͒ overpotentials.

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“…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. E.g., Dobelhofer et al report the formation of crystalline CuCl bulk and CuBr bulk upon copper deposition from acidic electrolytes containing 0.3 M CuSO 4 , 2.2 M H 2 SO 4 and trace amounts of halides (2 mM Br ) or Cl ) , respectively) [35]. Here, it is the high concentration of cuprous ions which gives rise to the exceeding of the CuX bulk solubility product upon copper deposition.…”

Section: Discussionmentioning

confidence: 99%

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

Cited by 34 publications

References 24 publications

Fabrication of high thermal conductivity copper/diamond composites by electrodeposition under potentiostatic conditions

Fabrication of high thermal conductivity copper/diamond composites by electrodeposition under potentiostatic conditions

Electrodeposition of Cu on Ru Barrier Layers for Damascene Processing

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

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