Morphology of Ni ultrathin films on Mo(1 1 0) and W(1 0 0) studied by LEED and STM

The morphology of ultrathin Ni films on Mo(1 1 0) and W(1 0 0) has been studied by low-energy electron diffraction and scanning tunneling microscopy. Ni films grow pseudomorphically on Mo(1 1 0) at 300 K for a coverage of 0.15 ML. A (8 × 1) structure is found at 0.4 ML, which develops into a (7 × 1) structure by 0.8 ML. The film undergoes a structural change to fcc Ni(1 1 1) at 6 ML. The growth mode switches from layer-by-layer to Stranski-Krastanov between 4 ML and 6 ML. Annealing at around 850 K results in alloying of submonolayer films with the substrate, while for higher coverages the Ni agglomerates into nanowedge islands. Ni films grow pseudomorphically on W(1 0 0) up to a coverage of around 2 ML at 300 K, above which there is a structural change from bcc to hcp Ni with the epitaxial relationship . This is accompanied by the formation of orthogonal domains of uniaxial strain-relieving dislocations from the third layer of the film. For coverages up to 1 ML the growth proceeds by formation of two-dimensional islands, but shifts to three-dimensional growth by 2 ML with rectangular islands aligned along the 〈0 1 1〉 substrate directions. Annealing at around 550 K results in agglomeration of Ni into larger islands and increasing film roughness.     

The epitaxial growth of Pd electrodeposition on Au(1 0 0) studied by LEED and RHEED

The epitaxial growth of Pd adlayers electrochemically deposited onto Au(1 0 0) has been studied by LEED, RHEED and AES. For the first 6 ML, the Pd deposits grow pseudomorphically on Au(1 0 0) with a lateral expansion of 4.5% with respect to bulk Pd. The strain in the expanded commensurate (1 × 1) Pd layers on Au(1 0 0) begins to be relieved at the Pd coverage between 6 and 9 ML range by formation of a compressed Pd film with respect to Au(1 0 0) surface and the compression increases continuously with thickness. At ca. 20 ML Pd the lattice constant of the film approaches to the bulk Pd and three-dimensional Pd islands develop since around 30 ML coverage. No superstructure due to the Pd-Au surface alloy can be found for coverages from monolayer up to 30 ML Pd on Au(1 0 0). A c(2 × 2) phase has been observed on the Pd-deposited Au(1 0 0) electrodes, which is ascribed to an ordered Cl adlayers adsorbed on Pd adlayers rather than a Pd-Au surface alloy.     

Herringbone and triangular patterns of dislocations in Ag, Au, and AgAu alloy films on Ru(0 0 0 1)

We have studied the dislocation structures that occur in films of Ag, Au, and Ag_0.5Au_0.5 alloy on a Ru(0 0 0 1) substrate. Monolayer (ML) films form herringbone phases while films two or more layers thick contain triangular patterns of dislocations. We use scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) to determine how the film composition affects the structure and periodicity of these ordered structures. One layer of Ag forms two different herringbone phases depending on the exact Ag coverage and temperature. Low-energy electron microscopy (LEEM) establishes that a reversible, first-order phase transition occurs between these two phases at a certain temperature. We critically compare our 1 ML Ag structures to conflicting results from an X-ray scattering study [H. Zajonz et al., Phys. Rev. B 67 (2003) 155417]. Unlike Ag, the herringbone phases of Au and AgAu alloy are independent of the exact film coverage. For two layer films in all three systems, none of the dislocations in the triangular networks thread into the second film layer. In all three systems, the in-plane atomic spacing of the second film layer is nearly the same as in the bulk. Film composition does, however, affect the details of the two layer structures. Ag and Au films form interconnected networks of dislocations, which we refer to as “trigons.” In 2 ML AgAu alloy, the dislocations form a different triangular network that shares features of both trigon and moiré structures. Yet another well-ordered structure, with square symmetry, forms at the boundaries of translational trigon domains in 2 ML Ag films but not in Au films.     

Temperature- and coverage-dependent evolution of the Au/Pd(1 1 0) surface structure

The morphology and the atomic scale structure of thin gold films (up to 2.5 ML) on Pd(1 1 0) were studied by means of scanning tunneling microscopy and surface X-ray diffraction. At room temperature the films exhibit a multilayer growth mode accompanied by the formation of highly anisotropic islands. Annealing above 500 K significantly increases the smoothness of the gold films, which are in registry with the substrate. Above a critical threshold of two monolayers a (1 × 2) missing-row reconstructed film is found. This reconstructed surface is well ordered after annealing at temperatures above 580 K. The specific gold film morphology is envisaged as a way to relax the strain caused by the mismatch between gold and palladium.     

Pd adsorption on Si(1 1 3) surface: STM and XPS study

Pd-induced surface structures on Si(1 1 3) have been studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). In the initial process of the Pd adsorption below 0.10 ML, Pd silicide (Pd₂Si) clusters are observed to form randomly on the surface. By increasing the Pd coverage to 0.10 ML, the clusters cover the entire surface, and an amorphous layer is formed. After annealing the Si(1 1 3)-Pd surface at 600 °C, various types of islands and chain protrusions appears. The agglomeration, coalescence and crystallization of these islands are observed by using high temperature (HT-) STM. It is also found by XPS that the islands correspond to Pd₂Si structure. On the basis of these results, evolution of Pd-induced structures at high temperatures is in detail discussed.     

Reconstruction and de-reconstruction of the Ir(1 0 0) surface and ultrathin Fe/Ir(1 0 0) films

The structure, energetics and magnetic properties of the quasihexagonal reconstruction of the Ir(1 0 0) surface and nanostructures formed by Fe atoms on this surface have been investigated using first-principles density functional theory with generalized gradient corrections. We find the reconstructed (1 × 5) surface to be 0.10 eV/(1 × 1) area lower in energy than the unreconstructed surface and we demonstrate that first-principles calculations can achieve quantitative agreement with experiment even for such long-period and deep-going reconstructions. For Fe coverage of 0.4 monolayers (ML) we have studied the stripe-like structure with biatomic Fe rows placed in the troughs of the (1 × 5)-reconstructed surface. Results of nonmagnetic calculations agree well with the structure inferred from STM data. Higher Fe coverages lead to a de-reconstruction of the Ir substrate. At 0.8 ML coverage a surface compound with composition Fe₄Ir is formed, which shows an appreciable buckling. In this case, a ferromagnetic calculation leads to good agreement with the low-temperature LEED data. We predict that the (1 × 5) periodicity of the mixed interface layer will persist also in thicker films with a pure Fe surface. Films with 1-4 ML Fe are predicted to be tetragonally distorted and ferromagnetic, with an axial ratio corresponding well to an elastic distortion of the Fe lattice.     

Selforganized nanopatterning of Si(0 0 1)

The (2 × n) superstructure of Si(0 0 1) consists of elongated (2 × 1) reconstructed stripes separated by a dimer-vacancy line every few nanometers, thus offering a means to obtain a nanopattered Si(0 0 1) surface. Scanning tunneling microscopy (STM) investigations of Si(0 0 1) substrates that were deoxidized at 880-920 °C reveal that the formation of the (2 × n) depends strongly on the Si coverage of the topmost surface layer. It forms only in a narrow coverage window ranging from 0.6 to 0.8 ML. Systematic Monte Carlo simulations by an algorithm that combines the diffusion of monomers and dimers with the simultaneous deposition of Si onto the Si(0 0 1) surface, corroborate the STM results and suggest Si deposition as a viable alternative for introducing dimer vacancies in a well-defined manner.     

Surface composition and structure of palladium ultra-thin films deposited on Ni(1 1 1)

Ultra-thin palladium films deposited on the Ni(1 1 1) surface were characterized by X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED) and X-ray photoelectron diffraction (XPD). For low coverage, LEED shows a (1 × 1) pattern similar to that of the substrate. For intermediate coverage, the LEED pattern displays extra spots around the main (1 × 1) spots, resembling a Moiré coincidence pattern, probably associated with the formation of Pd bi-dimensional islands oriented in different directions on the Ni(1 1 1) surface. The results obtained by XPS and XPD corroborate this finding. The LEED pattern displays this structure up to 500 °C. Annealing at 650 °C brings back the (1 × 1) pattern, which is associated with a Pd island coalescence and alloy formation by Pd diffusion in the first atomic layers of the Ni(1 1 1). In this paper we present a detailed study of this surface structure via a comparison between XPD experiment and theory.     

Self-assembled germanium nano-clusters on silver(1 1 0)

The adsorption of germanium on Ag(1 1 0) has been investigated by scanning tunnelling microscopy (STM), as well as surface X-ray diffraction (SXRD). At 0.5 germanium monolayer (ML) coverage, Low Energy Electron Diffraction (LEED) patterns reveals a sharp c(4 × 2) superstructure. Based on STM images and SXRD measurements, we present an atomic model of the surface structure with Ge atoms forming tetramer nano-clusters perfectly assembled in a two-dimensional array over the silver top layer. The adsorption of the germanium atoms induces a weak perturbation of the Ag surface. Upon comparison with results obtained on the (1 1 1) and (1 0 0) faces, we stress the role played by the relative interactions between silver and germanium on the observed surface structures.     

Nanowedge island formation on Mo(1 1 0)

The deposition of ultrathin Fe films on the Mo(1 1 0) surface at elevated temperatures results in the formation of distinctive nanowedge islands. The model of island formation presented in this work is based on both experiment and DFT calculations of Fe adatom hopping barriers. Also, a number of classical molecular dynamics simulations were carried out to illustrate fragments of the model. The islands are formed during a transition from a nanostripe morphology at around 2 ML coverage through a Bales-Zangwill type instability. Islands nucleate when the meandering step fronts are sufficiently roughened to produce a substantial overlap between adjacent steps. The islands propagate along the substrate [0 0 1] direction due to anisotropic diffusion/capture processes along the island edges. It was found that the substrate steps limit adatom diffusion and provide heterogeneous nucleation sites, resulting in a higher density of islands on a vicinal surface. As the islands can be several layers thick at their thinnest end, we propose that adatoms entering the islands undertake a so-called “vertical climb” along the sides of the island. This is facilitated by the presence of mismatch-induced dislocations that thread to the sides of the islands and produce local maxima of compressive strain. Dislocation lines also trigger initial nucleation on the surface with 2-3 ML Fe coverage. The sides of the nanowedge islands typically form along low-index crystallographic directions but can also form along dislocation lines or the substrate miscut direction.     

Electronic properties of Au nano-particles supported on stoichiometric and reduced TiO2(1 1 0) substrates

Growth modes and electronic properties were analyzed for Au nano-particles grown on stoichiometric and reduced TiO₂(1 1 0) substrates by medium energy ion scattering (MEIS) and photoelectron spectroscopy(PES) using synchrotron-radiation-light. Initially, two-dimensional islands (2D) with a height of one and two atomic layers grow and higher coverage increases the islands height to form three-dimensional (3D) islands for the stoichiometric TiO₂(1 1 0) substrate. In contrast, 3D islands start to grow from initial stage with a small Au coverage (?0.1 ML, 1 ML = 1.39 × 10¹⁵  atoms/cm²: Au(1 1 1)) probably due to O-vacancies acting as a nucleation site. Above 0.7 ML, all the islands become 3D ones taking a shape of a partial sphere and the Au clusters change to metal for both substrates. We observed the Au 4f and Ti 3p core level shifts together with the valence band spectra. The Ti 3p peak for the O-deficient surface shifts to higher binding energy by 0.25 ± 0.05 eV compared to that for the stoichiometric surface, indicating downward band bending by an electron charge transfer from an O-vacancy induced surface state band to n-type TiO₂ substrate. Higher binding energy shifts of Au 4f peaks observed for both substrates reveal an electron charge transfer from Au to TiO₂ substrates. The work functions of Au nano-particles supported on the stoichiometric and reduced TiO₂ substrates were also determined as a function of Au coverage and explained clearly by the above surface and interface dipoles.     

Growth, thermal stability and structure of ultrathin Zn-layers on Pd(1 1 1)

Low-energy ion scattering with monolayer sensitivity was applied to investigate ultrathin films of zinc on Pd(1 1 1). Uptake curves taken at 150 K indicate the simultaneous growth of multilayers with negligible interlayer transport. Annealing experiments for two-monolayer films reveal a rapid decrease in the zinc content on the surface layer at temperatures above 300 K, forming a metastable state with a Pd:Zn surface ratio of approx. 1:1 in the temperature region between 400 and 550 K. This state is most easily explained as a slightly buckled p(2 × 1)-PdZn surface alloy, with Zn atoms located approx. 0.25 Å above their Pd counterparts.     

Hydrogen adsorption and diffusion on Pd(1 1 1)

The adsorption, diffusion and ordering of hydrogen on Pd(1 1 1) was studied by scanning tunneling microscopy in the temperature range of 37-90 K. At low coverage isolated hydrogen atoms were observed. They formed √3×√3-1H islands as the coverage increased. Above 1/3 monolayer (ML) coverage areas of a new phase with √3×√3-2H structure were formed, with both structures coexisting between 1/3 and 2/3 ML. Finally a 1 × 1 structure was formed after high exposures of hydrogen above 50 K, with a coverage close to 1 ML. Atomically resolved images reveal that H binds to fcc hollow sites.     

Ultra-thin Si overlayers on the TiO2 (1 1 0)-(1 × 2) surface: Growth mode and electronic properties

The growth of thin subnanometric silicon films on TiO₂ (1 1 0)-(1 × 2) reconstructed surfaces at room temperature (RT) has been studied in situ by X-ray and ultra-violet photoelectron spectroscopies (XPS and UPS), Auger electron and electron-energy-loss spectroscopies (AES and ELS), quantitative low energy electron diffraction (LEED-IV), and scanning tunneling microscopy (STM). For Si coverage up to one monolayer, a heterogeneous layer is formed. Its composition consists of a mixture of different suboxides SiO_x (1 < x ? 2) on top of a further reduced TiO₂ surface. Upon Si coverage, the characteristic (1 × 2) LEED pattern from the substrate is completely attenuated, indicating absence of long-range order. Annealing the SiO_x overlayer results in the formation of suboxides with different stoichiometry. The LEED pattern recovers the characteristic TiO₂ (1 1 0)-(1 × 2) diagram. LEED I-V curves from both, substrate and overlayer, indicate the formation of nanometric sized SiO_x clusters.     

Growth mode and electronic structure of Au nano-clusters on NiO(0 0 1) and TiO2(1 1 0)

The growth mode and electronic structure of Au nano-clusters grown on NiO and TiO₂ were analyzed by reflection high-energy electron diffraction, a field-emission type scanning electron microscope, medium energy ion scattering and photoelectron spectroscopy. Au was deposited on clean NiO(0 0 1)-1 × 1 and TiO₂(1 1 0)-1 × 1 surfaces at room temperature with a Knudsen cell at a rate of 0.25-0.35 ML/min (1 ML = 1.39 × 10¹⁵ atoms/cm²:Au(1 1 1)). Initially two-dimensional (2D) islands with thickness of one Au-atom layer grow epitaxially on NiO(0 0 1) and then neighboring 2D-islands link each other to form three-dimensional (3D)-islands with the c-axis oriented to the [1 1 1] direction. The critical size to form 3D-islands is estimated to be about 5 nm². The shape of the 3D-islands is well approximated by a partial sphere with a diameter d and height h ranging from 2.0 to 11.8 nm and from 0.95 to 4.2 nm, respectively for Au coverage from 0.13 to 4.6 ML. The valence band spectra show that the Au/NiO and Au/TiO₂ surfaces have metallic characters for Au coverage above 0.9 ML. We observed Au 4f spectra and found no binding energy shift for Au/NiO but significant higher binding energy shifts for Au/TiO₂ due to an electron charge transfer from Au to TiO₂. The work function of Au/NiO(0 0 1) gradually increases with increase in Au coverage from 4.4 eV (NiO(0 0 1)) to 5.36 eV (Au(1 1 1)). In contrast, a small Au deposition(0.15 to 1.5 ML) on TiO₂(1 1 0) leads to reduction of the work function, which is correlated with an electron charge transfer from Au to TiO₂ substrate.     

Growth morphology of ultra-thin Ni films on Pd(1 0 0)

A series of thin Ni films, with thicknesses between 0.2 ML to 13 ML, were deposited on a Pd(1 0 0) substrate (a = 3.89 Å) at room temperature (RT). The growth morphology was investigated using scanning tunneling microscopy (STM). STM images indicate the existence of three different growth modes as a function of increasing coverage. Up to 6.5 ML, the films grow pseudomorphically, consistent with a face-centered tetragonal (fct) structure. From 6.5 ML to 10.5 ML a new apparent interlayer distance of 1.0 ± 0.1 Å is established. The new structure is accompanied by the appearance of an arrangement of filaments on the top layer surface. These filaments are presumably related to a strain relief mechanism of the fct films. Finally above 10.5 ML the Ni films recover the face-centered cubic (fcc) lattice constants. The filaments evolve, as a function of coverage, to form a net-like structure over the whole surface.     

Growth of ultra-thin cerium oxide layers on Cu(1 1 1)

The reactive vacuum deposition of CeO₂ on Cu(1 1 1) surface in oxygen atmosphere provides high quality epitaxial ceria overlayers. We report the growth characteristics of Ce oxide, the structures, and the temperature stability of the oxide phases as investigated by low-energy electron diffraction (LEED) and X-ray photoelectron spectroscopy. We find that Ce oxide on the Cu(1 1 1) grows initially in the form of islands giving sharp hexagonal LEED pattern of the CeO₂(1 1 1) structure corresponding to the (1.5 × 1.5) structure. The CeO₂-Cu(1 1 1) films exhibited mixed valence states and temperature dependent CeO₂-Ce₂O₃ transition above 900 K due to the vacuum annealing. The transition progressed more rapidly at the surface, probably by formation of oxygen vacancies.     

Alloy formation of Co/Ni/Pt(1 1 1)

The initial growth and alloy formation of ultrathin Co films deposited on 1 ML Ni/Pt(1 1 1) were investigated by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and ultraviolet photoelectron spectroscopy (UPS). A sequence of samples of d_Co Co/1 ML Ni/Pt(1 1 1) (d_Co = 1, 2, and 3 ML) were prepared at room temperature, and then heated up to investigate the diffusion process. The Co and Ni atoms intermix at lower annealing temperature, and Co-Ni intermixing layer diffuses into the Pt substrate to form Ni-Co-Pt alloys at higher annealing temperature. The diffusion temperatures are Co coverage dependent. The evolution of UPS with annealing temperatures also shows the formation of surface alloys. Some interesting LEED patterns of 1 ML Co/1 ML Ni/Pt(1 1 1) show the formation of ordered alloys at different annealing temperature ranges. Further studies in the Curie temperature and concentration analysis, show that the ordered alloys corresponding to different LEED patterns are Ni_xCo_1−xPt and Ni_xCo_1−xPt₃. The relationship between the interface structure and magnetic properties was investigated.     

Structure and electronic properties of gold adsorbed on Ti(0 0 0 1)

The Au/Ti(0 0 0 1) adsorption system was studied by low energy electron diffraction (LEED) and photoemission spectroscopy with synchrotron radiation after step-wise Au evaporation onto the Ti(0 0 0 1) surface. For adsorption of Au at 300 K, no additional superstructures were observed and the (1 × 1) pattern of the clean surface simply became diffuse. Annealing of gold layers more than 1 ML thick resulted in the formation of an ordered Au-Ti surface alloy. Depending on the temperature and annealing time, three surface reconstructions were observed by LEED: (√3 × √3) R30°, (2 × 2) and a one-dimensional incommensurate (√3 × √3) rectangular pattern. The Au 4f core level and valence band photoemission spectra provided evidence of a strong chemical interaction between gold and titanium. The data indicated formation of an intermetallic interface and associated valence orbital hybridization, together with diffusion of gold into the bulk. Au core-level shifts were found to be dependent on the surface alloy stoichiometry.     

Spectroscopic interpretation for Na-induced phase transitions on Na/Si(1 1 1)3 × 1

Na adsorption at room temperature causes the Na/Si(1 1 1)3 × 1 surface with Na coverage of 1/3 monolayer (ML) to transit into the Na/Si(1 1 1)6 × 1 surface at 1/2 ML and sequentially into the Na/Si(1 1 1)3 × 1 surface at 2/3 ML. The phase transition was studied by Si 2p core-level photoemission spectroscopy. The detailed line shape analysis of the Si 2p core-level spectrum of the Na/Si(1 1 1)3 × 1 surface (2/3 ML) is presented and compared to the Na/Si(1 1 1)3 × 1 surface (1/3 ML) which is composed of Si honeycomb chain-channel structures. This suggests that as additional Na atoms form atomic chains resulting in the Na/Si(1 1 1)3 × 1 surface (2/3 ML), the inner atoms of the Si honeycomb chain-channel structure is buckled due to the additional Na atoms.