The adsorption of carbon monoxide on TiO2(110) supported palladium

Palladium overlayers deposited on TiO₂(110) by metal vapour deposition have been investigated using LEED, XPS and FT-RAIRS of adsorbed CO. Low coverages of palladium (<3 ML) deposited at 300 K adsorb CO exclusively in a bridged configuration with a band (B₁ at 1990 cm⁻¹) characteristic of CO adsorption on Pd(110) and Pd(100) surfaces. When annealed to 500 K, XPS and LEED indicate the nucleation of Pd particles on which CO adsorbs predominantly as a strongly bound linear species which we associate with edge sites on the Pd particles (L* band at 2085 cm⁻¹). Both bridged and linear CO bands are exhibited as increases in reflectivity at the resonant frequency, indicating the retention of small particle size during the annealing process. Palladium overlayers of intermediate coverages (10–20 ML) deposited at 300 K undergo some nucleation during growth, and adsorbed CO exhibits both absorption and transmission bands in the B₁ (1990 cm⁻¹) and B₂ (1940 cm⁻¹) regions. The latter is associated with the formation of Pd(111) facets. Highly dispersed Pd particles are produced on annealing at 500 K. This is evidenced by the dominance of transmission bands for adsorbed CO and a significant concentration of edge sites, which accommodate the strongly bound linear species at 300 K. Adsorption of CO at low temperature also allows the identification of the constituent faces of Pd and the conversion of Pd(110)/(100) facets to Pd(111) facets during the annealing process. High coverages of palladium (100 ML) produce only absorption bands in FT-RAIRS of adsorbed CO associated with the Pd facets, but annealing these surfaces also shows a conversion to Pd(111) facets. LEED indicates that at coverages above 10 ML, the palladium particles exhibit (111) facets parallel to the substrate and aligned with the TiO₂(110) unit cell, and that this ordering in the particles is enhanced by annealing.     

A multitechnique surface science examination of Sn deposition on Pt(100)

Interfaces prepared by vapor deposition of Sn onto Pt(100) surfaces have been examined using the following techniques: Auger electron and X-ray photoelectron spectroscopy (AES and XPS), low-energy electron diffraction (LEED), and low-energy ion surface scattering (LEISS) with Ne⁺ ions. Tin deposition was conducted at 320 and 600 K, and the surface composition and order was examined as a function of further annealing to 1200 K. The AES uptake plots (signal versus deposition time) indicate that the Sn growth mode can be described by a layer-by-layer process only up to one adayer at 320 K. Some evidence of 3D growth is inferred from LEED and LEISS data for higher Sn coverages. For deposition at 600 K, AES data indicate significant interdiffusion and surface alloy formation. LEED observations (recorded at a substrate temperature of 320 K) show that the characteristic hexagonal Pt(100) reconstruction disappears with Sn exposures of 4.6 × 10¹⁴ atoms cm² (θ_Sn = 0.35 monolayer (ML)). Further Sn deposition results in a c(2 × 2) LEED pattern starting at a coverage of slightly above 0.5 ML. The c(2 × 2) LEED pattern becomes progressively more diffuse with increasing Sn exposure with eventual loss of all LEED features above 2.2 ML. Annealing experiments with various precoverages of Sn on Pt(100) are also described by AES, LEED, and LEISS results. For specific Sn precoverages and annealing conditions, c(2 × 2), p(3√2 × √2)R45°, and a combination of the two LEED patterns are observed. These ordered LEED patterns are suggested to arise from ordered PtSn surface alloys. In addition, the chemisorption of CO and O₂ at the ordered annealed Sn/Pt(100) surfaces was also examined using thermal desorption mass spectroscopy (TDMS), AES, and LEED.     

X-ray and electron beam modification of thiophene overlayers on TiO2(100)1 × 1 and 1 × 3

The effects of electron and X-ray beams on thiophene overlayers on TiO₂(100) 1 × 1 and 1 × 3 surfaces have been investigated using AES, UPS and XPS. Mg K X-rays were found to polymerise a thiophene multilayer condensed at 120 K. The evidence points to a substrate-secondary-electron mediated process. A 3 keV electron beam also modifies a condensed thiophene overlayer, probably by polymerisation.     

The interaction of D2O with Zr(0001) at 80 K

The adsorption of D₂O on Zr(0001) at 80 K and its subsequent reactions at higher temperatures have been studied by thermal desorption spectroscopy (TDS), work-function measurements (Δф), nuclear reaction analysis (NRA), LEED, infrared reflection spectroscopy (FTIR-RAS), Auger electron spectroscopy (AES), and static secondary ion mass spectroscopy (SSIMS). D₂O adsorption on Zr(0001) at 80 K is accompanied by a Δф of −1.33 eV. The adsorbed D₂O can be characterized into three layers by TDS: a chemisorbed layer (up to 0.23 ML), a second adsorbed layer, and an ice layer. The chemisorbed D₂O dissociates into OD_ad and D_ad at 80 K (possibly also into O_ad) and no desorption products could be detected, implying that the reaction products dissolved into the zirconium at temperatures appropriate for each component. The ice layer and most of the second adsorbed layer desorb as molecular water during heating. The water adsorbed at 80 K did not form any long-range ordered structure, but a (2 × 2) LEED pattern that was formed by heating the sample to temperatures above 430 K is believed due to be an ordered oxygen superstructure.     

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.     

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.     

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.     

Studies on the ZrO/W(100) surface by means of low-energy electron diffraction and X-ray photoelectron spectroscopy

The low work-function ZrO/W(100) surface was examined with the aim of understanding the reducing mechanism of the work function. Low-energy electron diffraction (LEED) was employed to analyze the surface atomic arrangement, and X-ray photoelectron spectroscopy (XPS) was used to identify the surface chemical condition. The ZrO/W(100) surface was made as follows: (i) around three monolayers of Zr were deposited on a clean W(100) surface, (ii) the sample was heat treated in an oxygen ambience of 1.3x10⁻⁵ Pa for several tens of minutes at 1500 K, and (iii) the sample was flash heated at 2000 K in ultrahigh vacuum (UHV). During heat treatment in O₂, the deposited Zr was oxidized to ZrO₂, and the LEED pattern formed was p(2×1). The work function increased to 5.3 eV. Subsequent flash heating in UHV changed the p(2×1) LEED pattern into a c(4×2) pattern, and transformed ZrO₂ into the so-called Zr–O complex, the oxidized level of which is between ZrO₂ and metallic Zr. A drastic decrease in the work function to 2.7 eV ensued. The angular dependence of XPS showed that the Zr–O complex segregated within a few monolayers at the surface.     

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.     

Ionic conduction properties of layer-type oxides NaxMx/2Ti1−x/2O2 (M=Ni, Co; 0.60≤x≤1.0)

Layer-type oxide Na_xM_x/2^IITi_1−x/2^IVO₂ (M=Co, Ni; 0.60≤x≤1.0) has been prepared by solid state reactions. In both series, two structural variants of type -NaFeO₂ (O3) and β-RbScO₂ (P2) have been obtained consecutively as x decreases with a borderline composition around x_c0.7. With the decrease of x, the ionic conductivity has been found to increase up to 8.4×10⁻² S cm⁻¹ at 770 K (Na_0.67Co_0.33Ti_0.67O₂). Compositions of P2 have been found to exhibit the conductivity values two to five times greater than those of O3, primarily due to the larger rectangular threshold available for the diffusion of Na⁺ ions. Such a structural effect has also been considered to depend on the polarizability of alkali ion. HT-XRD and ²³Na-NMR data of Na_0.67Co_0.33Ti_0.67O₂ strongly suggest that the diffusion of Na⁺ ion is deeply related with the local distortion of trigonal prismatic sites, leading to the change of activation energy around 430 K.     

A LEED, TPD and HREELS investigation of NO adsorption on Sn/Pt(111) surface alloys

The adsorption of NO on Pt(111), and the (2 × 2)Sn/Pt(111) and (√3 × √3)R30°Sn/Pt(111) surface alloys has been studied using LEED, TPD and HREELS. NO adsorption produces a (2 × 2) LEED pattern on Pt(111) and a (2√3 × 2√3)R30° LEED pattern on the (2 × 2)Sn/Pt(111) surface. The initial sticking coefficient of NO on the (2 × 2)Sn/Pt(111) surface alloy at 100 K is the same as that on Pt(111), S₀ = 0.9, while the initial sticking coefficient of NO on the (√3 × √3)R30°Sn/Pt(111) surface decreases to 0.6. The presence of Sn in the surface layer of Pt(111) strongly reduces the binding energy of NO in contrast to the minor effect it has on CO. The binding energy of β-state NO is reduced by 8–10 kcal/mol on the Sn/Pt(111) surface alloys compared to Pt(111). HREELS data for saturation NO coverage on both surface alloys show two vibrational frequencies at 285 and 478 cm⁻¹ in the low frequency range and only one N-O stretching frequency at 1698 cm⁻¹. We assign this NO species as atop, bent-bonded NO. At small NO coverage, a species with a loss at 1455 cm⁻¹ was also observed on the (2 × 2)Sn/ Pt(111) surface alloy, similar to that observed on the Pt(111) surface. However, the atop, bent-bonded NO is the only species observed on the (√3 × √3)R30°Sn/Pt(111) surface alloy at any NO coverage studied.     

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.     

The adsorbate-induced removal of the Pt{100} surface reconstruction Part I: NO

The molecular adsorption of NO on both the reconstructed (hex) and unreconstructed (1 × 1) surfaces of Pt{100} has been studied using a combination of infrared reflection-absorption spectroscopy (IRAS) and low energy electron diffraction (LEED) at temperatures between 90 and 300 K. On the (1 × 1) surface at 300 K adsorbed NO gives rise to an N-O stretching band at initially 1596 cm⁻¹ shifting to 1641 cm⁻¹ at a coverage of θ = 0.5. The LEED pattern at this coverage is interpreted in terms of a c(4 × 2) structure in which all the molecules occupy a single type of adsorption site between the on-top and bridge positions. At temperatures below 300 K, a higher coverage disordered phase is observed, giving rise to an N-O stretching band at 1680 cm⁻¹ associated with an on-top NO species. On the (hex) phase surface above 210 K, NO adsorption gives rise to bands characteristic of adsorption on the (1 × 1) phase indicating that the reconstruction is immediately lifted. Below 200 K initial adsorption actually occurs directly on the (hex) phase, resulting in a band at 1680 cm⁻¹, which is assigned to on-top NO. This band increases in intensity until, at a critical coverage dependent on temperature, the (hex) → (1 × 1) surface phase transition is induced. This is indicated by the disappearance of the band at 1680 cm⁻¹ and its replacement by bands characteristic of adsorption on islands of the (1 × 1) structure.     

Oxygen interaction with Cu(100) studied by AES, ELS, Leed and work function changes

The interaction of oxygen with Cu(100) surfaces was investigated from 85 to 800 K by AES, ELS, LEED and work function change. At T300 K three different states of oxygen bonding are observed:

1. Chemisorption of oxygen (dosages up to 10²L), indicated by an increase of the work function change Δφ and O(KLL) signal height.

2. Incorporation of oxygen into the Cu sublayer with further oxygen uptake accompanied by a decrease of Δφ, and a shift of the O(KLL) Auger transition to lower energy (10²−10⁶L).

3. Growing of Cu(I) oxide, characterized by an increase of Δφ, shifts of the oxygen and copper Auger transitions and significant changes in ELS and AES line shapes (3×10⁶L, 10⁻³−5×10⁻¹torr). At low temperature (85 K) a second adsorbed oxygen species is detected.     

Adsorption and reaction of oxygen and deuterium on a Pd(110) surface, studied by Δφ and TDS

The co-adsorption of oxygen and deuterium at 100 K on a Pd(110) surface has been studied by measurements of the change in work function (Δφ) and by thermal desorption spectroscopy (TDS). When the surface with co-adsorbed species is heated, the adsorbates O and D react to form D₂O which desorbs from the surface at T > 200 K. The D₂O desorption peaks shift continuously to lower temperatures as the surface D coverage (θ_D) increases. The maximum production of D₂O is estimated to be 0.26 ML (1 ML = 9.5 × 10¹⁴ atoms cm⁻²), resulting from reaction in a layer containing 0.65 ML D and 0.3 ML O. The maximum work function increase caused by adsorption of D to saturation onto oxygen precovered Pd(110) decreases almost linearly with Δφ_O of the oxygen precovered surface. On a surface with pre-adsorbed D however, the maximum Δφ increase contributed by oxygen adsorption decreases abruptly at Δφ_D > 200 mV. This sharp change occurs at θ_D > 1 ML and is believed to be associated with the development of the reconstructed (1 × 2) phase of D/Pd(110).     

Hydrogen adsorption on Mo1−xRex(110) (x=0–0.25) surfaces

The effects of adsorbed H on the Mo_1−xRe_x(110), x=0, 0.05, 0.15, and 0.25, surfaces have been investigated using low-energy electron diffraction (LEED) and high-resolution electron energy loss spectroscopy (HREELS). For the x=0.15 alloy only, a c(2×2) LEED pattern is observed at a coverage Θ0.25 ML. A (2×2) pattern is observed for H coverages around Θ0.5 ML from surfaces with x=0, 0.05, and 0.15. Both c(2×2) and (2×2) patterns are attributed to reconstruction of the substrate. At higher coverages, a (1×1) pattern is observed. For the alloy surface with x=0.25, only a (1×1) pattern is obtained for all H coverages. Two H vibrations are observed in HREELS spectra for all Re concentrations, which shift to higher energies at intermediate coverages. Both peaks exhibit an isotopic shift, confirming their assignment to hydrogen. For Re concentrations of x=0.15 and higher, a third HREELS peak appears at 50 meV as H (D) coverage approaches saturation. This peak does not shift in energy with isotopic substitution, yet cannot be explained by contamination. The intrinsic width of the loss peaks depends on the Re concentration in the surface region and becomes broader with increasing x. This broadening can be attributed to surface inhomogeneity, but may also reflect increased delocalization of the adsorbed hydrogen atom.     

High critical current density YBa2Cu3O7−δ tapes prepared by the surface-oxidation epitaxy method

YBa₂Cu₃O_7−δ (YBCO) films with high critical current density (J_c) were successfully fabricated on nickel tapes buffered with epitaxial NiO. NiO was prepared on the textured nickel tape by the surface-oxidation epitaxy (SOE) method. We have reported so far a critical temperature (T_c) of 87 K and J_c=4–6×10⁴ A/cm² (77 K, 0 T) for the YBCO films on NiO/Ni tapes. To enhance the superconducting properties of the YBCO films on the SOE-grown NiO, depositions of thin oxide cap layers such as YSZ, CeO₂, and MgO on NiO were investigated. These oxide cap layers were epitaxially grown on NiO and provided the template for the epitaxial growth of YBCO films. Substantially improved data of T_c=88 K and J_c=3×10⁵ A/cm² (77 K, 0 T) and 1×10⁴ A/cm² (77 K, Hc, 4 T) were obtained for YBCO film on NiO, by using a MgO cap layer with a thickness of 50 nm. The method described in this paper is a simple way to produce long YBCO tape conductors with high-J_c values.     

Er3+掺杂的锗碲酸盐玻璃结构及光谱性能研究

采用熔融淬冷法制备了新型的Er³⁺/RE³⁺（RE³⁺=Ce³⁺,Tb³⁺）掺杂的GeO₂-TeO₂-Na₂O玻璃。测试了样品的差示扫描分析曲线、可见/近红外透过率、拉曼光谱、吸收光谱和1.53 μm发光光谱。研究发现适量的TeO₂对GeO₂的取代提高了玻璃的热稳定性,缩短了样品的吸收截止边。拉曼分析表明该系统玻璃有着宽广的红外透过范围。同时研究了980 nm激发下稀土离子（RE³⁺=Ce³⁺,Tb³⁺）的加入对Er³⁺掺杂的45GeO₂-45TeO₂-10Na₂O玻璃的光谱性能和能量传递的影响。发现随着Ce³⁺浓度增加大大地提高了1.53 μm的发光强度,CeO₂的最佳掺杂摩尔分数为0.1%,而Tb³⁺的共掺降低了1.53 μm的发光强度。可见Er³⁺/Ce³⁺掺杂的45GeO₂-45TeO₂-10Na₂O玻璃在C波段光纤放大器方面有潜在的应用前景。     

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.