RF Models for Plasma-Surface Interactions
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Deuterium and helium plasma exposures on bulk TiB2 and ZrB2 samples were performed using the PISCES-RF linear plasma device. 40 and 90 eV deuterium ion plasma exposures were performed at 240 and 800 °C sample temperatures, and 80 eV helium ion plasma exposures were performed at 800 °C sample temperatures. Following plasma exposures, it was discovered that two plasma conditions (90 eV deuterium and 80 eV helium at 800 °C) resulted in thick (>200 nm) tantalum-rich (>10 at%) surface features on the targets, presumably from tantalum sourced from a tantalum adapter mask or cap used as part of the target holder. This work aims to characterize these tantalum-rich features and examine the mechanisms of impurity deposition.Plasma-induced surface morphology of the tantalum-rich surface layers depends on plasma properties and target temperature and chemistry. Greater titanium sputtering compared to zirconium resulted in more distinct surface features in the TiB2 samples compared to the ZrB2 samples via increased, prompt deposition onto tantalum surface impurities. There is still uncertainty as to why thick tantalum deposition only occurred under some plasma exposure conditions but not others; it is likely due to tantalum sputtering by a combination of boron molecules from the targets and carbon-impurities in the tantalum mask or targets. Impurity driven surface features are a well-documented phenomena in samples exposed to plasma from linear plasma device facilities—this work confirms the occurrence of this and emphasizes the need for chemistry characterization of isolated post-mortem surface features in plasma-exposed samples.
Lithium sulfide (Li 2 S) is under intense study because it is the insulating discharge product of ultra-high energy density lithium-sulfur (Li-S) batteries and a candidate cathode material for lithium metal-free Li-S cells. In this work, we report the fabrication of an apparatus for sputter deposition of Li 2 S films ranging in thickness from a few nanometers to several microns at rates over 2 nm min -1 . High-temperature annealing of the films is shown to produce crystalline films of high chemical purity Li 2 S for the first time. We provide evidence that sputter deposition produces a unique sulfide structure composed of chains of Li 2 S units, and that the electrochemistry of these films is markedly different from annealed crystalline Li 2 S, which is shown to be electrochemically inactive. Lastly, we explore trends in the plasma chemistry that lead to nonstoichiometry and depth inhomogeneity during Li 2 S sputter deposition.
The review of recent theoretical and experimental research on the complex surface chemistry processes that evolve from low-Z material conditioning on plasma-facing materials under extreme fusion plasma conditions is presented. A combination of multi-scale computational physics and chemistry modeling with real-time diagnosis of the plasma-material interface in tokamak fusion plasma edge is complemented by ex-vessel in-situ single-effect experimental facilities to unravel the evolving characteristics of low-Z components under irradiation. Effects of the lithium and boron coatings at carbon surfaces to the retention of deuterium and chemical sputtering of the plasma-facing surfaces are discussed in detail. The critical role of oxygen in the surface chemistry during hydrogen-fuel irradiation is found to drive the kinetics and dynamics of these surfaces as they interact with fusion edge plasma that ultimately could have profound effects on fusion plasma confinement behavior. Computational studies also extend in spatio-temporal scales not accessible by empirical means and therefore open the opportunity for a strategic approach at irradiation surface science studies that combined these powerful computational tools with in-vessel and ex-vessel in-situ diagnostics.
We often look "through a glass, darkly" at solar system bodies with tenuous atmospheres and direct surface exposure to the local space environment. Space weathering exposure acts via universal space-surface interaction processes to produce a thin patina of outer material covering, potentially obscuring endogenic surface materials of greatest interest for understanding origins and interior evolution. Examples of obscuring exogenic layers are radiation crusts on cometary nuclei and iogenic components of sulfate hydrate deposits on the trailing hemisphere of Europa. Weathering processes include plasma ion implantation into surfaces, sputtering by charged particles and solar ultraviolet photons, photolytic chemistry driven by UV irradiation, and radiolytic chemistry evolving from products of charged particle irradiation. Regolith structure from impacts, and underlying deeper structures from internal evolution, affects efficacy of certain surface interactions, e.g. sputtering as affected by porosity and surface irradiation dosage as partly attenuated by local topographic shielding. These processes should be regarded for mission science planning as potentially enabling, e.g. since direct surface sputtering, and resultant surface-bound exospheres, can provide in-situ samples of surface composition to ion and neutral mass spectrometers on orbital spacecraft. Sample return for highest sensitivity compOSitional and structural analyses at Earth will usually be precluded by limited range of surface sampling, long times for return, and high cost. Targeted advancements in instrument technology would be more cost efficient for local remote and in-situ sample analysis. More realistic laboratory simulations, e.g. for bulk samples, are needed to interpret mission science observations of weathered surfaces. Space environment effects on mission spacecraft and science operations must also be specified and mitigated from the hourly to monthly changes in space weather and from longer term (e.g., solar cycle) evolution of space climate. Capable instrumentation on planetary missions can and should be planned to contribute to knowledge of interplanetary space environments. Evolving data system technologies such as virtual observatories should be explored for more interdisciplinary application to the science of planetary surface, atmospheric, magnetospheric, and interplanetary interactions.
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The Cassini Ultraviolet Imaging Spectrograph (UVIS) has major new findings in all aspects of Saturn science: Saturn, its rings, Titan and the icy satellites, and the Saturn magnetosphere. Dynamic interactions between neutrals, ions, rings, moons and meteoroids produce a highly structured and time variable Saturn system. Highlights and outstanding new results will be reported, focusing on Saturn s moons and their interaction with their environment. The UVIS is one of Cassini s suite of remote sensing instruments. The UVIS instrument includes channels for extreme UV (55 to 110 nm) and far UV (110 to 190 nm) spectroscopic imaging, high speed photometry of stellar occultations, solar EUV occultation, and a hydrogen/deuterium absorption cell. UVIS has detected products of water dissociation, neutral oxygen and OH, which dominate the Saturn inner magnetosphere, in contrast to Jupiter, and H fills the entire magnetosphere apparently extending through the magnetopause at far greater density than the ion population. The O and OH and a fraction of the H are probably the products of water physical chemistry, and derived ultimately from water ice. Observed fluctuations indicate close interactions with plasma sources. Sputtering from the satellites water ice surfaces is insufficient to supply the observed mass. Stochastic events in the E ring may be the ultimate source.
The surface structure and cathodoluminescence (CL) spectra of thin films of Y{sub 2}O{sub 3}:Eu obtained by HF ion plasma sputtering were investigated by varying the activator concentration in the range of 1.0–7.5 mole%. The possibility of creating irregular solutions of yttrium and europium oxides and the structural features of the small and large crystallites that form the Y{sub 2}O{sub 3}:Eu film were demonstrated on the basis of the shape of the CL spectra at different activator concentrations. The critical distance for interaction between the Eu{sup 3+} ions at nodes with C{sub 2} and C{sub 3i} point symmetry was estimated, and a mechanism of energy migration between these centers was proposed.
Anticipating the plasma and electrical environments in permanently shadowed regions (PSRs) of the moon is critical in understanding local processes of space weathering, surface charging, surface chemistry, volatile production and trapping, exo-ion sputtering, and charged dust transport. In the present study, we have employed the open-source XOOPIC code [I] to investigate the effects of solar wind conditions and plasma-surface interactions on the electrical environment in PSRs through fully two-dimensional pattic1e-in-cell simulations. By direct analogy with current understanding of the global lunar wake (e.g., references) deep, near-terminator, shadowed craters are expected to produce plasma "mini-wakes" just leeward of the crater wall. The present results (e.g., Figure I) are in agreement with previous claims that hot electrons rush into the crater void ahead of the heavier ions, fanning a negative cloud of charge. Charge separation along the initial plasma-vacuum interface gives rise to an ambipolar electric field that subsequently accelerates ions into the void. However, the situation is complicated by the presence of the dynamic lunar surface, which develops an electric potential in response to local plasma currents (e.g., Figure Ia). In some regimes, wake structure is clearly affected by the presence of the charged crater floor as it seeks to achieve current balance (i.e. zero net current to the surface).
A detailed treatment is presented of the dialog known as plasma surface interactions (PSI) with respect to the coating process and its tribological behavior. Adsorption, morphological changes, defect formation, sputtering, chemical etching, and secondary electron emission are all discussed as promoting and enhancing the surface chemistry, thus influencing the tribological properties of the deposited flux. Phenomenological correlations of rate of deposition, flux composition, microhardness, and wear with the plasma layer variables give an insight to the formation of chemical bonding between the deposited flux and the substrate surface.
Rene 41 and Ti-6Al-4V alloys were radio frequency sputter coated with titanium carbide by several techniques in order to determine the most effective. Coatings were evaluated in pin-on-disk tests. Surface analysis by X-ray photoelectron spectroscopy was used to relate adherence to interfacial chemistry. For Rene 41, good coating adherence was obtained when a small amount of acetylene was added to the sputtering plasma. The acetylene carburized the alloy surface and resulted in better bonding to the TiC coating. For Ti-6Al-4V, the best adherence and wear protection was obtained when a pure titanium interlayer was used between the coating and the alloy. The interlayer is thought to prevent the formation of a brittle, fracture-prone, aluminum oxide layer.
Inductively coupled plasma (ICP)–reactive ion etching (RIE) patterning is a standard processing step for UV and optical photonic devices based on III-nitride materials. There is little research on ICP-RIE of high Al-content AlGaN alloys and for nonpolar nitride orientations. The authors present a comprehensive study of the ICP-RIE of c- and a-plane AlGaN in Cl{sub 2}/Ar plasma over the entire Al composition range. The authors find that the etch rate decreases in general with increasing Al content, with different behavior for c- and a-plane AlGaN. They also study the effect of BCl{sub 3} deoxidizing plasma pretreatment. An ICP deoxidizing BCl{sub 3} plasma with the addition of argon is more efficient in removal of surface oxides from Al{sub x}Ga{sub 1−x}N than RIE alone. These experiments show that Al{sub x}Ga{sub 1−x}N etching is affected by the higher binding energy of AlN and the higher affinity of oxygen to aluminum compared to gallium, with oxides on a-plane AlGaN more difficult to etch as compared to oxides on c-plane AlGaN, specifically for high Al composition materials. The authors achieve reasonably high etch rate (∼350 nm/min) for high Al-content materials with a smooth surface morphology at a low DC bias of ∼−45 VDC.
This work demonstrates the use of focused ion beam (FIB) implanted Ga as a lithographic mask for plasma etching of Nb films. Using a highly collimated Ga beam of a FIB, Nb is implanted 12 nm deep with a 14 nm thick Ga layer providing etch selectivity better than 15:1 with fluorine based etch chemistry. Implanted square test patterns, both 10 μm by 10 μm and 100 μm by 100 μm, demonstrate that doses above than 7.5 × 10{sup 15 }cm{sup −2} at 30 kV provide adequate mask protection for a 205 nm thick, sputtered Nb film. The resolution of this dry lithographic technique is demonstrated by fabrication of nanowires 75 nm wide by 10 μm long connected to 50 μm wide contact pads. The residual resistance ratio of patterned Nb films was 3. The superconducting transition temperature (T{sub c}) = 7.7 K was measured using a magnetic properties measurement system. This nanoscale, dry lithographic technique was extended to sputtered TiN and Ta here and could be used on other fluorine etched superconductors such as NbN, NbSi, and NbTi.
The field of plasma etching is reviewed. Plasma etching, a revolutionary extension of the technique of physical sputtering, was introduced to integrated circuit manufacturing as early as the mid 1960s and more widely in the early 1970s, in an effort to reduce liquid waste disposal in manufacturing and achieve selectivities that were difficult to obtain with wet chemistry. Quickly, the ability to anisotropically etch silicon, aluminum, and silicon dioxide in plasmas became the breakthrough that allowed the features in integrated circuits to continue to shrink over the next 40 years. Some of this early history is reviewed, and a discussion of the evolution in plasma reactor design is included. Some basic principles related to plasma etching such as evaporation rates and Langmuir–Hinshelwood adsorption are introduced. Etching mechanisms of selected materials, silicon, silicon dioxide, and low dielectric-constant materials are discussed in detail. A detailed treatment is presented of applications in current silicon integrated circuit fabrication. Finally, some predictions are offered for future needs and advances in plasma etching for silicon and nonsilicon-based devices.
Plasma facing surfaces (PFS) have a profound influence on plasma performance and choice of material for PFSs is a burning issue for tokamak reactors. Using lithium wall conditioning in NSTX has resulted in a beneficial influence on plasma behavior including control of hydrogen recycling and improvements in energy confinement, longer confinement times, edge density control, and the elimination of Edge Localized Modes. A major challenge for the NSTX-U (increased power flux, increased campaign time) as well as for other magnetic fusion devices is to extend high-performance plasmas for very long durations, and to integrate this high performance with plasma facing components (PFCs) that can withstand very high heat and particle fluxes while maintaining structural integrity with minimal retention of fusion fuel. This project directly contributed to filling up the knowledge gaps and data for the dynamics of the plasma-facing interfaces in the NSTX-U at nano and nano-to-micro scales. This was achieved by both deciphering the poorly understood nanoscale phenomenology of plasma-surface interactions and providing the connection and comparison with the experiments which provide understanding at the mesoscopic scales. We modelled the dynamic response and evolution of a mixed material surfaces (D, Li, C, B, O) to bombardment by plasma particles, and investigated microstructure changes, erosion, surface chemistry, deuterium implantation and permeation. The main objectives of the project are i) a comparison of Li and B effects when deposited on carbon, and ii) the role of oxygen and other impurities (e.g. carbon, boron) in the lithium performance. In addition to predicting and understanding the phenomenology of the processes, the project achieved deliverables on the i) plasma induced erosion rates of PFCs (outer wall, divertor, etc.), including chemical and physical sputtering yields at various temperatures (300-700K), ii) deuterium uptake/recycling rates, and iii) accurate probability rates for the processes and reactions in i-ii which were used to understand the experimental results of the J.P. Allain and B. Koel NSTX-U projects. Lithium was a distinctive focus of the project. It easily charges in contact with other fusion material atoms, giving partially or fully its external electron cloud to other atoms in its vicinity and polarizing the mixed material. Our research strategy used experimentally validated multiscale theory applied to the large, multicomponent material surface systems. With the use of US supercomputing facilities we simulated evolution of atomic charges, chemistry, retention of deuterium, sputtering and morphology by introducing the corrections to the classical molecular dynamics, like are electronegativity equalization method (EEM) and quantum-classical molecular dynamics (QCMD). The goal was to understand and quantify the dynamics of the creation and evolution of the plasma-material interface under irradiation by atoms and molecules at boronized carbon, lithiated carbon, and boronized-lithiated carbon for both solid and self-healing liquid-metal divertor.
We have used a combination of pico-to-nano temporal/spatial scale computational physics and chemistry modeling of plasma–material interfaces in the tokamak fusion plasma edges to unravel the evolving characteristics, not readily accessible by empirical means, of lithium-, oxygen-, and hydrogen-containing materials of plasma-facing components under irradiation by hydrogen and its isotopes. In the present calculation, amorphous lithium compound surfaces containing oxygen, Li 2 O, and LiOH were irradiated by 1-100 eV particles at incident angles on the surface ranging from perpendicular to almost grazing angles. Consequential surface processes, reflection, retention, and sputtering were studied at “the same footing” and compared to earlier results from amorphous Li and LiH surfaces. In conclusion, the critical role of charging dynamics of lithium, oxygen, and hydrogen atoms in the surface chemistry during hydrogen-fuel irradiation was found to drive the kinetics and dynamics of these surfaces in unexpected ways that ultimately could have profound effects on fusion plasma confinement behavior and surface erosion.
Structural and chemical impact of the heliospheric space environment on exposed planetary surfaces and interplanetary dust grains may be generally defined as space weathering . In the inner solar system, from the asteroid belt inwards towards the Sun, the surface regolith structures of airless bodies are primarily determined by cumulative meteoritic impacts over billions of years, but the molecular composition to meters in depth can be substantially modified by irradiation effects. Plasma ions at eV to keV energies may both erode uppermost surfaces by sputtering, and implant or locally produce exogenic material, e.g. He-3 and H2O, while more energetic ions drive molecular change through electronic ionization. Galactic cosmic ray ions and more energetic solar ions can impact chemistry to meters in depth. High energy cosmic ray interactions produce showers of secondary particles and energetic photons that present hazards for robotic and human exploration missions but also enable detection of potentially useable resources such as water ice, oxygen, and many other elements. Surface sputtering also makes ejected elemental and molecular species accessible for in-situ compositional analysis by spacecraft with ion and neutral mass spectrometers. Modeling of relative impacts for these various space weathering processes requires knowledge of the incident species-resolved ion flux spectra at plasma to cosmic ray energies and as integrated over varying time scales. Although the main drivers for investigations of these processes come from NASA's planetary science and human exploration programs, the NASA heliophysics program provides the requisite data measurement and modeling resources to enable specification of the field & plasma and energetic particle irradiation environments for application to space weather and surface weathering investigations. The Virtual Heliospheric Observatory (VHO), Virtual Energetic Particle Observatory (VEPO), Lunar Solar Origins Exploration (LunaSOX), and Space Physics Data Facility (SPDF) services now provide a wide range of inner heliospheric spacecraft data that can be applied to space weathering of potential exploration destinations including the Moon, asteroids, and the moons of Mars, as well to radiation hazard assessment for the spacecraft and human explorers. For example, the new VEPO service for time-averaging of multi-source ion flux spectra enables the specification of composite flux spectra from a variety of ongoing and legacy missions for applications to surface interaction modeling. Apollo to Artemis data resources of LunaSOX enable specific space weathering investigations for the Moon, while VHO more generally covers the space field and plasma environments of the inner and outer solar system from the sunward-most perihelia of the twin Helios spacecraft to the ongoing heliosheath passages of the twin Voyagers. Composite multi-source spectra from VEPO can also be applied to the continuing compilation of accumulated 1-AU fluence spectra, mostly contributed by solar wind plasma and energetic particle events, for determination of time-averaged particle compositional and kinetic energy output from the Sun and for modeling of long-term irradiation impacts on planetary surfaces.
We describe controlled, self-limited etching of a polystyrene polymer using a composite etching cycle consisting of sequential deposition of a thin reactive layer from precursors produced from a polymer-coated electrode within the etching chamber, modification using O{sub 2} exposure, and subsequent low-pressure Ar plasma etching, which removes the oxygen-modified deposited reactive layer along with Almost-Equal-To 0.1 nm unmodified polymer. Deposition prevents net etching of the unmodified polymer during the etching step and enables self-limited etch rates of 0.1 nm/cycle.