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At least 271 records · Page 15

Direct Visualization of Current-Stimulated Oxygen Migration in YBa 2 Cu 3 O 7–δ Thin Films

The past years have witnessed major advancements in all-electrical doping control on cuprates. In the vast majority of cases, the tuning of charge carrier density has been achieved via electric field effect by means of either a ferroelectric polarization or using a dielectric or electrolyte gating. Unfortunately, these approaches are constrained to rather thin superconducting layers and require large electric fields in order to ensure sizable carrier modulations. In this work, we focus on the investigation of oxygen doping in an extended region through current-stimulated oxygen migration in YBa 2 Cu 3 O 7–δ superconducting bridges. The underlying methodology is rather simple and avoids sophisticated nanofabrication process steps and complex electronics. Here, a patterned multiterminal transport bridge configuration allows us to electrically assess the directional counterflow of oxygen atoms and vacancies. Importantly, the emerging propagating front of current-dependent doping δ is probed in situ by optical microscopy and scanning electron microscopy. The resulting imaging techniques, together with photoinduced conductivity and Raman scattering investigations, reveal an inhomogeneous oxygen vacancy distribution with a controllable propagation speed permitting us to estimate the oxygen diffusivity. These findings provide direct evidence that the microscopic mechanism at play in electrical doping of cuprates involves diffusion of oxygen atoms with the applied current. The resulting fine control of the oxygen content would permit a systematic study of complex phase diagrams and the design of electrically addressable devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elucidating the Role of Electric Fields in Fe Oxidation via an Environmental Atom Probe

Abstract We quantify the effects of intensely applied electric fields on the Fe oxidation mechanism. The specimen are pristine Fe single crystals exposing a variety of surface structures identified by field ion microscopy. These crystals are simultaneously exposed to low pressures of pure oxygen gas, on the order of 10 −7 mbar, while applying intense electric fields on their surface of several tens of volts per nanometer. The local composition of the different surface structures is probed directly and in real time using an Environmental Atom Probe and successfully compared with first principles‐based models. We found that rough Fe{244} and Fe{112} facets are more reactive toward oxygen than compact Fe{024} and Fe{011} facets. Results demonstrate that the influence of an electric field on the oxidation kinetics depends on the timescales that are involved as the system evolves toward equilibrium. The initial oxidation kinetics show that strong increases in electric fields facilitate the formation of an oxide. However, as one approaches equilibrium, high field values mitigate this formation. Ultimately, this study elucidates how high externally applied electric fields can be used to dynamically exploit reaction dynamics at the nanoscale towards desired products in a catalytic reaction at mild reaction conditions.

Lambeets, Sten V. [Physical and Computational Scie↗

Quantitative Electron Beam‐Single Atom Interactions Enabled by Sub‐20‐pm Precision Targeting

The ability to probe and control matter at the picometer scale is essential for advancing quantum and energy technologies. Scanning transmission electron microscopy offers powerful capabilities for materials analysis and modification, but sample damage, drift, and scan distortions hinder single atom analysis and deterministic manipulation. Materials analysis and modification via electron–solid interactions can be transformed by precise delivery of electrons to a specified atomic location, maintaining the beam position despite drift, and minimizing collateral dose. Here a fast, low-dose, sub-20-pm precision electron beam positioning technique is developed, “atomic lock-on,” (ALO), which offers the ability to position the beam on a specific atomic column without previously irradiating that column. This technique is used to lock onto a single selected atomic location to repeatedly measure its weak electron energy loss signal despite sample drift. Moreover, electron beam-matter interactions in single atomic events are measured with μ s time resolution. This enables observation of single-atom dynamics, such as atomic bistability, revealing partially bonded atomic configurations and recapture phenomena. This opens prospects for using electron microscopy for high-precision measurements and deterministic control of matter for quantum technologies.

2D materials↗

Electron Microscopy Approaches to Unraveling the Structure of Amorphous Materials

Determining atomic structures in crystalline materials—where atoms are arranged in rigid, periodic lattices—has been highly successful using probes such as electrons, X-rays, and neutrons. In contrast, amorphous materials, despite their ubiquity and technological importance, remain far more challenging to characterize with comparable accuracy and precision. This review highlights existing, emerging, and potential (scanning) transmission electron microscopy ((S)TEM) techniques for probing short- and medium-range order in amorphous materials. Approaches ranging from high-resolution (S)TEM imaging and selected electron diffraction pattern to four-dimensional STEM (4D-STEM) based pair distribution function, fluctuation electron microscopy, tomography, ptychography, and spectroscopic methods are discussed, emphasizing their ability to provide complementary insights across multiple length scales—from sub-angstrom local environments to nanometer-scale correlations. Here, we further explore the promise of multimodal and correlative strategies, as well as the growing role of machine learning and physics-informed AI in enabling real-time, quantitative interpretation of complex structural signatures. Together, these advances point toward a future where electron microscopy not only reveals the hidden order in amorphous systems but also establishes robust structure–property relationships, paving the way for materials innovation in disordered matter.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Facile Tensile Testing Platform for In Situ Transmission Electron Microscopy of Nanomaterials

In situ tensile testing using transmission electron microscopy (TEM) is a powerful technique to probe structure-property relationships of materials at the atomic scale. In this work, a facile tensile testing platform for in situ characterization of materials inside a transmission electron microscope is demonstrated. The platform consists of: 1) a commercially available, flexible, electron-transparent substrate (e.g., TEM grid) integrated with a conventional tensile testing holder, and 2) a finite element simulation providing quantification of specimen-applied strain. The flexible substrate (carbon support film of the TEM grid) mitigates strain concentrations usually found in free-standing films and enables in situ straining experiments to be performed on materials that cannot undergo localized thinning or focused ion beam lift-out. The finite element simulation enables direct correlation of holder displacement with sample strain, providing upper and lower bounds of expected strain across the substrate. The tensile testing platform is validated for three disparate material systems: sputtered gold-palladium, few-layer transferred tungsten disulfide, and electrodeposited lithium, by measuring lattice strain from experimentally recorded electron diffraction data. The results show good agreement between experiment and simulation, providing confidence in the ability to transfer strain from holder to sample and relate TEM crystal structural observations with material mechanical properties.

2D materials↗

Quantitative three-dimensional imaging of chemical short-range order via machine learning enhanced atom probe tomography

Abstract Chemical short-range order (CSRO) refers to atoms of specific elements self-organising within a disordered crystalline matrix to form particular atomic neighbourhoods. CSRO is typically characterized indirectly, using volume-averaged or through projection microscopy techniques that fail to capture the three-dimensional atomistic architectures. Here, we present a machine-learning enhanced approach to break the inherent resolution limits of atom probe tomography enabling three-dimensional imaging of multiple CSROs. We showcase our approach by addressing a long-standing question encountered in body-centred-cubic Fe-Al alloys that see anomalous property changes upon heat treatment. We use it to evidence non-statistical B 2 -CSRO instead of the generally-expected D0 3 -CSRO. We introduce quantitative correlations among annealing temperature, CSRO, and nano-hardness and electrical resistivity. Our approach is further validated on modified D0 3 -CSRO detected in Fe-Ga. The proposed strategy can be generally employed to investigate short/medium/long-range ordering phenomena in different materials and help design future high-performance materials.

36 MATERIALS SCIENCE↗

Effect of substrate temperature on the growth of Nb$_3$Sn film on Nb by multilayer sputtering

Nb3Sn films were fabricated by multilayer sequential sputtering on Nb substrates at substrate temperatures ranging from room temperature to 250 °C. The film material properties were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, atomic force microscopy, and transmission electron microscopy. The films’ superconducting properties were studied by four-point probe resistivity measurements from room temperature to below the superconducting critical temperature Tc. The highest Tc was17.76 K, when the multilayers were deposited at room temperature. A superconducting Nb3Sn thin film with a smoother surface morphology but a lower Tc of 17.58 K was obtained on the film deposited at a substrate temperature of 250 °C.

Sayeed, Md. Nizam↗

Cost-Effective Thermomechanical Processing of Nanostructured Ferritic Alloys: Microstructure and Mechanical Properties Investigation

Nanostructured ferritic alloys (NFAs), such as oxide-dispersion strengthened (ODS) alloys, play a vital role in advanced fission and fusion reactors, offering superior properties when incorporating nanoparticles under irradiation. Despite their importance, the high cost of mass-producing NFAs through mechanical milling presents a challenge. This study delves into the microstructure-mechanical property correlations of three NFAs produced using a novel, cost-effective approach combining severe plastic deformation (SPD) with the continuous thermomechanical processing (CTMP) method. Analysis using scanning electron microscopy (SEM)-electron backscatter diffraction (EBSD) revealed nano-grain structures and phases, while scanning transmission electron microscopy (STEM)-energy dispersive X-ray spectroscopy (EDS) quantified the size and density of Ti-N, Y-O, and Cr-O fine particles. Atom probe tomography (APT) further confirmed the absence of finer Y-O particles and characterized the chemical composition of the particles, suggesting possible nitride dispersion strengthening. Correlation of microstructure and mechanical testing results revealed that CTMP alloys, despite having lower nanoparticle densities, exhibit strength and ductility comparable to mechanically milled ODS alloys, likely due to their fine grain structure. However, higher nanoparticle densities may be necessary to prevent cavity swelling under high-temperature irradiation and helium gas production. Further enhancements in uniform nanoparticle distribution and increased sink strength are recommended to mitigate cavity swelling, advancing their suitability for nuclear applications.

36 MATERIALS SCIENCE↗

Mending cracks atom-by-atom in rutile TiO2 with electron beam radiolysis

Abstract Rich electron-matter interactions fundamentally enable electron probe studies of materials such as scanning transmission electron microscopy (STEM). Inelastic interactions often result in structural modifications of the material, ultimately limiting the quality of electron probe measurements. However, atomistic mechanisms of inelastic-scattering-driven transformations are difficult to characterize. Here, we report direct visualization of radiolysis-driven restructuring of rutile TiO 2 under electron beam irradiation. Using annular dark field imaging and electron energy-loss spectroscopy signals, STEM probes revealed the progressive filling of atomically sharp nanometer-wide cracks with striking atomic resolution detail. STEM probes of varying beam energy and precisely controlled electron dose were found to constructively restructure rutile TiO 2 according to a quantified radiolytic mechanism. Based on direct experimental observation, a “two-step rolling” model of mobile octahedral building blocks enabling radiolysis-driven atomic migration is introduced. Such controlled electron beam-induced radiolytic restructuring can be used to engineer novel nanostructures atom-by-atom.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radiation-Enhanced Anion Transport in Hematite

The influence of radiation-induced (1 MeV energy H+ to ~0.1 dpa at 450°C), non-equilibrium point defect populations on mass transport is studied with an integrated campaign of experimental and theoretical methods. Using epitaxial thin films of hematite with embedded 18O tracer layers and nanoscale atom probe tomography measurements, it is shown that anion self-diffusion is enhanced by at least 2 orders of magnitude under irradiation compared to thermal diffusion alone. Complementary scanning transmission electron microscopy of vacuum annealed specimens, reveals associated microstructural changes in the oxide films, including local phase transformation to Fe3O4 and the development of nanoscale voids from vacancy coalescence. Point defect formation and migration energies were computed from density functional theory and applied within the context of chemical rate theory to analyze contributions from both interstitial and vacancy mechanisms to self-diffusion in thermal and irradiation conditions. Comparisons are made between calculated, literature and newly measured self-diffusion values, revealing good agreement on the magnitude of radiation-enhanced anion diffusion. Further, the model suggests a transition from vacancy to interstitialcy mechanisms at low temperatures and high oxygen activity, consistent with the varied activation energies reported from prior studies.

iron oxides, isotopic tracers, atom probe tomograp↗

Revealing latent pole and zone line information in atom probe detector maps using crystallographically correlated metrics

Poles and zone lines observed within atom probe field evaporation images are useful for a range of atom probe crystallography studies, including calibration of the reconstruction and crystallographic characterisation of microstructural features such as grain boundaries. However, this information is not always readily apparent. Techniques for plotting crystallographically correlated metrics contained within atom probe data to enhance pole and zone line contrast across the detector space are developed. This includes consideration of the electric field, molecular ions, lattice structure retained within the reconstruction, specific elemental species, the number of pulses between detection events, and the lateral distance between sequential detection events. These approaches are then applied to experimental atom probe tomography datasets on technically pure Al, nanocrystalline Al, highly doped Si, and additively manufactured Inconel 738, Haynes 282, and Ti–6Al–4V. The results facilitate the extension of atom probe crystallography studies to a broader range of crystalline datasets where crystallographic information is not readily apparent from existing methods, as well as a deeper understanding of field evaporation behaviour during an atom probe experiment.

47 OTHER INSTRUMENTATION↗

Tunable Few-Layer van der Waals Crystals and Heterostructures as Emerging Energy and Quantum Materials (Final Technical Report)

2D and layered (van der Waals) semiconductors offer extraordinary opportunities for manipulating optically excited charge carriers, many-body excitations, and non-charge based quantum numbers. To date, research has focused on a limited group of materials, mostly transition metal dichalcogenides in the monolayer limit. Other van der Waals semiconductors, and especially few-layer to multilayer crystals and their heterostructures, carry large potential for the discovery of phenomena of interest for future energy and information technologies. But they remain largely unexplored, often due to a lack of access to high-quality materials and approaches for measuring their properties at the relevant scales. The goal of this project was to develop an EPSCoR-State/National Laboratory Partnership that addresses the challenges of preparing high-quality van der Waals semiconductors and of probing their structure, composition, and especially their optoelectronic and photonic properties, near the atomic scale using electron microscopy techniques. A central component of the project was the development of advanced methods for electron microscopy and electron-excited spectroscopy, taking advantage of unique samples as well as leading capabilities and expertise at the partner institutions. Efforts to advance leading-edge techniques was supported by ancillary developments, such as precision sample preparation for electron microscopy/spectroscopy, coordinated chemical imaging, and analytical electron microscopy. Experiments in materials synthesis and technique development were closely linked to theory and computation. The results obtained under this project yielded multifaceted benefits to the involved partners and their institutions, DOE-BES, the wider scientific community, and society at large, particularly in the State of Nebraska through dividends from knowledge and human capital generated under the project.

36 MATERIALS SCIENCE↗

Hydrogen bonded trimesic acid networks on Cu(111) reveal how basic chemical properties are imprinted in HR-AFM images

High resolution non-contact atomic force microscopy measurements characterize assemblies of trimesic acid molecules on Cu(111) and the link group interactions, providing the first fingerprints utilizing CO-based probes for this widely studied paradigm for hydrogen bond driven molecular self assembly. The enhanced submolecular resolution offered by this technique uniquely reveals key aspects of the competing interactions. Accurate comparison between full-density-based modeled images and experiment allows to identify key structural elements in the assembly in terms of the electron-withdrawing character of the carboxylic groups, interactions of those groups with Cu atoms in the surface, and the valence electron density in the intermolecular region of the hydrogen bonds. This study of trimesic acid assemblies on Cu(111) combining high resolution atomic force microscopy measurements with theory and simulation forges clear connections between fundamental chemical properties of molecules and key features imprinted in force images with submolecular resolution.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Measurement of G-phase volume fraction and number density in duplex stainless steels using transmission electron microscopy

Duplex stainless steels (DSS) have a high toughness and strength due the presence of both austenitic and ferritic phases. These alloys have had limited use in power production applications due to thermal embrittlement caused by spinodal decomposition and development of G-phase precipitates in the ferrite. Lean grade DSS alloys (e.g., 2101, 2003) may offer improved thermal stability due to the reduction of Cr- and Ni-equivalent elements when compared to standard grade compositions (e.g., 2205, 2209). The abundance of the G-phase was measured in five duplex stainless steels, three wrought alloys (2101, 2003, 2205) and their matching filler metals (2101-w, 2209-w), after aging at 427 °C for 1000 h and 10,000 h. The G-phase volume fraction, number density, size, and precipitate spacing were found using quantitative analysis of transmission electron microscopy dark field images and the composition of G-phase precipitates on other clusters were characterized with atom probe tomography (APT). In the welded alloys, the G-phase was found to develop rapidly, relative to the wrought material. A positive correlation was found between the nickel equivalent composition of the alloy and the G-phase volume fraction. The alloys 2205, 2209, and 2101-w, which are higher in Cr and Ni, all showed significant G-phase precipitation, further strengthening the hypothesis that lean grade DSS alloys are more thermally stable against precipitation in the ferrite. Electron diffraction showed a secondary phase present in the 2101 wrought alloy at 10,000 h, but it was not crystallographically consistent with the G-phase; APT showed the presence of nanoclusters rich in both nickel and copper for this alloy. In conclusion, no secondary phases or clusters were found in 2003 after 10,000 h of aging, so it may be a candidate alloy for applications that require long-life times at high operating temperatures.

36 MATERIALS SCIENCE↗

Effect of substrate temperature on the growth of Nb 3 Sn film on Nb by multilayer sputtering

Here, we report on the fabrication of niobium tin (Nb 3 Sn) films by multilayer sequential sputtering on niobium at substrate temperatures ranging from room temperature to 250 °C. The multilayers were then annealed inside a separate vacuum furnace at 950 °C for 3 h. The material properties of the films were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, atomic force microscopy, and transmission electron microscopy. The superconducting properties of the films were studied by four-point probe resistivity measurements from room temperature to below the superconducting critical temperature T c . The highest film T c was 17.76 K, obtained when the multilayers were deposited at room temperature. When the deposition temperature was raised to 250 °C, a significant reduction in voids was achieved while the film's T c was 17.58 K.

36 MATERIALS SCIENCE↗

Electron inelastic mean free path in water

Liquid phase transmission electron microscopy (LPTEM) is rapidly developing as a powerful tool for probing processes in liquid environments with close to atomic resolution. Knowledge of the water thickness is needed for reliable interpretation and modelling of analytical studies in LPTEM, and is particularly essential when using thin liquid layers, required for achieving the highest spatial resolutions. Furthermore, the log-ratio method in electron energy-loss spectroscopy (EELS) is often applied in TEM to quantify the sample thickness, which is measured relative to the inelastic mean free path ( λ IMFP ). However, λ IMFP itself is dependent on sample material, the electron energy, and the convergence and divergence angles of the microscope electronoptics. Here, we present a detailed quantitative analysis of the λ IMFP of water as functions of the EELS collection angle ( β ) at 120 keV and 300 keV in a novel nanochannel liquid cell. We observe good agreement with earlier studies conducted on ice, but find that the most widely used theoretical models significantly underestimate λ IMFP of water. We determine an adjusted average energy-loss term E m, water , and characteristic scattering angle θ E, water that improve the accuracy. The results provide a comprehensive knowledge of the λ IMFP of water (or ice) for reliable interpretation and quantification of observations in LPTEM and cryo-TEM studies.

77 NANOSCIENCE AND NANOTECHNOLOGY↗