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At least 1,243 records · Page 69

In-house synthesized poly(ether ether ketone) ionenes. I. ToF-SIMS spectra in the positive ion mode

Static time-of-flight secondary ion mass spectrometry (ToF-SIMS) was performed for acquiring the high-resolution surface spectra of four types of synthesized imidazolium ionene membranes. These novel membranes have aromatic ether–ketone–ether linkages inspired by poly(ether ether ketone) (PEEK). The PEEK-ionenes synthesized for this study have imidazolium cations placed in the polymeric backbone with bistriflimide [Tf 2 N]- counterions. The attention given to synthetically modified PEEK derivatives, such as PEEK-ionenes, is considerable due to their ability to selectively capture CO 2 molecules and other light gases. Therefore, it is important to characterize the surface of these synthesized novel PEEK-ionenes. In this work, characteristic and unique peaks were identified in the positive spectra of each sample. The differences in mass spectra among the samples provide insights for optimizing or fine-tuning the PEEK-ionenes synthesis to achieve a high-performance CO 2 separation membrane with enhanced permeability, selectivity, and mechanical stability. The SIMS spectra and identified characteristic peaks of these synthesized ionenes will serve as a reference in the positive mode, complementing the corresponding spectra reported in the negative ion mode (Paper II).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In-house synthesized poly(ether ether ketone) ionenes. II. ToF-SIMS spectra in the negative ion mode

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to analyze poly(ether ether ketone) (PEEK) based membranes. PEEK membranes have been shown to be effective in the separation of CO 2 from flue gases (post-combustion technique). The PEEK membranes were synthesized using novel aromatic ether-ketone linkages inspired by PEEK with polymeric backbone bistriflimide [Tf2N]− counterions. One of the keys to advancing this technology is developing membranes that are selective and permeable toward CO 2 , in which PEEK based membranes have been shown to be. Furthermore, the compatibility between various water lean solvents also needs to be investigated. Surface analytical techniques such as x-ray photoelectron spectroscopy and ToF-SIMS are useful for investigating chemical changes between membranes. Herein, we present ToF-SIMS data obtained in the negative ion mode for four different PEEK membranes designed for use in CO 2 capture systems. Positive ion mode spectra are reported in Paper I.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Future of plasma etching for microelectronics: Challenges and opportunities

Plasma etching is an essential semiconductor manufacturing technology required to enable the current microelectronics industry. Along with lithographic patterning, thin-film formation methods, and others, plasma etching has dynamically evolved to meet the exponentially growing demands of the microelectronics industry that enables modern society. At this time, plasma etching faces a period of unprecedented changes owing to numerous factors, including aggressive transition to three-dimensional (3D) device architectures, process precision approaching atomic-scale critical dimensions, introduction of new materials, fundamental silicon device limits, and parallel evolution of post-CMOS approaches. The vast growth of the microelectronics industry has emphasized its role in addressing major societal challenges, including questions on the sustainability of the associated energy use, semiconductor manufacturing related emissions of greenhouse gases, and others. The goal of this article is to help both define the challenges for plasma etching and point out effective plasma etching technology options that may play essential roles in defining microelectronics manufacturing in the future. The challenges are accompanied by significant new opportunities, including integrating experiments with various computational approaches such as machine learning/artificial intelligence and progress in computational approaches, including the realization of digital twins of physical etch chambers through hybrid/coupled models. These prospects can enable innovative solutions to problems that were not available during the past 50 years of plasma etch development in the microelectronics industry. To elaborate on these perspectives, the present article brings together the views of various experts on the different topics that will shape plasma etching for microelectronics manufacturing of the future.

Engineering↗

Low-temperature etching of silicon oxide and silicon nitride with hydrogen fluoride

Etching of high aspect ratio features into alternating SiO 2 and SiN layers is an enabling technology for the manufacturing of 3D NAND flash memories. In this paper, we study a low-temperature or cryo plasma etch process, which utilizes HF gas together with other gas additives. Compared with a low-temperature process that uses separate fluorine and hydrogen gases, the etching rate of the SiO 2 /SiN stack doubles. Both materials etch faster with this so-called second generation cryo etch process. Pure HF plasma enhances the SiN etching rate, while SiO 2 requires an additional fluorine source such as PF 3 to etch meaningfully. Further, the insertion of H 2 O plasma steps into the second generation cryo etch process boosts the SiN etching rate by a factor of 2.4, while SiO 2 etches only 1.3 times faster. We observe a rate enhancing effect of H 2 O coadsorption in thermal etching experiments of SiN with HF. Ammonium fluorosilicate (AFS) plays a salient role in etching of SiN with HF with and without plasma. AFS appears weakened in the presence of H 2 O. Density functional theory calculations confirm the reduction of the bonding energy when NH 4 F in AFS is replaced by H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Report on laser-induced fluorescence transitions relevant for the microelectronics industry and sustainability applications

A wide variety of feed gases are used to generate low-temperature plasmas for the microelectronics and sustainability applications. These plasmas often have a complex combination of reactive and nonreactive species which may have spatial and temporal variations in density, temperature, and energy. Accurate knowledge of these parameters and their variations is critically important for understanding and advancing these applications through validated and predictive modeling and the design of relevant devices. Laser-induced fluorescence (LIF) provides both spatial and temporally resolved information about the plasma-produced radicals, ions, and metastables. However, the use of this powerful diagnostic tool requires the knowledge of optical transitions including excitation and fluorescence wavelengths which may not be available or scattered through a huge literature domain. In this paper, we collected, analyzed, and compiled the available transitions for laser-induced fluorescence for more than 160 chemical species relevant to the microelectronics industry and the sustainability applications. A list of species with overlapping LIF excitations and fluorescence wavelengths have been identified. Finally, this summary is intended to serve as a data reference for LIF transitions and should be updated in the future.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Line emission mapper microcalorimeter spectrometer

The line emission mapper (LEM) is a probe-class mission concept that is designed to detect x-ray emission lines from hot ionized gas (T > 10 6 K) that will enable us to test galaxy evolution theories. It will permit us to study the effects of stellar and black-hole feedback and flows of baryonic matter into and out of galaxies. The key to being able to study the hot gases that are otherwise invisible to current imaging x-ray spectrometers is that the energy resolution is sufficient to use cosmological redshift to separate extragalactic source lines from foreground Milky Way emission. LEM incorporates a large-format microcalorimeter array instrument called the LEM microcalorimeter spectrometer (LMS) with a light-weight x-ray optic with 10” half power diameter angular resolution. The LMS microcalorimeter array has pixels with 15" pixel pitch over a 33' field of view (FOV) optimized for the 0.3 to 2 keV energy band. The central 7' region of the array has an energy resolution of 1.3 eV at 1 keV and the rest of the FOV has 2.5 eV energy resolution at 1 keV. The array will be read out with state-of-the-art time-division multiplexing. We present an overview of the LMS instrument, including details of the entire detection chain, the focal plane assembly, as well as the cooling system and overall mechanical and thermal design. For each of the key technologies, we discuss the current technology readiness level and the plan to advance them to be ready for flight. We also describe the current system design and our estimate for the mass, power, and data rate of the instrument. The design details presented concentrate primarily on the unique aspects of the LMS design compared with prior missions and confirm that the type of microcalorimeter instrument needed for LEM is not only feasible but also technically mature.

47 OTHER INSTRUMENTATION↗

One-shot gas detection with transformer paired neural networks in Mako collected longwave infrared hyperspectral imagery

To date, careful data treatment workflows and statistical detectors are used to perform hyperspectral image (HSI) detection of any gas contained in a spectral library, which is often expanded with physics models to incorporate different spectral characteristics. In general, surrounding evidence or known gas-release parameters are used to provide confidence in or confirm detection capability, respectively. This makes quantifying detection performance difficult as it is nearly impossible to develop an absolute ground truth for gas target pixel presence in collected HSI. Consequently, developing and comparing new detection methods, especially machine learning (ML)-based methods, is susceptible to subjectivity in derived detection map quality. Here, in this work, we demonstrate the first use of transformer-based paired neural networks (PNNs) for one-shot gas target detection for multiple gases while providing quantitative classification and detection metrics for their use on labeled data. Terabytes of training data are generated from a database of long-wave infrared HSI obtained from historical Mako sensor campaigns over Los Angeles. By incorporating labels, singular signature representations, and a model development pipeline, we can tune and select PNNs to detect multiple gas targets that are not seen in training on a quantitative basis. We additionally assess our test set detections using interpretability techniques widely employed with ML-based predictors, but less common with detection methods relying on learned latent spaces.

Hyperspectral imaging↗

Quantitative far-infrared band strengths of iodine monochloride (ICl), a molten salt off-gas product

The gaseous (by)products generated from molten salt reactors need to be monitored to prevent the release of potentially toxic gases to the environment. In particular, 129I has a long half-life and its toxicity and persistence in the environment make iodine and iodine-containing compounds (such as ICl from chloride containing molten salt systems) of great concern. Optical spectroscopy tools, including Raman and Fourier-transform infrared (FTIR) spectroscopies, are ideal for monitoring and quantifying such off-gas products. Iodine (I2) has a strong and distinct Raman signature and the change in signal with a change in concentration can be used for quantification of these byproducts. Iodine monochloride (ICl) has distinct signatures in both the Raman and the infrared, and its spectrum can also potentially be used for quantitative measurement of this species. In this paper we discuss our recent results on the quantification of iodine monochloride using infrared spectroscopy, in particular first reports of the absolute infrared band strength of ICl.

infrared (IR) spectroscopy, Molten Salt Reactors, ↗

Thermoacoustic Soret separation

In a fluid mixture in a channel with an axial time-averaged temperature gradient, high-amplitude oscillating flow can greatly increase the axial flux of thermal diffusion (Soret) separation of the components of the mixture. The enhancement occurs when the oscillating lateral temperature gradient greatly exceeds the axial gradient, causing a large oscillating concentration that can be favorably time-phased with the oscillating flow. This process can occur even with a negligible pressure oscillation or with a negligible temperature response to pressure, as is the case in most liquid solutions. The thermal boundary condition imposed by realistic solids on thermoacoustic liquids is imperfect, adding mathematical complications that are absent for typical gases, for which the solid surface is temporally isothermal. Compared with gas mixtures, the high Lewis number in typical liquid solutions reduces the separation flux associated with the time-averaged temperature gradient, but it also reduces the remixing associated with the time-averaged mole-fraction gradient. For large enough channels, the second-law separation efficiency is only slightly reduced from that of steady liquid Soret separation.

36 MATERIALS SCIENCE↗

Strong suppression of heat conduction in a laboratory replica of galaxy-cluster turbulent plasmas

In conventional gases and plasmas, it is known that heat fluxes are proportional to temperature gradients, with collisions between particles mediating energy flow from hotter to colder regions and the coefficient of thermal conduction given by Spitzer’s theory. However, this theory breaks down in magnetized, turbulent, weakly collisional plasmas, although modifications are difficult to predict from first principles due to the complex, multiscale nature of the problem. Understanding heat transport is important in astrophysical plasmas such as those in galaxy clusters, where observed temperature profiles are explicable only in the presence of a strong suppression of heat conduction compared to Spitzer’s theory. To address this problem, we have created a replica of such a system in a laser laboratory experiment. Our data show a reduction of heat transport by two orders of magnitude or more, leading to large temperature variations on small spatial scales (as is seen in cluster plasmas).

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

In situ temperature measurements in sooting methane/air flames using synchrotron x-ray fluorescence of seeded krypton atoms

Synchrotron x-ray fluorescence has been used to measure temperatures in optically dense gases where traditional methods would fail. These data provide a benchmark for stringent tests of computational fluid dynamics models for complex systems where physical and chemical processes are intimately linked. The experiments measured krypton number densities in a sooting, atmospheric pressure, nonpremixed coflow flame that is widely used in combustion research. The experiments not only form targets for the models, but the simulations also identify potential sources of uncertainties in the measurements, allowing for future improvements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optically controllable magnetism in atomically thin semiconductors

We report evidence that ferromagnetic order in electrostatically doped, monolayer transition metal dichalcogenide (TMD) semiconductors can be stabilized and controlled at zero magnetic field by local optical pumping. We use circular dichroism (CD) in reflectivity from excitonic states as a spatially resolved probe of charge-carrier spin polarization. At electron densities $n_e$ ~ 10 12 cm -2 , a diffraction-limited, circularly polarized optical pump breaks symmetry between oppositely polarized magnetic states and stabilizes long-range magnetic order, with carrier polarization exceeding 80% over an 8 μm by 5 μm extent. In time-resolved measurements with pulsed optical excitation, we observe that magnetic interactions amplify the initial pump-induced spin polarization by more than an order of magnitude. The optical control of magnetism with local optical pumps will unlock advancements in spin and optical technologies and provides a versatile tool in the study of correlated phases in two-dimensional electron gases.

36 MATERIALS SCIENCE↗

Chiral edge state control of thermoelectric effects

Thermoelectric responses in two-dimensional electron gases subjected to magnetic fields have the potential to provide unique information about quasiparticle statistics. In this study, we show that chiral edge states play a key role in thermoelectric Hall bar measurements by completely controlling the direction of the internal thermal gradient. To this end, we perform measurements of the magnetothermoelectric responses of cadmium arsenide quantum wells. The magnetothermoelectric responses in the quantum Hall regime agree with theoretical predictions if one considers the role of chiral edge states, which flow in opposite directions on either side of the Hall bar and establish an internal temperature gradient that is perpendicular to the externally applied thermal gradient. We show that the results are self-consistent within this picture under different measurement conditions. We discuss potential applications of the findings, such as in nanoscale control of local temperature gradients and thermoelectric effects along with the characterization of other topological systems with chiral edges states.

Science & Technology - Other Topics↗

A nitrogenase-like enzyme system catalyzes methionine, ethylene, and methane biogenesis

Bacterial production of hydrocarbon gases like ethylene and methane affects soil ecosystems and the climate. This study reveals that methane and ethylene from land and freshwater bacteria are directly produced by a previously unknown methionine biosynthesis pathway. This pathway employs a nitrogenase-like reductase that is distinct from known nitrogenases and nitrogenase-like reductases. The nitrogenase-like methylthio-alkane reductase specifically functions in carbon-sulfur bond breakage to reduce ubiquitous and significant volatile organic sulfur compounds such as dimethyl sulfide and (2-methylthio)ethanol. The liberated methanethiol serves as the immediate precursor to methionine. Whereas ethylene or methane is released into the environment. This pathway provides a biological route to the synthesis of ethylene in the absence of oxygen. Finally, anaerobic ethylene production by this pathway apparently explains the long-standing observation of ethylene accumulation in oxygen-depleted soils Methane production reveals an additional bacterial pathway that is distinct from archaeal methanogenesis.

10 SYNTHETIC FUELS↗

Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization

The current scale of plastics production and the accompanying waste disposal problems represent a largely untapped opportunity for chemical upcycling. Tandem catalytic conversion by platinum supported on γ-alumina converts various polyethylene grades in high yields (up to 80 weight percent) to low-molecular-weight liquid/wax products, in the absence of added solvent or molecular hydrogen, with little production of light gases. The major components are valuable long-chain alkylaromatics and alkylnaphthenes (average ~C 30 , dispersity Ð = 1.1). Coupling exothermic hydrogenolysis with endothermic aromatization renders the overall transformation thermodynamically accessible despite the moderate reaction temperature of 280°C. This approach demonstrates how waste polyolefins can be a viable feedstock for the generation of molecular hydrocarbon products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crossover between strongly coupled and weakly coupled exciton superfluids

Following a crossover Superfluidity in fermionic systems occurs through the pairing of fermions into bosons, which can undergo condensation. Depending on the strength of the interactions between fermions, the pairs range from large and overlapping to tightly bound. The crossover between these two limits has been explored in ultracold Fermi gases. Liu et al . observed the crossover in an electronic system consisting of two layers of graphene separated by an insulating barrier and placed in a magnetic field. In this two-dimensional system, the pairs were excitons formed from an electron in one layer and a hole in the other. The researchers used magnetic field and layer separation to tune the interactions and detected the signatures of superfluidity through transport measurements. —JS

Science & Technology - Other Topics↗

Quantum metric nonlinear Hall effect in a topological antiferromagnetic heterostructure

Quantum geometry in condensed matter physics has two components: the real part quantum metric and the imaginary part Berry curvature. Whereas the effects of Berry curvature have been observed through phenomena such as the quantum Hall effect in 2D electron gases and the anomalous Hall effect (AHE) in ferromagnets, quantum metric has rarely been explored. Here, in this paper, we report a nonlinear Hall effect induced by quantum metric dipole by interfacing even-layered MnBi 2 Te 4 with black phosphorus. The quantum metric nonlinear Hall effect switches direction upon reversing the AFM spins and exhibits distinct scaling that is independent of the scattering time. Our results open the door to discovering quantum metric responses predicted theoretically and pave the way for applications that bridge nonlinear electronics with AFM spintronics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗