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

Abstract

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.

Nanoscale imaging of oxidized copper foil covered with chemical vapor deposition‐grown graphene layers

“…9,22,23 Among them, the orientation-dependent oxidation of Cu substrates under ambient conditions has drawn an increasing attention due to the prospective application of graphene as barrier layers. [24][25][26] Since the pioneering work by Chen et al in 2011, 27 the atomically thick graphene layer has been supposed to be a promising anticorrosion coating owing to its excellent thermal and chemical stability as well as impermeability to molecules. It has been demonstrated that CVD growth graphene can effectively prevent oxidative species reaching the underlying Cu surface and thus protects Cu from being oxidized under ambient conditions for long time (months) 13,25,26 and harsh conditions for short time (hours to days).…”

“…[24][25][26] Since the pioneering work by Chen et al in 2011, 27 the atomically thick graphene layer has been supposed to be a promising anticorrosion coating owing to its excellent thermal and chemical stability as well as impermeability to molecules. It has been demonstrated that CVD growth graphene can effectively prevent oxidative species reaching the underlying Cu surface and thus protects Cu from being oxidized under ambient conditions for long time (months) 13,25,26 and harsh conditions for short time (hours to days). 23,[28][29][30][31] Nevertheless, from the perspective of long-term anti-corrosion performance, graphene coating has been found to accelerate the oxidation of the Cu substrate in ambient atmosphere at room temperature.…”

“…33 With further investigation, it has been reported that the oxidation of the polycrystalline Cu substrate covered by CVD-grown graphene in ambient condition depends strongly on the Cu orientation owing to the varying strength of interaction. 13,24,25 Most recently, Luo et al found that the orientation of graphene layers also plays an important role in the orientationdependent oxidation of Cu surface. 35 Unfortunately, if compared with the orientation of Cu substrates, the effect of orientation of graphene layers has been seriously undermined by researchers, thus leading to highly controversial experimental findings 18,24,25 as well as unclear mechanisms 10,12,19,[36][37][38] for Cu oxidation reported by different research groups.…”

Effect of Functionalization of Reduced Graphene Oxide Coatings with Nitrogen and Sulfur Groups on Their Anti-Corrosion Properties

“…On the other hand, the conducting graphene layers might accelerate the corrosion in some instances [ 1 ]. Moreover, under ambient conditions, metal crystallographic orientation (especially for copper) is dominant to determine the degree of oxidation of substrate beneath graphene [ 2 ]. Deposition of the impeccable graphene coatings on a metal substrate is a rather challenging task.…”

Chemical Vapour Deposition of Graphene for Durable Anticorrosive Coating on Copper

“…Braeuninger-Weimer et al have studied the effect of copper crystal orientation on graphene growth and anticorrosive properties. According to the authors, Cu crystal orientations such as (011) exhibiting weak interaction force with graphene cannot prevent the intercalation of corrosive agents, hence resulting into corrosion [ 30 ]. However, copper with crystal orientations as Cu(111)and Cu(311) offer relatively strong interfacial coupling with graphene leading to an improved anticorrosive behaviour [ 30 , 31 ].…”