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Paramagnon dispersion and damping in doped Na x Ca 2 – x CuO 2 Cl 2

Here, using resonant inelastic x-ray scattering, we measure the paramagnon dispersion and damping of undoped, antiferromagnetic Ca 2 CuO 2 Cl 2 as well as doped, superconducting Na x Ca 2–x CuO 2 Cl 2 . Our estimation of the spin-exchange parameter and width of the paramagnon peak at the zone boundary X=(0.5, 0) confirms that no simple relation can be drawn between these parameters and the critical temperature T c . Consistently with other cuprate compounds, we show that upon doping there is a slight softening at (0.25,0) but not at the zone boundary X. In combination with these measurements we perform calculations of the dynamical spin structure factor of the one-band Hubbard model using cluster dynamical mean-field theory. The calculations are in excellent agreement with the experiment in the undoped case, both in terms of energy position and width. While the increase in width is also captured upon doping, the dynamical spin structure factor shows a sizable softening at X, which provides insightful information on the length-scale of the spin fluctuations in doped cuprates.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Level structure of light neutron-rich La isotopes beyond the 𝑁 = 82 shell closure

Here, the high spin excited states of Lanthanum isotopes 140–143 La, above the 𝑁 = 82 closed shell, were populated in fission reactions. The prompt 𝛾-ray transitions were measured using two complementary methods: (a) in coincidence with the isotopically identified fragments produced in the fission of the 238 U + 9 Be system using the Variable Mode Spectrometer (VAMOS++) and the Advanced Gamma Tracking Array (AGATA) spectrometer, and (b) high statistics threefold 𝛾−𝛾−𝛾 and fourfold 𝛾−𝛾−𝛾−𝛾 coincidence data from the spontaneous fission of 252 Cf using the Gammasphere. This work reports the first identification of a pair of parity doublet structures in 143 La and the new high spin level structure in 140–142 La from prompt 𝛾-ray spectroscopy. The level structures are interpreted in terms of the systematics of neighboring odd-𝑍 nuclei above the 𝑍 = 50 shell closure and large-scale shell model calculations. The present results indicate the presence of stable octupole deformation in 143 La. The excitation energy pattern and their comparison with neighboring isotones, moving away from the 𝑁 = 82 closed shell, point towards a transition from single-particle structures to an alternating parity rotational band structure in the La isotopic chain.

Navin, A. [Centre National de la Recherche Scienti↗

Coupling between plasmonic and photonic crystal modes in suspended three-dimensional meta-films

A complementary metal oxide semiconductor (CMOS) compatible fabrication method for creating three-dimensional (3D) meta-films is presented. In contrast to metasurfaces, meta-films possess structural variation throughout the thickness of the film and can possess a sub-wavelength scale structure in all three dimensions. Here we use this approach to create 2D arrays of cubic silicon nitride unit cells with plasmonic inclusions of elliptical metallic disks in horizontal and vertical orientations with lateral array-dimensions on the order of millimeters. Fourier transform infrared (FTIR) spectroscopy is used to measure the infrared transmission of meta-films with either horizontally or vertically oriented ellipses with varying eccentricity. Shape effects due to the ellipse eccentricity, as well as localized surface plasmon resonance (LSPR) effects due to the effective plasmonic wavelength are observed in the scattering response. The structures were modeled using rigorous coupled wave analysis (RCWA), finite difference time domain (Lumerical), and frequency domain finite element (COMSOL). The silicon nitride support structure possesses a complex in-plane photonic crystal slab band structure due to the periodicity of the unit cells. We show that adjustments to the physical dimensions of the ellipses can be used to control the coupling to this band structure. The horizontally oriented ellipses show narrow, distinct plasmonic resonances while the vertically oriented ellipses possess broader resonances, with lower overall transmission amplitude for a given ellipse geometry. We attribute this difference in resonance behavior to retardation effects. The ability to couple photonic slab modes with plasmonic inclusions enables a richer space of optical functionality for design of metamaterial-inspired optical components.

42 ENGINEERING↗

THERMAL/STRUCTURAL ANALYSIS OF THE AXION QUANTUM METROLOGY CAVITY AND ITS COMPONENTS

This research was centered around maximizing the capability to cool dielectric material within a containment unit, or Photonic Band Gap (PBG) cavity, designed for detecting axion dark matter and identifying the unit’s thermal properties. There are multiple types of PBG cavities, but the latest version that axion researchers wish to use has been theorized to contain possible issues related to its thermal properties. Thermal conductivity is an issue with the dielectric material because it is made from alumina which is highly insulative. This is important since the research is being done in a cryogenic environment and the thermal noise affects the quantum bit used for detecting the axion to photon conversion process. Therefore, any improvements to this unit should be justified and implemented but are not entirely limited to thermal contact related aspects of PBG cavities. A prospect of using sapphire in place of alumina also exists, but this is a more expensive, less tested, and more elusive material to justify the creation of a full dielectric structure out of sapphire. Thermal aspects of the cavity were analyzed using finite element method (FEM) and an experiment designed to test different thermal joint materials. FEM was used to check the contraction of the cavity during cooling, the contact quality between the dielectric material and cavity wall, theheat flow rate through the assembly, and helps visualize the cavity’s reaction to different design changes. A simple comparison between thermal conductivity curves justified the usage of sapphire over alumina from a thermal property point of view. Thus, the method of experimentation had an additional dielectric material, sapphire, to test with and compare to alumina. The thermal test identified which material is best to use for a thermal joint but also simultaneously found the conductance of the joint and dielectric material as well as an estimate for what the temperature is inside the larger scale cavity since a thermometer cannot be placed inside the PBG when it cools. Initially, the cavity simulation was tested for structural deformation properties and stress distribution since it is made of copper which contracts heavily in comparison to most other materials. The reduction in volume of the cavity was less than anticipated which gave more room for a possible usage of a modified thermal joint for additional contact area and higher conductivity.

43 PARTICLE ACCELERATORS↗

Nonresonant two-photon x-ray absorption in Cu

We present a real-space Green's function theory and calculations of two-photon x-ray absorption (TPA). Our focus is on nonresonant 𝐾-shell TPA in metallic Cu, which has been observed experimentally at intense x-ray free electron laser (XFEL) sources. The theory is based on an independent particle Green's function treatment of the Kramers-Heisenberg equation and an approximation for the sum over nonresonant intermediate states in terms of a static quadrupole transition operator. XFEL effects are modeled by a partially depleted 𝑑 band. This approach is shown to give results for 𝐾-shell TPA in quantitative agreement with XFEL experiment and with a Bethe-Salpeter equation approach. Furthermore, we also briefly discuss many-body corrections and TPA sum rules.

Approximation methods for many-body systems↗

Experiments and simulations of isochorically heated warm dense carbon foam at the Texas Petawatt Laser

An experimental and simulation study of warm dense carbon foams at ambient density (n e ~10 21 cm –3 ) is presented. This study of isochorically heated foams is motivated by their potential application in carbon-atmosphere white-dwarf envelopes, where there are modeling uncertainties due to the equation of state. The foams are heated on an approximately picosecond time scale with a laser-accelerated proton beam. The cooling and expansion of the heated foams can be modeled with appropriately initialized radiation-hydrodynamics codes; xRAGE code is used in this work. The primary experimental diagnostic is the streaked optical pyrometer, which images a narrow band of radiation from the rear surface of the heated material. Presented are xRAGE modeling results for both solid aluminum targets and carbonized resorcinol-formaldehyde foam targets, showing that the foam appears to cool slowly on the pyrometer because of partial transparency. So that simulations of cooling foam are processed properly, it is necessary to account for finite optical depth in the photosphere calculation, and the methods for performing that calculation are presented in depth.

36 MATERIALS SCIENCE↗

Band gap predictions of double perovskite oxides using machine learning

Abstract The compositional and structural variety inherent to oxide perovskites spawn wide-ranging applications. In perovskites, the band gap E g , a key material parameter for these applications, can be optimally controlled by varying the composition. Here, we implement a hierarchical screening process in which two cross-validated and predictive machine learning models for band gap classification and regression, trained using exhaustive datasets that span 68 elements of the periodic table, are applied sequentially. The classification model separates wide band gap materials, with E g ≥ 0.5 eV, from materials which have zero or relatively small band gaps, namely E g < 0.5 eV, and the second regression model quantitatively predicts the gap value of the wide band gap compounds. The study down-selects 13,589 cubic oxide perovskite compositions that are predicted to be experimentally formable, thermodynamically stable, and have a wide band gap. Of these, a subset of 310 compounds, which are predicted to be stable and formable with a confidence greater than 90%, are identified for further investigation. Our models are methodically analyzed via performance metrics and inter-dependence of model features to gain physical insight into the band gap prediction problem. Design maps to identify the variation of band gap with substitution of different elements are also presented.

36 MATERIALS SCIENCE↗

Hydroporphyrin-Doped Near-Infrared-Emitting Polymer Dots for Cellular Fluorescence Imaging

We report Near-infrared (NIR) fluorescent semiconductor polymer dots (Pdots) have shown great potential for fluorescence imaging due to their exceptional chemical and photophysical properties. This paper describes the synthesis of NIR emitting Pdots with great control and tunability of emission peak wavelength. The Pdots were prepared by doping poly [(9,9-dioctylfluorenyl-2,7-diyl)-altco-(1,4-benzo-(2,1’,3)-thiadiazole)] (PFBT), a semiconducting polymer commonly used as a host polymer in luminescent Pdots, with a series of chlorins and bacteriochlorins with varying functional groups. Chlorins and bacteriochlorins are ideal dopants due to their high hydrophobicity, which precludes their use as molecular probes in aqueous biological media but on the other hand prevents their leakage when doped into Pdots. Additionally, chlorins and bacteriochlorins have narrow deep-red to NIR emission bands and the wide array of synthetic modifications available for modifying their molecular structure enables tuning their emission predictably and systematically. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements show the chlorin and bacteriochlorin-doped Pdots to be nearly spherical with an average diameter of 46±12 nm. Efficient energy transfer between PFBT and the doped chlorins or bacteriochlorins decreases the PFBT donor emission to near baseline level and increases the emission of the doped dyes that serve as acceptors. The chlorin and bacteriochlorindoped Pdots show narrow emission bands ranging from 640 nm to 820 nm depending on the doped dye. The paper demonstrates the utility of the systematic chlorin and bacteriochlorin synthesis approach by preparing Pdots of varying emission peak wavelength, utilizing them to visualize multiple targets using wide field fluorescence microscopy, binding them to secondary antibodies, and determining the binding of secondary antibody-conjugated Pdots to primary antibody-labeled receptors in plant cells. Additionally, the chlorin and bacteriochlorin doped Pdots show a blinking behavior that could enable their use in super resolution imaging methods like STORM.

13C-NMR↗

Utilization of Novel (KNbO 3 ) 1− x (Ba 2 FeNbO 6 ) x ( x = 0.1, 0.2, 0.3) Solid Solutions for Efficient Photo‐Assisted Fenton Degradation of Methylene Blue Dye

Novel (KNbO 3 ) 1− x (Ba 2 FeNbO 6 ) x ( x = 0.1, 0.2, 0.3) solid solutions corresponding to K 0.82 Ba 0.18 Fe 0.09 Nb 0.91 O 3 , K 0.64 Ba 0.36 Fe 0.18 Nb 0.82 O 3 , and K 0.46 Ba 0.54 Fe 0.27 Nb 0.73 O 3 compounds have been synthesized via molten salt method. X‐ray diffraction confirms the formation of solid solutions, while transmission electron microscopy combined with energy‐dispersive spectroscopy results demonstrates a homogeneous distribution of elements. The obtained solid solutions crystallized in a cubic crystal structure, whereas the parent KNbO 3 possesses an orthorhombic structure. The wide bandgap semiconductor KNbO 3 transformed into a visible‐light‐active material, with its bandgap energy reduced from 3.56 eV to ≈2.4 eV. The substitution of K in KNbO 3 with Ba is responsible for structural modification from orthorhombic to cubic symmetry, whereas both structural modification and the substitution of Nb with Fe correlated with optical properties. The photocatalytic activities of all obtained solid solutions are improved compared with the parent KNbO 3 and Ba 2 FeNbO 6 compounds for photocatalytic degradation of methylene blue (MB) dye. Among the series of solid solutions, K 0.82 Ba 0.18 Fe 0.09 Nb 0.91 O 3 photocatalysts show the highest MB removal efficiency owing to its relatively higher surface area, suppressed charge carrier recombination, and more negative conduction band edge. Moreover, K 0.82 Ba 0.18 Fe 0.09 Nb 0.91 O 3 photocatalyst (0.1 g) combined with hydrogen peroxide (H 2 O 2 ) to form a novel photo‐Fenton system, achieving almost complete degradation of 100 mL of 10 mg L −1 MB dye in 30 min.

Avcıoğlu, Celal [Technische Universität Berlin, Fa↗

The Crystal Structure of BaZn 2 Se 2 (OH) 2 Featuring Brownmillerite‐Type Layers

Abstract A bimetallic hydroxychalcogenide, BaZn 2 Se 2 (OH) 2 , was synthesized through hydrothermal pouch methods. The single crystal X‐ray diffraction and electron diffraction indicates that the phase crystallizes in the orthorhombic space group Pnma and is composed of anionic layers [ZnSe 3/3 (OH) 1/1 ] − that are separated and charged balanced by Ba 2+ cations. The [ZnSe 3/3 (OH) 1/1 ] – layer comprises two unique Zn sites, which form interpenetrating zigzag chains with an in‐plane dipole moment and adopts a brownmillerite‐type structural motif. The adjacent layers contain tetrahedrally coordinated Zn chains of opposite handedness related by an inversion center, which cancel the microscopic dipoles to minimize the macroscopic electric polarization. The adoption of a brownmillerite structural motif in BaZn 2 Se 2 (OH) 2 can be rationalized by the distinct charge difference between Se 2− and OH − anions, which creates a sufficient dipole moment in the ZnSe 3 (OH) tetrahedra to allow the occurrence of twisted chains. FTIR spectroscopy confirms the existence of OH − anions and DFT calculations indicate that BaZn 2 Se 2 (OH) 2 is a semiconductor with a direct band gap. This work expands the chemistry of the brownmillerite family from traditional homoanionic oxides to multianion hydroxychalcogenides, offering a new opportunity to explore tunable structural complexity for better design of functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Colloidal Synthesis Path to 2D Crystalline Quantum Dot Superlattices

By combining colloidal nanocrystal synthesis, self-assembly, and solution phase epitaxial growth techniques, we developed a general method for preparing single dot thick atomically attached quantum dot (QD) superlattices with high-quality translational and crystallographic orientational order along with state-of-the-art uniformity in the attachment thickness. The procedure begins with colloidal synthesis of hexagonal prism shaped core/shell QDs (e.g., CdSe/CdS), followed by liquid subphase self-assembly and immobilization of superlattices on a substrate. Solution phase epitaxial growth of additional semiconductor material fills in the voids between the particles, resulting in a QD-in-matrix structure. The photoluminescence emission spectra of the QD-in-matrix structure retains characteristic 0D electronic confinement. Importantly, annealing of the resulting structures removes inhomogeneities in the QD–QD inorganic bridges, which our atomistic electronic structure calculations demonstrate would otherwise lead to Anderson-type localization. The piecewise nature of this procedure allows one to independently tune the size and material of the QD core, shell, QD–QD distance, and the matrix material. These four choices can be tuned to control many properties (degree of quantum confinement, quantum coupling, band alignments, etc.) depending on the specific applications. Lastly, cation exchange reactions can be performed on the final QD-in-matrix, as demonstrated herein with a CdSe/CdS to HgSe/HgS conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NSUF Report EBSD analyses on metallic fuel samples: Tips and improvements in sample preparation

EBSD (Electron Backscatter Diffraction) is an analytic technique used to evaluate the microstructure of a specimen. It can be used to evaluate interesting crystallographic data ranging from grains size to grain orientation, from grain boundaries to stresses. Moreover, in the field of nuclear materials EBSD can aid in estimating properties important for reactor performance, such as dislocation and residual strain [1]. EBSD patterns are generated by focusing a stationary electron gun on the specimen and detecting the backscatter electrons that satisfy Bragg conditions, and thus are diffracted by the crystal planes forming the so called Kikuchi bands. These bands correspond to each of the lattice diffracting crystal planes and are detected on a phosphor screen via a low-light CCD camera [2]. The patterns are generated within a small interaction volume located at a depth of less than 50-100 nm. Because of this, the data quality is extremely sensitive to the integrity of the crystallographic lattice order at the surface of the sample and thus to sample preparation and to oxidation [3]. While conventional sample preparation methods are widely used in materials science, they often do not lead to quality electron backscatter patterns needed for the characterization of nuclear materials [4]. This has been related by many authors to the challenges associated with handling radiological specimens, their rapid oxidation, and artifacts in such samples (e.g. high number of defects, precipitates and/or porosities) [4-8]. EBSD, however, can be an invaluable technique to evaluate microstructural evolution during fabrication and after irradiation at the required mesoscale for model and simulation. It also provides important information on grain structure necessary to understand irradiation effect, such as grain subdivision. Thus, it is of paramount importance to further the application of this technique to nuclear materials and especially irradiated fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Operation of Cs–Sb–O activated GaAs in a high voltage DC electron gun at high average current

Negative Electron Affinity (NEA) activated GaAs photocathodes are the most popular option for generating a high current (>1 mA) spin-polarized electron beam. Despite its popularity, a short operational lifetime is the main drawback of this material. Recent works have shown that the lifetime can be improved by using a robust Cs–Sb–O NEA layer with minimal adverse effects. In this work, we operate GaAs photocathodes with this new activation method in a high voltage environment to extract a high current. We demonstrate that improved chemical resistance of Cs–Sb–O activated GaAs photocathodes allowed them to survive a day-long transport process from a separate vacuum system using a vacuum suitcase. During beam running, we observed spectral dependence on lifetime improvement. In particular, we saw a 45% increase in the lifetime at 780 nm on average for Cs–Sb–O activated GaAs compared to Cs–O activated GaAs.

47 OTHER INSTRUMENTATION↗

Anisotropic epitaxial stabilization of a low-symmetry ferroelectric with enhanced electromechanical response

Here piezoelectrics interconvert mechanical energy and electric charge and are widely used in actuators and sensors. The best performing materials are ferroelectrics at a morphotropic phase boundary, where several phases coexist. Switching between these phases by electric field produces a large electromechanical response. In ferroelectric BiFeO3, strain can create a morphotropic-phase-boundary-like phase mixture and thus generate large electric-field-dependent strains. However, this enhanced response occurs at localized, randomly positioned regions of the film. Here, we use epitaxial strain and orientation engineering in tandem-anisotropic epitaxy-to craft a low-symmetry phase of BiFeO3 that acts as a structural bridge between the rhombohedral-like and tetragonal-like polymorphs. Interferometric displacement sensor measurements reveal that this phase has an enhanced piezoelectric coefficient of x2.4 compared with typical rhombohedral-like BiFeO3. Band-excitation frequency response measurements and first-principles calculations provide evidence that this phase undergoes a transition to the tetragonal-like polymorph under electric field, generating an enhanced piezoelectric response throughout the film and associated field-induced reversible strains. These results offer a route to engineer thin-film piezoelectrics with improved functionalities, with broader perspectives for other functional oxides.

36 MATERIALS SCIENCE↗

Electric field dependence of nanoscale cathodoluminescence inside Cr doped β-Ga 2 O 3 interfaces

Chromium (Cr) is a common impurity in β-Ga 2 O 3 crystals, where its characteristic R1 and R2 luminescence lines are susceptible to both the host crystal field and externally applied fields. Here, in this work, we demonstrate that the Cr cathodoluminescence (CL) quenches toward the bulk of the crystal but enhances with applied reverse bias, reflecting the effect of free carrier depletion with increasing electric field. Furthermore, we illustrate that the R1/R2 CL intensity ratio, measured as the integrated area ratio of R1 to R2, can be used as a direct probe of the electric field in a Ni-β-Ga 2 O 3 : Cr Schottky diode. This optical calibration method provides a complementary approach to conventional C–V and I–V measurements for determining electric field strength in the depletion region of β-Ga 2 O 3 -based Schottky diodes and can be extended to other semiconductors and multilayer device structures.

36 MATERIALS SCIENCE↗

Single-crystalline orthorhombic GdAlGe as a rare-earth magnetic Dirac nodal-line metal

Crystal engineering is a method for discovering new quantum materials and phases, which may be achieved using external pressure or strain. Chemical pressure is unique in that it generates internal pressure perpetually to the lattice. As an example, GdAlSi from the rare-earth (𝑅) 𝑅⁢Al⁢𝑋 (𝑋=Si or Ge) family of Weyl semimetals is considered. Replacing Si with the larger isovalent element Ge creates sufficiently large chemical pressure to induce a structural transition from the tetragonal structure of GdAlSi, compatible with a Weyl semimetallic state, to an orthorhombic phase in GdAlGe, resulting in an inversion-symmetry-protected nodal-line metal. We find that GdAlGe hosts an antiferromagnetic ground state with two successive orderings, at 𝑇 N ⁢1=35K and 𝑇 N ⁢2=30K. In-plane isothermal magnetization shows a magnetic field induced metamagnetic transition at 6.2 T for 2 K. Furthermore, electron-hole compensation gives rise to a large magnetoresistance of ∼100% at 2 K and 14 T. Angle-resolved photoemission spectroscopy measurements and density functional theory calculations reveal a Dirac-like linear band dispersion over an exceptionally large energy range of ∼1.5eV with a high Fermi velocity of ∼10 6 m/s, a rare feature not observed in any magnetic topological materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Compositional heterogeneity in Cs y FA 1- y Pb(Br x I 1- x ) 3 perovskite films and its impact on phase behavior

Hybrid organic inorganic lead halide perovskite semiconductors of the form Cs y FA 1-y Pb(Br x I 1-x ) 3 are promising candidate materials for high-efficiency photovoltaics. Notably, cation and anion substitution can be used to tune the band gaps to optimize performance and improve stability. However, multi-component materials can be prone to compositional and structural inhomogeneity and the extent, length scale and impact of this heterogeneity on lead halide perovskite properties are not well understood. Here we use synchrotron X-ray diffraction to probe the evolution of crystal structure across the tetragonal-to-cubic phase transition for a series of Cs y FA 1-y Pb(Br x I 1-x ) 3 thin films with x = 0.05 to 0.3 and y = 0.17 to 0.40. We find that the transition occurs across a broad temperature range of approximately 40 °C, much larger than for pure compounds such as MAPbI 3 and MAPbBr 3 . Finally, we hypothesize that this smearing of the phase transition is due to compositional inhomogeneities that give rise to a distribution of local transition temperatures and we estimate the composition varies by about 10% to 15% with likely greater heterogeneity for the halide anion than the cation. This approach of mapping the transition is a simple and effective method of assessing heterogeneity, enabling evaluation of its impact.

36 MATERIALS SCIENCE↗

Bending effects and optical properties of WSe 2 nanoribbons of topological phase

A WSe 2 monolayer of 1T' phase is a large band gap quantum spin Hall insulator, supporting dissipationless charge and spin transports through the topologically protected edge states. Here, in this work, we explore the nanoribbon forms of 1T' phase WSe 2 by first-principles density functional calculations and the many-body perturbation GW and Bethe-Salpeter equation method. We found that the 1T' WSe 2 nanoribbon can show topological edge states with a ribbon width of ~4-6 nm. Those edge bands show crossing through the Fermi level an odd number of times, with one kind of spin-polarization connecting the valence band continuum and conduction band continuum. The topological features of the edge bands hold even under small and medium bending in the nanoribbon, while large bending induces large band splitting, resulting in a topological switch-off in the edge bands. The semiconducting 1T' WSe2 nanoribbon shows a large tunability with bending in optical absorption spectra and exciton states. The lowest-energy exciton is changed from optically dark in the flat nanoribbon to bright in the bent nanoribbons. These properties in the 1T' WSe 2 nanoribbons suggest potential applications in controllable quantum electronics and exciton-based quantum information processes.

36 MATERIALS SCIENCE↗