Interdiffusion of adsorbed Pb and Bi on Cu(1 0 0)

The impingement and interdiffusion of adsorbed Pb and Bi layers spreading from separated 3D pure bulk sources on Cu(1 0 0) has been studied, at T = 513 K, by in situ scanning Auger microscopy. When the leading edges of the pure Pb and Bi diffusion profiles impinge, they both consist of low-coverage lattice gas surface alloyed phases. In these low-coverage phases, Pb displaces surface alloyed Bi and the point of intersection of the profiles drifts towards the Bi source. These features lead to the conclusion that Pb atoms are more strongly bound at surface alloyed sites in Cu(1 0 0) than Bi atoms. Once the total coverage (Pb + Bi) on the substrate reaches about one monolayer, Pb and Bi are dealloyed from the substrate, and the interdiffusion profiles become essentially symmetric. Pb and Bi mix in all proportions, with an interdiffusion coefficient of ∼10⁻¹³ m²/s. This is considerably smaller than the self-diffusion coefficients previously observed for pure Pb and Bi in their respective high-coverage phases, indicating that the mechanism of interdiffusion is different from that of self-diffusion. As interdiffusion proceeds, the point of intersection of the Pb and Bi profiles reverses its drift direction, leading to the conclusion that binding of Bi atoms to the Cu(1 0 0) substrate is stronger than that of Pb atoms in the highest-coverage surface dealloyed layers.     

Impact of surface phase transitions and structure on surface diffusion profiles of Pb and Bi over Cu(1 0 0)

Surface diffusion of Pb and Bi over Cu(1 0 0) surfaces has been studied by scanning Auger microscopy techniques. The diffusion profiles of Pb and Bi have been found to be quite different. The results show that three major factors control the shapes of the surface diffusion profiles: (a) First order phase transitions, which lead to phase coexistence over specified coverage ranges, tend to produce abrupt changes in coverage versus distance profiles; (b) profiles can be affected by the existence of significant differences in the diffusion coefficients of the various phases present, and by the possibility (c) of important changes in diffusivity within a given phase, as a function of coverage, due to interactions between the diffusing atoms. In addition, it has been shown that the strong connection between diffusion profile shapes and the 2D phase diagram allows certain features of the 2D phase diagram to be determined from diffusion profiles.     

A density functional theory study of ethylene adsorption on Ni10(1 1 1), Ni13(1 0 0) and Ni10(1 1 0) surface cluster models and Ni13 nanocluster

Ethylene adsorption was studied by use of DFT/B3LYP with basis set 6-31G(d,p) in Gaussian’03 software. It was found that ethylene has adsorbed molecularly on all clusters with π adsorption mode. Relative energy values were calculated to be −50.86 kcal/mol, −20.48 kcal/mol, −32.44 kcal/mol and −39.27 kcal/mol for Ni₁₃ nanocluster, Ni₁₀(1 1 1), Ni₁₃(1 0 0) and Ni₁₀(1 1 0) surface cluster models, respectively. Ethylene adsorption energy is inversely proportional to Ni coordination number when Ni₁₀(1 1 1), Ni₁₃(1 0 0) and Ni₁₀(1 1 0) cluster models and Ni₁₃ nanocluster are compared with each other.     

Structural analysis of the c(4 × 2) reconstruction in Si(0 0 1) and Ge(0 0 1) surfaces by low-energy electron diffraction

The c(4 × 2) structures in (0 0 1) surfaces of Si and Ge have been studied by low-energy electron diffraction (LEED). Using a proper cleaning method for the Si surface, we were able to observe clear c(4 × 2) LEED patterns up to incident energy of ∼400 eV as well as the Ge surface. Extensive experimental intensity-voltage curves allowed us to optimize the asymmetric dimer model up to the eighth layer (including the dimer layer) in depth in the dynamical LEED calculation. Optimized structural parameters are almost the same for the Si and Ge except for the height of the buckled-up atom of the asymmetric dimer. For the Ge surface, the structural parameters are in excellent agreement with those obtained by a previous theoretical calculation. The tilt angle and bond length of the dimer are 18 ± 1 (19 ± 1)° and 2.4 ± 0.1 (2.5 ± 0.1) Å for the Si(0 0 1) (Ge(0 0 1)), respectively.     

Asymmetric adsorption-site of potassium atoms in the (3 × 2)-p2mg structure formed on Cu(0 0 1)

The adsorption of K atoms on Cu(0 0 1) has been studied by low-energy electron diffraction (LEED) at room temperature (RT) and 130 K. At RT, a (3 × 2)-p2mg LEED pattern with single-domain was observed at coverage of 0.33, whereas the orthogonal two-domain was found at 130 K. At 130 K, a c(4 × 2) pattern with orthogonal two-domain was observed at coverage 0.25. Both the (3 × 2)-p2mg and c(4 × 2) structures have been determined by a tensor LEED analysis. It is demonstrated that K atoms are adsorbed on surface fourfold hollow sites in the c(4 × 2), while in the (3 × 2) structure two K atoms in the unit cell are located at an asymmetric site with a glide-reflection-symmetry. The asymmetric site is at near the midpoint between the exact hollow site and bridge-site but slightly close to the hollow site. A rumpling of 0.07 Å in the first Cu layer was confirmed, which might stabilize K atoms at the asymmetric site. Surface structures appearing in a coverage range 0.25-0.33 are discussed in terms of the occupation of the asymmetric site with increase of coverage.     

Theoretical STM images of alkaline-earth metal adsorbed Si(1 1 1)3 × 2 surfaces

We have performed total-energy calculations to study theoretical scanning tunneling microscopy (STM) images of the Si(1 1 1)3 × 2 surfaces induced by the adsorption of alkaline-earth metals (AEMs). Previously, in a series of works on Ba/Si(1 1 1) system, we have found that the observed Si(1 1 1)3 × 1-Ba LEED phase indeed has a 3 × 2 periodicity with a Ba coverage of 1/6 ML and the HCC substrate structure. Based on results of the Ba case, we proposed that the HCC structure is also adopted for other AEM atoms, which was confirmed by our recent work. In this paper, we mainly report the STM simulations for different AEM systems to compare with existing experimental data. We discuss the difference in the detailed STM images for different AEM adsorbates. Especially, the difference in filled-state images between Mg and other AEM atoms is attributed to the strong Mg-Si interaction.     

STM image visualization of Si(1 1 1) 7 × 7 surface (graphic simulation and implementation)

The possibilities of graphic STM image simulation of a clean Si(1 1 1) 7 × 7 surface at atomic level are indicated. The presented procedure takes into account various types of deformation on the surface near the Fermi level in order to classify them and explain their origin. It also gives a clear hint to insert relevant physical phenomena in a suggested analysis. This goal is achieved exploiting the results of DAS (dimmer adatom stacing fault) model by means of standard mathematical programmes. A clean Si(1 1 1) 7 × 7 surface is considered as the representative example, but similar evaluation is possible for another non-metal and metal surfaces.     

A study of Ga layers on Si(1 0 0)-(2 × 1) by SR-PES: Influence of adsorbed water

Results for deposition and thermal annealing of gallium on the Si(1 0 0)-(2 × 1) surface achieved by synchrotron radiation photoelectron spectroscopy (SR-PES) and low energy electron diffraction (LEED) are presented. In addition to deposition of Ga on a clean surface, the influence of water adsorption on the arrangement of gallium atoms was also studied. The results on Ga deposition at a higher temperature (490 °C) are consistent with a Ga ad-dimer model showing equivalent bond arrangement of all Ga atoms for coverages up to 0.5 ML. The deposition onto a surface with adsorbed water at room temperature led to a disordered gallium growth. In this case gallium atoms bind to silicon dimers already binding fragments of adsorbed water. A subsequent annealing of these layers leads to a surface structure similar to the Ga-(2 × 2), however, it is less ordered, probably due to the presence of silicon oxides formed from water fragments.     

Vertical bonding distances of PTCDA on Au(1 1 1) and Ag(1 1 1): Relation to the bonding type

The vertical bonding distance of 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) above the Au(1 1 1) surface has been measured by the normal incidence X-ray standing wave (NIXSW) technique. The carbon skeleton of PTCDA has a vertical distance of D = (3.27 ± 0.02) Å to the Au(1 1 1) substrate. This distance corresponds very nearly to the sum of the van der Waals radii of carbon and gold, suggesting the adsorption to be a physisorptive one. In contrast, the PTCDA/Ag(1 1 1) interface which according to spectroscopic data follows the standard model of chemisorption very closely, shows a considerably smaller bonding distance of D = (2.86 ± 0.01) Å [A. Hauschild, K. Karki, B.C.C. Cowie, M. Rohlfing, F.S. Tautz, M. Sokolowski, Phys. Rev. Lett. 94 (2005) 036106, comment: Rurali et al., Phys. Lett. 95 (2005) 209205, reply: Phys. Rev. Lett. 95 (2005) 209206]. The different vertical adsorption heights of PTCDA on gold and silver are discussed in relation to the different bonding mechanisms on both noble metal surfaces.     

Growth kinetics of metastable (3 3 1) nanofacet on Au and Pt(1 1 0) surfaces

A theoretical epitaxial growth model with realistic barriers for surface diffusion is investigated by means of kinetic Monte Carlo simulations to study the growth modes of metastable (3 3 1) nanofacets on Au and Pt(1 1 0) surfaces. The results show that under experimental atomic fluxes, the (3 3 1) nanofacets grow by 2D nucleation at low temperature in the submonolayer regime. A metastable growth phase diagram that can be useful to experimentalists is presented and looks similar to the one found for the stationary growth of the bcc(0 0 1) surface in the kinetic 6-vertex model.     

Structural study of Si(1 1 1)-6 × 1-Ag surface using surface X-ray diffraction

The surface structure of Si(1 1 1)-6 × 1-Ag was investigated using surface X-ray diffraction techniques. By analyzing the CTR scattering intensities along 00 rod, the positions of the Ag and reconstructed Si atoms perpendicular to the surface were determined. The results agreed well with the HCC model proposed for a 3 × 1 structure induced by alkali-metals on a Si(1 1 1) substrate. The heights of the surface Ag and Si atoms did not move when the surface structure changed from Si(1 1 1)-√3 × √3-Ag to Si(1 1 1)-6 × 1-Ag by the desorption of the Ag atoms. From the GIXD measurement, the in-plane arrangement of the surface Ag atoms was determined. The results indicate that the Ag atoms move large distances at the phase transition between the 6 × 1 and 3 × 1 structures.     

Layer-resolved photoelectron diffraction from Si(0 0 1) and GaAs(0 0 1)

Photoelectron diffraction in the layer-resolved mode brings more detailed information about local atomic arrangement than is obtained in the standard mode. This is demonstrated in crystals with diamond and zinc-blende structures, both for unpolarized photon excitation as well as for circularly polarized excitation. The full angular distributions of photoemission intensities are evaluated for large atomic clusters representing ideally truncated surfaces of Si(0 0 1) and GaAs(0 0 1). Highly structured layer-resolved patterns enable a more detailed understanding of the standard mode outcomes. Photoelectron intensities from atomic layers placed at different depths under the crystal surface provide direct evidence about electron attenuation and its anisotropy in crystals.     

Density functional theory study of selenium adsorption on Fe(1 1 0)

The adsorption of atomic Se on a Fe(1 1 0) surface is examined using the density functional theory (DFT). Selenium is adsorbed in high-symmetry adsorption sites: the -short and long-bridge, and atop sites at 1/2, 1/4, and 1 monolayer (ML) coverages. The long bridge (LB) site is found to be the most stable, followed by the short bridge (SB) and top sites (T). The following overlayer structures were examined, p(2 × 2), c(2 × 2), and p(1 × 1), which correspond to 1/4 ML, 1/2 ML, and 1 ML respectively. Adsorption energy is −5.23 eV at 1/4 ML. Se adsorption results in surface reconstruction, being more extensive for adsorption in the long bridge site at 1/2 ML, with vertical displacements between +8.63 and −6.69% -with regard to the original Fe position-, affecting the 1st and 2nd neighbours. The largest displacement in x or y-directions was determined to be 0.011, 0.030, and 0.021 Å for atop and bridge sites. Comparisons between Se-adsorbed and pure Fe surfaces revealed reductions in the magnetic moments of surface-layer Fe atoms in the vicinity of the Se. At the long bridge site, the presence of Se causes a decrease in the surface Fe d-orbital density of states between 4 and 5 eV below Fermi level. The density of states present a contribution of Se states at −3.1 eV and −12.9 eV. stabilized after adsorption. The Fe-Fe overlap population decrease and a Fe-Se bond are formed at the expense of the metallic bond.     

Growth and morphology of the epitaxial Fe(1 1 0)/MgO(1 1 1)/Fe(1 1 0) Trilayers

Growth and surface morphology of epitaxial Fe(1 1 0)/MgO(1 1 1)/Fe(1 1 0) trilayers constituting a magnetic tunnel junction were investigated by low-energy electron diffraction (LEED) and scanning tunneling microscopy (STM). STM reveals a grain-like growth mode of MgO on Fe(1 1 0) resulting in dense MgO(1 1 1) films at room temperature as well as at 250 °C. As observed by STM, initial deposition of MgO leads to a partial oxidation of the Fe(1 1 0) surface which is confirmed by Auger electron spectroscopy. The top Fe layer deposited on MgO(1 1 1) at room temperature is relatively rough consisting of clusters which can be transformed by annealing to an atomically flat epitaxial Fe(1 1 0) film.     

Surface phase transition and electronic structure of c(5√2 × √2)R45°-Pb/Cu(1 0 0)

The c(5√2 × √2)R45°-Pb/Cu(1 0 0) surface phase is investigated by means of angle resolved ultraviolet photoemission and low energy electron diffraction in the temperature range between 300 and 550 K. We identify and characterize a temperature-induced surface phase transition at 440 K from the room temperature c(5√2 × √2) R45° phase to a (√2 × √2)R45° structure with split superstructure spots. The phase transition is fully reversible and takes place before the two-dimensional melting of the structure at 520 K. The electronic structure of the split (√2 × √2)R45° phase is characterized by a metallic free-electron like surface band. This surface band is backfolded with c(5√2 × √2)R45° periodicity phase at room temperature, giving rise to a surface band gap at the Fermi energy. We propose that a gain in electronic energy explains in part the stability of the c(5√2 × √2)R45° phase.     

Surface pre-melting and surface flattening of Bi nanofilms on Si(1 1 1)-7 × 7

We report on the in situ observation of temperature-driven drastic morphology evolution and surface pre-melting of the Bi(0 0 1) nanofilm deposited on the Si(1 1 1)-7 × 7 surface by use of spot-profile-analyzing low-energy electron diffraction (SPA-LEED). Surface step density of the single-crystalline, epitaxial Bi(0 0 1) film decreases above 350 K in a critical manner. On annealed Bi(0 0 1) films, we have detected surface pre-melting with a transition temperature of 350 K, which yields reversible diffraction intensity drop in addition to the harmonic Debye-Waller behavior. The observed surface flattening of the as-deposited film is driven by the increased amount of mobile adatoms created through the surface pre-melting.     

Perturbation of Ge(1 1 1) and Si(1 1 1)√3α-Sn surfaces by adsorption of dopants

We test the response of the √3 × √3α reconstructions formed by 1/3 monolayer of tin adatoms on silicon and germanium (1 1 1) surfaces upon doping with electrons or holes, using potassium or iodine as probes/perturbers of the initial electronic structures. From detailed synchrotron radiation photoelectron spectroscopy studies we show that doping with either electrons or holes plays a complimentary role on the Si and Ge surfaces and, especially, leads to complete conversion of the Sn 4d two-component spectra into single line shapes. We find that the low binding energy component of the Sn core level for both Si and Ge surfaces corresponds to Sn adatoms with higher electronic charge, than the Sn adatoms that contribute to the core level high binding energy signal. This could be analyzed as Sn adatoms with different valence state.     

Theoretical studies of electronic states and phonon modes on the TiC(0 0 1)(1 × 1) surface

We present a comprehensive picture of structural and electronic properties of the TiC(0 0 1)(1 × 1) surface. Our investigations are based on first-principles calculations within the local-density approximation of the density-functional theory. Good agreement has been observed between our calculation and experimental data for the atomic geometry of the surface. In particular, the calculated bond lengths between the first-layer C and the second-layer Ti (d_1C-2Ti = 2.188 Å) and between the first-layer Ti and the second-layer C (d_1Ti-2C = 2.031 Å) are in good agreement with the corresponding experimental values of 2.25 Å and 2.14 Å, respectively. We have also identified surface electronic states and provided clear support for previously available photoemission measurements. We have further calculated surface phonon modes at the zone centre and at the zone-edge point X using a linear response scheme based on the ab initio pseudopotential method. Our calculated surface phonon results are in excellent agreement with electron energy loss spectroscopy results.     

Adsorption and reactivity of SO2 on Ir(1 1 1) and Rh(1 1 1)

The adsorption and reactivity of SO₂ on the Ir(1 1 1) and Rh(1 1 1) surfaces were studied by surface science techniques. X-ray photoelectron spectroscopy measurements showed that SO₂ was molecularly adsorbed on both the Ir(1 1 1) surface and the Rh(1 1 1) surface at 200 K. Adsorbed SO₂ on the Ir(1 1 1) surface disproportionated to atomic sulfur and SO₃ at 300 K, whereas adsorbed SO₂ on the Rh(1 1 1) surface dissociated to atomic sulfur and oxygen above 250 K. Only atomic sulfur was present on both surfaces above 500 K, but the formation process and structure of the adsorbed atomic sulfur on Ir(1 1 1) were different from those on Rh(1 1 1). On Ir(1 1 1), atomic sulfur reacted with surface oxygen and was completely removed from the surface, whereas on Rh(1 1 1), sulfur did not react with oxygen.     

Comparative investigation of the c(2 × 2)-Si/Cu(0 1 1) and (√3 × √3)R30°-Cu2Si/Cu(1 1 1) surface alloys using DFT

The electronic structure of the c(2 × 2)-Si/Cu(0 1 1) surface alloy has been investigated and compared to the structures seen in the three phases of the (√3 × √3)R30°Cu₂Si/Cu(1 1 1) system, using LCAO-DFT. The weighted surface energy increase between the alloyed Cu(0 1 1) and Cu(1 1 1) surfaces is 126.7 meV/Si atom. This increase in energy for the (0 1 1) system when compared to the (1 1 1) system is assigned to the transition from a hexagonal to a rectangular local bonding environment for the Si ion cores, with the hexagonal environment being energetically more favorable. The Si 3s state is shown to interact covalently with the Cu 4s and 4p states whereas the Si 3p state, and to a lesser extent the Si 3d state, forms a mixture of covalent and metallic bonds with the Cu states. The Cu 4s and 4p states are shown to be altered by approximately the same amount by both the removal of Cu ion cores and the inclusion of Si ion cores during the alloying of the Cu(0 1 1) surface. However, the Cu 3d states in the surface and second layers of the alloy are shown to be more significantly altered during the alloying process by the removal of Cu ion cores from the surface layer rather than by the addition of Si ion cores. This is compared to the behavior of the Cu 3d states in the surface and second layers of the each phase of the (√3 × √3)R30°-Cu₂Si/Cu(1 1 1) alloy and consequently the loss of Cu-Cu periodicity during alloying of the Cu(0 1 1) surface is conjectured as the driving force for changes to the Cu 3d states. The accompanying changes to the Cu 4s and 4p states in both the c(2 × 2)-Si/Cu(0 1 1) and (√3 × √3)R30°-Cu₂Si/Cu(1 1 1) alloys are quantified and compared. The study concludes with a brief quantitative study of changes in the bond order of the Cu-Cu bonds during alloying of both Cu(0 1 1) and Cu(1 1 1) surfaces.