In-situ atomic-scale studies of the mechanisms and dynamics of metal dissolution by high-speed STM

Magnussen, Olaf M.; Zitzler, L.; Gleich, B.; Vogt, Monika; Behm, R. J.

doi:10.1016/s0013-4686(01)00654-5

“…In fact, domain boundaries in the c(22) Cl adlayer were only observed in the presence of S ad , whereas in extensive previous video-STM studies of Cu(100) in sulfide-free HCl solution [7,9] the Cu terraces always appeared to be covered by a single c(22) domain. Probably the fast, unimpeded domain boundary motion within the pure Cl adlayer either prevents the STM imaging of these boundaries or leads to rapid ripening of the domain distribution, resulting in a single domain on each terrace.…”

mentioning

confidence: 75%

“…We have applied this technique in the past for studies of metal deposition and dissolution [7][8][9] as well as of collective nanoscale transport phenomena during the formation of the potential-induced Au reconstruction. [10][11][12] Recently, we made the first in situ measurements of adsorbate surface diffusion with this method.…”

Section: Introductionmentioning

confidence: 99%

In Situ Video‐STM Studies of Adsorbate Dynamics at Electrochemical Interfaces

Tansel

¹

,

Taranovskyy

²

,

Magnussen

³

2010

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The dynamic behavior of individual adsorbates at electrochemical interfaces was studied directly by in situ high-speed scanning tunneling microscopy, using sulfur adsorbed on Cu(100) electrodes in 0.01 M HCl solution as an example. By dosing from diluted Na(2)S solutions S(ad) coverages of a few percent can be prepared, with the sulfur adsorbates occupying positions within the c(2x2) lattice of coadsorbed chloride. S(ad) tracer diffusion occurs via hopping between neighboring c(2x2) lattice sites at considerably higher rates than those of sulfur on Cu(100) under UHV conditions, indicating a pronounced influence of the electrochemical environment on the adsorbate surface dynamics. The diffusion barrier linearly increases by 0.5 eV per V with potential and is strongly affected by neighboring S(ad) and surface defects. The S(ad)-S(ad) interactions extend over approximately 7 A. They are repulsive between nearest-neighbor and attractive between next-nearest-neighbor sites, respectively, and result in significantly reduced diffusion barriers. S(ad) on the upper terrace side of steps are transiently trapped and exhibit lower diffusion rates, leading to the formation of small metastable p(2x2) domains. Attractive interactions between S(ad) and domain boundaries in the c(2x2) adlayer result in boundary pinning as well as transient trapping and enhanced diffusion of S(ad) along the boundary.

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“…The on-going trend of miniaturization towards the nanometer scale requires a more sophisticated understanding of the relevant interface properties of those devices containing such reactive materials as copper. An atomic scale understanding of copper corrosion phenomena, corrosion inhibition by organics [3][4][5][6], oxidation and precursor films for oxidation [7][8][9][10], anodic dissolution [11][12][13][14][15][16][17] and the formation of passive films [18,19] is thus of vital interest and has consequently been the focus of numerous fundamental studies. Since modern processing lines of chip fabrication also include ''wet'' chemical deposition processes the mastering of copper-electrolyte interfaces with or without potential control can be regarded as a particular challenge.…”

Section: Introductionmentioning

confidence: 99%

“…Local phenomena of copper dissolution in acidic electrolytes have been intensively studied using in situ STM [11][12][13][14][15][16]. Active sites for dissolution or deposition are exclusively kinks at step edges.…”

Section: Introductionmentioning

confidence: 99%

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

Broekmann

¹

,

Hai

²

,

Wandelt

³

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 first in situ atomic-scale visualization of this growth mechanism was recently demonstrated for the incorporation of chloride ions at kink positions of the c(2 × 2) chloride adlayer on Cu(100) in 0.01 M HCl [144]. If the rate of advance of the growing circular center is controlled by symmetrical hemicylindrical (surface) diffusion about an axis perpendicular to the 2D nucleus one obtains…”

Section: Growthmentioning

confidence: 99%

Phase Transitions in Two‐dimensional Adlayers at Electrode Surfaces: Thermodynamics, Kinetics, and Structural Aspects

Wandlowski¹

2002

Encyclopedia of Electrochemistry

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The sections in this article are Introduction Thermodynamic Aspects Phase Transitions and Order Parameter Adsorption Isotherms and Lateral Interactions Kinetics of 2 D Phase Formation and Dissolution Diffusion, Adsorption, Autocatalysis Nucleation and Growth Mechanisms Nucleation Growth Coupling of Nucleation and Growth Dissolution of 2 D Condensed Monolayers Examples Phase Transitions in Anionic Adlayers Introduction Phase Formation in Halide Adlayers Phase Transitions in Adlayers of Oxoanions Phase Transitions in UPD —Adlayers Introduction Underpotential Deposition of Copper Ions on Au ( hkl ) Underpotential Deposition of Copper Ions on Pt ( hkl ) Underpotential Deposition of Lead on Ag ( hkl ) Phase Transitions in Organic Monolayers General Aspects Thermodynamic Aspects Kinetic Aspects Case Study I—Coumarin at the Mercury–Aqueous Electrolyte Interface Case Study III —2,2 ′ ‐Bipyridine (2,2 ′ ‐ BP ) on Au ( hkl ) Conclusion and Outlook Acknowledgment

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In-situ atomic-scale studies of the mechanisms and dynamics of metal dissolution by high-speed STM

Cited by 114 publications

References 8 publications

In Situ Video‐STM Studies of Adsorbate Dynamics at Electrochemical Interfaces

In Situ Video‐STM Studies of Adsorbate Dynamics at Electrochemical Interfaces

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

Phase Transitions in Two‐dimensional Adlayers at Electrode Surfaces: Thermodynamics, Kinetics, and Structural Aspects

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