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1.
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   

2.
In attempt to correlate electronic properties and chemical composition of atomic hydrogen cleaned GaAs(1 0 0) surface, high-resolution photoemission yield spectroscopy (PYS) combined with Auger electron spectroscopy (AES) and mass spectrometry has been used. Our room temperature investigation clearly shows that the variations of surface composition and the electronic properties of a space charge layer as a function of atomic hydrogen dose display three successive interaction stages. There exists a contamination etching stage which is observed up to around 250 L of atomic hydrogen dose followed by a transition stage and a degradation stage which is observed beyond 700 L of exposure. In the first stage, a linear shift in the surface Fermi level is observed towards the conduction band by 0.14 eV, in agreement to the observed restoration of the surface stoichiometry and contamination removal. The next stage is characterized by a drop in ionization energy and work function, which quantitatively agrees with the observed Ga-enrichment as well as the tail of the electronic states attributed to the breaking As-dimers. As a result of the strong hydrogenation, the interface Fermi level EF − Ev has been pinned at the value of 0.75 eV what corresponds to the degradation stage of the GaAs(1 0 0) surface that exhibits metallic density of states associated with GaAs antisites defects. The results are discussed quantitatively in terms of the surface molecule approach and compared to those obtained by other groups.  相似文献   

3.
A high resolution (0.0018 cm−1) Fourier transform instrument has been used to record the spectrum of an enriched 34S (95.3%) sample of sulfur dioxide. A thorough analysis of the ν2, 2ν2 − ν2, ν1, ν1 + ν2 − ν2, ν3, ν2 + ν3 − ν2, ν1 + ν2 and ν2 + ν3 bands has been carried out leading to a large set of assigned lines. From these lines ground state combination differences were obtained and fit together with the existing microwave, millimeter, and terahertz rotational lines. An improved set of ground state rotational constants were obtained. Next, the upper state rotational levels were fit. For the (0 1 0), (1 1 0) and (0 1 1) states, a simple Watson-type Hamiltonian sufficed. However, it was necessary to include explicitly interacting terms in the Hamiltonian matrix in order to fit the rotational levels of the (0 2 0), (1 0 0) and (1 0 1) states to within their experimental accuracy. More explicitly, it was necessary to use a ΔK = 2 term to model the Fermi interaction between the (0 2 0) and (1 0 0) levels and a ΔK = 3 term to model the Coriolis interaction between the (1 0 0) and (0 0 1) levels. Precise Hamiltonian constants were derived for the (0 0 0), (0 1 0), (1 0 0), (0 0 1), (0 2 0), (1 1 0) and (0 1 1) vibrational states.  相似文献   

4.
Zn1−xMnxSe/GaAs (1 0 0) epilayers were grown using a hot-wall epitaxy method. The spectroscopic ellipsometry was used to determine the optical dielectric constant. The obtained pseudodielectric function spectra revealed the distinct structures at energies of E0, E0 + Δ0, E1, E1 + Δ1, E2 and  + Δ0 critical points (CPs) at lower Mn composition range. These critical points were determined by analytical line-shapes fitted to numerically calculated derivatives of their pseudodielectric functions. The peak characteristics were changed with the change in Mn composition. The spectral dependence of pseudodielectric function 〈?〉 was used to obtain the fundamental energy gaps E0 including a unique relation with Mn composition. Also, the shifting and broadening of the CPs were observed with increasing Mn composition.  相似文献   

5.
The far-infrared and middle-infrared emission spectra of deuterated water vapour were measured at temperatures 1370, 1520, and 1940 K in the ranges 320-860 and 1750-3400 cm−1. The measurements were performed in an alumina cell with an effective length of hot gas of about 50 cm. More than 3550 new measured lines for the D216O molecule corresponding to transitions from highly excited rotational levels of the (0 2 0), (1 0 0), and (0 0 1) vibrational states are reported. These new lines correspond to rotational states with higher values of the rotational quantum numbers compared to previously published determinations: Jmax = 29 and Ka(max) = 22 for the (0 2 0) state, Jmax = 29 and Ka(max) = 25 for the (1 0 0) state, and Jmax = 30 and Ka(max) = 23 for the (0 0 1) state. The extended set of 1987 experimental rotational energy levels for the (0 2 0), (1 0 0), and (0 0 1) vibration states including all previously available data has been determined. For the data reduction we used the generating function model. The root mean square (RMS) deviation between observed and calculated values is 0.004 cm−1 for 1952 rovibrational levels of all three vibration states. A comparison of the observed energy levels with the best available values from the literature and with the global predictions from molecular electronic potential energy surfaces of water isotopic species [H. Partridge, D.W. Schwenke, J. Chem. Phys. 106 (1997) 4618] is discussed. The latter confirms a good consistency of mass-dependent DBOC corrections in the PS potential function with new experimental rovibrational data.  相似文献   

6.
We present experimental results on the structural and magnetic properties of series of Fe thin films evaporated onto Si(1 1 1), Si(1 0 0) and glass substrates. The Fe thickness, t, ranges from 6 to110 nm. X-ray diffraction (XRD) and atomic force microscopy (AFM) have been used to study the structure and surface morphology of these films. The magnetic properties were investigated by means of the Brillouin light scattering (BLS) and magnetic force microscopy (MFM) techniques. The Fe films grow with (1 1 0) texture; as t increases, this (1 1 0) texture becomes weaker for Fe/Si, while for Fe/glass, the texture changes from (1 1 0) to (2 1 1). Grains are larger in Fe/Si than in Fe/glass. The effective magnetization, 4πMeff, inferred from BLS was found to be lower than the 4πMS bulk value. Stress induced anisotropy might be in part responsible for this difference. MFM images reveal stripe domain structure for the 110 nm thick Fe/Si(1 0 0) only.  相似文献   

7.
The solid-state synthesis of magnetically soft phase FePd3 in epitaxial Pd(0 0 1)/Fe(0 0 1)/MgO(0 0 1) film systems was studied experimentally. The system had a Fe to Pd ratio of 1:3. An increase to 450 °C leads to the formation of three variants of ordered L10-FePd crystallites. At 500 °C, the solid-state reaction of unreacted Pd with L10-FePd crystallites initiates the growth of an ordered epitaxial L12-FePd3(0 0 1) layer. When annealing at 650 °С, a gradual disordering is observed. The magnetic anisotropy (K1=−2.0×103 erg/cm3) and the saturation magnetization (MS=650 emu/cm3) of the disordered FePd3 phase were determined.  相似文献   

8.
In this paper, the InGa-terminated InGaAs(1 0 0) (4 × 2)/c(8 × 2) surface was studied in detail, which turned out to be the most suitable to develop an InGaAs/GaAsSb interface that is as sharp as possible. In ultra high vacuum the InGaAs surface was investigated with low-energy electron diffraction, scanning tunneling microscopy and UV photoelectron spectroscopy employing synchrotron radiation as light source. Scanning the ΓΔX direction by varying the photon energy between 8.5 eV and 50 eV, two surface states in the photoelectron spectra were observed in addition to the valence band peaks.  相似文献   

9.
E.L. Wilson  G. Thornton 《Surface science》2006,600(12):2555-2561
Reflection absorption infrared spectroscopy (RAIRS) has been used to investigate the adsorption of CO on CeO2−x-supported Pd nanoparticles at room temperature. The results show that when CeO2−x is initially grown on Pt(1 1 1), a small proportion of the surface remains as bare Pt sites. However, when Pd is deposited onto CeO2−x/Pt(1 1 1), most of the Pd grows directly on top of the CeO2−x(1 1 1). RAIR spectra of CO adsorption on 1 ML Pd/CeO2−x/Pt(1 1 1) show a broad CO-Pd band, which is inconsistent with a single crystal Pd surface. However, the 5 ML and 10 ML Pd/CeO2−x/Pt(1 1 1) spectra show vibrational bands consistent with the presence of Pd(1 1 1) and (1 0 0) faces, suggesting the growth of Pd nanostructures with well defined facets.  相似文献   

10.
The ν9 fundamental band of ethane occurs in the 12 μm region. It is the strongest band of ethane in a terrestrial window and is commonly used for the identification of ethane in the Jovian planets. The ν9 + ν4 − ν4 band occurs in the same region; neither can be analysed as an isolated band, since both are embedded in the torsional bath of the ground vibrational state. We report here two global fit models including data from both of these bands as well as the ν3 fundamental and the ν4, 2ν4 − ν4, and 3ν4 torsional transitions. The first is restricted to −5 ? KΔK ? 15 in the hot band and gives an excellent fit to the included data. Three resonant interactions are identified in this fit—a Coriolis interaction with two resonant cases between the ν9 torsional stack and that of the ground vibrational state (gs) and a resonant Fermi interaction between the ν3 fundamental and the gs. Hot band lines with KΔK < −5 are influenced by a fourth perturbation, with a crossing at −11 < KΔK < −10, which has been attributed to an interaction with the ν12 fundamental. A second fit, demonstrating a promising treatment of this interaction, is also presented.  相似文献   

11.
J. Wang 《Surface science》2006,600(21):4855-4859
Presented are thermal desorption spectroscopy (TDS) and adsorption probability measurements of iso-butane on the Zn-terminated surface of ZnO. The initial adsorption probability, S0, decreases linearly from 0.57 to 0.22 (±0.02) with impact energy, Ei = 0.74-1.92 eV, and is independent of adsorption temperature, Ts = 91-114 K (±5 K), indicating non-activated molecular adsorption. The coverage, Θ, dependent adsorption probabilities, S(Θ), show a cross-over from adsorbate-assisted adsorption (S increases with Θ) to Kisliuk-like dynamics at about the desorption temperature of iso-butane bi-layers (∼110 K). Thus, the adsorption dynamics are precursor-mediated. The enhanced (gas-surface) mass-match, caused by forming a second layer of the alkane, leads to adsorbate-assisted adsorption. A direct fitting procedure of the TDS data yields a pre-exponential factor of 2.5 × 1013/s and a coverage dependent heat of adsorption of Ed(Θ) = 39 − 6 ∗ Θ + 2.5 ∗ exp(−Θ/0.07) kJ/mol.  相似文献   

12.
The initial stages of oxidation of the In-rich InAs(0 0 1)-(4 × 2)/c(8 × 2) surface by molecular oxygen (O2) were studied using scanning tunneling microscopy (STM) and density functional theory (DFT). It was shown that the O2 dissociatively chemisorbs along the rows in the [1 1 0] direction on the InAs surface either by displacing the row-edge As atoms or by inserting between In atoms on the rows. The dissociative chemisorption is consistent with being autocatalytic: there is a high tendency to form oxygen chemisorption sites which grow in length along the rows in the [1 1 0] direction at preexisting oxygen chemisorption sites. The most common site size is about 21-24 Å in length at ∼25% ML coverage, representing 2-3 unit cell lengths in the [1 1 0] direction (the length of ∼5-6 In atoms on the row). The autocatalysis was confirmed by modeling the site distribution as non-Poisson. The autocatalysis and the low sticking probability (∼10−4) of O2 on the InAs(0 0 1)-(4 × 2)/c(8 × 2) are consistent with activated dissociative chemisorption. The results show that is it critical to protect the InAs surface from oxygen during subsequent atomic layer deposition (ALD) or molecular beam epitaxy (MBE) oxide growth since oxygen will displace As atoms.  相似文献   

13.
The growth of ultrathin ZrO2 films on Si(1 0 0)-(2 × 1) and Si(1 1 1)-(7 × 7) has been studied with core level photoelectron spectroscopy and X-ray absorption spectroscopy. The films were deposited sequentially by chemical vapor deposition in ultra-high vacuum using zirconium tetra-tert-butoxide as precursor. Deposition of a > 50 Å thick film leads in both cases to tetragonal ZrO2 (t-ZrO2), whereas significant differences are found for thinner films. On Si(1 1 1)-(7 × 7) the local structure of t-ZrO2 is not observed until a film thickness of 51 Å is reached. On Si(1 0 0)-(2 × 1) the local geometric structure of t-ZrO2 is formed already at a film thickness of 11 Å. The higher tendency for the formation of t-ZrO2 on Si(1 0 0) is discussed in terms of Zr-O valence electron matching to the number of dangling bonds per surface Si atom. The Zr-O hybridization within the ZrO2 unit depends furthermore on the chemical composition of the surrounding. The precursor t-butoxy ligands undergo efficient C-O scission on Si(1 0 0), leaving carbonaceous fragments embedded in the interfacial layer. In contrast, after small deposits on Si(1 1 1) stable t-butoxy groups are found. These are consumed upon further deposition. Stable methyl and, possibly, also hydroxyl groups are found on both surfaces within a wide film thickness range.  相似文献   

14.
In situ electrochemical scanning tunneling microscopy (STM) has been applied to study the initial stages of hydroxide formation and its reduction on Co(0 0 0 1) in 0.1 M NaOH. XPS investigations give chemical information about the adlayer composition after oxidation and at the different reduction stages. In the subpotential range of oxidation at E<−0.55 V (SHE) the formation of a Co(OH)2(0 0 0 1) superstructure is observed. It shows a hexagonal symmetry with an average periodicity of P=1.25±0.20 nm. The coincidence cell of the observed structure consists of 16 unit cells Co(OH)2(0 0 0 1) showing an average lattice parameter of a=0.33±0.05 nm and thus the Co(OH)2 monolayer forms a 5 × 5 superstructure with respect to the underlying metallic Co(0 0 0 1) substrate. XPS results clearly prove the presence of hydroxide and exclude the formation of CoO in the subpotential range.At the very beginning of the reduction process small two-dimensional metal clusters and islands can be observed. It is assumed that they are crystallization nuclei for metal formation. They enlarge and grow together with other islands or larger terraces. During this reduction process two-dimensional adatomic arrays consisting of OH-Co2+- OH trimers appear on the surface. Some of these trimers accumulate at step edges, and finally decorate them. This decoration builds up an energy barrier for further metal incorporation and prevents further growth of the terraces with remaining metal clusters on their surfaces. The reduction of the Co(OH)2 layer is found to be not completed which is confirmed by XPS results.  相似文献   

15.
R. Armitage  J. Suda  T. Kimoto 《Surface science》2006,600(7):1439-1449
ZrB2(0 0 0 1) crystals grown by the rf-floating zone technique were characterized by X-ray photoelectron spectroscopy, reflection high-energy electron diffraction, and atomic force microscopy. These characteristics were investigated as a function of thermal cleaning temperature up to 1000 °C in vacuum for as-received substrates as well as substrates treated ex situ in HF aqueous solution. The HF treatment process removed the ZrO2 native oxide layer present on as-received substrates and resulted in ZrB2(0 0 0 1) surfaces exhibiting long-range order. Upon annealing the HF-treated surface in high vacuum, two types of reconstructions were observed: an incommensurate reconstruction from 650 to 900 °C related to residual H2 gas, and n × n reconstructions at 1000 °C, possibly related to oxygen.  相似文献   

16.
Materials and ion transport property characterization in Solid Polymer Electrolyte (SPE) membranes: (1 − x) PEO: x KIO3, where x = 0, 10, 20, 30, 40, 50 wt.%, have been studied. SPE films have been prepared following two casting techniques: a novel hot-press (extrusion) and the traditional solution cast. Hot-press technique is a completely dry/solvent free/rapid/inexpensive procedure as compared to solution cast method and has recently been receiving wider acceptability to cast membranes of ion conducting polymeric electrolytes.‘Log σ − x’ study revealed σ-maxima at salt concentration x = 30 wt.% for SPE film prepared by both the methods. However, hot-pressed SPE film: 70 PEO: 30 KIO3 exhibited relatively higher room temperature conductivity (σ ∼ 4.40 × 10− 7 S cm− 1) than that of the solution casted film. This has been referred to as Optimum Conducting Composition (OCC) SPE film. Materials characterization in OCC SPE film has been done by XRD, FTIR and DSC techniques. These studies confirmed the complexation of salt in the polymeric host. Some basic ionic parameters viz. conductivity (σ), ionic mobility (μ), mobile ion concentration (n), ionic transference number (tion) have been determined using different experimental procedures to understand the ion transport behaviour in OCC SPE material. The temperature dependent conductivity measurement has also been carried out and the activation energy (Ea) has been computed from the linear least square fitting of ‘log σ − 1 / T’ Arrhenius plot.  相似文献   

17.
Surface segregation studies of Sn and Sb in Cu(1 0 0)-0.14 at.% Sn-0.12 at.% Sb ternary alloy, have been done by making use of Auger Electron Spectroscopy. The method of Linear Temperature Ramp (LTR) was employed, whereby the sample was heated and cooled linearly at a constant rate. The positive heating rate showed both a kinetic segregation profile, as well as a narrow equilibrium segregation region, at higher temperatures. The equilibrium segregation profile was extended by cooling the sample. Sn was first to segregate to the surface due to its higher diffusion coefficient, mainly from a smaller activation energy ESn. Sb, due to its higher segregation energy, eventually replaced Sn from the surface. The modified Darken model was used to simulate the profile yielding the following segregation parameters: Do(Sn) = 6.3 × 10−6 m2/s, Do(Sb) = 2.8 × 10−5 m2/s; ESn = 175.4 kJ/mol, ESb = 186.3 kJ/mol; , ; ΩCu-Sn = 3.4 kJ/mol, ΩCu-Sb = 15.9 kJ/mol and ΩSn-Sb = −5.4 kJ/mol.  相似文献   

18.
We have investigated the oxidation behavior of MBE grown epitaxial Y(0 0 0 1)/Nb(1 1 0) films on sapphire substrates at elevated temperatures under atmospheric conditions with a combination of experimental methods. At room temperature X-ray diffraction (XRD) reveals the formation of a 25 Å thick YOxHx layer at the surface, while simultaneously oxide growth proceeds along defect lines normal to the film plane, resulting in the formation of a single crystalline cubic Y2O3 (2 2 2) phase. Furthermore, nuclear resonance analysis (NRA) reveals that hydrogen penetrates into the sample and transforms the entire Y film into the hydride YH2 phase. Additional annealing in air leads to further oxidation radially out from the already existing oxide channels. Finally material transport during oxidation results in the formation of conically shaped oxide precipitations at the surface above the oxide channels as observed by atomic force microscopy (AFM).  相似文献   

19.
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   

20.
Phase relationships, thermal expansion and electrical properties of Mg1 − xFexO (x = 0.1-0.45) cubic solid solutions and Fe3 − x − yMgxCryO4 ± δ (x = 0.7-0.95; y = 0 or 0.5) spinels were studied at 300-1770 K in the oxygen partial pressure range from 10 Pa to 21 kPa. Increasing iron content enlarges the spinel phase stability domain at reduced oxygen pressures and elevated temperatures. The total conductivity of the spinel ceramics is predominantly n-type electronic and is essentially p(O2)-independent within the stability domain. The computer simulations using molecular dynamics technique confirmed that overall level of ion diffusion remains low even at high temperatures close to the melting point. Temperature dependencies of the total conductivity in air exhibit a complex behavior associated with changing the dominant defect-chemistry mechanism from prevailing formation of the interstitial cations above 1370-1470 K to the generation of cation vacancies at lower temperatures, and with kinetically frozen cation redistribution in spinel lattice below 700-800 K. The average thermal expansion coefficients of the spinel ceramics calculated from dilatometric data in air vary in the range (9.6-10.0) × 10− 6 K− 1 at 300-500 K and (13.2-16.1) × 10− 6 K− 1 at 1050-1370 K. Mg1 − xFexO solid solutions undergo partial decomposition on heating under oxidizing and mildly reducing conditions, resulting in the segregation of spinel phase and conductivity decrease.  相似文献   

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