The Reaction of Gases on the Surface of a Single Crystal of Copper. I. Oxygen.

Gwathmey, Allan T.; Benton, Arthur F.

doi:10.1021/j150422a021

Cited by 26 publications

(9 citation statements)

References 12 publications

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“…It is well-known that a graphene coating can change the Cu oxidation behavior, and this effect is widely used to optically characterize graphene coverage and defects. ,− The optical contrast and color can thereby be linked to the Cu oxide thickness, ranging from metallic white (unoxidized) to yellow, orange, and red with increasing thickness of the Cu oxide. − We verify the correlation between optical contrast and degree of Cu oxidation via a combination of X-ray photoelectron spectroscopy (XPS) microscopy, Raman spectroscopy, and AFM. For XPS analysis, the sample was annealed at 100 °C in vacuum to remove surface contamination.…”

Section: Resultsmentioning

confidence: 90%

Crystal Orientation Dependent Oxidation Modes at the Buried Graphene–Cu Interface

et al. 2020

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We combine spatially resolved scanning photoelectron spectroscopy with confocal Raman and optical microscopy to reveal how the oxidation of the buried graphene–Cu interface relates to the Cu crystallographic orientation. We analyze over 100 different graphene covered Cu (high and low index) orientations exposed to air for 2 years. Four general oxidation modes are observed that can be mapped as regions onto the polar plot of Cu surface orientations. These modes are (1) complete, (2) irregular, (3) inhibited, and (4) enhanced wrinkle interface oxidation. We present a comprehensive characterization of these modes, consider the underlying mechanisms, compare air and water mediated oxidation, and discuss this in the context of the diverse prior literature in this area. This understanding incorporates effects from across the wide parameter space of 2D material interface engineering, relevant to key challenges in their emerging applications, ranging from scalable transfer to electronic contacts, encapsulation, and corrosion protection.

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Section: Resultsmentioning

confidence: 90%

Crystal Orientation Dependent Oxidation Modes at the Buried Graphene–Cu Interface

et al. 2020

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“…At the oxygen pressure, temperature and exposure times used in these studies, only cuprous oxide is expected to form 39,225,226 . We review studies showing that the growth of cuprous oxide on low-index copper surfaces is epitaxial with the substrate 14,[227][228][229][230] , through nucleation and coalescence of nanoislands 113,114,202,203,227,231,232 (as schematically represented in Fig. 6).…”

Section: Oxide Film Growthmentioning

confidence: 99%

“…Clean copper surfaces have been found to oxidize at different rates, with the Cu(100) face reported to have the fastest rate of oxidation, at odds with the oxidation rates measured for the formation and growth of oxide nano-islands. Indeed, Young 228 et al and Gwathmey 229 et al found that the order of oxidation rate for the low-index surfaces is (100), (111), (110) with (100) the fastest oxidising facet, for a wide range of temperatures. Rhodin 274 found instead the order to be (100), ( 110), (111) with (100).…”

Section: Long-term Copper Oxidationmentioning

confidence: 99%

Atomistic details of oxide surfaces and surface oxidation: the example of copper and its oxides

Gattinoni

Michaelides

2015

Surface Science Reports

280

258

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The oxidation and corrosion of metals are fundamental problems in materials science and technology that have been studied using a large variety of experimental and computational techniques. Here we review some of the recent studies that have led to significant advances in our atomic-level understanding of copper oxide, one of the most studied and better understood metal oxides. We show that a good atomistic understanding of the physical characteristics of cuprous (Cu 2 O) and cupric (CuO) oxide and of some key processes of their formation has been obtained. Indeed, the growth of the oxide has been proven to be epitaxial with the surface and to proceed, in most cases, through the formation of oxide nano-islands which, with continuous oxygen exposure, grow and eventually coalesce. We also show how electronic structure calculations have become increasingly useful in helping to characterise the structures and energetics of various Cu oxide surfaces. However a number of challenges remain. For example, it is not clear under which conditions the oxidation of copper in air at room temperature (known as native oxidation) leads to the formation of a cuprous oxide film only, or also of a cupric overlayer. Moreover, the atomistic details of the nucleation of the oxide islands are still unknown. We close our review with a perspective on future work and discuss how recent advances in experimental techniques, bringing greater temporal and spatial resolution, along with improvements in the accuracy, realism and timescales achievable with computational approaches make it possible for these questions to be answered in the near future.

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“…This paper presents the results of a study of the surface-structure sensitivity of the initial oxidation of Cu( hkl ) surfaces. The oxidation of Cu single crystals, specifically Cu(111), has been studied experimentally − and with theory , for decades. Scanning tunneling microscopy (STM) studies by Matsumoto et al showed that upon room-temperature exposure to O 2 , step edges on the Cu(111) surface were faceted into three directions that were aligned with the close-packed directions of the Cu(111) terrace .…”

Section: Introductionmentioning

confidence: 99%

Initial Oxidation of Cu(hkl) Surfaces Vicinal to Cu(111): A High-Throughput Study of Structure Sensitivity

et al. 2012

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The initial stage in the oxidation of Cu single crystal surfaces has been studied on a surface structure spread single crystal (S 4 C) exposing a continuous distribution of all Cu(hkl) surface orientations lying within 10°polar angle of the (111) plane, Cu(111) ± 10°-S 4 C. The uptake of oxygen across the Cu(111) ± 10°-S 4 C during exposure to O 2 at 300 K has been measured using spatially resolved X-ray photoelectron spectroscopy (XPS), and the resulting Cu 2 O surface oxide layer has been imaged using scanning tunneling microscopy (STM). Uptake of oxygen is dependent on surface step density and increases with increasing polar angle relative to the (111) pole. In contrast, the oxygen uptake does not depend on the crystallographic orientation of the step edge or, in other words, the kink density along the step edge. STM images reveal that once oxidation of the step edges begins, all of the boundaries of the Cu 2 O step oxide layer are oriented along (100) step edges in the Cu(111) terrace independent of the initial orientation of the step. In other words, the oxidizing step edges have no memory of their original orientation, and thus, the step growth depends only on step density and not on the kink density along the step edge. The combined use of both spatially resolved XPS and atomic scale imaging with STM on a Cu(111) ± 10°-S 4 C has provided unique insight into the origins of structure-sensitive surface chemistry.

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The Reaction of Gases on the Surface of a Single Crystal of Copper. I. Oxygen.

Cited by 26 publications

References 12 publications

Crystal Orientation Dependent Oxidation Modes at the Buried Graphene–Cu Interface

Crystal Orientation Dependent Oxidation Modes at the Buried Graphene–Cu Interface

Atomistic details of oxide surfaces and surface oxidation: the example of copper and its oxides

Initial Oxidation of Cu(hkl) Surfaces Vicinal to Cu(111): A High-Throughput Study of Structure Sensitivity

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