Field electron emission and field desorption of cesium from graphene

Field electron emission and field desorption of cesium ions from a monatomic graphene film on Ir and graphene clusters in amorphous carbon are investigated using field electron microscopy and continuous-mode field desorption microscopy. The deposition of cesium on amorphous carbon with graphite clusters leads to inversion of the emission (i.e., emission from the emission centers disappears against the back-ground of uniform emission from the previously nonemitting surface). In both systems, ion current pulses are observed during field desorption in a stationary electric field. During field desorption from the graphene film, current pulses of Cs⁺ ions with a duration shorter than 0.1 s appear from the plane faces of the iridium point. During desorption from graphite clusters, ion current pulses form a pattern of “collapsing rings” on the screen. Possible mechanisms of the observed processes are considered using the model of cesium intercalation by graphite and by the graphene layer and the desorption of Cs atoms under the action of the electric field, as well as the “flip” of the dipole moment during the cesium intercalation.     

Role of edge atoms of graphene islands on metals in nucleation,growth, alkali metal intercalation

Physics of the Solid State - The effect of edge carbon atoms in graphene islands grown on a metal surface on the kinetics of nucleation, growth and dissolution of these islands, as well as of a...     

Physicochemical processes in multiphase systems on metal surfaces containing nano-carbon: Segregation,dissolution, graphene nucleation,and growth

A carbon phase equilibria on the surface of metals during graphene nucleation and initial graphite growth is considered thermodynamically. Three phases are shown to be necessarily taken into account: C atoms dissolved in a metal substrate bulk, C atoms chemisorbed on the surface, and graphene (polycondensed carbon phase). Applicability of the Gibbs phase rule to this particular case is analyzed, with surface tension taken into account as an independent thermodynamic degree of freedom. A specific role of boundary atoms of graphene islands, which can be considered (with some limitations) as an independent quasi-1D phase is revealed.     

Graphene-graphite phase transition at the surface of a carbonized metal

A phase transition leading to the transformation of a graphene layer into a multilayer graphite film at the surface of a carbonized metal has been experimentally studied on the atomic level under ultrahigh-vacuum conditions. It has been shown that this process is governed by dynamic equilibrium between edge atoms of graphene islands and a chemisorbed carbon phase, two-dimensional carbon “gas,” and is observed in the temperature range of 1000–1800 K. The features of the phase transition at the surfaces Ni(111), Rh(111), and Re(10-10) are similar, although the specific kinetic characteristics of the process depend on the properties of the substrate. It has been shown that change in the emissivity of the substrate after the formation of a multilayer graphite film increases the rate of the phase transition and leads to a temperature hysteresis.     

The nature of the adsorption bond between graphite islands and iridium surface

To reveal the nature of adsorption bonds between two-dimensional graphite islands and iridium (111) and (100) faces, a study has been made of the adsorption of potassium and cesium atoms on the surface of these systems, using thermal desorption and Auger electron spectroscopy, as well as surface ionization and thermionic emission techniques. The graphite islands are shown to be weakly bound to the iridium substrate by Van der Waals forces. The unsaturated valence bonds at the periphery of the graphite islands are “lowered down” on to the metal. The recess between the graphite layer and the metal is filled by adsorbing particles through defects in the graphite layer. The atoms can penetrate into the recess in two ways: at T > 1000 K directly from the flux incident on the surface, and at T < 1000 K also by migration from the graphite island surface. The adsorption capacity of this state is ～ (2?3) × 10¹⁴cm^-2. Thermal destruction of the islands at T > 1900 K liberates the potassium and cesium atoms from under the graphite islands. Our study suggests that the reason for the “raised” position of the islands lies in the valence bonds of the graphite layer being saturated, the valence bonds of the metal and its crystallographic orientation being less significant. Therefore one may expect the graphite layer to be raised also above other metals as well. The filling by cesium of the recess between the graphite layer and iridium and of the adsorption phase on the graphite surface, does not change the general “graphitic” shape of the carbon Auger peak. This cesium results, however, in a pronounced splitting of the negative spike on the carbon peak (which provides information on its location relative to the graphite layer) indicating the appearance in the valence band of graphite near the Fermi level of two narrow (～ 2?3 eV) regions with an enhanced density of states originating from the presence of the alkali metal.     

Epitaxial growth of a graphene single crystal on the Ni(111) surface

The thermally controlled synthesis of graphene from propylene molecules on the Ni(111) surface in ultrahigh vacuum is studied by scanning tunneling microscopy and density functional theory. It is established that the adsorption of propylene on Ni(111) atomic terraces at room temperature results in the dehydration of propylene molecules with the formation of single-atomic carbon chains and in the complete dissociation of propylene at the edges of atomic steps with the subsequent diffusion of carbon atoms below the surface. The annealing of such a sample at 500°С leads to the formation of multilayer graphene islands both from surface atomic chains and by the segregation of carbon atoms collected in the upper nickel atomic layers. The process of formation of an epitaxial graphene monolayer until the complete filling of the nickel surface is controllably observed. Atomic defects seen on the graphene surface are interpreted as individual nickel atoms incorporated into graphene mono- or bivacancies.     

Interaction of scandium and titanium atoms with a carbon surface containing five- and seven-membered rings

The use of carbon nanotubes coated by atoms of transition metals to store molecular hydrogen is associated with the problem of the aggregation of these atoms, which leads to the formation of metal clusters. The quantum-chemical simulation of cluster models of the carbon surface of a graphene type with scandium and titanium atoms has been performed. It has been shown that the presence of five- and seven-membered rings, in addition to six-membered rings, in these structures makes it possible to strongly suppress the processes of the migration of metal atoms over the surface, preventing their clustering.     

Anomalous changes in electron emission during adsorption of alkali metals on a carbon film

An anomalous change was discovered in the field of electron emission during the adsorption of alkali metal atoms on the surface of an amorphous carbon film. The phenomenon involves the disappearance of electron emission from graphite nanoclusters that were local emission sources before the deposition of cesium. The observed effect is explained on the basis of surface diffusion processes of cesium atoms in a nonuniform electric field and intercalation graphite nanostructures by cesium.     

Cesium ion emission from a graphene surface on iridium in a high-intensity electric field

Features of cesium ion emission from a graphene film on iridium in a 10⁷–10⁸ V cm^?1 electric field of are studied. Field electron and desorption images demonstrate that the film consists of regions (islands) 20–100 nm in size. Intercalated cesium lies under the film. There is continuous desorption of cesium ions from the defects in the graphene film and the regions of where islands abut one another. Cesium ions arrive at the desorption sites from the intercalated state.     

Influence of cesium atoms on the thermal decomposition of graphene films on (10-10)Re

A sharp rise in the decomposition temperature of a graphene layer obtained on the (10-10)Re surface by underneath intercalation of cesium atoms is found. The graphene decomposition temperature increases by about 500 K and achieves a record high value for graphene, 2200 K.     

Intercalation of graphene on iridium with samarium atoms

Intercalation of graphene on Ir (111) with Sm atoms is studied by methods of thermal desorption spectroscopy and thermionic emission. It is shown that adsorption of samarium at T = 300 K on graphene to concentrations of N ≤ 6 × 10¹⁴ atoms cm^–2 followed by heating of the substrate leads to practically complete escape of adsorbate underneath the graphene layer. At N > 6 × 10¹⁴ atoms cm^–2 and increasing temperature, a fraction of adsorbate remains on graphene in the form of two-dimensional “gas” and samarium islands and are desorbed in the range of temperatures of 1000–1200 K. Samarium remaining under the graphene is desorbed from the surface in the temperature range 1200–2150 K. Model conceptions for the samarium–graphene–iridium system in a wide temperature range are developed.     

The Determining Influence of the Perimeter of Graphene Islands on Phase Equilibria in Graphene–Metal System Containing Dissolved Carbon

Physics of the Solid State - It was found that an insignificant increase of the concentration of carbon atoms in the volume of metal (~2–3%) leads to a significant increase (by 3–4...     

Ultrahigh-vacuum STM studies of the structure of a graphene layer on the Ir(111) surface

The atomic structure of a two-dimensional graphite film formed on the Ir(111) surface is studied. In order to weaken the interaction of the graphite film with the metal surface, cesium atoms are intercalated beneath the film. The studies by scanning tunneling microscopy in ultrahigh vacuum provide support for the formation of a continuous graphite layer, with the regular arrangement of carbon atoms at extended surface regions. From comparison of the roughness of the film and that of the substrate, it follows that the spacing between the film and metal surface varies within the limits of 1 nm. Characteristic structural defects of configuration (5, 7) are detected in the film.     

Growth kinetics of graphene and graphite films on the \operatorname{Re} (10\bar 10) surface

Growth kinetics of graphene and graphite layers on the surface of carbon-saturated rhenium has been investigated. The experimental data agree well with the results of the mathematical analysis of diffusion processes in the metal bulk with the participation of carbon atoms and the subsequent precipitation of carbon on the surface. It has been established that graphene layers of rigorously specified thickness in the range of 1–50 layers can be grown on metal in the temperature range of 1300–1500 K.     

6H-SiC(0001)表面graphene逐层生长的分子动力学研究

利用经典分子动力学方法和模拟退火技术分析研究了6H-ＳiC（0001）表面graphene的逐层生长过程及其形貌结构特点．研究表明,经过高温蒸发表面硅原子后,6H-ＳiC（0001）表面的碳原子能够通过自组织过程生成稳定的局部单原子层graphene结构．这种过程类似于6H-ＳiC（0001）表面graphene的形成,其生长和结构形貌演化主要取决于退火温度和表面碳原子的覆盖程度． 研究发现,当退火温度高于1400K时,6H-ＳiC（0001）表面碳原子能形成局部的单原子层graphene结构．这一转变温 关键词： graphene 碳化硅 分子动力学     

Contact conductance between graphene and quantum wires

The contact conductance between graphene and two quantum wires which serve as the leads to connect graphene and electron reservoirs is theoretically studied. Our investigation indicates that the contact conductance depends sensitively on the graphene-lead coupling configuration. When each quantum wire couples solely to one carbon atom, the contact conductance vanishes at the Dirac point if the two carbon atoms coupling to the two leads belong to the same sublattice of graphene. We find that such a feature arises from the chirality of the Dirac electron in graphene. Such a chirality associated with conductance zero disappears when a quantum wire couples to multiple carbon atoms. The general result irrelevant to the coupling configuration is that the contact conductance decays rapidly with the increase of the distance between the two leads. In addition, in the weak graphene-lead coupling limit, when the distance between the two leads is much larger than the size of the graphene-lead contact areas and the incident electron energy is close to the Dirac point, the contact conductance is proportional to the square of the product of the two graphene-lead contact areas, and inversely proportional to the square of the distance between the two leads.     

扫描电子显微镜法测定金属衬底上石墨烯薄膜的覆盖度

利用化学气相沉积法生长在金属衬底上的石墨烯薄膜,由于其尺寸的可控性和转移的便利性,被广泛用作各种透明电极.石墨烯薄膜的方块电阻是衡量其品质的重要指标之一,而石墨烯覆盖完全是保证薄膜拥有优良导电性能的基本前提.本文通过研究评估不确定度的分量,提出利用扫描电子显微镜像素计算微区和宏观覆盖度的方法.考虑到石墨烯薄膜覆盖区域与未覆盖区域边界的确定,以及晶畴数目的选取这两个因素对覆盖度测定造成的误差.通过微区有效扫描电子显微镜图像的确定、宏观石墨烯薄膜有效扫描电子显微镜图像的测量数目以及宏观石墨烯薄膜覆盖均匀性的表达,系统研究了化学气相沉积法生长在金属衬底上的石墨烯薄膜的微区覆盖度、宏观覆盖度和覆盖均匀性.该方法通过获得有限次微区扫描电子显微镜图像,不仅可以计算宏观石墨烯薄膜的覆盖度,还可以给出覆盖均匀性,既节省了测量时间,同时也能保证测量有效性.     

原位生长技术制备石墨烯强化铜基复合材料

利用等离子增强化学气相沉积方法,在铜粉表面原位生长了站立石墨烯,用于制备石墨烯强化铜基复合材料.研究表明,石墨烯包覆在铜粉外表面,微观尺度实现了两者的均匀混合;生长的初期阶段,碳、氢等离子基团可将铜粉表面的氧化层还原,有助于铜粉-石墨烯之间形成良好的界面;石墨烯的成核是一个生长/刻蚀相互竞争的过程,其尺寸可受制备温度调控.利用放电等离子烧结方法将粉末压制成型,测试结果显示,添加石墨烯样品的电阻率降低了一个数量级,维氏硬度和屈服强度分别提高了15.6%和28.8%.     

Carbon phases on nickel surfaces

The conditions of the formation of different carbon surface phases on nickel substrates by the example of a planar Ni( 110) surface and a stepped Ni(771 ) surface similar in structure were determined. The structure of the phases was investigated by means of scanning tunneling microscopy (STM), and the influence of carbon on the structure of the nickel surface was demonstrated. The process of graphene synthesis by propylene cracking is described. A method for forming graphene islands on nickel is proposed. A variety of phase transitions between the carbon surface phases (e.g., surface carbide, graphene, and graphene islands) and the reasons for their irreversibility are discussed. The relation between the structures of the surface carbide phases and the crystal structures of the initial surfaces for two different substrates is shown.     

On the mechanism of carbon nanotube formation in electrochemical processes

Quantum-chemical methods are used to analyze the mechanism of carbon nanotube formation in the electrochemical bath, where tiny fragments of graphene planes are in the environment of atoms and ions of alkali metals and halogens. In the optimal configuration, alkali metal atoms move toward the edge of a graphene fragment, whereas halogen atoms remain at the sites of their initial attachment. When the graphene fragments “burdened” by alkali metal and halogen atoms interact with each other, the overall graphene configuration twists in a natural way into a nanotube-like open-end structure.