Direct CVD Graphene Growth on Semiconductors and Dielectrics for Transfer‐Free Device Fabrication

Graphene is the most broadly discussed and studied two‐dimensional material because of its preeminent physical, mechanical, optical, and thermal properties. Until now, metal‐catalyzed chemical vapor deposition (CVD) has been widely employed for the scalable production of high‐quality graphene. However, in order to incorporate the graphene into electronic devices, a transfer process from metal substrates to targeted substrates is inevitable. This process usually results in contamination, wrinkling, and breakage of graphene samples ‐ undesirable in graphene‐based technology and not compatible with industrial production. Therefore, direct graphene growth on desired semiconductor and dielectric substrates is considered as an effective alternative. Over the past years, there have been intensive investigations to realize direct graphene growth using CVD methods without the catalytic role of metals. Owing to the low catalytic activity of non‐metal substrates for carbon precursor decomposition and graphene growth, several strategies have been designed to facilitate and engineer graphene fabrication on semiconductors and insulators. Here, those developed strategies for direct CVD graphene growth on semiconductors and dielectrics for transfer‐free fabrication of electronic devices are reviewed. By employing these methods, various graphene‐related structures can be directly prepared on desired substrates and exhibit excellent performance, providing versatile routes for varied graphene‐based materials fabrication.     

新型碳纳米管微焦点电子源研究

介绍了一种基于碳纳米管场发射的新型微焦点电子源技术.利用激光烧蚀镍金属表面使内部未氧化的镍金属熔化喷出暴露于基底表面,再通过化学气相沉积制备出直径约为350μm的半球壳型碳纳米管薄膜阴极.场发射测试表明,电子源具有低开启电场(<1V/μm)、高发射电流(可达1A/cm2)和高压强发射稳定等特点.通过复合石墨烯和750℃...     

Graphene‐Based Electrodes

Graphene, the thinnest two dimensional carbon material, has become the subject of intensive investigation in various research fields because of its remarkable electronic, mechanical, optical and thermal properties. Graphene‐based electrodes, fabricated from mechanically cleaved graphene, chemical vapor deposition (CVD) grown graphene, or massively produced graphene derivatives from bulk graphite, have been applied in a broad range of applications, such as in light emitting diodes, touch screens, field‐effect transistors, solar cells, supercapacitors, batteries, and sensors. In this Review, after a short introduction to the properties and synthetic methods of graphene and its derivatives, we will discuss the importance of graphene‐based electrodes, their fabrication techniques, and application areas.     

Highly efficient electron field emission from graphene oxide sheets supported by nickel nanotip arrays

Electron field emission is a quantum tunneling phenomenon whereby electrons are emitted from a solid surface due to a strong electric field. Graphene and its derivatives are expected to be efficient field emitters due to their unique geometry and electrical properties. So far, electron field emission has only been achieved from the edges of graphene and graphene oxide sheets. We have supported graphene oxide sheets on nickel nanotip arrays to produce a high density of sharp protrusions within the sheets and then applied electric fields perpendicular to the sheets. Highly efficient and stable field emission with low turn-on fields was observed for these graphene oxide sheets, because the protrusions appear to locally enhance the electric field and dramatically increase field emission. Our simple and robust approach provides prospects for the development of practical electron sources and advanced devices based on graphene and graphene oxide field emitters.     

Fabrication of ion-induced carbon-cobalt nanocomposite fibers: effect of cobalt supply rate

Graphite surfaces were irradiated by argon (Ar+) ions at 1 keV with a simultaneous cobalt (Co) supply at room temperature. Various kinds of carbon nanocomposites, such as nanocones with and without single nanofibers on their tops, nanorods and fish-scale-like nanoprotrusions, were formed depending on Co supply rates. It has been observed that with increasing the Co supply rate the formation of nanoprotrusions without nanofibers became prominent. Both nanofibers and nanoprotrusions were surely composed of carbon and Co, as confirmed by energy-dispersive X-ray analysis. The cobalt carbon nanocomposite fibers (CCNFs), -1.5 microm in average length, were grown on the top of the nanocones at the Co supply rate of 1.0 nm/min. The field electron emission characteristics of CCNFs thus grown indicated that there is an optimum parameter for the CCNF growth to achieve the better emission performance than that of pristine Ar(+)-induced carbon nanofibers.     

Process Optimization for Pulse Reverse Electrodeposition of Graphene-Reinforced Copper Nanocomposites

In the present study, processing of graphene-reinforced copper nanocomposite foils with homogenous dispersion of graphene throughout the matrix, exhibiting good mechanical properties by a simple, cost-effective, and scalable pulse reverse electrodeposition technique (PRED) with special focus on the influence of graphene content in the electrolyte to tailor the properties. A systematic approach has been adopted for enhancing the properties. Distribution of graphene nanosheets in the copper metal matrix and the microstructural properties have been studied by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). Interesting observations have been made from nanoindentation studies, where hardness (～2.7 GPa) enhanced mainly with increase in graphene content (0–0.75 g/L), while maximum elastic modulus (～139 GPa) is achieved for a graphene content of 0.5 g/L in the electrolyte. Four-point probe testing has been adopted to evaluate the electrical features. The major contribution in enhancement of properties is found to be the presence of graphene and its uniform individual dispersion and distribution as nanosheets in the copper matrix.     

Field emission microscopy of graphene on iridium point emitter

The field electron emission from the surface of an iridium point emitter covered by a monolayer graphene film has been studied. An analysis of the field emission images showed that electron emission takes place at the boundaries between graphene islands with dimensions up to several dozen nanometers. Intercalation of alkali metal (cesium) atoms under the graphene film decreases the work function of the emitter but does not change the image. Field ion desorption images obtained in the fields where the surface diffusion of Cs atoms is impossible reveal the presence of a submonolayer concentration of cesium at the defects representing graphene island contacts.     

Utilization of ZnO nanocones for the photocatalytic degradation of acridine orange

A facile aqueous solution process was used to synthesize well-crystalline ZnO nanocones at 60 degrees C by using zinc nitrate hexahydrate and sodium hydroxide. The morphological, structural and optical properties of the synthesized ZnO nanocones were investigated by using field emission scanning electron microscopy (FESEM) attached with energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM) equipped with high-resolution (HRTEM), X-ray diffraction (XRD) pattern, Fourier transform infrared (FTIR) spectroscopy and UV-Vis. spectroscopy measurements. The structural and optical properties of the as-synthesized nanocones confirmed a pure and well crystalline product possessing wurtzite hexagonal phase. The as-synthesized ZnO nanocones were used as photocatalyst for the efficient photocatalytic degradation of acridine orange. The acridine orange was almost completely degraded within 105 minutes. This research demonstrates that the simply synthesized ZnO nanostructures could be efficient photocatalyst for the photocatalytic degradation of various organic dyes and chemicals.     

Hydrothermal fabrication of copper sulfide nanocones and nanobelts

Novel copper sulfide nanocones and nanobelts have been hydrothermally fabricated at 140 °C for 24 h with acrylamide and sodium dodecyl benzene sulfonate (SDBS) as surfactants, respectively. X-ray diffraction (XRD) pattern indicates that the as-prepared samples are the pure hexagonal phase CuS. XPS spectra show that the ratio of Cu/S is about 1:1.084. The morphology was characterized by scanning electron microscopy (SEM) and field emission scanning electron microscopy (FE-SEM) techniques. Transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) images reveal that nanocones and nanobelts grow along the [110] axis. The surfactant is found to be critical to the morphologies of the products. The possible formation mechanism is also discussed.     

Carbon Nanotubes for Cold Electron Sources

Technological advances in the field of microelectronic fabrication techniques have triggered a great interest in vacuum microelectronics. In contrast to solid‐state microelectronics, which entails scattering‐dominated electron transport in semiconducting solids, vacuum microelectronics relies on the scattering‐free, ballistic motion of electrons in vacuum. Since the first international conference on vacuum microelectronics substantial progress in this field has been made. The first technological devices using micrometer‐sized electron emitting structures are currently being commercialized. Field‐emission flat‐panel displays (FED) seem to be an especially promising competitor to LCD displays. Today there is only one mature technology for producing micro‐gated field‐emission arrays: the Spindt metal‐tip process. The drawbacks of this technology are expensive production, critical lifetime in vacuum, and high operating voltage. Carbon nanotubes (CNT) can be regarded as the potential second‐generation technology to the Spindt metal micro‐tip. In this review we show that the field emission (FE) behavior of CNT can be accurately described by Fowler–Nordheim tunneling and that the field‐enhancement factor β is the most prominent factor. Therefore the FE properties of a CNT thin film can be understood in terms of local field enhancement β(x,y), which can be determined with scanning anode field emission microscopy (SAFEM). To characterize the FE properties of an ensemble of electron emitters we used a statistical approach (as for thin film emitters), where f(β)dβ gives the number of emitters on a unit area with field‐enhancement factors within the interval [β,β + dβ]. We show that the field‐enhancement distribution function f(β) gives an almost complete characterization of the FE properties.     

Direct CVD Growth of Graphene on Traditional Glass: Methods and Mechanisms

Chemical vapor deposition (CVD) on catalytic metal surfaces is considered to be the most effective way to obtain large‐area, high‐quality graphene films. For practical applications, a transfer process from metal catalysts to target substrates (e.g., poly(ethylene terephthalate) (PET), glass, and SiO₂/Si) is unavoidable and severely degrades the quality of graphene. In particular, the direct growth of graphene on glass can avoid the tedious transfer process and endow traditional glass with prominent electrical and thermal conductivities. Such a combination of graphene and glass creates a new type of glass, the so‐called “super graphene glass,” which has attracted great interest from the viewpoints of both fundamental research and daily‐life applications. In the last few years, great progress has been achieved in pursuit of this goal. Here, these growth methods as well as the specific growth mechanisms of graphene on glass surfaces are summarized. The typical techniques developed include direct thermal CVD growth, molten‐bed CVD growth, metal‐catalyst‐assisted growth, and plasma‐enhanced growth. Emphasis is placed on the strategy of growth corresponding to the different natures of glass substrates. A comprehensive understanding of graphene growth on nonmetal glass substrates and the latest status of “super graphene glass” production are provided.     

Lowering the Schottky Barrier Height by Graphene/Ag Electrodes for High‐Mobility MoS2 Field‐Effect Transistors

2D transition metal dichalcogenides (TMDCs) have emerged as promising candidates for post‐silicon nanoelectronics owing to their unique and outstanding semiconducting properties. However, contact engineering for these materials to create high‐performance devices while adapting for large‐area fabrication is still in its nascent stages. In this study, graphene/Ag contacts are introduced into MoS₂ devices, for which a graphene film synthesized by chemical vapor deposition (CVD) is inserted between a CVD‐grown MoS₂ film and a Ag electrode as an interfacial layer. The MoS₂ field‐effect transistors with graphene/Ag contacts show improved electrical and photoelectrical properties, achieving a field‐effect mobility of 35 cm² V^?1 s^?1, an on/off current ratio of 4 × 10⁸, and a photoresponsivity of 2160 A W^?1, compared to those of devices with conventional Ti/Au contacts. These improvements are attributed to the low work function of Ag and the tunability of graphene Fermi level; the n‐doping of Ag in graphene decreases its Fermi level, thereby reducing the Schottky barrier height and contact resistance between the MoS₂ and electrodes. This demonstration of contact interface engineering with CVD‐grown MoS₂ and graphene is a key step toward the practical application of atomically thin TMDC‐based devices with low‐resistance contacts for high‐performance large‐area electronics and optoelectronics.     

Vertically aligned one-dimensional AlN nanostructures on conductive substrates: Synthesis and field emission

Herein we report the synthesis of vertically aligned AlN nanostructures on conductive substrates through the chemical reaction between AlCl₃ and NH₃ in the temperature range of 650-850 °C. The morphologies of the AlN nanostructures could be controllably modulated from cone-like to rod-like geometries by increasing the reaction temperature. The formation mechanism of the AlN nanostructures on the nitrified Ti substrates has been discussed based on the analysis of the intermediate products. The field emission (FE) property of AlN nanocones grown on the nitrified Ti substrate is better than that for AlN nanocones on Si substrate. The improvement of FE property can be attributed to the lower resistance between AlN nanocones and the nitrified Ti substrate because the conductive titanium nitride film can directly contact with AlN emitters while a high-resistive silica layer would easily form between Si substrate and AlN nanocones. These results indicate that the deposition of nanoscale filed emitters on conductive substrates is an effective way to improve the FE behavior, and may find potential applications in FE devices.     

2D AlN Layers Sandwiched Between Graphene and Si Substrates

Due to the superior thickness‐dependent properties, 2D materials have exhibited great potential for applications in next‐generation optoelectronic devices. Despite the significant progress that has been achieved, the synthesis of 2D AlN remains challenging. This work reports on the epitaxial growth of 2D AlN layers via utilizing physically transferred graphene on Si substrates by metal–organic chemical vapor deposition. The 2D AlN layers sandwiched between graphene and Si substrates are confirmed by annular bright‐field scanning transmission electron microscopy and the effect of hydrogenation on the formation of 2D AlN layers is clarified by theoretical calculations with first‐principles calculations based on density functional theory. Moreover, the bandgap of as‐grown 2D AlN layers is theoretically predicted to be ≈9.63 eV and is experimentally determined to be 9.20–9.60 eV. This ultrawide bandgap semiconductor shows great promise in deep‐ultraviolet optoelectronic applications. These results are expected to support innovative and front‐end development of optoelectronic devices.     

3D graphene/fly ash waste material for hybrid supercapacitor electrode: specific capacitance analysis

The performance of supercapacitor energy storage is depending on the type of the material that is used as supercapacitor electrode. Graphene has been widely used as the base material for a lot of applications due to its remarkable properties. In this research, we try to combine 3D Graphene with waste material fly ash to be used as the electrode of supercapacitor. Fly ash is a residual material from burning pulverized coal in electric generation power plants which contain metal oxide materials such as iron oxide and aluminum oxide. This residual material might be usable as an electrode for supercapacitor due to its material contained. As the base material, the 3D graphene was successfully fabricated by using low pressure chemical vapor deposition (LPCVD) method and afterwards the fly ash was coated on the top of 3D graphene. The chemical properties and surface structure of the electrode material was studied by using Raman spectroscopy and field emission scanning electron spectroscopy (FESEM). 3 electrode systems were used to analyze the cyclic voltammetry results. According to the results, they show that the highest specific capacitance of 3D graphene/fly ash (FA) was about 0.025 F/cm2 at the lowest scan rate of 5 mV/s and it is recommended to use as the supercapacitor electrode.     

Gold nanocones fabricated by nanotransfer printing and their application for field emission

Arrays of gold nanocones have been fabricated by the nanotransfer printing (nTP) method and we have utilized these nanocones for field emission. By the nature of the printing, any shape of metal structure can be fabricated only at desired locations and a step-and-repeat process, which enables large-area fabrication, is possible. We demonstrate step-and-repeat printing with gold nanocone patterns occupying an area of 9?mm × 8?mm.     

Molecular Self‐Assembly on Graphene

The formation of ordered arrays of molecules via self‐assembly is a rapid, scalable route towards the realization of nanoscale architectures with tailored properties. In recent years, graphene has emerged as an appealing substrate for molecular self‐assembly in two dimensions. Here, the first five years of progress in supramolecular organization on graphene are reviewed. The self‐assembly process can vary depending on the type of graphene employed: epitaxial graphene, grown in situ on a metal surface, and non‐epitaxial graphene, transferred onto an arbitrary substrate, can have different effects on the final structure. On epitaxial graphene, the process is sensitive to the interaction between the graphene and the substrate on which it is grown. In the case of graphene that strongly interacts with its substrate, such as graphene/Ru(0001), the inhomogeneous adsorption landscape of the graphene moiré superlattice provides a unique opportunity for guiding molecular organization, since molecules experience spatially constrained diffusion and adsorption. On weaker‐interacting epitaxial graphene films, and on non‐epitaxial graphene transferred onto a host substrate, self‐assembly leads to films similar to those obtained on graphite surfaces. The efficacy of a graphene layer for facilitating planar adsorption of aromatic molecules has been repeatedly demonstrated, indicating that it can be used to direct molecular adsorption, and therefore carrier transport, in a certain orientation, and suggesting that the use of transferred graphene may allow for predictible molecular self‐assembly on a wide range of surfaces.     

Cl‐Doped ZnO Nanowire Arrays on 3D Graphene Foam with Highly Efficient Field Emission and Photocatalytic Properties

An environmentally friendly, low‐cost, and large‐scale method is developed for fabrication of Cl‐doped ZnO nanowire arrays (NWAs) on 3D graphene foam (Cl‐ZnO NWAs/GF), and investigates its applications as a highly efficient field emitter and photocatalyst. The introduction of Cl‐dopant in ZnO increases free electrons in the conduction band of ZnO and also leads to the rough surface of ZnO NWAs, which greatly improves the field emission properties of the Cl‐ZnO NWAs/GF. The Cl‐ZnO NWAs/GF demonstrates a low turn‐on field (≈1.6 V μm⁻¹), a high field enhancement factor (≈12844), and excellent field emission stability. Also, the Cl‐ZnO NWAs/GF shows high photocatalytic efficiency under UV irradiation, enabling photodegradation of organic dyes such as RhB within ≈75 min, with excellent recyclability. The excellent photocatalytic performance of the Cl‐ZnO NWAs/GF originates from the highly efficient charge separation efficiency at the heterointerface of Cl‐ZnO and GF, as well as improved electron transport efficiency due to the doping of Cl. These results open up new possibilities of using Cl‐ZnO and graphene‐based hybrid nanostructures for various functional devices.     

Graphene-reinforced metal matrix nanocomposites – a review

The research works of graphene-reinforced metal matrix composites will be summarised in this paper. Comparatively, much less research works have been undertaken in this field. Graphene has been thought to be an ideal reinforcement material for composites due to its unique two-dimensional structure and outstanding physical and mechanical properties. It is expected to yield structural materials with high specific strength or functional materials with exciting thermal and electrical characteristics. This paper will introduce all kinds of graphene-reinforced metal matrix composites that have been studied. The microstructure and mechanical properties, processing techniques, graphene dispersion, strengthening mechanisms, interfacial reactions between graphene and the metal matrix and future research works in this field will be discussed.     

Sulfur and Nitrogen Co‐Doped Graphene for Metal‐Free Catalytic Oxidation Reactions

Sulfur and nitrogen co‐doped reduced graphene oxide (rGO) is synthesized by a facile method and demonstrated remarkably enhanced activities in metal‐free activation of peroxymonosulfate (PMS) for catalytic oxidation of phenol. Based on first‐order kinetic model, S–N co‐doped rGO (SNG) presents an apparent reaction rate constant of 0.043 ± 0.002 min^?1, which is 86.6, 22.8, 19.7, and 4.5‐fold as high as that over graphene oxide (GO), rGO, S‐doped rGO (S‐rGO), and N‐doped rGO (N‐rGO), respectively. A variety of characterization techniques and density functional theory calculations are employed to investigate the synergistic effect of sulfur and nitrogen co‐doping. Co‐doping of rGO at an optimal sulfur loading can effectively break the inertness of carbon systems, activate the sp²‐hybridized carbon lattice and facilitate the electron transfer from covalent graphene sheets for PMS activation. Moreover, both electron paramagnetic resonance (EPR) spectroscopy and classical quenching tests are employed to investigate the generation and evolution of reactive radicals on the SNG sample for phenol catalytic oxidation. This study presents a novel metal‐free catalyst for green remediation of organic pollutants in water.