Abstract: By means of synchrotron x-ray and electron diffraction, we studied the structural changes at the charge order transition T-CO = 176 K in the mixed-valence quadruple perovskite (NaMn3)Mn4O12. Below T-CO we find satellite peaks indicating a commensurate structural modulation with the same propagation vector q = ( 1/2,0,-1/2) of the CE magnetic structure that orders at low temperatures, similarly to the case of simple perovskites such as La0.5Ca0.5MnO3. In the present case, the modulated structure, together with the observation of a large entropy change at T-CO, gives evidence of a rare case of full Mn3+/Mn4+ charge and orbital order, consistent with the Goodenough-Kanamori model.

Abstract: The structure and defect structure of superconducting ferromagnetic bulk RuSr2GdCu2O8 has been investigated using high-resolution transmission electron microscopy and high-resolution scanning transmission microscopy. Two distinct, but closely related structures, due to ordering of rotated RuO6 octahedra and due to Cu substitution in the Ru-O layer, have been revealed. The structure of Ru1-xSr2GdCu2+xO8-delta can be described as a periodic alteration along the c axis of CuO4 planes and RuO6 octahedra. The unit-cell parameters of this phase are root 2a(p) x root 2a(p) x 2c. The possible influence of this phase and defect structure on the sensitivity of the superconductivity and magnetic properties is discussed. Local defects such as 90 S domain boundaries, (130) antiphase boundaries, and the associated dislocations are analyzed.

Abstract: An interface modification of (LaCa)MnO3-BaTiO3 superlattices was found to massively influence magnetic and magnetotransport properties. Moreover it determines the crystal structure of the manganite layers, changing it from orthorhombic (Pnma) for the conventional superlattice (cSL), to rhombohedral (R3̅ c) for the modified one (mSL). While the cSL shows extremely nonlinear ac transport, the mSL is an electrically homogeneous material. The observations go beyond an oversimplified picture of dead interface layers and evidence the importance of electronic correlations at perovskite interfaces.

Abstract: The transport and magnetic measurements of polycrystalline Pb1.6V8O16 hollandite reveal a concomitant metal to insulator and antiferromagnetic transition at TMI≈140 K. A clear localization is found below TMI, evidenced by a rapid increase in the absolute value of the negative Seebeck coefficient. The structural study by x-ray and transmission electron microscopy confirms the hollandite structure and shows that no structural transition occurs at TMI, ruling out a possible charge orbital ordering. The negative Seebeck coefficient observed from 50 K up to 900 K, with values reaching S=−38 μV K−1 at 900 K, is explained by the electron doping of ∼1.4e− in the V empty t2g orbitals responsible for the bad metal resistivity (ρ900 K∼2 mΩ cm). As this S value is close to that obtained by considering only the spin and orbital degeneracies, it is expected that |S| for such vanadates will not be sensitive at high temperature to the t2g band filling

Abstract: (La2/3Ca1/3MnO3)n/(BaTiO3)m (LCMOn/BTOm) superlattices on MgO and SrTiO3 substrates with different layer thicknesses (n = 10, 38, 40 and m = 5, 18, 20) have been grown by metal organic aerosol deposition (MAD) and have been fully characterized down to the atomic scale to study the interface characteristics. Scanning transmission electron microscopy combined with spatially resolved electron energy-loss spectroscopy provides clear evidence for the existence of atomically sharp interfaces in MAD grown films, which exhibit epitaxial growth conditions, a uniform normal strain, and a fully oxidized state. Below a critical layer thickness the LCMO structure is found to change from the bulk Pnma symmetry to a pseudocubic R3̅ c symmetry. An atomically flat interface reconstruction consisting of a single Ca-rich atomic layer is observed on the compressively strained BTO on LCMO interface, which is thought to partially neutralize the total charge from the alternating polar atomic layers in LCMO as well as relieving strain at the interface. No interface reconstruction is observed at the tensile strained LCMO on BTO interface.

Abstract: This report describes the effect of light irradiation on the synthesis of silver nanowires by the well-known polyol method. High quality nanowires are produced in high yields when the reaction suspension is irradiated with 400500 nm light during the nucleation stage. These studies suggest that light accelerates the formation of the nanoparticle seeds most appropriate for nanowire growth.

Abstract: The one-step preparation of capped PbS nanoparticles in an inorganic matrix via UV-induced decomposition of lead thiosulfate complexes intercalated into a hydrotalcite-type layered double hydroxide is reported.

Abstract: The limitations of the loading of the porous metalorganic framework [Zn4O(bdc)3] (bdc = benzene-1,4-dicarboxylate; MOF-5 or IRMOF-1) with Pd nanoparticles was investigated. First, the volatile organometallic precursor [Pd(5-C5H5)(3-C3H5)] was employed to get the inclusion compound [Pd(5-C5H5)(3-C3H5)]x@MOF-5 via gas-phase infiltration at 10-3 mbar. A loading of four molecules of [Pd(5-C5H5)(3-C3H5)] per formula unit of MOF-5 (x = 4) can be reached (35 wt.% Pd). Second, the metalorganic precursor [Pd(acac)2] (acac = 2,4-pentanedionate) was used and the inclusion materials [Pd(acac)2]x@MOF-5 of different Pd loadings were obtained by incipient wetness infiltration. However, the maximum loading was lower as compared with the former case with about two precursor molecules per formula unit of MOF-5. Both loading routes are suitable for the synthesis of Pd nanoparticles inside the porous host matrix. Homogeneously distributed nanoparticles with diameter of 2.4(±0.2) nm can be achieved by photolysis of the inclusion compounds [Pd(5-C5H5)(3-C3H5)]x@MOF-5 (x 4), while the hydrogenolysis of [Pd(acac)2]x@MOF-5 (x 2) leads to a mixture of small particles inside the network (< 3 nm) and large Pd agglomerates (40 nm) on the outer surface of the MOF-5 specimens. The pure Pdx@MOF-5 materials proved to be stable under hydrogen pressure (2 bar) at 150 °C over many hours. Neither hydrogenation of the bdc linkers nor particle growth was observed. The new composite materials were characterized by 1H/13C-MAS-NMR, powder XRD, ICP-AES, FT-IR, N2 sorption measurements and high resolution TEM. Raising the Pd loading of a representative sample Pd4@MOF-5 (35 wt.% Pd) by using [Pd(5-C5H5)(3-C3H5)] as precursor in a second cycle of gas-phase infiltration and photolysis was accompanied by the collapse of the long-range crystalline order of the MOF.

Abstract: Successful encapsulation of polyoxometalate (POM) within the framework of a mesoporous iron trimesate MIL-100(Fe) sample has been achieved by direct hydrothermal synthesis in the absence of fluorine. XRPD, 31P MAS NMR, IR, EELS, TEM and 57Fe Mössbauer spectrometry corroborate the insertion of POM within the cavities of the MOF. The experimental Mo/Fe ratio is 0.95, in agreement with the maximum theoretical amount of POM loaded within the pores of MIL-100(Fe), based on steric hindrance considerations. The POM-MIL-100(Fe) sample exhibits a pore volume of 0.373 cm3 g−1 and a BET surface area close to 1000 m2 g−1, indicating that small gas molecules can easily diffuse inside the cavities despite the presence of heavy phosphomolybdates. These latter contribute to the decrease in the overall surface area, due to the increase in molar weight, by 65%. Moreover, the resulting Keggin containing MIL-100(Fe) solid is stable in aqueous solution with no POM leaching even after more than 2 months. In addition, no exchange of the Keggin anions by tetrabutylammonium perchlorate in organic media has been observed.

Abstract: Defect mediated high temperature ferromagnetism in oxide nanocrystallites is the central feature of this work. Here, we report the development of room temperature ferromagnetism in nanosized Co-doped barium titanate particles with a size of around 14 nm, synthesized by a solvothermal drying method. A combination of x-ray diffraction with state-of-the-art electron microscopy techniques confirms the intrinsic doping of Co into BaTiO3. The development of the room temperature ferromagnetism was tracked down to the different donor defects, namely hydroxyl groups at the oxygen site (\mathrm {OH}_{\mathrm {(O)}}

Abstract: The complex dielectric susceptibility and spin glass properties of polycrystalline CuCr0.5V 0.5O2 delafossite have been investigated. Electron diffraction, high resolution electron microscopy and electron energy loss spectroscopy show that the Cr3+ and V 3+ magnetic cations are randomly distributed on the triangular network of CdI2-type layers. In contrast to CuCrO2, CuCr0.5V 0.5O2 exhibits two distinctive (magnetic and electric) glassy states evidenced by memory effects in electric and magnetic susceptibilities. A large magnetodielectric coupling is observed at low temperature.