Angle-resolved photoelectron spectroscopy of geometrically nonuniform surfaces

The formation of angle-resolved photoelectron spectra for crystal surfaces with a complex geometric relief is considered. A simple model of a thin corrugated single-crystal film is proposed which illustrates the main specific features of this process. It is shown that photoelectron spectra of these surfaces exhibit features that, rather than reflecting the true electronic structure of the system, result from its superposition with the geometric structure. The validity of the model is demonstrated with the use of a physical system based on Ni(771) and Ni(755) stepped surfaces with periodic steps. It is revealed that, as a graphite coating grows to a monolayer thickness, these surfaces become faceted to form a geometrically nonuniform surface relief. The photoelectron spectra obtained for such a surface can be used to derive a quantitative characteristic of both the electronic structure of the surface and its geometric properties. The surface topography of the system is determined independently using scanning tunneling microscopy.     

Characterization of plasma fluorinated zirconia for dental applications by X-ray photoelectron spectroscopy

This paper discusses fluorination of biomedical-grade yttria-stabilized zirconia (YSZ) by sulfur hexafluoride plasma treatment and characterization of near-surface chemistry products by X-ray photoelectron spectroscopy (XPS). Deconvolution of the Zr 3d and Y 3d XPS core level spectra revealed formation of both ZrF₄ and YF₃. In addition, seven-coordinate ZrO₂F₅ and/or ZrO₃F₄ phases were deconvolved, retaining similar atomic coordination as the parent oxide and believed to have formed by substitutional displacement of oxygen by fluorine. No additional components attributed to yttria oxyfluoride were deconvolved. Argon ion sputter depth profiling determined the overlayer to be ∼4.0 nm in thickness, and angle resolved XPS showed no angle dependence on component percentages likely due to fluorination extending into the grain boundaries of the polycrystalline substrates. Importantly, the conversion layer did not induce any apparent change in zirconia crystallinity by inspection of Zr-O 3d_5/2,3/2 peak positions and full-width-at-half-maximum values, important for retaining its desirable mechanical properties.     

A study of dilute tin alloys by x-ray photoelectron spectroscopy

X-ray photoelectron spectra of Pb₉₈Sn₂, Ag₉₅Sn₅, Sb₉₅Sn₅ and Cd_99.6Sn_0.4 have been recorded using a VG Scientific ESCA-3 Mk. II electron spectrometer. In all cases the Sn 3d level in the alloys is compared with the 3d level in pure tin. The binding energy shifts are explained on the basis of electronegativity and near-neighbour interactions. It is found that increased coordination number as well as increased electronegativity of the neighbouring atoms increases the binding energy of the core electron level.     

Study of nanocrystalline V02 thin films prepared by magnetron sputtering and post-oxidation

Nanocrystalline VO2 thin films were deposited onto glass slides by direct current magnetron sputtering and postoxidation. These films undergo semiconductor-metal transition at 70 ℃, accompanied by a resistance drop of two magnitude orders. The crystal structures and surface morphologies of the VO2 films were characterized by x-ray diffraction （XRD） and atomic force microscope （AFM）, respectively. Results reveal that the average grain size of VO2 nanograins measured by XRD is smaller than those measured by AFM. In addition, Raman characterization indicates that stoichiometric VO2 and oxygen-rich VO2 phases coexist in the films, which is supported by x-ray photoelectron spectroscopy （XPS） results. Finally, the optical properties of the VO2 films in UV-visible range were also evaluated. The optical band gap corresponding to 2p-3d inter-band transition was deduced according to the transmission and reflection spectra. And the deduced value, Eopt2p-3d ： 1.81 eV, is in good agreement with that previously obtained by theoretical calculation.     

X-ray photoelectron spectroscopy study of Pd oxidation by RF discharge in oxygen

The low-temperature oxidation of polycrystalline palladium by RF oxygen plasma was studied via X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Detailed information about the electronic states of palladium and oxygen was obtained based on the XPS curve fitting analysis of Pd3d and Pd3p + O1s lines. The results showed that Pd oxidation by oxygen plasma was different from Pd oxidation in pure O₂ at high temperature. SEM shows well-structured submicron PdO particles result from oxidation in pure O₂, whereas plasma oxidation results in the predominant formation of two-dimensional PdO structures covering the initial crystallites of the Pd foil. Further oxidation to a three-dimensional PdO phase occurs under prolonged treatment with oxygen plasma. The formation of a PdO_x (x > 1) species, characterized by a E_b(Pd3d_5/2) = 338.0–338.2 eV value that is close to the Pd⁴⁺ oxidation state, was also observed. This PdO_x species was found to have low thermal stability (T < 400 K). It is proposed that the PdO_x species can be localized within the boundaries of crystallites.     

X射线光电子能谱

X射线光电子能谱（X-ray photoelectron spectroscopy，XPS）技术也被称作用于化学分析的电子能谱（electron spectroscopy for chemical analysis，ESCA）．XPS属表面分析法，它可以给出固体样品表面所含的元素种类、化学组成以及有关的电子结构重要信息，在各种固体材料的基础研究和实际应用中起着重要的作用．文章简要介绍了XPS仪器的工作原理和分析方法，并给出了XPS在科学研究工作中的应用实例．     

Study of nanocrystalline VO2 thin films prepared by magnetron sputtering and post-oxidation

Nanocrystalline VO2 thin films were deposited onto glass slides by direct current magnetron sputtering and postoxidation. These films undergo semiconductor-metal transition at 70°C, accompanied by a resistance drop of two magnitude orders. The crystal structures and surface morphologies of the VO2 films were characterized by x-ray diffraction (XRD) and atomic force microscope (AFM), respectively. Results reveal that the average grain size of VO2 nanograins measured by XRD is smaller than those measured by AFM. In addition, Raman characterization indicates that stoichiometric VO2 and oxygen-rich VO2 phases coexist in the films, which is supported by x-ray photoelectron spectroscopy (XPS) results. Finally, the optical properties of the VO2 films in UV-visible range were also evaluated. The optical band gap corresponding to 2p-3d inter-band transition was deduced according to the transmission and reflection spectra. And the deduced value, E opt2p-3d = 1.81 eV, is in good agreement with that previously obtained by theoretical calculation.     

X射线光电子能谱

X射线光电子能谱（X-ray photoelectron spectroscopy, XPS）技术也被称作用于化学分析的电子能谱（electron spectroscopy for chemical analysis,ESCA）.XPS属表面分析法,它可以给出固体样品表面所含的元素种类、化学组成以及有关的电子结构重要信息,在各种固体材料的基础研究和实际应用中起着重要的作用.文章简要介绍了XPS仪器的工作原理和分析方法,并给出了XPS在科学研究工作中的应用实例.     

Angle-resolved UV photoelectron spectroscopy of ethylene and benzene on nickel

A review of results obtained by Angle-Resolved UV-Photoelectron Spectroscopy (ARUPS) using linearly polarized synchrotron radiation is presented for two model systems, ethylene/Ni and benzene/Ni. It is shown that for these systems detailed conclusions concerning adsorbate/substrate and adsorbate/adsorbate interactions can be derived from ARUPS spectra using symmetry selection rules, and in combination with model calculations. In particular, electronic structure, bonding, orientation and symmetry of the adsorbates in dilute and saturated layers will be discussed. It is shown that at high adsorbate coverages lateral interactions in the adsorbate layer play a dominant role. Steric effects in densely packed layers can lead to a reorientation of the molecules as compared to the orientation of the single molecules. The ARUPS spectra of well ordered, densely packed layers exhibit significant (up to 2 eV) dispersion of the various adsorbate bands and allow detailed conclusions on two-dimensional adsorbate band structures.     

Investigations of CdS and Ag-CdS nanoparticles by X-ray photoelectron spectroscopy

In the present report, CdS and Ag-CdS nanoparticles were synthesized using cysteine as a capping agent. Surface properties CdS and Ag-CdS nanoparticles were studied by X-ray photoelectron spectroscopy (XPS). XPS study of CdS nanoparticles was carried out as a function of pH and for a refluxed sample at pH 11.2. Effect of dopant concentration on surface properties of Ag-CdS nanoparticles was also studied for as prepared samples as well as for annealed sample at 2% doping. Effect of pH, dopant concentration, and effect of particle size on different sulfur species present in the system was studied. Features of Cd 3d, S 2p and Ag 3d core level have been discussed in detail.     

Angle-resolved electron spectroscopy of laser-assisted Auger decay induced by a few-femtosecond x-ray pulse

Two-color (x-ray+infrared) electron spectroscopy is used for investigating laser-assisted KLL Auger decay following 1s photoionization of atomic Ne with few-femtosecond x-ray pulses from the Linac Coherent Light Source. In an angle-resolved experiment, the overall width of the laser-modified Auger-electron spectrum and its structure change significantly as a function of the emission angle. The spectra are characterized by a strong intensity variation of the sidebands revealing a gross structure. This variation is caused, as predicted by theory, by the interference of electrons emitted at different times within the duration of one optical cycle of the infrared dressing laser, which almost coincides with the lifetime of the Ne 1s vacancy.     

An x-ray photoelectron spectroscopy study of the activated cobalt-molybdenum-alumina hydrodesulfurization catalysts

ESCA was used to monitor the chemical modification of a series of commercial cobalt-molybdenum-alumina hydrodesulfurization catalysts subjected to different reaction conditions. In the oxide form, the surface phase $\text{resembles}$ MoO₃ and CoAl₂O₄. Reduction and sulfiding using a 15:85 H₂S/H₂ mixture shifts the molybdenum peaks to the region of MoS₂. Part of the cobalt is apparently reduced and sulfided, but this species is susceptible to re-oxidation by moist air. The supported cobalt which is not changed by this treatment is interpreted as actually being CoAl₂O₄ formed by interaction of the dispersed material with the support during calcination. The presence of this aluminate phase seems to be important for the stability of the catalyst under the harsh conditions of industrial usage. Reduction of the oxide form by pure hydrogen leaves the molybdenum binding energy unchanged and shifts the cobalt peak to higher binding energy. This is interpreted as arising from a shift in reference level and it is concluded that the actual transformation     

Transition metal oxide perovskites by photoelectron and x-ray absorption spectroscopy

X-ray and ultraviolet photoelectron spectroscopy as well as x-ray absorption spectroscopy have been employed to investigate transition metal oxide perovskites of the general formula ABO₃ (A = La or rare-earth ion, B=trivalent transition metal ion). Systematics in the core levels and in the valence bands in the series of LaBO₃ compounds have been discussed. Lanthanum chemical shifts in the x-ray absorption spectra in this series show interesting trends. Photoelectron spectra of the solid solutions, LaNi_1−x Co _x O₃, LaNi_1−x Fe _x O₃ and LaFe_1−x Co _x O₃ show that the rigid band model is applicable to these systems. It is shown that x-ray photoelectron spectroscopy can be employed to identify multiple oxidation states of transition metal ions in oxide perovskites. Communication No. 30 from the Solid State and Structural Chemistry Unit. An erratum to this article is available at .     

Near surface composition of some alloys by X-ray photoelectron spectroscopy

Chemical compositions of the alloys of CuNi (Cu_0.10Ni_0.90, Cu_0.30Ni_0.70, Cu_0.70Ni_0.30) and BiSb (Bi_0.80Sb_0.20, Bi_0.64Sb_0.34, Bi_0.55Sb_0.45) are determined by X-ray photoelectron spectroscopy. The stoichiometries are determined and are compared with the bulk compositions. Possible sources of systematic errors contributing to the results are discussed. Errors arising out of preferential etching in these alloys have been investigated. It has been inferred from such studies that the preferential etching does not enrich the surface composition with a particular component for the two systems reported here. Quantitative results of CuNi system indicate that the surface regions of the Cu_0.70Ni_0.30 alloy is Cu-rich, although no such evidence is observed in case of BiSb system.     

低速高电荷态重离子辐照的GaN晶体表面X射线光电子能谱研究

利用低速高电荷态Xeq+和Pbq+离子对在蓝宝石衬底上生长的GaN晶体膜样品进行辐照,并利用X射线光电子能谱(XPS)对样品表面化学组成和元素化合态进行了分析.结果表明,高电荷态离子对样品表面有显著的刻蚀作用;经高电荷态离子辐照的GaN样品表面氮元素贫乏而镓元素富集;随着入射离子剂量和所携带电荷数的增大,Ga—Ga键相对含量增大;辐照后,GaN样品中Ga—Ga键对应的Ga3d5/2电子的束缚能偏小,晶格损伤使内层轨道电子束缚能向低端方向偏移.     

Standards for x-ray photoelectron spectroscopy of boron compounds

A set of standard compounds for x-ray photoelectron spectroscopy (XPS): KBH₄, NaBPh₄, and KBF₄ has been identified. Literature data on XPS for salts of the anions , , and , the donor-acceptor complexes LBF₃, and also their related compounds was analyzed with a view toward the validity of the data. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 886–895, November–December, 2008.     

磁性隧道结热稳定性的x射线光电子能谱研究

通过XPS等微观分析手段证实了磁性隧道结在高温退火后，反铁磁层中的Mn元素扩散到被钉 扎铁磁层及势垒层中，破坏了势垒层/铁磁层界面，从而导致了磁性隧道结高温退火后TMR的 下降.然而在反铁磁层和被钉扎铁磁层之间插入一层纳米氧化层后，Mn的扩散得到了抑制， 使磁性隧道结的热稳定性得以提高. 关键词： 磁性隧道结 纳米氧化层 x射线光电子能谱     

等电子法测量小能量激光打靶等离子体电子温度

以低Z的CHO薄膜作为样品靶，在星光激光装置上以小能量激光辐照样品靶产生温度较低的等离子体，采用每毫米2400线的平焦场光栅谱仪测量等离子体发射的碳和氧离子发射谱线强度比，并与理论计算相应线强比较，获得了电子温度，建立了等电子法测量较低温度(100eV左右)等离子体电子温度的诊断技术. 关键词： 电子温度 激光等离子体 等电子x射线谱法     

Angle-resolved ultraviolet photoelectron spectroscopy of expitaxial films of vanadyl-phthalocyanine grown on alkali halides

The molecular orientation of Vanadyl-Phthalocyanine (VOPc) grown on alkali halides was studied by Angle-Resolved Ultraviolet Photoelectron Spectroscopy (ARUPS). To avoid charging up of the specimen during ARUPS measurment, thin epitaxial films of alkali halides grown on GaAs (0 0 1) were used as substrates. Photoelectrons emitted from the highest occupied molecular orbital band of VOPc showed strong angular distribution leading to the conclusion that the molecules stay almost parallel on the surface. This was in accordance with the expectation based on the reflection high-energy electron diffraction analysis of the film.     

Angle-resolved photoelectron spectroscopy of benzene and hexafluorobenzene as a function of photon energy

Angle-resolved photoelectron spectra of benzene have been recorded using synchrotron radiation as the photon source. From these results the angular dis the first three orbitals; 1e_1g(π), 3e_2g (σ) and 1a_2u(π). Calculations of β employing the MS Xα method have also b and theory for the first two orbitals is excellent. Poor agreement in the core of the third orbital is believed to be due to overlap of the second and has been verified by data obtained for perfluorobenzene. The universality of the energy dependence of β for π orbitals, noted previously for unsatu aromatic systems. The importance of the results for benzene for the future application of angle-resolved photoelectron spectroscopy to complex molecule