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1.
We have studied the growth of cerium films on Rh(1 1 1) using STM (scanning tunneling microscopy), LEED (low energy electron diffraction), XPS (X-ray photoelectron spectroscopy) and AES (Auger electron spectroscopy). Measurements of the Ce films after room temperature deposition showed that Ce is initially forming nanoclusters in the low coverage regime. These clusters consist of 12 Ce atoms and have the shape of pinwheels. At a coverage of 0.25 ML (monolayer, ML) an adatom layer with a (2 × 2) superstructure is observed. Above 0.4 ML, Rh is diffusing through pinholes into the film, forming an unstructured mixed layer. Annealing at 250 °C leads to the formation of ordered Ce-Rh compounds based on the bulk compound CeRh3. At a coverage of 0.1 ML, small ordered (2 × 2) surface alloy domains are observed. The exchanged Rh atoms form additional alloy islands situated on the pure Rh(1 1 1) surface, showing the same (2 × 2) superstructure as the surface alloy. At a coverage of 0.25 ML, the surface is completely covered by the surface alloy and alloy islands. The (2 × 2) structure is equivalent to a (1 1 1)-plane of CeRh3, contracted by 6%. Annealing a 1 ML thick Ce layer leads to a flat surface consisting of different rotational domains of CeRh3(1 0 0). The Rh needed for alloy formation comes from 50 Å deep pits in the substrate. Finally we show that LEIS (low energy ion scattering) is not suitable for the characterization of Ce and CeRh films due to strong effects of neutralization.  相似文献   

2.
The growth of thin subnanometric silicon films on TiO2 (1 1 0)-(1 × 2) reconstructed surfaces at room temperature (RT) has been studied in situ by X-ray and ultra-violet photoelectron spectroscopies (XPS and UPS), Auger electron and electron-energy-loss spectroscopies (AES and ELS), quantitative low energy electron diffraction (LEED-IV), and scanning tunneling microscopy (STM). For Si coverage up to one monolayer, a heterogeneous layer is formed. Its composition consists of a mixture of different suboxides SiOx (1 < x ? 2) on top of a further reduced TiO2 surface. Upon Si coverage, the characteristic (1 × 2) LEED pattern from the substrate is completely attenuated, indicating absence of long-range order. Annealing the SiOx overlayer results in the formation of suboxides with different stoichiometry. The LEED pattern recovers the characteristic TiO2 (1 1 0)-(1 × 2) diagram. LEED I-V curves from both, substrate and overlayer, indicate the formation of nanometric sized SiOx clusters.  相似文献   

3.
The structure of a nickel oxide film 2 ML thick has been investigated by LEED intensity analysis. The NiO film was prepared by evaporating Ni in presence of O2 at a pressure in the 10−6 mbar range. The growth of the oxide film was followed by XPS, LEIS and LEED. In the early stages of deposition, the film shows a (2 × 1) superstructure in LEED. After deposition of 2 ML of NiO, a sharp (1 × 1) LEED pattern is observed. The intensity versus electron energy curves of the LEED spots were measured for this NiO(1 × 1) film and analysed by means of the tensor LEED method. A good level of agreement of the experimental LEED intensities with those calculated for a pseudomorphic NiO(0 0 1) film was obtained. We found that oxygen atoms at the oxide-substrate interface are on-top silver atoms. The interlayer distance in the oxide does not differ significantly from that in bulk NiO(0 0 1), within the accuracy of the analysis. An outward displacement (0.05 ± 0.05 Å) of oxygen atoms with respect to nickel atoms was found at the oxide film surface. The interlayer distance at the silver-nickel oxide interface is 2.43 ± 0.05 Å.  相似文献   

4.
The reactive vacuum deposition of CeO2 on Cu(1 1 1) surface in oxygen atmosphere provides high quality epitaxial ceria overlayers. We report the growth characteristics of Ce oxide, the structures, and the temperature stability of the oxide phases as investigated by low-energy electron diffraction (LEED) and X-ray photoelectron spectroscopy. We find that Ce oxide on the Cu(1 1 1) grows initially in the form of islands giving sharp hexagonal LEED pattern of the CeO2(1 1 1) structure corresponding to the (1.5 × 1.5) structure. The CeO2-Cu(1 1 1) films exhibited mixed valence states and temperature dependent CeO2-Ce2O3 transition above 900 K due to the vacuum annealing. The transition progressed more rapidly at the surface, probably by formation of oxygen vacancies.  相似文献   

5.
We report a photoelectron spectroscopic study of the valence bands of epitaxial Ce(1 1 1) films grown on W(1 1 0) at room temperature. The evolution of γ → α → γ like phase transition of Ce is observed with increasing Ce coverage and the valence-band structures of γ-like Ce film are determined. The 4f and 5d photoemission cross sections in the photon energy region from 20 eV to 130 eV are presented and discussed. A 5d-like surface state and a 6s band bottom are identified.  相似文献   

6.
P. Hanyš 《Surface science》2007,601(18):3717-3721
An ultra thin Sn layer (6 Å) was deposited onto Rh(1 1 1) single crystal surface. We followed changes in low energy electron diffraction (LEED) pattern during progressive annealing together with development of CO adsorption capacity and photoelectron spectra obtained using synchrotron radiation. Surface bimetallic alloy development with increasing temperature was followed by LEED and synchrotron radiation photoelectron spectroscopy (SRPES). LEED results show several surface structure of Sn/Rh(1 1 1) sample in dependence on sample temperature. If it increases, the surface structure develops to the stable ordered (√3 × √3)R30° structure. Surface CO adsorption depends strongly on the amount of Sn in the top sample layer then it corresponds to the development of the surface structure. The CO adsorption capacity raises with increasing temperature.Photoelectron spectra of Sn and Rh core levels and their shifts and shapes were studied during the annealing and CO adsorption. The resulting spectra are used to discuss the Sn-Rh surface alloy creation.The goal of this paper is to demonstrate the CO adsorption on the Sn/Rh(1 1 1) surface. Valence band spectra measured at different primary energies are presented to demonstrate this effect. These spectra show different adsorption properties of the studied system in dependence on the amount of Sn in the top layer and geometric structure of the surface.  相似文献   

7.
The adsorption of calcium (Ca) atoms on a Cu(0 0 1) surface has been studied by low-energy electron diffraction (LEED) at 130, 300 and 400 K. It is found that a (4 × 4) was the only LEED pattern appeared at 400 K while a quasi-hexagonal structure was formed in a wide range of submonolayer coverage at 130 K. At 300 K, the (4 × 4) LEED spots were broad and weak. The (4 × 4) structure formed at 400 K was determined by a tensor LEED I-V analysis. It is a new-type of surface alloys consisting of five substitutional Ca atoms, nine surface Cu atoms, and two atomic vacancies in the unit cell. In spite of a quite large size-difference between Ca (3.94 Å) and Cu (2.55 Å) atoms, all Ca atoms are located at the substitutional sites. Among surface alloys so far reported, the atomic size ratio between Cu and Ca in the (4 × 4), 1.54, is the largest. Optimized structural parameters reveal that large lateral displacements of surface Cu atoms, being enabled by the appearance of the vacancies, allow the formation of the (4 × 4) structure.  相似文献   

8.
W. Gao 《Surface science》2006,600(12):2572-2580
The interaction of vanadium oxide with epitaxial anatase films exposing (1 0 1) terraces was characterized. The TiO2 films were grown on vicinal LaAlO3 (1 1 0) substrates by oxygen plasma-assisted molecular beam epitaxy (OPA-MBE); reflection high energy and low energy electron diffraction (RHEED and LEED) indicated that the films exposed (1 0 1) terraces of the anatase TiO2 polymorph. When a vanadium oxide monolayer was deposited onto the anatase surface by OPA-MBE at 725 K, only (1 × 1) RHEED and LEED patterns were observed. The V X-ray photoelectron spectroscopy (XPS) peak intensities indicated that the monolayer wetted the anatase surface and so the diffraction patterns were attributed to an epitaxial vanadia layer. Analysis of the vanadium oxide monolayer by X-ray and ultraviolet photoelectron spectroscopies revealed that the V was predominantly 5+. When the vanadia coverage was increased at 725 K, Auger electron spectra showed only very slow attenuation of the anatase Ti peaks while spots began to develop in RHEED patterns recorded along the LaAlO3 direction; both indicative of 3-D cluster formation. In the orthogonal direction, the RHEED patterns showed unusual diagonal streaks. Meanwhile, the (1 × 1) LEED pattern persisted even after 30 nm of vanadia was deposited. This was attributed to gaps between the 3-D clusters exposing the epitaxial monolayer. Core level XPS spectra of the 3-D clusters revealed a broad V 2p3/2 peak that was centered at the position expected for V4+ but could be deconvoluted into three peaks corresponding to V3+, V4+, and V5+. It is shown that crystallographic shear that accommodates such variations in the oxygen content of V oxides can lead to the diagonal streaks in RHEED patterns recorded along the LaAlO3 [0 0 1] direction even as the pattern in the orthogonal direction shows sharp transmission spots. The results show that vanadia growth on anatase (1 0 1) proceeds through the Stranski-Krastanov mode with a strong vanadia-titania interaction stabilizing a dispersed vanadia monolayer. The results are compared with previous data for vanadia growth on anatase (0 0 1) where smooth, epitaxial VO2 films grow ad infinitum.  相似文献   

9.
A quantitative low energy electron diffraction (LEED) analysis has been performed for the p(2 × 2)-S and c(2 × 2)-S surface structures formed by exposing the (1 × 1) phase of Ir{1 0 0} to H2S at 750 K. S is found to adsorb on the fourfold hollow sites in both structures leading to Pendry R-factor values of 0.17 for the p(2 × 2)-S and 0.16 for the c(2 × 2)-S structures. The distances between S and the nearest and next-nearest Ir atoms were found to be similar in both structures: 2.36 ± 0.01 Å and 3.33 ± 0.01 Å, respectively. The buckling in the second substrate layer is consistent with other structural studies for S adsorption on fcc{1 0 0} transition metal surfaces: 0.09 Å for p(2 × 2)-S and 0.02 Å for c(2 × 2)-S structures. The (1 × 5) reconstruction, which is the most stable phase for clean Ir{1 0 0}, is completely lifted and a c(2 × 2)-S overlayer is formed after exposure to H2S at 300 K followed by annealing to 520 K. CO temperature-programmed desorption (TPD) experiments indicate that the major factor in the poisoning of Ir by S is site blocking.  相似文献   

10.
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.  相似文献   

11.
Using synchrotron radiation, W 4f7/2 and valence-band (VB) photoelectron spectroscopy was used to study the oxidation states of the p(3 × 1) reconstructed surface of W(1 0 0) produced by oxygen adsorption at 1500 K. The W 4f7/2 study showed two features at 0.40 and 1.50 eV higher binding energies relative to the bulk feature which represent shifts to lower binding energies compared to the W 4f7/2 features of the as-grown oxygen films on W(1 0 0). Co-existence of these features is a characteristic of the formation of the p(3 × 1) structure. The VB studies of this system and as-grown oxygen films at room temperature (RT) showed an oxygen-induced feature for the p(3 × 1) structure for which the peak maximum had shifted by 0.9 eV to higher binding energies compared to the as-grown films. The direction of shifts in the W 4f7/2 and VB spectra for the p(3 × 1) structure confirmed the reduction of the charge transfer from W to oxygen compared to the as-grown films. A study of the VB changes with photon energy shows that the main component of the oxygen-induced feature in the p(3 × 1) VB at 6.6 ± 0.2 eV is related to a hybridized state between W 5d and O 2p electrons.  相似文献   

12.
Ming-Shu Chen 《Surface science》2007,601(22):5162-5169
The adsorption of K atoms on Cu(0 0 1) has been studied by low-energy electron diffraction (LEED) at room temperature (RT) and 130 K. At RT, a (3 × 2)-p2mg LEED pattern with single-domain was observed at coverage of 0.33, whereas the orthogonal two-domain was found at 130 K. At 130 K, a c(4 × 2) pattern with orthogonal two-domain was observed at coverage 0.25. Both the (3 × 2)-p2mg and c(4 × 2) structures have been determined by a tensor LEED analysis. It is demonstrated that K atoms are adsorbed on surface fourfold hollow sites in the c(4 × 2), while in the (3 × 2) structure two K atoms in the unit cell are located at an asymmetric site with a glide-reflection-symmetry. The asymmetric site is at near the midpoint between the exact hollow site and bridge-site but slightly close to the hollow site. A rumpling of 0.07 Å in the first Cu layer was confirmed, which might stabilize K atoms at the asymmetric site. Surface structures appearing in a coverage range 0.25-0.33 are discussed in terms of the occupation of the asymmetric site with increase of coverage.  相似文献   

13.
M. Walker  M. Draxler 《Surface science》2006,600(16):3327-3336
The initial growth of Pt on the Ni(1 1 0)-(3 × 1)-O and NiO(1 1 0) surfaces has been studied by coaxial impact collision ion scattering spectroscopy (CAICISS), low energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). Prior to Pt deposition, the atomic structure of the near-surface regions of the Ni(1 1 0)-(3 × 1)-O and NiO(1 1 0) structures were studied using CAICISS, finding changes to the interlayer spacings due to the adsorption of oxygen. Deposition of Pt on the Ni(1 1 0)-(3 × 1)-O surface led to a random substitutional alloy in the near-surface region at Pt coverages both below and in excess of 1 ML. In contrast, when the surface was treated with 1800 L of atomic oxygen in order to form a NiO(1 1 0) surface, a thin Pt layer was formed upon room temperature Pt deposition. XPS and LEED data are presented throughout to support the CAICISS observations.  相似文献   

14.
The co-adsorption of CO and O on the unreconstructed (1 × 1) phase of Ir{1 0 0} was examined by low energy electron diffraction (LEED) and temperature programmed desorption (TPD). When CO is adsorbed at 188 K onto the Ir{1 0 0} surface precovered with 0.5 ML O, a mixed c(4 × 2)-(2O + CO) overlayer is formed. All CO is oxidised upon heating and desorbs as CO2 in three distinct stages at 230 K, 330 K and 430 K in a 2:1:2 ratio. The excess oxygen left on the surface after all CO has reacted forms an overlayer with a LEED pattern with p(2 × 10) periodicity. This overlayer consists of stripes with a local p(2 × 1)-O arrangement of oxygen atoms separated by stripes of uncovered Ir. When CO is adsorbed at 300 K onto the surface precovered with 0.5 ML O an apparent (2 × 2) LEED pattern is observed. LEED IV analysis reveals that this pattern is a superposition of diffraction patterns from islands of c(2 × 2)-CO and p(2  × 1)-O structures on the surface. Heating this co-adsorbed overlayer leads to the desorption of CO2 in two stages at 330 K and 430 K; the excess CO (0.1 ML) desorbs at 590 K.LEED IV structural analysis of the mixed c(4 × 2) O and CO overlayer shows that both the CO molecules and the O atoms occupy bridge sites. The O atoms show significant lateral displacements of 0.14 Å away from the CO molecules; the C-O bond is slightly expanded with respect to the gas phase (1.19 Å); the modifications of the Ir substrate with respect to the bulk-terminated surface are very small.  相似文献   

15.
Titanium dioxide films were grown on Re(1 0 −1 0) by Ti vapor deposition in oxygen at T = 830 K and studied by means of low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), low-energy ion scattering (LEIS) and X-ray diffraction (XRD). The Ti oxide stoichiometry was determined by XPS as Ti:O = 1:2, with the Ti oxidation state (4+). The TiO2 growth was monitored by means of LEED as a function of film thickness. Extending the coverage from the submonolayer into the multilayer regime gives rise to a p(2 × 2) pattern, a (poorly ordered) (1 × 1), and, finally, a stable (2 × 2) structure, the latter being associated with a homogeneous TiO2 phase. For normal electron incidence, the (2 × 2) LEED pattern exhibits systematically extinguished beams at (n ± 1/2, 0) positions, indicating a glide mirror plane. The pg(2 × 2) structure could be explained by both a rutile(0 1 1)-(2 × 1) reconstructed surface and a bulk truncated brookite(0 0 1) surface. Faceting phenomena, i.e. running LEED spots, observed with thin TiO2 films point to the formation of a rutile(0 1 1)-(2 × 1) surface with two domains and {0 1 1}-(2 × 1) facets and rule out the brookite alternative. Confirmation of this assignment was obtained by an XRD analysis performed at the Berlin synchrotron facility BESSY.  相似文献   

16.
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.  相似文献   

17.
This study first reports the initial growth stages of sodium chloride (NaCl) on Ag(1 1 0) at room temperature. NaCl grows in bi-layer mode along its [1 0 0] axis and gives rise to (4 × 1) and (1 × 2) reconstructed domains for coverages lower than two monolayers (ML), a minimal thickness inducing a bi-dimensional closed film. In addition, a 10 ML NaCl film has been examined by low energy electron diffraction (LEED). LEED analysis leads to the dissociation of the NaCl deposit in a few minutes. The NaCl dissociation implies Cl desorption from the surface and Na remaining on it. The residual Na is arranged in the form of a (2 × 1) surface reconstruction and is found to be strongly bounded to the Ag substrate. These findings have been established by using the X-ray photoelectron spectroscopy technique.  相似文献   

18.
The c(4 × 2) structures in (0 0 1) surfaces of Si and Ge have been studied by low-energy electron diffraction (LEED). Using a proper cleaning method for the Si surface, we were able to observe clear c(4 × 2) LEED patterns up to incident energy of ∼400 eV as well as the Ge surface. Extensive experimental intensity-voltage curves allowed us to optimize the asymmetric dimer model up to the eighth layer (including the dimer layer) in depth in the dynamical LEED calculation. Optimized structural parameters are almost the same for the Si and Ge except for the height of the buckled-up atom of the asymmetric dimer. For the Ge surface, the structural parameters are in excellent agreement with those obtained by a previous theoretical calculation. The tilt angle and bond length of the dimer are 18 ± 1 (19 ± 1)° and 2.4 ± 0.1 (2.5 ± 0.1) Å for the Si(0 0 1) (Ge(0 0 1)), respectively.  相似文献   

19.
S. Funk 《Applied Surface Science》2007,253(17):7108-7114
We attempt to correlate qualitatively the surface structure with the chemical activity for a metal surface, Cr(1 1 0), and one of its surface oxides, Cr2O3(0 0 0 1)/Cr(1 1 0). The kinetics and dynamics of CO2 adsorption have been studied by low energy electron diffraction (LEED), Aug er electron spectroscopy (AES), and thermal desorption spectroscopy (TDS), as well as adsorption probability measurements conducted for impact energies of Ei = 0.1-1.1 eV and adsorption temperatures of Ts = 92-135 K. The Cr(1 1 0) surface is characterized by a square shaped LEED pattern, contamination free Cr AES, and a single dominant TDS peak (binding energy Ed = 33.3 kJ/mol, first order pre-exponential 1 × 1013 s−1). The oxide exhibits a hexagonal shaped LEED pattern, Cr AES with an additional O-line, and two TDS peaks (Ed = 39.5 and 30.5 kJ/mol). The initial adsorption probability, S0, is independent of Ts for both systems and decreases exponentially from 0.69 to 0.22 for Cr(1 1 0) with increasing Ei, with S0 smaller by ∼0.15 for the surface oxide. The coverage dependence of the adsorption probability, S(Θ), at low Ei is approx. independent of coverage (Kisliuk-shape) and increases initially at large Ei with coverage (adsorbate-assisted adsorption). CO2 physisorbs on both systems and the adsorption is non-activated and precursor mediated. Monte Carlo simulations (MCS) have been used to parameterize the beam scattering data. The coverage dependence of Ed has been obtained by means of a Redhead analysis of the TDS curves.  相似文献   

20.
The growth and oxidation of a thin film of Ni3Al grown on Ni(1 0 0) were studied using Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and high resolution electron energy loss spectroscopy (EELS). At 300 K, a 12 Å thick layer of aluminium was deposited on a Ni(1 0 0) surface and subsequently annealed to 1150 K resulting in a thin film of Ni3Al which grows with the (1 0 0) plane parallel to the (1 0 0) surface of the substrate. Oxidation at 300 K of Ni3Al/Ni(1 0 0) until saturation leads to the growth of an aluminium oxide layer consisting of different alumina phases. By annealing up to 1000 K, a well ordered film of the Al2O3 film is formed which exhibits in the EEL spectra Fuchs-Kliewer phonons at 420, 640 and 880 cm−1. The LEED pattern of the oxide shows a twelvefold ring structure. This LEED pattern is explained by two domains with hexagonal structure which are rotated by 90° with respect to each other. The lattice constant of the hexagonal structure amounts to ∼2.87 Å. The EELS data and the LEED pattern suggest that the γ-Al2O3 phase is formed which grows with the (1 1 1) plane parallel to the Ni(1 0 0) surface.  相似文献   

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