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At least 109 records · Page 6

F-region dynamics

The U.S. research efforts in the last four years, relating to an understanding of upper atmosphere or thermosphere and F-region dynamics are reported. Simultaneous measurements of atmospheric parameters from the Atmosphere Explorer satellites were used in photochemistry and photoenergetics studies. Studies of the magnetosphere as a major source of energy and momentum for the thermosphere are outlined. Time-dependent ionosphere models which describe the thermal structure, composition, photoelectron spectrum, and airglow emissions in F-regions are discussed. Solar tides, magnetic disturbances, and gravity waves in the thermosphere are considered. It is noted that planetary explorations will help to understand scientific problems of the space environment.

Mayr, H. G.↗

The infrared continuum spectrum of x ray illuminated molecular gas

In starburst galaxies, active galaxies, and the mysterious ultraluminous infrared galaxies, x rays are likely to interact with molecular gas and dust, thereby inducing infrared emission. X ray heated thermal dust will emit the IR continuum, and x ray photoelectrons will excite an IR emission-line spectrum. Here, researchers model the IR continuum emission characteristic of some selected x ray spectral fluxes, in particular the x ray bremsstrahlung characteristic of supernova and stellar wind bubble shocks in dense media and the power law spectra characteristic of active galactic nuclei. These models are part of a larger project to determine the complete IR spectra, lines plus continuum, of x ray sources embedded in molecular gas. They modeled the thermal emission from grains by calculating a grain temperature/size/composition distribution function, f(T,a,Comp.), which accounts for temperature fluctuations by averaging over all grain thermal histories. In determining the grain thermal distribution, researchers account for both direct grain heating (by x ray absorption and subsequent electron energy deposition) and indirect grain heating (by absorption of the UV emission stimulated by non-thermal photo- and Auger electrons in the gas phase). We let the grain size distribution be proportional to a(exp -3.5), and they consider two types of grain composition: graphites, which we assume to be pure carbon, and silicates, which contain all other depleted heavy elements. They derive the grain composition distribution function from solar abundances and interstellar depletion data.

Voit, G. Mark↗

Consistency Between SC#21REF Solar XUV Energy Input and the 1973 Pioneer 10 Observations of the Jovian Photoelectron Excited H2 Airglow

It has been suggested in the literature that the F74113 solar spectrum for the solar minimum condition needs to be modified to explain the production of photoelectrons in the Earth's atmosphere. We have studied here the effect of another solar minimum spectrum, SC#21REF, on the Jovian upper atmosphere emissions and we have compared the predicted photoelectron excited H2 airglow with the 1973 Pioneer 10 observations, analyzed according to the methodology of Shemansky and Judge (1988). In this model calculation we find that in 1973, the Jovian H2 band emissions can be accounted for almost entirely by photoelectron excitation, if the preflight calibration of the Pioneer 10 ultraviolet photometer is adopted. If the SC#21REF flux shortward of 250 A is multiplied by 2 as proposed by Richards and Torr (1988) then the Pioneer 10 calibration and/or the airglow model used must be modified in order to have a self consistent set of observations.

Gangopadhyay, P.↗

Mechanisms and dynamics of the NH + 2 + H + and NH + + H + + H fragmentation channels upon single-photon double ionization of NH 3

We present state-selective measurements on the NH$_2^{+}$ + H$^{+}$ and NH$^{+}$ + H$^{+}$ + H dissociation channels following single-photon double ionization at 61.5 eV of neutral NH$_{3}$, where the two photoelectrons and two cations are measured in coincidence using 3-D momentum imaging. Three dication electronic states are identified to contribute to the NH$_2^{+}$ + H$^{+}$ dissociation channel, where the excitation in one of the three states undergoes intersystem crossing prior to dissociation, producing a cold NH$_2^+$ fragment. In contrast, the other two states directly dissociate, producing a ro-vibrationally excited NH$_2^+$ fragment with roughly 1 eV of internal energy. The NH$^{+}$ + H$^{+}$ + H channel is fed by direct dissociation from three intermediate dication states, one of which is shared with the NH$_2^{+}$ + H$^{+}$ channel. We find evidence of autoionization contributing to each of the double ionization channels. Finally, the distributions of the relative emission angle between the two photoelectrons, as well as the relative angle between the recoil axis of the molecular breakup and the polarization vector of the ionizing field, are also presented to provide insight on the ionization mechanisms for the different dication states.

74 ATOMIC AND MOLECULAR PHYSICS↗

Infrared Emission From Interstellar PAHs, New Probes of the Interstellar Medium

Tremendous strides have been made in the understanding of interstellar material over the past twenty years thanks to significant, parallel developments in two closely related areas: observational IR astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely unknown and the notion of abundant, gas phase, polycyclic aromatic hydrocarbons (PAHs) anywhere in the interstellar medium (ISM) considered impossible. Today the dust composition of the diffuse and dense ISM is reasonably well constrained and the spectroscopic case for interstellar PAHs, impossibly large molecules by early interstellar chemistry standards, is very strong. PAH spectral features are now being used as new probes of the ISM. PAH ionization states reflect the ionization balance of the medium while PAH size and structure reflect the energetic and chemical history of the medium. Aromatic carbon-rich materials ranging in size from PAHs and PAH nanoclusters, to sub-micron and micron-sized dust grains represent an important component of the ISM. These species: (1) dominate the heating and cooling of interstellar clouds via energetic photoelectron ejection and infrared (IR) emission; (2) moderate the ionization balance in photodissociation regions and molecular clouds; (3) moderate the composition of the gas phase and play an important role in determining the chemistry of the ISM; (4) contribute to the interstellar extinction in the near IR, visible, and UV spectral regions; and (5) convert UV, visible, and near-IR radiation to mid- and far-IR radiation in the ISM and, as such, are responsible for the well known, widespread family of mid-IR emission features with major components near 3.3, 6.2, 7.7, 8.6, and 11.3 microns.

Hudgins, D. M.↗

Steep sulfur gradient in CZTSSe solar cells by H 2 S-assisted rapid surface sulfurization

Sulfur/selenium grading is a widely used optimization strategy in kesterite thin-film solar cells to obtain a bandgap-graded absorber material and to optimize optical and electrical properties of the solar-cell device. In this work, we present a novel approach to introduce a [S]/([S] + [Se]) grading for Cu 2 ZnSn(S,Se) 4 solar cells. In contrast to commonly used methods with slow process dynamics, the presented approach aims to create a fast sulfurization reaction on the surface of pure selenide kesterite absorbers by using highly reactive H 2 S gas and high sulfurization temperatures in a rapid flash-type process. With a combination of X-ray photoelectron spectroscopy, X-ray emission spectroscopy, Raman spectroscopy, and Raman-shallow angle cross sections spectroscopy, we gain depth-varied information on the [S]/([S] + [Se]) ratio and discuss the impact of different process parameter variations on the material and device properties. The results demonstrate the potential of the developed process to generate a steep gradient of sulfur that is confined mainly to the surface region of the absorber film.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal-dielectric interactions

Metal direlectric surface interactions and dielectric films on metal substrates were investigated. Since interfacial interaction depends so heavily on the nature of the surfaces, analytical surface tools such as Auger emission spectroscopy, X-ray photoelectron spectroscopy and field ion microscopy were used to assist in surface and interfacial characterization. The results indicate that with metals contacting certain glasses in the clean state interfacial, bonding produces fractures in the glasses while when a film such as water is present, fractures occur in the metal near the interface. Friction forces were used to measure the interfacial bond strengths. Studies with metals contacting polymers using field ion microscopy revealed that strong bonding forces could develop being between a metal and polymer surface with polymer transferring to the metal surface in various ways depending upon the forces applied to the surface in contact. With the deposition of refractory carbides, silicides and borides onto metal and alloy substrates the presence of oxides at the interface or active gases in the deposition plasma were shown to alter interfacial properties and chemistry. Auger ion depth profile analysis indicated the chemical composition at the interface and this could be related to the mechanical, friction, and wear behavior of the coating.

Buckley, D. H.↗

Diamond Analyzed by Secondary Electron Emission Spectroscopy

Diamond is a promising semiconductor material for novel electronic applications because of its chemical stability and inertness, heat conduction properties, and so-called negative electron affinity (NEA). When a surface has NEA, electrons generated inside the bulk of the material are able to come out into the vacuum without any potential barrier (work function). Such a material would have an extremely high secondary electron emission coefficient o, very high photoelectron (quantum) yield, and would probably be an efficient field emitter. Chemical-vapor-deposited (CVD) polycrystalline diamond films have even more advantages than diamond single crystals. Their fabrication is relatively easy and inexpensive, and they can be grown with high levels of doping--consequently, they can have relatively high conductivity. Because of these properties, diamond can be used for cold cathodes and photocathodes in high-power electronics and in high-frequency and high-temperature semiconductor devices.

Krainsky, Isay L.↗

Solar Irradiance and Thermospheric Airglow Rocket Experiments

This report describes work done in support of the Solar Irradiance and Thermospheric Air-glow Rocket Experiments at the University of Colorado for NASA grant NAG5-5021 under the direction of Dr. Stanley C. Solomon. (The overall rocket program is directed by Dr. Thomas N. Woods, formerly at the National Center for Atmospheric Research, and now also at the University of Colorado, for NASA grant NAG5-5141.) Grant NAG5-5021 provided assistance to the overall program through analysis of airglow and solar data, support of two graduate students, laboratory technical services, and field support. The general goals of the rocket program were to measure the solar extreme ultraviolet spectral irradiance, measure the terrestrial far-ultraviolet airglow, and analyze their relationship at various levels of solar activity, including near solar minimum. These have been met, as shown below. In addition, we have used the attenuation of solar radiation as the rocket descends through the thermosphere to measure density changes. This work demonstrates the maturity of the observational and modeling methods connecting energetic solar photon fluxes and airglow emissions through the processes of photoionization and photoelectron production and loss. Without a simultaneous photoelectron measurement, some aspects of this relationship remain obscure, and there are still questions pertaining to cascade contributions to molecular and atomic airglow emissions. However, by removing the solar irradiance as an "adjustable parameter" in the analysis, significant progress has been made toward understanding the relationship of far-ultraviolet airglow emissions to the solar and atmospheric conditions that control them.

Solomon, Stanley C.↗

Nitrogen airglow sources - Comparison of Triton, Titan, and earth

The individual contributions of direct solar excitation, photoelectron excitation, and magnetospheric electron excitation of Triton and Titan airglow observed by the Voyager Ultraviolet Spectrometer (UVS) are quantified. The principal spectral features of Triton's airglow are shown to be consistent with precipitation of magnetospheric electrons with power dissipation about 500 million W. Solar excitation rates of the dominant N2 and N(+) emission features are factors of 2-7 weaker than magnetospheric electron excitation. On Titan, the calculated disk center and bright limb N(+) 1085 A intensities due to solar excitation agree with observed values, while the 970 A feature is mostly N21 c5 band emission. The calculated LBH intensity by photoelectrons suggests that magnetospheric electrons play a minor role in Titan's UV airglow. On earth, solar/photoelectron excitation explains the observed N(+) 1085 A and LBH intensites and accounts for only 40 percent of the N(+) 916 A intensity.

Strobel, Darrell F.↗

Multiscale Investigation of the Mechanisms Controlling the Corrosion of Borosilicate Glasses in Hyper-Alkaline Media

The overarching goal of the present multiscale investigation is to unearth the kinetics and mechanisms of corrosion of borosilicate glasses in hyper-alkaline (pH = 13) environments as a function of their chemical composition. Accordingly, a series of 3- to 6-component borosilicate glasses have been designed starting from Na 2 O–B 2 O 3 –SiO 2 ternary, wherein the compositional complexity has been added in a systematic tiered approach, finally resulting in the composition of the well-known international simple glass (ISG). Tetramethylammonium hydroxide (TMAH), one of the most widely used alkaline etchant in the glass and electronics industry, has been used as the corrosion media. A series of state-of-the-art characterization techniques including magic angle spinning nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma optical emission spectroscopy, elastic recoil detection analysis, and high-resolution transmission electron microscopy have been employed to unearth the compositional dependence of glass corrosion in hyper-alkaline environments. The glass compositions underwent congruent corrosion in the forward rate regime, whereas the controlling mechanism of corrosion in the residual rate regime depends on the presence/absence of Ca in the surrounding environment and can be explained on the basis of the dissolution–reprecipitation model. The dependence of corrosion kinetics and the chemistry of alteration products (in the residual rate regime) on the glass composition have been discussed. Here, the results presented in this contribution will ultimately supplement the scientific literature attempting to understand the fundamental science governing the aqueous corrosion of silicate-based glass chemistries and add to the growing database required to develop non-empirical predictive models for designing glasses with controlled dissolution rates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Tuning Bulk Redox and Altering Interfacial Reactivity in Highly Fluorinated Cation-Disordered Rocksalt Cathodes

Lithium-excess, cation-disordered rocksalt (DRX) materials have been subject to intense scrutiny and development in recent years as potential cathode materials for Li-ion batteries. Despite their compositional flexibility and high initial capacity, they suffer from poorly understood parasitic degradation reactions at the cathode-electrolyte interface. These interfacial degradation reactions deteriorate both the DRX material and electrolyte, ultimately leading to capacity fade and voltage hysteresis during cycling. In this work, differential electrochemical mass spectrometry (DEMS) and titration mass spectrometry are combined to quantify the extent of bulk redox and surface degradation reactions for a set of Mn 2+/4+ -based DRX oxyfluorides during initial cycling with a high-voltage charging cutoff (4.8 V vs Li/Li + ). Increasing the fluorine content from 7.5 to 33.75% is shown to diminish oxygen redox and suppresses high-voltage O 2 evolution from the DRX surface. Additionally, electrolyte degradation processes resulting in the formation of both gaseous species and electrolyte-soluble protic species are observed. Subsequently, DEMS is paired with a fluoride-scavenging additive to demonstrate that increasing fluorine content leads to increased dissolution of fluorine from the DRX material into the electrolyte. Finally, a suite of ex situ spectroscopy techniques (X-ray photoelectron spectroscopy, inductively coupled plasma optical emission spectroscopy, and solid-state nuclear magnetic resonance spectroscopy) are employed to study the change in DRX composition during charging, revealing the dissolution of manganese and fluorine from the DRX material at high voltages. Here this work provides insight into the degradation processes occurring at the DRX-electrolyte interface and points toward potential routes of interfacial stabilization.

25 ENERGY STORAGE↗

Metal-dielectric interactions

There is a wide variety of situations wherein metals are in solid state contact with dielectric materials. The paper reviews some of the factors that influence solid state interactions for metals in contact with dielectric surfaces. Since surfaces play an important part in these reactions, the use of analytical tools in characterizing surfaces is discussed. Adhesion, friction, and wear are utilized as indicators of the nature of interfacial bonding between metals and dielectrics can be effectively determined with adhesion and friction force measurements. Films present on the surface, such as oxygen or water vapor, markedly alter adhesive bond strength which in turn affects friction force and interfacial fracture when attempts are made to separate the contact regions. Analytical surface tools such as the field ion microscope, Auger emission spectroscopy, and X-ray photoelectron spectroscopy are very effective in providing insight into the effect of contact on the surfaces of metals and dielectrics.

Buckley, D. H.↗

Effect of LEO Exposure on Aromatic Polymers Containing Phenylphosphine Oxide Groups

As part of the Materials on The International Space Station Experiment (MISSE), aromatic polymers containing phenylphosphine oxide groups were exposed to low Earth orbit (LEO) for approximately 4 years. All of the aromatic polymers containing phenylphosphine oxide groups survived the exposure despite the high fluence of atomic oxygen that completely eroded other polymer films such as Kapton and Mylar of comparable or greater thickness. The samples consisted of a colorless polyimide film and a poly(arylene ether benzimidazole) film and thread. The samples were characterized for changes in physical properties, thermal/optical properties (i.e. solar absorptivity and thermal emissivity), surface chemistry (X-ray photoelectron spectroscopy), and surface topography (atomic force microscopy). The data from the polymer samples on MISSE were compared to samples from the same batch of material stored under ambient conditions on Earth. In addition, comparisons were made between the MISSE samples and those subjected to shorter term space flight exposures. The results of these analyses will be presented.

Watson, K. A.↗

Experimental Investigation of Space Radiation Processing in Lunar Soil Ilmenite: Combining Perspectives from Surface Science and Transmission Electron Microscopy

Energetic ions mostly from the solar wind play a major role in lunar space weathering because they contribute structural and chemical changes to the space-exposed surfaces of lunar regolith grains. In mature mare soils, ilmenite (FeTiO3) grains in the finest size fraction have been shown in transmission electron microscope (TEM) studies to exhibit key differences in their response to space radiation processing relative to silicates [1,2,3]. In ilmenite, solar ion radiation alters host grain outer margins to produce 10-100 nm thick layers that are microstructurally complex, but dominantly crystalline compared to the amorphous radiation-processed rims on silicates [1,2,3]. Spatially well-resolved analytical TEM measurements also show nm-scale compositional and chemical state changes in these layers [1,3]. These include shifts in Fe/Ti ratio from strong surface Fe-enrichment (Fe/Ti >> 1), to Fe depletion (Fe/Ti < 1) at 40-50 nm below the grain surface [1,3]. These compositional changes are not observed in the radiation-processed rims on silicates [4]. Several mechanism(s) to explain the overall relations in the ilmenite grain rims by radiation processing and/or additional space weathering processes were proposed by [1], and remain under current consideration [3]. A key issue has concerned the ability of ion radiation processing alone to produce some of the deeper- penetrating compositional changes. In order to provide some experimental constraints on these questions, we have performed a combined X-ray photoelectron spectroscopy (XPS) and field-emission scanning transmission electron (FE-STEM) study of experimentally ion-irradiated ilmenite. A key feature of this work is the combination of analytical techniques sensitive to changes in the irradiated samples at depth scales going from the immediate surface (approx.5 nm; XPS), to deeper in the grain interior (5-100 nm; FE-STEM).

Christoffersen, R.↗

Mapping the composition of planetary surfaces by Auger electron spectroscopy

The feasibility of AES as a remote-sensing technique to map the composition of the sunlit surfaces of planetary bodies without atmospheres is studied. Solar X-rays eject photoelectrons from the planetary surface. The resulting ions relax by emission of fluorescence X-rays or Auger electrons, with energies characteristic of the element which is ionized. The spectrum of Auger electrons and photoelectrons is computed for a variety of elements and for representative lunar rock types illuminated by soft-X-ray line and continuum emission typical of solar long-lived coronal active regions. The Auger electron lines for O, Si, Mg, Al, Fe, and Ca in lunar rocks stand well above the continuum background from photoelectrons and backscattered interplanetary electrons, with typical line-to-continuum ratios from about 20 to over 1000.

Lin, R. P.↗