Recent developments in high curie temperature perovskite single crystals

The temperature behavior of various relaxor-PT piezoelectric single crystals was investigated. Owing to a strongly-curved morphotropic phase boundary, the usage temperature of these perovskite single crystals is limited by T/sub R-T/- the rhombohedral to tetragonal phase transformation temperature - which occurs at the significantly lower temperatures than the Curie temperature T/sub c/. Attempts to modify the temperature usage range of Pb(Zn/sub 1/3/Nb/sub 2/3/)O/sub 3/-PbTiO/sub 3/ (PZNT) and Pb(Mg/sub 1/3/Nb/sub 2/3/)O/sub 3/-PbTiO/sub 3/ (PMNT) rhombohedral crystals (T/sub c/ /spl sim/ 150-170/spl deg/C, T/sub R-T/ /spl sim/ 60-120/spl deg/C) using minor dopant modifications were limited, with little success. Of significant potential are crystals near the morphotropic phase boundary in the Pb(Yb/sub 1/2/Nb/sub 1/2/)O/sub 3/-PbTiO/sub 3/ (PYNT) system, with a T/sub c/ > 330/spl deg/C, even though T/sub R-T/ was found to be only half the value at /spl sim/160/spl deg/C. Single crystals in the novel BiScO/sub 3/-PbTiO/sub 3/ system offer significantly higher T/sub c/s > 400/spl deg/C, while exhibiting electromechanical coupling coefficients k/sub 33/ > 90% being nearly constant till the T/sub R-T/ temperature around 350/spl deg/C, which greatly increases the temperature range for transducer applications.     

Pyroelectric performances of rhombohedral 0.42Pb(In₁/₂)Nb₁/₂)O₃-0.3Pb(Mg₁/₃Nb₂/₃)O₃-0.28PbTiO₃ single crystals

Relaxor-based ferroelectric single crystals xPb(In?/?)Nb?/?)O?-yPb(Mg?/?Nb?/?)O?-(1-x-y)PbTiO? {PIMNT [100x/100y/100(1-x-y)]} have been grown by a modified Bridgman technique. The as-grown PIMNT (42/30/28) crystal with rhombohedral perovskite-type structure shows higher Curie temperature TC ~ 187 °C, and higher ferroelectric rhombohedral-to-tetragonal phase transition temperature TRT ~ 152 °C, both about 50 °C higher than those found for 0.71Pb(In?/?)Nb?/?)O?-0.3Pb(Mg?/?Nb?/?)O?-0.29PbTiO? crystals. Moreover, as a core parameter of pyroelectric material, the detectivity figures-of-merit of PIMNT (42/30/28) crystal are higher than other typical relaxor-based ferroelectric crystals, which primarily stems from the lower dielectric loss, making it promising candidate for infrared detector applications.     

Face shear piezoelectric properties of relaxor-PbTiO(3) single crystals

Poling relaxor-PbTiO(3) single crystals along pseudocubic [011] results in a macroscopic symmetry of mm2, enabling a large face shear d(36) in Zt±45° cut crystals. In order to allow the determination of electrical properties by the resonance method, square samples are required. Using Pb(In(0.5)Nb(0.5))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) crystals, piezoelectric d(36) coefficients were determined to be in the range of 2000-2500 pC∕N, with electromechanical coupling factor k(36)～0.80-0.83. Mechanical quality factor Q～180 and ultralow frequency constant of ～500 Hz m were obtained. Together with the wide temperature usage range (up to ～110 °C) and high ac driving field stability (～5 kV∕cm), such face shear crystals have a promising potential for ultralow-frequency-transducer applications.     

Characterization of flux-grown PZN-PT single crystals for high-performance piezo devices

Relaxor ferroelectric Pb(Zn(1/3)Nb(2/3))O(3-x)PbTiO(3) (PZN-PT) and Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3)(PMN-PT) single crystals are the potential candidates for future high-performance piezoelectric devices due to their exceptionally high dielectric and piezoelectric properties. Characterization on flux-grown PZN-PT single crystals of different orientations revealed that PZN-(6-7)%PT single crystals show good homogeneity in dielectric and electromechanical properties and composition. When poled in [001] direction, these crystals exhibit high longitudinal-mode properties with dielectric constant (K(T)) approximately equal to 7000, piezoelectric coefficients (d(33)) approximately equal to 2800 pC/N, and electromechanical coupling factors (k(33)) > or = 0.92. For [011]-cut crystals, optimally poled PZN-7%PT single crystal exhibits very high transverse-mode dielectric and piezoelectric properties with K(T) > or = 5000, d(32) approximately equal to -3800 pC/N and k(32) > or = 0.90. [011]- poled PZN 6%PT has d(32) approximately equal to -3000 pC/N and comparable k(32) and K(T) values. In comparison with melt-grown PMNPT single crystals, flux-grown PZN-PT single crystals show good compositional homogeneity, superior and consistent dielectric and electromechanical properties, and higher depolarization temperatures (TDP).     

Field stability of piezoelectric shear properties in PIN-PMN-PT crystals under large drive field

The coercive fields (E(C)) of Pb(In?.?Nb?.?)O?-Pb(Mg(1/?)Nb(2/?)O?-PbTiO? (PIN-PMN-PT) ternary single crystals were found to be 5 kV/cm, double the value of binary Pb(Mg(1/?)Nb(2/?)O?-PbTiO? (PMNT) crystals, further increased to 6 to 9 kV/cm using Mn modifications. In addition to an increased EC, the acceptor modification resulted in the developed internal bias (E(int)), on the order of ~1 kV/cm. The piezoelectric shear properties of unmodified and Mn-modified PIN-PMN-PT crystals with various domain configurations were investigated. The shear piezoelectric coefficients and electromechanical coupling factors for different domain configurations were found to be >2000 pC/N and >0.85, respectively, with slightly reduced properties observed in Mn-modified tetragonal crystals. Fatigue/cycling tests performed on shearmode samples as a function of ac drive field level demonstrated that the allowable ac field levels (the maximum applied ac field before the occurrence of depolarization) were only ~2 kV/cm for unmodified crystals, less than half of their coercive field. Allowable ac drive levels were on the order of 4 to 6 kV/cm for Mn-modified crystals with rhombohedral/orthorhombic phase, further increased to 5 to 8 kV/cm in tetragonal crystals, because of their higher coercive fields. It is of particular interest that the allowable ac drive field level for Mn-modified crystals was found to be ≥ 60% of their coercive fields, because of the developed E(int), induced by the acceptor-oxygen vacancy defect dipoles.     

Electromechanical properties of Pb(In(1∕2)Nb(1∕2))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) single crystals

The Pb(In(1∕2)Nb(1∕2))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) (PIN-PMN-PT) crystals were studied as function of phase and orientation. The properties, including the Curie temperature T(C), ferroelectric-ferroelectric phase transition temperature T(R∕O-T), coercive field, and piezoelectric∕dielectric responses, were systematically investigated with respect to the composition of PIN-PMN-PT crystals. The Curie temperature T(C) was found to increase from 160 to 220 °C with ferroelectric-ferroelectric phase transition temperature T(R-T) and T(O-T) being in the range of 120-105 °C and105-50 °C, respectively. The piezoelectric activity of PIN-PMN-PT crystals was analyzed by Rayleigh approach. The ultrahigh piezoelectric response for domain engineered [001] (1600-2200 pC∕N) and [011] (830-1550 pC∕N) crystals was believed to be mainly from the intrinsic contribution, whereas the enhanced level of piezoelectric and dielectric losses at the compositions around morphotropic phase boundaries (MPBs) was attributed to the phase boundaries motion.     

Domain size engineering in tetragonal Pb(In(1∕2)Nb(1∕2))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) crystals

The effect of domain size on the dielectric and piezoelectric properties of [111]-oriented tetragonal Pb(In(1∕2)Nb(1∕2))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) crystals was investigated. The dielectric permittivity (?(33?) (T)∕?(0)) and piezoelectric coefficient (d(33)) were found to be on the order of 13 800 and 1630 pC∕N, respectively, for samples with domain size of ～500?nm, a 3-fold increase to crystals with domain size of ～50?μm. Rayleigh analysis revealed that the extrinsic contribution to the piezoelectric response increased from ～8% to 30% with decreasing domain size, due to the increased domain wall density and associated irreversible domain wall motion. The enhanced properties were thought to relate to the fine domain structures, however, showing a poor electric field and temperature stabilities with domain size of 500?nm. Of particular significance is that samples with domain size being on the order of 5?μm exhibit field and temperature stabilities, with yet high piezoelectric properties, make it potential for transducer applications.     

A double-mode piezoelectric single-crystal ultrasonic micro-actuator

Ternary Pb(In(1/2)Nb(1/2))O(3)-Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PIN-PMN-PT) single crystals with higher coercive field (E(C) ~9 kV/cm) and higher ferroelectric-transition temperature (T(R-T) = 108°C) were grown, and correspondingly, a double-mode piezoelectric ultrasonic micro-actuator made of PIN-PMN-PT crystal brick (5 x 1.5 x 1.32 mm) and operated in the first longitudinal and the second bending modes was developed. The ferroelectric, dielectric, electromechanical, and resonance displacement properties of the micro-actuator were characterized for miniature linear piezo-motor applications. The longitudinal displacement of the actuator is ~0.11 μm (with an applied voltage of 5 V), which is comparable to that of a multilayer piezoelectric-ceramic actuator of the same size. This crystal micro-actuator was successfully used to drive a slider moving linearly.     

Modified single crystals for high-power underwater projectors

Underwater electroacoustic projectors using single crystals based on the lead magnesium niobate-lead titanate (PMNT) composition were investigated. The large electromechanical coupling coefficient (k(33) > 0.90) and piezoelectric coefficient (d(33) > 1500 pC/N) of PMNT have been demonstrated to improve transducer bandwidth and source level relative to conventional piezoelectric ceramics. The low mechanical quality factor (Q(M) < 200) and low temperature stability (T(RT) < 95°C) of PMNT, however, limit its utility in high-power, high-duty-cycle applications. Use of modified single crystals was shown to result in transducers which exhibit up to 5 dB improvement in source level over PMNT when operated at resonance. Compared with a PZT4 transducer, these modified crystals offer similar source level and power handling capability at resonance, but the available bandwidth is doubled and a 6 dB improvement in maximum source level is achieved when driven off resonance.     

Dielectric and piezoelectric properties of perovskite materials at cryogenic temperatures

Dielectric and piezoelectric properties of perovskite materials including La modified Pb(Zr, Ti)O3 (PZT's), (Ba, Sr)TiO3 (BST) polycrystalline ceramics and Pb(Zn1/3 Nb2/3)O3-PbTiO3 (PZN-PT) single crystals were investigated for capacitor and actuator applications at cryogenic temperatures. PZTs were compositionally engineered to have decreased Curie temperatures (Tc) by La and Sn doping in order to compensate for the loss of extrinsic contributions to piezoelectricity at cryogenic temperatures. Enhanced extrinsic contributions resulted in piezoelectric coefficients (d33) as high as 250 pC/N at 30 K, superior to that of conventional DOD Type PZT's (d33~100 pC/N). This property enhancement was associated with retuning to the MPB at cryogenic temperatures. 5/95 BST with a dielectric maximum at 57 K was investigated to obtain high electrostrictive properties or E-field induced piezoelectricity. Coupling coefficients (k31) 25% comparable to those of the cryogenic PLZT piezoelectrics were observed at d.c. bias of 1.5 kV/cm and 50 K. Though significantly lower than the room temperature values, PZN-PT rhombohedral single crystals exhibited d33> 500 pC/N at 30 K.     

Advantages and challenges of relaxor-PbTiO3 ferroelectric crystals for electroacoustic transducers – A review

Relaxor-PbTiO₃ (PT) based ferroelectric crystals with the perovskite structure have been investigated over the last few decades due to their ultrahigh piezoelectric coefficients (d₃₃ > 1500 pC/N) and electromechanical coupling factors (k₃₃ > 90%), far outperforming state-of-the-art ferroelectric polycrystalline Pb(Zr,Ti)O₃ ceramics, and are at the forefront of advanced electroacoustic applications. In this review, the performance merits of relaxor-PT crystals in various electroacoustic devices are presented from a piezoelectric material viewpoint. Opportunities come from not only the ultrahigh properties, specifically coupling and piezoelectric coefficients, but through novel vibration modes and crystallographic/domain engineering. Figure of merits (FOMs) of crystals with various compositions and phases were established for various applications, including medical ultrasonic transducers, underwater transducers, acoustic sensors and tweezers. For each device application, recent developments in relaxor-PT ferroelectric crystals were surveyed and compared with state-of-the-art polycrystalline piezoelectrics, with an emphasis on their strong anisotropic features and crystallographic uniqueness, including engineered domain–property relationships. This review starts with an introduction on electroacoustic transducers and the history of piezoelectric materials. The development of the high performance relaxor-PT single crystals, with a focus on their uniqueness in transducer applications, is then discussed. In the third part, various FOMs of piezoelectric materials for a wide range of ultrasound applications, including diagnostic ultrasound, therapeutic ultrasound, underwater acoustic and passive sensors, tactile sensors, acoustic tweezers and ultrasonic motors, are evaluated to provide a thorough understanding of the materials’ behavior under operational conditions. Structure–property–performance relationships are then established. Finally, the impacts and challenges of relaxor-PT crystals are summarized to guide on-going and future research in the development of relaxor-PT crystals for the next generation electroacoustic transducers.     

弛豫铁电单晶及织构陶瓷的研究进展

综述了近年来弛豫铁电单晶和织构陶瓷的制备及其介电、压电性能的研究进展。弛豫铁电单晶的制备方法主要有高温溶液法、布里奇曼法和固态再结晶法，尺寸可达40mm以上，(001)切片压电常数d33最大可达3000pC／N，k3达到0.93，但是成分不均匀仍是影响晶体压电性能的一个主要因素。织构陶瓷的制备方法主要为固态再结晶法(TGG法和RTGG法)，其耗时短、成本低，压电性能可达到单晶的60％～80％，介电常数甚至可以超过部分单晶，是一个新的发展方向。     

Investigation of single and multidomain Pb(In(0.5)Nb(0.5))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) crystals with mm2 symmetry

The piezoelectric properties of Pb(In(0.5)Nb(0.5))O(3)-Pb(Mg(1∕3)Nb(2∕3))O(3)-PbTiO(3) crystals with various engineered domain configurations were investigated. Rhombohedral and monoclinic∕orthorhombic crystals poled along their crystallographic [011] directions were found to possess macroscopic mm2 symmetry, with "2R" and "1O" domain, respectively. Crystals with the "2R" domain configuration were found to exhibit high extensional piezoelectric coefficients d(33) (～1300 pC∕N) and d(32) (～-1680 pC∕N), while crystals with the "1O" configuration possessed high shear coefficients d(15) (～3500 pC∕N) and d(24) (～2070 pC∕N), with relatively low extensional piezoelectric coefficients d(33) (～340 pC∕N) and d(32) (～-260 pC∕N). The observed results were explained by "polarization rotation" model, as related to their respective domain configurations.     

Electromechanical properties and anisotropy of single- and multi-domain 0.72Pb(Mg(1∕3)Nb(2∕3))O(3)-0.28PbTiO(3) single crystals

Complete sets of elastic, piezoelectric, and dielectric constants of 0.72Pb(Mg(1∕3)Nb(2∕3))O(3)-0.28PbTiO(3) single crystal poled along [111](c) (single domain) as well as non-polar axes [001](c) and [011](c) (multidomain) have been measured under natural conditions. These data allowed us to evaluate accurately the extrinsic contributions to the superior piezoelectric properties. Very large extrinsic contributions to the unusual anisotropies in multidomain crystals are confirmed. We found that the instability of domain structures is the origin of the low mechanical quality factor Q for the multidomain relaxor-based ferroelectric single crystals. Our results can provide useful guidance in future design of domain engineered materials.     

High-performance PMN-PT thick films

This article describes some of our work on ?.??Pb(Mg?/?Nb(?/?)O?-?.??PbTiO? (0.65PMN-0.35PT) thick films printed on alumina substrates. These thick films, with the nominal composition ?.??Pb(Mg?/?Nb(?/?)O?-?.??PbTiO?, were produced by screen-printing and firing a paste prepared from an organic vehicle and pre-reacted fine particles of avery chemically homogeneous powder. To improve the adhesion of the 0.65PMN-0.35PT to the platinized alumina substrate,a Pb(Zr?.??Ti?.??)O? layer was deposited between the electrode and the substrate. The samples were then sintered at 950 °C for 2 h with various amounts of packing powder on the alumina (Al?O?) substrates. The sintering procedure was optimized to obtain dense 0.65PMN-0.35PT films. The films were then characterized using scanning electron microscopy as well as measurements of the dielectric and piezoelectric constants.The electrostrictive behavior of the 0.65PMN-0.35PT thick films was investigated using an atomic force microscope(AFM). Finally, substrate-free, large-displacement bending type actuators were prepared and characterized, and the normalized displacement (i.e., the displacement per unit length) of the actuators was determined to be 55 μm/cm at 3.6 kV/cm.     

Measurements along the growth direction of PMN-PT crystals: dielectric, piezoelectric, and elastic properties

Property measurements are reported for Pb(Mg1/3Nb2/3)03-PbTiO3 (PMN-PT) single crystals grown along (001) by a seeded-melt method. Chemical segregation occurs during crystal growth, leading to property changes along the growth direction. Variations in dielectric, piezoelectric, and elastic properties were evaluated for specimens selected from the crystals. Room-temperature data are correlated with Tc and composition that ranged from 27 to 32% PT, i.e., in the vicinity of the morphotropic phase boundary (MPB). While there was little change in the high electromechanical coupling factor k33 (0.87-0.92), both the piezoelectric charge coefficient d33 (1100-1800 pC/N) and the free dielectric constant K3 (4400-7000) were found to vary significantly with position. Increases in d33 and KT33 were relatively offsetting in that the ratio yielded a relatively stable piezoelectric voltage coefficient g33 (27-31 x 10(-3) Vm/N). Values are also reported for the elastic compliance (3.3-6.3 x 10(-11) m2/N) determined from resonance measurements. Enhancements in d33 and K(T)33 were associated with lattice softening (increasing sE33) as the composition approached the MPB. Details are reported for the piezoelectric, dielectric, and elastic properties as a function of growth direction, Tc, and composition. The results are useful for an understanding of properties in PMN-PT crystals and for the design of piezoelectric devices.     

Electric-field and stress effects on depoling and overpoling phenomena in [001]-poled transverse mode Pb(Zn1/3Nb2/3)O3-(6-7)%PbTiO3 single crystal of [110] length cut

Solid-solution Pb(Zn(1/3)Nb(2/3))O(3)-PbTiO(3) (PZN-PT) single crystals, touted as next-generation piezoelectric materials, have been studied extensively in the past decade. This work addresses the advantages and limitations of transducers made of transverse mode PZN-(6-7)%PT single crystals of [110](L) X [001](T)(P) cut. This cut exhibits superior electromechanical properties, with k(31) ≈ 0.85 and d(31) ≈-1450 pC/N, and an extremely high d(31)/S(E)(11) value of >35 C/m(2). It also has relatively high overpoling, i.e., rhombohedralto- tetragonal phase transformation, field of ≈2 kV/mm. This overpoling field further decreases with increase in axial compressive stress. Despite these good attributes, this crystal cut has a low depoling field of ≤ 0.3 kV/mm, a result of low coercive fields of [001]-poled relaxor-based single crystals, which decreases further with increasing axial compressive stress, limiting its bipolar drive capability. The axial compressive stress required to cause overpoling via rhombohedral-to-tetragonal phase transformation of relevant domain variants in the crystal is found to be >90 MPa. In contrast, this crystal cut depolarizes at comparatively low axial tensile stress of ≈15 MPa, the magnitude of which is not significantly affected by the moderate forward field applied.     

Complete set of material properties of [011](c) poled 0.24Pb(In(1/2)Nb(1/2))O(3)-0.46Pb(Mg(1/3)Nb(2/3))O(3)-0.30PbTiO(3) single crystal

A complete set of elastic, piezoelectric, and dielectric constants of [011](c) poled multidomain 0.24Pb(In(1/2)Nb(1/2))O(3)-0.46Pb(Mg(1/3)Nb(2/3))O(3)-0.30PbTiO(3) ternary single crystal has been determined using resonance and ultrasonic methods and the temperature dependence of the dielectric permittivity has been measured at 3 different frequencies. The experimental results revealed that this [011](c) poled ternary single crystal has very large transverse piezoelectric coefficient d(32) = -1693 pC/N, transverse dielectric constant ε(11)/ε(0) ~ 7400 and a high electromechanical coupling factor k(32) ~ 90%. In addition, its coercive field is 2 times of that of the corresponding binary 0.7Pb(Mg(1/3)Nb(2/3))O(3)-0.30PbTiO(3) single system with much better temperature stability. Therefore, the crystal is an excellent candidate for transverse mode electromechanical devices.     

Interpretation of T(m) and T* in relaxor ferroelectric 0.93Pb(Zn₁/₃Nb₂/₃)O₃-0.07PbTiO₃

The dielectric property of relaxor ferroelectric 0.93Pb(Zn?/?Nb?/?)O?-0.07PbTiO? single crystals (PZN-0.07PT) is studied to investigate the ferroelectric phase transition. The temperature dependence of the susceptibility of the central peak in the light scattering shows a very similar behavior to the real part of the dielectric constant, indicating that the diffuse peak in the temperature dependence of the dielectric constant is induced by relaxation of the polarization. We suggest that the origin of the relaxation above T(m) is the non-180° polarization flipping of a small polar nanoregion (PNR). Additionally, the behavior of the PNRs is interpreted through both the Brillouin spectra and high-energy synchrotron-radiation powder diffraction patterns. Our results reveal that T*~ 499K is the temperature below which the growth rate of the dynamic polarization fluctuation is suppressed by the additional random electric field induced by the generation of the static PNRs.     

Modeling of elastic nonlinearities in ferroelectric materials including nonlinear losses: application to nonlinear resonance mode of relaxors single crystals

(1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-PT) and (1-x)Pb(Zn1/3Nb2/3)O3-xPbTiO3 (PZN-PT) single crystals are considered to behave like soft Pb(Zr,Ti)O3 (PZT) ceramics because of their small mechanical quality factor Qm and poor stability under external disturbances (Qm > 500-1000 for hard PZT ceramic, and Qm < 100 for soft PZT and PMN-PT and PZN-PT single crystals). At weak signal excitation of the first resonance mode, the displacement at the end of a lateral bar is proportional to the Q31d31 figure of merit that is very close to that found for hard PZT. Indeed the very large piezoelectric coefficient compensates the low Qm. But increasing alternating current (AC) field results in the appearance of strong non-linearities through a shift of the resonance frequency and jumps phenomenon observed on increasing and decreasing frequency sweep. It is shown in this paper that these nonlinearities are due to the nonlinear elastic compliance that can be modeled by a third order development of the constitutive piezoelectric equations. Experiments on PMN-PT and PZN-PT single crystals are used for comparison with the model to show the viability of the approach. Both the frequency shift and jumps phenomenon are simulated with a very good agreement with experimental results. The importance is also shown of losses associated with the third order term responsible for the large decrease of the mechanical quality factor for high strain levels. Thus, the nonlinear losses are related to the hysteresis of domain wall motion when subjected to large displacements.