RT growth of acetonitrile and acrylonitrile on Si(0 0 1)-2 × 1 studied by XPS and LEED

In this work we show the adsorption of acetonitrile (CH₃CN) and acrylonitrile (CH₂CHCN) on Si(0 0 1)-2 × 1 at room temperature by increasing the molecular doses. Especially, by means of XPS and LEED data, we stress the action of these molecules on the silicon surface locating the dangling-bonds quasi-saturation within 10 L. The shortage of nitrogen XPS signal and some anomalies in carbon spectra point to an invading action from a traditional X-ray source (Al-K_α line) against chemisorbed molecules. In particular, we think that a long exposure to this radiation could break carbon-silicon bonds changing some adsorption geometries and making desorb molecular fragments.     

Oxygen-induced nano-faceting of Ir(2 1 0)

The adsorption of oxygen and the nanometer-scale faceting induced by oxygen have been studied on Ir(2 1 0). Oxygen is found to chemisorb dissociatively on Ir(2 1 0) at room temperature. The molecular desorption process is complex, as revealed by a detailed kinetic analysis of desorption spectra. Pyramid-shaped facets with {3 1 1} and (1 1 0) orientations are formed on the oxygen-covered Ir(2 1 0) surface when annealed to T?600 K. The surface remains faceted for substrate temperatures T<850 K. For T>850 K, the substrate structure reverts to the oxygen-covered (2 1 0) planar state and does so reversibly, provided that oxygen is not lost due to desorption or via chemical reactions upon which the planar (2 1 0) structure remains. A clean faceted surface was prepared through the use of low temperature surface cleaning methods: using CO oxidation, or reaction of H₂ to form H₂O, oxygen can be removed from the surface while preserving (“freezing”) the faceted structure. The resulting clean faceted surface remains stable for T<600 K. For temperatures above this value, the surface irreversibly relaxes to the planar state.     

Substitutional adsorption geometry for Pb(1 1 1)-(√3 × √3)R30°-K

Intermixed structures for alkalis (larger than Li) on close-packed substrates have previously been observed only on Al(1 1 1). This study shows that K forms an ordered intermixed structure on Pb(1 1 1). The structures of clean Pb(1 1 1) and Pb(1 1 1)-(√3 × √3)R30°-K were studied using dynamical low-energy electron diffraction (LEED). The clean Pb(1 1 1) surface at 47 K was found to be a relaxed version of the bulk structure, in agreement with an earlier study of the same surface [Y.S. Li, F. Jona, P.M. Marcus, Phys. Rev. B 43 (1991) 6337]. At room temperature, adsorption of K on this surface results in a (√3 × √3)R30° structure, which was shown using dynamical LEED to consist of K atoms substituted in surface vacancies. The K-Pb bond length was found to be 3.62 ± 0.3 Å, with no significant change to the Pb interlayer spacings.     

Formation of ordered arrays of Ag nanowires and nanodots on Si(5 5 7) surface

The ordered arrays of Ag nanowires and nanodots have been grown in ultra-high vacuum on the Si(5 5 7) surface containing regular steps of three bilayer height. Formation of Ag nanostructures have been studied by scanning tunneling microscopy, low energy electron diffraction and Auger electron spectroscopy at room temperature. It was shown that a sample exposure in the vacuum before Ag growth affects the shape of the forming Ag islands. This effect is caused by oxygen adsorption on the silicon surface from the residual atmosphere in the vacuum chamber. When Ag is deposited on the clean silicon surface the islands, overlapping several (1 1 1) neighboring terraces, form. The arrays of silver nanowires elongated along steps and silver nanodots, arranged in lines parallel to the steps, can be formed on the Si(5 5 7) surface depending on the amount of adsorbed oxygen.     

Structure analysis of W(0 0 1)2 × 1-O surface at room and liquid nitrogen temperatures

Surface structure of O-adsorbed W(0 0 1) surface after annealing to 1200 K has been analyzed by low energy electron diffraction at 77 K as well as at room temperature. The optimum structure has tungsten missing rows and oxygen double rows. Furthermore, the R-factor is minimized at the structure that O atoms are adsorbed on one of the two different threefold hollow sites of the (1 1 0) facet appearing on the W(0 0 1)2 × 1 with missing row. However, the results suggest that two domains of O atoms adsorbed on both the two different threefold hollow sites coexist. Then, I-V curves have been analyzed as a function of the mixing ratio of the two domains having different O adsorption sites at room and low temperatures. The energy difference between these two sites has been estimated to be 6.5 meV from the temperature dependence of the mixing ratio.     

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.     

Reversible electromigration of thallium adatoms on the Si(1 1 1) surface

By means of low-energy electron diffraction (LEED), we found a reversible structural change of on thallium (Tl) adsorbed Si(1 1 1) surfaces by switching the polarity of applied DC voltage for heating the sample. It was shown in the literature that Tl adatoms are located on the T₄ sites of the bulk-terminated surface both in the (1 × 1) and . It is clarified that the structural change is caused by the electromigration of the Tl adatoms. Tl atoms migrate towards the cathode, being induced by the electric field (10-20 V/cm). We discussed an atomic process of the electromigration.     

Surface pre-melting and surface flattening of Bi nanofilms on Si(1 1 1)-7 × 7

We report on the in situ observation of temperature-driven drastic morphology evolution and surface pre-melting of the Bi(0 0 1) nanofilm deposited on the Si(1 1 1)-7 × 7 surface by use of spot-profile-analyzing low-energy electron diffraction (SPA-LEED). Surface step density of the single-crystalline, epitaxial Bi(0 0 1) film decreases above 350 K in a critical manner. On annealed Bi(0 0 1) films, we have detected surface pre-melting with a transition temperature of 350 K, which yields reversible diffraction intensity drop in addition to the harmonic Debye-Waller behavior. The observed surface flattening of the as-deposited film is driven by the increased amount of mobile adatoms created through the surface pre-melting.     

The CuGaSe2(0 0 1) surface: A (4 × 1) reconstruction

We report on the formation of a stable (4 × 1) reconstruction of the chalcopyrite CuGaSe₂(0 0 1) surface. Using Ar⁺ ion-bombardment and annealing of epitaxial CuGaSe₂ films grown on GaAs(0 0 1) substrates it was possible to obtain flat, well-ordered surfaces showing a clear (4 × 1) reconstruction. The cleanliness and structure were analyzed in situ by AES and LEED. AES data suggest a slight Se-enrichment and Cu-depletion upon surface preparation. Our results demonstrate that (0 0 1) surfaces of the Cu-III-VI₂(0 0 1) material can show stable, unfacetted surfaces.     

A study of Ga layers on Si(1 0 0)-(2 × 1) by SR-PES: Influence of adsorbed water

Results for deposition and thermal annealing of gallium on the Si(1 0 0)-(2 × 1) surface achieved by synchrotron radiation photoelectron spectroscopy (SR-PES) and low energy electron diffraction (LEED) are presented. In addition to deposition of Ga on a clean surface, the influence of water adsorption on the arrangement of gallium atoms was also studied. The results on Ga deposition at a higher temperature (490 °C) are consistent with a Ga ad-dimer model showing equivalent bond arrangement of all Ga atoms for coverages up to 0.5 ML. The deposition onto a surface with adsorbed water at room temperature led to a disordered gallium growth. In this case gallium atoms bind to silicon dimers already binding fragments of adsorbed water. A subsequent annealing of these layers leads to a surface structure similar to the Ga-(2 × 2), however, it is less ordered, probably due to the presence of silicon oxides formed from water fragments.     

Lateral interactions and nonequilibrium in adsorption and desorption. Part 1. Experimental results for (2 × 2)-(3O + NO)/Ru(0 0 1)

Extending earlier vibrational spectroscopy and thermal desorption measurements on this system, its geometrical structure and its adsorption/desorption kinetics have been investigated in detail. The adsorption and desorption of NO proceed, with little influence on the 3O template, on its (2 × 2) lattice of empty hcp sites. The desorption kinetics, with splitting of the TPD spectra into two peaks, are far from the expected behavior for independent sites. Also, the vibrational band structure shows dispersion beyond dipole-dipole interactions. So, despite the quite large NO-NO distance and their screening by the O atoms, there is clear evidence for static and dynamic lateral interactions which should be extractable from the data. A qualitative analysis suggests that these interactions are due to elastic coupling between the positions and vibrations, respectively, of the O and NO adsorbates. However, quantitative conclusions cannot be drawn directly as the kinetic data cannot be interpreted in a quasiequilibrium approach, as would be the normal procedure, due to the presence of strong nonequilibrium effects. The lack of internal equilibration is presumably caused by slow diffusion. The results are sufficiently complete and detailed to justify the effort of theoretical modeling with the aim to quantitatively describe both the lateral interactions and the nonequilibrium effects.     

CuPc molecules adsorbed on Au(1 1 0)-(1 × 2): growth morphology and evolution of valence band states

We present the growth morphology, the long-range ordering, and the evolution of the valence band electronic states of ultrathin films of copper phthalocyanine (CuPc) deposited on the Au(1 1 0)-(1 × 2) reconstructed surface, as a function of the organic molecule coverage. The low energy electron diffraction patterns present a (5 × 3) reconstruction from the early adsorption stages. High-resolution UV photoelectron spectroscopy data show the disappearance of the Au surface states related to the (1 × 2) reconstruction, and the presence of new electronic features related to the molecule-substrate interaction and to the CuPc molecular states. The CuPc highest occupied molecular orbital gradually emerges in the valence band, while the interface electronic states are quenched, upon increasing the coverage.     

LCAO study of the Cu(1 1 0)-p(2 × 1)O surface

We have performed semi-empirical LCAO calculations of the electronic structure of the Cu(1 1 0)-p(2 × 1)O surface. This has been done accounting for the Cu-Cu interactions by means of a recently proposed set of parameters, which give very good results for the bulk as well as for the surfaces of lowest Miller indices. Furthermore, the O-O interactions, which have been neglected in the preceding similar studies, have been taken into account. The resulting surface bands are in very good agreement with the overall set of the available experimental data. Several issues concerning the physical properties of this surface are addressed in the present paper: the changes induced on the clean surface bands by the adsorption and the reconstruction; the arrangement of the Cu and O atoms in the added rows; the position of the p_y antibonding band of the oxygen. In particular, we have found that the latter has an energy of −0.2 eV at the point. This result confirms an experimental indication in the same direction previously reported by Courths et al. [R. Courths, S. Hüfner, P. Kemkes, G. Wiesen, Surf. Sci. 376 (1997) 43].     

Reflection high-energy positron diffraction pattern from a Si(1 1 1)-(7 × 7) surface

We have investigated the feature of reflection high-energy positron diffraction (RHEPD) pattern from a Si(1 1 1)-(7 × 7) surface. The RHEPD pattern observed in the total reflection condition is quite different from the conventional reflection high-energy electron diffraction (RHEED) pattern. This fact is attributed to the different penetration depths of positrons and electrons. We show that the intensity distribution of RHEPD pattern is reproduced considering the dimer-adatom-stacking fault (DAS) model with optimized atomic positions and scattering potentials of adatoms and rest atoms.     

Structural and statistical analysis of Yb/Si(1 1 1) and Eu/Si(1 1 1) reconstructions

We have performed the structural and statistical analysis of Yb/Si(1 1 1) and Eu/Si(1 1 1) surfaces in the submonolayer regime utilizing low-energy electron diffraction and scanning tunneling microscopy (STM). The almost identical series of one-dimensional chain structures (e.g., 3 × 2/3 × 1, 5 × 1, 7 × 1, 9 × 1, and 2 × 1 phases) are found in order of increasing metal coverage for both adsorbed systems, however, only the Eu/Si system reveals the ‘√3’-like reconstruction before the 2 × 1 endpoint phase. The atomic models of chain structures are proposed and discussed. In particular, our results suggest the odd-order n×1 (n=5,7,9,…) intermediate reconstructions to incorporate the Seiwatz chains and honeycomb chains with the proportion of m:1, where . The statistical analysis of STM images is carried out to examine the correlation of atomic rows on Eu/Si and Yb/Si surfaces. It is found that Eu stabilizes more ordered row configuration compared to Yb, which can be explained in terms of indirect electronic interaction of atomic chains or/and different magnetic properties of adsorbed species.     

Holographic diffuse LEED image reconstruction for simultaneous occupation of different oxygen adsorption sites on Ni(1 1 1)

We determined the local adsorption structure of disordered oxygen on the Ni(1 1 1) surface by means of diffuse holographic LEED. The measurements have been performed above the critical temperature (T_c=450 K) for the oxygen order-disorder phase transition at 500 K and at a coverage of Θ=0.25 ML. At this temperature we found, in agreement with a previous LEED-IV-analysis [Surf. Sci. 349 (1996) 185], that besides the fcc threefold sites also hcp sites are occupied. In addition, a small amount seems to be located also at top and bridge sites. Reconstructing the holographic wavefield information, the different oxygen adsorption geometries are superimposed in the real space image. Nevertheless, a spatial resolution of 0.5-1 Å was sufficient to clearly distinguish between them. The influence of algorithmic parameters on the image quality was tested.     

Structure and composition of the NiPd(1 1 0) surface

The NiPd(1 1 0) alloy surface was studied using low energy electron diffraction to measure the structure and composition of the first three atomic layers. The surface layer is highly enriched in Pd and has a significantly buckled structure. The second layer is also buckled, with displacements even larger than the surface layer. The second layer also exhibits intralayer segregation (chemical ordering), with alternate close-packed rows of atoms being Ni enriched and Pd enriched. The third layer has a structure and composition close to that of the bulk alloy. These results are compared with results for the other low index faces of NiPd, the extensive literature on NiPt alloy surfaces, and the growing body of theoretical literature for NiPd alloy surfaces.     

The dense α-√3 × √3Pb/Si(1 1 1) phase: A comprehensive STM and SPA-LEED study of ordering, phase transitions and interactions

The T-θ phase diagram for the system Pb/Si(1 1 1) was determined in the coverage range 6/5 ML < θ < 4/3 ML from complementary STM and SPA-LEED experiments. This coverage is within the range where a “Devil’s Staircase” (DS) has been realized. The numerous DS phases answer conflicting information in the Pb/Si(1 1 1) literature and update the previously published phase diagram. The measurements reveal the thermal stability of the different linear DS phases with the transition temperature found to be a function of phase period. Because of additional complexity in the experimental system (i.e. two-dimensionality and 3-fold symmetry) the linear DS phases transform at higher temperature into commensurate phases of 3-fold symmetry HIC (historically named “hexagonal incommensurate phase”). Different types of HIC phases have been discovered differing in the size of the supercell built out of √3 × √3 domains separated by domain walls of the √7 × √3 phase. The detailed structures of these HIC phases (coverage, binding site, twist angle, etc.) have been deduced from the comparison of STM images and diffraction patterns. After heating the system to even higher temperature the HIC phase transforms into the disordered phase. For sufficiently high coverage a SIC (“striped incommensurate phase” which is also built from √3 × √3 domains but meandering √7 × √3 domain walls) is observed which also disorders at high temperatures.     

Formation and hydrogenation of p(2 × 2)-N on Pt(1 1 1)

The formation of a well-ordered p(2 × 2) overlayer of atomic nitrogen on the Pt(1 1 1) surface and its reaction with hydrogen were characterized with reflection absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The p(2 × 2)-N overlayer is formed by exposure of ammonia to a surface at 85 K that is covered with 0.44 monolayer (ML) of molecular oxygen and then heating to 400 K. The reaction between ammonia and oxygen produces water, which desorbs below 400 K. The only desorption product observed above 400 K is molecular nitrogen, which has a peak desorption temperature of 453 K. The absence of oxygen after the 400 K anneal is confirmed with AES. Although atomic nitrogen can also be produced on the surface through the reaction of ammonia with an atomic, rather than molecular, oxygen overlayer at a saturation coverage of 0.25 ML, the yield of surface nitrogen is significantly less, as indicated by the N₂ TPD peak area. Atomic nitrogen readily reacts with hydrogen to produce the NH species, which is characterized with RAIRS by an intense and narrow (FWHM ∼ 4 cm⁻¹) peak at 3322 cm⁻¹. The areas of the H₂ TPD peak associated with NH dissociation and the XPS N 1s peak associated with the NH species indicate that not all of the surface N atoms can be converted to NH by the methods used here.