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The effects of plasma exposure and vacuum ultraviolet irradiation on photopatternable low-k dielectric materials

The effects of plasma exposure and vacuum-ultraviolet (VUV) irradiation on photopatternable low-k (PPLK) dielectric materials are investigated. In order to examine these effects, current-voltage measurements were made on PPLK materials before and after exposure to a variety of inert plasma-exposure conditions. In order to examine the effects of photon irradiation alone, PPLK samples were also exposed to monochromatic synchrotron radiation with 10 eV photon energy. It was found that plasma exposure causes significant degradation in electrical characteristics, resulting in increased leakage-currents and decreased breakdown voltage. X-ray photoelectron spectroscopy measurements also show appreciable carbon loss near the sample surface after plasma exposure. Conversely, VUV exposure was found to increase breakdown voltage and reduce leakage-current magnitudes.

36 MATERIALS SCIENCE↗

The tropospheric-stratospheric polar vortex breakdown of January 1977

An extraordinary warming of the stratosphere in December-January 1976-77 was followed by tropospheric warming in the polar region and cooling in middle latitudes. During January 10-20, the associated polar anticyclone extended from the surface to 10 mb. Antecedents of the polar vortex breakdown are reviewed with the aid of results of zonal-harmonic analyses of planetary waves, for heights of the pressure surfaces (700-10 mb), temperature, and mean stratospheric temperature (the latter determined from satellite radiation measurements). Wave 1 in height and temperature played a dominant role in the stratosphere, attaining amplitudes of 1600 gpm and 25 C, respectively, at 10 mb. On the other hand, superposition of retrogressing wave 1 and quasi-stationary wave 2 in the height of the 300-mb surface, with individual amplitudes exceeding 300 gpm, is judged to have been an important factor in the overall development.

Quiroz, R. S.↗

Carbon-Based Wear Coatings: Properties and Applications

The technical function of numerous engineering systems - such as vehicles, machines, and instruments - depends on the processes of motion and on the surface systems. Many processes in nature and technology depend on the motion and dynamic behavior of solids, liquids, and gases. Smart surface systems are essential because of the recent technological push toward higher speeds, loads, and operating temperatures; longer life; lighter weight and smaller size (including nanotechnology); and harsh environments in mechanical, mechatronic, and biomechanical systems. If proper attention is not given to surface systems, then vehicles, machines, instruments, and other technical systems could have short lives, consume excessive energy, experience breakdowns, result in liabilities, and fail to accomplish their missions. Surface systems strongly affect our national economy and our lifestyles. At the NASA Glenn Research Center, we believe that proper attention to surface systems, especially in education, research, and application, could lead to economic savings of between 1.3 and 1.6 percent of the gross domestic product. Wear coatings and surface systems continue to experience rapid growth as new coating and surface engineering technologies are discovered, more cost-effective coating and surface engineering solutions are developed, and marketers aggressively pursue, uncover, and exploit new applications for engineered surface systems in cutting tools and wear components. Wear coatings and smart surface systems have been used widely in industrial, consumer, automotive, aerospace, and biomedical applications. This presentation expresses the author's views of and insights into smart surface systems in wear coatings. A revolution is taking place in carbon science and technology. Diamond, an allotrope of carbon, joins graphite, fullerenes, and nanotubes as its major pure carbon structures. It has a unique combination of extreme properties: hardness and abrasion resistance; adhesion and friction; thermal conductivity; chemical and thermal inertness; corrosion and wear resistance; radiation resistance and biocompatibility; electronic, acoustic, and electrochemical characteristics; and environmental compatibility. These properties make diamond attractive for a wide range of diverse applications. In particular, chemical-vapor-deposited (CVD) diamond coatings offer a broad potential, since size and cost are not as limiting. The production of large, superhard diamond films or sheets at low cost make designer materials possible. This presentation is divided into two sections: properties and applications of hard coatings. The first section is concerned with the fundamental properties of the surfaces of CVD diamonds and related materials. The surface properties of hard coatings with favorable coefficients of friction (less than or equal to 0.1) and dimensional wear coefficients (less than or equal to 10(exp -6) cubic millimeters/N.m) in specific environments are discussed. The second section is devoted to applications. Examples of actual, successful applications and of potential challenging applications of the coatings.such as CVD diamond, diamondlike carbon, and cubic boron nitride-are described. Cutting tools coated with CVD diamond are of immediate commercial interest. Other applications, such as microelectromechanical systems (MEMS), valves, and bearings of CVD diamond, are being developed, but at a slow pace. There is a continually growing interest in commercializing diamondlike carbon for wear parts applications, such as biomedical parts and implants, forming dies, transport guides, magnetic tapes and disks, valves, and gears. Cubic boron nitride films are receiving attention because they can be used on tools to machine ferrous materials or on wear parts in sliding contact with ferrous materials.

Miyoshi, Kazuhisa↗

Remote Raman - laser induced breakdown spectroscopy (LIBS) geochemical investigation under Venus atmospheric conditions

The extreme Venus surface temperatures ({approx}740 K) and atmospheric pressures ({approx}93 atm) create a challenging environment for surface missions. Scientific investigations capable of Venus geochemical observations must be completed within hours of landing before the lander will be overcome by the harsh atmosphere. A combined remote Raman - LIBS (Laser Induced Breakdown Spectroscopy) instrument is capable of accomplishing the geochemical science goals without the risks associated with collecting samples and bringing them into the lander. Wiens et al. and Sharma et al. demonstrated that both analytical techniques can be integrated into a single instrument capable of planetary missions. The focus of this paper is to explore the capability to probe geologic samples with Raman - LIBS and demonstrate quantitative analysis under Venus surface conditions. Raman and LIBS are highly complementary analytical techniques capable of detecting both the mineralogical and geochemical composition of Venus surface materials. These techniques have the potential to profoundly increase our knowledge of the Venus surface composition, which is currently limited to geochemical data from Soviet Venera and VEGA landers that collectively suggest a surface composition that is primarily tholeiitic basaltic with some potentially more evolved compositions and, in some locations, K-rich trachyandesite. These landers were not equipped to probe the surface mineralogy as can be accomplished with Raman spectroscopy. Based on the observed compositional differences and recognizing the imprecise nature of the existing data, 15 samples were chosen to constitute a Venus-analog suite for this study, including five basalts, two each of andesites, dacites, and sulfates, and single samples of a foidite, trachyandesite, rhyolite, and basaltic trachyandesite under Venus conditions. LIBS data reduction involved generating a partial least squares (PLS) model with a subset of the rock powder standards to quantitatively determine the major elemental abundance of the remaining samples. PLS analysis suggests that the major element compositions can be determined with root mean square errors ca. 5% (absolute) for SiO{sub 2}, Al{sub 2}O{sub 3}, Fe{sub 2}O{sub 3}(total), MgO, and CaO, and ca. 2% or less for TiO{sub 2}, Cr{sub 2}O{sub 3}, MnO, K{sub 2}O, and Na{sub 2}O. Finally, the Raman experiments have been conducted under supercritical CO{sub 2} involving single-mineral and mixed-mineral samples containing talc, olivine, pyroxenes, feldspars, anhydrite, barite, and siderite. The Raman data have shown that the individual minerals can easily be identified individually or in mixtures.

36 MATERIALS SCIENCE↗

Demonstration and analysis of a 600 V, 10 A, 4H-SiC lateral single RESURF MOSFET for power ICs applications

This paper reports the demonstration of a 600 V 4H-SiC lateral MOSFET with a large current handling capability (10 A). To achieve a high breakdown voltage in a lateral architecture, a REduced SURface Field (RESURF) structure was implemented to alleviate surface electric field crowding. A single RESURF (P-top) design on an N-drift on a 6-in. N+ substrate demonstrated a voltage supporting capability of 120 V/ μ m, resulting in a breakdown voltage of 600 V. The total width of 198 mm for the interdigitated gate fingers was designed to accomplish the high current capability. It turned out that, for relatively low voltage SiC lateral MOSFETs (<600 V), more focus needs to be placed on achieving a low channel, contact, metal, and JFET region resistance than a low drift layer resistance to further improve the on-resistance. Device design, fabrication, and electrical characterization of the proposed 600 V, 10 A, 4H-SiC lateral single RESURF MOSFETs are discussed in this paper.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Filamentary surface plasma discharge flow length and time scales

Nanosecond surface dielectric barrier discharges (ns-SDBDs) are a class of plasma actuators that utilize a high-voltage pulse of nanosecond duration between two surface-mounted electrodes to create an electrical breakdown of air, along with rapid heating. These actuators usually produce multiple filaments when operated at high pulse frequencies, and the rapid heating leads to the formation of shock waves and complex flow fields. In this work we replicate a single filament of the ns-SDBDs and characterize the induced flow using velocity measurements from particle image velocimetry and density measurements from background-oriented schlieren. The discharge is produced by a high voltage electrical pulse between two copper electrodes on an acrylic base. A hot gas kernel characterizes the flow field formed close to the electrodes that expands and cools over time and a vortex ring that propagates away from the surface while entraining cold ambient fluid. The gas density deficit inside the kernel displays a power-law decay over time. Based on the observations, we develop a simplified theoretical model based on vortex-driven cooling and perform a scaling analysis to obtain the induced flow length and time scales. The results show that the cooling process's time scales correspond to a circulation-based time scale of the vortex ring, and the length scale of the kernel corresponds to the vortex ring radius. Furthermore, these findings can guide the choice of optimal filament spacing and pulse frequencies in the design, deployment, and operation of ns-SDBDs for flow control.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Kinetic simulations of gas breakdown in the dense plasma focus

We describe the first fully-kinetic, collisional, and electromagnetic simulations of the breakdown phase of a MA-scale dense plasma focus and are shown to agree with measured electrical characteristics, including breakdown time. In the model, avalanche ionization is driven by cathode electron emission and this results in incomplete gas breakdown along the insulator. This reinforces the importance of the conditioning process that creates a metallic layer on the insulator surface. The simulations, nonetheless, help explain the relationship between the gas pressure, the insulator length, and the coaxial gap width. In the past, researchers noted three breakdown patterns related to pressure. Simulation and analytic results show that at low pressures, long ionization path lengths lead to volumetric breakdown, while high pressures lead to breakdown across the relatively small coaxial electrode gap. In an intermediate pressure regime, ionization path lengths are comparable to the insulator length which promotes ideal breakdown along the insulator surface.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Study of dielectric breakdown in liquid xenon with XeBrA: The xenon breakdown apparatus

Maintaining the electric fields necessary for the current generation of noble liquid time projection chambers (TPCs), with drift lengths exceeding 1 m, requires a large negative voltage applied to their cathode. Delivering such high voltage is associated with an elevated risk of electrostatic discharge and electroluminescence, which would be detrimental to the performance of the experiment. The Xenon Breakdown Apparatus (XeBrA) is a 5-l, high voltage test chamber built to investigate the contributing factors to electrical breakdown in noble liquids. Here, in this work, we present the main findings after conducting scans over stressed electrode areas, surface finish, pressure, and high voltage ramp speed in the medium of liquid xenon. Area scaling and surface finish were observed to be the dominant factors affecting breakdown, whereas no significant changes were observed with varying pressure or ramp speed. A general rise in both the anode current and photon rate was observed in the last 30 s, leading up to a breakdown, with a marked increase in the last couple of seconds. In addition, the position of breakdowns was reconstructed with a system of high-speed cameras and a moderate correlation with the Fowler–Nordheim field emission model was found. Tentative evidence for bubble nucleation being the originating mechanism of breakdown in the liquid was also observed. We deem the results presented in this work to be of particular interest for the design of future, large TPCs, and practical recommendations are provided.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

X ray photoelectron analysis of oxide-semiconductor interface after breakdown in Al{sub 2}O{sub 3}/InGaAs stacks

In this work, the post-breakdown characteristics of metal gate/Al{sub 2}O{sub 3}/InGaAs structures were studied using surface analysis by x ray photoelectron spectroscopy. The results show that for dielectric breakdown under positive bias, localized filaments consisting of oxidized substrate atoms (In, Ga and As) were formed, while following breakdown under negative bias, a decrease of oxidized substrate atoms was observed. Such differences in the microstructure at the oxide-semiconductor interface after breakdown for positive and negative voltages are explained by atomic diffusion of the contact atoms into the gate dielectric in the region of the breakdown spot by the current induced electro-migration effect. These findings show a major difference between Al{sub 2}O{sub 3}/InGaAs and SiO{sub 2}/Si interfaces, opening the way to a better understanding of the breakdown characteristics of III-V complementary-metal-oxide-semiconductor technology.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Characterization of Ice Roughness Variations in Scaled Glaze Icing Conditions

Because of the significant influence of surface tension in governing the stability and breakdown of the liquid film in flooded stagnation regions of airfoils exposed to glaze icing conditions, the Weber number is expected to be a significant parameter governing the formation and evolution of ice roughness. To investigate the influence of the Weber number on roughness formation, 53.3-cm (21-in.) and 182.9-cm (72-in.) NACA 0012 airfoils were exposed to flow conditions with essentially the same Weber number and varying stagnation collection efficiency to illuminate similarities of the ice roughness created on the different airfoils. The airfoils were exposed to icing conditions in the Icing Research Tunnel (IRT) at the NASA Glenn Research Center. Following exposure to the icing event, the airfoils were then scanned using a ROMER Absolute Arm scanning system. The resulting point clouds were then analyzed using the self-organizing map approach of McClain and Kreeger (2013) to determine the spatial roughness variations along the surfaces of the iced airfoils. The roughness characteristics on each airfoil were then compared using the relative geometries of the airfoil. The results indicate that features of the ice shape and roughness such as glaze-ice plateau limits and maximum airfoil roughness were captured well by Weber number and collection efficiency scaling of glaze icing conditions. However, secondary ice roughness features relating the instability and waviness of the liquid film on the glaze-ice plateau surface are scaled based on physics that were not captured by the local collection efficiency variations.

Roughness Formation↗

Adaptation of ion beam technology to microfabrication of solid state devices and transducers

It was found that ion beam texturing of silicon surfaces can be used to increase the effective surface area of MOS capacitors. There is, however, a problem with low dielectric breakdown. Preliminary work was begun on the fabrication of ion implanted resistors on textured surfaces and the potential improvement of wire bond strength by bonding to a textured surface. In the area of ion beam sputtering, the techniques for sputtering PVC were developed. A PVC target containing valinomycin was used to sputter an ion selective membrane on a field effect transistor to form a potassium ion sensor.

Topich, J. A.↗

Partial Least Squares and Neural Networks for Quantitative Calibration of Laser-induced Breakdown Spectroscopy (LIBs) of Geologic Samples

The ChemCam instrument [1] on the Mars Science Laboratory (MSL) rover will be used to obtain the chemical composition of surface targets within 7 m of the rover using Laser Induced Breakdown Spectroscopy (LIBS). ChemCam analyzes atomic emission spectra (240-800 nm) from a plasma created by a pulsed Nd:KGW 1067 nm laser. The LIBS spectra can be used in a semiquantitative way to rapidly classify targets (e.g., basalt, andesite, carbonate, sulfate, etc.) and in a quantitative way to estimate their major and minor element chemical compositions. Quantitative chemical analysis from LIBS spectra is complicated by a number of factors, including chemical matrix effects [2]. Recent work has shown promising results using multivariate techniques such as partial least squares (PLS) regression and artificial neural networks (ANN) to predict elemental abundances in samples [e.g. 2-6]. To develop, refine, and evaluate analysis schemes for LIBS spectra of geologic materials, we collected spectra of a diverse set of well-characterized natural geologic samples and are comparing the predictive abilities of PLS, cascade correlation ANN (CC-ANN) and multilayer perceptron ANN (MLP-ANN) analysis procedures.

Anderson, R. B.↗

Formation and breakdown of a protective layer of chromium sesquioxide on L-605 alloy at 1100 C

The formation and breakdown of a protective layer of Cr2O3 on the cobalt-base alloy L-605 during oxidation at 1100 C was evaluated. Deformed surface layers, pressure, and moisture were variables. Increasing surface deformation, decreasing pressure, and decreasing moisture increased time to breakdown. A model was deduced. The breakdown of the Cr2O3 layer was caused by a combination of growth stresses and volatilization. Breakdown exposed a chromium-depleted alloy to air, resulting in very rapid oxidation, which continued until consumption of the depletion zone was complete.

Lowell, C. E.↗

Fermi surface in the absence of a Fermi liquid in the Kondo insulator SmB 6

The search for a Fermi surface in the absence of a conventional Fermi liquid has thus far yielded very few potential candidates. Among promising materials are spin-frustrated Mott insulators near the insulator–metal transition, where theory predicts a Fermi surface associated with neutral low-energy excitations. In this paper, we reveal another route to experimentally realize a Fermi surface in the absence of a Fermi liquid by the experimental study of a Kondo insulator SmB 6 positioned close to the insulator–metal transition. We present experimental signatures down to low temperatures (<<1 K) associated with a Fermi surface in the bulk, including a sizeable linear specific heat coefficient, and on the application of a finite magnetic field, bulk magnetic quantum oscillations, finite quantum oscillatory entropy, and substantial enhancement in thermal conductivity well below the charge gap energy scale. Finally, the weight of evidence indicates that despite an extreme instance of Fermi liquid breakdown in Kondo insulating SmB 6 , a Fermi surface arises from novel itinerant low-energy excitations that couple to magnetic fields, but not weak DC electric fields.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

CRADA Final Report, 2011S003, Faraday Technologies

This Phase I SBIR program addressed the need for an improved manufacturing process for electropolishing niobium RF superconducting cavities for the International Linear Collider (ILC). The ILC is a proposed particle accelerator that will be used to gain a deeper understanding of the forces of energy and matter by colliding beams of electrons and positrons at nearly the speed of light. The energy required for this to happen will be achieved through the use of advanced superconducting technology, specifically ~16,000 RF superconducting cavities operating at near absolute zero. The RF superconductor cavities will be fabricated from highly pure Nb, which has an extremely low surface resistance at 2 Kelvin when compared to other materials. To take full advantage of the superconducting properties of the Nb cavities, the inner surface must be a) polished to a microscale roughness < 0.1 µm with removal of at least 100 µm of material, and b) cleaned to be free of impurities that would degrade performance of the ILC. State-of-the-art polishing uses either chemical polishing or electropolishing, both of which require hydrofluoric acid to achieve breakdown of the strong passive film on the surface. In this Phase I program, Faraday worked with its collaborators at the Thomas Jefferson National Accelerator Facility (JLab) to demonstrate the feasibility of an electropolishing process for pure niobium, utilizing an environmentally benign alternative to chemical or electrochemical polishing electrolytes containing hydrofluoric acid. Faraday utilized a 31 wt% aqueous sulfuric acid solution (devoid of hydrofluoric acid) in conjunction with the FARADAYICSM Process, which uses pulse/pulse reverse fields for electropolishing, to demonstrate the ability to electropolish niobium to the desired surface finish. The anticipated benefits of the FARADAYICSM Electropolishing process will be a simpler, safer, and less expensive method capable of surface finishing high purity niobium cavities. Another potential benefit would be for the medical industry that uses hydrofluoric acid to electropolish niobium-alloy materials. The FARADAYICSM Electropolishing process will eliminate the environmental hazards posed by the use of hydrofluoric acid employed by chemical polishing and conventional electropolishing. Further, improved performance benefits may be possible. The overall objective of the Phase I program was to demonstrate that FARADAYIC Electropolishing of niobium cavities in electrolytes free of hydrofluoric acid can meet the RF superconducting performance criteria of those cavities. The FARADAYIC Electropolishing Process developed in the Phase I program was used to polish 50 mm Nb disks to a surface roughness (RA) of < 1 nm over a small area through process and post-processing optimization. An excellent level of surface cleanliness was achieved. While the desired 2K RF performance has not yet been achieved, Faraday believes that surface oxide state can be controlled through manipulation of the process parameters, to meet the 2K RF standard. Faraday is establishing apparatus and facilities infrastructure for single-cell SRF cavity electropolishing, through a synergistic effort with the Fermi National Accelerator Facility (Fermilab) to scale-up electropolishing of superconducting RF cavities. Faraday proposes to commercialize the subject technology via an IP based strategic relationship with a partner with established market channels within two primary commercialization avenues: 1) the superconducting particle accelerator community, 2) the medical device and implant market. Faraday will initially maintain Low Rate Initial Production capabilities for an application, but latterly seek a strategic partner who is solely dedicated to high rate production.

36 MATERIALS SCIENCE↗

Hydroxide melt induced corrosion of Ni at elevated temperatures under steam electrolysis conditions

Molten alkali electrolyte based high temperature water electrolysis (HTWE) process offers an efficient pathway to integrate renewable energy resources for large scale and economic hydrogen production. Long term and stable operation of these systems require an in-depth understanding of materials stability under anodic and cathodic exposure conditions of the cell and cell stacks. In the present study, we report our findings on the corrosion of Ni in the presence and absence of (LieNa) hydroxide melt at 600 °C under oxidizing and reducing conditions representative of HTWE. While the Ni electrode was found to remain thermodynamically stable in metallic form under cathodic (reducing) exposure conditions, the corrosion rate in molten hydroxide under oxidizing conditions was found to be nonparabolic in nature. A cyclic voltammetry study provides the breakdown of the passive metal-oxide surface layer at the anodic overpotential region between 0.45 V and 2 V in molten hydroxide under oxidizing conditions. As a result, a thermochemical process for accelerated corrosion based on the oxide scale fluxing in hydroxide melt has been developed.

08 HYDROGEN↗

Three-Dimensional Chiral Lattice Fermion in Floquet Systems

Here, we show that the Nielsen-Ninomiya no-go theorem still holds on a Floquet lattice: there is an equal number of right-handed and left-handed Weyl points in a three-dimensional Floquet lattice. However, in the adiabatic limit, where the time evolution of the low-energy subspace is decoupled from the high-energy subspace, we show that the bulk dynamics in the low-energy subspace can be described by Floquet bands with extra left- or right-handed Weyl points, despite the no-go theorem. Assuming adiabatic evolution of two bands, we show that the difference of the number of right-handed and left-handed Weyl points equals twice the winding number of the adiabatic Floquet operator over the Brillouin zone. Based on these findings, we propose a realization of purely left- or right-handed Weyl particles on a 3D lattice using a Hamiltonian obtained through dimensional reduction of a four-dimensional quantum Hall system. We argue that the breakdown of the adiabatic approximation on the surface facilitates unusual closed orbits of wave packets in an applied magnetic field, which traverse alternatively through the low-energy and high-energy sector of the spectrum.

74 ATOMIC AND MOLECULAR PHYSICS↗

Acidic attack of perfluorinated alkyl ether lubricant molecules by metal oxide surfaces

The reactions of linear perfluoropolyalkylether (PFAE) lubricants with alpha-Fe2O3 and Fe2O3-based solid superacids were studied. The reaction with alpha-Fe2O3 proceeds in two stages. The first stage is an initial slow catalytic decomposition of the fluid. This reaction releases reactive gaseous products which attach the metal oxide and convert it to FeF3. The second stage is a more rapid decomposition of the fluid, effected by the surface FeF3. A study of the inital breakdown step was performed using alpha-Fe2O3, alpha-Fe2O3 preconverted to FeF3, and sulfate-promoted alpha-Fe2O3 superacids. The results indicate that the breakdown reaction involves acidic attack at fluorine atoms on acetal carbons in the linear PFAE. Possible approaches to combat the problem are outlined.

Zehe, Michael J.↗