Lead-free piezoelectric ceramics with composition of (0.97−x)Na1/2Bi1/2TiO3-0.03NaNbO3-xBaTiO3

Compositions in (Na_1/2Bi_1/2)TiO₃ based ternary system, (0.97 – x) (Na_1/2Bi_1/2)TiO₃-0.03NaNbO₃-xBaTiO₃ (x = 0, 0.01, 0.02, 0.04, 0.05, 0.06, 0.08) are synthesized using conventional solid state reaction method. Influence of BaTiO₃ on crystal structure, dielectric and piezoelectric properties are investigated. All compositions can form single perovskite phase. Powder x-ray diffraction patterns can be indexed assuming a pseudo-cubic structure. Lattice constant increases with the increase of BaTiO₃ concentration. Rhombohedral distortion is observed in poled samples with BaTiO₃ concentration up to 6 mol%. Temperature dependence of dielectric constant and dissipation factor measurement reveals that all compositions experience two phase transitions: from ferroelectric to antiferroelectric and from antiferroelectric to paraelectric. Both transition temperatures, T _c and T _f, are lowered due to introduction of BaTiO₃. Ferroelectric to antiferroelectric phase transition has relaxor characteristics. Piezoelectric properties have relatively higher value around 1 mol% to 4 mol% BaTiO₃. In ceramics with x = 0.02, thickness electromechanical coupling factor (k _t) of 0.51 and piezoelectric charge constant (d ₃₃) of 110 × 10^–12 C/N are obtained. Addition of small amount of BaTiO₃ (x = 0.01, 0.02) improves piezoelectric properties compared to NBT-NN binary system, while T _f remains above 140°C, higher than that of NBT-BT binary system composition with similar piezoelectric properties. This is in favor of the possible application of them as lead-free piezoelectric ceramics.     

Depolarization temperature and piezoelectric properties of Na1/2Bi1/2TiO3-Na1/2Bi1/2(Zn1/3Nb2/3)O3 ceramics by two-stage calcination method

A new group of NBT-based lead-free piezoelectric ceramics, Na_1/2Bi_1/2TiO₃-Na_1/2Bi_1/2(Zn_1/3Nb_2/3)O₃, was synthesized using the two-stage calcination method and depolarization temperatures and piezoelectric properties were also investigated. The XRD analysis showed that the ceramics system had a morphotropic phase boundary (MPB) between the rhombohedral and the tetragonal structure. The highest piezoelectric properties of d ₃₃ = 97 pC/N and k _t = 0·46 were obtained near MPB compositions. Furthermore, the depolarization temperatures near MPB compositions were slightly decreased and the lowest T _d was maintained at 210°C.     

Ferroelectric and piezoelectric properties of new NaNbO<Subscript>3</Subscript>–Bi<Subscript>0.5</Subscript>K<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> lead-free ceramics

New lead-free ceramics (1–x)NaNbO₃–xBi_0.5K_0.5TiO₃ have been fabricated by the conventional ceramic sintering technique, and their ferroelectric and piezoelectric properties have been studied. The results of X-ray diffraction reveal that Bi_0.5K_0.5TiO₃ diffuses into the NaNbO₃ lattices to form a new perovskite-type solid solution with orthorhombic symmetry. The addition of a small amount of Bi_0.5K_0.5TiO₃ (x ≥ 0.025) transforms the ceramics from antiferroelectric to ferroelectric. The ceramic with x = 0.10 possesses the largest remanent polarization P _r and thus exhibits the optimum piezoelectric properties, giving d ₃₃ = 71 pC/N, k _p = 16.6% and k _t = 39.7%. The ceramics with low doping level of Bi_0.5K_0.5TiO₃ are normal ferroelectrics and the ferroelectric-paraelectric phase transition becomes diffusive gradually with the doping level x of Bi_0.5K_0.5TiO₃ increasing. Our results show the (1–x)NaNbO₃–xBi_0.5K_0.5TiO₃ ceramics is one of the good candidates for lead-free piezoelectric and ferroelectric materials.     

Morphotropic phase boundary and piezoelectric properties of (Bi1/2Na1/2)1 − x(Bi1/2K1/2)xTiO3-0.03(Na0.5K0.5)NbO3 ferroelectric ceramics

Lead-free piezoelectric ceramics, (Bi_1/2Na_1/2)_1 − x(Bi_1/2K_1/2)_xTiO₃-0.03(Na_0.5K_0.5)NbO₃ (x = 0.10-0.40) were synthesized by conventional solid-state sintering. A morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases was confirmed. Two dielectric anomalies can be observed, showing diffused phase transition behavior. There is no shift of the dielectric maximum temperature with frequency due to the contribution of space charge at high temperatures, similar to pure (Bi_1/2Na_1/2)TiO₃. The materials near MPB show a strong compositional dependence with the optimal properties of a d₃₃ of 167 pC/N, a k_p of 35.5%, a P_r of 27.6 μC/cm² and a E_c of 27.9 kV/cm, suitable for future application.     

The synthesis of lead-free ferroelectric Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3 thin films by sol-gel method

(1 − x)Bi_0.5Na_0.5TiO₃-xBi_0.5K_0.5TiO₃ [BNT-BKT-100x] thin films have been successfully deposited on Pt/Ti/SiO₂/Si substrates by a sol-gel process together with rapid thermal annealing. A morphotropic phase boundary (MPB) between Bi_0.5Na_0.5TiO₃ and Bi_0.5K_0.5TiO₃ was determined around x ∼ 0.15. Near the MPB, the film exhibits the largest grain size, the highest ε value (360) and the largest P_r value (13.8 μC/cm²). The BNT-BKT thin film system is expected to be a new and promising candidate for lead-free piezoelectric applications.     

Dielectric properties of Pb[(1?x)(Zr1/2Ti1/2)?x(Zn1/3Ta2/3)]O3 ceramics prepared by columbite and wolframite methods

Polycrystalline samples of Pb[(1 − x)(Zr_1/2Ti_1/2) − x(Zn_1/3Ta_2/3)]O ₃ , where x = 0.1–0.5 were prepared by the columbite and wolframite methods. The crystal structure, microstructure, and dielectric properties of the sintered ceramics were investigated as a function of composition via X-ray diffraction (XRD), scanning electron microscopy (SEM), and dielectric spectroscopy. The results indicated that the presence of Pb(Zn_1/3Ta_2/3)O₃ (PZnTa) in the solid solution decreased the structural stability of overall perovskite phase. A transition from tetragonal to pseudo-cubic symmetry was observed as the PZnTa content increased and a co-existence of tetragonal and pseudo-cubic phases was observed at a composition close to x = 0.1. Examination of the dielectric spectra indicated that PZT–PZnTa exhibited an extremely high relative permittivity at the MPB composition. The permittivity showed a ferroelectric to paraelectric phase transition at 330 °C with a maximum value of 19,600 at 100 Hz at the MPB composition.     

Effects of La occupation site on the dielectric and piezoelectric properties of [Bi0.5(Na0.75K0.15Li0.10)0.5]TiO3 ceramics

The crystal structure, phase transition and ferroelectric (FE)/piezoelectric properties were investigated for three types of La-doped [Bi_0.5(Na_0.75K_0.15Li_0.10)_0.5]TiO₃ ceramics. The dielectric measurements showed that the transition between FE and antiferroelectric (AFE) phases near 180 °C became pronounced by La addition, and the maximum permittivity was observed at 360 °C in La-doped samples, whereas at 290 °C in non-doped samples. Normal FE and excellent piezoelectric properties were observed by P–E hysteresis loop and piezoelectric measurements in samples without vacancy. However, when the A-site or B-site vacancies were formed, the temperature range of AFE phase extended even appeared at room temperature, which resulted in the presence of deformed P–E curves and decrease of piezoelectric properties. It was suggested that the AFE phase originated from the decoupling effect between BO₆ octahedra in ABO₃ perovskites due to the A-site and/or B-site vacancies.     

Effect of La and K on the microstructure and dielectric properties of Bi0.5Na0.5TiO3-PbTiO3

Small amounts of lanthanum and potassium dopants could modify the microstructure and dielectric properties of 0.90Bi_0.5Na_0.5TiO₃-0.10PbTiO₃ and 0.88Bi_0.5Na_0.5TiO₃-0.12PbTiO₃ solid solutions. La lowered both phase transition temperatures of ferroelectric to antiferroelectric and antiferroelectric to paraelectric. It also decreased the maximum value of relative dielectric permittivity of the composition. In contrast, K shifted the first phase transition to the lower temperature but insignificantly affected the Curie temperature and raised the maximum dielectric permittivity. Furthermore, K influenced the microstructure in the way to enhance the long grains of this solid solution but La inhibited this effect.     

Piezoelectric properties of [Bi<Subscript>0.5</Subscript>(Na<Subscript>0.7</Subscript>K<Subscript>0.25</Subscript>Li<Subscript>0.05</Subscript>)<Subscript>0.5</Subscript>]TiO<Subscript>3</Subscript>−Ba(Ti,Zr)O<Subscript>3</Subscript> binary system ceramics

Dense lead-free binary system piezoelectric ceramics (1 − x)[Bi_0.5(Na_0.7K_0.25Li_0.05)_0.5]TiO₃−xBa(Ti_0.95Zr_0.05)O₃ (BNKLT–BZT) were prepared by a two-step sintering process. A phase transition from rhombohedral to tetragonal was observed with increasing BZT fraction in the range x = 0.06–0.1 and the morphotropic phase boundary (MPB) between rhombohedral and tetragonal appears in this range. Ceramics containing 10 mol% BZT with tetragonal phase near the MPB region has the maximum piezoelectric constant d ₃₃(151pC/N).     

Evolution of the tetragonal to rhombohedral transition in (1 − x)(Bi1/2Na1/2)TiO3 − xBaTiO3 (x ≤ 7%)

Abstract

(1 ? x)(Bi_1/2Na_1/2)TiO₃ ? xBaTiO₃ has been the most studied Pb-free piezoelectric material in the last decade; however, puzzles still remain about its phase transitions, especially around the important morphotropic phase boundary (MPB). By introducing the strain glass transition concept from the ferroelastic field, it was found that the phase transition from tetragonal (T, P4bm) to rhombohedral (R, R3c) was affected by a strain glass transition at higher temperature for x ≥ 4%. In these compositions, the T–R transition was delayed or even totally suppressed and displayed huge thermal hysteresis upon cooling and heating. Also, isothermal phase transitions were predicted and realized successfully in the crossover region, where the interaction between the T–R transition and the strain glass transition was strong. Our results revealed the strain glass nature in compositions around the MPB in this important material, and also provide new clues for understanding the transition complexity in other (Bi_1/2Na_1/2)TiO₃-based Pb-free piezoelectric materials.     

Quenching-induced nonergodicity in ergodic Na1/2Bi1/2TiO3–BaTiO3–AgNbO3 ceramics

Quenching from sintering temperature enhances the depolarization temperature (T_d) in Na_1/2Bi_1/2TiO₃-based ceramics without significant deterioration of piezoelectric properties (d₃₃). In this work, quenching effects in an ergodic relaxor 0.97(0.94Na_0.5Bi_0.5TiO₃–0.06BaTiO₃)–0.03AgNbO₃ (NBT–6BT–3AN) were investigated based on structure, ferroelectric, and dielectric properties. The ergodicity to nonergodicity transition was obtained by quenching NBT–6BT–3AN above 1000 °C. The temperature stability of the quenching-induced nonergodicity was examined by annealing the quenched sample at 300 °C and 600 °C. The effect of oxygen vacancy on ergodicity to nonergodicity transition was investigated by comparing ferroelectric and electrostrain responses of the quenched and nitrogen-atmosphere-annealed samples. The influence of quenching on the structure including the average crystal structure, phase fraction and lattice distortion and the local structure including bond lengths and ordering of ions was analyzed. The ergodicity to nonergodicity transition upon quenching is ascribed to the contribution of the off-centered Bi³⁺ ions and ordered local structure.

Graphical abstract

     

Design for Highly Piezoelectric and Visible/Near‐Infrared Photoresponsive Perovskite Oxides

Defect‐engineered perovskite oxides that exhibit ferroelectric and photovoltaic properties are promising multifunctional materials. Though introducing gap states by transition metal doping on the perovskite B‐site can obtain low bandgap (i.e., 1.1–3.8 eV), the electrically leaky perovskite oxides generally lose piezoelectricity mainly due to oxygen vacancies. Therefore, the development of highly piezoelectric ferroelectric semiconductor remains challenging. Here, inspired by point‐defect‐mediated large piezoelectricity in ferroelectrics especially at the morphotropic phase boundary (MPB) region, an efficient strategy is proposed by judiciously introducing the gap states at the MPB where defect‐induced local polar heterogeneities are thermodynamically coupled with the host polarization to simultaneously achieve high piezoelectricity and low bandgap. A concrete example, Ni²⁺‐mediated (1–x)Na_0.5Bi_0.5TiO₃‐xBa(Ti_0.5Ni_0.5)O_3–δ (x = 0.02–0.08) composition is presented, which can show excellent piezoelectricity and unprecedented visible/near‐infrared light absorption with a lowest ever bandgap ≈0.9 eV at room temperature. In particular, the MPB composition x = 0.05 shows the best ferroelectricity/piezoelectricity (d₃₃ = 151 pC N^–1, Pr = 31.2 μC cm^–2) and a largely enhanced photocurrent density approximately two orders of magnitude higher compared with classic ferroelectric (Pb,La)(Zr,Ti)O₃. This research provides a new paradigm for designing highly piezoelectric and visible/near‐infrared photoresponsive perovskite oxides for solar energy conversion, near‐infrared detection, and other multifunctional applications.     

Phase diagram and electric properties of the (Mn, K)-modified Bi0.5Na0.5TiO3–BaTiO3 lead-free ceramics

In this study, the phase diagram and electric properties were demonstrated for a (Mn, K)-modified Bi_0.5Na_0.5TiO₃ (BNT)-based solid solution. (0.935−x) Bi_0.5Na_0.5TiO₃−xBi_0.5K_0.5TiO₃−0.065BaTiO₃ with 0.5% mol Mn doping was prepared by a conventional solid-state reaction method. A morphotropic phase boundary (MPB) formed between the ferroelectric rhombohedral and tetragonal phases around x of 0.04 with the MPB tolerance factor t of 0.984–0.986. The temperature and composition dependence of the dielectric, piezoelectric, ferroelectric properties along with the strain characteristics were investigated in detail and a phase diagram was presented. Around the MPB region, the maximum values of piezoelectric constant d₃₃^* d_{33}^{*} of 290 pC/N, d ₃₃ of 155 pC/N, dielectric constant e₃₃^T /e₀ \varepsilon_{33}^{T} /\varepsilon_{0} of 1059 and low dielectric loss tangent tan δ of 0.017 were obtained. In addition, the authors also suggest that the solid solution with composition x of 0.24, exhibiting both high-depolarization temperature T _d of 182 °C, d₃₃^* d_{33}^{*} of 156 pC/N, d ₃₃ of 130 pC/N, will be favorable for high-temperature actuator and sensor applications.     

Structure and electrical properties of Bi0.5Na0.5TiO3-Y0.5Na0.5TiO3-BaTiO3 lead-free piezoelectric ceramics

New (1 – x ? y)Bi_0.5Na_0.5TiO₃-xY_0.5Na_0.5TiO₃-yBaTiO₃ lead-free ceramics have been prepared by a conventional ceramic fabrication technique, and their structure and electrical properties have been studied. A morphotropic phase boundary (MPB) of rhombohedral and tetragonal phases is formed at 0.04 < y < 0.10. As compared to pure Bi_0.5Na_0.5TiO₃ ceramic, the partial substitutions of Y³⁺ for Bi³⁺ and Ba²⁺ for (Bi_0.5Na_0.5)²⁺ in the A-sites of Bi_0.5Na_0.5TiO₃ lower effectively the coercive field E _c and increase the remanent polarization P _r of the ceramics. Because of low E _c, large P _r and the MPB, the ceramics with x = 0–0.02 and y = 0.06 exhibit the optimum piezoelectric properties: d ₃₃ = 155–159 pC/N and k _p = 28.8–36.7%. The temperature dependences of dielectric properties of the ceramics show relaxor-like behaviors. The ferroelectric properties at different temperature suggest that the ceramics may contain both the polar and non-polar regions near/above T _d.     

Structure and ferroelectric properties in (K0.5Bi0.5)TiO3-BiScO3-PbTiO3 piezoelectric ceramic system

(K_0.5Bi_0.5)TiO₃-BiScO₃-PbTiO₃ ceramics were synthesized by conventional solid-state method. A morphotropic phase boundary (MPB) was confirmed with the aid of structural analysis. Two dielectric anomalous peaks were observed, the one around dielectric maximum temperature (T_m) due to phase transformation from ferroelectric to paraelectric while the second one could be ascribed to space charges. Furthermore, the existence of space charges also resulted in the independence of T_m with frequency at low lead composition. A new high temperature piezoelectric ceramic, 0.30(K_0.5Bi_0.5)TiO₃-0.30BiScO₃-0.40PbTiO₃ close to MPB exhibited excellent electrical properties with T_m of 384 °C, d₃₃ of 247 pC/N, k_p of 38.9%, P_r of 19.41 μC/cm², and E_c of 2.25 kV/mm, indicative of a candidate for high temperature application.     

Effect of substitution of titanium by magnesium and niobium on structure and piezoelectric properties in (Bi1/2Na1/2)TiO3 ceramics

To develop new (Bi_1/2Na_1/2)TiO₃-based ceramics with excellent piezoelectric properties, the similarities and the differences between PZT and (Bi_1/2Na_1/2)TiO₃ ceramics were analysed. Based on the analysis, a new (Bi_1/2Na_1/2)TiO₃-based piezoelectric ceramic of B-site substitution of complex ions (Mg_1/3Nb_2/3)⁴⁺ for Ti⁴⁺ was prepared by a conventional ceramic technique, and the effect of complex ions (Mg_1/3Nb_2/3)⁴⁺ addition on the microstructure, dielectric and piezoelectric properties was investigated. The research results show that all compositions are mono-perovskite phase and the grain size increases with increasing content of (Mg_1/3Nb_2/3)⁴⁺. The piezoelectric constant d ₃₃ first increases and then decreases, and electromechanical coupling factor k _p varies insignificantly with increasing content of (Mg_1/3Nb_2/3)⁴⁺.     

Piezoelectric and dielectric properties of Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–Ba0.77Ca0.23TiO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x)Bi_0.5(Na_0.84K_0.16)_0.5TiO₃–xBa_0.77Ca_0.23TiO₃ (BNKT–xBCT, x = 0–0.04) were synthesized by conventional solid-state reaction method. The piezoelectric, dielectric, and ferroelectric characteristics of the ceramics are investigated and discussed. The XRD results show that Ba_0.77Ca_0.23TiO₃ (BCT) has diffused into Bi_0.5(Na_0.84K_0.16)_0.5TiO₃ (BNKT) lattices to form a new solid solution. It is shown that moderate additive of BCT (x ≤ 0.025) in BNKT–xBCT ceramics can enhance their piezoelectric and ferroelectric properties. Three dielectric anomalies are observed in BNKT–xBCT (x ≤ 0.03) ceramics. The piezoelectric measurements and P–E hysteresis loops reveal that BNKT–0.025BCT ceramic has the highest piezoelectric performance and strongest ferroelectricity in all the samples. Piezoelectric constants d ₃₃, k _p, and k _t of 175 pC/N, 29.1, and 54% are, respectively, achieved. Remnant polarization P _r and coercive field E _c reach 28.3 μC/cm² and 24.2 kV/cm, respectively.     

Dielectric, ferroelectric and piezoelectric properties of Bi0.5Na0.5TiO3-(Ba0.7Ca0.3)TiO3 ceramics at morphotropic phase boundary composition

(1 − x)Bi_0.5Na_0.5TiO₃-x(Ba_0.7Ca_0.3)TiO₃ (BNT-xBCT, 0 ≤ x ≤ 0.15) solid solutions have been synthesized by a conventional solid state sintering method for obtaining a morphotropic phase boundary (MPB) with good piezoelectric properties. X-ray diffraction patterns reveal that a MPB of rhombohedral and tetragonal phases is formed at compositions 0.09 ≤ x ≤ 0.12. Addition of BCT into BNT greatly lowered coercive field E_c without degrading remanent polarization P_r. The specimen with x = 0.09 has the good piezoelectric properties: d₃₃ = 125 pC/N and k_p = 0.33. A modified Curie-Weiss law was used to fit the dielectric constant of BNT-xBCT ceramics, and a frequency dispersion was observed during the phase transitions from antiferroelectric to paraelectric in specimens with x exceeding 0.06.     

Electric field–temperature phase diagram of sodium bismuth titanate-based relaxor ferroelectrics

The electric field–temperature phase diagrams of three bismuth sodium titanate-based relaxor ferroelectrics are reported, namely 0.94(Na_1/2Bi_1/2TiO₃)–0.06(BaTiO₃), 0.80(Na_1/2Bi_1/2TiO₃)–0.20(K_1/2Bi_1/2TiO₃) and 0.75(Na_1/2Bi_1/2TiO₃)–0.25(SrTiO₃). Relaxor behavior is demonstrated by temperature-dependent dielectric permittivity measurements in the unpoled and poled states, as well as by the field-induced phase transition into a ferroelectric phase from the relaxor phase. From temperature-dependent thermometry measurements, we identified the threshold electric field to induce the ferroelectric phase and obtained the released latent heat of the phase transition. We determined the nonergodic and ergodic relaxor phase temperature range based on the absence or presence of reversibility of the relaxor to ferroelectric transition. For all three compositions, the electric field–temperature phase diagram was constructed and a critical point was identified. The constructed electric field–temperature phase diagrams are useful to find optimum operational ranges of ferroelectrics and relaxors for electromechanical and electrocaloric applications.     

Effect of mechanical depoling on piezoelectric properties of Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–<Emphasis Type="Italic">x</Emphasis>BaTiO<Subscript>3</Subscript> in the morphotropic phase boundary region

The effect of mechanical stress on the direct piezoelectric properties of pre-poled (1 ? x)(Na_0.5Bi_0.5)TiO₃–xBaTiO₃ (NBT–xBT) in the range 4% ≤ x ≤ 13% was studied in situ using a mechanical load frame. Prior to mechanical loading, compositions near the morphotropic phase boundary (MPB, x = 6–7% BT) exhibited enhanced ferroelectric and piezoelectric properties compared to compositions further from the MPB. Specifically, the lowest ferroelectric coercive field and highest piezoelectric coefficient within this composition range occur at x = 7% BT. During mechanical compression, the MPB compositions exhibited the lowest depoling stress. The results demonstrate that, while favorable piezoelectric and ferroelectric properties can be obtained at compositions near the MPB, these compositions are also the most susceptible to the effects of mechanical depoling. Ferroelastic domain wall motion is suggested as the primary factor that may be responsible for these behaviors.