Evaluation of the uncertainty of element determination using the energy‐dispersive x‐ray fluorescence technique and the emission–transmission method

A detailed study of the uncertainty quantification procedure for the determination of element mass fractions in a soil matrix by using energy‐dispersive x‐ray fluorescence spectrometry and the emission–transmission method was carried out. The particular case of secondary target excitation with an Mo target and Mo anode x‐ray tube was addressed. The effects of simplification of the theoretical model on the determined mass fractions of elements were studied. The main contributions to the uncertainty were identified and the ways of reducing their magnitude were indicated. The approach was found to be helpful in designing an optimum analytical strategy. It can also be used as guidance for assessing the uncertainty in other modes of x‐ray fluorescence analysis. Copyright © 2003 John Wiley & Sons, Ltd.     

Nondestructive elemental depth profiling of Japanese lacquerware ‘Tamamushi‐nuri’ by confocal 3D‐XRF analysis in comparison with micro GE‐XRF

We have applied recently two XRF (micro x‐ray fluorescence) methods [micro‐Grazing Exit XRF (GE‐XRF) and confocal 3D‐XRF] to Japanese lacquerware ‘Tamamushi‐nuri.’ A laboratory grazing‐exit XRF (GE‐XRF) instrument was developed in combination with a micro‐XRF setup. A micro x‐ray beam was produced by a single capillary and a pinhole aperture. Elemental x‐ray images (2D images) obtained at different analyzing depths by micro GE‐XRF have been reported. However, it was difficult to directly obtain depth‐selective x‐ray spectra and 2D images. A 3D XRF instrument using two independent polycapillary x‐ray lenses and two x‐ray sources (Cr and Mo targets) was also applied to the same sample. 2D XRF images of a Japanese lacquerware showed specific distributions of elements at the different depths, indicating that ‘Tamamushi‐nuri’ lacquerware has a layered structure. The merits and disadvantages of both the micro GE‐XRF and confocal micro XRF methods are discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

A simple calibration procedure of polycapillary based portable micro‐XRF spectrometers for reliable quantitative analysis of cultural heritage materials

Portable micro‐X‐ray fluorescence (micro‐XRF) spectrometers mostly utilize a polycapillary X‐ray lens along the excitation channel to collect, propagate and focus down to few tens of micrometers the X‐ray tube radiation. However, the polycapillary X‐ray lens increases the complexity of the quantification of micro‐XRF data because its transmission efficiency is strongly dependent on the lens specifications and the propagated X‐ray energy. This feature results to a significant and not easily predicted modification of the energy distribution of the primary X‐ray tube spectrum. In the present work, we propose a simple calibration procedure of the X‐ray lens transmission efficiency based on the fundamental parameters approach in XRF analysis. This analytical methodology is best suited for compact commercial and portable micro‐XRF spectrometers. The developed calibration procedure is validated through the quantitative analysis of a broad range of samples with archeological relevance such as glasses, historical copper alloys, silver and gold alloys offering an overall accuracy of less than 10%–15%. Copyright © 2015 John Wiley & Sons, Ltd.     

Prototype GaAs X‐ray detector and preamplifier electronics for a deep seabed mineral XRF spectrometer

Work towards developing a prototype GaAs based X‐ray fluorescence spectrometer focusing on the detector‐preamplifier system for in situ characterisation of deep seabed minerals is presented. Such an instrument could be useful for marine geology and provide insight into hydrothermal processes. It would also be beneficial for deep sea mining applications. The GaAs photodiode was electrically characterised at 4 °C (ambient seawater temperature) and 33 °C. A system energy resolution (full width at half maximum) at 5.9 keV of 580 eV at 4°C, limited by the dielectric noise, broadening to 680 eV at 33°C, was recorded. The spectral performance of the system was characterised across the energy range 4.95 keV to 21.17 keV, at 33°C, using high‐purity X‐ray fluorescence calibration samples excited by a Mo target X‐ray tube. The charge output from the system was found to be linear with incident photon energy. The energy resolution was found to broaden from 695 eV at 4.95 keV to 735 eV at 21.17 keV, attributed to the increasing Fano noise with energy. The same X‐ray tube was used to fluoresce an unprepared manganese nodule (revealing the presence of Mn, Fe, Ni, Cu, Zn, Pb, Sr, and Mo) and a black smoker hydrothermal vent sample (containing Fe, Co, Ni, Cu, Zn, Pb, and Mo). Such a spectrometer may also find use in future space missions to study the hydrothermal vents that are believed to exist in the oceans of Jupiter's moon Europa.     

A new microfocus x‐ray source,iMOXS, for highly sensitive XRF analysis in scanning electron microscopes

Scanning electron microscopes are usually equipped with energy‐dispersive X‐ray detectors for electron probe microanalysis. This widespread analytical method allows investigators to determine the elemental composition of specimens with a spatial resolution of about 1 µm. However, owing to the electron–specimen interaction, the emitted spectra reveal, in addition to characteristic lines, also a high level of continuous bremsstrahlung background. As a result, elements with low concentrations cannot be identified. The minimum detection limit can be diminished by two orders of magnitude if the characteristic lines are excited as fluorescence by an additional x‐ray source. In this case, the emergence of bremsstrahlung is considerably reduced. Combining a high‐brilliance microfocus x‐ray tube with efficient polycapillary optics enables one to realize an experimental arrangement for performing local fluorescence analysis at the same point where the electron beam hits the sample. The polycapillary optics under consideration focuses the emitted x‐radiation onto focal spots between 30 and 100 µm in diameter. Count rates of several thousands cps have been achieved. Elemental maps have been obtained by means of the motorized specimen stage of the microscope. Copyright © 2005 John Wiley & Sons, Ltd.     

Optical performance of materials for X‐ray refractive optics in the energy range 8–100 keV

A quantitative analysis of the crucial characteristics of currently used and promising materials for X‐ray refractive optics is performed in the extended energy range 8–100 keV. According to the examined parameters, beryllium is the material of choice for X‐ray compound refractive lenses (CRLs) in the energy range 8–25 keV. At higher energies the use of CRLs made of diamond and the cubic phase of boron nitride (c‐BN) is beneficial. It was demonstrated that the presence of the elements of the fourth (or higher) period has a fatal effect on the functional X‐ray properties even if low‐Z elements dominate in the compound, like in YB₆₆. Macroscopic properties are discussed: much higher melting points and thermal conductivities of C and c‐BN enable them to be used at the new generation of synchrotron radiation sources and X‐ray free‐electron lasers. The role of crystal and internal structure is discussed: materials with high density are preferable for refractive applications while less dense phases are suitable for X‐ray windows. Single‐crystal or amorphous glass‐like materials based on Li, Be, B or C that are free of diffuse scattering from grain boundaries, voids and inclusions are the best candidates for applications of highly coherent X‐ray beams.     

Influence of photo and Auger electrons of the elements with high atomic numbers on formation of carbon x‐ray fluorescence intensity

The x‐ray fluorescence radiation of carbon was studied in the presence of elements with high atomic numbers in the material irradiated. It was found that photo and Auger electrons of such elements originating from ionization of shells remote from nucleus (L‐, M‐ and N‐shells) effectively excite atoms of carbon. Hence, using a matrix with Z > 30, the influence of the electrons should be considered, and using a matrix with Z > 50 this influence becomes decisive. Calculations of carbon x‐ray fluorescence intensity were executed for different x‐ray tube anodes. Their correctness is confirmed by agreement with experimental results. Copyright © 2005 John Wiley & Sons, Ltd.     

Layout and first XRF applications of the BAMline at BESSY II

The first hard x‐ray beamline at BESSY II has been installed by BAM and PTB at a superconducting 7 T wavelength shifter. The main optical elements of the beamline are a double‐multilayer monochromator and a double‐crystal monochromator. Depending on the application, the two devices are used separately or in‐line. The main applications of the monochromatic radiation with photon energies up to 60 keV are x‐ray fluorescence analysis, micro computed tomography, x‐ray topography, detector calibration and reflectometry. Calculable undispersed radiation up to 200 keV is available for radiometric applications. Copyright © 2004 John Wiley & Sons, Ltd.     

Characterization of x‐rays emerging from between reflector and sample carrier in reflector‐assisted TXRF analysis

The possible application of an Si reflector, which is placed just above the sample carrier in total reflection x‐ray fluorescence (TXRF) analysis, was investigated. The x‐rays that were emitted from an Mo tube and passed between the Si reflector and the Si sample carrier were analyzed with an Si drift detector. In our experimental setup, the angle between the reflector and the sample carrier can be changed by adjusting the inclination of the reflector. The intensity of the x‐rays that emerged from between the two Si surfaces drastically changed depending on the reflector angle. At a proper reflector angle, this intensity showed a maximum and, in addition, the Compton peak in the x‐ray spectrum was suppressed. When this x‐ray beam was used for excitation of TXRF signals, the highest intensity of x‐ray fluorescence emitted from the sample was detected, indicating that these experimental conditions are useful for the enhancement of TXRF intensities. Copyright © 2004 John Wiley & Sons, Ltd.     

Quantitative thickness determination using x‐ray fluorescence: application to multiple layers

The fundamental parameter method using x‐ray fluorescence was applied to the quantitative determination of single and multiple layer thicknesses using a compact experimental setup. Focused white‐beam radiation was obtained from a high‐voltage Mo x‐ray tube and the fluorescence spectra were acquired using a Peltier‐cooled Si solid‐state detector. The results show that in the case of single layers the accuracy of the thicknesses obtained is very good whereas for multiple layer structures the agreement is poorer, especially for the thinnest layers. This indicates a possible drawback of the standard‐free thickness determination scheme based on fundamental parameters for complex samples. Copyright © 2004 John Wiley & Sons, Ltd.     

Literature trends in x‐ray emission spectrometry in the period 1990–2000–a review

A quantitative overview is given of the role that x‐ray emission analysis methods, in their various forms, play in the literature for the period from January 1990 to the end of December 2000. The major sources of information were computerized searches through Chemical Abstracts and Web of Science and, specifically for 1998, a manual search through Analytical Abstracts. Areas that are covered in this review pertain to the recent trends in x‐ray emission spectrometry in general and in some specific techniques such as x‐ray fluorescence analysis, synchrotron radiation‐induced and particle‐induced x‐ray emission, total‐reflection and micro‐x‐ray fluorescence analysis. A brief outline of recent developments in the specific fields is given, with emphasis on the various excitation and detection modes, on different application areas and on relative contributions of different countries and languages to the x‐ray emission spectrometry literature. It appears that environmental monitoring and research continue to be particularly important publication fields for x‐ray spectrometry. Copyright © 2003 John Wiley & Sons, Ltd.     

Silicon nitride transmission X‐ray mirrors

Transmission X‐ray mirrors have been fabricated from 300–400 nm‐thick low‐stress silicon nitride windows of size 0.6 mm × 85 mm. The windows act as a high‐pass energy filter at grazing incidence in an X‐ray beam for the beam transmitted through the window. The energy cut‐off can be selected by adjusting the incidence angle of the transmission mirror, because the energy cut‐off is a function of the angle of the window with respect to the beam. With the transmission mirror at the target angle of 0.22°, a 0.3 mm × 0.3 mm X‐ray beam was allowed to pass through the mirror with a cut‐off energy of 10 keV at the Cornell High Energy Synchrotron Source. The energy cut‐off can be adjusted from 8 to 12 keV at an angle of 0.26° to 0.18°, respectively. The observed mirror transmittance was above 80% for a 300 nm‐thick film.     

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.     

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.     

A simple x‐ray monochromator based on an alligator lens

Alligator lenses, i.e. two inclined arrays of sawteeth or prisms, which face each other, can focus x‐rays with photon energies >4 keV. The inclination angle can be changed easily, and thus either the focal length for fixed photon energy or the photon energy in a fixed slit position can be varied. The material distribution in this condition is approximately parabolic along the teeth axis, hence it is of the shape required for aberration‐free focusing at a given photon energy. As the refractive index varies significantly with photon energy in the x‐ray range, these lenses suffer from chromatic aberrations, if illuminated with white x‐rays. In combination with a slit such a lens can therefore be used as an easily insertable inline monochromator. In this work, a simple universal function for the dependence of the transmission on the photon energy was derived for this application. The required tolerances for the shape of the sawteeth are found to be compatible with standard workshop machining procedures. A laboratory‐made lens of Plexiglas is shown to increase the flux density in a laboratory setup by a factor of 3, i.e. 50% of the expected result for a perfect lens. The discrepancy can be consistently ascribed to macroscopic defects of the sawteeth tips. Expectations for the performance of these lenses as monochromators at synchrotron radiation sources are presented. A single Be alligator lens is expected to provide tuning between at least 8 keV and 20 keV photon energy with a bandpass of 6%, sufficient for XRF and SAXS experiments. Consequently, such a lens pair is all that is needed for building simple synchrotron radiation beamlines for special x‐ray experiments. Copyright © 2004 John Wiley & Sons, Ltd.     

Protective radiolucent aluminium oxide coatings for beryllium X‐ray optics

Beryllium, being one of the most transparent materials to X‐ray radiation, has become the material of choice for X‐ray optics instrumentation at synchrotron radiation sources and free‐electron laser facilities. However, there are concerns due to its high toxicity and, consequently, there is a need for special safety regulations. The authors propose to apply protective coatings in order to seal off beryllium from the ambient atmosphere, thus preventing degradation processes providing additional protection for users and prolonging the service time of the optical elements. This paper presents durability test results for Be windows coated with atomic‐layer‐deposition alumina layers run at the European Synchrotron Radiation Facility. Expositions were performed under monochromatic, pink and white beams, establishing conditions that the samples could tolerate without radiation damage. X‐ray treatment was implemented in various environments, i.e. vacuum, helium, nitrogen, argon and dry air at different pressures. Post‐process analysis revealed their efficiency for monochromatic and pink beams.     

Measurements of Coster–Kronig enhancement factors of some elements in the atomic number range 66 ≤ Z ≤ 72

The Lι, Lα, Lβ and Lγ x‐ray production cross‐sections in four elements with Z ranging from 66 to 72 at seven different energies in the interval 8.265–11.730 keV were measured. Experimental measurements were carried out on a few elemental samples to examine the effect of Coster–Kronig transitions on fluorescence cross‐sections for the L x‐ray line using an Si(Li) detector system with an energy resolution of 160 eV at 5.96 keV x‐ray energy. Absolute values of L x‐ray cross‐sections were calculated with incorporation of the enhancement due to the Coster–Kronig effect for these elements. The measured enhancement factors are smaller than predicted by theory. Copyright © 2003 John Wiley & Sons, Ltd.     

The role of Compton scattering in the low‐Z elements X‐ray fluorescence formation

The paper reviews the ionization of elements with low atomic numbers (boron, carbon, nitrogen, oxygen, and fluorine) by incoherent scattering of primary radiation and under the influence of Compton electrons. It is shown that at high energy of primary photons, the total contribution of these processes to X‐ray fluorescence formation becomes significant; at the energy of 80 keV, it becomes dominant. Copyright © 2013 John Wiley & Sons, Ltd.