Structural properties of Bi-terminated GaAs(0 0 1) surface

Electronic and structural properties of Bi-terminated reconstructions on GaAs(0 0 1) surface have been studied by scanning tunneling microscopy (STM) and synchrotron radiation core-level spectroscopy. A 2-3 monolayer thick Bi-layer was evaporated on a Ga-terminated GaAs(0 0 1) surface. By heating the surface, the reconstruction changed from (2 × 1) to (2 × 4). The α2 phase with one top Bi dimer and one As or Bi dimer in the third atomic layer per surface unit cell is proposed to explain the STM images of the Bi/GaAs(0 0 1)(2 × 4) surface heated at 400 °C. Bi 5d photoemission from the Bi/GaAs(2 × 4) consisted of two components suggesting two different bonding sites for Bi atoms on the (2 × 4) surface. The variation of the surface sensitivity of the photoemission induced no changes in the intensities of the components indicating that the origins of both components lie in the first surface layer.     

Chemically prepared well-ordered InP(0 0 1) surfaces

In the present work HCl-isopropanol treated and vacuum annealed InP(0 0 1) surfaces were studied by means of low-energy electron diffraction (LEED), soft X-ray photoemission (SXPS), and reflectance anisotropy (RAS) spectroscopies. The treatment removes the natural oxide and leaves on the surface a physisorbed overlayer containing InCl_x and phosphorus. Annealing at 230 °C induces desorption of InCl_x overlayer and reveals a P-rich (2 × 1) surface. Subsequent annealing at higher temperature induces In-rich (2 × 4) surface. The structural properties of chemically prepared InP(0 0 1) surfaces were found to be similar to those obtained by decapping of As/P-capped epitaxial layers.     

Boron and indium substitution in GaAs(0 0 1) surfaces: Density-functional supercell calculations of the surface stability

Using the density-functional method and surface supercells the surface formation energies are calculated for the most stable GaAs(0 0 1) surface reconstructions without and with up to four indium or/and boron substitutions. Optimal conditions for the growth of the alloys are derived from calculated surface stability diagrams. The incorporation of indium into GaAs without phase separation is possible under strong As-rich conditions and medium to In-rich conditions. Less As-rich conditions can lead to the formation of an InAs phase. Ga-rich conditions give an InGa phase. Isovalent boron incorporation into GaAs without phase separation is possible under strong arsenic and reduced boron exposure. A BAs phase can be formed under more B-rich conditions. More Ga-rich conditions lead to the boron substitution in arsenic positions. The formed boron dimers can be a starting point for the formation of a boron phase. A true antisite boron substitution is less probable. Using the suitable growth conditions obtained for the ternary alloys it is energetically more favourable to incorporate both indium and boron (formation of BInGaAs) than to incorporate only one of the two elements (In or B). The antisite boron incorporation is not favoured in combination with isovalent boron or indium.     

Characterisation of the interaction of glycine with Cu(1 0 0) and Cu(1 1 1)

Reflection-absorption infrared spectroscopy (RAIRS) has been used to characterise the interaction of standard and fully deuterated glycine with Cu(1 0 0) and Cu(1 1 1). RAIRS shows clearly that the surface interaction leads to formation of the adsorbed deprotonated glycinate (NH₂CH₂COO-) species, with some evidence for changes in orientation with coverage previously seen on Cu(1 1 0). Qualitative low energy electron diffraction observations were also conducted to characterise the long-range ordering, although effects of electron-beam-induced radiation damage limited the information obtained. Nevertheless, the results do suggest some subtle isotopic-mass-related structural variations. The results are discussed in the context of previously published scanning tunnelling microscopy and photoelectron diffraction measurements.     

Electronic structures of the suboxide films formed on TiC(1 0 0) and ZrC(1 0 0) surfaces: Density functional theory studies

Density functional theory (DFT) calculations have been performed to elucidate the electronic structures of the TiO-like film on TiC(1 0 0) and the ZrO-like film on ZrC(1 0 0), which are assumed to be monolayers of suboxide films with (1 × 1) periodicity with respect to the substrate (1 0 0) surfaces. It was revealed that the electronic structures of both films were characterized by the existence of a band around 6 eV and a band around the Fermi level. The former and latter bands were mostly composed of O 2p and metal d orbitals, respectively, indicating the substantial ionic nature of the film. The calculated DOS well reproduced the previously obtained photoelectron spectra. From the inspection of the optimized structures, it was found that the both suboxide films have rippled structures; the metal and oxygen atoms are displaced vertically downward and upward, respectively, maintaining the (1 × 1) structures.     

A real-time investigation by RHEED of the homoepitaxial growth of GaAs on (0 0 1) oriented surfaces

In this letter we report on the formation of long-range surface disorder features during the growth by molecular beam epitaxy (MBE) of homoepitaxial GaAs (0 0 1) films having the β2(2 × 4) reconstruction. Observations were made in real-time at the growth temperature using reflection high energy electron diffraction (RHEED) and analyzed kinematically. We show that kinks (cooperative shifts of whole columns of 2 × 4 units along the [1 1 0] direction) form rapidly as growth commences and that the antiphase domain structure present on the substrate prior to growth as a result of the arrangement of As-As dimers persists. This produces a surface with two types of long-range disorder. We speculate on the role of incident Ga atoms on this process.     

Structure of ordered and disordered InxGa1−xP(0 0 1) surfaces prepared by metalorganic vapor phase epitaxy

Ordered and disordered InGaP(0 0 1) films were grown by metalorganic vapor-phase epitaxy and studied by low energy electron diffraction, reflectance difference spectroscopy, and X-ray photoemission spectroscopy. Both alloy surfaces were covered with a monolayer of buckled phosphorus dimers, where half of the phosphorus atoms were terminated with hydrogen. Ordered InGaP(0 0 1) appeared indium rich, and exhibited a reflectance difference spectrum like that of InP(0 0 1). These results support a model whereby the strain energy on the ordered InGaP surface is reduced by aligning the group III atoms in alternating [1 1 0] rows, with the indium and gallium bonding to the buckled-down and buckled-up phosphorus atoms, respectively.     

Pb induced charge accumulation on InAs(1 1 1)B

The Pb/InAs(1 1 1)B interface has been studied by synchrotron radiation photoelectron spectroscopy (SR-PES) of valence band and In4d, As3d and Pb5d core levels. Room temperature deposition of ∼1 ML of Pb on InAs(1 1 1)B leads to an ordered overlayer that induces a metallic channel at the surface, as seen through a weak emission in the vicinity of the Fermi level. Its narrow localization in reciprocal space supports the formation of a two-dimensional free electron gas (2DEG) in the surface region. It is proposed that the adsorbed metal layer swaps the initial polarisation of the surface and thus pulls electrons back to the surface. This charge re-arrangement increases the charge density in the accumulation layer and reduces the screening length and thus the depth of the potential well at the surface.     

Initial stages of oxidation of Cu(1 1 1)

Several surface analysis techniques were combined to study the initial stages of oxidation of Cu(1 1 1) surfaces exposed to O₂ at low pressure (<5 × 10⁻⁶ mbar) and room temperature. Scanning tunneling microscopy (STM) results show that the reactivity is governed by the restructuring of the Cu(1 1 1) surface. On the terraces, oxygen dissociative adsorption leads to the formation of isolated O adatoms and clusters weakly bound to the surface. The O adatoms are located in the fcc threefold hollow sites of the unrestructured terraces. Friedel oscillations with an amplitude lower than 5 pm have been measured around the adatoms. At step edges, surface restructuring is initiated and leads to the nucleation and growth of a two-dimensional disordered layer of oxide precursor. The electronic structure of this oxide layer is characterised by a band gap measured by scanning tunneling spectroscopy to be ∼1.5 eV wide. The growth of the oxide islands progresses by consumption of the upper metal terraces to form triangular indents. The extraction of the Cu atoms at this interface generates a preferential orientation of the interface along the close-packed directions of the metal. A second growth front corresponds to the step edges of the oxide islands and progresses above the lower metal terraces. This is where the excess Cu atoms extracted at the first growth front are incorporated. STM shows that the growing disordered oxide layer consists of units of hexagonal structure with a first nearest neighbour distance characteristic of a relaxed Cu-Cu distance (∼0.3 nm), consistent with local Cu₂O(1 1 1)-like elements. Exposure at 300 °C is necessary to form an ordered two-dimensional layer of oxide precursor. It forms the so-called “29” superstructure assigned to a periodic distorted Cu₂O(1 1 1)-like structure.     

Orientation and structure of triple step staircase on vicinal Si(1 1 1) surfaces

The vicinal Si(1 1 1) surface, inclined towards the direction, was investigated by scanning tunnelling microscopy and spot profile analysing low energy electron diffraction. It has been established that the surface, consisting of regularly spaced triple steps and (1 1 1) terraces with a width equal to that of a single unit cell of the Si(1 1 1)-7 × 7 surface structure, has the (7 7 10) orientation. An atomic model of the triple step is proposed.     

Early stages of interface formation of C60 on GaAs(1 0 0)

We present a detailed investigation of the electronic properties of C₆₀ grown on GaAs(1 0 0) substrates, as a function of the fullerene coverage, from the very early stages of interface formation up to the development of a bulk-like fullerene film. We monitor the chemical interactions and the energy levels alignment by means of X-rays, ultraviolet and inverse photoemission spectroscopies. The two latter techniques allow to investigate the electronic structure close to the Fermi level. Energy levels alignment at the interfaces of C₆₀ with p-doped and GaAs(1 0 0) are obtained and discussed.     

Infrared reflection absorption study of carbon monoxide adsorption on Cu(1 0 0)-c(2 × 2)-Pd surfaces formed by palladium vacuum-depositions at various temperatures

Using infrared reflection absorption spectroscopy (IRRAS) and temperature programmed desorption (TPD), we investigated carbon monoxide (CO) adsorption and desorption behaviors on atomic checkerboard structures of Cu and Pd formed by Pd vacuum deposition at various temperatures of Cu(1 0 0). The 0.15-nm-thick Pd deposition onto a clean Cu(1 0 0) surface at room temperature (RT) showed a clear c(2 × 2) low-energy electron diffraction (LEED) pattern, i.e. Cu(1 0 0)-c(2 × 2)-Pd. The RT-CO exposure to the c(2 × 2) surfaces resulted in IRRAS absorption caused by CO adsorbed on the on-top sites of Pd. The LEED patterns of the Pd-deposited Cu(1 0 0) at higher substrate temperatures revealed less-contrasted c(2 × 2) patterns. The IRRAS intensities of the linearly bonded CO bands on 373-K-, 473-K-, and 673-K-deposited c(2 × 2) surfaces are, respectively, 25%, 22%, and 10% less intense than those on the RT-deposited surface, indicating that Pd coverages at the outermost c(2 × 2) surfaces decrease with increasing deposition temperature. In the initial stage of the 90-K-CO exposure to the RT surface, the band attributable to CO bonded to the Pd emerged at 2067 cm⁻¹ and shifted to higher frequencies with increasing CO exposure. At saturation coverage, the band was located at 2093 cm⁻¹. In contrast, two distinct bands around 2090 cm⁻¹ were apparent on the spectrum of the 473-K-deposited surface: the CO saturation spectrum was dominated by an apparent single absorption at 2090 cm⁻¹ for the 673-K-deposited surface. The TPD spectra of the surfaces showed peaks at around 200 and 300 K, which were ascribable respectively to Cu-CO and Pd-CO. Taking into account the TPD and IRRAS results, we discuss the adsorption-desorption behaviors of CO on the ordered checkerboard structures.     

Photoelectron spectroscopy study of oxygen adsorption on Mo2C(0 0 0 1)

Oxygen adsorption on the α-Mo₂C(0 0 0 1) surface has been investigated with X-ray photoelectron spectroscopy and valence photoelectron spectroscopy utilizing synchrotron radiation. It is found that oxygen adsorbs dissociatively at room temperature, and the adsorbed oxygen atoms interact with both Mo and C atoms to form an oxycarbide layer. As the O-adsorbed surface is heated at ≧800 K, the C-O bonds are broken and the adsorbed oxygen atoms are bound only to Mo atoms. Valence PES study shows that the oxygen adsorption induces a peculiar state around the Fermi level, which enhances the emission intensity at the Fermi edge in PES spectra.     

Surface alloy formation after deposition of Ce on Rh(1 1 0)

Vapour deposition of Ce onto a Rh(1 1 0) single crystal at room temperature is studied by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and low energy electron diffraction (LEED). The thicknesses of the deposited Ce layers are estimated to be between 2 and 9 Å. To study the changes in the Ce-Rh surface layer, the samples are annealed at temperatures between 500 and 1000 °C after Ce deposition.After heating, a c(2 × 2) LEED pattern appears for the sample with the thinnest deposited Ce layer (2.4 Å). For samples with thicker Ce-films, the LEED pattern co-exists of a c(2 × 2) structure and a more diffuse 6% contracted (2 × 1) structure. This appears at the same temperature as the Ce 3d and Rh 3d core levels exhibit sharp intensity changes and binding energy shifts.The intensity of the f⁰, f¹ and f² multiplets in the Ce 3d core level spectra change when the annealing temperature is increased. The relative intensity of the Ce 3d f⁰ and f² features compared to the Ce 3d f¹ features is largest after annealing to 500 °C. This is below the temperature at which the ordered surface alloy is formed. When the sample is heated above the formation temperature of the surface alloy, the relative intensity of the Ce 3d f⁰ and f² features decrease.     

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.     

Ultra-thin film growth of titanium dioxide on W(1 0 0)

We have employed low energy electron diffraction (LEED) and X-ray photoelectron spectroscopy to follow the epitaxial growth of thin films of TiO₂ on W(1 0 0). The films were grown both by metal vapour deposition of titanium onto the substrate in UHV with subsequent annealing in a low partial pressure of oxygen, and by metal vapour deposition in a low partial pressure of oxygen. LEED patterns showed the characteristic patterns of (1 1 0) oriented rutile. A systematic spot splitting was observed and attributed to a stepped surface. The calculated step height was found to be in good agreement with that expected for rutile TiO₂(1 1 0), 3.3 Å. Titanium core level shifts were used to identify oxidation states as a function of film thickness allowing the interpretation in terms of a slightly sub-stoichiometric interface layer in contact with the substrate. In combination with the LEED patterns, the film structure is therefore determined to be (1 1 0) oriented rutile with a comparable level of stoichiometry to UHV prepared bulk crystals. The ordered step structure indicates considerable structural complexity of the surface.     

Sulfur poisoning of the CO adsorption on Co(0 0 0 1)

CO adsorption on a sulfur covered cobalt surface at 185 K has been studied using XPS, TDS, LEED, and WF measurements. As in the case of CO adsorption on the clean Co(0 0 0 1) surface, CO adsorbs and desorbs molecularly and no dissociation was observed. The saturation coverage of CO decreases linearly from 0.54 ML to 0.27 ML when the S pre-coverage increases to 0.25 ML. The WF increased during CO adsorption, but did not reach the value obtained for CO adsorption on the clean surface. The smaller work function change is explained by the reduced adsorption of CO on the sulfur-precovered surface. A reduction in the activation energy of desorption for CO from 113 kJ/mol to 88 kJ/mol was observed indicating weaker bonding of the CO molecules to the surface. The behavior of the CO/S/Co(0 0 0 1) system was explained by a combination of steric and electronic effects.     

Electron surface states in short-period superlattices: (GaAs)2/(AlAs)2(1 0 0)-c(4 × 4)

The electronic structure of (GaAs)₂/(AlAs)₂(1 0 0)-c(4 × 4) superlattice surfaces was studied by means of angular-resolved photoelectron spectroscopy (ARUPS) in the photon energy range 20-38 eV. Four samples with different surface termination layers were grown and As-capped by molecular beam epitaxy (MBE). ARUPS measurements were performed on decapped samples with perfect c(4 × 4) reconstructed surfaces. An intensive surface state was, for the first time, observed below the top of the valence band. This surface state was found to shift with superlattices’ different surface termination in agreement with theoretical predictions.     

Surface phonons of clean, hydrogen- and deuterium-terminated Si(0 0 1) surfaces

We present a comprehensive vibrational study of the clean and hydrogen- or deuterium-terminated silicon (0 0 1) surface. The modes related to the clean as well as to the H:Si, D:Si, and 2H:Si, 2D:Si surfaces are studied by means of high resolution electron energy loss spectroscopy (HREELS). We pay special attention to the modification of the phonon modes by the surface treatments and compare the data with reported experimental and theoretical results. The analysis of the relative phonon intensities of the clean, mono- and dihydride surfaces yields the assignment of the modes related to the dimer bonds. The isotopic shifts of vibrons related to the Si-H and Si-D bonds and to the surface phonon are discussed and applied to the characterisation of the surface excitations.     

The comparative study of two dimensional condensation of Xe and Kr physisorbed on Ag(1 1 1) and Ag(1 0 0)

Adsorption isobars of Xe and Kr on Ag(1 1 1) and Ag(1 0 0) were observed simultaneously by an extremely-low-current low energy electron diffraction and an ellipsometry in the temperature range between 60 K and 90 K and in the equilibrium pressure range between 8 × 10⁻⁶ Pa and 2 × 10⁻⁴ Pa. Two dimensional condensation of the first layer of Xe on Ag(1 1 1) occurred at the temperature 0.3 ± 0.1 K higher than that on Ag(1 0 0). In the case of Kr on Ag(1 1 1) and Ag(1 0 0), the temperature difference was 0.2 ± 0.1 K. This temperature difference was discussed on the assumption that it is caused by the repulsive interaction between the dipoles induced in rare gas atoms. We estimated the difference of the induced dipole moment μ: μ of Xe atom on Ag(1 0 0) is 6% larger than that on Ag(1 1 1) and μ of Kr atom on Ag(1 0 0) is 14% larger than that on Ag(1 1 1).