Confined step-flow growth of Cu intercalated between graphene and a Ru(0001) surface

By comparing the growth of Cu thin films on bare and graphene-covered Ru(0001) surfaces, we demonstrate the role of graphene as a surfactant allowing the formation of flat Cu films. Low-energy electron microscopy, X-ray photoemission electron microscopy and X-ray absorption spectroscopy reveal that depositing Cu at 580 K leads to distinct behaviors on both types of surfaces. On bare Ru, a Stranski-Krastanov growth is observed, with first the formation of an atomically flat and monolayer-thick wetting layer, followed by the nucleation of three-dimensional islands. In sharp contrast, when Cu is deposited on a graphene-covered Ru surface under the very same conditions, Cu intercalates below graphene and grows in a step-flow manner: atomically-high growth fronts of intercalated Cu form at the graphene edges, and extend towards the center of the flakes. Our findings suggest potential routes in metal heteroepitaxy for the control of thin film morphology.Comment: 9 pages, 4 figure

Twins and their boundaries during homoepitaxy on Ir(111)

The growth and annealing behavior of strongly twinned homoepitaxial films on Ir(111) has been investigated by scanning tunneling microscopy, low energy electron diffraction and surface X-ray diffraction. In situ surface X-ray diffraction during and after film growth turned out to be an efficient tool for the determination of twin fractions in multilayer films and to uncover the nature of side twin boundaries. The annealing of the twin structures is shown to take place in a two step process, reducing first the length of the boundaries between differently stacked areas and only then the twins themselves. A model for the structure of the side twin boundaries is proposed which is consistent with both the scanning tunneling microscopy and surface X-ray diffraction data.Comment: 13 pages, 11 figure

Strains Induced by Point Defects in Graphene on a Metal

Strains strongly affect the properties of low-dimensional materials, such as graphene. By combining in situ, in operando, reflection high energy electron diffraction experiments with first-principles calculations, we show that large strains, above 2%, are present in graphene during its growth by chemical vapor deposition on Ir(111) and when it is subjected to oxygen etching and ion bombardment. Our results unravel the microscopic relationship between point defects and strains in epitaxial graphene and suggest new avenues for graphene nanostructuring and engineering its properties through introduction of defects and intercalation of atoms and molecules between graphene and its metal substrate

Intercalating cobalt between graphene and iridium (111): a spatially-dependent kinetics from the edges

Using low-energy electron microscopy, we image in real time the intercalation of a cobalt monolayer between graphene and the (111) surface of iridium. Our measurements reveal that the edges of a graphene flake represent an energy barrier to intercalation. Based on a simple description of the growth kinetics, we estimate this energy barrier and find small, but substantial, local variations. These local variations suggest a possible influence of the graphene orientation with respect to its substrate and of the graphene edge termination on the energy value of the barrier height. Besides, our measurements show that intercalated cobalt is energetically more favorable than cobalt on bare iridium, indicating a surfactant role of graphene

Modulating charge density and inelastic optical response in graphene by atmospheric pressure localized intercalation through wrinkles

The intercalation of an oxide barrier between graphene and its metallic substrate for chem- ical vapor deposition is a contamination-free alternative to the transfer of graphene to dielectric supports, usually needed for the realization of electronic devices. Low-cost pro- cesses, especially at atmospheric pressure, are desirable but whether they are achievable remains an open question. Combining complementary microscopic analysis, providing structural, electronic, vibrational, and chemical information, we demonstrate the spontaneous reactive intercalation of 1.5 nm-thick oxide ribbons between graphene and an iridium substrate, at atmospheric pressure and room temperature. We discover that oxygen-containing molecules needed for forming the ribbons are supplied through the graphene wrinkles, which act as tunnels for the efficient diffusion of molecules entering their free end. The intercalated oxide ribbons are found to modify the graphene-support interaction, leading to the formation of quasi-free-standing high quality graphene whose charge density is modulated in few 10-100 nm-wide ribbons by a few 10^12 cm-2, where the inelastic optical response is changed, due to a softening of vibrational modes - red-shifts of Raman G and 2D bands by 6 and 10 cm-1, respectively.Comment: Carbon (2013) available onlin

Local deformations and incommensurability of high quality epitaxial graphene on a weakly interacting transition metal

We investigate the fine structure of graphene on iridium, which is a model for graphene weakly interacting with a transition metal substrate. Even the highest quality epitaxial graphene displays tiny imperfections, i.e. small biaxial strains, ca. 0.3%, rotations, ca. 0.5^{\circ}, and shears over distances of ca. 100 nm, and is found incommensurate, as revealed by X-ray diffraction and scanning tunneling microscopy. These structural variations are mostly induced by the increase of the lattice parameter mismatch when cooling down the sample from the graphene preparation temperature to the measurement temperature. Although graphene weakly interacts with iridium, its thermal expansion is found positive, contrary to free-standing graphene. The structure of graphene and its variations are very sensitive to the preparation conditions. All these effects are consistent with initial growth and subsequent pining of graphene at steps

Foreword: Recent advances in 2D materials Physics

International audienc

Universal classification of twisted, strained and sheared graphene moir\'e superlattices

Moir\'e superlattices in graphene supported on various substrates have opened a new avenue to engineer graphene's electronic properties. Yet, the exact crystallographic structure on which their band structure depends remains highly debated. In this scanning tunneling microscopy and density functional theory study, we have analysed graphene samples grown on multilayer graphene prepared onto SiC and on the close-packed surfaces of Re and Ir with ultra-high precision. We resolve small-angle twists and shears in graphene, and identify large unit cells comprising more than 1,000 carbon atoms and exhibiting non-trivial nanopatterns for moir\'e superlattices, which are commensurate to the graphene lattice. Finally, a general formalism applicable to any hexagonal moir\'e is presented to classify all reported structures.Comment: 14 pages, 6 figure

Magnetism of cobalt nanoclusters on graphene on iridium

The structure and magnetic properties of Co clusters, comprising from 26 to 2700 atoms, self-organized or not on the graphene/Ir(111) moir\'e, were studied in situ with the help of scanning tunneling microscopy and X-ray magnetic circular dichroism. Surprisingly the small clusters have almost no magnetic anisotropy. We find indication for a magnetic coupling between the clusters. Experiments have to be performed carefully so as to avoid cluster damage by the soft X-rays

Epitaxial graphene prepared by chemical vapor deposition on single crystal thin iridium films on sapphire

Uniform single layer graphene was grown on single-crystal Ir films a few nanometers thick which were prepared by pulsed laser deposition on sapphire wafers. These graphene layers have a single crystallographic orientation and a very low density of defects, as shown by diffraction, scanning tunnelling microscopy, and Raman spectroscopy. Their structural quality is as high as that of graphene produced on Ir bulk single crystals, i.e. much higher than on metal thin films used so far.Comment: To appear in Appl. Phys. Let