Correlation of Interface Interdiffusion and Skyrmionic Phases.

Magnetic skyrmions are prime candidates for the next generation of spintronic devices. Skyrmions and other topological magnetic structures are known to be stabilized by the Dzyaloshinskii-Moriya interaction (DMI) that occurs when the inversion symmetry is broken in thin films. Here, we show by first-principles calculations and atomistic spin dynamics simulations that metastable skyrmionic states can also be found in nominally symmetric multilayered systems. We demonstrate that this is correlated with the large enhancement of the DMI strength due to the presence of local defects. In particular, we find that metastable skyrmions can occur in Pd/Co/Pd multilayers without external magnetic fields and can be stable even near room temperature conditions. Our theoretical findings corroborate with magnetic force microscopy images and X-ray magnetic circular dichroism measurements and highlight the possibility of tuning the intensity of DMI by using interdiffusion at thin film interfaces.

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.

Spin tuning of electron-doped metal-phthalocyanine layers.

The spin state of organic-based magnets at interfaces is to a great extent determined by the organic environment and the nature of the spin-carrying metal center, which is further subject to modifications by the adsorbate-substrate coupling. Direct chemical doping offers an additional route for tailoring the electronic and magnetic characteristics of molecular magnets. Here we present a systematic investigation of the effects of alkali metal doping on the charge state and crystal field of 3d metal ions in Cu, Ni, Fe, and Mn phthalocyanine (Pc) monolayers adsorbed on Ag. Combined X-ray absorption spectroscopy and ligand field multiplet calculations show that Cu(II), Ni(II), and Fe(II) ions reduce to Cu(I), Ni(I), and Fe(I) upon alkali metal adsorption, whereas Mn maintains its formal oxidation state. The strength of the crystal field at the Ni, Fe, and Mn sites is strongly reduced upon doping. The combined effect of these changes is that the magnetic moment of high- and low-spin ions such as Cu and Ni can be entirely turned off or on, respectively, whereas the magnetic configuration of MnPc can be changed from intermediate (3/2) to high (5/2) spin. In the case of FePc a 10-fold increase of the orbital magnetic moment accompanies charge transfer and a transition to a high-spin state.

Location, speciation, and quantification of carbon in silica phytoliths using synchrotron scanning transmission X-ray microspectroscopy.

Phytoliths of biogenic silica play a vital role in the silicon biogeochemical cycle and occlude a fraction of organic carbon. The location, chemical speciation, and quantification of this carbon within phytoliths have remained elusive due to limited direct experimental evidence. In this work, phytoliths (bilobate morphotype) from the sugarcane stalk epidermis are sectioned with a focused ion beam to produce lamellas (≈10 × 10 µm2 size, <500 nm thickness) and probed by synchrotron scanning transmission X-ray microspectroscopy (≈100-200 nm pixel size; energies near the silicon and carbon K-absorption edges). Analysis of the spectral image stacks reveals the complementarity of the silica and carbon spatial distributions, with carbon found at the borders of the lamellas, in islands within the silica, and dispersed in extended regions that can be described as a mixed silica-carbonaceous matrix. Carbon spectra are assigned mainly to lignin-like compounds as well as to proteins. Carbon contents of 3-14 wt.% are estimated from the spectral maps of four distinct phytolith lamellas. The results provide unprecedented spatial and chemical information on the carbon in phytoliths obtained without interference from wet-chemical digestion.

Spin structure of surface-supported single-molecule magnets from isomorphous replacement and X-ray magnetic circular dichroism.

Surface-supported arrays of Fe(4)-type Single-Molecule Magnets retain a memory effect and are of current interest in the frame of molecule-based information storage and spintronics. To reveal the spin structure of [Fe(4)(L)(2)(dpm)(6)] (1) on Au, an isomorphous compound [Fe(3)Cr(L)(2)(dpm)(6)] was synthesized and structurally and magnetically characterized (H(3)L is tripodal ligand 11-(acetylthio)-2,2-bis(hydroxymethyl)undecan-1-ol and Hdpm is dipivaloylmethane). The new complex contains a central Cr(3+) ion and has a S = 6 ground state as opposed to S = 5 in 1. Low-temperature X-ray Magnetic Circular Dichroism studies at Fe- and Cr-L(2,3) edges revealed that the antiparallel alignment between Fe and Cr spins is preserved on surfaces. Moreover, the different Fe-L(2,3) spectral features found in the homo- and heterometallic species disclose the opposing contribution of the central Fe(3+) ion in the former compound, proving that its ferrimagnetic spin structure is retained on surfaces.

Energy-dispersive X-ray absorption spectroscopy at LNLS: investigation on strongly correlated metal oxides.

An energy-dispersive X-ray absorption spectroscopy beamline mainly dedicated to X-ray magnetic circular dichroism (XMCD) and material science under extreme conditions has been implemented in a bending-magnet port at the Brazilian Synchrotron Light Laboratory. Here the beamline technical characteristics are described, including the most important aspects of the mechanics, optical elements and detection set-up. The beamline performance is then illustrated through two case studies on strongly correlated transition metal oxides: an XMCD insight into the modifications of the magnetic properties of Cr-doped manganites and the structural deformation in nickel perovskites under high applied pressure.

Pressure-induced magnetic switching and linkage isomerism in K0.4Fe4[Cr(CN)6]2.8 x 16 H2O: X-ray absorption and magnetic circular dichroism studies.

The effect of applied pressure on the magnetic properties of the Prussian blue analogue K0.4Fe4[Cr(CN)6]2.8 x 16 H2O (1) has been analyzed by dc and ac magnetic susceptibility measurements. Under ambient conditions, 1 orders ferromagnetically at a critical temperature (T(C)) of 18.5 K. Under application of pressure in the 0-1200 MPa range, the magnetization of the material decreases and its critical temperature shifts to lower temperatures, reaching T(C) = 7.5 K at 1200 MPa. Pressure-dependent Raman and Mossbauer spectroscopy measurements show that this striking behavior is due to the isomerization of some Cr(III)-C[triple bond]N-Fe(II) linkages to the Cr(III)-N[triple bond]C-Fe(II) form. As a result, the ligand field around the iron(II) centers increases, and the diamagnetic low-spin state is populated. As the number of diamagnetic centers in the cubic lattice increases, the net magnetization and critical temperature of the material decrease considerably. The phenomenon is reversible: releasing the pressure restores the magnetic properties of the original material. However, we have found that under more severe pressure conditions, a metastable sample containing 22% Cr(III)-N[triple bond]C-Fe(II) linkages can be obtained. X-ray absorption spectroscopy and magnetic circular dichroism of this metastable sample confirm the linkage isomerization process.

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.

Self-assembled monolayer of Cr7Ni molecular nanomagnets by sublimation.

We show, by complementary spectroscopic and STM analysis, that Cr(7)Ni derivatives are suitable to be sublimed in UHV conditions. Cr(7)Ni-bu weakly bonds to gold surface and can diffuse relatively freely on it, forming monolayers with hexagonal 2D packing. Conversely, by adding a functional thiol group to the central dibutylamine, a covalent bond between the molecule and surface gold adatoms is promoted, leading to a strong molecular grafting and the formation of a disordered monolayer. These two examples demonstrate the possibility to control the assembly of a large molecular complex, as rationalized by DFT calculations that establish different energy scales in the deposition processes. Moreover, low-temperature XMCD sprectra show that the magnetic features of Cr(7)Ni rings deposited in UHV on gold remain unchanged with respect to those of the corresponding bulk sample.

Addressing the magnetic properties of sub-monolayers of single-molecule magnets by X-ray magnetic circular dichroism.

We report on a comparative study of electronic and magnetic properties of Mn6 single-molecule magnets (SMMs) grafted on gold surface. Two derivatives with spin-ground states S=4 and S=12 have been functionalized with 3-tp-CO2- (3-thiophene carboxylate, tpc) ligands and characterized as thick films (TFs) as well as sub-monolayers (sMLs) by synchrotron based techniques. X-ray absorption spectroscopy at the Mn L2,3 edges shows the modification of the spectral lineshape in the sMLs with respect to the TFs suggesting that the local symmetry at the Mn sites changes once the molecules are deposited on gold surface. In spite of this, the expected MnIII oxidation state is preserved. X-ray magnetic circular dichroism (XMCD) spectra show that the total magnetic moment is only given by spin part because of the quenched orbital moment. Moreover, variable temperature and variable field XMCD spectra reveal an effective decrease of the Mn spin moment for both derivatives.

Linear and circularly polarized light to study anisotropy and resonant scattering in magnetic thin films.

The remarkable polarization properties of synchrotron light have lead to the advent of modern synchrotron-related spectroscopic studies with angular and/or magnetic selectivity. Here an overview is given of the prominent aspects of the polarization of the light delivered by a bending magnet, and some dichroic properties in X-ray absorption spectroscopy (XAS). Two studies developed at the Brazilian Synchrotron Light Laboratory are then reported, exemplifying the profit gained using linear and circular polarization of X-rays for the study of magnetic thin films and multilayers. Angle-resolved XAS was used in strained manganite thin films to certify a model of local distortion limited within the MnO6 polyhedron. A pioneering experience of X-ray magnetic scattering at grazing incidence associated with dispersive XAS in a Co/Gd multilayer draws new perspectives for magnetic studies in thin films and multilayers under atmospheric conditions in the hard X-ray range.