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At least 307 records · Page 17

Low-temperature etching of silicon oxide and silicon nitride with hydrogen fluoride

Etching of high aspect ratio features into alternating SiO 2 and SiN layers is an enabling technology for the manufacturing of 3D NAND flash memories. In this paper, we study a low-temperature or cryo plasma etch process, which utilizes HF gas together with other gas additives. Compared with a low-temperature process that uses separate fluorine and hydrogen gases, the etching rate of the SiO 2 /SiN stack doubles. Both materials etch faster with this so-called second generation cryo etch process. Pure HF plasma enhances the SiN etching rate, while SiO 2 requires an additional fluorine source such as PF 3 to etch meaningfully. Further, the insertion of H 2 O plasma steps into the second generation cryo etch process boosts the SiN etching rate by a factor of 2.4, while SiO 2 etches only 1.3 times faster. We observe a rate enhancing effect of H 2 O coadsorption in thermal etching experiments of SiN with HF. Ammonium fluorosilicate (AFS) plays a salient role in etching of SiN with HF with and without plasma. AFS appears weakened in the presence of H 2 O. Density functional theory calculations confirm the reduction of the bonding energy when NH 4 F in AFS is replaced by H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plasma-catalyst modeling for materials selection: challenges and opportunities in nitrogen oxidation

Reliable kinetic models are essential to rationalize observations and to guide the selection of appropriate plasma-catalyst combinations. Kinetic models coupling plasma- and heterogeneous-catalytic-chemistries, however, are primitive. Here, we combine reduced plasma chemistries and density functional theory parameterized surface reactions to model NO formation from N2 oxidation, an alternative nitrogen fixation process. We first show plasma excited species can enhance turnover frequencies of both Pt and Au. The enhancing potential is a function of plasma species and their densities. We then compare NO production between plasma/Pt and plasma/Au with an integral reactor model and explore the dependence of NO production as a function of plasma conditions, reactor configurations and chemical compositions. Plasma/Pt generates more NO than plasma/Au under most thermal and plasma parametric conditions. Plasma/Au outperforms plasma/Pt under high plasma excitations at low temperatures. Furthermore, these results highlight that selection of plasma-catalyst combinations should consider the properties of plasmas, materials and the coupling of the two.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Plasma chemistry for inorganic materials

Practical application of plasma chemistry to the development of inorganic materials using both low temperature and warm plasmas are summarized. Topics cover: the surface nitrification and oxidation of metals; chemical vapor deposition; formation of minute oxide particles; the composition of oxides from chloride vapor; the composition of carbides and nitrides; freezing high temperature phases by plasma arc welding and plasma jet; use of plasma in the development of a substitute for petroleum; the production of silicon for use in solar cell batteries; and insulating the inner surface of nuclear fusion reactor walls.

Matsumoto, O.↗

Coating Development for GRCop-84 Liners for Reusable Launch Vehicles Aided by Modeling Studies

The design of the next generation of reusable launch vehicles calls for using GRCop-84 copper alloy liners based on a composition invented at the NASA Glenn Research Center. Despite its considerable advantage over other copper alloys, it is expected that GRCop-84 will suffer from environmental degradation depending on the type of rocket fuels used and on thermomechanical fatigue. Applying protective coatings on GRCop-84 substrates can minimize or eliminate many of these problems and extend the operational life of the combustion liner. This could increase component reliability, shorten depot maintenance turnaround times, and lower operating costs. Therefore, Glenn is actively pursuing the development of advanced coatings technology for GRCop-84 liners. Technology is being developed in four major areas: (1) new metallic coating compositions, (2) application techniques, (3) test methods, and (4) life prediction design methodology using finite element analysis. The role of finite element analysis in guiding the coating effort is discussed in this report. Thermal analyses were performed at Glenn for different combinations of top- and bondcoat compositions to determine the temperature variation across the coated cross section with the thickness of the top coat. These calculations were conducted for simulated LH2/LO2 booster engine conditions assuming that the bond coat had a constant thickness of 50 m. The preceding graphs show the predicted temperatures at the outer surface of the top coat (hot wall), at the top-coat/bond-coat interface, at the bond-coat/GRCop-84 interface, and at the GRCop-84 cold wall as a function of top-coat thickness for Cu- 26(wt%)Cr top coat (top graph), Ni-17(wt%)Cr-6%Al-0.5%Y top coat and Cu-26%Cr bond coat, and NiAl top coat and Ni bond coat. In all cases, the temperature of the top coat at the hot wall increased with increasing top-coat thickness and with corresponding decreases in the temperatures at the two interfaces and the cold wall. These temperatures are not acutely sensitive to the thermal conductivity of the top coat when it exceeds 25 and 50 W/m/K for low and high heat flux engines. This observation is significant for two reasons. First, several different top-coat compositions can be evaluated as potential protective coatings without loss in the heat-transfer efficiency of the coated system. Second, materials with thermal conductivities less than the critical values of 25 or 50 W/m/K are more likely to act as thermal barrier coatings. The deposition of overlay coatings on GRCop-84 substrates results in the development of residual stresses. The presence of these residual stresses influences the probability of coating spallation, the thermal cycling life, and the fatigue properties of the coated substrate during use. Since it is important to understand how these stresses develop during the vacuum-plasma-spraying coating deposition process, the nature and magnitudes of the cool-down residual stresses were calculated and compared with experimentally determined values across the coated cross section of a disk specimen. The calculations were conducted assuming that the specimen cools down to room temperature from vacuum plasma-spraying temperatures of either 250 or 650 C. The effects of coating the substrate with and without grit blasting were also theoretically examined. The final graph compares the predicted and the experimental results for a GRCop-84 disk coated with about a 50- m-thick Ni bond coat and a 75- to 100- m NiAl top coat, where the curves for NASA-2 assume the presence of a prior residual stress generated by grit blasting under conditions similar to the experimental situation. The predicted cool-down in-plane stresses were compressive in both the NiAl top coat and the Ni bond coat. They were also compressive in the substrate to a depth of about 0.25 mm from the Ni/GRCop-84 interface when the vacuum-plasma-spraying temperature was low. However, using a higher plasma spraying temperaturs likely to leave the substrate under a small tensile stress to counter the compressive stresses in the bond and top coats because of the relaxation of residual stresses generated in the substrate during the grit blasting of its surface prior to spraying. These results suggest that the NiAl and Ni coatings are unlikely to spall after spraying as confirmed by the microstructural observations shown in the following photomicrograph of an as-sprayed specimen. Finally, it is noted that the calculated and experimental results are not in complete agreement, which indicates that both the experimental and modeling techniques need further refinement.

Raj, Sai V.↗

Signatures of shock drivers in the solar wind and their dependence on the solar source location

Solar wind and energetic ion observations following 40 interplanetary shocks with well-established solar source locations have been examined in order to determine whether signatures characteristic of the coronal material forming the shock driver are present. The signatures considered include magnetic-field-aligned bidirectional ion flows observed by the ISEE 3 and IMP 8 spacecraft; bidirectional solar wind electron heat fluxes; solar wind plasma proton and electron temperature depressions; low-beta plasma; enhanced, low-variance magnetic fields; and energetic ion depressions. Several shock driver signatures are commonly observed following shocks originating from within about 50 deg of central meridian, and are generally absent for other events. We conclude that shock drivers generally extend up to about 100 deg in longitude, centered on the solar source longitude. Since shocks from central meridian events are not usually associated with all the shock driver signatures examined, the absence of a driver cannot be confirmed from consideration of one of these signatures alone. We also find evidence that a few bidirectional energetic ion and solar wind electron heat flux events following shocks (in particular from far eastern sources) may occur on open field lines outside of shock drivers.

Richardson, I. G.↗

Efficient ECCD non-inductive plasma current start-up, ramp-up, and sustainment for an ST fusion reactor

The elimination of the need for an Ohmic heating solenoid may be the most impactful design driver for the realization of economical compact fusion tokamak reactor systems. However, this would require fully non-inductive start-up and current ramp-up from zero plasma current and low electron temperature of sub-keV to the full plasma current of ~10–15 MA at 20–30 keV electron temperature. To address this challenge, an efficient solenoid-free start-up and ramp-up scenario utilizing a low-field-side-launched extraordinary mode at the fundamental electron cyclotron harmonic frequency (X–I) is proposed, which has more than two orders of magnitude higher electron cyclotron current drive (ECCD) efficiency than the conventional ECCD for the sub-keV start-up regime. A time dependent model was developed to simulate the start-up scenarios. For the Spherical Tokamak Advanced Reactor (STAR) (Menard et al 2023 Next-Step Low-Aspect-Ratio Tokamak Design Studies (IAEA)), it was found that to fully non-inductively ramp-up to 15 MA, it would take about 25 MW of EC power at 170 GHz. Because of the relatively large plasma volume of STAR, radiation losses must be considered. It is important to make sure that high Z impurities are kept sufficiently low during the early current start-up phase where the temperature is sub-keV range. Since the initial current ramp up takes place at a factor of ten lower density compared to the sustained regimes, it is important to transition into a higher bootstrap fraction discharge at lower density to minimize the ECCD power requirement during the densification. For the sustainment phase an array of eight gyrotron launchers with a total of about 60 MW of fundamental O-mode was found to be sufficient to provide the required axis-peaked external current drive. High efficiencies between 19–57 kA MW –1 were found with optimal aiming, and these were resilient to small changes in aiming angles and density and temperature profiles.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Computational Fluid Dynamics Modeling of Low Temperature Ignition Processes From a Nanosecond Pulsed Discharge at Quiescent Conditions

Recent interest in nonequilibrium plasma discharges as sources of ignition for the automotive industry has not yet been accompanied by the availability of dedicated models to perform this task in computational fluid dynamics (CFD) engine simulations. The need for a low-temperature plasma (LTP) ignition model has motivated much work in simulating these discharges from first principles. Most ignition models assume that an equilibrium plasma comprises the bulk of discharge kernels. LTP discharges, however, exhibit highly nonequilibrium behavior. In this work, a method to determine a consistent initialization of LTP discharge kernels for use in engine CFD codes like CONVERGE is proposed. The method utilizes first principles discharge simulations. Such an LTP kernel is introduced in a flammable mixture of air and fuel, and the subsequent plasma expansion and ignition simulation is carried out using a reacting flow solver with detailed chemistry. Finally, the proposed numerical approach is shown to produce results that agree with experimental observations regarding the ignitability of methane-air and ethylene-air mixtures by LTP discharges.

33 ADVANCED PROPULSION SYSTEMS↗

Microwave diagnostic for the determination of the electron temperature of a low density shock-heated argon plasma

The diffraction, defocusing and beam bending effects of microwaves transmitted through a bounded shock-heated argon plasma with low electron density are investigated with the purpose of developing an accurate method for electron temperature (Te) determination. This report describes the evaluation technique and presents results for an argon plasma with pressure between 3 and 10 torr, and T2 between 5500 and 9500 K. The electron temperature values obtained have a range of uncertainty between -20% and +10% only. The electron temperature is equal or lower by approximately 1000 K in comparison to the heavy particle temperature (T2).

Schneider, C. P.↗

Toward sustainable production of N-containing products via nonthermal plasma-enhanced conversion of natural gas resources

Nonthermal plasmas can directly activate and cleave the strong chemical bonds in molecular nitrogen and methane to facilitate the transformation of these inherently stable molecules through the application of electrical energy. Here, we report a low temperature, atmospheric pressure, nonthermal plasma for the “one-pot” synthesis of olefins, alkynes, higher molecular weight hydrocarbons, ammonia, and nitrogen-containing liquids from a representative shale gas feed enriched with nitrogen. Furthermore, we reproducibly observe a wide range of valuable and synthetically challenging gas-phase and liquid-phase products containing C-N, C-C, and N-H bonding by controlling the N 2 concentration in the inlet feed stream. In nitrogen-lean regimes, hydrocarbon products dominate (e.g., ethylene, acetylene, etc.), while nitrogen-rich regimes promote incorporation of nitrogen into the products, leading to the formation of ammonia and liquid products containing a variety of functionalities (e.g., nitriles, amines, heterocycles). High resolution electrospray ionization mass spectrometry was used to measure molecular weights and identify the chemical formulas of the liquid products. Van Krevelen diagrams were created and showed many products with compositions around H/C = 2 and N/C = 0.5, indicating the potential importance of intermediate species with these ratios for liquid formation (e.g., CH 3 CN + H).

03 NATURAL GAS↗

Electron-field instability: Excitation of electron plasma waves by an electric field

Electric fields are commonplace in plasmas and affect transport by driving currents and, in some cases, instabilities. The necessary condition for instability in collisionless plasmas is commonly understood to be described by the Penrose criterion, which quantifies a sufficient relative drift between different populations of particles that must be present for wave amplification via inverse Landau damping. For example, electric fields generate drifts between electrons and ions that can excite the ion-acoustic instability. Here, we use particle-in-cell simulations and linear stability analysis to show that the electric field can drive a fundamentally different type of kinetic instability, named the electron-field instability. This instability excites electron plasma waves with wavelengths ≳30λ De , has a growth rate that is proportional to the electric field strength, and does not require a relative drift between electrons and ions. The Penrose criterion does not apply when accounting for the electric field. Furthermore, the large value of the observed frequency, near the electron plasma frequency, further distinguishes it from the standard ion-acoustic instability, which oscillates near the ion plasma frequency. The ubiquity of macroscopic electric fields in quasineutral plasmas suggests that this instability is possible in a host of systems, including low-temperature and space plasmas. In fact, damping from neutral collisions in such systems is often not enough to completely damp the instability, adding to the robustness of the instability across plasma conditions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Understanding the Impact of Return-Current Losses on the X-Ray Emission from Solar Flares

I obtain and examine the implications of one-dimensional analytic solutions for return-current losses on an initially power-law distribution of energetic electrons with a sharp low-energy cutoff in flare plasma with classical (collisional) resistivity. These solutions show, for example, that return-current losses are not sensitive to plasma density, but are sensitive to plasma temperature and the low energy cutoff of the injected nonthermal electron distribution. A characteristic distance from the electron injection site, x(sub rc), is derived. At distances less than x(sub rc) the electron flux density is not reduced by return-current losses, but plasma heating can be substantial in this region, in the upper, coronal part of the flare loop. Before the electrons reach the collisional thick-target region of the flare loop, an injected power-law electron distribution with a low-energy cutoff maintains that structure, but with a flat energy distribution below the cutoff energy, which is now determined by the total potential drop experienced by the electrons. Modifications due to the presence of collisional losses are discussed. I compare these results with earlier analytical results and with more recent numerical simulations. Emslie's 1980 conjecture that there is a maximum integrated X-ray source brightness on the order of 10(exp -15) photons per square centimeter per second per square centimeter is examined. I find that this is not actually a maximum brightness and its value is parameter dependent, but it is nevertheless a valuable benchmark for identifying return-current losses in hard X-ray spectra. I discuss an observational approach to identifying return-current losses in flare data, including identification of a return-current "bump" in X-ray light curves at low photon energies.

Holman, Gordon D.↗

Experimental and theoretical study of the plasma physics of antihydrogen generation and trapping. Final Scientific Report

The main goal of the project was to determine if matter and antimatter are exact conjugates. According to the current best understanding of the universe, this property should hold. The ALPHA collaboration performed a series of high precision measurements on trapped antihydrogen and compared the results to those that would be expected for hydrogen. Any difference would have enormous implications for our understanding of basic physics because a difference would mean the CPT theorem is violated. In pursuit of this goal, we needed to understand plasma and atomic processes for a novel set of plasma parameters: extremely low temperature (a few 10's of K) and high magnetic field (a couple T). Our attempts to control/manipulate these plasmas led to important goals related directly to plasma physics. For example, the radiative coupling of the cyclotron motion to a microwave cavity can display collective effects as the number of positrons increases. This DOE award mainly provided support for theoretical studies of the atomic and plasma processes that determine the outcome of the experiments.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Spacecraft Charging in Low Temperature Environments

Spacecraft charging in plasma and radiation environments is a temperature dependent phenomenon due to the reduction of electrical conductivity in dielectric materials at low temperatures. Charging time constants are proportional to l/conductivity may become very large (on the order of days to years) at low temperatures and accumulation of charge densities in insulators in charging environments traditionally considered benign at ambient temperatures may be sufficient to produce charge densities and electric fields of concern in insulators at low temperatures. Low temperature charging is of interest because a number of spacecraft-primarily infrared astronomy and microwave cosmology observatories-are currently being design, built, and or operated at very cold temperatures on the order of 40K to 100K. This paper reviews the temperature dependence of spacecraft charging processes and material parameters important to charging as a function of temperature with an emphasis on low temperatures regimes.

Parker, Linda N.↗

The impedance characteristic of a spherical probe in an isotropic plasma.

Experimental investigation of the impedance characteristic of a spherical plasma probe for a quantitative assessment of theoretical work, and of hydrodynamic or fluid theory in particular. A stable, low-temperature (about 500K) plasma was produced in nitrogen by a cold-cathode discharge, with a plasma frequency of the order of 15 MHz and with an electron collision frequency in the range from one to ten million per sec. Hydrodynamic probe theory was tested against the experimental results for the specific cases corresponding to the probe at floating potential and at space potential. Good agreement was obtained for both the real and imaginary parts. The real part of the impedance shows a peak near the plasma frequency, a small shift being explicable in terms of realistic sheath profiles. Electron density can thus be deduced rather accurately, and electron temperature approximately, on the basis of hydrodynamic theory. Accurate values of the electron-neutral collision frequency were also obtained for plasmas where the collision frequency was larger than 0.4 times the radian plasma frequency. At lower pressures the presence of collisionless or Landau damping was clearly established, and the more accurate kinetic theory is necessary to explain the experimental results.

Tarstrup, J.↗

Impact of CH 4 addition on the electron properties and electric field dynamics in a Ar nanosecond-pulsed dielectric barrier discharge

Non-equilibrium plasmas derive their low temperature reactivity from producing and driving energetic electrons and active species under large electric fields. Therefore, the impact of reactants on the plasma properties including electron number density, electric field, and electron temperature is critical for applications such as plasma CH 4 reforming. Due to experimental complexity, electron properties and the electric field are rarely measured together in the same discharge. Here, we combine time-resolved Thomson scattering and electric field induced second harmonic generation (EFISH) to probe electron temperature, electron density, and electric field strength in a 60 Torr CH 4 /Ar nanosecond-pulsed dielectric barrier discharge (ns-DBD) while varying the CH 4 mole fraction from 0 to 8%. These measurements are compared to a 1-D numerical model to benchmark its predictions and identify areas of uncertainty. Nonlinear coupling between CH 4 addition, electron temperature, electron density, and the electric field was directly observed. Contrary to previous measurements in He, the electron temperature increased with CH 4 mole fraction. This rise in electron temperature is identified as electron heating by residual electric fields that increased with larger CH 4 mole fraction. Moreover, the electron number density has been found to decrease rapidly with the increase of methane mole fraction. Comparison of these measurements with the model yielded better agreement at higher CH 4 mole fractions and with the usage of ab initio calculated Ar electron-impact cross-sections from the B-spline R-matrix (BSR) database. Furthermore, the calculated plasma properties are shown to be sensitive to the residual surface charge implanted on the quartz dielectric surfaces. Without considering surface charge in the simulations, the calculated electric field profiles agreed well with the measurements, but the electron properties were underpredicted by more than a factor of three. Therefore, measurements of either the electric field or electron properties measurements alone are insufficient to fully validate modelling predictions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Crystallographic and temperature effects in low-energy collisions for plasma–material interactions

The interaction of plasma with materials is critical for the fundamental understanding of non-equilibrium processes and their wide application. Recent achievements in fusion energy research emphasize the importance of this problem. Because modelling and predicting plasma–material interactions (PMI) require considering a tremendous number of single plasma particle–surface interaction events, this type of modelling was, until recently, possible only within a binary collision approximation (BCA). The BCA approach considers materials as uniform temperature-insensitive media. The research presented here addresses the PMI problem within an atomistic-based approach for the first time at a statistically significant level. Approximately 10 5 molecular dynamics trajectories were generated for 100 eV deuterium ions interacting with a tungsten surface. The research demonstrated the critical importance of incorporating the discrete lattice structure of matter into the model. Deuterium penetration depth and fraction of backscattered deuterium ions strongly depend on the surface orientation, the impact incident ion directions, and the ions’ initial positions. On average, the BCA-based calculations underestimate the penetration depth by a factor of two or more, and the fraction of backscattered atoms is overestimated by a factor of two or more. As a result, increasing the material temperature from 500 to 3000 K reduces penetration depth by about 30% and increases the fraction of backscattered atoms by 250%.

36 MATERIALS SCIENCE↗

Plasma catalysis: separating plasma and surface contributions for an Ar/N 2 /O 2 atmospheric discharge interacting with a Pt catalyst

Atmospheric pressure non-equilibrium plasmas can form nitrogen oxide (NO x ) compounds directly from nitrogen and oxygen without a catalyst, and at lower catalyst temperatures than would be possible without plasma. In this work, the oxidation of plasma-produced NO from an Ar/N 2 /O 2 non-equilibrium atmospheric-pressure plasma-jet (APPJ) over a platinum-on-alumina powder catalyst was investigated with in-situ infrared spectroscopy. Products downstream of the catalyst bed were analyzed along with catalyst surface species. The catalyst was exposed to plasma at both constant temperature and a cyclic temperature ramp in order to study long-lasting and transient surface changes. Primary incident reactive species to the catalyst were assessed to be NO and O 3 . Pt-Al 2 O 3 at 350 °C increased oxidation of NO relative to Al 2 O 3 or an empty chamber. The surface state of Pt-Al 2 O 3 evolves during plasma-effluent exposure and requires upwards of 20 min exposure for stabilization compared to Al 2 O 3 . Once stable surface conditions are achieved, thermal cycling reveals a repeatable hysteresis pattern in downstream products. At low temperature, oxygen and NO x accumulate on the catalyst surface and react at elevated temperatures to form NO 2 . Increasing plasma power and O 2 :N 2 ratio increases the hysteresis of the heating relative to the cooling curves in the pattern of NO 2 formation. The limitation on NO oxidation at high temperatures was assessed to be Pt-O which is depleted as the catalyst is heated. Once stored species have been depleted, NO oxidation rates are determined by incoming reactants. Two overlapping NO oxidation patterns are identified, one determined by surface reactants formed at low temperature, and the other by reactants arriving at the surface at high temperature. As a result, the plasma is responsible for providing the reactants to the catalyst surface, while the catalyst enables reaction at high temperature or storage at low temperature for subsequent reaction.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Moisture resistant and anti-reflection optical coatings produced by plasma polymerization of organic compounds

The need for protective coatings on critical optical surfaces, such as halide crystal windows or lenses used in spectroscopy, has long been recognized. It has been demonstrated that thin, one micron, organic coatings produced by polymerization of flourinated monomers in low temperature gas discharge (plasma) exhibit very high degrees of moisture resistence, e.g., hundreds of hours protection for cesium iodide vs. minutes before degradation sets in for untreated surfaces. The index of refraction of these coatings is intermediate between that of the halide substrate and air, a condition for anti-reflection, another desirable property of optical coatings. Thus, the organic coatings not only offer protection, but improved transmittance as well. The polymer coating is non-absorbing over the range 0.4 to 40 microns with an exception at 8.0 microns, the expected absorption for C-F bonds.

Hollahan, J. R.↗