XPS and RBS investigations of Si–Er–O interactions on a Si(1 0 0)-2x1 surface

The interactions among erbium, oxygen and silicon atoms on a Si(1 0 0)-2x1 reconstructed surface have been studied by means of X-ray photoelectron spectroscopy and Rutherford backscattering spectrometry. Erbium and oxygen were deposited at 600 °C on the Si surface and their behavior has been observed after different thermal processes. It was found that at 600 °C, the formation of a stable surface complex Er–O–Si is obtained together with Si oxidation; after an 800 °C annealing, the amount of oxygen bound to Si decreases and the remaining O atoms are mainly bonded to Er. An abrupt change was observed after 900 and 1000 °C annealings, which bury the Er atoms about 60 Å below the substrate surface. Our results give some hints to hypotise the O diffusion towards the Si bulk.     

Local adsorption sites and bondlength changes in Ni(1 0 0)/H/CO and Ni(1 0 0)/CO

The local adsorption geometry of CO adsorbed in different states on Ni(1 0 0) and on Ni(1 0 0) precovered with atomic hydrogen has been determined by C 1s (and O 1s) scanned-energy mode photoelectron diffraction, using the photoelectron binding energy changes to characterise the different states. The results confirm previous spectroscopic assignments of local atop and bridge sites both with and without coadsorbed hydrogen. The measured Ni–C bondlengths for the Ni(1 0 0)/CO states show an increase of 0.16 ± 0.04 Å in going from atop to bridge sites, while comparison with similar results for Ni(1 1 1)/CO for threefold coordinated adsorption sites show a further lengthening of the bond by 0.05 ± 0.04 Å. These changes in the Ni–CO chemisorption bondlength with bond order (for approximately constant adsorption energy) are consistent with the standard Pauling rules. However, comparison of CO adsorbed in the atop geometry with and without coadsorbed hydrogen shows that the coadsorption increases the Ni–C bondlength by only 0.06 ± 0.04 Å, despite the decrease in adsorption energy of a factor of 2 or more. This result is also reproduced by density functional theory slab calculations. The results of both the experiments and the density functional theory calculations show that CO adsorption onto the Ni(1 0 0)/H surface is accompanied by significant structural modification; the low desorption energy may then be attributed to the energy cost of this restructuring rather than weak local bonding.     

The atomic and electronic structure of the TiO2- and BaO-terminated BaTiO3(0 0 1) surfaces in a paraelectric phase

Relaxation and rumpling of BaTiO₃(0 0 1) surface with two different terminations have been investigated from ab initio local density approximation calculations. Large displacements of ions deviated from their crystalline sites have been obtained. These kinds of displacements lead to the formation the surface rumpling, dipole moments and electric field in the near-surface region. Band structures, density of states, bond population and electronic density redistributions have been obtained. Considerable enhancement of Ti–O chemical bond covalency nearby the surface, especially for the TiO₂ termination surface, has been found.     

Regular step formation on concave-shaped surfaces on 6H–SiC(0 0 0 1)

A concave-shaped surface has been prepared in a 6H–SiC(0 0 0 1) substrate by mechanical grinding. As a consequence, the different crystallographic planes building up the 6H–SiC polytype are cut under continuously changing polar angles in all azimuthal directions. Through hydrogen etching, this curved surface breaks up into a whole set of surfaces vicinal to the initial 6H(0 0 0 1) orientation. The local structural reorganisation after hydrogen etching has been studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Two types of local bond environments are present at the step edges leading to a strong anisotropy in the surface etching with hydrogen. As a result, the distribution of the terrace width and the step heights varies with the azimuthal angle and reflects the sixfold symmetry of the bulk crystal. For most azimuthal directions, an alternation of large and small terraces, separated by steps of 0.75 nm heights (height of half the 6H polytype, three bilayers) is observed and only for well defined azimuthal directions, equally spaced terraces separated by steps of 1.5 nm height (one unit cell of 6H–SiC, six bilayers) are found. In addition, the polar variations have been studied by taking various line-scans along the concave-shaped surface with AFM. It seems that for polar angles above 3°, step bunching of several SiC steps occurs whereas below 3° the bimodal terrace width distribution is observed.     

The origin of photoluminescence in Ge-implanted SiO2 layers

Ge ions were implanted at 100 keV with 3×10¹⁶ cm⁻² into a 300  nm thick SiO₂ layer on Si. Visible photoluminescence (PL) around 2.1 eV from an as-implanted sample is observed, and faded out by subsequent annealing at 900°C for 2 h. However, PL shows up again after annealing above 900°C at the same peak position. Compared with the as-implanted sample, significant increase of Ge–Ge bonds is measured in X-ray photoelectron spectroscopy, and the formation of Ge nanocrystals with a diameter of 5 nm are observed in transmission electron microscopy from the sample annealed at 1100°C. We conclude that the PL peak from the sample annealed above 900°C is caused by the quantum confinement effects from Ge nanocrystals, while the luminescence from the as-implanted sample is due to some radiative defects formed by Ge implantation.     

Short period (Si6Ge4)p superlattices: photoluminescence and electron microscopy study

Si–Ge heterostructures made of 6 monolayers of Si and 4 monolayers of Ge repeated p times (Si₆Ge₄)_p, strained on Si (1 0 0) substrates, have been investigated by photoluminescence measurements and electron microscopy. The films were grown at 400°C by molecular beam epitaxy, using Sb as surfactant. The photoluminescence results of the whole set of samples show similar spectra, for both the single Ge quantum well (p=1) and the thicker heterostructure (p=30). The phonon assisted transverse optical line is measured at about 40 meV far from the no-phonon one, and this corresponds to the Ge–Ge vibration. Our results demonstrate that excitonic recombination occurs mainly in the Ge layers and it is indirect in nature, whatever the repetition number (p) is. Furthermore, we evidenced a high localization of the photoluminescence process excluding any superperiodicity effect.     

The structure of oxygen on Cu(1 0 0) at low and high coverages

The local adsorption structure of oxygen on Cu(1 0 0) has been studied using O 1s scanned-energy mode photoelectron diffraction. A detailed quantitative determination of the structure of the 0.5 ML (√2×2√2)R45°-O ordered phase confirms the missing-row character of this reconstruction and agrees well with earlier structural determinations of this phase by other methods, the adsorbed O atoms lying only approximately 0.1 Å above the outermost Cu layer. At much lower coverages, the results indicate that the O atoms adopt unreconstructed hollow sites at a significantly larger O–Cu layer spacing, but with some form of local disorder. The best fit to these data is achieved with a two-site model involving O atoms at Cu–O layer spacings of 0.41 and 0.70 Å in hollow sites; these two sites (also implied by an earlier electron-energy-loss study) are proposed to be associated with edge and centre positions in very small c(2×2) domains as seen in a recent scanning tunnelling microscopy investigation.     

Well-ordered (1 0 0) InAs surfaces using wet chemical treatments

Atomic ordering of HCl-isopropanol (HCl-iPA) treated and vacuum annealed (1 0 0) InAs surfaces was studied by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and reflectance anisotropy spectroscopy (RAS). On the as-treated surface, a diffused (1 × 1) pattern is observed, which successively evolves to the β₂(2 × 4)/c(2 × 8) and (4 × 2)/c(8 × 2) ones after annealing to 330 °C and 410 °C, respectively. At the intermediate temperature of 370 °C, an ₂(2 × 4)/(4 × 2) mixed reconstruction is observed. Reflectance anisotropy spectra are compared with those of the corresponding reconstructions observed after As-decapping and found to be quite similar. Therefore we conclude that high-quality (1 0 0) InAs surfaces can be obtained by wet chemical treatment in an easy, inexpensive and practical way.     

Determination of the K adsorption site on Fe(1 1 0) with XSW

We have used X-ray standing waves (XSW) in near normal incidence to determine the K–Fe bond length and the adsorption site of K at the saturation coverage at room temperature on the Fe(1 1 0) surface. Three different scattering geometries were used to enable the determination of the adsorption site by triangulation. From the results we conclude that the potassium atoms adsorb in a distorted hexagonal overlayer. The Fe–K distance, as determined from the measurements in the (2 2 0) Bragg reflection, is 3.4±0.2 Å. The long bridge site seems to be the preferred adsorption site for the potassium atoms in the distorted hexagonal overlayer. This geometry not only fits all the XSW data, but also explains all spots in the LEED pattern without the need to introduce multiple scattering. Comparison of the measured and simulated XSW data, based on the distorted hexagonal overlayer, enables a more accurate determination of the Fe–K bond length to 3.36±0.14 Å. This corresponds to a potassium hard sphere radius of r_K=2.12±0.14 Å. This radius is among the largest reported for potassium on a metal, which is attributed to the high coverage and coordination of the K atoms in this overlayer arrangement.     

LEED structure determination of the Ni(1 1 1)(√3×√3)R30°-Sn surface

Quantitative low energy electron diffraction has been used to determine the structure of the Ni(1 1 1)(√3×√3)R30°-Sn surface phase. The results confirm that the surface layer comprises a substitutional alloy of composition Ni₂Sn as previously found by low energy ion scattering (LEIS), and also shows that there is no stacking fault at the substrate/alloy interface as has been found in (√3×√3)R30°-Sb surface alloys on Ag and Cu(1 1 1). The surface alloy layer is rumpled with the Sn atoms 0.45 ± 0.03 Å higher above the substrate than the surrounding Ni atoms. This rumpling amplitude is almost identical to that previously reported on the basis of the LEIS study. Comparison with similar results for Sn-induced surface alloy phases on Ni(1 0 0) and Ni(1 1 0) shows a clear trend to reduced rumpling with reduced surface atomic layer density, an effect which can be rationalised in terms of the different effects of valence electron charge smoothing at the surface.     

The IR spectra of Mg5C(CO) complexes on the (0 0 1) surfaces of polycrystalline and single crystal MgO

The FTIR spectroscopy of carbon monoxide adsorbed on polycrystalline MgO smoke has been investigated as a function of the CO equilibrium pressure at constant temperature (60 K) (optical isotherm) and of the temperature (in the 300–60 K range) at constant CO pressure (optical isobar). In both cases the spectra fully reproduce those of CO adsorbed on the (0 0 1) surface of UHV cleaved single crystals [Heidberg et al., Surf. Sci. 331–333 (1995) 1467]. This result, never attained in previous investigations on dispersed MgO, contribute to bridging the gap which is commonly supposed to exist between surface science and the study of “real” (defective) systems. Depending on the surface coverage θ the main spectral features due to the CO/MgO smoke interaction are a single band shifting from 2157.5 (at θ→0) to 2150.2 cm⁻¹ (at θ=1/4) or a triplet, at 2151.5, 2137.2 and 2132.4 cm⁻¹ (at θ>1/4). These manifestations are due to the ν(CO) modes of Mg_5C²⁺· · · CO adducts formed on the (0 0 1) terminations of the cubic MgO smoke microcrystals. The formation of the CO monolayer is occurring in two different phases: (i) a first phase with CO oscillators perpendicularly oriented to the surface (2157–2150 cm⁻¹) and (ii) a second phase constituted by an array of coexisting perpendicular and tilted species (triplet at 2151.5, 2137.2 and 2132.4 cm⁻¹). A much weaker feature at 2167.5–2164 cm⁻¹ is assigned to Mg_4C²⁺· · · CO adducts at the edges of the microcrystals. The heat of adsorption of the perpendicular Mg_5C²⁺· · · CO complex in the first phase has been estimated from the optical isobar and results to be 11 kJ mol⁻¹.     

Enhanced dispersion and stability of gold nanoparticles on stoichiometric and reduced TiO2(1 1 0) surface in the presence of molybdenum

Mo, Au and their coadsorbed layers were produced on nearly stoichiometric and oxygen-deficient titania surfaces by physical vapor deposition (PVD) and characterized by low energy ion scattering (LEIS), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and scanning tunnelling microscopy (STM). The behavior of Au/Mo bimetallic layers was studied at different relative metal coverages and sample temperatures.

STM data indicated clearly that the deposition of Au on the Mo-covered stoichiometric TiO₂(1 1 0) surface results in an enhanced dispersion of gold at 300 K. The mean size of the Au nanoparticles formed at 300 K on the Mo-covered TiO₂(1 1 0) was significantly less than on the Mo-free titania surface (2 ± 0.5 nm and 4 ± 1 nm, respectively). Interestingly, the deposition of Mo at 300 K onto the stoichiometric TiO₂(1 1 0) surface covered by Au nanoparticles of 3–4 nm (0.5 ML) also resulted in an increased dispersity of gold. The driving force for the enhanced wetting at 300 K is that the Au–Mo bond energy is larger than the Au–Au bond energy in 3D gold particles formed on stoichiometric titania. In contrast, 2D gold nanoparticles produced on ion-sputtered titania were not disrupted in the presence of Mo at 300 K, indicating a considerable kinetic hindrance for breaking of the strong Au-TiO_x bond.

The annealing of the coadsorbed layer formed on a strongly reduced surface to 740 K did not cause a decrease in the wetting of titania surface by gold. The preserved dispersion of Au at higher temperatures is attributed to the presence of the oxygen-deficient sites of titania, which were retained through the reaction of molybdenum with the substrate. Our results suggest that using a Mo-load to titania, Au nanoparticles can be produced with high dispersion and high thermal stability, which offers the fabrication of an effective Au catalyst.     

Surface properties of Hafnium diboride(0 0 0 1) as determined by X-ray photoelectron spectroscopy and scanning tunneling microscopy

The surface structure and properties of the HfB₂(0 0 0 1) (Hafnium diboride, HfB₂) surface have been investigated with X-ray photoelectron spectroscopy, low energy electron diffraction (LEED), and scanning tunneling microscopy (STM). Annealing temperatures above 1900°C produce a sharp (1×1) LEED pattern, which corresponds to STM images showing flat (0 0 0 1) terraces with a very low contamination level separated by steps 3.4 Å in height, corresponding to the separation of adjacent Hf planes in the HfB₂ bulk structure. For lower annealing temperatures, extra p(2×2) spots were observed with LEED, which correspond to intermediate terraces of a p(2×1) missing row structure as observed with STM.     

Growth and thermal properties of ultrathin cerium oxide layers on Rh(1 1 1)

Ultrathin layers of cerium oxide have been deposited on a Rh(1 1 1) surface and their growth morphology, structure, and thermal stability have been investigated by LEED, STM, XPS, and valence band resonant photoemission. STM and LEED indicate that the ceria grows epitaxially in form of ordered CeO₂ islands at elevated substrate temperature (250–300 °C), with (1 1 1) faces parallel and orientationally aligned to the main azimuthal directions of the substrate. The ultrathin ceria films contain significant amounts of reduced Ce³⁺ species, which appear to be located predominantly at the ceria–Rh interface. For thicker films (>6 equivalent monolayers) stoichiometric CeO₂ is detected in XPS. Vacuum annealing produces morphologically well-defined hexagonal islands, accompanied by partial reduction and the formation of oxygen vacancies at the ceria surface. The thermal stability and the degree of reduction is a function of the oxide layer thickness, with thinner layers being thermally less stable. At temperatures >800 °C, the ceria decomposes and Ce–Rh alloy phases are identified.     

Surface reconstructions of the Si(100)–Ge system

The surface reconstruction of epitaxial Ge layer on Si(100) was studied with ultrahigh vacuum scanning tunneling microscopy. The surface with 0.8 ML Ge grown in the presence of a hydrogen surfactant reveals the same structures as found in chemical-vapor-deposited Ge on Si(100): (i) defective (2×1) structure at 290°C, (ii) irregular (2×N) in Ge layer and defective (2×1) in bare Si regions at 420°C, and (iii) (2×N) in Ge-covered regions and c(4×4) in bare Si regions at 570°C. The morphology of step edges does not change with temperature, implying that the c(4×4) reconstruction is anisotropic in nature.     

A photoelectron diffraction investigation of vanadyl phthalocyanine on Au(1 1 1)

Scanned-energy mode photoelectron diffraction using the O 1s and V 2p emission perpendicular to the surface has been used to investigate the orientation and internal conformation of vanadyl phthalocyanine (VOPc) adsorbed on Au(1 1 1). The results confirm earlier indications from scanning tunnelling microscopy that the VO vanadyl bond points out of, and not into, the surface. The VO bondlength is 1.60 ± 0.04 Å, not significantly different from its value in bulk crystalline VOPc. However, the V atom in the adsorbed molecule is almost coplanar with the surrounding N atoms and is thus pulled down into the approximately planar region defined by the N and C atoms by 0.52 (+0.14/−0.10) Å, relative to its location in crystalline VOPc. This change must be attributed to the bonding interaction between the molecule and the underlying metal surface.     

Influence of the surface-termination of hexagonal SiC(0 0 0 1) on the temperature dependences of Ge growth modes and desorption

With the aim of comparing initial Ge adsorption and desorption modes on different surface terminations of 4H-SiC(0 0 0 1) faces, 3 × 3, √3×√3R30° (R3) and 6√3×6√3R30° (6R3) reconstructions, of decreasing Si surface richness, have been prepared by standard surface preparation procedures. They are controlled by reflection high energy electron diffraction (RHEED), low energy electron diffraction and photoemission. One monolayer of Ge has been deposited similarly at room temperature on each of these three surfaces, followed by the same set of isochronal heatings at increasing temperatures up to complete Ge desorption. At each step of heating, the structural and chemical status of the Ge ad-layer has been probed. Marked differences between the Si- (3 × 3 and R3) and C-rich (6R3) terminations have been obtained. Ge wetting layers are only obtained up to 400 °C on 3 × 3 and R3 surfaces in the form of a 4 × 4 reconstruction. The wetting is more complete on the R3 surface, whose atomic structure is the closest to an ideally Si-terminated 1 × 1 SiC surface. At higher temperatures, the wetting layer stage transiets in Ge polycrystallites followed by the unexpected appearance on the 3 × 3 surface of a more ordered Si island structure. It denotes a Si clustering of the initial Si 3 × 3 excess, induced by the presence of Ge. A phase separation mechanism between Si and Ge prevails therefore over alloying by Ge supply onto a such Si-terminated 3 × 3 surface. Conversely, no wetting is obtained on the 6R3 surface and island formation of exclusively pure Ge takes place already at low temperature. These islands exhibit a better epitaxial relationship characterized by Ge(1 1 1)//SiC(0 0 0 1) and Ge〈1 1 −2〉//SiC〈1 −1 0 0〉, ascertained by a clear RHEED spot pattern. The absence of any Ge-C bond signature in the X-ray photoelectron spectroscopy Ge core lines indicates a dominant island nucleation on heterogeneous regions of the surface denuded by the 6R3 graphite pavings. Owing to the used annealing cycles, the deposited Ge amount desorbs on the three surfaces at differentiated temperatures ranging from 950 to 1200 °C. These differences probably reflect the varying morphologies formed at lower temperature on the different surfaces. Considering all these results, the use of imperfect 6R3 surfaces appears to be suited to promote the formation of pure and coherent Ge islands on SiC.     

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.     

Growth of metallic nanowires on anisotropic Si substrates: Pb on vicinal Si(0 0 1), Si(7 5 5), Si(5 3 3), and Si(1 1 0)

The spontaneous formation of mesoscopic Pb-wires, on 4° off-cut Si(0 0 1) vicinal surface, Si(7 5 5), Si(5 3 3), and Si(1 1 0) substrates was studied by low-energy electron microscopy. Before the deposition of Pb the substrates were modified by predeposition of a submonolayer amount of Au followed by annealing. The Au-induced reconstruction creates quasi-one-dimensional facets and superstructures. Their width ranged from several hundred nm in the case of the vicinal Si(0 0 1) down to atomic scale size, for the Si(1 1 0) surface. The best-developed arrays of parallel aligned mesoscopic wires were obtained during the deposition of Pb on substrates cooled slightly below room temperature. Wires with length to width ratio reaching 130 were produced on the Si(7 5 5) and the Si(5 3 3) substrates. The width of these nanowires was uniform over the whole substrate and was about 60 nm. The driving forces for the formation of the mesoscopic wires are the anisotropic strain due to the large misfit between the Pb and the Si lattice and one-dimensional diffusion of Pb.     

Surface deformation phenomena induced by electron-beam irradiation in strained InGaAs/AlGaAs layers on GaAs (1 0 0) and (3 1 1)B substrates

The strained InGaAs/AlGaAs layer structures have been grown on GaAs ( 10 0) and (3 1 1)B substrates in a horizontal low-pressure metalorganic vapor-phase epitaxy system at a temperature of 800°C. In the surface observation using a high-resolution scanning electron microscope, we have found that surface deformation phenomena induced by electron-beam irradiation in strained In_0.36Ga_0.64As,/Al_0.3Ga_0.7As layers on GaAs (1 0 0) and (3 1 1)B substrates. The change of the surface morphology was observed in real time on the display of SEM with the accelerating voltage of 30 kV and the irradiated time of 60–120 s. The surface deformation through mass transport seems to be the cause of the residual strain relaxation due to electron-beam irradiation.