Algae like diatoms are widely studied as a means to remediate anthropogenically contaminated sites. In the present study, CL (cathodoluminescence) and EDX (energy-dispersive X-ray) spectroscopy in an SEM (scanning electron microscope) were optimized for the detection of Eu(III) sorbed on diatom biosilica. The required stability of biosilica under a focused electron beam was extensively investigated. Using experimentally determined data of thermal properties, the temperature increase within biosilica exposed to an electron beam was simulated by finite element calculations based on results from Monte Carlo simulations of electron scattering. Complementary thermogravimetric studies substantiated a chemical stability of biosilica in a wide temperature range, confirming its suitability for long-lasting SEM investigations. In subsequent EDX measurements, characteristic Eu lines were detected. Eu was found to preferentially accumulate and aggregate on silica fragments. CL spectra were obtained for the Eu(III) reference material, EuCl3. For Eu-loaded biosilica, even parts without detectable Eu signal in the EDX spectra show significant Eu(III) signals in the CL spectra. This highlights the sensitivity of CL in studying f-element sorption. CL data showed that Eu(III) was distributed on the entire surface. In conclusion, this work demonstrates the merit of CL and EDX methods for sorption studies on biogenic materials.

Atomic mapping of nanomaterials, in particular nanoparticles, using atom probe tomography (APT) is of great interest, as their properties strongly depend on shape, size, and composition. However, APT analyses of nanoparticles are extremely challenging, and there is an urgent need for developing robust and universally applicable sample preparation methods. Herein, we explored a method based on pulse electrodeposition to embed Ag nanoparticles in a Ni matrix and prepare APT specimens from the resulting composite film. By systematically varying the duty cycle during pulse electrodeposition, the dispersion and number density of the nanoparticles within the matrix was significantly enhanced as compared to DC electrodeposition. Several Ag nanoparticles were analyzed with APT from such samples. Shape distortions and biased compositions were observed for the Ag nanoparticles after applying a standard data reconstruction protocol. Numerical simulations of the field evaporation process showed that such artifacts were caused by a difference in the evaporation field of Ni and Ag and a local magnification effect. We expect such detrimental effects to be mitigated by a careful selection of the matrix material, matching the evaporation field of the nanoparticles. Furthermore, we anticipate that the method presented herein can be extended to a wider range of nanomaterials.

Determining free lime content in steelmaking slag is crucial for its safe reuse in road construction. A simple method has been recently developed to rapidly derive this value via cathodoluminescence (CL) imaging of steelmaking slag, previously quenched from 1,000°C to room temperature, according to the illuminated areas corresponding to free lime (luminescence peak at 600 nm). This quenching is required to obtain intense CL from free lime, but the mechanism of such signal enhancement is still unknown. Therefore, the present study investigated the mechanism by comparing the microstructures, CL images, and CL spectra of free lime in quenched and unquenched steelmaking slag. Large amounts of defects, including dislocations, were observed in the free lime emitting intense luminescence at 600 nm, whereas the samples without clear CL exhibited only a few defects. These results and previous studies suggest that the luminescence at 600 nm from free lime is enhanced by the CL originating from oxygen vacancies (380 nm); therefore, the enhancement of the intensity of the free lime CL peak could be attributed to the increase in the oxygen vacancies via quenching from 1,000°C to room temperature.

High-temperature differential scanning calorimetry was used to understand the thermal properties of Si-rich metal–silicon alloys. Insoluble metals (A and B) were found to produce an alloy with discrete ASi2 and BSi2 dispersed phases. In contrast, metals that form a solid solution result in a dispersed phase that has a composition of AxB1−xSi2, where x varies continuously across each inclusion. This complex composition distribution is putatively caused by differences in the solidification temperatures of ASi2 versus BSi2. Though this behavior was observed for several different combinations of metals, we focus here specifically on the Cr/V/Si system. To better understand the range and most probable element concentrations in the dispersed silicide domains, a method was devised to generate histograms of their Cr and V concentrations from energy-dispersive X-ray spectroscopy hyperspectral images. Varying the Cr/V/Si ratio was found to change the shape of the element histograms, indicating that the distribution of silicide compositions that form is controlled by the input composition. Adding aluminum was found to result in dispersed phases that had a single composition rather than a range of Cr and V concentrations. This demonstrates that aluminum can be an effective additive for altering solidification kinetics in silicon alloys.

Electron probe microanalysis is a nondestructive technique widely used to determine the elemental composition of bulk samples. This was extended to layered specimens, with the development of appropriate software. The traditional quantification method requires the use of matrix correction procedures based upon models of the ionization depth distribution, the so-called ϕ(ρz) distribution. Most of these models have led to commercial quantification programs but only few of them allow the quantification of layered specimens. Therefore, we developed BadgerFilm, a free open-source thin film program available to the general public. This program implements a documented ϕ(ρz) model as well as algorithms to calculate fluorescence in bulk and thin film samples. Part 1 of the present work aims at describing the operation of the implemented ϕ(ρz) distribution model and validating its implementation against experimental measurements and Monte Carlo simulations on bulk samples. The program has the ability to predict absolute X-ray intensities that can be directly compared to Monte Carlo simulations. We demonstrate that the implemented model works very well for bulk materials. And as will be shown in Part 2, BadgerFilm predictions for thin film specimens are also shown to be in good agreements with experimental and Monte Carlo results.

Atomically sharpened tips have attracted much interest in the imaging and manufacturing fields due to their high spatial resolutions. Typically, tungsten (W) is mainly used as the material of such a tip, but when the W tip is used in an oxygen environment, a limit is revealed due to corrosiveness stemming from a reaction with the oxygen gas. To solve this problem, methods of depositing a metal on W that does not react with oxygen have been studied. In this study, we introduce a method of depositing iridium (Ir) directly onto an insulating layer without an additional pretreatment to remove the insulating layer remaining on the W surface, forming an Ir-nanopyramid structure at the apex of the W tip by field evaporation and faceting. Field ion microscopy and atom probe tomography were used to analyze the crystal structure and composition at the apex during the faceting process, and the overall tip shape change after faceting was compared and analyzed with transmission electron microscopy. The proposed method does not have a tip heating step when creating an atomically sharp tip such that it can be made easily with a simpler equipment configuration than in the existing method.

The measurement of the composition of ε-Ga2O3 and the quantification of Sn doping in ε-Ga2O3:Sn by laser-assisted atom probe tomography (APT) may be inaccurate depending on the experimental conditions. Both the role of the laser energy and surface electric field were investigated, and the results clearly indicate that deviations from stoichiometry are observed changing the electric field conditions during APT. The measured atomic fraction of Ga can change from 0.45 at low field to 0.38 at high field, to be compared with the expected 0.4. This was interpreted in terms of preferential evaporation of Ga at high field and deficit of O at low field, which was caused by the formation of neutrals. The quantification of Sn-doping is accurate at low-field conditions, with an overestimation of the detected Sn-metallic fraction at high field. This suggests that Sn has a higher evaporation field compared to Ga. Finally, multiple detection events were in-depth studied, revealing that three dissociation reactions occur during APT: GaO2+ → Ga+ + O+; Ga2O22+ → Ga+ + GaO2+; Ga3O22+ → Ga+ + Ga2O2+. Nevertheless, only 2% of the detected events are related to such dissociation reactions, too small a fraction to fully explain the observed deviation from the stoichiometric composition in ε-Ga2O3.

Atom probe tomography is a powerful tool for investigating nanostructures such as interfaces and nanoparticles in material science. Advanced analysis tools are particularly useful for analyzing these nanostructures characterized very often by curved shapes. However, these tools are very limited for complex materials with non-negligible peak overlaps in their respective mass-to-charge ratio spectra. Usually, an analyst solves peak overlaps in the bulk regions, but the behavior at interfaces is rarely considered. Therefore, in this work, we demonstrate how the proximity histogram generated for a specific interface can be corrected by using the natural abundances of isotopes. This leads to overlap-solved proximity histograms with a resolution of up to 0.1 nm. This work expands on previous work that showed the advantage of a maximum-likelihood peak overlap solving. The corrected proximity histograms together with the maximum-likelihood peak overlap algorithm were implemented in a user-friendly software suite called EPOSA.

In the field of high-temperature superconductors, atom probe tomography is a relatively new instrument, with the ability to provide a new perspective on the 3D nanoscale microstructure. However, field evaporation of nonmetallic materials is fraught with unique challenges that matter little in the world of metallic evaporation. In this study, we review the laser absorption, correlated evaporation, molecular dissociation, and the crystallographic effects on the field evaporation of 800-m ${\rm RB}{\rm a}_ 2{\rm C}{\rm u}_ 3{\rm O}_{ 7-{\rm \delta }}$ (R = Gd, Sm) coated conductor tapes deposited by Reactive Co-Evaporation Cyclic Deposition and Reaction (RCE-CDR). Ultraviolet 355 nm laser pulsing was found to have a substantial beneficial effect on minimizing the fracture probability compared with 532 nm illumination, especially when evaporating insulating oxide precipitates. This, in turn, allows for the 3D compositional analysis of defects such as flux pinning centers introduced by precipitation and doping. As a result, evidence for the precipitation of nanoscale ${\rm G}{\rm d}_ 2{\rm C}{\rm u}_ 2{\rm O}_ 5$ is discussed. The effect of crystallographic orientation is studied, where [001] aligned evaporation is found to develop compositional aberrations.

Local magnification artifacts in atom probe tomography (APT) caused by multiphase materials with heterogeneous evaporation behavior are a well-known problem. In particular, the analysis of the exact size, shape, and composition of small precipitates is, therefore, not trivial. We performed numerical simulations of APT measurements to predict the reconstructed morphology of precipitates with contrasting evaporation thresholds. Based on a statistical approach that avoids coarse graining, the simulated data are evaluated to develop a model for the calculation of the original size of the precipitates. The model is tested on experimental APT data of precipitates with a higher and lower evaporation field in a ferritic alloy. Accurate sizes, proven by a complementary investigation by transmission electron microscopy, are obtained. We show further, how the size information can be used to obtain compositional information of the smallest precipitates and present a new methodology to determine a correct in-depth scaling of the APT reconstruction in case no complementary geometric information about the specimen exists or if no lattice planes are visible in the reconstruction.

The microstructure and texture evolution of Ni-5 at%W (Ni5W) alloy substrates were investigated by in situ tensile testing along the rolling direction (RD), transverse direction (TD), and at 45° to the RD (45°-RD), as well as by electron backscatter diffraction characterization. The tensile stress direction had a significant influence on the texture evolution. The cubic texture in the Ni-5 at%W alloy exhibited severe degradation when the tensile angle was 45°-RD. In contrast, the cubic texture was relatively stable under high deformation along the RD or TD. It was found that the slip line system in the 45°-RD specimen was the key to the contrasting behavior. The effect of the tensile testing angle on the cubic texture evolution for Ni–W substrates was investigated, and the corresponding effect on the superconducting properties of coated materials was studied.

Multilayers that comprise thin films of heavy metals and ferromagnets have been shown to host Néel-type magnetic skyrmions at room temperature. Fresnel defocus imaging in Lorentz transmission electron microscopy is a widely used technique for recording magnetic information about skyrmions. However, the visibility of Néel-type skyrmions in Fresnel defocus images is typically low, both because only a small component of their magnetic field contributes to the signal and because of the presence of diffraction contrast from the polycrystalline multilayer structure. Here, we take advantage of the out-of-plane hysteresis in such samples to record background-subtracted Fresnel defocus images. We demonstrate an improvement in magnetic signal-to-noise ratio and spatial resolution by a factor of 3 for a (Pt/Co/NiFe)×5 multilayer. We also use simulated Fresnel defocus images of Néel-type magnetic skyrmions to understand the influence of defocus on apparent skyrmion size.

Since the 1960s, thicknesses and compositions of thin-film specimens have been determined by using the nondestructive technique of electron probe microanalysis. This approach, refined in the 1990s, is based upon models of the ionization depth distribution, the so-called ϕ(ρz) distribution, and is capable of analyzing layered specimens. Most of these quantification models have led to commercial programs. However, these programs may have possible limitations: some may not be directly compatible with modern computers, they often are “black boxes” making it difficult to assess the reliability of the results, and they are sometimes expensive enough to restrain many labs from purchasing them. We present a user-friendly, free, open-source program, BadgerFilm, implementing a documented ϕ(ρz) model and algorithms allowing the quantification of stratified samples. The program has the ability to calculate absolute X-ray intensities that can be directly compared with Monte Carlo simulations. We give a detailed explanation for the operation of the employed ϕ(ρz) model in thin films. A wide range of detailed Monte Carlo simulations and experimental data have been used to evaluate and validate the accuracy of the implemented algorithms. BadgerFilm demonstrated excellent quantification results for the films and in many cases for the substrates.

Nanowire-based nanocomposite materials are being developed as transparent and flexible electrodes or as stretchable conductors and dielectrics for biosensing. Here, we theoretically investigate the use of scanning dielectric microscopy (SDM) to characterize these materials in a nondestructive way, with a special focus on the achievable spatial resolution and the possibility of detection of the capacitive coupling between nearby nanowires. Numerical calculations with models involving single and multiple buried nanowires have been performed. We demonstrate that the capacitance gradient spread function of a single buried nanowire consists of a modified Lorenzianan with a cubic decay. We show that the achievable spatial resolution can be determined with good accuracy with the help of this spread function. It is shown that, in general, the spatial resolution worsens when any system parameter decreases the maximum of the nanowire spread function or increases its width, or both. Finally, we show that SDM measurements are also sensitive to the capacitive coupling between nearby nanowires. This latter result is of utmost relevance since the macroscopic electric properties of nanowire nanocomposites largely depend on the electric interaction between nearby nanowires. The present results show that SDM can be a valuable nondestructive subsurface characterization technique for nanowire nanocomposite materials.