RESUMO
The secondary nature of polarization in improper ferroelectrics promotes functional properties beyond those of conventional ferroelectrics. In technologically relevant ultrathin films, however, the improper ferroelectric behavior remains largely unexplored. Here, we probe the emergence of the coupled improper polarization and primary distortive order parameter in thin films of hexagonal YMnO3. Combining state-of-the-art in situ characterization techniques separately addressing the improper ferroelectric state and its distortive driving force, we reveal a pronounced thickness dependence of the improper polarization, which we show to originate from the strong modification of the primary order at epitaxial interfaces. Nanoscale confinement effects on the primary order parameter reduce the temperature of the phase transition, which we exploit to visualize its order-disorder character with atomic resolution. Our results advance the understanding of the evolution of improper ferroelectricity within the confinement of ultrathin films, which is essential for their successful implementation in nanoscale applications.
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We identify a transient enhancement of the depolarizing field, leading to an unexpected quench of net polarization, during the growth of a prototypical metal-ferroelectric-metal epitaxial system made of BaTiO_{3} and SrRuO_{3}. Reduced conductivity and, hence, charge screening efficiency in the early growth stage of the SrRuO_{3} top electrode promotes a breakdown of ferroelectric BaTiO_{3} into domains. We demonstrate how a thermal annealing procedure can recover the single-domain state. By tracking the polarization state in situ, using optical second harmonic generation, we bring new understanding to interface-related electrostatic effects in ferroelectric capacitors.
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III-V compound semiconductors are indispensable materials for today's high-end electronic and optoelectronic devices and are being explored for next-generation transistor logic and quantum technologies. III-V surfaces and interfaces play the leading role in determining device performance, and therefore, methods to control their electronic properties have been developed. Typically, surface passivation studies demonstrated how to limit the density of surface states. Strain has been widely used to improve the electronic transport properties and optoelectronic properties of III-Vs, but the potential of this technology to modify the surface properties still remains to be explored. Here we show that uniaxial stress induces a shift in the energy of the surface states of III-V nanowires, modifying their electronic properties. We demonstrate this phenomenon by modulating the conductivity of InAs nanowires over 4 orders of magnitude with axial strain ranging between -2.5% in compression and 2.1% in tension. The band bending at the surface of the nanostructure is modified from accumulation to depletion reversibly and reproducibly. We provide evidence of this physical effect using a combination of electrical transport measurement, Raman spectroscopy, band-structure modeling, and technology computer aided design (TCAD) simulations. With this methodology, the deformation potentials for the surface states are quantified. These results reveal that strain technology can be used to shift surface states away from energy ranges in which device performance is negatively affected and represent a novel route to engineer the electronic properties of III-V devices.
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A hybrid growth process was developed in order to epitaxially integrate nano-layers of the multi-functional perovskite BaTiO3 onto Si(001) substrates. In particular, we combined molecular beam epitaxy (MBE) with radio-frequency sputtering. Due to its strong influence on the functional properties, the crystalline structure of the layers was thoroughly investigated throughout our study. MBE-grown seed layers are tetragonal and c-axis oriented up to a thickness of 20 nm. A transition into a-axis films is visible for thicker layers. When the seed layer thickness exceeds 6 nm, subsequently sputtered BaTiO3 films are epitaxial. However, their crystalline structure, their orientation with respect to the substrate, and their morphology are strongly dependent on the deposition and post-deposition thermal budget. Consistently with their crystalline symmetry, thin MBE BaTiO3 films are piezo- and ferroelectric with a spontaneous polarization perpendicular to the surface. Also for thick films, the functional response, as determined via piezo-force microscopy, is in good agreement with the structural properties.
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The performance of ferroelectric devices, for example, the ferroelectric field effect transistor, is reduced by the presence of crystal defects such as edge dislocations. For example, it is well-known that edge dislocations play a crucial role in the formation of ferroelectric dead-layers at interfaces and hence finite size effects in ferroelectric thin films. The detailed lattice structure including the relevant electromechanical coupling mechanisms in close vicinity of the edge dislocations is, however, not well-understood, which hampers device optimization. Here, we investigate edge dislocations in ferroelectric BiFeO3 by means of spherical aberration-corrected scanning transmission electron microscopy, a dedicated model-based structure analysis, and phase field simulations. Unit-cell-wise resolved strain and polarization profiles around edge dislocation reveal a wealth of material states including polymorph nanodomains and multiple domain walls characteristically pinned to the dislocation. We locally determine the piezoelectric tensor and identify piezoelectric coupling as the driving force for the observed phenomena, explaining, for example, the orientation of the domain wall with respect to the edge dislocation. Furthermore, an atomic model for the dislocation core is derived.
Assuntos
Berílio/química , Eletricidade , Compostos Férricos/química , Nanoestruturas/química , Microscopia Eletrônica de Transmissão e Varredura , Tamanho da Partícula , Transistores EletrônicosRESUMO
Domain walls (DWs) substantially influence a large number of applications involving ferroelectric materials due to their limited mobility when shifted during polarization switching. The discovery of greatly enhanced conduction at BiFeO(3) DWs has highlighted yet another role of DWs as a local material state with unique properties. However, the lack of precise information on the local atomic structure is still hampering microscopical understanding of DW properties. Here, we examine the atomic structure of BiFeO(3) 109° DWs with pm precision by a combination of high-angle annular dark-field scanning transmission electron microscopy and a dedicated structural analysis. By measuring simultaneously local polarization and strain, we provide direct experimental proof for the straight DW structure predicted by ab initio calculations as well as the recently proposed theory of diffuse DWs, thus resolving a long-standing discrepancy between experimentally measured and theoretically predicted DW mobilities.
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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.
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We determine the atomic structure of the pseudotetragonal T phase and the pseudorhombohedral R phase in highly strained multiferroic BiFeO(3) thin films by using a combination of atomic-resolution scanning transmission electron microscopy and electron energy-loss spectroscopy. The coordination of the Fe atoms and their displacement relative to the O and Bi positions are assessed by direct imaging. These observations allow us to interpret the electronic structure data derived from electron energy-loss spectroscopy and provide evidence for the giant spontaneous polarization in strained BiFeO(3) thin films.
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We report direct experimental evidence for a room-temperature, â¼130 µC/cm(2) ferroelectric polarization from the tetragonal-like BiFeO(3) phase. The physical origin of this remarkable enhancement of ferroelectric polarization has been investigated by a combination of x-ray absorption spectroscopy, scanning transmission electron microscopy, and first principles calculations. A large strain-induced Fe-ion displacement relative to the oxygen octahedra, combined with the contribution of Bi 6s lone pair electrons, is the mechanism driving the large ferroelectric polarization in this tetragonal-like phase.
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The size distribution of particles, which is essential for many properties of nanomaterials, is equally important for the mechanical behaviour of the class of alloys whose strength derives from a dispersion of nanoscale precipitates. However, particle size distributions formed by solid-state precipitation are generally not well controlled. Here we demonstrate, through the example of core-shell precipitates in Al-Sc-Li alloys, an approach to forming highly monodisperse particle size distributions by simple solid-state reactions. The approach involves the use of a two-step heat treatment, whereby the core formed at high temperature provides a template for growth of the shell at lower temperature. If the core is allowed to grow to a sufficient size, the shell develops in a 'size focusing' regime, where smaller particles grow faster than larger ones. These results suggest strategies for manipulating precipitate size distributions in similar systems through simple variations in thermal treatments.
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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.
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Electric-field control of magnetization has many potential applications in magnetic memory storage, sensors and spintronics. One approach to obtain this control is through multiferroic materials. Instead of using direct coupling between ferroelectric and ferromagnetic order parameters in a single-phase multiferroic material, which only shows a weak magnetoelectric effect, a unique method using indirect coupling through an intermediate antiferromagnetic order parameter can be used. In this article, we demonstrate electrical control of exchange bias using a field-effect device employing multiferroic (ferroelectric/antiferromagnetic) BiFeO(3) as the dielectric and ferromagnetic La(0.7)Sr(0.3)MnO(3) as the conducting channel; we can reversibly switch between two distinct exchange-bias states by switching the ferroelectric polarization of BiFeO(3). This is an important step towards controlling magnetization with electric fields, which may enable a new class of electrically controllable spintronic devices and provide a new basis for producing electrically controllable spin-polarized currents.
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In conventional solid-state photovoltaics, electron-hole pairs are created by light absorption in a semiconductor and separated by the electric field spaning a micrometre-thick depletion region. The maximum voltage these devices can produce is equal to the semiconductor electronic bandgap. Here, we report the discovery of a fundamentally different mechanism for photovoltaic charge separation, which operates over a distance of 1-2 nm and produces voltages that are significantly higher than the bandgap. The separation happens at previously unobserved nanoscale steps of the electrostatic potential that naturally occur at ferroelectric domain walls in the complex oxide BiFeO(3). Electric-field control over domain structure allows the photovoltaic effect to be reversed in polarity or turned off. This new degree of control, and the high voltages produced, may find application in optoelectronic devices.
Assuntos
Eletroquímica/instrumentação , Nanotecnologia/instrumentação , Fotoquímica/instrumentação , Eletricidade , Eletricidade EstáticaRESUMO
We present an unreported magnetic configuration in epitaxial La(1-x) Sr(x) MnO3 (x â¼ 0.3) (LSMO) films grown on strontium titanate (STO). X-ray magnetic circular dichroism indicates that the remanent magnetic state of thick LSMO films is opposite to the direction of the applied magnetic field. Spectroscopic and scattering measurements reveal that the average Mn valence varies from mixed Mn(3+)/Mn(4+) to an enriched Mn3+ region near the STO interface, resulting in a compressive lattice along the a, b axis and a possible electronic reconstruction in the Mn e(g) orbital (d(3)z(2)-r(2). This reconstruction may provide a mechanism for coupling the Mn3+ moments antiferromagnetically along the surface normal direction, and in turn may lead to the observed reversed magnetic configuration.
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Piezoelectric materials, which convert mechanical to electrical energy and vice versa, are typically characterized by the intimate coexistence of two phases across a morphotropic phase boundary. Electrically switching one to the other yields large electromechanical coupling coefficients. Driven by global environmental concerns, there is currently a strong push to discover practical lead-free piezoelectrics for device engineering. Using a combination of epitaxial growth techniques in conjunction with theoretical approaches, we show the formation of a morphotropic phase boundary through epitaxial constraint in lead-free piezoelectric bismuth ferrite (BiFeO3) films. Electric field-dependent studies show that a tetragonal-like phase can be reversibly converted into a rhombohedral-like phase, accompanied by measurable displacements of the surface, making this new lead-free system of interest for probe-based data storage and actuator applications.
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Using ultrafast spectroscopy, we investigated electron-lattice coupling and acoustic vibrations in self-assembled silver nanocolumns embedded in an amorphous Al2O3 matrix. The measured electron-lattice energy exchange time is smaller in the nanocolumns than in bulk silver, with a value very close to that of isolated nanospheres with comparable surface to volume ratio. Two vibration modes were detected and ascribed to the breathing and extensional mode of the nanocolumns, in agreement with numerical simulations.