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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 73 records · Page 4

Single Entity Electrochemistry in Nanopore Electrode Arrays: Ion Transport Meets Electron Transfer in Confined Geometries

Electrochemical measurements conducted in confined volumes provide a powerful and direct means to address scientific questions at the nexus of nanoscience, biotechnology, and chemical analysis. How are electron transfer and ion transport coupled in confined volumes and how does understanding them require moving beyond macroscopic theories? Also, how do these coupled processes impact electrochemical detection and processing? We address these questions by studying a special type of confined-volume architecture, the nanopore electrode array, or NEA, which is designed to be commensurate in size with physical scaling lengths, such as the Debye length, a concordance that offers performance characteristics not available in larger scale structures. The experiments described here depend critically on carefully constructed nanoscale architectures that can usefully control molecular transport and electrochemical reactivity. We begin by considering the experimental constraints that guide the design and fabrication of zero-dimensional nanopore arrays with multiple embedded electrodes. These zero-dimensional structures are nearly ideal for exploring how permselectivity and unscreened ion migration can be combined to amplify signals and improve selectivity by enabling highly efficient redox cycling. Our studies also highlight the benefits of arrays, in that molecules escaping from a single nanopore are efficiently captured by neighboring pores and returned to the population of active redox species being measured, benefits that arise from coupling ion accumulation and migration. These tools for manipulating redox species are well-positioned to explore single molecule and single particle electron transfer events through spectroelectrochemistry, studies which are enabled by the electrochemical zero-mode waveguide (ZMW), a special hybrid nanophotonic/nanoelectronic architecture in which the lower ring electrode of an NEA nanopore functions both as a working electrode to initiate electron transfer reactions and as the optical cladding layer of a ZMW. Furthermore, while the work described here is largely exploratory and fundamental, we believe that the development of NEAs will enable important applications that emerge directly from the unique coupled transport and electron-transfer capabilities of NEAs, including in situ molecular separation and detection with external stimuli, redox-based electrochemical rectification in individually encapsulated nanopores, and coupled sorters and analyzers for nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of a New Generation of Stable, Tunable, and Catalytically Active Nanoparticles Produced by the Helium Nanodroplet Deposition Method

Nanoparticles (NPs) are revolutionizing many areas of science and technology, often delivering unprecedented improvements to properties of the conventional materials. However, despite important advances in NPs synthesis and applications, numerous challenges still remain. Development of alternative synthetic method capable of producing very uniform, extremely clean and very stable NPs is urgently needed. If successful, such method can potentially transform several areas of nanoscience, including environmental and energy related catalysis. Here we present the first experimental demonstration of catalytically active NPs synthesis achieved by the helium nanodroplet isolation method. This alternative method of NPs fabrication and deposition produces narrowly distributed, clean, and remarkably stable NPs. The fabrication is achieved inside ultra-low temperature, superfluid helium nanodroplets, which can be subsequently deposited onto any substrate. Lastly, this technique is universal enough to be applied to nearly any element, while achieving high deposition rates for single element as well as composite core-shell NPs.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Direct Observation of the Pressure-Induced Structural Variation in Gold Nanoclusters and the Correlated Optical Response

The ability to gradually modify the atomic structures of nanomaterials and directly identify such structural variation is important in nanoscience research. Here, we present the first example of a high-pressure single-crystal X-ray diffraction analysis of atomically precise metal nanoclusters. The pressure-dependent, subangstrom structural evolution of an ultrasmall gold nanoparticle, Au 25 S 18 , has been directly identified. We found that a 0.1 Å decrease of the Au–Au bond length could induce a blue-shift of 30 nm in the photoluminescence spectra of gold nanoclusters. From theoretical calculations, the origins of the blue-shift and enhanced photoluminescence under pressure are investigated, which are ascribed to molecular orbital symmetry and conformational locking, respectively. Here, the combination of the high-pressure in situ X-ray results with both theoretical and experimental optical spectra provides a direct and generalizable avenue to unveil the underlying structure–property relations for nanoclusters and nanoparticles which cannot be obtained through traditional physical chemistry measurements.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Intrinsically Slow Cooling of Hot Electrons in CdSe Nanocrystals Compared to CdS

The utilization of excited charge carriers in semiconductor nanocrystals (NCs) for optoelectronic technologies has been a long-standing goal in the field of nanoscience. Experimental efforts to extend the lifetime of excited carriers have therefore been a principal focus. To understand the limits of these lifetimes, in this work, we theoretically study the time scales of pure electron relaxation in negatively charged NCs composed of two prototypical materials: CdSe and CdS. We find that hot electrons in CdSe have lifetimes that are 5 to 6 orders of magnitude longer than in CdS when the relaxation is governed only by the intrinsic properties of the materials. Although these two materials are known to have somewhat different electronic structure, we elucidate how this enormous difference in lifetimes arises from relatively small quantitative differences in electronic energy gaps and phonon frequencies, as well as the crucial role of Fröhlich-type electron–phonon couplings.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Polarization Control via He-Ion Beam Induced Nanofabrication in Layered Ferroelectric Semiconductors

Rapid advanced in nanoscience rely on continuous improvements of matter manipulation at near atomic scales. Currently, well characterized, robust, resist-based lithography carries the brunt of the nanofabrication process. However, use of local electron, ion and physical probe methods is also expanding, driven largely by their ability to fabricate without the multi-step preparation processes that can result in contamination from resists and solvents. Furthermore, probe based methods extend beyond nanofabrication to nanomanipulation and imaging, vital ingredients to rapid transition to prototyping and testing of layered 2D heterostructured devices. In this work we demonstrate that helium ion interaction, in a Helium Ion Microscope (HIM), with the surface of bulk copper indium thiophosphate CuM III P 2 X 6 (M = Cr, In; X= S, Se), (CITP) results in the control of ferroelectric domains, and growth of cylindrical nanostructures with enhanced conductivity; with material volumes scaling with the dosage of the beam. The nanostructures are oxygen rich, sulfur poor, and with the copper concentration virtually unchanged as confirmed by Energy Dispersive X-ray (EDX). Scanning Electron Microscopy (SEM) imaging contrast as well as Scanning Microwave Microscopy (SMM) measurements suggest enhanced conductivity in the formed particle, whereas Atomic Force Microscopy (AFM) measurements indicate that the produced structures have lower dissipation and a lower Young s modulus.

2D crystals↗

Mechanics of an Asymmetric Hard-Soft Lamellar Nanomaterial

Nanolayered lamellae are common structures in nanoscience and nanotechnology, but most are nearly symmetric in layer thickness. Here, we report on the structure and mechanics of highly asymmetric and thermodynamically stable soft–hard lamellar structures self-assembled from optimally designed PS 1 -(PI-b-PS 2 ) 3 miktoarm star block copolymers. The remarkable mechanical properties of these strong and ductile PS (polystyrene)-based nanomaterials can be tuned over a broad range by varying the hard layer thickness while maintaining the soft layer thickness constant at 13 nm. Upon deformation, thin PS lamellae (<100 nm) exhibited kinks and predamaged/damaged grains, as well as cavitation in the soft layers. In contrast, deformation of thick lamellae (>100 nm) manifests cavitation in both soft and hard nanolayers. In situ tensile-SAXS experiments revealed the evolution of cavities during deformation and confirmed that the damage in such systems reflects both plastic deformation by shear and residual cavities. The aspects of the mechanics should point to universal deformation behavior in broader classes of asymmetric hard–soft lamellar materials, whose properties are just being revealed for versatile applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Big, Deep, and Smart Data in Scanning Probe Microscopy

Scanning probe microscopy techniques open the door to nanoscience and nanotechnology by enabling imaging and manipulation of structure and functionality of matter on nanometer and atomic scales. We analyze the discovery process by SPM in terms of information flow from tip-surface junction to the knowledge adoption by scientific community. Furthermore, we discuss the challenges and opportunities offered by merging of SPM and advanced data mining, visual analytics, and knowledge discovery technologies.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Atomic Layer Deposition of Metal Sulfide Materials

The field of nanoscience is delivering increasingly intricate yet elegant geometric structures incorporating an ever-expanding palette of materials. Atomic layer deposition (ALD) is a powerful driver of this field, providing exceptionally conformal coatings spanning the periodic table and atomic-scale precision independent of substrate geometry. This versatility is intrinsic to ALD and results from sequential and self-limiting surface reactions. This characteristic facilitates digital synthesis, in which the film grows linearly with the number of reaction cycles. While the majority of ALD processes identified to date produce metal oxides, novel applications in areas such as energy storage, catalysis, and nanophotonics are motivating interest in sulfide materials. Recent progress in ALD of sulfides has expanded the diversity of accessible materials as well as a more complete understanding of the unique chalcogenide surface chemistry.

Dasgupta, Neil P.↗

Direct in Situ Observation of Nanoparticle Synthesis in a Liquid Crystal Surfactant Template

Controlled synthesis of nanostructures is essential for many applications, from energy storage/generation and catalysis to semiconductor and biomedical devices. Normally, nanostructures are characterized after synthesis and growth mechanisms are assumed. Here we show the first direct observation of nanoparticle synthesis in a liquid crystal surfactant template using an electron microscope fluid stage. The nanoparticles first sinter (to ~5nm), then grow connections to each other around the micelles to form clusters. Upon reaching a critical size (>10-15nm), the clusters become highly mobile in the template, displacing micelles to form spherical nanoparticles. This ability to observe and understand fundamental growth mechanisms on the nanoscale in real time and in aqueous environments will impact every branch of nanoscience where precise control over nanostructure is essential. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Probing local bias-induced transitions using photothermal excitation contact resonance atomic force microscopy and voltage spectroscopy

In this paper, nanomechanical properties are closely related to the states of matter, including chemical composition, crystal structure, mesoscopic domain configuration, etc. Investigation of these properties at the nanoscale requires not only static imaging methods, e.g., contact resonance atomic force microscopy (CR-AFM), but also spectroscopic methods capable of revealing their dependence on various external stimuli. Here we demonstrate the voltage spectroscopy of CR-AFM, which was realized by combining photothermal excitation (as opposed to the conventional piezoacoustic excitation method) with the band excitation technique. We applied this spectroscopy to explore local bias-induced phenomena ranging from purely physical to surface electromechanical and electrochemical processes. Our measurements show that the changes in the surface properties associated with these bias-induced transitions can be accurately assessed in a fast and dynamic manner, using resonance frequency as a signature. Finally, with many of the advantages offered by photothermal excitation, contact resonance voltage spectroscopy not only is expected to find applications in a broader field of nanoscience but also will provide a basis for future development of other nanoscale elastic spectroscopies.

36 MATERIALS SCIENCE↗

Dynamic and programmable morphology and size evolution via a living hierarchical self-assembly strategy

Recent advances in the preparation of shape-shifting and size-growing nanostructures are hot topics in development of nanoscience, because many intelligent functions are always relied on their shape and dimension. Here we report a tunable manipulation of sequential self-assembled transformation in situ via a hierarchical assembly strategy based on a living thiol–disulfide exchange reaction. By tailoring the external stimuli, the reactive points can be generated at the ends of initially unimolecular micelles, which subsequently drive the pre-assemblies to periodically proceed into the hierarchically micellar connection, axial growth, bending, and cyclization processes from nanoscopic assemblies to macroscopic particles. Of particular interest would be systems that acquired the shape control and size adjustment of self-assemblies after termination or reactivation of disulfide reshuffling reaction by regulating external stimuli whenever needed. Such a hierarchical strategy for self-assembled evolution is universally applicable not only for other disulfide-linked dendritic polymers but also for exploitation of biological applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Observing crystal nucleation in four dimensions using atomic electron tomography

Nucleation plays a critical role in many physical and biological phenomena that range from crystallization, melting and evaporation to the formation of clouds and the initiation of neurodegenerative diseases. However, nucleation is a challenging process to study in experiments, especially in the early stage when several atoms or molecules start to form a new phase from a parent phase. A number of experimental and computational methods have been used to investigate nucleation processes, but experimental determination of the three-dimensional atomic structure and the dynamics of early stage nuclei has been unachievable. Here we use atomic electron tomography to study early stage nucleation in four dimensions (4D: that is, including time) at atomic resolution. Using FePt nanoparticles as a model system, we find that early stage nuclei are irregularly shaped, each has a core of one to a few atoms with the maximum order parameter, and the order parameter gradient points from the core to the boundary of the nucleus. We capture the structure and dynamics of the same nuclei undergoing growth, fluctuation, dissolution, merging and/or division, which are regulated by the order parameter distribution and its gradient. These experimental observations are corroborated by molecular dynamics simulations of heterogeneous and homogeneous nucleation in liquid–solid phase transitions of Pt. Our experimental and molecular dynamics results differ from classical nucleation theory, indicating that a theory beyond this is needed to describe early stage nucleation at the atomic scale. Looking forward, we anticipate that the reported approach will open the door to the study of many fundamental problems in materials science, nanoscience, condensed matter physics and chemistry, such as phase transition, atomic diffusion, grain boundary dynamics, interface motion, defect dynamics and surface reconstruction with 4D atomic resolution.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Nanosulfur: A Potent Fungicide Against Food Pathogen, Aspergillus niger

Elemental sulfur (S{sup 0}), man's oldest eco-friendly fungicide for curing fungal infections in plants and animals, is registered in India as a non-systemic and contact fungicide. However due to its high volume requirement, Indian agrochemical industry and farmers could not effectively use this product till date. We hypothesize that intelligent nanoscience applications might increase the visibility of nanosulfur in Indian agriculture as a potent and eco-safe fungicide. Sulfur nanoparticles (NPs) were synthesized bottom-up via a liquid synthesis method with average particle size in the range of 50-80 nm and the shapes of the NPs were spherical. A comparative study of elemental and nano-sulfur produced has been tested against facultative fungal food pathogen, Aspergillus niger. Results showed that nanosulfur is more efficacious than its elemental form.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Dispersion and waves in bounded plasmas with subwavelength inhomogeneities: Genesis of MEFIB

Bounded plasma exhibit many interesting behavior that are not found in plasmas of 'infinite' extent such as space and astrophysical plasmas. Our studies have revealed that the dispersion properties of waves in a bounded magnetoplasma deviates considerably from the predictions of the Clemmow-Mullaly-Allis (CMA) model, giving rise to new regimes of wave propagation and absorption. The anisotropy of the medium dictated by the length scales of plasma nonuniformity and magnetostatic field inhomogeneity lead to rotation of the polarization axis an effect similar to the Cotton-Mouton effect in a magneto-optic medium but with distinct differences due to wave induced resonances. This article highlights some of these interesting effects observed experimentally and corroborated with Monte Carlo simulations. One of the principal outcomes of this research is the genesis of a novel multielement focused ion beam (MEFIB) system that utilizes compact bounded plasmas in a minimum – B field to provide intense focused ion beams of a variety of elements for new research in nanoscience and technology.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Few-cycle plasmon oscillations controlling photoemission from metal nanoparticles

Few-cycle optical excitation of nanosystems holds promise of fundamental discoveries and applications in ultrafast nanoscience, the development of nanostructured photocathodes, and many more. For these, surface plasmon generation on unprecedented timescales needs to be controlled. For this, few-cycle plasmon oscillations on a metal nanoparticle can be generated by keeping considerable electric field enhancement factors. As an initial application of such a high spatiotemporal localization of an ultrashort laser pulse, we numerically demonstrate the control of photoelectrons on a true sub-fs timescale in nanometric spatial domains. We show that it is only off-resonant nanoparticles that can provide few-cycle plasmons and electron control on this timescale.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Properties of a finite fully spin-polarized free homogeneous one-dimensional electron gas

The homogeneous electron gas model has been quite successful to predict the bulk properties of systems of electrons at various densities. In many occasions, a simplified free homogeneous electron gas model represents a powerful first approximation to a real system. Despite our considerable knowledge on the bulk properties of a homogeneous electron gas, advances in nanoscience and nanotechnology call for a greater effort to understand the opposite limit of small finite systems of electrons with size-dependent properties. In this work, we provide a detailed description of the properties of a finite fully spin-polarized (spinless) free homogeneous one-dimensional electron gas, the simplest of the free homogeneous electron gases. We derive exact analytical results for various quantities such as the one-particle density function, two-particle density function, one-particle density matrix, pair correlation function and energy of finite systems with an arbitrary number of electrons. The results obtained provide a detailed view on how various quantities corresponding to a finite system approach their bulk (thermodynamic limit) value.

36 MATERIALS SCIENCE↗

Novel structures and physics of nanomagnets (invited)

Nanoscale magnets with characteristic dimensions in the range of 1–100 nm are important in several areas of nanoscience and technology. First, this length scale spans the typical important dimensions of exchange lengths and domain-wall widths, which means that significant control of magnetic properties can be obtained by varying grain or particle dimensions. Second, the nonequilibrium synthetic processes used for clusters, particles, and films, often lead to new real-space crystal structures with completely novel spin structures and magnetic properties. Third, a basic-science challenge in this class of matter involves the spin-polarized quantum mechanics of many-electron systems containing 10–10 000 atoms. Finally, the materials under study may have important future applications in high-density data storage, ultra-small spintronic devices, or high-energy magnetic materials. In this article, we discuss our recent work on novel Fe-Au nanoclusters, MnAu-Mn core-shell structures, and complex high-anisotropy Co-rich intermetallic compound clusters. We also present new results on Fe-based alloys including the magnetic properties of semiconducting FeSi{sub 2} nanoclusters and spin correlations in FeGe nanocluster films.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗