Phase control of La2CuO4 in thin-film synthesis

The lanthanum copper oxide, La2CuO4, which is an end member of the prototype high-Tc superconductors (La,Sr)2CuO4 and (La,Ba)2CuO4, crystallizes in the "K2NiF4" structure in high-temperature bulk synthesis. The crystal chemistry, however, predicts that La2CuO4 is at the borderline of the K2NiF4 stability and that it can crystallize in the Nd2CuO4 structure at low synthesis temperatures. In this article we demonstrate that low-temperature thin-film synthesis actually crystallizes La2CuO4 in the Nd2CuO4 structure. We also show that the phase control of "K2NiF4"-type La2CuO4 versus "Nd2CuO4"-type La2CuO4 can be achieved by varying the synthesis temperature and using different substrates.Comment: 4 pages, 5 figures, submitted to PRB, revte

Phase Relations in the Li2O-V2O3-V2O5 System at 700 C: Correlations with Magnetic Defect Concentration in Heavy Fermion LiV2O4

The phase relations in the Li2O-V2O3-V2O5 ternary system at 700 C for compositions in equilibrium with LiV2O4 are reported. This study clarified the synthesis conditions under which low and high magnetic defect concentrations can be obtained within the spinel structure of LiV2O4. We confirmed that the LiV2O4 phase can be obtained containing low (0.006 mol%) to high (0.83 mol%) magnetic defect concentrations n{defect} and with consistently high magnetic defect spin S values between 3 and 6.5. The high n{defect} values were obtained in the LiV2O4 phase in equilibrium with V2O3, Li3VO4, or LiVO2 and the low values in the LiV2O4 phase in equilibrium with V3O5. A model is suggested to explain this correlation.Comment: 6 pages, 7 figures; Phys. Rev. B (accepted

Single-crystal growth and magnetic properties of the metallic molybdate pyrochlore Sm2Mo2O7

We have successfully grown cm3-size single crystals of the metallic-ferromagnet Sm2Mo2O7 by the floating-zone method using an infrared-red image furnace. The growth difficulties and the remedies found using a 2-mirror image furnace are discussed. Magnetization studies along the three crystalline axes of the compound are presented and discussed based on our recent proposal of an ordered spin-ice ground state for this compoun

Magnetic and Charge Correlations in La{2-x-y}Nd_ySr_xCuO_4: Raman Scattering Study

Two aspects in connection with the magnetic properties of La_{2-x-y}Nd_ySr_xCuO_4 single crystals are discussed. The first is related to long wavelength magnetic excitations in x = 0, 0.01, and 0.03 La_{2-x}Sr_xCuO_4 detwinned crystals as a function of doping, temperature and magnetic field. Two magnetic modes were observed within the AF region of the phase diagram. The one at lower energies was identified with the spin-wave gap induced by the antisymmetric DM interaction and its anisotropic properties in magnetic field could be well explained using a canonical form of the spin Hamiltonian. A new finding was a magnetic field induced mode whose dynamics allowed us to discover a spin ordered state outside the AF order which was shown to persist in a 9 T field as high as 100 K above the N\'eel temperature T_N for x = 0.01. For these single magnon excitations we map out the Raman selection rules in magnetic fields and demonstrate that their temperature dependent spectral weight is peaked at the N\'eel temperature. The second aspect is related to phononic and magnetic Raman scattering in La_{2-x-y}Nd_ySr_xCuO_4 with three doping concentrations: x = 1/8, y = 0; x = 1/8, y = 0.4; and x = 0.01, y = 0. We observed that around 1/8 Sr doping and independent of Nd concentration there exists substantial disorder in the tilt pattern of the CuO_6 octahedra in both the orthorhombic and tetragonal phases which persist down to 10 K and are coupled to bond disorder in the cation layers. The weak magnitude of existing charge/spin modulations in the Nd doped structure did not allow us to detect specific Raman signatures on lattice dynamics or two-magnon scattering around 2200 cm-1.Comment: 26 pages, 22 figure

Ultrahigh Surface Area Three-Dimensional Porous Graphitic Carbon from Conjugated Polymeric Molecular Framework

Porous graphitic carbon is essential for many applications such as energy storage devices, catalysts, and sorbents. However, current graphitic carbons are limited by low conductivity, low surface area, and ineffective pore structure. Here we report a scalable synthesis of porous graphitic carbons using a conjugated polymeric molecular framework as precursor. The multivalent cross-linker and rigid conjugated framework help to maintain micro- and mesoporous structures, while promoting graphitization during carbonization and chemical activation. The above unique design results in a class of highly graphitic carbons at temperature as low as 800 ??C with record-high surface area (4073 m2 g-1), large pore volume (2.26 cm-3), and hierarchical pore architecture. Such carbons simultaneously exhibit electrical conductivity >3 times more than activated carbons, very high electrochemical activity at high mass loading, and high stability, as demonstrated by supercapacitors and lithium-sulfur batteries with excellent performance. Moreover, the synthesis can be readily tuned to make a broad range of graphitic carbons with desired structures and compositions for many applications.clos

Hole concentration and phonon renormalization in Ca-doped YBa_2Cu_3O_y (6.76 < y < 7.00)

In order to access the overdoped regime of the YBa_2Cu_3O_y phase diagram, 2% Ca is substituted for Y in YBa_2Cu_3O_y (y = 7.00,6.93,6.88,6.76). Raman scattering studies have been carried out on these four single crystals. Measurements of the superconductivity-induced renormalization in frequency (Delta \omega) and linewidth (\Delta 2\gamma) of the 340 cm^{-1} B_{1g} phonon demonstrate that the magnitude of the renormalization is directly related to the hole concentration (p), and not simply the oxygen content. The changes in \Delta \omega with p imply that the superconducting gap (\Delta_{max}) decreases monotonically with increasing hole concentration in the overdoped regime, and \Delta \omega falls to zero in the underdoped regime. The linewidth renormalization \Delta 2\gamma is negative in the underdoped regime, crossing over at optimal doping to a positive value in the overdoped state.Comment: 18 pages; 5 figures; submitted to Phys. Rev. B Oct. 24, 2002 (BX8292

Selective Laser Sintering of Alumina-Boron Oxide Composites

The selection of an optimum composite system for selective laser sintering (SLS) is based on materials properties such as the melting point and the wettability between the components in the composite powder. The alumina-boron oxide composite system is attractive for SLS because the presence of the low melting component B203 (melting point 4500 C) can enhance sintering. A better wetting of solid alumina powder by molten boron oxide can also aid densification process. The alumina-boron oxide conlposite system has been investigated by SLS and selective laser reactive sintering (SLRS). The role of boron oxide content as a binder, laser power density, and secondary heat treatment on the microstructure and mechanical properties is discussed.Mechanical Engineerin

Multifunctional semi-interpenetrating polymer network-nanoencapsulated cathode materials for high-performance lithium-ion batteries

As a promising power source to boost up advent of next-generation ubiquitous era, high-energy density lithium-ion batteries with reliable electrochemical properties are urgently requested. Development of the advanced lithium ion-batteries, however, is staggering with thorny problems of performance deterioration and safety failures. This formidable challenge is highly concerned with electrochemical/thermal instability at electrode material-liquid electrolyte interface, in addition to structural/chemical deficiency of major cell components. Herein, as a new concept of surface engineering to address the abovementioned interfacial issue, multifunctional conformal nanoencapsulating layer based on semi-interpenetrating polymer network (semi-IPN) is presented. This unusual semi-IPN nanoencapsulating layer is composed of thermally-cured polyimide (PI) and polyvinyl pyrrolidone (PVP) bearing Lewis basic site. Owing to the combined effects of morphological uniqueness and chemical functionality (scavenging hydrofluoric acid that poses as a critical threat to trigger unwanted side reactions), the PI/PVP semi-IPN nanoencapsulated-cathode materials enable significant improvement in electrochemical performance and thermal stability of lithium-ion batteries.open

Development of Nanocomposites for Solid Freeform Fabrication

Nanocomposites in which the constituents are mixed on a nanorneter scale can provide important advantages in the Selective Laser Sintering (SLS) and Selective Laser Reactive Sintering (SLRS) processes. The larger surface area and grain boundaries in the nanocolnposites compared to that in the conventional microcomposites are expected to enhance the solid state diffusion during laser irradiation as well as during any other subsequent processes. Our strategy is to design and develop nanocomposites in which one nanosize cOlnponent has a lower melting point than the other nanosize component, either of which can serve as the matrix phase. The nanoscale dispersion of the low melting component can aid the sintering process during SLS or SLRS. Nanocomposite powders of AI203-COOx, Ab03-NiO, A1203-CO and A1203-Ni have been synthesized by sol-gel processing and are evaluated by SLS.Mechanical Engineerin

Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries

Undesired electrode-electrolyte interactions prevent the use of many high-energy-density cathode materials in practical lithium-ion batteries. Efforts to address their limited service life have predominantly focused on the active electrode materials and electrolytes. Here an advanced three-dimensional chemical and imaging analysis on a model material, the nickel-rich layered lithium transition-metal oxide, reveals the dynamic behaviour of cathode interphases driven by conductive carbon additives (carbon black) in a common nonaqueous electrolyte. Region-of-interest sensitive secondary-ion mass spectrometry shows that a cathode-electrolyte interphase, initially formed on carbon black with no electrochemical bias applied, readily passivates the cathode particles through mutual exchange of surface species. By tuning the interphase thickness, we demonstrate its robustness in suppressing the deterioration of the electrode/electrolyte interface during high-voltage cell operation. Our results provide insights on the formation and evolution of cathode interphases, facilitating development of in situ surface protection on high-energy-density cathode materials in lithium-based batteries.ope