Multiferroic BiFeO3 films: domain structure and polarization dynamics

Epitaxial Pb(Zr0.35Ti0.65)O3 (PZT) thin films with tetragonal symmetry and thicknesses ranging from 45 to 230 nm were grown at 540 °C on SrRuO3-coated (001)SrTiO3 substrates by pulse-injected metalorganic chemical vapor deposition. The effect of the film thickness on the ferroelectric domain structure and the dielectric and ferroelectric properties were systematically investigated. Domain structure analysis of epitaxial PZT films was accomplished with high-resolution X-ray diffraction reciprocal space mapping and high-resolution transmission electron microscopy. Fully polar-axis (c-axis)-oriented epitaxial PZT thin films with high ferroelectric polarization values [e.g., remanent polarization (Pr) ~ 90 μC/cm2] were observed for film thicknesses below 70 nm. Films thicker than 70 nm had a c/a/c/a polydomain structure and the relative volume fraction of c-domains monotonously decreased to about 72% on increasing the film thickness up to 230 nm , and finally Pr diminished to about 64 μC/cm2 for the 230-nm-thick epitaxial film. These polarization values were in good agreement with the estimated values taking into account the volume fraction of the c-axis-oriented domains while assuming a negligible contribution of 90° domain reorientation caused by an externally applied electric field.

The ferroelectric domain structures of epitaxial BiFeO3 thin films on miscut substrates were studied using a phase-field model. The effects of substrate vicinality towards (100) are considered by assuming charge-compensated surface and film/substrate interface. The predicted domain structures show remarkable agreement with existing experimental observations, including domain wall orientations and local topological domain configurations. The roles of elastic, electric, and gradient energies on the domain structures were analyzed. It is shown that the substrate strain anisotropy due to the miscut largely determines the domain variant selection and domain configurations.

The specific features of the antiferromagnetic domain structure, magnetization, and polarization induced by an inhomogeneous micromagnetic distribution in films of bismuth ferrite multiferroics have been investigated. It has been shown that the magnetic domain structure correlates with the ferroelectric domain structure, and the character of the rotation of the antiferromagnetic vector depends on the type of ferroelectric domain walls. An asymmetry in the distribution of the antiferromagnetic vector has been observed for the cases of 109° and 71° ferroelectric domain walls. It has been demonstrated that there are differences in the distributions of the polarization and magnetization in bismuth ferrite films with ferroelectric domains separated by 109° and 71° walls. The basic mechanisms responsible for the magnetization in domain walls in multiferroics have been considered.

Interface control of tetragonal ferroelectric phase in ultrathin Si-doped HfO2 epitaxial films

We report the impact of intrinsic defects in epitaxial BiFeO3 films on charge conduction and resistive switching of Pt/BiFeO3/SrRuO3 capacitors, although the BiFeO3 films show very similar ferroelectric domain types probed by piezoresponse force microscopy. Capacitors with p-type Bi-deficient and n-type Bi-rich BiFeO3 films exhibit switchable diode and conventional bipolar resistive switching behaviors, respectively. Both the capacitors show good retention properties with a high ON/OFF ratio of >100 in Bi-deficient films and that of >1000 in Bi-rich films. The present investigation advances considerably understanding of interface control through defect engineering of BiFeO3 thin films for non-volatile memory application.

We report the ferroelectric domain mapping of a PbTiO3 (PTO) thin film using the combination of atomic force microscopy (AFM) and self-assembled polyelectrolytes. Epitaxial PTO thin films (50-nm-thick) deposited onto a Nb-doped SrTiO3 substrate via pulsed laser deposition exhibit 180° stripe ferroelectric domain structures with a mean domain width of about 10 nm. The ferroelectric PTO domain with upward (downward) polarization is selectively attached to a negatively (positively) charged poly acrylic acid (poly allylamine hydrochloride) layer as a polyelectrolyte through Coulomb interactions. Thereby, the ferroelectric PTO domains can be selectively detected using AFM.

Ti-rich PbZr1−xTixO3 (x = 0.65, PZT65) single crystals with the dimensions of 1 × 1 × 0.2 mm3 were grown by the self-flux method. Micron-sized ferroelectric domains were observed and characterized via piezoresponse force microscopy (PFM) and switching spectroscopy PFM. Both out-of-plane and in-plane components of polarization were obtained by detecting vertical and lateral vibrations of the PFM cantilever. The piezoresponse image examination revealed a clear lamellar domain structure due to apparent twinning and the formation of 90° domains. A negative self-polarization was observed in the studied crystals leading to the asymmetry of piezoresponse hysteresis loops and the polarization imprint. The polarization switching mechanism under the external electric field applied via a PFM tip was investigated. The 90° domain wall width was determined from the local PFM measurements and tentatively attributed to the oblique domain walls and chemical disorder. The time-dependent PFM imaging revealed a slow polarization relaxation process with a characteristic time of about 200 min.

The recent resurgence of bismuth ferrite (BiFeO3) as a multiferroic material was triggered by the revelation of its true bulk physical properties in the mid 2000s. Subsequently, multiferroic properties of BiFeO3 have been found to improve when it is grown as epitaxial film owing to the biaxial strain imposed by substrate materials. Since the crystal and microstructural modifications caused by the strain dominate the multiferroic property changes in BiFeO3, tremendous efforts have been devoted to the investigation of structural changes in epitaxial BiFeO3 films. However, details about strain-induced structural modifications remain elusive owing to the remarkably complex nature of BiFeO3. In this review, we discuss the followings: (1) what are the pros and cons between transmission electron microscopy (TEM) and X-ray diffraction (XRD) techniques, (2) a noble methodology of how to apply TEM and XRD to unambiguously identify crystal symmetries in epitaxial BiFeO3, and (3) once crystal symmetries are clearly identified, how can the misfit strain be accurately evaluated.

Epitaxial BiFeO3 films were grown on the (001)-, (110)-, and (111)-oriented SrTiO3 substrates. Using CoFe as ferromagnetic layer, we have shown that both large exchange bias and coercive field enhancement can be observed in the (001)- and (110)-oriented BiFeO3. But no exchange bias was found in the (111)-oriented BiFeO3 films, which can be understood by the lack of either 109° or 71° ferroelectric domain walls and the preservation of the spatial modulated cycloid spin structure. The observation of large exchange bias field with the (110)-oriented BiFeO3 film may lead to an alternative choice towards reversible control exchange bias by electrical field.

Polarization switching mechanisms in ferroelectric materials are fundamentally linked to local domain structure and the presence of the structural defects, which both can act as nucleation and pinning centers and create local electrostatic and mechanical depolarization fields affecting wall dynamics. However, the general correlative mechanisms between domain structure and polarization dynamics are only weakly explored, precluding insight into the associated physical mechanisms. Here, the correlation between local domain structures and switching behavior in ferroelectric materials is explored using convolutional encoder-decoder networks, enabling image to spectral (im2spec) and spectral to image (spec2im) translations via encoding of latent variables. The latter reflect the assumption that the relationship between domain structure and polarization switching is parsimonious, i.e., is based upon a small number of local mechanisms. The analysis of latent variables distributions and their real-space representations provides insight into the predictability of the local switching behavior and hence associated physical mechanisms. We further pose that the regions where these correlative relationships are violated, i.e., predictability of the polarization dynamics from domain structure is reduced, represent the obvious target for detailed studies, e.g., in the context of automated experiments. This approach provides a workflow to establish the presence of correlation between local spectral responses and local structure and can be universally applied to spectral imaging techniques such as piezoresponse force microscopy (PFM), scanning tunneling microscopy (STM) and spectroscopy, and electron energy loss spectroscopy (EELS) in scanning transmission electron microscopy (STEM).

A phase-field model was developed for studying the magnetoelectric coupling effect in epitaxial ferroelectric and magnetic nanocomposite thin films. The model can simultaneously take into account the ferroelectric and magnetic domain structures, the electrostrictive and magnetostrictive effects, substrate constraint, as well as the long-range interactions such as magnetic, electric, and elastic interactions. As an example, the magnetic-field-induced electric polarization in BaTiO3–CoFe2O4 nanocomposite film was analyzed. The effects of the film thickness, morphology of the nanocomposite, and substrate constraint on the degree of magnetoelectric coupling were discussed.

Optical properties of ferroelectric lanthanum lithium niobate

Ferroic materials are defined by having an order parameter that can be oriented in more than one direction. Within a ferroic material, then, there can be regions (domains) with different orientation of the order parameter: magnetic domains in ferromagnets, polar domains in ferroelectrics, twins in ferroelastics. Domain walls, or domain boundaries, are the separations between adjacent domains. In the last few years, domain walls have moved from being regarded as an inevitable by-product of the domains, to regions of interest in their own right, with unique electronic properties that may be used as the active ingredient in new electronic device paradigms, in what has been called “domain wall nanoelectronics”. The present book chapter outlines the basic physics of domain walls from their thickness and internal structure to their properties and dynamics. We will draw the connection between the fundamental properties and their experimental observation. The last section will discuss current unresolved challenges in this exciting and emerging field.

We have analyzed the defect contributions to the in-plane polarization switching of epitaxial (001) BiFeO3 thin films on (110) TbScO3 substrates. Interdigitated electrodes were patterned with respect to ferroelectric stripe domains in the BiFeO3 film. Polarization measurements exhibited a clear double hysteresis caused by the presence of a static defect field (∼40 kV/cm); the field resulted from ordered defect-dipoles initially aligned to the spontaneous polarization. By monitoring the defect field, both realignment and disassociation of the defect-dipoles were demonstrated. These results establish the arrangement of defect-dipoles in epitaxial ferroelectric thin films, guiding technologies and opening an avenue for defect related studies.

We present a simple technique for fabricating quasi-periodic bulk sub-μm ferroelectric domain gratings in Rb-doped KTiOPO4 (RKTP) based on self-organized ferroelectric domain formation. One-dimensional ferroelectric domain structures, with an average periodicity of 650 ± 200 nm and extending throughout 1 mm thick crystals, are obtained by etching and subsequent electric field poling using planar electrodes. The sub-μm structures in RKTP were used to demonstrate 5th order non-collinear quasi-phase matched backward second harmonic generation.