Solid Solutions of Plastic/Ferroelectric Crystals: Toward Tailor-Made Functional Materials.

Plastic crystals that show ferroelectricity are highly promising materials for a wide range of applications. Their inherent remarkable malleability and highly symmetric cubic structures in the plastic crystal phase ensure that their ferroelectricity and related properties are retained in their bulk polycrystals. To develop functional materials based on such plastic/ferroelectric crystals, methods to tune their properties for specific applications are required. Here, we report the preparation of solid solutions of plastic/ferroelectric ionic crystals by mixing crystals with a common anion but different cations, or crystals with a common cation but different anions, which allows a continuous modification of the Curie temperature of the ferroelectric system over a range of 100 K. This adjustment of the Curie temperature allows the flexible tuning of the pyroelectric properties of the solid solutions, including a significant enhancement of room-temperature performance. The solid solutions also exhibit morphotropic phase boundaries in the composition-temperature phase diagrams, which shows an abrupt change in crystal structures with a variation of composition. This study showcases a simple and versatile property-tuning method that can be expected to pave the way for major progress in the development of materials based on plastic/ferroelectric crystals, which will eventually advance to the stage of pursuing tailor-made functional materials with desired properties.

Plastic/Ferroelectric Crystals with Easily Switchable Polarization: Low-Voltage Operation, Unprecedentedly High Pyroelectric Performance, and Large Piezoelectric Effect in Polycrystalline Forms.

Molecular ferroelectric crystals have attracted growing interest as potential alternatives to conventional lead-based ceramic ferroelectrics. We have recently discovered that a class of compounds known as plastic crystals can show multiaxial ferroelectricity, which allows ferroelectric performance even in polycrystalline forms. Here, we report new plastic/ferroelectric ionic molecular crystals that exhibit remarkably small coercive electric fields at room temperature. The easily switchable ferroelectric polarization enables low-voltage switching operations and high-frequency performance. Such ferroelectric crystals can be readily processed into bulk polycrystalline forms with desired shapes that are characterized by unprecedentedly high pyroelectric figures of merit and large piezoelectricity. These multifunctional molecular crystals represent highly attractive prospects for device elements with a diverse range of applications, which will significantly boost the development of molecular ferroelectric crystals.