双层转角石墨烯的结构和电学性质

石墨烯是第一个被发现的层状二维材料,它的电学性质对层数和层间的堆垛方式有很强的 依赖性。而层间的转角可以被看作是调控石墨烯电学性质的又一个可控的自由度。本文主要综述 双层转角石墨烯的基本结构与性质,重点讲述转角对双层石墨烯电学性质的影响。我们将从理论 与实验结合的角度出发,介绍双层转角石墨烯中Dirac 费米子的新奇物理特性,重点阐述如何通 过转角来调控石墨烯的电学性质。最后我们对双层转角石墨烯的研究现状进行总结和展望。     

氢化与氟化五边形石墨烯双层电子性能调控的第一性原理研究

基于密度泛函理论的第一性原理计算方法，我们研究了氢化、氟化及氢氟化五边形石墨烯双层对其电子性能的调控.计算结果表明，氢化和氟化的五边形石墨烯双层可分别在价带顶及导带底形成局域的电子态而显著降低带隙.基于这一特性，我们进一步研究氢氟化的五边形石墨烯双层结构对电子能带的影响，并且发现通过调控氢氟化覆盖度能够有效调节带隙，进而实现五边形石墨烯双层从半导体到金属态的转变.     

退火温度调控多层折叠石墨烯力学性能的分子动力学模拟

退火是石墨烯宏观组装材料常用的制备工艺之一,广泛用于其性能的调控.在石墨烯基材料中,石墨烯片层由于其自身的二维特性通常在微纳米尺度下呈现出多层折叠的结构.然而这种微观结构对材料力学性能退火调控的影响仍未得到充分的了解.为了阐明多层折叠石墨烯力学性能与退火温度间的调控关系,基于分子动力学模拟研究了材料弹性模量、拉伸强度、极限应变以及断裂韧性等关键力学性能参数随退火温度的变化规律,进而结合观察微观结构的演化过程揭示了性能调控现象的物理机制.结果表明:更高的退火温度将增强多层折叠石墨烯的弹性模量与拉伸强度,但同时削弱了其极限应变,并且其断裂韧性能够在一定退火温度范围内实现强化.研究发现,以上力学性能的调控作用归因于更高的退火温度将造成更加密集的层间交联,从而增强了折叠区域层间界面的相互作用,并限制了折叠结构的形态展开,致使结构破坏模式发生转变.     

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.     

扭转形变对石墨烯吸附O原子电学和光学性质影响的电子理论研究

基于密度泛函理论的第一性原理方法研究了扭转形变对石墨烯吸附O体系结构稳定性、电子结构和光学性质,包括吸附能、带隙、吸收系数及反射率的影响.研究发现,吸附O原子后,距O原子最近的C原子被拔起,导致石墨烯平面发生扭曲.吸附能计算表明,扭转形变使石墨烯吸附O原子体系结构稳定性下降,而扭转程度对结构稳定性影响微弱.能带结构分析发现,O原子的吸附使石墨烯由金属变成半导体,扭转形变发生时,可实现其从半导体到金属、再到半导体特性的转变.扭转角为12°的吸附O原子体系为间接带隙,而其他出现带隙的体系均为直接带隙.与本征石墨烯受扭体系相比,吸附O原子体系的电子结构对扭转形变的敏感度降低,其中扭转角在10°—16°范围内变化时,带隙始终稳定在0.11 eV附近,即在此扭转角范围内始终对应窄带隙半导体.在光学性能中,受扭转形变的吸附体系吸收系数和反射率峰值较未受扭转形变石墨烯吸附O原子体系均减弱,且随着扭转程度的加剧,均出现红移到蓝移的转变.     

基于温度的亚稳态氧化石墨烯性能

单片层氧化石墨烯由于其优异的物理化学性能,在离子和分子筛选、水脱盐和净化、气体分离、生物传感、质子导体、锂电池和超级电容等领域有巨大的潜在应用.然而普遍采用的Hummers法等化学、物理方法制备的氧化石墨烯是一种亚稳态材料.其最终形态的物理化学性能的转变与调控至关重要,亟需系统研究.本文采用恒温处理方法对氧化石墨烯亚稳态的转变进行调控,利用X射线光电子吸收谱、傅里叶红外吸收谱、扫描电子显微镜等方法检测氧化石墨烯含氧基团的含量、类型和形貌与温度的变化关系,并利用Zeta电位、紫外吸收谱、拉力测试分析温度对氧化石墨烯在转变过程中的溶液悬浮稳定性、光子能带、拉伸强度等性能的影响.所得定量测试结果发现,氧化石墨烯亚稳态的转变过程中存在环氧减少、羟基增加,以及整体含氧量下降的现象,而在此过程中氧化石墨烯的单片层形貌并无明显变化.但是这种结构的转变使得悬浮液黏稠度和亲水性大幅度增强,能带减小和拉伸强度增强效应明显.而当转变过程足够长时,氧化石墨烯的亲水性转而下降,并出现沉淀现象,表明羟基之间进一步发生了脱水转变.另外,本文还分析了恒温处理的时间、悬浮液的浓度对这种转变过程的影响.相关研究结果有利于理解亚稳态氧化石墨烯悬浮液随温度变化的性能转变,对氧化石墨烯具体应用有一定参考价值.     

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.     

B/N掺杂对双层石墨烯电子特性影响的第一性原理研究

利用平面波超软赝势方法研究了B/N原子单掺杂和共掺杂对双层石墨烯电子特性的影响.对掺杂双层石墨烯进行结构优化,并计算了能带结构、态密度、分波态密度等.分析表明,层间范德瓦尔斯相互作用对双层石墨烯的电子特性有比较明显的影响;B/N原子单掺杂分别对应p型和n型掺杂,会使掺杂片层的能带平移,使得体系能带结构产生较大分裂;双层掺杂的石墨烯能带结构与掺杂原子的相对位置和距离有关,对电子特性有明显的调控作用.其中特别有意义的是,B/N双层共掺杂在不同位置情况下会得到金属性或禁带宽度约为0.3 eV的半导体能带.     

石墨烯谐振式力学量传感器研究进展

传统谐振式传感器的谐振敏感元件大多采用金属、石英晶体、硅等材料制成,但随着谐振式传感器朝着小型化、微型化、实用化的趋势发展,不但要求新型谐振子材料可进行微纳加工,还对其灵敏度和精度提出了更高的要求.石墨烯这种新型二维纳米材料,因具有出色的力学、电学、光学、热学特性,在谐振传感领域有着巨大的应用潜力和研究价值,因此基于石墨烯材料的力学量传感器有望在小型化、高性能和环境适应性等多方面超越硅基力学量传感器.本文针对石墨烯谐振式力学量传感器,介绍了石墨烯材料的基本性质、制备与转移方法,阐述了谐振式传感器的工作原理与应用特点,进而分析了关于石墨烯谐振特性优化与谐振器制备的理论与实验研究;在此基础上,重点总结了石墨烯谐振器在压力、加速度、质量等传感器领域的研究进展,梳理了石墨烯谐振式力学量传感器在薄膜转移、结构制备与激振/拾振等方面的技术问题,同时也明确了石墨烯在谐振传感领域的研究价值和发展潜力.     

石墨烯射频器件研究进展

石墨烯因具有优良的电学特性,在半导体行业中受到广泛关注,特别因其具有超薄的结构和极高的载流子迁移率,为解决短沟道效应提供了可能,并且在高速电子领域具有应用前景.近年来,使用石墨烯作为沟道材料制备射频晶体管及射频电路是发挥石墨烯材料优势的一个重要研究方向.制造高性能的射频器件,首先要制备出高性能的石墨烯材料.在金属衬底上沉积均匀的单层石墨烯材料或者在绝缘衬底上外延生长单层、双层石墨烯材料都是获得高质量石墨烯材料的常用方法.器件结构及工艺流程的设计也是提升晶体管射频性能的重要因素,多指栅结构、T型栅结构、埋栅结构以及自对准工艺的发展能够有效改善石墨烯射频晶体管的截止频率及最大振荡频率.石墨烯晶体管独特的电学特性使得其除了可以构造与其他半导体材料电路相似的射频电路结构,还可以构造出功能完整并且结构更加简单的新型射频电路结构.     

Probing interlayer coupling in twisted single‐crystal bilayer graphene by Raman spectroscopy

Twisted bilayer graphene, in which interlayer interaction plays a critical role in this coupled system, is characterized for its angle‐dependent electronic and optical properties. Here, we present a systematic Raman study of single‐crystal twisted bilayer graphene grains, with the spectra of each bilayer graphene precisely correlated to its twist angle using combined transmission electron microscopic technique. Van Hove singularities develop as a result of band rehybridization at the crossing Dirac cones of the two layers, giving rise to a critical twist angle that determines the energy separation between the saddle points in the band structure and the resonance Raman spectra accordingly. The 2D mode becomes sensitive to the twist angle, showing the angle‐dependent position, peak width, and intensity. Our results interpreted in the framework of angle‐dependent double resonance scattering provide an important experimental perspective in understanding the coupled bilayer graphene system. Copyright © 2014 John Wiley & Sons, Ltd.     

旋转双层石墨烯的电子结构

本文将第一性原理和紧束缚方法结合起来, 研究了层间不同旋转角度对双层石墨烯的电子能带结构和态密度的影响. 分析发现, 旋转双层石墨烯具有线性的电子能量色散关系, 但其费米速度随着旋转角度的减小而降低. 进一步研究其电子能带结构发现, 不同旋转角度的双层石墨烯在M点可能会出现大小不同的的带隙, 而这些能隙会增强双层石墨烯的拉曼模强度, 并由拉曼光谱实验所证实. 通过对比双层石墨烯的晶体结构和电子态密度, 发现M点处带隙来自于晶体结构中的“类AB堆垛区”. 关键词： 旋转双层石墨烯 第一性原理 紧束缚 电子结构     

垂直电场下扭转双层石墨烯光学吸收性质的理论研究

层间扭转角度是对石墨烯物理性质宽波段可调谐的一个新参量.本文采用2°<θ<15°扭转角度下的连续近似模型,获得了不同扭转角度双层石墨烯分别在有、无电场下的能带结构,通过电子-光子相互作用跃迁速率,计算模拟了范霍夫奇点附近电子带内跃迁和带间跃迁所引起的光学吸收谱.结果表明,在无外加电场时,带间跃迁吸收峰的位置随着扭转角度的增大而发生从红外到可见光波段的蓝移,且吸收系数增大,带内跃迁的光学吸收系数相对于带间跃迁高出2个数量级;而存在外加电场时,两个范霍夫奇点在波矢空间的位置发生偏移,带间跃迁吸收峰发生分裂,且两个分裂的吸收峰位置随着电场强度的不断增大而反向行进.上述研究结果对石墨烯材料在光电器件方面的应用有一定指导作用.     

Theoretical study of broadband near-field optical spectrum of twisted bilayer graphene

We theoretically study the broadband near-field optical spectrum of twisted bilayer graphene (TBG) at various twist angles near the magic angle using two different models. The spectrum at low Fermi energy is characterized by a series of peaks that are almost at the same energies as the peaks in the far-field optical conductivity of TBG. When the Fermi energy is near a van Hove singularity, an additional strong peak appears at finite energy in the near-field spectrum, which has no counterpart in the optical conductivity. Based on a detailed calculation of the plasmon dispersion, we show that these spectroscopic features are associated with interband and intraband plasmons, which can provide critical information about the local band structure and plasmonic excitations in TBG. The near-field peaks evolve systematically with the twist angle, so they can serve as fingerprints for identifying the spatial dependent twist angle in TBG samples. Our findings pave the way for future experimental studies of the novel optical properties of TBG in the nanoscale.     

Graphite,Graphene, and the Flat Band Superconductivity

Superconductivity has been observed in bilayer graphene [1, 2]. The main factor that determines the mechanism of the formation of this superconductivity is the “magic angle” of twist of two graphene layers, at which the electronic band structure becomes nearly flat. The specific role played by twist and by the band flattening has been earlier suggested for explanations of the signatures of room-temperature superconductivity observed in the highly oriented pyrolytic graphite (HOPG), when the quasi two-dimensional interfaces between the twisted domains are present. The interface contains the periodic array of misfit dislocations (analogs of the boundaries of the unit cell of the Moiré superlattice in bilayer graphene), which provide the possible source of the flat band. This demonstrates that it is high time for combination of the theoretical and experimental efforts in order to reach the reproducible room-temperature superconductivity in graphite or in similar real or artificial materials.     

Single-layer behavior and its breakdown in twisted graphene layers

We report high magnetic field scanning tunneling microscopy and Landau level spectroscopy of twisted graphene layers grown by chemical vapor deposition. For twist angles exceeding ~3° the low energy carriers exhibit Landau level spectra characteristic of massless Dirac fermions. Above 20° the layers effectively decouple and the electronic properties are indistinguishable from those in single-layer graphene, while for smaller angles we observe a slowdown of the carrier velocity which is strongly angle dependent. At the smallest angles the spectra are dominated by twist-induced van Hove singularities and the Dirac fermions eventually become localized. An unexpected electron-hole asymmetry is observed which is substantially larger than the asymmetry in either single or untwisted bilayer graphene.     

Tunable bandgaps and flat bands in twisted bilayer biphenylene carbon

Owing to the interaction between the layers, the twisted bilayer two-dimensional(2 D) materials exhibit numerous unique optical and electronic properties different from the monolayer counterpart, and have attracted tremendous interests in current physical research community. By means of first-principles and tight-binding model calculations, the electronic properties of twisted bilayer biphenylene carbon(BPC) are systematically investigated in this paper. The results indicate that the effect of twist will not only leads to a phase transition from semiconductor to metal, but also an adjustable band gap in BPC(0 me V to 120 me V depending on the twist angle). Moreover, unlike the twisted bilayer graphene(TBG), the flat bands in twisted BPC are no longer restricted by "magic angles", i.e., abnormal flat bands could be appeared as well at several specific large angles in addition to the small angles. The charge density of these flat bands possesses different local modes, indicating that they might be derived from different stacked modes and host different properties. The exotic physical properties presented in this work foreshow twisted BPC a promising material for the application of terahertz and infrared photodetectors and the exploration of strong correlation.     

Optical conductivity of twisted bilayer graphene near the magic angle

We theoretically study the band structure and optical conductivity of twisted bilayer graphene(TBG) near the magic angle considering the effects of lattice relaxation. We show that the optical conductivity spectrum is characterized by a series of peaks associated with the van Hove singularities in the band structure, and the peak energies evolve systematically with the twist angle. Lattice relaxation effects in TBG modify its band structure, especially the flat bands, which leads to significant shifts of the peaks in the optical conductivity. These results demonstrate that spectroscopic features in the optical conductivity can serve as fingerprints for exploring the band structure, band gap, and lattice relaxation in magic-angle TBG as well as identifying its rotation angle.     

Faraday rotations,ellipticity, and circular dichroism in magneto-optical spectrum of moiré superlattices

We study the magneto-optical conductivity of a number of van der Waals heterostructures, namely, twisted bilayer graphene, AB-AB and AB-BA stacked twisted double bilayer graphene and monolayer graphene and AB-stacked bilayer graphene on hexagonal boron nitride. As the magnetic field increases, the absorption spectrum exhibits a self-similar recursive pattern reflecting the fractal nature of the energy spectrum. Whilst twisted bilayer graphene displays only weak circular dichroism, the other four structures display strong circular dichroism with monolayer graphene and AB-stacked bilayer graphene on hexagonal boron nitride being particularly pronounced owing to strong inversion symmetry breaking properties of the hexagonal boron nitride layer. As the left and right circularly polarized light interact with these structures differently, plane-polarized incident light undergoes a Faraday rotation and gains an ellipticity when transmitted. The size of the respective angles is on the order of a degree.     

Raman spectroscopy study of twisted tetralayer graphene

We present a systematic Raman study of twisted tetralayer graphene (t(2 + 2)LG), under excitation of two laser lines. In t(2 + 2)LG samples, top Bernal stacked bilayer graphene (2LG stands for Bernal‐stacked bilayer graphene) twists different angle relative to bottom 2LG. It is found that 2D and 2D′ peaks of t(2 + 2)LG show positive wavenumber shift relative to those of 2LG. We propose a simplified electronic band structure for t(2 + 2)LG; interlayer interaction‐induced changing in electronic band structure can be used to understand the aforementioned spectral features. The electronic structures of t(2 + 2)LG samples are then probed from resonant Raman studies of 2D and 2D′ peaks using two laser lines; electronic dispersions in t(2 + 2)LG samples are given. Our study facilitates understanding of twist angle‐dependent electronic properties of tetralayer graphene superlattice. Copyright © 2016 John Wiley & Sons, Ltd.