A pyridinic Fe-N[subscript 4] macrocycle models the active sites in Fe/N-doped carbon electrocatalysts
Abstract not provided
Marshall-Roth, Travis↗
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Magnon damping and mode softening in quantum double-exchange ferromagnets
We present a comprehensive analysis of the magnetic excitations and electronic properties of fully quantum double-exchange ferromagnets, i.e. systems where ferromagnetic (FM) ordering emerges from the competition between spin, charge, and orbital degrees of freedom, but without the canonical approximation of using classical localized spins. Specifically, we investigate spin excitations within the Kondo lattice-like model, as well as a two-orbital Hubbard Hamiltonian in proximity to the orbital-selective Mott phase. Computational analysis of the magnon dispersion, damping, and spectral weight within these models reveals unexpected phenomena, such as magnon mode softening and the anomalous decoherence of magnetic excitations as observed in earlier experimental efforts, but explained here without the use of the phononic degrees of freedom. We show that these effects are intrinsically linked to incoherent spectral features near the Fermi level, which arise due to the quantum nature of the local (on-site) triplets. This incoherent spectrum leads to a Stoner-like continuum on which spin excitations scatter, governing magnon lifetime and strongly influencing the dynamical spin structure factor. Our study explores the transition from coherent to incoherent magnon spectra by varying the electron density. Furthermore, we demonstrate that the magnitude of the localized spin mitigates decoherence by suppressing the incoherent spectral contributions near the Fermi level. We also discuss the effective J 1 –J 2 spin Hamiltonian, which can accurately describe the large doping region characterized by the magnon-mode softening. Finally, we show that this behavior is also present in multiorbital models with partially filled orbitals, namely, in systems without localized spin moments, provided that the model is in a strong coupling regime. Our results potentially have far-reaching implications for understanding FM ordering in various multi-band systems. These findings establish a previously unknown direct connection between the electronic correlations of those materials and spin excitations.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Highly crystalline MoS{sub 2} thin films grown by pulsed laser deposition
Highly crystalline thin films of MoS{sub 2} were prepared over large area by pulsed laser deposition down to a single monolayer on Al{sub 2}O{sub 3} (0001), GaN (0001), and SiC-6H (0001) substrates. X-ray diffraction and selected area electron diffraction studies show that the films are quasi-epitaxial with good out-of-plane texture. In addition, the thin films were observed to be highly crystalline with rocking curve full width half maxima of 0.01°, smooth with a RMS roughness of 0.27 nm, and uniform in thickness based on Raman spectroscopy. From transport measurements, the as-grown films were found to be p-type.
36 MATERIALS SCIENCE↗
Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets
This paper reports the fabrication and electrochemical performance of a hybrid catalyst composed of Pd nanoparticles and atomically dispersed Mn active centers integrated into the nitrogen-doped three-dimensional graphene nanosheets (Pd/Mn-N-3D-GNS). Our results show that the synergistic integration of both Pd nanoparticles and atomically dispersed Mn can be used to enhance the activity toward the electrochemical oxidation of organic acids at biologically relevant pH values. The hybrid catalyst (Pd/Mn-N-3D-GNS) showed increased maximum currents toward the oxidation of oxalic acid when compared to its individual catalysts, namely, Pd/3D-GNS and Mn N-3D-GNS catalysts. The hybrid also showed a decreased onset potential for oxidation of mesoxalic acid as compared to Mn-N-3D-GNS and decreased onset potentials for the oxidation of glyoxalic acid when compared to both of its constituent catalysts. Oxidation of formic acid was also tested and the hybrid was shown to catalyze both dehydration and dehydrogenation mechanisms of formic acid electro-oxidation. Using density functional theory calculations, it was elucidated that a two-site catalysis most likely promotes dehydrogenation reaction for formic acid oxidation, which can explain the selectivity of Pd nanoparticles and atomically dispersed Mn towards the dehydrogenation/ dehydration pathway.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Spin and orbital metallic magnetism in rhombohedral trilayer graphene
We provide a theoretical interpretation of the metallic broken spin-valley (flavor) symmetry states recently discovered in hole-doped rhombohedral trilayer (ABC) graphene in large electric displacement fields. Our conclusions about the phase diagram and phase transitions combine insights from ABC graphene electronic structure models and mean-field theory, and are guided by the precise magneto-oscillation Fermi-surface-area measurements of recent experiments. We find that the principle of momentum-space condensation plays a key role in determining Fermi-surface reconstructions enabled by broken flavor symmetries when the single-particle bands imply thin annular Fermi seas. The reconstructed Fermi sea consists of one large outer Fermi-surface-enclosed majority-flavor states in reciprocal-space area A maj and one or more small inner holelike Fermi-surface-enclosed minority-flavor states in A min that are primarily responsible for nematic order. The competing ground states (valley-Ising, valley-XY, and spin-polarized state) have different A maj /A min and exchange energy maximizes this ratio and selects valley-XY nematic metal as the lowest-energy state. Here, we discuss how the nematic pockets explain the observed fractionalization of quantum oscillation frequencies, and propose anisotropic transport and the nonlinear Hall effect as additional observables.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Final Report: Vapor Transport Deposition for Thin Film III-V Photovoltaics
Silicon, the dominant photovoltaic (PV) technology, is reaching its fundamental performance limits as a single absorber/junction technology. Higher efficiency devices are needed to reduce cost further because the balance of systems account for about two-thirds of the overall cost of the solar electricity. III-V semiconductors such as GaAs are used to make the highest-efficiency photovoltaic devices, but the costs of manufacture are much too high for non-concentrated terrestrial applications. The cost of III-V’s is driven by two factors: (1) metal-organic chemical vapor deposition (MOCVD), the dominant growth technology, employs expensive, toxic and pyrophoric gas-phase precursors, and (2) the growth substrates conventionally required for high-performance devices are monocrystalline III-V wafers. The primary goal of this project was to show that close-spaced vapor transport (CSVT), using water vapor as a transport agent, is a scalable deposition technology for growing low-cost epitaxial III-V photovoltaic devices. The secondary goal was to integrate those devices on Si substrates for high-efficiency tandem applications using interface nanopatterning to address the lattice mismatch. In the first task, we developed a CSVT process that used only safe solid-source powder precursors to grow epitaxial GaAs with controlled n and p doping and mobilities/lifetimes similar to that obtainable via MOCVD. Using photoelectrochemical characterization, we showed that the best material had near unity internal quantum efficiency for carrier collection and minority carrier diffusions lengths in of ~ 8 μm, suitable for PV devices with >25% efficiency. In the second task we developed the first pn junction photovoltaics using CSVT and showed unpassivated structures with open circuit photovoltages > 915 mV and internal quantum efficiencies >0.9. We also characterized morphological and electrical defects and identified routes to reduce those defects. In task three we grew epitaxial ternary GaAsxP 1-x and In 0.5 Ga 0.5 P alloys, with composition set by the ratio of GaAs/GaP or InP/GaP mixed as the source powder. GaAs 0.3 P 0.7 has the appropriate bandgap to serve as a top cell on Si and In 0.5 Ga 0.5 P is near the composition used as a surface passivation layer on GaAs pn junction photovoltaics. In the final task we demonstrated III-V selective area epitaxy using CSVT as a first step toward the growth of III-V micro- or nanostructures for an integrated tandem solar cell on Si. We also found that direct epitaxial growth on Si appears to be impossible in the current H 2 O-CSVT reactor design, likely due to the formation of SiO x . This work sets the stage for targeted development of an improved CSVT process and for the scale up of the proof-of-concept work from a research to manufacturing-relevant platform. Replacing H 2 O as a transport agent with HCl would provide the ability to deposit directly on Si by avoiding oxide formation and to allow for the deposition of Al-containing alloys that would otherwise oxidize. Improved engineering design and implementation of an in-line multi-station CSVT would allow for direct deposition of device structures in a single system.
14 SOLAR ENERGY↗
Facile and Scalable Synthesis of Metal- and Nitrogen-Doped Carbon Nanotubes for Efficient Electrochemical CO 2 Reduction
Metal- and nitrogen-doped carbon (M–N–C) is a promising material to catalyze electrochemical CO 2 reduction reaction (CO 2 RR). However, most M–N–C catalysts in the literature require complicated synthesis procedures and produce small quantities per batch, limiting the commercialization potential. In this work, we developed a simple and scalable synthesis method to convert metal-impurity-containing commercial carbon nanotubes (CNTs) and nitrogen-containing organic precursors into M–N–C via one-step moderate-temperature (650 °C) pyrolysis without any other treatment nor the need to add metal precursors. Batches of catalysts in varied mass up to 10 g (150 mL in volume) per batch were synthesized, and repeatable catalytic performances were demonstrated. To the best of our knowledge, the 10 g batch is one of the largest batches of CO2RR catalysts synthesized in the literature while requiring minimal synthesis steps. The catalyst possessed single-atomic iron–nitrogen (Fe–N) sites, enabling a high performance of >95% CO product selectivity at a high current density of 400 mA/cm 2 and high stability for 45 h at 100 mA/cm 2 in a flow cell testing. The catalyst outperformed a benchmark noble-metal nanoparticle catalyst and achieved longer stability than many other reported M–N–C catalysts in the literature. The scalable and cost-effective synthesis developed in this work paves a pathway toward practical CO 2 RR applications. The direct utilization of metal impurities from raw CNTs for efficient catalyst synthesis with minimal treatment is a green and sustainable engineering approach.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A Survey of Transparent Conducting Films and Optoelectrical Materials for High Optical Power Applications
The lifetime laser damage performance of a wide range of transparent conductive materials is assessed, including ultrathin metal films, doped metal oxides, doped compound semiconductors, and graphene whose carrier densities span five orders of magnitude from 10 18 to 10 23 cm -3 . Lifetime laser damage thresholds are determined by exposing material surfaces to repeated nanosecond laser pulses at near IR wavelengths (1064 nm). Near threshold fluences, two distinct damage modes, i.e., bulk and discrete, emerge depending on carrier density. These bulk and discrete damage modes are attributed to free carrier-induced bulk and localized, defect-driven absorption processes, respectively. For polycrystalline films with free carrier densities greater than ≈10 20 cm -3 , laser damage thresholds are less than 5 J cm -2 . In contrast, bulk absorption is not apparent at thresholds substantially higher than ≈10 J cm-2 in single-crystal films with free carrier concentrations lower than ≈10 19 cm -3 . By increasing thickness, films with lower carrier densities can deliver relevant levels of sheet conductance (<200 Ω sq -1 ) while remaining transparent. These lifetime laser damage threshold measurements offer systematic criteria to select materials aimed at handling high optical powers in optoelectronics devices and emerging plasmonic and metamaterials for lasers.
36 MATERIALS SCIENCE↗
Understanding and Controlling Conductivity Transitions in Correlated Solids: Spectroscopic Studies of Electronic Structure in Vanadates (Final Report)
This research project is focused on synchrotron radiation based x-ray spectroscopic studies of the metal to insulator transition in vanadium oxides. In doing so, we developed a fundamental understanding of the origins of conductivity transitions in correlated electron materials. Conductivity transitions can be driven by external and internal mechanisms, including electric and magnetic fields, chemical doping, defects, disorder, pressure, dimensionality, and temperature. Vanadium oxides, and vanadium dioxide in particular, display particularly complex electronic phenomena. Binary vanadium oxides, and ternary oxides with substituted metal cations, exhibit a broad range of complex conductivity transitions, as well as charge ordering transitions, structural phase transitions, frustrated spin structures, superconductivity, and unusual magnetic properties. As such, vanadates are a prototypical class of correlated material, where fundamentally important physical themes can be explored, both experimentally and theoretically. The experimental tools used were soft x-ray emission spectroscopy (XES), soft x-ray absorption spectroscopy (XAS), resonant inelastic soft x ray scattering (RIXS), x-ray photoemission spectroscopy (XPS), angle resolved photoemission spectroscopy (ARPES), and spectroscopic photoemission low energy electron microscopy (SPELEEM). This broad range of techniques delivered data that was used to understand the electronic structure in these oxides. Vanadium oxides as single crystals, thin films, polycrystalline powders, and nanoparticles were studied to determine the influence of the physical structure the materials properties. A rich and varied selection of experiments were performed, and by combining the information gathered by our x-ray spectroscopic techniques, we developed a comprehensive understanding of electronic structure in vanadium oxides. We measured band structures and Fermi surfaces, studied the coupling between collective excitations and quasi-particles, measured the local, site and element specific electronic structure, as well as the cation charge state, measured orbital hybridization, and measured element specific low energy valence excitations such as dd* and charge transfer excitations.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Growing Aligned Carbon Nanotubes for Interconnections in ICs
A process for growing multiwalled carbon nanotubes anchored at specified locations and aligned along specified directions has been invented. Typically, one would grow a number of the nanotubes oriented perpendicularly to a silicon integrated-circuit (IC) substrate, starting from (and anchored on) patterned catalytic spots on the substrate. Such arrays of perpendicular carbon nanotubes could be used as electrical interconnections between levels of multilevel ICs. The process (see Figure 1) begins with the formation of a layer, a few hundred nanometers thick, of a compatible electrically insulating material (e.g., SiO(x) or Si(y)N(z) on the silicon substrate. A patterned film of a suitable electrical conductor (Al, Mo, Cr, Ti, Ta, Pt, Ir, or doped Si), having a thickness between 1 nm and 2 m, is deposited on the insulating layer to form the IC conductor pattern. Next, a catalytic material (usually, Ni, Fe, or Co) is deposited to a thickness between 1 and 30 nm on the spots from which it is desired to grow carbon nanotubes. The carbon nanotubes are grown by plasma-enhanced chemical vapor deposition (PECVD). Unlike the matted and tangled carbon nanotubes grown by thermal CVD, the carbon nanotubes grown by PECVD are perpendicular and freestanding because an electric field perpendicular to the substrate is used in PECVD. Next, the free space between the carbon nanotubes is filled with SiO2 by means of CVD from tetraethylorthosilicate (TEOS), thereby forming an array of carbon nanotubes embedded in SiO2. Chemical mechanical polishing (CMP) is then performed to remove excess SiO2 and form a flat-top surface in which the outer ends of the carbon nanotubes are exposed. Optionally, depending on the application, metal lines to connect selected ends of carbon nanotubes may be deposited on the top surface. The top part of Figure 2 is a scanning electron micrograph (SEM) of carbon nanotubes grown, as described above, on catalytic spots of about 100 nm diameter patterned by electron-beam lithography. These and other nanotubes were found to have lengths ranging from 2 to 10 m and diameters ranging from 30 to 200 nm, the exact values of length depending on growth times and conditions and the exact values of diameter depending on the diameters and thicknesses of the catalyst spots. The bottom part of Figure 2 is an SEM of an embedded array of carbon nanotubes after CMP.
Li, Jun↗
Effect of glutathione-coated Mn-doped ZnS quantum dots on nutrient delivery in basil ( Ocimum basilicum ) plants
Ensuring efficient nutrient delivery while minimizing environmental impacts remains a significant challenge for modern agriculture. Nanotechnology-based fertilizers offer promising strategies to improve nutrient uptake and bioavailability in plants. This research aims to evaluate the use of Glutathione-coated Manganese-doped Zinc Sulfide quantum dots (GSH-ZnS-Mn QDs) as a potential nano fertilizer for basil (Ocimum basilicum). QDs' physicochemical properties were characterized using UV–Vis spectroscopy, photoluminescence, FTIR, and energy-dispersive X-ray spectroscopy, confirming successful Mn doping and glutathione surface functionalization. Basil plants were exposed to different concentrations of GSH-ZnS-Mn QDs under soil and hydroponic conditions. Plant growth parameters, oxidative stress responses, photosynthetic pigments, and macro- and micronutrient uptake were assessed using biochemical assays and inductively coupled plasma optical emission spectrometry (ICP-OES). Elemental uptake, spatial distribution, and zinc speciation were further investigated using synchrotron-based micro-X-ray fluorescence (μ-XRF) imaging and X-ray absorption near-edge structure (XANES) spectroscopy. Results show that exposure to GSH-ZnS-Mn QDs resulted in a concentration-dependent increase in leaf and stem biomass, accompanied by enhanced Zn accumulation in plant tissues. Catalase activity decreased across all tested concentrations, suggesting a shift toward glutathione-dependent antioxidant pathways rather than oxidative damage. Chlorophyll levels exhibited moderate reductions at higher concentrations. The higher increase in macronutrient (K, Ca, and Mg) uptake was reported in plants exposed to 200 ppm of QDs. μ-XRF imaging indicated a selective accumulation of Zn in roots and stems, with partial translocation to leaves. XANES analyses revealed that Zn from QDs was mainly converted into organic Zn species, such as Zn-phytate, Zn-acetate, and Zn-cysteine, indicating transformation and complexation within the plant. The findings demonstrate that a glutathione coating on GSH-ZnS-Mn QDs improves biocompatibility and nutrient delivery efficiency. These results highlight the relevance of surface functionalization in regulating nanoparticle fate, transformation, and nutrient bioavailability, supporting the potential application of GSH–ZnS–Mn QDs as modern nano fertilizers.
Basil↗
Enhanced ferromagnetic order in Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} featuring canted [MnO{sub 4}]{sub ∞} spin chains of mixed-valent Mn(III)/Mn(IV). Aliovalent substitution of the Sr{sub 4−x}Ln{sub x}Mn{sup III}{sub 2+x}Mn{sup IV}{sub 1−x}O{sub 3}(GeO{sub 4}){sub 3} solid-solution
Crystals of Sr{sub 4−x}Ln{sub x}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} (x=0; x∼0.15 for Ln=La, Pr, Nd, Sm. Eu, Gd, Dy; x∼0.3 for Ln=Gd) were isolated upon using high-temperature, solid-state methods in molten-salt media. These compounds are isostructural with the previously reported Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} (Ln=La, Sm, Gd) series that contains the same [MnO{sub 4}]{sub ∞} spin chains. The synthesis of the Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} (x=0) phase was carried out by a double aliovalent substitution with respect to the Sr{sup 2+} and Ge{sup 4+} ions that replace Na{sup +}/Ln{sup 3+} and As{sup 5+} in Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}, respectively. The title series contains mixed-valent Mn(III)/Mn(IV) and shows a limited range of solid solution, both of which were not observed in the previously reported Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} series. To form the Sr{sub 4−x}Ln{sub x}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} solid solution, one of the Sr{sup 2+} sites, i.e., the original Ln-site in Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}, is partially substituted by Ln{sup 3+} in a statistical disorder of Sr{sub 1−x}/Ln{sub x}. Initial magnetic investigations of selected derivatives reveal higher ferromagnetic ordering temperatures than those reported for the Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3} series, presumably attributed to a lesser degree of canting as a result of introducing non-Jahn–Teller Mn{sup 4+} ions. Also intriguing is the observation of multiple anomalies at low temperatures which appear to be of electronic origins. - Graphical abstract: Sr{sub 4−x}Ln{sub x}Mn(III){sub 2+x}Mn(IV){sub 1−x}O{sub 3}(GeO{sub 4}){sub 3}. Display Omitted - Highlights: • Double aliovalent substitution: Sr{sub 4}Mn{sub 3}O{sub 3}(GeO{sub 4}){sub 3} with respect to Na{sub 3}LnMn{sub 3}O{sub 3}(AsO{sub 4}){sub 3}. • Solid solution with respect to statistical disorder of Sr{sub 1−x}Ln{sub x} in one of the two Sr sites. • Mn{sup 3+}/Mn{sup 4+} magnetic ions are spatially arranged in a triangular kagomé fashion. • Enhanced ferromagnetic ordering attributed to doping non-Jahn–Teller Mn{sup 4+}.
36 MATERIALS SCIENCE↗
Phase stabilization and oxidation of a continuous composition spread multi-principal element (AlFeNiTiVZr) 1-x Cr x alloy
Multi-Principal Element Alloys (MPEA) have been hypothesized to maintain a stable single alloy phase and resist corrosion at high temperatures, which are desirable in various functional applications, including material of turbine blades. However, studies into oxidation resistant alloys have been constrained to individual MPEA systems or a limited selection of compositions within those systems. Here, High-Throughput Experimental (HTE) techniques were utilized to rapidly assess phase stability and resistance to oxidation of an (AlFeNiTiVZr) 1-x Cr x continuous composition spread (CCS) thin-film alloy system. High-throughput synchrotron diffraction and Raman spectroscopy were used to identify phases, especially high symmetry structures and oxides, as a function of annealing time and composition. The formation of two distinct phase regions, R 1 and R 2 , across the CCS was observed. One of these phase regions, R 2 , exhibited a stable high symmetry BCC-like phase at Cr concentrations greater than 25.4 at%, and grew a passivating mixed metal surface oxide; whereas, the R 1 phase region, decomposed on oxidation to multiple oxides and reacted with the substrate to form silicides. The passivating mixed metal oxide layer appears to prevent destabilization of the (AlFeNiTiVZr) 1-x Cr x MPEA BCC solid solution. Furthermore, at longer annealing times the passivating phase was seen only above 29.2 at% Cr. High Cr-doped (AlFeNiTiVZr) 1-x Cr x appear to be a good candidate for high temperature, oxidation-resistant structural alloys.
36 MATERIALS SCIENCE↗
Fundamentals of SrCoO 3-δ Based Oxygen Deficient Perovskites as Cathodes for Solid Oxide Fuel Cells
The local structure and oxygen stoichiometry in oxide systems have a profound impact on oxygen electrocatalysis encountered in metal-air batteries and solid oxide fuel cells (SOFCs). However, this knowledge is often obtained under conditions different from the real working conditions of the material, resulting in misinterpretation and misunderstanding. This PhD dissertation aims to obtain the structure and oxygen-stoichiometry information of a class of perovskite oxides under their real working conditions in solid oxide fuel cells. Several perovskite oxides were selected for the study: Sr 0.9 Y 0.1 CoO 3-δ (SYC10), Sr 0.9 Y 0.3 CoO 3-δ (SYC30), SrCo 0.9 Nb 0.1 O 3-δ (SCN10) and SrCo 0.9 Ta0.1O 3-δ (SCT10). The local crystal structure and oxygen stoichiometry of these materials were systematically characterized with in-situ neutron diffraction (ND). The oxygen stoichiometry was also measured by thermogravimetric analysis (TGA) and iodometric titration methods. To establish the correlation among structure, oxygen stoichiometry and oxygen reduction reaction (ORR) activity, high temperature electrochemical impedance spectroscopy, oxygen permeation and single cell testing were also performed. In chapter 2, SYC10 is described to have a more symmetrical structure and $V_o^{··}$ distribution, and higher $V_o^{··}$ concentration than SYC30. Molecular orbital energy analysis based on the local structure of the ORR-active Co1-polyhedra indicates SYC30 has a higher Fermi level relative to O-2p energy level in the active Co1-polyhedra, and thus a higher motional enthalpy for $V_o^{··}$ migration. However, the ORR activity of Y-doped SrCoO 3-δ (SCO) are found uncompetitive with other popular catalysts. In chapter 3 and 4, systematic structural studies are presented for Nb and Ta-doped SCO, namely SCN10 and SCT10, respectively. The methodology of unrevealing the structure-activity relationships in chapter 2 is also found applicable to SYC10, SCN10 and SCT10 as presented in chapter 5. The electrochemical tests indicate that SCT10 is the best catalyst due to its excellent thermal and electrochemical stability. In chapter 6, SCT10 is evaluated in a real solid oxide fuel cell in the form of nanoscaled SCT10 layer coating on the commercial (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ (LSCF). The bilayer structured cathode shows excellent properties of coarsening-resistant, Sr-segregation-free and high ORR-activity.
Yang, Tianrang↗
Interrogating Proton Affinities of Organophosphonate Species Via Atmospheric Flow Tube Mass Spectrometry and Computational Methods
Within trace vapor analysis in environmental monitoring, defense, and industry, atmospheric flow tube mass spectrometry (AFT-MS) can fill a role that incorporates non-contact vapor analysis with the selectivity and low detection limits of mass spectrometry. AFT-MS has been applied to quantitating certain explosives by selective clustering with nitrate and more recently applied to detecting tributyl phosphate and dimethyl methylphosphonate as protonated species. Developing AFT-MS methods for organophosphorus species is appealing, given that this class of compounds includes a range of pollutants, chemical warfare agent (CWA) simulants, and CWA degradation products. A key aspect of targeting organophosphorus analytes has included the use of dopant ion chemistry to form adducts that impart additional analytical selectivity. The assessment of potential dopant molecules suited to enhance detection of these compounds is hindered by few published ion thermochemical properties for organophosphorus species, such as proton affinity, which can be used for approximating proton-bound dimer bond strength. As a preliminary investigation for the progression of sensing methods involving AFT-MS, we have applied both the extended kinetic method and computational approaches to eight organophosphorus CWA simulants to determine their respective gas-phase proton affinities. Notable observed trends, supported by computational efforts, include an increase in proton affinity as the alkyl chain lengths on the phosphonates increased. .
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
The Readout Electronics of the Mu2e Electromagnetic Calorimeter
The Mu2e electromagnetic calorimeter has been designed to measure ~100 MeV electrons with energy resolution σE/E <10%, time resolution σt < 500ps and position resolution σx < 1cm. The detector is composed of 1348 un-doped CsI crystals coupled to two large area Silicon Photomultipliers (SiPMs). Each SiPM is connected to a Front End Electronics (FEE) chip which hosts the shaping amplifier and the high voltage linear regulator. A group of 20 FEE is controlled by one Mezzanine Board (MB) which transmits the amplified signals to one Digitizer ReAdout Controller board (DiRAC). The DiRAC samples the waveforms at 200 MHz with 12-bit ADCs, packs the data according to the Mu2e custom format and transmits them to the event builder through an optical transceiver. To limit the number of pass-through connectors and the length of the cables, the readout and digitization electronics is located inside the detector cryostat and close to the interaction target. The boards will have to sustain a neutron fluence of about 5x10 10 n/cm 2 @ 1 MeVeq (Si)/y and a Total Ionizing Dose of about 12 krad, while working into a 1T magnetic field and a vacuum of 10 (-4) Torr. This harsh operational environment has made the electronics design challenging and required an extended campaign of tests to select and qualify the employed electronic components. In this paper we report on the board architecture and design, on the qualification of the prototypes, as well as on the results of the first vertical slice test of the Mu2e calorimeter.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Selective Isolation of Surface Grain Boundaries by Oxide Dielectrics Improves Cd(Se,Te) Device Performance
Cd(Se,Te) photovoltaics (PV) are the most widely deployed thin-film solar technology globally, yet continued efficiency improvements are stymied by challenges at the device hole contacts. The inclusion of solution-processed oxide layers such as AlGaO x in the contact stack has yielded improved device open-circuit voltages (V OC ) and fill factors (FF). However, contradictory mechanisms by which these layers improve the device properties have been proposed by the research community. We demonstrate in this work that an underappreciated property of such spin-coated layers is the preferential deposition at grain boundaries, a process that isolates the grain boundaries during contact metallization. The effects of grain-boundary isolation are probed by varying the coverage of solution-processed AlGaO x “barrier” layers on the Cd(Se,Te) surface, quantified by scanning Auger microscopy. Examining coverage-dependent V OC and FF, it was observed that isolating the grain boundaries during metallization is sufficient to prevent damage to the absorber that occurs in devices lacking a barrier layer, while additional coverage contributes to the increased series resistance. Such an effect is agnostic to the material used as a barrier layer, as long as the material does not itself damage the absorber. Spin-coated SiO x was used in place of AlGaO x for an equally beneficial effect. This grain-boundary isolation phenomenon is also observed during Mo deposition and in absorbers that have been contacted with a nitrogen-doped ZnTe layer. The mechanisms by which metallization may degrade the absorber are discussed, as are contact design strategies leveraging barrier layers, which may lead to improved device efficiencies.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Technetium and Iodine Getters to Improve Cast Stone Performance
To determine the effectiveness of the various getter materials prior to their solidification in Cast Stone, a series of batch sorption experiments was performed at Pacific Northwest National Laboratory. To quantify the effectiveness of the removal of Tc(VII) and I(I) from solution by getters, the distribution coefficient, Kd (mL/g), was calculated. Testing involved placing getter material in contact with spiked waste solutions at a 1:100 solid-to-solution ratio for periods up to 45 days with periodic solution sampling. One Tc getter was also tested at a 1:10 solid-to-solution ratio. Two different solution media, 18.2 MΩ deionized water (DI H2O) and a 7.8 M Na LAW simulant, were used in the batch sorption tests. Each test was conducted at room temperature in an anoxic chamber containing N2 with a small amount of H2 (0.7%) to maintain anoxic conditions. Each getter-solution combination was run in duplicate. Three Tc- and I-doping concentrations were used separately in aliquots of both the 18.2 MΩ DI H2O and a 7.8 M Na LAW waste simulant. The 1× concentration was developed based on Hanford Tank Waste Operations Simulator (HTWOS) model runs to support the River Protection Project System Plan Revision 6. The other two concentrations were 5× and 10× of the HTWOS values. The Tc and I tests were run separately (i.e., the solutions did not contain both solutes). Sampling of the solid-solution mixtures occurred nominally after 0.2, 1, 3, 6, 9, 12, 15 days and ~35 to 45 days. Seven getter materials were tested for Tc and five materials were tested for I. The seven Tc getters were blast furnace slag 1 (BFS1) (northwest source), BFS2 (southeast source), Sn(II)-treated apatite, Sn(II) chloride, nano tin phosphate, KMS (a potassium-metal-sulfide), and tin hydroxapatite. The five iodine getters were layered bismuth hydroxide (LBH), argentite mineral, synthetic argentite, silver-treated carbon, and silver-treated zeolite. The Tc Kd values measured from experiments conducted using the 7.8 M Na LAW simulant (the simulant selected to represent LAW) for the first 15 days for four Tc getters (BFS1, BFS2, Sn(II)-treated apatite, and Sn(II) chloride) show no, to a very small, capacity to remove Tc from the LAW simulant. For the Tc-getter experiments in the 7.8 M LAW simulant, the majority of the effluent samples show very small drops in Tc concentrations for the 35-day compared to the 15-day samplings. However, the Tc concentration in the simulant blanks also dropped slightly during this period, so the effect of the getter contacting LAW simulant at 35 days compared to 15 days is minimal; except that the BFS1 1:10 test shows a slow but steady decrease in Tc concentration in the LAW simulant supernatant from the beginning to the 35 day contact at which point about 20% of the original Tc has been removed from solution. Lastly, the KMS getter gives the highest Kd value for Tc at 35 days where Kd values have increased to 104 mL/g. When considering the different I getters reacting with the 7.8 M LAW simulant, two getters are much more effective than the others: Ag zeolite and Syn Arg. The other getters have calculated iodide distribution coefficients that show very limited effectiveness in the caustic conditions created by the LAW simulant. These are preliminary results that will need more detailed analyses including both pre- and post-batch sorption getter solid-phase characterization using state-of-the-art instrumentation such as synchrotron X ray absorption spectroscopy, which can delineate the oxidation state of the Tc and likely iodine species as well as some of the getters key major components, sulfur and iron in the BFS, and tin and sulfur in the tin-bearing and sulfur-bearing getters. This report also describes future experimental studies to be performed to better elucidate the mechanisms controlling the Tc and I sequestration processes in the various getters and leach tests of getter-bearing Cast Stone monoliths.
Tc getters, I getters, Cast Stone, Waste Forms↗