Electrochemical Phase Formation and Growth

Budevski, E.; Staikov, G.; Lorenz, W. J.

doi:10.1002/9783527614936

Cited by 654 publications

(646 citation statements)

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“…The Pb UPD peak is very sharp and occurs at an underpotential of approximately +0.18 V; this is preceded by several smaller and broader cathodic peaks, which occur at higher underpotentials (0.350 and 0.240 V). The general agreement is that the Pb UPD process starts with the adsorption of Pb or Pb-OH species on defects at the Au surface, such as steps and dislocations [13]. The broad cathodic peak at ≈0.375 V is associated with the initial decoration of the Au (111) surface defects by Pb adatoms [31].…”

Section: Underpotential Deposition (Upd)supporting

confidence: 58%

“…The broad cathodic peak at ≈0.375 V is associated with the initial decoration of the Au (111) surface defects by Pb adatoms [31]. The broad shoulder and cathodic peak at ≈0.235 V are associated with nucleation and growth of Pb UPD layer on Au (111) terraces [13]. Most of the current/charge associated with the main Pb UPD peak is due to densification of the Pb UPD layer, which initially nucleates and grows as a low-density phase [13].…”

Section: Underpotential Deposition (Upd)mentioning

confidence: 99%

“…Developments in scanning probe microscopy and X-ray scattering techniques have renewed the interest in UPD phenomena. In the 1980s and 1990s numerous UPD systems were re-examined in detail, providing additional information about the UPD process, its description, and diversity [13,14].…”

Section: Underpotential Deposition (Upd)mentioning

confidence: 99%

“…UPD denotes a potential-dependent adsorption process with great sensitivity and selectivity toward the nature of the metal surface and its termination [12,13].…”

Section: Underpotential Deposition (Upd)mentioning

confidence: 99%

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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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Section: Underpotential Deposition (Upd)supporting

confidence: 58%

Section: Underpotential Deposition (Upd)mentioning

confidence: 99%

Section: Underpotential Deposition (Upd)mentioning

confidence: 99%

“…UPD denotes a potential-dependent adsorption process with great sensitivity and selectivity toward the nature of the metal surface and its termination [12,13].…”

Section: Underpotential Deposition (Upd)mentioning

confidence: 99%

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Electrochemical Surface Processes and Opportunities for Material Synthesis

Brankovic¹,

Zangari²

2015

Advances in Electrochemical Sciences and Engineering

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“…We note in passing that a monolayer of copper deposited on gold has a tendency to form a surface alloy after several hours; [6] this is further evidence for the ease with which these two metals form alloys in an electrochemical environment, even without the impact of a tip.…”

mentioning

confidence: 99%

On the Stability of Electrochemically Generated Nanoclusters-A Computer Simulation

Pópolo

Leiva

Schmickler

2001

Angew. Chem. Int. Ed.

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Multi-method Analysis of the Metal/Electrolyte Interface: Scanning Force Microscopy (SFM), Quartz Microbalance Measurements (QMB), Fourier Transform Infrared Spectroscopy (FTIR) and Grazing Incidence X-ray Diffractometry (GIXD) at a Polycrystalline Copper Electrode

Kautek

Geuss

Sahre

et al. 1997

Surf. Interface Anal.

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The successful application of various in situ and ex situ analytical techniques has been demonstrated at the buried interface between a metal and an electrolyte. Scanning force microscopy (SFM), electrochemical quartz microbalance measurements (EQMB), grazing incidence x‐ray diffractometry (GIXD), Fourier transform infrared spectroscopy (FTIR) in the specular reflection absorption mode and electrochemical charge measurements proved complementary in the characterization of a polycrystalline copper electrode in alkaline 0.1 M sulphate, perchlorate, fluoride and chloride electrolyte contact at pH 12. The surface exhibited a mixture of Cu(111) and Cu(200) grains of the order of 100 nm. Repeated potential scanning in the double layer and passive oxide region, between ‐1.4 and +0.1 VMSE, resulted in a complete reorganization of the surface morphology but no detectable corrosion. The electrochemical exchange of H2O and OH− between the electrolyte and the oxide film took place reversibly in accordance with a solid‐state growth mechanism. The copper atoms were redeposited at crystallographically preferred sites, generating comparatively homogeneously oriented, narrow Cu(111)‐edged grain ridges of length 200 nm. In the Cu(I) potential range, the formation of several monolayers of amorphous Cu2O could be confirmed. Only after extended time periods in the Cu(II) oxide potential region, Cu2O recrystallized to a (111) phase accompanied by Cu2O(200) and Cu2O(110). In this region, one observed the formation of amorphous Cu(OH)2 concurrent with further growth of Cu2O. Strong CuOH IR stretching bands excluded the existence of CuO. At corrosive potentials of +0.25 VMSE, high anodic currents and substantial mass losses led to an electropolished surface with isolated features of <300 nm width and <70 nm height.© 1997 John Wiley & Sons, Ltd.

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Electrochemical Phase Formation and Growth

Cited by 654 publications

References 0 publications

Electrochemical Surface Processes and Opportunities for Material Synthesis

Electrochemical Surface Processes and Opportunities for Material Synthesis

On the Stability of Electrochemically Generated Nanoclusters-A Computer Simulation

Multi-method Analysis of the Metal/Electrolyte Interface: Scanning Force Microscopy (SFM), Quartz Microbalance Measurements (QMB), Fourier Transform Infrared Spectroscopy (FTIR) and Grazing Incidence X-ray Diffractometry (GIXD) at a Polycrystalline Copper Electrode

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