Results for “Microwave chemistry” — Page 14

NASA NTRS2011

Discovery of Interstellar Anions in Cepheus and Auriga

We report the detection of microwave emission lines from the hydrocarbon anion C6H(-) and its parent neutral C6H in the star-forming region LI251 A (in Cepheus), and the pre-stellar core LI512 (in Auriga). The carbon chain-bearing species C4H, HC3N, HC5N, HC7N, and C3S are also detected in large abundances. The observations of L1251A constitute the first detections of anions and long-chain polyynes and cyanopolyynes (with more than five carbon atoms) in the Cepheus Flare star-forming region, and the first detection of anions in the vicinity of a protostar outside of the Taurus molecular cloud complex, indicating a possible wider importance for anions in the chemistry of star formation. Rotational excitation temperatures have been derived from the HC3N hyperfine structure lines and are found to be 6.2 K for L1251A and 8.7 K for LI5l2. The anion-to-neutral ratios are 3.6% and 4.1%, respectively, which are within the range of values previously observed in the interstellar medium, and suggest a relative uniformity in the processes governing anion abundances in different dense interstellar clouds. This research contributes toward the growing body of evidence that carbon chain anions are relatively abundant in interstellar clouds throughout the Galaxy, but especially in the regions of relatively high density and high depletion surrounding pre-stellar cores and young, embedded protostars.

Cordiner, M. A.↗

DOE OSTI2022

Establishing Self-Dopant Design Principles from Structure–Function Relationships in Self-n-Doped Perylene Diimide Organic Semiconductors

Self-doping is a particular doping method that has been applied to a wide range of organic semiconductors. However, there is a lack of understanding regarding the relationship between dopant structure and function. A structurally diverse series of self-n-doped perylene diimides (PDIs) is investigated to study the impact of steric encumbrance, counterion selection, and dopant/PDI tether distance on functional parameters such as doping, stability, morphology, and charge-carrier mobility. The studies show that self-n-doping is best enabled by the use of sterically encumbered ammoniums with short tethers and Lewis basic counterions. Additionally, water is found to inhibit doping, which concludes that thermal degradation is merely a phenomenological feature of certain dopants, and that residual solvent evaporation is the primary driver of thermally activated doping. In situ grazing-incidence wide-angle X-ray scattering studies show that sample annealing increases the π–π stacking distance and shrinks grain boundaries for improved long-range ordering. These features are then correlated to contactless carrier-mobility measurements with time-resolved microwave conductivity before and after thermal annealing. In conclusion, the collective relationships between structural features and functionality are finally used to establish explicit self-n-dopant design principles for the future design of materials with improved functionality.

36 MATERIALS SCIENCE↗

NASA NTRS2006

Long-term Evolution of Upper Stratospheric Ozone at Selected Stations of the Network for the Detection of Stratospheric Change (NDSC)

The long-term evolution of upper stratospheric ozone has been recorded by lidars and microwave radiometers within the ground-based Network for the Detection of Stratospheric Change (NDSC), and by the space-borne Solar Backscatter Ultra-Violet instruments (SBUV), Stratospheric Aerosol and Gas Experiment (SAGE), and Halogen Occultation Experiment (HALOE). Climatological mean differences between these instruments are typically smaller than 5% between 25 and 50 km. Ozone anomaly time series from all instruments, averaged from 35 to 45 km altitude, track each other very well and typically agree within 3 to 5%. SBUV seems to have a slight positive drift against the other instruments. The corresponding 1979 to 1999 period from a transient simulation by the fully coupled MAECHAM4-CHEM chemistry climate model reproduces many features of the observed anomalies. However, in the upper stratosphere the model shows too low ozone values and too negative ozone trends, probably due to an underestimation of methane and a consequent overestimation of ClO. The combination of all observational data sets provides a very consistent picture, with a long-term stability of 2% or better. Upper stratospheric ozone shows three main features: (1) a decline by 10 to 15% since 1980, due to chemical destruction by chlorine; (2) two to three year fluctuations by 5 to 10%, due to the Quasi-Biennial Oscillation (QBO); (3) an 11-year oscillation by about 5%, due to the 11-year solar cycle. The 1979 to 1997 ozone trends are larger at the southern mid-latitude station Lauder (45 S), reaching 8%/decade, compared to only about 6%/decade at Table Mountain (35 N), Haute Provence/Bordeaux (approximately equal to 45 N), and Hohenpeissenberg/Bern(approximately equal to 47 N). At Lauder, Hawaii (20 N), Table Mountain, and Haute Provence, ozone residuals after subtraction of QBO- and solar cycle effects have levelled off in recent years, or are even increasing. Assuming a turning point in January 1997, the change of trend is largest at southern mid-latitude Lauder, +11%/decade, compared to +7%/decade at northern mid-latitudes. This points to a beginning recovery of upper stratospheric ozone. However, chlorine levels are still very high and ozone will remain vulnerable. At this point the most northerly mid-latitude station, Hohenpeissenberg/Bern differs from the other stations, and shows much less clear evidence for a beginning recovery, with a change of trend in 1997 by only +3%/decade. In fact, record low upper stratospheric ozone values were observed at Hohenpeissenberg/Bern, and to a lesser degree at Table Mountain and Haute Provence, in the winters 2003/2004 and 2004/2005.

Steinbrecht, W.↗

NASA NTRS2009

On the Quality of the Nimbus 7 LIMS Version 6 Water Vapor Profiles and Distributions

This report describes the quality of the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) water vapor (H2O) profiles of 1978/79 that were processed with a Version 6 (V6) algorithm and archived in 2002. The V6 profiles incorporate a better knowledge of the instrument attitude for the LIMS measurements along its orbits, leading to improvements for its temperature profiles and for the registration of its water vapor radiances with pressure. As a result, the LIMS V6 zonal-mean distributions of H2O exhibit better hemispheric symmetry than was the case from the original Version 5 (V5) dataset that was archived in 1982. Estimates of the precision and accuracy of the V6 H2O profiles are developed and provided. Individual profiles have a precision of order 5% and an estimated accuracy of about 19% at 3 hPa, 14% at 10 hPa, and 26% at 50 hPa. Profile segments within about 2 km of the tropopause are often affected by emissions from clouds that appear in the finite field-of-view of the detector for the LIMS H2O channel. Zonally-averaged distributions of the LIMS V6 H2O are compared with those from the more recent Microwave Limb Sounder (MLS) satellite experiment for November, February, and May of 2004/2005. The patterns and values of their respective distributions are similar in many respects. Effects of a strengthened Brewer-Dobson circulation are indicated in the MLS distributions of the recent decade versus those of LIMS from 1978/79. A tropical tape recorder signal is present in the 7-month time series of LIMS V6 H2O with lowest values in February 1979, and the estimated, annually-averaged "entry-level" H2O is 3.5 to 3.8 ppmv. It is judged that this historic LIMS water vapor dataset is of good quality for studies of the near global-scale chemistry and transport for pressure levels from 3 hPa to about 70 to 100 hPa.

Remsberg, E. E.↗

NASA NTRS2012

Recent Advances in Ozone Data Assimilation at the GMAO - Towards a New Reanalysis

This presentation summarized ongoing work on improving the representation of ozone in the GEOS Data Assimilation Systems. Data from two EOS Aura sensors was used: the total column ozone from the Ozone Monitoring Instrument (OMI) and high vertical resolution stratospheric profiles from Microwave Limb Sounder (MLS, version 3.3). As several previous studies have demonstrated, assimilation of this data can constrain the stratospheric and tropospheric ozone columns with relatively good accuracy. However, the representation of the vertical structures in the troposphere and near tropopause region is often deficient. Since both these layers of the atmosphere are critical to the understanding of the radiative forcing as well as the ozone budget in the troposphere, current work will focus on improving the assimilated product between the surface and the 50 hPa pressure level. The discussion included recent steps that have been taken towards refining the treatment of ozone in GEOS-5. Impacts of improved tropospheric chemistry model were discussed including the introduction of efficiency factors ("averaging kernels") for OMI total ozone, and direct assimilation of radiances from the MLS instrument. In particular, advantages and challenges involved in assimilating limb radiances rather than retrieved product were discussed. This work is, in part, a preparation for a planned reanalysis of the EOS Aura data from 2005 to present.

Krzysztof, Wargan↗

NASA NTRS2012

The Response of Lower Atmospheric Ozone to ENSO in Aura Measurements and a Chemistry-Climate Simulation

The El Nino-Southern Oscillation (ENSO) is the dominant mode of tropical variability on interannual time scales. ENSO appears to extend its influence into the chemical composition of the tropical troposphere. Recent work has revealed an ENSO-induced wave-1 anomaly in observed tropical tropospheric column ozone. This results in a dipole over the western and eastern tropical Pacific, whereby differencing the two regions produces an ozone anomaly with an extremely high correlation to the Nino 3.4 Index. We have successfully reproduced this feature using the Goddard Earth Observing System Version 5 (GEOS-5) general circulation model coupled to a comprehensive stratospheric and tropospheric chemical mechanism forced with observed sea surface temperatures over the past 25 years. An examination of the modeled ozone field reveals the vertical contributions of tropospheric ozone to the column over the western and eastern Pacific region. We will show composition sensitivity in observations from NASA s Aura satellite Microwave Limb Sounder (MLS) and the Tropospheric Emissions Spectrometer (TES) and a simulation to provide insight into the vertical structure of these ENSO-induced ozone changes. The ozone changes due to the Quasi-Biennial Oscillation (QBO) in the extra-polar upper troposphere and lower stratosphere in MLS measurements will also be discussed.

Oman, L. D.↗

DOE OSTI2022

High-resolution infrared spectroscopy of supersonically cooled singlet carbenes: Bromomethylene (HCBr) in the CH stretch region

First high-resolution spectra of cold (~35 K) singlet bromomethylene HCBr in the CH stretching (v 1 ) region from 2770 to 2850 cm-1 are reported using near quantum shot-noise limited laser absorption methods in a slit jet supersonic discharge expansion source. Three rovibrational bands are identified at high S/N (20:1 - 40:1) and rotationally assigned to i) the CH stretch fundamental (v 1 ) band $\tilde{X}$(1,0,0) ← $\tilde{X}$ (0,0,0) and ii) vibrational hot bands ($\tilde{X}$(1,1,0) ← $\tilde{X}$(0,1,0) and $\tilde{X}$(1,0,1) ← $\tilde{X}$(0,0,1)) arising from vibrationally excited HCBr populated in the discharge with single quanta in either the H–C–Br bend (v 2 ) or C–Br stretch (v 3 ) modes. Precision rotational constants are reported for a total of six states, with an experimentally determined CH stretch vibrational frequency (2799.38 cm -1 ) in good agreement with previous low-resolution fluorescence studies. Detailed analysis of the fundamental v 1 band highlights the presence of perturbations in the $\tilde{X}$(1,0,0) level, which we tentatively attribute to arise from the nearby triplet state $\tilde{a}$(0,0,1) through spin-orbit interaction or the multiple quanta $\tilde{X}$(0,2,1) singlet state via c-type Coriolis coupling. Reduced-Doppler resolution (60 MHz) in the slit-jet IR spectrometer permits clear observation of nuclear spin hyperfine structure, with experimental line shapes well reproduced by nuclear quadrupole/spin-rotation coupling constants from microwave studies. Lastly, the a-type to b-type transition intensity ratio for the fundamental CH stretch band is notably larger than predicted by a bond-dipole model, which from high level ab initio quantum calculations (CCSD(T)/PVQZ) can be attributed to vibrationally induced “charge-sloshing” of electron density along the polar C–Br bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1995

Characterization of silicon-carbon clusters by infrared laser spectroscopy. The nu 1 band of SiC4

The nu 1 fundamental vibration of linear SiC4 has been observed by infrared diode laser spectroscopy of a supersonic cluster beam. Twenty-four rovibrational transitions were measured in the spectral region of 2094.6 to 2097.1 cm-1, the rotational temperature was 10 K. A combined least-squares fit of these transitions with previously reported microwave data yielded the following molecular constants: nu 1 = 2095.45806(37) cm-1, B" = 0.051161131(52) cm-1, and B' = 0.0509157(96) cm-1. These results are compared to vibrational spectroscopy measurements of SiC4 trapped in a solid Ar matrix and to ab initio calculations.

NASA Discipline Exobiology↗

NASA NTRS1982

CO2 lidar for measurements of trace gases and wind velocities

CO2 lidar systems technology and signal processing requirements relevant to measurement needs and sensitivity are discussed. Doppler processing is similar to microwave radar, with signal reception controlled by a computer capable of both direct and heterodyne operations. Trace gas concentrations have been obtained with the NASA DIAL system, and trace gas transport has been determined with Doppler lidar measurements for wind velocity and turbulence. High vertical resolution measurement of trace gases, wind velocity, and turbulence are most important in the planetary boundary layer and in regions between the PBL and the lower stratosphere. Shear measurements are critical for airport operational safety. A sensitivity analysis for heterodyne detection with the DIAL system and for short pulses using a Doppler lidar system is presented. The development of transient injection locking techniques, as well as frequency stability by reducing chirp and catalytic control of closed cycle CO2 laser chemistry, is described.

Hess, R. V.↗

NASA NTRS1990

Submillimeter and millimeter observations of solar system objects

Microwave spectroscopy of solar system objects was supported. It necessarily involves millimeter and submillimeter wavelengths where rotational transitions reside. The existing national facilities are at OVRO, the 12-meter at Kitt Peak, UC array at Hat Creek, the Caltech CSO on Mauna Kea, and the 14-meter at the Univ. of Massachusetts, near Amherst. The group used all of these instruments in the last year except the Univ. of Massachusetts 14-meter. This wavelength range (0.3 to 3 mm) is about to enjoy an explosion of interest as submillimeter receivers become better and easier to use. This region of the spectrum is rich in transitions of molecules that exist in the planetary atmospheres which can be studied for temperature-pressure profiles, wind tracers, and atmospheric chemistry. The list of solar system objects that have been recently addressed with these techniques include: (1) Venus: CO studies of T-P profiles, winds, and photochemistry; SO2 detections; Continuum mapping remains to be done at 1 mm; (2) Earth H2O, CO, NO, NO2, O(18)O, etc. as a test bed for other atmospheres; (3) Mars: H2O, CO, O(18)O studies of T-P profiles, winds (fall of 1990), and photochemistry; (4) Saturn: Same as Jupiter plus submillimeter and millimeter mapping of the ring system; (5) Uranus and Neptune: Continuum thermal mapping; and (6) Titan: CO, HCN, and HC3NT-P information and photochemistry. Recent results are given.

Muhleman, Duane O.↗

NASA NTRS1996

On the Capabilities of Using AIRSAR Data in Surface Energy/Water Balance Studies

The capabilities of using remote sensing data, and in particular multifrequency/multipolarization SAR data, like AIRSAR, for the retrieval of surface parameters, depend considerably on the specificity of each application. The potentials, and limitations, of SAR data in ecological investigations are well known. Because the chemistry is a major component in such studies and because of the almost lacking chemical information at the wavelengths of SAR data, the capabilities of using SAR-derived information in such studies are considerably limited. However, in the case of surface energy/water balance studies, the determination of the amount of water content, both in the soil and in the plants, is a major component in all modeling approaches. As the information about water content is present in the SAR signal, then the role of SAR data in studies where water content is to be determined becomes clearly predominant. Another situation where the role of SAR data becomes dominant over other remote sensing systems is the case of dense canopies. Because of the penetration capabilities of microwave data, which is especially superior as compared to optical data, information about the canopy as a whole and even the underlying soil is contained in the SAR data, while only the top canopy provides the information content in the case of optical data. In the case of relatively dense canopies, as has been demonstrated in this study, such different penetration capabilities provide very different results in terms of the derived total canopy water content, for instance. However, although all such capabilities are well known, unfortunately there are also well known limitations. Apart from calibration-related aspects (that we will not consider in this study), and apart from other intrinsic problems (like image noise, topographic corrections, etc.) which also significantly affect the derived results, we will concentrate on the problem of extracting information from the data. Even at this level, methods are still not fully well established, especially over vegetation-covered areas. In this paper, an algorithm is described which allows derivation of three fundamental parameters from SAR data: soil moisture, soil roughness and canopy water content, accounting for the effects of vegetation cover by using optical (Landsat) data as auxiliary. Capabilities and limitations of the data and algorithms are discussed, as well as possibilities to use these data in energy/water balance modeling studies. All the data used in this study were acquired as part of the Intensive Observation Period in June-July 1991 (European Multisensor Aircraft Campaign-91), as part of the European Field Experiment in a Desertification- threatened Area (EFEDA), a European contribution to the global-change research sponsored by the IGBP program (Bolle et al., 1993).

Moreno, Jose F.↗

NASA NTRS1986

The organic aerosols of Titan

A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan prepared by continuous dc discharge through a 0.9 N2/0.1 CH4 gas mixture at 0.2 mb is determined from X-ray to microwave frequencies. Values of n (approx. 1.65) and k (approx. 0.004 to 0.08) in the visible are consistent with deductions made by groundbased and spaceborne observations of Titan. Many infrared absorption features are present in k(lambda), including the 4.6 micrometer nitrile band. Molecular analysis of the volatile components of this tholin was performed by sequential and nonsequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycylic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition,acid hydrolysis produces a racemic mixture of biological and nonbiological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.

Khare, B. N.↗

NASA NTRSDate not supplied

GEOS Constituent Data Assimilation beyond Aura MLS: Assimilating NASA SAGE III/ISS profiles of stratospheric water vapor

Water vapor in the lower stratosphere is an important trace gas for atmospheric chemistry and radiative budget with direct impact on climate. During the last quarter of the 20th century, the Stratospheric Aerosol and Gas Experiment (SAGE) missions were crucial in monitoring the stratospheric ozone loss and the subsequent recovery as well as trends in water vapor linked to surface temperature trends. The SAGE III instrument aboard the International Space Station (ISS) continues the SAGE mission record, with high vertical resolution profiles of water vapor (and other constituents) since mid-2017. The NASA GEOS Earth system model has the capability to assimilate multi-constituents from ground and space-based instruments using the GEOS Constituent Data Assimilation System (CoDAS). Reanalysis products of stratospheric water vapor without data constraints are historically poor, and two recent reanalyses which assimilated stratospheric constituents observed by the Microwave Limb Sounder (MLS) improve the representation of stratospheric composition, including water vapor, when compared against independent observations. The MLS instrument is on NASA's Aura satellite which is expected to be decommissioned in the coming years. Here we demonstrate that while the number of solar occultation observations a day from SAGE III/ISS is about 1 % of the total number of profiles observed globally by MLS, the chemical timescales of water vapor in the lower stratosphere are long enough that the SAGE III/ISS data can provide a useful constraint on the assimilated product. Analyzed water vapor fields from assimilating only SAGE III/ISS water vapor profiles agree well with independent stratospheric observations, including when compared against the frost-point hygrometers at the three NOAA stations. Over the five-year period from 2017 through 2022, the analyzed water vapor using SAGE III/ISS captures many of the features seen with the assimilation of MLS observations. Note, this ability is reduced over regions where the SAGE III/ISS instrument provides infrequent or no observations (associated with the orbit of the ISS), as highlighted in the case study period following the eruption of the tropical underwater volcano Hunga Tonga in early 2022. Nevertheless, there is a clear benefit to the assimilation of stratospheric water vapor from SAGE III/ISS observations, allowing us to continue to monitor stratospheric composition for climate assessments following the impending loss of Aura.

K. Emma Knowland↗

NASA NTRSDate not supplied

GEOS Constituent Data Assimilation Beyond Aura MLS: Assimilating NASA SAGE III/ISS Profiles of Stratospheric Water Vapor

Water vapor in the lower stratosphere is an important trace gas for atmospheric chemistry and radiative budget with direct impact on climate. During the last quarter of the 20th century, the Stratospheric Aerosol and Gas Experiment (SAGE) missions were crucial in monitoring the stratospheric ozone loss and the subsequent recovery as well as trends in water vapor linked to surface temperature trends. The SAGE III instrument aboard the International Space Station (ISS) continues the SAGE mission record, with high vertical resolution profiles of water vapor (and other constituents) since mid-2017. The NASA GEOS Earth system model has the capability to assimilate multi-constituents from ground and space-based instruments using the GEOS Constituent Data Assimilation System (CoDAS). Reanalysis products of stratospheric water vapor without data constraints are historically poor, and two recent reanalyses which assimilated stratospheric constituents observed by the Microwave Limb Sounder (MLS) improve the representation of stratospheric composition, including water vapor, when compared against independent observations. The MLS instrument is on NASA's Aura satellite which is expected to be decommissioned in the coming years. Here we demonstrate that while the number of solar occultation observations a day from SAGE III/ISS is about 1 % of the total number of profiles observed globally by MLS, the chemical timescales of water vapor in the lower stratosphere are long enough that the SAGE III/ISS data can provide a useful constraint on the assimilated product. Analyzed water vapor fields from assimilating only SAGE III/ISS water vapor profiles agree well with independent stratospheric observations, including when compared against the frost-point hygrometers at the three NOAA stations. Over the five-year period from 2017 through 2022, the analyzed water vapor using SAGE III/ISS captures many of the features seen with the assimilation of MLS observations. Note, this ability is reduced over regions where the SAGE III/ISS instrument provides infrequent or no observations (associated with the orbit of the ISS), as highlighted in the case study period following the eruption of the tropical underwater volcano Hunga Tonga in early 2022. Nevertheless, there is a clear benefit to the assimilation of stratospheric water vapor from SAGE III/ISS observations, allowing us to continue to monitor stratospheric composition for climate assessments following the impending loss of Aura.

K. Emma Knowland↗

NASA NTRSDate not supplied

GEOS Constituent Data Assimilation Beyond Aura MLS: Assimilating NASA SAGE III/ISS Profiles of Stratospheric Water Vapor

Water vapor in the lower stratosphere is an important trace gas for atmospheric chemistry and radiative budget with direct impact on climate. During the last quarter of the 20th century, the Stratospheric Aerosol and Gas Experiment (SAGE) missions were crucial in monitoring the stratospheric ozone loss and the subsequent recovery as well as trends in water vapor linked to surface temperature trends. The SAGE III instrument aboard the International Space Station (ISS) continues the SAGE mission record, with high vertical resolution profiles of water vapor (and other constituents) since mid-2017. The NASA GEOS Earth system model has the capability to assimilate multi-constituents from ground and space-based instruments using the GEOS Constituent Data Assimilation System (CoDAS). Reanalysis products of stratospheric water vapor without data constraints are historically poor, and two recent reanalyses which assimilated stratospheric constituents observed by the Microwave Limb Sounder (MLS) improve the representation of stratospheric composition, including water vapor, when compared against independent observations. The MLS instrument is on NASA's Aura satellite which is expected to be decommissioned in the coming years. Here we demonstrate that while the number of solar occultation observations a day from SAGE III/ISS is about 1 % of the total number of profiles observed globally by MLS, the chemical timescales of water vapor in the lower stratosphere are long enough that the SAGE III/ISS data can provide a useful constraint on the assimilated product. Analyzed water vapor fields from assimilating only SAGE III/ISS water vapor profiles agree well with independent stratospheric observations, including when compared against the frost-point hygrometers at the three NOAA stations. Over the five-year period from 2017 through 2022, the analyzed water vapor using SAGE III/ISS captures many of the features seen with the assimilation of MLS observations. Note, this ability is reduced over regions where the SAGE III/ISS instrument provides infrequent or no observations (associated with the orbit of the ISS), as highlighted in the case study period following the eruption of the tropical underwater volcano Hunga Tonga in early 2022. Nevertheless, there is a clear benefit to the assimilation of stratospheric water vapor from SAGE III/ISS observations, allowing us to continue to monitor stratospheric composition for climate assessments following the impending loss of Aura.

K. Emma Knowland↗

DOE OSTI2021

Optoelectronic property comparison for isostructural Cu 2 BaGeSe 4 and Cu 2 BaSnS 4 solar absorbers

To target mitigation of anti-site defect formation in Cu 2 ZnSnS 4–x Se x , a new class of chalcogenides, for which Ba or Sr (group 2) replace Zn (group 12), has recently been introduced for prospective solar absorber application. Cu 2 BaGeSe 4 (CBGSe) and Cu 2 BaSnS 4 (CBTS) are two such compounds, which share a common trigonal crystal structure (P3 1 space group) and similar quasi-direct band gap (~2 eV). While CBTS-based films have already been studied, there are no reports yet on films and solar cells based on related CBGSe. To identify key differences and similarities in the electronic properties between these two materials, electronic characteristics (e.g., carrier concentration, mobility, electron affinity, defect levels, recombination, and charge carrier kinetics) of vacuum-deposited CBGSe and CBTS films are compared using a variety of characterization methods. Hall effect measurements reveal that CBGSe films have relatively higher hole carrier concentration and lower mobility (3 × 10 15 cm –3 , 0.6 cm 2 V –1 s –1 ) compared to CBTS (5 × 10 12 cm –3 , 3.5 cm 2 V –1 s –1 ). Photoelectron spectroscopy yields low electron affinity values for both CBGSe (3.7 eV) and CBTS (3.3 eV), pointing to the necessity of pursuing low electron affinity buffer materials for both types of absorbers. At low temperatures, CBGSe films show free-exciton photoluminescence, as well as pronounced deep-level emission at ~1.4 eV, while CBTS films exhibit a strong bound-exciton signal with noticeably less intense deep-level emission than for CBGSe. Charge carrier kinetics, transport, and recombination properties of both types of films are also analyzed using optical-pump terahertz-probe spectroscopy and time-resolved microwave conductivity. The first CBGSe prototype solar cells (using chemical bath deposited CdS as a buffer layer) show a maximum of 1.5% efficiency with ~0.62 V open-circuit voltage. Furthermore, the measured properties point to possible limiting factors for CBGSe and related films for PV and optoelectronics and provide insights on possible approaches for improvement within this multinary chalcogenide family.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1984

Laboratory degradation of Kapton in a low energy oxygen ion beam

An atomic oxygen ion beam, accelerated from a tunable microwave resonant cavity, was used at Lewis Research Center to bombard samples of the widely used polyimide Kapton. The Kapton experienced degradation and mass loss at high rates, which may be comparable to those found in Space Shuttle operations if the activation energy supplied by the beam enabled surface reactions with the ambient oxygen. The simulation reproduced the directionality (ram-wake dependence) of the degradation, the change in optical properties of the degraded materials, and the structure seen in scanning electron micrographs of samples returned on the Shuttle Trails with a substituted argon ion beam produced no rapid degradation. Energy Dispersive X-ray Analysis (EDAX) showed significant surface composition changes in all bombarded samples. Mass loss rates and surface composition changes are discussed in terms of the possible oxidation chemistry of the interaction. Finally, the question of how the harmful degradation of materials in low Earth orbit can be minimized is addressed.

Ferguson, D. C.↗

NASA NTRS1983

Laboratory degradation of Kapton in a low energy oxygen ion beam

An atomic oxygen ion beam, accelerated from a tunable microwave resonant cavity, was used at Lewis Research Center to bombard samples of the widely used polyimide Kapton. The Kapton experienced degradation and mass loss at high rates, which may be comparable to those found in Space Shuttle operations if the activation energy supplied by the beam enabled surface reactions with the ambient oxygen. The simulation reproduced the directionality (ram-wake dependence) of the degradiation, the change in optical properties of the degraded materials, and the structure seen in scanning electron micrographs of samples returned on the Shuttle Trails with a substituted argon ion beam produced no rapid degradation. Energy Dispersive X-ray Analysis (EDAX) showed significant surface composition changes in all bombarded samples. Mass loss rates and surface composition changes are discussed in terms of the possible oxidation chemistry of the interaction. Finally, the question of how the harmful degradation of materials in low earth orbit can be minimized is addressed.

Ferguson, D. C.↗