双空位掺杂氟化石墨烯的电子性质和磁性

基于密度泛函理论,计算了外来原子X(Al,P,Ga,As,Si)双空位替代掺杂氟化石墨烯的电子特性和磁性.通过对计算结果分析发现,与石墨烯的双空位掺杂类似,氟化石墨烯的双空位掺杂也是一种较为理想的掺杂方式.通过不同原子掺杂,氟化石墨烯的电子性质与磁性均发生很大变化:Al和Ga掺杂使氟化石墨烯由半导体变为金属,并且具有磁性;P和A8掺杂使氟化石墨烯变为自旋半导体;Si掺杂氟化石墨烯仍是半导体,只改变带隙且没有磁性.进一步讨论磁性产生机制获得了掺杂原子浓度与磁性的关系,并且发现不同掺杂情况的磁性是由不同原子的不同轨道电子引起的.双空位掺杂不仅丰富了氟化石墨烯的掺杂方式,其不同电磁特性也使此类掺杂结构在未来的电子器件中具有潜在应用.     

Electronic and magnetic properties of silicon adsorption on graphene

Graphene has proved to be extremely sensitive to its surrounding environment, such as the supporting substrate and guest adatoms. In this work, the structural stabilities, and electronic and magnetic properties of graphene with low-coverage adsorption of Si atoms and dimers are studied using a first-principles method. Our results show that graphene with Si adatoms is metallic and magnetic with a tiny structural change in the graphene, while graphene with Si addimers is semi-metallic and nonmagnetic with a visible deformation of the graphene. The spin-polarized density of states is calculated in order to identify the electronic origin of the magnetic and nonmagnetic states. The present results suggest that the electronic and magnetic behaviors of graphene can be tuned simply via Si adsorptions.     

过渡金属掺杂的扶手椅型氮化硼纳米带的磁电子学特性及力-磁耦合效应

基于密度泛函理论的第一性原理计算方法,研究了多种过渡金属(TM)掺杂扶手椅型氮化硼纳米带(ABNNR-TM)的结构特点、磁电子特性及力-磁耦合效应.计算的结合能及分子动力学模拟表明ABNNRTM的几何结构是较稳定的,同时发现对于不同的TM掺杂,ABNNRs能表现出丰富的磁电子学特性,可以是双极化磁性半导体、一般磁性半导体、无磁半导体或无磁金属.双极化磁性半导体是一种重要的稀磁半导体材料,它在巨磁阻器件和自旋整流器件上有重要的应用.此外,力-磁偶合效应研究表明:ABNNR-TM的磁电子学特性对应力作用十分敏感,能实现无磁金属、无磁半导体、磁金属、磁半导体、双极化磁性半导体、半金属等之间的相变.特别是呈现的宽带隙半金属对于发展自旋电子器件有重要意义.这些结果表明:可以通过力学方法来调控ABNNR-TM的磁电子学特性.     

Ab initio study of graphene on SiC

Employing density-functional calculations we study single and double graphene layers on Si- and C-terminated 1x1-6H-SiC surfaces. We show that, in contrast with earlier assumptions, the first carbon layer is covalently bonded to the substrate and cannot be responsible for the graphene-type electronic spectrum observed experimentally. The characteristic spectrum of freestanding graphene appears with the second carbon layer, which exhibits a weak van der Waals bonding to the underlying structure. For Si-terminated substrate, the interface is metallic, whereas on C face it is semiconducting or semimetallic for single or double graphene coverage, respectively.     

Near-field infrared response of graphene on copper substrate

The electronic properties of graphene are very sensitive to its dielectric environment. The coupling to a metal substrate can give rise to many novel quantum effects in graphene, such as band renormalization and plasmons with unusual properties, which are of high technological interest. Infrared nanoimaging are very suitable for exploring these effects considering their energy and length scales. Here, we report near-field infrared nanoimaging studies of graphene on copper synthesized by chemical vapor deposition. Remarkably, our measurements reveal three different types of near-field optical responses of graphene, which are very distinct from the near-field edge fringes observed in the substrate. These results can be understood from the modification of optical conductivity of graphene due to its coupling with the substrate. Our work provides a framework for identifying the near-field response of graphene in graphene/metal systems and paves the way for studying their novel physics and potential applications.     

The importance of defects for carbon nanoribbon based electronics

The utilization of graphene nanoribbons for next generation nanoelectronics is commonly expected to depend on the controlled synthesis that yields a low density of defects. Edge roughness and vacancies have been shown to have a large impact on the performance of graphene nanoribbon transistors. In contrast, we show how certain defects can be used to enhance the electronic and magnetic properties of graphene nanoribbons. We explore the properties of hybrid graphene nanoribbons with armchair and zigzag features joined by an array of pentagon–heptagon structural defects. The graphene nanoribbons display an increased density of states at the Fermi level, and half metallicity in absence of external fields. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

First-principle study of magnetism induced by vacancies in graphene

Spin-polarized density functional theory has been used to study the effects of vacancy defects on the magnetic properties of graphene. Structural optimization shows that introducing a carbon vacancy cluster into a graphene sheet changes the spatial distribution of the neighbor atoms, particularly those located around the vacancy. From spin-polarized DOS and LPDOS calculations, we find that only vacancies containing unpaired electrons show magnetism. These results lead us to formulate a relation between the vacancy-induced magnetic moment and the size and shape of the vacancy clusters in graphene sheet.     

Electronic states on the surface of graphite

Graphite consists of graphene layers in an AB (Bernal) stacking arrangement. The introduction of defects can reduce the coupling between the top graphene layers and the bulk crystal producing new electronic states that reflect the degree of coupling. We employ low temperature high magnetic field scanning tunneling microscopy (STM) and spectroscopy (STS) to access these states and study their evolution with the degree of coupling. STS in magnetic field directly probes the dimensionality of electronic states. Thus two-dimensional states produce a discrete series of Landau levels while three-dimensional states form Landau bands providing a clear distinction between completely decoupled top layers and ones that are coupled to the substrate. We show that the completely decoupled layers are characterized by a single sequence of Landau levels with square-root dependence on field and level index indicative of massless Dirac fermions. In contrast weakly coupled bilayers produce special sequences reflecting the degree of coupling, and multilayers produce sequences reflecting the coexistence of massless and massive Dirac fermions. In addition we show that the graphite surface is soft and that an STM tip can be quite invasive when brought too close to the surface and that there is a characteristic tip-sample distance beyond which the effect of sample-tip interaction is negligible.     

Intercalation of germanium oxide beneath large-area and high-quality epitaxial graphene on Ir(111) substrate

Epitaxial growth on transition metal surfaces is an effective way to prepare large-area and high-quality graphene.However,the strong interaction between graphene and metal substrates suppresses the intrinsic excellent properties of graphene and the conductive metal substrates also hinder its applications in electronics.Here we demonstrate the decoupling of graphene from metal substrates by germanium oxide intercalation.Germanium is firstly intercalated into the interface between graphene and Ir(111) substrate.Then oxygen is subsequently intercalated,leading to the formation of a GeO_x layer,which is confirmed by x-ray photoelectron spectroscopy.Low-energy electron diffraction and scanning tunneling microscopy studies show intact carbon lattice of graphene after the GeO_x intercalation.Raman characterizations reveal that the intercalated layer effectively decouples graphene from the Ir substrate.The transport measurements demonstrate that the GeO_x layer can act as a tunneling barrier in the fabricated large-area high-quality vertical graphene/GeO_x/Ir heterostructure.     

Investigation of the transport mechanism in graphene-induced metal-oxide-semiconductor capacitors (MOSCAP)

Graphene is the most promising contender for the future generation of electronic and photonic devices, based on its extraordinary properties. The effect of the metal interface with graphene, however, which completely alters its properties, is of great importance. The effects of the substrate supporting the graphene matrix, the graphene/metal contact resistance and the overall metal oxide semiconductor capacitors (MOSCAP) for possible CMOS circuitry have been thoroughly investigated in this research work. We have fabricated a structure with pertinent deposition techniques and performed a detailed electrical analysis to obtain the transport characteristics. Nickel (Ni) is chosen as the transition metal which makes the chemisorption bonding with graphene while qualifying as an interface. We present an analysis of the metal contacts, a study of the metal resistivity at various planes, a study of the graphene (carbon) atom's resistance at the atomistic scale, the graphene based MOSCAP leakages, the necessary charge accumulation at the metal–graphene interface and the charge inversion just beneath the oxide layer.     

Effect of strain on geometric and electronic structures of graphene on Ru(0001) surface

The atomic and electronic structures of a graphene monolayer on a Ru(0001) surface under compressive strain are investigated by using first-principles calculations. Three models of graphene monolayers with different carbon periodicities due to the lattice mismatch are proposed in the presence and the absence of the Ru(0001) substrate separately. Considering the strain induced by the lattice mismatch, we optimize the atomic structures and investigate the electronic properties of the graphene. Our calculation results show that the graphene layers turn into periodic corrugations and there exist strong chemical bonds in the interface between the graphene N×N superlattice and the substrate. The strain does not induce significant changes in electronic structure. Furthermore, the results calculated in the local density approximation (LDA) are compared with those obtained in the generalized gradient approximation (GGA), showing that the LDA results are more reasonable than the GGA results when only two substrate layers are used in calculation.     

Defective graphene and nanoribbons: electronic,magnetic and structural properties

We make use of first-principles calculations, based on the density functional theory(DFT), to investigate the alterations at the structural, energetic, electronic andmagnetic properties of graphene and zigzag graphene nanoribbons (ZGNRs) due to theinclusion of different types of line and punctual defects. For the graphene it is foundthat the inclusion of defects breaks the translational symmetry of the crystal withdrastic changes at its electronic structure, going from semimetallic to semiconductor andmetallic. Regarding the magnetic properties, no magnetization is observed for thedefective graphene. We also show that the inclusion of defects at ZGNRs is a good way tocreate and control pronounced peaks at the Fermi level. Furthermore, defective ZGNRsstructures show magnetic moment by supercell up to 2.0μ_B. For the non defectiveZGNRs is observed a switch of the magnetic coupling between opposite ribbon edges from theantiferromagnetic to the ferrimagnetic and ferromagnetic configurations.     

Electronic properties and interfacial coupling in Pb islands on single-crystalline graphene

Introducing metal thin films on two-dimensional (2D) material may present a system to possess exotic properties due to reduced dimensionality and interfacial effects. We deposit Pb islands on single-crystalline graphene on a Ge(110) substrate and studied the nano- and atomic-scale structures and low-energy electronic excitations with scanning tunneling microscopy/spectroscopy (STM/STS). Robust quantum well states (QWSs) are observed in Pb(111) islands and their oscillation with film thickness reveals the isolation of free electrons in Pb from the graphene substrate. The spectroscopic characteristics of QWSs are consistent with the band structure of a free-standing Pb(111) film. The weak interface coupling is further evidenced by the absence of superconductivity in graphene in close proximity to the superconducting Pb islands. Accordingly, the Pb(111) islands on graphene/Ge(110) are free-standing in nature, showing very weak electronic coupling to the substrate.     

A cosmological model for corrugated graphene sheets

Defects play a key role in the electronic structure of graphene layers flat or curved. Topological defects in which an hexagon is replaced by an n-sided polygon generate long range interactions that make them different from vacancies or other potential defects. In this work we review previous models for topological defects in graphene. A formalism is proposed to study the electronic and transport properties of graphene sheets with corrugations as the one recently synthesized. The formalism is based on coupling the Dirac equation that models the low energy electronic excitations of clean flat graphene samples to a curved space. A cosmic string analogy allows to treat an arbitrary number of topological defects located at arbitrary positions on the graphene plane. The usual defects that will always be present in any graphene sample as pentagon–heptagon pairs and Stone-Wales defects are studied as an example. The local density of states around the defects acquires characteristic modulations that could be observed in scanning tunnel and transmission electron microscopy.     

Rashba coupling induced spin susceptibility and magnetic phase transition of conduction electrons in monolayer graphene

Isolated graphene cannot be obtained by the known synthesis processes and it should be placed on a substrate. This substrate introduces a new type of spin–orbit interaction known as Rashba coupling. Using the Kubo formalism, the magnetic properties of the system in the linear regime have been investigated. Mainly the effect of non-magnetic substrate on the spin susceptibility is calculated. Results show that the Rashba coupling has a central role in the magnetic response function of the system and it is really remarkable since this type of spin orbit coupling can be effectively controlled by an external gate voltage. Most importantly, it was shown that, in the presence of the Rashba interaction a magnetic phase transition could be observed. This magnetic phase corresponds to a magnetic order of conduction electrons that takes place at some special frequencies of external magnetic field.     

Graphene films grown on sapphire substrates via solid source molecular beam epitaxy

A method for growing graphene on a sapphire substrate by depositing an SiC buffer layer and then annealing at high temperature in solid source molecular beam epitaxy (SSMBE) equipment was presented. The structural and electronic properties of the samples were characterized by reflection high energy diffraction (RHEED), X-ray diffraction Φ scans, Raman spectroscopy, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results of the RHEED and Φ scan, as well as the Raman spectra, showed that an epitaxial hexagonal α-SiC layer was grown on the sapphire substrate. The results of the Raman and NEXAFS spectra revealed that the graphene films with the AB Bernal stacking structure were formed on the sapphire substrate after annealing. The layer number of the graphene was between four and five, and the thickness of the unreacted SiC layer was about 1--1.5 nm.     

Silicene: compelling experimental evidence for graphenelike two-dimensional silicon

Because of its unique physical properties, graphene, a 2D honeycomb arrangement of carbon atoms, has attracted tremendous attention. Silicene, the graphene equivalent for silicon, could follow this trend, opening new perspectives for applications, especially due to its compatibility with Si-based electronics. Silicene has been theoretically predicted as a buckled honeycomb arrangement of Si atoms and having an electronic dispersion resembling that of relativistic Dirac fermions. Here we provide compelling evidence, from both structural and electronic properties, for the synthesis of epitaxial silicene sheets on a silver (111) substrate, through the combination of scanning tunneling microscopy and angular-resolved photoemission spectroscopy in conjunction with calculations based on density functional theory.     

金属衬底上高质量大面积石墨烯的插层及其机制

石墨烯作为一种新型二维材料,因其优异的性质,在科学和应用领域具有非常重要的意义.而其超高的载流子迁移率、室温量子霍尔效应等,使其在信息器件领域备受关注.如何获得高质量并且与当代硅基工艺兼容的石墨烯功能器件,是未来将石墨烯应用于电子学领域的关键.近年来,研究人员发展了一种在外延石墨烯和金属衬底之间实现硅插层的技术,将金属表面外延石墨烯高质量、大面积的特点与当代硅基工艺结合起来,实现了无需转移且无损地将高质量石墨烯置于半导体之上.通过系统的实验研究并结合理论计算,揭示了插层过程包含四个主要阶段:诱导产生缺陷、异质原子插层、石墨烯自我修复和异质原子扩散成膜,并证实了这一插层机制的普适性.拉曼和角分辨光电子能谱实验结果表明,插层后的石墨烯恢复了本征特性,接近自由状态.此外,还实现了多种单质元素的插层.不同种类的原子形成不同的插层结构,从而构成了多种石墨烯/插层异质结.这为调控石墨烯的性质提供了实验基础,也展现了该插层技术的普适性.     

Effect of edge vacancies on localized states in a semi-infinite zigzag graphene sheet

The effect of vacancies on the robustness of zero-energy edge electronic states in zigzag-type graphene layer is studied at different concentrations and distributions of defects. All calculations are performed by using the Green’s function method and the tight-binding approximation. It is found that the arrangement of defects plays a crucial role in the destruction of the edge states. We have specified a critical distance between edge vacancies when their mutual influence becomes significant and affects markedly the density of electronic states at graphene edge.     

Competition between ferromagnetic and anti-ferromagnetic couplings in Co doped ZnO with vacancies and Ga co-dopants

Spin-polarized first-principles electronic structure and total energy calculations have been performed to better understand the magnetic properties of Co doped ZnO (ZnO:Co) with vacancies and Ga co-dopants. The paramagnetic state of ZnO:Co, in which Co ions lose their magnetic moments, has been found to be unstable. The total energy results show that acceptor-like Zn vacancies and donor-like Ga co-dopants render the anti-ferromagnetic (AFM) and ferromagnetic (FM) states to be more favorable, respectively. With O vacancies, ZnO:Co has been found to be in the weak FM state. These magnetic properties can be understood by the calculated O- and Zn-vacancies and Ga co-dopant induced changes of the electronic structure, which suggest that AFM and FM Co-Co couplings are mediated by O 2p-Co majority (↑)-spin 3d hybridized states in the valence band of ZnO and O-vacancy-derived p states or Ga sp states in the ZnO band gap, respectively. For ZnO:Co with Zn vacancies (Ga co-dopants) the AFM (FM) coupling outweighs the FM (AFM) coupling and results in the AFM (FM) state, while for ZnO:Co with O vacancies, both the FM and AFM couplings are enhanced by similar degrees and result in the weak FM state. This study reveals a competition between FM and AFM couplings in ZnO:Co with vacancies and Ga co-dopants, the detailed balancing between which determines the magnetic properties of these materials.