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At least 145 records · Page 8

Imaging and Segmenting Grains and Subgrains Using Backscattered Electron Techniques

We present two new methods of processing data from backscattered electron signals in a scanning electron microscope to image grains and subgrains. The first combines data from multiple backscattered electron images acquired at different specimen geometries to (1) better reveal grain boundaries in recrystallized microstructures and (2) distinguish between recrystallized and unrecrystallized regions in partially recrystallized microstructures. The second utilizes spherical harmonic transform indexing of electron backscatter diffraction patterns to produce high angular resolution orientation data that enable the characterization of subgrains. Subgrains are produced during high-temperature plastic deformation and have boundary misorientation angles ranging from a few degrees down to a few hundredths of a degree. Here, we also present an algorithm to automatically segment grains from combined backscattered electron image data or grains and subgrains from high angular resolution electron backscatter diffraction data. Together, these new techniques enable rapid measurements of individual grains and subgrains from large populations.

36 MATERIALS SCIENCE↗

Antiferromagnetic V 2 ⁢O 3 based exchange coupling

Vanadium sesquioxide (V 2 ⁢O 3 ) is a strongly correlated electronic material that famously undergoes a triple coupled first-order transition where it transitions from a paramagnetic metal with a rhombohedral structure at high temperature to an antiferromagnetic insulator with a monoclinic structure. While several studies have used one of both electronic and structural transitions to control the properties of a heterostructure, evidence of magnetic coupling has notoriously yet to be found. In this paper, we report on a robust magnetic coupling between the antiferromagnetic (AFM) V 2 ⁢O 3 and ferromagnetic (FM) Permalloy (Py) layers that results in a significant exchange bias and strain-induced coercivity enhancement. We provide a temperature and angle-dependent study of magnetic properties, which clearly indicates exchange bias at the AFM/FM interface that appears at the onset of the metal-insulator transition. The magnitude of the exchange bias is strongest when the field is applied along the [001] V 2 ⁢O 3 crystallographic orientation which corresponds to an AFM spin configuration on the [110] surface. Here, this opens the door to designing and implementing novel functionalities in transition metal oxide-based computing using the connection between magnetism and the metal-insulator transition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High Pressure Synthesis of Ultrasmall Nanodiamonds with Nitrogen Vacancy Centers

C–H terminated nanometer scale diamonds ( d = 1 to 15 nm) are synthesized from 1-fluoroadamantane at high pressure (6–8 GPa) and high temperature (500–1500 °C) in a multianvil press. High resolution transmission electron microscopy, X-ray diffraction, Raman, diffuse reflectance Fourier transform infrared, and X-ray absorption spectroscopies demonstrate the excellent crystallinity and atomically flat C–H terminated surfaces of nanodiamonds with (111) and (110) facets. The importance of hydrogen to the synthesis of nanodiamond and its faceting is discussed. Following vacancy generation, annealing and oxidation of the nanodiamonds, optically detected magnetic resonance and electron spin resonance coherence times ( T 2 = 0.9 and 2.1 μs) of nitrogen vacancy (NV) centers are measured. Finally, the obtained T 2 values are equivalent to the shallow NV centers (depth <10 nm) in bulk diamond crystals and larger nanocrystals prepared by mechanical milling.

36 MATERIALS SCIENCE↗

Chemical bond and phase stability of Ga-doped Sm2Fe17Cx magnet

Sm2Fe17C3 phase (2:17) is metastable and exhibits excellent intrinsic hard magnetic properties. Doping elements such as Ga facilitate the formation of a single-phase 2:17 structure in arc-melted Sm2Fe17Cx alloys, which opens a promising route for fabricating fully dense bulk Sm2Fe17Cx magnets via high-temperature techniques such as melting and sintering. First-principles electronic structure calculation indicates that Ga prefers to partially replace Fe at the 9d and 18h crystallographic sites in Sm2Fe17C3 and Sm2Fe17, respectively. This difference in site preference is attributed to the distinct chemical environments surrounding the Fe atoms in the two compounds. Ga substitution favors the Sm–Ga bonding formation while avoiding Ga–C interactions. Doped Ga atoms result in more negative formation energy in Sm2(Fe, Ga)17C3, indicating improved structural stability. Crystal Orbital Hamilton Population analysis reveals that carbon insertion weakens the bonding of Sm-Fe (18h) and Sm-Fe (18f) in Sm2Fe17C3. Ga doping facilitates electron redistribution across chemical bonds, thereby reinforcing Fe(18h)–Sm and Fe(18f)–Sm interactions and stabilizing the carbon-centered octahedral local structure. This synergistic effect contributes significantly to the observed enhancement in phase stability of Sm2(Fe, Ga)17Cx. These findings suggest that chemical bond engineering through the selective doping of Ga can enhance phase stability and facilitate the synthesis of Sm2Fe17C3, providing a viable strategy for developing advanced magnets.

Liu, Xubo [Critical Materials Innovation Hub, Divi↗

Supermodulation-driven evolution of the nodal structure of bismuth-based cuprate superconductors

Recent work has shown novel properties of twisted cuprates. In this paper, I point out that related phenomena occur intrinsically in bismuth-based cuprate superconductors due to the presence of the BiO supermodulation. As the ratio of the supermodulation potential to the superconducting energy gap increases, two critical points are found where semi-Dirac nodes form (that is, they have quadratic dispersion in one direction and linear dispersion in the orthogonal direction). The first critical point should be realized in Bi2212, the second in Bi2201. Implications of these findings are discussed.

Cuprates↗

Designing multicomponent hydrides with potential high T c superconductivity

While hydrogen-rich materials have been demonstrated to exhibit high T c superconductivity at high pressures, there is an ongoing search for ternary, quaternary, and more chemically complex hydrides that achieve such high critical temperatures at much lower pressures. First-principles searches are impeded by the computational complexity of solving the Eliashberg equations for large, complex crystal structures. Here, we adopt a simplified approach using electronic indicators previously established to be correlated with superconductivity in hydrides. This is used to study complex hydride structures, which are predicted to exhibit promisingly high critical temperatures for superconductivity. In particular, we propose three classes of hydrides inspired by the Fm$\overline{3}$ m RH 3 structures that exhibit strong hydrogen network connectivity, as defined through the electron localization function. The first class [RH 11 X 3 Y] is based on a Pm$\overline{3}$m structure showing moderately high T c , where the T c estimate from electronic properties is compared with direct Eliashberg calculations and found to be surprisingly accurate. The second class of structures [(RH 11 ) 2 X 6 YZ] improves on this with promisingly high density of states with dominant hydrogen character at the Fermi energy, typically enhancing T c . The third class [(R 1 H 11 )(R 2 H 11 )X 6 YZ] improves the strong hydrogen network connectivity by introducing anisotropy in the hydrogen network through a specific doping pattern. These design principles and associated model structures provide flexibility to optimize both T c and the structural stability of complex hydrides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Perfect Coulomb drag and exciton transport in an excitonic insulator

Strongly coupled electron-hole bilayers can host quantum states of interlayer excitons, such as high-temperature exciton condensates at zero magnetic field. This state is predicted to feature perfect Coulomb drag, where a current in one layer is accompanied by an equal but opposite current in the other. We used an optical technique to probe the electrical transport of correlated electron-hole bilayers based on MoSe2/hBN/WSe2 heterostructures. We observed perfect Coulomb drag in the excitonic insulator phase at low temperatures; the counterflow resistance of interlayer excitons remained finite. These results indicate the formation of an exciton gas that does not condense into a superfluid. Our work demonstrates that dynamic optical spectroscopy provides a powerful tool for probing exciton transport behavior in correlated electron-hole fluids.

Qi, Ruishi↗

Thermodynamics, local structure, and transport of protons in triple-conducing oxide, BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ (BCFZY4411)

Triple-conducting oxides (TCOs) are an emerging class of mixed ionic and electronically conducting materials that show great promise for oxygen reduction/oxygen evolution (ORR/OER) electrocatalysis—primarily in high-temperature ceramic electrochemical cells— but also in aqueous alkaline environments. Their high activity is attributed, at least in part, to their ability to incorporate and transport three mobile charge carriers: protons, oxygen vacancies, and electron-holes Despite their promise, fundamental studies of TCOs are challenging, as transport dynamics from three charge carriers cannot be fully disentangled via traditional electrical measurement techniques. Characterizing proton dynamics in TCOs is particularly difficult as protons are generally the minority carrier, and their conduction response is typically obscured by the oxygen vacancies and electron holes. Here, we demonstrate successful isolation of the proton behavior in an archetypal TCO, BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ (BCFZY4411), using a combination of non-electrical techniques. We determine proton uptake and oxygen non-stoichiometry (δ) using thermogravimetric analysis (TGA). X-ray absorption near edge structure (XANES) and neutron diffraction (ND) are used to validate the oxidation state of Co and the δ values obtained through TGA. We apply 1H solid-state magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) to provide insights into local structure, dynamics, and proton kinetics. Finally, the proton transport properties are further quantified using tracer isotope exchange with time-of-flight secondary ion mass spectrometry (ToF-SIMS). Despite the very low proton concentrations in BCFZY4411 (<0.2% under most conditions), our analysis suggests that the oxygen Manuscript File Click here to view linked References 2 reduction and evolution reactions are nevertheless limited by the oxygen ion kinetics (e.g., oxygen surface exchange) rather than the proton kinetics at the reduced operating temperatures (<500 °C) that are targeted for electrochemical cell applications. These findings provide a comprehensive understanding of proton behavior in BCFZY4411 and pave the way for advancing the fundamental study of TCOs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

2D Vacancy Confinement in Anatase TiO 2 for Enhanced Photocatalytic Activities

Abstract Light‐driven energy conversion devices call for the atomic‐level manipulation of defects associated with electronic states in solids. However, previous approaches to produce oxygen vacancy (V O ) as a source of sub‐bandgap energy levels have hampered the precise control of the distribution and concentration ofV O . Here, a new strategy to spatially confineV O at the homo‐interfaces is demonstrated by exploiting the sequential growth of anatase TiO 2 under dissimilar thermodynamic conditions. Remarkably, metallic behavior with high carrier density and electron mobility is observed after sequential growth of the TiO 2 films under low pressure and temperature (L‐TiO 2 ) on top of high‐quality anatase TiO 2 epitaxial films (H‐TiO 2 ), despite the insulating properties of L‐TiO 2 and H‐TiO 2 single layers. Multiple characterizations elucidate that theV O layer is geometrically confined within 4 unit cells at the interface, along with low‐temperature crystallization of upper L‐TiO 2 films; this 2DV O layer is responsible for the formation of in‐gap states, promoting photocarrier lifetime (≈300%) and light absorption. These results suggest a synthetic strategy to locally confine functional defects and emphasize how sub‐bandgap energy levels in the confined imperfections influence the kinetics of light‐driven catalytic reactions.

Chemistry↗

Thermal Conversion of Ultrathin Nickel Hydroxide for Wide Band Gap 2D Nickel Oxides

Wide band gap (WBG) semiconductors (E g > 2.0 eV) are integral to the advancement of next-generation electronics, optoelectronics, and power industries owing to their capability for high-temperature operation, high breakdown voltage, and efficient light emission. Enhanced power efficiency and functional performance can be attained through miniaturization, specifically via the integration of device fabrication into a two-dimensional (2D) structure enabled by WBG 2D semiconductors. However, as an essential subgroup of WBG semiconductors, 2D transition metal oxides (TMOs) remain largely underexplored in terms of physical properties and applications in 2D optoelectronic devices, primarily due to the scarcity of sufficiently large 2D crystals. Thus, our goal is to develop synthesis pathways for 2D TMOs possessing large crystal domains (e.g., >10 μm), expanding the 2D TMO family and providing insights for future engineering of 2D TMOs. Here, we demonstrate the synthesis of WBG 2D nickel oxide (NiO) (E g > 2.7 eV) thermally converted from 2D nickel hydroxide (Ni(OH) 2 ) with a lateral domain size larger than 10 μm. Moreover, the conversion process is investigated using various microscopic techniques, such as atomic force microscopy, Raman spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy, providing significant insights into morphology and structural variations under different oxidative conditions. The electronic structure of the converted Ni x O y is further investigated using multiple soft X-ray spectroscopies, such as X-ray absorption and emission spectroscopies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Versatile Cell Design for Molten Fluoride Salt Spectroscopy: Investigating Metal-Ion Speciation in Molten Fluoride Salts

Fluoride-based molten salts are widely used in industrial applications including aluminum production, thermal energy storage, optical crystal growth, and advanced nuclear reactor designs. Despite the wide range of uses, fundamental understandings of coordination chemistry and methods for probing molten fluorides are scarce, likely due to the difficulty of probing fluoride melts with spectroscopic techniques. Performing spectroscopic measurements of fluoride-based salts is challenging due to the highly corrosive nature of these salts, which can degrade many common optical materials. Here, in this work, we present a versatile optical cell design that enables spectroscopic measurements of corrosive melts. This innovative cell design overcomes the challenges posed by the corrosive nature of the salts, allowing for an accurate and consistent spectroscopic analysis. This work reports temperature-dependent absorption measurements for Co 2+ , Ni 2+ , and Cr 3+ analytes in LiF-NaF-KF eutectic salt (i.e., FLiNaK), which are common corrosion products originating from structural alloys in molten-fluoride handling. Absorption spectra were used to understand interactions of these analytes with FLiNaK, particularly ligand field coordination. The analysis of absorption spectra was complemented by structural analyses using ab initio molecular dynamics (AIMD) simulations, providing deeper insights into the behavior of the analytes in FLiNaK. Our findings indicate that the analytes studied in this work exist in octahedral or near-octahedral coordination states that remain stable across the temperature range of 500–600 °C. This work not only highlights an applied solution to performing optical spectroscopy in corrosive, high-temperature melts but also provides important fundamental insight on coordination behavior of transition-metal species in molten fluorides.

Fluoride salt spectroscopy↗

d -Electron Heavy Fermion Behavior in a Near-Room-Temperature Polar Metallic Ferrimagnet: A Case of Mn 5 SiC

Polycrystalline Mn 5 SiC was synthesized by using a high-temperature solid-state method. Mn 5 SiC adopts a polar space group (Cmc2 1 ) with six crystallographic Mn sites confirmed by X-ray and neutron diffraction, transmission electron microscopy, and second harmonic generation experiments. The complex crystal structure features edge-sharing trigonal prisms and icosahedra, as well as face/edge-sharing pentagonal prisms. Magnetic measurements indicate ferrimagnetic ordering with a transition temperature of 284 K. The ferrimagnetic structure (magnetic space group Cm’c’2 1 ) was further identified by powder neutron diffraction, where collinear Mn spins align along the crystallographic c-axis. The refined magnetic moment for each crystallographic Mn site at 4 K is 1.8(2), −2.42(9), −1.72(8), 0.51(6), 0.50(4), and 1.7(2) μ B . Density functional theory calculations confirm both the metallic behavior and the ferrimagnetic structure observed experimentally and further provide insight into the observed Mn moment dependence across crystallographic sites. The resistivity and specific heat measurements and density functional theory calculations reveal a substantially large Kadowaki–Woods ratio of 5 × 10 –5 μΩ·cm/(mJ/mol) 2 and a many-body renormalization factor of 5.5, indicating the unusual heavy Fermion behavior in such an itinerant magnetic metal.

Messegee, Zachary T. [George Mason University, Fai↗

Embedding Reverse Electron Transfer Between Stably Bare Cu Nanoparticles and Cation‐Vacancy CuWO 4

Cu nanoparticles (NPs) have attracted widespread attention in electronics, energy, and catalysis. However, conventionally synthesized Cu NPs face some challenges such as surface passivation and agglomeration in applications, which impairs their functionalities in the physicochemical properties. Here, the issues above by engineering an embedded interface of stably bare Cu NPs on the cation-vacancy CuWO 4 support is addressed, which induces the strong metal-support interactions and reverse electron transfer. Various atomic-scale analyses directly demonstrate the unique electronic structure of the embedded Cu NPs with negative charge and anion oxygen protective layer, which mitigates the typical degradation pathways such as oxidation in ambient air, high-temperature agglomeration, and CO poisoning adsorption. Kinetics and in situ spectroscopic studies unveil that the embedded electron-enriched Cu NPs follow the typical Eley-Rideal mechanism in CO oxidation, contrasting the Langmuir-Hinshelwood mechanism on the traditional Cu NPs. This mechanistic shift is driven by the Coulombic repulsion in anion oxygen layer, enabling its direct reaction with gaseous CO to form the easily desorbed monodentate carbonate.

Cu nanoparticles↗

Alternate InP synthesis with aminophosphines: solution–liquid–solid nanowire growth

Indium phosphide nanowires are important components in high-speed electronics and optoelectronics, including photodetectors and photovoltaics. However, most syntheses either use high-temperature and costly vapor-phase methodology or highly toxic and pyrophoric tris(trimethylsilyl)phosphine. To expand on the success of the aminophosphine-based InP colloidal quantum dot synthesis, we developed a synthesis for thin (~11 nm) zinc blende InP nanowires at 180 °C using indium tris(trifluoroacetate) and tris(diethylamino)phosphine. A flat nanoribbon morphology was identified by transmission electron and atomic force microscopy analysis, with the stoichiometric (110) lattice plane exposed. Nanowire growth proceeded through a solution–liquid–solid mechanism from in situ-formed indium metal nanoparticles. Molecular byproducts of tris(oleylamino)phosphine oxide and N-oleyltrifluoroacetamide observed by 31 P and 19 F NMR spectroscopy inform a proposed mechanism of indium reduction by the aminophosphine. Morphological control over the nanowire product was achieved by varying the phosphorus injection to control the aspect ratio, the In : P ratio to toggle between nanowires and multipods, and the pre-hot injection evacuation step to favor a quantum dot product. Furthermore, replacing the indium precursor with indium tris(trifluoromethanesulfonate) was found to make bulk zinc blende InP nanowires with an average diameter of >250 nm and tens of microns in length.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Two-component exciton condensates in an electron–hole bilayer

Macroscopic quantum coherence emerges when bosons condense into a Bose–Einstein condensate (BEC). Excitons are a long-sought solid-state route to high-temperature BECs with strong interactions, electrical tunability and potentially multicomponent spinor order, but conclusive evidence for equilibrium condensation has remained elusive. Here we report evidence for two-component exciton BECs in MoSe 2 /hBN/WSe 2 electron–hole bilayers by probing the spin–valley susceptibility of constituent electrons and holes. This heterostructure hosts equilibrium exciton fluids with four spin–valley flavours. Magneto-optical spectroscopy in a dilution refrigerator reveals three exciton condensate phases with distinct flavour polarizations. At zero magnetic field, the many-body ground state is a coherent superposition of two condensed intravalley exciton flavours. Under a magnetic field, the intravalley exciton condensate first switches to a two-component intervalley condensate through a first-order quantum phase transition at a weak critical field and then turns into a fully polarized single-component condensate at high fields. The condensate signatures form a dome in density–temperature space, persisting up to approximately 1.8 K. Our results establish van der Waals electron–hole bilayers as a versatile platform for strongly interacting, multicomponent exciton BECs.

Qi, Ruishi [University of California, Berkeley, CA↗

Room-temperature valley-selective emission in Si-MoSe 2 heterostructures enabled by high-quality-factor chiroptical cavities

Transition metal dichalcogenides possess valley pseudospin, enabling coupling between photon spin and electron spin for classical and quantum information processing. However, rapid valley-dephasing processes have impeded the development of scalable, high-performance valleytronic devices operating at room temperature. Here we demonstrate that a chiral resonant metasurface can enable room-temperature valley-selective emission in MoSe 2 monolayers independent of excitation polarization. This platform provides circular eigen-polarization states with a high quality factor (Q-factor) and strong chiral near-field enhancement. The fabricated Si chiral metasurfaces exhibit chiroptical resonances with Q-factors up to 450 at visible wavelengths. We reveal degrees of circular polarization (DOP) reaching a record high of 0.5 at room temperature. Our measurements show that the high DOP can be attributed to the significantly increased chiroptical local density of states, which enhances valley-specific radiative transition rates by a factor of ~13. Our work could facilitate the development of ultracompact chiral classical and quantum light sources.

42 ENGINEERING↗

RePED 250: Manufacturing and Market Analysis of High-Temperature Alternators

The novel repetitive pulsed electric drill 250 (RePED 250) has the potential to greatly lower the costs and drilling times of geothermal projects. This tool discharges electric pulses through hard rock formations, shattering the rock in tension and allowing it to be quickly removed. One hurdle in bringing this technology to market is the RePED 250 downhole alternator. This component is essential for supplying power to the electronic drilling tool. There are currently no downhole tools on the market that meet the RePED 250 alternator's high temperature and power requirements. This report focuses on the path to commercialization for this novel alternator technology being developed as part of the RePED 250 project. One aim of this work is to identify the geothermal market size for the RePED 250 alternator, as well as other potential markets for this technology outside of geothermal. The geothermal market is very small, with only approximately 13 wells drilled in the United States each year. The worldwide market is several times this size and growing each year. The ability of the RePED 250 technology to drastically reduce the cost of geothermal projects may also lead to an increase in this market size. Technology developed for the high-temperature, high-power RePED 250 alternator can also be used to create high-temperature and high-power motors. These motors and alternators will have potential applications in oil and gas drilling, a $300 billion dollar industry in the United States alone, as well as in more distant industries such as aircraft, weapon systems, space exploration, and electric vehicles. Other aspects of the RePED 250 alternator's path to commercialization are also analyzed, including the supply chain for production materials and potential manufacturing methods. The supply chain and manufacturing practices for low-temperature motors and alternators are well established and require relatively minor changes for the high-temperature and high-power RePED 250 alternator. Sourcing for high-temperature materials has been identified, as well as potential supply chain risks. These most notably include electrical steel and high-temperature samarium cobalt (SmCo) magnets. Overall, these risks are not expected to be significant at the likely manufacturing scale required for the RePED 250.

15 GEOTHERMAL ENERGY↗

Heliostat sizing methodology for concentrating solar thermal industrial process heat projects

This study presents a method to obtain a heliostat size that minimizes the levelized cost of heat (LCOH) of a heliostat-based concentrating solar thermal system for applications of solar heating for industrial processes at operating temperatures from 565 to 1550°C. The method extends prior work by embedding a routine for system design that obtains near-optimal subsystem sizes, increasing the fidelity of drive cost functions, and adding an optical performance model to supplement the previously developed cost models, which we update to reflect current pricing trends. An illustrative business case is developed for Daggett, California, targeting specified annual thermal energy outputs of 50 to 400 GWh th . Optical performance is modeled using verified estimates from the literature. A surrogate heliostat cost model, derived from commercial heliostat designs and scaled for production volume, installation, and operations and maintenance costs, is used to develop cost functions. Results show that heliostat size strongly affects the LCOH, producing a characteristic U-shaped trend with a robust near-optimal window of 7-20 m 2 ; the heliostat size producing the lowest project cost in our study grows slightly as the project size increases, and is reduced as the operating temperature increases. The findings in this study are consistent with the general trend of smaller heliostats being deployed at existing projects for high-temperature industrial process heat and reflect the significant reduction in power electronics and other per-heliostat costs. The methodology we propose is general and can be tailored to revised cost curves as the technology continues to evolve.

14 SOLAR ENERGY↗