Lateral inhomogeneity of unoccupied states for PbPc films

Micro-spot two-photon photoemission (micro-2PPE) spectroscopy is used to probe unoccupied electronic levels at sub-monolayer (ML) films of lead phthalocyanine (PbPc) on graphite (HOPG). The high-energy resolution (30 meV) 2PPE spectra with high-lateral resolution (0.4 μm) show well-resolved features due to molecule-derived occupied/unoccupied levels and the image potential state (IPS). The surface images based on photoemission from the highest occupied molecular orbital (HOMO) become laterally uniform after an annealing procedure. By contrast, the images based on the peak due to the lowest unoccupied molecular orbital (LUMO) and the next LUMO (LUMO + 1) are laterally inhomogeneous even after the annealing. The IPS peak is broadened to higher energy by 0.3 eV for sub-ML films and becomes sharp when a 1 ML film is formed. The broadening indicates that the electron in the IPS is scattered by molecules within the mean free path in the range from 1 to 10 nm. PbPc molecules are randomly distributed including nm-clusters. The LUMO and LUMO + 1 levels are stabilized as the cluster size increases. The inhomogeneity of the surface image due to the LUMO + 1 peak arises from the size distribution of the nm-clusters. The present results demonstrate that the unoccupied levels are more sensitive to the environment than the occupied levels.     

Initial stages of Bi/Ge(111) interface formation: A detailed STM study

We present a detailed scanning tunneling microscopy investigation of ultra-thin Bi films on Ge(111)-c(2 × 8) in the range up to 1.5 ML. During growth at 300 K, the second/third atomic layer of Bi already starts to nucleate before the completion of the first/second layer correspondingly. Laterally isolated first layer Bi atoms, clusters and islands posses no electronic states in the range ~ 0.5 eV above the Fermi level of the substrate. In contrast, metallic electronic properties are found for continuous films when Bi coverage nears 1 ML. Annealing the as-deposited Bi films at 450 K causes lateral redistribution of Bi due to surface diffusion: coarsening of two-dimensional Bi islands with no long range order in the adsorbate layer is observed up to 1 ML; long range ordered (√3 × √3)-Bi/Ge(111) interface plus three-dimensional Bi clusters are obtained for coverages in excess of 1 ML.     

Rare earth free exchange spring magnet FeCo/FePt(001): Giant magnetic anisotropy and energy product

Using the full potential linearized augmented plane wave (FLAPW) method, we have investigated the thickness dependent magnetic properties of rare earth free exchange spring magnet FeCo/FePt(001). The FeCo adlayer thickness is increased from one monolayer (ML) to four ML coverage. It is observed that the FeCo adlayers and Fe atoms in FePt substrate show almost half metallic behavior, while an ordinary metallic feature is found in Pt atoms. The average magnetization increases with FeCo thickness and the estimated maximum energy product reaches 66 MGOe in FeCo(4 ML)/FePt(001). A giant perpendicular magnetocrystalline anisotropy (MCA) energy of 18.20 meV/cell is found in pure FePt(001) and it becomes 17.35 meV/cell even in FeCo(4 ML)/FePt(001). In addition, we find very large coercivity field in FeCo/FePt(001) systems. For instance, the calculated maximum coercivity field in FeCo(4 ML)/FePt(001) is about 188 kOe. Both energy product and coercivity field calculations may imply that the FeCo/FePt can be utilized for potential rare earth free exchange spring magnet material.     

Momentum-resolved lifetimes of image-potential states on Ag(001)

Binding energies and decay rates of image potential states at an Ag(001) surface have been investigated with time-resolved two-photon photoemission. For the first four image potential states the binding energies are determined to be 561, 170, 72 and 37 meV with respect to the vacuum level. Lifetimes of the first three states are extracted to be 57, 165 and 380 fs at k_∥ = 0. With increasing parallel momentum k_∥ the lifetime of the n = 1 state decreases such that the inverse lifetime scales proportional to the kinetic energy within the parallel motion with 34 meV/eV. As light source for the pump-probe photoemission experiments a novel all fiber based femtosecond laser system with a repetition rate of 1.5 MHz has been used.     

Interaction of Ag with the Si(1 1 1)1 × 1–H surface

Synchrotron radiation based photoemission spectroscopy (SRPES) and low energy electron diffraction (LEED) are used to study the interaction between Ag atoms and the Si(1 1 1)1 × 1–H surface. At an Ag coverage of 0.063 monolayers (ML) on the Si(1 1 1)1 × 1–H surface, the Si 2p component corresponding to Si–H bonds decreases, and an additional Si 2p component appears which shifts to a lower binding energy by 109 meV with respect to the Si bulk peak. The new Si 2p component is also observed for 0.25 ML Ag on the Si(1 1 1)7 × 7 surface. These findings suggest that Ag atoms replace the H atoms of the Si(1 1 1)1 × 1–H surface and form direct Ag–Si bonds. Contrary to the widely accepted view that there is no chemical interaction between Ag particles and the H-passivated Si surface, these results are in good agreement with recent first-principles calculations.     

Symmetrical transition of an atomic arrangement for 2D Bi films on Rh(111)

The atomic arrangement of submonolayer Bi films on Rh(111) surface was examined using low-energy electron diffraction (LEED) and scanning tunneling microscopy (STM). With low coverage, the LEED patterns showed incommensurate (IC) spots. The unit cell of IC was close to c(2 × 4) and had twofold symmetry. As the coverage increased, the unit cell shrank continuously along the [$\overline{1}10$] direction, and the commensurate c(2 × 4) was formed at a coverage of 0.5 ML. At the coverage above 0.5 ML, two different structures of c(2 × 4) and (4 × 4) were observed by STM. When the surface is fully saturated by monolayer Bi atoms, Bi atoms formed the uniform (4 × 4) structure with sixfold symmetry. This is due to a strong Bi–Rh attractive interaction resulting in the two-dimensional localization of Bi adsorbates on the surface. As a result, a symmetrical transition of Bi films from twofold to sixfold symmetry occurred on Rh(111).     

Correlated development of a (2 × 2) reconstruction and a charge accumulation layer on the InAs(111)–Bi surface

We have studied the formation of a Bi-induced (2 × 2) reconstruction on the InAs(111)B surface. In connection to the development of the (2 × 2) reconstruction, a two dimensional charge accumulation layer located at the bottom of the InAs conduction band appears as seen through a photoemission structure at the Fermi level. Not well ordered Bi layers do not induce a charge accumulation. The Bi-induced reconstruction reduces the polarization of the pristine surface and changes the initial charge distribution. InAsBi alloying occurs below the surface where Bi acts as charge donor leading to the charge accumulation layer.     

Ga-induced restructuring of Si(5 5 12) − 2 × 1 reconstructed surface at room temperature

Motivated by the need to form 1D-nanostructured dopants on silicon surfaces, we have attempted to grow Ga on the high index Si(5 5 12) surface which has a highly trenched (1D) morphology. The evolution of the interface with Ga adsorption in the monolayer regime has been probed by in situ AES, LEED and EELS. Controlling the kinetics by changing the Ga flux rates shows an interesting difference in the 1.0 to 1.5 ML region. The low flux rate (0.03 ML/minute) results in a Frank van der Merwe (layer by layer) growth mode up to 2 ML, while the higher flux rate (0.1 ML/minute) shows a transient island formation after the completion of 1 ML. The low rate shows the formation of 2 × (3 3 7) and (2 2 5) superstructures, while only the 2 × (3 3 7) is observed in a wide coverage range for the higher rate. The results demonstrate the ability to kinetically control the surface phases with different electronic properties of this technologically important interface.     

Adsorption of chlorine on Ru(0001)—A combined density functional theory and quantitative low energy electron diffraction study

Chlorine adsorption on Ru(0001) surface has been studied by a combined density functional theory (DFT) and quantitative low energy electron diffraction (LEED) approach. The (√3 × √3)R30°-Cl phase with Θ_Cl = 1/3 ML and chlorine sitting in fcc sites has been identified by DFT calculations as the most stable chlorine adsorbate structure on Ru(0001) with an adsorption energy of ? 220 kJ/mol. The atomic geometry of (√3 × √3)R30°-Cl was determined by quantitative LEED. The achieved agreement between experimental and simulated LEED data is quantified by a Pendry factor of r_P = 0.19 for a fcc adsorption site with a Cl-Ru bond length of 2.52 Å. At chlorine coverages beyond 1/3 ML LEED reveals diffuse diffraction rings, indicating a continuous compression of the hexagonal Cl overlayer with a preferred average Cl–Cl distance of 4.7 Å in the (√3 × √3)R30°-Cl, Θ_Cl = 1/3 ML phase towards 3.9 Å at saturation coverage of 0.48 ML.     

Texture and strain in CoPt/Ag nanocomposite films

The texture and microstrain in CoPt/Ag nanocomposite films is monitored as a function of film thickness. Perpendicular anisotropy due to (0 0 1) texturing is achieved by annealing films with thickness below 15 nm at 600°C. As a function of film thickness δ the texture evolves from weak (0 0 1) below 9 nm to strong (0 0 1) at δ=12 nm which deteriorates rapidly above 15 nm and evolves to (1 1 1) above 40 nm. The strain is minimized in the range of film thickness where the (0 0 1) texturing is optimum indicating a texturing mechanism related to the reduction of mechanical strain energy.     

Stabilization of high spin FCC Fe in (Fe/Pd)n multilayers

Polycrystalline (Fe/Pd)_n multilayers are grown onto sapphire substrates at room temperature in a UHV system. The number of periods n=40 and the thickness of Pd layers of t_Pd=4 nm are kept constant, whereas the thickness of the Fe layers is varied from 1.5 to 5 nm. Structural properties are studied by in situ reflection high energy diffraction (RHEED), scanning tunnelling microscopy (STM) and ex situ by X-ray diffraction at small angles and large angles. Analyzing the experimental data using the program SUPREX we obtain interplanar distances of d_Fe=2.03±0.01 Å for an Fe layer thickness larger than about 2.5 nm as expected for (1 1 0) planes of BCC Fe. For Fe layers with thicknesses less than about 2.5 nm the interplanar distance is d_Fe=2.1±0.01 Å, which is close to the distance between (1 1 1) planes of FCC Fe with a lattice parameter of a=3.64 Å. Magnetic susceptibility measurements at temperatures between 1.5 and 300 K for (Fe/Pd)_n multilayers with FCC Fe yield a magnetic moment per Fe atom of μ=2.7±0.1 μ_B, which is about 20% larger compared to μ=2.2 μ_B for BCC Fe. We show that the occurrence of the large magnetic moment originates from FCC Fe being in the high spin (HS) state rather than from polarization effects of Pd at Fe/Pd interfaces.     

Epitaxial alloyed films out of the bulk stability domain: Surface structure and composition of Ni3Al and NiAl films on a stepped Ni(1 1 1) surface

We have studied by Spot Profile Analysis Low Energy Electron Diffraction (SPA-LEED) and Auger Electron Spectroscopy (AES) Ni–Al alloyed layers formed by annealing, around 780 K, Al deposits on a stepped Ni(1 1 1) surface. The surface structure and composition of the thin epitaxial Ni₃Al and NiAl films, obtained respectively below and above a critical Al initial coverage θ_c, differ markedly from those of corresponding bulk alloys.The Ni₃Al ordered films form in a concentration range larger than the stability domain of the L1₂ Ni₃Al phase. The NiAl films present a marked distortion with respect to the lattice unit cell of the B2 NiAl phase, which slowly decreases when the film thickness increases.It also appears that the value of θ_c depends on the morphology of the Ni(1 1 1) substrate, increasing from θ_c = 4.5 ML for a flat surface to θ_c = 10 ML for a surface with a miscut of 0.4°. This could be directly related to the presence of steps, which favour Ni–Al interdiffusion.     

Surface X-ray diffraction analysis of Fe nanostructured films grown on c(2 × 2)-N/Cu(100)

We report the results of a Surface X-Ray Diffraction (SXRD) study of Fe nanostructured films deposited on c(2 × 2)-N/Cu(100) at room temperature (RT), with Fe coverage Θ_Fe = 0.5 ML and Θ_Fe = 1 ML. The c(2 × 2)-N/Cu(100) surface is an example of self-organised system, that can be used for growth of arrays of metal nano-islands and organic molecules assemblies. We chose two different values of N coverage, Θ_N = 0.3 ML and Θ_N = 0.5 ML, the second value corresponding to N saturation. We monitored the presence of surface diffraction peaks in hk scans and we performed Crystal Truncation Rods (CTR) analysis with ROD fitting programme. In the case of Θ_N = 0.5 ML, i.e. at saturation coverage, the CTR could be fitted with one surface domain with p4gm(2 × 2) symmetry. In the surface cell adopted, N atoms occupy four-fold hollow sites, with Fe (intermixed with Cu) giving rise to a “clock” reconstruction previously observed on iron nitride films obtained by co-deposition and annealing. This result is an indirect confirmation of N surface segregation on top of the Fe films, occurring during the growth at RT. When subsaturation N coverage (Θ_N = 0.3 ML) is used as a substrate for Fe deposition, the best results could be obtained with a model where two surface domains are present: the first one corresponds to a surface cell with Fe sitting in four-fold hollow sites on bare Cu areas, with possible interdiffusion in the second lattice. The second domain is assigned to growth of Fe on the N-covered square islands occurring once the bare Cu areas are fully covered. The SXRD analysis on N-covered surface domains shows that the mechanism of reconstruction and of N segregation on top layer is already active at RT for all N-coverage values.     

Characterisation of thin films obtained by laser ablation of Ge28Se60Sb12 glasses

Films of nominal composition Ge₂₈Se₆₀Sb₁₂ were deposited on microscope slides by pulsed laser deposition (PLD), using either bulk or powdered glassy targets and a Nd:YAG laser (λ=266 nm). The films with thickness comprised between 400 and 800 nm showed a smooth and dense morphology. They were homogeneous in composition all over the samples with a composition somewhat deficient in selenium compared to the nominal one: Ge_28.1±0.3Se_56.1±0.1Sb_15.8±0.2 and Ge_29.0±0.3Se_55.5±0.1Sb_15.5±0.2 for films obtained from powdered glassy targets and bulk targets, respectively. The optical characteristics of the films were extracted from the transmission spectra recorded between 250 and 2500 nm. In particular, the refractive index at 1.5 μm was found to be 2.75±0.03, close to that of the bulk glass, as expected for dense films. The decrease in the optical band gap and the increase in the Urbach absorption edge with the film thickness were attributed to an increase in disorder.     

Microstructures and nano mechanical properties of the metal tungsten film

The W film was prepared on 1045 steel by magnetron sputtering, with the thickness of 2 μm, its surface and cross-section morphologies were investigated with SEM, and the phase structure was analyzed with XRD. X-ray stress determinator was utilized to measure its residual stress, and the nano-hardness and elastic modulus of the film were surveyed by nano-indentation tester. The results show that the surface of W film is very compact and smooth; the particles arranged regularly, the granularity of the thin film is about 1 μm. The microcracks, cavities and desquamation were not found in the film and interface, and the bonding between the W film and substrate is well. The XRD results showed that the W film had a body-centered cubic structure, the lattice constant: a = 0.316 nm, the growth preferred orientations are (1 1 0) and (2 2 0). The compressive stress (−169 MPa) was found on the surface. The average nano-hardness and elastic modulus of W film are 15.22 GPa, 176.64 GPa, respectively, and the mechanical properties of W film are well.     

Magnetic anisotropy of epitaxial Fe layers grown on Si(0 0 1)

The magnetic properties of epitaxial iron films up to 80 monolayers (ML) thickness grown on Si(0 0 1) by using a template technique were investigated by means of superconducting quantum interference device and magneto-optic Kerr effect techniques. The thinnest films investigated (∼3 ML) exhibit a composition close to Fe₃Si with a Curie temperature below room temperature (RT) and strong out-of-plane remanent magnetization that reflects the presence of a dominant second order surface anisotropy term. Thicker films (⩾4 ML) are ferromagnetic at RT with remanent magnetization in film-plane and a composition closer to pure Fe with typically 8–10% silicon content. When deposited at normal incidence such films show simple in-plane fourfold anisotropy without uniaxial contribution. The relevant fourth-order effective anisotropy constant K₄^eff was measured versus film thickness and found to change its sign near 18 ML. The origin of this remarkable behavior is investigated by means of a Néel model and mainly traced back to fourth-order surface anisotropy and magneto-elastic effects related to the large biaxial in-plane compressive strain up to 3.5% in the thinnest (⩽25 ML) films.     

A two-dimensional alloy of immiscible Bi and Sn atoms on Rh(111)

We studied the atomic arrangements and the phase diagram of two-dimensional (2D) Bi–Sn binary films on Rh(111) with low-energy electron diffraction and scanning tunneling microscopy (STM). The 2D binary films exhibited (“2” × √3)-(Bi,Sn), (√7 × √7)R19°-(Bi,Sn), and (7 × 3√3)-(Bi,Sn) structures, depending on the compositional ratio of Bi and Sn. Atomically resolved STM images revealed that the binary films formed a BiSn₃ ordered alloy for the (√7 × √7)R19°-(Bi,Sn) structure and a solid solution alloy for the (“2” × √3)-(Bi,Sn) structure. The atomic configuration for the (7 × 3√3)-(Bi,Sn) structure was closely related to that of (√7 × √7) R19°-(Bi,Sn).     

In situ magneto-optical Kerr effect study of uncovered Fe films on ZnSe(0 0 1)

The magnetic properties of uncovered Fe/ZnSe/GaAs(1 0 0) ultrathin films have been determined in situ by magneto-optical Kerr effect (MOKE). Fe films up to 10 monolayers (ML) thick were deposited on c(2×2) Zn-rich ZnSe/GaAs(0 0 1) surfaces at 180 °C. We have studied the thickness dependence of the in-plane lattice parameter of the Fe films and of the MOKE hysteresis loops in the longitudinal geometry, at 150 K, under magnetic fields up to 0.1 T applied along the [1 1 0] and [1-1 0] directions of the ZnSe(0 0 1). Reflection high energy electron diffraction show that in the low thickness regime the Fe films present an in-plane structural anisotropy characterized by an expansion along the [1 1 0] direction. Hysteretic loops were obtained only starting from ∼5 ML Fe. We found the onset of an uniaxial magnetic anisotropy with [1 1 0] magnetic easy axis at 7 ML Fe.     

The growth of Ag films on a TiO2(110)-(1×1) surface

We report here the growth of Ag film and its thermal stability on the TiO₂(1 1 0)-(1×1) surface using combination techniques of low-energy ion scattering (LEIS), X-ray photoelectron spectroscopy (XPS), and low-energy electron diffraction (LEED). At a surface temperature as low as 125 K, a 2D growth of Ag films seems to occur for submonolayer coverages up to ∼0.8 ML. Annealing of low temperature grown Ag films to 500 K for coverage of 1–2.4 ML would result in the formation of metastable Ag layers with rest of Ag forming 3D needle-like islands on top of this Ag film.