Formation of nanoislands in the course of copper deposition on a Cu(111)-(9 × 9)-Ag surface

The process of copper deposition on a structured Cu(111)-(9 × 9)-Ag surface, which represents a (9 × 9) loop dislocation network, is studied by scanning tunneling microscopy. It is found that, when the substrate temperature is 100 K and the copper coverage is 0.1–0.4 of a monolayer, islands of a size no greater than 50 Å are formed at the Ag/Cu(111) interface. The islands remain stable as the sample is heated to room temperature. The shape and boundaries of the nanoislands follow the initial surface superstructure and are determined by the nonuniformity of the interaction of the upper silver layer with the copper substrate. The mechanism of island formation and the origin of their stability are explained in terms of the atom exchange between the adsorbate and substrate.     

LEED study of the epitaxial growth of the thin film Au(111)/Ag(111) system

An analysis of LEED data from the Ag(111) surface at room temperature and 5° ? Θ ? 16°, φ = 12° has been carried out in order to test three different model potentials for the exchange and correlation part of the one-electron LEED potential. Clean Au(111) surfaces have been grown on Ag(111) at room temperature at a deposition rate of 0.15 Å s^?1. Similar method of calculation and potentials have been employed for the Au overlay er on Ag(111). After the deposition of ? 2.5 monolayers of Au/Ag(111) the growth of Au can proceed in two different ways. One of them matches satisfactorily with the theoretical calculation for the Au(111) overlayer on Ag(111) following the fcc sequence. The other seems to be concerned with the diffusion of Ag during the Au growth. Similar curves have been obtained during the diffusion of Ag through 350 Å of Au(111).     

Structural transformations on an oxidized Ag(111) surface

The structure of the Ag(111) surface after the adsorption of molecular oxygen at a temperature of 300 K is studied by low-temperature scanning tunneling microscopy. It is established that local surface oxide is formed at the first stage of adsorption. The subsequent adsorption of O results in the appearance of new objects with a size of 3–8 Å and a height of 1.0–1.5 Å on the Ag(111) surface, which form quasi-ordered structures with increasing degree of coating. The heating of the system obtained up to 500 K leads to a structural transition resulting in the formation of single islands of the p (4×4) phase on the surface. Surface structures are identified by a simulation based on the density functional theory.     

Atomic processes in vacancy island motion on Ag(111)

We present results of molecular dynamics simulations of the motion of monatomic-deep vacancy islands on Ag(111), using interaction potentials from the embedded atom method. The individual processes appearing in a large set of runs, at three different temperatures, are identified. From the statistics thus collected, we find that the predominant mechanism underlying the diffusion of vacancy islands on Ag(111) is the diffusion of atoms along the periphery of the vacancy islands.     

Ag growth on Si(111) with an Sb surfactant investigated by scanning tunneling microscopy

We have investigated a room-temperature growth mode of ultrathin Ag films on a Si(111) surface with an Sb surfactant using STM in a UHV system. On the Sb-passivated Si surface, small sized islands were formed up to 1.1 ML. Flat Ag islands were dominant at 2.1 ML, coalescing into larger islands at 3.2 ML. Although the initial growth mode of Ag films on the Sb-terminated Si(111) surface was Volmer-Weber (island growth), the films were much more uniform than Ag growth on clean (Si(111) at the higher coverages. From the analysis of STM images of Ag films grown with and without an Sb surfactant, the uniform growth of Ag films using an Sb surfactant appears to be caused by the kinetic effects of Ag on the preadsorbed Sb layer. Our STM results indicated that Sb suppresses the surface diffusion of Ag atoms and increases the Ag-island density. The increased island density is believed to cause coalescence of Ag islands at higher coverages of Ag, resulting in the growth of atomically flat and uniform Ag islands on the Sb surfactant layer.     

Structure of the Ag on Si(111) 7 × 7 interface by means of surface exafs

Polarization dependent surface extended X-ray absorption fine structure (SEXAFS) measurements are used to determine the structure of the Ag on Si(111)7 × 7 system at the early stages (< 3 monolayers (ML)) of interface formation. At room temperature (RT) Ag is found to initially (< 0.5 ML) chemisorb in the threefold hollow site, approximately 0.7 Å above the outermost Si layer with an average Ag-Si distance of 2.48±0.05 Å. Above monolayer coverage the SEXAFS spectrum is dominated by the Ag-Ag distance indicating Ag island formation on the surface. Upon heating (200 ?T? 600°C) a (√3 ×√3)R30° LEED pattern is observed. At the lowest coverage ( < 0.7 ML) this pattern is determined to arise from Ag atoms which are embedded in the threefold hollows, ~ 0.7 Å below the first and above the second Si layer, with a Ag-Si distance of 2.48 ± 0.04 Å. At higher coverage ($\text{\$}\text{?}$1 ML) Ag clusters are found to grow on this interface with the same Ag-Ag distance as in Ag metal. Our results are discussed in the context of previous experimental and theoretical results.     

Adsorption-desorption properties and surface structural chemistry of chlorine on Cu(111) and Ag(111)

The adsorption, desorption, and structural properties of chlorine adlayers on Cu(111) and Ag(111) have been studied by LEED, Auger, Δ?, and thermal desorption measurements. Ancillary experiments were also carried out on cuprous chloride for purposes of comparison with the Cu(111)-Cl data. Chlorine adsorption is rapid on both metals and follows precursor kinetics, the absolute initial sticking probabilities being ~1.0 (Cu) and ~0.5 (Ag). Δ? results suggest that significant depolarisation of the chemisorption bond occurs at high coverages, the maximum values being + 1.2 eV (Cu) and + 1.8 eV (Ag). On Cu(111), adsorption leads to the formation of a sequence of well-ordered phases; in order of increasing coverage, these are as follows: (√3 × √3)R30°, (12√3 × 12√3)R30°, (4√7 × 4√7)R19.2°, and (6√3 × 6√3)R30°. On Ag(111) (√3 × √3)R30°, and (10 × 10) structures are observed. All six structures are susceptible to a straightforward interpretation in terms of coincidence lattices resulting from the progressive uniform compression of a hexagonal layer of Cl atoms. This interpretation is consistent with all the experimental results, and gives values for the nearest-neighbour ClCl spacing on both Cu(111) and Ag(111) which are in good agreement with other work on other surfaces. Chlorine desorbs exclusively as atoms from both metals with first-order desorption kinetics, and apparent desorption energies of 236 (Cu) and 209 (Ag) kJ mol^?1. These values, which depend on an assumed pre-exponential factor of 10¹³ s^?1, are shown to be inconsistent with the thermochemical constraints on the system necessitated by the complete absence of Cl₂ desorption. Lower limits for the pre-exponential factors are then deduced, and the values are found to be consistent with the differences between the CuCl and AgCl systems.     

低能原子沉积在Pt(111)表面的分子动力学模拟

采用嵌入原子方法的原子间相互作用势,利用分子动力学方法模拟了六种贵金属原子(Ni,Pd,Pt,Cu,Ag,Au)分别在Pt(111)表面低能沉积的动力学过程.结果表明:随着入射能量从0.1eV升高到200eV,基体表面原子是按层迁移的,沉积过程对基体表面的影响和沉积原子在基体表层的作用均存在两个转变能量(ET1≈5eV,ET2≈70eV).当入射能量低于5eV时,基体表面几乎没有吸附原子和空位形成,沉积原子在基体表层几乎没有注入产生;当入射能量在5—70eV范围内时,沉积原子在基体表层有注入产生,其注入深度小于两个原子层,即为亚注入,此时吸附原子主要由基体表层原子形成,基体表面第三层以下没有空位形成;当入射能量高于70eV时,沉积原子的注入深度大于两个原子层,将会导致表面以下第三层形成空位,并且空位产额随入射能量的升高而急剧增加.基于分子动力学模拟的结果,对低能沉积作用下的薄膜生长以及最优沉积参数的选择进行了讨论.     

IR absorption enhancement for physisorbed methanol on Ag island films deposited on the oxidized and H-terminated Si(111) surfaces: effect of the metal surface morphology

Infrared absorption measurements using a multiple internal reflection geometry are reported for condensed methanol at 90 K on Ag island films deposited on the oxidized and hydrogen-terminated surfaces of Si(111). The attenuated total reflection (ATR) spectra obtained as a function of methanol exposure (up to 14 L) show that a 1-nm mass thickness of Ag island film on the oxidized Si(111) surface yields an absorption intensity 2–3 times larger than the intensity in the absence of Ag on the oxidized surface. Deposition of the same thickness of Ag on the hydrogen-terminated Si(111) surface results in approximately twice the enhancement. The different magnitudes of the enhancement are discussed based on SEM micrographs for Ag island films formed on the oxidized and H-terminated Si(111) surfaces. Received: 1 March 1999 / Accepted: 8 March 1999 / Published online: 5 May 1999     

Initial growth process and surface structure of Ag on Si(111) studied by low-energy Ion-Scattering Spectroscopy (ISS) and LEED-AES

The growth process of silver on a Si(111) substrate has been studied in detail by low-energy ion-scattering spectroscopy (ISS) combined with LEED-AES. Neon ions of 500 eV were used as probe ions of ISS. The ISS experiments have revealed that the growth at room temperature and at high temperature are quite different from each other even in the submonolayer coverage range. The following growth models have been proposed for the respective temperatures. At room temperature, the deposited Ag forms a two-dimensional (2D) island at around 2/3 monolayer (ML) coverage, where the Ag atoms are packed commensurately with the Si(111)1 substrate. One third of the substrate Si surface remains uncovered there. Then it starts to develop into Ag crystal, and at a few ML coverage a 3D island of bulk Ag crystal grows directly on the substrate. An intermediate layer, which covers uniformly the whole surface before the growth of Ag crystal, does not exist. At high temperatures (>~200°C), the well-known Si(111)√3-Ag layer is formed as an intermediate layer, which consists of 2/3 ML of Ag atoms and covers the whole surface uniformly. These Ag atoms are embedded in the first double layer of the Si substrate. It is concluded that the formation of the √3 structure needs relatively high activation energy which may originate from the large displacement of Si atoms owing to the embedment of the Ag atoms, and does not proceed below about 200°C. The most stable state of the Ag atoms on the outermost Si layer is in the shape of an island, both for the Si(111) surface and for the Si(111)√3-Ag surface.     

The anomalous RHEED patterns observed from (111)Ag-(111)Cu bilayers

RHEED patterns obtained from thin expitaxial bilayers consisting of Ag grown on smooth (111)Cu surfaces have been shown by Gradmann and Krause to contain anomalous reflections. Previously, these reflections were interpreted as due to a regular arrangement of interfacial dislocations or to multiple diffraction effects. In the present work a thin film technique was used to form smooth, easily detachable (111)Ag/Cu bilayers from which RHEED patterns containing these extra reflections were obtained. These films were grown, annealed, and examined in situ by UHV-RHEED techniques. They were then removed from the vacuum system, detached from their substrates and examined by TEM and TED. Thus, contrary to previous work, the present observations consisted of a series of experiments using RHEED, TED, and TEM carried out on the same specimen. No evidence was obtained to indicate that the anomalous reflections were due to interfacial dislocations. Rather, all the observed phenomena could be explained entirely by multiple diffraction effects.     

Electronic structure and ordering of multilayers of Co and Ag on Cu(111) investigated by photoelectron spectroscopy

The growth and the electronic structure of multilayers of Co and Ag on Cu(111) at room temperature have been studied with photoelectron spectroscopy and low-energy electron diffraction (LEED). The coverage range spans from Co and Ag layers between one monolayer (ML) to stacking of several monolayers. Surface states and ordered structures have been identified at room temperature. A Ag-related surface state with a binding energy of 0.30 eV is identified in normal emission in the ultraviolet photoelectron spectra when silver constitutes the top layer. Core-level binding energy shifts of Ag 3d_5/2 reflect the changing surroundings of Ag. Hexagonal diffraction patterns are observed for sandwiches of consecutive layers of Co and Ag up to 5 layers. Since no interlayer diffusion is observed in the layer-by-layer formation of the films, multilayers of consecutive silver and cobalt on Cu(111) offer preparation of sandwiched magnetic–non-magnetic structures.     

Diffusion Dynamics of Cux Cluster on Cu(111) Surface

利用分子动力学与修正分析型嵌入原子模型研究了从200K至800 K范围内,Cux (1·x·8)小团簇在(111)面的自扩散动力学行为,计算了Cu小团簇的扩散系数与激活能. 计算结果表明,密排的Cu7团簇的激活能最高,其扩散前因子比单个吸附原子的高3个数量级,这与其他类似金属的实验结果一致. 另外,还定量讨论了薄膜生长与团簇扩散的关系.     

Molecular dynamics simulation of nanoscale surface diffusion of heterogeneous adatoms clusters

Molecular dynamics simulation employing the embedded atom method potential is utilized to investigate nanoscale surface diffusion mechanisms of binary heterogeneous adatoms clusters at 300 K, 500 K, and 700 K. Surface diffusion of heterogeneous adatoms clusters can be vital for the binary island growth on the surface and can be useful for the formation of alloy-based thin film surface through atomic exchange process. The results of the diffusion process show that at 300 K, the diffusion of small adatoms clusters shows hopping, sliding, and shear motion; whereas for large adatoms clusters(hexamer and above), the diffusion is negligible. At 500 K, small adatoms clusters, i.e., dimer, show almost all possible diffusion mechanisms including the atomic exchange process; however no such exchange is observed for adatoms clusters greater than dimer. At 700 K, the exchange mechanism dominates for all types of clusters, where Zr adatoms show maximum tendency and Ag adatoms show minimum or no tendency toward the exchange process. Separation and recombination of one or more adatoms are also observed at 500 K and 700 K. The Ag adatoms also occupy pop-up positions over the adatoms clusters for short intervals. At 700 K, the vacancies are also generated in the vicinity of the adatoms cluster,vacancy formation, filling, and shifting can be observed from the results.     

Reversible shape transition of pb islands on Cu(111)

Using low-energy electron microscopy, we have observed a reversible transition in the shape of Pb adatom and vacancy islands on Cu(111). With increasing temperature, circular islands become elongated in one direction. In previous work we have shown that surface stress domain patterns are observed in this system with a characteristic feature size which decreases with increasing temperature. We show that the island shape transition occurs when the ratio of the island size to this characteristic feature size reaches a particular value. The observed critical ratio matches the value expected from stress domains.     

Ag(111)和Au(111)上铋的初始生长行为

半金属铋(Bi)的表面合金具有的Rashba效应,和其具体结构性质有重要关联.本文结合扫描隧道显微镜(STM)和密度泛函理论(DFT),系统地研究了Bi原子在Ag(111)和Au(111)上的不同初始生长行为.在室温Ag(111)上,连续的Ag2Bi合金薄膜会优先在Ag台阶边缘形成;在570 K Ag(111)上,随着...     

Methanol decomposition on platinum (111)

The interaction of methanol with clean and oxygen-covered Pt(111) surfaces has been examined with high resolution electron loss spectroscopy (EELS) and thermal desorption spectroscopy (TDS). On the clean Pt(111) surface, methanol dehydrogenated above 140 K to form adsorbed carbon monoxide and hydrogen. On a Pt(111)-p(2 × 2)O surface, methanol formed a methoxy species (CH₃O) and adsorbed water. The methoxy species was unstable above 170 K and decomposed to form adsorbed CO and hydrogen. Above room temperature, hydrogen and carbon monoxide desorbed near 360 and 470 K, respectively. The instability of methanol and methoxy groups on the Pt surface is in agreement with the dehydrogenation reaction observed on W, Ru, Pd and Ni surfaces at low pressures. This is in contrast with the higher stability of methoxy groups on silver and copper surfaces, where decomposition to formaldehyde and hydrogen occurs. The hypothesis is proposed that metals with low heats of adsorption of CO and H₂ (Ag, Cu) may selectively form formaldehyde via the methoxy intermediate, whereas other metals with high CO and H₂ chemisorption heats rapidly dehydrogenate methoxy species below room temperature.     

Long-range electronic interactions at a high temperature: bromine adatom islands on Cu(111)

Long-range electronic interactions between Br adatom islands, which are formed at approximately 600 K, on Cu(111) are mediated by substrate surface-state electrons at that elevated temperature. Using scanning tunneling microscopy at 4 K, we have quantified nearest neighbor island separations and found favored spacings to be half-multiples of the Fermi wavelength of Cu(111). The strong interaction potential and decay length of the interisland interactions are discussed in terms of the interaction of Br with the substrate surface state.     

Decorated Ag19 on Pt(111) or the "rare gas necklace"

Ag19 cluster ions are mass selected and deposited on a Pt(111) surface covered by five monolayers of Kr. Almost monodispersed hexagonal shaped Ag islands are observed after Kr evaporation at 125 K. The identification of the island shape and the exact number of atoms has been successful by decorating the clusters with Kr atoms which can be counted by high resolution scanning tunneling microscopy.     

Reactive epitaxy of cobalt disilicide on Si(111)

A study of the mechanism governing the initial stages in silicide formation under deposition of 1–10 monolayers of cobalt on a heated Si(111) 7×7 crystal is reported. The structural data were obtained by an original method of diffraction of inelastically scattered medium-energy electrons, which maps the atomic structure of surface layers in real space. The elemental composition of the near-surface region to be analyzed was investigated by Auger electron spectroscopy. Reactive epitaxy is shown to stimulate epitaxial growth of a B-oriented CoSi₂(111) film on Si(111). In the initial stages of cobalt deposition (1–3 monolayers), the growth proceeds through island formation. The near-surface layer of a CoSi₂(111) film about 30 Å thick does not differ in elemental composition from the bulk cobalt disilicide, and the film terminates in a Si-Co-Si monolayer triad.