Surface polarization profile of ferroelectric thin films probed by X-ray standing waves and photoelectron spectroscopy.

Understanding the mechanisms underlying a stable polarization at the surface of ferroelectric thin films is of particular importance both from a fundamental point of view and to achieve control of the surface polarization itself. In this study, we demonstrate that the X-ray standing wave technique allows the surface polarization profile of a ferroelectric thin film, as opposed to the average film polarity, to be probed directly. The X-ray standing wave technique provides the average Ti and Ba atomic positions, along the out-of-plane direction, near the surface of three differently strained [Formula: see text] thin films.

Flexoelectric Enhancement of Strain Gradient Elasticity Across a Ferroelectric-to-Paraelectric Phase Transition.

We study the temperature dependent elastic properties of BaSrTiO freestanding membranes across the ferroelectric-to-paraelectric phase transition using an atomic force microscope. The bending rigidity of thin membranes can be stiffer compared to stretching due to strain gradient elasticity (SGE). We measure the Young's modulus of freestanding BaSrTiO drumheads in bending and stretching dominated deformation regimes on a variable temperature platform, finding a peak in the difference between the two Young's moduli obtained at the phase transition.

Photostrictive Actuators Based on Freestanding Ferroelectric Membranes.

Complex oxides offer a wide range of functional properties, and recent advances in the fabrication of freestanding membranes of these oxides are adding new mechanical degrees of freedom to this already rich functional ecosystem. Here, photoactuation is demonstrated in freestanding thin film resonators of ferroelectric Barium Titanate (BaTiO) and paraelectric Strontium Titanate (SrTiO). The free-standing films, transferred onto perforated supports, act as nano-drums, oscillating at their natural resonance frequency when illuminated by a frequency-modulated laser.

Highly reversible extrinsic electrocaloric effects over a wide temperature range in epitaxially strained SrTiO films.

Electrocaloric effects have been experimentally studied in ferroelectrics and incipient ferroelectrics, but not incipient ferroelectrics driven ferroelectric using strain. Here we use optimally oriented interdigitated surface electrodes to investigate extrinsic electrocaloric effects in low-loss epitaxial SrTiO films near the broad second-order 243 K ferroelectric phase transition created by biaxial in-plane coherent tensile strain from DyScO substrates. Our extrinsic electrocaloric effects are an order of magnitude larger than the corresponding effects in bulk SrTiO over a wide range of temperatures including room temperature, and unlike electrocaloric effects associated with first-order transitions they are highly reversible in unipolar applied fields.

Freestanding complex-oxide membranes.

Complex oxides show a vast range of functional responses, unparalleled within the inorganic solids realm, making them promising materials for applications as varied as next-generation field-effect transistors, spintronic devices, electro-optic modulators, pyroelectric detectors, or oxygen reduction catalysts. Their stability in ambient conditions, chemical versatility, and large susceptibility to minute structural and electronic modifications make them ideal subjects of study to discover emergent phenomena and to generate novel functionalities for next-generation devices. Recent advances in the synthesis of single-crystal, freestanding complex oxide membranes provide an unprecedented opportunity to study these materials in a nearly-ideal system (e.

Enabling ultra-low-voltage switching in BaTiO.

Single crystals of BaTiO exhibit small switching fields and energies, but thin-film performance is considerably worse, thus precluding their use in next-generation devices. Here, we demonstrate high-quality BaTiO thin films with nearly bulk-like properties. Thickness scaling provides access to the coercive voltages (<100 mV) and fields (<10 kV cm) required for future applications and results in a switching energy of <2 J cm (corresponding to <2 aJ per bit in a 10 × 10 × 10 nm device).

The role of lattice dynamics in ferroelectric switching.

Reducing the switching energy of ferroelectric thin films remains an important goal in the pursuit of ultralow-power ferroelectric memory and logic devices. Here, we elucidate the fundamental role of lattice dynamics in ferroelectric switching by studying both freestanding bismuth ferrite (BiFeO) membranes and films clamped to a substrate. We observe a distinct evolution of the ferroelectric domain pattern, from striped, 71° ferroelastic domains (spacing of ~100 nm) in clamped BiFeO films, to large (10's of micrometers) 180° domains in freestanding films.

Correlating Surface Crystal Orientation and Gas Kinetics in Perovskite Oxide Electrodes.

Solid-gas interactions at electrode surfaces determine the efficiency of solid-oxide fuel cells and electrolyzers. Here, the correlation between surface-gas kinetics and the crystal orientation of perovskite electrodes is studied in the model system La Sr Co Fe O . The gas-exchange kinetics are characterized by synthesizing epitaxial half-cell geometries where three single-variant surfaces are produced [i.

Strain relaxation dynamics of multiferroic orthorhombic manganites.

Resonant ultrasound spectroscopy has been used to characterise strain coupling and relaxation behavior associated with magnetic/magnetoelectric phase transitions in GdMnO, TbMnOand TbMnFeOthrough their influence on elastic/anelastic properties. Acoustic attenuation ahead of the paramagnetic to colinear-sinusoidal incommensurate antiferromagnetic transition at ∼41 K correlates with anomalies in dielectric properties and is interpreted in terms of Debye-like freezing processes. A loss peak at ∼150 K is related to a steep increase in electrical conductivity with a polaron mechanism.

Beyond Substrates: Strain Engineering of Ferroelectric Membranes.

Strain engineering in perovskite oxides provides for dramatic control over material structure, phase, and properties, but is restricted by the discrete strain states produced by available high-quality substrates. Here, using the ferroelectric BaTiO , production of precisely strain-engineered, substrate-released nanoscale membranes is demonstrated via an epitaxial lift-off process that allows the high crystalline quality of films grown on substrates to be replicated. In turn, fine structural tuning is achieved using interlayer stress in symmetric trilayer oxide-metal/ferroelectric/oxide-metal structures fabricated from the released membranes.

Large magnetoelectric coupling in multiferroic oxide heterostructures assembled via epitaxial lift-off.

Epitaxial films may be released from growth substrates and transferred to structurally and chemically incompatible substrates, but epitaxial films of transition metal perovskite oxides have not been transferred to electroactive substrates for voltage control of their myriad functional properties. Here we demonstrate good strain transmission at the incoherent interface between a strain-released film of epitaxially grown ferromagnetic LaSrMnO and an electroactive substrate of ferroelectric 0.68Pb(MgNb)O-0.

Voltage-driven annihilation and creation of magnetic vortices in Ni discs.

Using photoemission electron microscopy (PEEM) to image ferromagnetism in polycrystalline Ni disks, and ferroelectricity in their single-crystal BaTiO substrates, we find that voltage-driven 90° ferroelectric domain switching serves to reversibly annihilate each magnetic vortex via uniaxial compressive strain, and that the orientation of the resulting bi-domain reveals the chirality of the annihilated vortex. Micromagnetic simulations reveal that only 60% of this strain is required for annihilation. Voltage control of magnetic vortices is novel, and should be energetically favourable with respect to the use of a magnetic field or an electrical current.

Shear-strain-mediated magnetoelectric effects revealed by imaging.

Large changes in the magnetization of ferromagnetic films can be electrically driven by non-180° ferroelectric domain switching in underlying substrates, but the shear components of the strains that mediate these magnetoelectric effects have not been considered so far. Here we reveal the presence of these shear strains in a polycrystalline film of Ni on a 0.68Pb(MgNb)O-0.

Glasslike Dynamics of Polar Domain Walls in Cryogenic SrTiO_{3}.

Polar and highly mobile domain walls in SrTiO_{3} move under electric and elastic fields. Two vastly different timescales dominate their dynamical behavior. The previously observed fast changes lead to anomalies near 40 K where the elastic moduli soften and the polarity of the walls becomes strong.

Evidence of a minority monoclinic LaNiO phase in lanthanum nickelate thin films.

LaNiO (LNO) thin films of 14 nm and 35 nm thicknesses grown epitaxially on LaAlO (LAO) and (LaAlO)(SrTaAlO) (LSAT) substrates are studied using High Resolution Transmission Electron Microscopy (HRTEM) and High Angle Annular Dark Field (HAADF) imaging. The strain state of the films is studied using Geometric Phase Analysis (GPA). Results show the successful in-plane adaptation of the films to the substrates, both in the compressive (LAO) and tensile (LSAT) cases.

Giant Optical Polarization Rotation Induced by Spin-Orbit Coupling in Polarons.

We have uncovered a giant gyrotropic magneto-optical response for doped ferromagnetic manganite La_{2/3}Ca_{1/3}MnO_{3} around the near room-temperature paramagnetic-to-ferromagnetic transition. At odds with current wisdom, where this response is usually assumed to be fundamentally fixed by the electronic band structure, we point to the presence of small polarons as the driving force for this unexpected phenomenon. We explain the observed properties by the intricate interplay of mobility, Jahn-Teller effect, and spin-orbit coupling of small polarons.

Two-dimensional electron gases at LaAlO3/SrTiO3 interfaces: orbital symmetry and hierarchy engineered by crystal orientation.

Recent findings show the emergence of two-dimensional electron gases (2DEGs) at LaAlO(3)/SrTiO(3) interfaces along different orientations; yet details on band reconstructions have remained so far unknown. Via x-ray linear dichroism spectroscopy, we demonstrate that crystal symmetry imposes distinctive 2DEG orbital hierarchies on (001)-and (110)-oriented quantum wells, allowing selective occupancy of states of different symmetry. Such orientational tuning expands the possibilities for electronic engineering of 2DEGs and opens up enticing opportunities to understand the link between orbital symmetry and complex correlated states at LaAlO(3)/SrTiO(3) quantum wells.

Surface symmetry-breaking and strain effects on orbital occupancy in transition metal perovskite epitaxial films.

The electron occupancy of 3d-orbitals determines the properties of transition metal oxides. This can be achieved, for example, through thin-film heterostructure engineering of ABO(3) oxides, enabling emerging properties at interfaces. Interestingly, epitaxial strain may break the degeneracy of 3d-e(g) and t(2g) orbitals, thus favoring a particular orbital filling with consequences for functional properties.