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1.
Photon-stimulated ion desorption from deuterated formic acid chemisorbed on Si(100) has been studied using pulsed synchrotron radiation in the energy region of the oxygen 1s electron excitation. The O 1s electrons of hydroxyl oxygen and carbonyl oxygen could be selectively excited in the O K-edge region because the chemical environments are different. It is found that the CDO+ yield is enhanced at the O 1s(C---O)→σ*(C---O) resonance and the CD+ yield at the O 1s(C=O)→σ*(C---O) resonance. The results indicate that ion desorption is related both to the antibonding character of excited molecular orbitals and the local character of core hole orbitals.  相似文献   

2.
Ion desorption induced by a resonant excitation of O 1s of condensed amorphous H2O has been studied by total ion and total electron yield spectroscopy, nonderivative Auger electron spectroscopy (AES) and Auger electron photo-ion coincidence (AEPICO) spectroscopy. The spectrum of total ion yield divided by total electron yield exhibits a characteristic threshold peak at hν = 533.4 eV, which is assigned to the 4a1 ← O 1s resonant transition. The AES at the 4a1 ← O 1s resonance is interpreted as being composed of the spectator-AES of the surface H2O, and the normal-AES of the bulk H2O, where the 4a1 electron is delocalized before Auger transitions. H+ is found to be the only ion species in AEPICO spectra measured at the 4a1 ← O 1s resonance and at the O 1s ionization (hν = 560 eV). The electron kinetic energy dependence of the AEPICO yield (AEPICO yield spectrum) at the 4a1 ← O 1s resonance is found to be greatly different from that at the O 1s ionization. The peak positions of the AEPICO yield spectrum at the 4a1 ← O 1s resonance are found to correspond to those of the spectator-AES of the surface H2O, which is extracted from the AES at the 4a1 ← O 1s resonance. Furthermore, the AEPICO yield is greatly enhanced at the 4a1 ← O 1s resonance as compared with that at the O 1s ionization. On the basis of these results, a spectator-Auger-stimulated ion desorption mechanism and/or ultra-fast ion desorption mechanism are concluded to be responsible for the H+ desorption at the 4a1 ← O 1s resonance. The enhancement of the H+ yield is ascribed to the O---H anti-bonding character of the 4a1 orbital.  相似文献   

3.
The chemical constitution of functionalized supports is an important parameter that determines their performance in a broad range of applications, e.g. for immobilization of biomolecules. Supports with amino functionalized surfaces are also often used for DNA microarray experiments. However, spectral data which have been reported for surfaces with amino functionalities suffer from some inconsistencies. In this article a detailed XPS (X-ray photoelectron spectroscopy) and NEXAFS (Near edge X-ray absorption fine structure) database for amino functionalized surfaces is presented. Amino-terminated surfaces prepared from aliphatic and aromatic aminosilanes or aminothiols and a field sample are considered. Effects of aging in air and damage by radiation are addressed as well.  相似文献   

4.
We have investigated photon-stimulated ion desorption from deuterated benzene (C6D6) adsorbed on Si(1 0 0) and Si(1 1 1) surfaces following C 1s core excitation. Using time-of-flight mass spectrometry combined with angle-dependent technique, we measured the dependences of mass-spectra of desorption ions on photon energies and on incident angle (θ) of synchrotron beam. We have found the ion yields for adsorbate-derived fragments of CD+ and CD2+ are enhanced in very small angles of incident X-rays. Moreover, molecular orientation effect appeared in excitation energy dependences of D+ ions from the Si(1 0 0) and Si(1 1 1) surfaces; that is, ion yield spectra measured at θ = 10° are different from that at θ = 65°. Furthermore, it was found that desorption ion yields increase greatly with decreasing incident angles. The angular dependences are consistently similar for all ion species, excitation energies, and indexes of substrates. Possible desorption processes are described on the basis of the observations.  相似文献   

5.
In this work we present results from density functional theory (DFT) cluster studies to determine polarization-dependent near edge X-ray absorption fine structure (NEXAFS) spectra of the vanadyl termination of the V2O3(0 0 0 1) surface. The oxygen K edge spectra are calculated for the relaxed surface geometry where geometric parameters are taken from recent periodic DFT work. A detailed analysis of energetic peak positions, relative intensities, and final state orbitals allows a deep understanding of the complex angular dependence of the calculated spectra on the basis of the local binding environment of differently coordinated oxygen species. Further, our theoretical analysis can assign and explain various spectral details in the experimental NEXAFS data, in particular, those related to vanadyl oxygen. This allows us to support the experimentally suggested vanadyl surface termination.  相似文献   

6.
J. Zhou 《Surface science》2006,600(7):1540-1546
Formaldehyde adsorption and reaction have been studied on cerium oxide thin films that were vapor deposited on Ru(0 0 0 1). The formaldehyde behavior was examined as a function of temperature, exposure and Ce oxidation state. Formaldehyde chemisorbs on fully oxidized CeO2 as dioxymethylene, CH2O2. The dioxymethylene decomposes and desorbs as formaldehyde between 200 K and 400 K. No other products are formed. On reduced ceria, formaldehyde also adsorbs as dioxymethylene. In addition to the formaldehyde desorption between 200 K and 400 K, a more strongly bound form of dioxymethylene is formed that produces formaldehyde at 440 K. Above 400 K, some of the dioxymethylene reacts to form formate and methoxy on the surface. These species decompose to produce H2, CO and CH2O above 500 K.  相似文献   

7.
Water is one of the obstacles for prolonged life-time of organic based field-effect-transistors (OFETs). Here, we show how H2O molecules adsorb and affect pentacene crystal by using photoelectron spectroscopic methods. Diffusion into the crystal is accompanied with accumulation of H2O onto the crystal. Valence band, core level, and X-ray absorption spectra show that H2O molecules physisorb on the pentacene surface via oxygen, resulting in the increase of the hole-injection barrier. The diffused molecules results in the deteriorated crystallinity, and they reflect the weakening inter-molecular interactions of pentacene crystal.  相似文献   

8.
The adsorption of naphthalene, vacuum deposited on a Ag(1 0 0) surface, was comprehensively investigated by means of low-energy electron diffraction (LEED), temperature-programmed thermal desorption (TPD) spectroscopy, X-ray photoelectron spectroscopy (XPS), and polarization-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the mono- and multilayer regime. A growth of long-range ordered monolayer at 140 K is observed with LEED. The polarization-dependent C 1s NEXAFS shows that the naphthalene molecules in the monolayer lie almost parallel to the Ag(1 0 0) surface. With increasing film thickness, the molecular orientation turns to upright position. Furthermore, NEXAFS measurements show that in the multilayer regime the molecular orientation depends on the substrate temperature during deposition.  相似文献   

9.
We have studied the thin film formation and the electronic structure of the organic molecular semiconductor 3,4,9,10 perylene tetracarboxylic dianhydride (PTCDA), on clean and on hydrogen-passivated Si(0 0 1) surfaces. The studies were made by means of high resolution X-ray photoelectron spectroscopy (HRXPS), angle-resolved photoelectron spectroscopy (ARPES), near edge X-ray absorption fine structure (NEXAFS) and low energy electron diffraction (LEED). On the H passivated surface the changes in the electronic structure of the substrate and the molecules with increasing film thickness are very small. The molecular orbitals show a dispersive behavior, indicating that the PTCDA layers are ordered. On the reactive clean surface the anhydride groups of the molecule interact with the substrate as indicated by changes in the core level binding energies. This results in a much lower ordering in the film compared to PTCDA on a passivated silicon surface. There is no sign of decomposition of the molecule because of the more reactive substrate.  相似文献   

10.
We investigated the growth of Fe nanostructured films on c(2 × 2)-N/Cu(1 0 0) surface with Fe K-edge X-ray absorption fine structure (XAFS) in the near edge and in the extended energy region. The high photon flux of the incident X-rays allowed us to perform multishell analysis of the XAFS oscillations for Fe coverage ΘFe < 1 ML. This data analysis yields a detailed investigation of the atom geometry and some insights in the film morphology. At ΘN < 0.5 ML (N saturation coverage) there is absence of contribution to XAFS from N atoms. First shell analysis of linearly polarized XAFS gives Fe-Fe (or Fe-Cu) bond length values varying between R1 = 2.526 ± 0.006 Å at the highest Fe coverage (3 ML ) and R1 = 2.58 ± 0.01 Å at ΘFe = 0.5 ML, ΘN = 0.3 ML, with incidence angle Θ = 35°. These values are different from the case of bcc Fe (R = 2.48 Å), and compatible with fcc Fe (R1 = 2.52 Å) and fcc Cu (R1 = 2.55 Å). At the Fe lowest coverage (ΘFe = 0.5 ML) the dependence of R1 on the incidence angle indicates expansion of the outmost layer. Near edge spectra and multishell analysis can be well reproduced by fcc geometry with high degree of static disorder. At N saturation pre-coverage (ΘN = 0.5 ML) the XAFS analysis has to keep into account the Fe-N bonding. The results suggest two different adsorption sites: one with Fe in a fcc hollow site, surrounded by other metal atoms as nearest neighbours, and one resulting from an exchange with a Cu atom underneath the N layer.  相似文献   

11.
Photostimulated ion desorption at the 4a1 ← N 1s resonant transition of condensed NH3 was studied using electron emission spectroscopy and Auger-electron photoion coincidence (AEPICO) spectroscopy. The total ion yield divided by the Auger-electron yield exhibited a threshold peak at hν = 399 eV which is ascribed to the resonant transition from the N 1s to the N---H antibonding 4a1 orbital. The electron emission spectrum at the 4a1 ← N 1s resonance is decomposed into three components: a valence photoelectron emission spectrum, and normal- and resonant-Auger-electron emission spectra. We ascribe the resonant-Auger-electron emission spectrum mainly to spectator-Auger transitions on the basis of the peak assignment. A series of AEPICO spectra at the 4a1 ← N 1s resonance was also measured as a function of the Auger-electron kinetic energy. The electron kinetic energy dependence of the H+ AEPICO yield displays a shape approximately similar to that of the mixed spectrum of normal- and spectator-Auger-electron emission spectra. Based on this result the H+ desorption at the 4a1 ← N 1s resonance is concluded to originate from the spectator-Auger transitions and from the normal-Auger transitions following the delocalization of the excited electron.  相似文献   

12.
We have studied the interface and thin film formation of the organic molecular semiconductor 3,4,9,10 perylene tetracarboxylic dianhydride (PTCDA) on clean and on hydrogen passivated Si(0 0 1) surfaces. The studies were made by means of high resolution X-ray photoelectron spectroscopy (HRXPS), near edge X-ray absorption fine structure (NEXAFS), low energy electron diffraction (LEED), and atomic force microscopy (AFM). On the passivated surface the LEED pattern is somewhat diffuse but reveals that the molecules grow in several ordered domains with equivalent orientations to the substrate. NEXAFS shows that the molecules are lying flat on the substrate. The Si 2p XPS line shape is not affected when the film is deposited so it can be concluded that the interaction at the interface between PTCDA and the substrate is weak. The evolution of the film formation appears to be homogeneous for the first monolayer with a nearly complete coverage of flat lying molecules based on the XPS attenuation. For layer thickness of 0.5-2 monolayers (ML) the molecules start to form islands, attracting the molecules in between, leaving the substrate partly uncovered. For thicker films there is a Stranski-Krastanov growth mode with thick islands and a monolayer thick film in between. For the clean surface the ordering of the film is much lower and angle resolved photoelectron spectroscopy (ARPES) of the molecular orbitals have only a small dependence of the emission angle. NEXAFS shows that the molecules do not lie flat on the surface and also reveal a chemical interaction at the interface.  相似文献   

13.
Methyl mercaptoacetate (MA) on Cu(1 1 1) surface was investigated using synchrotron radiation-based X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. MA adsorbs on the surface via thiolate formation and weak interaction of the carbonyl group with the surface. Two different adsorption states previously reported for methanethiolate and ethanethiolate were confirmed, besides atomic sulfur. NEXAFS measurements support gauche-type conformation of MA whose skeleton lies on the surface.  相似文献   

14.
Thin silicon Phthalocyanine dichloride films on HOPG were prepared and the sample was heated in the vacuum with laser.The thickness of the thin sample on HOPG was checked by X-ray photoemission spectroscopy.The orientation of the molecules in respect to the substrate plane Was investigated by measuring the silicon K-edge near edge X-ray absorption fine structure(NEXAFS).In the NEXAFS spectra of the thin sample,two clear peaks which were assigned to 1s→σ*Si-N and 1s→σ*Si-C1 appeared around 1847.2 eV and 1843.1 eV respectively.The intensities of the resonance peaks showed strong polarization dependence.A quantitative analysis of the polarization dependence revealed that the Si-N bond tended to lie down while the Si-C1 bond was out of the molecular plane.  相似文献   

15.
16.
Layers of the DNA bases adenine, cytosine, and guanine were deposited onto hydrogen passivated Si(1 1 1) surfaces. The average tilt angles of these molecules with respect to the substrate surface were determined by the angular dependence of the Near Edge X-ray Absorption Fine Structure (NEXAFS) of the carbon K-edge. The interpretation of the NEXAFS spectra was assisted by a semi-empirical approach to the calculation of the π-transition region which employs density functional theory calculations and core level photoemission data.  相似文献   

17.
Adsorption behavior of atomic deuterium on a hexagonal boron nitride (h-BN) thin film is studied by photon-stimulated ion desorption (PSID) of D+ and near edge X-ray absorption fine structure (NEXAFS) at the B and N K-edges. After the adsorption of atomic deuterium, D+ desorption yield η() shows clear enhancement at the B K-edge and almost no enhancement at the N K-edge. NEXAFS spectra show a large change in the B K-edge and a small change in the N K-edge after the adsorption. We propose selective adsorption of atomic deuterium on the h-BN thin film based on the experimental results, and mention the effectiveness of applying the PSID method with X-ray to study hydrogen storage materials.  相似文献   

18.
The adsorption of l-cysteine and l-methionine amino acids on a chiral Cu{5 3 1} surface was investigated with high resolution X-ray photoelectron spectroscopy (XPS) and carbon K-edge near edge X-ray absorption fine structure (NEXAFS) Spectroscopy using synchrotron radiation. XPS shows that at 300 K l-cysteine adsorbs through two oxygen, a nitrogen and a sulfur atom, in a four point ‘quadrangular footprint’, whereas l-methionine adsorbs through only two oxygen and a nitrogen atom in a ‘triangular footprint’. NEXAFS was used to clarify the adsorption geometry of both molecules, which suggests a binding orientation to the top layer and second layer atoms in two different orientations associated with adsorption sites on {1 1 0} and {3 1 1} microfacets of the Cu{5 3 1} surface.  相似文献   

19.
Ex-situ prepared films of 4-aminothiophenol (4-ATP) on Au(1 1 1) have been studied by core-level photoemission using synchrotron radiation, ultra-high-vacuum scanning tunneling microscopy and spectroscopy (UHV-STM, STS), and X-ray absorption (NEXAFS). Photoemission measurements suggest that the film contains a relatively low percentage of 4-ATP bonded to the Au surface, with the presence of free 4-ATP, with oxidised and possibly dimerised molecules also present. We find a lower oxide content than has previously been observed, with well-resolved STM images. These images show a disruption of the long range order of the Au(1 1 1)-(22 × √3) reconstruction, with local nucleation of the reconstruction apparently induced by the 4-ATP, and bias-dependent contrast images. This latter effect, together with the asymmetry observed in STS, is ascribed to the presence of oriented molecular dipole layers between the metal and the organic material. NEXAFS data suggest a broadly upright geometry, with, however, considerable uncertainties.  相似文献   

20.
We have investigated the photon-stimulated ion-desorption from deuterated formic acid (DCOOD) monolayer chemisorbed on Si(100) crystal by applying a photoion-photoion-coincidence technique. The true-coincidence yields of an ion pair C+---D+ are given in the photon energy range (275–400 eV) above the C 1s absorption edge. The partial ion yields and Auger electron yields re presented for comparison. It was found that the multielectron (shake-off) excitation promotes the multiple bond-breaking of the adsorbate and the ion pair C+–D+ desorption events.  相似文献   

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