Computational study of cycloaddition reactions on the SiC(1 0 0)-c(2 × 2) surface

Cycloaddition reactions between 1,3-butadiene and the C-terminated SiC(1 0 0)-c(2 × 2) surface have been addressed using quantum-chemical methods. The c(2 × 2) structure consists of ---CC--- bridges between underlayer Si atoms which themselves form Si---Si bonds. Of various possible reaction products, the one formed by a [2 + 4] reaction with the ---CC--- bridge (giving a species resembling 1,4-cyclohexadiene) is the lowest in energy. Density functional calculations for the bare c(2 × 2) surface, using a cluster model with mechanical embedding, gave good agreement with structural parameters obtained in previous fully ab initio studies. Similar calculations for the cycloaddition product and for the transition state gave a reaction energy of −50.3 kcal/mol and an activation energy of +6.1 kcal/mol to form a planar ring structure lying normal to the surface. Detailed results for the frequency and infrared polarization behavior of adsorbate vibrational modes have also been obtained.     

A first-principles study of surface and subsurface H on and in Ni(1 1 1): diffusional properties and coverage-dependent behavior

Periodic, self-consistent, density functional theory (GGA-PW91) calculations are performed for both surface and subsurface atomic hydrogen on and in Ni(1 1 1). At a low coverage (θ=0.25 ML), the binding energies (BEs) of a hydrogen atom in surface fcc, subsurface octahedral (first layer), and subsurface octahedral (second layer) sites are −2.89, −2.18, and −2.11 eV, respectively. The activation energy barriers for hydrogen diffusion from the surface to the first subsurface layer and from the first to the second subsurface layer are estimated to be 0.88 and 0.52 eV, respectively. In the entire coverage range studied, hydrogen occupies surface fcc and hcp sites and subsurface octahedral sites. In addition, the magnitude of the BE per hydrogen atom and the magnetization of the nickel slabs both decrease as hydrogen coverage increases. Vibrational frequencies of hydrogen at various surface and subsurface sites are calculated and are in reasonable agreement with experimental data. A phase stability calculation with a 2 × 2 surface unit cell shows that a p(2 × 2)-2H overlayer structure (θ=0.5 ML) and a p(1 × 1)-1H structure (θ=1.0 ML) are stable at low hydrogen pressures, in agreement with numerous experimental results. A very large increase in pressure is required to populate subsurface sites. After such an increase occurs, the first subsurface layer is filled completely.     

Adsorption of oxygen on Rh(110): a LEED, Auger electron spectroscopy and thermal desorption study

The adsorption of oxygen on the Rh(110) surface has been studied by a variety of techniques. Low-energy electron diffraction shows the following patterns: (2 × 1)p2mg at 1 ML coverage and temperatures between 125 and 300 K; (2 × 2)p2mg at 0.5 ML coverage after heating to above 470 K; c(2 × 8) and complex streaked c(2 × 2n) patterns at coverages above 0.5 after heating to 470 K. These results are in partial agreement with previous work. Models for the first two structures are suggested. In the (2 × 2) structure, the oxygen is found to be much less reactive with CO at room temperature than in the (2 × 1) structure, suggesting that it is subsurface. A metastable (1 × 2) structure was produced from the (2 × 2) by reduction of the oxygen by CO at 450 K, and is interpreted as a surface reconstruction.     

An AFM study of the processing of hydrogen passivated silicon(1 1 1) of a low miscut angle

We present atomic force microscopy (AFM) measurements from a passivated silicon crystal miscut by 0.1° and show the etching regime to be significantly different from surfaces with a larger miscut angle. A simple kinetic model is developed to explain the results and is used to derive the optimal etching conditions for nominally flat Si(1 1 1)–(1×1)H. We show that small changes in miscut angle can alter the kinetic steady state and promote the formation of deep etch pits, even on the least stable, miscut surface. Collisions of steps with these pits result in arrays of stable, self-aligned ‘etch hillocks' over micron dimensions. Following preparation, we use AFM to observe the initial growth of native oxide on the Si(1 1 1)–(1×1)H surface, and demonstrate that AFM is a sensitive probe to surface oxidation in the sub-monolayer regime.     

Modeling of electron-stimulated mobility and disordering of adsorbed particles

The electron-stimulated mobility and the electron-stimulated disordering of adsorbed particles is studied for a two-dimensional lattice gas model on a square lattice using kinetical Monte Carlo simulations. Pairwise nearest-neighbor repulsive interactions are considered which induce c(2 × 2) ordering of the lattice gas at low temperatures around half coverage. Adsorbed particles are allowed to perform thermally activated as well as electron-induced jumps to nearest-neighbor sites. The calculations are performed taking full advantage of the numerical power of a supermassive parallel computer.

It was found that the electron-induced mobility of adatoms causes the complete breakdown of the c(2 × 2) ordering at low temperatures if the fraction of electron-induced jumps exceeds a critical value. The breakdown of the ordering is accompanied by substantial changes of the chemical and tracer surface diffusion coefficients.     

Surface reconstructions and phase transitions on the GaAs(111)B surface

The (111)B surface of GaAs has been investigated using scanning tunneling microscopy (STM) and a number of different reconstructions have been found at different surface stoichiometries. In accordance with electron diffraction studies, we find the series (2 × 2), (1 × 1)_LT, ( ) and (1 × 1)_HT with increasing annealing temperature, corresponding to decreasing surface As concentration. The (1 × 1)_LT is of particular interest, since it only occurs in a narrow temperature window between the two more established reconstructions, the (2 × 2) and the ( ). We find the (1 × 1)_LT to take the form of a mixture of the local structures of both the (2 × 2) and ( ) phases, rather than having a distinct structure. This is behaviour consistent with a kinetically limited system, dominated by the supply of As adatoms to the surface, and may be an example of a continuous phase transition. Above the (1 × 1)_LT transition, atomic resolution images of the ( ) surface reveal only a three-fold symmetry of the hexagonal structural units, brought about by inequivalent surface bonding due to the 23.4° rotation of the surface unit cell relative to the substrate. This is responsible for the disorder found in the ( ) reconstruction, since the structure may form in one of two domains. At lower surface As concentration, the (1 × 1)_HT surface adopts a structure combining small domains of a 19.1° structure and random disorder. There is no apparent similarity between the (1 × 1)_LT and (1 × 1)_HT structures, which may be due to our measurements being conducted at room temperature and without an As flux to control the surface As concentration.     

Formation of subsurface carbon induced by oxygen adsorption on carbon-covered W(001)

The adsorption of oxygen on the carbon-covered W(001) surface was studied by AES and low energy ion scattering. At low carbon and oxygen coverages, both species can be accommodated on the surface. At higher coverages, the oxygen displaces the carbon into the near-surface (selvedge) region. When oxygen is adsorbed on the W(001)-p(5 × 1)C surface (formed by exposure to more than 50 L of ethylene at 1500 K), carbon is displaced in a nearly one for one manner. Annealing the oxygen-covered p(5 × 1)C surface to 950 K removes up to 0.5 ML oxygen as CO. Interestingly, the surface carbon coverage is unchanged by CO desorption at 950 K and subsurface carbon is partially replenished by diffusion from the bulk. Oxygen adsorption in excess of 0.5 ML suppresses carbon segregation from the bulk at 950 K. The additional oxygen does not desorb until 1300 K. Surface carbon is restored by annealing to 1500 K.. The degree and rate of carbon segregation depend on the initial ethylene exposure even though the resulting W(001)-p(5 × 1)C surfaces are identical according to AES, LEED, and ion scattering.     

Morphology and composition of Au films on Si(100)

Spot profile analysis low-energy electron diffraction, low-energy ion scattering and Auger electron spectroscopy were employed to study the morphology and composition of Au films on Si(100). After annealing, two distinct surface reconstructions were observed: a two-domain c(8×2) phase and a four-domain incommensurate (5×3.2)R5.7° phase. During the transition from the c(8×2) to the (5×3.2)R5.7° phase, the subsurface composition changes drastically from Au-rich to Si-rich, whereas the outermost layer composition remains almost constant (about 65 at.% Au). Detailed information concerning the domain structure for the two phases is subtracted from the profiles of the LEED spots.     

The Si(001) c(4×4) surface reconstruction: a comprehensive experimental study

We have carried out a comprehensive experimental study of the Si(001) c(4×4) surface reconstruction by scanning tunneling microscopy (STM) (at room temperature and elevated temperatures), Auger electron spectroscopy (AES), reflection high-energy electron diffraction (RHEED) and low-energy electron diffraction (LEED). Si(001) samples were kept under ultra-high vacuum (UHV) at around 550°C until the c(4×4) reconstruction appeared. STM contrast of the c(4×4) reconstruction is strongly influenced by electronic effects and changes considerably over a range of bias voltages.

The c(4×4) surface reconstruction is a result of stress which is caused by incorporation of impurities or adsorbates in sub-surface locations. The resulting c(4×4) reconstruction in the top layer is a pure silicon structure. The main structural element is a one-dimer vacancy (1-DV). At this vacancy, second layer Si-atoms rebond and cause the adjacent top Si-dimers to brighten up in the STM image at low bias voltages. At higher bias voltage the contrast is similar to Si-dimers on the (2×1) reconstructed Si(001). Therefore, besides the 1-DV and the two adjacent Si-dimers, another Si-dimer under tensile stress may complete the 4× unit cell. This is a refinement of the missing dimer model.     

Asymmetric versus symmetric dimerization on the Si(001) and As/Si(001)2 × 1 reconstructed surfaces as observed by grazing incidence X-ray diffraction

The atomic structures of the clean Si(001) and As/Si(001)2 × 1, 1 × 2 reconstructed surfaces prepared in situ have been obtained by grazing incidence X-ray diffraction under ultra high vacuum. In the former case an asymmetric dimer inclined by 7.4° on the surface plane with a slightly contracted dimer bond length (−1.5% compared to the bulk value) has been indentified as the structural basis, whereas a symmetric dimer is found after adsorption of one monolayer of As at 350 ° C. The induced displacements in the first subsurface silicon layer have been derived in both cases. These results are compatible with the models proposed on the basis of spectroscopic and direct imaging methods.     

Spatially resolved dynamics of the TiO2(1 1 0) surface reconstruction

We use low-energy electron microscopy to image the reversible transformation of the TiO₂(1 1 0) surface between a high-temperature 1 × 1 structure and a low-temperature 1 × 2 structure. The reconstruction dynamics are novel: 1 × 2 bands nucleated during cooling at the steps of the starting 1 × 1 surface and then grew laterally from the steps. The transformation kinetics are dominated by mass flow from the surface to the bulk, a process that facilitates converting the high-density 1 × 1 phase to the lower-density 1 × 2 phase. We have also imaged how the 1 × 1 surface reconstructs to 1 × 2 phase after sufficient oxygen is removed from the crystal’s bulk during vacuum annealing. 1 × 2 bands also nucleated and grew laterally from the initial 1 × 1-surface’s steps. However, because this isothermal 1 × 1-to-1 × 2 transition occurs largely by mass redistribution on the surface, the steps of the initial 1 × 1 surface and final 1 × 2 surface are offset. We propose models of mass redistribution during the 1 × 1/1 × 2 phase transition to explain this effect. We conclude that the phase transition is first-order because it always occurred by the nucleation and growth of discrete phases. Finally, we show that quenching can roughen TiO₂’s surface by forming pits and that changing temperature causes step motion on 1 × 2 surfaces.     

A novel (8 × 4) superstructure as precursor to the c(4 × 4) phase during Sb/Si(0 0 1) desorption

The role of kinetics in the superstructure formation of the Sb/Si(0 0 1) system is studied using in situ surface sensitive techniques such as low energy electron diffraction, Auger electron spectroscopy and electron energy loss spectroscopy. Sb adsorbs epitaxially at room-temperature on a double-domain (DD) 2 × 1 reconstructed Si(0 0 1) surface at a flux rate of 0.06 ML/min. During desorption, multilayer Sb agglomerates on a stable Sb monolayer (ML) in a DD (2 × 1) phase before desorbing. The stable monolayer desorbs in the 600–850 °C temperature range, yielding DD (2 × 1), (8 × 4), c(4 × 4), DD (2 × 1) phases before retrieving the clean Si(0 0 1)-DD (2 × 1) surface. The stable 0.6-ML (8 × 4) phase here is a precursor phase to the recently reported 0.25-ML c(4 × 4) surface phase, and is reported for the first time.     

Surface and subsurface distortions of the Au{110}-(1×2) structure

The reconstruction of the Au{110}-(1×2) missing-row surface has been studied by means of the new scattering and recoiling imaging spectrometry (SARIS) technique. The three-dimensional focusing patterns observed for scattering of 4 keV He⁺, Ne⁺ and Ar⁺ ions are highly sensitive to the structure of both the surface and subsurface layers. Classical ion trajectory simulations using the scattering and recoiling imaging code (SARIC) were used to simulate the scattering patterns. Using an R-factor comparison of the experimental and simulated images, it is demonstrated that SARIS is sensitive to changes of the order of 0.02 Å in the structural parameters of this Au surface. These parameters involve interlayer spacings, row pairing and row buckling in the first-through fifth atomic layers. Results for the shallow surface layers are in general agreement with the those of previous studies. The new results include structural parameters for the deeper subsurface layers and the observation of an oscillatory behavior of the layer spacings which is damped towards deeper layers.     

A mimic model of Pt---Rh catalyst prepared by electrochemical deposition of Rh on the Pt(100) surface

Electrochemical deposition of Rh ions on a (5 × 20) Pt(100) surface gave a (1 × 1) LEED pattern with high background intensity. By exposing the (1 × 1) Rh/Pt(100) surface to O₂ or NO, a characteristic p(3 × 1) Rh---O overlayer is built up at about 400 K, which is the same structure observed on the Pt_0.25Rh_0.75(100) surface exposed to NO or O₂. Once the p(3 × 1) Rh---O overlayer is formed, a reversible structural change, ,p(3 × 1) (1 × 1), can be caused at room temperature by adding H₂ and O₂. The p(3 × 1) Rh---O overlayer on the Pt(100) surface may represent a highly efficient catalyst for NO_x reduction.     

Hydrogen adsorption on Mo1−xRex(110) (x=0–0.25) surfaces

The effects of adsorbed H on the Mo_1−xRe_x(110), x=0, 0.05, 0.15, and 0.25, surfaces have been investigated using low-energy electron diffraction (LEED) and high-resolution electron energy loss spectroscopy (HREELS). For the x=0.15 alloy only, a c(2×2) LEED pattern is observed at a coverage Θ0.25 ML. A (2×2) pattern is observed for H coverages around Θ0.5 ML from surfaces with x=0, 0.05, and 0.15. Both c(2×2) and (2×2) patterns are attributed to reconstruction of the substrate. At higher coverages, a (1×1) pattern is observed. For the alloy surface with x=0.25, only a (1×1) pattern is obtained for all H coverages. Two H vibrations are observed in HREELS spectra for all Re concentrations, which shift to higher energies at intermediate coverages. Both peaks exhibit an isotopic shift, confirming their assignment to hydrogen. For Re concentrations of x=0.15 and higher, a third HREELS peak appears at 50 meV as H (D) coverage approaches saturation. This peak does not shift in energy with isotopic substitution, yet cannot be explained by contamination. The intrinsic width of the loss peaks depends on the Re concentration in the surface region and becomes broader with increasing x. This broadening can be attributed to surface inhomogeneity, but may also reflect increased delocalization of the adsorbed hydrogen atom.     

A LEED, TPD and HREELS investigation of NO adsorption on Sn/Pt(111) surface alloys

The adsorption of NO on Pt(111), and the (2 × 2)Sn/Pt(111) and (√3 × √3)R30°Sn/Pt(111) surface alloys has been studied using LEED, TPD and HREELS. NO adsorption produces a (2 × 2) LEED pattern on Pt(111) and a (2√3 × 2√3)R30° LEED pattern on the (2 × 2)Sn/Pt(111) surface. The initial sticking coefficient of NO on the (2 × 2)Sn/Pt(111) surface alloy at 100 K is the same as that on Pt(111), S₀ = 0.9, while the initial sticking coefficient of NO on the (√3 × √3)R30°Sn/Pt(111) surface decreases to 0.6. The presence of Sn in the surface layer of Pt(111) strongly reduces the binding energy of NO in contrast to the minor effect it has on CO. The binding energy of β-state NO is reduced by 8–10 kcal/mol on the Sn/Pt(111) surface alloys compared to Pt(111). HREELS data for saturation NO coverage on both surface alloys show two vibrational frequencies at 285 and 478 cm⁻¹ in the low frequency range and only one N-O stretching frequency at 1698 cm⁻¹. We assign this NO species as atop, bent-bonded NO. At small NO coverage, a species with a loss at 1455 cm⁻¹ was also observed on the (2 × 2)Sn/ Pt(111) surface alloy, similar to that observed on the Pt(111) surface. However, the atop, bent-bonded NO is the only species observed on the (√3 × √3)R30°Sn/Pt(111) surface alloy at any NO coverage studied.     

Impact of the growth on the stability–instability transition at Si (111) during step bunching induced by electromigration

The central result of this work is the definite proof that the mechanisms of the direct current induced step bunching in the middle and high temperature domains are different. We used the recently developed technique for reflection electron microscopy (REM) observation of Si surfaces during equilibrium and during crystal growth to document the impact of the growth on the process of step bunching induced by direct current heating of an Si crystal. We found completely different effects of crystal growth on the stability of the vicinal surfaces in the two temperature domains 1160–1240°C and 1260–1320°C. In the high temperature domain step bunching takes place at step-down direction of the electric current during sublimation, equilibrium and growth; whereas in the 1160–1240°C domain bunching takes place at step-up current during sublimation and at step-down current during growth. These findings support the concept of local mass transport in the high temperature domain — the surface migration of adatoms is effectively interrupted at each step by a high rate exchange between the adlayer and the crystal phase. At 1160–1240°C the mass transport is global — adatoms easily cross the steps without taking part in the crystal–adlayer exchange. Since earlier studies of other researchers support the concept of local mass transport in the low temperature domain, 900–1050°C, a difficult question arises — why do the properties of the steps, with respect to the mass transport over the crystal surface, have a temperature dependence which is not monotonous? To explain the transition from local mass transport in the low temperature domain to global mass transport in the middle temperature domain we advance a hypothesis for a transition from a low temperature state of adsorption (Takayanagi-like adatoms, existing above the (7×7)↔(1×1) transition) to a high temperature state of adsorption (adatom with three dangling bonds) with much lower activation energy for desorption.     

ESDIAD studies of the structure of TiO2(110)(1 × 1) and (1 × 2) surfaces and interfaces in conjunction with LEED and STM

The TiO₂(110)-(1 × 1) surface and its reconstruction as a (1 × 2) form have been studied with low energy electron diffraction (LEED), electron stimulated desorption ion angular distribution (ESDIAD) and scanning tunnelling microscopy (STM). Oxygen ion desorption occurs within a lobe perpendicular to the (1 × 1) surface, changing to two off-normal lobes for the (1 × 2) reconstruction. This transformation in the ESDIAD pattern is consistent with the added Ti₂O₃ row model of the (1 × 2) reconstruction proposed by Onishi and Iwasawa. STM studies of the stoichiometric and electron irradiated surfaces reinforce the association of the O⁺ ESD contribution with majority sites at the surface. Adsorption of acetic acid on the (1 × 1) surface produces a (2 × 1) overlayed and induces a reconstruction of the underlying substrate. ESDIAD reveals H⁺ ions emitted off-normally from dissociatively adsorbed acetate, and along the surface normal from surface hydroxyls. Adsorption of acetic acid on the (1 × 2) surface does not modify the LEED pattern, but ESDIAD reveals H⁺ desorption with a weaker off-normal contribution consistent with the Ti₂O₃ model of the reconstruction.     

The adsorbate-induced removal of the Pt{100} surface reconstruction Part I: NO

The molecular adsorption of NO on both the reconstructed (hex) and unreconstructed (1 × 1) surfaces of Pt{100} has been studied using a combination of infrared reflection-absorption spectroscopy (IRAS) and low energy electron diffraction (LEED) at temperatures between 90 and 300 K. On the (1 × 1) surface at 300 K adsorbed NO gives rise to an N-O stretching band at initially 1596 cm⁻¹ shifting to 1641 cm⁻¹ at a coverage of θ = 0.5. The LEED pattern at this coverage is interpreted in terms of a c(4 × 2) structure in which all the molecules occupy a single type of adsorption site between the on-top and bridge positions. At temperatures below 300 K, a higher coverage disordered phase is observed, giving rise to an N-O stretching band at 1680 cm⁻¹ associated with an on-top NO species. On the (hex) phase surface above 210 K, NO adsorption gives rise to bands characteristic of adsorption on the (1 × 1) phase indicating that the reconstruction is immediately lifted. Below 200 K initial adsorption actually occurs directly on the (hex) phase, resulting in a band at 1680 cm⁻¹, which is assigned to on-top NO. This band increases in intensity until, at a critical coverage dependent on temperature, the (hex) → (1 × 1) surface phase transition is induced. This is indicated by the disappearance of the band at 1680 cm⁻¹ and its replacement by bands characteristic of adsorption on islands of the (1 × 1) structure.     

Observation of true c(8 × 2) symmetry in scanning tunnelling microscopy images of the clean InSb(001) surface

Filled and empty state scanning tunnelling microscopy images of the sputtered and annealed InSb(001) surface are presented. The sputter-anneal preparation generates a surface with two distinct phases. The dominant phase possesses a unit cell with true c(8 × 2) symmetry, whereas the other phase is attributed to an asymmetric 1 × 3 reconstruction. The presence of a c(8 × 2) unit cell in filled state images is in contrast to previous reports, which identified only a 4 × 1 unit cell. The true c(8 × 2) symmetry further indicates, the available structural model is used as a guide, that the current interpretation of features in filled state images is incorrect. This result may necessitate a reevaluation of the structural model for the InSb(001)-c(8 × 2) surface.