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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Monitoring the growth dynamics of colloidal gold-silver core-shell nanoparticles using in situ second harmonic generation and extinction spectroscopy

The growth dynamics of gold-silver core-shell (Au@Ag) nanoparticles are studied using in situ time-dependent second harmonic generation (SHG) and extinction spectroscopy to investigate the nanoparticle shell formation. The silver shell is grown by reduction of silver cations onto a 14 nm gold core using ascorbic acid in colloidal aqueous solution under varying reaction concentrations producing Au@Ag nanoparticles of final sizes ranging from 51 to 78 nm in diameter. The in situ extinction spectra show a rapid increase in intensity on the timescale of 5–6 s with blue shifting and narrowing of the plasmonic peak during the silver shell formation. The in situ SHG signals show an abrupt rise at early times of the reaction, followed by a time-dependent biexponential decrease, where the faster SHG lifetime corresponds to the timescale of the shell growth, and where the slower SHG lifetime is attributed to changes in the nanoparticle surface charge density. A large enhancement in the SHG signal at early stages of the reaction is caused by plasmonic hot spots due to the nanoparticle surface morphology, which becomes smoother as the reaction proceeds. The final extinction spectra are compared to finite-difference time-domain (FDTD) calculations, showing general agreement with experiment, where the plasmon peak red shifts and increases in spectral width as the silver shell thickness increases. These in situ SHG and extinction spectroscopy results, combined with FDTD calculations, help characterize the complicated processes involved in colloidal nanoparticle shell formation in real time for developing potential plasmon-enhanced nanomaterial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Identification of the defect dominating high temperature reverse leakage current in vertical GaN power diodes through deep level transient spectroscopy

Deep level defects in wide bandgap semiconductors, whose response times are in the range of power converter switching times, can have a significant effect on converter efficiency. We use Deep Level Transient Spectroscopy (DLTS) to evaluate such defect levels in the n- drift layer of vertical GaN (v-GaN) power diodes with VBD ~ 1500 V. DLTS reveals three energy levels that are at ~0.6 eV (highest density), ~0.27 eV (lowest density) and ~ 45 meV (a dopant level) from the conduction band. Dopant extraction from Capacitance-Voltage measurement test (C-V) at multiple temperatures enables trap density evaluation, and the ~0.6 eV trap has a density of 1.2 × 10 15 cm -3 . Here, the 0.6 eV energy level and its density are similar to a defect that is known to cause current collapse in GaN based surface conducting devices (like HEMTs). Analysis of reverse bias currents over temperature in the v-GaN diodes indicates a predominant role of the same defect in determining reverse leakage current at high temperatures, reducing switching efficiency.

42 ENGINEERING↗
DOE OSTI2025

Three rate-determining protein roles in photosynthetic O 2 -evolution addressed by time-resolved experiments on genetically modified photosystems

Light-driven water splitting by plants, algae and cyanobacteria is pivotal for global bioenergetics and biomass formation. A manganese cluster bound to the photosystem II proteins catalyzes the complex reaction at high rate, but the rate-determining factors are insufficiently understood. Here we trace the oxygen-evolution transition by time-resolved polarography and infrared spectroscopy for cyanobacterial photosystems genetically modified at two strategic sites, complemented by computational chemistry. Our results highlight three rate-determining roles of the protein environment of the metal cluster: acceleration of proton-coupled electron transfer, acceleration of substrate-water insertion after O 2 -formation, and balancing of rate-determining enthalpic and entropic contributions. Whereas in general the substrate-water insertion step may be unresolvable in time-resolved experiments, here it likely becomes traceable because of deceleration by genetic modification. Our results may stimulate new time-resolved experiments on substrate-water insertion in photosynthesis, clarification of enthalpy-entropy compensation in enzyme catalysis, and knowledge-guided development of inorganic catalyst materials.

Bioenergetics↗
DOE OSTI2023

Cadmium Magnesium Telluride for Next-Generation X-Ray Free Electron Laser, Synchrotron, and Many Other Applications

We developed a picosecond photodetector based on our Bridgman-grown and specially engineered cadmium magnesium telluride (Cd 1–x MgxTe) single crystal that is sensitive to both optical and X-ray pulses for coarse timing in free-electron laser applications. Cd 1–x MgxTe is a widebandgap semiconductor with potential applications, not only in optoelectronics, but also in particle physics as an intense pulse radiation detector for bremsstrahlung, X-ray/gamma-ray radiation, thermal neutrons, and medical imaging. For femtosecond optical and X-ray crosscorrelation, the material must have a very short lifetime, a condition that is opposite to that required for nuclear spectroscopy applications. At the same time, the material also needs to have a very low bulk leakage current, in the 10–90 nA range for voltages to even 1000 V. Hence, the ability to tailor or engineer the material is very crucial. Picosecond response and the crystal growth of this specially engineered Cd 1–x MgxTe material are presented. Furthermore, other characterization and transient measurements are discussed along with room-temperature semiconductor detector performance for other nuclear radiation detection applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Cadmium Magnesium Telluride for Next Generation X-Ray Free Electron Laser, Synchrotron and Many Other Applications

We developed a picosecond photodetector based on our Bridgman grown and specially engineered Cadmium Magnesium Telluride (Cd 1-x Mg x Te) single crystal that is sensitive to both optical and x-ray pulses for coarse timing in Free Electron Laser applications. Cd 1-x Mg x Te is a wide bandgap semiconductor material with potential applications, not only in optoelectronics, but also in particle physics as an intense pulse radiation detector for bremsstrahlung, X-ray/gamma ray radiation, thermal neutrons, and medical imaging. However, for femtosecond optical and x-ray cross correlation, the material has to have very short lifetime, a condition that is opposite to that required for nuclear spectroscopy applications. At the same time, the material also needs to have very low bulk leakage current, in the 0.10 pA range. Hence the ability to tailor or engineer the material is very crucial. In this paper, picosecond response and the crystal growth of this specially engineered cadmium magnesium telluride material will be presented. Other material characterization and transient measurements will also be discussed along with room temperature semiconductor detector performance for other nuclear radiation detection applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Excited-State Charge Distribution of a Donor–π–Acceptor Zn Porphyrin Probed by N K-Edge Transient Absorption Spectroscopy

Zinc porphyrin solar cell dyes with donor-π–acceptor architectures combine light absorber (π), electron-donor, and electron-acceptor moieties inside a single molecule with atomic precision. The donor-π–acceptor design promotes the separation of charge carriers following optical excitation. Here, we probe the excited-state electronic structure within such molecules by combining time-resolved X-ray absorption spectroscopy at the N K-edge with first-principles time-dependent density functional theory (TD-DFT) calculations. Furthermore, customized Zn porphyrins with strong-donor triphenylamine groups or weak-donor tri-tert-butylbenzene groups were synthesized. Energetically well-separated N K-edge absorption features simultaneously probe the excited-state electronic structure from the perspectives of the macrocycle and triphenylamine N atoms. New absorption transitions between the macrocycle N atoms and the excited-state HOMO vacancy are observed, and the triphenylamine associated absorption feature blue-shifts, consistent with partial oxidation of the donor groups in the excited state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Metallofullerene photoswitches driven by photoinduced fullerene-to-metal electron transfer

We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of Y x Sc 3-x N@C 80 (x = 0–3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S 1 –T 1 gap decrease in this row. For Sc 3 N@C 80 , we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin–lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14 N, 45 Sc, and 89 Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y 3 N to Sc 3 N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Comparison of excitation temperature of a laser-produced plasma by combining emission and absorption spectroscopy

Measurement of the temporal evolution of laser-produced plasma temperature is very important for many of its applications, and several plasma diagnostic tools are routinely used by researchers. However, it is very challenging to measure the properties of the plasma at the early and late times of its evolution using a single diagnostic tool. In this study, we combined emission and laser absorption spectroscopy to compare the excitation temperatures of a laser-produced uranium plasma system. Several U I transitions in the near-infrared spectral range (775–800 nm) were considered, and the Boltzmann plot method was used to measure the excitation temperatures using both emission and absorption spectroscopy. Emission spectroscopy provided early-time temperature measurements of the plasma up to times 2–20 µs, while absorption spectroscopy provided temperature measurements at late times of plasma evolution (for times 5–80 µs). The emission and absorbance of U I transitions were found to follow the Boltzmann distribution, indicating the plasma is likely in the state of local thermodynamic equilibrium even at late times of its lifetime. The emission and absorption-based time-resolved excitation temperatures demonstrated good agreement at earlier times (≤15 µs) in the overlapped temporal region, while a deviation in the measured values was seen at times (≥15 µs), and potential reasons for such a disagreement are discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Role of matrix elements in the time-resolved photoemission signal

Time- and angle-resolved photoemission spectroscopy (TR-ARPES) provides access to the ultrafast evolution of electrons andmany-body interactions in solid-state systems. However, themomentum- and energy-resolved transient photoemission intensitymay not be unambiguously described by the intrinsic relaxation dynamics of photoexcited electrons alone.The interpretation of the time-dependent photoemission signal can be affected by the transient evolution of the electronic distribution, and both the one-electron removal spectral function aswell as the photoemissionmatrix elements. Here we investigate the topological insulator Bi 1.1 Sb 0.9 Te 2 S to demonstrate, bymeans of a detailed probe-polarization dependent study, the transient contribution ofmatrix elements toTR-ARPES.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Reconceptualizing the Ir III Role in Metallaphotoredox Catalysis: From Strong Photooxidant to Potent Energy Donor

Dual Ir III /L n Ni II metallaphotoredox catalyzed C(sp 3 )–C(sp 2 ) cross-coupling reactions are widely assumed to proceed by photoinduced single electron transfer steps due to the highly oxidizing Ir III * excited state (Ir III = [Ir(dF(CF 3 )ppy) 2 (dtbbpy)] + [PF 6 ] – ; dF(CF 3 )ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; L n = dtbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). Using time-resolved absorption and emission spectroscopy, we reveal that energy transfer between Ir III * and various LnNi II precatalysts and intermediates with k q ≥ 10 8 M –1 s –1 also drives catalysis. Specifically, the excited states of L n Ni II dihalide precatalysts/organometallic intermediates accessible by energy transfer appear to drive bond homolysis, halogen radical elimination, and reductive elimination reactions that facilitate formation of cross-coupled products. Energy transfer dynamics consequently circumvent the need for photoinduced electron transfer, thereby extending substrate scopes to coupling partners that cannot be oxidized by Ir III *. Within a cross-electrophile coupling model reaction between 4-bromobenzotrifluoride and bromocyclohexane, energy transfer activates the L n Ni II precatalyst at early reaction times before nucleophilic reductants are present. In the absence of Ir III , direct excitation of L n Ni II (Br) 2 also activates the precatalyst to form a L n Ni II (Br)(Aryl) intermediate. To compare energy transfer and electron transfer kinetics, we determined rate constants for reductive quenching by Br – (k SET = 4.1 × 10 8 M –1 s –1 ) and for the subsequent electron transfer from reduced Ir III•– to L n Ni II (Br) 2 (k SET = 4.1 × 10 7 M –1 s –1 ) using Stern-Volmer analysis and pulse radiolysis, respectively. Energy transfer rate constants are competitive with the electron transfer rate constants and energy transfer is a parallel pathway within metallaphotoredox catalysis. Exploiting the energy transfer mechanism, we demonstrate highly selective cross-electrophile coupling between 4-chlorobenzotrifluoride and bromocyclohexane to form exclusively cross-coupled product. Here, with alkyl-trifluoroborate nucleophiles that do not reductively quench IrIII* emission, transmetalation with L n Ni II (Br/Cl)(Aryl) followed by energy transfer also drives excited state reductive elimination to form C(sp 3 )–C(sp 2 ) cross-coupled product. Similarly, energy transfer rather than Ni II oxidation drives C(sp 2 )–OR reductive elimination, despite the strongly oxidizing ability of Ir III *. In total, these reactions demonstrate energy transfer processes from Ir III * to L n Ni II in metallaphotoredox catalysis that can unlock alternative reactive pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2014

Organics Exposure in Orbit (OREOcube): A Next-Generation Space Exposure Platform

The OREOcube (ORganics Exposure in Orbit cube) experiment on the International Space Station (ISS) will investigate the effects of solar and cosmic radiation on organic thin films supported on inorganic substrates. Probing the kinetics of structural changes and photomodulated organic− inorganic interactions with real-time in situ UV−visible spectroscopy, this experiment will investigate the role played by solid mineral surfaces in the (photo)chemical evolution, transport, and distribution of organics in our solar system and beyond. In preparation for the OREOcube ISS experiment, we report here laboratory measurements of the photostability of thin films of the 9,10-anthraquinone derivative anthrarufin (51 nm thick) layered upon ultrathin films of iron oxides magnetite and hematite (4 nm thick), as well as supported directly on fused silica. During irradiation with UV and visible light simulating the photon flux and spectral distribution on the surface of Mars, anthrarufin/iron oxide bilayer thin films were exposed to CO2 (800 Pa), the main constituent (and pressure) of the martian atmosphere. The time-dependent photodegradation of anthrarufin thin films revealed the inhibition of degradation by both types of underlying iron oxides relative to anthrarufin on bare fused silica. Interactions between the organic and inorganic thin films, apparent in spectral shifts of the anthrarufin bands, are consistent with presumed free-electron quenching of semiquinone anion radicals by the iron oxide layers, electively protecting the organic compound from photodegradation. Combining such in situ real-time kinetic measurements of thin films in future space exposure experiments on the ISS with postflight sample return and analysis will provide time-course studies complemented by in-depth chemical analysis. This will facilitate the characterization and modeling of the chemistry of organic species associated with mineral surfaces in astrobiological contexts.

Organics↗
DOE OSTI2020

Ring currents modulate optoelectronic properties of aromatic chromophores at 25 T

The properties of organic molecules can be influenced by magnetic fields, and these magnetic field effects are diverse. They range from inducing nuclear Zeeman splitting for structural determination in NMR spectroscopy to polaron Zeeman splitting organic spintronics and organic magnetoresistance. A pervasive magnetic field effect on an aromatic molecule is the aromatic ring current, which can be thought of as an induction of a circular current of π-electrons upon the application of a magnetic field perpendicular to the π-system of the molecule. While in NMR spectroscopy the effects of ring currents on the chemical shifts of nearby protons are relatively well understood, and even predictable, the consequences of these modified electronic states on the spectroscopy of molecules has remained unknown. In this work, we find that photophysical properties of model phthalocyanine compounds and their aggregates display clear magnetic field dependences up to 25 T, with the aggregates showing more drastic magnetic field sensitivities depending on the intermolecular interactions with the amplification of ring currents in stacked aggregates. These observations are consistent with ring currents measured in NMR spectroscopy and simulated in time-dependent density functional theory calculations of magnetic field-dependent phthalocyanine monomer and dimer absorption spectra. Here, we propose that ring currents in organic semiconductors, which commonly comprise aromatic moieties, may present new opportunities for the understanding and exploitation of combined optical, electronic, and magnetic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Optical Spin Polarization of a Narrow-Linewidth Electron-Spin Qubit in a Chromophore/Stable-Radical System

Photoexcited organic chromophores appended to stable radicals can serve as qubit and/or qudit candidates for quantum information applications. 1,6,7,12-Tetra-(4-tert-butylphenoxy)-perylene-3,4 : 9,10-bis(dicarboximide) (tpPDI) linked to a partially deuterated α,γ-bisdiphenylene-β-phenylallyl radical (BDPA-d 16 ) was synthesized and characterized by time-resolved optical and electron paramagnetic resonance (EPR) spectroscopies. Photoexcitation of tpPDI-BDPA-d 16 results in ultrafast radical-enhanced intersystem crossing to produce a quartet state (Q) followed by formation of a spin-polarized doublet ground state (D 0 ). Pulse-EPR experiments confirmed the spin multiplicity of Q and yielded coherence times of T m =2.1±0.1 μs and 2.8±0.2 μs for Q and D 0 , respectively. BDPA-d 16 eliminates the dominant 1 H hyperfine couplings, resulting in a single narrow line for both the Q and D 0 states, which enhances the spectral resolution needed for good qubit addressability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Local Multimodal Electro-Chemical-Structural Characterization of Solid-Electrolyte Grain Boundaries

Typical models of polycrystalline ionic materials treat the grain boundary properties as single valued, without consideration of the full range of values that define the macroscopically measured average. Here a unique experimental platform suitable for local multimodal characterization of individual grain boundaries in bicrystal fibers is reported. A variation of three orders of magnitude in the grain boundary conductivity of ceria is observed, as measured across six individual bicrystals by both alternating current impedance spectroscopy and direct current (D.C.) linear sweep voltammetry. Nonlinear behavior of the D.C. measurements is consistent with resistance due to a space charge effect. Time-of-flight secondary ion beam spectroscopy reveals a correlation between grain boundary resistance and the concentration of impurities Si, Al, and Ca segregated at the grain boundaries, although the bulk concentrations of these impurities are negligible. Electron backscatter diffraction analysis of the crystal orientations suggests a correlation between the misorientation across the grain boundaries and grain boundary resistance. These correlations point towards a grain boundary resistance that arises from impurity-generated space charge effects and variations in impurity concentration and hence resistivity driven by the energetics of impurity segregation to grain boundaries of differing surface energies.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Contamination, Transportation or Transmutation in LENR Material Analyses

LENR experiments using various loading and triggering mechanisms rely on a variety of elemental and isotopic assays to determine LENR effects. These assays include optical microscopy, Scanning Electron Microscopy with Energy Dispersive X-Ray Analysis (SEM/EDX), X-Ray Photoelectron Spectroscopy (XPS) and Transmission Electron Microscopy (TEM). All of these methods observe the surface of a material. By dissolving or vaporizing the sample, Inductively Coupled Plasma Optical Element Spectroscopy (ICP-OES) can determine elemental composition (ppb) or with mass spectroscopy, isotopes (ICP/MS). One can use a focused ion beam (FIB) to cut open a sample and observe the “cut” with either SEM/EDX, or Time-of-Flight Secondary Ion Mass Spectroscopy (TOF-SIMS). High Purity Gamma Ray Spectroscopy (HPGe) and alpha/ beta Liquid Scintillator spectroscopy can be used. We’ve employed these assay methods in our NASA GRC research under both the Advanced Energy Conversion and Lattice Confinement Fusion Projects. However, there are limitations associated with each of these methods ranging from handling contamination, instrumental limitations including sensitivity and field of view, and sample preparation.

Low Energy Nuclear Reactions↗
DOE OSTI2021

Transparent window 2D IR spectroscopy of proteins

Proteins are complex, heterogeneous macromolecules that exist as ensembles of interconverting states on a complex energy landscape. A complete, molecular-level understanding of their function requires experimental tools to characterize them with high spatial and temporal precision. Infrared (IR) spectroscopy has an inherently fast time scale that can capture all states and their dynamics with, in principle, bond-specific spatial resolution. Two-dimensional (2D) IR methods that provide richer information are becoming more routine but remain challenging to apply to proteins. Spectral congestion typically prevents selective investigation of native vibrations; however, the problem can be overcome by site-specific introduction of amino acid side chains that have vibrational groups with frequencies in the “transparent window” of protein spectra. This Perspective provides an overview of the history and recent progress in the development of transparent window 2D IR of proteins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗