Structural transition at 360 K in the CaFe5O7 ferrite: toward a new charge ordering distribution.

An efficient synthesis route is proposed to obtain single phase powder ceramic of CaFe5O7. This complex structure can be described as an intergrowth between one CaFe2O4 unit and n = 3 slices of FeO Wüstite-type structure. A detailed structural study has been carried out at room temperature combining transmission electron microscopy (TEM) observations (ED, HREM), scanning transmission electron microscopy (STEM-HAADF), and X-ray diffraction data. The analysis of these data has revealed an unexpected supercell with a monoclinic symmetry. From the hkl conditions deduced from the electron diffraction study and the analysis of X-ray diffraction data by simulated annealing, a structural model considering the centrosymmetric P21/m setting can be proposed. In addition the first magnetic and electrical transport measurements are reported showing a sharp peak in magnetic susceptibility and a strong localization around 360 K, associated to a structural change from monoclinic setting to orthorhombic one.

Large oxygen nonstoichiometry in La(0.77)Sr(3.23)Co(2.75)C(0.25)O(8.40+δ) oxide (δ = 0, 1.3) related to n = 3 RP series.

An original Ruddlesden-Popper phase, La(0.77)Sr(3.23)Co(2.75)C(0.25)O(8.40+δ), was isolated and studied by electron, X-ray, and neutron diffraction. This structure has complex crystal chemistry resulting from a high degree of flexibility in the structure, comprising the disordered introduction of carbonates into a cobalt layer and an important oxygen deficiency with a preferential repartition of vacancies along the layers stacking sequence. The former is necessary for the stabilization of the system, while the latter can be tuned by postsynthetic treatment, yielding in a large variety of cobalt species formal oxidation states ranging from Co(2+)/Co(3+) in the as-made phase to Co(3+)/Co(4+) when annealed under oxygen pressure. The potential richness deriving from this flexibility is illustrated in terms of the magnetotransport properties and includes a resistivity that varies within a range of 5 orders of magnitude after modulation of the oxygen content with the appearance of negative magnetoresistance and ferromagnetic interactions due to Co(3+)/Co(4+) mixed-valence state.

Thermodynamic model of the coupled valence and spin state transition in cobaltates.

A class of cobalt-based oxides exhibits a peculiar type of transition, entangling valence and spin state degrees of freedom of 4f and 3d elements. It constitutes one of the most spectacular illustrations of the interplay between charge, spin and lattice degrees of freedom in strongly correlated materials. In this work, we present a thermodynamic model capable to reproduce the main features of this transition. Our approach is based on the minimization of a free energy combining the contributions of two sublattices and the interaction between them. The coupling energies introduced in the model are related to well-known chemical pressure effects in the perovskite structure. The results of this model are compared to experimental data derived from x-ray absorption spectroscopy.

Searching for new thermoelectric materials: some examples among oxides, sulfides and selenides.

Different families of thermoelectric materials have been investigated since the discovery of thermoelectric effects in the mid-19th century, materials mostly belonging to the family of degenerate semi-conductors. In the last 20 years, new thermoelectric materials have been investigated following different theoretical proposals, showing that nanostructuration, electronic correlations and complex crystallographic structures (low dimensional structures, large number of atoms per lattice, presence of 'rattlers'…) could enhance the thermoelectric properties by enhancing the Seebeck coefficient and/or reducing the thermal conductivity. In this review, the different strategies used to optimize the thermoelectric properties of oxides and chalcogenides will be presented, starting with a review on thermoelectric oxides. The thermoelectric properties of sulfides and selenides will then be discussed, focusing on layered materials and low dimensional structures (TiS2 and pseudo-hollandites). Some sulfides with promising ZT values will also be presented (tetrahedrites and chalcopyrites).

Jumps in entropy and magnetic susceptibility at the valence and spin-state transition in a cobalt oxide.

A wide family of cobalt oxides of formulation (Pr(1-y)Ln(y))(1-x)Ca(x)CoO3 (Ln being a lanthanide) exhibits a coupled valence and spin-state transition (VSST) at a temperature T*, which involves two concomitant modifications: (i) a change in the spin state of Co(3+) from low-spin (T < T*) to a higher spin state (T > T*) and (ii) a change in the valence state of Pr, from a mixed Pr(4+)/Pr(3+) state (T < T*) to a purely trivalent state (T > T*), accompanied by an ~ 90 K is investigated by magnetization and heat capacity measurements.First, we quantitatively characterized the jumps in magnetic susceptibility (χ) and entropy (S) around T*. Then, these values were compared to those calculated as a function of the variations in the population of the different cationic species involved in the VSST. X-ray absorption spectroscopy experiments recently showed that the higher spin state above T* should be regarded as an inhomogeneous mixture between low-spin (LS) and high-spin (HS) states. In the frame of this description, we demonstrate that the jumps in both χ and S can be associated with the same change in the Co(3+) HS content around T*. This result lends further support to the relevance of the LS/HS picture for the VSST, challenging the currently dominant interpretation based on the occurrence of an intermediate-spin (IS) state of Co(3+) above T*.

Zero magnetization in a disordered (La(1-x/2)Bi(x/2))(Fe(0.5)Cr(0.5))O(3) uncompensated weak ferromagnet.

The orthorhombic perovskite, (La(1-x/2)Bi(x/2))(Fe(0.5)Cr(0.5))O(3) was investigated for 0≤x≤1. Its space group, Pnma, compatible with the disordering of iron and chromium in the B sites, confirms previous observations. More importantly this compound is found to be an uncompensated weak ferromagnet, with a very peculiar zero magnetization behaviour, generally observed for ordered magnetic cations in the B sites. It exhibits a magnetic transition at high temperature (T(C)) above 450 K, while the zero magnetization occurs between 100 and 160 K depending on the x-value. The AC magnetic susceptibility study shows that this compound does not exhibit a spin glass or cluster glass behaviour, in contrast to what was suggested for the x = 0 compound. This zero magnetization phenomenon can be interpreted by the fact that this perovskite is an uncompensated weak ferromagnet, which consists of canted weak ferromagnetic domains and clusters of pure chromium and pure iron composition, antiferromagnetically coupled through Cr-O-Fe interactions.