Adsorption of oxygen and carbon dioxide on cesium-reconstructed Ag(1 1 0) surface

The adsorption of oxygen and carbon dioxide on cesium-reconstructed Ag(1 1 0) surface has been studied with scanning tunneling microscopy (STM) and temperature programmed desorption (TPD). At 0.1 ML Cs coverage the whole surface exhibits a mixture of (1 × 2) and (1 × 3) reconstructed structures, indicating that Cs atoms exert a cooperative effect on the surface structures. Real-time STM observation shows that silver atoms on the Cs-covered surface are highly mobile on the nanometer scale at 300 K. The Cs-reconstructed Ag(1 1 0) surface alters the structure formed by dissociative adsorption of oxygen from p(2 × 1) or c(6 × 2) to a p(3 × 5) structure which incorporates 1/3 ML Ag atoms, resulting in the formation of nanometer-sized (10–20 nm) islands. The Cs-induced reconstruction facilitates the adsorption of CO₂, which does not adsorb on unreconstructed, clean Ag(1 1 0). CO₂ adsorption leads to the formation of locally ordered (2 × 1) structures and linear (2 × 2) structures distributed inhomogeneously on the surface. Adsorbed CO₂ desorbs from the Cs-covered surface without accompanied O₂ desorption, ruling out carbonate as an intermediate. As a possible alternative, an oxalate-type surface complex [OOC–COO] is suggested, supported by the occurrence of extensive isotope exchange between oxygen atoms among CO₂(a). Direct interaction between CO₂ and Cs may become significant at higher Cs coverage (>0.3 ML).     

Deposition of lead iodide films on Rh(1 0 0) electrodes from colloidal solutions––the effect of an iodine adlayer

The growth of PbI₂ precipitates on single crystal substrates from colloidal solutions has been investigated with in air scanning tunneling microscopy and synchrotron-based X-ray photoelectron spectroscopy. The PbI₂ growth on Rh(1 0 0) results in nano-clusters with lateral dimensions between 30 and 60 Å, consistent with earlier reports. However, the growth of PbI₂ on a well-ordered iodinated Rh(1 0 0), denoted as (√2×√2)R45°-I, leads to atomically smooth PbI₂ films having a hexagonal symmetry with lattice constant identical to the bulk value of 4.5 Å. The heteroepitaxy is believed to be effected by the atomic iodine monolayer that helps to accommodate large lattice mismatch between PbI₂ and Rh surface with short-range van der Waals interaction.     

Adsorption and dissociation of Si2H6 on Ge(001)2 × 1

Adsorption and thermally-induced dissociation of disilane (Si₂H₆) on clean Ge(001)2 × 1 surfaces have been investigated using a combination of Auger electron spectroscopy (AES), electron energy loss spectroscopy (EELS), reflection high-energy electron diffraction (RHEED), and scanning tunneling microscopy (STM). With initial Si₂H₆ exposure at room temperature, the Si surface coverage increased monotonically, the EELS surface dangling bond peak intensities continuously decreased, and the intensity of half-order RHEED diffraction rods decreased. The low-coverage Si₂H₆ sticking probability at 300 K on Ge(001) was found to be 0.5 while the saturation coverage was 0.5 ML. A new EELS feature, GSH, involving Si-H and Ge-H bond states was observed at Si₂H₆ exposures φ 3.4 × 10¹³ cm⁻². In contrast to Si₂H₆ -saturated Si(001), the saturated Ge(001) surface significant fraction of dimerized bonds. Adsorbed overlayers were highly disordered with the primary species on saturated surfaces being SiH₂, GeH, and undissociated SiH₃· Si₂H₆-saturated Ge(001)2 × 1 substrates were annealed for l min at temperatures T_a between 425 and 825 K. Admolecules were mobile at T_a = 545 K giving rise to significant ordering in one-dimensional chains. By T_a = 605 K, essentially all of the admolecules were captured into coarsened islands. Dangling-bond EELS peaks reappeared by 625 K and the intensities of the half-order RHEED diffraction rods increased. Ge segregation to the surface, which began at T_a 625 K, occurred rapidly at T_a 675 K. All H was desorbed by 725 K.     

LEED studies of the adsorption of CO2 on thin epitaxial NaCl(100) films

The adsorption of CO₂ on the NaCl(100) surface was studied with a high-resolution LEED-system. Measurements without charging up at low electron energies and without damage by the e-beam could be performed by using ultrathin epitaxial films on a conducting Ge(100) substrate. The adsorption behavior was recorded as a function of time and pressure at constant substrate temperatures of 78 and 83 K and CO₂ partial pressures from 4 × 10⁻⁸−2 × 10⁻³ Pa. The adsorption system shows a first-order two-dimensional phase transition to a (2 × 1) superstructure including glide planes (herringbone-like structure) at p = 7.2 × 10⁻⁸Pa (T = 78 K). The condensation of the CO₂ solid is starting at p = 1.5 × 10⁻⁴ Pa (T = 78 K). The LEED-pattern shows in this c(2 × 2) superstructure, which corresponds to the pyrite-like structure of the CO₂ solid. Both observed superstructures are commensurable with the NaCl(100) surface. Observation of island growth shows that the domains of the (2 × 1) superstructures have already at coverage of 5% of a monolayer an average lateral size of at least 200 A.     

Defects and Pd growth on the reduced SnO2(1 0 0) surface

Scanning tunneling microscopy experiments on a clean, reduced SnO₂(1 0 0)-(1 × 1) surface reveal surface defects with zero-, one-, and two-dimensions. Point defects consist of missing SnO/SnO₂ units. Line defects are probably crystallographic shear planes that extend to the surface and manifest themselves as rows of atoms, shifted half a unit cell along the [0 1 0] direction. Their ends act as preferential nucleation sites for the formation of Pd clusters upon vapor deposition. Areas of a more reduced surface phase, still with a (1 × 1) structure and a half-unit cell deep, form at [0 0 1]-oriented step edges.     

Single crystal RuO2/Ti and RuO2/TiO2 interface: LEED, Auger and XPS study

The interactions at the evolving RuO₂/titanium interface have been studied by LEED, AES and XPS. Titanium films of up to 5 monolayers were evaporated onto well ordered and ion sputtered ruthenium dioxide crystal surfaces of (110) and (100) orientation. Stabilization of the surface oxygen content under thermal treatment in UHV (up to 600°C) with increasing titanium coverage was established. After extended (up to 4 h) annealing in O₂ at 600°C an epitaxial ordering of TiO₂ on RuO₂(110) was observed. The (1 × 1) LEED patterns from the epitaxial layer exhibit a reduced background level when compared to the RuO₂ substrate itself. These findings are correlated with the XPS data and are interpreted in connection with the disappearance of the defect RuO₂ phase in the surface layer of the RuO₂. The appearance of the (1 × 2) surface reconstruction at the RuO₂(100)/Ti interface is discussed in the context of maximum cation coordination by oxygen atoms.     

X-ray diffraction studies of epitaxy in orthorhombic- DyMnO3/Er1Ba2Cu3O7-δ thin film heterostructures on LaAlO3 (100) substrates

The heteroepitaxy in DyMnO₃/Er₁Ba₂Cu₃O_7-δ bilayer thin films on LaAlO₃ (100) substates was characterized by four-circle X-ray diffractometry. The Er₁Ba₂Cu₃O_7-δ thin films on LaAlO₃ (100) substrates were prepared by molecular-beam deposition (MBD) and post-growth annealing in wet and dry O₂ at 880°C, whereas the DyMnO₃ thin films on the Er₁Ba₂Cu₃O_7-δ/LaAlO₃ (100) heterostructure were deposited by MBD and post-growth annealing in dry O₂ at 750°C. The conventional X-ray diffraction (XRD) patterns as well as pole figures (φ-scans) for specific (hkl) reflections were acquired. The Er₁Ba₂Cu₃O_7-δ thin film in the DyMnO₃/Er₁Ba₂Cu₃O_7-δ/LaAlO₃ (100) heterostructure showed [001] oriented epitaxial growth, as expected. The DyMnO₃ thin film on the Er₁Ba₂Cu₃O_7-δ epilayer in the heterostructure grew with (110) epitaxy in its metastable orthorhombic phase (lattice constants: a_o=5.272 Å, b_o=5.795 Å and c_o=7.38 Å). The heteroepitaxial relationships at the orthorhombic-DyMnO O₃ (110) /Er₁Ba₂Cu₃O_7-δ (001) interface was determined as the following: DyMnO₃ (110) Er₁Ba₂Cu₃O_7-δ (001), DyMnO₃ [1 0] ¶r; Er₁Ba₂Cu₃O_7-δ[100] or Er₁Ba₂Cu₃O_7-δ[010], and DyMnO₃ [001] ¶r; Er₁Ba₂Cu₃O _7-δ[010] or Er₁Ba₂Cu₃O_7-δ [100].     

Interaction between CO and NH3 coadsorbed on Ru(001): its effects on the ordering in mixed adlayers and the ammonia dissociation

The coadsorption of CO and ammonia on Ru(001) has been investigated by low-energy electron diffraction (LEED), temperature-programmed desorption (TPD) and high-resolution electron energy-loss spectroscopy (HREELS). The main focus has been on the interaction between different admolecules on the surface and its important role in surface reaction. Exposing CO-precovered Ru(001) to ammonia at 100 K leads to the formation of mixed ordered layers with a (2 × 2) periodicity. It was found that two types of (2 × 2) structures are formed depending on the CO precoverage. One of the (2 × 2) structures (-phase) contains one CO and two ammonia molecules per (2 × 2) unit cell and the other (β-phase) contains two CO and one ammonia. Structure models for the two phases are proposed based on vibrational spectra measured for the coadsorbed phases of CO and ammonia (¹⁵NH₃ or ND₃). TPD results suggest that the ammonia dissociation takes place on clean and CO-precovered Ru(001). The amount of dissociated ammonia decreased initially with increasing CO precoverage, passed a minimum at θ_CO = 0.25, increased with a further increase of CO coverage, and eventually reached a saturation value above θ_CO = 0.5. The dissociation of ammonia in the β−(2 × 2) structure was found to be enhanced by a factor of 4–6 as compared with the dissociation in the −(2 × 2) structure. The HREEL spectra indicated that the C_3v molecular axis of ammonia is tilted in the coadsorbed layers, the tilting being most pronounced in the β−(2 × 2) phase with a high CO partial coverage. This observation suggests that the tilting of ammonia due to the interaction with CO facilitates electron donation from Ru 4d to LUMO of ammonia, leading to the N-H bond dissociation. The microscopic model for the CO-NH₃ interaction on metal surfaces is presented.     

Monte Carlo simulation for temperature dependence of Ga diffusion length on GaAs(0 0 1)

Diffusion length of Ga on the GaAs(0 0 1)-(2×4)β2 is investigated by a newly developed Monte Carlo-based computational method. The new computational method incorporates chemical potential of Ga in the vapor phase and Ga migration potential on the reconstructed surface obtained by ab initio calculations; therefore we can investigate the adsorption, diffusion and desorption kinetics of adsorbate atoms on the surface. The calculated results imply that Ga diffusion length before desorption decreases exponentially with temperature because Ga surface lifetime decreases exponentially. Furthermore, Ga diffusion length L along and [1 1 0] on the GaAs(0 0 1)-(2×4)β2 are estimated to be and L_[110]200 nm, respectively, at the incorporation–desorption transition temperature (T860 K).     

The surface structure of the metallic sodium tungsten bronze Na0.667WO3(001)

Scanning tunnelling microscopy has been used to identify a number of surface reconstructions on the (001) surface of the cubic metallic sodium tungsten bronze, Na_0.667WO₃. Which is dominant has been found to depend critically on sample preparation. As well as a reconstruction that bears a striking similarity to that of the parent material, tungsten trioxide, regions of (2×1) periodicity are observed that can only be explained in terms of an Na_yO surface layer. In the current work, we relate the effect of sample preparation on the surface electronic structure of Na_0.667WO₃(001) with that on the atomic structure by comparing photoemission spectra with STM images. Particular interest is focused on band gap defect states in photoemission spectra which, in contrast to similar states in spectra from WO₃, do not appear to correlate with the appearance of localised defects or highly reduced terraces in STM images. The existence of peroxide-like oxygen dimers at the (2×2) reconstructed surface, on the other hand, is characterised by the appearance of identifiable states in the valence band spectrum.     

Structure and stability of the anatase TiO2 (101) and (001) surfaces

Well-defined (101) and (001) surfaces of anatase TiO₂ were studied for the first time by secondary-electron imaging and low-energy electron diffraction. Initially, both surfaces show a crystalline structure corresponding to the bulk anatase phase, buried under an atomically thin contamination layer. After mild sputtering with 500 eV Ne⁺ ions, we have observed a surface phase transition from tetragonal anatase to face-centered cubic titanium monoxide TiO. Subsequent annealing at 900 K restores the (1×1) anatase structure at the (101) surface. On the (001) surface, however, a (1×4) reconstruction appears. The unreconstructed structure can be recovered by exposing the surface to oxygen. These observations demonstrate the stability of the anatase surfaces and illustrate the feasibility of preparing and investigating clean surfaces of this technological important form of TiO₂.     

Buffers for high temperature superconductor coatings. Low temperature growth of CeO2 films by metal–organic chemical vapor deposition and their implementation as buffers

Smooth, epitaxial cerium dioxide thin films have been grown in-situ in the 450–650°C temperature range on (001) yttria-stabilized zirconia (YSZ) substrates by metal–organic chemical vapor deposition (MOCVD) using a new fluorine-free liquid Ce precursor. As assessed by X-ray diffraction, transmission electron microscopy (TEM), and high-resolution electron microscopy (HREM), the epitaxial films exhibit a columnar microstructure with atomically abrupt film-substrate interfaces and with only minor bending of the crystal plane parallel to the substrate surface near the interface and at the column boundaries. With fixed precursor temperature and gas flow rate, the CeO₂ growth rate decreases from 10 Å/min at 450°C to 6.5 Å/min at 540°C. The root-mean-square roughness of the films also decreases from 15.5 Å at 450°C to 4.3 Å at 540°C. High-quality, epitaxial YBa₂C₃O_7−x films have been successfully deposited on these MOCVD-derived CeO₂ films grown at temperatures as low as 540°C. They exhibit T_c=86.5 K and J_c=1.08×10⁶ A/cm² at 77.4 K.     

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.     

Reversible H2 passivation of Si ≡ Si3 interface defects in (1 1 1)Si/SiO2

K-band electron spin resonance (ESR) at 4.3 K has revealed the dipole-dipole (DD) interaction effects between [1 1 1]P_b centers (^*Si ≡ Si₃ defects with unpaired sp³ hybrid [1 1 1]) at the 2 dimensional (1 1 1)Si/SiO₂ interface. This has been enabled by the perfectly reversible H₂ passivation of P_b, which affects the defect's spin state. Sequential hydrogenation at 253–353°C and degassing treatments in high vacuum at 743–835°C allowed to vary the P_b density in the range 5 × 10¹⁰ < [P_b] (1.14 ± 0.06) × 10¹³ cm^-2. With increasing [P_b] fine structure doublets are clearly resolved. It is found that (1 1 1)Si/SiO₂ interfaces, dry thermally grown at ≈920°C, naturally comprise a ^*Si ≡ Si₃ defect density — passivated or not — of 1.14 × 10¹³ cm^-2.     

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.     

Growth and characterization of model oxide catalysts

Oxide catalysts are frequently used to convert toxic species to environmentally benign molecules, and to prevent the formation of toxic species in the first place. In this paper, growth and characterization of model oxide systems employed in both approaches is discussed. An example of the former approach is the selective catalytic reduction (SCR) of NO emitted from power plants by NH₃, which employs tungsten and vanadium oxides supported on the anatase polymorph of TiO₂. To model SCR catalysts, epitaxial titanium, vanadium and tungsten oxide films were grown using molecular beam epitaxy and magnetron sputtering. Two different anatase orientations were grown on LaAlO₃ substrates and their interactions with vanadia were characterized. On LaAlO₃ (0 0 1), anatase exposed a (4 × 1) reconstructed (0 0 1) surface. Vanadia lifted the reconstruction and at 1 ML a (1 × 1) surface with mostly V⁵⁺ was observed. Continued V₂O₅ growth led to loss of order, but at high temperatures epitaxial VO₂ could be grown; vanadia behaved similarly on anatase films on LaAlO₃ (1 1 0). Results suggested that the monolayer is pseudomorphic with O adsorption oxidizing the surface V to 5+, since the anatase structure cannot accommodate more bulk oxygen, only a monolayer can be pseudomorphic and have only V⁵⁺. Thus the vanadia monolayer has unique structural and chemical properties that can help explain why vanadia monolayers on TiO₂ are much more active than bulk V₂O₅. For WO₃, a series of added row reconstructions were observed as the epitaxial films were reduced. The effect of these structures on surface chemistry was characterized by studying 1-propanol adsorption. The results indicated that the structure of the WO₃ surface did not alter its catalytic function but had a strong effect on reaction kinetics. As an example of a system where catalysts prevent the formation of toxic species, the reactivity of oxidized Pd surfaces used in CH₄ catalytic combustion were studied. An ordered PdO-like monolayer was found to be less reactive towards CO than adsorbed O on Pd. On the other hand, the PdO layer favored a lower activation energy C₃H₆ oxidation pathway. The results indicated that Pd oxidation reduces the sticking coefficient of reactive species but once molecules adsorb, the oxide surface can reduce the activation energy for subsequent reaction.     

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.     

Luminescence of molecules adsorbed on surfaces of wide gap materials

We report on the photoluminescence spectra of thin films of chain-like π-conjugated molecules on well-defined surfaces of wide gap inorganic materials. The aim is to study the energy transfer processes across the organic/substrate interface which limit the luminescence of molecules in close contact to substrate surfaces. We discuss quaterthiophene (4 T) adsorbed on the c(2×2)-ZnSe(0 0 1) surface and tetracene (Tc) on the surface of a thin epitaxial Al₂O₃ film on Ni₃Al(1 1 1). For thin films vapor-deposited at low substrate temperatures, we observe no luminescence signal for both systems, which indicates the presence of fast luminescence quenching processes at the organic/inorganic interface. After annealing, luminescence spectra corresponding to those of the bulk crystals are obtained. This can be explained by the formation of 3D-crystallites, which effectively separate most molecules from the organic/inorganic interface.     

Highly stable passivation of a Si(1 1 1) surface using bilayer-GaSe

As a stable and ‘epitaxial’ passivation of a Si surface, we propose the bilayer-GaSe termination of a Si(1 1 1) surface. This surface is fabricated by depositing one monolayer of Ga on a clean Si(1 1 1) surface and subsequent annealing in a Se flux at around 520 °C, which results in unreconstructed 1×1 termination of the Si(1 1 1) surface by bilayer-GaSe. We found by scanning tunneling microscopy observation that slow cooling of the clean Si(1 1 1) surface from 850 to 520 °C with simultaneous deposition of a Ga flux results in better termination of the Si(1 1 1) surface. It was also found that this surface is stable against heating around 400 °C in O₂ atmosphere of 3×10⁻³ Pa. By utilizing these properties of the bilayer-GaSe terminated surface, we have succeeded in fabricating ZnO quantum dots on this substrate.