Influences of Liquid‐Phase Sintering on Structure,Grain Growth,and Dielectric Behavior of PbZr0.52Ti0.48O3 Ceramics

In this work, to formulate piezoceramic systems such as PbZr_0.52Ti_0.48O₃ (PZT) for low‐temperature co‐fired ceramic (LTCC)‐based devices, liquid‐phase sintering approach is demonstrated. ZnO–B₂O₃ (ZB) binary glass system is used as sintering aid. X‐ray diffraction (XRD) study confirms the formation of morphotropic phase boundary (MPB; tetragonal + rhombohedral) in PZT prepared by hydrothermal route. ZB is found to induce change in tetragonal/rhombohedral ratio in MPB of PZT. 1%ZB in PZT is found to raise the tetragonality from 71% to 92% in MPB region of PZT. ZB addition in PZT has reduced the sintering temperature from 1250 to 825°C for relative density about 91% with sustaining MPB phase. 1% ZB content is optimal percentage to enhance sinterability and relative density. Uniform dispersion of glass in PZT matrix is confirmed by SEM images. ZB content in PZT is found to controlling grain growth during sintering. Highest dielectric constant and lowest dielectric loss with low sintering temperature (825°C) of 1%ZB among all glass added in PZT exhibit technical suitability of 1%ZB + PZT to use as LTCC‐based energy storage devices.     

Orientation-dependent,field-induced phase transitions in soft lead zirconate titanate piezoceramics

In situ high-energy X-ray diffraction (XRD) was performed on lead-zirconate-titanate-based ferroelectric materials with composition near the morphotropic phase boundary (MPB). The utilization of the two-dimensional area detector in in situ field-dependent experiments enables the complete analysis of the material response with respect to all azimuthal angles at each field amplitude. The studies reveal that the field-induced phase transition from tetragonal to rhombohedral is dependent on crystal orientation in Nb-doped PbZr_0.53Ti_0.47O₃ that is in close compositional proximity to the MPB. However, only domain wall motion is activated in Nb-doped PbZr_0.50Ti_0.50O₃, which is further in composition from the MPB. This synchrotron-based XRD characterization approach illustrates the importance in evaluating the orientation-dependence of phase transitions in piezoelectric and ferroelectric polycrystalline materials.     

Study of PbZr0.53Ti0.47O3 solid solution formation by interaction of perovskite phases

The formation of Pb(Zr_0.53Ti_0.47)O₃ solid solution around the MPH was studied by mutual interaction of perovskite PZT phases (rhombohedral and tetragonal) and by interaction of PZT phases with PbTiO₃ or PbZrO₃ at sintering temperature. Starting perovskite phases were prepared by the mechanical homogenization of oxidic precursors and calcination of mixtures at 1000 °C. The final Pb(Zr_0.53Ti_0.47)O₃ ceramic systems prepared from perovskite mixtures were monophasic (tetragonal symmetry) in comparison with the biphasic ceramics prepared from calcinate with the same stoichiometry. The magnitude of deviation from equilibrium chemical composition or fluctuation from final stoichiometry in PZT phase in starting powder perovskite mixtures was not crucial for the formation of monophase Pb(Zr_0.53Ti_0.47)O₃ ceramic system prepared using such a method.     

Microstructure Evolution of In Situ Pulsed‐Laser Crystallized Pb(Zr0.52Ti0.48)O3 Thin Films

Integration of lead zirconate titanate (PZT) films with temperature‐sensitive substrates (CMOS, polymers) would benefit from growth at substrate temperatures below 400°C. In this work, in situ pulsed‐laser annealing [Rajashekhar et al. (2013) Appl. Phys. Lett., 103 [3] 032908] was used to grow crystalline lead zirconate titanate (PbZr_0.52Ti_0.48O₃) thin films at a substrate temperature of ~370°C on PbZr_0.30Ti_0.70O₃‐buffered platinized silicon substrates. Transmission electron microscopy analysis indicated that the films were well crystallized into columnar grains, but with pores segregated at the grain boundaries. Lateral densification of the grain columns was significantly improved by reducing the partial pressure of oxygen from 120 to 50 mTorr, presumably due to enhanced adatom mobility at the surface accompanying increased bombardment. It was found that varying the fractional annealing duration with respect to the deposition duration produced little effect on lateral grain growth. However, increasing the fractional annealing duration led to shift of 111 PZT X‐ray diffraction peaks to higher 2θ values, suggesting residual in‐plane tensile stresses in the films. Thermal simulations were used to understand the annealing process. Evolution of the film microstructure is described in terms of transient heating from the pulsed laser determining the nucleation events, while the energy of the arriving species dictates grain growth/coarsening.     

Pyroelectric energy harvesting using low–TC (1–x)(Ba0.7Ca0.3)TiO3–xBa(Zr0.2Ti0.8)O3 bulk ceramics

Lead‐free ferroelectric ceramics (1–x)(Ba_0.7Ca_0.3)TiO₃–xBa(Zr_0.2Ti_0.8)O₃ (BCTZ100x) with x = 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, and 0.80 were evaluated for their pyroelectric energy harvesting performance, using the Olsen cycle. As the composition ratio x increased, the crystal phase changed to tetragonal, orthorhombic, rhombohedral, and cubic; the phase boundaries crossed each other in the vicinity of BCTZ70. The crossover phase transition behavior between first‐order and diffuse phase transition changed to only the diffusion phase transition with increasing x. A pinching effect occurred because an increase in dielectric constant was also observed. Energy densities N_D of 229 mJ/cm³ and 256 mJ/cm³ for BCTZ50 and BCTZ80 were obtained, respectively, in temperature of 30°C‐100°C and an electric field of 0‐30 kV/cm. These N_D values are over two times higher than that of soft–Pb(Ti,Zr)O₃ (PZT), which exhibits piezoelectric performance equivalent to BCTZ50 at room temperature. Compared with soft–PZT, BCTZ50 and BCTZ80 exhibited larger N_D values owing to their lower Curie temperatures (T_C ~ 50°C‐110°C). We conclude that low–T_C ferroelectrics are useful for pyroelectric energy conversion based on the Olsen cycle even if they are unsuitable for piezoelectric applications at high temperatures.     

Triple Hysteresis Loops of PLZST Ceramics Related to Coexistence of Ferroelectricity and Antiferroelectricity

The hysteresis behaviors and phase characteristics of Pb_0.97La_0.02(Zr_0.90Sn_0.025Ti_0.075)O₃ (PLZST) ceramics were investigated in this work. A single mini hysteresis loop at 3 kV/mm with the maximum polarization (P_max) of 8.3 μC/cm² and triple hysteresis loops at 6.6 kV/mm were observed, which indicates the coexistence of rhombohedral ferroelectric phase and tetragonal antiferroelectric phase. The X‐ray Diffraction patterns and dielectric temperature spectra both demonstrate this coexistence. Moreover, the hysteresis loops with increasing temperature indicated that a ferroelectric–antiferroelectric phase transition occurred at about 60°C. These phenomena would be useful for understanding the domain evolution during ferroelectric and antiferroelectric phase transition.     

Structure,electrical, and thermal expansion properties of PZnTe–PZT ternary system piezoelectric ceramics

xPb(Zn_0.5Te_0.5)O₃–(1?x)Pb(Zr_0.5Ti_0.5)O₃ (PZnTe–PZT) ceramics were prepared by the solid‐state reaction method. The phase structure, microstructure, ferroelectric and dielectric properties and thermal expansion properties were systematically investigated. X‐ray diffraction analysis showed the morphotropic phase boundary (MPB) existed at the composition of x = 0.08, which was the coexistence of the rhombohedral phase and the tetragonal phase. The grain size of ceramics decreased rapidly from 10‐20 μm to 1‐3 μm when the PZnTe was added in. The PZnTe–PZT ceramics at the MPB composition showed the largest high field effective piezoelectric coefficient and the lowest strain hysteresis H. The dielectric permittivity and phase transition temperature exhibited strongly compositional dependence. A good linear relation was shown in T_m temperature vs x content and a DPT behavior was found in xPZnTe–(1?x)PZT (x = 0.02‐0.08). The thermal expansion properties showed a low thermal expansion coefficient in the low temperature while a high thermal expansion coefficient in the high temperature. Besides, the thermal expansion curve also showed the characteristic of DPT in PZnTe–PZT ceramics.     

Deformation Control During Thermal Treatment of Electrospun PbZr0.52Ti0.48O3 Nanofiber Mats

This paper focuses on the deformation origin of PbZr_0.52Ti_0.48O₃ (PZT) fiber mats obtained by electrospinning. The main cause of deformation of the green mats during heating was found to be a nonuniform relaxation of the stretched PVP polymer, due to nonuniform thermal decomposition of the Pb‐hexanoate in the fibers. This relaxation starts under 100°C, well below the polymer decomposition temperature. The shrinkage was found to accelerate above the polymer glass transition point, giving rise to an overall linear change of almost 50%. The “green” PZT mats were easily separated from the collector by first depositing a pure PVP sublayer on the collector. An optimal fabrication and slow multistep thermal treatment process that provides fiber mats with desired PZT phase and overcomes the nonuniform deformation is described.     

Spherical ferroelectric PbZr0.52Ti0.48O3 nanoparticles with high permittivity: Switchable dielectric phase transition with temperature

The spherical ferroelectric PbZr_0.52Ti_0.48O₃ (PZT 52/48) nanoparticles are prepared via simple and environment friendly high temperature solid state method. The crystal structure and morphology of these particles are characterized by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and field emission scanning electron microscopy (FESEM). XRD analysis and selected area electron diffraction (SAED) pattern of PZT particles revealed its crystalline nature. The energy involved in the synthesis especially during the initiation and termination processes for the formation of PZT particles is found from the high temperature calorimetric study. These particles are spherical in nature with an average diameter of ≤20 nm. The bulk and surface chemical composition of these particles are investigated by Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). XPS study reveals that the prepared PZT particles contain titanium ion in two different oxidation states namely Ti³⁺ and Ti⁴⁺. The PZT particles exhibit high permittivity with relatively low dielectric loss. From temperature dependent dielectric analysis, it is seen that there is a switchable dielectric phase transition at or above 80 °C.     

Structural,dielectric and ferroelectric properties of lead-free Ba0.85Ca0.15Zr0.10Ti0.90O3 ceramics prepared by Plasma Activated Sintering

Lead-free Ba_0.85Ca_0.15Zr_0.10Ti_0.90O₃ (BCZT) ceramics were prepared by Plasma Activated Sintering (PAS). The influence of PAS sintering temperature on the crystalline phase, microstructure, and, dielectric and ferroelectric properties of BCZT ceramics were studied. The phase structure of BCZT ceramics first changed from rhombohedral phase to the coexistence of rhombohedral and tetragonal phases and then to tetragonal phase as the sintering temperature increased. Microstructural characterization of BCZT ceramics indicated that PAS can obtain a compact microstructure at lower temperatures of 1150–1300 °C compared with that from common pressureless sintering. The BCZT ceramics showed different degrees of diffuseness with increased temperature, and the diffuseness exponents C are all approximately on the order of 10⁵ °C. The dielectric and ferroelectric properties of BCZT ceramics were enhanced with increased sintering temperature. BCZT ceramics sintered at 1250 °C exhibited optimum properties of room-temperature ε_r=2863, ε_m=6650, and 2P_r=25.24 μC/cm², resulting from the relatively higher tetragonal phase content of the MPB between tetragonal and rhombohedral phases together with a compact microstructure.     

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.     

Metastable Ferroelectric Phase Induced by Electric Field in xPb(Zn1/3Nb2/3)O3–(1–x)Pb(Zr0.95Ti0.05)O3 Ceramics

A xPb(Zn_1/3Nb_2/3)O₃–(1–x)Pb(Zr_0.95Ti_0.05)O₃ (xPZN–(1–x) PZT) system close to antiferroelectric–ferroelectric (AFE–FE) morphotropic phase boundary has been prepared and investigated. The XRD results reveal PZN addition induces a phase transition from the orthorhombic (AFE) to rhombohedral (FE) phase through a phase coexistence region (AFE+FE). The polarization–electric field (P–E) measurements indicate that the AFE phase can be induced into a metastable FE (FE_m) phase. And the FE_m can recover to AFE around a critical temperature indicated by temperature‐dependent P–E loops. A composition‐temperature phase diagram was generalized within a certain range of PZN content in which an AFE–FE phase boundary connecting orthorhombic antiferroelectric to rhombohedral ferroelectric phase zones is formed near room temperature.     

High‐energy storage density and excellent temperature stability in antiferroelectric/ferroelectric bilayer thin films

The antiferroelectric/ferroelectric (PbZrO₃/PbZr_0.52Ti_0.48O₃) bilayer thin films were fabricated on a Pt(111)/Ti/SiO₂/Si substrate using sol‐gel method. PbZr_0.52Ti_0.48O₃ layer acts as a buffered layer and template for the crystallization of PbZrO₃ layer. The PbZrO₃ layer with improved quality can share the external voltage due to its smaller dielectric constant and thinner thickness, resulting in the enhancements of electric field strength and energy storage density for the PbZrO₃/PbZr_0.52Ti_0.48O₃ bilayer thin film. The greatly improved electric breakdown strength value of 2615 kV/cm has been obtained, which is more than twice the value of individual PbZr_0.52Ti_0.48O₃ film. The enhanced energy storage density of 28.2 J/cm³ at 2410 kV/cm has been achieved in PbZrO₃/PbZr_0.52Ti_0.48O₃ bilayer film at 20°C, which is higher than that of individual PbZr_0.52Ti_0.48O₃ film (15.6 J/cm³). Meanwhile, the energy storage density and efficiency of PbZrO₃/PbZr_0.52Ti_0.48O₃ bilayer film increase slightly with the increasing temperature from 20°C to 120°C. Our results indicate that the design of antiferroelectric/ferroelectric bilayer films may be an effective way for developing high power energy storage density capacitors with high‐temperature stability.     

Actuation mechanisms in mixed-phase K0.5Bi0.5TiO3-BiFeO3-PbTiO3 ceramics

We report an in-situ synchrotron X-ray diffraction study of K_0.5Bi_0.5TiO₃-BiFeO₃-PbTiO₃ ceramics, which exhibit a T_c of around 450 °C. The electromechanical actuation mechanisms comprise contributions from coexisting tetragonal and rhombohedral phases. The tetragonal {200} grain family exhibited the highest effective lattice strain, up to 8.2 × 10⁻³ at 5 kV/mm. Strong strain anisotropy in the tetragonal phase and field-induced intergranular stresses facilitate a partial transformation from tetragonal (high strain anisotropy) to rhombohedral (low strain anisotropy) at high electric field levels, with an average linear transformation strain of -1.54 × 10^-3. The domain switching behavior was effectively enhanced in both tetragonal and rhombohedral phases after the phase transformation, due to the release of intergranular stress. This observed self-adapting mechanism in tuning intergranular stress through partial phase switching in the morphotropic KBT-BF-PT composition with large lattice distortion could also be exploited in other perovskite systems in order to achieve high performance high temperature piezoelectric ceramics.     

Growth of thin film ferroelectric PZT,PHT, and antiferroelectric PHO from atomic layer deposition precursors

We present a conformal method of growing ferroelectric lead hafnate-titanate (PbHf_xTi_1−xO₃, PHT) and lead zirconate-titanate (PbZr_xTi_1−xO₃, PZT) using atomic layer deposition (ALD) precursors. The 4+ cation precursors consist of tetrakis dimethylamino titanium (TDMAT), tetrakis dimethylamino zirconium (TDMAZ) and tetrakis dimethyl amino hafnium (TDMAH) for Ti, Zr, and Hf, respectively. The Pb (2+) precursor was Lead bis(3-N,N-dimethyl-2-methyl-2-propanoxide) [Pb(DMAMP)₂]. PZT was limited to lead titanate (PTO)-rich compositions, where x <0.25 for PbZr_xTi_1−xO₃, and exhibited a remnant polarization of 26-27 µC/cm² with a coercive field between 150 and 170 kV/cm. The 3D-structure coating capability of PZT was demonstrated by deposition on micromachined trench sidewalls 45 µm deep. We fabricated Microelectromechanical systems (MEMS) cantilever arrays with PZT thin films grown using the present method and demonstrated piezoelectric actuation. Alternatively, PHT was deposited with Ti and Hf compositions within ±1 at.% of the morphotropic phase boundary (MPB). The PHT exhibited a remanent polarization of 7.0-8.7 µC/cm² with a coercive field between 84-100 kV/cm. We applied the same Pb and Hf precursors from the PHT process to grow antiferroelectric lead-hafnate (PHO), which showed the characteristic electric field-induced ferroelectric phase transition at approximately ±280 kV/cm and a maximum polarization of approximately ±32.8 µC/cm².     

Heterogeneous domain configurations in ferroelectric crystals during thermal depolarization

The phase transition and domain configurations in emerging ternary Mn‐doped Pb(In_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ ferroelectric crystals have been investigated by high‐resolution X‐ray diffraction. Phase transition sequences of cubic→rhombohedral and monoclinic A→tetragonal→cubic were determined under zero‐field‐cooling and zero‐field‐heating after poling, respectively. Most importantly, a monoclinic‐like heterogeneous domain configuration was observed in the conventional high‐symmetry tetragonal phase field due to the coexistence of multiscale tetragonal variants. Our results provide further evidence that superlattices with low‐symmetry can be assisted by tetragonal nano‐twins.     

Composition-dependent xBa(Zr0.2Ti0.8)O3-(1-x)(Ba0.7Ca0.3)TiO3 bulk ceramics for high energy storage applications

This work reports the composition dependent microstructure, dielectric, ferroelectric and energy storage properties, and the phase transitions sequence of lead free xBa(Zr_0.2Ti_0.8)O₃-(1-x)(Ba_0.7Ca_0.3)TiO₃ [xBZT-(1-x)BCT] ceramics, with x?=?0.4, 0.5 and 0.6, prepared by solid state reaction method. The XRD and Raman scattering results confirm the coexistence of rhombohedral and tetragonal phases at room temperature (RT). The temperature dependence of Raman scattering spectra, dielectric permittivity and polarization points a first phase transition from ferroelectric rhombohedral phase to ferroelectric tetragonal phase at a temperature (T_R-T) of 40?°C and a second phase transition from ferroelectric tetragonal phase - paraelectric pseudocubic phase at a temperature (T_T-C) of 110?°C. The dielectric analysis suggests that the phase transition at T_T-C is of diffusive type and the BZT-BCT ceramics are a relaxor type ferroelectric materials. The composition induced variation in the temperature dependence of dielectric losses was correlated with full width half maxima (FWHM) of A₁, E(LO) Raman mode. The saturation polarization (P_s) ≈8.3?μC/cm² and coercive fields ≈2.9?kV/cm were found to be optimum at composition x?=?0.6 and is attributed to grain size effect. It is also shown that BZT-BCT ceramics exhibit a fatigue free response up to 10⁵ cycles. The effect of a.c. electric field amplitude and temperature on energy storage density and storage efficiency is also discussed. The presence of high T_T-C (110?°C), a high dielectric constant (ε_r ≈?12,285) with low dielectric loss (0.03), good polarization (P_s ≈?8.3?μC/cm²) and large recoverable energy density (W?=?121?mJ/cm³) with an energy storage efficiency (η) of 70% at an electric field of 25?kV/cm in 0.6BZT-0.4BCT ceramics make them suitable candidates for energy storage capacitor applications.     

Thermally‐induced phase transformations in Na0.5Bi0.5TiO3–KNbO3 ceramics

The structures and functional properties of Na_0.5Bi_0.5TiO₃–xKNbO₃ (NBT‐xKN) solid solutions, with x in the range from 0.01 to 0.09, were investigated using a combination of high‐resolution synchrotron X‐ray powder diffraction (SXPD) and ferroelectric property measurements. For low KN contents, an irreversible transformation from cubic to rhombohedral phases was observed after the application of a high electric field, indicating that the polar nanoregions (PNRs) in the unpoled state can be transformed into metastable long‐range ordered ferroelectric domains in the poled state. In contrast, the near‐cubic phase of the unpoled ceramics was found to be remarkably stable and was retained on cooling to a temperature of ?175°C. Upon heating, the field‐induced metastable ferroelectric rhombohedral phase transformed back to the nanopolar cubic state at the structural transformation temperature, T_ST, which was determined as approximately 225°C and 125°C for KN contents of 3% and 5% respectively. For the field‐induced rhombohedral phase in the poled specimens, the pseudo‐cubic lattice parameter, a_p, exhibited an anomalous reduction while the inter‐axial angle increased towards a value of 90° on heating, resulting in an overall increase in volume. The observed structural changes were correlated with the results of temperature‐dependent dielectric, ferroelectric and depolarization measurements, enabling the construction of a phase diagram to define the stable regions of the different ferroelectric phases as a function of composition and temperature.     

Photonic Sintering of Aerosol Jet Printed Lead Zirconate Titanate (PZT) Thick Films

Lead Zirconate Titanate (PZT) is a commonly used piezoelectric material due to its high piezoelectric response. We demonstrate a new method of printing and sintering micro‐scale PZT films with low substrate temperature increase. Self‐prepared PZT ink was Aerosol‐Jet printed on stainless steel substrates. After drying for 2 h in vacuum at 200°C, the printed PZT films were divided into two groups. The first group was traditionally sintered, using a thermal process at 1000°C for 1 h in an Argon environment. The second group was photonically sintered using repetitive sub‐msec pulses of high intensity broad spectrum light in an atmospheric environment. The highest measured substrate temperature during photonic sintering was 170.7°C, enabling processing on low melting point substrates. Ferroelectric measurements were performed with a low‐frequency sinusoidal signal. The remanent polarization (P_r) and coercive field (E_c) for thermally sintered PZT film were 17.1 μC/cm² and 6.3 kV/cm, respectively. The photonically sintered film had 32.4 μC/cm² P_r and 6.7 kV/cm E_c. After poling the samples with 20 kV/cm electric field for 2 h at 150°C, the piezoelectric voltage constant (g₃₃) was measured for the two film groups yielding ?16.9 × 10^?3 (V·m)·N^?1 (thermally sintered) and ?17.9 × 10^?3 (V·m)·N^?1 (photonically sintered). Both factors indicate the PZT films were successfully sintered using both methods, with the photonically sintered material exhibiting superior electrical properties. To further validate photonic sintering of PZT on low melting point substrates, the process and measurements were repeated using a polyethylene terephthalate (PET) substrate. The measured P_r and E_c were 23.1 μC/cm² and 5.1 kV/cm, respectively. The g₃₃ was ?17.3 × 10^?3 (V·m)·N^?1. Photonic sintering of thick film PZT directly on low melting point substrates eliminates the need for complex layer transfer processes often associated with flexible PZT transducers.     

Domain Structure Evolutions During the Poling Process for [011]‐Oriented PMN–xPT Crystals Across the MPB Region

The poling effect on the [011]‐oriented (1?x)Pb(Mg_1/3Nb_2/3)O₃‐xPbTiO₃ (PMN–xPT) single crystals across the morphotropic phase boundary (MPB) was studied. The dielectric and piezoelectric properties were investigated as a function of the poling field. Domain structure evolutions during the poling process were recorded. In the unpoled PMN–xPT phase diagram, an apparent rhombohedral (R)‐tetragonal (T) phase boundary exists. With room‐temperature poling, the structure transformation sequence strongly depends on the composition. The crystal experiences a direct transition to the 2R/2T domain state in the rhombohedral or tetragonal phase field beyond the MPB region, whereas within the MPB zone it is hard to achieve the 2R/2T engineered configuration although the initial state is either rhombohedral or tetragonal as well. The piezoelectric responses of the MPB·PMN–xPTs are extraordinary weak (d₃₃ ~ 250 pC/N), in contrast to the [011]‐oriented multidomain PMN–xPTs with ultrahigh‐piezoelectric coefficient (d₃₃ > 1000 pC/N). We demonstrate that a slight composition variation near the MPB will significantly influence the domain evolution route and piezoelectricity for the [011]‐oriented PMN–xPT crystals. We also confirm the feasibility to realize the 2R/2T engineered domain configuration for the [011]‐oriented MPB crystals, which will extend the desired portion of the Bridgeman‐grown boules with optimal piezoelectric properties.