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At least 235 records · Page 13

Metallic support films reduce optical heating in cryogenic correlative light and electron tomography

Super-resolved cryogenic correlative light and electron tomography is an emerging method that provides both the single-molecule sensitivity and specificity of fluorescence imaging, and the molecular scale resolution and detailed cellular context of tomography, all in vitrified cells preserved in their native hydrated state. Technical hurdles that limit these correlative experiments need to be overcome for the full potential of this approach to be realized. Chief among these is sample heating due to optical excitation which leads to devitrification, a phase transition from amorphous to crystalline ice. Here, in this work, we show that much of this heating is due to the material properties of the support film of the electron microscopy grid, specifically the absorptivity and thermal conductivity. We demonstrate through experiment and simulation that the properties of the standard holey carbon electron microscopy grid lead to substantial heating under optical excitation. In order to avoid devitrification, optical excitation intensities must be kept orders of magnitude lower than the intensities commonly employed in room temperature super-resolution experiments. We further show that the use of metallic films, either holey gold grids, or custom made holey silver grids, alleviate much of this heating. For example, the holey silver grids permit 20× the optical intensities used on the standard holey carbon grids. Super-resolution correlative experiments conducted on holey silver grids under these increased optical excitation intensities have a corresponding increase in the rate of single-molecule fluorescence localizations. This results in an increased density of localizations and improved correlative imaging without deleterious effects from sample heating.

59 BASIC BIOLOGICAL SCIENCES↗

Time-resolved cryogenic electron tomography for the study of transient cellular processes

Cryogenic electron tomography (cryo-ET) is the highest resolution imaging technique applicable to the life sciences, enabling sub-nanometer visualization of specimens preserved in their near native states. The rapid plunge freezing process used to prepare samples lends itself to time-resolved studies, which researchers have pursued for in vitro samples for decades. Here, we focus on developing a freezing apparatus for time-resolved studies in situ. The device mixes cellular samples with solution-phase stimulants before spraying them directly onto an electron microscopy grid that is transiting into cryogenic liquid ethane. By varying the flow rates of cell and stimulant solutions within the device, we can control the reaction time from tens of milliseconds to over a second prior to freezing. In a proof-of-principle demonstration, the freezing method is applied to a model bacterium, Caulobacter crescentus, mixed with an acidic buffer. Through cryo-ET we resolved structural changes throughout the cell, including surface-layer protein dissolution, outer membrane deformation, and cytosolic rearrangement, all within 1.5 seconds of reaction time. This new approach, Time-Resolved cryo-ET (TR-cryo-ET), enhances the capabilities of cryo-ET by incorporating a sub-second temporal axis and enables the visualization of induced structural changes at the molecular, organelle, or cellular level.

59 BASIC BIOLOGICAL SCIENCES↗

Revealing the Crystalline Architecture of Semicrystalline Ion Exchange Membranes for the Design of Conductive and Durable Alkaline Anion Exchange Membranes

Alkaline anion exchange membrane (AAEM) fuel cells offer a cost-effective alternative to proton exchange membrane (PEM) fuel cells by eliminating the need for expensive precious metal catalysts. In both PEMs and AAEMs, semicrystalline polymers are a common choice, as the crystalline domains can act as mechanical reinforcements that limit swelling and promote mechanical durability in the material. However, spatially resolved characterization of crystalline organization in ion exchange membranes beyond ensemble-averaged X-ray scattering is underrepresented, likely in part due to ionization damage limitations in soft materials. Here, in this study, we resolve the nanometer-size crystallites in semicrystalline ion exchange membranes by applying cryogenic four-dimensional scanning transmission electron microscopy (cryo-4D-STEM) along with data-processing algorithms designed to optimize signals at a low dose to minimize radiation damage. We investigate the effects of synthesis components, including molecular weight and thermal treatment, on a model system of AAEMs in comparison to Nafion, the most commonly used and commercially successful PEM today. We find that excess water uptake in polymer membranes, a property directly associated with weak mechanical durability and with possible negative impacts on ion conductivity, can be reduced by over 30% by varying the polymer's crystalline morphology through changes in synthesis parameters such as molecular weight and thermal history. Our results indicate that this improvement is correlated with smaller crystalline domains with a more homogeneous distribution. More broadly, these results demonstrate how the crystalline architecture of polymer membranes can be tuned through their chemistry and thermal treatment in order to improve their conductivity and durability for commercial fuel cell performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Grain boundary zirconia-modified garnet solid-state electrolyte

Here, we report a method for promoting electrochemical stability in garnet Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 solid-state electrolyte based on a composite two-phase oxide–oxide microstructure. Grain boundary precipitation of the controlled distribution of amorphous zirconium oxide microparticles is achieved through the addition of reactive tantalum carbide. During ambient-atmosphere sintering, the carbide decomposes through an in situ reaction, the ‘extra’ Ta substituting for Zr within the Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 lattice. Density functional theory (DFT) calculations identify a thermodynamically favourable reaction path and show how substituting Ta 5+ at Zr 4+ sites affects the crystal structure as well as bulk ionic and electronic conductivities. Quantitative stereology highlights that zirconia also acts as a sintering aid, reducing compact porosity. Cryogenic focused-ion-beam scanning electron microscopy and fractography analysis of cycled solid-state electrolytes illustrates that near-universally observed intergranular Li-metal dendrite propagation is suppressed by the two-phase microstructure, favouring transgranular dendrites instead. Importantly, DFT demonstrates that compared with the Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 surface, the zirconium oxide surface per se is less electronically conductive and does not trap excess electrons to reduce Li ions. This is a key reason for the substantial improvement in the electrochemical properties over the single-phase baseline.

36 MATERIALS SCIENCE↗

Real-space visualization of atomic displacements in a long-wavelength charge density wave using cryogenic 4D-STEM

EuA⁢l 4 , a known skyrmion magnet, represents a class of materials that show complex electronic behaviors involving long-wavelength charge density wave (CDW). Here we realize direct real-space imaging of the concomitant periodic lattice distortion (PLD) with picometer precision in EuA⁢l 4 . Simultaneous imaging of microstructure, polarization, and interatomic distance is made possible using cryogenic four-dimensional scanning transmitting electron microscopy (cryo-4DSTEM). With this approach, we determined that the PLD in EuA⁢l 4 incorporates two out-of-phase atomic displacement modes on the Eu and Al sublattices. The PLD introduces periodic local symmetry fluctuations from the average symmetry of the bulk EuA⁢l 4 crystal. This critical local structural insight helps understanding of charge-spin-lattice couplings behind the intertwined quantum order in EuA⁢l 4 . Furthermore, our results also demonstrate cryo-4DSTEM as an indispensable approach for probing CDW and related quantum materials at low temperatures.

Ni, Haoyang↗

Low-temperature failure mechanism of [001] niobium micropillars under uniaxial tension

The plasticity of body-centered cubic (bcc) metals is dependent of temperature as well as sample dimension at the micrometer scale, but the effects of cryogenic temperature on the plasticity and the related failure process in micron-sized bcc metals have not been studied under uniaxial tension. In this work, we utilized in situ cryogenic micro-tensile tests, transmission electron microscopy, and dislocation dynamic simulations to examine the plasticity and failure processes of [001]-oriented bcc niobium micropillars. Our study reveals that a strong suppression of cross-slip at low temperatures prevents dislocation multiplication and leads to a dislocation starvation state, at which no mobile dislocation exists due to the rapid annihilation of dislocations at free surfaces. New dislocations are then nucleated until stress concentration at a slip step creates a micro-crack, the propagation of which leads to catastrophic failure. As a result, this unique failure process results from the combined effects of sample dimension and temperature.

36 MATERIALS SCIENCE↗

Difficult Measurements of Materials Systems at Cryogenic Temperatures: Cryo-EELS and Cryo-4D-STEM

Scanning/transmission electron microscopy (S/TEM) in materials science has traditionally been accomplished at room temperature due to their solid state in this temperature range and relative insensitivity to radiolysis damage. Cooling to cryogenic temperatures tended to introduce instabilities such as vibration and drift and can lead to the buildup of carbon contamination or ice reducing contrast. The need to expand TEM experimental techniques into new fields such as quantum and battery materials led to new efforts to reduce these instabilities while achieving temperatures at or well below liquid nitrogen (77 K). Further, developments in detector and spectrometer technology brought new capabilities for high resolution electron energy loss spectroscopy (EELS) and scanning nanodiffraction (4D-STEM). These experimental modalities can require even tighter controls of drift, vibration, and exposure time. Here this presentation will discuss accomplishing difficult experiments at cryogenic temperatures in honor of the late Dr. Lena Kourkoutis who inspired and led many such experiments.

36 MATERIALS SCIENCE↗

Mechanical Milling – Induced Microstructure Changes in Argyrodite LPSCl Solid-State Electrolyte Critically Affect Electrochemical Stability

Microstructure of argyrodite solid-state electrolyte (SSE) critically affects lithium metal electrodeposition/dissolution. While the stability of unmodified SSE is mediocre, once optimized state-of-the-art electrochemical performance is achieved (symmetric cells, full cells with NMC811) without secondary interlayers or functionalized current collectors. Planetary mechanical milling in wet media (m-xylene) is employed to alter commercial Li 6 PS 5 Cl (LPSCl) powder. Quantitative stereology demonstrates how milling progressively refines grain and pore size/distribution in the SSE compact, increases its density, and geometrically smoothens the SSE-Li interface. Mechanical indentation demonstrates that these changes lead to reduced site-to-site variation in the compact's hardness. Milled microstructures promote uniform early-stage electrodeposition on foil collectors and stabilize solid electrolyte interphase (SEI) reactivity. Analysis of half-cells with bilayer electrolytes demonstrates the importance of microstructure directly contacting current collector, with interface roughness due to pore and grain size distribution being key. For the first time, short-circuiting Li metal dendrite is directly identified, employing 1.5 mm diameter “mini” symmetrical cell and cryogenic focused ion beam (cryo-FIB) electron microscopy. The branching sheet-like dendrite traverses intergranularly, filling the interparticle voids and forming an SEI around it. Importantly, mesoscale modeling reveals the relationship between Li-SSE interface morphology and the onset of electrochemical instability, based on underlying reaction current distribution.

25 ENERGY STORAGE↗

Magnetic Phase Diagram of 2D Magnet Fe 5– x GeTe 2 Revealed by Cryogenic Lorentz 4D-STEM

A two-dimensional van der Waals ferromagnet Fe 5–x GeTe 2 (F5GT) exhibits room-temperature magnetic transition and magnetic anisotropy. Studies have identified diverse magnetic states, including stripe domains, skyrmionic type-I and topologically trivial type-II bubbles, depending on the magnetic and thermal history. Yet, the underlying micromagnetic energetics driving these states remains unclear. Here, we establish the magnetic phase diagram of bulk F5GT using cryogenic Lorentz four-dimensional scanning transmission electron microscopy. We reveal that stripe domains spontaneously form upon zero-field cooling, while metastable magnetic bubbles are stabilized by external fields. Transitions from type-I to type-II bubbles are driven by an oblique external field. Micromagnetic simulations confirm that these transitions arise from the interplay of uniaxial anisotropy, dipolar interactions, and external fields, without requiring significant Dzyaloshinskii–Moriya Interaction (DMI). In conclusion, these findings clarify the micromagnetic origin of spin textures of F5GT and establish it as a tunable platform for nanoscale topological magnetism.

2D Magnets↗

Kinetics and mechanism of light-induced phase separation in a mixed-halide perovskite

Halide ion phase separation is a barrier to the application of mixed-halide perovskites, whereby the presence of large populations of photo-generated or injected carriers causes undesirable changes in the local band gap. Here, we investigate the mechanism of phase separation in CsPbI x Br 3-x perovskite single crystals driven by light. The phase separation process and its dynamics are visualized at the nanometer scale at cryogenic temperatures using in-situ scanning transmission electron microscopy and cathodoluminescence. Combined with phase field modeling that accounts for the coupling between electronic and chemical driving forces, our observations point to a spinodal decomposition mechanism in which both the amplitude of composition fluctuation and the characteristic length scale grow non-linearly with time. Our findings provide microscopic insights that can assist in further engineering mixed-halide perovskites either for stability or for intentional programming of the local halide ion composition, opening pathways to a wide range of applications.

36 MATERIALS SCIENCE↗

Twist-Angle-Dependent Excitons in Moiré MoTe 2 Visualized by Cryogenic STEM and Monochromated EELS

van der Waals twisted bilayers of transition-metal dichalcogenides exhibit diverse excitonic phenomena arising from moiré superlattices and lattice reconstruction. While interlayer strain and relaxation reshape their electronic bands, their nanoscale influence on the excitonic fine structure remains poorly understood. Here, we study the interplay between spin–orbit coupling (SOC) and the moiré lattice by probing excitons in H-type twisted (∼8-layer × 8-layer) MoTe 2 using atomic-resolution scanning transmission electron microscopy (STEM) combined with monochromated electron energy loss spectroscopy (EELS) at cryogenic temperature. Spatially resolved spectra reveal moiré-site-dependent variations in excitonic absorption, including modulation of the X B exciton across the moiré unit cell. We find that SOC in MoTe 2 increases with the twist angle within the studied range (2–4.5°), with the largest value observed at 4°. Furthermore, these findings establish the twist angle as a tunable parameter for SOC via moiré engineering and link local structural relaxation to excitonic fine structure in twisted MoTe 2 .

cryogenic STEM/EELS↗

Aging of Self-Assembled Lead Halide Perovskite Nanocrystal Superlattices: Effects on Photoluminescence and Energy Transfer

Excitonic coupling, electronic coupling, and cooperative interactions in self-assembled lead halide perovskite nanocrystals were reported to give rise to a red-shifted collective emission peak with accelerated dynamics. Here we report that similar spectroscopic features could appear as a result of the nanocrystal reactivity within the self-assembled superlattices. This is demonstrated by studying CsPbBr 3 nanocrystal superlattices over time with room-temperature and cryogenic micro-photoluminescence spectroscopy, X-ray diffraction, and electron microscopy. It is shown that a gradual contraction of the superlattices and subsequent coalescence of the nanocrystals occurs over several days of keeping such structures under vacuum. As a result, a narrow, low-energy emission peak is observed at 4 K with a concomitant shortening of the photoluminescence lifetime due to the energy transfer between nanocrystals. When exposed to air, self-assembled CsPbBr 3 nanocrystals develop bulk-like CsPbBr 3 particles on top of the superlattices. At 4 K, these particles produce a distribution of narrow, low-energy emission peaks with short lifetimes and excitation fluence-dependent, oscillatory decays. Overall, the aging of CsPbBr 3 nanocrystal assemblies dramatically alters their emission properties and that should not be overlooked when studying collective optoelectronic phenomena nor confused with superfluorescence effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Morphology and Luminescence Properties of Transition Metal Doped Zinc Selenide Crystals

Zinc selenide is an excellent matrix material to dope with rare-earth and transition metal to achieve mid-infrared luminescence to develop high power lasers. The luminescence, morphology and refractive index is significantly affected by the doping and defects generated due to size and valency of dopants, concentration, growth process and convection during the growth. The aim of the study is to investigate effect of point and line defects generated due to low doping of iron and chromium on the emission and morphology of the zinc selenide. Luminescence and morphological properties of large iron and chromium doped zinc selenide single crystals were studied to evaluate the effect of extremely low residual impurities and defects associated with the doping process. The emission properties following both short wavelength (i.e., ultraviolet; 350 – 370 nm) excitation and longer wavelength (i.e., near infrared; 850 – 870 nm) excitation were characterized. Luminescence emission bands were identified in both doped crystals. In addition to the primary emission bands, satellite peaks and intra-center transitions were also observed. Due to local population defects associated with the residual impurities (ppm to ppb) in the Fe-ZnSe and Cr-ZnSe crystals, peak emission wavelengths were observed to shift. Raman studies using 266 and 532 – nm excitation revealed different positions of longitudinal and transverse peaks for Fe-ZnSe and Cr-ZnSe crystals, associated with different levels of defects due to the different ion sizes. The emission bands were found to decrease in intensity due to recombination of residual impurity co-dopants and complex defects generated during growth and fabrication. Cryogenic temperature analyses revealed a very clean emission band due to freezing of some of the point and line defects. An emission band observed at 980 nm for both crystals at room temperature as well as cryogenic temperatures indicates a vibronic peak in ZnSe. The scanning electron microscopy (SEM) images of the local morphology support the conclusion that small crystallites in doped crystals are also present.

Zinc selenide↗

Nanoscale Mapping of Hydrogen Distribution in Nuclear Structural Materials Using Cryogenic Transfer Atom Probe Tomography

Analyzing hydrogen distribution in nuclear structural materials at sub-nanometer scale spatial resolution has been challenging by electron microscopy. Furthermore, methods such as thermal desorption spectroscopy only provides a bulk estimate of hydrogen concentration with no nanoscale spatial resolution. In the last decade, cryogenic transfer atom probe tomography (APT) has been emerging as an invaluable characterization technique for analyzing the nanoscale distribution of hydrogen isotopes in materials.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Integrated fluorescence light microscopy-guided cryo-focused ion beam-milling for in situ montage cryo-ET

Cryogenic-electron tomography (cryo-ET) permits the in situ visualization of biological macromolecules at the molecular level. Owing to the variable thickness of cells, tissues and organisms, frozen specimens may need to be thinned by cryo-focused ion beam (FIB) milling to produce thin (<500 nm) cryo-lamellae suitable for cryo-ET. Locating regions of interest remains a challenge because untargeted milling can lead to inadvertent ablation and removal of regions of interest. Correlative light and electron microscopy, combined with cryo-FIB milling, can guide the identification of labeled targets in the cellular milieu. Multiple transfers between cryo-imaging instruments, cumbersome correlation algorithms, limited accuracy and low throughput have hindered the routine adoption of cryo-FIB milling within a multimodal correlative workflow for in situ structural biology. Here, in this study, we present a workflow for 3D correlative cryo-fluorescence light microscopy-FIB-ET that streamlines fluorescence light microscopy-guided FIB milling, improving throughput while preserving both structural and contextual information. The complete integration of hardware and software described here minimizes sample contamination from cross-platform exchanges and greatly enhances the efficiency of 3D targeting in cryo-milling. We then describe procedures for implementing montage parallel array cryo-ET (MPACT), which can be easily adapted to any modern life-science transmission electron microscope. MPACT supports high-throughput cryo-ET acquisitions (10 tilt series in 1.5 h) for structure determination and comprehensive contextual understanding of macromolecules within their native surroundings. A complete session from sample preparation to MPACT data processing takes 5−7 d for an individual experienced in both cryo-EM and cryo-FIB milling.

Yang, Jie E. [Univ. of Wisconsin, Madison, WI (Uni↗

Direct determination of the morphology, structure and composition of cometary and interstellar ice analogs in the laboratory

Ices of various kinds (H2O, CO, CO2, CH4, NH3, CH3OH, etc.) comprise a volumetrically significant proportion of objects in the solar system (comets, outer planets, planetary rings, satellites) as well as in interstellar space (astrophysical ices). The refinement of analytical electron microscopy (AEM) procedures for storing, preparing and analyzing ices and other materials at cryogenic temperatures is discussed. These procedures will be essential to the successful analysis of returned comet nucleus samples.

Blake, D. F.↗

Comparison of the dielectric and magnetocaloric properties of bulk and film of GdFe 0.5 Cr 0.5 O 3

Here, we report a comparison of the magnetic, magnetocaloric, and dielectric properties of 50% iron substituted GdCrO 3 (GdFe 0.5 Cr 0.5 O 3 ) bulk pellet and 960 nm thick film of GdFe 0.5 Cr 0.5 O 3 (GFCO). The 960 nm film was synthesized on a platinized-silicon substrate by chem. soln. deposition and spin-coating methods. The X-ray diffraction scans of the bulk sample and the film as well as the morphology of the film as examined by the field-emission scanning electron microscope indicate phase-pure and polycrystalline nature of these samples. XPS was used to deermine the valence states of Gd, Fe, and Cr. The temp. dependence of the dielectric const. from 225 to 700 K shows peaks at T C = 525 K for the bulk and ≈450 K for the film due to ferroelectric to paraelectric transitions, since elec. polarization vs elec. field hysteresis loops are observed. at room temp. The dielectric studies in the bulk GFCO for T > T C indicate a relaxor-like behavior. The measurements of the magnetization (M) of the samples as a function of temp. (5-350 K) and magnetic field (H) up to 7 T (=70 kOe) depict hysteresis behavior at low temps. due to the canted antiferromagnetic order of Fe 3+ /Cr 3+ below the Néel temp. of ≈275 K. The M vs H isotherms at various temps. are used to det. and compare the magnetic entropy change (-ΔS) and relative cooling power (RCP) of the two samples, yielding (-ΔS) = 30.7 J/kg K (18.8 J/kg K) and RCP = 566.5 J/kg (375 J/kg) for the bulk (960 nm film) samples of GFCO at 7 K and 7 T, resp. The plot of RCP vs T shows that magnetic cooling for this system is most effective for T < 30 K. Comparatively smaller magnitudes of (-ΔS) and RCP for the film vis-a-vis the bulk sample of GFCO scale with its reduced magnetization. This suggests that further improvements in the quality of the films are needed to improve their magnetization and hence their magnetocaloric properties, possibly making them useful for on-chip cooling in miniaturized devices.

36 MATERIALS SCIENCE↗