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At least 1,135 records · Page 63

All sources NASA NTRS DOE OSTI

DOE OSTI2014

Structure in multilayer films of zinc sulfide and copper sulfide via atomic layer deposition

Multilayer film stacks of ZnS and Cu{sub x}S (x ∼ 2) were made via atomic layer deposition. The precursors were bis(2,2,6,6-tetramethyl-3,5-heptanedionato)zinc, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)copper, and H{sub 2}S generated in situ for sulfur. Samples were deposited at 200 °C, in layers ranging from approximately 2 to 20 nm thick, based on binary growth rates. The properties of the film stacks were studied with atomic force microscopy, ultraviolet–visible spectroscopy, and extended x-ray absorption fine structure. The results demonstrate that the structure of films with the thinnest layers is dominated by Cu{sub x}S, whereas in the thicker films, the structure is determined by whichever material is first deposited. This can be attributed to the crystal structure mismatch of ZnS and Cu{sub x}S.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2014

Synthesis of copper nitride films doped with Fe, Co, or Ni by reactive magnetron sputtering

Copper nitride (Cu{sub 3}N) and Fe-, Co-, and Ni-doped Cu{sub 3}N films were prepared by reactive magnetron sputtering. The films were deposited on silicon substrates at room temperature using pure Cu target and metal chips. The molar ratio of Cu to N atoms in the as-prepared Cu{sub 3}N film was 2.7:1, which is comparable with the stoichiometry ratio 3:1. X-ray diffraction measurements showed that the films were composed of Cu{sub 3}N crystallites with anti-ReO{sub 3} structure and adopted different preferred orientations. The reflectance of the four samples decreased in the wavelength range of 400–830 nm, but increased rapidly within wavelength range of 830–1200 nm. Compared with the Cu{sub 3}N films, the resistivity of the doped Cu{sub 3}N films decreased by three orders of magnitude. These changes have great application potential in optical and electrical devices based on Cu{sub 3}N films.

36 MATERIALS SCIENCE↗

DOE OSTI2018

The Influence of Copper Impurity on the Electronic Structure and Optical Properties of TmNi{sub 5} Compound

Investigations of the electronic structure and optical properties of TmNi{sub 5–х}Сu{sub x} (х = 0, 1, 2, 3) compounds were performed. Self-consistent calculations of the band spectrum have been performed in the local electron-spin-density approximation with a correction on strong electron interactions within the LSDA + U method. Total and partial densities of electron states associated with thulium, nickel, and copper atoms have been calculated. Optical conductivity, the behavior of which is interpreted for each compound taking into account the performed calculations, has been measured by the ellipsometry method in a wide wavelength range of 0.22–16 μm. Concentration dependences of plasma and relaxation frequencies of conduction electrons have been determined.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2015

Synthesis and crystal structure of a copper complex with (E)-2-(4-(1H-1,2,4-triazol-1-yl)benzylidene)-3, 4-dihydronaphthalen-1(2H)-one ligand

The title compound, C{sub 35}H{sub 23}CuF{sub 6}N{sub 3}O{sub 5}S{sub 2} (1), was synthesized by the reaction of Cu(tta){sub 2} and L{sup 1}, (L{sup 1} = (E)-2-(4-(1H-1,2,4-triazol-1-yl)benzylidene)-3, 4-dihydronaphthalen-1(2H)-one) in the dichloromethane solution. It crystallizes in the monoclinic, space group P2{sub 1}/c with a = 33.8388(5), b = 9.3874(2), c = 21.8194(4) Å, β = 95.522(2), V = 6898.9(2) Å{sup 3}, Z = 8, D{sub x} = 1.554 Mg/m{sup 3}, F(000) = 3272, µ = 0.834 mm{sup –1}, R{sub 1} = 0.0639, wR{sub 2} = 0.1637. The copper(II) ion of 1 is in a distorted square-pyramidal environment with four O atoms of the two tta ligands and one N atom of triazole ligand L{sup 1}. Single-crystal X-ray diffraction data revealed that the hydrogen bonds, weak C–H···π and π···π interactions in the crystals link the coordination units to form 3D supramolecular structures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2012

Photoelectric and electric properties of four-component copper chalcogenides

The results of investigation of the electrophysical and photoelectric properties of complex copper chalcogenides are presented, namely, the properties of CuSnAsSe{sub 3}, which exhibits ferroelectric properties, and CuInAsS{sub 3}, which exhibits ionic conductivity. The spectral and temperature regions of photosensitivity of these crystals are determined. The depth of the level of carrier trapping centers, which manifest themselves under thermal activation, are evaluated from the analysis of thermally stimulated conductivity (TSC) curves in CuInAsS{sub 3}.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Maturation of Rhodobacter capsulatus Multicopper Oxidase CutO Depends on the CopA Copper Efflux Pathway and Requires the cutF Product

Copper (Cu) is an essential cofactor required for redox enzymes in all domains of life. Because of its toxicity, tightly controlled mechanisms ensure Cu delivery for cuproenzyme biogenesis and simultaneously protect cells against toxic Cu. Many Gram-negative bacteria contain extracytoplasmic multicopper oxidases (MCOs), which are involved in periplasmic Cu detoxification. MCOs are unique cuproenzymes because their catalytic center contains multiple Cu atoms, which are required for the oxidation of Cu 1+ to the less toxic Cu 2+ . Hence, Cu is both substrate and essential cofactor of MCOs. Here, we investigated the maturation of Rhodobacter capsulatus MCO CutO and its role in periplasmic Cu detoxification. A survey of CutO activity of R. capsulatus mutants with known defects in Cu homeostasis and in the maturation of the cuproprotein cbb 3 -type cytochrome oxidase ( cbb 3 -Cox) was performed. This revealed that CutO activity is largely independent of the Cu-delivery pathway for cbb 3 -Cox biogenesis, except for the cupric reductase CcoG, which is required for full CutO activity. The most pronounced decrease of CutO activity was observed with strains lacking the cytoplasmic Cu chaperone CopZ, or the Cu-exporting ATPase CopA, indicating that CutO maturation is linked to the CopZ-CopA mediated Cu-detoxification pathway. Our data demonstrate that CutO is important for cellular Cu resistance under both aerobic and anaerobic growth conditions. CutO is encoded in the cutFOG operon, but only CutF, and not CutG, is essential for CutO activity. No CutO activity is detectable when cutF or its putative Cu-binding motif are mutated, suggesting that the cutF product serves as a Cu-binding component required for active CutO production. Bioinformatic analyses of CutF-like proteins support their widespread roles as putative Cu-binding proteins for several Cu-relay pathways. Our overall findings show that the cytoplasmic CopZ-CopA dependent Cu detoxification pathway contributes to providing Cu to CutO maturation, a process that strictly relies on cutF .

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1950

Dependence of the elastic strain coefficient of copper on the pre-treatment

The effect of various pre-treatments on the elastic strain coefficient (alpha) (defined as the reciprocal of the modulus of elasticity E) (Epsilon) and on the mechanical hysteresis of copper has been investigated. Variables comprising the pre-treatments were pre-straining by stretching in a tensile testing machine and by drawing through a die, aging at room and elevated temperatures and annealing. The variation of the elastic strain coefficient with test stress was also investigated.

RODS - TENSION↗

DOE OSTI2011

Differential Reactivity between Two Copper Sites in Peptidylglycine r-Hydroxylating Monooxygenase

Peptidylglycine {alpha}-hydroxylating monooxygenase (PHM) catalyzes the stereospecific hydroxylation of the C{alpha} of C-terminal glycine-extended peptides and proteins, the first step in the activation of many peptide hormones, growth factors, and neurotransmitters. The crystal structure of the enzyme revealed two nonequivalent Cu sites (Cu{sub M} and Cu{sub H}) separated by {approx}11 {angstrom}. In the resting state of the enzyme, Cu{sub M} is coordinated in a distorted tetrahedral geometry by one methionine, two histidines, and a water molecule. The coordination site of the water molecule is the position where external ligands bind. The Cu{sub H} has a planar T-shaped geometry with three histidines residues and a vacant position that could potentially be occupied by a fourth ligand. Although the catalytic mechanism of PHM and the role of the metals are still being debated, Cu{sub M} is identified as the metal involved in catalysis, while Cu{sub H} is associated with electron transfer. To further probe the role of the metals, we studied how small molecules such as nitrite (NO{sub 2}{sup -}), azide (N{sub 3}{sup -}), and carbon monoxide (CO) interact with the PHM copper ions. The crystal structure of an oxidized nitrite-soaked PHMcc, obtained by soaking for 20 h in mother liquor supplemented with 300 mM NaNO{sub 2}, shows that nitrite anion coordinates Cu{sub M} in an asymmetric bidentate fashion. Surprisingly, nitrite does not bind Cu{sub H}, despite the high concentration used in the experiments (nitrite/protein > 1000). Similarly, azide and carbon monoxide coordinate Cu{sub M} but not Cu{sub H} in the PHMcc crystal structures obtained by cocrystallization with 40 mM NaN{sub 3} and by soaking CO under 3 atm of pressure for 30 min. This lack of reactivity at the Cu{sub H} is also observed in the reduced form of the enzyme: CO binds Cu{sub M} but not Cu{sub H} in the structure of PHMcc obtained by exposure of a crystal to 3 atm CO for 15 min in the presence of 5 mM ascorbic acid (reductant). The necessity of Cu{sub H} to maintain its redox potential in a narrow range compatible with its role as an electron-transfer site seems to explain the lack of coordination of small molecules to Cu{sub H}; coordination of any external ligand will certainly modify its redox potential.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2016

Single-Crystal Copper Research

Presentation on the use of single-crystal copper to examine whether texture in polycrystalline metals is important, and when.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Self‐Trapped and Free Exciton Dynamics in Vacuum‐Deposited Cesium Copper Iodide Thin Films

Abstract Highly photoluminescent, lead‐free perovskites are of interest for displays and solid‐state light‐emitting devices. In this report, streak camera‐based time‐resolved emission and transient absorption spanning visible to deep‐ultraviolet (UV) wavelengths are utilized to study self‐trapped and free exciton dynamics in vacuum‐deposited cesium copper halide thin films of CsCu 2 I 3 and Cs 3 Cu 2 I 5 . Self‐trapped exciton emission of CsCu 2 I 3 exhibits more noticeable changes with time in the peak position and width than Cs 3 Cu 2 I 5 . UV‐to‐blue emission is detectable for both compositions, where free exciton emission is distinct for CsCu 2 I 3 . Transient absorption shows loss of ground‐state bleach signals at early time delays for both, and the bleach signal shifts toward higher energy as time delay increases, likely due to strains induced by the newly created self‐trapped excitons. Global analysis performed on the transient absorption results yields time constants in these materials that build an overall dynamic scheme. This work aids in building a complete picture regarding light emission in these promising materials.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Compact 3D Copper with Uniform Porous Structure Derived by Electrochemical Dealloying as Dendrite-Free Lithium Metal Anode Current Collector

Here, the development of lithium (Li) metal anodes Li metal batteries faces huge challenges such as uncontrolled Li dendrite growth and large volume change during Li plating/stripping, resulting in severe capacity decay and high safety hazards. A 3D porous copper (Cu) current collector as a host for Li deposition can effectively settle these problems. However, constructing a uniform and compact 3D porous Cu structure is still an enormous challenge. Herein, an electrochemical etching method for Cu–Zinc (Zn) alloy is reported to precisely engrave a 3D Cu structure with uniform, smooth, and compact porous network. Such a continuous structure endows 3D Cu excellent mechanical properties and high electrical conductivity. The uniform and smooth pores with a large internal surface area ensures well dispersed current density for homogeneous Li metal deposition and accommodation. A smooth and stable solid electrolyte interphase is formed and meanwhile Li dendrites and dead Li are effectively suppressed. The Li metal anode conceived 3D Cu current collector can stably cycle for 400 h under an Li plating/stripping capacity of 1 mA h cm –2 and a current density of 1 mA cm –2 . The Li@3D Cu||LiFePO 4 full cells present excellent cycling and rate performances. The electrochemical dealloying is a robust method to construct 3D Cu current collectors for dendrite–free Li metal anodes.

25 ENERGY STORAGE↗

DOE OSTI2017

Spectroscopic Evidence for a Monomeric Copper(I) Hydride and Crystallographic Characterization of a Monomeric Silver(I) Hydride

(1,3-bis[2,6-bis[di(4-tert-butylphenyl)methyl]-4-methylphenyl]imidazol-2-ylidene)CuOPh [(IPr**)CuOPh] reacts with poly(methylhydrosiloxane) as the hydride donor to afford the monomeric (IPr**)CuH complex, which was spectroscopically characterized. The latter is in equilibrium in solution with [(IPr**)CuH]2, the dimer being exclusively present in the solid state. In this work, these results support the hypothesis that copper hydride aggregates dissociate in solution. In contrast, addition of pinacolborane to [(IPr**)AgOPh] at –40 °C allows the isolation of the monomeric (IPr**)AgH complex, which was crystallographically characterized.