We report on a robust method for chemical element-sensitive imaging by scanning electron microscopy (SEM). The commercial Auriga FE-SEM microscope (Carl Zeiss, Oberkochen, Germany), equipped with an energy-selective grid detector (EsB) as a part of the experimental setup, was applied for generation of chemical contrast at low accelerating voltages, which is gentle for sensitive samples. The EsB-grid detector, conceptually adapted by us as an energy retarding field analyzer (RFA), was used to detect the two-dimensional (2D) energy spectrum for the first time. The electron energy spectrum measured by sweeping the retarding grid potential revealed thresholds corresponding to electronic transitions in the specimen, followed by 2D-derivation treatment applied just at the observed thresholds. This allowed chemical mapping by SEM. In this report the 273 eV Auger transition in carbon deposited onto the Si(100) sample was chosen as a source for chemical contrast in the SEM image. In addition to Auger electrons, we expect analogous energy-selective contrast enhancement for inelastically scattered electrons, for example, in plasmonic contrast and elastically scattered electrons, for example in phase contrast, our method, proved for carbon, is expected to apply to a broader list of elements as a general capability of chemical mapping, at several-fold better lateral resolution when compared with energy dispersive spectroscopy (EDS).

In this study, µ-XRF was applied as a novel surface technique for quick acquisition of elemental X-ray maps of rocks, image analysis of which provides quantitative information on texture and rock-forming minerals. Bench-top µ-XRF is cost-effective, fast, and non-destructive, can be applied to both large (up to a few tens of cm) and fragile samples, and yields major and trace element analysis with good sensitivity. Here, X-ray mapping was performed with a resolution of 103.5 µm and spot size of 30 µm over sample areas of about 5×4 cm of Euganean trachyte, a volcanic porphyritic rock from the Euganean Hills (NE Italy) traditionally used in cultural heritage. The relative abundance of phenocrysts and groundmass, as well as the size and shape of the various mineral phases, were obtained from image analysis of the elemental maps. The quantified petrographic features allowed identification of various extraction sites, revealing an objective method for archaeometric provenance studies exploiting µ-XRF imaging.

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.

We describe a hybrid pixel array detector (electron microscope pixel array detector, or EMPAD) adapted for use in electron microscope applications, especially as a universal detector for scanning transmission electron microscopy. The 128×128 pixel detector consists of a 500 µm thick silicon diode array bump-bonded pixel-by-pixel to an application-specific integrated circuit. The in-pixel circuitry provides a 1,000,000:1 dynamic range within a single frame, allowing the direct electron beam to be imaged while still maintaining single electron sensitivity. A 1.1 kHz framing rate enables rapid data collection and minimizes sample drift distortions while scanning. By capturing the entire unsaturated diffraction pattern in scanning mode, one can simultaneously capture bright field, dark field, and phase contrast information, as well as being able to analyze the full scattering distribution, allowing true center of mass imaging. The scattering is recorded on an absolute scale, so that information such as local sample thickness can be directly determined. This paper describes the detector architecture, data acquisition system, and preliminary results from experiments with 80–200 keV electron beams.

Bioavailability of arsenic in contaminated soils and wastes can be reduced to insignificant levels by precipitation of mimetite Pb5(AsO4)3Cl. The objective of this study is to elucidate mechanisms of the reaction between solution containing lead ions and arsenates adsorbed on synthetic goethite (AsO4-goethite), or arsenate ions in the solution and goethite saturated with adsorbed Pb (Pb-goethite). These reactions, in the presence of Cl, result in rapid crystallization of mimetite. Formation of mimetite is faster than desorption of AsO4 but slower than desorption of Pb from the goethite surface. Slow desorption of arsenates from AsO4-goethite results in heterogeneous precipitation and formation of mimetite incrustation on goethite crystals. Desorption of lead from Pb-goethite is at least as fast as diffusion and advection of AsO4 and Cl in suspension allowing for homogeneous crystallization of mimetite in intergranular solution. Therefore, the mechanism of nucleation is primarily driven by the kinetics of constituent supply to the saturation front, rather than by the thermodynamics of nucleation. The products of the reactions are well documented using microscopy methods such as scanning electron microscopy, electron backscattered diffraction, X-ray diffraction, and Fourier transform infrared spectroscopy.

In electron probe microanalysis where materials are coated with a thin conductive carbon coat before analysis, the X-ray intensity detected from a specimen may be affected to various degrees by the thickness of the carbon coating. Differences in the carbon film thickness between specimens and standards may lead to errors in analytical results, particular for lower energy X-rays. In this study, we demonstrate that the location and the distance of the specimen relative to the carbon tip in the coating chamber can affect the thickness of the carbon film produced on the specimen surface during carbon coating. The closer the specimen is to the carbon tip contacting point, the thicker is the carbon film deposited. A mathematical model to calculate the carbon film thickness at different locations on the coater plate is established, based on the assumption that carbon atoms evaporate from the carbon tip equally in all directions during the coating process. In order to reduce the differences in the carbon coating thickness, we suggest moving the carbon rod to a higher position, moving the thinner samples to the center and thicker samples to the edge of the coater plate, and using a rotating circular coater plate during coating.

We present a simple, fast method for thickness characterization of suspended graphene/graphite flakes that is based on transmission electron microscopy (TEM). We derive an analytical expression for the intensity of the transmitted electron beam I0(t), as a function of the specimen thickness t (t<<λ; where λ is the absorption constant for graphite). We show that in thin graphite crystals the transmitted intensity is a linear function of t. Furthermore, high-resolution (HR) TEM simulations are performed to obtain λ for a 001 zone axis orientation, in a two-beam case and in a low symmetry orientation. Subsequently, HR (used to determine t) and bright-field (to measure I0(0) and I0(t)) images were acquired to experimentally determine λ. The experimental value measured in low symmetry orientation matches the calculated value (i.e., λ=225±9 nm). The simulations also show that the linear approximation is valid up to a sample thickness of 3–4 nm regardless of the orientation and up to several ten nanometers for a low symmetry orientation. When compared with standard techniques for thickness determination of graphene/graphite, the method we propose has the advantage of being simple and fast, requiring only the acquisition of bright-field images.

When the value of the dispersion coefficient is “greatly different from 0.5,” as is the case for “free-electron” materials such as sodium (Na), the approximate expression for the volume plasmon critical wave vector (PCV) used by Hadji stops being valid and a different, more precise, expression must be used. Here a more accurate PCV formula is used to get a more accurate expression for plasmon scattering cross-section per atom (PSCA) species. This PSCA is then employed to calculate some physical quantities for several “free-electron” materials and together with the techniques from the quoted paper to determine values for physical quantities from amorphous silicon (a-Si) experimental data. The program source used to obtain these values is supplied. Any valid formula for the PSCA species is, in fact, relevant for use together with the two quoted techniques. The PCV and the dispersion coefficient have upper limits. Negative dispersion coefficient values are allowed. A PCV-related dimensionless universal function that can represent all ideal “free-electron” materials is given. “Not greatly different from 0.5” is mathematically expressed.

In the present work, the dielectric response of III-nitride semiconductors is studied using density functional theory (DFT) band structure calculations. The aim of this study is to improve our understanding of the features in the low-loss electron energy-loss spectra of ternary alloys, but the results are also relevant to optical and UV spectroscopy results. In addition, the dependence of the most remarkable features with composition is tested, i.e. applying Vegard’s law to band gap and plasmon energy. For this purpose, three wurtzite ternary alloys, from the combination of binaries AlN, GaN, and InN, were simulated through a wide compositional range (i.e., AlxGa1−xN, InxAl1−xN, and InxGa1−xN, with x=[0,1]). For this DFT calculations, the standard tools found in Wien2k software were used. In order to improve the band structure description of these semiconductor compounds, the modified Becke–Johnson exchange–correlation potential was also used. Results from these calculations are presented, including band structure, density of states, and complex dielectric function for the whole compositional range. Larger, closer to experimental values, band gap energies are predicted using the novel potential, when compared with standard generalized gradient approximation. Moreover, a detailed analysis of the collective excitation features in the dielectric response reveals their compositional dependence, which sometimes departs from a linear behavior (bowing). Finally, an advantageous method for measuring the plasmon energy dependence from these calculations is explained.