The presence of dislocations and grain boundaries has a crucial influence on strain behaviors and oxygen migration dynamics and therefore drastically changes the electronic and mechanical properties of dielectric and ferroelectric materials. In this paper, we discuss our recent investigations of the polymorphic nanodomain phenomena with grain boundaries, including the structural phase segregation, strain relaxation with oxygen vacancy migrations, and ionic defect dynamics at interfacial and bulk regions in prototypical dielectrics, SrTiO3 (STO) single- and bi- crystals and ferroelectric, BaZr0.2Ti0.8O3 (BZT) films by second harmonic generation methods. We reveal that the grain boundary in STO bicrystal acts as a barrier to the oxygen vacancy migration, and a strain gradient is developed on both sides of the boundary. The misfit strain and the interphase electromechanical interactions in BZT are shown to introduce a bimodal nanodomain structure, which correlates well with polymorphic phase boundaries and provides a promising alternative to chemical compositional design, for the optimization of dielectric thin films used in capacitive energy storage applications.
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