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.
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.
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.
We report on the evidence of significant contribution of charged domain walls to low frequency dielectric permittivity in KNN ferroelectric ceramics in the frequency range 10-10 6 Hz. The effect has been attributed to the Maxwell-Wagner-Sillars relaxation.
information storage, [1,2] memristors based on tunneling, [3,4] energy storage devices, [5] etc. Tailoring the defect structure permits fine tuning of the functional properties of ferroelectrics. [6][7][8][9][10] The surfaces and interfaces are directly influenced by the nearby defects, and bulk properties are rendered by the defects via multiple mechanisms. [11,12] Up to date, the number of techniques allowing studies of defects with a high spatial resolution is limited, and they are mainly based on local monitoring of the crystalline structure or chemical composition. [13][14][15][16] Most of these local compositional methods like transmission electron microscopy, X-ray tomography, electron holography, etc. do not have a high enough sensitivity or need challenging sample preparation. [13] The optical method of second harmonic generation can be used to monitor the defect concentration and off-stoichiometry, [16] however it is limited in resolving the type of charged defects and yields only micrometer-scale spatial resolution. Thus, the novel experimental approaches allowing accurate measurement of the defect concentration and/or corresponded functional properties at the nanoscale are highly desirable.In ferroelectrics, charged defects affect polarization reversal as they directly participate in the screening of the depolarization electric field [8,[17][18][19][20] since they can become mobile Monitoring the charged defect concentration at the nanoscale is of critical importance for both the fundamental science and applications of ferroelectrics. However, up-to-date, high-resolution study methods for the investigation of structural defects, such as transmission electron microscopy, X-ray tomography, etc., are expensive and demand complicated sample preparation. With an example of the lanthanum-doped bismuth ferrite ceramics, a novel method is proposed based on the switching spectroscopy piezoresponse force microscopy (SSPFM) that allows probing the electric potential from buried subsurface charged defects in the ferroelectric materials with a nanometer-scale spatial resolution. When compared with the compositionsensitive methods, such as neutron diffraction, X-ray photoelectron spectroscopy, and local time-of-flight secondary ion mass spectrometry, the SSPFM sensitivity to the variation of the electric potential from the charged defects is shown to be equivalent to less than 0.3 at% of the defect concentration. Additionally, the possibility to locally evaluate dynamics of the polarization screening caused by the charged defects is demonstrated, which is of significant interest for further understanding defect-mediated processes in ferroelectrics.
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 BaZr 0.2 Ti 0.8 O 3 and Ba 0.7 Ca 0.3 TiO 3 , 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 BaTiO 3 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. V C 2015 AIP Publishing LLC.
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