Validation and traceability of XRF and SEM‐EDS elemental analysis results for solder in high‐reliability applications

A procedure and calibration samples were developed for X‐ray fluorescence spectrometry and scanning electron microscopy (SEM) with energy dispersive spectrometry (EDS) analysis methods for Sn and Pb amounts in solder and coatings. Test methods are needed by laboratories that perform destructive physical analysis of high‐reliability electronics for MIL‐STD‐1580B. Calibrants are prepared by evaporative deposition of multiple, alternating quantities of pure Sn and pure Pb having mass per unit area proportional to mass fractions of Sn and Pb in a solder being mimicked. Validation reference materials are prepared by evaporative deposition of thin films of SRM 1729 Tin Alloy (97Sn–3Pb). Films are created on high‐purity Ni foil to mimic some actual electronics structures and prevent charging during SEM‐EDS measurements. Maximum thickness of films prepared this way must be kept below approximately 1 µm to ensure that the entire thickness is probed by the primary X‐ray or electron beam and that measured X‐rays come from the entire thickness of all films. Detailed procedures are presented, and method performance was characterized. The primary purpose is to create calibrations for Sn and Pb that are simple to implement and establish traceability to the international system of units. The secondary purpose is to validate calibrations using a certified reference material to prove that, for simpler structures of thin solder coatings on metal, both X‐ray fluorescence and SEM‐EDS provide accurate results. Keeping films thin may be unrealistic in comparison with some, if not many, electronic structures, but this approach enables a laboratory to demonstrate competence in a controlled manner. Copyright © 2014 John Wiley & Sons, Ltd.     

3D imaging of a rice pollen grain using transmission X‐ray microscopy

For the first time, the three‐dimensional (3D) ultrastructure of an intact rice pollen cell has been obtained using a full‐field transmission hard X‐ray microscope operated in Zernike phase contrast mode. After reconstruction and segmentation from a series of projection images, complete 3D structural information of a 35 µm rice pollen grain is presented at a resolution of ～100 nm. The reconstruction allows a clear differentiation of various subcellular structures within the rice pollen grain, including aperture, lipid body, mitochondrion, nucleus and vacuole. Furthermore, quantitative information was obtained about the distribution of cytoplasmic organelles and the volume percentage of each kind of organelle. These results demonstrate that transmission X‐ray microscopy can be quite powerful for non‐destructive investigation of 3D structures of whole eukaryotic cells.     

MISTRAL: a transmission soft X‐ray microscopy beamline for cryo nano‐tomography of biological samples and magnetic domains imaging

The performance of MISTRAL is reported, the soft X‐ray transmission microscopy beamline at the ALBA light source (Barcelona, Spain) which is primarily dedicated to cryo soft X‐ray tomography (cryo‐SXT) for three‐dimensional visualization of whole unstained cells at spatial resolutions down to 30 nm (half pitch). Short acquisition times allowing for high‐throughput and correlative microscopy studies have promoted cryo‐SXT as an emerging cellular imaging tool for structural cell biologists bridging the gap between optical and electron microscopy. In addition, the beamline offers the possibility of imaging magnetic domains in thin magnetic films that are illustrated here with an example.     

Synchrotron microanalysis techniques applied to potential photovoltaic materials

X‐ray synchrotron radiation techniques are used to characterize photovoltaic‐related semiconductors. Micro‐X‐ray‐fluorescence and X‐ray beam induced current mapping of multicrystalline silicon photovoltaic cells show metallic impurities accumulating at the interface of crystallographic defects, and current variations over the cell that are attributed to bulk defects and structural variation of the silicon. Similarly, studies on a single‐crystal GaAs using X‐ray fluorescence and X‐ray excited optical luminescence show an inhomogeneous As distribution correlated with the photoluminescence signal, with higher As concentration regions having stronger photoluminescence signal. Both examples show how the combination of synchrotron microanalysis techniques can contribute to a better understanding of the optical properties of photovoltaic materials.     

Micro‐Raman innovative methodology to identify Ag–Cu mixed sulphides as tarnishing corrosion products

Mixed Cu–Ag alloys with different compositions have been produced and subjected to an accelerated sulphidation process which causes the development of a mixed sulphide‐rich corroded film on their surface. It was called tarnishing, that is, the formation of a blue‐brownish patina when Cu–Ag alloys are exposed in a sulfur‐containing atmosphere. The structures of the pristine alloys have been determined by the combined analytical techniques as scanning electron microscopy energy dispersive X‐ray microanalysis and X‐ray diffraction. The experimental conclusions confirmed the occurrence of micro phase separation with the formation of different dendritic domains of about 10 µm in width. The sulphidized samples were firstly investigated by optical microscopy and X‐ray diffraction in order to verify the homogeneity of the patina and to identify the different AgCuS phases appearing on the alloy surfaces. It was observed that, despite the inherent micro‐heterogeneity of the alloys, the sulphide layer was throughout uniform in composition at the micro‐scale. The complex scenario of the relative stability of all the various mixed sulphides involved was then explored by micro‐Raman spectroscopy (μ‐RS), pointing out that the Cu‐for‐Ag substitution in the crystal lattice of the mixed Ag–Cu sulphides caused a monotonous blue shift of the vibrational wavenumbers in Raman spectra. This study has unveiled microscopic details of the tarnishing process, furnishing an innovative, cheap and non‐destructive methodology based on μ‐Raman spectroscopy for the evaluation of the silver‐copper artefacts via the compositions of their corroded products. Copyright © 2016 John Wiley & Sons, Ltd.     

Investigation of nanoscale element distributions at surfaces with grazing incidence X‐ray spectroscopy techniques – an instrumentation study

Grazing incidence X‐ray methods are well‐established in the characterization of nanostructures at interfaces and surfaces. The purpose of the experiments reviewed in this work is the comparative characterization of different instrumentation concepts for grazing incidence X‐ray fluorescence analyses. Fluorescence scans recorded with a total reflection X‐ray fluorescence spectrometer featuring a variable angle of incidence are compared with data obtained with synchrotron radiation. The conclusions to the element distribution profiles, which are drawn from fluorescence scans carried out with the respective instrument, are compared. This way, the suitability of the total reflection X‐ray fluorescence spectrometer to complement synchrotron radiation facilities and the possibility to transfer surface and interface analyses from the synchrotron to the laboratory are assessed. The structures investigated include an Au on Si surfaces in the form of layers and particles, submicrometer‐sized droplets, a liquid film, and ions implanted into a Si wafer. Copyright © 2014 John Wiley & Sons, Ltd.     

Development of a single‐cell X‐ray fluorescence flow cytometer

An X‐ray fluorescence flow cytometer that can determine the total metal content of single cells has been developed. Capillary action or pressure was used to load cells into hydrophilic or hydrophobic capillaries, respectively. Once loaded, the cells were transported at a fixed vertical velocity past a focused X‐ray beam. X‐ray fluorescence was then used to determine the mass of metal in each cell. By making single‐cell measurements, the population heterogeneity for metals in the µM to mM concentration range on fL sample volumes can be directly measured, a measurement that is difficult using most analytical methods. This approach has been used to determine the metal composition of 936 individual bovine red blood cells (bRBC), 31 individual 3T3 mouse fibroblasts (NIH3T3) and 18 Saccharomyces cerevisiae (yeast) cells with an average measurement frequency of ～4 cells min^?1. These data show evidence for surprisingly broad metal distributions. Details of the device design, data analysis and opportunities for further sensitivity improvement are described.     

X‐ray spectromicroscopy in soil and environmental sciences

X‐ray microscopy is capable of imaging particles in the nanometer size range directly with sub‐micrometer spatial resolution and can be combined with high spectral resolution for spectromicroscopy studies. Two types of microscopes are common in X‐ray microscopy: the transmission X‐ray microscope and the scanning transmission X‐ray microscope; their set‐ups are explained in this paper. While the former takes high‐resolution images from an object with exposure times of seconds or faster, the latter is very well suited as an analytical instrument for spectromicroscopy. The morphology of clusters or particles from soil and sediment samples has been visualized using a transmission X‐ray microscope. Images are shown from a cryo‐tomography experiment based on X‐ray microscopy images to obtain information about the three‐dimensional structure of clusters of humic substances. The analysis of a stack of images taken with a scanning transmission X‐ray microscope to combine morphology and chemistry within a soil sample is shown. X‐ray fluorescence is a method ideally applicable to the study of elemental distributions and binding states of elements even on a trace level using X‐ray energies above 1 keV.     

Synchrotron‐based spectroscopy of X‐ray channeling through hollow capillary microchannels inside glass plates

Here, soft X‐ray synchrotron radiation transmitted through microchannel plates is studied experimentally. Fine structures of reflection and XANES Si L‐edge spectra detected on the exit of silicon glass microcapillary structures under conditions of total X‐ray reflection are presented and analyzed. The phenomenon of the interaction of channeling radiation with unoccupied electronic states and propagation of X‐ray fluorescence excited in the microchannels is revealed. Investigations of the interaction of monochromatic radiation with the inner‐shell capillary surface and propagation of fluorescence radiation through hollow glass capillary waveguides contribute to the development of novel X‐ray focusing devices in the future.     

Multivariate analysis of hyperspectral hard X‐ray images

This article describes methods to analyse and process hyperspectral hard X‐ray imaging data. We focus on the use of multivariate techniques that exploit the spectral information to make informed decisions on the material content within each pixel of an X‐ray image. These analysis methods have the ability to auto‐segment data without prior knowledge of the sample composition or structure, and are particularly useful for studying completely unknown, diluted or complex specimens. We demonstrate the methods on a variety of hard X‐ray images including X‐ray fluorescence and absorption data recorded using a hard X‐ray imaging spectrometer. The multivariate methods described are very powerful with the ability to segment, distinguish and, in some cases, identify different materials within a single X‐ray image. Potential uses of hyperspectral X‐ray imaging are discussed varying from materials science to industrial or security applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Quantitative phase retrieval in X‐ray Zernike phase contrast microscopy

In recent years, increasing attention has been devoted to X‐ray phase contrast imaging, since it can provide high‐contrast images by using phase variations. Among the different existing techniques, Zernike phase contrast microscopy is one of the most popular phase‐sensitive techniques for investigating the fine structure of the sample at high spatial resolution. In X‐ray Zernike phase contrast microscopy, the image contrast is indeed a mixture of absorption and phase contrast. Therefore, this technique just provides qualitative information on the object, which makes the interpretation of the image difficult. In this contribution, an approach is proposed for quantitative phase retrieval in X‐ray Zernike phase contrast microscopy. By shifting the phase of the direct light by π/2 and 3π/2, two images of the same object are measured successively. The phase information of the object can then be quantitatively retrieved by a proper combination of the measured images. Numerical experiments were carried out and the results confirmed the feasibility of the proposed method. It is expected that the proposed method will find widespread applications in biology, materials science and so on.     

Status of the hard X‐ray microprobe beamline ID22 of the European Synchrotron Radiation Facility

The ESRF synchrotron beamline ID22, dedicated to hard X‐ray microanalysis and consisting of the combination of X‐ray fluorescence, X‐ray absorption spectroscopy, diffraction and 2D/3D X‐ray imaging techniques, is one of the most versatile instruments in hard X‐ray microscopy science. This paper describes the present beamline characteristics, recent technical developments, as well as a few scientific examples from recent years of the beamline operation. The upgrade plans to adapt the beamline to the growing needs of the user community are briefly discussed.     

Quantitative determination of mineral phase effects observed in APXS analyses of geochemical reference materials

Calibration of the Curiosity Rover's alpha particle X‐ray spectrometer (APXS) was accomplished using geochemical reference materials and a fundamental parameters treatment of the X‐ray fluorescence and particle‐induced X‐ray emission (PIXE) excitation processes. For most major and minor elements the influence of different rock types was not significant. For the three light elements, Na, Mg, and Al, which are excited almost entirely by PIXE, systematic differences among felsic and mafic rocks were observed. A qualitative explanation is found in the very shallow interrogation depth (a few microns), which suggests that the X‐rays of these elements must emerge from a single mineral rather than an assumed average over the various minerals present. A quantitative explanation was sought by determining the mineralogy of several reference materials and computing their expected PIXE X‐ray yields with an adaptation of the yield prediction sub‐routine GUYLS in the Guelph PIXE software package GUPIX. The complexity of assigning the certified overall element mass fractions to specific minerals limited this exercise to cases with only a few minerals present. Good agreement was found between the X‐ray yields determined in the calibration exercise and those predicted in this new approach. It is expected that automation of the computational approach may enable examination of mineralogically more complex reference materials. This might also offer a means of coupling results from the X‐ray diffraction and APXS instruments on Mars. Copyright © 2014 John Wiley & Sons, Ltd.     

Current status of the TwinMic beamline at Elettra: a soft X‐ray transmission and emission microscopy station

The current status of the TwinMic beamline at Elettra synchrotron light source, that hosts the European twin X‐ray microscopy station, is reported. The X‐ray source, provided by a short hybrid undulator with source size and divergence intermediate between bending magnets and conventional undulators, is energy‐tailored using a collimated plane‐grating monochromator. The TwinMic spectromicroscopy experimental station combines scanning and full‐field imaging in a single instrument, with contrast modes such as absorption, differential phase, interference and darkfield. The implementation of coherent diffractive imaging modalities and ptychography is ongoing. Typically, scanning transmission X‐ray microscopy images are simultaneously collected in transmission and differential phase contrast and can be complemented by chemical and elemental analysis using across‐absorption‐edge imaging, X‐ray absorption near‐edge structure or low‐energy X‐ray fluorescence. The lateral resolutions depend on the particular imaging and contrast mode chosen. The TwinMic range of applications covers diverse research fields such as biology, biochemistry, medicine, pharmacology, environment, geochemistry, food, agriculture and materials science. They will be illustrated in the paper with representative results.     

Towards tender X‐rays with Zernike phase‐contrast imaging of biological samples at 50 nm resolution

X‐ray microscopy is a commonly used method especially in material science application, where the large penetration depth of X‐rays is necessary for three‐dimensional structural studies of thick specimens with high‐Z elements. In this paper it is shown that full‐field X‐ray microscopy at 6.2 keV can be utilized for imaging of biological specimens with high resolution. A full‐field Zernike phase‐contrast microscope based on diffractive optics is used to study lipid droplet formation in hepatoma cells. It is shown that the contrast of the images is comparable with that of electron microscopy, and even better contrast at tender X‐ray energies between 2.5 keV and 4 keV is expected.     

Fluorescence imaging of reactive oxygen species by confocal laser scanning microscopy for track analysis of synchrotron X‐ray photoelectric nanoradiator dose: X‐ray pump–optical probe

Bursts of emissions of low‐energy electrons, including interatomic Coulomb decay electrons and Auger electrons (0–1000 eV), as well as X‐ray fluorescence produced by irradiation of large‐Z element nanoparticles by either X‐ray photons or high‐energy ion beams, is referred to as the nanoradiator effect. In therapeutic applications, this effect can damage pathological tissues that selectively take up the nanoparticles. Herein, a new nanoradiator dosimetry method is presented that uses probes for reactive oxygen species (ROS) incorporated into three‐dimensional gels, on which macrophages containing iron oxide nanoparticles (IONs) are attached. This method, together with site‐specific irradiation of the intracellular nanoparticles from a microbeam of polychromatic synchrotron X‐rays (5–14 keV), measures the range and distribution of OH radicals produced by X‐ray emission or superoxide anions () produced by low‐energy electrons. The measurements are based on confocal laser scanning of the fluorescence of the hydroxyl radical probe 2‐[6‐(4′‐amino)phenoxy‐3H‐xanthen‐3‐on‐9‐yl] benzoic acid (APF) or the superoxide probe hydroethidine‐dihydroethidium (DHE) that was oxidized by each ROS, enabling tracking of the radiation dose emitted by the nanoradiator. In the range 70 µm below the irradiated cell, radicals derived mostly from either incident X‐ray or X‐ray fluorescence of ION nanoradiators are distributed along the line of depth direction in ROS gel. In contrast, derived from secondary electron or low‐energy electron emission by ION nanoradiators are scattered over the ROS gel. ROS fluorescence due to the ION nanoradiators was observed continuously to a depth of 1.5 mm for both oxidized APF and oxidized DHE with relatively large intensity compared with the fluorescence caused by the ROS produced solely by incident primary X‐rays, which was limited to a depth of 600 µm, suggesting dose enhancement as well as more penetration by nanoradiators. In conclusion, the combined use of a synchrotron X‐ray microbeam‐irradiated three‐dimensional ROS gel and confocal laser scanning fluorescence microscopy provides a simple dosimetry method for track analysis of X‐ray photoelectric nanoradiator radiation, suggesting extensive cellular damage with dose‐enhancement beyond a single cell containing IONs.     

The multi‐purpose hard X‐ray beamline BL10 at the DELTA storage ring

The layout and the characteristics of the hard X‐ray beamline BL10 at the superconducting asymmetric wiggler at the 1.5 GeV Dortmund Electron Accelerator DELTA are described. This beamline is equipped with a Si(111) channel‐cut monochromator and is dedicated to X‐ray studies in the spectral range from ～4 keV to ～16 keV photon energy. There are two different endstations available. While X‐ray absorption studies in different detection modes (transmission, fluorescence, reflectivity) can be performed on a designated table, a six‐axis kappa diffractometer is installed for X‐ray scattering and reflectivity experiments. Different detector set‐ups are integrated into the beamline control software, i.e. gas‐filled ionization chambers, different photodiodes, as well as a Pilatus 2D‐detector are permanently available. The performance of the beamline is illustrated by high‐quality X‐ray absorption spectra from several reference compounds. First applications include temperature‐dependent EXAFS experiments from liquid‐nitrogen temperature in a bath cryostat up to ～660 K by using a dedicated furnace. Besides transmission measurements, fluorescence detection for dilute sample systems as well as surface‐sensitive reflection‐mode experiments are presented.     

Non‐invasive approach in the study of polychrome terracotta sculptures: employment of the portable XRF to investigate complex stratigraphy

In the field of conservation science, in situ non‐invasive analytical techniques are widely used to investigate polychrome surfaces as frescoes, mural or easel paintings. Indeed, these techniques allow achieving information on materials composition and they often reduce the micro‐sampling. In this work, in situ non‐invasive techniques have been used to study a complex system, terracotta polychrome sculptures. The presence of the priming, the numerous painted layers and the ground layer spread on a porous material substrate are the main features of these sculptures; therefore, their study requires a scientific approach based on results obtained by different analytical techniques. In order to evaluate potentialities and limitations of the non‐invasive approach to this complex case, the results of energy‐dispersive X‐ray fluorescence (EDXRF), spectrophotometry and optical microscopy have been compared with the data achieved by laboratory analytical investigation as optical and scanning electron microscopy, energy‐dispersive X‐ray microanalysis and Raman spectroscopy. In particular, XRF data collected on several polychrome terracotta are here re‐examined on the basis of the results obtained by laboratory techniques. Even if, in some cases, portable XRF may induce to a wrong interpretation of the stratigraphy, it can be considered a suitable instrument for a preliminary diagnostic campaign of terracotta polychrome sculptures. Copyright © 2011 John Wiley & Sons, Ltd.     

An interactive graphical user interface (GUI) for the CATGIXRF program – for microstructural evaluation of thin film and impurity doped surfaces

This paper is a continuation and extension of our earlier work (X‐ray Spectrom. 2010 , 39, 127–134, DOI:10.1002/xrs.1215) on the development of a software platform CATGIXRF, as a solution to provide non‐destructive evaluation of nanostructured materials. Here, we describe an interactive graphical user interface (GUI) for the CATGIXRF program. The newly developed GUI interface facilitates determination of microstructural parameters on angstrom length scale for the nanostructured thin layered materials using synchrotron as well as laboratory X‐ray sources. It allows combined analysis capabilities for both the X‐ray reflectivity and grazing incidence X‐ray fluorescence (GIXRF) data simultaneously, thus enabling us a greater sensitivity for the determination of microstructural parameters such as thickness, interface mixing, and roughness of a thin film medium with improved accuracies. The utility and various newly added salient features of the GUI‐CATGIXRF program are described by providing example calculations as well as by analyzing experimentally a few thin film structures with different surface‐interface properties. Copyright © 2016 John Wiley & Sons, Ltd.     

X射线管激发X荧光光谱连续本底扣除方法研究

X射线管是目前X射线荧光光谱分析中最常采用的激发源,它所产生的原级谱成为了X荧光光谱中本底成分的主要来源,在对这种光谱进行进一步的分析处理之前需要对其本底进行扣除,对本底估计的准确性直接影响后续处理步骤的效果。对射线管激发X荧光光谱的成分进行了分析,针对其本底特点构造了一种本底强度的估计方法,并根据实测谱线构建了理论测试谱线以便对光谱处理算法的效果进行评价。该方法利用测得X射线荧光光谱中不包含特征峰的谱段对X射线管原级谱造成的本底成分进行估计,使用只包含连续本底的谱段对整个测量谱段进行插值,从而避免了谱线特征峰重叠或对半高宽估计不当时所产生的影响。利用构建的测试光谱对SNIP法、傅里叶变换法和本文的本底估计方法的使用效果进行了比较,使用该方法估计的本底与理论本底更加接近。结果表明使用的方法对X射线管激发的X荧光光谱的本底估计准确,可以采用这种方法对连续本底进行扣除,在对实际测得的X射线荧光光谱的本底扣除中取得了较好的应用效果。