Structural, electronic and magnetic properties of manganese doping in the upper layer of bilayer graphene

First-principles spin-polarized calculations have been conducted to investigate the structural, electronic and magnetic properties of 3d transition metal Mn doping into two typical sites in the upper layer of bilayer graphene with the AB Bernal structure. One of the doping sites is above the center of a carbon hexagon of the lower graphene layer (called the H site) and the other is directly on top of a carbon atom of the lower graphene layer (called the T site). We found that Mn doping enlarges the interlayer distance in bilayer graphene. Charge density distribution indicates that the region between the upper and lower graphene layer has apparent covalent-bonding characters due to the Mn doping. In the spin-polarized band structure of H?site doping, the π and π(*) bands separate from each other at the Dirac point both in majority spin and minority spin. In the band structure of T site doping, the Fermi level is located above the Dirac point and moves to the conduction bands in majority spin and minority spin, making the bilayer graphene n doped. A high spin polarization of 95% is achieved due to the H site doping. The local moment of Mn for H and T site doping is reduced to 1.76?μ(B) and 1.88?μ(B), respectively, which are smaller than the value (5?μ(B)) in the free state.     

Effects of Pb Intercalation on the Structural and Electronic Properties of Epitaxial Graphene on SiC

The effects of Pb intercalation on the structural and electronic properties of epitaxial single‐layer graphene grown on SiC(0001) substrate are investigated using scanning tunneling microscopy (STM), noncontact atomic force microscopy, Kelvin probe force microscopy (KPFM), X‐ray photoelectron spectroscopy, and angle‐resolved photoemission spectroscopy (ARPES) methods. The STM results show the formation of an ordered moiré superstructure pattern induced by Pb atom intercalation underneath the graphene layer. ARPES measurements reveal the presence of two additional linearly dispersing π‐bands, providing evidence for the decoupling of the buffer layer from the underlying SiC substrate. Upon Pb intercalation, the Si 2p core level spectra show a signature for the existence of Pb? Si chemical bonds at the interface region, as manifested in a shift of 1.2 eV of the bulk SiC component toward lower binding energies. The Pb intercalation gives rise to hole‐doping of graphene and results in a shift of the Dirac point energy by about 0.1 eV above the Fermi level, as revealed by the ARPES measurements. The KPFM experiments have shown that decoupling of the graphene layer by Pb intercalation is accompanied by a work function increase. The observed increase in the work function is attributed to the suppression of the electron transfer from the SiC substrate to the graphene layer. The Pb intercalated structure is found to be stable in ambient conditions and at high temperatures up to 1250 °C. These results demonstrate that the construction of a graphene‐capped Pb/SiC system offers a possibility of tuning the graphene electronic properties and exploring intriguing physical properties such as superconductivity and spintronics.     

Light non-metallic atom (B, N, O and F)-doped graphene: a first-principles study

First-principles calculations are performed to study the geometry, electronic structure and magnetic properties of light non-metallic atom-doped graphene (B, N, O and F). The planar structure and the quasi-linear energy dispersion near the Dirac point remain through doping with B and N atoms, by which p-type doping and n-type doping graphene are respectively induced. A bandgap of about 0.5 eV is generated through O doping, and geometrically the O atom is also in the graphene plane. No magnetic moment is detected in B- , N- and O-doped graphene. For F doping, the F atom bonds with one of the carbon atoms close to the vacancy, with the other two carbon atoms undergoing a Jahn-Teller distortion. A weak polarized magnetic moment of 0.71 μ(B) is detected through F doping.     

Electrical contacts in monolayer blue phosphorene devices

Semiconducting monolayer (ML) blue phosphorene (BlueP) shares similar stability with ML black phosphorene (BP), and it has recently been grown on an Au surface. Potential ML BlueP devices often require direct contact with metal to enable the injection of carriers. Using ab initio electronic structure calculations and quantum transport simulations, for the first time, we perform a systematic study of the interfacial properties of ML BlueP in contact with metals spanning a wide work function range in a field effect transistor (FET) configuration. ML BlueP has undergone metallization owing to strong interaction with five metals. There is a strong Fermi level pinning (FLP) in the ML BlueP FETs due to the metal-induced gap states (MIGS) with a pinning factor of 0.42. ML BlueP forms n-type Schottky contact with Sc, Ag, and Pt electrodes with electron Schottky barrier heights (SBHs) of 0.22, 0.22, and 0.80 eV, respectively, and p-type Schottky contact with Au and Pd electrodes with hole SBHs of 0.61 and 0.79 eV, respectively. The MIGS are eliminated by inserting graphene between ML BlueP and the metal electrode, accompanied by a transition from a strong FLP to a weak FLP. Our study not only provides insight into the ML BlueP–metal interfaces, but also helps in the design of ML BlueP devices.

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Transport properties of graphene nanoroads in boron nitride sheets

We demonstrate that the one-dimensional (1D) transport channels that appear in the gap when graphene nanoroads are embedded in boron nitride (BN) sheets are more robust when they are inserted at AB/BA grain boundaries. Our conclusions are based on ab initio electronic structure calculations for a variety of different crystal orientations and bonding arrangements at the BN/C interfaces. This property is related to the valley Hall conductivity present in the BN band structure and to the topologically protected kink states that appear in continuum Dirac models with position-dependent masses.     

Surface morphology control of the SiC (0001) substrate during the graphene growth

Abstract

The dependence of surface morphology of the SiC(0001) substrate on the rate with which it is heated up to the temperature of graphene growth was studied by three techniques: atomic force microscopy, Raman spectroscopy and Kelvin probe force microscopy. The study was carried out for the rates of substrates heating ranging from 100?°C/min to 320?°C/min. As a result, it was found out that both the width of the terraces forming on the surface of SiC substrate and the uniformity of the graphene layers covering these terraces significantly depend on the applied rate of the heating. It was also shown that the most homogeneous monolayer graphene with the minimum of double-layers inclusions is formed if the rate of SiC heating is about 250?°C/min.     

Growth Mechanism of Metal Clusters on a Graphene/Ru(0001) Template

Using first‐principles calculations combined with scanning tunneling microscopy experiments, we investigated the adsorption configurations, electronic structures and the corresponding growth mechanism of several transition metal (TM) atoms (Pt, Ru, Ir, Ti, Pd, Au, Ag, and Cu) on a graphene/Ru(0001) moiré template (G/Ru(0001)) at low coverage. We find that Pt, Ru, Ir, and Ti selectively adsorb on the fcc region of G/Ru(0001) and form ordered dispersed metal nanoclusters. This behavior is due to the unoccupied d orbital of the TM atoms and the strong sp³ hybridization of carbon atoms in the fcc region of G/Ru(0001). Pd, Au, Ag, and Cu form nonselective structures because of the fully occupied d orbital. This mechanism can be extended to metals on a graphene/Rh(111) template. By using Pt as an example, we provide a layer by layer growth path for Pt nanoclusters in the fcc region of the G/Ru(0001). The simulations of growth mechanism agree well with the experimental observations. Moreover, they also provide guidance for the selection of suitable metal atoms to form ordered dispersed metal nanoclusters on similar templates.     

Movement of Dirac points and band gaps in graphyne under rotating strain

The introduction of lattice anisotropy causes Dirac cones to shift in response to the applied strain,leaving a pseudogap at the original Dirac points.Here,a group-theory analysis is combined with first-principles calculations to reveal the movement characteristics of Dirac points and band gaps in various graphynes under rotating uniaxial and shear strains.Graphene,where linear effects dominate,is different from a-,β-,and y-graphynes,which generate strong nonlinear responses due to their bendable acetylenic linkages.However,the linear components of the electronic response,which are essential in determining material performance such as intrinsic carrier mobility due to electron-phonon coupling,can be readily separated,and are well described by a unified theory.The movement of the Dirac points in a-graphyne is circular under a rotating strain,and the pseudogap opening is isotropic with a magnitude of only 2％ that in graphene.In comparison,the movement in β-graphyne is elliptical and the center is displaced from the origin.For y-graphyne,three branches of gaps change with the applied strains with a sine/cosine dependence on the strain angle.The developed methodology is useful in determining the electronic response to various strains of Dirac materials and two-dimensional semiconductors.     

掺杂单层MoS_2电子结构的第一性原理计算

采用第一性原理研究Cu,Ag,Au掺杂单层MoS_2的键长畸变、能带结构和态密度。探讨Cu,Ag,Au掺杂对单层MoS_2电子结构的影响。结果表明:Cu,Ag,Au在S位掺杂的杂质能都低于在Mo位掺杂的杂质能,其在S位掺杂的体系的稳定性强于在Mo位掺杂的体系。在S位掺杂时,杂质与最近邻的Mo,S原子的键长都发生了畸变,畸变率最大的是dAu-Mo,达23.8%。与单层MoS_2的超胞相比,掺杂体系的禁带中出现了4条新能级,导带和价带的能量向低能区移动。杂质原子周围存在着电荷聚集,同时也存在电荷损失。     

Modification of carbon solubility in metals at preparation of graphene from the metal/SiC structure

Graphene has, due to its favourable features, a wide usage in a range of industries. A number of methods are being used for its preparation, each of them being suitable for another application of graphene. One of the methods is based on annealing of a metal/SiC structure at temperatures ranging from 800 to 1000?°C; graphene is formed here on the basis of carbon segregation from the metallization. This process is dependent on the reaction of metals with SiC and on solubility of carbon within metals. Our work was focused on modification of solubility of carbon in basic metals (Ni and Co) by adding suitable admixtures—Ge, Cu, Au. Principal influence onto parameters of graphene films had copper added into the metallization with cobalt. We succeeded to prepare graphene containing two carbon mono-layers (BLG).     

Strain effects in graphene and graphene nanoribbons: The underlying mechanism

A tight-binding analytic framework is combined with first-principles calculations to reveal the mechanism underlying the strain effects on electronic structures of graphene and graphene nanoribbons (GNRs). It provides a unified and precise formulation of the strain effects under various circumstances-including the shift of the Fermi (Dirac) points, the change in band gap of armchair GNRs with uniaxial strain in a zigzag pattern and its insensitivity to shear strain, and the variation of the k-range of edge states in zigzag GNRs under uniaxial and shear strains which determine the gap behavior via the spin polarization interaction.      

Graphene epitaxy by chemical vapor deposition on SiC

We demonstrate the growth of high quality graphene layers by chemical vapor deposition (CVD) on insulating and conductive SiC substrates. This method provides key advantages over the well-developed epitaxial graphene growth by Si sublimation that has been known for decades. (1) CVD growth is much less sensitive to SiC surface defects resulting in high electron mobilities of ～1800 cm(2)/(V s) and enables the controlled synthesis of a determined number of graphene layers with a defined doping level. The high quality of graphene is evidenced by a unique combination of angle-resolved photoemission spectroscopy, Raman spectroscopy, transport measurements, scanning tunneling microscopy and ellipsometry. Our measurements indicate that CVD grown graphene is under less compressive strain than its epitaxial counterpart and confirms the existence of an electronic energy band gap. These features are essential for future applications of graphene electronics based on wafer scale graphene growth.     

Structure and magnetic properties of mono- and bi-layer graphene films on ultraprecision figured 4H-SiC(0001) surfaces

Monolayer and bilayer graphene films with a few hundred nm domain size were grown on ultraprecision figured 4H-SiC(0001) on-axis and 8 degrees -off surfaces by annealing in ultra-high vacuum. Using X-ray photoelectron spectroscopy (XPS), atomic force microscopy, reflection high-energy electron diffraction, low-energy electron diffraction (LEED), Raman spectroscopy, and scanning tunneling microscopy, we investigated the structure, number of graphene layers, and chemical bonding of the graphene surfaces. Moreover, the magnetic property of the monolayer graphene was studied using in-situ surface magneto-optic Kerr effect at 40 K. LEED spots intensity distribution and XPS spectra for monolayer and bilayer graphene films could become an obvious and accurate fingerprint for the determination of graphene film thickness on SiC surface.     

Stability,magnetic and electronic properties of SiC sheet doped with B,N, Al and P

Using DFT-based calculations, we study chemical doping of silicene–graphene hybrid with (B, N, Al and P). Planar structure of SiC sheet remains unaffected on doping and all the systems are stable. P and N dopants are strongly bonded to the hybrid compared with Al and N. Charge transfer calculations show that (B, N)/(Al, P) behave like acceptors/donors, respectively. All configurations retain the semi-conductor character of pure SiC and show magnetic order. Curie temperature is determined for the ferromagnetic structures. These results provide the possibility of tuning the gap and inducing magnetism in SiC as required for future applications.     

Visualizing local doping effects of individual water clusters on gold(111)-supported graphene

The local charge carrier density of graphene can exhibit significant and highly localized variations that arise from the interaction between graphene and the local environment, such as adsorbed water, or a supporting substrate. However, it has been difficult to correlate such spatial variations with individual impurity sites. By trapping (under graphene) nanometer-sized water clusters on the atomically well-defined Au(111) substrate, we utilize scanning tunneling microscopy and spectroscopy to characterize the local doping influence of individual water clusters on graphene. We find that water clusters, predominantly nucleated at the atomic steps of Au(111), induce strong and highly localized electron doping in graphene. A positive correlation is observed between the water cluster size and the local doping level, in support of the recently proposed electrostatic-field-mediated doping mechanism. Our findings quantitatively demonstrate the importance of substrate-adsorbed water on the electronic properties of graphene.     

Scanning gate microscopy on graphene: charge inhomogeneity and extrinsic doping

We have performed scanning gate microscopy (SGM) on graphene field effect transistors (GFET) using a biased metallic nanowire coated with a dielectric layer as a contact mode tip and local top gate. Electrical transport through graphene at various back gate voltages is monitored as a function of tip voltage and tip position. Near the Dirac point, the response of graphene resistance to the tip voltage shows significant variation with tip position, and SGM imaging displays mesoscopic domains of electron-doped and hole-doped regions. Our measurements reveal substantial spatial fluctuation in the carrier density in graphene due to extrinsic local doping from sources such as metal contacts, graphene edges, structural defects and resist residues. Our scanning gate measurements also demonstrate graphene's excellent capability to sense the local electric field and charges.     

Structural and electronic properties of hydrogen adsorptions on BC₃ sheet and graphene: a comparative study

We have systematically investigated the effect of hydrogen adsorption on a single BC? sheet as well as graphene using first-principles calculations. Specifically, a comparative study of the energetically favorable atomic configurations for both H-adsorbed BC? sheets and graphene at different hydrogen concentrations ranging from 1/32 to 4/32 ML and 1/8 to 1 ML was undertaken. The preferred hydrogen arrangement on the single BC? sheet and graphene was found to have the same property as that of the adsorbed H atoms on the neighboring C atoms on the opposite sides of the sheet. Moreover, at low coverage of H, the pattern of hydrogen adsorption on the BC? shows a proclivity toward formation on the same ring, contrasting their behavior on graphene where they tend to form the elongated zigzag chains instead. Lastly, both the hydrogenated BC? sheet and graphene exhibit alternation of semiconducting and metallic properties as the H concentration is increased. These results suggest the possibility of manipulating the bandgaps in a single BC? sheet and graphene by controlling the H concentrations on the BC? sheet and graphene.     

Modulating the Surface State of SiC to Control Carrier Transport in Graphene/SiC

Silicon carbide (SiC) with epitaxial graphene (EG/SiC) shows a great potential in the applications of electronic and photoelectric devices. The performance of devices is primarily dependent on the interfacial heterojunction between graphene and SiC. Here, the band structure of the EG/SiC heterojunction is experimentally investigated by Kelvin probe force microscopy. The dependence of the barrier height at the EG/SiC heterojunction to the initial surface state of SiC is revealed. Both the barrier height and band bending tendency of the heterojunction can be modulated by controlling the surface state of SiC, leading to the tuned carrier transport behavior at the EG/SiC interface. The barrier height at the EG/SiC(000‐1) interface is almost ten times that of the EG/SiC(0001) interface. As a result, the amount of carrier transport at the EG/SiC(000‐1) interface is about ten times that of the EG/SiC(0001) interface. These results offer insights into the carrier transport behavior at the EG/SiC heterojunction by controlling the initial surface state of SiC, and this strategy can be extended in all devices with graphene as the top layer.     

Heat conduction across monolayer and few-layer graphenes

We report the thermal conductance G of Au/Ti/graphene/SiO(2) interfaces (graphene layers 1 ≤ n ≤ 10) typical of graphene transistor contacts. We find G ≈ 25 MW m(-2) K(-1) at room temperature, four times smaller than the thermal conductance of a Au/Ti/SiO(2) interface, even when n = 1. We attribute this reduction to the thermal resistance of Au/Ti/graphene and graphene/SiO(2) interfaces acting in series. The temperature dependence of G from 50 ≤ T ≤ 500 K also indicates that heat is predominantly carried by phonons through these interfaces. Our findings suggest that metal contacts can limit not only electrical transport but also thermal dissipation from submicrometer graphene devices.     

In situ high-temperature scanning tunneling microscopy study of bilayer graphene growth on 6H-SiC(0001)

Using in situ high-temperature (1395 K), ultra-high vacuum, scanning tunneling microscopy (STM), we investigated the growth of bilayer graphene on 6H-SiC(0001). From the STM images, we measured areal coverages of SiC and graphene as a function of annealing time and found that graphene grows at the expense of SiC. Graphene domains were observed to grow, at comparable rates, at (I) graphene-free SiC step edges, (II) graphene-SiC interfaces, and (III) the existing graphene domain edges. Based upon our results, we suggest that the rate-limiting step controlling bilayer graphene growth is the desorption of Si from the substrate.