Preparation and characterisation of Au(1 1 0) and Cu(1 1 0) surfaces for applications in ambient environments

The preparation of metal surfaces that in ambient conditions are flat and smooth over micron length scales is desirable for a wide range of applications. Scanning probe microscopy (SPM) studies of biomolecular adsorption and cell attachment require such well-prepared substrates. Standard polishing finishes are often found to exhibit considerable roughness and damage including scratches when investigated by SPM. We have prepared by means of UHV technology Au(1 1 0) and Cu(1 1 0) surfaces that when in ambient air exhibit a more homogeneous morphology and are considerably smoother than conventional polished surfaces. SPM techniques and the optical technique of reflection anisotropy spectroscopy (RAS) are used to characterise the morphological and electronic properties of these surfaces, respectively. The RA response of both Au(1 1 0) and Cu(1 1 0) surfaces in ambient conditions can be interpreted in terms of optical transitions between surface-modified bulk bands.     

ARPES and STS investigation of noble metal Shockley states: Confinement in vicinal Au(1 1 1) surfaces and self-organized nanostructures

Spectroscopic effects associated with the superperiodic surface structure have been observed in Au(1 1 1) vicinal surfaces and nanostructured systems. In the vicinal Au(23 23 21) surface, high resolution angle resolved photoemission spectroscopy shows the opening of several gaps in the surface band structure, whereas scanning tunneling spectroscopy reveals the energy dependence of the electronic density. These combined spectroscopic data allow to determine the reconstruction potential by deducing their first Fourier components. We also demonstrate that due to the peculiar growth on this Au vicinal surface, we can obtain a self-assembled superlattice of triangular Ag islands. The high ordering of the nanostructures leads to homogenous electronic properties.     

Atomic structure and electronic properties of Ta(1 1 2) and W(1 1 2) surfaces

We present results of theoretical and experimental studies of the structural and electronic properties of Ta(1 1 2) and W(1 1 2) surfaces. Atomic geometries of these surfaces and their electronic structures have been obtained from the first-principles pseudo-potential calculations based on the density functional theory and the use of the plane wave basis set. In the experimental part of our studies we have performed measurements of the photofield emission spectroscopy. The calculated density-of-states distributions are compared and discussed with energy distributions of electrons extracted from photofield emission characteristics. The photofield emission spectra measured for the surface regions of considered systems present very dense structures of features, while the corresponding dependences obtained for the bulk have much more smooth shape. Experimental results correspond very well with calculated density-of-states distributions.     

Effects of hyperthermal proton bombardment on alkanethiol self-assembled monolayer on Au(1 1 1)

The effects of hyperthermal proton bombardment on alkanethiol self-assembled monolayer (SAM) on Au(1 1 1) are studied with scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS). The STM and XPS results show that proton bombardment with proton energy as low as 2 eV can induce cross-linking of the adsorbed alkanethiols and transform the original ordered SAM lattice to an array of nanoclusters of the cross-linked alkanethiols. For a bombardment at 3 eV with a fluence of 3×10¹⁵ cm⁻², the typical cluster size is about 5 nm. In addition, the cluster size distribution is narrow, with no cluster larger than 8 nm. The cluster growth can be promoted by increasing the fluence at a fixed bombardment energy or increasing the energy at a fixed fluence. This indicates that surface diffusion of alkanethiols and cluster growth can be harnessed by the control of the bombardment energy and fluence.     

Growth and oxidation of aluminum thin films deposited on Ag(1 1 1)

Auger electron spectroscopy (AES) and low energy electron diffraction (LEED) were used to study the first steps of growth and oxidation of aluminum on Ag(1 1 1) substrate. We find that the growth of aluminum at room temperature (RT) shows the formation of a complete monolayer (ML) in epitaxy with the substrate. After deposition at RT of one aluminum ML, the dissolution kinetics is recorded at 200 °C and the bulk diffusion coefficient is deduced. We also show that the oxidation at RT of one aluminum ML is very rapid, and that both aluminum and oxygen do not dissolve in silver up to 500 °C. From the AES intensities variations, we deduce the composition profile of the oxide layer which corresponds probably to the stacking …/Ag/Ag/Al/O.     

Influence of growth temperature on structural and magnetic characterization of (In, Cr)As quantum dots

(In, Cr)As ferromagnetic semiconductor quantum dots (QDs) were grown by molecular beam epitaxy on GaAs (001) substrates. The growth temperature effects on structure and magnetism of the QDs were investigated systematically. The Cr2+3d⁴ states and quantum confined effect are assumed to play an important role in the room-temperature ferromagnetism of (In, Cr)As QDs.     

Atomistic simulation of Pt trimer on Pt(1 1 1) surface

The diffusion of Platinum trimer on Pt(1 1 1) is studied at different temperatures by molecular dynamics (MD) simulation. The structure stability is studied by cluster binding energy. The interaction between adatoms and surface atoms is discussed based on the calculated phonon density of state of Pt trimer. The diffusion coefficients of Pt trimer are derived from mean square displacement of cluster’s mass-center, which is obtained by long simulation times (?0.2 s) and tracing of interstitial atoms on surface. Then the diffusion prefactor and migration energy are deduced from Arrhenius relation. The calculated results are in reasonable agreement with experiment. In addition, using the diffusion prefactor and migration energy, the efficiency of Pt trimer as a critical nucleus for three-dimensional growth of thin films is discussed.     

Electronic structure of PdAg(1 0 0) ordered surface alloys using synchrotron radiation

PdAg(1 0 0) ordered surface alloys have been prepared by e-beam evaporation technique in situ in UHV and were investigated using high energy photoemission and normal incidence X-ray standing wave (NIXSW) techniques with wiggler radiation. The line shapes of 3d core levels of Ag and Pd exhibited interesting changes with the increase of Pd concentration in the alloys. The Ag 3d core level exhibited a disorder induced broadening that gradually increased with Pd concentration. On the other hand Pd 3d core level exhibited an asymmetry on the high binding energy side of the peak which gradually increased with Pd concentration. Interestingly, Pd core level did not exhibit a broadening with increase of Pd content in the alloy.     

Ag nanostructures on Au(7 8 8): A self-assembled superlattice of metallic quantum resonators

We have studied by scanning tunneling microscopy (STM) the effect of the reconstruction of a stepped Au(1 1 1) surface on the growth of silver sub-monolayer deposition. For narrow terraces, the reconstruction is disturbed and its pattern changes, Ag growth is therefore influenced. Thus growth of Ag on Au(7 8 8) vicinal surface can be controlled and leads to the formation of a highly ordered superlattice of nanostructures. Moreover, we show by tunneling conductance images that Ag islands exhibit electronic confinement effects of the Shockley surface state. Due to the homogeneity of their shapes and sizes, all the nanostructures of the self-assembled superlattice should exhibit similar electronic properties.     

An example of chemistry-morphology interaction: making up for the geometric and energetic heterogeneities of the (1 0 0) surface of single crystalline silicon by high-temperature treatments in H2

A lot of work has been carried out to prepare chemically homogeneous (1 0 0) silicon surfaces. The hydrogen-terminated (1 0 0) silicon surfaces are the most promising ones, especially in view of their remarkable environmental stability. The simplest way to produce hydrogen-terminated surfaces (attack in water solution of HF of a sacrificial, thermally grown, oxide) results in strongly heterogeneous rough surfaces (although with prevailing dihydride terminations). These surfaces can, however, be flattened and homogenized by treating them in H₂ at high temperature (>850 C). The morphological and chemical changes undergone by the surface during the treatment are studied X-ray photoelectron spectroscopy, atomic force microscopy, scanning tunnelling microscopy, infrared absorption spectroscopy in the attenuated total reflection mode, reflection high energy electron diffraction and thermal programmed desorption, and the mechanisms responsible for them are discussed.     

A theoretical study of structural and electronic properties of a missing dimer defect on Si- and C-terminated SiC(0 0 1)

We present a theoretical study of the geometrical and electronic properties of the C- and Si-terminated -SiC(0 0 1) surfaces in the vicinity of the missing dimer defect. The experimental results suggest that the atomic structures of these two surfaces may be considerably modified by external stress. In our present study we have considered the possible influence of this factor on the surface geometry of both systems. We have shown that the structural differences between the C- and Si-terminated surfaces lead to their different behaviour in the presence of a missing dimer and applied stress. In the case of the C-terminated c(2×2) surface, the missing dimer defect causes the buckling of the adjacent carbon dimers lying in the line of the defect (dimer atoms adjacent to the defect have vertical positions lower by 0.18 Å). This effect becomes more pronounced in the presence of compressive stress — the stress of 8% leads to the buckling of these two dimers of around 0.5 Å. The vertical positions of silicon atoms located directly below the defect were increased by 0.2 Å. We have also found that the missing dimer influences the structure of the carbon dimers on the neighbouring lines of dimers. Contrary to the C-terminated surface, the missing dimer defect on the Si-terminated SiC(0 0 1)-p(2×1) surface remains neutral for silicon dimers located in the line of defect, i.e. the dimers do not change their geometrical properties in unstrained structure nor in the presence of a tensile stress. On the other hand, this defect modifies considerably the geometry of the dimers from the two neighbouring lines of dimers by reducing their bond lengths and vertical positions. Changes in the geometrical properties of the second neighbour dimers (with respect to the defect) in these two lines are also noticeable. Moreover, we have found that the presence of a missing dimer modifies significantly the positions of the adjacent subsurface carbon atoms.     

Thickness dependence of X-ray absorption and photoemission in Fe thin films on Si(0 0 1)

To investigate the initial growth of Fe films on Si(0 0 1) and the Fe/Si interface, Fe films at various thicknesses have been systematically studied by soft X-ray absorption spectroscopy (XAS) and X-ray photoemission spectroscopy (XPS). The Fe L edge XAS spectrum shows a strong thickness dependence with broader line-width for thinner films. Detailed analysis of the Fe absorption signal as a function of the thickness shows that the broad linewidth of Fe L edge XAS spectra is mostly contributed by the first Fe layer at the Fe/Si interface. In contrast to XAS, Fe 2p photoemission spectra for these films are identical. However, valence band photoemission also shows a strong thickness dependence. Comparing the valence band photoemission spectra of the thin Fe/Si(0 0 1) films with that of pure Si and the thickest Fe film, the difference spectra at all thicknesses show almost identical shape indicating the same origin: the Fe/Si interface. Thus, it is mainly the first Fe layer at Fe/Si layer that is reactive with the Si substrate changing its electronic structure.     

Thionin adsorption on silicon (1 0 0): Structural analysis

In the search of new photoactive species that may be of use either in energy conversion or in photodynamic therapy, we studied the functionalization of silicon (1 0 0) with thionin using the glutaraldehyde coupling reaction. Surface properties were obtained by ellipsometric measurements, atomic force microscopy, and luminescence spectroscopy, which indicated the formation of a well organised monolayer in the silicon surface. In addition, the comparison of Raman spectroscopy data with first-principles pseudopotential calculations of the vibrational modes of the thionin molecule also indicate the formation of a monolayer of intact thionin molecules. Therefore, the simple functionalization process (involving only mild aqueous solution chemistry) described here works well and can be used to construct smooth monolayers of photoactive molecules with functional amine groups.     

Unidirectional hexagonal rare-earth disilicide nanowires on vicinal Si(100)-2×1

Rare-earth disilicide nanowires grown on vicinal Si(100) with a miscut of 2–2.5° toward the [110] azimuth at 600 °C were studied by scanning tunneling microscopy and compared with those grown on flat Si(001). In contrast to rare-earth disilicide nanowires grown on flat Si(100) surfaces, the nanowires grow unidirectionally along the [01̄1] direction of the vicinal Si(100) surface. Rare-earth disilicide nanowires form bundles composed of single nanowire units on both flat and vicinal surfaces. Yet, on the vicinal surface, the bundle width is comparable to the width of the terrace. The average nanowire length on the vicinal substrate is longer than that on the flat substrate. Scanning tunneling spectroscopy shows that the rare-earth disilicide nanowires have metallic properties. PACS 81.07.Vb; 81.16.Dn; 68.65.La; 68.37.Ef     

Pt-induced structures on Si(1 1 0) studied by STM

The structures induced by platinum (Pt) adsorption on Si(1 1 0) surface have been studied by scanning tunneling microscopy (STM) for coverage up to 2 monolayers (ML). Three surface phases have been found to form: “5×4”, “13×2” and “6×5” for Pt coverages 0.3, 0.5 and 1 ML respectively. All structures are formed by one-dimensional rows aligned along the direction. At the coverage >1 ML islands of, probably, Pt silicide start to form in form of 1D nanowires.     

Bi induced step-flow growth in the homoepitaxial growth of Au(1 1 1)

Homoepitaxial growth of Au on Bi-covered Au(1 1 1) was studied at room temperature using reflection high-energy electron diffraction (RHEED) and Auger electron spectroscopy (AES). From observations of RHEED it is found that the Au(1 1 1) (23 × 1) reconstruction structure changes to a (1 × 1) by about 0.16-0.5 ML deposition of Bi and to a (2√3 × 2√3)R30° by about 1.0 ML deposition of Bi, respectively. The surface morphology evolution by Bi deposition leads to a change of Au homoepitaxial growth behavior from layer-by-layer to step flow. This indicates that the surface diffusion distance of Au atoms on the Bi-precovered (1 × 1) and (2√3 × 2√3)R30° surfaces is longer than that on the Au(1 1 1) (23 × 1) clean surfaces. A strong surface segregation of Bi was found at top of surface. It is concluded that Bi atoms acted as an effective surfactant in the Au homoepitaxial growth by promoting Au intralayer mass transport.     

One-dimensional chain structure produced by Ce on vicinal Si(1 0 0)

One-dimensional Ce nanowires have been grown on a single-domain vicinal Si(1 0 0) surface. The growth mode, including the structural and electronic properties as a function of the substrate temperature and Ce coverage, was studied using scanning tunneling microscopy and scanning tunneling spectroscopy. The results show the formation of Ce nanowires along the step edges on the vicinal Si(1 0 0) substrate at 580 °C.     

Electrochemical Au deposition on stepped Si(1 1 1)-H surfaces: 3D versus 2D growth studied by AFM and X-ray diffraction

In order to grow magnetic layers on silicon substrates, a non-magnetic buffer layer is often needed to avoid silicide formation and to reproduce the perpendicular magnetic anisotropy obtained on metal single crystals, as in the case of Co on Au(1 1 1) and Pt(1 1 1). In this context, we have studied the electrochemical growth of Au buffer layers, and show that it is possible to obtain different film morphologies on hydrogen-terminated vicinal Si(1 1 1) surfaces by varying the electrochemical deposition parameters and solution composition. Two different morphologies have been obtained as observed by atomic force microscopy: continuous 2D Au films (chloride solution at pH 4), and films consisting in flat top 3D Au islands decorating the Si(1 1 1) step edges (cyanide solution at pH 14). X-ray diffraction measurements reveal that the gold layer and islands have Au(1 1 1) orientation and are in epitaxy with the Si(1 1 1) surface. In the case of islands, the lateral facets have also Au(1 1 1) orientation. Results are discussed within a model in which the breaking of the Si-H surface bonds plays a major role in the Au nucleation and growth mechanisms.     

Buffer effects of Ag layers on magneto-optical Co/Ge(1 0 0) ultrathin films

Magnetic properties of the Co/Ag/Ge(1 0 0) films grown at room temperature and 200 K were studied by the surface magneto-optical Kerr effect (SMOKE). More than 1.5 monolayer Ag buffer layers not only effectively block the interdiffusion between the capped Co layers and the Ge(1 0 0) substrate but also stabilize the magnetic phase. The temperature and thickness dependence on coercivity measurements show that interactions upon the interfaces are strongly correlated to the microstructures.     

Reconstructed (1 1 0) surfaces of FCC transition metals

The energies of the ideal, missing row (MR) and missing column (MC) (1 1 0) surfaces have been calculated by using modified embedded atom method (MEAM) for seven face centered cubic (FCC) transition metals Au, Pt, Ag, Pd, Rh, Cu and Ni. The results, that the MC reconstruction can not be formed for all metals, while the MR reconstruction can be formed naturally for Au and Pt, inductively for Ag, Pd, Rh and Cu and difficultly for Ni, are better than EAM calculated results in comparing with experimental results. In addition to the surface energy explanation, the results are also related to the surface topography and valence electron structure.