Sample records for wafer-level cu-cu bonds

  1. Wafer-Level Hermetic Package by Low-Temperature Cu/Sn TLP Bonding with Optimized Sn Thickness

    NASA Astrophysics Data System (ADS)

    Wu, Zijian; Cai, Jian; Wang, Qian; Wang, Junqiang; Wang, Dejun

    2017-10-01

    In this paper, a wafer-level package with hermetic sealing by low-temperature Cu/Sn transient liquid phase (TLP) bonding for a micro-electromechanical system was introduced. A Cu bump with a Sn cap and sealing ring were fabricated simultaneously by electroplating. The model of Cu/Sn TLP bonding was established and the thicknesses of Cu and Sn were optimized after a series of bonding experiments. Cu/Sn wafer-level bonding was undertaken at 260°C for 30 min under a vacuum condition. An average shear strength of 50.36 MPa and a fine leak rate of 1.9 × 10-8 atm cc/s were achieved. Scanning electron microscope photos of the Cu/Sn/Cu interlayers were presented, and energy dispersive x-ray analysis was conducted simultaneously. The results showed that the Sn was completely consumed to form the stable intermetallic compound Cu3Sn. An aging test of 200 h at 200°C was conducted to test the performance of the hermetic sealing, while the results of shear strength, fine leak rate and bonding interface were also set out.

  2. SEMICONDUCTOR TECHNOLOGY: Wafer level hermetic packaging based on Cu-Sn isothermal solidification technology

    NASA Astrophysics Data System (ADS)

    Yuhan, Cao; Le, Luo

    2009-08-01

    A novel wafer level bonding method based on Cu-Sn isothermal solidification technology is established. A multi-layer sealing ring and the bonding processing are designed, and the amount of solder and the bonding parameters are optimized based on both theoretical and experimental results. Verification shows that oxidation of the solder layer, voids and the scalloped-edge appearance of the Cu6Sn5 phase are successfully avoided. An average shear strength of 19.5 MPa and an excellent leak rate of around 1.9 × 10-9 atm cc/s are possible, meeting the demands of MIL-STD-883E.

  3. Wafer-level Cu-Sn micro-joints with high mechanical strength and low Sn overflow

    NASA Astrophysics Data System (ADS)

    Duan, Ani; Luu, Thi-Thuy; Wang, Kaiying; Aasmundtveit, Knut; Hoivik, Nils

    2015-09-01

    In this paper, we report wafer-level bonding using solid-liquid inter-diffusion (SLID) processes for fabricating micro-joints Cu-Sn at low temperature (270 °C). The evolution of multilayer Cu/Sn to micro-joint alloys has been characterized by optical microscopy and mechanical die-shear testing. The Cu-Sn joints with line width from 80 to 200 μm prove to be reliable packaging materials for bonding vacuum micro-cavities with controllable Sn overflow, as well as high mechanical strength (>70 MPa). A thermodynamic model has been performed to further understand the formation of Cu-Sn intermetallic alloys. There are two important findings for this work: 1) Using a two-step temperature profile may significantly reduce the amount of Sn overflow; 2) for packaging, a bond frame width greater than 80 μm will result in high yield.

  4. Direct, CMOS In-Line Process Flow Compatible, Sub 100 °C Cu-Cu Thermocompression Bonding Using Stress Engineering

    NASA Astrophysics Data System (ADS)

    Panigrahi, Asisa Kumar; Ghosh, Tamal; Kumar, C. Hemanth; Singh, Shiv Govind; Vanjari, Siva Rama Krishna

    2018-05-01

    Diffusion of atoms across the boundary between two bonding layers is the key for achieving excellent thermocompression Wafer on Wafer bonding. In this paper, we demonstrate a novel mechanism to increase the diffusion across the bonding interface and also shows the CMOS in-line process flow compatible Sub 100 °C Cu-Cu bonding which is devoid of Cu surface treatment prior to bonding. The stress in sputtered Cu thin films was engineered by adjusting the Argon in-let pressure in such a way that one film had a compressive stress while the other film had tensile stress. Due to this stress gradient, a nominal pressure (2 kN) and temperature (75 °C) was enough to achieve a good quality thermocompression bonding having a bond strength of 149 MPa and very low specific contact resistance of 1.5 × 10-8 Ω-cm2. These excellent mechanical and electrical properties are resultant of a high quality Cu-Cu bonding having grain growth between the Cu films across the boundary and extended throughout the bonded region as revealed by Cross-sectional Transmission Electron Microscopy. In addition, reliability assessment of Cu-Cu bonding with stress engineering was demonstrated using multiple current stressing and temperature cycling test, suggests excellent reliable bonding without electrical performance degradation.

  5. Cu Pillar Low Temperature Bonding and Interconnection Technology of for 3D RF Microsystem

    NASA Astrophysics Data System (ADS)

    Shi, G. X.; Qian, K. Q.; Huang, M.; Yu, Y. W.; Zhu, J.

    2018-03-01

    In this paper 3D interconnects technologies used Cu pillars are discussed with respect to RF microsystem. While 2.5D Si interposer and 3D packaging seem to rely to cu pillars for the coming years, RF microsystem used the heterogeneous chip such as GaAs integration with Si interposers should be at low temperature. The pillars were constituted by Cu (2 micron) -Ni (2 micron) -Cu (3 micron) -Sn (1 micron) multilayer metal and total height is 8 micron on the front-side of the wafer by using electroplating. The wafer backside Cu pillar is obtained by temporary bonding, thinning and silicon surface etching. The RF interposers are stacked by Cu-Sn eutectic bonding at 260 °C. Analyzed the reliability of different pillar bonding structure.

  6. Fabrication of nano-scale Cu bond pads with seal design in 3D integration applications.

    PubMed

    Chen, K N; Tsang, C K; Wu, W W; Lee, S H; Lu, J Q

    2011-04-01

    A method to fabricate nano-scale Cu bond pads for improving bonding quality in 3D integration applications is reported. The effect of Cu bonding quality on inter-level via structural reliability for 3D integration applications is investigated. We developed a Cu nano-scale-height bond pad structure and fabrication process for improved bonding quality by recessing oxides using a combination of SiO2 CMP process and dilute HF wet etching. In addition, in order to achieve improved wafer-level bonding, we introduced a seal design concept that prevents corrosion and provides extra mechanical support. Demonstrations of these concepts and processes provide the feasibility of reliable nano-scale 3D integration applications.

  7. Texturization of diamond-wire-sawn multicrystalline silicon wafer using Cu, Ag, or Ag/Cu as a metal catalyst

    NASA Astrophysics Data System (ADS)

    Wang, Shing-Dar; Chen, Ting-Wei

    2018-06-01

    In this work, Cu, Ag, or Ag/Cu was used as a metal catalyst to study the surface texturization of diamond-wire-sawn (DWS) multi-crystalline silicon (mc-Si) wafer by a metal-assisted chemical etching (MACE) method. The DWS wafer was first etched by standard HF-HNO3 acidic etching, and it was labeled as AE-DWS wafer. The effects of ratios of Cu(NO3)2:HF, AgNO3:HF, and AgNO3:Cu(NO3)2 on the morphology of AE-DWS wafer were investigated. After the process of MACE, the wafer was treated with a NaF/H2O2 solution. In this process, H2O2 etched the nanostructure, and NaF removed the oxidation layer. The Si {1 1 1} plane was revealed by etching the wafer in a mixture of 0.03 M Cu(NO3)2 and 1 M HF at 55 °C for 2.5 min. These parallel Si {1 1 1} planes replaced some parallel saw marks on the surface of AE-DWS wafers without forming a positive pyramid or an inverted pyramid structure. The main topography of the wafer is comprised of silicon nanowires grown in <1 0 0> direction when Ag or Ag/Cu was used as a metal catalyst. When silicon is etched in a mixed solution of Cu(NO3)2, AgNO3, HF and H2O2 at 55 °C with a concentration ratio of [Cu2+]/[Ag+] of 50 or at 65 °C with a concentration ratio of [Cu2+]/[Ag+] of 33, a quasi-inverted pyramid structure can be obtained. The reflectivity of the AE-DWS wafers treated with MACE is lower than that of the multiwire-slurry-sawn (MWSS) mc-Si wafers treated with traditional HF + HNO3 etching.

  8. Low temperature wafer-level bonding for hermetic packaging of 3D microsystems

    NASA Astrophysics Data System (ADS)

    Tan, C. S.; Fan, J.; Lim, D. F.; Chong, G. Y.; Li, K. H.

    2011-07-01

    Metallic copper-copper (Cu-Cu) thermo-compression bonding, oxide-oxide (SiO2-SiO2) fusion bonding and silicon-silicon (Si-Si) direct bonding are investigated for potential application as hermetic seal in 3D microsystem packaging. Cavities are etched to a volume of 1.4 × 10-3 cm3 in accordance with the MIL-STD-883E standard prescribed for microelectronics packaging. In the case of metal bonding, a clean Cu layer with a thickness of 300 nm and a Ti barrier layer with an underlying thickness of 50 nm are used. The wafer pair is bonded at 300 °C under the application of a bonding force of 5500 N for 1 h. On the other hand, Si-Si bonding and SiO2-SiO2 bonding are initiated at room ambient after surface activation, followed by annealing in inert ambient at 300 °C for 1 h. The bonded cavities are stored in a helium bomb chamber and the leak rate is measured with a mass spectrometer. An excellent helium leak rate below 5 × 10-9 atm cm3 s-1 is detected for all cases and this is at least ten times better than the reject limit.

  9. Characterization of low temperature Cu/In bonding for fine-pitch interconnects in three-dimensional integration

    NASA Astrophysics Data System (ADS)

    Panchenko, Iuliana; Bickel, Steffen; Meyer, Jörg; Mueller, Maik; Wolf, Jürgen M.

    2018-02-01

    This study presents the results for Cu/In bonding based on the solid-liquid interdiffusion (SLID) principle for fine-pitch interconnects in three-dimensional integration. The microbumps were fabricated on Si wafers (55 µm pitch, 25 µm top bump diameter, 35 µm bottom bump diameter). In was electroplated directly on Cu only on the top die microbumps. Two different In thicknesses were manufactured (3 and 5 µm). The interconnects were successfully fabricated at a bonding temperature of 170 °C. High temperature storage was carried out at 150 and 200 °C for different times between 2 and 72 h directly after the interconnect formation in order to investigate the temperature stability. The microstructure was analyzed by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The intermetallic compound (IMC) found in the microbumps after electroplating was CuIn2. The intermetallic interlayer consists of Cu11In9 and a thin layer of Cu2In after bonding and isothermal storage.

  10. Wafer-level hermetic vacuum packaging by bonding with a copper-tin thin film sealing ring

    NASA Astrophysics Data System (ADS)

    Akashi, Teruhisa; Funabashi, Hirofumi; Takagi, Hideki; Omura, Yoshiteru; Hata, Yoshiyuki

    2018-04-01

    A wafer-level hermetic vacuum packaging technology intended for use with MEMS devices was developed based on a copper-tin (CuSn) thin film sealing ring. To allow hermetic packaging, the shear strength of the CuSn thin film bond was improved by optimizing the pretreatment conditions. As a result, an average shear strength of 72.3 MPa was obtained and a cavity that had been hermetically sealed using wafer-level packaging (WLP) maintained its vacuum for 1.84 years. The total pressures in the cavities and the partial pressures of residual gases were directly determined with an ultra-low outgassing residual gas analyzer (RGA) system. Hermeticity was evaluated based on helium leak rates, which were calculated from helium pressures determined with the RGA system. The resulting data showed that a vacuum cavity following 1.84 years storage had a total pressure of 83.1 Pa, contained argon as the main residual gas and exhibited a helium leak rate as low as 1.67  ×  10-17 Pa · m3 s-1, corresponding to an air leak rate of 6.19  ×  10-18 Pa · m3 s-1. The RGA data demonstrate that WLP using a CuSn thin film sealing ring permits ultra-high hermeticity in conjunction with long-term vacuum packaging that is applicable to MEMS devices.

  11. Alternatives for joining Si wafers to strain-accommodating Cu for high-power electronics

    NASA Astrophysics Data System (ADS)

    Faust, Nicholas; Messler, Robert W.; Khatri, Subhash

    2001-10-01

    Differences in the coefficients of thermal expansion (CTE) between silicon wafers and underlying copper electrodes have led to the use of purely mechanical dry pressure contacts for primary electrical and thermal connections in high-power solid-state electronic devices. These contacts are limited by their ability to dissipate I2R heat from within the device and by their thermal fatigue life. To increase heat dissipation and effectively deal with the CTE mismatch, metallurgical bonding of the silicon to a specially-structured, strain-accommodating copper electrode has been proposed. This study was intended to seek alternative methods for and demonstrate the feasibility of bonding Si to structured Cu in high-power solid-state devices. Three different but fundamentally related fluxless approaches identified and preliminarily assessed were: (1) conventional Sn-Ag eutectic solder; (2) a new, commercially-available active solder based on the Sn-Ag eutectic; and (3) solid-liquid interdiffusion bonding using the Au-In system. Metallurgical joints were made with varying quality levels (according to nonde-structive ultrasonic C-scan mapping, SEM, and electron microprobe) using each approach. Mechanical shear testing resulted in cohesive failure within the Si or the filler alloys. The best approach, in which eutectic Sn-Ag solder in pre-alloyed foil form was employed on Si and Cu substrates metallized (from the substrate outward) with Ti, Ni and Au, exhibited joint thermal conduction 74% better than dry pressure contacts.

  12. Development and Status of Cu Ball/Wedge Bonding in 2012

    NASA Astrophysics Data System (ADS)

    Schneider-Ramelow, Martin; Geißler, Ute; Schmitz, Stefan; Grübl, Wolfgang; Schuch, Bernhard

    2013-03-01

    Starting in the 1980s and continuing right into the last decade, a great deal of research has been published on Cu ball/wedge (Cu B/W) wire bonding. Despite this, the technology has not been established in industrial manufacturing to any meaningful extent. Only spikes in the price of Au, improvements in equipment and techniques, and better understanding of the Cu wire-bonding process have seen Cu B/W bonding become more widespread—initially primarily for consumer goods manufacturing. Cu wire bonding is now expected to soon be used for at least 20% of all ball/wedge-bonded components, and its utilization in more sophisticated applications is around the corner. In light of this progress, the present paper comprehensively reviews the existing literature on this topic and discusses wire-bonding materials, equipment, and tools in the ongoing development of Cu B/W bonding technology. Key bonding techniques, such as flame-off, how to prevent damage to the chip (cratering), and bond formation on various common chip and substrate finishes are also described. Furthermore, apart from discussing quality assessment of Cu wire bonds in the initial state, the paper also provides an overview of Cu bonding reliability, in particular regarding Cu balls on Al metalization at high temperatures and in humidity (including under the influence of halide ions).

  13. Modified pulse laser deposition of Ag nanostructure as intermediate for low temperature Cu-Cu bonding

    NASA Astrophysics Data System (ADS)

    Liu, Ziyu; Cai, Jian; Wang, Qian; Liu, Lei; Zou, Guisheng

    2018-07-01

    To lower the Cu-Cu bonding temperature and save the time of the bonding process applied for 3D integration, the Ag nanostructure deposited by pulsed laser deposition (PLD) was designed and decorated on the Cu pads as intermediate. Influences of different PLD process parameters on the designed Ag nanostructure morphology were investigated in this work. The large nanoparticles (NP) defects, NPs coverage rate on the Cu pad, and NPs size distribution were adopted to evaluate the PLD parameters based on the NPs morphology observation and the Cu-Cu bonding quality. The medium laser power of 0.8 W, smaller distance between target and substrate, and protective container should be applied in the optimized PLD to obtain the Ag nanostructure. Then a loose 3D mesh Ag nanostructure consisted of the protrusions and grooves was formed and the morphology observation proved the nanostructure deposition mechanism was contributed to the block of nano-film nucleation and nanoparticles absorption. Finally, the relationship between the bonding temperature and pressure suitable for the Ag nanostructure had been determined based on shear strength and interface observation. The results revealed the combination of higher bonding temperature (250 °C) and lower pressure (20 MPa), or lower bonding temperature (180 °C) and higher pressure (50 MPa) can both achieve the bonding process with the short bonding time of 5 min and annealing at 200 °C for 25 min in vacuum furnace.

  14. Plasma combined self-assembled monolayer pretreatment on electroplated-Cu surface for low temperature Cu-Sn bonding in 3D integration

    NASA Astrophysics Data System (ADS)

    Wang, Junqiang; Wang, Qian; Wu, Zijian; Tan, Lin; Cai, Jian; Wang, Dejun

    2017-05-01

    A novel pretreatment of plasma combined self-assembled monolayer (PcSAM) was proposed to improve surface properties of electroplated Cu for low temperature Cu-Sn bonding in 3D integration. Measurement results revealed that self-assemble monolayer (SAM) would be easier absorbed on plasma-activated Cu surface and protect the clean surface from re-oxidation when storage. The absorbed SAM layer could be removed by thermal desorption during bonding process. With optimal PcSAM pretreatment, oxygen content of the Cu surface was reduced to as low as 1.39%. The followed Cu-Sn bonding was realized at low temperature of 200 °C. Finally, bonding interface exhibited a defect-free interconnection, and bonding strength has reached as high as 68.7 MPa.

  15. Optimized ultra-thin manganin alloy passivated fine-pitch damascene compatible bump-less Cu-Cu bonding at sub 200 °C for three-dimensional Integration applications

    NASA Astrophysics Data System (ADS)

    Panigrahi, Asisa Kumar; Hemanth Kumar, C.; Bonam, Satish; Ghosh, Tamal; Rama Krishna Vanjari, Siva; Govind Singh, Shiv

    2018-02-01

    Enhanced Cu diffusion, Cu surface passivation, and smooth surface at the bonding interface are the key essentials for high quality Cu-Cu bonding. Previously, we have demonstrated optimized 3 nm thin Manganin metal-alloy passivation from oxidation and also helps to reduce the surface roughness to about 0.8 nm which substantially led to high quality Cu-Cu bonding. In this paper, we demonstrated an ultra fine-pitch (<25 µm) Cu-Cu bonding using an optimized Manganin metal-alloy passivation. This engineered surface passivation approach led to high quality bonding at sub 200 °C temperature and 0.4 MPa. Very low specific contact resistance of 1.4 × 10-7 Ω cm2 and the defect free bonded interface is clear indication of high quality bonding for future multilayer integrations. Furthermore, electrical characterization of the bonded structure was performed under various robust conditions as per International Technology Roadmap for Semiconductors (ITRS Roadmap) in order to satisfy the stability of the bonded structure.

  16. Characterization of wafer-level bonded hermetic packages using optical leak detection

    NASA Astrophysics Data System (ADS)

    Duan, Ani; Wang, Kaiying; Aasmundtveit, Knut; Hoivik, Nils

    2009-07-01

    For MEMS devices required to be operated in a hermetic environment, one of the main reliability issues is related to the packaging methods applied. In this paper, an optical method for testing low volume hermetic cavities formed by anodic bonding between glass and SOI (silicon on insulator) wafer is presented. Several different cavity-geometry structures have been designed, fabricated and applied to monitor the hermeticity of wafer level anodic bonding. SOI wafer was used as the cap wafer on which the different-geometry structures were fabricated using standard MEMS technology. The test cavities were bonded using SOI wafers to glass wafers at 400C and 1000mbar pressure inside a vacuum bonding chamber. The bonding voltage varies from 200V to 600V. The bonding strength between glass and SOI wafer was mechanically tested using shear tester. The deformation amplitudes of the cavity cap surface were monitored by using an optical interferometer. The hermeticity of the glass-to-SOI wafer level bonding was characterized through observing the surface deformation in a 6 months period in atmospheric environment. We have observed a relatively stable micro vacuum-cavity.

  17. Combined surface activated bonding using H-containing HCOOH vapor treatment for Cu/Adhesive hybrid bonding at below 200 °C

    NASA Astrophysics Data System (ADS)

    He, Ran; Fujino, Masahisa; Akaike, Masatake; Sakai, Taiji; Sakuyama, Seiki; Suga, Tadatomo

    2017-08-01

    Cu/adhesive hybrid bonding is an attractive approach to three-dimensional (3D) integration because it provides direct Cusbnd Cu vertical interconnects and high mechanical stability. However, Cu/adhesive hybrid bonding at below 200 °C is still challenging because of bonding temperature mismatch between Cusbnd Cu and polymer adhesives and lacking of effective adhesive-compatible Cu surface activation methods. In this paper, we investigate and demonstrate a ;Cu-first; hybrid bonding technique by using hydrogen(H)-containing formic acid (HCOOH) vapor prebonding surface treatment for the first time. In this technique, high-quality Cusbnd Cu bonding is obtained at 180-200 °C that is close to or even lower than the temperature of subsequent adhesive curing. We experimentally investigate the effects of the H-containing HCOOH vapor treatment for Cusbnd Cu bonding and cyclo-olefin polymer adhesive-adhesive bonding. This technique enables Cu/adhesive hybrid bonding at below 200 °C, promising smaller thermal stress, higher throughput, and lower cost comparing to the existing ;adhesive-first; hybrid bonding method.

  18. IR and TPD studies of the interaction of alkenes with Cu + sites in CuNaY and CuNaX zeolites of various Cu content. The heterogeneity of Cu + sites

    NASA Astrophysics Data System (ADS)

    Datka, J.; Kukulska-Zajaç, E.; Kozyra, P.

    2006-08-01

    Cu + ions in zeolites activate organic molecules containing π electrons by π back donation, which results in a distinct weakening of multiple bonds. In this study, we followed the activation of alkenes (ethene and propene) by Cu + ions in CuY and CuX zeolites of various Cu content. We also studied the strength of bonding of alkenes to Cu + ions. IR studies have shown that there are two kinds of Cu + sites of various electron donor properties. We suppose that they could be attributed to the presence of Cu + ions of various number of oxygen atoms surrounding the cation. IR studies have shown that Cu ions introduced into Y and X zeolites in the first-order (at low Cu content) form Cu + ions of stronger electron donor properties (i.e. activate alkenes to larger extend) than Cu ions introduced in the next order (at higher Cu content). IR and TPD studies of alkenes desorption evidenced that Cu + ions of stronger electron donor properties bond alkenes stronger than less electron donor ones. It suggests that π back donation has more important contribution to the strength of bonding alkenes to cation than π donation.

  19. Evidence for a novel chemisorption bond: Formate (HCO/sub 2/) on Cu(100)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Stoehr, J.; Outka, D.A.; Madix, R.J.

    1985-03-25

    Surface extended-x-ray-absorption fine-structure measurements reveal that formate (HCO/sub 2/) groups on Cu(100) chemisorb via the two oxygen atoms in adjacent fourfold hollow sites with an average O-Cu nearest-neighbor bond length of 2.38 +- 0.03 A. This distance is sig- nificantly (approx.0.4 A) longer than typical O-Cu bonds in bulk compounds and all known surface complexes. The unusually large O-Cu distance is attributed to a steric effect involving the C atom in HCO/sub 2/ and the nearest-neighbor Cu surface atoms.

  20. X-ray absorption edge spectroscopy and computational studies on LCuO2 species: Superoxide-Cu(II) versus peroxide-Cu(III) bonding.

    PubMed

    Sarangi, Ritimukta; Aboelella, Nermeen; Fujisawa, Kiyoshi; Tolman, William B; Hedman, Britt; Hodgson, Keith O; Solomon, Edward I

    2006-06-28

    The geometric and electronic structures of two mononuclear CuO2 complexes, [Cu(O2){HB(3-Ad-5-(i)Prpz)3}] (1) and [Cu(O2)(beta-diketiminate)] (2), have been evaluated using Cu K- and L-edge X-ray absorption spectroscopy (XAS) studies in combination with valence bond configuration interaction (VBCI) simulations and spin-unrestricted broken symmetry density functional theory (DFT) calculations. Cu K- and L-edge XAS data indicate the Cu(II) and Cu(III) nature of 1 and 2, respectively. The total integrated intensity under the L-edges shows that the 's in 1 and 2 contain 20% and 28% Cu character, respectively, indicative of very covalent ground states in both complexes, although more so in 1. Two-state VBCI simulations also indicate that the ground state in 2 has more Cu (/3d8) character. DFT calculations show that the in both complexes is dominated by O2(n-) character, although the O2(n-) character is higher in 1. It is shown that the ligand L plays an important role in modulating Cu-O2 bonding in these LCuO2 systems and tunes the ground states of 1 and 2 to have dominant Cu(II)-superoxide-like and Cu(III)-peroxide-like character, respectively. The contributions of ligand field (LF) and the charge on the absorbing atom in the molecule (Q(mol)M) to L- and K-edge energy shifts are evaluated using DFT and time-dependent DFT calculations. It is found that LF makes a dominant contribution to the edge energy shift, while the effect of Q(mol)M is minor. The charge on the Cu in the Cu(III) complex is found to be similar to that in Cu(II) complexes, which indicates a much stronger interaction with the ligand, leading to extensive charge transfer.

  1. In Situ Study of Reduction Process of CuO Paste and Its Effect on Bondability of Cu-to-Cu Joints

    NASA Astrophysics Data System (ADS)

    Yao, Takafumi; Matsuda, Tomoki; Sano, Tomokazu; Morikawa, Chiaki; Ohbuchi, Atsushi; Yashiro, Hisashi; Hirose, Akio

    2018-04-01

    A bonding method utilizing redox reactions of metallic oxide microparticles achieves metal-to-metal bonding in air, which can be alternative to lead-rich high-melting point solder. However, it is known that the degree of the reduction of metallic oxide microparticles have an influence on the joint strength using this bonding method. In this paper, the reduction behavior of CuO paste and its effect on Cu-to-Cu joints were investigated through simultaneous microstructure-related x-ray diffraction and differential scanning calorimetry measurements. The CuO microparticles in the paste were gradually reduced to submicron Cu2O particles at 210-250°C. Subsequently, Cu nanoparticles were generated instantaneously at 300-315°C. There was a marked difference in the strengths of the joints formed at 300°C and 350°C. Thus, the Cu nanoparticles play a critical role in sintering-based bonding using CuO paste. Furthermore, once the Cu nanoparticles have formed, the joint strength increases with higher bonding temperature (from 350°C to 500°C) and pressure (5-15 MPa), which can exceed the strength of Pb-5Sn solder at higher temperature and pressure.

  2. Highly charged swelling mica reduces free and extractable Cu levels in Cu-contaminated soils.

    PubMed

    Stuckey, Jason W; Neaman, Alexander; Ravella, Ramesh; Komarneni, Sridhar; Martínez, Carmen Enid

    2008-12-15

    Smelting of copper (Cu) results in the atmospheric deposition of Cu onto surrounding soils. Excess concentrations of Cu in soils can be absorbed by soil biota to toxic levels or leached into the groundwater, threatening the entire ecosystem. A means to restrict Cu mobility and uptake by plants is to remove it from the aqueous phase by applying an adsorptive material. A synthetic clay (highly charged swelling mica) was tested for its ability to decrease the levels of free and 0.1 M KNO3-extractable Cu in 15 surface soils from three different Cu mining areas in central Chile. The soils contained excessive total Cu levels (112-2790 mg Cu (kg soil)(-1)), while extractable Cu ranged from 0.3 to 22.9 mg Cu L(-1). The mica was applied to each soil at rates of 0.1%, 1%, and 2% (w/w). A 2% sodium-montmorillonite treatment and the nonamended soil served as controls. The order of treatment efficacy in reducing extractable Cu and free Cu2+ for low pH soils ( 1% mica > 2% montmorillonite > 0.1% mica. At 120 days, the 2% mica treatment maintained reductions of up to 93% in the free Cu2+ activity and up to 75% in the extractable Cu concentration upon acidification to the original soil pH value. In addition, Cu retention in mica-treated soils was more resistant to acidification than in lime-treated soils. This mica has promise for the remediation of acidic soils with metal contamination at the surface.

  3. Near-neighbor mixing and bond dilation in mechanically alloyed Cu-Fe

    NASA Astrophysics Data System (ADS)

    Harris, V. G.; Kemner, K. M.; Das, B. N.; Koon, N. C.; Ehrlich, A. E.; Kirkland, J. P.; Woicik, J. C.; Crespo, P.; Hernando, A.; Garcia Escorial, A.

    1996-09-01

    Extended x-ray-absorption fine-structure (EXAFS) measurements were used to obtain element-specific, structural, and chemical information of the local environments around Cu and Fe atoms in high-energy ball-milled CuxFe1-x samples (x=0.50 and 0.70). Analysis of the EXAFS data shows both Fe and Cu atoms reside in face-centered-cubic sites where the first coordination sphere consists of a mixture of Fe and Cu atoms in a ratio which reflects the as-prepared stoichiometry. The measured bond distances indicate a dilation in the bonds between unlike neighbors which accounts for the lattice expansion measured by x-ray diffraction. These results indicate that metastable alloys having a positive heat of mixing can be prepared via the high-energy ball-milling process.

  4. Low-temperature direct copper-to-copper bonding enabled by creep on (111) surfaces of nanotwinned Cu

    PubMed Central

    Liu, Chien-Min; Lin, Han-Wen; Huang, Yi-Sa; Chu, Yi-Cheng; Chen, Chih; Lyu, Dian-Rong; Chen, Kuan-Neng; Tu, King-Ning

    2015-01-01

    Direct Cu-to-Cu bonding was achieved at temperatures of 150–250 °C using a compressive stress of 100 psi (0.69 MPa) held for 10–60 min at 10−3 torr. The key controlling parameter for direct bonding is rapid surface diffusion on (111) surface of Cu. Instead of using (111) oriented single crystal of Cu, oriented (111) texture of extremely high degree, exceeding 90%, was fabricated using the oriented nano-twin Cu. The bonded interface between two (111) surfaces forms a twist-type grain boundary. If the grain boundary has a low angle, it has a hexagonal network of screw dislocations. Such network image was obtained by plan-view transmission electron microscopy. A simple kinetic model of surface creep is presented; and the calculated and measured time of bonding is in reasonable agreement. PMID:25962757

  5. Characterization and Modeling of Fine-Pitch Copper Ball Bonding on a Cu/Low- k Chip

    NASA Astrophysics Data System (ADS)

    Che, F. X.; Wai, L. C.; Zhang, Xiaowu; Chai, T. C.

    2015-02-01

    Cu ball bonding faces more challenges than Au ball bonding, for example, excessive deformation of the bond pad and damage of Cu/low- k structures, because of the much greater hardness of Cu free air balls. In this study, dynamic finite-element analysis (FEA) modeling with displacement control was developed to simulate the ball-bonding process. The three-dimensional (3D) FEA simulation results were confirmed by use of stress-measurement data, obtained by use of stress sensors built into the test chip. Stress comparison between two-dimensional (2D) and 3D FEA models showed the 2D plain strain model to be a reasonable and effective model for simulation of the ball-bonding process without loss of accuracy; it also saves computing resources. The 2D FEA model developed was then used in studies of a Cu/low- k chip to find ways of reducing Al bond pad deformation and stresses of low- k structures. The variables studied included Al pad properties, capillary geometry, bond pad design (Al pad thickness, Al pad coated with Ni layer), and the effect of ultrasonic bonding power.

  6. Analysis of the bonding in XH3Cu+ (XB, Al, Ga) complexes

    NASA Astrophysics Data System (ADS)

    Corral, Inés; Mó, Otilia; Yáñez, Manuel

    High-level density functional theory (DFT) calculations on XH3Cu+ (XB, Al, Ga) complexes show that the attachment of the metal cation to the base takes place through agostic-type interactions. These interactions that can be viewed as dative bonds from the σXH bonding orbitals of the base toward low-lying empty 4s orbitals of the metal cation, and back-donations from the lone pairs of the metal into the σ *XH antibonding orbitals of the neutral, are particularly favored when the XH bonds have a high X+δH-δ polarity. Accordingly, the AlH3 and GaH3 Cu+ binding energies are very similar, but much larger than that of BH3. Depopulation of the σXH bonding orbital and the concomitant population of the σ *XH antibonding orbital involved in the agostic interaction result in a significant weakening of the corresponding XH linkages, whose bond length increases and whose stretching frequency appears red-shifted.

  7. Hydrogen bonding in basic copper salts: a spectroscopic study of malachite, Cu2(OH)2CO3, and brochantite, Cu4(OH)6SO4

    NASA Astrophysics Data System (ADS)

    Schmidt, M.; Lutz, H. D.

    1993-05-01

    Infrared and Raman spectra of the basic copper salts malachite, Cu2(OH)2CO3, and brochantite, Cu4(OH)6SO4, as well as of deuterated and 13C substituted samples are presented and discussed in terms of group theory and the hydrogen bonds present. The main results are that (i) the hydrogen donor strengths of the OH- ions are strongly increased due to the very great synergetic effect of the copper ions, (ii) the acceptor strengths of the H-bond acceptor groups (SO4 2-, CO3 2-, and OH- ions) are significantly modified by the linkage and coordination of the acceptor atoms — this complicates true assignment of the OH bands observed to the two and six different OH- ions present in malachite and brochantite, respectively -, and (iii) the Cu — O stretching modes at 430 590 cm-1 and 420 520 cm-1 for malachite and brochantite, respectively, exhibit strong, partially covalent Cu — O bonding.

  8. Wafer-to-wafer bonding of nonplanarized MEMS surfaces using solder

    NASA Astrophysics Data System (ADS)

    Sparks, D.; Queen, G.; Weston, R.; Woodward, G.; Putty, M.; Jordan, L.; Zarabadi, S.; Jayakar, K.

    2001-11-01

    The fabrication and reliability of a solder wafer-to-wafer bonding process is discussed. Using a solder reflow process allows vacuum packaging to be accomplished with unplanarized complementary metal-oxide semiconductor (CMOS) surface topography. This capability enables standard CMOS processes, and integrated microelectromechanical systems devices to be packaged at the chip-level. Alloy variations give this process the ability to bond at lower temperatures than most alternatives. Factors affecting hermeticity, shorts, Q values, shifting cavity pressure, wafer saw cleanliness and corrosion resistance will be covered.

  9. TPD IR studies of CO desorption from zeolites CuY and CuX

    NASA Astrophysics Data System (ADS)

    Datka, Jerzy; Kozyra, Paweł

    2005-06-01

    The desorption of CO from zeolites CuY and CuX was followed by TPD-IR method. This is a combination of temperature programmed desorption and IR spectroscopy. In this method, the status of activated zeolite (before adsorption), the process of adsorption, and the status of adsorbed molecules can be followed by IR spectroscopy, and the process of desorption (with linear temperature increase) can be followed both by IR spectroscopy and by mass spectrometry. IR spectra have shown two kinds of Cu + sites in both CuY and CuX. Low frequency (l.f.) band (2140 cm -1 in CuY and 2130 cm -1 in CuX) of adsorbed CO represents Cu + sites for which π back donation is stronger and σ donation is weaker whereas high frequency h.f. band (2160 cm -1 in CuY and 2155 cm -1 in CuX) represent Cu + sites for which π back donation is weaker and σ donation is stronger. The TPD-IR experiments evidenced that the Cu + sites represented by l.f. band bond CO more weakly than those represented by h.f. one, indicating that σ donation has more important impact to the strength of Cu +-CO bonding. On the contrary, π back donation has bigger contribution to the activation of adsorbed molecules.

  10. Strain relaxation in nm-thick Cu and Cu-alloy films bonded to a rigid substrate

    NASA Astrophysics Data System (ADS)

    Herrmann, Ashley Ann Elizabeth

    In the wide scope of modern technology, nm-thick metallic films are increasingly used as lubrication layers, optical coatings, plating seeds, diffusion barriers, adhesion layers, metal contacts, reaction catalyzers, etc. A prominent example is the use of nm-thick Cu films as electroplating seed layers in the manufacturing of integrated circuits (ICs). These high density circuits are linked by on-chip copper interconnects, which are manufactured by filling Cu into narrow trenches by electroplating. The Cu fill by electroplating requires a thin Cu seed deposited onto high-aspect-ratio trenches. In modern ICs, these trenches are approaching 10 nm or less in width, and the seed layers less than 1 nm in thickness. Since nm-thick Cu seed layers are prone to agglomeration or delamination, achieving uniform, stable and highly-conductive ultra-thin seeds has become a major manufacturing challenge. A fundamental understanding of the strain behavior and thermal stability of nm-thick metal films adhered to a rigid substrate is thus critically needed. In this study, we focus on understanding the deformation modes of nm-thick Cu and Cu-alloy films bonded to a rigid Si substrate and under compressive stress. The strengthening of Cu films through alloying is also studied. In-situ transport measurements are used to monitor the deformation of such films as they are heated from room temperature to 400 °C. Ex-situ AFM is then used to help characterize the mode of strain relaxation. The relaxation modes are known to be sensitive to the wetting and adhesive properties of the film-substrate interface. We use four different liners (Ta, Ru, Mo and Co), interposed between the film and substrate to provide a wide range of interfacial properties to study their effect on the film's thermal stability. Our measurements indicate that when the film/liner interfacial energy is low, grain growth is the dominant relaxation mechanism. As the interface energy increases, grain growth is suppressed, and

  11. Atomic resolution chemical bond analysis of oxygen in La2CuO4

    NASA Astrophysics Data System (ADS)

    Haruta, M.; Nagai, T.; Lugg, N. R.; Neish, M. J.; Nagao, M.; Kurashima, K.; Allen, L. J.; Mizoguchi, T.; Kimoto, K.

    2013-08-01

    The distorted CuO6 octahedron in La2CuO4 was studied using aberration-corrected scanning transmission electron microscopy at atomic resolution. The near-edge structure in the oxygen K-edge electron energy-loss spectrum was recorded as a function of the position of the electron probe. After background subtraction, the measured spectrum image was processed using a recently developed inversion process to remove the mixing of signals on the atomic columns due to elastic and thermal scattering. The spectra were then compared with first-principles band structure calculations based on the local-density approximation plus on-site Coulomb repulsion (LDA + U) approach. In this article, we describe in detail not only anisotropic chemical bonding of the oxygen 2p state with the Cu 3d state but also with the Cu 4p and La 5d/4f states. Furthermore, it was found that buckling of the CuO2 plane was also detectable at the atomic resolution oxygen K-edge. Lastly, it was found that the effects of core-hole in the O K-edge were strongly dependent on the nature of the local chemical bonding, in particular, whether it is ionic or covalent.

  12. X-ray Absorption Spectroscopic and Theoretical Studies on (L)2[Cu2(S2)n]2+ Complexes: Disulfide Versus Disulfide(•1−) Bonding

    PubMed Central

    Sarangi, Ritimukta; York, John T.; Helton, Matthew E.; Fujisawa, Kiyoshi; Karlin, Kenneth D.; Tolman, William B.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

    2008-01-01

    Cu K-, L- and S K-edge X-ray absorption spectroscopic (XAS) data have been combined with density functional theory (DFT) calculations on [{(TMPA)Cu}2S2](ClO4)2 (1), [{Cu[HB(3,5-Pri2pz)3]}2(S2)] (2) and [{(TMEDA)Cu}2(S2)2](OTf)2 (3) to obtain a quantitative description of their ground state wavefunctions. The Cu L-edge intensities give 63% and 37% Cu d-character in the ground state of 1 and 2, respectively while the S K-pre-edge intensities reflect 20% and 48% S character in their ground states. These data indicate a more than two-fold increase in the total disulfide bonding character in 2 relative to 1. The increase in the number of Cu-S bonds in 2 (µ-η2:η2 S22− bridge) compared to 1 ((µ-η1:η1 S22− bridge), dominantly determines the large increase in covalency and Cu-disulfide bond strength in 2. Cu K- and L- and S K-pre-edge energy positions directly demonstrate the CuII/(S2−)2 nature of 3. The two disulfide(•1−)’s in 3 undergo strong bonding interactions which destabilize the resultant filled antibonding π* orbitals of the (S2−)2 fragment relative to the Cu 3d levels. This leads to an inverted bonding scheme in 3 with dominantly ligand based holes in its ground state, consistent with its description as a dicopper(II)-bis-disulfide(•1−) complex. PMID:18076173

  13. Effect Of Impurity On Cu Electromigration

    NASA Astrophysics Data System (ADS)

    Hu, C.-K.; Angyal, M.; Baker, B. C.; Bonilla, G.; Cabral, C.; Canaperi, D. F.; Choi, S.; Clevenger, L.; Edelstein, D.; Gignac, L.; Huang, E.; Kelly, J.; Kim, B. Y.; Kyei-Fordjour, V.; Manikonda, S. L.; Maniscalco, J.; Mittal, S.; Nogami, T.; Parks, C.; Rosenberg, R.; Simon, A.; Xu, Y.; Vo, T. A.; Witt, C.

    2010-11-01

    The impact of the existence of Cu grain boundaries on the degradation of Cu interconnect lifetime at the 45 nm technology node and beyond has suggested that improved electromigra-tion in Cu grain boundaries has become increasingly important. In this paper, solute effects of non-metallic (C, Cl, O and S) and metallic (Al, Co, In, Mg, Sn, and Ti) impurities on Cu elec-tromigration were investigated. The Cu alloy interconnects were fabricated by adjusting Cu electroplating solutions or by depositing a Cu alloy seed, a thin film layer of impurity, an alloy liner, or a metal cap. A large variation of Cu grain structure in the samples was achieved by adjusting the wafer fabrication process steps. The non-metallic impurities were found to be less than 0.1% in the electroplated Cu with no effect on Cu electromigration lifetimes. Most of the metallic impurities reduced Cu interface and grain boundary mass flows and enhanced Cu lifetime, but Al, Co, and Mg impurities did not mitigate Cu grain boundary diffusion.

  14. Synthesis of CuO by Cu-CPPs with the determination of Cu(II) coordination modes from a novel complex of [Cu(terpyOH){sub 2}]·(HBTC)·2H{sub 2}O

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang, Yu, E-mail: wangyu1012@hit.edu.cn; Chen, Gang, E-mail: gchen@hit.edu.cn; Han, Li

    2013-10-15

    In this study, we investigated the synthesis of CuO microrods by simple calcination of copper-based coordination polymer particles (Cu-CPPs) at high temperature in air. The photocatalytic activity of the CuO microrods was tested by the decomposition of aqueous solution of RhB, which was completely decomposed by irradiation with light. To analyze the relationship of metal ions and ligands in the Cu-CPPs, the single crystal of [Cu(terpyOH){sub 2}]∙(HBTC)∙2H{sub 2}O (1) (terpyOH=4′-hydroxy-2,2′:6′,2″-terpyridine, BTC=1,3,5-benzene tricarboxylate) was first prepared and characterized by X-ray single crystal structural analysis. A variety of hydrogen bonds constructing the 3D complex structure in [Cu(terpyOH){sub 2}]∙(HBTC)∙2H{sub 2}O (1) were observed.more » - Graphical abstract: Demonstrating a general method to synthesize CuO microrods via simple calcination of Cu-CPPs and Cu(II) coordination modes from a novel complex of [Cu(terpyOH){sub 2}]∙(HBTC)·2H{sub 2}O constructed by hydrogen bonding. Display Omitted - Highlights: • The formation of microrods CuO from thermal treatment of Cu-CPPs through an “escape-by-crafty-scheme” strategy has been studied. • Determination of Cu(II) coordination modes in Cu-CPPs from a novel complex of [Cu(terpyOH){sub 2}]∙(HBTC) 2H{sub 2}O. • Invested the behave of hydrogen bonding to construct the 3D complex structure. • Commendable photodegradation performance was observed.« less

  15. Local Environment Sensitivity of the Cu K-Edge XANES Features in Cu-SSZ-13: Analysis from First-Principles.

    PubMed

    Zhang, Renqin; McEwen, Jean-Sabin

    2018-05-22

    Cu K-edge X-ray absorption near-edge spectra (XANES) have been widely used to study the properties of Cu-SSZ-13. In this Letter, the sensitivity of the XANES features to the local environment for a Cu + cation with a linear configuration and a Cu 2+ cation with a square-linear configuration in Cu-SSZ-13 is reported. When a Cu + cation is bonded to H 2 O or NH 3 in a linear configuration, the XANES has a strong peak at around 8983 eV. The intensity of this peak decreases as the linear configuration is broken. As for the Cu 2+ cations in a square-planar configuration with a coordination number of 4, two peaks at around 8986 and 8993 eV are found. An intensity decrease for both peaks at around 8986 and 8993 eV is found in an NH 3 _4_Z 2 Cu model as the N-Cu-N angle changes from 180 to 100°. We correlate these features to the variation of the 4p state by PDOS analysis. In addition, the feature peaks for both the Cu + cation and Cu 2+ cation do not show a dependence on the Cu-N bond length. We further show that the feature peaks also change when the coordination number of the Cu cation is varied, while these feature peaks are independent of the zeolite topology. These findings help elucidate the experimental XANES features at an atomic and an electronic level.

  16. Application of Au-Sn eutectic bonding in hermetic radio-frequency microelectromechanical system wafer level packaging

    NASA Astrophysics Data System (ADS)

    Wang, Qian; Choa, Sung-Hoon; Kim, Woonbae; Hwang, Junsik; Ham, Sukjin; Moon, Changyoul

    2006-03-01

    Development of packaging is one of the critical issues toward realizing commercialization of radio-frequency-microelectromechanical system (RF-MEMS) devices. The RF-MEMS package should be designed to have small size, hermetic protection, good RF performance, and high reliability. In addition, packaging should be conducted at sufficiently low temperature. In this paper, a low-temperature hermetic wafer level packaging scheme for the RF-MEMS devices is presented. For hermetic sealing, Au-Sn eutectic bonding technology at temperatures below 300°C is used. Au-Sn multilayer metallization with a square loop of 70 µm in width is performed. The electrical feed-through is achieved by the vertical through-hole via filling with electroplated Cu. The size of the MEMS package is 1 mm × 1 mm × 700 µm. The shear strength and hermeticity of the package satisfies the requirements of MIL-STD-883F. Any organic gases or contamination are not observed inside the package. The total insertion loss for the packaging is 0.075 dB at 2 GHz. Furthermore, the robustness of the package is demonstrated by observing no performance degradation and physical damage of the package after several reliability tests.

  17. Bonding in d9 complexes derived from EPR: Application to CuCl2-4, CuBr2-4, and CdCl2:Cu2+

    NASA Astrophysics Data System (ADS)

    Aramburu, J. A.; Moreno, M.

    1985-12-01

    In this work are reported the theoretical expressions for the [g], hyperfine, and superhyperfine (shf) tensors of a d9 square-planar complex within a molecular orbital (MO) scheme. These expressions include contributions arising from crystal field and charge transfer excitations calculated up to third and second order perturbations, respectively. This makes the present framework more general than those previously used. Through those expressions we have derived from the experimental EPR and optical data the MO coefficients corresponding to the valence b1g(x2-y2), b2g(xy), and eg(xz,yz) levels and also the core polarization contribution K to the hyperfine tensor for the systems CuCl2-4, CuBr2-4, and CdCl2:Cu2+. The 3d charge obtained for CuCl2-4 is equal to 0.61, 0.83, and 0.85 for the antibonding 3b1g, 2b2g, and 2eg levels, respectively. These figures are much closer to the Xα results by Bencini and Gatteschi [J. Am. Chem. Soc. 105, 5535 (1983)] than to those by Desjardins et al. [J. Am. Chem. Soc. 105, 4590 (1983)]. The σ and π covalency for CuBr2-4 are both higher than for CuCl2-4 in accord to the lower electronegativity for bromine. However, only for the antibonding 3b1g level of CuBr2-4 have we obtained an electronic charge lying mainly on ligands. The covalency of CdCl2:Cu2+ is smaller than that found for CuCl2-4, a fact associated to a higher metal-ligand distance for the former. Evidence of this statement are also given from the analysis of crystal-field spectra and isotropic shf constant. The values of K derived for CuCl2-4 (128.1×10-4 cm-1), CuBr2-4 (103.6×10-4 cm-1), and CdCl2:Cu2+ (123.9×10-4 cm-1) point out the dependence of K on the equatorial covalency but also on the existence of axial ligands. The [g] tensor of CuBr2-4 is dominated by the charge transfer contribution while the crystal field one is negative. Finally an analysis of the importance of each one of the involved contributions to the spin-Hamiltonian parameters is reported for the

  18. Influence of Cu Content on the Microstructure and Mechanical Properties of Cr-Cu-N Coatings

    PubMed Central

    Ding, Ji Cheng; Zhang, Teng Fei; Wan, Zhi Xin; Mei, Hai Juan; Kang, Myung Chang

    2018-01-01

    The Cr-Cu-N coatings with various Cu contents (0–25.18 (±0.17) at.%) were deposited on Si wafer and stainless steel (SUS 304) substrates in reactive Ar+N2 gas mixture by a hybrid coating system combining pulsed DC and RF magnetron sputtering techniques. The influence of Cu content on the coating composition, microstructure, and mechanical properties was investigated. The microstructure of the coatings was significantly altered by the introduction of Cu. The deposited coatings exhibit solid solution structure with different compositions in all of the samples. Addition of Cu is intensively favored for preferred orientation growth along (200) direction by restricting in (111) direction. With increasing Cu content, the surface and cross-sectional morphology of coatings were changed from triangle cone-shaped, columnar feature to broccoli-like and compact glassy microstructure, respectively. The mechanical properties including the residual stress, nanohardness, and toughness of the coatings were explored on the basis of Cu content. The highest hardness was obtained at the Cu content of 1.49 (±0.10) at.%. PMID:29552269

  19. Influence of Cu Content on the Microstructure and Mechanical Properties of Cr-Cu-N Coatings.

    PubMed

    Ding, Ji Cheng; Zhang, Teng Fei; Wan, Zhi Xin; Mei, Hai Juan; Kang, Myung Chang; Wang, Qi Min; Kim, Kwang Ho

    2018-01-01

    The Cr-Cu-N coatings with various Cu contents (0-25.18 (±0.17) at.%) were deposited on Si wafer and stainless steel (SUS 304) substrates in reactive Ar+N 2 gas mixture by a hybrid coating system combining pulsed DC and RF magnetron sputtering techniques. The influence of Cu content on the coating composition, microstructure, and mechanical properties was investigated. The microstructure of the coatings was significantly altered by the introduction of Cu. The deposited coatings exhibit solid solution structure with different compositions in all of the samples. Addition of Cu is intensively favored for preferred orientation growth along (200) direction by restricting in (111) direction. With increasing Cu content, the surface and cross-sectional morphology of coatings were changed from triangle cone-shaped, columnar feature to broccoli-like and compact glassy microstructure, respectively. The mechanical properties including the residual stress, nanohardness, and toughness of the coatings were explored on the basis of Cu content. The highest hardness was obtained at the Cu content of 1.49 (±0.10) at.%.

  20. Formation of [Cu 2 O 2 ] 2+ and [Cu 2 O] 2+ toward C–H Bond Activation in Cu-SSZ-13 and Cu-SSZ-39

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ipek, Bahar; Wulfers, Matthew J.; Kim, Hacksung

    Cu-exchanged small-pore zeolites (CHA and AEI) form methanol from methane (>95% selectivity) using a 3-step cyclic procedure (Wulfers et al. Chem. Commun. 2015, 51, 4447-4450) with methanol amounts higher than Cu-ZSM-5 and Cu-mordenite on a per gram and per Cu basis. Here, the CuxOy species formed on Cu-SSZ-13 and Cu-SSZ-39 following O2 or He activation at 450 °C are identified as trans-μ-1,2-peroxo dicopper(II) ([Cu2O2]2+) and mono-(μ-oxo) dicopper(II) ([Cu2O]2+) using synchrotron X-ray diffraction, in situ UV–vis, and Raman spectroscopy and theory. [Cu2O2]2+ and [Cu2O]2+ formed on Cu-SSZ-13 showed ligand-to-metal charge transfer (LMCT) energies between 22,200 and 35,000 cm–1, Cu–O vibrations atmore » 360, 510, 580, and 617 cm–1 and an O–O vibration at 837 cm–1. The vibrations at 360, 510, 580, and 837 cm–1 are assigned to the trans-μ-1,2-peroxo dicopper(II) species, whereas the Cu–O vibration at 617 cm–1 (Δ18O = 24 cm–1) is assigned to a stretching vibration of a thermodynamically favored mono-(μ-oxo) dicopper(II) with a Cu–O–Cu angle of 95°. On the basis of the intensity loss of the broad LMCT band between 22,200 and 35,000 cm–1 and Raman intensity loss at 571 cm–1 upon reaction, both the trans-μ-1,2-peroxo dicopper(II) and mono-(μ-oxo) dicopper(II) species are suggested to take part in methane activation at 200 °C with the trans-μ-1,2-peroxo dicopper(II) core playing a dominant role. A relationship between the [Cu2Oy]2+ concentration and Cu(II) at the eight-membered ring is observed and related to the concentration of [CuOH]+ suggested as an intermediate in [Cu2Oy]2+ formation.« less

  1. Bonding Cu to Al2O3 with Bi-B-Zn Oxide Glass Via Oxidation-Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Chen, Jianqiang; Li, Yufeng; Miao, Weiliang; Mai, Chengle; Li, Mingyu

    2018-01-01

    Bonding Cu on Al2O3 is a key and difficult technology applied in high-power semiconductor devices. A method proposed in this work investigates bonding with a kind of Bi-B-Zn oxide glass powder paste as a solder. Oxidation-reduction reactions between the Cu plate and the solder took place and generated Bi metal during the joining procedure. With an increase in the joining temperature, the tensile strength increased due to the increase of Bi metal formation. The Bi metal played an important role in joining Cu and Al2O3 because of its much better wettability on Cu than that of the oxides. A compound ZnAl2O4 was observed to form between the Al2O3 ceramic and oxide layer, which strengthened the bond.

  2. Comparative Reliability Studies and Analysis of Au, Pd-Coated Cu and Pd-Doped Cu Wire in Microelectronics Packaging

    PubMed Central

    Chong Leong, Gan; Uda, Hashim

    2013-01-01

    This paper compares and discusses the wearout reliability and analysis of Gold (Au), Palladium (Pd) coated Cu and Pd-doped Cu wires used in fineline Ball Grid Array (BGA) package. Intermetallic compound (IMC) thickness measurement has been carried out to estimate the coefficient of diffusion (Do) under various aging conditions of different bonding wires. Wire pull and ball bond shear strengths have been analyzed and we found smaller variation in Pd-doped Cu wire compared to Au and Pd-doped Cu wire. Au bonds were identified to have faster IMC formation, compared to slower IMC growth of Cu. The obtained weibull slope, β of three bonding wires are greater than 1.0 and belong to wearout reliability data point. Pd-doped Cu wire exhibits larger time-to-failure and cycles-to-failure in both wearout reliability tests in Highly Accelerated Temperature and Humidity (HAST) and Temperature Cycling (TC) tests. This proves Pd-doped Cu wire has a greater potential and higher reliability margin compared to Au and Pd-coated Cu wires. PMID:24244344

  3. NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction

    DOE PAGES

    Shan, Junjun; Liu, Jilei; Li, Mengwei; ...

    2017-12-29

    Here, NiCu single atom alloy (SAA) nanoparticles supported on silica are reported to catalyze the non-oxidative dehydrogenation of ethanol, selectively to acetaldehyde and hydrogen products by facilitating the C—H bond cleavage. The activity and selectivity of the NiCu SAA catalysts were compared to monometallic copper and to PtCu and PdCu single atom alloys, in a flow reactor at moderate temperatures. In-situ DRIFTS showed that the silica support facilitates the O—H bond cleavage of ethanol to form ethoxy intermediates over all the supported alloy catalysts. However, these remain unreactive up to 250°C for the Cu/SiO 2 monometallic nanoparticles, while in themore » NiCu SAA, acetaldehyde is formed at much lower temperatures, below 150°C. In situ DRIFTS was also used to identify the C—H activation step as the rate determining step of this reaction on all the copper catalysts we examined. The presence of atomically dispersed Ni in Cu significantly lowers the C—H bond activation barrier, whereas Pt and Pd atoms were found less effective. This work provides direct evidence that the C—H bond cleavage is the rate determining step in ethanol dehydrogenation over this type catalyst.« less

  4. NiCu single atom alloys catalyze the C—H bond activation in the selective non- oxidative ethanol dehydrogenation reaction

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shan, Junjun; Liu, Jilei; Li, Mengwei

    Here, NiCu single atom alloy (SAA) nanoparticles supported on silica are reported to catalyze the non-oxidative dehydrogenation of ethanol, selectively to acetaldehyde and hydrogen products by facilitating the C—H bond cleavage. The activity and selectivity of the NiCu SAA catalysts were compared to monometallic copper and to PtCu and PdCu single atom alloys, in a flow reactor at moderate temperatures. In-situ DRIFTS showed that the silica support facilitates the O—H bond cleavage of ethanol to form ethoxy intermediates over all the supported alloy catalysts. However, these remain unreactive up to 250°C for the Cu/SiO 2 monometallic nanoparticles, while in themore » NiCu SAA, acetaldehyde is formed at much lower temperatures, below 150°C. In situ DRIFTS was also used to identify the C—H activation step as the rate determining step of this reaction on all the copper catalysts we examined. The presence of atomically dispersed Ni in Cu significantly lowers the C—H bond activation barrier, whereas Pt and Pd atoms were found less effective. This work provides direct evidence that the C—H bond cleavage is the rate determining step in ethanol dehydrogenation over this type catalyst.« less

  5. Ab-initio atomic level stress and role of d-orbitals in CuZr, CuZn and CuY

    NASA Astrophysics Data System (ADS)

    Ojha, Madhusudan; Nicholson, Don M.; Egami, Takeshi

    2015-03-01

    Atomic level stress offers a new tool to characterize materials within the local approximation to density functional theory (DFT). Ab-initio atomic level stresses in B2 structures of CuZr, CuZn and CuY are calculated and results are explained on the basis of d-orbital contributions to Density of States (DOS). The overlap of d-orbital DOS plays an important role in the relative magnitude of atomic level stresses in these structures. The trends in atomic level stresses that we observed in these simple B2 structures are also seen in complex structures such as liquids, glasses and solid solutions. The stresses are however modified by the different coordination and relaxed separation distances in these complex structures. We used the Locally Self-Consistent Multiple Scattering (LSMS) code and Vienna Ab-initio Simulation Package (VASP) for ab-initio calculations.

  6. Cu-Sn Intermetallic Compound Joints for High-Temperature Power Electronics Applications

    NASA Astrophysics Data System (ADS)

    Lee, Byung-Suk; Yoon, Jeong-Won

    2018-01-01

    Cu-Sn solid-liquid interdiffusion (SLID) bonded joints were fabricated using a Sn-Cu solder paste and Cu for high-temperature power electronics applications. The interfacial reaction behaviors and the mechanical properties of Cu6Sn5 and Cu3Sn SLID-bonded joints were compared. The intermetallic compounds formed at the interfaces in the Cu-Sn SLID-bonded joints significantly affected the die shear strength of the joint. In terms of thermal and mechanical properties, the Cu3Sn SLID-bonded joint was superior to the conventional solder and the Cu6Sn5 SLID-bonded joints.

  7. CuCrZr alloy microstructure and mechanical properties after hot isostatic pressing bonding cycles

    NASA Astrophysics Data System (ADS)

    Frayssines, P.-E.; Gentzbittel, J.-M.; Guilloud, A.; Bucci, P.; Soreau, T.; Francois, N.; Primaux, F.; Heikkinen, S.; Zacchia, F.; Eaton, R.; Barabash, V.; Mitteau, R.

    2014-04-01

    ITER first wall (FW) panels are a layered structure made of the three following materials: 316L(N) austenitic stainless steel, CuCrZr alloy and beryllium. Two hot isostatic pressing (HIP) cycles are included in the reference fabrication route to bond these materials together for the normal heat flux design supplied by the European Union (EU). This reference fabrication route ensures sufficiently good mechanical properties for the materials and joints, which fulfil the ITER mechanical specifications, but often results in a coarse grain size for the CuCrZr alloy, which is not favourable, especially, for the thermal creep properties of the FW panels. To limit the abnormal grain growth of CuCrZr and make the ITER FW fabrication route more reliable, a study began in 2010 in the EU in the frame of an ITER task agreement. Two material fabrication approaches have been investigated. The first one was dedicated to the fabrication of solid CuCrZr alloy in close collaboration with an industrial copper alloys manufacturer. The second approach investigated was the manufacturing of CuCrZr alloy using the powder metallurgy (PM) route and HIP consolidation. This paper presents the main mechanical and microstructural results associated with the two CuCrZr approaches mentioned above. The mechanical properties of solid CuCrZr, PM CuCrZr and joints (solid CuCrZr/solid CuCrZr and solid CuCrZr/316L(N) and PM CuCrZr/316L(N)) are also presented.

  8. Composition dependence of the in-plane Cu-O bond-stretching LO phonon mode in YBa2Cu3O6+x

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Stercil, F.; Egami, T.; Mook Jr, Herbert A

    An inelastic pulsed neutron scattering study was performed on the dependence of the dispersion and spectral intensity of the in-plane Cu-O bond-stretching LO phonon mode on doped charge density. The measurements were made in the time-of-flight mode with the multiangle position sensitive spectrometer of the ISIS facility on single crystals of YBa{sub 2}Cu{sub 3}O{sub 6+x} (x=0.15, 0.35, 0.6, 0.7, and 0.95). The focus of the study is the in-plane Cu-O bond-stretching LO phonon mode, which is known for strong electron-phonon coupling and unusual dependence on composition and temperature. It is shown that the dispersions for the samples with x=0.35, 0.6,more » and 0.7 are similar to the superposition of those for x=0.15 and 0.95 samples, and cannot be explained in terms of the structural anisotropy. It is suggested that the results are consistent with the model of nanoscale electronic phase separation, with the fraction of the phases being dependent on the doped charge density.« less

  9. Improved Epitaxy and Surface Morphology in YBa2Cu3Oy Thin Films Grown on Double Buffered Si Wafers

    NASA Astrophysics Data System (ADS)

    Gao, J.; Kang, L.; Wong, H. Y.; Cheung, Y. L.; Yang, J.

    Highly epitaxial thin films of YBCO have been obtained on silicon wafers using a Eu2CuO4/YSZ (yttrium-stabilized ZrO2) double buffer. Our results showed that application of such a double buffer can significantly enhance the epitaxy of grown YBCO. It also leads to an excellent surface morphology. The average surface roughness was found less than 5 nm in a large range. The results of X-ray small angle reflection and positron spectroscpy demonstrate a very clear and flat interface between YBCO and buffer layers. The Eu2CuO4/YSZ double buffer could be promising for coating high-TC superconducting films on various reactive substrates.

  10. The local environment of Cu+ in Cu-Y zeolite and its relationship to the synthesis of dimethyl carbonate.

    PubMed

    Drake, Ian J; Zhang, Yihua; Briggs, Daniel; Lim, Bomyi; Chau, Tanguy; Bell, Alexis T

    2006-06-22

    Cu-exchanged Y zeolite was investigated in order to determine the location of the copper cations relative to the zeolite framework and to determine which Cu cations are active for the oxidative carbonylation of methanol to dimethyl carbonate (DMC). Cu-Y zeolite was prepared by vapor-phase exchange of H-Y with CuCl. The oxidation state, local coordination, and bond distances of Al and Cu were determined using Al K-edge and Cu K-edge X-ray absorption spectroscopy (XAS). Complimentary information was obtained by H2 temperature-programmed reduction and by in-situ infrared spectroscopy. Cu-Y has a Cu/Al ratio of unity and very little occluded CuCl. The average Al-O and Al-Cu bond distances are 1.67 angstroms and 2.79 angstroms, respectively, and the average Cu-O and Cu-Si(Al) bond distances are 1.99 angstroms and 3.13 angstroms, respectively. All of the Cu exchanged is present as Cu+ in sites I', II, and III'. Cu-Y is active for the oxidative carbonylation of methanol, and at low reactant contact time produces DMC as the primary product. With increasing reactant contact time, DMC formation decreases in preference to the formation of dimethoxy methane (DMM) and methylformate (MF). The formation of DMM and MF is attributed to the hydrogenation of DMC and the hydrogenolysis of DMM, respectively. Observation of the catalyst under reaction conditions reveals that most of the copper cations remain as Cu+, but some oxidation of Cu+ to Cu2+ does occur. It is also concluded that only those copper cations present in site II and III' positions are accessible to the reactants, and hence are catalytically active. The dominant adsorbed species on the surface are methoxy groups, and adsorbed CO is present as a minority species. The relationship of these observations to the kinetics of DMC synthesis is discussed.

  11. MEMS packaging with etching and thinning of lid wafer to form lids and expose device wafer bond pads

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chanchani, Rajen; Nordquist, Christopher; Olsson, Roy H

    In wafer-level packaging of microelectromechanical (MEMS) devices a lid wafer is bonded to a MEMS wafer in a predermined aligned relationship. Portions of the lid wafer are removed to separate the lid wafer into lid portions that respectively correspond in alignment with MEMS devices on the MEMS wafer, and to expose areas of the MEMS wafer that respectively contain sets of bond pads respectively coupled to the MEMS devices.

  12. An Alternative Cu-Based Bond Layer for Electric Arc Coating Process

    NASA Astrophysics Data System (ADS)

    Fadragas, Carlos R.; Morales, E. V.; Muñoz, J. A.; Bott, I. S.; Lariot Sánchez, C. A.

    2011-12-01

    A Cu-Al alloy has been used as bond coat between a carbon steel substrate and a final coating deposit obtained by applying the twin wire electric arc spraying coating technique. The presence of a copper-based material in the composite system can change the overall temperature profile during deposition because copper exhibits a thermal conductivity several times higher than that of the normally recommended bond coat materials (such as nickel-aluminum alloys or nickel-chromium alloys). The microstructures of 420 and 304 stainless steels deposited by the electric arc spray process have been investigated, focusing attention on the deposit homogeneity, porosity, lamellar structure, and microhardness. The nature of the local temperature gradient during deposition can strongly influence the formation of the final coating deposit. This study presents a preliminary study, undertaken to investigate the changes in the temperature profile which occur when a Cu-Al alloy is used as bond coat, and the possible consequences of these changes on the microstructure and adhesion of the final coating deposit. The influence of the thickness of the bond layer on the top coating temperature has also been also evaluated.

  13. Vertical integration of array-type miniature interferometers at wafer level by using multistack anodic bonding

    NASA Astrophysics Data System (ADS)

    Wang, Wei-Shan; Wiemer, Maik; Froemel, Joerg; Enderlein, Tom; Gessner, Thomas; Lullin, Justine; Bargiel, Sylwester; Passilly, Nicolas; Albero, Jorge; Gorecki, Christophe

    2016-04-01

    In this work, vertical integration of miniaturized array-type Mirau interferometers at wafer level by using multi-stack anodic bonding is presented. Mirau interferometer is suitable for MEMS metrology and for medical imaging according to its vertical-, lateral- resolutions and working distances. Miniaturized Mirau interferometer can be a promising candidate as a key component of an optical coherence tomography (OCT) system. The miniaturized array-type interferometer consists of a microlens doublet, a Si-based MEMS Z scanner, a spacer for focus-adjustment and a beam splitter. Therefore, bonding technologies which are suitable for heterogeneous substrates are of high interest and necessary for the integration of MEMS/MOEMS devices. Multi-stack anodic bonding, which meets the optical and mechanical requirements of the MOEMS device, is adopted to integrate the array-type interferometers. First, the spacer and the beam splitter are bonded, followed by bonding of the MEMS Z scanner. In the meanwhile, two microlenses, which are composed of Si and glass wafers, are anodically bonded to form a microlens doublet. Then, the microlens doublet is aligned and bonded with the scanner/spacer/beam splitter stack. The bonded array-type interferometer is a 7- wafer stack and the thickness is approximately 5mm. To separate such a thick wafer stack with various substrates, 2-step laser cutting is used to dice the bonded stack into Mirau chips. To simplify fabrication process of each component, electrical connections are created at the last step by mounting a Mirau chip onto a flip chip PCB instead of through wafer vias. Stability of Au/Ti films on the MEMS Z scanner after anodic bonding, laser cutting and flip chip bonding are discussed as well.

  14. Modeling of direct wafer bonding: Effect of wafer bow and etch patterns

    NASA Astrophysics Data System (ADS)

    Turner, K. T.; Spearing, S. M.

    2002-12-01

    Direct wafer bonding is an important technology for the manufacture of silicon-on-insulator substrates and microelectromechanical systems. As devices become more complex and require the bonding of multiple patterned wafers, there is a need to understand the mechanics of the bonding process. A general bonding criterion based on the competition between the strain energy accumulated in the wafers and the surface energy that is dissipated as the bond front advances is developed. The bonding criterion is used to examine the case of bonding bowed wafers. An analytical expression for the strain energy accumulation rate, which is the quantity that controls bonding, and the final curvature of a bonded stack is developed. It is demonstrated that the thickness of the wafers plays a large role and bonding success is independent of wafer diameter. The analytical results are verified through a finite element model and a general method for implementing the bonding criterion numerically is presented. The bonding criterion developed permits the effect of etched features to be assessed. Shallow etched patterns are shown to make bonding more difficult, while it is demonstrated that deep etched features can facilitate bonding. Model results and their process design implications are discussed in detail.

  15. Carbon tolerance of Ni-Cu and Ni-Cu/YSZ sub-μm sized SOFC thin film model systems

    NASA Astrophysics Data System (ADS)

    Götsch, Thomas; Schachinger, Thomas; Stöger-Pollach, Michael; Kaindl, Reinhard; Penner, Simon

    2017-04-01

    Thin films of YSZ, unsupported Ni-Cu 1:1 alloy phases and YSZ-supported Ni-Cu 1:1 alloy solutions have been reproducibly prepared by magnetron sputter deposition on Si wafers and NaCl(001) single crystal facets at two selected substrate temperatures of 298 K and 873 K. Subsequently, the layer properties of the resulting sub-μm thick thin films as well as the tendency towards carbon deposition following treatment in pure methane at 1073 K has been tested comparatively. Well-crystallized structures of cubic YSZ, cubic NiCu and cubic NiCu/YSZ have been obtained following deposition at 873 K on both substrates. Carbon is deposited on all samples following the trend Ni-Cu (1:1) = Ni-Cu (1:1)/YSZ > pure YSZ, indicating that at least the 1:1 composition of layered Ni-Cu alloy phases is not able to suppress the carbon deposition completely, rendering it unfavorable for usage as anode component in sub-μm sized fuel cells. It is shown that surfaces with a high Cu/Ni ratio nevertheless prohibit any carbon deposition.

  16. Low-temperature wafer-level gold thermocompression bonding: modeling of flatness deviations and associated process optimization for high yield and tough bonds

    NASA Astrophysics Data System (ADS)

    Stamoulis, Konstantinos; Tsau, Christine H.; Spearing, S. Mark

    2005-01-01

    Wafer-level, thermocompression bonding is a promising technique for MEMS packaging. The quality of the bond is critically dependent on the interaction between flatness deviations, the gold film properties and the process parameters and tooling used to achieve the bonds. The effect of flatness deviations on the resulting bond is investigated in the current work. The strain energy release rate associated with the elastic deformation required to overcome wafer bow is calculated. A contact yield criterion is used to examine the pressure and temperature conditions required to flatten surface roughness asperities in order to achieve bonding over the full apparent area. The results are compared to experimental data of bond yield and toughness obtained from four-point bend delamination testing and microscopic observations of the fractured surfaces. Conclusions from the modeling and experiments indicate that wafer bow has negligible effect on determining the variability of bond quality and that the well-bonded area is increased with increasing bonding pressure. The enhanced understanding of the underlying deformation mechanisms allows for a better controlled trade-off between the bonding pressure and temperature.

  17. Low-temperature wafer-level gold thermocompression bonding: modeling of flatness deviations and associated process optimization for high yield and tough bonds

    NASA Astrophysics Data System (ADS)

    Stamoulis, Konstantinos; Tsau, Christine H.; Spearing, S. Mark

    2004-12-01

    Wafer-level, thermocompression bonding is a promising technique for MEMS packaging. The quality of the bond is critically dependent on the interaction between flatness deviations, the gold film properties and the process parameters and tooling used to achieve the bonds. The effect of flatness deviations on the resulting bond is investigated in the current work. The strain energy release rate associated with the elastic deformation required to overcome wafer bow is calculated. A contact yield criterion is used to examine the pressure and temperature conditions required to flatten surface roughness asperities in order to achieve bonding over the full apparent area. The results are compared to experimental data of bond yield and toughness obtained from four-point bend delamination testing and microscopic observations of the fractured surfaces. Conclusions from the modeling and experiments indicate that wafer bow has negligible effect on determining the variability of bond quality and that the well-bonded area is increased with increasing bonding pressure. The enhanced understanding of the underlying deformation mechanisms allows for a better controlled trade-off between the bonding pressure and temperature.

  18. Effect of Embedding Cu-Graphene Hybrid Powder into 2-Phase In-Cu Solders on Its Suitability as Metallic Thermal Interface Material

    NASA Astrophysics Data System (ADS)

    Sharma, Deepak; Jain, Aman; Somaiah, Nalla; Narayanan, P. Ramesh; Kumar, Praveen

    2018-05-01

    The effect of embedding Cu-graphene hybrid powder, namely "graphene nano-sheet Cu" (GNS-Cu) powder, into In-40 vol.% Cu solder alloy on the electrical and mechanical properties of In-Cu solder is investigated. GNS-Cu hybrid powders were prepared by mixing reduced graphene oxide powders and CuSO4·5H2O, followed by reduction of the mixture with hydrazine. Subsequently, In-Cu solders with GNS-Cu powders were prepared using a 2-step process, comprising liquid phase sintering (LPS) of In and Cu powders followed by accumulative roll bonding (ARB). During ARB, the GNS-Cu powders were embedded as distinct layers into In-Cu composite solders. Electrical conductivity of the GNS-Cu embedded solders increased by > 20% as compared to pure In-Cu solders processed through the same combination of LPS-ARB steps. The yield strength of In-Cu solder increased by only 10% with the addition of GNS-Cu powders and thus retained the moderate strength often associated with pure In-Cu composite solders. Moreover, the thermal conductivity of GNS-Cu-embedded solders was estimated theoretically to increase by > 60%. These promising findings suggest that GNS-Cu-embedded In-Cu solders can be suitable for next-generation metallic thermal interface material and package-level interconnect applications.

  19. Solid Liquid Interdiffusion Bonding of (Pb, Sn)Te Thermoelectric Modules with Cu Electrodes Using a Thin-Film Sn Interlayer

    NASA Astrophysics Data System (ADS)

    Chuang, T. H.; Lin, H. J.; Chuang, C. H.; Yeh, W. T.; Hwang, J. D.; Chu, H. S.

    2014-12-01

    A (Pb, Sn)Te thermoelectric element plated with a Ni barrier layer and a Ag reaction layer has been joined with a Cu electrode coated with Ag and Sn thin films using a solid-liquid interdiffusion bonding method. This method allows the interfacial reaction between Ag and Sn such that Ag3Sn intermetallic compounds form at low temperature and are stable at high temperature. In this study, the bonding strength was about 6.6 MPa, and the specimens fractured along the interface between the (Pb, Sn)Te thermoelectric element and the Ni barrier layer. Pre-electroplating a film of Sn with a thickness of about 1 μm on the thermoelectric element and pre-heating at 250°C for 3 min ensures the adhesion between the thermoelectric material and the Ni barrier layer. The bonding strength is thus increased to a maximal value of 12.2 MPa, and most of the fractures occur inside the thermoelectric material. During the bonding process, not only the Ag3Sn intermetallics but also Cu6Sn5 forms at the Ag3Sn/Cu interface, which transforms into Cu3Sn with increases in the bonding temperature or bonding time.

  20. Bonding quandary in the [Cu3S2]3+ core: insights from the analysis of domain averaged fermi holes and the local spin.

    PubMed

    Ponec, Robert; Ramos-Cordoba, Eloy; Salvador, Pedro

    2013-03-07

    The electronic structure of the trinuclear symmetric complex [(tmedaCu)3S2 ](3+), whose Cu3S2 core represents a model of the active site of metalloenzymes involved in biological processes, has been in recent years the subject of vigorous debate. The complex exists as an open-shell triplet, and discussions concerned the question whether there is a direct S-S bond in the [Cu3S2](3+) core, whose answer is closely related to the problem of the formal oxidation state of Cu atoms. In order to contribute to the elucidation of the serious differences in the conclusions of earlier studies, we report in this study the detailed comprehensive analysis of the electronic structure of the [Cu3S2](3+) core using the methodologies that are specifically designed to address three particular aspects of the bonding in the core of the above complex, namely, the presence and/or absence of direct S-S bond, the existence and the nature of spin-spin interactions among the atoms in the core, and the formal oxidation state of Cu atoms in the core. Using such a combined approach, it was possible to conclude that the picture of bonding consistently indicates the existence of a weak direct two-center-three-electron (2c-3e) S-S bond, but at the same time, the observed lack of any significant local spin in the core of the complex is at odds with the suggested existence of antiferromagnetic coupling among the Cu and S atoms, so that the peculiarities of the bonding in the complex seem to be due to extensive delocalization of the unpaired spin in the [Cu3S2](3+) core. Finally, a scrutiny of the effective atomic hybrids and their occupations points to a predominant formal Cu(II) oxidation state, with a weak contribution of partial Cu(I) character induced mainly by the partial flow of electrons from S to Cu atoms and high delocalization of the unpaired spin in the [Cu3S2](3+) core.

  1. Nanoporous Al sandwich foils using size effect of Al layer thickness during Cu/Al/Cu laminate rolling

    NASA Astrophysics Data System (ADS)

    Yu, Hailiang; Lu, Cheng; Tieu, A. Kiet; Li, Huijun; Godbole, Ajit; Kong, Charlie

    2018-06-01

    The roll bonding technique is one of the most widely used methods to produce metal laminate sheets. Such sheets offer interesting research opportunities for both scientists and engineers. In this paper, we report on an experimental investigation of the 'thickness effect' during laminate rolling for the first time. Using a four-high multifunction rolling mill, Cu/Al/Cu laminate sheets were fabricated with a range of thicknesses (16, 40, 70 and 130 μm) of the Al layer. The thickness of the Cu sheets was a constant 300 μm. After rolling, TEM images show good bonding quality between the Cu and Al layers. However, there are many nanoscale pores in the Al layer. The fraction of nanoscale pores in the Al layer increases with a reduction in the Al layer thickness. The finite element method was used to simulate the Cu/Al/Cu rolling process. The simulation results reveal the effect of the Al layer thickness on the deformation characteristics of the Cu/Al/Cu laminate. Finally, we propose that the size effect of the Al layer thickness during Cu/Al/Cu laminate rolling may offer a method to fabricate 'nanoporous' Al sandwich laminate foils. Such foils can be used in electromagnetic shielding of electrical devices and noisy shielding of building.

  2. Effect of thione primers on adhesive bonding between an indirect composite material and Ag-Pd-Cu-Au alloy.

    PubMed

    Imai, Hideyuki; Koizumi, Hiroyasu; Shimoe, Saiji; Hirata, Isao; Matsumura, Hideo; Nikawa, Hiroki

    2014-01-01

    The current study evaluated the effect of primers on the shear bond strength of an indirect composite material joined to a silverpalladium-copper-gold (Ag-Pd-Cu-Au) alloy (Castwell). Disk specimens were cast from the alloy and were air-abraded with alumina. Eight metal primers were applied to the alloy surface. A light-polymerized indirect composite material (Solidex) was bonded to the alloy. Shear bond strength was determined both before and after the application of thermocycling. Two groups primed with Metaltite (thione) and M. L. Primer (sulfide) showed the greatest post-thermocycling bond strength (8.8 and 6.5 MPa). The results of the X-ray photoelectron spectroscopic (XPS) analysis suggested that the thione monomer (MTU-6) in the Metaltite primer was strongly adsorbed onto the Ag-Pd-Cu-Au alloy surface even after repeated cleaning with acetone. The application of either the thione (MTU-6) or sulfide primer is effective for enhancing the bonding between a composite material and Ag-Pd-Cu-Au alloy.

  3. Transient Liquid-Phase Diffusion Bonding of Aluminum Metal Matrix Composite Using a Mixed Cu-Ni Powder Interlayer

    NASA Astrophysics Data System (ADS)

    Maity, Joydeep; Pal, Tapan Kumar

    2012-07-01

    In the present study, the transient liquid-phase diffusion bonding of an aluminum metal matrix composite (6061-15 wt.% SiCp) has been investigated for the first time using a mixed Cu-Ni powder interlayer at 560 °C, 0.2 MPa, for different holding times up to 6 h. The microstructure of the isothermally solidified zone contains equilibrium precipitate CuAl2, metastable precipitate Al9Ni2 in the matrix of α-solid solution along with the reinforcement particles (SiC). On the other hand, the microstructure of the central bond zone consists of equilibrium phases such as NiAl3, Al7Cu4Ni and α-solid solution along with SiC particles (without any segregation) and the presence of microporosities. During shear test, the crack originates from microporosities and propagates along the interphase interfaces resulting in poor bond strength for lower holding times. As the bonding time increases, with continual diffusion, the structural heterogeneity is diminished, and the microporosities are eliminated at the central bond zone. Accordingly, after 6-h holding, the microstructure of the central bond zone mainly consists of NiAl3 without any visible microporosity. This provides a joint efficiency of 84% with failure primarily occurring through decohesion at the SiC particle/matrix interface.

  4. CuPt and CuPtRu Nanostructures for Ammonia Oxidation Reaction

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Manso, R H.; Song, L.; Liang, Z.

    Liquid fuels, such as methanol, ethanol, and ammonia, are attractive alternative to hydrogen for fuel cells due to their lower costs for storage and distribution. However, lack of sufficiently active catalysts for their oxidation reactions is a roadblock. Our previous study found that Pt 3Cu nanodendrites yielded higher activity and durability than Pt nanoparticles for methanol oxidation reaction (MOR) in acid. In this study, we synthesized two types of nanostructures of CuPt and CuPtRu catalysts via seed-mediated growth of Pt and Ru on Cu and tested their performance for ammonia oxidation reaction (AOR) in alkaline solution. Unlike for MOR, themore » nanodendrites do not promote AOR activity - CuPt performs similar to Pt and CuPtRu is less active than Pt. Interestingly, the AOR peak current is increased by 64% on CuPt nanowires and 330% on CuPtRu nanowires as compared to Pt nanoparticles. These results suggest that AOR prefers extended surface on long nanowires, distinctly differing from MOR. This can be contributed to two factors: NH 3 oxidization to N 2 involves dimerization of two N-containing intermediates to form the N-N bond and diffusion batters for adsorbed intermediates are generally lower on terrace than at low-coordination sites. This demonstrated strong effect of surface morphology will be further studied and utilized in developing advanced AOR nanocatalysts.« less

  5. CuPt and CuPtRu Nanostructures for Ammonia Oxidation Reaction

    DOE PAGES

    Manso, R H.; Song, L.; Liang, Z.; ...

    2018-04-01

    Liquid fuels, such as methanol, ethanol, and ammonia, are attractive alternative to hydrogen for fuel cells due to their lower costs for storage and distribution. However, lack of sufficiently active catalysts for their oxidation reactions is a roadblock. Our previous study found that Pt 3Cu nanodendrites yielded higher activity and durability than Pt nanoparticles for methanol oxidation reaction (MOR) in acid. In this study, we synthesized two types of nanostructures of CuPt and CuPtRu catalysts via seed-mediated growth of Pt and Ru on Cu and tested their performance for ammonia oxidation reaction (AOR) in alkaline solution. Unlike for MOR, themore » nanodendrites do not promote AOR activity - CuPt performs similar to Pt and CuPtRu is less active than Pt. Interestingly, the AOR peak current is increased by 64% on CuPt nanowires and 330% on CuPtRu nanowires as compared to Pt nanoparticles. These results suggest that AOR prefers extended surface on long nanowires, distinctly differing from MOR. This can be contributed to two factors: NH 3 oxidization to N 2 involves dimerization of two N-containing intermediates to form the N-N bond and diffusion batters for adsorbed intermediates are generally lower on terrace than at low-coordination sites. This demonstrated strong effect of surface morphology will be further studied and utilized in developing advanced AOR nanocatalysts.« less

  6. Magnetic behavior in heterometallic one-dimensional chains or octanuclear complex regularly aligned with metal-metal bonds as -Rh-Rh-Pt-Cu-Pt

    NASA Astrophysics Data System (ADS)

    Uemura, Kazuhiro

    2018-06-01

    Heterometallic one-dimensional chains, [{Rh2(O2CCH3)4}{Pt2Cu(piam)4(NH3)4}]n(PF6)2n (1 and 2, piam = pivalamidate) and [{Rh2(O2CCH3)4}{Pt2Cu(piam)4(NH3)4}2](CF3CO2)2(ClO4)2·2H2O (3), are paramagnetic one-dimensional chains or octanuclear complexes that are either aligned as -Rh-Rh-Pt-Cu-Pt- (1 and 2) or as Pt-Cu-Pt-Rh-Rh-Pt-Cu-Pt (3) with metal-metal bonds. Compounds 1-3 have rare structures, from the standpoint of that the paramagnetic species of Cu atoms are linked by direct metal-metal bonds. Magnetic susceptibility measurements for 1-3 performed at temperatures of 2 K-300 K indicated that the unpaired electrons localize in the Cu 3dx2-y2 orbitals, where S = 1/2 Cu(II) atoms are weakly antiferromagnetically coupled with J = -0.35 cm-1 (1), -0.47 cm-1 (2), and -0.45 cm-1 (3).

  7. Preliminary assessment of metal-porcelain bonding strength of CoCrW alloy after 3wt.% Cu addition.

    PubMed

    Lu, Yanjin; Zhao, Chaoqian; Ren, Ling; Guo, Sai; Gan, Yiliang; Yang, Chunguang; Wu, Songquan; Lin, Junjie; Huang, Tingting; Yang, Ke; Lin, Jinxin

    2016-06-01

    In this work, a novel Cu-bearing CoCrW alloy fabricated by selective laser melting for dental application has been studied. For its successful application, the bonding strength of metal-porcelain is essential to be systematically investigated. Therefore, the aim of this study was to evaluate the metal-porcelain bonding strength of CoCrWCu alloy by three-point bending test, meanwhile the Ni-free CoCrW alloy was used as control. The oxygen content was investigated by an elemental analyzer; X-ray photoelectron spectroscopy (XPS) was used to analyze the surface chemical composition of CoCrW based alloy after preoxidation treatment; the fracture mode was investigated by X-ray energy spectrum analysis (EDS) and scanning electron microscope (SEM). Result from the oxygen content analysis showed that the content of oxygen dramatically increased after the Cu addition. And the XPS suggested that Co-oxidation, Cr2O3, CrO2, WO3, Cu2O and CuO existed on the preoxidated surface of the CoCrWCu alloy; the three-point bending test showed that the bonding strength of the CoCrWCu alloy was 43.32 MPa, which was lower than that of the CoCrW group of 47.65 MPa. However, the average metal-porcelain bonding strength is significantly higher than the minimum value in the ISO 9693 standard. Results from the SEM images and EDS indicated that the fracture mode of CoCrWCu-porcelain was mixed between cohesive and adhesive. Based on the results obtained in this study, it can be indicated that the Cu-bearing CoCrW alloy fabricated by the selective laser melting is a promising candidate for use in dental application. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Highly charged swelling mica reduces Cu bioavailability in Cu-contaminated soils.

    PubMed

    Stuckey, Jason W; Neaman, Alexander; Ravella, Ramesh; Komarneni, Sridhar; Martínez, Carmen Enid

    2009-01-01

    This is the first test of a highly charged swelling mica's (Na-2-mica) ability to reduce the plant-absorbed Cu in Cu-contaminated soils from Chile. Perennial ryegrass (Lolium perenne L.) was grown in two acid soils (Sector 2: pH 4.2, total Cu = 172 mg Cu kg(-1) and Sector 3: pH 4.2, total Cu = 112 mg Cu kg(-1)) amended with 0.5% and 1% (w/w) mica, and 1% (w/w) montmorillonite. At 10 weeks of growth, both mica treatments decreased the shoot Cu of ryegrass grown in Sector 2 producing shoot Cu concentrations above 21-22 mg Cu kg(-1) (the phytotoxicity threshold for that species), yet the mica treatments did not reduce shoot Cu concentrations when grown in Sector 3, which were at a typical level. The mica treatments improved shoot growth in Sector 3 by reducing free and extractable Cu to low enough levels where other nutrients could compete for plant absorption and translocation. In addition, the mica treatments improved root growth in both soils, and the 1% mica treatment reduced root Cu in both soils. This swelling mica warrants further testing of its ability to assist re-vegetation and reduce Cu bioavailability in Cu-contaminated surface soils.

  9. C-H...Cl relevant discrepancy on structure, magnetic and electronic conductivity of two mixed-valence Cu{sup I}Cu{sup II} coordination polymers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shi Ling; Yang Ping; School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510631

    Two mixed-valence Cu{sup I}Cu{sup II} coordination polymers [Cu{sup I}Cu{sup II}(qdiol)ClL]{sub n} (qdiol{sup 2-}=2,3-dioxyquinoxalinate, L=2,2'-bipyridine, 1; L=1,10-phenanthroline, 2) were obtained in basic ethanolic solution of CuCl{sub 2}, 1,4-dihydro-2,3-quinoxalinedione and L under the solvothermal condition. 1 and 2 are similar in composition, but differ remarkably in structure. The coordination modes of Cu{sup II}, qdiol{sup 2-} and L are identical in both complexes. But the Cu{sup I} ions are two- and three-coordinated, and the Cl{sup -} ions are terminal and bridging, in 1 and 2, respectively, which are relevant to the significantly different C-H...Cl hydrogen bonding pattern of bpy and phen. The temperaturemore » variable magnetic susceptibilities show that 1 is paramagnetic and 2 is weakly antiferromagnetic. The complex impedance spectroscopic studies indicate that both 1 and 2 are semiconductors and 2 is more conducting. - Graphical Abstract: Subtly different C-H...Cl bonding nature leads to diverse coordination modes and supramolecular networks, as well as physical properties of two Cu{sup I}Cu{sup II} coordination polymers with similar compositions. Highlights: > Two new Cu(I)-Cu(II) mixed-valence coordination polymers are obtained. > Environments of Cu(I) and Cl are different caused by C-H...Cl H-bonding. > Supramolecular networks are hence diverse. > Magnetic and semiconducting properties are influenced by the structures.« less

  10. Electronic states of the Cu 3O 1217- model cluster

    NASA Astrophysics Data System (ADS)

    Chen, Xue-an; Chen, Zhi-fang; Heng, Fu; Tang, Youqi; Ye, Xue-qi; Zhu, Min-hui

    1991-03-01

    The Fenske-Hall molecular orbital calculations were performed on the model cluster Cu 3O 1217-. The calculated results revealed that the major contribution to the electronic states near the Fermi level comes from the orbitals of Cu 3d and O 2p, with dominantly oxygen p character, and the oxidation beyond the Cu 2+ state does not lead to Cu 3+ but to O - state. There exists the strong covalent bonding between copper and neighboring oxygen ions, especially between the chain Cu(1) and bridge O(4) ions. The slight displacement of O(4) along the c-axis toward Cu(2) can result in a decrease in the HOMO-LUMO gap and a strengthening of the chain-plane coupling.

  11. Dissociation mechanisms of HFO-1336mzz(Z) on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Huo, Erguang; Liu, Chao; Xu, Xiaoxiao; Li, Qibin; Dang, Chaobin

    2018-06-01

    The catalytic effect of Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces on the decomposition of HFO-1336mzz(Z) have been investigated by using Density Functional Theory (DFT) calculations. On the basis of adsorption energy analysis, the most stable adsorption energies of HFO-1336mzz(Z) and relevant products on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces were studied, respectively, and the co-adsorption structures of relevant species were obtained. Finally, four initiation decomposition reactions of HFO-1336mzz(Z) on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces were proposed and investigated, respectively. At the same time, the four similar homolytic reactions of free HFO-1336mzz(Z) molecular were calculated to compare with the dissociation reactions occurred on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces and illuminate the catalytic effect of Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces on the HFO-1336mzz(Z) decomposition. The results indicated that Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces had a good catalytic effect on the decomposition of HFO-1336mzz(Z). The fracture reactions of Cdbnd C bonds on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces were easier to occur than that of other reactions. Cu(1 0 0) surface had the highest catalytic activity and the lowest for Cu(1 1 1) surface.

  12. Crystal growth and physical properties of SrCu2As2, SrCu2Sb2, and BaCu2Sb2

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Anand, V.K.; Perera, P. Kanchana; Pandey, Abhishek

    2012-06-25

    We report the growth of single crystals of SrCu2As2, SrCu2Sb2, SrCu2(As0.84Sb0.16)2, and BaCu2Sb2 using the self-flux technique and their structural, magnetic, thermal, and transport properties that were investigated by powder x-ray diffraction (XRD), magnetic susceptibility χ, specific heat Cp, and electrical resistivity ρ measurements versus temperature T from 1.8 to 350 K. Rietveld refinements of XRD patterns for crushed crystals confirm that SrCu2As2 crystallizes in the ThCr2Si2-type body-centered tetragonal structure (space group I4/mmm) and SrCu2Sb2 crystallizes in the CaBe2Ge2-type primitive tetragonal structure (space group P4/nmm). However, as reported previously, BaCu2Sb2 is found to have a large unit cell consisting ofmore » three blocks. Here a ThCr2Si2-type block is sandwiched between two CaBe2Ge2-type blocks along the c axis with an overall symmetry of I4/mmm, as reported, but likely with a monoclinic distortion. The χ data of all these compounds are diamagnetic and reveal nearly T-independent anisotropic behavior. The χ of SrCu2As2 is found to be larger in the ab plane than along the c axis, as also previously reported for pure and doped BaFe2As2, whereas the χ values of SrCu2Sb2 and BaCu2Sb2 are larger along the c axis. This difference in anisotropy appears to arise from the differences between the crystal structures. The finite values of the Sommerfeld linear specific heat coefficients γ and the T dependences of ρ reveal metallic character of all four compounds. The electronic and magnetic properties indicate that these compounds are sp metals with Cu in the nonmagnetic 3d10 electronic configuration corresponding to the oxidation state Cu+1, as previously predicted theoretically for SrCu2As2 by Singh [ Phys. Rev. B 79 153102 (2009)]. We present a brief review of theoretical and experimental work on the doping character of transition metals for Fe in BaFe2As2. The As–As covalent interlayer bond distances in the collapsed-tetragonal (Ca,Sr,Ba)Cu

  13. Tribromobenzene on Cu(111): Temperature-dependent formation of halogen-bonded, organometallic, and covalent nanostructures

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Fan, Qitang; Wang, Tao; Zhu, Junfa, E-mail: jfzhu@ustc.edu.cn

    2015-03-14

    The temperature-controlled surface-assisted synthesis of halogen bonded, organometallic, and covalent nanostructures based on 1,3,5-tribromo-benzene (TriBB) was studied with scanning tunneling microscopy and X-ray photoemission spectroscopy in ultrahigh vacuum. Vapor deposition of TriBB onto a Cu(111) surface held at 90 K leads to the formation of large domains of a honeycomb-like organic monolayer structure stabilized by triangular nodes with Br⋯Br intermolecular bonds. Upon annealing the organic monolayer to ∼140 K, a new hexagonal close-packed structure with intact TriBB molecules connected by Cu adatoms is formed. Further warming up the sample to 300 K gives rise to the scission of C–Br bondsmore » and formation of C–Cu–C bonds between phenyl fragments such that stable dendritic organometallic networks are formed. Larger islands of organometallic networks are obtained by maintaining the temperature of Cu(111) at 420 K during deposition of TriBB. Simultaneously, large islands of Br atoms are formed around the organometallic networks. Annealing the more extended organometallic network (prepared at 420 K) to 520 K leads to the formation of a branched covalent organic framework (COF) which comprises structural elements of porous graphene and is surrounded by Br islands. These organometallic networks and COFs appear as small dendritic and branched domains, most likely due to the steric influence exerted by the Br islands.« less

  14. Thermochemical process for recovering Cu from CuO or CuO.sub.2

    DOEpatents

    Richardson, deceased, Donald M.; Bamberger, Carlos E.

    1981-01-01

    A process for producing hydrogen comprises the step of reacting metallic Cu with Ba(OH).sub.2 in the presence of steam to produce hydrogen and BaCu.sub.2 O.sub.2. The BaCu.sub.2 O.sub.2 is reacted with H.sub.2 O to form Cu.sub.2 O and a Ba(OH).sub.2 product for recycle to the initial reaction step. Cu can be obtained from the Cu.sub.2 O product by several methods. In one embodiment the Cu.sub.2 O is reacted with HF solution to provide CuF.sub.2 and Cu. The CuF.sub.2 is reacted with H.sub.2 O to provide CuO and HF. CuO is decomposed to Cu.sub.2 O and O.sub.2. The HF, Cu and Cu.sub.2 O are recycled. In another embodiment the Cu.sub.2 O is reacted with aqueous H.sub.2 SO.sub.4 solution to provide CuSO.sub.4 solution and Cu. The CuSO.sub.4 is decomposed to CuO and SO.sub.3. The CuO is decomposed to form Cu.sub.2 O and O.sub.2. The SO.sub.3 is dissolved to form H.sub.2 SO.sub.4. H.sub.2 SO.sub.4, Cu and Cu.sub.2 O are recycled. In another embodiment Cu.sub.2 O is decomposed electrolytically to Cu and O.sub.2. In another aspect of the invention, Cu is recovered from CuO by the steps of decomposing CuO to Cu.sub.2 O and O.sub.2, reacting the Cu.sub.2 O with aqueous HF solution to produce Cu and CuF.sub.2, reacting the CuF.sub.2 with H.sub.2 O to form CuO and HF, and recycling the CuO and HF to previous reaction steps.

  15. The Effect of CuO Nanoparticles on Antimicrobial Effects and Shear Bond Strength of Orthodontic Adhesives

    PubMed Central

    Toodehzaeim, Mohammad Hossein; Zandi, Hengameh; Meshkani, Hamidreza; Hosseinzadeh Firouzabadi, Azadeh

    2018-01-01

    Statement of the Problem: Orthodontic appliances facilitate microbial plaque accumulation and increase the chance of white spot lesions. There is a need for new plaque control methods independent of patient's cooperation. Purpose: The aim of this study was to determine the effects of incorporating copper oxide (CuO) nanoparticles on antimicrobial properties and bond strength of orthodontic adhesive. Materials and Method: CuO nanoparticles were added to the composite transbond XT at concentrations of 0.01, 0.5 and 1 wt.%. To evaluate the antimicrobial properties of composites containing nanoparticles, the disk agar diffusion test was used. For this purpose, 10 discs from each concentration of nano-composites (totally 30 discs) and 10 discs from conventional composite (as the control group) were prepared. Then the diameter of streptococcus mutans growth inhibition around each disc was determined in blood agar medium. To evaluate the shear bond strength, with each concentration of nano-composites as well as the control group (conventional composite), 10 metal brackets were bonded to the human premolars and shear bond strength was determined using a universal testing machine. Results: Nano-composites in all three concentrations showed significant antimicrobial effect compared to the control group (p< 0.001). With increasing concentration of nanoparticles, antimicrobial effect showed an upward trend, although statistically was not significant. There was no significant difference between the shear bond strength of nano-composites compared to control group (p= 0.695). Conclusion: Incorporating CuO nanoparticles into adhesive in all three studied concentrations added antimicrobial effects to the adhesive with no adverse effects on shear bond strength. PMID:29492409

  16. The Effect of CuO Nanoparticles on Antimicrobial Effects and Shear Bond Strength of Orthodontic Adhesives.

    PubMed

    Toodehzaeim, Mohammad Hossein; Zandi, Hengameh; Meshkani, Hamidreza; Hosseinzadeh Firouzabadi, Azadeh

    2018-03-01

    Orthodontic appliances facilitate microbial plaque accumulation and increase the chance of white spot lesions. There is a need for new plaque control methods independent of patient's cooperation. The aim of this study was to determine the effects of incorporating copper oxide (CuO) nanoparticles on antimicrobial properties and bond strength of orthodontic adhesive. CuO nanoparticles were added to the composite transbond XT at concentrations of 0.01, 0.5 and 1 wt.%. To evaluate the antimicrobial properties of composites containing nanoparticles, the disk agar diffusion test was used. For this purpose, 10 discs from each concentration of nano-composites (totally 30 discs) and 10 discs from conventional composite (as the control group) were prepared. Then the diameter of streptococcus mutans growth inhibition around each disc was determined in blood agar medium. To evaluate the shear bond strength, with each concentration of nano-composites as well as the control group (conventional composite), 10 metal brackets were bonded to the human premolars and shear bond strength was determined using a universal testing machine. Nano-composites in all three concentrations showed significant antimicrobial effect compared to the control group ( p < 0.001). With increasing concentration of nanoparticles, antimicrobial effect showed an upward trend, although statistically was not significant. There was no significant difference between the shear bond strength of nano-composites compared to control group ( p = 0.695). Incorporating CuO nanoparticles into adhesive in all three studied concentrations added antimicrobial effects to the adhesive with no adverse effects on shear bond strength.

  17. MOFzyme: Intrinsic protease-like activity of Cu-MOF

    NASA Astrophysics Data System (ADS)

    Li, Bin; Chen, Daomei; Wang, Jiaqiang; Yan, Zhiying; Jiang, Liang; Deliang Duan; He, Jiao; Luo, Zhongrui; Zhang, Jinping; Yuan, Fagui

    2014-10-01

    The construction of efficient enzyme mimetics for the hydrolysis of peptide bonds in proteins is challenging due to the high stability of peptide bonds and the importance of proteases in biology and industry. Metal-organic frameworks (MOFs) consisting of infinite crystalline lattices with metal clusters and organic linkers may provide opportunities for protease mimic which has remained unknown. Herein, we report that Cu2(C9H3O6)4/3 MOF (which is well known as HKUST-1 and denoted as Cu-MOF here), possesses an intrinsic enzyme mimicking activity similar to that found in natural trypsin to bovine serum albumin (BSA) and casein. The Michaelis constant (Km) of Cu-MOF is about 26,000-fold smaller than that of free trypsin indicating a much higher affinity of BSA for Cu-MOF surface. Cu-MOF also exhibited significantly higher catalytic efficiency than homogeneous artificial metalloprotease Cu(II) complexes and could be reused for ten times without losing in its activity. Moreover, Cu-MOF was successfully used to simulate trypsinization in cell culture since it dissociated cells in culture even without EDTA.

  18. Solid Liquid Interdiffusion Bonding of Zn4Sb3 Thermoelectric Material with Cu Electrode

    NASA Astrophysics Data System (ADS)

    Lin, Y. C.; Lee, K. T.; Hwang, J. D.; Chu, H. S.; Hsu, C. C.; Chen, S. C.; Chuang, T. H.

    2016-10-01

    The ZnSb intermetallic compound may have thermoelectric applications because it is low in cost and environmentally friendly. In this study, a Zn4Sb3 thermoelectric element coated with a Ni barrier layer and a Ag reaction layer was bonded with a Ag-coated Cu electrode using a Ag/Sn/Ag solid-liquid interdiffusion bonding process. The results indicated that a Ni5Zn21 intermetallic phase formed easily at the Zn4Sb3/Ni interface, leading to sound adhesion. In addition, Sn film was found to react completely with the Ag layer to form a Ag3Sn intermetallic layer having a melting point of 480°C. The resulting Zn4Sb3 thermoelectric module can be applied at the optimized operation temperature (400°C) of Zn4Sb3 material as a thermoelectric element. The bonding strengths ranged from 14.9 MPa to 25.0 MPa, and shear tests revealed that the Zn4Sb3/Cu-joints fractured through the interior of the thermoelectric elements.

  19. Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu(-)(cytidine) and Cu(-)(uridine).

    PubMed

    Li, Xiang; Ko, Yeon-Jae; Wang, Haopeng; Bowen, Kit H; Guevara-García, Alfredo; Martínez, Ana

    2011-02-07

    The copper-nucleoside anions, Cu(-)(cytidine) and Cu(-)(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu(-)(cytidine) and Cu(-)(uridine), respectively. According to our calculations, Cu(-)(cytidine) and Cu(-)(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostatic interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu(-)(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.

  20. Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu-(cytidine) and Cu-(uridine)

    NASA Astrophysics Data System (ADS)

    Li, Xiang; Ko, Yeon-Jae; Wang, Haopeng; Bowen, Kit H.; Guevara-García, Alfredo; Martínez, Ana

    2011-02-01

    The copper-nucleoside anions, Cu-(cytidine) and Cu-(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu-(cytidine) and Cu-(uridine), respectively. According to our calculations, Cu-(cytidine) and Cu-(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostatic interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu-(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.

  1. Applications of the silicon wafer direct-bonding technique to electron devices

    NASA Astrophysics Data System (ADS)

    Furukawa, K.; Nakagawa, A.

    1990-01-01

    A silicon wafer direct-bonding (SDB) technique has been developed. A pair of bare silicon wafers, as well as an oxidized wafer pair, are bonded throughout the wafer surfaces without any bonding material. Conventional semiconductor device processes can be used for the bonded wafers, since the bonded interface is stable thermally, chemically, mechanically and electrically. Therefore, the SDB technique is very attractive, and has been applied to several kinds of electron devices. Bare silicon to bare silicon bonding is an alternative for epitaxial growth. A thick, high quality and high resistivity layer on a low resistivity substrate was obtained without autodoping. 1800 V insulated gate bipolar transistors were developed using these SDB wafers. No electrical resistance was observed at the bonded bare silicon interfaces. If oxidized wafers are bonded, the two wafers are electrically isolated, providing silicon on insulator (SOI) wafers. Dielectrically isolated photodiode arrays were fabricated on the SOI wafers and 500 V power IC's are now being developed.

  2. High-throughput tool to discriminate effects of NMs (Cu-NPs, Cu-nanowires, CuNO3, and Cu salt aged): transcriptomics in Enchytraeus crypticus.

    PubMed

    Gomes, Susana I L; Roca, Carlos P; Pegoraro, Natália; Trindade, Tito; Scott-Fordsmand, Janeck J; Amorim, Mónica J B

    2018-05-01

    The current testing of nanomaterials (NMs) via standard toxicity tests does not cover many of the NMs specificities. One of the recommendations lays on understanding the mechanisms of action, as these can help predicting long-term effects and safe-by-design production. In the present study, we used the high-throughput gene expression tool, developed for Enchytraeus crypticus (4 × 44k Agilent microarray), to study the effects of exposure to several copper (Cu) forms. The Cu treatments included two NMs (spherical and wires) and two copper-salt treatments (CuNO 3 spiked and Cu salt field historical contamination). To relate gene expression with higher effect level, testing was done with reproduction effect concentrations (EC 20 , EC 50 ), using 3 and 7 days as exposure periods. Results showed that time plays a major role in the transcriptomic response, most of it occurring after 3 days. Analysis of gene expression profiles showed that Cu-salt-aged and Cu-nanowires (Nwires) differed from CuNO 3 and Cu-nanoparticles (NPs). Functional analysis revealed specific mechanisms: Cu-NPs uniquely affected senescence and cuticle pattern formation, which can result from the contact of the NPs with the worms' tegument. Cu-Nwires affected reproduction via male gamete generation and hermaphrodite genitalia development. CuNO 3 affected neurotransmission and locomotory behavior, both of which can be related with avoidance response. Cu salt-aged uniquely affected phagocytosis and reproductive system development (via different mechanisms than Cu-Nwires). For the first time for Cu (nano)materials, the adverse outcome pathways (AOPs) drafted here provide an overview for common and unique effects per material and linkage with apical effects.

  3. LED Die-Bonded on the Ag/Cu Substrate by a Sn-BiZn-Sn Bonding System

    NASA Astrophysics Data System (ADS)

    Tang, Y. K.; Hsu, Y. C.; Lin, E. J.; Hu, Y. J.; Liu, C. Y.

    2016-12-01

    In this study, light emitting diode (LED) chips were die-bonded on a Ag/Cu substrate by a Sn-BixZn-Sn bonding system. A high die-bonding strength is successfully achieved by using a Sn-BixZn-Sn ternary system. At the bonding interface, there is observed a Bi-segregation phenomenon. This Bi-segregation phenomenon solves the problems of the brittle layer-type Bi at the joint interface. Our shear test results show that the bonding interface with Bi-segregation enhances the shear strength of the LED die-bonding joints. The Bi-0.3Zn and Bi-0.5Zn die-bonding cases have the best shear strength among all die-bonding systems. In addition, we investigate the atomic depth profile of the deposited Bi-xZn layer by evaporating Bi-xZn E-gun alloy sources. The initial Zn content of the deposited Bi-Zn alloy layers are much higher than the average Zn content in the deposited Bi-Zn layers.

  4. Effect of nanoscale surface roughness on the bonding energy of direct-bonded silicon wafers

    NASA Astrophysics Data System (ADS)

    Miki, N.; Spearing, S. M.

    2003-11-01

    Direct wafer bonding of silicon wafers is a promising technology for manufacturing three-dimensional complex microelectromechanical systems as well as silicon-on-insulator substrates. Previous work has reported that the bond quality declines with increasing surface roughness, however, this relationship has not been quantified. This article explicitly correlates the bond quality, which is quantified by the apparent bonding energy, and the surface morphology via the bearing ratio, which describes the area of surface lying above a given depth. The apparent bonding energy is considered to be proportional to the real area of contact. The effective area of contact is defined as the area sufficiently close to contribute to the attractive force between the two bonding wafers. Experiments were conducted with silicon wafers whose surfaces were roughened by a buffered oxide etch solution (BOE, HF:NH4F=1:7) and/or a potassium hydroxide solution. The surface roughness was measured by atomic force microscopy. The wafers were direct bonded to polished "monitor" wafers following a standard RCA cleaning and the resulting bonding energy was measured by the crack-opening method. The experimental results revealed a clear correlation between the bonding energy and the bearing ratio. A bearing depth of ˜1.4 nm was found to be appropriate for the characterization of direct-bonded silicon at room temperature, which is consistent with the thickness of the water layer at the interface responsible for the hydrogen bonds that link the mating wafers.

  5. MOFzyme: Intrinsic protease-like activity of Cu-MOF

    PubMed Central

    Li, Bin; Chen, Daomei; Wang, Jiaqiang; Yan, Zhiying; Jiang, Liang; Deliang Duan; He, Jiao; Luo, Zhongrui; Zhang, Jinping; Yuan, Fagui

    2014-01-01

    The construction of efficient enzyme mimetics for the hydrolysis of peptide bonds in proteins is challenging due to the high stability of peptide bonds and the importance of proteases in biology and industry. Metal-organic frameworks (MOFs) consisting of infinite crystalline lattices with metal clusters and organic linkers may provide opportunities for protease mimic which has remained unknown. Herein, we report that Cu2(C9H3O6)4/3 MOF (which is well known as HKUST-1 and denoted as Cu-MOF here), possesses an intrinsic enzyme mimicking activity similar to that found in natural trypsin to bovine serum albumin (BSA) and casein. The Michaelis constant (Km) of Cu-MOF is about 26,000-fold smaller than that of free trypsin indicating a much higher affinity of BSA for Cu-MOF surface. Cu-MOF also exhibited significantly higher catalytic efficiency than homogeneous artificial metalloprotease Cu(II) complexes and could be reused for ten times without losing in its activity. Moreover, Cu-MOF was successfully used to simulate trypsinization in cell culture since it dissociated cells in culture even without EDTA. PMID:25342169

  6. Electromigration Failure Mechanism in Sn-Cu Solder Alloys with OSP Cu Surface Finish

    NASA Astrophysics Data System (ADS)

    Chu, Ming-Hui; Liang, S. W.; Chen, Chih; Huang, Annie T.

    2012-09-01

    Organic solderable preservative (OSP) has been adopted as the Cu substrate surface finish in flip-chip solder joints for many years. In this study, the electromigration behavior of lead-free Sn-Cu solder alloys with thin-film under bump metallization and OSP surface finish was investigated. The results showed that severe damage occurred on the substrate side (cathode side), whereas the damage on the chip side (cathode side) was not severe. The damage on the substrate side included void formation, copper dissolution, and formation of intermetallic compounds (IMCs). The OSP Cu interface on the substrate side became the weakest point in the solder joint even when thin-film metallization was used on the chip side. Three-dimensional simulations were employed to investigate the current density distribution in the area between the OSP Cu surface finish and the solder. The results indicated that the current density was higher along the periphery of the bonding area between the solder and the Cu pad, consistent with the area of IMC and void formation in our experimental results.

  7. Crystallographic and optical properties and band diagrams of CuGaS2 and CuGa5S8 phases in Cu-poor Cu2S-Ga2S3 pseudo-binary system

    NASA Astrophysics Data System (ADS)

    Maeda, Tsuyoshi; Yu, Ying; Chen, Qing; Ueda, Kenta; Wada, Takahiro

    2017-04-01

    We synthesized Cu-poor Cu-Ga-S samples such, as CuGaS2 and CuGa5S8 with the composition of (1 - x)Cu2S-(x)Ga2S3 with 0.5 ≤ x ≤ 1.0, by a mechanochemical process and sequential heating. The crystal structure changes from tetragonal chalcopyrite-type CuGaS2 (0.5 ≤ x ≤ 0.55) to tetragonal stannite-type CuGa5S8 (x = 0.8). For samples with 0.60 ≤ x ≤ 0.75, the diffraction peaks were identified to be those of a mixed phase of the chalcopyrite- and stannite-type structures. The band-gap energies of Cu-poor Cu-Ga-S samples increase in a stepwise manner with increasing x. The band-gap energy of CuGa5S8 (x = 0.8) with the tetragonal stannite-type structure is approximately 2.66 eV, which is wider than that of chalcopyrite-type CuGaS2 (2.45 eV). The energy levels of valence band maxima (VBMs) were estimated from the ionization energies measured by photoemission yield spectroscopy (PYS). The energy levels of the VBM and conduction band minimum (CBM) of the Cu-poor Cu-Ga-S samples decrease significantly with increasing x (decreasing Cu/Ga ratio). The energy level of the VBM of CuGaS2 (-5.8 eV) is considerably deeper than those of CuInSe2 (-5.2 eV) and CuInS2 (-5.5 eV). The VBM of stannite-type CuGa5S8 with x = 0.8 (-6.4 eV) is much deeper than that of chalcopyrite-type CuGaS2 (-5.8 eV) and stannite-type CuIn3Se5 (-5.6 eV). In order to understand the band structures of chalcopyrite-type CuGaS2 and stannite-type CuGa5S8, we performed first-principles calculations using the Heyd-Scuseria-Ernzerhof (HSE06), nonlocal screened hybrid density functional method. The theoretical band-gap energy of stannite-type CuGa5S8 (2.2 eV) is wider than that of chalcopyrite-type CuGaS2 (2.0 eV). Both the theoretical and experimental band gaps of stannite-type CuGa5S8 are about 0.2 eV wider than those of chalcopyrite-type CuGaS2.

  8. MOFzyme: Intrinsic protease-like activity of Cu-MOF.

    PubMed

    Li, Bin; Chen, Daomei; Wang, Jiaqiang; Yan, Zhiying; Jiang, Liang; Deliang Duan; He, Jiao; Luo, Zhongrui; Zhang, Jinping; Yuan, Fagui

    2014-10-24

    The construction of efficient enzyme mimetics for the hydrolysis of peptide bonds in proteins is challenging due to the high stability of peptide bonds and the importance of proteases in biology and industry. Metal-organic frameworks (MOFs) consisting of infinite crystalline lattices with metal clusters and organic linkers may provide opportunities for protease mimic which has remained unknown. Herein, we report that Cu₂(C₉H₃O₆)₄/₃ MOF (which is well known as HKUST-1 and denoted as Cu-MOF here), possesses an intrinsic enzyme mimicking activity similar to that found in natural trypsin to bovine serum albumin (BSA) and casein. The Michaelis constant (Km) of Cu-MOF is about 26,000-fold smaller than that of free trypsin indicating a much higher affinity of BSA for Cu-MOF surface. Cu-MOF also exhibited significantly higher catalytic efficiency than homogeneous artificial metalloprotease Cu(II) complexes and could be reused for ten times without losing in its activity. Moreover, Cu-MOF was successfully used to simulate trypsinization in cell culture since it dissociated cells in culture even without EDTA.

  9. Cohesive zone model for direct silicon wafer bonding

    NASA Astrophysics Data System (ADS)

    Kubair, D. V.; Spearing, S. M.

    2007-05-01

    Direct silicon wafer bonding and decohesion are simulated using a spectral scheme in conjunction with a rate-dependent cohesive model. The cohesive model is derived assuming the presence of a thin continuum liquid layer at the interface. Cohesive tractions due to the presence of a liquid meniscus always tend to reduce the separation distance between the wafers, thereby opposing debonding, while assisting the bonding process. In the absence of the rate-dependence effects the energy needed to bond a pair of wafers is equal to that needed to separate them. When rate-dependence is considered in the cohesive law, the experimentally observed asymmetry in the energetics can be explained. The derived cohesive model has the potential to form a bridge between experiments and a multiscale-modelling approach to understand the mechanics of wafer bonding.

  10. Accumulative Roll Bonding and Post-Deformation Annealing of Cu-Al-Mn Shape Memory Alloy

    NASA Astrophysics Data System (ADS)

    Moghaddam, Ahmad Ostovari; Ketabchi, Mostafa; Afrasiabi, Yaser

    2014-12-01

    Accumulative roll bonding is a severe plastic deformation process used for Cu-Al-Mn shape memory alloy. The main purpose of this study is to investigate the possibility of grain refinement of Cu-9.5Al-8.2Mn (in wt.%) shape memory alloy using accumulative roll bonding and post-deformation annealing. The alloy was successfully subjected to 5 passes of accumulative roll bonding at 600 °C. The microstructure, properties as well as post-deformation annealing of this alloy were investigated by optical microscopy, scanning electron microscopy, x-ray diffraction, differential scanning calorimeter, and bend and tensile testing. The results showed that after 5 passes of ARB at 600 °C, specimens possessed α + β microstructure with the refined grains, but martensite phases and consequently shape memory effect completely disappeared. Post-deformation annealing was carried out at 700 °C, and the martensite phase with the smallest grain size (less than 40 μm) was obtained after 150 s of annealing at 700 °C. It was found that after 5 passes of ARB and post-deformation annealing, the stability of SME during thermal cycling improved. Also, tensile properties of alloys significantly improved after post-deformation annealing.

  11. Room temperature radiolytic synthesized Cu@CuAlO(2)-Al(2)O(3) nanoparticles.

    PubMed

    Abedini, Alam; Saion, Elias; Larki, Farhad; Zakaria, Azmi; Noroozi, Monir; Soltani, Nayereh

    2012-01-01

    Colloidal Cu@CuAlO(2)-Al(2)O(3) bimetallic nanoparticles were prepared by a gamma irradiation method in an aqueous system in the presence of polyvinyl pyrrolidone (PVP) and isopropanol respectively as a colloidal stabilizer and scavenger of hydrogen and hydroxyl radicals. The gamma irradiation was carried out in a (60)Co gamma source chamber with different doses up to 120 kGy. The formation of Cu@CuAlO(2)-Al(2)O(3) nanoparticles was observed initially by the change in color of the colloidal samples from colorless to brown. Fourier transform infrared spectroscopy (FTIR) confirmed the presence of bonds between polymer chains and the metal surface at all radiation doses. Results of transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDX), and X-ray diffraction (XRD) showed that Cu@CuAlO(2)-Al(2)O(3) nanoparticles are in a core-shell structure. By controlling the absorbed dose and precursor concentration, nanoclusters with different particle sizes were obtained. The average particle diameter increased with increased precursor concentration and decreased with increased dose. This is due to the competition between nucleation, growth, and aggregation processes in the formation of nanoclusters during irradiation.

  12. A theoretical investigation on Cu/Ag/Au bonding in XH2P⋯MY(X = H, CH3, F, CN, NO2; M = Cu, Ag, Au; Y = F, Cl, Br, I) complexes

    NASA Astrophysics Data System (ADS)

    Wang, Zhaoxu; Liu, Yi; Zheng, Baishu; Zhou, Fengxiang; Jiao, Yinchun; Liu, Yuan; Ding, XunLei; Lu, Tian

    2018-05-01

    Intermolecular interaction of XH2P...MY (X = H, CH3, F, CN, NO2; M = Cu, Ag, Au; Y = F, Cl, Br, I) complexes was investigated by means of an ab initio method. The molecular interaction energies are in the order Ag < Cu < Au and increased with the decrease of RP...M. Interaction energies are strengthened when electron-donating substituents X connected to XH2P, while electron-withdrawing substituents produce the opposite effect. The strongest P...M bond was found in CH3H2P...AuF with -70.95 kcal/mol, while the weakest one was found in NO2H2P...AgI with -20.45 kcal/mol. The three-center/four-electron (3c/4e) resonance-type of P:-M-:Y hyperbond was recognized by the natural resonance theory and the natural bond orbital analysis. The competition of P:M-Y ↔ P-M:Y resonance structures mainly arises from hyperconjugation interactions; the bond order of bP-M and bM-Y is in line with the conservation of the idealized relationship bP-M + bM-Y ≈ 1. In all MF-containing complexes, P-M:F resonance accounted for a larger proportion which leads to the covalent characters for partial ionicity of MF. The interaction energies of these Cu/Ag/Au complexes are basically above the characteristic values of the halogen-bond complexes and close to the observed strong hydrogen bonds in ionic hydrogen-bonded species.

  13. Use of π-π forces to steer the assembly of a NTA complex of Cu(II) into hydrogen bonded supramolecular layers (H 3NTA = nitrilotriacetic acid)

    NASA Astrophysics Data System (ADS)

    Dey, Biswajit; Choudhury, Somnath Ray; Suresh, Eringathodi; Jana, Atish Dipankar; Mukhopadhyay, Subrata

    2009-03-01

    We propose a crystal engineering principle where we show that it might be possible to direct the organization of molecular complexes into hydrogen bonded supramolecular layers through the use of suitable co-ligands possessing both the hydrogen-bonding as well as π-π stacking capability. This principle has been tested for the organization of [Cu(NTA) 2] units (H 3NTA = nitrilotriacetic acid, N(CH 2CO 2H) 3) in the molecular complex with formula (2-A-PH) 4[Cu(NTA) 2]·6H 2O ( 1), where 2-A-PH is protonated 2-amino-4-picoline. In 1, the 2-amino-4-picoline co-ligands have been utilized to direct the organization of [Cu(NTA) 2] units into hydrogen bonded layers. The linear stacking of π-π bonded protonated 2-amino-4-picoline molecules can be thought as the influencing agent for the organization of [Cu(NTA) 2] units into hydrogen bonded layers.

  14. Electronic structures of the YBa2Cu3O7-x surface and its modification by sputtering and adatoms of Ti and Cu

    NASA Astrophysics Data System (ADS)

    Meyer, H. M., III; Hill, D. M.; Wagener, T. J.; Gao, Y.; Weaver, J. H.; Capone, D. W., II; Goretta, K. C.

    1988-10-01

    metal as the overlayer thickens (Cu 2p2/3 binding energy 932.5 eV for Cu metal, 933.1 eV for Cu1+, and 932.8 eV for the superconductor). Valence-band results during interface formation show the disappearance of emission near the Fermi level, consistent with the loss of Cu2+-O covalent bonds of the superconductor.

  15. Controlling superstructural ordering in the clathrate-I Ba 8 M 16 P 30 (M = Cu, Zn) through the formation of metal–metal bonds

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dolyniuk, J.; Whitfield, P. S.; Lee, K.

    2017-01-01

    Order–disorder–order phase transitions in the clathrate-I Ba8Cu16P30 were induced and controlled by aliovalent substitutions of Zn into the framework. Unaltered Ba8Cu16P30 crystallizes in an ordered orthorhombic (Pbcn) clathrate-I superstructure that maintains complete segregation of metal and phosphorus atoms over 23 different crystallographic positions in the clathrate framework. The driving force for the formation of this Pbcn superstructure is the avoidance of Cu–Cu bonds. This superstructure is preserved upon aliovalent substitution of Zn for Cu in Ba8Cu16-xZnxP30 with 0 < x < 1.6 (10% Zn/Mtotal), but vanishes at greater substitution concentrations. Higher Zn concentrations (up to 35% Zn/Mtotal) resulted in themore » additional substitution of Zn for P in Ba8M16+yP30-y (M = Cu, Zn) with 0 ≤ y ≤ 1. This causes the formation of Cu–Zn bonds in the framework, leading to a collapse of the orthorhombic superstructure into the more common cubic subcell of clathrate-I (Pm[3 with combining macron]n). In the resulting cubic phases, each clathrate framework position is jointly occupied by three different elements: Cu, Zn, and P. Detailed structural characterization of the Ba–Cu–Zn–P clathrates-I via single crystal X-ray diffraction, joint synchrotron X-ray and neutron powder diffractions, pair distribution function analysis, electron diffraction and high-resolution electron microscopy, along with elemental analysis, indicates that local ordering is present in the cubic clathrate framework, suggesting the evolution of Cu–Zn bonds. For the compounds with the highest Zn content, a disorder–order transformation is detected due to the formation of another superstructure with trigonal symmetry and Cu–Zn bonds in the clathrate-I framework. It is shown that small changes in the composition, synthesis, and crystal structure have significant impacts on the structural and transport properties of Zn-substituted Ba8Cu16P30.« less

  16. Mid-Gap States and Normal vs Inverted Bonding in Luminescent Cu+- and Ag+-Doped CdSe Nanocrystals.

    PubMed

    Nelson, Heidi D; Hinterding, Stijn O M; Fainblat, Rachel; Creutz, Sidney E; Li, Xiaosong; Gamelin, Daniel R

    2017-05-10

    Mid-gap luminescence in copper (Cu + )-doped semiconductor nanocrystals (NCs) involves recombination of delocalized conduction-band electrons with copper-localized holes. Silver (Ag + )-doped semiconductor NCs show similar mid-gap luminescence at slightly (∼0.3 eV) higher energy, suggesting a similar luminescence mechanism, but this suggestion appears inconsistent with the large difference between Ag + and Cu + ionization energies (∼1.5 eV), which should make hole trapping by Ag + highly unfavorable. Here, Ag + -doped CdSe NCs (Ag + :CdSe) are studied using time-resolved variable-temperature photoluminescence (PL) spectroscopy, magnetic circularly polarized luminescence (MCPL) spectroscopy, and time-dependent density functional theory (TD-DFT) to address this apparent paradox. In addition to confirming that Ag + :CdSe and Cu + :CdSe NCs display similar broad PL with large Stokes shifts, we demonstrate that both also show very similar temperature-dependent PL lifetimes and magneto-luminescence. Electronic-structure calculations further predict that both dopants generate similar localized mid-gap states. Despite these strong similarities, we conclude that these materials possess significantly different electronic structures. Specifically, whereas photogenerated holes in Cu + :CdSe NCs localize primarily in Cu(3d) orbitals, formally oxidizing Cu + to Cu 2+ , in Ag + :CdSe NCs they localize primarily in 4p orbitals of the four neighboring Se 2- ligands, and Ag + is not oxidized. This difference reflects a shift from "normal" to "inverted" bonding going from Cu + to Ag + . The spectroscopic similarities are explained by the fact that, in both materials, photogenerated holes are localized primarily within covalent [MSe 4 ] dopant clusters (M = Ag + , Cu + ). These findings reconcile the similar spectroscopies of Ag + - and Cu + -doped semiconductor NCs with the vastly different ionization potentials of their Ag + and Cu + dopants.

  17. Electronic and total energy properties of ternary and quaternary semiconductor compounds, alloys, and superlattices: Theoretical study of Cu/graphite bonding

    NASA Technical Reports Server (NTRS)

    Lambrecht, Walter R. L.

    1992-01-01

    The goals of the research were to provide a fundamental science basis for why the bonding of Cu to graphite is weak, to critically evaluate the previous analysis of the wetting studies with particular regard to the values used for the surface energies of Cu and graphite, and to make recommendations for future experiments or other studies which could advance the understanding and solution of this technological problem. First principles electronic structure calculations were used to study the problem. These are based on density functional theory in the local density approximation and the use of the linear muffin-tin orbital band structure method. Calculations were performed for graphite monolayers, single crystal graphite with the hexagonal AB stacking, bulk Cu, Cu(111) surface, and Cu/graphite superlattices. The study is limited to the basal plane of graphite because this is the graphite plane exposed to Cu and graphite surface energies and combined with the measured contact angles to evaluate the experimental adhesion energy.

  18. The nature of the bonding in XCO for X = Fe, Ni, and Cu

    NASA Technical Reports Server (NTRS)

    Bauschlicher, C. W., Jr.; Bagus, P. S.; Nelin, C. J.; Roos, B. O.

    1986-01-01

    The bonding in the (5,3)Sigma - and 3Delta states of FeCO, the (3,1)Sigma + , 3Delta, and 3Pi states of NiCO, and the 2Sigma + state of CuCO are analyzed using the constrained-space orbital-variation (CSOV) technique for both (CASSCF) and SCF wave functions. The bonding is discussed in terms of sigma repulsion between the metals 4s and the CO 5-sigma and CO-to-metal sigma donation when there is an empty or partly occupied d-sigma orbital and metal-to-CO 2pi(asterisk) backdonation. The bonding is compared for the different metals and between the different states.

  19. Copper diffusion and mechanical toughness at Cu-silica interfaces glued with polyelectrolyte nanolayers

    NASA Astrophysics Data System (ADS)

    Gandhi, D. D.; Singh, A. P.; Lane, M.; Eizenberg, M.; Ramanath, G.

    2007-04-01

    We demonstrate the use of polyallylamine hydrochloride (PAH)-polystyrene sulfonate (PSS) nanolayers to block Cu transport into silica. Cu/PSS-PAH/SiO2 structures show fourfold enhancement in device failure times during bias thermal annealing at 200 °C at an applied electric field of 2 MV/cm, when compared with structures with pristine Cu-SiO2 interfaces. Although the bonding at both Cu-PSS and PAH-SiO2 interfaces are strong, the interfacial toughness measured by the four-point bend tests is ˜2 Jm-2. Spectroscopic analysis of fracture surfaces reveals that weak electrostatic bonding at the PSS-PAH interface is responsible for the low toughness. Similar behavior is observed for Cu-SiO2 interfaces modified with other polyelectrolyte bilayers that inhibit Cu diffusion. Thus, while strong bonding at Cu-barrier and barrier-dielectric interfaces may be sufficient for blocking copper transport across polyelectrolyte bilayers, strong interlayer molecular bonding is a necessary condition for interface toughening. These findings are of importance for harnessing MNLs for use in future device wiring applications.

  20. Deuterium transport in Cu, CuCrZr, and Cu/Be

    NASA Astrophysics Data System (ADS)

    Anderl, R. A.; Hankins, M. R.; Longhurst, G. R.; Pawelko, R. J.

    This paper presents the results of deuterium implantation/permeation experiments and TMAP4 simulations for a CuCrZr alloy, for OFHC-Cu and for a Cu/Be bi-layered structure at temperatures from 700 to 800 K. Experiments used a mass-analyzed, 3-keV D 3+ ion beam with particle flux densities of 5 × 10 19 to 7 × 10 19 D/m 2 s. Effective diffusivities and surface molecular recombination coefficients were derived giving Arrhenius pre-exponentials and activation energies for each material: CuCrZr alloy, (2.0 × 10 -2 m 2/s, 1.2 eV) for diffusivity and (2.9 × x10 -14 m 4/s, 1.92 eV) for surface molecular recombination coefficients; OFHC Cu, (2.1 × 10 -6 m 2/s, 0.52 eV) for diffusivity and (9.1 × 10 -18 m 4/s, 0.99 eV) for surface molecular recombination coefficients. TMAP4 simulation of permeation data measured for a Cu/Be bi-layer sample was achieved using a four-layer structure (Cu/BeO interface/Be/BeO back surface) and recommended values for diffusivity and solubility in Be, BeO and Cu.

  1. From magic to technology: materials integration by wafer bonding

    NASA Astrophysics Data System (ADS)

    Dragoi, Viorel

    2006-02-01

    Wafer bonding became in the last decade a very powerful technology for MEMS/MOEMS manufacturing. Being able to offer a solution to overcome some problems of the standard processes used for materials integration (e.g. epitaxy, thin films deposition), wafer bonding is nowadays considered an important item in the MEMS engineer toolbox. Different principles governing the wafer bonding processes will be reviewed in this paper. Various types of applications will be presented as examples.

  2. Cu(II) and Cu(I) complexes with 1,2-dithiosquarate as a ligand; from molecular compounds to supramolecular network structures

    NASA Astrophysics Data System (ADS)

    Calatayud, M. Luisa; Castro, Isabel; Julve, Miguel; Sletten, Jorunn

    2008-03-01

    Four new complexes of copper(II) and/or copper(I) with 1,2-dtsq as a ligand have been synthesized and characterized by single crystal X-ray diffraction methods, [Cu II(terpy)(1,2-dtsq)] ( 1), [Cu II(dmen)(1,2-dtsq)] n ( 2), {[Cu II(dmen) 2][Cu I(1,2-dtsq)] 2} n·2nH 2O( 3) and {[Cu II(men) 2][Cu I (1,2-dtsq)] 2} n·nH 2O ( 4) (1,2-dtsq = 1,2-dithiosquarate, dianion of 3,4-dimercapto-1-cyclobutene-1,2-dione; dmen = N, N-dimethylethylenediamine; men = N-methylethylenediamine, terpy = 2,2':6,2″-terpyridine). Compound 1 consists of neutral [Cu II(terpy)(1,2-dtsq)] mononuclear units which are held together by O⋯H-C and van der Waals interactions. Compound 2 is built of neutral [Cu II(dmen)(1,2-dtsq)] entities which are connected through weak Cu-S (pairs) and Cu-O (single) interactions into a layer structure. The structures of 3 and 4 feature polynuclear [Cu(1,2-dtsq)]nn- chains, in which dtsq groups are linking copper(I) ions in the μ-1,1, μ-1,1,1 and μ-1,2 bridging modes. The dtsq groups in these chains connect to the copper(II) ions of the [Cu IIL 2] 2+ cations [L being the bidentate dmen ( 3) and men ( 4) ligands], but in different manners in the two structures. The connections in compound 3 are unsymmetrical, so that columns of {[Cu II(dmen) 2][Cu I(1,2-dtsq)] 2} n where the copper(II) ions bind to 1,2-dtsq oxygen atoms with relatively strong axial bonds may be identified. These columns are further connected to each other through weak axial Cu II⋯S interactions, creating a three-dimensional (3D) network with channels containing the solvent water. In compound 4, on the other hand, the two crystallographically independent cations each forms a symmetrical link between the anionic chains through, respectively, O-Cu II-O and S-Cu II-S axial bonds, again creating a 3D structure with channels running parallel to the chain axis. The reduction of copper(II) to copper(I) by 1,2-dtsq is precluded when the coordination sphere of the copper(II) ion is partially

  3. Copper(II) perrhenate Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2}: Synthesis from isopropanol and CuReO{sub 4}, structure and properties

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mikhailova, D., E-mail: d.mikhailova@ifw-dresden.de; Institute for Complex Materials, IFW Dresden, Helmholtzstrasse 20, D-01069 Dresden; Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, D-01187 Dresden

    2015-12-15

    The crystal structure of Cu{sup +}Re{sup 7+}O{sub 4} is capable of a quasi-reversible incorporation of C{sub 3}H{sub 7}OH molecules. A room-temperature reaction between CuReO{sub 4} and C{sub 3}H{sub 7}OH under oxidizing conditions leads to the formation of a novel metal-organic hybrid compound Cu{sup 2+}(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2}. Upon heating under reducing conditions, this compound transforms back into CuReO{sub 4}, albeit with ReO{sub 2} and metallic Cu as by-products. The crystal structure of Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2} solved from single-crystal X-ray diffraction (Pbca, a=10.005(3) Å, b=7.833(2) Å, and c=19.180(5) Å) reveals layers of corner-sharing CuO{sub 6}-octahedra andmore » ReO{sub 4}-tetrahedra, whereas isopropyl groups are attached to both sides of these layers, thus providing additional connections within the layers through hydrogen bonds. Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2} is paramagnetic down to 4 K because the spatial arrangement of the Cu{sup 2+} half-filled orbitals prevents magnetic superexchange. The paramagnetic effective moment of 2.0(1) μ{sub B} is slightly above the spin-only value and typical for Cu{sup 2+} ions. - Highlights: • Novel Cu(C{sub 3}H{sub 7}OH){sub 2}(ReO{sub 4}){sub 2} compound has a sequence of inorganic and organic layers. • Hydrogen bonds provide an additional bonding Isopropanol molecules serve as a reducing agent during decomposition. • No direct Cu-O-Re-O-Cu connections via d{sub x2-y2} orbital of Cu{sup 2+} explain paramagnetism. • Hydrogen bonds provide an additional bonding. • Isopropanol molecules serve as a reducing agent during decomposition.« less

  4. Room Temperature Radiolytic Synthesized Cu@CuAlO2-Al2O3 Nanoparticles

    PubMed Central

    Abedini, Alam; Saion, Elias; Larki, Farhad; Zakaria, Azmi; Noroozi, Monir; Soltani, Nayereh

    2012-01-01

    Colloidal Cu@CuAlO2-Al2O3 bimetallic nanoparticles were prepared by a gamma irradiation method in an aqueous system in the presence of polyvinyl pyrrolidone (PVP) and isopropanol respectively as a colloidal stabilizer and scavenger of hydrogen and hydroxyl radicals. The gamma irradiation was carried out in a 60Co gamma source chamber with different doses up to 120 kGy. The formation of Cu@CuAlO2-Al2O3 nanoparticles was observed initially by the change in color of the colloidal samples from colorless to brown. Fourier transform infrared spectroscopy (FTIR) confirmed the presence of bonds between polymer chains and the metal surface at all radiation doses. Results of transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDX), and X-ray diffraction (XRD) showed that Cu@CuAlO2-Al2O3 nanoparticles are in a core-shell structure. By controlling the absorbed dose and precursor concentration, nanoclusters with different particle sizes were obtained. The average particle diameter increased with increased precursor concentration and decreased with increased dose. This is due to the competition between nucleation, growth, and aggregation processes in the formation of nanoclusters during irradiation. PMID:23109893

  5. Fluorescence Lifetime Imaging of Physiological Free Cu(II) Levels in Live Cells with a Cu(II)-Selective Carbonic Anhydrase-Based Biosensor

    PubMed Central

    McCranor, Bryan J.; Szmacinski, Henryk; Zeng, Hui Hui; Stoddard, A.K.; Hurst, Tamiika; Fierke, Carol A.; Lakowicz, J.R.

    2014-01-01

    Copper is a required trace element that plays key roles in a number of human enzymes, such that copper deficiency or genetic defects in copper transport lead to serious or fatal disease. Rae, et al., had famously predicted that free copper ion levels in the cell cytoplasm were extremely low, typically too low to be observable. We recently developed a variant of human apocarbonic anhydrase II for sensing metal ions that exhibits 25-fold better selectivity for Cu(II) over Zn(II) than the wild type protein, enabling us to accurately measure Cu(II) in the presence of ordinary cellular (picomolar) concentrations of free zinc. We inserted a fluorescent labeled Cu(II)-specific variant of human apocarbonic anhydrase into PC-12 cells and found that the levels are indeed extremely low (in the femtomolar range). We imaged the free Cu(II) levels in living cells by means of frequency-domain fluorescence lifetime microscopy. Implications of this finding are discussed. PMID:24671220

  6. Density functional theory meta-GGA + U study of water incorporation in the metal-organic framework material Cu-BTC.

    PubMed

    Cockayne, Eric; Nelson, Eric B

    2015-07-14

    Water absorption in the metal-organic framework (MOF) material Cu-BTC, up to a concentration of 3.5 H2O per Cu ion, is studied via density functional theory at the meta-GGA + U level. The stable arrangements of water molecules show chains of hydrogen-bonded water molecules and a tendency to form closed cages at high concentration. Water clusters are stabilized primarily by a combination of water-water hydrogen bonding and Cu-water oxygen interactions. Stability is further enhanced by van der Waals interactions, electric field enhancement of water-water bonding, and hydrogen bonding of water to framework oxygens. We hypothesize that the tendency to form such stable clusters explains the particularly strong affinity of water to Cu-BTC and related MOFs with exposed metal sites.

  7. Wafer-Level Vacuum Packaging of Smart Sensors.

    PubMed

    Hilton, Allan; Temple, Dorota S

    2016-10-31

    The reach and impact of the Internet of Things will depend on the availability of low-cost, smart sensors-"low cost" for ubiquitous presence, and "smart" for connectivity and autonomy. By using wafer-level processes not only for the smart sensor fabrication and integration, but also for packaging, we can further greatly reduce the cost of sensor components and systems as well as further decrease their size and weight. This paper reviews the state-of-the-art in the wafer-level vacuum packaging technology of smart sensors. We describe the processes needed to create the wafer-scale vacuum microchambers, focusing on approaches that involve metal seals and that are compatible with the thermal budget of complementary metal-oxide semiconductor (CMOS) integrated circuits. We review choices of seal materials and structures that are available to a device designer, and present techniques used for the fabrication of metal seals on device and window wafers. We also analyze the deposition and activation of thin film getters needed to maintain vacuum in the ultra-small chambers, and the wafer-to-wafer bonding processes that form the hermetic seal. We discuss inherent trade-offs and challenges of each seal material set and the corresponding bonding processes. Finally, we identify areas for further research that could help broaden implementations of the wafer-level vacuum packaging technology.

  8. Wafer-Level Vacuum Packaging of Smart Sensors

    PubMed Central

    Hilton, Allan; Temple, Dorota S.

    2016-01-01

    The reach and impact of the Internet of Things will depend on the availability of low-cost, smart sensors—“low cost” for ubiquitous presence, and “smart” for connectivity and autonomy. By using wafer-level processes not only for the smart sensor fabrication and integration, but also for packaging, we can further greatly reduce the cost of sensor components and systems as well as further decrease their size and weight. This paper reviews the state-of-the-art in the wafer-level vacuum packaging technology of smart sensors. We describe the processes needed to create the wafer-scale vacuum microchambers, focusing on approaches that involve metal seals and that are compatible with the thermal budget of complementary metal-oxide semiconductor (CMOS) integrated circuits. We review choices of seal materials and structures that are available to a device designer, and present techniques used for the fabrication of metal seals on device and window wafers. We also analyze the deposition and activation of thin film getters needed to maintain vacuum in the ultra-small chambers, and the wafer-to-wafer bonding processes that form the hermetic seal. We discuss inherent trade-offs and challenges of each seal material set and the corresponding bonding processes. Finally, we identify areas for further research that could help broaden implementations of the wafer-level vacuum packaging technology. PMID:27809249

  9. On the CH...Cu agostic interaction: chiral copper(II) compounds with ephedrine and pseudoephedrine derivatives.

    PubMed

    Castro, Miguel; Cruz, Julián; López-Sandoval, Horacio; Barba-Behrens, Norah

    2005-08-14

    The ephedrine derivative, (H2ceph), yields [Cu(Hceph)2], showing a CH...Cu(II) agostic interaction; while in the analogous compound [Cu(Hcpse)2], with pseudoephedrine (H2cpse), that interaction is absent, despite the fact that these two diasteromers differ only in the orientation of the methyl and phenyl groups: erythro in H2ceph and threo in H2cpse. The X-ray crystal structure of [Cu(Hceph)2], indicates a Cu...HC length of 2.454 A and the theoretical study reveals the formation of a Cu...HC bond since the associated electronic density shows both a bond critical point and a bond ring critical point.

  10. Compositional ratio effect on the surface characteristics of CuZn thin films

    NASA Astrophysics Data System (ADS)

    Choi, Ahrom; Park, Juyun; Kang, Yujin; Lee, Seokhee; Kang, Yong-Cheol

    2018-05-01

    CuZn thin films were fabricated by RF co-sputtering method on p-type Si(100) wafer with various RF powers applied on metallic Cu and Zn targets. This paper aimed to determine the morphological, chemical, and electrical properties of the deposited CuZn thin films by utilizing a surface profiler, atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), UV photoelectron spectroscopy (UPS), and a 4-point probe. The thickness of the thin films was fixed at 200 ± 8 nm and the roughness of the thin films containing Cu was smaller than pure Zn thin films. XRD studies confirmed that the preferred phase changed, and this tendency is dependent on the ratio of Cu to Zn. AES spectra indicate that the obtained thin films consisted of Cu and Zn. The high resolution XPS spectra indicate that as the content of Cu increased, the intensities of Zn2+ decreased. The work function of CuZn thin films increased from 4.87 to 5.36 eV. The conductivity of CuZn alloy thin films was higher than pure metallic thin films.

  11. Comparison of Cu2+ and Zn2+ thermalcatalyst in treating diazo dye

    NASA Astrophysics Data System (ADS)

    Lau, Y. Y.; Wong, Y. S.; Ong, S. A.; Lutpi, N. A.; Ho, L. N.

    2018-05-01

    This research demonstrates the comparison between copper (II) sulphate (CuSO4) and zinc oxide (ZnO) as thermalcatalysts in thermolysis process for the treatment of diazo reactive black 5 (RB 5) wastewater. CuSO4 was found to be the most effective thermalcatalyst in comparison to ZnO. The color removal efficiency of RB 5 catalysed by CuSO4 and ZnO were 91.55 % at pH 9.5 and 7.36 % at pH 2, respectively. From the UV-Vis wavelength scan, CuSO4 catalyst is able to cleave the molecular structure bonding more efficiently compared to ZnO. ZnO which only show a slight decay on the main chemical network strands: azo bond, naphthalene and benzene rings whereas CuSO4 catalyst is able to fragment azo bond and naphthalene more effectively. The degradation reactions of CuSO4 and ZnO as thermalcatalysts in thermolysis process were compared.

  12. Very large scale heterogeneous integration (VLSHI) and wafer-level vacuum packaging for infrared bolometer focal plane arrays

    NASA Astrophysics Data System (ADS)

    Forsberg, Fredrik; Roxhed, Niclas; Fischer, Andreas C.; Samel, Björn; Ericsson, Per; Hoivik, Nils; Lapadatu, Adriana; Bring, Martin; Kittilsland, Gjermund; Stemme, Göran; Niklaus, Frank

    2013-09-01

    Imaging in the long wavelength infrared (LWIR) range from 8 to 14 μm is an extremely useful tool for non-contact measurement and imaging of temperature in many industrial, automotive and security applications. However, the cost of the infrared (IR) imaging components has to be significantly reduced to make IR imaging a viable technology for many cost-sensitive applications. This paper demonstrates new and improved fabrication and packaging technologies for next-generation IR imaging detectors based on uncooled IR bolometer focal plane arrays. The proposed technologies include very large scale heterogeneous integration for combining high-performance, SiGe quantum-well bolometers with electronic integrated read-out circuits and CMOS compatible wafer-level vacuum packing. The fabrication and characterization of bolometers with a pitch of 25 μm × 25 μm that are arranged on read-out-wafers in arrays with 320 × 240 pixels are presented. The bolometers contain a multi-layer quantum well SiGe thermistor with a temperature coefficient of resistance of -3.0%/K. The proposed CMOS compatible wafer-level vacuum packaging technology uses Cu-Sn solid-liquid interdiffusion (SLID) bonding. The presented technologies are suitable for implementation in cost-efficient fabless business models with the potential to bring about the cost reduction needed to enable low-cost IR imaging products for industrial, security and automotive applications.

  13. Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu{sup -}(cytidine) and Cu{sup -}(uridine)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li Xiang; Ko, Yeon-Jae; Wang Haopeng

    2011-02-07

    The copper-nucleoside anions, Cu{sup -}(cytidine) and Cu{sup -}(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu{sup -}(cytidine) and Cu{sup -}(uridine), respectively. According to our calculations, Cu{sup -}(cytidine) and Cu{sup -}(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostaticmore » interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu{sup -}(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.« less

  14. Deciphering ligands' interaction with Cu and Cu2O nanocrystal surfaces by NMR solution tools.

    PubMed

    Glaria, Arnaud; Cure, Jérémy; Piettre, Kilian; Coppel, Yannick; Turrin, Cédric-Olivier; Chaudret, Bruno; Fau, Pierre

    2015-01-12

    The hydrogenolysis of [Cu2{(iPrN)2(CCH3)}2] in the presence of hexadecylamine (HDA) or tetradecylphosphonic acid (TDPA) in toluene leads to 6-9 nm copper nanocrystals. Solution NMR spectroscopy has been used to describe the nanoparticle surface chemistry during the dynamic phenomenon of air oxidation. The ligands are organized as multilayered shells around the nanoparticles. The shell of ligands is controlled by both their intermolecular interactions and their bonding strength on the nanocrystals. Under ambient atmosphere, the oxidation rate of colloidal copper nanocrystals closely relies on the chemical nature of the employed ligands (base or acid). Primary amine molecules behave as soft ligands for Cu atoms, but are even more strongly coordinated on surface Cu(I) sites, thus allowing a very efficient corrosion protection of the copper core. On the contrary, the TDPA ligands lead to a rapid oxidation rate of Cu nanoparticles and eventually to the re-dissolution of Cu(II) species at the expense of the nanocrystals. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Wafer-Level Membrane-Transfer Process for Fabricating MEMS

    NASA Technical Reports Server (NTRS)

    Yang, Eui-Hyeok; Wiberg, Dean

    2003-01-01

    A process for transferring an entire wafer-level micromachined silicon structure for mating with and bonding to another such structure has been devised. This process is intended especially for use in wafer-level integration of microelectromechanical systems (MEMS) that have been fabricated on dissimilar substrates. Unlike in some older membrane-transfer processes, there is no use of wax or epoxy during transfer. In this process, the substrate of a wafer-level structure to be transferred serves as a carrier, and is etched away once the transfer has been completed. Another important feature of this process is that two electrodes constitutes an electrostatic actuator array. An SOI wafer and a silicon wafer (see Figure 1) are used as the carrier and electrode wafers, respectively. After oxidation, both wafers are patterned and etched to define a corrugation profile and electrode array, respectively. The polysilicon layer is deposited on the SOI wafer. The carrier wafer is bonded to the electrode wafer by using evaporated indium bumps. The piston pressure of 4 kPa is applied at 156 C in a vacuum chamber to provide hermetic sealing. The substrate of the SOI wafer is etched in a 25 weight percent TMAH bath at 80 C. The exposed buried oxide is then removed by using 49 percent HF droplets after an oxygen plasma ashing. The SOI top silicon layer is etched away by using an SF6 plasma to define the corrugation profile, followed by the HF droplet etching of the remaining oxide. The SF6 plasma with a shadow mask selectively etches the polysilicon membrane, if the transferred membrane structure needs to be patterned. Electrostatic actuators with various electrode gaps have been fabricated by this transfer technique. The gap between the transferred membrane and electrode substrate is very uniform ( 0.1 m across a wafer diameter of 100 mm, provided by optimizing the bonding control). Figure 2 depicts the finished product.

  16. Sulfur passivation techniques for III-V wafer bonding

    NASA Astrophysics Data System (ADS)

    Jackson, Michael James

    The use of direct wafer bonding in a multijunction III-V solar cell structure requires the formation of a low resistance bonded interface with minimal thermal treatment. A wafer bonded interface behaves as two independent surfaces in close proximity, hence a major source of resistance is Fermi level pinning common in III-V surfaces. This study demonstrates the use of sulfur passivation in III-V wafer bonding to reduce the energy barrier at the interface. Two different sulfur passivation processes are addressed. A dry sulfur passivation method that utilizes elemental sulfur vapor activated by ultraviolet light in vacuum is compared with aqueous sulfide and native oxide etch treatments. Through the addition of a sulfur desorption step in vacuum, the UV-S treatment achieves bondable surfaces free of particles contamination or surface roughening. X-ray photoelectron spectroscopy measurements of the sulfur treated GaAs surfaces find lower levels of oxide and the appearance of sulfide species. After 4 hrs of air exposure, the UV-S treated GaAs actually showed an increase in the amount of sulfide bonded to the semiconductor, resulting in less oxidation compared to the aqueous sulfide treatment. Large area bonding is achieved for sulfur treated GaAs / GaAs and InP / InP with bulk fracture strength achieved after annealing at 400 °C and 300 °C respectively, without large compressive forces. The electrical conductivity across a sulfur treated 400 °C bonded n-GaAs/n-GaAs interface significantly increased with a short anneal (1-2 minutes) at elevated temperatures (50--600 °C). Interfaces treated with the NH4OH oxide etch, on the other hand, exhibited only mild improvement in accordance with previously published studies in this area. TEM and STEM images revealed similar interfacial microstructure changes with annealing for both sulfur treated and NH4OH interfaces, whereby some areas have direct semiconductor-semiconductor contact without any interfacial layer. Fitting the

  17. Graphitized silicon carbide microbeams: wafer-level, self-aligned graphene on silicon wafers

    NASA Astrophysics Data System (ADS)

    Cunning, Benjamin V.; Ahmed, Mohsin; Mishra, Neeraj; Ranjbar Kermany, Atieh; Wood, Barry; Iacopi, Francesca

    2014-08-01

    Currently proven methods that are used to obtain devices with high-quality graphene on silicon wafers involve the transfer of graphene flakes from a growth substrate, resulting in fundamental limitations for large-scale device fabrication. Moreover, the complex three-dimensional structures of interest for microelectromechanical and nanoelectromechanical systems are hardly compatible with such transfer processes. Here, we introduce a methodology for obtaining thousands of microbeams, made of graphitized silicon carbide on silicon, through a site-selective and wafer-scale approach. A Ni-Cu alloy catalyst mediates a self-aligned graphitization on prepatterned SiC microstructures at a temperature that is compatible with silicon technologies. The graphene nanocoating leads to a dramatically enhanced electrical conductivity, which elevates this approach to an ideal method for the replacement of conductive metal films in silicon carbide-based MEMS and NEMS devices.

  18. Benzotriazole removal on post-Cu CMP cleaning

    NASA Astrophysics Data System (ADS)

    Jiying, Tang; Yuling, Liu; Ming, Sun; Shiyan, Fan; Yan, Li

    2015-06-01

    This work investigates systematically the effect of FA/O II chelating agent and FA/O I surfactant in alkaline cleaning solutions on benzotriazole (BTA) removal during post-Cu CMP cleaning in GLSI under the condition of static etching. The best detergent formulation for BTA removal can be determined by optimization of the experiments of single factor and compound cleaning solution, which has been further confirmed experimentally by contact angle (CA) measurements. The resulting solution with the best formulation has been measured for the actual production line, and the results demonstrate that the obtained cleaning solution can effectively and efficiently remove BTA, CuO and abrasive SiO2 without basically causing interfacial corrosion. This work demonstrates the possibility of developing a simple, low-cost and environmentally-friendly cleaning solution to effectively solve the issues of BTA removal on post-Cu CMP cleaning in a multi-layered copper wafer. Project supported by the Major National Science and Technology Special Projects (No. 2009ZX02308).

  19. A wafer-level vacuum package using glass-reflowed silicon through-wafer interconnection for nano/micro devices.

    PubMed

    Jin, Joo-Young; Yoo, Seung-Hyun; Yoo, Byung-Wook; Kim, Yong-Kweon

    2012-07-01

    We propose a vacuum wafer-level packaging (WLP) process using glass-reflowed silicon via for nano/micro devices (NMDs). A through-wafer interconnection (TWIn) substrate with silicon vias and reflowed glass is introduced to accomplish a vertical feed-through of device. NMDs are fabricated in the single crystal silicon (SCS) layer which is formed on the TWIn substrate by Au eutectic bonding including Cr adhesion layer. The WLPof the devices is achieved with the capping glass wafer anodically bonded to the SCS layer. In order to demonstrate the successful hermetic packaging, we fabricated the micro-Pirani gauge in the SCS layer, and packaged it in the wafer-level. The vacuum level inside the packaging was measured to be 3.1 Torr with +/- 0.12 Torr uncertainty, and the packaging leakage was not detected during 24 hour after the packaging.

  20. Systematics of Structural, Phase Stability, and Cohesive Properties of η'-Cu6(Sn,In)5 Compounds Occurring in In-Sn/Cu Solder Joints

    NASA Astrophysics Data System (ADS)

    Ramos, S. B.; González Lemus, N. V.; Deluque Toro, C. E.; Cabeza, G. F.; Fernández Guillermet, A.

    2017-07-01

    Motivated by the high solubility of In in ( mC44) η'-Cu6Sn5 compound as well as the occurrence of an In-doped η'-intermetallic in the microstructure of Cu/In-Sn/Cu solder joints, a theoretical study has been carried out to investigate the various physical effects of incorporating In at Sn Wyckoff sites of the binary η'-phase. Systematic ab initio calculations using the projected augmented wave method and Vienna Ab initio Simulation Package were used to determine the composition dependence of the structural and cohesive properties of η'-Cu6(Sn,In)5 compounds, compared with those expected from the binary end-member compounds Cu6Sn5 and Cu6In5. The molar volume shows significant deviations from Vegard's law. The predicted composition dependence of the cohesive properties is discussed using two complementary approaches, viz. a valence-electron density approach as well as a bond-number approach, both accounting for the roughly linear dependence of the cohesive energy on the In content. A microscopic interpretation for this general trend is given in terms of the key contributions to chemical bonding in this class of compounds, namely Cu d-electron overlap and hybridization of Cu d-states with In and Sn p-electron states. Moreover, a crystallographic site approach is developed to accurately establish the phase-stabilizing effect of incorporating In at specific Wyckoff positions of the ( mC44) η'-Cu6Sn5 structure.

  1. Stress and plasticity in Cu thin films

    NASA Astrophysics Data System (ADS)

    Weihnacht, Volker; Brückner, Winfried

    1999-11-01

    Aim of the work was to get more detailed knowledge about the processes of plasticity in thin Cu films. For this purpose, stress measurements and microstructural investigations have been done on 535nm thick Cu films on oxidized Si substrates. The film stress was measured by wafer-curvature technique using a home-made laser-optical apparatus. This apparatus allowed four-point bending experiments additionally to thermal cycling. It turned out that applied bending strains even higher than 0.5% did not leave significant plastic strains after relief of bending stress. It is concluded, that the elastic interaction of parallel dislocations at the film-substrate interface may play an important role in strain hardening even after small plastic strains.

  2. Symmetry and novelty in the electronic and geometric structure of nanoalloys:. the case of Ag27Cu7

    NASA Astrophysics Data System (ADS)

    Ortigoza, M. Alcántara; Rahman, T. S.

    2008-04-01

    Nanoparticles of bimetallic alloys have been shown to possess composition dependent characteristics which distinguish themselves from the corresponding bulk alloys. Taking the 34-atom nanoalloy of Ag and Cu (Ag27Cu7), we show using first principles electronic structure calculations that this core-shell alloy indeed has perfect D5h symmetry and consists of only 6 non-equivalent (2 Cu and 4 Ag) atoms. Analysis of the interatomic bond lengths and detailed electronic structure further reveal that the Cu atoms play a major role in controlling the characteristics of the nanoalloy. The higher cohesive energy, together with shorter bond length for Cu, compared to Ag, conspire to produce a hierarchy in the relative strengths of the Ag - Cu, Ag - Ag, and Cu - Cu bonds and corresponding interatomic bond lengths, point to the uniqueness in the characteristics of this nanoalloy. Charge density plots of Ag27Cu7 provide further insights into the relative strengths of the various interatomic bonds.

  3. CeO2-CuO/Cu2O/Cu monolithic catalysts with three-kind morphologies Cu2O layers for preferential CO oxidation

    NASA Astrophysics Data System (ADS)

    Jing, Guojuan; Zhang, Xuejiao; Zhang, Aiai; Li, Meng; Zeng, Shanghong; Xu, Changjin; Su, Haiquan

    2018-03-01

    The supports of copper slices with three-kind morphologies Cu2O layers were prepared by the hydrothermal method. The Cu2O layers are rod-like structure, three-dimensional reticular and porous morphology as well as flower-like morphology, respectively. The CeO2-CuO/Cu2O/Cu monolithic catalysts present porous and network structure or foam morphology after loading CeO2 and CuO. Cu and Ce elements are uniformly dispersed onto the support surface. It is found that the monolithic catalyst with flower-like Cu2O layer displays better low-temperature activity because of highly-dispersed CuO and high Olatt concentration. The monolithic catalysts with rod-like or reticular-morphology Cu2O layers present high-temperature activity due to larger CuO crystallite sizes and good synergistic effect at copper-ceria interfacial sites. The as-prepared CeO2-CuO/Cu2O/Cu monolithic catalysts show good performance in the CO-PROX reaction. The generation of Cu2O layers with three-kind morphologies is beneficial to the loading and dispersion of copper oxides and ceria.

  4. CH4 dehydrogenation on Cu(1 1 1), Cu@Cu(1 1 1), Rh@Cu(1 1 1) and RhCu(1 1 1) surfaces: A comparison studies of catalytic activity

    NASA Astrophysics Data System (ADS)

    Zhang, Riguang; Duan, Tian; Ling, Lixia; Wang, Baojun

    2015-06-01

    In the CVD growth of graphene, the reaction barriers of the dehydrogenation for hydrocarbon molecules directly decide the graphene CVD growth temperature. In this study, density functional theory method has been employed to comparatively probe into CH4 dehydrogenation on four types of Cu(1 1 1) surface, including the flat Cu(1 1 1) surface (labeled as Cu(1 1 1)) and the Cu(1 1 1) surface with one surface Cu atom substituted by one Rh atom (labeled as RhCu(1 1 1)), as well as the Cu(1 1 1) surface with one Cu or Rh adatom (labeled as Cu@Cu(1 1 1) and Rh@Cu(1 1 1), respectively). Our results show that the highest barrier of the whole CH4 dehydrogenation process is remarkably reduced from 448.7 and 418.4 kJ mol-1 on the flat Cu(1 1 1) and Cu@Cu(1 1 1) surfaces to 258.9 kJ mol-1 on RhCu(1 1 1) surface, and to 180.0 kJ mol-1 on Rh@Cu(1 1 1) surface, indicating that the adsorbed or substituted Rh atom on Cu catalyst can exhibit better catalytic activity for CH4 complete dehydrogenation; meanwhile, since the differences for the highest barrier between Cu@Cu(1 1 1) and Cu(1 1 1) surfaces are smaller, the catalytic behaviors of Cu@Cu(1 1 1) surface are very close to the flat Cu(1 1 1) surface, suggesting that the morphology of Cu substrate does not obviously affect the dehydrogenation of CH4, which accords with the reported experimental observations. As a result, the adsorbed or substituted Rh atom on Cu catalyst exhibit a better catalytic activity for CH4 dehydrogenation compared to the pure Cu catalyst, especially on Rh-adsorbed Cu catalyst, we can conclude that the potential of synthesizing high-quality graphene with the help of Rh on Cu foils may be carried out at relatively low temperatures. Meanwhile, the adsorbed Rh atom is the reaction active center, namely, the CVD growth can be controlled by manipulating the graphene nucleation position.

  5. Band structure calculations of CuAlO2, CuGaO2, CuInO2, and CuCrO2 by screened exchange

    NASA Astrophysics Data System (ADS)

    Gillen, Roland; Robertson, John

    2011-07-01

    We report density functional theory band structure calculations on the transparent conducting oxides CuAlO2, CuGaO2, CuInO2, and CuCrO2. The use of the hybrid functional screened-exchange local density approximation (sX-LDA) leads to considerably improved electronic properties compared to standard LDA and generalized gradient approximation (GGA) approaches. We show that the resulting electronic band gaps compare well with experimental values and previous quasiparticle calculations, and show the correct trends with respect to the atomic number of the cation (Al, Ga, In). The resulting energetic depths of Cu d and O p levels and the valence-band widths are considerable improvements compared to LDA and GGA and are in good agreement with available x-ray photoelectron spectroscopy data. Lastly, we show the calculated imaginary part of the dielectric function for all four systems.

  6. Controlling intermetallic compound growth in SnAgCu/Ni-P solder joints by nanosized Cu6Sn5 addition

    NASA Astrophysics Data System (ADS)

    Kao, Szu-Tsung; Lin, Yung-Chi; Duh, Jenq-Gong

    2006-03-01

    Nanosized Cu6Sn5 dispersoids were incorporated into Sn and Ag powders and milled together to form Sn-3Ag-0.5Cu composite solders by a mechanical alloying process. The aim of this study was to investigate the interfacial reaction between SnAgCu composite solder and electroless Ni-P/Cu UBM after heating for 15 min. at 240°C. The growth of the IMCs formed at the composite solder/EN interface was retarded as compared to the commercial Sn3Ag0.5Cu solder joints. With the aid of the elemental distribution by x-ray color mapping in electron probe microanalysis (EPMA), it was revealed that the SnAgCu composite solder exhibited a refined structure. It is proposed that the Cu6Sn5 additives were pinned on the grain boundary of Sn after heat treatment, which thus retarded the movement of Cu toward the solder/EN interface to form interfacial compounds. In addition, wetting is an essential prerequisite for soldering to ensure good bonding between solder and substrate. It was demonstrated that the contact angles of composite solder paste was <25°, and good wettability was thus assured.

  7. Mechanics of wafer bonding: Effect of clamping

    NASA Astrophysics Data System (ADS)

    Turner, K. T.; Thouless, M. D.; Spearing, S. M.

    2004-01-01

    A mechanics-based model is developed to examine the effects of clamping during wafer bonding processes. The model provides closed-form expressions that relate the initial geometry and elastic properties of the wafers to the final shape of the bonded pair and the strain energy release rate at the interface for two different clamping configurations. The results demonstrate that the curvature of bonded pairs may be controlled through the use of specific clamping arrangements during the bonding process. Furthermore, it is demonstrated that the strain energy release rate depends on the clamping configuration and that using applied loads usually leads to an undesirable increase in the strain energy release rate. The results are discussed in detail and implications for process development and bonding tool design are highlighted.

  8. A ternary Cu2O-Cu-CuO nanocomposite: a catalyst with intriguing activity.

    PubMed

    Sasmal, Anup Kumar; Dutta, Soumen; Pal, Tarasankar

    2016-02-21

    In this work, the syntheses of Cu2O as well as Cu(0) nanoparticle catalysts are presented. Copper acetate monohydrate produced two distinctly different catalyst particles with varying concentrations of hydrazine hydrate at room temperature without using any surfactant or support. Then both of them were employed separately for 4-nitrophenol reduction in aqueous solution in the presence of sodium borohydride at room temperature. To our surprise, it was noticed that the catalytic activity of Cu2O was much higher than that of the metal Cu(0) nanoparticles. We have confirmed the reason for the exceptionally high catalytic activity of cuprous oxide nanoparticles over other noble metal nanoparticles for 4-nitrophenol reduction. A plausible mechanism has been reported. The unusual activity of Cu2O nanoparticles in the reduction reaction has been observed because of the in situ generated ternary nanocomposite, Cu2O-Cu-CuO, which rapidly relays electrons and acts as a better catalyst. In this ternary composite, highly active in situ generated Cu(0) is proved to be responsible for the hydride transfer reaction. The mechanism of 4-nitrophenol reduction has been established from supporting TEM studies. To further support our proposition, we have prepared a compositionally similar Cu2O-Cu-CuO nanocomposite using Cu2O and sodium borohydride which however displayed lower rate of reduction than that of the in situ produced ternary nanocomposite. The evolution of isolated Cu(0) nanoparticles for 4-nitrophenol reduction from Cu2O under surfactant-free condition has also been taken into consideration. The synthetic procedures of cuprous oxide as well as its catalytic activity in the reduction of 4-nitrophenol are very convenient, fast, cost-effective, and easily operable in aqueous medium and were followed spectrophotometrically. Additionally, the Cu2O-catalyzed 4-nitrophenol reduction methodology was extended further to the reduction of electronically diverse nitroarenes. This

  9. Effects of temperature and holding time on bonding W and W-Cu composites with an amorphous W-Fe coated copper foil as the interlayer by hot-pressing

    NASA Astrophysics Data System (ADS)

    Zhao, Pei; Wang, Song; Guo, Shibin; Chen, Yixiang; Ling, Yunhan; Li, Jiangtao

    2013-07-01

    W and W-Cu composites were bonded with an amorphous W-Fe coated copper foil as the interlayer at different temperature and holding time by hot pressing method. Effects of the bonding temperature and holding time on the microstructure and thermal conductivity of the bonded specimens were investigated. The thermal conductivity of the bonded sample increased with the bonding temperature and reached the maximum at 1000 °C, but essentially unchanged with the holding time. Because at 1000 °C more W-Fe compounds would be formed at the interlayer, which were helpful for tight bonding of W and W-Cu composites, and the grain size was larger which could reduce thermal resistance. The W-Cu FGM bonded by this method showed good resistance to thermal load, and performed well when facing to short pulse plasma in experimental advanced superconducting tokamak (the first full superconductive fusion device in the world).

  10. Theoretical and experimental studies of the molecular orbital bonding coefficients for Cu{sup 2+} ion in cesium hydrogen oxalate single crystals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kalfaoğlu, Emel, E-mail: emelkalfaoglu@mynet.com; Karabulut, Bünyamin

    2016-03-25

    Electron paramagnetic resonance (EPR) and optical absorption spectra of Cu{sup 2+} ions in cesium hydrogen oxalate single crystals have been investigated at room temperature. The spin-Hamiltonian parameters (g and A), have been determined. Crystalline field around the Cu{sup 2+} ion is almost axially symmetric. The results show a single paramagnetic site which confirms the triclinic crystal symmetry. Molecular orbital bonding coefficients are studied from the EPR and optical data. Theoretical octahedral field parameter and the tetragonal field parameters have been evaluated from the superposition model. Using these parameters, various bonding parameters are analyzed and the nature of bonding in themore » complex is discussed. The theoretical results are supported by experimental results.« less

  11. Fabrication of uniform nanoscale cavities via silicon direct wafer bonding.

    PubMed

    Thomson, Stephen R D; Perron, Justin K; Kimball, Mark O; Mehta, Sarabjit; Gasparini, Francis M

    2014-01-09

    Measurements of the heat capacity and superfluid fraction of confined (4)He have been performed near the lambda transition using lithographically patterned and bonded silicon wafers. Unlike confinements in porous materials often used for these types of experiments(3), bonded wafers provide predesigned uniform spaces for confinement. The geometry of each cell is well known, which removes a large source of ambiguity in the interpretation of data. Exceptionally flat, 5 cm diameter, 375 µm thick Si wafers with about 1 µm variation over the entire wafer can be obtained commercially (from Semiconductor Processing Company, for example). Thermal oxide is grown on the wafers to define the confinement dimension in the z-direction. A pattern is then etched in the oxide using lithographic techniques so as to create a desired enclosure upon bonding. A hole is drilled in one of the wafers (the top) to allow for the introduction of the liquid to be measured. The wafers are cleaned(2) in RCA solutions and then put in a microclean chamber where they are rinsed with deionized water(4). The wafers are bonded at RT and then annealed at ~1,100 °C. This forms a strong and permanent bond. This process can be used to make uniform enclosures for measuring thermal and hydrodynamic properties of confined liquids from the nanometer to the micrometer scale.

  12. Cu-catalyzed C(sp³)-H bond activation reaction for direct preparation of cycloallyl esters from cycloalkanes and aromatic aldehydes.

    PubMed

    Zhao, Jincan; Fang, Hong; Han, Jianlin; Pan, Yi

    2014-05-02

    Cu-catalyzed dehydrogenation-olefination and esterification of C(sp(3))-H bonds of cycloalkanes with TBHP as an oxidant has been developed. The reaction involves four C-H bond activations and gives cycloallyl ester products directly from cycloalkanes and aromatic aldehydes.

  13. Cu(II)-catalyzed esterification reaction via aerobic oxidative cleavage of C(CO)-C(alkyl) bonds.

    PubMed

    Ma, Ran; He, Liang-Nian; Liu, An-Hua; Song, Qing-Wen

    2016-02-04

    A novel Cu(II)-catalyzed aerobic oxidative esterification of simple ketones for the synthesis of esters has been developed with wide functional group tolerance. This process is assumed to go through a tandem sequence consisting of α-oxygenation/esterification/nucleophilic addition/C-C bond cleavage and carbon dioxide is released as the only byproduct.

  14. Porous HKUST-1 derived CuO/Cu2O shell wrapped Cu(OH)2 derived CuO/Cu2O core nanowire arrays for electrochemical nonenzymatic glucose sensors with ultrahigh sensitivity

    NASA Astrophysics Data System (ADS)

    Yu, Cuiping; Cui, Jiewu; Wang, Yan; Zheng, Hongmei; Zhang, Jianfang; Shu, Xia; Liu, Jiaqin; Zhang, Yong; Wu, Yucheng

    2018-05-01

    Self-supported CuO/Cu2O@CuO/Cu2O core-shell nanowire arrays (NWAs) are successfully fabricated by a simple and efficient method in this paper. Anodized Cu(OH)2 NWAs could in-situ convert to HKUST-1 at room temperature easily. Cu(OH)2 NWAs cores and HKUST-1 shells transform into CuO/Cu2O simultaneously after calcinations and form CuO/Cu2O@CuO/Cu2O core-shell NWAs. This smart configuration of the core-shell structure not only avoids the agglomeration of the traditional MOF-derived materials in particle-shape, but also facilitates the ion diffusion and increases the active sites. This novel structure is employed as substrate to construct nonenzymatic glucose sensors. The results indicate that glucose sensor based on CuO/Cu2O@CuO/Cu2O core-shell NWAs presents ultrahigh sensitivity (10,090 μA mM-1 cm-2), low detection limit (0.48 μM) and wide linear range (0.99-1,330 μM). In addition, it also shows excellent anti-interference ability toward uric acid, ascorbic acid and L-Cysteine co-existing with glucose, good reproducibility and superior ability of real sample analysis.

  15. Cu(I)/Cu(II) mixed-valence surface complexes of S-[(2-hydroxyamino)-2-oxoethyl]-N,N-dibutyldithiocarbamate: Hydrophobic mechanism to malachite flotation.

    PubMed

    Liu, Sheng; Zhong, Hong; Liu, Guangyi; Xu, Zhenghe

    2018-02-15

    Hydroxamate and sulfhydryl surfactants are effective collectors for flotation of copper minerals. The combination application of hydroxamate and sulfhydryl collectors has been proved to be an effective approach for improving the flotation recovery of non-sulfide copper minerals. A surfactant owing both hydroxamate and dithiocarbamate groups might exhibit strong affinity to non-sulfide copper minerals through double sites adsorption, rendering an enhanced hydrophobization to non-sulfide copper minerals flotation. The flotation performance of S-[(2-hydroxyamino)-2-oxoethyl]- N,N-dibutyldithiocarbamate (HABTC) to malachite, calcite and quartz were first evaluated through systematic micro-flotation experiments. HABTC's hydrophobic mechanism to malachite was further investigated and analyzed by zeta potential, Fourier transform infrared spectroscopy (FTIR), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The micro-flotation results demonstrated HABTC was an excellent collector for malachite flotation and exhibited favorable selectivity for flotation separation of malachite from quartz or calcite under pH 8.5-10.3. Zeta potential and FTIR implied that HABTC might bond with the surface copper atoms of malachite, with releasing the H + ions of its hydroxamate group into pulp. ToF-SIMS provided clear evidences that the Cu-hydroxamate and Cu-dithiocarbamate groups were formed on malachite surfaces after HABTC adsorption. XPS revealed that Cu(I)/Cu(II) mixed-valence surface complexes of HABTC anchored on malachite through formation of Cu(I)S and Cu(II)O bonds, accompanying with reduction of partial surface Cu(II) to Cu(I). The Cu(I)/Cu(II) mixed-valence double chelating character and "chair"-shape N,N-dibutyldithiocarbamate hydrophobic group, resulting in an enhanced affinity and hydrophobization of HABTC to malachite flotation. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Differential affinity of BsSCO for Cu(II) and Cu(I) suggests a redox role in copper transfer to the Cu(A) center of cytochrome c oxidase.

    PubMed

    Hill, Bruce C; Andrews, Diann

    2012-06-01

    SCO (synthesis of cytochrome c oxidase) proteins are involved in the assembly of the respiratory chain enzyme cytochrome c oxidase acting to assist in the assembly of the Cu(A) center contained within subunit II of the oxidase complex. The Cu(A) center receives electrons from the reductive substrate ferrocytochrome c, and passes them on to the cytochrome a center. Cytochrome a feeds electrons to the oxygen reaction site composed of cytochrome a(3) and Cu(B). Cu(A) consists of two copper ions positioned within bonding distance and ligated by two histidine side chains, one methionine, a backbone carbonyl and two bridging cysteine residues. The complex structure and redox capacity of Cu(A) present a potential assembly challenge. SCO proteins are members of the thioredoxin family which led to the early suggestion of a disulfide exchange function for SCO in Cu(A) assembly, whereas the copper binding capacity of the Bacillus subtilis version of SCO (i.e., BsSCO) suggests a direct role for SCO proteins in copper transfer. We have characterized redox and copper exchange properties of apo- and metalated-BsSCO. The release of copper (II) from its complex with BsSCO is best achieved by reducing it to Cu(I). We propose a mechanism involving both disulfide and copper exchange between BsSCO and the apo-Cu(A) site. This article is part of a Special Issue entitled: Biogenesis/Assembly of Respiratory Enzyme Complexes. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Microstructure and Thermal Conductivity of Carbon Nanotube Reinforced Cu Composites.

    PubMed

    Chen, Pingan; Zhang, Jian; Shen, Qiang; Luo, Guoqiang; Dai, Yang; Wang, Chuanbing; Li, Meijuan; Zhang, Lianmeng

    2017-04-01

    Microstructure and thermal conductivity (TC) of carbon nanotubes reinforced Cu (CNT-Cu) composites have been studied. When CNTs were coated with nano Cu by electroless plating, the TC of CNT-Cu composites showed a noticeable improvement and increased with CNT contents. When 1.0 vol% CNTs was added, the TC of CNT-Cu composites increased to 420.4 W/(m · K), 30% higher than that of monolithic Cu (323.1 W/(m · K)). According to the measured TC of CNT-Cu composites, the interfacial thermal resistance of CNT-Cu composites was calculated as 3.0 × 10⁻⁹ m² K/W which was lower than the reported values of CNTs reinforced polymer matrix composites and ceramic matrix composites. Microstructures showed that CNTs modified with nano Cu were homogeneously dispersed and embedded in the Cu matrix, indicating that there was strong bonding between CNTs and Cu. The homogeneously dispersed CNTs and reduction of interfacial thermal resistance resulted in the improvement of thermal conductivity of CNT-Cu composites. Therefore, the prepared CNT-Cu composites are promising materials for thermal management applications.

  18. In situ imaging of the soldering reactions in nanoscale Cu/Sn/Cu and Sn/Cu/Sn diffusion couples

    NASA Astrophysics Data System (ADS)

    Yin, Qiyue; Gao, Fan; Gu, Zhiyong; Wang, Jirui; Stach, Eric A.; Zhou, Guangwen

    2018-01-01

    The soldering reactions of three-segmented Sn/Cu/Sn and Cu/Sn/Cu diffusion couples are monitored by in-situ transmission electron microscopy to reveal the metallurgical reaction mechanism and the associated phase transformation pathway. For Sn/Cu/Sn diffusion couples, there is no ɛ-Cu3Sn formation due to the relatively insufficient Cu as compared to Sn. Kirkendall voids form initially in the Cu segment and then disappear due to the volume expansion associated with the continued intermetallic compound (IMC) formation as the reaction progresses. The incoming Sn atoms react with Cu to form η-Cu6Sn5, and the continuous reaction then transforms the entire nanowire to η-Cu6Sn5 grains with remaining Sn. With continued heating slightly above the melting point of Sn, an Sn-rich liquid phase forms between η-Cu6Sn5 grains. By contrast, the reaction in the Cu/Sn/Cu diffusion couples results in the intermetallic phases of both Cu3Sn and Cu6Sn5 and the development of Cu6Sn5 bulges on Cu3Sn grains. Kirkendall voids form in the two Cu segments, which grow and eventually break the nanowire into multiple segments.

  19. CuO-Functionalized Silicon Photoanodes for Photoelectrochemical Water Splitting Devices.

    PubMed

    Shi, Yuanyuan; Gimbert-Suriñach, Carolina; Han, Tingting; Berardi, Serena; Lanza, Mario; Llobet, Antoni

    2016-01-13

    One main difficulty for the technological development of photoelectrochemical (PEC) water splitting (WS) devices is the fabrication of active, stable and cost-effective photoelectrodes that ensure high performance. Here, we report the development of a CuO/Silicon based photoanode, which shows an onset potential for the water oxidation of 0.53 V vs SCE at pH 9, that is, an overpotential of 75 mV, and high stability above 10 h. These values account for a photovoltage of 420 mV due to the absorbed photons by silicon, as proven by comparing with analogous CuO/FTO electrodes that are not photoactive. The photoanodes have been fabricated by sputtering a thin film of Cu(0) on commercially available n-type Si wafers, followed by a photoelectrochemical treatment in basic pH conditions. The resulting CuO/Cu layer acts as (1) protective layer to avoid the corrosion of nSi, (2) p-type hole conducting layer for efficient charge separation and transportation, and (3) electrocatalyst to reduce the overpotential of the water oxidation reaction. The low cost, low toxicity, and good performance of CuO-based coatings can be an attractive solution to functionalize unstable materials for solar energy conversion.

  20. [Co(NH3)6]3[Cu4(OH)(CO3)8].2H2O--a new carbonato-copper(II) anion stabilized by extensive hydrogen bonding.

    PubMed

    Abrahams, Brendan F; Haywood, Marissa G; Robson, Richard

    2004-04-21

    Addition of Co(NH3)6(3+) to aqueous solutions of Cu(II) in excess carbonate promotes the assembly of a new highly charged carbonato-copper(II) anion, [Cu4(OH)(CO3)8](9-), which contains an unusual mu4 hydroxo-bridged square Cu4 arrangement, stabilised in the crystal by no less than forty hydrogen bonds (< 3 Angstrom) to hexammine cations.

  1. High-κ Al2O3 material in low temperature wafer-level bonding for 3D integration application

    NASA Astrophysics Data System (ADS)

    Fan, J.; Tu, L. C.; Tan, C. S.

    2014-03-01

    This work systematically investigated a high-κ Al2O3 material for low temperature wafer-level bonding for potential applications in 3D microsystems. A clean Si wafer with an Al2O3 layer thickness of 50 nm was applied as our experimental approach. Bonding was initiated in a clean room ambient after surface activation, followed by annealing under inert ambient conditions at 300 °C for 3 h. The investigation consisted of three parts: a mechanical support study using the four-point bending method, hermeticity measurements using the helium bomb test, and thermal conductivity analysis for potential heterogeneous bonding. Compared with samples bonded using a conventional oxide bonding material (SiO2), a higher interfacial adhesion energy (˜11.93 J/m2) and a lower helium leak rate (˜6.84 × 10-10 atm.cm3/sec) were detected for samples bonded using Al2O3. More importantly, due to the excellent thermal conductivity performance of Al2O3, this technology can be used in heterogeneous direct bonding, which has potential applications for enhancing the performance of Si photonic integrated devices.

  2. Metal-organic framework: Structure and magnetic properties of [Cu3(BTC)2 (L)x·(CuO)y]n (L=H2O, DMF)

    NASA Astrophysics Data System (ADS)

    da Silva, Gilvaldo G.; Machado, F. L. A.; Junior, S. Alves; Padrón-Hernández, E.

    2017-09-01

    The compounds [Cu3(BTC)2(L)x·(CuO)y], with BTC (benzene 1,3,5-tricarboxylate) and L (H2O or DMF) were prepared using electrochemical synthesis. Structural and morphologic characterizations were performed by X-ray diffraction and scanning electronic microscopy. The [Cu3(BTC)2 (L)x·(CuO)y] contain dimeric [Cu2(O2CR)]4 units with three possible spin configurations arising from Cu(II) 3d9 states and Cu-Cu δ bond. We observed an unusual very strong antiferromagnetic coupling in temperatures ranging from 100 K to 350 K for [Cu3(BTC)2.(H2O)3. (CuO)y]n. The inverse susceptibility versus temperature shows a linearity from 20 K up to 65 K fitting the Curie-Weiss law, for L = DMF. The CW X-band electron paramagnetic resonance spectroscopy (EPR) was important to explore the coordination state for DMF in the network. It was observed that DMF is located in an equatorial geometry of the coordination network experimenting interactions from the nitrogen and copper ions.

  3. Quantitative analysis of desorption and decomposition kinetics of formic acid on Cu(111): The importance of hydrogen bonding between adsorbed species

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo

    2015-12-21

    Quantitative analysis of desorption and decomposition kinetics of formic acid (HCOOH) on Cu(111) was performed by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy, and time-resolved infrared reflection absorption spectroscopy. The activation energy for desorption is estimated to be 53–75 kJ/mol by the threshold TPD method as a function of coverage. Vibrational spectra of the first layer HCOOH at 155.3 K show that adsorbed molecules form a polymeric structure via the hydrogen bonding network. Adsorbed HCOOH molecules are dissociated gradually into monodentate formate species. The activation energy for the dissociation into monodentate formate species is estimated to be 65.0 kJ/mol atmore » a submonolayer coverage (0.26 molecules/surface Cu atom). The hydrogen bonding between adsorbed HCOOH species plays an important role in the stabilization of HCOOH on Cu(111). The monodentate formate species are stabilized at higher coverages, because of the lack of vacant sites for the bidentate formation.« less

  4. Formation of highly preferred orientation of β-Sn grains in solidified Cu/SnAgCu/Cu micro interconnects under temperature gradient effect

    NASA Astrophysics Data System (ADS)

    Zhao, N.; Zhong, Y.; Dong, W.; Huang, M. L.; Ma, H. T.; Wong, C. P.

    2017-02-01

    β-Sn grain orientation and configuration are becoming crucial factors to dominate the lifetime of solder interconnects in three-dimensional integrated circuit packaging. In this paper, we found that a temperature gradient during solidification significantly dominated the orientation and configuration of the final β-Sn grains in Cu/SnAgCu/Cu micro interconnects. Being different from the random orientations and growth fronts meeting or cyclic twin boundary forming near the center after homogeneous temperature bonding, the β-Sn grains solidified under a certain temperature gradient were observed to follow a highly preferred orientation with their c-axis departing from the direction of temperature gradient by about 45°-88°. Meanwhile, these preferred oriented β-Sn grains consisted of low angle grain boundary structures with misorientation in the range of 0°-15°. The mechanism was explained in terms of the anisotropy and directional growth of β-Sn grains. The results pave the way for grain orientation control in 3D packaging technology.

  5. Indium-free, highly transparent, flexible Cu2O/Cu/Cu2O mesh electrodes for flexible touch screen panels.

    PubMed

    Kim, Dong-Ju; Kim, Hyo-Joong; Seo, Ki-Won; Kim, Ki-Hyun; Kim, Tae-Wong; Kim, Han-Ki

    2015-11-19

    We report on an indium-free and cost-effective Cu2O/Cu/Cu2O multilayer mesh electrode grown by room temperature roll-to-roll sputtering as a viable alternative to ITO electrodes for the cost-effective production of large-area flexible touch screen panels (TSPs). By using a low resistivity metallic Cu interlayer and a patterned mesh structure, we obtained Cu2O/Cu/Cu2O multilayer mesh electrodes with a low sheet resistance of 15.1 Ohm/square and high optical transmittance of 89% as well as good mechanical flexibility. Outer/inner bending test results showed that the Cu2O/Cu/Cu2O mesh electrode had a mechanical flexibility superior to that of conventional ITO films. Using the diamond-patterned Cu2O/Cu/Cu2O multilayer mesh electrodes, we successfully demonstrated TSPS of the flexible film-film type and rigid glass-film-film type TSPs. The TSPs with Cu2O/Cu/Cu2O mesh electrode were used to perform zoom in/out functions and multi-touch writing, indicating that these electrodes are promising cost-efficient transparent electrodes to substitute for conventional ITO electrodes in large-area flexible TSPs.

  6. Indium-free, highly transparent, flexible Cu2O/Cu/Cu2O mesh electrodes for flexible touch screen panels

    NASA Astrophysics Data System (ADS)

    Kim, Dong-Ju; Kim, Hyo-Joong; Seo, Ki-Won; Kim, Ki-Hyun; Kim, Tae-Wong; Kim, Han-Ki

    2015-11-01

    We report on an indium-free and cost-effective Cu2O/Cu/Cu2O multilayer mesh electrode grown by room temperature roll-to-roll sputtering as a viable alternative to ITO electrodes for the cost-effective production of large-area flexible touch screen panels (TSPs). By using a low resistivity metallic Cu interlayer and a patterned mesh structure, we obtained Cu2O/Cu/Cu2O multilayer mesh electrodes with a low sheet resistance of 15.1 Ohm/square and high optical transmittance of 89% as well as good mechanical flexibility. Outer/inner bending test results showed that the Cu2O/Cu/Cu2O mesh electrode had a mechanical flexibility superior to that of conventional ITO films. Using the diamond-patterned Cu2O/Cu/Cu2O multilayer mesh electrodes, we successfully demonstrated TSPS of the flexible film-film type and rigid glass-film-film type TSPs. The TSPs with Cu2O/Cu/Cu2O mesh electrode were used to perform zoom in/out functions and multi-touch writing, indicating that these electrodes are promising cost-efficient transparent electrodes to substitute for conventional ITO electrodes in large-area flexible TSPs.

  7. Interfacial Phenomena in Al/Al, Al/Cu, and Cu/Cu Joints Soldered Using an Al-Zn Alloy with Ag or Cu Additions

    NASA Astrophysics Data System (ADS)

    Pstruś, Janusz; Gancarz, Tomasz

    2014-05-01

    The studies of soldered joints were carried out in systems: Al/solder/Al, Al/solder/Cu, Cu/solder/Cu, where the solder was (Al-Zn)EUT, (Al-Zn)EUT with 0.5, 1.0, and 1.5 at.% of Ag and (Al-Zn)EUT with 0.5, 1.0, and 1.5 at.% of Cu addition. Brazing was performed at 500 °C for 3 min. The EDS analysis indicated that the composition of the layers starting from the Cu pad was CuZn, Cu5Zn8, and CuZn4, respectively. Wetting tests were performed at 500 °C for 3, 8, 15, and 30 min, respectively. Thickness of the layers and their kinetics of growth were measured based on the SEM micrographs. The formation of interlayers was not observed from the side of Al pads. On the contrary, dissolution of the Al substrate and migration of Al-rich particles into the bulk of the solder were observed.

  8. The influence of Cu+ binding to hypoxanthine on stabilization of mismatches involving hypoxanthine and DNA bases: A DFT study.

    PubMed

    Masoodi, Hamid Reza; Bagheri, Sotoodeh; Ghaderi, Zahra

    2018-05-14

    In the present work, the influence of Cu + binding to N3- and N7-positions of hypoxanthine on energetic, geometrical and topological properties of hypoxanthine-guanine, hypoxanthine-adenine, hypoxanthine-cytosine, hypoxanthine-thymine and hypoxanthine-hypoxanthine mismatches is theoretically investigated. The calculations, in gas phase, are performed at B3LYP/6-311++G(3df,3pd) level of theory. Unlike the other mispairs, Cu + binding to N3-position of hypoxanthine causes the proton transfer process from enol form of hypoxanthine to imino forms of adenine and cytosine. This process also occurs in all mismatches having enol form of hypoxanthine when Cu + binds to N7-position of hypoxanthine. The mismatches are stabilized by hydrogen bonds. The influence of Cu + on hydrogen bonds is also examined by atoms in molecules (AIM) and natural bond orbital (NBO) analyses.

  9. Tailoring Graphene Morphology and Orientation on Cu(100), Cu(110), and Cu(111)

    NASA Astrophysics Data System (ADS)

    Jacobberger, Robert; Arnold, Michael

    2013-03-01

    Graphene CVD on Cu is phenomenologically complex, yielding diverse crystal morphologies, such as lobes, dendrites, stars, and hexagons, of various orientations. We present a comprehensive study of the evolution of these morphologies as a function of Cu surface orientation, pressure, H2:CH4, and nucleation density. Growth was studied on ultra-smooth, epitaxial Cu films inside Cu enclosures to minimize factors that normally complicate growth. With low H2:CH4, Mullins-Sekerka instabilities propagate to form dendrites, indicating transport limited growth. In LPCVD, the dendrites extend hundreds of microns in the 100, 111, and 110 directions on Cu(100), (110), and (111) and are perturbed by twin boundaries. In APCVD, multiple preferred dendrite orientations exist. With increasing H2:CH4, the dendritic nature of growth is suppressed. In LPCVD, square, rectangle, and hexagon crystals form on Cu(100), (110) and (111), reflecting the Cu crystallography. In APCVD, the morphology becomes hexagonal on each surface. If given ample time, every growth regime yields high-quality monolayers with D:G Raman ratio <0.1. The understanding gained here provides a framework to rationally tailor the graphene crystal morphology and orientation.

  10. Well-studied Cu-BTC still serves surprises: evidence for facile Cu2+/Cu+ interchange.

    PubMed

    Szanyi, Janos; Daturi, Marco; Clet, Guillaume; Baer, Donald R; Peden, Charles H F

    2012-04-07

    Cu-BTC (also known as HKUST-1) is a well-characterized metal-organic framework material produced in an industrial scale and widely studied for a number of potential applications by the scientific community. The co-existence of Cu(+) and Cu(2+) entities has already been observed in this material, but the presence of Cu(+) ions was attributed to oxide impurities. The results presented here clearly demonstrate that Cu(+) ions can be present in high concentrations inside the hybrid structure. Furthermore, switching between the two copper oxidation states can be induced by redox treatments, using vacuum and/or reducing gases at different sample temperatures.

  11. Well-studied Cu-BTC still serves surprises: evidence for facile Cu2+/Cu+ interchange

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Szanyi, Janos; Daturi, Marco; Clet, Guillame

    2012-03-08

    Cu-BTC (also known as HKUST-1) is a well-characterized Metal Organic Framework material produced in industrial scale and widely studied for a number of potential applications by the scientific community. The co-existence of Cu+ and Cu2+ entities has already been observed in this material, but the presence of Cu+ ions was attributed to oxide impurities. The results presented here clearly demonstrate that Cu+ ions can be present in high concentrations inside the hybrid structure. Furthermore, switching between the two copper oxidation states can be induced by redox treatments, using vacuum and/or reducing gases at different sample temperatures.

  12. Heterogeneous integration based on low-temperature bonding for advanced optoelectronic devices

    NASA Astrophysics Data System (ADS)

    Higurashi, Eiji

    2018-04-01

    Heterogeneous integration is an attractive approach to manufacturing future optoelectronic devices. Recent progress in low-temperature bonding techniques such as plasma activation bonding (PAB) and surface-activated bonding (SAB) enables a new approach to integrating dissimilar materials for a wide range of photonics applications. In this paper, low-temperature direct bonding and intermediate layer bonding techniques are focused, and their state-of-the-art applications in optoelectronic devices are reviewed. First, we describe the room-temperature direct bonding of Ge/Ge and Ge/Si wafers for photodetectors and of GaAs/SiC wafers for high-power semiconductor lasers. Then, we describe low-temperature intermediate layer bonding using Au and lead-free Sn-3.0Ag-0.5Cu solders for optical sensors and MEMS packaging.

  13. Cu gettering by phosphorus-doped emitters in p-type silicon: Effect on light-induced degradation

    NASA Astrophysics Data System (ADS)

    Inglese, Alessandro; Laine, Hannu S.; Vähänissi, Ville; Savin, Hele

    2018-01-01

    The presence of copper (Cu) contamination is known to cause relevant light-induced degradation (Cu-LID) effects in p-type silicon. Due to its high diffusivity, Cu is generally regarded as a relatively benign impurity, which can be readily relocated during device fabrication from the wafer bulk, i.e. the region affected by Cu-LID, to the surface phosphorus-doped emitter. This contribution examines in detail the impact of gettering by industrially relevant phosphorus layers on the strength of Cu-LID effects. We find that phosphorus gettering does not always prevent the occurrence of Cu-LID. Specifically, air-cooling after an isothermal anneal at 800°C results in only weak impurity segregation to the phosphorus-doped layer, which turns out to be insufficient for effectively mitigating Cu-LID effects. Furthermore, we show that the gettering efficiency can be enhanced through the addition of a slow cooling ramp (-4°C/min) between 800°C and 600°C, resulting in the nearly complete disappearance of Cu-LID effects.

  14. Preparation and Optoelectrical Properties of p-CuO/n-Si Heterojunction by a Simple Sol-Gel Method

    NASA Astrophysics Data System (ADS)

    He, Bo; Xu, Jing; Ning, Huanpo; Zhao, Lei; Xing, Huaizhong; Chang, Chien-Cheng; Qin, Yuming; Zhang, Lei

    The Cuprous oxide (CuO) thin film was prepared on texturized Si wafer by a simple sol-gel method to fabricate p-CuO/n-Si heterojunction photoelectric device. The novel sol-gel method is very cheap and convenient. The structural, optical and electrical properties of the CuO film were studied by X-ray diffraction (XRD), Scanning Electron Microscope (SEM), X-ray photoelectron spectroscopy (XPS), UV-Vis spectrophotometer and Hall effect measurement. A good nonlinear rectifying behavior is obtained for the p-CuO/n-Si heterojunction. Under reverse bias, good photoelectric behavior is obtained.

  15. Multi-wafer bonding technology for the integration of a micromachined Mirau interferometer

    NASA Astrophysics Data System (ADS)

    Wang, Wei-Shan; Lullin, Justine; Froemel, Joerg; Wiemer, Maik; Bargiel, Sylwester; Passilly, Nicolas; Gorecki, Christophe; Gessner, Thomas

    2015-02-01

    The paper presents the multi-wafer bonding technology as well as the integration of electrical connection to the zscanner wafer of the micromachined array-type Mirau interferometer. A Mirau interferometer, which is a key-component of optical coherence tomography (OCT) microsystem, consists of a microlens doublet, a MOEMS Z-scanner, a focusadjustment spacer and a beam splitter plate. For the integration of this MOEMS device heterogeneous bonding of Si, glass and SOI wafers is necessary. Previously, most of the existing methods for multilayer wafer bonding require annealing at high temperature, i.e., 1100°C. To be compatible with MEMS devices, bonding of different material stacks at temperatures lower than 400°C has also been investigated. However, if more components are involved, it becomes less effective due to the alignment accuracy or degradation of surface quality of the not-bonded side after each bonding operation. The proposed technology focuses on 3D integration of heterogeneous building blocks, where the assembly process is compatible with the materials of each wafer stack and with position accuracy which fits optical requirement. A demonstrator with up to 5 wafers bonded lower than 400°C is presented and bond interfaces are evaluated. To avoid the complexity of through wafer vias, a design which creates electrical connections along vertical direction by mounting a wafer stack on a flip chip PCB is proposed. The approach, which adopts vertically-stacked wafers along with electrical connection functionality, provides not only a space-effective integration of MOEMS device but also a design where the Mirau stack can be further integrated with other components of the OCT microsystem easily.

  16. Indium-free, highly transparent, flexible Cu2O/Cu/Cu2O mesh electrodes for flexible touch screen panels

    PubMed Central

    Kim, Dong-Ju; Kim, Hyo-Joong; Seo, Ki-Won; Kim, Ki-Hyun; Kim, Tae-Wong; Kim, Han-Ki

    2015-01-01

    We report on an indium-free and cost-effective Cu2O/Cu/Cu2O multilayer mesh electrode grown by room temperature roll-to-roll sputtering as a viable alternative to ITO electrodes for the cost-effective production of large-area flexible touch screen panels (TSPs). By using a low resistivity metallic Cu interlayer and a patterned mesh structure, we obtained Cu2O/Cu/Cu2O multilayer mesh electrodes with a low sheet resistance of 15.1 Ohm/square and high optical transmittance of 89% as well as good mechanical flexibility. Outer/inner bending test results showed that the Cu2O/Cu/Cu2O mesh electrode had a mechanical flexibility superior to that of conventional ITO films. Using the diamond-patterned Cu2O/Cu/Cu2O multilayer mesh electrodes, we successfully demonstrated TSPS of the flexible film-film type and rigid glass-film-film type TSPs. The TSPs with Cu2O/Cu/Cu2O mesh electrode were used to perform zoom in/out functions and multi-touch writing, indicating that these electrodes are promising cost-efficient transparent electrodes to substitute for conventional ITO electrodes in large-area flexible TSPs. PMID:26582471

  17. Electromigration in Cu(Al) and Cu(Mn) damascene lines

    NASA Astrophysics Data System (ADS)

    Hu, C.-K.; Ohm, J.; Gignac, L. M.; Breslin, C. M.; Mittal, S.; Bonilla, G.; Edelstein, D.; Rosenberg, R.; Choi, S.; An, J. J.; Simon, A. H.; Angyal, M. S.; Clevenger, L.; Maniscalco, J.; Nogami, T.; Penny, C.; Kim, B. Y.

    2012-05-01

    The effects of impurities, Mn or Al, on interface and grain boundary electromigration (EM) in Cu damascene lines were investigated. The addition of Mn or Al solute caused a reduction in diffusivity at the Cu/dielectric cap interface and the EM activation energies for both Cu-alloys were found to increase by about 0.2 eV as compared to pure Cu. Mn mitigated and Al enhanced Cu grain boundary diffusion; however, no significant mitigation in Cu grain boundary diffusion was observed in low Mn concentration samples. The activation energies for Cu grain boundary diffusion were found to be 0.74 ± 0.05 eV and 0.77 ± 0.05 eV for 1.5 μm wide polycrystalline lines with pure Cu and Cu (0.5 at. % Mn) seeds, respectively. The effective charge number in Cu grain boundaries Z*GB was estimated from drift velocity and was found to be about -0.4. A significant enhancement in EM lifetimes for Cu(Al) or low Mn concentration bamboo-polycrystalline and near-bamboo grain structures was observed but not for polycrystalline-only alloy lines. These results indicated that the existence of bamboo grains in bamboo-polycrystalline lines played a critical role in slowing down the EM-induced void growth rate. The bamboo grains act as Cu diffusion blocking boundaries for grain boundary mass flow, thus generating a mechanical stress-induced back flow counterbalancing the EM force, which is the equality known as the "Blech short length effect."

  18. A first-principles study of the structural, mechanical and electronic properties of precipitates of Al2Cu in Al-Cu alloys.

    PubMed

    Ouyang, Y F; Chen, H M; Tao, X M; Gao, F; Peng, Q; Du, Y

    2018-01-03

    The properties of precipitates are important in understanding the strengthening mechanism via precipitation during heat treatment and the aging process in Al-Cu based alloys, where the formation of precipitates is sensitive to temperature and pressure. Here we report a first-principles investigation of the effect of temperature and pressure on the structural stability, elastic constants and formation free energy for precipitates of Al 2 Cu, as well as their mechanical properties. Based on the formation enthalpy of Guinier-Preston (GP(I)) zones, the size of the GP(I) zone is predicted to be about 1.4 nm in diameter, which is in good agreement with experimental observations. The formation enthalpies of the precipitates are all negative, suggesting that they are all thermodynamically stable. The present calculations reveal that entropy plays an important role in stabilizing θ-Al 2 Cu compared with θ C '-Al 2 Cu. The formation free energies of θ''-Al 3 Cu, θ C '-Al 2 Cu, θ D '-Al 5 Cu 3 and θ t '-Al 11 Cu 7 increase with temperature, while those of θ'-Al 2 Cu, θ O '-Al 2 Cu and θ-Al 2 Cu decrease. The same trend is observed with the effect of pressure. The calculated elastic constants for the considered precipitation phases indicate that they are all mechanically stable and anisotropic, except θ C '-Al 2 Cu. θ D '-Al 5 Cu 3 has the highest Vicker's hardness. The electronic structures are also calculated to gain insight into the bonding characteristics. The present results can help in understanding the formation of precipitates by different treatment processes.

  19. Elucidation of the Human Serum Albumin (HSA) Binding Site for the Cu-PTSM and Cu-ATSM Radiopharmaceuticals

    PubMed Central

    Basken, Nathan E.; Mathias, Carla J.; Green, Mark A.

    2008-01-01

    The Cu-PTSM (pyruvaldehyde bis(N4-methylthiosemicarbazonato)copper(II)) and Cu-ATSM (diacetyl bis(N4-methylthiosemicarbazonato)copper(II)) radiopharmaceuticals exhibit strong, species-dependent binding to human serum albumin (HSA), while Cu-ETS (ethylglyoxal bis(thiosemicarbazonato)copper(II)) appears to only exhibit non-specific binding to human and animal serum albumins. This study examines the structural basis for HSA binding of Cu-PTSM and Cu-ATSM via competition with drugs having known albumin binding sites. Warfarin, furosemide, ibuprofen, phenylbutazone, benzylpenicillin, and cephmandole were added to HSA solutions at drug:HSA mole ratios from 0 to 8:1, followed by quantification of radiopharmaceutical binding to HSA by ultrafiltration. Warfarin, a site IIA drug, progressively displaced both [64Cu]Cu-PTSM and [64Cu]Cu-ATSM from HSA. At 8:1 warfarin:HSA mole ratios, free [64Cu]Cu-PTSM and [64Cu]Cu-ATSM levels increased 300–500%. This was in contrast to solutions containing ibuprofen, a site IIIA drug; no increase in free [64Cu]Cu-PTSM or [64Cu]Cu-ATSM was observed except at high ibuprofen:HSA ratios, where secondary ibuprofen binding to the IIA site may cause modest radiopharmaceutical displacement. By contrast, and consistent with earlier findings suggesting Cu-ETS exhibits only non-specific associations, [64Cu]Cu-ETS binding to HSA was unaffected by the addition of drugs that bind in either site. We conclude that the species-dependence of Cu-PTSM and Cu-ATSM albumin binding arises from interaction(s) with the IIA site of HSA. PMID:18937368

  20. Interstitial copper defect induced reconstruction of a new ;CuO4; quadrilateral in CaCu3Ti4O12: A first-principles study

    NASA Astrophysics Data System (ADS)

    Xiao, Haibo; Xu, Linfang; Wang, Ruilong; Yang, Changping

    2017-09-01

    The geometric structure, electronic structure and formation energy of CaCu3Ti4O12 (CCTO) with interstitial copper atom have been studied using the density-functional method within the GGA approximation. Result of structural optimization shows that the interstitial Cu-atom (Cu7) prefers to occupy a special location which is symmetrical with an intrinsic copper atom (Cu13) deviated from the normal site. The mulliken analysis indicates the loss of electrons from interstitial atom (Cu7) and Cu13 are only half more of the losing in other copper atom, which reveals a characteristics of covalent bonding between Cu7/Cu13 and surrounding oxygen atoms respectively. Meanwhile, it is found from electron density difference (EDD) and orbital analysis that the introduction of interstitial Cu atom causes prominent structural reconstruction of a new ;CuO4; quadrilateral. Moreover, the new ;CuO4; planar leads to a corresponding electronic reconstruction in the hybridization between Cu7/Cu13 3d and O 2p at the vicinity of fermi surface, for which a new conductive filament channel comes into being. Besides, the formation energies of the interstitial defects in various charge states are corrected with the value of 2.18, -4.17 and -9.46 eV for charge of 0, 1+ and 2+, respectively.

  1. Novel bimetallic thiocyanate-bridged Cu(II)-Hg(II) compounds—synthesis, X-Ray studies and magnetic properties

    NASA Astrophysics Data System (ADS)

    Machura, B.; Świtlicka, A.; Zwoliński, P.; Mroziński, J.; Kalińska, B.; Kruszynski, R.

    2013-01-01

    Seven novel heterobimetallic Cu/Hg polymers based on thiocyanate bridges have been synthesised and characterised by means of IR, EPR, magnetic measurements and single crystal X-Ray. Three of them, [Cu(pzH)4Hg(SCN)4]n (1) [Cu(indH)4Hg(SCN)4]n (2) and [Cu(ampy)2Hg(SCN)4]n (3), have one-dimensional coordination structure. Two compounds [Cu(pzH)2Hg(SCN)4]n (4) and [Cu(abzimH)Hg(SCN)4]n (5) form two-dimensional nets, whereas the complexes [Cu(pyCN)2Hg(SCN)4]n (6) and [Cu(pyCH(OH)(OMe))2Hg(SCN)4]n (7) are three-dimensional coordination polymers. The chains of 1 are connected by the intermolecular N-H•••N hydrogen bonds to the three dimensional net. In 2 the N-H•••S hydrogen bonds link the polymeric chains to the two dimensional layer extending along crystallographic (0 0 1) plane. The polymeric chains of compound 3 are joined by the intermolecular N-H•••N and N-H•••S hydrogen bonds to the three dimensional net. The polymeric layers of 4 are connected by the intermolecular N-H•••N hydrogen bonds to the three dimensional net.

  2. Evaluation of different strategies for quantitative depth profile analysis of Cu/NiCu layers and multilayers via pulsed glow discharge - Time of flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Muñiz, Rocío; Lobo, Lara; Németh, Katalin; Péter, László; Pereiro, Rosario

    2017-09-01

    There is still a lack of approaches for quantitative depth-profiling when dealing with glow discharges (GD) coupled to mass spectrometric detection. The purpose of this work is to develop quantification procedures using pulsed GD (PGD) - time of flight mass spectrometry. In particular, research was focused towards the depth profile analysis of Cu/NiCu nanolayers and multilayers electrodeposited on Si wafers. PGDs are characterized by three different regions due to the temporal application of power: prepeak, plateau and afterglow. This last region is the most sensitive and so it is convenient for quantitative analysis of minor components; however, major elements are often saturated, even at 30 W of applied radiofrequency power for these particular samples. For such cases, we have investigated two strategies based on a multimatrix calibration procedure: (i) using the afterglow region for all the sample components except for the major element (Cu) that was analyzed in the plateau, and (ii) using the afterglow region for all the elements measuring the ArCu signal instead of Cu. Seven homogeneous certified reference materials containing Si, Cr, Fe, Co, Ni and Cu have been used for quantification. Quantitative depth profiles obtained with these two strategies for samples containing 3 or 6 multilayers (of a few tens of nanometers each layer) were in agreement with the expected values, both in terms of thickness and composition of the layers.

  3. Aging Studies of Cu-Sn Intermetallics in Cu Micropillars Used in Flip Chip Attachment onto Cu Lead Frames

    NASA Astrophysics Data System (ADS)

    Roma, Maria Penafrancia C.; Kudtarkar, Santosh; Kierse, Oliver; Sengupta, Dipak; Cho, Junghyun

    2018-02-01

    Copper micropillars plated onto a silicon die and soldered with Sn-Ag solder to a copper lead frame in a flip chip on lead package have been subjected to high-temperature storage at 150°C and 175°C for 500 h, 1000 h, and 1500 h. Cu6Sn5 and Cu3Sn intermetallic compounds were found on both sides of the solder, but the growth rates were not the same as evidenced by different values of the growth exponent n. Cu and Sn diffusion controlled the Cu3Sn growth in the Cu pillar interface ( n ≈ 0.5), while interface reactions controlled the growth in the Cu lead frame interface ( n ≈ 0.8). Increasing the aging temperature increased the growth of Cu3Sn as well as the presence of microvoids in the Cu lead frame side. Adding Ni as a barrier layer on the Cu pillar prevented the growth of Cu3Sn in the Cu pillar interface and reduced its growth rate on the lead frame side, even at higher aging temperatures.

  4. Electronic Structure of TlBa2CaCu2O(7-Delta)

    NASA Technical Reports Server (NTRS)

    Vasquez, R. P.; Novikov, D. L.; Freeman, A. J.; Siegal, M. P.

    1997-01-01

    The core levels of TlBa2CaCu2O(7-delta) (Tl-1212) epitaxial films have been measured with X-ray photoelectron spectroscopy (XPS). The valence electronic structure has been determined using the full-potential linear muffin-tin-orbital band-structure method and measured with XPS. The calculations show that a van Hove singularity (VHS) lies above the Fermi level (E(sub F)) for the stoichiometric compound (delta = 0.5), while for 50% oxygen vacancies in the Tl-O layer (delta = 0.5) E(sub F) is in close proximity to the VHS. Samples annealed in nitrogen (to reduce the hole overdoping by the removal of oxygen) exhibit higher core-level binding energies and a higher T(sub c), consistent with a shift of E(sub F) closer to the VHS. Comparisons are made to the core levels and valence bands of Tl2Ba2CaCu2O(8 + delta)(Tl-2212) and HgBa2CaCu2O)6 + delta) (Hg- 1212). The similarity of the Cu 2p(sub 3/2) spectra for Tl-1212 and Tl-2212 indicates that the number of Tl-O layers has little effect on the Cu-O bonding. However, the Tl-1212 and Hg-1212 Cu 2p(sub 3/2) signals exhibit differences which suggest that the replacement of T(sup 3+) with Hg(sup 2+) results in a decrease in the O 2p right arrow Cu 3d charge-transfer energy and differences in the probabilities of planar vs apical oxygen charge transfer and/or Zhang-Rice singlet-state formation. Differences between the Tl-1212 and the Tl-2212 and Hg-1212 measured valence bands are consistent with the calculated Cu 3d and (Tl,Hg) 6s/5d partial densities of states.

  5. Assessment of copper nanoparticles (Cu-NPs) and copper (II) oxide (CuO) induced hemato- and hepatotoxicity in Cyprinus carpio

    NASA Astrophysics Data System (ADS)

    Noureen, Aasma; Jabeen, Farhat; Tabish, Tanveer A.; Yaqub, Sajid; Ali, Muhammad; Shakoor Chaudhry, Abdul

    2018-04-01

    Recently, Cu-based nanoparticles have drawn considerable attention for their various fascinating roles in multiple biological systems. It is recognized that their frequent use can create compatibility challenges for the recipient systems. Nevertheless, it is unclear how various biological interactions affect the compatibility of Cu oxide II (CuO) and Cu oxide nanoparticles (Cu-NPs) for different organisms. Consequently, it has been difficult to perform structured risk assessments for their use in biological systems. Therefore, this study compared the effects of different doses of waterborne Cu-NPs and CuO on the blood and liver of selected groups of Cyprinus (C) carpio. These fish while housed in suitable water tanks were exposed to one of the following treatments for 14 d: control (no added Cu) or 0.5 or 1 or 1.5 mg Cu as Cu-NPs or CuO l-1 of water. We found significant changes in all assessed blood parameters of fish in response to increasing doses from 0 to 1.5 mg of Cu-NPs or CuO. Similarly, increased levels of lipid peroxide and reduced glutathione (GSH) were also observed in the livers of C. carpio in Cu-NPs or CuO treated groups. Enhanced levels of lipid peroxidation and GSH were also recorded in the Cu-NP treated groups compared with the CuO treated groups in a dose dependent manner. The lowest catalase activity was observed in the liver of C. carpio treated with the higer dose of Cu-NPs. Cu-NP or CuO exposure induced significant histological alterations in the liver of C. carpio including focal necrosis, cloudy swelling of hepatocytes, degenerative hepatocytes, vacuolization, pyknotic nuclei, damaged central vein, nuclear hypertrophy, dilated sinusoid, vacuolated degeneration, congestion, and complete degeneration in a dose dependent manner. Substantial alterations in blood and liver specimens were observed in the Cu-NP treated fish when compared with the CuO treated fish. It appeared that the Cu-NPs were more toxic than the CuO as shown by the hemato- and

  6. Metallicity of Ca 2Cu 6P 5 with single and double copper-pnictide layers

    DOE PAGES

    Li, Li; Parker, David; Chi, Miaofang; ...

    2016-02-16

    We report thermodynamic and transport properties, and also theoretical calculations, for Cu-based compound Ca 2Cu 6P 5 and compare with CaCu 2-δP 2. Both materials have layers of edge-sharing copper pnictide tetrahedral CuP 4, similar to Fe–As and Fe–Se layers (with FeAs 4, FeSe 4) in the iron-based superconductors. Despite the presence of this similar transition-metal pnictide layer, we find that both Ca 2Cu 6P 5 and CaCu 2-δP 2 have temperature-independent magnetic susceptibility and show metallic behavior with no evidence of either magnetic ordering or superconductivity down to 1.8 K CaCu 2-δP 2 is slightly off-stoichiometric, with δ =more » 0.14. Theoretical calculations suggest that unlike Fe 3d-based magnetic materials with a large density of states (DOS) at the Fermi surface, Cu have comparatively low DOS, with the majority of the 3d spectral weight located well below Fermi level. The room-temperature resistivity value of Ca 2Cu 6P 5 is only 9 μΩ-cm, due to a substantial plasma frequency and an inferred electron-phonon coupling λ of 0.073 (significantly smaller than that of metallic Cu). Also, microscopy result shows that Cu–Cu distance along the c-axis within the double layers can be very short (2.5 Å), even shorter than metallic elemental copper bond (2.56 Å). The value of dρ/dT for CaCu 2-δP 2 at 300 K is approximately three times larger than in Ca 2Cu 6P 5, which suggests the likelihood of stronger electron-phonon coupling. Lastly, this study shows that the details of Cu–P layers and bonding are important for their transport characteristics. In addition, it emphasizes the remarkable character of the DOS of ‘122’ iron-based materials, despite much structural similarities.« less

  7. Thermal conversion of Cu4O3 into CuO and Cu2O and the electrical properties of magnetron sputtered Cu4O3 thin films

    NASA Astrophysics Data System (ADS)

    Murali, Dhanya S.; Aryasomayajula, Subrahmanyam

    2018-03-01

    Among the three oxides of copper (CuO, Cu2O, and Cu4O3), Cu4O3 phase (paramelaconite is a natural, and very scarce mineral) is very difficult to synthesize. It contains copper in both + 1 and + 2 valence states, with an average composition Cu2 1+Cu2 2+O3. We have successfully synthesized Cu4O3 phase at room temperature (300 K) by reactive DC magnetron sputtering by controlling the oxygen flow rate (Murali and Subrahmanyam in J Phys D Appl Phys 49:375102, 2016). In the present communication, Cu4O3 thin films are converted to CuO phases by annealing in the air at 680 K and to Cu2O phase when annealed in argon at 720 K; these phase changes are confirmed by temperature-dependent Raman spectroscopy studies. Probably, this is the first report of the conversion of Cu4O3-CuO and Cu2O by thermal annealing. The temperature-dependent (300-200 K) electrical transport properties of Cu4O3 thin films show that the charge transport above 190 K follows Arrhenius-type behavior with activation energy of 0.14 eV. From photo-electron spectroscopy and electrical transport measurements of Cu4O3 thin films, a downward band bending is observed at the surface of the thin film, which shows its p-type semiconducting nature. The successful preparation of phase pure p-type semiconducting Cu4O3 could provide opportunities to further explore its potential applications.

  8. Cu-catalyzed esterification reaction via aerobic oxygenation and C-C bond cleavage: an approach to α-ketoesters.

    PubMed

    Zhang, Chun; Feng, Peng; Jiao, Ning

    2013-10-09

    The Cu-catalyzed novel aerobic oxidative esterification reaction of 1,3-diones for the synthesis of α-ketoesters has been developed. This method combines C-C σ-bond cleavage, dioxygen activation and oxidative C-H bond functionalization, as well as provides a practical, neutral, and mild synthetic approach to α-ketoesters which are important units in many biologically active compounds and useful precursors in a variety of functional group transformations. A plausible radical process is proposed on the basis of mechanistic studies.

  9. Microstructure and Properties of the Al-27Si/Cu/Al-50Si Joint Brazed by the Partial Transient Liquid Phase Bonding

    NASA Astrophysics Data System (ADS)

    Sun, Qingzhu; Wang, Haibo; Yang, Cheng

    2018-06-01

    Al-27Si and Al-50Si were brazed by using a thin Cu interlayer. The metallurgical bonding without obvious defects is achieved, and a wide brazing seam consisting of fine eutectic structures and coarse Si particles is formed in the Al-27Si/Cu/Al-50Si joint. The deposition of Si element in the liquid phases during solidification results in the formation of the larger Si particles and ultra-small Si particles in the brazing seam. The shear strength of the joint reaches 63 MPa.

  10. Microstructure and Properties of the Al-27Si/Cu/Al-50Si Joint Brazed by the Partial Transient Liquid Phase Bonding

    NASA Astrophysics Data System (ADS)

    Sun, Qingzhu; Wang, Haibo; Yang, Cheng

    2018-04-01

    Al-27Si and Al-50Si were brazed by using a thin Cu interlayer. The metallurgical bonding without obvious defects is achieved, and a wide brazing seam consisting of fine eutectic structures and coarse Si particles is formed in the Al-27Si/Cu/Al-50Si joint. The deposition of Si element in the liquid phases during solidification results in the formation of the larger Si particles and ultra-small Si particles in the brazing seam. The shear strength of the joint reaches 63 MPa.

  11. Microwave Induced Direct Bonding of Single Crystal Silicon Wafers

    NASA Technical Reports Server (NTRS)

    Budraa, N. K.; Jackson, H. W.; Barmatz, M.

    1999-01-01

    We have heated polished doped single-crystal silicon wafers in a single mode microwave cavity to temperatures where surface to surface bonding occurred. The absorption of microwaves and heating of the wafers is attributed to the inclusion of n-type or p-type impurities into these substrates. A cylindrical cavity TM (sub 010) standing wave mode was used to irradiate samples of various geometry's at positions of high magnetic field. This process was conducted in vacuum to exclude plasma effects. This initial study suggests that the inclusion of impurities in single crystal silicon significantly improved its microwave absorption (loss factor) to a point where heating silicon wafers directly can be accomplished in minimal time. Bonding of these substrates, however, occurs only at points of intimate surface to surface contact. The inclusion of a thin metallic layer on the surfaces enhances the bonding process.

  12. Microfluidic reactor synthesis and photocatalytic behavior of Cu@Cu2O nanocomposite

    NASA Astrophysics Data System (ADS)

    Xu, Lei; Srinivasakannan, C.; Peng, Jinhui; Yan, Mi; Zhang, Di; Zhang, Libo

    2015-03-01

    The Cu@Cu2O nanocomposites were synthesized by solution-phase synthesis of Cu nanoparticles in microfluidic reactor at room temperature, followed by controlling the oxidation process. The size, morphology, elemental compositions, and the chemical composition on the surface of Cu@Cu2O nanocomposite were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Experimental results demonstrated that the surface of the Cu nanoparticles was oxidized to Cu2O which serves as the shell of nanoparticle. The amount of Cu2O can be controlled by varying the drying temperature. Additionally the binary Cu@Cu2O nanocomposite along with H2O2 exhibited its potential as an excellent photocatalyst for degradation of methylene blue (MB) under UV irradiation.

  13. Cu(II) salen complex with propylene linkage: An efficient catalyst in the formation of Csbnd X bonds (X = N, O, S) and biological investigations

    NASA Astrophysics Data System (ADS)

    Azam, Mohammad; Dwivedi, Sourabh; Al-Resayes, Saud I.; Adil, S. F.; Islam, Mohammad Shahidul; Trzesowska-Kruszynska, Agata; Kruszynski, Rafal; Lee, Dong-Ung

    2017-02-01

    The catalytic property of a mononuclear Cu(II) salen complex in Chan-Lam coupling reaction with phenyl boronic acid at room temperature is reported. The studied complex is found to be potential catalyst in the preparation of carbon-heteroatom bonds with excellent yields. The studied Cu(II) salen complex is monoclinic with cell parameters, a = 9.6807(5) (α 90°), (b = 17.2504(8) (β 112.429 (2), c = 11.1403 (6) (γ = 90°), and has distorted square planar environment around Cu(II) ion. Furthermore, there is no π⋯π interactions in the reported complex due to large distance between the centroid of aromatic rings. In addition, DNA binding study of Cu(II) salen complex by fluorescence and absorption spectroscopy is also reported. Moreover, the reported Cu(II) salen complex exhibits significant anticancer activity against MCF-7 cancer cell lines, and displays potential antimicrobial biofilm activity against P. aeruginosa, suggesting antimicrobial biofilm an important tool for suppression of resistant infections caused by P. aeruginosa.

  14. Selection for Cu-Tolerant Bacterial Communities with Altered Composition, but Unaltered Richness, via Long-Term Cu Exposure

    PubMed Central

    Berg, Jeanette; Brandt, Kristian K.; Al-Soud, Waleed A.; Holm, Peter E.; Hansen, Lars H.; Sørensen, Søren J.

    2012-01-01

    Toxic metal pollution affects the composition and metal tolerance of soil bacterial communities. However, there is virtually no knowledge concerning the responses of members of specific bacterial taxa (e.g., phyla or classes) to metal toxicity, and contradictory results have been obtained regarding the impact of metals on operational taxonomic unit (OTU) richness. We used tag-coded pyrosequencing of the 16S rRNA gene to elucidate the impacts of copper (Cu) on bacterial community composition and diversity within a well-described Cu gradient (20 to 3,537 μg g−1) stemming from industrial contamination with CuSO4 more than 85 years ago. DNA sequence information was linked to analysis of pollution-induced community tolerance (PICT) to Cu, as determined by the [3H]leucine incorporation technique, and to chemical characterization of the soil. PICT was significantly correlated to bioavailable Cu, as determined by the results seen with a Cu-specific bioluminescent biosensor strain, demonstrating a specific community response to Cu. The relative abundances of members of several phyla or candidate phyla, including the Proteobacteria, Bacteroidetes, Verrumicrobia, Chloroflexi, WS3, and Planctomycetes, decreased with increasing bioavailable Cu, while members of the dominant phylum, the Actinobacteria, showed no response and members of the Acidobacteria showed a marked increase in abundance. Interestingly, changes in the relative abundances of classes frequently deviated from the responses of the phyla to which they belong. Despite the apparent Cu impacts on Cu resistance and community structure, bioavailable Cu levels did not show any correlation to bacterial OTU richness (97% similarity level). Our report highlights several bacterial taxa responding to Cu and thereby provides new guidelines for future studies aiming to explore the bacterial domain for members of metal-responding taxa. PMID:22904046

  15. Deposition rate and substrate temperature effects on the structure and properties of bulk-sputtered OFHC Cu and Cu-0.15Zr. [Oxygen-Free High-Conductivity

    NASA Technical Reports Server (NTRS)

    Hecht, R. J.; Mullaly, J. R.

    1975-01-01

    Bulk-sputtered OFHC Cu and Cu-0.15 Zr used as inner walls of advanced regeneratively cooled thrust chambers are evaluated as to microstructure, surface topography, and fractography. It is found that under conditions of low substrate temperature, crystallite size and openness of the structure increase with increasing deposition rate for both materials. At elevated temperatures, an equiaxed ductile structure of OFHC Cu is produced only at low deposition rates; at higher deposition rate, open structures are observed with recrystallized equiaxed grains within large poorly bonded crystallites. The Cu-0.15 Zr alloy sputtered from the hollow cathode using a diode discharge shows open-type structures for all conditions evaluated. The use of a triode discharge in generating a dense non-voided structure of Cu-0.15 Zr is discussed.

  16. Generalized stacking fault energies, cleavage energies, ionicity and brittleness of Cu(Al/Ga/In)Se2 and CuGa(S/Se/Te)2

    NASA Astrophysics Data System (ADS)

    Xue, H. T.; Tang, F. L.; Gruhn, T.; Lu, W. J.; Wan, F. C.; Rui, Z. Y.; Feng, Y. D.

    2014-04-01

    We calculate the generalized stacking fault (GSF) energies and cleavage energies γcl of the chalcopyrite compounds CuAlSe2, CuGaSe2, CuInSe2, CuGaS2 and CuGaTe2 using first principles. From the GSF energies, we obtain the unstable stacking fault energies γus and intrinsic stacking fault energies γisf. By analyzing γus and γisf, we find that the \\langle \\bar{{1}}\\,1\\,0\\rangle (1 1 2) direction is the easiest slip direction for these five compounds. Also, for CuInSe2, it is most possible to undergo a dislocation-nucleation-induced plastic deformation along the \\langle \\bar{{1}}\\,1\\,0\\rangle (1 1 2) slip direction. We show that the (1 1 2) plane is the preferable plane for fracture in the five compounds by comparing γcl of the (0 0 1) and (1 1 2) planes. It is also found that both γus and γcl decrease as the cationic or anionic radius increases in these chalcopyrites, i.e. along the sequences CuAlSe2 → CuGaSe2 → CuInSe2 and CuGaS2 → CuGaSe2 → CuGaTe2. Based on the values of the ratio γcl/γus, we discuss the brittle-ductile properties of these compounds. All of the compounds can be considered as brittle materials. In addition, a strong relationship between γcl/γus and the total proportion of ionic bonding in these compounds is found.

  17. Mechanism of C-C and C-H bond cleavage in ethanol oxidation reaction on Cu2O(111): a DFT-D and DFT+U study.

    PubMed

    Xu, Han; Miao, Bei; Zhang, Minhua; Chen, Yifei; Wang, Lichang

    2017-10-04

    The performance of transition metal catalysts for ethanol oxidation reaction (EOR) in direct ethanol fuel cells (DEFCs) may be greatly affected by their oxidation. However, the specific effect and catalytic mechanism for EOR of transition metal oxides are still unclear and deserve in-depth exploitation. Copper as a potential anode catalyst can be easily oxidized in air. Thus, in this study, we investigated C-C and C-H bond cleavage reactions of CH x CO (x = 1, 2, 3) species in EOR on Cu 2 O(111) using PBE+U calculations, as well as the specific effect of +U correction on the process of adsorption and reaction on Cu 2 O(111). It was revealed that the catalytic performance of Cu 2 O(111) for EOR was restrained compared with that of Cu(100). Except for the C-H cleavage of CH 2 CO, all the reaction barriers for C-C and C-H cleavage were higher than those on Cu(100). The most probable pathway for CH 3 CO to CHCO on Cu 2 O(111) was the continuous dehydrogenation reaction. Besides, the barrier for C-C bond cleavage increased due to the loss of H atoms in the intermediate. Moreover, by the comparison of the traditional GGA/PBE method and the PBE+U method, it could be concluded that C-C cleavage barriers would be underestimated without +U correction, while C-H cleavage barriers would be overestimated. +U correction was proved to be necessary, and the reaction barriers and the values of the Hubbard U parameter had a proper linear relationship.

  18. Growth Behavior of Intermetallic Compounds at SnAgCu/Ni and Cu Interfaces

    NASA Astrophysics Data System (ADS)

    Qi, Lihua; Huang, Jihua; Zhang, Hua; Zhao, Xingke; Wang, Haitao; Cheng, Donghai

    2010-02-01

    The growth behavior of reaction-formed intermetallic compounds (IMCs) at Sn3.5Ag0.5Cu/Ni and Cu interfaces under thermal-shear cycling conditions was investigated. The results show that the morphology of (Cu x Ni1- x )6Sn5 and Cu6Sn5 IMCs formed both at Sn3.5Ag0.5Cu/Ni and Cu interfaces gradually changed from scallop-like to chunk-like, and different IMC thicknesses developed with increasing thermal-shear cycling time. Furthermore, Cu6Sn5 IMC growth rate at the Sn3.5Ag0.5Cu/Cu interface was higher than that of (Cu x Ni1- x )6Sn5 IMC under thermal-shear cycling. Compared to isothermal aging, thermal-shear cycling led to only one Cu6Sn5 layer at the interface between SnAgCu solder and Cu substrate after 720 cycles. Moreover, Ag3Sn IMC was dispersed uniformly in the solder after reflow. The planar Ag3Sn formed near the interface changed remarkably and merged together to large platelets with increasing cycles. The mechanism of formation of Cu6Sn5, (Cu x Ni1- x )6Sn5 and Ag3Sn IMCs during thermal-shear cycling process was investigated.

  19. YBa2Cu307 superconducting microbolometer linear arrays

    NASA Astrophysics Data System (ADS)

    Johnson, Burgess R.; Ohnstein, Thomas R.; Marsh, Holly A.; Dunham, Scott B.; Kruse, Paul W.

    1992-09-01

    Single pixels and linear arrays of microbolometers employing the high-T(subscript c) superconductor YBa(subscript 2)Cu(subscript 3)O(subscript 7) have been fabricated by silicon micromachining techniques. The substrates are 3 in. diameter silicon wafers upon which buffer layers of Si(subscript 3)N(subscript 4) and yttria-stabilized zirconia (YSZ) have been deposited. The YBa(subscript 2)Cu(subscript 3)O(subscript 7) was deposited by ion beam sputtering upon the yttria-stabilized zirconia (YSZ), then photolithographically patterned into serpentines 4 micrometers wide. Anisotropic etching in KOH removed the silicon underlying each pixel, thereby providing the necessary thermal isolation. When operated at 70 degree(s)K with 1 (mu) A dc bias, the D(superscript *) is 7.5 X 10(superscript 8) cm Hz(superscript 1/2)/Watt with a thermal response time of 24 msec.

  20. Wafer-level vacuum/hermetic packaging technologies for MEMS

    NASA Astrophysics Data System (ADS)

    Lee, Sang-Hyun; Mitchell, Jay; Welch, Warren; Lee, Sangwoo; Najafi, Khalil

    2010-02-01

    An overview of wafer-level packaging technologies developed at the University of Michigan is presented. Two sets of packaging technologies are discussed: (i) a low temperature wafer-level packaging processes for vacuum/hermeticity sealing, and (ii) an environmentally resistant packaging (ERP) technology for thermal and mechanical control as well as vacuum packaging. The low temperature wafer-level encapsulation processes are implemented using solder bond rings which are first patterned on a cap wafer and then mated with a device wafer in order to encircle and encapsulate the device at temperatures ranging from 200 to 390 °C. Vacuum levels below 10 mTorr were achieved with yields in an optimized process of better than 90%. Pressures were monitored for more than 4 years yielding important information on reliability and process control. The ERP adopts an environment isolation platform in the packaging substrate. The isolation platform is designed to provide low power oven-control, vibration isolation and shock protection. It involves batch flip-chip assembly of a MEMS device onto the isolation platform wafer. The MEMS device and isolation structure are encapsulated at the wafer-level by another substrate with vertical feedthroughs for vacuum/hermetic sealing and electrical signal connections. This technology was developed for high performance gyroscopes, but can be applied to any type of MEMS device.

  1. Organic acids, amino acids compositions in the root exudates and Cu-accumulation in castor (Ricinus communis L.) Under Cu stress.

    PubMed

    Huang, Guoyong; Guo, Guangguang; Yao, Shiyuan; Zhang, Na; Hu, Hongqing

    2016-01-01

    Ricinus communis L. is a hyperaccumulation plant newly discovered in an abandoned land of Cu mine in China. A hydroponic experiment was then carried out to determine the root exudates in the Cu-tolerant castor (Ricinus communis L.). Plants were grown in nutrient solution with increasing level of Cu doses (0, 100, 250, 500, and 750 μmol/L Cu) in the form of CuSO4. Cu accumulation in the roots and shoots of castor, and root exudates collected from the castor were measured. The results indicated that the castor had a high Cu accumulation capacity and the Cu concentrations in the shoots and roots of the castor treated with 750 μmol/L Cu were 177.1, 14586.7 mg/kg, respectively. Tartaric was the largest in the root exudates in terms of concentrations, which reached up to 329.13 μmol/g (dry plant) in the level of 750 μmol/L Cu. There was a significantly positive linear relationship between the Cu concentration in root and the concentration of succinic (R = 0.92, P < 0.05), tartaric (R = 0.96, P < 0.01), and citric (R = 0.89, P < 0.05). These results indicated that the difference in root exudation from castor could affect their Cu tolerance. What is more, significant is that the high tartaric and citric, the low oxalic and cysteine in the root exudation of castor contributed to toleration of high Cu concentrations.

  2. Development of Cu Clad Cu-Zr Based Metallic Glass and Its Solderability

    NASA Astrophysics Data System (ADS)

    Terajima, Takeshi; Kimura, Hisamichi; Inoue, Akihisa

    Soldering is a candidate technique for joining metallic glasses. It can be processed far below the crystallization temperatures of the various metallic glasses so that there is no possibility of crystallization. However, wettability of Cu-Zr based metallic glass by Pb free solder is poor because a strong surface oxide film interferes direct contact between them. To overcome the problem, Cu thin film clad metallic glass was developed. It was preliminary produced by casting a melt of Cu36Zr48Al8Ag8 pre-alloy into Cu mold cavity, inside which Cu thin film with 2 mm in thickness was set on the wall. Cu36Zr48Al8Ag8 metallic glass, whose surface Cu thin film was welded to, was successfully produced. From the microstructure analyses, it was found that reaction layer was formed at the interface between Cu and Cu36Zr48Al8Ag8 metallic glass, however, there was no oxide in the Cu clad layer. Solderability to the metallic glass was drastically increased. The Cu clad layer played an important role to prevent the formation of surface oxide film and consequently improved the solderability.

  3. The impact of highly concentrated Mo and Cu dietary supplements, fed as a bolus, on the efficacy of chelated versus inorganic Cu in cattle on a low-Cu diet.

    PubMed

    Grace, N D; West, D M; Smith, S L; Knowles, S O

    2013-11-01

    To compare the efficacy of chelated versus inorganic forms of dietary Cu supplements, fed as a bolus, when challenged by a daily bolus of dietary Mo in cattle on a low-Cu diet. Forty non-lactating, Friesian dairy cows of adequate Cu status were assigned to four groups and fed a basal diet of baled silage containing 5.3 mg Cu and 0.4 mg Mo/kg DM. The experimental design was a factorial of two chemical forms of supplemental Cu and two levels of Mo intake, provided as pelleted grain supplements made from crushed barley/molasses plus Cu and Mo. The supplements contained 140 mg Cu/kg as Cu sulphate pentahydrate (CS), 140 mg Cu/kg as Cu glycinate (CG), CS plus 38 mg Mo/kg as sodium molybdate (CS+Mo), or CG plus 38 mg Mo/kg (CG+Mo). Commencing on Day 0, supplements were fed once daily (offered 1-1.2 kg/cow) and were completely consumed within 5-10 minutes, which constitutes a bolus type of administration. Liver samples were collected by biopsy at Days -24, 13, 41 or 47, and 69 for Cu determinations. The diets fed to the Cu+Mo groups were roughly equivalent to 25 mg Cu and 5.7 mg Mo/kg DM. Mean initial concentration of Cu in liver for all groups was 516 (SE 54) μmol Cu/kg fresh tissue. In cows supplemented with CS and CG, the final (Day 69) concentrations increased (p<0.01) to 939 (SE 166) and 853 (SE 163) μmol Cu/kg, respectively. These values were not different (p=0.72). For groups CS+Mo and CG+Mo, the final concentrations of 535 (SE 122) and 453 (SE 102) μmol Cu/kg were not different from initial values or from each other (p>0.25). The rate of accumulation of Cu in liver following bolus Cu and Mo intake was highly variable but was not affected by initial concentration of Cu in liver (p>0.9) or by the form of Cu (p>0.6). Mean rates of accumulation of Cu in liver were 4.0 (SD 3.8) and 0.65 (SD 2.0) μmol Cu/kg fresh tissue/day for the Cu-only treatments and the Cu+Mo treatments, respectively. When fed together as a bolus, high Mo intake negated the effect

  4. Stability enhancement of Cu2S against Cu vacancy formation by Ag alloying.

    PubMed

    Barman, Sajib K; Huda, Muhammad N

    2018-04-25

    As a potential solar absorber material, Cu 2 S has proved its importance in the field of renewable energy. However, almost all the known minerals of Cu 2 S suffer from spontaneous Cu vacancy formation in the structure. The Cu vacancy formation causes the structure to possess very high p-type doping that leads the material to behave as a degenerate semiconductor. This vacancy formation tendency is a major obstacle for this material in this regard. A relatively new predicted phase of Cu 2 S which has an acanthite-like structure was found to be preferable than the well-known low chalcocite Cu 2 S. However, the Cu-vacancy formation tendency in this phase remained similar. We have found that alloying silver with this structure can help to reduce Cu vacancy formation tendency without altering its electronic property. The band gap of silver alloyed structure is higher than pristine acanthite Cu 2 S. In addition, Cu diffusion in the structure can be reduced with Ag doped in Cu sites. In this study, a systematic approach is presented within the density functional theory framework to study Cu vacancy formation tendency and diffusion in silver alloyed acanthite Cu 2 S, and proposed a possible route to stabilize Cu 2 S against Cu vacancy formations by alloying it with Ag.

  5. Stability enhancement of Cu2S against Cu vacancy formation by Ag alloying

    NASA Astrophysics Data System (ADS)

    Barman, Sajib K.; Huda, Muhammad N.

    2018-04-01

    As a potential solar absorber material, Cu2S has proved its importance in the field of renewable energy. However, almost all the known minerals of Cu2S suffer from spontaneous Cu vacancy formation in the structure. The Cu vacancy formation causes the structure to possess very high p-type doping that leads the material to behave as a degenerate semiconductor. This vacancy formation tendency is a major obstacle for this material in this regard. A relatively new predicted phase of Cu2S which has an acanthite-like structure was found to be preferable than the well-known low chalcocite Cu2S. However, the Cu-vacancy formation tendency in this phase remained similar. We have found that alloying silver with this structure can help to reduce Cu vacancy formation tendency without altering its electronic property. The band gap of silver alloyed structure is higher than pristine acanthite Cu2S. In addition, Cu diffusion in the structure can be reduced with Ag doped in Cu sites. In this study, a systematic approach is presented within the density functional theory framework to study Cu vacancy formation tendency and diffusion in silver alloyed acanthite Cu2S, and proposed a possible route to stabilize Cu2S against Cu vacancy formations by alloying it with Ag.

  6. Novel bimetallic thiocyanate-bridged Cu(II)-Hg(II) compounds-synthesis, X-Ray studies and magnetic properties

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Machura, B., E-mail: basia@ich.us.edu.pl; Switlicka, A.; Zwolinski, P.

    2013-01-15

    Seven novel heterobimetallic Cu/Hg polymers based on thiocyanate bridges have been synthesised and characterised by means of IR, EPR, magnetic measurements and single crystal X-Ray. Three of them, [Cu(pzH){sub 4}Hg(SCN){sub 4}]{sub n} (1) [Cu(indH){sub 4}Hg(SCN){sub 4}]{sub n} (2) and [Cu(ampy){sub 2}Hg(SCN){sub 4}]{sub n} (3), have one-dimensional coordination structure. Two compounds [Cu(pzH){sub 2}Hg(SCN){sub 4}]{sub n} (4) and [Cu(abzimH)Hg(SCN){sub 4}]{sub n} (5) form two-dimensional nets, whereas the complexes [Cu(pyCN){sub 2}Hg(SCN){sub 4}]{sub n} (6) and [Cu(pyCH(OH)(OMe)){sub 2}Hg(SCN){sub 4}]{sub n} (7) are three-dimensional coordination polymers. The chains of 1 are connected by the intermolecular N-H Bullet Bullet Bullet N hydrogen bonds to the threemore » dimensional net. In 2 the N-H Bullet Bullet Bullet S hydrogen bonds link the polymeric chains to the two dimensional layer extending along crystallographic (0 0 1) plane. The polymeric chains of compound 3 are joined by the intermolecular N-H Bullet Bullet Bullet N and N-H Bullet Bullet Bullet S hydrogen bonds to the three dimensional net. The polymeric layers of 4 are connected by the intermolecular N-H Bullet Bullet Bullet N hydrogen bonds to the three dimensional net. - Graphical abstract: Novel bimetallic thiocyanate-bridged Cu(II)-Hg(II) compound-synthesis,X-Ray studies and magnetic properties. Highlights: Black-Right-Pointing-Pointer Novel heterobimetallic Cu/Hg coordination polymers were synthesised. Black-Right-Pointing-Pointer The multidimensional structures have been proved by single X-ray analysIs. Black-Right-Pointing-Pointer A variation in the crystalline architectures was observed depending on auxiliary ligands. Black-Right-Pointing-Pointer Magnetic measurements indicate weak exchange interaction between Cu(II) in the crystal lattices below 10 K.« less

  7. Complete Fabrication of a Traversable 3 µm Thick NbN Film Superconducting Coil with Cu plated layer of 42m in Length in a Spiral Three-Storied Trench Engraved in a Si Wafer of 76.2 mm in Diameter Formed by MEMS Technology for a Compact SMES with High Energy Storage Volume Density

    NASA Astrophysics Data System (ADS)

    Suzuki, Yasuhiro; Iguchi, Nobuhiro; Adachi, Kazuhiro; Ichiki, Akihisa; Hioki, Tatsumi; Hsu, Che-Wei; Sato, Ryoto; Kumagai, Shinya; Sasaki, Minoru; Noh, Joo-Hyong; Sakurahara, Yuuske; Okabe, Kyohei; Takai, Osamu; Honma, Hideo; Watanabe, Hideo; Sakoda, Hitoshi; Sasagawa, Hiroaki; Doy, Hideyuki; Zhou, Shuliang; Hori, H.; Nishikawa, Shigeaki; Nozaki, Toshihiro; Sugimoto, Noriaki; Motohiro, Tomoyoshi

    2017-09-01

    Based on the concept of a novel approach to make a compact SMES unit composed of a stack of Si wafers using MEMS process proposed previously, a complete fabrication of a traversable 3 µam thick NbN film superconducting coil lined with Cu plated layer of 42m in length in a spiral three-storied trench engraved in and extended over a whole Si-wafer of 76.2 mm in diameter was attained for the first time. With decrease in temperature, the DC resistivity showed a metallic decrease indicating the current pass was in the Cu plated layer and then made a sudden fall to residual contact resistance indicating the shift of current pass from the Cu plated layer to the NbN film at the critical temperature Tc of 15.5K by superconducting transition. The temperature dependence of I-V curve showed the increase in the critical current with decrease in the temperature and the highest critical current measured was 220 mA at 4K which is five times as large as that obtained in the test fabrication as the experimental proof of concept presented in the previous report. This completion of a one wafer superconducting NbN coil is an indispensable step for the next proof of concept of fabrication of series-connected two wafer coils via superconductive joint which will read to series connected 600 wafer coils finally, and for replacement of NbN by high Tc superconductor such as YBa2Cu3O7-x for operation under the cold energy of liquid hydrogen or liquid nitrogen.

  8. Analysis of scattering lengths in Co/Cu/Co and Co/Cu/Co/Cu spin-valves using a Ru barrier

    NASA Astrophysics Data System (ADS)

    Strijkers, G. J.; Willekens, M. M. H.; Swagten, H. J. M.; de Jonge, W. J. M.

    1996-10-01

    We use uncoupled Co/Cu/Co and Co/Cu/Co/Cu spin-valve structures with a Ru barrier shifted through the top Co and Cu layer, respectively, to measure the longest of the electron mean free paths in Co and Cu as originally suggested by Parkin. From semiclassical transport calculations and careful analysis of the magnetoresistance data we conclude that the exponential behavior of ΔG is uniquely related to the longest of the Co and Cu mean free paths under the condition of effective spin-dependent filtering at the interfaces or in the bulk of the Co. In this regime we have compared λlong in Co and Cu with bulk conductivities (~λshort+λlong), yielding no strong evidence for bulk spin-dependent scattering in Co.

  9. First principles Study on Transparent High-Tc Superconductivity in hole-doped Delafossite CuAlO2

    NASA Astrophysics Data System (ADS)

    Nakanishi, Akitaka; Katayama-Yoshida, Hiroshi

    2012-02-01

    The CuAlO2 is the transparent p-type conductor without any intentional doping. Transparent superdoncutivity and high thermoelectric power are suggested in p-type CuAlO2 [1]. Katayama-Yoshida et al. proposed that it may cause a strong electron-phonon interaction and a superconductivity. But, the calculation of superconducting critical temperature Tc is not performed. We performed the first principles calculation about the Tc of hole-doped CuAlO2 by shifting the Fermi level rigidly. In lightly hole-doped CuAlO2, the Fermi level is located at Cu and O anti-bonding band. The electrons of this band strongly interact with the A1L1 phonon mode because the direction of O-Cu-O dumbbell is parallel to the oscillation direction of the A1L1 phonon mode. As a result, Tc of lightly hole-doped CuAlO2 is about 50 K. We also discuss the materials design to enhance the Tc based on the charge-excitation-induced negative effective U system.[4pt] [1] H. Katayama-Yoshida, T. Koyanagi, H. Funashima, H. Harima, A. Yanase: Solid State Communication 126 (2003) 135. [0pt] [2] A. Nakanishi and H. Katayama-Yoshida: Solid State Communication, in printing. (arXiv:1107.2477v3

  10. Yield strength of Cu and an engineered material of Cu with 1% Pb

    NASA Astrophysics Data System (ADS)

    Buttler, William; Gray, George, III; Fensin, Saryu; Grover, Mike; Stevens, Gerald; Stone, Joseph; Turley, William

    2015-06-01

    To study the effects of engineered elastic-plastic yield on the mass-ejection from shocked materials we fielded explosively driven Cu and CuPb experiments. The Cu and CuPb experiments fielded fully annealed disks in contact with PBX 9501; the CuPb was extruded with 1% Pb that aggregates at the Cu grain boundaries. The elastic-plastic yield strength is explored as a difference of ejecta production of CuPb versus Cu, where the ejecta production of solid materials ties directly to the surface perturbation geometries of wavelengths (fixed at 65 μm) and amplitudes (which were varied). We observed that the Cu performs as expected, with ejecta turning on at the previously observed yield threshold, but the CuPb ejects mass in much larger quantities, at much lower wavenumber (k = 2 π/ λ) amplitude (h) products (kh), implying a reduced elastic-plastic yield stress of the engineered material, CuPb.

  11. MgCu metallic glass

    NASA Astrophysics Data System (ADS)

    Durandurdu, Murat

    2018-03-01

    We generate an amorphous MgCu model using the rapid solidification of the melt through a first-principles molecular dynamics approach within a generalised gradient approximation and reveal, for the first time, its structural features and mechanical properties in details. The liquid and glassy MgCu are found to acquire slightly distinct local structures. Yet in both forms of MgCu, most Cu atoms have a tendency to form the ideal and defective icosahedrons while Mg atoms are arranged in complex configurations. The mean coordination number of Cu and Mg at 300 K is 11.31 and 13.73, respectively. The short-range order of MgCu glass is projected to be different than the known crystalline MgCu and Mg2Cu phases. The mechanical properties of MgCu glass and the CsCl-type MgCu crystal are computed and compared. On the basis of the enthalpy analyses, a possible pressure-induced crystallisation of the MgCu glass into a CsCl-type structure is proposed to occur at around 11 GPa.

  12. Effects of fluoride residue on thermal stability in Cu/porous low-k interconnects

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kobayashi, Y.; Ozaki, S.; Nakamura, T.

    2014-06-19

    We have investigated the effects of fluoride residue on the thermal stability of a Cu/barrier metal (BM)/porous low-k film (k < 2.3) structure. We confirmed that the Cu agglomerated more on a BM/inter layer dielectric (ILD) with a fluoride residue. To consider the effect of fluoride residue on Cu agglomeration, the structural state at the Cu/BM interface was evaluated with a cross-section transmission electron microscope (TEM) and atomic force microscope (AFM). In addition, the chemical bonding state at the Cu/BM interface was evaluated with the interface peeling-off method and X-ray photoelectron spectroscopy (XPS). Moreover, we confirmed the ionization of fluoridemore » residue and oxidation of Cu with fluoride and moisture to clarify the effect of fluoride residue on Cu. Our experimental results indicated that the thermal stability in Cu/porous low-k interconnects was degraded by enhancement of Cu oxidation with fluoride ions diffusion as an oxidizing catalyst.« less

  13. A bronze matryoshka: the discrete intermetalloid cluster [Sn@Cu12@Sn20](12-) in the ternary phases A12Cu12Sn21 (A = Na, K).

    PubMed

    Stegmaier, Saskia; Fässler, Thomas F

    2011-12-14

    The synthesis and crystal structure of the first ternary A-Cu-Sn intermetallic phases for the heavier alkali metals A = Na to Cs is reported. The title compounds A(12)Cu(12)Sn(21) show discrete 33-atom intermetalloid Cu-Sn clusters {Sn@Cu(12)@Sn(20)}, which are composed of {Sn(20)} pentagonal dodecahedra surrounding {Cu(12)} icosahedra with single Sn atoms at the center. Na(12)Cu(12)Sn(21) and K(12)Cu(12)Sn(21) were characterized by single-crystal XRD studies, and the successful synthesis of analogous A-Cu-Sn compounds with A = Rb and Cs is deduced from powder XRD data. The isotypic A(12)Cu(12)Sn(21) phases crystallize in the cubic space group Pn ̅3m (No. 224), with the Cu-Sn clusters adopting a face centered cubic arrangement. A formal charge of 12- can be assigned to the {Sn@Cu(12)@Sn(20)} cluster unit, and the interpretation of the title compounds as salt-like intermetallic phases featuring discrete anionic intermetalloid [Sn@Cu(12)@Sn(20)](12-) clusters separated by alkali metal cations is supported by electronic structure calculations. For both Na(12)Cu(12)Sn(21) and K(12)Cu(12)Sn(21), DFT band structure calculations (TB-LMTO-ASA) reveal a band gap. The discrete [Sn@Cu(12)@Sn(20)](12-) cluster is analyzed in consideration of the molecular orbitals obtained from hybrid DFT calculations (Gaussian 09) for the cluster anion. The [Sn@Cu(12)@Sn(20)](12-) cluster MOs can be classified with labels indicating the numbers of radial and angular nodes, in the style of spherical shell models of cluster bonding. © 2011 American Chemical Society

  14. Chemical Trend of Superconducting Critical Temperatures in Hole-Doped CuBO2, CuAlO2, CuGaO2, and CuInO2

    NASA Astrophysics Data System (ADS)

    Nakanishi, Akitaka; Katayama-Yoshida, Hiroshi; Ishikawa, Takahiro; Shimizu, Katsuya

    2016-09-01

    We calculated the superconducting critical temperature (Tc) for hole-doped CuXO2 (X = B, Al, Ga, and In) compounds using first-principles calculations based on rigid band model. The compounds with X = Al, Ga, and In have delafosite-type structures and take maximum Tc values at 0.2-0.3 with respect to the number of holes (Nh) in the unit-cell: 50 K for CuAlO2, 10 K for CuGaO2, and 1 K for CuInO2. The decrease of Tc for this change in X is involved by covalency reduction and lattice softening associated with the increase of ionic mass and radius. For CuBO2 which is a lighter compound than CuAlO2, the delafosite structure is unstable and a body-centered tetragonal structure emerges as the most stable structure. As the results, the electron-phonon interaction is decreased and Tc is lower by approximately 43 K than that of CuAlO2 at the hole-doping conditions of Nh = 0.2-0.3.

  15. Cu retention in an acid soil amended with perlite winery waste.

    PubMed

    Rodríguez-Salgado, Isabel; Pérez-Rodríguez, Paula; Gómez-Armesto, Antía; Nóvoa-Muñoz, Juan Carlos; Arias-Estévez, Manuel; Fernández-Calviño, David

    2016-02-01

    The effect of perlite waste from a winery on general soil characteristics and Cu adsorption was assessed. The studied soil was amended with different perlite waste concentrations corresponding to 10, 20, 40 and 80 Mg ha(-1). General soil characteristics and Cu adsorption and desorption curves were determined after different incubation times (from 1 day to 8 months). The addition of perlite waste to the soil increased the amounts of organic matter as well as soil nutrients such as phosphorus and potassium, and these increments were stable with time. An increase in Cu adsorption capacity was also detected in the perlite waste-amended soils. The effect of perlite waste addition to the soil had special relevance on its Cu adsorption capacity at low coverage concentrations and on the energy of the soil-Cu bonds.

  16. Cu diffusivity in granitic melts with application to the formation of porphyry Cu deposits

    NASA Astrophysics Data System (ADS)

    Ni, Huaiwei; Shi, Huifeng; Zhang, Li; Li, Wan-Cai; Guo, Xuan; Liang, Ting

    2018-06-01

    We report new experimental data of Cu diffusivity in granite porphyry melts with 0.01 and 3.9 wt% H2O at 0.15-1.0 GPa and 973-1523 K. A diffusion couple method was used for the nominally anhydrous granitic melt, whereas a Cu diffusion-in method using Pt95Cu5 as the source of Cu was applied to the hydrous granitic melt. The diffusion couple experiments also generate Cu diffusion-out profiles due to Cu loss to Pt capsule walls. Cu diffusivities were extracted from error function fits of the Cu concentration profiles measured by LA-ICP-MS. At 1 GPa, we obtain {D_{{Cu, dry, 1 GPa}}}=\\exp [ {( - {13.89} ± {0.42}) - {{12878} ± {540}}/T} ], and {D_{{Cu, 3}{.9 wt% }{{H}2}{O},{ 1 GPa}}}=\\exp [ {( - 16.31 ± 1.30) - {{8148} ± {1670}}/T} ], where D is Cu diffusivity in m2/s and T is temperature in K. The above expressions are in good agreement with a recent study on Cu diffusion in rhyolitic melt using the approach of Cu2S dissolution. The observed pressure effect over 0.15-1.0 GPa can be described by an activation volume of 5.9 cm3/mol for Cu diffusion. Comparison of Cu diffusivity to alkali diffusivity and its variation with melt composition implies fourfold-coordinated Cu+ in silicate melts. Our experimental results indicate that in the formation of porphyry Cu deposits, the diffusive transport of magmatic Cu to sulfide liquids or fluid bubbles is highly efficient. The obtained Cu diffusivity data can also be used to assess whether equilibrium Cu partitioning can be reached within certain experimental durations.

  17. Understanding the fast phase-change mechanism of tetrahedrally bonded Cu2GeTe3 : Comprehensive analyses of electronic structure and transport phenomena

    NASA Astrophysics Data System (ADS)

    Kobayashi, Keisuke; Skelton, Jonathan M.; Saito, Yuta; Shindo, Satoshi; Kobata, Masaaki; Fons, Paul; Kolobov, Alexander V.; Elliott, Stephen; Ando, Daisuke; Sutou, Yuji

    2018-05-01

    Cu2GeTe3 (CGT) phase-change material, a promising candidate for advanced fast nonvolatile random-access-memory devices, has a chalcopyritelike structure with s p3 bonding in the crystalline phase; thus, the phase-change (PC) mechanism is considered to be essentially different from that of the standard PC materials (e.g., Ge-Sb-Te) with threefold to sixfold p -like bonding. In order to reveal the PC mechanism of CGT, the electronic structure change due to PC has been investigated by laboratory hard x-ray photoelectron spectroscopy and combined first-principles density-functional theory molecular-dynamics simulations. The valence-band spectra, in both crystalline and amorphous phases, are well simulated by the calculations. An inherent tendency of Te 5 s lone-pair formation and an enhanced participation of Cu 3 d orbitals in the bonding are found to play dominant roles in the PC mechanism. The electrical conductivity of as-deposited films and its change during the PC process is investigated in connection with valence-band spectral changes near the Fermi level. The results are successfully analyzed, based on a model proposed by Davis and Mott for chalcogenide amorphous semiconductors. The results suggest that robustness of the defect-band states against thermal stress is a key to the practical application of this material for memory devices.

  18. Yield strength of Cu and a CuPb alloy (1% Pb)

    NASA Astrophysics Data System (ADS)

    Buttler, W. T.; Gray, G. T.; Fensin, S. J.; Grover, M.; Prime, M. B.; Stevens, G. D.; Stone, J. B.; Turley, W. D.

    2017-01-01

    With PBX9501 we explosively loaded fully annealed OFHC-Cu and an OFHC-CuPb (extruded with 1% Pb that aggregates at the Cu grain boundaries) to study the effects of the 1% Pb on the elastic-plastic yield Y of Cu. The yield-stress Y was studied through observation of surface velocimetry and total ejected mass ρA from periodic surface perturbations machined onto the sample surfaces. The perturbation's wavelengths were λ ≈ 65 µm, and their amplitudes h were varied to determine the wavenumber (2π/λ) amplitude product kh at which ejecta production for the Cu and CuPb begins, which relates to Y. The Y of the two materials is apparently different.

  19. The Effect of Composition of Different Ecotoxicological Test Media on Free and Bioavailable Copper from CuSO4 and CuO Nanoparticles: Comparative Evidence from a Cu-Selective Electrode and a Cu-Biosensor

    PubMed Central

    Käkinen, Aleksandr; Bondarenko, Olesja; Ivask, Angela; Kahru, Anne

    2011-01-01

    The analysis of (bio)available copper in complex environmental settings, including biological test media, is a challenging task. In this study, we demonstrated the potential of a recombinant Pseudomonas fluorescens-based biosensor for bioavailability analysis of CuSO4 and CuO nanoparticles (nano-CuO) in seventeen different ecotoxicological and microbiologial test media. In parallel, free Cu in these test media was analysed using Cu-ion selective electrode (Cu-ISE). In the case of CuSO4, both free and bioavailable Cu decreased greatly with increasing concentration of organics and phosphates in the tested media. A good correlation between free and bioavailable Cu was observed (r = 0.854, p < 0.01) indicating that the free Cu content in biological test media may be a reasonably good predictor for the toxicity of CuSO4. As a proof, it was demonstrated that when eleven EC50 values for CuSO4 from different organisms in different test media were normalized for the free Cu in these media, the difference in these EC50 values was decreased from 4 to 1.8 orders of magnitude. Thus, toxicity of CuSO4 to these organisms was attributed to the properties of the test media rather than to inherent differences in sensitivity between the test organisms. Differently from CuSO4, the amount of free and bioavailable Cu in nano-CuO spiked media was not significantly correlated with the concentration of organics in the test media. Thus, the speciation of nano-CuO in toxicological test systems was not only determined by the complexation of Cu ions but also by differential dissolution of nano-CuO in different test conditions leading to a new speciation equilibrium. In addition, a substantial fraction of nano-CuO that was not detectable by Cu-ISE (i.e., not present as free Cu-ions) was bioavailable to Cu-biosensor bacteria. Thus, in environmental hazard analysis of (nano) particulate materials, biosensor analysis may be more informative than other analytical techniques. Our results demonstrate

  20. Effects of Al addition on atomic structure of Cu-Zr metallic glass

    NASA Astrophysics Data System (ADS)

    Li, Feng; Zhang, Huajian; Liu, Xiongjun; Dong, Yuecheng; Yu, Chunyan; Lu, Zhaoping

    2018-02-01

    The atomic structures of Cu52Zr48 and Cu45Zr48Al7 metallic glasses (MGs) have been studied by molecular dynamic simulations. The results reveal that the molar volume of the Cu45Zr48Al7 MG is smaller than that of the Cu52Zr48 MG, although the size of the Al atom is larger than that of the Cu atom, implying an enhanced atomic packing density achieved by introducing Al into the ternary MG. Bond shortening in unlike atomic pairs Zr-Al and Cu-Al is observed in the Cu45Zr48Al7 MG, which is attributed to strong interactions between Al and (Zr, Cu) atoms. Meanwhile, the atomic packing efficiency is enhanced by the minor addition of Al. Compared with the Cu52Zr48 binary MG, the potential energy of the ternary MG decreases and the glass transition temperature increases. Structural analyses indicate that more Cu- and Al-centered full icosahedral clusters emerge in the Cu45Zr48Al7 MG as some Cu atoms are substituted by Al. Furthermore, the addition of Al leads to more icosahedral medium-range orders in the ternary MG. The increase of full icosahedral clusters and the enhancement of the packing density are responsible for the improved glass-forming ability of Cu45Zr48Al7.

  1. Wafer-level packaging with compression-controlled seal ring bonding

    DOEpatents

    Farino, Anthony J

    2013-11-05

    A device may be provided in a sealed package by aligning a seal ring provided on a first surface of a first semiconductor wafer in opposing relationship with a seal ring that is provided on a second surface of a second semiconductor wafer and surrounds a portion of the second wafer that contains the device. Forcible movement of the first and second wafer surfaces toward one another compresses the first and second seal rings against one another. A physical barrier against the movement, other than the first and second seal rings, is provided between the first and second wafer surfaces.

  2. Sorption of Cu(2+) on humic acids sequentially extracted from a sediment.

    PubMed

    Yang, Kun; Miao, Gangfen; Wu, Wenhao; Lin, Daohui; Pan, Bo; Wu, Fengchang; Xing, Baoshan

    2015-11-01

    In addition to the diverse properties of humic acids (HAs) extracted from different soils or sediments, chemical compositions, functional groups and structures of HAs extracted from a single soil or sediment could also be diverse and thus significantly affect sorption of heavy metals, which is a key process controlling the transfer, transformation and fate of heavy metals in the environment. In this study, we sequentially extracted four HA fractions from a single sediment and conducted the sorption experiments of Cu(2+) on these HA fractions. Our results showed that aromaticity and acidic group content of HA fraction decreased with increasing extraction. Earlier extracted HA fraction had higher sorption capacity and affinity for Cu(2+). There were two fractions of adsorbed Cu(2+) on HAs, i.e., ion exchanged fraction and surface bonded fraction, which can be captured mechanically by the bi-Langmuir model with good isotherm fitting. The ion exchanged fraction had larger sorption capacity but lower sorption affinity, compared with the surface bonded fraction. The dissociated carboxyl groups of HAs were responsible for both fractions of Cu(2+) sorption, due to the more Cu(2+) sorption on the earlier extracted HA fraction with more carboxyl groups and at higher pH. The intensive competition between H(+) and the exchangeable Cu(2+) could result in the decrease of ion exchanged capacity and affinity for Cu(2+) on HAs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Room-temperature wafer bonding of LiNbO3 and SiO2 using a modified surface activated bonding method

    NASA Astrophysics Data System (ADS)

    Takigawa, Ryo; Higurashi, Eiji; Asano, Tanemasa

    2018-06-01

    In this paper, we report room-temperature bonding of LiNbO3 (LN) and SiO2/Si for the realization of a LN on insulator (LNOI)/Si hybrid wafer. We investigate the applicability of a modified surface activated bonding (SAB) method for the direct bonding of LN and a thermally grown SiO2 layer. The modified SAB method using ion beam bombardment demonstrates the room-temperature wafer bonding of LN and SiO2. The bonded wafer was successfully cut into 0.5 × 0.5 mm2 dies without interfacial debonding owing to the applied stress during dicing. In addition, the surface energy of the bonded wafer was estimated to be approximately 1.8 J/m2 using the crack opening method. These results indicate that a strong bond strength can be achieved, which may be sufficient for device applications.

  4. Reliability Assessment and Activation Energy Study of Au and Pd-Coated Cu Wires Post High Temperature Aging in Nanoscale Semiconductor Packaging.

    PubMed

    Gan, C L; Hashim, U

    2013-06-01

    Wearout reliability and high temperature storage life (HTSL) activation energy of Au and Pd-coated Cu (PdCu) ball bonds are useful technical information for Cu wire deployment in nanoscale semiconductor device packaging. This paper discusses the influence of wire type on the wearout reliability performance of Au and PdCu wire used in fine pitch BGA package after HTSL stress at various aging temperatures. Failure analysis has been conducted to identify the failure mechanism after HTSL wearout conditions for Au and PdCu ball bonds. Apparent activation energies (Eaa) of both wire types are investigated after HTSL test at 150 °C, 175 °C and 200 °C aging temperatures. Arrhenius plot has been plotted for each ball bond types and the calculated Eaa of PdCu ball bond is 0.85 eV and 1.10 eV for Au ball bond in 110 nm semiconductor device. Obviously Au ball bond is identified with faster IMC formation rate with IMC Kirkendall voiding while PdCu wire exhibits equivalent wearout and or better wearout reliability margin compare to conventional Au wirebond. Lognormal plots have been established and its mean to failure (t 50 ) have been discussed in this paper.

  5. New Production Routes for Medical Isotopes 64Cu and 67Cu Using Accelerator Neutrons

    NASA Astrophysics Data System (ADS)

    Kin, Tadahiro; Nagai, Yasuki; Iwamoto, Nobuyuki; Minato, Futoshi; Iwamoto, Osamu; Hatsukawa, Yuichi; Segawa, Mariko; Harada, Hideo; Konno, Chikara; Ochiai, Kentaro; Takakura, Kosuke

    2013-03-01

    We have measured the activation cross sections producing 64Cu and 67Cu, promising medical radioisotopes for molecular imaging and radioimmunotherapy, by bombarding a natural zinc sample with 14 MeV neutrons. We estimated the production yields of 64Cu and 67Cu by fast neutrons from \\text{natC(d,n) with 40 MeV 5 mA deuterons. We used the present result together with the evaluated cross section of Zn isotopes. The calculated 64Cu yield is 1.8 TBq (175 g 64Zn) for 12 h of irradiation; the yields of 67Cu by 67Zn(n,p)67Cu and 68Zn(n,x)67Cu were 249 GBq (184 g 67Zn) and 287 GBq (186 g 68Zn) at the end of 2 days of irradiation, respectively. From the results, we proposed a new route to produce 67Cu with very little radionuclide impurity via the 68Zn(n,x)67Cu reaction, and showed the 64Zn(n,p)64Cu reaction to be a promising route to produce 64Cu. Both 67Cu and 64Cu are noted to be produced using fast neutrons.

  6. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation

    NASA Astrophysics Data System (ADS)

    Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei; Wimble, Joshua M.; Lucci, Felicia R.; Lee, Sungsik; Michaelides, Angelos; Flytzani-Stephanopoulos, Maria; Stamatakis, Michail; Sykes, E. Charles H.

    2018-03-01

    The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards the synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu-based catalysts are not practical due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Using Pt/Cu single-atom alloys (SAAs), we examine C-H activation in a number of systems including methyl groups, methane and butane using a combination of simulations, surface science and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke-resistant C-H activation chemistry, with the added economic benefit that the precious metal is diluted at the atomic limit.

  7. Enhanced thermal stability of Cu alloy films by strong interaction between Ni and Zr (or Fe)

    NASA Astrophysics Data System (ADS)

    Zheng, Yuehong; Li, Xiaona; Cheng, Xiaotian; Li, Zhuming; Liu, Yubo; Dong, Chuang

    2018-04-01

    Low resistivity, phase stability and nonreactivity with surrounding dielectrics are the key to the application of Cu to ultra-large-scale integrated circuits. Here, a stable solid solution cluster model was introduced to design the composition of barrierless Cu-Ni-Zr (or Fe) seed layers. The third elements Fe and Zr were dissolved into Cu via a second element Ni, which is soluble in both Cu and Zr (or Fe). The films were prepared by magnetron sputtering on the single-crystal p-Si (1 0 0) wafers. Since the diffusion characteristics of the alloying elements are different, the effects of the strong interaction between Ni and Zr (or Fe) on the film’s stability and resistivity were studied. The results showed that a proper addition of Zr-Ni (Zr/Ni  ⩽  0.6/12) into Cu could form a large negative lattice distortion, which inhibits Cu-Si interdiffusion and enhances the stability of Cu film. When Fe-Ni was co-added into Cu, the lattice distortion of Cu reached a lower value, 0.0029 Å  ⩽  |Δa|  ⩽  0.0046 Å, and the films showed poor stability. Therefore, when the model is applied to the composition design of the films, the strong interaction between the elements and the addition ratio should be taken into consideration.

  8. Kinetically inert Cu in coastal waters.

    PubMed

    Kogut, Megan B; Voelker, Bettina M

    2003-02-01

    Many studies have shown that Cu and other metals in natural waters are mostly bound by unidentified compounds interpreted to be strong ligands reversibly complexing a given metal. However, commonly applied analytical techniques are not capable of distinguishing strongly but reversibly complexed metal from metal bound in kinetically inert compounds. In this work, we use a modified competitive ligand exchange adsorptive cathodic stripping voltammetry method combined with size fractionation to show that most if not all of the apparently very strongly (log K > or = 13) bound Cu in samples from five New England coastal waters (1-18 nM, 10-60% of total Cu) is actually present as kinetically inert compounds. In three of the five samples examined by ultrafiltration, a significant portion of the 0.2-microm-filtrable inert Cu was retained by a 0.02-microm-pore size filter, suggesting that at least some of the Cu was kinetically inert because it was physically sequestered in colloidal material. The rest of the ambient Cu, and Cu added in titrations, were reversibly bound in complexes that could be modeled as having conditional stability constants of 10(10)-10(13). The Cu-binding ability of these complexes was equivalent to that of seawater containing reasonable concentrations of humic substances from terrestrial sources, approximately 0.15-0.45 mg of C/L. Both the inert compounds and the reversible ligands were important for determining [Cu2+] at ambient Cu levels in our samples.

  9. Cu6Sn5 Whiskers Precipitated in Sn3.0Ag0.5Cu/Cu Interconnection in Concentrator Silicon Solar Cells Solder Layer

    PubMed Central

    Zhang, Liang; Liu, Zhi-quan; Yang, Fan; Zhong, Su-juan

    2017-01-01

    Cu6Sn5 whiskers precipitated in Sn3.0Ag0.5Cu/Cu interconnection in concentrator silicon solar cells solder layer were found and investigated after reflow soldering and during aging. Ag3Sn fibers can be observed around Cu6Sn5 whiskers in the matrix microstructure, which can play an active effect on the reliability of interconnection. Different morphologies of Cu6Sn5 whiskers can be observed, and hexagonal rod structure is the main morphology of Cu6Sn5 whiskers. A hollow structure can be observed in hexagonal Cu6Sn5 whiskers, and a screw dislocation mechanism was used to represent the Cu6Sn5 growth. Based on mechanical property testing and finite element simulation, Cu6Sn5 whiskers were regarded as having a negative effect on the durability of Sn3.0Ag0.5Cu/Cu interconnection in concentrator silicon solar cells solder layer. PMID:28772686

  10. Colloidal synthesis of Cu-ZnO and Cu@CuNi-ZnO hybrid nanocrystals with controlled morphologies and multifunctional properties

    NASA Astrophysics Data System (ADS)

    Zeng, Deqian; Gong, Pingyun; Chen, Yuanzhi; Zhang, Qinfu; Xie, Qingshui; Peng, Dong-Liang

    2016-06-01

    Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities.Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications

  11. Synthesis of Cu/CuO nanoparticles in mesoporous material by solid state reaction

    NASA Astrophysics Data System (ADS)

    Sohrabnezhad, Sh.; Valipour, A.

    2013-10-01

    The Mobil Composition of Matter No. 41 (MCM-41) containing 1.0 and 5.0 wt.% of Cu was synthesized under solid state reaction. The calcinations of samples were done at two different temperatures, 500 and 300 °C. X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM) were used for samples characterization. Powder X-ray diffraction showed that when Cu(CH3COO)2 content is about 1.0 wt.% in Cu/MCM-41, the guest CuO-NPs and copper ions is formed on the silica channel wall, and more exists in the crystalline state. When Cu(CH3COO)2 content exceeds this value (5.0 wt.%), CuO nanoparticles and Cu2+ ions can be observed in low crystalline state. From the diffuse reflectance spectra it was confirmed that 5 wt.% Cu/MCM-41 sample calcined at 500 °C show plasmon resonance band due to Cu nanoparticles in the range between 500 and 600 nm and small copper clusters Cun in 450 nm. It also shows that some of the Cu2+ ions are present octahedrally in extraframework position in all samples. Both fourier transform infrared and diffuse reflectance spectra indicate that some of Cu2+ ions are tetrahedrally within the framework position in 1 wt.% Cu/MCM-41 samples. TEM images indicated that nanoparticles size of CuO is in range of 30-40 nm.

  12. Hydrodynamic evolution and jet energy loss in Cu + Cu collisions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Schenke, Bjoern; Department of Physics, McGill University, 3600 University Street, Montreal, Quebec, H3A 2T8; Jeon, Sangyong

    2011-04-15

    We present results from a hybrid description of Cu + Cu collisions using (3 + 1)-dimensional hydrodynamics (music) for the bulk evolution and a Monte Carlo simulation (martini) for the evolution of high-momentum partons in the hydrodynamical background. We explore the limits of this description by going to small system sizes and determine the dependence on different fractions of wounded nucleon and binary collisions scaling of the initial energy density. We find that Cu + Cu collisions are well described by the hybrid description at least up to 20% central collisions.

  13. Reactions in Electrodeposited Cu/Sn and Cu/Ni/Sn Nanoscale Multilayers for Interconnects

    PubMed Central

    Chia, Pay Ying; Haseeb, A. S. M. A.; Mannan, Samjid Hassan

    2016-01-01

    Miniaturization of electronic devices has led to the development of 3D IC packages which require ultra-small-scale interconnections. Such small interconnects can be completely converted into Cu-Sn based intermetallic compounds (IMCs) after reflow. In an effort to improve IMC based interconnects, an attempt is made to add Ni to Cu-Sn-based IMCs. Multilayer interconnects consisting of stacks of Cu/Sn/Cu/Sn/Cu or Cu/Ni/Sn/Ni/Sn/Cu/Ni/Sn/Ni/Cu with Ni = 35 nm, 70 nm, and 150 nm were electrodeposited sequentially using copper pyrophosphate, tin methanesulfonic, and nickel Watts baths, respectively. These multilayer interconnects were investigated under room temperature aging conditions and for solid-liquid reactions, where the samples were subjected to 250 °C reflow for 60 s and also 300 °C for 3600 s. The progress of the reaction in the multilayers was monitored by using X-ray Diffraction, Scanning Electron Microscope, and Energy dispersive X-ray Spectroscopy. FIB-milled samples were also prepared for investigation under room temperature aging conditions. Results show that by inserting a 70 nanometres thick Ni layer between copper and tin, premature reaction between Cu and Sn at room temperature can be avoided. During short reflow, the addition of Ni suppresses formation of Cu3Sn IMC. With increasing Ni thickness, Cu consumption is decreased and Ni starts acting as a barrier layer. On the other hand, during long reflow, two types of IMC were found in the Cu/Ni/Sn samples which are the (Cu,Ni)6Sn5 and (Cu,Ni)3Sn, respectively. Details of the reaction sequence and mechanisms are discussed. PMID:28773552

  14. Changes in urinary Cu, Zn, and Se levels in cancer patients after treatment with Sha Shen Mai Men Dong Tang

    PubMed Central

    Lai, Tung-Yuan; Kuo, Hsien-Wen

    2015-01-01

    Sha Shen Mai Men Dong Tang (SMD-2; 沙參麥冬湯 shā shēn mài dōng tāng) is a Chinese medicinal herb (CMH; 中草藥 zhōng cǎo yào) used to treat symptoms associated with cancer therapy. The objective of this study was to assess the effect of SMD-2 on the levels of urinary copper (Cu), zinc (Zn), and selenium (Se) in lung cancer patients and head and neck cancer patients receiving chemoradiotherapy. Forty-two head and neck cancer patients and 10 lung cancer patients participated in our clinical trial. Each patient received chemoradiotherapy for 4 weeks. In addition, each patient was treated with SMD-2 for 8 weeks, including 2 weeks prior to and after the chemoradiotherapy treatment. Comparison of urinary Cu, Zn, and Se levels and the ratios of Zn to Cu and Se to Cu at three time points in the two types of cancer were assessed using the generalized estimating equations (GEEs). After the patients received chemoradiotherapy for 4 weeks, SMD-2 treatment was found to be associated with a significant decrease in urinary Cu levels, whereas urinary Zn and Se levels increased significantly. In addition, the ratios of Zn to Cu and Se to Cu in the urine samples of these patients also increased significantly. Both the urinary Zn levels and the ratio of Zn to Cu in head and neck cancer patients were significantly higher than in lung cancer patients. Urinary Zn and Se levels and the ratios of Zn to Cu and Se to Cu, but not urinary Cu levels, increased significantly during and after treatment when assessed using the GEE model. The SMD-2 treatments significantly increased Zn and Se levels in the urine of head and neck cancer patients. Increased Zn and Se levels in urine strengthened immune system. PMID:27114935

  15. Gas Suppression via Copper Interlayers in Magnetron Sputtered Al-Cu2O Multilayers.

    PubMed

    Kinsey, Alex H; Slusarski, Kyle; Sosa, Steven; Weihs, Timothy P

    2017-07-05

    The use of thin-foil, self-propagating thermite reactions to bond components successfully depends on the ability to suppress gas generation and avoid pore formation during the exothermic production of brazes. To study the mechanisms of vapor production in diluted thermites, thin film multilayer Al-Cu-Cu 2 O-Cu foils are produced via magnetron sputtering, where the Cu layer thickness is systematically increased from 0 to 100 nm in 25 nm increments. The excess Cu layers act as diffusion barriers, limiting the transport of oxygen from the oxide to the Al fuel, as determined by slow heating differential scanning calorimetry experiments. Furthermore, by adding excess Cu to the system, the temperature of the self-propagating thermite reactions drops below the boiling point of Cu, eliminating the metal vapor production. It is determined that Cu vapor production can be eliminated by increasing the Cu interlayer thickness above 50 nm. However, the porous nature of the final products suggests that only metal vapor production is suppressed via dilution. Gas generation via oxygen release is still capable of producing a porous reaction product.

  16. Cohesive properties of (Cu,Ni)-(In,Sn) intermetallics: Database, electron-density correlations and interpretation of bonding trends

    NASA Astrophysics Data System (ADS)

    Ramos, S. B.; González Lemus, N. V.; Cabeza, G. F.; Fernández Guillermet, A.

    2016-06-01

    This paper presents a systematic and comparative study of the composition and volume dependence of the cohesive properties for a large group of Me-X intermetallic phases (IPs) with Me=Cu,Ni and X=In,Sn, which are of interest in relation with the design of lead-free soldering (LFS) alloys. The work relies upon a database with total-energy versus volume information developed by using projected augmented waves (PAW) calculations. In previous papers by the current authors it was shown that these results account satisfactorily for the direct and indirect experimental data available. In the present work, the database is further expanded to investigate the composition dependence of the volume (V0), and the composition and volume dependence of the bulk modulus (B0) and cohesive energy (Ecoh). On these bases, an analysis is performed of the systematic effects of replacing Cu by Ni in several Me-X phases (Me=Cu,Ni and X=In,Sn) reported as stable and metastable, as well as various hypothetical compounds involved in the thermodynamic modeling of IPs using the Compound-Energy Formalism. Moreover, it is shown that the cohesion-related quantities (B0/V0)½ and (Ecoh½/V0) can be correlated with a parameter expressing the number of valence electrons per unit volume. These findings are compared in detail with related relations involving the Miedema empirical electron density at the boundary of the Wigner-Seitz cell. In view of the co-variation of the cohesive properties, Ecoh is selected as a key property and its composition and structure dependence is examined in terms of a theoretical view of the bonding which involves the hybridization of the d-states of Cu or Ni with the s and p-states of In or Sn, for this class of compounds. In particular, a comparative analysis is performed of the DOS of various representative, iso-structural Me-X compounds. Various effects of relevance to understand the consequences of replacing Cu by Ni in LFS alloys are highlighted and explained

  17. Structural morphology of YBa 2Cu 3O 7- x

    NASA Astrophysics Data System (ADS)

    Sun, B. N.; Hartman, P.; Woensdregt, C. F.; Schmid, H.

    1990-03-01

    The structural morphology of YBa 2Cu 3O 7- x (YBCO) has been investigated by application of the periodic bond chain (PBC) theory. For x=1, the F forms were found to be {001}, {011}, {013}, {112} and {114}. Attachment energies have been calculated in broken bond model and in an electrostatic point charge model. For x=1 the theoretical growth habit is tabular to platy {001} with {011} as side faces. For x=0 {010} also becomes an F form. The habit is isometric with large {001} and {011} and small {010} faces. The outermost layer of {001} contains half of the Cu + ( x=1) or Cu 3+ and O 2- ( x=0) ions in an ordered arrangement based on a c(2x2) quadratic lattice. For the outermost layer of (010) ( x=0) an ordering scheme of the copper and oxygen ions is proposed. The occurrence of {010} rather than {011} on grown crystals has to be ascribed to external factors.

  18. 64Cu-ATSM and 18FDG PET uptake and 64Cu-ATSM autoradiography in spontaneous canine tumors: comparison with pimonidazole hypoxia immunohistochemistry

    PubMed Central

    2012-01-01

    Background The aim of this study was to compare 64Cu-diacetyl-bis(N4-methylsemicarbazone) (64Cu-ATSM) and 18FDG PET uptake characteristics and 64Cu-ATSM autoradiography to pimonidazole immunohistochemistry in spontaneous canine sarcomas and carcinomas. Methods Biopsies were collected from individual tumors between approximately 3 and 25 hours after the intravenous injection of 64Cu-ATSM and pimonidazole. 64Cu-ATSM autoradiography and pimonidazole immunostaining was performed on sectioned biopsies. Acquired 64Cu-ATSM autoradiography and pimonidazole images were rescaled, aligned and their distribution patterns compared. 64Cu-ATSM and 18FDG PET/CT scans were performed in a concurrent study and uptake characteristics were obtained for tumors where available. Results Maximum pimonidazole pixel value and mean pimonidazole labeled fraction was found to be strongly correlated to 18FDG PET uptake levels, whereas more varying results were obtained for the comparison to 64Cu-ATSM. In the case of the latter, uptake at scans performed 3 h post injection (pi) generally showed strong positive correlated to pimonidazole uptake. Comparison of distribution patterns of pimonidazole immunohistochemistry and 64Cu-ATSM autoradiography yielded varying results. Significant positive correlations were mainly found in sections displaying a heterogeneous distribution of tracers. Conclusions Tumors with high levels of pimonidazole staining generally displayed high uptake of 18FDG and 64Cu-ATSM (3 h pi.). Similar regional distribution of 64Cu-ATSM and pimonidazole was observed in most heterogeneous tumor regions. However, tumor and hypoxia level dependent differences may exist with regard to the hypoxia specificity of 64Cu-ATSM in canine tumors. PMID:22704363

  19. DFT studies of the effectiveness of p-substituted diphenyl amine antioxidants in styrene-butadiene rubber through their Cu(II) coordination ability

    NASA Astrophysics Data System (ADS)

    Puškárová, Ingrid; Breza, Martin

    2017-07-01

    Structures of a series of diphenyl amine (DPA) antioxidants and of their complexes with Cu2+ were optimized at B3LYP level of theory. DPAs may be divided into two groups according to their molar antioxidant effectiveness (AEM). The effectiveness of high-AEM DPA antioxidants at 130 °C rises with decreasing spin densities at Cu atoms and with the increasing electron density Laplacian at Cu-N bond critical points in the 2[DPA…Cu]2+ complexes similarly as in the case of p-phenylene diamine antioxidants. No such trends are observed at 25 °C and for low- AEM DPA antioxidants.

  20. Novel dimeric interface and electrostatic recognition in bacterial Cu,Zn superoxide dismutase

    PubMed Central

    Bourne, Yves; Redford, Susan M.; Steinman, Howard M.; Lepock, James R.; Tainer, John A.; Getzoff, Elizabeth D.

    1996-01-01

    Eukaryotic Cu,Zn superoxide dismutases (CuZnSODs) are antioxidant enzymes remarkable for their unusually stable β-barrel fold and dimer assembly, diffusion-limited catalysis, and electrostatic guidance of their free radical substrate. Point mutations of CuZnSOD cause the fatal human neurodegenerative disease amyotrophic lateral sclerosis. We determined and analyzed the first crystallographic structure (to our knowledge) for CuZnSOD from a prokaryote, Photobacterium leiognathi, a luminescent symbiont of Leiognathid fish. This structure, exemplifying prokaryotic CuZnSODs, shares the active-site ligand geometry and the topology of the Greek key β-barrel common to the eukaryotic CuZnSODs. However, the β-barrel elements recruited to form the dimer interface, the strategy used to forge the channel for electrostatic recognition of superoxide radical, and the connectivity of the intrasubunit disulfide bond in P. leiognathi CuZnSOD are discrete and strikingly dissimilar from those highly conserved in eukaryotic CuZnSODs. This new CuZnSOD structure broadens our understanding of structural features necessary and sufficient for CuZnSOD activity, highlights a hitherto unrecognized adaptability of the Greek key β-barrel building block in evolution, and reveals that prokaryotic and eukaryotic enzymes diverged from one primordial CuZnSOD and then converged to distinct dimeric enzymes with electrostatic substrate guidance. PMID:8917495

  1. Bimetallic AgCu/Cu2O hybrid for the synergetic adsorption of iodide from solution.

    PubMed

    Mao, Ping; Liu, Ying; Liu, Xiaodong; Wang, Yuechan; Liang, Jie; Zhou, Qihang; Dai, Yuexuan; Jiao, Yan; Chen, Shouwen; Yang, Yi

    2017-08-01

    To further improve the capacity of Cu 2 O to absorb I - anions from solution, and to understand the difference between the adsorption mechanisms of Ag/Cu 2 O and Cu/Cu 2 O adsorbents, bimetallic AgCu was doped into Cu 2 O through a facile solvothermal route. Samples were characterized and employed to adsorb I - anions under different experimental conditions. The results show that the Cu content can be tuned by adding different volumes of Ag sols. After doping bimetallic AgCu, the adsorption capacity of the samples can be increased from 0.02 mmol g -1 to 0.52 mmol g -1 . Moreover, the optimal adsorption is reached within only 240 min. Meanwhile, the difference between the adsorption mechanisms of Ag/Cu 2 O and Cu/Cu 2 O adsorbents was verified, and the cooperative adsorption mechanism of the AgCu/Cu 2 O hybrid was proposed and verified. In addition, the AgCu/Cu 2 O hybrid showed excellent selectivity, e.g., its adsorption efficiencies are 85.1%, 81.9%, 85.9% and 85.7% in the presence of the Cl - , CO 3 2- , SO 4 2- and NO 3 - competitive anions, respectively. Furthermore, the AgCu/Cu 2 O hybrid can worked well in other harsh environments (e.g., acidic, alkaline and seawater environments). Therefore, this study is expected to promote the development of Cu 2 O into a highly efficient adsorbent for the removal of iodide from solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Spectroscopic Definition of the CuZ° Intermediate in Turnover of Nitrous Oxide Reductase and Molecular Insight into the Catalytic Mechanism.

    PubMed

    Johnston, Esther M; Carreira, Cíntia; Dell'Acqua, Simone; Dey, Somdatta Ghosh; Pauleta, Sofia R; Moura, Isabel; Solomon, Edward I

    2017-03-29

    Spectroscopic methods and density functional theory (DFT) calculations are used to determine the geometric and electronic structure of Cu Z °, an intermediate form of the Cu 4 S active site of nitrous oxide reductase (N 2 OR) that is observed in single turnover of fully reduced N 2 OR with N 2 O. Electron paramagnetic resonance (EPR), absorption, and magnetic circular dichroism (MCD) spectroscopies show that Cu Z ° is a 1-hole (i.e., 3Cu I Cu II ) state with spin density delocalized evenly over Cu I and Cu IV . Resonance Raman spectroscopy shows two Cu-S vibrations at 425 and 413 cm -1 , the latter with a -3 cm -1 O 18 solvent isotope shift. DFT calculations correlated to these spectral features show that Cu Z ° has a terminal hydroxide ligand coordinated to Cu IV , stabilized by a hydrogen bond to a nearby lysine residue. Cu Z ° can be reduced via electron transfer from Cu A using a physiologically relevant reductant. We obtain a lower limit on the rate of this intramolecular electron transfer (IET) that is >10 4 faster than the unobserved IET in the resting state, showing that Cu Z ° is the catalytically relevant oxidized form of N 2 OR. Terminal hydroxide coordination to Cu IV in the Cu Z ° intermediate yields insight into the nature of N 2 O binding and reduction, specifying a molecular mechanism in which N 2 O coordinates in a μ-1,3 fashion to the fully reduced state, with hydrogen bonding from Lys397, and two electrons are transferred from the fully reduced μ 4 S 2- bridged tetranuclear copper cluster to N 2 O via a single Cu atom to accomplish N-O bond cleavage.

  3. Ultrasonic soldering of Cu alloy using Ni-foam/Sn composite interlayer.

    PubMed

    Xiao, Yong; Wang, Qiwei; Wang, Ling; Zeng, Xian; Li, Mingyu; Wang, Ziqi; Zhang, Xingyi; Zhu, Xiaomeng

    2018-07-01

    In this study, Cu alloy joints were fabricated with a Ni-foam reinforced Sn-based composite solder with the assistance of ultrasonic vibration. Effects of ultrasonic soldering time on the microstructure and mechanical properties of Cu/Ni-Sn/Cu joints were investigated. Results showed that exceptional metallurgic bonding could be acquired with the assistance of ultrasonic vibration using a self-developed Ni-foam/Sn composite solder. For joint soldered for 5 s, a (Cu,Ni) 6 Sn 5 intermetallic compound (IMC) layer was formed on the Cu substrate surface, Ni skeletons distributed randomly in the soldering seam and a serrated (Ni,Cu) 3 Sn 4 IMC layer was formed on the Ni skeleton surface. Increasing the soldering time to 20 s, the (Ni,Cu) 3 Sn 4 IMC layer grew significantly and exhibited a loose porous structure on the Ni skeleton surface. Further increase the soldering time to 30 s, Ni skeletons were largely dissolved in the Sn base solder, and micro-sized (Ni,Cu) 3 Sn 4 particles were formed and dispersed homogeneously in the soldering seam. The formation of (Ni,Cu) 3 Sn 4 particles was mainly ascribed to acoustic cavitations induced erosion and grain refining effects. The joint soldered for 30 s exhibited the highest shear strength of 64.9 ± 3.3 MPa, and the shearing failure mainly occurred at the soldering seam/Cu substrate interface. Copyright © 2018 Elsevier B.V. All rights reserved.

  4. Detection of esophageal cancer cell by photoelectrochemical Cu2O/ZnO biosensor (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Hsu, Chao-Hsin; Chu, Cheng-Hsun; Chen, Weichung; Wu, I.-Chen; Wu, Ming Tsang; Kuo, Chie-Tong; Tsiang, Raymond Chien-Chao; Wang, Hsiang-Chen

    2016-03-01

    We have demonstrated a Cu2O/ZnO nanorods (NRs) array p-n heterostructures photoelectrochemical biosensor. The electrodeposition of Cu2O at pH 12 acquired the preferably (111) lattice planes, resulting in the largest interfacial electric field between Cu2O and ZnO, which finally led to the highest separation efficiency of photogenerated charge carriers. High verticality ZnO nanorods by seed layer and thermal annealing assist the hydrothermal growth. The optimized Cu2O/ZnO NRs array p-n heterostructures exhibited enhanced PEC performance, such as elevated photocurrent and photoconversion efficiency, as well as excellent sensing performance for the sensitive detection of four strains of different races and different degree of cancer cell which made the device self-powered. We got spectral response characteristics and operating wavelength range of biosensor, and to verify the biological characteristics of cancer cells wafer react with different stages of cancer characterized by a cancer measured reaction experiment.

  5. Binuclear Cu A formation in biosynthetic models of Cu A in azurin proceeds via a novel Cu(Cys) 2His mononuclear copper intermediate

    DOE PAGES

    Chakraborty, Saumen; Polen, Michael J.; Chacon, Kelly N.; ...

    2015-09-09

    Cu A is a binuclear electron transfer (ET) center found in cytochrome c oxidases (C cOs), nitrous oxide reductases (N 2ORs), and nitric oxide reductase (NOR). In these proteins, the Cu A centers facilitate efficient ET ( k ET > 10 4 s –1) under low thermodynamic driving forces (10–90 mV). While the structure and functional properties of Cu A are well understood, a detailed mechanism of the incorporation of copper into the protein and the identity of the intermediates formed during the Cu A maturation process are still lacking. Previous studies of the Cu A assembly mechanism in vitromore » using a biosynthetic model Cu A center in azurin (Cu AAz) identified a novel intermediate X (I x) during reconstitution of the binuclear site. However, because of the instability of I x and the coexistence of other Cu centers, such as Cu A' and type 1 copper centers, the identity of this intermediate could not be established. In this paper, we report the mechanism of Cu A assembly using variants of Glu114XCu AAz (X = Gly, Ala, Leu, or Gln), the backbone carbonyl of which acts as a ligand to the Cu A site, with a major focus on characterization of the novel intermediate I x. We show that Cu A assembly in these variants proceeds through several types of Cu centers, such as mononuclear red type 2 Cu, the novel intermediate I x, and blue type 1 Cu. Our results show that the backbone flexibility of the Glu114 residue is an important factor in determining the rates of T2Cu → I x formation, suggesting that Cu A formation is facilitated by swinging of the ligand loop, which internalizes the T2Cu capture complex to the protein interior. The kinetic data further suggest that the nature of the Glu114 side chain influences the time scales on which these intermediates are formed, the wavelengths of the absorption peaks, and how cleanly one intermediate is converted to another. Through careful understanding of these mechanisms and optimization of the conditions, we have obtained I x in

  6. Synthesis of porous Cu from Al-Cu-Co decagonal quasicrystalline alloys

    NASA Astrophysics Data System (ADS)

    Kalai Vani, V.; Kwon, O. J.; Hong, S. M.; Fleury, E.

    2011-07-01

    The formation of a porous Cu structure from cast Al-Cu-Co decagonal quasicrystalline alloys has been studied using a selective corrosion technique. Two alkaline solutions were selected based on the electrochemical properties of the constituent elements. Selective corrosion of Al and Co was achieved by chemical immersion of the cast Al-Cu-Co alloy in both 5 M NaOH and 0.5 M Na2CO3 solutions; values for BET surface-to-weight ratio of up to 30 m2/g could be reached. Microstructural analyses indicated that the architecture of the resulting porous structures was composed of a needle-type phase, remaining from the decagonal phase, in addition to Cu and Cu-Co phases.

  7. Colloidal synthesis of Cu-ZnO and Cu@CuNi-ZnO hybrid nanocrystals with controlled morphologies and multifunctional properties.

    PubMed

    Zeng, Deqian; Gong, Pingyun; Chen, Yuanzhi; Zhang, Qinfu; Xie, Qingshui; Peng, Dong-Liang

    2016-06-02

    Metal-semiconductor hybrid nanocrystals have received extensive attention owing to their multiple functionalities which can find wide technological applications. The utilization of low-cost non-noble metals to construct novel metal-semiconductor hybrid nanocrystals is important and meaningful for their large-scale applications. In this study, a facile solution approach is developed for the synthesis of Cu-ZnO hybrid nanocrystals with well-controlled morphologies, including nanomultipods, core-shell nanoparticles, nanopyramids and core-shell nanowires. In the synthetic strategy, Cu nanocrystals formed in situ serve as seeds for the heterogeneous nucleation and growth of ZnO, and it eventually forms various Cu-ZnO hetero-nanostructures under different reaction conditions. These hybrid nanocrystals possess well-defined and stable heterostructure junctions. The ultraviolet-visible-near infrared spectra reveal morphology-dependent surface plasmon resonance absorption of Cu and the band gap absorption of ZnO. Furthermore, we construct a novel Cu@CuNi-ZnO ternary hetero-nanostructure by incorporating the magnetic metal Ni into the pre-synthesized colloidal Cu nanocrystals. Such hybrid nanocrystals possess a magnetic Cu-Ni intermediate layer between the ZnO shell and the Cu core, and exhibit ferromagnetic/superparamagnetic properties which expand their functionalities. Finally, enhanced photocatalytic activities are observed in the as-prepared non-noble metal-ZnO hybrid nanocrystals. This study not only provides an economical way to prepare high-quality morphology-controlled Cu-ZnO hybrid nanocrystals for potential applications in the fields of photocatalysis and photovoltaic devices, but also opens up new opportunities in designing ternary non-noble metal-semiconductor hybrid nanocrystals with multifunctionalities.

  8. Adsorption and desorption of Cu2+ on paddy soil aggregates pretreated with different levels of phosphate.

    PubMed

    Dai, Jun; Wang, Wenqin; Wu, Wenchen; Gao, Jianbo; Dong, Changxun

    2017-05-01

    Interactions between anions and cations are important for understanding the behaviors of chemical pollutants and their potential risks in the environment. Here we prepared soil aggregates of a yellow paddy soil from the Taihu Lake region, and investigated the effects of phosphate (P) pretreatment on adsorption-desorption of Cu 2+ of soil aggregates, free iron oxyhydrates-removed soil aggregates, goethite, and kaolinite with batch adsorption method. The results showed that Cu 2+ adsorption was reduced on the aggregates pretreated with low concentrations of P, and promoted with high concentrations of P, showing a V-shaped change. Compared with the untreated aggregates, the adsorption capacity of Cu 2+ was reduced when P application rates were lower than 260, 220, 130 and 110mg/kg for coarse, clay, silt and fine sand fractions, respectively. On the contrary, the adsorption capacity of Cu 2+ was higher on P-pretreated soil aggregates than on the control ones when P application rates were greater than those values. However, the desorption of Cu 2+ was enhanced at low levels of P, but suppressed at high levels of P, displaying an inverted V-shaped change over P adsorption. The Cu 2+ adsorption by the aggregate particles with and without P pretreatments was well described by the Freundlich equation. Similar results were obtained on P-pretreated goethite. However, such P effects on Cu 2+ adsorption-desorption were not observed on kaolinite and free iron oxyhydrates-removed soil aggregates. The present results indicate that goethite is one of the main soil substances responsible for the P-induced promotion and inhibition of Cu 2+ adsorption. Copyright © 2016. Published by Elsevier B.V.

  9. Fabrication and surface enhanced Raman scattering effect of centimeter level AgCuAu composite nanowires

    NASA Astrophysics Data System (ADS)

    Xu, Dapeng; Zhang, Song; Yang, Wei; Chen, Jian

    2017-10-01

    Centimeter level AgCuAu composite nanowires were prepared by a solid-state ionics method under a direct current electric field (DCEF) using fast ionic conductor RbAg4I5 films and vacuum thermal evaporation method. The surface morphology and chemical composition of the AuAgCu composite nanowires were characterized by scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS), respectively. Raman enhancement performance of the AgCuAu composite nanowires substrates was detected by Rhodamine 6G (R6G) aqueous solutions as probe molecules. Long-range order and short-range order AgCuAu composite nanowires with the length of 1 cm were prepared. The nanowires were bamboo-shaped with high surface roughness and the diameters of nanowires ranged from 60 to 100 nm. The molar ratio of Ag:Cu:Au in composite nanowires is 15:2:1. The intrinsic Raman peaks of 10-16 mol/L R6G at 612, 773, 1125, 1182, 1307, 1361, 1418, 1506, 1545, 1575, 1597, 1650 cm-1 are all present when AgCuAu composite nanowires were used as the SERS substrates.

  10. High-temperature stability of Au/Pd/Cu and Au/Pd(P)/Cu surface finishes

    NASA Astrophysics Data System (ADS)

    Ho, C. E.; Hsieh, W. Z.; Lee, P. T.; Huang, Y. H.; Kuo, T. T.

    2018-03-01

    Thermal reliability of Au/Pd/Cu and Au/Pd(4-6 wt.% P)/Cu trilayers in the isothermal annealing at 180 °C were investigated by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), and transmission electron microscopy (TEM). The pure Pd film possessed a nanocrystalline structure with numerous grain boundaries, thereby facilitating the interdiffusion between Au and Cu. Out-diffusion of Cu through Pd and Au grain boundaries yielded a significant amount of Cu oxides (CuO and Cu2O) over the Au surface and gave rise to void formation in the Cu film. By contrast, the Pd(P) film was amorphous and served as a good diffusion barrier against Cu diffusion. The results of this study indicated that amorphous Pd(P) possessed better oxidation resistance and thermal reliability than crystalline Pd.

  11. Metal-ligand bond directionality in the M2-NH3 complexes (M = Cu, Ag and Au)

    NASA Astrophysics Data System (ADS)

    Eskandari, K.; Ebadinejad, F.

    2018-05-01

    The metal-ligand bonds in the M2-NH3 complexes (M = Au, Ag and Cu) are directional and the M-M-N angles tend to be linear. Natural energy decomposition analysis (NEDA) and localised molecular orbital energy decomposition analysis (LMOEDA) approaches indicate that the metal-ligand bonds in these complexes are mainly electrostatic in nature, however, the electrostatic is not the cause of the linearity of M-M-N arrangements. Instead, NEDA shows that the charge transfer and core repulsion are mainly responsible for the directionality of these bonds. In the LMOEDA point of view, the repulsion term is the main reason for the linearity of these complexes. Interacting quantum atoms (IQA) analysis shows that inter-atomic and inter-fragment interactions favour the nonlinear arrangements; however, these terms are compensated by the atomic self-energies, which stabilise the linear structure.

  12. The effect of pressure on Cu-btc: framework compression vs. guest inclusion.

    PubMed

    Graham, Alexander J; Tan, Jin-Chong; Allan, David R; Moggach, Stephen A

    2012-02-01

    Here we present detailed structural data on the effect of high pressure on Cu-btc. Application of pressure causes solvent to be squeezed into the pores until a phase transition occurs, driven by the sudden compression and expansion of equatorial and axial Cu-O bonds. This journal is © The Royal Society of Chemistry 2012

  13. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei

    The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu- based catalysts are not practical for this chemistry due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Utilizing Pt/Cu single atom alloys (SAAs) we examine C-H activation in a number of systems including methyl groups, methane, and butane using a combination of simulations, surface science, and catalysismore » studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke resistant C-H activation chemistry with the added economic benefit that the precious metal is diluted at the atomic limit.« less

  14. Si-H induced synthesis of Si/Cu2O nanowire arrays for photoelectrochemical water splitting

    NASA Astrophysics Data System (ADS)

    Zhang, Shaoyang; She, Guangwei; Li, Shengyang; Mu, Lixuan; Shi, Wensheng

    2018-01-01

    We report a facile and low-cost method to synthesize Si/Cu2O heterojunction nanowire arrays, without SiOx, at the Si/Cu2O interface. The reductive Si-H bonds on the surface of Si nanowires plays a key role in situ by reducing Cu(II) ions to Cu2O nanocubes and avoiding the SiOx interface layer. Different pH values would vary the electrochemical potential of reactions and as a result, different products would be formed. Utilized as a photoanode for water splitting, Si/Cu2O nanowire arrays exhibit good photoelectrochemical performance.

  15. Photocatalytic property and structural stability of CuAl-based layered double hydroxides

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lv, Ming; Liu, Haiqiang, E-mail: Liuhaiqiang1980@126.com

    2015-07-15

    Three types of CuMAl layered double hydroxides (LDHs, M=Mg, Zn, Ni) were successfully synthesized by coprecipitation. Powder X-ray diffraction (XRD), inductively coupled plasma atomic emission spectrometry (ICP-AES) and UV–Vis diffuse reflectance spectrum (UV–vis) were used to confirm the formation of as-synthesized solids with good crystal structure. The photocatalytic activity of those LDH materials for CO{sub 2} reduction under visible light was investigated. The experimental results show that CuNiAl-LDHs with narrowest band gap and largest surface areas behave highest efficiency for methanol generation under visible light compared with CuMgAl-LDHs and CuZnAl-LDHs. The CuNiAL-LDH showed high yield for methanol production i.e. 0.210more » mmol/g h, which was high efficient. In addition, the influence of the different M{sup 2+} on the structures and stability of the CuMAl-LDHs was also investigated by analyzing the geometric parameters, electronic arrangement, charge populations, hydrogen-bonding, and binding energies by density functional theory (DFT) analysis. The theoretical calculation results show that the chemical stability of LDH materials followed the order of CuMgAl-LDHs>CuZnAl-LDHs>CuNiAl-LDHs, which is just opposite with the photocatalytic activity and band gaps of three materials. - Graphical abstract: The host–guest calculation models and XRD patterns of CuMAl-LDHs: CuMgAl-LDHs (a), CuZnAl-LDHs (b) and CuNiAl-LDHs (c). - Highlights: • Three types of CuMAl layered double hydroxides (LDHs, M=Mg, Zn, Ni) has been synthesized. • CuMgNi shows narrower band gap and more excellent textural properties than other LDHs. • The band gap: CuMgAl« less

  16. Effect of Cu concentration on morphology of Sn-Ag-Cu solders by mechanical alloying

    NASA Astrophysics Data System (ADS)

    Kao, Szu-Tsung; Duh, Jenq-Gong

    2004-12-01

    The mechanical alloying (MA) process is considered an alternative approach to produce solder materials. In this study, the effect of Cu concentration in the ternary Sn-3.5Ag-xCu (x=0.2, 0.7, and 1) solder by MA was investigated. The (Cu,Sn) solid solution was precipitated as the Cu6Sn5 intermetallic compound (IMC), which was distributed nonuniformly through the microstructure. The Cu6Sn5 IMC, which was present in the SnAgCu solder with high Cu composition, causes the as-milled MA particle to fracture to a smaller size. Appreciable distinction on morphology of as-milled MA powders with different Cu content was revealed. When the Cu concentration was low (x=0.2), MA particle aggregated to a spherical ingot with large particle size. For higher Cu concentration (x=0.7 and x=1), the MA particle turned to flakes with smaller particle size. The distinction of the milling mechanism of Sn-3.5Ag-xCu (x=0.2, 0.7, and 1) solder by the MA process was discussed. An effective approach was developed to reduce the particle size of the SnAgCu solder from 1 mm down to 10-100 µm by doping the Cu6Sn5 nanoparticle during the MA process. In addition, the differential scanning calorimetry (DSC) results also ensure the compatibility to apply the solder material for the reflow process.

  17. Reliable four-point flexion test and model for die-to-wafer direct bonding

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tabata, T., E-mail: toshiyuki.tabata@cea.fr; Sanchez, L.; Fournel, F.

    2015-07-07

    For many years, wafer-to-wafer (W2W) direct bonding has been very developed particularly in terms of bonding energy measurement and bonding mechanism comprehension. Nowadays, die-to-wafer (D2W) direct bonding has gained significant attention, for instance, in photonics and microelectro-mechanics, which supposes controlled and reliable fabrication processes. So, whatever the stuck materials may be, it is not obvious whether bonded D2W structures have the same bonding strength as bonded W2W ones, because of possible edge effects of dies. For that reason, it has been strongly required to develop a bonding energy measurement technique which is suitable for D2W structures. In this paper, bothmore » D2W- and W2W-type standard SiO{sub 2}-to-SiO{sub 2} direct bonding samples are fabricated from the same full-wafer bonding. Modifications of the four-point flexion test (4PT) technique and applications for measuring D2W direct bonding energies are reported. Thus, the comparison between the modified 4PT and the double-cantilever beam techniques is drawn, also considering possible impacts of the conditions of measures such as the water stress corrosion at the debonding interface and the friction error at the loading contact points. Finally, reliability of a modified technique and a new model established for measuring D2W direct bonding energies is demonstrated.« less

  18. Copper interstitial recombination centers in Cu 3 N

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam

    We present a comprehensive study of the earth-abundant semiconductor Cu 3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies V Cu have shallow defect levels while copper interstitials Cu i behave as deep potential wells in the conduction band which mediate Shockley-Read-Hall recombination. The existence of Cu i defects has been experimentally verified using photothermal deflection spectroscopy. A Cu 3N/ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. Finally, the absencemore » of photocurrent can be explained by a large concentration of Cu i recombination centers capturing electrons in p-type Cu 3N.« less

  19. Copper interstitial recombination centers in Cu 3 N

    DOE PAGES

    Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam; ...

    2018-06-04

    We present a comprehensive study of the earth-abundant semiconductor Cu 3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies V Cu have shallow defect levels while copper interstitials Cu i behave as deep potential wells in the conduction band which mediate Shockley-Read-Hall recombination. The existence of Cu i defects has been experimentally verified using photothermal deflection spectroscopy. A Cu 3N/ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. Finally, the absencemore » of photocurrent can be explained by a large concentration of Cu i recombination centers capturing electrons in p-type Cu 3N.« less

  20. Soil solution dynamics of Cu and Zn in a Cu- and Zn-polluted soil as influenced by gamma-irradiation and Cu-Zn interaction.

    PubMed

    Luo, Y M; Yan, W D; Christie, P

    2001-01-01

    A pot experiment was conducted to study soil solution dynamics of Cu and Zn in a Cu/Zn-polluted soil as influenced by gamma-irradiation and Cu-Zn interaction. A slightly acid sandy loam was amended with Cu and Zn (as nitrates) either singly or in combination (100 mg Cu and 150 mg Zn kg(-1) soil) and was then gamma-irradiated (10 kGy). Unamended and unirradiated controls were included, and spring barley (Hordeum vulgare L. cv. Forrester) was grown for 50 days. Soil solution samples obtained using soil moisture samplers immediately before transplantation and every ten days thereafter were used directly for determination of Cu, Zn, pH and absorbance at 360 nm (A360). Cu and Zn concentrations in the solution of metal-polluted soil changed with time and were affected by gamma-irradiation and metal interaction. gamma-Irradiation raised soil solution Cu substantially but generally decreased soil solution Zn. These trends were consistent with increased dissolved organic matter (A360) and solution pH after gamma-irradiation. Combined addition of Cu and Zn usually gave higher soil solution concentrations of Cu or Zn compared with single addition of Cu or Zn in gamma-irradiated and non-irradiated soils, indicating an interaction between Cu and Zn. Cu would have been organically complexed and consequently maintained a relatively high concentration in the soil solution under higher pH conditions. Zn tends to occur mainly as free ion forms in the soil solution and is therefore sensitive to changes in pH. The extent to which gamma-irradiation and metal interaction affected solubility and bioavailability of Cu and Zn was a function of time during plant growth. Studies on soil solution metal dynamics provide very useful information for understanding metal mobility and bioavailability.

  1. The mechanism of transition-metal (Cu or Pd)-catalyzed synthesis of benzimidazoles from amidines: theoretical investigation.

    PubMed

    Li, Juan; Gu, Honghong; Wu, Caihong; Du, Lijuan

    2014-11-28

    In this study, the Cu(OAc)2- and [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines were theoretically investigated using density functional theory calculations. For the Cu-catalyzed system, our calculations supported a four-step-pathway involving C-H activation of an arene with Cu(II) via concerted metalation-deprotonation (CMD), followed by oxidation of the Cu(II) intermediate and deprotonation of the imino group by Cu(III), and finally reductive elimination from Cu(III). In our calculations, the barriers for the CMD step and the oxidation step are the same. The results are different from the ones reported by Fu et al. in which the whole reaction mechanism includes three steps and the CMD step is rate determining. On the basis of the calculation results for the [PdCl2(PhCN)2]-catalyzed system, C-H bond breaking by CMD occurs first, followed by the rate-determining C-N bond formation and N-H deprotonation. Pd(III) species is not involved in the [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines.

  2. The growth of intermetallic compounds at Sn-Ag-Cu solder/Cu and Sn-Ag-Cu solder/Ni interfaces and the associated evolution of the solder microstructure

    NASA Astrophysics Data System (ADS)

    Zribi, A.; Clark, A.; Zavalij, L.; Borgesen, P.; Cotts, E. J.

    2001-09-01

    The evolution of intermetallics at and near SnAgCu/Cu and SnAgCu/Ni interfaces was examined, and compared to the behavior, near PbSn/metal and Sn/metal interfaces. Two different solder compositions were considered, Sn93.6Ag4.7Cu1.7 and Sn95.5Ag3.5Cu1.0 (Sn91.8Ag5.1 Cu3.1 and Sn94.35Ag3.8Cu1.85 in atomic percent). In both cases, phase formation and growth at interfaces with Cu were very similar to those commonly observed for eutectic SnPb solder. However, the evolution of intermetallics at SnAgCu/Ni interfaces proved much more complex. The presence of the Cu in the solder dramatically altered the phase selectivity at the solder/Ni interface and affected the growth kinetics of intermetallics. As long as sufficient Cu was available, it would combine with Ni and Sn to form (Cu,Ni)6)Sn5 which grew instead of the Ni3Sn4 usually observed in PbSn/Ni and Sn/Ni diffusion couples. This growing phase would, however, eventually consume essentially all of the available Cu in the solder. Because the mechanical properties of Sn-Ag-Cu alloys, depend upon the Cu content, this consumption can be expected to alter the mechanical properties of these Pb-free solderjoints. After depletion of the Cu from the solder, further annealing then gradually transformed the (Cu,Ni)6Sn5 phase into a (Ni,Cu)3Sn4 phase.

  3. The effect of Mg-doping and Cu nonstoichiometry on the photoelectrochemical response of CuFeO 2

    DOE PAGES

    Wuttig, Anna; Krizan, Jason W.; Gu, Jing; ...

    2016-11-14

    Here, we report the tuning of CuFeO 2 photoelectrodes by Mg doping and Cu deficiency to demonstrate the effects of carrier concentration on the photoresponse. Carrier type and concentration were quantitatively assessed using the Hall effect on pure, Mg-incorporated, and Cu-deficient pellets (CuFe 1–xMg xO 2 and Cu 1–yFeO 2, x = 0, 0.0005, 0.005, 0.02, and y = 0.005, 0.02) over the range of thermodynamic stability achievable using solid-state synthesis. The same samples were used in a photoelectrochemical cell to measure their photoresponse. We find that the material with the lowest p-type carrier concentration and the highest carrier mobilitymore » shows the largest photoresponse. Furthermore, we show that increasing the p-type carrier concentration and thus the conductivity to high levels is limited by the delafossite defect chemistry, which changes the majority carrier type from p-type to n-type near the Mg solubility limit (x = 0.05) and at high Cu defect concentrations.« less

  4. Structural, electronic, and optical properties of representative Cu-flavonoid complexes.

    PubMed

    Lekka, Ch E; Ren, Jun; Meng, Sheng; Kaxiras, Efthimios

    2009-05-07

    We present density functional theory (DFT) results on the structural, electronic, and optical properties of Cu-flavonoid complexes for molar ratios 1:1, 1:2, and 1:3. We find that the preferred chelating site is close to the 4-oxo group and in particular the 3-4 site followed by the 3'-4' dihydroxy group in ring B. For the Cu-quercetin complexes, the large bathochromic shift of the first absorbance band upon complexation, which is in good agreement with experimental UV-vis spectra, results from the reduction of the electronic energy gap. The HOMO states for these complexes are characterized by pi-bonding between the Cu d orbitals and the C, O p orbitals except for the case of 1:1 complex (spin minority), which corresponds to sigma-type bonds. The LUMO states are attributed to the contribution of Cu p(z) orbitals. Consequently, the main features of the first optical absorption maxima are essentially due to pi --> pi transitions, while the 1:1 complex exhibits also sigma --> pi transitions. Our optical absorption calculations based on time-dependent DFT demonstrate that the 1:1 complex is responsible for the spectroscopic features at pH 5.5, whereas the 1:2 complex is mainly the one responsible for the characteristic spectra at pH 7.4. These theoretical predictions explain in detail the behavior of the optical absorption for the Cu-flavonoid complexes observed in experiments and are thus useful in elucidating the complexation mechanism and antioxidant activity of flavonoids.

  5. Corrosion characteristics of alpha-Ti and Ti2Cu composing Ti-Cu alloys.

    PubMed

    Takada, Yukyo; Okuno, Osamu

    2005-12-01

    A series of binary Ti-Cu alloys containing 5-20 mass% Cu was prepared, and the corrosion behavior of alpha-Ti and Ti2Cu composing the Ti-Cu alloys were examined based on the anodic polarization curves and released ions in 0.9% NaCl and 1% lactic acid solutions. In both solutions, the Ti-Cu alloys showed the same anodic polarization curves as titanium in the condition below 1.4 V. However, precipitation of Ti2Cu contributed to a small increase in current densitiy in the transpassive region beyond 1.4 V. The amount of Cu ions released from Ti2Cu was 0.260 and 1.003 (microg/cm2/7 days) in 0.9% NaCl and 1% lactic acid solutions respectively. Although these values were larger than those from alpha-Ti (0.0379 +/- 0.0041 and 0.0962 +/- 0.0327 (microg/cm2/7days) in NaCl and lactic acid solutions respectively), they were not greater than those from type 4 gold alloy under the same conditions.

  6. Development of interface-dominant bulk Cu/V nanolamellar composites by cross accumulative roll bonding

    PubMed Central

    Zeng, L. F.; Gao, R.; Xie, Z. M.; Miao, S.; Fang, Q. F.; Wang, X. P.; Zhang, T.; Liu, C. S.

    2017-01-01

    Traditional nanostructured metals are inherently comprised of a high density of high-energy interfaces that make this class of materials not stable in extreme conditions. Therefore, high performance bulk nanostructured metals containing stable interfaces are highly desirable for extreme environments applications. Here, we reported an attractive bulk Cu/V nanolamellar composite that was successfully developed by integrating interface engineering and severe plastic deformation techniques. The layered morphology and ordered Cu/V interfaces remained stable with respect to continued rolling (total strain exceeding 12). Most importantly, for layer thickness of 25 nm, this bulk Cu/V nanocomposite simultaneously achieves high strength (hardness of 3.68 GPa) and outstanding thermal stability (up to 700 °C), which are quite difficult to realize simultaneously in traditional nanostructured materials. Such extraordinary property in our Cu/V nanocomposite is achieved via an extreme rolling process that creates extremely high density of stable Cu/V heterophase interfaces and low density of unstable grain boundaries. In addition, high temperature annealing result illustrates that Rayleigh instability is the dominant mechanism driving the onset of thermal instability after exposure to 800 °C. PMID:28094346

  7. L10 FePtCu bit patterned media

    NASA Astrophysics Data System (ADS)

    Brombacher, C.; Grobis, M.; Lee, J.; Fidler, J.; Eriksson, T.; Werner, T.; Hellwig, O.; Albrecht, M.

    2012-01-01

    Chemically ordered 5 nm-thick L10 FePtCu films with strong perpendicular magnetic anisotropy were post-patterned by nanoimprint lithography into a dot array over a 3 mm-wide circumferential band on a 3 inch Si wafer. The dots with a diameter of 30 nm and a center-to-center pitch of 60 nm appear as single domain and reveal an enhanced switching field as compared to the continuous film. We demonstrate successful recording on a single track using shingled writing with a conventional hard disk drive write/read head.

  8. Elastocaloric effect in CuAlZn and CuAlMn shape memory alloys under compression

    PubMed Central

    Qian, Suxin; Wang, Yi; Pillsbury, Thomas E.; Hada, Yoshiharu; Yamaguchi, Yuki; Fujimoto, Kenjiro; Hwang, Yunho; Radermacher, Reinhard; Cui, Jun; Yuki, Yoji; Toyotake, Koutaro; Takeuchi, Ichiro

    2016-01-01

    This paper reports the elastocaloric effect of two Cu-based shape memory alloys: Cu68Al16Zn16 (CuAlZn) and Cu73Al15Mn12 (CuAlMn), under compression at ambient temperature. The compression tests were conducted at two different rates to approach isothermal and adiabatic conditions. Upon unloading at a strain rate of 0.1 s−1 (adiabatic condition) from 4% strain, the highest adiabatic temperature changes (ΔTad) of 4.0 K for CuAlZn and 3.9 K for CuAlMn were obtained. The maximum stress and hysteresis at each strain were compared. The stress at the maximum recoverable strain of 4.0% for CuAlMn was 120 MPa, which is 70% smaller than that of CuAlZn. A smaller hysteresis for the CuAlMn alloy was also obtained, about 70% less compared with the CuAlZn alloy. The latent heat, determined by differential scanning calorimetry, was 4.3 J g−1 for the CuAlZn alloy and 5.0 J g−1 for the CuAlMn alloy. Potential coefficients of performance (COPmat) for these two alloys were calculated based on their physical properties of measured latent heat and hysteresis, and a COPmat of approximately 13.3 for CuAlMn was obtained. This article is part of the themed issue ‘Taking the temperature of phase transitions in cool materials’. PMID:27402936

  9. Microwave-assisted template-free synthesis of butterfly-like CuO through Cu2Cl(OH)3 precursor and the electrochemical sensing property

    NASA Astrophysics Data System (ADS)

    Xie, Hanjie; Zhu, Lianjie; Zheng, Wenjun; Zhang, Jing; Gao, Fubo; Wang, Yan

    2016-11-01

    An energy-efficient and environmentally friendly microwave-assisted method was adopted for synthesis of butterfly-like CuO assembled by nanosheets through a Cu2Cl(OH)3 precursor, using no template. Formation mechanism of the butterfly-like CuO was explored and discussed systematically for the first time on the basis of both experimental results and crystal structure transformations in atomic level. The electrochemical sensing properties of the butterfly-like CuO modified electrode to ascorbic acid (AA) were studied for the first time. The results reveal that Cu(OH)2 nanowires were formed once the Cu2+ ions, located in between two CuO4 parallelogram chains of a Cu2Cl(OH)3 precursor, dissolve into the solution as Cu(OH)42- complex ions after ion exchange reactions and simultaneous assemble along a axis. Upon microwave irradiation, the adjacent CuO4 parallelogram chains of the Cu(OH)2 nanowires dehydrate and assemble along c axis, forming CuO nanosheets with (002) as the main exposed facet, which were further assembled to butterfly-like CuO under the action of microwave field, suggesting that microwave field functions like a 'directing agent'. The butterfly-like CuO modified electrode shows good electrochemical sensing properties to AA with a low detecting limit, short response time and wide linear response range.

  10. A Stable Plasmonic Cu@Cu2 O/ZnO Heterojunction for Enhanced Photocatalytic Hydrogen Generation.

    PubMed

    Lou, Yongbing; Zhang, Yake; Cheng, Lin; Chen, Jinxi; Zhao, Yixin

    2018-05-09

    The localized surface plasmon resonance (LSPR) effect has been widely utilized in photocatalysis, but most reported LSPR materials are based on noble metals of gold or silver with high chemical stability. Plasmonic copper nanoparticles that exhibit an LSPR absorbance at 600 nm are promising for many applications, such as photocatalysis. Unfortunately, plasmonic copper nanoparticles are affected by serious surface oxidation in air. Herein, a novel lollipop-shaped Cu@Cu 2 O/ZnO heterojunction nanostructure was designed, for the first time, to stabilize the plasmonic Cu core by decorating Cu@Cu 2 O core-shell structures with ZnO nanorods. This Cu@Cu 2 O/ZnO nanostructure exhibited significantly enhanced stability than that of regular Cu@Cu 2 O, which accounted for the remarkably enhanced photocatalytic H 2 evolution rate through water splitting, relative to pristine ZnO nanorods, over an extended wavelength range due to the plasmonic Cu core. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Phonon Dispersion Measurements of YBa 2Cu 3O 6.15 and YBa 2Cu 3O 6.95 by Time-of-Flight Neutron Spectroscopy

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chung, J.-H.; Egami, T.; McQueeny, R. J.

    We measured the phonon dispersions of YBa{sub 2}Cu{sub 3}O{sub 6.15} and YBa{sub 2}Cu{sub 3}O{sub 6.95} by time-of-flight inelastic neutron scattering. The in-plane bond-stretching modes in the metallic phase showed a distinct a-b plane anisotropy beyond what is expected for structural origin. Such anisotropy in the longitudinal optical modes, which is absent in the TO, suggests strong in-plane anisotropy in the underlying electronic structure. Apical oxygen bond-stretching modes showed a large frequency change between the insulating and the metallic phases. This large softening also is beyond structural origin, and suggests the effect of local electronic environment.

  12. Atomistic Modeling of Surface and Bulk Properties of Cu, Pd and the Cu-Pd System

    NASA Technical Reports Server (NTRS)

    Bozzolo, Guillermo; Garces, Jorge E.; Noebe, Ronald D.; Abel, Phillip; Mosca, Hugo O.; Gray, Hugh R. (Technical Monitor)

    2002-01-01

    The BFS (Bozzolo-Ferrante-Smith) method for alloys is applied to the study of the Cu-Pd system. A variety of issues are analyzed and discussed, including the properties of pure Cu or Pd crystals (surface energies, surface relaxations), Pd/Cu and Cu/Pd surface alloys, segregation of Pd (or Cu) in Cu (or Pd), concentration dependence of the lattice parameter of the high temperature fcc CuPd solid solution, the formation and properties of low temperature ordered phases, and order-disorder transition temperatures. Emphasis is made on the ability of the method to describe these properties on the basis of a minimum set of BFS universal parameters that uniquely characterize the Cu-Pd system.

  13. Relationship between morphologies and orientations of Cu{sub 6}Sn{sub 5} grains in Sn3.0Ag0.5Cu solder joints on different Cu pads

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tian, Yanhong, E-mail: tianyh@hit.edu.cn; Zhang, Rui; Hang, Chunjin

    2014-02-15

    The morphologies and orientations of Cu{sub 6}Sn{sub 5} intermetallic compounds in the Sn3.0Ag0.5Cu solder joints both on polycrystalline and single crystal Cu pads under different peak reflow temperatures and times above liquids were investigated. The relationship between Cu{sub 6}Sn{sub 5} grain orientations and morphologies was clarified. At the interface of Sn3.0Ag0.5Cu/polycrystalline Cu pad, scalloped Cu{sub 6}Sn{sub 5} intermetallic compounds formed at 250 °C and roof shape Cu{sub 6}Sn{sub 5} formed at 300 °C. Both scalloped Cu{sub 6}Sn{sub 5} and roof shape Cu{sub 6}Sn{sub 5} had a preferred orientation of (0001) plane being parallel to polycrystalline Cu pad surface. Besides, themore » percentage of large angle grain boundaries increased as the peak reflow temperature rose. At the interface of Sn3.0Ag0.5Cu/(111) single crystal Cu pad, the Cu{sub 6}Sn{sub 5} intermetallic compounds were mainly scallop-type at 250 °C and were prism type at 300 °C. The prismatic Cu{sub 6}Sn{sub 5} grains grew along the three preferred directions with the inter-angles of 60° on (111) single crystal Cu pad while along two perpendicular directions on (100) single crystal Cu pad. The orientation relationship between Cu{sub 6}Sn{sub 5} grains and the single crystal Cu pads was investigated by electron backscatter diffraction technology. In addition, two types of hollowed Cu{sub 6}Sn{sub 5} intermetallic compounds were found inside the joints of polycrystalline Cu pads. The long hexagonal Cu{sub 6}Sn{sub 5} strips were observed in the joints reflowing at 250 °C while the hollowed Cu{sub 6}Sn{sub 5} strips with the ‘▪’ shape cross-sections appeared at 300 °C, which was attributed to the different grain growth rates of different Cu{sub 6}Sn{sub 5} crystal faces. - Highlights: • The orientation of interfacial Cu{sub 6}Sn{sub 5} grains was obtained by EBSD technology. • Two types of hollowed Cu{sub 6}Sn{sub 5} strips were found at different temperatures. • The

  14. Growth kinetics of Cu6Sn5 intermetallic compound at liquid-solid interfaces in Cu/Sn/Cu interconnects under temperature gradient

    PubMed Central

    Zhao, N.; Zhong, Y.; Huang, M.L.; Ma, H.T.; Dong, W.

    2015-01-01

    The growth behavior of intermetallic compounds (IMCs) at the liquid-solid interfaces in Cu/Sn/Cu interconnects during reflow at 250 °C and 280 °C on a hot plate was investigated. Being different from the symmetrical growth during isothermal aging, the interfacial IMCs showed clearly asymmetrical growth during reflow, i.e., the growth of Cu6Sn5 IMC at the cold end was significantly enhanced while that of Cu3Sn IMC was hindered especially at the hot end. It was found that the temperature gradient had caused the mass migration of Cu atoms from the hot end toward the cold end, resulting in sufficient Cu atomic flux for interfacial reaction at the cold end while inadequate Cu atomic flux at the hot end. The growth mechanism was considered as reaction/thermomigration-controlled at the cold end and grain boundary diffusion/thermomigration-controlled at the hot end. A growth model was established to explain the growth kinetics of the Cu6Sn5 IMC at both cold and hot ends. The molar heat of transport of Cu atoms in molten Sn was calculated as + 11.12 kJ/mol at 250 °C and + 14.65 kJ/mol at 280 °C. The corresponding driving force of thermomigration in molten Sn was estimated as 4.82 × 10−19 N and 6.80 × 10−19 N. PMID:26311323

  15. Controlled Synthesis of Nanomaterials at the Undergraduate Laboratory: Cu(OH)[subscript 2] and CuO Nanowires

    ERIC Educational Resources Information Center

    da Silva, Anderson G. M.; Rodrigues, Thenner S.; Parussulo, Andre´ L. A.; Candido, Eduardo G.; Geonmonond, Rafael S.; Brito, Hermi F.; Toma, Henrique E.; Camargo, Pedro H. C.

    2017-01-01

    Undergraduate-level laboratory experiments that involve the synthesis of nanomaterials with well-defined/controlled shapes are very attractive under the umbrella of nanotechnology education. Herein we describe a low-cost and facile experiment for the synthesis of Cu(OH)[subscript 2] and CuO nanowires comprising three main parts: (i) synthesis of…

  16. 64Cu-ATSM Reflects pO2 Levels in Human Head and Neck Cancer Xenografts but Not in Colorectal Cancer Xenografts: Comparison with 64CuCl2.

    PubMed

    Li, Fan; Jørgensen, Jesper T; Forman, Julie; Hansen, Anders E; Kjaer, Andreas

    2016-03-01

    The hypoxia PET tracer (64)Cu-diacetyl-bis(N(4)-methylthiosemicarbazonate) ((64)Cu-ATSM) has shown promising results in clinical studies. However, concerns have been raised with regard to the possible effect of copper metabolism and free copper on tumor uptake and thereby the robustness of (64)Cu-ATSM as a hypoxia marker. In this study, accumulation and distribution of (64)Cu-ATSM and (64)CuCl2 in tumor tissue were compared with partial pressure of oxygen (pO2) probe measurements. One-hour dynamic PET scans were performed on nude mice bearing subcutaneous human head and neck tumors (FaDu) and human colorectal tumors (HT29) after administration of either (64)Cu-ATSM or (64)CuCl2. Subsequently, tracks were generated and track markers were positioned in tumors to allow for registration of their exact location on the high-resolution CT scan. After completion of the CT scan, pO2 probe measurements were performed along each track. PET and CT images were coregistered and ROIs drawn on the basis of the location of track markers and pO2 probe measurement depth. A linear mixed model for repeated measures was applied for the comparison of PET tracer uptake to corresponding pO2 values. Comparable uptake of (64)Cu-ATSM and (64)CuCl2 was found in the kidney, muscle, and liver of all animals, but (64)CuCl2 showed a higher uptake 10-60 min after injection in both tumor models. Significant differences were also found for both tumor-to-muscle and tumor-to-liver ratios. The intratumoral distribution of (64)Cu-ATSM, but not (64)CuCl2, showed a significant negative relationship with pO2 measurements in FaDu tumors. However, this relationship was not found in HT29 tumors. (64)Cu-ATSM and (64)CuCl2 displayed different uptake in tumors. In human head and neck xenografts, (64)Cu-ATSM but not (64)CuCl2 reflected pO2 measurements, indicating that (64)Cu-ATSM is a hypoxia-specific marker in this tumor type. However, data from colorectal cancer xenografts indicated that (64)Cu-ATSM may not be

  17. Sol-gel deposited Cu2O and CuO thin films for photocatalytic water splitting.

    PubMed

    Lim, Yee-Fun; Chua, Chin Sheng; Lee, Coryl Jing Jun; Chi, Dongzhi

    2014-12-21

    Cu2O and CuO are attractive photocatalytic materials for water splitting due to their earth abundance and low cost. In this paper, we report the deposition of Cu2O and CuO thin films by a sol-gel spin-coating process. Sol-gel deposition has distinctive advantages such as low-cost solution processing and uniform film formation over large areas with a precise stoichiometry and thickness control. Pure-phase Cu2O and CuO films were obtained by thermal annealing at 500 °C in nitrogen and ambient air, respectively. The films were successfully incorporated as photocathodes in a photoelectrochemical (PEC) cell, achieving photocurrents of -0.28 mA cm(-2) and -0.35 mA cm(-2) (for Cu2O and CuO, respectively) at 0.05 V vs. a reversible hydrogen electrode (RHE). The Cu2O photocurrent was enhanced to -0.47 mA cm(-2) upon incorporation of a thin layer of a NiOx co-catalyst. Preliminary stability studies indicate that CuO may be more stable than Cu2O as a photocathode for PEC water-splitting.

  18. Effect of Cu Salt Molarity on the Nanostructure of CuO Prolate Spheroid

    NASA Astrophysics Data System (ADS)

    Sabeeh, Sabah H.; Hussein, Hashim Abed; Judran, Hadia Kadhim

    Copper sulfate pentahydrate was used as a source of Cu ion with five different molarities (0.02, 0.05, 0.1, 0.15, 2 and 0.25M). XRD, FE-SEM and TEM techniques all showed that CuO samples have polycrystalline monoclinic structure. CuO prolate spheroid is assembled from nanoparticles as building units. It was demonstrated that the purity, morphology, size range of prolate spheroid and density of nano building units are significantly influenced by Cu precursor’s molarity. The pure phase of CuO prolate spheroid was produced via molarity of 0.2M with crystallite size of 15.1565nm while the particle size of building units ranges from 16nm to 21nm. The stability of CuO nanosuspension or nanofluid was evaluated by zeta potential analysis. The obtained properties of specific structure with large surface area of CuO prolate spheroid make it a promising candidate for wide range of potential applications as in nanofluids for cooling purposes.

  19. New evidence for Cu-decorated binary-oxides mediating bacterial inactivation/mineralization in aerobic media.

    PubMed

    Rtimi, S; Pulgarin, C; Bensimon, M; Kiwi, J

    2016-08-01

    Binary oxide semiconductors TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 (TiO2-ZrO2-Cu) uniform films were sputtered on polyester (PES). These films were irradiated under low intensity solar simulated light and led to bacterial inactivation in aerobic and anaerobic media as evaluated by CFU-plate counting. But bacterial mineralization was only induced by TiO2-ZrO2-Cu in aerobic media. The highly oxidative radicals generated on the films surface under light were identified by the use of appropriate scavengers. The hole generated on the TiO2-ZrO2 films is shown to be the main specie leading to bacterial inactivation. TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 films release Zr and Ti <1ppb and Cu 4.6ppb/cm(2) as determined by inductively coupled plasma mass spectrometry (ICP-MS) This level is far below the citotoxicity permitted level allowed for mammalian cells suggesting that bacterial disinfection proceeds through an oligodynamic effect. By Fourier transform attenuated infrared spectroscopy (ATR-FTIR) the systematic shift of the predominating νs(CH2) vibrational-rotational peak making up most of the bacterial cell-wall content in C was monitored. Based on this evidence a mechanism suggested leading to CH bond stretching followed by cell lysis and cell death. Bacterial inactivation cycling was observed on TiO2-ZrO2-Cu showing the stability of these films leading to bacterial inactivation. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Electrochemical, Structural and Magnetic Analysis of Electrodeposited CoCu/Cu Multilayers: Influence of Cu Layer Deposition Potential

    NASA Astrophysics Data System (ADS)

    Tekgül, Atakan; Kockar, Hakan; Kuru, Hilal; Alper, Mürsel; ÜnlÜ, C. Gökhan

    2018-03-01

    The electrochemical, structural and magnetic properties of CoCu/Cu multilayers electrodeposited at different cathode potentials were investigated from a single bath. The Cu layer deposition potentials were selected as - 0.3, V - 0.4 V, and - 0.5 V with respect to saturated calomel electrode (SCE) while the Co layer deposition potential was constant at - 1.5 V versus SCE. For the electrochemical analysis, the current-time transients were obtained. The amount of noble non-magnetic (Cu) metal materials decreased with the increase of deposition potentials due to anomalous codeposition. Further, current-time transient curves for the Co layer deposition and capacitance were calculated. In the structural analysis, the multilayers were found to be polycrystalline with both Co and Cu layers adopting the face-centered cubic structure. The (111) peak shifts towards higher angle with the increase of the deposition potentials. Also, the lattice parameters of the multilayers decrease from 0.3669 nm to 0.3610 nm with the increase of the deposition potentials from - 0.3 V to - 0.5 V, which corresponds to the bulk values of Cu and Co, respectively. The electrochemical and structural results demonstrate that the amount of Co atoms increased and the Cu atoms decreased in the layers with the increase of deposition potentials due to anomalous codeposition. For magnetic measurements, the saturation magnetizations, M_s obtained from the magnetic curves of the multilayers were obtained as 212 kA/m, 276 kA/m, and 366 kA/m with - 0.3 V, - 0.4 V, and - 0.5 V versus SCE, respectively. It is seen that the M_s values increased with the increase of the deposition potentials confirming the increase of the Co atoms and decrease of the Cu amount. The results of electrochemical and structural analysis show that the deposition potentials of non-magnetic layers plays important role on the amount of magnetic and non-magnetic materials in the layers and thus on the magnetic properties of the multilayers.

  1. Thermally promoted evolution of open-volume defects and Cu precipitates in the deformed FeCu alloys

    NASA Astrophysics Data System (ADS)

    Jin, Shuoxue; Cao, Xingzhong; Cheng, Guodong; Lian, Xiangyu; Zhu, Te; Zhang, Peng; Yu, Runsheng; Wang, Baoyi

    2018-04-01

    We have studied the effect of isothermal annealing on the evolution of the open-volume defect and the Cu precipitate in deformed Fe0.15Cu, Fe0.3Cu and Fe0.6Cu alloys. Using the coincidence Doppler broadening, positron annihilation lifetime and the S-W couples, the evolution of local electronic circumstance around the annihilation sites, open-volume defects and interaction between open-volume defects and Cu precipitates were measured as a function of the isothermal annealing temperatures. Cold rolling deformation induced an obvious increment in S parameters due to the formation of open-volume defects. Annealing not only resulted in gradual recovery of open-volume defects and Cu thermal precipitation, but also promoted the combination and interaction between defects and Cu precipitates. The interaction between open-volume defects and Cu precipitates was revealed clearly by the view point of S-W relationship. The S-W interaction for the different CumVn complexes was also calculated theoretically by MIKA-Doppler, which supports our experimental observations qualitatively. The results indicate that open-volume defects were formed first after cold rolling, followed by the Cu precipitation and recovery of open-volume defects, Cu precipitates recovered at the end. It is interesting that the trajectory of (S, W) points with increasing annealing temperature formed a similar closed "Parallelogram" shape. It is benefit for revealing the behavior of Cu thermal precipitation and their evolution in various Cu-bearing steels under thermal treatment. In addition, we also investigated the Cu content effect on the Cu precipitation in FeCu alloys, and the Cu precipitate phenomenon was enhanced in higher Cu content alloys.

  2. Versatile Three-Dimensional Porous Cu@Cu2 O Aerogel Networks as Electrocatalysts and Mimicking Peroxidases.

    PubMed

    Ling, Pinghua; Zhang, Qiang; Cao, Tingting; Gao, Feng

    2018-06-04

    A facile strategy is presented to form 3D porous Cu@Cu 2 O aerogel networks by self-assembling Cu@Cu 2 O nanoparticles with the diameters of ca. 40 nm for constructing catalytic interfaces. Unexpectedly, the prepared Cu@Cu 2 O aerogel networks display excellent electrocatalytic activity to glucose oxidation at a low onset potential of ca. 0.25 V. Moreover, the Cu@Cu 2 O aerogels also can act as mimicking-enzymes including horseradish peroxidase and NADH peroxidase, and show obvious enzymatic catalytic activities to the oxidation of dopamine (DA), o-phenyldiamine (OPD), 3,3,5,5-tetramethylbenzidine (TMB), and dihydronicotinamide adenine dinucleotide (NADH) in the presence of H 2 O 2 . These 3D Cu@Cu 2 O aerogel networks are a new class of porous catalytic materials as mimic peroxidases and electrocatalysts and offer a novel platform to construct catalytic interfaces for promising applications in electrochemical sensors and artificial enzymatic catalytic systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Abundant defects and defect clusters in kesterite Cu2ZnSnS4 and Cu2ZnSnSe4

    NASA Astrophysics Data System (ADS)

    Chen, Shiyou; Wang, Lin-Wang; Walsh, Aron; Gong, Xin-Gao; Wei, Su-Huai

    2013-03-01

    Cu2ZnSnS4 and Cu2ZnSnSe4 are drawing intensive attention as the light-absorber materials in thin-film solar cells. A large variety of intrinsic defects can be formed in these quaternary semiconductors, which have important influence on their optical and electrical properties, and hence their photovoltaic performance. We will present our first-principles calculation study on a series of intrinsic defects and defect clusters in Cu2ZnSnS4 and Cu2ZnSnSe4, and discuss: (i) strong phase-competition between the kesterites and the coexisting secondary compounds; (ii) the dominant CuZn antisites and Cu vacancies which determine the intrinsic p-type conductivity, and their dependence on the elemental ratios; (iii) the high population of charge-compensated defect clusters (like VCu + ZnCu and 2CuZn + SnZn) and their contribution to non-stoichiometry ; (iv) the deep-level defects which act as recombination centers. Based on the calculation, we will explain the experimental observation that Cu poor and Zn rich conditions give the highest solar cell efficiency, as well as suggesting an efficiency limitation in Cu2ZnSn(S,Se)4 cells with high S composition. Supported by NSF of China, JCAP: a U.S. DOE Energy Innovation Hub, Royal Society of U.K. and EPSRC, and U.S. DOE.

  4. Chemical reactions and morphological stability at the Cu/Al2O3 interface.

    PubMed

    Scheu, C; Klein, S; Tomsia, A P; Rühle, M

    2002-10-01

    The microstructures of diffusion-bonded Cu/(0001)Al2O3 bicrystals annealed at 1000 degrees C at oxygen partial pressures of 0.02 or 32 Pa have been studied with various microscopy techniques ranging from optical microscopy to high-resolution transmission electron microscopy. The studies revealed that for both oxygen partial pressures a 20-35 nm thick interfacial CuAlO2 layer formed, which crystallises in the rhombohedral structure. However, the CuAlO2 layer is not continuous, but interrupted by many pores. In the samples annealed in the higher oxygen partial pressure an additional reaction phase with a needle-like structure was observed. The needles are several millimetres long, approximately 10 microm wide and approximately 1 microm thick. They consist of CuAlO2 with alternating rhombohedral and hexagonal structures. Solid-state contact angle measurements were performed to derive values for the work of adhesion. The results show that the adhesion is twice as good for the annealed specimen compared to the as-bonded sample.

  5. Cu/Cu2O nanocomposite films as a p-type modified layer for efficient perovskite solar cells.

    PubMed

    Chen, You-Jyun; Li, Ming-Hsien; Huang, Jung-Chun-Andrew; Chen, Peter

    2018-05-16

    Cu/Cu 2 O films grown by ion beam sputtering were used as p-type modified layers to improve the efficiency and stability of perovskite solar cells (PSCs) with an n-i-p heterojunction structure. The ratio of Cu to Cu 2 O in the films can be tuned by the oxygen flow ratio (O 2 /(O 2  + Ar)) during the sputtering of copper. Auger electron spectroscopy was performed to determine the elemental composition and chemical state of Cu in the films. Ultraviolet photoelectron spectroscopy and photoluminescence spectroscopy revealed that the valence band maximum of the p-type Cu/Cu 2 O matches well with the perovskite. The Cu/Cu 2 O film not only acts as a p-type modified layer but also plays the role of an electron blocking buffer layer. By introducing the p-type Cu/Cu 2 O films between the low-mobility hole transport material, spiro-OMeTAD, and the Ag electrode in the PSCs, the device durability and power conversion efficiency (PCE) were effectively improved as compared to the reference devices without the Cu/Cu 2 O interlayer. The enhanced PCE is mainly attributed to the high hole mobility of the p-type Cu/Cu 2 O film. Additionally, the Cu/Cu 2 O film serves as a protective layer against the penetration of humidity and Ag into the perovskite active layer.

  6. Graphene-like Networks in the lattice of Ag, Cu and Al metals

    NASA Astrophysics Data System (ADS)

    Salamanca-Riba, Lourdes; Ge, Xiaoxiao; Isaacs, Romaine; Jaim, Hm Iftekar; Wuttig, Manfred; Rashkeev, Sergey; Kuklja, Maija; Hu, Lianbing; Covetics Team Team

    Graphene-like networks form in the lattice of metals such as silver, copper and aluminum via an electrocharging assisted process. In this process a high current of >80A is applied to the liquid metal containing particles of activated carbon. The resulting material is called M covetic (M =Al, Ag Cu). We have previously reported that this process gives rise to carbon nanostructures with sp2 bonding embedded in the lattice of the metal. The carbon bonds to the metal as evidenced by Raman scattering and first principles simulation of the phonon density of states. With this process we have observed that graphene nanoribbons form along preferential crystalline directions and form 3D epitaxial structures with Al and Ag hosts. Bulk Cu covetic was used to deposit films by e-beam deposition and PLD. The PLD films contain higher C content and show higher transmittance (~90%) and resistance to oxidation than pure copper films of the same thickness. We compare the electrical and mechanical properties of covetics containing C in the 0 to 10 wt % and the transmittance of Cu covetic films compared to pure Cu films of the same thickness. Supported by ONR Grant N000141410042

  7. Kinetics of Isothermal Reactive Diffusion Between Solid Cu and Liquid Sn

    NASA Astrophysics Data System (ADS)

    O, M.; Suzuki, T.; Kajihara, M.

    2018-01-01

    The Cu/Sn system is one of the most fundamental and important metallic systems for solder joints in electric devices. To realize reliable solder joints, information on reactive diffusion at the solder joint is very important. In the present study, we experimentally investigated the kinetics of the reactive diffusion between solid Cu and liquid Sn using semi-infinite Cu/Sn diffusion couples prepared by an isothermal bonding technique. Isothermal annealing of the diffusion couple was conducted in the temperature range of 533-603 K for various times up to 172.8 ks (48 h). Using annealing, an intermetallic layer composed of Cu6Sn5 with scallop morphology and Cu3Sn with rather uniform thickness is formed at the original Cu/Sn interface in the diffusion couple. The growth of the Cu6Sn5 scallop occurs much more quickly than that of the Cu3Sn layer and thus predominates in the overall growth of the intermetallic layer. This tendency becomes more remarkable at lower annealing temperatures. The total thickness of the intermetallic layer is proportional to a power function of the annealing time, and the exponent of the power function is close to unity at all the annealing temperatures. This means that volume diffusion controls the intermetallic growth and the morphology of the Cu6Sn5/Sn interface influences the rate-controlling process. Adopting a mean value of 0.99 for the exponent, we obtain a value of 26 kJ/mol for the activation enthalpy of the intermetallic growth.

  8. Based on Cu as framework constructed nanoporous CuO/Cu composites by a dealloy method for sodium-ion battery anode

    NASA Astrophysics Data System (ADS)

    Zheng, Tian; Li, Guangda; Li, Deming; Meng, Xiangeng

    2018-05-01

    Nanoporous CuO/Cu composites with a continuous channel structure were fabricated through a corroding Cu-Al alloy process. The width of the continuous channels was about 20 50 nm. Nanoporous structure could effectively sustain the volume expansion during the Na+ insertion/extraction process and shorten the Na+ diffusion length as well, which thus helps improve the Na+ storage performance. Moreover, the nanoporous structure can improve the contact area between the electrolyte and the electrode, leading to an increment in the number of Na+ insertion/extraction sites. When used as the anode for sodium-ion batteries, the CuO/Cu exhibited an initial capacity of 580 mAh g-1, and the capacity is maintained at 200 mAh g-1 after 200 cycles at a current density of 500 mA g-1.

  9. Properties of spin-1/2 triangular-lattice antiferromagnets CuY2Ge2O8 and CuLa2Ge2O8

    NASA Astrophysics Data System (ADS)

    Cho, Hwanbeom; Kratochvílová, Marie; Sim, Hasung; Choi, Ki-Young; Kim, Choong Hyun; Paulsen, Carley; Avdeev, Maxim; Peets, Darren C.; Jo, Younghun; Lee, Sanghyun; Noda, Yukio; Lawler, Michael J.; Park, Je-Geun

    2017-04-01

    We found new two-dimensional (2D) quantum (S =1 /2 ) antiferromagnetic systems: Cu R E2G e2O8 (R E =Y and La). According to our analysis of high-resolution x-ray and neutron diffraction experiments, the Cu network of Cu R E2G e2O8 (R E =Y and La) exhibits a 2D triangular lattice linked via weak bonds along the perpendicular b axis. Our bulk characterizations from 0.08 to 400 K show that they undergo a long-range order at 0.51(1) and 1.09(4) K for the Y and La systems, respectively. Interestingly, they also exhibit field induced phase transitions. For theoretical understanding, we carried out the density functional theory (DFT) band calculations to find that they are typical charge-transfer-type insulators with a gap of Eg≅2 eV . Taken together, our observations make Cu R E2G e2O8 (R E =Y and La) additional examples of low-dimensional quantum spin triangular antiferromagnets with the low-temperature magnetic ordering.

  10. Ab initio local-energy and local-stress analysis of tensile behaviours of tilt grain boundaries in Al and Cu

    NASA Astrophysics Data System (ADS)

    Wang, Hao; Kohyama, Masanori; Tanaka, Shingo; Shiihara, Yoshinori

    2017-01-01

    Tensile deformation and failure of Σ9 tilt grain boundaries (GBs) in Al and Cu have been examined by first-principles tensile tests (FPTTs). Local-energy and local-stress schemes were applied to clarify the variations of local energies and local hydrostatic stresses for all atoms during the deformation process. The GBs in Al and Cu exhibited quite different tensile behaviours in the FPTTs, despite their similar initial configurations. For the Al GB, there are two stages of deformation before failure. In the first stage, the back bonds of the interfacial bonds are mainly stretched, due to special high strength of the interfacial reconstructed bonds. In the second stage, the interfacial bonds begin to be significantly stretched due to high concentrated stresses, while stretching of the back bonds is suppressed. The atoms at the interfacial, back and bulk bonds have very different variations of local energies and local stresses during each stage, because the behaviour of each atom is significantly dependent on each local structural change due to the high sensitivity of sp electrons to the local environment in Al. The Cu GB has much higher tensile strength, and a natural introduction of stacking faults (SFs) occurs via the {111}< 112> shear slip in the bulk regions between the interfaces before the maximum stress is reached. This is caused by the smaller SF energy and lower ideal shear strength of Cu than Al, and is triggered by highly accumulated local energies and stress at the interface atoms. The local-energy distribution around the SF is consistent with the previous theoretical estimation. After the introduction of the SF, the local energies and stresses of all the atoms in the Cu GB supercell tend to become similar to each other during the tensile process, in contrast to the inhomogeneity in the Al GB. The origins of the different tensile behaviours observed for Al and Cu GBs are discussed with respect to the different bonding natures of Al and Cu, which are

  11. Atomistic models of Cu diffusion in CuInSe2 under variations in composition

    NASA Astrophysics Data System (ADS)

    Sommer, David E.; Dunham, Scott T.

    2018-03-01

    We construct an analytic model for the composition dependence of the vacancy-mediated Cu diffusion coefficient in undoped CuInSe2 using parameters from density functional theory. The applicability of this model is supported numerically with kinetic lattice Monte Carlo and Onsager transport tensors. We discuss how this model relates to experimental measurements of Cu diffusion, arguing that our results can account for significant contributions to the bulk diffusion of Cu tracers in non-stoichiometric CuInSe2.

  12. Structural investigation of Y1-xNixBa2Cu3O7-δ superconductor

    NASA Astrophysics Data System (ADS)

    Hadi-Sichani, Behnaz; Shakeripour, Hamideh; Salamati, Hadi

    2018-07-01

    Y1-xNixBa2Cu3O7-δ superconducting samples with 0 ≤ x ≤ 0.02 were synthesized by standard solid-state reaction and characterized by the X-ray powder diffraction technique. The Rietveld fitted XRD refinements show that all samples are crystallized in single phase, having orthorhombic structure with Pmmm space group. We investigated the effect of adding a magnetic element on the structure of this superconductor. The c cell parameter increases by doping of Ni until to an optimal value of Ni content, x ∼ 0.004, and then starts to decrease by higher value of Ni substitution. Moreover, it is seen that Cu(2)sbnd O(2) bond length decreases with increasing Ni up to the optimal concentration of Ni, too. The CuO2 planes become more distorted and hence charge carriers may have better chances of transportation to the CuO2 planes. By further increasing of Ni content than the optimal value, the Cu(2)sbnd O(2) bond lengths start to increase, and cause CuO2 planes to be flatten. We suggest, besides affecting the magnetic characteristic of Ni impurity, the Ni substitution leads to interesting crystallographic changes.

  13. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using X-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  14. Near-edge study of gold-substituted YBa2Cu3O(7-delta)

    NASA Technical Reports Server (NTRS)

    Ruckman, Mark W.; Hepp, Aloysius F.

    1991-01-01

    The valence of Cu and Au in YBa2Au0.3Cu2.7O7-delta was investigated using x-ray absorption near edge structure (XANES). X-ray and neutron diffraction studies indicate that Au goes on the Cu(1) site and Cu K-edge XANES shows that this has little effect on the oxidation state of the remaining copper. The Au L3 edge develops a white line feature whose position lies between that of trivalent gold oxide and monovalent potassium gold cyanide, and whose height relative to the edge step is smaller than in the two reference compounds. The appearance of the Au L3 edge suggests that fewer Au 3d states are involved in forming the Au-O bond in YBa2Au0.3Cu2.7O7-delta than in trivalent gold oxide.

  15. Cohesive zone modelling of wafer bonding and fracture: effect of patterning and toughness variations

    NASA Astrophysics Data System (ADS)

    Kubair, D. V.; Spearing, S. M.

    2006-03-01

    Direct wafer bonding has increasingly become popular in the manufacture of microelectromechanical systems and semiconductor microelectronics components. The success of the bonding process is controlled by variables such as wafer flatness and surface preparation. In order to understand the effects of these variables, spontaneous planar crack propagation simulations were performed using the spectral scheme in conjunction with a cohesive zone model. The fracture-toughness on the bond interface is varied to simulate the effect of surface roughness (nanotopography) and patterning. Our analysis indicated that the energetics of crack propagation is sensitive to the local surface property variations. The patterned wafers are tougher (well bonded) than the unpatterned ones of the same average fracture-toughness.

  16. Influence of stacking fault energy on defect structures and microhardness of Cu and Cu alloys.

    PubMed

    Tao, Jing-Mei; Li, Dai; Li, Cai-Ju; Zhu, Xin-Kun

    2011-12-01

    Nano-structured Cu, Cu-10 wt%Zn and Cu-2 wt%Al with stacking fault energies (SFE) of 78, 35 and 37 mJ/m2, respectively, were preprared through high energy ball milling. X-ray diffraction and Vickers microharness test were used to investigate the microstructure and microhardness of all the samples after ball milling. X-ray diffraction measurements indicate that lower SFEs lead both to decrease in grain size and increase in microstrain, dislocation and twin densities for Cu-10 wt%Zn and Cu-2 wt%Al after 5 h of ball milling. The microhardnesses of Cu-10 wt%Zn and Cu-2 wt%Al reach to nearly the same values of 2.5 GPa after 5 h of ball milling, which is higher than that of Cu of 2.0 GPa. Two factors are considered to contribute to the finer grian size and higher microhardness of Cu-10 wt%Zn and Cu-2 wt%Al: (1) the effect of solid solution strengthening, which result in the interaction of solute atoms with screw dislocations; (2) the introduction of deformation twins during ball milling process by the decreasing of SFE, which results in the grain refinement.

  17. Mechanisms of dietary Cu uptake in freshwater rainbow trout: evidence for Na-assisted Cu transport and a specific metal carrier in the intestine.

    PubMed

    Nadella, Sunita Rao; Grosell, Martin; Wood, Chris M

    2007-05-01

    Copper (Cu) is both a vital nutrient and a potent toxicant. The objective of this study was to analyze the mechanistic nature of intestinal Cu transport in rainbow trout using radiolabeled Cu (64Cu) and an in vitro gut sac technique. Reduction of mucosal NaCl levels inhibited Cu transport while increase caused stimulation; Na(2)SO(4) had an identical effect, implicating Na(+) rather than the anion. These responses were unrelated to solvent drag, osmotic pressure or changes in transepithelial potential. The presence of elevated luminal Ag stimulated Cu and Na(+) uptake. Phenamil caused a partial inhibition of both Cu and Na(+) uptake while hypercapnia stimulated Na(+) and Cu transport. Cu uptake was sensitive to luminal pH and inhibited by a tenfold excess of Fe and Zn. These factors had no effect on Na(+ )uptake. On the basis of these results we propose a novel Na(+)-assisted mechanism of Cu uptake wherein the Na(+) gradient stimulates an increase in the H(+) concentration of the brushborder creating a suitable microenvironment for the effective transport of Cu via either DMT1 or Ctr1.

  18. Recycled tetrahedron-like CuCl from waste Cu scraps for lithium ion battery anode.

    PubMed

    Hou, Hongying; Yao, Yuan; Liu, Song; Duan, Jixiang; Liao, Qishu; Yu, Chengyi; Li, Dongdong; Dai, Zhipeng

    2017-07-01

    The wide applications of metal Cu inevitably resulted in a large quantity of waste Cu materials. In order to recover the useful Cu under the mild conditions and reduce the environmental emission, waste Cu scraps were recycled in the form of CuCl powders with high economic value added (EVA) via the facile hydrothermal route. The recycled CuCl powders were characterized in terms of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD). The results suggested that the recycled CuCl powders consisted of many regular tetrahedron-like micro-particles. Furthermore, in order to reduce the cost of lithium ion battery (LIB) anode and build the connection of waste Cu scraps and LIB, the recycled CuCl powders were evaluated as the anode active material of LIB. As expected, the reversible discharge capacity was about 171.8mAh/g at 2.0C even after 50 cycles, implying the satisfactory cycle stability. Clearly, the satisfactory results may open a new avenue to develop the circular economy and the sustainable energy industry, which would be very important in terms of both the resource recovery and the environmental protection. Copyright © 2017. Published by Elsevier Ltd.

  19. Two-Phase Eutectic Growth in Al-Cu and Al-Cu-Ag

    NASA Astrophysics Data System (ADS)

    Senninger, Oriane; Peters, Matthew; Voorhees, Peter W.

    2018-02-01

    The microstructure developed by two-phase lamellar eutectics (α ) -(θ {-Al}2{Cu}) in Al-Cu and Al-Cu-Ag alloys is analyzed. A model of two-phase eutectic growth in multicomponent alloys is used to determine the scaling law of the eutectic microstructure using the alloy thermophysical properties. The application of the model to these alloys shows that the addition of Ag to Al-Cu alloys does not significantly change the length scale of the microstructure, which is in agreement with previous experimental studies. This is explained by the combined phenomena of the decrease in interface energies with the addition of Ag and the superheating of the (α ) phase interface induced by the Ag composition profile.

  20. Levels of processing with free and cued recall and unilateral temporal lobe epilepsy.

    PubMed

    Lespinet-Najib, Véronique; N'Kaoua, Bernard; Sauzéon, Hélène; Bresson, Christel; Rougier, Alain; Claverie, Bernard

    2004-04-01

    This study investigates the role of the temporal lobes in levels-of-processing tasks (phonetic and semantic encoding) according to the nature of recall tasks (free and cued recall). These tasks were administered to 48 patients with unilateral temporal epilepsy (right "RTLE"=24; left "LTLE"=24) and a normal group (n=24). The results indicated that LTLE patients were impaired for semantic processing (free and cued recall) and for phonetic processing (free and cued recall), while for RTLE patients deficits appeared in free recall with semantic processing. It is suggested that the left temporal lobe is involved in all aspects of verbal memory, and that the right temporal lobe is specialized in semantic processing. Moreover, our data seem to indicate that RTLE patients present a retrieval processing impairment (semantic condition), whereas the LTLE group is characterized by encoding difficulties in the phonetic and semantic condition.

  1. One-pot synthesis of hierarchical Cu{sub 2}O/Cu hollow microspheres with enhanced visible-light photocatalytic activity

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hong, Tianjie; Tao, Feifei, E-mail: feifeitao@usx.edu.cn; Lin, Jiudong

    2015-08-15

    The hierarchical Cu{sub 2}O/Cu hollow microspheres have been fabricated by the one-pot solvothermal redox method, which is one-step approach without any surfactant and template. By using the HRTEM, XRD, XPS and UV–vis spectroscopy, the as-prepared product is composed of Cu{sub 2}O and Cu with energy band gap of 1.72 eV. Based on the time-dependent experiments, the content of Cu{sub 2}O and Cu compositions can be effectively controlled by adjusting the reaction time and a possible mechanism is proposed. In addition, using various dye molecules to stimulate pollutants, the hierarchical Cu{sub 2}O/Cu hollow microspheres reacted for 8 h exhibit excellent visible-lightmore » photocatalytic activities, which is much higher than those of the Cu{sub 2}O/Cu catalysts formed at the shorter reaction time, commercial Cu{sub 2}O powder and the mixture of alone Cu{sub 2}O and Cu. This enhanced photocatalytic performance makes these hierarchical Cu{sub 2}O/Cu hollow microspheres a kind of efficient visible-light photocatalyst in removing some organic compounds in wastewater. - Graphical abstract: The hierarchical Cu{sub 2}O/Cu hollow microspheres with adjustable components have been synthesized by one-step solvothermal redox approach. The special structures and composition lead to the excellent visible-light photocatalytic activity. - Highlights: • The hierarchical Cu{sub 2}O/Cu hollow microspheres are fabricated by one-step approach. • The content of Cu{sub 2}O and Cu can be controlled by adjusting the reaction time. • The material exhibits a better visible-light photocatalytic activity and stability. • Degradation kinetics of MO by Cu{sub 2}O/Cu fits the pseudo first-order model.« less

  2. Effect of Cu content on wear resistance and mechanical behavior of Ti-Cu binary alloys

    NASA Astrophysics Data System (ADS)

    Yu, Feifei; Wang, Hefeng; Yuan, Guozheng; Shu, Xuefeng

    2017-04-01

    Arc melting with nonconsumable tungsten electrode and water-cooled copper crucible was used to fabricate Ti-Cu binary alloys with different Cu contents in an argon atmosphere. The compositions and phase structures of the fabricated alloys were investigated by glow discharge optical emission spectroscopy (GDOES) and X-ray diffraction (XRD). Nanoindentation tests through continuous stiffness measurement were then performed at room temperature to analyze the mechanical behaviors of the alloys. Results indicated that the composition of each Ti-Cu binary alloy was Ti(100- x) Cu x ( x = 43, 60, 69, and 74 at.%). The XRD analysis results showed that the alloys were composed of different phases, indicating that different Cu contents led to the variations in alloy hardness. The wear tests results revealed that elemental Cu positively affects the wear resistance properties of the Ti-Cu alloys. Nanoindentation testing results showed that the moduli of the Ti-Cu alloys were minimally changed at increasing Cu content, whereas their hardness evidently increased according to the wear test results.

  3. Hot Deformation Behavior and Processing Maps of Diamond/Cu Composites

    NASA Astrophysics Data System (ADS)

    Zhang, Hongdi; Liu, Yue; Zhang, Fan; Zhang, Di; Zhu, Hanxing; Fan, Tongxiang

    2018-03-01

    The hot deformation behaviors of 50 vol pct uncoated and Cr-coated diamond/Cu composites were investigated using hot isothermal compression tests under the temperature and strain rate ranging from 1073 K to 1273 K (800 °C to 1000 °C) and from 0.001 to 5 s-1, respectively. Dynamic recrystallization was determined to be the primary restoration mechanism during deformation. The Cr3C2 coating enhanced the interfacial bonding and resulted in a larger flow stress for the Cr-coated diamond/Cu composites. Moreover, the enhanced interfacial affinity led to a higher activation energy for the Cr-coated diamond/Cu composites (238 kJ/mol) than for their uncoated counterparts (205 kJ/mol). The strain-rate-dependent constitutive equations of the diamond/Cu composites were derived based on the Arrhenius model, and a high correlation (R = 0.99) was observed between the calculated flow stresses and experimental data. With the help of processing maps, hot extrusions were realized at 1123 K/0.01 s-1 and 1153 K/0.01 s-1 (850 °C/0.01 s-1 and 880 °C/0.01 s-1) for the uncoated and coated diamond/Cu composites, respectively. The combination of interface optimization and hot extrusion led to increases of the density and thermal conductivity, thereby providing a promising route for the fabrication of diamond/Cu composites.

  4. Hot Deformation Behavior and Processing Maps of Diamond/Cu Composites

    NASA Astrophysics Data System (ADS)

    Zhang, Hongdi; Liu, Yue; Zhang, Fan; Zhang, Di; Zhu, Hanxing; Fan, Tongxiang

    2018-06-01

    The hot deformation behaviors of 50 vol pct uncoated and Cr-coated diamond/Cu composites were investigated using hot isothermal compression tests under the temperature and strain rate ranging from 1073 K to 1273 K (800 °C to 1000 °C) and from 0.001 to 5 s-1, respectively. Dynamic recrystallization was determined to be the primary restoration mechanism during deformation. The Cr3C2 coating enhanced the interfacial bonding and resulted in a larger flow stress for the Cr-coated diamond/Cu composites. Moreover, the enhanced interfacial affinity led to a higher activation energy for the Cr-coated diamond/Cu composites (238 kJ/mol) than for their uncoated counterparts (205 kJ/mol). The strain-rate-dependent constitutive equations of the diamond/Cu composites were derived based on the Arrhenius model, and a high correlation ( R = 0.99) was observed between the calculated flow stresses and experimental data. With the help of processing maps, hot extrusions were realized at 1123 K/0.01 s-1 and 1153 K/0.01 s-1 (850 °C/0.01 s-1 and 880 °C/0.01 s-1) for the uncoated and coated diamond/Cu composites, respectively. The combination of interface optimization and hot extrusion led to increases of the density and thermal conductivity, thereby providing a promising route for the fabrication of diamond/Cu composites.

  5. CuAlO2 and CuAl2O4 thin films obtained by stacking Cu and Al films using physical vapor deposition

    NASA Astrophysics Data System (ADS)

    Castillo-Hernández, G.; Mayén-Hernández, S.; Castaño-Tostado, E.; DeMoure-Flores, F.; Campos-González, E.; Martínez-Alonso, C.; Santos-Cruz, J.

    2018-06-01

    CuAlO2 and CuAl2O4 thin films were synthesized by the deposition of the precursor metals using the physical vapor deposition technique and subsequent annealing. Annealing was carried out for 4-6 h in open and nitrogen atmospheres respectively at temperatures of 900-1000 °C with control of heating and cooling ramps. The band gap measurements ranged from 3.3 to 4.5 eV. Electrical properties were measured using the van der Pauw technique. The preferred orientations of CuAlO2 and CuAl2O4 were found to be along the (1 1 2) and (3 1 1) planes, respectively. The phase percentages were quantified using a Rietveld refinement simulation and the energy dispersive X-ray spectroscopy indicated that the composition is very close to the stoichiometry of CuAlO2 samples and with excess of aluminum and deficiency of copper for CuAl2O4 respectively. High resolution transmission electron microscopy identified the principal planes in CuAlO2 and in CuAl2O4. Higher purities were achieved in nitrogen atmosphere with the control of the cooling ramps.

  6. Microwave Spectra and Structure of {H_2-CuF}: Overview of the Complexes of Hydrogen with Metal-Containing Diatomics

    NASA Astrophysics Data System (ADS)

    Grubbs, G. S. Grubbs, Ii; Frohman, Daniel J.; Yu, Zhenhong; Novick, Stewart E.

    2013-06-01

    We present here the FTMW spectra of the various isotopologues of the intermediate strength bound complex of dihydrogen with copper fluoride. The bond between the two moieties is surprisingly strong, the H-H forming the cross of the T with the Cu closest to H_2 in the C_{{2v}} structure. Laser ablation was used to produce both copper isotopologues of p-H_2-CuF, o-D_2-CuF, and HD-CuF whose J = 1 - 0 transitions were observed. Significant changes in the nuclear quadrupole coupling constants for the copper nucleus in H_2-CuF compared to that in uncomplexed CuF suggests bonding greater than that typical of van der Waals interactions. This talk will serve as the introduction to presentations at this meeting of other H_2 metal containing diatomics. D. J. Frohman, {G. S. Grubbs II}, Z. Yu, S. E. Novick, Inorg. Chem., 52, 816-822 (2013).

  7. Interactions between C and Cu atoms in single-layer graphene: direct observation and modelling.

    PubMed

    Kano, Emi; Hashimoto, Ayako; Kaneko, Tomoaki; Tajima, Nobuo; Ohno, Takahisa; Takeguchi, Masaki

    2016-01-07

    Metal doping into the graphene lattice has been studied recently to develop novel nanoelectronic devices and to gain an understanding of the catalytic activities of metals in nanocarbon structures. Here we report the direct observation of interactions between Cu atoms and single-layer graphene by transmission electron microscopy. We document stable configurations of Cu atoms in the graphene sheet and unique transformations of graphene promoted by Cu atoms. First-principles calculations based on density functional theory reveal a reduction of energy barrier that caused rotation of C-C bonds near Cu atoms. We discuss two driving forces, electron irradiation and in situ heating, and conclude that the observed transformations were mainly promoted by electron irradiation. Our results suggest that individual Cu atoms can promote reconstruction of single-layer graphene.

  8. Transfer of InP epilayers by wafer bonding

    NASA Astrophysics Data System (ADS)

    Hjort, Klas

    2004-08-01

    Wafer bonding increases the freedom of design in the integration of dissimilar materials. For example, it is interesting to combine III-V compounds that have direct band gap and high mobility with silicon (Si) that is extensively used in microelectronic applications. The interest to integrate III-V-based materials with Si arises primarily from two types of applications: smart pixels for optical intra- and inter-chip interconnects in the so-called optoelectronic integrated circuits, and optoelectronic devices using some material advantages of combining III-V with Si. Also, in the III-V industry larger substrates are crucial for higher efficiency in high-volume production, and especially so for monolithic microwave integrated circuits (MMIC). For indium phosphide (InP) the development of large-area substrates has not been able to keep up with market demands. One way to circumvent this problem is to use silicon substrates that are large-area, low-cost, and mechanically strong with high thermal conductivity. In addition, silicon is transparent at the emission wavelengths most often used in InP-based optoelectronics. Unfortunately, the large lattice-mismatch, 8.1%, between silicon and InP, has limited the success of heteroepitaxial growth. Hence, one alternative to be reviewed is InP-to-Si wafer bonding. When a direct semiconductor interface is not needed there are several other means of wafer bonding, e.g. adhesive, eutectic, and solid-state. These processes can be used for direct integration of small islets of epitaxially thin InP microelectronics onto other substrates, e.g. by transferring of InP-based epilayers to a Si-based microwave circuit by pick-and-place, BCB resist adhesive bonding and sacrificing of the InP substrate.

  9. The microstructure and magnetic properties of Cu/CuO/Ni core/multi-shell nanowire arrays

    NASA Astrophysics Data System (ADS)

    Yang, Feng; Shi, Jie; Zhang, Xiaofeng; Hao, Shijie; Liu, Yinong; Feng, Chun; Cui, Lishan

    2018-04-01

    Multifunctional metal/oxide/metal core/multi-shell nanowire arrays were prepared mostly by physical or chemical vapor deposition. In our study, the Cu/CuO/Ni core/multi-shell nanowire arrays were prepared by AAO template-electrodeposition and oxidation processes. The Cu/Ni core/shell nanowire arrays were prepared by AAO template-electrodeposition method. The microstructure and chemical compositions of the core/multi-shell nanowires and core/shell nanowires have been characterized using transmission electron microscopy with HADDF-STEM and X-ray diffraction. Magnetization measurements revealed that the Cu/CuO/Ni and Cu/Ni nanowire arrays have high coercivity and remanence ratio.

  10. Exploring low-temperature dehydrogenation at ionic Cu sites in beta zeolite to enable alkane recycle in dimethyl ether homologation

    DOE PAGES

    Farberow, Carrie A.; Cheah, Singfoong; Kim, Seonah; ...

    2017-04-24

    Cu-based catalysts containing targeted functionalities including metallic Cu, oxidized Cu, ionic Cu, and Bronsted acid sites were synthesized and evaluated for isobutane dehydrogenation. Hydrogen productivities, combined with operando X-ray absorption spectroscopy, indicated that Cu(I) sites in Cu/BEA catalysts activate C-H bonds in isobutane. Computational analysis revealed that isobutane dehydrogenation at a Cu(I) site proceeds through a two-step mechanism with a maximum energy barrier of 159 kJ/mol. Furthermore, these results demonstrate that light alkanes can be reactivated on Cu/BEA, which may enable re-entry of these species into the chain-growth cycle of dimethyl ether homologation, thereby increasing gasoline-range (C 5+) hydrocarbon yield.

  11. Depth Profile of Induced Magnetic Polarization in Cu Layers of Co/Cu(111) Metallic Superlattices by Resonant X-ray Magnetic Scattering at the Cu K Absorption Edge

    NASA Astrophysics Data System (ADS)

    Uegaki, Shin; Yoshida, Akihiro; Hosoito, Nobuyoshi

    2015-03-01

    We investigated induced spin polarization of 4p conduction electrons in Cu layers of antiferromagnetically (AFM) and ferromagnetically (FM) coupled Co/Cu(111) metallic superlattices by resonant X-ray magnetic scattering at the Cu K absorption edge. Magnetic reflectivity profiles of the two superlattices were measured in the magnetic saturation state with circularly polarized synchrotron radiation X-rays at 8985 eV. Depth profiles of the resonant magnetic scattering length of Cu, which corresponds to the induced spin polarization of Cu, were evaluated in the two Co/Cu superlattices by analyzing the observed magnetic reflectivity profiles. We demonstrated that the spin polarization induced in the Cu layer was distributed around the Co/Cu interfaces with an attenuation length of several Å in both AFM and FM coupled superlattices. The uniform component, which exists in Au layers of Fe/Au(001) superlattices, was not found in the depth distribution of induced magnetic polarization in the Cu layers of Co/Cu(111) superlattices.

  12. Effects of limited cu supply on soldering reactions between SnAgCu and Ni

    NASA Astrophysics Data System (ADS)

    Ho, C. E.; Lin, Y. W.; Yang, S. C.; Kao, C. R.; Jiang, D. S.

    2006-05-01

    The volume difference between the various types of solder joints in electronic devices can be enormous. For example, the volume difference between a 760-µm ball grid array solder joint and a 75-µm flip-chip solder joint is as high as 1000 times. Such a big difference in volume produces a pronounced solder volume effect. This volume effect on the soldering reactions between the Sn3AgxCu (x=0.4, 0.5, or 0.6 wt.%) solders and Ni was investigated. Three different sizes of solder spheres (300, 500, and 760 µm in diameter) were soldered onto Ni soldering pads. Both the Cu concentration and the solder volume had a strong effect on the type of the reaction products formed. In addition, (Cu,Ni)6Sn5 massively spalled from the interface under certain conditions, including smaller joints and those with lower Cu concentration. We attributed the massive spalling of (Cu,Ni)6Sn5 to the decrease of the available Cu in the solders. The results of this study suggest that Cu-rich SnAgCu solders can be used to prevent this massive spalling.

  13. Halo and Pseudohalo Cu(I)-Pyridinato Double Chains with Tunable Physical Properties.

    PubMed

    Hassanein, K; Amo-Ochoa, P; Gómez-García, C J; Delgado, S; Castillo, O; Ocón, P; Martínez, J I; Perles, J; Zamora, F

    2015-11-16

    The properties recently reported on the Cu(I)-iodide pyrimidine nonporous 1D-coordination polymer [CuI(ANP)]n (ANP = 2-amino-5-nitropyridine) showing reversible physically and chemically driven electrical response have prompted us to carry a comparative study with the series of [CuX(ANP)]n (X = Cl (1), X = Br (2), X = CN (4), and X = SCN (5)) in order to understand the potential influence of the halide and pseudohalide bridging ligands on the physical properties and their electrical response to vapors of these materials. The structural characterization of the series shows a common feature, the presence of -X-Cu(ANP)-X- (X = Cl, Br, I, SCN) double chain structure. Complex [Cu(ANP)(CN)]n (4) presents a helical single chain. Additionally, the chains show supramolecular interlinked interactions via hydrogen bonding giving rise to the formation of extended networks. Their luminescent and electrical properties have been studied. The results obtained have been correlated with structural changes. Furthermore, the experimental and theoretical results have been compared using the density functional theory (DFT). The electrical response of the materials has been evaluated in the presence of vapors of diethyl ether, dimethyl methylphosphonate (DMMP), CH2Cl2, HAcO, MeOH, and EtOH, to build up simple prototype devices for gas detectors. Selectivity toward gases consisting of molecules with H-bonding donor or acceptor groups is clearly observed. This selective molecular recognition is likely due to the 2-amino-5-nitropyridine terminal ligand.

  14. Electronic properties of Y-Ba-Cu-O superconductors as seen by Cu and O NMR/NQR

    NASA Technical Reports Server (NTRS)

    Brinkmann, D.

    1995-01-01

    Nuclear Magnetic Resonance (NMR) and Nuclear Quadrupole Resonance (NQR) allow the investigation of electronic properties at the atomic level. We will report on such studies of typical members of the the Y-Ba-Cu-O family such as YBa2Cu30(6 + x) (1-2-3-(6 + x)), YBa2Cu4O8 (1-2-4) and Y2Ba4Cu7015 (2-4-7) with many examples of recent work performed in our laboratory. In particular, we will deal with Knight shift and relaxation studies of copper and oxygen. We will discuss important issues of current studies such as: (1) Existence of a common electronic spin-susceptibility in the planes (and perhaps in the chains) of 1-2-4; (2) Strong evidence for the existence of a pseudo spin-gap of the antiferromagnetic fluctuations in 1-2-4 and 2-4-7; (3) Evidence for d-wave pairing in 1-2-4; (4) Strong coupling of inequivalent Cu-O planes in 2-4-7 and possible origin for the high Tc value of this compound; and (5) The possibility to describe NMR data in the framework of a charge-excitation picture.

  15. Proteomic response of mussels Mytilus galloprovincialis exposed to CuO NPs and Cu²⁺: an exploratory biomarker discovery.

    PubMed

    Gomes, Tânia; Chora, Suze; Pereira, Catarina G; Cardoso, Cátia; Bebianno, Maria João

    2014-10-01

    absence of the mussel genome precluded the identification of other proteins relevant to clarify the effects of CuO NPs in mussels' tissues, proteomics analysis provided additional knowledge of their potential effects at the protein level that after confirmation and validation can be used as putative new biomarkers in nanotoxicology. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Enhancement in visible light photocatalytic activity by embedding Cu nanoparticles over CuS/MCM-41 nanocomposite

    NASA Astrophysics Data System (ADS)

    Sohrabnezhad, Sh.; Karamzadeh, M.

    2017-07-01

    This article indicate the biogenic synthesis of copper nanoparticles (Cu NPs) using the borage flowers extract of Borago officinalis over CuS/MCM-41 nanocomposite (NC). No external reducing was utilized in the developed method. The CuS-MCM-41 NC was used as stabilizing agent. The synthesis of CuS nanostructure in MCM-41 material has been realized by hydrothermal method. Their physiochemical properties have been characterized by X-ray diffraction, transmission electron microscopy (TEM), UV-Visible diffuse reflectance spectroscopy, and Fourier transform infrared spectroscopy. On the basis of TEM images, a layer of Cu NPs has been located over CuS/MCM-41 NC with average diameter of 60-80 nm. The results revealed the spherical nature of the prepared Cu NPs with diameter less than 10 nm. The DR spectra of Cu NPs in MCM-41 and CuS-MCM-41 NCs showed surface plasmon resonance bands at 570 and 500-600 nm, respectively. The photocatalytic activity was evaluated under visible light irradiation using the photocatalytic degradation of methylene blue (MB) as a model reaction. The prepared Cu/CuS/MCM-41 nanocomposite microspheres showed higher photodegradation ability for MB than CuS/MCM-41. The degradation of MB achieved up to 80% after 60 min and the nanocomposite could be recycled and reused.

  17. On the hydrothermal stability of Cu/SSZ-13 SCR catalysts

    DOE PAGES

    Gao, Feng; Szanyi, Janos

    2018-05-07

    Cu/SSZ-13 SCR catalysts have been extensively studied in the past decade or so. Hydrothermal stability of these catalysts has been identified as the most important criterion for application. In this perspective, we describe recent atomic-level understanding of their hydrothermal stability. In particular, electron paramagnetic resonance (EPR) is shown to rather accurately quantify isolated Cu(II) ions and CuO clusters in fresh and aged catalysts to demonstrate the remarkable hydrothermal stability for Cu 2+ ions located in 6-membered ring windows, and the conversion of [Cu(OH)] + ions in Chabazite cages to CuO clusters. The hydrothermal stability difference of the two isolated Cu(II)more » ions is confirmed with DFT simulations and the conversion of [Cu(OH)] + to CuO is proposed to involve formation, migration and condensation of Cu(OH) 2 intermediates. The structural destructive role of CuO clusters is attributed to mesopore formation from their migration, which more severely damages the catalysts than dealumination. Lastly, perspectives are given on new strategies for low-temperature NO x removal, rational design and refinement of Cu/SSZ-13, and development of new Cu/zeolite SCR catalysts with even better performance than the state-of-the-art Cu/SSZ-13.« less

  18. On the hydrothermal stability of Cu/SSZ-13 SCR catalysts

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gao, Feng; Szanyi, Janos

    Cu/SSZ-13 SCR catalysts have been extensively studied in the past decade or so. Hydrothermal stability of these catalysts has been identified as the most important criterion for application. In this perspective, we describe recent atomic-level understanding of their hydrothermal stability. In particular, electron paramagnetic resonance (EPR) is shown to rather accurately quantify isolated Cu(II) ions and CuO clusters in fresh and aged catalysts to demonstrate the remarkable hydrothermal stability for Cu 2+ ions located in 6-membered ring windows, and the conversion of [Cu(OH)] + ions in Chabazite cages to CuO clusters. The hydrothermal stability difference of the two isolated Cu(II)more » ions is confirmed with DFT simulations and the conversion of [Cu(OH)] + to CuO is proposed to involve formation, migration and condensation of Cu(OH) 2 intermediates. The structural destructive role of CuO clusters is attributed to mesopore formation from their migration, which more severely damages the catalysts than dealumination. Lastly, perspectives are given on new strategies for low-temperature NO x removal, rational design and refinement of Cu/SSZ-13, and development of new Cu/zeolite SCR catalysts with even better performance than the state-of-the-art Cu/SSZ-13.« less

  19. Raman spectroscopy of the multianion mineral gartrellite-PbCu(Fe3+,Cu)(AsO4)2(OH,H2O)2

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; Xi, Yunfei; Palmer, Sara J.

    2012-04-01

    The multianion mineral gartrellite PbCu(Fe3+,Cu)(AsO4)2(OH,H2O)2 has been studied by a combination of Raman and infrared spectroscopy. The vibrational spectra of two gartrellite samples from Durango and Ashburton Downs were compared. Gartrellite is one of the tsumcorite mineral group based upon arsenate and sulphate anions. Crystal symmetry is either triclinic in the case of an ordered occupation of two cationic sites, triclinic due to ordering of the H bonds in the case of species with 2 water molecules per formula unit, or monoclinic in the other cases. Characteristic Raman spectra of the minerals enable the assignment of the bands to specific vibrational modes. These spectra are related to the structure of gartrellite. The position of the hydroxyl and water stretching vibrations are related to the strength of the hydrogen bond formed between the OH unit and the AsO4 anion.

  20. Cu-modified alkalinized g-C3N4 as photocatalytically assisted heterogeneous Fenton-like catalyst

    NASA Astrophysics Data System (ADS)

    Dong, Qimei; Chen, Yingying; Wang, Lingli; Ai, Shasha; Ding, Hanming

    2017-12-01

    Alkalinized graphitic carbon nitride (CNK-OH) has been synthesized by one-step thermal poly-condensation method, and Cu-modified alkalinized g-C3N4 (Cu-CNK-OH) has been prepared by impregnation approach over CNK-OH. These copper species in Cu-CNK-OH are embedded in the frame of CNK-OH mostly via the Cu-N bonds. Cu-CNK-OH has been employed as a heterogeneous Fenton-like catalyst to degrade rhodamine B (RhB). Both the production efficiency of hydroxyl radicals and the transformation rate of Cu(II)/Cu(I) redox pair increase under visible-light irradiation. As a result, Cu-CNK-OH exhibits improved Fenton-like catalytic activity on the degradation of RhB. The synergetic interaction between Fenton-like process and photocatalytic process also contributes such improvement. The hydroxyl radicals and holes are the major reactive species in the photocatalytically assisted Fenton-like process. This study provides a valuable strategy for metal modification of alkalinized g-C3N4 with enhanced Fenton-like catalytic performance for the degradation of organic contaminants.

  1. Treatment of reverse osmosis (RO) concentrate by the combined Fe/Cu/air and Fenton process (1stFe/Cu/air-Fenton-2ndFe/Cu/air).

    PubMed

    Ren, Yi; Yuan, Yue; Lai, Bo; Zhou, Yuexi; Wang, Juling

    2016-01-25

    To decompose or transform the toxic and refractory reverse osmosis (RO) concentrate and improve the biodegradability, 1stFe/Cu/air-Fenton-2ndFe/Cu/air were developed to treat RO concentrate obtained from an amino acid production plant in northern China. First, their operating conditions were optimized thoroughly. Furthermore, 5 control experiments were setup to confirm the superiority of 1stFe/Cu/air-Fenton-2ndFe/Cu/air and synergistic reaction between Fe/Cu/air and Fenton. The results suggest that the developed method could obtain high COD removal (65.1%) and BOD5/COD ratio (0.26) due to the synergistic reaction between Fe/Cu/air and Fenton. Under the optimal conditions, the influent and effluent of 1stFe/Cu/air-Fenton-2ndFe/Cu/air and 5 control experiments were analyzed by using UV, FTIR, EEM and LC, which confirm the superiority of 1stFe/Cu/air-Fenton-2ndFe/Cu/air. Therefore, the developed method in this study is a promising process for treatment of RO concentrate. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Cu-67 Photonuclear Production

    NASA Astrophysics Data System (ADS)

    Starovoitova, Valeriia; Foote, Davy; Harris, Jason; Makarashvili, Vakhtang; Segebade, Christian R.; Sinha, Vaibhav; Wells, Douglas P.

    2011-06-01

    Cu-67 is considered as one of the most promising radioisotopes for cancer therapy with monoclonal antibodies. Current production schemes using high-flux reactors and cyclotrons do not meet potential market need. In this paper we discuss Cu-67 photonuclear production through the reaction Zn-68(γ,p)Cu-67. Computer simulations were done together with experiments to study and optimize Cu-67 yield in natural Zn target. The data confirms that the photonuclear method has potential to produce large quantities of the isotope with sufficient purity to be used in medical field.

  3. Relativity-Induced Bonding Pattern Change in Coinage Metal Dimers M2 (M = Cu, Ag, Au, Rg).

    PubMed

    Li, Wan-Lu; Lu, Jun-Bo; Wang, Zhen-Ling; Hu, Han-Shi; Li, Jun

    2018-05-07

    The periodic table provides a fundamental protocol for qualitatively classifying and predicting chemical properties based on periodicity. While the periodic law of chemical elements had already been rationalized within the framework of the nonrelativistic description of chemistry with quantum mechanics, this law was later known to be affected significantly by relativity. We here report a systematic theoretical study on the chemical bonding pattern change in the coinage metal dimers (Cu 2 , Ag 2 , Au 2 , Rg 2 ) due to the relativistic effect on the superheavy elements. Unlike the lighter congeners basically demonstrating ns- ns bonding character and a 0 g + ground state, Rg 2 shows unique 6d-6d bonding induced by strong relativity. Because of relativistic spin-orbit (SO) coupling effect in Rg 2 , two nearly degenerate SO states, 0 g + and 2 u , exist as candidate of the ground state. This relativity-induced change of bonding mechanism gives rise to various unique alteration of chemical properties compared with the lighter dimers, including higher intrinsic bond energy, force constant, and nuclear shielding. Our work thus provides a rather simple but clear-cut example, where the chemical bonding picture is significantly changed by relativistic effect, demonstrating the modified periodic law in heavy-element chemistry.

  4. Self-supported three-dimensional Cu/Cu2O-CuO/rGO nanowire array electrodes for an efficient hydrogen evolution reaction.

    PubMed

    Ye, Lin; Wen, Zhenhai

    2018-06-14

    We report the fabrication of self-supported Cu/Cu2O-CuO/rGO nanowire arrays on commercial porous copper foam, which exhibit excellent activity and durability for electrochemical hydrogen evolution, presenting a small onset potential of 84 mV and a low overpotential of 105 mV at a current density of 10 mA cm-2.

  5. High-Q Wafer Level Package Based on Modified Tri-Layer Anodic Bonding and High Performance Getter and Its Evaluation for Micro Resonant Pressure Sensor.

    PubMed

    Wang, Liying; Du, Xiaohui; Wang, Lingyun; Xu, Zhanhao; Zhang, Chenying; Gu, Dandan

    2017-03-16

    In order to achieve and maintain a high quality factor (high-Q) for the micro resonant pressure sensor, this paper presents a new wafer level package by adopting cross-layer anodic bonding technique of the glass/silicon/silica (GSS) stackable structure and integrated Ti getter. A double-layer structure similar to a silicon-on-insulator (SOI) wafer is formed after the resonant layer and the pressure-sensitive layer are bonded by silicon direct bonding (SDB). In order to form good bonding quality between the pressure-sensitive layer and the glass cap layer, the cross-layer anodic bonding technique is proposed for vacuum package by sputtering Aluminum (Al) on the combination wafer of the pressure-sensitive layer and the resonant layer to achieve electrical interconnection. The model and the bonding effect of this technique are discussed. In addition, in order to enhance the performance of titanium (Ti) getter, the prepared and activation parameters of Ti getter under different sputtering conditions are optimized and discussed. Based on the optimized results, the Ti getter (thickness of 300 nm to 500 nm) is also deposited on the inside of the glass groove by magnetron sputtering to maintain stable quality factor (Q). The Q test of the built testing system shows that the number of resonators with a Q value of more than 10,000 accounts for more than 73% of the total. With an interval of 1.5 years, the Q value of the samples remains almost constant. It proves the proposed cross-layer anodic bonding and getter technique can realize high-Q resonant structure for long-term stable operation.

  6. Ab initio molecular dynamics study of thermite reaction at Al and CuO nano-interfaces at different temperatures

    NASA Astrophysics Data System (ADS)

    Tang, Cui-Ming; Chen, Xiao-Xu; Cheng, Xin-Lu; Zhang, Chao-Yang; Lu, Zhi-Peng

    2018-05-01

    The thermite reaction at Al/CuO nano-interfaces is investigated with ab initio molecular dynamics calculations in canonical ensemble at 500 K, 800 K, 1200 K and 1500 K, respectively. The reaction process and reaction products are analyzed in terms of chemical bonds, average charge, time constants and total potential energy. The activity of the reactants enhances with increasing temperature, which induces a faster thermite reaction. The alloy reaction obviously expands outward at Cu-rich interface of Al/CuO system, and the reaction between Al and O atoms obviously expands outward at O-rich interface as temperature increases. Different reaction products are found at the outermost layer of different interfaces in the Al/CuO system. In generally, the average charge of the outer layer aluminum atoms (i.e., Al1, Al2, Al5 and Al6) increases with temperature. The potential energy of Al/CuO system decreases significantly, which indicates that drastic exothermic reaction occurs at the Al/CuO system. This research enhances fundamental understanding in temperature effect on the thermite reaction at atomic level, which can potentially open new possibilities for its industrial application.

  7. Novel calix[4]pyrrole assembly: Punctilious recognition of F- and Cu+2 ions

    NASA Astrophysics Data System (ADS)

    Bhatt, Keyur D.; Shah, Hemangini; Modi, Krunal M.; Kongor, Anita; Panchal, Manthan; Jain, Vinod K.

    2017-12-01

    A new tetra hydroxyl methoxy substituted calix[4]pyrrole (HMCP) has been synthesized and found to form stable complex with F- ions and Cu+2 ions. The red-shift in absorption band of HMCP was observed due to the presence of both cation (Cu+2) and anion (F-). These results displayed that formation of the complex is mainly attributed to the charge-transfer interactions between HMCP with electron deficient pyrrole rings and the electron-rich guest ions. Molecular dynamics simulation predicts intermolecular H-bonds and van der Waals types of interaction for the complex formation of HMCP-Cu+2 and HMCP-F-.

  8. Thermochemistry of paddle wheel MOFs: Cu-HKUST-1 and Zn-HKUST-1.

    PubMed

    Bhunia, Manas K; Hughes, James T; Fettinger, James C; Navrotsky, Alexandra

    2013-06-25

    Metal-organic framework (MOF) porosity relies upon robust metal-organic bonds to retain structural rigidity upon solvent removal. Both the as-synthesized and activated Cu and Zn polymorphs of HKUST-1 were studied by room temperature acid solution calorimetry. Their enthalpies of formation from dense assemblages (metal oxide (ZnO or CuO), trimesic acid (TMA), and N,N-dimethylformamide (DMF)) were calculated from the calorimetric data. The enthalpy of formation (ΔHf) of the as-synthesized Cu-HKUST-H2O ([Cu3TMA2·3H2O]·5DMF) is -52.70 ± 0.34 kJ per mole of Cu. The ΔHf for Zn-HKUST-DMF ([Zn3TMA2·3DMF]·2DMF) is -54.22 ± 0.57 kJ per mole of Zn. The desolvated Cu-HKUST-dg [Cu3TMA2] has a ΔHf of 16.66 ± 0.51 kJ/mol per mole Cu. The ΔHf for Zn-HKUST-amorph [Zn3TMA2·2DMF] is -3.57 ± 0.21 kJ per mole of Zn. Solvent stabilizes the Cu-HKUST-H2O by -69.4 kJ per mole of Cu and Zn-HKUST-DMF by at least -50.7 kJ per mole of Zn. Such strong chemisorption of solvent is similar in magnitude to the strongly exothermic binding at low coverage for chemisorbed H2O on transition metal oxide nanoparticle surfaces. The strongly exothermic solvent-framework interaction suggests that solvent can play a critical role in obtaining a specific secondary building unit (SBU) topology.

  9. Low-lying level structure of 56Cu and its implications for the rp process

    NASA Astrophysics Data System (ADS)

    Ong, W.-J.; Langer, C.; Montes, F.; Aprahamian, A.; Bardayan, D. W.; Bazin, D.; Brown, B. A.; Browne, J.; Crawford, H.; Cyburt, R.; Deleeuw, E. B.; Domingo-Pardo, C.; Gade, A.; George, S.; Hosmer, P.; Keek, L.; Kontos, A.; Lee, I.-Y.; Lemasson, A.; Lunderberg, E.; Maeda, Y.; Matos, M.; Meisel, Z.; Noji, S.; Nunes, F. M.; Nystrom, A.; Perdikakis, G.; Pereira, J.; Quinn, S. J.; Recchia, F.; Schatz, H.; Scott, M.; Siegl, K.; Simon, A.; Smith, M.; Spyrou, A.; Stevens, J.; Stroberg, S. R.; Weisshaar, D.; Wheeler, J.; Wimmer, K.; Zegers, R. G. T.

    2017-05-01

    The low-lying energy levels of proton-rich 56Cu have been extracted using in-beam γ -ray spectroscopy with the state-of-the-art γ -ray tracking array GRETINA in conjunction with the S800 spectrograph at the National Superconducting Cyclotron Laboratory at Michigan State University. Excited states in 56Cu serve as resonances in the 55Ni(p ,γ )56Cu reaction, which is a part of the rp process in type-I x-ray bursts. To resolve existing ambiguities in the reaction Q value, a more localized isobaric multiplet mass equation (IMME) fit is used, resulting in Q =639 ±82 keV. We derive the first experimentally constrained thermonuclear reaction rate for 55Ni(p ,γ )56Cu . We find that, with this new rate, the rp process may bypass the 56Ni waiting point via the 55Ni(p ,γ ) reaction for typical x-ray burst conditions with a branching of up to ˜40 % . We also identify additional nuclear physics uncertainties that need to be addressed before drawing final conclusions about the rp -process reaction flow in the 56Ni region.

  10. Communication: Surface-to-bulk diffusion of isolated versus interacting C atoms in Ni(111) and Cu(111) substrates: A first principle investigation.

    PubMed

    Harpale, Abhilash; Panesi, Marco; Chew, Huck Beng

    2015-02-14

    Using first principle calculations, we study the surface-to-bulk diffusion of C atoms in Ni(111) and Cu(111) substrates, and compare the barrier energies associated with the diffusion of an isolated C atom versus multiple interacting C atoms. We find that the preferential Ni-C bonding over C-C bonding induces a repulsive interaction between C atoms located at diagonal octahedral voids in Ni substrates. This C-C interaction accelerates C atom diffusion in Ni with a reduced barrier energy of ∼1 eV, compared to ∼1.4-1.6 eV for the diffusion of isolated C atoms. The diffusion barrier energy of isolated C atoms in Cu is lower than in Ni. However, bulk diffusion of interacting C atoms in Cu is not possible due to the preferential C-C bonding over C-Cu bonding, which results in C-C dimer pair formation near the surface. The dramatically different C-C interaction effects within the different substrates explain the contrasting growth mechanisms of graphene on Ni(111) and Cu(111) during chemical vapor deposition.

  11. Antiferromagnetism in EuCu 2As 2 and EuCu 1.82Sb 2 single crystals

    DOE PAGES

    Anand, V. K.; Johnston, D. C.

    2015-05-07

    Single crystals of EuCu 2As 2 and EuCu 2Sb 2 were grown from CuAs and CuSb self-flux, respectively. The crystallographic, magnetic, thermal, and electronic transport properties of the single crystals were investigated by room-temperature x-ray diffraction (XRD), magnetic susceptibility χ versus temperature T, isothermal magnetization M versus magnetic field H, specific heat C p(T), and electrical resistivity ρ(T) measurements. EuCu 2As 2 crystallizes in the body-centered tetragonal ThCr 2Si 2-type structure (space group I4/mmm), whereas EuCu 2Sb 2 crystallizes in the related primitive tetragonal CaBe 2Ge 2-type structure (space group P4/nmm). The energy-dispersive x-ray spectroscopy and XRD data for themore » EuCu 2Sb 2 crystals showed the presence of vacancies on the Cu sites, yielding the actual composition EuCu 1.82Sb 2. The ρ(T) and C p(T) data reveal metallic character for both EuCu 2As 2 and EuCu 1.82Sb 2. Antiferromagnetic (AFM) ordering is indicated from the χ(T),C p(T), and ρ(T) data for both EuCu 2As 2 (T N = 17.5 K) and EuCu 1.82Sb 2 (T N = 5.1 K). In EuCu 1.82Sb 2, the ordered-state χ(T) and M(H) data suggest either a collinear A-type AFM ordering of Eu +2 spins S = 7/2 or a planar noncollinear AFM structure, with the ordered moments oriented in the tetragonal ab plane in either case. This ordered-moment orientation for the A-type AFM is consistent with calculations with magnetic dipole interactions. As a result, the anisotropic χ(T) and isothermal M(H) data for EuCu 2As 2, also containing Eu +2 spins S = 7/2, strongly deviate from the predictions of molecular field theory for collinear AFM ordering and the AFM structure appears to be both noncollinear and noncoplanar.« less

  12. Metal Flux Growth, Structural Relations, and Physical Properties of EuCu2Ge2 and Eu3T2In9 (T = Cu and Ag).

    PubMed

    Subbarao, Udumula; Roy, Soumyabrata; Sarma, Saurav Ch; Sarkar, Sumanta; Mishra, Vidyanshu; Khulbe, Yatish; Peter, Sebastian C

    2016-10-17

    Single crystals (SCs) of the compounds Eu 3 Ag 2 In 9 and EuCu 2 Ge 2 were synthesized through the reactions run in liquid indium. Eu 3 Ag 2 In 9 crystallizes in the La 3 Al 11 structure type [orthorhombic space group (SG) Immm] with the lattice parameters: a = 4.8370(1) Å, b = 10.6078(3) Å, and c = 13.9195(4) Å. EuCu 2 Ge 2 crystallizes in the tetragonal ThCr 2 Si 2 structure type (SG I4/mmm) with the lattice parameters: a = b = 4.2218(1) Å, and c = 10.3394(5) Å. The crystal structure of Eu 3 Ag 2 In 9 is comprised of edge-shared hexagonal rings consisting of indium. The one-dimensional chains of In 6 rings are shared through the edges, which are further interconnected with other six-membered rings forming a three-dimensional (3D) stable crystal structure along the bc plane. The crystal structure of EuCu 2 Ge 2 can be explained as the complex [CuGe] (2+δ)- polyanionic network embedded with Eu ions. These polyanionic networks present in the crystal structure of EuCu 2 Ge 2 are shared through the edges of the 011 plane containing Cu and Ge atoms, resulting in a 3D network. The structural relationship between Eu 3 T 2 In 9 and EuCu 2 Ge 2 has been discussed in detail, and we conclude that Eu 3 T 2 In 9 is the metal deficient variant of EuCu 2 Ge 2 . The magnetic susceptibilities of Eu 3 T 2 In 9 (T = Cu and Ag) and EuCu 2 Ge 2 were measured between 2 and 300 K. In all cases, magnetic susceptibility data followed Curie-Weiss law above 150 K. Magnetic moment values obtained from the measurements indicate the probable mixed/intermediate valent behavior of the europium atoms, which was further confirmed by X-ray absorption studies and bond distances around the Eu atoms. Electrical resistivity measurements suggest that Eu 3 T 2 In 9 and EuCu 2 Ge 2 are metallic in nature.

  13. Corrosion and runoff rates of Cu and three Cu-alloys in marine environments with increasing chloride deposition rate.

    PubMed

    Odnevall Wallinder, Inger; Zhang, Xian; Goidanich, Sara; Le Bozec, Nathalie; Herting, Gunilla; Leygraf, Christofer

    2014-02-15

    Bare copper sheet and three commercial Cu-based alloys, Cu15Zn, Cu4Sn and Cu5Al5Zn, have been exposed to four test sites in Brest, France, with strongly varying chloride deposition rates. The corrosion rates of all four materials decrease continuously with distance from the coast, i.e. with decreasing chloride load, and in the following order: Cu4Sn>Cu sheet>Cu15Zn>Cu5Al5Zn. The patina on all materials was composed of two main layers, Cu2O as the inner layer and Cu2(OH)3Cl as the outer layer, and with a discontinuous presence of CuCl in between. Additional minor patina constituents are SnO2 (Cu4Sn), Zn5(OH)6(CO3)2 (Cu15Zn and Cu5Al5Zn) and Zn6Al2(OH)16CO3·4H2O/Zn2Al(OH)6Cl·2H2O/Zn5Cl2(OH)8·H2O and Al2O3 (Cu5Al5Zn). The observed Zn- and Zn/Al-containing corrosion products might be important factors for the lower sensitivity of Cu15Zn and Cu5Al5Zn against chloride-induced atmospheric corrosion compared with Cu sheet and Cu4Sn. Decreasing corrosion rates with exposure time were observed for all materials and chloride loads and attributed to an improved adherence with time of the outer patina to the underlying inner oxide. Flaking of the outer patina layer was mainly observed on Cu4Sn and Cu sheet and associated with the gradual transformation of CuCl to Cu2(OH)3Cl of larger volume. After three years only Cu5Al5Zn remains lustrous because of a patina compared with the other materials that appeared brownish-reddish. Significantly lower release rates of metals compared with corresponding corrosion rates were observed for all materials. Very similar release rates of copper from all four materials were observed during the fifth year of marine exposure due to an outer surface patina that with time revealed similar constituents and solubility properties. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

  14. Solid phase selective separation and preconcentration of Cu(II) by Cu(II)-imprinted polymethacrylic microbeads.

    PubMed

    Dakova, Ivanka; Karadjova, Irina; Ivanov, Ivo; Georgieva, Ventsislava; Evtimova, Bisera; Georgiev, George

    2007-02-12

    Ion-imprinted polymer (IIP) particles are prepared by copolymerization of methacrylic acid as monomer, trimethylolpropane trimethacrylate as crosslinking agent and 2,2'-azo-bis-isobutyronitrile as initiator in the presence of Cu(II), a Cu(II)-4-(2-pyridylazo)resorcinol (Cu(II)-PAR) complex, and PAR only. A batch procedure is used for the determination of the characteristics of the Cu(II) solid phase extraction from the IIP produced. The results obtained show that the Cu(II)-PAR IIP has the greatest adsorption capacity (37.4 micromol g(-1) of dry copolymer) among the IIPs investigated. The optimal pH value for the quantitative preconcentration is 7, and full desorption is achieved by 1 M HNO(3). The selectivity coefficients (S(Cu/Me)) for Me=Ni(II), Co(II) are 45.0 and 38.5, respectively. It is established that Cu(II)-PAR IIPs can be used repeatedly without a considerable adsorption capacity loss. The determination of Cu(II) ions in seawater shows that the interfering matrix does not influence the preconcentration and selectivity values of the Cu(II)-PAR IIPs. The detection and quantification limits are 0.001 micromol L(-1) (3sigma) and 0.003 micromol L(-1) (6sigma), respectively.

  15. Eco-friendly graphene synthesis on Cu foil electroplated by reusing Cu etchants

    PubMed Central

    Kwon, Ki Chang; Ham, Juyoung; Kim, Sungjun; Lee, Jong-Lam; Kim, Soo Young

    2014-01-01

    Graphene film grown by chemical vapor deposition using Cu substrate is promising for industrial applications. After etching the Cu substrate, which is essential step in graphene transfer process, the etchant solution must be chemically treated to prevent water pollution. Here we investigated that a method of reusing Cu etchant used to synthesize graphene, the synthesis of graphene on the resulting reused Cu films (R-G), and the application of R-G to organic light-emitting diodes (OLEDs) and organic photovoltaic cells (OPVs). The turn-on voltage of OLEDs based on the R-G electrode was 4.2 V, and the efficiencies of OPVs based on the R-G electrode were 5.9–5.95%, that are similar to or better than those of the indium-tin-oxide-based devices. These results suggest that the reusing of Cu foil by the electroplating method could reduce the cost of graphene synthesis, thus opening a wide range of applications in graphene electronics. PMID:24777344

  16. Structural and electronic snapshots during the transition from a Cu(II) to Cu(I) metal center of a lytic polysaccharide monooxygenase by X-ray photoreduction.

    PubMed

    Gudmundsson, Mikael; Kim, Seonah; Wu, Miao; Ishida, Takuya; Momeni, Majid Hadadd; Vaaje-Kolstad, Gustav; Lundberg, Daniel; Royant, Antoine; Ståhlberg, Jerry; Eijsink, Vincent G H; Beckham, Gregg T; Sandgren, Mats

    2014-07-04

    Lytic polysaccharide monooxygenases (LPMOs) are a recently discovered class of enzymes that employ a copper-mediated, oxidative mechanism to cleave glycosidic bonds. The LPMO catalytic mechanism likely requires that molecular oxygen first binds to Cu(I), but the oxidation state in many reported LPMO structures is ambiguous, and the changes in the LPMO active site required to accommodate both oxidation states of copper have not been fully elucidated. Here, a diffraction data collection strategy minimizing the deposited x-ray dose was used to solve the crystal structure of a chitin-specific LPMO from Enterococcus faecalis (EfaCBM33A) in the Cu(II)-bound form. Subsequently, the crystalline protein was photoreduced in the x-ray beam, which revealed structural changes associated with the conversion from the initial Cu(II)-oxidized form with two coordinated water molecules, which adopts a trigonal bipyramidal geometry, to a reduced Cu(I) form in a T-shaped geometry with no coordinated water molecules. A comprehensive survey of Cu(II) and Cu(I) structures in the Cambridge Structural Database unambiguously shows that the geometries observed in the least and most reduced structures reflect binding of Cu(II) and Cu(I), respectively. Quantum mechanical calculations of the oxidized and reduced active sites reveal little change in the electronic structure of the active site measured by the active site partial charges. Together with a previous theoretical investigation of a fungal LPMO, this suggests significant functional plasticity in LPMO active sites. Overall, this study provides molecular snapshots along the reduction process to activate the LPMO catalytic machinery and provides a general method for solving LPMO structures in both copper oxidation states. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

  17. Accurate characterization of wafer bond toughness with the double cantilever specimen

    NASA Astrophysics Data System (ADS)

    Turner, Kevin T.; Spearing, S. Mark

    2008-01-01

    The displacement loaded double cantilever test, also referred to as the "Maszara test" and the "crack opening method" by the wafer bonding community, is a common technique used to evaluate the interface toughness or surface energy of direct wafer bonds. While the specimen is widely used, there has been a persistent question as to the accuracy of the method since the actual specimen geometry differs from the ideal beam geometry assumed in the expression used for data reduction. The effect of conducting the test on whole wafer pairs, in which the arms of cantilevers are wide plates rather than slender beams, is examined in this work using finite element analysis. A model is developed to predict the equilibrium shape of the crack front and to develop a corrected expression for calculating interface toughness from crack length measurements obtained in tests conducted on whole wafer pairs. The finite element model, which is validated through comparison to experiments, demonstrates that using the traditional beam theory-based expressions for data reduction can lead to errors of up to 25%.

  18. A novel fabrication of Cu{sub 2}O@Cu{sub 7}S{sub 4} core-shell micro/nanocrystals from Cu{sub 2}O temples and enhanced photocatalytic activities

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Junqi, E-mail: sfmlab@163.com; Sun, Long; Yan, Ying

    2016-08-15

    Highlights: • The Cu{sub 2}O@Cu{sub 7}S{sub 4} core-shell crystals maintained the same morphology with template. • The crystals exhibit enhanced photocatalytic activity than the pure Cu{sub 2}O crystals. • The photocatalytic activity of different R crystals is diverse from each other. • A possible formation mechanism has been proposed. - Abstract: Uniform and monodispersed Cu{sub 2}O@Cu{sub 7}S{sub 4} core-shell micro/nanocrystals have been synthesized successfully at room temperature via a simple chemical etching reaction, using Cu{sub 2}O as sacrificial template. The structure and properties of the crystals were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM),more » X-ray photoelectron spectra (XPS). The photocatalytic activity of the Cu{sub 2}O@Cu{sub 7}S{sub 4} crystals was evaluated by photocatalytic decolorization of MeO (methyl orange) aqueous solution at ambient temperature under visible-light irradiation. The results show that the as-prepared Cu{sub 2}O@Cu{sub 7}S{sub 4} crystals revealed core-shell structure, which maintained the same morphology with corresponding template and were composed of cuboctahedron Cu{sub 7}S{sub 4} shell and active Cu{sub 2}O core. Due to the unique Cu{sub 2}O@Cu{sub 7}S{sub 4} core-shell structure, the crystals exhibit enhanced photocatalytic activity than that of the pure Cu{sub 2}O crystals, and the photocatalytic activity of different R crystals is diverse from each other. A possible formation mechanism has been proposed.« less

  19. First-principles study of roles of Cu and Cl in polycrystalline CdTe

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yang, Ji -Hui; Yin, Wan -Jian; Park, Ji -Sang

    2016-01-25

    In this study, Cu and Cl treatments are important processes to achieve high efficiency polycrystalline cadmium telluride (CdTe) solar cells, thus it will be beneficial to understand the roles they play in both bulk CdTe and CdTe grain boundaries (GBs). Using first-principles calculations, we systematically study Cu and Cl-related defects in bulk CdTe. We find that Cl has only a limited effect on improving p-type doping and too much Cl can induce deep traps in bulk CdTe, whereas Cu can enhance ptype doping of bulk CdTe. In the presence of GBs, we find that, in general, Cl and Cu willmore » prefer to stay at GBs, especially for those with Te-Te wrong bonds, in agreement with experimental observations.« less

  20. First-principles study of roles of Cu and Cl in polycrystalline CdTe

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yang, Ji-Hui; Park, Ji-Sang; Metzger, Wyatt

    2016-01-28

    Cu and Cl treatments are important processes to achieve high efficiency polycrystalline cadmium telluride (CdTe) solar cells, thus it will be beneficial to understand the roles they play in both bulk CdTe and CdTe grain boundaries (GBs). Using first-principles calculations, we systematically study Cu and Cl-related defects in bulk CdTe. We find that Cl has only a limited effect on improving p-type doping and too much Cl can induce deep traps in bulk CdTe, whereas Cu can enhance p-type doping of bulk CdTe. In the presence of GBs, we find that, in general, Cl and Cu will prefer to staymore » at GBs, especially for those with Te-Te wrong bonds, in agreement with experimental observations.« less

  1. Spatial part-set cuing facilitation.

    PubMed

    Kelley, Matthew R; Parasiuk, Yuri; Salgado-Benz, Jennifer; Crocco, Megan

    2016-07-01

    Cole, Reysen, and Kelley [2013. Part-set cuing facilitation for spatial information. Journal of Experimental Psychology: Learning, Memory, & Cognition, 39, 1615-1620] reported robust part-set cuing facilitation for spatial information using snap circuits (a colour-coded electronics kit designed for children to create rudimentary circuit boards). In contrast, Drinkwater, Dagnall, and Parker [2006. Effects of part-set cuing on experienced and novice chess players' reconstruction of a typical chess midgame position. Perceptual and Motor Skills, 102(3), 645-653] and Watkins, Schwartz, and Lane [1984. Does part-set cuing test for memory organization? Evidence from reconstructions of chess positions. Canadian Journal of Psychology/Revue Canadienne de Psychologie, 38(3), 498-503] showed no influence of part-set cuing for spatial information when using chess boards. One key difference between the two procedures was that the snap circuit stimuli were explicitly connected to one another, whereas chess pieces were not. Two experiments examined the effects of connection type (connected vs. unconnected) and cue type (cued vs. uncued) on memory for spatial information. Using chess boards (Experiment 1) and snap circuits (Experiment 2), part-set cuing facilitation only occurred when the stimuli were explicitly connected; there was no influence of cuing with unconnected stimuli. These results are potentially consistent with the retrieval strategy disruption hypothesis, as well as the two- and three-mechanism accounts of part-set cuing.

  2. Facile Fabrication of Cu2O Nanobelts in Ethanol on Nanoporous Cu and Their Photodegradation of Methyl Orange

    PubMed Central

    Yang, Yulin; Qin, Fengxiang; Wang, Hao; Chang, Hui

    2018-01-01

    Thin cupric oxide (Cu2O) nanobelts with width of few tens of nanometers to few hundreds of nanometers were fabricated in anhydrous ethanol on nanoporous copper templates that was prepared via dealloying amorphous Ti40Cu60 ribbons in hydrofluoric acid solutions at 348 K. The Cu2O octahedral particles preferentially form in the water, and nanobelts readily undergo the growth along the lengthwise and widthwise in the anhydrous ethanol. The ethanol molecules serve as stabilizing or capping reagents, and play a key role of the formation of two-dimensional Cu2O nanobelts. Cu atoms at weak sites (i.e., twin boundary) on the nanoporous Cu ligaments are ionized to form Cu2+ cations, and then react with OH− to form Cu2O and H2O. The two-dimensional growth of Cu2O nanostructure is preferred in anhydrous ethanol due to the suppression of random growth of Cu2O nanoarchitectures by ethanol. Cu2O nanobelts have superior photodegradation performance of methyl orange, three times higher than nanoporous Cu. PMID:29562692

  3. The influence of tumor oxygenation on hypoxia imaging in murine squamous cell carcinoma using [64Cu]Cu-ATSM or [18F]Fluoromisonidazole positron emission tomography.

    PubMed

    Matsumoto, Ken-Ichiro; Szajek, Lawrence; Krishna, Murali C; Cook, John A; Seidel, Jurgen; Grimes, Kelly; Carson, Joann; Sowers, Anastasia L; English, Sean; Green, Michael V; Bacharach, Stephen L; Eckelman, William C; Mitchell, James B

    2007-04-01

    [64Cu]Cu(II)-ATSM (64Cu-ATSM) and [18F]-Fluoromisonidazole (18F-FMiso) tumor binding as assessed by positron emisson topography (PET) was used to determine the responsiveness of each probe to modulation in tumor oxygenation levels in the SCCVII tumor model. Animals bearing the SCCVII tumor were injected with 64Cu-ATSM or 18F-FMiso followed by dynamic small animal PET imaging. Animals were imaged with both agents using different inspired oxygen mixtures (air, 10% oxygen, carbogen) which modulated tumor hypoxia as independently assessed by the hypoxia marker pimonidazole. The extent of hypoxia in the SCCVII tumor as monitored by the pimonidazole hypoxia marker was found to be in the following order: 10% oxygen>air>carbogen. Tumor uptake of 64Cu-ATSM could not be changed if the tumor was oxygenated using carbogen inhalation 90 min post-injection suggesting irreversible cellular uptake of the 64Cu-ATSM complex. A small but significant paradoxical increase in 64Cu-ATSM tumor uptake was observed for animals breathing air or carbogen compared to 10% oxygen. There was a positive trend toward 18F-FMiso tumor uptake as a function of changing hypoxia levels in agreement with the pimonidazole data. 64Cu-ATSM tumor uptake was unable to predictably detect changes in varying amounts of hypoxia when oxygenation levels in SCCVII tumors were modulated. 18F-FMiso tumor uptake was more responsive to changing levels of hypoxia. While the mechanism of nitroimidazole binding to hypoxic cells has been extensively studied, the avid binding of Cu-ATSM to tumors may involve other mechanisms independent of hypoxia that warrant further study.

  4. Toward Rational Design of Cu/SSZ-13 Selective Catalytic Reduction Catalysts: Implications from Atomic-Level Understanding of Hydrothermal Stability

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Song, James; Wang, Yilin; Walter, Eric D.

    The hydrothermal stability of Cu/SSZ-13 SCR catalysts has been extensively studied, yet atomic level understanding of changes to the zeolite support and the Cu active sites during hydrothermal aging are still lacking. In this work, via the utilization of spectroscopic methods including solid-state 27Al and 29Si NMR, EPR, DRIFTS, and XPS, together with imaging and elemental mapping using STEM, detailed kinetic analyses, and theoretical calculations with DFT, various Cu species, including two types of isolated active sites and CuOx clusters, were precisely quantified for samples hydrothermally aged under varying conditions. This quantification convincingly confirms the exceptional hydrothermal stability of isolatedmore » Cu2+-2Z sites, and the gradual conversion of [Cu(OH)]+-Z to CuOx clusters with increasing aging severity. This stability difference is rationalized from the hydrolysis activation barrier difference between the two isolated sites via DFT. Discussions are provided on the nature of the CuOx clusters, and their possible detrimental roles on catalyst stability. Finally, a few rational design principles for Cu/SSZ-13 are derived rigorously from the atomic-level understanding of this catalyst obtained here. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. Computing time was granted by a user proposal at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC). The experimental studies described in this paper were performed in the EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.« less

  5. Explanation of the photocurrent generation of Cu2O quantum dots (QDs) sensitized p-CuSCN stable photoelectrochemical cells

    NASA Astrophysics Data System (ADS)

    Karunarathna, P. G. D. C. K.; Samarakoon, S. P. A. U. K.; Fernando, C. A. N.

    2018-01-01

    Fabrication of Cu2O quantum dots (QDs) sensitized p-CuSCN photoelectrode provides a significant photocurrent enhancement in photoelectrochemical medium for the first time. The variation of photocurrent quantum efficiency (Ф%) with Cu2O amount formed on p-CuSCN was presented. Here, two maxima of photocurrent could be observed in Cu/p-CuSCN/Cu2O photoelectrodes. The first photocurrent peak was due to the Cu2O QDs sensitization on p-CuSCN layer, and the second photocurrent peak was due to the formation of p-n junction. Time development of the photocurrent for Cu/p-CuSCN/n-Cu2O photoelectrodes and material characterization from Fourier transform infrared (FTIR) spectra, scanning electron microscope (SEM) images, energy dispersive x-ray spectroscopy (EDX) and x-ray diffraction (XRD) were done in this study in detailed.

  6. Perpendicular Growth Characteristics of Cu-Sn Intermetallic Compounds at the Surface of 99Sn-1Cu/Cu Solder Interconnects

    NASA Astrophysics Data System (ADS)

    Chen, Zhiwen; Liu, Changqing; Wu, Yiping; An, Bing

    2015-12-01

    The growth of intermetallic compounds (IMCs) on the free surface of 99Sn-1Cu solder joints perpendicular to the interdiffusion direction has been investigated in this work. The specimens were specifically designed and polished to reveal a flat free surface at the solder/Cu interface for investigation. After aging at 175°C for progressively increased durations, the height of the perpendicular IMCs was examined and found to follow a parabolic law with aging duration that could be expressed as y = 0.11√ t, where t is the aging duration in hours and y is the height of the perpendicular IMCs in μm. For comparison, the planar growth of IMCs along the interdiffusion direction was also investigated in 99Sn-1Cu/Cu solder joints. After prolonged aging at 175°C, the thickness of the planar interfacial IMC layers also increased parabolically with aging duration and could be expressed as h_{{IMC}} = 0.27√ t + 4.6, where h is the thickness in μm and t is the time in hours. It was found that both the planar and perpendicular growth of the IMCs were diffusion-controlled processes, but the perpendicular growth of the IMCs was much slower than their planar growth due to the longer diffusion distance. It is proposed that Cu3Sn forms prior to the formation of Cu6Sn5 in the perpendicular IMCs, being the reverse order compared with the planar IMC growth.

  7. Superconductivity of Cu/CuOx interface formed by shock-wave pressure

    NASA Astrophysics Data System (ADS)

    Shakhray, D. V.; Avdonin, V. V.; Palnichenko, A. V.

    2016-11-01

    A mixture of powdered Cu and CuO has been subjected to shock-wave pressure of 350 kbar with following quenching of the vacuum-encapsulated product to 77 K. The ac magnetic susceptibility measurements of the samples have revealed metastable superconductivity with Tc ≈ 19 K, characterized by glassy dynamics of the shielding currents below Tc . Comparison of the ac susceptibility and the DC magnetization measurements infers that the superconductivity arises within the granular interfacial layer formed between metallic Cu and its oxides due to the shock-wave treatment.

  8. Physics of bandgap formation in Cu-Sb-Se based novel thermoelectrics: the role of Sb valency and Cu d levels.

    PubMed

    Do, Dat; Ozolins, Vidvuds; Mahanti, S D; Lee, Mal-Soon; Zhang, Yongsheng; Wolverton, C

    2012-10-17

    In this paper we discuss the results of ab initio electronic structure calculations for Cu(3)SbSe(4) (Se4) and Cu(3)SbSe(3) (Se3), two narrow bandgap semiconductors of thermoelectric interest. We find that Sb is trivalent in both the compounds, in contrast to a simple nominal valence (ionic) picture which suggests that Sb should be 5 + in Se4. The gap formation in Se4 is quite subtle, with hybridization between Sb 5s and the neighboring Se 4s, 4p orbitals, position of Cu d states, and non-local exchange interaction, each playing significant roles. Thermopower calculations show that Se4 is a better p-type system. Our theoretical results for Se4 agree very well with recent experimental results obtained by Skoug et al (2011 Sci. Adv. Mater. 3 602).

  9. Electronic, optical properties and chemical bonding in six novel 1111-like chalcogenide fluorides AMChF (A=Sr, Ba; M=Cu, Ag; and Ch=S, Se, Te) from first principles calculations

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bannikov, V.V.; Shein, I.R.; Ivanovskii, A.L., E-mail: ivanovskii@ihim.uran.ru

    2012-12-15

    Employing first-principles band structure calculations, we have examined the electronic, optical properties and the peculiarities of the chemical bonding for six newly synthesized layered quaternary 1111-like chalcogenide fluorides SrAgSF, SrAgSeF, SrAgTeF, BaAgSF, BaAgSeF, and SrCuTeF, which are discussed in comparison with some isostructural 1111-like chalcogenide oxides. We found that all of the studied phases AMChF (A=Sr, Ba; M=Cu, Ag; and Ch=S, Se, Te) are semiconductors for which the fitted 'experimental' gaps lie in the interval from 2.23 eV (for SrAgSeF) to 3.07 eV (for SrCuTeF). The near-Fermi states of AMChF are formed exclusively by the valence orbitals of the atomsmore » from the blocks (MCh); thus, these phases belong to the layered materials with 'natural multiple quantum wells'. The bonding in these new AMChF phases is described as a high-anisotropic mixture of ionic and covalent contributions, where ionic M-Ch bonds together with covalent M-Ch and Ch-Ch bonds take place inside blocks (MCh), while inside blocks (AF) and between the adjacent blocks (MCh)/(AF) mainly ionic bonds emerge. - Graphical Abstract: Isoelectronic surface for SrAgSeF and atomic-resolved densities of states for SrAgTeF, and SrCuTeF. Highlights: Black-Right-Pointing-Pointer Very recently six new layered 1111-like chalcogenide fluorides AMChF were synthesized. Black-Right-Pointing-Pointer Electronic, optical properties for AMChF phases were examined from first principles. Black-Right-Pointing-Pointer All these materials are characterized as non-magnetic semiconductors. Black-Right-Pointing-Pointer Bonding is highly anisotropic and includes ionic and covalent contributions. Black-Right-Pointing-Pointer Introduction of magnetic ions in AMChF is proposed for search of novel magnetic materials.« less

  10. Interface structure and properties of CNTs/Cu composites fabricated by electroless deposition and spark plasma sintering

    NASA Astrophysics Data System (ADS)

    Wang, Hu; Zhang, Zhao-Hui; Hu, Zheng-Yang; Song, Qi; Yin, Shi-Pan

    2018-01-01

    In this paper, we fabricated a novel copper matrix composites reinforced by carbon nanotubes (CNTs) using electroless deposition (ED) and spark plasma sintering technique. Microstructure, mechanical, electric conductivity, and thermal properties of the CNTs/Cu composites were investigated. The results show that a favorable interface containing C-O and O-Cu bond was formed between CNTs and matrix when the CNTs were coated with nano-Cu by ED method. Thus, we accomplished the uniformly dispersed CNTs in the CNTs/Cu powders and compacted composites, which eventually leads to the enhancement of the mechanical properties of the CNTs/Cu composites in the macro-scale environment. However, the interface structure can hinder the movement of carriers and free electrons and increase the interface thermal resistance, which leads to modest decrease of electrical and thermal conductivity of the CNTs/Cu composites.

  11. Valence-band and core-level photoemission study of single-crystal Bi2CaSr2Cu2O8 superconductors

    NASA Astrophysics Data System (ADS)

    Shen, Z.-X.; Lindberg, P. A. P.; Wells, B. O.; Mitzi, D. B.; Lindau, I.; Spicer, W. E.; Kapitulnik, A.

    1988-12-01

    High-quality single crystals of Bi2CaSr2Cu2O8 superconductors have been prepared and cleaved in ultrahigh vacuum. Low-energy electron diffraction measurements show that the surface structure is consistent with the bulk crystal structure. Ultraviolet photoemission and x-ray photoemission experiments were performed on these well-characterized sample surfaces. The valence-band and the core-level spectra obtained from the single-crystal surfaces are in agreement with spectra recorded from polycrystalline samples, justifying earlier results from polycrystalline samples. Cu satellites are observed both in the valence band and Cu 2p core level, signaling the strong correlation among the Cu 3d electrons. The O 1s core-level data exhibit a sharp, single peak at 529-eV binding energy without any clear satellite structures.

  12. Activation of CuZn superoxide dismutases from Caenorhabditis elegans does not require the copper chaperone CCS.

    PubMed

    Jensen, Laran T; Culotta, Valeria Cizewski

    2005-12-16

    Reactive oxygen species are produced as the direct result of aerobic metabolism and can cause damage to DNA, proteins, and lipids. A principal defense against reactive oxygen species involves the superoxide dismutases (SOD) that act to detoxify superoxide anions. Activation of CuZn-SODs in eukaryotic cells occurs post-translationally and is generally dependent on the copper chaperone for SOD1 (CCS), which inserts the catalytic copper cofactor and catalyzes the oxidation of a conserved disulfide bond that is essential for activity. In contrast to other eukaryotes, the nematode Caenorhabditis elegans does not contain an obvious CCS homologue, and we have found that the C. elegans intracellular CuZn-SODs (wSOD-1 and wSOD-5) are not dependent on CCS for activation when expressed in Saccharomyces cerevisiae. CCS-independent activation of CuZn-SODs is not unique to C. elegans; however, this is the first organism identified that appears to exclusively use this alternative pathway. As was found for mammalian SOD1, wSOD-1 exhibits a requirement for reduced glutathione in CCS-independent activation. Unexpectedly, wSOD-1 was inactive even in the presence of CCS when glutathione was depleted. Our investigation of the cysteine residues that form the disulfide bond in wSOD-1 suggests that the ability of wSODs to readily form this disulfide bond may be the key to obtaining high levels of activation through the CCS-independent pathway. Overall, these studies demonstrate that the CuZn-SODs of C. elegans have uniquely evolved to acquire copper without the copper chaperone and this may reflect the lifestyle of this organism.

  13. One-Step Catalytic Synthesis of CuO/Cu2O in a Graphitized Porous C Matrix Derived from the Cu-Based Metal-Organic Framework for Li- and Na-Ion Batteries.

    PubMed

    Kim, A-Young; Kim, Min Kyu; Cho, Keumnam; Woo, Jae-Young; Lee, Yongho; Han, Sung-Hwan; Byun, Dongjin; Choi, Wonchang; Lee, Joong Kee

    2016-08-03

    The hybrid composite electrode comprising CuO and Cu2O micronanoparticles in a highly graphitized porous C matrix (CuO/Cu2O-GPC) has a rational design and is a favorable approach to increasing the rate capability and reversible capacity of metal oxide negative materials for Li- and Na-ion batteries. CuO/Cu2O-GPC is synthesized through a Cu-based metal-organic framework via a one-step thermal transformation process. The electrochemical performances of the CuO/Cu2O-GPC negative electrode in Li- and Na-ion batteries are systematically studied and exhibit excellent capacities of 887.3 mAh g(-1) at 60 mA g(-1) after 200 cycles in a Li-ion battery and 302.9 mAh g(-1) at 50 mA g(-1) after 200 cycles in a Na-ion battery. The high electrochemical stability was obtained via the rational strategy, mainly owing to the synergy effect of the CuO and Cu2O micronanoparticles and highly graphitized porous C formed by catalytic graphitization of Cu nanoparticles. Owing to the simple one-step thermal transformation process and resulting high electrochemical performance, CuO/Cu2O-GPC is one of the prospective negative active materials for rechargeable Li- and Na-ion batteries.

  14. Loss of reserves of Cu in liver when Cu supplements are withdrawn from dairy herds in the Waikato region.

    PubMed

    Hittmann, A R; Grace, N D; Knowles, S O

    2012-03-01

    To monitor the consequences of withdrawing mineral Cu supplements from two dairy herds with initially high concentrations of Cu in liver. Two herds were selected from dairy farms in the Waikato region of New Zealand that participated in an earlier survey of Cu supplementation practices and Cu status of dairy cows. The herds were fed pasture, grass and maize silage, plus palm kernel expeller (PKE) containing 25-30 mg Cu/kg dry matter (DM) fed at 2-4 kg/cow/day. No mineral Cu supplements were supplied from January 2009. Pasture samples were collected for mineral analysis in September 2008 and April 2009. Concentration of Cu in liver biopsies from the same 9-10 cows per herd was measured on three occasions between April 2009 and May 2010. Pastures on both farms contained 10 mg Cu/kg DM, 0.1-0.5 mg Mo/kg DM and 3.5-4.0 g S/kg DM. The initial herd mean concentrations of Cu in liver were 1,500 (SD 590) and 1,250 (SD 640) μmol Cu/kg fresh tissue. In the absence of mineral Cu supplements, those mean concentrations decreased over 12 months to 705 (SD 370) and 1,120 (SD 560) μmol Cu/kg fresh tissue, respectively. For cows in the first herd, the rate of depletion of liver Cu reserves was influenced by initial concentration of Cu, such that high concentration led to faster loss according to first-order kinetics. Mineral Cu supplementation was not necessary over 12 months for two dairy herds with mean concentrations of Cu in liver >1,250 μmol Cu/kg fresh tissue, grazing pastures containing 10 mg Cu/kg DM and concentrations of Mo <1 mg/kg DM. The quantity and particularly the duration of feeding PKE appeared to be a factor in whether or not the herd lost substantial reserves of Cu in liver during the year. However, the Cu status of both herds in this study was more than adequate to support late pregnancy and mating. CLINICAL REVELANCE: Copper status of the herd should be monitored and on-farm management of Cu nutrition should take into account all sources contributing to

  15. Low-Temperature Bonding of Bi0.5Sb1.5Te3 Thermoelectric Material with Cu Electrodes Using a Thin-Film In Interlayer

    NASA Astrophysics Data System (ADS)

    Lin, Yan-Cheng; Yang, Chung-Lin; Huang, Jing-Yi; Jain, Chao-Chi; Hwang, Jen-Dong; Chu, Hsu-Shen; Chen, Sheng-Chi; Chuang, Tung-Han

    2016-09-01

    A Bi0.5Sb1.5Te3 thermoelectric material electroplated with a Ni barrier layer and a Ag reaction layer was bonded with a Ag-coated Cu electrode at low temperatures of 448 K (175 °C) to 523 K (250 °C) using a 4- μm-thick In interlayer under an external pressure of 3 MPa. During the bonding process, the In thin film reacted with the Ag layer to form a double layer of Ag3In and Ag2In intermetallic compounds. No reaction occurred at the Bi0.5Sb1.5Te3/Ni interface, which resulted in low bonding strengths of about 3.2 MPa. The adhesion of the Bi0.5Sb1.5Te3/Ni interface was improved by precoating a 1- μm Sn film on the surface of the thermoelectric element and preheating it at 523 K (250 °C) for 3 minutes. In this case, the bonding strengths increased to a range of 9.1 to 11.5 MPa after bonding at 473 K (200 °C) for 5 to 60 minutes, and the shear-tested specimens fractured with cleavage characteristics in the interior of the thermoelectric material. The bonding at 448 K (175 °C) led to shear strengths ranging from 7.1 to 8.5 MPa for various bonding times between 5 and 60 minutes, which were further increased to the values of 10.4 to 11.7 MPa by increasing the bonding pressure to 9.8 MPa. The shear strengths of Bi0.5Sb1.5Te3/Cu joints bonded with the optimized conditions of the modified solid-liquid interdiffusion bonding process changed only slightly after long-term exposure at 473 K (200 °C) for 1000 hours.

  16. Transient Liquid Phase Bonding of Cu-Cr-Zr-Ti Alloy Using Ni and Mn Coatings: Microstructural Evolution and Mechanical Properties

    NASA Astrophysics Data System (ADS)

    Venkateswaran, T.; Ravi, K. R.; Sivakumar, D.; Pant, Bhanu; Janaki Ram, G. D.

    2017-08-01

    High-strength copper alloys are used extensively in the regenerative cooling parts of aerospace structures. Transient liquid phase (TLP) bonding of a Cu-Cr-Zr-Ti alloy was attempted in the present study using thin layers of elemental Ni and Mn coatings applied by electroplating. One of the base metals was given a Ni coating of 4 µm followed by a Mn coating of 15 µm, while the other base metal was given only the Ni coating (4 µm). The bonding cycle consisted of the following: TLP stage—heating to 1030 °C and holding for 15 min; homogenization stage—furnace cooling to 880 °C and holding for 2 h followed by argon quenching to room temperature. Detailed microscopy and electron probe microanalysis analysis of the brazed joints were carried out. The braze metal was found to undergo isothermal solidification within the 15 min of holding time at 1030 °C. At the end of TLP stage, the braze metal showed a composition of Cu-17Ni-9Mn (wt.%) at the center of the joint with a steep gradient in Ni and Mn concentrations from the center of the braze metal to the base metal interfaces. After holding for 2 h at 880 °C (homogenization stage), the compositional gradients were found to flatten significantly and the braze metal was found to develop a homogeneous composition of Cu-11Ni-7Mn (wt.%) at the center of the joint. In lap-shear tests, failures were always found to occur in the base metal away from the brazed region. The copper alloy base metal was found to undergo significant grain coarsening due to high-temperature exposure during brazing and, consequently, suffer considerable reduction in yield strength.

  17. Reaction pathways of furfural, furfuryl alcohol and 2-methylfuran on Cu(111) and NiCu bimetallic surfaces

    DOE PAGES

    Xiong, Ke; Wan, Weiming; Chen, Jingguang G.

    2016-02-23

    Hydrodeoxygenation (HDO) is an important reaction for converting biomass-derived furfural to value-added 2-methylfuran, which is a promising fuel additive. In this work, the HDO of furfural to produce 2-methylfuran occurred on the NiCu bimetallic surfaces prepared on either Ni(111) or Cu(111). The reaction pathways of furfural were investigated on Cu(111) and Ni/Cu(111) surfaces using density functional theory (DFT) calculations, temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS) experiments. These studies provided mechanistic insights into the effects of bimetallic formation on enhancing the HDO activity. Specifically, furfural weakly adsorbed on Cu(111), while it strongly adsorbed on Ni/Cu(111)more » through an η 2(C,O) configuration which led to the HDO of furfural on Ni/Cu(111). Lastly, the ability to dissociate H 2 on Ni/Cu(111) is also an important factor for enhancing the HDO activity over Cu(111).« less

  18. Reaction pathways of furfural, furfuryl alcohol and 2-methylfuran on Cu(111) and NiCu bimetallic surfaces

    NASA Astrophysics Data System (ADS)

    Xiong, Ke; Wan, Weiming; Chen, Jingguang G.

    2016-10-01

    Hydrodeoxygenation (HDO) is an important reaction for converting biomass-derived furfural to value-added 2-methylfuran, which is a promising fuel additive. In this work, the HDO of furfural to produce 2-methylfuran occurred on the NiCu bimetallic surfaces prepared on either Ni(111) or Cu(111). The reaction pathways of furfural were investigated on Cu(111) and Ni/Cu(111) surfaces using density functional theory (DFT) calculations, temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) experiments. These studies provided mechanistic insights into the effects of bimetallic formation on enhancing the HDO activity. Specifically, furfural weakly adsorbed on Cu(111), while it strongly adsorbed on Ni/Cu(111) through an η2(C,O) configuration, which led to the HDO of furfural on Ni/Cu(111). The ability to dissociate H2 on Ni/Cu(111) is also an important factor for enhancing the HDO activity over Cu(111).

  19. CuO nanowire/microflower/nanowire modified Cu electrode with enhanced electrochemical performance for non-enzymatic glucose sensing.

    PubMed

    Li, Changli; Yamahara, Hiroyasu; Lee, Yaerim; Tabata, Hitoshi; Delaunay, Jean-Jacques

    2015-07-31

    CuO nanowire/microflower structure on Cu foil is synthesized by annealing a Cu(OH)2 nanowire/CuO microflower structure at 250 °C in air. The nanowire/microflower structure with its large surface area leads to an efficient catalysis and charge transfer in glucose detection, achieving a high sensitivity of 1943 μA mM(-1) cm(-2), a wide linear range up to 4 mM and a low detection limit of 4 μM for amperometric glucose sensing in alkaline solution. With a second consecutive growth of CuO nanowires on the microflowers, the sensitivity of the obtained CuO nanowire/microflower/nanowire structure further increases to 2424 μA mM(-1) cm(-2), benefiting from an increased number of electrochemically active sites. The enhanced electrocatalytic performance of the CuO nanowire/microflower/nanowire electrode compared to the CuO nanowire/microflower electrode, CuO nanowire electrode and CuxO film electrode provides evidence for the significant role of available surface area for electrocatalysis. The rational combination of CuO nanowire and microflower nanostructures into a nanowire supporting microflower branching nanowires structure makes it a promising composite nanostructure for use in CuO based electrochemical sensors with promising analytical properties.

  20. Ni Nanobuffer Layer Provides Light-Weight CNT/Cu Fibers with Superior Robustness, Conductivity, and Ampacity.

    PubMed

    Zou, Jingyun; Liu, Dandan; Zhao, Jingna; Hou, Ligan; Liu, Tong; Zhang, Xiaohua; Zhao, Yonghao; Zhu, Yuntian T; Li, Qingwen

    2018-03-07

    Carbon nanotube (CNT) fiber has not shown its advantage as next-generation light-weight conductor due to the large contact resistance between CNTs, as reflected by its low conductivity and ampacity. Coating CNT fiber with a metal layer like Cu has become an effective solution to this problem. However, the weak CNT-Cu interfacial bonding significantly limits the mechanical and electrical performances. Here, we report that a strong CNT-Cu interface can be formed by introducing a Ni nanobuffer layer before depositing the Cu layer. The Ni nanobuffer layer remarkably promotes the load and heat transfer efficiencies between the CNT fiber and Cu layer and improves the quality of the deposited Cu layer. As a result, the new composite fiber with a 2 μm thick Cu layer can exhibit a superhigh effective strength >800 MPa, electrical conductivity >2 × 10 7 S/m, and ampacity >1 × 10 5 A/cm 2 . The composite fiber can also sustain 10 000 times of bending and continuously work for 100 h at 90% ampacity.

  1. Ab initio X-ray absorption modeling of Cu-SAPO-34: Characterization of Cu exchange sites under different conditions

    DOE PAGES

    Zhang, Renqin; Helling, Kathy; McEwen, Jean-Sabin

    2016-03-29

    Copper-exchanged SAPO-34 (Cu-SAPO-34) provides excellent catalytic activity and hydrothermal sta-bility in the selective catalytic reduction (SCR) of NOxby using NH3as a reductant. Here, we find that the6-membered ring (6MR) site is the most energetically favorable for a Cu+ion while the 8-memberedring (8MR) sites are less favorable by about 0.5 eV with respect to the 6MR site in Cu-SAPO-34. Uponadsorption of molecular species (H2O, O, OH, O2), the energy differences between Cu in the 8MR and 6MRsites decreases and almost disappears. Further, a thermodynamic phase diagram study shows that a Cu+ion bound to a single H2O molecule is the most stablemore » species at low oxygen potential values while aCu2+ion bound to 2 OH species is more stable when the oxygen chemical potential is sufficiently high. Bycomparing Cu K-edge XANES between Cu-SSZ-13 and Cu-SAPO-34 with Cu in different oxidation states,we conclude that it is difficult to differentiate the simulated XANES of Cu in these structures at a givenoxidation state. By studying the Cu K-edge XANES of several favorable structures in Cu-SAPO-34 in thepresence of adspecies, the simulated XANES results capture the real trend of the edge shift with oxidationstate and gives new insights into the experimentally determined XANES of Cu-SAPO-34 obtained understandard SCR conditions.« less

  2. Structure and magnetism of [n-BuNH3]12[Cu4(GeW9O34)2].14H2O sandwiching a rhomblike Cu4(8+) tetragon through alpha-Keggin linkage.

    PubMed

    Yamase, Toshihiro; Abe, Hiroko; Ishikawa, Eri; Nojiri, Hiroyuki; Ohshima, Yuhgo

    2009-01-05

    A sandwich-type polyoxometalate, [Cu(4)(GeW(9)O(34))(2)](12-) (1a), in which two B-alpha-[GeW(9)O(34)](12-) ligands sandwich a rhomblike Cu(4)(8+) tetragon through alpha-Kappaeggin linkage, is first isolated as a [n-BuNH(3)](+) salt, [n-BuNH(3)](12)[Cu(4)(GeW(9)O(34))(2)].14H(2)O (1). A Cu(4)O(14) cluster for the rhomblike Cu(4)(8+) tetragon in 1a with C(2h) local symmetry consists of two Jahn-Teller (JT) distorted CuO(6) octahedra (at internal sites) with a short diagonal Cu(int)...Cu(int) distance of 3.10-3.11 A and two CuO(5) square pyramids (at external site) with a long diagonal Cu(ext)...Cu(ext) distance of 5.34-5.35 A, the feature of which is different from [Cu(4)(H(2)O)(2)(GeW(9)O(34))(2)](12-) (2a), comprising the four JT-distorted CuO(6) octahedral Cu(4)(8+) tetragons through beta-Keggin linkage: the axial Cu(ext)-O bond distance (2.27-2.29 A) for 1a is shorter than the corresponding JT-axial distance (2.36 A) for 2a. Measurements of magnetic susceptibility, magnetization, and electron spin resonance spectroscopy for 1 are carried out for better understanding of the molecular magnetism of the Cu(4)(8+) tetragon in comparison with 2a. The analysis of the magnetic behavior, based on the isotropic Heisenberg spin Hamiltonian comprising three exchange parameters (J, J', and J''), gives J = -24.1 cm(-1) for the Cu(ext)..Cu(int) sides, J' = -99.1 cm(-1) for the Cu(int)...Cu(int) diagonal, and J'' = +0.04 cm(-1) for the Cu(ext)...Cu(ext) diagonal of the Cu(4)(8+) rhombus. The S = 1 ground state of 1 displays g(||) = 2.42, g( perpendicular)= 2.07, D = -1.44 x 10(-2) cm(-1), and |A(Cu||)| = 46.5 x 10(-4) cm(-1). An observation of the asymmetric magnetization between a positive and a negative pulsed field (up to 10(3) T/s) at 0.5 K on the hysteresis loop indicates the quantum tunneling at zero field. The magnetic exchange interactions of four unpaired d(x(2)-y(2))-electron spins are discussed in terms of the point-dipole approximation, and the primary contribution

  3. Distinct oxidative cleavage and modification of bovine [Cu-Zn]-SOD by an ascorbic acid/Cu(II) system: Identification of novel copper binding site on SOD molecule

    PubMed Central

    Uehara, Hiroshi; Luo, Shen; Aryal, Baikuntha; Levine, Rodney L.; Rao, V. Ashutosh

    2016-01-01

    We investigated the combined effect of ascorbate and copper [Asc/Cu(II)] on the integrity of bovine [Cu-Zn]-superoxide dismutase (bSOD1) as a model system to study the metal catalyzed oxidation (MCO) and fragmentation of proteins. We found Asc/Cu(II) mediates specific cleavage of bSOD1 and generates 12.5 and 3.2 kDa fragments in addition to oxidation/carbonylation of the protein. The effect of other tested transition metals, a metal chelator, and hydrogen peroxide on the cleavage and oxidation indicated that binding of copper to a previously unknown site on SOD1 is responsible for the Asc/Cu(II) specific cleavage and oxidation. We utilized tandem mass spectrometry to identify the specific cleavage sites of Asc/Cu(II)-treated bSOD1. Analyses of tryptic- and AspN-peptides have demonstrated the cleavage to occur at Gly31 with peptide bond breakage with Thr30 and Ser32 through diamide and α-amidation pathways, respectively. The three-dimensional structure of bSOD1 reveals the imidazole ring of His19 localized within 5 Angstrom from the α-carbon of Gly31 providing a structural basis that copper ion, most likely coordinated by His19, catalyzes the specific cleavage reaction. PMID:26872685

  4. Distinct oxidative cleavage and modification of bovine [Cu- Zn]-SOD by an ascorbic acid/Cu(II) system: Identification of novel copper binding site on SOD molecule.

    PubMed

    Uehara, Hiroshi; Luo, Shen; Aryal, Baikuntha; Levine, Rodney L; Rao, V Ashutosh

    2016-05-01

    We investigated the combined effect of ascorbate and copper [Asc/Cu(II)] on the integrity of bovine [Cu-Zn]-superoxide dismutase (bSOD1) as a model system to study the metal catalyzed oxidation (MCO) and fragmentation of proteins. We found Asc/Cu(II) mediates specific cleavage of bSOD1 and generates 12.5 and 3.2kDa fragments in addition to oxidation/carbonylation of the protein. The effect of other tested transition metals, a metal chelator, and hydrogen peroxide on the cleavage and oxidation indicated that binding of copper to a previously unknown site on SOD1 is responsible for the Asc/Cu(II) specific cleavage and oxidation. We utilized tandem mass spectrometry to identify the specific cleavage sites of Asc/Cu(II)-treated bSOD1. Analyses of tryptic- and AspN-peptides have demonstrated the cleavage to occur at Gly31 with peptide bond breakage with Thr30 and Ser32 through diamide and α-amidation pathways, respectively. The three-dimensional structure of bSOD1 reveals the imidazole ring of His19 localized within 5Å from the α-carbon of Gly31 providing a structural basis that copper ion, most likely coordinated by His19, catalyzes the specific cleavage reaction. Published by Elsevier Inc.

  5. Investigating the atomic level influencing factors of glass forming ability in NiAl and CuZr metallic glasses

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sedighi, Sina; Kirk, Donald Walter; Singh, Chandra Veer, E-mail: chandraveer.singh@utoronto.ca

    2015-09-21

    Bulk metallic glasses are a relatively new class of amorphous metal alloy which possess unique mechanical and magnetic properties. The specific concentrations and combinations of alloy elements needed to prevent crystallization during melt quenching remains poorly understood. A correlation between atomic properties that can explain some of the previously identified glass forming ability (GFA) anomalies of the NiAl and CuZr systems has been identified, with these findings likely extensible to other transition metal–transition metal and transition metal–metalloid (TM–M) alloy classes as a whole. In this work, molecular dynamics simulation methods are utilized to study thermodynamic, kinetic, and structural properties ofmore » equiatomic CuZr and NiAl metallic glasses in an attempt to further understand the underlying connections between glass forming ability, nature of atomic level bonding, short and medium range ordering, and the evolution of structure and relaxation properties in the disordered phase. The anomalous breakdown of the fragility parameter as a useful GFA indicator in TM–M alloy systems is addressed through an in-depth investigation of bulk stiffness properties and the evolution of (pseudo)Gruneisen parameters over the quench domain, with the efficacy of other common glass forming ability indicators similarly being analyzed through direct computation in respective CuZr and NiAl systems. Comparison of fractional liquid-crystal density differences in the two systems revealed 2-3 times higher values for the NiAl system, providing further support for its efficacy as a general purpose GFA indicator.« less

  6. Studies of Cu adatom island ripening on Cu(100) by LEEM

    NASA Astrophysics Data System (ADS)

    Bussmann, Ezra; Kellogg, Gary L.

    2007-03-01

    Simple metal surfaces are model systems for characterizing kinetic processes governing the growth and stability of nanoscale structures. It is generally presumed that diffusive transport of adatoms across terraces determines the rate of these processes. However, STM studies in the temperature range T˜330-420 K reveal that transport between step edges on the Cu(100) surface is limited by detachment barriers at the step edges, rather than by the adatom diffusion barrier.^1 This is because on the Cu(100) surface, mass transport is mediated primarily by vacancies, instead of adatoms. We have used low energy electron microscopy (LEEM) movies to characterize coarsening of Cu islands on the Cu(100) surface in the range T˜460-560 K. By measuring the temperature dependence of the island decay rate we find an activation barrier of 0.9±0.1 eV. This value is comparable to the 0.80±0.03 eV barrier found in STM studies.^1 However, we are not able to conclude that transport is entirely detachment limited at these elevated temperatures. This work serves as background to establish whether or not Pd alloying in the Cu(100) surface will slow Cu surface transport. ^2 1. C. Kl"unker, et al., PRB 58, R7556 (1998). 2. M. L. Grant, et al., PRL 86, 4588 (2001). Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the U.S. DOE NNSA, Contract No. DE-AC04-94AL85000.

  7. Syntheses, structures, and properties of imidazolate-bridged Cu(II)-Cu(II) and Cu(II)-Zn(II) dinuclear complexes of a single macrocyclic ligand with two hydroxyethyl pendants.

    PubMed

    Li, Dongfeng; Li, Shuan; Yang, Dexi; Yu, Jiuhong; Huang, Jin; Li, Yizhi; Tang, Wenxia

    2003-09-22

    The imidazolate-bridged homodinuclear Cu(II)-Cu(II) complex, [(CuimCu)L]ClO(4).0.5H(2)O (1), and heterodinuclear Cu(II)-Zn(II) complex, [(CuimZnL(-)(2H))(CuimZnL(-)(H))](ClO(4))(3) (2), of a single macrocyclic ligand with two hydroxyethyl pendants, L (L = 3,6,9,16,19,22-hexaaza-6,19-bis(2-hydroxyethyl)tricyclo[22,2,2,2(11,14)]triaconta-1,11,13,24,27,29-hexaene), have been synthesized as possible models for copper-zinc superoxide dismutase (Cu(2),Zn(2)-SOD). Their crystal structures analyzed by X-ray diffraction methods have shown that the structures of the two complexes are markedly different. Complex 1 crystallizes in the orthorhombic system, containing an imidazolate-bridged dicopper(II) [Cu-im-Cu](3+) core, in which the two copper(II) ions are pentacoordinated by virtue of an N4O environment with a Cu.Cu distance of 5.999(2) A, adopting the geometry of distorted trigonal bipyramid and tetragonal pyramid, respectively. Complex 2 crystallizes in the triclinic system, containing two similar Cu-im-Zn cores in the asymmetric unit, in which both the Cu(II) and Zn(II) ions are pentacoordinated in a distorted trigonal bipyramid geometry, with the Cu.Zn distance of 5.950(1)/5.939(1) A, respectively. Interestingly, the macrocyclic ligand with two arms possesses a chairlike (anti) conformation in complex 1, but a boatlike (syn) conformation in complex 2. Magnetic measurements and ESR spectroscopy of complex 1 have revealed the presence of an antiferromagnetic exchange interaction between the two Cu(II) ions. The ESR spectrum of the Cu(II)-Zn(II) heterodinuclear complex 2 displayed a typical signal for mononuclear trigonal bipyramidal Cu(II) complexes. From pH-dependent ESR and electronic spectroscopic studies, the imidazolate bridges in the two complexes have been found to be stable over broad pH ranges. The cyclic voltammograms of the two complexes have been investigated. Both of the two complexes can catalyze the dismutation of superoxide and show rather high activity.

  8. Growth of Pt/Cu(100): An Atomistic Modeling Comparison with the Pd/Cu(100) Surface Alloy

    NASA Technical Reports Server (NTRS)

    Demarco, Gustavo; Garces, Jorge E.; Bozzolo, Guillermo

    2002-01-01

    The Bozzolo, Ferrante, and Smith (BFS) method for alloys is applied to the study of Pt deposition on Cu(100). The formation of a Cu-Pt surface alloy is discussed within the framework of previous results for Pd/Cu(100). In spite of the fact that both Pd and Pt share the same basic behavior when deposited on Cu, it is seen that subtle differences become responsible for the differences in growth observed at higher cover-ages. In agreement with experiment, all the main features of Pt/Cu(100) and Pd/Cu(100) are obtained by means of a simple modeling scheme, and explained in terms of a few basic ingredients that emerge from the BFS analysis.

  9. I-line stepper based overlay evaluation method for wafer bonding applications

    NASA Astrophysics Data System (ADS)

    Kulse, P.; Sasai, K.; Schulz, K.; Wietstruck, M.

    2018-03-01

    In the last decades the semiconductor technology has been driven by Moore's law leading to high performance CMOS technologies with feature sizes of less than 10 nm [1]. It has been pointed out that not only scaling but also the integration of novel components and technology modules into CMOS/BiCMOS technologies is becoming more attractive to realize smart and miniaturized systems [2]. Driven by new applications in the area of communication, health and automation, new components and technology modules such as BiCMOS embedded RF-MEMS, high-Q passives, Sibased microfluidics and InP-SiGe BiCMOS heterointegration have been demonstrated [3-6]. In contrast to standard VLSI processes fabricated on front side of the silicon wafer, these new technology modules additionally require to process the backside of the wafer; thus require an accurate alignment between the front and backside of the wafer. In previous work an advanced back to front side alignment technique and implementation into IHP's 0.25/0.13 µm high performance SiGe:C BiCMOS backside process module has been presented [7]. The developed technique enables a high resolution and accurate lithography on the backside of BiCMOS wafer for additional backside processing. In addition to the aforementioned back side process technologies, new applications like Through-Silicon Vias (TSV) for interposers and advanced substrate technologies for 3D heterogeneous integration demand not only single wafer fabrication but also processing of wafer stacks provided by temporary and permanent wafer bonding [8-9]. In this work, the non-contact infrared alignment system of the Nikon® i-line Stepper NSR-SF150 for both alignment and the overlay determination of bonded wafer stacks with embedded alignment marks are used to achieve an accurate alignment between the different wafer sides. The embedded field image alignment (FIA) marks of the interface and the device wafer top layer are measured in a single measurement job. By taking the

  10. Response time modeling reveals multiple contextual cuing mechanisms.

    PubMed

    Sewell, David K; Colagiuri, Ben; Livesey, Evan J

    2017-08-24

    Contextual cuing refers to a response time (RT) benefit that occurs when observers search through displays that have been repeated over the course of an experiment. Although it is generally agreed that contextual cuing arises via an associative learning mechanism, there is uncertainty about the type(s) of process(es) that allow learning to influence RT. We contrast two leading accounts of the contextual cuing effect that differ in terms of the general process that is credited with producing the effect. The first, the expedited search account, attributes the cuing effect to an increase in the speed with which the target is acquired. The second, the decision threshold account, attributes the cuing effect to a reduction in the response threshold used by observers when making a subsequent decision about the target (e.g., judging its orientation). We use the diffusion model to contrast the quantitative predictions of these two accounts at the level of individual observers. Our use of the diffusion model allows us to also explore a novel decision-level locus of the cuing effect based on perceptual learning. This novel account attributes the RT benefit to a perceptual learning process that increases the quality of information used to drive the decision process. Our results reveal both individual differences in the process(es) involved in contextual cuing but also identify several striking regularities across observers. We find strong support for both the decision threshold account as well as the novel perceptual learning account. We find relatively weak support for the expedited search account.

  11. Electrochemical properties and structures of the mixed-valence lithium cuprates Li 3Cu 2O 4 and Li 2NaCu 2O 4

    NASA Astrophysics Data System (ADS)

    Raekelboom, E. A.; Hector, A. L.; Weller, M. T.; Owen, J. R.

    The electrochemical performances of Li 3Cu 2O 4 and Li 2NaCu 2O 4 as cathode materials in lithium coin type batteries have been studied. In Li 3Cu 2O 4, the copper was oxidised to the III level when cycling. The replacement of the lithium by the sodium ions in the octahedral sites in Li 2NaCu 2O 4 might have an effect on the pathway of the lithium ions during the (de)intercalations.

  12. Metal-ligand delocalization and spin density in the CuCl2 and [CuCl4](2-) molecules: Some insights from wave function theory.

    PubMed

    Giner, Emmanuel; Angeli, Celestino

    2015-09-28

    The aim of this paper is to unravel the physical phenomena involved in the calculation of the spin density of the CuCl2 and [CuCl4](2-) systems using wave function methods. Various types of wave functions are used here, both variational and perturbative, to analyse the effects impacting the spin density. It is found that the spin density on the chlorine ligands strongly depends on the mixing between two types of valence bond structures. It is demonstrated that the main difficulties found in most of the previous studies based on wave function methods come from the fact that each valence bond structure requires a different set of molecular orbitals and that using a unique set of molecular orbitals in a variational procedure leads to the removal of one of them from the wave function. Starting from these results, a method to compute the spin density at a reasonable computational cost is proposed.

  13. Study on the formation of graphene by ion implantation on Cu, Ni and CuNi alloy

    NASA Astrophysics Data System (ADS)

    Kim, Janghyuk; Kim, Hong-Yeol; Jeon, Jeong Heum; An, Sungjoo; Hong, Jongwon; Kim, Jihyun

    2018-09-01

    This study identifies the details for direct synthesis of graphene by carbon ion implantation on Cu, Ni and CuNi alloy. Firstly, diffusion and concentration of carbon atoms in Cu and Ni are estimated separately. The concentrations of carbon atoms near the surfaces of Cu and Ni after carbon ion implantation and subsequent thermal annealing were correlated with the number of atoms and with the coverage or thickness of graphene. Systematic experiments showed that the Cu has higher carbon diffusivity and graphene coverage than Ni but higher temperatures and longer annealing times are required to synthesize graphene, similar to those in chemical vapor deposition method. The CuNi system shows better graphene coverage and quality than that on a single metal catalyst even after a short annealing time, as it has larger carbon diffusivity and lower carbon solubility than Ni and shows lower activation energy than Cu.

  14. Magnetic behaviour of multisegmented FeCoCu/Cu electrodeposited nanowires

    NASA Astrophysics Data System (ADS)

    Núñez, A.; Pérez, L.; Abuín, M.; Araujo, J. P.; Proenca, M. P.

    2017-04-01

    Understanding the magnetic behaviour of multisegmented nanowires (NWs) is a major key for the application of such structures in future devices. In this work, magnetic/non-magnetic arrays of FeCoCu/Cu multilayered NWs electrodeposited in nanoporous alumina templates are studied. Contrarily to most reports on multilayered NWs, the magnetic layer thickness was kept constant (30 nm) and only the non-magnetic layer thickness was changed (0 to 80 nm). This allowed us to tune the interwire and intrawire interactions between the magnetic layers in the NW array creating a three-dimensional (3D) magnetic system without the need to change the template characteristics. Magnetic hysteresis loops, measured with the applied field parallel and perpendicular to the NWs’ long axis, showed the effect of the non-magnetic Cu layer on the overall magnetic properties of the NW arrays. In particular, introducing Cu layers along the magnetic NW axis creates domain wall nucleation sites that facilitate the magnetization reversal of the wires, as seen by the decrease in the parallel coercivity and the reduction of the perpendicular saturation field. By further increasing the Cu layer thickness, the interactions between the magnetic segments, both along the NW axis and of neighbouring NWs, decrease, thus rising again the parallel coercivity and the perpendicular saturation field. This work shows how one can easily tune the parallel and perpendicular magnetic properties of a 3D magnetic layer system by adjusting the non-magnetic layer thickness.

  15. Moisture barrier properties of single-layer graphene deposited on Cu films for Cu metallization

    NASA Astrophysics Data System (ADS)

    Gomasang, Ploybussara; Abe, Takumi; Kawahara, Kenji; Wasai, Yoko; Nabatova-Gabain, Nataliya; Thanh Cuong, Nguyen; Ago, Hiroki; Okada, Susumu; Ueno, Kazuyoshi

    2018-04-01

    The moisture barrier properties of large-grain single-layer graphene (SLG) deposited on a Cu(111)/sapphire substrate are demonstrated by comparing with the bare Cu(111) surface under an accelerated degradation test (ADT) at 85 °C and 85% relative humidity (RH) for various durations. The change in surface color and the formation of Cu oxide are investigated by optical microscopy (OM) and X-ray photoelectron spectroscopy (XPS), respectively. First-principle simulation is performed to understand the mechanisms underlying the barrier properties of SLG against O diffusion. The correlation between Cu oxide thickness and SLG quality are also analyzed by spectroscopic ellipsometry (SE) measured on a non-uniform SLG film. SLG with large grains shows high performance in preventing the Cu oxidation due to moisture during ADT.

  16. Thermoelectric transport properties of PbTe-based composites incorporated with Cu2Se nano-inclusions

    NASA Astrophysics Data System (ADS)

    Guo, Haifeng; Xin, Hongxing; Qin, Xiaoying; Jian, Zhang; Li, Di; Li, Yuanyue; Li, Cong

    2016-02-01

    Thermoelectric transport properties of Lead telluride (PbTe)-based composites incorporated with Cuprous selenide (Cu2Se) nano-inclusions were investigated from 300 K to 800 K. Here, except for the transition from p-type to n-type conduction that occurs in pristine PbTe at ~530 K due to the difference of mobility between thermally electron and hole at high temperature, another transition from p-type to n-type conduction at 300 K with an increasing proportion of Cu2Se could be due to the donor levels introduced by defects and unsaturated bonds at the interfaces. Moreover, by incorporating a small proportion (5 vol.%) of Cu2Se nanoparticles into the PbTe matrix to form nano-composites, both a reduction (~55%) in lattice thermal conductivity and an enhanced electrical conductivity compared with that of pristine PbTe are obtained, which allows the thermoelectric power factor to reach a larger value (~11.2 μW cm-1 K-2). Consequently, a maximum value ZT  =  0.91 is obtained at 760 K in the PbTe-5 vol.% Cu2Se sample.

  17. A fully wafer-level packaged RF MEMS switch with low actuation voltage using a piezoelectric actuator

    NASA Astrophysics Data System (ADS)

    Park, Jae-Hyoung; Lee, Hee-Chul; Park, Yong-Hee; Kim, Yong-Dae; Ji, Chang-Hyeon; Bu, Jonguk; Nam, Hyo-Jin

    2006-11-01

    In this paper, a fully wafer-level packaged RF MEMS switch has been demonstrated, which has low operation voltage, using a piezoelectric actuator. The piezoelectric actuator was designed to operate at low actuation voltage for application to advanced mobile handsets. The dc contact type RF switch was packaged using the wafer-level bonding process. The CPW transmission lines and piezoelectric actuators have been fabricated on separate wafers and assembled together by the wafer-level eutectic bonding process. A gold and tin composite was used for eutectic bonding at a low temperature of 300 °C. Via holes interconnecting the electrical contact pads through the wafer were filled completely with electroplated copper. The fully wafer-level packaged RF MEMS switch showed an insertion loss of 0.63 dB and an isolation of 26.4 dB at 5 GHz. The actuation voltage of the switch was 5 V. The resonant frequency of the piezoelectric actuator was 38.4 kHz and the spring constant of the actuator was calculated to be 9.6 N m-1. The size of the packaged SPST (single-pole single-through) switch was 1.2 mm × 1.2 mm including the packaging sealing rim. The effect of the proposed package structure on the RF performance was characterized with a device having CPW through lines and vertical feed lines excluding the RF switches. The measured packaging loss was 0.2 dB and the return loss was 33.6 dB at 5 GHz.

  18. H2 gas sensing properties of a ZnO/CuO and ZnO/CuO/Cu2O Heterostructures

    NASA Astrophysics Data System (ADS)

    Ababii, N.; Postica, V.; Hoppe, M.; Adelung, R.; Lupan, O.; Railean, S.; Pauporté, T.; Viana, B.

    2017-03-01

    The most important parameters of gas sensors are sensitivity and especially high selectivity to specific chemical species. To improve these parameters we developed sensor structures based on layered semiconducting oxides, namely CuO/Cu2O, CuO:Zn/Cu2O:Zn, NiO/ZnO. In this work, the ZnO/CuxO (where x = 1, 2) bi-layer heterostructure were grown via a simple synthesis from chemical solution (SCS) at relatively low temperatures (< 95 °C), representing a combination of layered n-type and p-type semiconducting oxides which are widely used as sensing material for gas sensors. The main advantages of the developed device structures are given by simplicity of the synthesis and technological cost-efficiency. Structural investigations showed high crystallinity of synthesized layers confirming the presence of zinc oxide nanostructures on the surface of the copper oxide film deposited on glass substrate. Structural changes in morphology of grown nanostructures induced by post-grown thermal annealing were observed by scanning electron microscopy (SEM) investigations, and were studied in detail. The influence of thermal annealing type on the optical properties was also investigated. As an example of practical applications, the ZnO/CuxO bi-layer heterojunctions and ZnO/CuO/Cu2O three-layered structures were integrated into sensor structures and were tested to different types of reducing gases at different operating temperatures (OPT), showing promising results for fabrication of selective gas sensors.

  19. Modeling Photoelectron Spectra of CuO, Cu2O, and CuO2 Anions with Equation-of-Motion Coupled-Cluster Methods: An Adventure in Fock Space.

    PubMed

    Orms, Natalie; Krylov, Anna I

    2018-04-12

    The experimental photoelectron spectra of di- and triatomic copper oxide anions have been reported previously. We present an analysis of the experimental spectra of the CuO - , Cu 2 O - , and CuO 2 - anions using equation-of-motion coupled-cluster (EOM-CC) methods. The open-shell electronic structure of each molecule demands a unique combination of EOM-CC methods to achieve an accurate and balanced representation of the multiconfigurational anionic- and neutral-state manifolds. Analysis of the Dyson orbitals associated with photodetachment from CuO - reveals the strong non-Koopmans character of the CuO states. For the lowest detachment energy, a good agreement between theoretical and experimental values is obtained with CCSD(T) (coupled-cluster with single and double excitations and perturbative account of triple excitations). The (T) correction is particularly important for Cu 2 O - . Use of a relativistic pseudopotential and matching basis set improves the quality of results in most cases. EOM-DIP-CCSD analysis of the low-lying states of CuO 2 - reveals multiple singlet and triplet anionic states near the triplet ground state, adding an extra layer of complexity to the interpretation of the experimental CuO 2 - photoelectron spectrum.

  20. Changes in the geometries of C₂H₂ and C₂H₄ on coordination to CuCl revealed by broadband rotational spectroscopy and ab-initio calculations.

    PubMed

    Stephens, Susanna L; Bittner, Dror M; Mikhailov, Victor A; Mizukami, Wataru; Tew, David P; Walker, Nicholas R; Legon, Anthony C

    2014-10-06

    The molecular geometries of isolated complexes in which a single molecule of C2H4 or C2H2 is bound to CuCl have been determined through pure rotational spectroscopy and ab-initio calculations. The C2H2···CuCl and C2H4···CuCl complexes are generated through laser vaporization of a copper rod in the presence of a gas sample undergoing supersonic expansion and containing C2H2 (or C2H4), CCl4, and Ar. Results are presented for five isotopologues of C2H2···CuCl and six isotopologues of C2H4···CuCl. Both of these complexes adopt C(2v), T-shaped geometries in which the hydrocarbon binds to the copper atom through its π electrons such that the metal is equidistant from all H atoms. The linear and planar geometries of free C2H2 and C2H4, respectively, are observed to distort significantly on attachment to the CuCl unit, and the various changes are quantified. The ∠(*-C-H) parameter in C2H2 (where * indicates the midpoint of the C≡C bond) is measured to be 192.4(7)° in the r0 geometry of the complex representing a significant change from the linear geometry of the free molecule. This distortion of the linear geometry of C2H2 involves the hydrogen atoms moving away from the copper atom within the complex. Ab-initio calculations at the CCSD(T)(F12*)/AVTZ level predict a dihedral ∠(HCCCu) angle of 96.05° in C2H4···CuCl, and the experimental results are consistent with such a distortion from planarity. The bonds connecting the carbon atoms within each of C2H2 and C2H4, respectively, extend by 0.027 and 0.029 Å relative to the bond lengths in the isolated molecules. Force constants, k(σ), and nuclear quadrupole coupling constants, χ(aa)(Cu), [χ(bb)(Cu) - χ(cc)(Cu)], χ(aa)(Cl), and [χ(bb)(Cl) - χ(cc)(Cl)], are independently determined for all isotopologues of C2H2···CuCl studied and for four isotopologues of C2H4···CuCl.

  1. Contextual cuing: the effects of stimulus variation, intentionality, and aging.

    PubMed

    Lyon, John; Scialfa, Charles; Cordazzo, Scheila; Bubric, Katherine

    2014-06-01

    Three experiments investigated the generalisation of contextual cuing and whether the effect is incidental or intentional in nature. Experiment 1 assessed contextual cuing across variations in display contrast, homogeneity, and spatial separation. Cuing effects were found with all display types and reaction-time disruption was manifested for repeated displays when consistent configurations had their target locations altered. Recognition memory for repeated displays was at chance levels. Experiment 2 showed that contextual cuing was insensitive to instructions to search for and remember repeated displays. Experiment 2A found that there were no age differences in contextual cuing or effects of intentional instructions, and no memory for repeated displays. Future research questions concern the generalisation of contextual cuing to a wider variety of display conditions and naturalistic tasks.

  2. Analysis of Relations Between the Level of Mg, Zn, Ca, Cu, and Fe and Depressiveness in Postmenopausal Women.

    PubMed

    Szkup, Małgorzata; Jurczak, Anna; Brodowska, Aleksandra; Brodowska, Agnieszka; Noceń, Iwona; Chlubek, Dariusz; Laszczyńska, Maria; Karakiewicz, Beata; Grochans, Elżbieta

    2017-03-01

    Numerous observations suggest a possible connection between the levels of Mg, Zn, Fe, and Zn and the incidence of depressive symptoms. Depression is two to three times more common in women than in men. The menopausal period is extremely conducive to depressive disorders. The aim of this study was to assess the severity of depressive symptoms in postmenopausal women depending on the levels of Mg, Zn, Ca, Cu, and Fe. The study included 198 healthy postmenopausal women at the average age of 56.26 ± 5.55 years. In the first part of the study, standardized research tools were used, namely the Primary Care Evaluation of Mental Disorders (PRIME-MD) and the Beck Depression Inventory (BDI). The second part involved biochemical analysis of Mg, Zn, Ca, Cu, and Fe levels in blood serum. The lowest Cu levels were observed in women without depressive symptoms (1.07 ± 0.22 mg/l) and the highest in those with severe depressive symptoms (1.19 ± 0.17 mg/l), (p ≤ 0.05). The lowest Mg levels were observed in women with depressive symptoms (14.28 ± 2.13 mg/l), and the highest in women without depressive symptoms (16.30 ± 3.51 mg/l), (p ≤ 0.05). The average serum Mg levels (15.75 ± 3.23 mg/l) decreased compared to the reference values (18.77-24 mg/l). What is striking is a potential relation between the levels of Mg and Cu and depressiveness. Our results indicate to a higher vulnerability to depression in a group of women with lower levels of Mg and higher levels of Cu.

  3. Inactivation of bacteria under visible light and in the dark by Cu films. Advantages of Cu-HIPIMS-sputtered films.

    PubMed

    Ehiasarian, A; Pulgarin, Cesar; Kiwi, John

    2012-11-01

    The Cu polyester thin-sputtered layers on textile fabrics show an acceptable bacterial inactivation kinetics using sputtering methods. Direct current magnetron sputtering (DCMS) for 40 s of Cu on cotton inactivated Escherichia coli within 30 min under visible light and within 120 min in the dark. For a longer DCMS time of 180 s, the Cu content was 0.294% w/w, but the bacterial inactivation kinetics under light was observed within 30 min, as was the case for the 40-s sputtered sample. This observation suggests that Cu ionic species play a key role in the E. coli inactivation and these species were further identified by X-ray photoelectron spectroscopy (XPS). The 40-s sputtered samples present the highest amount of Cu sites held in exposed positions interacting on the cotton with E. coli. Cu DC magnetron sputtering leads to thin metallic semi-transparent gray-brown Cu coating composed by Cu nanoparticulate in the nanometer range as found by electron microscopy (EM). Cu cotton fabrics were also functionalized by bipolar asymmetric DCMSP. Sputtering by DCMS and DCMSP for longer times lead to darker and more compact Cu films as detected by diffuse reflectance spectroscopy and EM. Cu is deposited on the polyester in the form of Cu(2)O and CuO as quantified by XPS. The redox interfacial reactions during bacterial inactivation involve changes in the Cu oxidation states and in the oxidation intermediates and were followed by XPS. High-power impulse magnetron sputtering (HIPIMS)-sputtered films show a low rugosity indicating that the texture of the Cu nanoparticulate films were smooth. The values of R (q) and R (a) were similar before and after the E. coli inactivation providing evidence for the stability of the HIPIMS-deposited Cu films. The Cu loading percentage required in the Cu films sputtered by HIPIMS to inactivate E. coli was about three times lower compared to DCMS films. This indicates a substantial Cu metal savings within the preparation of antibacterial

  4. Size effect model on kinetics of interfacial reaction between Sn-xAg-yCu solders and Cu substrate

    PubMed Central

    Huang, M. L.; Yang, F.

    2014-01-01

    The downsizing of solder balls results in larger interfacial intermetallic compound (IMC) grains and less Cu substrate consumption in lead-free soldering on Cu substrates. This size effect on the interfacial reaction is experimentally demonstrated and theoretically analyzed using Sn-3.0Ag-0.5Cu and Sn-3.5Ag solder balls. The interfacial reaction between the Sn-xAg-yCu solders and Cu substrates is a dynamic response to a combination of effects of interfacial IMC growth, Cu substrate consumption and composition variation in the interface zone. A concentration gradient controlled (CGC) kinetics model is proposed to explain the combined effects. The concentration gradient of Cu at the interface, which is a function of solder volume, initial Cu concentration and reaction time, is the root cause of the size effect. We found that a larger Cu concentration gradient results in smaller Cu6Sn5 grains and more consumption of Cu substrate. According to our model, the growth kinetics of interfacial Cu6Sn5 obeys a t1/3 law when the molten solder has approached the solution saturation, and will be slower otherwise due to the interfering dissolution mechanism. The size effect introduced in this model is supported by a good agreement between theoretical and experimental results. Finally, the scope of application of this model is discussed. PMID:25408359

  5. Scalable fabrication of SnO2 thin films sensitized with CuO islands for enhanced H2S gas sensing performance

    NASA Astrophysics Data System (ADS)

    Van Toan, Nguyen; Chien, Nguyen Viet; Van Duy, Nguyen; Vuong, Dang Duc; Lam, Nguyen Huu; Hoa, Nguyen Duc; Van Hieu, Nguyen; Chien, Nguyen Duc

    2015-01-01

    The detection of H2S, an important gaseous molecule that has been recently marked as a highly toxic environmental pollutant, has attracted increasing attention. We fabricate a wafer-scale SnO2 thin film sensitized with CuO islands using microelectronic technology for the improved detection of the highly toxic H2S gas. The SnO2-CuO island sensor exhibits significantly enhanced H2S gas response and reduced operating temperature. The thickness of CuO islands strongly influences H2S sensing characteristics, and the highest H2S gas response is observed with 20 nm-thick CuO islands. The response value (Ra/Rg) of the SnO2-CuO island sensor to 5 ppm H2S is as high as 128 at 200 °C and increases nearly 55-fold compared with that of the bare SnO2 thin film sensor. Meanwhile, the response of the SnO2-CuO island sensor to H2 (250 ppm), NH3 (250 ppm), CO (250 ppm), and LPG (1000 ppm) are low (1.3-2.5). The enhanced gas response and selectivity of the SnO2-CuO island sensor to H2S gas is explained by the sensitizing effect of CuO islands and the extension of electron depletion regions because of the formation of p-n junctions.

  6. Construction of leaf-like CuO-Cu2O nanocomposites on copper foam for high-performance supercapacitors.

    PubMed

    He, Dong; Wang, Guanda; Liu, Guolong; Suo, Hui; Zhao, Chun

    2017-03-07

    Leaf-like CuO-Cu 2 O nanosheets have been prepared on copper foam by a one-step simple anodization method, which can be used as an advanced binder-free supercapacitor electrode. The performance of the CuO-Cu 2 O/Cu foam electrode was optimized through controlling and restraining the current density and reaction time. The prepared electrode exhibits a very high specific capacitance (1.954 F cm -2 at a scan rate of 2 mV s -1 ), excellent durability (120% retention after 5000 cycles), remarkable rate capability (91.8% retention upon increasing the current density by 10 times) and good coulombic efficiency (78.2% at a current density of 2 mA cm -2 ). The facile and cost-effective fabrication process is also suitable for large scale practical production. These results indicate the leaf-like CuO-Cu 2 O/Cu foam electrode would be a promising electrode for high-performance supercapacitor applications.

  7. Experimental Liquidus Studies of the Pb-Cu-Si-O System in Equilibrium with Metallic Pb-Cu Alloys

    NASA Astrophysics Data System (ADS)

    Shevchenko, M.; Nicol, S.; Hayes, P. C.; Jak, E.

    2018-03-01

    Phase equilibria of the Pb-Cu-Si-O system have been investigated in the temperature range from 1073 K to 1673 K (800 °C to 1400 °C) for oxide liquid (slag) in equilibrium with solid Cu metal and/or liquid Pb-Cu alloy, and solid oxide phases: (a) quartz or tridymite (SiO2) and (b) cuprite (Cu2O). High-temperature equilibration on silica or copper substrates was performed, followed by quenching, and direct measurement of Pb, Cu, and Si concentrations in the liquid and solid phases using the electron probe X-ray microanalysis has been employed to accurately characterize the system in equilibrium with Cu or Pb-Cu metal. All results are projected onto the PbO-"CuO0.5"-SiO2 plane for presentation purposes. The present study is the first-ever systematic investigation of this system to describe the slag liquidus temperatures in the silica and cuprite primary phase fields.

  8. Development of Ag-Pd-Au-Cu alloy for multiple dental applications. Part 1. Effects of Pd and Cu contents, and addition of Ga or Sn on physical properties and bond with ultra-low fusing ceramic.

    PubMed

    Goto, S; Miyagawa, Y; Ogura, H

    2000-09-01

    Ag-Pd-Au-Cu quaternary alloys consisting of 30-50% Ag, 20-40% Pd, 10-20% Cu and 20% Au (mother alloys) were prepared. Then 5% Sn or 5% Ga was added to the mother alloy compositions, and another two alloy systems (Sn-added alloys and Ga-added alloys) were also prepared. The bond between the prepared alloys and an ultra-low fusing ceramic as well as their physical properties such as the solidus point, liquidus point and the coefficient of thermal expansion were evaluated. The solidus point and liquidus point of the prepared alloys ranged from 802 degrees C to 1142 degrees C and from 931 degrees C to 1223 degrees C, respectively. The coefficient of thermal expansion ranged from 14.6 to 17.1 x 10(-6)/degrees C for the Sn- and Ga-added alloys. In most cases, the Pd and Cu contents significantly influenced the solidus point, liquidus point and coefficient of thermal expansion. All Sn- and Ga-added alloys showed high area fractions of retained ceramic (92.1-100%), while the mother alloy showed relatively low area fractions (82.3%) with a high standard deviation (20.5%). Based on the evaluated properties, six Sn-added alloys and four Ga-added alloys among the prepared alloys were suitable for the application of the tested ultra-low fusing ceramic.

  9. STM/STS study on electronic superstructures in the superconducting state of high-Tc cuprate Bi2Sr2CaCu2O8+δ

    NASA Astrophysics Data System (ADS)

    Mizuta, S.; Kurosawa, T.; Takeyama, K.; Momono, N.; Ishii, Y.; Yoshida, H.; Oda, M.; Ido, M.

    2018-03-01

    We report STM/STS measurements at 8 K in underdoped Bi2Sr2CaCu2O8+δ crystals (T c = 76 K and hole-doping level p ∼ 0.12) whose energy spectra around the Fermi level are characterized by a two-gap structure consisting of spatially inhomogeneous pseudogap (PG) and comparatively homogeneous superconducting gap (SCG). Two electronic superstructures, checkerboard modulation (CBM) and Cu-O-Cu bond-centered modulation (BCM), are observed with mapping spectral weights at low energies within the SCG and the ratio of spectral weights at ±ΔPG (PG energy), respectively. On the basis of the present findings, we suggest that the lower-energy scale CBM is an intrinsic property of Cu-O planes and can coexist with the BCM whose characteristic energy is ∼ΔPG in identical regions in real space.

  10. Main reinforcement effects of precipitation phase Mg2Cu3Si, Mg2Si and MgCu2 on Mg-Cu-Si alloys by ab initio investigation

    NASA Astrophysics Data System (ADS)

    Shi, Xue-Feng; Wang, Hai-Chen; Tang, Ping-Ying; Tang, Bi-Yu

    2017-09-01

    To predict and compare the main reinforcement effects of the key precipitation phases Mg2Cu3Si, Mg2Si and MgCu2 in Mg-Cu-Si alloy, the structural, mechanical and electronic properties of these phases have been studied by ab initio calculations. The lowest formation enthalpy and cohesive energy indicate that Mg2Cu3Si has the strongest alloying ability and structural stability. The mechanical modulus indicates that Mg2Cu3Si has the strongest resistance to reversible shear/volume distortion and has maximum hardness. The characterization of brittle (ductile) behavior manifests that MgCu2 has favorable ductility. Meanwhile the evaluation of elastic anisotropy indicates that Mg2Si possesses elastic isotropy. Debye temperature prediction shows that Mg2Si and Mg2Cu3Si have better thermal stability. To achieve an unbiased interpretation on the phase stability and mechanical behavior of these precipitation phases, the density of states and differential charge densities are also analyzed. The current study deepens the comprehensive understanding of main reinforcement effects of these precipitation phases on Mg-Cu-Si alloys, and also benefits to optimize the overall performances of Mg-Cu-Si alloy from the hardness, ductility and thermal stability by controlling these second precipitation phases during the heat treatment process.

  11. Optimization of photoelectrochemical performance in Pt-modified p-Cu2O/n-Cu2O nanocomposite

    NASA Astrophysics Data System (ADS)

    Wang, Yichen; Lou, Zirui; Niu, Wenzhe; Ye, Zhizhen; Zhu, Liping

    2018-04-01

    As it is expected to be one of the most promising materials for utilizing solar energy, Cu2O has attracted considerable attention with respect to the achievement of solar energy conversion. Until now, the photocurrent densities of all planar structure of the Cu2O photocathode have not even come close to the theoretical value of -14.7 mA cm-2 due to the incompatible light absorption and charge carrier diffusion lengths. Here, we have fabricated p-n Cu2O homojunction nanocomposite by multiple steps of electrochemical deposition processing with the optimization of deposition periods. The p-Cu2O/n-Cu2O nanocomposite fabricated by optimized pH (4.9) and deposition time (4 min) exhibited double the photocurrent density of that of the bare p-Cu2O photocathode. And the highest photocurrent density of nanostructured p-n Cu2O nanorod homojunction photocathode with a p-Cu2O blocking layer reached -10.0 mA cm-2 at 0 V versus the reversible hydrogen electrode under simulated AM 1.5G illumination (100 mW cm-2).

  12. A comparative study of heterostructured CuO/CuWO4 nanowires and thin films

    NASA Astrophysics Data System (ADS)

    Polyakov, Boris; Kuzmin, Alexei; Vlassov, Sergei; Butanovs, Edgars; Zideluns, Janis; Butikova, Jelena; Kalendarev, Robert; Zubkins, Martins

    2017-12-01

    A comparative study of heterostructured CuO/CuWO4 core/shell nanowires and double-layer thin films was performed through X-ray diffraction, confocal micro-Raman spectroscopy and electron (SEM and TEM) microscopies. The heterostructures were produced using a two-step process, starting from a deposition of amorphous WO3 layer on top of CuO nanowires and thin films by reactive DC magnetron sputtering and followed by annealing at 650 °C in air. The second step induced a solid-state reaction between CuO and WO3 oxides through a thermal diffusion process, revealed by SEM-EDX analysis. Morphology evolution of core/shell nanowires and double-layer thin films upon heating was studied by electron (SEM and TEM) microscopies. A formation of CuWO4 phase was confirmed by X-ray diffraction and confocal micro-Raman spectroscopy.

  13. Fast photocatalytic degradation of sulforhodamine B using ZnO:Cu nanorods

    NASA Astrophysics Data System (ADS)

    Raji, R.; Gopchandran, K. G.

    2018-02-01

    In this work, ZnO:Cu nanorods with tunable Cu content were successfully synthesized via co-precipitation method and investigations were made on the use of these nanorods as photocatalyst by observing the photodegradation of a representative dye pollutant of sulforhodamine B (SRB) under sunlight. The X-ray diffraction analysis and high resolution transmission electron microscopy showed that ZnO:Cu nanorods possess wurtzite phase with preferential growth along (101) plane. The formation of additional defect levels in these nanorods on doping with Cu and its dependence on the concentration of Cu were studied using photoluminescence and X-ray photoelectron spectroscopy. ZnO:Cu nanorods results in faster degradation of dye as compared to the undoped ZnO and is found that Cu doping enhances the photodegradation activity significantly and is highly sensitive to Cu doping level. The fast photocatalytic degradation is attributed to the fact that Cu ions promote the interfacial charge transfer and favors the effective charge separation of photogenerated electrons and holes generated during sunlight irradiation, increasing the rate of production of reactive oxygen species needed for the degradation of the dye. The chemical oxygen demand analysis of the dye solution after sunlight irradiation indicates that rate of mineralization is slower than the decoloration. The possible mechanism for degradation of dye under sunlight irradiation is described with a schematic. Additionally, the photostability of the ZnO:Cu nanorods was also tested through three repetitive cycles. This work suggest that the prepared ZnO:Cu nanorods are suitable for cost-effective water purification.

  14. CuMnOS Nanoflowers with Different Cu+/Cu2+ Ratios for the CO2-to-CH3OH and the CH3OH-to-H2 Redox Reactions

    NASA Astrophysics Data System (ADS)

    Chen, Xiaoyun; Abdullah, Hairus; Kuo, Dong-Hau

    2017-01-01

    A conservative CO2-Methanol (CH3OH) regeneration cycle, to capture and reutilize the greenhouse gas of CO2 by aqueous hydrogenation for industry-useful CH3OH and to convert aqueous CH3OH solution by dehydrogenation for the clean energy of hydrogen (H2), is demonstrated at normal temperature and pressure (NTP) with two kinds of CuMnOS nanoflower catalysts. The [Cu+]-high CuMnOS led to a CH3OH yield of 21.1 mmol·g-1catal.·h-1 in the CuMnOS-CO2-H2O system and the other [Cu+]-low one had a H2 yield of 7.65 mmol·g-1catal.·h-1 in the CuMnOS-CH3OH-H2O system. The successful redox reactions at NTP rely on active lattice oxygen of CuMnOS catalysts and its charge (hole or electron) transfer ability between Cu+ and Cu2+. The CO2-hydrogenated CH3OH in aqueous solution is not only a fuel but also an ideal liquid hydrogen storage system for transportation application.

  15. CuMnOS Nanoflowers with Different Cu+/Cu2+ Ratios for the CO2-to-CH3OH and the CH3OH-to-H2 Redox Reactions

    PubMed Central

    Chen, Xiaoyun; Abdullah, Hairus; Kuo, Dong-Hau

    2017-01-01

    A conservative CO2-Methanol (CH3OH) regeneration cycle, to capture and reutilize the greenhouse gas of CO2 by aqueous hydrogenation for industry-useful CH3OH and to convert aqueous CH3OH solution by dehydrogenation for the clean energy of hydrogen (H2), is demonstrated at normal temperature and pressure (NTP) with two kinds of CuMnOS nanoflower catalysts. The [Cu+]-high CuMnOS led to a CH3OH yield of 21.1 mmol·g−1catal.·h−1 in the CuMnOS-CO2-H2O system and the other [Cu+]-low one had a H2 yield of 7.65 mmol·g−1catal.·h−1 in the CuMnOS-CH3OH-H2O system. The successful redox reactions at NTP rely on active lattice oxygen of CuMnOS catalysts and its charge (hole or electron) transfer ability between Cu+ and Cu2+. The CO2-hydrogenated CH3OH in aqueous solution is not only a fuel but also an ideal liquid hydrogen storage system for transportation application. PMID:28117456

  16. CuMnOS Nanoflowers with Different Cu+/Cu2+ Ratios for the CO2-to-CH3OH and the CH3OH-to-H2 Redox Reactions.

    PubMed

    Chen, Xiaoyun; Abdullah, Hairus; Kuo, Dong-Hau

    2017-01-24

    A conservative CO 2 -Methanol (CH 3 OH) regeneration cycle, to capture and reutilize the greenhouse gas of CO 2 by aqueous hydrogenation for industry-useful CH 3 OH and to convert aqueous CH 3 OH solution by dehydrogenation for the clean energy of hydrogen (H 2 ), is demonstrated at normal temperature and pressure (NTP) with two kinds of CuMnOS nanoflower catalysts. The [Cu + ]-high CuMnOS led to a CH 3 OH yield of 21.1 mmol·g -1 catal.·h -1 in the CuMnOS-CO 2 -H 2 O system and the other [Cu + ]-low one had a H 2 yield of 7.65 mmol·g -1 catal.·h -1 in the CuMnOS-CH 3 OH-H 2 O system. The successful redox reactions at NTP rely on active lattice oxygen of CuMnOS catalysts and its charge (hole or electron) transfer ability between Cu + and Cu 2+ . The CO 2 -hydrogenated CH 3 OH in aqueous solution is not only a fuel but also an ideal liquid hydrogen storage system for transportation application.

  17. The interaction between dietary Fe, Cu and stress in Cu-67 retention and serum ceruloplasmin (Cp) activity in rats

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pellett, L.; Kattelmann, K.; Zinn, K.

    1991-03-15

    The objectives of the study were to determine the effects of dietary Fe and stress on Cu-67 retention and serum Cp activity in the rat. A 2 {times} 2 {times} 2 factorial arrangement of treatments was utilized. Male Sprague Dawley weanling rats were fed AIN-76 diets ad lib containing 0.8 ppm Cu (CuD) or 5.7 ppm Cu (CuA) with 22.5 ppm Fe (FeA) or 280 ppm Fe (FeE). After 19 days, one-half of the animals of each treatment were stressed by an intramuscular injection of 0.1 ml turpentine/100 gm body weight. Forty-eight hours later, animals were gavaged with Cu-67 andmore » counted over a 7 day period in a whole body high resolution gamma counter. Cu-67 retention was 20% higher in CuD rats compared to CuA rats. There were no significant effects caused by Fe or stress or the interaction between these variables on Cu-67 retention. In rats fed FeE-CuA diets, serum Cp activity was significantly depressed compared to rats fed FeA-CuA diets. These reductions in the acute phase protein Cp, were 85% and 70% in nonstressed and stressed rats, respectively. The results of this study suggest that the negative interaction effects of excess Fe on Cu utilization does not occur at the site of Cu absorption, but within the body and specifically in the liver.« less

  18. Multi-functional ultrathin Pd xCu 1-x and Pt~Pd xCu 1-x one-dimensional nanowire motifs for various small molecule oxidation reactions

    DOE PAGES

    Liu, Haiqing; Wong, Stanislaus S.; Adzic, Radoslav R.

    2015-11-18

    Developing novel electrocatalysts for small molecule oxidation processes, including formic acid oxidation (FAOR), methanol oxidation reaction (MOR), and ethanol oxidation reaction (EOR), denoting the key anodic reactions for their respective fuel cell configurations, is a significant and relevant theme of recent efforts in the field. Herein, in this report, we demonstrated a concerted effort to couple and combine the benefits of small size, anisotropic morphology, and tunable chemical composition in order to devise a novel “family” of functional architectures. In particular, we have fabricated not only ultrathin 1-D Pd 1–xCu x alloys but also Pt-coated Pd 1–xCu x (i.e., Pt~Pdmore » 1–xCu x; herein the ~ indicates an intimate association, but not necessarily actual bond formation, between the inner bimetallic core and the Pt outer shell) core–shell hierarchical nanostructures with readily tunable chemical compositions by utilizing a facile, surfactant-based, wet chemical synthesis coupled with a Cu underpotential deposition technique. Our main finding is that our series of as-prepared nanowires are functionally flexible. More precisely, we demonstrate that various examples within this “family” of structural motifs can be tailored for exceptional activity with all 3 of these important electrocatalytic reactions. In particular, we note that our series of Pd 1–xCu x nanowires all exhibit enhanced FAOR activities as compared with not only analogous Pd ultrathin nanowires but also commercial Pt and Pd standards, with Pd 9Cu representing the “optimal” composition. Moreover, our group of Pt~Pd 1–xCu x nanowires consistently outperformed not only commercial Pt NPs but also ultrathin Pt nanowires by several fold orders of magnitude for both the MOR and EOR reactions in alkaline media. As a result, the variation of the MOR and EOR performance with the chemical composition of our ultrathin Pt~Pd 1–xCu x nanowires was also discussed.« less

  19. Efficient removal of methyl orange using Cu2O as a dual function catalyst

    NASA Astrophysics Data System (ADS)

    Zhang, Fan; Dong, Guohui; Wang, Mian; Zeng, Yubin; Wang, Chuanyi

    2018-06-01

    In this study, we synthesized Cu2O particles with rough surfaces by a facile solvothermal method as a dual-function material that can degrade contaminants not only under light irradiation but also in dark circumstance. Both the as-prepared Cu2O and commercial Cu2O exhibited excellent performance for the removal of methyl orange under visible light irradiation through a photocatalysis-based strategy. However, the former was found to show remarkable capability under dark circumstances by means of molecular oxygen activation, while the latter performed poor efficiently under the same condition. This significant difference of performances under dark circumstances was related to rich oxygen vacancies existed on the as-prepared Cu2O surfaces that are associated with the single-electron reduction of O2 to generate radO2-, which play a dominant role in the generation of Cu+. In addition, Cu+ was identified to play key roles in the broken of azo bond. Then, the generated intermediates were mineralized by radOH generated through molecular oxygen activation process. This study could not only deep the understanding of the MO removal mechanism by Cu2O but also show a novel direction of amphibious application for photocatalytic materials.

  20. Photo-reduced Cu/CuO nanoclusters on TiO2 nanotube arrays as highly efficient and reusable catalyst

    NASA Astrophysics Data System (ADS)

    Jin, Zhao; Liu, Chang; Qi, Kun; Cui, Xiaoqiang

    2017-01-01

    Non-noble metal nanoparticles are becoming more and more important in catalysis recently. Cu/CuO nanoclusters on highly ordered TiO2 nanotube arrays are successfully developed by a surfactant-free photoreduction method. This non-noble metal Cu/CuO-TiO2 catalyst exhibits excellent catalytic activity and stability for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with the presence of sodium borohydride (NaBH4). The rate constant of this low-cost Cu/CuO based catalyst is even higher than that of the noble metal nanoparticles decorated on the same TiO2 substrate. The conversion efficiency remains almost unchanged after 7 cycles of recycling. The recycle process of this Cu/CuO-TiO2 catalyst supported by Ti foil is very simple and convenient compared with that of the common powder catalysts. This catalyst also exhibited great catalytic activity to other organic dyes, such as methylene blue (MB), rhodamine B (RhB) and methyl orange (MO). This highly efficient, low-cost and easily reusable Cu/CuO-TiO2 catalyst is expected to be of great potential in catalysis in the future.

  1. CuI as Hole-Transport Channel for Enhancing Photoelectrocatalytic Activity by Constructing CuI/BiOI Heterojunction.

    PubMed

    Sun, Mingjuan; Hu, Jiayue; Zhai, Chunyang; Zhu, Mingshan; Pan, Jianguo

    2017-04-19

    In this paper, CuI, as a typical hole-transport channel, was used to construct a high-performance visible-light-driven CuI/BiOI heterostructure for photoelectrocatalytic applications. The heterostructure combines the broad visible absorption of BiOI and high hole mobility of CuI. Compared to pure BiOI, the CuI/BiOI heterostructure exhibited distinctly enhanced photoelectrocatalytic performance for the oxidation of methanol and organic pollutants under visible-light irradiation. The photogenerated electron-hole pairs of the excited BiOI can be separated efficiently through CuI, in which the CuI acts as a superior hole-transport channel to improve photoelectrocatalytic oxidization of methanol and organic pollutants. The outstanding photoelectrocatalytic activity shows that the p-type CuI works as a promising hole-transport channel to improve the photocatalytic performance of traditional semiconductors.

  2. Outstanding features of Cu-doped ZnS nanoclusters

    NASA Astrophysics Data System (ADS)

    Tawfik, Wael Z.; Farghali, A. A.; Moneim, Ahmed; Imam, N. G.; El-Dek, S. I.

    2018-05-01

    ZnS and their Cu-doped nanoclusters (NCs) were synthesized successfully using the wet chemical route with different Cu content. The crystalline structure was investigated using x-ray powder diffraction which assured the single-phase formation in cubic symmetry. High-resolution transmission electron microscope indicated the microstructure of NCs with a size ranging from 2–4 nm. A butterfly hysteresis (M-H) loop was observed at room temperature with large values of coercivity for the Cu content of x = 0.05. Photoluminescence emission spectra were recorded from 500–615 nm for pure and Cu-doped ZnS NCs at a 350 nm excitation wavelength. The sample exhibited green fluorescence bands peaking at 535, 544, 552.5, 558.2, and 560.6 nm, which confirmed the characteristic feature of Zn2+ as luminescent centers in the lattice. The additional yellow and orange emissions are due to defect levels or/and impurity centers. The dielectric constant as well as the conductivity values increased with increasing Cu content.

  3. Effects of the molecule-electrode interface on the low-bias conductance of Cu-H2-Cu single-molecule junctions.

    PubMed

    Jiang, Zhuoling; Wang, Hao; Shen, Ziyong; Sanvito, Stefano; Hou, Shimin

    2016-07-28

    The atomic structure and electronic transport properties of a single hydrogen molecule connected to both symmetric and asymmetric Cu electrodes are investigated by using the non-equilibrium Green's function formalism combined with the density functional theory. Our calculations show that in symmetric Cu-H2-Cu junctions, the low-bias conductance drops rapidly upon stretching, while asymmetric ones present a low-bias conductance spanning the 0.2-0.3 G0 interval for a wide range of electrode separations. This is in good agreement with experiments on Cu atomic contacts in a hydrogen environment. Furthermore, the distribution of the calculated vibrational energies of the two hydrogen atoms in the asymmetric Cu-H2-Cu junction is also consistent with experiments. These findings provide clear evidence for the formation of asymmetric Cu-H2-Cu molecular junctions in breaking Cu atomic contacts in the presence of hydrogen and are also helpful for the design of molecular devices with Cu electrodes.

  4. EPR and ESE of CuS4 complex in Cu(dmit)2: g-Factor and hyperfine splitting correlation in tetrahedral Cu-sulfur complexes

    NASA Astrophysics Data System (ADS)

    Hoffmann, Stanisław K.; Goslar, Janina; Lijewski, Stefan; Zalewska, Alina

    2013-11-01

    Pseudotetrahedral CuS4 complexes of Cu(dmit)2 compound in DMF solution were studied by EPR, UV-Vis and electron spin echo methods. After rapid freezing at 77 K a good glassy state is formed and the CuS4 complex has a D2d symmetry of a compressed tetrahedron with xy ground state and spin-Hamiltonian parameters g|| = 2.089, g⊥ = 2.026, A|| = 146 × 10-4 cm-1 and A⊥ = 30 × 10-4 cm-1. The complex is not deformed in the glassy state and is very rigid as indicated by the echo detected spectrum and by electron spin relaxation which is governed by reorientations of methyl groups of surrounding DMF molecules as shown by electron spin echo envelope modulation (ESEEM) spectrum. The g|| and A|| of Cu(dmit)2 and other CuS4 complexes collected in Peisach-Blumberg correlation diagram were analyzed using extended Molecular Orbital theory. We explain why the correlation line for copper-sulfur complexes has larger slope compared to the CuO4 and CuN4 tetrahedra. Along the correlation line the delocalization of unpaired electron density onto ligand is constant and varies from β = 0.78-0.83 for g|| in the range 2.06-2.10 of correlation diagram. The slope of the line is determined by the product of MO-coefficients αc1, where α is a parameter characterizing delocalization of unpaired electron in x2-y2 and c1 < 1 is a mixing parameter decreasing when 4p contribution grows. We found, unexpectedly, that αc1≈0.7 for all CuS4 complexes suggesting a correlation between degree of tetrahedral deformation and MO-parameters. MO-coefficients for Cu(dmit)2 are α = 0.753, β = 0.752 and c1 = 0.930 confirming a strong delocalization of unpaired electron in xy and x2-y2 orbitals.

  5. Effects of CuO nanoparticles on Lemna minor.

    PubMed

    Song, Guanling; Hou, Wenhua; Gao, Yuan; Wang, Yan; Lin, Lin; Zhang, Zhiwei; Niu, Qiang; Ma, Rulin; Mu, Lati; Wang, Haixia

    2016-12-01

    Copper dioxide nanoparticles (NPs), which is a kind of important and widely used metal oxide NP, eventually reaches a water body through wastewater and urban runoff. Ecotoxicological studies of this kind of NPs effects on hydrophyte are very limited at present. Lemna minor was exposed to media with different concentrations of CuO NPs, bulk CuO, and two times concentration of Cu 2+ released from CuO NPs in culture media. The changes in plant growth, chlorophyll content, antioxidant defense enzyme activities [i.e., peroxidase (POD), catalase (CAT), superoxide dismutase (SOD) activities], and malondialdehyde (MDA) content were measured in the present study. The particle size of CuO NPs and the zeta potential of CuO NPs and bulk CuO in the culture media were also analyzed to complementally evaluate their toxicity on duckweed. Results showed that CuO NPs inhibited the plant growth at lower concentration than bulk CuO. L. minor roots were easily broken in CuO NPs media under the experimental condition, and the inhibition occurred only partly because CuO NPs released Cu 2+ in the culture media. The POD, SOD, and CAT activities of L. minor increased when the plants were exposed to CuO NPs, bulk CuO NPs and two times the concentration of Cu 2+ released from CuO NPs in culture media, but the increase of these enzymes were the highest in CuO NPs media among the three kinds of materials. The MDA content was significantly increased compared with that of the control from 50 mg L -1 CuO NP concentration in culture media. CuO NPs has more toxicity on L. minor compared with that of bulk CuO, and the inhibition occurred only partly because released Cu 2+ in the culture media. The plant accumulated more reactive oxygen species in the CuO NP media than in the same concentration of bulk CuO. The plant cell encountered serious damage when the CuO NP concentration reached 50 mg L -1 in culture media. The toxicology of CuO NP on hydrophytes must be considered because that hydrophytes

  6. Size effect on atomic structure in low-dimensional Cu-Zr amorphous systems.

    PubMed

    Zhang, W B; Liu, J; Lu, S H; Zhang, H; Wang, H; Wang, X D; Cao, Q P; Zhang, D X; Jiang, J Z

    2017-08-04

    The size effect on atomic structure of a Cu 64 Zr 36 amorphous system, including zero-dimensional small-size amorphous particles (SSAPs) and two-dimensional small-size amorphous films (SSAFs) together with bulk sample was investigated by molecular dynamics simulations. We revealed that sample size strongly affects local atomic structure in both Cu 64 Zr 36 SSAPs and SSAFs, which are composed of core and shell (surface) components. Compared with core component, the shell component of SSAPs has lower average coordination number and average bond length, higher degree of ordering, and lower packing density due to the segregation of Cu atoms on the shell of Cu 64 Zr 36 SSAPs. These atomic structure differences in SSAPs with various sizes result in different glass transition temperatures, in which the glass transition temperature for the shell component is found to be 577 K, which is much lower than 910 K for the core component. We further extended the size effect on the structure and glasses transition temperature to Cu 64 Zr 36 SSAFs, and revealed that the T g decreases when SSAFs becomes thinner due to the following factors: different dynamic motion (mean square displacement), different density of core and surface and Cu segregation on the surface of SSAFs. The obtained results here are different from the results for the size effect on atomic structure of nanometer-sized crystalline metallic alloys.

  7. A hermetic and room-temperature wafer bonding technique based on integrated reactive multilayer systems

    NASA Astrophysics Data System (ADS)

    Braeuer, J.; Gessner, T.

    2014-11-01

    This paper focuses on direct deposition and patterning of reactive and nano-scale multilayer films at wafer level. These multilayer structures are called integrated reactive material systems (iRMS). In contrast to the typically used nickel (Ni)/ aluminum (Al) systems, in this work we needed to have our total multilayer film thicknesses smaller than 2.5 µm to reduce stress within the multilayer as well as deposition costs. Thus, we introduced new high energetic iRMS. These films were deposited by using alternating magnetron sputtering from high purity Al- and palladium (Pd)-targets to obtain films with a defined Al:Pd atomic ratio. In this paper, we present the result for reaction characteristics and reaction velocities which were up to 72.5 m s-1 for bond frames with lateral dimensions as low as 20 µm. Furthermore, the feasibility of silicon (Si)-Si, Si-glass as well as Si-ceramic hermetic and metallic wafer bonding at room temperature is presented. We show that by using this bond technology, strong (maximum shear strengths of 235 MPa) and hermetically sealed bond interfaces can be achieved without any additional solder material.

  8. Exhibition of veiled features in diffusion bonding of titanium alloy and stainless steel via copper

    NASA Astrophysics Data System (ADS)

    Thirunavukarasu, Gopinath; Kundu, Sukumar; Laha, Tapas; Roy, Deb; Chatterjee, Subrata

    2017-11-01

    An investigation was carried out to know the extent of influence of bonding-time on the interface structure and mechanical properties of diffusion bonding (DB) of TiA|Cu|SS. DB of Ti6Al4V (TiA) and 304 stainless steel (SS) using pure copper (Cu) of 200-μm thickness were processed in vacuum using 4-MPa bonding-pressure at 1123 K from 15 to 120 min in steps of 15 min. Preparation of DB was not possible when bonding-time was less than 60 min as the bonding at Cu|SS interface was unsuccessful in spite of effective bonding at TiA|Cu interface; however, successful DB were produced when the bonding-time was 60 min and beyond. DB processed for 60 and 75 min (classified as shorter bonding-time interval) showed distinctive characteristics (structural, mechanical, and fractural) as compared to the DB processed for 90, 105, and 120 min (classified as longer bonding-time interval). DB processed for 60 and 75 min exhibited layer-wise Cu-Ti-based intermetallics at TiA|Cu interface, whereas Cu|SS interface was completely free from reaction products. The layer-wise structure of Cu-Ti-based intermetallics were not observed at TiA|Cu interface in the DB processed for longer bonding-time; however, the Cu|SS interface had layer-wise ternary intermetallic compounds (T1, T2, and T3) of Cu-Fe-Ti-based along with σ phase depending upon the bonding-time chosen. Diffusivity of Ti-atoms in Cu-layer (DTi in Cu-layer) was much greater than the diffusivity of Fe-atoms in Cu-layer (DFe in Cu-layer). Ti-atoms reached Cu|SS interface but Fe-atoms were unable to reach TiA|Cu interface. It was observed that DB fractured at Cu|SS interface when processed for shorter bonding-time interval, whereas the DB processed for longer bonding-time interval fractured apparently at the middle of Cu-foil region predominantly due to the existence of brittle Cu-Fe-Ti-based intermetallics.

  9. The mechanism of Cu+ transport ATPases: interaction with CU+ chaperones and the role of transient metal-binding sites.

    PubMed

    Padilla-Benavides, Teresita; McCann, Courtney J; Argüello, José M

    2013-01-04

    Cu(+)-ATPases are membrane proteins that couple the hydrolysis of ATP to the efflux of cytoplasmic Cu(+). In cells, soluble chaperone proteins bind and distribute cytoplasmic Cu(+), delivering the ion to the transmembrane metal-binding sites in the ATPase. The structure of Legionella pneumophila Cu(+)-ATPase (Gourdon, P., Liu, X. Y., Skjørringe, T., Morth, J. P., Møller, L. B., Pedersen, B. P., and Nissen, P. (2011) Nature 475, 59-64) shows that a kinked transmembrane segment forms a "platform" exposed to the cytoplasm. In addition, neighboring invariant Met, Asp, and Glu are located at the "entrance" of the ion path. Mutations of amino acids in these regions of the Archaeoglobus fulgidus Cu(+)-ATPase CopA do not affect ATPase activity in the presence of Cu(+) free in solution. However, Cu(+) bound to the corresponding chaperone (CopZ) could not activate the mutated ATPases, and in parallel experiments, CopZ was unable to transfer Cu(+) to CopA. Furthermore, mutation of a specific electronegative patch on the CopZ surface abolishes the ATPase activation and Cu(+) transference, indicating that the region is required for the CopZ-CopA interaction. Moreover, the data suggest that the interaction is driven by the complementation of the electropositive platform in the ATPase and the electronegative Cu(+) chaperone. This docking likely places the Cu(+) proximal to the conserved carboxyl and thiol groups in the entrance site that induce metal release from the chaperone via ligand exchange. The initial interaction of Cu(+) with the pump is transient because Cu(+) is transferred from the entrance site to transmembrane metal-binding sites involved in transmembrane translocation.

  10. Production of 64Cu and 67Cu radiopharmaceuticals using zinc target irradiated with accelerator neutrons

    NASA Astrophysics Data System (ADS)

    Kawabata, Masako; Hashimoto, Kazuyuki; Saeki, Hideya; Sato, Nozomi; Motoishi, Shoji; Nagai, Yasuki

    2014-09-01

    Copper radioisotopes have gained a lot of attention in radiopharmaceuticals owing to their unique decay characteristics. The longest half-life β emitter, 67Cu, is thought to be suitable for targeted radio-immunotherapy. Adequate production of 67Cu to meet the demands of clinical studies has not been fully established. Another attractive copper isotope, 64Cu has possible applications as a diagnostic imaging tracer combined with a therapeutic effect. This work proposes a production method using accelerator neutrons in which two copper radioisotopes can be produced: 1) 68Zn(n,x)67Cu and 2) 64Zn(n,p)64Cu using ~14 MeV neutrons generated by natC(d, n) reaction, both from natural or enriched zinc oxides. The generated 64,67Cu were separated from the target zinc oxide using a chelating and an anion exchange columns and were labelled with two widely studied chelators where the labelling efficiency was found to be acceptably good. The major advantage of this method is that a significant amount of 64,67Cu with a very few impurity radionuclides are produced which also makes the separation procedure simple. Provided an accelerator supplying an Ed = ~ 40 MeV, a wide application of 64,67Cu based drugs in nuclear medicine is feasible in the near future. We will present the characteristics of this production method using accelerator neutrons including the chemical separation processes.

  11. Interfacial reaction and microstructure between the Sn3Ag0.5Cu solder and Cu-Co dual-phase substrate

    NASA Astrophysics Data System (ADS)

    Li, Chao; Hu, Xiaowu; Jiang, Xiongxin; Li, Yulong

    2018-07-01

    In this study, interfacial reactions and microstructures of the Sn3Ag0.5Cu (SAC305)/Cu- xCo ( x = 0, 30 and 50 wt%) systems were investigated during reflowing at 290 °C and solid-state aging at 150 °C for various time. The effects of different contents of Co in substrate on interfacial reaction in SAC305/Cu- xCo system were discussed. It was found that the addition of Co into pure copper substrate to achieve alloying would effectively inhibit the growth of IMC layers. Comparison among the thickness of the intermetallic compound (IMC) in three kinds of SAC305/Cu-Co systems indicated that the IMC layer of SAC305/Cu joint was thicker than that of the other two types of solder joints. The composition of the SAC305/Cu IMC layers was Cu6Sn5 and Cu3Sn. Three kinds of reaction phases (Cu,Co)6Sn5, (Cu,Co)Sn2 and (Cu,Co)3Sn were found at the interfaces of the SAC305/Cu-30Co and SAC305/Cu-50Co joints. Remarkably the (Cu,Co)Sn2 phase was found adjacent to the Co-rich phase after soldering and eliminated after the aging treatment. While the (Cu,Co)3Sn phase accumulated increasingly adjacent to the substrate with the increased aging time. The results suggested that the Co content increased from 30 to 50 wt% in substrate lead to significant restraint of the growth of interfacial IMC. In addition, the thickness of the interfacial IMC layer was linear with the square root of the aging time during the aging process. The reaction rate between Sn atoms in solder and Cu, Co atoms in substrate was quite different, which lead to the fact that the interface of SAC305/Cu-Co is uneven on the side of substrate after reflowing and aging.

  12. Enantiospecific electrodeposition of chiral CuO films on single-crystal Cu(111).

    PubMed

    Bohannan, Eric W; Kothari, Hiten M; Nicic, Igor M; Switzer, Jay A

    2004-01-21

    Epitaxial films of monoclinic CuO have been electrodeposited on single-crystal Cu(111) from solutions containing either (S,S)- or (R,R)-tartrate. X-ray pole figure analysis reveals that the CuO film grown from (S,S)-tartrate exhibits a (1) out-of-plane orientation while the film grown from (R,R)-tartrate has a (11) orientation. Even though CuO does not crystallize within a chiral space group, the orientations obtained exhibit a surface chirality similar to that obtained from high index fcc metal surfaces. The films were shown to be enantioselective toward the catalytic oxidation of tartrate molecules by cyclic voltammetry. The technique should prove to be applicable to the electrodeposition of chiral surfaces of other low-symmetry materials on achiral substrates and should prove to be of use to those interested in the synthesis, separation, and detection of chiral molecules.

  13. Functional Testing and Characterisation of ISFETs on Wafer Level by Means of a Micro-droplet Cell#

    PubMed Central

    Poghossian, Arshak; Schumacher, Kerstin; Kloock, Joachim P.; Rosenkranz, Christian; Schultze, Joachim W.; Müller-Veggian, Mattea; Schöning, Michael J.

    2006-01-01

    A wafer-level functionality testing and characterisation system for ISFETs (ion-sensitive field-effect transistor) is realised by means of integration of a specifically designed capillary electrochemical micro-droplet cell into a commercial wafer prober-station. The developed system allows the identification and selection of “good” ISFETs at the earliest stage and to avoid expensive bonding, encapsulation and packaging processes for non-functioning ISFETs and thus, to decrease costs, which are wasted for bad dies. The developed system is also feasible for wafer-level characterisation of ISFETs in terms of sensitivity, hysteresis and response time. Additionally, the system might be also utilised for wafer-level testing of further electrochemical sensors.

  14. Facile fabrication of Cu(II)-porphyrin MOF thin films from tetrakis(4-carboxyphenyl)porphyrin and Cu(OH)2 nanoneedle array

    NASA Astrophysics Data System (ADS)

    La, Duong Duc; Thi, Hoai Phuong Nguyen; Kim, Yong Shin; Rananaware, Anushri; Bhosale, Sheshanath V.

    2017-12-01

    Herein, we report a facile synthetic protocol to grow thin films of Cu(II) tetrakis(4-carboxyphenyl)porphyrin (CuTCPP) metal-organic frameworks (MOF) from a tetrakis(4-carboxyphenyl)porphyrin (H2TCPP) solution and the copper hydroxide (Cu(OH)2) nanoneedle array formed on a Cu substrate at room temperature. The formations of Cu-centered TCPP ligands and crystalline platelet-like Cu MOFs were successfully probed by SEM, XRD, FTIR, UV-vis and XPS. The formation process from Cu(OH)2 was monitored by using SEM images obtained at different reaction times during the first 24 h, thus suggesting the reaction pathway of Cu(OH)2 dissolution followed by the reprecipitation of CuTCPP MOFs at a near surface. In addition, the CuTCPP MOFs exhibited a high specific surface area of 408 m2/g.

  15. Syntheses, crystal structures, and characterization of two new Tl+-Cu2+-Te6+ oxides: Tl4CuTeO6 and Tl6CuTe2O10

    NASA Astrophysics Data System (ADS)

    Yeon, Jeongho; Kim, Sang-Hwan; Green, Mark A.; Bhatti, Kanwal Preet; Leighton, C.; Shiv Halasyamani, P.

    2012-12-01

    Crystals and polycrystalline powders of two new oxide materials, Tl4CuTeO6 and Tl6CuTe2O10, have been synthesized by hydrothermal and solid-state methods. The materials were structurally characterized by single-crystal X-ray diffraction. Tl4CuTeO6 and Tl6CuTe2O10 exhibit one dimensional anionic slabs of [CuTeO6]4- and [CuTe2O10]6-, respectively. Common to both slabs is the occurrence of Cu2+O4 distorted squares and Te6+O6 octahedra. The slabs are separated by Tl+ cations. For Tl4CuTeO6, magnetic measurements indicate a maximum at ∼8 K in the temperature dependence of the susceptibility. Low temperature neutron diffraction data confirm no long-range magnetic ordering occurs and the susceptibility was adequately accounted for by fits to a Heisenberg alternating chain model. For Tl6CuTe2O10 on the other hand, magnetic measurements revealed paramagnetism with no evidence of long-range magnetic ordering. Infrared, UV-vis spectra, thermogravimetric, and differential thermal analyses are also reported. Crystal data: Tl4CuTeO6, Triclinic, space group P-1 (No. 2), a=5.8629(8) Å, b=8.7848(11) Å, c=9.2572(12) Å, α=66.0460(10), β=74.2010(10), γ=79.254(2), V=417.70(9) Å3, and Z=2; Tl6CuTe2O10, orthorhombic, space group Pnma (No. 62), a=10.8628(6) Å, b=11.4962(7) Å, c=10.7238(6) Å, V=1339.20(13) Å3, and Z=4.

  16. Electron and positron states in HgBa2CuO4

    NASA Astrophysics Data System (ADS)

    Barbiellini, B.; Jarlborg, T.

    1994-08-01

    Local-density-calculations of the electronic structure of HgBa2CuO4 have been performed with the self-consistent linear muffin-tin orbital method. The positron-density distribution and its sensitivity due to different potentials are calculated. The annihilation rates are computed in order to study the chemical bonding and to predict the Fermi-surface signal. Comparisons are made with previous calculations on other high-Tc copper oxides concerning the Fermi-surface properties and electron-positron overlap. We discuss the possibility of observing the Fermi surface associated with the Cu-O planes in positron-annihilation experiments.

  17. Wafer-level manufacturing technology of glass microlenses

    NASA Astrophysics Data System (ADS)

    Gossner, U.; Hoeftmann, T.; Wieland, R.; Hansch, W.

    2014-08-01

    In high-tech products, there is an increasing demand to integrate glass lenses into complex micro systems. Especially in the lighting industry LEDs and laser diodes used for automotive applications require encapsulated micro lenses. To enable low-cost production, manufacturing of micro lenses on wafer level base using a replication technology is a key technology. This requires accurate forming of thousands of lenses with a diameter of 1-2 mm on a 200 mm wafer compliant with mass production. The article will discuss the technical aspects of a lens manufacturing replication process and the challenges, which need to be solved: choice of an appropriate master for replication, thermally robust interlayer coating, choice of replica glass, bonding and separation procedure. A promising approach for the master substrate material is based on a lens structured high-quality glass wafer with high melting point covered by a coating layer of amorphous silicon or germanium. This layer serves as an interlayer for the glass bonding process. Low pressure chemical vapor deposition and plasma enhanced chemical vapor deposition processes allow a deposition of layer coatings with different hydrogen and doping content influencing their chemical and physical behavior. A time reduced molding process using a float glass enables the formation of high quality lenses while preserving the recyclability of the mother substrate. The challenge is the separation of the replica from the master mold. An overview of chemical methods based on optimized etching of coating layer through small channels will be given and the impact of glass etching on surface roughness is discussed.

  18. Copper Selenidophosphates Cu4P2Se6, Cu4P3Se4, Cu4P4Se3, and CuP2Se, Featuring Zero-, One-, and Two-Dimensional Anions.

    PubMed

    Kuhn, Alexander; Schoop, Leslie M; Eger, Roland; Moudrakovski, Igor; Schwarzmüller, Stefan; Duppel, Viola; Kremer, Reinhard K; Oeckler, Oliver; Lotsch, Bettina V

    2016-08-15

    Five new compounds in the Cu/P/Se phase diagram have been synthesized, and their crystal structures have been determined. The crystal structures of these compounds comprise four previously unreported zero-, one-, and two-dimensional selenidophosphate anions containing low-valent phosphorus. In addition to two new modifications of Cu4P2Se6 featuring the well-known hexaselenidohypodiphosphate(IV) ion, there are three copper selenidophosphates with low-valent P: Cu4P3Se4 contains two different new anions, (i) a monomeric (zero-dimensional) selenidophosphate anion [P2Se4](4-) and (ii) a one-dimensional selenidophosphate anion [Formula: see text], which is related to the well-known gray-Se-like [Formula: see text] Zintl anion. Cu4P4Se3 contains one-dimensional [Formula: see text] polyanions, whereas CuP2Se contains the 2D selenidophosphate [Formula: see text] polyanion. It consists of charge-neutral CuP2Se layers separated by a van der Waals gap which is very rare for a Zintl-type phase. Hence, besides black P, CuP2Se constitutes a new possible source of 2D oxidized phosphorus containing layers for intercalation or exfoliation experiments. Additionally, the electronic structures and some fundamental physical properties of the new compounds are reported. All compounds are semiconducting with indirect band gaps of the orders of around 1 eV. The phases reported here add to the structural diversity of chalcogenido phosphates. The structural variety of this family of compounds may translate into a variety of tunable physical properties.

  19. Reply to Comment on ‘Oxygen vacancy-induced magnetic moment in edge-sharing CuO2 chains of Li2CuO2-δ ’

    NASA Astrophysics Data System (ADS)

    Shu, G. J.; Tian, J. C.; Lin, C. K.; Hayashi, M.; Liou, S. C.; Chen, W. T.; Wong, Deniz P.; Liou, H. L.; Chou, F. C.

    2018-05-01

    In this reply to the comment on ‘Oxygen vacancy-induced magnetic moment in edge-sharing CuO2 chains of {{{Li}}}2{{{CuO}}}2-δ ’ (2017 New Journal of Physics 19 023206), we have clarified several key questions and conflicting results regarding the size of the intra-chain nearest neighbor coupling J 1 and the sign of the Weiss temperature Θ defined in the Curie–Weiss law of χ(T) = χ ◦ + C/(T ‑ Θ). Additional data analysis is conducted to verify the validity of the Curie–Weiss law fitting protocol, including the negative sign and size of Θ based on the high-temperature linear temperature dependence of 1/χ(T) for T > J 1 and \\tfrac{g{μ }B{SH}}{{k}BT}\\ll 1. The consistency between the magnetic antiferromagnetic (AF) ground state below T N and the negative sign of Θ in the high-temperature paramagnetic (PM) state is explained via the reduction of thermal fluctuation for a temperature-independent local field due to magnetic interaction of quantum nature. A magnetic dipole–dipole (MDD)-type interaction among FM chains is identified and proposed to be necessary for the 3D AF magnetic ground state formation, i.e., the Heisenberg model of an exchange-type interaction alone is not sufficient to fully describe the quasi-1D spin chain system of {{{Li}}}2{{{CuO}}}2. Several typical quasi-1D spin chain compounds, including {{{Li}}}2{{{CuO}}}2,{{{CuAs}}}2{{{O}}}4,{{{Sr}}}3{{{Fe}}}2{{{O}}}5, and CuGeO3, are compared to show why different magnetic ground states are achieved from the chemical bond perspective.

  20. A novel nonenzymatic amperometric hydrogen peroxide sensor based on CuO@Cu2O nanowires embedded into poly(vinyl alcohol).

    PubMed

    Chirizzi, Daniela; Guascito, Maria Rachele; Filippo, Emanuela; Tepore, Antonio

    2016-01-15

    A new, very simple, rapid and inexpensive nonenzymatic amperometric sensor for hydrogen peroxide (H2O2) detection is proposed. It is based on the immobilization of cupric/cuprous oxide core shell nanowires (CuO@Cu2O-NWs) in a poly(vinyl alcohol) (PVA) matrix directly drop casted on a glassy carbon electrode surface to make a CuO@Cu2O core shell like NWs PVA embedded (CuO@Cu2O-NWs/PVA) sensor. CuO nanowires with mean diameters of 120-170nm and length in the range 2-5μm were grown by a simple catalyst-free thermal oxidation process based on resistive heating of pure copper wires at ambient conditions. The oxidation process of the copper wire surface led to the formation of a three layered structure: a thick Cu2O bottom layer, a CuO thin intermediate layer and CuO nanowires. CuO nanowires were carefully scratched from Cu2O layer with a sharp knife, dispersed into ethanol and sonicated. Then, the NWs were embedded in PVA matrix. The morphological and spectroscopic characterization of synthesized CuO-NWs and CuO@Cu2O-NWs/PVA were performed by transmission electron microscopy (TEM), selected area diffraction pattern (SAD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) analysis. Moreover a complete electrochemical characterization of these new CuO@Cu2O-NWs/PVA modified glassy carbon electrodes was performed by Cyclic Voltammetry (CV) and Cronoamperometry (CA) in phosphate buffer (pH=7; I=0.2) to investigate the sensing properties of this material against H2O2. The electrochemical performances of proposed sensors as high sensitivity, fast response, reproducibility and selectivity make them suitable for the quantitative determination of hydrogen peroxide substrate in batch analysis. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Valence charge fluctuations in YBa/sub 2/Cu/sub 3/O/sub 7-//sub delta/ from core-level spectroscopies

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Balzarotti, A.; De Crescenzi, M.; Motta, N.

    1988-10-01

    From x-ray photoemission and Auger measurements of the Cu 2p and O 1s core levels of YBa/sub 2/Cu/sub 3/O/sub 7-//sub delta/ as a function of the oxygen concentration delta, the average copper charge is determined. Evidence is found of dynamic charge fluctuations on the oxygen sublattice giving rise to a greater concentration of trivalent copper at the Cu(1) sites with respect to that determined by the analysis of neutron-diffraction data. On the basis of our experimental results, we introduce a molecular cluster description for the Cu states. The lowest final-states configurations of Cu/sup 2+/ and Cu/sup 3+/ are c3d/sup 10/Lmore » and c3d/sup 10/L/sup 2/, respectively, where c and L denote core holes on copper and oxygen atoms. Oxygen holes have high mobility and a Hubbard correlation energy less than 2 eV, a signature of their delocalization. The effect of temperature on the spectra is minor. Surface degradation modifies the relative intensity of the structures, particularly those of the O spectrum.« less

  2. Influence of Donor on the Sensing Performance of a Series of Through-Bond Energy Transfer-Based Two-photon Fluorescent Cu(2+) Probes.

    PubMed

    Zhang, Yu-Jin; Wang, Xin; Zhou, Yong; Wang, Chuan-Kui

    2016-07-01

    Optical properties of a series of molecular two-photon fluorescent Cu(2+) probes containing the same acceptor (rhodamine group) are analyzed using time-dependent density functional theory in combination with analytical response theory. Special emphasis is placed on evolution of the probes' optical properties in the presence of Cu(2+) . In this study, the compound with naphthalene as the donor is shown to be excellent ratiometric fluorescent chemosensor, whereas the compound with quinoline derivative as the donor shows off/on-typed colorimetric fluorescent response. For the compound with naphthalimide derivative as the donor, changing the connection between the donor and acceptor can efficiently prevent the fluorescent quenching of the probe both in the absence and presence of Cu(2+) . The donor moiety and the connection between donor and acceptor are thus found to play dominant roles on sensing performance of these probes. Moreover, distributions of molecular orbitals involved in the excitation and emission of the probes are analyzed to explore responsive mechanism of the probes. The through-bond energy transfer process is theoretically demonstrated. Our results are used to elucidate the available experimental measurements. This work is helpful to understand the relationships of structure with optical properties for the studied probes. © 2016 The American Society of Photobiology.

  3. Eu3 + amidst ionic copper in glass: Enhancement through energy transfer from Cu+, or quenching by Cu2 +?

    NASA Astrophysics Data System (ADS)

    Jiménez, José A.

    2017-02-01

    A barium-phosphate glass system doped with europium(III) and containing a high concentration of copper(I) together with a copper(II) remnant has been studied spectroscopically. The main object is to elucidate whether the orange-red emission of Eu3 + ions succeeds through sensitization via luminescent Cu+ ions or else is preferentially quenched by non-radiative transfer to Cu2 +. A characterization of the melt-quenched glass was first performed by UV/Vis optical absorption, 31P nuclear magnetic resonance and infrared absorption spectroscopy. A photoluminescence (PL) spectroscopy and emission decay dynamics assessment was subsequently performed. Despite the concentration of Cu+ being estimated to be much higher than that of Cu2 +, the data shows that quenching of Eu3 + PL by Cu2 + dominates. The lifetime analysis of emitting centers Cu+ and Eu3 + points to the origin of the manifestation being that the Eu3 + → Cu2 + non-radiative transfer rate responsible for the quenching is almost two times higher than that for the Cu+ → Eu3 + transfer accountable for the enhancement. Finally, an effort was made for the determination of Cu2 + in the glass containing Cu+, Cu2 + and Eu3 + ions based on the Eu3 + (5D0) emission decay rates. It was found to be in excellent agreement with the UV/Vis spectrophotometric approach, thus supporting the utility of Eu3 + ions for optical sensing of copper(II) in the solid state.

  4. Visible-light responsive photocatalytic fuel cell based on WO(3)/W photoanode and Cu(2)O/Cu photocathode for simultaneous wastewater treatment and electricity generation.

    PubMed

    Chen, Quanpeng; Li, Jinhua; Li, Xuejin; Huang, Ke; Zhou, Baoxue; Cai, Weimin; Shangguan, Wenfeng

    2012-10-16

    A visible-light driven photocatalytic fuel cell (PFC) system comprised of WO(3)/W photoanode and Cu(2)O/Cu photocathode was established for organic compounds degradation with simultaneous electricity generation. The central idea for its operation is the mismatched Fermi levels between the two photoelectrodes. Under light illumination, the Fermi level of WO(3)/W photoanode is higher than that of Cu(2)O/Cu photocathode. An interior bias can be produced based on which the electrons of WO(3)/W photoanode can transfer from the external circuit to combine with the holes of Cu(2)O/Cu photocathode then generates the electricity. In this manner, the electron/hole pairs separations at two photoelectrodes are facilitated to release the holes of WO(3)/W photoanode and electrons of Cu(2)O/Cu photocathode. Organic compounds can be decomposed by the holes of WO(3)/W photoanode due to its high oxidation power (+3.1-3.2 V(NHE)). The results demonstrated that various model compounds including phenol, Rhodamine B, and Congo red can be successfully decomposed in this PFC system, with the degradation rate after 5 h operation were obtained to be 58%, 63%, and 74%, respectively. The consistent operation for continuous water treatment with the electricity generation at a long time scale was also confirmed from the result. The proposed PFC system provides a self-sustained and energy-saving way for simultaneous wastewater treatment and energy recovery.

  5. Electromigration in Sn-Cu intermetallic compounds

    NASA Astrophysics Data System (ADS)

    Wei, C. C.; Chen, C. F.; Liu, P. C.; Chen, Chih

    2009-01-01

    As the shrinking in bump size continues, the effect of intermetallic compounds (IMCs) on electromigration becomes more pronounced. Electromigration in Sn-Cu intermetallic compounds was examined using edge displacement method. It was found that Cu6Sn5 compounds are more susceptible to electromigration than Cu3Sn compounds. The lower solidus temperature and higher resistivity of the Cu6Sn5 IMCs are responsible for its higher electromigration rate. Length-dependent electromigration behavior was found in the stripes of various lengths and the critical length was determined to be between 5 and 10 μm at 225 °C, which corresponded to a critical product between 2.5 and 5 A/cm. Furthermore, the Sn-Cu compounds were proven to have better electromigration resistance than eutectic SnAgCu solder.

  6. The Melting Characteristics and Interfacial Reactions of Sn-ball/Sn-3.0Ag-0.5Cu-paste/Cu Joints During Reflow Soldering

    NASA Astrophysics Data System (ADS)

    Huang, J. Q.; Zhou, M. B.; Zhang, X. P.

    2017-03-01

    In this work, the melting characteristics and interfacial reactions of Sn-ball/Sn-3.0Ag-0.5Cu-paste/Cu (Sn/SAC305-paste/Cu) structure joints were studied using differential scanning calorimetry, in order to gain a deeper and broader understanding of the interfacial behavior and metallurgical combination among the substrate (under-bump metallization), solder ball and solder paste in a board-level ball grid array (BGA) assembly process, which is often seen as a mixed assembly using solder balls and solder pastes. Results show that at the SAC305 melting temperature of 217°C, neither the SAC305-paste nor the Sn-ball coalesce, while an interfacial reaction occurs between the SAC305-paste and Cu. A slight increase in reflow temperature (from 217°C to 218°C) results in the coalescence of the SAC305-paste with the Sn-ball. The Sn-ball exhibits premelting behavior at reflow temperatures below its melting temperature, and the premelting direction is from the bottom to the top of the Sn-ball. Remarkably, at 227°C, which is nearly 5°C lower than the melting point of pure Sn, the Sn-ball melts completely, resulting from two eutectic reactions, i.e., the reaction between Sn and Cu and that between Sn and Ag. Furthermore, a large amount of bulk Cu6Sn5 phase forms in the solder due to the quick dissolution of Cu substrate when the reflow temperature is increased to 245°C. In addition, the growth of the interfacial Cu6Sn5 layer at the SAC305-paste/Cu interface is controlled mainly by grain boundary diffusion, while the growth of the interfacial Cu3Sn layer is controlled mainly by bulk diffusion.

  7. Dioxygen Binding, Activation, and Reduction to H2O by Cu Enzymes.

    PubMed

    Solomon, Edward I

    2016-07-05

    Oxygen intermediates in copper enzymes exhibit unique spectroscopic features that reflect novel geometric and electronic structures that are key to reactivity. This perspective will describe: (1) the bonding origin of the unique spectroscopic features of the coupled binuclear copper enzymes and how this overcomes the spin forbiddenness of O2 binding and activates monooxygenase activity, (2) how the difference in exchange coupling in the non-coupled binuclear Cu enzymes controls the reaction mechanism, and (3) how the trinuclear Cu cluster present in the multicopper oxidases leads to a major structure/function difference in enabling the irreversible reductive cleavage of the O-O bond with little overpotential and generating a fully oxidized intermediate, different from the resting enzyme studied by crystallography, that is key in enabling fast PCET in the reductive half of the catalytic cycle.

  8. Enhanced visible light photocatalytic activity in N-doped edge- and corner-truncated octahedral Cu2O

    NASA Astrophysics Data System (ADS)

    Zou, Mingming; Liu, Honghong; Feng, Lu; Thomas, Tiju; Yang, Minghui

    2017-03-01

    Edge- and corner-truncated octahedral Cu2O is successfully synthesized using an aqueous mixture of CuCl2, sodium dodecyl sulfate, NaOH, and NH2OH3·HCl. Cu2O1-xNx(150 °C, 30 min) samples are synthesized by nitridation of Cu2O using an ammonothermal process. Cu retains a formal valence state through and beyond the nitridation process. N concentration in this sample is 1.73 at%, out of which 1.08 at% is substitutional in nature. Photocatalytic activity of Cu2O1-xNx(150 °C, 30 min) sample is investigated and compared to that of pristine edge- and corner-truncated octahedral Cu2O. Results show that Cu2O1-xNx(150 °C, 30 min) sample with dominant {110} facets has a higher photocatalytic activity than the pristine Cu2O material. Higher surface energy and a greater density of the ;Cu; dangling bonds on {110} facets of edge- and corner-truncated octahedral Cu2O1-xNx is the plausible reason for the observed optimum catalytic activity. Furthermore defect states induced by nitridation results in improved visible light adsorption. And also the band edge states changes which brought about by N doping. This is an interesting result since it bypasses the usual challenge faced by pristine Cu2O which have band edge states between which transitions are normally forbidden. Selective radical quenching experiments suggest that photocatalytic activity of Cu2O1-xNx is due to formation of hydroxyl radicals in water, subsequent to photogeneration of charge carriers in the photocatalyst.

  9. Mechanical and Thermal Properties of Pulsed Electric Current Sintered (PECS) Cu-Diamond Compacts

    NASA Astrophysics Data System (ADS)

    Ritasalo, Riina; Kanerva, Ulla; Ge, Yanling; Hannula, Simo-Pekka

    2014-04-01

    In this work, dispersion strengthening of copper by diamonds is explored. In particular, the influence of 50- and 250-nm diamonds at contents of 3 and 6 vol. pct on the mechanical and thermal properties of pulsed electric current sintered (PECS) Cu composites is studied. The composite powders were prepared by mechanical alloying in argon atmosphere using a high-energy vibratory ball mill. The PECS compacts prepared had high density (>97 pct of T.D.) with quite evenly distributed diamonds. The effectiveness of dispersoids in increasing the microhardness was more pronounced at a smaller particle size and larger volume fraction, explained by Hall-Petch and Orowan strengthening models. The microhardness of Cu with 6 and 3 vol. pct nanodiamonds and pure sm-Cu (submicron-sized Cu) was 1.77, 1.46, and 1.02 GPa, respectively. In annealing experiments at 623 K to 873 K (350 °C to 600 °C), the composites with 6 vol. pct dispersoids retained their hardness better than those with less dispersoids or sm-Cu. The coefficient of thermal expansion was lowered when diamonds were added, being the lowest at about 14 × 10-6 K-1 between 473 K and 573 K (200 °C and 300 °C). Good bonding between the copper and diamond was qualitatively demonstrated by nanoindentation. In conclusion, high-quality Cu-diamond composites can be produced by PECS with improved strength and better thermal stability than for sm-Cu.

  10. Improved sensitivity of polychlorinated-biphenyl-orientated porous-ZnO surface photovoltage sensors from chemisorption-formed ZnO-CuPc composites

    PubMed Central

    Li, Mingtao; Meng, Guowen; Huang, Qing; Zhang, Shile

    2014-01-01

    We report a new mechanism for the enhancement of porous-ZnO surface photovoltage (SPV) response to polychlorinated biphenyls (PCBs, a notorious class of persistent organic pollutants as global environmental hazard) based on copper phthalocyanine (CuPc) chemisorptive bonding on porous-ZnO. A new ZnO-CuPc composite is formed on the porous-ZnO surface due to the interaction between the surface ZnO and CuPc, with its valence band (VB) energy level being higher than that of the pristine porous-ZnO. So that the efficiency of the photogenerated-electron transfer from the composite VB to the adjacent ZnO's surface states is drastically increased due to the reduced energy gap between the transition states. As a result, the sensitivity of the PCB-orientated SPV sensor is much improved by showing amplified variation of the SPV-signals perturbed by PCBs adsorbed on the ZnO-CuPc@porous-ZnO sensitive material. PMID:24594662

  11. Temporal variations of Cu in Jiaozhou Bay 1982-1986

    NASA Astrophysics Data System (ADS)

    Yang, Dongfang; Zhu, Sixi; Wang, Zhikang; Su, Chunhua; Wang, Qiang

    2017-12-01

    This paper analyzed the temporal variations of Cu in Jiaozhou Bay during 1982-1986. Results showed that Cu contents in study years were 0.15-5.31 μg L-1, 0.77-20.60 μg L-1, 0.11-4.00 μg L-1, 0.10-0.43 μg L-1 and 0.18-0.77 μg L-1, respectively. The Cu pollution level in this bay was moderate during 1982-1983, yet for temporal variations Cu contents in surface waters were showing decreasing trend. Cu contents in spring, summer and autumn were 0.11-20.60 μg L-1, 0.10-4.86 μg L-1 and 0.11-3.56 μg L-1, respectively. This bay was moderate pollution in spring in 1982-1983, while in other seasons in study years was still slight. These indicated that the temporal variations of Cu pollution in this bay should be taken in to account in decision-making of pollution control practice.

  12. Stabilizing CuPd Nanoparticles via CuPd Coupling to WO 2.72 Nanorods in Electrochemical Oxidation of Formic Acid

    DOE PAGES

    Xi, Zheng; Li, Junrui; Su, Dong; ...

    2017-10-05

    Stabilizing a 3d-transition metal component M from an MPd alloy structure in an acidic environment is key to the enhancement of MPd catalysis for various reactions. Here we show a strategy to stabilize Cu in 5 nm CuPd nanoparticles (NPs) by coupling the CuPd NPs with perovskite-type WO 2.72 nanorods (NRs). The CuPd NPs are prepared by controlled diffusion of Cu into Pd NPs and the coupled CuPd/WO 2.72 are synthesized by growing WO 2.72 NRs in the presence of CuPd NPs. The CuPd/WO 2.72 can stabilize Cu in 0.1 M HClO4 solution and, as a result, they show Cu,more » Pd composition dependent activity for the electrochemical oxidation of formic acid in 0.1 M HClO 4 + 0.1 M HCOOH. Among three different CuPd/WO 2.72 studied, the Cu 48Pd 52/WO 2.72 is the most efficient catalyst with its mass activity reaching 2086 mA/mgPd in a broad potential range of 0.40 to 0.80 V (vs. RHE) and staying at this value after the 12 h chronoamperometry test at 0.40 V. The synthesis can be extended to obtain other MPd/WO 2.72 (M = Fe, Co, Ni), making it possible to study MPd-WO 2.72 interactions and MPd stabilization on enhancing MPd catalysis for various chemical reactions.« less

  13. Protonation state of the Cu4S2 CuZ site in nitrous oxide reductase: redox dependence and insight into reactivity

    PubMed Central

    Johnston, Esther M.; Dell’Acqua, Simone; Pauleta, Sofia R.; Moura, Isabel; Solomon, Edward I.

    2015-01-01

    Spectroscopic and computational methods have been used to determine the protonation state of the edge sulfur ligand in the Cu4S2 CuZ form of the active site of nitrous oxide reductase (N2OR) in its 3CuICuII (1-hole) and 2CuI2CuII (2-hole) redox states. The EPR, absorption, and MCD spectra of 1-hole CuZ indicate that the unpaired spin in this site is evenly delocalized over CuI, CuII, and CuIV. 1-hole CuZ is shown to have a μ2-thiolate edge ligand from the observation of S-H bending modes in the resonance Raman spectrum at 450 and 492 cm−1 that have significant deuterium isotope shifts (−137 cm−1) and are not perturbed up to pH 10. 2-hole CuZ is characterized with absorption and resonance Raman spectroscopies as having two Cu-S stretching vibrations that profile differently. DFT models of the 1-hole and 2-hole CuZ sites are correlated to these spectroscopic features to determine that 2-hole CuZ has a μ2-sulfide edge ligand at neutral pH. The slow two electron (+1 proton) reduction of N2O by 1-hole CuZ is discussed and the possibility of a reaction between 2-hole CuZ and O2 is considered. PMID:26417423

  14. Evidence for Cu2-xSe platelets at grain boundaries and within grains in Cu(In,Ga)Se2 thin films

    NASA Astrophysics Data System (ADS)

    Simsek Sanli, E.; Ramasse, Q. M.; Mainz, R.; Weber, A.; Abou-Ras, D.; Sigle, W.; van Aken, P. A.

    2017-07-01

    Cu(In,Ga)Se2 (CIGS)-based solar cells reach high power-conversion efficiencies of above 22%. In this work, a three-stage co-evaporation method was used for their fabrication. During the growth stages, the stoichiometry of the absorbers changes from Cu-poor ([Cu]/([In] + [Ga]) < 1) to Cu-rich ([Cu]/([In] + [Ga]) > 1) and finally becomes Cu-poor again when the growth process is completed. It is known that, according to the Cu-In-Ga-Se phase diagram, a Cu-rich growth leads to the presence of Cu2-xSe (x = 0-0.25), which is assumed to assist in recrystallization, grain growth, and defect annihilation in the CIGS layer. So far, Cu2-xSe precipitates with spatial extensions on the order of 10-100 nm have been detected only in Cu-rich CIGS layers. In the present work, we report Cu2-xSe platelets with widths of only a few atomic planes at grain boundaries and as inclusions within grains in a polycrystalline, Cu-poor CIGS layer, as evidenced by high-resolution scanning transmission electron microscopy (STEM). The chemistry of the Cu-Se secondary phase was analyzed by electron energy-loss spectroscopy, and STEM image simulation confirmed the identification of the detected phase. These results represent additional experimental evidence for the proposed topotactical growth model for Cu-Se-assisted CIGS thin-film formation under Cu-rich conditions.

  15. Al and Si Alloying Effect on Solder Joint Reliability in Sn-0.5Cu for Automotive Electronics

    NASA Astrophysics Data System (ADS)

    Hong, Won Sik; Oh, Chulmin; Kim, Mi-Song; Lee, Young Woo; Kim, Hui Joong; Hong, Sung Jae; Moon, Jeong Tak

    2016-12-01

    To suppress the bonding strength degradation of solder joints in automotive electronics, we proposed a mid-temperature quaternary Pb-free Sn-0.5Cu solder alloy with minor Pd, Al, Si and Ge alloying elements. We manufactured powders and solder pastes of Sn-0.5Cu-(0.01,0.03)Al-0.005Si-(0.006-0.007)Ge alloys ( T m = 230°C), and vehicle electronic control units used for a flame-retardant-4 printed circuit board with an organic solderability preservative finish were assembled by a reflow soldering process. To investigate the degradation properties of solder joints used in engine compartments, thermal cycling tests were conducted from -40°C to 125°C (10 min dwell) for 1500 cycles. We also measured the shear strength of the solder joints in various components and observed the microstructural evolution of the solder joints. Based on these results, intermetallic compound (IMC) growth at the solder joints was suppressed by minor Pd, Al and Si additions to the Sn-0.5Cu alloy. After 1500 thermal cycles, IMC layers thicknesses for 100 parts per million (ppm) and 300 ppm Al alloy additions were 6.7 μm and 10 μm, compared to the as-reflowed bonding thicknesses of 6 μm and 7 μm, respectively. Furthermore, shear strength degradation rates for 100 ppm and 300 ppm Al(Si) alloy additions were at least 19.5%-26.2%. The cause of the improvement in thermal cycling reliability was analyzed using the (Al,Cu)-Sn, Si-Sn and Al-Sn phases dispersed around the Cu6Sn5 intermetallic at the solder matrix and bonding interfaces. From these results, we propose the possibility of a mid-temperature Sn-0.5Cu(Pd)-Al(Si)-Ge Pb-free solder for automotive engine compartment electronics.

  16. Degradation of Gate Oxide Integrity by Formation of Tiny Holes by Metal Contamination of Raw Wafer

    NASA Astrophysics Data System (ADS)

    Chen, Po-Ying

    2008-12-01

    Heavy metal atoms (such as Cu) spontaneously undergo a dissolution reaction when they come into contact with silicon. Most investigations in this extensively studied area begin with a clean, bare wafer and focus on metal contamination during the IC manufacturing stage. In this work, the effect of Fe and Cu contamination on raw wafers was elucidated. When two batches of raw wafers are scheduled, one uncontaminated and one with various degrees of contamination ranging from 0.1 to 10 ppb undergo the typical steps of the 90 nm LOGIC complementary metal-oxide-semiconductor (CMOS) semiconductor manufacturing process. The main contribution of this work is the discovery of a previously unidentified cause of gate oxide leakage: the formation of tiny holes by metal contamination during the wafer manufacturing stage. Because tiny holes are formed, a spontaneous reaction can occur even with at very low metal concentration (0.2 ppb), revealing that the wafer manufacturing stage is more vulnerable to metal contamination than the IC manufacturing stage and therefore requires stricter contamination control.

  17. Effect of Current Density and Plating Time on Cu Electroplating in TSV and Low Alpha Solder Bumping

    NASA Astrophysics Data System (ADS)

    Jung, Do-Hyun; Sharma, Ashutosh; Kim, Keong-Heum; Choo, Yong-Chul; Jung, Jae-Pil

    2015-03-01

    In this study, copper filling in through-silicon via (TSV) by pulse periodic reverse electroplating and low alpha solder bumping on Cu-filled TSVs was investigated. The via diameter and depth of TSV were 60 and 120 µm, respectively. The experimental results indicated that the thickness of electrodeposited copper layer increased with increasing cathodic current density and plating time. The electroplated Cu in TSV showed a typical bottom-up filling. A defectless, complete, and fast 100% Cu-filled TSV was achieved at cathodic and anodic current densities of -8 and 16 mA/cm2 for a plating time of 4 h, respectively. A sound low alpha solder ball, Sn-1.0 wt.% Ag-0.5 wt.% Cu (SAC 105) with a diameter of 83 µm and height of 66 µm was reflow processed at 245 °C on Cu-filled TSV. The Cu/solder joint interface was subjected to high temperature aging at 85 °C for 150 h, which showed an excellent bonding characteristic with minimum Cu-Sn intermetallic compounds growth.

  18. Electromigration in epitaxial Cu(001) lines

    NASA Astrophysics Data System (ADS)

    Ramanath, G.; Kim, H.; Goindi, H. S.; Frederick, M. J.; Shin, C.-S.; Goswami, R.; Petrov, I.; Greene, J. E.

    2002-04-01

    We report the electromigration (EM) response of single-domain epitaxial Cu(001) lines on layers of Ta, TaN, and TiN. Epitaxial Cu(001) lines on nitride layers exhibit nearly two orders of magnitude higher mean-time-to-failure (MTTF) values than those on Ta, indicating the strong influence of the underlayer. The activation energy of EM for Cu on the nitrides is ˜0.8-1.2 eV, and that of Cu on Ta is ˜0.2 eV, for 200-300 °C. Our results also indicate that the MTTF values correlate inversely to the crystal quality of the Cu layers measured by X-ray diffraction. The EM resistance of epitaxial Cu lines with different crystal quality on TaN were measured to separate the effects of interface chemistry and crystal quality. While higher quality epitaxial films reveal a higher EM resistance, the magnitude of the change is smaller than that obtained by changing the interface chemistry. Epitaxial lines exhibit more than 3-4 orders of magnitude higher MTTF than polycrystalline lines on the same underlayer. Based upon our results, we propose that the Cu/underlayer interface chemistry and presence of grain boundary diffusion play important roles in unpassivated Cu films.

  19. [Density functional theory studies on structure and spectrum of Cu3 Ti cluster].

    PubMed

    Wei, Yong-Hui; Cheng, Jian-Bo; Zhao, Bing; Lombardi, John R

    2008-07-01

    Bulk intermetallic Ti-Cu compounds have been found to possess special properties, including increased hardness, as well as displaying enhanced sound absorption and e shape memory. Since only one Raman progression is observed, there is not sufficient information to determine the structure of TiCu3. The different structures and vibrational frequencies of the Cu3 Ti cluster were studied by means of the density functional theory with SVWN5, B3LYP and BPW91 methods at basis sets of lanl2dz, 6-31g, 6-311g, 6-311g(d), 6-311 +/- g(2df) and 6-311 +/- g(3d2f). The calculated results show that the ground state of the Cu3 Ti cluster is a e-type structure with the C2v point group symmetry, and the bond lengths and vibrational frequencies of Cu3 T are considerably dependent on the variation of basis sets. We observed only a single Raman progression in approximately 300 cm(-1). This progression is most likely the totally symmetric stretch. The computed and observed Raman spectra were also compared with each other.

  20. Soldering-induced Cu diffusion and intermetallic compound formation between Ni/Cu under bump metallization and SnPb flip-chip solder bumps

    NASA Astrophysics Data System (ADS)

    Huang, Chien-Sheng; Jang, Guh-Yaw; Duh, Jenq-Gong

    2004-04-01

    Nickel-based under bump metallization (UBM) has been widely used as a diffusion barrier to prevent the rapid reaction between the Cu conductor and Sn-based solders. In this study, joints with and without solder after heat treatments were employed to evaluate the diffusion behavior of Cu in the 63Sn-37Pb/Ni/Cu/Ti/Si3N4/Si multilayer structure. The atomic flux of Cu diffused through Ni was evaluated from the concentration profiles of Cu in solder joints. During reflow, the atomic flux of Cu was on the order of 1015-1016 atoms/cm2s. However, in the assembly without solder, no Cu was detected on the surface of Ni even after ten cycles of reflow. The diffusion behavior of Cu during heat treatments was studied, and the soldering-process-induced Cu diffusion through Ni metallization was characterized. In addition, the effect of Cu content in the solder near the solder/intermetallic compound (IMC) interface on interfacial reactions between the solder and the Ni/Cu UBM was also discussed. It is evident that the (Cu,Ni)6Sn5 IMC might form as the concentration of Cu in the Sn-Cu-Ni alloy exceeds 0.6 wt.%.

  1. Ionic Diffusion in Cu6PS5Br Studied by 63Cu NMR

    NASA Astrophysics Data System (ADS)

    Ohki, H.; Harazono, K.; Erata, T.; Tasaki, A.; Ikeda, R.

    1993-10-01

    Applying 63Cu NMR technique, we observed exchange between the nonequivalent copper sites in crystalline Cu6PS5Br, known as a member of the mineral "argyrodite". Below 200 K, where the motion of the copper (I) ion is slow, we could distinguish several nonequivalent copper sites. On increasing the temperature, the chemical exchange between the nonequivalent cation sites was seen on the 63Cu NMR spectra. We could determine the activation energy for this motion to be 35 kJ mol-1 , in good agreement with the published ionic conductivity.

  2. CuCo 2O 4 ORR/OER Bi-functional catalyst: Influence of synthetic approach on performance

    DOE PAGES

    Serov, Alexey; Andersen, Nalin I.; Roy, Aaron J.; ...

    2015-02-07

    A series of CuCo 2O 4 catalysts were synthesized by pore forming, sol-gel, spray pyrolysis and sacrificial support methods. Catalysts were characterized by XRD, SEM, XPS and BET techniques. The electrochemical activity for the oxygen reduction and oxygen evolution reactions (ORR and OER) was evaluated in alkaline media by RRDE. Density Functional Theory was used to identify two different types of active sites responsible for ORR/OER activity of CuCo 2O 4 and it was found that CuCo 2O 4 can activate the O-O bond by binding molecular oxygen in bridging positions between Co or Co and Cu atoms. It wasmore » found that the sacrificial support method (SSM) catalyst has the highest performance in both ORR and OER and has the highest content of phase-pure CuCo 2O 4. It was shown that the presence of CuO significantly decreases the activity in oxygen reduction and oxygen evolution reactions. As a result, the half-wave potential (E 1/2) of CuCo 2O 4-SSM was found as 0.8 V, making this material a state-of-the-art, unsupported oxide catalyst.« less

  3. A discrete Cu cluster and a 3D MnII-CuII framework based on assembly of Mn2Cu4 clusters: synthesis, structure and magnetic properties.

    PubMed

    Chakraborty, Anindita; Escuer, Albert; Ribas, Joan; Maji, Tapas Kumar

    2016-10-04

    The synthesis, single-crystal structure characterization and detailed magnetic study of a homometallic hexanuclear Cu II cluster [Cu 6 (μ 3 -OH) 2 (ppk) 6 (H 2 O) 2 (NO 3 ) 4 ] (1) and a three-dimensional (3D) compound [{MnCu 2 (dpkO 2 H) 2 (dpkO 2 )N 3 }·(NO 3 )·H 2 O] n (2) (ppk = phenyl-2-pyridyl ketoxime; dpk = di-2-pyridyl ketone) consisting of heterometallic Mn II -Cu II hexanuclear cores as secondary building units are reported in this paper. In compound 1, two symmetry-related Cu 3 triangles consisting of a hydroxido-bridged trinuclear unit, [Cu 3 (μ 3 -OH)(ppk) 3 (H 2 O)(NO 3 )] + , are assembled through nitrate bridging giving rise to the homometallic Cu 6 cluster. Compound 2 contains heterometallic {MnCu} cores, which are further connected to each other through an azido bridging ligand in all the crystallographic directions, resulting in a 3D metal-organic framework. Construction of such a heterometallic 3D framework from {MnCu} units is until now, unknown. Magnetic studies of both 1 and 2 were performed in detail and both compounds show dominant antiferromagnetic interaction in the respective clusters. Compound 1 reveals significant spin frustration and anti-symmetric exchange interaction in the trinuclear cores, with a significantly high value of J av (-655 cm -1 ). Furthermore, compound 2 exhibits a dominant antiferromagnetic interaction, which is also supported by an extensive magneto-structural correlation which considers the different magnetic pathways.

  4. Effect of Intermetallic on Electromigration and Atomic Diffusion in Cu/SnAg3.0Cu0.5/Cu Joints: Experimental and First-Principles Study

    NASA Astrophysics Data System (ADS)

    Zhou, Wei; Liu, Lijuan; Li, Baoling; Wu, Ping

    2009-06-01

    Electromigration phenomena in a one-dimensional Cu/SnAg3.0Cu0.5/Cu joint were investigated with current stressing. The special effect of intermetallic compound (IMC) layers on the formation of serious electromigration damage induced by nonuniform current density distribution was discussed based on experimental results. Meanwhile, hillocks were observed both at the anode and near the cathode of the joint, and they were described as the result of diffusion of atoms and compressive stress released along grain boundaries to the relatively free surface. Moreover, the diffusion behavior of Cu at the cathode was analyzed with the electromigration equation, and the stability of Ag atoms in the solder during electromigration was evaluated with a first-principles method.

  5. CO adsorption on the “29” Cu xO/Cu(111) surface: An integrated DFT, STM, and TPD study

    DOE PAGES

    Hensley, Alyssa J. R.; Therrien, Andrew J.; Zhang, Renqin; ...

    2016-10-04

    The elucidation of an accurate atomistic model of surface structures is crucial for the design and understanding of effective catalysts, a process requiring a close collaboration between experimental observations and theoretical models. Any developed surface theoretical model must agree with experimental results for the surface when both clean and adsorbate covered. Here, we present a detailed study of the adsorption of CO on the “29” Cu xO/ Cu(111) surface, which is important in the understanding of ubiquitous Cubased catalysis. This study uses scanning tunneling microscopy, temperatureprogrammed desorption, and density functional theory to analyze CO adsorption on the “29” Cu xO/Cu(111)more » surface. From the experimental scanning tunneling microscopy images, CO was found to form six different ordered structures on the “29” Cu xO/Cu(111) surface depending on the surface CO coverage. By modeling the adsorption of CO on our atomistic model of the “29” Cu xO/Cu(111) surface at different coverages, we were able to match the experimentally observed CO ordered structures to specific combinations of sites on the “29” Cu xO/Cu(111) surface. Lastly, the high degree of agreement seen here between experiment and theory for the adsorption of CO on the “29” Cu xO/Cu(111) surface at various CO coverages provides further support that our atomistic model of the “29” Cu xO/Cu(111) surface is experimentally accurate.« less

  6. Single-particle excitations in the level structure of 64Cu

    NASA Astrophysics Data System (ADS)

    Samanta, S.; Das, S.; Bhattacharjee, R.; Chatterjee, S.; Raut, R.; Ghugre, S. S.; Sinha, A. K.; Garg, U.; Neelam, Kumar, N.; Jones, P.; Laskar, Md. Sazedur R.; Babra, F. S.; Biswas, S.; Saha, S.; Singh, P.; Palit, R.

    2018-01-01

    Excited states of the 64Cu(Z =29 ,N =35 ) nucleus have been probed using heavy-ion-induced fusion evaporation reaction and an array of Compton-suppressed Clovers as detection system for the emitted γ rays. More than 50 new transitions have been identified and the level scheme of the nucleus has been established up to an excitation energy Ex˜6 MeV and spin ˜10 ℏ . The experimental results have been compared with those from large-basis shell-model calculations that facilitated an understanding of the single-particle configurations underlying the level structure of the nucleus.

  7. Interplay of Cu and oxygen vacancy in optical transitions and screening of excitons in ZnO:Cu films

    NASA Astrophysics Data System (ADS)

    Darma, Yudi; Seng Herng, Tun; Marlina, Resti; Fauziah, Resti; Ding, Jun; Rusydi, Andrivo

    2014-02-01

    We study room temperature optics and electronic structures of ZnO:Cu films as a function of Cu concentration using a combination of spectroscopic ellipsometry, photoluminescence, and ultraviolet-visible absorption spectroscopy. Mid-gap optical states, interband transitions, and excitons are observed and distinguishable. We argue that the mid-gap states are originated from interactions of Cu and oxygen vacancy (Vo). They are located below conduction band (Zn4s) and above valence band (O2p) promoting strong green emission and narrowing optical band gap. Excitonic states are screened and its intensities decrease upon Cu doping. Our results show the importance of Cu and Vo driving the electronic structures and optical transitions in ZnO:Cu films.

  8. Simplified nonplanar wafer bonding for heterogeneous device integration

    NASA Astrophysics Data System (ADS)

    Geske, Jon; Bowers, John E.; Riley, Anton

    2004-07-01

    We demonstrate a simplified nonplanar wafer bonding technique for heterogeneous device integration. The improved technique can be used to laterally integrate dissimilar semiconductor device structures on a lattice-mismatched substrate. Using the technique, two different InP-based vertical-cavity surface-emitting laser active regions have been integrated onto GaAs without compromising the quality of the photoluminescence. Experimental and numerical simulation results are presented.

  9. A basin-hopping Monte Carlo investigation of the structural and energetic properties of 55- and 561-atom bimetallic nanoclusters: the examples of the ZrCu, ZrAl, and CuAl systems.

    PubMed

    De Souza, Douglas G; Cezar, Henrique M; Rondina, Gustavo G; de Oliveira, Marcelo F; Da Silva, Juarez L F

    2016-05-05

    We report a basin-hopping Monte Carlo investigation within the embedded-atom method of the structural and energetic properties of bimetallic ZrCu, ZrAl, and CuAl nanoclusters with 55 and 561 atoms. We found that unary Zr55, Zr561, Cu55, Cu561, Al55, and Al561 systems adopt the well known compact icosahedron (ICO) structure. The excess energy is negative for all systems and compositions, which indicates an energetic preference for the mixing of both chemical species. The ICO structure is preserved if a few atoms of the host system are replaced by different species, however, the composition limit in which the ICO structure is preserved depends on both the host and new chemical species. Using several structural analyses, three classes of structures, namely ideal ICO, nearly ICO, and distorted ICO structures, were identified. As the amounts of both chemical species change towards a more balanced composition, configurations far from the ICO structure arise and the dominant structures are nearly spherical, which indicates a strong minimization of the surface energy by decreasing the number of atoms with lower coordination on the surface. The average bond lengths follow Vegard's law almost exactly for ZrCu and ZrAl, however, this is not the case for CuAl. Furthermore, the radial distribution allowed us to identify the presence of an onion-like behavior in the surface of the 561-atom CuAl nanocluster with the Al atoms located in the outermost surface shell, which can be explained by the lower surface energies of the Al surfaces compared with the Cu surfaces. In ZrCu and ZrAl the radial distribution indicates a nearly homogeneous distribution for the chemical species, however, with a slightly higher concentration of Al atoms on the ZrAl surface, which can also be explained by the lower surface energy.

  10. Environment-Modulated Crystallization of Cu2O and CuO Nanowires by Electrospinning and Their Charge Storage Properties.

    PubMed

    Harilal, Midhun; G Krishnan, Syam; Pal, Bhupender; Reddy, M Venkatashamy; Ab Rahim, Mohd Hasbi; Yusoff, Mashitah Mohd; Jose, Rajan

    2018-02-06

    This article reports the synthesis of cuprous oxide (Cu 2 O) and cupric oxide (CuO) nanowires by controlling the calcination environment of electrospun polymeric nanowires and their charge storage properties. The Cu 2 O nanowires showed higher surface area (86 m 2 g -1 ) and pore size than the CuO nanowires (36 m 2 g -1 ). Electrochemical analysis was carried out in 6 M KOH, and both the electrodes showed battery-type charge storage mechanism. The electrospun Cu 2 O electrodes delivered high discharge capacity (126 mA h g -1 ) than CuO (72 mA h g -1 ) at a current density of 2.4 mA cm -2 . Electrochemical impedance spectroscopy measurements show almost similar charge-transfer resistance in Cu 2 O (1.2 Ω) and CuO (1.6 Ω); however, Cu 2 O showed an order of magnitude higher ion diffusion. The difference in charge storage between these electrodes is attributed to the difference in surface properties and charge kinetics at the electrode. The electrode also shows superior cyclic stability (98%) and Coulombic efficiency (98%) after 5000 cycles. Therefore, these materials could be acceptable choices as a battery-type or pseudocapacitive electrode in asymmetric supercapacitors.

  11. Interaction of intermetallic compound formation in Cu/SnAgCu/NiAu sandwich solder joints

    NASA Astrophysics Data System (ADS)

    Xia, Yanghua; Lu, Chuanyan; Chang, Junling; Xie, Xiaoming

    2006-05-01

    The interaction between Cu/solder interface and solder/Ni interface at a Cu/SnAgCu/NiAu sandwich solder joint with various surface finishes and solder heights was investigated. The interfacial microstructure and composition of intermetallic compounds (IMCs) were characterized by a scanning electron microscope (SEM) equipped with energy-dispersive x-ray spectroscopy (EDX). The phase structure of IMC was identified by x-ray diffraction (XRD). It is found that ternary (Cu,Ni)6Sn5 IMCs form at both interfaces. The composition, thickness, and morphology of the ternary IMCs depend not only on the interface itself, but also on the opposite interface. That is to say, strong coupling effects exist between the two interfaces. Lattice parameters of (Cu,Ni)6Sn5 shrink with increasing Ni content, in agreement with Vegard’s law. The mechanism of ternary IMC formation and interface coupling effects are discussed in this paper.

  12. Fabrication of 10 μm-scale conductive Cu patterns by selective laser sintering of Cu complex ink

    NASA Astrophysics Data System (ADS)

    Min, Hyungsuk; Lee, Byoungyoon; Jeong, Sooncheol; Lee, Myeongkyu

    2017-02-01

    A Cu complex ink was synthesized using copper formate as a precursor and its potential for laser patterning was investigated. The Cu ink was spin-coated onto a substrate and the coated film was space-selectively sintered using a nanosecond-pulsed ultraviolet laser. The unexposed Cu ink could be removed from the film by rinsing it with the dispersing agent used to synthesize the ink, disclosing a conductive Cu pattern. A minimum resistivity of 8.46×10-5 Ω cm was obtained for the Cu lines with 10-20 μm widths. The feasibility of this method for metallization was demonstrated by fabricating a complex Cu electric circuit on an indium tin oxide-coated glass substrate. The selective laser sintering approach provides a simple, cost-effective alternative to conventional lithography for the production of electrode or metallization patterns.

  13. Fabricating capacitive micromachined ultrasonic transducers with a novel silicon-nitride-based wafer bonding process.

    PubMed

    Logan, Andrew; Yeow, John T W

    2009-05-01

    We report the fabrication and experimental testing of 1-D 23-element capacitive micromachined ultrasonic transducer (CMUT) arrays that have been fabricated using a novel wafer-bonding process whereby the membrane and the insulation layer are both silicon nitride. The membrane and cell cavities are deposited and patterned on separate wafers and fusion-bonded in a vacuum environment to create CMUT cells. A user-grown silicon-nitride membrane layer avoids the need for expensive silicon-on-insulator (SOI) wafers, reduces parasitic capacitance, and reduces dielectric charging. It allows more freedom in selecting the membrane thickness while also providing the benefits of wafer-bonding fabrication such as excellent fill factor, ease of vacuum sealing, and a simplified fabrication process when compared with the more standard sacrificial release process. The devices fabricated have a cell diameter of 22 microm, a membrane thickness of 400 nm, a gap depth of 150 nm, and an insulation thickness of 250 nm. The resonant frequency of the CMUT in air is 17 MHz and has an attenuation compensated center frequency of approximately 9 MHz in immersion with a -6 dB fractional bandwidth of 123%. This paper presents the fabrication process and some characterization results.

  14. Development and production integration of a planarized AlCu interconnect process for submicron CMOS

    NASA Astrophysics Data System (ADS)

    Brown, Kevin C.; Hill, Rodney; Reddy, Krishna; Gadepally, Kamesh

    1995-09-01

    A planarized aluminum alloy interconnect has been developed as an alternative to tungsten plugs for a 0.65 (mu) CMOS technology. Contact resistance can increase with either an inadequate RF sputter clean or titanium that is too thin to reduce the native oxide. Diffusion barrier results show that a minimum amount of titanium nitride, whether deposited conventionally or with collimation, is necessary for low junction leakage and good sort yield. Stacked contacts and vias are supported while via resistance and defect density are improved. Electrical bridging due to silicon residues from AlSiCu can be minimized with metal overetching, but not to the extent of AlCu. Sidewall pitting was observed to be due to galvanic corrosion from copper precipitate formation. Overall yield has been improved along with decreased wafer cost compared to conventional tungsten plug technology.

  15. The Effect of Different Levels of Cu, Zn and Mn Nanoparticles in Hen Turkey Diet on the Activity of Aminopeptidases.

    PubMed

    Jóźwik, Artur; Marchewka, Joanna; Strzałkowska, Nina; Horbańczuk, Jarosław Olav; Szumacher-Strabel, Małgorzata; Cieślak, Adam; Lipińska-Palka, Paulina; Józefiak, Damian; Kamińska, Agnieszka; Atanasov, Atanas G

    2018-05-11

    The aim of the study was to estimate the influence of the different levels of Cu, Zn, and Mn nanoparticles on the activity of aminopeptidases in turkey. An experiment was carried out on 144 turkey hen Hybrid Converter. The birds were divided into groups given standard- and nanoparticle-supplementation of different level of copper (Cu 20, 10, 2 mg/kg), zinc (Zn 100, 50, 10 ppm), and manganese (Mn 100, 50, 10 ppm), covering respectively 100%, 50%, and 10% of the physiological demands for those minerals in the diet. The activity of aminopeptidases (alanyl: AlaAP, leucyl: LeuAP and arginyl: ArgAP) after supplementation of minerals was determined in the breast and thigh turkey muscle. The strongest effect of interaction among minerals supplementation form and dose on the activity levels of the aminopeptidases in thigh muscle was observed for nano-Cu already at the lowest dose of 2 mg/kg. In this dose (covering 10% of the birds’ demand) nano form of supplementation significantly increased the activity of Ala-, Leu-, and ArgAP (877, 201, and 719, respectively), compared to standard form of supplementation (461, 90.5, and 576, respectively). In turn, in breast muscle, after supplementation covering 10% of the demand with the nano-Cu, nano-Zn, and nano-Mn compared to the standard form, we did not observe any significant difference in the activity levels of any of the investigated aminopeptidases, except for AlaAP under Zn supplementation. Supplementation with the 20 mg/kg of Nano-Cu (100% of demand) and with 10 mg/kg of Nano-Cu (50% of demand) inhibited the activity of all of the three aminopeptidases in thigh muscle. Supplementation of the minerals in nano form into the diet, especially of Cu and Zn in the dose covering 10% of the demand is relevant to maintain homeostasis in turkey muscles, as indicated by the activity of the aminopeptidases.

  16. Study of GO-Cu2O and RGO-Cu nanocomposite monolayer sheets prepared by modified Langmuir Blodgett route

    NASA Astrophysics Data System (ADS)

    Botcha, V. Divakar; Sutar, D. S.; Major, S. S.

    2018-07-01

    The modified Langmuir-Blodgett (MLB) technique has been improvised and extended to transfer GO-Cu2O nanocomposite monolayer sheets, by introducing Cu2+ ions into the subphase at room temperature. Morphological studies of as-transferred sheets revealed the presence of closely spaced GO monolayer sheets, with slightly enhanced roughness. XPS studies of as-transferred sheets confirmed the presence of copper, either as metallic Cu or Cu2O, along with significant Cu(OH)2 component, but TEM results confirmed the formation of Cu2O nanocrystallites of size (7 ± 2) nm, distributed uniformly over GO sheets. After heat treatment in vacuum at 400 °C, the nanocomposite sheets were covered with a uniform distribution of larger size nanoparticles. Based on Raman, XPS and TEM studies it has been confirmed that heat treatment at 400 °C in vacuum results in the formation of agglomerated Cu nanoparticles of size (23 ± 9) nm distributed uniformly over reduced graphene oxide (RGO) sheets. The electrical characterization of nanocomposite sheets on SiO2/Si in back-gated FET geometry revealed that the electrical conductivity of as-transferred GO-Cu2O sheets was similar to that usually observed for GO monolayer sheets. The RGO-Cu sheets also displayed electrical conductivity and field effect mobility values comparable to those reported for RGO sheets obtained by chemical/thermal reduction, and was unaffected by the presence of Cu nanoparticles.

  17. Investigation of the 66Zn(p,2pn) 64Cu and 68Zn(p,x) 64Cu nuclear processes up to 100 MeV: Production of 64Cu

    NASA Astrophysics Data System (ADS)

    Szelecsényi, F.; Steyn, G. F.; Kovács, Z.; Vermeulen, C.; van der Meulen, N. P.; Dolley, S. G.; van der Walt, T. N.; Suzuki, K.; Mukai, K.

    2005-11-01

    Cross-sections of the 66Zn(p,2pn)64Cu and 68Zn(p,x)64Cu nuclear processes were measured on highly enriched zinc targets using the stacked-foil activation technique up to 100 MeV. The new cross-sections were compared to literature data. The optimum energy range for production of 64Cu was found to be 70 → 35 MeV on 66Zn and 37 → 20 MeV on 68Zn. The thick-target yields were determined as 777 MBq/μAh (21.0 mCi/μAh) and 185 MBq/μAh (5.0 mCi/μAh), respectively. The yields of the longer-lived contaminant copper radioisotopes (i.e. 61Cu when using 66Zn as target material and both 61Cu and 67Cu in the case of 68Zn target material) were also calculated. The results obtained from the present study indicate that both reactions are suited for the production of 64Cu at a medium energy cyclotron. The optimum energy ranges are also complementary therefore the potential to utilize tandem targetry exists.

  18. [A novel method for extracting leaf-level solar-induced fluorescence of typical crops under Cu stress].

    PubMed

    Qu, Ying; Liu, Su-hong; Li, Xiao-wen

    2012-05-01

    The leaf-level solar-induced fluorescence changes when the typical crops are under Cu stress, which can be considered as a sensitive indicator to estimate the stress level. In the present study, wheat (Triticum aestivum L.), pea (Pisum sativum L.) and Chinese cabbage (Brassica campestris L.) were selected and cultured with copper solutions or copper polluted soil with different Cu stress. The apparent reflectance of leaves was measured by an ASD Fieldspec spectrometer and an integrating sphere. As the apparent reflectance was seldom affected by the fluorescence emission at 580-650 and 800-1000 nm, so the apparent solar-induced fluorescence can be separated from the apparent reflectance based on PROSPECT model. The re-absorption effect of chlorophyll was corrected by three methods, called GM (Gitelson et al.'s model), AM (Agati et al.'s model) and LM (Lagorio et al.'s model). After the re-absorption correction, the solar-induced fluorescence under different Cu stress was obtained, and a positive relationship was found between the height of far RED fluorescence (FRF) and the copper contents in leaves.

  19. Energy band engineering and controlled p-type conductivity of CuAlO2 thin films by nonisovalent Cu-O alloying

    NASA Astrophysics Data System (ADS)

    Yao, Z. Q.; He, B.; Zhang, L.; Zhuang, C. Q.; Ng, T. W.; Liu, S. L.; Vogel, M.; Kumar, A.; Zhang, W. J.; Lee, C. S.; Lee, S. T.; Jiang, X.

    2012-02-01

    The electronic band structure and p-type conductivity of CuAlO2 films were modified via synergistic effects of energy band offset and partial substitution of less-dispersive Cu+ 3d10 with Cu2+ 3d9 orbitals in the valence band maximum by alloying nonisovalent Cu-O with CuAlO2 host. The Cu-O/CuAlO2 alloying films show excellent electronic properties with tunable wide direct bandgaps (˜3.46-3.87 eV); Hall measurements verify the highest hole mobilities (˜11.3-39.5 cm2/Vs) achieved thus far for CuAlO2 thin films and crystals. Top-gate thin film transistors constructed on p-CuAlO2 films were presented, and the devices showed pronounced performance with Ion/Ioff of ˜8.0 × 102 and field effect mobility of 0.97 cm2/Vs.

  20. Interfacial reactions and compound formation of Sn-Ag-Cu solders by mechanical alloying on electroless Ni-P/Cu under bump metallization

    NASA Astrophysics Data System (ADS)

    Kao, Szu-Tsung; Duh, Jenq-Gong

    2005-08-01

    Electroless Ni-P under bump metallization (UBM) has been widely used in electronic interconnections due to the good diffusion barrier between Cu and solder. In this study, the mechanical alloying (MA) process was applied to produce the SnAgCu lead-free solder pastes. Solder joints after annealing at 240°C for 15 min were employed to investigate the evolution of interfacial reaction between electroless Ni-P/Cu UBM and SnAgCu solder with various Cu concentrations ranging from 0.2 to 1.0 wt.%. After detailed quantitative analysis with an electron probe microanalyzer, the effect of Cu content on the formation of intermetallic compounds (IMCs) at SnAgCu solder/electroless Ni-P interface was evaluated. When the Cu concentration in the solder was 0.2 wt.%, only one (Ni, Cu)3Sn4 layer was observed at the solder/electroless Ni-P interface. As the Cu content increased to 0.5 wt.%, (Cu, Ni)6Sn5 formed along with (Ni, Cu)3Sn4. However, only one (Cu, Ni)6Sn5 layer was revealed, if the Cu content was up to 1 wt.%. With the aid of microstructure evolution, quantitative analysis, and elemental distribution by x-ray color mapping, the presence of the Ni-Sn-P phase and P-rich layer was evidenced.

  1. Covellite CuS as a matrix for "invisible" gold: X-ray spectroscopic study of the chemical state of Cu and Au in synthetic minerals

    NASA Astrophysics Data System (ADS)

    Tagirov, Boris R.; Trigub, Alexander L.; Kvashnina, Kristina O.; Shiryaev, Andrey A.; Chareev, Dmitriy A.; Nickolsky, Maximilian S.; Abramova, Vera D.; Kovalchuk, Elena V.

    2016-10-01

    .3 for both positions of Cu. This result is confirmed by theoretical analysis of electron density performed using quantum theory of atoms in molecules (QTAIM). Modeling of the Au L3 edge EXAFS/XANES spectra showed that Au in covellite exists in the form of the isomorphous solid solution formed by substitution for Cu atoms in triangular coordination with the Me-S distance in the first coordination shell increased by 0.18 Å relative to the pure CuS structure. The ;formal; oxidation state of Au in covellite is +1. The Bader partial atomic charge for Au in covellite is lower than the charge of Cu (+0.2 e vs. +0.5 e) indicating that the degree of covalency for the Au-bearing covellite is higher than that of pure CuS. The analysis of electronic density of states shows that this structural position of Au results in strong interactions between hybridized Au s,p,d, S p, and Cu p,d orbitals. Such chemical bonding of Au to S and Cu can result in the formation of Au-bearing solid solution with other minerals in the Cu-Fe-S system.

  2. A Bispidol Chelator with a Phosphonate Pendant Arm: Synthesis, Cu(II) Complexation, and 64Cu Labeling.

    PubMed

    Gillet, Raphaël; Roux, Amandine; Brandel, Jérémy; Huclier-Markai, Sandrine; Camerel, Franck; Jeannin, Olivier; Nonat, Aline M; Charbonnière, Loïc J

    2017-10-02

    Here we present the synthesis and characterization of a new bispidine (3,7-diazabicyclo[3.3.1]nonane) ligand with N-methanephosphonate substituents (L 2 ). Its physicochemical properties in water, as well as those of the corresponding Cu(II) and Zn(II) complexes, have been evaluated by using UV-visible absorption spectroscopy, potentiometry, 1 H and 31 P NMR, and cyclic voltammetry. Radiolabeling experiments with 64 Cu II have been carried out, showing excellent radiolabeling properties. Quantitative complexation was achieved within 60 min under stoichiometric conditions, at room temperature and in the nanomolar concentration range. It was also demonstrated that the complexation occurred below pH 2. Properties have been compared to those of the analogue bispidol bearing a N-methanecarboxylate substituent (L 1 ). Although both systems meet the required criteria to be used as new chelator for 64/67 Cu in terms of the kinetics of formation, thermodynamic stability, selectivity for Cu(II), and kinetic inertness regarding redox- or acid-assisted decomplexation processes, substitution of the carboxylic acid function by the phosphonic moiety is responsible for a significant increase in the thermodynamic stability of the Cu(II) complex (+2 log units for pCu) and also leads to an increase in the radiochemical yields with 64 Cu II which is quantitative for L 2 .

  3. [Kinetics of Cu crossing human erythrocyte membrane].

    PubMed

    Dun, Zhu Ci Ren

    2014-12-01

    This study was aimed to investigate various factors influencing the proceduction of Cu(II) crossing human erythrocyte membrane, including concentration of Cu²⁺, pH value of the medium, temperature and time of incubation, and to derive kinetic equation of Cu(II) crossing human erythrocyte membrane. Suspension red blood cells were incubated by Cu²⁺, then content of Cu²⁺ crossed human erythrocyte membrane was determined by atomic absorption spectrometry under various conditions after digestion. The results showed that content of Cu²⁺ crossed human erythrocyte membrane increased with the increase of extracellular Cu²⁺ and enhancement of incubation temperature, and the content of Cu²⁺ crossed human erythrocyte membrane showed a increasing tendency when pH reached to 6.2-7.4, and to maximum at pH 7.4, then gradually decreased at range of pH 7.4-9.2. It is concluded that the Cu²⁺ crossing human erythrocyte has been confirmed to be the first order kinetics characteristics within 120 min, and the linear equation is 10³ × Y = 0.0497t +6.5992.

  4. The effect of Na on Cu-K-In-Se thin film growth

    NASA Astrophysics Data System (ADS)

    Muzzillo, Christopher P.; Tong, Ho Ming; Anderson, Timothy J.

    2018-04-01

    Co-evaporation of Cu-KF-In-Se was performed on substrates with varied Na supply. Compositions of interest for photovoltaic absorbers were studied, with ratios of (K + Cu)/In ∼ 0.85 and K/(K + Cu) ∼ 0-0.57. Bare soda-lime glass (SLG) substrates had the highest Na supply as measured by secondary ion mass spectrometry, while SLG/Mo and SLG/SiO2/Mo substrates led to 3x and 3000x less Na in the growing film, respectively. Increased Na supply favored Cu1-xKxInSe2 (CKIS) alloy formation as proven by X-ray diffraction (XRD), while decreased Na supply favored the formation of CuInSe2 + KInSe2 mixed-phase films. Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed the KInSe2 precipitates to be readily recognizable planar crystals. Extrinsic KF addition during film growth promoted diffusion of Na out from the various substrates and into the growing film, in agreement with previous reports. Time-resolved photoluminescence showed enhanced minority carrier lifetimes for films with moderate K compositions (0.04 < K/(K + Cu) < 0.14) grown on SLG/Mo. Due to the relatively high detection limit of KInSe2 by XRD and the low magnitude of chalcopyrite lattice shift for CKIS alloys with these compositions, it is unclear if the lifetime gains were associated with CKIS alloying, minor KInSe2 content, or both. The identified Na-K interdependency can be used to engineer alkali metal bonding in Cu(In,Ga)(Se,S)2 absorbers to optimize both initial and long-term photovoltaic power generation.

  5. The effect of Na on Cu-K-In-Se thin film growth

    DOE PAGES

    Muzzillo, Christopher P.; Tong, Ho Ming; Anderson, Timothy J.

    2018-02-27

    Co-evaporation of Cu-KF-In-Se was performed on substrates with varied Na supply. Compositions of interest for photovoltaic absorbers were studied, with ratios of (K + Cu)/In ~ 0.85 and K/(K + Cu) ~ 0-0.57. Bare soda-lime glass (SLG) substrates had the highest Na supply as measured by secondary ion mass spectrometry, while SLG/Mo and SLG/SiO 2/Mo substrates led to 3x and 3000x less Na in the growing film, respectively. Increased Na supply favored Cu 1-xK xInSe 2 (CKIS) alloy formation as proven by X-ray diffraction (XRD), while decreased Na supply favored the formation of CuInSe 2 + KInSe 2 mixed-phase films.more » Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed the KInSe 2 precipitates to be readily recognizable planar crystals. Extrinsic KF addition during film growth promoted diffusion of Na out from the various substrates and into the growing film, in agreement with previous reports. Time-resolved photoluminescence showed enhanced minority carrier lifetimes for films with moderate K compositions (0.04 < K/(K + Cu) < 0.14) grown on SLG/Mo. Due to the relatively high detection limit of KInSe 2 by XRD and the low magnitude of chalcopyrite lattice shift for CKIS alloys with these compositions, it is unclear if the lifetime gains were associated with CKIS alloying, minor KInSe 2 content, or both. The identified Na-K interdependency can be used to engineer alkali metal bonding in Cu(In,Ga)(Se,S) 2 absorbers to optimize both initial and long-term photovoltaic power generation.« less

  6. The effect of Na on Cu-K-In-Se thin film growth

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Muzzillo, Christopher P.; Tong, Ho Ming; Anderson, Timothy J.

    Co-evaporation of Cu-KF-In-Se was performed on substrates with varied Na supply. Compositions of interest for photovoltaic absorbers were studied, with ratios of (K + Cu)/In ~ 0.85 and K/(K + Cu) ~ 0-0.57. Bare soda-lime glass (SLG) substrates had the highest Na supply as measured by secondary ion mass spectrometry, while SLG/Mo and SLG/SiO 2/Mo substrates led to 3x and 3000x less Na in the growing film, respectively. Increased Na supply favored Cu 1-xK xInSe 2 (CKIS) alloy formation as proven by X-ray diffraction (XRD), while decreased Na supply favored the formation of CuInSe 2 + KInSe 2 mixed-phase films.more » Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed the KInSe 2 precipitates to be readily recognizable planar crystals. Extrinsic KF addition during film growth promoted diffusion of Na out from the various substrates and into the growing film, in agreement with previous reports. Time-resolved photoluminescence showed enhanced minority carrier lifetimes for films with moderate K compositions (0.04 < K/(K + Cu) < 0.14) grown on SLG/Mo. Due to the relatively high detection limit of KInSe 2 by XRD and the low magnitude of chalcopyrite lattice shift for CKIS alloys with these compositions, it is unclear if the lifetime gains were associated with CKIS alloying, minor KInSe 2 content, or both. The identified Na-K interdependency can be used to engineer alkali metal bonding in Cu(In,Ga)(Se,S) 2 absorbers to optimize both initial and long-term photovoltaic power generation.« less

  7. Room-temperature bonding of epitaxial layer to carbon-cluster ion-implanted silicon wafers for CMOS image sensors

    NASA Astrophysics Data System (ADS)

    Koga, Yoshihiro; Kadono, Takeshi; Shigematsu, Satoshi; Hirose, Ryo; Onaka-Masada, Ayumi; Okuyama, Ryousuke; Okuda, Hidehiko; Kurita, Kazunari

    2018-06-01

    We propose a fabrication process for silicon wafers by combining carbon-cluster ion implantation and room-temperature bonding for advanced CMOS image sensors. These carbon-cluster ions are made of carbon and hydrogen, which can passivate process-induced defects. We demonstrated that this combination process can be used to form an epitaxial layer on a carbon-cluster ion-implanted Czochralski (CZ)-grown silicon substrate with a high dose of 1 × 1016 atoms/cm2. This implantation condition transforms the top-surface region of the CZ-grown silicon substrate into a thin amorphous layer. Thus, an epitaxial layer cannot be grown on this implanted CZ-grown silicon substrate. However, this combination process can be used to form an epitaxial layer on the amorphous layer of this implanted CZ-grown silicon substrate surface. This bonding wafer has strong gettering capability in both the wafer-bonding region and the carbon-cluster ion-implanted projection range. Furthermore, this wafer inhibits oxygen out-diffusion to the epitaxial layer from the CZ-grown silicon substrate after device fabrication. Therefore, we believe that this bonding wafer is effective in decreasing the dark current and white-spot defect density for advanced CMOS image sensors.

  8. A Chelator-Free Multifunctional [64Cu]-CuS Nanoparticle Platform for Simultaneous Micro-PET/CT Imaging and Photothermal Ablation Therapy

    PubMed Central

    Zhou, Min; Zhang, Rui; Huang, Miao; Lu, Wei; Song, Shaoli; Melancon, Marites P.; Tian, Mei; Liang, Dong; Li, Chun

    2010-01-01

    We synthesized and evaluated a novel class of chelator-free [64Cu]-CuS nanoparticles (NPs) suitable for both PET imaging and as photothermal coupling agents for photothermal ablation. [64Cu]-CuS NPs were simple to make, possessed excellent stability, and allowed robust noninvasive micro-PET imaging. Furthermore, CuS NPs displayed strong absorption in the near-infrared (NIR) region (peak 930 nm), passive targeting prefers the tumor site, and mediated ablation of U87 tumor cells upon exposure to NIR light both in vitro and in vivo after either intratumoral or intravenous injection. The combination of small diameter (~11 nm diameter), strong NIR absorption, and integration of 64Cu as a structural component makes [64Cu]-CuS NPs ideally suited for multifunctional molecular imaging and therapy. PMID:20942456

  9. Optimization of Post-selenization Process of Co-sputtered CuIn and CuGa Precursor for 11.19% Efficiency Cu(In, Ga)Se2 Solar Cells

    NASA Astrophysics Data System (ADS)

    Cheng, Ke; Han, Kaikai; Kuang, Zhongcheng; Jin, Ranran; Hu, Junxia; Guo, Longfei; Liu, Ya; Lu, Zhangbo; Du, Zuliang

    2017-04-01

    In this work, CuInGa alloy precursor films are fabricated by co-sputtering of CuIn and CuGa targets simultaneously. After selenization in a tube-type rapid thermal annealing system under a Se atmosphere, the Cu(In, Ga)Se2 (CIGS) absorber layers are obtained. Standard soda lime glass (SLG)/Mo/CIGS/CdS/i-ZnO/ITO/Ag grid structural solar cells are fabricated based on the selenized CIGS absorbers. The influences of selenization temperatures on the composition, crystallinity, and device performances are systematically investigated by x-ray energy dispersive spectroscopy, x-ray diffraction, Raman spectroscopy, and the current density-voltage ( J- V) measurement. It is found that the elemental ratio of Cu/(In + Ga) strongly depends on the selenization temperatures. Because of the appropriate elemental ratio, a 9.92% conversion efficiency is reached for the CIGS absorber selenized at 560°C. After the additional optimization by pre-annealing treatment at 280°C before the selenization, a highest conversion efficiency of 11.19% with a open-circuit ( V oc) of 456 mV, a short-circuit ( J sc) of 40.357 mA/cm2 and a fill factor of 60.82% without antireflection coating has been achieved. Above 13% efficiency improvement was achievable. Our experimental findings presented in this work demonstrate that the post-selenization of co-sputtered CuIn and CuGa precursor is a promising way to fabricate high quality CIGS absorbers.

  10. Atomic layer deposition of Cu( i ) oxide films using Cu( ii ) bis(dimethylamino-2-propoxide) and water

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Avila, J. R.; Peters, A. W.; Li, Zhanyong

    2017-01-01

    To grow fIlms of Cu2O, bis-(dimethylamino-2-propoxide)Cu(II), or Cu(dmap), is used as an atomic layer deposition precursor using only water vapor as a co-reactant. Between 110 and 175 °C, a growth rate of 0.12 ± 0.02 Å per cycle was measured using an in situ quartz crystal microbalance (QCM). X-ray photoelectron spectroscopy (XPS) confirms the growth of metal– oxide films featuring Cu(I).

  11. Mixed-ligand Cu II complexes with Me 5dien and heterocyclic acids. Synthesis, antioxidant and anti-inflammatory activity. Crystal structure of [Cu(Me 5dien)(tpaa)(H 2O)](ClO 4)

    NASA Astrophysics Data System (ADS)

    Christidis, Panayiotis C.; Georgousis, Zacharias D.; Hadjipavlou-Litina, Dimitra; Bolos, Christos A.

    2008-01-01

    The reaction of sodium salt of 2-thiophenecarboxylic acid (tpca), 2-thiopheneacetic acid (tpaa), 2-furoic acid (fa) and picolinic acid (pica), with [Cu(Me 5dien)(ClO 4) 2] ( 1) (Me 5dien = N, N, N', N″ N″-pentamethyldiethylenetriamine) in a 1:1 molar ratio, afforded new mixed-ligand compounds of the type [Cu(Me 5dien)(tpca)(H 2O)](ClO 4) ( 2), [Cu(Me 5dien)(tpaa)(H 2O)](ClO 4) ( 3), [Cu(Me 5dien)(fa)](BPh 4) ( 4) and [Cu(Me 5dien)(pica)](ClO 4) ( 5). The new mixed-ligand complexes are mononuclear, paramagnetic, conductive compounds with a distorted square pyramidal geometry. The square pyramidal stereochemistry proposed by spectroscopic (IR, UV-vis) data was further confirmed by the X-ray structure analysis of the compound ( 3) in which the Cu atom is coordinated by the three N atoms from the Me 5dien ligand, one O atom from the mono-carboxylate anion, lying on the equatorial square plane, and one O atom from the water molecule, occupying the axial position. The two Cu sbnd O bond distances are 1.955(2) and 2.212(2) Ǻ, respectively. The complexes were tested for antioxidant/anti-inflammatory activity. Complex 4 is the most active against soybean lipoxygenase with IC 50 = 100 μM. The presence of a furoic ring leads to higher lipoxygenase inhibition, whereas the picolinyl-ring supports scavenging activity.

  12. Physical Characterization of Cu-Ni-P Thin Films aiming at Cu/Cu-Ni-P Thermocouples

    NASA Astrophysics Data System (ADS)

    Tomachevski, F.; Sparvoli, M.; dos Santos Filho, S. G.

    2015-03-01

    Cu-Ni-P thin films have a high-thermoelectric power, which allows the fabrication of very sensitive heat-flux sensors based on planar technology. In this work, (100) silicon surfaces were pre-activated in a diluted hydrofluoric acid solution containing PdCl2. Following, Cu-Ni-P thin films were chemically deposited using an alkaline chemical bath containing 15 g/l NiSO4.6H2O; 0.2 g/l CuSO4.5H2O; 15 g/l Na2HPO2.H2O and 60 g/l Na3C6H5O7.2H2O at temperature of 80 °C where NH4OH was added until pH was 8.0. It was noteworthy that the stoichiometric percentages of Ni and Cu vary substantially for immersion times in the range of 1 to 3 min and they become almost stable at 50% and 35%, respectively, when the immersion time is higher than 3 min. In addition, the percentage of P remains almost constant around 1718 % for all the immersion times studied. On the other hand, the sheet resistance also varies substantially for immersion times in the range of 1 to 3 min. Based on the surface morphology, smaller grains with size in the range of 0.02 to 0.1 μm are initially grown on the silicon surface and exposed regions of silicon without deposits are also observed for immersion times in the range of 1 to 3min. Therefore, the discontinuities and non uniformities of the films are promoting, respectively, the observed behaviours of sheet resistance and stoichiometry.

  13. Cyclic Thermal Stress-Induced Degradation of Cu Metallization on Si3N4 Substrate at -40°C to 300°C

    NASA Astrophysics Data System (ADS)

    Lang, Fengqun; Yamaguchi, Hiroshi; Nakagawa, Hiroshi; Sato, Hiroshi

    2015-01-01

    The high-temperature reliability of active metal brazed copper (AMC) on Si3N4 ceramic substrates used for fabricating SiC high-temperature power modules was investigated under harsh environments. The AMC substrate underwent isothermal storage at 300°C for up to 3000 h and a thermal cycling test at -40°C to 300°C for up to 3000 cycles. During isothermal storage at 300°C, the AMC substrate exhibited high reliability, characterized by very little deformation of the copper (Cu) layer, low crack growth, and low oxidation rate of the Cu layer. Under thermal cycling conditions at -40°C to 300°C, no detachment of the Cu layer was observed even after the maximum 3000 cycles of the experiment. However, serious deformation of the Cu layer occurred and progressed as the number of thermal cycles increased, thus significantly roughening the surface of the Cu metallized layer. The cyclic thermal stress led to a significant increase in the crack growth and oxidation of the Cu layer. The maximum depth of the copper oxides reached up to 5/6 of the Cu thickness. The deformation of the Cu layer was the main cause of the decrease of the bond strength under thermal cycling conditions. The shear strength of the SiC chips bonded on the AMC substrate with a Au-12 wt.%Ge solder decreased from the original 83 MPa to 14 MPa after 3000 cycles. Therefore, the cyclic thermal stress destroyed the Cu oxides and enhanced the oxidation of the Cu layer.

  14. Exploring the mechanism and kinetics of Fe-Cu-Ag trimetallic particles for p-nitrophenol reduction.

    PubMed

    Yuan, Yue; Yuan, Donghai; Zhang, Yunhong; Lai, Bo

    2017-11-01

    Preparation conditions of Fe-Cu-Ag trimetallic particles were optimized by single-factor and response surface methodology (RSM) batch experiments to obtain high-reactive Fe 0 -based materials for p-nitrophenol (PNP) removal. Under the optimal conditions (i.e., Fe 0 dosage of 34.86 g L -1 , theoretical Cu mass loading of 81.87 mg Cu/g Fe, theoretical Ag mass loading of 1.15 mg Ag/g Fe, and preparation temperature of 52.1 °C), the actual rate constant (k obs ) of PNP reduction in 5 min was 1.64 min -1 , which shows a good agreement between the model prediction (1.85 min -1 ) of RSM and the experimental data. Furthermore, the high reactivity of Fe 0 -based trimetals was mainly attributed to the plating order of transition metals (i.e., Ag and Cu). Furthermore, we propose a new theory that the pyramid trimetallic structure of Fe-Cu-Ag could improve the electron transport and create active sites with high electron density at the surface (Ag layer) that could enhance the generation of surface-bonded atomic hydrogen ([H] abs ) or the direct reduction of pollutant. Moreover, Fe-Cu-Ag trimetallic particles were characterized by SEM, EDS, and XPS, which also could confirm the proposed theory. In addition, the leached Cu 2+ (<10 μg L -1 ) and Ag + (below detection limits) in Fe-Cu-Ag system could be neglected completely, which suggests that Fe-Cu-Ag is reliable, safe, and environment friendly. Therefore, Fe-Cu-Ag trimetallic system would be promising for the removal of pollutants from industrial wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Macroscopic and molecular approaches of enrofloxacin retention in soils in presence of Cu(II).

    PubMed

    Graouer-Bacart, Mareen; Sayen, Stéphanie; Guillon, Emmanuel

    2013-10-15

    The co-adsorption of copper and the fluoroquinolone antibiotic enrofloxacin (ENR) at the water-soil interface was studied by means of batch adsorption experiments, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The system was investigated over a pH range between 6 and 10, at different contact times, ionic strengths, and ENR concentrations. Adsorption coefficient - Kd - was determined at relevant environmental concentrations and the value obtained in water at a ionic strength imposed by the soil and at soil natural pH was equal to 0.66Lg(-1). ENR adsorption onto the soil showed strong pH dependence illustrating the influence of the electrostatic interactions in the sorption processes. The simultaneous co-adsorption of ENR and Cu(II) on the soil was also investigated. The presence of Cu(II) strongly influenced the retention of the antibiotic, leading to an increase up to 35% of adsorbed ENR amount. The combined quantitative and spectroscopic results showed that Cu(II) and ENR directly interacted at the water-soil interface to form ternary surface complexes. Cu K-edge EXAFS data indicated a molecular structure where the carboxylate and carbonyl groups of ENR coordinate to Cu(II) to form a 6-membered chelate ring and where Cu(II) bridges between ENR and the soil surface sites. Cu(II) bonds bidentately to the surface in an inner-sphere mode. Thus, the spectroscopic data allowed us to propose the formation of ternary surface complexes with the molecular architecture soil-Cu(II)-ENR. Copyright © 2013 Elsevier Inc. All rights reserved.

  16. Direct Epoxidation of Propylene over Stabilized Cu + Surface Sites on Ti Modified Cu 2O

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yang, X.; Kattel, S.; Xiong, K.

    2015-07-17

    Direct propylene epoxidation by O 2 is a challenging reaction because of the strong tendency for complete combustion. Results from the current study demonstrate the feasibility to tune the epoxidation selectivity by generating highly dispersed and stabilized Cu + active sites in a TiCuO x mixed oxide. The TiCuO x surface anchors the key surface intermediate, oxametallacycle, leading to higher selectivity for epoxidation of propylene.

  17. Effect of crystallization water on the structural and electrical properties of CuWO{sub 4} under high pressure

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang, Li; Yan, Jiejuan; Liu, Cailong

    2015-11-16

    The effect of crystallization water on the structural and electrical properties of CuWO{sub 4} under high pressure has been investigated by in situ X-ray diffraction and alternating current impedance spectra measurements. The crystallization water was found to be a key role in modulating the structural stability of CuWO{sub 4} at high pressures. The anhydrous CuWO{sub 4} undergoes two pressure-induced structural transitions at 8.8 and 18.5 GPa, respectively, while CuWO{sub 4}·2H{sub 2}O keeps its original structure up to 40.5 GPa. Besides, the crystallization water makes the electrical transport behavior of anhydrous CuWO{sub 4} and CuWO{sub 4}·2H{sub 2}O quite different. The charge carrier transportationmore » is always isotropic in CuWO{sub 4}·2H{sub 2}O, but anisotropic in the triclinic and the third phase of anhydrous CuWO{sub 4}. The grain resistance of CuWO{sub 4}·2H{sub 2}O is always larger than that of anhydrous CuWO{sub 4} in the entire pressure range. By analyzing the relaxation response, we found that the large number of hydrogen bonds can soften the grain characteristic frequency of CuWO{sub 4}·2H{sub 2}O over CuWO{sub 4} by one order of magnitude.« less

  18. Cu2O/CuO Bilayered Composite as a High-Efficiency Photocathode for Photoelectrochemical Hydrogen Evolution Reaction

    NASA Astrophysics Data System (ADS)

    Yang, Yang; Xu, Di; Wu, Qingyong; Diao, Peng

    2016-10-01

    Solar powered hydrogen evolution reaction (HER) is one of the key reactions in solar-to-chemical energy conversion. It is desirable to develop photocathodic materials that exhibit high activity toward photoelectrochemical (PEC) HER at more positive potentials because a higher potential means a lower overpotential for HER. In this work, the Cu2O/CuO bilayered composites were prepared by a facile method that involved an electrodeposition and a subsequent thermal oxidation. The resulting Cu2O/CuO bilayered composites exhibited a surprisingly high activity and good stability toward PEC HER, expecially at high potentials in alkaline solution. The photocurrent density for HER was 3.15 mA·cm-2 at the potential of 0.40 V vs. RHE, which was one of the two highest reported at the same potential on copper-oxide-based photocathode. The high photoactivity of the bilayered composite was ascribed to the following three advantages of the Cu2O/CuO heterojunction: (1) the broadened light absorption band that made more efficient use of solar energy, (2) the large space-charge-region potential that enabled a high efficiency for electron-hole separation, and (3) the high majority carrier density that ensured a faster charge transportation rate. This work reveals the potential of the Cu2O/CuO bilayered composite as a promising photocathodic material for solar water splitting.

  19. Cu2O/CuO Bilayered Composite as a High-Efficiency Photocathode for Photoelectrochemical Hydrogen Evolution Reaction

    PubMed Central

    Yang, Yang; Xu, Di; Wu, Qingyong; Diao, Peng

    2016-01-01

    Solar powered hydrogen evolution reaction (HER) is one of the key reactions in solar-to-chemical energy conversion. It is desirable to develop photocathodic materials that exhibit high activity toward photoelectrochemical (PEC) HER at more positive potentials because a higher potential means a lower overpotential for HER. In this work, the Cu2O/CuO bilayered composites were prepared by a facile method that involved an electrodeposition and a subsequent thermal oxidation. The resulting Cu2O/CuO bilayered composites exhibited a surprisingly high activity and good stability toward PEC HER, expecially at high potentials in alkaline solution. The photocurrent density for HER was 3.15 mA·cm−2 at the potential of 0.40 V vs. RHE, which was one of the two highest reported at the same potential on copper-oxide-based photocathode. The high photoactivity of the bilayered composite was ascribed to the following three advantages of the Cu2O/CuO heterojunction: (1) the broadened light absorption band that made more efficient use of solar energy, (2) the large space-charge-region potential that enabled a high efficiency for electron-hole separation, and (3) the high majority carrier density that ensured a faster charge transportation rate. This work reveals the potential of the Cu2O/CuO bilayered composite as a promising photocathodic material for solar water splitting. PMID:27748380

  20. Neutron scattering study of spin ordering and stripe pinning in superconducting La 1.93 Sr 0.07 CuO 4

    DOE PAGES

    Jacobsen, H.; Zaliznyak, I. A.; Savici, A. T.; ...

    2015-11-20

    Tmore » he relationships among charge order, spin fluctuations, and superconductivity in underdoped cuprates remain controversial. We use neutron scattering techniques to study these phenomena in La 1.93 Sr 0.07 CuO 4 a superconductor with a transition temperature of c = 20 K. At << c, we find incommensurate spin fluctuations with a quasielastic energy spectrum and no sign of a gap within the energy range from 0.2 to 15 meV. A weak elastic magnetic component grows below ~ 10 K, consistent with results from local probes. Regarding the atomic lattice, we have discovered unexpectedly strong fluctuations of the CuO 6 octahedra about Cu-O bonds, which are associated with inequivalent O sites within the CuO 2 planes. Moreover, we observed a weak elastic (3 ⁻30) superlattice peak that implies a reduced lattice symmetry. he presence of inequivalent O sites rationalizes various pieces of evidence for charge stripe order in underdoped La 2-xSr xCuO 4. he coexistence of superconductivity with quasi-static spin-stripe order suggests the presence of intertwined orders; however, the rotation of the stripe orientation away from the Cu-O bonds might be connected with evidence for a finite gap at the nodal points of the superconducting gap function.« less

  1. Neutron scattering study of spin ordering and stripe pinning in superconducting La 1.93 Sr 0.07 CuO 4

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jacobsen, H.; Zaliznyak, I. A.; Savici, A. T.

    Tmore » he relationships among charge order, spin fluctuations, and superconductivity in underdoped cuprates remain controversial. We use neutron scattering techniques to study these phenomena in La 1.93 Sr 0.07 CuO 4 a superconductor with a transition temperature of c = 20 K. At << c, we find incommensurate spin fluctuations with a quasielastic energy spectrum and no sign of a gap within the energy range from 0.2 to 15 meV. A weak elastic magnetic component grows below ~ 10 K, consistent with results from local probes. Regarding the atomic lattice, we have discovered unexpectedly strong fluctuations of the CuO 6 octahedra about Cu-O bonds, which are associated with inequivalent O sites within the CuO 2 planes. Moreover, we observed a weak elastic (3 ⁻30) superlattice peak that implies a reduced lattice symmetry. he presence of inequivalent O sites rationalizes various pieces of evidence for charge stripe order in underdoped La 2-xSr xCuO 4. he coexistence of superconductivity with quasi-static spin-stripe order suggests the presence of intertwined orders; however, the rotation of the stripe orientation away from the Cu-O bonds might be connected with evidence for a finite gap at the nodal points of the superconducting gap function.« less

  2. Spin orbit and tetragonal crystalline field interaction in the valence band of CuInSe2-related ordered vacancy compound CuIn7Se12

    NASA Astrophysics Data System (ADS)

    Reena Philip, Rachel; Pradeep, B.; Shripathi, T.

    2005-04-01

    Thin films of the off-tie-line ordered vacancy compound CuIn7Se12 were deposited on optically flat glass substrates by multi-source co-evaporation method. The preliminary structural, compositional and morphological characterizations were done using X-ray diffraction, energy dispersive X-ray analysis and atomic force microscopy. The X-ray diffraction data were further analysed applying the Nelson-Riley method and CTB plus = experiment rule, respectively, for lattice constants (a = 5.746 Å and c = 11.78 Å) and bond length estimations (RCu-Se = 2.465 Å and RIn-Se = 2.554 Å). A detailed analysis of the optical absorption spectra of the compound, which exhibited a three-fold optical absorption structure in the fundamental gap region, yielded three characteristic direct energy gaps at 1.37, 1.48(7) and 1.72(8) eV indicative of valence band splitting, which were evaluated using Hopfield's quasi-cubic model. The 0.04 eV increase in spin-orbit splitting parameter of the compound (0.27 eV) compared to that of CuInSe2 (0.23 eV) is found to be suggestive of the smaller contribution of Cu d orbitals to hybridization (determined by the linear hybridization model) in this Cu-deficient compound. Spectral response spectra exhibit, in addition to a maximum around 1.34 ± 0.03 eV, two other defect transition peaks near 1.07 and 0.85 eV. The binding energies of Cu, In and Se in the compound were determined using X-ray photoelectron spectroscopy.

  3. The Triple Roles of Glutathione for a DNA-Cleaving DNAzyme and Development of a Fluorescent Glutathione/Cu2+-Dependent DNAzyme Sensor for Detection of Cu2+ in Drinking Water.

    PubMed

    Wang, Shijin; Liu, Chengcheng; Li, Guiying; Sheng, Yongjie; Sun, Yanhong; Rui, Hongyue; Zhang, Jin; Xu, Jiacui; Jiang, Dazhi

    2017-03-24

    Pistol-like DNAzyme (PLDz) is an oxidative DNA-cleaving catalytic DNA with ascorbic acid as cofactor. Herein, glutathione was induced into the reaction system to maintain reduced ascorbic acid levels for higher efficient cleavage. However, data indicated that glutathione played triple roles in PLDz-catalyzed reactions. Glutathione alone had no effect on PLDz, and showed inhibitory effect on ascorbic acid-induced PLDz catalysis, but exhibited stimulating effect on Cu 2+ -promoted self-cleavage of PLDz. Further analysis of the effect of glutathione/Cu 2+ on PLDz indicated that H 2 O 2 played a key role in PLDz catalysis. Finally, we developed a fluorescent Cu 2+ sensor (PL-Cu 1.0) based on the relationship between glutathione/Cu 2+ and catalytic activity of PLDz. The fluorescent intensity showed a linear response toward the logarithm concentration of Cu 2+ over the range from 80 nM to 30 μM, with a detection limit of 21.1 nM. PL-Cu 1.0 provided only detection of Cu 2+ over other divalent metal ions. Ca 2+ and Mg 2+ could not interfere with Cu 2+ detection even at a 1000-fold concentration. We further applied PL-Cu 1.0 for Cu 2+ detection in tap and bottled water. Water stored in copper taps overnight had relatively high Cu 2+ concentrations, with a maximum 22.3 μM. Trace Cu 2+ (52.2 nM) in deep spring was detected among the tested bottled water. Therefore, PL-Cu 1.0 is feasible to detect Cu 2+ in drinking water, with a practical application.

  4. Preparation of wafer-level glass cavities by a low-cost chemical foaming process (CFP).

    PubMed

    Shang, Jintang; Chen, Boyin; Lin, Wei; Wong, Ching-Ping; Zhang, Di; Xu, Chao; Liu, Junwen; Huang, Qing-An

    2011-04-21

    A novel foaming process-chemical foaming process (CFP)-using foaming agents to fabricate wafer-level micro glass cavities including channels and bubbles was investigated. The process consists of the following steps sequentially: (1) shallow cavities were fabricated by a wet etching on a silicon wafer; (2) powders of a proper foaming agent were placed in a silicon cavity, named 'mother cavity', on the etched silicon surface; (3) the silicon cavities were sealed with a glass wafer by anodic bonding; (4) the bonded wafers were heated to above the softening point of the glass, and baked for several minutes, when the gas released by the decomposition of the foaming agent in the 'mother cavity' went into the other sealed interconnected silicon cavities to foam the softened glass into cylindrical channels named 'daughter channels', or spherical bubbles named 'son bubbles'. Results showed that wafer-level micro glass cavities with smooth wall surfaces were achieved successfully without contamination by the CFP. A model for the CFP was proposed to predict the final shape of the glass cavity. Experimental results corresponded with model predictions. The CFP provides a low-cost avenue to preparation of micro glass cavities of high quality for applications such as micro-reactors, micro total analysis systems (μTAS), analytical and bio-analytical applications, and MEMS packaging.

  5. Long-range effect of ion irradiation on Cu surface segregation in a Cu sbnd Ni system

    NASA Astrophysics Data System (ADS)

    Zhang, Li; Tang, Guangze; Ma, Xinxin; Russell, F. Michael; Cao, Xingzhong; Wang, Baoyi; Zhang, Peng

    2011-05-01

    Ni films were deposited on one side of single crystal Cu substrate discs of 1.0 and 1.5 mm thickness. These discs were irradiated on the Cu side with argon ions. Evidence for enhanced Cu segregation at the Ni surface was found for both thicknesses. This effect decreased with increasing distance between the diffusion zone and the irradiated surface. Slow positron annihilation results indicate lower vacancy-like defects at the subsurface layer after Ar irradiation on the other surface of Cu disks. Such long-range effect is here interpreted on the basis of a particular type of mobile discrete breather called quodon.

  6. Corrosion Behavior of Plasma-Passivated Cu

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Barbour, J.C.; Braithwaite, J.W.; Son, K.A.

    1999-07-09

    A new approach is being pursued to study corrosion in Cu alloy systems by using combinatorial analysis combined with microscopic experimentation (the Combinatorial Microlab) to determine mechanisms for copper corrosion in air. Corrosion studies are inherently difficult because of complex interactions between materials and environment, forming a multidimensional phase space of corrosion variables. The Combinatorial Microlab was specifically developed to address the mechanism of Cu sulfidation, which is an important reliability issue for electronic components. This approach differs from convention by focusing on microscopic length scales, the relevant scale for corrosion. During accelerated aging, copper is exposed to a varietymore » of corrosive environments containing sulfidizing species that cause corrosion. A matrix experiment was done to determine independent and synergistic effects of initial Cu oxide thickness and point defect density. The CuO{sub x} was controlled by oxidizing Cu in an electron cyclotron resonance (ECR) O{sub 2} plasma, and the point defect density was modified by Cu ion irradiation. The matrix was exposed to 600 ppb H{sub 2}S in 65% relative humidity air atmosphere. This combination revealed the importance of oxide quality in passivating Cu and prevention of the sulfidizing reaction. A native oxide and a defect-laden ECR oxide both react at 20 C to form a thick Cu{sub 2}S layer after exposure to H{sub 2}S, while different thicknesses of as-grown ECR oxide stop the formation of Cu{sub 2}S. The species present in the ECR oxide will be compared to that of an air oxide, and the sulfide layer growth rate will be presented.« less

  7. Grindability of cast Ti-Cu alloys.

    PubMed

    Kikuchi, Masafumi; Takada, Yukyo; Kiyosue, Seigo; Yoda, Masanobu; Woldu, Margaret; Cai, Zhuo; Okuno, Osamu; Okabe, Toru

    2003-07-01

    The purpose of the present study was to evaluate the grindability of a series of cast Ti-Cu alloys in order to develop a titanium alloy with better grindability than commercially pure titanium (CP Ti), which is considered to be one of the most difficult metals to machine. Experimental Ti-Cu alloys (0.5, 1.0, 2.0, 5.0, and 10.0 mass% Cu) were made in an argon-arc melting furnace. Each alloy was cast into a magnesia mold using a centrifugal casting machine. Cast alloy slabs (3.5 mm x 8.5 mm x 30.5 mm), from which the hardened surface layer (250 microm) was removed, were ground using a SiC abrasive wheel on an electric handpiece at four circumferential speeds (500, 750, 1000, or 1250 m/min) at 0.98 N (100 gf). Grindability was evaluated by measuring the amount of metal volume removed after grinding for 1min. Data were compared to those for CP Ti and Ti-6Al-4V. For all speeds, Ti-10% Cu alloy exhibited the highest grindability. For the Ti-Cu alloys with a Cu content of 2% or less, the highest grindability corresponded to an intermediate speed. It was observed that the grindability increased with an increase in the Cu concentration compared to CP Ti, particularly for the 5 or 10% Cu alloys at a circumferential speed of 1000 m/min or above. By alloying with copper, the cast titanium exhibited better grindability at high speed. The continuous precipitation of Ti(2)Cu among the alpha-matrix grains made this material less ductile and facilitated more effective grinding because small broken segments more readily formed.

  8. Improvement of the field-trapping capabilities of bulk Nd Ba Cu O superconductors using Ba Cu O substrates

    NASA Astrophysics Data System (ADS)

    Matsui, Motohide; Nariki, Shinya; Sakai, Naomichi; Iwafuchi, Kengo; Murakami, Masato

    2006-07-01

    We used Ba-Cu-O substrates to fabricate bulk Nd-Ba-Cu-O superconductors using a top-seeded melt-growth method. There were several advantages for the use of Ba-Cu-O substrate compared to conventional substrate materials such as MgO, ZrO2, Al2O3, RE123 and RE211 (RE = rare earth). The Ba-Cu-O did not react with the precursor and minimized liquid loss. Accordingly, the introduction of large-sized cracks was suppressed. We also found that Tc values were high at the bottom regions, which was ascribed to the beneficial effect of Ba-Cu-O in suppressing Nd/Ba substitution. As a result, we obtained bulk Nd-Ba-Cu-O superconductors that exhibited fairly good field-trapping capabilities, even at the bottom surfaces.

  9. Investigation of thin film solar cells based on Cu2S and ternary compounds such as CuInS2

    NASA Technical Reports Server (NTRS)

    Loferski, J. J.

    1975-01-01

    Production and characterization in thin film form of Cu2S and related Cu compounds such as CuInS2 for photovoltaic cells are examined. The low cost process technology being reported, namely the sulfurization method, is capable of producing films on various substrates. Cathodoluminescence is being used as a diagnostic tool to identify Cu(x)S and CuInS2 compounds. Also, single crystals of CuInS2 are being prepared and it is contemplated that p-n junctions will be made in such crystals.

  10. Characterization of CuCrZr and CuCrZr/SS joint strength for different blanket components manufacturing conditions

    NASA Astrophysics Data System (ADS)

    Gillia, Olivier; Briottet, Laurent; Chu, Isabelle; Lemoine, Patrick; Rigal, Emmanuel; Peacock, Alan

    2009-04-01

    This work describes studies on the strength of CuCrZr/SS joints for different manufacturing conditions foreseen for the fabrication of blanket components. In the meantime, as junction strength is expected to be strongly related to CuCrZr properties, investigation on the properties of the CuCrZr itself after the different manufacturing conditions is also presented. The initial manufacturing conditions retained were made of a HIP treatment combined with a fast cooling plus a subsequent ageing treatment. For security reasons, the HIP-quenching operation was not possible. A supplementary solutionning cycle with fast cooling has thus been inserted in the heat treatment process just after the HIP bonding treatment. The influence of solutionning temperature (1040 °C or 980 °C), the cooling rate after solutionning (70 °C/min to water quench), the ageing temperature (480 °C or 560 °C) and the HIP temperature (1040 °C or 980 °C) have been addressed. Test results show that the ageing temperature is very important for keeping high strength of material whereas elongation properties are not very sensible to the manufacturing conditions. 1040 °C HIP or solutionning temperature gives better strength properties, as well as a higher cooling rate after solutionning. Concerning samples with joints, it appears that CT test is more selective than other tests since tensile test does not give rupture at joint and KCU test eliminates a route without classifying other routes.

  11. Multishelled Si@Cu Microparticles Supported on 3D Cu Current Collectors for Stable and Binder-free Anodes of Lithium-Ion Batteries.

    PubMed

    Zhang, Zailei; Wang, Zhong Lin; Lu, Xianmao

    2018-04-24

    Silicon has proved to be a promising anode material of high-specific capacity for the next-generation lithium ion batteries (LIBs). However, during repeated discharge/charge cycles, Si-based electrodes, especially those in microscale size, pulverize and lose electrical contact with the current collectors due to large volume expansion. Here, we introduce a general method to synthesize Cu@M (M = Si, Al, C, SiO 2 , Si 3 N 4 , Ag, Ti, Ta, SnIn 2 O 5 , Au, V, Nb, W, Mg, Fe, Ni, Sn, ZnO, TiN, Al 2 O 3 , HfO 2 , and TiO 2 ) core-shell nanowire arrays on Cu substrates. The resulting Cu@Si nanowire arrays were employed as LIB anodes that can be reused via HCl etching and H 2 -reduction. Multishelled Cu@Si@Cu microparticles supported on 3D Cu current collectors were further prepared as stable and binder-free LIB anodes. This 3D Cu@Si@Cu structure allows the interior conductive Cu network to effectively accommodate the volume expansion of the electrode and facilitates the contact between the Cu@Si@Cu particles and the current collectors during the repeated insertion/extraction of lithium ions. As a result, the 3D Cu@Si@Cu microparticles at a high Si-loading of 1.08 mg/cm 2 showed a capacity retention of 81% after 200 cycles. In addition, charging tests of 3D Cu@Si@Cu-LiFePO 4 full cells by a triboelectric nanogenerator with a pulsed current demonstrated that LIBs with silicon anodes can effectively store energy delivered by mechanical energy harvesters.

  12. Charge dynamics of 57Fe probe atoms in La2Li0.5Cu0.5O4

    NASA Astrophysics Data System (ADS)

    Presniakov, I. A.; Sobolev, A. V.; Rusakov, V. S.; Moskvin, A. S.; Baranov, A. V.

    2018-06-01

    The objective of this study is to characterize the electronic state and local surrounding of 57Fe Mössbauer probe atoms within iron-doped layered perovskite La2Li0.5Cu0.5O4 containing transition metal in unusual formal oxidation states "+3". An approach based on the qualitative energy diagrams analysis and the calculations within the cluster configuration interaction method have been developed. It was shown that a large amount of charge is transferred via Cu-O bonds from the O: 2p bands to the Cu: 3d orbitals and the ground state is dominated by the d9L configuration ("Cu2+-O-" state). The dominant d9L ground state for the (CuO6) sublattice induces in the environment of the 57Fe probe cations a charge transfer Fe3+ + O-(L) → Fe4+ + O2-, which transforms "Fe3+" into "Fe4+" state. The experimental spectra in the entire temperature range 77-300 K were described with the use of the stochastic two-level model based on the assumption of dynamic equilibrium between two Fe3+↔Fe4+ valence states related to the iron atom in the [Fe(1)O4]4- center. The relaxation frequencies and activation energies of the corresponding charge fluctuations were estimated based on Mössbauer data. The results are discussed assuming a temperature-induced change in the electronic state of the [CuO4]5- clusters in the layered perovskite.

  13. High pressure synthesis and magnetic studies of quasi one dimensional systems Sr(n-1)Cu(n+1)O(2n) (n=3,5)

    NASA Technical Reports Server (NTRS)

    Azuma, M.; Hiroi, Z.; Takano, M.; Ishida, K.; Kitaoka, Y.

    1995-01-01

    SrCu2O3 and Sr2Cu3O5 containing two-leg and three-leg S = 1/2 ladders made of antiferromagnetic Cu-O-Cu linear bonds, respectively, were synthesized at high pressure, and their crystallographic and magnetic properties were investigated. Both susceptibility and T(1) data of NMR (nuclear magnetic resonance) revealed the existence of a large spin gap only for SrCu2O3. Superconductivity, which had been predicted theoretically for carrier-doped SrCu2O3 could not be realized although partial substitution of La(3+) for Sr(2+) seemed to be carried out successfully. Electron carriers injected seems to remain localized.

  14. Dielectric properties of (CuO, CaO2, and BaO)y/CuTl-1223 composites

    NASA Astrophysics Data System (ADS)

    Mumtaz, M.; Kamran, M.; Nadeem, K.; Jabbar, Abdul; Khan, Nawazish A.; Saleem, Abida; Tajammul Hussain, S.; Kamran, M.

    2013-07-01

    We synthesized (CuO, CaO2, and BaO)y/Cu0.5Tl0.5Ba2Ca2Cu3O10-δ (y = 0, 5%, 10%, 15%) composites by solid-state reaction and characterized them by x-ray diffraction, scanning electron microscopy, dc-resistivity, and Fourier transform infrared spectroscopy. Frequency and temperature dependent dielectric properties, such as real and imaginary parts of the dielectric constant, dielectric loss, and ac-conductivity of these composites were studied by capacitance and conductance measurements as a function of frequency (10 kHz to 10 MHz) and temperature (78 to 300 K). X-ray diffraction analysis reveals that the characteristic behavior of the superconductor phase and the structure of Cu0.5Tl0.5Ba2Ca2Cu3O10-δ are nearly undisturbed by doping with nanoparticles. Scanning electron microscopy images show the improvement in the intergranular linking between the superconducting grains occurring with increasing nanoparticle concentration. Microcracks are healed up with these nanoparticles, and superconducting volume fraction is also increased. Dielectric properties of these composites strongly depend on the frequency and temperature. Zero resistivity critical temperature and dielectric properties show opposite trends with the addition of nanoparticles to the Cu0.5Tl0.5Ba2Ca2Cu3O10-δ superconductor matrix.

  15. CFA-13 - a bifunctional perfluorinated metal-organic framework featuring active Cu(i) and Cu(ii) sites.

    PubMed

    Fritzsche, J; Denysenko, D; Grzywa, M; Volkmer, D

    2017-11-07

    The synthesis and crystal structure of the mixed-valent perfluorinated metal-organic framework (Me 2 NH 2 )[CFA-13] (Coordination Framework Augsburg University-13), (Me 2 NH 2 )[CuCu(tfpc) 4 ] (H 2 -tfpc = 3,5-bis(trifluoromethyl)-1H-pyrazole-4-carboxylic acid) is described. The copper-containing MOF crystallizes in the monoclinic crystal system within the space group P2 1 /n (no. 14) and the unit cell parameters are as follows: a = 22.3887(19), b = 13.6888(8), c = 21.1804(13) Å, β = 90.495(3)°, V = 6491.0(8) Å 3 . (Me 2 NH 2 )[CFA-13] features a porous 3-D structure constructed from two types of secondary building units (SBUs). Besides novel trinuclear [Cu(pz) 4 ] - coordination units, the network also exhibits Cu(ii) paddle-wheel SBUs. (Me 2 NH 2 )[CFA-13] is fully characterized by single crystal X-ray diffraction, thermogravimetric analysis, variable temperature powder X-ray diffraction, IR spectroscopy, photoluminescence, gas sorption measurements and pulse chemisorption experiments. M[CFA-13] (M = K + , Cs + ) frameworks were prepared by postsynthetic exchange of interchannel dimethylammonium cations. Moreover, it was shown that CO molecules can be selectively bound at Cu(i) sites of [Cu(pz) 4 ] - units, whereas Cu(ii) paddle-wheel units bind selectively NH 3 molecules.

  16. Digestive proteases of the lugworm (Arenicola marina) inhibited by Cu from contaminated sediments

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chen, Z.; Mayer, L.M.

    1998-03-01

    The authors examined potential toxic effects of copper released from contaminated sediments during deposit feeding of the lugworm, Arenicola marina. Titration of Cu solution into gut fluids can result in decreases in protease activity if sufficient Cu is added. The effects of Cu on gut proteases were confirmed by incubation of gut fluids with Cu-contaminated harbor sediments. Monitoring of Cu titration into gut fluids shows that enzyme inhibition and quenching of gut protein fluorescence occur only when sufficient Cu has been added to allow inorganic Cu species to become abundant. This threshold level probably represents the exhaustion of strong bindingmore » sites that act as protection against enzyme inhibition. Thus, sediments contaminated with Cu may have inhibitory effects on digestive processes in lugworms.« less

  17. Phase relations in the CuVS system

    USGS Publications Warehouse

    Wu, D.; Chang, L.L.Y.; Knowles, C.R.

    1986-01-01

    Phase relations in the system Cu-V-S were studied by using a sealedcapsule technique, reflected-light microscopy, X-ray powder diffraction and electron microprobe analysis. In the temperature range between 300 and 900 ??C, six vanadium sulfides exist in the V-S system. These are VS, V7S8, V3S4, V5S8, V3S5 and VS4. In the Cu-V-S system, three Cu-V sulfides are stable. Both Cu3VS4 (sulvanite) and CuV2S4 are cubic with a = 5.391 ?? 0.005 A ?? and a = 9.789 ?? 0.005 A ?? respectively, and the third has a composition Cu0.8V1.1S2. CuV2S4 forms equilibrium assemblages with all vanadium sulfides, which restricts their effects on the phase relations in the system to a small region. ?? 1986.

  18. Level Densities of Residual Nuclei from particle evaporation of 64Cu

    NASA Astrophysics Data System (ADS)

    Oginni, B. M.; Grimes, S. M.; Voinov, A. V.; Adekola, A. S.; Brune, C. R.; Carter, D.; Heinen, Z.; Jacobs, D.; Massey, T. N.; O'Donnell, J.

    2009-07-01

    The reactions of 6Li on 58Fe and 7Li on 57Fe have been studied at beam energy 15 MeV. These two reactions produce the same compound nucleus, 64Cu. The neutron, proton, and alpha spectra were measured at backward angles. The data obtained have been compared with Hauser Fesh-bach model calculations. The level density parameters of the residual nuclei have been obtained from the particle evaporation spectra.

  19. Synthesis of Two-Electron Bimetallic Cu-Ag and Cu-Au Clusters by using [Cu13 (S2 CNn Bu2 )6 (C≡CPh)4 ]+ as a Template.

    PubMed

    Silalahi, Rhone P Brocha; Chakrahari, Kiran Kumarvarma; Liao, Jian-Hong; Kahlal, Samia; Liu, Yu-Chiao; Chiang, Ming-Hsi; Saillard, Jean-Yves; Liu, C W

    2018-03-02

    Atomically precise Cu-rich bimetallic superatom clusters have been synthesized by adopting a galvanic exchange strategy. [Cu@Cu 12 (S 2 CN n Bu 2 ) 6 (C≡CPh) 4 ][CuCl 2 ] (1) was used as a template to generate compositionally uniform clusters [M@Cu 12 (S 2 CN n Bu 2 ) 6 (C≡CPh) 4 ][CuCl 2 ], where M=Ag (2), Au (3). Structures of 1, 2 and 3 were determined by single crystal X-ray diffraction and the results were supported by ESI-MS. The anatomies of clusters 1-3 are very similar, with a centred cuboctahedral cationic core that is surrounded by six di-butyldithiocarbamate (dtc) and four phenylacetylide ligands. The doped Ag and Au atoms were found to preferentially occupy the centre of the 13-atom cuboctahedral core. Experimental and theoretical analyses of the synthesized clusters revealed that both Ag and Au doping result in significant changes in cluster stability, optical characteristics and enhancement in luminescence properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Effect of annealing process on the heterostructure CuO/Cu2O as a highly efficient photocathode for photoelectrochemical water reduction

    NASA Astrophysics Data System (ADS)

    Du, Fan; Chen, Qing-Yun; Wang, Yun-Hai

    2017-05-01

    CuO/Cu2O photocathodes were successfully prepared via simply annealing the electrodeposited Cu2O on fluoride doped tin oxide (FTO) substrate. They were characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscope (TEM), UV-vis absorption spectra and X-ray photoelectron spectroscopy (XPS). The results showed that the heterojunction of CuO/Cu2O was formed during the annealing process and presented the nature of p-type semiconductor. The photocurrent density and photoelectrochemical (PEC) stability of the p-type heterostructure CuO/Cu2O photocathode was improved greatly compared with the pure Cu2O, which was greatly affected by annealing time and temperature. The highest photo current density of -0.451 mA/cm2 and highest stability was obtained via annealing at 650 °C for 15 min (at -0.3 V vs. Ag/AgCl), which gave a remarkable improvement than the as-deposited Cu2O (-0.08 mA/cm2). This suggested that the CuO/Cu2O heterojunction facilitated the electron-hole pair separation and improved the photocathode's current and stability.

  1. Application of 67Cu Produced by 68Zn(n,n'p+d)67Cu to Biodistribution Study in Tumor-Bearing Mice

    NASA Astrophysics Data System (ADS)

    Sugo, Yumi; Hashimoto, Kazuyuki; Kawabata, Masako; Saeki, Hideya; Sato, Shunichi; Tsukada, Kazuaki; Nagai, Yasuki

    2017-02-01

    67Cu produced by the 68Zn(n,n'p+d)67Cu reaction was used for the first time to determine the biodistribution of 67CuCl2 in colorectal tumor-bearing mice. A high uptake of 67Cu was observed in the tumor as well as in the liver and kidney, which are the major organs for copper metabolism. The result showing 67Cu accumulation in the tumor suggests that 67CuCl2 can be a potential radionuclide agent for cancer radiotherapy. It should also encourage further studies on the therapeutic effect on small animals using an increased dose of 67Cu produced by the 68Zn(n,n'p+d)67Cu reaction using presently available intense neutrons.

  2. Stable Cu and Zn isotope ratios as tracers of sources and transport of Cu and Zn in contaminated soil

    NASA Astrophysics Data System (ADS)

    Bigalke, Moritz; Weyer, Stefan; Kobza, Jozef; Wilcke, Wolfgang

    2010-12-01

    Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ 65Cu, δ 66Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g -1 Cu and 2084 μg g -1 Zn in the organic horizons. The δ 65Cu values varied little (-0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ 66Zn IRMM values were isotopically lighter in ash (-0.41‰) and organic horizons (-0.85‰ to -0.47‰) than in bedrock (-0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ 66Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ 66Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ 66Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources

  3. Fabrication of a high aspect ratio thick silicon wafer mold and electroplating using flipchip bonding for MEMS applications

    NASA Astrophysics Data System (ADS)

    Kim, Bong-Hwan; Kim, Jong-Bok

    2009-06-01

    We have developed a microfabrication process for high aspect ratio thick silicon wafer molds and electroplating using flipchip bonding with THB 151N negative photoresist (JSR micro). This fabrication technique includes large area and high thickness silicon wafer mold electroplating. The process consists of silicon deep reactive ion etching (RIE) of the silicon wafer mold, photoresist bonding between the silicon mold and the substrate, nickel electroplating and a silicon removal process. High thickness silicon wafer molds were made by deep RIE and flipchip bonding. In addition, nickel electroplating was developed. Dry film resist (ORDYL MP112, TOK) and thick negative-tone photoresist (THB 151N, JSR micro) were used as bonding materials. In order to measure the bonding strength, the surface energy was calculated using a blade test. The surface energy of the bonding wafers was found to be 0.36-25.49 J m-2 at 60-180 °C for the dry film resist and 0.4-1.9 J m-2 for THB 151N in the same temperature range. Even though ORDYL MP112 has a better value of surface energy than THB 151N, it has a critical disadvantage when it comes to removing residue after electroplating. The proposed process can be applied to high aspect ratio MEMS structures, such as air gap inductors or vertical MEMS probe tips.

  4. Synthesis methods influence characteristics, behaviour and toxicity of bare CuO NPs compared to bulk CuO and ionic Cu after in vitro exposure of Ruditapes philippinarum hemocytes.

    PubMed

    Volland, Moritz; Hampel, Miriam; Katsumiti, Alberto; Yeste, María Pilar; Gatica, José Manuel; Cajaraville, Miren; Blasco, Julián

    2018-06-01

    Copper oxide (CuO) nanoparticles (NPs) are increasingly investigated, developed and produced for a wide range of industrial and consumer products. Notwithstanding their promising novel applications, concern has been raised that their increased use and disposal could consequently increase their release into marine systems and potentially affect species within. To date the understanding of factors and mechanisms of CuO (nano-) toxicity to marine invertebrates is still limited. Hence, we studied the characteristics and behaviour of two commercially available CuO NPs of similar size, but produced employing distinct synthesis methods, under various environmentally and experimentally relevant conditions. In addition, cell viability and DNA damage, as well as gene expression of detoxification, oxidative stress, inflammatory response, DNA damage repair and cell death mediator markers were studied in primary cultures of hemocytes from the marine clam Ruditapes philippinarum and, where applicable, compared to bulk CuO and ionic Cu (as CuSO 4 ) behaviour and effects. We found that the synthesis method can influence particle characteristics and behaviour, as well as the toxicity of CuO NPs to Ruditapes philippinarum hemocytes. Our results further indicate that under the tested conditions aggregating behaviour influences the toxicity of CuO NPs by influencing their rate of extra- and intracellular dissolution. In addition, gene expression analysis identified similar transcriptional de-regulation for all tested copper treatments for the here measured suite of genes. Finally, our work highlights various differences in the aggregation and dissolution kinetics of CuO particles under environmental (marine) and cell culture exposure conditions that need consideration when extrapolating in vitro findings. Copyright © 2018 Elsevier B.V. All rights reserved.

  5. Phase relations in the system Cu-Gd-O and Gibbs energy of formation of CuGd[sub 2]O[sub 4

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jacob, K.T.; Mathews, T.; Hajra, J.P.

    1993-07-01

    The phase relations in the system Cu-Gd-O have been determined at 1,273 K by X-ray diffraction, optical microscopy, and electron microprobe analysis of samples equilibrated in quartz ampules and in pure oxygen. Only one ternary compound, CuGd[sub 2]O[sub 4], was found to be stable. The Gibbs free energy of formation of this compound has been measured using the solid-state cell Pt, Cu[sub 2]O + CuGd[sub 2]O[sub 4] + Gd[sub 2]O[sub 3]//(Y[sub 2]O[sub 3])ZrO[sub 2]//CuO + Cu[sub 2]O, Pt in the temperature range of 900 to 1,350 K. For the formation of CuGd[sub 2]O[sub 4] from its binary component oxides, CuOmore » (s) + Gd[sub 2]O[sub 3] (s) [r arrow] CuGd[sub 2]O[sub 4] (s) [Delta]G[degree] = 8230 - 11.2T([plus minus]50)J/mol. Since the formation is endothermic, CuGd[sub 2]O[sub 4] becomes thermodynamically unstable with respect to CuO and Gd[sub 2]O[sub 3] below 735 K. When the oxygen partial pressure over CuGd[sub 2]O[sub 4] is lowered, it decomposes according to the reaction 4CuGd[sub 2]O[sub 4] (s) [r arrow] 4Gd[sub 2]O[sub 3] (s) + 2Cu[sub 2]O (s) + O[sub 2] (g) for which the equilibrium oxygen potential is given by [Delta][mu][sub o][sub 2] = [minus]227,970 + 143.2T([plus minus]500)J/mol. An oxygen potential diagram for the system Cu-Gd-O at 1,273 is presented.« less

  6. Evaluation of (64)Cu-labeled DOTA-D-Phe(1)-Tyr (3)-octreotide ((64)Cu-DOTA-TOC) for imaging somatostatin receptor-expressing tumors.

    PubMed

    Hanaoka, Hirofumi; Tominaga, Hideyuki; Yamada, Keiich; Paudyal, Pramila; Iida, Yasuhiko; Watanabe, Shigeki; Paudyal, Bishnuhari; Higuchi, Tetsuya; Oriuchi, Noboru; Endo, Keigo

    2009-08-01

    In-111 ((111)In)-labeled octreotide has been clinically used for imaging somatostatin receptor-positive tumors, and radiolabeled octreotide analogs for positron emission tomography (PET) have been developed. Cu-64 ((64)Cu; half-life, 12.7 h) is an attractive radionuclide for PET imaging and is produced with high specific activity using a small biomedical cyclotron. The aim of this study is to produce and fundamentally examine a (64)Cu-labeled octreotide analog, (64)Cu-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid-D: -Phe(1)-Tyr(3)-octreotide ((64)Cu-DOTA-TOC). (64)Cu produced using a biomedical cyclotron was reacted with DOTA-TOC for 30 min at 45 degrees C. The stability of (64)Cu-DOTA-TOC was evaluated in vitro (incubated with serum) and in vivo (blood collected after administration) by HPLC analysis. Biodistribution studies were performed in normal mice by administration of mixed solution of (64)Cu-DOTA-TOC and (111)In-DOTA-TOC and somatostatin receptor-positive U87MG tumor-bearing mice by administration of (64)Cu-DOTA-TOC or (64)Cu-1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetraacetic acid-octreotide ((64)Cu-TETA-OC). The tumor was imaged using (64)Cu-DOTA-TOC, (64)Cu-TETA-OC, and FDG with an animal PET scanner. (64)Cu-DOTA-TOC can be produced in amounts sufficient for clinical study with high radiochemical yield. (64)Cu-DOTA-TOC was stable in vitro, but time-dependent transchelation to protein was observed after injection into mice. In biodistribution studies, the radioactivity of (64)Cu was higher than that of (111)In in all organs except kidney. In tumor-bearing mice, (64)Cu-DOTA-TOC showed a high accumulation in the tumor, and the tumor-to-blood ratio reached as high as 8.81 +/- 1.17 at 6 h after administration. (64)Cu-DOTA-TOC showed significantly higher accumulation in the tumor than (64)Cu-TETA-OC. (64)Cu-DOTA-TOC PET showed a very clear image of the tumor, which was comparable to that of (18)F-FDG PET and very similar to that of (64)Cu

  7. Small changes in Cu redox state and speciation generate large isotope fractionation during adsorption and incorporation of Cu by a phototrophic biofilm

    NASA Astrophysics Data System (ADS)

    Coutaud, Margot; Méheut, Merlin; Glatzel, Pieter; Pokrovski, Gleb S.; Viers, Jérôme; Rols, Jean-Luc; Pokrovsky, Oleg S.

    2018-01-01

    Despite the importance of phototrophic biofilms in metal cycling in freshwater systems, metal isotope fractionation linked to metal adsorption and uptake by biofilm remains very poorly constrained. Here, copper isotope fractionation by a mature phototrophic biofilm during Cu surface adsorption and incorporation was studied in batch reactor (BR) and open drip flow reactor (DFR) systems at ambient conditions. X-ray Absorption Spectroscopy (both Near Edge Structure, XANES, and Extended Fine Structure, EXAFS) at Cu K-edge of the biofilm after its interaction with Cu in BR experiments allowed characterizing the molecular structure of assimilated Cu and quantifying the degree of CuII to CuI reduction linked to Cu assimilation. For both BR and DFR experiments, Cu adsorption caused enrichment in heavy isotope at the surface of the biofilm relative to the aqueous solution, with an apparent enrichment factor for the adsorption process, ε65Cuads, of +1.1 ± 0.3‰. In contrast, the isotope enrichment factor during copper incorporation into the biofilm (ε65Cuinc) was highly variable, ranging from -0.6 to +0.8‰. This variability of the ε65Cuinc value was likely controlled by Cu cellular uptake via different transport pathways resulting in contrasting fractionation. Specifically, the CuII storage induced enrichment in heavy isotope, whereas the toxicity response of the biofilm to Cu exposure resulted in reduction of CuII to CuI, thus yielding the biofilm enrichment in light isotope. EXAFS analyses suggested that a major part of the Cu assimilated by the biofilm is bound to 5.1 ± 0.3 oxygen or nitrogen atoms, with a small proportion of Cu linked to sulfur atoms (NS < 0.6) of sulfhydryl groups. XANES analyses showed that the proportion of CuIIvs CuI, compared to the initial CuII/CuI ratio, decreased by 14% after the first hour of reaction and by 6% after 96 h of reaction. The value of ε65Cuinc of the biofilm exhibited a similar trend over time of exposure. Our study

  8. Numerical analysis and optimization of Cu2O/TiO2, CuO/TiO2, heterojunction solar cells using SCAPS

    NASA Astrophysics Data System (ADS)

    Sawicka-Chudy, Paulina; Sibiński, Maciej; Wisz, Grzegorz; Rybak-Wilusz, Elżbieta; Cholewa, Marian

    2018-05-01

    In the presented work, the Cu2O/TiO2 and CuO/TiO2 heterojunction solar cells have been analyzed by the help of Solar Cell Capacitance Simulator (SCAPS). The effects of various layer parameters like thickness and defect density on the cell performance have been studied in details. Numerical analysis showed how the absorber (CuO, Cu2O) and buffer (TiO2) layers thickness influence the short-circuit current density (Jsc) and efficiency (η) of solar cells. Optimized solar cell structures of Cu2O/TiO2 and CuO/TiO2 showed a potential efficiency of ∼9 and ∼23%, respectively, under the AM1.5G spectrum. Additionally, external quantum efficiency (EQE) curves of the CuO/TiO2 and Cu2O/TiO2 solar cells for various layers thickness of TiO2 were calculated and the optical band gap (Eg) for CuO and Cu2O was obtained. Finally, we examined the effects of defect density on the photovoltaic parameters.

  9. CuSb(S,Se)2 thin film heterojunction photovoltaic devices

    NASA Astrophysics Data System (ADS)

    Welch, Adam W.

    Thin film heterojunction solar cells based on CuSb(S,Se)2 absorbers are investigated for two primary reasons. First, antimony is more abundant and less expensive than elements used in current thin film photovoltaics, In, Ga, and Te, and so, successful integration of Sb based materials offers greater diversification and scalability of solar energy. Second, the CuSb(S,Se) 2 ternary is chemically, electronically, and optically similar to the well-known, high efficiency, CuIn(S,Se)2 based materials. It is therefore postulated that the copper antimony ternaries will have similar defect tolerant electronic transport that may allow for similar highly efficient photoconversion. However, CuSb(S,Se)2 forms a layered crystal structure, different from the tetrahedral coordination found in conventional solar absorbers, due to the non-bonding lone pair of electrons on the antimony site. Thus examination of 2D antimony ternaries will lend insight into the role of structure in photoconversion processes. To address these questions, the semiconductors of interest (CuSbS 2 & CuSbSe2) were first synthesized on glass by combinatorial methods, to more quickly optimize process condi- tions. Radio-frequency (RF) magnetron co-sputtering from Sb2(S,Se)3 and Cu 2(S,Se) targets were used, without rotation, to produce chemical and flux graded libraries which were then subjected to high throughput characterization of structure (XRD), composition (XRF), conductivity (4pp), and optical absorption (UV/Vis/NIR). This approach rapidly identified processes that generated phase pure material with tunable carrier concentration by applying excess Sb 2(S,Se)3 within a temperature window bound by the volatility of Sb2(S,Se)3 and stability of the ternary phase. The resulting phase pure thin films were then incor- porated into the traditional CuInGaSe2 (CIGS) substrate photovoltaic (PV) architecture, and the resulting device performance was correlated to gradients in composition, sputter flux, absorber

  10. Bactericidal behavior of Cu-containing stainless steel surfaces

    NASA Astrophysics Data System (ADS)

    Zhang, Xiangyu; Huang, Xiaobo; Ma, Yong; Lin, Naiming; Fan, Ailan; Tang, Bin

    2012-10-01

    Stainless steels are one of the most common materials used in health care environments. However, the lack of antibacterial advantage has limited their use in practical application. In this paper, antibacterial stainless steel surfaces with different Cu contents have been prepared by plasma surface alloying technology (PSAT). The steel surface with Cu content 90 wt.% (Cu-SS) exhibits strong bactericidal activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) within 3 h. Although the Cu-containing surface with Cu content 2.5 wt.% (CuNi-SS) can also kill all tested bacteria, this process needs 12 h. SEM observation of the bacterial morphology and an agarose gel electrophoresis were performed to study the antibacterial mechanism of Cu-containing stainless steel surfaces against E. coli. The results indicated that Cu ions are released when the Cu-containing surfaces are in contact with bacterial and disrupt the cell membranes, killing the bacteria. The toxicity of Cu-alloyed surfaces does not cause damage to the bacterial DNA. These results provide a scientific explanation for the antimicrobial applications of Cu-containing stainless steel. The surfaces with different antibacterial abilities could be used as hygienic surfaces in healthcare-associated settings according to the diverse requirement of bactericidal activities.

  11. Metal-ligand delocalization and spin density in the CuCl{sub 2} and [CuCl{sub 4}]{sup 2−} molecules: Some insights from wave function theory

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Giner, Emmanuel, E-mail: gnrmnl@unife.it; Angeli, Celestino, E-mail: anc@unife.it

    2015-09-28

    The aim of this paper is to unravel the physical phenomena involved in the calculation of the spin density of the CuCl{sub 2} and [CuCl{sub 4}]{sup 2−} systems using wave function methods. Various types of wave functions are used here, both variational and perturbative, to analyse the effects impacting the spin density. It is found that the spin density on the chlorine ligands strongly depends on the mixing between two types of valence bond structures. It is demonstrated that the main difficulties found in most of the previous studies based on wave function methods come from the fact that eachmore » valence bond structure requires a different set of molecular orbitals and that using a unique set of molecular orbitals in a variational procedure leads to the removal of one of them from the wave function. Starting from these results, a method to compute the spin density at a reasonable computational cost is proposed.« less

  12. Commensurate Superstructure of the {Cu(NO3)(H2O)}(HTae)(Bpy) Coordination Polymer: An Example of 2D Hydrogen-Bonding Networks as Magnetic Exchange Pathway.

    PubMed

    Fernández de Luis, Roberto; Larrea, Edurne S; Orive, Joseba; Lezama, Luis; Arriortua, María I

    2016-11-21

    The average and commensurate superstructures of the one-dimensional coordination polymer {Cu(NO 3 )(H 2 O)}(HTae)(Bpy) (H 2 Tae = 1,1,2,2-tetraacetylethane, Bpy = 4,4'-bipyridine) were determined by single-crystal X-ray diffraction, and the possible symmetry relations between the space group of the average structure and the superstructure were checked. The crystal structure consists in parallel and oblique {Cu(HTae)(Bpy)} zigzag metal-organic chains stacked along the [100] crystallographic direction. The origin of the fivefold c axis in the commensurate superstructure is ascribed to a commensurate modulation of the coordination environment of the copper atoms. The commensurately ordered nitrate groups and coordinated water molecules establish a two-dimensional hydrogen-bonding network. Moreover, the crystal structure shows a commensurate to incommensurate transition at room temperature. The release of the coordination water molecules destabilizes the crystal framework, and the compound shows an irreversible structure transformation above 100 °C. Despite the loss of crystallinity, the spectroscopic studies indicate that the main building blocks of the crystal framework are retained after the transformation. The hydrogen-bonding network not only plays a crucial role stabilizing the crystal structure but also is an important pathway for magnetic exchange transmission. In fact, the magnetic susceptibility curves indicate that after the loss of coordinated water molecules, and hence the collapse of the hydrogen-bonding network, the weak anti-ferromagnetic coupling observed in the initial compound is broken. The electron paramagnetic resonance spectra are the consequence of the average signals from Cu(II) with different orientations, indicating that the magnetic coupling is effective between them. In fact, X- and Q-band data are reflecting different situations; the X-band spectra show the characteristics of an exchange g-tensor, while the Q-band signals are coming from

  13. Raman spectra of oriented and non-oriented Cu hydroxy-phosphate minerals: libethenite, cornetite, pseudomalachite, reichenbachite and ludjibaite.

    PubMed

    Kharbish, Sherif; Andráš, Peter; Luptáková, Jarmila; Milovská, Stanislava

    2014-09-15

    Oriented cornetite [Cu3PO4(OH)3], libethenite [Cu2PO4(OH)] and pseudomalachite [Cu5(PO4)2(OH)4] and non-oriented reichenbachite [Cu5(PO4)2(OH)4] and ludjibaite [Cu5(PO4)2(OH)4] minerals from Ľubietová and Špania Dolina dump fields, Banská Bystrica, Slovakia were examined by polarized Raman spectroscopy. The examined minerals display the characteristic vibrational modes of PO4 and OH groups and further lattice modes. The PO4 stretching and bending vibrations of the investigated minerals occur between 1150 and 900 cm(-1) and between 700 and 350 cm(-1), respectively. On the other hand, the hydroxyl group stretching and bending modes appear above 3350 cm(-1) and between 900 and 700 cm(-1), respectively. The lattice vibrations occur below 350 cm(-1). The different bond distances of the PO4 groups readily explain the shift of the bands to higher or lower wavenumbers among the studied Cu hydroxy-phosphate minerals. Copyright © 2014. Published by Elsevier B.V.

  14. Behavior of Brazed W/Cu Mockup Under High Heat Flux Loads

    NASA Astrophysics Data System (ADS)

    Chen, Lei; Lian, Youyun; Liu, Xiang

    2014-03-01

    In order to transfer the heat from the armor to the coolant, tungsten has to be connected with a copper heat sink. The joint technology is the most critical issue for manufacturing plasma facing components. Consequently, the reliability of the joints should be verified by a great number of high-heat-flux (HHF) tests to simulate the real load conditions. W/Cu brazed joint technology with sliver free filler metal CuMnNi has been developed at Southwestern Institute of Physics (SWIP). Screening and thermal fatigue tests of one small-scale flat tile W/CuCrZr mockup were performed on a 60 kW electron-beam Material testing scenario (EMS-60) constructed recently at SWIP. The module successfully survived screening test with the absorbed power density (Pabs) of 2 MW/m2 to 10 MW/m2 and the following 1000 cycles at Pabs of 7.2 MW/m2 without hot spots and overheating zones during the whole test campaign. Metallurgy and SEM observations did not find any cracks at both sides and the interface, indicating a good bonding of W and CuCrZr alloy. In addition, finite element simulations by ANSYS 12.0 under experimental load conditions were performed and compared with experimental results.

  15. Revealing the halide effect on the kinetics of the aerobic oxidation of Cu(I) to Cu(II)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Deng, Yi; Zhang, Guanghui; Qi, Xiaotian

    2015-01-01

    In situ infrared (IR) and X-ray absorption near-edge structure (XANES) spectroscopic investigations reveal that different halide ligands have distinct effects on the aerobic oxidation of Cu(I) to Cu(II) in the presence of TMEDA (tetramethylethylenediamine). The iodide ligand gives the lowest rate and thus leads to the lowest catalytic reaction rate of aerobic oxidation of hydroquinone to benzoquinone. Further DFT calculations suggest that oxidation of CuI–TMEDA involves a side-on transition state, while oxidation of CuCl–TMEDA involves an end-on transition state which has a lower activation energy.

  16. Spectroscopic Studies of Perturbed T1 Cu Sites in the Multicopper Oxidases Saccharomyces Cerevisiae Fet3p And Rhus Vernicifera Laccase: Allosteric Coupling Between the T1 And Trinuclear Cu Sites

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Augustine, A.J.; Kragh, M.E.; Sarangi, R.

    2009-04-30

    The multicopper oxidases catalyze the 4e{sup -} reduction of O{sub 2} to H{sub 2}O coupled to the 1e{sup -} oxidation of 4 equiv of substrate. This activity requires four Cu atoms, including T1, T2, and coupled binuclear T3 sites. The T2 and T3 sites form a trinuclear cluster (TNC) where O{sub 2} is reduced. The T1 is coupled to the TNC through a T1-Cys-His-T3 electron transfer (ET) pathway. In this study the two T3 Cu coordinating His residues which lie in this pathway in Fet3 have been mutated, H483Q, H483C, H485Q, and H485C, to study how perturbation at the TNCmore » impacts the T1 Cu site. Spectroscopic methods, in particular resonance Raman (rR), show that the change from His to Gln to Cys increases the covalency of the T1 Cu?S Cys bond and decreases its redox potential. This study of T1?TNC interactions is then extended to Rhus vernicifera laccase where a number of well-defined species including the catalytically relevant native intermediate (NI) can be trapped for spectroscopic study. The T1 Cu?S covalency and potential do not change in these species relative to resting oxidized enzyme, but interestingly the differences in the structure of the TNC in these species do lead to changes in the T1 Cu rR spectrum. This helps to confirm that vibrations in the cysteine side chain of the T1 Cu site and the protein backbone couple to the Cu?S vibration. These changes in the side chain and backbone provide a possible mechanism for regulating intramolecular T1 to TNC ET in NI and partially reduced enzyme forms for efficient turnover.« less

  17. Creating a single twin boundary between two CdTe (111) wafers with controlled rotation angle by wafer bonding

    NASA Astrophysics Data System (ADS)

    Sun, Ce; Lu, Ning; Wang, Jinguo; Lee, Jihyung; Peng, Xin; Klie, Robert F.; Kim, Moon J.

    2013-12-01

    The single twin boundary with crystallographic orientation relationship (1¯1¯1¯)//(111) [01¯1]//[011¯] was created by wafer bonding. Electron diffraction patterns and high-resolution transmission electron microscopy images demonstrated the well control of the rotation angle between the bonded pair. At the twin boundary, one unit of wurtzite structure was found between two zinc-blende matrices. High-angle annular dark-field scanning transmission electron microscopy images showed Cd- and Te-terminated for the two bonded portions, respectively. The I-V curve across the twin boundary showed increasingly nonlinear behavior, indicating a potential barrier at the bonded twin boundary.

  18. Superconductivity in (Cu 0.5Tl 0.25Li 0.25)Ba 2Ca 2Cu 3- ySi yO 10- δ samples

    NASA Astrophysics Data System (ADS)

    Khan, Nawazish A.; Qasim, Irfan; Khurram, A. A.

    2010-07-01

    The (Cu 0.5Tl 0.25Li 0.25)Ba 2Ca 2Cu 3- ySi yO 10- δ ( y = 0, 0.25 0.5, 0.75, 1.0, 1.25) superconductor samples have been prepared by solid-state reaction method. The critical temperature and as well as the magnitude of diamagnetism is increased up to Si concentration y = 1.0, however, from the doping level y = 1.25 a decrease in the critical temperature along with the vanishing of the diamagnetism was observed. The carrier's in the conducting CuO 2/SiO 2 planes were optimized by carrying out post-annealing in oxygen and an increase in the critical temperature was observed in all Si doped samples. The doping efficiency of Cu 0.5Tl 0.5Ba 2O 4- δ charge reservoir layer in (Cu 0.5Tl 0.25Li 0.25)Ba 2Ca 2Cu 3- ySi yO 10- δ ( y = 0, 0.25 0.5, 0.75, 1.0, 1.25) samples is enhanced by doping Li +1 ion; as alkali metals are known to easily loose their outer most electron which could be supplied to CuO 2/SiO 2 conducting planes and would suppress the anti-ferromagnetism in the inner conducting planes. The FTIR absorption measurements have provided an indirect evidence of Si substitution at in CuO 2 planes.

  19. Ultrathin Cr added Ru film as a seedless Cu diffusion barrier for advanced Cu interconnects

    NASA Astrophysics Data System (ADS)

    Hsu, Kuo-Chung; Perng, Dung-Ching; Yeh, Jia-Bin; Wang, Yi-Chun

    2012-07-01

    A 5 nm thick Cr added Ru film has been extensively investigated as a seedless Cu diffusion barrier. High-resolution transmission electron microscopy micrograph, X-ray diffraction (XRD) pattern and Fourier transform-electron diffraction pattern reveal that a Cr contained Ru (RuCr) film has a glassy microstructure and is an amorphous-like film. XRD patterns and sheet resistance data show that the RuCr film is stable up to 650 °C, which is approximately a 200 °C improvement in thermal stability as compared to that of the pure Ru film. X-ray photoelectron spectroscopy depth profiles show that the RuCr film can successfully block Cu diffusion, even after a 30-min 650 °C annealing. The leakage current of the Cu/5 nm RuCr/porous SiOCH/Si stacked structure is about two orders of magnitude lower than that of a pristine Ru sample for electric field below 1 MV/cm. The RuCr film can be a promising Cu diffusion barrier for advanced Cu metallization.

  20. Thermodynamic understanding of Sn whisker growth on the Cu surface in Cu(top)-Sn(bottom) bilayer system upon room temperature aging

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Huang, Lin; Jian, Wei; Lin, Bing

    2015-06-07

    Sn whiskers are observed by scanning electron microscope on the Cu surface in Cu(top)-Sn(bottom) bilayer system upon room temperature aging. Only Cu{sub 6}Sn{sub 5} phase appears in the X-ray diffraction patterns and no Sn element is detected in the Cu sublayer by scanning transmission electron microscopy. Based on the interfacial thermodynamics, the intermetallic Cu{sub 6}Sn{sub 5} compound phase may form directly at the Sn grain boundary. Driven by the stress gradient during the formation of Cu{sub 6}Sn{sub 5} compound at Sn grain boundaries, Sn atoms segregate onto the Cu surface and accumulate to form Sn whisker.