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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods

Mononuclear Fe ions ligated by nitrogen (FeN x ) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O 2 reduction and thermocatalytic aerobic oxidations. Despite their promise as replacements for precious metals in a variety of practical applications, such as fuel cells, the discovery of new Fe-N-C catalysts has relied primarily on empirical approaches. In this context, the development of quantitative structure–reactivity relationships and benchmarking of catalysts prepared by different synthetic routes and by different laboratories would be facilitated by the broader adoption of methods to quantify atomically dispersed FeN x active centers. In the present study, we develop a kinetic probe reaction method that uses the aerobic oxidation of a model hydroquinone substrate to quantify the density of FeN x centers in Fe- N-C catalysts. The kinetic method is compared with low-temperature Mössbauer spectroscopy, CO pulse chemisorption, and electrochemical reductive stripping of NO derived from NO 2 – on a suite of Fe-N-C catalysts prepared by diverse routes and featuring either the exclusive presence of Fe as FeN x sites or the coexistence of aggregated Fe species in addition to FeN x . The FeN x site densities derived from the kinetic method correlate well with those obtained from CO pulse chemisorption and Mössbauer spectroscopy. The broad survey of Fe-N-C materials also reveals the presence of outliers and challenges associated with each site quantification approach. Furthermore, the kinetic method developed here does not require pretreatments that may alter active-site distributions nor specialized equipment beyond reaction vessels and analytical instrumentation (e.g., NMR).

36 MATERIALS SCIENCE↗
DOE OSTI2024

Overcoming the doping limit in GaAs by ion implantation and pulsed laser melting

Most semiconductors exhibit a saturation of free carriers when heavily doped with extrinsic dopants. This carrier saturation or “doping limit” is known to be related to the formation of native compensating defects, which, in turn, depends on the energy positions of their conduction band minimum and valence band maximum. Here, we carried out a systematic study on the n-type doping limit of GaAs via ion implantation and showed that this doping limitation can be alleviated by the transient process of pulsed laser melting (PLM). For n-type doping, both group VI (S) and amphoteric group IV (Si and Ge) dopants were implanted in GaAs. For comparison, p-type doping was also studied using Zn as the acceptor. Implanted dopants were activated by the PLM method, and the results are compared to rapid thermal annealing (RTA). Our results reveal that for all n-type dopants, while implantation followed by the RTA results in a similar saturation electron concentration of 2–3 × 10 18 cm –3 , the transient PLM process is capable of trapping high concentration of dopants in the substitutional site, giving rise to a carrier concentration of >10 19 cm –3 , exceeding the doping limit of GaAs. However, due to scatterings from point defects generated during PLM, the mobility of n-type GaAs after PLM is low (~80–260 cm 2 /V s). Subsequent RTA after PLM (PLM + RTA) is able to remove these point defects and recover the mobility to ~1000–2000 cm2/V s. The carrier concentrations of these PLM + RTA samples are reduced but are still a factor of 3 higher than RTA only GaAs. This can be understood as the dopants are already incorporated in the substitutional site after PLM; they are less likely to be “deactivated” by subsequent RTA. This work is significant to the understanding of doping mechanisms in semiconductors and provides a means for device applications, which require materials with ultra-high doping.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Direct and Inverse Photoelectron Spectroscopy Evidence for a Revised Picture of Electronic States of Negative Polarons in n‐Doped C 60

Abstract Determining the electronic levels associated with polarons, the fundamental charge carriers in organic semiconductors, is key to understanding the charge transport properties of these materials. Recent findings challenge the traditional view of these electronic levels by highlighting the importance of intra‐molecular Coulomb interactions in polarons. Experimental evidence was previously presented for a revised model of the negative polaron in the case of the polymer semiconductor poly(NDI2OD‐T 2 ); there, the addition of an excess electron was seen to lead to the emergence of a singly occupied state within the energy gap of the undoped material and an unoccupied state above the edge of the conduction states . Here, focus is on a small‐molecule semiconductor, C 60 , and spectral evidence is provided of a similar picture for the new states appearing upon polaron formation. Specifically, direct and inverse photoemission spectroscopy is used to investigate the density of states in C 60 films n‐doped with two dimeric dopants. The Coulomb interaction energy (Hubbard U ) of the C 60 anion is experimentally determined to be ≈1.1 eV, a value that aligns closely with theoretical predictions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Siloxyaluminate and Siloxygallate Complexes as Models for Framework and Partially Hydrolyzed Framework Sites in Zeolites and Zeotypes.

Anionic molecular models for nonhydrolyzed and partially hydrolyzed aluminum and gallium framework sites on silica, M[OSi(OtBu) 3 ] 4 - and HOM[OSi(OtBu) 3 ] 3 - (where M=Al or Ga), were synthesized from anionic chlorides Li{M[OSi(OtBu) 3 ] 3 Cl} in salt metathesis reactions. Sequestration of lithium cations with [12]crown-4 afforded charge-separated ion pairs composed of monomeric anions M[OSi(OtBu) 3 ] 4 - with outer-sphere [([12]crown-4) 2 Li] + cations, and hydroxides {HOM[OSi(OtBu) 3 ] 3 } with pendant [([12]crown-4)Li] + cations. These molecular models were characterized by single-crystal X-ray diffraction, vibrational spectroscopy, mass spectrometry and NMR spectroscopy. Upon treatment of monomeric [([12]crown-4)Li]{HOM[OSi(OtBu) 3 ] 3 } complexes with benzyl alcohol, benzyloxide complexes were formed, modeling a possible pathway for the formation of active sites for Meerwin-Ponndorf-Verley (MPV) transfer hydrogenations with Al/Ga-doped silica catalysts.

Dombrowski, James P↗
DOE OSTI2025

Harnessing Cation Disorder for Enhancing Ionic Conductivity in Lithium Inverse Spinel Halides

Halides are promising solid-state electrolytes for all-solid-state lithium batteries due to their exceptional oxidation stability, high Li-ion conductivity, and mechanical deformability. However, their practicality is limited by the reliance on rare and expensive metals. This study investigates the Li 2 MgCl 4 inverse spinel system as a cost-effective alternative. Molecular dynamics simulations reveal that lithium disordering at elevated temperatures significantly reduces the activation energy in Li 2 MgCl 4 . To stabilize this disorder at lower temperatures, we experimentally explored the Li x Zr 1–x/2 Mg x/2 Cl 4 system and found that Zr doping induces both Zr and Li disorder at the 16c site at room temperature (RT). This leads to a 2 order-of-magnitude increase in ionic conductivity for the Li 1.25 Zr 0.375 Mg 0.625 Cl 4 composition, achieving 1.4 × 10 –5 S cm –1 at RT, compared to pristine Li 2 MgCl 4 . By deconvoluting the role of lithium vacancies and dopants, we reveal that cation disordering to the 16c site predominantly enhances ionic conductivity, whereas lithium vacancy concentration has a very limited effect.

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

Atomistic mechanisms for catalytic transformations of NO to NH3, N2O, and N2 by Pd

The industrial pollutant NO is a potential threat to the environment and to human health. Thus, selective catalytic reduction of NO into harmless N2, NH3, and/or N2O gas is of great interest. Among many catalysts, metal Pd has been demonstrated to be most efficient for selectivity of reducing NO to N2. However, the reduction mechanism of NO on Pd, especially the route of N−N bond formation, remains unclear, impeding the development of new, improved catalysts. We report here the elementary reaction steps in the reaction pathway of reducing NO to NH3, N2O, and N2, based on density functional theory (DFT)-based quantum mechanics calculations. We show that the formation of N2O proceeds through an Eley-Rideal (E−R) reaction pathway that couples one adsorbed NO* with one non−adsorbed NO from the solvent or gas phase. This reaction requires high NO* surface coverage, leading first to the formation of the trans-(NO)2* intermediate with a low N−N coupling barrier (0.58 eV). Notably, trans-(NO)2* will continue to react with NO in the solvent to form N2O, that has not been reported. With the consumption of NO and the formation of N2O* in the solvent, the Langmuir-Hinshelwood (L-H) mechanism will dominate at this time, and N2O* will be reduced by hydrogenation at a low chemical barrier (0.42 eV) to form N2. In contrast, NH3 is completely formed by the L-H reaction, which has a higher chemical barrier (0.87 eV). Our predicted E-R reaction has not previously been reported, but it explains some existing experimental observations. In addition, we examine how catalyst activity might be improved by doping a single metal atom (M) at the NO* adsorption site to form M/Pd and show its influence on the barrier for forming the N−N bond to provide control over the product distribution.

Physics↗
DOE OSTI2024

Multi-microscopy characterization of threading dislocations in CVD-grown diamond films

We present site-coincident imaging of a high dislocation density boron-doped chemical vapor deposition-grown homoepitaxial (001) diamond film using electron channeling contrast imaging (ECCI), cathodoluminescence, transmission electron microscopy (TEM), and scanning secondary ion mass spectroscopy (SIMS). With growing interest in large area heteroepitaxial substrates, we show that ECCI is a promising technique to accurately evaluate dislocations in diamond films. We find the electron backscatter yield is sufficient to distinguish individual threading dislocations in ECCI despite the low atomic number of carbon, and we have generally good agreement between dislocations observed in ECCI and TEM of the same region. Importantly, relying on luminescence in the 430 nm dislocation-related A-band alone results in an underestimation of the defect density as we find only 20%–40% of the threading dislocations luminesce. Here, we further show that dislocations do not perturb the spatial uniformity of boron doping measured by SIMS, even when the dislocations are clustered with high density, and we can tentatively rule out strong segregation effects at the dislocations. Our results establish the complementary use of microscopy and microanalysis methods to rapidly characterize and understand the impact of dislocations in diamond thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Electrochemical Doping of Halide Perovskites by Noble Metal Interstitial Cations

Abstract Metal halide perovskites are an attractive class of semiconductors, but it has proven difficult to control their electronic doping by conventional strategies due to screening and compensation by mobile ions or ionic defects. Noble‐metal interstitials represent an under‐studied class of extrinsic defects that plausibly influence many perovskite‐based devices. In this work, doping of metal halide perovskites is studied by electrochemically formed Au + interstitial ions, combining experimental data on devices with a computational analysis of Au + interstitial defects based on density functional theory (DFT). Analysis suggests that Au + cations can be easily formed and migrate through the perovskite bulk via the same sites as iodine interstitials (I i + ). However, whereas I i + compensates n‐type doping by electron capture, the noble‐metal interstitials act as quasi‐stable n‐dopants. Experimentally, voltage‐dependent, dynamic doping by current density–time ( J–t ), electrochemical impedance, and photoluminescence measurements are characterized. These results provide deeper insight into the potential beneficial and detrimental impacts of metal electrode reactions on long‐term performance of perovskite photovoltaic and light‐emitting diodes, as well as offer an alternative doping explanation for the valence switching mechanism of halide‐perovskite‐based neuromorphic and memristive devices.

14 SOLAR ENERGY↗
DOE OSTI2025

Reducing Dark Conductivity of Cesium Tin Halide Perovskites with Donor Doping

The inorganic tin halide perovskites (such as Cs Sn Br 3 and Cs Sn I 3 ) exhibit high hole concentrations, which have been attributed to the presence of intrinsic defects such as cation vacancies. Despite their promise as photovoltaic materials, this high intrinsic conductivity limits deployment. Using hybrid density functional theory, we examine the impact of these intrinsic defects on the electronic properties of Cs Sn Br 3 and Cs Sn I 3 . We find that tin and cesium vacancies have low formation energies, especially under Sn -poor conditions, in agreement with prior work, and that the presence of these native acceptor defects can lead to high hole concentrations. However, effective donor doping of these systems can be obtained via Sc or Y incorporation. These impurities substitute on the Sn site, where they act as single donors. By examining the formation energy of these dopants versus the native defects, we show that Sc or Y doping should lead to a strong compensation, reducing hole concentrations under Sn -rich conditions. Published by the American Physical Society 2025

Lyons, John L. (ORCID:0000000180233055)↗
DOE OSTI2023

Spectral Signatures of a Negative Polaron in a Doped Polymer Semiconductor: Energy Levels and Hubbard U Interactions

The modern picture of negative charge carriers on conjugated polymers invokes the formation of a singly occupied (spin-up/spin-down) level within the polymer gap and a corresponding unoccupied level above the polymer conduction band edge. The energy splitting between these sublevels is related to on-site Coulomb interactions between electrons, commonly termed Hubbard U. However, spectral evidence for both sublevels and experimental access to the U value is still missing. Here, in this work, we provide evidence by n-doping the polymer P(NDI 2 OD-T 2 ) with [RhCp*Cp] 2 , [N-DMBI] 2 , and cesium. Changes in the electronic structure after doping are studied with ultraviolet photoelectron and low-energy inverse photoemission spectroscopies (UPS, LEIPES). UPS data show an additional density of states (DOS) in the former empty polymer gap while LEIPES data show an additional DOS above the conduction band edge. These DOS are assigned to the singly occupied and unoccupied sublevels, allowing determination of a U value of ~1 eV.

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

An exciton crystal in a moiré excitonic insulator

Strong Coulomb interactions can drive electrons to crystallize into a Wigner lattice. Achieving the bosonic analogue—a crystal of excitons—has remained challenging owing to their short lifetimes and weaker interactions. Here we report the observation of a thermodynamically stable exciton crystal in an excitonic insulator coupled to a moiré potential. Using an electron–hole bilayer composed of a monolayer MoSe 2 and a WS 2 /WSe 2 moiré superlattice, we constructed a tunable extended Bose–Hubbard system with electrical control over exciton and charge doping in thermal equilibrium. Optical spectroscopy revealed spontaneous crystallization of long-lived excitons at one exciton filling per three moiré sites, manifested as strong Umklapp scattering peaks. Exciton transport measurements further showed a pronounced exciton resistance peak at the same filling. When doped away from net charge neutrality, this moiré electron–hole bilayer can host correlated insulating phases in which dipolar excitonic insulators form on top of the background of a hole Mott insulator or generalized Wigner crystals. In conclusion, these findings establish moiré electron–hole bilayers as a versatile platform for realizing correlated crystalline phases of bosons and fermions.

Qi, Ruishi [University of California, Berkeley, CA↗
DOE OSTI2022

Rare-earth-doped electrospun scheelite CaWO 4 nanofibers with excitation-dependent photoluminescence and high-linearity cathodoluminescence for ratiometric UV wavelength and radiation sensors

Scheelite structured AWO 4 compounds (A = Ba, Ca, Pb and Sr) are efficient hosts for rare-earth dopants. In this work, high-aspect-ratio AWO 4 (A = Ba, Ca, Pb and Sr) nanofibers, doped with 5 mol.% Tb and 5 mol.% Eu on A site, were synthesized using a sol-gel electrospinning technique, and their performances as a ratiometric sensor for the detection of UV light wavelength were comparatively studied. High-resolution electron microscopy reveals the presence of nanosized grains composing the nanofibers. The AWO 4 :5Tb-5Eu nanofibers exhibit strong characteristic photoluminescence (PL) and cathodoluminescence (CL) emission from both Tb 3+ and Eu 3+ ions. In the case of CaWO 4 lattice, the emission intensity ratio of Tb 3+ /Eu 3+ is found to show a linear relationship with the excitation wavelength in the tested range of 240–330 nm, with efficient energy transfer from host lattice to rare-earth ions. However, a similar result is not observed in other scheelite structured BaWO 4 , PbWO 4 , and SrWO 4 nanofibers. Here, the unique PL emission characteristics of CaWO 4 :5Tb-5Eu under different UV excitation wavelengths are due to its unique excitation band. This study reveals a potential new application of CaWO 4 :5Tb-5Eu as a fluorescent probe for UV wavelength detection. Additionally, the CL intensities from CaWO 4 :5Tb-5Eu nanofibers exhibit highly linear dependences on the applied voltage and current without saturation, which can be utilized for radiation detection.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Enhanced Magnetization in CoFe 2 O 4 Through Hydrogen Doping

Magnetic spinel oxides have attracted extensive research interest due to their rich physics and wide range of applications. However, these materials invariably suffer suppressed magnetization, due to structural imperfections (e.g., disorder, anti-site defects, etc.). Herein, a dramatic enhanced magnetization is obtained with an increasement of 5 µ B /u.c in CoFe 2 O 4 (CFO) through ionic liquid gating induced hydrogen doping. Further, the intercalated hydrogen ions lead to both distinct lattice expansion of ≈0.7% and notable Fe valence state reduction through electron doping, in which ≈17% Fe 3+ is reduced into Fe 2+ . These facts collectively trigger a site-specific spin-flip on tetrahedrally coordinated Co 2+ sites that enhances the net ferrimagnetic moment nearly to its theoretical maximum for perfect CFO.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Identification of In Situ Generated High-Spin Fe(II)-N 4 Active Sites for Acidic Oxygen Reduction Reaction via Operando 57 Fe Mössbauer Spectroscopy

Iron-nitrogen-carbon (FeNC) catalysts are considered among the most promising alternative to Pt catalysts in acidic oxygen reduction reaction (ORR), yet the geometric and electronic structures of the true active site under reaction conditions have not been clearly elucidated. Herein, we synthesized a representative FeNC catalyst by pyrolyzing Fe 3+ absorbed on ZIF-8-derived N-doped carbon at a mild temperature under the H 2 /Ar atmosphere, where a formation mechanism of FeN 4 sites through a Zn-mediated Fe nanoparticle atomization process was proposed. The resulting FeNC-750 catalyst shows high acidic ORR activity with a half-wave potential of 0.838 V and a peak power density of 1 W cm -2 in proton-exchange membrane fuel cell (PEMFC). By using operando 57 Fe Mössbauer spectroscopy on FeNC-750, it was revealed that the pyrrolic N-coordinated high-spin Fe 2+ N 4 sites, which are in situ generated from high-spin Fe 3+ N 4 during ORR, are identified as catalytic active states. Density functional theory calculations further verified that, compared to the pyridinic N-coordinated low-spin Fe 2+ N 4 , the pyrrolic N-coordinated high-spin Fe 2+ exhibits optimized adsorption energy for reaction intermediates, thereby lowering the energy barrier of the rate-determining step (RDS) and facilitating OH* desorption. In conclusion, this work provides both experimental and theoretical evidence of the true active site in the FeNC during acidic ORR, offering significant insights for the rational design of high-performance materials for acidic fuel cells.

FeNC catalyst↗
DOE OSTI2022

First-principles calculation of gate-tunable ferromagnetism in magic-angle twisted bilayer graphene under pressure

Magic-angle twisted bilayer graphene (MATBG) is notable as a highly tunable platform for investigating strongly correlated phenomena such as unconventional superconductivity and quantum spin liquids, due to easy control of doping level through gating and sensitive dependence of the magic angle on hydrostatic pressure. Experimental observations of correlated insulating states, unconventional superconductivity and ferromagnetism in MATBG indicate that this system exhibits rich exotic phases. In this work, using density functional theory calculations in conjunction with the effective screening medium method, we find the MATBG under pressure at a twisting angle of 2.88 °and simulate how its electronic states evolve when doping level and electric field perpendicular to plane are tuned by gating. Our calculations show that, at doping levels between two electrons and four holes per moiré unit cell, a ferromagnetic (FM) solution with spin density localized at AA stacking sites is lower in energy than the nonmagnetic solution. The magnetic moment of this FM state decreases with both electron and hole doping and vanishes at four electrons/holes doped per moiré unit cell. Hybridization between the flat bands at the Fermi level and the surrounding dispersive bands can take place at finite doping. On increasing the out-of-plane electric field at zero doping, a transition from the FM state to the nonmagnetic one is seen. An investigation of impurity effects shows that both absorption of O 2 molecules and occurrence of Stone–Wales impurities suppress the FM state, and the mechanisms are understood from our calculations. We also analyze the interlayer bonding character due to flat bands via Wannier functions. Finally, we report trivial band topology of the flat bands in the FM state at a certain doping level.

Physics↗