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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.

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., The use of ferroelectric materials in memory device applications is held back by low retention times. Here, the authors demonstrate that by intentionally introducing defective nanoregions which increase the activation field for domain wall motion, retention times larger than a year can be achieved.

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.

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.

Topological defects in ferroelectric materials have attracted much attention due to the emergence of conductive, ferroic, and magnetic functionalities. However, many topological configurations dynamically evolve during the switching processes, making them a challenge to characterize via traditional techniques. Here, we implement an automated experimentation approach for the exploration of functional properties in BiFeO3 thin films. Specifically, we visualize the ferroelectric domain structures via single frequency piezoresponse force microscopy and implement a computer vision-based algorithm to discover features of interest at which spectroscopic measurements are taken. Subsequently, we employ dimensionality reduction techniques to reveal characteristic polarization behaviors at these features. This approach can be extended to other spectroscopies and modalities to probe only specific features of interest, ultimately enabling dynamical processes in ferroelectrics to be studied.

Bismuth ferrite (BiFeO3 – BFO) is a prototypical lead-free single phase multiferroic which shows strong ferroelectric and antiferromagnetic properties simultaneously, together with high ferroelectric Curie temperature (TFE ∼ 1103 K) and Neel temperature (TN ∼ 643 K). BFO thin films and nanomaterials (collectively termed here ‘nanostructured BFO’) show many fascinating functional properties are not observed in the parent bulk compound. In this review we focus on chemical route-derived nanostructured BFO: thin films, nanowires and nanoparticles. The review covers governing factors in a detailed and systematic manner so as to give readers a clear picture of the current state of the art in the development of nanostructured BFO via chemical routes. We discuss the process pathways for each of the chemical (or soft) based synthesis techniques, highlighting both the advantages and challenges faced for each method. Specific emphasis is placed on understanding the role of each processing ingredient and development of optimized precursors. Finally we identify the opportunities posed by further development of chemical routes for this fascinating materials system. The review thus sheds significant insight into successfully achieving high-quality nanostructured BFO via chemical process techniques.

International audience; In ferroelectric thin films, the domain structure defines ferroelectric switching pathways and thus influences device performance. In epitaxial bismuth ferrite (BiFeO3) films, fractal-like domains have been observed, but direct evidence of their origins has remained unclear. Here, we show that the nature of the ferroelectric domain structure-i.e. striped vs. fractal-like-in epitaxial BiFeO3 is defined by the strain profile across the film-substrate interface. In samples with fractal-like domains, X-ray diffraction analysis reveals strong strain gradients, while geometric phase analysis using atomic resolution scanning transmission electron microscopy reveals that within a few nanometers of the film-substrate interface, the out of plane strain shows an anomalous dip while the in-plane strain is constant. Electron energy-loss near edge structure at the oxygen K edge shows that in the vicinity of the interface, the oxygen coordination is locally modified; this combined with the anomalous strain behavior thus drives the formation of fractal-like domains. Conversely, if uniform strain is maintained across the interface, characteristic striped domains are formed. Interestingly, conversion from the fractal-like arrangement to striped domains is found possible by an ex-situ thermal treatment step. Critically, the antiferromagnetic state of the BiFeO3 is influenced by the domain structure, whereby the fractal-like domains disrupt the long-range spin cycloid. Finally, as a demonstration of the applicability of this concept, we show that a carefully engineered lower electrode with large strain gradient can be used to induce fractal domains.

A nonvolatile highly scalable multilevel memory based on ferroelectric domain walls is demonstrated., 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 (

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.

In specific solid-state materials, under the right conditions, collections of magnetic dipoles are known to spontaneously form into a variety of rather complex geometrical patterns, exemplified by vortex and skyrmion structures. While theoretically, similar patterns should be expected to form from electrical dipoles, they have not been clearly observed to date: the need for continued experimental exploration is therefore clear. In this Letter we report the discovery of a rather complex domain arrangement that has spontaneously formed along the edges of a thin single crystal ferroelectric sheet, due to surface-related depolarizing fields. Polarization patterns are such that nanoscale "flux-closure" loops are nested within a larger mesoscale flux closure object. Despite the orders of magnitude differences in size, the geometric forms of the dual-scale flux closure entities are rather similar.

Domain stability and structures in Pb(Zr0.3Ti0.7)O3/Pb(Zr0.7Ti0.3)O3 bilayer films under different substrate strains are studied using the phase field method. It is demonstrated that the domain structure of the bilayer film is very different from those of the corresponding single layer films grown on the same silicon substrate with an incoherent interface. Moreover, the predicted rhombohedral domains in the Pb(Zr0.7Ti0.3)O3 layer of the bilayer film have smaller sizes than those in the single layer case. These results are compared with experimental observations and previous thermodynamic analyses. The polarization distributions of the ferroelectric–paraelectric bilayer are analyzed as a function of the thickness of the bilayer film, where there is a “ferroelectric proximity effect” due to dipole–dipole interactions. The phase diagrams for both the bilayer and single layer films as a function of temperature and effective in-plane substrate strain are constructed.

Nanometer-scale electronic transport in engineered interfaces in ferroelectrics, such as domains and topological defects, has emerged as a topic of broad interest due to potential applications in information storage, sensors and photovoltaic devices. Scanning probe microscopy (SPM) methods led to rapid growth in the field by enabling correlation of the unique functional properties with microstructural features in the aforementioned highly localized phenomena. In addition to conduction localized at interfaces, polarization-mediated control of conduction through domains in nanoscale ferroelectrics suggests significant potential for use in memristor technologies. In parallel with experiment, theory based on thermodynamic Landau-Ginzburg-Devonshire (LGD) framework has seen rapid development, both rationalizing the observations, and hinting at possibilities for local, deterministic control of order parameters. These theories can successfully account for static interface conductivity at charged, nominally uncharged and topologically protected domain walls. Here, recent experimental and theoretical progress in SPM-motivated studies on domain wall conduction in both standard and improper ferroelectrics are reviewed. SPM studies on transport through ferroelectrics reveal that both domains and topological defects in oxides can be exploited as individual elements for use in functional nanoscale devices. Future prospects of the field are discussed.

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.

The nonlinear response of a ferroic to an applied fi eld has been studied through the phenomenological Rayleigh Law for over a hundred years. Yet, despite this, the fundamental physical mechanisms at the nanoscale that lead to macroscopic Rayleigh behavior have remained largely elusive, and experimental evidence at small length scales is limited. Here, it is shown using a combination of scanning probe techniques and phase fi eld modeling, that nanoscale piezoelectric response in prototypical Pb(Zr,Ti)O 3 fi lms appears to follow a distinctly non-Rayleigh regime. Through statistical analysis, it is found that an averaging of local responses can lead directly to Rayleigh-like behavior of the strain on a macroscale. Phase-fi eld modeling confi rms the twist of the ferroelastic interface is key in enhancing piezoelectric response. The studies shed light on the nanoscale origins of nonlinear behavior in disordered ferroics.

Recent advances in thin-fi lm engineering leads to a new type of mixed-phase system in BiFeO 3 (BFO) epitaxial fi lms driven by substrate strain. [ 1 ] Single-phase multiferroic BFO had attracted great interests due to its robust ferroelectric and antiferromagnetic orderings at room temperatures. [ 2–11 ] Under a strong compressive strain ( > 4%), the stable crystal structure of BFO transformed from the rhombohedral-like monoclinics (R) to tetragonal-like monoclinics (T), [ 12 , 13 ] and with suitable strain relaxation through thickness, the coexistence of R-BFO and T-BFO phases can be obtained in the same fi lm. [ 1 , 14–18 ]

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.

This paper proposes a method to engineer the effects of mesa aspect ratio on polarization switching for single-crystal and polycrystalline PZT nanostructures. The out-of-plane polarization switching of single-crystal and polycrystalline structures as a function of crystallographic orientation, epitaxial strain and mesa aspect ratio are explored. The results are summarized in terms of the mesa geometrical parameters, crystallographic orientation and expitaxial strain. The results demonstrate a strong correlation of single-crystal properties to the polarization hysteresis behavior of a central representative grain in a polycrystalline film. The average remnant polarization and its reliability are controlled through the aspect ratio of the mesa. Calculations demonstrate that the stresses at the edges are relaxed for film height, h f , to mesa width, w , ratios h f / w ⩽ 1 × 10 −4 . For h f / w ⩾ 1 × 10 −2 , the effective in-plane stress is relaxed throughout the deposited film. Moreover, the effective stresses at the center of the mesa are 15% of the stresses of an infinite film.

Ferroelectrics are non-centrosymmetric crystalline materials that possess a spontaneous polarization that can be switched by an electric field. The electric-field-dependent optical response of these materials makes them important for optical devices, such as modulators or beam deflectors. In the inexorable drive to miniaturization, the concept of integrated thin film optical devices has led to the incorporation of ferroelectric thin films on single-crystal substrates. These structures have appealing electro-optic modulation characteristics, interesting strain-dependent bandgaps and refractive index, as well as promising possibilities for solar harvesting. Here, we review the work on epitaxial ferroelectric (FE) films for optical applications. We first show that FE thin film materials are attractive for integrated electro-optic modulators and then show that epitaxial strain can be used to enhance the FE and optical functionality of films. Next, we describe some of the photovoltaic functionality of FE thin film materials' systems and conclude the review by highlighting some thin-film devices that exploit the aforementioned optical effects.

Flux-mediated epitaxy of self-assembled ferroelectric Bi4Ti3O12 (BIT) nanoplates on SrTiO3 (001) is investigated with vanadium oxide (VOx) as the flux medium. It is shown that precoverage of a SrTiO3 (001) substrate with VOx helps to nucleate thin rutile TiO2 (001) crystallites that act as templates for the subsequent growth of (110)-oriented BIT nanoplates. Piezoresponse force microscopy reveals the presence of 90° domain walls even within a single BIT nanoplate, similar to BIT bulk single crystals.

High-performance piezoelectric devices based on ferroelectric materials rely heavily on ferroelastic domain wall switching. Here we present visual evidence for the local mechanisms that underpin domain wall dynamics in ferroelastic nanodomains. State-of-the-art band excitation switching spectroscopy piezoforce microscopy (PFM) reveals distinct origins for the reversible and irreversible components of ferroelastic domain motion. Extrapolating the PFM images to case for uniform fields, we posit that, while reversible switching is essentially a linear motion of the ferroelastic domains, irreversible switching takes place via domain wall twists. Critically, real-time images of in situ domain dynamics under an external bias reveal that the reversible component leads to reduced coercive voltages. Finally, we show that junctions representing three-domain architecture represent facile interfaces for ferroelastic domain switching, and are likely responsible for irreversible processes in the uniform fields. The results presented here thus provide (hitherto missing) fundamental insight into the correlations between the physical mechanisms that govern ferroelastic domain behavior and the observed functional response in domain-engineered thin film ferroelectric devices.

Experimental results on entirely complex oxide ferromagnetic/ferroelectric/ ferromagnetic tunnel junctions are presented in which the tunneling magnetoresistance is modified by applying low electric field pulses to the junctions. The experiments indicate that ionic displacements associated with the polarization reversal in the ferroelectric barrier affect the complex band structure at ferromagnetic-ferroelectric interfaces. The results are discussed in the framework ofthe theoretically predicted magnetoelectric interface effect and may lead to novel multistate memory devices.

The discovery of a universal behavior in rare-earth (RE)-substituted perovskite BiFe0 3 is reported. The structural transition from the ferroelectric rhombohedral phase to an orthorhombic phase exhibiting a double-polarization hysteresis loop and substantially enhanced electromechanical properties is found to occur independent of the RE dopant species. The structural transition can be universally achieved by controlling the average ionic radius of the A-site cation. Using calculations based on first principles, the energy landscape of BiFe0 3 is explored, and it is proposed that the origin of the double hysteresis loop and the concomitant enhancement in the piezoelectric coefficient is an electric-field-induced transformation from a paraelectric orthorhombic phase to the polar rhombohedral phase.

We present a comprehensive study of the physical properties of epitaxial cobalt-doped BiFeO3 films ∼50 nm thick grown on (001) LaAlO3 substrates. X-ray diffraction and magnetic characterization demonstrate high quality purely tetragonal-like (T′) phase films with no parasitic impurities. Remarkably, the step-and-terrace film surface morphology can be fully recovered following a local electric-field-induced rhombohedral-like to T′ phase transformation. Local switching spectroscopy experiments confirm the ferroelectric switching to follow previously reported transition pathways. Critically, we show unequivocal evidence for conduction at domain walls between polarization variants in T′-like BFO, making this material system an attractive candidate for domain wall-based nanoelectronics.

The local atomic structure and nanoscale chemistry of an antipolar phase in Bi0.9Sm0.1FeO3 epitaxial thin films are examined by an array of transmission electron microscopy (TEM) coupled with electron diffraction and electron energy-loss spectroscopy methods. The observations are tied to macroscopic properties of the films, namely, polarization-electric field hysteresis loops, dielectric constant-electric field hysteresis loops, and the dielectric loss. At room temperature, the local Sm deficiency was determined to destabilize the long-range ferroelectric state, resulting in the formation of local antipolar clusters with the appearance of PbZrO3-like antiparallel cation displacements, which give rise to 1/4{011} and 1/4{211} reflections as well as 1/2{321}, because of in-phase oxygen octahedral tilts. Aberration-corrected TEM analysis reveals that the antipolar structure is actually a lamellar of highly dense ferroelectric domains with alternating polarizations. With increasing temperature, a phase transi...

The phase stability of ultra-thin (0 0 1) oriented ferroelectric PbZr1-xTixO3(PZT) epitaxial thin films as a function of the film composition, film thickness, and the misfit strain is analyzed using a non-linear Landau-Ginzburg-Devonshire thermodynamic model taking into account the electrical and mechanical boundary conditions. The theoretical formalism incorporates the role of the depolarization field as well as the possibility of the relaxation of in-plane strains via the formation of microstructural features such as misfit dislocations at the growth temperature and ferroelastic polydomain patterns below the paraelectric-ferroelectric phase transformation temperature. Film thickness-misfit strain phase diagrams are developed for PZT films with four different compositions (x = 1, 0.9, 0.8 and 0.7) as a function of the film thickness. The results show that the so-called rotational r-phase appears in a very narrow range of misfit strain and thickness of the film. Furthermore, the in-plane and out-of-plane dielectric permittivities ε11and ε33, as well as the out-of-plane piezoelectric coefficients d33for the PZT thin films, are computed as a function of misfit strain, taking into account substrate-induced clamping. The model reveals that previously predicted ultrahigh piezoelectric coefficients due to misfit-strain-induced phase transitions are practically achievable only in an extremely narrow range of film thickness, composition and misfit strain parameter space. We also show that the dielectric and piezoelectric properties of epitaxial ferroelectric films can be tailored through strain engineering and microstructural optimization. Refereed/Peer-reviewed

Grain-to-grain long-range interactions and the ensuing collective dynamics in the domain behavior of nanostructured polycrystalline Pb(Zr,Ti)O 3 ferroelectric thin films have been investigated. To identify the key factors and interactions controlling local polarization dynamics we utilize a synergistic approach based on focused ion beam (FIB) milled damage-free nanostructures to isolate single grains and grain clusters, time-resolved piezoresponse force microscopy and switching spectroscopy PFM (SSPFM) (PFM) to address polarization dynamics within individual grains, and finite-element simulations to quantify the local ferroelectric interactions and hence assess the weight of several possible switching mechanisms. The experiments find that of the three possible switching mechanisms, namely direct electromechanical coupling, local built-in electric field and strain, and grain boundary electrostatic charges, the last one is the dominant mechanism. Although finite-element simulations find that direct electromechanical coupling and local built-in field-induced switching are possible, calculations confirm that for the utilized material properties, the aforementioned mechanisms are energetically unfavored.

We present a theoretical investigation of the elastic interactions in a heteroepitaxial bilayer consisting of a (001) tetragonal PbZrxTi1-xO3and (001) rhombohedral PbZr1-xTixO3on a thick (001) passive substrate. Analytical expressions for the elastic interaction energies between the layers and the resultant ferroelastic twin formation have been derived as a function of the lattice misfit strain (between layers and the substrate), composition of the ferroelectric and thickness. It is found that the elastic coupling between the tetragonal and rhombohedral layers leads to the equilibrium domain fraction in the tetragonal layer several time larger than that in single-layer films of similar thickness. Most critically, the model finds a significant change in the ferroelastic domain volume fraction in the presence of an applied electric field and hence enhanced piezoelectric properties compared to single-layered epitaxial PZT thin films. Refereed/Peer-reviewed

The property of ferroelectricity was first reported in 1921 in Rochelle salt (sodium potassium tartrate). Once considered a rare phenomenon limited to a comparatively small class of crystals, the discovery of ferroelectricity in the binary oxide compound barium titanate (BaTiO3) in the mid-1940s paved the way for rapid advances in the search of new materials. Since that time, a great many other ferroelectric compounds and solid solutions have been found and there has been broad interest in ferroelectric materials that has continued essentially uninterrupted until the present time. Ferroelectric materials remain subjects of intensive investigation today for three principal reasons. First, the unique dielectric, pyroelectric, piezoelectric, and electro-optic properties exhibited by ferroelectric crystals, ceramics, composites, and thin films can be exploited in great many devices of commercial importance. Second, apart from their many technological applications, ferroelectric materials as a class exhibit a great diversity of phase transitions that make them ideal objects for scientific investigations into the origins and mechanisms of a wide range of structural transformation phenomena. Finally, advances in thin-film deposition and nanoscale fabrication techniques made over the past two decades have created new possibilities for the integration of these materials into the ever expanding array of microelectronic devices. Ferroelectrics form a sub-group of functional (or smart) materials whose physical properties are sensitive to changes in external conditions such as temperature, pressure, and electric fields. Below some critical temperature TC, the dielectric displacement (electric polarization) spontaneously assumes non-zero values in the absence of any externally applied force. The transition between non-ferroelectric and ferroelectric phases is accompanied by a loss of symmetry, characterized by double-well minima below the transition temperature, resulting in a switchable polarization that is accompanied by a hysteresis in the electric field–dielectric displacement response. As a class of materials, ferroelectrics also exhibit unusually large and nonlinear generalized susceptibilities; their dielectric, piezoelectric, elastic, and other properties display critical behavior near the ferroelectric phase transformation temperature. Ferroelectrics may be regarded as high energydensity materials as well that can be configured to store, release or interconvert electrical and mechanical energy in a well-controlled manner. Their exceptionally large piezoelectric compliances, pyroelectric coefficients, and dielectric susceptibilities can be exploited in a variety of microelectronic devices. Important examples of these include piezoelectric sensors and actuators, pyroelectric thermal imaging devices, high-dielectric constant capacitors, electro-optic light valves, and thin-film memories. Because of their strongly non-linear dielectric response ferroelectrics can be utilized in applications such as frequency-agile phase shifters and filters in wireless telecommunications systems. Because the properties of ferroelectric materials that are exploited in technological applications are intimately S. P. Alpay (&) G. A. Rossetti Jr. Materials Science and Engineering Program, Departments of Chemical, Materials, and Biomolecular Engineering, University of Connecticut, Storrs, CT, USA e-mail: p.alpay@ims.uconn.edu

We present a detailed investigation of the chemistry at the growth interface between the bottom electrode and ferroelectric film in (001)-oriented epitaxial ferroelectric thin-film heterostructures. Three different ferroelectric systems, namely PbZr0.2Ti0.8O3, PbZr0.52Ti0.48O3, and BaTiO3 deposited on SrRuO3/SrTiO3, were investigated to compare and contrast the role of lattice mismatch versus the volatility of the deposited cation species. A combination of transmission electron microscopy-based imaging and spectroscopy reveals distinct correlations among the ferroelectric thin-film composition, the deposition process, and chemical gradients observed across the ferroelectric–electrode interface. Sr diffusion from the electrode into the ferroelectric film was found to be dominant in PbZr0.2Ti0.8O3/SrRuO3/SrTiO3 thin films. Conversely, Pb diffusion was found to be prevalent in PbZr0.52Ti0.48O3/SrRuO3/SrTiO3 thin films. The BaTiO3/SrRuO3/SrTiO3 heterostructure was found to have atomically sharp interfaces with no signature of any interdiffusion. We show that controlling the volatility of the cation species is as crucial as lattice mismatch in the fabrication of defect-free ferroelectric thin-film devices.

Heterostructured thin films differing either in their structure, composition, or in both have shown novel magnetic, superconducting, ferroelectric, or electromechanical responses. In the case of ferroelectrics, multilayers or superlattices have displayed enhanced polarization, high dielectric permittivity and in some instances, entirely new structural phases. These observations have been accounted for on the basis of electric-field-induced coupling, epitaxial strain, and specific polar interactions between the interfacial layers. As most ferroelectrics have a strong non-negligible ferroelastic self-strain associated with their phase transformation, an aspect that should be equally fascinating is that of the elastic interactions between such multilayers. The interactions lead to the formation of ferroelastic domains, arranged in the form of periodalternating lamellae in order to relax the excess elastic energy. When these lamellae are of the same phase but of different crystallographic orientations, they are generally referred to as ‘‘twins’’. The ferroelastic-domain-wall (extrinsic) contribution to the dielectric, piezoelectric, and elastic properties of ferroelectrics is indeed quite significant in the case of bulk ceramics and single-crystals, and this can be several times larger than the intrinsic lattice piezoresponse. In the case of ferroelectric thin films, the issue of movement of ferroelastic domains is not without debate. Earlier experimental studies proposed that the ferroelastic ‘‘herringbone’’ pattern in thin films demonstrated very limited (if any) ability to move under external stress or electric field. This has been contradicted in more recent experiments on polycrystalline films. Nevertheless, gross quantitative enhancement has been reported only under special conditions, such as films patterned into

Bismuth ferrite (BiFeO$_3$) is one of the very few known single-phase multiferroic materials. While the bulk compound is rhombohedral (R), the discovery of an epitaxial strain-induced structural transition into a so-called 'super tetragonal-phase' (T-phase) in this material incited a flurry of research activity focused on gaining an understanding of this phase transition and its possible functionalities. This metastable phase of BiFeO$_3$ is also multiferroic, with giant ferroelectric polarization and coexisting antiferromagnetic order, but above all it is the strain relaxation-induced phase mixtures and their outstanding piezoelectric and magnetoelectric responses which continue to intrigue and motivate the physicist and materials scientist communities. Here, we review the research into the T-phase and mixed-phase BiFeO$_3$ system. We begin with a brief summary of the history of the T-phase and an analysis of the structure of the various phases reported in the literature. We then address important questions regarding the symmetry and octahedral rotation patterns and the (as yet underexplored) important role of chemistry in the formation of the metastable T-phase. We follow by describing the phase transitions in this material, and how these may hold promise for large magnetoelectric responses. Finally we point out some experimental challenges inherent to the study of such a system, and potential pathways for how they may be overcome. It is our intention with this work to highlight important issues that, in our opinion, should be carefully considered by the community in order to use this fascinating materials system for a new paradigm of functionality., Comment: 25 pages, 6 figures

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.

The scaling of the piezoelectric and dielectric constants with film thickness in ultra-thin ferroelectric heterostructures is investigated. Epitaxial (001) PbZr0.2Ti0.8O3 films ranging in thickness from 5 nm to 30 nm with top and bottom SrRuO3 electrodes were grown onto (001) SrTiO3 substrates via pulsed laser deposition. Piezoelectric and dielectric measurements were performed using an atomic force microscope. The remnant value of the out of plane piezoresponse (d33) decreases from 60 pm/V for the 30 nm film to just 7 pm/V for the 5 nm film. This systematic decline in d33 is accompanied by a corresponding increase in the coercive field. The d33 loops show a systematic increase in tilt towards the applied field axis as function of reducing thickness coupled with a decrease in piezoelectric tunability. The small-signal relative dielectric response in the direction normal to the film-substrate interface decreases from 140 for a 50 nm film to just 60 for a 8 nm film. A similar drop is also observed in the dielectric tunability, from ∼17% to approximately −2% at an electric field of 750 kV/cm with the film thickness decreasing from 50 nm to 8 nm. We show that these observations cannot be explained using a straightforward application of a modified Landau-Devonshire thermodynamic model that incorporates the internal stresses due to the lattice and thermal expansion mismatch between the film and the substrate. We attribute this behavior to degradation in the polarization due to an intrinsic finite size effect.

We present a sensitive method to simultaneously acquire the C(V ) characteristics and piezoresponse of sub-micron size ferroelectric capacitors using an Atomic Force Microscope (AFM). Model Pt/(La0.5,Sr0.5)CoO3/PbZr0.4Ti0.6 O3/(La0.5,Sr0.5)CoO3/La:SrTiO3/Si nanocapacitors were fabricated by focused ion beam milling from 100 μm2 down to 0.04 μm2. With this AFM based capacitance measurement technique we show clear “double-humped” C(V ) for all sizes with no significant change in the peak value of the er down to capacitors with the smallest area of 0.04 μm2. The smallest capacitance measured is only of the order a few femtofarads, demonstrating the high sensitivity of the technique. Simultaneously, the piezoelectric response is recorded for each measurement, thus the technique facilitates simultaneous piezoresponse and dielectric characterization of ferroelectric memory devices.

In this paper we demonstrate a modified focused ion beam (FIB) milling approach integrated with self-alignment to synthesize ferroelectric nanostructures. Nanoscale holes ranging from 500 nm down to 100 nm in diameter are created on 'spun-on' amorphous TiO2 on Pt/TiO2/Si using FIB milling. It is found that spin-coating of PbZr0.4Ti0.6O3 (PZT) sol–gel precursors on these templated surfaces followed by low-temperature (~400 °C) annealing leads to a ferroelectric phase only within the holes. Piezoresponse force microscopy (PFM) was used to confirm that the crystallized phase within the holes were ferroelectric and switchable. The smallest lateral size shown to be ferroelectric is roughly 70–80 nm in diameter. Quantitative PFM of the nanoscale ferroelectric regions yielded a value of 17 pm V−1, in good agreement with previously published data on polycrystalline PZT. Additionally this method facilitates the integration of interlayer dielectrics or 'spun-on' glass during the synthesis without the need for additional lithography and processing.

La0.5Sr0.5CoO3/Pb(Zr x Ti1−x)O3/La0.5Sr0.5CoO3 capacitors have been successfully fabricated by liquid delivery metalorganic chemical vapor deposition on Si wafers using SrTiO3 thin layer (20 nm) as a template. Zr(dmhd)4 in tetrahydrofuran was used as Zr precursor for compatible thermal behavior with Pb(thd)2 and Ti(OiPr)2(thd)2 precursors. The dependence of the ferroelectric film composition on the precursor mixing ratio and growth temperature has been systematically studied by Rutherford Backscattering (RBS). Ferroelectric and piezoelectric properties at the composition close to morphotropic phase boundary region (Pb(Zr0.5Ti0.5)O3) have been investigated for application in nonvolatile ferroelectric random access memories and microelectromechanical system (MEMS). These capacitors show desirable ferroelectric properties, which proves that this approach is very promising for both fundamental study and potential applications. The changes of spontaneous polarization (P s ) and piezoelectric coefficient (d33) with Ti/(Zr + Ti) ratio are also presented and compared with theoretical values.

Wetting of the pore walls of porous templates is a simple and convenient method to prepare nanotubes. Ferroelectric lead zirconate titanate and barium titanate nanotubes were fabricated by wetting of porous silicon templates of polymeric precursors. The ferro- and piezoelectric properties of an individual ferroelectric either of a PZT or a BaTiO3 nanotube were electrically characterized by measuring the local piezoelectric hysteresis. A sharp switching at the coercive voltage of about 2 V was shown from the hysterisis loop. The corresponding effective remnant piezoelectric coefficient is about 90 pm/V. We also expect that free-standing ferroelectric nanotubes obtained by partial etching of the silicon template will be used as building blocks of miniaturized devices and can have a significant impact in the field of nano-electromechanical systems.

We have performed depth profile studies of the structure of PbZr0.2Ti0.8O3 films of different thicknesses deposited on SrTiO3 substrates prepared by pulsed laser deposition, using grazing incident x-ray scattering (GIXS). The in-plane structure of the films reveals these consist of up to three domains, one c-axis domain, and two a-axis domains, denoted a1 and a2. GIXS measurements show the evolution of in-plane compression of the lattice parameter as a function of depth within the films, particularly in the a1 domains. This strain evolution is accompanied by the presence of twist grain boundaries in the plane in some films. The measured in-plane lattice parameters are asymmetric, which suggests an orthorhombic distortion of the lattice in the plane of the films.

We investigate photo-induced ferroelectric domain switching in a series of Pb(Zr0.2Ti0.8)O3/La0.7Sr0.3MnO3 (PZT/LSMO) bilayer thin films with varying surface morphologies by piezoresponse force microscopy under light illumination. We demonstrate that reverse poled ferroelectric regions can be almost fully recovered under laser irradiation of the PZT layer and that the recovery process is dependent on the surface morphology on the nanometer scale. The recovery process is well described by the Kolmogorov-Avrami-Ishibashi model, and the evolution speed is controlled by light intensity, sample thickness, and initial write voltage. Our findings shed light on optical control of the domain structure in ferroelectric thin films with different surface morphologies.

We investigate ferroelectric domain structure and piezoelectric response under variable mechanical compressive stress in Pb(Zr0.2TiO0.8)O3 (PZT) thin films using high-resolution piezoresponse force microscopy (PFM) and an in situ sample bending stage. Measurements reveal a drastic change in the ferroelectric domain structure which is presented along with details of the mediating switching process involving domain wall motion, nucleation, and domain wall roughening under an applied external mechanical stimulus. Furthermore, local PFM hysteresis loops reveal significant changes in the observed coercive biases under applied stress. The PFM hysteresis loops become strongly imprinted under increasing applied compressive stress.

Interfacial control of a polar-(rhombohedral) to-non-polar (orthorhombic) phase transition in (001)-oriented epitaxial $\mathrm{BiFe}{\mathrm{O}}_{3}\text{/}(\mathrm{B}{\mathrm{i}}_{1\ensuremath{-}x}\mathrm{S}{\mathrm{m}}_{x})\mathrm{Fe}{\mathrm{O}}_{3}$ superlattices is presented. We demonstrate controlling the composition at which a polar phase transformation takes place by tuning the strength of the interlayer interactions while holding the average composition constant. It is shown that the thickness of the superlattice layers has a strong influence on the interlayer polar coupling, which in turn changes the phase transition. For the shortest periods studied (layers 5- and 10-nm thick) the onset of the phase transition is suppressed along with a significant broadening (as a function of $\mathrm{S}{\mathrm{m}}^{3+}$ concentration) of an incommensurately modulated phase determined by two-dimensional x-ray diffraction mapping. Consequently, a ferroelectric character with robust polarization hysteresis and enhanced dielectric constant is observed even for substitution concentration of $\mathrm{S}{\mathrm{m}}^{3+}$ which would otherwise lead to a leaky paraelectric in single-layer $(\mathrm{B}{\mathrm{i}}_{1\ensuremath{-}x}\mathrm{S}{\mathrm{m}}_{x})\mathrm{Fe}{\mathrm{O}}_{3}$ films. The experimental results are fully consistent with a mean-field thermodynamic theory which reveals that the strength of the interlayer coupling is strongly affected by the polar-polar interaction across the interface.

Ferroelectrics have been used as memory storage devices, with an upper bound on the total possible memory levels generally dictated by the number of degenerate states allowed by the symmetry of the ferroelectric phase. Here, we introduce a new concept for storage wherein the polarization can be rotated arbitrarily, effectively decoupling it from the crystallographic symmetry of the ferroelectric phase on the mesoscale. By using a Bi5Ti3FeO15-CoFe2O4 film and via Band-Excitation Piezoresponse Force Microscopy, we show the ability to arbitrarily rotate polarization, create a spectrum of switched states, and suggest the reason for polarization rotation is an abundance of sub-50 nm nanodomains. Transmission electron microscopy-based strain mapping confirms significant local strain undulations imparted on the matrix by the CoFe2O4 inclusions, which causes significant local disorder. These experiments point to controlled tuning of polarization rotation in a standard ferroelectric, and hence the potential to greatly extend the attainable densities for ferroelectric memories.

We present a theoretical description of the influence of misfit strain on mobile defects dynamics in thin strained ferroelectric films. Self-consistent solutions obtained by coupling the Poissons equation for electric potential with continuity equations for mobile donor and electron concentrations and time-dependent Landau-Ginzburg-Devonshire equations reveal that the Vegard mechanism (chemical pressure) leads to the redistribution of both charged and electro-neutral defects in order to decrease the effective stress in the film. Internal electric fields, both built-in and depolarization ones, lead to a strong accumulation of screening space charges (charged defects and electrons) near the film interfaces. Importantly, the corresponding screening length is governed by the misfit strain and Vegard coefficient. Mobile defects dynamics, kinetics of polarization and electric current reversal are defined by the complex interplay between the donor, electron and phonon relaxation times, misfit strain, finite size effect and Vegard stresses., Comment: 34 pages, 7 figures, supplementary materials

We report observations of the ferroelectric domain structure in epitaxial lead zirconate titanate (PZT) ferroelectric thin films using piezoresponse microscopy. EpitaxialPZT films with a nominal composition of PbZr0.2Ti0.8O3were deposited onto single crystal SrTiO3 substrates by pulsed laser deposition, with an epitaxial layer of La-Sr-Co-O as the bottom electrode. By manipulating thefilm thickness, a uniform 2-dimensional grid of 90° domains (a-domains, i.e., c-axis in the plane of the film) has been induced. Our studies show that the polarization direction in the film is substantially preferentially oriented and that nucleation of reverse 180° domains occurs preferentially at 90° domain interfaces. Polarization reversal occurs through the nucleation and subsequent growth of “semicircular/elliptical” reverse domains, which subsequently consume the entire region as a function of reversal time. The reversal is seen to fit a stretched exponential.

Epitaxial ferroelectric films undergoing a cubic-tetragonal phase transformation relax internal stresses due to the structural phase transformation and the difference in the thermal expansion coefficients of the film and the substrate by forming polydomain structures. The most commonly observed polydomain structure is the c/a/c/a polytwin which only partially relieves the internal stresses. Relatively thicker films may completely reduce internal stresses if all three variants of the ferroelectric phase are brought together such that the film has the same in-plane size as the substrate. In this article, we provide experimental evidence on the formation of the three-domain structure based on transmission electron microscopy in 450 nm thick (001) PbZr0.2Ti0.8O3 films on (001) SrTiO3 grown by pulsed laser deposition. X-ray diffraction studies show that the film is fully relaxed. Experimental data is analyzed in terms of a domain stability map. It is shown that the observed structure in epitaxial ferroelectric...

We have studied the effect of misfit strain on the microstructure and properties of ferroelectric lead zirconate titanate thin films. We have changed the misfit strain by varying the film thickness and studied the thickness effect on the domain formation of epitaxial PbZr0.2Ti0.8O3 (PZT) films grown by pulsed laser deposition on (001) LaAlO3 substrates with La0.5Sr0.5CoO3 (LSCO) electrodes. The nominal thickness of the PZT films was varied from 60 to 400 nm with the LSCO electrode thickness kept constant at 50 nm. X-ray diffraction experiments show that the films relax via the formation of a domains, the fraction of which increase with the ferroelectric film thickness. The c-axis lattice constant of PZT films calculated from the 002 reflection decreases with increasing film thickness and approaches the bulk value of ∼0.413 nm in the films thicker than 300 nm. Cross-sectional transmission electron microscopy images reveal that the a-domain fraction and period increase with increasing film thickness. The relaxation of misfit strain in the film is accompanied by systematic changes in the polarization properties, as well as the switching fields, quantified by the coercive field and the activation field.