Elastic origin of the O/Cu(1 1 0) self-ordering evidenced by GIXD

We have studied by grazing incidence X-ray diffraction the self-ordering of the Cu-CuO stripe pattern. By comparing the experimental results to molecular dynamics simulations and anisotropic linear elastic calculations, we have been able to determine the atomic relaxations within the Cu substrate. The results show the importance of the crystalline anisotropy in the relaxation field. These relaxations are due to the surface stress difference Δσ between oxygen-covered and bare Cu(1 1 0) regions. For the different oxygen coverages studied, we have always found Δσ=1.0±0.1 N m⁻¹. This surface stress difference is shown to be the origin of the self-ordering.     

Boundaries between square-shaped,nitrogen-adsorbed islands on Cu(001): Two relief mechanisms of the stress induced by atomic adsorbates

We have performed a scanning tunneling microscopy study on a grid-like mesoscopic pattern formed by nitrogen adsorption on a Cu(001) surface. Two types of boundaries are present between square-shaped N-adsorbed islands: a fine straight line of monoatomic width (“monoatomic line”) and a bare Cu(001) belt of several atoms wide (“multiatomic belt”). The boundary type depends on whether c(2 × 2) protrusions in neighboring islands are aligned in-phase or out-of-phase across the boundary. Considering that an adsorbed N atom prefers to be coordinated by four Cu atoms on a plane and that the topmost Cu layer is expanded by 2–3% by N adsorption, we propose the missing-Cu-atom model for a monoatomic line where a single Cu row is ejected by a compressive stress exerted from neighboring N-islands. The reconstruction maintains the planar 4-fold coordination of Cu atoms to an N atom in the case of in-phase alignment, and relieves the N-induced compressive stress very efficiently. Whereas, the Cu row ejection would destroy the stable local structure in the out-of-phase case. The N-induced compressive stress is relieved in the other mechanism where it is compensated with a tensile stress in a bare Cu(001) region. The region is imaged as a multiatomic belt. The above models for a monoatomic line and a multiatomic belt explain well various features observed in the grid pattern. Moreover, the missing-Cu-atom model rationalizes the attractive interaction between N-islands which was difficult to understand in a traditional, elasticity-based view on the self-organization.     

First principles calculations of relationship between the Cu surface states and relaxations

In this paper the relationship between the surface relaxations and the electron density distributions of surface states of Cu(100), Cu(110), and Cu(111) surfaces is obtained by first-principles calculations. The calculations indicate that relaxations mainly occur in the layers at which the surface states electrons are localized, and the magnitudes of the multilayer relaxations correspond to the difference of electron density of surface states between adjacent layers. The larger the interlayer relaxation is, the larger the difference of electron density of surface states between two layers is.     

Diffusion mechanism of Cu adatoms on a Cu(001) surface

Ab initio calculations on surface diffusion of Cu adatoms on Cu(001) are presented. The hopping mechanism with a calculated energy barrier of 0.69 eV is found to be favorable over the exchange mechanism with 0.97 eV. We find from the geometry relaxations that adatoms are significantly attracted to the surface and push away nearest-neighbor atoms in the surface. Lateral relaxations of atoms in the surface are larger than vertical ones.     

Step interactions on Pt(111) vicinal surfaces determined by grazing incidence X-ray diffraction: Influence of the step orientation

We have studied the step–step interactions on the Pt(997) vicinal surface. Grazing incidence X-ray diffraction (GIXD) allowed us to measure the elastic atomic relaxations near the surface due to the steps. By means of the model of buried elastic dipoles, within the framework of anisotropic linear elasticity (ALE) calculations, the surface stress of Pt(111), and the elastic interaction between steps are deduced. The values so-obtained are compared to the values previously measured on the Pt(779) surface with the same technique. The comparison shows the strong influence of step geometry on step interactions.     

Direct evidence for mesoscopic relaxations in cobalt nanoislands on Cu(001)

Surface x-ray diffraction in combination with scanning tunneling microscopy and molecular dynamics calculations provide first quantitative evidence for unusually large relaxations in nanometer-sized Co islands deposited on Cu(001) at 170 K. These lead to sharply reduced interatomic Co distances as low as 2.36 A as compared to bulk Co (2.51 A) involving low symmetry Co adsorption sites. Our results prove the validity of the concept of mesoscopic mismatch which governs the strain relaxation of nanosized islands in general.     

Atomic and nanostructures of monolayer c(2 × 2)NiN on Cu(0 0 1)

Structures of monolayer nickel nitride (NiN) on Cu(0 0 1) surface are studied by X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). Formations of Ni–N chemical bonds and NiN monolayer at the surface are confirmed by XPS on the N-adsorbed Cu(0 0 1) surfaces after Ni deposition and subsequent annealing to 670 K. A c(2 × 2) structure is always observed in the LEED patterns, which is a quite contrast to the (2 × 2)p4g structure observed usually at the N-adsorbed Ni(0 0 1) surface. Atomic images by STM indicate the mixture of Ni–N and Cu–N structures at the surface. Density of the trenches on the N-saturated surface decreases and the grid pattern on partially N-covered surfaces becomes disordered with increasing the Ni coverage. These results are attributed to the decrease of the surface compressive stress at the N-adsorbed Cu surface by mixing Ni atoms.     

Correlation of stress and atomic-scale surface roughness evolution during intermittent homoepitaxial growth of (111)-oriented Ag and Cu

Stress evolution during intermittent homoepitaxial growth of (111)-oriented Cu and Ag thin films has been studied. A tensile stress change is observed when growth is stopped, but the change is reversed when growth is resumed. Reflection high energy electron diffraction analysis of the atomic scale surface roughness during intermittent growth demonstrates a strong correlation between the surface structure and reversible stress evolution. The results are discussed in terms of an evolving surface defect population.     

Femtosecond laser induced submicrometer structures on the ablation crater walls of II-VI semiconductors in water

Femtosecond laser ablations (100 fs, 800 nm, 0.2 mJ/pulse) were performed to produce craters on CdS, ZnS:Cu and ZnSe wafers in water. On the surface of the crater walls, a variety of submicrostructural formations were presented, such as the ripples and network structures for CdS, the subwavelength ripples and columnar structures for ZnS:Cu, even the regular cubic-shaped submicron rods for ZnSe. Based on the field-emission scanning electron microscope (FE-SEM) study of the different characteristic surface morphologies, the possible formation mechanisms were discussed correspondingly. For example, two distinct mechanisms are contributing to the different styles of ripples formed on CdS and ZnS:Cu. The former is the interference effects between the incoming laser beam and scattered surface wave, while the latter is the self-organization structure formation. In addition, the re-crystallization of the water-confined hot plasma would play an important role in the formation of ZnS:Cu column structures and ZnSe rods.     

Self-organization of iron-atom nanostructures in the first layer of the (100) copper surface

Mechanisms of the diffusion of surface vacancies and iron atoms in the first layer of the Cu(100) surface have been studied by molecular dynamics and the kinetic Monte Carlo method. The diffusion of embedded atoms results in the self-organization of bound iron-atom nanostructures. The time dependences of the number of most widespread nanostructures have been obtained. According to the results, the self-organization of embedded nanostructures can be divided into three stages in which the copper surface has significantly different morphologies.     

New relaxation phenomena in the outer atomic layers of Fe{211}

A low-energy electron diffraction analysis of a {211} surface of body-centered cubic iron reveals relaxations in the directions perpendicular and parallel to the surface plane. Both relaxations alternate in successive layers. The perpendicular relaxation goes from contraction of 10.5% to expansion of 5% to contraction of 1%. The parallel relaxation goes from a shift of the first layer of 0.24Å (10% of the nearest neighbor distance) toward more symmetrical registration with the second layer, to an opposite shift of 0.035 Å of the second layer with respect to the third.     

Atomic geometry of Si(111) 7×7 by dynamical low-energy electron diffraction

A complete determination of individual atomic coordinates for the Si(111) 7×7 surface has been carried out by dynamical low-energy electron diffraction. The dimer-adatom-stacking fault (DAS) model, after large vertical and lateral relaxations, was found to produce calculated spectra in remarkably good agreement with the data. Atoms in the faulted half of the unit cell are raised from those of the unfaulted half. Adatoms at corner sites are higher than those at center sites.     

Density functional theory studies on stress stabilization of the Cu(1 1 0) striped phase

Under oxygen exposure, the Cu(1 1 0) surface shows a striped phase consisting of alternating bare (1 1 0) surface areas and added-row (2 × 1)O reconstructions. Density functional theory is used to show that the major origin for the formation of the striped phase is the elastic interaction between these areas. The difference between the surface stress of the bare surface and the (2 × 1)O covered surface is predicted to be 1.3 N/m in reasonable agreement with values derived from grazing incidence X-ray diffraction. Supercell calculations for periods of up to 62 Å confirm that the formation of the striped phase is favorable compared to an added-row (4 × 1)O reconstruction with the same coverage. But the predicted equilibrium period of roughly 30 Å is significantly smaller than in experiment. The calculations are impeded by the surface energy alternating with the number of layers in the slab. This behavior is related to a quantum well behavior of the Cu 4s-electrons. A simple model for this behavior is discussed and compared to ab initio results.     

Chlorine chemisorption on Cu(0 0 1) by surface X-ray diffraction: Geometry and substrate relaxation

We report on the precise location of Cl atoms chemisorbed on a Cu(0 0 1) surface and the interlayer relaxations of the metal surface. Previous studies have shown that chlorine dissociates on Cu(0 0 1) to form a c(2 × 2) chemisorbed layer with Cl atoms occupying four-fold hollow sites. A Cu-Cl interlayer spacing of 1.60 Å and a slightly expanded Cu-Cu first interlayer spacing of 1.85 Å (1.807 Å for bulk Cu) was determined by LEED. The resulting Cu-Cl bond length, 2.41 Å, is very similar to the SEXAFS value of 2.37 Å. Contradictory results were obtained by angle-resolved photoemission extended fine structure: while confirming the Cu-Cl interlayer spacing of 1.60 Å, no first Cu-Cu interlayer relaxation has been observed. On the other hand, a small corrugation of the second Cu layer was pointed out. We carried out a detailed structural determination of the Cu(0 0 1)-c(2 × 2)-Cl system using surface X-ray diffraction technique with synchrotron radiation. We find a Cu-Cl interlayer spacing of 1.584(5) Å and confirm the expansion of the first Cu-Cu interlayer, with an average spacing of 1.840(5) Å. In addition, we observe a small corrugation of the second Cu layer, with Cu atoms just below Cl atoms more tightly bound to the surface layer, and even a second Cu-Cu interlayer expansion.     

Acetylene on Cu(111): imaging a molecular surface arrangement with a constantly rearranging tip

Acetylene on Cu(111) is investigated by scanning tunnelling microscopy (STM); a surface pattern previously derived from diffraction measurements can be validated, if the variation of the STM image transfer function through absorption of an acetylene molecule onto the tip apex is taken into account. Density functional theory simulations point to a balance between short-range repulsive interactions of acetylene/Cu(111) associated with surface stress and longer range attractive interactions as the origin of the ordering.     

Bonding of nitrogen atoms on Cu(001) surfaces: A cluster approach

A study of the chemisorption of nitrogen atoms on a copper surface has been performed, based on an analysis of the electronic structure of the Cu₅N cluster obtained from self-consistent-field Xα scattered-wave calculations. Our calculations show that the chemisorption of nitrogen on Cu(001) surfaces induces peaks below and above the Cu d-band region in the total density of states curve. The bonding orbitals formed between the N 2p and the Cu valence orbitals are generally found near the bottom of the Cu d-band region, while the antibonding orbitals formed between the N 2p and Cu orbitals are found to lie above the Cu d-band region. These hybridized orbitals involving the N 2p orbital gave a satisfactory interpretation of the adsorbate-induced structure reported in N/Cu(001) ultraviolet photoemission (UPS) studies. In addition, the separate contributions of the N 2p⊥ and 2p∥ states to the total density of states curve of the Cu₅N cluster are given. This information may be useful in interpreting angleresolved UPS data.     

Surface relaxation and surface stress of 4d transition metals

Using the density functional theory formulated within the framework of the exact muffin-tin orbitals method, we present a systematic study of the top layer relaxation and surface stress of 4d transition metals. Our calculations predict layer contractions for most surfaces. We also find that the relaxations of the close packed surfaces decrease with increasing atomic number through the 4d series. We propose that the relaxation is mainly due to the reduction of the number of sp electrons in the surface layer relative to bulk. The surface stress is found to be very sensitive to the relaxation and, therefore, an accurate determination of the layer relaxation is necessary for obtaining reliable values for the surface stress. Comparing the top layer relaxations for the close packed surfaces, we see essential deviations between data derived in different ab initio calculations. At the same time, the overall trend for the present surface stress of 4d metals is in reasonable agreement with recent full-potential data.     

Improvement of Field Emission Characteristics of Copper Nitride Films with Increasing Copper Content

A copper nitride （Cu3N） thin film is deposited on a Si substrate by the reactive magnetron sputtering method. The XPS measurements of the composite film indicate that the Cu content in the film is increased to 80.82 at. % and the value of the Cu/N ratio to 4.2：1 by introducing 4% 112 into the reactive gas. X-ray diffraction measurements show that the film is composed of Cu3N crystallites with an anti-ReO3 structure. The effects of the increase of copper content on the field emission characteristics of the Cu3N thin film are investigated. Significant improvement in emission current density and emission repeatability could be attributed to the geometric field enhancement, caused by numerous surface nanotips, and the decrease of resistivity of the film.     

Magnetic properties of Fe and Co nanoclusters embedded in the first Cu(100) surface layer

The magnetic anisotropy energies, as well as spin and orbital magnetic moments of the atoms involved in the simplest nanostructures formed due to the self-organization within the first Cu(100) surface layer, are calculated in the framework of the density functional theory. The critical role of the surface relaxation, which leads to the rotation of the easy magnetization axis in iron nanoclusters, is demonstrated in the calculations of magnetic anisotropy.     

First-principles-based surface phase diagram of fully relaxed binary alloy surfaces

The combination of density-functional theory (DFT) calculations of geometrically fully relaxed binary alloy surfaces with concepts from statistical physics is applied to construct a DFT-based phase diagram for a binary alloy surface. As a first example, we studied the appearance of Co antisite atoms at CoAl(100) surfaces. The structural parameters as multilayer relaxations, surface buckling, lateral order, and segregation profile of the predicted stable surface phases are in excellent agreement with experimental structure determinations applying low-energy electron diffraction.