Atomic structure of β-SiC(100) surfaces: an ab initio study

We examine several different reconstructions of the β-SiC(100) surface by the ab initio Car-Parrinello method. Our results confirm that the lowest energy c(2 × 2) reconstructed surface consists of triply bonded carbon dimers in a bridging position between neighboring underlying silicon dimers. Added hydrogen atoms bond to the carbon dimers, resulting in a lengthened double-bonded dimer, and a larger separation for the underlying silicon dimers, although those Si bonds do not disappear. The most stable structure found for the (3 × 2) reconstructed surface with a 1/3 monolayer excess of silicon is an alternate dimer row structure rather than the added dimer row model proposed by others. The energetics of various surface reactions that may be involved in growth of SiC are discussed.     

Photoelectron diffraction imaging for C2H2 and C2H4 chemisorbed on Si(100) reveals a new bonding configuration

A new adsorption site for adsorbed acetylene on Si(100) is observed by photoelectron imaging based on the holographic principle. The diffraction effects in the carbon 1s angle-resolved photoemission are inverted (including the small-cone method) to obtain an image of the atom's neighboring carbon. The chemisorbed acetylene molecule is bonded to four silicon surface atoms. In contrast to the C2H2 case, the image for adsorbed C2H4 shows it bonded to two Si surface atoms.     

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.     

金刚石延(111)面生长的第一性原理研究

利用密度泛函理论(DFT)对碳原子在镍(111)表面吸附结构进行了计算，得到了吸附能以及态密度 (density of state, DOS)分布，分析了吸附在镍(111)面的碳原子和金刚石(111)面的碳原子的分波态密度(PDOS)，结果表明吸附在镍表面的碳原子具有与金刚石表面碳原子相类似的电子结构特点，即两者都存在孤对的和成键的sp³杂化电子,进而发现吸附在镍表面的碳原子极易与金刚石表面相互作用形成稳定的类金刚石几何结构. 关键词： 密度泛函理论 化学吸附 电子结构 金刚石生长     

Real time investigation of the growth of silicon carbide nanocrystals on Si(1 0 0) using synchrotron X-ray diffraction

The growth of silicon carbide nanocrystals on Si(1 0 0) is studied by synchrotron surface X-ray diffraction (SXRD) during annealing at high temperature. A chemisorbed methanol monolayer is used as carbon source, allowing to have a fixed amount of carbon atoms to feed the growth. At room temperature, minor changes in the 2 × 1 reconstruction of silicon are observed due to the formation of Si-O-CH₃ and Si-H bonds from methanol molecules. When annealed at 500 °C, carbon incorporation into the silicon leads only to local modifications of the surface structure. Above 600 °C, tri-dimensional silicon carbide nanocrystals growth takes place, together with surface roughening and sharp decrease of domain sizes of the 2 × 1 reconstruction. The different processes taking place at each temperature are clearly distinguished and identified during the real time SXRD measurements.     

Modification of the structural and electronic properties of graphene by the benzene molecule adsorption

A survey of the literature data on the adsorption of benzene on graphene or carbon nanotubes indicates that the distance between the graphene sheet and benzene molecule is determined from weak van der Waals forces (∼3.40 Å). In our theoretical study, it was found that the benzene/graphene structure (in a specific configuration with carbon atoms located at the atop positions, stacked directly on the top of each other) forms strong covalent bonds, if the distance between the graphene and benzene is about 1.60 Å. Such a short distance corresponds to about a half of the usual separation between the graphite layers. It was also shown that at such a short distance the carbon atoms of the benzene molecule move towards the graphene sheet, whereas the hydrogen atoms move in a different direction, thus breaking the benzene planar structure.     

A study of Ga layers on Si(1 0 0)-(2 × 1) by SR-PES: Influence of adsorbed water

Results for deposition and thermal annealing of gallium on the Si(1 0 0)-(2 × 1) surface achieved by synchrotron radiation photoelectron spectroscopy (SR-PES) and low energy electron diffraction (LEED) are presented. In addition to deposition of Ga on a clean surface, the influence of water adsorption on the arrangement of gallium atoms was also studied. The results on Ga deposition at a higher temperature (490 °C) are consistent with a Ga ad-dimer model showing equivalent bond arrangement of all Ga atoms for coverages up to 0.5 ML. The deposition onto a surface with adsorbed water at room temperature led to a disordered gallium growth. In this case gallium atoms bind to silicon dimers already binding fragments of adsorbed water. A subsequent annealing of these layers leads to a surface structure similar to the Ga-(2 × 2), however, it is less ordered, probably due to the presence of silicon oxides formed from water fragments.     

Molecular dynamics simulation of CH3 interaction with Si(1 0 0) surface

Molecular dynamics simulations of the CH₃ interaction with Si(1 0 0) were performed using the Tersoff-Brenner potential. The H/C ratio obtained from the simulations is in agreement with available experimental data. The results show that H atoms preferentially react with Si. SiH is the dominant form of SiH_x generated. The amount of hydrogen that reacts with silicon is essentially energy-independent. H atoms do not react with adsorbed carbon atoms. The presence of C-H bonds on the surface is due to molecular adsorption.     

Hydrogen-induced surface metallization of beta-SiC(100)-(3x2) revisited by density functional theory calculations

Recent experiments on the silicon terminated (3 x 2)-SiC(100) surface indicated an unexpected metallic character upon hydrogen adsorption. This effect was attributed to the bonding of hydrogen to a row of Si atoms and to the stabilization of a neighboring dangling bond row. Here, on the basis of density-functional calculations, we show that multiple-layer adsorption of H at the reconstructed surface is compatible with a different geometry: in addition to saturating the topmost Si dangling bonds, H atoms are adsorbed at rather unusual sites, i.e., stable bridge positions above third-layer Si dimers. The results thus suggest an alternative interpretation for the electronic structure of the metallic surface.     

金刚石/硅(001)异质界面的分子动力学模拟研究

采用分子动力学方法模拟研究了未重构的金刚石/硅(001)面相接触时界面层原子的弛豫过程及所形成的异质界面的结构特征.硅碳二元系统中原子间的相互作用采用Tersoff多体经验势描述.弛豫前沿[110]与[110]方向界面碳硅原子数之比均为3∶2.界面碳硅原子总数之比为9∶4.弛豫后金刚石与硅界面处晶格匹配方式改变为[110]方向基本上以3∶2关系对准,而[110]方向大致以1∶1关系对准.相应地,界面碳硅原子总数之比接近3∶2.界面下方部分第二层硅原子在弛豫过程中向上迁移至界面是引起这种变化的原因,同时该层其他原子及其底下一到两个原子层厚度的区域在[001]方向上出现一定程度的无序化转变倾向.金刚石/硅异质界面处的硅碳原子发生强烈键合,形成平均键长为0.189nm的硅碳键.研究证实,晶格匹配主要呈现界面及其附近硅原子迎合界面碳原子排列的特点. 关键词： 金刚石 硅 异质界面 分子动力学     

Structure and bonding of hydrocarbon plasma generated carbon films: An electron energy loss study

Electron energy loss spectroscopy has been used to study the structure and the bonding in hard amorphous carbon films (aC:H) prepared by plasma decomposition of benzene. EXAFS spectra indicate an amorphous and not a microcrystalline structure for aC:H films. The near-edge structure of the carbon K-amsorption edge reveals a considerable amount of π bonding in the aC:H films. The optical constants were derived by a Kramers-Kronig analysis of the loss functions for energies less than 40 eV. From the sum rule for ε₂, we derive that $\text{1}\text{3}$ of the carbon atoms are trigonally bonded and 273 of the carbon atoms are tetrahedrally bonded.     

辉光放电等离子体辅助XeCl准分子激光溅射沉积碳氮薄膜

利用直流辉光放电等离子体辅助的脉冲激光沉积技术在Si衬底上生长了碳氮薄膜.通过扫描电子显微镜、X射线衍射、X射线光电子能谱、俄歇电子能谱等多种手段,对薄膜的形貌、成分、晶体结构、价键状态等特性进行了分析和确定.结果表明,沉积薄膜为含有非晶SiN和晶态氮化碳颗粒结构,晶态成分呈多晶态,主要为α-C₃N₄相、β-C₃N₄相,晶粒大小为40—60nm.碳氮之间主要以C-N非极性共价键形式相结合. 关键词： 脉冲激光沉积 直流辉光放电 碳氮薄膜     

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.     

基于第一性原理的CVD金刚石涂层表面氧原子作用分析

采用第一性原理方法研究了氧原子在CVD金刚石涂层表面吸附形成的两种氧掺杂结构的差异及脱附CO的难易程度.仿真计算结果表明：氧原子在金刚石表面顶位和桥位吸附形成C=O羰结构和C-O-C醚结构,改变与其直接成键的局部金刚石结构;C-O-C结构吸附能比C=O结构大,其结构更加稳定;C=O结构断键脱附形成CO的能垒比C-O-C结构更低,CVD金刚石涂层表面脱附CO主要是以C=O断键形成;氢终止表面能够增强碳原子之间成键,提高C=O脱附的能垒,而氧终止表面作用相反,降低脱附能垒.     

Investigation of electronic structure and associated nuclear quadrupole interaction of adsorbed fluorine atoms on silicon surface

The electronic energy levels and wave functions of fluorine and chlorine atoms adsorbed at the <111> surface of silicon are obtained by the Hartree-Fock procedure applied to clusters simulating the surface structure. Minimising the total energy with respect to the positions of the halogen atoms, the Si-Cl distance in the adsorbed system was found to be in good agreement with that from a recent SEXAFS measurement, there being no corresponding data presently available for fluorine on silicon surface. The calculated¹⁹ f ^* nuclear quadrupole coupling constants using the electronic wave functions for SiH₃F and the larger cluster Si₄H₉F, simulating the surface, differed substantially in contrast to the situation for the Si-F distance, indicating that the quadrupole coupling is a more sensitive indicator of the adequacy of the cluster chosen to represent the surface system. Experimental results for the coupling constants are awaited for comparison with theory.     

Structure and electronic factors in benzene coordination to Cr(CO)3 and to cluster models of Ni,Pt, and Ag (111) surfaces

Bonding of benzene to a chromium tricarbonyl fragment and to cluster models of silver, nickel, and platinum (111) surfaces is found by means of molecular orbital calculations to be dominated by a benzene donation bond involving its π (e_1g) orbitals and metal d orbitals. Three-fold hollow sites on the clusters are calculated to be most stable for benzene coordination, a conclusion reached in a number of experimental studies of benzene on metal surfaces. On the Ag, Ni, and pt clusters, the benzene CH bonds are found to bend away from the surface by ?2°, 8° and 19°, respectively, a result of carbon atom hybridization to maximize overlap with metal orbitals. For benzene chromium tricarbonyl, the CH bonds are calculated to bend 3° toward the metal, compared to a 1.7° bend reported in a diffraction study. The direction and magnitude of the CH bending are shown to depend on the metal d orbital occupancy (an electronic factor) and the proximity of metal atoms in the adsorption site (a structure factor). Small Kekulé distortions are calculated for the chromium complex and for the C_3v sites on Pt(111). Finally, recent experimental studies showing a decrease in benzene adsorption energy when potassium is coadsorbed on Pt(111) may be understood to result from decreased π donation which accompanies the shift up of the metal d band with cathodic charging.     

Thermally activated reconstruction in Yb-Si(111) thin-film structures

The electronic properties and mechanisms of formation of Yb-Si(111) thin-film structures, produced by room-temperature deposition of Yb atoms on the Si(111)7×7 surface are studied by Auger electron and LEED spectroscopy and the contact potential difference method. A study is also made of the effect of heating to 800 K on the properties of these structures. The interface is shown to form by the Stransky-Krastanov mechanism. Heating the Yb-Si(111) system is found to result in a very high (up to 1 eV) increase of the work function for all Yb atom concentrations on the silicon surface. In the adsorption stage, this increase is due to the growth of 2D ytterbium domains, which is accompanied by the formation of polarized domains from the silicon surface atoms with dangling valence bonds. The dipoles are oriented in such a way that their formation reduces the total energy of the Yb-Si(111) system and increases the work function. In the stage of silicide formation, the increase of the work function under heating is ultimately due to the appearance of a layer of silicon atoms on the Yb-Si(111) surface. Fiz. Tverd. Tela (St. Petersburg) 39, 1672–1678 (September 1997)     

Adsorption stage in the formation of Eu-Si(111) thin-film structures

The adsorption stage in the formation of the Eu-Si(111) interface has been studied within a broad temperature range by thermal and isothermal desorption spectroscopy, low-energy-electron diffraction, Auger electron spectroscopy, and the contact potential difference method. It is shown that the ordering of an adsorbed europium film is accompanied by silicon surface reconstruction throughout the coverage range studied, 0<θ≤1.8. This self-organized process is also shown to be thermally activated. Ordered adsorbed europium layers have been found to be made up of 2D islands, whose structure depends on the amount of the metal deposited on the surface. The energy required to remove atoms from an island to vacuum has been determined. This energy decreases with decreasing 2D lattice constant of the islands. This pattern of its variation is accounted for, in the final count, by the decrease of the number of the Si surface atoms not bound directly to Eu atoms.     

High resolution NEXAFS studies of aromatic molecules adsorbed and condensed on Ni(111)

High resolution near-edge X-ray absorption fine structure measurements have been performed on benzene, pyridine and pyrazine adsorbed and condensed on Ni(111). The carbon K-edge multilayer data show the splitting of the e_2u level of benzene into b₁ and a₂ levels for pyridine and into b_3u and a_u levels for pyrazine; the corresponding π resonances are asymmetric due to the vibrational fine structure. At the nitrogen K-edge the transitions into the a₂ and a_u levels are not observed. The benzene data suggest that the Rydberg orbitais are quenched in the condensed phase and that the broad structure above a photon energy of ~ 300 eV is made up of (at least) two σ resonances. On adsorption the π resonances are considerably broadened at the adsorption edges of atoms which interact strongly with the substrate.     

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.