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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Edge States Drive Exciton Dissociation in Ruddlesden–Popper Lead Halide Perovskite Thin Films

Efficient photovoltaic cells based on thin films of solution-processed 2D Ruddlesden–Popper hybrid perovskites (RPPs) represent an exciting breakthrough due to their enhanced tunability and chemical stability relative to those fabricated from 3D phases. However, reports of efficient charge separation and current collection are in apparent contradiction with the well-known enhancement of the exciton binding energy in multilayered halide perovskites, which should lower the device’s internal quantum efficiency and voltage. This controversy has led to various proposals for the electronic and physical structure of RPP thin films, including phase inhomogeneity as the driving force for exciton dissociation and transport. We address this apparent paradox in high-quality hot-cast RPP films by correlating ultrafast transient absorption spectroscopy with X-ray scattering measurements. We show that a hot-casting fabrication method produces highly phase pure n = 3 (BA) 2 (MA) n-1 Pb n I 3n+1 RPP structures. The high-phase purity and large grain sizes allow us to observe vertical transport of excitons via a diffusive process and allow us to determine that charge separation is primarily driven by dissociation at surface localized subgap electronic states. Furthermore, we analyze the differential absorption kinetics in films of varying thickness to directly determine that the excitonic diffusion constant is ~0.18 cm 2 s –1 . We propose that a surface localized structural distortion, observed using surface selective grazing incidence X-ray scattering measurements, is responsible for the creation of the surface localized defect states. We find that the density and spatial distribution of these defect states is a function of preparation conditions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Phase Transitions in Metal–Organic Frameworks Directly Monitored through In Situ Variable Temperature Liquid-Cell Transmission Electron Microscopy and In Situ X-ray Diffraction

Zr 6 -based metal–organic frameworks (MOFs) with tetratopic organic linkers have been extensively investigated owing to their versatile structural tunability. While diverse topologies and polymorphism in the resulting MOFs are often encountered with tetratopic linkers and Zr 6 nodes, reports on phase transitions within these systems are rare. Thus, we have a limited understanding of polymorph transformations, hindering the rational development of pure phase materials. In this study, a phase transition from a microporous MOF, scu-NU-906, to a mesoporous MOF, csq-NU-1008, was discovered and monitored through in situ variable temperature liquid-cell transmission electron microscopy (VT-LCTEM), high-resolution transmission electron microscopy (HRTEM), and in situ variable temperature powder X-ray diffraction (VT-PXRD). Furthermore, it was found that the microporous- to-mesoporous transformation in the presence of formic acid occurs via a concomitant dissolution–reprecipitation process.

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

Autonomous reinforcement learning agent for chemical vapor deposition synthesis of quantum materials

Abstract Predictive materials synthesis is the primary bottleneck in realizing functional and quantum materials. Strategies for synthesis of promising materials are currently identified by time-consuming trial and error and there are no known predictive schemes to design synthesis parameters for materials. We use offline reinforcement learning (RL) to predict optimal synthesis schedules, i.e., a time-sequence of reaction conditions like temperatures and concentrations, for the synthesis of semiconducting monolayer MoS 2 using chemical vapor deposition. The RL agent, trained on 10,000 computational synthesis simulations, learned threshold temperatures and chemical potentials for onset of chemical reactions and predicted previously unknown synthesis schedules that produce well-sulfidized crystalline, phase-pure MoS 2 . The model can be extended to multi-task objectives such as predicting profiles for synthesis of complex structures including multi-phase heterostructures and can predict long-time behavior of reacting systems, far beyond the domain of molecular dynamics simulations, making these predictions directly relevant to experimental synthesis.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Spinodal enhancement of fluctuations in nucleus-nucleus collisions

Subensemble Acceptance Method (SAM) [1, 2] is an essential link between measured event-by-event fluctuations and their grand canonical theoretical predictions such as lattice QCD. The method allows quantifying the global conservation law effects in fluctuations. In its basic formulation, SAM requires a sufficiently large system such as created in central nucleus-nucleus collisions and sufficient space-momentum correlations. Directly in the spinodal region of the First Order Phase Transition (FOPT) different approximations should be used that account for finite size effects. Thus, we present the generalization of SAM applicable in both the pure phases, metastable and unstable regions of the phase diagram [3]. Obtained analytic formulas indicate the enhancement of fluctuations due to crossing the spinodal region of FOPT and are tested using molecular dynamics simulations. A rather good agreement is observed. Using transport model calculations with interaction potential we show that the spinodal enhancement of fluctuations survives till the later stages of collision via the memory effect [4]. However, at low collision energies the space-momentum correlation is not strong enough for this signal to be transferred to second and third order cumulants measured in momentum subspace. This result agrees well with recent HADES data on proton number fluctuations at $\sqrt{S_{NN}}$ = 2.4 GeV which are found to be consistent with the binomial momentum space acceptance [5].

Poberezhnyuk, Roman↗
DOE OSTI2023

Mg and Al-induced phase transformation and stabilization of Ga 2 O 3 -based $\gamma$-phase spinels

Ga 2 O 3 films were deposited on (100) MgAl 2 O 4 spinel substrates at 550, 650, 750, and 850 °C using metal-organic chemical vapor deposition and investigated using x-ray diffraction and transmission electron microscopy. A phase-pure γ-Ga 2 O 3 -based material having an inverse spinel structure was formed at 850 °C; a mixture of the γ-phase and β-Ga 2 O 3 was detected in films grown at 750 °C. Only β-Ga 2 O 3 was determined in the films deposited at 650 and 550 °C. A β- to γ-phase transition occurred from the substrate/film interface during growth at 750 °C. The growth and stabilization of the γ-phase at the outset of film growth at 850 °C was affected by the substantial Mg and Al chemical interdiffusion from the MgAl 2 O 4 substrate observed in the energy-dispersive x-ray spectrum. Further, atomic-scale investigations via scanning transmission electron microscopy of the films grown at 750 and 850 °C revealed a strong tetrahedral site preference for Ga and an octahedral site preference for Mg and Al. It is postulated that the occupation of these atoms in these particular sites drives the β-Ga 2 O 3 to γ-phase transition and markedly enhances the thermal stability of the latter phase at elevated temperatures.

42 ENGINEERING↗
DOE OSTI2022

Phase controlled synthesis of transition metal carbide nanocrystals by ultrafast flash Joule heating

Nanoscale carbides enhance ultra-strong ceramics and show activity as high-performance catalysts. Traditional lengthy carburization methods for carbide syntheses usually result in coked surface, large particle size, and uncontrolled phase. Here, a flash Joule heating process is developed for ultrafast synthesis of carbide nanocrystals within 1 s. Various interstitial transition metal carbides (TiC, ZrC, HfC, VC, NbC, TaC, Cr 2 C 3 , MoC, and W 2 C) and covalent carbides (B 4 C and SiC) are produced using low-cost precursors. By controlling pulse voltages, phase-pure molybdenum carbides including β-Mo 2 C and metastable α-MoC 1-x and η-MoC 1-x are selectively synthesized, demonstrating the excellent phase engineering ability of the flash Joule heating by broadly tunable energy input that can exceed 3000 K coupled with kinetically controlled ultrafast cooling (>10 4 K s –1 ). Theoretical calculation reveals carbon vacancies as the driving factor for topotactic transition of carbide phases. The phase-dependent hydrogen evolution capability of molybdenum carbides is investigated with β-Mo 2 C showing the best performance.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Spontaneous formation of robust two-dimensional perovskite phases

The two-dimensional on three-dimensional (2D/3D) perovskite bilayer heterostructure can improve the stability and performance of perovskite solar cells. We show that the 2D/3D perovskite stack in a device evolves dynamically during its end-of-life decomposition. Initially phase-pure 2D interlayers can evolve differently, resulting in different device stabilities. We show that a robust 2D interlayer can be formed using mixed solvents to regulate its crystallinity and phase purity. The resulting 2D/3D devices achieved 25.9% efficiency and had good durability, retaining 91% of their initial performance after 1074 hours at 85°C using maximum power point tracking.

14 SOLAR ENERGY↗
DOE OSTI2026

NOx mediated formation of ε – UO 3 during thermal decomposition of uranyl nitrate hexahydrate under static air conditions

The thermal decomposition of uranyl nitrate hexahydrate in air at temperatures of 650 – 800 °C is expected to yield α – U 3 O 8 through intermediate UO 3 phases. Here, n this study, Raman spectroscopy complimented by powder X-ray diffraction revealed the unexpected formation of ε – UO 3 as an accompanying phase during thermal decomposition of UNH at 700 °C under static air conditions. Experiments demonstrated that ε – UO 3 does not form during the initial ramp up stage nor during the high temperature heating period; but instead forms during the cooling stage between 250 – 400 °C. Additional experiments revealed that UNH initially decomposes through an amorphous UO 3 intermediate prior to α – U 3 O 8 formation. Attempts to bypass the U 3 O 8 precursor in the formation of ε – UO 3 were unsuccessful, supporting the necessity of U 3 O 8 (α – U 3 O 8 in this study) in the formation of ε – UO 3 . The observed phase evolution is proposed to result from the NOx species generated during UNH thermal decomposition, which create localized oxidizing conditions within the furnace under static air conditions. Furthermore, a predominantly phase pure ε – UO 3 was synthesized under static air conditions through the addition of an extra plateau at 250 °C during the cooling step. These findings demonstrate the importance of gas-phase chemistry and cooling conditions in uranium oxide phase evolution and provide additional insight into ε – UO 3 formation pathways.

Epsilon uranium trioxide↗
DOE OSTI2021

A series of Rb 4 Ln 2 (P 2 S 6 )(PS 4 ) 2 (Ln = La, Ce, Pr, Nd, Sm, Gd) rare earth thiophosphates with two distinct thiophosphate units [P V S 4 ] 3- and [P IV 2 S 6 ] 4-

A series of rubidium rare earth thiophosphates with the formula Rb 4 Ln 2 (P 2 S 6 )(PS 4 ) 2 (Ln = La, Ce, Pr, Nd, Sm, and Gd) were synthesized using the high temperature molten flux crystal growth method utilizing a RbBr flux. Single crystals of all title compounds, as well as phase pure powders of the La-, Ce-, and Sm-containing compositions, were obtained. Single crystals of the title compounds were characterized by single crystal and powder X-ray diffraction for structure and phase identification. Rb 4 Ln 2 (P 2 S 6 )(PS 4 ) 2 crystallizes in the monoclinic crystal system adopting the P2 1 /n space group for the large rare earths (Ln = La, Ce, Pr) and the C2/c space group for the smaller rare earths (Ln = Nd, Sm, Gd). This Rb 4 Ln 2 (P 2 S 6 )(PS 4 ) 2 series is a rare example of thiophosphates containing both tetrahedral [P V S 4 ] 3– and dimeric [P IV 2 S 6 ] 4– thiophosphate units that, in this structural family, link corrugated rare earth sulfide chains into sheets. Here, the band gaps of the materials were determined from UV–Vis data and the fluorescence spectrum of Rb 4 Ce 2 (P 2 S 6 )(PS 4 ) 2 was collected. Optical band gaps were estimated to be 2.9 and 2.4 for the Nd and Sm analogues, respectively.

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

Studies on the structure and the magnetic properties of high-entropy spinel oxide (MgMnFeCoNi)Al 2 O 4

The study of high-entropy materials has attracted enormous interest since they could show new functional properties that are not observed in their related parent phases. Here, we report single crystal growth, structure, thermal transport, and magnetic property studies on a novel high-entropy oxide with the spinel structure (MgMnFeCoNi)Al 2 O 4 . We have successfully grown high-quality single crystals of this high-entropy oxide using the optical floating zone growth technique for the first time. The sample was confirmed to be a phase pure high-entropy oxide using x-ray diffraction and energy-dispersive spectroscopy. Through magnetization measurements, we found (MgMnFeCoNi)Al 2 O 4 exhibits a cluster spin glass state, though the parent phases show either antiferromagnetic ordering or spin glass states. Furthermore, we also found that (MgMnFeCoNi)Al 2 O 4 has much greater thermal expansion than its CoAl 2 O 4 parent compound using high resolution neutron Larmor diffraction. We further investigated the structure of this high-entropy material via Raman spectroscopy and extended x-ray absorption fine structure spectroscopy (EXAFS) measurements. From Raman spectroscopy measurements, we observed (MgMnFeCoNi)Al 2 O 4 to display a combination of the active Raman modes in its parent compounds with the modes shifted and significantly broadened. This result, together with the varying bond lengths probed by EXAFS, reveals severe local lattice distortions in this high-entropy phase. Additionally, we found a substantial decrease in thermal conductivity and suppression of the low temperature thermal conductivity peak in (MgMnFeCoNi)Al 2 O 4 , consistent with the increased lattice defects and strain. These findings advance the understanding of the dependence of thermal expansion and transport on the lattice distortions in high-entropy materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Solution‐Phase Metathesis of Li 3 N and FeCl 3 to Synthesize Fe 2 N/Fe 3 N Nanoparticles

Soft magnetic materials play key roles in the flow of energy in electrically driven machines and power conversion electronics, and there is a great need for improvements in their magnetic properties to provide the right combination of high saturation magnetization, low coercivity, and high permeability. Most phases of iron nitride (Fe x N) are soft magnetic materials with these characteristics, but they exist as numerous phases which are not all stoichiometric compounds. While the production and magnetic properties of the different phases of bulk iron nitride are well known, accessing phase‐pure nanoscale iron nitride consistently remains a challenge. Most methods for the synthesis of iron nitride nanoparticles require complicated apparatus to achieve high‐temperature nitriding of nanoparticle precursors with gaseous nitrogen sources such as ammonia. The first solution‐phase metathesis reaction between FeCl 3 and Li 3 N in oleylamine is developed to directly synthesize Fe 2 N/Fe 3 N nanoparticles, requiring only a fume hood, glove box, standard chemistry laboratory glassware, and equipment. Finally, the ≈10–15 nm spheres display nearly soft magnetic behavior with a saturation magnetization ≈50–60 A m 2 kg −1 , coercivities between 40–50 kA m −1 , and susceptibility values from 0.0001–0.0006 m 3 kg −1 , well within the ranges reported with other published Fe x N nanoparticle synthesis methods.

iron nitride↗
DOE OSTI2020

Effect of Cr(III) Adsorption on the Dissolution of Boehmite Nanoparticles in Caustic Solution

Incorporation of relatively minor impurity metals onto metal (oxy)hydroxides can strongly impact solubility. In complex highly alkaline multicomponent tank waste such as that at the Hanford Nuclear Reservation, tests indicate that the surface area-normalized dissolution rate of boehmite ($γ$-AlOOH) nanomaterials is at least an order of magnitude lower than that predicted for the pure phase. In this work we examine the dissolution kinetics of boehmite coated by adsorbed Cr(III), which adheres at saturation coverages as sparse chemisorbed monolayer clusters. Using 40 nm boehmite nanoplates as a model system, temperature-dependent dissolution rates of pure versus Cr(III)-adsorbed boehmite showed that the initial rate for the latter is consistently several times lower, with an apparent activation energy 16 kJ·mol -1 higher. Although the surface coverage is only around 50%, solution analytics coupled to multimethod solids characterization reveals a phyicochemical armoring effect by adsorbed Cr(III) that substantially reduces the number of dissolution-active sites on particle surfaces. Such findings could help improve kinetics models of boehmite and/or metal ion adsorbed boehmite nanomaterials, ultimately providing a stronger foundation for the development of more robust complex radioactive liquid waste processing strategies.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Steam-Assisted Ammonolysis of MoO2 as a Synthetic Pathway to Oxygenated δ-MoN

A common route for the synthesis of molybdenum nitrides is through the temperature-programmed reaction of molybdenum oxides with NH3, or ammonolysis. In this work, the role of precursor phase, gas phase chemistry (impact of H2O), and temperature profile on the reaction outcome (700 °C) was examined, which resulted in varying amounts of MoO2, H2MoO5, and the nitride phases—cubic γ (nominally Mo2N) and hexagonal δ (nominally MoN). The phase fraction of the δ phase increased with precursor in the sequence MoO2 > MoO3 > H2MoO5. Steam in the reaction gas also favored the production of δ over γ, but with too much steam, MoO2 was obtained in the product. Synthesis conditions for obtaining nearly phase-pure δ were identified: MoO2 as the precursor, 2% H2O in the gas stream, and a moderate heating rate (3 °C/min). In situ X-ray diffraction provided insights into the reaction pathway. Extensive physico-chemical analysis of the δ phase, including synchrotron X-ray and neutron diffraction, electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, and prompt gamma activation analysis, revealed its stoichiometry to be MoO0.108(8)N0.892(8)H0.012(5), indicating non-trivial oxygen incorporation. The presence of N/O ordering and an impurity phase Mo5N6 were also revealed, detectable only by neutron diffraction. Notably, a computationally predicted MoON phase (doi: 10.1103/PhysRevLett.123.236402), of interest due to its potential to display a metal-insulator transition, did not appear under any reaction condition examined.

Pandey, Shobhit↗
DOE OSTI2023

Wet to Dry Controls Lanthanide Scandate Synthesis

The choice of temperature and gas conditions used in a water pressure-controlled reactor is guided by density functional theory (DFT) to synthesize nearly phase pure lanthanide scandate nanoparticles (LnScO 3 , Ln = La, Nd, Sm, Gd). In this synthetic method, low water vapor partial pressures, well below water’s gas liquidus, inhibit particle growth, while an excess of water vapor results in undesired rare earth hydroxide and oxyhydroxide secondary phases. The optimal humidity for high-purity LnScO 3 particle synthesis is shown to vary with the lanthanide; DFT is used to calculate the thermodynamics of secondary phase formation for each lanthanide tested, such that the role of water vapor may be quantified and used to maintain phase purity (greater than 96 mol%) across the series. Furthermore, the combination of thermodynamic calculation and experimental confirmation with this pressure-controlled reactor provides an opportunity to explore analogous syntheses of other inorganic perovskite nanoparticles.

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

Intense Pulse Light Annealing of Perovskite Photovoltaics Using Gradient Flashes

Perovskite solar cells (PSCs) have been fabricated through high-speed and low-cost depositions but often require long annealing. Intense pulse light (IPL) can anneal thin films in seconds after deposition by inducing very high temperatures lasting for milliseconds, and multiple flashes can be used to tune the temperature profile. In this study, a gradient flash annealing (GFA) approach is introduced and compared to uniform flash annealing (UFA) by investigating the crystallinity, morphology, and phase evolution of the CH 3 NH 3 PbI 3 perovskite films and their impact on PSC performance. Unlike UFA, low-intensity pulsed irradiation during the pre-annealing stage of GFA played a significant role on enhancing the PSC performance by forming pure-phase CH 3 NH 3 PbI 3 perovskite thin films with superior morphology and high crystallinity. To understand the kinetics, a transient thermal simulation using ANSYS was developed and confirmed with an experimental setup. The results combined with microscopy and spectrophotometry were used to visualize how duration, delay time, photon flux, and flash count parameters participated in crystallization, phase, and morphology evolution. The IPL annealing induced rapid surface temperature increase, reaching as high as 800 °C, while produced well-developed and bound perovskite grains without any surface defects in an uncontrolled ambient environment with high humidity (>60%). The study resulted in PSCs with maximum efficiency and fill factor of 9.27 and 69.92% for the UFA and 11.75 and 68% when annealed through the GFA approach, respectively. Lastly, this work utilized IPL as the sole thermal source for post-deposition annealing to rapidly fabricate efficient PSCs in only 10 s, which opens the pathway for high-speed, low-cost, and large-scale automated fabrication of perovskite photovoltaics and semiconductors.

14 SOLAR ENERGY↗
DOE OSTI2025

Low-temperature access to active iron and iron/nickel nitrides as potential electrocatalysts for the oxygen evolution reaction

Low-temperature, scalable routes to transition metal nitride (TMN) nanoparticles are desirable for a wide range of applications, yet their synthesis typically requires high temperatures (>350 °C) and reactive gas environments (e.g., NH 3 or H 2 /N 2 ). Here, we report a colloidal synthesis of mono- and bimetallic TMN nanoparticles using preformed metal carbonyl clusters as precursors and urea or diethylenetriamine (DETA) as nitrogen sources. This strategy enables access to size-controlled, phase-pure ε-Fe 3 N x and Fe y Ni 3−y N nanoparticles at temperatures below 300 °C, without the need for flowing reactive gas atmospheres. By systematically varying nitrogen precursor, reaction temperature, and cluster identity, we achieve tunable nitrogen stoichiometry (x) and phase selectivity between N-rich and N-poor TMNs. Structural and magnetic characterization confirms clean decomposition of the precursors and phase formation consistent with controlled nitridation at the nanoscale. Preliminary electrochemical measurements in alkaline media demonstrate that these materials exhibit oxygen evolution reaction (OER) overpotentials comparable to RuO 2 , highlighting their viability for future electrocatalytic applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2026

Understanding the structural and morphological effects of synthesis route on NpO 2

The availability of actinide standard materials for use in nuclear safeguard applications is critical, as is thorough characterization thereof. Although accurate trace element compositions and isotopic considerations are paramount for deployment of reference standards, structural characterization is also essential towards accurately describing the chemical form and potential matrix effects in candidate materials. Here, to this end, samples of NpO 2 were synthesized via a direct denitration (DD) method and probed with powder X-ray diffraction (PXRD), Raman spectroscopy, and scanning electron microscopy (SEM) for structural and morphological characterization and comparison with NpO 2 materials produced via modified direct denitration (MDD). PXRD confirmed the bulk identity of NpO 2 , and no additional phases were identified using this method. Analysis of Raman data collected using a 532 nm excitation wavelength indicates that samples are mostly phase pure; however, some variability in spectral features is observed. Analysis of additional spectroscopic data collected with a 785 nm excitation wavelength revealed variability in the relative intensity of spectral features. Raman spectroscopy indicates that the sample is primarily NpO 2 ; however, additional signals indicate possible structural disorder, oxidized species, or potential contributions from other Np phases. To further investigate the possibility of additional phase contributions within the sample of NpO 2 , Raman spectroscopic mapping was employed to examine the homogeneity of the sample produced via DD. From this analysis, we determined that despite variability in the intensity of Raman-active vibrational modes, consistent spectra are obtained throughout the area of the sample investigated. SEM images show aggregates with variable sizes and shapes, with rounded, primary particles possessing an average diameter of approximately 100 nm. Comparison of the results of these multimodal analyses to the literature indicates that the crystal chemical, spectroscopic, and microstructural properties of NpO 2 vary based on synthesis method, even if X-ray diffraction data indicate that the bulk phase is NpO 2 .

Direct denitration↗