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At least 307 records · Page 17

Synthesis of 2D layered transition metal (Ni, Co) hydroxides via edge-on condensation

Abstract Layered transition metal hydroxides (LTMHs) with transition metal centers sandwiched between layers of coordinating hydroxide anions have attracted considerable interest for their potential in developing clean energy sources and storage technologies. However, two-dimensional (2D) LTMHs remain largely understudied in terms of physical properties and applications in electronic devices. Here, for the first time we report > 20 μm α-Ni(OH) 2 2D crystals, synthesized from hydrothermal reaction. And an edge-on condensation mechanism assisted with the crystal field geometry is proposed to understand the 2D intra-planar growth of the crystals, which is also testified through series of systematic comparative studies. We also report the successful synthesis of 2D Co(OH) 2 crystals (> 40 μm) with more irregular shape due to the slightly distorted octahedral geometry of the crystal field. Moreover, the detailed structural characterization of synthesized α-Ni(OH) 2 are performed. The optical band gap energy is extrapolated as 2.54 eV from optical absorption measurements and the electronic bandgap is measured as 2.52 eV from reflected electrons energy loss spectroscopy (REELS). We further demonstrate its potential as a wide bandgap (WBG) semiconductor for high voltage operation in 2D electronics with a high breakdown strength, 4.77 MV/cm with 4.9 nm thickness. The successful realization of the 2D LTMHs opens the door for future exploration of more fundamental physical properties and device applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plasma decay of nanosecond pulsed laser-produced Ar and Ar–H 2 O sparks at atmospheric pressure

Time-resolved diagnostics were applied to investigate free-electron properties in nanosecond laser-produced discharges generated in atmospheric pressure Ar and in Ar–3%H 2 O. The discharges were generated using 23 ns, 1064 nm laser pulses. Broadband plasma imaging and laser Thomson scattering were combined with optical emission spectroscopy, with particular emphasis on the Stark broadening of the H α and H β lines. The plasma exhibited a bright emission that persists for up to 30–40 µs after breakdown. Plasma emission was then followed by a very weak glow emission that persisted for up to 19 ms after breakdown. Peak electron number density of ∼2 × 10 17 cm −3 and electron temperature of ∼7 eV were measured. An excellent agreement between both techniques was obtained regarding absolute electron number densities. The inferred free-electron temporal decay dynamics are consistent with processes dominated by hydrodynamic expansion and two- and three-body electron–ion recombination. These results provide benchmark data for modeling nanosecond laser discharges and demonstrate the reliability of combining Thomson scattering with Stark broadening in atmospheric laser sparks.

Thomson scattering↗

Prediction of Solution Behavior via Calorimetric Measurements Allows for Detailed Elucidation of Polyoxometalate Transformation

The solution behavior of a polyoxometalate cluster, LiNa-U 24 Pp 12 (Li 24 Na 24 [(UO 2 O 2 ) 24 (P 2 O 7 ) 12 ]) that consists of 24 uranyl ions, peroxide groups, and 12 pyrophosphate linkers, was successfully predicted based on new thermodynamic results using a calorimetric method recently described for uranyl peroxide nanoclusters (UPCs), molybdenum blues, and molybdenum browns. The breakdown of LiNa-U 24 Pp 12 and formation of U 24 (Li 24 [UO 2 O 2 OH] 24 ) was monitored in situ via Raman spectroscopy using a custom heating apparatus. A combination of analytical techniques confirmed the simultaneous existence of U 24 Pp 12 and U 24 midway through the conversion process and U 24 as the single end product. The application of a molecular weight filter resulted in a complete and successful separation of UPCs from solution and, in conjunction with DOSY results, confirmed the presence of large intermediate cluster building blocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vertical β -Ga2O3 metal–insulator–semiconductor diodes with an ultrathin boron nitride interlayer

In this work, we demonstrate the high performance of β-Ga2O3 metal–insulator–semiconductor (MIS) diodes. An ultrathin boron nitride (BN) interlayer is directly grown on the Ga2O3 substrate by pulsed laser deposition. X-ray photoelectron spectroscopy, Raman spectroscopy, and high-resolution transmission electron microscopy confirm the existence of a 2.8 nm BN interlayer. Remarkably, with the insertion of the ultrathin BN layer, the breakdown voltage is improved from 732 V for Ga2O3 Schottky barrier diodes to 1035 V for Ga2O3 MIS diodes owing to the passivated surface-related defects and reduced reverse leakage currents. Our approach shows a promising way to improve the breakdown performance of Ga2O3-based devices for next-generation high-power electronics.

Physics↗

Nuclear Science Symposium, 30th, and Symposium on Nuclear Power Systems, 15th, San Francisco, CA, October 19-21, 1983, Proceedings

The range of disciplines covered includes physics instrumentation, data acquisition, FASTBUS, radiation detectors, scintillators, photomultipliers and optical detectors, subnanosecond 2-D imaging, medical and health instrumentation, reactor instrumentation, and space instrumentation. Cerenkov detectors, the prevention and rate capability of breakdown processes in wire chambers, and an interactive parallel processor for data analysis are studied. Attention is also given to bismuth germanate's role in gamma-ray spectroscopy, and the construction of a broadband universal sampling head is described. Gamma-ray imaging with a rotating hexagonal uniform redundant array, and broadband X-ray astronomical spectrometry are considered.

Nakamura, M.↗

Variation of the urban NO2 concentration during a ground inversion situation

In February 1985 the NO2 concentration over Goeteborg, a major Swedish city, was monitored during two inversion situations. The differential absorption technique was employed and the results show the build-up of the concentration. In this experiment the laser beam was scanned horizontally over Goeteborg. The results were presented as maps over the NO2 concentration distribution. For security reasons the beam was not parallel to the ground, which gives a height gradient in some measurements. During the measurement period the NO2 concentration variation build-up from the morning to the afternoon was monitored. Great concentration variations were seen. Later the mixing below the inversion layer, resulting in a more uniform, high concentration was seen. The breakdown of the inversion when stronger winds start was also seen. Comparisons with a traditional point-measuring chemiluminiscence instrument and an optical method DOAS (Differential Optical Absorption Spectroscopy), were made. The results are discussed. Strong spatial concentration variations are shown by the lidar measurements. For a point-measuring system, the instrument must be very carefully placed since its location will strongly influence the values it gives.

Sunesson, A.↗

Microscopic Origins of the Nonlinear Behavior of Particle-Filled Rubber Probed with Dynamic Strain XPCS

The underlying microscopic response of filler networks in reinforced rubber to dynamic strain is not well understood due to the experimental difficulty of directly measuring filler network behavior in samples undergoing dynamic strain. This difficulty can be overcome with in situ X-ray photon correlation spectroscopy (XPCS) measurements. The contrast between the silica filler and the rubber matrix for X-ray scattering allows us to isolate the filler network behavior from the overall response of the rubber. This in situ XPCS technique probes the microscopic breakdown and reforming of the filler network structure, which are responsible for the nonlinear dependence of modulus on strain, known in the rubber science community as the Payne effect. These microscopic changes in the filler network structure have consequences for the macroscopic material performance, especially for the fuel efficiency of tire tread compounds. In this work, we elucidate the behavior with in situ dynamic strain XPCS experiments on industrially relevant, vulcanized rubbers filled (13 vol %) with novel air-milled silica of ultrahigh-surface area (UHSA) (250 m 2 /g). The addition of a silane coupling agent to rubber containing this silica causes an unexpected and counterintuitive increase in the Payne effect and decrease in energy dissipation. For this rubber, we observe a nearly two-fold enhancement of the storage modulus and virtually equivalent loss tangent compared to a rubber containing a coupling agent and conventional silica. Interpretation of our in situ XPCS results simultaneously with interpretation of traditional dynamic mechanical analysis (DMA) strain sweep experiments reveals that the debonding or yielding of bridged bound rubber layers is key to understanding the behavior of rubber formulations containing the silane coupling agent and high-surface area silica. These results demonstrate that the combination of XPCS and DMA is a powerful method for unraveling the microscale filler response to strain which dictates the dynamic mechanical properties of reinforced soft matter composites. With this combination of techniques, we have elucidated the great promise of UHSA silica when used in concert with a silane coupling agent in filled rubber. Such composites simultaneously exhibit large moduli and low hysteresis under dynamic strain.

36 MATERIALS SCIENCE↗

Wear in particle based CSP systems from particle abrasion and attrition at high temperature

High temperature particle-based receivers offer distinct advantages over conventional molten salt receivers due to their ability to achieve temperatures above 700 ºC, direct absorption of solar energy as they fall through a beam of concentrated sunlight, and the relative ease of storage (and retrieval using a secondary working fluid) in insulated storage tanks. The use of particles, however, also raises concerns with material degradation from the flow of hot or cold particles through discharge hoppers or along the inner receiver surfaces and other system components (e.g. tubes, valves etc.), depending on operating mode of the receiver. The flow of particles over surfaces may result in loss of material from abrasive wear, impact erosion from impingement under gravitational fall and particle attrition as particles fall and move on top of each other. In the present study, the performance of candidate materials and particles were evaluated through a series of abrasion erosion and particle attrition experiments at room temperature as well as at 800 °C. Candidate materials were subject to abrasive wear from particles at low particle to material velocities inside a resistance heated kiln, and analyzed for changes in mass and surface morphology using cross-sectional scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS) tests. The wear rate for different specimens was noted to be largely driven by the strength of chromia scales built on the specimens from exposure to high temperature. Particle attrition measurements explored the susceptibility of particles to breakdown from particle to particle interaction and the generation of fines from this process. At the low velocities expected in particle based CSP plants, the particles tested exhibited near negligible breakdown. However, changes in the particle hardness at 800 ºC resulted in a significantly higher particle breakdown to sizes <40 microns raising potential environmental concerns. In addition to particle breakdown, it was also noted that the sample had oxides from the stainless steel test setup mixed in with the particles. Similar oxides can be expected to turn up in the utility scale particle based CSP plants as well. The presence of oxide was also noted to affect the solar absorptivity of the mixture compared to a clean initial specimen, potentially resulting in a change in the overall efficiency of the CSP plant.

14 SOLAR ENERGY↗

Properties and device performance of BN thin films grown on GaN by pulsed laser deposition

Wide and ultrawide-bandgap semiconductors lie at the heart of next-generation high-power, high-frequency electronics. Here, in this paper, we report the growth of ultrawide-bandgap boron nitride (BN) thin films on wide-bandgap gallium nitride (GaN) by pulsed laser deposition. Comprehensive spectroscopic (core level and valence band x-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and Raman) and microscopic (atomic force microscopy and scanning transmission electron microscopy) characterizations confirm the growth of BN thin films on GaN. Optically, we observed that the BN/GaN heterostructure is second-harmonic generation active. Moreover, we fabricated the BN/GaN heterostructure-based Schottky diode that demonstrates rectifying characteristics, lower turn-on voltage, and an improved breakdown capability (~234 V) as compared to GaN (~168 V), owing to the higher breakdown electrical field of BN. Our approach is an early step toward bridging the gap between wide and ultrawide-bandgap materials for potential optoelectronics as well as next-generation high-power electronics.

42 ENGINEERING↗

Position-Specific Carbon Isotope Fingerprinting of Fluorinated Organics and Degradation Products

Fluorinated organic compounds are of growing environmental and forensic relevance due to their widespread use in pharmaceuticals, agrochemicals, and consumer products, their environmental persistence, and potential ecological and human health impacts. Elucidating their sources and transformation pathways is therefore a major focus of current research. Stable carbon isotope analysis provides a powerful approach for tracing molecular origins and linking parent compounds to degradation products. Recent isotope measurements have largely relied on mass-spectrometry techniques, which provide only an average isotope ratio across a compound. In this work, we employ a novel nuclear magnetic resonance (NMR) spectroscopy tool to determine position-specific carbon isotope ratios ( 13 C/ 12 C) in organofluorine compounds and their degradation products. This approach enables isotope measurements without combustion or extensive purification and, crucially, resolves ratios at individual carbon positions rather than bulk averages. The resulting intramolecular isotope fingerprints are unique to a molecule’s source. Applied to selected pharmaceuticals and pesticides, these fingerprints allow discrimination of chemically identical compounds. Moreover, we show that the 13 C/ 12 C signature at the fluorinated carbon persists through degradation, demonstrated for lansoprazole and fipronil. The 19 F NMR data produced for the 13 C/ 12 C analyses are also well suited for impurity profiling, providing an additional dimension for fingerprinting fluorinated organics. These findings suggest that position-specific isotope analysis can serve as part of a broader suite of tools for source characterization of organofluorine compounds and their breakdown derivatives, with potential applications in product validation, forensics, and linking these compounds to their breakdown products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-shot ultrafast dynamics of nanosecond pulsed plasmas: Transition from ps–ns nonequilibrium to near-full ionization

The ultrafast multi-stage evolution of state-defining properties in atmospheric-pressure nanosecond pulsed plasmas is quantified using single-discharge, jitter-free, continuous streak-sweep spectroscopy of N 2 (C → B) molecular and N + /O + ionic species with a single-shot time resolution as short as ∼160 ps. An early period of extreme nonequilibrium is observed with vibrational temperatures [T V (C)] dropping from ∼8000 K at <200 ps after plasma breakdown to <4000 K within ∼1 ns, with near-ambient rotational temperatures [T R (C)] ∼ 300 K due to limited collisional energy transfer. This early-time T V (C) trend is representative of a direct and unquenched look into the high-energy tail of the electron energy distribution function; thus, it tracks real-time changes in the mean electron energy via the N2(C) emission signatures. This is followed by the rapid onset of N + /O + ionic emission after a distinct time delay of ∼14.9 ns due to multistep chemical kinetics. The ionic emission enables determination of electron densities (n e ) >2 × 10 19 cm −3 and electron temperatures (T e ) >36 000 K, indicating the transition to a nearly fully ionized regime. The ps–ns temporal dynamics are also compared between air and N 2 plasmas to assess the influence of collisional partners, as well as across the anode, cathode, and central gap regions to identify spatial variations in plasma behavior. Finally, this work demonstrates versatile continuously probing approach capable of spectro-temporal and spatially resolved single-shot measurements of key state variables in the ps–ns evolution of atmospheric-pressure nanosecond pulsed plasmas.

Electric discharges↗

Core hole processes in x-ray absorption and photoemission by resonant Auger-electron spectroscopy and first-principles theory

Electron–core hole interactions are critical for proper interpretation of core-level spectroscopies commonly used as analytical tools in materials science. Here we utilize resonant Auger-electron spectroscopy to uniquely identify exciton, shake, and charge-transfer processes that result from the sudden creation of the core hole in both x-ray-absorption and photoemission spectra. These effects are captured for the transition-metal compounds SrTiO 3 and MoS 2 by fully ab initio, combined real-time cumulant, and Bethe-Salpeter equation approaches to account for core hole dynamics and screening. Atomic charges and excited-state electron-density fluctuations reflect materials’ solid-state electronic structure, loss of translational symmetry around the core hole, and breakdown of the sudden approximation. They also demonstrate competition between long- and short-range screening in a solid.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effective Selective Area Doping for GaN Vertical Power Transistors Enabled by Innovative Materials Engineering

GaN vertical power transistors have emerged as promising candidates for future high efficiency high power electronic applications, with the potential to outperform conventional GaN lateral power devices in terms of power, breakdown, and avalanche characteristics. However, the development of current GaN vertical power transistors is seriously hindered by the poor materials performance of selective area doped p-n junctions. A mechanistic understanding of these fundamental materials issues is essential in order to achieve high performance selective area doped p-n junctions and consequently to advance the GaN vertical power transistor technology. To address this challenge, we carried out a comprehensive research program that advance fundamental knowledge in the selective area doping for GaN materials, and which will lead to the development of high performance GaN vertical power transistors. First, we developed innovative fabrication processes, including novel surface etching, surface passivation, and metalorganic chemical vapor deposition (MOCVD) growth, which provided enhanced opportunities for solving the unique challenges of selective area doping in GaN materials. Second, we performed a fundamental materials study using powerful characterization methods including transmission electron microscopy (TEM), ultraviolet (UV-), x-ray and angle-resolved photoelectron spectroscopy (UPS/XPS/ARPES), electron holography, and cathodoluminescence (CL); Third, we investigated several related issues, including Mg incorporation, polarization effects in carrier transport, and non-ideal material effects, which have rarely been explored so far. At the end of this project, we successfully demonstrated (1) fundamental understanding of selective area etching, regrowth, and doping of GaN, and associated knowledge on defects, interface, and breakdown properties. (2) Effective etch and regrowth processing recipes to achieve etch/regrowth GaN p-n diodes with very low leakage of 3.5 nA at 600 V, which meets the ARPA-E target. (2) High performance vertical GaN p-n didoes and vertical junction termination extension (JTE) devices with breakdown voltage of ~ 2 kV, and breakdown electric field of ~ 3.5 MV/cm, which are close to the performance limit of GaN. The successful outcome has resulted in new fundamental understandings in the selective area doping and regrowth process for GaN, which will lead to groundbreaking GaN vertical transistors for high performance next generation power electronics.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Experimental study of high-energy single-pulse nanosecond discharges in pin-to-pin configuration

Single-pulse pin-to-pin nanosecond pulsed discharges in ambient air (gap distances of 3–7 mm) were investigated at high pulse energies (∼20–30 mJ deposited energy per 11 ns full width at half maximum pulse). A Michelson interferometry setup (532 nm continuous-wave laser) was employed to record time-resolved interferograms of the discharge, enabling spatially resolved calculation of the electron number density. An intensified charge-coupled device camera was used to capture the spatiotemporal evolution of the discharge (streamer formation and spark channel development), and Coherent Anti-Stokes Raman Spectroscopy (CARS) was used to measure post-discharge N 2 vibrational temperatures. Discharge current and voltage were monitored with a back-current shunt. The discharge was initiated with simultaneous cathode-directed and anode-directed streamers that bridge the gap within ∼1 ns and form a luminous, filamentary plasma channel immediately after breakdown. Laser interferometry measurements showed peak electron number densities of the order of 10 1 7–10 18 cm −3 , occurring about 15–20 ns after pulse arrival at the discharge gap. Shorter gap discharges yielded higher peak electron densities, consistent with the higher energy density in the smaller gaps. Spatially, the electron density was highest near the electrodes and decreased toward the midgap region, with 5 and 7 mm gaps exhibiting a pronounced drop in the central channel. CARS indicated initial vibrational temperatures of approximately 4000–6000 K in the spark core of ∼50 ns after the discharge onset, decaying on a ∼500 ns timescale as the plasma cooled and recombined.

Coherent anti-Stokes Raman spectroscopy↗

Detection limits for laser absorption spectroscopy of Li in laser ablation plumes

A high-sensitivity laser absorption spectroscopy (LAS) method is demonstrated for rapid and non-contact analysis of Li in solids. Glass samples with Li concentrations ranging from 1-500 ppm by mass are ablated in 5 Torr air, and time-resolved Li atomic absorption is measured using a tunable laser near 671 nm. Significant improvements in analytical performance over prior laser-induced breakdown techniques are demonstrated. Here, a single-shot limit of detection (LOD) of 180 ppb is shown for fixed wavelength operation, improving to 6 ppb with averaging over 1000 ablation shots (100 s acquisition time). Isotope-resolved Li absorption spectra are measured with a 17 ppb LOD in 40 s. Methods for optimizing LOD based on noise/averaging properties of LAS experiments in LA plumes are discussed.

(020.3260) Isotope shifts↗

Magnetic Breakdown and Topology in the Kagome Superconductor CsV 3 Sb 5 under High Magnetic Field

The recently discovered layered kagome metals of composition AV 3 Sb 5 (A = K, Rb, Cs) exhibit a complex interplay among superconductivity, charge density wave order, topologically nontrivial electronic band structure and geometrical frustration. Here, we probe the electronic band structure underlying these exotic correlated electronic states in CsV 3 Sb 5 with quantum oscillation measurements in pulsed fields up to 86 T. The high-field data reveal a sequence of magnetic breakdown orbits that allows the construction of a model for the folded Fermi surface of CsV 3 Sb 5 . The dominant features are large triangular Fermi surface sheets that cover almost half the folded Brillouin zone. These sheets have not yet been detected in angle resolved photoemission spectroscopy and display pronounced nesting. In conclusion, the Berry phases of the electron orbits have been deduced from Landau level fan diagrams near the quantum limit without the need for extrapolations, thereby unambiguously establishing the nontrivial topological character of several electron bands in this kagome lattice superconductor.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Role of Metal Selection in the Radiation Stability of Isostructural M-UiO-66 Metal–Organic Frameworks

Robust and versatile metal–organic frameworks (MOFs) have emerged as sophisticated scaffolds to meet the critical needs of the nuclear community, but their performance depends on their underexplored structural integrities in high- radiation fields. The contributions of selected metal nodes in the radiation stability of MOFs within the isostructural M-UiO-66 series (where M = Zr, Ce, Hf, Th, and Pu; Zr-UiO-66 experiments were executed in a previous work) have been determined. Ce-, Hf-, and Th-UiO-66 MOF samples were irradiated via gamma and He-ion methodologies to obtain doses up to 3 MGy and 85 MGy, respectively, the latter strikingly higher than that obtained in most other studies. Appreciable self-irradiation constituted the total absorbed doses, up to 31 MGy of the gamma-irradiated Pu-UiO-66 samples. Structural degradation was ascertained by powder X-ray diffraction, X-ray total scattering, vibrational spectroscopy, and, where possible, N 2 physisorption isotherms. Diffuse reflectance infrared Fourier transform spectroscopy provided atomic-level mechanistic insights to reveal that the node-linker connection was most susceptible to radiation damage. Density functional theory calculations were performed on cluster models to evaluate the binding energy of the linkers to each metal node. Here, while the isostructures disclosed the same breakdown signatures, distinct radiation sensitivity as a function of metal selection was evident and followed the trend Hf-UiO-66 ~ Zr-UiO-66 > Th-UiO-66 > Pu-UiO-66 > Ce-UiO-66. We anticipate that these endeavors will contribute to the rational design of radiation-resistant materials for targeted applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗