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At least 19 records

O(-) identified at high temperatures in CaO-based catalysts for oxidative methane dimerization

A technique called charge-distribution analysis (CDA) is employed to study mobile charge carriers in the oxidation catalysts CaO, CaO with 11 percent Na2O, and CaO with 10 percent La2O3. A threshold temperature of about 550-600 C is identified at which highly mobile charge carriers are present, and the CDA studies show that they are O(-) states. The present investigation indicates the usefulness of CDA in catalysis research with pressed powder samples and gas/solid reactions.

Freund, F.↗

Charge Generation and Propagation in Igneous Rocks

Various electrical phenomena have been reported prior to or concurrent with earthquakes such as resistivity changes, ground potentials, electromagnetic (EM), and luminous signals. Doubts have been raised as to whether some of these phenomena are real and indeed precursory. One of the reasons for uncertainty is that, despite decades of intense work, there is still no physically coherent model. Using low- to medium-velocity impacts to measure electrical signals with microsecond time resolution, it has now been observed that when dry gabbro and diorite cores are impacted at relatively low velocities, approximately 100 m/s, highly mobile charge carriers are generated in a small volume near the impact point. They spread through the rocks, causing electric potentials exceeding +400 mV, EM, and light emission. As the charge cloud spreads, the rock becomes momentarily conductive. When a dry granite block is impacted at higher velocity, approximately 1.5 km/s, the propagation of the P and S waves is registered through the transient piezoelectric response of quartz. After the sound waves have passed, the surface of the granite block becomes positively charged, suggesting the same charge carriers as observed during the low-velocity impact experiments, expanding from within the bulk. During the next 2-3 ms the surface potential oscillates, indicating pulses of electrons injected from ground and contact electrodes. The observations are consistent with positive holes, e.g., defect electrons in the O(2-) sublattice, traveling via the O 2p-dominated valence band of the silicate minerals. Before activation, the positive holes lay dormant in the form of electrically inactive positive hole pairs (PHP), chemically equivalent to peroxy links, O3X/OO\XO3, with X=Si(4+), Al(3+), etc. PHPs are introduced into the minerals by way of hydroxyl,O3X-OH, which all nominally anhydrous minerals incorporate when crystallizing in H2O-laden environments. The fact that positive holes can be activated by low-energy impacts, and their attendant sound waves, suggests that they can also be activated by microfracturing. Depending on where in the stressed rock volume the charge carriers are activated, they will form rapidly moving or fluctuating charge clouds that may account for earthquake-related electrical signals and EM emission. Wherever such charge clouds intersect the surface, high fields are expected, causing electric discharges and earthquake lights.

Freund, Friedemann↗

Highly mobile oxygen hole-type charge carriers in fused silica

Some peculiar positive charge carriers are thermally generated in fused silica above 500 C. These charge carriers appear to be positive holes, chemically O-states, probably arising from dissociation of peroxy defects. The charge carriers give rise to a pronounced positive surface charge which disappears upon cooling but can be quenched by rapid quenching from about 800 C. Reheating to 200 C remobilizes these charge carriers and causes them to anneal below 400 C. The generation of positive holes charge carriers may be important to understand failure mechanisms of SiO2 insulators.

Freund, Friedemann↗

Charge Generation and Propagation in Igneous Rocks

Resistivity changes, ground potentials, electromagnetic (EM) and luminous signals prior to or during earthquakes have been reported, in addition to ground uplift and tilt, and to changes in the seismic wave propagation parameters. However, no physical model exists that ties these diverse phenomena together. Through time-resolved impacts experiments it has been observed that, when igneous rocks (gabbro, diorite, granite) are impacted at low velocities (approx. 100 m/sec), highly mobile electronic charge carriers are generated, spreading from a small volume near the impact point, causing electric potentials, EM and light emission. The rock becomes momentarily conductive. When impacted at higher velocities (approx. 1.5 km/sec), the propagation of the P and S waves is registered through the transient piezoelectric response of quartz. At the same time, the rock volume is filled with mobile charge carriers, and a positive surface potential is registered. During the next 1-2 msec the surface potential oscillates, due to electron injection from ground. These observations are consistent with positive holes, e.g. defect electrons in the O(2-) sublattice, that can travel via the O 2p-dominated valence band of the silicate minerals at the speed of a phonon-mediated charge transfer. Before activation, the positive hole charge carriers lay dormant in form of positive hole pairs, PHP, electrically inactive, chemically equivalent to peroxy links in the structures of constituent minerals. PHPs are introduced by way of hydroxyl (O3Si-OH) incorporated into nominally anhydrous minerals when they crystallize in water-laden environments. Given that sound waves of even relatively low intensity appear to cause PHPs dissociation, thus generating mobile positive holes, it is proposed that microfracturing during rock deformation cause PHP dissociation. Depending on where and how much the rock volume is stressed, the positive holes are expected to form fluctuating charge clouds in the earthquake source region that may account for earthquake-related electrical phenomena and the reported low frequency EM signals.

Freund, Friedemann↗

Electrical Conductivity of Rocks and Dominant Charge Carriers: Thermally Activated Positive Holes - Part 1

The prevailing view in the geophysics community is that the electrical conductivity structure of the Earth's continental crust over the 5-35 km depth range can best be understood by assuming the presence of intergranular fluids and/or of intragranular carbon films. Based on single crystal studies of melt-grown MgO, magma-derived sanidine and anorthosite feldspars and upper mantle olivine, we present evidence for the presence of electronic charge carriers, which derive from peroxy defects that are introduced during cooling, under non-equilibrium conditions, through a redox conversion of pairs of solute hydroxyl arising from dissolution of H2O.The peroxy defects become thermally activated in a 2-step process, leading to the release of defect electrons in the oxygen anion sublattice. Known as positive holes and symbolized by h(dot), these electronic charge carriers are highly mobile. Chemically equivalent to O(-) in a matrix of O(2-) they are highly oxidizing. Being metastable they can exist in the matrix of minerals, which crystallized in highly reduced environments. The h(dot) are highly mobile. They appear to control the electrical conductivity of crustal rocks in much of the 5-35 km depth range.

Freund, Friedemann T.↗

Stress-Activated Positive Holes (O− in a Matrix of O2–) Cause DNA Damage in Surface-Dwelling Organisms: Unveiling Mutation-Induced Secrets of Nature

Peroxy defects consist of pairs of tightly bonded oxygen anions in the –1 valence state such as in O3X/OO\YO3 with X, Y = Si4+, Al3+ etc. They commonly occur in igneous, metamorphic and many sedimentary rocks. When such rocks are stressed by tectonic forces, peroxy defects break up, releasing highly mobile electronic charge carriers: defect electrons in the O2– sublattice, i.e. unbound O–, known as “positive holes”, h•. The h• can flow out of stressed rock volumes, spreading far and wide, causing electric currents and electrochemical reactions. This study explores how the h• impact the electron flow in the electron transport chain (ETC) of organisms on the surface of rocks such as gabbro and granite. We found that, by forming hydroxyl radicals and superoxide anions, the h• disrupt the in vivo coordination of reduction-oxidation reactions that are essential for the timing of the redox cycle. Our observations show that stress activation of h• delays the sprouting of certain plant seeds and impedes the growth of yeast cultures, Saccharomyces cerevisiae. The h• induce mutations and affect plant development as evidenced by reduced stem length and leaf size. At the same time, the h• serve as a source of abiotic oxidation, capable of forming various organic compounds in situ. Through the generation of radical species that create new carbon-carbon bonds the h• facilitate the abiotic synthesis of hydrocarbons and other organic molecules essential to life, including porphyrins. Our findings highlight the intricate interplay between positive holes, redox timing, and biological processes, revealing their significant role in influencing the growth and development of organisms in tectonically stressed crustal environments. Understanding these effects enhances our broader comprehension of redox biology and the influence of environmental factors on cellular development in natural settings.

astrobiology↗

Inter-Valence-Subband/Conduction-Band-Transport IR Detectors

Infrared (IR) detectors characterized by a combination of (1) high-quantum-efficiency photoexcitation of inter-valence-subband transitions of charge carriers and (2) high-mobility conduction- band transport of the thus-excited charge carriers have been proposed in an effort to develop focal-plane arrays of such devices for infrared imaging. Like many prior quantum-well infrared photodetectors (QWIPs), the proposed devices would be made from semiconductor heterostructures. In order to obtain the combination of characteristics mentioned above, the proposed devices would be designed and fabricated in novel InAs/GaSb superlattice configurations that would exploit a phenomenon known in the semiconductor art as type-II broken-gap band offset.

Ting, David↗

High temperature Hall-effect apparatus

A high-temperature Hall-effect apparatus is described which allows measurements up to temperatures greater than 1200 K using the van der Pauw method. The apparatus was designed for measurements on refractory materials having high charge carrier concentrations and generally low mobilities. Pressure contacts are applied to the samples. Consequently, special contacting methods, peculiar to a specific sample material, are not required. The apparatus has been semiautomated to facilitate measurements. Results are presented on n- and p-type silicon.

Wood, C.↗

Charge distribution and response time for a modulation-doped extrinsic infrared detector

The electric charge distribution and response time of a modulation-doped extrinsic infrared detector are determined. First, it is demonstrated theoretically that the photoconductive layer is effectively depleted of ionized majority-impurity charges so that scattering is small and mobility is high for photogenerated carriers. Then, using parameters appropriate to an actual detector, the predicted response time is 10 to the -8th to about 10 to the -9th s, which is much faster than comparable conventional detectors. Thus, the modulation-doped detector design would be valuable for heterodyne applications.

Hadek, Victor↗

Effect of Rare Earth Elements (Er, Ho) on Semi-Metallic Materials (ScN) in an Applied Electric Field

The development of materials and fabrication technology for field-controlled spectrally active optics is essential for applications such as membrane optics, filters for LIDARs, windows for sensors, telescopes, spectroscopes, cameras and flat-panel displays. The dopants of rare earth elements, in a host of optical systems, create a number of absorption and emission band structures and can easily be incorporated into many high quality crystalline and amorphous hosts. In wide band-gap semiconductors like ScN, the existing deep levels can capture or emit the mobile charges, and can be ionized with the loss or capture of the carriers which are the fundamental basis of concept for smart optic materials. The band gap shrinkage or splitting with dopants supports the possibility of this concept. In the present work, a semi-metallic material (ScN) was doped with rare earth elements (Er, Ho) and tested under an applied electric field to characterize spectral and refractive index shifts by either Stark or Zeeman Effect. These effects can be verified using the UV-Vis spectroscopy, the Hall Effect measurement and the ellipsometric spectroscopy. The optical band gaps of ScN doped with Er and doped with Ho were experimentally estimated as 2.33eV and 2.24eV ( 0.2eV) respectively. This is less than that of undoped ScN (2.5 0.2eV). The red-shifted absorption onset is a direct evidence for the decrease of band gap energy (Eg), and the broadening of valence band states is attributable to the doping cases. A decrease in refractive index with an applied field was observed as a small shift in absorption coefficient using a variable angle spectroscopic ellipsometer. In the presence of an electric field, mobile carriers are redistributed within the space charge region (SCR) to produce this electro-refractive effect. The shift in refractive index is also affected by the density and location of deep potential wells within the SCR. In addition, the microstructure change was observed by a TEM analysis. These results give an insight for future applications for the field-controlled spectrally active material systems.

Kim, Hyunjung↗

Ion-implanted epitaxially grown ZnSe

The use of ZnSe to obtain efficient, short wavelength injection luminescence was investigated. It was proposed that shorter wavelength emission and higher efficiency be achieved by employing a p-i-n diode structure rather than the normal p-n diode structure. The intervening i layer minimizes concentration quenching effects and the donor-acceptor pair states leading to long wavelength emission. The surface p layer was formed by ion implantation; implantation of the i layer rather than the n substrate permits higher, uncompensated p-type doping. An ion implanted p-n junction in ZnSe is efficiency-limited by high electron injection terminating in nonradiative recombination at the front surface, and by low hole injection resulting from the inability to obtain high conductivity p-type surface layers. While the injection ratio in p-n junctions was determined by the radio of majority carrier concentrations, the injection ratio in p-i-n structures was determined by the mobility ratios and/or space charge neutrality requirements in the i layer.

Chernow, F.↗

New measurement of the Fano factor of mercuric iodide

It is pointed out that mercuric iodide (HgI2) shows great promise as a high-resolution X-ray detector for use in X-ray astronomy. Development of mercuric iodide for astronomical work has required investigation of the temperature dependence of the HgI2 crystal parameters such as leakage current, resolution, and mobility of the charge carriers. The first studies in connection with these investigations have led to a new value of the Fano factor of 0.19 + or - 0.03. The best value previously reported was 0.27 measured at room temperature. The new upper limit of 0.19 for the HgI2 Fano factor was determined by cooling the HgI2 crystal and preamp to -20 C. It is concluded that room-temperature energy resolution of HgI2 is not limited by charge generation statistics but rather by collection efficiency.

Ricker, G. R.↗

Nanowire Thermoelectric Devices

Nanowire thermoelectric devices, now under development, are intended to take miniaturization a step beyond the prior state of the art to exploit the potential advantages afforded by shrinking some device features to approximately molecular dimensions (of the order of 10 nm). The development of nanowire-based thermoelectric devices could lead to novel power-generating, cooling, and sensing devices that operate at relatively low currents and high voltages. Recent work on the theory of thermoelectric devices has led to the expectation that the performance of such a device could be enhanced if the diameter of the wires could be reduced to a point where quantum confinement effects increase charge-carrier mobility (thereby increasing the Seebeck coefficient) and reduce thermal conductivity. In addition, even in the absence of these effects, the large aspect ratios (length of the order of tens of microns diameter of the order of tens of nanometers) of nanowires would be conducive to the maintenance of large temperature differences at small heat fluxes. The predicted net effect of reducing diameters to the order of tens of nanometers would be to increase its efficiency by a factor of .3. Nanowires made of thermoelectric materials and devices that comprise arrays of such nanowires can be fabricated by electrochemical growth of the thermoelectric materials in templates that contain suitably dimensioned pores (10 to 100 nm in diameter and 1 to 100 microns long). The nanowires can then be contacted in bundles to form devices that look similar to conventional thermoelectric devices, except that a production version may contain nearly a billion elements (wires) per square centimeter, instead of fewer than a hundred as in a conventional bulk thermoelectric device or fewer than 100,000 as in a microdevice. It is not yet possible to form contacts with individual nanowires. Therefore, in fabricating a nanowire thermoelectric device, one forms contacts on nanowires in bundles of the order of 10-microns wide. The fill factor for the cross-section of a typical bundle is about 1/2. Nanowires have been grown in alumina templates with pore diameters of 100 and 40 nm.

Borshchevsky, Alexander↗

NASA Tech Briefs, March 2014

Topics include: Data Fusion for Global Estimation of Forest Characteristics From Sparse Lidar Data; Debris and Ice Mapping Analysis Tool - Database; Data Acquisition and Processing Software - DAPS; Metal-Assisted Fabrication of Biodegradable Porous Silicon Nanostructures; Post-Growth, In Situ Adhesion of Carbon Nanotubes to a Substrate for Robust CNT Cathodes; Integrated PEMFC Flow Field Design for Gravity-Independent Passive Water Removal; Thermal Mechanical Preparation of Glass Spheres; Mechanistic-Based Multiaxial-Stochastic-Strength Model for Transversely-Isotropic Brittle Materials; Methods for Mitigating Space Radiation Effects, Fault Detection and Correction, and Processing Sensor Data; Compact Ka-Band Antenna Feed with Double Circularly Polarized Capability; Dual-Leadframe Transient Liquid Phase Bonded Power Semiconductor Module Assembly and Bonding Process; Quad First Stage Processor: A Four-Channel Digitizer and Digital Beam-Forming Processor; Protective Sleeve for a Pyrotechnic Reefing Line Cutter; Metabolic Heat Regenerated Temperature Swing Adsorption; CubeSat Deployable Log Periodic Dipole Array; Re-entry Vehicle Shape for Enhanced Performance; NanoRacks-Scale MEMS Gas Chromatograph System; Variable Camber Aerodynamic Control Surfaces and Active Wing Shaping Control; Spacecraft Line-of-Sight Stabilization Using LWIR Earth Signature; Technique for Finding Retro-Reflectors in Flash LIDAR Imagery; Novel Hemispherical Dynamic Camera for EVAs; 360 deg Visual Detection and Object Tracking on an Autonomous Surface Vehicle; Simulation of Charge Carrier Mobility in Conducting Polymers; Observational Data Formatter Using CMOR for CMIP5; Propellant Loading Physics Model for Fault Detection Isolation and Recovery; Probabilistic Guidance for Swarms of Autonomous Agents; Reducing Drift in Stereo Visual Odometry; Future Air-Traffic Management Concepts Evaluation Tool; Examination and A Priori Analysis of a Direct Numerical Simulation Database for High-Pressure Turbulent Flows; and Resource-Constrained Application of Support Vector Machines to Imagery.

Source record↗

Transit time and charge storage measurements in heavily doped emitters

A first direct measurement of the minority-carrier transit time in a transparent heavily doped emitter layer is reported. The value was obtained by a high-frequency conductance method recently developed and used for low-doped Si. The transit time coupled with the steady-state current enables the determination of the quasi-static charge stored in the emitter and the quasi-static emitter capacitance. Using a transport model, from the measured transit time, the value for the minority-carrier diffusion coefficient and mobility is estimated. The measurements were done using a heavily doped emitter of the Si p(+)-n-p bipolar transistor. The new result indicates that the position-averaged minority-carrier diffusion coefficients may be much smaller than the corresponding majority-carrier values for emitters having a concentration ranging from about 3 x 10 to the 19th per cu cm to 10 to the 20th per cu cm.

Neugroschel, A.↗

Mixed-Domain Charge Transport in the S-Se System from First Principles

Lithium-sulfur (Li-S) batteries are emerging systems heralded for the inexpensive cathode component (in S)and higher energy density than that of typical Li-ion batteries [1–5]. For the latter reason in particular, they are drawing high levels of interest for long-range electric air-craft applications where high gravimetric energy density is of utmost importance. Unfortunately, S by itself has a much too low electrical conductivity to be useful asa stand-alone cathode material. One effort to alleviate these shortcomings is to alloy sulfur with selenium [6–13],which is expected to improve the paltry conductivity of S as Se, depending on the phase, is 10∼30 times more conductive. This, however, comes at the cost of the heavier mass of Se that works against the gravimetric energy density. The charge transport behavior in the S1−xSex alloy system, not yet fully known or understood, is necessary for one to navigate the trade-offs between conductivity and other variables such as energy density en route to ultimately determining the optimum Se content, on demand. Charting carrier mobilities and conductivities in the S-Se system throughout the compositional spectrum from first principles at a predictive level is therefore critical.

Junsoo Park↗

Stimulated Mid-Infrared Luminescence Experiment: Contribution to the Study of Pre-Earthquake Phenomena and UV Absorption by Interstellar Dust

The work performed under this proposal is based on the experimentally supported observation - or inference - that a small fraction of the oxygen anions in silicate minerals in igneous and high-grade metamorphic rocks on Earth may not be in the usual 2- oxidation state, O(sup 2-), but in a higher oxidation state, as O(sup -). If this is true, the same would likely apply to the fine dust that fills the diffuse interstellar medium. An (sup -) in a matrix of O(sup 2-) represents a defect electron in the valence band, also known as positive hole or p-hole for short. When two O(sup -) combine, they undergo spin-pairing and form a positive hole pair, PHP. Chemically speaking a PHP is a peroxy bond. In an oxide matrix a peroxy bond takes the form of a peroxy anion, O2(sup 2-). In a silicate matrix it probably exists in the form of peroxy links between adjacent [SiO4] tetrahedral, O3Si00\SiO3. From a physics perspective a PHP is an electrically inactive point defect, which contains dormant electronic charge carriers. When the peroxy bond breaks, p-hole charge carriers are released. These p-holes are diffusively mobile and spread through the O 2p-dominated valence band of the otherwise insulating mineral matrix.

Freund, Friedemann↗

Critical review of electrical conductivity measurements and charge distribution analysis of magnesium oxide

The electrical conductivity sigma of MgO single crystals shows a sharp increase at 500-800 C, in particular of sigma surface, generally attributed to surface contamination. Charge Distribution Analysis (CDA), a new technique providing information on fundamental properties that was previously unavailable, allows for the determination of surface charges, their sign and associated internal electric field. Data on 99.99% purity, arc-fusion grown MgO crystals show that mobile charge carriers start to appear in the bulk of the MgO crystals between 200 and 400 C when sigma (measured by conventional techniques) is in t he 10(exp -14) to 10(exp -16) /omega/cm range. Above 500 C, as sigma increases to 10(exp -6) to 10(exp -7)/omega/cm, more charges appear giving rise to a strong positive surface charge supported by a strong internal field. This indicates that charges are generated in the bulk and diffuse to the surface by an internally controlled process. On the basis of their positive sign they are identified as holes (defect electrons). Because of the low cation content of these very pure MgO crystals, theses holes cannnot be associated with transition metal impurties. Instead, they are associated with the O(2-) sublattice, e.g. consist of O(-) states or positive holes. This conclusion is supported by magnetic susceptibility data showing the appearance of 1000 +/- 500 ppm paramagnetic species between 200-500 C. The magnetic data are consistent with strongly coupled, diamagnetic O(-) pairs below 200-500 C, chemically equivalent to peroxy anions, O2(2-), and probably associated with cation vacancies in the MgO matrix. The formation of O2(2-) in arc-fusion grown MgO crystals is very unexpected because of the highly reducing growth conditions. Their presence implies an internal redox reaction involving dissolved 'water' by which OH(-) pairs convert to O2(2-) plus H2 molecules. This redox conversion is supported by mass spectroscopic measurements of the H2 release from highly OH(-)-doped, finely divided MgO and by wet-chemical analysis of its oxidant concentration.

Freund, Friedemann↗