Epitaxial growth and erosion on (110) crystal surfaces: structure and dynamics of interfacial States

We study nonequilibrium interfacial states in multilayer epitaxial growth and erosion on rectangular symmetry crystal surfaces. We elucidate a recently observed transition between two kinds of rippled states on (110) surfaces. We predict several novel interface states intervening, via consecutive transitions, between the two rippled states. We predict coarsening laws of the dynamics of the rippled and the intervening states on (110) crystal surfaces.     

Study of translational,librational and intra-molecular motion of adsorbed liquid water monolayers at various TiO2 interfaces

Equilibrium classical molecular dynamics (MD) simulations have been performed to investigate the vibrational motion of water in contact with rutile-(110), rutile-(100), rutile-(001), anatase-(101) and anatase-(001) surfaces at room temperature (300?K). The vibrational density of states (VDOS) of the first adsorbed monolayer of liquid water has been analysed for each surface. These have been compared with reported experimental INS values involving rutile and anatase polymorph surfaces, along with ab initio MD results. It is observed that good qualitative agreement is obtained for the rutile-(110) and the anatase-(101) surfaces with the corresponding experimental VDOS. A significant contribution from librational dynamics is found for planar rutile surfaces, but no such demarcation is seen in the experimental VDOS.     

Cu 表面性质的第一性原理分析

采用第一性原理赝势平面波方法, 计算并详细分析了面心立方Cu晶体及其 (100), (110) 和 (111) 这3个低指数表面的原子结构、 表面能量及表面电子态密度. 表面能的计算结果表明, Cu (111) 表面的结构稳定性最好, Cu (100) 表面次之, Cu (110)表面的结构稳定性最差. 3个表面的表面原子弛豫量随着层数的增加而逐渐减弱. Cu (110) 表面的最表层原子相对收缩最大, Cu (100)表面次之, Cu (111) 表面的最表层原子相对收缩最小. 表面原子弛豫不仅引起表面几何结构的变化, 而且使表面层原子的电子态密度峰形相对晶体内部发生变化, 这是表面能产生的主要原因, 而Cu (110)表面相对于Cu (100)与Cu (111)表面具有高表面活性的主要原因则源于其表面层原子电子态密度在高能级处的波峰相对晶体内部显著的升高. 关键词： Cu 晶体 表面结构 表面能 态密度     

Cluster model approach for electronic structure of Si and Ge(111) and GaAs(110) surfaces

For the purpose of exploring how realistic a cluster model can be for semiconductor surfaces, extended Huckel theory calculations are performed on clusters modeling Si and Ge(111) and GaAs(110) surfaces as prototypes. Boundary conditions of the clusters are devised to be reduced. The ideal, relaxed, and reconstructed Si and Ge(111) surfaces are dealt with. Hydrogen chemisorbed (111) clusters of Si and Ge are also investigated as prototypes of chemisorption systems. Some comparison of the results with finite slab calculations and experiments is presented. The cluster-size dependence of the calculated energy levels, local densities of states, and charge distributions is examined for Si and Ge(111) clusters. It is found that a 45-atom cluster which has seven layers along the [111] direction is large enough to identify basic surface states and study the hydrogen chemisorption on Si and Ge(111) surfaces. Also, it is presented that surface states on the clean Si and Ge(111) clusters exist independent of relaxation. Further, the calculation for the relaxed GaAs(110) cluster gives the empty and filled dangling-orbital surface states comparable to experimental data and results of finite slab calculations. The cluster approach is concluded to be a highly useful and economical one for semiconductor surface problems.     

Electronic structure of ideal and relaxed InSb(110) surfaces

We report electronic structure calculations for the ideal and relaxed InSb (110) surfaces which were carried out using the tight binding scattering theoretic method. The bulk material is described by a realistic ETBM Hamiltonian and spin-orbit coupling has been taken into account explicitly. Our results show, that the spin-orbit interaction has only small influence on the surface electronic structure of InSb(110). Our results are discussed in terms of surface band structures, wavevector-resolved layer densities of states and angular-resolved weighted layer densities of states.     

Relaxation and electronic states of Au(100), (110) and (111) surfaces

Using a first-principles method based on density functional theory, we investigate the surface relaxation and electronic states of Au(100), (110) and (111) surfaces. The calculated results show that the relaxations of the (100) and (110) surfaces of the metal are inward relaxations. However, the Au(111) surface shows an ‘anomalous’ outward relaxation, although several previous theoretical studies have predicted inward relaxations that are contrary to the experimental measurements. Electronic densities of states and the respective charge density distribution along the Z-axis of the relaxed surfaces are analyzed, and the origin of inward and outward relaxation is discussed in detail.     

Reconstruction behaviour of fcc(110) transition metal surfaces and their vicinals

The fcc(110) surfaces are well known for their strong tendency to missing-row (MR) type reconstructions either in the clean state (Au, Pt) or driven by adsorbates (Ni, Cu, Pd, Ag). The present knowledge on the different reconstruction behaviour of flat (110) surfaces is reviewed. The survey focuses on recent scanning tunneling microscopy (STM) studies, which for the first time also elucidate the dynamics of the reconstruction process for the various systems. An overview of our recent STM and low energy electron diffraction studies on vicinal Au(110) and Ni(110) surfaces is given, aiming for a deeper understanding of the influence of steps on reconstruction behaviour of fcc(110) surfaces on the one hand, and on the stability of reconstructing vicinal surfaces on the other. Finally, we report on the reconstruction behaviour of Ir(110), which stabilizes in the clean state by formation of mesoscopic (331) facets and dereconstructs to the (1×1) phase upon oxygen adsorption at 700–900 K.     

Energy barriers of single-adatoms diffusion on unreconstructed and reconstructed (110) surfaces

The present paper is aimed mainly to investigate theoretically the diffusion of Ag, Cu, Au and Pt adatoms on the (1 × 1) unreconstructed geometry for Ag, Cu and Pt (110), and reconstructed geometries ((1 × 2), (1 × 3) and (1 × 4)) for Pt and Au (110) surfaces. We consider the single adatom diffusion when additional atoms are deposited in adjacent row. For this study, we have used the molecular statics simulations combined with the embedded atom method. For several systems, we have calculated the activation barriers for hopping mechanism. For the diffusion on the unreconstructed surfaces, the trends for the activation barriers are the same for all considered systems except for Cu/Ag (110) system, where the activation barrier do not change. Further, our results indicate that additional atoms lead to a small decreasing of activation barriers for diffusion on reconstructed surfaces for some systems, while for other systems; the activation barrier remains practically unchanged.     

Adsorption of water molecule on (001) and (110) surfaces of MgH2

First principle calculations have been performed to explore the adsorption characteristics of water molecule on (001) and (110) surfaces of magnesium hydride. The stable adsorption configurations of water molecule on the surfaces of MgH₂ were identified by comparing the total energies of different adsorption states. The (110) surface shows a higher reactivity with H₂O molecule owing to the larger adsorption energy than the (001) surface, and the adsorption mechanisms of water molecule on the two surfaces were clarified from electronic structures. For both (001) and (110) surface adsorptions, the O p orbitals overlapped with the Mg s and p orbitals leading to interactions between O and Mg atoms and weakening the O–H bonds in water molecule. Due to the difference of the bonding strength between O and Mg atoms in the (001) and (110) surfaces, the adsorption energies and configurations of water molecule on the two surfaces are significantly different.     

Oxygen adsorption on the LaB6(100), (110) and (111) surfaces

Oxygen adsorption on the LaB₆(100), (110) and (111) clean surfaces has been studied by means of UPS, XPS and LEED. The results on oxygen adsorption will be discussed on the basis of the structurs and the electronic states on the LaB₆(100), (110) and (111) clean surfaces. The surface states on LaB₆(110) disappear at the oxygen exposure of 0.4 L where a c(2 × 2) LEED pattern disappears and a (1 × 1) LEED pattern appears. The work function on LaB₆(110) is increased to ～3.8 eV by an oxygen exposure of ～2 L. The surface states on LaB₆(111) disappear at an oxygen exposure of ～2 L where the work function has a maximum value of ～4.4 eV. Oxygen is adsorbed on the surface boron atoms of LaB₆(111) until an exposure of ～2 L. Above this exposure, oxygen is adsorbed on another site to lower the work function from ～4.4 to ～3.8 eV until an oxygen exposure of ～100L. The initial sticking coefficient on LaB₆(110) has the highest value of ～1 among the (100), (110) and (111) surfaces. The (100) surface is most stable to oxygen among these surfaces. It is suggested that the dangling bonds of boron atoms play an important role in oxygen adsorption on the LaB₆ surfaces.     

Nanoscale depth-resolved cathodoluminescence spectroscopy of ZnO surfaces and metal interfaces

The electronic properties of ZnO surfaces and interfaces has until recently been relatively unexplored. We have used a complement of ultrahigh vacuum scanning electron microscope (SEM)-based, depth-resolved cathodoluminescence spectroscopy (DRCLS), temperature-dependent charge transport, trap spectroscopy, and surface science techniques to probe the electronic and chemical properties of clean surfaces and interfaces on a nanometer scale. DRCLS reveals remarkable nanoscale correlations of native point defect distributions with surface and sub-surface defects calibrated with capacitance trap spectroscopies, atomic force microscopy, and Kelvin probe force microscopy. The measurement of these near-surface states associated with native point defects in the ZnO bulk and those induced by interface chemical bonding is a powerful extension of cathodoluminescence spectroscopy that provides a guide to understanding and controlling ZnO electronic contacts.     

Surface states at the clean surfaces of cleaved Si(111) and GaAs(110)

A combination of ellipsometric data on the electronic transitions from occupied to unoccupied surface states and published photoemission data on the energy distribution of the occupied surface states has been used to construct models of the surface states densities at the cleaved Si (111) and GaAs (110) surfaces.     

Vibrations spectra of oxygen chemisorbed on nickel (110) surfaces

Using a simple tight-binding scheme to describe the nickel d states and the oxygen p states, we calculate the positions and the vibration frequencies of chemisorbed oxygen atoms on nickel (110) surfaces. The comparison between our results and the high resolution electron loss measurements suggests a longbridge chemisorption site at low and high oxygen coverages on the nickel surface.     

Theoretical investigation of hydroxylated oxide surfaces

A self-consistent electronic structure calculation, in the slab geometry, is performed to model the dissociative adsorption of water on several oxide surfaces in the limit of complete saturation. We discuss the adsorption characteristics along a series of oxides presenting a growing acidity: BaO, SrO, CaO, MgO, TiO₂, and SiO₂, and on three MgO surfaces: (100), (110), and (211) on which the atoms have different environments. Special emphasis is borne on the charge transfers, the densities of states and the oxide gap modification upon hydroxylation. We show that these quantities are dependent upon the coverage and that unstable MgO surfaces are more reactive towards water dissociation. Finally, by optimizing the geometry on the three MgO surfaces, we discuss the link between the electronic and structural degrees of freedom on hydroxylated surfaces.     

Magnetism at surfaces and interfaces

The current state-of-the-art of ab-initio calculations of the magnetic structures of surfaces and interfaces is highlighted by presenting results obtained with the recently developed full-potential linearized augmented plane wave method for thin films. In particular, spin density maps, (induced) magnetic moments and hyperfine-fields are presented for the clean metal surfaces Fe(001), Ni(001) and Pt(001). The magnetic moments on an interface are discussed for the prototypical case Ni/Cu.     

Atomic,electronic, and vibronic structure of semiconductor surfaces

A brief review on recent progress in the theory of electronic, structural, and vibronic properties of semiconductor surfaces is presented with particular emphasis on the empirical and selfconsistent scattering theoretical method for semiinfinite systems. The current knowledge of the Si(001) (2×1) surface is discussed in detail. The Ge(001) (2×1) surface, as well as, the clean and the Ge-covered GaAs(110) surfaces are addressed, in addition. In the discussion of the results it is shown, that the scattering theoretical method is an extremely versatile tool for calculating electronic surface properties unambiguously with high spectral resolution concerning energy, wavevector, layer-index and orbital type. Currently used approaches for calculating the total energy, Hellmann-Feynman forces and optimal structure models are summarized. Using the total energy as a starting point, the calculation of atomic force constants and surface phonon spectra is exemplified.     

Substrate-induced spin-orbit splitting of quantum-well and interface states in Au,Ag, and Cu layers of different thicknesses on W(110) and Mo(110) surfaces

The substrate-induced spin-orbit splitting of interface and quantum-well states formed in Au, Ag, and Cu layers on W(110) and Mo(110) surfaces has been revealed using angle- and spin-resolved photoelectron spectroscopy. It has been shown that the magnitude of the splitting depends noticeably on the atomic number of the substrate material and is markedly larger for layers of these metals on W(110), i.e., on the surface of a metal with a larger atomic number (Z _W = 74), than on the surface of Mo(110), i.e., an element with a smaller atomic number (Z _Mo = 42), while depending only weakly on the atomic number of the adsorbed metal. Measurements of the dispersion of the formed quantum-well states have shown that the substrate-induced spin-orbit splitting increases with increasing parallel component of the photoelectron momentum (which correlates with the Rashba model) for all thicknesses of deposited films (up to 10 ML). The magnitude of induced spin-orbit splitting of the interface states evolving in monolayer Au, Ag, and Cu coatings on W(110) and Mo(110) decreases with increasing parallel component of the excited photoelectron momentum.     

Hyperfine fields at surfaces and interfaces

Magnetism and hyperfine fields at transition metal surfaces are discussed using state-of-the-art local spin density methods. Emphasis is placed on recent results obtained for the Fe(001), Ni(001), Cr(001) and Ag/Fe(001) ferromagnetic surfaces, and for the Knight shift in Pt(001).