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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 523 records · Page 29

Thermally reconfigurable monoclinic nematic colloidal fluids

Fundamental relationships are believed to exist between the symmetries of building blocks and the condensed matter phases that they form. For example, constituent molecular and colloidal rods and disks impart their uniaxial symmetry onto nematic liquid crystals, such as those used in displays. Low-symmetry organizations could form in mixtures of rods and disks, but entropy tends to phase-separate them at the molecular and colloidal scales, whereas strong elasticity-mediated interactions drive the formation of chains and crystals in nematic colloids. To have a structure with few or no symmetry operations apart from trivial ones has so far been demonstrated to be a property of solids alone, but not of their fully fluid condensed matter counterparts, even though such symmetries have been considered theoretically and observed in magnetic colloids. In this work, we show that dispersing highly anisotropic charged colloidal disks in a nematic host composed of molecular rods provides a platform for observing many low-symmetry phases. Depending on the temperature, concentration and surface charge of the disks, we find nematic, smectic and columnar organizations with symmetries ranging from uniaxial to orthorhombic and monoclinic. With increasing temperature, we observe unusual transitions from less- to more-ordered states and re-entrant phases. Most importantly, we demonstrate the presence of reconfigurable monoclinic colloidal nematic order, as well as the possibility of thermal and magnetic control of low-symmetry self-assembly. Our experimental findings are supported by theoretical modelling of the colloidal interactions between disks in the nematic host and may provide a route towards realizing many low-symmetry condensed matter phases in systems with building blocks of dissimilar shapes and sizes, as well as their technological applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Non-toxic silver iodide (AgI) quantum dots sensitized solar cells

Highlights: • We have demonstrated AgI sensitized solar cell for the first time. • Obtained mesoporous titania powders possessed small crystallite size, high purity and surface area, and developed mesopores with a narrow pore size distribution. • Photovoltaic measurements revealed the electron injection from AgI to TiO{sub 2}. • The assembled AgI-QD solar cells yielded a power conversion efficiency of 0.64% under one sun illumination. • AgI may be a suitable candidate material for use as a non-toxic sensitizer in QDSSC. - Abstract: The present study reports the performance of a new photosensitizer -AgI quantum dots (QDs)- and mesoporous titania (TiO{sub 2}) nanocrystals synthesized by sol–gel (SG) method for solar cells. Furthermore, the effects of n-heptane on the textural properties of TiO{sub 2} nanocrystals were comprehensively investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), N{sub 2} adsorption–desorption measurements, and UV–vis spectroscopy. TiO{sub 2} powders exhibited an anatase-type mesoporous structure with a high surface area of 89.7 m{sup 2}/g. Afterwards, the QDs were grown on mesoporous TiO{sub 2} surface to fabricate a TiO{sub 2}/AgI electrode by a successive ionic layer adsorption and reaction (SILAR) deposition route. Current–voltage characteristics and electrochemical impedance spectroscopy (EIS) data demonstrated that the injection of photoexcited electrons from AgI QDs into the TiO{sub 2} matrix produces photocurrents. The assembled AgI-QD solar cells yielded a power conversion efficiency of 0.64% and a short-circuit current of 2.13 mA/cm{sup 2} under one sun illumination.

36 MATERIALS SCIENCE↗

Integrated Nanotechnologies

Nanomaterials offer exceptional properties for photonic, electronic, quantum, magnetic, structural, mechanical, chemical, nuclear, and biological functionality. However, real access to enhanced functionality remains limited without connecting the nanoscale across the mesoscale to macroscale assemblies and the ability to define and control nanomaterials organization, interactions, and interfaces. Integration is essential for accessing and controlling functionality to harness nanomaterials properties while also generating new behaviors and properties. Integration thus provides a route to discovering, generating, and using intrinsic and emergent nanomaterials properties, which define the two focus areas of this leadership theme.

36 MATERIALS SCIENCE↗

Design and Characterization of Carbon Nanotube Nanocomposites

Revolutionary design concepts in future aerospace vehicles will depend on extraordinary material properties to permit significant reduction of mass and size of components, while imparting intelligence. Due to their combination of remarkable electrical and mechanical properties, carbon nanotubes (CNT) are expected to enable this paradigm shift in design concepts. However, significant challenges still exist in translating these CNT properties into the macrostructures required for future generations of aerospace vehicles. While an accepted route for making the leap from nanostructures to useful macrostructures has not been fully charted, this paper will give an overview of the approach taken by some researchers at NASA Langley Research Center to sort out issues involved in the development of CNT nanocomposites for multifunctional structures. Specifically, the dispersion of carbon nanotubes in polymer matrices, characterization of nanocomposites, the role of quantum computation in providing guidance for processing and the use of computational analysis in data interpretation will be covered. Significant improvements in mechanical and electrical properties of CNT nanocomposites with very low loadings of CNTs are described and lend credence to the potential for using CNTs in achieving technological leaps in composite development.

Siochi, Emilie J.↗

Optical magnetism in planar metamaterial heterostructures

Harnessing artificial optical magnetism has previously required complex two- and three-dimensional structures, such as nanoparticle arrays and split-ring metamaterials. By contrast, planar structures, and in particular dielectric/metal multilayer metamaterials, have been generally considered non-magnetic. Although the hyperbolic and plasmonic properties of these systems have been extensively investigated, their assumed non-magnetic response limits their performance to transverse magnetic (TM) polarization. We propose and experimentally validate a mechanism for artificial magnetism in planar multilayer metamaterials. We also demonstrate that the magnetic properties of high-index dielectric/metal hyperbolic metamaterials can be anisotropic, leading to magnetic hyperbolic dispersion in certain frequency regimes. We show that such systems can support transverse electric polarized interface-bound waves, analogous to their TM counterparts, surface plasmon polaritons. Here, our results open a route for tailoring optical artificial magnetism in lithography-free layered systems and enable us to generalize the plasmonic and hyperbolic properties to encompass both linear polarizations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Tuning interfacial exchange interactions via electronic reconstruction in transition-metal oxide heterostructures

The impact of interfacial electronic reconstruction on the magnetic characteristics of La0.7Sr0.3CoO3 (LSCO)/La0.7Sr0.3MnO3 (LSMO) superlattices was investigated as a function of layer thickness using a combination of soft x-ray magnetic spectroscopy and bulk magnetometry. We found that the magnetic properties of the LSCO layers are impacted by two competing electronic interactions occurring at the LSCO/substrate and LSMO/LSCO interfaces. For thin LSCO layers (< 5 nm), the heterostructures exist in a highly coupled state where the chemically distinct layers behave as a single magnetic compound with magnetically active Co2+ ions. As the LSCO thickness increases, a high coercivity LSCO layer develops which biases a low coercivity layer, which is composed not only of the LSMO layer, but also an interfacial LSCO layer. These results suggest a new route to tune the magnetic properties of transition metal oxide heterostructures through careful control of the interface structure.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Characterization of an active metasurface using terahertz ellipsometry

Switchable metasurfaces fabricated on a doped epi-layer have become an important platform for developing techniques to control terahertz (THz) radiation, as a DC bias can modulate the transmission characteristics of the metasurface. To model and understand this performance in new device configurations accurately, a quantitative understanding of the bias-dependent surface characteristics is required. In this work, we perform THz variable angle spectroscopic ellipsometry on a switchable metasurface as a function of DC bias. By comparing these data with numerical simulations, we extract a model for the response of the metasurface at any bias value. Using this model, we predict a giant bias-induced phase modulation in a guided wave configuration. Lastly, these predictions are in qualitative agreement with our measurements, offering a route to efficient modulation of THz signals.

36 MATERIALS SCIENCE↗

Confocal Raman imaging of skin sections containing hair follicles using classical least squares regression and multivariate curve resolution – alternating least squares

Confocal Raman microscopy (CRM) is applied ex vivo for imaging of the spatial distribution of different skin components in skin sections containing hair follicles. For multivariate data analysis, different methods are used in order to spectrally decompose the reference spectra of the skin components (dermis, viable epidermis, stratum corneum and hair). Classical least squares regression (CLS) and multivariate curve resolution–alternating least squares (MCR-ALS) are chosen as suitable methods. In comparison to other optical methods, the advantage of CRM is molecular specificity and dispensability of labelling dyes, which is e.g. necessary in fluorescence microscopy. Therefore, a useful future application of CRM in combination with multivariate data analysis lies in the analysis of penetration routes of topically applied substances, such as cosmetic formulations or drugs into the skin, which is particularly interesting in and around hair follicles. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Criticality and Magnetic Phases of Ising Shastry–Sutherland Candidate Holmium Tetraboride

Frustrated magnetic systems arising in geometrically constrained lattices represent rich platforms for exploring unconventional phases of matter, including fractional magnetization plateaus, incommensurate orders and complex domain dynamics. However, determining the microscopic spin configurations that stabilize such phases is a key challenge, especially when in-plane and out-of-plane spin components coexist and compete. Here, we combine neutron scattering and magnetic susceptibility experiments with simulations to investigate the emergence of field-induced fractional plateaus and the related criticality in a frustrated magnet holmium tetraboride (HoB 4 ) that represents the family of rare earth tetraborides that crystalize in a Shastry–Sutherland lattice in the ab plane. We focus on the interplay between classical and quantum criticality near phase boundaries, as well as the role of material defects in the stabilization of the ordered phases. We find that simulations using classical annealing can explain certain observed features in the experimental Laue diffraction and the origin of multiple magnetization plateaus. Our results show that defects and out-of-plane interactions play an important role and can guide the route towards resolving microscopic spin textures in highly frustrated magnets.

Frustration↗

A general time-dependent route to Resonance-Raman spectroscopy including Franck-Condon, Herzberg-Teller and Duschinsky effects

We present a new formulation of the time-dependent theory of Resonance-Raman spectroscopy (TD-RR). Particular attention has been devoted to the generality of the framework and to the possibility of including different effects (Duschinsky mixing, Herzberg-Teller contributions). Furthermore, the effects of different harmonic models for the intermediate electronic state are also investigated. Thanks to the implementation of the TD-RR procedure within a general-purpose quantum-chemistry program, both solvation and leading anharmonicity effects have been included in an effective way. The reliability and stability of our TD-RR implementation are validated against our previously proposed and well-tested time-independent procedure. Practical applications are illustrated with some closed- and open-shell medium-size molecules (anthracene, phenoxyl radical, benzyl radical) and the simulated spectra are compared to the experimental results. More complex and larger systems, not limited to organic compounds, can be also studied, as shown for the case of Tris(bipyridine)ruthenium(II) chloride.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding and Curing Structural Defects in Colloidal GaAs Nanocrystals

Nearly three decades since the first report on the synthesis of colloidal GaAs nanocrystals (NCs), the preparation and properties of this material remain highly controversial. Traditional synthetic routes either fail to produce the GaAs phase or result in materials that do not show expected optical properties such as excitonic transitions. In this work, we demonstrate a variety of synthetic routes toward crystalline GaAs NCs. By using a combination of Raman, EXAFS and transient absorption spectroscopies, we conclude that unusual optical properties of 2 colloidal GaAs NCs can be related to the presence of vacancies and lattice disorder. We introduce novel molten salt based annealing approach to alleviate these structural defects and show the emergence of size-dependent excitonic transitions in colloidal GaAs quantum dots.

Colloidal Nanocrystals↗

Reactions of CH3, CH3O, and CH3O2 radicals with O3

Ozone was photolyzed at 253.7 nm at 25 and -52 degrees in the presence of CH4 and O2 to measure the reactions of O3 with CH3, CH3O, and CH3O2. The O(1D) atoms produced in the primary photochemical act react with CH4 to give CH3 radicals which in turn can react with O2 to give CH3O2 and CH3O radicals. At very high O2 to O3 concentration ratios, the quantum yield of O3 disappearance approached 1.0, indicating that O3 reactions with CH3O2 and CH3O are slow. Upper limits to the rate coefficients at 25 degrees were computed. At lower values of the concentration ratio, chain decomposition of O3 occurred which could be explained by the reaction of O3 with CH3 radicals to produce CH2O, O2, and H atoms all the time. The two routes to these products are considered, and the preferred reaction channel is found.

Simonaitis, R.↗

Ball-grid array architecture for microfabricated ion traps

State-of-the-art microfabricated ion traps for quantum information research are approaching nearly one hundred control electrodes. We report here on the development and testing of a new architecture for microfabricated ion traps, built around ball-grid array (BGA) connections, that is suitable for increasingly complex trap designs. In the BGA trap, through-substrate vias bring electrical signals from the back side of the trap die to the surface trap structure on the top side. Gold-ball bump bonds connect the back side of the trap die to an interposer for signal routing from the carrier. Trench capacitors fabricated into the trap die replace area-intensive surface or edge capacitors. Wirebonds in the BGA architecture are moved to the interposer. These last two features allow the trap die to be reduced to only the area required to produce trapping fields. The smaller trap dimensions allow tight focusing of an addressing laser beam for fast single-qubit rotations. Performance of the BGA trap as characterized with {sup 40}Ca{sup +} ions is comparable to previous surface-electrode traps in terms of ion heating rate, mode frequency stability, and storage lifetime. We demonstrate two-qubit entanglement operations with {sup 171}Yb{sup +} ions in a second BGA trap.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Controlling and visualizing Dirac physics in topological semimetal heterostructures

A bulk crystal of cadmium arsenide is a three-dimensional Dirac semimetal, but, in a thin film, it can behave like a three-dimensional topological insulator. This tunability provides unique opportunities to manipulate and explore a topological insulator phase. However, an obstacle to engineering such tunability is the subtlety of transport-based discriminants for topological phases. In this work, the quantum capacitance of cadmium arsenide–based heterostructures provides two direct experimental signatures of three-dimensional topological insulator physics: an insulating three-dimensional bulk and a Landau level at zero energy that does not disperse in a magnetic field. We proceed to join our ability to see these fingerprints of the topological surface states with flexibility afforded by our epitaxial heterostructures to demonstrate a route toward controlling the energy of the Dirac nodes on each surface. These results point to new avenues for engineering topological insulators based on cadmium arsenide.

36 MATERIALS SCIENCE↗

Multicomponent Protein Cage Architectures for Photocatalysis

The primary goal of the project was to develop protein-templated approaches for the synthesis and directed assembly of semiconductor nanomaterials that are efficient for visible light absorption and hydrogen production. In general, visible-light-driven photocatalysis reactions exhibit low quantum efficiency for solar energy conversion primarily because of materials-related issues and limitations, such as the control of the band gap, band structure, photochemical stability, and available reactive surface area of the photocatalyst. Synthesis of multicomponent hierarchical nano-architectures, consisting of semiconductor nanoparticles (NPs) with desired optical properties fabricated to maximize spatial proximity for optimum electron and energy transfer represents an attractive route for addressing the problem. Virus capsids are highly symmetrical, self-assembling protein cage nanoparticles that exist in a range of sizes and symmetries. Selective deposition of inorganic, by design, at specific locations on virus capsids affords precise control over the size, spacing, and assembly of nanomaterials, resulting in uniform and reproducible nano-architectures. We utilized the self-assembling capabilities of the 420 subunit, 60 nm icosahedral, P22 virus capsid to direct the nucleation, growth, and proximity of a range of component materials. Controlled fabrication on the exterior of the temperature stable shell was achieved by genetically encoding specific binding peptides into an externally exposed loop which is displayed on each of the 420 coat protein subunits. Localization of complimentary materials to the interior of the particle was achieved through the use “scaffolding-fusion proteins. The scaffolding domain drives coat protein polymerization resulting in a coat protein shell surrounding a core of approximately 300 scaffolding/fusion molecules. The fusion domain comprises a peptide which specifically binds the semiconductor material of interest.

08 HYDROGEN↗

Computationally Driven Discovery of a Family of Layered LiNiB Polymorphs

Abstract Two novel lithium nickel boride polymorphs, RT ‐LiNiB and HT ‐LiNiB, with layered crystal structures are reported. This family of compounds was theoretically predicted by using the adaptive genetic algorithm (AGA) and subsequently synthesized by a hydride route with LiH as the lithium source. Unique among the known ternary transition‐metal borides, the LiNiB structures feature Li layers alternating with nearly planar [NiB] layers composed of Ni hexagonal rings with a B–B pair at the center. A comprehensive study using a combination of single crystal/synchrotron powder X‐ray diffraction, solid‐state 7 Li and 11 B NMR spectroscopy, scanning transmission electron microscopy, quantum‐chemical calculations, and magnetism has shed light on the intrinsic features of these polymorphic compounds. The unique layered structures of LiNiB compounds make them ultimate precursors for exfoliation studies, thus paving a way toward two‐dimensional transition‐metal borides, MBenes.

Gvozdetskyi, Volodymyr↗

Computationally Driven Discovery of a Family of Layered LiNiB Polymorphs

Abstract Two novel lithium nickel boride polymorphs, RT ‐LiNiB and HT ‐LiNiB, with layered crystal structures are reported. This family of compounds was theoretically predicted by using the adaptive genetic algorithm (AGA) and subsequently synthesized by a hydride route with LiH as the lithium source. Unique among the known ternary transition‐metal borides, the LiNiB structures feature Li layers alternating with nearly planar [NiB] layers composed of Ni hexagonal rings with a B–B pair at the center. A comprehensive study using a combination of single crystal/synchrotron powder X‐ray diffraction, solid‐state 7 Li and 11 B NMR spectroscopy, scanning transmission electron microscopy, quantum‐chemical calculations, and magnetism has shed light on the intrinsic features of these polymorphic compounds. The unique layered structures of LiNiB compounds make them ultimate precursors for exfoliation studies, thus paving a way toward two‐dimensional transition‐metal borides, MBenes.

Gvozdetskyi, Volodymyr↗

Semi-synthetic strategy

Semi-artificial photosynthesis offers advantages over purely natural or synthetic routes to producing chemicals from solar energy, but devices based on it have remained elusive. Now, researchers couple a dye-sensitized photoanode with natural components to generate H2 photoelectrochemically from water without additional bias.

14 SOLAR ENERGY↗