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At least 703 records · Page 39

Ferroelectric Al1 − xBxN thin films integrated on Si

Ferroelectric Al0.93B0.07N thin films are prepared (100) Si substrates. The necessary c-axis out-of-plane orientation to observe macroscopic ferroelectric switching was achieved by implementing an initial Ar/N2 plasma treatment, followed by a thin layer of AlN to initiate the desired texture and a 150 nm W layer. The plasma treatment facilitates crystallinity enhancement of the AlN template layer, allowing for subsequent growth of highly oriented W and Al0.93B0.07N layers. The W layer exhibits random in-plane orientation and exclusive (110) out-of-plane orientation with a rocking curve width of 1.4°. When grown on these W surfaces, 175 nm thick Al0.93B0.07N films exhibit random in-plane orientation and exclusive (001) texture with rocking curve full-width-half-max values of 1.6° and RMS roughness values less than 1 nm. Polarization hysteresis measurements show robust hysteresis with coercive field values of 5.4 MV/cm and remanent polarization values of 136 μC/cm2. XPS depth profile analysis suggests that the plasma treatment converts the existing native oxide to a nitrogen rich oxynitride with approximate composition Si3O0.5N3.67. Cross-sectional TEM reveals that the oxynitride interlayer is amorphous and ∼3.4 nm thick, more than double the native oxide thickness measured by multiwavelength ellipsometry, implying that (oxy)nitride growth continues after conversion of the native oxide. This new family of ferroelectric wurtzites is interesting from an integration perspective given their chemical compatibility with mainstream semiconductors. Developing synthesis routes that promote needed texture while preserving compatible processing windows is an important step toward practical integration.

Physics↗

Fine-root functional trait responses to experimental warming: a global meta-analysis

Whether and how warming alters functional traits of absorptive plant roots remains to be answered across the globe. Tackling this question is crucial to better understanding terrestrial responses to climate change as fine-root traits drive many ecosystem processes. In this work, we carried out a detailed synthesis of fine-root trait responses to experimental warming by performing a meta-analysis of 964 paired observations from 177 publications. Warming increased fine-root biomass, production, respiration and nitrogen concentration as well as decreased root carbon : nitrogen ratio and nonstructural carbohydrates. Warming effects on fine-root biomass decreased with greater warming magnitude, especially in short-term experiments. Furthermore, the positive effect of warming on fine-root biomass was strongest in deeper soil horizons and in colder and drier regions. Total fine-root length, morphology, mortality, life span and turnover were unresponsive to warming. Our results highlight the significant changes in fine-root traits in response to warming as well as the importance of warming magnitude and duration in understanding fine-root responses. These changes have strong implications for global soil carbon stocks in a warmer world associated with increased root-derived carbon inputs into deeper soil horizons and increases in fine-root respiration.

59 BASIC BIOLOGICAL SCIENCES↗

Coordinated resource allocation to plant growth–defense tradeoffs

Summary Plant resource allocation patterns often reveal tradeoffs that favor growth (G) over defense (D), or vice versa. Ecologists most often explain G–D tradeoffs through principles of economic optimality, in which negative trait correlations are attributed to the reconciliation of fitness costs. Recently, researchers in molecular biology have developed ‘big data’ resources including multi‐omic (e.g. transcriptomic, proteomic and metabolomic) studies that describe the cellular processes controlling gene expression in model species. In this synthesis, we bridge ecological theory with discoveries in multi‐omics biology to better understand how selection has shaped the mechanisms of G–D tradeoffs. Multi‐omic studies reveal strategically coordinated patterns in resource allocation that are enabled by phytohormone crosstalk and transcriptional signal cascades. Coordinated resource allocation justifies the framework of optimality theory, while providing mechanistic insight into the feedbacks and control hubs that calibrate G–D tradeoff commitments. We use the existing literature to describe the coordinated resource allocation hypothesis (CoRAH) that accounts for balanced cellular controls during the expression of G–D tradeoffs, while sustaining stored resource pools to buffer the impacts of future stresses. The integrative mechanisms of the CoRAH unify the supply‐ and demand‐side perspectives of previous G–D tradeoff theories.

Monson, Russell K.↗

Supramolecular assembly of blue and green halide perovskites with near-unity photoluminescence

The metal-halide ionic octahedron is the optoelectronic unit for halide perovskites, and a crown ether–assisted supramolecular assembly approach can pack various ionic octahedra into tunable symmetries. In this work, we demonstrate near-unity photoluminescence quantum yield (PLQY) blue and green emission with the supramolecular assembly of hafnium (Hf) and zirconium (Zr) halide octahedral clusters. (18C6@K) 2 HfBr 6 powders showed blue emission with a near-unity PLQY (96.2%), and green emission was also achieved with (18C6@K) 2 ZrCl 4 Br 2 powders at a PLQY of 82.7%. In conclusion, these highly emissive powders feature facile low-temperature solution-based synthesis conditions and maintain high PLQY in solution-processable semiconductor inks under ambient conditions, and they were used in thin-film displays and emissive three-dimensional–printed architectures that exhibited high spatial resolution.

36 MATERIALS SCIENCE↗

Spatiotemporal evolution of melt ponds on Arctic sea ice

Melt ponds on sea ice play an important role in the Arctic climate system. Their presence alters the partitioning of solar radiation: decreasing reflection, increasing absorption and transmission to the ice and ocean, and enhancing melt. The spatiotemporal properties of melt ponds thus modify ice albedo feedbacks and the mass balance of Arctic sea ice. The Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition presented a valuable opportunity to investigate the seasonal evolution of melt ponds through a rich array of atmosphere-ice-ocean measurements across spatial and temporal scales. In this study, we characterize the seasonal behavior and variability in the snow, surface scattering layer, and melt ponds from spring melt to autumn freeze-up using in situ surveys and auxiliary observations. We compare the results to satellite retrievals and output from two models: the Community Earth System Model (CESM2) and the Marginal Ice Zone Modeling and Assimilation System (MIZMAS). During the melt season, the maximum pond coverage and depth were 21% and 22 ± 13 cm, respectively, with distribution and depth corresponding to surface roughness and ice thickness. Compared to observations, both models overestimate melt pond coverage in summer, with maximum values of approximately 41% (MIZMAS) and 51% (CESM2). This overestimation has important implications for accurately simulating albedo feedbacks. During the observed freeze-up, weather events, including rain on snow, caused high-frequency variability in snow depth, while pond coverage and depth remained relatively constant until continuous freezing ensued. Both models accurately simulate the abrupt cessation of melt ponds during freeze-up, but the dates of freeze-up differ. MIZMAS accurately simulates the observed date of freeze-up, while CESM2 simulates freeze-up one-to-two weeks earlier. This work demonstrates areas that warrant future observation-model synthesis for improving the representation of sea-ice processes and properties, which can aid accurate simulations of albedo feedbacks in a warming climate.

54 ENVIRONMENTAL SCIENCES↗

Multiscale modeling and laser diagnostics to reveal non-equilibrium reaction chemistry at a plasma-liquid interface

Low-temperature, atmospheric-pressure plasmas in contact with liquid are at the core of a wide range of applications including water treatment, medicine, materials synthesis, and chemical transformation. In general, plasma-liquid processes are scientifically compelling because reactivity can be produced without a catalyst, in relatively inert molecules, such as air or nitrogen and liquid water, in their native states at ambient conditions. However, reactions at a plasma-liquid interface are extremely complex, occurring at a multiphase, gas-liquid boundary where excited or dissociate gaseous species dissolve and react with solution-phase species, and unique reaction pathways are induced by non-equilibrium chemistry. In particular, detailed knowledge of the physical and chemical processes, including what species are produced in the gas phase and how these species are subsequently transported across and react near the interfacial region, remains largely unanswered. In this project, modeling of the non-equilibrium reaction chemistry at the interface of low-temperature, atmospheric-pressure plasmas and liquid water is developed, supported by advanced laser diagnostics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Final Technical Report: In-Silico Heterogeneous Catalyst Design for GHG Reduction via Bulk Chemicals

This project has advanced the understanding of ammonia synthesis by developing novel thermochemical catalysts, setting a new benchmark for energy and carbon efficiency in large-scale bulk chemicals production. This research leverages a proprietary computational discovery platform and high-throughput experimental validation, significantly accelerating catalyst optimization and enabling ammonia synthesis at lower temperature and pressure conditions than conventional processes. As a result, green ammonia can be produced at a cost that meets or exceeds established targets, supporting a viable pathway toward decarbonized ammonia for fuel, fertilizers, and hydrogen supply applications.

Grose, Jacob E [Copernic Catalysts, Inc.]↗

Solid-State Synthesis of Highly Dispersed Nitrogen-Coordinated Single Iron Atom Electrocatalysts for Proton Exchange Membrane Fuel Cells

Fe–N–C with atomically dispersed Fe single atoms is the most promising candidate to replace platinum for the oxygen reduction reaction (ORR) in fuel cells. However, the conventional synthesis procedures require quantities solvents and metal precursors, sluggish adsorption process, and tedious washing, resulting in limited metal doping and uneconomical for large-scale production. Here, for the first time, Fe 2 O 3 is adopted as the Fe precursor to derive abundant single Fe atoms dispersed on carbon surfaces. The Fe–N–C catalyst synthesized by this simple method shows an excellent ORR activity with half-wave potentials of 0.82 and 0.90 V in acidic and alkaline solutions, respectively. A single fuel cell with an optimized Fe–N–C cathode shows a high peak power density of 0.84 W cm –2 . The solid-state transformation synthesis method developed in this study may shed light on mass production of single-atom-based catalysts.

25 ENERGY STORAGE↗

Role of Capping Agents in the Synthesis of Salicylate-Capped Zinc Oxide Nanoparticles

Capping agents are often used for controlling the size, aggregation, and properties of nanoparticles. To guide the design of improved nanomaterials for targeted performance, one can use mechanistic insights into the interactions between capping agents and nanoparticles. Here, we employ density functional theory (DFT), reactive force-field molecular dynamics (ReaxFF MD) simulations, and optical spectroscopy to study the interactions between salicylate, as a model capping agent, and zinc oxide (ZnO) nanoparticles. In this work, we find that salicylate strongly interacts with the nanoparticle via the formation of O–Zn bonds in a distorted six-membered coordination ring structure. We describe the mechanisms of capping of ZnO nanoparticles by salicylate via three different binding modes. Simulations indicate that salicylate undergoes dissociative adsorption at the highly active surface Zn sites via a hydrogen-transfer process, thereby forming a tridentate configuration. The water-mediated interaction also facilitates the dissociative adsorption, leading to two salicylate O atoms coordinating with a surface Zn atom, while the other salicylate O atom bonds with another surface Zn atom. For molecular adsorption, binding free energies indicate that salicylate binds more strongly to ZnO, often in a bidentate configuration, than water does. The formation of the salicylate–ZnO complex is substantiated by UV–visible and Fourier transform infrared spectra. We find that the C=O stretching mode of salicylate becomes softened when it interacts with the nanoparticle, suggesting chemisorption of salicylate on ZnO. Although DFT predicts strong interaction between salicylate and ZnO, ReaxFF MD simulation indicates the moderate interaction between these two components in aqueous solution. Water molecules in close contact with the nanoparticle surface undergo dissociation, thus resulting in a surface hydroxyl, a reactive oxygen species that may influence the nanoparticle’s catalytic properties. Overall, the atomic-level information provided here can guide the selection process of salicylate as an appropriate agent for ZnO nanoparticle synthesis when strong interactions of particles with capping agents are required.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Even Higher-Level Synthesis: An Exploration of AI Hardware Accelerators using HLS4ML

With the rise of artificial intelligence, the popularization of deep learning, and a constantly evolving industry, the demand for flexible and efficient tools has never been greater. As algorithms grow more complex, their runtime and energy consumption increase exponentially. Customized hardware accelerators, long used for specific mathematical operations, remain essential for managing modern applications' computational and power demands. Hardware accelerators can speed up complex computations by orders of magnitude, but their manual design and verification processes are often challenging and time-consuming. High-Level Synthesis (HLS) provides a solution by transforming high-level algorithm descriptions, typically written in C++ or SystemC, into synthesizable RTL suitable for hardware implementation. This approach reduces development time for RTL engineers while offering flexibility beyond what traditional handwritten RTL can provide. We extended this capability to the machine-learning domain with the open-source framework hls4ml, which allows neural networks trained in Python frameworks like Tensorflow or PyTorch to be synthesized into efficient hardware representations for the traditional FPGA and ASIC flows. This breakthrough addresses the growing need for reduced design turnaround and easy verification of ML hardware accelerators with low latency and power efficiency constraints. During this tutorial, we will demonstrate how Python complements HLS by simplifying the ML design process, bridging the gap between software and hardware development. Attendees will explore how we translate neural networks modeled in Python into fixed-point C++ models suitable for HLS workflows. We will dive into strategies like Value-Range Analysis and Quantization-Aware Training, which optimize these designs for deployment and evaluate their accuracy, power consumption, and energy efficiency. To exemplify these concepts, experts from Fermilab will share their experiences applying this technology to high-energy physics experiments, where real-time, low-latency processing is critical. Over the years, Fermilab engineers have demonstrated how deep neural networks, optimized for hardware using hls4ml, can meet the stringent requirements of trigger systems at the CERN Large Hadron Collider. These systems rely on rapid decision-making to process immense data volumes while retaining only the most relevant events for further analysis. The application of hls4ml has also been extended to innovative technologies like smart pixel arrays. These smart pixels integrate ML inference capabilities directly into sensor devices, enabling localized data processing at the pixel level. This approach drastically reduces the need to transmit raw data to external processing units, significantly decreasing power consumption and latency. By embedding neural networks within the pixel architecture, the smart pixels can identify and prioritize relevant data in real time, providing a highly efficient solution for edge computing in scenarios such as particle detectors and imaging systems. Fermilab's work highlights the potential of hardware-accelerated ML in scenarios where both speed and power efficiency are mission-critical. Through this tutorial, attendees will gain valuable insights into the challenges and solutions of deploying ML in hardware. Understanding how HLS and hls4ml streamline the development of neural network-based hardware accelerators is fundamental for the industry's future. Participants will learn how these technologies are shaping the future of AI and scientific computing.

Di Guglielmo, Giuseppe [Fermilab]↗

Guiding Self-Assembly of Active Colloids by Temporal Modulation of Activity

Self-organization phenomena in ensembles of self-propelled particles open pathways to the synthesis of new dynamic states not accessible by traditional equilibrium processes. The challenge is to develop a set of principles that facilitate the control and manipulation of emergent active states. In this study, we report that dielectric rolling colloids energized by a pulsating electric field self-organize into alternating square lattices with a lattice constant controlled by the parameters of the field. We combine experiments and simulations to examine spatiotemporal properties of the emergent collective patterns and investigate the underlying dynamics of the self-organization.We reveal the resistance of the dynamic lattices to compression and expansion stresses leading to a hysteretic behavior of the lattice constant. The general mechanism of pattern synthesis and control in active ensembles via temporal modulation of activity can be applied to other active colloidal systems.

36 MATERIALS SCIENCE↗

Synthesis and Purity Specifications for N,N'-Dicyclohexyl-N"-(10-nonadecyl)guanidinium Chloride for Use in Next Generation Caustic-Side Solvent Extraction

This report describes a synthesis procedure for the alkylguanidine, N,N'-dicyclohexyl-N"-(10-nonadecyl)guanidine (DCNDG), which has been identified as a promising candidate for replacing the less stable N,N',N"-tri(3,7-dimethyloctyl)guanidine (TiDG) suppressor in the Next Generation Caustic-Side Solvent Extraction (NG-CSSX) process. A verified procedure for the preparation of the amine used in this synthesis is also included. In addition, requirements for the purity of DCNDG to be utilized in the NG-CSSX process without adverse effect on the Cs + extraction and stripping are given.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessing the cumulative effects of nearshore habitat restoration actions for multiple populations of juvenile salmon in Whidbey Basin, Washington: foundation and approach for synthesis and evaluation

Ecosystem restoration is a common tool for re-establishing ecosystem processes, structures, and functions to improve biodiversity and services in coastal and estuarine ecosystems. In the Salish Sea, salmon habitats have been fragmented, reduced in size, and diminished in quality, and the ecosystem processes that form and sustain these habitats have been degraded and disrupted as well. This loss is especially prevalent in estuaries, where up to 90% of former salmon habitat has been lost or compromised. Salmon species are integral to the identities and cultures of people in the Pacific Northwest, yet salmon abundances remain at historic lows, especially in urbanized areas. Recent investments in restoration are creating rearing habitat and repairing lost ecosystem function. However, restoration efforts in this region have largely proceeded at the site scale, with less attention to big-picture thinking regarding how restoration will effectively recover degraded or lost habitats for target species. As a result, no landscape-scale evaluation program exists, and the cumulative benefits of multiple interventions are unknown. We describe innovative methods for science synthesis related to the evaluation of cumulative effects of ecosystem restoration for Pacific salmon, using years of existing, but disparate data. Building from previous work on cumulative effects evaluation and incorporating a hierarchy of hypotheses approach, we propose using causal inference across numerous hypotheses in a framework to assess the cumulative benefits to Pacific salmon from multiple estuarine restoration projects. We present the framework as a method that can be used to address many complex questions and provide examples from the Salish Sea where the approach is being implemented. The framework draws on science synthesis from numerous fields and uses a hierarchy of hypotheses, causal analysis at multiple scales, and a new hierarchy of synthesis for assessing multiple lines of evidence documenting restoration effects on Pacific salmon. We propose causal inference to synthesize dissimilar data streams, in our case, to identify various manifestations of cumulative effects of restoration and benefits to salmon, and to further inform restoration and recovery planning. A unifying framework would allow for the detection of thresholds at which restoration provides measurable improvement and would greatly advance understanding of the effects of restoration on ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗

Review of Solid State Consolidation Processing Techniques of ODS Steels (Hot Extrusion, Hot Isostatic Pressing, Spark Plasma Sintering, and Stir Friction Consolidation): Resulting Microstructures and Mechanical Properties

This paper reviews the solid-state consolidation processing techniques for Oxide Dispersion Strengthened steels and compares them in terms of the resulting microstructure and reported mechanical properties. Synthesis techniques include hot extrusion, hot isostatic pressing, spark plasma sintering and friction consolidation. The effects of process parameters on the resulting microstructures and performance are discussed for each technique. Average oxide size, average grain size, and porosity are compared across techniques, as well as mechanical strength and ductility. Across consolidation techniques where temperature can be controlled, a low sintering temperature with a high sintering pressure is favorable for keeping oxide sizes, grain sizes, and porosity low. The use of yttrium and titanium for oxide formation has been evidenced to reduce oxide sizes, and tungsten additions have been shown to improve strength. Current literature suggests that the more mature hot extrusion technique produces stronger steel with consistently fine oxides, while other alternative solid-state consolidation, while promising, offer margin for improvement.

36 MATERIALS SCIENCE↗

Reaching the Excitonic Limit in 2D Janus Monolayers by In Situ Deterministic Growth

Abstract Named after the two‐faced Roman god of transitions, transition metal dichalcogenide (TMD) Janus monolayers have two different chalcogen surfaces, inherently breaking the out‐of‐plane mirror symmetry. The broken mirror symmetry and the resulting potential gradient lead to the emergence of quantum properties such as the Rashba effect and the formation of dipolar excitons. Experimental access to these quantum properties, however, hinges on the ability to produce high‐quality 2D Janus monolayers. Here, these results introduce a holistic 2D Janus synthesis technique that allows real‐time monitoring of the growth process. This prototype chamber integrates in situ spectroscopy, offering fundamental insights into the structural evolution and growth kinetics, that allow the evaluation and optimization of the quality of Janus monolayers. The versatility of this method is demonstrated by synthesizing and monitoring the conversion of SWSe, SNbSe, and SMoSe Janus monolayers. Deterministic conversion and real‐time data collection further aid in conversion of exfoliated TMDs to Janus monolayers and unparalleled exciton linewidth values are reached, compared to the current best standard. The results offer an insight into the process kinetics and aid in the development of new Janus monolayers with high optical quality, which is much needed to access their exotic properties.

2D materials↗

Shifting Defect Self-Regulation via Disordered Vacancies in Hollow Tin Perovskites

Tin(II)-based hybrid halide perovskites typically suffer from severe self-doping behavior as a result of facile oxidation of Sn(II) to Sn(IV), leading to high carrier densities (holes) and metallic-like conductivities that limit their applications. In this contribution, we describe how substituting the large ethylenediammonium cation for methylammonium in the intentionally defective “hollow” perovskite family, MA 1−x en x Sn 1−0.7x I 3−0.4x (MA = methylammonium, en = ethylenediammonium), where 0 ≤ x ≤ 0.38, effectively minimizes the intrinsic self-doping behavior. The use of a solvent-free, mechanochemical synthesis route further circumvents oxidative side reactions typical in solution processing, enabling more precise control and understanding of both composition and defect chemistry. Dark and time-resolved microwave conductivity measurements of these materials as a function of “x” reveal two regimes of conductivity suppression: at low x incorporation (x ≤ 0.15), the carrier density decreases by an order of magnitude via defect-mediated charge compensation, while higher substitution (0.15 < x ≤ 0.38) greatly reduces the carrier mobility. At these lower substitution levels, the observations suggest that intrinsic equilibrium tin vacancies are compensated instead by ionic defects in lieu of mobile holes. For the higher substitution levels, the less mobile carriers exhibit long recombination lifetimes, consistent with polaron-mediated transport. These findings establish a strategy for relatively low iodine chemical potential synthesis and defect-driven control of the carrier concentration in tin halide perovskites, advancing the rational discovery of dopable hybrid semiconductors.

36 MATERIALS SCIENCE↗

Hybrid Nanostructured Ni(OH) 2 /NiO for High Capacity Lithium–ion Battery Anodes

A straightforward hydrothermal process followed by a controlled calcination technique is introduced for the synthesis of a Ni(OH) 2 modified NiO nanohybrid structure. Conversion materials as Li-ion battery anodes, NiO in this case, suffer from capacity fade and structural/morphological instability during lithiation and delithiation. The novelty of this work is in utilizing this hybrid configuration to increase the specific capacity and enable reversible electrochemistry. Here, we study the lithiation/delithiation process of NiO using a suite of spectroscopy and microscopy techniques from the atomic to electrode scale. We propose a mechanism for a reversible redox couple behavior of the NiO electrode by means of a hybrid Ni(OH)2/NiO structure. The ultimate objective of this work is to guide the development of anode with rationally-designed heterogeneity to create high capacity Li-ion batteries with excellent cycling and rate performance.

25 ENERGY STORAGE↗

Conserving Land–Atmosphere Synthesis Suite (CLASS)

Accurate estimates of terrestrial water and energy cycle components are needed to better understand climate processes and improve models’ ability to simulate future change. Various observational estimates are available for the individual budget terms; however, these typically show inconsistencies when combined in a budget. In this work, a Conserving Land–Atmosphere Synthesis Suite (CLASS) of estimates of simultaneously balanced surface water and energy budget components is developed. Individual CLASS variable datasets, where possible, 1) combine a range of existing variable product estimates, and hence overcome the limitations of estimates from a single source; 2) are observationally constrained with in situ measurements; 3) have uncertainty estimates that are consistent with their agreement with in situ observations; and 4) are consistent with each other by being able to solve the water and energy budgets simultaneously. First, available datasets of a budget variable are merged by implementing a weighting method that accounts both for the ability of datasets to match in situ measurements and the error covariance between datasets. Then, the budget terms are adjusted by applying an objective variational data assimilation technique (DAT) that enforces the simultaneous closure of the surface water and energy budgets linked through the equivalence of evapotranspiration and latent heat. Comparing component estimates before and after applying the DAT against in situ measurements of energy fluxes and streamflow showed that modified estimates agree better with in situ observations across various metrics, but also revealed some inconsistencies between water budget terms in June over the higher latitudes.

54 ENVIRONMENTAL SCIENCES↗