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 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.     

Graphene on Group‐IV Elementary Semiconductors: The Direct Growth Approach and Its Applications

Since the first development of large‐area graphene synthesis by the chemical vapor deposition (CVD) method in 2009, CVD‐graphene has been considered to be a key material in the future electronics, energy, and display industries, which require transparent, flexible, and stretchable characteristics. Although many graphene‐based prototype applications have been demonstrated, several important issues must be addressed in order for them to be compatible with current complementary metal‐oxide‐semiconductor (CMOS)‐based manufacturing processes. In particular, metal contamination and mechanical damage, caused by the metal catalyst for graphene growth, are known to cause severe and irreversible deterioration in the performance of devices. The most effective way to solve the problems is to grow the graphene directly on the semiconductor substrate. Herein, recent advances in the direct growth of graphene on group‐IV semiconductors are reviewed, focusing mainly on the growth mechanism and initial growth behavior when graphene is synthesized on Si and Ge. Furthermore, recent progress in the device applications of graphene with Si and Ge are presented. Finally, perspectives for future research in graphene with a semiconductor are discussed.     

Toward Mass Production of CVD Graphene Films

Chemical vapor deposition (CVD) is considered to be an efficient method for fabricating large‐area and high‐quality graphene films due to its excellent controllability and scalability. Great efforts have been made to control the growth of graphene to achieve large domain sizes, uniform layers, fast growth, and low synthesis temperatures. Some attempts have been made by both the scientific community and startup companies to mass produce graphene films; however, there is a large difference in the quality of graphene synthesized on a laboratory scale and an industrial scale. Here, recent progress toward the mass production of CVD graphene films is summarized, including the manufacturing process, equipment, and critical process parameters. Moreover, the large‐scale homogeneity of graphene films and fast characterization methods are also discussed, which are crucial for quality control in mass production.     

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.     

Germanium‐Assisted Direct Growth of Graphene on Arbitrary Dielectric Substrates for Heating Devices

Direct growth of graphene on dielectric substrates is a prerequisite to the development of graphene‐based electronic and optoelectronic devices. However, the current graphene synthesis methods on dielectric substrates always involve a metal contamination problem, and the direct production of graphene patterns still remains unattainable and challenging. Herein, a semiconducting, germanium (Ge)‐assisted, chemical vapor deposition approach is proposed to produce monolayer graphene directly on arbitrary dielectric substrates. By the prepatterning of a catalytic Ge layer, the graphene with desired pattern can be achieved conveniently and readily. Due to the catalysis of Ge, monolayer graphene is able to form on Ge‐covered dielectric substrates including SiO₂/Si, quartz glass, and sapphire substrates. Optimization of the process parameters leads to complete sublimation of the catalytic Ge layer during or immediately after formation of the monolayer graphene, enabling direct deposition of large‐area and continuous graphene on dielectric substrates. The large‐area, highly conductive graphene synthesized on a transparent dielectric substrate using the proposed approach has exhibited a wide range of applications, including in both defogger and thermochromic displays, as already successfully demonstrated here.     

Controlled Growth of Single-Crystal Graphene Films

Grain boundaries produced during material synthesis affect both the intrinsic properties of materials and their potential for high-end applications. This effect is commonly observed in graphene film grown using chemical vapor deposition and therefore caused intense interest in controlled growth of grain-boundary-free graphene single crystals in the past ten years. The main methods for enlarging graphene domain size and reducing graphene grain boundary density are classified into single-seed and multiseed approaches, wherein reduction of nucleation density and alignment of nucleation orientation are respectively realized in the nucleation stage. On this basis, detailed synthesis strategies, corresponding mechanisms, and key parameters in the representative methods of these two approaches are separately reviewed, with the aim of providing comprehensive knowledge and a snapshot of the latest status of controlled growth of single-crystal graphene films. Finally, perspectives on opportunities and challenges in synthesizing large-area single-crystal graphene films are discussed.     

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.     

Direct Synthesis of Few‐Layer Graphene on NaCl Crystals

Chemical vapor deposition is used to synthesize few‐layer graphene on micro crystalline sodium chloride (NaCl) powder. The water‐soluble nature of NaCl makes it convenient to produce free standing graphene layers via a facile and low‐cost approach. Unlike traditional metal‐catalyzed or oxygen‐aided growth, the micron‐size NaCl crystal planes play an important role in the nucleation and growth of few‐layer graphene. Moreover, the possibility of synthesizing cuboidal graphene is also demonstrated in the present approach for the first time. Raman spectroscopy, optical microscopy, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy are used to evaluate the quality and structure of the few‐layer graphene along with cuboidal graphene obtained in this process. The few‐layer graphene synthesized using the present method has an adsorption ability for anionic and cationic dye molecules in water. The present synthesis method may pave a facile way for manufacturing few‐layer graphene on a large scale.     

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...     

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。     

模拟浮法在线工艺制备多功能TiN镀膜玻璃

本文模拟浮法玻璃在线CVD镀膜工艺,利用常压化学气相沉积小型镀膜机,以TiCl_4和NH_3作为反应物前驱体,成功地在玻璃表面镀制一层TiN薄膜,获得了具有高阻隔紫外及反射红外的多功能镀膜玻璃。对其性能进行分析显示:随着反应物NH3流量的增加,TiN薄膜阻隔紫外线的性能逐渐提高,在近红外区的Drude型反射区域有所缩小,但其在高频近红外波段的反射率有所提高。当NH_3达到300sccm时,能够完全阻隔低于380nm的紫外线波段,反射红外线效果良好。随着基板移动速率的增大,在一定程度内可以提高薄膜对近红外线的反射能力,但阻隔紫外线的性能逐渐降低。     

Ultrafast Graphene Growth on Insulators via Metal‐Catalyzed Crystallization by a Laser Irradiation Process: From Laser Selection,Thickness Control to Direct Patterned Graphene Utilizing Controlled Layer Segregation Process

Despite the vast progress in chemical vapor deposition (CVD) graphene grown on metals, the transfer process is still a major bottleneck, being not devoid of wrinkles and polymer residues. In this paper, a structure is introduced to directly synthesize few layer graphene on insulating substrates by a laser irradiation heating process. The segregation of graphene layers can be manipulated by tuning the metal layer thickness and laser power at different scanning rates. Graphene deposition and submicrometer patterning resolution can be achieved by patterning the intermediate metal layer using standard lithography methods in order to overcome the scalability issue regardless the resolution of the laser beam. The systematic analysis of the process based on the formation of carbon microchannels by the laser irradiation process can be extended to several materials, thicknesses, and methods. Furthermore, hole and electron mobilities of 500 and 950 cm²V^?1s^?1 are measured. The laser‐synthesized graphene is a step forward along the direct synthesis route for graphene on insulators that meets the criteria for photonics and electronics.