电沉积铁族薄膜的磁性圆二色研究

采用循环伏安法在GaAs(100)单晶表面电沉积了铁族金属单质薄膜. 扫描电子显微镜(SEM)结果显示, Fe族金属薄膜的晶粒较小, 薄膜平整度较高。通过X射线衍射(XRD)谱分析了Fe, Co, Ni在GaAs(100)晶面上的外延生长. 使用磁光克尔效应装置研究了Fe族金属薄膜的宏观磁性, 用同步辐射圆偏振软X射线测量了铁族单质磁性薄膜的吸收谱, 获得了X射线磁性圆二色谱, 并通过加和定则计算了磁性薄膜中Fe族金属原子的轨道磁距和自旋磁矩.     

Surface-interface investigations of an ultrathin pulsed laser deposited NiO/ZnO bilayer structure

We hereby report detailed structural and morphological studies for an ultrathin NiO/ZnO bilayer structure grown on sapphire (001) substrate using pulsed laser deposition technique. The combined X-ray reflectivity (XRR) and grazing incidence X-ray fluorescence (GIXRF) studies revealed formation of a low-density defective ZnO interfacial layer of thickness ~32 Å at the ZnO/sapphire interface prior to growth of main ZnO layer. Our results further indicate that the variation of electron density across the NiO/ZnO bilayer structure is smooth and we do not observe presence of any interface layer between them. X-ray diffraction measurements show that deposited ZnO layer is epitaxial in nature whereas NiO is highly oriented along (100) direction. The angle dependent X-ray absorption near edge fine structure (XANES) measurements at Ni–K edge has been utilized to determine depth-resolved oxidation state of Ni and the results have been correlated with the depth-resolved electron density of NiO layer. The method described here offers nondestructive determination of the microstructural parameters as well as depth-resolved mapping of oxidation state of a thin film-based heterojunction device. It extends several advantages over destructive methods which are abundantly reported in literature.     

Identification of CO adsorption sites in supported Pt catalysts using high-energy-resolution fluorescence detection X-ray spectroscopy

High-energy-resolution fluorescence detection (HERFD) X-ray spectroscopy is presented as a new tool for the identification of the bonding sites of reactants in supported metal catalysts. The type of adsorption site of CO on an alumina-supported platinum catalyst and the orbitals involved in the bonding are identified. Because X-ray absorption spectroscopy (XAS) is element-specific and can be used under high pressures and temperatures, in situ HERFD XAS can be applied to a swathe of catalytic systems, including alloys.     

Co-Ni合金薄膜的电化学外延及同步辐射XMCD研究

采用电化学循环伏安法在单晶GaAs(001)衬底上外延沉积了Co-Ni二元合金薄膜. 扫描电子显微镜观察结果显示, 薄膜厚度约180 nm, 其表面由约40 nm大小的颗粒组成. 用X射线荧光法确定了薄膜的组分为Co66Ni34, XRD确定了其为面心立方结构. 用同步辐射圆偏振软X射线分别测量了样品中Co和Ni的吸收谱(XAS), 从而得到X射线磁性圆二色(XMCD)谱, 通过加和定则分别计算出了合金中Co和Ni的轨道磁矩和自旋磁矩, 与纯的Co和Ni样品相比, 它们都有不同程度的增加.     

Element-specific probe of the magnetic and electronic properties of Dy incar-fullerenes

The magnetic and electronic properties of a single atom and a pair of Dy atoms encapsulated inside fullerene carbon cages have been examined using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) as well as resonant photoelectron spectroscopy (RESPES) across the Dy M(4,5)-edge. The comparison of the measured XAS spectra with multiplet calculations indicates that the encaged Dy has a 4f( 9) configuration. The presence of Dy 5d spectral weight in the valence band is not detected by RESPES, indicating that Dy is in a formally trivalent state. The evolution of the encaged Dy orbital and spin moments of the 4f orbitals as a function of the applied magnetic field and temperature has been obtained from XMCD measurements. At 6.9 T and 4 K, both the orbital and the spin magnetic moments of the encaged Dy 4f electrons are dramatically smaller than those expected for the free Dy(3+) at saturation.     

Picosecond X-ray absorption spectroscopy of a photoinduced iron(II) spin crossover reaction in solution

In this study, we perform steady-state and time-resolved X-ray absorption spectroscopy (XAS) on the iron K-edge of [Fe(tren(py)3)](PF6)2 dissolved in acetonitrile solution. Static XAS measurements on the low-spin parent compound and its high-spin analogue, [Fe(tren(6-Me-py)3)](PF6)2, reveal distinct spectroscopic signatures for the two spin states in the X-ray absorption near-edge structure (XANES) and in the X-ray absorption fine structure (EXAFS). For the time-resolved studies, 100 fs, 400 nm pump pulses initiate a charge-transfer transition in the low-spin complex. The subsequent electronic and geometric changes associated with the formation of the high-spin excited state are probed with 70 ps, 7.1 keV, tunable X-ray pulses derived from the Advanced Light Source (ALS). Modeling of the transient XAS data reveals that the average iron-nitrogen (Fe-N) bond is lengthened by 0.21+/-0.03 A in the high-spin excited state relative to the ground state within 70 ps. This structural modification causes a change in the metal-ligand interactions as reflected by the altered density of states of the unoccupied metal orbitals. Our results constitute the first direct measurements of the dynamic atomic and electronic structural rearrangements occurring during a photoinduced FeII spin crossover reaction in solution via picosecond X-ray absorption spectroscopy.     

Artificial construction of the layered Ruddlesden-Popper manganite La2Sr2Mn3O10 by reflection high energy electron diffraction monitored pulsed laser deposition

Pulsed laser deposition has been used to artificially construct the n = 3 Ruddlesden-Popper structure La(2)Sr(2)Mn(3)O(10) in epitaxial thin film form by sequentially layering La(1-x)Sr(x)MnO(3) and SrO unit cells aided by in situ reflection high energy electron diffraction monitoring. The interval deposition technique was used to promote two-dimensional SrO growth. X-ray diffraction and cross-sectional transmission electron microscopy indicated that the trilayer structure had been formed. A site ordering was found to differ from that expected thermodynamically, with the smaller Sr(2+) predominantly on the R site due to kinetic trapping of the deposited cation sequence. A dependence of the out-of-plane lattice parameter on growth pressure was interpreted as changing the oxygen content of the films. Magnetic and transport measurements on fully oxygenated films indicated a frustrated magnetic ground state characterized as a spin glass-like magnetic phase with the glass temperature T(g) ≈ 34 K. The magnetic frustration has a clear in-plane (ab) magnetic anisotropy, which is maintained up to temperatures of 150 K. Density functional theory calculations suggest competing antiferromagnetic and ferromagnetic long-range orders, which are proposed as the origin of the low-temperature glassy state.     

Theory of surface states in spin wave resonance

Following a concise review of present achievements in the study of magnetic surface states by spin wave resonance, a discussion of surface state theory and experimentally observed effects is given. The theoretical treatment, starting from the general model assumptions made when dealing with thin magnetic films, concentrates specifically on the Surface Inhomogeneity Model, for which a Hamiltonian is established and diagonalized, leading to the elementary magnetic excitation i.e. spin waves of the system. The appropriate spin wave resonance theory is developed in detail, and the resonance effects are expounded on the basis of a Pinning Diagram, especially constructed for this purpose. Particular attention is given to the existence conditions for surface states, the experimental identification of their respective resonance lines, as well as the use of these lines when determining the surface conditions of the thin film and measuring its magnetic surface anisotropy. The analysis of the surface state properties is based on the exact solution of the eigenvalue problem of a finite linear chain with arbitrary (asymmetric) boundary conditions.     

Metal-to-ligand and ligand-to-metal charge transfer in thin films of Prussian blue analogues investigated by X-ray absorption spectroscopy

A series of thin films of Prussian blue analogues is investigated by X-ray absorption spectroscopy (XAS) at the Fe, Co and Mn L(2,3)-edges. The ligand field multiplet theory enables us to examine accurately the electronic structure of these materials. Experimental XAS spectra of CoFe Prussian blue analogues are successfully reproduced using a ground state configuration including metal-to-ligand (MLCT) and ligand-to-metal charge transfer (LMCT) at the Co and Fe L(2,3)-edges. In particular, a huge improvement is achieved for satellite peaks at the Co(iii) L(2,3)-edges compared to previous calculations in the literature based on LMCT effects only. On the other hand, XAS spectra of MnFe analogues synthesized for the first time, can be reproduced conveniently by taking into account either MLCT or LMCT depending on the conditions of the sample preparation. For each thin film, the proportion of the different oxidation states of Co, Fe and Mn is evaluated. Unexpectedly, this analysis reveals the presence of a significant amount of a reduced phase, which turns out to be strongly dependent on the sample synthesis and storage conditions.     

Pentacene films on Cu(119)

The molecular structure of thin pentacene film grown on a Cu(119) surface has been studied by near-edge X-ray absorption fine structure spectroscopy and scanning tunneling microscopy. The interaction between the π-molecular orbitals delocalized on the aromatic rings and the underlying copper substrate was deduced from XAS spectra. Pentacene molecules arrange with the main axis almost parallel with the Cu terraces according to the measured polarization dependence of the C 1s absorption spectra. For thickness exceeding 4 nm an upright arrangement of the molecules was observed with a dense herringbone-like ordering. The present study thus demonstrates that highly ordered pentacene films can be obtained on a Cu(119) vicinal surface both in a flat orientation for low coverages and in a bulk-like herringbone orientation for higher coverages.     

A solution study on the local and global structure changes of cytochrome c: an unfolding process induced by urea

The local and global structural changes of cytochrome c induced by urea in aqueous solution have been studied using X-ray absorption spectroscopy (XAS) and small-angle X-ray scattering (SAXS). According to the XAS result, both the native (folded) protein and the unfolded protein exhibit the same preedge features taken at Fe K-edge, indicating that the Fe(III) in the heme group of the protein maintains a six-coordinated local structure in both the folded and unfolded states. Furthermore, the discernible differences in the X-ray absorption near-edge structure (XANES) of these two states are attributed to a possible spin transition of the Fe(III) from a low-spin state to a high-spin state during the unfolding process. The perseverance of six-coordination and the spin transition of the iron are reconciled by a proposed ligand exchange, with urea and water molecules replacing the methionine-80 and histidine-18 axial ligands, respectively. The SAXS result reveals a significant morphology change of cytochrome c from a globular shape of a radius of gyration R(g) = 12.8 A of the native protein to an elongated ellipsoid shape of R(g) = 29.7 A for the unfolded protein in the presence of concentrated urea. The extended X-ray absorption fine structure (EXAFS) data unveil the coordination geometries of Fe(III) in both the folded and unfolded state of cytochrome c. An initial spin transition of Fe(III) followed by an axial ligand exchange, accompanied by the change in the global envelope, is proposed for what happened in the protein unfolding process of cytochrome c.     

Investigation of Structure and Growth of Self-Assembled Polyelectrolyte Layers by X-ray and Neutron Scattering under Grazing Angles

The structure of self-assembled polyelectrolyte thin films on float glass has been investigated by interface sensitive X-ray and neutron scattering methods. Special emphazis was given to the adsorption process of poly (ethylene imine) and polystyrole sulfonate as an important model system which is often used as a basis for subsequent multilayer buildup. From complementary X-ray and neutron reflectivity data, the vertical film density profile was derived for various growth parameters, including kinetic effects of different adsorption times. In addition to specular reflectivity, we have for the first time employed nonspecular X-ray scattering to study lateral structure parameters in self-assembled polyelectrolyte films. Furthermore, the technique of time-resolved in situ X-ray reflectivity during film growth has been demonstrated and is discussed in view of its future potential. Copyright 2000 Academic Press.     

New approaches to quantitative x-ray microanalysis of thin films and surfaces

Quantitative analysis of thin films using an electron probe micro-analyser requires the accurate knowledge of the depth distributions of X-ray production (Ø(z) curves) and the influence of the thin film- substrate interface on that distribution. A Gaussian expression for Ø(z) curves has been used which is modified at the interface by the ratio of Ø(0) values. In this way, quantitative predictions of the dependence of X-ray intensity on depth and substrate have been made. Analysis requires the use of only pure element or compound standards. The sensitivity for detection of thin films is about one monolayer for most elements. By measuring X-ray intensity as a function of electron energy, concentration profiles up to a depth of approximately 1 um. can be measured with a depth resolution of the order of 1 nm. in favourable cases.     

Spectroscopy and Structure of Sol-Gel Systems

Sol-gel derived glasses may differ from conventional melt-quenched glasses owing to the peculiar microstructures existing at the gel state, such that, even after gel densification, some differences may remain in their composition and molecular structure.This paper discusses structural characteristics of thin film oxide gels and glasses, with a special emphasis on SiO2-TiO2 based systems, which are of particular interest for sol-gel integrated optics applications. Short range structure aspects are discussed based on infrared, X-ray photoemission and X-ray photoabsorption spectroscopies. The chemical homogeneity of sol-gel materials is evaluated, based on X-ray photoemission and nuclear magnetic resonance spectroscopies, dealing in particular with the issue of homo- vs. heterocondensation. Finally, some microstructural features of sol-gel derived films are analyzed, namely the relationship between infrared absorption and porosity and the structure of nanocrystalline sol-gel films, based on grazing incidence X-ray diffraction and micro-Raman spectroscopy. The types of structural information obtainable by each different technique are compared in detail.     

Gallium-containing zeolites: characterization of catalytic role of gallium species in converting light paraffins to aromatics

The structures and the chemical nature of gallium species in gallium-containing zeolite catalysts prepared by hydrothermal synthesis and post-synthesis treatments are discussed based on the results of X-ray absorption spectroscopy (XAS), including X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS), and nuclear magnetic resonance (NMR) investigations. The in-situ analysis of properties of gallium active sites during oxidation/reduction cycles has been found to be further helpful on the understanding of the catalytic role of gallium species in the aromatization of alkanes.     

X-ray absorption spectroscopic investigation of the spin-transition character in a series of single-site perturbed iron(II) complexes

Select ferrous spin-transition complexes with the pentadentate ligand 2,6-bis(bis(2-pyridyl)methoxymethane)pyridine (PY5) were examined using variable-temperature solution solid-state magnetic susceptibility, crystallography, X-ray absorption spectroscopy (XAS), and UV/vis absorption spectroscopy. Altering the single exogeneous ligand, X, of [Fe(PY5)(X)]n)+ is sufficient to change the spin-state of the complexes. When X is the weak-field ligand Cl-, the resultant Fe complex is high-spin from 4 to 300 K, whereas the stronger-field ligand MeCN generates a low-spin complex over this temperature range. With intermediate-strength exogenous ligands (X = N3-, MeOH), the complexes undergo a spin-transition. [Fe(PY5)(N3)]+, as a crystalline solid, transitions gradually from a high-spin to a low-spin complex as the temperature is decreased, as evidenced by X-ray crystallography and solid-state magnetic susceptibility measurements. The spin-transition is also evident from changes in the pre-edge and EXAFS regions of the XAS Fe K-edge spectra on a ground crystalline sample. The spin-transition observed with [Fe(PY5)(MeOH)]2+ appears abrupt by solid-state magnetic susceptibility measurements, but gradual by XAS analysis, differences attributed to sample preparation. This research highlights the strengths of XAS in determining the electronic and geometric structure of such spin-transition complexes and underscores the importance of identical sample preparation in the investigation of these physical properties.     

Room temperature ferromagnetism in sol–gel deposited un-doped ZnO films

Dilute magnetic semiconductors are fast emerging spintronic materials where advantage of magnetic properties of semiconductor materials (usually doped with small quantities of magnetic ions) is being explored. Sol–gel technique, being low-cost simple and application oriented method, has been used in the present case. ZnO films of <150 nm thickness have been deposited by spin coating onto single crystal p-type Si substrates. The optimized sol is of paramagnetic nature, whereas, mixed para- dia-magnetic phase is observed for the as-prepared films. A complete ferromagnetic phase transition has been observed after heating the films in vacuum at a temperature of 300 °C. These sol–gel prepared films exhibit hexagonal wurtzite structure as observed by X-ray diffraction. After the magnetic field annealing in vacuum the films showed strengthened magnetic as well as structural properties. This work presents a clear evidence of ferromagnetic behavior of the un-doped ZnO films deposited by sol–gel at room temperature. It is also pointed out that Zn vacancies rather than oxygen deficiency are responsible for ferromagnetism in these sol–gel deposited ZnO thin films, whereas, the experimental evidence has been substantiated with the theoretical calculations using density functional theory.     

Structural and magnetic properties of nano-crystalline FeCoNiN thin films

Iron cobalt nickel nitride (FeCoNiN) thin films are prepared by sol-gel spin coating route. The structural, magnetic and surface properties of the thin films are evaluated. The crystalline nature of thin films was enhanced upon annealing, leading to increased crystallite size. The X-ray diffraction shows mixed phases with crystallite size in the range of 20–26.93 nm. Thin films show ferromagnetism at room temperature. Coercivity and saturation magnetization are in the range of 642–716 Oe and 2.5–7.5 emu/cm³ respectively. Both coercivity and saturation magnetization increased with annealing of thin films. Magnetic properties are related to the crystallinity of thin films. The increase in crystallite size results into an increase of magnetic properties. Rectangular shaped particles are seen on the surface of thin films. The same type of grains can be seen on the surface of thin films which confirmed the formation of FeCoNiN as predicted by XRD. These novel thin films might be used in memory devices and optoelectronic applications.     

X-ray absorption fine structure study of amorphous metal oxide thin films prepared by photochemical metalorganic deposition

The oxidation state and local geometry of the metal centers in amorphous thin films of Fe₂O₃ (Fe³⁺ oxidation state), CoFe₂O₄ (Co²⁺/Fe³⁺ oxidation states), and Cr₂O₃ (Cr³⁺ oxidation state) are determined using K edge X-ray absorption near-edge structure (XANES) spectroscopy and extended X-ray absorption fine structure (EXAFS) spectroscopy. The metal oxide thin films were prepared by the solid-state photochemical decomposition of the relevant metal 2-ethylhexanoates, spin cast as thin films. No peaks are observed in the X-ray diffraction patterns, indicating the metal oxides are X-ray amorphous. The oxidation state of the metals is determined from the edge position of the K absorption edges, and in the case of iron-containing samples, an analysis of the pre-edge peaks. In all cases, the EXAFS analysis indicates the first coordination shell consists of oxygen atoms in an octahedral geometry, with a second shell consisting of metals. No higher shells are observed beyond 3.5 Å for all samples, indicating the metal oxides are truly amorphous, consistent with X-ray diffraction results.     

In situ X-ray probing reveals fingerprints of surface platinum oxide

In situ X-ray absorption spectroscopy (XAS) at the Pt L(3) edge is a useful probe for Pt-O interactions at polymer electrolyte membrane fuel cell (PEMFC) cathodes. We show that XAS using the high energy resolution fluorescence detection (HERFD) mode, applied to a well-defined monolayer Pt/Rh(111) sample where the bulk penetrating hard X-rays probe only surface Pt atoms, provides a unique sensitivity to structure and chemical bonding at the Pt-electrolyte interface. Ab initio multiple-scattering calculations using the FEFF code and complementary extended X-ray absorption fine structure (EXAFS) results indicate that the commonly observed large increase of the white-line at high electrochemical potentials on PEMFC cathodes originates from platinum oxide formation, whereas previously proposed chemisorbed oxygen-containing species merely give rise to subtle spectral changes.