石墨烯的化学气相沉积生长与过程工程学研究

化学气相沉积法(CVD)在制备高质量、大尺寸石墨烯方面显示出巨大 的优势 [11~13] , 该方法成本低廉, 更能够和目前的集 成 电 路 工 艺 相 兼 容 .

We investigate the carrier mobility in monolayer and bilayer graphene with a top HfO2 dielectric, as a function of the HfO2 film thickness and temperature. The results show that the carrier mobility decreases during the deposition of the first 2–4 nm of top dielectric and remains constant for thicker layers. The carrier mobility shows a relatively weak dependence on temperature indicating that phonon scattering does not play a dominant role in controlling the carrier mobility. The data strongly suggest that fixed charged impurities located in close proximity to the graphene are responsible for the mobility degradation.

In this research, we have investigated the unintended graphene nucleation problem and its damaging effects on monolayer graphene synthesis in low-pressure chemical vapor deposition (LPCVD) process. This problem is the growth of graphene on the copper surface with no carbon feedstock. A new source of undesired carbon species was identified which has not been addressed so far. The hydrogen-rich heating stage was diagnosed as the onset of the unintended nucleation for the first time owing to the determinant catalytic role of hydrogen in this stage. It was found out that this problem leads to uncontrollable growth of multilayer graphene, growth of defective graphene film and also inhibition of the reliable synthesis of monolayer graphene. We managed to grow enhanced-quality monolayer graphene by developing some innovative solutions to the problem containing a general solution based on the hydrogen effects in the heating stage. The results reveal a significant decrease in the unintended nucleation density from ∼2000 to almost zero domains per 100 × 100 μm2 copper area. Furthermore, Raman, HRTEM and SAED analysis confirm the defect-free growth of monolayer graphene after employing the solutions. These findings could pave the way for the reliable synthesis of high-quality monolayer graphene as well as large-sized graphene domains.

Transfer-free growth of polymer-derived graphene on dielectric substrate from mobile hot-wire-assisted dual heating system

ConspectusGraphene, a one-atom-thick layer of carbon with a honeycomb lattice, has drawn great attention due to its outstanding properties and its various applications in electronic and photonic devices. Mechanical exfoliation has been used for preparing graphene flakes (from monolayer to multilayer with thick pieces also typically present), but with sizes limited typically to less than millimeters, its usefulness is limited. Chemical vapor deposition (CVD) has been shown to be the most effective technique for the scalable preparation of graphene films with high quality and uniformity. To date, CVD growth of graphene on the most commonly used substrates (Cu and Ni foils) has been demonstrated and intensively studied. However, a survey of the existing literature and earlier work using Cu or Ni substrates for CVD growth indicates that the bilayer and multilayer graphene over a large area, particularly single crystals, have not been obtained.In this Account, we review current progress and development in the CVD growth of graphene and highlight the important challenges that need to be addressed, for example, how to achieve large single crystal graphene films with a controlled number of layers. A single-layer graphene film grown on polycrystalline Cu foil was first reported by our group, and since then various techniques have been devoted to achieving the fast growth of large-area graphene films with high quality. Commercially available Cu/Ni foils, sputtered Cu/Ni thin films, and polycrystalline Cu/Ni foils have been used for the CVD synthesis of bilayer, trilayer, and multilayer graphene. Cu/Ni alloy substrates are particularly interesting due to their greater carbon solubility than pure Cu substrates and this solubility can be finely controlled by changing the alloy composition. These substrates with controlled compositions have shown the potential for the growth of layer-tunable graphene films in addition to providing a much higher growth rate due to their stronger catalytic activity. However, the well-controlled preparation of single crystal graphene with a defined number of layers on Cu/Ni substrates is still challenging.Due to its small lattice mismatch with graphene, a single crystal Cu(111) foil has been shown to be an ideal substrate for the epitaxial growth of graphene. Our group has reported the synthesis of large-size single crystal Cu(111) foils by the contact-free annealing of commercial Cu foils, and single crystal Cu/Ni(111) alloy foils have also been obtained after the heat-treatment of Ni-coated Cu(111) foils. The use of these single crystal foils (especially the Cu/Ni alloy foils) as growth substrates has enabled the fast growth of single crystal single-layer graphene films. By increase of the Ni content, single crystal bilayer, trilayer, and even multilayer graphene films have been synthesized. In addition, we also discuss the wafer-scale growth of single-layer graphene on the single crystalline Cu/Ni(111) thin films.Recent research results on the large-scale preparation of single crystal graphene films with different numbers of layers on various types of Cu/Ni alloy substrates with different compositions are reviewed and discussed in detail. Despite the remarkable progress in this field, further challenges, such as the wafer-scale synthesis of single crystal graphene with a controlled number of layers and a deeper understanding of the growth mechanism of bilayer and multilayer graphene growth on Cu/Ni substrates, still need to be addressed.

Promoter-assisted chemical vapor deposition of graphene

Graphene, the atomic thin carbon film with honeycomb lattice, holds great promise in a wide range of applications, due to its unique band structure and excellent electronic, optical, mechanical, and thermal properties. Scientists are researching this star material because of the development of various emerging preparation techniques, among which chemical vapor deposition (CVD) has received the fastest advances in the past few years. For the CVD growth of graphene, the ultimate goal is to achieve the highest quality in the largest scale and lowest cost with a precise control of layer thickness, stacking order, and crystallinity. To meet this goal, researchers need a comprehensive understanding and effective controlling of the growth process, especially to its elementary steps. In this Account, we focus on our recent progresses toward the controlled surface growth of graphene and its two-dimensional (2D) hybrids via rational designs of CVD elementary processes, namely, process engineering. A typical CVD process consists of four main elementary steps: (A) adsorption and catalytic decomposition of precursor gas, (B) diffusion and dissolution of decomposed carbon species into bulk metal, (C) segregation of dissolved carbon atoms onto the metal surface, and finally, (D) surface nucleation and growth of graphene. Absence or enhancement of each elementary step would lead to significant changes in the whole growth process. Metals with certain carbon solubility, such as nickel and cobalt, involve all four elementary steps in a typical CVD process, thus providing us an ideal system for process engineering. The elementary segregation process can be completely blocked if molybdenum is introduced into the system as an alloy catalyst, yielding perfect monolayer graphene almost independent of growth parameters. On the other hand, the segregation-only process of predissolved solid carbons is also capable of high-quality graphene growth. By using a synergetic Cu-Ni alloy, we are able to further enhance the control to such a segregation technique, especially for the thickness of graphene. By designing a cosegregation process of carbon atoms with other elements, such as nitrogen, doped graphene could be synthesized directly with a tunable doping profile. Copper with negligible carbon solubility provides another platform for process engineering, where both carbon dissolution and segregation steps are negligible in the CVD process. Carbon atoms decomposed from precursors diffuse on the surface and build up the thermodynamically stable honeycomb lattice. As a result, graphene growth on copper is self-limited, and formation of multilayer graphene is generally prohibited. Being able to control this process better, as well as the high quality produced, makes copper-based growth the dominating synthesis procedure in the graphene community. We designed a two-temperature zone system to spatially separate the catalytic decomposition step of carbon precursors and the surface graphitization step for breaking this self-limited growth feature, giving high-quality Bernal stacked bilayer graphene via van der Waals epitaxy. We performed the so-called wrinkle engineering by growing graphene on nanostructured copper foil together with a structure-preserved surface transfer. In such a way, we controlled the wrinkling or folding on graphene and further fabricated graphene nanoribbon arrays by self-masked plasma etching. Moreover, by designing a two-step patching growth process on copper, we succeeded in synthesizing the mosaic graphene, a patchwork of intrinsic and nitrogen-doped graphene connected by single crystalline graphene p-n junctions. By following a general concept of process engineering, our work on the designed CVD growth of graphene and its 2D hybrids provides a unique insight of this research field. It enables the precise growth control of graphene together with the in-depth understanding of CVD growth process, which would further stimulate the pace of graphene applications.

Graphene is a single layer of sp2 bonded carbon atoms that crystallizes in the honeycomb structure. Because of its true two-dimensional structure, it has very unique electrical properties, including a very high carrier mobility that is symmetric for holes and electrons. To realize these unique properties, it is important to develop a method for growing graphene films with uniform thickness and low defect density. One of the most popular methods of growth is by chemical vapor deposition on Cu substrates, because it is self-limited. However many applications require the growth of graphene films that are more than one atomic layer thick. In this research project, the growth of graphene on CuNi substrates has been studied. The presence of Ni in the alloy results in an increase in the catalytic activity of the surface. This results in lower deposition pressures than for pure Cu and also increases the carbon solubility, which allows the growth of films that are more than one atomic layer thick.

The controlled growth of large-area single-crystalline graphene via epitaxial methods such as chemical vapor deposition (CVD) is essential in the eventual widespread realization of graphene-based devices. In this endeavor, one startling obstacle is the emergence of abundant grain boundaries in a growing graphene layer. Here, we carry out comparative studies of single-layer graphene films grown on optimized Cu(111) and Cu–Ni(111) alloyed substrates using various experimental probes and first-principles calculations. We demonstrate, convincingly, that the use of the Ni substitutionally alloyed Cu substrate results in drastic elimination of grain boundaries in graphene films compared to those grown on pure Cu. The underlying mechanism of the highly preferred single-crystalline growth is the elimination of the orientational disorder of multiple initial nucleation islands on the Cu–Ni(111) surface, as demonstrated theoretically and confirmed experimentally. The present study not only unveils the atomistic growth mechanism of single-crystalline monolayered graphene on Cu–Ni alloys with a fast growth rate and mass productivity but also sheds light on the controlled CVD growth of large-area twist-angle bilayer graphene, multilayered graphene, and other 2D vdW materials in general.

It is known that low-field mobility of graphene depends largely on the substrate material on which it is transferred. We measured Drude optical conductivity of graphene on various substrates and determined the carrier density and carrier scattering rate. The carrier density varies widely depending on the substrate material. However the scattering rate is almost constant, approximately 100 cm(-1), for 5 different substrates. We calculate carrier mobility of graphene using the two quantities, i.e., carrier density and scattering rate, to find that it agrees with the mobility measured from dc transport experiment. We conclude that substrate-depent mobility of graphene originates from different carrier density but not from the scattering rate.

The employment of Ni–Mo films has recently been shown to yield strictly homogeneous single-layer graphene. In this study, we systematically investigate the different stages of nucleation and growth of graphene over Ni–Mo layers. The studies reveal that the Ni film breaks up and diffuses into the underlying Mo foil, forming a Ni–Mo intermetallic. Nucleation only occurs from Ni sites, and thus, the nucleation density can be controlled by the Ni film thickness. Both nucleation and growth of the graphene are shown to be susceptible to very efficient self-termination processes to the formation of molybdenum carbide, and this guarantees the formation of large area graphene that consists entirely of monolayer graphene.

A new kinetic model of isothermal growth of single-layer graphene on a copper catalyst as a result of the chemical vapor deposition of hydrocarbons on it at a low pressure has been developed on the basis of in situ measurements of the growth of graphene in the process of its synthesis. This model defines the synthesis of graphene with regard for the chemisorption and catalytic decomposition of ethylene on the surface of a copper catalyst, the diffusion of carbon atoms in the radial direction to the nucleation centers within the thin melted near-surface copper layer, and the nucleation and autocatalytic growth of graphene domains. It is shown that the time dependence of the rate of growth of a graphene domain has a characteristic asymmetrical bell-like shape. The dependences of the surface area and size of a graphene domain and the rate of its growth on the time at different synthesis temperatures and ethylene concentrations have been obtained. Time characteristics of the growth of graphene domains depending on the parameters of their synthesis were calculated. The results obtained can be used for determining optimum regimes of synthesis of graphene in the process of chemical vapor deposition of hydrocarbons on different catalysts with a low solubility of carbon.

Stainless steel has been widely utilized due to it high resistance of corrosion, rust, and stain more than ordinary steel. However, a hardness of stainless-steel surface is not high resulting in engineering applications of stainless steel are limited. Graphene is an extremely hard material therefore the growth of graphene on stainless steel can increase the surface hardness of stainless steel. Vegetable oil consists of triglyceride which has abundant carbon in the constituent. Vegetable oil has been widely used for cooking. After the cooking, a huge amount of the waste vegetable oil is flushed down the drain resulting in water pollution. However, the waste vegetable oil still contains abundant carbon which can be used as a carbon source for graphene growth on stainless steel by chemical vapor deposition (CVD). In this study, the surface hardening of stainless steel through graphene growth on stainless steel by CVD using waste palm oil as a carbon source is demonstrated. The results show that the fourth-used palm oil can be utilized as a carbon source for the growth of graphene on stainless steel by CVD. Moreover, the graphene growth on stainless steel by CVD using the fourth-used palm oil can increase the surface hardness of stainless steel by 175%.

Chemical vapor deposition (CVD) is an affordable method for the preparation of large-scale and high-quality graphene. With the increase in CVD reactor size, gas mass transfer, flow state, and gas phase dynamics become more complicated. In this study, computational fluid dynamics is used to investigate factors affecting the uniformity of large-scale graphene growth under different growth conditions and reactor configurations. The dimensionless number defined in this paper and the Grashof number are utilized to distinguish the species transfer patterns and the flow states, respectively. A gas-surface dynamics model is established to simulate the graphene growth. Results reveal that the graphene growth rate uniformity is the highest at very low pressure and flow rate due to the flow symmetry and diffusion-dominated species transfer. At an increased pressure of 20 Torr, the uniformity of the graphene growth rate becomes higher axially and lower circumferentially with an increasing inlet mass flow rate. When the flow rate is fixed at 1500 SCCM and pressure is reduced from 20 to 2 Torr, graphene growth uniformity first increases and then decreases due to the influence of gas phase dynamics. Graphene growth rates are analyzed across ordinary reactor configurations and four configurations with inner tubes at 20 Torr pressure and 1500 SCCM flow rate. Comprehensive evaluation suggests that the ordinary reactor configuration performs best under these conditions. This research offers insights into the macroscopic growth mechanism of large-scale graphene and provides guidance for designing growth conditions in large-area graphene production.

The controlled preparation of high-quality graphene is essential for its practical application. Chemical vapor deposition (CVD) emerging as a prominent means to synthesize the material owing to its superior controllability and compatibility. To address the complex transfer issues associated with graphene growth on metal substrates via CVD, growing graphene directly on insulating substrates is a promising alternative. However, this method has several limitations, such as small domain size, high defect density, and slow growth rates. Despite numerous strategies for enhancing graphene growth on insulators, the intrinsic mechanisms that affect energy changes during CVD processes remain underexplored. The review provides an in-depth analysis of these strategies, focusing on their effects on the three critical stages of CVD growth: precursor decomposition, nucleation, and edge growth. The energy dynamics at each stage are examined, highlighting the role of metal additives and alternative precursors in reducing the pyrolysis energy barriers and improving growth efficiency. In Addition, this review discusses the strategies for enhancing graphene nucleation and edge growth to achieve high-quality monolayer graphene. Finally, the challenges and future prospects of the direct growth of high-quality graphene on insulating substrates are presented, offering insights into the path forward for industrial-scale graphene production.