Size-Dependence and High Temperature Stability of Radial Vortex Magnetic Textures Imprinted by Superconductor Stray Fields.

Swirling spin textures, including topologically nontrivial states, such as skyrmions, chiral domain walls, and magnetic vortices, have garnered significant attention within the scientific community due to their appeal from both fundamental and applied points of view. However, their creation, controlled manipulation, and stability are typically constrained to certain systems with specific crystallographic symmetries, bulk or interface interactions, and/or a precise stacking sequence of materials. Recently, a new approach has shown potential for the imprint of magnetic radial vortices in soft ferromagnetic compounds making use of the stray field of YBa2Cu3O7-δ superconducting microstructures in ferromagnet/superconductor (FM/SC) hybrids at temperatures below the superconducting transition temperature (TC). Here, we explore the lower size limit for the imprint of magnetic radial vortices in square and disc shaped structures as well as the persistence of these spin textures above TC, with magnetic domains retaining partial memory. Structures with circular geometry and with FM patterned to smaller radius than the superconductor island facilitate the imprinting of magnetic radial vortices and improve their stability above TC, in contrast to square structures where the presence of magnetic domains increases the dipolar energy. Micromagnetic modeling coupled with a SC field model reveals that the stabilization mechanism above TC is mediated by microstructural defects. Superconducting control of swirling spin textures, and their stabilization above the superconducting transition temperature by means of defect engineering holds promising prospects for shaping superconducting spintronics based on magnetic textures.

Large Magnetoresistance of Isolated Domain Walls in La2/3 Sr1/3 MnO3 Nanowires.

Generation, manipulation, and sensing of magnetic domain walls are cornerstones in the design of efficient spintronic devices. Half-metals are amenable for this purpose as large low field magnetoresistance signals can be expected from spin accumulation at spin textures. Among half metals, La1- x Srx MnO3 (LSMO) manganites are considered as promising candidates for their robust half-metallic ground state, Curie temperature above room temperature (Tc = 360 K, for x = 1/3), and chemical stability. Yet domain wall magnetoresistance is poorly understood, with large discrepancies in the reported values and conflicting interpretation of experimental data due to the entanglement of various source of magnetoresistance, namely, spin accumulation, anisotropic magnetoresistance, and colossal magnetoresistance. In this work, the domain wall magnetoresistance is measured in LSMO cross-shape nanowires with single-domain walls nucleated across the current path. Magnetoresistance values above 10% are found to be originating at the spin accumulation caused by the mistracking effect of the spin texture of the domain wall by the conduction electrons. Fundamentally, this result shows the importance on non-adiabatic processes at spin textures despite the strong Hund coupling to the localized t2g electrons of the manganite. These large magnetoresistance values are high enough for encoding and reading magnetic bits in future oxide spintronic sensors.

Complex structural ordering of the oxygen deficiency in La0.5Ca2.5Mn2O7-δ Ruddlesden-Popper phases.

Ruddlesden-Popper oxides, (AO)(ABO3)n, occupy a prominent place in the landscape of materials research because of their intriguing potential applications. Compositional modifications to the cation sublattices, A or B, have been explored in order to achieve enhanced functionalities. However, changes to the anionic sublattice have been much less explored. In this work, new oxygen-deficient manganese Ruddlesden-Popper-related phases, La0.5Ca2.5Mn2O6.5 and La0.5Ca2.5Mn2O6.25, have been synthesized by controlled reduction of the fully oxidized n = 2 term La0.5Ca2.5Mn2O7. A complete structural and compositional characterization, by means of neutron diffraction, electron diffraction and atomically resolved scanning transmission electron microscopy and electron energy-loss spectroscopy techniques, allows the proposition of a topotactic reduction pathway through preferential oxygen removal in the [MnO2] layers along [031] and [0{\bar 1}3] directions. The gradual decrease of the Mn oxidation state, accommodated by short-range ordering of anionic vacancies, reasonably explains the breaking of ferromagnetic interactions reinforcing the emergence of antiferromagnetic ones. Additional short-range order-disorder phenomena of La and Ca cations have been detected in the reduced La0.5Ca2.5Mn2O7-δ, as previously reported in the parent compound.

In operando evidence of deoxygenation in ionic liquid gating of YBa2Cu3O7-X.

Field-effect experiments on cuprates using ionic liquids have enabled the exploration of their rich phase diagrams [Leng X, et al. (2011) Phys Rev Lett 107(2):027001]. Conventional understanding of the electrostatic doping is in terms of modifications of the charge density to screen the electric field generated at the double layer. However, it has been recently reported that the suppression of the metal to insulator transition induced in VO2 by ionic liquid gating is due to oxygen vacancy formation rather than to electrostatic doping [Jeong J, et al. (2013) Science 339(6126):1402-1405]. These results underscore the debate on the true nature, electrostatic vs. electrochemical, of the doping of cuprates with ionic liquids. Here, we address the doping mechanism of the high-temperature superconductor YBa2Cu3O7-X (YBCO) by simultaneous ionic liquid gating and X-ray absorption experiments. Pronounced spectral changes are observed at the Cu K-edge concomitant with the superconductor-to-insulator transition, evidencing modification of the Cu coordination resulting from the deoxygenation of the CuO chains, as confirmed by first-principles density functional theory (DFT) simulations. Beyond providing evidence of the importance of chemical doping in electric double-layer (EDL) gating experiments with superconducting cuprates, our work shows that interfacing correlated oxides with ionic liquids enables a delicate control of oxygen content, paving the way to novel electrochemical concepts in future oxide electronics.

3D elemental mapping with nanometer scale depth resolution via electron optical sectioning.

Electron energy loss spectroscopy in the scanning transmission electron microscope has long been used to perform elemental mapping but has not previously exhibited depth sensitivity. The key to depth resolution with optical sectioning is the transfer of sufficiently high lateral spatial frequencies. By performing spectrum imaging with atomic resolution we achieve nanometer scale depth resolution, enabling us to optically section an oxide heterostructure spectroscopically. Such 3D elemental mapping is sensitive to atomic scale changes in structure and composition and is more interpretable than Z-contrast imaging alone.

Water-Free Proton Conduction in Discotic Pyridylpyrazolate-based Pt(II) and Pd(II) Metallomesogens.

In this work we report on water-free proton conductivity in liquid-crystal pyridylpyrazolate-based Pt(II) and Pd(II) complexes [M(pz(R(n,n)py))2] (pz(R(n,n)py) = 3-(3,5-dialkyloxyphenyl)-5-(pyridin-2-yl)pyrazolate, R(n,n) = C6H3(OCnH2n+1)2; n = 4, 12, 16, M = Pd; n = 12, M = Pt) with potential application as electrolyte materials in proton exchange membrane fuel cells. The columnar ordering of the complexes in the liquid-crystalline phase opens nanochannels, which are used for fast proton exchange as detected by impedance spectroscopy and NMR. The NMR spectra indicate that the proton conduction mechanism is associated with a novel C-H···N proton transfer, which persists above the clearing point of the material. The highest conductivity of ∼0.5 µS cm(-1) at 180 °C with an activation energy of 1.2 eV is found for the Pt(II) compound in the mesophase. The Pd(II) complexes with different chain length (n = 4, 12, and 16) show lower conductivity but smaller activation energies, in the range of 0.74-0.93 eV.

Mapping chemical disorder and ferroelectric distortions in the double perovskite compound Sr 2-x Gd x MnTiO6 by atomic resolution electron microscopy and spectroscopy.

In this work we report a study of the chemical and structural order of the double perovskite compound Sr 2-x Gd x MnTiO6 for compositions x=0, 0.25, 0.5, 0.75, and 1. A noticeable disorder at the B-site in the Mn and Ti sublattice is detected at the atomic scale by electron energy-loss spectroscopy for all x values, resulting in Mn-rich and Ti-rich regions. For x ≥ 0.75, the cubic unit cell doubles and lowers its symmetry because of structural rearrangements associated with a giant ferroelectric displacement of the perovskite B-site cation. We discuss this finding in the light of the large electroresistance observed in Sr 2-x Gd x MnTiO6, x ≥ 0.75.

Electron doping by charge transfer at LaFeO3/Sm2CuO4 epitaxial interfaces.

Using X-ray absorption spectroscopy and electron energy loss spectroscopy with atomic-scale spatial resolution, experimental evidence for charge transfer at the interface between the Mott insulators Sm2 CuO4 and LaFeO3 is obtained. As a consequence of the charge transfer, the Sm2 CuO4 is doped with electrons and thus epitaxial Sm2 CuO4 /LaFeO3 heterostructures become metallic.

Tailoring disorder and dimensionality: strategies for improved solid oxide fuel cell electrolytes.

Reducing the operation temperature of solid oxide fuel cells is a major challenge towards their widespread use for power generation. This has triggered an intense materials research effort involving the search for novel electrolytes with higher ionic conductivity near room temperature. Two main directions are being currently followed: the use of doping strategies for the synthesis of new bulk materials and the implementation of nanotechnology routes for the fabrication of artificial nanostructures with improved properties. In this paper, we review our recent work on solid oxide fuel cell electrolyte materials in these two directions, with special emphasis on the importance of disorder and reduced dimensionality in determining ion conductivity. Substitution of Ti for Zr in the A(2)Zr(2-) (y)Ti(y)O(7) (A = Y, Dy, and Gd) series, directly related to yttria stabilized zirconia (a common fuel cell electrolyte), allows controlling ion mobility over wide ranges. In the second scenario we describe the strong enhancement of the conductivity occurring at the interfaces of superlattices made by alternating strontium titanate and yttria stabilized zirconia ultrathin films. We conclude that cooperative effects in oxygen dynamics play a primary role in determining ion mobility of bulk and artificially nanolayered materials and should be considered in the design of new electrolytes with enhanced conductivity.