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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 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

All-Epitaxial Integration of Long-Wavelength Infrared Plasmonic Materials and Detectors for Enhanced Responsivity

Here, infrared detectors using monolithically integrated doped semiconductor “designer metals” are proposed and experimentally demonstrated. We leverage the “designer metal” groundplanes to form resonant cavities with enhanced absorption tuned across the long-wave infrared (LWIR). Detectors are designed with two target absorption enhancement wavelengths: 8 and 10 μm. The core of our detectors are quantum-engineered LWIR type-II superlattice p-i-n detectors with total thicknesses of only 1.42 and 1.80 μm for the 8 and 10 μm absorption enhancement devices, respectively. Our 8 and 10 μm structures show peak external quantum efficiencies of 45 and 27%, which are 4.5× and 2.7× enhanced, respectively, compared to control structures. We demonstrate the clear advantages of this detector architecture, both in terms of ease of growth/fabrication and enhanced device performance. The proposed architecture is absorber- and device-structure agnostic, much thinner than state-of-the-art LWIR T2SLs, and offers the opportunity for the integration of low dark current LWIR detector architectures for significant enhancement of IR detectivity.

42 ENGINEERING↗
DOE OSTI2021

PCET-Based Ligand Limits Charge Recombination with an Ir(III) Photoredox Catalyst

Upon photoinitiated electron transfer, charge recombination limits the quantum yield of photoredox reactions for which the rates for the forward reaction and back electron transfer are competitive. Taking inspiration from a proton-coupled electron transfer (PCET) process in Photosystem II, here a benzimidazole-phenol (BIP) has been covalently attached to the 2,2'-bipyridyl ligand of [Ir(dF(CF 3 )ppy) 2 (bpy)][PF 6 ] (dF(CF 3 )ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; bpy = 2,2'-bipyridyl). Excitation of the [Ir(dF(CF 3 )ppy) 2 (BIP-bpy)][PF 6 ] photocatalyst results in intramolecular PCET to form a charge-separated state with oxidized BIP. Subsequent reduction of methyl viologen dication (MV 2+ ), a substrate surrogate, by the reducing moiety of the charge separated species demonstrates that the inclusion of BIP significantly slows the charge recombination rate. The effect of ~24-fold slower charge recombination in a photocatalytic phthalimide ester reduction resulted in a greater than 2-fold increase in reaction quantum efficiency.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2021

A Tunable Multivariate Metal–Organic Framework as a Platform for Designing Photocatalysts

Catalysts for photochemical reactions underlie many foundations in our lives, from natural light harvesting to modern energy storage and conversion, including processes such as water photolysis by TiO 2 . Recently, metal–organic frameworks (MOFs) have attracted large interest within the chemical research community, as their structural variety and tunability yield advantages in designing photocatalysts to address energy and environmental challenges. Here, we report a series of novel multivariate metal–organic frameworks (MTV-MOFs), denoted as MTV-MIL-100. They are constructed by linking aromatic carboxylates and AB 2 OX 3 bimetallic clusters, which have ordered atomic arrangements. Synthesized through a solvent-assisted approach, these ordered and multivariate metal clusters offer an opportunity to enhance and fine-tune the electronic structures of the crystalline materials. Moreover, mass transport is improved by taking advantage of the high porosity of the MOF structure. Combining these key advantages, MTV-MIL-100(Ti,Co) exhibits a high photoactivity with a turnover frequency of 113.7 mol H2 gcat. –1 min –1 , a quantum efficiency of 4.25%, and a space time yield of 4.96 × 10 –5 in the photocatalytic hydrolysis of ammonia borane. Bridging the fields of perovskites and MOFs, this work provides a novel platform for the design of highly active photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Anionic Lipids Regulate the Light-Harvesting Complex 1-Reaction Center Photocycle in Purple Bacteria

Photosynthetic purple bacteria can capture and convert sunlight with a remarkable, nearly 100% quantum efficiency. The light-harvesting complex 1-reaction center (LH1-RC) core complex is the membrane complex fundamentally responsible for solar energy conversion. LH1-RC has a highly conserved surrounding lipid composition known to favor anionic lipids for an unknown function. Here, in this work, we compared experimentally the rate of LH1-to-RC energy transfer in detergent, membrane nanodiscs with varying lipid compositions, purified membrane fragments, and live cells. The energy transfer rate indicated that RC turnover decreased in neutral lipids, yet was partially restored in anionic lipids, revealing an unexpected lipid dependence. In complementary molecular dynamics simulations, the anionic lipid cardiolipin showed electrostatic interactions with LH1-RC that may mediate quinone exchange, providing a mechanism for the observed lipid dependence. Overall, these results revealed that anionic lipids facilitate LH1-RC redox cycling, identifying a functional role for membrane composition in photosynthetic solar energy conversion.

bacteria↗
DOE OSTI2026

Distinct Kinetic Signatures of Photodesorption from Metal Nanoparticles

Visible photon fluxes can influence the rate and selectivity of heterogeneously catalyzed reactions on metal nanoparticle surfaces. Models describing the influence of photon fluxes have typically introduced photon flux dependent apparent thermal kinetic parameters (reaction orders, activation energies, binding energies, etc.). This has relied on empirical fitting of reaction rate data, making mechanistic interpretations of how photon fluxes influence elementary step rates challenging and inconsistent with fundamental descriptions of photochemistry on metal surfaces developed from surface science studies. Using the CO adsorption–desorption quasi-equilibrium reaction on Pt/Al 2 O 3 catalysts as a model system, we measured steady state adsorbed CO (CO*) coverages under isothermal and isobaric (1 mbar CO) conditions as a function of temperature (473–573 K) and of 440 nm photon flux ((0.1–5.2) × 10 3 # hv Pt site –1 s –1 ) using in situ IR spectroscopy. Steady state CO* coverage on Pt was photon flux dependent with increasing photon flux causing decreasing coverage, consistent with photons driving CO* desorption rates faster than thermal CO* desorption rates. However, photon flux dependent CO* coverages were essentially temperature independent, inconsistent with models that describe photon effects using perturbations to apparent thermal kinetic parameters. Instead, 120 steady state CO* coverages as a function of temperature and photon flux are quantitatively described by a kinetic model in which the overall desorption rate is a summation of independent thermal and photon induced CO* desorption rates. Site-resolved analysis reveals distinct kinetic parameters for photon driven desorption of CO* from well-coordinated, under-coordinated, and highly under-coordinated Pt sites, with temperature-dependent apparent quantum efficiencies (AQE) consistent with temperature dependence of vibrational quanta distribution of adsorbed CO. The rigorous kinetic rate laws for independent photon and thermal driven pathways allow for predictive modeling of the influence of photon fluxes on the rates of CO* desorption under catalytic conditions. Further, the analysis provides evidence that steady state continuous wave photon fluxes can drive desorption/adsorption reactions on metal surfaces out of thermal equilibrium, reconciling surface science observations of molecular photodesorption with applied catalysis. The work establishes a general kinetic framework to be considered for photon driven processes on metals, and defines catalyst, reaction, and photon flux characteristic design principles for breaking Sabatier limitations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Energetic robustness to large scale structural fluctuations in a photosynthetic supercomplex

Abstract Photosynthetic organisms transport and convert solar energy with near-unity quantum efficiency using large protein supercomplexes held in flexible membranes. The individual proteins position chlorophylls to tight tolerances considered critical for fast and efficient energy transfer. The variability in protein organization within the supercomplexes, and how efficiency is maintained despite variability, had been unresolved. Here, we report on structural heterogeneity in the 2-MDa cyanobacterial PSI-IsiA photosynthetic supercomplex observed using Cryo-EM, revealing large-scale variances in the positions of IsiA relative to PSI. Single-molecule measurements found efficient IsiA-to-PSI energy transfer across all conformations, along with signatures of transiently decoupled IsiA. Structure based calculations showed that rapid IsiA-to-PSI energy transfer is always maintained, and even increases by three-fold in rare conformations via IsiA-specific chls. We postulate that antennae design mitigates structural fluctuations, providing a mechanism for robust energy transfer in the flexible membrane.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Spin-orbit-splitting-driven nonlinear Hall effect in NbIrTe 4

The Berry curvature dipole (BCD) serves as a one of the fundamental contributors to emergence of the nonlinear Hall effect (NLHE). Despite intense interest due to its potential for new technologies reaching beyond the quantum efficiency limit, the interplay between BCD and NLHE has been barely understood yet in the absence of a systematic study on the electronic band structure. Here, we report NLHE realized in NbIrTe 4 that persists above room temperature coupled with a sign change in the Hall conductivity at 150 K. First-principles calculations combined with angle-resolved photoemission spectroscopy (ARPES) measurements show that BCD tuned by the partial occupancy of spin-orbit split bands via temperature is responsible for the temperature-dependent NLHE. Our findings highlight the correlation between BCD and the electronic band structure, providing a viable route to create and engineer the non-trivial Hall effect by tuning the geometric properties of quasiparticles in transition-metal chalcogen compounds.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Structure of a biohybrid photosystem I-platinum nanoparticle solar fuel catalyst

Biohybrid solar fuel catalysts leverage natural light-driven enzymes to produce valuable fuel products. One useful biological platform for such a system is photosystem I, a pigment-protein complex that captures sunlight and converts it into chemical energy with near unity quantum efficiency, which generates low potential reducing equivalents for metabolism. Realizing and understanding the molecular basis for an approach that utilizes those electrons and stores solar energy as a fuel is therefore appealing. Here, we report the 2.27-Å global resolution cryo-EM structure of a photosystem I complex with bound platinum nanoparticles that catalyzes light-driven H 2 production. The platinum nanoparticle binding sites and possible stabilizing interactions are described. Overall, the investigation reveals a direct structural look at a photon-to-fuels photosynthetic biohybrid system.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Unidirectional luminescence from InGaN/GaN quantum-well metasurfaces

III–nitride light-emitting diodes (LEDs) are the backbone of ubiquitous lighting and display applications. Imparting directional emission is an essential requirement for many LED implementations. Although optical packaging, nanopatterning and surface roughening4 techniques can enhance LED extraction, directing the emitted light requires bulky optical components. Optical metasurfaces provide precise control over transmitted and reflected waveforms, suggesting a new route for directing light emission. However, it is difficult to adapt metasurface concepts for incoherent light emission, due to the lack of a phase-locking incident wave. Here, we demonstrate a metasurface-based design of InGaN/GaN quantum-well structures that generate narrow, unidirectional transmission and emission lobes at arbitrary engineered angles. We further demonstrate 7-fold and 100-fold enhancements of total and air-coupled external quantum efficiencies, respectively. The results present a new strategy for exploiting metasurface functionality in light-emitting devices.

inorganic LEDs↗
DOE OSTI2021

Bright and stable light-emitting diodes made with perovskite nanocrystals stabilized in metal–organic frameworks

Perovskite nanocrystals are exceptional candidates for light-emitting diodes (LEDs). However, they are unstable in the solid film and tend to degrade back to the bulk phase, which undermines their potential for LEDs. Here we demonstrate that perovskite nanocrystals stabilized in metal–organic framework (MOF) thin films make bright and stable LEDs. The perovskite nanocrystals in MOF thin films can maintain the photoluminescence and electroluminescence against continuous ultraviolet irradiation, heat and electrical stress. As revealed by optical and X-ray spectroscopy, the strong emission originates from localized carrier recombination. Bright LEDs made from perovskite-MOF nanocrystals are demonstrated with a maximum external quantum efficiency of over 15% and a high brightness of over 10 5 cd m -2 after the device reaches stabilization. During LED operation, the nanocrystals can be well preserved, free of ion migration or crystal merging through protection by the MOF matrix, leading to a stable performance over 50 hours.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Long lifetime of bialkali photocathodes operating in high gradient superconducting radio frequency gun

Abstract High brightness, high charge electron beams are critical for a number of advanced accelerator applications. The initial emittance of the electron beam, which is determined by the mean transverse energy (MTE) and laser spot size, is one of the most important parameters determining the beam quality. The bialkali photocathodes illuminated by a visible laser have the advantages of high quantum efficiency (QE) and low MTE. Furthermore, Superconducting Radio Frequency (SRF) guns can operate in the continuous wave (CW) mode at high accelerating gradients, e.g. with significant reduction of the laser spot size at the photocathode. Combining the bialkali photocathode with the SRF gun enables generation of high charge, high brightness, and possibly high average current electron beams. However, integrating the high QE semiconductor photocathode into the SRF guns has been challenging. In this article, we report on the development of bialkali photocathodes for successful operation in the SRF gun with months-long lifetime while delivering CW beams with nano-coulomb charge per bunch. This achievement opens a new era for high charge, high brightness CW electron beams.

43 PARTICLE ACCELERATORS↗
DOE OSTI2021

An adaptive approach to machine learning for compact particle accelerators

Abstract Machine learning (ML) tools are able to learn relationships between the inputs and outputs of large complex systems directly from data. However, for time-varying systems, the predictive capabilities of ML tools degrade if the systems are no longer accurately represented by the data with which the ML models were trained. For complex systems, re-training is only possible if the changes are slow relative to the rate at which large numbers of new input-output training data can be non-invasively recorded. In this work, we present an approach to deep learning for time-varying systems that does not require re-training, but uses instead an adaptive feedback in the architecture of deep convolutional neural networks (CNN). The feedback is based only on available system output measurements and is applied in the encoded low-dimensional dense layers of the encoder-decoder CNNs. First, we develop an inverse model of a complex accelerator system to map output beam measurements to input beam distributions, while both the accelerator components and the unknown input beam distribution vary rapidly with time. We then demonstrate our method on experimental measurements of the input and output beam distributions of the HiRES ultra-fast electron diffraction (UED) beam line at Lawrence Berkeley National Laboratory, and showcase its ability for automatic tracking of the time varying photocathode quantum efficiency map. Our method can be successfully used to aid both physics and ML-based surrogate online models to provide non-invasive beam diagnostics.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Photosystem stoichiometry adjustment is a photoreceptor-mediated process in Arabidopsis

Abstract Plant growth under spectrally-enriched low light conditions leads to adjustment in the relative abundance of the two photosystems in an acclimatory response known as photosystem stoichiometry adjustment. Adjustment of photosystem stoichiometry improves the quantum efficiency of photosynthesis but how this process perceives light quality changes and how photosystem amount is regulated remain largely unknown. By using a label-free quantitative mass spectrometry approach in Arabidopsis here we show that photosystem stoichiometry adjustment is primarily driven by the regulation of photosystem I content and that this forms the major thylakoid proteomic response under light quality. Using light and redox signaling mutants, we further show that the light quality-responsive accumulation of photosystem I gene transcripts and proteins requires phytochrome B photoreceptor but not plastoquinone redox signaling as previously suggested. In far-red light, the increased acceptor side limitation might deplete active photosystem I pool, further contributing to the adjustment of photosystem stoichiometry.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Rugged bialkali photocathodes encapsulated with graphene and thin metal film

Protection of free-electron sources has been technically challenging due to lack of materials that transmit electrons while preventing corrosive gas molecules. Two-dimensional materials uniquely possess both of required properties. Here, we report three orders of magnitude increase in active pressure and factor of two enhancement in the lifetime of high quantum efficiency (QE) bialkali photocathodes (cesium potassium antimonide (CsK 2 Sb)) by encapsulating them in graphene and thin nickel (Ni) film. The photoelectrons were extracted through the graphene protection layer in a reflection mode, and we achieved QE of ~ 0.17% at ~ 3.4 eV, 1/e lifetime of 188 h with average current of 8.6 nA under continuous illumination, and no decrease of QE at the pressure of as high as ~ 1 × 10 –3 Pa. In comparison, the QE decreased drastically at 10 –6 Pa for bare, non-protected CsK 2 Sb photocathodes and their 1/e lifetime under continuous illumination was ~ 48 h. We attributed the improvements to the gas impermeability and photoelectron transparency of graphene.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Pulsed laser deposition assisted epitaxial growth of cesium telluride photocathodes for high brightness electron sources

The development of high-brightness electron sources is critical to state-of-the-art electron accelerator applications like X-ray free electron laser (XFEL) and ultra-fast electron microscopy. Cesium telluride is chosen as the electron source material for multiple cutting-edge XFEL facilities worldwide. This manuscript presents the first demonstration of the growth of highly crystalized and epitaxial cesium telluride thin films on 4H-SiC and graphene/4H-SiC substrates with ultrasmooth film surfaces. The ordering of the film was characterized by in situ reflection high energy electron diffraction and multiple X-ray diagnostics. The results of the quantum efficiency performance for epitaxial cesium telluride photocathodes are also reported.

43 PARTICLE ACCELERATORS↗
DOE OSTI2025

Improved robustness of sequentially deposited potassium cesium antimonide photocathodes achieved by increasing the potassium content towards theoretical stoichiometry

Alkali antimonide semiconductor photocathodes are promising candidates for high-brightness electron sources for advanced accelerators, including free-electron lasers (FEL), due to their high quantum efficiency (QE), low emittance, and high temporal resolution. Two challenges with these photocathodes are (1) the lack of a universal deposition recipe to achieve crystal stoichiometries and (2) their high susceptibility to vacuum contamination, which restricts their operation pressure to ultrahigh vacuums and leads to a short lifetime and low extraction charge. To resolve these issues, it is essential to understand the elemental compositions of deposited photocathodes and correlate them to robustness. Here, we report depth profiles for potassium cesium antimonide photocathodes, which were investigated using synchrotron radiation x-ray photoelectron spectroscopy, and the robustness of those photocathodes. We prepared two types of photocathodes with different potassium contents via sequential thermal evaporation. Depth profiles revealed that the photocathodes with a potassium deficit had excess cesium at the surface, while the ratio of potassium and cesium to antimony decreased rapidly within the film. In contrast, the photocathodes with sufficient potassium had close to the theoretical stoichiometry of K 2 CsSb at the surface and maintained that stoichiometry for over half the entire film thickness. Both photocathode types had a similar maximum QE at 532 nm; however, exposure to oxygen revealed that the photocathode with a crystalline stoichiometry of K 2 CsSb maintained QE at one order of magnitude higher pressure compared to its potassium-deficit counterpart. These results highlight the importance of synthesizing potassium cesium antimonide photocathodes with sufficient potassium to achieve the theoretical crystalline stoichiometry for both high QE and improved robustness.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

Metal-free photocatalysts for hydrogen evolution

This review focuses on the discussion of the latest progress and remaining challenges in selected metal-free photocatalysts for hydrogen production. The scope of this review is limited to the metal-free elemental photocatalysts (i.e. B, C, P, S, Si, Se etc.), binary photocatalysts (i.e. BC 3 , B 4 C, C x N y , h-BN etc.) and their heterojunction, ternary photocatalysts (i.e. BCN) and their heterojunction, and different types of organic photocatalysts (i.e. linear, covalent organic frameworks, microporous polymer, covalent triazine frameworks etc.) and their heterostructures. Following a succinct depiction of the latest progress in hydrogen evolution on these photocatalysts, discussion has been extended to the potential strategies that are deemed necessary to attain high quantum efficiency and high solar-to-hydrogen (STH) conversion efficiency. Issues with reproducibility and the disputes in reporting the hydrogen evolution rate have been also discussed with recommendations to overcome them. A few key factors are highlighted that may facilitate the scalability of the photocatalyst from microscale to macroscale production in meeting the targeted 10% STH. This review is concluded with additional perspectives regarding future research in fundamental materials aspects of high efficiency photocatalysts followed by six open questions that may need to be resolved by forming a global hydrogen taskforce in order to translate bench-top research into large-scale production of hydrogen.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A new platform for development of photosystem I based thin films with superior photocurrent: TCNQ charge transfer salts derived from ZIF-8

The transmembrane photosynthetic protein complex Photosystem I (PSI) is highly sought after for incorporation into biohybrid photovoltaic devices due to its remarkable photoactive electrochemical properties, chiefly driving charge separation with ~1 V potential and ~100% quantum efficiency. In pursuit of these integrated technologies, three factors must be simultaneously tuned, namely, direct redox transfer steps, three-dimensional coordination and stabilization of PSI aggregates, and interfacial connectivity with conductive pathways. Building on our recent successful encapsulation of PSI in the metal–organic framework ZIF-8, herein we use the zinc and imidazole cations from this precursor to form charge transfer complexes with an extremely strong organic electron acceptor, TCNQ. Specifically, the PSI-Zn-H 2 mim-TCNQ charge transfer salt complex was drop cast on ITO to form dense films. Subsequent voltammetric cycling induced cation exchange and electrochemical annealing of the film was used to enhance electron conductivity giving rise to a photocurrent in the order of 15 μA cm -2 . This study paves the way for a myriad of future opportunities for successful integration of this unique class of charge transfer salt complexes with biological catalysts and light harvesters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗