Noise Reduction of Low-Count STEM-EDX Data by Low-Rank Regularized Spectral Smoothing.

Statistically weighted principal component analysis (wPCA) is widely used to reduce the noise of scanning transmission electron microscopy-energy-dispersive X-ray (STEM-EDX) spectroscopic data. It is beneficial to retain the spatial resolution of observation in each step of the analysis, but the direct application of wPCA without preprocessing, such as spatial averaging, often fails against low-count STEM-EDX data. To enhance the applicability of wPCA while retaining spatial resolution, a step-by-step noise reduction method is considered in this study. Specifically, a numerical optimization is developed to simultaneously characterize the smoothness of EDX spectra and the low rankness of the data. In the presented approach, low-count data are first spectrally smoothed by solving this optimization problem, and then further denoised by using wPCA to project onto a subspace rigorously spanned by a small number of components. A challenging example is provided, and the improved noise reduction performance is demonstrated and compared to existing spectral smoothing techniques.

A Comparison of Solidification Structures and Submicroscale Cellular Segregation in Rapidly Solidified Stainless Steels Produced via Two-Piston Splat Quenching and Laser Powder Bed Fusion.

Fusion-based additive manufacturing techniques leverage rapid solidification (RS) conditions to create parts with complex geometries, unique microscale/nanoscale morphological features, and elemental segregation. Three custom composition stainless steel alloys with varying chromium equivalence to nickel equivalence ratio (Creq/Nieq) between 1.53 and 1.95 were processed using laser powder bed fusion (LPBF) and/or two-piston splat quenching (SQ) to produce solidification rates estimated between 0.4 and 0.8 m/s. Both scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were utilized to collect high-resolution images, electron backscatter diffraction (EBSD) phase identification, and measure cellular segregation. Similar features were observed in both LPBF and SQ samples including phase and microstructure, nanoscale oxide particles, cell size, and segregation behavior. However, dislocation pileup was observed along the cell boundaries only in the LPBF austenite solidified microstructure. Targeted adjustment of the SQ feedstock Cr and Ni concentrations, within the ASTM A240 specification for 316L resulted in no observable impact on the cell size, oxide particle size, or magnitude of segregation. Also, the amount of Ni segregation in the ferrite solidified microstructures did not significantly differ, regardless of Cr/Nieq or processing technique. SQ is demonstrated as capable of simulating RS rates and microstructures similar to LPBF for use as an alternative screening tool for new RS alloy compositions.

In Vivo Formation of HgSe Nanoparticles and Hg-Tetraselenolate Complex from Methylmercury in Seabirds-Implications for the Hg-Se Antagonism.

In vivo and in vitro evidence for detoxification of methylmercury (MeHg) as insoluble mercury selenide (HgSe) underlies the central paradigm that mercury exposure is not or little hazardous when tissue Se is in molar excess (Se:Hg > 1). However, this hypothesis overlooks the binding of Hg to selenoproteins, which lowers the amount of bioavailable Se that acts as a detoxification reservoir for MeHg, thereby underestimating the toxicity of mercury. This question was addressed by determining the chemical forms of Hg in various tissues of giant petrels Macronectes spp. using a combination of high energy-resolution X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopy, and transmission electron microscopy coupled to elemental mapping. Three main Hg species were identified, a MeHg-cysteinate complex, a four-coordinate selenocysteinate complex (Hg(Sec)4), and a HgSe precipitate, together with a minor dicysteinate complex Hg(Cys)2. The amount of HgSe decreases in the order liver > kidneys > brain = muscle, and the amount of Hg(Sec)4 in the order muscle > kidneys > brain > liver. On the basis of biochemical considerations and structural modeling, we hypothesize that Hg(Sec)4 is bound to the carboxy-terminus domain of selenoprotein P (SelP) which contains 12 Sec residues. Structural flexibility allows SelP to form multinuclear Hgx(Se,Sec)y complexes, which can be biomineralized to HgSe by protein self-assembly. Because Hg(Sec)4 has a Se:Hg molar ratio of 4:1, this species severely depletes the stock of bioavailable Se for selenoprotein synthesis and activity to one µg Se/g dry wet in the muscle of several birds. This concentration is still relatively high because selenium is naturally abundant in seawater, therefore it probably does not fall below the metabolic need for essential selenium. However, this study shows that this may not be the case for terrestrial animals, and that muscle may be the first tissue potentially injured by Hg toxicity.

Voids and compositional inhomogeneities in Cu(In,Ga)Se2 thin films: evolution during growth and impact on solar cell performance.

Structural defects such as voids and compositional inhomogeneities may affect the performance of Cu(In,Ga)Se2 (CIGS) solar cells. We analyzed the morphology and elemental distributions in co-evaporated CIGS thin films at the different stages of the CIGS growth by energy-dispersive x-ray spectroscopy in a transmission electron microscope. Accumulation of Cu-Se phases was found at crevices and at grain boundaries after the Cu-rich intermediate stage of the CIGS deposition sequence. It was found, that voids are caused by Cu out-diffusion from crevices and GBs during the final deposition stage. The Cu inhomogeneities lead to non-uniform diffusivities of In and Ga, resulting in lateral inhomogeneities of the In and Ga distribution. Two and three-dimensional simulations were used to investigate the impact of the inhomogeneities and voids on the solar cell performance. A significant impact of voids was found, indicating that the unpassivated voids reduce the open-circuit voltage and fill factor due to the introduction of free surfaces with high recombination velocities close to the CIGS/CdS junction. We thus suggest that voids, and possibly inhomogeneities, limit the efficiency of solar cells based on three-stage co-evaporated CIGS thin films. Passivation of the voids' internal surface may reduce their detrimental effects.

Radial Nanowire Light-Emitting Diodes in the (AlxGa1-x)yIn1-yP Material System.

Nanowires have the potential to play an important role for next-generation light-emitting diodes. In this work, we present a growth scheme for radial nanowire quantum-well structures in the AlGaInP material system using a GaInP nanowire core as a template for radial growth with GaInP as the active layer for emission and AlGaInP as charge carrier barriers. The different layers were analyzed by X-ray diffraction to ensure lattice-matched radial structures. Furthermore, we evaluated the material composition and heterojunction interface sharpness by scanning transmission electron microscopy energy dispersive X-ray spectroscopy. The electro-optical properties were investigated by injection luminescence measurements. The presented results can be a valuable track toward radial nanowire light-emitting diodes in the AlGaInP material system in the red/orange/yellow color spectrum.

Improving Signal-to-Noise Ratio in Scanning Transmission Electron Microscopy Energy-Dispersive X-Ray (STEM-EDX) Spectrum Images Using Single-Atomic-Column Cross-Correlation Averaging.

Acquiring an atomic-resolution compositional map of crystalline specimens has become routine practice, thus opening possibilities for extracting subatomic information from such maps. A key challenge for achieving subatomic precision is the improvement of signal-to-noise ratio (SNR) of compositional maps. Here, we report a simple and reliable solution for achieving high-SNR energy-dispersive X-ray (EDX) spectroscopy spectrum images for individual atomic columns. The method is based on standard cross-correlation aided by averaging of single-column EDX maps with modifications in the reference image. It produces EDX maps with minimal specimen drift, beam drift, and scan distortions. Step-by-step procedures to determine a self-consistent reference map with a discussion on the reliability, stability, and limitations of the method are presented here.

Segregation of In to dislocations in InGaN.

Dislocations are one-dimensional topological defects that occur frequently in functional thin film materials and that are known to degrade the performance of InxGa1-xN-based optoelectronic devices. Here, we show that large local deviations in alloy composition and atomic structure are expected to occur in and around dislocation cores in InxGa(1-x)N alloy thin films. We present energy-dispersive X-ray spectroscopy data supporting this result. The methods presented here are also widely applicable for predicting composition fluctuations associated with strain fields in other inorganic functional material thin films.

Hard-Soft Core-Shell Architecture Formation from Cubic Cobalt Ferrite Nanoparticles.

Cubic bi-magnetic hard-soft core-shell nanoarchitectures were prepared starting from cobalt ferrite nanoparticles, prevalently with cubic shape, as seeds to grow a manganese ferrite shell. The combined use of direct (nanoscale chemical mapping via STEM-EDX) and indirect (DC magnetometry) tools was adopted to verify the formation of the heterostructures at the nanoscale and bulk level, respectively. The results showed the obtainment of core-shell NPs (CoFe2O4@MnFe2O4) with a thin shell (heterogenous nucleation). In addition, manganese ferrite was found to homogeneously nucleate to form a secondary nanoparticle population (homogenous nucleation). This study shed light on the competitive formation mechanism of homogenous and heterogenous nucleation, suggesting the existence of a critical size, beyond which, phase separation occurs and seeds are no longer available in the reaction medium for heterogenous nucleation. These findings may allow one to tailor the synthesis process in order to achieve better control of the materials' features affecting the magnetic behaviour, and consequently, the performances as heat mediators or components for data storage devices.

Low-Dose Sparse-View HAADF-STEM-EDX Tomography of Nanocrystals Using Unsupervised Deep Learning.

High-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) can be acquired together with energy dispersive X-ray (EDX) spectroscopy to give complementary information on the nanoparticles being imaged. Recent deep learning approaches show potential for accurate 3D tomographic reconstruction for these applications, but a large number of high-quality electron micrographs are usually required for supervised training, which may be difficult to collect due to the damage on the particles from the electron beam. To overcome these limitations and enable tomographic reconstruction even in low-dose sparse-view conditions, here we present an unsupervised deep learning method for HAADF-STEM-EDX tomography. Specifically, to improve the EDX image quality from low-dose condition, a HAADF-constrained unsupervised denoising approach is proposed. Additionally, to enable extreme sparse-view tomographic reconstruction, an unsupervised view enrichment scheme is proposed in the projection domain. Extensive experiments with different types of quantum dots show that the proposed method offers a high-quality reconstruction even with only three projection views recorded under low-dose conditions.

Atomic-Scale Interface Modification Improves the Performance of Cu(In1-xGax)Se2/Zn(O,S) Heterojunction Solar Cells.

Cadmium-free buffer layers deposited by a dry vacuum process are mandatory for low-cost and environmentally friendly Cu(In1-xGax)Se2 (CIGS) photovoltaic in-line production. Zn(O,S) has been identified as an alternative to the chemical bath deposited CdS buffer layer, providing comparable power conversion efficiencies. Recently, a significant efficiency enhancement has been reported for sputtered Zn(O,S) buffers after an annealing treatment of the complete solar cell stack; the enhancement was attributed to interdiffusion at the CIGS/Zn(O,S) interface, resulting in wide-gap ZnSO4 islands formation and reduced interface defects. Here, we exclude interdiffusion or island formation at the absorber/buffer interface after annealing up to 200 °C using high-resolution scanning transmission electron microscopy (HR-STEM) and energy-dispersive X-ray spectroscopy (EDX). Interestingly, HR-STEM imaging reveals an epitaxial relationship between a part of the Zn(O,S) buffer layer grains and the CIGS grains induced by annealing at such a low temperature. This alteration of the CIGS/buffer interface is expected to lead to a lower density of interface defects, and could explain the efficiency enhancement observed upon annealing the solar cell stack, although other causes cannot be excluded.

Analysis of γ' Precipitates, Carbides and Nano-Borides in Heat-Treated Ni-Based Superalloy Using SEM, STEM-EDX, and HRSTEM.

The microstructure of a René 108 Ni-based superalloy was systematically investigated by X-ray diffraction, light microscopy, energy-dispersive X-ray spectroscopy, and electron microscopy techniques. The material was investment cast in a vacuum and then solution treated (1200 °C-2h) and aged (900 °C-8h). The γ matrix is mainly strengthened by the ordered L12 γ' phase, with the mean γ/γ' misfit, δ, +0.6%. The typical dendritic microstructure with considerable microsegregation of the alloying elements is revealed. Dendritic regions consist of secondary and tertiary γ' precipitates. At the interface of the matrix with secondary γ' precipitates, nano M5B3 borides are present. In the interdendritic spaces additionally primary γ' precipitates, MC and nano M23C6 carbides were detected. The γ' precipitates are enriched in Al, Ta, Ti, and Hf, while channels of the matrix in Cr and Co. The highest summary concentration of γ'-formers occurs in coarse γ' surrounding MC carbides. Borides M5B3 contain mostly W, Cr and Mo. All of MC carbides are enriched strongly in Hf and Ta, with the concentration relationship between these and other strong carbide formers depending on the precipitate's morphology. The nano M23C6 carbides enriched in Cr have been formed as a consequence of phase transformation MC + γ → M23C6 + γ' during the ageing treatment.

Comparative study of cytotoxicity by platinum nanoparticles and ions in vitro systems based on fish cell lines.

Emission of platinum nanoparticles (Pt NPs) especially from vehicle exhaust catalysts and pharmaceutics cause an increase in concentrations of this metal in aquatic environments. In this study, small (4-9 nm) uncoated and polyvinylpyrrolidone (PVP) coated Pt NPs were synthetized and their dispersion in different exposure media were evaluated. Pt NP uptake in two established fish cell lines were investigated and comparative in vitro cytotoxicity of Pt NPs and ions were assessed. The coated and uncoated Pt NPs dispersions in minimum essential medium (MEM) with fetal bovine serum (FBS) displayed high colloidal stability. Transmission electron microscopy (TEM) and high-resolution scanning electron microscope equipped with an energy-dispersive X-ray spectrometer (STEM/EDX) indicated no detectable cellular uptake of Pt NPs in both cell line monolayers. But with ICP-MS analysis, trace amount of Pt content was determined in all digested monolayer cell samples. The cytotoxicity of both Pt NPs and Pt ions on both fish cell lines after 48 h exposure was investigated through three assays to monitor different endpoints of cytotoxicity. In all studied concentrations (0.325-200 mg/L) no significant cytotoxicity (p > .5) compared to controls were observed in the cells exposed to coated Pt NPs. Uncoated Pt NP and ion exposed cells indicated similar concentration dependent cytotoxicity on both cell lines.

Multi-approach analysis to assess the chromium(III) immobilization by Ochrobactrum anthropi DE2010.

Ochrobactrum anthropi DE2010 is a microorganism isolated from Ebro Delta microbial mats and able to resist high doses of chromium(III) due to its capacity to tolerate, absorb and accumulate this metal. The effect of this pollutant on O. anthropi DE2010 has been studied assessing changes in viability and biomass, sorption yields and removal efficiencies. Furthermore, and for the first time, its capacity for immobilizing Cr(III) from culture media was tested by a combination of High Angle Annular Dark Field (HAADF) Scanning Transmission Electron Microscopy (STEM) imaging coupled to Energy Dispersive X-ray spectroscopy (EDX). The results showed that O. anthropi DE2010 was grown optimally at 0-2 mM Cr(III). On the other hand, from 2 to 10 mM Cr(III) microbial plate counts, growth rates, cell viability, and biomass decreased while extracellular polymeric substances (EPS) production increases. Furthermore, this bacterium had a great ability to remove Cr(III) at 10 mM (q = 950.00 mg g-1) immobilizing it mostly in bright polyphosphate inclusions and secondarily on the cellular surface at the EPS level. Based on these results, O. anthropi DE2010 could be considered as a potential agent for bioremediation in Cr(III) contaminated environments.

Hierarchically Structured Core-Shell Design of a Lithium Transition-Metal Oxide Cathode Material for Excellent Electrochemical Performance.

Tuning geometrical parameters of lithium-mixed transition-metal oxide (LiTM) cathode materials is a promising strategy for resource-efficient design of high-performance Li-ion batteries. In this paper, we demonstrate that simple and facile geometrical tailoring of the secondary microstructure of LiTM cathode materials without complex chemical modification or heterostructure engineering can significantly improve overall electrochemical performance of the active cathode materials. An optimized LiTM with a bimodal size distribution of primary particles inside the secondary particles exhibits a 53.8% increase in capacity at a high discharge rate (10 C) compared to a commercially available reference and comparable rate capability after 100 charge/discharge cycles. The key concept of this approach is to maximize the beneficial effects arising from the controlled sizes of primary particles. Multimodal/multiscale microscopic characterizations based on electron tomography and scanning transmission electron microscopy, combined with electron energy-loss spectroscopy and energy-dispersive X-ray spectroscopy from the atomic level to the microscale level, were employed to elucidate structural origins of enhanced battery performance. This study paves the way for the resource-efficient microstructure design of LiTM cathode materials to maximize capacity and stability via simple adjustment of processing conditions, which is advantageous for mass-production applications.

Correlation of Interface Impurities and Chemical Gradients with High Magnetoelectric Coupling Strength in Multiferroic BiFeO3-BaTiO3 Superlattices.

The detailed understanding of magnetoelectric (ME) coupling in multiferroic oxide heterostructures is still a challenge. In particular, very little is known to date concerning the impact of the chemical interface structure and unwanted impurities that may be buried within short-period multiferroic BiFeO3-BaTiO3 superlattices during growth. Here, we demonstrate how trace impurities and elemental concentration gradients contribute to high ME voltage coefficients in thin-film superlattices, which are built from 15 double layers of BiFeO3-BaTiO3. Surprisingly, the highest ME voltage coefficient of 55 V cm-1 Oe-1 at 300 K was measured for a superlattice with a few atomic percent of Ba and Ti that diffused into the nominally 5 nm thin BiFeO3 layers, according to analytical transmission electron microscopy. In addition, highly sensitive enhancements of the cation signals were observed in depth profiles by secondary ion mass spectrometry at the interfaces of BaTiO3 and BiFeO3. As these interface features correlate with the ME performance of the samples, they point to the importance of charge effects at the interfaces, that is, to a possible charge mediation of ME coupling in oxide superlattices. The challenge is to provide cleaner materials and processes, as well as a well-defined control of the chemical interface structure, to push forward the application of oxide superlattices in multiferroic ME devices.