The chemical composition of a metal/ceramic interface on an atomic scale: The Cu/MgO {111} interface

The chemical composition profile across a Cu/MgO {111}-type heterophase interface, produced by the internal oxidation of a Cu(Mg) single-phase alloy at 1173 K, is measured via atom-probe field-ion microscopy with a spatial resolution of 0.121 nm; this resolution is equal to the interplanar spacing of the {222} MgO planes. In particular, we demonstrate directly that the bonding across a Cu/MgO {111}-type heterophase interface, along a <111> direction common to both the Cu matrix and an MgO precipitate, has the sequence Cu|O|Mg... and not Cu|Mg|O...; this result is achieved without any deconvolution of the experimental data. Before determining this chemical sequence, it was established, via high-resolution electron microscopy, that the morphology of an MgO precipitate in a Cu matrix is an octahedron faceted on {111} planes with a cube-on-cube relationship between a precipitate and the matrix; that is, {111}_Cu//{222}_MgO and <110>_Cu // <110>_MgO.     

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.     

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).     

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.     

On the atomic structure of {001}W

Results of a field ion microscope study of the clean surface structure of the {001} surface plane of tungsten are presented. The major conclusions are that {001}W is reconstructed over the temperature range 15–580 K, and that the reconstructed surface contains an alternating vertical component to the displacements of the W surface atoms. There are two magnitudes of verticaldisplacement, each arrayed with p(2 × 2) symmetry, and if the differences in the magnitude are neglected, the vertical displacements are arrayed in the well known (√2 × √2)R45° configuration. Details of this newly developed experimental approach for the study of surface reconstruction are reported, along with a number of control experiments which exclude the possibility that these results are artifacts due to the experimental technique. The discussion includes a comparison of the present results with those drawn from other experimental techniques, primarily low energy electron diffraction.     

Adsorption and desorption of no from Rh{111} and Rh{331} surfaces

The adsorption and desorption chemistry of NO on the clean Rh{111} and Rh{331} single crystal surfaces was followed with SIMS, XPS, and LEED. Results suggest dissociative NO adsorption occurs at step and/or defect sites. At saturation coverage there was ～ 10 times more dissociated species on the Rh{331} surface at 300 K than on the Rh{111} surface. On both surfaces two molecular states of NO_ads have been identified as β₁, and β₂ which possess different chemical reactivity. Under the condition of saturation coverage the β₁ and β₂ states are populated on the Rh{111} surface in a different proportion than on the Rh{331} surface. Further, their population on both surfaces is coverage and temperature dependent. When the sample is heated to desorb the saturation overlayer formed on the Rh{111} and Rh{331} crystal surfaces, approximately 50% of the overlayer is found to desorb below ? 400 K primarily from the β₂ state, molecularly as NO(g). Between 300 and 400 K the β₁ state dissociates as binding sites necessary to coordinate N_ads and O_ads are freed by desorption of NO(g).     

Yet another vibrat1onal study of the adsorption system Pt{111}-CO

Infrared spectra of CO adsorbed on Pt{111} indicate only one linear and one bridging species below θ = 0.5. The linear band is subject to a positive dipole-coupling shift and a negative chemical one, both of which exhibit a maximum when plotted as a function of coverage. When q > 0.50, a complex temperature-dependent pattern of shifts and splittings arises in both bands. The temperature-dependent behaviour of the bridging band reported in an earlier paper by Hayden and Bradshaw was not observed. In addition to the bands characteristic of the perfect surface, a second linear band, about 15 cm⁻¹ below the first, is produced by defect sites: we show that such defects are likely to have produced very significant effects in earlier studies of the Pt{111}-CO system. We also propose a real-space interpretation of the low-coverage LEED patterns first reported by Steininger et al.     

Evidence for 2 × 1 building block in the atomic structure of Si{111} 7 × 7

The well known experimental Si {111} 7 × 7 LEED pattern is shown to exhibit systematic enhancement of diffracted intensity at the $\text{1}\text{2}$-order positions, thus revealing the existence of 2 × 1 or 2 × 2 structural components in the 7 × 7 structure with a single domain Si {111} 2 × 1 cleaved structure reveals remarkable similarities. The conclusion is that the fundamental building block of the 7 × 7 structure is a 2 × 1 subunit which closely resembles the unit cell of the cleaved 2 × 1 structure.     

A HREELS study of the UV photon-induced chemistry of C6H5Cl adsorbed on Ag{111}

The UV photochemistry of both monolayer and multilayer C₆H₅Cl adsorbed on Ag{111} surfaces has been studied using high resolution electron energy loss spectroscopy (HREELS). Photon-induced dissociation via the cleavage of the CCl bonds was observed as a common feature. For the monolayer, chemisorbed biphenyl appears to be formed on the surface after photolysis at 110 K and subsequent annealing to 300 K. The two phenyl rings are found to lie parallel to the metal surface. The photon-induced dissociation of multilayer C₆H₅Cl leads, however, to photopolymerization as shown by the high thermal stability of the surface species formed and the detection of simple additive products in thermal desorption.     

Electron energy loss spectroscopy of A {111} oriented aluminum single crystal

Recently, the electron energy loss spectroscopy (ELS) and secondary electron spectroscopy (SES) of the interaction of oxygen with polycrystalline aluminum were reported for primary energies in the range 30 ? E_p ? 250 eV. Two new transitions were resolved in the ELS spectra (one at 4 eV for clean aluminum and the other at 12 eV for oxide-covered aluminum) for low primary energies (E_p ~ 30 eV). In this paper we report on experiments utilizing a {111} oriented single crystal of aluminum that confirm the existence of these loss peaks for low primary energies and show that the 4 eV peak position for pure aluminum depends on the primary beam energy. This suggests that this low energy loss peak is due to direct nonvertical inter- and intraband transitions which differs from the previous assignment.     

Chemisorption of nitrogen on platinum {111}: Reflection-absorption infrared spectroscopy

Reflection-absorption infrared spectroscopy has been combined with thermal desorption and surface coverage measurements to study nitrogen adsorption on a {111}-oriented platinum ribbon under ultrahigh vacuum conditions. Desorption spectra show a single peak (at 180 K) after adsorption at 120 K, giving a coverage-independent activation energy for desorption'of ～40 kJmol^?1. The initial sticking probability at this temperature is 0.15, and the maximum uptake was ～1.1 × 10¹⁴ molecule cm^?2. The adsorbed nitrogen was readily displaced by CO, h₂ and O₂. An infrared absorption band was observed with a peak located at 2238 ± 1 cm^?1, and a halfwidth of 9 cm^?1, with a molecular intensity comparable to that reported for CO on Pt{111}. The results are compared with data for chemisorption on other group VIII metals. An earlier assignment of infrared active nitrogen to B₅ sites on these metals is brought into question by the present results.     

A Rutherford scattering study of the chemical composition of native oxides on GaP

The chemical compositions of two types of protective oxide films on single crystal GaP have been studied by Rutherford backscattering (2 MeV He⁺) combined with ion channeling. Films of 350–1400 Å thickness were grown by immersing GaP slices in hydrogen peroxide, with or without externally applied anodic bias. Films grown by a galvanic coupling process have compositions of about 1:1·1:4·5 (Ga:P:O) and are believed to be vitreous mixtures of Ga₂O₃+P₂O₅. Films grown with anodic bias exhibited a deficiency of Ga in a ～200 Å region at the GaP-oxide interface.     

Etching models for A {111} diamond surface: Calculation of trigon slopes

A mathematical analysis of the etching of {111} diamond surfaces is developed. The slopes of etch pit faces are computed in terms of the specific rate constants, k₂ and k₃, for removal of two- and three-bonded atoms along 〈1&#x0304;10〉 steps and the specific rate constant, k_d, for step nucleation at the central initiating defect. Interactions between neighboring steps are neglected. Two limiting etching regimes are found, i.e., one in which the step velocity increases linearly with step length and a regime of constant step velocity. If k_d is limited by a no overhang criterion, i.e., nucleation of a new step cannot occur until the prior step has moved out of the way, k_d and etch pit slope are functions of the size of the initiating defect. This allows etch pits of vastly different slope to be formed at the same $\text{k}{}_2\text{k}{}_3$ ratio. Point bottom pits with shallow (less than 2°) slopes form from small initiating defects, e.g., dislocation outcrops. At the same $\text{k}{}_2\text{k}{}_3$ ratio flat bottom pits with steep (70° 32') outer faces are formed by etching from large shallow defects, e.g., ring cracks or inclusions. Some preliminary conclusions are drawn about the chemical environment present during the latter stages of diamond genesis.