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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Multibeam Electron Diffraction

One of the primary uses for transmission electron microscopy (TEM) is to measure diffraction pattern images in order to determine a crystal structure and orientation. In nanobeam electron diffraction (NBED), we scan a moderately converged electron probe over the sample to acquire thousands or even millions of sequential diffraction images, a technique that is especially appropriate for polycrystalline samples. However, due to the large Ewald sphere of TEM, excitation of Bragg peaks can be extremely sensitive to sample tilt, varying strongly for even a few degrees of sample tilt for crystalline samples. In this paper, we present multibeam electron diffraction (MBED), where multiple probe-forming apertures are used to create multiple scanning transmission electron microscopy (STEM) probes, all of which interact with the sample simultaneously. We detail designs for MBED experiments, and a method for using a focused ion beam to produce MBED apertures. We show the efficacy of the MBED technique for crystalline orientation mapping using both simulations and proof-of-principle experiments. We also show how the angular information in MBED can be used to perform 3D tomographic reconstruction of samples without needing to tilt or scan the sample multiple times. Finally, we also discuss future opportunities for the MBED method.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

A Roadmap for Edge Computing Enabled Automated Multidimensional Transmission Electron Microscopy

The advent of modern, high-speed electron detectors has made the collection of multidimensional hyperspectral transmission electron microscopy datasets, such as 4D-STEM, a routine. However, many microscopists find such experiments daunting since analysis, collection, long-term storage, and networking of such datasets remain challenging. Some common issues are their large and unwieldy size that often are several gigabytes, non-standardized data analysis routines, and a lack of clarity about the computing and network resources needed to utilize the electron microscope. The existing computing and networking bottlenecks introduce significant penalties in each step of these experiments, and thus, real-time analysis-driven automated experimentation for multidimensional TEM is challenging. One solution is to integrate microscopy with edge computing, where moderately powerful computational hardware performs the preliminary analysis before handing off the heavier computation to high-performance computing (HPC) systems. In this work, we trace the roots of computation in modern electron microscopy, demonstrate deep learning experiments running on an edge system, and discuss the networking requirements for tying together microscopes, edge computers, and HPC systems.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

Mechanistic Insights into Superlattice Transformation at a Single Nanocrystal Level Using Nanobeam Electron Diffraction

Understanding the mechanism and ultimately directing nanocrystal (NC) superlattice assembly and attachment have important implications on future advances in this emerging field. Here, we use 4D-STEM to investigate a monolayer of PbS NCs at various stages of the transformation from a hexatic assembly to a nonconnected square-like superlattice over large fields of view. Maps of nanobeam electron diffraction patterns acquired with an electron microscope pixel array detector (EMPAD) offer unprecedented detail into the 3D crystallographic alignment of the polyhedral NCs. Our analysis reveals that superlattice transformation is dominated by translation of prealigned NCs strongly coupled along the <11n>AL direction and occurs stochastically and gradually throughout single grains. We validate the generality of the proposed mechanism by examining the structure of analogous PbSe NC assemblies using conventional transmission electron microscopy and selected area electron diffraction. Here, the experimental results presented here provide new mechanistic insights into NC self-assembly and oriented attachment.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Nanoscale Tracking of the High-Temperature Spin-State Transition in LaCoO 3

The high-temperature spin and electronic transitions in LaCoO 3 have recently been leveraged to create neuromorphic (brain-inspired) devices. While these devices have shown the potential for impactful functionality in next-generation computing systems, the nanoscale dynamics of the spin and electronic transitions that underlie their operation are not well understood. Inhomogeneities related to interfaces, electrode contacts, strain, and crystal defects can all affect device performance, making nanoscale characterization of the transitions essential for producing consistent and reliable devices. Here, we demonstrate the first nanoscale in situ measurement of the spin transition in LaCoO 3 at device-relevant temperatures (25–325 °C) over length scales of tens of nanometers using STEM-EELS. This measurement is enabled by an Al 2 O 3 coating, which prevents unwanted reduction of the LaCoO 3 specimen at high temperature and vacuum. The detailed understanding of LaCoO 3 transition dynamics enabled by such measurements will be crucial for optimizing LaCoO 3 -based neuromorphic devices and increasing reliability for real-world application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Atomic Structure of Surface-Densified Phases in Ni-Rich Layered Compounds

In this work, we report the presence of surface-densified phases (β-Ni 5 O 8 , γ-Ni 3 O 4 , and δ-Ni 7 O 8 ) in LiNiO 2 (LNO)- and LiNi 0.8 Al 0.2 O 2 (LNA)-layered compounds by combined atomic level scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS). These surface phases form upon electrochemical aging at high state of charge corresponding to a fully delithiated state. A unique feature of these phases is the periodic occupancy by Ni 2+ in the Li layer. This periodic Ni occupancy gives rise to extra diffraction reflections, which are qualitatively similar to those of the LiNi 2 O 4 spinel structure, but these surface phases have a lower Ni valence state and cation content than spinel. Furthermore, these experimental results confirm the presence of thermodynamically stable surface phases and provide new insights into the phenomena of surface phase formation in Ni-rich layered structures.

25 ENERGY STORAGE↗
DOE OSTI2025

Unraveling Impurity-Dependent Morphological and Chemical Evolution of Ni–20Cr Alloy in Eutectic LiCl–KCl Molten Salt

Understanding the interfacial evolution of alloys in molten salt with different amounts of water (H 2 O) and oxygen (O 2 ) impurities is significant for applications in many fields, including concentrated solar power, molten salt reactors, and applications in pyrochemical reprocessing and electrorefining. Additionally, the impurity-driven corrosion mechanisms that lead to various morphological and chemical evolution characteristics at the interfaces of structural alloys and molten salts are not fully understood. In the present work, the three-dimensional (3D) morphological evolution of Ni-20Cr microwires in LiCl-KCl was studied at 500 °C under different moisture and oxygen conditions using in situ synchrotron transmission X-ray microscopy (TXM) and scanning transmission electron microscopy (STEM) techniques. No significant morphological changes were observed in Ni-20Cr microwires under vacuum conditions. However, the wires exhibited distinct morphological evolutions when exposed to molten salt containing H 2 O alone, as well as when both H 2 O and O 2 were present. Furthermore, Cr 2 O 3 precipitates were observed in the molten salt during corrosion with only H 2 O present, while Cr 6+ species were identified in the salt when O 2 was added. Further, these findings are crucial for understanding the corrosion mechanisms of molten salt with different amounts of H 2 O and O 2 contamination, providing insights for developing corrosion mitigation methods and improving the stability of containment alloys in molten salt applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Structural and Valence State Modification of Cobalt in CoPt Nanocatalysts in Redox Conditions

Platinum is the primary catalyst for many chemical reactions in the field of heterogeneous catalysis. However, platinum is both expensive and rare. Therefore, it is advantageous to combine Pt with another metal to reduce cost while also enhancing stability. To that end, Pt is often combined with Co to form Co-Pt nanocrystals. However, dynamical restructuring effects that occur during reaction in Co-Pt ensembles can impact catalytic properties. In this study, model Co 2 Pt 3 nanoparticles supported on carbon were characterized during a redox cycle with two in situ approaches, namely X-ray absorption spectroscopy (XAS) and scanning transmission electron microscopy (STEM) using a multimodal microreactor. The sample was exposed to temperatures up to 500 °C under H 2 , and then to O 2 at 300 °C. Irreversible segregation of Co in the Co-Pt particles was seen during redox cycling and substantial changes of the oxidation state of Co were observed. After the H 2 treatment, a fraction of Co could not be fully reduced and incorporated into a mixed Co-Pt phase. Re-oxidation of the sample increased Co segregation, and the segregated material had a different valence state than in the fresh, oxidized sample. Furthermore, this in situ study describes dynamical restructuring effects in CoPt nano-catalysts at the atomic scale that are crucial to understand to improve the design of catalysts used in major chemical processes.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Probing Oxidation-Driven Amorphized Surfaces in a Ta(110) Film for Superconducting Qubit

Recent advances in superconducting qubit technology have led to significant progress in quantum computing, but the challenge of achieving a long coherence time remains. Despite the excellent lifetime performance that tantalum (Ta) based qubits have demonstrated to date, the majority of superconducting qubit systems, including Ta-based qubits, are generally believed to have uncontrolled surface oxidation as the primary source of the two-level system loss in two-dimensional transmon qubits. Therefore, atomic-scale insight into the surface oxidation process is needed to make progress toward a practical quantum processor. Here, in this study, the surface oxidation mechanism of native Ta films and its potential impact on the lifetime of superconducting qubits were investigated using advanced scanning transmission electron microscopy (STEM) techniques combined with density functional theory calculations. The results suggest an atomistic model of the oxidized Ta(110) surface, showing that oxygen atoms tend to penetrate the Ta surface and accumulate between the two outermost Ta atomic planes; oxygen accumulation at the level exceeding a 1:1 O/Ta ratio drives disordering and, eventually, the formation of an amorphous Ta 2 O 5 phase. In addition, we discuss how the formation of a noninsulating ordered TaO 1–δ (δ < 0.1) suboxide layer could further contribute to the losses of superconducting qubits. Subsurface oxidation leads to charge redistribution and electric polarization, potentially causing quasiparticle loss and decreased current-carrying capacity, thus affecting superconducting qubit coherence. The findings enhance the comprehension of the realistic factors that might influence the performance of superconducting qubits, thus providing valuable guidance for the development of future quantum computing hardware.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Structural Characterization of the Platinum Nanoparticle Hydrogen-Evolving Catalyst Assembled on Photosystem I by Light-Driven Chemistry

Directed assembly of abiotic catalysts onto biological redox protein frameworks is of interest as an approach for the synthesis of biohybrid catalysts that combine features of both synthetic and biological materials. In this report, we provide a multiscale characterization of the platinum nanoparticle (NP) hydrogen-evolving catalysts that are assembled by light-driven reductive precipitation of platinum from an aqueous salt solution onto the photosystem I protein (PSI), isolated from cyanobacteria as trimeric PSI. The resulting PSI-NP assemblies were analyzed using a combination of X-ray energy-dispersive spectroscopy (XEDS), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), small-angle X-ray scattering (SAXS), and high-energy X-ray scattering with atomic pair distribution function (PDF) analyses. The results show that the PSI-supported NPs are approximately 1.8 nm diameter disk-shaped particles that assemble at discrete sites with 145 Å separation. This separation is too large to be consistent with NP nucleation and growth at a site adjacent to the F B cofactor site. Instead, we suggest a mechanism for NP growth at hydrophobic sites on the PSI stromal surface. The NPs photoreductively assembled on the PSI stromal surface are found to be analogous to the nanostructures produced by successive cycles of atomic layer deposition (ALD) of platinum onto 40 nm porous anodic alumina oxide supports, although the mechanisms for nucleation appear to differ. In conclusion, this work establishes a foundation for the investigation of the reductive assembly of abiotic metal catalysts at sites connected to photochemically reducing equivalent production in PSI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Structural and Mechanical Analysis of Individual Mineralized Collagen Fibrils Using In Situ Transmission Electron Microscopy

Bone serves as an example of nature’s architectured material with its characteristic blend of strength and toughness, all at a lightweight design. Given the hierarchical nature of these materials, it is essential to understand the governing mechanisms and organization of their constituents across length scales for bioinspired structural design. Despite recent advances in transmission electron microscopy (TEM) that have allowed us to witness the hierarchical arrangement of bone at micro-down to the nanoscale, we are still missing the details about the structural organization and mechanical properties of the main building blocks of bone─mineralized collagen fibrils (MCFs). Here, we present a method to extract individual MCFs from nature’s model material, mineralized turkey leg tendon, using a dropcasting procedure. By isolating the MCFs onto TEM supporting grids, we visualized the arrangement of organic and mineral phases within individual MCFs at the nanoscale. Using a four-dimensional scanning transmission electron microscopy (4D-STEM) approach, the orientation of individual mineral crystals within the MCFs was examined. Furthermore, we conducted in situ tensile experiments, revealing exceptional tensile strains of at least 8%, demonstrating the intricate relationship between structural organization and the mechanical behavior of MCFs. These insights into the ultrastructure of mineralized tissue building blocks, as well as the proposed sample-extraction method compatible with in situ mechanical testing, provide a strong basis for research into nature-inspired material design.

4D-STEM↗
DOE OSTI2021

Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries

Mixed cationic and anionic redox cathode chemistry is emerging as conventional cationic-redox of transition metal based layered oxides are reaching their theoretical capacity limit. However, these anionic redox in transition metal oxide-based cathodes attained by taking excess lithium has resulted in stability issues due to weak metal - oxygen ligand covalency. Here, we present an alternative approach of improving metal - ligand covalency by introducing less electronegative chalcogen ligand (sulfur) in the cathode structural framework where the metal dband penetration into ligand p-band thereby utilizing reversible mixed anionic and cationic redox chemistry. Through this design strategy, we report possibility of developing a new family of layered cathode materials when partially filled d orbital redox couples like Fe 2+/3+ are introduced in the Li-ion conducting phase (Li 2 SnS 3 ). Further, the electron energy loss spectroscopy (EELS) and X-ray absorption near-edge structure (XANES) analysis are used to qualitatively identify the charge contributors at the metal and ligand sites during Li + extraction. The detailed high-resolution transmission electron microscopy (HR-TEM) and high annular dark field-scanning transmission electron microscopy (HAADF-STEM) investigation reveal the multi redox induced structural modifications and its surface amorphization with nanopore formation during cycling. Findings from this study will shed light on designing Ni and Co free chalcogen cathodes and various functional materials in the chalcogen based dual anionic and cationic redox cathode avenue.

25 ENERGY STORAGE↗
DOE OSTI2021

Intrinsic helical twist and chirality in ultrathin tellurium nanowires

Robust atomic-to-meso-scale chirality is now observed in the one-dimensional form of tellurium. This enables a large and counter-intuitive circular-polarization dependent second harmonic generation response above 0.2 which is not present in two-dimensional tellurium. Orientation variations in 1D tellurium nanowires obtained by four-dimensional scanning transmission electron microscopy (4D-STEM) and their correlation with unconventional non-linear optical properties by second harmonic generation circular dichroism (SHG-CD) uncovers an unexpected circular-polarization dependent SHG response from 1D nanowire bundles – an order-of-magnitude higher than in single-crystal two-dimensional tellurium structures – suggesting the atomic- and meso-scale crystalline structure of the 1D material possesses an inherent chirality not present in its 2D form; and which is strong enough to manifest even in the aggregate non-linear optical (NLO) properties of aggregates.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Proton surface exchange kinetics of perovskite triple conducting thin films for protonic ceramic electrolysis cells: BaPr 0.9 Y 0.1 O 3–δ (BPY) vs. Ba 1–x Co 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3–δ (BCFZY)

Protonic ceramic electrolysis cells (PCECs) are an attractive green H 2 production technology, given their intermediate-temperature operating range and ability to produce dry H 2 . However, PCECs will benefit from development of more efficient and durable “triple conducting” anodes where steam is split, H incorporated, and oxygen evolved. In this work, we evaluated the kinetics of the steam-splitting/H incorporation reaction on BaPr 0.9 Y 0.1 O 3–δ (BPY) in comparison to the benchmark Ba 1–x Co 0.4 Fe 0.4 Z r0.1 Y 0.1 O 3–δ (BCFZY) composition, replacing most of the transition metal elements (Co, Fe, Zr) with the lanthanide Pr. We prepared geometrically well-defined perovskite BPY and BCFZY thin films by pulsed laser deposition and performed simultaneous optical transmission relaxation and electrical conductivity relaxation measurements at 400–500 °C in 0.21 atm O 2 during switching of the steam partial pressure to isolate and compare their proton surface exchange coefficients (k). The k values of BPY were comparable to those of BCFZY and more stable over time. According to angle-resolved XPS and STEM-EDS mapping of FIB cross-sections, the surface of BPY exhibited Ba enrichment, Pr deficiency, and Si contamination. In contrast, BCFZY exhibited Ba deficiency throughout, no obvious surface segregation, and less Si contamination. The Ba segregation on the BPY film appears to have promoted steam splitting/H incorporation kinetics even though the more basic surface reacted with the acidic environmental SiO x H y . Faster kinetics observed on stoichiometric BCFZY vs. Ba-deficient BCFZY confirmed the benefit of a high A-site Ba concentration. This result contrasts with most work on perovskites applied in solid oxide electrolysis cell anodes, in which A-site segregation is considered deleterious for surface reaction kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Unveiling Structural Heterogeneity and Imbalance of Gold Decahedral Nanoparticles using Four-dimensional Scanning Transmission Electron Microscopy

Multi-twinned structures have been observed in technologically important crystal systems, for example diamond cubic and face-centered cubic (FCC) lattices, that include materials such as diamond, silicon, a wide range of noble metals, and their nanoscale counterparts. Beyond atomic building blocks, the special arrangements also occur in the self-assembly of nanoparticles (NP) and μm-sized colloidal particles and occupy parts of their phase diagrams. Spanning a wide range of length scales, the universality of the structures arises when the systems attempt to achieve multitwinned structures by overcoming geometric misfits during minimizing surface energies with entirely {111} or close-packing facets. While it is fundamental to understand how strain is sustained upon twinned structures and symmetry breaking, the knowledge will be paramount in practical aspects such as guiding and controlling the thin film growth, anisotropic NP growth, and self-assembly of NPs. Au decahedral (Dh) NP, as the most prevalent multi-twinned model system, fits five tetrahedral motifs into a circle by sharing an axis resulting in a geometric misfit angle of 7.35°, or a disclination with power of -7.35°. Postulating how Au FCC lattice adopts the misfit, theoretical models have been developed to address the underlying lattice symmetry and inhomogeneous strain distribution separately. Yet, experimental reports regarding the former have been limited due to the relatively large X-ray beam sizes that do not fit the sizes of NPs. On the other hand, though the latter has been widely adapted in the thermodynamics of small (<10 nm) multi-twinned nanoparticles, previous literature has shown that, at edge length of 17 nm, the theory’s is invalidated by shear strain that is observed in a defect-free Au Dh NP by high-resolution transmission electron microscopy (HR-TEM) imaging. Though the advancement of aberrationcorrected scanning transmission electron microscopy (AC-STEM) imaging and ab initio calculation techniques brings new opportunities, along with challenges in complicated image analysis and limitation in particle size (usually below 10 nm), the gap between nanoscale and mesoscale has never been extended to gain insight from atomic system with straightforward interaction potentials.

4D-STEM↗
DOE OSTI2022

Spatial resolution in secondary-electron microscopy

Here, we first review the significance of resolution and contrast in electron microscopy, and the effect of the electron optics on these two quantities. We then outline the physics of the generation of secondary electrons (SE) and their transport and emission from the surface of a specimen. Contrast and resolution are discussed for different kinds of SE imaging in scanning (SEM) and scanning-transmission (STEM) instruments, with some emphasis on the observation of individual atoms and atomic columns in a thin specimen. The possibility of achieving atomic resolution from a bulk specimen at SEM energies is also considered.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Improved Three-Dimensional Reconstructions in Electron Ptychography through Defocus Series Measurements

A detailed analysis of ptychography for three-dimensional (3D) phase reconstructions of thick specimens is performed. Here, we introduce multi-focus ptychography, which incorporates a 4D-STEM defocus series to enhance the quality of 3D reconstructions along the beam direction through a higher overdetermination ratio. This method is compared with established multi-slice ptychography techniques, such as conventional ptychography, regularized ptychography, and multi-mode ptychography. Additionally, we contrast multi-focus ptychography with an alternative method that uses virtual optical sectioning through a reconstructed scattering matrix (S-matrix), which offers more precise 3D structure information compared to conventional ptychography. Our findings from multiple 3D reconstructions based on simulated and experimental data demonstrate that multi-focus ptychography surpasses other techniques, particularly in accurately reconstructing the surfaces and interface regions of thick specimens.

3D reconstruction↗
DOE OSTI2025

Nanoscale Phase Identification Using Two-Dimensional Pair Correlation Functions: A Case Study on Hafnium Oxide

Accurate identification of local phases in nanocrystalline materials is essential for understanding their functional properties, but it remains a significant challenge for polymorphic materials to locally differentiate them at nanoscale. This challenge is further compounded in polycrystalline materials with randomly oriented grains and the coexistence of multiple phases. In this report, we present a methodology for phase and orientation identification at the nanoscale by leveraging vector pair correlation functions extracted from atomically resolved scanning transmission electron microscopy (STEM) images. We demonstrate the accuracy of the methodology on both simulated and experimental data from HfO 2 -based films, a material that exhibits multiple coexisting phases in films with thicknesses ranging from 5 to 20 nm. While demonstrated on HfO 2 films, the methodology can be extended to other polymorphic nanocrystalline systems with complex phase coexistence.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Reuniting philosophy and science to advance cancer research

Cancers rely on multiple, heterogeneous processes at different scales, pertaining to many biomedical fields. Therefore, understanding cancer is necessarily an interdisciplinary task that requires placing specialised experimental and clinical research into a broader conceptual, theoretical, and methodological framework. Without such a framework, oncology will collect piecemeal results, with scant dialogue between the different scientific communities studying cancer. We argue that one important way forward in service of a more successful dialogue is through greater integration of applied sciences (experimental and clinical) with conceptual and theoretical approaches, informed by philosophical methods. By way of illustration, we explore six central themes: (i) the role of mutations in cancer; (ii) the clonal evolution of cancer cells; (iii) the relationship between cancer and multicellularity; (iv) the tumour microenvironment; (v) the immune system; and (vi) stem cells. In each case, we examine open questions in the scientific literature through a philosophical methodology and show the benefit of such a synergy for the scientific and medical understanding of cancer.

59 BASIC BIOLOGICAL SCIENCES↗