Electric-field-induced strain and piezoelectric properties of a high Curie temperature Pb(In1/2Nb1/2)O3-PbTiO3 single crystal

The temperature dependence of dielectric and piezoelectric properties, electric-field-induced strains of 0.66 Pb(In_1/2Nb_1/2)O₃-0.34 PbTiO₃ single crystals, which were grown directly from melt by using the modified Bridgman technique with the allomeric Pb(Mg_2/3Nb_1/3)O₃-PbTiO₃ seed crystals, were determined as a function of crystallographic orientation with respect to the prototypic (cubic) axes. Ultrahigh piezoelectric response (d₃₃∼2000 pC/N, k₃₃∼94%) and strain levels up to 0.8%, comparable to rhombohedral (1−x)Pb(Mg_2/3Nb_1/3)O₃-xPbTiO₃ and (1−x)Pb(Zn_2/3Nb_1/3)O₃-xPbTiO₃ single crystals, were observed for the 〈0 0 1〉-oriented crystals. Strain levels up to 0.47% and piezoelectric constant d₃₃∼1600 pC/N could be achieved being related to an electric-field-induced rhombohedral-orthorhombic phase transition for the 〈1 1 0〉-oriented crystals. In addition, high electromechanical coefficients k₃₃ (∼88%) can be achieved even heating to 110 °C. High T_C (∼200 °C), large electromechanical coefficients k₃₃ (∼94%) and low dielectric loss factor (∼1%), along with large strain make the crystals promising candidates for a wide range of electromechanical transducers.     

Comparative investigation of structure and dielectric properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 (65/35) and 10% PbZrO3-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (65/35) ceramics prepared by a modified precursor method

Relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) and 10% PbZrO₃-doped Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramics were both prepared by a modified precursor method, which was based on the high-temperature synthesis of an oxide precursor that contained all the B-site cations for the consideration of B-site homogeneity. The dielectric properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramic was more of normal ferroelectric behavior, but the high dielectric constant (?_m = 34,200 at 1 kHz) and piezoelectric constant (d₃₃ = 709 pC/N) were observed for this composition close to the morphotropic phase boundary. Comparatively, introduction of 10% PbZrO₃ into Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramics enhanced the diffuse phase transition as well as the rhombohedral to tetragonal phase transition temperature, while it also kept the high dielectric constant (?_m = 29,600 at 1 kHz) and piezoelectric constant (d₃₃ = 511 pC/N).     

Effect of Pb(Fe1/2Nb1/2)O3 modification on dielectric and piezoelectric properties of Pb(Mg1/3Nb2/3)O3-PbZr0.52Ti0.48O3 ceramics

10 mol% Pb(Fe_1/2Nb_1/2)O₃ (PFN) modified Pb(Mg_1/3Nb_2/3)O₃-PbZr_0.52Ti_0.48O₃ (PMN-PZT) relaxor ferroelectric ceramics with compositions of (0.9 − x)PMN-0.1PFN-xPZT (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9) were prepared. X-ray diffraction investigations indicated that as-prepared ceramics were of pure perovskite phase and the sample with composition of x = 0.8 was close to morphotropic phase boundary (MPB) between rhombohedral and tetragonal phase. Dielectric properties of the as-prepared ceramics were measured, and the Curie temperature (T_c) increased sharply with increasing PZT content and could be higher than 300 °C around morphotropic phase boundary (MPB) area. At 1 kHz, the sample with composition of x = 0.1 had the largest room temperature dielectric constant ?_r = 3519 and maximum dielectric constant ?_m = 20,475 at T_m, while the sample with composition of x = 0.3 possessed the maximum dielectric relaxor factor of γ = 1.94. The largest d₃₃ = 318 pC/N could be obtained from as-prepared ceramics at x = 0.9. The maximum remnant polarization (P_r = 28.3 μC/cm²) was obtained from as-prepared ceramics at x = 0.4.     

The influence of defects on ferroelectric and pyroelectric properties of Pb(Mg1/3Nb2/3)O3-0.28PbTiO3 single crystals

Relaxor-based ferroelectric single crystals 0.72Pb(Mg_1/3Nb_2/3)O₃-0.28PbTiO₃ (PMN-0.28PT) were grown by a modified Bridgman technique. The direct current (dc) conductivity was investigated and corresponding conduction mechanisms were discussed. V^″Pb−VO defects are dominant from 245 °C to 650 °C. The ferroelectric properties of [1 1 1]-oriented PMN-0.28PT were systematically investigated, with the coercive field (E_c) of 5.2 kV cm⁻¹ and remnant polarization (P_r) of 37.8 μC cm⁻² at room temperature. Moreover, the dielectric and pyroelectric performances of PMN-0.28PT were measured and the integrated pyroelectric performances greatly enhanced after annealing in oxygen at 500 °C for 20 h. This is due to the decrease of oxygen vacancies in the single crystals when being annealed in the oxygen-rich atmosphere. These make [1 1 1]-oriented PMN-0.28PT crystals a promising candidate for infrared detectors and thermal imagers used at room temperature.     

Stoichiometric Pb(Mg1/3Nb2/3)O3 perovskite ceramics produced by reaction-sintering process

Stoichiometric lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), perovskite ceramics produced by reaction-sintering process were investigated. Without calcination, a mixture of PbO, Nb₂O₅, and Mg(NO₃)₂ was pressed and sintered directly. Stoichiometric PMN ceramics of 100% perovskite phase were obtained for 1, 2, and 4 h sintering at 1250 and 1270 °C. PMN ceramics with density 8.09 g/cm³ (99.5% of theoretical density 8.13 g/cm³) and K_max 19,900 under 1 kHz were obtained.     

Neutron powder diffraction and magnetic study of perovskites Pb(Mn1/2Nb1/2)O3 and Pb(Mn1/4Fe1/4Nb1/2)O3

The structural and magnetic properties of the complex metal oxides Pb(Mn_1/2Nb_1/2)O₃ (PMNO) and Pb(Mn_1/4Fe_1/4Nb_1/2)O₃ (PMFNO), which belong to a class of disordered perovskites have been studied. The magnetic susceptibilities of PMNO showed hysteresis between field cooled and zero-field cooled conditions below the transition of 15 K, suggesting that the material has a spin-glass feature. Neutron diffraction patterns of PMNO showed no evidence of a long-range magnetic ordering at 1.5 K, which is consistent with spin-glass behavior. Rietveld refinements of neutron powder diffraction data collected at different temperatures between 1.5 and 700 K have been carried out in order to extract structural information. The crystal structure of this compound is cubic (space group Pmm) within the whole temperature interval. The Mn and Nb ions were found to be disordered over the perovskite B-sites. The main feature of this structure is the positional disorder at the Pb site, the importance of which in connection with the ferroic transitions is briefly discussed. The Pb cations show a positional disorder shifting from their high-symmetry positions along the [1 1 1] direction. The effect of Fe-doping on PMNO has been studied. The substitution of Fe at the Mn site in PMFNO results in a small changes of the magnetic properties without significant differences in the crystal structures. The factors governing the observed structural and magnetic properties of PMNO and PMFNO are discussed and compared with those of other quaternary Mn-containing perovskites. For the PbB³⁺_1/2Nb_1/2O₃ series with the isomorphous substitution B³⁺, graphs of average lattice parameters of the perovskite phase and the temperatures of ferroelectric and magnetic phase transitions as functions of the B³⁺ cation radius were constructed and are discussed. Influence of A-cation sublattice on magnetic properties is also considered.     

Triple-like hysteresis loop and microdomain-macrodomain transformation in the relaxor-based 0.76Pb(Mg1/3Nb2/3)O3-0.24PbTiO3 single crystal

Polarization and depolarization behavior of the relaxor-based 0.76Pb(Mg_1/3Nb_2/3)O₃-0.24PbTiO₃ single crystal has been studied between 25 and 200 °C by means of dielectric measurement with or without dc bias, Polarization-Electric field (P-E) hysteresis loop and discharging current measurements. Triple-like P-E loops were obtained in a temperature range between 80 and 90 °C, disclosing the transformation between microdomain state and metastable macrodomain state. For the poled crystals, the microdomain state with dipoles partially oriented was indicated to exist in the similar temperature range and mediate between the lower temperature macrodomain state with dipoles oriented and the higher temperature microdomain state with dipoles in a random system.     

Electrical properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 ceramics modified with WO3

Ferroelectrics 0.67Pb (Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ (PMN-PT) + x mol% WO₃ (x=0.1, 0.5, 1, 2) were prepared by columbite precursor method. Electrical properties of WO₃-modified ferroelectrics were investigated. X-ray diffraction (XRD) was used to identify crystal structure, and pyrochlore phase were observed in 0.67Pb (Mg_1/3Nb_2/3)O₃-0.33PbTiO₃+2 mol% WO₃. Dielectric peak temperature decreased with WO₃ doping, indicating that W⁶⁺ incorporated into PMN-PT lattice. Lattice constant, pyrochlore phase and grain size contribute to the variation of K_max. Both piezoelectric constant (d₃₃) and electromechanical coupling factors (k_p) were enhanced by doping 0.1 mol% WO₃, which results from the introduction of “soft” characteristics into PMN-PT, while further WO₃ addition was detrimental. We consider that the two factors, introduction of “soft” characteristics and the formation of pyrochlore phase, appear to act together to cause the variation of piezoelectric properties of 0.67PMN-0.33PT ceramics doping with WO₃.     

Crystal structures of KBa2Nb5O15 and LaK2Nb5O15 with the TTB-type structure

Single crystals of two niobates, KBa₂Nb₅O₁₅ and LaK₂Nb₅O₁₅, were synthesized by high-temperature reaction and the crystal structures were determined by single crystal X-ray diffraction data. Although the space groups for these compounds were different (the non-centrosymmetrical space group P4bm (#100) for KBa₂Nb₅O₁₅ and the centrosymmetrical one P4/mbm (#127) for LaK₂Nb₅O₁₅), both compounds had the same tetragonal tungsten bronze-type (hereafter TTB-type) structure. The lattice parameters and R-factors of KBa₂Nb₅O₁₅ (LaK₂Nb₅O₁₅) were a = 12.533(2) (12.563(2)) and c = 4.0074(9) (3.9179(9)) Å, and R₁ = 0.040 (0.047) and wR₂=0.131 (0.120), respectively. From the crystal structural analysis, it was clarified that distribution of two large cations was different from each other in the way that K and Ba atoms in KBa₂Nb₅O₁₅ were distributed statistically at two crystallographic sites and K and La atoms in LaK₂Nb₅O₁₅ were ordered.     

Nb NMR and Fe EPR study of local magnetic properties of magnetoelectric Pb(Fe1/2Nb1/2)O3

The ⁹³Nb NMR and Fe³⁺ EPR spectra of a magnetoelectric Pb(Fe_1/2Nb_1/2)O₃ (PFN) single crystal as well as of PFN ceramics and nanopowder have been measured. The relation between the chemical disorder and the local magnetic structure has been determined. The data show the occurrence of an antiferromagnetic (AFM) phase transition at 145 and 135 K in both single crystal and ceramic samples, respectively. The AFM phase transition is however essentially smeared out in the nanopowder. Two different Nb sites exist which have different local magnetic fields which are essentialy distributed in value. These two Nb sites correspond to different types of “chemical” order: Fe rich, Nb poor and Fe poor, Nb rich regions. The temperature dependences of the sublattice magnetizations and the values of the superhyperfine fields at the Nb ions are obtained. NMR data suggest that a spin-glass like state of PFN below T = 20 K arises from the Fe poor, Nb rich regions.     

Effect of doping with Nd ions on the structural and ferroelectric properties of Ca0.28Ba0.72Nb2O6 single crystal

The crystal structure of Ca_0.28Ba_0.72Nb₂O₆ (CBN-28) crystal with Nd-doping has been determined from X-ray single crystal diffraction data, in the tetragonal system with space group P4bm and the following parameters: a = b = 12.458 Å, c = 3.954 Å, V = 613.688 Å³, and Z = 5. X-ray diffraction results on a Nd-doped CBN-28 single crystal also have demonstrated that Nd³⁺ and Ca²⁺ occupy the same site in the crystal structure. Dielectric and ferroelectric measurements have been performed. Transition from ferroelectric to paraelectric at around 223 °C has been observed. The Nd-doped crystal has a lower Curie temperature (T_m) than that of undoped CBN-28 crystal. The spontaneous polarization (P_s) and coercive electric field (E_c) also decrease compared with their values in the undoped CBN-28 crystal.     

Enhanced ferroelectric properties of Pb(Zr0.80Ti0.20)O3/PbO thin films prepared by radio frequency magnetron sputtering

The Pb(Zr_0.80Ti_0.20)O₃ (PZT) thin films with and without a PbO buffer layer were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by radio frequency (rf) magnetron sputtering method. The PbO buffer layer improves the microstructure and electrical properties of the PZT thin films. High phase purity and good microstructure of the PZT thin films with a PbO buffer layer were obtained. The effect of the PbO buffer layer on the ferroelectric properties of the PZT thin films was also investigated. The PZT thin films with a PbO buffer layer possess better ferroelectric properties with higher remnant polarization (P_r = 25.6 μC/cm²), and lower coercive field (E_c = 60.5 kV/cm) than that of the films without a PbO buffer layer (P_r = 9.4 μC/cm², E_c = 101.3 kV/cm). Enhanced ferroelectric properties of the PZT thin films with a PbO buffer layer is attributed to high phase purity and good microstructure.     

Distribution of pyrochlore phase in Pb(Mg1/3Nb2/3)O3-PbTiO3 films and suppression with a Pb(Zr0.52Ti0.48)O3 interfacial layer

Thin films of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) on Pt/Ti/SiO₂/Si (Pt/Si) substrates both with and without a Pb(Zr_0.52Ti_0.48)O₃ (PZT) interfacial layer were investigated. Perovskite and pyrochlore coexistence was observed for PMN-PT thin films without a PZT interfacial layer. Interestingly, most of the pyrochlore phase was observed in single-coated films and in the first layer of multi-coated films. The pyrochlore phase exhibited grains with an average size of about 25 nm, which is smaller than those of the perovskite phase (about 90 nm). In contrast, for PMN-PT thin films grown on a PZT interfacial layer, the formation of a pyrochlore phase at the interface between PMN-PT layers and the substrate is completely suppressed. Moreover, small grains are not observed in the films with a PZT interfacial layer. The measured polarization-electric field (P-E) hysteresis loops of PMN-PT films with and without PZT layers indicate that enhanced electrical properties can be obtained when a PZT interfacial layer is used. These enhanced properties include an increase in the value of remanent polarization P_r from 2.7 to 5.8 μC/cm² and a decrease in the coercive field E_c from 60.5 to 28.0 kV/cm.     

Effect of MnO2 addition on the piezoelectric properties in Pb(Mg1/3Nb2/3)O3 relaxor ferroelectrics

The effects of MnO₂ addition on the piezoelectric properties in Pb(Mg_1/3Nb_2/3)O₃ relaxor ferroelectrics were studied in the ferroelectricity-dominated temperature range from −40 to 30°C. Dielectric, piezoelectric, and electrostrictive properties were examined to clarify the effect of MnO₂ addition. As an added amount of MnO₂ increases, the dielectric constant decreases and the mechanical quality factor increases in Pb(Mg_1/3Nb_2/3)O₃. From the experimental results, it has been found that Mn behaves as a ferroelectric domain pinning element.     

Growth and properties of Ca0.28Ba0.72Nb2O6 single crystals

Calcium barium niobate Ca_0.28Ba_0.72Nb₂O₆ (CBN-28) crystals were successfully grown by the Czochralski method. X-ray powder diffraction experiments indicated that CBN single crystals are tetragonal with a = 12.432(±0.002) Å and c = 3.957(±0.001) Å, which have almost the same structure as the Sr_0.50Ba_0.50Nb₂O₆ (SBN-50) crystal. The thermal expansion coefficient perpendicular to Z-direction had been measured to be 1.25 × 10⁻⁵ K⁻¹ between 293.15 and 572.15 K, and along Z-axis was negative between 298.15 and 543.15 K. The specific heat of the crystal had been measured by the differential scanning calorimetric experiments. The transmittance spectra from 200 to 3200 nm were also measured. The measured temperature dependence of dielectric constants showed that the Curie temperature of the CBN-28 crystals is 260 °C, which is about 200 °C higher than that of the (SBN) crystal.     

Piezoelectric shear-mode properties of Pb(Yb1/2Nb1/2)O3-PbTiO3 ceramics

A Pb(Yb_1/2Nb_1/2)O₃-PbTiO₃ [PYNT] solid solution was synthesized and characterized for its potential use. The shear-mode dielectric and piezoelectric behaviors of PYNT with a morphotropic phase boundary (MPB) composition were studied as a function of temperature. Dielectric permittivity K₁₁^T and loss were found to be 2310 and 2.5%, respectively, at room temperature. Piezoelectric coefficient d₁₅ and electromechanical coupling factor k₁₅ were calculated to be 710 pC/N and 0.70, respectively, maintaining nearly constant up to 300 °C, resistivity and RC time constant were observed to be 2.4 × 10⁹ Ω cm and 1.07 s, respectively, at 350 °C. These good piezoelectric properties, together with the high Curie temperature (T_c ∼ 370 °C), indicate that PYNT is a promising candidate for high temperature-shear sensor and inkjet actuator applications.     

Effects of Fe2O3 doping on the microstructure and piezoelectric properties of 0.55Pb(Ni1/3Nb2/3)O3-0.45Pb(Zr0.3Ti0.7)O3 ceramics

0.55Pb(Ni_1/3Nb_2/3)O₃-0.45Pb(Zr_0.3Ti_0.7)O₃(PNN-PZT) ceramics with different concentration of xFe₂O₃ doping (where x = 0.0, 0.8, 1.2, 1.6 mol%) were synthesized by the conventional solid state sintering technique. X-ray diffraction analysis reveals that all specimens are a pure perovskite phase without pyrochlore phase. The density and grain size of Fe-doped ceramics tend to increase slightly with increasing concentration of Fe₂O₃. Comparing with the undoped ceramics, the piezoelectric, ferroelectric and dielectric properties of the Fe-doped PNN-PZT specimens are significantly improved. Properties of the piezoelectric constant as high as d₃₃ ~ 956 pC/N, the electromechanical coupling factor k_p ~ 0.74, and the dielectric constant ε_r ~ 6095 are achieved for the specimen with 1.2 mol% Fe₂O₃ doping sintered at 1200 °C for 2 h.     

Effects of Mn doping on the structure and electrical properties of high-temperature BiScO3-PbTiO3-Pb(Zn1/3Nb2/3)O3 piezoelectric ceramics

The effects of Mn addition on the structure, ferroelectric, and piezoelectric properties of the 0.35BiScO₃-0.60PbTiO₃-0.05Pb(Zn_1/3Nb_2/3)O₃ ceramics were studied. The results demonstrate that the addition of small amounts of Mn did not cause a remarkable change in crystal structure, but resulted in an evident evolution in microstructure and ferro-piezoelctric properties. The addition of Mn can induce combinatory “hard” and “soft” piezoelectric characteristics due to aliovalent substitutions. The optimal electrical properties are obtained in the 0.25 mol% Mn-doped composition with a high Curie temperature, indicating that Mn doping contributes to the electrical properties of the ceramics. It can be expected that the improved piezoelectric material can be a promising candidate for high-temperature piezoelectric applications.     

Morphotropic phase boundary in Pb(Sc1/2Nb1/2)O3-BiScO3-PbTiO3 high temperature piezoelectrics

The solid solutions in the 0.36BiScO₃-0.64(1 − x)PbTiO₃-0.64xPb(Sc_1/2Nb_1/2)O₃ system were fabricated using wolframite precursor method. A coexistence of rhombohedral and tetragonal phases is formed in the studied compositions range and a wide morphotropic phase boundary region is confirmed by X-ray diffraction results. After the addition of Pb(Sc_1/2Nb_1/2)O₃, a relaxor behavior is induced and the dielectric maximum temperature shifts to higher temperatures with increasing measuring frequencies. The presence of relaxor can be ascribed to the formation of polar nanoregions. The studied composition exhibits the optimal ferroelectric and piezoelectric properties with d₃₃ of 453 pC/N and K_p of 0.58, T_m of 405 °C for x = 0.10 composition, which is suitable for future high-temperature piezoelectric application.     

Diffuse transition and piezoelectric properties of Pb[(Zr1−xTix)0.74(Mg1/3Nb2/3)0.20(Zn1/3Nb2/3)0.06]O3 Ceramics

In this work, the piezoelectric ceramic system of Pb[(Zr_1−xTi_x)_0.74(Mg_1/3Nb_2/3)_0.20(Zn_1/3Nb_2/3)_0.06]O₃, 0.47≤x≤0.57, with composition close to the morphotropic phase boundary, was studied. From the results of X-ray diffraction and piezoelectric measurement, ceramics near x=0.51 were found at the morphotropic phase boundary (MPB) between the tetragonal and pseudocubic perovskite. The planar coupling factor (k_p=0.72) is high at compositions near the MPB, but the mechanical quality factor (Q_m=75) is low. The calculation of the diffuseness of phase transition shows that the region of phase coexistence of this system is broader than that of the ternary system.