Monolayer Graphene Domains Research Articles

Evolution of cellulose acetate to monolayer graphene

Converting biomass waste into high-value products presents a challenging task in the environmental field. Growth of graphene from solid-state precursors is cost-effective and is becoming a hot research topic. However, the underlying mechanisms are as yet unclear. In this work, we report a novel method for directly growing adlayer-free large area graphene from cellulose acetate, the main component of cigarette filter waste. The evolution of cellulose acetate to reduced graphene oxide and finally to graphene is shown in this work for the first time. The effect of various growth parameters, hydrogen concentration and Cu grain boundaries on the size and qualities of the monolayer graphene domains is clarified. Finally, the mechanism for the growth of graphene from a solid-state precursor is proposed. The field-effect-transistor fabricated from transferred monolayer graphene demonstrated high electron and hole mobilities ∼1500 cm2/(V·s). This work presents a new opportunity for converting biomass waste into high-value graphene products.

In Situ Variable-Temperature Scanning Tunneling Microscopy Studies of Graphene Growth Using Benzene on Pd(111).

Using a combination of in situ ultrahigh-vacuum variable-temperature scanning tunneling microscopy, ex situ Raman spectroscopy, and scanning electron microscopy, we investigated the growth of graphene using benzene on Pd(111) at temperatures up to 1100 K. Benzene adsorbs readily on Pd(111) at room temperature and forms an ordered superstructure upon annealing at 473 K. Exposure to benzene at 673 K enhances Pd step motion and yields primarily amorphous carbon upon cooling to room temperature. Monolayer graphene domains, 10-30 nm in size, appear during annealing this sample at 873 K. Dosing benzene at 1100 K results in graphene domains with varying degrees of crystallinity, while post-deposition annealing at 1100 K for 1200 s yields monolayer graphene domains larger than 150 × 150 nm2. Our results, which indicate that graphene growth on Pd(111) using benzene requires deposition/annealing temperatures higher than 673 K, are in striking contrast with the reported growth of graphene using benzene at temperatures as low as 373 K on relatively inert Cu surfaces.

Characterization of graphene grown on copper foil by chemical vapor deposition (CVD) at ambient pressure conditions

AbstractIn the aim to get high quality graphene films, with large domains and free from impurities, minimizing also the manufacturing costs, we investigate the graphene grown on copper (Cu) foil by chemical vapor deposition at ambient pressure conditions, by using methane (CH4) as carbon source, diluted in a suitable mixture of argon (Ar) and hydrogen (H2). Several graphene samples were synthesized, for variable exposure times to hydrocarbon precursor, in the range from 1 min to 1 hr. The quality of the graphene films and their structural, morphological, and electronic properties were evaluated by micro‐Raman spectroscopy and other techniques, including, scanning tunneling microscopy, atomic force microscopy, and scanning electronic microscopy. In particular, samples obtained with shorter growth time (less than 10 min) exhibit a non‐uniform coverage of the Cu surface, whereas those synthesized with exposure time between 10 and 30 min show a prevalence of well‐ordered monolayer graphene domains. For longer deposition, the amount of disordered domains increases, as revealed by Raman analysis, and the resulting film shows a nonself‐limiting growth behavior for chemical vapor deposition at atmospheric conditions. In addition, we observed 2 kinds of monolayer graphene, in terms of coupling with the Cu surface, for the samples synthesized between 10 and 30 min. To the best of our knowledge, “coupled” and “decoupled” graphene regions have never been reported at the same time on Cu surface. Furthermore, a Raman statistical analysis has been performed on the G and 2D bands measured in both the kinds of regions, gaining evidence of a bimodal behavior for the graphene spots, corresponding to “coupled” and “decoupled” configurations. This difference, which is appreciable also by the optical microscopy inspection, could be related to the local Cu oxidation and to oxygen intercalation after graphene growth.

Direct Growth of Graphene on Silicon by Metal-Free Chemical Vapor Deposition

The metal-free synthesis of graphene on single-crystal silicon substrates, the most common commercial semiconductor, is of paramount significance for many technological applications. In this work, we report the growth of graphene directly on an upside-down placed, single-crystal silicon substrate using metal-free, ambient-pressure chemical vapor deposition. By controlling the growth temperature, in-plane propagation, edge-propagation, and core-propagation, the process of graphene growth on silicon can be identified. This process produces atomically flat monolayer or bilayer graphene domains, concave bilayer graphene domains, and bulging few-layer graphene domains. This work would be a significant step toward the synthesis of large-area and layer-controlled, high-quality graphene on single-crystal silicon substrates.

Seed-Assisted Growth of Single-Crystalline Patterned Graphene Domains on Hexagonal Boron Nitride by Chemical Vapor Deposition.

Vertical heterostructures based on two-dimensional layered materials, such as stacked graphene and hexagonal boron nitride (G/h-BN), have stimulated wide interest in fundamental physics, material sciences and nanoelectronics. To date, it still remains challenging to obtain high quality G/h-BN heterostructures concurrently with controlled nucleation density and thickness uniformity. In this work, with the aid of the well-defined poly(methyl methacrylate) seeds, effective control over the nucleation densities and locations of graphene domains on the predeposited h-BN monolayers was realized, leading to the formation of patterned G/h-BN arrays or continuous films. Detailed spectroscopic and morphological characterizations further confirmed that ∼85.7% of such monolayer graphene domains were of single-crystalline nature with their domain sizes predetermined throughout seed interspacing. Density functional theory calculations suggested that a self-terminated growth mechanism can be applied for the related graphene growth on h-BN/Cu. In turn, as-constructed field-effect transistor arrays based on such synthesized single-crystalline G/h-BN patterning were found to be compatible with fabricating devices with nice and steady performance, hence holding great promise for the development of next-generation graphene-based electronics.

Control of the nucleation and quality of graphene grown by low-pressure chemical vapor deposition with acetylene

Although many studies have reported the chemical vapor deposition (CVD) growth of large-area monolayer graphene from methane, synthesis of graphene using acetylene as the source gas has not been fully explored. In this study, the low-pressure CVD (LPCVD) growth of graphene from acetylene was systematically investigated. We succeeded in regulating the domain size, defects density, layer number and the sheet resistance of graphene by changing the acetylene flow rates. Scanning electron microscopy and Raman spectroscopy were employed to confirm the layer number, uniformity and quality of the graphene films. It is found that a low flow rate of acetylene (0.28sccm) is required to form high-quality monolayer graphene in our system. On the other hand, the high acetylene flow rate (7sccm) will induce the growth of the bilayer graphene domains with high defects density. On the basis of selected area electron diffraction (SAED) pattern, the as-grown monolayer graphene domains were analyzed to be polycrystal. We also discussed the relation between the sheet resistacne and defects density in graphene. Our results provide great insights into the understanding of the CVD growth of monolayer and bilayer graphene from acetylene.

Oxidation-assisted graphene heteroepitaxy on copper foil.

We propose an innovative, easy-to-implement approach to synthesize aligned large-area single-crystalline graphene flakes by chemical vapor deposition on copper foil. This method doubly takes advantage of residual oxygen present in the gas phase. First, by slightly oxidizing the copper surface, we induce grain boundary pinning in copper and, in consequence, the freezing of the thermal recrystallization process. Subsequent reduction of copper under hydrogen suddenly unlocks the delayed reconstruction, favoring the growth of centimeter-sized copper (111) grains through the mechanism of abnormal grain growth. Second, the oxidation of the copper surface also drastically reduces the nucleation density of graphene. This oxidation/reduction sequence leads to the synthesis of aligned millimeter-sized monolayer graphene domains in epitaxial registry with copper (111). The as-grown graphene flakes are demonstrated to be both single-crystalline and of high quality.

Hexagonal Graphene Onion Rings

Precise spatial control of materials is the key capability of engineering their optical, electronic, and mechanical properties. However, growth of graphene on Cu was revealed to be seed-induced two-dimensional (2D) growth, limiting the synthesis of complex graphene spatial structures. In this research, we report the growth of onion ring like three-dimensional (3D) graphene structures, which are comprised of concentric one-dimensional hexagonal graphene ribbon rings grown under 2D single-crystal monolayer graphene domains. The ring formation arises from the hydrogenation-induced edge nucleation and 3D growth of a new graphene layer on the edge and under the previous one, as supported by first principles calculations. This work reveals a new graphene-nucleation mechanism and could also offer impetus for the design of new 3D spatial structures of graphene or other 2D layered materials. Additionally, in this research, two special features of this new 3D graphene structure were demonstrated, including nanoribbon fabrication and potential use in lithium storage upon scaling.

Square-Shaped, Single-Crystal, Monolayer Graphene Domains by Low-Pressure Chemical Vapor Deposition

Square-shaped, single-crystal, monolayer graphene domains are grown on Cu foils by low-pressure chemical vapor deposition. The domains are remarkably well-aligned along the direction of flow of the gases. Scanning electron microscopy shows that these ‘square’ domains have clean, smooth edges which permit seamless, defect-free merging of the domains. Raman spectra and transmission electron microscopy together demonstrate that individual domains are single layer, and electron diffraction reveals that these domains are single crystals. The expansion mechanism of ‘square’ graphene domains is discussed in the context of our aligned, tailored domain shapes. This work represents an important step toward realization of fabrication of larger area, single-crystal monolayer graphene sheets with controllable shape and alignment.

Growth of large domain epitaxial graphene on the C-face of SiC

Growth of epitaxial graphene on the C-face of SiC has been investigated. Using a confinement controlled sublimation (CCS) method, we have achieved well controlled growth and been able to observe propagation of uniform monolayer graphene. Surface patterns uncover two important aspects of the growth, i.e., carbon diffusion and stoichiometric requirement. Moreover, a new “stepdown” growth mode has been discovered. Via this mode, monolayer graphene domains can have an area of hundreds of square micrometers, while, most importantly, step bunching is avoided and the initial uniformly stepped SiC surface is preserved. The stepdown growth provides a possible route towards uniform epitaxial graphene in wafer size without compromising the initial flat surface morphology of SiC.

Correction to Controllable Synthesis of Submillimeter Single-Crystal Monolayer Graphene Domains on Copper Foils by Suppressing Nucleation

Correction to Controllable Synthesis of Submillimeter Single-Crystal Monolayer Graphene Domains on Copper Foils by Suppressing Nucleation

Toward the Synthesis of Wafer-Scale Single-Crystal Graphene on Copper Foils

In this research, we constructed a controlled chamber pressure CVD (CP-CVD) system to manipulate graphene's domain sizes and shapes. Using this system, we synthesized large (~4.5 mm(2)) single-crystal hexagonal monolayer graphene domains on commercial polycrystalline Cu foils (99.8% purity), indicating its potential feasibility on a large scale at low cost. The as-synthesized graphene had a mobility of positive charge carriers of ~11,000 cm(2) V(-1) s(-1) on a SiO(2)/Si substrate at room temperature, suggesting its comparable quality to that of exfoliated graphene. The growth mechanism of Cu-based graphene was explored by studying the influence of varied growth parameters on graphene domain sizes. Cu pretreatments, electrochemical polishing, and high-pressure annealing are shown to be critical for suppressing graphene nucleation site density. A pressure of 108 Torr was the optimal chamber pressure for the synthesis of large single-crystal monolayer graphene. The synthesis of one graphene seed was achieved on centimeter-sized Cu foils by optimizing the flow rate ratio of H(2)/CH(4). This work should provide clear guidelines for the large-scale synthesis of wafer-scale single-crystal graphene, which is essential for the optimized graphene device fabrication.

Interface Formation in Monolayer Graphene-Boron Nitride Heterostructures

The ability to control the formation of interfaces between different materials has become one of the foundations of modern materials science. With the advent of two-dimensional (2D) crystals, low-dimensional equivalents of conventional interfaces can be envisioned: line boundaries separating different materials integrated in a single 2D sheet. Graphene and hexagonal boron nitride offer an attractive system from which to build such 2D heterostructures. They are isostructural, nearly lattice-matched, and isoelectronic, yet their different band structures promise interesting functional properties arising from their integration. Here, we use a combination of in situ microscopy techniques to study the growth and interface formation of monolayer graphene-boron nitride heterostructures on ruthenium. In a sequential chemical vapor deposition process, boron nitride grows preferentially at the edges of existing monolayer graphene domains, which can be exploited for synthesizing continuous 2D membranes of graphene embedded in boron nitride. High-temperature growth leads to intermixing near the interface, similar to interfacial alloying in conventional heterostructures. Using real-time microscopy, we identify processes that eliminate this intermixing and thus pave the way to graphene-boron nitride heterostructures with atomically sharp interfaces.

Controllable Synthesis of Submillimeter Single-Crystal Monolayer Graphene Domains on Copper Foils by Suppressing Nucleation

Submillimeter single-crystal monolayer and multilayer graphene domains were prepared by an atmospheric pressure chemical vapor deposition method with suppressing nucleation on copper foils through an annealing procedure. A facile oxidation visualization method was applied to study the nucleation density and morphology of graphene domains on copper foils. Scanning electron microscopy, transmission electron microscopy, atomic force microscopy, polarized optical microscopy, and Raman spectra showed that the submillimeter graphene domains were monolayer single crystals.

Si intercalation/deintercalation of graphene on 6H-SiC(0001)

The intercalation and deintercalation mechanisms of Si deposited on monolayer graphene grown on SiC(0001) substrates and after subsequent annealing steps are investigated using low-energy electron microscopy (LEEM), photoelectron spectroscopy (PES), and micro-low-energy electron diffraction (\ensuremath{\mu}-LEED). After Si deposition on samples kept at room temperature, small Si droplets are observed on the surface, but no intercalation can be detected. Intercalation is revealed to occur at an elevated temperature of about 800 \ifmmode^\circ\else\textdegree\fi{}C. The Si is found to migrate to the interface region via defects and domain boundaries. This observation may provide an answer to the problem of controlling homogeneous bi-/multilayer graphene growth on nearly perfect monolayer graphene samples prepared on SiC(0001). Likewise, Si penetrates more easily small monolayer graphene domains because of the higher density of domain boundaries. Upon annealing at 1000--1100 \ifmmode^\circ\else\textdegree\fi{}C, formation of SiC on the surface is revealed by the appearance of a characteristic surface state located at about 1.5 eV below the Fermi level. A streaked \ensuremath{\mu}-LEED pattern is also observed at this stage. The SiC formed on the surface is found to decompose again after annealing at temperatures higher than 1200 \ifmmode^\circ\else\textdegree\fi{}C.

Graphene on Pt(111): Growth and substrate interaction

In situ low-energy electron microscopy (LEEM) of graphene growth combined with measurements of the graphene structure and electronic band structure has been used to study graphene on Pt(111). Growth by carbon segregation produces macroscopic monolayer graphene domains extending continuously across Pt(111) substrate steps and bounded by strongly faceted edges. LEEM during cooling from the growth temperature shows the propagation of wrinkles in the graphene sheet, driven by thermal stress. The lattice mismatch between graphene and Pt(111) is accommodated by moir\'e structures with a large number of different rotational variants, without a clear preference for a particular interface geometry. Fast and slow growing graphene domains exhibit moir\'e structures with small [e.g., ${(3\ifmmode\times\else\texttimes\fi{}3)}_{\text{G}}$, $(\sqrt{6}\ifmmode\times\else\texttimes\fi{}\sqrt{6})\text{R}{2}_{\text{G}}$, and $(2\ifmmode\times\else\texttimes\fi{}2)\text{R}{4}_{\text{G}}$] and large unit cells [e.g., $(\sqrt{44}\ifmmode\times\else\texttimes\fi{}\sqrt{44})\text{R}{15}_{\text{G}}$, $(\sqrt{52}\ifmmode\times\else\texttimes\fi{}\sqrt{52})\text{R}{14}_{\text{G}}$, and ${(8\ifmmode\times\else\texttimes\fi{}8)}_{\text{G}}$], respectively. A weak substrate coupling, suggested by the growth and structural properties of monolayer graphene on Pt(111), is confirmed by maps of the band structure, which is close to that of isolated graphene aside from minimal hole doping due to charge transfer from the metal. Finally, the decoupled graphene monolayer on Pt(111) appears impenetrable to carbon diffusion, which self-limits the graphene growth at monolayer thickness. Thicker graphene domains, which can form at boundaries between monolayer domains, have been used to characterize the properties of few-layer graphene on Pt(111).

Graphene growth on polycrystalline Ru thin films

Monolayer graphene has been grown on polycrystalline Ru thin films on SiO2/Si substrates. The Ru films have columnar structure with strongly aligned grains exposing flat (0001) surface facets. Adjacent grains show small relative tilts of their [0001] axes and variations in in-plane orientation. Graphene layers grown on this template cover the entire surface and have uniform monolayer thickness. Analysis of the graphene/Ru moiré structure shows that monocrystalline graphene domains are coherent across a large number of substrate grains. Hence, the size of monolayer graphene domains is not limited by grain boundaries in the metal template.