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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 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Nanometer-Thick Sr 2 IrO 4 Freestanding Films for Flexible Electronics

In this article, we report the structural and optical properties of nanoscale Sr 2 IrO 4 freestanding thin-films fabricated using a water-soluble Sr 3 Al 2 O 6 layer. The coherent lattice structure, phonon modes, two-magnon Raman scattering, and optical absorption spectra of the Sr 2 IrO 4 nanomembrane are analogous to those of the layered iridate epitaxial thin-films and single crystals. Remarkably, the formation of 3-unit-cell-thick SrIrO 3 and interfacial composite layers alleviates the antiphase boundaries at the Sr 2 IrO 4 /Sr 3 Al 2 O 6 interface, resulting in structurally-robust nanomembranes. Our experimental results show that this freestanding thin-film approach of layered oxides can provide techniques for tuning or realizing unprecedented states beyond conventional thin-film methods, suggesting a pathway in achieving flexible layered-oxide electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Electrochemical Window of the Li-Ion Solid Electrolyte Li 7 La 3 Zr 2 O 12

The recent discovery of fast ion-conducting solid electrolytes could enable solid-state and other advanced battery chemistries with higher energy densities and enhanced safety. In addition to high ionic conductivity, a viable electrolyte should also exhibit an electrochemical window that is wide enough to suppress undesirable electronic transport (i.e., self-discharge and/or short circuiting) arising from charge injection or extraction from the electrodes. Here, direct current chronoamperometry, alternating current electrochemical impedance spectroscopy, and optical absorption band gap measurements are combined with first-principles calculations to systematically characterize the electrochemical window of the promising superionic conductor Li 7 La 3 Zr 2 O 12 (LLZO). Negligible electronic current was measured within LLZO for a wide range of voltages relevant for high-voltage cathodes. This auspicious behavior is consistent with both the large band gap (~6 eV) predicted for LLZO and the absolute positions of its band edges. These features imply that a wide electrochemical window is an intrinsic property of LLZO, facilitating its use in next-generation batteries.

Thompson, Travis↗
DOE OSTI2020

Spatially Resolved Persistent Photoconductivity in MoS2–WS2 Lateral Heterostructures

The optical and electronic properties of 2D semiconductors are intrinsically linked via the strong interactions between optically excited bound species and free carriers. Here we use near-field scanning microwave microscopy (SMM) to image spatial variations in photoconductivity in MoS 2 –WS 2 lateral multijunction heterostructures using photon energy-resolved narrowband illumination. We find that the onset of photoconductivity in individual domains corresponds to the optical absorption onset, confirming that the tightly bound excitons in transition metal dichalcogenides can nonetheless dissociate into free carriers. These photogenerated carriers are most likely n-type and are seen to persist for up to days. Informed by finite element modeling we reveal that they can increase the carrier density by up to 200 times. This persistent photoconductivity appears to be dominated by contributions from the multilayer MoS 2 domains, and we attribute the flake-wide response in part to charge transfer across the heterointerface. Spatial correlation of our SMM imaging with photoluminescence (PL) mapping confirms the strong link between PL peak emission photon energy, PL intensity, and the local accumulated charge. This work reveals the spatially and temporally complex optoelectronic response of these systems and cautions that properties measured during or after illumination may not reflect the true dark state of these materials but rather a metastable charged state.

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

Single-Particle Measurements Reveal the Origin of Low Solar-to-Hydrogen Efficiency of Rh-Doped SrTiO 3 Photocatalysts

Solar-powered photochemical water splitting using suspensions of photocatalyst nanoparticles is an attractive route for economical production of green hydrogen. SrTiO 3 -based photocatalysts have been intensely investigated due to their stability and recently demonstrated near-100% external quantum yield (EQY) for water splitting using wavelengths below 360 nm. To extend the optical absorption into the visible, SrTiO 3 nanoparticles have been doped with various transition metals. Here, in this work, we demonstrate that doping SrTiO 3 nanoparticles with 1% Rh introduces midgap acceptor states which reduce the free electron concentration by 5 orders of magnitude, dramatically reducing built-in potentials which could otherwise separate electron–hole (e–h) pairs. Rhodium states also function as recombination centers, reducing the photocarrier lifetime by nearly 2 orders of magnitude and the maximum achievable EQY to 10%. Furthermore, the absence of built-in electric fields within Rh-doped SrTiO 3 nanoparticles suggests that modest e–h separation can be achieved by exploiting a difference in mobility between electrons and holes.

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

Alkaline Earth-Based Ternary Chalcogenide Nanocrystals: Cadmium- and Lead-Free Optical Materials

As some of the most abundant elements on the Earth’s crust, alkaline earths bear great potential in Cd- and Pb-free catalytic, energy conversion, and light-emitting devices. Further, because large electropositive alkaline earths (Ae) can adopt high coordination numbers, they offer structural complexity beyond the tetrahedral (c-Si, II–VI, III–V) or octahedral (IV–VI) atomic sites that─with the notable exception of halide perovskites─are ubiquitous among nanocrystalline semiconductors. Here, in this work, we present a general route to photoluminescent 6–125 nm nanocrystals of ternary AeIn 2 Ch 4 semiconductors (Ae = Sr, Ba; Ch = S, Se) featuring eight- (Ae) as well as four-coordinate (In and Ch) atomic sites. Powder X-ray diffraction, electron microscopy, optical absorption, photoluminescence, and solid-state (ss)NMR spectroscopies attest to the ternary composition and phase purity of the nanocrystals. Continuous shape measures pinpoint the degree of distortion of individual crystallographic sites from ideal coordination polyhedra, allowing us to identify two very distinct types of Se coordination environments. Based on their higher order, pseudo-3-fold rotational symmetry, we assign 77 Se ssNMR peaks with negligible chemical shift anisotropy (CSA) to pyramidalized Se sites with vacant-trigonal bipyramid-like geometries and those with larger CSA to lower symmetry Se sites with seesaw-distorted geometries. Calculations help to better understand the electronic band structure of these materials. The nanocrystals are stable at room temperature in open air for several weeks, and some compositions up to 1000 °C under Ar, making them strong candidates for practical applications.

alkaline earth↗
DOE OSTI2017

Photoresponse of Natural van der Waals Heterostructures

Van der Waals heterostructures consisting of two-dimensional materials offer a platform to obtain materials by design and are very attractive owing to unique electronic states. Research on 2D van der Waals heterostructures (vdWH) has so far been focused on fabricating individually stacked atomically thin unary or binary crystals. Such systems include graphene, hexagonal boron nitride, and members of the transition metal dichalcogenide family. In this paper, we present our experimental study of the optoelectronic properties of a naturally occurring vdWH, known as franckeite, which is a complex layered crystal composed of lead, tin, antimony, iron, and sulfur. We present here that thin film franckeite (60 nm < d < 100 nm) behaves as a narrow band gap semiconductor demonstrating a wide-band photoresponse. We have observed the band-edge transition at ~1500 nm (~830 meV) and high external quantum efficiency (EQE ≈ 3%) at room temperature. Laser-power-resolved and temperature-resolved photocurrent measurements reveal that the photocarrier generation and recombination are dominated by continuously distributed trap states within the band gap. To understand wavelength-resolved photocurrent, we also calculated the optical absorption properties via density functional theory. Finally, we have shown that the device has a fast photoresponse with a rise time as fast as ~1 ms. Finally, our study provides a fundamental understanding of the optoelectronic behavior in a complex naturally occurring vdWH, and may pave an avenue toward developing nanoscale optoelectronic devices with tailored properties.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Radiation Tolerant Nanowire Array Solar Cells

Space power systems require photovoltaics that are lightweight, efficient, reliable, and capable of operating for years or decades in space environment. Current solar panels use planar multi-junction, III-V based solar cells with very high efficiency, but their specific power (power to weight ratio) is limited by the added mass of radiation shielding (e.g. coverglass) required to protect the cells from the high-energy particle radiation that occurs in space. Here we demonstrate that III-V nanowire-array solar cells have dramatically superior radiation performance relative to planar solar cell designs and show this for multiple cell geometries and materials, including GaAs and InP. Nanowire cells exhibit damage thresholds ranging from ~10-40 times higher than planar control solar cells when subjected to irradiation by 100-350 keV protons and 1 MeV electrons. Furthermore, using Monte Carlo simulations, we show that this improvement is due in part to a reduction in the displacement defect generation within the wires arising from their nanoscale dimensions. Radiation tolerance, combined with the efficient optical absorption and the improving performance of nanowire photovoltaics, indicates that nanowire arrays could provide a pathway to realize high-specific-power, substrate-free, III-V space solar cells with substantially reduced shielding requirements. More broadly, the exceptional reduction in radiation damage suggests that nanowire architectures may be useful in improving the radiation tolerance of other electronic and optoelectronic devices.

14 SOLAR ENERGY↗
DOE OSTI2025

Controlling Ligand Excimer Formation with Dipole Changes in Emissive Rare-Earth/Phosphonic Acid Complexes

The interactions between substituted arylvinyl phosphonic acid (AVPA) ligands within a Eu-AVPA complex are shown to influence the outcomes of excited state evolution after photoexcitation. Compared with unfunctionalized AVPAs, pairs of ligands functionalized with CF 3 in the para position preassociate in the ground state of complexes with Eu 3+ according to calculated geometry optimizations. The CF 3 -substituted AVPA complexes show evidence of red-shifted optical absorption and undergo more efficient excimer formation, as revealed by transient absorption spectroscopy. We rationalize this behavior through simulations of excited-state geometry optimizations that reveal evolution toward interligand phenyl-phenyl planarity for specific excited states. Emission from complexed Eu 3+ after energy transfer from the ligand is found to be weaker with CF 3 substitution, which we hypothesize is due to intracomplex, interligand aggregates with excimer-promoting geometries. These observations point to the need to consider ground-state geometries as well as dynamic excited-state processes to understand the flow of energy in rare earth coordination complexes.

09 BIOMASS FUELS↗
DOE OSTI2017

Fine-Tuning the Optoelectronic Properties of Freestanding Borophene by Strain

Two-dimensional boron (borophene) is a promising, newly synthesized monolayer metal with promising electronic and optical properties. Borophene has only been recently synthesized on silver substrates, and displays a variety of crystal structures and substrate-induced strains depending on the growth conditions and surface orientation. Here, we present an extensive first-principles study of the structural and optoelectronic properties of the two proposed structures of borophene, β 12 and δ 6 , under strain. With a density functional theory analysis, we determine that the optical absorbance and electronic band structure are continuously tunable upon application of few percent of strain. While both structures remain metallic with moderate strains of up to 6% applied, key features of the band structure, as well as the inplane anisotropy of the complex dielectric function and optical absorption, can be significantly modified.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Mechanistic Studies of Photoinduced Spin Crossover and Electron Transfer in Inorganic Complexes

Electronic excited-state phenomena provide a compelling intersection of fundamental and applied research interests in the chemical sciences. This holds true for coordination chemistry, where harnessing the strong optical absorption and photocatalytic activity of compounds depends on our ability to control fundamental physical and chemical phenomena associated with the nonadiabatic dynamics of electronic excited states. The central events of excited-state chemistry can critically influence the dynamics of electronic excited states, including internal conversion (transitions between distinct electronic states) and intersystem crossing (transitions between electronic states with different spin multiplicities), events governed by nonadiabatic interactions between electronic states in close proximity to conical intersections, as well as solvation and electron transfer. The diversity of electronic and nuclear dynamics also makes the robust interpretation of experimental measurements challenging. Developments in theory, simulation, and experiment can all help address the interpretation and understanding of chemical dynamics in organometallic and coordination chemistry. Synthesis presents the opportunity to chemically engineer the strength and symmetry of the metal–ligand interactions. This chemical control can be exploited to understand the influence of electronic ground state properties on electronic excited-state dynamics. New time-resolved experimental methods and the insightful exploitation of established methods have an important role in understanding, and ideally controlling, the photophysics and photochemistry of transition metal complexes. Techniques that can disentangle the coupled motion of electrons and nuclear dynamics warrant emphasis. In this work, we present a review of electron localization dynamics in charge transfer excited states and the dynamics of photoinitiated spin crossover dynamics. Both electron localization and spin crossover have been investigated by numerous research groups with femtosecond resolution spectroscopy, but challenges in experimental interpretation have left significant uncertainty about the molecular properties that control these phenomena. Our Account will emphasize how tailoring the experimental probe, femtosecond resolution vibrational anisotropy for electron localization, and femtosecond resolution hard X-ray fluorescence for spin crossover can make a significant impact on the interpretability of experimental measurements. The emphasis on thorough and robust interpretation has also led to an emphasis on simpler molecular systems. This enables iteration between experiment and theory, a requirement for the development of a more predictive understanding of electronic excited-state phenomena and an essential step to the development of design rules for solar materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

High Yield Synthesis of Mesoscopic Conductive and Dispersible Carbon Nanostructures via Ultrasonication of Commercial Precursors

The need to produce large quantities of graphenic materials displaying excellent conductivity, thermal resistance, and tunable properties for industrial applications has spurred interest in new techniques for exfoliating graphite. In this paper, sonication-assisted exfoliation of graphitic precursors in the presence of chloroform is shown to produce chemically and structurally unique exfoliated graphitic materials in high yields. These exfoliated graphites, referred to as mesographite and mesographene, respectively, exhibit unique properties which depend on the number of layers and exfoliation conditions. Structural characterization of mesographene reveals the presence of nanoscale two-dimensional graphene layers, and threedimensional carbon nanostructures sandwiched between layers, similar to those found in ball-milled and intercalated graphites. The conductivities of mesographite and mesographene are 2700 and 2000 S/m, respectively, indicating high conductivity despite flake damage. Optical absorption measurements of mesographite sonicated in various solvents showed significant changes in dispersion characteristics, and also indicated significant changes to mesoscopic colloidal behavior. A mechanism for functionalization and formation of capped carbon nanostructures is proposed by integrating the chemical and structural characterization in relation to the various carbon structures observed by electron microscopy. Composites based on common polymers were prepared by solution processing, and changes in thermal properties indicate improved dispersion of mesographite in polar polymers.

Srivastava, Vikram K↗
DOE OSTI2021

Design of High-Performance Lead-Free Quaternary Antiperovskites for Photovoltaics via Ion Type Inversion and Anion Ordering

The emergence of halide double perovskites significantly increases the compositional space for lead-free and air-stable photovoltaic absorbers compared to halide perovskites. Nevertheless, most halide double perovskites exhibit oversized band gaps (>1.9 eV) or dipole-forbidden optical transition, which are unfavorable for efficient single-junction solar cell applications. The current device performance of halide double perovskite is still inferior to that of lead-based halide perovskites, such as CH 3 NH 3 PbI 3 (MAPbI 3 ). Here, by ion type inversion and anion ordering on perovskite lattice sites, two new classes of pnictogen-based quaternary antiperovskites with the formula of X 6 B 2 AA' and X 6 BB'A 2 are designed. Phase stability and tunable band gaps in these quaternary antiperovskites are demonstrated based on first-principles calculations. Further photovoltaic-functionality-directed screening of these materials leads to the discovery of 5 stable compounds (Ca 6 N 2 AsSb, Ca 6 N 2 PSb, Sr 6 N 2 AsSb, Sr 6 N 2 PSb, and Ca 6 NPSb 2 ) with suitable direct band gaps, small carrier effective masses and low exciton binding energies, and dipole-allowed strong optical absorption, which are favorable properties for a photovoltaic absorber material. The calculated theoretical maximum solar cell efficiencies based on these five compounds are all larger than 29%, comparable to or even higher than that of the MAPbI 3 based solar cell. Finally, our work reveals the huge potential of quaternary antiperovskites in the optoelectronic field and provides a new strategy to design lead-free and air-stable perovskite-based photovoltaic absorber materials.

three-dimensional electronic transport↗
DOE OSTI2024

Ligand Desorption and Fragmentation in Oleate-Capped CdSe Nanocrystals under High-Intensity Photoexcitation

Semiconductor nanocrystals (NCs) offer prospective use as active optical elements in photovoltaics, light-emitting diodes, lasers, and photocatalysts due to their tunable optical absorption and emission properties, high stability, and scalable solution processing, as well as compatibility with additive manufacturing routes. Over the course of experiments, during device fabrication, or while in use commercially, these materials are often subjected to intense or prolonged electronic excitation and high carrier densities. The influence of such conditions on ligand integrity and binding remains underexplored. Here, in this study, we expose CdSe NCs to laser excitation and monitor changes in oleate that is covalently attached to the NC surface using nuclear magnetic resonance as a function of time and laser intensity. Higher photon doses cause increased rates of ligand loss from the particles, with upward of 50% total ligand desorption measured for the longest, most intense excitation. Surprisingly, for a range of excitation intensities, fragmentation of the oleate is detected and occurs concomitantly with formation of aldehydes, terminal alkenes, H 2 , and water. After illumination, NC size, shape, and bandgap remain constant although low-energy absorption features (Urbach tails) develop in some samples, indicating formation of substantial trap states. The observed reaction chemistry, which here occurs with low photon to chemical conversion efficiency, suggests that ligand reactivity may require examination for improved NC dispersion stability but can also be manipulated to yield desired photocatalytically accessed chemical species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Pursuing Heteroleptic Ligand Design Principles for Photoactive Fe Complexes with Ultrafast X-ray Emission and Variable-Temperature Optical Spectroscopies

Understanding the key parameters that govern the photophysical and photochemical properties of transition metal complexes is essential for the development of efficient photosensitizers for photocatalytic applications. Achieving this objective necessitates clear and detailed investigations of their electronic excited states, for which time-resolved metal Kβ X-ray emission spectroscopy (XES) has proven highly effective. Here, we present a time-resolved Fe Kβ XES study of a heteroleptic Fe(II) polypyridyl carbene complex, [Fe(phen) 2 (C 4 H 10 N 4 )] 2+ (1; phen = 1,10-phenanthroline), utilizing both the valence-to-core and Kβ mainline spectral regions, complemented by variable-temperature transient optical absorption (VT-TA) spectroscopy. Detailed analysis of the time-resolved Kβ XES data, supported by density functional theory (DFT) calculations and an Eyring analysis of the VT-TA data, reveals parallel excited state relaxation dynamics that support an assignment of the long-lived excited state to a triplet metal-centered state. Placing these results in the context of prior studies of heteroleptic Fe(II) polypyridyl cyanide complexes motivated a series of DFT calculations to investigate the effects of ligand structural flexibility and arrangement. These calculations reinforce the experimentally derived conclusion that constraining structural flexibility with multidentate ligands significantly impacts the excited state relaxation dynamics. Furthermore, our study emphasizes that the arrangement of strong field ligands in heteroleptic complexes substantially affects the energy of Jahn–Teller active triplet metal-centered states in low-spin d 6 metal complexes. Together, these findings provide synthetic design principles for extending metal-to-ligand charge transfer excited state lifetimes of heteroleptic Fe complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

PdSe 2 : Pentagonal Two-Dimensional Layers with High Air Stability for Electronics

Most studied two-dimensional (2D) materials exhibit isotropic behavior due to high lattice symmetry; however, lower-symmetry 2D materials such as phosphorene and other elemental 2D materials exhibit very interesting anisotropic properties. In this work, we report the atomic structure, electronic properties, and vibrational modes of few-layered PdSe 2 , exfoliated from bulk crystals, a pentagonal 2D layered noble transition metal dichalcogenide with a puckered morphology that is air-stable. Micro-absorption optical spectroscopy and first-principles calculations reveal a wide band gap variation in this material from ~0 (bulk) to ~1.3 eV (monolayer). The Raman active vibrational modes of PdSe 2 were identified using polarized Raman spectroscopy, and the strong interlayer interaction was revealed from the large thickness-dependent Raman peak shifts, agreeing with first-principles Raman simulations. Field-effect transistors made from the few-layer PdSe 2 display tunable ambipolar charge carrier conduction with a high electron apparent field-effect mobility of ~158 cm 2 V -1 s -1 , indicating the promise of this anisotropic, air-stable, pentagonal 2D material for 2D electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Optical Enhancement in Heteroleptic Ru(II) Polypyridyl Complexes Using Electron-Donor Ancillary Ligands

Organic dyes are a viable alternative to silicon for energy conversion. Using simulations from first-principles, we show that chemical manipulation is a powerful tool for tuning the optical absorption spectra of a special class of dyes in a way that is convenient for exploitation in dye-sensitized solar cells. Specifically, we have carried out density functional theory calculations on three Ru(II) polypyridyl complexes with electron-donor ancillary ligands. These complexes were recently developed to study how different electron-donor ancillary ligands affect the photophysical and electrochemical properties of these dyes for light harvesting and photon-to-electron conversion efficiency. We found that the electron-donor ancillary ligands significantly enhance the light harvesting in the visible and the near-infrared regions relative to the reference dye N3. Furthermore, we detected a decrease in the ionization potential, which improves the energy alignment with the redox potentials of the electrolyte. These findings demonstrated that better organic materials for energy applications were developed.

Chemistry↗
DOE OSTI2011

Anomalously Large Polarization Effect Responsible for Excitonic Red Shifts in PbSe Quantum Dot Solids

The formation of solid thin films from colloidal semiconductor quantum dots (QDs) is often accompanied by red shifts in excitonic transitions, but the mechanisms responsible for the red shifts are under debate. We quantitatively address this issue using optical absorption spectroscopy of two-dimensional (2D) and three-dimensional (3D) arrays of PbSe QDs with controlled inter-QD distance, which was determined by the length of alkanedithiol linking molecules. With decreasing inter-QD distance, the first and second exciton absorption peaks show increasing red shifts. Using thin films consisting of large and isolated QDs embedded in a matrix of small QDs, we determine that a dominant contribution to the observed red shift is due to changes in polarization of the dielectric environment surrounding each QD ({approx}88%), while electronic or transition dipole coupling plays a lesser role. However, the observed red shifts are more than 1 order of magnitude larger than theoretical predictions based on the dielectric polarization effect for spherical QDs. We attribute this anomalously large polarization effect to deviations of the exciton wave functions from eigenfunctions of the idealized spherical quantum well model.

36 MATERIALS SCIENCE↗