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Thin Film Synthesis of SrZn2P2 with SrI2 Post-Annealing for Enhanced Crystallinity and Optoelectronic Quality

Ternary Zintl phosphides are promising light-absorbing semiconductors for thin-film optoelectronic applications, but strategies for controlling their microstructure and optoelectronic quality remain underexplored. Here, we report the synthesis of phase-pure SrZn2P2 thin films using radio-frequency co-sputtering in a PH3 + Ar atmosphere and investigate the impact of post-growth processing on their structural and optical properties. Grazing-incidence X-ray scattering and Raman spectroscopy confirm the formation of crystalline SrZn2P2 films over a finite compositional window. Optical measurements reveal clear absorption near the direct-band-gap energy (~1.8 eV) and near-band-edge photoluminescence. Further, we have studied the effects of chemically compatible halide-assisted annealing. It is found that SrI2 treatments lead to pronounced grain growth and reduced diffraction peak broadening while preserving phase purity, in contrast to rapid thermal or forming-gas annealing. Notably, annealing with SrI2 at 450 degrees C significantly enhances both the intensity and spatial uniformity of the photoluminescence, thus connecting the observed microstructural consolidation with improved radiative recombination. Our study demonstrates that halide-assisted annealing provides an effective pathway for microstructural control in SrZn2P2 thin films and highlights a generalizable processing strategy for advancing Zintl phosphide semiconductors toward optoelectronic applications.

14 SOLAR ENERGY

Global Model Estimates of Atmospheric Al, Ca, Fe, Si, and Ti from Dust and Non-Dust Aerosols Informed by EMIT Surface Mineralogy and Evaluated Against Observations

Atmospheric deposition of micro-nutrients like Fe has been shown to be important for ocean biogeochemistry. The largest source of atmospheric Fe and other elements (e.g., Ca, Al, Si, and Ti) is desert dust, although there are significant non-dust sources in some regions. However, past estimates of these elements have been substantially uncertain due to limited information about the composition of the desert source regions. Here we use elemental distributions estimated from new Earth Surface Mineral Dust Source Investigation (EMIT) observations, which provide mineralogical composition at the surface of the Earth based on imaging spectroscopy measurements from the International Space Station. We add in other sources of these elements (anthropogenic and natural) and compare to a compilation of available surface concentration data from stations over land and from shipborne observations. Our results suggest that the modeled distribution is similar to available observations, but discrepancies still exist in both natural desert dust regions as well as regions dominated by anthropogenic sources. Global budgets for the elements Ca, Al, Fe, Si, and Ti suggest that desert dust remains the dominant source for these elements but anthropogenic or volcanic sources are also important for these elements. Changes in elemental distributions since preindustrial times were also estimated.

aerosols

Photovoltage behaviour of p-Sb 2 S 3 photocathodes for hydrogen evolution: effect of n-In 2 S 3 passivation layers

The 1.76 eV band gap of antimony(iii) sulphide (Sb 2 S 3 ) makes this semiconductor material a promising light absorber for photoelectrochemical water splitting, but scalable fabrication approaches to efficient devices are still lacking. Here we show that compact Sb 2 S 3 films on FTO can be obtained by electrochemical growth from aqueous colloidal sulphur and antimony trichloride solutions, followed by mild annealing. These films can be converted into hydrogen evolution photocathodes after coating with In 2 S 3 passivation layers and the addition of Pt proton reduction co-catalysts. For the first time, vibrating Kelvin probe surface photovoltage (VKP-SPV) spectroscopy is used to observe the carrier dynamics in such photoelectrodes. While the bare Sb 2 S 3 films suffer from high surface recombination rates and poor electron extraction, the In 2 S 3 overlayer is found to raise the photovoltage and cathodic photocurrent density, due to passivation of surface defects and formation of a p–n heterojunction. In thick In 2 S 3 films, these benefits are offset by shading and slow electron transfer. Also, we find that O 2 strongly affects the band bending in the Sb 2 S 3 –air and In 2 S 3 –air junctions and their photovoltage. The optimised devices evolve H 2 at 77.5% Faradaic efficiency and with 0.084% applied bias photon-to-current efficiency (ABPE) at 0.12 V vs. RHE. The low ABPE value is attributed to Sb 2 S 3 sub-bandgap defects visible in SPV spectra, the random orientation of Sb 2 S 3 crystallites in the films, which inhibits charge transport, the absence of crystal facets of Sb 2 S 3 , and a detrimental Schottky junction at the FTO|Sb 2 S 3 interface.

de Araújo, Moisés A. [University of California, Da

Restoration of weak localization in bilayer graphene by a molecular thin film

Quantum coherent effects can be probed in multilayer graphene through electronic transport measurements at low temperatures. In particular, bilayer graphene (BLG) is known to be susceptible to quantum interference corrections of the conductivity, presenting weak localization at all electronic densities, and dependent on different scattering mechanisms such as those related to the trigonal warping of the electron dispersion near the K and K′ valleys. Proximity effects with a molecular thin film influence these scattering mechanisms, which can be quantified through the known theory of magnetoconductance for BLG. Here, we present electronic transport measurements in a copper-phthalocyanine (CuPc) / BLG / hexagonal boron nitride (h-BN) heterostructure that suggest the restoration of weak localization in BLG, associated to a reduction of trigonal warping effects, that are known to suppress weak localization in BLG. Additionally, we observe a charge transfer of 3.6×10 12 cm −2 from the BLG to the molecules, as well as a very small degradation of the mobility of the BLG/h-BN heterostructure upon the deposition of CuPc. The molecular arrangement of the CuPc thin film is characterized in a control sample through transmission electron microscopy, that we relate to the electronic transport results.

bilayer graphene

Oxidation Chemistry of Bicarbonate and Peroxybicarbonate: Implications for Carbonate Management in Energy Storage

Carbonate formation presents a major challenge to energy storage applications based on low-temperature CO 2 electrolysis and recyclable metal–air batteries. While direct electrochemical oxidation of (bi)carbonate represents a straightforward route for carbonate management, knowledge of the feasibility and mechanisms of direct oxidation is presently lacking. Herein, we report the isolation and characterization of the bis(triphenylphosphine)iminium salts of bicarbonate and peroxybicarbonate, thus enabling the examination of their oxidation chemistry. Infrared spectroelectrochemistry combined with time-resolved infrared spectroscopy reveals that the photoinduced oxidation of HCO 3 – by an Ir(III) photoreagent results in the generation of the short-lived bicarbonate radical in less than 50 ns. The highly acidic bicarbonate radical undergoes proton transfer with HCO 3 – to furnish the carbonate radical anion and H 2 CO 3 , leading to the eventual release of CO 2 and H 2 O, thus accounting for the appearance of H 2 O and CO 2 in both electrochemical and photochemical oxidation experiments. Here, the back reaction of the carbonate radical subsequently oxidizes the Ir(II) photoreagent, leading to carbonate. In the absence of this back reaction, dimerization of the carbonate radical provides entry into peroxybicarbonate, which we show undergoes facile oxidation to O 2 and CO 2 . Together, the results reported identify tangible pathways for the design of catalysts for the management of carbonate in energy storage applications.

25 ENERGY STORAGE

Multiple Peaks and a Long Precursor in the Type IIn Supernova 2021qqp: An Energetic Explosion in a Complex Circumstellar Environment

Abstract We present optical photometry and spectroscopy of the Type IIn supernova (SN) 2021qqp. Its unusual light curve is marked by a long precursor for ≈300 days, a rapid increase in brightness for ≈60 days, and then a sharp increase of ≈1.6 mag in only a few days to a first peak ofM r ≈ −19.5 mag. The light curve then declines rapidly until it rebrightens to a second distinct peak ofM r ≈ −17.3 mag centered at ≈335 days after the first peak. The spectra are dominated by Balmer lines with a complex morphology, including a narrow component with a width of ≈1300 km s −1 (first peak) and ≈2500 km s −1 (second peak) that we associate with the circumstellar medium (CSM) and a P Cygni component with an absorption velocity of ≈8500 km s −1 (first peak) and ≈5600 km s −1 (second peak) that we associate with the SN–CSM interaction shell. Using the luminosity and velocity evolution, we construct a flexible analytical model, finding two significant mass-loss episodes with peak mass loss rates of ≈10 and ≈5M ⊙ yr −1 about 0.8 and 2 yr before explosion, respectively, with a total CSM mass of ≈2–4M ⊙ . We show that the most recent mass-loss episode could explain the precursor for the year preceding the explosion. The SN ejecta mass is constrained to be ≈5–30M ⊙ for an explosion energy of ≈(3–10) × 10 51 erg. We discuss eruptive massive stars (luminous blue variable, pulsational pair instability) and an extreme stellar merger with a compact object as possible progenitor channels.

Astronomy & Astrophysics

Scientific Highlights and Status of the Mars Science Laboratory Mission, Years 9 through 12

We present the scientific highlights and status from years 9-12 of NASA’s Mars Science Laboratory mission, with its Curiosity rover. A thermochemolysis-based sample analysis revealed a variety of organic molecules preserved in clay mineral-rich lake/lake margin deposits of the Glen Torridon region. The stratigraphically higher clay-sulfate mineral transition on Aeolis Mons was found to be associated with a lithological change from lacustrine to dry aeolian depositional environments. Water intermittently returned to the surface after the increase in aridity, including during the deposition of wave ripple strata which indicate a climate capable of sustaining an ice-free lake in the early Hesperian. The overlying Mg sulfate-bearing unit has both poly- and monohydrated Mg sulfates and is also enriched in iron carbonate of a purity consistent with chemical sedimentation and therefore atmospheric sequestration. A channel-incised canyon within Gediz Vallis and distal alluvial deposits recorded numerous fluvial and debris flow events after the deposition, lithification, and erosion of the clay- and sulfate-bearing units. Bright clasts found in Gediz Vallis canyon are composed of native sulfur. The investigation of the modern atmosphere and environment focused on the influence of the crater and mountain topography and captured high-altitude noctilucent and iridescent clouds. Radiation monitoring now spans an 11-year solar cycle. Rover systems and science instruments remain capable of addressing mission scientific objectives. All ten scientific instruments continue to return high-value data despite degradation of the Chemistry and Camera instrument’s high-voltage system, loss of multispectral imaging capability, and loss of active neutron spectroscopy. The mission has mitigated the loss of redundant brakes on two arm joints, additional wheel wear, and highly reduced capability of the redundant flight computer. Efficiency improvements in rover energy utilization and operations staffing have allowed the mission team to maintain a high level of productivity despite declining rover power generation and funding.

Mars

Phonon-mediated ultrafast dynamics in self-assembled monolayers of 4-mercaptobenzoic acid on gold

Non-equilibrium interactions between plasmonic metals and adsorbed molecules lie at the heart of emerging applications such as plasmonic photocatalysis and sensing, though the ultrafast charge and energy transfer mechanisms arising from these interactions are not well understood. Herein, we investigate the ultrafast dynamics of Au nano-islands tethered with a self-assembled monolayer (SAM) of electron-withdrawing 4-mercaptobenzoic acid (4MBA) molecules. Ultrafast UV-visible transient absorption spectroscopy following excitation of the interband transition in Au reveals three well-known, characteristic time constants that quantify electron–electron (el–el), electron–phonon (el–ph) and phonon–phonon (ph–ph) scattering lifetimes. When comparing the dynamics of bare Au and 4MBA-Au, we find that the el–ph and ph–ph scattering lifetimes are notably longer in 4MBA-Au. Density functional perturbation theory calculations ascribe the elongation in el–ph lifetimes in 4MBA-Au to the significant coupling of acoustic phonon modes of Au with certain molecular vibrations of 4MBA, leading to decreased spatial overlap between carrier electronic states and the acoustic modes. We speculate that the elongation of ph–ph scattering lifetimes in 4MBA-Au arises due to poor thermal conductivity of the SAM which disrupts efficient energy dissipation from Au to the environment, thus slowing down the thermalization of phonons. This work provides a glimpse into how molecular adsorbates modify the charge carrier and phonon dynamics of Au and sets the stage for further systematic exploration of plasmonic metal–molecule interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Semi-Transparent Perovskite Solar Cells in a Stacked Tandem Module: Cooperative Research and Development Final Report, CRADA Number CRD-19-00810

This project seeks to develop device design, materials composition, and processing tools and parameters to fabricate semi-transparent perovskite solar cells and modules for application in stand-alone products or added to other solar cells in a mechanically stacked tandem configuration. This technology presents significant advanced manufacturing challenges and opportunities in getting to scale, including development of perovskite inks, scalable perovskite and heterojunction deposition and annealing processes, heterojunction composition, transparent electrode composition and deposition process, anti-reflection layer composition and deposition process, and cell to module integration processes. Modification 5: The proposed project seeks to develop device design, materials composition, and processing tools and parameters to fabricate semi-transparent perovskite solar cells and modules for application in stand-alone products or added to other solar cells in a mechanically-stacked tandem configuration. This technology presents significant advanced manufacturing challenges and opportunities in getting to scale, including development of perovskite inks, scalable perovskite and heterojunction deposition and annealing processes, heterojunction composition, transparent electrode composition and deposition process, passivation layers including in module scribes, anti-reflection layer composition and deposition process, and cell to module integration processes. Advanced metrology and characterization will be performed on perovskite films, cells and module. Furthermore, we will examine module or materials recycling for circular economy considerations. Modifcation 6: Gigahertz frequency microwave pump-probe spectroscopies are highly sensitive to thin film semiconductor photoconductivity of individual and stacks of layers that comprise perovskite solar cells. As such, these techniques will be used to qualify reproducibility and quality correlations during the manufacturing process. Modification 7: Mechanical adhesion of top contacts within perovskite modules significantly impacts the durability of the module when exposed to accelerated degradation testing. The adhesion between the perovskite/transport layer interface and the transport layer/top contact interface are both very sensitive small changes in processing. ALD processing conditions of the transport layer will be tuned to optimize the mechanical adhesion within the perovskite module stack.

14 SOLAR ENERGY

Scattering theory of frequency-entangled biphoton states facilitated by cavity polaritons

The use of quantum light to probe exciton properties in semiconductor and molecular nanostructures typically occurs in the low-intensity regime. A substantial enhancement of exciton-photon coupling can be achieved with photonic cavities, where excitons hybridize with cavity modes to form polariton states. Here, to provide a theoretical framework for interpreting emerging experimental efforts in this direction, we develop a scattering theory describing the interaction of frequency-entangled photon pairs with cavity polariton and bipolariton states under various coupling regimes. Employing the Tavis-Cummings model in combination with our scattering approach, we present a quantitative analysis of how the interaction of the entangled photon pair with the polariton or bipolariton modifies its joint spectral amplitude (JSA). Specifically, we examine the effects of the cavity-mode steady-state population, exciton-cavity coupling strength, and different forms of the input photon JSA. Our results show that the entanglement entropy of the scattered photons is highly sensitive to the interplay between the input JSA and the spectral line shapes of the polariton resonances, emphasizing the cavity filtering effects. We suggest that biphoton-scattering quantum light spectroscopy best serves as a sensitive probe of polariton and bipolariton states in the photon-vacuum cavity state. Our approach is not only robust to various regimes of cavity-exciton coupling, but also amenable to extensions beyond the Tavis-Cummings model, enabling the representation of a broad class of molecular systems and solid state quantum materials.

36 MATERIALS SCIENCE

ARCTRON: A Rapid Experimental Proving Ground for TPS Experiments and Arcjet Technology Development

Innovation in high-enthalpy facilities is fundamentally limited by the cost and risk of experimentation. New concepts for plasma control, diagnostics, facility components, and plasma-material interaction often require repeated iterations that are impractical to perform in production arcjets. As a result, promising ideas may remain unexplored or reach operational facilities only after significant development effort. ARCTRON is being developed as a rapid experimental proving ground where new ideas in plasma science, arcjet engineering, diagnostics, and material response can be conceived, tested, and quantitatively evaluated before transition to large-scale facilities. The platform combines radio-frequency (RF) and DC arc plasma generation, externally applied magnetic fields, configurable gas composition, reduced-pressure operation, laser heating, electrical biasing, and modular diagnostic access. These capabilities permit the plasma source, applied forcing, test article, and measurement configuration to be modified independently, allowing individual physical mechanisms to be isolated more readily than in a traditional test environment. One class of investigations addresses fundamental plasma-surface interaction physics. Conventional material tests often expose a specimen simultaneously to convective heating, reactive species, pressure, shear, radiation, and surface-current effects. The resulting material response may be measured accurately, while the contribution of each mechanism remains difficult to identify. ARCTRON is designed to vary these effects selectively. Plasma chemistry can be changed independently through configurable gas mixtures; magnetic fields and electrical biasing can modify charged-particle transport; laser heating can provide a non-plasma thermal input; and pressure, flow, and discharge mode can be varied over a broad operating space. This enables controlled tests of hypotheses involving surface catalycity, reactive-species transport, plasma-assisted oxidation, electromagnetic effects, shear, and the relative contributions of thermal and chemical loading. A second class of investigations enabled by this approach concerns the engineering of high-enthalpy facilities themselves. Arc-heated facilities are limited by electrode erosion, unstable arc attachment, localized heating, and damage to nozzles and other plasma-facing components. ARCTRON provides a lower-cost environment for testing concepts intended to mitigate these limitations. Candidate investigations include the use of applied magnetic fields to alter current paths and reduce plasma interaction with nozzle walls, ExB forcing to introduce controlled plasma rotation, magnetic or geometric approaches for distributing arc attachment, and alternative electrode or discharge configurations intended to reduce erosion and improve stability. Because the platform is reconfigurable, these concepts can be evaluated through repeated design--build--test cycles before they are considered for implementation in operational facilities. The platform also supports the development and validation of diagnostics that may be difficult to introduce initially into a large arcjet. Current and planned measurements include spatially resolved optical emission spectroscopy, electrostatic probes, fast imaging, pyrometry, calorimetry, laser-induced fluorescence, and absorption spectroscopy. These diagnostics are intended not merely to document a nominal operating condition, but to constrain the local plasma state and its relationship to component or material response. The modular facility geometry allows diagnostic concepts to be tested, calibrated, and compared under repeatable conditions before deployment in more demanding environments. ARCTRON is also supported by an integrated software suite. Automated control and data acquisition allow discharge parameters, gas composition, magnetic fields, diagnostic timing, and test configuration to be recorded as part of each experiment (STARDAC - Software for Testing, Analysis, Research Data, and Control). The Backend for Experiment Analysis, Storage, and Traceability (BEAST) is a database that provides the infrastructure needed to associate heterogeneous measurements with facility configuration, specimen identity, calibration state, geometry, and analysis provenance. This backend is particularly important for exploratory campaigns, in which many related configurations may be tested, and the value of an individual experiment depends on its connection to earlier and subsequent iterations. Complementary analysis capabilities, including computer-vision-based transient response measurements (arcjetCV), three-dimensional surface reconstruction (STARSCAN), and model-based Bayesian inference (SHIELD), and tomography data analysis (TOMATO, PuMA) can be incorporated when required by a specific hypothesis without becoming the focus of every campaign. The central objective of ARCTRON is therefore not to maximize heat flux or reproduce a complete flight environment. Its purpose is to reduce the cost and time required to ask consequential questions about plasma behavior, plasma-facing materials, diagnostics, and arcjet technology. By providing a controlled environment for rapid reconfiguration, mechanism isolation, quantitative measurement, and iterative engineering, ARCTRON can help mature concepts that would otherwise remain too speculative or too risky for evaluation in production facilities. The resulting knowledge can then guide the design of material models, focus test objectives in larger arcjets, reduce facility-development risk, and improve the physical basis of high-enthalpy ground testing. This work will present the ARCTRON architecture, operating modes, diagnostic suite, and digital experimental workflow. Initial experimental results from the first integrated operation of the facility will be presented, including flow characterization, power limitations, and deployment of the initial diagnostic suite. Ongoing development efforts aimed at catalycity characterization, magnetic plasma control, and advanced optical diagnostics will also be discussed, illustrating how the platform supports rapid iteration from concept to experiment.

experimental diagnostics

ARCTRON: A Rapid Experimental Proving Ground for TPS Experiments and Arcjet Technology Development

Innovation in high-enthalpy facilities is fundamentally limited by the cost and risk of experimentation. New concepts for plasma control, diagnostics, facility components, and plasma-material interaction often require repeated iterations that are impractical to perform in production arcjets. As a result, promising ideas may remain unexplored or reach operational facilities only after significant development effort. ARCTRON is being developed as a rapid experimental proving ground where new ideas in plasma science, arcjet engineering, diagnostics, and material response can be conceived, tested, and quantitatively evaluated before transition to large-scale facilities. The platform combines radio-frequency (RF) and DC arc plasma generation, externally applied magnetic fields, configurable gas composition, reduced-pressure operation, laser heating, electrical biasing, and modular diagnostic access. These capabilities permit the plasma source, applied forcing, test article, and measurement configuration to be modified independently, allowing individual physical mechanisms to be isolated more readily than in a traditional test environment. One class of investigations addresses fundamental plasma-surface interaction physics. Conventional material tests often expose a specimen simultaneously to convective heating, reactive species, pressure, shear, radiation, and surface-current effects. The resulting material response may be measured accurately, while the contribution of each mechanism remains difficult to identify. ARCTRON is designed to vary these effects selectively. Plasma chemistry can be changed independently through configurable gas mixtures; magnetic fields and electrical biasing can modify charged-particle transport; laser heating can provide a non-plasma thermal input; and pressure, flow, and discharge mode can be varied over a broad operating space. This enables controlled tests of hypotheses involving surface catalycity, reactive-species transport, plasma-assisted oxidation, electromagnetic effects, shear, and the relative contributions of thermal and chemical loading. A second class of investigations enabled by this approach concerns the engineering of high-enthalpy facilities themselves. Arc-heated facilities are limited by electrode erosion, unstable arc attachment, localized heating, and damage to nozzles and other plasma-facing components. ARCTRON provides a lower-cost environment for testing concepts intended to mitigate these limitations. Candidate investigations include the use of applied magnetic fields to alter current paths and reduce plasma interaction with nozzle walls, ExB forcing to introduce controlled plasma rotation, magnetic or geometric approaches for distributing arc attachment, and alternative electrode or discharge configurations intended to reduce erosion and improve stability. Because the platform is reconfigurable, these concepts can be evaluated through repeated design--build--test cycles before they are considered for implementation in operational facilities. The platform also supports the development and validation of diagnostics that may be difficult to introduce initially into a large arcjet. Current and planned measurements include spatially resolved optical emission spectroscopy, electrostatic probes, fast imaging, pyrometry, calorimetry, laser-induced fluorescence, and absorption spectroscopy. These diagnostics are intended not merely to document a nominal operating condition, but to constrain the local plasma state and its relationship to component or material response. The modular facility geometry allows diagnostic concepts to be tested, calibrated, and compared under repeatable conditions before deployment in more demanding environments. ARCTRON is also supported by an integrated software suite. Automated control and data acquisition allow discharge parameters, gas composition, magnetic fields, diagnostic timing, and test configuration to be recorded as part of each experiment (STARDAC - Software for Testing, Analysis, Research Data, and Control). The Backend for Experiment Analysis, Storage, and Traceability (BEAST) is a database that provides the infrastructure needed to associate heterogeneous measurements with facility configuration, specimen identity, calibration state, geometry, and analysis provenance. This backend is particularly important for exploratory campaigns, in which many related configurations may be tested, and the value of an individual experiment depends on its connection to earlier and subsequent iterations. Complementary analysis capabilities, including computer-vision-based transient response measurements (arcjetCV), three-dimensional surface reconstruction (STARSCAN), and model-based Bayesian inference (SHIELD), and tomography data analysis (TOMATO, PuMA) can be incorporated when required by a specific hypothesis without becoming the focus of every campaign. The central objective of ARCTRON is therefore not to maximize heat flux or reproduce a complete flight environment. Its purpose is to reduce the cost and time required to ask consequential questions about plasma behavior, plasma-facing materials, diagnostics, and arcjet technology. By providing a controlled environment for rapid reconfiguration, mechanism isolation, quantitative measurement, and iterative engineering, ARCTRON can help mature concepts that would otherwise remain too speculative or too risky for evaluation in production facilities. The resulting knowledge can then guide the design of material models, focus test objectives in larger arcjets, reduce facility-development risk, and improve the physical basis of high-enthalpy ground testing. This work will present the ARCTRON architecture, operating modes, diagnostic suite, and digital experimental workflow. Initial experimental results from the first integrated operation of the facility will be presented, including flow characterization, power limitations, and deployment of the initial diagnostic suite. Ongoing development efforts aimed at catalycity characterization, magnetic plasma control, and advanced optical diagnostics will also be discussed, illustrating how the platform supports rapid iteration from concept to experiment.

experimental diagnostics

Emergence of low-energy spin waves in superconducting electron-doped cuprates

In order to fully utilize the technological potential of unconventional superconductors, an enhanced understanding of the superconducting mechanism is necessary. In the best performing superconductors, the cuprates, superconductivity is intimately linked with magnetism, although the details of this coupling remain elusive. Here, we address this gap by studying the electron-doped cuprate Nd 1.85 Ce 0.15 CuO 4−δ that has an antiferromagnetic ground state when synthesized and only becomes superconducting after a reductive annealing process. Using neutron spectroscopy, we show that the as-grown crystal exhibits a large spin pseudogap in the magnetic fluctuation spectrum. Annealing removes defects introduced by the commonly employed synthesis method and significantly reduces the spin pseudogap. While the spin pseudogap in the annealed sample likely arises from superconductivity, in the as-grown sample it results from the absence of long-wavelength spin waves. These results reveal a direct connection between defects, magnetism, and superconductivity, offering new insight into the mechanisms underlying high-temperature superconductivity and guiding the design of improved superconducting materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND

Kondo effect in ferromagnetic quantum critical CeRh 6 ⁢Ge 4

The mechanism of a pressure-induced quantum critical point in the heavy fermion ferromagnet CeRh 6 ⁢Ge 4 has attracted interest, as ferromagnetic quantum criticality in a clean itinerant Ce compound is typically avoided. The localized versus itinerant character of the 4⁢𝑓 electrons is a key aspect for understanding this behavior. We investigated the electronic structure of the 4⁢𝑓 shell in CeRh 6 ⁢Ge 4 using core-level photoelectron and x-ray absorption spectroscopy, demonstrating the hybridization of Ce 4⁢𝑓 with the conduction electrons. Linearly polarized x-ray absorption reveals a temperature-dependent linear dichroism consistent with the crystal-electric-field sequence as inferred from the static susceptibility. This dichroism cannot be described by an ionic full-multiplet model alone, but is reproduced by including the Kondo effect within a single-impurity Anderson model in the noncrossing approximation. The Kondo effect mixes higher-lying crystal-field states into a resulting multiorbital ground state with 4⁢𝑓 occupancy, 𝑛 𝑓 ∼ 0.9. Deviations at low temperatures between the measured linear dichroism and calculated dichroism suggest an orbital-dependent Kondo effect. A scenario in which there is a multiorbital ground state and orbital-dependent Kondo hybridization should be a starting point for a model of pressure-induced criticality in CeRh 6 ⁢Ge 4 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND

Cr plasma-material-interaction in PISCES-RF: D thermal release, retention, and erosion

Pure chromium (Cr) targets were exposed to high-flux deuterium (D) plasmas in the Pisces-RF linear plasma device, and measurements of D retention, release, and erosion were subsequently performed. Post-exposure D retention was quantified using temperature-programmed desorption on Cr targets irradiated by 50 eV ions over a broad range of exposure temperatures (423–873 K) and ion fluences (3 × 10 24 – 3 × 10 26 m −2 ). The retained D inventory was observed to decrease rapidly with increased exposure temperature, from approximately ∼7 × 10 20 m −2 at ∼ 420 K, to then saturate near ∼ 10 20 m −2 for exposure temperatures above ∼550 K. Separately, at fixed exposure temperature (∼450 K), D retention was found to have only a weak dependence on increasing ion fluence. Lastly, the erosion of Cr in D plasma was investigated for ion impact energies in the range 40 ≤ E i ≤ 250 eV. Erosion was inferred using optical emission spectroscopy (OES) from the ratio of emission lines (Cr I (425.4 nm)/D I (656.1 nm)) measured close to the target. Conversion of the OES yield data to net erosion yield was made with singular ion energy target mass-loss measurements. These net erosion yield data were then further corrected to obtain gross erosion yield by accounting for a re-deposition factor, computed using a simple model. The gross erosion yield is found to be 2–4 times lower than predicted by SDTrimSP, consistent with that typically observed for light-ion sputtering under high-flux plasma conditions.

Chromium

Gas-mediated defect engineering in earth-abundant Mn-rich layered oxides for non-aqueous sodium-based batteries

Gases are often by-products of battery materials during cell formation and degradation, affecting the cycle life and safety of rechargeable batteries. However, understanding gas-mediated (electro)-chemical reactions and nanoscale structural transformations during the synthesis of battery electrode materials remains challenging because of the lack of suitable characterization routes and the complexity of the interplay between thermodynamics and kinetics. Here, in this study, we use operando synchrotron X-ray diffraction, in situ transmission X-ray microscopy and multiscale modelling to elucidate the reaction pathways and microstructural defect development of earth-abundant Mn-rich layered oxides as positive electrode materials for sodium-based batteries. In particular, we demonstrate the dominant role of CO 2 over O 2 and H 2 O (g) in modulating the competition between entropy and enthalpy during solid-state synthesis. Using Ni 0.25 Mn 0.75 CO 3 as a model precursor, we reveal that CO 2 generation favours the formation of entropy-driven metastable intermediates, suppresses closed pore/nanovoids formation and decreases chemical heterogeneity and residual lattice strain of Mn-rich layered oxides during the synthesis. This result motivates a fast-sintering strategy to promote CO 2 release, which ultimately leads to improved chemo-mechanical and electrochemical stability of the Mn-rich positive electrodes when tested in non-aqueous Na metal coin cells.

36 MATERIALS SCIENCE

Ion Transport and Crystal Rotation in Plastic Crystal Electrolytes Under Applied Electric Fields

Organic ionic plastic crystal electrolytes, containing a plastic crystal and lithium salt, offer a potential balance between mechanical and electrochemical properties for solid state lithium-ion battery electrolytes. These electrolytes contain multiple mobile ionic species (three or four), resulting in complex transport mechanisms which have not yet been established. Plastic crystals are defined by long-range positional order and short-range rotational disorder. It is therefore necessary to quantify changes in the local crystal structure of the electrolyte as current flows through it. Herein, we examine the electrochemical properties of pyrrolidinium-based plastic crystal electrolytes containing lithium salt and zwitterion additives, including measurements of current fraction and limiting current. We obtain species-specific insight into electrolyte transport using pulsed-field gradient nuclear magnetic resonance spectroscopy and find that, while the zwitterion additive increases ionic conductivity, it decreases lithium diffusivity with respect to other ionic components. With operando spatiotemporally resolved wide-angle X-ray scattering we observe location-specific crystal rotations due to the passage of ionic current. In conclusion, we posit that reducing energy dissipation due to rotation is essential for using plastic crystal electrolytes in practical applications.

Yap, Kyra M. K. [University of California, Berkele

Physical Parameters of Space Mission Asteroid Targets

Ground-based characterization of asteroids that are planned or potential targets of space missions provides important data on their physical parameters and properties. Knowledge of the properties of mission targets is important especially during mission preparation and planning, as it serves to select best or suitable targets for specific purpose of a given mission, to prepare mission plans, to constrain possible mission scenarios, and to design mission experiments. Such characterization efforts may be particularly critical for flyby missions that take only limited data during the high-speed flybys of their target asteroids, but they also provide very crucial data for targets of rendezvous missions. Moreover, long-term observations taken from Earth also allows the modelling of, or constraining, processes acting on the asteroids over extended time scales. Over the past years and decades we have obtained rich data on physical parameters of 82 asteroids that are planned or potential targets of space missions. Our primary observing technique is time-resolved (lightcurve) photometry, but we use also data obtained with other techniques, such as spectroscopy, thermal or radar observations. 15 of the 82 characterized asteroids are planned or possible targets of several space missions that are in flight or preparation, such as ESA’s Hera, RAMSES and PRIAMOS, NASA’s OSIRIS-APEX, JAXA’s Hayabusa2#, DESTINY+ and Next Generation Sample Return (NGSR), the Emirates Mission to Asteroids (EMA), and Karman+’s High Frontier, but we have also characterized 67 asteroids that are potential targets of space missions for their low delta-V’s and were announced as being “of interest to NASA” in the Small-Bodies-Observations- NASA mailing list or listed on the NHATS page of “Accessible NEAs”. The sample of asteroid targets span 3 orders of magnitude in size, with absolute magnitudes H from 12.57 to 26.8, corresponding to diameters from about 10 m to about 10 km. The sample contains a variety of taxonomic types and physically or dynamically interesting objects. Among them, we have identified 5 binary asteroids and 20 tumblers (i.e., asteroids in excited, non-principal axis rotation states). Rotation periods of the characterized asteroids range from 1.45 min to 280 h, reflecting diversity of their properties and formation/evolution paths. We will present an overview of the data set and highlight several representative cases.

Petr Pravec