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At least 91 records · Page 5

On the importance of excited state species in low pressure capacitively coupled plasma argon discharges

In the past three decades, first principles-based fully kinetic particle-in-cell Monte Carlo collision (PIC/MCC) simulations have been proven to be an important tool for the understanding of the physics of low pressure capacitive discharges. However, there is a long-standing issue that the plasma density determined by PIC/MCC simulations shows quantitative deviations from experimental measurements, even in argon discharges, indicating that certain physics may be missing in previous modeling of the low pressure radio frequency (rf) driven capacitive discharges. In this work, we report that the energetic electron-induced secondary electron emission (SEE) and excited state atoms play an important role in low pressure rf capacitive argon plasma discharges. The ion-induced secondary electrons are accelerated by the high sheath field to strike the opposite electrode and produce a considerable number of secondary electrons that lead to additional ionizing impacts and further increase of the plasma density. Importantly, the presence of excited state species even further enhances the plasma density via excited state neutral and resonant state photon-induced SEE on the electrode surface. The PIC/MCC simulation results show good agreement with the recent experimental measurements in the low pressure range (1–10 Pa) that is commonly used for etching in the semiconductor industry. At the highest pressure (20 Pa) and driving voltage amplitudes 250 and 350 V explored here, the plasma densities from PIC/MCC simulations considering excited state neutrals and resonant photon-induced SEE are quantitatively higher than observed in the experiments, requiring further investigation on high pressure discharges.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Simple hydrogenic estimates for the exchange and correlation energies of atoms and atomic ions, with implications for density functional theory

Exact density functionals for the exchange and correlation energies are approximated in practical calculations for the ground-state electronic structure of a many-electron system. An important exact constraint for the construction of approximations is to recover the correct non-relativistic large-Z expansions for the corresponding energies of neutral atoms with atomic number Z and electron number N = Z, which are correct to leading order (–0.221 Z 5/3 and –0.021 Z ln Z respectively) even in the lowest-rung or local density approximation. We find that hydrogenic densities lead to E x (N,Z) ≈ –0.354 N 2/3 Z (as known before only for Z >> N >> 1) and E c ≈ –0.02 N ln N . These asymptotic estimates are most correct for atomic ions with large N and Z >> N, but we find that they are qualitatively and semi- quantitatively correct even for small N and for N ≈ Z. The large-N asymptotic behavior of the energy is pre-figured in small-N atoms and atomic ions, supporting the argument that widely-predictive approximate density functionals should be designed to recover the correct asymptotics. Here, it is shown that the exact Kohn-Sham correlation energy, when calculated from the pure ground-state wavefunction, should have no contribution proportional to Z in the Z → ∞ limit for any fixed N.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Generation of focusing ion beams by magnetized electron sheath acceleration

Abstract We present the first 3D fully kinetic simulations of laser driven sheath-based ion acceleration with a kilotesla-level applied magnetic field. The application of a strong magnetic field significantly and beneficially alters sheath based ion acceleration and creates two distinct stages in the acceleration process associated with the time-evolving magnetization of the hot electron sheath. The first stage delivers dramatically enhanced acceleration, and the second reverses the typical outward-directed topology of the sheath electric field into a focusing configuration. The net result is a focusing, magnetic field-directed ion source of multiple species with strongly enhanced energy and number. The predicted improvements in ion source characteristics are desirable for applications and suggest a route to experimentally confirm magnetization-related effects in the high energy density regime. We additionally perform a comparison between 2D and 3D simulation geometry, on which basis we predict the feasibility of observing magnetic field effects under experimentally relevant conditions.

42 ENGINEERING↗

Lithium Dendrite-Free Li 7 N 2 I-LiOH Solid Electrolytes for High Energy Lithium Batteries

All-solid-state lithium batteries (ASSLBs) hold great potential to improve the safety and energy density of today’s lithium-ion batteries by using non-flammable inorganic solid electrolytes. Solid electrolytes (SEs) are believed to prevent Li dendrite growth because of high mechanical strength and high Li+ transference numbers. Significant advances in SE have been achieved, among which, Li7La3Zr2O12 (LLZO) and Li2S–P2S5 (LPS) are the most promising SEs for bulk-type solid-state lithium batteries because of high ionic conductivities (>10-4 S/cm2). However, in contrast to our expectations, the growth of lithium dendrites is not suppressed but is facilitated in LLZOs and LPSs regardless of dopants, porosity, and crystallinity of the electrolytes. Despite the unity Li transference number and over two-times of shear modulus than that of Li metal, the critical current densities for Li plating and stripping in these SEs are less than 1.0 mA cm-2, which is one-fourth to one-tenth of that in liquid electrolytes at room temperature. The incompatibility between LLZO and LPS with Li metal seriously limits the energy density of all-solid-state batteries. The mechanism for lithium dendrite formation and growth in SEs are still disputable. Lack of understanding of the Li dendrite formation mechanism seriously impeded the development of solid-state lithium batteries. The development of the criterion for Li dendrite suppression is essential for the success of solid electrolyte lithium batteries. In this project, a criterion for Li dendrite suppression will be developed through thermodynamics and kinetics analysis of lithium dendrite nucleation/growth, which will guide the solid-state electrolyte design. Li7N2I-LiOH, Li5NI2-LiOH and Li3YCl6 solid electrolyte with high ionic conductivity and low electronic conductivity were used to validate the criterion for lithium dendrite suppression. Different surface modifications were also explored to enhance the dendrite suppression capability of SSEs.

25 ENERGY STORAGE↗

Efficiency enhancement of thermonuclear DD reaction in femtosecond laser plasma with the use of structured low-average-density targets

An increase in the yield of fast neutrons is experimentally demonstrated by exciting a nuclear DD reaction in the interaction of a relativistically intense (over 10{sup 18} W cm{sup −2}) ultrashort laser pulse with a deuterated low-average-density target volume-structured at the wavelength scale. It is shown that decreasing the average target density from 0.78 to 0.35 g cm{sup −3} doubles the neutron flux, which reaches 7 × 10{sup 4} particles per 1 J of input energy. The effect may be associated with an increase in the number of accelerated deuterium ions due to the three dimensional expansion of individual elements of the target structure. (paper)

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Synergies between H, He and radiation damage in dual and triple ion irradiation of candidate fusion blanket materials

Three ferritic/martensitic alloys were studied to understand the synergistic effect between single ion beam (Fe 2+ ), dual ion beam (Fe 2+ +He 2+ and Fe 2+ +H + ), and triple ion beam (Fe 2+ +He 2+ +H + ) irradiations on cavity evolution. A commercial alloy, F82H, a castable nanostructured alloy, CNA3, and a high purity model alloy, Fe8Cr2W, were irradiated at 400°C to 600°C to a damage level of 50 dpa at a damage rate of 1 × 10 –3 dpa/s with He and H injection rates of 10 and 40 appm/dpa, respectively. Post-irradiation characterization via bright field transmission electron microscopy and high-angle annular dark-field scanning transmission electron microscopy was performed on all irradiated conditions to characterize the cavity size distribution and determine the effects of H/He injection on cavity microstructure. In all three alloys, hydrogen co-injection with helium resulted in an increased cavity number density and maximum cavity size, producing an increase in swelling over that from helium injection alone. Swelling in F82H appears to peak between 450°C and 500°C. At 600°C, swelling was minimal and cavities of high density and small size were confined to grain boundaries and dislocations while at 400°C, swelling is also low with a nearly homogeneous, high density, distribution of very small cavities throughout. Swelling was least in the commercial alloy F82H due to the high sink strength. The CNA3 alloy underwent dissolution of precipitates that lowered the sink strength and resulted in higher swelling than F82H, but less than the model alloy. Electron energy loss spectroscopy (EELS) elemental mapping revealed hydrogen forming a halo-like structure about the periphery of the cavities and helium residing within the cavities themselves. Finally, this observation suggests that hydrogen reduces the surface energy of helium-filled cavities which results in both increased cavity number density and cavity size in triple beam irradiation over dual beam irradiation.

36 MATERIALS SCIENCE↗

Flux effects in precipitation under irradiation simulation of Fe-Cr alloys

Radiation-enhanced precipitation of Cr-rich α’ in irradiated Fe-Cr alloys, which results in hardening and embrittlement, depends on the irradiating particle and the displacement per atom (dpa) rate. Here, we utilize a Cahn-Hilliard phase-field based approach, that includes simple models for nucleation, irradiating particle and rate dependent radiation-enhanced diffusion and cascade mixing to simulate α’ evolution under neutrons, heavy ions, and electron irradiations. Different irradiating particles manifest very different cascade mixing efficiencies. The model was calibrated using neutron data. For cascade inducing neutron/heavy-ion dpa rates at 300 °C between 10-8 and 10-6 dpa/s the model predicts approximately constant number density, decreasing radius, decreasing α’ Cr composition, and lower α’ volume fraction. The model then predicts a dramatic transition to no α’ formation above approximately 10-5 dpa/s, while electron irradiation, with weak mixing, had little effect at dpa rates up to 10-3 dpa/s. These model predictions are consistent with experiments. We explain the results in terms of the flux dependence of the radiation enhanced diffusion, cascade mixing, and their ratio, which all vary significantly in relevant flux ranges for neutron and cascade inducing ion irradiations. These results show that both cascade mixing and radiation enhanced diffusion must be accounted for when attempting to emulate neutron-irradiation effects using accelerated ion irradiations.

Ke, Jia-Hong↗

Mechanistic insights into structural parameters maximizing energy storage density in Si mesoporous electrodes for Li-ion batteries

Mesoporous Si electrodes have an interesting set of structural parameters, which, when carefully optimized, can lead to ultrahigh energy density Si electrodes for Li-ion batteries. We present here in this paper details of a systematic research leading to the discovery of an “ideal” structure of mesoporous Si electrode, which results in exceptional cracking/damage resistance, while simultaneously having very high specific (>2000 mAh g-1) and total (>1.5 mAh cm-2) capacities for large number of cycles. The electrodes near the “ideal” value of the characteristic structural parameter (the ratio of Si wall thickness to pore diameter) are free from first-cycle capacity degradation, and are efficient in accommodating the volume changes during lithiation by uniformly filling up the porous space between Si walls. Interestingly, these electrodes are also found to be structurally damage-resistant, surviving through many lithiation-delithiation cycles. Using charge-discharge cycling and electron microscopy we show that ideal structure is the key for achieving ultrahigh energy storage density in Si mesoporous electrodes for Li-ion batteries.

25 ENERGY STORAGE↗

Atom Probe Tomography Characterization of High-Dose Ion Irradiated MA957

This paper presents a comprehensive characterization study of the microstructural responses to ion irradiation of the oxide dispersion strengthened (ODS) ferritic alloy MA957 using atom probe tomography (APT). The MA957 specimens were irradiated by 1.8 MeV Cr3+ ions to doses and temperatures relevant to advanced fast reactors (100 and 500 dpa at 400-500 °C). The average sizes of the YTiO particles decreased slightly after irradiation at all temperatures, with the most pronounced change at 400 °C. The particle number densities for 400 and 500 °C were slightly below number densities for the unirradiated condition, while the values were slightly higher at 420 and 450 °C. This behavior is consistent with the Nelson-Hudson-Mazey rate theory model that considers the competing effects between recombination and dissolution. An increase in the Y/Ti ratio of the YTiO particles was observed at the two lower temperatures. The formation of Cr-rich precipitates (a') was observed in specimens irradiated at temperatures up to 450 °C. Irradiation-induced segregation on grain boundaries was also investigated. Grain boundary element concentration profiles and ion maps demonstrate differences among the irradiation temperatures, with most datasets differing from the unirradiated condition. A key focus of this ion irradiation study is the high-dose response, and this quantitative assessment revealed relatively small but distinct effects of irradiation on microstructure evolution. Overall, these results showing minor second phase evolution suggest that MA957 should retain mechanical performance generally well up to 500 dpa for the irradiation temperatures studied.

Wang, Jing↗

Temperature effects of ion irradiation on the nanostructural features in ductile-phase-toughened tungsten composites

Ductile-phase toughened tungsten (DPT W) composites have emerged as promising candidates for load-bearing components behind the plasma-facing tungsten armor in fusion reactors due to their enhanced thermomechanical properties. This study focuses on a composite consisting of W particles embedded in a ductile NiFeW solution matrix, hot-rolled to a thickness reduction of 87% (87R DPT W). Sequential irradiations with Ni2+ and He+ ions were performed to identical doses and helium concentrations at room temperature (RT) and 1273 K. Irradiation at RT produced no discernible nanostructural features due to the immobility of mono-vacancies, whereas cavity formation was observed at 973 K. At 1273 K, the W phase exhibited larger cavities, reduced cavity number density, and lower volumetric swelling compared to 973 K. Notably, nanosized NiFeW precipitates formed within the W phase at 1273 K, a phenomenon absent at 973 K. A new phase of cubic (NiFe)6W6C was also observed at the interphase boundary. In contrast, the NiFeW matrix showed no nanostructural changes at 1273 K, likely due to cavity dissociation. Separate irradiations at 1273 K indicated that Ni2+ ions induced precipitate formation in the W phase, while He+ ions exclusively caused cavity formation. The microstructure of 87R DPT W irradiated at RT and subsequently annealed at 1273 K closely resembled that of material irradiated directly at 1273 K. Like oxide-dispersion-strengthened steels, the observed nanoparticle-embedded W can inhibit dislocation propagation, potentially delaying the ductile-to-brittle transition temperature. These findings highlight the potential of NiFeW nanoparticle-reinforced W composites as irradiation-resistant materials for fusion reactors.

Jiang, Weilin (ORCID:0000000183028313)↗

Large deviations of ionic currents in dilute electrolytes

Here, we evaluate the exponentially rare fluctuations of the ionic current for a dilute electrolyte by means of macroscopic fluctuation theory. We consider the fluctuating hydrodynamics of a fluid electrolyte described by a stochastic Poisson–Nernst–Planck equation. We derive the Euler–Lagrange equations that dictate the optimal concentration profiles of ions conditioned on exhibiting a given current, whose form determines the likelihood of that current in the long-time limit. For a symmetric electrolyte under small applied voltages, number density fluctuations are small, and ionic current fluctuations are Gaussian with a variance determined by the Nernst–Einstein conductivity. Under large applied potentials, the ionic current distribution is generically non-Gaussian. Its structure is constrained thermodynamically by Gallavotti–Cohen symmetry and the thermodynamic uncertainty principle.

Farhadi, Jafar [University of California, Berkeley↗

Nanostructured polyelectrolytes for ion-selective membranes

Nanostructured polyelectrolyte bilayers deposited by Layer-by-Layer deposition on nanoporous membranes can be selectively crosslinked to modify the polyelectrolyte charge density and control ionic selectivity independent of ionic conductivity. For example, the polyelectrolyte bilayer can comprise a cationic polymer layer, such as poly(ethyleneimine), and an anionic polymer layer, such as poly(acrylic acid). Increasing the number of bilayers increases the cation selectivity when the poly(ethyleneimine) layer is crosslinked with glutaraldehyde. Crosslinking the membranes also increases the chemical and mechanical strength of the polyelectrolyte films. This controllable and inexpensive method can be used to create ion-selective and mechanically robust membranes on porous supports for a wide range of applications.

25 ENERGY STORAGE↗

HfZr_BCC_SolidSolution_128atoms_VASP6

We performed density functional theory (DFT) calculations for body-centered-cubic (BCC) structures with 128 lattices sites of solid solution binary alloys hafnium-zirconium (Hf-Zr). The electronic structures of alloys have been calculated using Vienna Ab initio Simulation Package (VASP). Within this package the DFT approach is used to reduce many-body Schrodinger equation to set of single particle Kohn-Sham (KS) equations. The generalized electronic exchange-correlation functional is described by generalized gradient approximation with the Perdew-Burke-Ernzerhof parametrization. The electron-ion interactions is described by pseudopotentials developed within the plane-wave basis projector augmented-wave (PAW) approach. These pseudopotentials are available at the VASP portal (http://cms.mpi.univie.ac.at/vasp/). Our calculations have been run with the pseudopotentials treating s and p semi-core states as valence in case for the elements Hf and Zr. The electronic densities and potentials are expanded over plane-waves with energy cutoff of 350 eV. 2x2x2 k-mesh and normal precision were used. The alloys were modeled by supercell containing 128 randomly distributed atoms. At initial step the atoms occupy perfect bcc lattice cites. This initial structure was optimized until energy changes less than 1e-6 eV, while forces acting on atoms don't exceed 1e-2 eV/angstrom. The electron-ion interaction is described by PAW pseudopotentials. The calculations have been collected by sampling chemical compositions across the entire compositional range. The chemical compositions have been sampled by progressively changing the number of atoms per constituent by 4. For each chemical composition of binaries and ternaries, the first-principle calculations have been run for 100 randomized arrangements of the constituents on the BCC lattice sites. We collected data for a total of 3,100 randomized atomic structures over 31 chemical compositions.

36 MATERIALS SCIENCE↗

Time-resolved velocity and ion sound speed measurements from simultaneous bow shock imaging and inductive probe measurements

We present a technique to measure the time-resolved velocity and ion sound speed in magnetized, supersonic high-energy-density plasmas. We place an inductive (“b-dot”) probe in a supersonic pulsed-power-driven plasma flow and measure the magnetic field advected by the plasma. As the magnetic Reynolds number is large (R M > 10), the plasma flow advects a magnetic field proportional to the current at the load. This enables us to estimate the flow velocity as a function of time from the delay between the current at the load and the signal at the probe. The supersonic flow also generates a hydrodynamic bow shock around the probe, the structure of which depends on the upstream sonic Mach number. By imaging the shock around the probe with a Mach–Zehnder interferometer, we determine the upstream Mach number from the shock Mach angle, which we then use to determine the ion sound speed from the known upstream velocity. We use the sound speed to infer the value of Z̄T e , where Z̄ is the average ionization and T e is the electron temperature. We use this diagnostic to measure the time-resolved velocity and sound speed of a supersonic (M S ~ 8), super-Alfvénic (M A ~ 2) aluminum plasma generated during the ablation stage of an exploding wire array on the Magpie generator (1.4 MA, 250 ns). The velocity and Z̄T e measurements agree well with the optical Thompson scattering measurements reported in the literature and with 3D resistive magnetohydrodynamic simulations in GORGON.

47 OTHER INSTRUMENTATION↗

High-temperature ion-thermal behavior from average-atom calculations

Atom-in-jellium calculations of the Einstein frequency were used to calculate the mean displacement of an ion over a wide range of compression and temperature. Expressed as a fraction of the Wigner-Seitz radius, the displacement is a measure of the asymptotic freedom of the ion at high temperature, and thus of the change in heat capacity from six to three quadratic degrees of freedom per atom. A functional form for free energy was proposed based on the Maxwell-Boltzmann distribution as a correction to the Debye free energy, with a single free parameter representing the effective density of potential modes to be saturated. Finally, this parameter was investigated using molecular dynamics simulations, and found to be ~0.2 per atom. In this way, the ion-thermal contribution can be calculated for a wide-range equation of state (EOS) without requiring a large number of molecular dynamics simulations. Example calculations were performed for carbon, including the sensitivity of key EOS loci to ionic freedom.

74 ATOMIC AND MOLECULAR PHYSICS↗

Energetics and Structure of Nickel Atoms and Nanoparticles on MgO(100)

The growth morphology and interfacial energetics of vapor deposited Ni on the MgO(100) surface at 300 and 100 K have been studied using single crystal adsorption calorimetry (SCAC), He + low-energy ion scattering spectroscopy (LEIS), X-ray photoelectron spectroscopy (XPS), and low-energy electron diffraction (LEED). At 300 K, the Ni atoms grow as three-dimensional nanoparticles with a saturation number density of 5 × 10 16 particles/m 2 . The differential heat of adsorption at 300 K increases rapidly with coverage, from 276 (initially) to 311 kJ/mol by 0.4 ML. Thereafter, it slowly increases asymptotically to the sublimation enthalpy of bulk Ni (430 kJ/ml) by 9 ML. The Ni 2p 3/2 XPS peak binding energy at 300 K is initially (i.e., at 0.16 ML) 1.4 eV higher than that for bulk Ni(solid), but it decreases to that value at high coverage. The Ni atoms form a metastable phase at 300 K when in nanoparticles with diameter <2.5 nm, and the adhesion energy of such Ni nanoparticles to MgO(100) was found to be 3.05 J/m 2 . At 100 K, the Ni atoms form single adatoms and then 0.17 nm thick 2D islands at low coverage with fewer Ni-Ni bonds compared to the Ni nanoparticles formed at 300 K. Thus, the initial heat (i.e., for the first ~0.03 ML) is 148 kJ/mol at 100 K, 128 kJ/mol lower than at 300 K, and remains lower for the 2D islands. With increasing coverage at 100 K, the tiny 2D Ni islands grow in size to cover nearly the entire surface before thickening. Lastly, the XPS Ni 2p 3/2 peak binding energy for 0.21 ML Ni on MgO(100) at 100 K is 2.2 eV higher than that for bulk Ni(solid), suggesting charge transfer from Ni to MgO(100) and formation of Ni 2+ at very low coverage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Estimating Electron Temperature and Density Using Van Allen Probe Data: Typical Behavior of Energetic Electrons in the Inner Magnetosphere

Abstract The Earth's inner magnetosphere contains multiple electron populations influenced by different factors. The cold electrons of the plasmasphere, warm plasma that contributes to the ring current, and the relativistic plasma of the radiation belts often seem to behave independently. Using omni‐directional flux and energy measurements from the HOPE and Magnetic Electron Ion Spectrometer instruments aboard the Van Allen Probes, we provide a detailed density and temperature description of the inner magnetosphere, offering a comprehensive statistical analysis of the entire Van Allen Probe era. While number density and temperature data at geosynchronous orbit are available, this study focuses on the warm plasma in the inner magnetosphere . Values of density and temperature are extracted by fitting energy and phase space density to obtain the distribution function. The fitted distributions are related to the zeroth and second moments to estimate the number density and temperature. Analysis has indicated that a two Maxwellian fit is sufficient over a wide range of and that there are two independent plasma populations. The more energetic population has a median number density of approximately and a temperature of around 130 keV, with a temperature peak observed between L * = 4 and L * = 4.5. This population is relatively uniform in magnetic local time (MLT). In contrast, the less energetic warm electron population has a median number density of about and a temperature of 7.4 keV. Strong statistical trends in density and temperature across both L * and MLT are presented, along with potential sources driving these variations.

58 GEOSCIENCES↗

Multi-microscopy characterization of threading dislocations in CVD-grown diamond films

We present site-coincident imaging of a high dislocation density boron-doped chemical vapor deposition-grown homoepitaxial (001) diamond film using electron channeling contrast imaging (ECCI), cathodoluminescence, transmission electron microscopy (TEM), and scanning secondary ion mass spectroscopy (SIMS). With growing interest in large area heteroepitaxial substrates, we show that ECCI is a promising technique to accurately evaluate dislocations in diamond films. We find the electron backscatter yield is sufficient to distinguish individual threading dislocations in ECCI despite the low atomic number of carbon, and we have generally good agreement between dislocations observed in ECCI and TEM of the same region. Importantly, relying on luminescence in the 430 nm dislocation-related A-band alone results in an underestimation of the defect density as we find only 20%–40% of the threading dislocations luminesce. Here, we further show that dislocations do not perturb the spatial uniformity of boron doping measured by SIMS, even when the dislocations are clustered with high density, and we can tentatively rule out strong segregation effects at the dislocations. Our results establish the complementary use of microscopy and microanalysis methods to rapidly characterize and understand the impact of dislocations in diamond thin films.

36 MATERIALS SCIENCE↗