Control and Characterization of Individual Grains and Grain Boundaries in Graphene Grown by Chemical Vapor Deposition

The strong interest in graphene has motivated the scalable production of high quality graphene and graphene devices. Since large-scale graphene films synthesized to date are typically polycrystalline, it is important to characterize and control grain boundaries, generally believed to degrade graphene quality. Here we study single-crystal graphene grains synthesized by ambient CVD on polycrystalline Cu, and show how individual boundaries between coalescing grains affect graphene's electronic properties. The graphene grains show no definite epitaxial relationship with the Cu substrate, and can cross Cu grain boundaries. The edges of these grains are found to be predominantly parallel to zigzag directions. We show that grain boundaries give a significant Raman "D" peak, impede electrical transport, and induce prominent weak localization indicative of intervalley scattering in graphene. Finally, we demonstrate an approach using pre-patterned growth seeds to control graphene nucleation, opening a route towards scalable fabrication of single-crystal graphene devices without grain boundaries.Comment: New version with additional data. Accepted by Nature Material

A new Raman metric for the characterisation of graphene oxide and its derivatives

Raman spectroscopy is among the primary techniques for the characterisation of graphene materials, as it provides insights into the quality of measured graphenes including their structure and conductivity as well as the presence of dopants. However, our ability to draw conclusions based on such spectra is limited by a lack of understanding regarding the origins of the peaks. Consequently, traditional characterisation techniques, which estimate the quality of the graphene material using the intensity ratio between the D and the G peaks, are unreliable for both GO and rGO. Herein we reanalyse the Raman spectra of graphenes and show that traditional methods rely upon an apparent G peak which is in fact a superposition of the G and D’ peaks. We use this understanding to develop a new Raman characterisation method for graphenes that considers the D’ peak by using its overtone the 2D’. We demonstrate the superiority and consistency of this method for calculating the oxygen content of graphenes, and use the relationship between the D’ peak and graphene quality to define three regimes. This has important implications for purification techniques because, once GO is reduced beyond a critical threshold, further reduction offers limited gain in conductivity

Laser-induced etching of few-layer graphene synthesized by Rapid-Chemical Vapour Deposition on Cu thin films

The outstanding electrical and mechanical properties of graphene make it very attractive for several applications, Nanoelectronics above all. However a reproducible and non destructive way to produce high quality, large-scale area, single layer graphene sheets is still lacking. Chemical Vapour Deposition of graphene on Cu catalytic thin films represents a promising method to reach this goal, because of the low temperatures (T < 900 Celsius degrees) involved during the process and of the theoretically expected monolayer self-limiting growth. On the contrary such self-limiting growth is not commonly observed in experiments, thus making the development of techniques allowing for a better control of graphene growth highly desirable. Here we report about the local ablation effect, arising in Raman analysis, due to the heat transfer induced by the laser incident beam onto the graphene sample.Comment: v1:9 pages, 8 figures, submitted to SpringerPlus; v2: 11 pages, PDFLaTeX, 9 figures, revised peer-reviewed version resubmitted to SpringerPlus; 1 figure added, figure 1 and 4 replaced,typos corrected, "Results and discussion" section significantly extended to better explain etching mechanism and features of Raman spectra, references adde

Nano-Architecture of nitrogen-doped graphene films synthesized from a solid CN source

New synthesis routes to tailor graphene properties by controlling the concentration and chemical configuration of dopants show great promise. Herein we report the direct reproducible synthesis of 2-3% nitrogen-doped ‘few-layer’ graphene from a solid state nitrogen carbide a-C:N source synthesized by femtosecond pulsed laser ablation. Analytical investigations, including synchrotron facilities, made it possible to identify the configuration and chemistry of the nitrogen-doped graphene films. Auger mapping successfully quantified the 2D distribution of the number of graphene layers over the surface, and hence offers a new original way to probe the architecture of graphene sheets. The films mainly consist in a Bernal ABA stacking three-layer architecture, with a layer number distribution ranging from 2 to 6. Nitrogen doping affects the charge carrier distribution but has no significant effects on the number of lattice defects or disorders, compared to undoped graphene synthetized in similar conditions. Pyridinic, quaternary and pyrrolic nitrogen are the dominant chemical configurations, pyridinic N being preponderant at the scale of the film architecture. This work opens highly promising perspectives for the development of self-organized nitrogen-doped graphene materials, as synthetized from solid carbon nitride, with various functionalities, and for the characterization of 2D materials using a significant new methodology

Electric double-layer capacitance between an ionic liquid and few-layer graphene

Ionic-liquid gates have a high carrier density due to their atomically thin electric double layer (EDL) and extremely large geometrical capacitance C-g. However, a high carrier density in graphene has not been achieved even with ionic-liquid gates because the EDL capacitance C-EDL between the ionic liquid and graphene involves the series connection of C-g and the quantum capacitance C-q, which is proportional to the density of states. We investigated the variables that determine C-EDL at the molecular level by varying the number of graphene layers n and thereby optimising C-q. The C-EDL value is governed by C-q at n, 4, and by C-g at n > 4. This transition with n indicates a composite nature for C-EDL. Our finding clarifies a universal principle that determines capacitance on a microscopic scale, and provides nanotechnological perspectives on charge accumulation and energy storage using an ultimately thin capacitor

Properties of Graphene: A Theoretical Perspective

In this review, we provide an in-depth description of the physics of monolayer and bilayer graphene from a theorist's perspective. We discuss the physical properties of graphene in an external magnetic field, reflecting the chiral nature of the quasiparticles near the Dirac point with a Landau level at zero energy. We address the unique integer quantum Hall effects, the role of electron correlations, and the recent observation of the fractional quantum Hall effect in the monolayer graphene. The quantum Hall effect in bilayer graphene is fundamentally different from that of a monolayer, reflecting the unique band structure of this system. The theory of transport in the absence of an external magnetic field is discussed in detail, along with the role of disorder studied in various theoretical models. We highlight the differences and similarities between monolayer and bilayer graphene, and focus on thermodynamic properties such as the compressibility, the plasmon spectra, the weak localization correction, quantum Hall effect, and optical properties. Confinement of electrons in graphene is nontrivial due to Klein tunneling. We review various theoretical and experimental studies of quantum confined structures made from graphene. The band structure of graphene nanoribbons and the role of the sublattice symmetry, edge geometry and the size of the nanoribbon on the electronic and magnetic properties are very active areas of research, and a detailed review of these topics is presented. Also, the effects of substrate interactions, adsorbed atoms, lattice defects and doping on the band structure of finite-sized graphene systems are discussed. We also include a brief description of graphane -- gapped material obtained from graphene by attaching hydrogen atoms to each carbon atom in the lattice.Comment: 189 pages. submitted in Advances in Physic

Micro-Raman and micro-transmission imaging of epitaxial graphene grown on the Si and C faces of 6H-SiC

Micro-Raman and micro-transmission imaging experiments have been done on epitaxial graphene grown on the C- and Si-faces of on-axis 6H-SiC substrates. On the C-face it is shown that the SiC sublimation process results in the growth of long and isolated graphene ribbons (up to 600 μm) that are strain-relaxed and lightly p-type doped. In this case, combining the results of micro-Raman spectroscopy with micro-transmission measurements, we were able to ascertain that uniform monolayer ribbons were grown and found also Bernal stacked and misoriented bilayer ribbons. On the Si-face, the situation is completely different. A full graphene coverage of the SiC surface is achieved but anisotropic growth still occurs, because of the step-bunched SiC surface reconstruction. While in the middle of reconstructed terraces thin graphene stacks (up to 5 layers) are grown, thicker graphene stripes appear at step edges. In both the cases, the strong interaction between the graphene layers and the underlying SiC substrate induces a high compressive thermal strain and n-type doping

Characterization of the second- and third-harmonic optical susceptibilities of atomically thin tungsten diselenide

Supplementary information accompanies this paper at https://doi.org/10.1038/s41598-018-28374-1We report the first detailed characterization of the sheet third-harmonic optical susceptibility, χ(3)s, of tungsten diselenide (WSe2). With a home-built multiphoton microscope setup developed to study harmonics generation, we map the second and third-harmonic intensities as a function of position in the sample, pump power and polarization angle, for single- and few-layers flakes of WSe2. We register a value of |χ(3)s| ≈ 0.9 × 10-28 m3 V-2 at a fundamental excitation frequency of ℏω = 0.8 eV, which is comparable in magnitude to the third-harmonic susceptibility of other group-VI transition metal dichalcogenides. The simultaneously recorded sheet second-harmonic susceptibility is found to be |χ(2)s| ≈ 0.7 × 10-19 m2 V-1 in very good agreement on the order of magnitude with recent reports for WSe2, which asserts the robustness of our values for |χ(3)s|.Y.W.H. acknowledges scholarship support from NGS. G.E. acknowledges financial support from National Research Foundation of Singapore (NRF Research Fellowship NRF-NRFF2011-02 and medium-sized centre programme) and Ministry of Education of Singapore (AcRF Tier 2 MOE2015-T2-2-123). V. M. P. acknowledges fnancial support from Ministry of Education of Singapore (FRC AcRF Tier 1 R-144-000-386-114). J.C.V.G. acknowledges fnancial support from CA2DM through National Research Foundation of Singapore (NRF-CRP Grant No. R-144-000-295-281)

A Tunable Phonon-Exciton Fano System in Bilayer Graphene

Interference between different possible paths lies at the heart of quantum physics. Such interference between coupled discrete and continuum states of a system can profoundly change its interaction with light as seen in Fano resonance. Here we present a unique many-body Fano system composed of a discrete phonon vibration and continuous electron-hole pair transitions in bilayer graphene. Mediated by the electron-phonon interactions, the excited state is described by new quanta of elementary excitations of hybrid phonon-exciton nature. Infrared absorption of the hybrid states exhibit characteristic Fano lineshapes with parameters renormalized by many-body interactions. Remarkably, the Fano resonance in bilayer graphene is continuously tunable through electrical gating. Further control of the phonon-exciton coupling may be achieved with an optical field exploiting the excited state infrared activity. This tunable phonon-exciton system also offers the intriguing possibility of a 'phonon laser' with stimulated phonon amplification generated by population inversion of band-edge electrons.Comment: 21 pages, 3 figure

Detection of Wolbachia in the Tick Ixodes ricinus is Due to the Presence of the Hymenoptera Endoparasitoid Ixodiphagus hookeri

The identification of micro-organisms carried by ticks is an important issue for human and animal health. In addition to their role as pathogen vectors, ticks are also the hosts for symbiotic bacteria whose impact on tick biology is poorly known. Among these, the bacterium Wolbachia pipientis has already been reported associated with Ixodes ricinus and other tick species. However, the origins of Wolbachia in ticks and their consequences on tick biology (known to be very diverse in invertebrates, ranging from nutritional symbionts in nematodes to reproductive manipulators in insects) are unknown. Here we report that the endoparasitoid wasp Ixodiphagus hookeri (Hymenoptera, Chalcidoidea, Encyrtidae) – strictly associated with ticks for their development - is infested at almost 100% prevalence by a W. pipientis strain belonging to a Wolbachia supergroup that has already been reported as associated with other hymenopteran parasitoids. In a natural population of I. ricinus that suffers high parasitism rates due to I. hookeri, we used specific PCR primers for both hymenopteran and W. pipientis gene fragments to show that all unfed tick nymphs parasitized by I. hookeri also harbored Wolbachia, while unparasitized ticks were Wolbachia-free. We demonstrated experimentally that unfed nymphs obtained from larvae exposed to I. hookeri while gorging on their vertebrate host also harbor Wolbachia. We hypothesize that previous studies that have reported W. pipientis in ticks are due to the cryptic presence of the endoparasitoid wasp I. hookeri. This association has remained hidden until now because parasitoids within ticks cannot be detected until engorgement of the nymphs brings the wasp eggs out of diapause. Finally, we discuss the consequences of this finding for our understanding of the tick microbiome, and their possible role in horizontal gene transfer among pathogenic and symbiotic bacteria