The Anodic Dissolution of Copper into Phosphoric Acid: II . Impedance Behavior

Glarum, S. H.; Marshall, J. H.

doi:10.1149/1.2113687

Cited by 40 publications

(29 citation statements)

References 15 publications

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“…-~aF [8] where c~ a is the transfer coefficient with a value on the order of magnitude of unity. The high frequency data (between 1 and 50 kHz) were fit to a semicircle to estimate Rn, Rp, and C~.…”

Section: Rtmentioning

confidence: 99%

“…8 Glarum and MarshalP previously questioned the plausibility of a water-acceptor mechanism because they believed that the diffusion coefficient necessary to explain the magnitude of the limiting current density is too small. Nevertheless, the present investigation shows that the measured diffusion coefficient is sufficiently small for water to be an acceptor.…”

Section: Introductionmentioning

confidence: 99%

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Copper Electropolishing in Concentrated Phosphoric Acid: I . Experimental Findings

Vidal

West

1995

J. Electrochem. Soc.

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The electropolishing of rotating copper-disk electrodes in concentrated phosphoric acid is studied by steady-state measurements, ac-impedance spectroscopy, and flow-modulation spectroscopy. The effects of applied potential, rotation speed, and temperature on the response of the system are investigated at the mass-transfer-limited plateau. Both the Arrhenius behavior of the limiting current and the ac-impedance data suggest that the rate of reaction is controlled by mass transfer of an accepter to the copper surface and not by precipitation of a salt film. It is not possible to determine from steady-state measurements the diffusion coefficient of the accepter because its identity and bulk concentration are not known with certainty. Therefore, the steady-state measurements are complemented with flow-modulation spectra which allow an estimation of the diffusion coefficient of the accepter without knowledge of its bulk concentration.

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Section: Rtmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Copper Electropolishing in Concentrated Phosphoric Acid: I . Experimental Findings

Vidal

West

1995

J. Electrochem. Soc.

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“…e.g., [6][7][8][9][10][11][12][13][14][15][16]). Other thoroughly studied oscillatory electrodissolution systems include, among others, copper in phosphoric acid [17][18][19][20][21], copper in chloride media [22,23], and nickel in sulfuric acid [24,25]. While early studies involved classical electrochemical characteristics of those processes, the more recent ones also include the analysis of these phenomena in terms of standard techniques of nonlinear dynamics.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical oscillations and bistability during anodic dissolution of vanadium electrode in acidic media—part I. Experiment

Gorzkowski

Wesołowska

Jurczakowski

et al. 2011

J Solid State Electrochem

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Dynamic instabilities, current oscillations and bistability observed during anodic dissolution of both stationary and rotating disk vanadium electrode in acidic phosphoric media, were reported using both dc and ac techniques. The effect of various experimental conditions, concentration of H 3 PO 4 , temperature, disk rotation rate, and external resistance, was analyzed. Systematic studies allowed the construction of bifurcation diagrams, showing the regions of oscillations and bistability, including the complex behaviors like coexistence of both dynamic regimes. Analogous comparative measurements and analyses were performed for other media-sulfuric, nitric, perchloric, and trifluoroacetic acids-also indicating complex dynamic behaviors. These complexities arise not only due to the difficulties with the precise identification of the composition of the passive layer in every acid but are also due to relatively fast dissolution of V electrode, even in the presence of passive layer, which causes permanent drift of the system's characteristics. Due to these experimental difficulties, theoretical modeling seems to be an appropriate method to analyze the essential nonlinear dynamic properties of the studied system.

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“…In addition, Cu electropolishing in phosphoric acid electrolytes has been a prototype for fundamental studies of electropolishing [7][8][9][10][11][12][13]. Despite intensive investigation, the identity of the solution phase species involved in the rate-determining step remains controversial, with some groups proposing phosphate-containing species and others water [5,7,10,12].…”

Section: Introductionmentioning

confidence: 99%

Water diffusion coefficients during copper electropolishing

Suni

2004

Journal of Applied Electrochemistry

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Cu electropolishing was studied using a rotating disc electrode in a variety of phosphoric acid-based electrolytes, including several with ethanol and other species added as diluents. Diluents allow a wider range of water concentrations and electrolyte viscosities to be accessed and also reduce the removal rate during Cu electropolishing, simplifying possible application to damascene processing. Transient and steady state currents in the mass transfer limited regime are shown to depend on both the number of water acceptor molecules associated with each dissolving Cu ion and on the effective diffusion coefficient of water. Transient analysis samples the bulk transport properties, whereas steady state analysis integrates them through the diffusion layer. Assuming that the effective diffusion coefficients appropriate to transient and steady state behavior are the same, about one water molecule is associated with each dissolving Cu ion. This analysis yields effective diffusion coefficients for water on the order of 10 )9 cm 2 s )1 . However, the data is also consistent with an assumption that six water molecules are associated with each dissolving Cu ion, but the effective diffusion coefficient appropriate for a Levich analysis is somewhat lower than that in the bulk electrolyte. This analysis yields effective diffusion coefficients for water on the order of 10 )8 -10 )7 cm 2 s )1 . The latter interpretation, that six water molecules are associated with each dissolving Cu ion, appears more likely since it provides almost exact agreement with the effective diffusion coefficient reported previously by Vidal and West. In combination with previously published impedance results ruling out a salt film mechanism, the good agreement between the transient and steady state analyses confirm that water is the acceptor species that complexes dissolving Cu ions in phosphoric acid-based electropolishing baths.

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The Anodic Dissolution of Copper into Phosphoric Acid: II . Impedance Behavior

Cited by 40 publications

References 15 publications

Copper Electropolishing in Concentrated Phosphoric Acid: I . Experimental Findings

Copper Electropolishing in Concentrated Phosphoric Acid: I . Experimental Findings

Electrochemical oscillations and bistability during anodic dissolution of vanadium electrode in acidic media—part I. Experiment

Water diffusion coefficients during copper electropolishing

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