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At least 1,459 records · Page 81

Pick-and-Place Transfer of Arbitrary-Metal Electrodes for van der Waals Device Fabrication

Van der Waals electrode integration is a promising strategy to create nearly perfect interfaces between metals and 2D materials, with advantages such as eliminating Fermi-level pinning and reducing contact resistance. However, the lack of a simple, generalizable pick-and-place transfer technology has greatly hampered the wide use of this technique. Here, we demonstrate the pick-and-place transfer of prefabricated electrodes from reusable polished hydrogenated diamond substrates without the use of any sacrificial layers due to the inherent low-energy and dangling-bond-free nature of the hydrogenated diamond surface. The technique enables transfer of arbitrary-metal electrodes and an electrode array, as demonstrated by successful transfer of eight different elemental metals with work functions ranging from 4.22 to 5.65 eV. We also demonstrate the electrode array transfer for large-scale device fabrication. The mechanical transfer of metal electrodes from diamond to van der Waals materials creates atomically smooth interfaces with no interstitial impurities or disorder, as observed with cross-section high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy. As a demonstration of its device application, we use the diamond transfer technique to create metal contacts to monolayer transition metal dichalcogenide semiconductors with high-work-function Pd, low-work-function Ti, and semimetal Bi to create n- and p-type field-effect transistors with low Schottky barrier heights. We also extend this technology to air-sensitive materials (trilayer 1T’ WTe 2 ) and other applications such as ambipolar transistors, Schottky diodes, and optoelectronics. This highly reliable and reproducible technology paves the way for new device architectures and high-performance devices.

2D materials↗

Structure and assembly of the diiron cofactor in the heme-oxygenase–like domain of the N-nitrosourea–producing enzyme SznF

In biosynthesis of the pancreatic cancer drug streptozotocin, the tridomain nonheme-iron oxygenase SznF hydroxylates N δ and N ω ' of N ω -methyl- L -arginine before oxidatively rearranging the triply modified guanidine to the N-methyl-N-nitrosourea pharmacophore. A previously published structure visualized the monoiron cofactor in the enzyme’s C-terminal cupin domain, which promotes the final rearrangement, but exhibited disorder and minimal metal occupancy in the site of the proposed diiron cofactor in the N-hydroxylating heme-oxygenase–like (HO-like) central domain. We leveraged our recent observation that the N-oxygenating µ-peroxodiiron(III/III) intermediate can form in the HO-like domain after the apo protein self-assembles its diiron(II/II) cofactor to solve structures of SznF with both of its iron cofactors bound. These structures of a biochemically validated member of the emerging heme-oxygenase–like diiron oxidase and oxygenase (HDO) superfamily with intact diiron cofactor reveal both the large-scale conformational change required to assemble the O 2 -reactive Fe 2 (II/II) complex and the structural basis for cofactor instability—a trait shared by the other validated HDOs. During cofactor (dis)assembly, a ligand-harboring core helix dynamically (un)folds. The diiron cofactor also coordinates an unanticipated Glu ligand contributed by an auxiliary helix implicated in substrate binding by docking and molecular dynamics simulations. The additional carboxylate ligand is conserved in another N-oxygenating HDO but not in two HDOs that cleave carbon–hydrogen and carbon–carbon bonds to install olefins. Among ~9,600 sequences identified bioinformatically as members of the emerging HDO superfamily, ~25% conserve this additional carboxylate residue and are thus tentatively assigned as N-oxygenases.

59 BASIC BIOLOGICAL SCIENCES↗

Materials Data on H2 by Materials Project

H2 is Magnesium structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is zero-dimensional and consists of two hydrogen molecules. H is bonded in a 1-coordinate geometry to atoms.

36 MATERIALS SCIENCE↗

Materials Data on H2 by Materials Project

H2 is Cubic alpha N2-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is zero-dimensional and consists of two hydrogen molecules. H is bonded in a single-bond geometry to one H atom. The H–H bond length is 0.75 Å.

36 MATERIALS SCIENCE↗

Materials Data on H2 by Materials Project

H2 crystallizes in the hexagonal P6_3/mmc space group. The structure is zero-dimensional and consists of two hydrogen molecules. H is bonded in a 1-coordinate geometry to atoms.

36 MATERIALS SCIENCE↗

Materials Data on H2 by Materials Project

H2 is gamma nitrogen structured and crystallizes in the orthorhombic Cmce space group. The structure is zero-dimensional and consists of four hydrogen molecules. H is bonded in a single-bond geometry to one H atom. The H–H bond length is 0.75 Å.

36 MATERIALS SCIENCE↗

Materials Data on H2 by Materials Project

H2 is Cubic alpha N2-like structured and crystallizes in the tetragonal I4/mmm space group. The structure is zero-dimensional and consists of two hydrogen molecules. H is bonded in a single-bond geometry to one H atom. The H–H bond length is 0.75 Å.

36 MATERIALS SCIENCE↗

Materials Data on H2 by Materials Project

H2 is Tungsten structured and crystallizes in the cubic Im-3m space group. The structure is zero-dimensional and consists of two hydrogen molecules. H is bonded in a 1-coordinate geometry to atoms.

36 MATERIALS SCIENCE↗

Materials Data on H2 by Materials Project

H2 is Copper structured and crystallizes in the cubic Fm-3m space group. The structure is zero-dimensional and consists of four hydrogen molecules. H is bonded in a 1-coordinate geometry to atoms.

36 MATERIALS SCIENCE↗

Materials Data on H2 by Materials Project

H2 is Cubic alpha N2-like structured and crystallizes in the tetragonal I4/mmm space group. The structure is zero-dimensional and consists of two hydrogen molecules. H is bonded in a single-bond geometry to one H atom. The H–H bond length is 0.75 Å.

36 MATERIALS SCIENCE↗

Materials Data on H2 by Materials Project

H2 is Cubic alpha N2-like structured and crystallizes in the orthorhombic Cmmm space group. The structure is zero-dimensional and consists of two hydrogen molecules. H is bonded in a single-bond geometry to one H atom. The H–H bond length is 0.74 Å.

36 MATERIALS SCIENCE↗

Materials Data on H2 by Materials Project

H2 is Cubic alpha N2-like structured and crystallizes in the orthorhombic Pnma space group. The structure is zero-dimensional and consists of eight hydrogen molecules. H is bonded in a single-bond geometry to one H atom. The H–H bond length is 0.74 Å.

36 MATERIALS SCIENCE↗

Materials Data on H2 by Materials Project

H2 is Cubic alpha N2-like structured and crystallizes in the orthorhombic P2_12_12_1 space group. The structure is zero-dimensional and consists of four hydrogen molecules. H is bonded in a single-bond geometry to one H atom. The H–H bond length is 0.75 Å.

36 MATERIALS SCIENCE↗

Materials Data on H2 by Materials Project

H2 is Cubic alpha N2-like structured and crystallizes in the monoclinic P2_1 space group. The structure is zero-dimensional and consists of sixteen hydrogen molecules. H is bonded in a single-bond geometry to one H atom. The H–H bond length is 0.75 Å.

36 MATERIALS SCIENCE↗

Materials Data on H2 by Materials Project

H2 is Cubic alpha N2-like structured and crystallizes in the orthorhombic Pnma space group. The structure is zero-dimensional and consists of eight hydrogen molecules. H is bonded in a single-bond geometry to one H atom. The H–H bond length is 0.75 Å.

36 MATERIALS SCIENCE↗

FWP FEAA149: “Next Generation Environmental Barrier Coatings”

Environmental barrier coatings (EBCs) are required coatings for utilization of SiC/SiC ceramic matrix composite (CMC) components in gas turbines, where the EBC represents the life-limiting factor for such components. EBC/CMC systems have shown success in aero-engine applications with increased turbine inlet temperatures and improved efficiencies, which are achieved through higher temperature stability, lower density, and decreased reliance on cooling air compared to traditional superalloys. While industrial gas turbines (IGTs) do not currently utilize SiC/SiC CMCs, the current shift towards low-carbon or carbon-free fuel sources for power generation could result in a need for EBC/CMC components with higher temperature capabilities. In this work, three tasks were outlined to improve understanding of EBC lifetimes to encourage use in IGTs with carbon-free fuel such as hydrogen: 1. Define the bond coating oxidation kinetics and EBC failure criteria, 2. Measure thermal expansion coefficients of each layered material, and 3. Perform advanced characterization and modeling to assess EBC lifetimes. Cyclic steam oxidation tests were conducted on various EBC/Si/SiC chemistries and EBC/SiC architectures to define substrate oxidation kinetics and EBC failure modes. An open-source code was developed to quantify the undulating thermally grown oxide thickness with thousands of measurements from specimen cross-section images. Bond coating oxidation kinetics were determined and used to develop a kinetic and thermodynamic model for predicting EBC lifetimes. High-temperature Raman spectroscopy was utilized for determining the SiO 2 thermally grown oxide phase transformation as the life-limiting feature for EBCs. Model efforts supported the claim that the SiO 2 phase transformation causes elevated stress during thermal cycling with associated cracking that decreases the adhesion strength of the EBC, eventually resulting in coating spallation. The finite element model subroutine will be made publicly available upon internal review. Further development of an EBC lifetime model for IGTs involves definition of a critical SiO 2 thickness for EBC spallation and must also consider both environmental (gas velocity, pressure, etc.) and specimen (EBC dopants, layer architectures, etc.) effects into predicted bond coating oxidation kinetics for long-lifetime components.

36 MATERIALS SCIENCE↗

Promoted Ru/PrOx Catalysts for Mild Ammonia Synthesis

Ammonia synthesis is one of the most important chemical reactions. Due to thermodynamic restrictions and the reaction requirements of the current commercial iron catalysts, it is also one of the worst reactions for carbon dioxide emissions and energy usage. Ruthenium-based catalysts can substantially improve the environmental impact as they operate at lower pressures and temperatures. In this work, we provide a screening of more than 40 metals as possible promoter options based on a Ru/Pr2O3 catalyst. Cesium was the best alkali promoter and was held constant for the series of double-promoted catalysts. Ten formulations outperformed the Ru-Cs/PrOx benchmark, with barium being the best second promoter studied and the most cost-effective option. Designs of experiments were utilized to optimize both the pretreatment conditions and the promoter weight loadings of the doubly promoted catalyst. As a result, optimization led to a more than five-fold increase in activity compared to the unpromoted catalyst, therefore creating the possibility for low-ruthenium ammonia synthesis catalysts to be used at scale. Further, we have explored the roles of promoters using kinetic analysis, X-ray Photoelectron Spectroscopy (XPS), and in situ infrared spectroscopy. Here, we have shown that the role of barium is to act as a hydrogen scavenger and donor, which may permit new active sites for the catalyst, and have demonstrated that the associative reaction mechanism is likely used for the unpromoted Ru/PrOx catalyst with hydrogenation of the triple bond of the dinitrogen occurring before any dinitrogen bond breakage.

Chemistry↗

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of catonic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrogen hydrolysis rate constant.

Johnson, H.↗