A. P. Turygin

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.

Domain structures and local switching in lead-free piezoceramics Ba0.85Ca0.15Ti0.90Zr0.10O3

Lead-free piezoelectrics are becoming increasingly important in view of environmental problems of currently used lead-based perovskites such as lead zirconate titanate (PZT). One of the recent candidates for PZT replacement, solid solutions of BaZr0.2Ti0.8O3 and Ba0.7Ca0.3TiO3, are investigated in this work by piezoresponse force microscopy. Coexistence of the tetragonal and rhombohedral phases in this material is observed, which probably gives rise to easy polarization switching due to multiple domain states. The period of observed domain lamella scales with the grain size obeying well-known square root dependence characteristic of BaTiO3 ceramics. Domain switching and relaxation are investigated at the nanoscale as a function of the applied voltage and duration of the applied voltage pulses. The observed distortion of piezoresponse hysteresis loops near grain boundaries is attested to the increased concentration of defects. Nanoscale piezoelectric properties of these materials are discussed.

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...

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.

Physical properties of strontium barium niobate thin films prepared by polymeric chemical method

ABSTRACT Randomly oriented Sr0.75Ba0.25Nb2O6 thin films have been deposited on Pt(111)/Ti/SiO2/Si substrates using a polymeric chemical method to study their physical properties. Refinements of the structure confirm the stoichiometry of the studied films. The relaxor behavior is evidenced by the dielectric measurements and Vögel-Fulcher analysis of the dielectric curves. Lowering the transition temperature (Tm) by about 100 K and asymmetries in the local hysteresis loops well above Tm are discussed in terms of the existence of complex defects in thin films.

Effect of surface disorder on the domain structure of PLZT ceramics

ABSTRACT Pb1-xLax(Zr0.65Ti0.35)1-x/4O3 (PLZT x/65/35) ceramics were studied by Piezoresponse Force Microscopy in order to understand the origin of domain structure as a function of La content. We show that the domain topology is mainly determined by the composition and grain size. The characteristic correlation length decreases with increasing La content, being sensitive also to the synthesis method. The behavior of the correlation length is linked to the macroscopic properties, showing a strong increase of disorder with La doping. The roughness exponent for the domain wall in PLZT 9/65/35 is close to 2/3 indicating 1D character of domain walls in relaxors.

Characterization of domain structure and domain wall kinetics in lead-free Sr2+ doped K0.5Na0.5NbO3 piezoelectric ceramics by piezoresponse force microscopy

ABSTRACT The domain structure and local polarization reversal were studied in lead-free ceramics (K0.5Na0.5)1-2xSrxNbO3 by various modes of scanning probe microscopy. It was shown that the increase in Sr concentration led to a decrease in both grain and domain sizes. The local polarization reversal study provided important information on the domain wall dynamics in this complicated system. The defect distribution in doped ceramics was proposed as a major factor limiting domain wall mobility and internal bias field decrease together with the increase of the activation field for domain wall motion.