Designing Perovskite Catalysts for Controlled Active Site Exsolution in the Microwave Dry Reforming of Methane
ACS Spring Meeting 2021, Virtual, April 5-16, 2021
Marin, Christopher↗
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MatLab Package for Whispering Gallery Mode Data
Dye-doped whispering gallery mode resonator (WGMR) microspheres yield highly structured emission spectra that are extremely sensitive to their environment and are of intense interest for use in a variety of sensing applications. Efforts to leverage the unique sensitivities of WGMRs have relied on stringent experimental requirements to correlate specific spectral shifts/changes to an analyte/stimulus such as 1) precise positional knowledge, 2) reference spectra for each microsphere, and 3) high mechanical stability. Consequently, these can hinder adequate mixing or incorporation of analytes and creates challenges for remote sensing. The MATLAB codes provided here are to be used in conjunction with a continuous flow technique for measuring WGM spectra of dye-doped microspheres suspended in solution. One MATLAB script, smooths the data, automatically baseline corrects it to isolate the whispering gallery modes (WGM) from the unwanted bulk emission, and assesses the similarity of each spectrum to aid in selecting a set of unique WGM spectra for further analysis. The next script is designed to analyze WGM spectra to determine the size of the resonator and the refractive index (RI) of its local environment without a priori knowledge of the individual microsphere. The final script allows the user to cluster spheres based on the product of their RI and radius and the contrast ratio of the RI of the sphere material and that of its environment by using a shared nearest neighbor spectral clustering algorithm.
Lilley, Laura↗
Method and apparatus for increasing resistance of bipolar buried layer integrated circuit devices to single-event upsets
Bipolar transistors fabricated in separate buried layers of an integrated circuit chip are electrically isolated with a built-in potential barrier established by doping the buried layer with a polarity opposite doping in the chip substrate. To increase the resistance of the bipolar transistors to single-event upsets due to ionized particle radiation, the substrate is biased relative to the buried layer with an external bias voltage selected to offset the built-in potential just enough (typically between about +0.1 to +0.2 volt) to prevent an accumulation of charge in the buried-layer-substrate junction.
Zoutendyk, John A.↗
Electrical and thermal transport properties of layered Bi{sub 2}YO{sub 4}Cu{sub 2}Se{sub 2}
Bi{sub 2}YO{sub 4}Cu{sub 2}Se{sub 2} possesses a low thermal conductivity and high electrical conductivity at room temperature, which was considered as a potential thermoelectric material. In this work, we have investigated the electrical and thermal transport properties of Bi{sub 2}YO{sub 4}Cu{sub 2}Se{sub 2} system in the temperature range from 300 K to 873 K. We found that the total thermal conductivity decreases from ~1.8 W m{sup −1} K{sup −1} to ~0.9 W m{sup −1} K{sup −1}, and the electrical conductivity decreases from ~850 S/cm to ~163 S/cm in the measured temperature range. To investigate how potential of Bi{sub 2}YO{sub 4}Cu{sub 2}Se{sub 2} system, we prepared the heavily Iodine doped samples to counter-dope intrinsically high carrier concentration and improve the electrical transport properties. Interestingly, the Seebeck coefficient could be enhanced to ~+80 μV/K at 873 K, meanwhile, we found that a low thermal conductivity of ~0.7 W m{sup −1} K{sup −1} could be achieved. The intrinsically low thermal conductivity in this system is related to the low elastic properties, such as Young's modulus of 70–72 GPa, and Grüneisen parameters of 1.55–1.71. The low thermal conductivity makes Bi{sub 2}YO{sub 4}Cu{sub 2}Se{sub 2} system to be a potential thermoelectric material, the ZT value ~0.06 at 873 K was obtained, a higher performance is expected by optimizing electrical transport properties through selecting suitable dopants, modifying band structures or by further reducing thermal conductivity through nanostructuring etc. - Highlights: • The total thermal conductivity decreases from 1.8 to 0.9 Wm{sup –1}K{sup –1} at 300–873K. • The electrical conductivity decreased from 850 to 163 S/cm at 300–873K. • The Seebeck coefficients were enhanced through heavily Iodine doping. • The ZT ~0.06 at 873K suggests that Bi{sub 2}YO{sub 4}Cu{sub 2}Se{sub 2} systems are potential thermoelectrical materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Er Al :Al 2 O 3 for telecom-band photonics: Electronic structure and optical properties
Er-doped Al 2 O 3 is a promising host for telecom-band integrated photonics. Here, in this study, we combine ab initio calculations with a symmetry-resolved analysis to elucidate substitutional Er on the Al site (Er Al ) in 𝛼−Al 2 O 3 . First-principles relaxations confirm the structural stability of Er Al . We then use the local trigonal crystal-field symmetry to classify the Er-derived impurity levels by irreducible representations and to derive polarization-resolved electric-dipole selection rules, explicitly identifying the symmetry-allowed 𝑓−𝑑 hybridization channels. Kubo-Greenwood absorption spectra computed from Kohn-Sham states quantitatively corroborate these symmetry predictions. Furthermore, we connect the calculated intra-4𝑓 line strengths to Judd-Ofelt theory, clarifying the role of 4𝑓−5𝑑 admixture in enabling optical activity. Notably, we predict a characteristic absorption near 1.47 µm (telecom band), relevant for on-chip amplification and emission. To our knowledge, a symmetry-resolved first-principles treatment of Er:Al 2 O 3 with an explicit Judd-Ofelt interpretation has not been reported, providing a transferable framework for tailoring rare-earth dopants in wide-band-gap oxides for integrated photonics. Our results for the optical spectra are in good agreement with experimental data. The resulting symmetry-based selection rules translate directly to polarization-dependent coupling in Al 2 O 3 integrated photonic waveguides and resonators, enabling device-level design of TE/TM-mode interaction with Er emitters in the 1.5-µm telecom band.
Er-doped Al2O3↗
Influence of seed layers on the vertical growth of ZnO nanowires by low-temperature wet chemical bath deposition on ITO-coated glass substrate
Aligned ZnO nanowires (NWs) were synthesized by low-temperature wet chemical bath deposition (CBD) technique on indium tin oxide (ITO)-coated glass substrates using c-axis orientated ZnO and AZO (Al-doped ZnO) seed layers through the RF sputtering deposition process under different conditions. The growth direction of ZnO NW was controlled by using the two different seed layers. Results showed single-crystalline structure of the ZnO NWs with the highest peak intensity in (002) crystalline direction. In addition, NWs seeding form AZO layer, grown on ITO coated glass, were vertically aligned and uniformly distributed on the substrate. The effects of precursor concentration, growth temperature, and seed layer on NW morphology were investigated in two different seed layers systematically. The intensity of broad emissions at 500–600 nm emission was observed in room temperature photoluminescence (PL) spectra for samples prepared under optimized parameters. In addition, the green emission intensity of ZnO NWs growth on the ZnO seed layer was much weaker than that of AZO seed layer. The experimental results indicate that the selection of seed layers, precursor concentration, and the growth temperature are key parameters to vertical growth of NWs for the application of nanoscale devices.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Morphological, structural and thermal studies of gallium nitride ferrite
We report the synthesis and Characterization of III-V doped Nano ferrite Ga{sub (2x+2)}N Fe{sub 2(49-x)}O{sub 3} for x=1 and x=5 by Sol-Gel method. The Morphological, structural and Thermal characterisation studies are done by using Transmission Electron Microscopy, Energy Dispersive X-ray Analysis, Selected Area Electron Diffraction, Thermo-Gravimetric Analysis and Differential Thermal Analysis. Using the Sci-Finder software we could not trace any reports related to GaNFe{sub 2}O{sub 3} in the literature. It has been observed from our studies that the particles are in the Cylindrical and the Globular structure. The particle diameter values from the Histograms are in good agreement with the XRD values that were communicated by us earlier. The SAED and the EDAX studies reveal the confirmation of the composition and also that the synthesized Ferrite exhibits crystalline nature. The TG-DTA results show that the compound indicates constant sample weight.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Oxygen Storage Properties of La 1– x Sr x FeO 3-δ for Chemical-Looping Reactions—An In Situ Neutron and Synchrotron X-ray Study
Oxygen storage materials (OSMs) provide lattice oxygen for a number of chemical-looping reactions including natural gas combustion and methane reforming. La 1–x Sr x FeO 3-δ has shown promise for use as an OSM in methane reforming reactions due to its high product selectivity, fast oxide diffusion, and cycle stability. Here, we investigate the structural evolution of the series La 1–x Sr x FeO 3-δ for x = 0, 1/3, 1/2, 2/3, and 1, using in situ synchrotron X-ray and neutron diffraction, as it is cycled under the conditions of a chemical-looping reactor (methane and oxygen atmospheres). In the compositions x = 1/3, 1/2, 2/3, and 1, we discover an envelope , or temperature range, of oxygen storage capacity (OSC), where oxygen can easily and reversibly be inserted and removed from the OSM. Our in situ X-ray and neutron diffraction results reveal that while samples with higher Sr contents had a higher OSC, those same samples suffered from slower reaction kinetics and some, such as the x = 1/2 and x = 2/3 compositions, had local variations in Sr content, which led to inhomogeneous regions with varying reaction rates. Therefore, we highlight the importance of in situ diffraction studies, and we propose that these measurements are required for the thorough evaluation of future candidate OSMs. Furthermore, we recommend La 2/3 Sr 1/3 FeO 3-δ as the optimal OSM in the series because its structure remains homogeneous throughout the reaction, and its OSC envelope is similar to that of the higher doped materials.
Taylor, Daniel D.↗
Small‐Band‐Gap Halide Double Perovskites
Abstract Despite their compositional versatility, most halide double perovskites feature large band gaps. Herein, we describe a strategy for achieving small band gaps in this family of materials. The new double perovskites Cs 2 AgTlX 6 (X=Cl ( 1 ) and Br ( 2 )) have direct band gaps of 2.0 and 0.95 eV, respectively, which are approximately 1 eV lower than those of analogous perovskites. To our knowledge, compound 2 displays the lowest band gap for any known halide perovskite. Unlike in A I B II X 3 perovskites, the band‐gap transition in A I 2 BB′X 6 double perovskites can show substantial metal‐to‐metal charge‐transfer character. This band‐edge orbital composition is used to achieve small band gaps through the selection of energetically aligned B‐ and B′‐site metal frontier orbitals. Calculations reveal a shallow, symmetry‐forbidden region at the band edges for 1 , which results in long (μs) microwave conductivity lifetimes. We further describe a facile self‐doping reaction in 2 through Br 2 loss at ambient conditions.
Slavney, Adam H.↗
Copper Tantalate by a Sodium-Driven Flux-Mediated Synthesis for Photoelectrochemical CO 2 Reduction
Copper-tantalate, Cu 2 Ta 4 O 11 (CTO), shows significant promise as an efficient photocathode for multi-carbon compounds (C 2+ ) production through photoelectrochemical (PEC) CO 2 reduction, owing to its suitable energy bands and catalytic surface. However, synthesizing CTO poses a significant challenge due to its metastable nature and thermal instability. In this study, this challenge is addressed by employing a flux-mediated synthesis technique using a sodium-based flux to create sodium-doped CTO (Na-CTO) thin films, providing enhanced nucleation and stabilization for the CTO phase. To evaluate the PEC performance and catalytic properties of the films, copper(II) oxide (CuO) at the Na-CTO surface is selectively etched. The etched Na-CTO shows a lower dark current, with decreased contribution from photocorrosion, unlike the non-etched Na-CTO which has remaining CuO on the surface. Furthermore, Na-CTO exhibits 7.3-fold ethylene selectivity over hydrogen, thus highlighting its promising potential as a photocathode for C 2+ production through PEC CO 2 reduction.
copper tantalate↗
The temperature and size distribution of large water clusters from a non-equilibrium model
A hybrid Lagrangian-Eulerian approach is used to examine the properties of water clusters formed in neon-water vapor mixtures expanding through microscale conical nozzles. Experimental size distributions were reliably determined by the sodium doping technique in a molecular beam machine. The comparison of computed size distributions and experimental data shows satisfactory agreement, especially for (H{sub 2}O){sub n} clusters with n larger than 50. Thus validated simulations provide size selected cluster temperature profiles in and outside the nozzle. This information is used for an in-depth analysis of the crystallization and water cluster aggregation dynamics of recently reported supersonic jet expansion experiments.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Intentional carbon doping reveals CH as an abundant charged impurity in nominally undoped synthetic WS 2 and WSe 2
Understanding the physical properties and controlling the generation of intrinsic and extrinsic defects is central to the technological adoption of 2D materials in devices. Here we identify a charged carbon-hydrogen complex at a chalcogen site (CH X ) as a common, charged impurity in synthetically grown transition metal dichalcogenides (TMDs). This conclusion is drawn by comparing high resolution scanning probe microscopy measurements of nominally undoped and intentionally carbon doped TMD samples. While CH impurity densities in undoped CVD-grown WS 2 and MOCVD-grown WSe 2 can range anywhere from parts per million to parts per thousand, CH densities in the percentage levels were selectively generated by a post-synthetic methane plasma treatment. Our study indicates that methane plasma treatment is a selective and clean method for the controlled introduction of a charged carbon-hydrogen complex at a surface chalcogen site, adefect that is commonly present in synthetic TMDs.
36 MATERIALS SCIENCE↗
Development and Properties of Advanced Internal Magnesium Infiltration (AIMI) Processed MgB2 Wires
The development, processing, properties, and formation mechanisms of Advanced Internal Magnesium Infiltration (AIMI) MgB2 wires are discussed against a background of the related and original processes, Internal-Magnesium-Diffusion (IMD) and Magnesium-Reactive-Liquid-Infiltration (Mg-RLI). First reviewed are the formation, properties and applications of Mg-RLI bulks as basis for discussions of Mg-RLI-processed and IMD-processed wires. The transition from Mg-RLI- and IMD- to AIMI wires is explained, and the relative performances of powder-in-tube (PIT), IMD and AIMI wires are summarized in the form of an iso-Je diagram of Jc,nb versus Anb/ATOT in which ATOT, Anb, Jc,nb, and Je are, respectively, the wire s cross-sectional area, the area inside the chemical barrier, the critical current (Ic) normalized to Anb, and Ic normalized to ATOT. After the details of AIMI wire fabrication selection of starting powders, dopants, and reaction heat treatments are introduced the report goes on to describe in detail the development of high performance AIMI wires: layer Jcs, fill factors, Jes, and the effects of wire size, multifilamentarization, doping with C, and co-doping with C and Dy2O3. The two-stage mechanism of layer formation in AIMI wires is discussed: first the reactive infiltration of liquid Mg into a porous B pack, a process that terminates with the formation of a dense MgB2 layer; second the slow diffusion of Mg into any remaining B through that MgB2 layer. The report concludes with a brief general discussion of anisotropy, current percolation, and the Jc field dependence of MgB2 wires.
Collings, Prof Edward William↗
Ultrawide-bandgap semiconductors: An overview
Ultrawide-bandgap (UWBG) semiconductor technology is presently going through a renaissance exemplified by advances in material-level understanding, extensions of known concepts to new materials, novel device concepts, and new applications. as such, this focus issue presents a timely selection of papers spanning the current state of the art in UWBG materials and applications, including both experimental results and theoretical developments. It covers broad research subtopics on UWBG bulk crystals and substrate technologies, UWBG defect science and doping, UWBG epitaxy, UWBG electronic and optoelectronic properties, and UWBG power devices and emitters. In this overview article, we consolidate the fundamentals and background of key UWBG semiconductors including aluminum gallium nitride alloys (Al x Ga 1– x N), boron nitride (BN), diamond, β-phase gallium oxide (β-Ga 2 O 3 ), and a number of other UWBG binary and ternary oxides.
36 MATERIALS SCIENCE↗
Quantum Transport in 2D Semiconductors
Leveraging progress in synthesis of ultra-pure transition metal dichalcogenide (TMD) crystals, our team has made key breakthroughs in the study of quantum states in two-dimensional (2D) TMD semiconductors. Using a capacitance spectroscopy technique, we have observed the first signatures of fractional quantum Hall states in monolayer WSe 2 and clear signatures of interlayer exciton condensates in bilayer WSe 2 . In a transport study of bilayer WSe 2 , we report observation of spin-selective magneto-conductivity in WSe 2 . To improve electrical transport studies, we have focused on metal-TMD contacts by studying the behavior of metal-TMD contacts in the clean limit, and developing a new contact doping technique that achieves Ohmic contact down to low temperature and low carrier density. Using this new technique, we study electrical transport in monolayer WSe 2 down to low temperature and low carrier density, finding record-high hole mobility and evidence of a metal-insulator transition at low density. Under high magnetic fields, we observe clear signatures of fractional quantum Hall effect in transport for the first time in a TMD.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
GaN Core-shell Nanofin Vertical Transistor (CoNVerT): A New Direction for Power Electronics (Final Scientific/Technical Report)
A novel power transistor architecture, the GaN c ore-shell n anofin ver tical transistor (CoNVerT) to address fundamental challenges in realizing the ultimate limit of GaN power transistor performance was explored experimentally. This technology promises ultra-high-efficiency high voltage/high power applications (e.g. DC/DC converters, motor control, fast charging, actuation), as well as to operate in harsh environments. The device exploits a vertical superjunction structure based on an experimentally-validated core-shell nanofin growth process in which lateral p-n heterojunctions are formed in a single growth step, while still maintaining vertical current flow for compact die size and low cost. The concept leverages the best properties of GaN for mid-range voltage applications: high mobility, high breakdown voltage, and native heterojunction enhancement-mode operation. Due to the crystallographic nature of the nanofin growth by molecular beam epitaxy, the sidewall heterojunctions occur on non-polar planes, resulting in ultra-smooth interfaces for high mobility, no sidewall etch damage and related surface/interface states, and elimination of piezoelectric effects that can limit reliability in conventional structures. This also facilitates superjunction formation for maximum device performance, and the selective-area growth of the nanofin results in dislocation-free growth, even on low-cost Si (111) substrate. In this program, core-shell nanofins were grown by molecular beam epitaxy, test structures to evaluate the doping, resistivity, and other electrical properties were fabricated, and the material and test structures were characterized in detail. The work identified clear potential (e.g., the doping was well controlled as required for superjunction concepts), but also additional areas that require additional effort to resolve (some unexpected crystal defects were encountered that require additional engineering to overcome). Simulation studies of the proposed concept validate that the fundamental approach is very promising, but additional effort in experimental realization is needed.
42 ENGINEERING↗
Vapor–Fed Electrolyzers for Carbon Dioxide Reduction Using Tandem Electrocatalysts: Cuprous Oxide Coupled with Nickel–Coordinated Nitrogen–Doped Carbon
We report ethylene is particularly attractive due to its major importance as a feedstock for various applications including the polymer industry. As such, catalyst and electrolyzer developments are crucial to achieve industrially relevant ethylene production and efficiency levels. In this work, a tandem electrocatalyst composed of copper nanocubes and nickel-coordinated nitrogen-doped carbon (NiNC) is presented, which is integrated into gas diffusion electrodes (GDEs) for direct conversion of vapor-fed CO 2 into ethylene. Evaluation of tandem GDEs in the vapor-fed flow electrolyzer shows significantly increased ethylene selectivity in terms of faradaic efficiency and C 2 H 4 /CO ratio compared to a non-tandem copper GDE. The enhancements are attributed to the increased local CO availability near the copper surface via effective CO 2 to CO conversion on neighboring NiNC. The experimental results are validated by 3D resolved continuum simulations, which show increased flux of higher-order prod-ucts with the added CO flux from NiNC. The practical viability of Cu/NiNC catalyst is further evaluated in a membrane electrode assembly electrolyzer, achieving 40% FE toward ethylene at 150 mA cm -2 and 3.2 V. These find-ings highlight the high selectivity and formation rate of ethylene achieved by successful device integration of the Cu/NiNC catalyst, demonstrating the potential for implementation in large-scale sustainable CO 2 electrolyzers.
36 MATERIALS SCIENCE↗