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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 1,099 records · Page 61
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Bimolecular crystal instability and morphology of bulk heterojunction blends in organic and perovskite solar cells

The performance of polymer:fullerene bulk heterojunction (BHJ) solar cells is significantly influenced by the morphology of electron donor and acceptor blends under the premise that electronic structure is complimentary regarding donor and acceptor materials. There are many cases where intimate mixing of donor and acceptor perturbs the electronic structure, which fundamentally changes the transport and photovoltaic characteristics. In this work, we present the bimolecular crystal packing of polymers and fullerenes, and investigate the correlation between device performance and structural details. We find that bimolecular crystallization can reorganize polymer chain packing, leading to poor electron transport and device performance. The size compatibility and the passivation of entropy penalty led to cocrystallization instability, which was clearly seen by in situ GIWAXS data. PC 61 BM is found to intercalate into side chains of PQT by reorganizing both PQT and PC 61 BM, forming stable, highly ordered bimolecular crystals. The poor electron transport in bimolecular crystal domain could account for the poor device performance in both perovskite and organic solar cells. Bis-PC 61 BM, on the other hand, only forms loosely packed aggregates in solution, and then rapidly phase separated into large domains with an edge-on interfacial orientation and performed poorly in solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Normal modes, rotational inertia, and thermal fluctuations of trapped ion crystals

The normal modes of a trapped ion crystal are derived using an approach based on the Hermitian properties of the system’s dynamical matrix. This method is equivalent to the standard Bogoliubov method, but for classical systems it is arguably simpler and more general in that canonical coordinates are not necessary. The theory is developed for stable, unstable, and neutrally-stable systems. The method is then applied to ion crystals in a Penning trap. Reduced eigenvalue problems for the case of large applied magnetic field are developed, for which the spectrum breaks into E x B drift modes, axial modes, and cyclotron modes. Thermal fluctuation levels in these modes are analyzed and shown to be consistent with the Bohr-van-Leeuwen theorem, provided that neutrally-stable modes associated with crystal rotations are included in the analysis. An expression for the rotational inertia of the crystal is derived, and a magnetic contribution to this inertia, which dominates in large magnetic fields, is described. An unusual limit is discovered for the special case of spherically-symmetric confinement, in which the rotational inertia does not exist and changes in angular momentum leave the rotation frequency unaffected.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Operando single crystal neutron diffraction reveals insight into the field response mechanisms in the hydrogen-bonded KH 2 PO 4 ferroelectric

The mechanism that facilitates polarization reorientation in KH 2 PO 4 (KDP) was investigated using operando single-crystal neutron diffraction. Diffraction data were measured from a KDP single crystal during the application of alternating electric fields and were then binned into 40 increments to enable field-dependent single-crystal structure refinements. The field-dependent structures are compared with an as-grown crystal to determine how the lattice and atomic sites evolve in response to the applied electric fields. These analyses provide evidence that the reorientation of the macroscopic polarization is facilitated through a cooperative change in hydrogen bonding, which results in the reversal of the spontaneous dipole. In addition, a decrease in secondary extinction near the coercive field indicates that the inversion of the macroscopic polarization is achieved through the nucleation and subsequent growth of new domains.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Zn acceptors in β-Ga 2 O 3 crystals

Electron paramagnetic resonance (EPR) is used to identify and characterize neutral zinc acceptors in Zn-doped β-Ga 2 O 3 crystals. Two EPR spectra are observed at low temperatures, one from Zn ions at tetrahedral Ga(1) sites (the $Zn$$^{0}_{Ga 1}$ acceptor) and one from Zn ions at octahedral Ga(2) sites (the $Zn$$^{0}_{Ga 2}$ acceptor). These Zn acceptors are small polarons, with the unpaired spin localized in each case on a threefold coordinated oxygen O(I) ion adjacent to the Zn ion. Resolved hyperfine interactions with neighboring 69 Ga and 71 Ga nuclei allow the EPR spectra from the two acceptors to be easily distinguished: $Zn$$^{0}_{Ga 1}$ acceptors interact equally with two Ga(2) ions and $Zn$$^{0}_{Ga 2}$ acceptors interact unequally with a Ga(1) ion and a Ga(2) ion. The as-grown crystals are compensated, with the Zn ions initially present as singly ionized acceptors ($Zn$$^{-}_{Ga 1}$ and $Zn$$^{-}_{Ga 2}$). Exposing a crystal to 325 nm laser light, while being held at 140 K, primarily produces neutral $Zn$$^{0}_{Ga 2}$ acceptors when photoinduced holes are trapped at $Zn$$^{-}_{Ga 2}$ acceptors. This suggests that there may be significantly more Zn ions at Ga(2) sites than at Ga(1) sites. Warming the crystal briefly to room temperature, after removing the light, destroys the EPR spectrum from the shallower $Zn$$^{0}_{Ga 2}$ acceptors and produces the EPR spectrum from the more stable $Zn$$^{0}_{Ga 1}$ acceptors. Furthermore, the $Zn$$^{0}_{Ga 2}$ acceptors decay in the 240–260 K region with a thermal activation energy near 0.65 eV, similar to $Mg$$^{0}_{Ga 2}$ acceptors, whereas the slightly deeper $Zn$$^{0}_{Ga 1}$ acceptors decay close to room temperature with an approximate thermal activation energy of 0.78 eV.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Observation of spatially resolved Rashba states on the surface of CH 3 NH 3 PbBr 3 single crystals

Hybrid organic-inorganic perovskites (HOIPs) are prime candidates for studying Rashba effects due to the heavy metal and halogen atoms in their crystal structure coupled with predicted inversion symmetry breaking. Nevertheless, observation of the Rashba effect in cubic CH 3 NH 3 PbBr 3 single crystals that possess bulk inversion symmetry is the subject of extensive debate due to the lack of conclusive experiments and theoretical explanations. In this work, we provide experimental evidence that Rashba state in cubic CH 3 NH 3 PbBr 3 single crystals at room temperature occurs exclusively on the crystal surface and depends on specific surface termination that results in local symmetry breaking. We demonstrate this using a suite of spatially resolved and depth-sensitive techniques, including circular photogalvanic effect, inverse spin Hall effect, and multiphoton microscopy, that are supported by first principle calculations. Our work suggests using surface Rashba states in these materials for spintronic applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Nucleation kinetics model for primary crystallization in Al–Y–Fe metallic glass

The high density of aluminum nanocrystals (>10 21 m -3 ) that develop during the primary crystallization in Al-based metallic glasses indicates a high nucleation rate (~10 18 m -3 s -1 ). Several studies have been advanced to account for the primary crystallization behavior, but none have been developed to completely describe the reaction kinetics. Recently, structural analysis by fluctuation electron microscopy has demonstrated the presence of the Al-like medium range order (MRO) regions as a spatial heterogeneity in as-spun Al 88 Y 7 Fe 5 metallic glass that is representative for the class of Al-based amorphous alloys that develop Al nanocrystals during primary crystallization. From the structural characterization, an MRO seeded nucleation configuration is established, whereby the Al nanocrystals are catalyzed by the MRO core to decrease the nucleation barrier. The MRO seeded nucleation model and the kinetic data from the delay time (τ) measurement provide a full accounting of the evolution of the Al nanocrystal density (N v ) during the primary crystallization under isothermal annealing treatments. Moreover, the calculated values of the steady state nucleation rates (J ss ) predicted by the nucleation model agree with the experimental results. Moreover, the model satisfies constraints on the structural, thermodynamic, and kinetic parameters, such as the critical nucleus size, the interface energy, and the volume-free energy driving force that are essential for a fully self-consistent nucleation kinetics analysis. In conclusion, the nucleation kinetics model can be applied more broadly to materials that are characterized by the presence of spatial heterogeneities.

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

Twinning microstructure in the solid-phase epitaxial crystallization of BaTiO 3

Amorphous BaTiO 3 layers deposited on SrTiO 3 (001) substrates at room temperature were subsequently crystallized using solid phase epitaxy (SPE). Heating an initially amorphous BaTiO 3 layer in air at 650 °C for 3 h resulted in crystallization with components in two distinct crystallographic orientation relationships with respect to the substrate. Part of the volume of the BaTiO 3 layer crystallized in a cube-on-cube relationship with the substrate. Other volumes crystallized in four variants of a 70.5° rotation about $\langle$110$\rangle$, resulting in a $\langle$221$\rangle$ surface normal in each case. Each of these four variants forms a Σ = 3 coincident site lattice with respect to the SrTiO 3 substrate and the cube-on-cube oriented BaTiO 3 . Heating for the same duration and temperature in a reducing gas atmosphere resulted in the formation of polycrystalline BaTiO 3 with no preferred crystallographic orientation. The dependence on the gas atmosphere indicates that it may be possible to tune the annealing time, temperature, and atmosphere to produce a single crystalline BTO on STO by SPE or produce a desired distribution of orientations.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Development and characterization of a laser-gated, high resolution x-ray radiography platform for high energy density experiments using toroidally bent crystals

Bent crystal x-ray imagers are a well-established diagnostic tool to study high energy density (HED) objects by acquiring two-dimensional x-ray radiographs. Often, studying these HED objects requires very high spatial resolution, which is limited by astigmatism when using spherically bent crystals. By using toroidal-shaped crystals instead, astigmatism can be reduced and the overall spatial resolution of the instrument improved. Here, the development and characterization of a laser-gated x-ray radiography platform at the National Ignition Facility using a toroidal crystal is presented. This includes measurements of the spatial and temporal profile, which is determined by the x-ray source. In conclusion, to properly validate the reduced astigmatism, a new multi-plane grid approach was implemented, which, for the first time, allows a depth of field measurement, alignment verification and x-ray source size estimate in a single shot, demonstrating the current platform’s capability to provide sub-10 μm resolution over a 0.9 mm depth of field with a temporal resolution of 110 ps.

Crystal optics↗
DOE OSTI2026

High-resolution bandpass x-ray imaging with crystal reflectors: Overcoming geometric aberrations

The imaging problem of a specular reflector is revisited. Retaining terms through the second order in the reflector surface expansion, we derive the form of the aberration-limiting aperture for arbitrary magnification, assuming no bandwidth limitations. A permissible relative aperture size of the reflector is limited by a set relative aberration tolerance and scales with the tangent of the central glancing angle of incidence. These limiting aberrations become practically insignificant near backscattering. The results extend to x-ray diffracting crystals in symmetric Bragg geometry shaped as an ellipsoid of revolution. This geometry permits polychromatic imaging for hard x-rays over a bandwidth defined by the accepted range of Bragg angles, thereby suppressing aberrations of higher orders. We assess ellipsoidal crystal imagers using ray tracing simulations for two high-magnification designs with Bragg angles far from and close to backscattering. Finally, in both cases, the ellipsoidal crystals produce images of higher quality compared to those formed by equivalent toroidal crystal imagers.

Bragg reflection↗
DOE OSTI2023

A methodology to generate crystal-based molecular structures for atomistic simulations

Abstract We propose a systematic method to construct crystal-based molecular structures often needed as input for computational chemistry studies. These structures include crystal ‘slabs’ with periodic boundary conditions (PBCs) and non-periodic solids such as Wulff structures. We also introduce a method to build crystal slabs with orthogonal PBC vectors. These methods are integrated into our code, Los Alamos Crystal Cut ( LCC ), which is open source and thus fully available to the community. Examples showing the use of these methods are given throughout the manuscript.

42 ENGINEERING↗
DOE OSTI2022

Modeling and experimental validation of dynamical effects in Bragg coherent x-ray diffractive imaging of finite crystals

Bragg coherent diffractive imaging (BCDI) is a noninvasive microscopy technique that can visualize the shape and internal lattice deviations of crystals with nanoscale spatial resolution and picometer deformation sensitivity. Its strain imaging capability relies on Fourier transform–based iterative phase retrieval algorithms, which are mostly developed under the kinematical approximation. Such approximation prohibits the application of BCDI on larger crystals, which are commonly seen in most emerging functional materials. Understanding the dynamical effect in BCDI, as well as developing a validated method for modeling BCDI at the dynamical diffraction limit, is crucial for applying BCDI to hierarchical systems that contain micron-sized crystals and grains. Thus we report a comparative study on the impact of dynamical diffraction effects by comparing the reconstruction results from two measurements of the same crystal. Forward simulation is implemented to show subtle changes of interference fringes in the diffraction pattern due to the dynamical diffraction, and is compared directly with the experimental data.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Unconventional crystal-field splitting in noncentrosymmetric BaTiO 3 thin films

Understanding the crystal-field splitting and orbital polarization in noncentrosymmetric systems such as ferroelectric materials is fundamentally important. In this work, taking BaTiO 3 as a representative material, we investigate titanium crystal-field splitting and orbital polarization in noncentrosymmetric TiO 6 octahedra with resonant x-ray linear dichroism at the Ti L 2,3 edge. The high-quality BaTiO 3 thin films were deposited on DyScO 3 (110) single crystal substrates in a layer-by-layer way by pulsed laser deposition. The reflection high-energy electron diffraction and element specific x-ray absorption spectroscopy were performed to characterize the structural and electronic properties of the films. In sharp contrast to conventional crystal-field splitting and orbital configuration (d xz /d yz < d xy < d 3z 2 -r 2 < d x 2 -y 2 or d xy < d xz /d yz < d x 2 -y 2 < d 3z 2 -r 2 ) expected from compressive or tensile epitaxial strain, respectively, it is revealed that d xz , d yz , and d xy orbitals are nearly degenerate, whereas d 3z 2 -r 2 and d x 2 -y 2 orbitals are split with an energy gap ~100 meV in the epitaxial BaTiO 3 films. We find that the unexpected degenerate orbitals d xz /d yz /d xy result from the competition between the orbital splitting induced by epitaxial strain and that induced by polar distortions of BaTiO 3 films. Our results provide a route to manipulate orbital degree of freedom by switching electric polarization in ferroelectric materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Data-centric framework for crystal structure identification in atomistic simulations using machine learning

Atomic-level modeling performed at large scales enables the investigation of mesoscale materials properties with atom-by-atom resolution. The spatial complexity of such cross-scale simulations renders them unsuitable for simple human visual inspection. Instead, specialized structure characterization techniques are required to aid interpretation. These have historically been challenging to construct, requiring significant intuition and effort. Here we propose an alternative framework for a fundamental structural characterization task: classifying atoms according to the crystal structure to which they belong. Our approach is data-centric and favors the employment of Machine Learning over heuristic rules of classification. A group of data-science tools and simple local descriptors of atomic structure are employed together with an efficient synthetic training set. We also introduce the first standard and publicly available benchmark data set for evaluation of algorithms for crystal-structure classification. Further, it is demonstrated that our data-centric framework outperforms all of the most popular heuristic methods—especially at high temperatures when lattices are the most distorted—while introducing a systematic route for generalization to new crystal structures. Moreover, through the use of outlier detection algorithms our approach is capable of discerning between amorphous atomic motifs (i.e., noncrystalline phases) and unknown crystal structures, making it uniquely suited for exploratory materials synthesis simulations.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Bent Laue crystal anatomy: new insights into focusing and energy-dispersion properties

X-ray Laue-type monochromators are common and essential optical components at many high-power X-ray facilities, e.g. synchrotron facilities. The X-ray optics of bent Laue crystals is a well developed area. An incident X-ray beam penetrating a bent Laue crystal will result in a diffracted beam with different angles and energies. There is a need for a way of organizing the rays that allows one to sort out the energy and spatial properties of the diffracted beam. The present work introduces a new approach for describing the general behaviour of bent Laue crystals from a ray-tracing point of view. This quasi-monochromatic beam approach provides an intuitive view of bent-crystal diffraction and leads to deeper understanding. It explains the energy and spatial properties of common and special cases of bent Laue optics, predicts phenomena that can improve energy-dispersion-related X-ray imaging techniques and provides a theoretical framework that makes ray-tracing simulation easier to realize.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Assessing an aqueous flow cell designed for in situ crystal growth under X-ray nanotomography and effects of radiolysis products

Nucleation and growth of minerals has broad implications in the geological, environmental and materials sciences. Recent developments in fast X-ray nanotomography have enabled imaging of crystal growth in solutions in situ with a resolution of tens of nanometres, far surpassing optical microscopy. Here, a low-cost, custom-designed aqueous flow cell dedicated to the study of heterogeneous nucleation and growth of minerals in aqueous environments is shown. To gauge the effects of radiation damage from the imaging process on growth reactions, radiation-induced morphological changes of barite crystals (hundreds of nanometres to ∼1 µm) that were pre-deposited on the wall of the flow cell were investigated. Under flowing solution, minor to major crystal dissolution was observed when the tomography scan frequency was increased from every 30 min to every 5 min (with a 1 min scan duration). The production of reactive radicals from X-ray induced water radiolysis and decrease of pH close to the surface of barite are likely responsible for the observed dissolution. The flow cell shown here can possibly be adopted to study a wide range of other chemical reactions in solutions beyond crystal nucleation and growth where the combination of fast flow and fast scan can be used to mitigate the radiation effects.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Enhanced X-ray diffraction of in vivo-grown μNS crystals by viscous jets at XFELs

μNS is a 70 kDa major nonstructural protein of avian reoviruses, which cause significant economic losses in the poultry industry. They replicate inside viral factories in host cells, and the μNS protein has been suggested to be the minimal viral factor required for factory formation. Thus, determining the structure of μNS is of great importance for understanding its role in viral infection. In the study presented here, a fragment consisting of residues 448–605 of μNS was expressed as an EGFP fusion protein in Sf9 insect cells. EGFP-μNS (448–605) crystallization in Sf9 cells was monitored and verified by several imaging techniques. Cells infected with the EGFP-μNS (448–605) baculovirus formed rod-shaped microcrystals (5–15 µm in length) which were reconstituted in high-viscosity media (LCP and agarose) and investigated by serial femtosecond X-ray diffraction using viscous jets at an X-ray free-electron laser (XFEL). The crystals diffracted to 4.5 Å resolution. A total of 4227 diffraction snapshots were successfully indexed into a hexagonal lattice with unit-cell parameters a = 109.29, b = 110.29, c = 324.97 Å. The final data set was merged and refined to 7.0 Å resolution. Preliminary electron-density maps were obtained. While more diffraction data are required to solve the structure of μNS (448–605) , the current experimental strategy, which couples high-viscosity crystal delivery at an XFEL with in cellulo crystallization, paves the way towards structure determination of the μNS protein.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

On single-crystal total scattering data reduction and correction protocols for analysis in direct space

Data reduction and correction steps and processed data reproducibility in the emerging single-crystal total-scattering-based technique of three-dimensional differential atomic pair distribution function (3D-ΔPDF) analysis are explored. All steps from sample measurement to data processing are outlined using a crystal of CuIr 2 S 4 as an example, studied in a setup equipped with a high-energy X-ray beam and a flat-panel area detector. Computational overhead as pertains to data sampling and the associated data-processing steps is also discussed. Various aspects of the final 3D-ΔPDF reproducibility are explicitly tested by varying the data-processing order and included steps, and by carrying out a crystal-to-crystal data comparison. Situations in which the 3D-ΔPDF is robust are identified, and caution against a few particular cases which can lead to inconsistent 3D-ΔPDFs is noted. Although not all the approaches applied herein will be valid across all systems, and a more in-depth analysis of some of the effects of the data-processing steps may still needed, the methods collected herein represent the start of a more systematic discussion about data processing and corrections in this field.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Crystal structures and comparisons of potassium rare-earth molybdates KRE(MoO 4 ) 2 (RE = Tb, Dy, Ho, Er, Yb, and Lu)

Six potassium rare-earth molybdates KRE(MoO 4 ) 2 (RE = Tb, Dy, Ho, Er, Yb, and Lu) were synthesized by flux-assisted growth in K 2 Mo 3 O 10 . The crystal structures were determined using single-crystal X-ray diffraction data. The synthesized molybdates crystallize with the orthorhombic Pbcn space group (No. 60). Trendlines for unit-cell parameters were calculated using data from the current study. The unit-cell parameters a and c increase linearly whereas b decreases with larger RE cations, based on crystal radii. The unit-cell volumes increase linearly and the densities decrease linearly with larger RE cations. The average distances between the RE cations and the nearest O atoms increase with larger cations whereas the average distances of Mo—O and K—O do not show specific trends.

36 MATERIALS SCIENCE↗