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At least 523 records · Page 29

Deep potential molecular dynamics simulations of ion-enhanced etching of silicon by atomic chlorine

The continued development of plasma-assisted processing techniques requires a fundamental understanding of plasma-surface interactions. Molecular dynamics (MD) simulations have been employed to complement experimental studies and better understand the properties of such systems. Recently, machine learning (ML) methods have enabled the development of ab initio-based interatomic potentials, which can be generalized to complex combinations of multiple atom types. In this work, we use ML potentials developed using the Deep Potential Molecular Dynamics (DeepMD) framework to provide a model of ion-enhanced etching of Si by Cl atoms. We demonstrate the importance of proper selection of the training data set to the accuracy of the DeepMD model and compare our results to MD results using empirical potentials, as well as to experimental measurements. Exposure of undoped Si at 300 K to thermal Cl atoms yields a steady-state Cl coverage of 1.25 monolayers, which is slightly lower than the value obtained in previous experimental studies. Predictions of Si etch yields by simultaneous Cl atom and Ar + ion impacts as a function of ion energy, neutral to ion flux ratio, and angle of incidence of the ions are in reasonably good agreement with classical MD results and experimental measurements. Finally, etch yields and SiCl x mixed layer thicknesses during simultaneous bombardment of the Si(100) surface by Cl atoms and Cl + ions are in good agreement with experimental data. In conclusion, the present work is a necessary condition for the extension of the DeepMD procedure to more complex systems of interest in plasma-surface interactions.

Artificial neural networks↗

Split-pulse X-ray photon correlation spectroscopy with seeded X-rays from X-ray laser to study atomic-level dynamics

Abstract With their brilliance and temporal structure, X-ray free-electron laser can unveil atomic-scale details of ultrafast phenomena. Recent progress in split-and-delay optics (SDO), which produces two X-ray pulses with time-delays, offers bright prospects for observing dynamics at the atomic-scale. However, their insufficient pulse energy has limited its application either to phenomena with longer correlation length or to measurement with a fixed delay-time. Here we show that the combination of the SDO and self-seeding of X-rays increases the pulse energy and makes it possible to observe the atomic-scale dynamics in a timescale of picoseconds. We show that the speckle contrast in scattering from water depends on the delay-time as expected. Our results demonstrate the capability of measurement using the SDO with seeded X-rays for resolving the dynamics in temporal and spatial scales that are not accessible by other techniques, opening opportunities for studying the atomic-level dynamics.

36 MATERIALS SCIENCE↗

Identification and characterization of extraterrestrial non-chondritic interplanetary dust

Interplanetary dust particles (IDPs) are among the most pristine and primitive extraterrestrial materials available for direct study. Most of the stratospheric particles selected for study from the JSC Curatorial Collection were chondritic in composition (major element abundances within a factor of two of chondritic meteorites) because this composition virtually ensures that the particle is from an extraterrestrial source. It is likely that some of the most interesting classes of IDP's have not been recognized simply because they are not chondritic or do not fit established criteria for extraterrestrial origin. Indeed, mass spectroscopy data from the Giotto Flyby of comet Halley indicate that a substantial fraction of the dust is in the submicron size range and that a majority of these particles contain C, H, O, and/or N as major elements. The preponderance of CHON particles in the coma of Halley implies that similar particles may exist in the JSC stratospheric dust collection. However, the JSC collection also contains a variety of stratospheric contaminants from terrestrial sources which have these same characteristics. Because established criteria for extraterrestrial origin may not apply to such particles in individual cases, and integrated approach is required in which a variety of analysis techniques are applied to the same particle. Non-chondritic IDP's, like their chondritic counterparts, can be used to elucidate pre- and early solar system processes and conditions. The study of non-chondritic IDP's may additionally yield unique information which bears on the nature of cometary bodies and the processing of carbonaceous and other low atomic number materials. A suite of complementary techniques, including Low Voltage Scanning Electron Microscopy (LVSEM), Energy-Dispersive X-ray Microanalysis (EDX), Secondary Ion Mass Spectrometry (SIMS) isotope-ratio imaging and Analytical Electron Microscopy (AEM), were utilized to accomplish the following two objectives: (1) to develop criteria for the unequivocal identification of extraterrestrial non-chondritic IDP's; and (2) to infer IDP parent body, solar nebula, and pre-solar conditions through the study of phases, textures, and components contained within non-chondritic IDP's. The general approach taken is designed to maximize the total information obtained from each particle. Techniques will be applied in order from least destructive to most destructive.

Blake, D. F.↗

Evaluation of current density measurement methods for high-current, low-beta electron beams

Recent current density measurements with a low-beta electron beam (β=0.5-0.75) are strongly affected by electron scatter and Cherenkov limits. These invasive measurements are heavily influenced by the electron energy and the intercepting material properties: density, index of refraction, and atomic number. We evaluate various measurement methods, including x-ray scintillation and Cherenkov emission. To optimize the x-ray scintillation technique for this energy regime, metal foils of differing atomic number (Z) and thickness were placed upstream of a scintillation screen. We have selected Cherenkov emitters, based on a material refractive index, in order to differentiate the contributions from electron scatter and produced fluorescence, Cherenkov emission, and total internal reflection. The observed distributions for both approaches are verified through MCNP6®. Additionally, the simulations provide insight as to what physical processes dominate the measured distribution. We conclude by determining the limits and optimal measurement range for each measurement technique.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Synchrotron-based techniques for characterizing STCH water-splitting materials

Understanding the role of oxygen vacancy–induced atomic and electronic structural changes to complex metal oxides during water-splitting processes is paramount to advancing the field of solar thermochemical hydrogen production (STCH). The formulation and confirmation of a mechanism for these types of chemical reactions necessitate a multifaceted experimental approach, featuring advanced structural characterization methods. Synchrotron X-ray techniques are essential to the rapidly advancing field of STCH in part due to properties such as high brilliance, high coherence, and variable energy that provide sensitivity, resolution, and rapid data acquisition times required for the characterization of complex metal oxides during water-splitting cycles. X-ray diffraction (XRD) is commonly used for determining the structures and phase purity of new materials synthesized by solid-state techniques and monitoring the structural integrity of oxides during water-splitting processes (e.g., oxygen vacancy–induced lattice expansion). X-ray absorption spectroscopy (XAS) is an element-specific technique and is sensitive to local atomic and electronic changes encountered around metal coordination centers during redox. While in operando measurements are desirable, the experimental conditions required for such measurements (high temperatures, controlled oxygen partial pressures, and H 2 O) practically necessitate in situ measurements that do not meet all operating conditions or ex situ measurements. Here, we highlight the application of synchrotron X-ray scattering and spectroscopic techniques using both in situ and ex situ measurements, emphasizing the advantages and limitations of each method as they relate to water-splitting processes. The best practices are discussed for preparing quenched states of reduction and performing synchrotron measurements, which focus on XRD and XAS at soft (e.g., oxygen K-edge, transition metal L-edges, and lanthanide M-edges) and hard (e.g., transition metal K-edges and lanthanide L-edges) X-ray energies. The X-ray absorption spectra of these complex oxides are a convolution of multiple contributions with accurate interpretation being contingent on computational methods. The state-of-the-art methods are discussed that enable peak positions and intensities to be related to material electronic and structural properties. Through careful experimental design, these studies can elucidate complex structure–property relationships as they pertain to nonstoichiometric water splitting. A survey of modern approaches for the evaluation of water-splitting materials at synchrotron sources under various experimental conditions is provided, and available software for data analysis is discussed.

08 HYDROGEN↗

Rate of the reaction of atomic hydrogen with propyne over an extended pressure and temperature range

The technique of flash photolysis coupled with time resolved detection of H via resonance fluorescence has been used to obtain rate constants for the reaction of atomic hydrogen with propyne at temperatures from 215 to 460 K and at pressures in the range 5-600 torr. The rate constants are strongly pressure dependent and the high pressure limiting values give rise to the Arrhenius expression K = approximately 6 x 10 to the minus 11th exp(-2450T) cu cm per molecule per sec. The results are discussed and compared with those of previous studies

Whytock, D. A.↗

Effect of energetic oxygen atoms on neutral density models.

The dissociative recombination of O2(+) and NO(+) in the F region results in the production of atomic oxygen and atomic nitrogen with substantially greater kinetic energy than the ambient atoms. In the exosphere these energetic atoms have long free paths. They can ascend to altitudes of several thousand kilometers and can travel horizontally to distances of the order of the earth's radius. The distribution of energetic oxygen atoms is derived by means of models of the ion and neutral densities for quiet and disturbed solar conditions. A distribution technique is used to study the motion of the atoms in the collision-dominated region. Ballistic trajectories are calculated in the spherical gravitational field of the earth. The present calculations show that the number densities of energetic oxygen atoms predominate over the ambient atomic oxygen densities above 1000 km under quiet solar conditions and above 1600 km under disturbed solar conditions.

Rohrbaugh, R. P.↗

Containerless high temperature property measurements by atomic fluorescence

The use of laser induced fluorescence (LIF) techniques for containerless study of high temperature processes and material properties is studied. Gas jet and electromagnetic levitation and electromagnetic and laser heating techniques are used with LIF in Earth-based containerless high temperature experiments. The work to date includes development of an apparatus and its use in studies of chemical reactions on Al2O3, molybdenum, and tungsten specimens, novel methods for noncontact specimen temperature measurement, and levitation jet properties. Brief summaries of these studies are given. The apparatus is described and detailed results for the current reporting period are presented.

Source record↗

Molecular beam simulation of planetary atmospheric entry: Some recent results

Molecular beam sources for producing fast beams containing CO2 and atomic oxygen are discussed. Results pertinent to the design and calibration of mass spectrometer ion source for measurement of the Martian atmosphere during the free molecule portion of the entry trajectory are also presented. The shortcomings and advantages of the simulation technique are discussed. It is shown that an open cavity configuration retains sensitivity to atomic oxygen, provides reasonable signal enhancement from the stagnation effect, is not highly sensitive to pitch and yaw effects, and presents no unforeseen problems in measuring CO2 or atomic oxygen. The simulation techniques used provide assistance in designing, developing, and (potentially) in testing and calibrating the required flight instrument.

French, J. B.↗

Ground-Laboratory to In-Space Effective Atomic-Oxygen Fluence Determined for DC 93-500 Silicone

Surfaces on the leading edge of spacecraft in low Earth orbit (e.g., surface facing the velocity direction), such as on the International Space Station, are subject to atomic oxygen attack, and certain materials are susceptible to erosion. Therefore, ground-based laboratory testing of the atomic oxygen durability of spacecraft materials is necessary for durability assessment when flight data are not available. For accurate space simulation, the facility is commonly calibrated on the basis of the mass loss of Kapton (DuPont, Wilmington, DE) as a control sample for effective fluence determination. This is because Kapton has a well-characterized atomic oxygen erosion yield (E(sub y), in cubic centimeters per atom) in the low Earth orbit (LEO) environment. Silicones, a family of commonly used spacecraft materials, do not chemically erode away with atomic oxygen attack like other organic materials that have volatile oxidation products. Instead, silicones react with atomic oxygen and form an oxidized hardened silicate surface layer. Often the loss of methyl groups causes shrinkage of the surface skin and "mud-tile" crazing degradation. But silicones often do not lose mass, and some silicones actually gain mass during atomic oxygen exposure. Therefore, the effective atomic oxygen fluence for silicones in a ground-test facility should not be determined on the basis of traditional mass-loss measurements, as it is with polymers that erode. Another method for determining effective fluence needs to be employed for silicones. A new technique has been developed at the NASA Glenn Research Center for determining the effective atomic oxygen fluence for silicones in ground-test facilities. This technique determines the equivalent amount of atomic oxygen oxidation on the basis of changes in the surface-oxide hardness. The specific approach developed was to compare changes in the surface hardness of ground-laboratory-exposed DC93-500 silicone with DC93-500 exposed to LEO atomic oxygen as part of a shuttle flight experiment. The on-the-ground to in-space effective atomic oxygen fluence was determined on the basis of the Kapton effective fluence in the ground-laboratory facility that produced the same hardness for the fluence in space.

deGroh, Kim K.↗

FAIR DEAL Grand Challenge Overview

While it is likely practically a bad idea to shrink a transistor to the size of an atom, there is no arguing that it would be fantastic to have atomic-scale control over every aspect of a transistor – a kind of crystal ball to understand and evaluate new ideas. This project showed that it was possible to take a niche technique used to place dopants in silicon with atomic precision and apply it broadly to study opportunities and limitations in microelectronics. In addition, it laid the foundation to attaining atomic-scale control in semiconductor manufacturing more broadly.

74 ATOMIC AND MOLECULAR PHYSICS↗

Transient local secondary structure in the intrinsically disordered C‐term of the Albino3 insertase

Albino3 (Alb3) is an integral membrane protein fundamental to the targeting and insertion of light‐harvesting complex (LHC) proteins into the thylakoid membrane. Alb3 contains a stroma‐exposed C‐terminus (Alb3‐Cterm) that is responsible for binding the LHC‐loaded transit complex before LHC membrane insertion. Alb3‐Cterm has been reported to be intrinsically disordered, but precise mechanistic details underlying how it recognizes and binds to the transit complex are lacking, and the functional roles of its four different motifs have been debated. Using a novel combination of experimental and computational techniques such as single‐molecule fluorescence resonance energy transfer, circular dichroism with deconvolution analysis, site‐directed mutagenesis, trypsin digestion assays, and all‐atom molecular dynamics simulations in conjunction with enhanced sampling techniques, we show that Alb3‐Cterm contains transient secondary structure in motifs I and II. The excellent agreement between the experimental and computational data provides a quantitatively consistent picture and allows us to identify a heterogeneous structural ensemble that highlights the local and transient nature of the secondary structure. This structural ensemble was used to predict both the inter‐residue distance distributions of single molecules and the apparent unfolding free energy of the transient secondary structure, which were both in excellent agreement with those determined experimentally. We hypothesize that this transient local secondary structure may play an important role in the recognition of Alb3‐Cterm for the LHC‐loaded transit complex, and these results should provide a framework to better understand protein targeting by the Alb3‐Oxa1‐YidC family of insertases.

Okoto, Patience S.↗

A Eulerian-Lagrangian Model to Simulate Two-Phase/Particulate Flows

Figure 1 shows a snapshot of liquid fuel spray coming out of an injector nozzle in a realistic gas-turbine combustor. Here the spray atomization was simulated using a stochastic secondary breakup model (Apte et al. 2003a) with point-particle approximation for the droplets. Very close to the injector, it is observed that the spray density is large and the droplets cannot be treated as point-particles. The volume displaced by the liquid in this region is significant and can alter the gas-phase ow and spray evolution. In order to address this issue, one can compute the dense spray regime by an Eulerian-Lagrangian technique using advanced interface tracking/level-set methods (Sussman et al. 1994; Tryggvason et al. 2001; Herrmann 2003). This, however, is computationally intensive and may not be viable in realistic complex configurations. We therefore plan to develop a methodology based on Eulerian-Lagrangian technique which will allow us to capture the essential features of primary atomization using models to capture interactions between the fluid and droplets and which can be directly applied to the standard atomization models used in practice. The numerical scheme for unstructured grids developed by Mahesh et al. (2003) for incompressible flows is modified to take into account the droplet volume fraction. The numerical framework is directly applicable to realistic combustor geometries. Our main objectives in this work are: Develop a numerical formulation based on Eulerian-Lagrangian techniques with models for interaction terms between the fluid and particles to capture the Kelvin- Helmholtz type instabilities observed during primary atomization. Validate this technique for various two-phase and particulate flows. Assess its applicability to capture primary atomization of liquid jets in conjunction with secondary atomization models.

Apte, S. V.↗

Atomic Oxygen Environments, Effects, and Mitigation

Atomic oxygen is the most predominant specie in low Earth orbit (LEO) and is contained in the upper atmosphere of many other planetary bodies. Formed by photo-dissociation of molecular oxygen, it is highly reactive and energetic enough to break chemical bonds on the surface of many materials and react with them to form either stable or volatile oxides. The extent of the damage for spacecraft depends a lot on how much atomic oxygen arrives at the surface, the energy of the atoms, the reactivity of the material that is exposed to it and other constituents in the atmosphere. Oxide formation can result in shrinkage, cracking, or erosion which can also result in changes in optical, thermal, or mechanical properties of the materials exposed. The extent of the reaction can be affected by mechanical loading, temperature, and other environmental components such as ultraviolet radiation or charged particles. Atomic oxygen generally causes a surface reaction, but it can scatter under coatings and into crevices causing oxidation much farther into a spacecraft surface or structure than would be expected. Atomic oxygen effects for LEO atomic oxygen compared to atomic oxygen effects in a Mars environment, effects atomic oxygen can have on typical spacecraft materials, and mitigation techniques will be presented.

Oxygen atoms↗

Controlling hydrocarbon transport and electron beam induced deposition on single layer graphene: Toward atomic scale synthesis in the scanning transmission electron microscope

Abstract Focused electron beam induced deposition (FEBID) is a direct write technique for depositing materials on a support substrate akin to 3D printing with an electron beam (e‐beam). Opportunities exist for merging this existing technique with aberration‐corrected scanning transmission electron microscopy to achieve molecular‐ or atomic‐level spatial precision. Several demonstrations have been performed using graphene as the support substrate. A common challenge that arises during this process is e‐beam‐induced hydrocarbon deposition, suggesting greater control over the sample environment is needed. Various strategies exist for cleaning graphene in situ. One of the most effective methods is to rapidly heat to high temperatures, for example, 600℃ or higher. While this can produce large areas of what appears to be atomically clean graphene, mobile hydrocarbons can still be present on the surfaces. Here, we show that these hydrocarbons are primarily limited to surface migration and demonstrate an effective method for interrupting the flow using e‐beam deposition to form corralled hydrocarbon regions. This strategy is effective for maintaining atomically clean graphene at high temperatures where hydrocarbon mobility can lead to substantial accumulation of unwanted e‐beam deposition.

36 MATERIALS SCIENCE↗

Structural Changes in Metal Chalcogenide Nanoclusters Associated with Single Heteroatom Incorporation

Atomically precise nanoclusters (NCs) are promising building blocks for designing materials and interfaces with unique properties. By incorporating heteroatoms into the core, the electronic and magnetic properties of NCs can be precisely tuned. To accurately predict these properties, density functional theory (DFT) is often employed, making the rigorous benchmarking of DFT results particularly important. In this study, we present a benchmarking approach based on metal chalcogenide NCs as a model system. We synthesized a series of bimetallic, iron-cobalt chalcogenide NCs [Co 6-x Fe x S 8 (PEt 3 ) 6 ] + (x = 0-6) (PEt = triethyl phosphine) and investigated the effect of heteroatoms in the octahedral metal chalcogenide core on their size and electronic properties. Using ion mobility-mass spectrometry (IM-MS), we observed a gradual increase in the collision cross section (CCS) with an increase in the number of Fe atoms in the core. DFT calculations combined with trajectory method CCS simulations successfully reproduced this trend, revealing that the increase in cluster size is primarily due to changes in metal-ligand bond lengths, while the electronic properties of the core remain largely unchanged. Moreover, this method allowed us to exclude certain multiplicity states of the NCs, as their CCS values were significantly different from those predicted for the lowest-energy structures. Here, this study demonstrates that gas-phase IM-MS is a powerful technique for detecting subtle size differences in atomically precise NCs, which are often challenging to observe using conventional NC characterization methods. Accurate CCS measurements are established as a benchmark for comparison with theoretical calculations. The excellent correspondence between experimental data and theoretical predictions establishes a robust foundation for investigating structural changes of transition metal NCs of interest to a broad range of applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On diamond, graphitic and amorphous carbons in primitive extraterrestrial solar system materials

Carbon is among the most abundant elements in the universe and carbon chemistry in meteorites and comets is an important key to understanding many Solar System and interstellar processes. Yet, the mineralogical properties and interrelations between various structural forms of elemental carbon remain ambiguous. Crystalline elemental carbons include rhombohedral graphite, hexagonal graphite, cubic diamond, hexagonal diamond (i.e., lonsdaleite or carbon-2H) and chaoite. Elemental carbon also occurs as amorphous carbon and poorly graphitized (or turbostratic) carbon but of all the forms of elemental carbon only graphite is stable under physical conditions that prevail in small Solar System bodies and in the interstellar medium. The recent discovery of cubic diamond in carbonaceous chondrites and hexagonal diamond in chondritic interplanetary dust particles (IDPs) have created a renewed interest in the crystalline elemental carbons that were not formed by shock processes on a parent body. Another technique, Raman spectroscopy, confirms a widespread occurrence of disordered graphite in the Allende carbonaceous chondrite and in chondritic IDPs. Elemental carbons have also been identified by their characteristic K-edge features in electron energy loss spectra (EELS). However, the spectroscopic data do not necessarily coincide with those obtained by selected area electron diffraction (SAED). In order to interpret these data in terms of rational crystalline structures, it may be useful to consider the principles underlying electron diffraction and spectroscopic analyses. Electron diffraction depends on electron scattering, on the type of atom and the distance between atoms in a crystal lattice. Spectroscopic data are a function of the type of atom and the energy of bonds between atoms. Also, SAED is a bulk sampling technique when compared to techniques such as Raman spectroscopy or EELS. Thus, it appears that combined analyses provide contradictory results and that amorphous, or short-range ordered, carbon identified by conventional TEM imaging and SAED may show evidence for sp(3) bonds in EELS spectra. It is suggested that complex, nanometer-scale, mineralogical interrelations are common to all elemental carbons irrespective of their origin. The subsequent thermal history, or energy balance, will determine the ultimate microstructure.

Rietmeijer, Frans J. M.↗

Visualizing the atomic-scale origin of metallic behavior in Kondo insulators

A Kondo lattice is often electrically insulating at low temperatures. However, several recent experiments have detected signatures of bulk metallicity within this Kondo insulating phase. In this study, we visualized the real-space charge landscape within a Kondo lattice with atomic resolution using a scanning tunneling microscope. We discovered nanometer-scale puddles of metallic conduction electrons centered around uranium-site substitutions in the heavy-fermion compound uranium ruthenium silicide (URu 2 Si 2 ) and around samarium-site defects in the topological Kondo insulator samarium hexaboride (SmB 6 ). These defects disturbed the Kondo screening cloud, leaving behind a fingerprint of the metallic parent state. Our results suggest that the three-dimensional quantum oscillations measured in SmB 6 arise from Kondo-lattice defects, although we cannot exclude other explanations. Finally, our imaging technique could enable the development of atomic-scale charge sensors using heavy-fermion probes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗