The effects of Bi(Mg2/3Nb1/3)O3 on piezoelectric and ferroelectric properties of K0.5Na0.5NbO3 lead-free piezoelectric ceramics

To improve the temperature stability of piezoelectric properties of Na_0.5K_0.5NbO₃ (KNN)-based ceramics, Bi(Mg_2/3Nb_1/3)O₃ (BMN) was used to modify Na_0.5K_0.5NbO₃ (KNN)-based ceramics by a conventional sintering technique. Piezoelectric and ferroelectric properties of 0.99K_0.5Na_0.5NbO₃-0.01Bi(Mg_2/3Nb_1/3)O₃ ceramics were studied. It is found that 0.01BMN-0.99KNN ceramics exhibits stable piezoelectric properties as the temperature changes due to the composition fluctuation on B sites (d₃₃ ≈ 130 pC/N, dielectric loss tg θ ≤ 5% in the range 25-300 °C). These results indicate that these materials are promising lead-free piezoelectric ceramic candidates for practical applications.     

Phase transition and piezoelectric properties of K0.48Na0.52NbO3-LiTa0.5Nb0.5O3-NaNbO3 lead-free ceramics

Plate-like NaNbO₃ (NN) particles were used as the raw material to fabricate (1 − x)[0.93 K_0.48Na_0.52Nb O₃-0.07Li(Ta_0.5Nb_0.5)O₃]-xNaNbO₃ lead-free piezoelectric ceramics using a conventional ceramic process. The effects of NN on the crystal structure and piezoelectric properties of the ceramics were investigated. The results of X-ray diffraction suggest that the perovskite phase coexists with the K₃Li₂Nb₅O₁₅ phase, and the tilting of the oxygen octahedron is probably responsible for the evolution of the tungsten-bronze-typed K₃Li₂Nb₅O₁₅ phase. The Curie temperature (T_C) is shifted to lower temperature with increasing NN content. (1 − x)[0.93 K_0.48Na_0.52NbO₃-0.07Li(Ta_0.5Nb_0.5)O₃]-xNaNbO₃ ceramics show obvious dielectric relaxor characteristics for x > 0.03, and the relaxor behavior of ceramics is strengthened by increasing NN content. Both the electromechanical coupling factor (k_p) and the piezoelectric constant (d₃₃) decrease with increasing amounts of NN. 0.01-0.03 mol of plate-like NaNbO₃ in 0.93 K_0.48Na_0.52NbO₃-0.07Li(Ta_0.5Nb_0.5)O₃ gives the optimum content for preparing textured ceramics by the RTGG method.     

Dielectric and piezoelectric properties of Sb doped (NaBi)0.38(LiCe)0.05[]0.14Bi2Nb2O9 ceramics

Sb⁵⁺-doped (NaBi)_0.38(LiCe)_0.05[]_0.14Bi₂Nb₂O₉ (represented as NBNLCS-x, where [] represents A-site vacancies) ceramics were prepared by the conventional solid-state route. The ceramics well sintered to approach ∼98.5% theoretical density and the tetragonality of crystal structure increased with Sb⁵⁺ additions. However, the Curie temperature (T_C) and the piezoelectric coefficient (d₃₃) of Sb⁵⁺-modified ceramics gradually decreased. The 3 mol% Sb⁵⁺-doped samples exhibited optimum properties with a d₃₃ value of ∼22 pC/N planar electromechanical coupling factor (k_p) of ∼11.2% and relatively high T_C of ∼765 °C. These results indicate that NBNLCS-x material is a promising candidate for high-temperature piezoelectric applications.     

The temperature-dependent electrical properties of Bi0.5Na0.5TiO3-BaTiO3-Bi0.5K0.5TiO3 near the morphotropic phase boundary

Bi_0.5Na_0.5TiO₃-BaTiO₃-Bi_0.5K_0.5TiO₃ (BNT-BT-BKT) lead-free piezoceramics with compositions near the rhombohedral-tetragonal morphotropic phase boundary (MPB) were prepared and investigated. At room temperature, all ceramics show excellent electrical properties. In this study, the best properties were observed in 0.884BNT-0.036BT-0.08BKT, with the remnant polarization, bipolar total strain, unipolar strain, piezoelectric constant, and planar electromechanical coupling factor being 34.4 μC cm⁻², 0.25%, 0.15%, 122 pC N⁻¹, and 0.30, respectively. Detailed analysis of the temperature dependence of polarization-electric field (P-E) loops and bipolar/unipolar strain-electric field (S-E) curves of this composition revealed a ferroelectric-antiferroelectric phase transition around 100 °C. Around this temperature, there is a significant shape change in both P-E and S-E curves, accompanied by enhanced strain and decreased polarization; the largest recoverable strain reaches 0.42%. These results can be explained by the formation of antiferroelectric order and the contribution of field-induced antiferroelectric-ferroelectric phase transition to piezoelectric response. Our results indicate that BNT-BT-BKT lead-free piezoceramics can have excellent electrical properties in compositions near the MPB and also reveal some insight into the temperature dependence of the electrical performance with the MPB composition.     

Effect of addition of Ba(W0.5Cu0.5)O3 in Pb(Mg1/3Nb2/3)O3-Pb(Zn1/3Nb2/3)O3-Pb(Zr0.52Ti0.48)O3 ceramics on the sintering temperature, electrical properties and phase transition

In this work, we report on the Pb(Mg_1/3Nb_2/3)O₃-Pb(Zn_1/3Nb_2/3)O₃-Pb(Zr_0.52Ti_0.48)O₃ (PMN-PZN-PZT) ceramics with Ba(W_0.5Cu_0.5)O₃ as the sintering aid that was manufactured in order to develop the low-temperature sintering materials for piezoelectric device applications. The phase transition, microstructure, dielectric, piezoelectric properties, and the temperature stability of the ceramics were investigated. The results showed that the addition of Ba(W_0.5Cu_0.5)O₃ significantly improved the sintering temperature of PMN-PZN-PZT ceramics and could lower the sintering temperature from 1005 to 920 °C. Besides, the obtained Ba(W_0.5Cu_0.5)O₃-doped ceramics sintered at 920 °C have optimized electrical properties, which are listed as follows: (K_p = 0.63, Q_m = 1415 and d₃₃ = 351 pC/N), and high depolarization temperature above 320 °C. These results indicated that this material was a promising candidate for high-power multilayer piezoelectric device applications.     

Effects of annealing atmosphere on the structural and electrical properties of (Na0.5K0.5)NbO3 thin films grown by RF magnetron sputtering

Amorphous (Na_0.5K_0.5)NbO₃ (NKN) thin films were grown at 300 °C and subsequently annealed at 800 °C under Na₂O, K₂O and NKN atmospheres. When the annealing time was less than 50 min, K₆Nb_10.88O₃₀ and Na₂Nb₄O₁₁ secondary phases were formed in all the films. Moreover, they were also found in films annealed at 750 °C for 180 min under NKN atmosphere, indicating that they were transient phases formed when the sintering time and temperature were not sufficient. For the film annealed for 50 min under Na₂O atmosphere, an Na-excess (Na_1?xK_x)NbO₃ (N_1?xK_xN) phase was formed, whereas a K-excess N_1?xK_xN phase was developed in the film annealed under K₂O atmosphere. On the other hand, a homogeneous NKN phase was developed in the film annealed under NKN atmosphere and this was maintained after a long period (100 min) of annealing at 800 °C. A high leakage current density and a small dielectric constant (ε_r) were observed for films annealed under Na₂O and K₂O atmospheres due to the evaporation of K₂O and Na₂O, respectively. Moreover, they exhibited a small remnant polarization (P_r) and a small coercive electric field (E_c). On the other hand, the film annealed under NKN atmosphere exhibited a very low leakage current density of 2.6 × 10^?9 A cm^?2 at 0.2 MV cm^?1 and had good ferroelectric and piezoelectric properties of ε_r = 620, P_r = 11.7 μC cm^?2, E_c = 133.8 kV cm^?1 and d₃₃ = 74 pm V^?2 at 50 kV cm^?1.     

Piezoelectric and dielectric properties of Dy2O3-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ + x wt% Dy₂O₃ with x = 0-0.3 ceramics were synthesized by conventional solid-state processes. The effects of Dy₂O₃ on the microstructure, the piezoelectric and dielectric properties were investigated. X-ray diffraction pattern confirmed that the coexistence of tetragonal and rhombohedral phases in the (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ composition was not changed by adding 0.05-0.3 wt% Dy₂O₃. SEM images indicate that all the ceramics have pore-free microstructures with high density, and that doping of Dy₂O₃ inhibits the grain growth of the ceramics. The addition of Dy₂O₃ shows the double effects on decreasing the piezoelectric and dielectric properties for 0 < x < 0.15 when Dy³⁺ ions substitute B-site Ti⁴⁺ ions, and increasing the properties for 0.15 < x < 0.3 when Dy³⁺ ions enters into A-site of the perovskite structure. The optimum electric properties of piezoelectric constant d₃₃ = 170 pC/N and the dielectric constant ?_r = 1900 (at a frequency of 1 kHz) are obtained at x = 0.3.     

Room temperature ferromagnetism and magnetoelectric coupling in (K0.5Na0.5)NbO3 PLD nanocrystalline films

(K_0.5Na_0.5)NbO₃ nanocrystalline films have been successfully prepared on conductive Si substrate under different conditions by pulsed laser deposition. Room temperature ferromagnetism has been achieved through the introduction of cation (K, Na) vacancies during deposition at the expense of the deterioration of ferroelectricity. In addition to positive magnetocapacitance effect and electrical manipulation of magnetization, the new phenomenon that the orthometric application of an electric field and magnetic field on the surface of film leads to an enormous enhancement of in-plane saturation magnetization has been first observed, indicative of a strong magnetoelectric coupling which has a memory effect on the saturation magnetization at room temperature.     

Effect of V doping on phase composition and electrical properties of K0.4Na0.6Nb1−xVxO3 thin films

Lead-free K_0.4Na_0.6Nb_1−xV_xO₃ thin films were prepared by chemical solution deposition method. The effects of V doping on the phase composition and electrical properties of the films were studied at room temperature. The results indicate that the films are composed of orthorhombic and tetragonal phases, and the phase composition is affected by V content. It is also found that the ferroelectric and dielectric properties are improved by V doping (2P_rmax = 35.5 μC/cm, ?_max = 1189). The enhanced electrical properties are attributed to the more T-phase content and better quality of K_0.4Na_0.6Nb_1−xV_xO₃ (x = 0.015) film.     

A diffuse phase transition study on Ba substituted (Na0.5Bi0.5)TiO3 ferroelectric ceramic

Polycrystalline perovskite lead free material (Na_0.5Bi_0.5)_0.91Ba_0.090TiO₃ was prepared by solid state reaction method. The crystal structure examined by X-ray powder diffraction indicates that the material was single phase with tetragonal structure. Dielectric studies exhibit a diffuse phase transition and characterized by a strong temperature and frequency dispersion of permittivity which relates cation disorder at A-site and exhibits relaxor behaviour. The dielectric relaxation has been modeled using the Vogel-Fulcher relationship, the calculated activation energy found to be E_a = 0.021 eV. Complex impedance analysis indicates the system undergoing a polydispersive non-Debye type relaxation. Also, used to characterize grain and grain-boundary resistivities of Ba substituted (Na_0.5Bi_0.5)TiO₃ ceramic. The phenomenon was also interpreted by accounting for microstructural differences. The corresponding relaxation times were also used to confirm the interpretation of complex impedance spectra. Overlapping of grain boundary and electrode relaxation processes can be separated above about 4000 C. Electrical modulus spectroscopy studies have been performed. The conductivity parameters such as ion-hopping rate (ω_p) and the charge carrier concentration (K¹) have been calculated using Almond and West formalism.     

Fabrication and characterization of ceramic thin films by RF magnetron sputtering using Zn-enriched (Ba0.3Sr0.7)(Zn1/3Nb2/3)O3 as target

Dielectric ceramic thin film was fabricated on SiO₂ (1 1 0) substrates by radio frequency (RF) magnetron sputtering method using a Zn-enriched (Ba_0.3Sr_0.7)(Zn_1/3Nb_2/3)O₃ target. The microstructure, components, and morphological properties of the thin films were characterized thoroughly. The results reveal that the main phases of the thin films are Ba_xSr_1−xNb₂O₆, which are of different compositions from that of the ceramic target due to Zn loss. The thin films are polycrystalline and of dense structure with uniform grain sizes and well-defined grain boundaries.     

Preparation and electrical properties of Bi0.5Na0.5TiO3-BaTiO3-KNbO3 lead-free piezoelectric ceramics

Lead-free (1 − x)Bi_0.47Na_0.47Ba_0.06TiO₃-xKNbO₃ (BNBT-xKN, x = 0-0.08) ceramics were prepared by ordinary ceramic sintering technique. The piezoelectric, dielectric and ferroelectric properties of the ceramics are investigated and discussed. The results of X-ray diffraction (XRD) indicate that KNbO₃ (KN) has diffused into Bi_0.47Na_0.47Ba_0.06TiO₃ (BNBT) lattices to form a solid solution with a pure perovskite structure. Moderate additive of KN (x ≤ 0.02) in BNBT-xKN ceramics enhance their piezoelectric and ferroelectric properties. Three dielectric anomaly peaks are observed in BNBT-0.00KN, BNBT-0.01KN and BNBT-0.02KN ceramics. With the increment of KN in BNBT-xKN ceramics, the dielectric anomaly peaks shift to lower temperature. BNBT-0.01KN ceramic exhibits excellent piezoelectric properties and strong ferroelectricity: piezoelectric coefficient, d₃₃ = 195 pC/N; electromechanical coupling factor, k_t = 58.9 and k_p = 29.3%; mechanical quality factor, Q_m = 113; remnant polarization, P_r = 41.8 μC/cm²; coercive field, E_c = 19.5 kV/cm.     

Relationship between structure and properties in high-temperature Bi(Al0.5Fe0.5)O3-PbTiO3 piezoelectric ceramics

Ceramic samples of xBi(Al_0.5Fe_0.5)O₃-(1 − x)PbTiO₃ (BAF-PT, x = 0.05-0.5) solid solutions were fabricated using the conventional solid state reaction method. X-ray diffraction analysis revealed that all compositions can form single perovskite phase with tetragonal symmetry. The relationship between the tetragonal lattice parameters, tetragonality c/a, cell volume, and ferro-piezoelectric characterization as a function of x was systematically investigated. The BAF modification can effectively improve the poling condition at a proper BAF content. A combination of piezoelectric constant of d₃₃ (50-60 pC/N), electromechanical planar coupling coefficients of k_p (20.3-22.5%), and high Curie temperature T_c (>478 °C) suggested that BAF-PT could be a good candidate for high-temperature piezoelectric applications.     

Phase transition-induced high electromechanical activity in [(K0.5Na0.5)1−xLix](Nb0.8Ta0.2)O3 lead-free ceramic system

A high electromechanical activity is observed in the [(K_0.5Na_0.5)_1−xLi_x](Nb_0.8Ta_0.2)O₃ (x = 0, 0.02, and 0.03) lead-free ceramic system at and around the orthorhombic (O)–tetragonal (T) phase transition temperature (T_O–T). This activity is found to originate from an O–T phase transition region at ambient temperature rather than a classical morphotropic phase boundary (MPB) region intrinsic in the Pb(Zr_1−xTi_x)O₃ (PZT) lead-based ceramic system. Li modification enables a large decrease in T_O–T instead of constituting a classical MPB. In contrast to the nearly temperature-independent classical MPB behavior in the PZT system, the strong temperature-dependent phase transition behavior in the system may impose a challenge to temperature demanding applications.     

Phase transition and electrical properties of (1 − x)K0.02Na0.98NbO3-xBaTiO3 ceramics

(1 − x)K_0.02Na_0.98NbO₃-xBaTiO₃ ceramics were prepared by the solid state reaction method, and their electrical properties were investigated. The samples showed crystal structure changing from monoclinic to orthorhombic, and then to tetragonal, with an increase in BaTiO₃ content. The addition of BaTiO₃ markedly enhanced ferroelectric and piezoelectric properties of K_0.02Na_0.98NbO₃ ceramics. Remnant polarization increased and coercive field decreased only in the samples with small amount of BaTiO₃. Piezoelectric properties were improved with the addition of BaTiO₃. The 0.9K_0.02Na_0.98NbO₃-0.1BaTiO₃ ceramics showed maximum piezoelectric constant (d₃₃ = 160 pC/N), which was even comparable with that of (1 − x)K_0.5Na_0.5NbO₃-xBaTiO₃ ceramics. Their good piezoelectric properties, along with a low ferroelectric-ferroelectric transition temperature (T_F-F), made the 0.9K_0.02Na_0.98NbO₃-0.1BaTiO₃ ceramics a potential candidate for lead-free piezoelectric applications.     

Characterization of sol-gel synthesised lead-free (1 − x)Na0.5Bi0.5TiO3-xBaTiO3-based ceramics

The crystal structure, microstructure, dielectric and ferroelectric properties of (1 − x)Na_0.5Bi_0.5TiO₃-xBaTiO₃ ceramics with x = 0, 0.03, 0.05, 0.07 and 0.1 are investigated. A structural variation according to the system composition was investigated by X-ray diffraction (XRD) analyses. The results revealed that the synthesis temperature for pure perovskite phase powder prepared by the present sol-gel process is much lower (800 °C), and a rhombohedral-tetragonal morphotropic phase boundary (MPB) is found for x = 0.07 composition which showing the highest remanent polarization value and the smallest coercive field. The optimum dielectric and piezoelectric properties were found with the 0.93Na_0.5Bi_0.5TiO₃-0.07BaTiO₃ composition. The piezoelectric constant d₃₃ is 120 pC/N and good polarization behaviour was observed with remanent polarization (P_r) of 12.18 pC/cm², coercive field (E_c) of 2.11 kV/mm, and enhanced dielectric properties ?_r > 1500 at room temperature. The 0.93Na_0.5Bi_0.5TiO₃-0.07BaTiO₃-based ceramic is a promising lead-free piezoelectric candidate for applications in different devices.     

Effect of lanthanum doping on linear and nonlinear-optical properties of Bi3TiNbO9 thin films

Lanthanum doped Bi₃TiNbO₉ thin films (LBTN-x, La³⁺ contents x = 5%, 15%, 25% and 35 mol.%) with layered perovskite structure were fabricated on fused silica by pulsed laser deposition method. Their linear and nonlinear optical properties were studied by transmittance measurement and Z-Scan method. All films exhibit good transmittance (>55%) in visible region. For lanthanum doping content are x = 5%, 15% and 25 mol.%, the nonlinear absorption coefficient of LBTN-x thin films increases with the La³⁺ content, then it drops down at x = 35 mol.% when the content of La³⁺ in (Bi₂O₂)²⁺ layers is high enough to aggravate the orthorhombic distortion of the octahedra. We found that, 25 mol.% is the optimal La³⁺ content for LBTN-x thin films to have the largest nonlinear absorption coefficient making the LBTN-x film a promising candidate for absorbing-type optical device applications.     

The structural and electric properties of Li- and K-substituted Bi0.5Na0.5TiO3 ferroelectric ceramics

The structure, dielectric properties and phase transition of lithium and potassium modified Bi_0.5Na_0.5TiO₃ ceramics were investigated widely. The phase transition behavior with respect to changes in composition and temperature was investigated using X-ray diffraction analysis, dielectric and ferroelectric characterizations. The experimental results show that there is a diffusion phase transition in (Na_1−xK_x)_0.5Bi_0.5TiO₃ ceramics at T_m and the diffuseness of the phase transition is more obvious for the samples near the morphotropic phase boundary. In (Na_1−xLi_x)_0.5Bi_0.5TiO₃ system, due to the space charge polarization induced by ions conductivity, the low frequency permittivity increases so remarkably at high temperature that the peak of maximum permittivity vanishes. The hysteresis loops at different temperatures indicate that there is no existence of anti-ferroelectrics in lithium and potassium modified Bi_0.5Na_0.5TiO₃ ceramics above the depolarization temperature T_d. The depolarization reason is that the tetragonal nonpolar phase occurs and leads to the macro-micro domain transformation at about T_d.     

Effects of Mn substitution on ferro- and piezoelectric properties of Bi0.86Sm0.14FeO3 thin films

The Bi_0.86Sm_0.14FeO₃ (BSFO) and Bi_0.86Sm_0.14Fe_1 − xMn_xO₃ (BSFMO) (x = 0.01, 0.03, 0.05) thin films were deposited on indium tin oxide/glass substrates via a metal organic deposition method. 1 at.% Mn doping leads to an evident reduction of the leakage current in BSFO film. More importantly, the Bi_0.86Sm_0.14Fe_0.99Mn_0.01O₃ film exhibits the lowest coercive field (E_c = 272 kV/cm), the largest remanent polarization (P_r = 53.6 μc/cm²) and the remanent out-of-plane piezoelectric coefficient (d₃₃ = 146 pm/V). However, further increase of Mn doping content results in the deterioration of the charge retaining capability and the piezoelectric properties of the films. The negative influence of high Mn doping contents was discussed based on the structure change and the contribution of irreversible movement of non-180° domain walls in the aged films.