Remote catalyzation for direct formation of graphene layers on oxides

Direct deposition of high-quality graphene layers on insulating substrates such as SiO(2) paves the way toward the development of graphene-based high-speed electronics. Here, we describe a novel growth technique that enables the direct deposition of graphene layers on SiO(2) with crystalline quality potentially comparable to graphene grown on Cu foils using chemical vapor deposition (CVD). Rather than using Cu foils as substrates, our approach uses them to provide subliming Cu atoms in the CVD process. The prime feature of the proposed technique is remote catalyzation using floating Cu and H atoms for the decomposition of hydrocarbons. This allows for the direct graphitization of carbon radicals on oxide surfaces, forming isolated low-defect graphene layers without the need for postgrowth etching or evaporation of the metal catalyst. The defect density of the resulting graphene layers can be significantly reduced by tuning growth parameters such as the gas ratios, Cu surface areas, and substrate-to-Cu distance. Under optimized conditions, graphene layers with nondiscernible Raman D peaks can be obtained when predeposited graphite flakes are used as seeds for extended growth.     

Recent trends in graphene materials synthesized by CVD with various carbon precursors

Graphene is a single layer of carbon atoms arranged in an sp²-hybridized structure with properties far superior compared to other materials. Research and development in graphene synthesis have been rapidly growing the past few years, especially using chemical vapor deposition (CVD) over various types of carbon precursor. The nature and the type of carbon precursor is one important parameter of growth by CVD, especially for graphene production, since they can dramatically impact graphene growth yield and rate. However, effects of the used carbon precursor on graphene growth mechanisms are rarely discussed. In the course of large-scale and low-cost graphene preparation, this review on the recent trends regarding the utilization of diverse carbon precursors used to synthesize graphene via the CVD method is of great interest for development of improved or alternative synthesis methods. The details and the mechanisms involved in graphene synthesis using carbon precursors in the form of gaseous, liquids and solids are compared, analyzed and discussed thoroughly. In this review, we present a thorough overview on the impact and mechanisms of carbon precursors in achieving high-quality graphene with competitive edge in the near future.     

Graphene epitaxy by chemical vapor deposition on SiC

We demonstrate the growth of high quality graphene layers by chemical vapor deposition (CVD) on insulating and conductive SiC substrates. This method provides key advantages over the well-developed epitaxial graphene growth by Si sublimation that has been known for decades. (1) CVD growth is much less sensitive to SiC surface defects resulting in high electron mobilities of ～1800 cm(2)/(V s) and enables the controlled synthesis of a determined number of graphene layers with a defined doping level. The high quality of graphene is evidenced by a unique combination of angle-resolved photoemission spectroscopy, Raman spectroscopy, transport measurements, scanning tunneling microscopy and ellipsometry. Our measurements indicate that CVD grown graphene is under less compressive strain than its epitaxial counterpart and confirms the existence of an electronic energy band gap. These features are essential for future applications of graphene electronics based on wafer scale graphene growth.     

Synthesis of hexagonal graphene on polycrystalline Cu foil from solid camphor by atmospheric pressure chemical vapor deposition

Understanding of graphene nucleation and growth on a metal substrate in chemical vapor deposition (CVD) process is critical to obtain high-quality single crystal graphene. Here, we report synthesis of individual hexagonal graphene and their large cluster on Cu foil using solid camphor as a carbon precursor in the atmospheric pressure CVD (AP-CVD) process. Optical and scanning electron microscopy studies show formation of hexagonal graphene crystals across the grain, grain boundaries and twin boundaries of polycrystalline Cu foil. Electron backscattered diffraction analysis is carried out before and after the growth to identify Cu grain orientation correlating with the graphene formation. The influence of growth conditions and Cu grain structure is explored on individual hexagonal graphene formation in the camphor-based AP-CVD process.     

Synthesis of monolayer hexagonal boron nitride on Cu foil using chemical vapor deposition

Hexagonal boron nitride (h-BN) is very attractive for many applications, particularly, as protective coating, dielectric layer/substrate, transparent membrane, or deep ultraviolet emitter. In this work, we carried out a detailed investigation of h-BN synthesis on Cu substrate using chemical vapor deposition (CVD) with two heating zones under low pressure (LP). Previous atmospheric pressure (AP) CVD syntheses were only able to obtain few layer h-BN without a good control on the number of layers. In contrast, under LPCVD growth, monolayer h-BN was synthesized and time-dependent growth was investigated. It was also observed that the morphology of the Cu surface affects the location and density of the h-BN nucleation. Ammonia borane is used as a BN precursor, which is easily accessible and more stable under ambient conditions than borazine. The h-BN films are characterized by atomic force microscopy, transmission electron microscopy, and electron energy loss spectroscopy analyses. Our results suggest that the growth here occurs via surface-mediated growth, which is similar to graphene growth on Cu under low pressure. These atomically thin layers are particularly attractive for use as atomic membranes or dielectric layers/substrates for graphene devices.     

Few-layer graphene direct deposition on Ni and Cu foil by cold-wall chemical vapor deposition

We report an alternative synthesis process, cold-wall thermal chemical vapor deposition (CVD), is replied to directly deposit single-layer and few-layer graphene films on Ar plasma treated Ni and Cu foils using CH4 as carbon source. Through optimizing the process parameters, large scale single-layer graphene grown on Ni foil is comparable to that grown on Cu foil. The graphene films were able to be transferred to other substrates such as SiO2/Si, flexible transparent PET and verified by optical microscopy, Raman microscopy and scanning electron microscopy. The sheet resistance and transmission of the transferred graphene films on PET substrate were also discussed.     

Control of thickness uniformity and grain size in graphene films for transparent conductive electrodes

Large-scale and transferable graphene films grown on metal substrates by chemical vapor deposition (CVD) still hold great promise for future nanotechnology. To realize the promise, one of the key issues is to further improve the quality of graphene, e.g., uniform thickness, large grain size, and low defects. Here we grow graphene films on Cu foils by CVD at ambient pressure, and study the graphene nucleation and growth processes under different concentrations of carbon precursor. On the basis of the results, we develop a two-step ambient pressure CVD process to synthesize continuous single-layer graphene films with large grain size (up to hundreds of square micrometers). Scanning electron microscopy and Raman spectroscopy characterizations confirm the film thickness and uniformity. The transferred graphene films on cover glass slips show high electrical conductivity and high optical transmittance that make them suitable as transparent conductive electrodes. The growth mechanism of CVD graphene on Cu is also discussed, and a growth model has been proposed. Our results provide important guidance toward the synthesis of high quality uniform graphene films, and could offer a great driving force for graphene based applications.     

Twinning and twisting of tri- and bilayer graphene

The electronic, optical, and mechanical properties of bilayer and trilayer graphene vary with their structure, including the stacking order and relative twist, providing novel ways to realize useful characteristics not available to single layer graphene. However, developing controlled growth of bilayer and trilayer graphene requires efficient large-scale characterization of multilayer graphene structures. Here, we use dark-field transmission electron microscopy for rapid and accurate determination of key structural parameters (twist angle, stacking order, and interlayer spacing) of few-layer CVD graphene. We image the long-range atomic registry for oriented bilayer and trilayer graphene, find that it conforms exclusively to either Bernal or rhombohedral stacking, and determine their relative abundances. In contrast, our data on twisted multilayers suggest the absence of such long-range atomic registry. The atomic registry and its absence are consistent with the two different strain-induced deformations we observe; by tilting the samples to break mirror symmetry, we find a high density of twinned domains in oriented multilayer graphene, where multiple domains of two different stacking configurations coexist, connected by discrete twin boundaries. In contrast, individual layers in twisted regions continuously stretch and shear independently, forming elaborate Moiré patterns. These results, and the twist angle distribution in our CVD graphene, can be understood in terms of an angle-dependent interlayer potential model.     

Molecular absorption and photodesorption in pristine and functionalized large-area graphene layers

We studied the photodesorption behavior of pristine and nitric acid (HNO(3)) treated graphene layers fabricated by chemical vapor deposition (CVD). The decrease in electrical conductivity and a negative shift of the Dirac point in graphene layers illuminated with ultraviolet light are caused by molecular photodesorption, while the UV illumination does not degrade the carrier mobility of graphene layers. When graphene layers were treated with concentrated HNO(3), the photodesorption-induced current decrease became less significant than for pristine graphene layers. We suggest this is due to the passivation of oxygen-bearing functionalities to CVD grown graphene structural defects by HNO(3) functionalization, which prevents the further absorption of gas molecules. Our results provide a new strategy for stabilizing the electrical performance of CVD grown large-area graphene layers for applications ranging from nanoelectronics to optoelectronics.     

Growth of large-area single- and Bi-layer graphene by controlled carbon precipitation on polycrystalline Ni surfaces

We report graphene films composed mostly of one or two layers of graphene grown by controlled carbon precipitation on the surface of polycrystalline Ni thin films during atmospheric chemical vapor deposition (CVD). Controlling both the methane concentration during CVD and the substrate cooling rate during graphene growth can significantly improve the thickness uniformity. As a result, one- or two- layer graphene regions occupy up to 87% of the film area. Single layer coverage accounts for 5%–11% of the overall film. These regions expand across multiple grain boundaries of the underlying polycrystalline Ni film. The number density of sites with multilayer graphene/graphite (>2 layers) is reduced as the cooling rate decreases. These films can also be transferred to other substrates and their sizes are only limited by the sizes of the Ni film and the CVD chamber. Here, we demonstrate the formation of films as large as 1 in². These findings represent an important step towards the fabrication of large-scale high-quality graphene samples. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users.     

Topology evolution of graphene in chemical vapor deposition, a combined theoretical/experimental approach toward shape control of graphene domains

Morphology control of thin film relies on understanding multiple ongoing processes during deposition and growth. To reveal the shape evolution of graphene domains on copper surfaces in chemical vapor deposition (CVD), a combinative study is performed on the CVD growth of graphene on copper surfaces. To identify the factors that influence the adsorption and diffusion of carbon atoms and further determine the domain shape, simulations based on kinetic Monte Carlo techniques are carried out. The results reveal the dependence of the graphene domain shapes on the crystalline orientation of the underlying copper substrate surfaces.     

Spinodal decomposition of mono- to few-layer graphene on Ni substrates at low temperature

Mono to few-layer graphene were prepared on pre-annealed polycrystalline nickel substrates by chemical vapor deposition at a relatively low temperature of 800 degrees C using fast cooling rate. It was observed that the reduced solubility of Carbon in Ni at low temperature and an optimum gas mixing ratio (CH4:H2 = 60/80 (sccm)) can be used to synthesize mano-layer graphene that covers about 100 microm2 area. The number of graphene layers strongly depends upon the hydrogen and methane flow rates. An increase in the methane flow is found to increase the growth density of the single-layer graphene. The number of graphene layers was identified from micro-Raman spectra. The thinnest areas containing mono-layer graphene formed at small Ni grains surrounded by large Ni Grains can be explained in terms of Spinodal decomposition. Scanning tunneling microscopy observations of the graphene samples indicate that the graphene structure exhibits no defects, and extremely symmetry hexagon carbon at flat graphene surface is observed.     

Vapour-phase graphene epitaxy at low temperatures

We report an epitaxial growth of graphene, including homo- and hetero-epitaxy on graphite and SiC substrates, at a temperature as low as ∼540 °C. This vapour-phase epitaxial growth, carried out in a remote plasma-enhanced chemical vapor deposition (RPECVD) system using methane as the carbon source, can yield large-area high-quality graphene with the desired number of layers over the entire substrate surfaces following an AB-stacking layer-by-layer growth model. We also developed a facile transfer method to transfer a typical continuous one layer epitaxial graphene with second layer graphene islands on top of the first layer with the coverage of the second layer graphene islands being 20% (1.2 layer epitaxial graphene) from a SiC substrate onto SiO₂ and measured the resistivity, carrier density and mobility. Our work provides a new strategy toward the growth of graphene and broadens its prospects of application in future electronics.      

Continuity of graphene on polycrystalline copper

The atomic structure of graphene on polycrystalline copper substrates has been studied using scanning tunneling microscopy. The graphene overlayer maintains a continuous pristine atomic structure over atomically flat planes, monatomic steps, edges, and vertices of the copper surface. We find that facets of different identities are overgrown with graphene's perfect carbon honeycomb lattice. Our observations suggest that growth models including a stagnant catalytic surface do not apply to graphene growth on copper. Contrary to current expectations, these results reveal that the growth of macroscopic pristine graphene is not limited by the underlying copper structure.     

Direct growth of graphene/hexagonal boron nitride stacked layers

Graphene (G) and atomic layers of hexagonal boron nitride (h-BN) are complementary two-dimensional materials, structurally very similar but with vastly different electronic properties. Recent studies indicate that h-BN atomic layers would be excellent dielectric layers to complement graphene electronics. Graphene on h-BN has been realized via peeling of layers from bulk material to create G/h-BN stacks. Considering that both these layers can be independently grown via chemical vapor deposition (CVD) of their precursors on metal substrates, it is feasible that these can be sequentially grown on substrates to create the G/h-BN stacked layers useful for applications. Here we demonstrate the direct CVD growth of h-BN on highly oriented pyrolytic graphite and on mechanically exfoliated graphene, as well as the large area growth of G/h-BN stacks, consisting of few layers of graphene and h-BN, via a two-step CVD process. The G/h-BN film is uniform and continuous and could be transferred onto different substrates for further characterization and device fabrication.     

Novel growth mechanism of epitaxial graphene on metals

Graphene, a hexagonal sheet of sp(2)-bonded carbon atoms, has extraordinary properties which hold immense promise for nanoelectronic applications. Unfortunately, the popular preparation methods of micromechanical cleavage and chemical exfoliation of graphite do not easily scale up for application purposes. Epitaxial graphene provides an attractive alternative, though there are many challenges, not least of which is the absence of any understanding of the complex atomistic assembly kinetics of graphene layers. Here, we present a simple rate theory of epitaxial graphene growth on close-packed metal surfaces. On the basis of recent low-energy electron-diffraction microscopy experiments, our theory supposes that graphene islands grow predominantly by the attachment of five-atom clusters. With optimized kinetic parameters, our theory produces a quantitative account of the measured time-dependent carbon adatom density. The temperature dependence of this density at the onset of nucleation leads us to predict that the smallest stable precursor to graphene growth is an immobile island composed of six five-atom clusters. This conclusion is supported by a recent study based on temperature-programmed growth of epitaxial graphene, which provides direct evidence of nanoclusters whose coarsening leads to the formation of graphene layers. Our findings should motivate additional high-resolution imaging experiments and more detailed simulations which will yield important input to developing strategies for the large-scale production of epitaxial graphene.     

Direct growth of graphene on vertically standing glass by a metal-free chemical vapor deposition method

A new method to directly grow graphene on quartz glass substrate by atmospheric-pressure chemical vapor deposition (CVD) without using any catalyst was developed. The prime feature of this method is to build a vertical-glass model in the quartz tube to significantly increase the collision probability of the carbon precursors and reactive fragments between each other with the glass surface. The growth rate of high-quality graphene on glass remarkably increases compared with the conventional gas flow CVD technique. The optical transmittance and sheet resistance of the graphene glass can be readily adjusted by regulating growth time. When growth time is 35?min, the graphene glass presents an intriguing sheet resistance of about 1.48 kΩ sq^?1 at a transmittance of 93.08% and exhibits an excellent hydrophobic performance. The method is simple and scalable, and might stimulate various potential applications of transparent and conductive graphene glass in practical fields.     

Rayleigh imaging of graphene and graphene layers

We investigate graphene and graphene layers on different substrates by monochromatic and white-light confocal Rayleigh scattering microscopy. The image contrast depends sensitively on the dielectric properties of the sample as well as the substrate geometry and can be described quantitatively using the complex refractive index of bulk graphite. For a few layers (<6), the monochromatic contrast increases linearly with thickness. The data can be adequately understood by considering the samples behaving as a superposition of single sheets that act as independent two-dimensional electron gases. Thus, Rayleigh imaging is a general, simple, and quick tool to identify graphene layers, which is readily combined with Raman scattering, that provides structural identification.     

Synthesis of graphene on SiC substrate via Ni-silicidation reactions

In this work, the features of graphene layers are studied with the aim of preparing the thinnest layers possible. The graphene layers were prepared by the annealing of Ni/SiC structures. The main advantage of this process is a relatively low temperature compared with the method of graphene epitaxial growth on SiC and short annealing times compared with the chemical vapor deposition method. We prepared graphene layers from several Ni/SiC structures in which the Ni layer thickness ranged from 1 to 200 nm. The parameters of the annealing process (temperature, rate of temperature increase, annealing time) were modified during the experiments. The formed graphene layers were analyzed by means of Raman spectroscopy. From the spectra, the basic parameters of graphene, such as the number of carbon layers and crystallinity, were determined. The annealing of the Ni(200 nm)/SiC structure at 1080 °C for 10 s, produced graphene in the form of 3-4 carbon monolayers. The value was verified by X-ray Photoelectron Spectroscopy (XPS). Good agreement was achieved in the results obtained using Raman spectroscopy and XPS.     

Thermal stability of multilayer graphene films synthesized by chemical vapor deposition and stained by metallic impurities

Thermal stability is an important property of graphene that requires thorough investigation. This study reports the thermal stability of graphene films synthesized by chemical vapor deposition (CVD) on catalytic nickel substrates in a reducing atmosphere. Electron microscopies, atomic force microscopy, and Raman spectroscopy, as well as electronic measurements, were used to determine that CVD-grown graphene films are stable up to 700?°C. At 800?°C, however, graphene films were etched by catalytic metal nanoparticles, and at 1000?°C many tortuous tubular structures were formed in the film and carbon nanotubes were formed at the film edges and at catalytic metal-contaminated sites. Furthermore, we applied our pristine and thermally treated graphene films as active channels in field-effect transistors and characterized their electrical properties. Our research shows that remnant catalytic metal impurities play a critical role in damaging graphene films at high temperatures in a reducing atmosphere: this damage should be considered in the quality control of large-area graphene films for high temperature applications.