The Initial Stages of Electrolytic Copper Deposition: An Atomistic View

Will, T.; Dietterle, M.; Kolb, Dieter M.

doi:10.1007/978-94-015-8435-7_9

Cited by 52 publications

(43 citation statements)

References 34 publications

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“…A similar enhanced 2D growth of copper on an Au(111) electrode has been observed when organic additives are added to the solution. 7,33,34 The present result is, however, the first evidence for the effect of the adsorption of reactant itself, i.e., PdCl 4 2-, during the electrochemical dimension growth.…”

Section: Resultsmentioning

confidence: 49%

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Electrochemical Layer-by-Layer Growth of Palladium on an Au(111) Electrode Surface: Evidence for Important Role of Adsorbed Pd Complex

1998

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The adsorption and electrochemical reduction of the tetrachloropalladate complex, PdCl 4 2-, on an Au(111) electrode in H 2 SO 4 solution containing PdCl 4 2-was investigated using an electrochemical quartz crystal microbalance (EQCM) and in situ electrochemical scanning tunneling microscopy (STM). The adlayer of PdCl 4 2-with a ( 7 × 7)R19.1°structure on the Au(111) substrate was observed by in situ STM measurement, and the amount of adsorbed PdCl 4 2-determined by the EQCM measurement was in good agreement with that estimated from this adlayer structure. In situ STM observation showed also that the electrochemical deposition of palladium proceeded with an epitaxial layer-by-layer growth mode and the PdCl 4 2-complex adsorbed on the deposited palladium layer with the same adlayer structure. The adsorption of the PdCl 4 2-complex seemed to play an important role for the layer-by-layer growth of palladium in a large area, since it inhibits the vertical but favors the lateral growth of the palladium layer. The formation of the Pd(111) bulk phase and the surface structure of Pd(111) was confirmed by X-ray diffraction (XRD) and the underpotential deposition of copper, respectively.

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Section: Resultsmentioning

confidence: 49%

“…The shape of CV in general and the positions of the UPD peaks in particular of metal electrodes are known to be very sensitive to the surface structure and order. [7][8][9][10][11] After the deposition of palladium in 50 mM H 2 SO 4 solution containing 0.01 mM PdCl 4 2-at 0.7 V for 30 min (ca. 2 ML), the electrode was rinsed with milli-Q water.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Layer-by-Layer Growth of Palladium on an Au(111) Electrode Surface: Evidence for Important Role of Adsorbed Pd Complex

1998

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“…This annealing treatment was previously demonstrated to produce a quality (111) surface, comparable to a massive (111) single crystal. 35 After resting and cooling in a hydrogen flux for 20-30 s, the sample was transferred to the electrochemical cell under potential control.…”

Section: Methodsmentioning

confidence: 99%

New Insights into Evaluation of Kinetic Parameters for Potentiostatic Metal Deposition with Underpotential and Overpotential Deposition Processes

2000

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Kinetics of copper deposition onto an Au(111) surface from sulfuric acid electrolyte, was evaluated using potentiostatic current transients. Measurements were conducted employing a new and nontraditional method, with gold electrode completely free from copper deposit at the beginning of the potential step (i.e., deposition process). The current transients obtained clearly show partial contribution from copper underpotential deposition (UPD) and copper overpotential deposition (OPD) processes. Quantitative evaluation of experimental transients was performed with the recently developed method for theoretical transient computer simulation. Detailed analysis of the kinetic parameters shows that copper UPD could be characterized as a two-dimensional nucleation and growth limited by the lattice incorporation (2D-LI) process and copper OPD as a three-dimensional nucleation process limited by diffusion-controlled growth (3D-DC). The UPD seems to be an inevitable part of the deposition process and takes place prior to OPD, regardless of the potential applied. Therefore, UPD should be treated as an early stage of the deposition process. Furthermore, our results show that the kinetics differs depending on whether deposition is initiated from a clean, bare Au(111) surface or from a gold surface already coated with a copper UPD adlayer. This indicates the role of the UPD process and the UPD adlayer on the course of OPD. Differences observed in deposition kinetics between electrolytic baths at pH 2 and 4 were likely due to adsorption of different sulfate species (sulfate or bisulfate anions) on the copper-deposit-modified Au(111) substrate (UPD, epitaxial monolayer) or bulk deposit adlayer (OPD).

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“…The complexity of UPD peaks is often dependent on the quality of the substrate surface and its preparation routine. In addition, the complexity of the voltammetry features arises due to existence of one or more UPD layer superstructures [27,28] and/or the number of UPD MLs formed [29,30].…”

Section: Underpotential Deposition (Upd)mentioning

confidence: 99%

Electrochemical Surface Processes and Opportunities for Material Synthesis

Brankovic¹,

Zangari²

2015

Advances in Electrochemical Sciences and Engineering

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Technological advances in the operation and performance of microelectronic, optical, magnetic, and, more recently, energy conversion devices depend in large part on an ever-increasing accuracy of material synthesis and film fabrication methods. In particular, the ongoing miniaturization of devices requires strict control of the crystal structure and microstructure in film as well as patterned structures, often down to the atomic scale.Electrodeposition has an important role to play in this pursuit toward miniaturization and enhanced performance [1]. Underpotential deposition (UPD) [2, 3] and surface-limited redox replacement (SLRR) [4] exploit the low energy of the metal ion precursors in solution (of the order of the thermal energy, 0.025-0.03 eV) to control the formation or replacement of single atomic layers via self-limiting processes. In UPD, a monoatomic layer of metal M is deposited on a conductive substrate S at a potential more positive than the redox potential of M [2]. This shift in redox potential is made possible by the fact that the M-S bond is stronger than the M-M bond; since the effective pair interaction V eff = V MM + V SS − 2V MS is typically in the order of 0.01-0.1 eV, only low energy precursors are sensitive to these energy differences, thus limiting the deposit to one (or sometimes two) atomic layers. SLRR involves UPD monolayer formation, followed by displacement of this layer with a full or partial monolayer of a more noble element, through a cementation process [4]. An analogous process, selective electrodesorption-based atomic layer deposition (SEBALD) consists in the formation at UPD of a sacrificial sulfur monolayer to induce UPD of late transition metals such as Fe, Co, and Ni in the form of monolayers or nanosized islands [5].Underpotential codeposition (UPCD) is a generalization of the UPD process, whereby alloy electrodeposition occurs at potentials more positive than the redox potential of the less noble element [6]. UPCD is made possible by the effective atomic pair interactions in the solid state, or equivalently by the alloying bond enthalpy. In contrast with UPD, UPCD is used to form alloy films of arbitrary

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The Initial Stages of Electrolytic Copper Deposition: An Atomistic View

Cited by 52 publications

References 34 publications

Electrochemical Layer-by-Layer Growth of Palladium on an Au(111) Electrode Surface: Evidence for Important Role of Adsorbed Pd Complex

Electrochemical Layer-by-Layer Growth of Palladium on an Au(111) Electrode Surface: Evidence for Important Role of Adsorbed Pd Complex

New Insights into Evaluation of Kinetic Parameters for Potentiostatic Metal Deposition with Underpotential and Overpotential Deposition Processes

Electrochemical Surface Processes and Opportunities for Material Synthesis

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