3D Elemental Distribution Research Articles

Analysis of 3D elemental distribution in nanomaterials: Towards higher throughput and dose efficiency.

Many advanced nanomaterials rely on carefully designed morphology and elemental distribution to achieve their functionalities. Among the few experimental techniques that can directly visualise the 3D elemental distribution on the nanoscale are approaches based on electron tomography in combination with energy-dispersive X-ray spectroscopy (EDXS) and electron energy loss spectroscopy (EELS). Unfortunately, these highly informative methods are severely limited by the fundamentally low signal-to-noise ratio, which makes long experimental times and high electron irradiation doses necessary to obtain reliable 3D reconstructions. Addressing these limitations has been the major research question for the development of these techniques in recent years. This short review outlines the latest progress on the methods to reduce experimental time and electron irradiation dose requirements for 3D elemental distribution analysis and gives an outlook on the development of this field in the near future.

Micromorphology, mineralogy, and geochemistry of ferromanganese nodules in tropical soils and their impacts on heavy metal sequestration

Ferromanganese nodules (FMNs) are important products of soil-forming processes that can reflect the historical pedogenic environment and affect the elemental cycle in the soil. Despite extensive investigations on the morphology, microstructure, and components of FMNs, non-destructive observation of the 3D microstructure and elemental distribution feature of FMNs remains difficult, owing to the limitations of conventional measurement techniques and instrumental accuracy. In this study, the micromorphological, mineralogical and geochemical characteristics of FMNs in basalt-derived soils in tropical China were examined using different techniques, including scanning electron microscopy, X-ray diffraction, chemical extraction, and synchrotron radiation-based X-ray microtomography and microfluorescence mapping. Mn and Fe in FMNs were found to be inversely distributed in concentric rings, with Mn mainly enriched in the interior and Fe mainly distributed at the edge of the nodule. A line scan of the cross-section of FMNs revealed symmetrical distributions of the peak Fe and Mn contents and Fe:Mn ratios, indicating alternating dry/wet conditions and oxidation/reduction reactions during the formation of FMNs. FMNs were significantly enriched in P and various heavy metals, including Ba, Co, Cu, and Ni. The enrichment factors of P, Ba, Co, Cu, and Ni were in the range of 1.20–4.68, 8.34–27.12, 12.92–24.74, 2.51–3.55, and 2.75–3.58, respectively, reflecting the potential of FMNs to influence the soil nutrient cycle and heavy metal sequestration. Factor analysis further verified the adsorption of heavy metals by FMNs and indicated that the formation of FMNs was accompanied by an increase in Mn-bearing mineral and a decrease in phyllosilicate. Our study demonstrates that FMNs provide important information for understanding changes in pedogenic environment and heavy metal behavior in tropical soils.

Tracking the Mn Diffusion in the Carbon-Supported Nanoparticles Through the Collaborative Analysis of Atom Probe and Evaporation Simulation.

Carbon-supported nanoparticles have been used widely as efficient catalysts due to their enhanced surface-to-volume ratio. To investigate their structure–property relationships, acquiring 3D elemental distribution is required. Here, carbon-supported Pt, PtMn alloy, and ordered Pt3Mn nanoparticles are synthesized and analyzed with atom probe tomography as model systems. A significant difference of Mn distribution after the heat-treatment was found. Finally, the field evaporation behavior of the carbon support was discussed and each acquired reconstruction was compared with computational results from an evaporation simulation. This paper provides a guideline for studies using atom probe tomography on the heterogeneous carbon-supported nanoparticle system that leads to insights toward a wide variety of applications.

Rare earth element identification and quantification in millimetre-sized Ryugu rock fragments from the Hayabusa2 space mission

Millimetre-sized primordial rock fragments originating from asteroid Ryugu were investigated using high energy X-ray fluorescence spectroscopy, providing 2D and 3D elemental distribution and quantitative composition information on the microscopic level. Samples were collected in two phases from two sites on asteroid Ryugu and safely returned to Earth by JAXA’s asteroid explorer Hayabusa2, during which time the collected material was stored and maintained free from terrestrial influences, including exposure to Earth’s atmosphere. Several grains of interest were identified and further characterised to obtain quantitative information on the rare earth element (REE) content within said grains, following a reference-based and computed-tomography-assisted fundamental parameters quantification approach. Several orders of magnitude REE enrichments compared to the mean CI chondrite composition were found within grains that could be identified as apatite phase. Small enrichment of LREE was found for dolomite grains and slight enrichment or depletion for the general matrices within the Ryugu rock fragments A0055 and C0076, respectively.Graphical

Quantification routines for full 3D elemental distributions of homogeneous and layered samples obtained with laboratory confocal micro XRF spectrometers

Confocal micro-X-ray fluorescence spectroscopy can be performed with laboratory spectrometers for elemental imaging and quantification with 3D resolution.

Identification of the Calcium, Aluminum, and Magnesium Distribution within Millimeter-Sized Extraterrestrial Materials Using Nonresonant X-ray Raman Spectroscopy in Preparation for the Hayabusa2 Sample Return Mission.

The nondestructive investigation of millimeter-sized meteoritic materials is often hindered by self-absorption effects. Using X-ray-based analytical methods, the information depth for many elements (Z < 30) is in the range of up to only a few hundred micrometers, and for low-Z elements (Z < 20), this is reduced even further to only a few tens of micrometers. However, the investigation of these low-Z elements, in particular calcium, aluminum, and magnesium, is of great importance to planetary geologists and cosmochemists, as these elements are regularly used to characterize and identify specific features of interest in extraterrestrial materials, especially primitive chondritic material. In this work, nonresonant inelastic X-ray scattering from core electrons was performed at beamline ID20 of the ESRF in a direct tomography approach in order to visualize these low-Z elements within the millimeter-sized meteoritic samples. The obtained 3D elemental distribution volumes were compared to results from X-ray fluorescence-CT and absorption CT experiments and were found to be in good agreement. Additionally, several regions of interest could be identified within the inelastic scattering volumes, containing information that is not available through the other presented means. As such, the proposed approach presents a valuable tool for the nondestructive investigation of low-Z elemental distributions within millimeter-sized extraterrestrial materials, such as the samples of the Hayabusa2 sample return mission.

Identification of core/shell structure in Cd‐Zn‐Se QDs inside silicate glasses using 3D elemental distribution analysis

AbstractCore‐shell structure in Cd‐Zn‐Se quantum dots (QDs) precipitated in the silicate glass matrix by continuous wave laser (λ = 532 nm) were demonstrated using transmission electron microscopy (TEM) and local electrode atom probe (LEAP) tomography. TEM images of the QDs in glasses after 60 min of irradiation at 9 W/cm2 show two portions with different contrasts, and diameters of 5.97 and 22.49 nm, respectively; 3D elemental distribution in these glasses from LEAP tomography shows areas of high Zn concentration near the CdSe QDs. Iso‐concentration images obtained using visualization software show that Cd‐rich clusters were not completely covered by the Zn‐rich shells in the glass after 15 min irradiation that resulted emission due to the surface defects of CdSe QDs. As the irradiation time increased to 60 min, the Zn‐rich cluster gradually surrounded the Cd‐rich core to form shells that eliminated the surface defects. During laser irradiation, CdSe QDs precipitated first due to the high degree of supersaturation of Cd and Se followed by the sequential incorporation of Zn on the Cd‐rich QDs forming shells.

XUV laser mass spectrometry for nano-scale 3D elemental profiling of functional thin films

Direct nano-scale microanalysis is important for photovoltaic functional thin films to characterize their homogeneity and purity. This demands combining spatial resolution in the micro/nano-scale and sensitivity in the trace-level range, which is at the moment beyond state-of-the-art. As dictated by counting statistics, the reduction of the spot size degrades the detection limit. The utilization of a tabletop XUV laser at λ = 46.9 nm has shown to dramatically improve the ablation efficiency with respect to that of visible lasers, such that ablation spot of 1 μm limits. Li-doped Cu2ZnSn(S,Se)4 (so-called kesterite) thin films were irradiated across 3D ablation arrays for hyperspectral mapping by means of time-of-flight mass spectrometry. The nominal 3D data node lattices were the initialisation perceptron, filled with measured values, and for a detailed supervised learning postprocessing, the node-to-node links were analysed by means of a 2D-kernel covariance algorithm. The latter permitted to obtain robust 3D elemental distribution functions well below the measurement spacing, giving insights into the inhomogeneity and impurities.

Potential of gas-assisted time-of-flight secondary ion mass spectrometry for improving the elemental characterization of complex metal-based systems

Enhancing the spatial resolution of TOF-SIMS, which provides 3D elemental distribution in combination with high sensitivity and molecular information, is currently one of the hottest topics in the field of chemical analysis at the nanoscale.

3D Imaging of Nanoparticles in an Inorganic Matrix Using TOF-SIMS Validated with STEM and EDX.

Imaging nano-objects in complex systems such as nanocomposites using time-of-flight secondary ion mass spectrometry (TOF-SIMS) is a challenging task. Due to a very small amount of the material and a matrix effect, the number of generated secondary ions can be insufficient to represent a 3D elemental distribution despite being detected in a mass spectrum. Therefore, a model sample consisting of a ZrCuAg matrix with embedded Al nanoparticles is designed. A high mass difference between the light Al and heavy matrix components limits mass interference. The chemical structure measurements using a pulsed 60 keV Bi32+ beam or a continuous 30 keV Ga+ beam reveals distinct Al signal segregation. This can indicate a spatially resolved detection of single 10s of nanometer large particles and/or their agglomerates for the first time. However, TOF-SIMS images of 50 nm or smaller objects do not necessarily represent their exact size and shape but can rather be their convolutions with the primary ion beam shape. Therefore, the size of nanoparticles (25-64 nm) was measured using scanning transmission electron microscopy. Our studies prove the capability of TOF-SIMS to image chemical structure of nanohybrids which is expected to help building new functional materials and optimize their properties.

Single-shot 3D coherent diffractive imaging of core-shell nanoparticles with elemental specificity

We report 3D coherent diffractive imaging (CDI) of Au/Pd core-shell nanoparticles with 6.1 nm spatial resolution with elemental specificity. We measured single-shot diffraction patterns of the nanoparticles using intense x-ray free electron laser pulses. By exploiting the curvature of the Ewald sphere and the symmetry of the nanoparticle, we reconstructed the 3D electron density of 34 core-shell structures from these diffraction patterns. To extract 3D structural information beyond the diffraction signal, we implemented a super-resolution technique by taking advantage of CDI’s quantitative reconstruction capabilities. We used high-resolution model fitting to determine the Au core size and the Pd shell thickness to be 65.0 ± 1.0 nm and 4.0 ± 0.5 nm, respectively. We also identified the 3D elemental distribution inside the nanoparticles with an accuracy of 3%. To further examine the model fitting procedure, we simulated noisy diffraction patterns from a Au/Pd core-shell model and a solid Au model and confirmed the validity of the method. We anticipate this super-resolution CDI method can be generally used for quantitative 3D imaging of symmetrical nanostructures with elemental specificity.

Enhanced Chemical Stability of Ag Nanowires by Slight Surface Modification with Pd

AbstractThe chemical stability of Ag nanowires (NWs) can be addressed by introducing a layer of noble metal alloy, in particular Ag–Pd alloy, on the Ag NW surface. Due to the high cost of noble metals, it is practically important to use the least amount of noble metals as possible while achieving the chemical and electrical properties required for the electrode. To minimize the amount of Pd added to Ag NWs, the electrode performance should be correlated with the elemental distribution of Pd in the Ag NW. In this study, the amount of Pd deposited on Ag NWs is varied and the 3D elemental distribution of Pd is characterized using atom probe tomography (APT). The results indicate that chemical stability against oxidation can be achieved when the surface layer contains a very small amount of Pd (≈5 at%), thereby maintaining the good electrical and mechanical properties of the pristine Ag NW electrode. This study demonstrates the suitability of Pd‐treated Ag NWs as electrodes for electro‐chemiluminescence involving corrosive oxidation reactions.

The three-dimensional elemental distribution based on the surface topography by confocal 3D-XRF analysis

Confocal three-dimensional micro-X-ray fluorescence (3D-XRF) is a good surface analysis technology widely used to analyse elements and elemental distributions. However, it has rarely been applied to analyse surface topography and 3D elemental mapping in surface morphology. In this study, a surface adaptive algorithm using the progressive approximation method was designed to obtain surface topography. A series of 3D elemental mapping analyses in surface morphology were performed in laboratories to analyse painted pottery fragments from the Majiayao Culture (3300–2900 BC). To the best of our knowledge, for the first time, sample surface topography and 3D elemental mapping were simultaneously obtained. Besides, component and depth analyses were also performed using synchrotron radiation confocal 3D-XRF and tabletop confocal 3D-XRF, respectively. The depth profiles showed that the sample has a layered structure. The 3D elemental mapping showed that the red pigment, black pigment, and pottery coat contain a large amount of Fe, Mn, and Ca, respectively. From the 3D elemental mapping analyses at different depths, a 3D rendering was obtained, clearly showing the 3D distributions of the red pigment, black pigment, and pottery coat. Compared with conventional 3D scanning, this method is time-efficient for analysing 3D elemental distributions and hence especially suitable for samples with non-flat surfaces.

STEM-EDX tomography of bimetallic nanoparticles: A methodological investigation

This paper presents an investigation of the limitations and optimisation of energy dispersive X-ray (EDX) tomography within the scanning transmission electron microscope, focussing on application of the technique to characterising the 3D elemental distribution of bimetallic AgAu nanoparticles. The detector collection efficiency when using a standard tomography holder is characterised using a tomographic data set from a single nanoparticle and compared to a standard low background double tilt holder. Optical depth profiling is used to investigate the angles and origin of detector shadowing as a function of specimen field of view. A novel time-varied acquisition scheme is described to compensate for variations in the intensity of spectrum images at each sample tilt. Finally, the ability of EDX spectrum images to satisfy the projection requirement for nanoparticle samples is discussed, with consideration of the effect of absorption and shadowing variations.

Methodology toward 3D micro X-ray fluorescence imaging using an energy dispersive charge-coupled device detector.

A new three-dimensional (3D) micro X-ray fluorescence (μXRF) methodology based on a novel 2D energy dispersive CCD detector has been developed and evaluated at the P06 beamline of the Petra-III storage ring (DESY) in Hamburg, Germany. This method is based on the illumination of the investigated sample cross-section by a horizontally focused beam (vertical sheet beam) while fluorescent X-rays are detected perpendicularly to the sheet beam by a 2D energy dispersive (ED) CCD detector allowing the collection of 2D cross-sectional elemental images of a certain depth within the sample, limited only by signal self-absorption effects. 3D elemental information is obtained by a linear scan of the sample in the horizontal direction across the vertically oriented sheet beam and combining the detected cross-sectional images into a 3D elemental distribution data set. Results of the 3D μXRF analysis of mineral inclusions in natural deep Earth diamonds are presented to illustrate this new methodology.

X-ray μ-Laue diffraction analysis of Cu through-silicon vias: A two-dimensional and three-dimensional study

Here, white X-ray μ-beam Laue diffraction is developed and applied to investigate elastic strain distributions in three-dimensional (3D) materials, more specifically, for the study of strain in Cu 10 μm diameter–80 μm deep through-silicon vias (TSVs). Two different approaches have been applied: (i) two-dimensional μ-Laue scanning and (ii) μ-beam Laue tomography. 2D μ-Laue scans provided the maps of the deviatoric strain tensor integrated along the via length over an array of TSVs in a 100 μm thick sample prepared by Focused Ion Beam. The μ-beam Laue tomography analysis enabled to obtain the 3D grain and elemental distribution of both Cu and Si. The position, size (about 3 μm), shape, and orientation of Cu grains were obtained. Radial profiles of the equivalent deviatoric strain around the TSVs have been derived through both approaches. The results from both methods are compared and discussed.

XEDS STEM tomography for 3D chemical characterization of nanoscale particles

We present a tomography technique which couples scanning transmission electron microscopy (STEM) and X-ray energy dispersive spectrometry (XEDS) to resolve 3D distribution of elements in nanoscale materials. STEM imaging when combined with XEDS mapping using a symmetrically arranged XEDS detector design around the specimen overcomes many of the obstacles in 3D chemical imaging of nanoscale materials and successfully elucidates the 3D chemical information in a large field of view of the transmission electron microscopy (TEM) sample. We employed this technique to investigate 3D distribution of Nickel (Ni), Manganese (Mn) and Oxygen (O) in a Li1.2Ni0.2Mn0.6O2 (LNMO) nanoparticle used as a cathode material in Lithium (Li) ion batteries. For this purpose, 2D elemental maps were acquired for a range of tilt angles and reconstructed to obtain 3D elemental distribution in an isolated LNMO nanoparticle. The results highlight the strength of this technique in 3D chemical analysis of nanoscale materials by successfully resolving Ni, Mn and O elemental distributions in 3D and discovering the new phenomenon of Ni surface segregation in this material. Furthermore, the comparison of simultaneously acquired high angle annular dark field (HAADF) STEM and XEDS STEM tomography results shows that XEDS STEM tomography provides additional 3D chemical information of the material especially when there is low atomic number (Z) contrast in the material of interest.

3D elemental distribution images in biological samples by XRFµCT

An X-ray transmission microtomography (CT) system combined with an X-ray fluorescence microtomography (XRFµCT) system was implemented in the Brazilian Synchrotron Light Laboratory (LNLS), Campinas, Brazil. The aim of this work was to determine the elemental distribution in biological samples (breast, prostate and lung samples) in order to verify the concentration of some elements correlated with characteristics and pathology of each tissue observed by the transmission CT. The experiments were performed at the X-ray fluorescence beamline (D09B-XRF) of the Brazilian Synchrotron Light Laboratory, Campinas, Brazil. A quasi-monochromatic beam produced by a multilayer monochromator was used as an incident beam. The sample was placed on a high-precision goniometer and translation stages that allow rotating as well as translating it perpendicularly to the beam. The fluorescence photons were collected with an energy dispersive HPGe detector placed at 90° to the incident beam, while transmitted photons were detected with a fast Na(Tl) scintillation counter placed behind the sample on the beam path. The CT images were reconstructed using a filtered-back projection algorithm and the XRFµCT images were reconstructed using a filtered-back projection algorithm with absorption corrections. The 3D images were reconstructed using the 3D-DOCTOR software. Results from the 3D visualization showed that the distribution of iron, copper and zinc is different and heterogeneous from the analyzed samples. Copyright © 2011 John Wiley & Sons, Ltd.

Preliminary Study on the Visualization and Quantification of Elemental Compositions in Individual Microdroplets using Solidification and Synchrotron Radiation Techniques

Quantifying the solute composition of a cloud droplet (or a whole droplet) is an important task for understanding formation processes and heating/cooling rates. In this study, a combination of droplet fixation and SR-XRF microprobe analysis was used to visualize and quantify elements in a micro-scale droplet. In this study, we report the preliminary outcome of this experiment. A spherical micro-scale droplet was successfully solidified through exposure to α-cyanoacrylate vapor without affecting its size or shape. An X-ray microprobe system equipped at the beam line 37XU of Super Photon ring 8 GeV (SPring-8) was applied to visualize and quantify the elemental composition in an individual micro-scale droplet. It was possible to reconstruct 2D elemental maps for the K and Cl contained in a microdroplet that was dispensed from the 10-ppm KCl standard solution. Multi-elemental peaks corresponding to X-ray energy were also successfully resolved. Further experiments to determine quantitative measures of elemental mass in individual droplets and high-resolution Xray microtomography (i.e., 3D elemental distribution) are planned for the future.

Toward quantitative core-loss EFTEM tomography

Core-loss EFTEM tomography provides three-dimensional structural and chemical information. Multiple inelastic scattering occurring in thick specimens as well as orientation-dependent diffraction contrast due to multiple elastic scattering, however, often limit its applications. After demonstrating the capability of core-loss EFTEM tomography to reconstruct just a few monolayers thin carbon layer covering a Fe catalyst particle we discuss its application to thicker samples. We propose an approximate multiple-scattering correction method based on the use of zero-loss images and apply it successfully to copper whiskers, providing a significant improvement of the reconstructed 3D elemental distribution. We conclude this paper by a general discussion on experimental parameters affecting the accuracy of EFTEM 3D elemental mapping.