Anisotropic epitaxial stabilization of a low-symmetry ferroelectric with enhanced electromechanical response.

Piezoelectrics interconvert mechanical energy and electric charge and are widely used in actuators and sensors. The best performing materials are ferroelectrics at a morphotropic phase boundary, where several phases coexist. Switching between these phases by electric field produces a large electromechanical response. In ferroelectric BiFeO3, strain can create a morphotropic-phase-boundary-like phase mixture and thus generate large electric-field-dependent strains. However, this enhanced response occurs at localized, randomly positioned regions of the film. Here, we use epitaxial strain and orientation engineering in tandem-anisotropic epitaxy-to craft a low-symmetry phase of BiFeO3 that acts as a structural bridge between the rhombohedral-like and tetragonal-like polymorphs. Interferometric displacement sensor measurements reveal that this phase has an enhanced piezoelectric coefficient of ×2.4 compared with typical rhombohedral-like BiFeO3. Band-excitation frequency response measurements and first-principles calculations provide evidence that this phase undergoes a transition to the tetragonal-like polymorph under electric field, generating an enhanced piezoelectric response throughout the film and associated field-induced reversible strains. These results offer a route to engineer thin-film piezoelectrics with improved functionalities, with broader perspectives for other functional oxides.

The Experimentalist's Guide to the Cycloid, or Noncollinear Antiferromagnetism in Epitaxial BiFeO3.

Bismuth ferrite (BiFeO3 ) is one of the most widely studied multiferroics. The coexistence of ferroelectricity and antiferromagnetism in this compound has driven an intense search for electric-field control of the magnetic order. Such efforts require a complete understanding of the various exchange interactions that underpin the magnetic behavior. An important characteristic of BiFeO3 is its noncollinear magnetic order; namely, a long-period incommensurate spin cycloid. Here, the progress in understanding this fascinating aspect of BiFeO3 is reviewed, with a focus on epitaxial films. The advances made in developing the theory used to capture the complexities of the cycloid are first chronicled, followed by a description of the various experimental techniques employed to probe the magnetic order. To help the reader fully grasp the nuances associated with thin films, a detailed description of the spin cycloid in the bulk is provided. The effects of various perturbations on the cycloid are then described: magnetic and electric fields, doping, epitaxial strain, finite size effects, and temperature. To conclude, an outlook on possible device applications exploiting noncollinear magnetism in BiFeO3 films is presented. It is hoped that this work will act as a comprehensive experimentalist's guide to the spin cycloid in BiFeO3 thin films.

Superior polarization retention through engineered domain wall pinning.

Ferroelectric materials possess a spontaneous polarization that is switchable by an electric field. Robust retention of switched polarization is critical for non-volatile nanoelectronic devices based on ferroelectrics, however, these materials often suffer from polarization relaxation, typically within days to a few weeks. Here we exploit designer-defect-engineered epitaxial BiFeO3 films to demonstrate polarization retention with virtually no degradation in switched nanoscale domains for periods longer than 1 year. This represents a more than 2000% improvement over the best values hitherto reported. Scanning probe microscopy-based dynamic switching measurements reveal a significantly increased activation field for domain wall movement. Atomic resolution scanning transmission electron microscopy indicates that nanoscale defect pockets pervade the entire film thickness. These defects act as highly efficient domain wall pinning centres, resulting in anomalous retention. Our findings demonstrate that defects can be exploited in a positive manner to solve reliability issues in ferroelectric films used in functional devices.

Deterministic optical control of room temperature multiferroicity in BiFeO3 thin films.

Controlling ferroic orders (ferroelectricity, ferromagnetism and ferroelasticity) by optical methods is a significant challenge due to the large mismatch in energy scales between the order parameter coupling strengths and the incident photons. Here, we demonstrate an approach to manipulate multiple ferroic orders in an epitaxial mixed-phase BiFeO3 thin film at ambient temperature via laser illumination. Phase-field simulations indicate that a light-driven flexoelectric effect allows the targeted formation of ordered domains. We also achieved precise sequential laser writing and erasure of different domain patterns, which demonstrates a deterministic optical control of multiferroicity at room temperature. As ferroic orders directly influence susceptibility and conductivity in complex materials, our results not only shed light on the optical control of multiple functionalities, but also suggest possible developments for optoelectronics and related applications.

Nonvolatile ferroelectric domain wall memory.

Ferroelectric domain walls are atomically sharp topological defects that separate regions of uniform polarization. The discovery of electrical conductivity in specific types of walls gave rise to "domain wall nanoelectronics," a technology in which the wall (rather than the domain) stores information. This paradigm shift critically hinges on precise nanoengineering of reconfigurable domain walls. Using specially designed nanofabricated electrodes and scanning probe techniques, we demonstrate a prototype nonvolatile ferroelectric domain wall memory, scalable to below 100 nm, whose binary state is defined by the existence or absence of conductive walls. The device can be read out nondestructively at moderate voltages (<3 V), exhibits relatively high OFF-ON ratios (~103) with excellent endurance and retention characteristics, and has multilevel data storage capacity. Our work thus constitutes an important step toward integrated nanoscale ferroelectric domain wall memory devices.

Dual strain mechanisms in a lead-free morphotropic phase boundary ferroelectric.

Electromechanical properties such as d33 and strain are significantly enhanced at morphotropic phase boundaries (MPBs) between two or more different crystal structures. Many actuators, sensors and MEMS devices are therefore systems with MPBs, usually between polar phases in lead (Pb)-based ferroelectric ceramics. In the search for Pb-free alternatives, systems with MPBs between polar and non-polar phases have recently been theorized as having great promise. While such an MPB was identified in rare-earth (RE) modified bismuth ferrite (BFO) thin films, synthesis challenges have prevented its realization in ceramics. Overcoming these, we demonstrate a comparable electromechanical response to Pb-based materials at the polar-to-non-polar MPB in Sm modified BFO. This arises from 'dual' strain mechanisms: ferroelectric/ferroelastic switching and a previously unreported electric-field induced transition of an anti-polar intermediate phase. We show that intermediate phases play an important role in the macroscopic strain response, and may have potential to enhance electromechanical properties at polar-to-non-polar MPBs.

Self-Assembled Epitaxial Core-Shell Nanocrystals with Tunable Magnetic Anisotropy.

Epitaxial core-shell CoO-CoFe2 O4 nanocrystals are fabricated by using pulsed laser deposition with the aid of melted material (Bi2 O3 ) addition and suitable lattice mismatch provided by substrates (SrTiO3 ). Well aligned orientations among nanocrystals and reversible core-shell sequence reveal tunable magnetic anisotropy. The interfacial coupling between core and shell further engineers the nanocrystal functionality.

Epitaxial Bi5Ti3FeO15-CoFe2O4 pillar-matrix multiferroic nanostructures.

Epitaxial self-assembled ferro(i)magnetic spinel (CoFe2O4 (CFO)) and ferroelectric bismuth layered perovskite (Bi5Ti3FeO15 (BTFO)) pillar-matrix nanostructures are demonstrated on (001) single-crystalline strontium titanate substrates. The CFO remains embedded in the BTFO matrix as vertical pillars (∼50 nm in diameter) up to a volume fraction of 50%. Piezoresponse force microscopy experiments evidence a weak out-of-plane and a strong in-plane ferroelectricity in the BTFO phase, despite previously reported paraelectricity along the c-axis in a pure BTFO film. Phenomenological Landau-Ginzburg-Devonshire-based thermodynamic computations show that the radial stress induced by the CFO nanopillars can influence these ferroelectric phases, thus signifying the importance of the nanopillars. The CFO pillars demonstrate robust ferromagnetic hysteresis loops with little degradation in the saturation magnetization (ca. 4 µB/f.u.). Thus BTFO-CFO nanocomposites show significant promise as a lead-free magnetoelectric materials system.

Doping BiFeO3: approaches and enhanced functionality.

BiFeO(3) is one of the most studied multiferroic materials. Both its magnetic and ferroelectric properties can be influenced by doping. A large body of work on the doped material has been presented in the past couple of years. In this paper we provide a perspective on general doping concepts and their impact on the material's functionality.

Nanoscale control of phase variants in strain-engineered BiFeO3.

Development of magnetoelectric, electromechanical, and photovoltaic devices based on mixed-phase rhombohedral-tetragonal (R-T) BiFeO(3) (BFO) systems is possible only if the control of the engineered R phase variants is realized. Accordingly, we explore the mechanism of a bias induced phase transformation in this system. Single point spectroscopy demonstrates that the T → R transition is activated at lower voltages compared to T → -T polarization switching. With phase field modeling, the transition is shown to be electrically driven. We further demonstrate that symmetry of formed R-phase rosettes can be broken by a proximal probe motion, allowing controlled creation of R variants with defined orientation. This approach opens a pathway to designing next-generation magnetoelectronic and data storage devices in the nanoscale.

Exploring topological defects in epitaxial BiFeO3 thin films.

Using a combination of piezoresponse force microscopy (PFM) and phase-field modeling, we demonstrate ubiquitous formation of center-type and possible ferroelectric closure domain arrangements during polarization switching near the ferroelastic domain walls in (100) oriented rhombohedral BiFeO(3). The formation of these topological defects is determined from the vertical and lateral PFM data and confirmed from the reversible changes in surface topography. These observations provide insight into the mechanisms of tip-induced ferroelastic domain control and suggest that formation of topological defect states under the action of local defect- and tip-induced fields is much more common than previously believed.

Synthesis of epitaxial metal oxide nanocrystals via a phase separation approach.

Perovskite phase instability of BiMnO3 has been exploited to synthesize epitaxial metal oxide magnetic nanocrystals. Thin film processing conditions are tuned to promote the breakdown of the perovskite precursor into Bi2O3 matrix and magnetic manganese oxide islands. Subsequent cooling in vacuum ensures complete volatization of the Bi2O3, thus leaving behind an array of self-assembled magnetic Mn3O4 nanostructures. Both shape and size can be systematically controlled by the ambient oxygen environments and deposition time. As such, this approach can be extended to any other Bi-based complex ternary oxide system as it primarily hinges on the breakdown of parent Bi-based precursor and subsequent Bi2O3 volatization.

Chemistry of the Fe2O3/BiFeO3 Interface in BiFeO3 Thin Film Heterostructures.

We investigate the interfacial chemistry of secondary Fe2O3 phases formed in a BiFeO3 (BFO) layer in BFO/ La0.67Sr0.33MnO3 (LSMO)/SrTiO3 (STO) heterostructures. A combination of high-resolution spherical aberration corrected scanning TEM and spectroscopy results, reveals that specific chemical and crystallographic similarities between Fe2O3 and BFO, enable the BFO layer to form a facile host for Fe2O3.

Unit-cell scale mapping of ferroelectricity and tetragonality in epitaxial ultrathin ferroelectric films.

Typically, polarization and strain in ferroelectric materials are coupled, leading to the generally accepted direct relation between polarization and unit-cell tetragonality. Here, by means of high-resolution transmission electron microscopy we map, on the unit-cell scale, the degree of tetragonality and the displacements of cations away from the centrosymmetry positions in an ultrathin epitaxial PbZr(0.2)Ti(0.8)O(3) film on a SrRuO(3) electrode layer deposited on a SrTiO(3) substrate. The lattice is highly tetragonal at the centre of the film, whereas it shows reduced tetragonality close to the interfaces. Most strikingly, we find that the maximum off-centre displacements for the central area of the film do not scale with the tetragonality. This challenges the fundamental belief in a strong polarization-tetragonality coupling in PbTiO(3)-based ferroelectrics, at such thicknesses. Furthermore, a systematic reduction of the atomic displacements is measured at the interfaces, suggesting that interface-induced suppression of the ferroelectric polarization plays a critical role in the size effect of nanoscale ferroelectrics.