Phase evolution and origin of the high piezoelectric properties in lead-free BiFeO3–BaTiO3 ceramics

La-substitution effects for Bi³⁺-site in 0.7Bi_1.03(1-x)La_xFeO₃-0.3BaTiO₃ (abbreviated as BF30BT-100xLF with x = 0.00, 0.01, 0.035, 0.06, 0.07 and 0.10) ceramics were investigated systematically. All ceramics were synthesized by a conventional solid-state reaction method and quenched in water from its sintering temperature. The crystal structure Rietveld refinement shows that undoped BF30BT ceramic exhibited dominant rhombohedral (R) symmetry and gradually changed to the tetragonal (T) phase with La-doping. However, for x ≥ 0.07 compositions the lattice distortions (c_T/a_T and 90°−α_R) significantly decrease as a result crystal structures become close to the cubic-like (CL) phase. Hence, two different morphotropic phase boundaries (MPBs) were reported for BF30BT-100xLa ceramic system; one MPB-I between the R and T phases and the other MPB-II between T and CL phases. The largest direct piezoelectric coefficient (d₃₃ = 274 pC/N) with a high Curie temperature (T_C = 532 °C) for BF30BT-1LF composition was obtained due to the typical MPB-I between R and T phases. However, a maximum electric field-induced strain (S_max = 0.27%) with a high converse piezoelectric coefficient (d₃₃* = 500 pm/V) for BF30BT-7LF ceramic was mainly attributed to the MPB-II of T + CL phases and soft ferroelectric switching properties.     

Structural modification and evaluation of dielectric and ferromagnetic properties of Ce-modified BiFeO3–BaTiO3 ceramics

An investigation on Rare earth constituent Ce incorporated BiFeO₃–BaTiO₃ ceramics has been focused in the present study. The ceramic samples of (Bi₀.₇Ba_0.3)_1-xCe_x(Fe₀.₇Ti_0.3)O₃ (x = 0–0.12) were formulated adopting the cost-effective solid-state sintering method. The influence of aliovalent Ce ions on the structural, microstructural, dielectric, ferromagnetic, and optical properties of BiFeO₃–BaTiO₃ was evaluated in this paper. The coexistence of the Tetragonal and the Rhombohedral phases was established by the Rietveld refinement process. The refined crystallographic parameters showed maximum cell volume (V_cell) and the highest percentage of the Rhombohedral phase for x = 0.06; and consequently, the ceramic exhibited the topmost dielectric constant of 946 at x = 0.06. The scanning electron microscopy of the samples revealed the manifestation of polygonal grain morphology. Besides, remarkably improved ferromagnetic properties were evinced for Ce doped ceramics. The magnitude of saturation (M_s) and remnant (M_r) magnetizations were boosted from 0 emu/g and 0.0019 emu/g to 0.9186 emu/g and 0.3745 emu/g respectively with increasing x from 0 to 0.12. Additionally, the optical band gaps of all the samples were evaluated and found to be in the range of 2.941–3.077 eV.     

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.     

High and temperature-insensitive piezoelectric performance in the lead-free Sm-doped BiFeO3–BaTiO3 ceramics with high Curie temperature

Large sensor piezoelectric constant (d₃₃ = 334 pC/N) and superior actuator piezoelectric constant (d₃₃* = 552 pm/V) as well as a high Curie temperature (T_C = 454 °C) were obtained simultaneously in the lead-free 0.67Bi_1.03FeO₃-0.33Ba_1-xSm_xTiO₃ ceramics. Such an excellent and temperature-insensitive piezoelectric performance with only 10% temperature variation of piezoelectric strain at the range of 25–125 °C is highly desirable for real applications. The structural origin of the enhanced piezoelectric performance is mainly attributed to the morphotropic phase boundary and the highest known tetragonality (c_T/a_T = 1.02) in such materials. Transmission electron microscopy and electro-mechanical phenomenological theory demonstrate that the superior d₃₃ and d₃₃* are associated with the hybrids nanodomains (60–90 nm) and flattened thermodynamic energy profile owing to the local structure heterogeneity. These results are superior as the piezoelectric properties are temperature-independent and the material has large d₃₃*, and high T_C compared to other lead-free piezoelectric ceramics.     

Properties of spark plasma sintered pseudocubic BiFeO3–BaTiO3 ceramics

Perovskite solid solution materials, namely, 0.67BiFeO₃-0.33BaTiO₃, were synthesized by spark plasma sintering method. The effects of the spark plasma sintering temperature on phase purity, microstructure, and electric properties of the as-prepared materials were investigated. The materials could be referred as pseudocubic phases based on the X-ray diffraction patterns. The bulk density first increased and then decreased. The 880 °C-sintered-ceramics had the maximal density and a compact microstructure with grain size of 0.77 ± 0.34 μm. The dielectric constant as a function of temperature exhibited a broad peak. At the optimal spark-plasma-sintering temperature, enhanced ferroelectric properties were observed with a value of P_r ～ 21 μC/cm². This investigation on the spark plasma sintering process confirms it as an efficient approach to prepare outstanding performance BiFeO₃–BaTiO₃ ceramics.     

Microstructure and luminescence properties of the high pressure high temperature sintered AlN–TiN ceramics

Composite ceramics of titanium nitride grains incorporated in an aluminium nitride matrix have been synthesized by high pressure high temperature treatment of a mechanical mixture of AlN–TiN (3 mol % TiN) powders. The microstructure of the samples analysed by means of electron beam microanalysis and Raman spectroscopy shows that the formation of cubic AlN in the composite begins near titanium nitride grains. The areas of mixed chemical composition, which can be assigned to the formation of the solid solutions Al_1?xTi_xN, have been observed at the phase interfaces. The luminescence properties of AlN–TiN ceramics have been considered focusing on the choice of high pressure and high temperature treatment conditions. Three main components at 2.0 eV, 2.4 eV and 3.1 eV are revealed in the cathodoluminescence spectra analysed quantitatively. The observed emission originates from the radiative transitions with participation of valence band states, oxygen-vacancy centres (V_Al–O_N), nitrogen vacancies V_N, and shallow donors which form a complex system of energy levels in the bandgap of the wurtzite-type AlN.     

Energy storage performance of BiFeO3–SrTiO3–BaTiO3 relaxor ferroelectric ceramics

Dielectric capacitors reveal great potential in the application of high power and/or pulsed power electronic devices owing to their ultrafast charge–discharge rate and ultrahigh power density. Among various dielectric capacitors, the environment-friendly lead-free dielectric ceramics have drawn extensive investigations in recent years. Nevertheless, the relatively small recoverable energy storage density (W_rec) is still an obstacle for their application. Herein, the (0.55−x)BiFeO₃–0.45SrTiO₃–xBaTiO₃ ternary ceramics with 0.1 wt% MnO₂ were prepared by the solid-state reaction, and achieved enhanced relaxor behavior as well as breakdown strength E_b. As a result, the x = 0.12 ceramic exhibited superior comprehensive energy storage performance of large E_b (50.4 kV/mm), ultrahigh W_rec (7.3 J/cm³), high efficiency η (86.3%), relatively fast charge–discharge speed (t_0.9 = 6.1 μs) and outstanding reliability under different frequency, fatigue, and temperature, indicating that the BiFeO₃-based relaxor ferroelectric ceramics are prospective alternatives for electrostatic energy storage.     

Ferroelectromagnetic characteristic of Na-doped 0.75BiFeO3–0.25BaTiO3 multiferroic ceramics

BiFeO₃-based materials are expected to have both ferroelectricity and ferromagnetism simultaneously. In this study, effects of Na-doping (0.5, 1.0, 3.0, and 5.0 mol%) on ferromagnetic and ferroelectric properties of 0.75BiFeO₃–0.25BaTiO₃ ceramics which have been fabricated by the solid state reaction technique are studied. The effects of Na-doped 0.75BiFeO₃–0.25BaTiO₃ ceramics on the crystal structure, and magnetic and electrical properties were investigated and discussed. Rhombohedrally distorted 0.75BiFeO₃–0.25BaTiO₃ showed weak ferromagnetic and ferroelectric properties. In addition, ferroelectric and ferromagnetic properties of 0.75BiFeO₃–0.25BaTiO₃ have been controlled by Na doping, and the maximum values of magnetization and polarization were observed at 5.0 mol%.     

High piezoelectric properties in 0.7BiFeO3–0.3BaTiO3 ceramics with MnO and MnO2 addition

BiFeO₃–BaTiO₃–based solid solutions are promising candidates for high–temperature piezoelectric devices because of their high Curie temperature (T_C) and considerable electrical properties. Here, we reported an optimum composition of 0.7Bi(Fe_0.999Mn_0.001)O₃–0.3BaTiO₃ ceramic with a large piezoelectric constant (d₃₃) of 230 pC/N and a high T_C of 505 °C, which was attributed to the intentional introducing of the ceramic with MnO and MnO₂ mixture. Furthermore, an in situ d₃₃ measurement was carried out, demonstrating excellent thermal stability for the 0.7Bi(Fe_0.999Mn_0.001)O₃–0.3BaTiO₃ specimen. The d₃₃ remained above 200 pC/N in the temperature range of 25 °C–400 °C and its fluctuation was less than ± 15 %. It was determined that the high d₃₃ in the 0.7BiFe_0.999Mn_0.001)O₃–0.3BaTiO₃ ceramic originated from a synergistic effect of rhombohedral distortion, intrinsic response, and ferroelectric order. The findings establish a solid correlation between electrical properties and phase/domain structure, and provide a novel approach to improve the piezoelectric properties for BiFeO₃–BaTiO₃–based ceramics.     

Structure–property relationships in BaTiO3–BiFeO3–BiYbO3 ceramics

Ba_1?xBi_xTi_1?xYb_x/2Fe_x/2O₃ ceramics were fabricated by the solid state reaction method. X-ray diffraction analyses show 0 ≤ x ≤ 0.04 ceramics to have an average crystal structure described by the non-centrosymmetric tetragonal P4 mm space group, whereas x ≥ 0.08 ceramics are consistent with a centrosymmetric cubic perovskite (space group Pm-3 m). Coexistence of both tetragonal and cubic symmetries is observed for x = 0.06. Raman spectroscopy analysis corroborate a change in average structure with increasing x, but also show the local crystal symmetry for x ≥ 0.08 ceramics to deviate from the idealized cubic perovskite structure. Dielectric data show a ferroelectric-to-relaxor crossover, which occurs in conjunction with the change in both the average and local crystal symmetry as indicated by X-ray and Raman data. For x ≥ 0.08, ceramics exhibit relaxor behavior, which is also accompanied by a shift of the permittivity maxima towards higher temperatures with increasing x.     

Grain size effect on electrical properties of Mn-modified 0.67BiFeO3–0.33BaTiO3 lead-free piezoelectric ceramics

To investigate how grain size affects the dielectric, ferroelectric, and piezoelectric properties of Mn-modified 0.67BiFeO₃–0.33BaTiO₃ ceramics, we prepared samples with a wide variety of grain sizes from 4.1 μm to 0.59 μm via a conventional solid-state process that use the normal and the two-step sintering methods. Small-signal dielectric measurements show that all the samples exhibit a relaxor-like behavior and that grain size has little influence on the room-temperature dielectric permittivity. For grain sizes below 2 μm, the remanent polarization P_r and piezoelectric coefficient d₃₃ decrease with the grain size, whereas they remain almost constant near P_r = 27 μC/cm² and d₃₃ = 70 pC/N in samples with grain sizes exceeding 2 μm. The mechanism underlying the observed grain size effect is discussed in terms of the electric-field-induced formation of macroscopic ferroelectric domains.     

Low sintering temperature,large strain and reduced strain hysteresis of BiFeO3–BaTiO3 ceramics for piezoelectric multilayer actuator applications

BiFeO₃–BaTiO₃ solid solutions with pseudo-cubic phase have received a lot of attention because of their large strain for potential piezoelectric multilayer actuator applications. However, the high sintering temperature, large dielectric loss and severe strain hysteresis hindered their real applications. In this work, Li₂CO₃ sintering aid modified 0.64BiFeO₃-0.36BaTiO₃ (BF-BT-L) ceramics were prepared by the high-temperature sintering method, and their phase structure, microstructure, electric properties as well as strain were investigated. With the increase of Li₂CO₃ content, the sintering temperature decreases down to 900 °C, and the relative density increases up to 96%. Of particular importance is that the dielectric loss and strain hysteresis of BF-BT-L ceramics are reduced by 40% and 47%, respectively, while BF-BT-L ceramics shows a large strain of 0.3% (60 kV/cm). The sintering temperature, relative density, strain, large-signal d₃₃* and strain hysteresis of BF-BT-L ceramics are 900 °C, 96.5%, 0.3%, 500 pm/V, and 25% respectively. The reduced dielectric loss and strain hysteresis result from the enhanced relative density, decreased concentration of defects and partial phase transition from partial pseudo-cubic to rhombohedral one by Li₂CO₃ additions. Furthermore, BF-BT-L ceramics show positive temperature dependent strain, with large d₃₃* and strain hysteresis of 675 pm/V and 15% at 200 °C respectively. The simple composition, low sintering temperature, large strain and reduced strain hysteresis of BF-BT-L ceramics indicate that they are promising candidates for high-performance and lead-free piezoelectric multilayer actuator applications.     

Optimized electric-energy storage in BiFeO3–BaTiO3 ceramics via tailoring microstructure and nanocluster

This study demonstrates the high energy-storage performance using 0.1 wt% MnO₂–added 0.7(Bi_1?xSm_xFeO₃)? 0.3(BaTiO₃) (x = 0–0.3) ceramics through tailoring microstructures and polar order. Sequential structure transitions were identified from a co-occurrence of nonpolar pseudo-cubic Pm-3m and ferroelectric rhombohedral R3c symmetries to antipolar orthorhombic Pbam and nonpolar orthorhombic Pnma symmetries as Sm substitution increases. Recoverable energy densities (W_rec) of 4.5 J/cm³ and 4.1 J/cm³ with efficiencies (η) of 62.1% and 78.1% were achieved respectively for x = 0.15 and 0.2 at a field of 220 kV/cm. The improved energy storage is associated with microstructure modification and complex grain matrix, consisting of grain boundaries, nanocluster/nanomosaic structures, core-shell structures, and polar nanoregions. The nanocluster/nanomosaic structures may act as barriers to suppress polar order and enhance dielectric breakdown strength. This work provides an efficient route to utilize binary BiFeO₃-BaTiO₃ ceramics for electrical energy storage.     

Enhanced resistivity and strain stability of BiFeO3–BaTiO3 ceramics by hot-press sintering in oxygen atmosphere

Even though BiFeO₃–BaTiO₃ (BF–BT) with high Curie temperature and excellent piezoelectric properties is very suitable for high-temperature applications, its rapid reduction in resistivity with temperature limits its further application. So far, there is no effective method to improve the resistivity of BF–BT at a high-temperature state. In this work, hot-press sintering combined with an oxygen atmosphere was used to prepare (1 − x)BF–xBT (x = 0.2–0.33) ceramics for the first time, which reduced the sintering temperature from 1000 to 920°C. The controllable grain size can be achieved by adjusting the sintering temperature and the applied pressure. The X-ray photoelectron spectroscopy results confirmed that using hot-press sintering effectively avoided the generation of heterovalent Fe ions, and the resistivity of BF–BT ceramics at the high-temperature stage was improved by two orders of magnitude. It was found that hot-press sintering can cause the oriented growth of the sample along the (1 1 0) direction, and further refined X-ray diffraction was used to accurately analyze the changes in the lattice structure. The hot-press sintered samples obtained larger polarization strength, especially the electro-induced strain showed excellent temperature stability in the wide temperature range of 30–170°C. Hot-pressing sintering combined with an oxygen atmosphere is more suitable for preparing high insulation and electrical breakdown resistance ceramics.     

Phase structure and energy storage performance for BiFeO3–BaTiO3 based lead-free ferroelectric ceramics

Recently, BiFeO₃–BaTiO₃ (BF-BT) lead-free ferroelectric ceramics have been widely concerned and deemed as one of the most promising candidates for lead-free energy-storage material because of their high spontaneous polarization and excellent energy storage properties. Herein, a series of Bi_1-zLa_zFeO₃-xBaTiO₃+yMnO₂ (BL_zF-xBT-yMn at 0.45 ≤ x ≤ 0.60 mol, 0.0 ≤ y ≤ 0.4% mol and z = 0 or 0.02 mol) ceramics were prepared to reveal their energy-storage performance. With increasing x, the breakdown strength (BDS) increases, while the maximum polarization (P_max), remanent polarization (P_r), and the difference value between P_max and P_r (ΔP) decrease. Because of the high BDS and ΔP, a large energy storage density W_re = 1.08 J/cm³ is achieved in BF-0.48BT ceramics as the electric field is 130 kV/cm. In addition, with increasing y and z, the increasing BDS and ΔP have been observed. Due to the improvement in BDS and ΔP, an excellent W_re = 1.22 J/cm³ was achieved in Bi_1-zLa_zFeO₃-xBaTiO₃+yMnO₂ ceramics at x = 0.48, y = 0.3% and z = 0.02. This work provides the clue for application of the high-power-energy BF-BT ceramics.     

Coexistence of three ferroelectric phases and enhanced piezoelectric properties in BaTiO3–CaHfO3 lead-free ceramics

Perovskite ferroelectrics possess the fascinating piezoelectric properties near a morphotropic phase boundary, attributing to a low energy barrier that the results in structural instability and easy polarization rotation. In this work, a new lead-free system of (1-x)BaTiO₃-xCaHfO₃ was designed, and characterized by a coexistence of ferroelectric rhombohedral-orthorhombic-tetragonal (R-O-T) phases. With the increase amount of CaHfO₃ (x), a stable coexistence region of three ferroelectric phases (R-O-T) exists at 0.06 ≤ x ≤ 0.08. Both large piezoelectric coefficient (d₃₃～400 pC/N), inverse piezoelectric coefficient (d₃₃^*～547 pm/V) and planar electromechanical coupling factor (k_p～58.2%) can be achieved for the composition with x = 0.08 near the coexistence of three ferroelectric phases. Our results show that the materials with the composition located at a region where the three ferroelectric R-O-T phases coexist would have the lowest energy barrier and thus greatly promote the polarization rotation, resulting in a strong piezoelectric response.     

Room temperature multiferroic properties of BiFeO3–MnFe2O4 nanocomposites

The novel functionalities of multiferroic magneto-electric nanocomposites have spawned substantial scope for fast-paced memory devices and sensor applications. Following this, herein we report the development of nanocomposites with soft ferromagnetic MnFe₂O₄ and ferroelectric BiFeO₃ to fabricate a system with engineered multiferroic properties. A modified sol-gel route called Pechini method is demonstrated for the preparation of the (1-x) BiFeO₃-x MnFe₂O₄ (x = 10%, 30%, 50%, 70%) nanocomposites. The crystallographic phase, structure, and morphology are characterized by XRD, FESEM, and HRTEM. The accurate crystallite size and lattice strain are determined by Williamson-Hall plot method and a comparative study with Scherer's equation is carried out. TEM image evidences the interface between BiFeO₃ and MnFe₂O₄ nanoparticles in the composite. The room temperature magnetic response reveals the strong dependence of magnetic saturation, remanent magnetization, and coercivity of the nanocomposites on MnFe₂O₄ addition. The dielectric response and impedance analysis of the prepared nanocomposites are observed. The electrical performance of the composite is affected by grain, grain boundaries, and oxygen vacancies. The unsaturated P-E loops exhibit the leaky ferroelectric behavior for the nanocomposite. The intrinsic magnetoelectric coupling between ferroelectric BiFeO₃ and ferromagnetic MnFe₂O₄ has been determined by varying H_dc/H_ac and its maximum coupling coefficient (α) is found to be 25.39 mV/cmOe for 70% BiFeO₃ -30% MnFe₂O₄ nanocomposite. These distinctive and achievable characteristics of the nanocomposite would enable the designing of magnetic field sensors, spintronic devices, and multiferroic memory devices.     

Enhanced aging behaviors and electric thermal stabilities in 0.75BiFeO3–0.25BaTiO3 piezoceramics by Mn modifications

Lead-free 0.75BiFeO₃–0.25BaTiO₃ (0.75BF–0.25BT) ceramics have been extensively studied because of their high Curie temperature. The aging behavior and thermal stability of piezoceramics play decisive roles in their device applications. In this work, effects of Mn doping on the phase structure, aging behavior, and thermal stability of 0.75BF–0.25BT ceramics were characterized and related mechanisms were investigated. With the increase in Mn content, the typical rhombohedral phase of 0.75BF–0.25BT ceramics changed to the coexistence of pseudo-cubic and rhombohedral phases. Mn modification enhanced the aging behavior and thermal stability of ceramics obviously. The aging rates of d₃₃ and k_p for 0.75BF-0.25BT ceramics with 1.0 mol% Mn are 1.3% and 1.1%, respectively, which are only 1/4 those values for the undoped ceramics. The variation of ε_r of 0.75BF-0.25BT ceramics with 1.0 mol% Mn is half of undoped ceramics under 500℃. The depoling temperature of 0.75BF-0.25BT ceramics with 1.0 mol% Mn was 450℃, which is about 200℃ higher than that of undoped ceramics. The enhanced aging behavior results from the decreased defect concentrations, and the better thermal stability is owing to the significantly improved poling state due to the enhanced resistivity, large grain size, and decreased crystal distortion by Mn modification. These results reflect that a proper amount of Mn doping is an effective way to enhance the aging behavior and electric thermal stability.     

Dielectric properties and related ferroelectric domain configurations in multiferroic BiFeO3–BaTiO3 solid solutions

Dielectric properties and ferroelectric domain configurations of multiferroic xBaTiO₃–(1 ? x)BiFeO₃ (x = 0.10–0.33) solid solutions synthesized by conventional solid-state reaction, were reported. A structural transition from rhombohedral to pseudo-cubic structures appeared around x = 0.33, and the formation of impurity phase of Bi₂Fe₄O₉ was effectively depressed by doping BaTiO₃. Dielectric constants of xBaTiO₃–(1 ? x)BiFeO₃ solid solutions decreased with increasing the frequency, and the degree of decrease was related to the doping content of BaTiO₃. Transmission electron microscopy images revealed that the ferroelectric domain configurations in the multiferroic BiFeO₃–BaTiO₃ solid solutions with rhombohedral symmetry, exhibited a wavy character whereas a predominant intricate domain structure with fluctuating mottled contrast was observed in the multiferroic BiFeO₃–BaTiO₃ solid solution with pseudo-cubic phase structure. The presence of 1/2{1 1 1} superlattice spots in the selected area electron diffraction patterns taken from the multiferroic BiFeO₃–BaTiO₃ solid solutions with rhombohedral symmetry indicated that the ordered regions have a doubled perovskite unit cell.     

Influence of sintering temperature on energy storage properties of BaTiO3–(Sr1−1.5xBix) TiO3 ceramics

The effect of sintering temperature on microstructure, dielectric properties and energy storage properties of BaTiO₃–(Sr_1?1.5xBi_x)TiO₃ (x = 0.09) (BT–SBT) ceramics was investigated. The sintering temperature has pronounced influence on the grain size, shrinkage, and dielectric properties of the BT–SBT ceramics. With increasing sintering temperature, the dielectric constant increases largely. However, the increasing tendency of the dielectric breakdown strength (BDS) is less noticeable but become more evident with the consideration of Weibull modulus. For the BT-SBT ceramics, the unreleased energy density decreases and the electric field stability of the energy storage efficiency enhances with the increase of sintering temperature.