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At least 739 records · Page 41

Polarization‐Engineered Near‐Field Generation Using a Hybrid Tip–Antenna System

Precise control of light polarization at the nanoscale is critical for accessing chiral optical responses and manipulating spin–photon interactions in advanced materials. Yet, conventional scattering-type near-field probes predominantly generate out-of-plane linear polarization and offer little control over phase or polarization state. Here, in this study, we introduce a polarization-engineered near-field methodology based on a combined metallic tip and planar dipole nanoantenna system. Using full-wave electromagnetic simulations, we show that the tip acts as a vertically oriented plasmonic resonator, while the antenna supports an in-plane dipolar mode. By tuning the tip–antenna geometry and tip height, the two orthogonal field components attain comparable amplitudes and a controllable ∼90° phase offset, producing circularly polarized nano-light in the antenna gap. The proposed system effectively functions as a nanoscale quarter-wave plate, converting linearly polarized illumination into circularly polarized hotspots without external polarization optics. This method establishes an experimentally accessible route toward polarization-programmable near-field nanoscopy, enabling chiral spectroscopy, selective excitation of spin/valley degrees of freedom, and quantum optical investigations at the nanoscale.

36 MATERIALS SCIENCE

Tip-based proximity ferroelectric switching and piezoelectric response in wurtzite multilayers

Proximity ferroelectricity is a paradigm for inducing ferroelectricity when a nonferroelectric polar material (such as Al⁢ N), which is unswitchable with an external field below the dielectric breakdown field, becomes a practically switchable ferroelectric in direct contact with a thin switchable ferroelectric layer (such as Al 1−𝑥 ⁢Sc 𝑥 ⁢N). Here, we develop a Landau-Ginzburg-Devonshire approach to study the proximity effect of local piezoelectric response and polarization reversal in wurtzite ferroelectric multilayers under a sharp electrically biased tip. Using finite-element modeling, we analyze the probe-induced nucleation of nanodomains, the features of local polarization hysteresis loops and coercive fields in the Al 1−𝑥 ⁢Sc 𝑥 ⁢N/Al⁢ N bilayers and three-layers. Similar to the wurtzite multilayers sandwiched between two parallel electrodes, the regimes of “proximity switching” (when all layers collectively switch) and the regime of “proximity suppression” (when they collectively do not switch) are the only two possible regimes in the probe-electrode geometry. However, the parameters and asymmetry of the local piezoresponse and polarization hysteresis loops depend significantly on the sequence of the layers with respect to the probe. The physical mechanism of proximity ferroelectricity in the local probe geometry is a depolarizing electric field determined by the polarization of the layers and their relative thickness. The field, whose direction is opposite to the polarization vector in the layer(s) with the larger spontaneous polarization (such as Al⁢ N), renormalizes the double-well ferroelectric potential to lower the steepness of the switching barrier in the “otherwise unswitchable” polar layers. Tip-based control of domains in otherwise nonferroelectric layers using proximity ferroelectricity can provide nanoscale control of domain reversal in memory, actuation, sensing, and optical applications. The ability of the tip-induced proximity switching to differentially switch multilayers, based on the order of the layers, provides a powerful tool for selective domain engineering.

36 MATERIALS SCIENCE

Dynamic Excitonic Beam Switching with Atomically‐Thin Binary Blazed Gratings

Abstract Beam steering metasurfaces are ultra‐compact optical coatings that offer on‐demand redirection of optical power to specific diffraction orders. To achieve this, spatial gradients are commonly introduced in the phase of light scattered by plasmon or Mie resonant nanoparticles within the metasurface grating's unit cell. However, these phase gradients are oftentimes difficult to tune post‐fabrication. Recently, excitons in monolayer 2D semiconductors have emerged as a new metasurface building block, due to their strong and electrically‐tunable resonant light‐matter interaction. These 2D excitonic metasurfaces offer the tantalizing prospect of beam switching within a single monolayer. Here, it is demonstrated how the 2D analog of binary blazed gratings enables such beam switching by mere nanopatterning of a large monolayer WS 2 , even though nanoscale ribbons of WS 2 do not support geometrical resonances. By introducing a gradient in the nanoribbon width within the metasurface unit cell, an amplitude gradient combined with a small phase gradient in the scattered fields results in asymmetric diffraction efficiencies. Using a scattered‐field analysis, it is shown that these gradients can be further engineered via interference effects with the substrate reflection. Finally, the electrical tunability of the exciton resonance is leveraged to achieve selective and dynamic beam switching with an atomically‐thin metasurface.

Guarneri, Ludovica [Van der Waals‐Zeeman Institute

Power and particle exhaust in the ST-E1 fusion power plant

Power exhaust challenges and potential solutions for a 5 m major radius, low-aspect ratio burning tokamak have been explored. 1D edge plasma models have been used to screen for access to detachment using short and long outer divertor legs in double and single null configurations, using Ar as the primary impurity and assuming tungsten plasma-facing components (PFCs). These show that detachment access can be accessed for all but the most conservative assumptions on scrape-off layer (SOL) width and power, but that trade-offs will be required between magnet engineering and the size of the acceptable window of as-yet uncertain plasma parameters. SOLPS-ITER was used to further model selected plasma scenarios, confirming that Ar seeding can be used to achieve dissipative divertor scenarios with peak deposited heat fluxes below 15 MWm -2 . Initial scoping of first wall loads and positioning of limiters has been carried out, showing the feasibility of protecting the breeding blanket wall during steady state without impeding tritium breeding. Initial PFC technology selection is also presented, identifying this as a critical area where further work is needed to find an attractive solution for helium-cooled PFCs that can handle high heat fluxes without excessive power requirements. Key questions and trade-offs for concept development have been identified, including: how to achieve high radiation for reduction of SOL power without core performance degradation; whether power exhaust can be well-controlled in a double null plasma; mechanical design and materials challenges of high-heat flux PFCs; and control of material erosion, redeposition and tritium retention.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY

Optimization of Ag Electrocatalyst Performance for CO2 to CO Conversion: Pairing Atomic Simulations with Experiments

Density-functional theory- based calculations that complement our series of experimental efforts on optimizing Ag electrocatalyst performance for CO2 to CO conversion were presented. Three key findings are drawn out from the combined UHV surface science, STM and electrochemical measurements: (1) Using a series of Ag nanoparticles with 2-6 nm average diameters, CO2 reduction reaction (CO2RR) activity increases, with particle between 2 nm and ∼4 nm demonstrating the highest combination of activity and selectivity; (2) Electronic metal−support interactions (EMSIs) between Ag and C dramatically improve CO2RR performance as evidenced by a scaling relationship between particle size and the relative Ag−C EMSIs strength, which improves the CO2-to-CO Faradaic efficiency of sub-2 nm Ag particles from 2 to ∼100% and increases the CO turnover frequency ∼15-fold compared with similarly sized bare Ag particles; (3) The performance Ag electrocatalysts is improved when supported on S-doped C materials. Computational modeling of 1−10 nm Ag particles predicts a nearly identical size-dependent trend with maximum CO2RR activity predicted for 3.7nm particles. The calculations support the promotional effect of C materials, showing a large charge transfer of 1.02 e from Ag clusters to defective C and a 0.41 eV less endergonic step of forming COOH intermediate on Ag/defective-C compared to the Ag/C system. Calculations indicate a more favorable energetic pathway of CO2-to-CO at the C-S-Ag interface, consistent with experiments.

CO2 utilization

Feedstock/Pretreatment Screening for Bioconversion of Sugars and Lignin Residues

This project will conduct biomass deconstruction (pretreatment and enzymatic saccharification) on two representative biomass feedstocks and four different pretreatment processes, including three high temperature steam/chemical pretreatments and one low temperature chemical/mechanical pretreatment. A third biomass feedstock will undergo biomass deconstruction with three different pretreatment processes, including two high temperature chemical pretreatments and one low temperature chemical/mechanical pretreatment. Several pretreatment conditions will be performed in a screening study using NLR pilot-scale pretreatment equipment to generate a range of pretreated biomass substrates. A selected number of these substrates will be chosen for enzymatic saccharification evaluation, based on standard compositional analysis of the pretreated substrates as a primary indicator of pretreatment efficacy. Resulting enzymatic hydrolysis slurries will be analyzed to determine overall biomass sugar yields. Additional compositional analysis will be performed to determine oligomeric sugar composition and structure, to analyze structural characteristics of solids fractions on native, pretreated, and enzymatically saccharified biomass residues for one of the biomass feedstocks, corn stover. The enzymatically saccharified materials will undergo 2,3-butanediol fermentation in a shaker flask as bench scale. Using relevant process performance data collected in these various conversion steps, technoeconomic analysis activities will be performed to compare the economic potential of the various biomass feedstock and pretreatment processes and to identify key economic drivers and sustainability metrics.

09 BIOMASS FUELS

Discovery, Design, Synthesis and Testing of High Performance Structural Alloys (Final Technical Report)

The overarching goal of this project is to understand the phase stability and mechanical behavior of non-stoichiometric multi-principal element alloy (MPEA) materials. In order to identify suitable alloys, we plan to use a combinatorial thin film screening approach, in collaboration with scientists at Lawrence Berkeley National Laboratory who are performing computational work as well as complementary experimental work. Specific tasks within the scope of this project include the fabrication, using thin film deposition from six sputtering targets, of combinatorial samples with multi-dimensional gradients in composition and microstructure. These samples are studied to screen MPEA systems for promising candidate alloys with specific composition(s), based on characterization of composition, structure and mechanical behavior across the thin film. We want to produce single-phase MPEAs with chemical homogeneity in a given thin film region, simple grain structures, and no intermetallic phases present. Gradient films facilitate first-pass screening for desirable characteristics and inform the next stage of work that involves fabrication of bulk MPEA specimens for (tensile) mechanical testing and characterization. To make the bulk alloys, metal (elemental) pieces are melted to form MPEAs, followed by heat treatment to homogenize the composition and microstructure. A subset of alloys is also cast, using vacuum arc melting, to yield larger samples (diameter ~1 cm and length ~5-10 cm) and these allow us to assess viability of scale-up for the alloys in structural applications. Further processing plans include rolling and heat treatment to recrystallize selected bulk MPEAs and grow grains to different extents, in order to investigate size effects in the mechanical behavior of MPEAs. Microspecimen testing will be performed (primarily in tension) to assess the mechanical behavior over a range of temperatures. The deformation microstructure of mechanically tested alloys will be characterized using transmission electron microscopy (TEM) to provide a scientific basis for understanding the structure-property relationships in MPEA mechanical behavior.

36 MATERIALS SCIENCE

Feasibility of Metal Oxide Glasses and Polymer Membranes as Sorbents for Gaseous Oxidized Mercury

Mass spectrometry methods are currently under development by the atmospheric mercury (Hg) research community to elucidate the identity of atmospheric oxidized mercury (Hg II ) compounds. Due to high instrument detection limits, materials that can quantitatively preconcentrate atmospheric Hg II without facilitating compound-altering chemical reactions are needed to support these methods. Cation exchange membranes (CEM) and nylon membranes are currently used to preconcentrate ambient Hg II for concentration measurements and Hg II compound estimation, respectively. However, CEM and nylon membranes are poor candidates for observations by mass spectrometry methods due to release of interfering compounds upon heating; glasses do not have this problem. Here, three metal oxide glasses were explored as potential alternatives for Hg II preconcentration for future use with mass spectrometry methods: calcium phosphate (CaP), iron phosphate (FeP), and calcium aluminate (CaAl). The glasses demonstrated quantitative selective capture of HgBr 2 without capture of Hg 0 . Under ambient conditions, the CaP, FeP, and CaAl sorbed 36.4 ± 12.6% of the total HgII as the CEM. However, when Hg concentrations were normalized to surface area, CaP, FeP, and CaAl sorbed more HgBr 2 in the laboratory and ambient HgII compared to CEM. The CEM and CaP retained similar concentrations of HgBr 2 when preloaded samples were deployed in the field. Additionally, a permeation tube-based calibrator was used to load sorbents with HgBr 2 for investigation of HgII retention on CEM and thermal desorption profile changes on nylon membranes during active sampling. Nylon membranes were purchased from three vendors and used to compare HgBr 2 retention; a different HgBr 2 thermal desorption profile was achieved for each vendor’s nylon membrane.

Amides

Hybrid Doping Strategy with High‐Entropy Cu/Fe Surface Modification and Zr Bulk Incorporation for Ni‐Rich Cathodes

A hybrid doping strategy combining Zr 4+ bulk doping with high-entropy Cu 2+ /Fe 3+ surface doping is developed to enhance the structural and interfacial stability of Ni-rich layered oxide cathodes. Cu and Fe are selectively introduced at the particle surface via a surface-selective ion-exchange process, forming a ≈15 nm Fe-rich layer while preserving the layered framework. Compared to the pristine cathode, the hybrid sample exhibits significantly improved electrochemical performance in both half-cell and full-cell configurations. In half-cells, the hybrid retains 88.5% and 90.2% after 100 cycles at 1C under 4.6 and 4.5 V, respectively. During high-voltage full-cell cycling, the hybrid cathode maintains over 80% capacity retention, whereas the pristine counterpart retains less than 10% under identical conditions over the same cycling period. XPS, EELS, and DEMS analyses confirm improved oxygen retention, suppressed gas evolution, and stable surface chemistry, while DFT calculations indicate enhanced Me–O bonding in the selected Fe 0.75 Cu 0.25 (Mn 1/16 Co 2/16 Ni 13/16 )O 2 surface composition, which is identified through DFT-calculated mixing energy reaching a minimum at this ratio, indicating the most thermodynamically favorable configuration. In conclusion, these results demonstrate the effectiveness of this hybrid doping strategy in mitigating coupled degradation pathways in Ni-rich cathodes.

15 GEOTHERMAL ENERGY

Diffusion of acceptor dopants in monoclinic 𝛽−Ga 2⁢ O 3

𝛽−Ga 2 ⁢O 3 is a promising material for next-generation power electronics because of its ultrawide band gap and high critical breakdown voltage. However, realizing its full potential requires precise control over dopant incorporation and stability. In this work, we use first-principles calculations to systematically assess the diffusion behavior of eight potential deep-level substitutional acceptors (Au, Ca, Co, Cu, Fe, Mg, Mn, and Ni) in 𝛽−Ga 2 ⁢O 3 . We consider two key diffusion mechanisms: (i) interstitial diffusion under nonequilibrium conditions relevant to ion implantation, and (ii) trap-limited diffusion (TLD) under near-equilibrium thermal annealing conditions. Our results reveal a strong diffusion anisotropy along the 𝑏 and 𝑐 axes, with dopant behavior governed by competition between diffusion and incorporation (or dissociation) activation energies. Under interstitial diffusion, Ca$^{2+}_{i}$ and Mg$^{2+}_{i}$ show the most favorable combination of low migration and incorporation barriers, making them promising candidates for efficient doping along the 𝑏 and 𝑐 axes, respectively. In contrast, Au$^{+}_{i}$ diffuses readily, but exhibits an incorporation barrier that exceeds 5 eV, rendering it ineffective as a dopant. From a thermal stability perspective, Co$^{2+}_{i}$ shows poor activation but high diffusion barriers, which may suppress undesirable migration at elevated temperatures. Under trap-limited diffusion, the dissociation of dopant-host complexes controls mobility. Mg$^{2+}_{i}$ again emerges as a leading candidate, exhibiting the lowest dissociation barriers along both axes, whereas Co$^{2+}_{i}$ and Fe$^{2+}_{i}$ display the highest barriers, suggesting improved dopant retention under thermal stress. In conclusion, our findings guide dopant selection by balancing activation and thermal stability, essential for robust semi-insulating substrates.

Defects

Deactivation of Mo/H-ZSM-5 in Microwave-Assisted and Thermal-Driven Methane Dehydroaromatization

A better understanding of catalyst deactivation is needed to improve catalyst design and performance in microwave-enhanced methane dehydroaromatization (MDA). Here, this study investigates the deactivation of a molybdenum supported H-ZSM-5 zeolite (Mo/H-ZSM-5) catalyst in MDA under microwave-heated conditions, comparing its performance to that of the same catalyst under conventional heating. While the microwave-assisted (MW) process achieved higher benzene yields, the catalyst experienced faster deactivation due to the selective and rapid deposition of coke within the pores of the zeolite, as confirmed through Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), ammonia-temperature programmed desorption (NH 3 -TPD), thermal gravimetric analysis (TGA), temperature programmed oxidation (TPO), and X-ray photoelectron spectroscopy (XPS) analyses. The quantification of total coke content via TGA/TPO and surface carbon (XPS) revealed that nearly twice as much coke was deposited on the catalyst under MW conditions compared to that on the conventionally heated material, and the coke exhibited a more conductive and graphitic nature. The accelerated deactivation rates were attributed to the formation of hot spots in the MW system, leading to enhanced coupling with coke formed in situ during the reaction and resulting in increased Mo reduction. Observations indicated that the CO activation used to carburize the catalyst prior to the reaction is not advantageous in the MW heating environment. The presence of large amounts of Mo oxides at elevated temperatures (through hot spots) exposed to methane leads to instability under the reaction conditions. Optimizing the activation environment and improvement of the Mo dispersion within the pores are potential strategies to improve catalyst stability.

Mo/H-ZSM-5 zeolite

Chemically Enhanced Electrodialysis (CEED) for Recovery of Rare Earth Elements

Rare-earth elements are crucial for numerous technologically relevant industries including energy, electronics, and aerospace; however, both the supply and separation of rare earths are pressing challenges. The long-term goal of the collaborative project is to develop a novel approach to existing extraction behaviors. To achieve this goal, a class of electrodialysis membranes with novel ion-gating functionality will be developed and paired with a conventional electrodialysis strategy. The hypothesis of the work is that incorporating sequestrants of suitable structures at the surface of the electrodialysis membrane will enhance extraction efficiency for ions of interest. Our ability to prepare sequestrants of diverse conformations and to adapt their molecular structure for binding lanthanides renders the proposed technology a versatile method for selective ion separation. Our approach will enable an entirely new technological approach to the separation of valuable rare-earth elements.

36 MATERIALS SCIENCE

Contracted, Not Converted: Photoluminescence Thermochromism in Ultrabright Pure Blue Emissive Hybrid Copper(I) Halide

Thermochromic luminescent materials are promising for applications such as sensors or display technologies. Understanding the mechanism of thermochromic luminescence in these materials plays an important role for their targeted applications. Here, a 0D copper(I) halide (TMP)2CuBr3 and 1D (TMP)Ag2Br3 (TMP = tetramethylphosphonium) are reported. While (TMP)Ag2Br3 is a weak light emitter, (TMP)2CuBr3 demonstrates ultrabright pure blue emission with photoluminescence (PL) quantum yield exceeding 90% within the temperature range 300–80 K. The emission in (TMP)2CuBr3 is attributed to the radiative recombination of self-trapped excitons (STEs) that arise localized on [CuBr3]2− anions. (TMP)2CuBr3 demonstrates excitation-selective PL thermochromism at low temperatures. In the literature, the origin of multiple STEs is often unclear in luminescent metal halides. Here, a detailed temperature-dependent spectroscopic and structural analysis suggests that the PL thermochromism in (TMP)2CuBr3 is associated with the appearance of a second STE state. The appearance of second STE is expected to have a structural origin, and it may be associated with the observed anomaly in thermal contraction near 200 K. The distinct PL features of melt-processible (TMP)2CuBr3 coupled with its remarkable photo- and thermal stability allow its consideration for practical optical applications, including temperature sensing.

Popy, Dilruba [University of Oklahoma, Norman]

Reticular Materials and AI-Driven Computer Simulations for Seawater Mining of Valuable Metals (Final Technical Report)

This Final Technical Report describes our exploratory efforts that combine reticular materials synthesis (hydrolytically robust metal–organic frameworks, MOFs) with AI‑enabled molecular simulations to develop mechanistic, quantitative design rules for recovering lithium and other alkali-metal ions from highly dilute, competitive aqueous resources (e.g., seawater). The central outcome is a joint experimental–computational study of ion uptake in MOF‑808 (Chemical Science, 2025) that quantifies both thermodynamics and kinetics of Li + , Na + , and K + uptake and identifies how pore size, pore hydration state, dehydration penalties, and pore-window transport barriers govern selectivity. Guided by these insights, we synthesized and tested functionalized MOF‑808 and multivariate MOFs incorporating ion-recognition motifs (including carboxylates and crown-ether linkers) and evaluated uptake in synthetic seawater, highlighting framework topology and pore chemistry as levers for improved Li + /Na + discrimination. We also developed transferable simulation models, enhanced-sampling protocols, and automated workflows that enable systematic screening of porous sorbents.

42 ENGINEERING

Band-Selective Spin-Charge Separation across the Charge Density Wave Transition in Quasi-1D NbSe 3

Non-Fermi liquid (non-FL) phase is a pivotal enigma in understanding intriguing quantum phases in strongly correlated systems, such as high-temperature superconductivity. Tomonaga-Luttinger liquid (TLL) theory, designed for one-dimensional (1D) systems, serves as one of the microscopic frameworks that elucidates non-FL behavior. Despite its theoretical concreteness, comprehensive experimental verification has remained incomplete. In particular, addressing the persistence of the TLL nature within ordered phases, such as charge density wave (CDW), has posed a significant challenge. We report the observation of TLL characteristics across the CDW transitions in a quasi-1D material NbSe 3 using angle-resolved photoemission spectroscopy. Spin-charge separation, a disentanglement of spin and charge degrees of freedom of electrons, is clearly observed within the band, accompanied by the suppression of spectral weight following a power-law behavior with anticipated temperature scaling. Surprisingly, the spin-charge separation persists even below the CDW transition temperatures, indicating the validity of the TLL nature in the CDW phase. In conclusion, our findings offer a unique opportunity to explore the interplay between the TLL and ordered phases, which could be connected to the interplay between non-FL and ordered phases in strongly correlated systems.

1-dimensional systems

Hydration size-dependent transport of ions across nanoporous graphene membranes

Nanoporous atomically-thin membranes are promising candidates for metal ion separations due to their chemical stability and high permeance and selectivity, but experimental evidence of the mechanisms responsible for ion-ion selectivity is sparse. Here, in this work, we measured the simultaneous diffusion of a dilute mixture of ten different Group I, Group II, and rare earth cations in a salt background across nanoporous graphene (NPG) membranes with sub-nanometer pores. The membranes exhibited ion-ion selectivity, including between similarly-charged ions. Cation transport was governed primarily by the hydrated ion size that was consistent with continuum models of ion diffusion, with additional influence of the ionic charge. Selectivity enhancement was achieved by modifying ion sizes using an ion-selective complexing agent. Our study provides evidence of the importance of size-sieving and electrostatic mechanisms governing ion transport across NPG, and allows for quantitative prediction of transport rates to guide future development of ion-selective atomically-thin membranes.

36 MATERIALS SCIENCE

Strategy for Direct Detection of Chiral Phonons with Phase-Structured Free Electrons

Chiral phonons possessing valley pseudoangular momentum (PAM) underlie a diversity of quantum phenomena of fundamental and applied importance, but are challenging to probe directly. We show that deficiencies of typical momentum-resolved electron energy loss measurements that make it impossible to distinguish the PAM of chiral phonons can be overcome by introducing pinwheel free electron states with well-defined PAM. Transitions between such states generate 2D periodic arrays of in-plane field vortices with polarization textures tailored to selectively couple to desired chiral mode symmetries.

chirality

Gaseous Hydrogen Embrittlement of L-PBF Ni-Based Superalloys for Service in Natural Gas Turbines

Efforts to improve efficiency of industrial gas turbine engines have focused on increasing operating temperatures by use of fuel-flexible gas blends. Ni-based superalloys are susceptible to hydrogen embrittlement (HE), leading to potential risk of premature component failure. Certain turbine components exposed to hydrogen-rich environments are manufactured from additive processes like laser powder bed fusion (L-PBF). The HE susceptibility was evaluated for three Ni-based superalloys: solid solution strengthened Alloy 625, γ’/γ’’-precipitation strengthened Alloy 718, and γ’-precipitation strengthened Haynes® 282®. L-PBF samples were pre-charged under medium and high pressure gaseous hydrogen before tensile testing at temperatures up to 260 °C using a fast strain rate. Selected samples were subjected to a service conditioning heat treatment prior to hydrogen charging to evaluate the change in susceptibility after prolonged service. The susceptibility to HE and HE mechanisms of these three alloys is compared.

additive manufacturing