Surface-Step-Induced Oscillatory Oxide Growth

Li, Liang; Luo, Langli; Ciston, Jim; Saidi, Wissam A.; Stach, Eric A.; Yang, Judith C.; Zhou, Guangwen

doi:10.1103/physrevlett.113.136104

Cited by 60 publications

(45 citation statements)

References 35 publications

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“…1 Previous experimental and theoretical studies have shown that the kinetics and morphology of Cu oxidation are complex and influenced by many factors, including surface orientation, ambient temperature, surface defects, and electric fields. [2][3][4][5][6][7][8][9] Most previous studies have focused on the formation of a monolayer (ML) of surface oxides. [10][11][12][13][14][15][16][17][18][19][20][21] However, the process of oxygen transport into the Cu sub-surface is a key step for the transformation between the oxygenated Cu surfaces and bulk oxides.…”

Section: Introductionmentioning

confidence: 99%

Calculations of oxide formation on low-index Cu surfaces

Lian

Xiao

Yang

et al. 2016

The Journal of Chemical Physics

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Density-functional theory is used to evaluate the mechanism of copper surface oxidation. Reaction pathways of O2 dissociation on the surface and oxidation of the sub-surface are found on the Cu(100), Cu(110), and Cu(111) facets. At low oxygen coverage, all three surfaces dissociate O2 spontaneously. As oxygen accumulates on the surfaces, O2 dissociation becomes more difficult. A bottleneck to further oxidation occurs when the surfaces are saturated with oxygen. The barriers for O2 dissociation on the O-saturated Cu(100)-c(2×2)-0.5 monolayer (ML) and Cu(100) missing-row structures are 0.97 eV and 0.75 eV, respectively; significantly lower than those have been reported previously. Oxidation of Cu(110)-c(6×2), the most stable (110) surface oxide, has a barrier of 0.72 eV. As the reconstructions grow from step edges, clean Cu(110) surfaces can dissociatively adsorb oxygen until the surface Cu atoms are saturated. After slight rearrangements, these surface areas form a "1 ML" oxide structure which has not been reported in the literature. The barrier for further oxidation of this "1 ML" phase is only 0.31 eV. Finally the oxidized Cu(111) surface has a relatively low reaction energy barrier for O2 dissociation, even at high oxygen coverage, and allows for facile oxidation of the subsurface by fast O diffusion through the surface oxide. The kinetic mechanisms found provide a qualitative explanation of the observed oxidation of the low-index Cu surfaces.

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Section: Introductionmentioning

confidence: 99%

Calculations of oxide formation on low-index Cu surfaces

Lian

Xiao

Yang

et al. 2016

The Journal of Chemical Physics

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“…An estimated 137 quadrillion (10 15 ) Joule of energy are lost yearly due to high-temperature corrosion problems 6 . Although the oxidation reaction of metal surfaces is highly complicated, different elementary processes, many of which are coupled, are involved from the onset of reaction.One good example for the metal oxidation study is the low-miller index surfaces of copper [7][8][9][10][11][12][13] . Recent studies using modern electron microscopy (EM) have revealed that the initial stages of Cu oxidation bear a striking resemblance to heteroepitaxial film growth where interfacial strain is the key factor in thin film growth and determines the shape of the oxide nano-island [14][15][16][17][18][19] .…”

mentioning

confidence: 99%

Step-Edge Directed Metal Oxidation

Zhu

Saidi

Yang

2016

J. Phys. Chem. Lett.

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Metal surface oxidation is governed by surface mass transport processes. Realistic surfaces have many defects such as step edges, which often dictate the oxide growth dynamics and result in novel oxide nanostructures. Here we present a comprehensive and systematic study of the oxidation of stepped (100), (110) and (111) Cu surfaces using a multiscale approach employing density functional theory (DFT) and reactive force field molecular dynamics (MD) simulations. We show that the early stages of oxidation of these stepped surfaces can be qualitatively understood from the potential energy surface of single oxygen adatoms, namely, adsorption energies and Ehrlich-Schwöbel barriers. These DFT predictions are then validated using classical MD simulations with a newly optimized ReaxFF force field. In turn, we show that the DFT results can be explained using a simple bond-counting argument that makes our results general and transferable to other metal surfaces.

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“…3 They often serve as a dynamic reservoir of atoms in cases where the surface itself is a reactant. The signature of such a reaction can be etching, recession, and/or faceting of the steps.…”

Section: Introductionmentioning

confidence: 99%

Reconstruction of steps on the Cu(111) surface induced by sulfur

Walen

Liu

et al. 2015

The Journal of Chemical Physics

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Arich menagerie of structures is identified at 5Kfollowing adsorption of lowcoverages (≤0.05 monolayers) of S on Cu(111) at room temperature. This paper emphasizes the reconstructions at the steps. The A-type closepacked step has 1 row of S atoms along its lower edge, where S atoms occupy alternating pseudo-fourfoldhollow (p4fh) sites. Additionally, there are 2 rows of S atoms of equal density on the upper edge, bridging a row of extra Cu atoms, together creating an extended chain. The B-type close-packed step exhibits an even more complex reconstruction, in which triangle-shaped groups of Cu atoms shift out of their original sites and form a base for S adsorption at (mostly) 4fh sites. We propose a mechanism by which these triangles could generate Cu-S complexes and short chains like those observed on the terraces. PHYSICS 142, 194711 (2015) Reconstruction of steps on the Cu(111) surface induced by sulfur A rich menagerie of structures is identified at 5 K following adsorption of low coverages (≤0.05 monolayers) of S on Cu(111) at room temperature. This paper emphasizes the reconstructions at the steps. The A-type close-packed step has 1 row of S atoms along its lower edge, where S atoms occupy alternating pseudo-fourfold-hollow (p4fh) sites. Additionally, there are 2 rows of S atoms of equal density on the upper edge, bridging a row of extra Cu atoms, together creating an extended chain. The B-type close-packed step exhibits an even more complex reconstruction, in which triangle-shaped groups of Cu atoms shift out of their original sites and form a base for S adsorption at (mostly) 4fh sites. We propose a mechanism by which these triangles could generate Cu-S complexes and short chains like those observed on the terraces. C 2015 AIP Publishing LLC.[http://dx

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Surface-Step-Induced Oscillatory Oxide Growth

Cited by 60 publications

References 35 publications

Calculations of oxide formation on low-index Cu surfaces

Calculations of oxide formation on low-index Cu surfaces

Step-Edge Directed Metal Oxidation

Reconstruction of steps on the Cu(111) surface induced by sulfur

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