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At least 253 records · Page 14

High performance etchant for thinning p(+)-InP and its application to p(+)n InP solar cell fabrication

An etchant, namely (o-H3PO4)u: (HNO3)v: (H2O2)t: (H2O)1-(u+v+t) is developed for thinning, after contacting, the p(+) emitter layer of p(+)n InP structures made by thermal diffusion. Varying u, v, and t, reproducible etch rates of 5 to 110 nm/min are obtained. After thinning the 0.6- to 2.5-micron thick p(+) InP layer down to 60-250 nm, specular surfaces are obtained at up to 80 nm/min etch rate. Due to its intrinsic qualities the resisual P-rich oxide after thinning the emitter layer provides surface passivation of p(+) InP surfaces and can also serve as a first-layer AR coating.

Faur, Maria↗

An overview of the spectroscopy of the atmosphere using far infrared emission experiment (SAFIRE)

The SAFIRE experiment was conceived to satisfy a long-standing need for simultaneous middle atmosphere observations of ozone and important O(y), HO(y), NO(y), ClO(y), and BrO(y) gases, coupled with dynamics data. This will be accomplished using interferometry and broadband radiometry to sound the Earth limb in the far IR and mid IR, respectively. The experiment will employ the latest developments in detector and cryogenic cooling technology in order to achieve the measurement objectives. Detailed instrument and simulated atmospheric retrieval studies show that important gases such as OH, HO2, H2O2, HDO, N2O5, and HOCl can be observed with good accuracy.

Russell, James M., III↗

Stratospheric spectroscopy with the far-infrared spectrometer (FIRS-2) - Overview and recent results

The Smithsonian Astrophysical Observatory's program of balloon-borne stratospheric spectroscopic measurements is described, including instrumentation, recent scientific results, and future plans. The design and operation of the FIRS-2 far-infrared spectrometer is discussed. The current status of our efforts to recover mixing-ratio profiles with about 1 percent precision is presented. Representative recent results are shown giving mixing-ratio profiles from 20 to 50 km, selected from the suite HOCl, HCl, HF, NO2, N2O, HNO3, OH, HO2, H2O2, H2O (and isotopes), O2 (and isotopes), O3 (and isotopes), and CO2 (and isotopes). The utility of O2 and CO2 spectral lines for information on view angle or temperature and pressure is discussed. Future plans are mentioned, including the use of FIRS-2 on a balloon platform for UARS correlative measurements, the use of FIRS-2 on the NASA DC-8 platform for polar measurements, and the potential benefits of a FIRS instrument on a Shuttle platform.

Traub, Wesley A.↗

Chemical kinetic studies of atmospheric reactions using tunable diode laser spectroscopy

IR absorption using tunable diode laser spectroscopy provides a sensitive and quantitative detection method for laboratory kinetic studies of atmospheric trace gases. Improvements in multipass cell design, real time signal processing, and computer controlled data acquisition and analysis have extended the applicability of the technique. We have developed several optical systems using off-axis resonator mirror designs which maximize path length while minimizing both the sample volume and the interference fringes inherent in conventional 'White' cells. Computerized signal processing using rapid scan (300 kHz), sweep integration with 100 percent duty cycle allows substantial noise reduction while retaining the advantages of using direct absorption for absolute absorbance measurements and simultaneous detection of multiple species. Peak heights and areas are determined by curve fitting using nonlinear least square methods. We have applied these techniques to measurements of: (1) heterogeneous uptake chemistry of atmospheric trace gases (HCl, H2O2, and N2O5) on aqueous and sulfuric acid droplets; (2) vapor pressure measurements of nitric acid and water over prototypical stratospheric aerosol (nitric acid trihydrate) surfaces; and (3) discharge flow tube kinetic studies of the HO2 radical using isotopic labeling for product channel and mechanistic analysis. Results from each of these areas demonstrate the versatility of TDL absorption spectroscopy for atmospheric chemistry applications.

Worsnop, Douglas R.↗

The atmospheric CH4 increase since the Last Glacial Maximum. II - Interactions with oxidants

Results of two studies of the effect of changing CH4 fluxes on global tropospheric oxidant levels, O3, OH, and H2O2, performed with a multibox photochemical model, are presented. A sensitivity study is conducted by scaling back CH4, CO, and NO emissions relative to the present-day budget. When the CH4 ice core record is compared to calculated CH4 abundances, corresponding CH4 fluxes for the preindustrial Holocene (PIH) and Last Glacial Maximum (LGM) are fairly well-constrained: 175-225 Tg CH/4/yr for PIH and 100-130 Tg CH4/yr for LGM. Specific scenarios for CH4/CO/NO are selected to represent sources for the PIH and LGM. The CH4 budget is taken from an evaluation of wetlands and other natural sources.

Thompson, Anne M.↗

Numerical simulations of turbulent premixed H2/O2/N2 flames with complex chemistry

Premixed stoichiometric H2/O2/N2 flames propagating in two-dimensional turbulence were studied using direct numerical simulation (simulations in which all fluid and thermochemical scales are fully resolved) including realistic chemical kinetics and molecular transport. Results are compared with earlier zero-chemistry (flame sheet) and one-step chemistry simulations. Consistent with the simpler models, the turbulent flame with realistic chemistry aligns preferentially with extensive strain rates in the tangent plane and flame curvature probability density functions are close to symmetric with near-zero means. By contrast to simple-chemistry results with non-unity Lewis numbers (ratio of thermal to species diffusivity), local flame structure does not correlate with curvature but rather with tangential strain rate. Turbulent straining results in substantial thinning of the flame relative to the steady unstrained laminar case. Heat release and H2O2 contours remain thin and connected ('flamelet-like') while species including H-atom and OH are more diffuse. Peak OH concentration occurs well behind the peak heat-release zone. The feasibility of incorporating realistic chemistry into full turbulence simulations to address issues such as pollutant formation in hydrocarbon-air flames is suggested.

Baum, M.↗

Measurement of HO2 and other trace gases in the stratosphere using a high resolution far-infrared spectrometer

This report covers the time period 1 Jul. to 31 Dec. 1993. There were no balloon or airplane flights during this reporting period, instead we concentrated on analyzing our existing data. This was facilitated by a recently completed program of enhancements made in our data reduction software. We are using our data sets to examine the changes in stratospheric chemistry over a variety of time scales. Ongoing projects include investigating the diurnal variation of OH, HO2, and H2O2 and exploring their relationships with other simultaneously measured species; measuring long term trends in HF and HCl; and looking for changes caused by the June 1991 Pinatubo eruption. We are also continuing to analyze the large set of data collected during the AASE 2.

Traub, Wesley A.↗

Peroxy radical measurements with NCAR's chemical amplifier

The present NCAR instrument for HO2/RO2 measurements has been described previously. It is based on the reactions involving HO2, RO2, and HO radicals with CO and NO. Since (HO2) + (RO2) + (HO) is much greater than (HO) for most atmospheres, it is useful as a peroxy radical detector. Operation of the instrument depends on the creation of a chemical chain reaction which is initiated as HO2 and RO2 radicals in ambient air encounter added NO gas; this forms an NO2 molecule and an HO or RO radical: HO2(RO2) + NO yields HO(RO) + NO2. RO radicals react relatively efficiently with O2 to form an HO2 radical, and subsequently an HO-radical, by reaction with NO. CO gas added to the reaction chamber during part of the operating cycle, recycles the HO to HO2; HO + CO (+O2) yields HO2 + CO2. The reaction sequence may form several hundred NO2 molecules per HO2 (RO2) originally present, before chain termination occurs. The added CO is replaced by N2 addition periodically so that the chain reaction is suppressed, and a 'blank' signal resulting from NO2, O3 and possibly other NO2-forming species (non-chain processes) in ambient air is recorded. The difference between the signal with and without CO is proportional to the peroxy radical concentration. The NO2 produced is monitored using a sensitive luminol chemiluminescence detector system. In the NCAR instrument the length of the amplification chain is determined using a stable source of HO2 radicals (H2O2 thermal decomposition); the ratio of the signal seen with CO present to that with N2 present gives the sensitivity of the instrument to HO2 (molecules of NO2 formed/peroxy radical). The instrument is automated to carry out in hourly repeated cycles: (1) chain length determination; (2) NO2 calibration; and (3) linearity check on the response of signals. One minute averages of signals are normally recorded. The sensitivity of the instrument to detect peroxy radicals is in the pptv range. The present instrument has operated continuously (24 hr/day) in the field studies which extended over a period of several weeks. The major advantages of this instrument are as follows: (1) its relative simplicity; (2) low power requirements; and (3) its rapid response to all types of peroxy radicals--HO2, CH3O2 and the higher alkyl and acyl peroxy radicals; however not all RO2 species generate HO2 radicals with perfect efficiency and hence have somewhat lower response/molecule than HO2 radicals.

Cantrell, Christopher↗

Stability of the Martian atmosphere: Is heterogeneous catalysis essential?

A comprehensive homogeneous gas phase photochemical model is developed to study the problem of stability of the Martian atmosphere. The one-dimensional model extends from the ground up to 220 km, passing through the homopause at 125 km. The model thus couples the lower (neutral) atmosphere to the ionosphere above which provides significant downward flux of carbon monoxide and oxygen atoms. It is concluded on the basic of currently accepted values for globally and seasonally averaged water vapor abundance, dust opacity and the middle atmospheric eddy mixing coefficient, as well as the relevant laboratory data (particularly the temperature dependence of CO2 absorption cross section and the rate constant for CO+OH reaction), that the rate of re-formation of carbon dioxide exceeds its photolytic destruction rate by about 40%. Furthermore, it is found that this result is virtually independent of the choice of eddy mixing coefficient, unless its value in the middle atmosphere exceeds 10(exp 8) sq cm/sec or is far smaller than 10(exp 5)sq cm/sec, or the dust opacity, unless it exceeds unity, or the water vapor mixing ratio at the surface, unless it is far smaller (less than or = 1 ppm) or far greater (greater than or = 500 ppm) than the average value (approximately 150 ppm). Since none of these extremes represent globally and seasonally averaged conditions on Mars, we propose that the present model requires existence of a mechanism to throttle down the recycling rate of carbon dioxide on Mars. Therefore, it is suggested that a heterogeneous process which provides a sink to the species that participate in the recycling of CO2, i.e., H2O, H2O2, OH, CO or O, in particular, may be necessary to bring about the balance between the CO2 recycling rate and its photolytic destruction rate. Aerosols of dust or ice (pure or doped water or carbon dioxide ice present in the atmosphere of Mars) can provide the appropriate adsorption sites for the above heterogeneous process. Despite our conclusion that some heterogeneous process may be needed, it is important to recognize that one-dimensional models can only provide first-order results which, most likely, represent globally and seasonally averaged conditions. However, it is only after actual temporal, latitudinal and longitudinal variations of relevant atmospheric parameters are included in the model that one can determine fuly whether the problem of atmospheric stabiltiy still continues to persist and whether some heterogeneous process is required to correct it.

Atreya, Sushil K.↗

Design of a three-layer antireflection coating for high efficiency indium phosphide solar cells using a chemical oxide as first layer

It is well known that the behavior of III-V compound based solar cells is largely controlled by their surface, since the majority of light generated carriers (63% for GaAs and 79% for InP) are created within 0.2 mu m of the surface of the illuminated cell. Consequently, the always observed high surface recombination velocity (SRV) on these cells is a serious limiting factor for their high efficiency performance, especially for those with p-n junction made by either thermal diffusion or ion implantation. A good surface passivation layer, ideally a grown oxide as opposed to a deposited one, will cause a significant reduction in the SRV without adding interface problems, thus improving the performance of III-V compound based solar cells. Another significant benefit to the overall performance of the solar cells can be achieved by a substantial reduction of their large surface optical reflection by the use of a well designed antireflection (AR) coating. In this paper, we demonstrate the effectiveness of using a chemically grown thermally and chemically stable oxide, not only for surface passivation but also as an integral part of a 3-layer AR coating for thermally diffused p+n InP solar cells. A phosphorus-rich interfacial oxide, In(PO3)3, is grown at the surface of the p+ emitter using an etchant based on HNO3, o-H3PO4 and H2O2. This oxide has the unique properties of passivating the surface as well as serving as an efficient antireflective layer yielding a measured record high AMO open-circuit voltage of 890.3 mV on a thermally diffused InP(Cd,S) solar cell. Unlike conventional single layer AR coatings such as ZnS, Sb2O3, SiO or double layer AR coatings such as ZnS/MgF2 deposited by e-beam or resistive evaporation, this oxide preserves the stoichiometry of the InP surface. We show that it is possible to design a three-layer AR coating for a thermally diffused InP solar cell using the In(PO3)3 grown oxide as the first layer and Al2O3 and MgF2 as the second and third layers respectively, so as to yield an overall theoretical reflectance of less than 2%. Since chemical oxides are readily grown on III-V semiconductors materials, the technique of using the grown oxide layer to both passivate the surface as well as serve as the first of a multilayer AR coating should work well for all III-V compound-based solar cells.

Moulot, Jacques↗

Oxygenic Photosynthesis and the Oxidation State of Mars

The oxidation state of the Earth's surface is one of the most obvious indications of the effect of life on this planet. The surface of Mars is highly oxidized, as evidenced by its red color, but the connection to life is less apparent. Two possibilities can be considered. First, the oxidant may be photochemically produced in the atmosphere. In this case the fundamental source of O2 is the loss of H2 to space and the oxidant produced is H2O2. This oxidant would accumulate on the surface and thereby destroy any organic material and other reductants to some depth. Recent models suggest that diffusion limits this depth to a few meters. An alternative source of oxygen is biological oxygen production followed by sequestration of organic material in sediments - as on the Earth. In this case, the net oxidation of the surface was determined billions of years ago when Mars was a more habitable planet and oxidative conditions could persist to great depths, over 100 m. Below this must be a compensating layer of biogenic organic material. Insight into the nature of past sources of oxidation on Mars will require searching for organics in the martian subsurface and sediments.

Hartman, Hyman↗

A Pilot-Scale Evaluation of a New Technology to Control NO(x) Emissions from Boilers at KSC: Hydrogen Peroxide Injection into Boiler Flue Gases Followed by Wet Scrubbing of Acid Gases

Emissions of nitrogen oxides NO(x) are a significant problem in the United States. NO(x) are formed in any combustion process, therefore it is not surprising that NO(x) are emitted from the boilers at KSC. Research at UCF has shown (in the laboratory) that injecting H2O2 into hot simulated flue gases can oxidize the NO and NO2 to their acid gas forms, HNO2 and HNO3, respectively. These acid gases are much more water soluble than their counterparts, and theoretically can be removed easily by wet scrubbing. This technology was of interest to NASA, both for their boilers at KSC, and for their combustion sources elsewhere. However, it was necessary to field test the technology and to provide pilot-scale data to aid in design of full-scale facilities. Hence this project was initiated in May of 1996.

Cooper, C. David↗

On the Stereoselective Synthesis of (+)-Pinoresinol in Forsythia Suspensa from its Achiral Precursor, Coniferyl Alcohol

The residue from Forsythia suspensa stems, upon removal of soluble enzymes, has provided the first evidence for a stereoselective coupling enzyme in lignan biosynthesis. This preparation catalyses the preferred formation (ca 65%) of (+)-[8,8'- C-14] pinoresinol from [8-C-14]coniferyl alcohol in the absence of exogenously provided cofactors; addition of H2O2 had little effect on enantiomeric composition. However, when NAD and malate were supplied, the stereoselectivity of the coupling reaction was significantly enhanced and pinoresinol consisting of ca 80% of the (+)-antipode was obtained. Clearly, the insoluble residue contains a specific coupling enzyme which catalyses (+)-pinoresinol formation from coniferyl alcohol. By contrast, when [8- C-14] sinapyl alcohol was employed as substrate, only racemic syringaresinols were formed: this non-stereoselective peroxidase-catalysed coupling reaction presumably accounts for the low levels of (-)-pinoresinol encountered in this system when coniferyl alcohol is used as a substrate.

Davin, Laurence B.↗

Stereoselectivity in Polyphenol Biosynthesis

Stereoselectivity plays an important role in the late stages of phenyl-propanoid metabolism, affording lignins, lignans, and neolignans. Stereoselectivity is manifested during monolignol (glucoside) synthesis, e.g., where the geometry (E or Z) of the pendant double bond affects the specificity of UDPG:coniferyl alcohol glucosyltransferases in different species. Such findings are viewed to have important ramifications in monolignol transport and storage processes, with roles for both E- and Z-monolignols and their glucosides in lignin/lignan biosynthesis being envisaged. Stereoselectivity is also of great importance in enantiose-lective enzymatic processes affording optically active lignans. Thus, cell-free extracts from Forsythia species were demonstrated to synthesize the enantiomerically pure lignans, (-)-secoisolariciresinol, and (-)-pinoresinol, when NAD(P)H, H2O2 and E-coniferyl alcohol were added. Progress toward elucidating the enzymatic steps involved in such highly stereoselective processes is discussed. Also described are preliminary studies aimed at developing methodologies to determine the subcellular location of late-stage phenylpropanoid metabolites (e.g., coniferyl alcohol) and key enzymes thereof, in intact tissue or cells. This knowledge is essential if questions regarding lignin and lignan tissue specificity and regulation of these processes are to be deciphered.

Lewis, Norman G.↗

Chemical Characteristics of Continental Outflow Over the Tropical South Atlantic Ocean from Brazil and Africa

The chemical characteristics of air parcels over the tropical South Atlantic during September - October 1992 are summarized by analysis of aged marine and continental outflow classifications. Positive correlations between CO and CH3CL and minimal enhancements of C2CL40, and various ChloroFluoroCarbon (CFC) species in air parcels recently advected over the South Atlantic basin strongly suggest an impact on tropospheric chemistry from biomass burning on adjacent continental areas of Brazil and Africa. Comparison of the composition of aged Pacific air with aged marine air over the South Atlantic basin from 0.3 to 12.5 km altitude indicates potential accumulation of long-lived species during the local dry season. This may amount to enhancements of up to two-fold for C2H6, 30% for CO, and 10% for CH3Cl. Nitric oxide and NO(x) were significantly enhanced (up to approx. 1 part per billion by volume (ppbv)) above 10 km altitude and poorly correlated with CO and CH3Cl. In addition, median mixing ratios of NO and NO(x) were essentially identical in aged marine and continental outflow air masses. It appears that in addition to biomass burning, lightning or recycled reactive nitrogen may be an important source of NO(x) to the upper troposphere. Methane exhibited a monotonic increase with altitude from approx. 1690 to 1720 ppbv in both aged marine and continental outflow air masses. The largest mixing ratios in the upper troposphere were often anticorrelated with CO, CH3Cl, and CO2, suggesting CH, contributions from natural sources. We also argue, based on CH4/CO ratios and relationships with various hydrocarbon and CFC species, that inputs from biomass burning and the northern hemisphere are unlikely to be the dominant sources of CO, CH4 and C2H6 in aged marine air. Emissions from urban areas would seem to be necessary to account for the distribution of at least CH4 and C2H6. Over the African and South American continents an efficient mechanism of convective vertical transport coupled with large-scale circulations conveys biomass burning, urban, and natural emissions to the upper troposphere over the South Atlantic basin. Slow subsidence over the eastern South Atlantic basin may play an important role in establishing and maintaining the rather uniform vertical distribution of long-lived species over this region. The common occurrence of values greater than 1 for the ratio CH3OOH/H2O2 in the upper troposphere suggests that precipitation scavenging effectively removed highly water soluble gases (H2O2, HNO3, HCOOH, and CH3COOH) and aerosols during vertical convective transport over the continents. However, horizontal injection of biomass burning products over the South Atlantic, particularly water soluble species and aerosol particles, was frequent below 6 km altitude.

Talbot, R. W.↗

Origin of Ozone NO(x) in the Tropical Troposphere: A Photochemical Analysis of Aircraft Observations Over the South Atlantic Basin

The photochemistry of the troposphere over the South Atlantic basin is examined by modeling of aircraft observations up to 12-km altitude taken during the TRACE A expedition in September-October 1992. A close balance is found in the 0 to 12-km column between photochemical production and loss Of O3, with net production at high altitudes compensating for weak net loss at low altitudes. This balance implies that O3 concentrations in the 0-12 km column can be explained solely by in situ photochemistry; influx from the stratosphere is negligible. Simulation of H2O2, CH3OOH, and CH2O concentrations measured aboard the aircraft lends confidence in the computations of O3 production and loss rates, although there appears to be a major gap in current understanding of CH2O chemistry in the marine boundary layer. The primary sources of NO(x) over the South Atlantic Basin appear to be continental (biomass burning, lightning, soils). There is evidence that NO(x) throughout the 0 to 12-km column is recycled from its oxidation products rather than directly transported from its primary sources. There is also evidence for rapid conversion of HNO3 to NO(x) in the upper troposphere by a mechanism not included in current models. A general representation of the O3 budget in the tropical troposphere is proposed that couples the large scale Walker circulation and in situ photochemistry. Deep convection in the rising branches of the Walker circulation injects NO(x) from combustion, soils, and lightning to the upper troposphere, leading to O3 production; eventually, the air subsides and net O3 loss takes place in the lower troposphere, closing the O3 cycle. This scheme implies a great sensitivity of the oxidizing power of the atmosphere to NO(x) emissions in the tropics.

Jacob, D. J.↗

Chemical Schemes for Surface Modification of Icy Satellites: A Road Map

The icy Galilean satellites of Jupiter are subject to magnetospheric plasma ion bombardment, which induces chemical changes within the ice. The possible detection of CO2 on the surface of Ganymede by the Galileo spacecraft makes for a more complicated chemistry and increases the number of chemical compounds that may then be present. We outline chemical schemes for the irradiation of pure and mixed ices H2O/CO2 and suggest species which observers may detect on Europa, Ganymede, and Callisto, such as C3O2, H2CO3, H2O2, CO3, HO2, CO, H2CO, CH2CO, as well as K2O, KOH, and SO3, from plasma implantation. Column abundances of compounds in the ice are calculated using a specified energy input and G values (yield per 100 eV).

Delitsky, Mona L.↗

SONEX-Hydrogen Peroxide, Methylhydroperoxide and Formaldehyde Measurements

We measured gas phase H2O2, CH3OOH, and CH2O on board the NASA DC-8 during the SONEX field mission, presented preliminary results at three scientific meetings, participated in two data workshops and contributed to joint publications of final results. The observations of peroxides and formaldehyde were instrumental in assessing odd-hydrogen radical chemistry, ozone chemistry, and in tracing meteorological transport paths.

Heikes, Brian↗