Search

The formation of complex hierarchical nanostructures has attracted a lot of attention from both the fundamental science and potential applications point of view. Spherulite structures with radial fibrillar branches have been found in various solids; however, their growth mechanisms remain poorly understood. Here, we report real time imaging of the formation of two-dimensional (2D) iron oxide spherulite nanostructures in a liquid cell using transmission electron microscopy (TEM). By tracking the growth trajectories, we show the characteristics of the reaction front and growth kinetics. Our observations reveal that the tip of a growing branch splits as the width exceeds certain sizes (5.5–8.5 nm). The radius of a spherulite nanostructure increases linearly with time at the early stage, transitioning to nonlinear growth at the later stage. Furthermore, a thin layer of solid is accumulated at the tip and nanoparticles from secondary nucleation also appear at the growing front which later develop into fibrillar branches. The spherulite nanostructure is polycrystalline with the co-existence of ferrihydrite and Fe3O4 through-out the growth. A growth model is further established, which provides rational explanations on the linear growth at the early stage and the nonlinearity at the later stage of growth. [Figure not available: see fulltext.].

Studies to date on ferromagnet/d-wave superconductor heterostructures focus mainly on the effects at or near the interfaces while the response of bulk properties to heterostructuring is overlooked. Here we use resonant soft x-ray scattering spectroscopy to reveal a novel c-axis ferromagnetic coupling between the in-plane Cu spins in YBa2Cu3O7-x (YBCO) superconductor when it is grown on top of ferromagnetic La0.7Ca0.3MnO3 (LCMO) manganite layer. This coupling, present in both normal and superconducting states of YBCO, is sensitive to the interfacial termination such that it is only observed in bilayers with MnO2 but not with La0.7Ca0.3O interfacial termination. Such contrasting behaviors, we propose, are due to distinct energetic of CuO chain and CuO2 plane at the La0.7Ca0.3O and MnO2 terminated interfaces respectively, therefore influencing the transfer of spin-polarized electrons from manganite to cuprate differently. Our findings suggest that the superconducting/ferromagnetic bilayers with proper interfacial engineering can be good candidates for searching the theorized Fulde-Ferrel-Larkin-Ovchinnikov (FFLO) state in cuprates and studying the competing quantum orders in highly correlated electron systems.

Magnetoelectric materials have great potential to revolutionize electronic devices due to the coupling of their electric and magnetic properties. Thickness varying La0.7Sr0.3MnO3 (LSMO)/PbZr0.2Ti0.8O3 (PZT) heterostructures were built and measured in this article by valence sensitive x-ray absorption spectroscopy. The sizing effects of the heterostructures on the LSMO/PZT magnetoelectric interfaces were investigated through the behavior of Mn valence, a property associated with the LSMO magnetization. We found that Mn valence increases with both LSMO and PZT thickness. Piezoresponse force microscopy revealed a transition from monodomain to polydomain structure along the PZT thickness gradient. The ferroelectric surface charge may change with domain structure and its effects on Mn valence were simulated using a two-orbital double-exchange model. The screening of ferroelectric surface charge increases the electron charges in the interface region, and greatly changes the interfacial Mn valence, which likely plays a leading role in the interfacial magnetoelectric coupling. The LSMO thickness dependence was examined through the combination of two detection modes with drastically different attenuation depths. The different length scales of these techniques' sensitivity to the atomic valence were used to estimate the depth dependence Mn valence. A smaller interfacial Mn valence than the bulk was found by globally fitting the experimental results.

Studies to date on ferromagnet/d-wave superconductor heterostructures focus mainly on the effects at or near the interfaces while the response of bulk properties to heterostructuring is overlooked. Here we use resonant soft x-ray scattering spectroscopy to reveal a novel c-axis ferromagnetic coupling between the in-plane Cu spins in YBa2Cu3O7-x (YBCO) superconductor when it is grown on top of ferromagnetic La0.7Ca0.3MnO3 (LCMO) manganite layer. This coupling, present in both normal and superconducting states of YBCO, is sensitive to the interfacial termination such that it is only observed in bilayers with MnO2 but not with La0.7Ca0.3O interfacial termination. Such contrasting behaviors, we propose, are due to distinct energetic of CuO chain and CuO2 plane at the La0.7Ca0.3O and MnO2 terminated interfaces respectively, therefore influencing the transfer of spin-polarized electrons from manganite to cuprate differently. Our findings suggest that the superconducting/ferromagnetic bilayers with proper interfacial engineering can be good candidates for searching the theorized Fulde-Ferrel-Larkin-Ovchinnikov (FFLO) state in cuprates and studying the competing quantum orders in highly correlated electron systems.

The control of material interfaces at the atomic level has led to novel interfacial properties and functionalities. In particular, the study of polar discontinuities at interfaces between complex oxides lies at the frontier of modern condensed matter research. Here we employ a combination of experimental measurements and theoretical calculations to demonstrate the control of a bulk property, namely ferroelectric polarization, of a heteroepitaxial bilayer by precise atomic-scale interface engineering. More specifically, the control is achieved by exploiting the interfacial valence mismatch to influence the electrostatic potential step across the interface, which manifests itself as the biased-voltage in ferroelectric hysteresis loops and determines the ferroelectric state. A broad study of diverse systems comprising different ferroelectrics and conducting perovskite underlayers extends the generality of this phenomenon.

Domain walls in multiferroics can exhibit intriguing behaviors that are significantly different from the bulk of the material. We investigate strong magnetoresistance in domain walls of the model multiferroic BiFeO3 by probing ordered arrays of 109° domain walls with temperature- and magnetic-field-dependent transport. We observe temperature-dependent variations in the transport mechanism and magnetoresistances as large as 60%. These results suggest that by locally breaking the symmetry of a material, such as at domain walls and structural interfaces, one can induce emergent behavior with properties that deviate significantly from the bulk.

Ferroelectric polarization switching in epitaxial (110) BiFeO3 films is studied using piezoresponse force microscopy of a model in-plane capacitor structure. The electrode orientation is chosen such that only two active domain variants exist. Studies of the kinetics of domain evolution allows clear visualization of nucleation sites, as well as forward and lateral growth stages of domain formation. It is found that the location of the reverse-domain nucleation is correlated with the direction of switching in a way that the polarization in the domains nucleated at an electrode is always directed away from it. The role of interface charge injection and surface screening charge on switching mechanisms is explored, and the nucleation is shown to be controllable by the bias history of the sample. Finally, the manipulation of domain nucleation through domain structure engineering is illustrated. These studies pave the way for the engineering and design of the ferroelectric device structures through control of individual steps of the switching process. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

We report the formation of a novel ferromagnetic state in the antiferromagnet BiFeO3 at the interface with ferromagnet La(0.7)Sr(0.3)MnO3. Using x-ray magnetic circular dichroism at Mn and Fe L(2,3) edges, we discovered that the development of this ferromagnetic spin structure is strongly associated with the onset of a significant exchange bias. Our results demonstrate that the magnetic state is directly related to an electronic orbital reconstruction at the interface, which is supported by the linearly polarized x-ray absorption measurement at the oxygen K edge.

The growth and characterization of functional oxide thin films that are ferroelectric, magnetic, or both at the same time are reviewed. The evolution of synthesis techniques and how advances in in situ characterization have enabled significant acceleration in improvements to these materials are described. Methods for enhancing the properties of functional materials or creating entirely new functionality at interfaces are covered, including strain engineering and layering control at the atomic-layer level. Emerging applications of these functional oxides such as achieving electrical control of ferromagnetism and the future of these complex functional oxides is discussed. © 2010 Elsevier B.V. All rights reserved.

The switching kinetics in epitaxial (001)-, (110)-, and (111)-oriented BiFeO3 thin films were investigated as a function of applied field and time. It was found that the ferroelectric switching behavior obeys the Kolmogorov-Avrami-Ishibashi theory only in the high field range. The detailed behavior depends on the film orientation. A comparison with standard systems, such as epitaxial Pb (Zr0.2 Ti0.8) O3 films, reveals some similarities as well as some differences. For instance, the presence of 109° and 71° ferroelastic domain walls might be ruled out as the source of the decrease in switched polarization at low applied fields, in contrast to what is the case for a/c domain walls in tetragonal Pb (Zr 0.2 Ti0.8) O3. © 2010 American Institute of Physics.

We report a photovoltaic effect in ferroelectric BiFeO3 thin films. The all-oxide heterostructures with SrRuO3 bottom and tin doped indium oxide top electrodes are characterized by open-circuit voltages ∼0.8-0.9 V and external quantum efficiencies up to ∼10% when illuminated with the appropriate light. Efficiencies are at least an order of magnitude larger than the maximum efficiency under sunlight (AM 1.5) thus far reported for ferroelectric-based devices. The dependence of the measured open-circuit voltage on film thickness suggests contributions to the large open-circuit voltage from both the ferroelectric polarization and band offsets at the BiFeO3 /tin doped indium oxide interface. © 2009 American Institute of Physics.

The leakage current in epitaxial BiFeO3 capacitors with bottom SrRuO3 and top Pt electrodes, grown by pulsed laser deposition on SrTiO3 (100), SrTiO3 (110), and SrTiO3 (111) substrates, is investigated by current-voltage (I-V) measurements in the 100-300 K temperature range. It is found that the leakage current is interface-limited and strongly dependent on the orientation of the substrate. The potential barriers at the electrode interfaces are estimated to about 0.6, 0.77, and 0.93 eV for the (100), (110), and (111) orientations, respectively. © 2009 American Institute of Physics.