Ferroelectric materials have a variety of technological applications, as transducers, capacitors, sensors, etc. Great interest in molecular ferroelectrics has emerged because of their structural flexibility, tunability, and homochirality. However, the discoveries of molecular ferroelectrics are not abundant. The lack of chemical design is the main challenge in realizing new molecular ferroelectrics. Consequently, chemical design approaches, including the ideas of introducing quasi-spherical theory, homochirality, and H/F substitution, have been developed recently. Through these advanced methodologies, a wide range of ferroelectrics were successfully synthesized, changing the blind search into a targeted chemical design. In this Perspective, we aim to provide insight into the fundamental chemistry and physics of molecular ferroelectrics and propose the concept of "ferroelectrochemistry", concerned with the targeted design and performance optimization of molecular ferroelectrics from the chemical point of view. We start with the basic theories used in the modification of chemical structures for new molecular ferroelectrics, such as the quasi-spherical theory. After that, we focus on the fundamentals of homochirality from the perspective of chemistry and advantages of introducing a homochiral molecule within the scope of ferroelectrics. Further, we explore another design strategy, H/F substitution, as an analogue of the H/D isotope effect. The introduction of a F atom usually does not change the polar point group but may induce a minor structural disruption that enhances physical properties such as Curie temperature and spontaneous polarization. We hope our comprehensive studies on the targeted design and performance optimization strategies for molecular ferroelectrics may build up and enrich the content of ferroelectrochemistry.

Molecular Design Principles for Ferroelectrics: Ferroelectrochemistry

Energy storage properties in Ba0.4Sr0.6TiO3 ceramics with addition of semi-conductive BaO–B2O3–SiO2–Na2CO3–K2CO3 glass

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https://ieeexplore.ieee.org/iel5/5176125/5179396/05179402.pdf

Soft FerritesߞProperties and Applications

The structural, electrical and magnetoelectric properties of SmFeO3 ceramic samples, synthesized using a soft-chemical method, were studied. A structural analysis of the material was carried out by the Rietveld refinement of room temperature x-ray diffraction data. The temperature dependence of the dielectric peaks was analyzed by fitting them with two Gaussian peaks corresponding to two phase transitions—one being electric, and the other being magnetic in nature. The depression angle of the semicircles in a Nyquist plot representing the grain and grain boundary contributions in the sample was estimated. The grain boundary effect, appearing at temperatures above 75 °C, is explained using the Maxwell–Wagner mechanism. The impedance study reveals a semi-conducting grain with an insulating grain boundary, leading to the formation of surface and internal barrier layer capacitors and resulting in a very high dielectric constant. The effect of dc conductivity on the loss tangent at low frequencies and high temperature has been analyzed. The frequency dependence of ac conductivity in the two different regions can be explained on the basis of correlated barrier hopping and quantum mechanical tunneling models. The material is found to exhibit canted antiferromagnetism and improper ferroelectric characteristics. The value of the magnetoelectric voltage-coupling coefficient (α) of a SmFeO3 ceramic is found to be 2.2 mV cm−1 Oe−1.

https://iopscience.iop.org/article/10.1088/0022-3727/49/3/035302/pdf

The structural, electrical and magnetoelectric properties of soft-chemically-synthesized SmFeO3 ceramics

Microwave-sintering (MWS) technique was employed to fabricate dense (Ba0.4Sr0.6)TiO3 (BST) ceramics. With respect to the high dielectric loss at room temperature, induced by the formation of oxygen defects during the MWS under vacuum atmosphere (−60 kPa), the as-sintered samples were thermally annealed in air to reduce tanδ and recover the insulating performance. Accompanied by the decreased tanδ, the energy storage properties for annealed MWS BST were optimized, with increasing energy density (γ) from 0.77 to 1.15 J/cm3 and energy efficiency (η) from 60% to 82%. The lower oxygen vacancy concentrations were believed to account for the enhanced insulating characteristics of grain boundaries and contribute to the improved properties after annealing. Electrical characterization of grain and grain boundary by impedance spectroscopy demonstrated that the annealing preferentially modified the grain boundary. In addition, resistances extracted from the high temperature impedance analysis were found to be inadequate for evaluating the electrical characteristics of materials affected by extrinsic mechanisms, such as the interfacial polarization. For comparison, annealing effect on energy storage properties were also discussed for conventionally sintered BST.

Improved Energy Storage Properties Accompanied by Enhanced Interface Polarization in Annealed Microwave-Sintered BST

Structural and dielectric properties of substituted barium titanate ceramics for capacitor applications

Synthesis and dielectric properties of substituted barium titanate ceramics

Enhancement in magnetoelectric coupling in PZT based composites

Dielectric properties of Zr substituted BST ceramics

Barium titanate (BT) is among the most studied ferroelectric material which has been used in various forms, e.g. bulk, thin and thick film, powder, in a number of applications. In order to achieve a material with desired properties, it is modified with a variety of substituents. Most common substituents have been strontium, calcium and zirconium. Here we report studies on lead and zirconium substituted BT. The material series with compositional formula Ba 0.80 Pb 0.20 Ti 1− x Zr x O 3 with, 0 x P r / P s ratio was determined. It was found to decrease with increase in x .

J. K. Juneja

Papers

Structural and dielectric properties of substituted barium titanate ceramics for capacitor applications

Synthesis and dielectric properties of substituted barium titanate ceramics

Enhancement in magnetoelectric coupling in PZT based composites

Dielectric properties of Zr substituted BST ceramics

Ferroelectric properties of substituted barium titanate ceramics