Transparent ferroelectric crystals with ultrahigh piezoelectricity.

Transparent piezoelectrics are highly desirable for numerous hybrid ultrasound-optical devices ranging from photoacoustic imaging transducers to transparent actuators for haptic applications1-7. However, it is challenging to achieve high piezoelectricity and perfect transparency simultaneously because most high-performance piezoelectrics are ferroelectrics that contain high-density light-scattering domain walls. Here, through a combination of phase-field simulations and experiments, we demonstrate a relatively simple method of using an alternating-current electric field to engineer the domain structures of originally opaque rhombohedral Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) crystals to simultaneously generate near-perfect transparency, an ultrahigh piezoelectric coefficient d33 (greater than 2,100 picocoulombs per newton), an excellent electromechanical coupling factor k33 (about 94 per cent) and a large electro-optical coefficient γ33 (approximately 220 picometres per volt), which is far beyond the performance of the commonly used transparent ferroelectric crystal LiNbO3. We find that increasing the domain size leads to a higher d33 value for the [001]-oriented rhombohedral PMN-PT crystals, challenging the conventional wisdom that decreasing the domain size always results in higher piezoelectricity8-10. This work presents a paradigm for achieving high transparency and piezoelectricity by ferroelectric domain engineering, and we expect the transparent ferroelectric crystals reported here to provide a route to a wide range of hybrid device applications, such as medical imaging, self-energy-harvesting touch screens and invisible robotic devices.

Ultrahigh piezoelectricity in ferroelectric ceramics by design.

Piezoelectric materials, which respond mechanically to applied electric field and vice versa, are essential for electromechanical transducers. Previous theoretical analyses have shown that high piezoelectricity in perovskite oxides is associated with a flat thermodynamic energy landscape connecting two or more ferroelectric phases. Here, guided by phenomenological theories and phase-field simulations, we propose an alternative design strategy to commonly used morphotropic phase boundaries to further flatten the energy landscape, by judiciously introducing local structural heterogeneity to manipulate interfacial energies (that is, extra interaction energies, such as electrostatic and elastic energies associated with the interfaces). To validate this, we synthesize rare-earth-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT), as rare-earth dopants tend to change the local structure of Pb-based perovskite ferroelectrics. We achieve ultrahigh piezoelectric coefficients d33 of up to 1,500 pC N-1 and dielectric permittivity ε33/ε0 above 13,000 in a Sm-doped PMN-PT ceramic with a Curie temperature of 89 °C. Our research provides a new paradigm for designing material properties through engineering local structural heterogeneity, expected to benefit a wide range of functional materials.

1-3 piezoelectric composites for high temperature transducer applications.

High temperature Pb(Zr,Ti)O3 /epoxy 1-3 composites were fabricated using the dice and fill method. The epoxy filler was modified with glass spheres in order to improve the thermal reliability of the composites at elevated temperatures. Temperature dependent dielectric and electromechanical properties of the composites were measured after aging at 250°C with different dwelling times. Obvious cracks were observed and the electrodes were damaged in the composite with unmodified epoxy after 200 hours, leading to the failure of the composite. In contrast, composites with >12 vol% glass sphere loaded epoxies were found to exhibit minimal electrical property variation after aging for 500 hours, with dielectric permittivity, piezoelectric coefficient and electromechanical coupling being on the order of 940, 310pC/N and 57%, respectively. This is due to the improved thermal expansion behavior of the modified filler.

Critical Property in Relaxor-PbTiO(3) Single Crystals --- Shear Piezoelectric Response.

The shear piezoelectric behavior in relaxor-PbTiO(3) (PT) single crystals is investigated in regard to crystal phase. High levels of shear piezoelectric activity, d(15) or d(24) >2000 pC N(-1), has been observed for single domain rhombohedral (R), orthorhombic (O) and tetragonal (T) relaxor-PT crystals. The high piezoelectric response is attributed to a flattening of the Gibbs free energy at compositions proximate to the morphotropic phase boundaries, where the polarization rotation is easy with applying perpendicular electric field. The shear piezoelectric behavior of pervoskite ferroelectric crystals was discussed with respect to ferroelectric-ferroelectric phase transitions and dc bias field using phenomenological approach. The relationship between single domain shear piezoelectric response and piezoelectric activities in domain engineered configurations were given in this paper. From an application viewpoint, the temperature and ac field drive stability for shear piezoelectric responses are investigated. A temperature independent shear piezoelectric response (d(24), in the range of -50°C to O-T phase transition temperature) is thermodynamically expected and experimentally confirmed in orthorhombic relaxor-PT crystals; relatively high ac field drive stability (5 kV cm(-1)) is obtained in manganese modified relaxor-PT crystals. For all thickness shear vibration modes, the mechanical quality factor Qs are less than 50, corresponding to the facilitated polarization rotation.

Influence of Domain Size on the Scaling Effects in Pb(Mg1/3Nb2/3)O3-PbTiO3 Ferroelectric Crystals.

The property degradation observed in thin Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PMN-PT) crystals is believed to relate to large domains and subsequent clamping induced by surface-boundary. In this work, the properties were investigated as function of domain size, using controlled poling. The degraded piezoelectric and dielectric properties of thin PMN-PT were found to increase significantly, by decreasing domain size. Furthermore, the fine domain structure was found to be stable at 3kV/cm after 7.0×10(5) negative-pulse cycles, hence, enabling PMN-PT crystals for high-frequency (>20 MHz) ultrasound-transducers.

Recent Developments on High Curie Temperature PIN-PMN-PT Ferroelectric Crystals.

Pb(In(0.5)Nb(0.5))O(3)-Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PIN-PMN-PT) ferroelectric crystals attracted extensive attentions in last couple years, due to their higher usage temperatures range (> 30°C) and coercive fields (~5kV/cm), meanwhile maintaining similar electromechanical couplings (k(33)> 90%) and piezoelectric coefficients (d(33)~1500pC/N), when compared to their binary counterpart Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3). In this article, we reviewed recent developments on the PIN-PMN-PT single crystals, including the Bridgman crystal growth, dielectric, electromechanical, piezoelectric and ferroelectric behaviors as function of temperature and dc bias. Mechanical quality factor Q was studied as function of orientation and phase. Of particular interest is the dynamic strain, which related to the Q and d(33), was found to be improved when compared to binary system, exhibiting the potential usage of PIN-PMN-PT in high power application. Furthermore, PIN-PMN-PT crystals exhibit improved thickness dependent properties, due to their small domain size, being on the order of 1µm. Finally, the manganese acceptor dopant in the ternary crystals was investigated and discussed briefly in this paper.

Thickness Dependent Properties of Relaxor-PbTiO(3) Ferroelectrics for Ultrasonic Transducers.

The electrical properties of Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PMN-PT) based polycrystalline ceramics and single crystals were investigated as a function of scale ranging from 500 microns to 30 microns. Fine-grained PMN-PT ceramics exhibited comparable dielectric and piezoelectric properties to their coarse-grained counterpart in the low frequency range (<10 MHz), but offered greater mechanical strength and improved property stability with decreasing thickness, corresponding to higher operating frequencies (>40 MHz). For PMN-PT single crystals, however, the dielectric and electromechanical properties degraded with decreasing thickness, while ternary Pb(In(1/2)Nb(1/2))O(3)-Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PIN-PMN-PT) exhibited minimal size dependent behavior. The origin of property degradation of PMN-PT crystals was further studied by investigating the dielectric permittivity at high temperatures, and domain observations using optical polarized light microscopy. The results demonstrated that the thickness dependent properties of relaxor-PT ferroelectrics are closely related to the domain size with respect to the associated macroscopic scale of the samples.

Polarization Fatigue in Pb(In(0.5)Nb(0.5))O(3)-Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) Single Crystals.

Electric fatigue tests have been conducted on pure and manganese modified Pb(In(0.5)Nb(0.5))O(3)-Pb(Mg(1/3)Nb(2/3))O(3)-PbTiO(3) (PIN-PMN-PT) single crystals along different crystallographic directions. Polarization degradation was observed to suddenly occur above 50-100 bipolar cycles in <110> oriented samples, while <001> oriented samples exhibited almost fatigue free characteristics. The fatigue behavior was investigated as a function of orientation, magnitude of the electric field and manganese dopant. It was found that <001> oriented PIN-PMN-PT crystals were fatigue free, due to its small domain size, being on the order of 1µm. The <110> direction exhibited a strong electrical fatigue behavior due to mechanical degradation. Micro/macro cracks were developed in fatigued <110> oriented single crystals. Fatigue and cracks were the results of strong anisotropic piezoelectric stress and non-180° domain switching, which completely locked the non-180° domains. Furthermore, manganese modified PIN-PMN-PT crystals were found to show improved fatigue behavior due to its enhanced coercive field.

New Sm-PMN-PT Ceramic-Based 2-D Array for Low-Intensity Ultrasound Therapy Application.

A two-dimensional (2-D) array with a small pitch (approximately 0.5λ in medium) can achieve complete 3-D control of ultrasound beams without grating lobes and enable the generation of multiple focal spots simultaneously, which is a desired tool for noninvasive therapy. However, the large electrical impedance of 2-D array elements owing to their small size results in a low energy transfer efficiency between a 2-D array and an electrical system, thereby limiting their practical applications. This article presents the development of a 1-MHz 256-element 2-D array ultrasonic transducer of low electrical impedance based on a new Sm-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (Sm-PMN-PT) piezoceramic with ultrahigh dielectric permittivity. The electrical impedance of the array element is decreased by 3.4 times as the Sm-PMN-PT replacing commercial PZT-5H. Consequently, the output acoustic pressure of the 2-D array made of Sm-PMN-PT ceramic is approximately twice that of the 2-D array made of PZT-5H ceramic under the same excitation conditions. Array elements are spaced at a 1.1-mm pitch ( 0.71λ in water), enabling a large steering range of the ultrasound beam. A multiple-target blood-brain barrier opening in vivo is demonstrated using the proposed 2-D array with electronic focusing and steering. The obtained results indicate that the 2-D array made of Sm-PMN-PT ceramic is promising for practical use in low-intensity ultrasound therapy applications.

Giant piezoelectricity of Sm-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 single crystals.

High-performance piezoelectrics benefit transducers and sensors in a variety of electromechanical applications. The materials with the highest piezoelectric charge coefficients (d 33) are relaxor-PbTiO3 crystals, which were discovered two decades ago. We successfully grew Sm-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (Sm-PMN-PT) single crystals with even higher d 33 values ranging from 3400 to 4100 picocoulombs per newton, with variation below 20% over the as-grown crystal boule, exhibiting good property uniformity. We characterized the Sm-PMN-PT on the atomic scale with scanning transmission electron microscopy and made first-principles calculations to determine that the giant piezoelectric properties arise from the enhanced local structural heterogeneity introduced by Sm3+ dopants. Rare-earth doping is thus identified as a general strategy for introducing local structural heterogeneity in order to enhance the piezoelectricity of relaxor ferroelectric crystals.

High-Performance Ultrasound Needle Transducer Based on Modified PMN-PT Ceramic With Ultrahigh Clamped Dielectric Permittivity.

A modified Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) polycrystalline ceramic with ultrahigh relative clamped dielectric permittivity ( ) and high piezoelectric properties ( pC/N, ) was used to fabricate high-frequency miniature ultrasound transducers. A 39-MHz high-frequency ultrasound needle transducer with a miniature aperture of 0.4 mm mm was designed and successfully characterized. The fabricated needle transducer had an electromechanical coupling factor of 0.55, large bandwidth of 80% at -6 dB, and low insertion loss of -13 dB. A wire phantom and porcine eyeball imaging study showed good imaging capability of this needle transducer. The transducer performance was found to be superior to that of other needle transducers with miniature apertures, making this modified PMN-PT ceramic-based needle transducer quite promising for minimally invasive procedures in medical applications.

Piezoelectric properties in (K0.5Bi0.5)TiO3-(Na0.5Bi0.5)TiO3-BaTiO3 lead-free ceramics.

Lead-free piezoelectric ceramics with compositions around the morphotropic phase boundary (MPB) x(Na0.5Bi0.5)TiO3-y(K0.5Bi0.5)TiO3-zBaTiO3 [x + y + z = 1; y:z = 2:1] were synthesized using conventional, solid-state processing. Dielectric maximum temperatures of 280 degrees C and 262 degrees C were found for tetragonal 0.79(Na0.5Bi0.5)TiO3-0.14(K0.5Bi0.5)TiO3-0.07BaTiO3 (BNBK79) and MPB composition 0.88(Na0.5Bi0.5)TiO3-0.08(K0.5Bi0.5)TiO3-0.04BaTiO3 (BNBK88), with depolarization temperatures of 224 degrees C and 162 degrees C, respectively. Piezoelectric coefficients d33 were found to be 135 pC/N and 170 pC/N for BNBK79 and BNBK88, and the piezoelectric d31 was determined to be -37 pC/N and -51 pC/N, demonstrating strong anisotropy. Coercive field values were found to be 37 kV/cm and 29 kV/cm for BNBK79 and BNBK88, respectively. The remanent polarization of BNBK88 (approximately 40 microC/cm2) was larger than that of BNBK79 (approximately 29 microC/cm2). The piezoelectric, electromechanical, and high-field strain behaviors also were studied as a function of temperature and discussed.

High-frequency ultrasound annular-array imaging. Part I: array design and fabrication.

This is Part I of a series of two papers describing the development of a digital high-frequency, annular-array, ultrasonic imaging system. In this paper, the design and fabrication of a high-frequency annular array as well as its performance will be reported. A six-element, 50 MHz array, which incorporated an acoustic lens to provide an initial focal point, was designed and fabricated. A submicron size grain lead titanate piezoelectric ceramic was used to both reduce lateral coupling and keep the electrical impedance matched close to the 50 ohm receive electronics. The array elements were isolated using laser micromachining to fully separate the annuli, and electrical interconnection was achieved by directly soldering thin wires to the elements. The resulting array attained an average impulse response that exhibited a 43 MHz center frequency, 30% relative bandwidth, and an average insertion loss of 31 dB at 45 MHz. Maximum next-element crosstalk was -27 dB in water.

New Pb(Mg1/3Nb2/3)O3-Pb(In1/2Nb1/2)O3-PbZrO3-PbTiO3 Quaternary Ceramics: Morphotropic Phase Boundary Design and Electrical Properties.

Four series of Pb(Mg1/3Nb2/3)O3-Pb(In1/2Nb1/2)O3-PbZrO3-PbTiO3 (PMN-PIN-PZ-PT) quaternary ceramics with compositions located at the morphotropic phase boundary (MPB) regions were prepared. The MPBs of the multicomponent system were predicted using a linear combination rule and experimentally confirmed by X-ray powder diffraction and electrical measurement. The positions of MPBs in multicomponent systems were found in linear correlation with the tolerance factor and ionic radii of non-PT end-members. The phase structure, piezoelectric coefficient, electromechanical coupling coefficient, unipolar strains, and dielectric properties of as-prepared ceramics were systematically investigated. The largest d33s were obtained at S36.8, L37.4, M39.6, and N35.8, with the corresponding values of 580, 450, 420, and 530 pC/N, respectively, while the largest kps were found at S34.8, L37.4, M39.6, and N35.8, with the respective values of 0.54, 0.50, 0.47, and 0.53. The largest unipolar strain Smax and high-field piezoelectric strain coefficients d33* were also observed around the respective MPB regions. The rhombohedral-to-tetragonal phase transition temperature Trt increased with increasing PIN and PZ contents. Of particular importance is that high Trt of 140-197 °C was achieved in the M series with PZ and PIN contents being around 0.208 and 0.158, which will broaden the temperature usage range.

The origin of ultrahigh piezoelectricity in relaxor-ferroelectric solid solution crystals.

The discovery of ultrahigh piezoelectricity in relaxor-ferroelectric solid solution single crystals is a breakthrough in ferroelectric materials. A key signature of relaxor-ferroelectric solid solutions is the existence of polar nanoregions, a nanoscale inhomogeneity, that coexist with normal ferroelectric domains. Despite two decades of extensive studies, the contribution of polar nanoregions to the underlying piezoelectric properties of relaxor ferroelectrics has yet to be established. Here we quantitatively characterize the contribution of polar nanoregions to the dielectric/piezoelectric responses of relaxor-ferroelectric crystals using a combination of cryogenic experiments and phase-field simulations. The contribution of polar nanoregions to the room-temperature dielectric and piezoelectric properties is in the range of 50-80%. A mesoscale mechanism is proposed to reveal the origin of the high piezoelectricity in relaxor ferroelectrics, where the polar nanoregions aligned in a ferroelectric matrix can facilitate polarization rotation. This mechanism emphasizes the critical role of local structure on the macroscopic properties of ferroelectric materials.

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 TR-T--the rhombohedral to tetragonal phase transformation temperature--which occurs a significantly lower temperatures than the Curie temperature Tc. Attempts to modify the temperature usage range of Pb(Zn1/3Nb2/3)O3--PbTiO3 (PZNT) and Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMNT) rhombohedral crystals (Tx to approximately 150-170 degrees C, TR-T to approximately 60-120 degrees C) using minor dopant modifications were limited, with little success. Of significant potential are crystals near the mor photropic phase boundary in the Pb(Yb1/2Nb1/2)O3-PbTiO3 (PYNT) system, with a Tc > 330 degrees C, even thoug TR-T was found to be only half that value at approximately 160 degrees C. Single crystals in the novel BiScO3-PbTiO3 system offer significantly higher Tcs > 400 degrees C, while exhibiting electromechanical coupling coefficients k33 > 90% being nearly constant till the TR-T temperature around 350 degrees C, which greatly increases the temperature range for transducer applications.

Elastic, piezoelectric, and dielectric characterization of modified BiScO3-PbTiO3 ceramics.

The perovskite solid solution system (1-x)BiScO3-(x)PbTiO3 represents an interesting new family of high-temperature piezoelectric materials. Compositions near the morphotropic phase boundary (x approximately 0.64) have been reported to have high Curie temperatures (Tc > 450 degrees C) and good piezoelectric coefficients (d33 approximately 460 pC/N). In this work, manganese additions were used to improve the high-temperature electrical resistivity and RC time constant of compositions near the morphotropic phase boundary. The addition of manganese was found to shift Tc to slightly lower temperatures (442 degrees C and 456 degrees C for x = 0.64 and x = 0.66, respectively). The piezoelectric activities of the modified materials were found to be reduced slightly due to the hardening effect of manganese; however, the temperature stability and resistivity of the modified materials were significantly enhanced. In this paper we present, for the first time, a complete set of materials constants, including the elastic (sij, cij), piezoelectric (dij, eij, gij, hij), dielectric (epsilonij, betaij), and electromechanical (kij) coefficients and compare them to both unmodified 0.36BiScO3-0.64PbTiO3 and PZT5A ceramics.

Variation of Piezoelectric properties and mechanisms across the relaxor-like/Ferroelectric continuum in BiFeO3- (K0.5Bi0.5)TiO3-PbTiO3 ceramics.

1- x - y)BiFeO3-x(K0.5Bi0.5)TiO3-yPbTiO3 (BFKBT- PT) piezoelectric ceramics were investigated across the compositional space and contrasted against the xBiFeO3- (1-x)(K0.5Bi0.5)TiO3 (BF-KBT) system, whereby a range of relaxor-like/ferroelectric behavior was observed. Structural and piezoelectric properties were closely related to the PbTiO3 concentration; below a critical concentration, relaxor-like behavior was identified. The mechanisms governing the piezoelectric behavior were investigated with structural, electrical, and imaging techniques. X-ray diffraction established that longrange non-centrosymmetric crystallographic order was evident above a critical PbTiO3 concentration, y > 0.1125. Commensurate with the structural analysis, electric-field-induced strain responses showed electrostrictive behavior in the PbTiO3-reduced compositions, with increased piezoelectric switching in PbTiO3-rich compositions. Positive-up-negative-down (PUND) analysis was used to confirm electric-field-induced polarization measurements, elucidating that the addition of PbTiO3 increased the switchable polarization and ferroelectric ordering. Piezoresponse force microscopy (PFM) of the BF-KBT-PT system exhibited typical domain patterns above a critical PbTiO3 threshold, with no ferroelectric domains observed in the BF-KBT system in the pseudocubic region. Doping of BiFeO3-PbTiO3 has been unsuccessful in the search for hightemperature materials that offer satisfactory piezoelectric properties; however, this system demonstrates that the partial substitution of alternative end-members can be an effective method. The partial substitution of PbTiO3 into BF-KBT enables long-range non-centrosymmetric crystallographic order, resulting in increased polar order and TC, compared with the pseudocubic region. The search for novel high-temperature piezoelectric ceramics can therefore exploit the accommodating nature of the perovskite family, which allows significant variance in chemical and physical characters in the exploration of new solid-solutions.

Electromechanical properties of fine-grain, 0.7 Pb(Mg(1/3)Nb(2/3))O3-0.3PbTiO3 ceramics.

A fine grain, relaxor-based piezoelectric ceramic 0.7 Pb(Mg(1/3)Nb(2/3))O3-0.3PbTiO3 (PMN-30% PT) has been investigated, which was fabricated using the columbite precursor method. The complete set of electromechanical properties of the piezoceramic at room temperature is determined using a combination of ultrasonic and resonance techniques. This fine-grain ceramic (grain size < or = 2.5 microm) exhibits ultra-high dielectric permittivity (epsilon33(T)/epsilon0 approximately 7000) and a high coupling coefficient k(33) (= 0.78). Ultrasonic spectroscopy was used to measure the dispersion of the phase velocity and attenuation for the longitudinal wave propagating in the poling direction. Lower attenuation and smaller velocity dispersion were observed compared to modified Pb(Zr(x)Ti(1-x)O3 (PZT-5H) ceramics. The measurement results show that this fine-grain PMN-30% PT ceramic is a very good material for making ultrasonic array transducers.

A 30-MHz piezo-composite ultrasound array for medical imaging applications.

Ultrasound imaging at frequencies above 20 MHz is capable of achieving improved resolution in clinical applications requiring limited penetration depth. High frequency arrays that allow real-time imaging are desired for these applications but are not yet currently available. In this work, a method for fabricating fine-scale 2-2 composites suitable for 30-MHz linear array transducers was successfully demonstrated. High thickness coupling, low mechanical loss, and moderate electrical loss were achieved. This piezo-composite was incorporated into a 30-MHz array that included acoustic matching, an elevation focusing lens, electrical matching, and an air-filled kerf between elements. Bandwidths near 60%, 15-dB insertion loss, and crosstalk less than -30 dB were measured. Images of both a phantom and an ex vivo human eye were acquired using a synthetic aperture reconstruction method, resulting in measured lateral and axial resolutions of approximately 100 microm.