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Despite extensive microscale studies, the macroscopic mechanical properties of monolayer graphene remain underexplored. Here, we report the Young's modulus ($E$ = 1.11 $\pm$ 0.04 TPa), tensile strength (${\sigma}$ = 27.40 $\pm$ 4.36 GPa), and failure strain (${\epsilon}_f$ = 6.01 $\pm$ 0.92 %) of centimeter-scale single-crystal monolayer graphene (SCG) 'dog bone' samples with edges aligned along the zigzag (zz) direction, supported by an ultra-thin polymer (polycarbonate) film. For samples with edges along the armchair (ac) direction, we obtain $E$ = 1.01 $\pm$ 0.10 TPa, ${\sigma}$ = 20.21 $\pm$ 3.22 GPa, ${\epsilon}_f$ = 3.69 $\pm$ 0.38 %, and for chiral samples whose edges were between zz and ac, we obtain $E$= 0.75 $\pm$ 0.12 TPa, ${\sigma}$ = 23.56 $\pm$ 3.42 GPa, and ${\epsilon}_f$ = 4.53 $\pm$ 0.40 %. The SCG is grown on single crystal Cu(111) foils by chemical vapor deposition (CVD). We used a home-built 'float-on-water' (FOW) tensile testing system for tensile loading measurements that also enabled in situ crack observation. The quantized fracture mechanics (QFM) analysis predicts an edge defect size from several to tens of nanometers based on chirality and notch angle. Through Weibull analysis and given that the fatal defects are confined on the edges of macroscale samples, we projected strength ranging from 13.67 to 18.43 GPa for an A4-size SCG according to their chirality. The exceptional mechanical performance of macroscale single crystal graphene (SCG) paves the way for its widespread use in a very wide variety of applications., Comment: 76 pages, 44 figures

We report the scientific and technical queries regarding the article reported by Kim et al.1 on the mechanical properties of graphene-poly(methyl methacrylate) (PMMA) composites. Our analysis finds that the current experimental data is insufficient to fully support the conclusions presented in the article. We suggest the enhancement in Youngs modulus and strength of the graphene-PMMA laminates (GPL) samples are mainly due to the heat treatment of the polymer rather than the incorporation of graphene. The Raman spectroscopy data (as per our analysis) for the GPL samples indicates that large cracks and defects were introduced during the hot rolling process used to fabricate the graphene-PMMA composite. We believe that the queries will aid the audience in better understanding the mechanical response of graphene-PMMA composites., Comment: 14 Pages, 4 Figures

Atomically thin boron nitride (BN) nanosheets are important two-dimensional nanomaterials with many unique properties distinct from those of graphene, but the investigation of their mechanical properties still greatly lacks. Here we report that high-quality single-crystalline mono- and few-layer BN nanosheets are one of the strongest electrically insulating materials. More intriguingly, few-layer BN shows mechanical behaviors quite different from those of few-layer graphene under indentation. In striking contrast to graphene, whose strength decreases by more than 30% when the number of layers increases from 1 to 8, the mechanical strength of BN nanosheets is not sensitive to increasing thickness. We attribute this difference to the distinct interlayer interactions and hence sliding tendencies in these two materials under indentation. The significantly better mechanical integrity of BN nanosheets makes them a more attractive candidate than graphene for several applications, e.g. as mechanical reinforcements.

We demonstrate terahertz time-domain spectroscopy (THz-TDS) to be an accurate, rapid and scalable method to probe the interaction-induced Fermi velocity renormalization {\nu}F^* of charge carriers in graphene. This allows the quantitative extraction of all electrical parameters (DC conductivity {\sigma}DC, carrier density n, and carrier mobility {\mu}) of large-scale graphene films placed on arbitrary substrates via THz-TDS. Particularly relevant are substrates with low relative permittivity (< 5) such as polymeric films, where notable renormalization effects are observed even at relatively large carrier densities (> 10^12 cm-2, Fermi level > 0.1 eV). From an application point of view, the ability to rapidly and non-destructively quantify and map the electrical ({\sigma}DC, n, {\mu}) and electronic ({\nu}F^* ) properties of large-scale graphene on generic substrates is key to utilize this material in applications such as metrology, flexible electronics as well as to monitor graphene transfers using polymers as handling layers., Comment: 23 pages, 8 figures

Notwithstanding numerous density functional studies on the chemically induced transformation of multilayer graphene into a diamond-like film, a comprehensive convincing experimental proof of such a conversion is still lacking. We show that the fluorination of graphene sheets in Bernal (AB)-stacked bilayer graphene (AB-BLG) grown by chemical vapor deposition on a single crystal CuNi(111) surface triggers the formation of interlayer carbon-carbon bonds, resulting in a fluorinated diamond monolayer (F-diamane). Induced by fluorine chemisorption, the phase transition from AB-BLG to single layer diamond was studied and verified by X-ray photoelectron, ultraviolet photoelectron, Raman, UV-Vis, electron energy loss spectroscopies, transmission electron microscopy, and DFT calculations., Comment: 61 pages, 27 figures, 2 tables

A foundation of the modern technology that uses single-crystal silicon has been the growth of high-quality single-crystal Si ingots with diameters up to 12 inches or larger. For many applications of graphene, large-area high-quality (ideally of single-crystal) material will be enabling. Since the first growth on copper foil a decade ago, inch-sized single-crystal graphene has been achieved. We present here the growth, in 20 minutes, of a graphene film of 5 x 50 cm2 dimension with > 99% ultra-highly oriented grains. This growth was achieved by: (i) synthesis of sub-metre-sized single-crystal Cu(111) foil as substrate; (ii) epitaxial growth of graphene islands on the Cu(111) surface; (iii) seamless merging of such graphene islands into a graphene film with high single crystallinity and (iv) the ultrafast growth of graphene film. These achievements were realized by a temperature-driven annealing technique to produce single-crystal Cu(111) from industrial polycrystalline Cu foil and the marvellous effects of a continuous oxygen supply from an adjacent oxide. The as-synthesized graphene film, with very few misoriented grains (if any), has a mobility up to ~ 23,000 cm2V-1s-1 at 4 K and room temperature sheet resistance of ~ 230 ohm/square. It is very likely that this approach can be scaled up to achieve exceptionally large and high-quality graphene films with single crystallinity, and thus realize various industrial-level applications at a low cost.

Surface interaction is extremely important to both fundamental research and practical application. Physisorption can induce shape and structural distortion (i.e. conformational changes) in macromolecular and biomolecular adsorbates, but such phenomenon has rarely been observed on adsorbents. Here, we demonstrate theoretically and experimentally that atomically thin boron nitride (BN) nanosheets as an adsorbent experience conformational changes upon surface adsorption of molecules, increasing adsorption energy and efficiency. The study not only provides new perspectives on the strong adsorption capability of BN nanosheets and many other two-dimensional nanomaterials but also opens up possibilities for many novel applications. For example, we demonstrate that BN nanosheets with the same surface area as bulk hBN particles are more effective in purification and sensing.

Black phosphorus (BP) has attracted significant interest as a monolayer or few-layer material with extraordinary electrical and optoelectronic properties. However, degradation in air and other environments is an unresolved issue that may limit future applications. In particular the role of different ambient species has remained controversial. Here, we report systematic experiments combined with ab-initio calculations that address the effects of oxygen and water in the degradation of BP. Our results show that BP rapidly degrades whenever oxygen is present, but is unaffected by deaerated (i.e., O2 depleted) water. This behavior is rationalized by oxidation involving a facile dissociative chemisorption of O2, whereas H2O molecules are weakly physisorbed and do not dissociate on the BP surface. Oxidation (by O2) turns the hydrophobic pristine BP surface progressively hydrophilic. Our results have implications on the development of encapsulation strategies for BP, and open new avenues for exploration of phenomena in aqueous solutions including solution-gating, electrochemistry, and solution-phase approaches for exfoliation, dispersion, and delivery of BP.

Due to the drastically different intralayer versus interlayer bonding strengths, the mechanical, thermal, and electrical properties of two-dimensional (2D) materials are highly anisotropic between the in-plane and out-of-plane directions. The structural anisotropy may also play a role in chemical reactions, such as oxidation, reduction, and etching. Here, the composition, structure, and electrical properties of mechanically exfoliated WSe2 nano- sheets on SiO2/Si substrates were studied as a function of the extent of thermal oxidation. A major component of the oxidation, as indicated from optical and Raman data, starts from the nano-sheet edges and propagates laterally towards the center. Partial oxidation also occurs in certain areas at the surface of the flakes, which are shown to be highly conductive by microwave impedance microscopy. Using secondary ion mass spectroscopy, we also observed extensive oxidation at the WSe2/SiO2 interface. The combination of multiple microcopy methods can thus provide vital information on the spatial evolution of chemical reactions on 2D materials and the nanoscale electrical properties of the reaction products., Comment: To appear in Nano Lett

In graphene growth, island symmetry can become lower than the intrinsic symmetries of both graphene and the substrate. First-principles calculations and Monte Carlo modeling explain the shapes observed in our experiments and earlier studies for various metal surface symmetries. For equilibrium shape, edge energy variations $\delta E$ manifest in distorted hexagons with different ground-state edge structures. In growth or nucleation, energy variation enters exponentially as $\sim e^{\delta E / k_{B} T}$, strongly amplifying the symmetry breaking, up to completely changing the shapes to triangular, ribbon-like, or rhombic.

Plasmonic metasurfaces represent a promising platform for enhancing light-matter interaction. Active control of the optical response of metasurfaces is desirable for applications such as beam-steering, modulators and switches, biochemical sensors, and compact optoelectronic devices. Here we use a plasmonic metasurface with two Fano resonances to enhance the interaction of infrared light with electrically controllable single layer graphene. It is experimentally shown that the narrow spectral width of these resonances, combined with strong light/graphene coupling, enables reflectivity modulation by nearly an order of magnitude leading to a modulation depth as large as 90%. . Numerical simulations demonstrate the possibility of strong active modulation of the phase of the reflected light while keeping the reflectivity nearly constant, thereby paving the way to tunable infrared lensing and beam steering

The conversion of multilayer graphenes into sp^3-bonded carbon films on metal surfaces (through hydrogenation or fluorination of the outer surface of the top graphene layer) is indicated through first-principles computations. The main driving force for this conversion is the hybridization between carbon sp^3 orbitals and metal surface dz^2 orbitals. The induced electronic gap states in the carbon layers are confined in a region within 0.5 nm of the metal surface. Whether the conversion occurs depend on the fraction of hydrogenated (fluorinated) C atoms and on the number of stacked graphene layers. In the analysis of the Eliashberg spectral functions for the sp^3 carbon films on diamagnetic metals, the strong covalent metal-sp^3 carbon bonds induce soft phonon modes that predominantly contribute to large electron-phonon couplings, suggesting the possibility of phonon-mediated superconductivity. Our results suggest a route to experimental realization of large-area ultrathin sp^3-bonded carbon films on metal surfaces., Comment: 23 pages and 5 figures

Non-destructive and rapid evaluation of graphene directly on the growth substrate (Cu foils) by dark field (DF) optical microscopy is demonstrated. Without any additional treatment, graphene on Cu foils with various coverages can be quickly identified by DF imaging immediately after chemical vapor deposition growth with contrast comparable to scanning electron microscopy. The improved contrast of DF imaging compared to bright field optical imaging was found to be due to Rayleigh scattering of light by the copper steps beneath graphene. Indeed, graphene adlayers are readily distinguished, due to the different height of copper steps beneath graphene regions of different thickness., Comment: 17 pages, including 4 figures and 5 supporting figures

Magnetism in graphene is an emerging field that has received much theoretical attention. In particular, there have been exciting predictions for induced magnetism through proximity to a ferromagnetic insulator as well as through localized dopants and defects. Here, we discuss our experimental work using molecular beam epitaxy (MBE) to modify the surface of graphene and induce novel spin-dependent phenomena. First, we investigate the epitaxial growth the ferromagnetic insulator EuO on graphene and discuss possible scenarios for realizing exchange splitting and exchange fields by ferromagnetic insulators. Second, we investigate the properties of magnetic moments in graphene originating from localized p_z-orbital defects (i.e. adsorbed hydrogen atoms). The behavior of these magnetic moments is studied using non-local spin transport to directly probe the spin-degree of freedom of the defect-induced states. We also report the presence of enhanced electron g-factors caused by the exchange fields present in the system. Importantly, the exchange field is found to be highly gate dependent, with decreasing g-factors with increasing carrier densities.

We have demonstrated the deposition of EuO films on graphene by reactive molecular beam epitaxy in a special adsorption-controlled and oxygen-limited regime, which is a critical advance toward the realization of the exchange proximity interaction (EPI). It has been predicted that when the ferromagnetic insulator (FMI) EuO is brought into contact with graphene, an overlap of electronic wavefunctions at the FMI/graphene interface can induce a large spin splitting inside the graphene. Experimental realization of this effect could lead to new routes for spin manipulation, which is a necessary requirement for a functional spin transistor. Furthermore, EPI could lead to novel spintronic behavior such as controllable magnetoresistance, gate tunable exchange bias, and quantized anomalous Hall effect. However, experimentally, EuO has not yet been integrated onto graphene. Here we report the successful growth of high quality crystalline EuO on highly-oriented pyrolytic graphite (HOPG) and single-layer graphene. The epitaxial EuO layers have (001) orientation and do not induce an observable D peak (defect) in the Raman spectra. Magneto-optic measurements indicate ferromagnetism with Curie temperature of 69 K, which is the value for bulk EuO. Transport measurements on exfoliated graphene before and after EuO deposition indicate only a slight decrease in mobility.

Monolayer graphene has been grown on crystallized Cu (111) films on standard oxidized Si 100 mm wafers. The monolayer graphene demonstrates high uniformity (>97% coverage), with immeasurable defects (>95% defect-negligible) across the entire wafer. Key to these results is the phase transition of evaporated copper films from amorphous to crystalline at the growth temperature as corroborated by X-ray diffraction and electron backscatter diffraction. Noticeably, phase transition of copper film is observed on technologically ubiquitous oxidized Si wafer where the oxide is a standard amorphous thermal oxide. Ion mass spectroscopy indicates that the copper films can be purposely hydrogen-enriched during a hydrogen anneal which subsequently affords graphene growth with a sole carbonaceous precursor for low defect densities. Owing to the strong hexagonal lattice match, the graphene domains align to the Cu (111) domains, suggesting a pathway for increasing the graphene grains by maximizing the copper grain sizes. Fabricated graphene transistors on a flexible polyimide film yield a peak carrier mobility ~4,930 cm2/Vs.

In addition to its exotic electronic properties graphene exhibits unusually high intrinsic thermal conductivity. The physics of phonons - the main heat carriers in graphene - was shown to be substantially different in two-dimensional (2D) crystals, such as graphene, than in three-dimensional (3D) graphite. Here, we report our experimental study of the isotope effects on the thermal properties of graphene. Isotopically modified graphene containing various percentages of 13C were synthesized by chemical vapor deposition (CVD). The regions of different isotopic composition were parts of the same graphene sheet to ensure uniformity in material parameters. The thermal conductivity, K, of isotopically pure 12C (0.01% 13C) graphene determined by the optothermal Raman technique, was higher than 4000 W/mK at the measured temperature Tm~320 K, and more than a factor of two higher than the value of K in a graphene sheets composed of a 50%-50% mixture of 12C and 13C. The experimental data agree well with our molecular dynamics (MD) simulations, corrected for the long-wavelength phonon contributions via the Klemens model. The experimental results are expected to stimulate further studies aimed at better understanding of thermal phenomena in 2D crystals., Comment: 14 pages, 3 figures

The ability to protect refined metals from reactive environments is vital to many industrial and academic applications. Current solutions, however, typically introduce several negative effects, including increased thickness and changes in the metal physical properties. In this paper, we demonstrate for the first time the ability of graphene films grown by chemical vapor deposition to protect the surface of the metallic growth substrates of Cu and Cu/Ni alloy from air oxidation. SEM, Raman spectroscopy, and XPS studies show that the metal surface is well protected from oxidation even after heating at 200 \degree C in air for up to 4 hours. Our work further shows that graphene provides effective resistance against hydrogen peroxide. This protection method offers significant advantages and can be used on any metal that catalyzes graphene growth.

The fundamental properties of graphene are making it an attractive material for a wide variety of applications. Various techniques have been developed to produce graphene and recently we discovered the synthesis of large area graphene by chemical vapor deposition (CVD) of methane on Cu foils. We also showed that graphene growth on Cu is a surface-mediated process and the films were polycrystalline with domains having an area of tens of square microns. In this paper we report on the effect of growth parameters such as temperature, and methane flow rate and partial pressure on the growth rate, domain size, and surface coverage of graphene as determined by Raman spectroscopy, and transmission and scanning electron microscopy. Based on the results, we developed a two-step CVD process to synthesize graphene films with domains having an area of hundreds of square microns. Scanning electron microscopy and Raman spectroscopy clearly show an increase in domain size by changing the growth parameters. Transmission electron microscopy further shows that the domains are crystallographically rotated with respect to each other with a range of angles from about 13 degrees to nearly 30 degrees. Electrical transport measurements performed on back-gated FETs show that overall films with larger domains tend to have higher carrier mobility, up to about 16,000 cm2 V-1 s-1 at room temperature., Comment: 13 pages, 1 table, 7 figures

Understanding and engineering the domain boundaries in chemically vapor deposited (CVD) monolayer graphene will be critical for improving its properties. In this study, a combination of transmission electron microscopy (TEM) techniques including selected area electron diffraction (SAED), high resolution transmission electron microscopy (HRTEM), and dark field (DF) TEM was used to study the boundary orientation angle distribution and the nature of the carbon bonds at the domain boundaries. This report provides an important first step towards a fundamental understanding of these domain boundaries. The results show that, for the graphene grown in this study, the 46 measured misorientation angles are all between 11-30 degrees (with the exception of one at 7 degrees). HRTEM images show the presence of adsorbates in almost all of the boundary areas. When a boundary was imaged, defects were seen (dangling bonds) at the boundaries that likely contribute to adsorbates binding at these boundaries. DFTEM images also showed the presence of a 'twin like' boundary.

Graphene growth by chemical vapor deposition has received a lot of attention recently owing to the ease with which large area films can be grown, but growth of large domain or equivalently large grain size has not been reported yet. In this brevia, we report on a CVD process that yields graphene with domains of hundreds of micrometers, by very low pressure CVD, less than 50 mTorr, and very low precursor flow rates using methane as the source of carbon on the inside of copper foil enclosures at high temperature, around 1000 oC. The carrier mobility for the large-domain graphene films is up to 21,000 cm2/Vs.

Using molecular dynamics simulations and first principles calculations, we have studied the structure and mechanical strength of tilt grain boundaries in graphene sheets that arise during CVD growth of graphene on metal substrates. Surprisingly, we find that for tilt boundaries in the vicinity of both the zig-zag and arm-chair orientations, large angle boundaries with a higher density of 5-7 defect pairs are stronger than the low-angle boundaries which are comprised of fewer defects per unit length. Interestingly, the trends in our results cannot be explained by a continuum Griffith-type fracture mechanics criterion, which predicts the opposite trend due to that fact that it does not account for the critical bonds that are responsible for the failure mechanism. We have identified the highly-strained bonds in the 7-member rings that lead to the failure of the sheets, and we have found that large angle boundaries are able to better accommodate the strained 7-rings. Our results provide guidelines for designing growth methods to obtain grain boundary structures that can have strengths close to that of pristine graphene.