ABSTRACT
Previous angle-resolved photoemission spectroscopy experiments in NaxCoO2 reported both a strongly renormalized bandwidth near the Fermi level and moderately renormalized Fermi velocities, leaving it unclear whether the correlations are weak or strong and how they could be quantified. We explain why this situation occurs and solve the problem by extracting clearly the coherent and incoherent parts of the band crossing the Fermi level. We show that one can use their relative weight to estimate self-consistently a quasiparticle weight Z=0.15+/-0.05. We suggest this method could be a reliable way to study the evolution of correlations in cobaltates and for comparison with other strongly correlated systems.
ABSTRACT
We have synthesized single crystals of the misfit-layered cobalt oxide, [Bi(1.5)Pb(0.5)Sr(2)O(4-δ)][CoO(2)](1.86), with quadruple NaCl-type layers, using a flux method, and measured their transport properties. From structural refinements, it is found that the modulation in the BiO layer observed in [Bi(1.74)Sr(2)O(4-δ)](RS)[CoO(2)](1.82) is suppressed by Pb substitution. The in-plane resistivity, thermopower, and Hall coefficient are 4.3 mΩ cm, 101 µV K(-1), and 1 × 10(-2) cm(3) C(-1) at 300 K, respectively; these are consistent with those of the misfit-layered cobalt oxides. All of these values are smaller than those of [Bi(1.74)Sr(2)O(4)][CoO(2)](1.82), indicating that the carrier concentration is larger than that of the undoped crystal. Moreover, the low T upturn of resistivity observed for most of the cobalt misfit oxides is replaced by a metallic behavior, following a T(2) dependence, indicating strong correlations in the Pb-doped crystal. Also, the magnetoresistance, usually negative for misfit oxides, is replaced by a small positive magnetoresistance. Doping with Pb is thus an efficient way to suppress the low T localized behavior usually observed for misfits.
ABSTRACT
Single crystals of thermoelectric misfit lamellar cobalt oxide phases in the Bi-Ca-Co-O and I-Bi-Ca-Co-O systems were synthesized. They are characterized by aperiodic structures involving two partially independent sublattices: a CdI(2)-type pseudohexagonal CoO(2) layer and a rocksalt-type BiCaO(2) slab allowing the intercalation of iodine. The crystal symmetry of these structures is discussed using the four-dimensional superspace formalism. The superspace Laue classes of the iodine-free and the intercalated compounds are P2/m(0delta(1/2)) (a(1) = 4.901, b(1) = 4.730, b(2) = 2.80, c(1) = 14.66 A, beta = 93.49 degrees ) and A2/m(0delta1) (a'1 = 4.903, b'1 = 4.742, c'1 = 36.51 A, beta = 87.30 degrees ), respectively. A comparison is given with the related Bi-Sr-Co-O misfit compounds. The present structures are compatible with the presence of an intrinsic modulation with a wavelength matching the misfit aperiodicity in the b direction. Preliminary partial structure refinements confirm the layer stacking of the structure and the intercalation of I between the Bi-O layers for the second phase. A comparison with other cobalt oxide phases, as well as symmetry and metric considerations allow us to predict average structures for these new phases and to describe the common structural features assumed for all these lamellar misfit cobalt oxides.
ABSTRACT
We report on the structural, microstructural, and electronic properties of iodine intercalated [Bi0.82CaO2]2[CoO2]1.69 misfit cobaltite. We first prove through a detailed and careful structural study that the block layer structure can be modified in the desired way. Iodine enters the material between the [BiO] double layers, and the c-cell parameter of the pristine compound is elongated by 3.6 Angstrom. On the basis of this result, we point out the coupling between the block-layer structure and the transport properties. Additionally, we provide in-depth commentary and discussion of some extra results, clarifying some doping effects in the quasi-2D studied phase. Finally, we also propose some expressions that might be useful to material scientists for the tuning of the properties of such compounds.
ABSTRACT
The incommensurate structure of lead cobalt tungstate has been refined by the Rietveld method on neutron data collected at 250 K. The space group is planar monoclinic 12/m(alpha0gamma)0s [a = 7.9602 (4), b = 5.6779 (3), c = 5.6967 (3) A, beta = 90.047 (5)degrees, q(inc) = 0.9000 (9)a* + 0.1735 (6)c*]. The use of powder diffraction techniques to investigate ferroelastic modulated phases is discussed and compared with a previous polydomain single-crystal structural analysis. The modulated displacements of light atoms have been determined, allowing an accurate description of the modulation of both the cations and the O-atom framework. The refinement suggests a displacive model for the phase transition, involving significant atomic shifts for Pb atoms and a quite complex mixing of tilt and deformation of the oxygen octahedra. The average character of this modulated structure is antiferroelectric.
ABSTRACT
The structure of the misfit layer compound [Bi0.87SrO2]2[CoO2]1.82, bismuth strontium cobaltite, was determined by single-crystal X-ray diffraction using the five-dimensional superspace-group formalism. This composite crystal, of monoclinic symmetry, is composed of two subsystems exhibiting incommensurate periodicities along b, the binary axis direction. The first composite part [Bi0.87SrO2] displays an intrinsic modulation of planar monoclinic type characterized by the wavevector q* = 0.293a* + 0.915c*. The second composite part [CoO2] shows two different centered lattice variants. The structure of the misfit layer crystal can be described as an alternation along c of distorted rock-salt-type slabs, formed from [BiO] and [SrO] layers (first subsystem), and of [CoO2] layers (second subsystem) displaying a distorted CdI2-type structure. Two main structural results are obtained. First, as a consequence of the intrinsic modulation, disordered zones, characterized by Bi vacancies, are regularly distributed in the [BiO] layers. Second, strong chemical bonds are implied between the strontium atoms of the first subsystem and the oxygen atoms of the second one.
ABSTRACT
Three orthorhombic crystals of chemical formula Eu(x)V(y)Mo(8+/-z)O(14) were investigated by X-ray diffraction (Mo Kalpha radiation, lambda = 0.71073 Å). They have nearly the same lattice parameters (a approximately 11.3, b approximately 10.0, c approximately 9.2 Å), display one-dimensional incommensurate modulations of wavevector q* = gammac* and are characterized by the same superspace group Cmca(00gamma)s00. The crystals differ both in their compositions (namely Eu(0.976(6))V(1.13(5))Mo(7.10(5))O(14), Eu(0.986(4))V(1.10(3))Mo(7.30(1))O(14) and EuMo(7.96(1))O(14)) and in their gamma components [0.195 (2), 0.245 (2) and 0.286 (3), respectively]. The average structures of these crystals appear closely related to the structures of LaMo(7.7)O(14) (not modulated) and LaMo(8)O(14) (modulated); however, two main differences are outlined: first, the modulation direction is c in the Eu-containing crystals but b in the modulated La-containing crystal [q* = (1/3)b*], second, the Eu-containing crystals have centrosymmetric structures while the La-containing crystals have polar structures (space group C2ca). The Mo (or Mo and V) atoms are stacked to form (001) layers of metallic clusters. The density modulation of these structures implies the existence of the new types of clusters Mo(9), Mo(10), Mo(6)V(4), Mo(7)V(3) and Mo(8)V(2) besides the clusters M(8) (Mo(8), Mo(6)V(2) and Mo(7)V) and M(7) (Mo(7) and Mo(6)V) which are already known. Mo(8) units with cis and trans configurations and Mo(6)V(2) units with a trans configuration appear as the main cluster types in these crystals. The nature of the metallic clusters changes along c, but inside one (001) layer it is likely that only one cluster type with a given configuration is present. The main structural result is the formation, in some unit cells, of strong intercluster Mo-Mo, Mo-V or V-V bonds with distances close to 2.6 Å within a layer as well as between two neighbouring layers.
ABSTRACT
A new mixed-valent monophosphate Sr(2)V(2)O(PO(4))(3) has been synthesized. Its 4-fold superstructure has been refined using the 4D formalism for modulated structures and using X-ray single-crystal diffraction data. The average structure can be described as a stacking of [V(2)P(3)O(13)](infinity) layers and [Sr(2)](infinity) layers. In these layers, the VO(6) octahedra, occupied by V(III), the VO(5) trigonal bipyramids, occupied by V(IV), and the PO(4) tetrahedra form chains running along b. The 4D description allows us to give a better description of the measured intensities in reciprocal space (main and first order satellite reflections) and particularly to explain why the second order satellite reflections are not observed using a classical X-ray source. The corresponding structural mechanism consists of an alternation of disordered ribbons of VO(5) bipyramids and PO(4) tetrahedra in two enantiomorphic configurations, separated by displacively modulated ribbons of VO(6) octahedra and PO(4) tetrahedra. Crystal data: monoclinic, superstructure space group P2(1)/c, Z = 8, a = 17.389(1) Å, b = 5.094(1) Å, c = 30.032(4) Å, beta = 132.17(1) degrees; superspace group P2(1)/m(0,0,(1)/(4))0s, Z = 2, c' = c/4.
