A nanometre-scale non-periodic structural variation in high temperature superconducting ceramics and the implications for properties

Non-periodic structural variation has been found in the high Tc cuprates, YBa2Cu3O7-x and Hg0.67Pb0.33Ba2Ca2Cu 3O8+δ, by image analysis of high resolution transmission electron microscope (HRTEM) images. We use two methods for analysis of the HRTEM images. The first method is a means for measuring the bending of lattice fringes at twin planes. The second method is a low-pass filter technique which enhances information contained by diffuse-scattered electrons and reveals what appears to be an interference effect between domains of differing lattice parameter in the top and bottom of the thin foil. We believe that these methods of image analysis could be usefully applied to the many thousands of HRTEM images that have been collected by other workers in the high temperature superconductor field. This work provides direct structural evidence for phase separation in high Tc cuprates, and gives support to recent stripes models that have been proposed to explain various angle resolved photoelectron spectroscopy and nuclear magnetic resonance data. We believe that the structural variation is a response to an opening of an electronic solubility gap where holes are not uniformly distributed in the material but are confined to metallic stripes. Optimum doping may occur as a consequence of the diffuse boundaries between stripes which arise from spinodal decomposition. Theoretical ideas about the high Tc cuprates which treat the cuprates as homogeneous may need to be modified in order to take account of this type of structural variation.

Growth and properties of a multilayer system based on Y1Ba 2Cu3Ox and amorphous Y-ZrO2

The growth of c-axis oriented Y1Ba2Cu 3Ox thin films on an amorphous buffer layer of Y-ZrO 2, deposited on sapphire substrates, was investigated. Both films were grown by a pulsed laser deposition technique. A strong correlation was observed between the properties of Y1Ba2Cu 3Ox and the thickness of the buffer layer. A Tc of 89 K was obtained for an optimal buffer layer thickness of 9 nm. A model that adequately describes the film growth process was developed. A multilayer system of Y1Ba2Cu3Ox and amorphous Y-ZrO2 was grown and a Tc of 87 K for the upper c-axis oriented layer was measured.

Properties of artificial grain boundary weak links grown on Y-ZrO 2 bicrystals

Weak links were fabricated by pulsed laser deposition of YBa 2Cu3Ox thin films on Y-ZrO2 bicrystal substrates. They were formed by transferring the bicrystal boundary into the epitaxial film during the film growth. Their properties were determined by the misorientation angle ( theta ) between the two halves of the bicrystal. The transport properties of the weak links were studied as a function of theta and an exponential dependence of the weak link critical current density was observed for angles up to 45 degrees . Clear Josephson effects with good microwave and magnetic field response were observed.

Yttrium barium copper oxide thin films on yttria-stabilized zirconia: growth and properties

Y Ba Cu oxide thin films were grown epitaxially on single cryst. yttria-stabilized zirconia substrates by laser deposition. [on SciFinder(R)]

Artificial grain boundary Josephson junctions : properties and applications

Engineered grain boundary Josephson junctions in YBaCuO were formed on bicrystal Y-ZrO2 substrates. Laser deposited films were patterned into micron size microbridges. The authors obsd. a pronounced correlation between superconducting transport properties of grain boundary junctions and the misorientation angle θ between the two halves of the bicrystal. The crit. Josephson current Ic decreased about four orders of magnitude as θ was increased from 0 to 45 degrees. Clear microwave and magnetic field responses were obsd. at 77 K. At this temp., crit. current times normal resistance products, IcRn, of up to 1 mV were measured for low angle grain boundaries, and Shapiro steps were obsd. up to that voltage. DC SQUIDs were fabricated, and best performance at 77 K was obtained for θ = 32° with a 4-μm strip width. To utilize the higher IcRn value of a lower θ, submicron junctions have to be developed. [on SciFinder(R)]

Torsional properties of bamboo-like structured Cu nanowires

Recently, researchers reported that nanowires (NWs) are often polycrystalline, which contain grain or twin boundaries that transect the whole NW normal to its axial direction into a bamboo like structure. In this work, large-scale molecular dynamics simulation is employed to investigate the torsional behaviours of bamboo-like structured Cu NWs. The existence of grain boundaries is found to induce a considerably large reduction to the critical angle, and the more of grain boundaries the less reduction appears, whereas, the presence of twin boundaries only results in a relatively smaller reduction to the critical angle. The introduction of grain boundaries reduces the torsional rigidity of the NW, whereas, the twin boundaries exert insignificant influence to the torsional rigidity. NWs with grain boundaries are inclined to produce a local HCP structure during loading, and the plastic deformation is usually evenly distributed along the axial axis of the NW. The plastic deformation of both perfect NW and NWs with twin boundaries is dominated by the nucleation and propagation of parallel intrinsic stacking faults. This study will enrich the current understanding of the mechanical properties of NWs, which will eventually shed lights on their applications.

Two-dimensional graphene heterojunctions: The tunable mechanical properties

We report the mechanical properties of different two-dimensional carbon heterojunctions (HJs) made from graphene and various stable graphene allotropes, including α-, β-, γ- and 6612-graphyne (GY), and graphdiyne (GDY). It is found that all HJs exhibit a brittle behaviour except the one with α-GY, which however shows a hardening process due to the formation of triple carbon rings. Such hardening process has greatly deferred the failure of the structure. The yielding of the HJs is usually initiated at the interface between graphene and graphene allotropes, and monoatomic carbon rings are normally formed after yielding. By varying the locations of graphene (either in the middle or at the two ends of the HJs), similar mechanical properties have been obtained, suggesting insignificant impacts from location of graphene allotropes. Whereas, changing the types and percentages of the graphene allotropes, the HJs exhibit vastly different mechanical properties. In general, with the increasing graphene percentage, the yield strain decreases and the effective Young’s modulus increases. Meanwhile, the yield stress appears irrelevant with the graphene percentage. This study provides a fundamental understanding of the tensile properties of the heterojunctions that are crucial for the design and engineering of their mechanical properties, in order to facilitate their emerging future applications in nanoscale devices, such as flexible/stretchable electronics.

Fabrication and electrocatalytic properties of polyaniline/Pt nanoparticle composites

Polyaniline (PANI)/Pt nanoparticle composites can be prepared by the spontaneous redox reaction of K2PtCl4 with PANI, to yield thin films that show electrocatalytic properties in both acidic and neutral aqueous media.

Formation of polyaniline/Pt nanoparticle composite films and their electrocatalytic properties

Polyaniline (PANI) thin films modified with platinum nanoparticles have been prepared by several methods, characterised and assessed in terms of electrocatalytic properties. These composite materials have been prepared by the in situ reduction of a platinum salt (K2PtCl4) by PANI, in a variety of solvents, resulting in the formation of platinum nanoparticles and clusters of different sizes. The further deposition of platinum clusters at spin cast thin films of PANI/Pt composites from a neutral aqueous solution of K2PtCl4 has also been demonstrated. Thin-film electrodes prepared from these materials have been investigated for their electrocatalytic activity by studying hydrazine oxidation and dichromate reduction. The properties of the composite materials have been determined using UV–visible spectroscopy, atomic force microscopy and transmission electron microscopy. The nature of the material formed is strongly dependent on the solvent used to dissolve PANI, the method of preparation of the PANI/Pt solution and the composition of the spin cast thin film before subsequent deposition of platinum from the aqueous solution of K2PtCl4.

Auto-inhibition of hydrogen gas evolution on gold in aqueous acid solution

It was demonstrated recently that dramatic changes in the redox behaviour of gold/aqueous solution interfaces may be observed following either cathodic or thermal electrode pretreatment. Further work on the cathodic pretreatment of gold in acid solution revealed that as the activity of the gold surface was increased, its performance as a substrate for hydrogen gas evolution under constant potential conditions deteriorated. The change in activity of the gold atoms at the interface, which was attributed to a hydrogen embrittlement process (the occurrence of the latter was subsequently checked by surface microscopy), was confirmed, as in earlier work, by the appearance of a substantial anodic peak at ca. 0.5 V (RHE) in a post-activation positive sweep. Changes in the catalytic activity of a metal surface reflect the fact that the structure (or topography), thermodynamic activity and electronic properties of a surface are dependent not only on pretreatment but also, in the case of the hydrogen evolution reaction, vary with time during the course of reaction. As will be reported shortly, similar (and often more dramatic) time-dependent behaviour was observed for hydrogen gas evolution on other metal electrodes.

Electrochemical properties of galvanically replaced iron nanocubes with gold and palladium

The galvanic replacement reaction has received considerable interest due to the creation of novel bimetallic nanomaterials that minimise the use of expensive metals while maintaining enhanced electrocatalytic properties for certain reactions. In this work we investigate the galvanic replacement of electrochemically synthesised iron nanocubes on glassy carbon, with gold and palladium. The resultant nanomaterials demonstrate quite a difference in morphology; the original cuboid like template is maintained in the case of gold but destroyed when palladium is used. The electrochemical and electrocatalytic behaviours of these materials are reported for reactions such as methanol oxidation, hydrogen evolution and oxygen reduction.

Galvanic Replacement of Semiconductor Phase I CuTCNQ Microrods with KAuBr4 to Fabricate CuTCNQ/Au Nanocomposites with Photocatalytic Properties

In this study, the reaction of semiconductor microrods of phase I copper 7,7,8,8-tetracyanoquinodimethane (CuTCNQ) with KAuBr4 in acetonitrile is reported. It was found that the reaction is redox in nature and proceeds via a galvanic replacement mechanism in which the surface of CuTCNQ is replaced with metallic gold nanoparticles. Given the slight solubility of CuTCNQ in acetonitrile, two competing reactions, namely CuTCNQ dissolution and the redox reaction with KAuBr4, were found to operate in parallel. An increase in the surface coverage of CuTCNQ microrods with gold nanoparticles occurred with an increased KAuBr4 concentration in acetonitrile, which also inhibited CuTCNQ dissolution. The reaction progress with time was monitored using UV−visible, FT-IR, and Raman spectroscopy as well as XRD and EDX analysis, and SEM imaging. The CuTCNQ/Au nanocomposites were investigated for their photocatalytic properties, wherein the destruction of Congo red, an organic dye, by simulated solar light was found dependent on the surface coverage of gold nanoparticles on the CuTCNQ microrods. This method of decorating CuTCNQ may open the possibility of modifying this and other metal-TCNQ charge transfer complexes with a host of other metals which may have significant applications.

The facile formation of silver dendritic structures in the absence of surfactants and their electrochemical and SERS properties

In this work a simple approach to the creation of highly dispersed electrocatalytically active silver microstructured dendrites on indium tin oxide in the absence of any surface modification or surfactant is presented. It is found that the addition of low concentrations of supporting electrolyte to the AgNO3 solution dramatically influences the morphology of electrodeposited silver which is independent of both the anion and the cation employed. The silver dendrites are characterized by SEM, XRD, XPS as well as by cyclic voltammetry under alkaline conditions. It is found that the surface oxide formation and removal processes are significantly influenced by the microstructured morphology of the silver electrodeposits compared to a smooth macrosized silver electrode. The facile formation of dendritic silver microstructures is also shown to be beneficial for the electrocatalytic oxidation of both formaldehyde and hydrazine and oxygen reduction. The formation of a continuous film of dendritic silver is also investigated for its SERS activity where the connectivity between the individual dendrites is found to be particularly important.

The anodized crystalline WO3 nanoporous network with enhanced electrochromic properties

We demonstrate that a three dimensional (3D) crystalline tungsten trioxide (WO3) nanoporous network, directly grown on a transparent conductive oxide (TCO) substrate, is a suitable working electrode material for high performance electrochromic devices. This nanostructure, with achievable thicknesses of up to 2 μm, is prepared at room temperature by the electrochemical anodization of a RF-sputtered tungsten film deposited on a fluoride doped tin oxide (FTO) conductive glass, under low applied anodic voltages and mild chemical dissolution conditions. For the crystalline nanoporous network with thicknesses ranging from 0.6 to 1 μm, impressive coloration efficiencies of up to 141.5 cm2 C−1 are achieved by applying a low coloration voltage of −0.25 V. It is also observed that there is no significant degradation of the electrochromic properties of the porous film after 2000 continuous coloration–bleaching cycles. The remarkable electrochromic characteristics of this crystalline and nanoporous WO3 are mainly ascribed to the combination of a large surface area, facilitating increased intercalation of protons, as well as excellent continuous and directional paths for charge transfer and proton migration in the highly crystalline material.

Electrodeposited α- and β-phase MoO3 films and investigation of their gasochromic properties

α- and β-Phase MoO3 are synthesized using an electrodeposition method on fluorine-doped tin oxide (FTO) glass substrates from sodium-molybdate (Na2MoO4) solutions. We show that it is possible to obtain both α- and β-MoO3 by manipulating the cyclic voltammetry (CV) parameters during electrodeposition. Raman spectroscopy, X-ray diffraction, and scanning electron microscopy indicate that the applied potential range and sweep rate are strongly influential on the phase obtained and the surface morphology of the electrodeposited thin films. Gasochromic measurements were carried out on the annealed samples by exposing them to H2 gas. It was revealed that α-MoO3 thin films provided better response to H2 interaction than β-MoO3 films did. Additionally, porous films provided significantly larger responses than smooth films.