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At least 127 records · Page 7

The influence of iron incorporation on the microstructure and crystal chemistry of UO 2 fuel

The incorporation of dopants into UO 2 is of interest for both doped advanced fuel and nuclear forensics research. Suitable forensics dopants, or taggants, for nuclear fuels are ones that do not adversely affect the performance of the parent material while still being traceable during key stages of the fuel’s life cycle. In this paper, we present our efforts to understand the effects of doping UO 2 with Fe 2 O 3 under multiple parameters, such as Fe concentration (0–3000 wppm), sintering temperature (1673 K, 1773 K, and 1973 K), sintering time (2–12 h), and atmosphere (reducing and inert). Here, we investigated densification behavior, microstructure evolution, and lattice defects based on the geometric densities, scanning electron microscopy (SEM), X-ray diffractograms, and Raman spectra. The effect of Fe on the microstructure and crystal chemistry of UO 2 is very complex, especially at the intermediate temperature (1773 K), where we found that densification kinetics are enhanced and that lattice contraction occurs for doping concentrations greater than 1000 wppm Fe.

Crystallography↗

An Optothermal Raman Model Accounting for Convection, Radiation, and Substrate Effects for Evaluation of the Thermal Conductivity of Two‐Dimensional Coatings

Thermal conductivity of two‐dimensional (2D) materials is important to characterize as this will govern thermal transport physics in the various thermal and energy applications benefitting from the unique properties of these materials. Here, analytical and numerical techniques are presented to determine the thermal conductivity and interfacial conductance of a 2D material coating using confocal micro‐Raman spectroscopy as a noncontact diagnostic. While several methods have been proposed for calculating the values of thermal conductivity, interfacial conductance, and spatial temperature profile, these models often do not consider effects of radiation, convection, and substrate resistance on the temperature and heat flux profiles. We present a model to calculate the thermal conductivity and interfacial conductance which accounts for convection, radiation, and substrate effects to characterize a variety of 2D material coatings, which is demonstrated using large area graphene transferred onto copper and nickel substrates. Convection and radiation effects are found to have a negligible effect on the temperature profile of supported coatings, while the substrate effects have a considerable effect and therefore impact the quantification of thermal conductivity and interfacial conductance in addition to limiting the spatial resolution of the technique. These findings will allow for more accurate and reproducible extraction of the thermal conductivity of graphene and other 2D material coatings when employing noncontact optothermal Raman spectroscopy methods.

2D coatings↗

Raman spectroscopy of neutron irradiated silicon carbide

The effects of neutron irradiation on microstructural evolution and the resultant changes in physical and mechanical properties are of critical importance for the development of silicon carbide (SiC) materials for nuclear applications. This study neutron-irradiated βSiC under a wide range of conditions at temperatures between 235 and 750°C and neutron doses of 0.01–11.8 displacements per atom, and then evaluated the effects on the SiC structure using Raman spectroscopy. The SiC optical phonon lines were shifted to lower wavenumbers by irradiation. Correlations were found among the wavenumber of the longitudinal optical phonon line, irradiation-induced swelling, and irradiation temperature. The peak shift also correlated indirectly with decreasing thermal conductivity of irradiated SiC. The irradiation-induced peak shift is explained by combinations of lattice strain, reduction of the elastic modulus, and other factors including decreasing coherent domain size. These findings bridge irradiation-induced microstructural changes and property changes and illustrate how Raman spectroscopy is a useful tool for nondestructively assessing irradiated SiC materials for nuclear applications.

Koyanagi, T.↗

Raman Scattering of Light by Molecules of Methyl Orange Dye on the Surface of Silicon Containing Ion-Synthesized Silver Nanoparticles

The possibility of using a new composite material based on porous silicon containing silver nanoparticles and synthesized by means of a unique implantation nanotechnology as an optically sensitive material in biological and chemical sensors is tested experimentally. It is demonstrated that detection of small amounts of the studied organic substance (methyl orange dye) is possible due to the effect of surface-enhanced Raman scattering (SERS) from the molecules affected by the local electromagnetic field of the silver nanoparticles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Atomic Coherence of 2 Minutes and Instability of 1.5 × 10 −18 at 1 s in a Wannier-Stark Lattice Clock

We explore the limits of atomic coherence and measurement precision in a 87 Sr optical lattice clock. We perform a detailed characterization of key effects, including lattice Raman scattering and atomic collisions in a shallow lattice configuration, determining a 174(28) s 3 𝑃 0 clock state lifetime. Investigation of atomic coherence across a range of lattice depths and atomic densities reveals decoherence mechanisms related to photon scattering and atomic interaction. At a reduced density, we observe a coherence time of 118(9) s, approaching the fundamental limit set by spontaneous emission. Guided by this coherence understanding, we demonstrate a clock instability for an atomic ensemble of 1.5 × 10 −18 at 1 s in fractional frequency units. Our results are important for further advancing the state of the art of an optical lattice clock for fundamental physics applications.

atomic, optical, & lattice clocks↗

Laser Crystallization and Dopant Activation of a-Si:H Carrier-Selective Layer in TOPCon Si Solar Cells

Herein, we present a pulsed-laser processing method for crystallization and dopant activation of a highly n-doped amorphous silicon (a-Si:H) carrier-selective layer in a tunnel oxide passivated contact (TOPCon) Si solar cell structure. Here, the laser method provides enhanced conductivity and implied open circuit voltage while reducing emitter saturation current density and surface heating, as opposed to conventional high-temperature furnace annealing of the bulk Si wafer with a TOPCon structure. We identify an appropriate laser wavelength, fluence, and layer thickness using modeling and simulations. Raman and Hall effect measurements demonstrate increased crystallinity and dopant activation, whereas photoconductive decay shows enhanced surface and interface passivation quality. Additionally, we examine the role of subsequent SiNx deposition on further improving the passivation of laser-processed TOPCon layers to achieve a 5.9 kΩ/sq film sheet resistance, 2 ms effective carrier lifetime, 718 mV implied open-circuit voltage (iVOC), and 8.6 fA/cm 2 one-side recombination current density (J0) with the potential for further passivation improvement via laser process and a-Si layer thickness optimization.

14 SOLAR ENERGY↗

DFT study of Raman scattering spectra of complexes of spiropyrans with the silver cluster

The computational simulation of structure, energy and spectral characteristics of spiropyrans and their complexes with the cluster containing ten silver atoms was carried out using the density functional theory method (B3LYP/6-31G(d,p)/SDD). A competitive coordination of oxygen-containing substituents in the indoline and benzopyran moieties in spirocyclic molecules to the metal atoms was studied and an effect of position of donor groups on the activity of CO vibrational bands was established in the calculated Raman spectra. We revealed compounds, whose trans-trans-trans isomers upon a complexation with the silver cluster are characterized by the more than 100 times enhanced activity of band associated with the valence vibrations of CO bond in the Raman spectrum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Origin of Large Effective Phonon Magnetic Moments in Monolayer MoS 2

Recent helicity-resolved magneto-Raman spectroscopy measurement demonstrates large effective phonon magnetic moments of ~2.5 μ B in monolayer MoS 2 , highlighting resonant excitation of bright excitons as a feasible route to activate Γ-point circularly polarized phonons in transition metal dichalcogenides. However, a microscopic picture of this intriguing phenomenon remains lacking. In this work, we show that an orbital transition between the split conduction bands (Δ 0 = 4 meV) of MoS 2 couples to the doubly degenerate E" phonon mode (Ω 0 = 33 meV), forming two hybridized states. Our phononic and electronic Raman scattering measurements capture these two states: (i) one with predominantly phonon contribution in the helicity-switched channels and (ii) one with primarily orbital contribution in the helicity-conserved channels. An orbital-phonon coupling model successfully reproduces the large effective magnetic moments of the circularly polarized phonons and explains their thermodynamic properties. Strikingly, the Raman mode from the orbital transition is superimposed on a strong quasi-elastic scattering background, indicating the presence of spin fluctuations. As a result, the electrons excited to the conduction bands through the exciton exhibit paramagnetic behavior although MoS 2 is generally considered as a nonmagnetic material. By depositing nanometer-thickness nickel thin films on monolayer MoS 2 , we tune the electronic structure so that the A exciton perfectly overlaps with the 633 nm laser. The optimization of resonance excitation leads to pronounced tunability of the orbital-phonon hybridized states. Our results generalize the orbital-phonon coupling model of effective phonon magnetic moments to material systems beyond the paramagnets and magnets.

2D transition metal dichalcogenide↗

SERS Theory: The Chemical Effect of Rhodamine 6G Adsorption on Silver Surfaces on Its Raman Spectrum

The SERS spectra of small organic molecules can be very sensitive to the physisorption or chemisorption of the molecules onto metallic surfaces. However it is challenging to model the results, as typical SERS substrates have a broad distribution of possible surface sites, and the populations of these sites and the SERS enhancement factors associated with them are very difficult to determine, especially when electromagnetic hot spots dominate the observed spectra. However it is important to account for these effects if one is to make a quantitative interpretation of measured SERS spectra. Indeed, the influence of different sites is important to both the electromagnetic and chemical mechanisms in SERS, where the former mechanism is concerned with local field enhancement effects arising from plasmon excitation, while the latter arises from the effect of chemisorption induced charged transfer on the Raman intensities, as can be modeled using static limit Raman intensity calculations[1]. Extensive studies have been performed on simple organics like pyridine bound to gold and silver clusters, and it was found that both the chemical and electrodynamic enhancement factors associated with binding pyridine in various orientations result in noticeable changes in the SERS spectra compared to the gas phase spectrum of pyridine.[2] One of the most important benchmark molecules for SERS and TERS studies is Rhodamine 6G (R6G). This is a strongly fluorescent dye molecule in solution, but when adsorbed onto SERS substrates, its fluorescence is quenched, and the resulting SERS intensities are among the largest observed for any molecule. As a result R6G has played a crucial role in the development of single molecule SERS, and in the development of SERS substrates. [3, 4] Previously, the SERS spectrum of R6G has been modeled as if it were a gas phase molecule. Jensen and Schatz[5] incorporated resonant effects as well as vibronic effects and found that resonance excitation to the S1 excited state of R6G resulted in good agreement with spectra obtained from SERS experiments. In another study, intermolecular charge transfer was studied with R6G bound to a Ag2 cluster.[6] It is unclear if a cluster model as small as two silver atoms can accurately capture the surface effects of a nanoparticle with thousands of atoms. Recent single molecule, ultra high vacuum, tip enhanced Raman spectroscopy (SM-UHV-TERS) measurements for R6G[3] were moderately reproduced by gas phase resonance Raman calculations. Of particular importance in this work was the comparison of TERS spectra at room temperature with those at a low temperature of 10K. It was found that lowering the temperature led to both sharpening of the vibrational spectra, and shifts in the spectra (up to 20 cm-1 with some lines shifting red, some blue and some not at all), suggesting that the molecule transitions from a largely gas phase molecule at room temperature to being strongly chemisorbed at 10K. A potential energy distribution analysis performed by Chulhai and Jensen[3] showed that the modes that were shifted from the gas phase had vibrational activity associated with the ethylamine component of R6G, which is the likely moiety associated with Raman calculations. What remains unresolved concerning the SM-UHV-TERS studies of R6G is direct evidence that the chemical binding of R6G to a silver nanoparticle surfaces causes frequency shifts and/or intensity changes in the Raman scattering intensities of specific modes, especially those involving vibrations of the ethylamine moiety. The theoretical work described in this chapter directly addresses this issue by calculating Raman spectra for R6G interacting with a 20-atom silver cluster, and with a flat Ag(111) surface. Tetrahedral Ag20 is chosen for part of these studies as it provides a model nanoparticle structure that has a well-defined fragment of a (111) surface, as well as having edges and vertices that can be used to model coordinately unsaturated sites on a particle. In addition, Ag20 has been found to provide a reasonable reference structure for determining the chemical contribution to SERS enhancements.[1] Two different geometries of the Ag20/R6G system are considered in the present study, corresponding to two different binding configurations of R6G to a pristine Ag(111) surface. In addition, we study adsorption of R6G on a flat Ag(111) surface of using plane wave DFT calculations to determine optimized geometries and normal mode properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The Crystal Structure, Raman Spectra, and Magnetic Properties of HoCrO{sub 3} Annealed in Different Atmospheres

The crystal structure, phonon Raman scattering, and magnetic properties of HoCrO{sub 3} were studied in a way of impacting the oxygen site by annealing treatment in argon and oxygen atmospheres. Although there are no dramatic changes in magnetic properties, a negative magnetization phenomenon below T{sub N} was observed in all prepared HoCrO{sub 3} samples and a certain of lattice distortion was affected due to the variation of Ho–O bond length and Cr–O–Cr bond angle and bond lengths. The Raman spectra exhibit an obvious shift of mode-related Ho ion instead of modes involved with Cr, which unconsciously leads to the variation of effective paramagnetic moments. The magnetic properties were systematically analyzed by Curie-Weiss and modified Curie-Weiss laws. The effective magnetic moment and symmetric and antisymmetric exchange interactions of J{sub e} and D were discussed. The reduced effective magnetic moments in HoCrO{sub 3} and annealed ones demonstrate possible vacancies of Ho and Cr, which was verified by elemental composition tested by energy-dispersive X-ray spectroscopy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Forward and backward stimulated Raman scattering in multi-speckled beams: Density dependence and effects on cross-beam energy transfer

Particle-in-cell simulations of cross-beam energy transfer (CBET) between multi-speckled beams reveal a potentially prominent energy loss from forward stimulated Raman scattering (FSRS) in the amplified seed beam [Yin et al., Phys. Plasmas 26, 082708 (2019)]. In this work, an intensity scan is used to examine this energy loss in the CBET-amplified seed beam at intensities of a few times 1014 W/cm2. Electron tracers demonstrate both the trapping in the electron plasma waves that is sustained over multiple speckles and the subsequent acceleration to velocities well beyond the phase velocity. Motivated by expanding our understanding of this energy loss mechanism, we isolate the FSRS density dependence by using a 2×1014 W/cm2 pulse to scan densities between 0.06 ncr and 0.12 ncr; a spectral analysis characterizes the energy losses from scattering with the changing densities. At saturation, both greater beam attenuation is measured at the laser frequency and larger scattering FSRS angles are observed as density increases, along with a rapid transition to primarily backscatter SRS between 0.10 ncr and 0.12 ncr, earlier than predicted by linear theory. Density gradients are shown to effectively mitigate oblique FSRS and beam energy losses in the two lower density cases, whereas 0° forward scattering is primarily suppressed in the higher density cases. Finally returning to the two-beam CBET system of interest, the interplay and mitigation of the secondary instabilities at larger domain and beam spatial scales are discussed, here also examining backward stimulated Brillouin scattering.

Stark, D. J. (ORCID:0000000203642733)↗

Ion-Beam Synthesis of the Crystalline Ge Phase in SiO{sub x}N{sub y} Films upon Annealing under High Pressure

The nucleation of the crystalline Ge phase in SiO{sub x}N{sub y} films implanted with Ge{sup +} ions with the energy 55 keV to doses of 2.1 × 10{sup 15}–1.7 × 10{sup 16} cm{sup –2} and then annealed at a temperature of T{sub a} = 800–1300°C under pressures of 1 bar and 1–12 kbar is studied. From analysis of the Raman spectra, it is concluded that amorphous Ge precipitates increase in size upon hydrostatic compression at a temperature of 1000°C. Raman scattering at optical phonons localized in Ge nanocrystals is observed only after annealing of the samples with the highest content of implanted atoms at a temperature of 1300°C. In the photoluminescence spectra, a peak is observed at the wavelength ∼730 nm. The peak is considered to be the manifestation of the quantum-confinement effect in nanocrystals ∼3 nm in size.

36 MATERIALS SCIENCE↗

Ab-initio simulations of coherent phonon-induced pumping of carriers in zirconium pentatelluride

Abstract Laser-driven coherent phonons can act as modulated strain fields and modify the adiabatic ground state topology of quantum materials. Here we use time-dependent first-principles and effective model calculations to simulate the effect of the coherent phonon induced by strong terahertz electric field on electronic carriers in the topological insulator ZrTe 5 . We show that a coherent A 1g Raman mode modulation can effectively pump carriers across the band gap, even though the phonon energy is about an order of magnitude smaller than the equilibrium band gap. We reveal the microscopic mechanism of this effect which occurs via Landau–Zener-Stückelberg tunneling of Bloch electrons in a narrow region in the Brillouin zone center where the transient energy gap closes when the system switches from strong to weak topological insulator. The quantum dynamics simulation results are in excellent agreement with recent pump-probe experiments in ZrTe 5 at low temperature.

36 MATERIALS SCIENCE↗

Pressure-induced polymorphism and piezochromism in Mn 2 FeSbO 6

In the last decade, major efforts have been devoted to searching for polar magnets due to their vast potential applications in spintronic devices. However, the polar magnets are rare because of conflicting electronic configuration requirements of ferromagnetism and electric polarization. Double-perovskite oxides with a polar structure containing transition metal elements represent excellent candidates for the polar magnet design. In this work, the crystal structure evolution of Mn 2 FeSbO 6 (MFSO) was investigated at pressures reaching ~50 GPa by in situ synchrotron X-ray diffraction (XRD), Raman scattering, and ab initio calculation techniques. The XRD results reveal ilmenite- to perovskite-type phase transition at around 35 GPa. An additional intermediate phase, observed in the range of 31–36 GPa by Raman spectroscopy, but not the XRD technique, is proposed to represent the polar LiNbO 3 phase. It is argued that this phase emerged due to the heating effect of the Raman-excitation laser. The LiNbO 3 -type MFSO compounds, displaying an intrinsic dipole ordering, represent a promising candidate for multiferroic materials. The detected phase transitions were found to be reversible although a significant hysteresis was noticeable between compression and decompression runs. Moreover, a pressure-induced piezochromism, signifying a bandgap change, was discovered by the direct visual observations and corroborated by ab initio calculations. The present study benefits an efficient high-pressure synthesis of polar magnetic double-perovskite oxides in the future.

36 MATERIALS SCIENCE↗

Simple Hydrothermal Synthesis for Mesoporous Pebble-Like NiCo{sub 2}O{sub 4} Nanostructures and Their Attractive Magnetic Properties

The mesoporous pebble-like NiCo{sub 2}O{sub 4} nanostructures were smoothly obtained via a simple hydrothermal route and the succeeding annealing treatment. Various techniques, including XRD, SEM, TEM, Raman spectra, FTIR, and MH curves have been used to study the obtained products. The obtained results exhibited that the morphology of spinel NiCo{sub 2}O{sub 4} could be controlled by adjusting the content of cetyltrimethylammonium bromide (CTAB). The morphology of NiCo{sub 2}O{sub 4} nanostructures transformed from a 300-nm popcorn-like to 30–40-nm pebble-like nanostructure by changing the content of CTAB. Compared with the popcorn-like NiCo{sub 2}O{sub 4} nanostructures, the pebble-like samples showed effective blue shifting of Raman spectroscopy, which might be due to the nano-sized effect of NiCo{sub 2}O{sub 4} particles. Finally, vibration sample magnetometer (VSM) measurements indicated the samples transformed from weak ferromagnetic (popcorn-like) to paramagnetic (pebble-like) due to small particle size.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Raman Scattering in InSb Spherical Nanocrystals Ion-Synthesized in Silicon-Oxide Films

The Raman spectra of SiO{sub 2} films containing InSb spherical nanocrystals produced by ion-beam synthesis are studied. TO- and LO-like modes in the spectra of the InSb nanocrystals are detected at frequencies of 187 and 195 cm{sup –1}, respectively. The shift of these modes to high frequencies with respect to the corresponding frequencies in InSb bulk crystals is analyzed from the viewpoint of the influence of the quantum-confinement effect, strains in nanocrystals, the surface phonon frequency, and scattering at the frequency corresponding to stretched anion–cation modes at the surface of polar spherical nanocrystals. The position of the 195-cm{sup –1} mode corresponds to LO phonons in InSb nanocrystals hydrostatically compressed in the SiO{sub 2} matrix at pressures of about 10 kbar. The 187-cm{sup –1} mode corresponds to resonance at the Fröhlich frequency.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Growth and characterization of Cu3SbSe4 thin films through thermally diffusing Sb2Se3 – CuSe by chemical bath deposition (CBD)

Highlights: • Cu{sub 3}SbSe{sub 4} films were formed by chemical bath deposition followed by a heat treatment. • Prepared Cu{sub 3}SbSe{sub 4} thin films have promising properties to absorbing layer in a solar cell or thermoelectric material. • Electrical conductivity values of Cu{sub 3}SbSe{sub 4} are high, considering its manufacturing method and the previous reports in the field. - Abstract: In the present work, Cu{sub 3}SbSe{sub 4} thin films have been successfully synthesized by chemical bath deposition (CBD) involving a sequential deposition of antimony selenide (Sb{sub 2}Se{sub 3}) and copper selenide (CuSe) films and then annealing in a vacuum atmosphere. The influence of CuSe deposition time on the previously deposited Sb{sub 2}Se{sub 3} films was investigated to obtain the ternary phase. A study of the structural, morphological, optical and electrical properties of these films was carried out using appropriate characterization techniques. X-ray diffraction analysis revealed that the films show a tetragonal crystalline crystalline structure corresponding to the Permingeatite phase (Cu{sub 3}SbSe{sub 4}). The crystal size increases with the CuSe deposition time. It is identified by Raman spectroscopy that at low CuSe deposition times a low concentration of Sb{sub 2}Se{sub 3} coexists in the thin film. The optical band gap energy of these films was evaluated in the range of 0.67–1.18 eV, decreasing by increasing CuSe deposition time. By field-emission scanning electron microscopy (FESEM) a morphological study was carried out, observing that by increasing the deposition time of CuSe there is an increase of agglomerates and decrease the porosity in the samples. An elemental analysis was carried out by energy dispersive X-ray spectroscopy to observe the composition and elemental distribution in the ternary compound. The films showed a p-type electrical conductivity with values between 0.417 and 55.55 (Ω cm{sup −1}). The mobility and carrier density were performed by Hall Effect and Thermoelectric measurements observing a slight increase in the values by increasing the time of CuSe deposition. All results obtained for thin films of Cu{sub 3}SbSe{sub 4} suggest that it could be used as an absorber material in a solar cell or thermoelectric material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE ASR Final Report on “Use of ARM Observations to Investigate the Role of Tropical Radiative Processes and Cloud Radiative Effects in Climate Simulations”

The overall objective of this ASR funded project is to investigate the role of cloud radiative effects, especially those associated with tropical thin cirrus clouds in the tropical tropopause layer, by analyzing the ARM observations combined with numerical models. In particular, we have processed and analyzed the observations from the Raman lidar at the ARM SGP and TWP sites. In the tenure of the project (8/15/2013 – 8/14/2016 and with a no-cost extension to 8/14/2017), we have been concentrating on (i) developing an automated feature detection scheme of clouds and aerosols for the ARM Raman lidar; (ii) developing an automated retrieval of cloud and aerosol extinctions for the ARM Raman lidar; (iii) investigating cloud radiative effects based on the observations on the simulated temperatures in the tropical tropopause layer using a radiative-convective model; and (iv) examining the effect of changes of atmospheric composition on the tropical lower-stratospheric temperatures. In addition, we have examined the biases in the CALIPSO-inferred aerosol direct radiative effects using ground-based Raman lidars at the ARM SGP and TWP sites, and estimated the impact of lidar detection sensitivity on assessing global aerosol direct radiative effects. We have also investigated the diurnal cycle of clouds and precipitation at the ARM site using the cloud radar observations along with simulations from the multiscale modeling framework. The main results of our research efforts are reported in the six referred journal publications that acknowledge the DOE Grant DE-SC0010557.

47 OTHER INSTRUMENTATION↗