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.     

Large Electromechanical Response in Lead‐Free La‐Doped BNKT–BST Piezoelectric Ceramics

Piezoceramics 0.99[(Bi_0.5Na_0.4K_0.1)_1?xLa_xTiO₃]?0.01[Ba_0.7Sr_0.3TiO₃] (BNKT–BST–La_x, x = 0–0.030) were synthesized using a conventional solid‐state reaction method. X‐ray diffraction revealed a phase transition from a tetragonal to cubic phase at x ≥ 0.005. The maximum dielectric constant as well as the depolarization temperature (T_d) decreased with increasing La content. La addition interrupted the polarization and strain hysteresis loops and demonstrates that the ferroelectric order of the BNKT–BST ceramics lead to a reduction in the remnant polarization and coercive field. However, the destabilization of the ferroelectric order is accompanied by a significant increase in the unipolar strain which is highest at x = 0.020 with a value of ~0.39% and corresponding normalized strain, d^*₃₃ (= S_max/E_max) of 650 pm/V. It was observed that the unipolar strain of x = 0.020 is very temperature insensitive up to 125°C, even at 125°C the d^*₃₃ is as high as ~431 pm/V. Moreover, an electric‐field‐dependent XRD was conducted to identify the main source of the high strain and a recoverable transformation from cubic to a rhombohedral–tetragonal mixed phase was observed. The recoverable field‐induced phase transformation is suggested to be the main cause for the obtained large strain at x = 0.020 in the BNKT–BST–La_x ceramics.     

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.     

Enhanced Piezoelectric Properties and Thermal Stability in the (K0.5Na0.5)NbO3:ZnO Lead‐Free Piezoelectric Composites

The piezoelectric properties of (K_0.5Na_0.5)NbO₃ (KNN) are normally enhanced by chemical substitutions or doping to form solid solutions. In this study, we report that the piezoelectric properties of KNN and thermal stability of piezoelectric coefficient d₃₃ can be both enhanced by forming the composite of KNN:ZnO. The d₃₃ of KNN:0.2ZnO can be improved to 110 pC/N by introducing the ZnO nanoparticles, which is better than the pure KNN (d₃₃ = 85 pC/N). The Curie temperature (T_C = 407°C) remains well comparable to the pure KNN (T_C = 408°C). Furthermore, the thermal stability of both remanent polarization (P_r) and piezoelectric parameter (d₃₃) is improved. The enhanced thermal stability could be related to the induced built‐in electric field or the enhanced sinterability by the addition of ZnO. The present results may help to optimize the piezoelectric properties of lead‐free materials by forming composite.     

Phase‐Composition‐Dependent Piezoelectric and Electromechanical Strain Properties in (Bi1/2Na1/2)TiO3–Ba(Ni1/2Nb1/2)O3 Lead‐Free Ceramics

New lead‐free perovskite solid solution ceramics of (1 ? x)(Bi_1/2Na_1/2)TiO₃–xBa(Ni_1/2Nb_1/2)O₃[(1?x)BNT–xBNN,x = 0.02–0.06) were prepared and their dielectric, ferroelectric, piezoelectric, and electromechanical properties were investigated as a function of the BNN content. The X‐ray diffraction results indicated that the addition of BNN has induced a morphotropic phase transformation from rhombohedral to pseudocubic symmetry approximately at x = 0.045, accompanying an evolution of dielectric relaxor behavior as characterized by enhanced dielectric diffuseness and frequency dispersion. In the proximity of the ferroelectric rhombohedral and pseudocubic phase coexistence zone, the x = 0.045 ceramics exhibited optimal piezoelectric and electromechanical coupling properties of d₃₃~121 pC/N and k_p~0.27 owing to decreased energy barriers for polarization switching. However, further addition of BNN could cause a decrease in freezing temperatures of polar nanoregions till the coexistence of nonergodic and ergodic relaxor phases occurred near room temperature, especially for the x = 0.05 sample which has negligible negative strains and thus show the maximum electrostrain of 0.3% under an external electric field of 7 kV/mm, but almost vanished piezoelectric properties. This was attributed to the fact that the induced long‐range ferroelectric order could reversibly switch back to its original ergodic state upon removal of external electric fields.     

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.     

Temperature‐insensitive piezoelectricity in lead‐free NaNbO3‐based ceramics

In this work, we report a lead‐free piezoelectric ceramic of (0.9‐x)NaNbO₃‐0.1BaTiO₃‐xBaZrO₃, and the effects of BaZrO₃ on the phase structure, microstructure, electrical properties and temperature stability are investigated. A morphotropic phase boundary‐like region consisting of rhombohedral (R) and tetragonal (T) phases is constructed in the compositions with x = 0.035‐0.04. More importantly, in situ temperature independence of the piezoelectric effect {piezoelectric constant (d₃₃) and strain} can be achieved below the Curie temperature (T_c). Intriguingly, the electric field‐induced strain is still observed at T ≥ T_c due to the combined actions of the electrostrictive effect and the electric field‐induced phase transition. We believe that NaNbO₃‐based ceramics of this type have potential for applications in actuators and sensors.     

Photoluminescence and Temperature Dependent Electrical Properties of Er‐Doped 0.94Bi0.5Na0.5TiO3‐0.06BaTiO3 Ceramics

Er‐doped 0.94Bi_0.5Na_0.5TiO₃‐0.06BaTiO₃ (BNT‐6BT: xEr, x is the molar ratio of Er³⁺ doping) lead‐free piezoceramics with x = 0–0.02 were prepared and their multifunctional properties have been comprehensively investigated. Our results show that Er‐doping has significant effects on morphology of grain, photoluminescence, dielectric, and ferroelectric properties of the ceramics. At room temperature, the green (550 nm) and red (670 nm) emissions are enhanced by Er‐doping, reaching the strongest emission intensity when x = 0.0075. The complex and composition‐dependent effects of electric poling on photoluminescence also have been measured. As for electrical properties, on the one hand, Er‐doping tends to flatten the dielectric constant‐temperature (ε_r‐T) curves, leading to temperature‐insensitive dielectric constant in a wide temperature range (50°C–300°C). On the other hand, Er‐doping significantly decreases the ferroelectric‐relaxor transition temperature (T_F–R) and depolarization temperature (T_d), with the T_F–R decreasing from 76°C to 42°C for x = 0–0.02. As a result, significant composition‐dependent electrical features were found in ferroelectric and piezoelectric properties at room temperature. In general, piezoelectric and ferroelectric properties tend to become weaker, as confirmed by the composition‐dependent piezoelectric coefficient (d₃₃), planar coupling factor (k_p), and the shape of polarization‐electric field (P–E), current‐electric field (J–E), bipolar/unipolar strain‐electric field (S–E) curves. Furthermore, to understand the relationship between the T_F–R/T_d and the electrical properties, the composition of x = 0.0075 has been intensively studied. Our results indicate that the BNT‐6BT: xEr with appropriate Er‐doping may be a promising multifunctional material with integrated photoluminescence and electrical properties for practical applications.     

High Power Performance of Manganese‐Doped BNT‐Based Pb‐Free Piezoelectric Ceramics

Electromechanical properties and high power characteristics of Pb‐free hard piezoelectric ceramics in the (BiNa_0.88K_0.08Li_0.04)_0.5 (Ti_1?xMn_x)O₃ (x = 0, 0.014, 0.015, and 0.016) system were studied. Mn doping resulted in a considerable enhancement of mechanical quality factor Q_m and vibration velocity. The lowest mechanical and dielectric losses were achieved in 1.5 mol% Mn‐doped ceramics with a planar Q_m of about 970 and tanδ of 0.89%. The heat dissipation and resonance frequency shift under high drive condition were remarkably suppressed upon Mn doping. The maximum vibration velocity was increased from 0.28 m/s in undoped ceramic to 0.6 m/s in 1.5 mol% Mn‐doped composition. The results of this study revealed that Mn‐doped BNT‐based piezoelectrics exhibited a superior high power performance compared to their lead‐based counterparts such as PZT4 and PZT8 ceramics.     

CuO‐added KNbO3‐BaZrO3 lead‐free piezoelectric ceramics with low loss and large electric field‐induced strain

CuO‐added (1‐x)KNbO₃‐x mol%BaZrO₃ ceramics with 0.0≤x≤7.0 were sintered at 960°C. Large double polarization vs electric field (P‐E) and sprout‐shaped strain vs electric field (S‐E) hysteresis curves were obtained from the specimens with x≤2.0. They exhibited large polarizing electric fields (E_P) owing to the presence of a large number of defect dipoles (P_Ds) that formed between Cu²⁺ ions and oxygen vacancies. Small double P‐E hysteresis curves were observed for the specimens with x≥3.0 with reduced E_P because of the decreased number of P_Ds and the presence of a polymorphic phase structure containing both orthorhombic and pseudocubic structures. In particular, the specimen with x=5.0 exhibited a large strain of 0.16% at 8.0 kV/mm with a small E_P of 1.2 kV/mm and good fatigue property: this specimen maintained a strain of 0.13% at 6.0 kV/mm after 10⁶ cycles of 3.0 kV/mm.     

The Relationship Between Phase Structure and Electrical Properties in (1 − x)(Bi0.5Na0.5TiO3–Ba0.5K0.5TiO3–BaTiO3)‐ xK0.5Na0.5NbO3 Quaternary Lead‐Free Piezoelectric Ceramics

(1 ? x)(0.85Bi_0.5Na_0.5TiO₃–0.11Ba_0.5K_0.5TiO₃–0.04BaTiO₃)‐ xK_0.5Na_0.5NbO₃ lead‐free piezoelectric ceramics with x = 0.00, 0.02, 0.03, 0.04, 0.05, and 0.10 were prepared by a conventional solid state method. A coexistence of rhombohedral (R) and tetragonal (T) phases was found in the system, which tended to evolve into pseudocubic symmetry when x increases. The x = 0.04 sample exhibited improved electrical properties: the dielectric constant ε_r = 1900 with the low loss tangents 0.06, the S_max/E_max of ~400 and ~460 pm/V under unipolar and bipolar electric field, respectively. Meanwhile, piezoelectric constant d₃₃ still maintained ~160 pC/N. These could be owed to the formation of polar nanoregions for relaxor phase.     

Structure,Ferroelectric, Piezoelectric,and Ferromagnetic Properties of BiFeO3‐BaTiO3‐Bi0.5Na0.5TiO3 Lead‐Free Multiferroic Ceramics

Lead‐free multiferroic ceramics of BiFeO₃‐BaTiO₃‐Bi_0.5Na_0.5TiO₃ have been prepared by a conventional ceramic technique. The microstructure, multiferroic, and piezoelectric properties of the ceramics have been studied. The ceramics sintered at 1000°C for 2 h possess a pure perovskite structure and a morphotropic phase boundary of rhombohedral and tetragonal phases is formed at x = 0.02. After the addition of Bi_0.5Na_0.5TiO₃, two dielectric anomalies are observed at high temperatures (T_m ~ 510°C–570°C and T₂ ~ 720°C). The phase transition around T_m becomes wider gradually with increasing x. The ferroelectricity, piezoelectricity, and ferromagnetism of the ceramics are significantly improved after the addition of Bi_0.5Na_0.5TiO₃. High resistivity (~1.3 × 10⁹ Ω·cm), strong ferroelectricity (P_r = 27.4 μC/cm²), good piezoelectricity (d₃₃ =140 pC/N, k_p = 31.4%), and weak magnetic properties (M_r =0.19 emu/g) are observed.     

Three Layer Perovskite‐Like Structured Pr3Ti2TaO11 Ferroelectrics with Super‐High Curie Point

Pr₃Ti₂TaO₁₁ was prepared by co‐precipitation and subsequent solid‐state reaction at 1300°C. The compound has a perovskite‐like layered structure belonging to space group Pmc2₁ with unit cell parameters a = 3.8689(3) Å, b = 20.389(2) Å, c = 5.5046(5) Å. Second harmonic generation results confirm the structure of Pr₃Ti₂TaO₁₁ as being noncentrosymmetric. Dense and textured ceramics were prepared by spark plasma sintering. Analysis of the X‐ray diffraction and transmission electron microscopy results showed that Pr₃Ti₂TaO₁₁ ceramics have an n = 3 (type II) heteroblock structure consisting of alternating n = 2 and 4 octahedral oxide layers. High‐resolution electron microscopy revealed the layered structure to be highly disordered, with faulting of the heteroblock structure and the coexistence of a n = 4 phase on a fine scale (nm), which was evident as a broadening of the X‐ray diffraction peaks of the ceramics. Pr₃Ti₂TaO₁₁ ceramic exhibits a super‐high Curie point (1415 ± 5°C). A small, but measurable piezoelectric constant d₃₃ between 0.1 and 0.2 pC/N was detected for the samples poled above 900°C under an electric field of 100–200 V/cm.     

Normal‐Relaxor‐Diffuse Ferroelectric Phase Transition and Electrical Properties of Bi(Mg1/2Ti1/2)3–PbZrO3–PbTiO3 Solid Solution Ceramics Near the Morphotropic Phase Boundary

Perovskite‐type xBi(Mg_1/2Ti_1/2)O₃–(0.56 ? x)PbZrO₃–0.44PbTiO₃ (xBMT–PZ–PT) ternary solid solution ceramics were synthesized via a conventional solid‐state reaction method. The phase transition behaviors, dielectric, ferroelectric, and piezoelectric properties were investigated as a function of the BMT content. The X‐ray diffraction analysis showed that the tetragonality of xBMT–PZ–PT was enhanced with increasing the BMT content, and a morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases was identified approximately in the composition of x = 0.08. In addition, the dielectric diffuseness and frequency dispersion behavior were induced with the addition of BMT and a normal‐relaxor‐diffuse ferroelectric transformation was observed from the PZ‐rich side to the BMT‐rich side. The electrical properties of xBMT–PZ–PT ceramics exhibit obviously compositional dependence. The x = 0.08 composition not only possessed the optimum properties with ε^T₃₃/ε₀ = 1450, Q_m = 69, d₃₃ = 390 pC/N, k_p = 0.46, P_r = 30 μC/cm², E_c = 1.4 kV/mm, T_c = 325°C, and a strain of 0.174% (d₃₃^* = 436 pm/V) under an electric field of 4 kV/mm as a result of the coexistence of two ferroelectric phases near the MPB, but also owned a good thermal‐depolarization behavior with a d₃₃ value of >315 pC/N up to 290°C and a frequency‐insensitive strain behavior.     

Temperature‐ and Frequency‐Dependent Properties of the 0.75Bi1/2Na1/2TiO3–0.25SrTiO3 Lead‐Free Incipient Piezoceramic

The dielectric and electromechanical properties of 0.75Bi_1/2Na_1/2TiO₃–0.25 SrTiO₃ (25ST) as a function of temperature and frequency were studied. It is shown that the 25ST is a relaxor ferroelectric as evidenced by the temperature‐dependent dielectric relaxations with an incipient piezoelectricity featured by the presence of a reversible electric‐field‐induced phase transformation at room temperature. The transition occurs on a broad electric field strength range depending on field amplitude and frequency. It is also accompanied by a huge strain that is attributed to repetitive poling and depoling originating due to the reversibility of the phase transition. The 25ST makes an attractive lead‐free candidate for stack actuators as it presents a high normalized d₃₃* of ~600 pm/V at a low electric field of 4 kV/mm for frequencies ranging from 0.1 up to 100 Hz.     

Microstructure,Ferroelectric, Piezoelectric,and Ferromagnetic Properties of Sc‐Modified BiFeO3–BaTiO3 Multiferroic Ceramics with MnO2 Addition

0.725BiFe_1?xSc_xO₃–0.275BaTiO₃ + y mol% MnO₂ multiferroic ceramics were fabricated by a conventional ceramic technique and the effects of Sc doping and sintering temperature on microstructure, multiferroic, and piezoelectric properties of the ceramics were studied. The ceramics can be well sintered at the wide low sintering temperature range 930°C–990°C and possess a pure perovskite structure. The ceramics with x/y = 0.01–0.02/1.0 sintered at 960°C possess high resistivity (~2 × 10⁹ Ω·cm), strong ferroelectricity (P_r = 19.1–20.4 μm/cm²), good piezoelectric properties (d₃₃ = 127–128 pC/N, k_p = 36.6%–36.9%), and very high Curie temperature (618°C–636°C). The increase in sintering temperature improves the densification, electric insulation, ferroelectric, and piezoelectric properties of the ceramics. A small amount of Sc doping (x ≤ 0.04) and the increase in the sintering temperature significantly enhance the ferromagnetic properties of the ceramics. Improved ferromagnetism with remnant magnetization M_r of 0.059 and 0.10 emu/g and coercive field H_c of 2.51 and 2.76 kOe are obtained in the ceramics with x/y = 0.04/1.0 (sintered at 960°C) and 0.02/1.0 (sintered at 1050°C), respectively. Because of the high T_C (636°C), the ceramic with x/y = 0.02/1.0 shows good temperature stability of piezoelectric properties. Our results also show that the addition of MnO₂ is essential to obtain the ceramics with good electrical properties and electric insulation.     

Enhanced Piezoelectric and Dielectric Responses in 92.5%(Bi0.5Na0.5) TiO3 ‐7.5%BaTiO3 Ceramics

Structure and piezoelectric coefficient (d₃₃) of lead‐free 7.5% mole BaTiO₃‐doped (Bi_0.5Na_0.5) TiO₃ (BNT‐7.5%BT) polycrystalline piezoceramics have been characterized systematically as a function of poling electric (E) field. Dielectric permittivity and loss were also measured as functions of frequency and temperature. The piezoelectric coefficient d₃₃ after poling at E = 35 kV/cm can reach d₃₃~186 pC/N, which is the highest value reported among (1?x) BNT–xBT compositions. A prior poling E field can reduce rhomobherdal lattice distortion, and enhance tetragonal phase and polarization ordering, that contribute significantly to the rapid raise of d₃₃ and lower depolarizing temperature (T_d). The reduced dielectric permittivity for the poled sample is attributed to ordered state and the pinning of field‐induced nanodomain walls by the presence of oxygen vacancies.     

Remarkably High‐Temperature Stability of Bi(Fe1−xAlx)O3–BaTiO3 Solid Solution with Near‐Zero Temperature Coefficient of Piezoelectric Properties

The 0.72Bi(Fe_1?xAl_x)O₃–0.28BaTiO₃ (x = 0, 0.01, 0.03, 0.05, and 0.07, abbreviated as BFAx–BT) lead‐free high‐temperature ceramics were prepared by the conventional ceramic processing. Systematic investigation on the microstructures, crystalline structures, dielectric and piezoelectric properties, and high‐temperature stability of piezoelectric properties was carried out. The crystalline structures of BFAx–BT ceramics evolve from rhombohedral structure with x < 0.01 to the coexistence of rhombohedral structure and pseudocubic phases with x ≈ 0.01, finally to pseudocubic phases when x > 0.03. Remarkably high‐temperature stability with near‐zero temperature coefficient of piezoelectric properties (TCk_p), together with improved piezoelectric properties has been achieved for x = 0.01 BFAx–BT ceramics. The BFAx–BT(x = 0.01) ceramics simultaneously show the excellent piezoelectric properties of d₃₃ = 151 pC/N, k_p = 0.31 and super‐high‐temperature stability of T_d = 420°C, TCk_p = 1 × 10^?4. It is considered that the observed strong piezoelectricity and remarkably high‐temperature stability should be ascribed to the phase coexistence of rhombohedral and pseudocubic phases. The rhombohedral phases have a positive TCk_p value and the pseudocubic phases possess a negative TCk_p value. Thus, the TCk_p value of BFAx–BT ceramics can be tuned by composition of x.     

Phase Diagram and Enhanced Piezoelectric Response of Lead‐Free BaTiO3–CaTiO3–BaHfO3 System

Three composition groups in the BaTiO₃–CaTiO₃–BaHfO₃ ternary system, (1 ? x)Ba(Hf_yTi_1?y)O₃–x(Ba_1?zCa_z)TiO₃ (abbreviated as BH_yT–xBC_zT with x = 0–1.0, y = 0.16, z = 0.20; x = 0–1.0, y = 0.16, z = 0.30; x = 0–1.0, y = 0.20, z = 0.30, respectively), have been designed for investigating the variation of the intermediate O‐phase region and its effect on the electrical properties. The temperature‐composition phase diagram of each group has been proposed based on the X‐ray diffraction patterns and the temperature‐dependent dielectric behaviors. The enhanced piezoelectric properties are achieved in the O–T phase boundary compositions of the three groups, which are BH_0.16T–0.58BC_0.20T, BH_0.16T–0.48BC_0.30T and BH_0.20T–0.53BC_0.30T, respectively. Piezoelectric coefficient d₃₃ of 448 pC/N is obtained in BH_0.20T–0.53BC_0.30T, which is higher than those of the other two phase boundary compositions. The O‐phase zone in BH_0.20T–xBC_0.30T is narrower than those in the BH_0.16T–xBC_0.20T and BH_0.16T–xBC_0.30T. In spite of its small O‐phase volume occupancy, the O‐phase plays a key role in the properties of the system. Our work confirms that the enhancement in piezoelectric properties is not only related to the O–T phase boundary near room temperature (RT), but also related to the shift of T_R‐O toward RT. In addition, a quantitative relation between the phase boundary composition and atomic mole ratio of Hf to Ca (R_m) is proposed, which the R_m value corresponding to the phase boundary is about 0.58. The results clearly demonstrate that in this system high piezoelectric properties are achieved by tuning the specific R_m value. Such a work may provide new clues for designing lead‐free piezoelectric materials with enhanced piezoelectric property.