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.     

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.     

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.     

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 of CO on clean {100} nickel

LEED experiments on the adsorption of CO on {100} nickel have been repeated with the addition of a quadrupole mass spectrometer. The results confirm earlier observations that CO does adsorb on this clean surface and further indicate that such a surface cannot be cleaned by heating alone. CO adsorption on the surface subsequent to prolonged heat treatment is greatly reduced due to diffusion of contamination from the bulk.     

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.     

Adsorption and reaction of nitric oxide and oxygen on Rh(111)

Adsorption of NO and O₂ on Rh(111) has been studied by TPD and XPS. Both gases adsorb molecularly at 120 K. At low coverages (θ_NO < 0.3) NO dissociates completely upon heating to form N₂ and O₂ which have peak desorption temperatures at 710 and 1310 K., respectively. At higher NO coverages NO desorbs at 455 K and a new N₂ state obeying first order kinetics appears at 470 K. At saturation, 55% of the adsorbed NO decomposes. Preadsorbed oxygen inhibits NO decomposition and produces new N₂ and NO desorption states, both at 400 K. The saturation coverage of NO on Rh(111) is approximately 0.67 of the surface atom density. Oxygen on Rh(111) has two strongly bound states with peak temperatures of 840 and 1125 K with a saturation coverage ratio of 1:2. Desorption parameters for the 1125 peak vary strongly with coverage and, assuming second-order kinetics, yield an activation energy of $\text{85 ± 5}\text{kcal}\text{mol}$ and a pre-exponential factor of 2.0 cm² s^?1 in the limit of zero coverage. A molecular state desorbing at 150 K and the 840 K state fill concurrently. The saturation coverage of atomic oxygen on Rh(111) is approximately 0.83 times the surface atom density. The behavior of NO on Rh and Pt low index planes is compared.