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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 271 records · Page 15

First-Principles Approach for Assessing Cold Electron Injection Efficiency of Dye-Sensitized Solar Cell: Elucidation of Mechanism of Charge Injection and Recombination

The adequacy of the inclusion of spacer units in the metal-free D-π–A organic dyes pertaining to the augmentation of dye-sensitized solar cell (DSSC) efficiency has been examined through the excited-state simulations of the charge injection and recombination processes at the dye–semiconductor interface. Within the framework of the time-dependent density functional theory, the proposed computational studies focus on the precise evaluation of pivotal factors controlling the rates of photoinduced charge-transfer and energy-transfer processes, including electronic coupling, reorganization energy, and threshold energy barrier in the semiclassical Marcus formalism. The estimation of the fluorescent state appears to be the crucial step while explaining the ultrafast electron injection process and the charge recombination at the Marcus inverted region, as revealed by the obtained results. The retardation of charge recombination is facilitated by the insertion of a thiophene moiety between the π-bridge and the acceptor units. The estimated cold electron injection efficiencies deploying the Onsager–Braun theory, that rely on the computations of cold electron injection lifetime and cold electron lifetime, show a linear correlation with the experimental photovoltaic parameters of the DSSC comprising short-circuit current density, open-circuit voltage, and power conversion efficiency. The outcomes of the present investigation establish a basis for unraveling the mechanism of intricate dynamical processes upon photoexcitation of the sensitizers, as well as devising plausible routes for functional DSSC materials.

14 SOLAR ENERGY↗

In Situ Monitoring of H 2 -Induced Nonstoichiometry in Cu 2 O

Nonstoichiometry plays a pivotal role in the functioning of oxide materials, but it is challenging to measure the non-stoichiometric formation and the resulting charge redistribution around the point defects. Using ambient-pressure X-ray photoelectron spectroscopy and Auger electron spectroscopy to monitor the reduction of Cu 2 O in H 2 , we identify the formation of an intermediate, oxygen-deficient Cu 2 O phase and its progressive inward growth into the deeper region of the oxide. Complemented by DFT modeling, we show that the oxygen-deficient Cu 2 O formation occurs via molecular H 2 adsorption at the Cu 2 O surface, which results in the loss of lattice O from the formation of H 2 O molecules that desorb spontaneously from the oxide surface. The resulting oxy-gen-deficient Cu 2 O is a stable intermediate that persists before the Cu 2 O is fully reduced to metallic Cu. The O vacancy induced charge redistribution of the coordinating Cu atoms results in a satellite feature in Cu LMM, which can be used a fingerprint to identify the nonstoichiometry and local charge transfer in non-stoichiometric oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Untapped Potential of Fluoride Ions in Maximizing the Electrochemical Stability of Deep Eutectic Solvents

Advancing the batteries is pivotal to propelling our society toward a sustainable, electrified future. The stability of electrolytes forms the backbone of energy storage systems. This is particularly the case for redox flow batteries (RFBs). Their deployability depends on their longevity and dependability. The presence of unstable electrolytes can trigger undesirable reactions, degrade performance, and lead to battery failure. Aqueous electrolytes, with limited electrochemical stability window (ESW), are prone to hydrogen and oxygen evolution. Conversely, non-aqueous electrolytes offer enhanced stability. In this study, we unveil the ESW of a non-aqueous eutectic solvent, comprising choline fluoride and ethylene glycol—a composition that has eluded experimental investigation until now. Our findings show that the stability window, reduction and oxidation potential limits of deep eutectic solvents, are sensitive to variations in the halide component of the ammonium salt. Furthermore, this work not only highlights the benefits of novel deep eutectic solvents but also sets the stage for their strategic use in future battery electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Black Phosphorus for Mid-Infrared Optoelectronics: Photophysics, Scalable Processing, and Device Applications

High efficiency mid-infrared (λ = 3-8 μm) light emitters and photodetectors are pivotal for advancing next-generation optoelectronics. However, narrow-bandgap semiconductors face fundamental challenges such as pronounced nonradiative carrier recombination and thermally generated noise, which impede device performance. Recently, two-dimensional layered black phosphorus (BP) and its alloys have attracted substantial interest for mid-infrared device applications, demonstrating superior performance relative to conventional III-V and II-VI semiconductors with similar bandgaps. In this review, we discuss the optical properties of BP, contrasting these with those of covalent compounds. Owing to its inherently self-terminated surface structure and reduced nonradiative recombination, BP exhibits high performance in light emission and photodetection at room temperature. Furthermore, this review highlights recent advances in the large-area processing of BP thin films, paving the way for practical device applications and integration. Finally, we explore ongoing challenges and emerging opportunities in the utilization of BP for functional mid-infrared devices.

Higashitarumizu, Naoki↗

Crossover from Conventional to Unconventional Superconductivity in 2M-WS 2

Leveraging the reciprocal-space proximity effect between superconducting bulk and topological surface states (TSSs) offers a promising way to topological superconductivity. However, elucidating the mutual influence of bulk and TSSs on topological superconductivity remains a challenge. Here, we report pioneering transport evidence of a thickness-dependent transition from conventional to unconventional superconductivity in 2M-phase WS 2 (2M-WS 2 ). As the sample thickness reduces, we see clear changes in key superconducting metrics, including critical temperature, critical current, and carrier density. Notably, while thick 2M-WS 2 samples show conventional superconductivity, with an in-plane (IP) upper critical field constrained by the Pauli limit, samples under 20 nm exhibit a pronounced IP critical field enhancement, inversely correlated with 2D carrier density. This marks a distinct crossover to unconventional superconductivity with strong spin-orbit-parity coupling. Furthermore, our findings underscore the crucial role of sample thickness in accessing topological states in 2D topological superconductors, offering pivotal insights into future studies of topological superconductivity.

2D topological superconductor↗

Dendritic Computing with Multigate Ferroelectric Field-Effect Transistors

Although inspired by neuronal systems in the brain, artificial neural networks generally employ point-neurons, which offer computational complexity far less than that of their biological counterparts. Neurons have dendritic arbors that connect to different sets of synapses and offer local nonlinear accumulation – playing a pivotal role in processing and learning. Inspired by this, we propose a novel neuron design based on a multigate ferroelectric field-effect transistor that mimics dendrites. It leverages ferroelectric nonlinearity for local computations within dendritic branches while utilizing the transistor action to generate the neuronal output. The branched architecture enables smaller crossbar arrays in hardware integration, improving efficiency. Using an experimentally calibrated device-circuit-algorithm cosimulation framework, we demonstrate that networks incorporating our dendritic neurons achieve superior performance compared to much larger networks without dendrites (∼ 17× fewer trainable weight parameters). These findings suggest that dendritic hardware can significantly improve computational efficiency and learning capacity of neuromorphic systems optimized for edge applications.

36 MATERIALS SCIENCE↗

SiO 2 Is Wasted Space in Single-Nanometer-Scale Silicon Nanoparticle-Based Composite Anodes for Li-Ion Electrochemical Energy Storage

The electrode processing conditions of silicon-based composite anodes play a pivotal role in the resulting interfacial chemical speciation and, thus, the electrochemical cycling behavior of the electrode. Systematically investigating how small chemical changes to the surface of the silicon nanoparticle (NP) affect larger, electrode-level properties is a strategy that will inform design principles to maximize electrode energy density and extend electrode lifetime. Here, we incorporate silicon nanoparticles (NPs) with an average diameter of 5.5 nm synthesized from the gas phase through a nonthermal plasma method into composite anode half-cell coin cells. We perform chemistry to functionalize the native hydride-terminated silicon NP surface with N-methylpyrrolidone (NMP) to improve slurry properties and reduce the silicon reactivity prior to composite electrode fabrication. We construct composite electrodes from these silicon NPs and observe an 86% capacity retention over 100 cycles at a rate of C/5, with an initial silicon specific capacity of 2600 mAh/g. We expose the same Si NPs to water that completely oxidizes these small-diameter NPs to SiO 2 and find that the SiO 2 NPs in the same electrode configuration exhibit no obvious lithium alloying capacity in the electrochemical potential range of lithium silicide alloy formation. As this result stands in contrast to existing literature, we provide a discussion on the origin of the discrepancies.

25 ENERGY STORAGE↗

Unveiling Morphology and Crystallinity Dynamics in Ni x Mn 1– x CO 3 Cathode Precursors through Batch-Mode Coprecipitation

This study delves into the synthesis and control of Ni x Mn 1–x CO 3 , a critical class of Mn-rich, Co-free precursors vital for cathode-oxide materials in energy storage and conversion technologies. Employing batch-mode coprecipitation, we systematically generated samples with varying Ni concentrations (x = 0, 0.1, 0.3, 0.5, 0.7, and 0.9) and conducted a comprehensive analysis of their compositions, crystallinities, transition-metal distributions, and particle morphologies through both experimental and computational methods. A significant variation in particle size and crystallinity was observed, contingent on the Ni content. Further, a pivotal transition emerged at Ni concentrations above x = ~0.5, transforming uniform morphologies, such as spherical, monodisperse, pseudo-single-crystalline particles, into bimodal, polycrystalline structures. Furthermore, the study highlights the role of Ni–ammonia complexes leading to Ni-deficient precipitates and underscores the importance of ammonia concentration in achieving precise Ni content control. This study unveils critical reaction conditions governing Mn-rich precursor properties that are vital for cathode-oxides, emphasizing the need for meticulous synthetic control and offering the potential for practical applications in advanced energy storage and conversion systems.

25 ENERGY STORAGE↗

Quantifying the Correlation between Coordination Chemistry, Interfacial Formation, and Electrochemical Performances for Mg Battery Electrolytes

Here, the rise of magnesium batteries as promising post-Li-ion energy storage technologies has sparked considerable attention toward understanding the fundamental aspects of coordination chemistry concerning Mg cations in multivalent electrolytes. This exploration includes investigating how coordination influences crucial electrolyte properties like solubility, electroreduction stability, and the formation of the interphase, all of which are pivotal for practical battery applications. Despite recent progress in developing a few functional electrolytes, a comprehensive understanding of the solvation structure that can facilitate efficient Mg deposition performance and the formulation of general design rules based on the solvation structure is still lacking. In our study, we endeavor to establish a connection between solvent and anion interactions with Mg 2+ , interface formation, and cycling performance through a series of organic ether solvents (tetrahydrofuran, glyme, diglyme, and triglyme) and amine solvents (dimethylamine, 3-methoxypropylamine, and dimethoxyethylamine). Our findings reveal a distinct coordination trend for solvent/Mg 2+ and (Mg-TFSI):solvent across various solvents, which dictates the extent of ion pairing for TFSI salts with increasing solvent molecule size and denticity. The solvated species in the bulk electrolyte across different solvents lead to diverse interfacial chemistries with varying decomposition components. We also explore the cycling efficiency as well as Mg deposition overpotentials for different solvents. A correlation analysis was conducted to assess the interplay between the structure and performance. Lastly, we apply the insights gained from these results to tailor the relative anion/Mg 2+ coordination structures using cosolvent systems, aiming for improved cell performance.

25 ENERGY STORAGE↗

Role of Surface Termination in the Metal–Insulator Transition of V 2 O 3 (0001) Ultrathin Films

Surface termination is known to play an important role in determining the physical properties of materials. It is crucial to know how surface termination affects the metal–insulator transition (MIT) of V 2 O 3 films for both fundamental understanding and its applications. By changing growth parameters, we achieved a variety of surface terminations in V 2 O 3 films that are characterized by low-energy electron diffraction (LEED) and photoemission spectroscopy techniques. Depending upon the terminations, our results show that MIT can be partially or fully suppressed near the surface region due to the different fillings of the electrons at the surface and subsurface layers and the change of screening length compared to the bulk. Across MIT, a strong redistribution of spectral weight and its transfer from a high-to-low-binding energy regime is observed in a wide energy scale. Our results show that the total spectral weight in the low-energy regime is not conserved across MIT, indicating a breakdown of the “sum rules of spectral weight”, signature of a strongly correlated system. Such a change in spectral weight is possibly linked to the change in hybridization, lattice volume (i.e., effective carrier density), and the spin degree of freedom in the system that occurs across MIT. We find that MIT in this system is strongly correlation-driven, where the electron–electron interactions play a pivotal role. Furthermore, our results provide better insight into the understanding of the electronic structure of strongly correlated systems and highlight the importance of accounting for surface effects during interpretation of the physical property data mainly using surface-sensitive probes, such as surface resistivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electrolyte Reactivity at the Charged Ni-Rich Cathode Interface and Degradation in Li-Ion Batteries

The chemical and electrochemical reactions at the positive electrode–electrolyte interface in Li-ion batteries are hugely influential on cycle life and safety. Ni-rich layered transition metal oxides exhibit higher interfacial reactivity than their lower Ni-content analogues, reacting via mechanisms that are poorly understood. Here, we study the pivotal role of the electrolyte solvent, specifically cyclic ethylene carbonate (EC) and linear ethyl methyl carbonate (EMC), in determining the interfacial reactivity at charged LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC111) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes by using both single-solvent model electrolytes and the mixed solvents used in commercial cells. While NMC111 exhibits similar parasitic currents with EC-containing and EC-free electrolytes during high voltage holds in NMC/Li 4 Ti 5 O 12 (LTO) cells, this is not the case for NMC811. Online gas analysis reveals that the solvent-dependent reactivity for Ni-rich cathodes is related to the extent of lattice oxygen release and accompanying electrolyte decomposition, which is higher for EC-containing than EC-free electrolytes. Combined findings from electrochemical impedance spectroscopy (EIS), TEM, solution NMR, ICP, and XPS reveal that the electrolyte solvent has a profound impact on the degradation of the Ni-rich cathode and the electrolyte. Higher lattice oxygen release with EC-containing electrolytes is coupled with higher cathode interfacial impedance, a thicker oxygen-deficient rock-salt surface reconstruction layer, more electrolyte solvent and salt breakdown, and higher amounts of transition metal dissolution. These processes are suppressed in the EC-free electrolyte, highlighting the incompatibility between Ni-rich cathodes and conventional electrolyte solvents. Finally, new mechanistic insights into the chemical oxidation pathways of electrolyte solvents and, critically, the knock-on chemical and electrochemical reactions that further degrade the electrolyte and electrodes curtailing battery lifetime are provided.

25 ENERGY STORAGE↗

Hierarchical, Self-Assembled Metasurfaces via Exposure-Controlled Reflow of Block Copolymer-Derived Nanopatterns

Here, nanopatterning for the fabrication of optical metasurfaces entails a need for high-resolution approaches like electron beam lithography that cannot be readily scaled beyond prototyping demonstrations. Block copolymer thin film self-assembly offers an attractive alternative for producing periodic nanopatterns across large areas, yet the pattern feature sizes are fixed by the polymer molecular weight and composition. Here, a general strategy is reported that overcomes the limitation of fixed feature size by treating the copolymer thin film as a hierarchical resist, in which the nanoscale pattern motif is defined by self-assembly. Feature sizes can then be tuned by thermal reflow controlled locally by irradiative crosslinking or chemical alteration using lithographic ultraviolet light or electron beam exposure. Using blends of polystyrene-block-poly(methylmethacrylate) (PS-b-PMMA) with PS and PMMA homopolymer, we demonstrate both self-assembled PS grating and hexagonal hole patterns; exposure-controlled reflow is then used to reduce hole diameter by as much as 50% or increase PS grating linewidth by more than 180%. Transferring these nanopatterns, or their inverse obtained by a lift-off approach, into silicon yields structural colors that may be prescriptively controlled based on nanoscale feature size. Furthermore, patterned exposure enables area-selective feature size control, yielding uniform structural color patterns across centimeter square areas. Electron beam lithography is also used to show that the lithographic resolution of this selective-area control can be extended to the nanoscale dimensions of the self-assembled features. The exposure-controlled reflow approach demonstrated here takes a pivotal step towards fabricating complex, hierarchical optical metasurfaces using scalable self-assembly methods.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Assessment of the Degradation Mechanisms of Cu Electrodes during the CO 2 Reduction Reaction

Catalyst degradation and product selectivity changes are two of the key challenges in the electrochemical reduction of CO 2 on copper electrodes. Yet, these aspects are often overlooked. Here, we combine in situ X-ray spectroscopy, in situ electron microscopy, and ex situ characterization techniques to follow the long-term evolution of the catalyst morphology, electronic structure, surface composition, activity, and product selectivity of Cu nanosized crystals during the CO 2 reduction reaction. We found no changes in the electronic structure of the electrode under cathodic potentiostatic control over time, nor was there any build-up of contaminants. In contrast, the electrode morphology is modified by prolonged CO 2 electroreduction, which transforms the initially faceted Cu particles into a rough/rounded structure. In conjunction with these morphological changes, the current increases and the selectivity changes from value-added hydrocarbons to less valuable side reaction products, i.e. , hydrogen and CO. Hence, our results suggest that the stabilization of a faceted Cu morphology is pivotal for ensuring optimal long-term performance in the selective reduction of CO 2 into hydrocarbons and oxygenated products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Trailblazing Kr/Xe Separation: The Birth of the First Kr-Selective Material

Efficient separation of Kr from Kr/Xe mixtures is pivotal in nuclear waste management and dark matter research. Thus far, scientists have encountered a formidable challenge: the absence of a material with the ability to selectively adsorb Kr over Xe at room temperature. This study presents a groundbreaking transformation of the renowned metal–organic framework (MOF) CuBTC, previously acknowledged for its Xe adsorption affinity, into an unparalleled Kr-selective adsorbent. This achievement stems from an innovative densification approach involving systematic compression of the MOF, where the crystal size, interparticle interaction, defects, and evacuation conditions are synergistically modulated. The resultant densified CuBTC phase exhibits exceptional mechanical resilience, radiation tolerance, and notably an unprecedented selectivity for Kr over Xe at room temperature. Simulation and experimental kinetic diffusion studies confirm reduced gas diffusion in the densified MOF, attributed to its small pore window and minimal interparticle voids. The lighter Kr element demonstrates facile surface passage and higher diffusivity within the material, while the heavier Xe encounters increased difficulty entering the material and lower diffusivity. This Kr-selective MOF not only represents a significant breakthrough in Kr separation but also demonstrates remarkable processability and scalability to kilogram levels. Furthermore, the findings presented herein underscore the transformative potential of engineered MOFs in addressing complex challenges, heralding a new era of Kr separation technologies.

36 MATERIALS SCIENCE↗

Controlling the Aspect Ratios of Au Nanocrystals with Ag+ Addition Time in Seed-Mediated Synthesis: Implications for Surface-Enhanced Raman Scattering

Among various factors playing pivotal roles in the typical seed-mediated growth of Au nanocrystals (NCs), the role of Ag (AgNO3) has remained debatable over time and seminal research efforts have helped us in reaching a consensus, albeit from the standpoint of [Ag+] concentration. This study aims to provide an understanding of the role of Ag+ from the perspective of time. Here, we show that different Au NCs with tunable aspect ratios (ARs) can be generated in one system in high yield simply by varying the time of addition of Ag+ in the growth solution. The generality of the method has been demonstrated in tuning the ARs of anisotropic Au NCs like concave cuboid (CCB, AR = 2) and elongated tetrahexahedra (AR = 2.5), where the delayed addition of Ag+ leads to the formation of their isotropic counterpart concave cube (CC, AR = 1) and tetrahexahedra (AR = 1), respectively. This work, apart from establishing timed addition of Ag+ as a crucial parameter in controlling the AR, may also help in the realization of a universal growth mechanism of Au NCs. The Au NCs with varying ARs (CCB, AR = 2 and CC, AR = 1) have been further explored as potential substrates for surface-enhanced Raman scattering (SERS) due to the presence of their high-index facets and sharp tips.

KEYWORDS:Au nanoparticles seed-mediated growth hig↗

Laser-Induced Trapping of Metastable Amorphous AlO x /C (2.5 < x ≤ 3.5) Nanocomposites: Implications for Use as Solid Phase Gas Generators

The synthesis of kinetically "frozen" metastable nanostructures remains elusive. This limitation has severely restricted the current paradigms in materials discovery. We overcame this challenge by phase-stabilizing unusually hyperoxidized and metastable amorphous aluminum oxide (a-AlO x ; 2.5 < x ≤ 3.5) nanostructures. Specifically, we employed laser ablation synthesis in solution (LASiS) as a one-pot nonequilibrium technique to achieve this pivotal advancement. Structural and compositional characterizations of the as-synthesized material reveal highly disordered a-AlO x nanoparticles that are remarkably stabilized by interfacial monolayers of ordered carbon atoms. Both structure and chemical composition were confirmed with disparate characterization methods at different length scales. The nanoparticles of sizes less than10 nm were stable even at elevated temperatures. Only at temperatures higher than 750 °C do the a-AlO x structures undergo a solid-solid phase transition that culminates in the formation of stable α-Al 2 O 3 while releasing excess trapped gases. In conclusion, such disruptive materials can find applications in emerging technologies seeking metastable phase-change materials for solid phase gas generators, batteries, neuromorphic computing, and energetic additives.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reverse Polarizability of Rare Earth Ions (La 3+ , Gd 3+ , Lu 3+ , Y 3+ ) in Tellurite Glasses and Glass Ceramics for Optical Limiting

All-optical modulation using inherent third-order optical nonlinearity of a medium has garnered considerable interest in photonics and optoelectronics. Herein, nonlinear optical (NLO) properties of tellurite glasses and glass ceramics (GCs) containing four different rare earths (RE = La, Gd, Lu, and Y) have been deliberated in near-infrared regions under an ultrafast regime. The La-based glass exhibits ~10 times higher nonlinear refraction (n 2 ) and absorption (α 2 ) than reported NLO materials. The NLO susceptibility [χ (3) ] trend in the studied glasses is La > Gd > Lu > Y, matching with RE 3+ polarizability. Furthermore, Ln 2 Te 6 O 15 nanocrystallite-embedded transparent GCs exhibit a larger NLO coefficient due to the enhanced local field from oxygen vacancies in crystallites. Interestingly, the trend of χ (3) in GCs follows the sequence of Y > Lu > Gd > La, precisely opposite to the glasses. This observation challenges the general polarizability approach of RE 3+ ions, emphasizing that quadratic hyperpolarizability of RE 3+ is pivotal for NLO properties of GCs. Among the studied matrices, Y-containing GCs showed the lowest optical limiting (OL) threshold (5.4 mJ/cm 2 at 800 nm), much lower than those of the reported NLO materials, suggesting its potential as a femtosecond NIR-laser safety material. A combination of large α 2 and n 2 from the studied matrices indicates their advantage for harmonic generation, potentially aiding in the design of ultrafast signal processing devices.

36 MATERIALS SCIENCE↗

Polymer, Additives, and Processing Effects on N95 Filter Performance

The current severe acute respiratory syndrome coronavirus 2 (SARS-COV-2) pandemic has highlighted the need for personal protective equipment, specifically filtering facepiece respirators like N95 masks. While it is common knowledge that polypropylene (PP) is the industry standard material for filtration media, trial and error is often required to identify suitable commercial precursors for filtration media production. This work aims to identify differences between several commercial grades of PP and demonstrate the development of N95 filtration media with the intent that the industry partners can pivot and help address N95 shortages. Three commercial grades of high melt flow index PP were melt blown at Oak Ridge National Laboratory and broadly characterized by several methods including differential scanning calorimetry (DSC), X-ray diffraction (XRD), and neutron scattering. Despite the apparent similarities (high melt flow and isotacticity) between PP feedstocks, the application of corona charging and charge enhancing additives improve each material to widely varying degrees. From the analysis performed here, the most differentiating factor appears to be related to crystallization of the polymer and the resulting electret formation. Materials with higher crystallization onset temperatures, slower crystallization rates, and larger number of crystallites form a stronger electret and are more effective at filtration.

36 MATERIALS SCIENCE↗