Diffusion driven concerted motion of surface atoms: Ge on Ge(001)

The diffusion of Ge dimers on the Ge(001) surface has been studied with scanning tunneling microscopy. We have identified three different diffusion pathways for the dimers: diffusion of on-top dimers over the substrate rows, diffusion across the substrate rows, and diffusion of dimers in the trough. We report on a heretofore unknown phenomenon, namely, diffusion driven concerted motion of substrate atoms. This concerted motion is a direct consequence of the rearrangement of substrate atoms in the proximity of the trough dimer adsorption site.     

Theory of adsorption: Ordered monolayers from Na to Cl on Si(001) and Ge(001)

First principles calculations of clean and adsorbate-covered surfaces of Si(001) and Ge(001) are reported. Chemical trends in the adsorption of ordered Na, K, Ge, As, Sb, S, Se and Cl overlayers are discussed. The calculations are based on the local-density approximation and employ non-local, norm-conserving pseudopotentials together with Gaussian orbital basis sets. The semi-infinite geometry of the substrate is properly taken into account by employing our scattering theoretical method. From total-energy minimization calculations we obtain optimal surface reconstructions which show asymmetric dimers for Si(001), Ge(001) and Ge:Si(001). For As:Si(001), Sb:Si(001) and Sb:Ge(001), we find symmetric adatom dimers in the equilibrium geometries. S or Se adlayers are found to be adsorbed in bridge positions forming a (1×1) unit cell with a geometry very close to the configuration of a terminated bulk lattice. Cl atoms adsorb on top of the dangling bonds of symmetric Si dimers residing in the first substrate-surface layer. Our calculations for Na:Si(001) and K:Si(001) confirm valley-bridge site adsorption for half monolayer coverage. For full monolayer alkali-metal coverage, adsorption in pedestal and valley-bridge positions is found to be energetically most favourable. The calculated optimal adsorption configurations are in excellent agreement with a whole body of recent experimental data on surface-structure determination. For these structural models, we obtain electronic surface band structures which agree very good with a wealth of data from angle-resolved photoemission spectroscopy investigations.     

Surface stress anisotropy of Ge(001)

By analyzing the equilibrium shape of vacancy islands on the Ge(001) surface we have determined the surface stress anisotropy, i.e., the difference between the compressive stress component along the substrate dimer rows and the tensile stress component perpendicular to the substrate dimer rows. In order to extract the surface stress anisotropy we have used a model recently put forward by Li et al. [Phys. Rev. Lett. 85, 1922 (2000)]. The surface stress anisotropy of the clean Ge(001) surface is found to be 80+/-30 meV/A(2). This value is comparable to the surface stress anisotropy of the closely related Si(001) surface.     

Pt-chain induced formation of Ge nanowires on the Ge(001) surface

A new reconstructed Pt/Ge(001)–4 × 2 surface structure of 0.25 ML Pt deposition is suggested based on density functional theory. The Ge dimers form nanowire arrays on a Pt-chain modified Ge(001) surface in which the chain is located between the two quasi-dimer rows and below the Ge nanowire. The simulated scanning tunneling microscope (STM) images of the surface are in excellent agreement with the previously observed STM features and sample bias dependence. It is the nanowire Ge dimers and not the Pt atoms that contribute to the STM images for occupied states at high sample biases, contrary to what has always been assumed in experiments. The surface bands of the Pt chain and quasi-dimer rows exhibit quasi-one-dimensional metallic behavior in the direction of the nanowire. When changing from the 4 × 2 to the 4 × 4 structure, there are likely pseudogaps opened at the new surface Brillouin zone boundary, which simultaneously reduce the metallicity. This may be related to the Peierls instability. The interaction between the Pt chain and the quasi-dimer row, as well as the inter-quasi-dimer row interaction, is of essential importance for stabilization.     

Second-harmonic spectroscopy of Ge/Si(001) and Si1-xGex(001)/Si(001)

0.9 Ge_0.1(001)/Si(001) films with SH photon energies 3.1<2hν<3.5 eV near the bulk E₁ critical point of Si(001) or Si_0.9Ge_0.1(001). Ge was deposited on Si(001) by using atomic layer epitaxy cycles with GeH₄ or Ge₂H₆ deposition at 410 K followed by hydrogen desorption. As Ge coverage increased from 0 to 2 monolayers the SH signal increased uniformly by a factor of seven with no detectable shift in the silicon E₁ resonant peak position. SH signals from Si_0.9Ge_0.1(001)/Si(001) were also stronger than those from intrinsic Si(001). Hydrogen termination of the Si_0.9Ge_0.1(001) and Ge/Si(001) surfaces strongly quenched the SH signals, which is similar to the reported trend on H/Si(001). We attribute the stronger signals from Ge-containingsurfaces to the stronger SH polarizability of asymmetric Ge-Si and Ge-Ge dimers compared to Si-Si dimers. Hydrogen termination symmetrizes all dimers, thus quenching the SH polarizability of all of the surfaces investigated. Received: 13 October 1998 / Revised version: 18 January 1999     

Surface Reconstruction of Pt/Si(001)

Platinum-induced surface reconstructions on Si(001) were investigated by scanning tunneling microscopy. The Si(001) surface shows c(4×6)+c(4×2)-type reconstruction after Pt hot deposition at 750 °C. The c(4×2) reconstruction is formed by regular arrangement of Pt ad-atoms at the hollow sites between two Si dimers on Si(001). The c(4×6) structure is formed by long-range ordering of Si dimers superimposed on the c(4×2) reconstruction. The surface reconstruction changes with the local Pt coverage and missing dimer density. An atomic model for c(4×6)+c(4×2) is proposed based on the observed c(4×4) surface reconstruction, a new surface reconstruction, which is observed following a high-temperature anneal at 900 °C. The c(4×4) surface reconstruction is regular and ordered in both the dimer-row direction and the direction perpendicular to the dimer rows. The reconstruction is formed by the regular arrangement of Si dimers and Pt ad-atoms sitting on top of the hollow sites surrounded by two dimers. An atomic model for this new reconstruction is proposed. PACS 68.35.Bs; 68.37.Ef; 68.43.Fg     

Structural phase transition on Si(001) and Ge(001) surfaces

Among a variety of solid surfaces, Si(001) and Ge(001) have been most extensively studied. Although they seem to be rather simple systems, there have been many conflicting arguments about the atomic structure on these surfaces. We first present experimental evidence indicating that the buckled dimer is the basic building block and that the structural phase transition between the low-temperature c(4x2) structure and the high-temperature (2x1) structure is of the order-disorder type. We then review recent theoretical work on this phase transition. The real system is mapped onto a model Ising-spin system and the interaction parameters are derived from total-energy calculations for different arrangements of buckled dimers. The calculated critical temperature agrees reasonably well with the experimental one. It is pointed out that the nature of the phase transition is crucially affected by a small amount of defects on the real surfaces.     

Ab initio study of platinum induced reconstructions on Ge(001)-(1×2) surface with dimerization

We present first principle total energy calculation of Pt induced reconstructions on Ge(001)-(1×2) surface with dimerization. Study was undertaken using localized orbitals basis set DFT using SIESTA to compare pure Ge dimerized Ge(001)-(1×2) surface with 0.5 and 1.0 Pt covered dimerized Ge(001)-(1×2) surface with the possibility of homo (Ge-Ge and Pt-Pt) and hetro (Pt-Ge) dimers. From total energy calculation results we calculated dimer bond lengths, buckling angles and formation energy of dimers on Ge(001)-(1×2) surface. By calculating the formation energy of different configurations we find that Ge-Ge buckled dimerized surface has least (−1.23 eV/dimer) and Pt-Pt symmetric dimerized surface has largest (+0.09 eV/dimer) formation energy with respect to unreconstructed surface. We further calculated the electronic DOS and band structure of Ge dimerized as well as Pt dimerized surface to see the change in semiconducting behavior on dimerization. By comparing the DOS and electronic band structure of homo Ge dimerized surface, we found metallicity of Ge(001)-(1×2) surface results from dimer formation. Also by comparing the electronic band structure of homo Ge dimerized surface with unreconstructed surface we find that less number of bands crossing the Fermi level which is perhaps due to the saturation of one dangling bond per Ge surface atom. By introducing Pt at 0.5 and 1.0 coverage in place of Ge, except for homo Pt buckled dimerized surface having 1.0 coverage of Pt, we find in all other cases increase in number of bands are crossing the Fermi level, indicating strong metallic behavior of Ge(001)-(1×2) surface.     

Anisotropic interaction of Ag-induced missing dimer vacancies on Si(001) surfaces

Ag-induced missing dimer vacancies on Si(001)2 × 1 surfaces are shown to form vacancy lines when the vacancy concentration is larger than ∼10%. The formation of the vacancy lines is driven by the short-range attractive interaction between the vacancies in adjacent dimer rows and the long-range repulsive interaction between them in the same dimer row. The form and magnitudes of the interactions are derived from the thermally-excited wandering of the vacancy lines.     

Dynamics of Au-induced nanowires on Ge(001)

We have studied the dynamics of Au-induced nanowires on Ge(001) using scanning tunnelling microscopy. The ridges of these nanowires consist of buckled dimers that have their dimer bond aligned in a direction perpendicular to the nanowire direction. Neighbouring dimers have a preference to buckle in an opposite direction, leading to rows with a zigzag appearance. Dimers located at anti-phase boundaries continuously flip back and forth between their two buckled configurations. This process is thermally induced and occurs at an average frequency of 25 Hz at room temperature.     

Initial stage of carbon incorporation into si(001) and one-dimensional ordering of embedded carbon

We investigate the initial stage of the C incorporation into Si(001) using thermal dissociation of C2H2. The scanning tunneling microscopy shows that C-induced dimer vacancies (DVs) with depressed adjacent dimers are generated on the surface and aligned in the dimer direction, forming the 2xn structure. The ab initio pseudopotential calculations reveal that, with the presence of a DV in the surface, the alpha site in the fourth subsurface layer directly below the DV is the most favorable for the incorporated C atoms. The embedded C atoms align one dimensionally due to the interaction which is attractive in neighboring dimer rows but repulsive in the same dimer row.     

Embedded Co islands on Ge(001)

The adsorption of Cobalt (Co) on Germanium (Ge) (001) surfaces has been studied using scanning tunneling microscopy. Upon annealing at temperatures of 500–550 K well-ordered rectangular shaped embedded islands are formed. Based on our scanning tunneling microscopy data we propose that the elementary building block of these embedded islands consist of six Co atoms arranged in a hexagonal pattern. A statistical analysis reveals that the embedded Co islands exhibit an attractive interaction in a direction perpendicular to the substrate dimer rows and a repulsive interaction in a direction along the substrate dimer rows. The embedded Co islands eventually convert to perfectly straight and micrometers long nanowires upon annealing at temperatures that exceed 700–750 K.     

Diffusion of Pb adatom and ad-dimer on Si(1 0 0) from ab initio studies

The diffusion pathways of Pb adatoms and ad-dimers on Si(1 0 0) are investigated by first-principles calculations. Pb adatoms are found to diffuse on top of the Si(1 0 0) dimer row with an energy barrier of 0.31 eV. However, Pb dimers are energetically more stable. Pb dimers on top of the dimer row have a high energy barrier (0.95 eV) to rotate from the lowest energy configuration to the orientation parallel to the underlying Si(1 0 0) dimer row. Once the ad-dimer is oriented parallel to Si(1 0 0) dimer row, they can diffuse along the dimer row with an energy barrier of only 0.32 eV.     

Two-dimensional carbon incorporation into Si(001): C amount and structure of Si(001)-c(4 x 4)

The C amount and the structure of the Si(001)-c(4 x 4) surface is studied using scanning tunneling microscopy (STM) and ab initio calculations. The c(4 x 4) phase is found to contain 1/8 monolayer C (1 C atom in each primitive unit cell). From the C amount and the symmetry of high-resolution STM images, it is inferred that the C atoms substitute the fourth-layer site below the dimer row. We construct a structure model relying on ab initio energetics and STM simulations. Each C atom induces an on-site dimer vacancy and two adjacent rotated dimers on the same dimer row. The c(4 x 4) phase constitutes the subsurface Si(0.875)C(0.125) delta layer with two-dimensionally ordered C atoms.     

单畴的单原子In纳米线阵列的制备与研究

利用Si（001）向［110］方向偏4°角的斜切表面作为衬底，成功地制备了分布均匀的单畴的单原子In链阵列.扫描隧道显微镜分析表明，沉积的In原子优先吸附在台面上沿着台阶内边缘的位置，并在两个Si的二聚体链之间形成稳定的In二聚体.In二聚体组成直的单原子链，其生长机理与Car提出的“表面聚合反应”相一致.另外，衬底具有非常窄的台面和双原子层台阶边的特殊结构是形成单畴的单原子链的关键. 关键词： 铟单原子链 硅邻近面 扫描隧道显微镜     

Changing the diffusion mechanism of Ge-Si dimers on Si(001) using an electric field

We change the diffusion mechanism of adsorbed Ge-Si dimers on Si(001) using the electric field of a scanning tunneling microscope tip. By comparing the measured field dependence with first-principles calculations we conclude that, in negative field, i.e., when electrons are attracted towards the vacuum, the dimer diffuses as a unit, rotating as it translates, whereas, in positive field the dimer bond is substantially stretched at the transition state as it slides along the substrate. Furthermore, the active mechanism in positive fields facilitates intermixing of Ge in the Si lattice, whereas intermixing is suppressed in negative fields.     

Theoretical consideration on dimer vacancy images in the STM observations of Si(001) surfaces in terms of the adsorption of O2 molecules

Geometric and electronic structures of dimers on the Si(001)-2 × 1 reconstructed surfaces before and after O₂ adsorption have been investigated with an ab initio molecular orbital (MO) calculation at the Hartree-Fock level. The theoretically predicted electron tunneling current in the dimer before and after O₂ adsorption has strongly suggested that the O₂-adsorbed dimer on clean Si(001) surfaces is observed as dark in the scanning tunneling microscope (STM) images. The dark spot images which have so far been recognized to be a dimer vacancy type defect could be due to the O₂ adsorption in parallel to a Si dimer.     

Energetics of Si(001) surfaces exposed to electric fields and charge injection

We perform density-functional calculations on the influence of external electric fields and electrons or holes injected into surface states on the relative stability of c(4x2) and p(2x2) reconstructed Si(001) surfaces. It is shown that an electric field parallel to the [001] direction or the insertion of electrons into surface states favors the formation of p(2x2) periodicities. Our results explain recent experimental studies reporting changes of surface reconstruction of Si and Ge(001) surfaces induced by the scanning tunneling microscope and the occurrence of p(2x2) reconstructions on (001) surfaces of n-doped Si.     

Sb/Si(001)表面的半经验研究

用基于Chadi模型和格林函数方法的一种计算表面应力的半经验方法研究了Sb吸附在Si(001) 衬底上的性质.结果显示,Sb原子在Si(001)表面形成对称的dimer,其键长为0.293nm,表 面以下层的弛豫很小.Sb/Si(001)2×1表面沿着dimer方向的张应力为1.0eV/(1×1cell),而 沿垂直于dimer方向的压应力为-1.1eV/(1×1cell).Sb/Si(001)表面应力的主要贡献来自于 最上面三层表面. 关键词： 表面应力 异质生长 格林函数方法     

Order-disorder transition on Si(001)

A phase transition between c(4x2) and 2x1 structures on the Si(001) surface has been observed at 200 K by low-energy electron diffraction. This transition is a second order order-disorder transition of the asymmetric dimer configuration. The streak pattern remains up to well above the transition temperature. The temperature dependence of the width and the length of the streak can be described in terms of the effects of a strong anisotropic coupling between adjacent asymmetric dimers.