Three-dimensional nano-foam of few-layer graphene grown by CVD for DSSC

We report a robust and direct route to fabricate a three-dimensional nano-foam of few-layer graphene (3D-NFG) with large area coverage via a chemical vapor deposition (CVD) technique. Pyrolysis of polymer/nickel precursor film under a hydrogen environment, simply prepared by spin-coating, leads to the creation of nano-foam in the film and the reduction process of nickel ions. Carbonized-C and the nickel nano-frame formed from the pyrolysis are used as a solid carbon source and as a catalyst for the growth of graphene under CVD conditions, respectively. We investigate the use of 3D-NFG, with the advantage of large surface area and high conductivity, as an alternative to the Pt counter electrode material in dye sensitized solar cells. The excellent properties of 3D-NFG, fabricated in this simple and direct manner, suggest a great potential for interconnected graphene networks in electronic devices and photocatalytic sensors as well as in energy-related materials.     

Oxygen-aided synthesis of polycrystalline graphene on silicon dioxide substrates

We report the metal-catalyst-free synthesis of high-quality polycrystalline graphene on dielectric substrates [silicon dioxide (SiO(2)) or quartz] using an oxygen-aided chemical vapor deposition (CVD) process. The growth was carried out using a CVD system at atmospheric pressure. After high-temperature activation of the growth substrates in air, high-quality polycrystalline graphene is subsequently grown on SiO(2) by utilizing the oxygen-based nucleation sites. The growth mechanism is analogous to that of growth for single-walled carbon nanotubes. Graphene-modified SiO(2) substrates can be directly used in transparent conducting films and field-effect devices. The carrier mobilities are about 531 cm(2) V(-1) s(-1) in air and 472 cm(2) V(-1) s(-1) in N(2), which are close to that of metal-catalyzed polycrystalline graphene. The method avoids the need for either a metal catalyst or a complicated and skilled postgrowth transfer process and is compatible with current silicon processing techniques.     

Optimization of Parameters of Graphene Synthesis on Copper Foil at Low Methan Pressure

Graphene films on copper foils were synthesized using low-pressure (2200-2800 Pa) chemical vapor deposition (CVD) from methane/hydrogen mixtures. The number of graphene layers is shown to be dependent on the composition of gas mixture and synthesis parameters. The annealing procedure of copper foils used as substrates was optimized to obtain high quality graphene. Atomic and electronic structures of graphene on copper and SiO₂/Si substrates were studied by Raman, X-ray photoelectron, and near-edge X-ray absorption fine structure spectroscopy methods.     

Morphology engineering and etching of graphene domain by low-pressure chemical vapor deposition

Controlled growth of single-crystal high-quality ‘track-and-field ground’ shaped graphene domains and the morphological evolution from hexagonal to hexagram graphene domain even square and circular graphene domain has been achieved by low-pressure CVD on solid copper substrate, thereby demonstrating that the shape of the graphene grains can potentially be precisely tuned by optimizing growth parameters. The etching reaction of graphene has also been studied, and results show that a low flow rate of hydrogen (99.999%) is favorable to form hexagonal structure for the etching reaction of graphene due to the exist of oxygen or oxidizing impurities in hydrogen gas commonly used. Controlled growth and etching reaction of graphene determine the final shape of graphene domains and all these efforts contribute to the study of size and morphology and the growth mechanism of graphene domains.     

Characterization of graphene grown on bulk and thin film nickel

We report on graphene films grown by atmospheric pressure chemical vapor deposition on bulk and thin film nickel. Carbon precipitation on the polycrystalline grains is controlled by the methane concentration and substrate cooling rate. It is found that graphene grows over multiple grains, with edges terminating along the grain boundaries and with dimensions directly correlated to the size of the underlying grains. This greatly restricts the resulting graphene size (<10 μm) in the thin film growth, whereas monolayer graphene with linear dimensions of hundreds of micrometers takes up the great majority of the surface overlayers on the bulk nickel (>50%). In addition, the number of layers can be better controlled in the bulk growth. Characterizations of the graphene sheets using transmission electron microscopy, Raman spectroscopy, and transport measurements in the field-effect configuration are also discussed.     

Selective graphene formation on copper twin crystals

Selective graphene growth on copper twin crystals by chemical vapor deposition has been achieved. Graphene ribbons can be formed only on narrow twin crystal regions with a (001) or high-index surface sandwiched between Cu crystals having (111) surfaces by tuning the growth conditions, especially by controlling the partial pressure of CH(4) in Ar/H(2) carrier gas. At a relatively low CH(4) pressure, graphene nucleation at steps on Cu (111) surfaces is suppressed, and graphene is preferentially nucleated and formed on twin crystal regions. Graphene ribbons as narrow as ～100 nm have been obtained in experiments. The preferential graphene nucleation and formation seem to be caused primarily by a difference in surface-dependent adsorption energies of reactants, which has been estimated by first principles calculations. Concentrations of reactants on a Cu surface have also been analyzed by solving a diffusion equation that qualitatively explains our experimental observations of the preferential graphene nucleation. Our findings may lead to self-organizing formation of graphene nanoribbons without reliance on top-down approaches in the future.     

Electrodeposition mechanism of nickel films on polycrystalline copper from dilute simple sulphate solutions

In this paper, we have studied the mechanism of nucleation and growth of nickel from a simple sulfate bath on polycrystalline copper (Cu) substrate. Cyclic voltammetry technique and current transients recorded during electrodeposition of nickel on Cu were used to evaluate the electrochemical deposition of nickel on copper. Results show that nickel starts to grow on copper from a typical potential of −0.7 V vs. Ag/AgCl. Increasing scan rate of cyclic voltammograms shifts the reduction peaks towards a more negative values. We plotted non-dimensional graphs according to the Scharifker-Hills theory and concluded an instantaneous nucleation and growth mechanism for nickel elecrodeposited on copper based on our experimental conditions.     

甲烷在O/Ni(100)表面上的反应动力学研究

甲烷在Ｏ／Ｎｉ（１００）表面上的反应动力学研究俞华根，程极源（中国科学院成都有机化学研究所，成都６１００１５）关键词甲烷，活化解离，预吸附氧，Ｎｉ（１００）表面，分子动力学，势能面甲烷在金属催化剂表面活化解离是重要的催化反应，受到了高度重视．近年来，...     

Ultrafast Electron Transfer Kinetics of Graphene Grown by Chemical Vapor Deposition

High electrochemical reactivity is required for various energy and sensing applications of graphene grown by chemical vapor deposition (CVD). Herein, we report that heterogeneous electron transfer can be remarkably fast at CVD‐grown graphene electrodes that are fabricated without using the conventional poly(methyl methacrylate) (PMMA) for graphene transfer from a growth substrate. We use nanogap voltammetry based on scanning electrochemical microscopy to obtain very high standard rate constants k⁰≥25 cm s^?1 for ferrocenemethanol oxidation at polystyrene‐supported graphene. The rate constants are at least 2–3 orders of magnitude higher than those at PMMA‐transferred graphene, which demonstrates an anomalously weak dependence of electron‐transfer rates on the potential. Slow kinetics at PMMA‐transferred graphene is attributed to the presence of residual PMMA. This unprecedentedly high reactivity of PMMA‐free CVD‐grown graphene electrodes is fundamentally and practically important.     

Low temperature growth of highly nitrogen-doped single crystal graphene arrays by chemical vapor deposition

The ability to dope graphene is highly important for modulating electrical properties of graphene. However, the current route for the synthesis of N-doped graphene by chemical vapor deposition (CVD) method mainly involves high growth temperature using ammonia gas or solid reagent melamine as nitrogen sources, leading to graphene with low doping level, polycrystalline nature, high defect density and low carrier mobility. Here, we demonstrate a self-assembly approach that allows the synthesis of single-layer, single crystal and highly nitrogen-doped graphene domain arrays by self-organization of pyridine molecules on Cu surface at temperature as low as 300 °C. These N-doped graphene domains have a dominated geometric structure of tetragonal-shape, reflecting the single crystal nature confirmed by electron-diffraction measurements. The electrical measurements of these graphene domains showed their high carrier mobility, high doping level, and reliable N-doped behavior in both air and vacuum.     

Preparation of different graphene nanostructures for hydrogen adsorption

In this study, different types of graphene were synthesized to investigate hydrogen adsorption capacity at different pressures (0–34 bar) at room temperature (298 K). Graphene and nanoporous graphene were prepared by Chemical Vapor Deposition (CVD) method, using methane as a carbon source at a temperature of 900 °C over copper plates and nickel oxide nanocatalyst. The nickel oxide nanocatalyst was prepared by sol–gel method, whereas graphene oxide was prepared through modified Hummer's method. The products were characterized by X‐ray diffraction, field emission‐scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller and Raman spectroscopy. The adsorption of hydrogen was done by volumetric method. High adsorption capacity was achieved in nanoporous graphene because of its high pore volume (2.11 cm³/g) and large specific surface area (850 m²/g). Hydrogen adsorption values for nanoporous graphene, graphene and graphene oxide were determined as 2.56, 1.70 and 0.74 wt%, respectively. In addition, the hydrogen adsorption of graphene nanostructures fitted nicely to the selected two‐parameter and three‐parameter adsorption isotherm models. The adsorption isotherm model coefficients have been found for a 0–34 bar pressure range. The parameter values for all adsorbents showed proper conformity to the model and experimental data. Copyright © 2016 John Wiley & Sons, Ltd.     

Fast growth of graphene on SiO2/Si substrates by atmospheric pressure chemical vapor deposition with floating metal catalysts

Graphene on dielectric substrates is essential for its electronic applications. Graphene is typically synthesized on the surface of metal and then transferred to an appropriate substrate for fabricating device applications. This post growth transfer process is detrimental to the quality and performance of the as-grown graphene. Therefore, direct growth of graphene films on dielectric substrates without any transfer process is highly desirable. However, fast growth of graphene on dielectric substrates remains challenging. Here, we demonstrate a transfer-free chemical vapor deposition (CVD) method to directly grow graphene films on dielectric substrates at fast growth rate using Cu as floating catalyst. A large area (centimeter level) graphene can be grown within 15 min using this CVD method, which is increased by 500 times compared to other direct CVD growth on dielectric substrate in the literatures. This research presents a significant progress in transfer-free growth of graphene and graphene device applications.     

Superclean Growth of Graphene Using a Cold-Wall Chemical Vapor Deposition Approach

Chemical vapor deposition (CVD) has become a promising approach for the industrial production of graphene films with appealing controllability and uniformity. However, in the conventional hot-wall CVD system, CVD-derived graphene films suffer from surface contamination originating from the gas-phase reaction during the high-temperature growth. Shown here is that the cold-wall CVD system is capable of suppressing the gas-phase reaction, and achieves the superclean growth of graphene films in a controllable manner. The as-received superclean graphene film, exhibiting improved optical and electrical properties, was proven to be an ideal candidate material used as transparent electrodes and substrate for epitaxial growth. This study provides a new promising choice for industrial production of high-quality graphene films, and the finding about the engineering of the gas-phase reaction, which is usually overlooked, will be instructive for future research on CVD growth of graphene.     

生物质羟基磷灰石作为模板制备三维石墨烯

As a new 2D material with excellent chemical stability, good electric conductivity, and high specific surface area, graphene has been widely used in energy storage and conversion devices. However, 2D graphene layers are easily stacked, which may significantly reduce the surface area and degrade the excellent electrical properties of graphene. To avoid this, one of the most effective methods is to construct 3D graphene (3DG) with specific porous microstructures. Chemical vapor deposition (CVD) is an important method for the synthesis of high-quality 3DG, where templates play a defining role in controlling the structure and cost of 3DG. Metallic materials with 3D microstructures, such as nickel foam, have proven to be useful as substrates for the growth of high-quality 3DG. However, metal substrates are usually expensive, and the pickling solution generated after etching may cause environmental problems. Therefore, non-metallic substrate materials with lower costs have been investigated for the preparation of 3DG. Herein, we developed a novel template material, mammal bone ashes, for the CVD preparation of 3DG. Mammal bone ash is an inexpensive and abundant biomass hydroxyapatite. During the high-temperature CVD reaction, the bone ash powders were slightly sintered to form a continuous porous structure with graphene coating. The morphology of 3DG is inherited from the microstructure of bone ash templates. After removing the bone ash template with hydrochloric acid, the template-grown 3DG was obtained with a unique bicontinuous structure, i.e. both the graphene framework and the void space were continuous. In addition, the pickling solution of the bone ash templates after etching was exactly the same as that for the raw materials for the production of phosphoric acid to achieve high atom utilization. We further optimized the graphitization degrees, layer number, and porous morphology of 3DGs. The microstructure evolution of 3DG is highly relevant to the layer thickness and uniformity of graphene layers. A short growth time would lead to a non-uniform and thin layer of graphene, which is not able to support a complex 3D porous structure. In contrast, a uniform graphene layer with proper thickness is capable of forming a robust 3D architecture. In addition, the facile CVD method can be extended to a series of metal phosphate templates, including tricalcium phosphate [Ca₃(PO₄)₂], trimagnesium phosphate [Mg₃(PO₄)₂], and aluminum phosphate [AlPO₄]. 3DG with bicontinuous morphology is promising as a conductive frame material in electrochemical energy storage devices. As an illustration, high-performance Li-S batteries were fabricated by the uniform composition of an S cathode on 3DG. In comparison with heavily stacked 2D graphene sheets in reduced graphene oxide / S composite, the non-flat structure of 3DGs remained unchanged even after the harsh melt-diffusion process of high-viscosity liquid sulfur. The resulting 3DG/S cathode delivered a high specific capacity of ~550 mAh∙g^-1 at a high current rate (2C). Our work opens an avenue to the low-cost and high-utility production of 3D graphene, which could be integrated with the well-developed phosphorus chemical industry.     

Superclean Growth of Graphene Using a Cold‐Wall Chemical Vapor Deposition Approach

Chemical vapor deposition (CVD) has become a promising approach for the industrial production of graphene films with appealing controllability and uniformity. However, in the conventional hot‐wall CVD system, CVD‐derived graphene films suffer from surface contamination originating from the gas‐phase reaction during the high‐temperature growth. Shown here is that the cold‐wall CVD system is capable of suppressing the gas‐phase reaction, and achieves the superclean growth of graphene films in a controllable manner. The as‐received superclean graphene film, exhibiting improved optical and electrical properties, was proven to be an ideal candidate material used as transparent electrodes and substrate for epitaxial growth. This study provides a new promising choice for industrial production of high‐quality graphene films, and the finding about the engineering of the gas‐phase reaction, which is usually overlooked, will be instructive for future research on CVD growth of graphene.     

石墨烯晶圆的制备：从高品质到规模化

石墨烯晶圆是引领未来的战略材料,在集成电路、微机电系统和传感器等领域具有广阔的应用前景。实现石墨烯晶圆广泛应用的前提是高品质材料的规模化制备。可控性高、工艺兼容性强、成本低的化学气相沉积(chemical vapor deposition,CVD)法,是高品质石墨烯晶圆规模化制备的首选方法。本文将综述石墨烯晶圆的CVD制备进展：首先探讨石墨烯晶圆的制备需求,从实用牵引和应用场景出发,提出石墨烯晶圆的制备品质等级;随后重点介绍石墨烯的晶圆级制备方法和石墨烯晶圆材料的规模化制备技术;最后,对石墨烯晶圆可行的制备路线进行总结,并展望未来可能的发展方向。     

Ga对在AlN衬底上直接生长石墨烯的远程催化

通过镓(Ga)远程催化, 采用化学气相沉积(CVD)方法在氮化铝(AlN)衬底上直接生长石墨烯薄膜. 研究了生长温度、 催化剂距离对石墨烯生长及其光学性质和电学性质的影响规律. 结果表明, 在生长温度1070 ℃下可以制备厚度约为5层的石墨烯薄膜, Ga周围1.4 cm范围内可以得到厚度均匀的石墨烯薄膜. 通过透光率和方阻表征了石墨烯的光学和电学性质, 结果表明, 400~800 nm波长范围内石墨烯薄膜透光率可达90%以上, 方阻约为230 Ω/□. 第一性原理计算结果表明, 石墨烯仍保持金属性, AlN衬底对石墨烯有吸附掺杂作用, 可有效降低石墨烯的方阻, 改善石墨烯和衬底的电学接触.     

石墨烯玻璃:玻璃表面上石墨烯的直接生长

玻璃是一种历史悠久、用途广泛的无定形硅酸盐材料,而石墨烯则是近年来发现的仅由碳原子组成的二维层状材料。石墨烯具有超高的机械强度、导电性、导热性和透明性,恰好与传统的玻璃形成互补。将石墨烯与玻璃结合在一起,在保持透明性的基础上,同时赋予普通玻璃导电性、导热性和表面疏水性,具有非常重要的实际意义和理论价值。相比于液相涂膜或者转移的方法,直接在玻璃表面生长石墨烯能够从根本上避免由于污染和破损引起的石墨烯性能的下降,从而发展出一种新型材料——石墨烯玻璃。本文介绍了我们研究组在各种玻璃表面直接生长石墨烯的研究进展,其中包括石墨烯在固态耐高温玻璃和熔融态玻璃表面的高温生长,以及利用等离子体辅助手段实现石墨烯在普通玻璃表面的低温生长,并以此为基础发展出多种基于石墨烯玻璃的应用实例。总结展望了石墨烯玻璃的制备和应用的未来挑战与发展方向。     

Detection of OH stretching mode of CH3OH chemisorbed on Ni3+ and Ni4+ by infrared photodissociation spectroscopy

Structures of nickel cluster ions adsorbed with methanol, Ni3+ (CH3OH)m (m = 1-3) and Ni4+ (CH3OH)m (m = 1-4) were investigated by using infrared photodissociation (IR-PD) spectroscopy based on a tandem-type mass spectrometer, where they were produced by passing Ni3,4+ through methanol vapor under a multiple collision condition. The IR-PD spectra were measured in the wavenumber region between 3100 and 3900 cm-1. In each IR-PD spectrum, a single peak was observed at a wavenumber lower by approximately 40 cm-1 than that of the OH stretching vibration of a free methanol molecule and was assigned to the OH stretching vibrations of the methanol molecules in Ni3,4+ (CH3OH)m. The photodissociation was analyzed by assuming that Ni3,4+ (CH3OH)m dissociate unimolecularly after the photon energy absorbed by them is statistically distributed among the accessible modes of Ni3,4+ (CH3OH)m. In comparison with the calculations performed by the density functional theory, it is concluded that (1) the oxygen atom of each methanol molecule is bound to one of the nickel atoms in Ni3,4+ (defined as molecular chemisorption), (2) the methanol molecules in Ni3,4+ (CH3OH)m do not form any hydrogen bonds, and (3) the cross section for demethanation [CH4 detachment from Nin+ (CH3OH)] is related to the electron density distribution inside the methanol molecule.     

Mutual Influence of Electrode Processes during Electrodeposition of Layered Structures by the Single-Bath Method: The Effect of Nickel Deposition and Hydrogen Evolution on the Transport of Copper Ions in Acetate and Sulfamate Electrolytes

The effect of nickel deposition and hydrogen evolution on the transport of copper-containing ions is studied by numerically solving an electrodiffusion problem with use made of variational values of the formation constants of nickel and copper complexes in acetate and sulfamate electrolytes and thicknesses of the diffusion layer. It is concluded that the major contribution to the mass transfer is made by the effects of exaltation of the migration current and by the agitation of the near-electrode layer of electrolyte by evolving hydrogen. The possibility of employing migration effects in order to reduce the limiting current of copper in the region of nickel deposition and hydrogen evolution is substantiated. This will decrease the copper content in a layer of alloy during electrodeposition of layered structures.