Controllable Growth of Graphene on Liquid Surfaces

Controllable fabrication of graphene is necessary for its practical application. Chemical vapor deposition (CVD) approaches based on solid metal substrates with morphology‐rich surfaces, such as copper (Cu) and nickel (Ni), suffer from the drawbacks of inhomogeneous nucleation and uncontrollable carbon precipitation. Liquid substrates offer a quasiatomically smooth surface, which enables the growth of uniform graphene layers. The fast surface diffusion rates also lead to unique growth and etching kinetics for achieving graphene grains with novel morphologies. The rheological surface endows the graphene grains with self‐adjusted rotation, alignment, and movement that are driven by specific interactions. The intermediary‐free transfer or the direct growth of graphene on insulated substrates is demonstrated using liquid metals. Here, the controllable growth process of graphene on a liquid surface to promote the development of attractive liquid CVD strategies is in focus. The exciting progress in controlled growth, etching, self‐assembly, and delivery of graphene on a liquid surface is presented and discussed in depth. In addition, prospects and further developments in these exciting fields of graphene growth on a liquid surface are discussed.     

铜基底预处理对CVD法生长石墨烯薄膜的影响

化学气相沉积法是制备大尺寸、高质量石墨烯的有效方法, 其中金属催化剂的性能直接关系到所制备的石墨烯材料的品质, 因此需对金属催化剂进行表面预处理。本文研究了不同的预处理工艺对常用的铜基底催化剂表面状态的影响, 提出了钝化膏酸洗和电化学抛光协同处理的有效方法, 并对电化学抛光工艺参数(抛光电压、时间)以及铜基底退火工艺(退火温度、时间)等进行了系统研究。研究表明: 电化学抛光电压过高、抛光时间过长容易导致过度抛光, 合适的抛光电压和抛光时间分别为8 V和8 min。退火温度和时间对铜催化剂表面晶粒形态影响较大, 经1000 ℃退火处理30 min后, 铜箔表面晶粒尺寸更大, 分布更均匀。此外, 对CVD法生长制备的石墨烯样品进行表征, 电镜图片和拉曼光谱显示, 获得的石墨烯薄膜的层数较少, 且结构缺陷较少。     

铜基底化学气相沉积石墨烯的研究现状与展望

采用粉末包埋法在中国低活性铁素体马氏体钢（RAFM）基底上制备了低活性渗铝层,利用扫描电镜（SEM）和能谱分析（EDS）对渗铝层的形貌和成分进行了分析。结果表明：低活性渗铝层表面铝含量（原子分数）约40％,主要由厚度为15-20μm的FeAl、Fe3-Al及α-Fe（Al）相组成,该渗铝层表面易发生烧结。为避免表面烧结...     

Copper‐Vapor‐Assisted Growth and Defect‐Healing of Graphene on Copper Surfaces

Although there is significant progress in the chemical vapor deposition (CVD) of graphene on Cu surfaces, the industrial application of graphene is not realized yet. One of the most critical obstacles that limit the commercialization of graphene is that CVD graphene contains too many vacancies or sp³‐type defects. Therefore, further investigation of the growth mechanism is still required to control the defects of graphene. During the growth of graphene, sublimation of the Cu catalyst to produce Cu vapor occurs inevitably because the process temperature is close to the melting point of Cu. However, to date few studies have investigated the effects of Cu vapor on graphene growth. In this study, how the Cu vapor produced by sublimation affects the chemical vapor deposition of graphene on Cu surfaces is investigated. It is found that the presence of Cu vapor enlarges the graphene grains and enhances the efficiency of the defect‐healing of graphene by CH₄. It is elucidated that these effects are due to the removal by Cu vapor of carbon adatoms from the Cu surface and oxygen‐functionalized carbons from graphene. Finally, these insights are used to develop a method for the synthesis of uniform and high‐quality graphene.     

超高真空CVD生长锗硅外延层的应变弛豫

用超高真空ＣＶＤ技术在７８０℃生长了锗硅外延层及组分渐变缓冲层,并利用双晶Ｘ射线衍射仪研究了缓冲层对外延层晶体质量的影响。结果表明,衬底与外延之间生长了组分几乎线性渐变的缓冲层,提高了外延层的晶体质量     

Orientation‐Dependent Strain Relaxation and Chemical Functionalization of Graphene on a Cu(111) Foil

Epitaxial graphene grown on single crystal Cu(111) foils by chemical vapor deposition is found to be free of wrinkles and under biaxial compressive strain. The compressive strain in the epitaxial regions (0.25–0.40%) is higher than regions where the graphene is not epitaxial with the underlying surface (0.20–0.25%). This orientation‐dependent strain relaxation is through the loss of local adhesion and the generation of graphene wrinkles. Density functional theory calculations suggest a large frictional force between the epitaxial graphene and the Cu(111) substrate, and this is therefore an energy barrier to the formation of wrinkles in the graphene. Enhanced chemical reactivity is found in epitaxial graphene on Cu(111) foils as compared to graphene on polycrystalline Cu foils for certain chemical reactions. A higher compressive strain possibly favors lowering the formation energy and/or the energy gap between the initial and transition states, either of which can lead to an increase in chemical reactivity.     

Adlayer‐Free Large‐Area Single Crystal Graphene Grown on a Cu(111) Foil

To date, thousands of publications have reported chemical vapor deposition growth of “single layer” graphene, but none of them has described truly single layer graphene over large area because a fraction of the area has adlayers. It is found that the amount of subsurface carbon (leading to additional nuclei) in Cu foils directly correlates with the extent of adlayer growth. Annealing in hydrogen gas atmosphere depletes the subsurface carbon in the Cu foil. Adlayer‐free single crystal and polycrystalline single layer graphene films are grown on Cu(111) and polycrystalline Cu foils containing no subsurface carbon, respectively. This single crystal graphene contains parallel, centimeter‐long ≈100 nm wide “folds,” separated by 20 to 50 µm, while folds (and wrinkles) are distributed quasi‐randomly in the polycrystalline graphene film. High‐performance field‐effect transistors are readily fabricated in the large regions between adjacent parallel folds in the adlayer‐free single crystal graphene film.     

Graphene Glass from Direct CVD Routes: Production and Applications

Recently, direct chemical vapor deposition (CVD) growth of graphene on various types of glasses has emerged as a promising route to produce graphene glass, with advantages such as tunable quality, excellent film uniformity and potential scalability. Crucial to the performance of this graphene‐coated glass is that the outstanding properties of graphene are fully retained for endowing glass with new surface characteristics, making direct‐CVD‐derived graphene glass versatile enough for developing various applications for daily life. Herein, recent advances in the synthesis of graphene glass, particularly via direct CVD approaches, are presented. Key applications of such graphene materials in transparent conductors, smart windows, simple heating devices, solar‐cell electrodes, cell culture medium, and water harvesters are also highlighted.     

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.     

Unraveling the Water Impermeability Discrepancy in CVD‐Grown Graphene

Graphene has recently attracted particular interest as a flexible barrier film preventing permeation of gases and moistures. However, it has been proved to be exceptionally challenging to develop large‐scale graphene films with little oxygen and moisture permeation suitable for industrial uses, mainly due to the presence of nanometer‐sized defects of obscure origins. Here, the origins of water permeable routes on graphene‐coated Cu foils are investigated by observing the micrometer‐sized rusts in the underlying Cu substrates, and a site‐selective passivation method of the nanometer‐sized routes is devised. It is revealed that nanometer‐sized holes or cracks are primarily concentrated on graphene wrinkles rather than on other structural imperfections, resulting in severe degradation of its water impermeability. They are found to be predominantly induced by the delamination of graphene bound to Cu as a release of thermal stress during the cooling stage after graphene growth, especially at the intersection of the Cu step edges and wrinkles owing to their higher adhesion energy. Furthermore, the investigated routes are site‐selectively passivated by an electron‐beam‐induced amorphous carbon layer, thus a substantial improvement in water impermeability is achieved. This approach is likely to be extended for offering novel barrier properties in flexible films based on graphene and on other atomic crystals.     

High‐Quality Monolayer Graphene Synthesis on Pd Foils via the Suppression of Multilayer Growth at Grain Boundaries

The segregation of carbon from metals in which carbon is highly soluble, such as Ni (≈1.1 atom% at 1000 °C), is a typical method for graphene growth; this method differs from the surface‐catalyzed growth of graphene that occurs on other metals such as Cu (<0.04 atom%). It has not been established whether strictly monolayer graphene could be synthesized through the traditional chemical vapor deposition route on metals where carbon is highly soluble, such as Pd (≈3.5 atom%). In this work, this issue is investigated by suppressing the grain boundary segregation using a pretreatment comprising the annealing of the Pd foils; this method was motivated by the fact that the typical thick growths at the grain boundaries revealed that the grain boundary functions as the main segregation channel in polycrystalline metals. To evaluate the high crystallinity of the as‐grown graphene, detailed atomic‐scale characterization with scanning tunneling microscopy is performed.