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.

Direct growth of graphene on gallium nitride by using chemical vapor deposition without extra catalyst

Graphene on gallium nitride （GaN） will be quite useful when the graphene is used as transparent electrodes to improve the performance of gallium nitride devices. In this work, we report the direct synthesis of graphene on GaN without an extra catalyst by chemical vapor deposition. Raman spectra indicate that the graphene films are uniform and about 5-6 layers in thickness. Meanwhile, the effects of growth temperatures on the growth of graphene films are systematically studied, of which 950 ℃ is found to be the optimum growth temperature. The sheet resistance of the grown graphene is 41.1 Ω/square, which is close to the lowest sheet resistance of transferred graphene reported. The mechanism of graphene growth on GaN is proposed and discussed in detail. XRD spectra and photoluminescence spectra indicate that the quality of GaN epi-layers will not be affected after the growth of graphene.

Influence of reaction parameters on synthesis of high-quality single-layer graphene on Cu using chemical vapor deposition

Large-area monolayer graphene samples grown on polycrystalline copper foil by thermal chemical vapor deposition with differing CH4 flux and growth time are investigated by Raman spectra, scanning electron microscopy, atomic force microscopy, and scanning tunneling microscopy. The defects, number of layers, and quality of graphene are shown to be controllable through tuning the reaction conditions： ideally to 2-3 sccm CH4 for 30 minutes.

Transfer-free chemical vapor deposition graphene for nitride epitaxy: challenges, current status and future outlook

Graphene, a two-dimensional material with outstanding electrical and mechanical properties, has attracted considerable attention in the field of semiconductor technologies due to its potential use as a buffer layer for the epitaxial Ⅲ-nitride growth. In recent years, significant progress has been made in the chemical vapor deposition growth of graphene on various insulating substrates for the nitride epitaxy, which offers a facile, inexpensive, and easily scalable methodology. However, certain challenges are still present in the form of producing high-quality graphene and achieving optimal interface compatibility with Ⅲ-nitride materials.In this review, we provide an overview of the bottlenecks associated with the transferred graphene fabrication techniques and the state-of-the-art techniques for the transfer-free graphene growth. The present contribution highlights the current progress in the transfer-free graphene growth on different insulating substrates, including sapphire, quartz, SiO_(2)/Si, and discusses the potential applications of transfer-free graphene in the Ⅲ-nitride epitaxy. Finally, it includes the prospects of the transfer-free graphene growth for the Ⅲ-nitride epitaxy and the challenges that should be overcome to realize its full potential in this field.

Chemical vapor deposition growth behavior of graphene

The optimized growth parameters of graphene with different morphologies,such as dendrites,rectangle,and hexagon,have been obtained by low-pressure chemical vapor deposition on polycrystalline copper substrates.The evolution of fractal graphene,which grew on the polycrystalline copper substrate,has also been observed.When the equilibrium growth state of graphene is disrupted,its intrinsic hexagonal symmetry structure will change into a non-hexagonal symmetry structure.Then,we present a systematic and comprehensive study of the evolution of graphene with different morphologies grown on solid copper as a function of the volume ratio of methane to hydrogen in a controllable manner.Moreover,the phenomena of stitching snow-like graphene together and stacking graphene with different angles was also observed.

Theoretical investigations on the growth of graphene by oxygenassisted chemical vapor deposition

Recently,graphene has drawn considerable attention in the field of electronics,owing to its favorable conductivity and high carrier mobility.Crucial to the industrialization of graphene is its high-quality microfabrication via chemical vapor deposition.However,many problems remain in its preparation,such as the not fully understood cracking mechanism of the carbon source,the mechanism of its substrate oxidation,and insufficient defect repair theory.To help close this capability gap,this study leverages density functional theory to explore the role of O in graphene growth.The effects of Cu substrate oxidation on carbon source cracking,nucleation barriers,crystal nucleus growth,and defect repairs are discussed.OCu was found to reduce energy change during dehydrogenation,rendering the process easier.Moreover,the adsorbed O in graphene or its Cu substrate can promote defect repair and edge growth.

Invisible vapor catalysis in graphene growth by chemical vapor deposition

Vapor catalysis was recently found to play a crucial role in superclean graphene growth via chemical vapor decomposition(CVD).However,knowledge of vapor-phase catalysis is scarce,and several fundamental issues,including vapor compositions and their impact on graphene growth,are ambiguous.Here,by combining density functional theory(DFT)calculations,an ideal gas model,and a designed experiment,we found that the vapor was mainly composed of Cui clusters with tens of atoms.The vapor pressure was estimated to be~10^(-12)-10^(-1)1 bar under normal low-pressure CVD system(LPCVD)conditions for graphene growth,and the exposed surface area of Cui clusters in the vapor was 22-269 times that of the Cu substrate surface,highlighting the importance of vapor catalysis.DFT calculations show Cu clusters,represented by Cu17,have strong capabilities for adsorption,dehydrogenation,and decomposition of hydrocarbons.They exhibit an adsorption lifetime and reaction flux six orders of magnitude higher than those on the Cu surface,thus providing a sufficient supply of active C atoms for rapid graphene growth and improving the surface cleanliness of the synthesized graphene.Further experimental validation showed that increasing the amount of Cu vapor improved the as-synthesized graphene growth rate and surface cleanliness.This study provides a comprehensive understanding of vapor catalysis and the fundamental basis of vapor control for superclean graphene rapid growth.

X-ray Diffraction and Raman Spectroscopy Characterization of Isotropic Pyrocarbon Obtained by Hot Wall Chemical Vapor Deposition

Varying the flow rate of natural gas from 50 to 80 to 120 l/h, isotropic pyrocarbon produced by hot wall chemical vapor deposition at 1000 ℃ were examined by X-ray diffraction and Raman spectroscopy. The X-ray data were evaluated by Scherrer equation, and the intensity ratio of D to G band derived from Raman data was used to evaluate the lateral extension of isotropic pyrocarbon. The experimental results show that the d002-spacing of isotropic pyroearbon decreases from 0.3499 nm to 0.3451 nm, while the stack height increases from 6.5 to 8.4 nm with the increase of flow rate of natural gas. The intensity ratio of D to G band and lateral extension of isotropie pyrocarbon increases with natural gas flow rate increasing. After heat treatment, all the crystallite parameters （stack height, lateral extension, and d002-spacing） decrease, indicating the improvement of the arrangement of the basic structural units of isotropic pyrocarbon.

Direct low-temperature synthesis of graphene on various glasses by plasma-enhanced chemical vapor deposition for versatile, cost-effective electrodes

Catalyst-free and scalable synthesis of graphene on various glass substrates at low temperatures is of paramount significance to numerous applications such as low-cost transparent electronics and state-of-the-art displays. However, systematic study within this promising research field has remained scarce thus far. Herein, we report the direct growth of graphene on various glasses using a low-temperature plasma-enhanced chemical vapor deposition method. Such a facile and scalable approach guarantees the growth of uniform, transfer-free graphene films on various glass substrates at a growth temperature range of 400-600 ℃. The morphological, surface wetting, optical, and electrical properties of the obtained graphene can be tailored by controlling the growth parameters. Our uniform and high-quality graphene films directly integrated with low-cost, commonly used glasses show great potential in the fabrication of multi-functional electrodes for versatile applications in solar cells, transparent electronics, and smart windows.

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.

Structural and optical properties of Al_(1-x)In_xN epilayers on GaN template grown by metalorganic chemical vapor deposition

This paper reports that Al1-xInxN epilayers were grown on GaN template by metalorganic chemical vapor deposition with an In content of 7%--20%. X-ray diffraction results indicate that all these Al1-xInxN epilayers have a relatively low density of threading dislocations. Rutherford backscattering/channeling measurements provide the exact compositional information and show that a gradual variation in composition of the Al1-xInxN epilayer happens along the growth direction. The experimental results of optical reflection clearly show the bandgap energies of Al1-xInxN epilayers. A bowing parameter of 6.5~eV is obtained from the compositional dependence of the energy gap. The cathodoluminescence peak energy of the Al1-xInxN epilayer is much lower than its bandgap, indicating a relatively large Stokes shift in the Al1-xInxN sample.

Porous Carbon Grown by Chemical Vapor Deposition on Copper Substrates

Amorphous porous carbon was synthesized by chemical vapor deposition on copper substrates. The average size of the pores is around 1.2 microns with some small pores decorating the big ones. Lamellar samples of this carbonaceous material can be separated from the copper support and may be useful as electrode due to its low electrical resistivity of the order of 0.4 Ωcm.

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.

Progress of graphene growth on copper by chemical vapor deposition:Growth behavior and controlled synthesis

Recently,chemical vapor deposition (CVD) on copper has been becoming a main method for preparing large-area and highquality monolayer graphene.In this paper,we first briefly introduce the preliminary understanding of the microstructure and growth behavior of graphene on copper,and then focus on the recent progress on the quality improvement,number of layers control and transfer-free growth of graphene.In the end,we attempt to analyze the possible development of CVD growth of graphene in future,including the controlled growth of large-size single-crystal graphene and bilayer graphene with different stacking orders.

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.

Insight into the rapid growth of graphene single crystals on liquid metal via chemical vapor deposition

Previous reports about the growth of large graphene single crystals on polycrystalline metal substrates usually adopted the strategy of suppressing the nucleation by lowering the concentration of the feedstock, which greatly limited the rate of the nucleation and the sequent growth. The emerging liquid metal catalyst possesses the characteristic of quasi-atomically smooth surface with high diffusion rate. In principle, it should be a naturally ideal platform for the lowdensity nucleation and the fast growth of graphene. However,the rapid growth of large graphene single crystals on liquid metals has not received the due attention. In this paper, we firstly purposed the insight into the rapid growth of large graphene single crystals on liquid metals. We obtained the millimeter-size graphene single crystals on liquid Cu. The rich free-electrons in liquid Cu accelerate the nucleation, and the isotropic smooth surface greatly suppresses the nucleation.Moreover, the fast mass-transfer of carbon atoms due to the excellent fluidity of liquid Cu promotes the fast growth with a rate up to 79 μm s^-1. We hope the research on the growth speed of graphene on liquid Cu can enrich the recognition of the growth behavior of two-dimensional(2 D) materials on the liquid metal. We also believe that the liquid metal strategy for the rapid growth of graphene can be extended to various 2 D materials and thus promote their future applications in the photonics and electronics.

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.

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.