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DISCOVERY OF THE METHOXY RADICAL, CH{sub 3}O, TOWARD B1: DUST GRAIN AND GAS-PHASE CHEMISTRY IN COLD DARK CLOUDS

We report on the discovery of the methoxy radical (CH{sub 3}O) toward the cold and dense core B1-b based on the observation, with the IRAM 30 m radio telescope, of several lines at 3 and 2 mm wavelengths. Besides this new molecular species we also report on the detection of many lines arising from methyl mercaptan (CH{sub 3}SH), formic acid (HCOOH), propynal (HCCCHO), acetaldehyde (CH{sub 3}CHO), dimethyl ether (CH{sub 3}OCH{sub 3}), methyl formate (CH{sub 3}OCOH), and the formyl radical (HCO). The column density of all these species is {approx_equal}10{sup 12} cm{sup -2}, corresponding to abundances of {approx_equal}10{sup -11}. The similarity in abundances for all these species strongly suggest that they are formed on the surface of dust grains and ejected to the gas phase through non-thermal desorption processes, most likely cosmic rays or secondary photons. Nevertheless, laboratory experiments indicate that the CH{sub 3}O isomer released to the gas phase is CH{sub 2}OH rather than the methoxy one. Possible gas-phase formation routes to CH{sub 3}O from OH and methanol are discussed.

79 ASTRONOMY AND ASTROPHYSICS↗

UNESE Data Analysis-Disko Elm Gas Transport Characteristics (NA-22 Quarterly Report)

Recently published papers have demonstrated the impact of sorption mechanisms on gas transport in the subsurface following an underground nuclear explosion. To include sorption processes in the multi-physics models of noble gas production and transport, researchers have conducted experiments of gas sorption in geologic materials and calibrated a linear (Henry’s law) sorption model for all gases in various geologic materials. As a part of Task #4, we requested the experimental data from Sandia Laboratories and derived a dual-mode (Henry’s absorption and Langmuir adsorption) sorption model. The derived model better describes the nonlinear sorption mechanism with much higher fitness with the experimental data. When gas concentrations are relatively low (in the conditions of field experiments or underground nuclear explosions) compared to those used sorption experiments, the nonlinear sorption model can be approximated as a linear sorption model. The equivalent Henry’s constant, which equals the product of Langmuir capacity and affinity, is systematically higher than the literature values. Further analyses and comparison of sorption models are planned in FY2020 Q4 and the sorption model will be coupled in models of nonisothermal multiphase transport for studying noble gas detectability.

58 GEOSCIENCES↗

A numerical assessment of cosmic-ray energy diffusion through turbulent media

How and where cosmic rays are produced, and how they diffuse through various turbulent media, represent fundamental problems in astrophysics with far-reaching implications, both in terms of our theoretical understanding of high-energy processes in the Milky Way and beyond, and the successful interpretation of space-based and ground based GeV and TeV observations. For example, recent and ongoing detections, e.g., by Fermi (in space) and HESS (in Namibia), of γ-rays produced in regions of dense molecular gas hold important clues for both processes. In this paper, we carry out a comprehensive numerical investigation of relativistic particle acceleration and transport through turbulent magnetized environments in order to derive broadly useful scaling laws for the energy diffusion coefficients.

79 ASTRONOMY AND ASTROPHYSICS↗

Front-End Processes for Conversion of Current HEU-Based Alkaline Processes to LEU Foil Targets: Volumes and Compositions of All Waste, Product, and Off-Gas Streams from Both Front-End Options

The Global Threat Reduction Initiative (GTRI) Conversion Program develops technology necessary to enable the conversion of civilian facilities using high enriched uranium (HEU) to low enriched uranium (LEU) fuels and targets. The main technology components of the program are as follows: • The development of advanced LEU fuels, • Design and safety analysis for research reactor conversion, and • Development of targets and processes for the non-HEU production of the medical isotope molybdenum-99 ( 99 Mo).

Jerden Jr., James L.↗

Strategies to Valorize the Hydrothermal Liquefaction-Derived Aqueous Phase into Fuels and Chemicals

Valorization options for the aqueous fraction produced by the hydrothermal liquefaction of terrestrial feedstocks were developed. The processes focused on carboxylic acids, which are abundant in the aqueous fraction. A clean up process for the aqueous phase based on activated carbon absorption followed by liquid-liquid extraction was demonstrated that significantly reduces color bodies and inorganic contaminants while simultaneously concentrating desirable organic constituents. Conversion of the cleaned aqueous phase was then demonstrated for both a ketonization reaction and steam reforming. Condensed phase ketonization over LaxZryOz catalyst was found to exhibit both excellent hydrothermal stability and ketonization activity. Necessity for feedstock cleanup was established and stable condensed phase ketonization operation was demonstrated for ~100 hours with HTL-process derived material. Steam reforming was also demonstrated by employing a dual-bed catalyst configuration whereby carboxylic acids first undergo ketonization over CeO2 in the vapor phase followed by steam reforming of the ketone intermediates over Co/CeO2. The dual-bed approach reduced coke deposition and thus catalyst stability improved. Techno-economic analysis was used to assess economic viability for producing fuel from the bio-oil fraction and either propene (formed via hydrogenation and dehydration of acetone, the primary ketonization product) or hydrogen from the aqueous stream. The ketonization and steam reforming cases were separately modeled and benchmarked to a process utilizing anaerobic digestion. Resulting minimum fuel selling prices of $3.7, $4.2, and $4.3/GGE were obtained for the production of olefins via ketonization, reduction and dehydration; steam reforming; and anaerobic digestion processes, respectively. Both the steam reforming and anaerobic digestion processes benefited by avoiding the need for natural gas by producing the hydrogen on-site required for biocrude hydrotreatment. However, the condensed ketonization process had the lowest minimum fuel selling price because of the co-product olefins generated for sale.

Biomass, hydrothermal liquefaction, techno economi↗

Enabling Staged Pressurized Oxy Combustion (SPOC): Improving Flexibility and Performance at Reduced Cost

Staged Pressurized Oxy-Combustion (SPOC) is a coal combustion power technology being developed by Washington University in St. Louis (WUSTL) that offers the potential to deliver low-carbon power at a reduced cost. Traditional oxy-combustion plants remove most of the nitrogen in air prior to combustion, thereby burning fuel in oxygen instead of air, producing a flue gas containing primarily CO 2 and water that allows relatively simple CO 2 capture at amounts > 90%. This technology relies on flue gas recycle (FGR) to reduce the peak temperature and radiation that would otherwise occur in a fuel/oxygen only flame. SPOC reduces the peak temperatures of combustion by utilizing two or more pressurized boiler modules connected in series to produce fuel staging; hence, only a portion of the fuel is combusted in any given furnace module. This means that the thermal energy released at each stage can be captured and removed from the gases prior to subsequent stages, when more fuel is introduced. This allows the SPOC process to operate with minimal FGR, avoiding the associated efficiency losses and additional costs. The SPOC process operates at an elevated gas-side pressure, reducing boiler size, enhancing heat transfer to achieve a compact boiler configuration as compared to an atmospheric-pressure boiler design, and allowing the recovery of the latent heat of the water from the flue gas at a temperature useful to the steam cycle. The resultant net efficiency of the system is up to 6 percentage points greater than traditional atmospheric-pressure oxy-combustion, representing a step-change improvement over first-generation oxy-combustion technologies. WUSTL has teamed up with the Electric Power Research Institute, Inc., American Air Liquide, Inc., Doosan Babcock Limited, and the U.S. Department of Energy to develop a practicable and workable boiler design concept associated with the application of SPOC. In particular, due to the staged nature of the heat release, the team has identified the potential for enhanced process flexibility for controlling power generation over a wider load range than is normally available to conventional coal-fired power plants. Improved flexibility is a critical need as coal power plants are being tasked with providing grid stability to balance the growth of intermittent renewables. Not only is flexible operation important, achieving efficient power generation at reduced loads will be key as the plants are likely to operate in this regime for significant periods of time as more renewables become available. At reduced loads, coal-fired steam generators typically face challenges in maintaining temperature control of the reheat steam and to a lesser extent the main steam due to the heat transfer characteristics of these circuits when flue gas quantities are lower. This results in inefficient operation, both in terms of the boiler efficiency and steam turbine heat rate. Since the SPOC process can be configured to deliver targeted heat input to each boiler circuit by adjusting the relative fuel firing rate of each stage, better temperature control can be achieved during dynamic conditions. Oxygen supply flexibility is also a key consideration for the overall flexibility of the SPOC process given the operating constraints of conventional air separation units. The boiler design concept assessment is being carried out to identify the maximum permissible compactness of the SPOC boiler heating surfaces. The assessment will determine the minimum overall height that will deliver appropriate tube operating metal temperatures at full load and achieve rated reheat steam temperatures at low operating loads, balanced against the needs of efficient coal combustion, and the resultant slagging and ash environments. The design parameters are being validated by combustion testing in the 100-kWth pressurized combustion test rig at WUSTL. Testing results and model validation that form the basis of a full-scale boiler design that will encompass both efficiency and flexibility improvements over conventional oxy-combustion processes will be presented.

20 FOSSIL-FUELED POWER PLANTS↗

EVALUATION OF SOLID SORBENTS AS A RETROFIT TECHNOLOGY FOR CO2 CAPTURE FROM COAL-FIRED POWER PLANTS

Through a U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL) funded cooperative agreement DE-NT0005649, ADA Environmental Solutions (ADA) has begun evaluating the use of solid sorbents for CO{sub 2} capture. The project objective was to address the viability and accelerate development of a solid-based CO{sub 2} capture technology. To meet this objective, initial evaluations of sorbents and the process/equipment were completed. First the sorbents were evaluated using a temperature swing adsorption process at the laboratory scale in a fixed-bed apparatus. A slipstream reactor designed to treat flue gas produced by coal-fired generation of nominally 1 kWe was designed and constructed, which was used to evaluate the most promising materials on a more meaningful scale using actual flue gas. In a concurrent effort, commercial-scale processes and equipment options were also evaluated for their applicability to sorbent-based CO{sub 2} capture. A cost analysis was completed that can be used to direct future technology development efforts. ADA completed an extensive sorbent screening program funded primarily through this project, DOE NETL cooperative agreement DE-NT0005649, with support from the Electric Power Research Institute (EPRI) and other industry participants. Laboratory screening tests were completed on simulated and actual flue gas using simulated flue gas and an automated fixed bed system. The following types and quantities of sorbents were evaluated: 87 supported amines; 31 carbon based materials; 6 zeolites; 7 supported carbonates (evaluated under separate funding); and 10 hydrotalcites. Sorbent evaluations were conducted to characterize materials and down-select promising candidates for further testing at the slipstream scale. More than half of the materials evaluated during this program were supported amines. Based on the laboratory screening four supported amine sorbents were selected for evaluation at the 1 kW scale at two different field sites. ADA designed and fabricated a slipstream pilot to allow an evaluation of the kinetic behavior of sorbents and provide some flexibility for the physical characteristics of the materials. The design incorporated a transport reactor for the adsorber (co-current reactor) and a fluidized-bed in the regenerator. This combination achieved the sorbent characterization goals and provided an opportunity to evaluate whether the potential cost savings associated with a relatively simple process design could overcome the sacrifices inherent in a co-current separation process. The system was installed at two field sites during the project, Luminant's Martin Lake Steam Electric Station and Xcel Energy's Sherburne County Generating Station (Sherco). Although the system could not maintain continuous 90% CO{sub 2} removal with the sorbents evaluated under this program, it was useful to compare the CO{sub 2} removal properties of several different sorbents on actual flue gas. One of the supported amine materials, sorbent R, was evaluated at both Martin Lake and Sherco. The 1 kWe pilot was operated in continuous mode as well as batch mode. In continuous mode, the sorbent performance could not overcome the limitations of the cocurrent adsorbent design. In batch mode, sorbent R was able to remove up to 90% CO{sub 2} for several cycles. Approximately 50% of the total removal occurred in the first three feet of the adsorption reactor, which was a transport reactor. During continuous testing at Sherco, CO{sub 2} removal decreased to approximately 20% at steady state. The lack of continuous removal was due primarily to the combination of a co-current adsorption system with a fluidized bed for regeneration, a combination which did not provide an adequate driving force to maintain an acceptable working CO{sub 2} capacity. In addition, because sorbent R consisted of a polymeric amine coated on a silica substrate, it was believed that the 50% amine loaded resulted in mass diffusion limitations related to the CO{sub 2} uptake rate. Three additional supported amine materials, sorbents AX, F, and BN, were selected for evaluation using the 1 kW pilot at Sherco. Sorbent AX was operated in batch mode and performed similarly to sorbent R (i.e. could achieve up to 90% removal when given adequate regeneration time). Sorbent BN was not expected to be subject to the same mass diffusion limitations as experienced with sorbent R. When sorbent BN was used in continuous mode the steady state CO{sub 2} removal was approximately double that of sorbent R, which highlighted the importance of sorbents without kinetic limitations.

01 COAL, LIGNITE, AND PEAT↗

On multidomain multiscale modeling and simulation of a novel partial pressure and temperature swing adsorptive reactor ($\mathrm{PPTSAR}$) with application to the water gas shift reaction

Here in this work, a dynamic, multidomain, multiscale model of a novel Partial Pressure and Temperature Swing Adsorptive Reactor (PPTSAR) Process is developed and simulated for a Water Gas Shift Reaction (WGSR) application. The proposed model couples the reactor wall, catalyst/adsorbent pellet, and fluid mixture domains at their respective scales to comprehensively model mass, momentum, and energy transport phenomena occurring within each domain. The resulting model elucidates the PPTSAR’s start-up, transient, and long-term, periodic, dynamic behavior, during both adsorption/reaction and desorption operating modes. In the WGSR application considered, the use of two PPTSARs is shown to allow continuous operation that delivers CO conversion greater than 95% with simultaneous complete CO 2 capture.

42 ENGINEERING↗

A Simple Condition for Sustained Super-Eddington Black Hole Growth

One of the most pressing questions in cosmology is how the black holes (BHs) powering quasars at high redshift grow to supermassive scales within a billion years of the Big Bang. Here we show that sustained super-Eddington accretion can be achieved for BHs with Eddington fractions f Edd ≳ 2/ϵ, where ϵ is the efficiency with which radiation is generated in the accretion process. In this regime, the radiation carries too little momentum to halt the accretion flow and the infalling gas traps the radiation. The BH growth then proceeds unimpeded until the gas supply is exhausted, in contrast to accretion at lower rates, which is limited by the radiation generated in the accretion process. The large gas supply available in massive high-redshift quasar host galaxies may be readily accreted onto seed BHs via this supply-limited mode of accretion, providing an explanation for how such supermassive BHs are assembled in the early universe. This sustained super-Eddington growth may also explain the short lifetimes inferred for the H ii regions surrounding high-redshift quasars, if the bulk of the BH growth occurs without the associated radiation escaping to ionize the intergalactic medium. It furthermore implies that a population of obscured rapidly growing BHs may be difficult to detect, perhaps explaining why so few quasars with Eddington fractions higher than a few have been observed. Finally, this simple condition for sustained super-Eddington growth can easily be implemented in cosmological simulations that can be used to assess in which environments it occurs.

79 ASTRONOMY AND ASTROPHYSICS↗

TRISO SiC Failure Probability for Reactivity Initiated Accidents in High-Temperature Gas-Cooled Reactors

This work analyzes the failure process of the silicon carbide (SiC) layer in tristructural isotropic (TRISO) during reactivity-initiated accident scenarios for a high-temperature gas-cooled reactor (HTGR) with BISON. Two cases are considered—a group control rod withdrawal (CRW) and a control rod ejection (CRE)—reproduced from a previous study. Failure probability is modeled using Weibull statistics, and worst-case scenario Weibull parameters are adopted to simulate the envelopes in BISON with a one-dimensional TRISO model. CRW scenario results are characterized by higher values of maximum energy deposition and final temperature and volumetric strain with respect to the CRE ones, but the latter have remarkably higher SiC failure probability, mainly due to the offset in strain rates between the two cases. This work also confirms the validity and conservatism of the performance envelopes produced in a previous work by replicating the envelope formulation using RELAP5-3D and RAVEN with a different sampling technique and obtaining consistent results. A sensitivity analysis using the Sobol variance decomposition method on SiC failure probability is then performed involving a set of inputs on both CRW and CRE. The two most important parameters are Weibull modulus and characteristic stress, and their relative importance depends on the specific case. The proposed interpretation of the results is that both energy deposition and strain rate influence the relative degree of importance of the failure parameters. Computation of 95% confidence intervals around worst-case scenario SiC failure probability values is also carried out for four different sets of Weibull parameters. Heren a new criterion for SiC TRISO quality classification built upon safety-based ranges of Weibull parameters is proposed to be integrated in future Fuel-Production Quality Assurance Plans.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Native top-down mass spectrometry for the structural characterization of human hemoglobin

Native mass spectrometry (MS) has become an invaluable tool for the characterization of proteins and non-covalent protein complexes under near physiological solution conditions. Here we report the structural characterization of human hemoglobin (Hb), a 64 kDa oxygen-transporting protein complex, by high resolution native top-down mass spectrometry using electrospray ionization (ESI) and a 15-Tesla Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. Native MS preserves the non-covalent interactions between the globin subunits, and electron capture dissociation (ECD) produces fragments directly from the intact Hb complex without dissociating the subunits. Using activated ion ECD, we observe the gradual unfolding process of the Hb complex in the gas phase. Without protein ion activation, the native Hb shows very limited ECD fragmentation from the N-termini, suggesting a tightly packed structure of the native complex and therefore low fragmentation efficiency. Precursor ion activation allows steady increase of N-terminal fragment ions, while the C-terminal fragments remain limited (38 c ions and 4 z ions on the α chain; 36 c ions and 2 z ions on the β chain). This ECD fragmentation pattern suggests that upon activation, the Hb complex starts to unfold from the N-termini of both subunits, whereas the C-terminal regions and therefore the potential regions involved in the subunit binding interactions remain intact. ECD-MS of the Hb dimer show similar fragmentation patterns as the Hb tetramer, providing further evidence for the hypothesized unfolding process of the Hb complex in the gas phase. Native top-down ECD-MS allows efficient probing of the Hb complex structure and the subunit binding interactions in the gas phase. Finally, it may provide a fast and effective means to probe the structure of novel protein complexes that are intractable to traditional structural characterization tools.

47 OTHER INSTRUMENTATION↗

Solar thermochemical hydrogen production with complex perovskite oxides

One promising method for solar energy storage is Solar Thermochemical Hydrogen (STCH) production. This two-step thermochemical process utilizes nonstoichiometric metal oxides to convert solar energy into hydrogen gas. The oxide first undergoes reduction via exposure to heat generated from concentrated solar power. When subsequently exposed to steam, the reduced oxide splits water molecules through its re-oxidation process, thus producing hydrogen gas. The viability of STCH depends on identifying redox-active materials that have fast redox kinetics, structural stability and low reduction temperatures. Complex perovskite oxides show promise for more efficient hydrogen production at lower reduction temperatures than current materials. In this work, a stagnation flow reactor was used to characterize the water splitting capabilities of BaCe 0.25 Mn 0.75 O 3 (BCM). In the future, the method outlined will be used to characterize structural analogues of BCM, to provide insight into the effect of material composition on water splitting behavior and ultimately guide the synthesis of more efficient STCH materials.

14 SOLAR ENERGY↗

Rigorous Kinetic Modeling and Optimization Study of a Modified Claus Unit for an Integrated Gasification Combined Cycle (IGCC) Power Plant with CO{sub 2} Capture

The modified Claus process is one of the most common technologies for sulfur recovery from acid gas streams. Important design criteria for the Claus unit, when part of an Integrated Gasification Combined Cycle (IGCC) power plant, are the ability to destroy ammonia completely and the ability to recover sulfur thoroughly from a relatively low purity acid gas stream without sacrificing flame stability. Because of these criteria, modifications to the conventional process are often required, resulting in a modified Claus process. For the studies discussed here, these modifications include the use of a 95% pure oxygen stream as the oxidant, a split flow configuration, and the preheating of the feeds with the intermediate pressure steam generated in the waste heat boiler (WHB). In the future, for IGCC plants with CO{sub 2} capture, the Claus unit must satisfy emission standards without sacrificing the plant efficiency in the face of typical disturbances of an IGCC plant, such as rapid change in the feed flow rates due to load-following and wide changes in the feed composition because of changes in the coal feed to the gasifier. The Claus unit should be adequately designed and efficiently operated to satisfy these objectives. Even though the Claus process has been commercialized for decades, most papers concerned with the modeling of the Claus process treat the key reactions as equilibrium reactions. Such models are validated by manipulating the temperature approach to equilibrium for a set of steady-state operating data, but they are of limited use for dynamic studies. One of the objectives of this study is to develop a model that can be used for dynamic studies. In a Claus process, especially in the furnace and the WHB, many reactions may take place. In this work, a set of linearly independent reactions has been identified, and kinetic models of the furnace flame and anoxic zones, WHB, and catalytic reactors have been developed. To facilitate the modeling of the Claus furnace, a four-stage method was devised so as to determine which set of linearly independent reactions would best describe the product distributions from available plant data. Various approaches are taken to derive the kinetic rate expressions, which are either missing in the open literature or found to be inconsistent. A set of plant data is used for optimal estimation of the kinetic parameters. The final model agrees well with the published plant data. Using the developed kinetics models of the Claus reaction furnace, WHB, and catalytic stages, two optimization studies are carried out. The first study shows that there exists an optimal steam pressure generated in the WHB that balances hydrogen yield, oxygen demand, and power generation. In the second study, it is shown that an optimal H{sub 2}S/SO{sub 2} ratio exists that balances single-pass conversion, hydrogen yield, oxygen demand, and power generation. In addition, an operability study has been carried out to examine the operating envelope in which both the H{sub 2}S/SO{sub 2} ratio and the adiabatic flame temperature can be controlled in the face of disturbances typical for the operation of an IGCC power plant with CO{sub 2} capture. Impact of CO{sub 2} capture on the Claus process has also been discussed.

20 FOSSIL-FUELED POWER PLANTS↗

Hybrid Capture for Net-Negative Emissions

The Energy & Environmental Research Center, in partnership with the U.S. Department of Energy and North Dakota ethanol producer Red Trail Energy, LLC (RTE), completed an initial engineering design (IED) for a potential hybrid capture system at the RTE CCS (carbon capture and storage) site. The RTE CCS Project is currently operating a CO2 capture facility, adjacent to the RTE ethanol facility in western North Dakota, and injecting the CO2 more than a mile below RTE property for permanent storage. This novel process would add capturing CO2 produced from natural gas boilers to the existing bioprocessing capture system to achieve a net-negative CO2 emissions industrial process at commercial scale (~310,000 tonnes/yr CO2). Initial findings of the IED showed the hybrid system to be technically viable with a moderate estimated cost of $55/tonne CO2 captured for the hybrid system. A cradle-to-gate life cycle assessment (LCA) was also conducted, showing preliminary net-negative carbon emissions potential anticipated from implementing a hybrid CCS system at a commercial scale. Recommended next steps toward potential implementation include hybrid capture system demonstration testing for detailed engineering and LCA model comparisons with low-carbon fuel incentive programs for financial support.

01 COAL, LIGNITE, AND PEAT↗

Designing a Nanoscale Three-phase Electrochemical Pathway to Promote Pt-catalyzed Formaldehyde Oxidation

Gas-phase heterogeneous catalysis is a process spatially constrained on the two-dimensional surface of a solid catalyst. Here, we introduce a new toolkit to open up the third dimension. We discovered that the activity of a solid catalyst can be dramatically promoted by covering its surface with a nanoscale-thin layer of liquid electrolyte while maintaining efficient delivery of gas reactants, a strategy we call three-phase catalysis. Introducing the liquid electrolyte converts the original surface catalytic reaction into an electrochemical pathway with mass transfer facilitated by free ions in a three-dimensional space. Furthermore, we chose the oxidation of formaldehyde as a model reaction and observed a 25000-times enhancement in the turnover frequency of Pt in three-phase catalysis as compared to conventional heterogeneous catalysis. We envision three-phase catalysis as a new dimension for catalyst design and anticipate its applications in more chemical reactions from pollution control to the petrochemical industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microwave ECR plasma electron flood for low pressure wafer charge neutralization

Modern ion implanters typically use dc arc discharge Plasma Electron Floods (PEFs) to neutralize wafer charge. The arc discharge requires using at least some refractory metal hardware, e.g. a thermionically emitting filament, which can be undesirable in applications where no metallic contamination is critical. rf discharge PEFs have been proposed to mitigate contamination risks but the gas flows required can result in high process chamber pressures. Axcelis has developed a microwave electron cyclotron resonance (ECR) PEF to provide refractory metals contamination-free wafer neutralization with low gas flow requirement. Our PEF uses a custom, reentrant cusp magnet field providing ECR and superior electron confinement. Stable PEF operation with extraction slits sized for 300 mm wafers can be attained at Xe gas flows lower than 0.2 sccm. Electron extraction currents can be as high as 20 mA at absorbed microwave powers < 70 W. On Axcelis' new medium current implanter, plasma generation has proven robust against pressure transients caused by, for example, photoresist outgassing by high power ion beams. Charge monitor and floating potential measurements along the wafer surface corroborate adequate wafer charge neutralization for low energy, high current ion beams.

43 PARTICLE ACCELERATORS↗

Incubation behavior of silicon nanowire growth investigated by laser-assisted rapid heating

We investigate the early stage of silicon nanowire growth by the vapor-liquid-solid mechanism using laser-localized heating combined with ex-situ chemical mapping analysis by energy-filtered transmission electron microscopy. By achieving fast heating and cooling times, we can precisely determine the nucleation times for nanowire growth. We find that the silicon nanowire nucleation process occurs on a time scale of ∼10 ms, i.e., orders of magnitude faster than the times reported in investigations using furnace processes. The rate-limiting step for silicon nanowire growth at temperatures in the vicinity of the eutectic temperature is found to be the gas reaction and/or the silicon crystal growth process, whereas at higher temperatures it is the rate of silicon diffusion through the molten catalyst that dictates the nucleation kinetics.

36 MATERIALS SCIENCE↗

Method and apparatus for physical separation of different sized nanostructures

The present application provides apparatuses and methods for the size-selective fractionation of ligand-capped nanoparticles that utilizes the tunable thermophysical properties of gas-expanded liquids. The nanoparticle size separation processes are based on the controlled reduction of the solvent strength of an organic phase nanoparticle dispersion through increases in concentration of the antisolvent gas, such as CO.sub.2, via pressurization. The method of nanomaterial separation contains preparing a vessel having a solvent and dispersed nanoparticles, pressurizing the chamber with a gaseous antisolvent, and causing a first amount of the nanoparticles to precipitate, transporting the solution to a second vessel, pressurizing the second vessel with the gaseous antisolvent and causing further nanoparticles to separate from the solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗