BUSCADOR RECOLECTA

The multifunctional (ferromagnetic and ferroelectric) response at room temperature that is elusive in single phase multiferroic materials can be achieved in a proper combination of ferroelectric perovskites and ferrimagnetic spinel oxides in horizontal heterostructures. In this work, lead-free CoFe 2 O 4 /BaTiO 3 bilayers are integrated with Si(001) using LaNiO 3 /CeO 2 /YSZ as a tri-layer buffer. They present structural and functional properties close to those achieved on perovskite substrates: the bilayers are fully epitaxial with extremely flat surface, and exhibit robust ferromagnetism and ferroelectricity at room temperature.

[EN] NiFe-carbon magnetic nanocomposites prepared using hybrid sebacate intercalated layered double hydroxides (LDHs) as precursors are shown to be of interest as supercapacitors. Here, the low-temperature formation mechanism of these materials has been deciphered by means of a combined study using complementaryin situ(temperature-dependent) techniques. Specifically, studies involving X-ray powder diffraction, thermogravimetry coupled to mass spectrometry (TG-MS), statistical Raman spectroscopy (SRS), aberration-corrected scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) have been carried out. The experimental results confirm the early formation of FeNi(3)nanoparticles atca.200-250 degrees C, preceding the concerted collapse of the starting NiFe-LDH laminar structure over just 50 degrees C (from 350 to 400 degrees C). At the same time, the catalytic interactions between the metallic atoms and the organic molecules permit the concomitant formation of a graphitic carbon matrix leading to the formation of the final FeNi3-carbon nanocomposite. Furthermore,in situtemperature-dependent experiments in the presence of the intrinsic magnetic field of the STEM-EELS allow observing the complete metal segregation of Ni and Fe even at 400 degrees C. These results provide fundamental insights into the catalytic formation of carbon-based nanocomposites using LDHs as precursors and pave the way for the fine-tuning of their properties, with special interest in the field of energy storage and conversion, Financial support from the European Union (ERC Advanced Grant Mol-2D 788222, ERC Starting Grant 2D-PnictoChem 804110, ERC Proof of Concept Grant Hy-MAC 713704, and COST-Action on Molecular Spintronics (MOLSPIN CA15128)), the Spanish MINECO (Projects MAT2017-89993-R, MAT2015-66888-C3-3-R, RTI2018-097895-B-C43 co-financed by FEDER, and the Unit of Excellence "Maria de Maeztu" MDM-2015-0538), and the Generalitat Valenciana (Prometeo Program and iDiFEDER/2018/061 co-financed by FEDER) is gratefully acknowledged. G. A. acknowledges the support by the Deutsche Forschungsgemeinschaft DFG (FLAG-ERA AB694/2-1) and the Generalitat Valenciana (CIDEGENT/2018/001 grant). G. A. received financial support through the Postdoctoral Junior Leader Fellowship Programme from "la Caixa" Banking Foundation. J. R. thanks the Spanish MINECO for his predoctoral grant. Electron microscopy observations were carried out at the ICTS ELECMI node at Centro Nacional de Microscopia Electronica at the Universidad Complutense de Madrid. The authors thank Dr Maria Dolores Jordan Martin for her kind assistance with the XPS measurements.

The aim of this work is to clarify how in-plane magnetic anisotropy and magnetoelasticity depend on the thickness of Ga-rich FeGa layers. Samples with an Fe72Ga28 composition were grown by sputtering in the ballistic regime in oblique incidence. Although for these growth conditions uniaxial magnetic anisotropy could be expected, in-plane anisotropy is only present when the sample thickness is above 100 nm. By means of differential X-ray absorption spectroscopy, we have determined the influence of both Ga pairs and tetragonal cell distortion on the evolution of the magnetic anisotropy with the increase of FeGa thickness. On the other hand, we have used the cantilever beam technique with capacitive detection to also determine the evolution of the magnetoelastic parameters with the thickness increase. In this case, experimental results can be understood considering the grain distribution. Therefore, the different physical origins for anisotropy and magnetoelasticity open up the possibility to independently tune these two characteristics in Ga-rich FeGa films.

The reduction of the lattice thermal conductivity is one of the crucial steps in improving thermoelectric materials. In skutterudites, a well-known approach is to reduce the thermal conductivity by filling the structural cage with rare-earth atoms. In this work, we show that it is not just the amount of such filling itself but its nanoscale structuration that lowers the thermal conductivity. A straightforward synthesis procedure under high pressure yields Ce- and Yb-filled CoSb3 skutterudites, with and without an inhomogeneous distribution of the filler atoms. The composition of the phases is evaluated from synchrotron Xray diffraction (SXRD) data; the highly nanostructured morphology is verified by high-resolution transmission electron microscopy (TEM). The filling fluctuation, i.e., the uneven distribution of filling atoms in the sample originating a phase segregation, brings about low lattice thermal conductivity, as a strong source of phonon scattering. This effect is prominent in the Ce-filled compound, where Ce is segregated into Ce-rich and Ce-poor regions, and the lattice contribution of the thermal conductivity kappa(L), shows a concomitant reduction, approaching values as low as 1.6 W m(-1) K-1 at 800 K. Although the level of filling is much higher in YbxCoSb3, its lattice thermal conductivity remains larger. Overall, though, its power factor is enhanced due to charge transfer from the Yb-filler. We thus define a new paradigm for the design of filled skutterudites with exceptionally low thermal conductivities, based on the nanoscale mixing of two phases with different filling factors, spontaneously induced by high-pressure synthesis conditions, which can be considered as pseudoamorphous structures with significant reduction in kappa(L).

Thermoelectric mischmetal-filled Mm(x)Co(4)Sb(12) (Mm: natural cocktail of rare-earth elements, mostly Ce and La) skutterudites have been synthesized and sintered in one step under high-pressure conditions at 3.5 GPa in a piston-cylinder hydrostatic press. Synchrotron X-ray diffraction patterns display a splitting of the diffraction peaks ascribed to purely Ce-, and Mm-filled skutterudite phases, which have been analyzed and confirmed by high-resolution TEM and EELS. A total thermal conductivity () of 1.51 W m(-1) K-1 is measured at 773 K for Mm(0.5)Co(4)Sb(12), below that of other filled skutterudites, which is promoted by the enhanced phonon scattering over a broad range of the phonon spectrum due to the inhomogeneous and nanoscale mischmetal inclusion. Compared to undoped CoSb3 skutterudite synthesized by conventional methods, is reduced by a factor of 3, while the power factor is also substantially enhanced.

Sb-doped Bi2Te3 is known since the 1950s as the best thermoelectric material for near-room temperature operation. Improvements in material performance are expected from nanostructuring procedures. We present a straightforward and fast method to synthesize already nanostructured pellets that show an enhanced ZT due to a remarkably low thermal conductivity and unusually high Seebeck coefficient for a nominal composition optimized for arc-melting: Bi0.35Sb1.65Te3. We provide a detailed structural analysis of the Bi2−xSbxTe3 series (0 ≤ x ≤ 2) based on neutron powder diffraction as a function of composition and temperature that reveals the important role played by atomic vibrations. Arc-melting produces layered platelets with less than 50 nm-thick sheets. The low thermal conductivity is attributed to the phonon scattering at the grain boundaries of the nanosheets. This is a fast and cost-effective production method of highly efficient thermoelectric materials.

In this chapter we will review a few examples of applications of atomic resolution aberration corrected scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) to complex oxide materials. These are most challenging systems where subtle changes in structure or chemistry may result in colossal responses in macroscopic physical behavior. Here, we will review how atomic resolution compositional mapping can be achieved in manganite thin films and single crystals, highlighting the importance of considering artifacts during quantification. Besides, minor changes in near edge fine structure may take place when the crystalline environment, and hence nearest neighbor configuration, is modified. These can also be tracked by atomic resolution EELS, as will be shown through the study of binary Fe oxides. Also, examples regarding the study of distributions of point defects such as 0 vacancies in cobaltite thin films will be discussed. In these materials, a combination of epitaxial strain and defects may promote physical behaviors not present in bulk, such as the stabilization of unexpected spin state superlattices. Last, a study of extended defects such as dislocation lines will be reviewed. In particular, we will show how chemical segregation at dislocation cores in yttria-stabilized zirconia grain boundaries results in the generation of static O vacancies that affect the local electrostatic potential and hence, the macroscopic ionic conduction properties.

Interfaces play a crucial role in composite magnetic materials and particularly in bimagnetic core/shell nanoparticles. However, resolving the microscopic magnetic structure of these nanoparticles is rather complex. Here, we investigate the local magnetization of antiferromagnetic/ferrimagnetic FeO/Fe3O4 core/shell nanocubes by electron magnetic circular dichroism (EMCD). The electron energy-loss spectroscopy (EELS) compositional analysis of the samples shows the presence of an oxidation gradient at the interface between the FeO core and the Fe3O4 shell. The EMCD measurements show that the nanoparticles are composed of four different zones with distinct magnetic moment in a concentric, onion-type, structure. These magnetic areas correlate spatially with the oxidation and composition gradient with the magnetic moment being largest at the surface and decreasing toward the core. The results show that the combination of EELS compositional mapping and EMCD can provide very valuable information on the inner magnetic structure and its correlation to the microstructure of magnetic nanoparticles., The authors acknowledge the financial support from the Spanish Minister of Science and Innovation (MICINN) through the projects PID2019-106165GB-C21, PID2019-106165GB-C22, and PID2019-106229RB-I00. They also acknowledge funding from Generalitat de Catalunya through the 2017-SGR-292 and 2017-SGR-776 projects. In addition, research at UCM was supported by MINECO/FEDER MAT2015-66888-C3-3-R and RTI2018-097895-B-C43 grants. ICN2 is funded by the CERCA programme/Generalitat de Catalunya. The ICN2 is supported by the Severo Ochoa Centres of Excellence programme, funded by the Spanish Research Agency (AEI, Grant SEV-2017-0706). M.E. thanks the Spanish MICINN and AEI/FSE for Ramón y Cajal contract (RYC2018-024396-I). A.L.O. acknowledges support from the Universidad Pública de Navarra (Grant PJUPNA2020). STEM-EELS observations carried out at the Centro Nacional de Microscopía Electrónica at Universidad Complutense de Madrid, Spain (ICTS ELECMI).