Surfactant properties of cesium in molecular beam epitaxy of GaAs(100)

The experimental and ab initio investigations of the effect of a decrease in the binding energy of surface arsenic atoms under the cesium adsorption on an As-stabilized GaAs(001)-(2 × 4) surface have been performed. The cesium-induced redistribution of the charge on the surface atoms reduces the electron density in the As-Ga bond of the upper layer of the GaAs(001) surface; thus, the As-Ga binding energy decreases and, as a result, the diffusion activation energy, as well as the arsenic atom desorption, decreases. An increase in the diffusion coefficient of surface atoms, along with the property of Cs to segregate on the surface of a growing semiconductor film, makes it possible to use cesium as a surfactant in the low-temperature growth of GaAs by molecular beam epitaxy.     

Decrease in the bond energy of arsenic atoms on the GaAs(100)-(2×4)/c(2×8) surface due to the effect of adsorbed cesium

It has been found experimentally that the bond energy of arsenic atoms on the GaAs(100) surface decreases under the influence of adsorbed cesium. This is manifested in the disordering of the As-stabilized surface and in a decrease of ～(100 K in the temperature of the transition to the Ga-stabilized (100)GaAs(4×2)/c(8×2) surface. This effect is caused by the redistribution of the valence electron density between the arsenic atoms in the upper layer and the gallium atoms in the lower-lying layer as a result of charge transfer from the electropositive adsorbate to the semiconductor. In combination with the analogous effect of a decrease in the bonding energy of gallium atoms on the Ga-stabilized GaAs surface upon the adsorption of electronegative adsorbates (halogens), the effect observed allows the atomic layer etching of the polar GaAs(100) face.     

Possibilities of C 1s XPS and N(E) C KVV Auger spectroscopy for identification of inherent peculiarities of diamond growth

The interaction of C-atoms and CH_n-radicals with uncleaned and argon cleaned silicon substrate and with diamond surface after H-treatment have been studied in situ by XPS and Auger spectroscopy. It was found the formation of a new chemical surface state of carbon atoms in the case of carbon atoms and radicals interaction with cleaned silicon. The same chemical state was revealed on the H-treated diamond surface. Graphite-like structure of carbon atoms was observed on the surface of unlearned silicon and H-treated diamond after interaction with carbon atoms and radicals. N(E) C KVV Auger spectrum for the new chemical state of carbon atoms significantly differs from typical spectra for sp²- and sp³-bonded carbon materials. The high energy part of this spectrum was interpreted under the hypothesis of sp³-bonded carbon atoms but with shifted fermi level position.     

Plasmon excitation in core-level photoemission

The surface and bulk plasmon satellites in photoemission from a core level are calculated, treating the photoelectron quantum mechanically and including plasmon dispersion. The long wavelength plasmon excitations are suppressed by interference between intrinsic and extrinsic processes, giving featureless satellites at low electron kinetic energy. Structure develops as the electron kinetic energy increases.     

Surface plasmon satellites in x-ray photoemission from core states of adsorbed atoms

It is shown that the kinetic energy spectrum of electrons emitted from core levels of atoms adsorbed on metal surfaces should exhibit surface plasmon satellites. At sufficiently high energies, the satellites arise only via the so-called “intrinsic” mechanism, namely, screening of a suddenly created hole by the metal electrons. Their observation for a suitable adsorption system would thus constitute the first unequivocal evidence for the “intrinsic” effect.     

Large-scale molecular dynamics simulations of high energy cluster impact on diamond surface

Large-scale molecular dynamics simulations with high acceleration energy on a diamond surface were performed in order to investigate the surface erosion process. Accelerated argon or CO₂ clusters (∼960 atoms, 100 keV/cluster) impacted on the (111) surface of diamond which consisted of more than 1,000,000 carbon atoms. A typical hemispherical crater appeared about 0.7 ps after the impact, and two or three-layered shockwaves were formed and propagated to certain directions, but the crater was immediately filled up with the fluidized hot carbon material due to the collective elastic recovery before the reflection of the shockwave. The impact energy of the cluster was at first transferred mainly as kinetic energy of the diamond surface in a short time, and the potential energy was activated later. The activated carbon and oxygen atoms from the impact cluster stimulated the evaporation from the diamond surface for the CO₂ cluster impact while the evaporation seemed to be suppressed by the argon atoms themselves for the argon cluster impact. Received 22 November 2000     

Surface energy anisotropy of iron surfaces by carbon adsorption

To investigate the surface energy anisotropy of carbon-adsorbed iron surfaces related to carbon nanotube growth we have performed self-consistent pseudopotential density-functional calculations. The iron particle’s equilibrium shape is obtained from the Wulff construction using the calculated surface energies. We investigate the adsorption and diffusion of carbon atoms on the iron surfaces. It is found that the desorption energy of the carbon atoms and the activation energy for carbon diffusion are very different on different facets. Using the energetics of carbon-adsorbed iron surfaces, we evaluate the formation energies of the surfaces as a function of carbon chemical potential. Since the surface energies of the low-index iron facets are affected differently by the presence of carbon, the crystal shape is changed correspondingly.     

Nonradiative charge transfer in collisions of protons with rubidium atoms

The nonradiative charge-transfer cross sections for protons colliding with Rb(5s) atoms are calculated by using the quantum-mechanical molecularorbital close-coupling method in an energy range of 10 3 keV-10 keV.The total and state-selective charge-transfer cross sections are in good agreement with the experimental data in the relatively low energy region.The importance of rotational coupling for chargetransfer process is stressed.Compared with the radiative charge-transfer process,nonradiative charge transfer is a dominant mechanism at energies above 15 eV.The resonance structures of state-selective charge-transfer cross sections arising from the competition among channels are analysed in detail.The radiative and nonradiative charge-transfer rate coefficients from low to high temperature are presented.     

Low temperature nuclear orientation studies of the magnetic structures of RNiAl4 in applied magnetic fields

The accumulation of iron and arsenic from aqueous solution by lettuce leaves biomass was investigated using Mössbauer and EXAFS spectroscopic techniques. Mössbauer spectroscopy results show that iron is oxidized during sorption while EXAFS results indicate that iron is coordinated by approximately 6 oxygen and 2 carbon atoms while arsenic is coordinated by approximately 4 oxygen atoms with iron as a second neighbor.     

Adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）： A first-principles density-functional study

First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co(200). The preferred site for the carbon atom on the surface is the hollow site, and the preferred site in the subsurface is the octahedral site. There is charge transfer from the surface to the adsorbed carbon atom, and for the most favorable adsorbed structure the charge transfer is largest. Moreover, the energy barriers for the diffusions of carbon atoms on the surface and from the surface into the subsurface and then back to the surface are calculated in detail. The results indicate that the energy barrier for the diffusion of carbon atoms on the surface is comparable to that from the subsurface to the surface. The results imply that both the direct surface nucleation and the surface segregation from Co bulk can be observed in the chemical vapor deposition growth of graphene on Co(200)substrate, which can gain a new insight into the growth mechanism of graphene.     

Cesium adsorption on the β2-GaAs(001) surface

The results of first-principles calculations of the cesium adsorption energy on the β2-GaAs(001) surface performed within approaches of the density functional theory are presented for two possible terminations of the surface. It is shown that, among the considered high-symmetry positions, the energy-preferred position for cesium is position T ₃ when the surface layer contains arsenic and position T ₄ for gallium terminated surface. Cesium introduces insignificant perturbations in the positions of surface-layer atoms, and surface dimers do not break even in the case of adsorption at the dimer bridge and top positions. It is shown that cesium bonding to the GaAs (001) substrate can be explained by sp hybridization of arsenic and gallium orbitals as well as by formation of cesium states mixed with delocalized states of a clean surface. At low coverage, more preferable adsorbate sites are those with nearest neighbor arsenic atoms for both surface terminations.     

Effect of coverage by carbon on the possibility of forming an interstitial solid solution in Fe(001) and Fe(111) subsurface layers

The interaction between carbon adatoms as a function of the coverage of the Fe(001) and Fe(111) surfaces by carbon has been theoretically investigated using first-principles calculations in terms of the density functional theory. It has been established for the first time that the sequential filling of the upper surface layer by carbon atoms leads to the embedding of a part of atoms in the subsurface iron layer due to the their collective interaction, which provides the possibility of forming the interstitial solid solution. It has been demonstrated that the high coverage of the (001) surface by carbon leads to a considerable decrease in the energy barrier to the diffusion of carbon atoms into the subsurface layer as compared to the diffusion barrier for single atoms.     

Nanoscale peculiarities of the thermally stimulated surface autosegregation of covalent crystals: Gallium arsenide

Nanoscale changes in the morphology and elemental composition of cleavage surfaces of gallium arsenide crystals, which arise due to thermally stimulated surface autosegregation, are investigated in detail and systematized. It is shown that, depending on the annealing conditions (temperature, duration, and evacuation), gallium arsenide dissociates, forming submicron nonstoichiometric layers on the surface or local phases of arsenic, gallium, and gallium oxide. The mechanism and nature of autosegregation are determined by the competing processes of arsenic sublimation and its surface diffusion with an activation energy of ～31 kJ/mol. The migration of arsenic atoms is described with the help of a crystallochemical model. The nanomorphology of the surface phases includes arsenic and gallium nanoparticles with sizes of 10-200 nm, their agglomerates, and gallium oxide nano- and microcrystallites combined in plate- and chainlike configurations.     

Calculation of the energy of binding of titanium and scandium complexes to the surface of carbon nanotubes

Complexes of zigzag-type carbon nanotubes (CNTs) with transition metal atoms, scandium and titanium, were studied. It was demonstrated that the energy of binding of both atoms with a carbon surface decreases whereas the rate of diffusion along the surface increases with increasing nanotube diameter. The rate constant of migration of scandium atoms over a CNT surface are several orders of magnitude higher than that for titanium atoms, because the CNT surface—Sc atom binding energy is substantially lower.     

单晶硅纳米切削中C–C键断裂对金刚石刀具磨损的影响

本文基于分子动力学方法模拟金刚石刀具纳米切削单晶硅, 从刀具的弹塑性变形、C–C键断裂对碳原子结构的影响以及金刚石刀具的石墨化磨损等方面对金刚石刀具的磨损进行分析, 采用配位数法和6元环法表征刀具上的磨损碳原子. 模拟结果表明: 在纳米切削过程中, 金刚石刀具表层C–C键的断裂使其两端碳原子由sp³杂化转变为sp²杂化, 同时, 表面上的杂化结构发生变化的碳原子与其第一近邻的sp²杂化碳原子所构成的区域发生平整, 由金刚石的立体网状结构转变为石墨的平面结构, 导致金刚石刀具发生磨损; 刀具表面低配位数碳原子的重构使其近邻区域产生扭曲变形, C–C键键能随之减弱, 在高温和高剪切应力的作用下, 极易发生断裂; 在切削刃的棱边上, 由于表面碳原子的配位严重不足, 断开较少的C–C键就可以使表面6 元环中碳原子的配位数都小于4, 导致金刚石刀具发生石墨化磨损.     

Encapsulation of methane molecules into carbon nanotubes

Methane gas (CH₄) is a chemical compound comprising a carbon atom surrounded by four hydrogen atoms, and carbon nanotubes have been proposed as possible molecular containers for the storage of such gases. In this paper, we investigate the interaction energy between a CH₄ molecule and a carbon nanotube using two different models for the CH₄ molecule, the first discrete and the second continuous. In the first model, we consider the total interaction as the sum of the individual interactions between each atom of the molecule and the nanotube. We first determine the interaction energy by assuming that the carbon atom and one of the hydrogen atoms lie on the axis of the tube with the other three hydrogen atoms offset from the axis. Symmetry is assumed with regard to the arrangement of the three hydrogen atoms surrounding the carbon atom on the axis. We then rotate the atomic position into 100 discrete orientations and determine the average interaction energy from all orientations. In the second model, we approximate the CH₄ molecule by assuming that the four hydrogen atoms are smeared over a spherical surface of a certain radius with the carbon atom located at the center of the sphere. The total interaction energy between the CH₄ molecule and the carbon nanotube for this model is calculated as the sum of the individual interaction energies between both the carbon atom and the spherical surface and the carbon nanotube. These models are analyzed to determine the dimensions of the particular nanotubes which will readily suck-up CH₄ molecules. Our results determine the minimum and maximum interaction energies required for CH₄ encapsulation in different tube sizes, and establish the second model of the CH₄ molecule as a simple and elegant model which might be exploited for other problems.     

CH基团与金刚石(111)面的碰撞反应及其对碳膜生长的影响

等离子体增强化学气相沉积技术中的碳膜选择性自组装机理是高性能碳膜制备过程中的挑战性基础课题.采用经典分子动力学方法,模拟了不同能量(1.625-65 eV)的CH基团在清洁金刚石和吸氢金刚石(111)面上的轰击行为,获得了吸附、反弹、反应等各类事件的发生概率,并据此探讨了含氢碳膜制备过程中CH基团的贡献.结果表明,随着入射能量的增加,CH基团对薄膜生长的贡献由单纯的吸附、反弹机理向反应、吸附混合机理转变,其中最主要的反应过程是释放一个或两个氢原子的反应,而释放氢分子的反应则很少发生.这些反应不仅使薄膜生长过程更均匀、薄膜表面更平整,还降低了薄膜的氢含量.生长机理的转变导致低能量条件下所成薄膜中的多数碳原子都包含一个氢原子作为配位原子,而高能量条件下的薄膜中的碳原子则很少有氢原子作为配位原子.另外,通过分析sp~3-C和sp~2-C数目的变化,研究了CH基团对金刚石基底的破坏作用.     

Reconstruction dependence of the etching and passivation of the GaAs(001) surface

The microscopic nature of the selective interaction of iodine with an As- and Ga-stabilized GaAs(001) surface has been investigated by the photoelectron emission and ab initio calculations. The adsorption of iodine on the Ga-stabilized (4 × 2)/c(8 × 2) surface leads to the formation of the prevailing chemical bond with gallium atoms; to a significant redistribution of the electron density between the surface Ga and As atoms; and, as a result, to a decrease in their binding energy. Iodine on the As-stabilized (2 × 4)/c(2 × 8) surface forms a bond predominantly with surface arsenic atoms. Such a selective interaction of iodine with the reconstructed surfaces gives rise to the etching of the Ga-stabilized surface and the passivation of the As-stabilized surface; this explains the layer-by-layer (“digital”) etching of GaAs(001) controlled by the reconstruction transitions on this surface.     

Chemical state of carbon atoms on the surface of nanodiamond particles

Auger electron spectroscopy study of the chemical state of carbon atoms on the surface of nanodiamond particles is performed. Auger spectra of nanodiamond particles indicate that carbon atoms in nanodiamond are in the same state as those in graphite, i.e., in the σ _s ¹ σ _p ² π¹ state, but the π band is displaced 1 eV in energy below the Fermi level. The surface of nanodiamond particles is inert with respect to the ambient medium.     

A theoretical examination of the chemisorption of benzene on Si(100)−(2 × 1)

A theoretical examination of the structure of the adsorbed state of benzene on the Si(100)-(2 × 1) surface is discussed. A number of potential candidate structures are examined. The local minimum in the total energy for each structure has been calculated with respect to variations in the atomic coordinates for the adsorbed benzene structure and the first four layers of the substrate. The preferred structure is the one with the lowest value for the total energy. This structure, in agreement with the experimental observations, describes a topology for the adsorbed benzene with no Si-H bonds and all the C-H bonds remaining intact. The benzene ring is oriented at an angle of 24° from the surface plane. Four of the carbon atoms are bonded to the silicon surface. Two silicon atoms are each bonded to two carbon atoms.