Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “electron localization”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Critical Role of Sc Substitution in Modulating Ferroelectricity in Multiferroic LuFeO 3

Understanding how individual dopants or substitutional atoms interact with host lattices enables us to manipulate, control, and improve the functionality of materials. However, because of the intimate coupling among various degrees of freedom in multiferroics, the atomic-scale influence of individual foreign atoms has remained elusive. Here, we unravel the critical roles of individual Sc substitutional atoms in modulating ferroelectricity at the atomic scale of typical multiferroics, Lu 1–x Sc x FeO 3 , by combining advanced microscopy and theoretical studies. Atomic variations in polar displacement of intriguing topological vortex domains stabilized by Sc substitution are directly correlated with Sc atom-mediated local chemical and electronic fluctuations. The local FeO 5 trimerization magnitude and Lu/Sc–O hybridization strength are found to be significantly reinforced by Sc, clarifying the origin of the strong dependence of improper ferroelectricity on Sc content. We find that this study could pave the way for correlating dopant-regulated atomic-scale local structures with global properties to engineer emergent functionalities of numerous chemically doped functional materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Expanded Analogs of Three‐Dimensional Lead‐Halide Hybrid Perovskites

Abstract Replacing the Pb−X octahedral building unit of A I PbX 3 perovskites (X=halide) with a pair of edge‐sharing Pb−X octahedra affords the expanded perovskite analogs: A II Pb 2 X 6 . We report seven members of this new family of materials. In 3D hybrid perovskites, orbitals from the organic molecules do not participate in the band edges. In contrast, the more spacious inorganic sublattice of the expanded analogs accommodates larger pyrazinium‐based cations with low‐lying π* orbitals that form the conduction band, substantially decreasing the band gap of the expanded lattice. The molecular nature of the conduction band allows us to electronically dope the materials by reducing the organic molecules. By synthesizing derivatives with A II =pyridinium and ammonium, we can isolate the contributions of the pyrazinium‐based orbitals in the band gap transition of A II Pb 2 X 6 . The organic‐molecule‐based conduction band and the inorganic‐ion‐based valence band provide an unusual electronic platform with localized states for electrons and more disperse bands for holes upon optical or thermal excitation.

Umeyama, Daiki↗
DOE OSTI2020

Expanded Analogs of Three-Dimensional Lead-Halide Hybrid Perovskites

Replacing the Pb-X octahedral building unit of A I PbX 3 perovskites (X=halide) with a pair of edge-sharing Pb-X octahedra affords the expanded perovskite analogs: A II Pb 2 X 6 . We report seven members of this new family of materials. In 3D hybrid perovskites, orbitals from the organic molecules do not participate in the band edges. In contrast, the more spacious inorganic sublattice of the expanded analogs accommodates larger pyrazinium-based cations with low-lying π* orbitals that form the conduction band, substantially decreasing the band gap of the expanded lattice. The molecular nature of the conduction band allows us to electronically dope the materials by reducing the organic molecules. By synthesizing derivatives with AII=pyridinium and ammonium, we can isolate the contributions of the pyrazinium-based orbitals in the band gap transition of A II Pb 2 X 6 . The organic-molecule-based conduction band and the inorganic-ion-based valence band provide an unusual electronic platform with localized states for electrons and more disperse bands for holes upon optical or thermal excitation.

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

Heterointercalation in Chevrel-Phase Sulfides: A Model Periodic Solid for the Investigation of Chain Electron Transfer

Modulation of electron density localization on periodic crystal solids through electron transfer from interstitial cations can directly influence the bonding configurations of small-molecule intermediates at the catalyst binding site. This study presents the microwave-assisted solid-state synthesis of four heterointercalant Chevrel-phase (CP) sulfides with varying metal cation intercalants with compositional and electronic structure investigations of the electron density redistribution as a result of intercalation. The heterointercalant CP sulfides, with the general formula Cu x M y Mo 6 S 8 (where M = Cr, Mn, Fe, Ni; x, y = 1.5−2.5), are presented here for the probe reaction of electrochemical CO 2 reduction. A change in product selectivity is observed toward the production of methanol at low overpotentials of −0.5 V vs reversible hydrogen electrode (RHE), as a result of the intercalant combination present within the CP interstitial cavity. Structural confirmation of all materials was examined through Rietveld refinement of the powder X-ray diffraction (PXRD) data, high-resolution transmission electron microscopy (HR-TEM), and selected-area electron diffraction (SAED). Electron transfer from the intercalated metal cations to the Mo 6 S 8 cluster was investigated via X-ray photoelectron spectroscopy (XPS) of the intercalated metal cations and the chalcogenide cluster. Electron transfer was further confirmed through X-ray absorption analysis (XAS) of the K-edges of Mo and intercalants. Intermediate studies of electrochemical reduction of formaldehyde to methanol resulted in a faradaic efficiency of ∼78% methanol production on Cu x Ni y Mo 6 S 8 . The results presented herein identify distinct principles for materials design that can be utilized in other compositional spaces within the broad families of periodic crystal solids.

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

Data-driven electron-diffraction approach reveals local short-range ordering in CrCoNi with ordering effects

Abstract The exceptional mechanical strength of medium/high-entropy alloys has been attributed to hardening in random solid solutions. Here, we evidence non-random chemical mixing in a CrCoNi alloy, resulting from short-range ordering. A data-mining approach of electron nanodiffraction enabled the study, which is assisted by neutron scattering, atom probe tomography, and diffraction simulation using first-principles theory models. Two samples, one homogenized and one heat-treated, are observed. In both samples, results reveal two types of short-range-order inside nanoclusters that minimize the Cr–Cr nearest neighbors (L1 2 ) or segregate Cr on alternating close-packed planes (L1 1 ). The L1 1 is predominant in the homogenized sample, while the L1 2 formation is promoted by heat-treatment, with the latter being accompanied by a dramatic change in dislocation-slip behavior. These findings uncover short-range order and the resulted chemical heterogeneities behind the mechanical strength in CrCoNi, providing general opportunities for atomistic-structure study in concentrated alloys for the design of strong and ductile materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Influence of Cation Size on the Local Atomic Structure and Electronic Properties of Ta Perovskite Oxynitrides

Partial anion substitution in transition metal oxides provides rich opportunities to control and tune physical and chemical properties, for example, combining the merits of oxides and nitrides. In addition, the possibility of resulting anion sublattice order provides a means to target polar and chiral structures based on a wide array of accessible structural archetypes by design. Here, in this work, we investigate the local structures of a family of perovskite tantalum oxynitrides—ATaO 2 N (A = Ba, Sr, and Ca)—using a combination of experimental and theoretical approaches including neutron total scattering, density functional theory (DFT), and ab initio molecular dynamics (AIMD) simulations. We present the first experimental study of chemical short-range order (CSRO) in CaTaO 2 N, confirming local cis N ordering of the anion sub-lattice. Our systematic exploration of a local structure across the A cation size series (from the larger Ba to the smaller Ca) reveals a perovskite motif increasingly distorted with respect to long-range average structures. DFT and AIMD simulations support the observed trends. Overall, structures with cis ordering of the nitrogen anions in each TaO 4 N 2 octahedron are favored over those with trans ordering. With diminishing A cation size, local cis ordering and Ta off-centering play decreasing roles in overall lattice stability, overshadowed by the stabilizing effects of octahedral tilting. The influence of these factors on local dipole formation and frustrated dipole ordering are discussed.

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

Interplay of itinerant electrons and Ising moments in a hybrid honeycomb quantum magnet TmNi 3 Al 9

The interplay between itinerant electrons and local magnetic moments in quantum materials brings about rich and fascinating phenomena and stimulates various developments in the theoretical framework. In this work, thermodynamic, electric transport, and neutron diffraction measurements were performed on a newly synthesized honeycomb lattice magnet TmNi 3 Al 9 . Based on the experimental data, a magnetic-field–temperature phase diagram was constructed, exhibiting three essentially different magnetic regions. Below T N =2.97±0.02KTm 3+ , moments order antiferromagnetically in zero field. We found that the Tm 3+ ions form a pseudodoublet ground state with the Ising-like moments lying normal to the two-dimensional honeycomb layers. Application of a magnetic field along the easy axis gradually suppresses the antiferromagnetic order in favor of an induced ferromagnetic state above the critical field B c =0.92±0.05T. In the vicinity of B c , a strong enhancement of the quantum spin fluctuations was observed. The quantum Ising nature of the local moments and the coupling to itinerant electrons are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

DMFT Reveals the Non-Hermitian Topology and Fermi Arcs in Heavy-Fermion Systems

When a strongly correlated system supports well-defined quasiparticles, it allows for an elegant one-body effective description within the non-Hermitian topological theory. While the microscopic many-body Hamiltonian of a closed system remains Hermitian, the one-body quasiparticle Hamiltonian is non-Hermitian due to the finite quasiparticle lifetime. We use such a non-Hermitian description in the heavy-fermion two-dimensional systems with the momentum-dependent hybridization to reveal a fascinating phenomenon which can be directly probed by the spectroscopic measurements, the bulk “Fermi arcs.” Starting from a simple two-band model, we first combine the phenomenological approach with the perturbation theory to show the existence of the Fermi arcs and reveal their connection to the topological exceptional points, special points in the Brillouin zone where the Hamiltonian is nondiagonalizable. The appearance of such points necessarily requires that the electrons belonging to different orbitals have different lifetimes. This requirement is naturally satisfied in the heavy-fermion systems, where the itinerant c electrons experience much weaker interaction than the localized f electrons. We then utilize the dynamical mean field theory to numerically calculate the spectral function and confirm our findings. We show here that the concept of the exceptional points in the non-Hermitian quasiparticle Hamiltonians is a powerful tool for predicting new phenomena in strongly correlated electron systems.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Chemical interactions that govern the structures of metals

Most metals adopt simple structures such as body-centered cubic (BCC), face-centered cubic (FCC), and hexagonal close-packed (HCP) structures in specific groupings across the periodic table, and many undergo transitions to surprisingly complex structures on compression, not expected from conventional free-electron-based theories of metals. First-principles calculations have been able to reproduce many observed structures and transitions, but a unified, predictive theory that underlies this behavior is not yet in hand. Discovered by analyzing the electronic properties of metals in various lattices over a broad range of sizes and geometries, a remarkably simple theory shows that the stability of metal structures is governed by electrons occupying local interstitial orbitals and their strong chemical interactions. The theory provides a basis for understanding and predicting structures in solid compounds and alloys over a broad range of conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Local lattice distortions and electronic phases in perovskite manganite Pr 0.5 Sr 0.5 MnO 3

We use variable temperature and magnetic field total x-ray scattering to study the crystal structure of the strongly correlated Pr 0.5 Sr 0.5 MnO 3 perovskite, which is a paramagnetic insulator at room temperature, becomes a ferromagnetic metal at 272 K and, upon further decreasing the temperature, turns into an antiferromagnetic insulator at 105 K. We find that a model featuring a monoclinic symmetry captures the structure and its temperature and field evolution well, eliminating the need to evoke a phase segregation scenario as done in prior studies. It appears that coupled variations in Mn–oxygen bonding distances and angles from their values in an undistorted perovskite lattice, i.e., coupled local lattice distortions, assist the phase transitions in Pr 0.5 Sr 0.5 MnO 3 , contributing to its unique physical properties. Local structural distortions thus emerge as an important degree of freedom in strongly correlated systems, in particular perovskite manganates, and, therefore, they should be fully accounted for when their fascinating physics is considered.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Near field excited state imaging via stimulated electron energy gain spectroscopy of localized surface plasmon resonances in plasmonic nanorod antennas

Continuous wave (cw) photon stimulated electron energy loss and gain spectroscopy (sEELS and sEEGS) is used to image the near field of optically stimulated localized surface plasmon resonance (LSPR) modes in nanorod antennas. An optical delivery system equipped with a nanomanipulator and a fiber-coupled laser diode is used to simultaneously irradiate plasmonic nanostructures in a (scanning) transmission electron microscope. The nanorod length is varied such that the m = 1, 2, and 3 LSPR modes are resonant with the laser energy and the optically stimulated near field spectra and images of these modes are measured. Various nanorod orientations are also investigated to explore retardation effects. Optical and electron beam simulations are used to rationalize the observed patterns. As expected, the odd modes are optically bright and result in observed sEEG responses. The m = 2 dark mode does not produce a sEEG response, however, when tilted such that retardation effects are operative, the sEEG signal emerges. Thus, we demonstrate that cw sEEGS is an effective tool in imaging the near field of the full set of nanorod plasmon modes of either parity.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Confinement of quasi-atomic structures in Ti 2 N and Ti 3 N 2 MXene electrides

Metal carbides, nitrides, or carbonitrides of early transition metals, better known as MXenes, possess notable structural, electrical, and magnetic properties. Analyzing electronic structures by calculating structural stability, band structure, density of states, Bader charge transfer, and work functions utilizing first principle calculations, we revealed that titanium nitride MXenes, namely Ti 2 N and Ti 3 N 2 , have excess anionic electrons in their lattice voids, making them MXene electrides. Bulk Ti 3 N 2 has competing antiferromagnetic (AFM) and ferromagnetic (FM) configurations with slightly more stable AFM configuration, while the Ti 2 N MXene is nonmagnetic. Although Ti 3 N 2 favors AFM configuration with hexagonal crystal systems having 6/ mmm point group symmetry, Ti 3 N 2 does not support altermagnetism. The monolayer of the Ti 3 N 2 MXene is a ferromagnetic electride. These unique properties of having non-nuclear interstitial anionic electrons in the electronic structure of titanium nitride MXene have not yet been reported in the literature. Density functional theory calculations show TiN is neither an electride, MXene, or magnetic.

Anionic electrons↗
DOE OSTI2020

Universal scaling of weak localization in graphene due to bias-induced dispersion decoherence

The differential conductance of graphene is shown to exhibit a zero-bias anomaly at low temperatures, arising from a suppression of the quantum corrections due to weak localization and electron interactions. A simple rescaling of these data, free of any adjustable parameters, shows that this anomaly exhibits a universal, temperature- (T) independent form. According to this, the differential conductance is approximately constant at small voltages (V < kBT/e), while at larger voltages it increases logarithmically with the applied bias. For theoretical insight into the origins of this behaviour, which is inconsistent with electron heating, we formulate a model for weak-localization in the presence of nonequilibrium transport. According to this model, the applied voltage causes unavoidable dispersion decoherence, which arises as diffusing electron partial waves, with a spread of energies defined by the value of the applied voltage, gradually decohere with one another as they diffuse through the system. The decoherence yields a universal scaling of the conductance as a function of eV/kBT, with a logarithmic variation for eV/kBT > 1, variations in accordance with the results of experiment. Our theoretical description of nonequilibrium transport in the presence of this source of decoherence exhibits strong similarities with the results of experiment, including the aforementioned rescaling of the conductance and its logarithmic variation as a function of the applied voltage.

42 ENGINEERING↗
DOE OSTI2020

Topological flat bands in frustrated kagome lattice CoSn

Electronic flat bands in momentum space, arising from strong localization of electrons in real space, are an ideal stage to realize strongly-correlated phenomena. Theoretically, the flat bands can naturally arise in certain geometrically frustrated lattices, often with nontrivial topology if combined with spin-orbit coupling. Here, we report the observation of topological flat bands in frustrated kagome metal CoSn, using angle-resolved photoemission spectroscopy and band structure calculations. Throughout the entire Brillouin zone, the bandwidth of the flat band is suppressed by an order of magnitude compared to the Dirac bands originating from the same orbitals. The frustration-driven nature of the flat band is directly confirmed by the chiral d-orbital texture of the corresponding real-space Wannier functions. Spin-orbit coupling opens a large gap of 80 meV at the quadratic touching point between the Dirac and flat bands, endowing a nonzero Z2 invariant to the flat band. These findings demonstrate that kagome-derived flat bands are a promising platform for novel emergent phases of matter at the confluence of strong correlation and topology.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Anomalous Drag in Electron-Hole Condensates with Granulated Order

We explain the strong interlayer drag resistance observed at low temperatures in bilayer electron-hole systems in terms of an interplay between local electron-hole-pair condensation and disorder-induced carrier density variations. Smooth disorder drives the condensate into a granulated phase in which interlayer coherence is established only in well-separated and disconnected regions, or grains, within which the densities of electrons and holes accidentally match. The drag resistance is then dominated by Andreev-like scattering of charge carriers between layers at the grains that transfers momentum between layers. We show that this scenario can account for the observed dependence of the drag resistivity on temperature and, on average, charge imbalance between layers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

0D Nanocrystals as Light‐Driven, Localized Charge‐Injection Sources for the Contactless Manipulation of Atomically Thin 2D Materials

A contactless charge‐injection scheme that allows the local and quasi‐permanent manipulation of atomically thin 2D materials, such as monolayer (1L‐)MoS 2 , over spatial extents of several tens of micrometers, is reported. The possibility to precisely position and localize the charge‐injection source to the micrometer scale post‐fabrication allows the investigation of local unperturbed electronic structure of the 2D material. Thanks to this novel approach, the important impact of sample inhomogeneity on the charge‐carrier percolation that occurs over the entire extent of the 2D flake and proliferates up to 40 μm away from the localized charge injection is elucidated. The apparent driving force for carrier relocation is the initial inhomogeneous electronic landscape of the 2D material. These studies demonstrate that local and contactless charge injection with submicrometer precision delivers an alternative route for charge injection and indicates that local 2D material electronic structure can serve as a key element for novel nanoscale device design.

Ghini, Michele↗
DOE OSTI2020

Origin of gaplike behaviors in URu 2 Si 2 : Combined study via quasiparticle scattering spectroscopy and resistivity measurements

In this work, we address two long-standing questions regarding the hidden order in URu 2 Si 2 : Is it associated with the hybridization process, and what are the distinct roles played by the localized and itinerant electrons? Our quasiparticle scattering spectroscopy reveals a hybridization gap ubiquitous in the entire phase space spanned by P and Fe substitutions in URu 2 Si 2 , including the no-order and antiferromagnetic regions, with minimal change upon crossing the phase boundary. This indicates its opening is not associated with the ordering, and thus localized electrons must be the major player. Towards a consistent understanding of all the other gaplike behaviors observed only below transition temperatures, we analyze the electrical resistivity using a model in which gapped bosonic excitations are the dominant scattering source. With their stiffness set to follow an unusual temperature dependence (decreasing with decreasing temperature), this model fits all of our resistivity data well including the jump at the transition. Remarkably, the extracted gap increases slowly with increasing Fe content, similarly to the gap detected by inelastic neutron scattering at $Q_1$ = (1.4, 0, 0), suggesting a common origin. Such a model can also naturally explain the Hall effect temperature dependence without invoking Fermi surface gapping.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Ex Situ Photoelectron Emission Microscopy of Polycrystalline Bismuth and Antimony Telluride Surfaces Exposed to Ambient Oxidation

The surfaces of textured polycrystalline N-type bismuth telluride and P-type antimony telluride materials were investigated using ex situ photoelectron emission microscopy (PEEM). PEEM enabled imaging of the work function for different oxidation times due to exposure to air across sample surfaces. The spatially averaged work function was also tracked as a function of air exposure time. N-type bismuth telluride showed an increase in the work function around grain boundaries relative to grain interiors during the early stages of air exposure-driven oxidation. At longer time exposure to air, the surface became homogenous after a ~5 nm-thick oxide formed. X-ray photoemission spectroscopy was used to correlate changes in PEEM imaging in real space and work function evolution to the progressive growth of an oxide layer. The observed work function contrast is consistent with the pinning of electronic surface states due to the defects at a grain boundary.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗