In situ transmission electron microscopy study of the microstructural origins for the electric field-induced phenomena in ferroelectric perovskites

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)(Bi1/2Na1/2)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 (K0.5Na0.5)NbO3-based ceramics, as demonstrated by an archetypical polymorphic phase boundary (PPB) composition of 0.948(K0.5Na0.5)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(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)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 [(Bi1/2Na1/2)0.95Ba0.05]0.98La0.02TiO3. 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(Mg1/3Nb2/3)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 [(Bi1/2Na1/2)0.95Ba0.05]0.98La0.02TiO3, 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

Stabilized antiferroelectricity in xBiScO3-(1-x)NaNbO3 lead-free ceramics with established double hysteresis loops

We previously reported various solid solution systems that demonstrated the stabilized antiferroelectric (P) phases in NaNbO 3 through lowering the tolerance factor. However, all those reported modifications were achieved by adding A 2+ B 4+ O 3 type solid solutions. A lead-free antiferroelectric (AFE) solid solution xBiScO 3 -(1-x)NaNbO 3 was rationalized by adopting the tolerance factor design rule. Specifically, adding BiScO 3 was found to effectively stabilize the AFE phase without changing the crystal symmetry of NaNbO 3 . Microstructure and electron zone axis diffraction patterns from transmission electron microscopy revealed the stabilized AFE (P) phase in this solid solution. Besides, the electric-field-induced polarization with a double-hysteresis loop was observed. The present results pointed out that the strategy could also be applied while adding A 3+ B 3+ O 3 type solid solutions. In addition, it expanded the compositional design that can be applied to antiferroelectric materials

Electrical poling below coercive field for large piezoelectricity

Isotropic polycrystalline ferroelectric ceramics have to be electrically poled to develop a net macroscopic polarization and hence piezoelectricity. It is well accepted that a sufficient poling can only be realized under an electric field that is much higher than the coercive field. In this study, we observed in (Bi1/2 Na 1/2)TiO3-BaTiO3 ceramics that large piezoelectricity can develop at poling fields far below the measured coercive field. Using in situ transmission electron microscopy, such an unusual behavior, is interpreted with the polarization alignment of polar nanodomains in the non-ergodic relaxor phase

Creation and Destruction of Morphotropic Phase Boundaries through Electrical Poling: A Case Study of Lead-Free (Bi1/2Na1/2)TiO3-BaTiO3 Piezoelectrics

We report the first direct evidence that the morphotropic phase boundary in ferroelectric materials, along with the associated strong piezoelectricity, can be created, destroyed, or even replaced by another morphotropic phase boundary through phase transitions during electrical poling. The real-time evolution of crystal structure and domain morphology during the poling-induced phase transitions in (Bi1/2Na1/2)TiO3-BaTiO3 is observed with in situ transmission electron microscopy. These observations elucidate the microstructural origin of the macroscopic piezoelectricity’s dependence on the poling field and previously unexplained strain behaviors. This study demonstrates that the ferroelectric-to-ferroelectric transitions during the poling process can completely alter the morphotropic phase boundaries and, hence, must be comprehensively investigated when interpreting the microscopic mechanism of macroscopic piezoelectric behaviors

Effect of Ba content on the stress-sensitivity of the antiferroelectric to ferroelectric phase transition in (Pb,La,Ba,)(Zr,Sn,Ti)O3 ceramics

The effect of Ba content on the stress sensitivity of the antiferroelectric to ferroelectric phase transition in (Pb0.94−xLa0.04Bax)[(Zr0.60Sn0.40)0.84Ti0.16]O3 ceramics is investigated through monitoring electric field-induced polarization and longitudinal strain under compressive prestresses. It is found that incorporation of Ba significantly suppresses the stress sensitivity of the phase transition, as manifested by slight decreases under prestresses up to 100 MPa in the maximum polarization (Pm) and longitudinal strain (xm). The energy storage density is even increased under the mechanical confinement in compositions x = 0.02 and 0.04. X-ray diffraction, transmission electron microscopy, and dielectric measurements indicate that the suppressed stress sensitivity is associated with the disruption of micrometersized antiferroelectric domains into nanodomains and the transition from antiferroelectric to relaxor behavior

Microstructural origin for the piezoelectricity evolution in (K0.5Na0.5)NbO3-based lead-free ceramics

Chemically modified (K0.5Na0.5)NbO3 compositions with finely tuned polymorphic phase boundaries (PPBs) have shown excellent piezoelectric properties. The evolution of the domain morphology and crystal structure under applied electric fields of a model material, 0.948(K0.5Na0.5)NbO3-0.052LiSbO3, was directly visualized using in situ transmission electron microscopy. The in situ observations correlate extremely well with measurements of the electromechanical response on bulk samples. It is found that the origin of the excellent piezoelectric performance in this lead-free composition is due to a tilted monoclinic phase that emerges from the PPB when poling fields greater than 14 kV/cm are applied. 2013 AIP Publishing LLC