In this review, the main concept of ferroelectricity of perovskite oxides and related materials at nanometer scale and existing difficulties in the synthesis of those nanocrystals are discussed. Important effects, such as depolarization field and size effect, on the existence of ferroelectricity in perovskite nanocrystals are deliberated. In the discussion of modeling works, different theoretical calculations are pinpointed focusing on their studies of lattice dynamics, phase transitions, new origin of ferroelectricity in nanostructures, etc. As the major part of this review, recent research progress in the facile synthesis, characterization and various applications of perovskite ferroelectric nanomaterials, such as BaTiO₃, PbTiO₃, PbZrO₃, and BiFeO₃, are also scrutinized. Perspectives concerning the future direction of ferroelectric nanomaterials research and its potential applications in renewable energy, etc., are presented. This review provides an overview in this area and guidance for further studies in perovskite ferroelectric nanomaterials and their applications.
Single crystalline nanoneedles of polyaniline (PANI) and polypyrrole (PPY) were synthesized using an interfacial polymerization for the first time. The interfacial crystallization of conductive polymers at the liquid/liquid interface allowed PANI and PPY polymers to form single crystalline nanocrystals in a rice-like shape in the dimensions of 63 nm x 12 nm for PANI and 70 nm x 20 nm for PPY. Those crystalline nanoneedles displayed a fast conductance switching in the time scale of milliseconds. An important growth condition necessary to yield highly crystalline conductive polymers was the extended crystallization time at the liquid/liquid interfaces to increase the degree of crystallization. As compared to other interfacial polymerization methods, lower concentrations of monomer and oxidant solutions were employed to further extend the crystallization time. While other interfacial growth of conducting polymers yielded noncrystalline polymer fibers, our interfacial method produced single crystalline nanocrystals of conductive polymers. We recently reported the liquid/liquid interfacial synthesis of conducting PEDOT nanocrystals; however, this liquid/liquid interfacial method needs to be extended to other conductive polymer nanocrystal syntheses in order to demonstrate that our technique could be applied as the general fabrication procedure for the single crystalline conducting polymer growth. In this report, we showed that the liquid/liquid interfacial crystallization could yield PANI nanocrystals and PPY nanocrystals, other important conductive polymers, in addition to PEDOT nanocrystals. The resulting crystalline polymers have a fast conductance switching time between the insulating and conducting states on the order of milliseconds. This technique will be useful to synthesize conducting polymers via oxidative coupling processes in a single crystal state, which is extremely difficult to achieve by other synthetic methods.
Tetragonal ferroelectric BaTiO3 nanoparticles are hydrolyzed inside peptide‐ring templates at room temperature and pressure (see figure). The sizes of the monodisperse BaTiO3 nanoparticles are controlled between 6 and 12 nm by varying the cavity size of the nanorings as a function of pH. The nanoparticles possess switching behavior under the influence of external electric fields.
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