Ferroelectrics are important materials due to their extensive technological applications, such as non-volatile memories, field-effect transistors, ferroelectric tunneling junctions, dielectric capacitors, piezoelectric transducers, sensors and actuators. As is well known, the outstanding dielectric, piezoelectric, and ferroelectric properties of these functional oxides originate from their ferroelectric domain arrangements and the corresponding evolution under external stimuli (e.g. electric field, stress, and temperature). Electric field has been known as the most efficient stimulus to manipulate the ferroelectric domains through polarization switching and alignment. Therefore, direct observation of the dynamic process of electric field-induced domain evolution and crystal structure transformation is of significant importance to understand the microstructural mechanisms for the functional properties of ferroelectrics.

In this dissertation, electric field in situ transmission electron microscopy (TEM) technique was employed to monitor the real-time evolution of the domain morphology and crystal structure during various electrical processes: (1) the initial poling process, (2) the electric field reversal process, and (3) the electrical cycling process. Two types of perovskite-structured ceramics, normal ferroelectrics and relaxor ferroelectrics, were used for this investigation. In addition to providing the microscopic insight for some well-accepted phase transformation rules, discoveries of some new or even unexpected physical phenomena were also demonstrated.

For the initial poling process, microstructural origins for the piezoelectricity development in the three most promising lead-free piezoceramic systems were investigated. For the non-ergodic relaxor ferroelectric compositions (x = 6% - 9%) in the (1-x)(Bi_1/2Na_1/2)TiO₃-xBaTiO₃ system, well-developed piezoelectricity was realized at poling fields far below the coercive field and phase transition field. Such an unusual behavior is attributed to the electric field-induced irreversible P4bm nanodomains coalescence into thin lamellar domains prior to the phase transition. In the (K_0.5Na_0.5)NbO₃-based ceramics, as demonstrated by an archetypical polymorphic phase boundary (PPB) composition of 0.948(K_0.5Na_0.5)NbO₃-0.052LiSbO₃, the origin of the excellent piezoelectric performance is due to a tilted monoclinic phase that emerges from the tetragonal and orthorhombic PPB at the poling fields beyond 14 kV/cm. This monoclinic phase, as manifested by the appearance of blotchy domains and 1/2{oeo} superlattice diffraction spots, was determined to possess a Pm symmetry with a⁰b⁺c⁰ oxygen octahedra tilting and antiparallel cation displacements. For the PPB composition of x = 0.5 in the (1-x)Ba(Zr_0.2Ti_0.8)O₃-x(Ba_0.7Ca_0.3)TiO₃ solid solution system, the original multi-domain state was found to transform into a unique single-domain state with orthorhombic symmetry at very moderate poling fields of 3~6 kV/cm. This single-domain state is suggested to be primarily responsible for the observed large piezoelectricity due to its significant elastic softening.

In the electrical reversal process, a highly unusual phenomenon of electric field-induced ferroelectric-to-relaxor phase transition was directly observed in a lead-free composition of [(Bi_1/2Na_1/2)_0.95Ba_0.05]_0.98La_0.02TiO₃. It is manifested by the disruption of large ferroelectric domains with long range polar order into polar nanodomains with short range orders when the polarity of electric field is reversed. This observation was further rationalized by a phenomenological model that takes the large difference in kinetics between the phase transition and the polarization reversal processes into account.

During the electrical cycling process, the microstructural mechanisms for electric fatigue behaviors of two ceramics were investigated. In 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃, the frozen domain configuration after 10³ cycles is responsible for the pronounced functionality degradation. Both seed inhibition and domain wall pinning mechanisms were suggested to be the reasons for the observed fatigue behavior. In the polycrystalline ceramic of [(Bi_1/2Na_1/2)_0.95Ba_0.05]_0.98La_0.02TiO₃, a novel phenomenological mechanism of domain fragmentation was found in addition to the domain wall pinning mechanism. Domain fragmentation contributes to the switchable polarization reduction by breaking the long-range polar orders, as visualized by the decomposition of large domains into domain fragments upon bipolar electrical cycling.