Spin-Glass-like State and Reversible Room-Temperature Magnetocaloric Effect in Double Distorted Perovskites Nd(Cu3-xMnx)Mn4O12.

The preparation, complex magnetic properties and room-temperature magnetocaloric effect in Nd(Cu3-xMnx)Mn4O12 with cation distribution (Nd3+)A(Cu3-x2+xMnx3+)A'(Mn1+x3+Mn3-x4+)BO122- (x = 1 and 1.5) have been reported. Both compounds show a sharp paramagnetic-ferromagnetic (FM) transition at TC of 300 and 280 K, respectively. The substitution of Cu by Mn at the A' site induces the emergence of a spin glass state below ≈63 K for x = 1 and ≈72 K for x = 1.5 compound. Another antiferromagnetic-like magnetic transition is also observed in both compounds at 23 and 28 K, respectively, which is discussed as the antiferromagnetic coupling between Nd3+ at the A' site and (Mn3+/Mn4+) at the B site. These two compounds exhibit room-temperature magnetocaloric effect. For a small field of 2 T, the maximum magnetic entropy changes -ΔSM are 1.5 J/kg K at 300 K and 1.4 J/kg K at 280 K, respectively. Moreover, the -ΔSM(T) curves show an asymmetric distribution, resulting in high refrigerant capacity values for both compounds. We further demonstrate the distinct roles of the A'- and B-site spins on the magnetic properties and the origin of the spin-glass-like state in double distorted perovskites Ln(Cu3-xMnx)Mn4O12 family of compounds.

Low Dimensional Magnetic Lattice and Room Temperature Magneto(di)electric Effect in Polyanion Ruddlesden-Popper Iron Oxides.

We have shown a new design strategy which exploits different oxyanions in a Ruddlesden-Popper (RP)-type phase to modulate the local crystal structure and magnetic lattice. Material (Sr4Fe2(SO4)0.5O6.5) with the larger voluminous oxyanion (SO4, S-O distance = 1.49 Å) as separating blocks between magnetic FeO layers shows a two-dimensional magnetic lattice. A three-dimensional magnetic lattice and spin reorientation transition is observed for the Sr4Fe2(CO3)O6, having CO3 (C-O distance = 1.25 Å), a smaller oxyanion, as a separating layer. Using mixed oxyanions (SO4 and CO3) in the central perovskite block of the RP3 phase, we have demonstrated a facile strategy to modulate the local crystal structure. The modulated displacement of the magnetic cations, which can break the local centrosymmetry, is suggested to originate the magnetodielectric effect near the magnetic ordering temperatures (higher than room temperature). Further, all CO3 containing samples show magnetodielectric coupling below room temperature due to the spin reorientation transition. The room temperature magnetodielectric effect coupled to the targeted local modulation of the crystal structure by oxyanions (in the absence of second-order Jahn-Teller active "distortion centers") opens a new door to the design of new multifunctional materials with the possibility for the room temperature application.

Tetrahedral chain ordering and low dimensional magnetic lattice in a new brownmillerite Sr2ScFeO5.

We report the synthesis, structure and physical properties of a hitherto unreported brownmillerite compound Sr2ScFeO5. We have shown a new ordering sequence of the interlayer iron tetrahedral chains. Reduced dimensionality of the magnetic lattice and the frustration in the two dimensional iron tetrahedral chains originate complex magnetic and magneto-dielectric effects. Our study highlights a novel approach to tailor the magnetic lattice in bulk oxides.

Deciphering local complex order by HAADF in a disordered mixed polyanion iron oxide: Sr4Fe2[Fe0.5(SO4)0.25(CO3)0.25]O7.25.

A layered iron compound involving two divalent polyanions (carbonate and sulfate anions) was synthesized by solid state chemistry in a closed ampule in the form of a ceramic. The Sr4Fe2[Fe0.5(SO4)0.25(CO3)0.25]O7.25 compound derives from the third term of the Ruddlesden and Popper family, Sr4Fe3O10. A multiscale approach through transmission electron microscopy (TEM) and powder neutron diffraction (PND) studies shows that SO4 and CO3 groups substitute for the iron polyhedron of the central layer of the perovskite blocks and the absence of long range ordering between sulfate and carbonates and FeO5 groups. Nevertheless, waves disturbing the expected periodicity of the atomic layer are evidenced in HAADF images. An accurate analysis of these images provides a view of the local cationic order correlated with SO4 and CO3 for FeO5 substitution.

Combining Multiscale Approaches for the Structure Determination of an Iron Layered Oxysulfate: Sr4Fe2.5O7.25(SO4)0.5.

The new iron layered oxysulfate Sr4Fe2.5O7.25(SO4)0.5 has been prepared by a solid-state reaction in closed ampules into the form of ceramics and single crystals. Its atomic structure has been solved by means of spectroscopy, diffraction techniques, and high-resolution electron microscopy. Sr4Fe2.5O7.25(SO4)0.5 is a layered structure that derives from the Ruddelsden-Popper (RP) phases with the layer stacking sequence SrO/SrFeO2.5/SrFe0.5(SO4)0.5O1.25/SrFeO2.5. Within the mixed Fe3+/SO42- layer, the sulfur atoms are slightly shifted from the B site of the perovskite and each sulfate group shares two corners with iron pyramids in the basal plan without any order phenomenon. The electronic conductivity is thermally activated, while no ionic conductivity is detected.

Silver intercalation in SPS dense TiS2: staging and thermoelectric properties.

Polycrystalline samples in the series AgxTiS2 with x varying from 0 to 0.2 were prepared using solid-liquid-vapor reaction and spark plasma sintering. Depending on the x content, it is found that different stages can occur with intercalation, from the so-called 1T-TiS2 (stage 1) to ordered Ag1/6TiS2 (stage 2). Randomly intercalated Ag cations in the van der Waals gap of stage 1 and stage 2 based TiS2 structures induce a strong decrease of lattice thermal conductivity through structural disorder. A decrease in electrical resistivity and the absolute value of the Seebeck coefficient with increasing Ag content supports also the charge transfer to the Ti 3d conduction band, enhancing the power factor in the specific temperature range. Thus, the combined effects of Ag intercalation are beneficial to the improvement in ZT, reaching around 0.45 at 700 K in Ag intercalated compounds.

Single sublattice endotaxial phase separation driven by charge frustration in a complex oxide.

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation.

Revisiting some chalcogenides for thermoelectricity.

Thermoelectric materials that are efficient well above ambient temperature are needed to convert waste-heat into electricity. Many thermoelectric oxides were investigated for this purpose, but their power factor (PF) values were too small (∼10-4 W m-1 K-2) to yield a satisfactory figure of merit zT. Changing the anions from O2- to S2- and then to Se2- is a way to increase the covalency. In this review, some examples of sulfides (binary Cr-S or derived from layered TiS2) and an example of selenides, AgCrSe2, have been selected to illustrate the characteristic features of their physical properties. The comparison of the only two semiconducting binary chromium sulfides and of a layered AgCrSe2 selenide shows that the PF values are also in the same order of magnitude as those of transition metal oxides. In contrast, the PF values of the layered sulfides TiS2 and Cu0.1TiS2 are higher, reaching ∼10-3 W m-1 K-2. Apparently the magnetism related to the Cr-S network is detrimental for the PF when compared to the d0 character of the Ti4+ based sulfides. Finally, the very low PF in AgCrSe2 (PF = 2.25 × 10-4 W m1 K-2 at 700 K) is compensated by a very low thermal conductivity (κ = 0.2 W m-1 K-1 from the measured Cp) leading to the highest zT value among the reviewed compounds (zT700K = 0.8). The existence of a glassy-like state for the Ag+ cations above 475 K is believed to be responsible for this result. This result demonstrates that the phonon engineering in open frameworks is a very interesting way to generate efficient thermoelectric materials.

Derivation of the heat capacity anomaly at a first-order transition by using a semi-adiabatic relaxation technique.

This paper deals with the problem of determining the heat capacity anomaly associated with a first-order transition when using relaxation calorimetry. A method of data recording and analysis is proposed, which is shown to be well suited to investigate such a feature, including its hysteretical character. This technique is applied to spinel vanadates, allowing us to shed light on a recent controversy about the double-transition which takes place in these oxides.