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Material for surface-enhanced Raman spectroscopy, and SER sensors and method for preparing same

Metal-doped sol-gel materials, suitable for use as sensors for surface-enhanced Raman spectroscopic analysis for trace chemical detection, are produced by effecting gelation and solvent removal of a doped sol-gel under mild temperature conditions. At least in certain instances reaction and drying will desirably be effected in an oxygen-starved environment. The metal of the sol-gel material functions, when irradiated, to produce a plasmon field for interaction with molecules of an analyte in contact therewith, increasing by orders of magnitude Raman photons that are generate by excitation radiation, and the method allows matching of the metal and metal particle size to a wavelength of light (or incident radiation, e.g., laser radiation) to generate surface plasmons. The porosity of the sol-gel material dramatically increases the surface area, and thereby the amount of metal exposed for analyte interaction. The sensors provided may be in the form of glass vials, fiber optics, multi-well micro-sample plates, etc., having surface coatings of the doped sol-gel material, to provide sampling systems for use in a Raman instrument.

Farquharson, Stuart↗

Structural evolution, electrochemical kinetic properties, and stability of A-site doped perovskite Sr(1-x)Yb(x)CoO(3-δ)

Mixed ionic and electronic conducting (MIEC) perovskite SrCoO(3-δ) is a widely studied (electro)catalyst for the oxygen reduction reaction (ORR) and possesses different crystal structures at different temperatures. These temperature dependent phase transitions significantly impact the ordering of oxygen vacancies and electrochemical kinetic properties as well as the reliability of the related devices. Some of the crystal structures formed, e.g. hexagonal phases, turn out to be almost impermeable to oxygen gas. Therefore, it is important to stabilize the crystal structure of SrCoO(3-δ) that favors the ORR over a wide temperature range. Herein, the partial substitution of the A-site Sr with Yb is systematically studied, including synthesis, characterization and analysis of structural evolution, electrochemical kinetic properties, thermal stability, and stability in a CO2-containing atmosphere. The results indicate that Sr(0.90)Yb(0.10)CoO(3-δ) is able to stabilize the tetragonal crystal structure with less ordered oxygen vacancies, leading to polarization resistances of 0.051, 0.115 and 0.272 U sq.cm at 750, 700 and 650 °C, respectively, on symmetrical cells. Sr(0.90)Yb(0.10)CoO(3-δ) demonstrates a very stable surface oxygen vacancy distribution and electronic structure near oxygen vacancies but dissociation of adsorbed oxygen molecules into atomic oxygen is affected by surface Sr segregation, and polarization resistance degradation is mainly induced by surface Sr segregation. Furthermore, Sr(0.90)Yb(0.10)CoO(3-δ) exhibits excellent thermal stability as well as excellent recovery stability and improved polarization performance after a few pure air/CO2-containing air treatment cycles at 700 °C. However, a hysteresis behavior of polarization performance is observed at 650 °C during gas cycling treatment, which may cause long-term degradation of the Sr(0.90)Yb(0.10)CoO(3-δ) electrode. The different polarization behaviors during gas cycling treatment are induced by different sensitivities of the formed surface strontium carbonate and chemisorbed surface oxo-carbonaceous species to different operating temperatures.

electrochemical kinetic↗

Behavior of lithium in irradiated solar cells.

The current state of the art in radiation resistant lithium-doped silicon solar cells is reviewed. Fabrication techniques are reviewed. Characteristics of lithium-doped cells are discussed. Behavior of lithium-doped cells during 1 MeV electron irradiation are studied for various types of cells. Effects of variations in lithium and oxygen concentration are shown and discussed. Capacitance measurements at various voltages, frequencies and temperatures are used to detect charges in lithium donor concentration and the formation of defects during irradiation. Physical models to explain the observed effects are presented.

Carter, J. R., Jr.↗

Effect of water on hydrogen permeability

Doping of hydrogen with CO and CO2 was developed to reduce hydrogen permeation in Stirling engines by forming a low permeability oxide coating on the inner surface of the heater head tubes. Although doping worked well, under certain circumstances the protective oxide could be chemically reduced by the hydrogen in the engine. Some oxygen is required in the hydrogen to prevent reduction. Eventually, all the oxygen in the hydrogen gas - whatever its source - shows up as water. This is the result of hydrogen reducing the CO, CO2, or the protective inner surface oxides. This water can condense in the engine system under the right conditions. If the concentration of water vapor is reduced to a low enough level, the hydrogen can chemically reduce the oxide coating, resulting in an increase in permeability. This work was done to define the minimum water content required to avoid this reduction in the oxide coating. The results of this testing show that a minimum of approximately 750 ppm water is required to prevent an increase in permeability of CG-27, a high temperature metal alloy selected for Stirling engine heater tubes.

Hulligan, David↗

Transparent conducting thin films for spacecraft applications

Transparent conductive thin films are required for a variety of optoelectronic applications: automotive and aircraft windows, and solar cells for space applications. Transparent conductive coatings of indium-tin-oxide (ITO)-magnesium fluoride (MgF2) and aluminum doped zinc oxide (AZO) at several dopant levels are investigated for electrical resistivity (sheet resistance), carrier concentration, optical properties, and atomic oxygen durability. The sheet resistance values of ITO-MgF2 range from 10(exp 2) to 10(exp 11) ohms/square, with transmittance of 75 to 86 percent. The AZO films sheet resistances range from 10(exp 7) to 10(exp 11) ohms/square with transmittances from 84 to 91 percent. It was found that in general, with respect to the optical properties, the zinc oxide (ZnO), AZO, and the high MgF2 content ITO-MgF2 samples, were all durable to atomic oxygen plasma, while the low MgF2 content of ITO-MgF2 samples were not durable to atomic oxygen plasma exposure.

Perez-Davis, Marla E.↗

Thermoelectric Properties in the TiO2/SnO2 System

Nanotechnology has provided a new interest in thermoelectric technology. A thermodynamically driven process is one approach in achieving nanostructures in bulk materials. TiO2/SnO2 system exhibits a large spinodal region with exceptional stable phase separated microstructures up to 1400 C. Fabricated TiO2/SnO2 nanocomposites exhibit n-type behavior with Seebeck coefficients greater than -300 .V/K. Composites exhibit good thermal conductance in the range of 7 to 1 W/mK. Dopant additions have not achieved high electrical conductivity (<1000 S/m). Formation of oxygen deficient composites, TixSn1-xO2-y, can change the electrical conductivity by four orders of magnitude. Achieving higher thermoelectric ZT by oxygen deficiency is being explored. Seebeck coeffcient, thermal conductivity, electrical conductance and microstructure will be discussed in relation to composition and doping.

Dynys, F.↗

Volatile products from the interaction of KCl(g) with Cr2O3 and LaCrO3 in oxidizing environments

Cooled target collection techniques and high pressure mass spectrometric sampling were used to measure the relative rates of oxidative vaporization and to identify the volatile products emanating from samples of chromia and Mg-doped lanthanum chromite. The materials were exposed to partial pressures of KCl with and without H2O in one atmosphere of slowly flowing oxygen at elevated temperatures. Chromia and fresh samples of lanthanum chromite exhibited enhanced rates of oxidative vaporization upon exposure to these reactants. Mass spectrometric identification showed that the enhancements resulted from the heterogeneous formation of complex molecules of the type KCl sub 1,2,3 CrO3 and KOH sub l,2 CrO3. Lanthanum chromite that had undergone prolonged oxidative vaporization exhibited no enhanced oxidation upon exposure to the reactants.

Kohl, F. J.↗

Effects of processing and dopant on radiation damage removal in silicon solar cells

Gallium and boron doped silicon solar cells, processed by ion implantation followed by either laser or furnace anneal were irradiated by 1 MeV electrons and their postirradiation recovery by thermal annealing was determined. During the postirradiation anneal, gallium doped cells prepared by both processes recovered more rapidly and exhibited none of the severe reverse annealing observed for similarly processed 2 ohm-cm boron doped cells. Ion implanted furnace annealed 0.1 ohm-cm boron doped cells exhibited the lowest post-irradiation annealing temperatures after irradiation. The drastically lowered recovery temperature is attributed to the reduced oxygen and carbon content of the 0.1 ohm-cm cells. Analysis based on defect properties and annealing kinetics indicates that further reduction in annealing temperature is attainable with further reduction in the silicon's carbon and/or divacancy content after irradiation.

Weinberg, I.↗

Cryo-Etched Black Silicon for Use as Optical Black

Stray light reflected from the surface of imaging spectrometer components in particular, the spectrometer slit degrade the image quality. A technique has been developed for rapid, uniform, and cost-effective black silicon formation based on inductively coupled plasma (ICP) etching at cryogenic temperatures. Recent measurements show less than 1-percent total reflectance from 350 2,500 nm of doped black silicon formed in this way, making it an excellent option for texturing of component surfaces for reduction of stray light. Oxygen combines with SF6 + Si etch byproducts to form a passivation layer atop the Si when the etch is performed at cryogenic temperatures. Excess flow of oxygen results in micromasking and the formation of black silicon. The process is repeatable and reliable, and provides control over etch depth and sidewall profile. Density of the needles can be controlled to some extent. Regions to be textured can be patterned lithographically. Adhesion is not an issue as the nanotips are part of the underlying substrate. This is in contrast to surface growth/deposition techniques such as carbon nanotubes (CNTs). The black Si surface is compatible with wet processing, including processing with solvents, the textured surface is completely inorganic, and it does not outgas. In radiometry applications, optical absorbers are often constructed using gold black or CNTs. This black silicon technology is an improvement for these types of applications.

Yee, Karl Y.↗

Oxygen reduction of several gold alloys in 1-molar potassium hydroxide

With rotated disk-and-ring equipment, polarograms and other electrochemical measurements were made of oxygen reduction in 1-molar potassium hydroxide on an equiatomic gold-copper (Au-Cu) alloy and a Au-Cu alloy doped with either indium (In) or cobalt (Co) and on Au doped with either nickel (Ni) or platinum (Pt). The results were compared with those for pure Au and pure Pt. The two-electron reaction dominated on all Au alloys as it did on Au. The polarographic results at lower polarization potentials were compared, assuming exclusively a two-step reduction. A qualified ranking of cathodic electrocatalytic activity on the freshly polished reduced disks was indicated: anodized Au Au-Cu-In Au-Cu Au-Cu-Co is equivalent or equal to Au-Pt Au-Ni. Aging in distilled water improved the electrocatalytic efficiency of Au-Cu-Co, Au-Cu, and (to a lesser extent) Au-Cu-In.

Miller, R. O.↗

Radiation damage and defect behavior in proton irradiated lithium-counterdoped n+p silicon solar cells

Two lithium-counterdoped n+p silicon solar cells with different lithium concentrations were irradiated by 10-MeV protons. Cell performance was measured as a function of fluence, and it was found that the cell with the highest concentration of lithium had the highest radiation resistance. Deep level transient spectroscopy which showed two deep level defects that were lithium related. Relating the defect energy levels obtained from this study with those from earlier work using 1-MeV electron irradiation shows no correlation of the defect energy levels. There is one marked similarity: the absence of the boron-interstitial-oxygen-interstitial defect. This consistency strengthens the belief that lithium interacts with oxygen to prevent the formation of the boron interstitial-oxygen interstitial defect. The results indicate that, in general, addition of lithium in small amounts to the p-base of a boron doped silicon solar cell such that the base remains p-type, tends to increase the radiation resistance of the cell.

Stupica, John↗

Growth studies of erbium-doped GaAs deposited by metalorganic vapor phase epitaxy using noval cyclopentadienyl-based erbium sources

Erbium-doped GaAS layers were grown by metalorganic vapor phase epitaxy using two new sources, bis(i-propylcyclopentadienyl)cyclopentadienyl erbium and tris(t-butylcyclopentadienyl) erbium. Controlled Er doping in the range of 10(exp 17) - 10(exp 18)/cu cm was achieved using a relatively low source temperature of 90 C. The doping exhibits a second-order dependence on inlet source partial pressure, similar to behavior obtained with cyclopentadienyl Mg dopant sources. Equivalent amounts of oxygen and Er are present in 'as-grown' films indicating that the majority of Er dopants probably exist as Er-O complexes in the material. Er(+3) luminescence at 1.54 micrometers was measured from the as-grown films, but ion implantation of additional oxygen decreases the emission intensity. Electrical compensation of n-type GaAs layers codoped with Er and Si is directly correlated to the Er concentration is proposed to arise from the deep centers associated with Er which are responsible for a broad emission band near 0.90 micrometers present in the photoluminescence spectra of GaAs:Si, Er films.

Redwing, J. M.↗

High Temperature Si-doped BN Interphases for Woven SiC/SiC Composites

The hydrolytic stability of high-temperature deposited Si-doped BN has been shown in the past to be superior in comparison to "pure" BN processed at similar or even higher temperatures. This type of material would be very desirable as a SiC/SiC composite interphase that is formed by chemical infiltration into multi-ply woven preform. However, due to rapid deposition on the preform outer surface at the high processing temperature, this has proven very difficult. To overcome this issue, single plies of woven fabric were infiltrated with Si-doped BN. Three composite panels of different SiC fiber types were fabricated with Si-doped BN interphases including Sylramic, Hi-Nicalon Type S and Sylramic-iBN fiber-types. The latter fiber-type possesses a thin in-situ grown BN layer on the fiber surface. High Si contents (approx. 7 to 10 a/o) and low oxygen contents (less than 1 a/o) were achieved. All three composite systems demonstrated reasonable debonding and sliding properties. The coated Sylramic fabric and composites were weak due to fiber degradation apparently caused during interphase processing by the formation of TiN crystals on the fiber surface. The Hi-Nicalon Type S composites with Si-doped BN interphase were only slightly weaker than Hi-Nicalon Type S composites with conventional BN when the strength on the load-bearing fibers at failure was compared. On the other hand, the Sylramic-iBN fabric and composites with Si-doped BN showed excellent composite and intermediate temperature stress-rupture properties. Most impressive was the lack of any significant interphase oxidation on the fracture surface of stress-ruptured specimens tested well above matrix cracking at 815C.

Morscher, Gregory N.↗

Gadolinia-Doped Ceria Cathodes for Electrolysis of CO2

Gadolinia-doped ceria, or GDC, (Gd(0.4)Ce(0.6)O(2-delta), where the value of delta in this material varies, depending on the temperature and oxygen concentration in the atmosphere in which it is being used) has shown promise as a cathode material for high-temperature electrolysis of carbon dioxide in solid oxide electrolysis cells. The polarization resistance of a GDC electrode is significantly less than that of an otherwise equivalent electrode made of any of several other materials that are now in use or under consideration for use as cathodes for reduction of carbon dioxide. In addition, GDC shows no sign of deterioration under typical temperature and gas-mixture operating conditions of a high-temperature electrolyzer. Electrolysis of CO2 is of interest to NASA as a way of generating O2 from the CO2 in the Martian atmosphere. On Earth, a combination of electrolysis of CO2 and electrolysis of H2O might prove useful as a means of generating synthesis gas (syngas) from the exhaust gas of a coal- or natural-gas-fired power plant, thereby reducing the emission of CO2 into the atmosphere. The syngas a mixture of CO and H2 could be used as a raw material in the manufacture, via the Fisher-Tropsch process, of synthetic fuels, lubrication oils, and other hydrocarbon prod

Adler, Stuart B.↗

Oxidative Recession, Sulfur Release, and Al203 Spallation for Y-Doped Alloys

Second-order spallation phenomena have been noted for Y-doped Rene'N5 after long term oxidation at 1150 degrees C. The reason for this behavior has not been conclusively identified. A mass equivalence analysis has shown that the surface recession resulting from oxidation has the potential of releasing about 0.15 monolayer of sulfur for every 1 mg/sq cm of oxygen reacted for an alloy containing 5 ppmw of sulfur. This amount is significant in comparison to levels that have been shown to result in first-order spallation behavior for undoped alloys. Oxidative recession is therefore speculated to be a contributing source of sulfur and second-order spallation for Y-doped alloys.

Smialek, James L.↗

Highly photoconducting O2-doped CdS films deposited by spray pyrolysis

CdS films have been prepared by spraying in air solutions of thiourea with either cadmium chloride or cadmium acetate with varying mole ratio and substrate temperature, and subsequently heat treating in oxygen. Substrates included both bare glass or sapphire and transparent conducting oxide-coated sapphire for electrical measurements lateral and transverse to the CdS plane, respectively. Dark resistances of over 10 to the 14th ohms and light-to-dark conductivities of up to 10 to the 7th were obtained using uncoated substrates. The use of Cd(C2H3O2)2 in place of CdCl2 greatly increased the speed of response although with some sacrifice in photoconductivity. Deposition of CdS on ITO-coated surfaces led to greatly reduced dark resistances for the case of CdCl2, but not Cd(C2H3O2)2, presumably due to HCl reaction with the ITO coating in the course of spraying with the former. Ion microprobe analysis detected indium within the CdS films exhibiting low dark resistance. Measurements of the dark and light conductivities at temperatures down to 77 K are given as are the response times for unetched and HCl-etched surfaces.

Richards, D.↗

Moessbauer spectroscopic studies of iron-doped rutile.

Moessbauer spectra were obtained of single crystal and powdered samples of rutile (TiO2) doped to about one percent by weight in isotopically enriched iron. It is shown that the oxidation state may be reversibly altered in situ. After reduction, the oxygen neighbors of the dopant ion are apparently shifted to accomodate the larger ferrous ion. The agreement of calculated quadrupole splittings with experimental results suggests that impurities and oxygen vacancies are uniformly distributed in powdered samples, giving the dopant ions an 'ideal lattice' local environment. The differences between the single crystal and powder sample hyperfine parameters are attributed to variations in stoichiometry, charge compensation mechanisms, or other diffusion related parameters.

Stampfl, P. P.↗

Multifunctional Electroactive Nanocomposites Based on Piezoelectric Boron Nitride Nanotubes

Space exploration missions require sensors and devices capable of stable operation in harsh environments such as those that include high thermal fluctuation, atomic oxygen, and high-energy ionizing radiation. However, conventional or state-of-the-art electroactive materials like lead zirconate titanate, poly(vinylidene fluoride), and carbon nanotube (CNT)-doped polyimides have limitations on use in those extreme applications. Theoretical studies have shown that boron nitride nanotubes (BNNTs) have strength-to-weight ratios comparable to those of CNTs, excellent high-temperature stability (to 800 C in air), large electroactive characteristics, and excellent neutron radiation shielding capability. In this study, we demonstrated the experimental electroactive characteristics of BNNTs in novel multifunctional electroactive nanocomposites. Upon application of an external electric field, the 2 wt % BNNT/polyimide composite was found to exhibit electroactive strain composed of a superposition of linear piezoelectric and nonlinear electrostrictive components. When the BNNTs were aligned by stretching the 2 wt % BNNT/polyimide composite, electroactive characteristics increased by about 460% compared to the nonstretched sample. An all-nanotube actuator consisting of a BNNT buckypaper layer between two single-walled carbon nanotube buck-paper electrode layers was found to have much larger electroactive properties. The additional neutron radiation shielding properties and ultraviolet/visible/near-infrared optical properties of the BNNT composites make them excellent candidates for use in the extreme environments of space missions. utilizing the unique characteristics of BNNTs.

Kang, Jin Ho↗