The effect of embedded Pb on Cu diffusion on Pb/Cu(1 1 1) surface alloys

We have used scanning tunneling microscopy and low-energy electron microscopy to measure the thermal decay of two-dimensional Cu, Pb-overlayer, and Pb-Cu alloy islands on Pb-Cu(1 1 1) surface alloys. Decay rates covering 6-7 orders of magnitude are accessible by applying the two techniques to the same system. We find that Cu adatom diffusion across the surface alloy is rate-limiting for the decay of both Pb and Pb-Cu islands on the surface alloy and that this rate decreases monotonically with increasing Pb concentration in the alloy. The decrease is attributed to repulsive interactions between Cu adatoms and embedded Pb atoms in the surface alloy. The measured temperature dependences of island decay rates are consistent with first-principles calculations of the Cu binding and diffusion energies related to this “site-blocking” effect.     

Precursor film controlled wetting of Pb on Cu

Wetting in a system where the kinetics of drop spreading are controlled by the rate of formation of a precursor film is modeled for the first time at the atomistic scale. Molecular dynamics simulations of Pb(l) wetting Cu(111) and Cu(100) show that a precursor film of atomic thickness evolves and spreads diffusively. This precursor film spreads significantly faster on Cu(111) than on Cu(100). For Cu(100), the kinetics of drop spreading are dramatically decreased by slow advancement of the precursor film. Slow precursor film kinetics on Cu(100) are partly due to the formation of a surface alloy at the solid-liquid interface which does not occur on Cu(111).     

Surface diffusion of Pb on clean Si surfaces

Pb diffusion on clean Si(111), (100), and (110) surfaces was studied by Auger electron spectroscopy and low energy electron diffraction in the temperature range from 100 to 300°C. It is shown that lead transport along sillicon surfaces takes place via the mechanism of solid-phase spreading with a sharp moving boundary. The temperature dependence of the Pb diffusion coefficients on Si(111), (100) and (110) surfaces have been obtained. A Si(110)-4×2-Pb surface structure has been observed for the first time.     

Exchanges between Si and Pb adatoms on Si(111)

Real-time observation by high-temperature scanning tunneling microscopy of exchanges between Si and Pb atoms on a Si(111)-√3 × √3 surface is reported. The exchange rate is obtained as a function of the temperature. The activation energy of the exchange is about 1.2 eV, and the prefactor, shown to depend on the Pb coverage, is from 2 × 10¹⁰ to 8 × 10¹¹ s⁻¹. This prefactor is much larger than that for the exchange between Pb and Ge adatoms on a Ge(111)-c(2 × 8) surface, indicating that the adatom arrangement greatly influences the exchange mechanism. We also report that metastable 9 × 9 reconstruction appears during Pb desorption.     

Pb液滴在Ni基底润湿铺展行为的分子动力学模拟

采用分子动力学方法研究了Pb液滴在Ni(100)晶面、(110)晶面和(111)晶面的铺展润湿行为. 结果表明: Pb液滴在Ni(100)及(111)基底上的润湿铺展现象呈各向同性, 而在Ni(110)基底上的润湿铺展现象呈明显的各向异性, 且这种各向异性源于Ni(110)晶面点阵结构上Pb原子沿不同晶向的扩散机制及速度的明显差异; Pb液滴在Ni(111)晶面上铺展时, 未发生表面合金化, 液滴铺展动力学描述近似满足 R² ∝ t, 而液滴在(100)晶面和(110)晶面上铺展时表面产生合金化现象, 铺展动力学关系近似满足 R⁴ ∝ t, 且液滴在(100)晶面上的铺展速度高于(110)晶面上的铺展速度. 关键词： 分子动力学 润湿各向异性 铺展膜 扩散机制     

How Pb-overlayer islands move fast enough to self-assemble on Pb-Cu surface alloys

Low-energy electron microscopy reveals that two-dimensional, approximately 50 000 atom, Pb-overlayer and vacancy islands both have diffusion coefficients of 25.6+/-0.8 nm2/sec at 400 degrees C on Pb-Cu surface alloys. This high mobility, key to self-assembly in this system, results from the fast transport of Pb atoms on the surface alloy and of Cu through the Pb overlayer. A high Pb vacancy concentration, predicted by ab initio calculations, facilitates the latter.     

Borderline magic clustering: the fabrication of tetravalent Pb cluster arrays on Si(111)-(7x7) surfaces

Well-ordered arrays of identical Pb clusters have been fabricated on a Si(111)-(7x7) substrate by the temperature-mediated surface clustering method. Interestingly, these clusters can easily transform into other forms when the growth temperature deviates slightly from the optimal values. In accord with experiments, first-principle total-energy calculations reveal several cluster structures centered on a mixed cluster model involving surface Pb and Si exchange. This borderline Pb/Si(111) system provides a unique, controlled way to study surface magic cluster formation and breakup dynamics.     

Calculation of the surface energy of fcc metals with modified embedded-atom method

The surface energies for 38 surfaces of fcc metals Cu, Ag, Au, Ni, Pd, Pt, A1, Pb, Rh and Ir have been calculated by using the modified embedded-atom method. The results show that, for Cu, Ag, Ni, A1, Pb and Ir, the average values of the surface energies are very close to the polycrystalline experimental data. For all fcc metals, as predicted, the close-packed (111) surface has the lowest surface energy. The surface energies for the other surfaces increase linearly with increasing angle between the surfaces (hkl) and (111). This can be used to estimate the relative values of the surface energy.     

Collective excitations and quantum size effects on the surfaces of Pb(111) films: An experimental study

Pb(111) film is a special system that exhibits strong quantum size effects in many electronic properties. The collective excitations, i.e., plasmons, in Pb(111) films are also expected to show signatures of the quantum size effect. Here, using high-resolution electron energy loss spectroscopy, we measured the plasmons on the surface of Pb(111) films with different film thicknesses and analyzed the plasmon dispersions. One surface plasmon branch exhibits prominent damping in the small momentum range, which can be attributed to the interaction between the top and bottom interfaces of the Pb(111)films. With the film thickness increasing, the critical momentum characterizing the damping in Pb(111) films decays not only much slower in Pb(111) films than in other metal films, and even in films with the thickness up to 40 monolayers the damping still exists. The slow decay of the surface plasmon damping, manifesting the strong quantum size effect in Pb(111) films, might be related to the strong nesting of the Fermi surface along the(111) direction.     

Adsorption and diffusion of OH on Mo modified Pt(111) surface: First-principles theory

A first-principles study of adsorption and diffusion of OH on Pt and PtMo(111) surfaces is described. It confirms that the dissociation of water is much easier on PtMo than on pure Pt. Furthermore, we also found that OH binds most strongly at Mo atop site with adsorption energy of −3.32 eV, which is ∼1 eV stronger than binding to the pure Pt(111) surface. OH is much more localized on the PtMo alloy surface than on pure Pt. Both the stranger bond and the higher localization of OH contribute to the enhanced fuel cell performance with PtMo electrodes compared to pure Pt.     

Modifying Quantum Well States of Pb Thin Films via Interface Engineering

We demonstrate the importance of interface modification on improving electron confinement by preparing Pb quantum islands on Si（111） substrates with two different surface reconstructions, i.e., Si（111）-7 ×7 and Si（111）- Root3×Root3-Pb （hereafter, 7 ×7 and R3）. Characterization with scanning tunneling microscopy/spectroscopy shows that growing Pb films directly on a 7 × 7 surface will generate many interface defects, which makes the lifetime of quantum well states （QWSs） strongly dependent on surface locations. On the other hand, QWSs in Pb films on an R3 surface are well defined with small variations in linewidth on different surface locations and are much sharper than those on the 7 × 7 surface. We show that the enhancement in quantum confinement is primarily due to the reduced electron-defect scattering at the interface.     

Interface behavior of Mn/PbTe(111) studied by scanning tunneling microscopy and X-ray photoemission spectroscopy

Mn overlayers growth on PbTe(111) have been investigated by using scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS). The strong chemical interactions were found during the formation of Mn/PbTe(111) interface. At the initial deposition of Mn, one part of Mn adatoms substitute Pb atoms on the PbTe(111) surface, forming a (√3 × √3)R30° MnTe phase, and the other part of Mn adatoms, together with the kicked-out Pb atoms, nucleate at the boundaries of the MnTe islands, forming loop islands around the MnTe islands as an intermediate state. Finally, they develop into regular 3D Pb capped Mn islands upon further Mn deposition. For Mn growth on the PbTe surface where Pb atoms are almost completely substituted by Mn, the deposited Mn atoms either cooperate into the 3D Pb capped Mn islands promoting the upright growth of the 3D Pb capped Mn islands, or nucleate and grow on the MnTe superstructure areas. Free Pb layer always floats on the top of surface, indicating that Pb layer has smaller surface energy, and Mn adatoms always exchange the positions with the underneath Pb atoms during the growth.     

Growth of Ag on Pb Island with Si(111) Substrate

We study the growth of Ag on Pb island surface with low temperature scanning tunnelling microscopy.Two growth modes,the subsurface island mode and the surface alloy mode,are observed on tie substrate at room temperature and at 100 K,respectively.In the surface alloy mode,the perfect alloy AgPb_2 is formed on the Pb island surface after annealing.The two growth modes at different substrate temperatures are attributed to the existence of an exchange barrier of Ag atoms on the Pb island surface.The modulation of the exchange barrier by the quantum well states is also observed on the Pb island.     

Alloy formation in an electrodeposited monolayer

We find that a Au(111) electrode is substantially roughened after a single monolayer of Pb is electro-plated and stripped from the surface in a linear sweep experiment. The roughened electrode surface rearranges into 20 to 150 Å diameter islands which are one atomic layer high, and separated by 20 to 50 Å. This process is observed on all samples, for sweep rates ranging from 0.5 to 1000 mV/s. If a partial layer of Pb is plated and then stripped, pitting and an increased overpotential for Pb deposition are observed only in the areas adjacent to the plated sites. We suggest that these observations are consistent with the formation of a PbAu alloy in the surface layer.     

Formation and diffusion of S-decorated Cu clusters on Cu(111)

S-decorated Cu trimers are a likely agent of S-enhanced Cu transport between islands on Cu(111). According to ab initio calculations, excellent S bonding to trimer-Cu dangling valence results in an ad- Cu(3)S(3) formation energy of only approximately 0.28 eV, compared to 0.79 eV for a self-adsorbed Cu atom, and a diffusion barrier < or =0. 35 eV.     

Thermal motion and energetics of self-assembled domain structures: Pb on Cu(111)

Low energy electron microscope measurements of the thermal motion of 50-200 nm diameter Pb islands on Cu(111) are used to establish the nature and determine the strength of interactions that give rise to self-assembly in this two-dimensional, two-phase system. The results show that self-assembled patterns arise from a temperature-independent surface stress difference of approximately 1.2 N/m between the two phases. With increasing Pb coverage, the domain patterns evolve in a manner consistent with models based on dipolar repulsions caused by elastic interactions due to a surface stress difference.     

Tuning of the periodicity of stable self-organized metallic templates

The atomic and electronic structures of Pb bilayer/Pt(111) are investigated with two theoretical calculations.We find that the stable (2 × 2)/(3 × 3) Pb/Pt(111) structure is a promising candidate for being used as a template with self-organized ordered Pb semi-cluster array on the first Pb monolayer.This stable structure can realize the ordered Au single-atom array around the Pb semi-clusters that can cause selective adsorption of noble atoms.The size of Pb magic number semi-cluster plays a more important role in determining the periodicity of the template than the lattice constant misfit between the substrate and the overlayer.This leads to quite a different periodicity between the two stable templates,which are (2 × 2)/(3 × 3) Pb/Pt(111) and Pb/Cu(111).Therefore,by considering the size of the stable semi-clusters and carefully selecting different substrate materials,we can tune the density of Pb semi-clusters as the nucleation points and then tune the periodicity of the stable template.     

A study of a coadsorbate surface diffusion (Pb on C/W)

The influence of a coadsorbed submonolayer (carbon) on the diffusion of adatoms (lead) along a crystal surface (tungsten) is studied in a preliminary manner by a field electron microscope technique. Experiments show that the surface diffusion of lead is strongly affected by the coadsorption of carbon: (1) The diffusion of Pb which is easy around (110) and (111) and difficult around (100) on clean tungsten becomes easier around (100) than around (110) and (111). (2) The diffusion anisotropy on the stepped surface around (100) is changed by carbon adsorption. (3) C adatoms enhance the diffusion of Pb especially around (100). (4) The mean carbon coverage required to observe these effects is only a few hundredths of a monolayer. The dependence of the surface diffusion on such small impurity coverages is discussed.     

A combined XPS/AES study of Cu segregation to the high and low index surfaces of a Cu-Ni alloy

Quantitative information was obtained regarding the equilibrium segregation of Cu to the high index surfaces (cut 5° off the (100) plane in the [001] and [011] directions) and low index surfaces ((100), (111) and (110)) of a Cu: Ni, 5: 95% alloy crystal. Data regarding segregation to the (111) surface of a Cu: Ni, 50: 50% alloy crystal was also obtained. Equilibrium surfaces were obtained by careful annealing in the temperature range 850–920 K to avoid Cu loss by evaporation. The surface composition profile was calculated using data from the combination of the X-ray Photo-electron Spectroscopy and Auger Electron Spectroscopy techniques. Using these techniques, a wide range of electron kinetic energies and associated electron escape depths can be probed, yielding information about the topmost layer concentration and about the concentration profile into the bulk. Extensive Cu segregation was observed for the 5% and 50% Cu alloys. Topmost layer compositions of 85–100% Cu were found for both the high and low index surfaces of the 5% Cu alloy. In the next two or three atomic layers the composition was found to drop swiftly to near bulk Cu levels. For atomic layers deeper than this, some experimental evidence suggested a rise in Cu composition over three or four layers to 8–17% Cu before bulk levels were finally regained. For the 50% Cu alloy sample, a topmost layer composition was found of 95–100% Cu. Bulk levels of Cu were regained in about four atomic layers. These results are discussed in relation to other theoretical and experimental studies of segregation in these Cu-Ni alloys. The significance of the measured composition in relation to an equilibrium surface is also considered.     

Surface diffusion of Ni on Si(111) with coadsorption of Co

The effect of the coadsorption of Co and Ni on an Si(111) surface structure and on the diffusion of adsorbed atoms is investigated by low-energy electron diffraction and Auger electron spectroscopy. It is established that surface structures similar to those formed with the adsorption of Co alone are formed with the Ni and Co coadsorption on an Si(111) surface. It is found that the contribution of surface diffusion to the transport of Ni atoms is sharply higher on an Si(111) surface with submonolayer Co concentrations in the temperature range 500–750 °C than for a pure surface, where the main mechanism of Ni transport along the surface is diffusion of Ni atoms through the bulk of Si. Fiz. Tverd. Tela (St. Petersburg) 41, 1489–1494 (August 1999)