Interference phenomena of synchrotron radiation in TEY spectra for silicon‐on‐insulator structure

The general matrix theory of the photoelectron/fluorescence excitation in anisotropic multilayer films at the total reflection condition of X‐rays has been developed. In a particular case the theory has been applied to explain the oscillation structure of L_2,3 XANES spectra for a SiO₂/Si/SiO₂/c‐Si sample in the pre‐edge region which has been observed by a sample current technique at glancing angles of synchrotron radiation. Remarkably the phase of the oscillations is reversed by a ～2° angle variation. The observed spectral features are found to be a consequence of waveguide mode creation in the middle layer of strained Si, which changes the radiation field amplitude in the top SiO₂ layer. The fit of the data required the correction of the optical constants for Si and SiO₂ near the Si L_2,3‐edges.     

Carbon K‐edge spectra of carbonate minerals

Carbon K‐edge X‐ray spectroscopy has been applied to the study of a wide range of organic samples, from polymers and coals to interstellar dust particles. Identification of carbonaceous materials within these samples is accomplished by the pattern of resonances in the 280–320 eV energy region. Carbonate minerals are often encountered in the study of natural samples, and have been identified by a distinctive resonance at 290.3 eV. Here C K‐edge and Ca L‐edge spectra from a range of carbonate minerals are presented. Although all carbonates exhibit a sharp 290 eV resonance, both the precise position of this resonance and the positions of other resonances vary among minerals. The relative strengths of the different carbonate resonances also vary with crystal orientation to the linearly polarized X‐ray beam. Intriguingly, several carbonate minerals also exhibit a strong 288.6 eV resonance, consistent with the position of a carbonyl resonance rather than carbonate. Calcite and aragonite, although indistinguishable spectrally at the C K‐edge, exhibited significantly different spectra at the Ca L‐edge. The distinctive spectral fingerprints of carbonates provide an identification tool, allowing for the examination of such processes as carbon sequestration in minerals, Mn substitution in marine calcium carbonates (dolomitization) and serpentinization of basalts.     

X‐ray absorption near‐edge structure anomalous behaviour in structures with buried layers containing silicon nanocrystals

Substructure and phase composition of silicon suboxide films containing silicon nanocrystals and implanted with carbon have been investigated by means of the X‐ray absorption near‐edge structure technique with the use of synchrotron radiation. It is shown that formation of silicon nanocrystals in the films' depth (more than 60 nm) and their following transformation into silicon carbide nanocrystals leads to abnormal behaviour of the X‐ray absorption spectra in the elementary silicon absorption‐edge energy region (100–104 eV) or in the silicon oxide absorption‐edge energy region (104–110 eV). This abnormal behaviour is connected to X‐ray elastic backscattering on silicon or silicon carbide nanocrystals located in the silicon oxide films depth.     

X‐ray absorption study of the local structure at the NiO/oxide interfaces

This work reports an X‐ray absorption near‐edge structure (XANES) spectroscopy study at the Ni K‐edge in the early stages of growth of NiO on non‐ordered SiO₂, Al₂O₃ and MgO thin films substrates. Two different coverages of NiO on the substrates have been studied. The analysis of the XANES region shows that for high coverages (80 Eq‐ML) the spectra are similar to that of bulk NiO, being identical for all substrates. In contrast, for low coverages (1 Eq‐ML) the spectra differ from that of large coverages indicating that the local order around Ni is limited to the first two coordination shells. In addition, the results also suggest the formation of cross‐linking bonds Ni—O—M (M = Si, Al, Mg) at the interface.     

Finite lifetime broadening of calculated X‐ray absorption spectra: possible artefacts close to the edge

X‐ray absorption spectra calculated within an effective one‐electron approach have to be broadened to account for the finite lifetime of the core hole. For methods based on Green's function this can be achieved either by adding a small imaginary part to the energy or by convoluting the spectra on the real axis with a Lorentzian. By analyzing the Fe K‐ and L_2,3‐edge spectra it is demonstrated that these procedures lead to identical results only for energies higher than a few core‐level widths above the absorption edge. For energies close to the edge, spurious spectral features may appear if too much weight is put on broadening via the imaginary energy component. Special care should be taken for dichroic spectra at edges which comprise several exchange‐split core levels, such as the L₃‐edge of 3d transition metals.     

Upgrade of beamline BL08B at Taiwan Light Source from a photon‐BPM to a double‐grating SGM beamline

During the last 20 years, beamline BL08B has been upgraded step by step from a photon beam‐position monitor (BPM) to a testing beamline and a single‐grating beamline that enables experiments to record X‐ray photo‐emission spectra (XPS) and X‐ray absorption spectra (XAS) for research in solar physics, organic semiconductor materials and spinel oxides, with soft X‐ray photon energies in the range 300–1000 eV. Demands for photon energy to extend to the extreme ultraviolet region for applications in nano‐fabrication and topological thin films are increasing. The basic spherical‐grating monochromator beamline was again upgraded by adding a second grating that delivers photons of energy from 80 to 420 eV. Four end‐stations were designed for experiments with XPS, XAS, interstellar photoprocess systems (IPS) and extreme‐ultraviolet lithography (EUVL) in the scheduled beam time. The data from these experiments show a large count rate in core levels probed and excellent statistics on background normalization in the L‐edge adsorption spectrum.     

Soft X‐ray absorption spectroscopy and resonant inelastic X‐ray scattering spectroscopy below 100 eV: probing first‐row transition‐metal M‐edges in chemical complexes

X‐ray absorption and scattering spectroscopies involving the 3d transition‐metal K‐ and L‐edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M‐edges, which are below 100 eV. Synchrotron‐based X‐ray sources can have higher energy resolution at M‐edges. M‐edge X‐ray absorption spectroscopy (XAS) and resonant inelastic X‐ray scattering (RIXS) could therefore provide complementary information to K‐ and L‐edge spectroscopies. In this study, M_2,3‐edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M_2,3‐edge RIXS on NiO, NiF₂ and two other covalent complexes have been performed and different d–d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M‐edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high‐sensitivity and high‐resolution superconducting tunnel junction X‐ray detectors below 100 eV is also illustrated and discussed.     

Extended X‐ray absorption fine structure and multiple‐scattering simulation of nickel dithiolene complexes Ni[S2C2(CF3)2]2n (n = −2, −1, 0) and an olefin adduct Ni[S2C2(CF3)2]2(1‐hexene)

A series of Ni dithiolene complexes Ni[S₂C₂(CF₃)]₂ⁿ (n = ?2, ?1, 0) ( 1 , 2 , 3 ) and a 1‐hexene adduct Ni[S₂C₂(CF₃)₂]₂(C₆H₁₂) ( 4 ) have been examined by Ni K‐edge X‐ray absorption near‐edge structure (XANES) and extended X‐ray absorption fine‐structure (EXAFS) spectroscopies. Ni XANES for 1 – 3 reveals clear pre‐edge features and approximately +0.7 eV shift in the Ni K‐edge position for `one‐electron' oxidation. EXAFS simulation shows that the Ni—S bond distances for 1 , 2 and 3 (2.11–2.16 Å) are within the typical values for square planar complexes and decrease by ～0.022 Å for each `one‐electron' oxidation. The changes in Ni K‐edge energy positions and Ni—S distances are consistent with the `non‐innocent' character of the dithiolene ligand. The Ni—C interactions at ～3.0 Å are analyzed and the multiple‐scattering parameters are also determined, leading to a better simulation for the overall EXAFS spectra. The 1‐hexene adduct 4 presents no pre‐edge feature, and its Ni K‐edge position shifts by ?0.8 eV in comparison with its starting dithiolene complex 3 . Consistently, EXAFS also showed that the Ni—S distances in 4 elongate by ～0.046 Å in comparison with 3 . The evidence confirms that the neutral complex is `reduced' upon addition of olefin, presumably by olefin donating the π‐electron density to the LUMO of 3 as suggested by UV/visible spectroscopy in the literature.     

Electronic structure effects on B K‐edge XANES of minerals

In order to assess the usability of X‐ray absorption near‐edge structure (XANES) for studying the structure of BO_n‐containing materials, the dependence of theoretical XANES at the B K‐edge on the way the scattering potential is constructed is investigated. Real‐space multiple‐scattering calculations are performed for self‐consistent and non‐self‐consistent potentials and for different ways of dealing with the core hole. It is found that in order to reproduce the principal XANES features it is sufficient to use a non‐self‐consistent potential with a relaxed and screened core hole. Employing theoretical modelling of XANES for studying the structure of boron‐containing glasses is thus possible. The core hole affects the spectrum significantly, especially in the pre‐edge region. In contrast to minerals, B K‐edge XANES of BPO₄ can be reproduced only if a self‐consistent potential is employed.     

Thickness and angular dependence of the L‐edge X‐ray absorption of nickel thin films

We report on the near‐edge X‐ray absorption fine structure spectroscopy of the L₃ (2p_3/2) and L₂ (2p_1/2) edges for ferromagnetic pure nickel transition metal and show that the L_2,3 edge peak intensity and satellite feature at ~6 eV above the L₃ edge in nickel increase with increasing nickel film thickness both in the total electron yield and transmission modes. The absorption spectra of nickel metal, however, exhibit strong angular‐dependent effects when measured in total electron yield mode. In addition, we calculated the mean electron escape depth of the emitted electrons (λ_e), which was found for pure nickel metal to be λ_e=25 ± 2 Å. We point out the advantages of the total electron yield technique for the study of the L‐edge of 3d transition metals. Copyright © 2011 John Wiley & Sons, Ltd.     

Magnesium K‐edge XANES spectroscopy of geological standards

Magnesium K‐edge X‐ray absorption near‐edge structure (XANES) spectra have been investigated to develop a systematic understanding of a suite of Mg‐bearing geological materials such as silicate and carbonate minerals, sediments, rocks and chemical reagents. For the model compounds the Mg XANES was found to vary widely between compounds and to provide a fingerprint for the form of Mg involved in geologic materials. The energy positions and resonance features obtained from these spectra can be used to specify the dominant molecular host site of Mg, thus shedding light on Mg partitioning and isotope fractionation in geologic materials and providing a valuable complement to existing knowledge of Mg geochemistry.     

The unoccupied electronic structure characterization of hydrothermally grown ThO2 single crystals

Single crystals of thorium dioxide ThO₂, grown by the hydrothermal growth technique, have been investigated by ultraviolet photoemission spectroscopy (UPS), inverse photoemission spectroscopy (IPES), and L₃, M₃, M₄, and M₅ X‐ray absorption near edge spectroscopy (XANES). The experimental band gap for large single crystals has been determined to be 6 eV to 7 eV, from UPS and IPES, in line with expectations. The combined UPS and IPES, place the Fermi level near the conduction band minimum, making these crystals n‐type, with extensive band tailing, suggesting an optical gap in the region of 4.8 eV for excitations from occupied to unoccupied edge states. Hybridization between the Th 6d/5f bands with O 2p is strongly implicated. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Early commissioning results for spectroscopic X‐ray Nano‐Imaging Beamline BL 7C sXNI at PLS‐II

For spectral imaging of chemical distributions using X‐ray absorption near‐edge structure (XANES) spectra, a modified double‐crystal monochromator, a focusing plane mirrors system and a newly developed fluorescence‐type X‐ray beam‐position monitoring and feedback system have been implemented. This major hardware upgrade provides a sufficiently stable X‐ray source during energy scanning of more than hundreds of eV for acquisition of reliable XANES spectra in two‐dimensional and three‐dimensional images. In recent pilot studies discussed in this paper, heavy‐metal uptake by plant roots in vivo and iron's phase distribution in the lithium–iron–phosphate cathode of a lithium‐ion battery have been imaged. Also, the spatial resolution of computed tomography has been improved from 70 nm to 55 nm by means of run‐out correction and application of a reconstruction algorithm.     

Electronic excitations and luminescence of SrMgF4 single crystals

The electronic and crystal structures of SrMgF₄ single crystals grown by the Bridgman method have been investigated. The undoped SrMgF₄ single crystals have been studied using low-temperature (T = 10 K) time-resolved fluorescence optical and vacuum ultraviolet spectroscopy under selective excitation by synchrotron radiation (3.7–36.0 eV). Based on the measured reflectivity spectra and calculated spectra of the optical constants, the following parameters of the electronic structure have been determined for the first time: the minimum energy of interband transitions E _g = 12.55 eV, the position of the first exciton peak E _n = 1 = 11.37 eV, the position of the maximum of the “exciton” luminescence excitation band at 10.7 eV, and the position of the fundamental absorption edge at 10.3 eV. It has been found that photoluminescence excitation occurs predominantly in the region of the low-energy fundamental absorption edge of the crystal and that, at energies above E _g , the energy transfer from the matrix to luminescence centers is inefficient. The exciton migration is the main excitation channel of photoluminescence bands at 2.6–3.3 and 3.3–4.2 eV. The direct photoexcitation is characteristic of photoluminescence from defects at 1.8–2.6 and 4.2–5.5 eV.     

Disentanglement of magnetic contributions in multi‐component systems by using X‐ray magnetic circular dichroism at a single absorption edge

X‐ray magnetic circular dichroism (XMCD) has become in recent years an outstanding tool for studying magnetism. Its element specificity, inherent to core‐level spectroscopy, combined with the application of magneto‐optical sum rules allows quantitative magnetic measurements at the atomic level. These capabilities are now incorporated as a standard tool for studying the localized magnetism in many systems. However, the application of XMCD to the study of the conduction‐band magnetism is not so straightforward. Here, it is shown that the atomic selectivity is not lost when XMCD probes the delocalized states. On the contrary, it provides a direct way of disentangling the magnetic contributions to the conduction band coming from the different elements in the material. This is demonstrated by monitoring the temperature dependence of the XMCD spectra recorded at the rare‐earth L₂‐edge in the case of RT₂ (R = rare‐earth, T = 3d transition metal) materials. These results open the possibility of performing element‐specific magnetometry by using a single X‐ray absorption edge.     

Improved charge transfer multiplet method to simulate M‐ and L‐edge X‐ray absorption spectra of metal‐centered excited states

Charge transfer multiplet (CTM) theory is a computationally undemanding and highly mature method for simulating the soft X‐ray spectra of first‐row transition metal complexes. However, CTM theory has seldom been applied to the simulation of excited‐state spectra. In this article, the CTM4XAS software package is extended to simulate M_2,3‐ and L_2,3‐edge spectra for the excited states of first‐row transition metals and also interpret CTM eigenfunctions in terms of Russell–Saunders term symbols. These new programs are used to reinterpret the recently reported excited‐state M_2,3‐edge difference spectra of photogenerated ferrocenium cations and to propose alternative assignments for the electronic state of these cations responsible for the spectroscopic features. These new programs were also used to model the L_2,3‐edge spectra of Fe^II compounds during nuclear relaxation following photoinduced spin crossover and to propose spectroscopic signatures for their vibrationally hot states.     

X‐ray fluorescence induced by standing waves in the grazing‐incidence and grazing‐exit modes: study of the Mg–Co–Zr system

The characterization of Mg–Co–Zr tri‐layer stacks using X‐ray fluorescence induced by X‐ray standing waves, in both the grazing‐incidence (GI) and the grazing‐exit (GE) modes, is presented. The introduction of a slit in the direction of the detector improves the angular resolution by a factor of two and significantly improves the sensitivity of the technique for the chemical characterization of the buried interfaces. By observing the intensity variations of the Mg Kα and Co Lα characteristic emissions as a function of the incident (GI mode) or detection (GE mode) angle, it is shown that the interfaces of the Si/[Mg/Co/Zr]_×30 multilayer are abrupt, whereas in the Si/[Mg/Zr/Co]_×30 multilayer a strong intermixing occurs at the Co‐on‐Zr interfaces. An explanation of this opposite behavior of the Co‐on‐Zr and Zr‐on‐Co interfaces is given by the calculation of the mixing enthalpies of the Co–Mg, Co–Zr and Mg–Zr systems, which shows that the Co–Zr system presents a negative value and the other two systems present positive values. Together with the difference of the surface free energies of Zr and Co, this leads to the Mg/Zr/Co system being considered as a Mg/Co_xZr_y bi‐layer stack, with x/y estimated around 3.5.     

First-principles study of the optical properties of PbTiO<Subscript>3</Subscript>

The optical properties of PbTiO₃ were studied from first principles using the density functional theory. The dielectric functions and optical constants are calculated using the full potential–linearized augmented plane wave (FP-LAPW) method with the generalized gradient approximation (GGA). The theoretical calculated optical properties and energy loss (EEL) spectrum yield a static refractive index of 2.83 and a plasmon energy of 23.1 eV for cubic phase. The effective electron number at low energy saturates near 20 eV with the value of 18.1 for the effective electron number. In the tetragonal phase the static refractive index decreases to 2.59 and yields a plasmon energy of 22.7 eV.     

Carbon contamination of soft X‐ray beamlines: dramatic anti‐reflection coating effects observed in the 1 keV photon energy region

Carbon contamination is a general problem of under‐vacuum optics submitted to high fluence. In soft X‐ray beamlines carbon deposit on optics is known to absorb and scatter radiation close to the C K‐edge (280 eV), forbidding effective measurements in this spectral region. Here the observation of strong reflectivity losses is reported related to carbon deposition at much higher energies around 1000 eV, where carbon absorptivity is small. It is shown that the observed effect can be modelled as a destructive interference from a homogeneous carbon thin film.     

Temperature dependence of pre‐edge features in Ti K‐edge XANES spectra for ATiO3 (A = Ca and Sr), A2TiO4 (A = Mg and Fe), TiO2 rutile and TiO2 anatase

XANES (X‐ray absorption near‐edge structure) spectra of the Ti K‐edges of ATiO₃ (A = Ca and Sr), A₂TiO₄ (A = Mg and Fe), TiO₂ rutile and TiO₂ anatase were measured in the temperature range 20–900 K. Ti atoms for all samples were located in TiO₆ octahedral sites. The absorption intensity invariant point (AIIP) was found to be between the pre‐edge and post‐edge. After the AIIP, amplitudes damped due to Debye–Waller factor effects with temperature. Amplitudes in the pre‐edge region increased with temperature normally by thermal vibration. Use of the AIIP peak intensity as a standard point enables a quantitative comparison of the intensity of the pre‐edge peaks in various titanium compounds over a wide temperature range.