The impact of secondary fluorescence on the material compositions measured by X-ray analysis for layered semiconductor thin films is assessed using simulations performed by the DTSA-II and CalcZAF software tools. Three technologically important examples are investigated: AlxGa1−xN layers on either GaN or AlN substrates, InxAl1−xN on GaN, and Si-doped (SnxGa1−x)2O3 on Si. Trends in the differences caused by secondary fluorescence are explained in terms of the propensity of different elements to reabsorb either characteristic or bremsstrahlung X-rays and then to re-emit the characteristic X-rays used to determine composition of the layer under investigation. Under typical beam conditions (7–12 keV), the quantification of dopants/trace elements is found to be susceptible to secondary fluorescence and care must be taken to prevent erroneous results. The overall impact on major constituents is shown to be very small with a change of approximately 0.07 molar cation percent for Al0.3Ga0.7N/AlN layers and a maximum change of 0.08 at% in the Si content of (SnxGa1−x)2O3/Si layers. This provides confidence that previously reported wavelength-dispersive X-ray compositions are not compromised by secondary fluorescence.

Microbial-induced calcite precipitation (MICP) has gained much attention in soil improvement studies, where it can enhance the physical properties of sandy soil. Small-scale sand cylinder tests were conducted to investigate the formation and failure of calcium carbonate precipitation bonding between individual sand particles. Bonding formation by precipitation was examined by scanning electron microscopy. Energy-dispersive X-ray spectroscopy analysis verified the existence of calcium, carbon, and oxygen, which could form CaCO3 after MICP-treatment. Focused-ion-beam milling was applied to study the interior structure of calcium carbonate precipitation during the MICP process.

In a thin specimen X-ray absorption and fluorescence can, to a first approximation, be ignored and the observed X-ray intensity ratios, IA/IB, can be converted into weight fraction ratios, , can be converted into weight fraction ratios, CA/CB, by multiplying by a constant , by multiplying by a constant kAB;

kAB values can be calculated or determined experimentally. The major correction which may have to be made to the calculated weight fraction ratio is for X-ray absorption within the specimen. The activated volume for analysis in a thin specimen is approximately 100 000 × less than in a bulk sample. Beam spreading within the specimen can be estimated using a simple formula based on a single elastic scattering event at the centre of the specimen. Examples are given of the application of the technique to obtain both qualitative and quantitative analyses from thin mineral specimens. The minimum detectable mass and the minimum mass fraction which can be measured using the technique are estimated.

A number of techniques for the characterization of rare earth minerals (REM) have been developed and are widely applied in the mining industry. However, most of them are limited to a global analysis due to their low spatial resolution. In this work, phase map analyses were performed on REM with an annular silicon drift detector (aSDD) attached to a field emission scanning electron microscope. The optimal conditions for the aSDD were explored, and the high-resolution phase maps generated at a low accelerating voltage identify phases at the micron scale. In comparisons between an annular and a conventional SDD, the aSDD performed at optimized conditions, making the phase map a practical solution for choosing an appropriate grinding size, judging the efficiency of different separation processes, and optimizing a REM beneficiation flowsheet.

Bryophytes are usually taken as good bioindicators. However, they represent a large group of terrestrial plants and they express an enormous range of peculiarities within the plant kingdom. With the aim to search for a common pattern of zinc binding, we established axenical in vitro cultures of a dozen bryophyte species that include hornworts, thallose, and leafy liverworts, as well as acrocarp and pleurocarp mosses. The species were grown free of contaminants for many years prior to the application of different treatments, i.e. offering Zn(II) from solid and liquid media and in combination with different anions. The localization and binding of zinc was detected by confocal microscopy using the zinc-specific dye FluoZin™-3. In one of the species, Hypnum cupressiforme (which is widely used for atmospheric heavy metal deposition studies in biomonitoring), semi-quantitative analyses of zinc were performed by energy dispersive X-ray microspectrometry (EDX) in a scanning electron microscope. The results suggest no common pattern of Zn(II) binding in different bryophyte species. Instead, the binding pattern seems to be species specific. Zinc is located in certain areas or cellular compartments, as clearly shown by the EDX measurements in H. cupressiforme.

The distribution patterns of several herbicide formulations sprayed on adaxial leaf surfaces were determined using scanning electron microscopy coupled with cathodoluminescence and x-ray microanalysis. The sodium and amine salts of MCPA {[(4-chloro-o-tolyl) oxy] acetic acid} sprayed on sugar beet (Beta vulgaris L.) leaves appeared as discrete deposits above the anticlinal cell walls that represented the location of spray drops that adhered to the leaf. When the sodium salt was applied to bermudagrass [Cynodon dactylon (L.) Pers.], the pattern of distribution was the same; however, each deposit was significantly smaller. The iso-octyl ester of MCPA coalesced into numerous, small, thick deposits on the cuticle of sugar beet leaves. The distribution of a wettable powder formulation of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino-s-triazine] appeared as uniform deposits over the anticlinal and periclinal cell walls that represented the location of aqueous spray drops after application. When a flowable formulation of atrazine was applied, there was a significant preferential accumulation of the herbicide at the edges of the separate deposits. One commercial formulation of propanil (3′,4′-dichloropropionanilide) yielded deposits that were crystalline, one that was partially crystalline, and one that was noncrystalline.

Modern analytical electron microscopes equipped with silicon drift detectors now allow for a wide range of geometrical configurations capable of performing quantitative X-ray spectrometry. Recent work has improved the collection solid angles of these detectors, however, the impact of increasing the solid angle on detection sensitivity as measured by the peak/background ratio has not been addressed. This work compares theoretical and experimental peak/background ratios for incident electron energies in the range of 20–200 keV, with X-ray detectors in both conventional orientations (on the electron entrance surface) as well as new geometries (the electron exit surface). The implications of these parameters on detectability limits for the next generations of “Lab-in-the-Gap” analytical microscope are also considered. It was found that theoretical calculations of the angular distribution of bremsstrahlung and their effects on the peak/background ratio match well with experimental measurements, and indicate that new geometries which can result in large solid angles provided an added benefit in addition to increased characteristic signal, namely increased sensitivity for the analyst.

A procedure has been developed to follow degradation of energy-dispersive spectroscopy (EDS) X-ray lateral resolution in a variable pressure scanning electron microscope. This procedure is based on evaluation of the EDS profile shape change for different experimental conditions. Some parameters affecting the X-ray resolution in high-vacuum mode have been taken into account. Good agreement between the simulated and experimental EDS profiles shows the reliability of the proposed procedure. A significant improvement in measurement of the EDS profile interfacial distance (DINT) has been achieved.

The aim of this study is to provide data that increase knowledge about the possible health effects of exposure to 90Sr contaminant in drinking water. 90Sr detection in the mouse bone model plays an important complementary role with computational dosimetry in these investigations. S-value (absorbed dose per unit cumulated activity) calculations using Monte Carlo (MC) simulations, 90Sr detection by liquid scintillation β counting in the femur bone and X-ray microanalysis were carried out. The present work is focused on using MCNPX and its validation at a cellular level. The cytoplasm (Cy), nucleus (N) and 90Sr radiation source were simulated with the MC code MCNPX. Cells are assumed to be spherical, with the radii of the cell and cell nucleus ranging from 2 to 10 μm. The S-value (in Gy/Bq.s) calculations were provided for a 90Sr source distributed uniformly in the cell nucleus or cytoplasm and for two source-target combinations (t←s). A comparison between the calculated MC results and the MIRD values agreed very well since the relative deviations are less than 4%. The earliest results of X-ray microanalysis indicated that the 90Sr was below the detection limit (<0.1%) in the bone tissue. However, the measurements by liquid scintillation showed the presence of 90Sr in the femur bone.

A Monte Carlo simulation was used to determine geometry correction factors that increase accuracy of quantitative X-ray microanalysis of laterally semithick biological materials. A model composed of cellulose with homogeneously distributed biological elements and lateral dimensions between 0.5–25 μm was chosen. The specimen was exposed to 5, 10, and 15 keV electrons, the net intensities of characteristic X-rays registered for the elements, and presented as a function of the lateral dimensions of the model. This showed the double decay exponential function fitted the distribution of X-ray intensities in relation to the model size. The applicability of the function as a correction method was successfully tested for 30 specimens with varying composition and dimensions. The value of relative error decreased from ±60% to ±5% when the correction was applied. Moreover, the minimal lateral size of the material was defined, below which the correction is not required. The simulation also revealed that the difference of the weighted sum of Z2/A between the unknown and the standard could reach 25% without significant influence on the quantitative results. The correction method could be helpful for accurate assessment of elemental composition in biological or organic matrices, when their lateral dimensions are smaller than the distribution range.

This article reviews different methods used to perform quantitative X-ray microanalysis in the electron microscope and also demonstrates the urgency of measuring the fundamental parameters of X-ray generation for the development of accurate standardless quantitative methods. Using ratios of characteristic lines acquired on the same X-ray spectrum, it is shown that the Cliff and Lorimer KA-B factor can be used in a general correction method that is appropriate for all types of specimens and electron microscopes, providing that appropriate corrections are made for X-ray absorption, fluorescence, and indirect generation. Since the fundamental parameters appear in the KA-B factor, only the ratio of the ionization cross sections needs to be known, not their absolute values. In this regard, the measurement of ratios of the KA-B factor (or intensities at different beam energies of the same material with no change of beam spreading in the material) permits the validation for the best models to compute the ratio of ionization cross sections. It is shown, using this method, that the nonrelativistic Bethe equation, to compute ionization cross section, is very close to the equation of E. Casnati et al. (J Phys B15, 155–167, 1982) and also to the equations proposed by D. Bote and F. Salvat (Phys Rev A77, 042701, 2008) for the computation of the ratio of ionization cross sections. The method is extended to show that it could be used to determine the values of the Coster-Kronig transitions factors, an important fundamental parameter for the generation of L and M lines that is mostly known with poor accuracy. The detector efficiency can be measured with specimens where their intensities were measured with an energy dispersive spectrometer detector, the efficiency of which has been measured in an X-ray synchrotron (M. Alvisi et al., Microsc Microanal12, 406–415, 2006). The spatial resolution should always be computed when performing quantitative X-ray microanalysis and the equations of R. Gauvin (Microsc Microanal13(5), 354–357, 2007) for bulk materials and the one presented in this article for thin films should be used. The effects of X-rays generated by fast secondary electrons and by Auger electrons are reviewed, and their effect can be detrimental for the spatial resolution of materials involving low-energy X-ray lines, in certain specific conditions. Finally, quantitative X-ray microanalysis of heterogeneous materials is briefly reviewed.

The rapid advance and falling costs of computing power and data storage during the last 40 years have greatly enhanced the data reduction speed and analytical capacity of energy dispersive spectroscopy (EDS) systems. At the same time, the solid state X-ray detector [until recently, the Si(Li) diode] has seen performance increases due to the use of advanced materials and processing techniques. In addition, the performance of the electronic components (field effect transistor, preamp, and pulse processor) of an EDS system has been constantly improved. These technology advances have resulted in improved spectral quality, excellent light element detection, and increased count rate performance. The results have been truly remarkable and driven by the needs of the analyst. This article will summarize the progress made in these areas in the last 40 years and make a brief reference to prospects for future development in EDS system performance.

Electron channeling effects can create measurable signal intensity variations in all product signals that result from the scattering of the electron beam within a crystalline specimen. Of particular interest to the X-ray microanalyst are any variations that occur within the characteristic X-ray signal that are not directly related to a specimen composition variation. Many studies have documented the effect of crystallographic orientation on the local X-ray yield; however, the vast majority of these studies were carried out on thin foil specimens examined in transmission. Only a few studies have addressed these effects in bulk specimen materials, and these analyses were generally carried out at common scanning electron microscope microanalysis overvoltages (>1.5). At these overvoltage levels, the anomalous transmission effect is weak. As a result, the effect of electron channeling on the characteristic X-ray signal intensity has traditionally been overlooked in the field of quantitative electron probe microanalysis. The present work will demonstrate that electron channeling can produce X-ray variations of up to 26%, between intensity maxima and minima, in low overvoltage X-ray microanalyses of bulk specimens. Intensity variations of this magnitude will significantly impact the accuracy of qualitative and quantitative X-ray microanalyses at low overvoltage on engineering structural materials.

The derivation of a universal equation to compute the range of emitted X rays is presented for homogeneous bulk materials. This equation is based on two fundamental assumptions: the φ(ρz) curve of X-ray generation is constant and the ratio of the emitted to the generated X-ray range is equal to the ratio of the emitted to the generated X-ray intensity. An excellent agreement is observed with data obtained from Monte Carlo simulations of 200,000 electron trajectories in C, Al, Cu, Ag, Au, and an Fe–B alloy with boron weight fractions equal to 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 0.99, performed with the electron beam energy varied from 1 to 30 keV in 1-keV steps. When the ratio of the generated X-ray range to the photon mean free path is much smaller than one, the emission X-ray range is equal to the generated X-ray range, but when this ratio is much greater than one, the emission X-ray range is constant and is given by the product of the effective photon mean free path multiplied by the sine of the take-off angle.

Cation exchange capacity (CEC) characterizes the number of fixed negative charges of plant cell walls and is an important parameter in studies dealing with the uptake of ions into plant tissues, especially in roots. Conventional methods of CEC determination use bulk tissue, the results are the mean of many cells, and differences in the CEC of different tissue types are masked. Energy-dispersive microanalysis (EDX) in the transmission electron microscope allows CEC determinations on much finer scales. Shoot and fine root tissue of Picea abies was acid washed to remove exchangeable cations. Tissue blocks or semithin tissue sections were loaded with 0.2 mM CaCl2, AlCl3, or Pb(NO3)2 at pH 4.0. The amount of Ca, Al, or Pb adsorbed to the exchange sites of cell walls was determined by EDX. The CEC of cell walls of different tissue types was highly different, ranging in shoot tissues from 0 to 856 mM Ca and 5.8 to 1463 mM Al (block loading) or 4.3 to 1116 mM Ca and 0 to 2830 mM Al (section loading). In root tissue, Pb adsorption to semithin sections yielded CEC values between 29.1 and 954 mM Pb. In most P. abies shoot tissues, the binding capacity was clearly higher for Al than for Ca.

Multivariate statistical analysis methods have been applied to scanning transmission electron microscopy (STEM) energy-dispersive X-ray spectral images. The particular application of the multivariate curve resolution (MCR) technique provides a high spectral contrast view of the raw spectral image. The power of this approach is demonstrated with a microelectronics failure analysis. Specifically, an unexpected component describing a chemical contaminant was found, as well as a component consistent with a foil thickness change associated with the focused ion beam specimen preparation process. The MCR solution is compared with a conventional analysis of the same spectral image data set.

A new Monte Carlo program, Win X-ray, is presented that predicts X-ray spectra measured with an energy dispersive spectrometer (EDS) attached to a scanning electron microscope (SEM) operating between 10 and 40 keV. All the underlying equations of the Monte Carlo simulation model are included. By simulating X-ray spectra, it is possible to establish the optimum conditions to perform a specific analysis as well as establish detection limits or explore possible peak overlaps. Examples of simulations are also presented to demonstrate the utility of this new program. Although this article concentrates on the simulation of spectra obtained from what are considered conventional thick samples routinely explored by conventional microanalysis techniques, its real power will be in future refinements to address the analysis of sample classifications that include rough surfaces, fine structures, thin films, and inclined surfaces because many of these can be best characterized by Monte Carlo methods. The first step, however, is to develop, refine, and validate a viable Monte Carlo program for simulating spectra from conventional samples.

Automatic qualitative analysis for peak identification is a standard feature of virtually all modern computer-aided analysis software for energy dispersive X-ray spectrometry with electron excitation. Testing of recently installed systems from four different manufacturers has revealed the occasional occurrence of misidentification of peaks of major constituents whose concentrations exceeded 0.1 mass fraction (10 wt%). Test materials where peak identification failures were observed included ZnS, KBr, FeS2, tantalum-niobium alloy, NIST Standard Reference Material 482 (copper–gold alloy), Bi2Te3, uranium–rhodium alloys, platinum–chromium alloy, GaAs, and GaP. These misidentifications of major constituents were exacerbated when the incident beam energy was 10 keV or lower, which restricted or excluded the excitation of the high photon energy K- and L-shell X-rays where multiple peaks, for example, Kα (K-L2,3)–Kβ (K-M2,3); Lα (L3-M4,5)–Lβ (L2-M4)–Lγ (L2-N4), are well resolved and amenable to identification with high confidence. These misidentifications are so severe as to properly qualify as blunders that present a serious challenge to the credibility of this critical analytical technique. Systematic testing of a peak identification system with a suite of diverse materials can reveal the specific elements and X-ray peaks where failures are likely to occur.

The intracellular distribution of the elements carbon, nitrogen, and oxygen was measured in cultured rat hepatocytes by energy dispersive electron probe X-ray microanalysis of 100-nm-thick freeze-dried cryosections. Electron irradiation with a dose up to 106 e/nm2 caused no or merely negligible mass loss in mitochondria and in cytoplasm. Cell nuclei lost carbon, nitrogen, and—to a clearly higher extent—oxygen with increasing electron irradiation. Therefore, electron doses less than 3 × 105 e/nm2 were used to measure the subcellular compartmentation of carbon, nitrogen, and oxygen in cytoplasm, mitochondria, and nuclei of the cells. The subcellular distribution of carbon, nitrogen, and oxygen reflects the intracellular compartmentation of various biomolecules. Cells exposed to inorganic mercury before cryofixation showed an increase of oxygen in nuclei and cytoplasm. Concomitantly the phosphorus/nitrogen ratio decreased in mitochondria. The data suggest mercury-induced production of ribonucleic acid (RNA) and decrease of adenosine triphosphate (ATP). Although biomolecules cannot be identified by X-ray microanalysis, measurements of the whole element spectrum including the light elements carbon, nitrogen, and oxygen can be useful to study specific biomolecular activity in cellular compartments depending on the functional state of the cell.

The microanalysis of nonconductive specimen in a scanning electron microscope is limited by charging effects. Using a charge density model for the electric field buildup in a nonconductive specimen irradiated by electrons, a Monte Carlo simulation method has been applied to alumina (Al2O3). The results show a change in the depth distribution for characteristic and bremsstrahlung X-ray, φ(ρz) curves, and ψ(ρz) curves (with absorption) for both elements' Kα lines. The influence of the electric field on the measured X-ray intensity is shown. The dependency of this influence by the three parameters, electron energy, X-ray energy, and charge density, is clarified.