The Effects of Chromophore Halogenation on the Stability of UV-Absorbing Organic Solar Cells
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We present new UV spectra of the nucleus of the Seyfert 1 galaxy NGC 5548, which we obtained with the Space Telescope Imaging Spectrograph at high spectral resolution, in conjunction with simultaneous Chandra X-ray Observatory spectra. Taking advantage of the low UV continuum and broad emission-line fluxes, we have determined that the deepest UV absorption component covers at least a portion of the inner, high-ionization narrow-line region (NLR). We find nonunity covering factors in the cores of several kinematic components, which increase the column density measurements of N V and C IV by factors of 1.2 to 1.9 over the full-covering case; however, the revised columns have only a minor effect on the parameters derived from our photoionization models. For the first time, we have simultaneous N V and C IV columns for component 1 (at -1040 km/s), and find that this component cannot be an X-ray warm absorber, contrary to our previous claim based on nonsimultaneous observations. We find that models of the absorbers based on solar abundances severely overpredict the O VI columns previously obtained with the Far Ultraviolet Spectrograph, and present arguments that this is not likely due to variability. However, models that include either enhanced nitrogen (twice solar) or dust, with strong depletion of carbon in either case, are successful in matching all of the observed ionic columns. These models result in substantially lower ionization parameters and total column densities compared to dust-free solar-abundance models, and produce little O VII or O VIII, indicating that none of the UV absorbers are X-ray warm absorbers.
Substantial evidence suggests that a UV Spectrally Absorbing Material (UV-SAM) exists on Triton's surface. This evidence is found in the positive slope in Triton's spectrum from the UV to the near-IR, and the increasing contrast in Triton's light curve in the blue and UV. Although it is now widely-thought that UV-SAM's exist on Triton, little is known about their distribution and spectral properties. The goal of this NDAP Project is to determine the spatial distribution and geological context of the UV-SAM material. We hope to determine if UV-SAM's on Triton are correlated with geologic wind streaks, craters, calderas, geomorphic/topographic units, regions containing (or lacking) volatile frosts, or some other process (e.g., magnetospheric interactions). Once the location and distribution of UV-SAM's has been determined, further constraints on their composition can be made by analyzing the spectrographic data set. To accomplish these goals, various data sets will be used, including Voyager 2 UV and visible images of Triton's surface, IUE and HST spectra of Triton, and a geologic map of the surface based on Voyager 2 and spectrophotometric data. The results of this research will be published in the planetary science literature.
Substantial evidence suggests that a UV spectrally Absorbing Material (UV-SAM) exists on Triton's surface. This evidence is found in the positive slope in Triton's spectrum from the UV to the near-IR, and the increasing contrast in Triton's light curve in the blue and UV. Although it is now widely-thought that UV-SAMs exist on Triton, little is known about their distribution and spectral properties. The goal of this NDAP Project is to determine the spatial distribution and geological context of the UV-SaM material. We hope to determine if UV-SAMs on Triton are correlated with geologic wind streaks, craters, calderas, geomorphic/topographic units, regions containing (or lacking) volatile frosts, or some other process (e.g., magnetospheric interactions). Once the location and distribution of UV-SAMs has been determined, further constraints on their composition cable made by analyzing the spectrographic data set. To accomplish these goals, various data sets will be used, including Voyager 2 UV and visible images of Triton's surface, IUE and HST spectra of Triton, and a geologic map of the surface based on voyager 2 and spectrophotometric data. The results of this research will be published in the planetary science literature.
Substantial evidence suggests that a UV (ultraviolet) Spectrally Absorbing Material (UV-SAM) exists on Triton's surface. This evidence is found in the positive slope in Triton's spectrum from the UV to the near-IR, and the increasing contrast in Triton's light curve in the blue and UV. Although it is now widely-thought that UV-SAM's exist on Triton, little is known about their distribution and spectral properties. The goal of this NDAP Project is to determine the spatial distribution and geological context of the UV-SAM material. We hope to determine if UV-SAM's on Triton are correlated with geologic wind streaks, craters, calderas, geomorphic/topographic units, regions containing (or lacking) volatile frosts, or some other process (e.g., magnetospheric interactions). Once the location and distribution of UV-SAM's has been determined, further constraints on their composition can be made by analyzing the spectrographic data set. To accomplish these goals, various data sets will be used, including Voyager 2 UV and visible images of Triton's surface, IUE and HST spectra of Triton, and a geologic map of the surface based on Voyager 2 and spectrophotometric data. The results of this research will be published in the planetary science literature.
Various common crystalline silicon cell technologies were exposed to UVA radiation (1.24 Wm-2 nm-1 at 340 nm peak) on the front and back faces at 45 degrees Celsius for periods up to 3000 h, representing about 3 y of solar exposure in Phoenix, Arizona, USA. The resulting degradation of the open-circuit voltage and short-circuit current is presented. Of the various cell types examined, significant levels of degradation were seen in all cases. Less degradation was generally found after UV irradiation of cell fronts and older cell types, whereas a bifacial PERC type exposed on the rear showed about 25% degradation in short circuit current, attributable to lack of a diffused surface field. Selected cells were exposed to UV irradiation with the addition of long pass UV filters to replicate UV-absorbers in encapsulants. Modern cell designs are sensitive to UV-ID because of reduced or eliminated front and back surface field and increased dependence on high quality surface passivation. Single transformation of the independent variable (t, kW h/m^2) could be used to achieve a linear model of the data to extrapolate to 50 y. Solar Advisor Model (SAM) shows appropriate filtering of UV-irradiation can improve LCOE and net present value of plant. Some advanced cell types are seen to be UV-resistant (cell level solutions also exist). Solutions therefore exist on the cell, glass, and encapsulant level. Changes over time in each of these would also need to be considered (solarization, encapsulant browning...).
Intermolecular charge-transfer excitons play a central role in determining the performance of organic solar cells as their voltage-dependent formation, dissociation, and recombination dynamics contribute to photocurrent generation, radiative/nonradiative voltage losses, and photovoltaic fill factor. Here, we explore the properties of brightly-emitting wide energy gap (>2 eV) charge transfer excitons by measuring the voltage-dependent photoluminescence, photocurrent, and ultrafast pump–probe transient absorption spectra of organic solar cells employing five UV-absorbing donor molecules that differ only by the length of the oligophenylene or acene group at their core. We find that organic solar cells with a strong correlation between their voltage-dependent photocurrent and charge-transfer exciton photoluminescence have low photovoltaic fill factors as they require voltage to facilitate efficient charge-transfer exciton dissociation. In contrast, solar cells that are efficient can readily generate charges without an applied field and have a separate population of tightly-bound charge-transfer excitons that are responsible for emission. Furthermore, considering that the sum of all excitation loss rates (i.e., recombination and charge extraction) must be equal to the excitation generation rate in the steady state, these voltage-dependent data allow us to solve for the voltage-dependent fate of all excitations in the solar cells and estimate upper and lower bounds for geminate and non-geminate recombination, respectively.
Ultraviolet absorption by atomic oxygen layer in earth atmosphere
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The goal of this program was a comprehensive multiwavelength study of absorption phenomena in active galactic nuclei (AGN). These include a variety of associated absorption systems: X-ray warm absorbers, X-ray cold absorbers. UV absorbers with high ionization lines, MgII absorbers, red quasars and BALQSOs. The aim is to determine the physical conditions in the absorbing outflows, study their inter-relations and their role in AGN. We designed several observing programs to achieve this goal: X-ray spectroscopy, UV spectroscopy, FLAY spectroscopy and X-ray imaging. We were very successful towards achieving the goal over the five year period as shown through following observing programs and papers. Copies of a few papers are attached with this report.
The presence of a 'warm absorber' was first suggested to explain spectral variability in an X-ray spectrum of the radio-quiet quasi-stellar object (QSO) MR 2251-178. A unified picture, in which X-ray warm absorbers and 'intrinsic' UV absorbers are the same, offers the opportunity to probe the nuclear environment of active galactic nuclei. To test this scenario and understand the physical properties of the absorber, we obtained a UV spectrum of MR 2251-178 with the Faint Object Spectrograph on board the Hubble Space Telescope (HST). The HST spectrum clearly shows absorption due to Lyalpha, N v, and C IV, blueshifted by 300 km s(exp -1) from the emission redshift of the QSO. The rarity of both X-ray and UV absorbers in radio-quiet QSOs suggests these absorbers are physically related, if not identical. Assuming the unified scenario, we place constraints on the physical parameters of the absorber and conclude the mass outflow rate is essentially the same as the accretion rate in MR 2251-178.
Introduction: The three Venus missions that were recently selected for upcoming flight (VERITAS, DAVINCI+, and EnVision) will be incredibly valuable to our understanding of Venus’ history, geology, and atmosphere. However, even once completed, key gaps in our knowledge of Venus, and more generally the formation and active processes on rocky, Earth-like planets, will still persist. Remaining questions include 1) how global intrinsic magnetic fields might be maintained on rocky worlds, and how they could then go extinct, and 2) what role atmospheric sulfur chemistry plays in climates of Earth-like planets, which is an increasingly timely subject as Earth’s own atmospheric sulfur content is climbing due to human activity. These questions require in-situ observations from Venus’ cloud deck, at the altitudes at which the UV absorber exists. The Venus Environment Research and Novel Exploration (VERNE) mission will address these questions with an aerial platform that will drift around the equatorial region of the planet for 9 days. VERNE will collect data to determine the identity of the mysterious UV absorber, while also taking magnetic field measurements over the tesserae, the regions on Venus that are most likely to retain remanent crustal magnetization, in order to understand the potential role of a past intrinsically-generated global magnetic field on Venus. Mission Objectives: The two major science objectives that drive the VERNE mission are: 1) Determine the identity of the Venusian unknown ultraviolet absorber(s). First observed approximately a century ago [1], the composition of Venus’ ultraviolet (UV) absorber is one of the oldest mysteries in Venus atmospheric chemistry [2,3]. While several candidate UV absorbers (mostly sulfur species) have been proposed, no consensus has been reached on its composition and its specific interactions with the atmosphere. Determining the identity of the UV absorber will aid climate models by showing how and where incident solar energy is absorbed by the atmosphere and make progress towards understanding the chemical and energetic processes taking place above Venus’ upper cloud deck [4]. 2) Determine if Venus retains evidence of a past, internally-generated magnetic field. While Venus does not currently have an intrinsically-generated magnetic field, evidence for the existence of a past field on Venus and a timeline of its decay will fill in a more holistic picture of the evolution of Venus’ geological record and atmosphere. As the oldest geologic units on the surface, Venus’ tesserae may still have remanent crustal magnetization signatures within the rocky composition [5]. In any case, the signatures detected will provide insight into Venus’ past geological and core dynamo activity. Mission Summary: VERNE includes a 3-part flight system made up of 1) an entry system with a HEEET (Heatshield for Extreme Entry Environment Technology) aeroshell, 2) an orbiter for data relay, and 3) an in-situ balloon and gondola. After entry into Venus’ atmosphere, the balloon will be deployed within the upper cloud deck, at an altitude of 62 km, over a tesserae region. The in-situ data collection will last for the duration of 2 full circumnavigations of the planet, which will take ~9 days. Instrumentation Suite: The four instruments that comprise VERNE’s instrument payload will enable the identification of the unknown UV absorber and the detection of remanent crustal magnetization if it exists in the tesserae. The proposed instrument suite cycle during mission operations is shown in Fig. 1. The four instruments are described below: 1) Adams (ion neutral mass spectrometer) has a range of 18-257 AMU and will detect and distinguish the mixing ratios of O₂, H₂O, H₂SO₄, S, S₂, S₃, S₄, S₅, S₆, S₇, S₈, SO, SO₂, OSSO, SO₃, Cl₂, FeCl₃ and other trace sulfur and organic species. The spatial (longitudinal) and temporal (day/night) variations will be observed throughout 2 circumnavigations with a sample cadence of 12 minutes. 2) Shelley (nephelometer) will determine the size distribution of the aerosols (0.4 to 36 um) in the atmosphere. With a size resolution of <0.7 um, it can determine which mode of H2SO4 is present and characterize the large (>30 um) organic particles previously detected by the Venera and Galileo missions [6,7]. 3) Herbert (UV imager) will measure UV radiance at 283 nm (the wavelength of SO2 absorption) and 365 nm (the unknown part of the absorber). UV images will be taken concurrently with the INMS and nephelometer to correlate UV absorption with abundances of the UV absorber species. 4) Vonnegut (magnetometer) has a range of >600 nT and a precision and accuracy of 1 nT. If magnetized by a past field, the crust may have retained a magnetization of up to 3 A/m2 [5]. With a noise floor of 10 nT, the magnetometer will be able to detect RCM from an altitude of 62 km, even if the thickness of the magnetized crust is just 1 km (Fig. 2). Mission Concept Design: VERNE will be launched with a mass of 3300 kg in an intermediate-high performance class vehicle with a 4-m fairing. The 475-day mission includes 466 days for the cruise, coasting, and orbit initialization phases before entry, descent, and balloon deployment. During the 9-day science phase, the aerial platform will make 2 circumnavigations of the planet at an altitude of 62 km. The INMS and the nephelometer will acquire data for 2 hours during the daytime and nighttime during each circumnavigation, while the UV imager will be on for the duration of the daytime, and the magnetometer will be operational throughout the entirety of the science phase. Data will be stored and processed with the JPL-designed Sphinx command and data handling system. Data will be sent from the balloon to the orbiter using an S-band relay link, stored on the orbiter, and then forwarded to Earth where it will be received by the DSN. Conclusion: VERNE will fill key gaps in our understanding of the history and ongoing processes related to the geology and atmosphere of Venus and rocky worlds in general. Even with adequate flight system contingencies and expected costs below the $900M New Frontiers cost cap, VERNE is not without its risks and challenges. Further trade spaces to explore include 1) using solely battery power vs. including solar panels to increase the mission duration and 2) investigating the use of lightweight materials and 3D-printed structures to reduce the gondola mass, among others. Acknowledgments: We would like to thank the JPL Planetary Science Summer School, especially our mentors Troy Hudson, Karl Mitchell, and Leslie Lowes, as well as our Team-X study lead Al Nash and the members of Team-X. We’d additionally like to thank our review panel for asking insightful questions and providing valuable feedback. References: [1] Ross, F. E. (1928) Astrophysical J., 68, 57-92. [2] Rossow, W. B. et al. (1980) J. Geophysical Research, 85, 8107-8128. [3] Pinto, J. P. et al. (2021) Nature Communications, 12, 175. [4] Titov, D. V. et al. (2007) Cosmic Research, 21, 401. [5] O’Rourke, J. et al. (2019) Geophysical Research Lett., 46, 5768–5777. [6] Limaye, S. S. et al. (2018) Astrobiology, 18(9), 1181-1198. [7] Grinspoon, D. H. et al. (2013) Planetary and Space Sci., 41(7), 515-542. [8] Parker, R. L. (2003) J. Geophysical Research, 108, 5006. *The cost information contained in this document is of a budgetary and planning nature and is intended for informational purposes only. It does not constitute a commitment on the part of JPL and/or Caltech.
The GNIRS instrument on the Gemini 8-‐m telescope observed comet 103P/Hartley on 2010-‐ Dec-‐04UT, a month after the EPOXI Mission encounter, and detected the 3.3 and 3.4 um bands in emission. The 3.3/3.4 ratio and the broad band widths are consistent with experiments of heated (approximately 600 K) aliphatic carbon (-CH3, -CH2) thin films. For the 3.4 micron band to be in emission, the aliphatic bonds must be attached to a carrier possessing the strongly UV-‐absorbing C=C aromatic rings, and these rings have to be less than 50-‐100 carbon atoms (4-6 Angstrom) for attached -CH bonds to also generate a 3.3 micron-band in emission. Slightly larger (≥10Å) Very Small Grains (VSGs) can absorb single UV photons comparable to or exceeding their heat capacity, thermally fluctuate and release IR photon(s). The 3.3 micron and 3.4 micron bands observed by GNIRS suggest that organic macromolecules/ nano-‐grains with both aliphatic and aromatic bonds are fluorescing/thermally fluctuating in the coma. Aliphatic and aromatic materials have been seen in Stardust samples and the primitive carbonaceous chondrite 'Tagish Lake'. The larger the ratio of the -CH2/-CH3 components of the aliphatic 3.4 micron band, the more 'primitive' the organic material. In a Stardust organic globule, some aliphatic bonds were transformed into aromatic bonds during the low dosage of Transmission Electron Microscope imaging. Conversely, lab experiments show irradiation of ices containing small PAHs generates aliphatic organics. Photo-‐processing of ices also likely forms the ubiquitous aliphatic coatings that appear on the surfaces of all silicate subgrains constituting nine cometary interplanetary dust particles. The aliphatic coatings, dominated by -CH2, likely were important in sticking the aggregates together, and existed prior to incorporation of dust aggregates into comet nuclei. These comet aliphatics may be some of the sought-‐after precursors to the more robust and complex organics studied as Insoluble Organic Matter in carbonaceous chondrites. Aliphatic coatings on submicron grains, however, will not be observable in absorption because they are fairly transparent, nor do the aliphatic carbonaceous coatings produce the 3.4 micron emission band because the particles they are attached to are too large (too many vibration modes). We must probe the nano-‐sized organic carriers that undergo substantive thermal fluctuations in cometary comae and emit at 3.3 3.4 micron. Observations of the 3.3 and 3.4 micron emission features contribute to characterizing the evolution of organics prior to their incorporation into cometary nuclei as well as their rapid evolution in cometary comae, which in turn contributes to deepening our understanding of the evolution of organics on the surfaces of asteroids and outer icy bodies in our solar system. Studying organics in comets contributes to understanding the formation and evolution pathways of ISM organics through to the formation of the robust insoluble organic matter in meteorites. A'Hearn, M.F., et al. 2011, Science, 332, 1396; Bockelee-‐Morvan, D. et al. 1995, Icarus, 116, 18; De Gregorio, B.T., et al. 2010, GCA, 74, 4454; Dello Russo, N., et al. 2011, ApJ, 734, L8; Dischler et al. 1983, Solid State Communications, 48, 105; Flynn, G., et al. 2010a, LPSC, 41, #1079; Flynn, G., et al. 2010b, COSPAR, 38, F31-‐0012-‐10; Flynn, G., Wirick, S. 2011, LPSC, 42, #1856; Fomenkova, et al. 1994, GCA 58, 4503; Matrajt, G., et al. 2013, ApJ, 765, 145; Schutte, et al. 1993, ApJ, 415, 397; Wooden, D.H. et al. 2011, EPSC-‐DPS, 1557; Wooden, D.H. et al. 2013, submitted.
Optical absorber coatings have been developed from carbon-based paints, metal blacks, or glassy carbon. However, such materials are not truly black and have poor absorption characteristics at longer wavelengths. The blackness of such coatings is important to increase the accuracy of calibration targets used in radiometric imaging spectrometers since blackbody cavities are prohibitively large in size. Such coatings are also useful potentially for thermal detectors, where a broadband absorber is desired. Au-black has been a commonly used broadband optical absorber, but it is very fragile and can easily be damaged by heat and mechanical vibration. An optically efficient, thermally rugged absorber could also be beneficial for thermal solar cell applications for energy harnessing, particularly in the 350-2,500 nm spectral window. It has been demonstrated that arrays of vertically oriented carbon nanotubes (CNTs), specifically multi-walled-carbon- nanotubes (MWCNTs), are an exceptional optical absorber over a broad range of wavelengths well into the infrared (IR). The reflectance of such arrays is 100x lower compared to conventional black materials, such as Au black in the spectral window of 350-2,500 nm. Total hemispherical measurements revealed a reflectance of approximately equal to 1.7% at lambda approximately equal to 1 micrometer, and at longer wavelengths into the infrared (IR), the specular reflectance was approximately equal to 2.4% at lambda approximately equal to 7 micrometers. The previously synthesized CNTs for optical absorber applications were formed using water-assisted thermal chemical vapor deposition (CVD), which yields CNT lengths in excess of 100's of microns. Vertical alignment, deemed to be a critical feature in enabling the high optical absorption from CNT arrays, occurs primarily via the crowding effect with thermal CVD synthesized CNTs, which is generally not effective in aligning CNTs with lengths less than 10 m. Here it has been shown that the electric field inherent in a plasma yields vertically aligned CNTs at small length scales (less than 10 m), which still exhibit broadband, and high-efficiency optical absorption characteristics from the ultraviolet (UV) to IR. A thin and yet highly absorbing coating is extremely valuable for detector applications for radiometry in order to enhance sensitivity. A plasma-based process also increases the potential of forming the optical absorbers at lower synthesis temperatures in the future, increasing the prospects of integrating the absorbers with flexible substrates for low-cost solar cell applications, for example.
This data package contains text files that describe geochemical measurements collected from 2017-2018 during isolated conifer needle decomposition field studies at the Lower Subalpine region of Washington Gulch in Crested Butte, CO. The files within include total carbon and nitrogen (CN) content and fourier-transform infrared spectroscopy (FTIR) results for the initial needles collected in 2016 and after decomposition in October 2018. DI water extractions were conducted with the initial harvested needles in 2016 to determine extractable dissolved organic carbon (DOC), total nitrogen (TN), UV absorbance at 254 nm (UV254), and specific UV absorbance (SUVA). This dataset also includes soil extractable DOC, TN, nitrate, nitrite, ammonium, total organic nitrogen (TON), and pH results from soil collections in 2017. Soil porewater results for DOC, TN, UV254, and SUVA analyses at 15 cm soil depth are also provided from 2017-2018. Gas flux raw data provides CO2, CH4, N2O, and NH3 measurements above needle decomposition over the two study years. Finally, soil samples for microbial DNA extractions were collected from the upper soil depth. This raw data is available in the NCBI SRA database under SRA accession number PRJNA605259. These datasets were generated to investigate the isolated decomposition of spruce and lodgepole conifer needles. The goal of this work was to understand how needle litter impacts terrestrial biogeochemical carbon and nitrogen cycling. Results from this work is detailed in the reference paper "A comparison of lodgepole and spruce needle chemistry impacts on terrestrial biogeochemical processes during isolated needle decomposition. DOI: 10.7717/peerj.9538."
The model predictions were compared with the Pioneer Venus probes and orbiter to determine the composition of the UV absorbing materials. The simulations were carried out with radiative transfer codes which included spacecraft constraints on the aerosol and gas characteristics in the Venus atmosphere; gaseous SO2 (a source of opacity at the wavelengths below 0.32 microns), and a second absorber (which dominates above 0.32 microns) were required. The UV contrast variations are due to the optical depth changes in the upper haze layer producing brightness variations between equatorial and polar areas, and to differences in the depth over which the second UV absorber is depleted in the highest portion of the main clouds.
A reaction kinetics based model of the photodegradation process, which measures all important rate constants, and a computerized model capable of predicting the photodegradation rate and failure modes of a 30 year period, were developed. It is shown that the computerized photodegradation model for polyethylene correctly predicts failure of ELVAX 15 and cross linked ELVAX 150 on outdoor exposure. It is indicated that cross linking ethylene vinyl acetate (EVA) does not significantly change its degradation rate. It is shown that the effect of the stabilizer package is approximately equivalent on both polymers. The computerized model indicates that peroxide decomposers and UV absorbers are the most effective stabilizers. It is found that a combination of UV absorbers and a hindered amine light stabilizer (HALS) is the most effective stabilizer system.
Aerosols scatter and absorb UV radiation and consequently either enhance or reduce the actinic fluxes and photolysis rates. Mineral dust particles are known to absorb UV radiation, but the impact on the photolysis rates is complicated by the optical properties dependency on the particle size, composition and wavelength. The high spatial and temporal variabilities of the dust size distribution add difficulties to the global analysis. The Georgia Tech/Goddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model has been used to simulate several years of the global distribution of mineral dust in the troposphere. The optical parameters (extinction efficiency, single scattering albedo and asymmetry parameter) of the seven particle sizes (from 0.1 to 5 microns), transported by the model, have been inserted in the Tropospheric Ultraviolet-Visible (TUV) radiation model version 4. The photodissociation rates of J(N02) and J(03 to O(1D)) have been calculated with TUV-4 with and without dust particles on the global scale. The effects of dust on J(N02) and J(03) will be analyzed with an emphasis on the difference between major dust sources in Africa and Asia.