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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 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Tunable electron beam pulser for picoseconds stroboscopic microscopy in transmission electron microscopes

For two decades, time-resolved transmission electron microscopes (TEM) have relied on pulsed-laser photoemission to generate electron bunches to explore sub-microsecond to sub-picosecond dynamics. Despite the vast successes of photoemission time-resolved TEMs, laser-based systems are inherently complex, thus tend not to be turn-key. In this paper, we report on the successful retrofit of a commercial 200 keV TEM, without an external laser, capable of producing continuously tunable pulsed electron beams with repetition rates from 0.1 GHz up to 12 GHz and a tunable bunch length from tens of nanoseconds down to 10 ps. This innovation enables temporal access into previously inaccessible regimes: i.e., high repetition rate stroboscopic experiments. Combination of a pair of RF-driven traveling wave stripline elements, quadrupole magnets, and a variable beam aperture enables operation of the instrument in (1) continuous waveform (CW) mode as though the instrument was never modified (i.e. convention TEM operation mode, where the electrons from the emission cathode randomly arrive at the sample without resolvable time information), (2) stroboscopic (pump-probe) mode, and (3) pulsed beam mode for dose rate sensitive materials. In order to analyze the effect of a pulsed beam on image quality, we examined Au nanoparticles using bright field, high-resolution TEM imaging and selected area diffraction in both continuous and pulsed-beam mode. Furthermore, in comparison of conventional TEMs, the add-on beam pulser enables the observation of ultrafast dynamic behavior in materials that are reversible under synchronized excitation.

36 MATERIALS SCIENCE↗
DOE OSTI2014

X-ray Energy-Dispersive Spectrometry During In Situ Liquid Cell Studies Using an Analytical Electron Microscope

The use of analytical spectroscopies during scanning/transmission electron microscope (S/TEM) investigations of micro- and nano-scale structures has become a routine technique in the arsenal of tools available to today's materials researchers. Essential to implementation and successful application of spectroscopy to characterization is the integration of numerous technologies, which include electron optics, specimen holders, and associated detectors. While this combination has been achieved in many instrument configurations, the integration of X-ray energy-dispersive spectroscopy and in situ liquid environmental cells in the S/TEM has to date been elusive. In this work we present the successful incorporation/modifications to a system that achieves this functionality for analytical electron microscopy.

Zaluzec, Nestor J.↗
DOE OSTI2016

Microwave Frequency Comb from a Semiconductor in a Scanning Tunneling Microscope

Abstract Quasi-periodic excitation of the tunneling junction in a scanning tunneling microscope, by a mode-locked ultrafast laser, superimposes a regular sequence of 15 fs pulses on the DC tunneling current. In the frequency domain, this is a frequency comb with harmonics at integer multiples of the laser pulse repetition frequency. With a gold sample the 200th harmonic at 14.85 GHz has a signal-to-noise ratio of 25 dB, and the power at each harmonic varies inversely with the square of the frequency. Now we report the first measurements with a semiconductor where the laser photon energy must be less than the bandgap energy of the semiconductor; the microwave frequency comb must be measured within 200 μ m of the tunneling junction; and the microwave power is 25 dB below that with a metal sample and falls off more rapidly at the higher harmonics. Our results suggest that the measured attenuation of the microwave harmonics is sensitive to the semiconductor spreading resistance within 1 nm of the tunneling junction. This approach may enable sub-nanometer carrier profiling of semiconductors without requiring the diamond nanoprobes in scanning spreading resistance microscopy.

Material Science↗
DOE OSTI2018

Visualizing and Quantifying the Cationic Mobility at {100} Surfaces of Ceria: Application to CO 2 Adsorption/Desorption Phenomena in the Environmental Transmission Electron Microscope

Environmental transmission electron microscopy in a dedicated instrument allows ultimate spatial resolution with chemical analysis capabilities similar to high resolution transmission electron microscopes (HRTEMs), while retaining partial pressures up to 20 mbar around the specimen. Finally, such instruments provide an optimized approach to study the early stages of catalytic reactions, which can start from very low partial pressure, at the atomic-scale.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Quantitative Assessment and Measurement of X-ray Detector Performance and Solid Angle in the Analytical Electron Microscope

A wide range of X-ray detectors and geometries are available today on transmission/scanning transmission analytical electron microscopes. While there have been numerous reports of their individual performance, no single experimentally reproducible metric has been proposed as a basis of comparison between the systems. In this paper, we detail modeling, experimental procedures, measurements, and specimens which can be used to provide a manufacturer-independent assessment of the performance of an analytical system. Using these protocols, the geometrical collection efficiency, system peaks, and minimum detection limits can be independently assessed and can be used to determine the best conditions to conduct modern hyperspectral and/or spectrally resolved tomographic analyses for an individual instrument. Here, a simple analytical formula and specimen is presented which after suitable system calibrations can be used to experimentally determine the X-ray detector solid angle.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Isotope-Resolved Electron Energy Loss Spectroscopy in a Monochromated Scanning Transmission Electron Microscope

The development and implementation of high-stability monochromators in state-of-the-art aberration-corrected scanning transmission electron microscopes has enabled materials characterization with an energy resolution as good as 3 meV. This allows the vibrational modes, which would otherwise be obscured by the energy spread of the electron beam, to be probed with very high precision in molecular materials. Since the vibrational energies depend on the weight of the atomic nuclei, vibrational spectroscopy can distinguish isotopes whose only difference lies in their neutron content. This opens up isotopic analysis and mapping in transmission electron microscopy as two important new research areas. In this paper, we review the monochromated electron energy loss spectroscopy (EELS) instrumentation, discuss optimal methods for probing beam-sensitive materials without destroying them, and review key nanoscale isotope-resolved results.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

First-Principles Simulation of Beam-Induced Processes Underlying Atomic Manipulation in Electron Microscopes

The development of experimental methods and apparatuses capable of promoting atomically precise material manipulations holds great promise for realizing the ultimate limit of feature miniaturization in materials and devices. The ability to modify materials atom by atom is anticipated to usher in new technologies in areas as diverse as separation science, medicine, and quantum information science. Historically, scanning probe-based techniques have been the most prominent approaches in this space. However, these methods are best suited for the manipulation of surface-exposed regions of materials, as the strong perturbations required for bond scission are delivered most effectively to atoms in the near-proximity to the scanning probe. In contrast, convergent electron beams with energies tuned slightly below the threshold for inducing irreversible knock-on damage have recently been employed (within scanning transmission electron microscopy) to promote atomic-scale bond rearrangements in various beam-stable solids. Currently, however, the efficiency and selectivity of beam-induced atomic manipulation processes with focused electron beams are such that long irradiation times are required to induce a desired atomic rearrangement. With a better understanding of the underlying physics dictating the outcome of a given irradiation event, methods can be devised to improve the efficiency of these techniques so that their promise can be fully realized through widespread adoption.To this end, this Account details our recent efforts to develop and apply tractable first-principles simulation approaches for studying the response of materials to electric beam-like external electric potentials applied in real space. We briefly review the concepts and capabilities in the area of atomically precise materials manipulation and review the early demonstrations of accomplishments in this area, focusing on studies using scanned convergent electron beam probes in particular. We expound upon the depth of the challenge and identify critical shortcomings of theoretical methods that have previously been employed in the simulation of beam-induced processes. We then describe the computational methods that we have generalized from the concepts and tools most commonly applied to the study of molecular photochemistry and how our adaptations of these methods can be employed to capture the relevant dynamical phenomena for beam-induced processes ranging from the initial electron scattering to the ensuing multistate reactions. Here, we contextualize these methods within the current state of the art in this area, which has historically focused primarily on the simulation of inelastic image formation in the electron microscope for the purpose of interpreting the results of quantitative electron microscopy experiments. We demonstrate that the spatial distribution of state-specific excitation rates due to the presence of an external (probe) electric charge is inhomogeneous, such that irradiation at particular locations in materials can favor specific electronic transitions (and disallow others). In addition to the potential for excited-state reaction pathways to be accessed through the initial inelastic scattering of the tightly focused electron beam from the targeted atoms, we also identify favorable conditions for the electronically nonadiabatic evolution of the highly vibrationally excited system to open complex multistate reaction pathways. Implications of the early results for understanding the mechanisms and potential routes to improved efficiency and selectivity in beam-induced reactions are discussed. We conclude with a summary of the current state of theory and modeling capabilities in this area and provide our perspective on future directions for theoretical and experimental developments that we view as crucial to advancing the use of convergent electron beams in mode-specific, atomically precise platforms for direct-write materials modifications.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Optical Microscopic Techniques for Synthetic Polymer Characterization

In this paper, we discuss how state-of-the-art optical microscopic techniques enhance our understanding of the morphological and dynamic properties of synthetic polymers. Microscopic/nanoscopic properties obtained using these techniques can be linked to the macroscopic rheological, mechanical, optical, electrical and/or chemical properties of synthetic polymers that are widely used in scientific research and/or in daily life. Lastly, detailed knowledge of nanoscale polymer properties is thus anticipated to facilitate designing novel polymers for various applications, including surface coating, chemical separations, chemical sensing, bioimaging, and organic electronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Snapshots of Proton Accommodation at a Microscopic Water Surface: Understanding the Vibrational Spectral Signatures of the Charge Defect in Cryogenically Cooled H+(H2O)n=2 – 28 Clusters

In this Article, we review the role of gas-phase, size-selected protonated water clusters, H+(H2O)n, in the analysis of the microscopic mechanics responsible for the behavior of the excess proton in bulk water. We extend upon previous studies of the smaller, two-dimensional sheet-like structures to larger (n≥10) assemblies with three-dimensional cage morphologies which better mimic the bulk environment. Indeed, clusters in which a complete second solvation shell forms around a surface-embedded hydronium ion yield vibrational spectra where the signatures of the proton defect display strikingly similar positions and breadth to those observed in dilute acids. We investigate effects of the local structure and intermolecular interactions on the large red shifts observed in the proton vibrational signature upon cluster growth using various theoretical methods. We show that, in addition to sizeable anharmonic couplings, the position of the excess proton vibration can be traced to large increases in the electric field exerted on the embedded hydronium ion upon formation of the first and second solvation shells. MAJ acknowledges support from the U.S. Department of Energy under Grant No. DE-FG02- 06ER15800 as well as the facilities and staff of the Yale University Faculty of Arts and Sciences High Performance Computing Center, and by the National Science Foundation under Grant No. CNS 08-21132 that partially funded acquisition of the facilities. SMK and SSX acknowledge support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Fournier, Joseph A.↗
DOE OSTI2015

Multimodal Broadband Vibrational Sum Frequency Generation (MM-BB-V-SFG) Spectrometer and Microscope

A broadband sum frequency generation (BB-SFG) spectrometer with multimodal (MM) capabilities was constructed, which could be routinely reconfigured for tabletop experiments in reflection, transmission, and total internal reflection (TIR) geometries, as well as microscopic imaging. The system was constructed using a Ti:sapphire amplifier (800 nm, pulse width = 85 fs, repetition rate = 2 kHz), an optical parameter amplification (OPA) system for production of broadband IR pulses tunable between 1000 and 4000 cm –1 , and two Fabry–Pérot etalons arranged in series for production of narrowband 800 nm pulses. The key feature allowing the MM operation was the nearly collinear alignment of the visible (fixed, 800 nm) and infrared (tunable, 1000–4000 cm –1 ) pulses which were spatially separated. Physical insights discussed in this paper include the comparison of spectral bandwidth produced with 40 and 85 fs pump beams, the improvement of spectral resolution using etalons, the SFG probe volume in bulk analysis, the normalization of SFG signals, the stitching of multiple spectral segments, and the operation in different modes for air/liquid and adsorbate/solid interfaces, bulk samples, as well as spectral imaging combined with principle component analysis (PCA). Finally, the SFG spectral features obtained with the MM-BB-SFG system were compared with those obtained with picosecond-scanning-SFG system and high-resolution BB-SFG system (HR-BB-SFG) for dimethyl sulfoxide, α-pinene, and various samples containing cellulose (purified commercial products, Cladophora cell wall, cotton and flax fibers, and onion epidermis cell wall).

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

Addition of Chloroform in a Solvent-in-Salt Electrolyte: Outcomes in the Microscopic Dynamics in Bulk and Confinement

Solvent-in-salt electrolytes (SISEs) are a promising alternative to the electrolytes currently used in commercial devices. Despite the SISEs’ advantages, their utilization is not yet realized due to the poor mobility of their chemical species. Here, we explore this problem by adding chloroform to a SISE formed by acetonitrile and a Li-salt. First, we performed illustrative cycling experiments to highlight the potential of this approach. Then, we focused on the description of the microscopic dynamics of the electrolytes and exposed the relevant aspects to be considered for their optimal performance. While the conductivity at low temperatures may be enhanced by the addition of chloroform, only subtle changes occur at room temperature. As revealed by molecular dynamics simulations and quasielastic neutron scattering (QENS) experiments, this effect is related to the preservation of the structure expected for a highly concentrated solution and promotion of the formation of ionic aggregates. These outcomes occur despite the increase in the overall mobility of the chemical species. The dynamics of the electrolytes in porous carbon was also investigated using QENS. In these circumstances, low concentrations of chloroform lead to diffusivities of the molecular species higher than those observed for the bulk electrolytes. As chloroform’s concentration increases, no further changes in the diffusivities are observed. Nonetheless, chloroform is mostly immobilized on the carbon surfaces and this behavior may be intensified at compositions closer to the eutectic mixture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Microscopic Theory of Long-Time Center-of-Mass Self-Diffusion and Anomalous Transport in Ring Polymer Liquids

We construct a microscopic theory at the level of segment-scale correlated space–time intermolecular forces for the long-time center-of-mass (CM) diffusion constant and intermediate-time non-Fickian transport in dense solutions and melts of ring polymers. The approach combines ideas of polymer, colloid, and liquid-state statistical mechanics to quantify how the multifractal intra-ring conformational structure and inter-ring packing correlations determine dynamic caging constraints and time-dependent friction. Breakdown of Rouse theory is predicted to occur due to length scale-dependent temporal correlation of forces exerted on pairs of tagged ring segments from surrounding polymers. At large enough degrees of polymerization (N), a stronger scaling of the CM diffusion constant (D ∝ N –2 ) is predicted, with a crossover N D proportional to the product of the system-specific macromolecular volume fraction and dimensionless compressibility. In analogy with caging effects in glass-forming fluids, the theory does appear to begin to fail at sufficiently high N/N D for the center-of-mass diffusivity, likely due to another crossover to an even slower activated transport regime. However, use of N/N D with the theoretically predicted N D , in conjunction with dynamic blob scaling ideas for local Rouse friction, collapses semidilute and concentrated solution simulation data onto a master curve. Based on the same physical ideas employed to predict the diffusion constant, a generalized Langevin equation description is formulated for intermediate-time CM transport. It predicts two subdiffusive regimes that emerge due to the self-similar nature of internal ring structure. Analytic and numerical predictions for the apparent non-Fickian exponent as a function of time, N/N D and dimensionless compressibility, the evolution of the maximum degree of subdiffusive motion with N/N D , and the time scale for recovering Fickian diffusion are made, all of which are in good accordance with melt simulations. Furthermore, the present work sets the stage to address activated dynamics and glass formation on the macromolecular scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

High cycle fatigue in the transmission electron microscope

One of the most common causes of structural failure in metals is fatigue induced by cyclic loading. Historically, microstructure-level analysis of fatigue cracks has primarily been performed post mortem. However, such investigations do not directly reveal the internal structural processes at work near micro- and nanoscale fatigue cracks and thus do not provide direct evidence of active microstructural mechanisms. In this paper, the tension–tension fatigue behavior of nanocrystalline Cu was monitored in real time at the nanoscale by utilizing a new capability for quantitative cyclic mechanical loading performed in situ in a transmission electron microscope (TEM). Controllable loads were applied at frequencies from one to several hundred hertz, enabling accumulations of 10 6 cycles within 1 h. The nanometer-scale spatial resolution of the TEM allows quantitative fatigue crack growth studies at very slow crack growth rates, measured here at ~10 –12 m·cycle –1 . This represents an incipient threshold regime that is well below the tensile yield stress and near the minimum conditions for fatigue crack growth. Evidence of localized deformation and grain growth within 150 nm of the crack tip was observed by both standard imaging and precession electron diffraction orientation mapping. Finally, these observations begin to reveal with unprecedented detail the local microstructural processes that govern damage accumulation, crack nucleation, and crack propagation during fatigue loading in nanocrystalline Cu.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Nanophotonic Atomic Force Microscope Transducers Enable Chemical Composition and Thermal Conductivity Measurements at the Nanoscale [Nanophotonic AFM Transducers Enable Chemical Composition and Thermal Conductivity Measurements at the Nanoscale]

The atomic force microscope (AFM) offers a rich observation window on the nanoscale, yet many dynamic phenomena are too fast and too weak for direct AFM detection. Integrated cavity-optomechanics is revolutionizing micromechanical sensing; however, it has not yet impacted AFM. Here, we make a groundbreaking advance by fabricating picogram-scale probes integrated with photonic resonators to realize functional AFM detection that achieve high temporal resolution (<10 ns) and picometer vertical displacement uncertainty simultaneously. The ability to capture fast events with high precision is leveraged to measure the thermal conductivity (η), for the first time, concurrently with chemical composition at the nanoscale in photothermal induced resonance experiments. The intrinsic η of metal–organic-framework individual microcrystals, not measurable by macroscale techniques, is obtained with a small measurement uncertainty (8%). The improved sensitivity (50×) increases the measurement throughput 2500-fold and enables chemical composition measurement of molecular monolayer-thin samples. In conclusion, our paradigm-shifting photonic readout for small probes breaks the common trade-off between AFM measurement precision and ability to capture transient events, thus transforming the ability to observe nanoscale dynamics in materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Direct Visualization and Control of Atomic Mobility at {100} Surfaces of Ceria in the Environmental Transmission Electron Microscope

We report that ceria is one of the world’s most prominent material for applications in heterogeneous catalysis, as catalyst support or catalyst itself. Despite an exhaustive literature on the structure of reactive facets of CeO 2 in line with its catalytic mechanisms, the temporal evolution of the atomic surface structure exposed to realistic redox conditions remains elusive. Here, we provide a direct visualization of the atomic mobility of cerium atoms on {100} surfaces of CeO 2 nanocubes at room temperature in high vacuum, O 2 , and CO 2 atmospheres in an environmental transmission electron microscope. Lastly, through quantification of the cationic mobility, we demonstrate the control of the surface dynamics under exposure to O 2 and CO 2 atmospheres, providing opportunities for a better understanding of the intimate catalytic mechanisms.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Probing Light Atoms at Subnanometer Resolution: Realization of Scanning Transmission Electron Microscope Holography

Atomic resolution imaging of light elements in electron-transparent materials has long been a challenge. Biomolecular materials, for example, are rapidly altered by incident electrons. We demonstrate a scanning transmission electron microscopy (STEM) technique, called STEM holography, capable of efficient structural analysis of beam-sensitive nanomaterials. STEM holography measures the absolute phase and amplitude of electrons passed through a specimen via interference with a vacuum reference wave. We use an amplitude-dividing nanofabricated grating to prepare multiple beams focused at the sample. We configure the postspecimen microscope imaging system to overlap the beams, forming an interference pattern. We record and analyze the pattern at each 2D-raster-scan-position, reconstructing the complex object wave. As a demonstration, we image gold nanoparticles on an amorphous carbon substrate at 2.4 Å resolution. In conclusion STEM holography offers higher contrast of the carbon while maintaining gold atomic lattice resolution compared to high angle annular dark field STEM.

4D-STEM↗
DOE OSTI2022

Microscopic Dynamics of Inverse Wormlike Micelles Probed Using X-ray Photon Correlation Spectroscopy

Wormlike micelles (WLMs) are ubiquitous viscoelastic modifiers that share properties with polymer solutions. While 5 their macroscopic rheology is well-understood, their microscopic dynamics are less studied because they span a large range of time 6 and length scales. In this work, we demonstrate the use of X-ray photon correlation spectroscopy to interrogate the segmental 7 dynamics of inverse WLM solutions swollen with a rubidium chloride solution. We observe a diffusive scaling of the dynamics and 8 extract a temperature-dependent diffusion coefficient, which we associate with the thermal interactions of the slow segmental 9 dynamics near entanglement points. Further, we probe this relaxation process across the unbranched to branched topological transition and 10 find no microstructural evidence of branch formation in the slow mode. Instead, we observe that the dynamics become more 11 homogeneous and prominent as the temperature is reduced and water content increases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Microscopic Theory of the Long-Time Diffusivity and Intermediate-Time Anomalous Transport of a Nanoparticle in Polymer Melts

The transport of a single nanoparticle in unentangled and entangled polymer melts is studied based on a microscopic, force-level, self-consistent generalized Langevin equation approach. Nanoparticle self-motion and length-scale-dependent polymer relaxation enter as two parallel and competing channels of force relaxation. For entangled melts, particle long-time mobility exhibits size-dependent non-Stokes–Einstein behaviors controlled by (i) fast diffusion and length-scale-dependent collective relaxation of the unentangled matrix for particles smaller than the tube diameter and (ii) polymer relaxation via reptation for nanoparticles larger than the tube diameter. The two regimes are connected by a relatively sharp but continuous crossover. Recovery of hydrodynamic behavior requires the nanoparticle to be roughly 10 times larger than the tube diameter. Theoretical predictions for the diffusion constant are in good agreement with recent simulations of unentangled and lightly entangled melts, including the crossover regime where the nanoparticle and tube diameters are roughly equal. The calculations are also in reasonable accord with several experiments in entangled synthetic polymer melts and DNA solutions, although the activated hopping motion not included in the present theory may be important in a narrow intermediate crossover regime for sufficiently entangled polymers. The predictions of the theory for intermediate-time anomalous diffusion are of mixed quality based on comparison to simulations. Furthermore, the significant limitations identified are associated with our minimalist treatment of collective density fluctuation relaxation on intermediate time and length scales, including the possible importance of non-reptation relaxation processes in entangled melts.

77 NANOSCIENCE AND NANOTECHNOLOGY↗