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.     

Depth‐selective elemental imaging of microSD card by confocal micro XRF analysis

A semiconductor device, a microSD card, was measured by using two XRF instruments. 2D elemental images were obtained using a micro‐XRF system with a spatial resolution of 10 µm. Elemental distributions of the near‐surface region of the sample were clearly shown. Titanium was observed in the resin constituting the sample. Nickel and gold were observed on a terminal and localization of the sample. Elemental distribution of copper reflected the circuit structure of the measurement area that was in the neighborhood of the sample surface. Moreover, the elemental depth distributions of the sample were measured by using a confocal micro‐XRF instrument. The confocal micro‐XRF instrument was constructed in the laboratory with fine‐focus polycapillary x‐ray optics. The depth resolution of the developed spectrometer was 13.7 µm at an energy of Au Lβ (11.4 keV). The elemental images obtained at near‐surface by confocal micro‐XRF were the same as the results obtained from 2D micro‐XRF. However, different Cu images were obtained at a depth of several tens of micrometers. This indicates that microSD cards consist of a few different Cu‐circuit structure designs. The elemental depth distributions of each circuit structure of the semiconductor device were clearly shown by confocal micro‐XRF. Copyright © 2013 John Wiley & Sons, Ltd.     

Improvements of the low‐energy performance of a micro‐focus x‐ray source for XRF analysis with the SEM

X‐ray Fluorescence (XRF) with a scanning electron microscope (SEM) is a valuable completion of the analytical capabilities of SEMs. Small and compact micro‐focus x‐ray sources are mounted to the microscope chamber, and the x‐ray spectra are monitored with conventional EDS systems. Up to now the x‐ray tubes used for the micro‐focus x‐ray sources are equipped with beryllium windows about 100 µm thick. The poly‐capillary x‐ray lenses have their transmission maximum at photon energies around 10 keV. It drops down in both low‐ and high‐energy ranges. Hence, L‐radiation from an Mo or Rh target will be strongly attenuated, and the excitation of fluorescence in the soft x‐ray range becomes very ineffective. A new micro‐focus x‐ray source was developed. It is characterised by a lower self‐absorption in the tube target, thin beryllium windows and an x‐ray optics having a large distance between its foci and the maximum of transmission at about 5 keV. Thus K line fluorescence of light elements becomes effectively excited by the L‐radiation from Mo or Rh tube targets. The detection limit for sodium oxide in glass was found to be below 1 mass%. Copyright © 2009 John Wiley & Sons, Ltd.     

Quantitative or semi‐quantitative?–laboratory‐based WD‐XRF versus portable ED‐XRF spectrometer: results obtained from measurements on nickel‐base alloys

‘Semi‐quantitative’ analytical procedures are becoming more and more popular. Using such procedures, the question of the accuracy of results arises. The accuracy of an analytical procedure depends to a great extent on spectral resolution, counting statistics and matrix correction. Two ‘semi‐quantitative’ procedures are compared with a quantitative analytical program. Using a laboratory‐based wavelength‐dispersive x‐ray fluorescence (WD‐XRF) spectrometer and a portable energy‐dispersive x‐ray fluorescence (ED‐XRF) spectrometer, 28 different nickel‐base alloy Certified Reference Materials (CRMs) were analyzed. Line interferences and inaccurate matrix correction are reasons for deviations from the reference value. As the comparison shows, ‘semi‐quantitative’ analyses on the WD‐XRF spectrometer can be accepted as quantitative determinations. The investigations show that the results obtained with the portable ED‐XRF spectrometer do not meet the quality requirements of laboratory analysis, but they are good enough for field investigations. Copyright © 2004 John Wiley & Sons, Ltd.     

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.     

Potentiality of non‐destructive XRF analysis for the determination of Corinthian B amphorae provenance

Numerous samples of archaic transport Corinthian B type amphorae coming from the archaeological excavations of Gela (Sicily, South Italy) were analysed using non‐destructive X‐ray fluorescence (portable InnovX‐Systems ‘Alpha 4000’). Between the 6th and the 5th century BC the Corinthian B amphorae were diffused throughout the Western Mediterranean regions and Greece. Some researchers assigned these amphorae to different production areas, both in Southern Italy and in Greece, although, up to now, the exact attribution to the production centres is still under discussion. In this paper, with the aim to characterise the production sites of this important typology of amphorae, common ceramics, undoubtedly produced in Corinth, Corfù and Sybaris, were also analysed as these important Greek and Magna Graecia cities are considered by the archaeologists as the production centres of ‘Corinthian B’ amphorae. The multivariate analysis, performed on selected elements, clearly distinguished two groups of amphorae which, on the basis of archeological considerations, and by the comparison with reference ceramics, were assigned to Magnae Grecia (Sybaris and surroundings) and Greek productions. Copyright © 2011 John Wiley & Sons, Ltd.     

Simulation of layer measurement with confocal micro‐XRF

A simple model to simulate the measurement of layered structures with confocal micro X‐ray fluorescence (micro‐XRF) was developed and implemented as a computer program. The model assumes monochromatic excitation, considers at the moment only K lines, and simplifies the volume defined by excitation and detection foci as a circle area. First simulation results and comparison with data acquired using the Atominstitut confocal micro‐XRF spectrometer are very promising. The simulation software enables us to perform parameter studies to have a better understanding of the analysis of layered structures with confocal micro‐XRF. Copyright © 2014 John Wiley & Sons, Ltd.     

Toward sub‐micro‐XRF working at nanometer range using capillary optics

Capillary optics are used for X‐ray fluorescence micro‐analysis using the Cu Kα line provided by a rotating anode. The excitation beam is focused using a polycapillary lens on a Co–Ti sample. Cylindrical glass capillaries of various diameters are fitted to the X‐ray detector (Energy Dispersive X‐Ray (EDX) analyzer) and displaced along the irradiated zone of the sample. The fluorescence is studied as a function of capillary position. Good agreement is found between experimental and calculated lateral widths of the fluorescence collection, taken into account the cylindrical capillary critical angles relevant in the experiment. The influence of the cylindrical capillary diameter on the signal level detected is studied to estimate the possibility of lateral resolution increase of X‐ray fluorescence technique both in‐lab and in synchrotron environment. Copyright © 2013 John Wiley & Sons, Ltd.     

Low‐wavelength emission of Nd‐doped lasers

This paper gives an overview of the results obtained with diode‐pumped Neodymium‐doped crystals operating below 900 nm. Operation at such low wavelengths requires considering the strong thermal population of the lower level of the laser transition. Based on a theoretical study and simulations, the paper presents the challenges related to the design of these three‐level lasers. Experimental results are given with Nd:YAG and Nd:vanadate crystals. It is explained how to deal with the line competition with emission at 946 nm or 912 nm. Finally, intracavity second‐harmonic generation is presented. The output powers reach a few hundred mW at wavelengths below 450 nm. Hence, the paper demonstrates the potential of Nd‐doped diode‐pumped solid‐state lasers for applications in the blue range, in replacement of gas lasers such as helium‐cadmium lasers.     

Direct chemical characterisation of clay suspensions by WD‐XRF

This study was performed to develop a method for directly controlling the chemical composition of clay slurries used in preparing ceramic floor and wall tile bodies by wavelength‐dispersive X‐ray fluorescence (WD‐XRF) spectrometry, without the prior need to dry and prepare the samples as fused beads or pellets for WD‐XRF measurement, owing to the importance of knowing the suspension chemical composition in real time for appropriate control of the industrial process. The study was conducted on a wide range of ceramic floor and wall tile bodies, which are used to prepare different suspensions. The influence of suspension viscosity (from 300 to 7000 cp), of suspension solids content (between 66 and 69%), and of the type of body composition (floor or wall tile) on the WD‐XRF measurement was determined. In these viscosity and solid content ranges, no appreciable differences were observed in the WD‐XRF measurement results, indicating that the possibly arising variations in viscosity and solids content in such clay suspensions in industrial practice do not influence the WD‐XRF measurement. In contrast, the type of body composition did influence the WD‐XRF measurement. The developed method is rapid, reproducible, and accurate, which was verified by analysis of the materials using the customary method of WD‐XRF measurement on fused beads. In addition, this method is cheaper and more harmless to the environment; it minimises waste generation, since no sample preparation is required and the plastic sample holders can be reused, thanks to the reusable sample holder system designed at the Instituto de Tecnología Cerámica laboratories. Copyright © 2011 John Wiley & Sons, Ltd.     

Micro‐Raman investigation of transition‐metal‐doped ZnO nanoparticles

We measured the Raman spectra of ZnO nanoparticles (ZnO‐NPs), as well as transition‐metal‐doped (5% Mn(II), Fe(II) or Co(II)) ZnO nanoparticles, with an average size of 9 nm. A typical Raman peak at 436 cm⁻¹ is observed in the ZnO‐NPs, whereas Zn_1−xMn_xO, Zn_1−xFe_xO and Zn_1−xCo_xO presented characteristic peaks at 661, 665 and 675 cm⁻¹, respectively. These peaks can be related to the formation of Mn₃O₄, Fe₃O₄ and Co₃O₄ species in the doped ZnO‐NPs. Moreover, these samples were analyzed at various laser powers. Here, we observed new vibrational modes (512, 571 and 528 cm⁻¹), which are specific to Mn, Fe and Co dopants, respectively, and ZnO‐NPs did not reveal any additional modes. The new peaks were interpreted either as disorder activated phonon modes or as local vibrations of Mn‐, Fe‐ and Co‐related complexes in ZnO. Copyright © 2007 John Wiley & Sons, Ltd.     

Light‐induced degradation in indium‐doped silicon

Light‐induced degradation of charge carrier lifetime was observed in indium‐doped silicon. After defect formation, an annealing step at 200 °C for 10 min deactivates the defect and the initial charge carrier lifetime is fully recovered. The observed time range of the defect kinetics is similar to the well known defect kinetics of the light‐induced degradation in boron‐doped samples. Differences between defect formation in boron‐ and indium‐doped silicon are detected and discussed. A new model based on an acceptor self‐interstitial A_Si–Si_i defect is proposed and established with experimental findings and existing ab‐initio simulations.

     

A confocal set‐up for micro‐XRF and XAFS experiments using diamond‐anvil cells

A confocal set‐up is presented that improves micro‐XRF and XAFS experiments with high‐pressure diamond‐anvil cells (DACs). In this experiment a probing volume is defined by the focus of the incoming synchrotron radiation beam and that of a polycapillary X‐ray half‐lens with a very long working distance, which is placed in front of the fluorescence detector. This set‐up enhances the quality of the fluorescence and XAFS spectra, and thus the sensitivity for detecting elements at low concentrations. It efficiently suppresses signal from outside the sample chamber, which stems from elastic and inelastic scattering of the incoming beam by the diamond anvils as well as from excitation of fluorescence from the body of the DAC.     

Characterization of chromium‐containing ceramic pigments by XRF and XRD

As no methodology was found in the literature for characterizing ceramic pigments chemically and mineralogically, the present study was undertaken to establish a methodology for the chemical and phase characterization of ceramic pigments by x‐ray fluorescence (XRF) spectrometry and x‐ray diffraction (XRD). In view of the large number of pigments described in the literature (around 44), the present study was limited to characterizing pigments that contained chromium, which is the most versatile chromophore used in ceramics. Copyright © 2004 John Wiley & Sons, Ltd.     

Chemical characterisation by WD‐XRF and XRD of silicon carbide‐based grinding tools

This paper addresses the chemical characterisation of silicon carbide‐based grinding tools. These are among the most widely used grinding tools in the ceramic sector, and instruments are required that enable the grinding tool quality to be controlled, despite the considerable complexity involved in determining grinding tool chemical composition. They contain components of quite different nature, ranging from the silicon carbide abrasive to the resin binder. To develop the analysis method, grinding tools containing silicon carbide with different grain sizes were selected from different tile polishing stages. To develop the grinding tool characterisation method, the different measurement process steps were studied, from sample preparation, in which different milling methods (each appropriate for the relevant type of test) were used, to the optimisation of the determination of grinding tool components by spectroscopic and elemental analyses. For each technique, different particle sizes were used according to their needs. For elemental analysis, a sample below 150 µm was used, while for the rest of the determinations a sample below 60 µm was used. After milling, the crystalline phases were characterised by X‐ray powder diffraction and quantified using the Rietvel method. The different forms of carbon (organic carbon from the resin, inorganic carbon from the carbonates and carbon from the silicon carbide) were analysed using a series of elemental analyses. The other elements (Si, Al, Fe, Ca, Mg, Na, K, Ti, Mn, P and Cl) were determined by wavelength‐dispersive X‐ray fluorescence spectrometry, preparing the sample in the form of pressed pellets and fused beads. The chemical characterisation method developed was validated with mixtures of reference materials, as there are no reference materials of grinding tools available. This method can be used for quality control of silicon carbide‐based grinding tools. Copyright © 2010 John Wiley & Sons, Ltd.     

Light‐induced degradation in copper‐contaminated gallium‐doped silicon

To date, gallium‐doped Czochralski (Cz) silicon has constituted a solar cell bulk material free of light‐induced degradation. However, we measure light‐induced degradation in gallium‐doped Cz silicon in the presence of copper impurities. The measured degradation depends on the copper concentration and the material resistivity. Gallium‐doped Cz silicon is found to be less sensitive to copper impurities than boron‐doped Cz silicon, emphasizing the role of boron in the formation of copper‐related light‐induced degradation. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Chemical reactivity of lithium‐doped fullerenes

The addition of free radicals and the 1,3 dipolar cycloaddition onto pristine and lithium‐doped C₆₀ were studied by means of the Perdew–Burke–Ernzerhof (PBE) and M06‐2X density functionals. In all cases, lithium increased the reactivity even though for the 1,3 dipolar cycloaddition onto C₆₀ the change observed with respect to bare C₆₀ was minimal. Both functionals employed gave similar encapsulation energies for Li@C₆₀ namely, 33.1 and 38.2 kcal/mol at the PBE/6‐31G* and M06‐2X/6‐31G*, respectively. However, the increased reactivity because of lithium doping determined at the PBE level is smaller as compared with that computed with the M06‐2X functional, whereas that determined at the second‐order Møller–Plesset (MP2) level is the largest one. For example, using the M06‐2X functional the binding energy of fluorine to Li@C₆₀ is 28.5 kcal/mol larger than that determined for C₆₀, whereas at the PBE/6‐31G* level it is predicted to be increased by 24.7 kcal/mol. The results clearly suggest that Li@C₆₀ is a much better free radical scavenger than C₆₀. Finally, the complex hindered rotations of lithium inside C₆₀ are expected to be strongly inhibited because lithium doping increases the well depth between the cage center and the equilibrium position near the addition site of the lithium atom. Copyright © 2011 John Wiley & Sons, Ltd.     

Fabrication of doped nano‐electromechanical systems

We present a new generation of nano‐electromechanical systems (NEMS), which are realized by doping the semiconductor base material. In contrast to the traditional approach these doped NEMS (D‐NEMS) do not require a metallization layer. This makes them far lighter and hence increases resonance frequency and quality factor. Additionally, D‐NEMS can be tuned from the conductive state into an insulating one. This will enable a host of new device designs, like mechanically tunable pin‐junctions and nanomechanical single electron switches. We demonstrate D‐NEMS fabrication and operation from the intrinsic, to the light, and to the heavy regime of doping. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Development of a high‐resolution confocal micro‐XRF instrument equipped with a vacuum chamber

A confocal micro‐X‐ray fluorescence (micro‐XRF) instrument equipped with a vacuum chamber was newly developed. The instrument is operated under a vacuum condition to reduce the absorption of XRF in the atmosphere. Thin metal layers were developed to evaluate the confocal volume, corresponding to depth resolution. A set of thin metal layers (Al, Ti, Cr, Fe, Ni, Cu, Zr, Mo, and Au) was prepared by a magnetron sputtering technique. The depth resolutions of the new instrument were varied from 56.0 to 10.9 µm for an energy range from 1.4 to 17.4 keV, respectively. The lower limit of detection (LLD) was estimated by comparison with a glass standard reference material NIST SRM 621). The LLDs obtained by a conventional micro‐XRF were compared with the LLDs obtained by a confocal micro‐XRF instrument. The LLDs were improved in the measurement under confocal configuration because of the reduction of background intensity. Finally, layered materials related to forensic investigation were measured. The confocal micro‐XRF instrument was able to nondestructively obtain the distribution of light elements that cannot be detected by measurement in air. Copyright © 2013 John Wiley & Sons, Ltd.     

Energy‐dispersive XRF spectrometer for Ti determination (TITAN)

An energy‐dispersive XRF analyser was designed and constructed for determining Ti in plant and peat materials at low (ppm) concentrations. The XRF analyzer for Ti analysis (TITAN) uses monochromatic excitation obtained from a crystal diffraction monochromator and Co target x‐ray diffraction tube. In addition to precise and sensitive analyses of Ti, other minor elements (Ca, K, Cl, S, P, Ba) in powdered plant and peat samples can be measured with only a minimum of sample preparation (drying, milling). The limits of detection obtained are K 2.5, Ca 1.5, Ti 0.9, Cr 0.7 and Mn 0.5 ppm using a 600 s acquisition time. The instrument was used to determine Ti concentrations in pre‐anthropogenic peat samples up to 9000 years old. Copyright © 2004 John Wiley & Sons, Ltd.