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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Non-classical crystallization in soft and organic materials

Classical nucleation and crystal growth theories describe how nuclei form, become stable after reaching a critical size and then enlarge through monomer attachment. More than two decades ago, non-classical pathways have been proposed for various types of (bio)molecules and materials, which can substantially alter the crystallization kinetics and outcomes. Direct observation of non-classical crystallization of inorganic nanomaterials, including metastable structure-mediated and particle attachment-based pathways that usually occur on the nanoscale, was enabled by in situ liquid-phase electron microscopy. However, it was not until recently that the crystallization dynamics of beam-sensitive soft materials were directly imaged with sufficient spatial resolution, and a level of microstructural understanding of defects and interfaces emerged. This article provides a high-level review of the non-classical crystallization pathways discovered in soft and organic materials and a forward-looking guide for future research. We first analyse how the characteristics of soft materials affect their crystallization pathways and kinetics. We then identify technical approaches to studying the crystallization trajectories of soft materials and discuss strategies to properly select and apply them to different systems. Breakthroughs made in understanding the crystallization of small organic molecules, (bio)macromolecules, colloids and reticular framework materials are examined. Lastly, we provide an outlook on the challenges in elucidating soft material crystallization pathways and the opportunities for assisting the design and synthesis of new materials and structures.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Enabling a novel approach to a controlled fabrication of 1D crystalline nanowires on suspended microstructures of arbitrary geometries using two direct-writing technologies

Recent progresses in additive manufacturing have inspired new technologies, such as direct laser writing technique, based on two-photon polymerization (2 PP), which complements and further enriches the nanofabrication tools portfolio. Here, we combine 2 PP and our mask-free scanning probe assisted ‘direct-write patterning’ (DWP) method to allow for: a) the fabrication of micro-bridge structures with sub-micrometer resolution, b) selective synthesis of crystalline ZnO nanowires at predefined locations, respectively. This synergistic approach enables cantilever probe patterning of catalysts directly on suspended micro-bridges for in-situ CVD growth of nanoscale material, in a templated manner. The study reported here represents the first proof-of-concept experiments demonstrating versatile and scalable methodology, which can be applied and straightforwardly extended to grow a variety of other nanomaterials, in a controlled and selective fashion, on freestanding micro/nanoscale structures, whose size and geometry can be conveniently varied via templating of sacrificial 2 PP polymeric scaffolds. Furthermore, the demonstration of the possibility to integrate this new approach with the conventional lithography techniques provides a step forward to the development of the novel class of hybrid polymer-silicon-1D or -2D materials, and systems. The quality of the produced ZnO nanowire assemblies was assessed using several physical characterization methods.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Low‐Loss Tunable Infrared Plasmons in the High‐Mobility Perovskite (Ba,La)SnO 3

Abstract BaSnO 3 exhibits the highest carrier mobility among perovskite oxides, making it ideal for oxide electronics. Collective charge carrier oscillations known as plasmons are expected to arise in this material, thus providing a tool to control the nanoscale optical field for optoelectronics applications. Here, the existence of relatively long‐lived plasmons supported by high‐mobility charge carriers in La‐doped BaSnO 3 (BLSO) is demonstrated. By exploiting the high spatial and energy resolution of electron energy‐loss spectroscopy with a focused beam in a scanning transmission electron microscope, the dispersion, confinement ratio, and damping of infrared localized surface plasmons (LSPs) in BLSO nanoparticles are systematically investigated. It is found that LSPs in BLSO exhibit a high degree of spatial confinement compared to those sustained by noble metals and have relatively low losses and high quality factors with respect to other doped oxides. Further analysis clarifies the relation between plasmon damping and carrier mobility in BLSO. The results support the use of nanostructured degenerate semiconductors for plasmonic applications in the infrared region and establish a solid alternative to more traditional plasmonic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Nanoscale insights into the structure of solution-processed graphene by x-ray scattering

Abstract Chemical exfoliation is an attractive approach for the synthesis of graphene due to its low cost and simplicity. However, challenges still remain in the characterization of solution-processed graphene, in particular with atomic resolution. Through this work we demonstrate the x-ray pair distribution function as a novel approach to study solution-processed graphene or other 2D materials with atomic resolution, directly in solution, produced by liquid-phase and electrochemical exfoliations. The results show the disappearance of long-range atomic correlations, in both cases, confirming the production of single and few-layer graphene. In addition, a considerable ring distortion has been observed as compared to graphite, irrespective of the solvent used: the normal surface angle to the sheet of the powder sample should be less than 6°, compatible with ripples formation observed in suspended graphene. We attribute this effect to the interaction of solvent molecules with the graphene nanosheets.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Multimodal hard X-ray nanoprobe techniques for operando investigations of photovoltaic devices

Compared with conventional laboratory-scale X-ray techniques, synchrotron based X-rays with higher brilliance and higher coherence allow for the investigation of various material properties with high spatial resolution. The microscopic behaviours of materials can be examined using the Hard X-ray Nanoprobe beamline (I14) at Diamond Light Source, which provides a 50 nm focused beam and has been successfully employed to identify nanoscale optoelectronic features in energy-harvesting materials such as halide perovskites that exhibit local heterogeneity. We have developed X-ray beam-induced current (XBIC) measurement capability at I14 to address the growing demand for operando analysis in energy-harvesting research. Here, we demonstrate that X-ray fluorescence (XRF)/XBIC multimodal measurements are feasible at I14 and apply these newly implemented techniques to study perovskite solar cells with various additive concentrations to understand the effect of the additive on nanoscale optoelectronic performance. This expanded operando characterization capability offers the possibility of monitoring nanometre-scale compositional variations and corresponding optoelectronic features of actual solar cell configurations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Three-dimensional topological magnetic monopoles and their interactions in a ferromagnetic meta-lattice

Topological magnetic monopoles (TMMs), also known as hedgehogs or Bloch points, are three-dimensional (3D) nonlocal spin textures that are robust to thermal and quantum fluctuations due to the topology protection. Although TMMs have been observed in skyrmion lattices, spinor Bose–Einstein condensates, chiral magnets, vortex rings and vortex cores, it has been difficult to directly measure the 3D magnetization vector field of TMMs and probe their interactions at the nanoscale. Here, we report the creation of 138 stable TMMs at the specific sites of a ferromagnetic meta-lattice at room temperature. We further develop soft x-ray vector ptycho-tomography to determine the magnetization vector and emergent magnetic field of the TMMs with a 3D spatial resolution of 10 nm. This spatial resolution is comparable to the magnetic exchange length of transition metals, enabling us to probe monopole-monopole interactions. We find that the TMM and anti-TMM pairs are separated by 18.3±1.6 nm, while the TMM and TMM, anti-TMM and anti-TMM pairs are stabilized at comparatively longer distances of 36.1±2.4 nm and 43.1±2.0 nm, respectively. We also observe virtual TMMs created by magnetic voids in the meta-lattice. This work demonstrates that ferromagnetic meta lattices could be used as a platform to create and investigate the interactions and dynamics of TMMs. Furthermore, we expect that soft x-ray vector ptycho-tomography can be broadly applied to quantitatively image 3D vector fields in magnetic and anisotropic materials at the nanoscale.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Revealing Progressive Degradation of Cobalt Oxide Nanoparticles During Thermochemical Redox Cycling via Operando STEM-EELS

Metal oxides are promising materials for long-duration thermochemical energy storage. Efforts to characterize their reaction kinetics, conversion rate, and morphological evolution during thermochemical cycling have largely focused on bulk and microscale measurements. However, the design of nanostructured metal oxides could improve the reaction reversibility and kinetics, warranting the development of platforms to investigate how these materials behave at the nanoscale. Here, we demonstrate the use of correlative, time-resolved electron energy loss spectroscopy and imaging in an environmental transmission electron microscope for studying the thermochemical cyclability of cobalt oxide nanoparticles with high spatial and temporal resolution. The spectroscopic data reveal a striking decrease in reaction kinetics after the first cycle, resulting from sintering-driven nanostructural densification. Comparison between cycling in humid and dry air shows that atmospheric conditions can modulate reaction transition temperatures but have limited effects on sintering over multiple cycles, suggesting long-term durability will instead rely on synthetic and/or nanostructural modifications.

25 ENERGY STORAGE↗
DOE OSTI2025

Observation of nanoparticle coalescence during core-shell metallic nanowire growth in colloids via nanoscale imaging

The surface morphology and shape of crystalline nanowires significantly influence their functional properties, including phonon transport, electrocatalytic performance, to name but a few. However, the kinetic pathways driving these morphological changes remain underexplored due to challenges in real-space and real-time imaging at single-particle and atomic resolutions. This study investigates the dynamics of shell (Au, Pd, Pt, Fe, Cu, Ni) deposition on AuAg alloy seed nanowires during core-shell formation. By using chiral/non-chiral seed nanowires, advanced imaging techniques, including liquid-phase transmission electron microscopy (LPTEM), cryogenic TEM, and three-dimensional electron tomography, a three-step deposition process is revealed: heterogeneous nucleation, nanoparticle attachment, and coalescence. It is found that colloidal Ostwald ripening, metal reactivity, and deposition amount modulate nanoparticle size and surface roughness, shaping final morphologies. Noble metal nanoparticles (Au, Ag, Pd, Pt) coalesce with seed nanowire along the 〈111〉 direction, distinct from that of other metals. These findings are consistent across different metals, including Ru, Cu, Fe, and Ni, highlighting the hypothesis of these processes in nanowire formation. These findings enhance traditional crystallographic theories and provide a framework for designing nanowire morphology. Additionally, our imaging techniques may be applied to investigate phenomena like electrodeposition, dendrite growth in batteries, and membrane deformation.

Yang, Dahai↗
DOE OSTI2024

STORM Super-Resolution Visualization of Self-Assembled γPFD Chaperone Ultrastructures in Methanocaldococcus jannaschii

Gamma-prefoldin (γPFD), a unique chaperone found in the extremely thermophilic methanogen Methanocaldococcus jannaschii, self-assembles into filaments in vitro, which so far have been observed using transmission electron microscopy and cryo-electron microscopy. Utilizing three-dimensional stochastic optical reconstruction microscopy (3D-STORM), here we achieve ~20 nm resolution by precisely locating individual fluorescent molecules, hence resolving γPFD ultrastructure both in vitro and in vivo. Through CF647 NHS ester labeling, we first demonstrate the accurate visualization of filaments and bundles with purified γPFD. Next, by implementing immunofluorescence labeling after creating a 3xFLAG-tagged γPFD strain, we successfully visualize γPFD in M. jannaschii cells. Through 3D-STORM and two-color STORM imaging with DNA, we show the widespread distribution of filamentous γPFD structures within the cell. These findings provide valuable insights into the structure and localization of γPFD, opening up possibilities for studying intriguing nanoscale components not only in archaea but also in other microorganisms.

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

High-resolution analogue of time-domain phonon spectroscopy in the transmission electron microscope

Femtosecond photoexcitation of semiconducting materials leads to the generation of coherent acoustic phonons (CAPs), the behaviours of which are linked to intrinsic and engineered electronic, optical and structural properties. While often studied with pump-probe spectroscopic techniques, the influence of nanoscale structure and morphology on CAP dynamics can be challenging to resolve with these all-optical methods. Here, we used ultrafast electron microscopy (UEM) to resolve variations in CAP dynamics caused by differences in the degree of crystallinity in as-prepared and annealed GaAs lamellae. Following in situ femtosecond photoexcitation, we directly imaged the generation and propagation dynamics of hypersonic CAPs in a mostly amorphous and, following an in situ photothermal anneal, a mostly crystalline lamella. Subtle differences in both the initial hypersonic velocities and the asymptotic relaxation behaviours were resolved via construction of space-time contour plots from phonon wavefronts. Comparison to bulk sound velocities in crystalline and amorphous GaAs reveals the influence of the mixed amorphous-crystalline morphology on CAP dispersion behaviours. Further, an increase in the asymptotic velocity following annealing establishes the sensitivity of quantitative UEM imaging to both structural and compositional variations through differences in bonding and elasticity. Lastly, implications of extending the methods and results reported here to elucidating correlated electronic, optical and structural behaviours in semiconducting materials are discussed.

42 ENGINEERING↗
DOE OSTI2024

Selected Area Manipulation of MoS 2 via Focused Electron Beam-Induced Etching for Nanoscale Device Editing

Here we demonstrate direct-write patterning of single and multilayer MoS 2 via a focused electron beam-induced etching (FEBIE) process mediated with the XeF 2 precursor. MoS 2 etching is performed at various currents, areal doses, on different substrates, and characterized using scanning electron and atomic force microscopies as well as Raman and photoluminescence spectroscopies. Scanning transmission electron microscopy reveals a sub-40 nm etching resolution and the progression of point defects and lateral etching of the consequent unsaturated bonds. The results confirm that the electron beam-induced etching process is minimally invasive to the underlying material in comparison to ion beam techniques, which damage the subsurface material. Single-layer MoS 2 field-effect transistors are fabricated, and device characteristics are compared for channels that are edited via the selected area etching process. The source–drain current at constant gate and source–drain voltage scale linearly with the edited channel width. Moreover, the mobility of the narrowest channel width decreases, suggesting that backscattered and secondary electrons collaterally affect the periphery of the removed area. Focused electron beam doses on single-layer transistors below the etching threshold were also explored as a means to modify/thin the channel layer. The FEBIE exposures showed demonstrative effects via the transistor transfer characteristics, photoluminescence spectroscopy, and Raman spectroscopy. While strategies to minimize backscattered and secondary electron interactions outside of the scanned regions require further investigation, here, we show that FEBIE is a viable approach for selective nanoscale editing of MoS 2 devices.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Single molecule insights into interfacial molecular recognition for model electrochemical DNA biosensors

Electrochemical sensors that use surface-immobilized DNA to bind analytes and transduce the binding into electrochemical signals, have the potential for rapid, specific, and sensitive detection of bioanalytes via a compact and portable platform. However, accessing the structure of these surfaces/interfaces at the relevant spatial scale (< 10 nm), which determines the interfacial interactions and ultimately sensing performance, remains an unsolved challenge. Here, we review studies that have used high resolution atomic force microscope imaging and spatial statistical analysis tools to understand crowding interactions between thiolated DNA probes immobilized on gold electrodes and how such interactions impact target binding. We also review related studies that attempt to control the nanoscale spatial arrangement of the immobilized recognition elements to optimize sensing performance. Furthermore, these efforts have led to new advances in understanding of the structure-function relationships of DNA-based electrochemical biosensors to move the field toward rational engineering of these biosensing interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Defect-mediated ripening of core-shell nanostructures

Abstract Understanding nanostructure ripening mechanisms is desirable for gaining insight on the growth and potential applications of nanoscale materials. However, the atomic pathways of nanostructure ripening in solution have rarely been observed directly. Here, we report defect-mediated ripening of Cd-CdCl 2 core-shell nanoparticles (CSN) revealed by in-situ atomic resolution imaging with liquid cell transmission electron microscopy. We find that ripening is initiated by dissolution of the nanoparticle with an incomplete CdCl 2 shell, and that the areas of the Cd core that are exposed to the solution are etched first. The growth of the other nanoparticles is achieved by generating crack defects in the shell, followed by ion diffusion through the cracks. Subsequent healing of crack defects leads to a highly crystalline CSN. The formation and annihilation of crack defects in the CdCl 2 shell, accompanied by disordering and crystallization of the shell structure, mediate the ripening of Cd-CdCl 2 CSN in the solution.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Spectral and polarization based imaging in deep-ultraviolet excited photoelectron microscopy

Using photoelectron emission microscopy, nanoscale spectral imaging of atomically thin MoS2 buried between Al2O3 and SiO2 is achieved by monitoring the wavelength and polarization dependence of the photoelectron signal excited by deep-ultraviolet light. Although photons induce the photoemission, images can exhibit resolutions below the photon wavelength as electrons sense the response. To validate this concept, the dependence of photoemission yield on the wavelength and polarization of the exciting light was first measured and then compared to simulations of the optical response quantified with classical optical theory. A close correlation between experiment and theory indicates that photoemission probes the optical interaction of UV-light with the material stack directly. The utility of this probe is then demonstrated when both the spectral and polarization dependence of photoemission observe spatial variation consistent with grains and defects in buried MoS2. Taken together, these new modalities of photoelectron microscopy allow mapping of optical property variation at length scales unobtainable with conventional light-based microscopy.

Beechem, Thomas E. (ORCID:0000000275360719)↗
DOE OSTI2023

Picosecond magneto-optic thermometry measurements of nanoscale thermal transport in AlN thin films

The thermal conductivity Λ of wide bandgap semiconductor thin films, such as AlN, affects the performance of high-frequency devices, power devices, and optoelectronics. However, accurate measurements of Λ in thin films with sub-micrometer thicknesses and Λ > 100 W m -1 K -1 is challenging. Widely used pump/probe metrologies, such as time–domain thermoreflectance (TDTR) and frequency–domain thermoreflectance, lack the spatiotemporal resolution necessary to accurately quantify thermal properties of sub-micrometer thin films with high Λ. In this work, we use a combination of magneto-optic thermometry and TiN interfacial layers to significantly enhance the spatiotemporal resolution of pump/probe thermal transport measurements. We use our approach to measure Λ of 100, 400, and 1000 nm AlN thin films. We coat AlN thin films with a ferromagnetic thin-film transducer with the geometry of (1 nm-Pt/0.4 nm-Co) x3 /(2 nm-TiN). This PtCo/TiN transducer has a fast thermal response time of <50 ps, which allows us to differentiate between the thermal response of the transducer, AlN thin film, and substrate. For the 100, 400, and 1000 nm thick AlN films, we determine Λ to be 200 ± 80, 165 ± 35, and 300 ± 70 W m -1 K -1 , respectively. We conclude with an uncertainty analysis that quantifies the errors associated with pump/probe measurements of thermal conductivity, as a function of transducer type, thin-film thermal conductivity, and thin-film thickness. Time resolved magneto-optic Kerr effect experiments can measure films that are three to five times thinner than is possible with standard pump/probe metrologies, such as TDTR. This advance in metrology will enable better characterization of nanoscale heat transfer in high thermal conductivity material systems like wide bandgap semiconductor heterostructures and devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Atomic Layer Deposition of Nanolayered Carbon Films

In this paper, carbon thin films were grown using the plasma-enhanced atomic layer deposition (PE-ALD). Methane (CH4) was used as the carbon precursor to grow the carbon thin film. The grown film was analyzed by the high-resolution transmission electron micrograph (TEM), X-ray photoelectron spectroscopy (XPS) analysis, and Raman spectrum analysis. The analyses show that the PE-ALD-grown carbon film has an amorphous structure. It was found that the existence of defective sites (nanoscale holes or cracks) on the substrate of copper foil could facilitate the formation of nanolayered carbon films. The mechanism for the formation of nanolayered carbon film in the nanoscale holes was discussed. This finding could be used for the controlled growth of nanolayered carbon films or other two-dimensional nanomaterials while combining with modern nanopatterning techniques.

Xiao, Zhigang (ORCID:0000000215950565)↗
DOE OSTI2024

Unraveling Interdiffusion Phenomena and the Role of Nanoscale Diffusion Barriers in the Copper–Gold System

Diffusion is one of the most fundamental concepts in materials science, playing a pivotal role in materials synthesis, forming, and degradation. Of particular importance is solid state interdiffusion of metals which defines the usable parameter space for material combinations in the form of alloys. This parameter space can be explored on the macroscopic scale by using diffusion couples. However, this method reaches its limit when going to low temperatures, small scales, and when testing ultrathin diffusion barriers. Therefore, this work transfers the principle of the diffusion couples to small scales by using core–shell nanowires and in situ heating. This allows us to delve into the interdiffusion dynamics of copper and gold, revealing the interplay between diffusion and the disorder–order phase transition. Our in situ TEM experiments in combination with chemical mapping reveal the interdiffusion coefficients of Cu and Au at low temperatures and highlight the impact of ordering processes on the diffusion behavior. The formation of ordered domains within the solid-solution is examined using high-resolution imaging and nanodiffraction including strain mapping. In addition, we examine the effectiveness of ultrathin Al 2 O 3 barrier layers to control interdiffusion of the diffusion couple. Our findings indicate that a 5 nm thick layer serves as an efficient diffusion barrier. Furthermore, this research provides valuable insights into the interdiffusion behavior of Cu and Au on the nanoscale, offering potential applications in the development of miniaturized integrated circuits and nanodevices.

alloys↗
DOE OSTI2022

Determinants of synapse diversity revealed by super-resolution quantal transmission and active zone imaging

Neural circuit function depends on the pattern of synaptic connections between neurons and the strength of those connections. Synaptic strength is determined by both postsynaptic sensitivity to neurotransmitter and the presynaptic probability of action potential evoked transmitter release (P r ). Whereas morphology and neurotransmitter receptor number indicate postsynaptic sensitivity, presynaptic indicators and the mechanism that sets P r remain to be defined. To address this, we developed QuaSOR, a super-resolution method for determining P r from quantal synaptic transmission imaging at hundreds of glutamatergic synapses at a time. We mapped the P r onto super-resolution 3D molecular reconstructions of the presynaptic active zones (AZs) of the same synapses at the Drosophila larval neuromuscular junction (NMJ). We find that P r varies greatly between synapses made by a single axon, quantify the contribution of key AZ proteins to P r diversity and find that one of these, Complexin, suppresses spontaneous and evoked transmission differentially, thereby generating a spatial and quantitative mismatch between release modes. Transmission is thus regulated by the balance and nanoscale distribution of release-enhancing and suppressing presynaptic proteins to generate high signal-to-noise evoked transmission.

59 BASIC BIOLOGICAL SCIENCES↗