CHaracterization of CO binding sites on Rh{111} and Rh{331} surfaces by XPS and LEED: Comparison to EELS results

Changes in the nature of the binding site of chemisorbed CO on the Rh{111} and Rh{331} single crystal surfaces during adsorption and desorption have been monitored by X-ray Photoelectron Spectroscopy (XPS) and Low Energy Electron Diffraction (LEED). Two bonding states of molecular CO have been identified from the O 1s photoemission line. These states are assigned as atop and bridge-bonded species and are observed to be coverage and temperature dependent. On both surfaces atop sites are populated first and at higher CO coverages bridge sites are filled. On Rh{111} the bridge sites are filled at a CO coverage of θ_CO ～ 0.50 and their presence is correlated with a change in the LEED pattern. The presence of the step atoms on the Rh{331} surface markedly influenced the sequential filling of binding sites in comparison to that observed on the Rh{111} surface. A comparison of our data to previous Electron Energy Loss Spectroscopy (EELS) work on Rh{111} is in remarkable quantitative agreement with EELS peak heights.     

Adsorption and desorption of CO and H2 on Rh(111): Laser-induced desorption

Isosteric heats of adsorption ΔH_ad of CO and sticking coefficients S for CO and H₂ on Rh(111) are determined by laser-induced thermal desorption (LITD) in which a pulsed laser beam is focused onto the surface, and rapid local heating yields a desorption signal that is proportional to the adsorbate coverage θ. ΔH_ad for CO falls from 32.0±2 kcal/mol at low coverage to 14 kcal/mol at saturation, and the desorption pre-exponential factor v_d decreases from 10^14±0.5 to 10¹⁰ s^-1. ΔH_ad, v_d, and S of CO all decline sharply above θ = 0.2, corresponding to the occupation of a second binding state. Sticking coefficients for CO and hydrogen indicate precursor intermediates in adsorption.     

Thermal desorption spectroscopy of condensed lead films on {100} GaAs surfaces

The desorption of Pb from MBE-grown {100} GaAs surfaces has been investigated using modulated-beam mass spectrometry, isothermal desorption rate measurements and temperature programmed thermal desorption spectroscopy. The results are in general agreement with a model in which desorption occurs from a disperse phase which is in equilibrium with adsorbate islands. From the independence of the activation energy of desorption on coverage from <10^–3 s monolayers to several tens of monolayers, single atom desorption is the probable rate limiting step. An important conclusion is that it is not possible to perform a unique analysis of temperature programmed desorption data from condensed films without prior knowledge of the dependence of the desorption activation energy on coverage.     

Bulk-like structure of diamond {111}

A LEED (low-energy electron diffraction) intensity analysis of C {111} 1 × 1 (diamond) has given good agreement with a surface structure which has bulk positions with small relaxation of the first interlayer spacing for both insulating and semiconducting specimens. The truncated-bulk character of C{111} 1 × 1 gives support to the previously determined bulk-like structure of stabilized Si{111} 1 × 1, and casts doubt on the disordered 7 × 7 structure suggested for the stabilized 1 × 1 phase by interpretation of photoemission measurements. In both cases rather than doubt the LEED structure, one can doubt the interpretation of the photoemission measurements.     

Atomic structure of Fe {111}

A clean Fe {111} surface was prepared and studied with LEED (low-energy electron diffraction) and AES (Auger electron spectroscopy). A LEED intensity analysis was carried out with a new computational scheme (THIN) specially designed for short interlayer spacings. The results are, for the fust interlayer spacing, d₁₂ = 0.70 ± 0.03 Å and for the inner potential V₀ = 11.1 ± 1.1 eV, the confidence intervals referring to 95% confidence level. Thus, the Fe {111} surface is contracted 15.4% with respect to the bulk (0.827 Å).     

Photon and electron stimulated desorption of adsorbates from W {100}

We have performed photon and electron stimulated desorption (PSD and ESD) studies of F⁺, Cl⁺ and O⁺ ions from a W {100} surface and have measured the kinetic energies for a small range of emission angles of these ions as well as the effect of different electron and photon excitation energies. We find that the PSD and ESD processes show essentially the same threshold energies and produce the same ion energy and angle distribution, and so evidently involve the same mechanism. For the case of O⁺ we also find clear evidence that substrate core-level excitation initiates the desorption process as proposed by Knotek and Feibelman for adsorbates bonded to surface atoms with a maximal valency configuration. The substrate levels are not seen to play a role in the F⁺ and Cl⁺ desorption, indicating a very different type of bonding for these species on the W surface.     

Electron states and atomic positions at the {001}, {110} and {111} faces of W and Mo

The results of ab initio calculations on the {001}, {110} and {111} surfaces of W and Mo and on the (√2 × √2)R45° reconstructed W {001} surface are presented. A distribution of surface states in reasonable agreement with experiment is found. A simple parametrisation of the short range repulsive force between transition metal atoms is used to predict, for all these surfaces, relaxations which are comparable with those observed. This same parametrisation indicates that the W and Mo {001} surfaces are stable to proposed reconstructive displacements.     

Coverage dependence of the kinetics for H2 desorption from Rh(111)

Coverage-dependent sticking probabilities and second-order rate constants for recombinative desorption of hydrogen from Rh(111) have been measured using molecular beam relaxation spectroscopy (MBRS) and time-resolved specular helium scattering. The sticking probability follows second-order Langmuir coverage dependence, with s₀ equal to 0.01 ± 0.005. Under isothermal and nearly isosteric conditions over the coverage range 0.2–0.7 ML, the second-order rate constant for desorption is essentially independent of hydrogen coverage, in contrast to kinetic parameters determined from thermal desorption spectra.     

Si｛111｝的吸附表面结构

利用低能电子衍射研究了金属和非金属吸附在Ｓｉ｛１１１｝表面的表面结构。结果显示出：对Ａｌ、Ｇａ、Ｂｉ和Ａｕ原子，形成α－Ｓｉ｛１１１｝３×３Ｒ３０°－Ｍ或β－Ｓｉ｛１１１｝３×３Ｒ３０°－Ｍ结构的共价吸附。对Ｌｉ、Ｎａ和Ａｇ原子，形成正离子吸附，全部经高温解吸后，便诱导出Ｓｉ｛１１１｝１×３重构。对Ｔｅ原子，形成负离子吸附，经高温解吸后，便诱导出Ｓｉ｛１１１｝类（１×１）结构。     

Velocity dependence of azimuthal anisotropies in ion scattering from rhodium {111}

The scattering of He⁺, Ne⁺ and Ar⁺ ions from Rh {111} is measured as a function of the azimuthal angle of the primary ion for an incident polar angle of 70° from the surface normal and an inplane collection angle of 60°. In this case anisotropy is defined as the ratio of the yield of ions scattered having the azimuth of 〈110〉 to the yield of those having the azimuth of 〈211〉. The yield ratio for all particle types correlates with particle velocity. The ratio is ～ 1 at low velocities, decreases to ～ 0.2 at 8 × 10⁶$\text{cm}\text{s}$ and then increases to a value of 1.4 at 25 × 10⁶$\text{cm}\text{s}$. Molecular dynamics calculations have been performed for Ne⁺ ion scattering from Rh{111} in order to understand the changes in anisotropy with particle velocity. Qualitative agreement with the experimental results is obtained without having to account for neutralization. A neutralization probability that depends on the collision time improves the agreement between the calculated and experimental yield ratios. A velocity dependent probability will not affect the ratio of yields in two different azimuthal directions.     

Adsorption and desorption of oxygen on stepped tungsten surfaces

The adsorption and desorption of oxygen on stepped tungsten surfaces with orientations close to the (110) orientation and steps parallel to the most densely packed crystal direction ([111]) is studied with low energy electron diffraction, Auger electron spectroscopy, work function measurements and thermal desorption spectroscopy. With increasing deviation from the (110) orientation, an increasing preference for the formation of the p(2 × 1) domain with the densely packed direction parallel to the steps is noted. The adsorption kinetics does not differ markedly from that on the flat (110) surface, however the desorption behaviour at low coverages (θ < 0.3) is quite different. The results are interpreted in terms of the dissociation of a mobile precursor at terrace and step sites, the competition between the two domains during their growth and a step-induced premature transition to the complex structure observed on flat (110) surfaces at $\text{θ ? 8}$. The steps are believed to play also a significant role in desorption.     

Damage studies on the system^{111} \mathop {In}\limits^ \to \underline {Ni}

Lattice damage after implantation of¹¹¹In in Ni has been studied applying the DPAC technique to the 171–245 keV -ray cascade in the daughter nucleus¹¹¹Cd. Implantations were carried out at 10 K and at 300 K. The low temperature implantation yields a higher regular substitutional fraction (80%) than the room temperature implantation (40%). The annealing behaviour of both implants above RT is the same. In addition, two distinct defect-associated sites were observed in isochronal annealing sequences. A microscopic model for these defects is presented, which takes into account magnetic and electric hyperfine interaction strengths, binding energies and site populations as a functions of temperature.     

Ferromagnetic resonance relations in {111}-oriented garnet films

Microwave resonance relations for a {111} garnet film have been derived including the uniaxial as well as the first and second order cubic anisotropy contributions. Special attention has been given to the in-plane resonance condition. For this case the calculation has been made up to second order inK ₁/MH andK ₂/MH taking into account the influence of a nonideal in-plane configuration of the film.The author wishes to express his thanks to Dr. Z. Frait for valuable discussions.