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Low-Cost Phased Array Antenna for Sounding Rockets, Missiles, and Expendable Launch Vehicles

A low-cost beamformer phased array antenna has been developed for expendable launch vehicles, rockets, and missiles. It utilizes a conformal array antenna of ring or individual radiators (design varies depending on application) that is designed to be fed by the recently developed hybrid electrical/mechanical (vendor-supplied) phased array beamformer. The combination of these new array antennas and the hybrid beamformer results in a conformal phased array antenna that has significantly higher gain than traditional omni antennas, and costs an order of magnitude or more less than traditional phased array designs. Existing omnidirectional antennas for sounding rockets, missiles, and expendable launch vehicles (ELVs) do not have sufficient gain to support the required communication data rates via the space network. Missiles and smaller ELVs are often stabilized in flight by a fast (i.e. 4 Hz) roll rate. This fast roll rate, combined with vehicle attitude changes, greatly increases the complexity of the high-gain antenna beam-tracking problem. Phased arrays for larger ELVs with roll control are prohibitively expensive. Prior techniques involved a traditional fully electronic phased array solution, combined with highly complex and very fast inertial measurement unit phased array beamformers. The functional operation of this phased array is substantially different from traditional phased arrays in that it uses a hybrid electrical/mechanical beamformer that creates the relative time delays for steering the antenna beam via a small physical movement of variable delay lines. This movement is controlled via an innovative antenna control unit that accesses an internal measurement unit for vehicle attitude information, computes a beam-pointing angle to the target, then points the beam via a stepper motor controller. The stepper motor on the beamformer controls the beamformer variable delay lines that apply the appropriate time delays to the individual array elements to properly steer the beam. The array of phased ring radiators is unique in that it provides improved gain for a small rocket or missile that uses spin stabilization for stability. The antenna pattern created is symmetric about the roll axis (like an omnidirectional wraparound), and is thus capable of providing continuous coverage that is compatible with very fast spinning rockets. For larger ELVs with roll control, a linear array of elements can be used for the 1D scanned beamformer and phased array, or a 2D scanned beamformer can be used with an NxN element array.

Mullinix, Daniel↗

NASA Tech Briefs, May 2009

Topics covered include: Valve-"Health"-Monitoring System; Microstrip Antenna for Remote Sensing of Soil Moisture and Sea Surface Salinity; Biomedical Wireless Ambulatory Crew Monitor; Wireless Avionics Packet to Support Fault Tolerance for Flight Applications; Aerobot Autonomy Architecture; Submillimeter Confocal Imaging Active Module; Traveling-Wave Maser for 32 GHz; System Synchronizes Recordings from Separated Video Cameras; Piecewise-Planar Parabolic Reflectarray Antenna; Reducing Interference in ATC Voice Communication; EOS MLS Level 1B Data Processing, Version 2.2; Auto-Generated Semantic Processing Services; Geospatial Authentication; Maneuver Automation Software; Event Driven Messaging with Role-Based Subscriptions; Estimating Relative Positions of Outer-Space Structures; Fabricating PFPE Membranes for Capillary Electrophoresis; Linear Actuator Has Long Stroke and High Resolution; Installing a Test Tap on a Metal Battery Case; Fabricating PFPE Membranes for Microfluidic Valves and Pumps; Room-Temperature-Cured Copolymers for Lithium Battery Gel Electrolytes; Catalysts for Efficient Production of Carbon Nanotubes; Amorphous Silk Fibroin Membranes for Separation of CO2; "Zero-Mass" Noninvasive Pressure Transducers; Radial-Electric-Field Piezoelectric Diaphragm Pumps; Ejector-Enhanced, Pulsed, Pressure-Gain Combustor; Suppressing Ghost Diffraction in E-Beam-Written Gratings; Target-Tracking Camera for a Metrology System; Polarimetric Imaging using Two Photoelastic Modulators; Miniature Wide-Angle Lens for Small-Pixel Electronic Camera; Modal Filters for Infrared Interferometry; Mo(3)Sb(7-x)Te(x) for Thermoelectric Power Generation; Two-Dimensional Quantum Model of a Nanotransistor; Scanning Miniature Microscopes without Lenses; Manipulating Neutral Atoms in Chip-Based Magnetic Traps; Expansion Compression Contacts for Thermoelectric Legs; Processing Electromyographic Signals to Recognize Words; Physical Principle for Generation of Randomness; DSN Beowulf Cluster-Based VLBI Correlator; Hybrid NN/SVM Computational System for Optimizing Designs; Criteria for Modeling in LES of Multicomponent Fuel Flow; Computerized Machine for Cutting Space Shuttle Thermal Tiles; Orbiting Depot and Reusable Lander for Lunar Transportation; FPGA-Based Networked Phasemeter for a Heterodyne Interferometer; Aquarius Digital Processing Unit; Three-Dimensional Optical Coherence Tomography; Benchtop Antigen Detection Technique using Nanofiltration and Fluorescent Dyes; Isolation of Precursor Cells from Waste Solid Fat Tissue; Identification of Bacteria and Determination of Biological Indicators; Further Development of Scaffolds for Regeneration of Nerves; Chemically Assisted Photocatalytic Oxidation System; Use of Atomic Oxygen for Increased Water Contact Angles of Various Polymers for Biomedical Applications; Crashworthy Seats Would Afford Superior Protection; Open-Access, Low-Magnetic-Field MRI System for Lung Research; Microfluidic Mixing Technology for a Universal Health Sensor; Microfluidic Extraction of Biomarkers using Water as Solvent; Microwell Arrays for Studying Many Individual Cells; Droplet-Based Production of Liposomes; and Identifying and Inactivating Bacterial Spores

Source record↗

Genesis Concentrator Target Particle Contamination Mapping and Material Identification

The majority of surface particles were found to be < 5 microns in diameter with increasing numbers close to the optical resolution limit of 0.3 microns. Acceleration grid EDS results show that the majority of materials appear to be from the SRC shell and SLA materials which include carbon-carbon fibers and Si-rich microspheres in a possible silicone binder. Other major debris material from the SRC included white paint, kapton, collector array fragments, and Al. Image analysis also revealed that SRC materials were also found mixed with the Utah mud and salt deposits. The EDS analysis of the acceleration grid showed that particles < 1 m where generally carbon based particles. Chemical cleaning techniques with Xylene and HF in an ultrasonic bath are currently being investigated for removal of small particles by the Genesis science team as well as ultra-pure water megasonic cleaning by the JSC team [4]. Removal of organic contamination from target materials is also being investigated by the science team with the use of UV-ozone cleaning devices at JSC and Open University [5]. In preparation for solar wind oxygen analyses at UCLA and Open University [1, 2], surface particle contamination on three Genesis concentrator targets was closely examined to evaluate cleaning strategies. Two silicon carbide (Genesis sample # 60001 and 60003) and one chemical vapor deposited (CVD) 13C concentrator target (60002) were imaged and mosaic mapped with optical microscopes. The resulting full target mosaic images and particle feature maps were subsequently compared with non-flight, but flight-like, concentrator targets and sample return capsule (SRC) materials. Contamination found on the flown concentrator acceleration grid was further examined using a scanning electron microscope (SEM). Energy dispersive X-ray spectroscopy (EDS) for particle identification was subsequently compared with the optical images from the flown targets. Figure 1 show that all three targets imaged in this report are fully intact and do not show any signs of material fractures. However, previous ellipsometry results and overview imaging of both flown SiC targets show a solar wind irradiation gradient from the center focal point to the outer edge [3]. In addition, due to the hard landing, each target has experienced varying degrees of impacts, scratches, and particle debris from the spacecraft and Utah impact site.

Calaway, Michael J.↗

Helicopter Flight Test of a Compact, Real-Time 3-D Flash Lidar for Imaging Hazardous Terrain During Planetary Landing

A second generation, compact, real-time, air-cooled 3-D imaging Flash Lidar sensor system, developed from a number of cutting-edge components from industry and NASA, is lab characterized and helicopter flight tested under the Autonomous Precision Landing and Hazard Detection and Avoidance Technology (ALHAT) project. The ALHAT project is seeking to develop a guidance, navigation, and control (GN&C) and sensing system based on lidar technology capable of enabling safe, precise crewed or robotic landings in challenging terrain on planetary bodies under any ambient lighting conditions. The Flash Lidar incorporates a 3-D imaging video camera based on Indium-Gallium-Arsenide Avalanche Photo Diode and novel micro-electronic technology for a 128 x 128 pixel array operating at a video rate of 20 Hz, a high pulse-energy 1.06 μm Neodymium-doped: Yttrium Aluminum Garnet (Nd:YAG) laser, a remote laser safety termination system, high performance transmitter and receiver optics with one and five degrees field-of-view (FOV), enhanced onboard thermal control, as well as a compact and self-contained suite of support electronics housed in a single box and built around a PC-104 architecture to enable autonomous operations. The Flash Lidar was developed and then characterized at two NASA-Langley Research Center (LaRC) outdoor laser test range facilities both statically and dynamically, integrated with other ALHAT GN&C subsystems from partner organizations, and installed onto a Bell UH-1H Iroquois "Huey" helicopter at LaRC. The integrated system was flight tested at the NASA-Kennedy Space Center (KSC) on simulated lunar approach to a custom hazard field consisting of rocks, craters, hazardous slopes, and safe-sites near the Shuttle Landing Facility runway starting at slant ranges of 750 m. In order to evaluate different methods of achieving hazard detection, the lidar, in conjunction with the ALHAT hazard detection and GN&C system, operates in both a narrow 1deg FOV raster-scanning mode in which successive, gimbaled images of the hazard field are mosaicked together as well as in a wider, 4.85deg FOV staring mode in which digital magnification, via a novel 3-D superresolution technique, is used to effectively achieve the same spatial precision attained with the more narrow FOV optics. The lidar generates calibrated and corrected 3-D range images of the hazard field in real-time and passes them to the ALHAT Hazard Detection System (HDS) which stitches the images together to generate on-the-fly Digital Elevation Maps (DEM's) and identifies hazards and safe-landing sites which the ALHAT GN&C system can then use to guide the host vehicle to a safe landing on the selected site. Results indicate that, for the KSC hazard field, the lidar operational range extends from 100m to 1.35 km for a 30 degree line-of-sight angle and a range precision as low as 8 cm which permits hazards as small as 25 cm to be identified. Based on the Flash Lidar images, the HDS correctly found and reported safe sites in near-real-time during several of the flights. A follow-on field test, planned for 2013, seeks to complete the closing of the GN&C loop for fully-autonomous operations on-board the Morpheus robotic, rocket-powered, free-flyer test bed in which the ALHAT system would scan the KSC hazard field (which was vetted during the present testing) and command the vehicle to landing on one of the selected safe sites.

Roback, VIncent E.↗

Investigating the impact of donor atoms of single-source precursors on f-element nanomaterial formation and mechanisms of initial bond cleavage

Nanotechnology is advancing exponentially, with novel discoveries and applications emerging every day across various fields, including environmental remediation, biomedicine, electronics, and textiles. Nanoparticles (NPs) are defined as particles with sizes ranging from 1 to 100 nm, and their properties are influenced by factors such as composition, phase, size, and shape. Single-source precursors (SSPs) offer a promising method for controlling the synthesis of phase-pure nanoparticles with the desired stoichiometry and have been successfully applied to prepare transition metal and lanthanide NPs. SSPs are molecular compounds that contain all the necessary components to form the final nanomaterial and decompose under mild conditions, such as heating, to create the solid-state product. The objective of this work was to garner a mechanistic understanding of cerium oxide NP formation from cerium SSPs. To achieve these goals, first, ligands with oxygen and sulfur donor atoms were synthesized; among the array of ligands synthesized, some were novel. These ligands were then chelated to cerium ions to synthesize cerium precursors. Initially, known cerium alkoxide precursors were synthesized. Subsequently, these basic cerium complexes were further manipulated through acid-base protonolysis reactions to install a diverse set of ligands. Within this body of work, 10 novel cerium precursors were successfully synthesized. The ligands and the SSPs were analyzed using nuclear magnetic resonance (NMR) and thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC). These SSPs were then introduced to a collision-induced dissociation mass spectrometer (CID-MS), and their dissociation pathways were studied.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

Quantifying the Variation in the Number of Donors in Quantum Dots Created Using Atomic Precision Advanced Manufacturing

Atomic-precision advanced manufacturing enables unique silicon quantum electronics built on quantum dots fabricated from small numbers of phosphorus dopants. The number of dopant atoms comprising a dot plays a central role in determining the behavior of charge and spin confined to the dots and thus overall device performance. Here in this work, we use both theoretical and experimental techniques to explore the combined impact of lithographic variation and stochastic kinetics on the number of P incorporations in quantum dots made using these techniques and how this variation changes as a function of the size of the dot. Using a kinetic model of PH3 dissociation augmented with novel reaction barriers, we demonstrate that for a 2 × 3 silicon dimer window the probability that no donor incorporates goes to zero, allowing for certainty in the placement of at least one donor. However, this still comes with some uncertainty in the precise number of incorporated donors (either one or two), and this variability may still impact certain applications. We also examine the impact of the size of the initial lithographic window, finding that the incorporation fraction saturates to δ-layer-like coverage as the circumference-to-area ratio decreases. We predict that this incorporation fraction depends strongly on the dosage of the precursor and that the standard deviation of the number of incorporations scales as ~√n, as would be expected for a sequence of largely independent incorporation events. Finally, we characterize an array of 36 experimentally prepared multidonor 3 × 3 nm lithographic windows with scanning tunneling microscopy, measuring the fidelity of the lithography to the desired array and the final location of PH x fragments within these lithographic windows. We use our kinetic model to examine the expected variability due to the observed lithographic error, predicting a negligible impact on incorporation statistics. We find good agreement between our model and the inferred incorporation locations in these windows from scanning tunneling microscope measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transferring orbital angular momentum to an electron beam reveals toroidal and chiral order

Orbital angular momentum (OAM) and torque transfer play central roles in a wide range of magnetic textures and devices including skyrmions and spin-torque electronics. Analogous topological structures are now also being explored in ferroelectrics, including polarization vortex arrays in ferroelectric/dielectric superlattices. Unlike magnetic toroidal order, electric toroidal order does not couple directly to linear external fields. Instead, we find that the presence of an electric toroidal moment in a ferrorotational phase transfers measurable torque and OAM to a localized electron beam in the ballistic limit. We record these torque transfers from a high-energy electron beam using a momentum-resolved detector. This approach provides a high-sensitivity method to detect polarization fields and their more complex order parameters and topologies. In addition to toroidal order, we also demonstrate high-precision measurements of vorticity and chirality for polar vortexlike phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Development of Leaky Wave Antennas for Layered Ridge Dielectric Waveguide

The millimeter wave, especially above 100 GHz, and the submillimeter wave frequency spectrum offers the possibility for narrow-beam, high-resolution antennas which are critical for high definition radars required for space debris tracking, airport ground avoidance radars, and missile tracking. In addition, the frequency which most atmospheric constituents may be detected lie in this part of the frequency spectrum. Therefore, the development of electronic components for millimeter/submillimeter wave passive sensors is required for environmental monitoring of the Earth's atmosphere. Typical microwave transmission lines such as microstrip and coplanar waveguide rely on two or more electrical conductors to concentrate and guide the electromagnetic energy. Unfortunately, the surface resistance of the conductors increases as the square root of frequency. In addition, the circuit dimensions must be decreased with increasing frequency to maintain a single mode transmission line which further increases the conductor loss. An alternative family of transmission lines are formed from two or more insulating materials and rely on the differences in the permittivities between the two materials to guide the wave. No metal conductors are required although some dielectric waveguides do utilize a metallic ground plane to facilitate the interconnections of active electrical elements or to reduce the transmission line size. Examples of such transmission lines are image guides, insulated image guides, trapped image guides, ridge guide, and layered ridge dielectric waveguide (LRDW). Although most dielectric waveguides have dimensions on the order of lambda to provide sufficient field confinement, the LRDW has been shown to provide good field confinement for electrically small lines. This offers an advantage in circuit integration. It has been shown that a periodic array of metallic strips placed either along or on top of a dielectric waveguide forms an effective radiator. This antenna is easy to fabricate and there is good background of microstrip type antenna design information in the literature. This paper reports the development of the first frequency scanning antenna fed by a LRDW.

Ponchak, George E.↗

Delta-Doped CCDs as Detector Arrays in Mass Spectrometers

In a conventional mass spectrometer, charged particles (ions) are dispersed through a magnetic sector onto an MCP at an output (focal) plane. In the MCP, the impinging charged particles excite electron cascades that afford signal gain. Electrons leaving the MCP can be read out by any of a variety of means; most commonly, they are post-accelerated onto a solid-state detector array, wherein the electron pulses are converted to photons, which, in turn, are converted to measurable electric-current pulses by photodetectors. Each step in the conversion from the impinging charged particles to the output 26 NASA Tech Briefs, February 2007 current pulses reduces spatial resolution and increases noise, thereby reducing the overall sensitivity and performance of the mass spectrometer. Hence, it would be preferable to make a direct measurement of the spatial distribution of charged particles impinging on the focal plane. The utility of delta-doped CCDs as detectors of charged particles was reported in two articles in NASA Tech Briefs, Vol. 22, No. 7 (July 1998): "Delta-Doped CCDs as Low-Energy-Particle Detectors" (NPO-20178) on page 48 and "Delta- Doped CCDs for Measuring Energies of Positive Ions" (NPO-20253) on page 50. In the present developmental miniature mass spectrometers, the above mentioned miniaturization and performance advantages contributed by the use of delta-doped CCDs are combined with the advantages afforded by the Mattauch-Herzog design. The Mattauch- Herzog design is a double-focusing spectrometer design involving an electric and a magnetic sector, where the ions of different masses are spatially separated along the focal plane of magnetic sector. A delta-doped CCD at the focal plane measures the signals of all the charged-particle species simultaneously at high sensitivity and high resolution, thereby nearly instantaneously providing a complete, high-quality mass spectrum. The simultaneous nature of the measurement of ions stands in contrast to that of a scanning mass spectrometer, in which abundances of different masses are measured at successive times.

Nikzad, Shouleh↗

KALYPSO: Linear array detector for high-repetition rate and real-time beam diagnostics

Synchrotrons and modern FEL light sources operate with bunch repetition rates in the MHz range. The profile of the electron beam inside the accelerator can be characterized with indirect experimental techniques where linear array detectors are employed to measure the emitted synchrotron radiation or the spectrum of a near-IR laser. To improve the performance of modern beam diagnostics we have developed KALYPSO, a detector system operating with a continuous frame rate of up to 2.7 MHz. To facilitate the integration in different experiments, a modular architecture has been adopted. Different semiconductor micro-strip sensors can be connected to front-end ASICs to optimize the quantum efficiency at different photon energies, ranging from visible light up to near-IR. The front-end electronics are integrated within an heterogeneous DAQ consisting of FPGAs and GPUs, which allows scientists to implement real-time data processing algorithms. The current version of the detector is in operation at the KARA synchrotron light source and at the European XFEL. Finally, in this contribution we present the detector architecture, the performance results and the on-going technical developments.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

N2 Lyman-Birge-Hopfield dayglow from ATLAS 1

Spectral measurements of the far ultraviolet dayglow were made from the ATLAS 1 shuttle mission using an intensified charge coupled device (CCD) imaging spectrometer array. The instrument imaged relatively large (177 A) segments of the spectrum simultaneously and had the capability to image altitude in the second dimension of the two-dimensional focal plane detector when the entrance slit of the instrument was oriented perpendicular to the limb of the Earth. The far ultraviolet (FUV) channel of the instrument used a CsTe photocathode rather than the more conventionally used and more solar blind CsI photocathode material. As a result, the spectra were also measured with good sensitivity at FUV wavelengths longer than 1500 A. In this paper, data are selected of specific interest to a study of the N2 Lyman-Birge-Hopfield system using two shuttle attitudes: In the first the field of view was held at a fixed tangent ray height of approximately 140 km while scanning in wavelength, providing repeated FUV spectra over a range of latitudes and allowing comparison with our thermospheric airglow model. In the second observing sequence the line of sight of the instrument was scanned down through the atmosphere but covered about 75% of the full wavelength range. This sequence allows comparison of height dependence,including O2 absorption effects, with the thermospheric model. In all cases, relatively good agreement is obtained with the model (run strictly in a predictive mode) in comparisions in which the line of sight must be intergrated along a path that spans a considerable range of conditions (height, local time, latitude, solar zenith angle). In the case of the data sets examined in this study the vibrational population distributions show mixed results. In one case the distribution agrees well with a theoretical model based on direct electron impact excitation without a significant cascade contribution. A second case indicated a lower population in nu' = 3 and a higher population in nu' = 6 than would be expected from direct impact excitation alone. This supports previous indications that conditions resulting in the cascade mechanism may not always be operative.

Torr, Marsha R.↗

Wafer-Free Crystalline Silicon Solar Cells (CRADA Final Report)

This CRADA project, based on the DOE Solar Energy Technologies Office (SETO) Solar Prize Voucher program, helped Leap Photovoltaics to develop methodologies to immobilize Si particles by permanently attaching them to an Al-coated substrate and thereby forming carrier-selective electrical contacts to the Si particles. The bigger goal was to help Leap Photovoltaics develop these immobilized and contacted particle arrays into relatively efficient, inexpensive, and industrially relevant solar cells. By using Si particles instead of wafers in a solar cell absorber layer, one can avoid costs associated with growing monocrystalline Si ingots, then diamond-sawing them into wafers, then processing wafers into cells – a mainstream practice in today's high-efficiency Si cell and module technology. Monocrystalline or polycrystalline Si particles can be obtained in various ways: for example, Si kerf from wafer sawing is monocrystalline; recycled Si cell wafers can be ball-milled into particles; particles can be grown using various gas-phase techniques (mostly from SiH4). These Si particles can be assembled onto a substrate and serve as an absorber layer for the solar cell, absorbing photons to generate photocarriers. The challenge with this technique is to collect photocarriers from individual Si particles, with separation of photogenerated electrons to the negative cell’s electrode and positive photogenerated holes to the positive electrode. Therefore, each particle must have two isolated, carrier-selective contacts: one for electrons and one for holes. Plus, particles need to be immobilized onto a solid substrate. The goal of this work was focused on the immobilization of Si particles and creating hole-selective contact to them at the same time, using industrially relevant Si photovoltaic (PV) cell technology: screen printing of Al back-surface field electrodes. This is used in the mainstream Propane Education and Research Council (PERC) technology for hole-collecting contacts at the back of the cell. The work performed at NREL consisted of screen printing of Al metal paste on substrates, spreading Si particles onto it, and thermally processing the structures to form hole-collecting contacts. The final structures were investigated by scanning electron microscopy (SEM) after focused ion beam (FIB) cross-sectioning and polishing. The work was done jointly by NREL staff and Leap Photovoltaics (Leap PV) employees stationed at NREL. The samples were then taken to Leap PV for further processing. Training the Leap PV employee on various NREL techniques (laser cutting, screen printing, thermal processing, characterization) was part of the scope.

14 SOLAR ENERGY↗

Quasiparticle excitations in a one-dimensional interacting topological insulator: Application for dopant-based quantum simulation

Here, we study the effects of electron-electron interactions on the charge excitation spectrum of the spinful Su-Schrieffer-Heeger (SSH) model, a prototype of a one-dimensional bulk obstructed topological insulator. In view of recent progress in the fabrication of dopant-based quantum simulators we focus on experimentally detectable signatures of interacting topology in finite lattices. To this end we use Lanczos-based exact diagonalization to calculate the single-particle spectral function in real space which generalizes the local density of states to interacting systems. Its spatial and spectral resolution allows for the direct investigation and identification of edge states. By studying the noninteracting limit, we demonstrate that the topological in-gap states on the boundary are robust against both finite-size effects as well as random bond and onsite disorder which suggests the feasibility of simulating the SSH model in engineered dopant arrays in silicon. While edge excitations become zero-energy spinlike for any finite interaction strength, our analysis of the spectral function shows that the single-particle charge excitations are gapped out on the boundary. Despite the loss of topological protection, we find that these edge excitations are quasiparticlelike as long as they remain within the bulk gap. Above a critical interaction strength of U c ≈5t these quasiparticles on the boundary lose their coherence which is explained by the merging of edge and bulk states. This is in contrast to the many-body edge excitations which survive the limit of strong coupling, as established in the literature. Our findings show that for moderate repulsive interactions the nontrivial phase of the interacting SSH model can be detected through remnant signatures of topological single-particle states using single-particle local measurement techniques such as scanning tunneling spectroscopy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

2D-EFICACY: Control of Metastable 2D Carbide[1]Chalcogenide Heterolayers: Strain and Moire Engineering

The experimental isolation of graphene led to the discovery of an entirely new world of two-dimensional (2D) materials in which the 2D nature often leads to emergent behaviors not seen in bulk systems. 2D transition metal dichalcogenides (TMDs) exhibit physico-chemical properties that depend on the transition metal, polymorph, thickness, and presence and type of defects. Recently, a group of thin (10-100nm) transition metal carbides (TMCs), such as Mo2C, has been synthesized that exhibit a thickness-dependent superconducting critical temperature (Tc). These thin TMCs are different from MXenes, another class of 2D materials consisting of few layers of nitrides or carbides (<5nm) produced by chemical etching and delamination. The goal of this renewal proposal is to combine experiment and computation to synthesize and elucidate the guiding principles that control the growth, orientation and strain of heterostacks of thin TMCs and TMDs composed with Nb, Ti and W. We expect to stabilize metastable hybrid phases of TMCs sandwiched between TMDs (H-TMD/Cs) with unprecedented physico-chemical properties. As part of previous DOE-funded work by the Terrones/Sinnott groups, thin (10-100 nm thick) Mo2C flakes were successfully synthesized by chemical vapor deposition (CVD). By subsequently exposing Mo2C to H2S, partial chalcogenization was achieved, resulting in heterostacks of MoCx phases and MoS2. The formation of MoS2 led to a deficiency of Mo atoms in the underlying Mo2C, resulting in an inhomogeneous phase change from α-Mo2C to γ’-MoCx and then to γ-MoC. The γ’-MoCx is a strained metastable phase and the heterostack of all three phases demonstrated an increased Tc relative to that of α-Mo2C, from 4 to 6K; its interleaved layered structure consisting of superconducting and semiconducting phases is ideal for future studies of Josephson junction series arrays. Moiré patterns in these heterostacked systems could result in new phenomena, as moiré patterns in bilayer graphene showed unconventional superconductivity and moiré excitons have been observed in twisted TMD heterobilayers. The scientific hypothesis of the proposed synergistic computational and experimental research is that orientation and strain control within confined thin metastable TMCs, sandwiched by stable phases of TMCs and layered TMDs, will depend on kinetic and thermodynamic “knobs” that include fast temperature changes, chalcogen diffusion through preferred crystallographic planes, reaction times, pressure, reactive atmosphere, precursors, and surfactants, which will also tailor properties such as superconductivity, magnetism, ferroelectricity, piezoelectricity, and catalytic performance. We will develop the guiding principles for the synthesis and stabilization of metastable H-TMD/Cs based on Nb, Ti and W. In order to validate the hypothesis, four tasks are proposed: The first task will synthesize ultra-thin TMCs based on Nb, W and Ti, by: 1) adapting the CVD method used for Mo2C, 2) plasma assisted CVD, 3) defect-mediated CVD processes, and 4) cryo-milling of carbide powders. The second task will accomplish the synthesis and basic physico-chemical characterizations of H-TMD/Cs by chalcogenization of the materials synthesized in task one, and by carbonization of TMDs. H-TMD/Cs will also be investigated for their suitability in energy conversion applications such as supercapacitors, Li and multivalent ion batteries, and electrocatalysts, topics of interest to DoE. These tasks will be carried out in close conjunction with density functional theory (DFT) calculations with insights into energetics, lattice parameters, stability, phase diagrams, band structures, and density of states of H-TMD/Cs. The third task will characterize and evaluate strain and moiré patterns at the interfaces of different H-TMD/Cs by high-resolution scanning transmission electron microscopy (HR-STEM), scanning tunneling microscopy (STM), and conductive tip atomic force microscopy. Nudged elastic band calculations with DFT will be performed to understand the chalcogen diffusion process, which will provide insights into the interfaces between different phases of TMCs and TMDs. The fourth task aims at quantifying the stability and dynamics of H-TMD/Cs by in-situ TEM and Raman studies under heating, strain, and electrical biasing. Phonon calculations using DFT will provide a basis for interpreting Raman spectra. This coherent framework involving synthesis, characterization, and computation will result in a broad scientific impact for energy related applications. The ability to develop new H-TMD/Cs will enhance a range of applications that include batteries, catalysts, switches, sensors, quantum computing components and smart coatings.

2-Dimensional materials↗

2D-EFICACY: Control of Metastable 2D Carbide Chalcogenide Heterolayers: Strain and Moire Engineering

The experimental isolation of graphene led to the discovery of an entirely new world of two-dimensional (2D) materials in which the 2D nature often leads to emergent behaviors not seen in bulk systems. 2D transition metal dichalcogenides (TMDs) exhibit physico-chemical properties that depend on the transition metal, polymorph, thickness, and presence and type of defects. Recently, a group of thin (10-100nm) transition metal carbides (TMCs), such as Mo 2 C, has been synthesized that exhibit a thickness-dependent superconducting critical temperature (Tc). These thin TMCs are different from MXenes, another class of 2D materials consisting of few layers of nitrides or carbides (<5nm) produced by chemical etching and delamination. The goal of this renewal proposal is to combine experiment and computation to synthesize and elucidate the guiding principles that control the growth, orientation and strain of heterostacks of thin TMCs and TMDs composed with Nb, Ti and W. We expect to stabilize metastable hybrid phases of TMCs sandwiched between TMDs (H-TMD/Cs) with unprecedented physico-chemical properties. As part of previous DOE-funded work by the Terrones/Sinnott groups, thin (10-100 nm thick) Mo 2 C flakes were successfully synthesized by chemical vapor deposition (CVD). By subsequently exposing Mo 2 C to H 2 S, partial chalcogenization was achieved, resulting in heterostacks of MoCx phases and MoS 2 . The formation of MoS 2 led to a deficiency of Mo atoms in the underlying Mo 2 C, resulting in an inhomogeneous phase change from α-Mo 2 C to γ’-MoCx and then to γ-MoC. The γ’-MoCx is a strained metastable phase and the heterostack of all three phases demonstrated an increased Tc relative to that of α-Mo 2 C, from 4 to 6K; its interleaved layered structure consisting of superconducting and semiconducting phases is ideal for future studies of Josephson junction series arrays. Moiré patterns in these heterostacked systems could result in new phenomena, as moiré patterns in bilayer graphene showed unconventional superconductivity and moiré excitons have been observed in twisted TMD heterobilayers. The scientific hypothesis of the proposed synergistic computational and experimental research is that orientation and strain control within confined thin metastable TMCs, sandwiched by stable phases of TMCs and layered TMDs, will depend on kinetic and thermodynamic “knobs” that include fast temperature changes, chalcogen diffusion through preferred crystallographic planes, reaction times, pressure, reactive atmosphere, precursors, and surfactants, which will also tailor properties such as superconductivity, magnetism, ferroelectricity, piezoelectricity, and catalytic performance. We will develop the guiding principles for the synthesis and stabilization of metastable H-TMD/Cs based on Nb, Ti and W. In order to validate the hypothesis, four tasks are proposed: The first task will synthesize ultra-thin TMCs based on Nb, W and Ti, by: 1) adapting the CVD method used for Mo 2 C, 2) plasma assisted CVD, 3) defect-mediated CVD processes, and 4) cryo-milling of carbide powders. The second task will accomplish the synthesis and basic physico-chemical characterizations of H-TMD/Cs by chalcogenization of the materials synthesized in task one, and by carbonization of TMDs. H-TMD/Cs will also be investigated for their suitability in energy conversion applications such as supercapacitors, Li and multivalent ion batteries, and electrocatalysts, topics of interest to DoE. These tasks will be carried out in close conjunction with density functional theory (DFT) calculations with insights into energetics, lattice parameters, stability, phase diagrams, band structures, and density of states of H-TMD/Cs. The third task will characterize and evaluate strain and moiré patterns at the interfaces of different H-TMD/Cs by high-resolution scanning transmission electron microscopy (HR-STEM), scanning tunneling microscopy (STM), and conductive tip atomic force microscopy. Nudged elastic band calculations with DFT will be performed to understand the chalcogen diffusion process, which will provide insights into the interfaces between different phases of TMCs and TMDs. The fourth task aims at quantifying the stability and dynamics of H-TMD/Cs by in-situ TEM and Raman studies under heating, strain, and electrical biasing. Phonon calculations using DFT will provide a basis for interpreting Raman spectra. This coherent framework involving synthesis, characterization, and computation will result in a broad scientific impact for energy related applications. The ability to develop new H-TMD/Cs will enhance a range of applications that include batteries, catalysts, switches, sensors, quantum computing components and smart coatings.

2-Dimensional Materials↗

Foundations of machine learning for low-temperature plasmas: methods and case studies

Abstract Machine learning (ML) and artificial intelligence have proven to be an invaluable tool in tackling a vast array of scientific, engineering, and societal problems. The main drivers behind the recent proliferation of ML in practically all aspects of science and technology can be attributed to: (a) improved data acquisition and inexpensive data storage; (b) exponential growth in computing power; and (c) availability of open-source software and resources that have made the use of state-of-the-art ML algorithms widely accessible. The impact of ML on the field of low-temperature plasmas (LTPs) could be particularly significant in the emerging applications that involve plasma treatment of complex interfaces in areas ranging from the manufacture of microelectronics and processing of quantum materials, to the LTP-driven electrification of the chemical industry, and to medicine and biotechnology. This is primarily due to the complex and poorly-understood nature of the plasma-surface interactions in these applications that pose unique challenges to the modeling, diagnostics, and predictive control of LTPs. As the use of ML is becoming more prevalent, it is increasingly paramount for the LTP community to be able to critically analyze and assess the concepts and techniques behind data-driven approaches. To this end, the goal of this paper is to provide a tutorial overview of some of the widely-used ML methods that can be useful, amongst others, for discovering and correlating patterns in the data that may be otherwise impractical to decipher by human intuition alone, for learning multivariable nonlinear data-driven prediction models that are capable of describing the complex behavior of plasma interacting with interfaces, and for guiding the design of experiments to explore the parameter space of plasma-assisted processes in a systematic and resource-efficient manner. We illustrate the utility of various supervised, unsupervised and active learning methods using LTP datasets consisting of commonly-available, information-rich measurements (e.g. optical emission spectra, current–voltage characteristics, scanning electron microscope images, infrared surface temperature measurements, Fourier transform infrared spectra). All the ML demonstrations presented in this paper are carried out using open-source software; the datasets and codes are made publicly available. The FAIR guiding principles for scientific data management and stewardship can accelerate the adoption and development of ML in the LTP community.

Physics↗

Liquid Interfacial Electron Microscopy Identifies Nanogalvanic Corrosion in Pearlitic Steel

The nanoscale mechanisms of localized corrosion in low carbon steels have remained elusive due to the complexity of studying the degradative material behavior at nanoscale solid-liquid interfaces. We identified various steps in the nanogalvanic corrosion processes using in-situ liquid-cell scanning transmission electron microscopy (STEM) using a microfluidic holder by Hummingbird Scientific. Initial work, performed at low magnification, identified the initiation point on a 1018 low-carbon steel surface. This initiation point was determined to be a triple junction of two ferrite grains bridging a cementite grain in contact with a baseline electrolyte of 6 uM CO2 dissolved in a buffered (2.78 uM Na2SO4) aqueous solution, pH 6.1. The pre-etched low-carbon steel surface was prepared using focused ion beam lift-out procedures to extract a cross-section of the low-carbon steel surface, which then was thinned to about 150 nm and transferred to a SiN membrane microfluidic window. The transfer was made using a lift-out needle to attach the low-carbon steel lamella to the corner of the SiN window, and then Pt/C deposition held the lamella in contact with the window while it was released from the lift out needle. To identify the triple point on the low carbon steel lamella, prior to attachment on the SiN window, the sample was characterized for compositional variations with energy dispersive x-ray spectroscopy mapping, grain orientation and phase mapping with precession electron diffraction, and thickness mapping with energy filtered transmission electron microscopy. This pre-characterization prior to the in-situ experiment provided a map of the multiphase and multigrain structure, where the in-situ liquid cell imaging provided a clear understanding of the initiation point on the sample. These data were cross-correlated to paint a holistic picture of the triple junction site, enabling low electron-fluence in-situ snapshot imaging to avoid dominating the native corrosion reactions with effects from the incident electron beam. This initial result identified that localized, nanogalvanic corrosion at the phase interface was the dominant corrosion process in the low-carbon steel, so we next targeted the observation of an array of these nanogalvanic features phase boundaries in a pearlite grain. Near-surface ferrite/cementite phase interfaces that typify pearlitic low-carbon steel were extracted, pre-characterized, and imaged for the in-situ corrosion processes. The sample was a cross-section from a pearlite grain, with alternating ferrite and cementite grains that extended microns down from the pre-etched low-carbon steel pipe surface. After contact with a buffered aqueous solution, the phase boundaries between the ferrite and cementite began to dissolve, with observable material loss and thickness changes in the dark-field and bright-field STEM images. Within minutes, the corrosion front proceeded deeper into the material, claiming a thin layer of ferrite around all exposed phase boundaries before progressing laterally into the ferrite matrix, converting the ferrite to corrosion product normal to each buried cementite grain. Formation of the corrosion product causes a volumetric expansion, creating a lateral wedging force that mechanically ejects the cementite grains from their grooves and leaves behind percolation channels into the steel substructure. Rapid and deleterious, this nanogalvanic corrosion pathway represents an important target for understanding and preventing run-away degradation in this common building material. Observation of this corrosion mechanism was enabled by the combination of pre-characterization using standard structural, grain, and compositional analysis in the TEM, which provides maps for understanding the reaction propagation captured in low-dose, in-situ, liquid-cell STEM.

corrosion↗

Characterization of an architecture for front-end pixel binning in an integrating pixel array detector

Optimization of an area detector involves compromises between various parameters like frame rate, read noise, dynamic range and pixel size. We have implemented and tested a novel front-end binning design in a photon-integrating hybrid pixel array detector using the MM-PAD- 2.0 pixel architecture. In this architecture, the pixels can be optionally binned in a 2 x 2 pixel configuration using a network of switches to selectively direct the output of 4 sensor pixels to a single amplifier input. Doing this allows a trade-off between frame rate and spatial resolution. Tests show that the binned pixels perform well, but with some degradation on performance as compared to an un-binned pixel. The increased parasitic input capacitance does reduce the signal collected per x-ray as well as increases the noise of the pixel. Here, the increase in noise is, however, less than the factor of 2 increase one would observe for binning in post-processing. Spatial scans across the binned pixels show that no measured signal intensity is lost at the inner binning unit boundaries. In the high flux regime, at a 2 x 2 pixel wide beam spot (FWHM) size, binned mode responds linearly up to a photon flux of 10 7 x-rays/s, and performs comparably with un-binned mode up to a photon flux of 10 8 x-rays/s. While this study demonstrates a proof of concept for front-end binning in integrating detectors, we also identify changes to this early-stage prototype which can further improve the performance of binning pixel structures.

47 OTHER INSTRUMENTATION↗