Measurement of relative line intensities for L‐shell X‐rays from selected elements between Z = 68 (Er) and Z = 79 (Au)

Relative line intensities of L1, L2 and L3 sub‐shell X‐rays were measured for Er, Tm, Yb, Hf, Ta, W, Pt and Au. The L‐shell X‐ray spectra were recorded by exciting pure element samples (eight cases) and oxide samples (two cases) with approximately 17‐keV exciting radiation from a filtered X‐ray tube source, and measuring the fluorescence spectra with a silicon drift detector. The spectra were carefully fitted to determine line energies and intensities, accounting for Lorentzian line broadening, incomplete charge collection and escape effects. A Monte Carlo approach was used to calculate attenuation and detector efficiency corrections. We report up to 15 line intensity ratios for each element and compare these to Scofield's theoretical predictions and Elam's extrapolated experimental database. Our measured relative line intensities agree best with Elam's data, but overall we find significant discrepancies with previously reported results. For the element Ta, we also find significant errors in the accepted L‐shell line energies in the widely used National Institute of Standard and Technology (NIST) database. Our results highlight the need for an experimental and theoretical re‐evaluation of L‐shell intensity databases to support high‐accuracy X‐ray analysis methods such as X‐ray fluorescence and particle‐induced X‐ray emission. Copyright © 2016 John Wiley & Sons, Ltd.     

A combined experimental and theoretical approach to determine X‐ray atomic fundamental quantities of tin

The knowledge of atomic fundamental parameters, such as the mass attenuation coefficients or fluorescence yields with low uncertainties, is of decisive importance in elemental quantification involving X‐ray fluorescence analysis techniques. For example, several databases giving the mass attenuation coefficients are accessible and frequently used within a large community of users. These compilations are most often in good agreement for photon energies in the hard X‐ray ranges. However, they significantly differ for low photon energies and around the absorption edges of the elements. In the case of the fluorescence yields, some authors made a review of measured values found in the literature. However, reliable measurements are not so many illustrating the inherent difficulties. Mass attenuation coefficients of tin were determined experimentally in the photon energy range from 100 eV to 35 keV by using monochromatized synchrotron radiation at SOLEIL (France). The fluorescence yields of the 3 L‐subshells of tin were also determined using a reflection geometry setup and the X‐ray fluorescence setup of Physikalisch‐Technische Bundesanstalt. The Coster–Kronig factors for the tin L‐shells were also experimentally determined. The application of high‐accuracy experimental techniques resulted in low uncertainty mass attenuation coefficients and L‐subshell fluorescence yields that are directly compared with existing databases and with updated relativistic configuration mixing Dirac–Fock calculations including Quantum electrodynamics (QED) corrections.     

Cascade Mi (i = 1–5) subshell X‐ray emission at incident photon energies across the Lj (j = 1–3) subshell absorption edges of 66Dy

The total M shell and the M_k (k = ξ, αβ, γ, m) X‐ray production cross sections for ₆₆Dy have been measured at incident photon energies across its L_j (j = 1–3) subshell absorption edge energies, ranging 7.8–9.2 keV. This study aims to investigate the evolution of the probability for cascade decay of L_j subshell vacancies as the tunable incident energy ionizes progressively different ₆₆Dy L_j subshells. The experimental X‐ray production cross sections have been compared with theoretical ones calculated using the nonrelativistic Hartree–Fock–Slater (HFS) model‐based photoionization cross sections; three sets of the X‐ray emission rates, fluorescence and Coster–Kronig yield based on the nonrelativistic Hartree–Slater (NRHS) model, Dirac–Hartree–Slater (DHS) model and Dirac–Fock (DF) model; the L_j (j = 1–3) subshell to the M_i (i = 1–5) subshell vacancy transfer probabilities evaluated in the present work. Presently measured total M shell and the M_αβ X‐ray production cross sections are found to be significantly lower than the theoretical ones evaluated using physical parameters based on the relativistic Dirac–Fock/Dirac–Hartree–Slater model calculations, whereas a much better agreement is observed with respect to the NRHS model‐based calculations; however, the measured X‐ray production cross sections are still systematically lower than the NRHS values.     

Generation of experimental L x‐ray fluorescence cross‐sections for inter‐elements at inter‐energies EL1 ≤ E ≤ EK (computer program IGELCS)

The experimental values of L x‐ray fluorescence (XRF) cross‐sections are not available for all the elements in the range La–U, at all the photon energies E in the range EL1 ≤ E ≤ EK. To generate L XRF cross‐sections, where experimental measurements are not available, two empirical relations have been developed, one between the L XRF cross‐sections and photon energy and the other between the L XRF cross‐sections and atomic number. For the measured data on L XRF cross‐sections at incident energies between Ll and K edges of an element and the data on L XRF cross‐sections for elements in the range 57 ≤ Z ≤ 92 at an energy value, polynomial fits have been derived. The L XRF cross‐section values generated with the derived empirical relations were found to be in agreement with the experimental values within their experimental uncertainties. Subsequently, a software code IGELCS was developed to interpolate and to generate the cross‐sections at inter‐energies and for inter‐elements in a single computer run. The running of the software requires minimum input data on five elements at five common energies. Copyright © 2003 John Wiley & Sons, Ltd.     

Optimization of L‐shell X‐ray fluorescence detection of lead in bone phantoms using synchrotron radiation

Closely related toxicity and retention mechanisms of lead (Pb) in the human body involve the bone tissues where Pb can accumulate and reside on a time scale ranging from years to tens of years. In vivo measurements of bone Pb can, therefore, play an important role in a comprehensive health risk assessment of Pb exposure. In vivo L‐shell X‐ray fluorescence (LXRF) measurement of bone Pb was first demonstrated over 4 decades ago. Implementation of the method, however, encountered challenges associated with low sensitivity and calibration procedure. In this study, the LXRF measurement was optimized by varying the incident photon energy and the excitation‐detection geometry. The Canadian Light Source synchrotron radiation was used to compare 2 different excitation‐detection geometries of 90^° and 135^° using 3 different X‐ray photon energies: 15.8, 16.6, and 17.5 keV. These energies optimized excitation of the L₃ subshell of Pb and simulated the most intense K‐shell emissions of zirconium, niobium, and molybdenum, respectively. Five rectangular plaster‐of‐Paris bone phantoms with Pb concentrations of 0, 7, 17, 26, and 34 μg/g, and one rectangular 3.1‐mm‐thick resin phantom mimicked the X‐ray attenuation properties of human bone and soft tissue, respectively. Optimal LXRF detection was obtained by the 15.8‐keV energy and the 90^° and 135^° geometries for the bare bone and the bone and soft tissue phantoms, respectively.     

What are the correct L‐subshell photoionization cross sections for quantitative X‐ray spectroscopy?

For fundamental parameter‐based, quantitative X‐ray fluorescence, X‐ray photoelectron spectroscopy or Auger electron spectroscopy, it is crucial to accurately know the photoionization cross sections (PCS). This atomic probability to absorb the exciting photon and eject a photoelectron, in general, followed by a subsequent decay resulting in the emission of a fluorescence photon or an Auger electron, strongly depends on the electron configuration and photon energy. Two contrary models for the photon energy dependence of the L‐subshell PCS, or the 2s, 2p ½ and 2p 3/2; energy levels, respectively, exist in the literature, and an experimental verification was not available until recently. In this work, the two models for calculating the PCS are discussed, and their influence on quantitative experiments is demonstrated by means of the fluorescence production cross sections for the three L shells. Depending on the excitation conditions, these fluorescence production cross sections and, thus, the derived quantitative results can differ significantly if the wrong PCS model is employed. Copyright © 2016 John Wiley & Sons, Ltd.     

Influence of different mass absorption coefficient datasets on PIXE yields

Tabulated mass absorption coefficient data from the XCOM, Chantler and ion beam analysis (IBA) Handbook are compared, and differences are shown against X‐ray energy and target atomic number. Over the X‐ray energy range 1–40 keV systematic differences of several tens of percent are noted between these datasets, particularly for the earlier IBA Handbook dataset. The influence of these different mass absorption coefficients on the X‐ray yields for thick target proton‐induced X‐ray emission (PIXE) are investigated and compared as a function of X‐ray energy and target atomic number. For contemporary experimental PIXE users trying to work quantitatively over a broad range of elements and X‐ray energies, differences between PIXE results obtained using these three separate mass attenuation coefficient datasets can be larger than the typical accuracy limits of ±3% to ±5%. There are systematic differences in the mass attenuation coefficients of 5–10% between the XCOM and Chantler, while the differences for the IBA Handbook dataset can be larger (up to 40% and greater) at high X‐ray energies. At this time, we recommend the dataset of Chantler as it is more recent, and the synchrotron experimental results seem to favour it over the older XCOM and IBA Handbook data. Copyright © 2013 John Wiley & Sons, Ltd.     

Measuring partial fluorescence yield using filtered detectors

Typically, X‐ray absorption near‐edge structure measurements aim to probe the linear attenuation coefficient. These measurements are often carried out using partial fluorescence yield techniques that rely on detectors having photon energy discrimination improving the sensitivity and the signal‐to‐background ratio of the measured spectra. However, measuring the partial fluorescence yield in the soft X‐ray regime with reasonable efficiency requires solid‐state detectors, which have limitations due to the inherent dead‐time while measuring. Alternatively, many of the available detectors that are not energy dispersive do not suffer from photon count rate limitations. A filter placed in front of one of these detectors will make the energy‐dependent efficiency non‐linear, thereby changing the responsivity of the detector. It is shown that using an array of filtered X‐ray detectors is a viable method for measuring soft X‐ray partial fluorescence yield spectra without dead‐time. The feasibility of this technique is further demonstrated using α‐Fe₂O₃ as an example and it is shown that this detector technology could vastly improve the photon collection efficiency at synchrotrons and that these detectors will allow experiments to be completed with a much lower photon flux reducing X‐ray‐induced damage.     

Physical parameters for atomic inner‐shell photoionization processes and analytical applications: a status report

The atomic inner‐shell vacancy decay processes comprising of radiative and non‐radiative transitions are characterized by the physical parameters, namely, the photoionization cross‐sections; X‐ray, Auger and Coster–Kronig (CK) transition rates; fluorescence and CK yields; and the vacancy transfer probabilities. These parameters are required to calculate the K‐shell and L_i (i = 1–3)/M_i (i = 1–5) sub‐shell X‐ray production cross‐sections and relative intensities which, in turn, are needed for different analytical applications. This report intended to provide a detailed account of the currently available data sets of different physical parameters for use in various analytical applications. Copyright © 2011 John Wiley & Sons, Ltd.     

X‐ray photon correlation spectroscopy under flow

X‐ray photon correlation spectroscopy was used to probe the diffusive dynamics of colloidal particles in a shear flow. Combining X‐ray techniques with microfluidics is an experimental strategy that reduces the risk of X‐ray‐induced beam damage and also allows time‐resolved studies of processes taking place in flow cells. The experimental results and theoretical predictions presented here show that in the low shear limit for a `transverse flow' scattering geometry (scattering wavevector q perpendicular to the direction of flow) the measured relaxation times are independent of the flow rate and determined only by the diffusive motion of the particles. This is not generally valid and, in particular, for a `longitudinal flow' ( q ∥ flow) scattering geometry the relaxation times are strongly affected by the flow‐induced motion of the particles. The results here show that the Brownian diffusion of colloidal particles can be measured in a flowing sample and that, up to flux limitations, the experimental conditions under which this is possible are easier to achieve at higher values of q.     

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.     

Differential phase contrast with a segmented detector in a scanning X‐ray microprobe

Scanning X‐ray microprobes are unique tools for the nanoscale investigation of specimens from the life, environmental, materials and other fields of sciences. Typically they utilize absorption and fluorescence as contrast mechanisms. Phase contrast is a complementary technique that can provide strong contrast with reduced radiation dose for weakly absorbing structures in the multi‐keV range. In this paper the development of a segmented charge‐integrating silicon detector which provides simultaneous absorption and differential phase contrast is reported. The detector can be used together with a fluorescence detector for the simultaneous acquisition of transmission and fluorescence data. It can be used over a wide range of photon energies, photon rates and exposure times at third‐generation synchrotron radiation sources, and is currently operating at two beamlines at the Advanced Photon Source. Images obtained at around 2 keV and 10 keV demonstrate the superiority of phase contrast over absorption for specimens composed of light elements.     

The materials science X‐ray beamline BL8 at the DELTA storage ring

The hard X‐ray beamline BL8 at the superconducting asymmetric wiggler at the 1.5 GeV Dortmund Electron Accelerator DELTA is described. This beamline is dedicated to X‐ray studies in the spectral range from ～1 keV to ～25 keV photon energy. The monochromator as well as the other optical components of the beamline are optimized accordingly. The endstation comprises a six‐axis diffractometer that is capable of carrying heavy loads related to non‐ambient sample environments such as, for example, ultrahigh‐vacuum systems, high‐pressure cells or liquid‐helium cryostats. X‐ray absorption spectra from several reference compounds illustrate the performance. Besides transmission measurements, fluorescence detection for dilute sample systems as well as surface‐sensitive reflection‐mode experiments have been performed. The results show that high‐quality EXAFS data can be obtained in the quick‐scanning EXAFS mode within a few seconds of acquisition time, enabling time‐resolved in situ experiments using standard beamline equipment that is permanently available. The performance of the new beamline, especially in terms of the photon flux and energy resolution, is competitive with other insertion‐device beamlines worldwide, and several sophisticated experiments including surface‐sensitive EXAFS experiments are feasible.     

Soft‐X‐ray ARPES facility at the ADRESS beamline of the SLS: concepts,technical realisation and scientific applications

Soft‐X‐ray angle‐resolved photoelectron spectroscopy (ARPES) with photon energies around 1 keV combines the momentum space resolution with increasing probing depth. The concepts and technical realisation of the new soft‐X‐ray ARPES endstation at the ADRESS beamline of SLS are described. The experimental geometry of the endstation is characterized by grazing X‐ray incidence on the sample to increase the photoyield and vertical orientation of the measurement plane. The vacuum chambers adopt a radial layout allowing most efficient sample transfer. High accuracy of the angular resolution is ensured by alignment strategies focused on precise matching of the X‐ray beam and optical axis of the analyzer. The high photon flux of up to 10¹³ photons s^?1 (0.01% bandwidth)^?1 delivered by the beamline combined with the optimized experimental geometry break through the dramatic loss of the valence band photoexcitation cross section at soft‐X‐ray energies. ARPES images with energy resolution up to a few tens of meV are typically acquired on the time scale of minutes. A few application examples illustrate the power of our advanced soft‐X‐ray ARPES instrumentation to explore the electronic structure of bulk crystals with resolution in three‐dimensional momentum, access buried heterostructures and study elemental composition of the valence states using resonant excitation.     

Can the HVL help the mechanical X‐ray tube characterization?

High‐intensity X‐ray beams are usually characterized by their kVp (kilovoltage peak) value and half‐value layer (HVL). While the first parameter is reasonably well known (apart from accelerating potential fluctuations), on the second, there is a greater deal of uncertainty. The HVL depends on the used filtration, the effective kVp value and on some of the X‐ray tube mechanical features, such as the anode angle. This last parameter is not always provided by the tube manufacturer, so we may question if the HVL dependence on the anode angle can be used to extract information on this angle. We tried to give an answer to this question using two different numerical models and a full Monte Carlo (MC) program to simulate the photon field produced by the X‐ray tube for several anode angles. One of the numerical models was developed by the Institute of Physics and Engineering in Medicine and gives X‐ray spectra and HVL values for a wide range of kVp values and anode angles. The other model, named SpekCalc, is based on a theoretical work developed by Gavin Poludniowski and Phil Evans. The MC simulation was done using the PENELOPE code for coupled electron‐photon transport. Using the computed photon spectra, HVLs were obtained and compared with experimental HVL values obtained with a Philips PW 2184/00 X‐ray tube with a 26° tungsten anode and accelerating potentials in the range of 40–90 kVp. We are now able to show the PENELOPE simulation can deliver the correct anode angle value. Copyright © 2011 John Wiley & Sons, Ltd.     

An accurate determination of the K‐shell X‐ray fluorescence yield of silicon

A measurement of the K‐shell fluorescence yield of silicon is undertaken in which identified sources of systematic errors in previous measurements are reduced or eliminated. This enables a stringent test of the only two sets of theoretical predictions available for atomic numbers less than 18. Our result ω_K = 0.0495 ± 0.0015 is very slightly lower than the non‐relativistic Hartree‐Fock‐Slater (HFS) prediction of 0.0514. This stringent test of the HFS predictions helps to refine the fundamental parameter database of the X‐ray fluorescence analysis technique, whose importance for light elements is increasing. Our work indicates the need for new theoretical calculations of K‐shell fluorescence yields for these elements. Copyright © 2012 John Wiley & Sons, Ltd.     

XDS: a flexible beamline for X‐ray diffraction and spectroscopy at the Brazilian synchrotron

The majority of the beamlines at the Brazilian Synchrotron Light Source Laboratory (LNLS) use radiation produced in the storage‐ring bending magnets and are therefore currently limited in the flux that can be used in the harder part of the X‐ray spectrum (above ～10 keV). A 4 T superconducting multipolar wiggler (SCW) was recently installed at LNLS in order to improve the photon flux above 10 keV and fulfill the demands set by the materials science community. A new multi‐purpose beamline was then installed at the LNLS using the SCW as a photon source. The XDS is a flexible beamline operating in the energy range between 5 and 30 keV, designed to perform experiments using absorption, diffraction and scattering techniques. Most of the work performed at the XDS beamline concentrates on X‐ray absorption spectroscopy at energies above 18 keV and high‐resolution diffraction experiments. More recently, new setups and photon‐hungry experiments such as total X‐ray scattering, X‐ray diffraction under high pressures, resonant X‐ray emission spectroscopy, among others, have started to become routine at XDS. Here, the XDS beamline characteristics, performance and a few new experimental possibilities are described.     

Improved Rayleigh to Compton scattering ratio curves for mass attenuation coefficients determination for X‐ray fluorescence analysis

Nondestructive assays are essentials for certain types of sample materials, and, among those, the X‐ray fluorescence technique enables the determinations of stable elements, and there is an increasing effort on the development of equipment to suit the various needs. Nevertheless, a great difficulty on the analysis of unknown materials' composition is to account for self‐absorption of the fluorescence photons that must be considered in the elemental concentration calculation. The correlation between the Rayleigh to Compton scattering ratio to the mass attenuation coefficient has proved to follow a single polynomial function for the first 20 elements of the periodical table with a correlation factor higher than of 0.998 for the sixth order function. The Rayleigh to Compton scattering ratios for pure elements and the 22.16 keV photons, the main energy from an X‐ray tube with silver anode, were determined with the MCNP6 Monte Carlo computer code. Two scattering angles were considered. Reference samples were measured, and the calculated results were compared to the literature values of the mass attenuation coefficient for some known samples and showed to be within 20% for de 90° scattering angle. Only Lucite was slightly above 20%. Curve fit coefficients are also presented for the 7.11‐ and 17.40‐keV photon energies.     

A study of KαL1 X‐ray satellite spectrum of the elements 27 ≤ Z ≤ 31 by photon excitation

K _α X‐ray satellite spectra of Co, Ni, Cu, Zn, and Ga generated by photon excitation are analyzed using a wavelength dispersion spectrometer. Spectra of Ni, Cu, Zn, and Ga are studied for the first time using a LiF420 crystal. Spectrum of Co was studied with LiF200 crystal in second order. K_αL¹ X‐ray satellite energies and relative intensities are measured. The energy shifts relative to diagram line are computed and are compared with theoretical and semi‐empirical values. Dependence of energy shifts and relative intensities on Z and mode of excitation is analyzed.