Production of a 100-m-long high-quality graphene transparent conductive film by roll-to-roll chemical vapor deposition and transfer process

ABSTRACTTwo-dimensional layered materials, materials with weak out-of-plane van der Waals bonding and strong in-plane covalent bonding, have attracted special attention in recent years since the isolation and characterization of monolayer graphite, the graphene. The electrical bandgap in Transition Metal Di-Chalcogenides (TMDCs), non-existent in graphene, make them a good alternative family of materials for novel electronic and optoelectronic applications. 2H- MoS2, one of the most stable TMDCs, has been extensively studied, including the synthesis methods, and its potential applications in photodetection. The chemical vapor deposition (CVD) synthesis method has increased its potential over the years. The advantages of this method are scalability compared to micromechanical exfoliation, common process used in research laboratories, and the maintenance of the quality and intrinsic properties of the material compared to the liquid exfoliation methods. In this work, we synthesized high quality pristine 2H-MoS2 via atmospheric pressure chemical vapor deposition (APCVD) by vapor phase reaction of MoO3 and S powder precursors. The samples were characterized via Raman and photoluminescence (PL) spectroscopy and compared to mechanically exfoliated MoS2 crystal by measuring the full-width half maxima (FWHM) of monolayer and few-layer mesoscopic flakes. In addition, the CVD synthesized single and few-layered MoS2 domains were transferred to different substrates using a high yield process, including a flexible substrate, preserving the quality of the material. Finally, and mechanically exfoliated MoS2 two-terminal photodetector was designed, fabricated, and measured. Demonstrating thus the capability of heterostructure fabrication and the quality of our synthesis and device fabrication process.

Carbon nanotube (CNT) devices receive much attention from both physical and technological points of view because of the ideal one-dimensional structure, nano-size dimension, and ultra-low power dissipation. In order to realize CNT integrated circuits, it is important to fabricate CNT field-effect transistors (FETs) at designed positions. In this work, we fabricated position-controlled CNT FETs by chemical vapor deposition (CVD) synthesis using metal catalysts patterned on a silicon wafer. Good FET operations have been obtained.

Graphene has a range of unique physical properties and could be of use in the development of a variety of electronic, photonic and photovoltaic devices. For most applications, large-area high-quality graphene films are required and chemical vapour deposition (CVD) synthesis of graphene on copper surfaces has been of particular interest due to its simplicity and cost effectiveness. However, the rates of growth for graphene by CVD on copper are less than 0.4 μm s-1, and therefore the synthesis of large, single-crystal graphene domains takes at least a few hours. Here, we show that single-crystal graphene can be grown on copper foils with a growth rate of 60 μm s-1. Our high growth rate is achieved by placing the copper foil above an oxide substrate with a gap of ∼15 μm between them. The oxide substrate provides a continuous supply of oxygen to the surface of the copper catalyst during the CVD growth, which significantly lowers the energy barrier to the decomposition of the carbon feedstock and increases the growth rate. With this approach, we are able to grow single-crystal graphene domains with a lateral size of 0.3 mm in just 5 s.

Many routes have been developed for the synthesis of carbon nanotubes, but their assembly into continuous fibers has been achieved only through postprocessing methods. We spun fibers and ribbons of carbon nanotubes directly from the chemical vapor deposition (CVD) synthesis zone of a furnace using a liquid source of carbon and an iron nanocatalyst. This process was realized through the appropriate choice of reactants, control of the reaction conditions, and continuous withdrawal of the product with a rotating spindle used in various geometries. This direct spinning from a CVD reaction zone is extendable to other types of fiber and to the spin coating of rotating objects in general.

Role of defects in the photoluminescence and photoresponse of WS2–graphene heterodevices

This work demonstrates precise control over the synthesis conditions and location during CNT formation, such that single chirality tubes are obtainable. This technique obviates two significant hurdles that prevent the exploitation of CNTs in micro- and nano-devices. Microelectronic applications require precise location and chirality of synthesized CNTs. Conventional CVD synthesis techniques typically yield mixtures of CNTs (semi-conducting and metallic types) that grow at random locations. Dip Pen Nanolithography (DPN) techniques were used to deposit the catalysts at precisely defined locations and to pattern the catalysts on a substrate with specific sizes as well as to control the catalyst composition. After deposition of catalysts, a low temperature Chemical Vapor Deposition (CVD) process was used to synthesize CNT. Various known catalysts were deposited. Characterization studies before and after CVD synthesis of CNT showed that the CNT were of a single chirality as well as uniform diameter (with a very narrow range of variability). The results indicate that the chirality of the synthesized CNT can be controlled by changing the synthesis conditions (e.g., size of the catalyst patterns, composition of the catalysts, temperature of CVD, gas flow rates, etc.).

<p indent=0mm>In 2004, graphene was successfully prepared by micromechanical exfoliation of graphite, which attracts wide attention in the scientific research community. After that, related research of two-dimensional (2D) materials has received continuous exploration. In particular, academia and industry have paid tremendous attention and high expectations on graphene, owing to its remarkable and tunable physical, electrical, optical, magnetic properties and its potential applications in various fields. These practical applications include high performance electronics and optoelectronics, such as field effect transistors, transparent and flexible electrodes, spintronic devices, solar cells and so on. However, as is well-known, the practical commercial applications are based on mature and repeatable preparation of materials. Great achievements have been made in developing synthesis techniques, including micromechanical exfoliation, epitaxial growth, chemical vapor deposition (CVD), chemical exfoliation, arc discharge, segregation growth and bottom-up synthesis and so on. Among these methods, CVD method is regarded as the most versatile platform to obtain high quality, large area, and controllable number of layers with good repeatability and low cost for real commercial applications. Up to now, the past decade has witnessed significant developments in the field of CVD graphene synthesis. Herein, we present the development of this field by firstly introducing the origin of graphene and the background of CVD method. Then, the main achievements in the development of graphene since 2008 are presented from the point of view of controllable preparation. The CVD synthesis of graphene is focused mainly on four aspects: the selection and modification of catalytic substrates, the manipulation of reaction conditions, bandgap engineering and clean transfer. The selection of catalytic substrate plays a critical role in the controllable preparation of graphene by CVD method. The representative catalytic mechanisms of different substrates for growing graphene are introduced, followed by various modifications of catalytic metal substrates. Besides, surface morphology and microstructure of substrates have a great impact on the quality and uniformity of as-grown graphene. Thus, due to the disadvantages of non-uniform surface energy, defects, wrinkles and impurities on the surface of solid metal, the introduction of liquid copper catalytic system helps to better control the nucleation uniformity and optimize the graphene growth. Moreover, the preparation of large-area monocrystalline metal foils for obtaining large-scale single-crystal graphene was also reviewed. In order to avoid the disadvantages such as the damage, wrinkle and polymer pollution of graphene associated with transfer process occurred in the cases of using metal substrates to grow graphene, direct synthesis of graphene on dielectric substrates is presented with focuses on two basic controls of nucleation density and growth rate. A series of techniques such as reaction medium regulation, substrate surface modification, and plasma-assisted growth, the introduction of gaseous metals and direct preparation of graphene on liquid glass are introduced. The development of graphene vertical and planar heterostructures with hexagonal boron nitride is also presented. Moreover, the disadvantage of graphene limits its application in logic circuits due to its zero bandgap without an acceptable on/off ratio, and three main ways to open graphene bandgap are discussed including doping, the preparation of a large area of AB stacking bilayer graphene and engineering graphene nanoribbons. After that, a brief introduction of transfer method used in graphene post-processing is given. Finally, we summarize the problems existing in the field, and the future opportunities and challenges are discussed.

A theoretical analysis of the Chemical Vapor Deposition (CVD) process for synthesis of carbon nanotubes, in order to predict the spatial distributions of the concentration, velocity and temperature inside the reactor has been presented in this paper. The analysis is performed by solving the governing differential equations pertaining to the process which involves catalytic chemical vapor deposition (CCVD) with acetylene as the carbon source and iron oxide as the catalyst. The system of equations, namely the momentum, energy and mass transport equations have been solved using the COMSOL software. The predicted values of the carbon nanotube yield from the chemical kinetics model have been verified using experimental results. The analysis presented offers an effective tool in designing the CVD furnace and deciding on the operational parameters to be used, in the synthesis of carbon nanotubes using the Chemical Vapor Deposition method.

Recently, two-dimensional (2D) layered materials, such as graphene and transition metal dichalcogenides (TMDCs), have garnered a lot of attention in energy storage/conversion-related fields due to their novel physical and chemical properties. Constructing flat graphene and TMDCs nanosheets into 3D architectures can significantly increase their exposed surface area and prevent the restacking of adjacent 2D layers, thus dramatically promoting their applications in various energy-related fields. Chemical Vapor Deposition (CVD) is a low-cost, facile, and scalable method, which has been widely employed to produce high-quality graphene and TMDCs nanosheets with 3D architectures. During the CVD process, the morphologies and properties of the 3D architectures of such 2D materials can be designed by selecting substrates with different compositions, stacking geometries, and micro-structures. In this review, we focus on the recent advances in the CVD synthesis of graphene, TMDCs, and their hybrids with 3D architectures on different 3D-structured substrates, as well as their applications in the electrocatalytic hydrogen evolution reaction (HER) and various secondary batteries. In addition, the challenges and future prospects for the CVD synthesis and energy-related applications of these unique layered materials will also be discussed.

ABSTRACTNext-generation electronic devices are expected to demonstrate greater utility, efficiency and durability. Meanwhile, plastics such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and variety of poly(para-xylylene) polymers enable transformational advantages to device shape, flexibility, weight, transparency and recyclability. Exhibiting a combination of outstanding mechanical, electrical, optical, and chemical properties of graphene with the plastic substrates could propose ideal material for the future flexible electronics. Chemical vapor deposition (CVD) allows cost-effective fabrication of a high-quality large-area graphene films, however, the critical issue is clean and noninvasive transfer of the films onto a desired substrate. The water-based delamination of CVD grown graphene on Cu can be considered as a “green” transfer process utilizing only hot deionized water. We investigated a method requiring only two essential steps: coating of 6-inch monolayer CVD graphene with transparent and flexible polymer, and Cu delamination in hot water. Proposed method is inexpensive, reproducible, environmentally friendly, waste-free and suitable for large-scale, high quality graphene. The transfer process demonstrated films with enhanced charge carrier mobility, high uniformity, free of mechanical defects, and sheet resistance as low as ∼50 Ω/sq with 96.5 % transparency at 550 nm wavelength.

In this article, the role of kinetics, in particular, the pressure of the reaction chamber in the chemical vapor deposition (CVD) synthesis of graphene using low carbon solid solubility catalysts (Cu), on both the large area thickness uniformity and the defect density are presented. Although the thermodynamics of the synthesis system remains the same, based on whether the process is performed at atmospheric pressure (AP), low pressure (LP) (0.1-1 Torr) or under ultrahigh vacuum (UHV) conditions, the kinetics of the growth phenomenon are different, leading to a variation in the uniformity of the resulting graphene growth over large areas (wafer scale). The kinetic models for APCVD and LPCVD are discussed, thereby providing insight for understanding the differences between APCVD vs LPCVD/UHVCVD graphene syntheses. Interestingly, graphene syntheses using a Cu catalyst in APCVD processes at higher methane concentrations revealed that the growth is not self-limiting, which is in contrast to previous observations for the LPCVD case. Additionally, nanoribbons and nanostrips with widths ranging from 20 to 100 nm were also observed on the APCVD grown graphene. Interactions between graphene nanofeatures (edges, folds) and the contaminant metal nanoparticles from the Cu etchant were observed, suggesting that these samples could potentially be employed to investigate the chemical reactivity of single molecules, DNA, and nanoparticles with monolayer graphene.

Direct synthesis of graphene with well-defined nanoscale pores over large areas can transform the fabrication of nanoporous atomically thin membranes (NATMs) and greatly enhance their potential for practical applications. However, scalable bottom-up synthesis of continuous sheets of nanoporous graphene that maintain integrity over large areas has not been demonstrated. Here, it is shown that a simple reduction in temperature during chemical vapor deposition (CVD) on Cu induces in-situ formation of nanoscale defects (≤2-3 nm) in the graphene lattice, enabling direct and scalable synthesis of nanoporous monolayer graphene. By solution-casting of hierarchically porous polyether sulfone supports on the as-grown nanoporous CVD graphene, large-area (>5 cm2 ) NATMs for dialysis applications are demonstrated. The synthesized NATMs show size-selective diffusive transport and effective separation of small molecules and salts from a model protein, with ≈2-100× increase in permeance along with selectivity better than or comparable to state-of-the-art commercially available polymeric dialysis membranes. The membranes constitute the largest fully functional NATMs fabricated via bottom-up nanopore formation, and can be easily scaled up to larger sizes permitted by CVD synthesis. The results highlight synergistic benefits in blending traditional membrane casting with bottom-up pore creation during graphene CVD for advancing NATMs toward practical applications.

It has been known that the crystalline orientation of Cu substrates plays a crucial role in chemical vapor deposition (CVD) synthesis of high-quality graphene. In particular, Cu (1 1 1) surface showing the minimum lattice mismatch with graphene is expected to provide an ideal catalytic reactivity that can minimize the formation of defects, which also induces larger single-crystalline domain sizes of graphene. Usually, the Cu (1 1 1) substrates can be epitaxially grown on single-crystalline inorganic substrates or can be recrystallized by annealing for more than 12 h, which limits the cost and time-effective synthesis of graphene. Here, we demonstrate a new method to optimize the crystalline orientations of vertically suspended Cu foils by tension control during graphene growth, resulting in large-area recrystallization into Cu (1 1 1) surface as the applied tension activates the grain boundary energy of Cu and promotes its abnormal grain growth to single crystals. In addition, we found a clue that the formation of graphene cooperatively assists the recrystallization into Cu (1 1 1) by minimizing the surface energy of Cu. The domain sizes and charge carrier mobility of graphene grown on the single-crystalline Cu (1 1 1) are 5 times and ~50% increased, respectively, in comparison with those of graphene from Cu (1 0 0), indicating that the less lattice mismatch and the lower interaction energy between Cu (1 1 1) and graphene allows the growth of larger single-crystalline graphene with higher charge carrier mobility. Thus, we believe that our finding provides a crucial idea to design a roll-to-roll (R2R) graphene synthesis system where the tension control is inevitably involved, which would be of great importance for the continuous production of high-quality graphene in the future.

Chemical vapour deposition (CVD) synthesis of graphene on copper has been broadly adopted since the first demonstration of this process1. However, widespread use of CVD-grown graphene for basic science and applications has been hindered by challenges with reproducibility2 and quality3. Here we identify trace oxygen as a key factor determining the growth trajectory and quality for graphene grown by low-pressure CVD. Oxygen-free chemical vapour deposition (OF-CVD) synthesis is fast and highly reproducible, with kinetics that can be described by a compact model, whereas adding trace oxygen leads to suppressed nucleation and slower/incomplete growth. Oxygen affects graphene quality as assessed by surface contamination, emergence of the Raman D peak and decrease in electrical conductivity. Epitaxial graphene grown in oxygen-free conditions is contamination-free and shows no detectable D peak. After dry transfer and boron nitride encapsulation, it shows room-temperature electrical-transport behaviour close to that of exfoliated graphene. A graphite-gated device shows well-developed integer and fractional quantum Hall effects. By highlighting the importance of eliminating trace oxygen, this work provides guidance for future CVD system design and operation. The increased reproducibility and quality afforded by OF-CVD synthesis will broadly influence basic research and applications of graphene.

Atomically thin MoS2 layer, a promising transition metal dichalcogenide (TMDC) material, has great potential for application in next-generation electronic and optoelectronic devices. Chemical vapor deposition (CVD) is the most effective technique for the synthesis of high-quality MoS2 layers. During CVD synthesis, monolayered MoS2 is generally synthesized by sulfidation of MoO3. Although qualitative reaction mechanisms for the sulfidation of MoO3 have been investigated by previous studies, the detailed reaction processes, including atomic-scale reaction pathways and growth kinetics, have yet to be fully understood. Here, we present quantum-mechanically informed and validated reactive molecular dynamics simulations of the direct sulfidation of MoO3 surfaces using S2 gas precursors. Our work clarifies the reaction mechanisms and kinetics of the sulfidation of MoO3 surfaces as follows: the reduction and sulfidation of MoO3 surfaces occur primarily at O-termination sites, followed by unsaturated Mo sites; these local reaction processes lead to nonuniform MoOxSy surface structures during the CVD process. After annealing the MoOxSy samples, the crystallized surface structures contain voids, and three different types of local surface complexes (MoOx, MoOxSy, and MoS2-like surface regions), depending on the fraction of S ingredients on the MoOxSy surface. These results, which have been validated by our reactive quantum molecular dynamics simulations and previous experimental results, provide valuable chemical insights into the CVD synthesis of large-scale and defect-free MoS2 layers and other layered TMDC materials.