Fabrication of Cu@MxOy (M = Cu,Mn, Co,Fe) Nanocable Arrays for Lithium‐Ion Batteries with Long Cycle Lives and High Rate Capabilities

A new strategy is reported to fabricate Cu@M_xO_y (M = Cu, Mn, Co, Fe) nanocable arrays using five‐fold twinned copper (Cu) nanowire (NW) arrays as starting materials, to promote both the cycling stability and high rate capability of M_xO_y as anodes for LIBs. Conductive Cu NW arrays were synthesized on Cu foil via chemical vapor deposition (CVD), followed by the oxidation of their surface so as to form Cu@Cu₂O nanocable arrays. The thickness of the active material (Cu₂O) on the Cu NW arrays can be tuned from 20 nm to 160 nm by simply controlling the oxidation time. Based on this accurate control, the optimal coating thickness of Cu₂O was determined to be around 35 nm. Additionally, the Cu₂O active material shell can be easily transformed to other metal oxides with even higher specific capacities via a “coordinating etching” strategy based on Pearson's principle, resulting in Cu@M_xO_y nanocable arrays (M = Mn, Co, Fe). When applied as electrodes for LIBs, these 3D electrodes show long cycle lives (over 300 cycles) and high rate capabilities.     

Spin-valve magnetoresistive structures based on Co/Tb multilayer films

The effect of the layer thickness on the magnetic properties of {Co/Tb}_n, {Co/Tb}_n/Co, and {Co/Tb}_n/Co/Cu/Co multilayer films is studied. The dependence of the hysteresis and magnetoresistive properties of {Co(1 nm)/Tb(1 nm)}_n/Co(5 nm)/Cu(L _Cu)/Co(5 nm) structures on the thickness of the {Co/Tb}_n layer and copper spacing are obtained. The feasibility of spin-valve structures based on {Co/Tb}_n multilayer films with in-plane anisotropy is demonstrated.     

High sensitivity GMR with small hysteresis in Ni–Fe/Cu multilayers

Giant magnetoresistance (GMR) effect and magnetisation reversal processes have been investigated in Py/Cu(Py=Ni₈₃Fe₁₇,permalloy) multilayers (Mls) obtained by face-to-face sputtering method. The investigated films had constant sublayer thicknesses both for Py and Cu (d_Cu=2nm,d_Py=2nm) and various numbers of ferromagnetic sublayers. It has been shown that for such Mls a high field sensitivity of GMR effect (S≈0.4%/Oe) and negligible hysteresis can be obtained for a low number of Py layers.     

Radiation-induced decomposition of the metal-organic molecule Bis(4-cyano-2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II)

The effects of vacuum ultraviolet radiation on the adsorbed copper center molecule bis(4-cyano-2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II) (or Cu(CNdpm)₂), (C₂₄H₃₆N₂O₄Cu, Cu(II)) was studied by photoemission spectroscopy. Changes in the ultraviolet photoemission spectra (UPS) of Cu(CNdpm)₂, adsorbed on Co(1 1 1), indicate that the ultraviolet radiation leads to decomposition of Cu(CNdpm)₂ and this decomposition is initially dominated by loss of peripheral hydrogen.     

Magnetic and structural properties of the electrochemically deposited arrays of Co and CoFe nanowires

Magnetic and structural properties of the arrays of 18 nm diameter nanowires of Co and Co₉₀Fe₁₀ electrodeposited in the pores of anodic alumina are investigated. Arrays of Co and Co₉₀Fe₁₀ nanowires show perpendicular magnetic anisotropy and textured crystallographic behaviour. Coercivity H_c (⊥) and remanence M_r/M_s (⊥) values of 2275 Oe (Co₉₀Fe₁₀); 1188 Oe (Co) and 96% (Co₉₀Fe₁₀), 81% (Co) are observed. The continuous films of Co and Co₉₀Fe₁₀ on Cu substrates show in plane magnetic anisotropy and coercivity values between 109 and 288 Oe.     

XAFS investigations of copper(II) complexes with tetradentate Schiff base ligands

X‐ray absorption fine structure spectra have been investigated at the K‐edge of copper in copper(II) salen/salophen complexes: [Cu(salen)] (1), [Cu(salen)CuCl₂].H₂O (2), [Cu(salophen)] (3) and [Cu(salophen) CuCl₂].H₂O (4), where salen^2? = N,N′‐ethylenebis (salicylidenaminato); salophen^2? = o‐phenylenediaminebis(salicylidenaminato). Complexes 1 and 3 are supposed to have one type of copper centers (called (Cu1)) and complexes 2 and 4 two types of copper centers (called (Cu1) and (Cu2)) having different coordination environments and geometries. A theoretical model has been generated using the available crystallographic data of complex 1 and it has been used for analysis of the extended X‐ray absorption fine structure (EXAFS) data of the four complexes to obtain the structural parameters for (Cu1) center. For this center, the obtained Cu–Cu distance (3.2 Å) verifies the binuclear nature of all the complexes. For determining the coordination geometry around (Cu2) center in 2 and 4, a theoretical model has been generated using the crystal structure of a Cu(II) complex, [Cu(C₁₆H₁₂N₂O₂Cl₂)]. This theoretical model has been fitted to the EXAFS data of 2 and 4 to obtain the structural parameters for (Cu2) center. The present analysis shows that (Cu1) center has square pyramidal geometry involving 2N and 3O donor atoms, whereas (Cu2) center has distorted tetrahedral geometry with 2O and 2Cl donor atoms. The values of the chemical shifts and presence of typical Cu(II) X‐ray absorption near‐edge spectroscopy features suggest that copper is in the +2 oxidation state in all these complexes. The intensity of ls → 3d pre‐edge feature has been used to investigate the geometry and binuclear nature of the complexes. Copyright © 2012 John Wiley & Sons, Ltd.     

Co/Cu multilayers studied by using the119Sn probe

To observe spin polarization in nonmagnetic layers sandwiched by magnetic layers,¹¹⁹Sn Mössbauer spectra of [Co(20 Å)/Cu(20-x Å)/¹¹⁹Sn(1.5 Å)/Cu(x Å)] (x=0, 5 and 10) multilayers were measured. A magnetic fraction is observed in every spectrum, and the average hyperfine field ¯H _f at Sn nuclei in a Cu layer changes from 14 kOe (x=0) to 8 kOe (x=10). It was also observed that the polarization is greatly reduced by adding a Cr layer of only 2 Å to the Co/Cu interfaces. The spectrum of thex=10 film, measured under an external field of 30 kOe, cannot be interpreted without assuming magnetic fractions both in parallel and antiparallel to the external field, which indicates an oscillation of spin polarization in a Cu layer.     

Induced spin polarization of copper spin 1/2 molecular layers

Thin films of the metal organic molecule bis(4-cyano-2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II) (or Cu(CNdpm)₂), (C₂₄H₃₆N₂O₄Cu, Cu(II)), deposited on ferromagnetic Co(111) at 40 K, exhibit a finite electron spin polarization. The spin polarization magnitude and sign for Cu(CNdpm)₂ deposited on Co(111) is coverage dependent, but deviates from the mean field expectations for a simple paramagnet on a ferromagnetic substrate. The spin asymmetry is seen to favor select molecular orbitals, consistent with the predicted single molecule density of states. The overlayer polarization observed indicates a strong influence of the ferromagnetic Co(111) substrate and some extra-molecular magnetic coupling.     

Effect of the nonmagnetic layer in a Co/Cu/CoO trilayer structure on the exchange coupling in it

The dependence of the exchange bias of epitaxial single-crystal Co/Cu/CoO trilayer films on the copper layer thickness and temperature is studied. The exchange bias of the hysteresis loops of the ferromagnetic cobalt layer as a function of the copper layer thickness is found to have a well-pronounced oscillating character. The oscillations manifest themselves over the entire temperature range in which an exchange bias takes place (77–220 K). The complex variation of the oscillation amplitude with the nonmagnetic layer thickness can be explained by the superposition of two interlayer exchange coupling oscillation periods (λ₁ ≈ 10–11 Å, λ₂ ≈ 20 Å) having differentamplitudes and temperature dependences.     

Synthesis and thermoelectric properties of Cu excess Cu2ZnSnSe4

Quaternary stannites with an excess of copper were successfully synthesized by reacting the constituent elements and subsequent solid state annealing, followed by densification by hot‐pressing. The composition for each specimen was confirmed with a combination of Rietveld refinement and elemental analysis. Their high temperature thermoelectric properties were measured from 300 K to 800 K and compared with that of Cu₂ZnSnSe₄. The thermal conductivity decreases significantly with increasing Cu content at elevated temperatures due to the crystal structure of this material system. A maximum ZT value of 0.86 was obtained at 800 K for the specimen with the highest Cu content, Cu_2.2Zn_0.8SnSe₄. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,Thermal Behavior,and Antimicrobial Activity of a Novel Macrocycle and its Transition Metal Complexes Derived from Thiosemicarbazide

The present study reports the synthesis of Co(II), Ni(II), Mn(II), Cu(II), and Zn(II) complexes with a new macrocyclic ligand (L₂)- 1,2,8,9,11,14-hexaazacyclopentadeca-12,13-dioxo-10,15-dithione-2,7-diene. The macrocycle was derived from thiosemicabazone (L₁) and diethyloxalate that were prepared by the reaction of thiosemicarbazide and glutaraldehyde in the ratio of 2:1. The synthesized complexes and ligands were characterized by elemental analysis and molar conductance, magnetic susceptibility, ¹HNMR, IR, electronic, and thermogravimetric analyses. The molar conductance values confirmed that the Ni(II), Cu(II), Zn(II), Mn(II) and Co(II) complexes were 1:2 electrolytes. On the basis of electronic spectral studies and molar conductance measurements, the authors proposed an octahedral structure for Ni(II), Mn(II), and Co(II) complexes, tetrahedral geometry for Zn(II) complex, and square planar geometry for Cu(II) complex. The thermal behavior of the compounds was studied by TGA in a nitrogen atmosphere up to 750°C at the rate of 20°C/min. The TGA results revealed that the complexes had higher thermal stability than the macrocycle. All the synthesized compounds were screened against 4 bacteria (i.e., Streptococcus aureus, Escherichia coli, Bacillus subtillis, Salmonella typhimurium) and 2 fungi (i.e., Fusarium oryzae, Candida albicans). The results showed that the metal complexes inhibited the growth of bacteria to a greater extent as compared to the ligand.     

DNA Binding and Photocleavage Study of Cationic Metalloporphyrins by Spectral Methods

The DNA binding and photocleavage specificities of the Zn(II), Cu(II), Co(III), Mn(III) complexes of 5,10,15-tris(1-methylpyridinium-4-yl)-20-(4-propionoxyphenyl)porphyrin have been studied by using a combination of absorption, fluorescence titration, surface-enhanced Raman spectroscopy (SERS), induced circular dichroism (ICD) spectroscopy, thermal DNA denaturation as well as gel electrophoresis experiment. It is found that Cu(II) porphyrin has comparable binding ability with the free base porphyrin while the axial-coordinated Zn(II), Co(III), and Mn(III) porphyrins have lower K_b because of the molecular steric hindrance. However, those metalloporphyrins with lower K_b have similar DNA cleavage efficiencies with the free base porphyrin. This could be best understood by the enhancement of the ¹O₂ productivity which may also result from the steric hindrance of the axial-coordinated metalloporphyrins.     

In situ X‐ray absorption spectroscopic studies of copper in a copper‐rich sludge during electrokinetic treatments

Speciation of copper in a copper‐rich chemical‐mechanical polishing sludge during electrokinetic treatment has been studied by in situ extended X‐ray absorption fine structure (EXAFS) and X‐ray absorption near‐edge structure (XANES) spectroscopy. The least‐squares‐fitted XANES spectra indicate that the main copper species in the sludge are Cu(OH)₂ (74%), nanosize CuO (20–60 nm) (13%) and CuO (>100 nm) (13%). The average bond distance and coordination number (CN) of Cu—O are 1.96 Å and 3.5, respectively. Under electrokinetic treatment (5 V cm^?1) for 120 min, about 85% of the copper is dissolved in the electrolyte, 13% of which is migrated and enriched on the cathode. Notably the copper nanoparticles in the sludge can also migrate to the cathode under the electric field. By in situ EXAFS, it is found that during the electrokinetic treatment the bond distance and CN of Cu—O are increased by 0.1 Å and 0.9, respectively.     

Magnetic properties of Co–Cu nanowire arrays fabricated in different conditions by SC electrodeposition

Magnetic Co–Cu alloy nanowires with low Cu content were prepared by SC electrodeposition in pores of anodic aluminum oxide templates. The as-deposited Co–Cu nanowires, with a diameter of 15 nm, show distinctive magnetic anisotropy as an applied magnetic field parallel to the axis of nanowires. With increase in the molar ratio of Co and Cu, the coercivity along nanowire axis increases and reaches a maximum value of 1977.5 Oe at the Co/Cu molar ratio of 60:1, but the maximum value of coercivity increases to 1743.6 Oe with the decrease of frequency to 2 Hz.     

Cu+ emission in Li2BPO5 material for thermoluminescence dosimetry

In this study, Li₂BPO₅ doped with Cu and that co-doped with Mg are synthesized by the wet chemical technique and exposed to γ rays of ⁶⁰Co to determine their thermoluminescence (TL) properties. The X-ray diffraction technique shows the crystalline nature of the prepared material. The photoluminescence (PL) emission spectra of Li₂BPO₅:Cu phosphor show the strong prominent peak at 368 nm in the violet region of the visible spectrum due to the transition of 3d⁹4s¹ ? 3d¹⁰ of monovalent copper ion. The PL emission of Li₂BPO₅:Cu is enhanced by the addition of Mg. The TL glow curves of γ-irradiated Li₂BPO₅:Cu sample show one glow peak at 143°C, indicating that only one set of traps is being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The trapping parameters associated with the prominent glow peak of Li₂BPO₅:Cu are calculated using the glow curve shape (Chen's) method. The release of hole/electron from defect centers at the characteristic trap site initiates the luminescence process in these materials. A linear TL response is observed in Li₂BPO₅:Cu in a long span of exposures. The sensitivity of Li₂BPO₅:Cu sample is observed to be 7.8 times that of (TLD-100) LiF:Mg, Ti.     

Matrix embedded cobalt-carbon nano-cluster magnets: behavior as room temperature single domain magnets

A new type of Co-C nanoparticles is synthesized from CH₂Cl₂ solution of Co₄(CO)_{1 2} by heating up to 210 ^°C in a closed vessel. Transmission electron microscope (TEM) and electron energy loss spectroscopy (EELS) observation show that the particles are embedded in amorphous carbon and their average size is 12 nm. The radial structure function obtained from the extended X-ray absorption fine structure (EXAFS) of the Co K-edge absorption of the Co-C nanoparticles provides a Co-C average distance of 2.08 Å and the Co-Co distances of 3.18 Å and 3.9 (±0.2) Å. The particles exhibit the magnetic hysteresis curve with a coercive force of 200 Oe at 20 K and 260 Oe at 300 K. The temperature dependence of the magnetic susceptibility measured under zero-field cooling and 10 Oe field cooling conditions exhibits the behavior characteristic of a set of single magnetic domain nanomagnets in an amorphous carbon matrix.     

Enhancement of radiosensitivity of oral carcinoma cells by iodinated chlorin p6 copper complex in combination with synchrotron X‐ray radiation

The combination of synchrotron X‐ray radiation and metal‐based radiosensitizer is a novel form of photon activation therapy which offers the advantage of treating malignant tumors with greater efficacy and higher precision than conventional radiation therapy. In this study the anticancer cytotoxic efficacy of a new chlorophyll derivative, iodinated chlorin p₆ copper complex (ICp₆‐Cu), combined with synchrotron X‐ray radiation (8–10 keV) in two human oral cancer cell lines is explored. Pre‐treatment of cells with 20 µM and 30 µM ICp₆‐Cu for 3 h was found to enhance the X‐ray‐induced cytotoxicity with sensitization enhancement ratios of 1.8 and 2.8, respectively. ICp₆‐Cu localized in cytoplasm, mainly in lysosomes and endoplasmic reticulum, and did not cause any cytotoxicity alone. The radiosensitization effect of ICp₆‐Cu accompanied a significant increase in the level of reactive oxygen species, damage to lysosomes, inhibition of repair of radiation‐induced DNA double‐strand breaks, increase in cell death and no significant effect on cell cycle progression. These results demonstrate that ICp₆‐Cu is a potential agent for synchrotron photon activation therapy of cancer.     

Effects of Ni buffer layer on giant magnetoresistance in Co/Cu/Co sandwich

In order to increase the sensitivity of Co/Cu/Co sandwiches, different thickness Ni layers were used as buffer layer. It was found that in the Co 55 Å/Cu 35 Å/Co 55 Å sandwiches with different thickness Ni buffer layers, MR ratios between 3.5% and 5.6% could be obtained, and the coercive forces were about 12 Oe. Hence, the maximum field sensitivity could be enhanced to about 1%/Oe. Further investigation from the results of atomic force microscopy showed the improvement of the interfacial flatness in the sandwiches with Ni buffer layer. The microstructure observed by high-resolution electron microscope demonstrated the different structure of the two Co layers in the Ni buffered sandwich, which directly determined the small saturation field of the sandwich. This was confirmed by the magnetic behaviors of the two Co layers calculated from the experimental hysteresis loops. All these showed that the usage of a Ni buffer layer could result in interfacial improvement, different crystalline structure, and small saturation field in the Co/Cu/Co sandwich. These enhanced the electron spin scattering at the Co–Cu interfaces and finally enlarged the giant magnetoresistance and the sensitivity in the sandwich.     

Synchrotron infrared reflectance microspectroscopy study of film formation and breakdown on copper

This work demonstrates the utility of synchrotron infrared reflectance microspectroscopy in the far‐ and mid‐IR for the determination of the composition of electrogenerated surface films formed during the general and localized corrosion of copper in alkaline and bicarbonate solutions. Back‐reflection geometry has been employed to identify the anodic film formed on copper in 0.1 M NaOH solution at 0.3 V (versus a Ag/AgCl reference) to be mainly CuO. In 0.01 M NaHCO₃ solution general corrosion occurs with passive film formation below 0.2 V. The surface film at 0.2 V consisted mainly of bicarbonate, copper carbonate dihydroxide or malachite [CuCO₃·Cu(OH)₂], Cu(OH)₂ and possibly some CuO. At higher potentials the passive film breaks down and localized corrosion occurs leading to the formation of pits. The composition of the surface films inside the pits formed at 0.6 V was found to be essentially the same as that outside but the relative amount of Cu(OH)₂ appears to be higher.     

Effect of Co underlayer on soft magnetic properties and microstructure of FeCo thin films

High saturation magnetization soft magnetic FeCo (=Fe₆₅Co₃₅) films were prepared using a thin Co underlayer. The FeCo/Co films exhibited a well-defined in-plane uniaxial anisotropy with easy axis coercivity (H_ce) of 10 Oe and hard axis coercivity (H_ch) of 3 Oe, and a half reduction of H_c with H_ce=4.8 Oe and H_ch=1.0 Oe was obtained when the composition was adjusted to 25 at% Co. The effective permeability of the films remains flat around 250 to 800 MHz. The saturation magnetostriction was 5.2×10⁻⁵ and the intrinsic stress was 0.8 GPa in FeCo single layer, both were slightly reduced by Co underlayer. The Co underlayer changed the preferred orientation of the FeCo films from (2 0 0) to (1 1 0) but more significantly, reduced the average grain size from ∼74 to ∼8.2 nm. It also reduced the surface roughness from 2.351 to 0.751 nm. The initial stage and interface diffusion properties were examined by TEM and XPS.