Zonghai Hu

Ultrafast growth of single-crystal graphene assisted by a continuous oxygen supply

Graphene has a range of unique physical properties and could be of use in the development of a variety of electronic, photonic and photovoltaic devices. For most applications, large-area high-quality graphene films are required and chemical vapour deposition (CVD) synthesis of graphene on copper surfaces has been of particular interest due to its simplicity and cost effectiveness. However, the rates of growth for graphene by CVD on copper are less than 0.4 μm s-1, and therefore the synthesis of large, single-crystal graphene domains takes at least a few hours. Here, we show that single-crystal graphene can be grown on copper foils with a growth rate of 60 μm s-1. Our high growth rate is achieved by placing the copper foil above an oxide substrate with a gap of ∼15 μm between them. The oxide substrate provides a continuous supply of oxygen to the surface of the copper catalyst during the CVD growth, which significantly lowers the energy barrier to the decomposition of the carbon feedstock and increases the growth rate. With this approach, we are able to grow single-crystal graphene domains with a lateral size of 0.3 mm in just 5 s.

Direct observation of ordered configurations of hydrogen adatoms on graphene.

Ordered configurations of hydrogen adatoms on graphene have long been proposed, calculated, and searched for. Here, we report direct observation of several ordered configurations of H adatoms on graphene by scanning tunneling microscopy. On the top side of the graphene plane, H atoms in the configurations appear to stick to carbon atoms in the same sublattice. Scanning tunneling spectroscopy measurements revealed a substantial gap in the local density of states in H-contained regions as well as in-gap states below the conduction band due to the incompleteness of H ordering. These findings can be well explained by density functional theory calculations based on double-sided H configurations. In addition, factors that may influence H ordering are discussed.

Evolution of the Raman spectrum of graphene grown on copper upon oxidation of the substrate

Significant changes in the Raman spectrum of single-layer graphene grown on a copper film were observed after the spontaneous oxidation of the underlying substrate that occurred under ambient conditions. The frequencies of the graphene G and 2D Raman modes were found to undergo red shifts, while the intensities of the two bands change by more than an order of magnitude. To understand the origin of these effects, we further characterized the samples by scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and atomic force microscopy (AFM). The oxidation of the substrate produced an appreciable corrugation in the substrate without disrupting the crystalline order of the graphene overlayer and/or changing the carrier doping level. We explain the red shifts of the Raman frequencies in terms of tensile strain induced by corrugation of the graphene layer. The changes in Raman intensity with oxidation arise from the influence of the thin cuprous oxide film on the efficiency of light coupling with the graphene layer in the Raman scattering process.

Quasi-one-dimensional graphene superlattices formed on high-index surfaces

(Received 8 December 2013; published 19 February 2014)We report preparation of large area quasi-one-dimensional (1D) monolayer graphene superlattices on aprototypical high-index surface Cu(410)-O and characterization by Raman spectroscopy, Auger electron spec-troscopy, low-energy electron diffraction, scanning tunneling microscopy, and scanning tunneling spectroscopy.The periodically stepped substrate gives a 1D modulation to graphene, forming a superlattice of the samesuperperiodicity.Consequently,themoirepatternisalsoquasi-1D,withadifferentperiodicity.Scanningtunneling´spectroscopy measurements revealed new Dirac points formed at the superlattice Brillouin zone boundary aspredicted by theories.DOI: 10.1103/PhysRevB.89.085416 PACS number(s): 73

Greatly Enhanced Anticorrosion of Cu by Commensurate Graphene Coating

Metal corrosion is a long-lasting problem in history and ultrahigh anticorrosion is one ultimate pursuit in the metal-related industry. Graphene, in principle, can be a revolutionary material for anticorrosion due to its excellent impermeability to any molecule or ion (except for protons). However, in real applications, it is found that the metallic graphene forms an electrochemical circuit with the protected metals to accelerate the corrosion once the corrosive fluids leaks into the interface. Therefore, whether graphene can be used as an excellent anticorrosion material is under intense debate now. Here, graphene-coated Cu is employed to investigate the facet-dependent anticorrosion of metals. It is demonstrated that as-grown graphene can protect Cu(111) surface from oxidation in humid air lasting for more than 2.5 years, in sharp contrast with the accelerated oxidation of graphene-coated Cu(100) surface. Further atomic-scale characterization and ab initio calculations reveal that the strong interfacial coupling of the commensurate graphene/Cu(111) prevents H2 O diffusion into the graphene/Cu(111) interface, but the one-dimensional wrinkles formed in the incommensurate graphene on Cu(100) can facilitate the H2 O diffusion at the interface. This study resolves the contradiction on the anticorrosion capacity of graphene and opens a new opportunity for ultrahigh metal anticorrosion through commensurate graphene coating.

A simple method to tune graphene growth between monolayer and bilayer

Selective growth of either monolayer or bilayer graphene is of great importance. We developed a method to readily tune large area graphene growth from complete monolayer to complete bilayer. In an ambient pressure chemical vapor deposition process, we used the sample temperature at which to start the H2 flow as the control parameter and realized the change from monolayer to bilayer growth of graphene on Cu foil. When the H2 starting temperature was above 700°C, continuous monolayer graphene films were obtained. When the H2 starting temperature was below 350°C, continuous bilayer films were obtained. Detailed characterization of the samples treated under various conditions revealed that heating without the H2 flow caused Cu oxidation. The more the Cu substrate oxidized, the less graphene bilayer could form.