Enhanced piezoelectric response and high-temperature sensitivity by site-selected doping of BiFeO3-BaTiO3 ceramics

Effect of Zn site-selected doping on electrical properties, high-temperature stability and sensitivity of piezoelectric response for BiFeO₃-BaTiO₃ ceramics was investigated. The results revealed that the addition of Zn leaded to an evident modification of the microstructure. The B-site selected doping was a more effective approach in improving piezoelectric properties as well as their thermal stability than those of A-site selected doping. Moreover, the enhanced piezoelectric properties accompanying by excellent high-temperature stability and sensitivity in B-site selected doping ceramics were obtained. The microstructure, domain switching behavior and temperature-dependent piezoelectric response in Zn site-selected doping ceramics were investigated, and their relationships with improving piezoelectric properties and high-temperature stability were explored. These results showed that the B-site selected doping ceramics had excellent piezoelectric properties (d₃₃ = 192pC/N) along with a high-temperature stability (T_d = 450 °C).     

Influence of secondary phases on ferroelectric properties of Bi0.5Na0.5TiO3 ceramics

The effects of secondary phases on ferroelectric properties of Bi_0.5Na_0.5TiO₃ (BNT) have been studied. Ceramic powders were prepared by solid state reaction employing different sintering temperatures and characterized by X-ray diffraction (XRD), Scanning Electron Microscopy and impedance spectroscopy. The perovskite structure was detected by XRD; together with small peaks corresponding to a secondary phase assigned to the Na₂Ti₆O₁₃-based phase in calcined powders. In addition, morphology and the content of the secondary phase were modified by the sintering temperatures, affecting the ferroelectric properties, and ac and dc conductivities. We believe that our results can benefit not only the understanding of BNT ceramics, but also expand the range of applications.     

Enhanced Curie temperature and superior temperature stability by site selected doping in BCZT based lead-free ceramics

In this work, Bi³⁺ doped Ba_0.98-3x/2Bi_xCa_0.02Zr_0.02Ti_0.976Cu_0.008O₃ [0 ≤ x ≤ 0.03] lead free ceramics, to be employed for structural, dielectric and ferroelectric studies, have been synthesized via conventional solid state reaction method. Rietveld refinement of the X-ray diffraction (XRD) data evidences the existence of a pure perovskite phase with tetragonal symmetry for all ceramics. The Scanning Electron Microscopy (SEM) reveals that the grain size, which is 16.14 μm for x = 0 reduced to 2.11 μm for x = 0.03. Dielectric studies demonstrate excellent dielectric behavior with high Curie temperature (T_C ～159 °C), high dielectric constant (ε_r ～834, ε_max ～ 3146), and a low dielectric loss (tanδ ～ 0.019), for an optimum value of x = 0.02. The analysis of temperature coefficient of the dielectric permittivity indicates the applicability of these materials in multilayer ceramic capacitors. Impedance studies, conducted to understand the underlying physical mechanisms, are found to be in good agreement with the results of structural and dielectric studies. Furthermore, the ferroelectric measurement confirms the ferroelectric nature for all samples with an energy storage efficiency (η) of ～42% for x = 0.02 composition.     

Enhanced piezoelectric properties in BF-BT based lead-free ferroelectric ceramics for high-temperature devices

Due to the high Curie temperature (T_C), BiFeO₃–BaTiO₃ (BF-BT) ceramics have been broadly investigated in high-temperature piezoelectric devices. The piezoelectric constant is one of the most significant factors in determining the sensitivity and reliability of piezoelectric functional components. However, the poor piezoelectric constant (d₃₃) of BF-BT ceramic has prevented the practical application of the material. In this work, we innovatively introduce the 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃ (0.93NBT-0.07BT) component to 0.7BF-0.3BT ceramic, to build a morphotropic phase boundary (MPB) for enhancing d₃₃. The XRD analysis shows that the (0.7BF-0.3BT)-x(0.93NBT-0.07BT) ceramics are still in the MPB region with R–PC phases coexistence, and exhibits a homogeneous solid solution. Moreover, the introduction of 0.93NBT-0.07BT ceramic suppresses the generation of defects and facilitates grain growth, thus enhancing piezoelectric property. In consequence, an optimum piezoelectricity d₃₃ = 213 pC/N along with T_c～450 °C was obtained in (0.7BF-0.3BT)-0.01(0.93NBT-0.07BT). This research provides a new idea for the application of BF-BT ceramics in high-temperature piezoelectric devices.     

Microstructure,ferroelectric and piezoelectric properties of Bi0.5K0.5TiO3-modified BiFeO3–BaTiO3 lead-free ceramics with high Curie temperature

The effects of composition, sintering temperature and dwell time on the microstructure and electrical properties of (0.75 ? x)BiFeO₃–0.25BaTiO₃–xBi_0.5K_0.5TiO₃ + 1 mol% MnO₂ ceramics were studied. The ceramics sintered at 1000 °C for 2 h possess a pure perovskite structure and a morphotropic phase boundary of rhombohedral and pseudocubic phases is formed at x = 0.025. The addition of Bi_0.5K_0.5TiO₃ retards the grain growth and induces two dielectric anomalies at high temperatures (T₁ ～ 450–550 °C and T₂ ～ 700 °C, respectively). After the addition of 2.5 mol% Bi_0.5K_0.5TiO₃, the ferroelectric and piezoelectric properties of the ceramics are improved and very high Curie temperature of 708 °C is obtained. Sintering temperature has an important influence on the microstructure and electrical properties of the ceramics. Critical sintering temperature is 970 °C. For the ceramic with x = 0.025 sintered at/above 970 °C, large grains, good densification, high resistivity and enhanced electrical properties are obtained. The weak dependences of microstructure and electrical properties on dwell time are observed for the ceramic with x = 0.025.     

Phase transition behavior and electrical properties of lead-free (1 − x)(0.98K0.5Na0.5NbO3–0.02LiTaO3)–x(0.96Bi0.5Na0.5TiO3–0.04BaTiO3) piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x)(0.98K_0.5Na_0.5NbO₃–0.02LiTaO₃)–x(0.96Bi_0.5Na_0.5TiO₃–0.04BaTiO₃) (KNN–LT–BNT–BT) with x = 0–0.10 have been synthesized by a conventional sintering technique. All samples possess pure perovskite structure, showing room temperature symmetries of orthorhombic at x < 0.02, and tetragonal at 0.05 ≤ x ≤ 0.10. A coexistence of orthorhombic and tetragonal phases in the composition range of 0.02 ≤ x < 0.05 in this system is caused by the temperature of the polymorphic phase transition (PPT) decreasing to around room temperature but not the behavior of the morphotropic phase boundary (MPB). The samples near the coexistence region exhibit improved properties, which are as follows: piezoelectric constant d₃₃ = 155 pC/N, remnant polarization P_r = 24.2 μC/cm², and coercive electric field E_c = 2 kV/mm. The results indicate that although this kind of ceramics displays good properties, further study is needed to promote the stabilities of the ceramics in order to utilize them in varying temperature environments.     

Composition and poling condition-induced electrical behavior of (Ba0.85Ca0.15)(Ti1−xZrx)O3 lead-free piezoelectric ceramics

Lead-free (Ba_0.85Ca_0.15)(Ti_1−xZr_x)O₃ (BCTZ) piezoelectric ceramics were fabricated by normal sintering in air atmosphere. BCTZ ceramics with x = 0.10 possess a coexistence of tetragonal and rhombohedral phases at ∼40 °C. The Curie temperature of BCTZ ceramics decreases with increasing the Zr content. Piezoelectric properties of BCTZ ceramics are dependent on the poling conditions (i.e., the poling temperature and the poling electric field), and the underlying physical mechanism is illuminated by the phase angle. The BCTZ (x = 0.10) ceramic, which locates at the existence of two phases and is poled at E ∼ 4.0 kV/mm and T_p ∼ 40 °C, exhibits an optimum electrical behavior at a room temperature of ∼20 °C: d₃₃ ∼ 423 pC/N, k_p ∼ 51.2%, 2P_r ∼ 18.86 μC/cm², 2E_c ∼ 0.47 kV/mm, ?_r ∼ 2892, and tan δ ∼ 1.53%.     

Enhancement of piezoelectric and ferroelectric properties of BaTiO3 ceramics by aluminum doping

Ferroelectric and piezoelectric properties of BaTiO₃ and Al-doped BaTiO₃ ceramics were investigated. The ferroelectric study demonstrated that, by doping Al³⁺ ions in the A-site of BaTiO₃, the polarization–electric field loop exhibited enhanced remnant polarization (from 12 to 17.5  μC/cm²), saturation and switching. In addition, the piezoelectric constant (d₃₃) increased with Al-doping for both static and dynamic strain values (from 75 to 135 and from 29.2 to 57.9 pC/N, respectively, at a maximum applied electric field of 16 kV/cm). Furthermore, the dielectric constant values increased and both the dielectric loss factor and leakage current decreased, even though the transition temperature shifted to lower temperature (from 121 to 113 °C) for the Al-doped sample. Therefore, the Al-doped BaTiO₃ has adjustable piezoelectric and ferroelectric properties.     

Influence of microwave sintering on electrical properties of BCTZ lead free piezoelectric ceramics

Barium titanate doped with calcium and zirconium (BCTZ) could be used at low temperature to replace lead based piezoelectric ceramics (PZT). The classical way to obtain BCTZ is the solid-state route coupled with conventional sintering, but this step is time-consuming. To reduce the duration of this process, microwave heating was used for sintering. It is a fast sintering method and the heating rate was around 200 °C/min in this study. Slightly better electrical properties with finer microstructures (d₃₃* = 706 pm/V, grain size about 42.1 ± 14.2 μm) were obtained for samples sintered by microwave heating during 50 min compared to the conventional sintering (d₃₃* = 622 pm/V, 22.6 ± 4.4 μm). The main result of this study is that by using microwave heating, the sintering step duration (including heating, dwell time and cooling) was drastically reduced: 1.5 h for microwave sintering against 12.5 h for conventional sintering.     

High piezoelectricity in CuO-modified Ba(Ti0.90Sn0.10)O3 lead-free ceramics with modulated phase structure

High piezoelectricity was achieved in Ba(Ti_0.90Sn_0.10)O₃ lead-free ceramics by optimizing CuO addition and sintering temperature. The phase structure of 1.0 mol% CuO-doped Ba(Ti_0.90Sn_0.10)O₃ ceramic is coexisting rhombohedral and tetragonal phases as sintered at 1300 °C. The coexistence of rhombohedral, tetragonal and orthorhombic phases appears in 1.0 mol% CuO-doped Ba(Ti_0.90Sn_0.10)O₃ ceramics as sintered at 1350–1450 °C, which leads to highly enhanced d₃₃ up to 650pC/N. This work demonstrates that high piezoelectric property (d₃₃ = 650pC/N) can be obtained in BaTiO₃-based lead-free piezoceramics with a simple composition modification by modulating phase structures, which also indicates that Ba(Ti,Sn)O₃ is a promising candidate to replace the lead-based piezoceramics.     

Improving fatigue properties,temperature stability and piezoelectric properties of KNN-based ceramics via sintering in reducing atmosphere

It has great research value and application potential to develop K_0.5Na_0.5NbO₃(KNN)-based ceramics with low sintering temperature (T_sinter) and excellent piezoelectric properties. However, it is difficult to achieve the two goals of reducing T_sinter and improving piezoelectric properties together. We provide a new process (NP) to solve this problem. Compared with traditional process (TP), T_sinter of 0.945K_0.48Na_0.52Nb_0.96Ta_0.04O₃-0.055BaZrO₃+6 mol%MnO (KNNT-0.055BZ+6 Mn) sintered by NP is reduced greatly and its piezoelectric strains are improved obviously. Reducing atmosphere is an important part for NP. The reducing atmosphere condition can improve piezoelectric strain by increasing extrinsic contribution of reversible non-180° domains and intrinsic contribution of reversible R(rhombohedral)-M(monoclinic) phase transition. NP ceramics sintered at low T_sinter = 1045 °C (NP1045) possess excellent d*₃₃ (575 pm/V) at the electric field (20 kV/cm). The NP1045 ceramics fatigued after 10⁶ unipolar cycles show excellent fatigue resistance. Its d*₃₃ (575 pm/V) varies less than 10 % from room temperature to 185 °C.     

Synthesis routes for enhanced piezoelectric properties in spark plasma sintered Ta-doped KNN ceramics

Ta substitution in K_0.5Na_0.5NbO₃ lead free piezoelectrics helps to prevent grain growth and has been shown to improve the piezoelectric properties but always leads to hetereogeneous microstructures. Two synthesis routes have been studied to prepare K_0.5Na_0.5Nb_0.8Ta_0.2O₃ (KNNTa) substituted powders. Then highly densified KNNTa ceramics have been obtained by spark plasma sintering (SPS). The use of a synthesized oxide precursor Nb_1.6Ta_0.4O₅ during the ceramic elaboration process clearly shows through accurate Rietveld study a successful Ta substitution with 92% of Amm2 K_0.485(8)Na_0.515(8)Nb_0.819(6)Ta_0.181(6)O₃ phase, confirmed by SEM-EDS analysis and a more homogeneous chemical composition. This leads to enhanced electromechanical coupling coefficients with an improvement of 50% of k_t, 15% for k_p and low electrical losses, compared to the conventional synthesis method with a simple mixing of commercial precursors.     

Enhanced dielectric and piezoelectric properties in Na0.5Bi4.5Ti4O15 ceramics with Pr-doping

The bismuth layer-structured Na_0.5Bi_4.5-xPr_xTi₄O₁₅ (x?=?0, 0.1, 0.2, 0.3, 0.4, and 0.5) (NBT-xPr³⁺) ceramics were fabricated using the traditional solid reaction process. The effect of different Pr³⁺ contents on dielectric, ferroelectric and piezoelectric properties of Na_0.5Bi_4.5Ti₄O₁₅ ceramics were investigated. The grain size of Pr³⁺-doping ceramics was found to be smaller than that of pure one, the maximum dielectric constant and Curie temperature T_c gradually decreased with increasing Pr³⁺ contents, and the dielectric loss decreased at high temperature by Pr³⁺-doping. Moreover, the activation energy (E_a), resistivity (Z’), remanent polarization (2P_r) and piezoelectric constant (d₃₃) increased by Pr³⁺-doping. The NBT-xPr³⁺ ceramics with x?=?0.3 achieved the optimal properties with the maximum dielectric constant of 1109.18, minimum loss of 0.00822 (250?kHz), E_a of 1.122?eV, Z’ of 7.9?kΩ?cm (725 ºC), d₃₃ of 18 pC/N, 2P_r of 12.04 μC/cm². The enhancement was due to the addition of Pr³⁺ which suppressed the decreasing of resistivity at high temperature and made it possible for NBT-xPr³⁺ ceramics to be poled in perpendicular direction, implying that it is a great improvement for Na_0.5Bi_4.5Ti₄O₁₅ ceramics in electrical properties.     

Enhanced piezoelectricity and non-contact optical temperature sensing performance in Er3+ ion modified (K,Na)NbO3-based multifunctional ceramics

Rare earth ions doped ferroelectrics have attracted wide attentions due to their multifunction characteristics with both ferroelectric/piezoelectric properties and intriguing photoluminescence performance, which show great prospects for future multifunctional devices. In this work, a novel rare earth Er³⁺ ion modified potassium-sodium niobate (KNN) based ceramics were elaborately designed and prepared by the conventional solid-state reaction. The microstructure, phase structure, electric properties and photoluminescence performance of the Er³⁺ ion modified KNN-based ceramics were systematically investigated. Enhanced piezoelectricity (a considerable d₃₃ of exceeding 300 pC/N and a large d₃₃* up to 500 p.m./V) was realized through optimizing the substitution of BaZrO₃ by (Er_0.5,Na_0.5)ZrO₃. Both down-conversion and up-conversion photoluminescence emissions were detected in the optimal composition. The temperature-dependent upconversion emissions of the optimal Er³⁺ modified ceramic sample in the temperature range of 303–573K were verified to be applicable for non-contact optical temperature sensing with a maximum sensitivity S_a of 0.0028 K^-1 and a peak relative sensitivity S_r of 0.96% K⁻¹. Moreover, low-temperature sensing performance with a maximum S_r of 16.7% K⁻¹ in the temperature range of 80–280K was also presented based on the temperature-dependent down-conversion emissions. With both decent electrical properties and intriguing photoluminescence performance, the Er³⁺-modified KNN-based ferroelectrics exhibit good application potential in the future multifunctional optoelectronic devices.     

Improving the photostriction of BiFeO3-based ceramics by bandgap and domain size engineering

The photostrictive properties of (1?x)BiFe_0.96Mn_0.04O₃-xBaTiO₃ (0.23 ≤ x ≤ 0.38) ceramics were investigated using the solid-state synthesis method. Appropriate addition of manganese significantly reduces the bandgap, while the introduction of BaTiO₃ changes the phase structure from rhombohedral to pseudo-cubic and significantly optimizes the ferroelectric domain size. The photostriction was observed in the visible light wavelength range with a response time of around 45 s. Specifically, both enhanced photo-induced deformation around 1.27×10^?3 and high photostrictive efficiency of 8.40×10^?12 m³ W^?1 were obtained for the 0.67BiFe_0.96Mn_0.04O₃-0.33BaTiO₃ ceramics. The significantly narrow bandgap (～1.89 eV) and the increased domain wall density due to reduction in ferroelectric domain size enhance the separation and motion of photo-generated carriers, and consequently improve the photostrictive performance. Besides, the prominent Raman peak redshift with the increasing of Raman power reveals the enhanced FeO₆ octahedral distortion and stretching vibration of Fe–O bond, which indicates the lattice expansion caused by the photoexcited charge carriers.     

Sintering temperature effect on microstructure,electrical properties and temperature stability of MnO-modified KNN-based ceramics

Lead-free 0.955K_0.5Na_0.5NbO₃-0.045Bi_0.5Na_0.5ZrO₃?+?0.6%MnO (KNN-0.045BNZ?+?Mn0.6) ceramics have been prepared by a conventional solid-state sintering method in air. All the samples sintered at different temperatures possess a coexisting phase boundary (CPB) between rhombohedral (R) phase and tetragonal (T) phase. The increase of sintering temperature (T_s) increases the phase fraction of T phase in CPB region. Mn²⁺, Mn³⁺ and Mn⁴⁺ ions coexist in all the KNN-0.045BNZ?+?Mn0.6 ceramics sintered at 1110?°C to 1190?°C. High sintering temperature can induce a transformation from ${\mathrm{M}\mathrm{n}}_{\mathrm{N}\mathrm{b}}^{\text{'}\text{'}}$ defects to ${\mathrm{M}\mathrm{n}}_{\mathrm{N}\mathrm{b}}^{\text{'}}$ defects. The samples with fine grain show stable octahedral structure. The KNN-0.045BNZ?+?Mn0.6 ceramics with fine grain possess excellent temperature stability of $d_{33}^{*}$ due to the wide phase transition region. The increase of sintering temperature induces the (R-T) phase transition temperature to move to room temperature.     

A compromise between piezoelectricity and transparency in KNN-based ceramics: The dual functions of Li2O addition

Transparent ceramics with good electrical performance have recently drawn broad interest as promising multifunctional materials. Here, we report that a superior transmittance (T = 75 % at 2000 nm) and good piezoelectricity (d₃₃ ∼ 150 pC/N) can be simultaneously realized in 0.93K_0.5Na_0.5NbO₃-0.07SrZrO₃ (KNN-SZ) ceramics by Li₂O regulation. The effect of Li₂O regulation has two parts: first, the presence of Li₂O facilitates the grain growth of KNN-SZ, considering that it melts at a relatively low temperature as a proper sintering aid; second, the introduced Li⁺ causes local lattice distortion, resulting in the coexistence of orthogonal and tetragonal (O–T) phases. The enlarged grains reduce the light scattering by grain boundaries for a higher optical transmittance; meanwhile, large grains stand as a prerequisite for the macroscopic domain structure favoured for decent piezoelectricity, which could also be partly caused by the coexistence of O–T phases. We believe that these findings might make KNN-based ceramics a preferable candidate for optoelectronic devices.     

Defect structure,ferroelectricity and piezoelectricity in Fe/Mn/Cu-doped K0.5Na0.5NbO3 lead-free piezoelectric ceramics

For perovskite Pb-based ceramics, outstanding hardening piezoelectric properties can be easily induced by acceptor dopings of Fe, Mn or Cu, but in this work, completely different hardening effects are observed in Fe/Mn/Cu-doped K_0.5Na_0.5NbO₃ ceramics. Pure K_0.5Na_0.5NbO₃ exhibits a well-saturated single P-E loop, giving low Q_m of 72. Fe₂O₃-doped ceramic exhibits the combined effects of dominant donor and slight acceptor, giving a slightly slanted single P-E loop and relatively low Q_m of 156. For MnO₂-doped ceramic, moderate hardening properties with a slightly pinched P-E loop and relatively high Q_m of 370 are exhibited. Unlike Fe₂O₃ and MnO₂-doped ceramics, a double P-E loop and superhigh Q_m of 1965 are obtained in CuO-doped ceramic. The defect structure and corresponding microscopic mechanisms in the ceramics have been systematically investigated. Our study shows that defect characteristics should be responsible for distinct hardening properties in Fe, Mn and Cu-doped K_0.5Na_0.5NbO₃ materials.     

Effect of the electrode-bulk interface on the dielectric properties of BBZT ceramics

The effects of the electrode-bulk interface on the dielectric properties of Ba_0.9988Bi_0.0008Zr_0.2Ti_0.8O₃ (BBZT) ceramics with a slight change in the thickness (≤15%) were investigated. In BBZT ceramics, the dielectric constant decreases with the increase of thickness, and the interface between electrode and bulk ceramics is considered the main reason. A formula is proposed to calculate the dielectric constant of bulk materials. According to the formula, the electrode-bulk interface has a slight influence on the frequency characteristics of the dielectric constant. However, the ferroelectric to paraelectric phase transition temperature changes from 10 °C to 15 °C for bulk ceramics when the electrode-bulk interface is taken into consideration. In a range of 0 °C–75 °C, obvious differences between ε_B and ε_T are observed due to the electric field induced by removable carriers. The dielectric tunability is degraded by the influence of electrode-bulk interface. BBZT ceramics have considerable tunability (>65% @100 kHz) and a low loss tangent (<0.006 @100 kHz) with an excellent FOM value (>270). This study demonstrates a method of calculating the dielectric constants of bulk ceramic layers and provides a theoretical basis for improving the performance of bulk materials using interfacial layers.