Wolf Trap continuation study Final report
Critical evaluation of light and X ray scatter, conductivity, and fluorescence as part of Wolf Trap extraterrestrial life detector development
Buckendahl, D.↗
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Influence of oxygen on defect production in electron-irradiated, boron-doped silicon
Deep level transient spectroscopy (DLTS) measurements were made on float-zone and crucible-grown, boron-doped silicon irradiated with 1-MeV electrons. The minority carrier trap attributed to a boron-related state, was not seen in low-resistivity, float-zone silicon. However, a new majority carrier trap was observed in these samples. In the case of more lightly doped material the minority carrier trap was present, and its introduction rate was lower in float-zone than in crucible-grown silicon. For 1- and 10-ohm-cm float-zone material that was oxidized during processing, the introduction rates for this trap were comparable to those for crucible-grown silicon. This behavior indicates that the minority carrier trap involves oxygen and that it may be due to a boron-oxygen complex. The majority carrier trap seen in heavily doped, float-zone silicon may also involve boron but not oxygen. Observed trap concentrations suggest that oxygen content in the regions examined by DLTS is affected by processing techniques. Other differences were observed in defect production and annealing behavior of electron-irradiated, float-zone and crucible-grown silicon.
Deangelis, H. M.↗
Spacecraft material applications: Long-term stability questions
An examination of the materials concerns for a variety of spacecraft components shows that long-term stability within the space environments is a major issue in the design of large space antenna systems. This survey paper will review some of the more recent work on the effect of space environment on (1) thin films, (2) structural composites, and (3) thermal control materials. Degradation in thermal-mechanical and optical properties associated with atmospheric and trapped particles and ultraviolet light will be highlighted. Finally, the dimensional instability associated with microcracking during thermal cycling will be examined and a methodology for estimating thermal fatigue effects from results of mechanical fatigue tests will be presented.
Crossman, F. W.↗
Operando Spectroscopic Analysis of Photovoltage Generation in Hematite Photoanodes
Solar-driven water splitting requires sufficient photovoltage to drive both water oxidation and proton reduction. Understanding the factors driving and limiting photovoltage generation is therefore crucial to optimizing photoelectrode design but has proven challenging to determine under operando conditions for photoanodes driving slow multiredox reactions such as water oxidation. In this work, operando optical spectroscopy is employed to measure the hole quasi-Fermi level (E F,p ) position in model hematite photoanodes as a function of applied bias and light intensity. The quasi-Fermi level splitting determined from these data are shown be in excellent agreement with the directly measured photovoltages, demonstrating the primarily electrochemical rather than primarily electrostatic origin of photovoltage in these photoelectrodes. E F,p pinning is observed at low light intensities and biases, indicative of hole trap states lying ∼0.2 eV above the valence band edge with a density of ∼1 nm −2 . Hole accumulation in these trap states is correlated with first order water oxidation. At higher light intensities and/or more anodic bias, E F,p becomes unpinned, assigned to saturation of these trap states, and correlated with the onset of third order water oxidation to molecular oxygen. Comparison with rate law analyses for other photoanodes indicates that such hole trap states may be a ubiquitous feature of metal oxides and suggests that materials processing strategies to suppress the density of such states would be a promising strategy to enhance photoanode performance.
Hematite↗
Effect of proton irradiation temperature on persistent photoconductivity in zinc oxide metal-semiconductor-metal ultraviolet photodetectors
The electrical and structural characteristics of 50-nm-thick zinc oxide (ZnO) metal-semiconductor-metal ultraviolet (UV) photodetectors subjected to proton irradiation at different temperatures are reported and compared. The devices were irradiated with 200 keV protons to a fluence of 1016 cm−2. Examination of the x-ray diffraction (XRD) rocking curves indicates a preferred (100) orientation prior to irradiation, with decrease in crystal quality afterward. Additionally, peak shifts in XRD and Raman spectra of the control sample relative to well-known theoretical positions are indicative of tensile strain in the as-deposited ZnO films. Shifts toward theoretical unstrained positions are observed in the irradiated films, which indicates partial relaxation. Raman spectra also indicate increase in oxygen vacancies (VO) and zinc interstitial defects (Zni) compared to the control sample. Additionally, transient photocurrent measurements performed on each sample at different temperatures showed up to 2× increase in photocurrent decay time constants for irradiated samples vs the control. This persistent photoconductive behavior is linked to the activation of electron and hole traps near the surface, and to the desorption and reabsorption of O2 molecules on the ZnO surface under the influence of UV light. Using an Arrhenius model, trap activation energies were extracted and, by comparing with known energies from the literature, the dominant defects contributing to persistent photoconductivity for each irradiation condition were identified. The persistence of differences in photocurrent transients between different samples months after irradiation indicates that the defects introduced by the suppression of thermally activated dynamic annealing processes have a long-term deleterious effect on device performance.
Heuser, Thomas A. (ORCID:0000000225642400)↗
Low-Reflectance Surfaces For Solar Cells
Improved method for increasing solar cell efficiency has potential application for space-based and terrestrial solar power systems and optoelectronic devices. Etched low-angle grooves help recover reflected light. Light reflected from v-grooved surface trapped in cover glass and adhesive by total internal reflection. Reflected light redirected onto surface, and greater fraction of incident light absorbed, producing more electrical energy in InP solar photovoltaic cell.
Bailey, Sheila G.↗
Spectroscopic Investigation of Shallow Hole Traps in Ga- and B-doped Czochralski Silicon: Insight into Light-Induced Degradation
We report the minority carrier lifetime in B-doped Czochralski (Cz) Si declines upon carrier injection due to light-induced degradation (LID), which is attributed to the formation of a recombination-active boron-oxygen complex. Ga-doped Cz Si does not undergo LID. Previously, we showed that B-doped Cz Si undergoes a transition from paramagnetic to diamagnetic due to LID. Herein, we show that Ga-doped Cz Si remains paramagnetic upon carrier injection. This suggests that either the shallow hole traps that are formed in B-doped Cz Si are absent in Ga-doped Cz Si, or the negative-U centers in Ga-doped Cz Si do not transform into a recombination-active configuration, because the shallow acceptor trap state is shallower than the Ga acceptor level in the forbidden gap. In contrast to B-doped Cz Si, the defect signatures in Ga-doped Cz Si do not change upon light exposure, as detected by both electron paramagnetic resonance and deep-level transient spectroscopy.
14 SOLAR ENERGY↗
Shallow-trap-induced positive absorptive two-beam coupling 'gain' and light-induced transparency in nominally undoped barium titanate
The asymmetry of beam coupling with respect to the orientation of the polar axis in a nominally undoped barium titanate crystal is used to determine the electro-optic and absorptive 'gain' in the usual beam-coupling geometry. For small grating wave vectors, the electrooptic coupling vanishes but the absorptive coupling remains finite and positive. Positive absorptive coupling at small grating wave vectors is correlated with the light-induced transparency of the crystal described herein. The intensity and grating wave vector dependence of the electrooptic and absorptive coupling, and the light-induced transparency are consistent with a model incorporating deep and shallow levels.
Garrett, M. H.↗
Measurements of Penning-Malmberg trap patch potentials and associated performance degradation
Antiprotons created by laser ionization of antihydrogen are observed to rapidly escape the ALPHA trap. Further, positron plasmas heat more quickly after the trap is illuminated by laser light for several hours. These phenomena can be caused by patch potentials—variations in the electrical potential along metal surfaces. A simple model of the effects of patch potentials explains the particle loss, and an experimental technique using trapped electrons is developed for measuring the electric field produced by the patch potentials. The model is validated by controlled experiments and simulations. Published by the American Physical Society 2024
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Chlorine retention enables the indoor light harvesting of triple halide wide bandgap perovskites
Chlorine incorporation in triple halide perovskites reduces trap density and enhances the efficiency of indoor light harvesting.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
High resolution threshold photoelectron spectroscopy by electron attachment
A system is provided for determining the stable energy levels of a species ion, of an atomic, molecular, or radical type, by application of ionizing energy of a predetermined level, such as through photoionization. The system adds a trapping gas to the gaseous species to provide a technique for detection of the energy levels. The electrons emitted from ionized species are captured by the trapping gas, only if the electrons have substantially zero kinetic energy. If the electrons have nearly zero energy, they are absorbed by the trapping gas to produce negative ions of the trapping gas that can be detected by a mass spectrometer. The applied energies (i.e. light frequencies) at which large quantities of trapping gas ions are detected, are the stable energy levels of the positive ion of the species. SF6 and CFCl3 have the narrowest acceptance bands, so that when they are used as the trapping gas, they bind electrons only when the electrons have very close to zero kinetic energy.
Chutjian, A.↗
Direct Evidence of Visible Light-Induced Homolysis in Chlorobis(2,9-dimethyl-1,10-phenanthroline)copper(II)
Developments in the field of photoredox catalysis that leveraged the long-lived excited states of Ir(III) and Ru(II) photosensitizers to enable radical coupling processes paved the way for explorations of synthetic transformations that would otherwise remain unrealized. While first row transition metal photocatalysts have not been as extensively investigated, valuable synthetic transformations covering broad scopes of olefin functionalization have been recently reported featuring photoactivated chlorobis(phenanthroline) Cu(II) complexes. In this study, the photochemical processes underpinning the catalytic activity of [Cu(dmp) 2 Cl]Cl (dmp = 2,9-dimethyl-1,10-phenanthroline) were studied. The combined results from static spectroscopic measurements and conventional photochemistry, ultrafast transient absorption, and electron paramagnetic resonance spin trapping experiments strongly support blue light (λ ex = 427 or 470 nm)-induced Cu–Cl homolytic bond cleavage in [Cu(dmp) 2 Cl] + occurring in <100 fs. On the basis of electronic structure calculations, this bond-breaking photochemistry corresponds to the Cl → Cu(II) ligand-to-metal charge transfer transition, unmasking a Cu(I) species [Cu(dmp) 2 ] + and a Cl atom, thereby serving as a departure point for both Cu(I)- or Cu(II)-based photoredox transformations. No net photochemistry was observed through direct excitation of the ligand-field transitions in the red (λ ex = 785 or 800 nm), and all combined experiments indicated no evidence of Cu–Cl bond cleavage under these conditions. As a result, the underlying visible light-induced homolysis of a metal–ligand bond yielding a one-electron-reduced photosensitizer and a radical species may form the basis for novel transformations initiated by photoinduced homolysis featuring in situ-formed metal–substrate adducts utilizing first row transition metal complexes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Mutually guided light and particle beam propagation
The polarizability of atoms and molecules gives rise to optical forces that trap particles and a refractive index that guides light beams, potentially leading to a self-guided laser and particle beam propagation. In this paper, the mutual interactions between an expanding particle beam and a diffracting light beam are investigated using an axisymmetric particle-light coupled simulation. The nonlinear coupling between particles and photons is dependent on the particle beam radius, particle density, particle velocity and temperature, polarizability, light beam waist, light frequency (with respect to the resonance frequency), and light intensity. The computational results show that the maximum propagation distance is achieved when the waveguiding effect is optimized to single-mode operation. The application of the coupled beam propagation as a space propulsion system is discussed.
42 ENGINEERING↗
Visible-Light-Initiated Free-Radical Polymerization by Homomolecular Triplet-Triplet Annihilation
Polymerization reactions initiated by ultraviolet light are ubiquitous in scores of industrial applications but would markedly benefit from visible-light activation to overcome stability, energy consumption, light penetration, and sample geometry limitations. The current work leverages visible-light-driven homomolecular triplet-triplet annihilation (TTA) in zinc(II) meso-tetraphenylporphyrin (ZnTPP) to initiate facile free-radical polymerization in trimethylolpropane triacrylate (TMPTA) and methyl acrylate (MA) monomers through ultrafast electron transfer quenching. Selective Q-band (S 1 ) excitation of ZnTPP in the green or yellow sensitizes TTA occurring between two 3 ZnTPP* energized chromophores, ultimately generating the highly reducing S 2 excited state on one ZnTPP molecule (E red = –2.13 V versus saturated calomel electrode, SCE). Subsequently, this S 2 state engages in electron transfer with TMPTA or MA, thereby initiating the radical polymerization process. Bimolecular electron transfer was confirmed through optically gated fluorescence upconversion. In conclusion, FT-IR and EPR spin-trapping experiments verified visible-light-initiated polymerization leading to the formation of well-defined macro- and microscopic objects.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Sculpting a Pre-Planetary Nebula with a Precessing Jet: IRAS 16342-3814
We have imaged the bipolar pre-planetary nebula IRAS 16342-3814 with the Keck adaptive optics (AO) system in four near-infrared bands in the 1.6-4.7 (micro)m range. The lobes, which showed smoothly varying brightness distributions in previous optical images taken with the Hubble Space Telescope, have a limb-brightened appearance in the AO images, with a remarkable corkscrew structure inscribed on the lobe walls. A well-collimated, precessing jet with a diameter less than or approximately equal to 100 AU and a precession period less than or approximately equal to 50 yr, interacting with ambient circumstellar material, is most likely responsible for the corkscrew structure and the lobes, as indicated by a detailed comparison of our observations with published numerical simulations. The very red colors of the lobes in the near-infrared, coupled with their visibility at optical wavelengths, require that at least half, but not all, of the light of the central star be trapped by a compact circumstellar dust cloud heated to approximately 600-700 K and reradiated in the infrared. The lobes are thus illuminated both by the infrared light from this dust cloud as well as by the optical light from the central star.
circumstellar matter↗
DEVELOPMENT OF A LIGHT-WEIGHT REGENERATIVELY COOLED THRUST CHAMBER WITH BRAZED RIBS AND BRAZED OUTER WIRE TRAP
Design and fabrication procedures are discussed of a brazed-ribtype thrust chamber fabricated from stainless steel or inconel for a Sooo-lb thrust 20: 1 expansion-area-ratio regeneratively cooled liquidpropellant rocket engine which is designated as the JPL 6K Engine and operates at a chamber pressure of 150 psia. Hydrazine is used as the fuel and regenerative coolant and nitrogen tetroxide as the oxidizer. The nozzle-throat diameter is 5.42 in. The thrust chamber consists of a sheet-metal gas-side liner with longitudinal ribs spotwelded and brazed to the outer surface. Wire is wrapped over the ribs circumferentially, spot-welded to the ribs, and brazed. The liner, ribs, and wire form the coolant-passage walls. There are three basic advantages to this type of thrust chamber: light weight, ease of fabrication, and comparatively low cost. The total dry weight of a thrust chamber of this type and size made of 347 stainless steel is 46.2 lb, and the wet weight is 56.3 Ib. A total of 87 static engine tests were made on 19 of 23 thrust chambers fabricated by this technique. Four of the chambers tested had an expansion-area ratio of 20:1, and 15, which were shorter but had the same throat diameter, had an expansion-area ratio of 3.5:l. Accumulated test time was 1926 sec, including 558 sec regenerative cooling with hydrazine and 1368 sec cooling with water. One 20:l thrust chamber was subjected to 16 separate engine tests, with an accumulated test time of 399 sec, and was still in very good operating condition after the tests were completed. With water flowing through the coolant passages at 10 lb/sec, the measured nominal pressure drop between coolant manifolds of a 20:l thrust chamber wrapped with flat wire was 17.2 psi.
Thrust Chamber↗
Role of Polycyclic Aromatic Alkylammonium Cations in Tuning the Electronic Properties and Band Alignment of Two-Dimensional Hybrid Perovskite Semiconductors
Two-dimensional hybrid organic–inorganic perovskites (HOIPs) have recently drawn intense attention as potential photovoltaic materials. However, n = 1 two-dimensional (2D) HOIPs face the challenge of low conductivity between the inorganic layers, leading to unsatisfactory device performance. Interestingly, 2D HOIPs employing π-conjugated molecules as organic moieties show energy and charge transfers between organic and inorganic layers, indicating potentially efficient carrier transport for photovoltaic applications. Nevertheless, the development of 2D HOIP-based solar cells especially utilizing polycyclic aromatic alkylammonium as cations is in its infancy. Herein, we investigated the electronic structure and band alignment of a series of n = 1 2D Ruddlesden–Popper (RP) phase HOIPs containing different polycyclic aromatic groups and alkyl chains, based on density functional theory calculations. We find that the polycyclic aromatic group plays an important role in controlling the functionality of 2D HOIPs by directly modifying band-edge states, and the band alignment at the organic–inorganic interface can be designed to promote either exciton trapping or dissociation for light-emitting or photovoltaic applications, respectively.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Solution phase high repetition rate laser pump x-ray probe picosecond hard x-ray spectroscopy at the Stanford Synchrotron Radiation Lightsource
We present a dedicated end-station for solution phase high repetition rate (MHz) picosecond hard x-ray spectroscopy at beamline 15-2 of the Stanford Synchrotron Radiation Lightsource. A high-power ultrafast ytterbium-doped fiber laser is used to photoexcite the samples at a repetition rate of 640 kHz, while the data acquisition operates at the 1.28 MHz repetition rate of the storage ring recording data in an alternating on-off mode. The time-resolved x-ray measurements are enabled via gating the x-ray detectors with the 20 mA/70 ps camshaft bunch of SPEAR3, a mode available during the routine operations of the Stanford Synchrotron Radiation Lightsource. As a benchmark study, aiming to demonstrate the advantageous capabilities of this end-station, we have conducted picosecond Fe K-edge x-ray absorption spectroscopy on aqueous [FeII(phen)3]2+, a prototypical spin crossover complex that undergoes light-induced excited spin state trapping forming an electronic excited state with a 0.6–0.7 ns lifetime. In addition, we report transient Fe Kβ main line and valence-to-core x-ray emission spectra, showing a unique detection sensitivity and an excellent agreement with model spectra and density functional theory calculations, respectively. Notably, the achieved signal-to-noise ratio, the overall performance, and the routine availability of the developed end-station have enabled a systematic time-resolved science program using the monochromatic beam at the Stanford Synchrotron Radiation Lightsource.
47 OTHER INSTRUMENTATION↗