arXiv subjects

G. Catalan

Publications and source records attributed to G. Catalan.

At least 19 recordsLinked to original sources

arXiv2025

Switching on Antiferroelectrics

Antiferroelectrics attract broad attention due to their unusual physical characteristics, chief among which is the double-hysteresis loop that separates their antipolar ground state from the voltage-induced polar phase, which is promising for applications in energy storage and electrocaloric cooling. However, their defining features (antipolar ground state and double-hysteresis loops) are increasingly challenged: materials with non-collinear and/or hybrid polar-antipolar order have been discovered, and double-hysteresis has been realized in materials without a conventional antipolar ground state. These developments add to the intensifying interest in fundamental and practical aspects of antiferroelectrics, and call for a fresh look at antiferroelectricity. In this Perspective, we provide an updated and all-encompassing definition of antiferroelectricity, discuss material systems with new antipolar orders and/or engineered double hysteresis, and reflect on emergent properties and theoretical approaches. This work casts a bird's eye view on the rapidly evolving trends that are shaping up the research on ferroics with antipolar order.

cond-mat.mtrl-sci↗

arXiv2021

A re-examination of antiferroelectric PbZrO$_3$ and PbHfO$_3$: an 80-atom $Pnam$ structure

First principles density functional theory (DFT) simulations of antiferroelectric (AFE) PbZrO$_3$ and PbHfO$_3$ reveal a dynamical instability in the phonon spectra of their purported low temperature $Pbam$ ground states. This instability doubles the $c$-axis of $Pbam$ and condenses five new small amplitude phonon modes giving rise to an 80-atom $Pnam$ structure. Compared with $Pbam$, the stability of this structure is slightly enhanced and highly reproducible as demonstrated through using different DFT codes and different treatments of electronic exchange & correlation interactions. This suggests that $Pnam$ is a new candidate for the low temperature ground state of both materials. With this finding, we bring parity between the AFE archetypes and recent observations of a very similar AFE phase in doped or electrostatically engineered BiFeO$_3$.

cond-mat.mtrl-sci↗

arXiv2019

BaTiO3 thin films as transitional ferrroelectrics with giant dielectric response

Proximity to phase transitions (PTs) is frequently responsible for the largest dielectric susceptibilities in ferroelectrics. The impracticality of using temperature as a control parameter to reach those large responses has motivated the design of solid solutions with phase boundaries between different polar phases at temperatures (typically room temperature) significantly lower than the paraelectric-ferroelectric critical temperature. The flat energy landscapes close to these PTs give rise to polarization rotation under external stimuli, being responsible for the best piezoelectrics so far and a their huge market. But this approach requires complex chemistry to achieve temperature-independent PT boundaries and often involves lead-containing compounds. Here we report that such a bridging state is possible in thin films of chemically simple materials such as BaTiO3. A coexistence of tetragonal, orthorhombic and their bridging low-symmetry phases are shown to be responsible for the continuous vertical polarization rotation, recreating a smear in-transition state and leading to giant temperature-independent dielectric response. These features are distinct from those of single crystals, multi-domain crystals, ceramics or relaxor ferroelectrics, requiring a different description. We believe that other materials can be engineered in a similar way to form a class of ferroelectrics, in which MPB solid solutions are also included, that we propose to coin as transitional ferroelectrics.

cond-mat.mtrl-sci↗

arXiv2012

Surface phase transitions in BiFeO3 below room temperature

We combine a wide variety of experimental techniques to analyze two heretofore mysterious phase transitions in multiferroic bismuth ferrite at low temperature. Raman spectroscopy, resonant ultrasound spectroscopy, EPR, X-ray lattice constant measurements, conductivity and dielectric response, specific heat and pyroelectric data have been collected for two different types of samples: single crystals and, in order to maximize surface/volume ratio to enhance surface phase transition effects, BiFeO3 nanotubes were also studied. The transition at T=140.3K is shown to be a surface phase transition, with an associated sharp change in lattice parameter and charge density at the surface. Meanwhile, the 201K anomaly appears to signal the onset of glassy behaviour.

cond-mat.mtrl-sci↗

arXiv2011

Reversal of Ferroelectric Polarization by Mechanical Means

Ferroelectric materials are characterized by the presence of an electric dipole that can be reversed by application of an external electric field, a feature that is exploited in ferroelectric memories. All ferroelectrics are piezoelectric, and therefore exhibit a strong intrinsic coupling between polarization and elastic deformation - a feature widely used in piezoelectric transducers and high-displacement actuators. A less explored and exploited property is flexoelectricity, i.e. the coupling between polarization and a strain gradient. Though flexoelectricity is an old concept (it was discovered in the Soviet Union almost 50 years ago), it is only with the advent of nanotechnology that its full potential is beginning to be realized, as gradients at the nanoscale can be much larger than at the macroscopic scale. Here, we demonstrate that the stress gradient generated by the tip of an atomic force microscope can be used to mechanically switch the polarization in the nanoscale volume of a ferroelectric film. This observation shows that pure mechanical force can be used as a dynamic tool for polarization control, enabling information processing in a new type of multiferroic high-density data storage devices where the memory bits are written mechanically and read electrically.

cond-mat.mes-hall↗

arXiv2011

Skin layer of BiFeO3 single crystals

A surface layer ("skin") that is functionally and structurally different from the bulk was found in single crystals of BiFeO3. Impedance analysis indicates that a previously reported anomaly at T* ~ 275 \pm 5 ^/circC corresponds to a phase transition confined at the surface of BiFeO3. X-ray photoelectron spectroscopy and X-ray diffraction as a function of both incidence angle and photon wavelength unambiguously confirm the existence of a skin with an estimated skin depth of few nanometres, elongated out-of-plane lattice parameter, and lower electron density. Temperature-dependent x-ray diffraction has revealed that the skin's out of plane lattice parameter changes abruptly at T*, while the bulk preserves an unfeatured linear thermal expansion. The distinct properties of the skin are likely to dominate in large surface to volume ratios scenarios such as fine grained ceramics and thin films, and should be particularly relevant for electronic devices that rely on interfacial couplings such as exchange bias.

cond-mat.mtrl-sci↗

arXiv2009

Topology of the polarization field in ferroelectric nanowires from first principles

The behaviour of the cross-sectional polarization field is explored for thin nanowires of barium titanate from first-principles calculations. Topological defects of different winding numbers have been obtained, beyond the known textures in ferroelectric nanostructures. They result from the inward accommodation of the polarization patterns imposed at the surface of the wire by surface and edge effects. Close to a topological defect the polarization field orients out of the basal plane in some cases, maintaining a close to constant magnitude, whereas it virtually vanishes in other cases.

cond-mat.mtrl-sci↗

arXiv2009

Epitaxial TbMnO3 thin films on SrTiO3 substrates: A structural study

TbMnO$_{3}$ films have been grown under compressive strain on (001)-oriented SrTiO$_{3}$ crystals. They have an orthorhombic structure and display the (001) orientation. With increasing thickness, the structure evolves from a more symmetric (tetragonal) to a less symmetric (bulk-like orthorhombic) structure, while keeping constant the in-plane compression thereby leaving the out-of-plane lattice spacing unchanged. The domain microstructure of the films is also revealed, showing an increasing number of orthorhombic domains as the thickness is decreased: we directly observe ferroelastic domains as narrow as 4nm. The high density of domain walls may explain the induced ferromagnetism observed in the films, while both the decreased anisotropy and the small size of the domains could account for the absence of a ferroelectric spin spiral phase.

cond-mat.mtrl-sci↗

arXiv2009

Effect of Chemical Pressure on the Magnetic Transition of Multiferroic Ca-BiFeO3

Multiferroic BiFeO3 ceramics have been doped with Ca. The smaller ionic size of Ca compared with Bi means that doping acts as a proxy for hydrostatic pressure, at a rate of 1%Ca=0.3GPa. It is also found that the magnetic Neel temperature (TNeel) increases as Ca concentration increases, at a rate of 0.66K per 1%Ca (molar). Based on the effect of chemical pressure on TNeel, we argue that applying hydrostatic pressure to pure BiFeO3 can be expected to increase its magnetic transition temperature at a rate around ~2.2K/GPa. The results also suggest that pressure (chemical or hydrostatic) could be used to bring the ferroelectric critical temperature, Tc, and the magnetic TNeel closer together, thereby enhancing magnetoelectric coupling, provided that electrical conductivity can be kept sufficiently low.

cond-mat.mtrl-sci↗

arXiv2009

Origin of Ferroelastic Domains in Free-Standing Single Crystal Ferroelectric Films

The origin of the unusual 90^o ferroelectric / ferroelastic domains, consistently observed in recent studies on meso and nanoscale free-standing single crystals of BaTiO3 [Schilling et al., Physical Review B, 74, 024115 (2006); Schilling et al., Nano Letters, 7, 3787 (2007)], has been considered. A model has been developed which postulates that the domains form as a response to elastic stress induced by a surface layer which does not undergo the paraelectric-ferroelectric, cubic-tetragonal phase transition. This model was found to accurately account for the changes in domain periodicity as a function of size that had been observed experimentally. The physical origin of the surface layer might readily be associated with patterning damage, seen in experiment; however, when all evidence of physical damage is removed from the BaTiO3 surfaces by thermal annealing, the domain configuration remains practically unchanged. This suggests a more intrinsic origin, such as the increased importance of surface tension at small dimensions. The effect of surface tension is also shown to be proportional to the difference in hardness between the surface and the interior of the ferroelectric. The present model for surface tension induced twinning should also be relevant for finely grained or core-shell structured ceramics.

cond-mat.mtrl-sci↗

arXiv2009

Structural Origin of the Metal-Insulator Transition of Multiferroic BiFeO3

We report X-ray structural studies of the metal-insulator phase transition in bismuth ferrite, BiFeO3, both as a function of temperature and of pressure (931 oC at atmospheric pressure and ca. 45 GPa at ambient temperature). Based on the experimental results, we argue that the metallic gamma-phase is not rhombohedral but is instead the same cubic Pm3m structure whether obtained via high temperature or high pressure, that the MI transition is second order or very nearly so, that this is a band-type transition due to semi-metal band overlap in the cubic phase and not a Mott transition, and that it is primarily structural and not an S=5/2 to S=1/2 high-spin/low-spin electronic transition. Our data are compatible with the orthorhombic Pbnm structure for the beta-phase determined definitively by the neutron scattering study of Arnold et al .[Phys. Rev. Lett. 2009]; the details of this beta-phase had also been controversial, with a remarkable collection of five crystal classes (cubic, tetragonal, orthorhombic, monoclinic, and rhombohedral!) all claimed in recent publications.

cond-mat.mtrl-sci↗

arXiv2008

Magnetoelastic-magnetoelectric phase transitions in multiferroic BiFeO3

Our measured dielectric constant and mechanical response of multiferroic BiFeO3 indicate four phase transitions below room temperature. Features correlate with those reported at 50K (from a peak in the zero-field-cooled magnetic susceptibility) and 230K (from splitting between field-cooled and zero-field-cooled magnetic data[1], and 200K (from magnon light scattering cross sections[2]). The primary order parameter is not the polarization in any of the low-T transitions. Instead, the transition near 230 K shows strong elastic coupling, while that at 50K is fundamentally magnetic, but magnetostrictively coupled to the the lattice. The low-T phase transitions display glassy behaviour. A further anomaly at 140K interpreted as spin reorientation[2,3] shows only weakly in dielectric and mechanical studies, indicating that it is predominantly magnetic with little coupling to any of the other order parameters.

cond-mat.mtrl-sci↗

arXiv2007

Strain gradient induced polarization in SrTiO3 single crystals

Piezoelectricity is inherent only in noncentrosymmetric materials, but a piezoelectric response can also be obtained in centrosymmetric crystals if subjected to inhomogeneous deformation. This phenomenon, known as flexoelectricity, affects the functional properties of insulators, particularly thin films of high permittivity materials. We have measured strain-gradient-induced polarization in single crystals of paraelectric SrTiO$_3$ as a function of temperature and orientation down to and below the 105 K phase transition. Estimates were obtained for all the components of the flexoelectric tensor, and calculations based on these indicate that local polarization around defects in SrTiO$_3$ may exceed the largest ferroelectric polarizations. A sign reversal of the flexoelectric response detected below the phase transition suggests that the ferroelastic domain walls of SrTiO$_3$ may be polar.

cond-mat.mtrl-sci↗

arXiv2007

Fractal dimension and size scaling of domains in thin films of multiferroic BiFeO3

We have analyzed the morphology of ferroelectric domains in very thin films of multiferroic BiFeO3. Unlike the more common stripe domains observed in thicker films BiFeO3 or in other ferroics, the domains tend not to be straight, but irregular in shape, with significant domain wall roughening leading to a fractal dimensionality. Also contrary to what is usually observed in other ferroics, the domain size appears not to scale as the square root of the film thickness. A model is proposed in which the observed domain size as a function of film thickness can be directly linked to the fractal dimension of the domains.

cond-mat.mtrl-sci↗

arXiv2007

Conformal oxide coating of Carbon Nanotubes

The International Roadmap for Ferroelectric Memories requires three-dimensional integration of high-dielectric materials onto metal interconnects or bottom electrodes by 2010. We report the first integration of high-dielectric oxide films onto carbon nanotube electrodes with an aim of ultra-high integration density of FeRAMs (Tb/in2).

cond-mat.mtrl-sci↗

arXiv2007

Smallest 90o domains in epitaxial ferroelectric films

Ferroelectrics display spontaneous and switchable electrical polarization. Until recently, ferroelectricity was believed to disappear at the nanoscale; now, nano-ferroelectrics are being considered in numerous applications. This renewed interest was partly fuelled by the observation of ferroelectric domains in films of a few unit cells thickness, promising further size reduction of ferroelectric devices. It turns out that at reduced scales and dimensionalities the material's properties depend crucially on the intricacies of domain formation, that is, the way the crystal splits into regions with polarization oriented along the different energetically equivalent directions, typically at 180o and 90o from each other. Here we present a step forward in the manipulation and control of ferroelectric domains by the growth of thin films with regular self-patterned arrays of 90o domains only 7 nm wide. This is the narrowest width for 90o domains in epitaxial ferroelectrics that preserves the film lateral coherence, independently of the substrate.

cond-mat.mtrl-sci↗

arXiv2007

Domains in Three-dimensional Ferroelectric Nanostructures: Theory and Experiment

Ferroelectric random access memory cells (FeRAMs) have reached 450 x 400 nm production (0.18 micron^2) at Samsung with lead zirconate-titanate (PZT), 0.13 micron^2 at Matsushita with strontium bismuth tantalate (SBT), and comparable sizes at Fujitsu with BiFeO3. However, in order to increase storage density, the industry roadmap requires by 2010 that such planar devices be replaced with three-dimensional structures. Unfortunately, little is known yet about even such basic questions as the domain scaling of 3-d nanodevices, as opposed to 2-d thin films. Here we report the experimental measurement of nano-domains in ferroelectric nanocolumns, together with a theory of domain size in 3-d structures which explains the observations.

cond-mat.mtrl-sci↗

arXiv2006

Universality of the Scaling Law for Ferroic Domains

We show how the periodicity of 180^{o} domains as a function of crystal thickness scales with the thickness of the domain walls both for ferroelectric and for ferromagnetic materials. We derive an analytical expression for the universal scaling factor and use this to calculate domain wall thickness and gradient coefficients (exchange constants) in some ferroic materials. We then use these to discuss some of the wider implications for the physics of ferroelectric nano-devices and periodically poled photonic crystals.

cond-mat.mtrl-sci↗