High and Frequency‐Insensitive Converse Piezoelectric Coefficient Obtained in AgSbO3‐Modified (Li,K, Na)(Nb,Ta)O3 Lead‐Free Piezoceramics

AgSbO₃ was doped into KNN‐based lead‐free piezoceramics with an optimized composition of Li_0.02(Na_0.53K_0.48)_0.98Nb_0.8Ta_0.2O₃ (abbreviated as LKNNT) to further enhance its piezoelectric property. The doping of AgSbO₃ was found to be effective in reducing the grain sizes, resulting in more uniform microstructure in AgSbO₃‐doped LKNNT ceramics. AgSbO₃ lowers tetragonal‐orthorhombic phase transition point (T_T‐O), but with a more gentle rate as compared with other dopants. A large converse piezoelectric coefficient d₃₃* up to 598 pm/V under a relatively low electric field of 1 kV/mm was obtained in the LKNNT‐5 mol% AgSbO₃ composition, whose tetragonal‐orthorhombic phase transition point (T_T‐O) was controlled near room temperature, but its Curie temperature was kept at 235°C. The d₃₃* obtained in the present material is a very high value for nontextured KNN‐based ceramics, which is attributed to the polymorphism phase transition effect and “soft” behavior caused by the addition of AgSbO₃.     

Investigation of MnO2‐doped (Ba,Ca)TiO3 lead‐free ceramics for high power piezoelectric applications

x% mol MnO₂‐doped Ba_0.925Ca_0.075TiO₃ ceramics (abbreviated as BCT‐Mnx, x=0‐1.5) were synthesized by conventional solid‐state reaction method. The effects of MnO₂ addition and (Ba+Ca)/Ti mole ratio (A/B ratio) on the microstructure and electrical properties of the ceramics were investigated. The internal bias filed E_i was determined from the asymmetrical polarization hysteresis loops and found to increase with the doping concentration of MnO₂. High mechanical quality factors (Q_m>1200) and low dielectric loss (tanδ<0.5%) were found in the BCT‐Mn0.75 and BCT‐Mn1.0 ceramics with E_i>3 kV/cm, meanwhile, the piezoelectric and electromechanical properties were found to decrease compared with the pure BCT, exhibiting a typical characteristic of “hard” behavior. Of particular interest is that the microstructure of BCT‐Mn0.75 ceramics could be controlled by changing the A/B ratio, where enhanced piezoelectric coefficient d₃₃ on the order of 190 pC/N was obtained in the BCT‐Mn0.75 ceramics with A/B=1.01 due to its fine‐grained microstructure, with yet high Q_m, being on the order of 1000. The high d₃₃ and Q_m in MnO₂‐doped BCT ceramics make it a promising candidate for high power piezoelectric applications.     

Properties and structures of nonstoichiometric (K,Na)NbO3‐based lead‐free ceramics

The 0.968[(K_0.48Na_0.52)]Nb_0.95+xSb_0.05O₃–0.032(Bi_0.5Na_0.5)ZrO₃ [KNN_xS–BNZ] lead‐free ceramics with nonstoichiometric niobium ion were fabricated via conventional solid‐state sintering technique and their piezoelectric, dielectric and ferroelectric properties were investigated. When x = 0.010, enhanced piezoelectric properties (d₃₃ ≈ 421 pC/N and k_p ≈ 0.47) were obtained due to the construction of rhombohendral—tetragonal phase boundary near room temperature. The KNN_xS–BNZ ceramics possesses enhanced Curie temperature (T_c) with improved piezoelectric constant. A large d₃₃ of ~421 pC/N and a high T_c ~256°C can be simultaneously induced in the ceramics with x = 0.010. Especially, good thermal stability was observed in a broad temperature range. The results indicated that our work could benefit development of KNN‐based ceramics and widen their application range.     

Large electric‐field‐induced strain and enhanced piezoelectric constant in CuO‐modified BiFeO3‐BaTiO3 ceramics

In this work, we fabricated the (1‐x)BiFeO₃‐xBaTiO₃+y‰ mol CuO ceramics by the modified thermal quenching technique. The pure perovskite phase was formed and a morphotropic phase boundary (MPB) was observed in the ceramics with x = 0.30‐0.33. The addition of CuO can significantly enhance the density of the BiFeO₃‐BaTiO₃ material. Importantly, an enhanced piezoelectric constant (d₃₃=165 pC/N), a large electric‐field‐induced strain (?S = 0.54%: peak to peak strain) and a large piezoelectric actuator constant (d₃₃*=449 pm/V) together with a high Curie temperature (T_C) of 503°C were observed in the ceramics with x = 0.30 and y = 5. As a result, the enhanced piezoelectricity and large electric‐field‐induced strain could significantly stimulate further researches in BFO‐based ceramics.     

High strain (0.4%) Bi(Mg2/3Nb1/3)O3‐BaTiO3‐BiFeO3 lead‐free piezoelectric ceramics and multilayers

The relationship between the piezoelectric properties and the structure/microstructure for 0.05Bi(Mg_2/3Nb_1/3)O₃‐(0.95‐x)BaTiO₃‐xBiFeO₃ (BBFT, x = 0.55, 0.60, 0.63, 0.65, 0.70, and 0.75) ceramics has been investigated. Scanning electron microscopy revealed a homogeneous microstructure for x < 0.75 but there was evidence of a core‐shell cation distribution for x = 0.75 which could be suppressed in part through quenching from the sintering temperature. X‐ray diffraction (XRD) suggested a gradual structural transition from pseudocubic to rhombohedral for 0.63 < x < 0.70, characterized by the coexistence of phases. The temperature dependence of relative permittivity, polarization‐electric field hysteresis loops, bipolar strain‐electric field curves revealed that BBFT transformed from relaxor‐like to ferroelectric behavior with an increase in x, consistent with changes in the phase assemblage and domain structure. The largest strain was 0.41% for x = 0.63 at 10 kV/mm. The largest effective piezoelectric coefficient (d₃₃^*) was 544 pm/V for x = 0.63 at 5 kV/mm but the largest Berlincourt d₃₃ (148 pC/N) was obtained for x = 0.70. We propose that d₃₃^* is optimized at the point of crossover from relaxor to ferroelectric which facilitates a macroscopic field induced transition to a ferroelectric state but that d₃₃ is optimized in the ferroelectric, rhombohedral phase. Unipolar strain was measured as a function of temperature for x = 0.63 with strains of 0.30% achieved at 175°C, accompanied by a significant decrease in hysteresis with respect to room temperature measurements. The potential for BBFT compositions to be used as high strain actuators is demonstrated by the fabrication of a prototype multilayer which achieved 3 μm displacement at 150°C.     

Thermal stability and electric‐field‐induced strain behaviors for PIN‐PSN‐PT piezoelectric ceramics

Pb (In_1/2Nb_1/2) O₃‐Pb (Sc_1/2Nb_1/2) O₃‐PbTiO₃ (PIN‐PSN‐PT) ternary ceramics with compositions near morphotropic phase boundary (MPB) were fabricated by solid‐state‐sintering process. Dielectric and piezoelectric properties of xPIN‐yPSN‐zPT (x = 0.19, 0.23 and z = 0.365, 0.385) ceramics were investigated as a function of temperature, showing high T_r‐t and T_c on the order of 160 ~ 200°C and 280 ~ 290°C, respectively. The xPIN‐yPSN‐0.365PT (x = 0.19 and 0.23) ceramics do not depolarize at the temperature up to 200°C, showing a better thermal stability when compared to the state‐of‐the‐art relaxor‐PbTiO₃ systems. A slight variation (<9%) of k_p, k_t, and k₃₃ was observed in the temperature range of 25°C‐160°C for xPIN‐yPSN‐0.385PT (x = 0.19 and 0.23) ceramics. Rayleigh analysis was employed to quantify the contribution of domain wall motion to piezoelectric response, where the domain wall contribution was found to increase with composition approaching MPB for PIN‐PSN‐PT system.     

Structural and piezoelectric properties of <001> textured PZT‐PZNN piezoelectric ceramics

Rhombohedral 0.69Pb(Zr_0.47Ti_0.53)‐0.31Pb(Zn_0.6Ni_0.4)NbO₃ (PZT‐PZNN) ceramics were textured using 10.0 vol. % BaTiO₃ (BT) platelets along the <001> direction at 950°C with a high Lotgering factor of 95.3%. BT platelets did not react with the PZT‐PZNN ceramics, and the textured PZT‐PZNN ceramic had a tetragonal structure. The PZT‐PZNN ceramics exhibited a strain of 0.174% with a piezoelectric strain constant (d*₃₃) of 580 pC/N at 3.0 kV/mm. The textured PZT‐PZNN ceramic showed an increased strain of 0.276% and d*₃₃ of 920 pC/N at 3.0 kV/mm, which can be explained by the domain rotation. However, the d₃₃ values of the textured specimens are smaller than those of the untextured specimens because of the small remanent polarization and relative dielectric constant of BT platelets. The textured PZT‐PZNN ceramic synthesized in this work can be used for piezoelectric multilayer actuators because of its large strain and low sintering temperature.     

Improved thermal stability of the piezoelectric properties of (Li,Ag)‐co‐modified (K,Na) NbO3‐based ceramics prepared by spark plasma sintering

High‐performance lead‐free piezoelectric ceramics 0.94(K_0.45Na_0.55)_1?xLi_x(Nb_0.85Ta_0.15)O₃–0.06AgNbO₃ (KNNLTAg‐x) were successfully prepared by spark plasma sintering technique. The doping effect of Li on the structural and electrical properties of KNNLTAg‐x (x=0, 0.02, 0.04, 0.06, 0.08 and 0.10) ceramics was studied. The lattice structure, ferroelectric and piezoelectric properties of the KNLNTAg‐x ceramics are highly dependent on the Li doping level. In particular, the Li dopant has a great impact on both Curie temperature T_c and orthorhombic‐tetragonal transition temperature T_O‐T. The 4% Li‐doped sample exhibited relatively high T_O‐T of 95°C, leading to a stable dynamic piezoelectric coefficient (d₃₃*) of 220‐240 pm/V in a broad temperature range from 25°C to 105°C. Additionally, the 2% Li‐doped sample shows a high d₃₃* of 320 pm/V at 135°C, suggesting its great potential for high‐temperature applications.     

Phase coexistence and large piezoelectricity in BaTiO3‐CaSnO3 lead‐free ceramics

Ferroelectric phase coexistence was constructed in (1?x)BaTiO₃‐xCaSnO₃ lead‐free ceramics, and its relationship with the piezoelectricity of the materials was investigated to ascertain potential factors for strong piezoelectric response. It is found that the addition of CaSnO₃ caused a series of phase transitions in the (1?x)BaTiO₃‐xCaSnO₃ ceramics, and a ferroelectric coexistence of rhombohedral, orthorhombic, and tetragonal phases is formed at x = 0.08, where the ceramics exhibit the lowest energy barrier and consequently facilitate the polarization rotation and extension, resulting in the optimal piezoelectricity of d₃₃ and k_p values of 550 pC/N and 0.60, respectively. Our study provides an intuitive insight to understand the origin of high piezoelectricity in the ceramics with the coexistence of multiferroelectric phases.     

Effects of Bi0.5Na0.5HfO3 addition on the phase structure and piezoelectric properties of (K,Na)NbO3‐based ceramics

Lead‐free perovskite (1‐x)(K_0.48Na_0.48Li_0.04)Nb_0.95Sb_0.05O₃‐x(Bi_0.5Na_0.5)HfO₃ piezoelectric ceramics were prepared by a traditional ceramic fabrication method. An investigation was conducted to assess the effects of (Bi_0.5Na_0.5)HfO₃ content on the crystal structure, microstructure, phase‐transition temperatures, and piezoelectric properties of the ceramics. The X‐ray diffraction results, combined with the temperature dependence of dielectric properties, revealed that the ceramics experienced a structural transition from an orthorhombic phase to a tetragonal phase with the addition of (Bi_0.5Na_0.5)HfO₃, and a coexistence of orthorhombic and tetragonal phases was identified in the composition range of 0.005≤x≤0.015. An obviously improved piezoelectric activity was obtained for the ceramics with compositions near the orthorhombic‐tetragonal phase boundary, among which the composition x=0.005 exhibited the maximum values of piezoelectric constant d₃₃, and planar and thickness electromechanical coupling coefficients (k_p and k_t) of 246 pC/N, 0.435, and 0.554, respectively. Furthermore, the Curie temperature of the ceramics was found decreasing with the increase in (Bi_0.5Na_0.5)HfO₃ content, but still maintaining above 300°C for the phase boundary compositions. These results indicate that the ceramics are promising lead‐free candidate materials for piezoelectric applications.     

Phase,domain, and microstructures in Sr2+ substituted low-temperature sintering PZT-based relaxor ferroelectrics

The Ag-Pd internal electrode of multilayer piezoelectric ceramics needs to be sintered below 1000°C, and lead wires and components need to be welded with lead-free solder at 260°C. PNN–PMW–PZT–xSr piezoelectric ceramics with high Curie temperature (T_c > 260°C) were synthesized at a low sintering temperature (960°C) to meet the requirements of multilayer piezoelectric devices. The relationship between structures (phase, domain, and microstructures) and electrical properties (piezo/ferroelectric properties, and dielectric relaxation) in the Sr²⁺ substituted ceramics was investigated. Rietveld refinement and Raman spectra show that Sr²⁺ substitution can cause the phase change and increase the force constant of [BO₆] octahedron. The piezoelectric response increases with increasing the content of the tetragonal phase (CTP) in the rhombohedral-tetragonal (R-T) coexisted ceramics. The ceramics with 0.6 mol% Sr²⁺ substitution have minimum activation energy for domain wall movement (E_a) of 0.0362 eV which favors the formation of nanometer-sized domains, and possess excellent electrical properties (d₃₃ = 623 pC/N, d₃₃^* =783 pm/V, T_c =295°C). The higher the CTP, the lower the E_a. The lower E_a favors the rotation of polarization direction and extension, and is beneficial to the generation of the nanometer-size domains, resulting in high piezoelectric properties.     

Defect‐driven evolution of piezoelectric and ferroelectric properties in CuSb2O6‐doped K0.5Na0.5NbO3 lead‐free ceramics

Defect greatly affects the microscopic structure and electrical properties of perovskite piezoelectric ceramics, but the microscopic mechanism of defect‐driven macroscopic properties in the materials is not still completely comprehended. In this work, K_0.5Na_0.5NbO₃+x mol CuSb₂O₆ lead‐free piezoelectric ceramics were fabricated by a solid‐state reaction method and the defect‐driven evolution of piezoelectric and ferroelectric properties was studied. The addition of CuSb₂O₆ induces the formation of dimeric (DC1) and trimeric (DC2) defect dipoles. At low doping concentration of CuSb₂O₆ (0.5‐1.0 mol%), DC1 and DC2 coexist in the ceramics and harden the ceramics, inducing a constricted double P‐E loop and high Q_m of 895 at x=0.01. However, DC2 becomes more dominant in the ceramics with high concentration of CuSb₂O₆ (≥1.5 mol%) and thus leads to softening behavior of piezoelectricity and ferroelectricity as compared to the ceramic with x=0.01, giving a single slanted P‐E loop and relatively low Q_m of 206 at x=0.025. All ceramics exhibit relatively high d₃₃ of 106‐126 pC/N. Our study shows that the piezoelectricity and ferroelectricity of K_0.5Na_0.5NbO₃ ceramics can be tailored by controlling defect structure of the materials.     

Structure‐property relationships in BiScO3–PbTiO3–PbMg1/3Nb2/3O3 ceramics near the morphotropic phase boundary

The phase structure, dielectric, ferroelectric, and piezoelectric properties of (1?2x)BiScO₃–xPbTiO₃–xPbMg_1/3Nb_2/3O₃ ceramics (x = 0.30‐0.46) were studied. It was found that an increase in x leads to a structural phase transition between the rhombohedral and tetragonal phase via an intermediate monoclinic phase and to a crossover from the nonergodic relaxor state to the ferroelectric one. It was proposed that at x > 0.42 the phase transition changes from second to first order. The assumption about the existence of a tricritical point on the phase diagram at x ≈ 0.42 with the enhanced dielectric response has been made. The observed structure‐property relationships of the studied solid solutions are discussed. It is shown that the solid solutions with x = 0.42 are characterized by the high piezoelectric parameters (d₃₃ = 509 pC/N, d₃₁ = ?178 pC/N, d_h = 153 pC/N), which makes possible their applications in sonar equipment.     

Piezoelectric properties of (Na0.5K0.5)(Nb1‐xSbx)O3‐SrTiO3 ceramics with tetragonal‐pseudocubic PPB structure

CuO‐added 0.96(Na_0.5K_0.5)(Nb_1‐xSb_x)O₃‐0.04SrTiO₃ ceramics sintered at the low temperature of 960°C for 10 hours showed dense microstructures and high relative densities. The specimens with 0.0 ≤  x ≤ 0.04 had orthorhombic‐tetragonal polymorphic phase boundary (PPB) structure. Tetragonal‐pseudocubic PPB structure was observed in specimens with 0.05 ≤  x ≤ 0.07, while the specimen with x = 0.08 has a pseudocubic structure. The structural variation in the specimens is explained by the decreases in the orthorhombic‐tetragonal transition temperature and Curie temperature with the addition of Sb⁵⁺ ions. The specimens with 0.05 ≤  x ≤ 0.07, which have tetragonal‐pseudocubic PPB structure, had large electric field‐induced strains of 0.14%‐0.016%. Moreover, these specimens also showed increased d₃₃ values between 280 pC/N and 358 pC/N. In particular, the specimen with x = 0.055 showed particularly enhanced piezoelectric properties: d₃₃ of 358 pC/N, k_p of 0.45, and the electric field‐induced strain of 0.16% at 4.5 kV/mm.     

Low‐temperature sintering and enhanced piezoelectric properties of random and textured PIN–PMN–PT ceramics with Li2CO3

Low‐temperature sintered random and textured 36PIN–30PMN–34PT piezoelectric ceramics were successfully synthesized at a temperature as low as 950°C using Li₂CO₃ as sintering aids. The effects of Li₂CO₃ addition on microstructure, dielectric, ferroelectric, and piezoelectric properties in 36PIN–30PMN–34PT ternary system were systematically investigated. The results showed that the grain size of the specimens increased with the addition of sintering aids. The optimum properties for the random samples were obtained at 0.5 wt% Li₂CO₃ addition, with piezoelectric constant d₃₃ of 450 pC/N, planar electromechanical coupling coefficient k_p of 49%, peak permittivity ε_max of 25 612, remanent polarization P_r of 36.3 μC/cm². Moreover, the low‐temperature‐sintered textured samples at 0.5 wt% Li₂CO₃ addition exhibited a higher piezoelectric constant d₃₃ of 560 pC/N. These results indicated that the low‐temperature‐sintered 36PIN–30PMN–34PT piezoelectric ceramics were very promising candidates for the multilayer piezoelectric applications.     

Electric‐Field‐Driven Phase Transition Process in (K,Na, Li)(Nb,Ta, Sb)O3 Lead‐Free Piezoceramics

The electric‐field‐driven phase transition in (K, Na, Li)(Nb, Ta, Sb)O₃ lead‐free piezoelectric ceramics was investigated by X‐ray diffraction, Raman spectra, and the temperature dependences of permittivity spectra. After poling under different electric fields, phase of the ceramics transformed gradually from orthorhombic–tetragonal coexisting phase to orthorhombic phase, indicating that the crystal structure of ceramics was strongly sensitive to electric field as an external stimulus. A secondary phase K₃Li₂Nb₅O₁₅ induced by electric field was detected in the ceramics with Li content of 7 mol%, which was close to the solubility limit of lithium. This field‐induced secondary phase resulted from the movement of Li ions and the structural deformation induced by electric field. Moreover, piezoelectric constant d₃₃ increased with the increasing poling field strength and the enhancement can be attributed to the field‐triggered domain switching. This study implied that in addition to temperature and composition, which has been reported in previous researches, electric field might be an effective way for inducing phase transition in lead‐free piezoelectric ceramics and improving the electrical performances simultaneously.     

Low‐Temperature Sintering and Piezoelectric Properties of CuO‐Added KNbO3 Ceramics

Dielectric and piezoelectric properties of CuO‐added KNbO₃ (KN) ceramics were investigated. The CuO reacted with the Nb₂O₅, formed a CuO–Nb₂O₅‐related liquid phase during the sintering, and assisted the densification of the KN ceramics at low temperatures. Moreover, some of the Cu²⁺ ions replaced the Nb⁵⁺ ions in the matrix and behaved as a hardener. The dielectric and piezoelectric properties of the KN ceramics were considerably influenced by the relative density. The 1.0 mol% CuO‐added KN ceramic sintered at 960°C for 1.0 h, which showed a maximum relative density, exhibited a high phase angle of 86.9°, P_r of 14.8 μC/cm², and E_c of 1.8 kV/mm. This specimen also exhibited good dielectric and piezoelectric properties: ε^T₃₃/ε_o of 364, d₃₃ of 122 pC/N, k_p of 0.29, and Q_m of 611.     

Improving piezoelectric properties and temperature stability for KNN‐based ceramics sintered in a reducing atmosphere

Lead‐free 0.955K_0.5Na_0.5Nb_1‐zTa_zO₃‐0.045Bi_0.5Na_0.5ZrO₃+0.4%MnO ceramics (abbreviated as KNNTaz‐0.045BNZ+0.4Mn) were prepared by a conventional solid‐state sintering method in a reducing atmosphere (oxygen partial pressure of 1 × 10^?10 atm). All ceramics with a pure perovskite structure show the two‐phase coexistence zone composed of rhombohedral and tetragonal phase. Ta⁵⁺ ions substitute for Nb⁵⁺ ions on the B‐site, which results in a decrease in the R phase fraction in the two‐phase coexistence zone. The R‐T phase transition temperature moves to room temperature due to the substitution of Nb⁵⁺ ions by Ta⁵⁺ ions. A complex domain structure composed of small nano‐domains (~70 nm) formed inside large submicron domains (~200 nm) exists in KNNTa0.02‐0.045BNZ+0.4Mn ceramics, which can induce a strong dielectric‐diffused behavior and improve the piezoelectric properties. The temperature stability for the reverse piezoelectric constant for the KNNTaz‐0.045BNZ+0.4Mn ceramics can be improved at z = 0.02. Excellent piezoelectric properties (d₃₃ = 328 pC/N, and  = 475 pm/V at E_max = 20 kV/cm) were obtained for the KNNTa_0.02‐0.045BNZ+0.4Mn ceramics.     

Sintering Behavior,Properties, and Applications of Co‐Fired Piezoelectric/Low Temperature Co‐Fired Ceramic (PZT‐SKN/LTCC) Multilayer Ceramics

Materials and processing conditions have been developed allowing co‐firing of fluxed PZT‐SKN materials with commercial low temperature co‐fired ceramic (LTCC) tapes. Previously, Pb(Zr_0.53, Ti_0.47)O₃–Sr(K_0.25, Nb_0.75)O₃ (PZT‐SKN) ceramics fluxed with 1 wt% LiBiO₂ and 1 wt% CuO addition were shown to sinter to high density at 900°C for 1 h, with a large d₃₃ piezoelectric coefficient of ~415 pm/V. Currently, the master sintering curve (MSC) approach has been used to study the densification behaviors of fluxed PZT‐SKN and LTCC tapes. Different sintering mechanisms for fluxed PZT‐SKN ceramics and LTCC materials are confirmed by analyzing the apparent activation energy (Q_a). Using knowledge gained from MSC results, an optimized sintering profile was developed. Multilayer PZT‐SKN/HL2000 (HeraLock^? Tape, Heraeus) stacks co‐fired at 900°C for 0.5 h maintain large piezoelectric coefficient (high field d₃₃ > 340 pm/V). EDS analysis reveal limited interdiffusion of Pb from PZT‐SKN layers in LTCC and the appearance of Al, Ca, and Si in the PZT‐SKN near the PZT‐SKN/LTCC interface. Further, elemental interdiffusion was not detected at the center of piezoelectric layer in PZT‐SKN/LTCC multilayer ceramics and no subsequent reduction in piezoelectric coefficient d₃₃ was observed. Finally, a piezoelectric microbalance with mass sensitivity of 150 kHz/mg was fabricated using the materials and methods developed.     

NaNbO3‐BaTiO3‐NaSbO3 lead and potassium‐free ceramics with thermally stable small‐signal piezoelectric properties

A new lead‐potassium‐free ceramic of (0.9‐x)NaNbO₃‐0.1BaTiO₃‐xNaSbO₃ (NN‐BT‐xNS) was successfully prepared via a solid‐state reaction method. The microstructure, phase structure, dielectric, ferroelectric, and piezoelectric properties were investigated as a function of NS content. The substitution of NS for NN was found to dramatically change the grain morphology from cube‐like grains typical for alkaline niobate‐based ceramics to conventional sphere‐like grains especially for Pb‐based perovskite ceramics. A normal to relaxor ferroelectric phase transformation was accompanied by a tetragonal (T) to rhombohedral (R) phase transition. A composition‐temperature phase diagram demonstrated a vertical morphotropic phase boundary between T and R phases in the composition range of x=0.03‐0.04, where optimum electrical properties of d₃₃=252 pC/N, k_p=36%, Q_m=168, =2063, and T_c=109°C were obtained in the x=0.035 ceramic sintered at 1260°C. Particularly, excellent temperature insensitivity of small‐signal piezoelectric properties suggested large application potentials in various actuators and sensors in comparison with other typical lead‐free materials.