Project description:Improving the ferromagnetism properties of pure carbon-based materials is extremely important for their application in spintronics. Hydrogenation of graphene is an effective way to induce magnetic moment into graphene with the advantage of reversibility. However, little experimental work has been done to prove the effect of hydrogen on the magnetic properties of graphene so far, except for systems containing a large amount of oxygen or plasma-induced vacancy which complicated the magnetic origin. Here we report a facile electrochemical cathodic method to generate hydrogenated multilayer graphene or few-layer graphite using graphite powder as the raw material, and observed hydrogen-induced ferromagnetism in samples annealed at different temperatures. The observed results suggest that ferromagnetism of hydrogenated multilayer graphene can be tuned by high temperature treatment, which is attributed to a changeable relative amount of hydrogen atoms chemisorpted on two different sublattices during thermal treatment.
Project description:The origin of the ferromagnetism in metal-free graphitic materials has been a decade-old puzzle. The possibility of long-range magnetic order in graphene has been recently questioned by the experimental findings that point defects in graphene, such as fluorine adatoms and vacancies, lead to defect-induced paramagnetism but no magnetic ordering down to 2 K. It remains controversial whether collective magnetic order in graphene can emerge from point defects at finite temperatures. This work provides a new framework for understanding the ferromagnetism in hydrogenated graphene, highlighting the key contribution of the spin-polarized pseudospin as a "mediator" of long-range magnetic interactions in graphene. Using first-principles calculations of hydrogenated graphene, we found that the unique 'zero-energy' position of H-induced quasilocalized states enables notable spin polarization of the graphene's sublattice pseudospin. The pseudospin-mediated magnetic interactions between the H-induced magnetic moments stabilize the two-dimensional ferromagnetic ordering with Curie temperatures of Tc = nH × 34,000 K for the atom percentage nH of H adatoms. These findings show that atomic-scale control of hydrogen adsorption on graphene can give rise to a robust magnetic order.
Project description:Since the successful exfoliation of graphene, various methodologies have been developed to identify the number of layers of exfoliated graphene. The optical contrast, Raman G-peak intensity, and 2D-peak line-shape are currently widely used as the first level of inspection for graphene samples. Although the combination analysis of G- and 2D-peaks is powerful for exfoliated graphene samples, its use is limited in chemical vapor deposition (CVD)-grown graphene because CVD-grown graphene consists of various domains with randomly rotated crystallographic axes between layers, which makes the G- and 2D-peaks analysis difficult for use in number identification. We report herein that the Raman Si-peak intensity can be a universal measure for the number identification of multilayered graphene. We synthesized a few-layered graphene via the CVD method and performed Raman spectroscopy. Moreover, we measured the Si-peak intensities from various individual graphene domains and correlated them with the corresponding layer numbers. We then compared the normalized Si-peak intensity of the CVD-grown multilayer graphene with the exfoliated multilayer graphene as a reference and successfully identified the layer number of the CVD-grown graphene. We believe that this Si-peak analysis can be further applied to various 2-dimensional (2D) materials prepared by both exfoliation and chemical growth.
Project description:The discovery of superconductivity and correlated electronic states in the flat bands of twisted bilayer graphene has raised a lot of excitement. Flat bands also occur in multilayer graphene flakes that present rhombohedral (ABC) stacking order on many consecutive layers. Although Bernal-stacked (AB) graphene is more stable, long-range ABC-ordered flakes involving up to 50 layers have been surprisingly observed in natural samples. Here, we present a microscopic atomistic model, based on first-principles density functional theory calculations, that demonstrates how shear stress can produce long-range ABC order. A stress-angle phase diagram shows under which conditions ABC-stacked graphene can be obtained, providing an experimental guide for its synthesis.
Project description:How atoms acquire three-dimensional bulk character is one of the fundamental questions in materials science. Before addressing this question, how atomic layers become a bulk crystal might give a hint to the answer. While atomically thin films have been studied in a limited range of materials, a recent discovery showing how to mechanically exfoliate bulk crystals has opened up the field to study the atomic layers of various materials. Here, we show systematic variation in the band structure of high mobility graphene with one to seven layers by measuring the quantum oscillation of magnetoresistance. The Landau fan diagram showed distinct structures that reflected differences in the band structure, as if they were finger prints of multilayer graphene. In particular, an even-odd layer number effect was clearly observed, with the number of bands increasing by one for every two layers and a Dirac cone observed only for an odd number of layers. The electronic structure is significantly influenced by the potential energy arising from carrier screening associated with a gate electric field.
Project description:Bilayer honeycomb lattice, with inter-layer tunneling energy, has a parabolic dispersion relation, and the inter-layer hopping can cause the charge imbalance between two sublattices. Here, we investigate the metal-insulator and magnetic phase transitions on the strongly correlated bilayer honeycomb lattice by cellular dynamical mean-field theory combined with continuous time quantum Monte Carlo method. The procedures of magnetic spontaneous symmetry breaking on dimer and non-dimer sites are different, causing a novel phase transition between normal anti-ferromagnet and layer anti-ferromagnet. The whole phase diagrams about the magnetism, temperature, interaction and inter-layer hopping are obtained. Finally, we propose an experimental protocol to observe these phenomena in future optical lattice experiments.
Project description:Nowadays, graphene/polymer composite films with multilayer structure have attracted significant attention for gas barrier application. In this study, a series of reduced graphene oxide/polyethyleneimine (RGO/PEI) composite films were created via recast and layer-by-layer deposition processes. By using the recast process, the myriad PEI molecules in the precursor solution (the PEI : GO feeding ratio is 0.02 : 0.1, 0.05 : 0.1, 0.1 : 0.1, 0.3 : 0.1 and 0.5 : 0.1) ensure more effective reduction and surface modification of the graphene oxide (GO) sheets, while the undesirable free PEI molecules are eventually removed via a filtration process. Then, the RGO/PEI composite films were synthesized on PET substrate using a layer-by-layer assembly. The resulting films show a homogeneous and compact brick-wall structure with excellent gas barrier properties. Barriers against water vapor, nitrogen/oxygen, and carbon dioxide require different content of PEI in the composite film for optimal performance; the ideal values are 19.7, 23.8, and 24.1 wt%, respectively. These values are much lower compared with previously reported studies. Further, the permeability, free volumes, component ratio, morphology, and density of the RGO/PEI composite films have been carefully investigated and discussed. The results revealed that the mechanism behind the excellent gas barrier property of the RGO/PEI composite films is a synergistic effect created by the combination of the brick-wall structure, the small free volume holes, the suitable PEI content (ranging from 19.7 wt% to 24.1 wt%), the high density, and the hydrophobicity.
Project description:Nitrogen doping opens possibilities for tailoring the electronic properties and band gap of graphene toward its applications, e.g., in spintronics and optoelectronics. One major obstacle is development of magnetically active N-doped graphene with spin-polarized conductive behavior. However, the effect of nitrogen on the magnetic properties of graphene has so far only been addressed theoretically, and triggering of magnetism through N-doping has not yet been proved experimentally, except for systems containing a high amount of oxygen and thus decreased conductivity. Here, we report the first example of ferromagnetic graphene achieved by controlled doping with graphitic, pyridinic, and chemisorbed nitrogen. The magnetic properties were found to depend strongly on both the nitrogen concentration and type of structural N-motifs generated in the host lattice. Graphenes doped below 5 at. % of nitrogen were nonmagnetic; however, once doped at 5.1 at. % of nitrogen, N-doped graphene exhibited transition to a ferromagnetic state at ∼69 K and displayed a saturation magnetization reaching 1.09 emu/g. Theoretical calculations were used to elucidate the effects of individual chemical forms of nitrogen on magnetic properties. Results showed that magnetic effects were triggered by graphitic nitrogen, whereas pyridinic and chemisorbed nitrogen contributed much less to the overall ferromagnetic ground state. Calculations further proved the existence of exchange coupling among the paramagnetic centers mediated by the conduction electrons.
Project description:The range of applications of diverse graphene-based devices could be limited by insufficient surface reactivity, unsatisfied shaping, or null energy gap of graphene. Engineering the graphene structure by laser techniques can adjust the transport properties and the surface area of graphene, providing devices of different nature with a higher capacitance. Additionally, the created periodic potential and appearance of the active external/inner/edge surface centers determine the multifunctionality of the graphene surface and corresponding devices. Here, we report on the first implementation of nonlinear laser lithography (NLL) for multilayer graphene (MLG) structuring, which offers a low-cost, single-step, and high-speed nanofabrication process. The NLL relies on the employment of a high repetition rate femtosecond Yb fiber laser that provides generation of highly reproducible, robust, uniform, and periodic nanostructures over a large surface area (1 cm2/15 s). NLL allows one to obtain clearly predesigned patterned graphene structures without fabrication tolerances, which are caused by contacting mask contamination, polymer residuals, and direct laser exposure of the graphene layers. We represent regularly patterned MLG (p-MLG) obtained by the chemical vapor deposition method on an NLL-structured Ni foil. We also demonstrate tuning of chemical (wettability) and electro-optical (transmittance and sheet resistance) properties of p-MLG by laser power adjustments. In conclusion, we show the great promise of fabricated devices, namely, supercapacitors, and Li-ion batteries by using NLL-assisted graphene patterning. Our approach demonstrates a new avenue to pattern graphene for multifunctional device engineering in optics, photonics, and bioelectronics.
Project description:Graphene, in single layer or multi-layer forms, holds great promise for future electronics and high-temperature applications. Resistance to oxidation, an important property for high-temperature applications, has not yet been extensively investigated. Controlled thinning of multi-layer graphene (MLG), e.g., by plasma or laser processing is another challenge, since the existing methods produce non-uniform thinning or introduce undesirable defects in the basal plane. We report here that heating to extremely high temperatures (exceeding 2000 K) and controllable layer-by-layer burning (thinning) can be achieved by low-power laser processing of suspended high-quality MLG in air in "cold-wall" reactor configuration. In contrast, localized laser heating of supported samples results in non-uniform graphene burning at much higher rates. Fully atomistic molecular dynamics simulations were also performed to reveal details of oxidation mechanisms leading to uniform layer-by-layer graphene gasification. The extraordinary resistance of MLG to oxidation paves the way to novel high-temperature applications as continuum light source or scaffolding material.