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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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Metal-doped semiconductor nanoparticles and methods of synthesis thereof

The present invention generally relates to binary or higher order semiconductor nanoparticles doped with a metallic element, and thermoelectric compositions incorporating such nanoparticles. In one aspect, the present invention provides a thermoelectric composition comprising a plurality of nanoparticles each of which includes an alloy matrix formed of a Group IV element and Group VI element and a metallic dopant distributed within the matrix.

Ren, Zhifeng↗

Fabrication of Metallic Hollow Nanoparticles

Metal and semiconductor nanoshells, particularly transition metal nanoshells, are fabricated using dendrimer molecules. Metallic colloids, metallic ions or semiconductors are attached to amine groups on the dendrimer surface in stabilized solution for the surface seeding method and the surface seedless method, respectively. Subsequently, the process is repeated with additional metallic ions or semiconductor, a stabilizer, and NaBH.sub.4 to increase the wall thickness of the metallic or semiconductor lining on the dendrimer surface. Metallic or semiconductor ions are automatically reduced on the metallic or semiconductor nanoparticles causing the formation of hollow metallic or semiconductor nanoparticles. The void size of the formed hollow nanoparticles depends on the dendrimer generation. The thickness of the metallic or semiconductor thin film around the dendrimer depends on the repetition times and the size of initial metallic or semiconductor seeds.

Kim, Jae-Woo↗

Thermoelectric Performance Enhancement by Surrounding Crystalline Semiconductors with Metallic Nanoparticles

Direct conversion of thermal energy to electricity by thermoelectric (TE) devices may play a key role in future energy production and utilization. However, relatively poor performance of current TE materials has slowed development of new energy conversion applications. Recent reports have shown that the dimensionless Figure of Merit, ZT, for TE devices can be increased beyond the state-of-the-art level by nanoscale structuring of materials to reduce their thermal conductivity. New morphologically designed TE materials have been fabricated at the NASA Langley Research Center, and their characterization is underway. These newly designed materials are based on semiconductor crystal grains whose surfaces are surrounded by metallic nanoparticles. The nanoscale particles are used to tailor the thermal and electrical conduction properties for TE applications by altering the phonon and electron transport pathways. A sample of bismuth telluride decorated with metallic nanoparticles showed less thermal conductivity and twice the electrical conductivity at room temperature as compared to pure Bi2Te3. Apparently, electrons cross easily between semiconductor crystal grains via the intervening metallic nanoparticle bridges, but phonons are scattered at the interfacing gaps. Hence, if the interfacing gap is larger than the mean free path of the phonon, thermal energy transmission from one grain to others is reduced. Here we describe the design and analysis of these new materials that offer substantial improvements in thermoelectric performance.

Kim, Hyun-Jung↗

Method of Creating Micro-scale Silver Telluride Grains Covered with Bismuth Nanoparticles

Provided is a method of enhancing thermoelectric performance by surrounding crystalline semiconductors with nanoparticles by contacting a bismuth telluride material with a silver salt under a substantially inert atmosphere and a temperature approximately near the silver salt decomposition temperature; and recovering a metallic bismuth decorated material comprising silver telluride crystal grains.

Kim, Hyun-Jung↗

Novel Materials, Processing and Device Technologies for Space Exploration with Potential Dual-Use Applications

We highlight results of a broad spectrum of efforts on lower-temperature processing of nanomaterials, novel approaches to energy conversion, and environmentally rugged devices. Solution-processed quantum dots of copper indium chalcogenide semiconductors and multiwalled carbon nanotubes from lower-temperature spray pyrolysis are enabled by novel (precursor) chemistry. Metal-doped zinc oxide (ZnO) nanostructured components of photovoltaic cells have been grown in solution at low temperature on a conductive indium tin oxide substrate. Arrays of ZnO nanorods can be templated and decorated with various semiconductor and metallic nanoparticles. Utilizing ZnO in a more broadly defined energy conversion sense as photocatalysts, unwanted organic waste materials can potentially be repurposed. Current efforts on charge carrier dynamics in nanoscale electrode architectures used in photoelectrochemical cells for generating solar electricity and fuels are described. The objective is to develop oxide nanowire-based electrode architectures that exhibit improved charge separation, charge collection and allow for efficient light absorption. Investigation of the charge carrier transport and recombination properties of the electrodes will aid in the understanding of how nanowire architectures improve performance of electrodes for dye-sensitized solar cells. Nanomaterials can be incorporated in a number of advanced higher-performance (i.e. mass specific power) photovoltaic arrays. Advanced technologies for the deposition of 4H-silicon carbide are described. The use of novel precursors, advanced processing, and process studies, including modeling are discussed from the perspective of enhancing the performance of this promising material for enabling technologies such as solar electric propulsion. Potential impact(s) of these technologies for a variety of aerospace applications are highlighted throughout. Finally, examples are given of technologies with potential spin-offs for dual-use or terrestrial applications.

solid state devices↗

Novel Materials, Processing, and Device Technologies for Space Exploration with Potential Dual-Use Applications

We highlight results of a broad spectrum of efforts on lower-temperature processing of nanomaterials, novel approaches to energy conversion, and environmentally rugged devices. Solution-processed quantum dots of copper indium chalcogenide semiconductors and multi-walled carbon nanotubes from lower-temperature spray pyrolysis are enabled by novel (precursor) chemistry. Metal-doped zinc oxide (ZnO) nanostructured components of photovoltaic cells have been grown in solution at low temperature on a conductive indium tin oxide substrate. Arrays of ZnO nanorods can be templated and decorated with various semiconductor and metallic nanoparticles. Utilizing ZnO in a more broadly defined energy conversion sense as photocatalysts, unwanted organic waste materials can potentially be re-purposed. Current efforts on charge carrier dynamics in nanoscale electrode architectures used in photoelectrochemical cells for generating solar electricity and fuels are described. The objective is to develop oxide nanowire-based electrode architectures that exhibit improved charge separation, charge collection and allow for efficient light absorption. Investigation of the charge carrier transport and recombination properties of the electrodes will aid in the understanding of how nanowire architectures improve performance of electrodes for dye-sensitized solar cells. Nanomaterials can be incorporated in a number of advanced higher-performance (i.e. mass specific power) photovoltaic arrays. Advanced technologies for the deposition of 4H-silicon carbide are described. The use of novel precursors, advanced processing, and process studies, including modeling are discussed from the perspective of enhancing the performance of this promising material for enabling technologies such as solar electric propulsion. Potential impact(s) of these technologies for a variety of aerospace applications are highlighted throughout. Finally, examples are given of technologies with potential spin-offs for dual-use or terrestrial applications.

thin films↗

Ordered nanoparticle arrays formed on engineered chaperonin protein templates

Traditional methods for fabricating nanoscale arrays are usually based on lithographic techniques. Alternative new approaches rely on the use of nanoscale templates made of synthetic or biological materials. Some proteins, for example, have been used to form ordered two-dimensional arrays. Here, we fabricated nanoscale ordered arrays of metal and semiconductor quantum dots by binding preformed nanoparticles onto crystalline protein templates made from genetically engineered hollow double-ring structures called chaperonins. Using structural information as a guide, a thermostable recombinant chaperonin subunit was modified to assemble into chaperonins with either 3 nm or 9 nm apical pores surrounded by chemically reactive thiols. These engineered chaperonins were crystallized into two-dimensional templates up to 20 microm in diameter. The periodic solvent-exposed thiols within these crystalline templates were used to size-selectively bind and organize either gold (1.4, 5 or 10nm) or CdSe-ZnS semiconductor (4.5 nm) quantum dots into arrays. The order within the arrays was defined by the lattice of the underlying protein crystal. By combining the self-assembling properties of chaperonins with mutations guided by structural modelling, we demonstrate that quantum dots can be manipulated using modified chaperonins and organized into arrays for use in next-generation electronic and photonic devices.

Chaperonins/chemistry/ultrastructure↗

Nanowire Photovoltaic Devices

Firefly Technologies, in collaboration with the Rochester Institute of Technology and the University of Wisconsin-Madison, developed synthesis methods for highly strained nanowires. Two synthesis routes resulted in successful nanowire epitaxy: direct nucleation and growth on the substrate and a novel selective-epitaxy route based on nanolithography using diblock copolymers. The indium-arsenide (InAs) nanowires are implemented in situ within the epitaxy environment-a significant innovation relative to conventional semiconductor nanowire generation using ex situ gold nanoparticles. The introduction of these nanoscale features may enable an intermediate band solar cell while simultaneously increasing the effective absorption volume that can otherwise limit short-circuit current generated by thin quantized layers. The use of nanowires for photovoltaics decouples the absorption process from the current extraction process by virtue of the high aspect ratio. While no functional solar cells resulted from this effort, considerable fundamental understanding of the nanowire epitaxy kinetics and nanopatterning process was developed. This approach could, in principle, be an enabling technology for heterointegration of dissimilar materials. The technology also is applicable to virtual substrates. Incorporating nanowires onto a recrystallized germanium/metal foil substrate would potentially solve the problem of grain boundary shunting of generated carriers by restricting the cross-sectional area of the nanowire (tens of nanometers in diameter) to sizes smaller than the recrystallized grains (0.5 to 1 micron(exp 2).

Forbes, David↗

Growth Mechanism of Nanowires: Ternary Chalcogenides

In the past two decades there has been a large rise in the investment and expectations for nanotechnology use. Almost every area of research has projected improvements in sensors, or even a promise for the emergence of some novel device technologies. For these applications major focuses of research are in the areas of nanoparticles and graphene. Although there are some near term applications with nanowires in photodetectors and other low light detectors, there are few papers on the growth mechanism and fabrication of nanowire-based devices. Semiconductor nanowires exhibit very favorable and promising optical properties, including high transparency and a several order of magnitude better photocurrent than thin film and bulk materials. We present here an overview of the mechanism of nanowire growth from the melt, and some preliminary results for the thallium arsenic selenide material system. Thallium arsenic selenide (TAS) is a multifunctional material combining excellent acousto-optical, nonlinear and radiation detection properties. We observed that small units of (TAS) nanocubes arrange and rearrange at moderate melt undercooling to form the building block of a nanowire. In some cases very long wires (less than mm) are formed. Since we avoided the catalyst, we observed self-nucleation and uncontrolled growth of wires from different places.

Singh, N. B.↗

Methods for synthesis of semiconductor nanocrystals and thermoelectric compositions

The present invention provides methods for synthesis of IV VI nanostructures, and thermoelectric compositions formed of such structures. In one aspect, the method includes forming a solution of a Group IV reagent, a Group VI reagent and a surfactant. A reducing agent can be added to the solution, and the resultant solution can be maintained at an elevated temperature, e.g., in a range of about 20.degree. C. to about 360.degree. C., for a duration sufficient for generating nanoparticles as binary alloys of the IV VI elements.

Ren, Zhifeng↗

Synthesis Methods, Microscopy Characterization and Device Integration of Nanoscale Metal Oxide Semiconductors for Gas Sensing in Aerospace Applications

A comparison is made between SnO2, ZnO, and TiO2 single-crystal nanowires and SnO2 polycrystalline nanofibers for gas sensing. Both nanostructures possess a one-dimensional morphology. Different synthesis methods are used to produce these materials: thermal evaporation-condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed. Practical issues associated with harvesting, purification, and integration of these materials into sensing devices are detailed. For comparison to the nascent form, these sensing materials are surface coated with Pd and Pt nanoparticles. Gas sensing tests, with respect to H2, are conducted at ambient and elevated temperatures. Comparative normalized responses and time constants for the catalyst and noncatalyst systems provide a basis for identification of the superior metal-oxide nanostructure and catalyst combination. With temperature-dependent data, Arrhenius analyses are made to determine an activation energy for the catalyst-assisted systems.

VanderWal, Randy L.↗

Growth Mechanism of Nanowires: Binary and Ternary Chalcogenides

Semiconductor nanowires exhibit very exciting optical and electrical properties including high transparency and a several order of magnitude better photocurrent than thin film and bulk materials. We present here the mechanism of nanowire growth from the melt-liquid-vapor medium. We describe preliminary results of binary and ternary selenide materials in light of recent theories. Experiments were performed with lead selenide and thallium arsenic selenide systems which are multifunctional material and have been used for detectors, acousto-optical, nonlinear and radiation detection applications. We observed that small units of nanocubes and elongated nanoparticles arrange and rearrange at moderate melt undercooling to form the building block of a nanowire. Since we avoided the catalyst, we observed self-nucleation and uncontrolled growth of wires from different places. Growth of lead selenide nanowires was performed by physical vapor transport method and thallium arsenic selenide nanowire by vapor-liquid-solid (VLS) method. In some cases very long wires (>mm) are formed. To achieve this goal experiments were performed to create situation where nanowires grew on the surface of solid thallium arsenic selenide itself.

Singh, N. B.↗

Nano-Ceramic Coated Plastics

Plastic products, due to their durability, safety, and low manufacturing cost, are now rapidly replacing cookware items traditionally made of glass and ceramics. Despite this trend, some still prefer relatively expensive and more fragile ceramic/glassware because plastics can deteriorate over time after exposure to foods, which can generate odors, bad appearance, and/or color change. Nano-ceramic coatings can eliminate these drawbacks while still retaining the advantages of the plastic, since the coating only alters the surface of the plastic. The surface coating adds functionality to the plastics such as self-cleaning and disinfectant capabilities that result from a photocatalytic effect of certain ceramic systems. These ceramic coatings can also provide non-stick surfaces and higher temperature capabilities for the base plastics without resorting to ceramic or glass materials. Titanium dioxide (TiO2) and zinc oxide (ZnO) are the candidates for a nano-ceramic coating to deposit on the plastics or plastic films used in cookware and kitchenware. Both are wide-bandgap semiconductors (3.0 to 3.2 eV for TiO2 and 3.2 to 3.3 eV for ZnO), so they exhibit a photocatalytic property under ultraviolet (UV) light. This will lead to decomposition of organic compounds. Decomposed products can be easily washed off by water, so the use of detergents will be minimal. High-crystalline film with large surface area for the reaction is essential to guarantee good photocatalytic performance of these oxides. Low-temperature processing (<100 C) is also a key to generating these ceramic coatings on the plastics. One possible way of processing nanoceramic coatings at low temperatures (< 90 C) is to take advantage of in-situ precipitated nanoparticles and nanostructures grown from aqueous solution. These nanostructures can be tailored to ceramic film formation and the subsequent microstructure development. In addition, the process provides environment- friendly processing because of the aqueous solution. Low-temperature processing has also shown versatility to generate various nanostructures. The growth of low-dimensional nanostructures (0-D, 1-D) provides a means of enhancing the crystallinity of the solution-prepared films that is of importance for photocatalytic performance. This technology can generate durable, fully functional nano-ceramic coatings (TiO2, ZnO) on plastic materials (silicone, Teflon, PET, etc.) that can possess both photocatalytic oxide properties and flexible plastic properties. Processing cost is low and it does not require any expensive equipment investment. Processing can be scalable to current manufacturing infrastructure.

Cho, Junghyun↗

Microscale Particulate Classifiers (MiPAC) Being Developed

The NASA Glenn Research Center is developing microscale sensors to characterize atmospheric-borne particulates. The devices are fabricated using MEMS (microelectromechanical systems) technologies. These technologies are derived from those originally developed in support of the semiconductor processing industry. The resulting microsensors can characterize a wide range of particles and are, therefore, suitable to a broad range of applications. This project is supported under a collaborative program called the Glennan Microsystems Initiative. The initiative comprises members of NASA Glenn Research Center, various university affiliates from the State of Ohio, and a number of participating industrial partners. Funding is jointly provided by NASA, the State of Ohio, and industrial members. The work described here is a collaborative arrangement between researchers at Glenn, the University of Minnesota, The National Institute of Standards and Technology (NIST), and the Cleveland State University. Actual device fabrication is conducted at Glenn and at the laboratories of Case Western Reserve University. Case Western is also located in Cleveland, Ohio, and is a participating member of the initiative. The principal investigator for this project is Paul S. Greenberg of Glenn. Two basic types of devices are being developed, and target different ranges of particle sizes. The first class of devices, which is used to measure nanoparticles (i.e., particles in the range of 0.002 to 1 mm), is based on the technique of Electrical Mobility Classification. This technique also affords the valuable ability of measuring the electrical charge state of the particles. Such information is important in the understanding of agglomeration mechanisms and is useful in the development of methods for particle repulsion. The second type of device being developed, which utilizes optical scattering, is suitable for particles larger than 1 mm. This technique also provides information on particle shape and composition. Applications for these sensors include fundamental planetary climatology, monitoring and filtration in spacecraft, human habitation modules and related systems, characterization of particulate emissions from propulsion and power systems, and as early warning sensors for both space-based and ter-restrial fire detection. These devices are also suitable for characterizing biological compounds such as allergens, infectious agents, and biotoxic agents.

Greenberg, Paul S.↗

Nanoscale Metal Oxide Semiconductors for Gas Sensing

A report describes the fabrication and testing of nanoscale metal oxide semiconductors (MOSs) for gas and chemical sensing. This document examines the relationship between processing approaches and resulting sensor behavior. This is a core question related to a range of applications of nanotechnology and a number of different synthesis methods are discussed: thermal evaporation- condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed, providing a processing overview to developers of nanotechnology- based systems. The results of a significant amount of testing and comparison are also described. A comparison is made between SnO2, ZnO, and TiO2 single-crystal nanowires and SnO2 polycrystalline nanofibers for gas sensing. The TECsynthesized single-crystal nanowires offer uniform crystal surfaces, resistance to sintering, and their synthesis may be done apart from the substrate. The TECproduced nanowire response is very low, even at the operating temperature of 200 C. In contrast, the electrospun polycrystalline nanofiber response is high, suggesting that junction potentials are superior to a continuous surface depletion layer as a transduction mechanism for chemisorption. Using a catalyst deposited upon the surface in the form of nanoparticles yields dramatic gains in sensitivity for both nanostructured, one-dimensional forms. For the nanowire materials, the response magnitude and response rate uniformly increase with increasing operating temperature. Such changes are interpreted in terms of accelerated surface diffusional processes, yielding greater access to chemisorbed oxygen species and faster dissociative chemisorption, respectively. Regardless of operating temperature, sensitivity of the nanofibers is a factor of 10 to 100 greater than that of nanowires with the same catalyst for the same test condition. In summary, nanostructure appears critical to governing the reactivity, as measured by electrical resistance of these SnO2 nanomaterials towards reducing gases. With regard to the sensitivity of the different nascent nanostructures, the electrospun nanofibers appear preferable

Hunter, Gary W.↗