Adsorption and diffusion of a Si adatom on the H/Si(1 1 1) surface: comparison with the H/Si(0 0 1) surface

Using a first-principles method, we investigate the adsorption and diffusion of a Si adatom on the H-terminated Si(1 1 1) substrate, which would be useful in understanding the initial stages of Si homoepitaxy using a H surfactant. The adatom substitutes H atom(s) to form a monohydride structure or a dihydride structure. In forming the monohydride structure, the energy barrier for H substitution is absent. The adatom migrates on the surface with alternating its chemical state between monohydride and dihydride. These behaviors of the adatom are quite similar to those on the H/Si(0 0 1)2 × 1 surface, despite the significant difference in the substrate structure between both orientations. The resulting diffusion barrier is 1.30 eV, which is also comparable to that on the H/Si(0 0 1)2 × 1 surface.     

The role of HH interactions in the formation of ordered structures on Ni and Pd single crystals

The interaction between H adatoms on a surface is calculated within the embedded cluster model of chemisorption. The model is first applied to the case of two H atoms on a free electron surface. The interaction energy is found to be an oscillatory function of the H-H separation R_ab. Application of the free electron model to the problem of chemisorption on transition metal surfaces leads to unphysical results with the prediction of formation of ordered H overlayers which are not observed in LEED experiments. We next include the l = 2 TM muffin tins. Results for H adsorption on the low index faces of Ni and Pd substrates are presented. Graphitic structures are predicted for the (111) faces of both Ni and Pd with the H atoms occupying both types of three-fold hollow sites on the surface. This agrees with the results of LEED experiments for H/Ni(111). Comparison with experiment is not possible in the case of H/Pd(111) owing to the lack of low temperature studies for that system. Zig-zag chains with the H atoms adsorbed in sites of three-fold coordination on alternate sides of the TM(110) rows are predicted for both Ni and Pd. This is in agreement with the results of He diffraction experiments for H/Ni(110). No structure determination has been done for H/Pd(110). Adsorption in the four-fold centre sites for H on the (100) faces of Ni and Pd is found to be unfavourable. The H atoms are expected to adsorb in sites of three-fold symmetry below the (100) surface for H on Pd with formation of a c(2 × 2) structure in agreement with the LEED observations. For H/Ni(100) the H atoms are believed to adsorb above the surface, away from the centre site and to bond to two surface Ni atoms. No short-range ordered structures are predicted in this case.     

第一性原理研究H_2O分子在CaCO_3(104)表面吸附

基于密度泛函理论的第一性原理方法模拟研究H_2O在CaCO_3(104)表面的吸附特征.首先,研究H_2O分子在CaCO_3(104)表面的顶位、桥位(短桥位、长桥位)和穴位上垂直和平行表面两种类型下的8种高对称吸附结构模型,结合吸附能和稳定吸附构象确定最优吸附位.而后,基于H_2O/CaCO_3(104)最优吸附结构模型,研究吸附前后H_2O和CaCO_3(104)表面的物理结构、电子结构(Mulliken电荷布居数、态密度、电子局域函数)的特征,分析H_2O/CaCO_3(104)表面之间的相互作用以及成键机理.研究结果:吸附能和体系稳定构象显示H_2O分子/CaCO_3(104)表面的最稳定吸附结构为穴位-平行.在穴位-平行位吸附后,H_2O分子的O-H键长和H-O-H键角均发生改变; CaCO_3晶体平行和垂直(104)表面方向上原子位置均发生改变,表面层变化最大;即吸附作用对H_2O分子和CaCO_3晶体的物理结构均产生较大影响; H_2O/CaCO3(104)最优吸附体系的Mulliken电荷布居数、电子态密度、电子局域函数的研究均说明H_2O分子与CaCO3(104)之间存在电子的转移形成化学键.其中,Ca-O(H_2O)形成离子键,H(H_2O)-O(CaCO_3)之间存在氢键作用.本文研究揭示了方解石表面水湿性的原因,同时为方解石润湿性的深入研究奠定基础.     

第一性原理研究O2和H2O在ZnO (101 ̅0)表面上的吸附行为

运用基于密度泛函理论(DFT)的第一性原理方法研究了O2和H2O单分子在ZnO (101 ̅0)表面上的吸附行为。吸附位点主要考虑了表面的Zn顶位和Zn桥位,同时也考虑了其它可能的吸附行为。对于O2在ZnO (101 ̅0)表面上的吸附设计了9个模型,H2O在ZnO (101 ̅0)表面上的吸附设计了12个模型。通过形成能计算发现,O2在表面上的吸附为正值,H2O的吸附为负值。O2和H2O单分子在表面上发生分子吸附,未见解离形态。对于O2吸附最稳定的结构是O2分子与表面相邻的Zn原子形成了Znslab1-Oads1-Oads2-Znslab2桥连键。其它较为稳定的结构是Oads1原子迁移到下一个表面重复晶胞的O原子位置附近,在表面上形成了Znslab1-Oads1键,同时Oads2原子扩散至表面沟渠上方。对于H2O吸附,不论以何种方式吸附结构都比较稳定。其中最稳定的构型是Oads迁移到下一个表面重复晶胞的O原子位置附近,形成了Znslab1-Oads键以及Oslab3-H氢键。另外较稳定的构型是Oads迁移到ZnO (101 ̅0)表面台阶上方,形成了Znslab1-Oads键以及Oslab1-H氢键。     

质子交换MgO:LiNbO3波导的双层结构

本文报导MgO:LiN_bO₃质子交换波导X射线双晶衍射和红外吸收的实验结果。这些结果表明质子交换波导由浅表面层和深表面层构成。浅表面层是一个连续应变层,有着大量随机排列的O—H—O形式的缔合OH^-基团。深表面层是一个均匀应变层,其内H⁺以自由OH^-基团形式出现。质子交换波导折射串不稳定性与双层结构中的结构驰豫密切相关。通过对质子交换过程的分析,提出两条避免双层结构的途径,其一为降低交换剂中的H⁺浓度,另一条是采用有限源工艺。     

Effect of elastic excitations on the surface structure of hadfield steel under friction

The structure of the Hadfield steel (H13) surface layer forming under dry friction is examined. The deformation of the material under the friction surface is studied at a low slip velocity and a low pressure (much smaller than the yields stress of H13 steel). The phase composition and defect substructure on the friction surface are studied using scanning, optical, and diffraction electron microscopy methods. It is shown that a thin highly deformed nanocrystalline layer arises near the friction surface that transforms into a polycrystalline layer containing deformation twins and dislocations. The nanocrystalline structure and the presence of oxides in the surface layer and friction zone indicate a high temperature and high plastic strains responsible for the formation of the layer. It is suggested that the deformation of the material observed far from the surface is due to elastic wave generation at friction.     

Effects of subsurface Na,H and C on the bonding of carbon to nickel surfaces

This paper reports the results of a theoretical study of Na, H and C subsurface atomic species in nickel and demonstrates how these interstitial atoms influence the reactivity of the Ni(111) surface and the structure of carbon species adsorbed on the surface. The benzene molecule, C₆H₆, in planar and nonplanar geometries, is used to probe bonding at the surface. Adsorption energies are calculated by ab initio configuration interaction techniques modelling the surface as an embedded cluster. Adsorption energies of planar C₆H₆ at the most stable, three-fold, adsorption site are 18 kcal/mol for the Ni(111) surface, and 10, 19 and 44 kcal/mol in the presence of the Na, H and C interstitials, respectively. The energies required for the planar to puckered distortion are 99 kcal/mol on Ni(111), 69 kcal/mol with the Na interstitial, 83 kcal/mol with H, and 134 kcal/mol with C compared to 198 kcal/mol for distortion of C₆H₆ in the gas phase. The possible relevance of these results to the nucleation of diamond on nickel are discussed. The results indicate that subsurface Na stabilizes tetrahedrally bonded carbon subunits of the diamond structure while subsurface C may make it easier for the overlayer to revert to a planar graphite structure.     

A LEED study of the Si{100}(1 × 1)H surface structure

Extensive LEED intensity-energy data have been collected for a Si{100}(1 × 1)H surface and dynamical theory LEED calculations have been performed using an ideal unreconstructed Si(100) surface to model this structure. Agreement between experiment and theory is good indicating that the probable structure for this surface does involve (weakly scattering) H atoms on the “dangling bonds” of an unreconstructed Si(100) surface, and that difficulties in achieving good agreement between experiment and theory for the clean Si{100}(2 × 1) surface is more probably due to deficiencies in the model structure than to deficiencies in the non-structural aspects of the LEED theory.     

Self-consistent electronic structure for a Mo (001) surface with saturated H adsorption

The band structure for a Mo (001) surface covered with a saturated monolayer of hydrogen is calculated self-consistently using the pseudopotential method in a mixed-basis representation. Two adsorbate bands are found below the bottom of the molybdenum bulk bands. Most of the intrinsic surface states of the clean (001) surface also exist on the hydrogen covered surface at lower energies. The results are used to identify H induced structures observed in recent photoemission studies of hydrogen on W (001).     

Hydrogen chemisorption on the 100 (2 × 1) surfaces of Si and Ge

This paper combines a theoretical study of the Si(100) surface having a monolayer of atomic hydrogen chemisorbed to it with an experimental study of the analogous Ge(100) and Ge(110) surfaces. In the theoretical work the underlying (100) silicon surface is taken to be reconstructed according to the Schlier-Farnsworth-Levine pairing model with the hydrogen located on the unfilled tetrahedral bonds of this structure. Self-consistent calculations of the electronic potential, charge density, spectrum, and occupied surface density of states are carried out. The force on the hydrogen atoms is then calculated using the Hellman-Feynman theorem. This force is found to be close to zero, confirming that the hydrogen atoms are indeed at the equilibrium position for the chosen silicon geometry. Features in the calculated photoemission spectrum for the Si(100) 2 × 1 : H surface are discussed in terms of related features in the photoemission spectrum of Si(111) : H, but are found not to agree with the previously measured photoemission spectrum of Si(100) 2 × 1 : H. Measured photoemission and ion-neutralization spectra for Ge(100) 2 × 1 : H agree in their major features with what is calculated for Si(100) 2 × 1 : H, however, suggesting that the Ge(100) 2 × 1 : H surface is reconstricted according to the pairing model. Similarly, measured spectra for clean Ge(100) 2 × 1 agree with calculations for the row dimerized Si(100) surface.     

不同密度氢吸附金刚石(100)表面的微观结构

利用基于广义梯度近似的密度泛函理论,计算了金刚石(100)表面不同氢吸附密度的平衡态几何结构和态密度.结果表明对于2×1构型,在平行和垂直表面两个方向上发生弛豫,而1×1构型仅在垂直表面方向上发生弛豫.另外,清洁2×1,2×1 ∶0.5H和1×1 ∶1.5H表面,带隙中存在空表面态;而对于1×1 ∶2H和2×1 ∶H两种表面结构,空表面态上移进入导带,带隙中不存在表面态.结合电荷密度分布,探讨了金刚石(100)不同构型和氢吸附密度表面的表面态诱发机理. 关键词： 氢吸附 金刚石 弛豫 表面态     

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.     

Hydrogen-induced metallization of the 3C-SiC(0 0 1)-(3 × 2) surface

A surprising metallization of the SiC(0 0 1)-(3 × 2) surface induced by hydrogen adsorption was discovered in recent experiments. The effect was ascribed to dangling bonds created on the third layer of the surface system by H adsorption and stabilized by steric hindrance. We have investigated the surface metallization by density functional calculations. Our total-energy minimizations show that dangling bonds on the third layer are very unstable. Instead, H adatoms form angular Si-H-Si bonds on the third layer after the asymmetric dimers on the top layer have been saturated by H forming monohydrides. The novel Si-H-Si bonds on the third layer give rise to a metallic surface, indeed. But the mechanism for metallization is very different from the one suggested originally. Likewise, H atoms can also occupy bridge positions in angular Si-H-Si bonds on the second layer and induce metallization, as well. In addition to monohydrides on the top-layer dimers, we have also investigated dihydride surfaces with additional H on the second and/or third layer. The dihydride surface structure with H adsorbed on both the second and third layers is energetically most favorable and is also metallic. In all three cases the new Si-H-Si bonds are the origin of the surface metallization while its nature is somewhat more intricate, as will be discussed.     

Growth mode and interface structure of Ag on the HF-treated Si(111):H surface

A growth mode and interface structure analysis has been performed for Ag deposited at a high temperature of 300°C on the HF-treated Si(111):H surface by means of medium-energy ion scattering and elastic recoil detection analysis of hydrogen. The measurements show that Ag grows in the Volmer-Weber mode and that the Ag islands on the surface are epitaxial with respect to the substrate. The preferential azimuthal orientation is A-type only when Ag is deposited slowly. The interface does not reconstruct to the √3 × √3-Ag structure, which is normally observed for Ag deposition above 200°C on the Si(111)7 × 7 surface, but retain bulk-like structure. The presence of hydrogen at the interface is demonstrated after deposition of thick (1100 Å) Ag films. However, the amount of hydrogen at the interface is not a full monolayer. This partial desorption of hydrogen from the interface explains why the Schottky barrier heights of Ag/Si(111):H diodes are close to those of Ag/Si(111)7 × 7 and Ag/Si(111)2 × 1.     

The surface structure of Si(100) surfaces using averaged leed: I. The(1 × 1)H structure

As a preliminary to the study of the Si(100) (2 × 1) clean surface structure, extensive LEED data has been collected from a sharp (1 × 1)H structure on this surface, and has been subjected to constant momentum transfer averaging. The results are markedly kinematical and can best be interpreted by hydrogen adsorbed on an unreconstructed Si(100) surface whose top (Si) layer spacing is contracted by less than 10%. These conclusions are weakened by possible interference of vestiges of multiple scattering information left in the averages.     

Structure Sensitive Reaction Channels of Molecular Hydrogen on Silicon Surfaces

The ability of the Si(001) surface to adsorb H2 molecules dissociatively increases by orders of magnitude when appropriate surface dangling bonds are terminated by H atoms. Through molecular beam techniques the energy dependent sticking probability at different adsorption sites on H-precovered and stepped surfaces is measured to obtain information about the barriers to adsorption, which decrease systematically with an increase in coadsorbed H atoms. With the help of density functional calculations for interdimer adsorption pathways, this effect is traced back to the electronic structure of the different adsorption sites and its interplay with local lattice distortions.     

ZrMn2（110）表面结构及吸氢机理的第一性原理研究

采用基于密度泛函理论(DFT)的平面波赝势(PW-PP)方法,研究了ZrMn2（110）清洁表面结构和氢原子在表面的吸附。弛豫表面结构的计算结果表明表面结构的最表层为曲面,且表面结构的原子间隙变小。由1Zr2Mn原子组成的空位是氢原子吸附在ZrMn2（110）表面的最佳吸附位,吸附能为3.352 eV,氢原子吸附后离表面的距离为1.140 Å。Mulliken电荷布居分析表明吸附的氢原子与表面原子的相互作用主要是接近氢原子的第一层原子与氢原子的相互作用。过渡态计算表明被吸附的氢原子进入表面内部需克服的最大势垒为1.033 eV。     

Structure determination of Pb/Ge(111)-β-(√3 × √3)R30° by dynamical low-energy electron diffraction analysis and first-principles calculation

We have determined the atomic structure of the Pb/Ge(111)-β-(√3 × √3)R30° surface, which was shown to exhibit a large Rashba spin splitting in a metallic surface state by dynamical low-energy electron diffraction analysis. The Pb coverage for the optimized atomic structure is 4/3 with one Pb atom located at every third H(3) site of the bulk-truncated Ge(111) surface and the other three near the T(1) sites but slightly displaced towards the T(4) sites. The determined atomic structure agrees well with the energetically optimized one obtained from the first-principles calculation. The calculation also revealed that the potential for the Pb atoms on the H(3) sites is very soft along the surface normal, suggesting that their vertical position is distributed within a range of about 0.2-0.3 ?. The previously proposed phase transition associated with the surface melting is discussed.     

B、N、S掺杂石墨烯表面质子吸附的第一性原理研究

表面吸附是石墨烯中质子(H~+)输运的基础步骤.本文基于第一性原理计算研究了B、N、S掺杂对石墨烯表面H~+吸附行为的影响.结果表明,B、N、S掺杂对石墨烯的晶体结构、内聚能及电子性质有重要影响,且影响程度与掺杂元素的性质密切相关,进而导致对石墨烯表面H~+吸附行为产生不同程度的影响.从吸附能的观点看,N、B、S掺杂对石墨烯表面H~+的吸附有利.研究结果对石墨烯在氢贮存、氢同位素分离、燃料电池等领域的应用具有重要的指导意义.     

Hydrogen chemisorption on Si(111)√ 3×√ 3R30∘-B passivated surface studied by thermal desorption and scanning tunneling microscopy

Atomic H chemisorption on the Si(111)√ 3×√ 3R30^°-B surface has been studied by thermal desorption spectroscopy (TDS) and scanning tunneling microscopy (STM). The B-modified Si surface is known to be inert towards adsorbates, since the surface dangling bonds of Si adatoms are passivated by B atoms sitting in sub-surface sites. However, it was found that even on a perfectly passivated surface, H is adsorbed on the surface by destroying the original √ 3 × √ 3 structure. STM observations revealed that H exposure led to the creation of defects at surface sites, and H was subsequently adsorbed as Si-monohydride at these sites. H exposure also caused cluster island formation at the top surface. The islands are composed of hydrogenated amorphous Si atoms or B-hydrogen complexes.