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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Unblocking Oxygen Charge Compensation for Stabilized High‐Voltage Structure in P2‐Type Sodium‐Ion Cathode

Abstract Layered transition‐metal (TM) oxides are ideal hosts for Li + charge carriers largely due to the occurrence of oxygen charge compensation that stabilizes the layered structure at high voltage. Hence, enabling charge compensation in sodium layered oxides is a fascinating task for extending the cycle life of sodium‐ion batteries. Herein a Ti/Mg co‐doping strategy for a model P2‐Na 2/3 Ni 1/3 Mn 2/3 O 2 cathode material is put forward to activate charge compensation through highly hybridized O 2 p TM 3 d covalent bonds. In this way, the interlayer OO electrostatic repulsion is weakened upon deeply charging, which strongly affects the systematic total energy that transforms the striking P2–O2 interlayer contraction into a moderate solid‐solution‐type evolution. Accordingly, the cycling stability of the codoped cathode material is improved superiorly over the pristine sample. This study starts a perspective way of optimizing the sodium layered cathodes by rational structural design coupling electrochemical reactions, which can be extended to widespread battery researches.

25 ENERGY STORAGE↗
DOE OSTI2021

Beyond the Anderson rule: importance of interfacial dipole and hybridization in van der Waals heterostructures

Vertical stacking of two-dimensional materials with weak van der Waals (vdW) interactions has laid the ground for breakthroughs in physics as well as in technological applications. Although vdW interactions dominate interlayer binding, interlayer electronic coupling may not be negligible and can lead to properties beyond the superposition of constituent monolayers. Here, studying heterobilayers of transition-metal dichalcogenides (MQ 2 ; M = Mo, Ni, Pt; Q = S, Se) by means of density functional theory calculations, we show two mechanisms that influence the band gaps of vdW heterostructures beyond the Anderson rule: (1) interfacial hybridization (mainly involving out-of-plane states, such as chalcogen p z -states), which leads to an upshift in the valence band maxima and accordingly a decrease in the band gap. (2) Formation of an interfacial electric dipole, resulting in an effective gap increase in type-II junctions. While the former is material specific, depending on the proximity of p z -states to each other and the valence band maxima, the latter can be generally described using a model based on the charge density decay outside the monolayers and the pristine band edge positions with respect to the vacuum level, irrespective of junction type.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Evolution of the Electronic and Excitonic Properties in 2D Ruddlesden–Popper Perovskites Induced by Bifunctional Ligands

2D Ruddlesden–Popper metal‐halide perovskites exhibit structural diversity due to a variety of choices of organic ligands. Incorporating bifunctional ligands in such materials is particularly intriguing since it can result in novel electronic properties and functions. However, an in‐depth understanding of the effects of bifunctional ligands on perovskite structures and, consequently, their electronic and excitonic properties, is still lacking. Here, in this work, n = 1 2D perovskites built with organic ligands containing ─CN, ─OH, ─COOH, ─phenyl (Ph), and ─CH 3 functional groups are investigated using ultraviolet and inverse photoemission spectroscopies, density functional theory calculations, and tight‐binding model analyses. The experimentally determined electronic gaps of the ─CN, ─COOH, ─Ph, and ─CH 3 based perovskites exhibit a strong correlation with the in‐plane Pb─I─Pb bond angle, while the ─OH based perovskite deviates from the linear trend. Based on the band structure calculations, this anomaly is attributed to the out‐of‐plane dispersion, caused predominantly by significant interlayer electronic coupling that is present in ─OH based perovskites. These results highlight the complex and diverse impacts of organic ligands on electronic properties, especially in terms of the involvement of strong interlayer electronic coupling. The impact of the bifunctional ligands on the evolution of the exciton binding energy is also addressed.

2D perovskites↗
DOE OSTI2020

High-temperature oxidation of transient-liquid phase bonded Ni-based alloys in 1 bar and 250 bar carbon dioxide

Compact microchannel heat exchanger designs for supercritical CO 2 power cycles are valued for equipment size reduction and increased heat transfer. They can be fabricated via transient-liquid phase (TLP) bonding, which utilizes a lower melting point interlayer for bonding facilitation of etched thin plates. Haynes 230 and 282 TLP bonded stacks were exposed to high-purity CO 2 at 1 bar/700 °C to 4000 h and 250 bar/720 °C (supercritical) to 1500 h. All samples obeyed parabolic kinetics after an oxide buildup stage of 500-1000 h. Mass gains were similar for the base and TLP bonded alloys, and oxide thicknesses and scales did not significantly differ around the TLP bond regions. Furthermore, there were some slight oxide compositional differences for the H282 TLP samples at 250 bar. There was a slight pressure effect on mass gain, as samples exposed at the higher pressure experienced higher initial mass gains, but then slower continued oxide growth.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Altermagnetism, kagome flat band, and Weyl fermion states in magnetically intercalated transition metal dichalcogenides

Altermagnetic (AM) compounds have recently emerged as a promising platform for realizing unconventional quantum phases, enabled by their unique spin-split band structure at zero net magnetization. Here, we present a first-principles investigation of magnetically intercalated transition metal dichalcogenides (TMDs) of the form XY 4 Z 8 (X = Mn, Fe, Co, Ni, Cr, or V; Y = Nb or Ta; and Z = Se or S), identifying a subset of new versatile AM candidates. Our results establish a systematic correlation between interatomic geometry, quantified by the ratio of interlayer to intralayer spacing, and the magnetic ground states. Systems with A-type antiferromagnetic order exhibit momentum-dependent spin splitting consistent with AM behavior. The combination of the AM spin-splitting and the spin-orbit coupling leads to the emergence of Weyl nodes together with the corresponding topological Fermi arc surface states. Moreover, we identify flat bands near the Fermi level that originate from the intercalant-induced formation of an effective kagome-like sublattice in the TMD layer. These results collectively establish magnetically intercalated TMDs as a promising platform for engineering altermagnetism, flat bands, and Weyl fermions within a single material family, facilitating the development of topological and spintronic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Martensitic transformation induced strength-ductility synergy in additively manufactured maraging 250 steel by thermal history engineering

Maraging steels are known for their exceptional strength but suffer from limited work hardening and ductility. Here, in this study, we report an intermittent printing strategy to tailor the microstructure and mechanical properties of maraging 250 steel via tuning the thermal history during wire-arc directed energy deposition. By introducing a dwell time between adjacent layers, the maraging 250 steel is cooled below the martensite start temperature, triggering thermally-driven martensitic transformation during the printing process. Thermal cycling during subsequent layer deposition results in the formation of reverted austenite which shows a refined microstructure and induces elemental segregation between martensite and reverted austenite. The Ni enrichment in the austenite promotes stabilization of the reverted austenite upon cooling to room temperature. The reverted austenite is metastable during deformation, leading to strain-induced martensitic transformation under loading. Specifically, a 3 min interlayer dwell time produces a maraging 250 steel with approximately 8% reverted austenite, resulting in improved work hardening via martensitic transformation induced plasticity during deformation. Meanwhile, the higher cooling rate and refined prior austenite grains lead to substantially refined martensitic grains (by approximately fivefold) together with an increased dislocation density. With 3 min interlayer dwell time, the yield strength of the printed maraging 250 steel increases from 836 MPa to 990 MPa, and the uniform elongation is doubled from 3.2% to 6.5%. This intermittent deposition strategy demonstrates the potential to tune the microstructure of maraging steels for achieving strength-ductility synergy by engineering the thermal history during additive manufacturing.

Additive manufacturing↗
DOE OSTI2021

Engineering of flat bands and Dirac bands in two-dimensional covalent organic frameworks (COFs): relationships among molecular orbital symmetry, lattice symmetry, and electronic-structure characteristics

Two-dimensional covalent organic frameworks (2D-COFs), also referred to as 2D polymer networks, display unusual electronic-structure characteristics, which can significantly enrich and broaden the fields of electronics and spintronics. In this Focus article, the objective of this report is to lay the groundwork for the conceptual description of the fundamental relationships among the COF electronic structures, the symmetries of their 2D lattices, and the frontier molecular orbitals (MOs) of their core and linker components. We focus on monolayers of hexagonal COFs and use tight-binding model analyses to highlight the critical role of the frontier-MO symmetry, in addition to lattice symmetry, in determining the nature of the electronic bands near the Fermi level. We rationalize the intriguing feature that, when the core unit has degenerate highest occupied MOs [or lowest unoccupied MOs], the COF highest valence band [or lowest conduction band] is flat but degenerate with a dispersive band at a high-symmetry point of the Brillouin zone; the consequences of having such band characteristics are briefly described. Multi-layer and bulk 2D COFs are found to maintain the salient features of the monolayer electronic structures albeit with a reduced bandgap due to the interlayer coupling. This Focus article is thus meant to provide an effective framework for the engineering of flat and Dirac bands in 2D polymer networks.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Substitution-Mediated Calcination of Nickel-Based Cathodes: Decoupling Lithiation and Crystallization

Nickel-based layered cathodes such as LiNiO 2 offer high energy density for lithium-ion batteries, yet improvements in cycling performance and safety are required for practical use–often achieved through manganese and cobalt substitution as in LiNi 0.80 Mn 0.10 Co 0.10 O 2 (NMC811). However, how such substitution impacts calcination, the key process that governs lithiation, structural ordering, crystallization, and ultimately the resulting material properties, remains unclear. Here, in this study, we investigate substitution-mediated calcination dynamics in NMC811 compared to LiNiO 2 using multiscale-correlated in situ spectroscopy and atomistic-to-mesoscale modeling. While both systems progress through the same sequence of intermediates toward the thermodynamically favored layered phase, NMC811 exhibits an earlier onset of layering, concurrent with hydroxide decomposition followed by sluggish crystallization. Modeling reveals that Mn and Co lower the energy barrier for lithium incorporation and ordering but increase the penalty for interlayer gliding, thereby slowing crystal growth at elevated temperatures. This substitution-mediated decoupling of lithiation and crystallization explains the fine-grained microstructure observed in NMC811 versus coarsened particles in LiNiO 2 and establishes a mechanistic framework for predictive microstructure engineering of Ni-based cathodes.

Calcination↗
DOE OSTI2022

Unconventional Pressure-Driven Metamagnetic Transitions in Topological van der Waals Magnets

Activating metamagnetic transitions between ordered states in van der Waals magnets and devices bring great opportunities in spintronics. Here we show that external pressure, which enhances the inter-layer hopping without introducing chemical disorders, triggers multiple metamagnetic transitions upon cooling in the topological van der Waals magnets Mn(Bi 1–x Sb x ) 4 Te 7 , where the antiferro magnetic interlayer superexchange coupling competes with the ferromagnetic interlayer coupling mediated by the antisite Mn spins. The temperature-pressure phase diagrams reveal that while the ordering temperature from the paramagnetic to ordered states is almost pressure-independent, the metamagnetic transitions show non-trivial pressure and temperature dependence, even re-entrance. For these highly anisotropic magnets, we attribute the former to the ordering temperature being only weakly dependent on the intralayer parameters, the latter to the parametrically different pressure and temperature dependence of the two interlayer couplings. Our independent probing of these disparate magnetic interactions paves an avenue for efficient magnetic manipulations in van der Waals magnets.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Magnetic and f-electron effects in LaNiO2 and NdNiO2 nickelates with cuprate-like $$3{d}_{{x}^{2}-{y}^{2}}$$ band

Recent discovery of superconductivity in the doped infinite-layer nickelates has renewed interest in understanding the nature of high-temperature superconductivity more generally. The low-energy electronic structure of the parent compound NdNiO 2 , the role of electronic correlations in driving superconductivity, and the possible relationship between the cuprates and the nickelates are still open questions. Here, by comparing LaNiO 2 and NdNiO 2 systematically within a parameter-free, all-electron first-principles density-functional theory framework, we reveal the role of Nd 4 f electrons in shaping the ground state of pristine NdNiO 2 . Strong similarities are found between the electronic structures of LaNiO 2 and NdNiO 2 , except for the effects of the 4 f electrons. Hybridization between the Nd 4 f and Ni 3 d orbitals is shown to significantly modify the Fermi surfaces of various magnetic states. In contrast, the competition between the magnetically ordered phases depends mainly on the gaps in the Ni \(3{d}_{{x}^{2}-{y}^{2}}\) band. Our estimated value of the on-site Hubbard U in the nickelates is similar to that in the cuprates, but the value of the Hund’s coupling J H is found to be sensitive to the Nd magnetic moment. In contrast with the cuprates, NdNiO 2 presents 3D magnetism with competing antiferromagnetic and (interlayer) ferromagnetic exchange, which may explain why the T c is lower in the nickelates.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Electrical Control and Transport of Tightly Bound Interlayer Excitons in a MoSe 2 /hBN/MoSe 2 Heterostructure

Controlling interlayer excitons in Van der Waals heterostructures holds promise for exploring Bose-Einstein condensates and developing novel optoelectronic applications, such as excitonic integrated circuits. Despite intensive studies, several key fundamental properties of interlayer excitons, such as their binding energies and interactions with charges, remain not well understood. Here we report the formation of momentum-direct interlayer excitons in a high-quality MoSe 2 /hBN/MoSe 2 heterostructure under an electric field, characterized by bright photoluminescence (PL) emission with high quantum yield and a narrow linewidth of less than 4 meV. These interlayer excitons show electrically tunable emission energy spanning ~1⁢8⁢0 meV through the Stark effect, and exhibit a sizable binding energy of ~8⁢1 meV in the intrinsic regime, along with trion binding energies of a few millielectronvolts. Remarkably, we demonstrate the long-range transport of interlayer excitons with a characteristic diffusion length exceeding 1⁢0 μ⁢m, which can be attributed, in part, to their dipolar repulsive interactions. Further, spatially and polarization-resolved spectroscopic studies reveal rich exciton physics in the system, such as valley polarization, local trapping, and the possible existence of dark interlayer excitons. Furthermore, the formation and transport of tightly bound interlayer excitons with narrow linewidth, coupled with the ability to electrically manipulate their properties, open exciting new avenues for exploring quantum many-body physics, including excitonic condensate and superfluidity, and for developing novel optoelectronic devices, such as exciton and photon routers.

2-dimensional systems↗
DOE OSTI2024

Mitigating Sodium Ordering for Enhanced Solid Solution Behavior in Layered NaNiO 2 Cathodes

Abstract The O‐type layered nickel oxides suffer from undesired cooperative Jahn–Teller distortion stemming from Ni 3+ ions and undergo multiple biphasic structural transformations during the insertion/extraction of large Na + ions, posing a significant challenge to stabilize the structural integrity. We present here a systematic investigation of the impact of substituting 5 % divalent (Mg 2+ ) or trivalent (Al 3+ or Co 3+ ) ions for Ni 3+ to alleviate Na + ion ordering and perturb the Jahn–Teller effect to enhance structural stability. We gauge a fundamental understanding of the Mg−O and Na−O or Mg−O−Na bonding interactions, noting that the ionicity of the Mg−O bond deshields the electronic cloud of oxygen from Na + ions. Furthermore, calculations of the Van Vleck distortion modes reveal a relaxation of NiO 6 octahedra from Jahn–Teller distortion and a reduced electron density at the interlayer with Mg 2+ substitution. Long‐range ( operando X‐ray diffraction) and short‐range (magic angle spinning nuclear magnetic resonance) structural analyses provide insights into reduced ordering, allowing a stable continuous solid solution. Overall, Mg‐substitution results in a high‐capacity retention of ~96 % even after 100 cycles, showcasing the potential of this strategy for overcoming the structural instabilities and enhancing the performance of sodium‐ion batteries.

Sada, Krishnakanth↗
DOE OSTI2024

Mitigating Sodium Ordering for Enhanced Solid Solution Behavior in Layered NaNiO 2 Cathodes

The O-type layered nickel oxides suffer from undesired cooperative Jahn–Teller distortion stemming from Ni 3+ ions and undergo multiple biphasic structural transformations during the insertion/extraction of large Na + ions, posing a significant challenge to stabilize the structural integrity. We present here a systematic investigation of the impact of substituting 5 % divalent (Mg 2+ ) or trivalent (Al 3+ or Co 3+ ) ions for Ni 3+ to alleviate Na + ion ordering and perturb the Jahn–Teller effect to enhance structural stability. Here, we gauge a fundamental understanding of the Mg−O and Na−O or Mg−O−Na bonding interactions, noting that the ionicity of the Mg−O bond deshields the electronic cloud of oxygen from Na + ions. Furthermore, calculations of the Van Vleck distortion modes reveal a relaxation of NiO 6 octahedra from Jahn–Teller distortion and a reduced electron density at the interlayer with Mg 2+ substitution. Long-range (operando X-ray diffraction) and short-range (magic angle spinning nuclear magnetic resonance) structural analyses provide insights into reduced ordering, allowing a stable continuous solid solution. Overall, Mg-substitution results in a high-capacity retention of ~96 % even after 100 cycles, showcasing the potential of this strategy for overcoming the structural instabilities and enhancing the performance of sodium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Reduced thermal resistance of Al-rich AlGaN HEMTs via top-side diamond integration

We report back-end-of-line growth of nanocrystalline diamond (NCD) on ultrawide bandgap (UWBG) high Al content aluminum gallium nitride (AlGaN) channel high electron mobility transistors for thermal management. A thin (∼15 nm) silicon nitride (SiN x ) interlayer was deposited to protect the device surface before performing a low temperature (500 °C) NCD growth process in an attempt to protect the gates on these fully fabricated devices. Notably, atomic force microscopy showed that the maximum lateral grain size exceeded 300 nm even though the film thickness was ∼250 nm. Comparing electrical (DC) performance before and after NCD growth, the gate leakage increased by ∼10 2 after NCD growth. Despite the lower NCD growth temperature, intermixing of the Ni and Au was observed in the Schottky gate metal stack; however, we believe there is another mechanism, possibly hydrogen-related, that is responsible for the measured increase in gate leakage. Regarding thermal management, the device-level thermal resistance (quantified using the average gate temperature rise measured by thermoreflectance imaging) was reduced by 29% through the incorporation of the top-side diamond film. Using time-domain thermoreflectance, the thermal conductivity of the ≈250 nm thick NCD film was measured to be 45 ± 25 W m −1 K −1 . This is expected to be at least 5× greater than the thermal conductivity of the thin disordered AlGaN alloy. There could also be a coupled electrothermal component contributing to the reduced temperature rise from electric field spreading and consequent heat spreading. This study demonstrates a promising first step toward device-level thermal management of high power UWBG Al-rich AlGaN devices.

Lundh, James Spencer [U.S. Naval Research Laborato↗
DOE OSTI2024

Superconductivity in pressurized trilayer La 4 Ni 3 O 10-$δ$ single crystals

In this study, the pursuit of discovering new high-temperature superconductors that diverge from the copper-based model has profound implications for explaining mechanisms behind superconductivity and may also enable new applications. Here our investigation shows that the application of pressure effectively suppresses the spin–charge order in trilayer nickelate La 4 Ni 3 O 10-δ single crystals, leading to the emergence of superconductivity with a maximum critical temperature (T c ) of around 30 K at 69.0 GPa. The d.c. susceptibility measurements confirm a substantial diamagnetic response below T c , indicating the presence of bulk superconductivity with a volume fraction exceeding 80%. In the normal state, we observe a strange metal behaviour, characterized by a linear temperature-dependent resistance extending up to 300 K. Furthermore, the layer-dependent superconductivity observed hints at a unique interlayer coupling mechanism specific to nickelates, setting them apart from cuprates in this regard. Our findings provide crucial insights into the fundamental mechanisms underpinning superconductivity, while also introducing a new material platform to explore the intricate interplay between the spin–charge order, flat band structures, interlayer coupling, strange metal behaviour and high-temperature superconductivity.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Single crystal growth, chemical defects, magnetic and transport properties of antiferromagnetic topological insulators ( Ge 1 – δ – x Mn x ) 2 Bi 2 Te 5 ( x ≤ 0.47 , 0.11 ≤ δ ≤ 0.20 )

Magnetic topological insulators provide a platform for emergent phenomena arising from the interplay between magnetism and band topology. Here we report the single crystal growth, crystal structure, magnetic and transport properties, as well as the neutron scattering studies of topological insulator series (Ge 1–δ–x Mn x ) 2 ⁢Bi 2 ⁢Te 5 (x ≤ 0.47, 0.11 ≤ δ ≤ 0.20). Upon doping up to x = 0.47, the lattice parameter c decreases by 0.8%, while the lattice parameter a remains nearly unchanged. Significant Ge vacancies and Ge/Bi site mixing are revealed via elemental analysis as well as refinements of the neutron and x-ray diffraction data, resulting in holes dominating the charge transport. At x = 0.47, below 10.8 K, a bilayer A-type antiferromagnetic ordered state emerges, featuring an ordered moment of 3.0(3) μ B /Mn at 5 K, with the c axis as the easy axis. Magnetization data unveils a much stronger effective interlayer antiferromagnetic exchange interaction and a much smaller uniaxial anisotropy compared to MnBi 2 ⁢Te 4 . We attribute the former to the shorter nearest-neighbor Mn-Mn interlayer superexchange path and the latter to the smaller ligand-field splitting in (Ge 1–δ–x ⁢Mn x ) 2 ⁢Bi 2 ⁢Te 5 . Finally, our study demonstrates that this series of materials holds promise for the investigation of the layer Hall effect and quantum metric nonlinear Hall effect.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thickness-Dependent Interlayer Charge Transfer in MoSe 2 /MoS 2 Heterostructures Studied by Femtosecond Transient Absorption Measurements

We report observations of a strong thickness dependence for charge transfer (CT) from MoSe 2 to MoS 2 , as evidenced by transient absorption measurements. By time-resolving CT from MoSe 2 monolayers (1Ls) to MoS 2 flakes of varying thicknesses, including 1L, bilayer (2L), and trilayer (3L), we find that the CT time is several picoseconds in the 1L-MoSe 2 /3L-MoS 2 heterostructure, which is much longer than that of 1L-MoSe 2 /1L-MoS 2 and 1L-MoSe 2 /2L-MoS 2 heterostructures. In addition, the recombination lifetime of the interlayer excitons in the 1L/3L heterostructure is several times longer than that of 1L/1L and 1L/2L heterostructures, reaching 800 ps. Furthermore, we show that a prepulse can reduce the CT time and enhance the interlayer exciton recombination in the 1L/3L heterostructure. Furthermore, these findings illustrate that layer thickness can be an important parameter to control the CT property of van der Waals heterostructures. These experimental results also provide important information for further refining the understanding of the physical mechanisms of CT in van der Waals heterostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Degradation by Kinking in Layered Cathode Materials

Layered cathode materials are commonly used in lithium and sodium ion batteries, but they are prone to degradation under electrochemical cycling during battery operation. Here we report a new type of degradation mechanism through the electrochemically induced mechanical buckling and delamination cracking of intercalation layers in a P2 Na 0.7 -Ni 0.3 Mn 0.6 Co 0.1 O 2 (Na-NMC) cathode material. Kinks form in the delaminated layers due to severe local bending, and each kink consists of a vertical array of dislocations, resulting from an easy slip between transition metal oxide layers. In situ mechanical compression experiments directly reveal the kink formation due to strong mechanical anisotropy parallel and perpendicular to the intercalation layers in single-crystal Na-NMC. In situ electrochemical experiments indicate that kinks form during the desodiation process. Our results unveil a new mechanism of electrochemically induced mechanical degradation stemming from weak interlayer bonding in layered cathode materials. In conclusion, this work has broad implications for the mitigation of degradation associated with irreversible interlayer slip in layered cathode materials.

25 ENERGY STORAGE↗