D. O. Alikin

Symmetry Breaking and Electrical Frustration during Tip-Induced Polarization Switching in the Nonpolar Cut of Lithium Niobate Single Crystals

Polarization switching in ferroelectric materials is governed by a delicate interplay between bulk polarization dynamics and screening processes at surfaces and domain walls. Here we explore the mechanism of tip-induced polarization switching at nonpolar cuts of uniaxial ferroelectrics. In this case, the in-plane component of the polarization vector switches, allowing for detailed observations of the resultant domain morphologies. We observe a surprising variability of resultant domain morphologies stemming from a fundamental instability of the formed charged domain wall and associated electric frustration. In particular, we demonstrate that controlling the vertical tip position allows the polarity of the switching to be controlled. This represents a very unusual form of symmetry breaking where mechanical motion in the vertical direction controls the lateral domain growth. The implication of these studies for ferroelectric devices and domain wall electronics are discussed.

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.

Formation of nanodomain structures during polarization reversal in congruent lithium niobate implanted with ar ions

We present the experimental study of the formation of self-similar nanodomain structures during polarization reversal in single-crystalline congruent lithium niobate (CLN) implanted by Ar ions. The formed dense surface nanodomain structure with charged domain walls differs drastically from the growth of the hexagonal domains in unimplanted CLN. The lack of wall shape stability during sideways domain wall motion was revealed. The analysis of the domain structure images in the bulk, obtained by Raman confocal microscopy, revealed the main stages of the domain structure evolution starting at unimplanted polar surface and consisting of nanodomain chain elongation, merging of isolated domains, and domain widening. The switching current data has been fitted by modification of Kolmogorov-Avrami formula for switching in a linearly increasing field. The observed experimental facts have been attributed to formation of an amorphous thin surface layer and increase of the bulk conductivity resulting from oxygen out-diffusion under radiation heating in vacuum during ion implantation. The formation of the experimentally obtained abnormal domain shapes has been explained while taking into account the step generation at the domain wall in the bulk during switching in a low electric field.

Domain switching by electron beam irradiation of Z+-polar surface in Mg-doped lithium niobate

The appearance of the static domains with depth above 200 μm in the bulk of MgO-doped lithium niobate single crystals as a result of focused electron beam irradiation of Z+-polar surface was demonstrated. The created domain patterns were visualized by high-resolution methods including piezoresponse force microscopy, scanning electron microscopy, and confocal Raman microscopy. The main stages of the domain structure formation were revealed and explained in terms of the original model.

Dielectric relaxation and charged domain walls in (K,Na)NbO3-based ferroelectric ceramics

The influence of domain walls on the macroscopic properties of ferroelectric materials is a well known phenomenon. Commonly, such “extrinsic” contributions to dielectric permittivity are discussed in terms of domain wall displacements under external electric field. In this work, we report on a possible contribution of charged domain walls to low frequency (10–106 Hz) dielectric permittivity in K1-xNaxNbO3 ferroelectric ceramics. It is shown that the effective dielectric response increases with increasing domain wall density. The effect has been attributed to the Maxwell-Wagner-Sillars relaxation. The obtained results may open up possibilities for domain wall engineering in various ferroelectric materials.

Tip-induced domain growth on the non-polar cuts of lithium niobate single-crystals

Currently, ferroelectric materials with designed domain structures are considered as a perspective material for new generation of photonic, data storage, and data processing devices. Application of external electric field is the most convenient way of the domain structure formation. Lots of papers are devoted to the investigation of domain kinetics on polar surface of crystals while the forward growth remains one of the most mysterious stages due to lack of experimental methods allowing to study it. Here, we performed tip-induced polarization reversal on X- and Y-non-polar cuts in single-crystal of congruent lithium niobate which allows us to study the forward growth with high spatial resolution. The revealed difference in the shape and length of domains induced on X- and Y-cuts is beyond previously developed theoretical approaches used for the theoretical consideration of the domains growth at non-polar ferroelectric surfaces. To explain experimental results, we used kinetic approach with anisotropy of screening efficiency along different crystallographic directions.

Quantitative phase separation in multiferroic Bi0.88Sm0.12FeO3 ceramics via piezoresponse force microscopy

BiFeO3 (BFO) is a classical multiferroic material with both ferroelectric and magnetic ordering at room temperature. Doping of this material with rare-earth oxides was found to be an efficient way to enhance the otherwise low piezoelectric response of unmodified BFO ceramics. In this work, we studied two types of bulk Sm-modified BFO ceramics with compositions close to the morphotropic phase boundary (MPB) prepared by different solid-state processing methods. In both samples, coexistence of polar R3c and antipolar Pbam phases was detected by conventional X-ray diffraction (XRD); the non-polar Pnma or Pbnm phase also has potential to be present due to the compositional proximity to the polar-to-non-polar phase boundary. Two approaches to separate the phases based on the piezoresponse force microscopy measurements have been proposed. The obtained fractions of the polar and non-polar/anti-polar phases were close to those determined by quantitative XRD analysis. The results thus reveal a useful method for qua...

Morphology and Piezoelectric Properties of Diphenylalanine Microcrystals Grown from Methanol-Water Solution

Morphology and piezoelectric properties of diphenylalanine microcrystals grown by drying the droplet of methanol and water mixture in various proportions have been studied. We have found that the increase of water concentration leads to the significant change of the microcrystal morphology from flat dendrite structures to elongated microcrystals: microtubes and microrods. The effect was attributed to increasing of the drying time. The morphology of the dendrite structures was revealed and empirical dependence of the dendrite thickness on diameter was found. Finally, the piezoelectric activity of the microtubes was demonstrated using the piezoresponse force microscopy.

Characterization of LiMn2O4 cathodes by electrochemical strain microscopy

Electrochemical strain microscopy (ESM) is a scanning probe microscopy (SPM) method in which the local electrodiffusion is probed via application of AC voltage to the SPM tip and registration of resulting electrochemical strain. Here, we implemented ESM to measure local strain in bulk LiMn2O4 cathodes of a commercial Li-battery in different states of charge to investigate distribution of Li-ion mobility and concentration. Ramped AC ESM imaging and voltage spectroscopy were used to find the most reliable regime of measurements allowing separating and diminishing different contributions to ESM. This is not a trivial task due to complex geometry of the sample and various obstacles resulting in less predictable contributions of different origins into ESM response: electrostatic tip–surface interactions, charge injection, electrostriction, and flexoelectricity. Understanding and control of these contributions is an important step towards quantitative interpretation of ESM data.

Ferroelectric Domain Structure and Local Piezoelectric Properties of Lead-Free (Ka0.5Na0.5)NbO3 and BiFeO3-Based Piezoelectric Ceramics

Recent advances in the development of novel methods for the local characterization of ferroelectric domains open up new opportunities not only to image, but also to control and to create desired domain configurations (domain engineering). The morphotropic and polymorphic phase boundaries that are frequently used to increase the electromechanical and dielectric performance of ferroelectric ceramics have a tremendous effect on the domain structure, which can serve as a signature of complex polarization states and link local and macroscopic piezoelectric and dielectric responses. This is especially important for the study of lead-free ferroelectric ceramics, which is currently replacing traditional lead-containing materials, and great efforts are devoted to increasing their performance to match that of lead zirconate titanate (PZT). In this work, we provide a short overview of the recent progress in the imaging of domain structure in two major families of ceramic lead-free systems based on BiFeO3 (BFO) and (Ka0.5Na0.5)NbO3 (KNN). This can be used as a guideline for the understanding of domain processes in lead-free piezoelectric ceramics and provide further insight into the mechanisms of structure–property relationship in these technologically important material families.