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At least 1,009 records · Page 56

Low-dimensional physics of clay particle size distribution and layer ordering

Abstract Clays are known for their small particle sizes and complex layer stacking. We show here that the limited dimension of clay particles arises from the lack of long-range order in low-dimensional systems. Because of its weak interlayer interaction, a clay mineral can be treated as two separate low-dimensional systems: a 2D system for individual phyllosilicate layers and a quasi-1D system for layer stacking. The layer stacking or ordering in an interstratified clay can be described by a 1D Ising model while the limited extension of individual phyllosilicate layers can be related to a 2D Berezinskii–Kosterlitz–Thouless transition. This treatment allows for a systematic prediction of clay particle size distributions and layer stacking as controlled by the physical and chemical conditions for mineral growth and transformation. Clay minerals provide a useful model system for studying a transition from a 1D to 3D system in crystal growth and for a nanoscale structural manipulation of a general type of layered materials.

42 ENGINEERING↗

Optoelectronic property comparison for isostructural Cu 2 BaGeSe 4 and Cu 2 BaSnS 4 solar absorbers

To target mitigation of anti-site defect formation in Cu 2 ZnSnS 4–x Se x , a new class of chalcogenides, for which Ba or Sr (group 2) replace Zn (group 12), has recently been introduced for prospective solar absorber application. Cu 2 BaGeSe 4 (CBGSe) and Cu 2 BaSnS 4 (CBTS) are two such compounds, which share a common trigonal crystal structure (P3 1 space group) and similar quasi-direct band gap (~2 eV). While CBTS-based films have already been studied, there are no reports yet on films and solar cells based on related CBGSe. To identify key differences and similarities in the electronic properties between these two materials, electronic characteristics (e.g., carrier concentration, mobility, electron affinity, defect levels, recombination, and charge carrier kinetics) of vacuum-deposited CBGSe and CBTS films are compared using a variety of characterization methods. Hall effect measurements reveal that CBGSe films have relatively higher hole carrier concentration and lower mobility (3 × 10 15 cm –3 , 0.6 cm 2 V –1 s –1 ) compared to CBTS (5 × 10 12 cm –3 , 3.5 cm 2 V –1 s –1 ). Photoelectron spectroscopy yields low electron affinity values for both CBGSe (3.7 eV) and CBTS (3.3 eV), pointing to the necessity of pursuing low electron affinity buffer materials for both types of absorbers. At low temperatures, CBGSe films show free-exciton photoluminescence, as well as pronounced deep-level emission at ~1.4 eV, while CBTS films exhibit a strong bound-exciton signal with noticeably less intense deep-level emission than for CBGSe. Charge carrier kinetics, transport, and recombination properties of both types of films are also analyzed using optical-pump terahertz-probe spectroscopy and time-resolved microwave conductivity. The first CBGSe prototype solar cells (using chemical bath deposited CdS as a buffer layer) show a maximum of 1.5% efficiency with ~0.62 V open-circuit voltage. Furthermore, the measured properties point to possible limiting factors for CBGSe and related films for PV and optoelectronics and provide insights on possible approaches for improvement within this multinary chalcogenide family.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pb dimerization greatly accelerates charge losses in MAPbI 3 : Time-domain ab initio analysis

Metal halide perovskites constitute a new type of semiconducting materials with long charge carrier lifetimes and efficient light-harvesting. The performance of perovskite solar cells and related devices is limited by nonradiative charge and energy losses, facilitated by defects. Combining nonadiabatic molecular dynamics and time-domain density functional theory, we demonstrate that charge losses depend strongly on the defect chemical state. By considering an extra Pb atom in CH 3 NH 3 PbI 3 , which is a common defect in lead halide perovskites, we investigate its influence on charge trapping and recombination. In a chemically inert form as a Pb interstitial, the extra Pb atom has only a mild influence on charge recombination. However, if the extra Pb atom binds to a native Pb atom to form a dimer, the charge trapping and recombination are greatly accelerated because the Pb-dimer creates a localized midgap trap state that couples strongly to the perovskite valence band edge. Holes disappear from the valence band two orders of magnitude faster than in the pristine perovskite and recombine with conduction band electrons one order of magnitude faster. The simulations identify the phonon modes involved in the nonradiative charge trapping and recombination and highlight the importance of rapid decoherence within the electronic subsystem for long carrier lifetimes. The detailed atomistic analysis of the charge trapping and recombination mechanisms enriches the understanding of defect properties and provides theoretical guidance for improving perovskite performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancement of the ultraviolet photoluminescence of ZnO films: Coatings, annealing, and environmental exposure studies

To realize the many potential applications of ZnO films, it is vital to produce films with high optical quality that exhibit strong UV luminescence. By combining annealing at an optimal temperature followed by the deposition of a coating, one can achieve a significant enhancement of photoluminescence (PL). The effectiveness of the coating over time is a crucial point to be considered. Three types of coating materials were investigated: MgO, SiO 2 , and Al 2 O 3 . Due to its strong bond energy, MgO was found to be the most effective coating material for passivation of the surfaces of the ZnO films; SiO 2 was the second best. The UV-PL intensity of MgO coated ZnO was found to increase by a factor of 52 relative to an uncoated film. The effectiveness of the coatings exhibited a linear correlation with their bond energies and is discussed in terms of competing mechanisms to surface passivation such as the adsorption of OH-groups; these can act as surface traps and diminish the UV-PL intensity. Annealing at 900 °C prior to the deposition of the coating was found to be an important step in realizing the optimal performance of the coating due to the reduction of Zn interstitials accompanied by improved crystallinity. Exposure to the environment, up to 294 days, results in the degradation of the UV-PL of the MgO coated film; this effect was not observed for the film coated with SiO 2 . This effect is discussed in terms of the strong reactivity of MgO with environmental contaminants from the OH-groups.

36 MATERIALS SCIENCE↗

Structural organization of space polymers

Extraterrestrial polymers of glycine with iron have been characterized by mass spectrometry to have a core mass of 1494 Da with dominant rod-like variants at mass to charge ratios of 1567 and 1639 [McGeoch et al., “Meteoritic proteins with glycine, iron and lithium,” arXiv:2102.10700 (2021)]. Several principal macro-structural morphologies are observed in solvent extracts from a chondritic Vigarano class alteration type 3 meteoritic material. The first is an extended sheet of linked (three-legged) triskelia containing the 1494 Da core entity that encloses gas bubbles in the solvent. A second is of fiber-like crystals found here, via x-ray diffraction, to be multiple-walled nanotubes made from a square lattice of the 1494 Da polymer. A third is a dispersion of floating phantom-like short tubes of up to 100 μm length with characteristic angled bends that suggest the influence of a specific underlying protein structure. Here, it is proposed that the angled tubes are the observable result of a space-filling superpolymerization of 1638 Da polymer subunits guided by the tetragonal symmetry of linking silicon bonds. Distorted hexagonal sheets are linked by perpendicular subunits in a three-dimensional hexagonal diamond structure to fill the largest possible volume. This extended very low-density structure is conjectured to have dominated in a process of chemical selection because it captured a maximum amount of molecular raw material in the ultra-low density of molecular clouds or of the proto-solar nebula. This could have led ultimately to the accretion of the earliest planetary bodies.

59 BASIC BIOLOGICAL SCIENCES↗

Two-dimensional perovskite heterostructures for single crystal semiconductor devices

Two-dimensional (2D) perovskites have gained much attention lately owing to their excellent optoelectronic properties, chemical tunability, and environmental stability. Multiple methods have been devised to synthesize high quality 2D perovskite single crystals, and recent progress in fabricating its heterostructures is notable as well. In particular, with growing interest in 2D van der Waals heterostructures, 2D perovskites have become a strong candidate as a new building block for heterostructures to reveal unique physical properties across different interfaces. Until now, various heterostructure devices of 2D perovskite single crystals with other types of 2D materials such as transition metal dichalcogenides (TMDs) and graphene have been studied, which have shown intriguing results including interlayer excitons and enhanced electronic properties. Here, we introduce various synthetic approaches to realize 2D perovskite single crystals and unique characteristics of their single crystal heterostructures fabricated with precision, possessing sharp interfaces. Moreover, recent studies of semiconductor devices based on 2D perovskite single crystal heterostructures are discussed in-depth. New perspectives to further the horizon in the field of 2D perovskite heterostructures are suggested in this work including the consideration of metal–2D material van der Waals contact, application of dry transfer techniques, electric bias driven ion diffusion studies, and nanocrystal array fabrication. 2D perovskite heterostructure single crystal devices factoring in these novel perspectives will further uncover the true potential of these materials for highly efficient and stable semiconductor devices.

Physics↗

Defect levels and self-compensation in iodine-doped CdTe single crystals

This study systematically documents defect levels in n-type iodine-doped cadmium telluride (CdTe:I) crystals as measured by thermoelectric effect spectroscopy, Hall-effect measurements, and photoluminescence and calculated by density functional theory. The primary donor, I Te , was identified with an activation energy of ∼0.05 eV (measured)/∼0.13 eV (calculated). Deep acceptor states, V Cd and I Te –V Cd complex, exhibited activation energies of ∼0.1 eV (measured)/∼0.19 eV (calculated) and ∼0.12 eV (measured)/∼0.24 eV (calculated), respectively. Self-compensation and Fermi level pinning were observed at ∼0.7 eV (measured)/∼1.08 eV (calculated), contributing to high resistivity in as-grown samples. Post-growth Cd annealing effectively removes compensation centers, releases iodine donors, and significantly reduces resistivity, resulting in an ideal n-type solar cell material.

Cd annealing↗

Spin pumping from antiferromagnetic insulator spin-orbit-proximitized by adjacent heavy metal: a first-principles Floquet-nonequilibrium Green function study

Motivated by the recent experiment on spin pumping from sub-THz radiation-driven uniaxial antiferromagnetic insulator (AFI) MnF 2 into heavy metal (HM) Pt hosting strong spin-orbit (SO) coupling, we compute and compare pumped spin currents in Cu/MnF 2 /Cu and Pt/MnF 2 /Cu heterostructures. Recent theories of spin pumping by AFI have relied on simplistic Hamiltonians (such as tight-binding) and the scattering approach to quantum transport yielding the so-called interfacial spin mixing conductance (SMC), but the concept of SMC ceases to be applicable when SO coupling is present directly at the interface. In contrast, we use a more general first-principles quantum transport approach which combines noncollinear density functional theory with Floquet-nonequilibrium Green's functions in order to take into account: SO-proximitized AFI as a new type of quantum material, different from isolated AFI and brought about by AFI hybridization with adjacent HM layer; strong SO coupling at the interface; and evanescent wavefunctions penetrating from Pt or Cu into AFI layer to make its interfacial region conducting rather than insulating as in the isolated AFI. The DC component of pumped spin current $I_\mathrm{DC}^{S_z}$ vs. precession cone angle $\theta_{\boldsymbol{l}}$ of the Néel vector l of AFI does not follow putative $I^{S_z}_\mathrm{DC} \propto \sin^2 \theta_{\boldsymbol{l}}$, except for very small angles $\theta_{\boldsymbol{l}} \lesssim 10^\circ$ for which we define an effective SMC from the prefactor and find that it doubles from MnF2/Cu to MnF2/Pt interface. In addition, the angular dependence $I^{S_z}_\mathrm{DC}(\theta_{\boldsymbol{l}})$ differs for opposite directions of precession of the Néel vector, leading to twice as large SMC for the right-handed than for the left-handed chirality of the precession mode.

36 MATERIALS SCIENCE↗

Reverse phonon thermal flux from an applied electric field

In the phenomenon known as electron drag, a phonon thermal flux is established in a conducting crystal by an electric field applied under isothermal conditions through directed transfer of quasimomentum from the electronic charge current to the phonon subsystem. Prior understanding of this phenomenon involves a thermal current composed of low-frequency acoustic phonons that is in the same direction as the charge current. This results in an increase of the Peltier thermopower. Here, we show that it is also possible to establish a phonon thermal current that is in the opposite direction to the charge current, which we refer to as a reverse phonon thermal flux. We demonstrate this behavior both through a simple qualitative model and through first-principles calculations performed for three materials: p-type 𝜃-TaN, n-type BAs, and n-type Si. The reverse phonon flux is shown to arise through intervalley electron-phonon scattering processes involving high-frequency acoustic phonons. Unlike n-BAs and n-Si, the combined features in the band structure and phonon dispersions of p-type 𝜃-TaN promote a particularly large reverse phonon thermal flux comparable in magnitude to the oppositely directed thermal flux from low-frequency phonons. Finally, this work highlights a previously unrecognized behavior in the coupled electron-phonon system and advances our understanding of the rich physics of transport in solids.

lattice dynamics↗

Electromagnon Signatures of a Metastable Multiferroic State

Magnetoelectric multiferroic materials, particularly type-II multiferroics where ferroelectric polarizations arise from magnetic order, offer significant potential for the simultaneous control of magnetic and electric properties. However, it remains an open question as to how the multiferroic ground states are stabilized on the free-energy landscape in the presence of intricate competition between the magnetoelectric coupling and thermal fluctuations. Here, in this work, by using terahertz time-domain spectroscopy in combination with an applied magnetic field, photoexcitation, and single-shot detection, we reveal the spectroscopic signatures of a magnetic-field-induced metastable multiferroic state in a hexaferrite. This state remains robust until thermal influences cause the sample to revert to the original paraelectric state. Our findings shed light on the emergence of metastable multiferroicity and its interplay with thermal dynamics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Statistically averaged molecular dynamics simulations of hydrogen diffusion in magnesium and magnesium hydrides

Magnesium has a different crystal structure from its dihydride with hydrogenation leading to a phase transition from the hexagonal closely packed Mg into a tetragonal α-MgH 2 rutile type structure. Such materials exhibit complex hydrogen uptake and release kinetics because hydrogen diffusivities significantly change when the crystal structure changes. To provide a foundational understanding of (de)hydrogenation kinetics that is applicable to all stages of the reaction, we performed statistically averaged molecular dynamics simulations to derive hydrogen diffusivities as a function of temperature and hydrogen content for both magnesium and magnesium hydride. Furthermore, our studies confirm that hydrogen diffusivities in magnesium hydride are much lower than in magnesium, in agreement with experimental data. Additionally, we observe that in either magnesium or magnesium hydride, higher hydrogen compositions result in reduced diffusivities. The latter was not revealed by prior experiments, which were conducted at fixed hydrogen composition. Finally, we discover a non-Arrhenius behavior in magnesium hydride. The physical origin of this behavior is also discussed.

36 MATERIALS SCIENCE↗

Understanding the Origin of Tabula Rasa Process-Induced Defects in CZ n-type c-Si

High-temperature annealing, known as Tabula Rasa (TR) has been the subject of recent studies as a method to make n-type CZ silicon material resistant to temperature-induced and process-induced lifetime degradation during solar cell fabrication. In this work, we study the defects responsible for the lifetime changes after TR treatment. We use temperature and injection dependent lifetime spectroscopy (T-IDLS) and the recently introduce defect parameter contour mapping to identify the Energy Level (E t ) and capture cross-section ratio (k) of the most likely process-induced defect. We also present a closer look at changes in surface recombination velocity before and after TR annealing.

bulk lifetime↗

Evaluation of Copper Catalytic Effects in Cable Insulation Polymers

This paper summarizes work performed to evaluate a phenomenon that occurs in electrical cable insulation polymers subjected to accelerated aging while in contact with copper metal. This effect, commonly known as the copper catalytic effect, is a result of chemical reactions that occur when copper ions diffuse into insulation polymers. This diffusion process is observed in various types of polymeric materials exposed to elevated temperatures and happens at the interface between the insulation and metallic components (e.g., conductor, shielding, etc.) in a cable. This polymer-metal interaction has only been observed in cables constructed with copper components (i.e., no interactions observed in cables with aluminum or other metal conductor/shielding) and results in a significant catalytic effect that increases the oxidation rate (e.g., aging) of the material. Under this research, the copper catalytic effects observed in cross-linked polyethylene, cross-linked polyolefin and ethylene propylene rubber insulated cables subjected to thermal accelerated aging were evaluated. These evaluations involved applying infrared spectroscopy, microscopy, and energy dispersive X-ray spectroscopy cross-sectional depth profiling to obtain an in-depth understanding of the aging characteristics of the materials under accelerated conditions. Based on the results of these assessments, the copper catalytic effect can have a significant impact on the mechanical, thermal, chemical, and electrical properties of cable insulation polymers. Here, the results acquired from this research provided the information needed to characterize the copper catalytic effects observed in these polymers, analyze how this phenomenon affected the polymer degradation process, and compare and understand the differences in the properties of the materials.

42 ENGINEERING↗

Structural Analysis Approach for the Defense Programs Package 3 (DPP-3)

The Pacific Northwest National Laboratory (PNNL) is the design authority for a new Type B hazardous materials transportation package designated as the Defense Programs Package 3 (DPP-3) for the U.S. Department of Energy (DOE) National Nuclear Security Administration (NNSA). The DPP-3 has been developed using similar materials and fabrication methods employed in previous U.S. Nuclear Regulatory Commission (NRC), DOE, and NNSA certified packages. The DPP-3 design criteria are derived from the American Society of Mechanical Engineers (ASME) Boiler and Pressure Vessel Code (BPVC), NNSA guidance and NRC regulatory guides in order to safely and securely transport a variety of payloads. Final regulatory approval by the NNSA will require physical testing to demonstrate that the containment vessel (CV) remains leaktight after enduring the entire regulatory testing sequence prescribed in Title 10 of the Code of Federal Regulations Part 71 (10 CFR 71). In order to gain confidence that the DPP-3 will remain leaktight after testing, the DPP-3 has been structurally analyzed using the Finite Element Analysis (FEA) software LS-DYNA. The FEA analyses serve two general purposes: first, they aid in design and development of the package, and second, they advise as to which drop orientations are expected to cause the most damage during regulatory testing. This paper will discuss how the design criteria are incorporated into analytical techniques needed to evaluate the FEA structural simulation results for 10 CFR 71 conditions to give confidence the DPP-3 testing campaign will be successful.

Sakalaukus Jr., Peter J.↗

Commercial Vehicle Driver Behaviors and Decision Making: Lessons Learned from Urban Ridealongs

As e-commerce and urban deliveries spike, cities grapple with managing urban freight more actively. In order to effectively manage urban deliveries, city planners and policy makers need to better understand driver behaviors and the challenges they experience in performing deliveries. In this study, we collected data on commercial vehicle (CV) driver behaviors by performing ridealongs with various logistics carriers. Ridealongs were performed in Seattle, Washington, covering a range of vehicles (cars, vans, and trucks), goods (parcels, mail, beverages, and printed materials), and customer types (residential, office, large and small retail). Observers collected qualitative observations and quantitative data on trip and dwell times, while also tracking vehicles through GPS devices. The results showed that, on average, urban CVs spent 80 percent of their daily operating time parked. The study also found that, unlike the common belief, drivers (especially those operating heavier vehicles) parked in authorized parking locations, with only less than 5 percent of stops occurring in the travel lane. Dwell times associated with authorized parking locations were significantly longer than those of other parking locations, and mail and heavy goods deliveries generally had longer dwell times. We also identified three main criteria CV drivers used for choosing a parking location: avoiding unsafe maneuvers, minimizing conflicts with other users of the road, and coopetition with other commercial drivers. Here, the results provide estimates for trip times, dwell times, and parking choice types, as well as insights into why those decisions are made and the factors affecting driver choices.

33 ADVANCED PROPULSION SYSTEMS↗

Initial Efforts Organizing WPNCS SG-8: Preservation of Expert Knowledge and Judgement Applied to Criticality Benchmarks

The Working Party on Nuclear Criticality Safety (WPNCS) under the guidance of the Organization for Economic Co-operation and Development (OECD) Nuclear Energy Agency (NEA) has over 20 years of experience addressing concerns related to static and transient configurations encountered within the nuclear fuel cycle: fuel fabrication, transportation, reprocessing, storage, and geological disposal. One of the cornerstone activities of the WPNCS is the International Criticality Safety Benchmark Evaluation Project (ICSBEP), which was established to identify a comprehensive set of criticality benchmark data, evaluate the data, including quantification of overall uncertainties; compile the data into a standardized format, perform sample calculations utilizing modern nuclear data sets and codes utilized in nuclear criticality safety, and formally document the work into a single source of verified benchmark data. Annually, members of the ICSBEP Technical Review Group (TRG) contribute evaluated benchmark data that undergoes comprehensive technical review prior to publication in the ICSBEP Handbook. In the years since the ICSBEP was established, there has been much work to prepare benchmark data to support validation activities in nuclear criticality safety. The 2020 edition of the ICSBEP Handbook contains acceptable benchmark specifications for 5,053 critical, subcritical, or near-critical configurations in 582 benchmark evaluations. Modern benchmark development benefits from decades of experienced international participants, a well-established handbook format, supplementary guides to deal with uncertainty quantification, and a comprehensive review process based upon independent reviews from international experts. The ICSBEP Handbook also contains 838 configurations deemed unacceptable to support criticality safety efforts. They are recorded, with the reasoning for their rejection, to preserve the experimental data, prevent reevaluation of data that are incomplete or contain known errors, and/or to potentially allow future reevaluation of the experiment pending the identification of sufficient data to resolve identified inconsistencies and errors. Users of the ICSBEP Handbook today might notice that the rigor and quality of modern criticality safety benchmarks is much greater than those prepared within the initial decade of the project. Benchmarks with 1s uncertainties in k eff greater than 1% were traditionally rejected unless they were identified as unique experiment types that encompassed materials, fuels, or designs not available from other benchmark experiments. However, benchmarks developed using modern experimental techniques and practices typically have uncertainties on the order of a few tenths of a percent. There have been ongoing efforts to improve the overall quality of previously published benchmark evaluations. Seventy-eight evaluations, containing approximately 600 configurations, have been revised just within the past decade. An additional eleven benchmarks are under revision for updated release in the 2020 edition of the ICSBEP Handbook. If some of the historic benchmarks were resubmitted in their current form to the TRG today, they would be rejected due to lack of data, missing components in the uncertainty analysis, or incomplete benchmark model development. The use of historic criticality safety benchmarks that underestimate the total uncertainty, lack properly quantified biases, or provide inadequate benchmark specifications do not sufficiently support modern criticality safety and nuclear data efforts. Although the ICSBEP Handbook is recognized by regulating bodies to support criticality safety, users are required to justify their reasons to ignore historic benchmark data and include additional safety margins within their designs. Discussions were held at the WPNCS 23rd Annual Meeting in September 2019 regarding the aforementioned issues. The resultant decision was to establish Subgroup 8 (SG-8): Preservation of Expert Knowledge and Judgement Applied to Criticality Benchmarks. The current activities of SG-8 are discussed herein.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Study of Conduction-Cooled Superconducting Quadrupole Magnets Combined with Dipole Correctors for the ILC Main Linac

A superconducting rf (SRF) cryomodule for International Linear Collider(ILC) Main Linac equips focus/steering magnets. The magnets are "superferric" magnets with four superconducting (SC) race track coils conductively cooled from the cryomodule LHe supply pipe. The quadrupole field gradient and dipole field are 40 T/m and 0.1 T, respectively. The magnet length and iron-pole radius are 1 m and 0.045 m, respectively. It is known that dark current is generated at SRF cavities and accelerated through the following linac string. The dark current reaches and heats the SC magnets. It is estimated that the power deposition in the magnet may reach more than a few watts and temperature of the SC coils may locally reach to critical temperature of NbTi. It is important to make the magnet not reach quench with sufficient conduction cooling. We aim to realize the SC magnet which can stably operate under such condition. We plan to develop test coils made of three types of SC materials, NbTi, Nb₃Sn, and MgB₂ and study thermal characteristics and stability . We will develop a short model magnet, based on the test coil results. Here, we will present the magnet design study and the R&D plan.

43 PARTICLE ACCELERATORS↗

Comparative Approach for Evaluating the Containment Performance of Legacy NM Storage Containers

Many different types of nuclear material storage containers are used throughout TA-55 and specifically PF-4, in some instances these containers are used outside of engineering control barriers in most cases these barriers are gloveboxes. When a container is used outside of a glovebox or open front hood the container itself is relied upon as the primary engineering control barrier for the user. For this reason a process must be established in order to evaluate Non- Manual Compliant or NMC containers used outside of a glovebox in a comparative approach against Manual compliant containers. Legacy containers are typically understood to be non-standards packaged prior to 1998. For the purposes of this document “legacy” refers to any non-Manual compliant containers.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗