化学气相沉积法制备大尺寸单晶石墨烯的工艺参数研究

石墨烯作为一种二维sp2杂化碳的同素异形体,具有优良的电学、光学、热学及力学等性质.产业化应用石墨烯要求其具有大的尺寸且性质均一.化学气相沉积法(CVD)的出现为制备大尺寸、高质量的石墨烯提供了可能.本文结合近几年CVD法制备石墨烯的研究进展,综述了影响大尺寸、单晶石墨烯制备的工艺参数,包括衬底选择与预处理、碳源与辅助气体流量调控、腔体温度和压力控制、沉积时间以及降温速率设定等.最后展望了制备大尺寸单晶石墨烯的研究方向.     

铜基底上双层至多层石墨烯常压化学气相沉积法制备与机理探讨

化学气相沉积是目前最重要的ー种制备高质量、大面积石墨烯的方法.而铜是化学气相沉积法制备石墨烯中最常用的生长基底.虽然有大量文章报道了关于石墨烯的生长条件及生长机理,但是作为最广泛采用的材料,铜基底上双层及多层石墨烯的生长机理仍然在探索中,本文采用常压化学气相沉积法,以乙醇为碳源在铜基底上生长石墨烯,并将其转移到SiO_2/Si基底上.用场发射扫描电镜、透射电镜、拉曼光谱、光学显微镜对所制备的石墨烯进行表征和层数分析,对转移到不同基底上的不同层数的石墨烯进行了透光性分析.结果表明,常压条件下铜箔表面能够生长出质量较高、连续性较好的双层至多层石墨烯.此外,我们还对铜基底上双层至多层石墨烯的生长机理进行了探讨.     

介电层表面直接生长石墨烯的研究进展

作为21世纪备受瞩目的材料,石墨烯兼具优异的电、热、光与力学性质,具有十分广阔的研究价值与应用价值.目前主要通过在金属基底上生长获得石墨烯,并将其转移至目标介电层基底上以构筑电子器件.转移过程不可避免地引入了褶皱、裂纹、破损以及聚合物/金属残留,严重损害了石墨烯的性能.因而直接在介电基底上制备高质量的石墨烯薄膜具有重要意义.本文总结了近年来在介电衬底上直接生长石墨烯的研究进展:阐述了金属辅助法、等离子体增强法以及热力学或动力学调控法等多种生长手段;介绍了多种介电/绝缘基底包括SiO_2/Si,Al_2O_3,SrTiO_3,h-BN,SiC,Si_3N_4以及玻璃表面生长石墨烯的特点与性能,分析了其可能的生长机理.根据拉曼谱图、薄层电阻、透光率、载流子迁移率等评估指标,将多种方法得到的石墨烯质量进行了总结与比较,并提出了直接在介电衬底上生成石墨烯的研究难点与趋势.     

石墨烯在金属表面防腐中的应用

石墨烯作为一种新型材料,因其出色的化学惰性和抗渗透性逐渐成为了防腐领域的研究热点.本文结合最新的研究成果,对包括石墨烯薄膜及石墨烯粉体在防腐领域的应用进行更加全面的讨论.从石墨烯防腐作用机理(主要包括阻隔、屏蔽、缓蚀、加固、阴极保护和自修复)和其相应的涂层制备方法 (化学气相沉积法制备的石墨烯薄膜及石墨烯粉体制备的复合涂料)开始,进而探讨不同影响因素(缺陷、导电性、氧化程度、片层大小及含量等)对石墨烯防腐效果的影响,最后对各种方法进行综合比较,并对未来的发展进行展望.本文通过对已有工作的回顾,为今后制备防腐性能更加优良的石墨烯材料提供重要的参考.     

高质量大面积石墨烯的化学气相沉积制备方法研究

石墨烯因其奇特的能带结构和优异的物理性能而成为近年来大家研究的热点, 但是目前单层石墨烯的质量与尺寸制约了其实际应用的发展. 本文采用常压化学气相沉积(CVD)方法, 基于铜箔衬底, 利用甲烷作为碳源制备了高质量大面积的单层与多层石墨烯. 研究发现: 高温度、稀薄的甲烷浓度、较短的生长时间以及合适的气体流速是制备高质量、大面积石墨烯的关键. Raman光谱, 扫描电子显微镜、透射电子显微镜等表征结果表明: 制备的石墨烯主要为单层, 仅铜箔晶界处有少量多层石墨烯. 电学测试表明CVD制备的石墨烯在低温时呈现出较明显的类半导体特性; 薄膜电阻随外界磁场的增大而减小.     

金属原子催化作用下缺陷石墨烯薄膜的自修复过程

采用分子动力学方法,模拟了金属原子存在条件下缺陷石墨烯的自修复过程.模拟采用了Ni和Pt两种金属原子作为催化剂,通过改变系统温度,得到了多组模拟结果.观察对比了模拟结束时获得的原子构型图,并通过计算修复过程中石墨烯内5,6,7元环的数量变化,研究了不同金属原子对缺陷石墨烯的催化修复效果,发现在适当的温度(1600 K和2000 K)下,与无金属原子条件下的修复结果相比,两种金属原子都表现出了一定的催化修复能力,且Ni表现出的催化修复能力要优于Pt.为了探究其背后的机理,我们模拟了部分典型的结构演变.发现Ni和Pt原子分别会导致"环内跳出"和"断环"的局部结构转变,并且在不同温度下均表现出不同程度捕获碳链的能力.此外,观察了两种金属原子在平面内外的不同迁移行为,并通过绘制金属原子的迁移路线,计算其迁移量,进一步研究了两种金属原子不同的催化修复机理.研究结果有利于认识不同金属原子具有的不同催化修复效果,理解不同金属原子的催化作用机制,有助于针对缺陷石墨烯的修复选择合适的催化剂.     

六方氮化硼表面石墨烯纳米带生长与物性研究

石墨烯作为二维原子晶体家族的典型代表,由于其优异的物理与化学特性而受到学术界与工业界的广泛关注.石墨烯纳米带是宽度仅有几纳米到几十纳米的石墨烯.纳米带不但继承了石墨烯大部分优异的性能,而且具备可调控带隙、自旋极化边界态等石墨烯所不具有的新奇物理特性.这些特性使石墨烯纳米带成为未来探索石墨烯电子学应用所需要重点研究的对象.利用与石墨烯晶格结构相似的六方氮化硼(h-BN)作为绝缘介质衬底进行石墨烯及石墨烯纳米带制备,不仅可以有效地保持它们优异的本征性质,还可以开发出与主流半导体工艺相兼容的电子器件工艺与应用.本文回顾了近几年h-BN表面石墨烯及石墨烯纳米带研究的发展历程,详细阐述了最近的材料制备和物性研究的进展,并对高质量h-BN衬底制备的最新进展进行介绍,以期为未来实现高质量h-BN表面石墨烯纳米带的规模化制备并最终实现电子器件应用奠定基础.最后本文对h-BN表面石墨烯及石墨烯纳米带的未来研究方向进行了展望.     

化学气相沉积石墨烯薄膜的洁净转移

石墨烯因其优异的性能在很多领域具有广阔的应用前景.目前石墨烯薄膜主要是以铜作为催化基底,通过化学气相沉积法制备.这种方法制备的石墨烯薄膜需要被转移到目标基底上进行后续应用,而转移过程则会对石墨烯造成污染,进而影响石墨烯的性质及器件的性能.如何减少或避免污染,实现石墨烯的洁净转移,是石墨烯薄膜转移技术研究的重要课题,也是本综述的主题.本综述首先简单介绍了石墨烯的转移方法;进而重点讨论由于转移而引入的各种污染物及其对石墨烯性质的影响,以及如何抑制污染物的引入或如何将其有效地去除;最后总结了石墨烯洁净转移所存在的挑战,展望了未来的研究方向和机遇.本综述不仅有助于石墨烯薄膜转移技术的研究,对整个二维材料器件的洁净制备也将有重要参考价值.     

双层石墨烯的化学气相沉积法制备及其光电器件

石墨烯是一种具有优异性质,在光电及能源领域具有巨大应用前景的二维材料.尽管单层石墨烯具有超高的迁移率,但是它的能带结构具有狄拉克锥(K点),即价带和导带并未有明显分离,所以在半导体器件方面的应用受到一定的限制.由双层石墨烯搭建而成的双门器件,在施加外加电场的情况下,它的带隙可以打开,并在一定范围内可调,这种性质赋予了双层石墨烯在半导体器件应用方面的前景.然而机械或者液相剥离石墨烯,在层数和大小方面可控性较差.如何通过化学气相沉积法可控制备双层石墨烯是目前研究的核心问题之一.本文主要综述了如何通过化学气相沉积法制备双层石墨烯和制备双层石墨烯器件的一系列工作,其中包括最新的研究进展,对生长机理的研究做了详细的介绍和讨论,并对该领域的发展进行了展望.     

纳米结构表面形貌成型机理及其对石墨烯拉曼光谱的影响

通过真空热蒸镀和高温退火法制备的金属纳米复结构SERS基底因其具有良好的灵敏度,稳定性和均匀性而广泛应用于各种检测领域。石墨烯具有优良的光学特性,化学惰性以及荧光猝灭效应,自被发现以后一直是光学微纳器件中的一大热门材料。石墨烯还可以有效分离探针分子与基底,优化拉曼光谱质量,因此广泛应用于SERS研究领域。同时石墨烯可以有效隔绝金属纳米结构与空气的直接接触防止金属纳米结构被氧化而失效,也可以催化氧化银的脱氧反应提升SERS基底的稳定性。在石墨烯/金属纳米复合结构SERS基底在制备过程中,受到金属膜的种类、厚度参数、气体种类、退火时间、温度和气压等因素的影响,制备的金属纳米结构形貌存在很大差异。石墨烯的拉曼光谱会因为应力和掺杂导致其拉曼特征峰出现不同程度的增强,移动以及展宽。（1）采用真空热蒸镀法和高温退火法制备石墨烯/银纳米复合结构SERS基底,建立了金属纳米颗粒成型机理的模型,从孔洞形成、孔洞生长、金属纳米岛形成三个阶段分析了金属纳米粒子的成型过程,实验沉积5,10,15以及20 nm的银薄膜,退火后银纳米结构的覆盖率分别为~35.1%,~24.4%,~30%以及~96.0%,在沉积银薄膜样品上使用湿法转移石墨烯,退火处理后发现石墨烯阻止了银纳米岛的形成过程;（2）理论分析了银薄膜厚度、石墨烯覆盖对复合结构的几何形貌、拉曼增强特性的影响,石墨烯由于其具有较高的杨氏模量和表面张力,可以有效抑制退火过程中银薄膜向纳米粒子转变的过程,从而实现对复合结构表面形貌的调控;（3）实验研究了银纳米粒结构形貌对石墨烯拉曼光谱的影响,并理论分析了蒸镀不同银薄膜厚度的样品对石墨烯的拉曼光谱增强,移动以及展宽影响的具体原因。     

Synthesis of Graphene and Its Applications: A Review

Graphene, one-atom-thick planar sheet of carbon atoms densely packed in a honeycomb crystal lattice, has grabbed appreciable attention due to its exceptional electronic and optoelectronic properties. The reported properties and applications of this two-dimensional form of carbon structure have opened up new opportunities for the future devices and systems. Although graphene is known as one of the best electronic materials, synthesizing single sheet of graphene has been less explored. This review article aims to present an overview of the advancement of research in graphene, in the area of synthesis, properties and applications, such as field emission, sensors, electronics, and energy. Wherever applicable, the limitations of present knowledgebase and future research directions have also been highlighted.     

Improvement of sensitivity of graphene photodetector by creating bandgap structure

Graphene has aroused large interest in optoelectronic applications because of its broad band absorption and ultrahigh electron mobility. However, the low absorption of 2.3% seriously limits its photoresponsivity and restricts the relevant applications. In this paper, a method to enhance the sensitivity of graphene photodetector is demonstrated by introducing electron trapping centers and creating a bandgap structure in graphene. The carrier lifetime obviously increases, and more carriers are collected by the electrodes. Compared with intrinsic graphene detector, the defective graphene photodetector possesses high photocurrent and low-driving-voltage, which gives rise to great potential applications in photodetector area.     

石墨烯：一种新的量子材料

石墨烯是一种仅由碳原子构成的二维材料.由于其独特的二维六角蜂窝状的晶格结构、载流子的狄拉克费米子行为及其他奇妙的物理特性,近些年来引起了人们的广泛关注.同时,它还展现出在电子、信息、能源等多个领域的巨大应用前景.曼彻斯特大学的安德烈.海姆（A.K.Geim）和康斯坦丁.诺沃肖洛夫（K.S.Novoselov）因其在石墨烯制备和研究方面的开创性工作获得了2010年的诺贝尔物理学奖.     

扭转双层石墨烯物理性质、制备方法及其应用的研究进展

石墨烯是一种准二维蜂窝网状结构新型纳米材料,石墨烯的层数和构型对其性能产生重要影响.固体中准粒子的量子状态由其本身的对称性质所决定,扭转双层石墨烯打破了对称性,引起了强烈的层间耦合作用,改变了扭转双层石墨烯的电子能带、声子色散、形成能垒等物性,产生了独特的性能,如可以连续调控带隙0-250 meV,光电效应的响应度相比于单层石墨烯提高了80倍,因此对扭转双层石墨烯功能化研究有重大意义.本文同时还论述了扭转双层石墨烯向类金刚石转变的理论与实验研究进展,发现扭转双层石墨烯呈现出具有类金刚石结构与性能特征.进一步阐述调控扭转双层石墨烯的扭转角度对其内在性能的影响,揭示这种新型纳米结构在原子层次的行为特征.最后介绍了如何调控制备扭转双层石墨,分析其调控机理,讨论了各种制备工艺的不足与发展趋势.因此本文从扭转双层石墨烯的输运性质、晶体结构转变、制备三个方面展开阐述,并对其在先进电子器件领域的潜在应用进行了展望.     

Introduction to graphene electronics – a new era of digital transistors and devices

The speed of silicon-based transistors has reached an impasse in the recent decade, primarily due to scaling techniques and the short-channel effect. Conversely, graphene (a revolutionary new material possessing an atomic thickness) has been shown to exhibit a promising value for electrical conductivity. Graphene would thus appear to alleviate some of the drawbacks associated with silicon-based transistors. It is for this reason why such a material is considered one of the most prominent candidates to replace silicon within nano-scale transistors. The major crux here, is that graphene is intrinsically gapless, and yet, transistors require a band-gap pertaining to a well-defined ON/OFF logical state. Therefore, exactly as to how one would create this band-gap in graphene allotropes is an intensive area of growing research. Existing methods include nanoribbons, bilayer and multi-layer structures, carbon nanotubes, as well as the usage of the graphene substrates. Graphene transistors can generally be classified according to two working principles. The first is that a single graphene layer, nanoribbon or carbon nanotube can act as a transistor channel, with current being transported along the horizontal axis. The second mechanism is regarded as tunnelling, whether this be band-to-band on a single graphene layer, or vertically between adjacent graphene layers. The high-frequency graphene amplifier is another talking point in recent research, since it does not require a clear ON/OFF state, as with logical electronics. This paper reviews both the physical properties and manufacturing methodologies of graphene, as well as graphene-based electronic devices, transistors, and high-frequency amplifiers from past to present studies. Finally, we provide possible perspectives with regards to future developments.     

Transfer-Free Graphene Growth on Dielectric Substrates: A Review of the Growth Mechanism

Ever since the more-than-decade-old discovery of application of mechanical exfoliation to obtain graphene, this 2-dimensional material was known for its soaring promise in various applications, owing to its excellent properties. Graphene, most popularly grown on metallic substrates by chemical vapour deposition, needs to be transferred onto dielectric substrates for multiple optical and electronic applications. During such complex and expensive transfer steps, defects are introduced into graphene, which deteriorates the quality and thus, properties of graphene. An alternative approach to surmount these problems is the elimination of the transfer process and to directly grow graphene on dielectric substrates, for future electronic and optical applications. This review presents a comprehensive and an up-to-date account of the development of synthesis methods, challenges and future directions for transfer-free graphene growth on dielectric substrates. Special emphasis is given on the fundamentals of growth mechanisms of various transfer-free graphene synthesis processes on dielectric materials.     

石墨烯纳米片电子结构和量子输运特性第一原理研究

用基于密度泛函理论的原子紧束缚方法计算研究单层石墨烯纳米圆片和纳米带的电子结构,并结合第一原理和非平衡函数法计算量子输运特性.通过电子能态和轨道密度分布研究纳米碳原子层的电子成键状态,结合电子透射谱、电导和电子势分布分析电子散射与输运机制.石墨烯纳米带和纳米圆片分别呈现金属和半导体的能带特征,片层边缘上电极化分别沿垂直和切向方向,电子电导出现较大的差异,来源于石墨烯纳米圆片边缘的突出碳原子环对电子的强散射.石墨烯纳米带的电子透射谱表现为近似台阶式变化并在费米能级处存在弹道电导峰,而石墨烯纳米圆片的电子能带和透射谱在费米能级处开口并且因量子限制作用呈现更加离散的多条高态密度窄能带和尖锐谱峰.     

Study of storage capacity in various carbon/graphene-based solid-state supercapacitors

Solid-state electrochemical double-layer capacitor (SEDLC) forms excellent energy storage device for high-power applications. They are highly reliable, with no electrolyte leaks, and can be packaged to suit various applications. The electrode material can be activated carbon to graphene. These can have a range of particle size, surface area, pore size and pore distribution for charge storage. The emphasis will be to optimize the graphene to carbon blend in the electrodes which would provide appreciable storage density of the SEDLC. We can use perfluorosulfonic acid polymer as the solid electrolyte in the SEDLC assembly. They have high ionic conductivity, good thermal stability, and mechanical strength. They also have excellent long-term chemical stability. Carbon is widely used for many practical applications, especially for the adsorption of ions and molecules, as it is possible to synthesize one-, two- or three-dimensional (1-, 2-, or 3-D) carbons. Some of the problems in activated carbon like varying micro or mesopores, poor ion mobility due to varying pore distribution, low electrical conductivity, can be overcome using graphene and blends of graphene with carbon of the right pore dimension and distribution. Graphene in various structural nomenclatures have been used by various groups for charge storage. Graphene nanoplates (GNP), with narrow mesopore distributions have been effectively used for SEDLCs. SEDLCs assembled with GNP and blends of GNP with Vulcan XC and solid polymer electrolyte like Nafion show exceptional performance. The cyclic voltammetric studies show that they support high scan rates with substantial smaller capacitance drop as we increase scan rates. Optimization of the electrode structure in terms of blend percentage, binder content and interface character in the frequency and time domain provides excellent insight into the double-layer interface.     

Large-area graphene synthesis and its application to interface-engineered field effect transistors

This article reviews recent advances in the large-area synthesis of graphene sheets and the applications of such sheets to graphene-based transistors. Graphene is potentially useful in a wide range of practical applications that could benefit from its exceptional electrical, optical, and mechanical properties. Tremendous effort has been devoted to overcoming several fundamental limitations of graphene, such as a zero band gap and a low direct current conductivity-to-optical conductivity ratio. The intrinsic properties of graphene depend on the synthetic and transfer route, and this dependence has been intensively investigated. Several representative reports describing the application of graphene as a channel and electrode material for use in flexible transparent transistor devices are discussed. A fresh perspective on the optimization of graphene as a 2D framework for crystalline organic semiconductor growth is introduced, and its effects on transistor performance are discussed. This critical review provides insights and a new perspective on the development of high-quality large-area graphene and the optimization of graphene-based transistors.