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At least 1,027 records · Page 57

Luminescence of defects in the structural transformation of layered tin dichalcogenides

Layered tin sulfide semiconductors are both of fundamental interest and attractive for energy conversion applications. Sn sulfides crystallize in several stable bulk phases with different Sn:S ratios (SnS 2 , Sn 2 S 3 , and SnS), which can transform into phases with a lower sulfur concentration by introduction of sulfur vacancies (V S ). How this complex behavior affects the optoelectronic properties remains largely unknown but is of key importance for understanding light-matter interactions in this family of layered materials. In this work, we use the capability to induce V S and drive a transformation between few-layer SnS 2 and SnS by electron beam irradiation, combined with in-situ cathodoluminescence spectroscopy and ab-initio calculations to probe the role of defects in the luminescence of these materials. In addition to the characteristic band-edge emission of the endpoint structures, our results show emerging luminescence features accompanying the SnS 2 to SnS transformation. Comparison with calculations indicates that the most prominent emission in SnS 2 with sulfur vacancies is not due to luminescence from a defect level but involves recombination of excitons bound to neutral V S in SnS 2 . These results provide insight into the intrinsic and defect-related optoelectronic properties of Sn chalcogenide semiconductors.

36 MATERIALS SCIENCE↗

Highly Asymmetric Graphene Layer Doping and Band Structure Manipulation in Rare Earth–Graphene Heterostructure by Targeted Bonding of the Intercalated Gadolinium

Heterostructures consisting of vertically stacked two-dimensional (2D) materials have recently gained large attention due to their highly controllable electronic properties and resulting quantum phases. In contrast to the mechanically stacked multilayered systems, which offer exceptional control over a stacking sequence or interlayer twist angles, the epitaxially grown 2D materials express unprecedented quality and stability over wafer-scale lengths. However, controlling the growth conditions remains a major obstacle toward the formation of complex, epitaxial heterostructures with well-defined electronic properties. Here, we synthesized a trilayer graphene heterostructure on the SiC(0001) substrate with two specific interlayer locations occupied by gadolinium. We applied multitechnique methodology based on low-temperature scanning tunneling microscopy/spectroscopy (STM/S) and angle-resolved photoelectron spectroscopy (ARPES) to determine the intercalant’s locations in the complex, epitaxial graphene heterostructure. Our approach relies on very high quality and large, micrometer-scale homogeneity of the synthesized system. The experimentally determined electronic structure is dominated by the two topmost graphene layers. Overall, our spectroscopic results show quantitative agreement between global ARPES, local STM/S, and density functional theory predictions. The characterized electronic properties primarily reflect highly anisotropic doping levels between the two corresponding graphene layers, which significantly affect the band structure topology. Two pairs of hybridized massive Dirac bands from our initial synthesis–the bilayer graphene on the SiC(0001) substrate–are transformed upon Gd intercalation into two pairs of massless Dirac bands with a new hybridization region in between. Our results open perspectives in the realization of exotic 2D quantum materials via atomically precise synthesis of epitaxial, multilayered graphene–rare earth heterostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Turbulent boundary-layer flow and structure on a convex wall and its redeveloment on a flat wall

Although the number of data sets which show the effects of convex curvature on turbulence has increased in the last 10 years, the development of really good calculational models is being held back by a lack of reliable data. The pesent investigation is concerned with a set of experiments which provide a litle more information regarding the response of a boundary-layer flow to convex curvature. Careful measurements were conducted to show the response of the boudnary layer to a sudden change from flat wall to curvature, and from curvature to flat wall. It was found that curvature effects were clearly apparent one or two boundary-layer thicknesses downstream of the start of curvature, while the disappearance of the curvature effects on a flat wall was an extremely slow process.

Gillis, J. C.↗

Effects of precipitation on the thermodynamic structure of the trade wind boundary layer

A model of the thermodynamic structure of the trade wind boundary layer is formulated to include the parameterization of precipitation in relatively shallow clouds. Although the area-averaged simulated precipitation rates are relatively small (less than 1 mm/day), the inclusion of precipitation has an appreciable effect on the predicted thermodynamic structure. The cloud layer structure simulated with precipitation is warmer, drier, and more stable than that simulated without precipitation. The simulated inversion height is lowered by as much as 60 mbar when precipitation is included.

Albrecht, Bruce A.↗

Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

The electrochemical lithiation and delithiation of the layered oxysulfide Sr 2 MnO 2 Cu 4-δ S 3 has been investigated by using a combination of in situ powder X-ray diffraction and ex situ neutron powder diffraction, X-ray absorption and 7 Li NMR spectroscopy, together with a range of electrochemical experiments. Sr 2 MnO 2 Cu 4-δ S 3 consists of [Sr 2 MnO 2 ] perovskite-type cationic layers alternating with highly defective antifluorite-type [Cu 4-δ S 3 ] (δ ≈ 0.5) anionic layers. It undergoes a combined displacement/intercalation (CDI) mechanism on reaction with Li, where the inserted Li replaces Cu, forming Li 4 S 3 slabs and Cu + is reduced and extruded as metallic particles. For the initial 2-3% of the first discharge process, the vacant sites in the sulfide layer are filled by Li; Cu extrusion then accompanies further insertion of Li. Mn 2.5+ is reduced to Mn 2+ during the first half of the discharge. The overall charging process involves the removal of Li and re-insertion of Cu into the sulfide layers with re-oxidation of Mn 2+ to Mn 2.5+ . However, due to the different diffusivities of Li and Cu, the processes operating on charge are quite different from those operating during the first discharge: charging to 2.75 V results in the removal of most of the Li, little reinsertion of Cu, and good capacity retention. A charge to 3.75 V is required to fully reinsert Cu, which results in significant changes to the sulfide sublattice during the following discharge and poor capacity retention. This detailed structure-property investigation will promote the design of new functional electrodes with improved device performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Eddy Current Techniques for Detection of Deep Fatigue Cracks in Multi-Layer Airframe Components

Thick, multi-layer aluminum structure has been widely used in aircraft design in critical wing splice areas. The multi-layer structure generally consists of three or four aluminum layers with different geometry and varying thickness, which are held together with fasteners. The detection of cracks under fasteners with ultrasonic techniques in subsurface layers away from the skin is impeded primarily by interlayer bonds and faying sealant condition. Further, assessment of such sealant condition is extremely challenging in terms of complexity of structure, limited access, and inspection cost. Although Eddy current techniques can be applied on in-service aircraft from the exterior of the skin without knowing sealant condition, the current eddy current techniques are not able to detect defects with wanted sensitivity. In this work a series of low frequency eddy current probes have been designed, fabricated and tested for this application. A probe design incorporating a shielded magnetic field sensor concentrically located in the interior of a drive coil has been employed to enable a localized deep diffusion of the electromagnetic field into the part under test. Due to the required low frequency inspections, probes have been testing using a variety of magnetic field sensors (pickup coil, giant magneto-resistive, anisotropic magneto-resistive, and spin-dependent tunneling). The probe designs as well as capabilities based upon a target inspection for sub-layer cracking in an airframe wing spar joint is presented.

Wincheski, Russell A.↗

Quasi-Coherent Structures In Turbulent Boundary Layers

Two-part report reviews knowledge of coherent structures in turbulent boundary layers. Part I describes processes and status of cooperative project to summarize data from research on boundary-layer turbulence. Part II presents results of study of numerically simulated flat-plate canonical turbulent boundary layer.

Robinson, S. K.↗

Ceramic Fiber Structures for Cryogenic Load-Bearing Applications

This invention is intended for use as a load-bearing device under cryogenic temperatures and/or abrasive conditions (i.e., during missions to the Moon). The innovation consists of small-diameter, ceramic fibers that are woven or braided into devices like ropes, belts, tracks, or cables. The fibers can be formed from a variety of ceramic materials like silicon carbide, carbon, aluminosilicate, or aluminum oxide. The fiber architecture of the weave or braid is determined by both the fiber properties and the mechanical requirements of the application. A variety of weave or braid architectures is possible for this application. Thickness of load-bearing devices can be achieved by using either a 3D woven structure, or a layered, 2D structure. For the prototype device, a belt approximately 0.10 in. (0.25 cm) thick, and 3.0 in. (7.6 cm) wide was formed by layering and stitching a 2D aluminosilicate fiber weave.

Jaskowiak, Martha H.↗

The Influence of Substrate Temperature of Seed Layer on the Structure and Superconducting Property of BaHfO{sub 3}-Doped Y{sub 0.5}Gd{sub 0.5}Ba{sub 2}Cu{sub 3}O{sub 7−δ} Film Prepared by Pulsed Laser Deposition

For various practical applications, excellent superconducting properties under magnetic field of REBa{sub 2}Cu{sub 3}O{sub 7−δ} (RE = rare earth elements (REBCO))-coated conductors are required, which can be fabricated by introducing artificial pinning centers, such as second-phase dopant. It is well known that BaMO{sub 3} (M = Zr, Sn, or Hf) can form self-organized nanorods in REBCO matrix and improve the critical current density (J{sub c}) under applied magnetic field. However, with increasing dopant level, the critical temperature T{sub c} and J{sub c} at 77 K in self-field decreased. In order to inhibit the degradation of the J{sub c} in self-field, we fabricated 5 mol% BaHfO{sub 3} (BHO)-doped Y{sub 0.5}Gd{sub 0.5}Ba{sub 2}Cu{sub 3}O{sub 7−δ} (YGBCO) seed layers on CeO{sub 2}-buffered IBAD-MgO tapes by pulse laser deposition (PLD) at a laser repetition of 10 Hz and different substrate temperature T{sub seed}, and subsequently deposited 5-mol% BHO-doped YGBCO upper layers at 160 Hz and higher substrate temperature. The effect of T{sub seed} on the quality of the 5-mol% BHO-doped YGBCO upper layer was investigated. With increasing T{sub seed} from 710 to 820 {sup ∘}C, the Δφ value of YGBCO (103) reflection first decreased and then increased, while the J{sub c} at 77 K increased with increasing T{sub seed} to 790 {sup ∘}C and decreased at higher T{sub seed}. The 5-mol% BHO-doped YGBCO layer with a seed layer deposited at 790 {sup ∘}C had the highest J{sub c} (77 K, self-field) of 4.0 MA/cm{sup 2}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Intercalated hybrid graphite fiber composite

The invention is directed to a highly conductive lightweight hybrid material and methods of producing the same. The hybrid composite is obtained by weaving strands of a high strength carbon or graphite fiber into a fabric-like structure, depositing a layer of carbon onto the structure, heat treating the structure to graphitize the carbon layer, and intercalating the graphitic carbon layer structure. A laminate composite material useful for protection against lightning strikes comprises at least one layer of the hybrid material over at least one layer of high strength carbon or graphite fibers. The composite material of the present invention is compatible with matrix compounds, has a coefficient of thermal expansion which is the same as underlying fiber layers, and is resistant to galvanic corrosion in addition to being highly conductive. These materials are useful in the aerospace industry, in particular as lightning strike protection for airplanes.

Gaier, James R.↗

Hidden Subsurface Reconstruction and Its Atomic Origins in Layered Oxide Cathodes

Structural transformations near surfaces of solid-state materials underpin functional mechanisms of a broad range of applications including catalysis, memory, and energy storage. It has been a long-standing notion that the outmost free surfaces, accompanied by broken translational symmetry and altered atomic configurations, are usually the birthplace for structural transformations. Here, in a layered oxide cathode for Li-ion batteries, we for the first time observe the incipient state of the well documented layered-to-spinel-like structural transformation, which is surprisingly initiated from subsurface layer, rather than the very surface. Coupling atomic level scanning transmission electron microscopy imaging with electron energy loss spectroscopy, we discover that the reconstructed subsurfaces, featuring a mix of discrete patches of layered and spinel-like structures, are associated with selective atomic species partition and consequent nanoscale non-uniform composition gradient distribution at the subsurface. In conclusion, our findings provide fundamental insights on atomic-scale mechanisms of structural transformation in layered cathodes.

25 ENERGY STORAGE↗

Terahertz Photoluminescence of Double Acceptors in Bulky Epitaxial HgCdTe Layers and HgTe/CdHgTe Structures with Quantum Wells

The photoluminescence of bulky films and heterostructures with HgCdTe quantum wells is studied in the far IR range upon interband optical excitation. Photoluminescence lines are found whose position is independent of temperature, and intensity nonmonotonically changes with increasing temperature. These lines are shown to be related to the radiative recombination of holes by singly ionized mercury vacancies. A drastic increase in the equilibrium recombination of such centers involved in the formation of the photoluminescence signal with the temperature change from 40 to 70 K leads to the nonmonotonic temperature dependence of the photoluminescence intensity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Oxidation of Cyclopentene with Manganese Oxides Octahedral Molecular Sieves with Layer and Tunnel Structures

We report manganese oxides type octahedral molecular sieves OL-1, OMS-1, and OMS-2 were synthesized, impregnated with sodium tungstate, and evaluated as catalysts for the selective epoxidation of cyclopentene (CPE) to cyclopentene oxide (CPO) in the sodium bicarbonate/hydrogen peroxide (BAP) system. OL-1 was the best catalyst with a conversion of 78.6 % and a selectivity to CPO of 31.4 %. Impregnation with sodium tungstate affected the structure and activity of OL-1 and OMS-1. Mn 2+ is required for the epoxidation of CPE. FTIR spectra provides evidence that tungstate ions react, during impregnation, with Mg 2+ and/or Mn 2+ present in OMS-1 and OL-1 producing an amorphous compound that is not active in the epoxidation reaction. The crystalline and chemical structure of OMS-2 was not affected by tungstate impregnation, since most of the manganese occurs as Mn 3+ and Mn 4+ , which in presence of hydrogen peroxide, tend to form radicals, active in the total oxidation of organic compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insights into the rapid two-phase transport dynamics in different structured porous transport layers of water electrolyzers through high-speed visualization

In proton exchange membrane electrolyzer cells (PEMECs), maintaining efficient two-phase transport is one of the most important functions of porous transport layers (PTLs). To enhance the two-phase transport in PTLs, thin/titanium liquid/gas diffusion layers (TT-LGDLs) are introduced in PEMECs, and their difference from the conventional Ti felt PTLs are analyzed in-situ through high-speed and microscale visualization and electrochemical characterizations. The visualization results show that unfavorable large slugs can be greatly reduced in the PEMEC with a TT-LGDL compared to the PEMEC with a Ti felt PTL. More importantly, the recovery capability of water starvation with different PTLs is studied. After water starvation, the PEMEC with the TT-LGDL can recover the water starvation much more rapidly than the Ti felt cell, benefiting from its short and straight-through flow paths. Furthermore, the TT-LGDL tends to generate oxygen bubbles that are almost six times smaller and 236 times more frequently than the Ti felt PTL, indicating significantly boosted removal efficiency of produced oxygen and PEMEC performance. Finally, this study offers new insights into the dynamic processes of two-phase transport and the recovery capability of water starvation for different PTLs, which will provide valuable guidance for further optimization of PTLs and performance enhancement of PEMECs.

08 HYDROGEN↗