The piezoelectric properties of relaxor based ferroelectric single crystals, such as Pb(Zn1/3Nb2/3)O3–PbTiO3 and Pb(Mg1/3Nb2/3)O3–PbTiO3 were investigated for electromechanical actuators. In contrast to polycrystalline materials such as Pb(Zr,Ti)O3, morphotropic phase boundary compositions were not essential for high piezoelectric strain. Piezoelectric coefficients (d33’s)>2500 pC/N and subsequent strain levels up to >0.6% with minimal hysteresis were observed. Crystallographically, high strains are achieved for 〈001〉 oriented rhombohedral crystals, although 〈111〉 is the polar direction. Ultrahigh strain levels up to 1.7%, an order of magnitude larger than those available from conventional piezoelectric and electrostrictive ceramics, could be achieved being related to an E-field induced phase transformation. High electromechanical coupling (k33)>90% and low dielectric loss <1%, along with large strain make these crystals promising candidates for high performance solid state actuators.

New morphotropic phase boundary (MPB) piezoelectrics, with ferroelectric phase transition (T c ) exceeding that of PbZrO 3 -PbTiO 3 (PZT), were investigated. Based on a perovskite tolerance factor-T c relationship, new high T c MPB systems were projected in the Bi(Me)O 3 -PbTiO 3 system, where Me is a relatively large B +3 -site cation. For the (1 − x)BiScO 3 -(x)PbTiO 3 solid solution, a MPB was found at x-0.64 separating the rhombohedral and tetragonal phases, with correspondingly enhanced dielectric and piezoelectric properties. A transition temperature T c of ∼ 450 • C was determined with evidence of T c 's on the order of ≥ 600 • C in the BiInO 3 and BiYbO 3 analogues, though issues of perovskite stability remain for the smaller tolerance end-member systems.

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Piezoelectric properties of barium titanate single crystals were investigated at room temperature as a function of crystallographic orientation. When a unipolar electric field was applied along [001], its strain vs electric-field curve showed a large hysteresis, and finally barium titanate crystal became to single-domain state with piezoelectric constant d 33 of 125 pC/N over 20 kV/cm. On the other hand, electric-field exposure below 6 kV/cm along [111] resulted in a high d 33 of 203 pC/N and a hysteresis-free strain vs electric-field behavior, which suggested the formation of an engineered domain configuration in a tetragonal barium titanate crystal. Moreover, when an electric field over 6 kV/cm was applied along [111], two discontinuous changes were observed in its strain vs electric-field curve. In situ domain observation and Raman measurement under an electric field suggested an electric-field-induced phase transition from tetragonal to monoclinic at around 10 kV/cm, and that from monoclinic to rhombohedral at around 30 kV/cm. Moreover, in a monoclinic barium titanate crystal, electric-field exposure along [111] resulted in the formation of another new engineered domain configuration with d 33 of 295 pC/N.

Dielectric and piezoelectric properties of BaTiO3 single crystals polarized along the 〈001〉 crystallographic axes were investigated as a function of temperature and dc bias. Electromechanical coupling (k33)∼85% and piezoelectric coefficients (d33)∼500 pC/N, better or comparable to those of lead-based Pb(Zr, Ti)O3 (PZT), were found from 〈001〉-oriented orthorhombic crystals at 0 °C, as a result of crystallographic engineering. A rhombohedral BaTiO3 crystal polarized along 〈001〉 also exhibited enhanced piezoelectric performance, i.e., k33∼79% and d33∼400 pC/N at −90 °C, superior to PZTs at the same temperature. It was found that the crystal structure determined the (in)stability of the engineered domain state in BaTiO3 single crystals. Rhombohedral (3m) crystals at −100 °C exhibited a stable domain configuration, whereas depoling occurred in crystals in the adjacent orthorhombic phase upon removal of the E field.