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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 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

GaSb doping facilitates conduction band convergence and improves thermoelectric performance in n-type PbS

P-type lead chalcogenides have superior thermoelectric performance because they exhibit the energy convergence of several valence bands. However, despite the existence of two conduction bands, there has been no report about conduction band (CB) convergence for n-type counterparts because of the large energy difference between them. Therefore, new strategies are required to manipulate the CBs if enhancing the electrical transport performance of n-type lead chalcogenides is to be achieved. PbS is a highly attractive member of the lead chalcogenides because of its high earth-abundance and low cost. Here, we report that the introduction of GaSb can successfully dope the PbS matrix with Ga and Sb atoms occupying the Pb site in its rock salt structure. GaSb doping leads to conduction band convergence and enlarged effective density of state mass for n-type PbS. This effect results in superior power factor and decreased lattice thermal conductivity caused by the soft phonon modes and point defect scattering of phonons. Consequently, a record-high average power factor PF avg of ~20.4 μW cm –1 K –2 and figure of merit ZT avg of ~0.84 in the temperature range of 400 K to 923 K were obtained, higher than any n- and p-type PbS-based thermoelectric materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Gaussian approximation potentials for accurate thermal properties of two-dimensional materials

Two-dimensional materials (2DMs) continue to attract a lot of attention, particularly for their extreme flexibility and superior thermal properties. Molecular dynamics simulations are among the most powerful methods for computing these properties, but their reliability depends on the accuracy of interatomic interactions. While first principles approaches provide the most accurate description of interatomic forces, they are computationally expensive. In contrast, classical force fields are computationally efficient, but have limited accuracy in interatomic force description. Machine learning interatomic potentials, such as Gaussian Approximation Potentials, trained on density functional theory (DFT) calculations offer a compromise by providing both accurate estimation and computational efficiency. Here, in this work, we present a systematic procedure to develop Gaussian approximation potentials for selected 2DMs, graphene, buckled silicene, and h-XN (X = B, Al, and Ga, as binary compounds) structures. We validate our approach through calculations that require various levels of accuracy in interatomic interactions. The calculated phonon dispersion curves and lattice thermal conductivity, obtained through harmonic and anharmonic force constants (including fourth order) are in excellent agreement with DFT results. HIPHIVE calculations, in which the generated GAP potentials were used to compute higher-order force constants instead of DFT, demonstrated the first-principles level accuracy of the potentials for interatomic force description. Molecular dynamics simulations based on phonon density of states calculations, which agree closely with DFT-based calculations, also show the success of the generated potentials in high-temperature simulations.

2D Materials↗
DOE OSTI2024

Structure, bonding and electronic characteristics of amorphous Se

Ovonic threshold switching (OTS) selector can effectively improve the storage density and suppress the leakage current of advanced phase-change memory. As a prototypical OTS material, amorphous GeSe is widely investigated. But the attentions paid to amorphous Se (i.e., the functional constituent in amorphous GeSe) is very limited up to now. Here, in this work, we have explored the structure, bonding and electronic characteristics of amorphous Se using ab initio molecular dynamics simulations. The results reveal that the Se atoms in amorphous Se tend to form the 2-coordinated configurations, and they connect with each other to form the long chains. The fraction of vibrational density of state located in high frequency range is relatively large, and the formation energy of Se-Se bond is as large as 4.44 eV, hinting that the Se-Se bonds in chains possess a high stability. In addition, the mid-gap state related to the OTS behavior is also found in the amorphous Se despite of the small proportion. Our findings enrich the knowledge of the amorphous Se, which contributes to the applications of Se-based OTS selectors.

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

All-electron ab initio Bethe-Salpeter equation approach to neutral excitations in molecules with numeric atom-centered orbitals

The Bethe-Salpeter equation (BSE) based on GW quasiparticle levels is a successful approach for calculating the optical gaps and spectra of solids and also for predicting the neutral excitations of small molecules. We here present an all-electron implementation of the GW+BSE formalism for molecules, using numeric atom-centered orbital (NAO) basis sets. We present benchmarks for low-lying excitation energies for a set of small organic molecules, denoted in the literature as “Thiel’s set.” Literature reference data based on Gaussian-type orbitals are reproduced to about one millielectron-volt precision for the molecular benchmark set, when using the same GW quasiparticle energies and basis sets as the input to the BSE calculations. For valence correlation consistent NAO basis sets, as well as for standard NAO basis sets for ground state density-functional theory with extended augmentation functions, we demonstrate excellent convergence of the predicted low-lying excitations to the complete basis set limit. A simple and affordable augmented NAO basis set denoted “tier2+aug2” is recommended as a particularly efficient formulation for production calculations. We finally demonstrate that the same convergence properties also apply to linear-response time-dependent density functional theory within the NAO formalism.

Liu, Chi↗
DOE OSTI2020

Effects of cation stoichiometry on surface morphology and crystallinity of ZnGeN 2 films grown on GaN by metalorganic chemical vapor deposition

ZnGeN 2 films were grown on GaN-on-sapphire templates via metalorganic chemical vapor deposition. Energy dispersive X-ray spectroscopy was used to estimate the Zn/(Zn+Ge) composition ratio in the films. This ratio decreased with increase in growth temperature but increased with increase in total reactor pressure or Zn/Ge precursor flow rate ratio. Systematic mapping of these key growth parameters has allowed us to identify the growth window to achieve ZnGeN 2 with stoichiometric cation composition. Compositional and statistical analyses performed on data acquired from atom probe tomography provided insight into the local compositional homogeneity. The cations Zn and Ge did not demonstrate segregation or clustering at the sub-nanometer level. Based on X-ray diffraction 2θ-ω scan profiles and transmission electron microscope nano-diffraction patterns, the films with near-stoichiometric cation ratios were single crystalline with planar surfaces, whereas zinc-rich or zinc-poor films were polycrystalline with nonplanar surfaces. The growth direction of the single crystalline ZnGeN 2 films on GaN templates was along the c-axis. Room temperature Raman spectra showed features associated with the phonon density of states, indicating the presence of cation disorder in the lattice. A cathodoluminescence peak associated with transitions involving deep level defects was observed around 640 nm. The intensity of this peak increased by almost 2.5 times as the temperature was reduced to 77 K from room temperature. A similar peak was observed in photoluminescence spectra collected at 80 K.

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

Thermal boundary conductance between high thermal conductivity boron arsenide and silicon

Thermal boundary conductance (TBC) is important for heat dissipation in light-emitting diodes (LEDs). In this study, we predicted the TBC between the high thermal conductivity boron arsenide (BAs) and silicon (Si) by nonequilibrium molecular dynamics (MD) simulations. From the thermal conductivity accumulation function with respect to phonon frequency, the dominant phonon frequencies for heat conduction in BAs are extremely different from those in Si. However, our nonequilibrium MD simulations indicated that the TBC of the BAs/Si interface was still high compared to most other interfaces, even though there was a major frequency mismatch in the thermal conductivity accumulation function between BAs and Si. The primary reason for the high TBC is the overlap of phonon density of states between BAs and Si in the frequency range of 5–8 THz. The range of predicted TBC of the BAs/Si interface was between 200 and 300 MW/m2 K in the temperature range of 300–700 K, and the values of the TBC were not sensitive to the temperature. We also found that the TBCs in Si/BAs and Si/Ge interfaces were close to each other considering the simulation uncertainty. This work indicates BAs as an excellent material for heat dissipation across the interfaces.

Wei, Zhiyong (ORCID:000000018686451X)↗
DOE OSTI2020

Predicting molecular dipole moments by combining atomic partial charges and atomic dipoles

The molecular dipole moment ( μ ) is a central quantity in chemistry. It is essential in predicting infrared and sum-frequency generation spectra as well as induction and long-range electrostatic interactions. Furthermore, it can be extracted directly—via the ground state electron density—from high-level quantum mechanical calculations, making it an ideal target for machine learning (ML). Here, we choose to represent this quantity with a physically inspired ML model that captures two distinct physical effects: local atomic polarization is captured within the symmetry-adapted Gaussian process regression framework which assigns a (vector) dipole moment to each atom, while the movement of charge across the entire molecule is captured by assigning a partial (scalar) charge to each atom. The resulting “MuML” models are fitted together to reproduce molecular μ computed using high-level coupled-cluster theory and density functional theory (DFT) on the QM7b dataset, achieving more accurate results due to the physics-based combination of these complementary terms. The combined model shows excellent transferability when applied to a showcase dataset of larger and more complex molecules, approaching the accuracy of DFT at a small fraction of the computational cost. We also demonstrate that the uncertainty in the predictions can be estimated reliably using a calibrated committee model. The ultimate performance of the models—and the optimal weighting of their combination—depends, however, on the details of the system at hand, with the scalar model being clearly superior when describing large molecules whose dipole is almost entirely generated by charge separation. These observations point to the importance of simultaneously accounting for the local and non-local effects that contribute to μ ; furthermore, they define a challenging task to benchmark future models, particularly those aimed at the description of condensed phases.

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

Superconductivity in type-II Weyl-semimetal WTe 2 induced by a normal metal contact

WTe 2 is a material with rich topological properties: it is a 2D topological insulator as a monolayer and a Weyl-semimetal and higher-order topological insulator in a bulk form. Inducing superconductivity in topological materials is a way to obtain topological superconductivity, which lays at the foundation for many proposals of fault tolerant quantum computing. Here, we demonstrate the emergence of superconductivity at the interface between WTe 2 and the normal metal palladium. The superconductivity has a critical temperature of about 1.2 K. By studying the superconductivity in a perpendicular magnetic field, we obtain the coherence length and the London penetration depth. These parameters correspond to a low Fermi velocity and a high density of states at the Fermi level. This hints to a possible origin of superconductivity due to the formation of flatbands. Furthermore, the critical in-plane magnetic field exceeds the Pauli limit, suggesting a non-trivial nature of the superconducting state.

Kononov, Artem↗
DOE OSTI2021

Spontaneous emission dynamics of Eu 3+ ions coupled to hyperbolic metamaterials

We show that sub-wavelength nanostructured systems with tunable electromagnetic properties, such as hyperbolic metamaterials (HMMs), provide a useful platform to tailor spontaneous emission processes. Here, we investigate a system comprising Eu 3+ (NO 3 ) 3 ·6H 2 O nanocrystals on an HMM structure featuring a hexagonal array of Ag nanowires in a porous Al2O 3 matrix. The HMM-coupled Eu 3+ ions exhibit up to a 2.4 fold increase in their decay rate, accompanied by an enhancement of the emission rate of the 5 D 0 → 7 F 2 transition. Using finite-difference time-domain modeling, we corroborate these observations with the increase in the photonic density of states seen by the Eu 3+ ions in the proximity of the HMM. Our results indicate that HMMs can serve as a valuable tool to control the emission from weak transitions and, hence, hint at a route toward more practical applications of rare-earth ions in nanoscale optoelectronics and quantum devices.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Electronic growth of Pd(111) nanostructures on MoS 2

Quantum confinement effects can induce the formation of discrete nanostructures with well-defined preferred heights in thin metallic films. In most systems, such electronic growth modes are weak and limited to cryogenic conditions. Recently, however, we have discovered that metals grown upon van der Waals surfaces can exhibit electronic growth at, or even above, room temperature to spontaneously form well-defined and highly stable nanostructures. Here, we explore the initial stages of room temperature deposition of Pd onto MoS 2 . We found that, even for minimal thicknesses, Pd spontaneously formed discrete islands with three atomic layers. The islands maintained this preferred height for nominal coverages below three atomic layers. At higher coverages, the preferred height switched abruptly to six atomic layers. Unlike previous studies using Au or Ag, the islands did not increase laterally with coverage but rather increased in number with lateral size remaining about the same. The preferred heights in Pd/MoS 2 correlate to the Pd Fermi surface topography and are also consistent with thicknesses showing minima in the density of states at the Fermi level, which suggest that the electronic growth modes are the driving factors in these self-assembled Pd nanostructures. The Pd system shows a preference for island nucleation compared to Au and Ag which grow laterally with increasing coverage. Furthermore, this is likely related to differences in bonding at the interface as Pd is typically much more reactive than Ag or Au.

36 MATERIALS SCIENCE↗
DOE OSTI2022

On analysis and stochastic modeling of the particle kinetic energy equation in particle-laden isotropic turbulent flows

In this study, we analyze three-dimensional particle-laden, isotropic turbulence to develop an understanding of inertial particle dynamics from a kinetic energy perspective. Data trends implying inhomogeneous sampling of the flow by particles are identified and used to support a proposed particle behavior: particles appear to accumulate in regions of low flow kinetic energy over time because they lose kinetic energy and slow down in such regions, ultimately causing them to spend more time there. To elucidate this behavior, we derive a particle kinetic energy equation from the particle momentum equation, which incorporates inertial effects through the Schiller–Naumann drag correlation. Upon extracting fundamental physics from this equation, hypotheses regarding the role of the Stokes number in the temporal change of particle kinetic energy and the previously proposed particle behavior are evaluated using simulation data considering three Stokes numbers. Finally, a Fokker–Planck equation is used to derive the steady-state probability density function of the particle kinetic energy. The model fits the simulation data well and provides a tool for further investigation into understanding preferential concentration, as well as a reduced order model for predicting particle kinetic energy in turbulent flows.

42 ENGINEERING↗
DOE OSTI2022

Nuclear–electronic orbital approach to quantization of protons in periodic electronic structure calculations

The nuclear–electronic orbital (NEO) method is a well-established approach for treating nuclei quantum mechanically in molecular systems beyond the usual Born–Oppenheimer approximation. In this work, we present a strategy to implement the NEO method for periodic electronic structure calculations, particularly focused on multicomponent density functional theory (DFT). The NEO-DFT method is implemented in an all-electron electronic structure code, FHI-aims, using a combination of analytical and numerical integration techniques as well as a resolution of the identity scheme to enhance computational efficiency. After validating this implementation, proof-of-concept applications are presented to illustrate the effects of quantized protons on the physical properties of extended systems, such as two-dimensional materials and liquid–semiconductor interfaces. Specifically, periodic NEO-DFT calculations are performed for a trans-polyacetylene chain, a hydrogen boride sheet, and a titanium oxide–water interface. The zero-point energy effects of the protons as well as electron–proton correlation are shown to noticeably impact the density of states and band structures for these systems. These developments provide a foundation for the application of multicomponent DFT to a wide range of other extended condensed matter systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Surface stability of SrNbO 3+δ grown by hybrid molecular beam epitaxy

4d transition metal oxides have emerged as promising materials for numerous applications including high mobility electronics. SrNbO 3 is one such candidate material, serving as a good donor material in interfacial oxide systems and exhibiting high electron mobility in ultrathin films. However, its synthesis is challenging due to the metastable nature of the d 1 Nb 4+ cation and the limitations in the delivery of refractory Nb. To date, films have been grown primarily by pulsed laser deposition (PLD), but development of a means to grow and stabilize the material via molecular beam epitaxy (MBE) would enable studies of interfacial phenomena and multilayer structures that may be challenging by PLD. To that end, SrNbO 3 thin films were grown using hybrid MBE for the first time using a tris(diethylamido)(tert-butylimido) niobium precursor for Nb and an elemental Sr source on GdScO 3 substrates. Varying thicknesses of insulating SrHfO 3 capping layers were deposited using a hafnium tert-butoxide precursor for Hf on top of SrNbO 3 films to preserve the metastable surface. Grown films were transferred in vacuo for x-ray photoelectron spectroscopy to quantify elemental composition, density of states at the Fermi energy, and Nb oxidation state. Ex situ studies by x-ray absorption near edge spectroscopy and scanning transmission electron microscopy illustrate that the SrHfO 3 capping plays an important role in preserving the crystalline quality of the material and the Nb 4d 1 metastable charge state under atmospheric conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Detection of high energy ionizing radiation using deeply depleted graphene–oxide–semiconductor junctions

Graphene’s linear band structure and two-dimensional density of states provide an implicit advantage for sensing charge. Here, these advantages are leveraged in a deeply depleted graphene–oxide–semiconductor (D2GOS) junction detector architecture to sense carriers created by ionizing radiation. Specifically, the room temperature response of a silicon-based D2GOS junction is analyzed during irradiation with 20 MeV Si4+ ions. Detection was demonstrated for doses ranging from 12 to 1200 ions with device functionality maintained with no substantive degradation. To understand the device response, D2GOS pixels were characterized post-irradiation via a combination of electrical characterization, Raman spectroscopy, and photocurrent mapping. This combined characterization methodology underscores the lack of discernible damage caused by irradiation to the graphene while highlighting the nature of interactions between the incident ions and the silicon absorber.

Ruiz, Isaac↗
DOE OSTI2022

Anomalous stability of non-van der Waals bonded B4C nanosheets through surface reconstruction

Boron carbide (B4C) has been well studied both theoretically and experimentally in its bulk form due to its exceptional hardness and use as a high-temperature thermoelectric. However, the properties of its two-dimensional nanosheets are not well established. In this paper, using van der Waals-corrected density-functional theory simulations, we show that bulk B4C can be cleaved along different directions to form B4C nanosheets with low formation energies. We find that there is minimal dependence of formation energies on cleavage planes and surface terminations, even though the bulk is not van der Waals layered. This anomalous stability of B4C nanosheets is found to be a result of surface reconstructions that are unique to B-rich systems. While the density of states of the bulk B4C indicate that it is a semiconductor, the B4C nanosheets are found to be predominantly metallic. We attribute this metallic behavior to a redistribution of charges on the surface bonds of the films. The Seebeck coefficients of the B4C films remain comparable to those of the bulk and are nearly constant as a function of temperature. Our results provide guidance for experimental synthesis efforts and future application of B4C nanosheets in nanoelectronic and thermoelectric applications.

Physics↗
DOE OSTI2023

Theory of photoemission from cathodes with disordered surfaces

Linear-accelerator-based applications like x-ray free electron lasers, ultrafast electron diffraction, electron beam cooling, and energy recovery linacs use photoemission-based cathodes in photoinjectors for electron sources. Most of these photocathodes are typically grown as polycrystalline materials with disordered surfaces. In order to understand the mechanism of photoemission from such cathodes and completely exploit their photoemissive properties, it is important to develop a photoemission formalism that properly describes the subtleties of these cathodes. Here, the Dowell–Schmerge (D–S) model often used to describe the properties of such cathodes gives the correct trends for photoemission properties like the quantum efficiency (QE) and the mean transverse energy (MTE) for metals; however, it is based on several unphysical assumptions. In the present work, we use Spicer’s three-step photoemission formalism to develop a photoemission model that results in the same trends for QE and MTE as the D–S model without the need for any unphysical assumptions and is applicable to defective thin-film semiconductor cathodes along with metal cathodes. As an example, we apply our model to Cs 3 Sb thin films and show that their near-threshold QE and MTE performance is largely explained by the exponentially decaying defect density of states near the valence band maximum.

43 PARTICLE ACCELERATORS↗
DOE OSTI2023

Electronic transport in copper–graphene composites

In this work, we investigate electronic transport properties of copper–graphene (Cu–G) composites using a density-functional theory (DFT) framework. Conduction in composites is studied by varying the interfacial distance of copper/graphene/copper (Cu/G/Cu) interface models. Electronic conductivity of the models computed using the Kubo–Greenwood formula shows that the conductivity increases with decreasing Cu–G distance and saturates below a threshold Cu–G distance. The DFT-based Bader charge analysis indicates increasing charge transfer between Cu atoms at the interfacial layers and the graphene with decreasing Cu–G distance. The electronic density of states reveals increasing contributions from both copper and carbon atoms near the Fermi level with decreasing Cu–G interfacial distance. By computing the space-projected conductivity of the Cu/G/Cu models, we show that the graphene forms a bridge to the electronic conduction at small Cu–G distances, thereby enhancing the conductivity.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Effect of surface functional groups on MXene conductivity

In this work, we report the in-plane electron transport in the MXenes (i.e., within the MXene layers) as a function of composition using the density-functional tight-binding method, in conjunction with the non-equilibrium Green’s functions technique. Our study reveals that all MXene compositions have a linear relationship between current and voltage at lower potentials, indicating their metallic character. However, the magnitude of the current at a given voltage (conductivity) has different trends among different compositions. For example, MXenes without any surface terminations (Ti 3 C 2 ) exhibit higher conductivity compared to MXenes with surface functionalization. Among the MXenes with –O and –OH termination, those with –O surface termination have lower conductivity than the ones with –OH surface terminations. Interestingly, conductivity changes with the ratio of –O and –OH on the MXene surface. Our calculated I–V curves and their conductivities correlate well with transmission functions and the electronic density of states around the Fermi level. The surface composition-dependent conductivity of the MXenes provides a path to tune the in-plane conductivity for enhanced pseudocapacitive performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗