One-step synthesis of novel snowflake-like Si-O/Si-C nanostructures on 3D graphene/Cu foam by chemical vapor deposition

The recent development of synthesis processes for three-dimensional （3D） graphene-based structures has tended to focus on continuous improvement of porous nanostructures, doping modification during thin-film fabrication, and mechanisms for building 3D architectures. Here, we synthesized novel snowflake- like Si-O/Si-C nanostructures on 3D graphene/Cu foam by one-step low-pressure chemical vapor deposition （CVD）. Through systematic micromorphological characterization, it was determined that the formation mechanism of the nanostructures involved the melting of the Cu foam surface and the subsequent condensation of the resulting vapor, 3D growth of graphene through catalysis in the presence of Cu, and finally , nudeation of the Si-O/Si-C nanostructure in the carbon-rich atmosphere. Thus, by tuning the growth temperature and duration, it should be possible to control the nucleation and evolution of such snowflake-like nanostructures with precision. Electrochemical measurements indicated that the snowflake-like nanostructures showed excellent performance as a material for energy storage. The highest specific capacitance of the Si-O/Si-C nanostructures was - 963.2 mF/cm2 at a scan rate of 1 mV/s. Further, even after 20,000 sequential cycles, the electrode retained 94.4% of its capacitance.

Fabrication of Graphene/Cu Composite by Chemical Vapor Deposition and Effects of Graphene Layers on Resultant Electrical Conductivity

Graphene(Gr)has unique properties including high electrical conductivity;Thus,graphene/copper(Gr/Cu)composites have attracted increasing attention to replace traditional Cu for electrical applications. However,the problem of how to control graphene to form desired Gr/Cu composite is not well solved. This paper aims at exploring the best parameters for preparing graphene with different layers on Cu foil by chemical vapor deposition(CVD)method and studying the effects of different layers graphene on Gr/Cu composite’s electrical conductivity. Graphene grown on single-sided and double-sided copper was prepared for Gr/Cu and Gr/Cu/Gr composites. The resultant electrical conductivity of Gr/Cu composites increased with decreasing graphene layers and increasing graphene volume fraction. The Gr/Cu/Gr composite with monolayer graphene owns volume fraction of less than 0.002%,producing the best electrical conductivity up to59.8 ×10^(6)S/m,equivalent to 104.5% IACS and 105.3% pure Cu foil.

High current limits in chemical vapor deposited graphene spintronic devices

Understanding the stability and current-carrying capacity of graphene spintronic devices is key to their applications in graphene channel-based spin current sensors,spin-torque oscillators,and potential spin-integrated circuits.However,despite the demonstrated high current densities in exfoliated graphene,the current-carrying capacity of large-scale chemical vapor deposited(CVD)graphene is not established.Particularly,the grainy nature of chemical vapor deposited graphene and the presence of a tunnel barrier in CVD graphene spin devices pose questions about the stability of high current electrical spin injection.In this work,we observe that despite structural imperfections,CVD graphene sustains remarkably highest currents of 5.2×10^(8)A/cm^(2),up to two orders higher than previously reported values in multilayer CVD graphene,with the capacity primarily dependent upon the sheet resistance of graphene.Furthermore,we notice a reversible regime,up to which CVD graphene can be operated without degradation with operating currents as high as 108 A/cm^(2),significantly high and durable over long time of operation with spin valve signals observed up to such high current densities.At the same time,the tunnel barrier resistance can be modified by the application of high currents.Our results demonstrate the robustness of large-scale CVD graphene and bring fresh insights for engineering and harnessing pure spin currents for innovative device applications.

Synthesis of Large-Area, Few-Layer Graphene on Iron Foil by Chemical Vapor Deposition

We demonstrate a simple and controllable way to synthesize large-area, few-layer graphene on iron substrates by an optimized chemical vapor deposition （CVD） method using a mixture of methane and hydrogen. Based on an analysis of the Fe-C phase diagram, a suitable procedure for the successful synthesis of graphene on Fe surfaces was designed. An appropriate temperature and cooling process were found to be very important in the synthesis of highly crystalline few-layer graphene. Graphene-based field-effect transistor （FET） devices were fabricated using the resulting few-layer graphene, and showed good quality with extracted mobilities of 300-1150 cm2/（V.s）.

Large-area chemical vapor deposition-grown monolayer graphene-wrapped silver nanowires for broad-spectrum and robust antimicrobial coating

New types of antimicrobial systems are urgently needed owing to the emergence of pathogenic microbial strains that gain resistance to antibiotics commonly used in daily life and medical care. In this study we developed for the first time a broad-spectrum and robust antimicrobial thin film coating based on large-area chemical vapor deposition （CVD）-grown graphene-wrapped silver nanowires （AgNWs）. The antimicrobial graphene/AgNW hybrid coating can be applied on commerdal flexible transparent ethylene vinyl acetate/polyethylene terephthalate （EVA/PET） plastic films by a full roll-to-roll process. The graphene/AgNW hybrid coating showed broad-spectrum antimicrobial activity against Gram-negative （Escherichia coli） and Gram-positive bacteria （Staphylococcus aureus）, and fungi （Candida albicans）. This effect was attributed to a weaker microbial attachment to the ultra-smooth graphene film and the sterilization capacity of Ag＋, which is sustainably released from the AgNWs and presumably enhanced by the electrochemical corrosion of AgNWs. Moreover, the robust antimicrobial activity of the graphene/AgNW coating was reinforced by AgNW encapsulation by graphene. Furthermore, the antimicrobial efficiency could be enhanced to -100% by water electrolysis by using the conductive graphene/AgNW coating as a cathode. We developed a transparent and flexible antimicrobial cover made of graphene/AgNW/EVA/PET and an antimicrobial denture coated by graphene/ AgNW, to show the potential applications of the antimicrobial materials.

TOPSIS based Taguchi design optimization for CVD growth of graphene using different carbon sources: Graphene thickness, defectiveness and homogeneity

Chemical inhomogeneity of chemical vapor deposition(CVD) grown graphene compromises its usage in highperformance devices. In this study, TOPSIS based Taguchi optimization was performed to improve thickness uniformity and defect density of CVD grown graphene. 1.56% decrease in the mean 2 D/G intensity ratio, 87.96% improvement in the mean D/G intensity ratio, 56.07% improvement in the standard deviation D/G intensity ratio, 25.21%improvement in the standard deviation 2 D/G intensity ratio, and 69.32% improvement in the surface roughness were achieved with TOPSIS based Taguchi optimization. The statistical differences between the copper and silicon substrates have been found significantly in terms of their impacts on the graphene's properties with the0.000 p-value for the mean D/G intensity ratio and with the 0.009 p-value for the mean 2 D/G intensity ratio, respectively. Graphene having 11% lower mean D/G intensity ratio(low defective graphene products) compared to the values given in the literature using single-response optimization was obtained using multi-response optimization.

Synthesis of Isotopically-Labeled Graphite Films by Cold-Wall Chemical Vapor Deposition and Electronic Properties of Graphene Obtained from Such Films

We report the synthesis of isotopically-labeled graphite films on nickel substrates by using cold-wall chemical vapor deposition(CVD).During the synthesis,carbon from^(12)C-and^(13)C-methane was deposited on,and dissolved in,a nickel foil at high temperature,and a uniform graphite film was segregated from the nickel surface by cooling the sample to room temperature.Scanning and transmission electron microscopy,micro-Raman spectroscopy,and X-ray diffraction prove the presence of a graphite film.Monolayer graphene films obtained from such isotopically-labeled graphite films by mechanical methods have electron mobility values greater than 5000 cm^(2)·V^(-1)·s^(-1)at low temperatures.Furthermore,such films exhibit the half-integer quantum Hall effect over a wide temperature range from 2 K to 200 K,implying that the graphite grown by this cold-wall CVD approach has a quality as high as highly oriented pyrolytic graphite(HOPG).The results from transport measurements indicate that^(13)C-labeling does not significantly affect the electrical transport properties of graphene.

Toward batch synthesis of high-quality graphene by cold-wall chemical vapor deposition approach

Chemical vapor deposition(CVD)has emerged as a promising approach for the controlled growth of graphene films with appealing scalability,controllability,and uniformity.However,the synthesis of high-quality graphene films still suffers from low production capacity and high energy consumption in the conventional hot-wall CVD system.In contrast,owing to the different heating mode,cold-wall CVD(CW-CVD)system exhibits promising potential for the industrial-scale production,but the quality of as-received graphene remains inferior with limited domain size and high defect density.Herein,we demonstrated an efficient method for the batch synthesis of high-quality graphene films with millimeter-sized domains based on CW-CVD system.With reduced defect density and improved properties,the as-received graphene was proven to be promising candidate material for electronics and anti-corrosion application.This study provides a new insight into the quality improvement of graphene derived from CW-CVD system,and paves a new avenue for the industrial production of high-quality graphene films for potential commercial applications.

Kinetics of defect formation in chemically vapor deposited （CVD） graphene during laser irradiation： The case of Raman investigation

The effect of laser irradiation on chemically vapor deposited （CVD） graphene was studied by analyzing the temporal evolution of Raman spectra acquired under various illumination conditions. The spectra showed that the normalized intensity of the defect-related peak increases with the square root of the exposure time and varies almost linearly with the laser power density. Furthermore, the hardness of graphene to radiation damage depends on its intrinsic structural quality. The results suggest that, contrary to the common belief, micro-Raman spectroscopy cannot be considered a noninvasive tool for the characterization of graphene. The experimental observations are compatible with a model that we derived from the interpretative approach of the Staebler-Wronski effect in hydrogenated amorphous silicon; this approach assumes that the recombination of photoexcited carriers induces the breaking of weak C-C bonds.

Safe growth of graphene from non-flammable gas mixtures via chemical vapor deposition

Chemical vapor deposition has emerged as the most promising technique for the growth of graphene.However, most reports of this technique use either flammable or explosive gases, which bring safety concerns and extra costs to manage risk factors. In this article, we demonstrate that continuous monolayer graphene can be synthesized via chemical vapor deposition technique on Cu foils using industrially safe gas mixtures. Important factors, including the appropriate ratio of hydrogen flow and carbon precursor,pressure, and growth time are considered to obtain graphene films. Optical measurements and electrical transport measurements indicate graphene films are with comparable quality to other reports. Such continuous large area graphene can be synthesized under non-flammable and non-explosive conditions, which opens a safe and economical method for mass production of graphene. It is thereby beneficial for integration of graphene into semiconductor electronics.

Impurity-induced formation of bilayered graphene on copper by chemical vapor deposition

High-quality single-layered and bilayered graphene (SLG and BLG) was synthesized on copper foil surfaces by controllable chemical vapor deposition (CVD). Impurity nanoparticles formed on the copper foil surface by hightemperature annealing were found to play a crucial role in the growth of BLG. Analysis of energy-dispersive spectrometry (EDS) data indicated that these nanoparticles consisted of silicon and aluminum. According to the inverted wedding cake model, these nanoparticles served as nucleation centers for BLG growth and the free space between a nanoparticle and graphene served as the center of C injection for the continuous growth of the adlayer beneath the top layer. By combining phase-field theory simulations, we confirmed the mechanism of BLG growth and revealed more details about it in comparison with SLG growth. For the first time, this study led to a complete understanding of the BLG growth mechanism from nucleation to continuous growth in the CVD process, and it has opened a door to the thickness-controllable synthesis of graphene. [Figure not available: see fulltext.] © 2016, Tsinghua University Press and Springer-Verlag Berlin Heidelberg.

An easy way to controllably synthesize one-dimensional Sm B_6 topological insulator nanostructures and exploration of their field emission applications

A convenient fabrication technique for samarium hexaboride（SmB6） nanostructures（nanowires and nanopencils） is developed, combining magnetron-sputtering and chemical vapor deposition. Both nanostructures are proven to be single crystals with cubic structure, and they both grow along the [001] direction. Formation of both nanostructures is attributed to the vapor-liquid-solid（VLS） mechanism, and the content of boron vapor is proposed to be the reason for their different morphologies at various evaporation distances. Field emission（FE） measurements show that the maximum current density of both the as-grown nanowires and nanopencils can be several hundred μA/cm^2, and their FN plots deviate only slightly from a straight line. Moreover, we prefer the generalized Schottky-Nordheim（SN） model to comprehend the difference in FE properties between the nanowires and nanopencils. The results reveal that the nonlinearity of FN plots is attributable to the effect of image potential on the FE process, which is almost independent of the morphology of the nanostructures.All the research results suggest that the SmB6 nanostructures would have a more promising future in the FE area if their surface oxide layer was eliminated in advance.

Simple Ultrasonic-Assisted Clean Graphene Transfer

Clean graphene transfer has received widespread research attention, where most methods are focused on cleaning the upper surface of graphene to improve the transfer technique. However, the residue formation on the bottom surface of graphene is also inevitable;therefore, cleaning the bottom surface is crucial. In this study, we proposed an improved graphene wet transfer method using an ultrasonic processing(UP) step for etching copper(Cu). Using this method, the bottom surface can be cleaned efficiently. The results of atomic force microscopy(AFM)and Raman spectroscopy mapping revealed that the graphene films transferred with UP had smoother and cleaner surfaces, less contamination, and higher quality than those transferred without UP.

High-quality graphene grown directly on stainless steel meshes through CVD process for enhanced current collectors of supercapacitors

High-quality graphene coating was directly grown on stainless steel meshes via chemical vapor deposition process,during which the morphology of the stainless steel was transformed rugged.When the graphene-coated stainless steel meshes were applied as current collectors of supercapacitors,the changes of the appearance and the graphene coating improved the contact between stainless steel meshes and the active materials,thus benefiting the performance of the supercapacitors.Furthermore,this simple method can be used to prepare the enhanced current collectors for other energy storage devices.

Removing contaminants from transferred CVD graphene

Chemical vapor deposition(CVD)is among the most utilized techniques to fabricate single-layer graphene on a large substrate.However,the substrate is limited to very few transition metals like copper.On the other hand,many applications involving graphene require technologically relevant substrates like semiconductors and metal oxide,and therefore,a subsequent process is often needed to transfer CVD to the new substrate.As graphene is fragile,a supporting material such as a polymer film,is introduced during the transfer process.This brings unexpected challenges,the biggest of which is the complete removal of this support material without contaminating graphene.Numerous methods have been developed,each having advantages and drawbacks.This review will first introduce the classic transfer method using poly(methyl methacrylate)(PMMA)as the support material.The operating procedure and issues of PMMA residuals will be discussed.Methods to minimize/eliminate contamination will be presented,together with alternative approaches that do not require the use of PMMA.

Quality assessment of graphene： Continuity, uniformity, and accuracy of mobility measurements

With the increasing availability of large-area graphene, the ability to rapidly and accurately assess the quality of the electrical properties has become critically important. For practical applications, spatial variability in carrier density and carrier mobility must be controlled and minimized. We present a simple framework for assessing the quality and homogeneity of large-area graphene devices. The field effect in both exfoliated graphene devices encapsulated in hexagonal boron nitride and chemical vapor-deposited （CVD） devices was measured in dual current-voltage configurations and used to derive a single, gate-dependent effective shape factor, t, for each device, β is a sensitive indicator of spatial homogeneity that can be obtained from samples of arbitrary shape. All 50 devices investigated in this study show a variation （up to tenfold） in β as a function of the gate bias. Finite element simulations suggest that spatial doping inhomogeneity, rather than mobility inhomogeneity, is the primary cause of the gate dependence of β, and that measurable variations of β can be caused by doping variations as small as 10^10 cm^-2. Our results suggest that local variations in the position of the Dirac point alter the current flow and thus the effective sample shape as a function of the gate bias. We also found that such variations lead to systematic errors in carrier mobility calculations, which can be revealed by inspecting the corresponding β factor.

Preparation of carbon-coated iron oxide nanoparticles dispersed on graphene sheets and applications as advanced anode materials for lithium-ion batteries

We report a novel chemical vapor deposition （CVD） based strategy to synthesize carbon-coated Fe203 nanoparticles dispersed on graphene sheets （Fe2Og@C@G）. Graphene sheets with high surface area and aspect ratio are chosen as space restrictor to prevent the sintering and aggregation of nanoparticles during high temperature treatments （800 ℃）. In the resulting nanocomposite, each individual Fe2O3 nanoparticle （5 to 20 nm in diameter） is uniformly coated with a continuous and thin （two to five layers） graphitic carbon shell. Further, the core-shell nanoparticles are evenly distributed on graphene sheets. When used as anode materials for lithium ion batteries, the conductive-additive-free Fe2OB@C@G electrode shows outstanding Li＋ storage properties with large reversible specific capacity （864 mAh/g after 100 cycles）, excellent cyclic stability （120% retention after 100 cycles at 100 mA/g）, high Coulombic efficiency （-99%）, and good rate capability.

A general and simple method for evaluating the electrical transport performance of graphene by the van der Pauw–Hall measurement

Expected for many promising applications in the field of electronics and optoelectronics, a reliable method for the characterization of graphene electrical transport properties is desired to predict its device performance or provide feedback for its synthesis.However, the commonly used methods of extracting carrier mobility from graphene field effect transistor or Hall-bar is time consuming, expensive, and significantly affected by the device fabrication process other than graphene itself.Here we reported a general and simple method to evaluate the electrical transport performance of graphene by the van der Pauw–Hall measurement.By annealing graphene in vacuum to remove the adsorbed dopants and then exposing it in ambient surroundings, carrier mobility as a function of density can be measured with the increase of carrier density due to the dopant re-adsorption from the surroundings.Further, the relationship between the carrier mobility and density can be simply fitted with a power equation to the first level approximation, with which any pair of measured carrier mobility and density can be normalized to an arbitrary carrier density for comparison.We experimentally demonstrated the reliability of the method, which is much simpler than making devices and may promote the standard making for graphene characterization.

Oxygen-assisted direct growth of large-domain and high-quality graphene on glass targeting advanced optical filter applications

Growing high quality graphene films directly on glass by chemical vapor deposition(CVD)meets a growing demand for constructing high-performance electronic and optoelectronic devices.However,the graphene synthesized by prevailing methodologies is normally of polycrystalline nature with high nucleation density and limited domain size,which significantly handicaps its overall properties and device performances.Herein,we report an oxygen-assisted CVD strategy to allow the direct synthesis of 6-inch-scale graphene glass harvesting markedly increased graphene domain size(from 0.2 to 1.8μm).Significantly,as-produced graphene glass attains record high electrical conductivity(realizing a sheet resistance of 900Ω·sq^(-1)at a visible-light transmittance of 92%)amongst the state-of-the-art counterparts,readily serving as transparent electrodes for fabricating high-performance optical filter devices.This work might open a new avenue for the scalable production and application of emerging graphene glass materials with high quality and low cost.