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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Mitigating challenges in aberration-corrected electron-beam lithography on electron-opaque substrates

Aberration-corrected electron-beam lithography (AC-EBL) using ultra-thin electron transparent membranes has achieved single-digit nanometer resolution in two widely used electron-beam resists: poly (methyl methacrylate) (PMMA) and hydrogen silsesquioxane. On the other hand, AC-EBL implementation on thick, electron-opaque substrates is appealing for conventional top-down fabrication of quantum devices with nanometer-scale features. To investigate the performance of AC-EBL on thick substrates, we measured the lithographic point spread function of a 200 keV aberration-corrected scanning transmission electron microscope by defining both positive and negative patterns in PMMA thin films, spin-cast on thick SiO 2 /Si substrates. We present the problems encountered during pre-exposure beam focusing and discuss methods to overcome them. In addition, applying some of these methods using commercial 50 nm thick SiN X membranes with thick Si support frames, we printed arrays of holes in PMMA with pitches around 26 nm on SiN X /Si substrates with increasing Si thickness. Here, our results show that proximity effects from even 50 nm thick SiN X membranes limit hole arrays to 20 nm pitch; however, down to this limit, the effect of the substrate thickness on the pattern quality is minimal. These results highlight the need for novel resists less susceptible to proximity effects, or resists which can be used directly, after development, as the dielectric material in periodic gates in 2D quantum devices.

2D quantum devices↗
NASA NTRS2016

On the Alignment and Focusing of the Marshall Grazing Incidence X-ray Spectrometer (MaGIXS)

The Marshall Grazing Incidence X-ray Spectrometer (MaGIXS) is a NASA sounding rocket instrument that is designed to observe soft X-ray emissions from 24 - 6.0 A (0.5 - 2.0 keV energies) in the solar atmosphere. For the rst time, high-temperature, low-emission plasma will be observed directly with 5 arcsecond spatial resolution and 22 mA spectral resolution. The unique optical design consists of a Wolter - I telescope and a 3-optic grazing- incidence spectrometer. The spectrometer utilizes a nite conjugate mirror pair and a blazed planar, varied line spaced grating, which is directly printed on a silicon substrate using e-beam lithography. The grating design is being nalized and the grating will be fabricated by the Massachusetts Institute of Technology (MIT) and Izentis LLC. Marshall Space Flight Center (MSFC) is producing the nickel replicated telescope and spectrometer mirrors using the same facilities and techniques as those developed for the ART-XC and FOXSI mirrors. The Smithsonian Astrophysical Observatory (SAO) will mount and align the optical sub-assemblies based on previous experience with similar instruments, such as the Hinode X-Ray Telescope (XRT). The telescope and spectrometer assembly will be aligned in visible light through the implementation of a theodolite and reference mirrors, in addition to the centroid detector assembly (CDA) { a device designed to align the AXAF-I nested mirrors. Focusing of the telescope and spectrometer will be achieved using the X-ray source in the Stray Light Facility (SLF) at MSFC. We present results from an alignment sensitivity analysis performed on the on the system and we also discuss the method for aligning and focusing MaGIXS.

solar↗
NASA NTRS1993

Curved grating fabrication techniques for concentric-circle grating, surface-emitting semiconductor lasers

We describe the fabrication and operational characteristics of a novel, surface-emitting semiconductor laser that makes use of a concentric-circle grating to both define its resonant cavity and to provide surface emission. A properly fabricated circular grating causes the laser to operate in radially inward- and outward-going circular waves in the waveguide, thus, introducing the circular symmetry needed for the laser to emit a beam with a circular cross-section. The basic circular-grating-resonator concept can be implemented in any materials system; an AlGaAs/GaAs graded-index, separate confinement heterostructure (GRINSCH), single-quantum-well (SQW) semiconductor laser, grown by molecular beam epitaxy (MBE), was used for the experiments discussed here. Each concentric-circle grating was fabricated on the surface of the AlGaAs/GaAs semiconductor laser. The circular pattern was first defined by electron-beam (e-beam) lithography in a layer of polymethylmethacrylate (PMMA) and subsequently etched into the semiconductor surface using chemically-assisted (chlorine) ion-beam etching (CAIBE). We consider issues that affect the fabrication and quality of the gratings. These issues include grating design requirements, data representation of the grating pattern, and e-beam scan method. We provide examples of how these techniques can be implemented and their impact on the resulting laser performance. A comparison is made of the results obtained using two fundamentally different electron-beam writing systems. Circular gratings with period lambda = 0.25 microns and overall diameters ranging from 80 microns to 500 microns were fabricated. We also report our successful demonstration of an optically pumped, concentric-circle grating, semiconductor laser that emits a beam with a far-field divergence angle that is less than one degree. The emission spectrum is quite narrow (less than 0.1 nm) and is centered at wavelength lambda = 0.8175 microns.

Jordan, Rebecca H.↗
NASA NTRS2011

Carbon Nanofiber-Based, High-Frequency, High-Q, Miniaturized Mechanical Resonators

High Q resonators are a critical component of stable, low-noise communication systems, radar, and precise timing applications such as atomic clocks. In electronic resonators based on Si integrated circuits, resistive losses increase as a result of the continued reduction in device dimensions, which decreases their Q values. On the other hand, due to the mechanical construct of bulk acoustic wave (BAW) and surface acoustic wave (SAW) resonators, such loss mechanisms are absent, enabling higher Q-values for both BAW and SAW resonators compared to their electronic counterparts. The other advantages of mechanical resonators are their inherently higher radiation tolerance, a factor that makes them attractive for NASA s extreme environment planetary missions, for example to the Jovian environments where the radiation doses are at hostile levels. Despite these advantages, both BAW and SAW resonators suffer from low resonant frequencies and they are also physically large, which precludes their integration into miniaturized electronic systems. Because there is a need to move the resonant frequency of oscillators to the order of gigahertz, new technologies and materials are being investigated that will make performance at those frequencies attainable. By moving to nanoscale structures, in this case vertically oriented, cantilevered carbon nanotubes (CNTs), that have larger aspect ratios (length/thickness) and extremely high elastic moduli, it is possible to overcome the two disadvantages of both bulk acoustic wave (BAW) and surface acoustic wave (SAW) resonators. Nano-electro-mechanical systems (NEMS) that utilize high aspect ratio nanomaterials exhibiting high elastic moduli (e.g., carbon-based nanomaterials) benefit from high Qs, operate at high frequency, and have small force constants that translate to high responsivity that results in improved sensitivity, lower power consumption, and im - proved tunablity. NEMS resonators have recently been demonstrated using topdown, lithographically fabricated ap - proaches to form cantilever or bridgetype structures. Top-down approaches, however, rely on complicated and expensive e-beam lithography, and often require a release mechanism. Reso - nance effects in structures synthesized using bottom-up approaches have also recently been reported based on carbon nanotubes, but such approaches have relied on a planar two-dimensional (2D) geometry. In this innovation, vertically aligned tubes synthesized using a bottom- up approach have been considered, where the vertical orientation of the tubes has the potential to increase integration density even further. The simulation of a vertically oriented, cantilevered carbon nanotube was performed using COMSOL Multi - physics, a finite element simulation package. All simulations were performed in a 2D geometry that provided consistent results and minimized computational complexity. The simulations assumed a vertically oriented, cantilevered nanotube of uniform density (1.5 g/cu cm). An elastic modulus was assumed to be 600 GPa, relative permittivity of the nanotube was assumed to be 5.0, and Poisson s ratio was assumed to be 0.2. It should be noted that the relative permittivity and Poisson s ratio for the nanotubes of interest are not known accurately. However, as in previous simulations, the relative permittivity and Poisson s ratios were treated as weak variables in the simulation, and no significant changes were recognized when these variables were varied.

Kaul, Anupama B.↗
NASA NTRS2001

Studies on Automated Manufacturing of High Performance Composites

The NASA Langley Research Center fiber placement facility has proven to be a valuable asset for obtaining data, experience, and insights into the automated fabrication of high performance composites. The facility consists of two automated devices: an Asea Brown Boveri (ABB) robotic arm with a modified heated head capable of hot gas and focused infrared heating and a 7' x 17' gantry containing a feeder head, rotating platform, focused infrared lamp and e-beam gun. While uncured thermoset tow and tape, e.g., epoxy and cyanate prepreg, can be placed with a robot, the placement facility s most powerful attribute is the ability to place thermoplastic and e-beam curable material to net shape. In recent years, ribbonizing techniques have been developed to make high quality thermoplastic and thermoset dry material forms to the standards required for robotic placement. A variety of composites have been fabricated from these ribbons by heated head tow and tape placement including both flat plates and cylinders. Composite mechanical property values of the former were between 85 and 100 percent of those obtained by hand lay-up/autoclave processing.

Cano, R. J.↗
NASA NTRS2009

Fabricating Radial Groove Gratings Using Projection Photolithography

Projection photolithography has been used as a fabrication method for radial grove gratings. Use of photolithographic method for diffraction grating fabrication represents the most significant breakthrough in grating technology in the last 60 years, since the introduction of holographic written gratings. Unlike traditional methods utilized for grating fabrication, this method has the advantage of producing complex diffractive groove contours that can be designed at pixel-by-pixel level, with pixel size currently at the level of 45 45 nm. Typical placement accuracy of the grating pixels is 10 nm over 30 nm. It is far superior to holographic, mechanically ruled or direct e-beam written gratings and results in high spatial coherence and low spectral cross-talk. Due to the smooth surface produced by reactive ion etch, such gratings have a low level of randomly scattered light. Also, due to high fidelity and good surface roughness, this method is ideally suited for fabrication of radial groove gratings. The projection mask is created using a laser writer. A single crystal silicon wafer is coated with photoresist, and then the projection mask, with its layer of photoresist, is exposed for patterning in a stepper or scanner. To develop the photoresist, the fabricator either removes the exposed areas (positive resist) of the unexposed areas (negative resist). Next, the patterned and developed photoresist silicon substrate is subjected to reactive ion etching. After this step, the substrate is cleaned. The projection mask is fabricated according to electronic design files that may be generated in GDS file format using any suitable CAD (computer-aided design) or other software program. Radial groove gratings in off-axis grazing angle of incidence mount are of special interest for x-ray spectroscopy, as they allow achieving higher spectral resolution for the same grating area and have lower alignment tolerances than traditional in-plane grating scheme. This is especially critical for NASA Constellation- X project that will utilize hundreds of gratings all of which need to be precisely aligned for x-ray observation of space.

Iazikov, Dmitri↗
NASA NTRS2005

A Preliminary Investigation of the E-Beam Induced Polymerization of Maleimide and Norbornene End-capped Polyimides

A research area of high activity in connection with aerospace engineering has been the development of polymer thermosetting resins that can resist temperature as high as 300 C while maintaining adequate toughness, and providing ease of processing to enable low temperature and low cost composite fabrication methods. In order to meet such requirements, sequential interpenetrating polymer networks (IPNs) based on bismaleimide (BMI) and cyanate ester (CE) monomers were investigated. In these systems, a polycyanurate network is first formed in the presence of BMI and appropriate reactive diluent monomers and in a second step, a network based on the BMI is created in the presence of a fully formed polycyanurate network. The materials developed can be processed at relatively low temperature (less than 150 C) and with the aid of electron beam (EB) curing. Of major importance to the success of this work was the identification of a reactive diluent that improves ease of processing and has tailored reactivity to allow for the controlled synthesis of CE-BMI sequential IPNs. Based on solubility and reactivity of a number of reactive diluents, N-acryloylmorpholine (AMP) was selected as a comonomer for BMI copolymerization. A donor-acceptoreaction mechanism was suggested to explain the relative reactivity of a variety of reactive diluents towards maleimide functionality. The optimum processing parameters for the formation of the first network were determined through the study of metal catalyzed cure and hydrolysis of cyanate esters, whereas the reaction behavior for second network formation in terms of the influence of EB dose rate and temperature was elucidated through an in-situ kinetics study of maleimide and AMP copolymerization. Structure-property relationships were developed which allowed for the design of improved resin systems. In particular, appropriate network coupler possessing cyanate ester and maleimide functionality was synthesized to link the polycyanurate first network to the BMI/AMP second network and thus form linked sequential IPNs (LIPNs). Consequently, Tg as high as 370 C was achieved and a fracture toughness of 120 Joules per square meters was obtained for resin systems that possess adequately low viscosity for processing using liquid molding techniques at low temperature.

Palmese, Giuseppe R.↗
NASA NTRS2008

Low Power, Wide Dynamic Range Carbon Nanotube Vacuum Gauges

This slide presentation presents carbon nanotube vacuum pressure sensor gauges that operate at low power and exhibit a wide-dynamic range based on microelectromechanical systems (MEMS) technology. The fabrication facility, and the formation process are shown. Pressure sensitivity was found to increase rapidly as the bias power was increased. In addition, by etching part of the thermal SiO2 beneath the tubes and minimizing heat conduction through the substrate, pressure sensitivity was extended toward lower pressures. Results are compared to a conventional thin film meander resistor, which was fabricated and whose pressure response was also measured for comparative purposes.

JEOL E-beam aligner↗
NASA NTRS1993

Fabrication of photovoltaic laser energy converterby MBE

A laser-energy converter, fabricated by molecular beam epitaxy (MBE), was developed. This converter is a stack of vertical p-n junctions connected in series by low-resistivity, lattice matched CoSi2 layers to achieve a high conversion efficiency. Special high-temperature electron-beam (e-beam) sources were developed especially for the MBE growth of the junctions and CoSi2 layers. Making use of the small (greater than 1.2 percent) lattice mismatch between CoSi2 and Si layers, high-quality and pinhole-free epilayers were achieved, providing a capability of fabricating all the junctions and connecting layers as a single growth process with one pumpdown. Well-defined multiple p-n junctions connected by CoSi2 layers were accomplished by employing a low growth temperature (greater than 700 C) and a low growth rate (less than 0.5 microns/hour). Producing negligible interdiffusion, the low growth temperature and rate also produced negligible pinholes in the CoSi2 layers. For the first time, a stack of three p-n junctions connected by two 10(exp -5) Ohm-cm CoSi2 layers was achieved, meeting the high conversion efficiency requirement. This process can now be optimized for high growth rate to form a practical converter with 10 p-n junctions in the stack.

Lu, Hamilton↗
NASA NTRS2018

Method of Fabricating X-Ray Absorbers for Low-Energy X-Ray Spectroscopy

A method of forming low-energy x-ray absorbers. Sensors may be formed on a semiconductor, e.g., silicon, wafer. A seed metal layer, e.g., gold, is deposited on the wafer and patterned into stem pads for electroplating. Stems, e.g., gold, are electroplated from the stem seed pads through a stem mask. An absorber layer, e.g., gold, is deposited on the wafer, preferably e-beam evaporated. After patterning the absorbers, absorber and stem mask material is removed, e.g., in a solvent bath and critical point drying.

Stevenson, Thomas R.↗
NASA NTRS2014

Increased Tensile Strength of Carbon Nanotube Yarns and Sheets through Chemical Modification and Electron Beam Irradiation

The inherent strength of individual carbon nanotubes offers considerable opportunity for the development of advanced, lightweight composite structures. Recent work in the fabrication and application of carbon nanotube (CNT) forms such as yarns and sheets has addressed early nanocomposite limitations with respect to nanotube dispersion and loading; and has pushed the technology toward structural composite applications. However, the high tensile strength of an individual CNT has not directly translated to macro-scale CNT forms where bulk material strength is limited by inter-tube electrostatic attraction and slippage. The focus of this work was to assess post processing of CNT sheet and yarn to improve the macro-scale strength of these material forms. Both small molecule functionalization and e-beam irradiation was evaluated as a means to enhance tensile strength and Youngs modulus of the bulk CNT material. Mechanical testing results revealed a tensile strength increase in CNT sheets by 57 when functionalized, while an additional 48 increase in tensile strength was observed when functionalized sheets were irradiated; compared to unfunctionalized sheets. Similarly, small molecule functionalization increased yarn tensile strength up to 25, whereas irradiation of the functionalized yarns pushed the tensile strength to 88 beyond that of the baseline yarn.

composites↗
NASA NTRS2010

Fabrication of Single, Vertically Aligned Carbon Nanotubes in 3D Nanoscale Architectures

Plasma-enhanced chemical vapor deposition (PECVD) and high-throughput manufacturing techniques for integrating single, aligned carbon nanotubes (CNTs) into novel 3D nanoscale architectures have been developed. First, the PECVD growth technique ensures excellent alignment of the tubes, since the tubes align in the direction of the electric field in the plasma as they are growing. Second, the tubes generated with this technique are all metallic, so their chirality is predetermined, which is important for electronic applications. Third, a wafer-scale manufacturing process was developed that is high-throughput and low-cost, and yet enables the integration of just single, aligned tubes with nanoscale 3D architectures with unprecedented placement accuracy and does not rely on e-beam lithography. Such techniques should lend themselves to the integration of PECVD grown tubes for applications ranging from interconnects, nanoelectromechanical systems (NEMS), sensors, bioprobes, or other 3D electronic devices. Chemically amplified polyhydroxystyrene-resin-based deep UV resists were used in conjunction with excimer laser-based (lambda = 248 nm) step-and-repeat lithography to form Ni catalyst dots = 300 nm in diameter that nucleated single, vertically aligned tubes with high yield using dc PECVD growth. This is the first time such chemically amplified resists have been used, resulting in the nucleation of single, vertically aligned tubes. In addition, novel 3D nanoscale architectures have been created using topdown techniques that integrate single, vertically aligned tubes. These were enabled by implementing techniques that use deep-UV chemically amplified resists for small-feature-size resolution; optical lithography units that allow unprecedented control over layer-to-layer registration; and ICP (inductively coupled plasma) etching techniques that result in near-vertical, high-aspect-ratio, 3D nanoscale architectures, in conjunction with the use of materials that are structurally and chemically compatible with the high-temperature synthesis of the PECVD-grown tubes. The techniques offer a wafer-scale process solution for integrating single PECVD-grown nanotubes into novel architectures that should accelerate their integration in 3D electronics in general. NASA can directly benefit from this technology for its extreme-environment planetary missions. Current Si transistors are inherently more susceptible to high radiation, and do not tolerate extremes in temperature. These novel 3D nanoscale architectures can form the basis for NEMS switches that are inherently less susceptible to radiation or to thermal extremes.

Kaul, Anupama B.↗
NASA NTRS1994

A combined electron beam/optical lithography process step for the fabrication of sub-half-micron-gate-length MMIC chips

Advanced radar and communication systems rely heavily on state-of-the-art microelectronics. Systems such as the phased-array radar require many transmit/receive (T/R) modules which are made up of many millimeter wave - microwave integrated circuits (MMIC's). The heart of a MMIC chip is the Gallium Arsenide (GaAs) field-effect transistor (FET). The transistor gate length is the critical feature that determines the operating frequency of the radar system. A smaller gate length will typically result in a higher frequency. In order to make a phased array radar system economically feasible, manufacturers must be capable of producing very large quantities of small-gate-length MMIC chips at a relatively low cost per chip. This requires the processing of a large number of wafers with a large number of chips per wafer, minimum processing time, and a very high chip yield. One of the bottlenecks in the fabrication of MIMIC chips is the transistor gate definition. The definition of sub-half-micron gates for GaAs-based field-effect transistors is generally performed by direct-write electron beam lithography (EBL). Because of the throughput limitations of EBL, the gate-layer fabrication is conventionally divided into two lithographic processes where EBL is used to generate the gate fingers and optical lithography is used to generate the large-area gate pads and interconnects. As a result, two complete sequences of resist application, exposure, development, metallization and lift-off are required for the entire gate structure. We have baselined a hybrid process, referred to as EBOL (electron beam/optical lithography), in which a single application of a multi-level resist is used for both exposures. The entire gate structure, (gate fingers, interconnects and pads), is then formed with a single metallization and lift-off process. The EBOL process thus retains the advantages of the high-resolution E-beam lithography and the high throughput of optical lithography while essentially eliminating an entire lithography/metallization/lift-off process sequence. This technique has been proven to be reliable for both trapezoidal and mushroom gates and has been successfully applied to metal-semiconductor and high-electron-mobility field-effect transistor (MESFET and HEMT) wafers containing devices with gate lengths down to 0.10 micron and 75 x 75 micron gate pads. The yields and throughput of these wafers have been very high with no loss in device performance. We will discuss the entire EBOL process technology including the multilayer resist structure, exposure conditions, process sensitivities, metal edge definition, device results, comparison to the standard gate-layer process, and its suitability for manufacturing.

Sewell, James S.↗
NASA NTRS2005

MOVPE of GaSb/InGaAsSb Multilayers and Fabrication of Dual Band Photodetectors

Metalorganic vapor phase epitaxy (MOVPE) of GaSb/InGaAsSb multilayer thin films and fabrication of bias-selectable dual band photodetectors are reported. For the dual band photodetectors the short wavelength detector, or the upper p- GaSb/n-GaSb junction photodiode, is placed optically ahead of the long wavelength one, or the lower photodiode. The latter is based on latticed-matched In0.13Ga0.87As0.11Sb0.89 with bandgap near 0.6 eV. Specifically, high quality multilayer thin films are grown sequentially from top to bottom as p+-GaSb/p-GaSb/n-GaSb/n-InGaAsSb/p-InGaAsSb/p-GaSb on undoped p-type GaSb substrate, and as n-GaSb/p-GaSb/p-InGaAsSb/n-InGaAsSb/n-GaSb on Te-doped n-type GaSb substrate respectively. The multilayer thin films are characterized by optical microscope, atomic force microscope (AFM), electron microprobe analyses etc. The photodiode mesa steps are patterned by photolithography with wet chemical etching and the front metallization is carried out by e-beam evaporation with Pd/Ge/Au/Ti/Au to give ohmic contact on both n- and p-type Sb based layer surfaces. Dark I-V measurements show typical diode behavior for both the upper and lower photodiodes. The photoresponsivity measurements indicate that both the upper and lower photodiodes can sense the infrared illumination corresponding to their cutoff wavelengths respectively, comparable with the simulation results. More work is underway to bring the long wavelength band to the medium infrared wavelength region near 4 micrometers.

Xiao, Ye-Gao↗
NASA NTRS1999

Copper-Based OHMIC Contracts for the Si/SiGe Heterojunction Bipolar Transistor Structure

Silicon based heterojunction bipolar transistors (HBT) with SiGe base are potentially important devices for high-speed and high-frequency microelectronics. These devices are particularly attractive as they can be fabricated using standard Si processing technology. However, in order to realize the full potential of devices fabricated in this material system, it is essential to be able to form low resistance ohmic contacts using low thermal budget process steps and have full compatibility with VLSI/ULSI processing. Therefore, a study was conducted in order to better understand the contact formation and to develop optimized low resistance contacts to layers with doping densities corresponding to the p-type SiGe base and n-type Si emitter regions of the HBTS. These as-grown doped layers were implanted with BF(sub 2) up to 1 X 10(exp 16)/CM(exp 2) and As up to 5 x 10(exp 15)/CM2, both at 30 keV for the p-type SiGe base and n-type Si emitter layers, respectively, in order to produce a low sheet resistance surface layer. Standard transfer length method (TLM) contact pads on both p and n type layers were deposited using an e-beam evaporated trilayer structure of Ti/CufTi/Al (25)A/1500A/250A/1000A). The TLM pads were delineated by a photoresist lift-off procedure. These contacts in the as-deposited state were ohmic, with specific contact resistances for the highest implant doses of the order of 10(exp -7) ohm-CM2 and lower.

Das, Kalyan↗
DOE OSTI2024

Permeation Properties of Disordered Metal-Organic Framework Membranes Made by Vapor Phase Ligand Treatment

Zeolitic imidazolate frameworks (ZIFs) are nanoporous molecular sieves offering exciting opportunities for membrane- and adsorption-based gas separations. The Tsapatsis group developed an all-vapor-phase ligand induced permselectivation (LIPS) method for the fabrication of ZIF nanocomposite membranes. The LIPS method consists of a combination of atomic layer deposition of a dense oxide inside the mesopores of a porous support followed by transformation of the dense oxide deposit to nanoporous ZIF by exposure to sublimated vapors of an imidazolate ligand. It enables the formation of thin nanocomposite films consisting of ZIF deposited inside pores with diameters smaller than 10 nm. Vapor-phase conversion of the impermeable ZnO to ZIF increases flux of certain gases more than others. Vapor phase linker/ligand treatment (VPLT) can further modify the properties of LIPS and other membranes. The combination of LIPS with VPLT provides an all-vapor methodology for making and modifying ZIF membranes with the ability to control the ZIF deposit composition and the level of confinement in a variety of mesoporous supports. The propylene/propane separation performance of LIPS/VPLT ZIF membranes confined (entirely or partially) inside mesopores is remarkably superior to that of most conventional ZIF membranes consisting of unconfined (deposited on the external surface of porous supports) polycrystalline films. The accomplishments of this award are: (i) understanding of the LIPS process using mathematical models of atomic layer deposition (ALD), (ii) development of surface modification methods (vapor, e-beam, plasma, and X-ray treatments) to tune permeation properties, (iii) microstructural control of ZIF-8 films using ALD (support modification, direct ALD, and by use of in situ permeability monitoring), (iv) molecular simulations, and (v) thin film characterization and adsorption measurements using spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Degradation of Poly- and Perfluoroalkyl Substances (PFAS) in Water via High Power, Energy-Efficient Electron Beam Accelerator

The goal of the 2-year workplan was to see if electron beam (EB) could be used to break down a sub-set of the larger chemical family of per and polyfluoroalkylated substances (PFAS) in an energy efficient and economical manner when compared to conventional water treatment technologies. Year one (Y1) work focused on sample EB treatment work in the Fermi National Accelerator Laboratory’s (FNALs) Accelerator Applications Demonstration and Development (A2D2) EB accelerator. While there are reportedly thousands of types of PFAS, for the point of most of the work herein, a small subset was examined, typically perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA). PFOA and PFOS are two of the most well studied PFAS and are studied for baseline evaluations and are considered most useful. The work from Y1 provided information about the optimal operating parameters and additives to use when treating PFOS and PFOA via EB. The data were then used to see where in a water treatment system an EB accelerator would be best suited to treat PFAS. A conventional water treatment technology, GAC, was then compared to e-beam treatment technology with respect to energy and costs for treatment. In year two (Y2), several conventional e-beam accelerator designs, and FNAL’s developmental compact SRF accelerator design, were evaluated for their suitability in PFAS treatment, from an energy efficiency and cost standpoint. Several EB parameters were evaluated and optimized for the removal of PFOA and PFOS from water at normal pressure and temperature, measured as total PFAS removal. Under the optimized test conditions both PFOA showed complete destruction to inorganic fluoride, and PFOS to inorganic fluoride and sulfate, with mass balance. The effect on PFAS removal relative to solution pH, total EB dose, EB dose rate, dissolved oxygen concentration (DO), temperature, and initial PFAS concentration were evaluated. In general, PFOA was easier to destroy than PFOS. Degradation products, typically observed under less-than-optimal EB conditions, provided insight to degradation mechanisms. Products were identified to rule out possible deleterious biproduct formation. The water radiolysis radical reaction kinetics with PFOS and PFOA were not dependent on the initial concentration over 5-orders of magnitude from 2 μg/L to 20 mg/L. This is thought to be because there was an overabundance of the reactive water radiolysis radicals relative to PFAS molecules and largely attributed to aqueous electrons. The reaction rates appeared to be diffusion limited. Testing at higher concentrations (100-200 mg/L) showed a decrease in removal efficiency, suggesting alternative kinetics, possibly second order rates, at higher concentrations. In all, we successfully defined a set of optimal EB parameters to treat PFOA and PFOS at concentrations of 20 mg/L in water with destruction efficiencies near 100%. We further tested the optimized EB parameters with other types of PFAS, including shorter and longer fluorocarbon chain homologs of PFOA and PFOS, and PFAS with alternative functional groups such as sulfonamides. Based on our results EB can be optimized as an effective destructive technology for removing PFAS from water. The conditions optimized for PFOA and PFOS were less effective with ultra-short fluorocarbon compounds like TFMS, PFES, PFPS and PFBS, and likely require re-optimization of parameters to them. In all, it was determined that from a cost and energy efficiency standpoint, EB would be best applied to waste streams with relatively high concentrations of PFOS and PFOA and is not as cost effective as GAC treatment for removing low concentrations of PFAS from water. Higher concentrations of PFAS can be found in the wastewater of conventional treatment processes such as RO and IE and therefore EB may be used to supplement such treatment technologies. Some real-world IE regeneration wash water and RO reject water containing higher concentrations of PFAS and obtained from pilot scale industrial wastewater treatment system at a fluorochemical manufacturing facility, showed that EB could remove PFAS from such types of wastewaters. The IE regenerant wash water appeared to be the most efficient of the two types of wastewaters tested. However, some further optimization of the EB parameters for the specific PFAS types present in those wastewaters may be required. Also, the effects of co-present TOC and mineral salts should be considered during such optimization efforts. From the experimental Y1 results it was seen that the aqueous electron drives degradation of the PFAS. In a hypothetical water treatment skid using EB for PFAS destruction the parameters of the system should be optimized to promote aqueous electron production. Before EB treatment, the PFAS should be preconcentrated when possible, the pH should be raised to pH 10 or higher to enhance aqueous electron production, and the water should be nitrogen purged to remove dissolved oxygen to minimize aqueous electron scavenging. An excel spreadsheet was created that calculates optimal conditions based on inlet PFAS concentration and desired outlet concentration, by optimizing the accelerator power, dose rate, water treatment rate, pH and dissolved oxygen levels to reach the desired endpoint. Given this information on accelerator operating conditions five different EB accelerator systems were compared. One EB system was a continuous-wave, linear superconducting accelerator being designed at Fermilab. Three other EB systems (IMPELA at 5% and 25% duty factor and the ILU-14) were normal conducting pulsed linear accelerators. The fifth system was an IBA Rhodotron which is a normal conducting, circular, continuous-wave accelerator. The accelerator efficiency (% of the incoming power that is used in water treatment) was the dominating factor in accelerator choice. The radio frequency (RF) power supply and the accelerator design (superconducting versus warm technology) drive the accelerator efficiency. The IBA Rhodotron was seen to be the most energy efficient commercially available technology with a wall-plug (total) power efficiency of 43% at 400 kW. The Fermilab design, with a prototype for a different application currently being fabricated, was the most energy efficient at 55% when driven by a Klystron RF power supply and as high as 77% when powered by a magnetron. As the Fermilab design was the most energy efficient by approximately 10-30%, further design work was done on the accelerator and beam delivery system specific to the destruction of PFAS in water. The Fermilab design is unique from industrial accelerators in that is superconducting. Superconducting technology allows for the acceleration of electrons without losses. The accelerator must be cooled to below the point where it is superconducting and is operated around 4 degrees Kelvin. The bulk of the design work for the accelerator is on making the accelerator as energy efficient as possible so that it does not require liquid helium and can be cooled with conduction cooling via cryocoolers. Final design work resulted in an EB accelerator that would operate at minimally 200 kW and 10 MeV. Prototype construction would cost $\$ $7.8 million dollars when driven by a Klystron power supply. A second version of the same accelerator would cost $\$ $5.5 million dollars when driven by a magnetron that is still under development. The commercially available 300 kW IBA Rhodotron cost was estimated at approximately $\$ $9 million. While it is hard to directly compare, an operational GAC system used by 3M for groundwater treatment capital cost (2022 dollars) was estimated to cost $\$ $3.3 million. While the capital expense of the EB accelerator systems was higher than GAC, the accelerator EB treatment would result in destruction of the PFAS and not just sequestration of PFAS to form a new waste stream that requires further treatment or disposal. The operating cost to destroy the PFAS via 400 kw EB system was less than $\$ $1000/kg of PFAS destroyed when treating at a 20 mg/L PFAS concentration, compared to GAC with operating costs that calculated at $\$ $27,530 per kg of PFAS sequestered when treating 100 μg/L PFOA and PFOS combined concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2007

Control of Space-Based Electron Beam Free Form Fabrication

Engineering a closed-loop control system for an electron beam welder for space-based additive manufacturing is challenging. For earth and space based applications, components must work in a vacuum and optical components become occluded with metal vapor deposition. For extraterrestrial applications added components increase launch weight, increase complexity, and increase space flight certification efforts. Here we present a software tool that closely couples path planning and E-beam parameter controls into the build process to increase flexibility. In an environment where data collection hinders real-time control, another approach is considered that will still yield a high quality build.

Seifzer. W. J.↗