Alexander Melville

A Strain-Driven Morphotropic Phase Boundary in BiFeO3

Biffed into Shape BiFeO3 is known to have a very large ferroelectric polarization. Although the bulk ground state is rhombohedral (with the electrical polarization along the [111] direction), in thin films and under epitaxial strain, the material can be tetragonally distorted (polarization along [001]). Zeches et al. (p. 977) show that under compressive strain, these films are monoclinic, a phase that is highly stable because it comprises the same symmetry as the monoclinic phase which has been reported at the so-called morphotropic phase boundaries in technologically important ferroelectrics. This work offers the possibility of obtaining large piezoelectric responses in lead-free systems. Growth of epitaxial films of BiFeO3 on various substrates may provide a route toward making lead-free ferroelectric devices. 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.

Photovoltaic effects in BiFeO3

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.

Domain Dynamics During Ferroelectric Switching

The role of defects and interfaces on switching in ferroelectric materials is observed with high-resolution microscopy. The utility of ferroelectric materials stems from the ability to nucleate and move polarized domains using an electric field. To understand the mechanisms of polarization switching, structural characterization at the nanoscale is required. We used aberration-corrected transmission electron microscopy to follow the kinetics and dynamics of ferroelectric switching at millisecond temporal and subangstrom spatial resolution in an epitaxial bilayer of an antiferromagnetic ferroelectric (BiFeO3) on a ferromagnetic electrode (La0.7Sr0.3MnO3). We observed localized nucleation events at the electrode interface, domain wall pinning on point defects, and the formation of ferroelectric domains localized to the ferroelectric and ferromagnetic interface. These results show how defects and interfaces impede full ferroelectric switching of a thin film.

Optical properties of quasi-tetragonal BiFeO3 thin films

Optical transmission spectroscopy and spectroscopic ellipsometry were used to extract the optical properties of an epitaxially grown quasi-tetragonal BiFeO3 thin film in the near infrared to near ultraviolet range. The absorption spectrum is overall blue shifted compared with that of rhombohedral BiFeO3, with an absorption onset near 2.25 eV, a direct 3.1 eV band gap, and charge transfer excitations that are ∼0.4 eV higher than those of the rhombohedral counterpart. We interpret these results in terms of structural strain and local symmetry breaking.

Atomic Scale Structure Changes Induced by Charged Domain Walls in Ferroelectric Materials

Charged domain walls (CDWs) are of significant scientific and technological importance as they have been shown to play a critical role in controlling the switching mechanism and electric, photoelectric, and piezoelectric properties of ferroelectric materials. The atomic scale structure and properties of CDWs, which are critical for understanding the emergent properties, have, however, been rarely explored. In this work, using a spherical-aberration-corrected transmission electron microscope with subangstrom resolution, we have found that the polarization bound charge of the CDW in rhombohedral-like BiFeO3 thin films not only induces the formation of a tetragonal-like crystal structure at the CDW but also stabilizes unexpected nanosized domains with new polarization states and unconventional domain walls. These findings provide new insights on the effects of bound charge on ferroelectric domain structures and are critical for understanding the electrical switching in ferroelectric thin films as well as in memory devices.

Probing mixed tetragonal/rhombohedral-like monoclinic phases in strained bismuth ferrite films by optical second harmonic generation

Epitaxial strain can induce the formation of morphotropic phase boundary in lead free ferroelectrics like bismuth ferrite, thereby enabling the coexistence of tetragonal and rhombohedral phases in the same film. The relative ratio of these phases is governed by the film thickness and theoretical studies suggest that there exists a monoclinic distortion of both the tetragonal as well as the rhombohedral unit cells due to imposed epitaxial strain. In this work we show that optical second harmonic generation can distinguish the tetragonal-like phase from the rhombohedral-like phase and enable detection of monoclinic distortion in only a pure tetragonal-like phase.

Giant Resistive Switching via Control of Ferroelectric Charged Domain Walls

Controlled switching of resistivity in ferroelectric thin films is demonstrated by writing and erasing stable, nanoscale, strongly charged domain walls using an in situ transmission electron microscopy technique. The resistance can be read nondestructively and presents the largest off/on ratio (≈10(5) ) ever reported in room-temperature ferroelectric devices, opening new avenues for engineering ferroelectric thin-film devices.

Ultrafast optical tuning of ferromagnetism via the carrier density

1Department of Materials, ETH Zurich, Wolfgang-Pauli-Stra sse 10, 8093 Zurich, Switzerland 2Physikalisches Institut, Universität Bonn, Nussallee 12 , 53115 Bonn, Germany 3Institut für Physik, Universität Augsburg, Augsburg 861 35, Germany 4Department of Materials Science and Engineering, Cornell U niversity, Ithaca, New York 14853-1501, USA 5Kavli Institute at Cornell for Nanoscale Science, Ithaca, N ew York 14853-1501, USA and 6Max Planck Institute for Solid State Research, Heisenbergs traße 1, 70569 Stuttgart, Germany (Dated: May 11, 2014)Interest in manipulating the magnetic order by ultrashort laser pulses has thrived since it was observed that such pulses can be used to alter the magnetization on a sub-picosecond timescale. Usually this involves demagnetization by laser heating or, in rare cases, a transient increase of magnetization. Here we demonstrate a mechanism that allows the magnetic order of a material to be enhanced or attenuated at will. This is possible in systems simultaneously possessing a low, tunable density of conduction band carriers and a high density of magnetic moments. In such systems, the thermalization time can be set such that adiabatic processes dominate the photoinduced change of the magnetic order--the three-temperature model for interacting thermalized electron, spin and lattice reservoirs is bypassed. In ferromagnetic Eu(1-x)Gd(x)O, we thereby demonstrate the strengthening as well as the weakening of the magnetic order by ~10% and within ≤3 ps by optically controlling the magnetic exchange interaction.

Lutetium-doped EuO films grown by molecular-beam epitaxy

The effect of lutetium doping on the structural, electronic, and magnetic properties of epitaxial EuO thin films grown by reactive molecular-beam epitaxy is experimentally investigated. The behavior of Lu-doped EuO is contrasted with doping by lanthanum and gadolinium. All three dopants are found to behave similarly despite differences in electronic configuration and ionic size. Andreev reflection measurements on Lu-doped EuO reveal a spin-polarization of 96% in the conduction band, despite non-magnetic carriers introduced by 5% lutetium doping.

High-quality EuO thin films the easy way via topotactic transformation

Epitaxy is widely employed to create highly oriented crystalline films. A less appreciated, but nonetheless powerful means of creating such films is via topotactic transformation, in which a chemical reaction transforms a single crystal of one phase into a single crystal of a different phase, which inherits its orientation from the original crystal. Topotactic reactions may be applied to epitactic films to substitute, add or remove ions to yield epitactic films of different phases. Here we exploit a topotactic reduction reaction to provide a non-ultra-high vacuum (UHV) means of growing highly oriented single crystalline thin films of the easily over-oxidized half-metallic semiconductor europium monoxide (EuO) with a perfection rivalling that of the best films of the same material grown by molecular-beam epitaxy or UHV pulsed-laser deposition. As the technique only requires high-vacuum deposition equipment, it has the potential to drastically improve the accessibility of high-quality single crystalline films of EuO as well as other difficult-to-synthesize compounds.