Structural properties of a monolayer graphite film on the (111)Ir surface

The structural properties of a monolayer graphite film prepared on the (111)Ir surface through thermal decomposition of benzene molecules were studied. The study was carried out in ultrahigh vacuum using scanning tunneling microscopy, which allowed observation of the atomic structure of the film. It is shown that, on extended smooth regions of the Ir surface, a continuous graphite film with a regular arrangement of carbon atoms in a planar hexagonal lattice is formed. The orientation of zigzag carbon atom chains coincides with the 〈110〉 direction on the Ir surface. Structural defects of the (5, 7) configuration were revealed in the film. A comparison of the topographies of the film and the (111)Ir surface shows that the graphite layer smoothly (without discontinuities) flows over subnanometer topographical features existing on the Ir surface and that the distance between the graphite film and the metal surface in this case can reach 1 nm.     

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.     

Interaction of silver atoms with iridium and with a two-dimensional graphite film on iridium: Adsorption,desorption, and dissolution

The initial stages in the interaction of silver with the (111)Ir surface and with a two-dimensional graphite film (2D GF) on (111)Ir were studied by high-resolution electron Auger spectroscopy in ultrahigh vacuum. The growth mechanisms of silver films and the desorption fluxes of Ag atoms were determined, and their desorption energies estimated. It was found that the Ag desorption fluxes from a 2D GF on Ir and from a thick silver film on the pure metal are similar and considerably (an order of magnitude) smaller than the sublimation fluxes from bulk silver at the same temperatures. The activation energy for desorption from a submonolayer film varies from 3.2 eV for coverage θ=1 to 3.7 eV at θ ～ 0. It was shown that silver atoms do not penetrate into the substrate bulk throughout the temperature range covered (300–1800 K).     

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.     

Intercalation of two-dimensional graphite films on metals by atoms and molecules

An analysis is made of some general laws governing a new physical effect, i.e., the spontaneous penetration of particles (atoms, C₆₀ molecules) adsorbed on a two-dimensional graphite film on a metal (Ir, Re, Pt, Mo,...) to beneath the graphite film (intercalation). It is shown that atoms having low ionization potentials (Cs, K, Na) intercalate a two-dimensional graphite film on iridium at T=300–400K with an efficiency χ≈0.5, accumulating beneath the film to a concentration of up to a monolayer. Atoms having high ionization potentials (Si, Pt, Ni, C, Mo, etc.) intercalate a two-dimensional graphite film on iridium at T≈1000K with an efficiency, χ≈1, forming beneath the film a thick intercalate layer which is strongly bonded chemically to the metal substrate but is probably weakly bonded to the graphite monolayer by van der Waals forces. The presence of a graphite “lid” impeding the escape of atoms from the intercalated state up to record high temperatures T∼2000K leads to superefficient diffusion (with an efficiency close to one) of various atoms (Cs, K) into the bulk of the substrate (Re, Ir). Zh. Tekh. Fiz. 69, 72–75 (September 1999)     

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.     

Specific features of the formation of ytterbium films on the Si(111) surface at room temperature

The processes accompanying the formation of ytterbium films on the Si(111) surface at room temperature are investigated by the contact potential difference method, Auger electron spectroscopy, low-energy electron diffraction, and thermal desorption spectroscopy. It is shown that the grown metal films are uniform in thickness and that Si atoms virtually do not dissolve in the films. The atoms of the silicon substrate can diffuse in limited amounts into the Yb metal film only when the surface is bombarded by high-energy primary electron beams employed in Auger electron spectroscopy. The results obtained permit the conclusion that the previously observed oscillations of the work function in Yb-Si(111) thin-film structures cannot originate from dissolution of silicon atoms in the ytterbium film.     

Sodium Intercalation of Graphene Films on Re( $$10\bar 10$$ 10 1 ¯ 0 )

It is shown that during low-temperature (300–500 K) intercalation of sodium atoms into thin multilayer graphene and graphite films on rhenium the first graphene layer plays the role of a trap to which atoms coming on the surface diffuse through a graphite film. The intercalation phase of the interlayer space in the graphite bulk is actively filled at a sodium atoms concentration under the first graphene layer close to the maximum possible (2 ± 0.5) × 10¹⁴ cm^–2. This phase capacity is proportional to the graphite film thickness that can be varied in this work from one graphene layer to ~50 atomic layers. The diffusion energy E _d of Na atoms through the graphite film was estimated to be E _d ≈ 1.4 eV.

     

Influence of the Porosity of the Surface of a Graphite Furnace on the Atomization of a Sample

The influence of the wear of a tube graphite furnace and the morphological features of its surface on the formation of an atomic-absorption signal has been investigated. Electron-microscopic and mass-spectrometric investigations have shown that, prior to atomization, copper in the form of elementary metal microparticles is found not only on the surface of the furnace but also in the bulk of its pores. Free atoms are formed as a result of the concurrent processes of atomization of a sample on the surface of the furnace and in the bulk of its pores. The change in the apparent energy of formation of free atoms of metals interacting actively with graphite in the process of atomization and the inflection on their Arrhenius plot have been explained qualitatively.     

Anomalous behavior of silver atoms in intercalation under a two-dimensional graphite film

It is shown that silver atoms, the only ones of many atoms studied previously (Si, C, Mo, Pt, Cu, Ir, Ni, Au, Cs, K, Na, Ba,...), do not intercalate, that is, do not penetrate under a two-dimensional graphite film (2DGF) on a metal either upon direct depositing in the temperature range 300–2000 K or annealing of a previously deposited silver film. Intercalation becomes possible if silver is deposited on a 2DGF with previously intercalated cesium; in this case, silver atoms displace Cs atoms from under the 2DGF upon heating up to 1100 K.     

Identification of solid electrolyte interphase formed on graphite electrode cycled in trifluoroethyl aliphatic carboxylate-based electrolytes for low-temperature lithium-ion batteries

Trifluoroethyl aliphatic carboxylates with different length of carbon-chain in acyl groups have been introduced into carbonate-based electrolyte as co-solvents to improve the low-temperature performance of lithium-ion batteries, both in capacity retention and lowering polarization of graphite electrode. To identify the further influence of trifluoroethyl aliphatic carboxylates on graphite electrode, the components and properties of the surface film on graphite electrode cycled in different electrolytes are investigated using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements. The IR and XPS results show that the chemical species of the solid electrolyte interphase (SEI) on graphite electrode strongly depend on the selection of co-solvent. For instance, among those species, the content of RCOOLi increases with an increasing number of carbon atoms in RCOOCH₂CF₃ molecule, wherein R was an alkyl with 1, 3, or 5 carbon atoms. We suggest that the thickness and components of the SEI film play a crucial role on the enhanced low-temperature performance of the lithium-ion batteries.     

Structure and dynamics of graphite-supported bimetallic nanoclusters

Molecular dynamics simulations are used to analyze the structure and dynamics of isolated bimetallic nanoclusters of 343 (Cu-Ni) and 1000 atoms (Cu-Ni and Pt-Au) deposited on a graphite substrate. The metal-metal interactions are modeled with the many-body Sutton-Chen potential, and a Lennard-Jones potential is used to describe the metal-carbon interactions. The nanocluster melting temperature is determined from caloric and heat capacity curves, and the atomic distribution is studied layer-by-layer as a function of temperature in a direction perpendicular to the substrate plane. Changes in the nanocluster shape as temperature increases are monitored through deformation parameters that show clear evidence of structural and melting transitions as well as of atomic surface diffusion in the cluster. Dynamic properties such as atomic and whole-cluster diffusion, and the motion of the metal atoms at the interface metal/graphite are characterized as a function of temperature.     

模板对异构体选择性生长的动力学控制作用与化学气相沉积金刚石的生长机理

阐述了模板的动力学控制作用对大尺度有序结构特别是亚稳相的生长，对自由能相差很小的异构体的选择生长所具有的重要作用.汲取现有金刚石生长理论的合理思想，以模板概念为基础给出了对化学气相沉积(CVD)过程的动力学热力学综合描述：1)碳原子在碳氢化合物中的化学势高于固相碳，气相碳氢化合物的碳原子有可能落到化学势较低的固态碳的各种异构体.2)气相碳通过表面反应实现向固相碳的转化.3)表面的模板作用是控制气相碳原子转换方式的主要动力学因素，不同的表面(石墨各种取向的表面及金刚石不同取向的表面)选择了落入其上的碳原子的结构方式及能量状态.4)因此,衬底的不同区域可发生几种不同的独立的表面反应过程,这些反应对应于不同表面的生长.5）而这些表面反应的方向性及速度受表面临域热力学因素的影响，反应的方向性决定了某种晶面是生长或刻蚀，在特定的温度、压强及各种气体分压下可以实现金刚石的生长和石墨的刻蚀.6)衬底局域晶格结构及键价结构和衬底表面气相的温度、压强及各种气体分压等热力学条件共同决定了成核的临界条件.7）与外界有能量和物质交换的等离子体系统，以及气相中发生的一系列化学反应，仅起到了维持某种固相表面生长所需要的非平衡热力学条件和化学条件的作用.金刚石和石墨表面具有的模板动力学控制作用，在特定热力学条件下主导自身外延层的生长方式；异质衬底的某些局域微观结构可以作为新相生长成核的局域模板；不同材料、不同的处理方法、及不同的化学环境下的衬底具有不同的局域微观结构，从而决定了多晶薄膜的取向优势. 关键词： 模板 异构体 选择性生长 金刚石薄膜     

Thin graphite overlayers: Graphene and alkali metal intercalation

Using LEED and angle resolved photoemission for characterisation we have prepared graphite overlayers with down to monolayer thickness by heating SiC crystals and monitored alkali metal intercalation for the multilayer films. The valence band structure of the monolayer is similar to that calculated for graphene though downshifted by around 0.8 eV and with a small gap at the zone corner. The shift suggests that the transport properties, which are of much present interest, are similar to that of a biased graphene sample. Upon alkali metal deposition the 3D character of the π states is lost and the resulting band structure becomes graphene like. A comparison with data obtained for ex situ prepared intercalation compounds indicates that the graphite film has converted to the stage 1 compounds C₈K or C₈Rb. Advantages with the present preparation method is that the graphite film can be recovered by desorbing small amounts of alkali metal and that the progress of compound formation can be monitored. The energy shifts measured after different deposits indicate that saturation is reached in three steps. Our interpretation is that in the first the alkali atoms are dispersed while the final steps are characterized by the formation of first one and then a second (2 × 2) ordered alkali metal layer adjacent to the uppermost carbon layer.     

Growth of ultrathin Pd films on Al(001) surfaces

High-energy ion backscattering spectroscopy (HEIS) and X-ray photoelectron spectroscopy (XPS) were used to determine the growth mode and the interface structure of ultrathin Pd films deposited on Al(001) surfaces at room temperature. Measured Al and Pd surface peak areas for MeV He⁺ ions incident normal to the surface show that Pd atoms intermix with and displace Al substrate atoms. The mixing continues for Pd coverages from 0–5 monolayers, at which point a Pd metal film begins to grow on the alloy surface. XPS measurements of the Pd 3d photopeaks show a chemical shift that is consistent with the formation of an AlPd-like compound during the mixing phase, and Pd metal thereafter. HEIS results further reveal that the alloyed overlayer as well as the Pd metal film have some degree of axial alignment with respect to the Al substrate. The XPS intensity measurements are consistent with this two-stage growth model.     

Influence of the metal substrate on the adsorption properties of thin oxide layers: Au atoms on a thin alumina film on NiAl(110)

Thin oxide films grown on metal substrates are widely used in surface science to model bulk oxides, assuming their chemical and electronic properties to be similar. In some cases, however, this might not be justified as the present scanning tunneling microscopy studies demonstrate for Au atoms on a thin alumina film on NiAl(110). Au atoms were evaporated onto the oxide film at a sample temperature of approximately 10 K. At low coverage, this leads to the formation of one-dimensional clusters with unusually large Au-Au distances of 5.6-6.0 A. A direct interaction between the Au atoms can be excluded, and a substrate-mediated mechanism is supposed instead. This assumption is strengthened by the finding that the Au chains exhibit a preferential orientation: They are almost aligned with the [001] direction of the NiAl(110) substrate, clearly indicating that the metal substrate participates in the binding of the Au atoms.     

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.     

脉冲激光诱导金属薄膜电离的分子动力学模拟

采用分子动力学方法模拟研究了激光诱导金属薄膜的电离过程,对激光等离子体形成早期原子的运动轨迹、薄膜表面的温度变化以及原子的电离特性进行了详细分析,并探究了脉冲激光参数对原子电离过程的影响.结果表明,在激光照射过程中,薄膜表面先熔化而后又气化,气化的原子继续吸收激光能量继而电离.激光的峰值功率密度越大,原子电离速率越快,电离数目越多,薄膜表面的温度越高.脉冲宽度越小,原子电离速率越快,薄膜表面的温度越高,但原子的电离数目先增加后减小.     

Electron spectroscopy of objects for nanoelectronics

An electron-spectroscopic analysis is made of layered nanostructures and clusters at the surface and in the bulk of a solid. A new method of forming metal/insulator/semiconductor (superconductor) nanostructures is proposed based on ion-stimulated metal segregation effects at the surface of low-temperature gallium arsenide and a 123 high-temperature superconductor. The geometric parameters and electronic structure of these nano-objects are studied. It is shown that their electronic properties can be controllably varied in situ by acting on the surface. The dimensional transformation of the electronic properties of metal clusters is studied for clusters in the insulator SiO₂, in the superconductor LTMBE-GaAs, and on silicon and graphite surfaces. The nature of this transformation is clarified. A diagnostics for cluster ensembles is developed by which one can determine the parameters needed to describe singleelectron transport: the average number of atoms per cluster, the average distance between clusters and isolated atoms, and the chemical state of the atoms. Ensembles of silver clusters with specified parameters are obtained on a silicon surface. It is shown that these ensembles are potentially useful for developing single-electron devices. Zh. Tekh. Fiz. 69, 85–89 (September 1999)