Operando Characterization and Molecular Simulations Reveal the Growth Kinetics of Graphene on Liquid Copper during Chemical Vapor Deposition
Valentina Rein, Hao Gao, Hendrik H. Heenen, Wissal Sghaier, Anastasios C. Manikas, Mehdi Saedi, Johannes T. Margraf, Costas Galiotis, Gilles Renaud, Oleg V. Kon… 展开作者
Valentina Rein, Hao Gao, Hendrik H. Heenen, Wissal Sghaier, Anastasios C. Manikas, Mehdi Saedi, Johannes T. Margraf, Costas Galiotis, Gilles Renaud, Oleg V. Konovalov, Irene M. N. Groot, Karsten Reuter, Maciej Jankowski
In recent years, liquid metal catalysts have emerged as a compelling choice for the controllable, large-scale, and high-quality synthesis of two-dimensional materials. At present, there is little mechanistic understanding of the intricate catalytic process, though, of its governing factors or what renders it superior to growth at the corresponding solid catalysts. Here, we report on a combined experimental and computational study of the kinetics of graphene growth during chemical vapor deposition on a liquid copper catalyst. By monitoring the growing graphene flakes in real time using in situ radiation-mode optical microscopy, we explore the growth morphology and kinetics over a wide range of CH4-to-H2 pressure ratios and deposition temperatures. Constant growth rates of the flakes' radius indicate a growth mode limited by precursor attachment, whereas methane-flux-dependent flake shapes point to limited precursor availability. Large-scale free energy simulations enabled by an efficient machine-learning moment tensor potential trained to density-functional theory data provide quantitative barriers for key atomic-scale growth processes. The wealth of experimental and theoretical data can be consistently combined into a microkinetic model that reveals mixed growth kinetics that, in contrast to the situation at solid Cu, is partly controlled by precursor attachment alongside precursor availability. Key mechanistic aspects that directly point toward the improved graphene quality are a largely suppressed carbon dimer attachment due to the facile incorporation of this precursor species into the liquid surface and a low-barrier ring-opening process that self-heals 5-membered rings resulting from remaining dimer attachments.
We evaluate how a second graphene layer forms and grows on Cu foils during chemical vapor deposition (CVD). Low-energy electron diffraction and microscopy is used to reveal that the second layer nucleates and grows next to the substrate, i.e., under a graphene layer. This underlayer mechanism can facilitate the synthesis of uniform single-layer films but presents challenges for growing uniform bilayer films by CVD. We also show that the buried and overlying layers have the same edge termination.
The data of experimental studies of optical characteristics of colloidal solutions, composition and morphology of its dispersed phase, resulting from laser ablation of zinc in aqueous solutions of anionic surfactants --- sodium dodecyl sulfate (SDS), dioctyl sodium sulfosuccinate (AOT) are presented. It is shown that by studying the optical absorption spectra of the colloid, X-ray spectra and AFM-images of extracted from colloid solid phase, it is possible to trace the dynamics of ZnO nanostructures formation from zinc nanoclasters size of several nanometers to ZnO fractal aggregates (FA) size…
We demonstrated that chemical vapor deposition of graphene on Cu films strongly enhances their thermal diffusivity and thermal conductivity. Deposition of graphene increases the thermal conductivity of 9 micrometer (25 micrometer) thick Cu films by up to 24% (16%) near room temperature. Interestingly, the observed improvement of thermal properties of graphene coated Cu films is primarily due to changes in Cu morphology during graphene deposition and associated with it temperature treatment rather than graphene's action as an additional heat conducting channel. Enhancement of thermal properties…
The discovery of graphene, a single layer of covalently bonded carbon atoms, has attracted intense interests. Initial studies using mechanically exfoliated graphene unveiled its remarkable electronic, mechanical and thermal properties. There has been a growing need and rapid development in large-area deposition of graphene film and its applications. Chemical vapour deposition on copper has emerged as one of the most promising methods in obtaining large-scale graphene films with quality comparable to exfoliated graphene. In this chapter, we review the synthesis and characterizations of graphene…
A novel route for the synthesis of large area graphene by an indigenously built electron cyclotron resonance (ECR) plasma enhanced chemical vapor deposition (PECVD) setup has been reported in this work. A unique 2.45 GHz permanent magnet type ECR PECVD system has been designed and developed for the growth of various nano-structures and films. The apparatus has a unique advantage to synthesize large area graphene at much lower additional substrate heating than heat supplied by an external oven in conventional thermal CVD method. A major amount of heat is supplied here by ECR plasma. Polycrystal…
This report introduces the electromagnetic absorption of the catalyst as a novel knob in optimizing chemical vapor deposition of graphene. A chromium film initially deposited at one side of a catalyst copper foil absorbs radiative thermal energy several times higher than the plain copper foil and migrates to the other side of the foil in the form of microscale grains. The process involves local melting of the copper which together with the increased operation temperature, improves the crystalline quality of growing graphene. Local melting of copper replaces the otherwise-necessary annealing pr…
Micron-scale single-crystal nanowires of metallic TaSe3, a material that forms -Ta-Se3-Ta-Se3- stacks separated from one another by a tubular van der Waals (vdW) gap, have been synthesized using chemical vapor deposition (CVD) on a SiO2/Si substrate, in a process compatible with semiconductor industry requirements. Their electrical resistivity was found unaffected by downscaling from the bulk to as little as 7 nm in width and height, in striking contrast to the resistivity of copper for the same dimensions. While the bulk resistivity of TaSe3 is substantially higher than that of bulk copper, a…
We propose a modified form of pair potential for metals. The parameters of the potential are obtained by fitting the cold curve of the potential to that obtained from the ab-initio calculations. Parameters have been obtained for Aluminum, Copper, Sodium and Potassium. To test the accuracy of the potentials, we performed particle-transfer molecular dynamics simulations and obtained the liquid-vapor coexistence curves of the above metals. We found that, in the cases of Sodium and Potassium, the present results improve significantly over those obtained from Morse potential (J.K. Singh et. al., Fl…
Rhombohedral-stacked few-layer graphene (FLG) has been receiving an ever-increasing attention owing to its peculiar electronic properties that could lead to enticing phenomena such as superconductivity and magnetic ordering. Up to now, experimental studies on such material have been mainly limited by the difficulty in isolating it in thickness exceeding 3 atomic layers with device-compatible size. In this work, rhombohedral graphene with thickness up to 9 layers and areas up to ~50 micrometers square is grown via chemical vapor deposition (CVD) on suspended Cu foils and transferred onto target…
An operando investigation of graphene growth on (100) grains of polycrystalline nickel (Ni) surfaces was performed by means of variable-temperature scanning tunneling microscopy complemented by density functional theory simulations. A clear description of the atomistic mechanisms ruling the graphene expansion process at the stepped regions of the substrate is provided, showing that different routes can be followed, depending on the height of the steps to be crossed. When a growing graphene flake reaches a monoatomic step, it extends jointly with the underlying Ni layer; for higher Ni edges, a …
We present a transfer-free preparation method for graphene on hexagonal boron nitride (h-BN) crystals by chemical vapor deposition of graphene via a catalytic proximity effect, i.e. activated by a Cu catalyst close-by . We demonstrate the full coverage by monolayer graphene of half-millimeter-sized hexagonal boron nitride crystals exfoliated on a copper foil prior to growth. We demonstrate that the proximity of the copper catalyst ensures high yield with the growth rate estimated between of 2μm/min to 5μm/min . Optical and electron microscopies together with confocal micro-Raman mapping confir…
We synthesize large-area graphene via atmospheric-pressure (AP) chemical vapor deposition (CVD) on copper, and transfer to SiO2 wafers. In contrast to low-pressure (LP) CVD on copper, optical contrast and atomic force microscopy measurements show AP-CVD graphene contains significant multi-layer areas. Raman spectroscopy always shows a single Lorentzian 2D peak, however systematic differences are observed in the 2D peak energy, width, and intensity for single- and multi-layer regions. We conclude that graphene multi-layers grown by AP-CVD on Cu are rotationally disordered.
The growth of graphene on copper by atmospheric pressure chemical vapor deposition in a system free of pumping equipment is investigated. The emphasis is put on the necessity of hydrogen presence during graphene synthesis and cooling. In the absence of hydrogen during the growth step or cooling at slow rate, weak carbon coverage, consisting mostly of oxidized and amorphous carbon, is obtained on the copper catalyst. The oxidation originates from the inevitable occurrence of residual oxidizing impurities in the reactor's atmosphere. Graphene with appreciable coverage can be grown within the vac…
Strain can be used as an alternate way to tune the electronic properties of graphene. Here we demonstrate that it is possible to tune the uniform strain of graphene simply by changing the chemical vapor deposition growth temperature of graphene on copper. Due to the cooling of the graphene on copper system, we can induce a uniform compressive strain on graphene. The strain is analyzed by Raman spectroscopy, where a shift in the 2D peak is observed and compared to our ab initio calculations of the graphene on copper system as a function of strain.
We present an electrochemical route for the integration of graphene with light sensitive copper-based alloys used in optoelectronic applications. Graphene grown using chemical vapor deposition (CVD) transferred to glass is found to be a robust substrate on which photoconductive Cu_{x}S films of 1-2 um thickness can be deposited. The effect of growth parameters on the morphology and photoconductivity of Cu_{x}S films is presented. Current-voltage characterization and photoconductivity decay experiments are performed with graphene as one contact and silver epoxy as the other.
We propose an experimental approach, by which thin films of copper polyphthalocyanine (CuPPC) can be directly synthesized in a chemical vapor deposition (CVD) set-up at mild temperature (420 °C). High polymerization degree and high crystallinity of the films was confirmed by TEM, FTIR and UV-VIS studies; the stacking structure of CuPPC layers was determined, inter-layer spacing was estimated from XRD and TEM electron-diffraction. Quantum-chemical study performed providing support for experimental structure determination and yielding information on the electronic structure.
By limiting the carbon segregation at the copper surface defects, a pulsed chemical vapor deposition method for single layer graphene growth is shown to inhibit the formation of few-layer regions, leading to a fully single-layered graphene homogeneous at the centimeter scale. Graphene field-effect devices obtained after transfer of pulsed grown graphene on oxidized silicon exhibit mobilities above 5000 cm^2.V^-1.s^-1.
We propose an innovative, easy-to-implement approach to synthesize large-area singlecrystalline graphene sheets by chemical vapor deposition on copper foil. This method doubly takes advantage of residual oxygen present in the gas phase. First, by slightly oxidizing the copper surface, we induce grain boundary pinning in copper and, in consequence, the freezing of the thermal recrystallization process. Subsequent reduction of copper under hydrogen suddenly unlocks the delayed reconstruction, favoring the growth of centimeter-sized copper (111) grains through the mechanism of abnormal grain grow…
Generalized Phase Diagrams for Graphene CVD growth on Copper
National Laboratory of Solid State Microstructures（固体微结构物理国家重点实验室）；School of Physics, Nanjing University（南京大学物理学院）；Collaborative Innovation Center of Advanced Microstructures（先进结构协同创新中心）
Graphene has been attracting great interest because of its distinctive band structure and physical properties. Today, graphene is limited to small sizes because it is produced mostly by exfoliating graphite. We grew large-area graphene films of the order of centimeters on copper substrates by chemical vapor deposition using methane. The films are predominantly single layer graphene with a small percentage (less than 5%) of the area having few layers, and are continuous across copper surface steps and grain boundaries. The low solubility of carbon in copper appears to help make this growth proc…
We report compressive mechanical response of graphene foams (GFs) and the thermal resistance ($R_{TIM}$) between copper (Cu) and GFs, where GFs were prepared by the chemical vapor deposition (CVD) method. We observe that Young's modulus ($E_{GF}$) and compressive strength ($σ_{GF}$) of GFs have a power law dependence on increasing density ($ρ_{GF}$) of GFs. The maximum efficiency of absorbed energy ($η_{max}$) for all GFs during the compression is larger than ~0.39. We also find that a GF with a higher $ρ_{GF}$ shows a larger $η_{max}$. In addition, we observe that the measured $R_{TIM}$ of Cu…
It is important to understand the electronic interaction between single-walled carbon nanotubes (SWNTs) and graphene in order to use them efficiently in multifunctional hybrid devices. Here we deposited SWNT bundles on graphene-covered copper and SiO2 substrates by chemical vapor deposition and investigated the charge transfer between them by Raman spectroscopy. Our results revealed that, on both copper and SiO2 substrates, graphene donates electrons to the SWNTs, resulting in p-type doped graphene and n-type doped SWNTs.
We synthesized three-dimensional nanoporous graphene films by a chemical vapor deposition method with nanoporous copper as a catalytic substrate. The resulting nanoporous graphene has the same average pore size as the underlying copper substrate. Our surface-enhanced Raman scattering (SERS) investigation indicates that the nanoporosity of graphene significantly improves the SERS efficiency of graphene as a substrate as compared to planar graphene substrates.
The growth of single-layer graphene (SLG) by chemical vapor deposition (CVD) on copper surfaces is very popular because of the self-limiting effect that prevents the growth of few-layer graphene (FLG). However, the reproducibility of the CVD growth of homogeneous SLG remains a major challenge, especially if one wants to avoid heavy surface treatments, monocrystalline substrates and expensive equipment to control the atmosphere inside the growth system. We demonstrate here that backside tungsten coating of copper foil allows the exclusive growth of SLG with full coverage by atmospheric pressure…
We report on electronic properties of graphene synthesized by chemical vapor deposition (CVD) on copper then transferred to SiO2/Si. Wafer-scale (up to 4 inches) graphene films have been synthesized, consisting dominantly of monolayer graphene as indicated by spectroscopic Raman mapping. Low temperature transport measurements are performed on micro devices fabricated from such CVD graphene, displaying ambipolar field effect (with on/off ratio ~5 and carrier mobilities up to ~3000 cm^2/Vs) and "half-integer" quantum Hall effect, a hall-mark of intrinsic electronic properties of monolayer graphe…
Chemical Vapor Deposition (CVD) of graphene on copper is one of the most efficient technologies for producing high quality graphene for large areas. Nevertheless, still high pressures and big quantities of precursor gas are currently required. The objective of this work is to deposit graphene using the monolayer-formation-time concept (t) from the kinetic theory of gases, which leads to an economization of the precursor gas, a minimization of the process pressure and the time needed to grow a graphene monolayer. Our process has been designed taking into account the dependence of t on the press…
The development of wafer-scale continuous single-crystal graphene layers is key in view of its prospective applications. To this end, here we pave the way for a graphene growth model in the framework of the Langmuir adsorption theory and two dimensional crystallization. In specific, we model the nucleation and growth of graphene on copper using methane as carbon precursor. The model leads to identification of the range of growth parameters (temperature and gas pressures) that uniquely entails the final surface coverage of graphene. This becomes an invaluable tool to address the fundamental pro…
The discovery of electric field induced bandgap opening in bilayer graphene opens new door for making semiconducting graphene without aggressive size scaling or using expensive substrates. However, bilayer graphene samples have been limited to um size scale thus far, and synthesis of wafer scale bilayer graphene posts tremendous challenge. Here we report homogeneous bilayer graphene films over at least 2 inch x 2 inch area, synthesized by chemical vapor deposition on copper foil and subsequently transferred to arbitrary substrates. The bilayer nature of graphene film is verified by Raman spect…
The exceptional electronic properties of monoatomic thin graphene sheets triggered numerous original transport concepts, pushing quantum physics into the realm of device technology for electronics, optoelectronics and thermoelectrics. At the conceptual pivot point is the particular twodimensional massless Dirac fermion character of graphene charge carriers and its volitional modification by intrinsic or extrinsic means. Here, interfaces between different electronic and structural graphene modifications promise exciting physics and functionality, in particular when fabricated with atomic precis…
Non-destructive and rapid evaluation of graphene directly on the growth substrate (Cu foils) by dark field (DF) optical microscopy is demonstrated. Without any additional treatment, graphene on Cu foils with various coverages can be quickly identified by DF imaging immediately after chemical vapor deposition growth with contrast comparable to scanning electron microscopy. The improved contrast of DF imaging compared to bright field optical imaging was found to be due to Rayleigh scattering of light by the copper steps beneath graphene. Indeed, graphene adlayers are readily distinguished, due t…
Bottom-up Synthesis of Metastable 2D Hexagonal Copper(I) Iodide on Monolayer and within Bilayer Graphene
Friedrich Schiller University Jena（耶拿弗里德里希·席勒大学）；Leibniz Institute of Photonic Technology (Leibniz-IPHT)（莱布尼茨光子技术研究所）；Ulm University（乌尔姆大学）；University of Nottingham（诺丁汉大学）；Freie Universität Berlin（柏林自由大学）；Leibniz Institute of Surface Engineering (IOM)（莱布尼茨表面工程研究所）
The compression of a low-density copper foam was simulated with a radiation, hydrodynamics code. In one simulation, the foam had a density of $ρ_0 = 1.3407$ g/cm$^3$, 15% the density of copper at standard temperature and pressure, and was composed of a tangle of standard density cylindrical copper filaments with a diameter of $4.0\times10^{-7}$ cm. In another simulation, the foam was a uniform material at the same density. The propagation velocity of the shock wave ($U_f$) through the foam was measured and compared with experimental results. The simulations show approximately the same agreemen…
Current methods of chemical vapor deposition (CVD) of graphene on copper are complicated by multiple processing steps and by high temperatures required in both preparing the copper and inducing subsequent film growth. Here we demonstrate a plasma-enhanced CVD chemistry that enables the entire process to take place in a single step, at reduced temperatures (< 420 C), and in a matter of minutes. Growth on copper foils is found to nucleate from arrays of well-aligned domains, and the ensuing films possess sub-nanometre smoothness, excellent crystalline quality, low strain, few defects and room te…
Although the high impermeability of graphene makes it an excellent barrier to inhibit metal oxidation and corrosion, graphene can form a galvanic cell with the underlying metal that promotes corrosion of the metal in the long term. Boron nitride (BN) nanosheets which have a similar impermeability could be a better choice as protective barrier, because they are more thermally and chemically stable than graphene and, more importantly, do not cause galvanic corrosion due to their electrical insulation. In this study, the performance of commercially available BN nanosheets grown by chemical vapor …
A bottom-up chemical vapor deposition (CVD) process for the growth of graphene nanomesh films is demonstrated. The process relies on silicon nanospheres to block nucleation sites for graphene CVD on copper substrates. These spheres are formed in a self-organized way through silicon diffusion through a 5 $μ$m copper layer on a silicon wafer coated with 400 nm of silicon nitride. The temperature during the growth process disintegrates the $Si_3$$N_4$ layer and silicon atoms diffuse to the copper surface, where they form the nanospheres. After graphene nanomesh growth, the Si nanospheres can be r…
Chemical vapour deposition (CVD) is a promising method for producing large-scale graphene (Gr). Nevertheless, microscopic inhomogeneity of Gr grown on traditional metal substrates such as copper or nickel results in a spatial variation of Gr properties due to long wrinkles formed when the metal substrate shrinks during the cooling part of the production cycle. Recently, molybdenum (Mo) has emerged as an alternative substrate for CVD growth of Gr, mainly due to a better matching of the thermal expansion coefficient of the substrate and Gr. We investigate the quality of multilayer Gr grown on Mo…
We developed a method of precise isotope labeling to visualize the continuous growth of graphene by chemical vapor deposition (CVD). This method allows us to see in real time the growth of graphene monocrystals at a resolution of a few seconds. This technique is used to extract the anisotropic growth rates, the formation of dendrites, and the dependence on adsorption area of methane on copper. We obtain a physical picture of the growth dynamics of graphene and its dependence on various parameters. Finally, our method is relevant to other CVD grown materials.
Understanding the influence that copper substrate surface symmetry and oxygen impurities have on the growth of graphene by chemical vapor deposition is important for developing techniques for producing high quality graphene. Therefore, we have studied the growth of graphene by catalytic decomposition of ethylene in an ultra-high vacuum chamber on both a clean Cu(100) surface and a Cu(100) surface pre-dosed with a layer of chemisorbed oxygen. The crystal structure of the graphene films was characterized with \emph{in-situ} low energy electron diffraction. By heating the clean Cu(100) substrate …
Graphene growth by chemical vapor deposition has received a lot of attention recently owing to the ease with which large area films can be grown, but growth of large domain or equivalently large grain size has not been reported yet. In this brevia, we report on a CVD process that yields graphene with domains of hundreds of micrometers, by very low pressure CVD, less than 50 mTorr, and very low precursor flow rates using methane as the source of carbon on the inside of copper foil enclosures at high temperature, around 1000 oC. The carrier mobility for the large-domain graphene films is up to 2…
Accurate assessment of the antibacterial activity of graphene requires consideration of both the graphene fabrication method and, for supported films, the properties of the substrate. Large-area graphene films produced by chemical vapor deposition were grown directly on copper substrates or transferred on a gold substrate and their effect on the viability and proliferation of the Gram-positive bacteria Staphylococcus aureus and the Gram-negative bacteria Escherichia coli were assessed. The viability and the proliferation of both bacterial species were not affected when they were grown on a gra…
Highly dendritic graphene crystals up to 0.25 mm in diameter are synthesized by low pressure chemical vapor deposition inside a copper enclosure. With their sixfold symmetry and fractal-like shape, the crystals resemble snowflakes. The evolution of the dendritic growth features is investigated for different growth conditions and surface diffusion is found to be the growth-limiting step responsible for the formation of dendrites. The electronic properties of the dendritic crystals are examined down to sub-Kelvin temperatures, showing a mobility of up to 6300 cm$^2$V$^{-1}$s$^{-1}$ and quantum H…
ATK-ForceField is a software package for atomistic simulations using classical interatomic potentials. It is implemented as a part of the Atomistix ToolKit (ATK), which is a Python programming environment that makes it easy to create and analyze both standard and highly customized simulations. This paper will focus on the atomic interaction potentials, molecular dynamics, and geometry optimization features of the software, however, many more advanced modeling features are available. The implementation details of these algorithms and their computational performance will be shown. We present thr…
In this report, we demonstrated a simple but efficient strategy to synthesize millimeter-sized graphene single crystal grains by regulating the supply of reactants in chemical vapor deposition process. Polystyrene was used as a carbon source. Pulse heating on the carbon source was utilized to minimize the nucleation density of graphene on copper foil, while the gradual increase in the temperature of carbon source and the flow rate of hydrogen is adapted to drive the continuous growth of graphene grain. As a result, the nucleation density of graphene grain can be controlled as lower as ~100 nuc…
A graphyne (GY) family composed of the triple (sp) and double (sp2) bonds-hybridized carbon atoms is a promising allotrope of carbon for the development of nanoscale electronic devices. Unlike graphene, the GY family containing carbon sp bonds remains an unsolved problem in efficient two-dimensional (2D) growth due to monomer instability and side reactions. Herein, we synthesize GY into a single 2D layer by chemical vapor deposition (CVD) at low temperatures preventing unexpected reactions, using 1,3,5-tribromo-2,4,6-triethynylbenzene (TBTEB). The CVD-grown GY via a surface-confined coupling b…
