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.     

Structure and electrical properties of (1 − x)Bi0.5Na0.5TiO3-xBi0.5K0.5TiO3 ceramics near morphotropic phase boundary

The binary lead-free piezoelectric ceramics with the composition of (1 − x)Bi_0.5Na_0.5TiO₃-xBi_0.5K_0.5TiO₃ were synthesized by conventional mixed-oxide method. The phase structure transformed from rhombohedral to tetragonal phase in the range of 0.16 ≤ x ≤ 0.20. The grain sizes varied with increasing the Bi_0.5K_0.5TiO₃ content. Electrical properties of ceramics are significantly influenced by the Bi_0.5K_0.5TiO₃ content. Two phase transitions at T_t (the temperature at which the phase transition from rhombohedral to tetragonal occurs) and T_c (the Curie temperature) were observed in all the ceramics. Adding Bi_0.5K_0.5TiO₃ content caused the variations of T_t and T_c. A diffuse character was proved by the linear fitting of the modified Curie-Weiss law. Besides, the ceramics with homogeneous microstructure and excellent electrical properties were obtained at x = 0.18 and sintered at 1170 °C. The piezoelectric constant d₃₃, the electromechanical coupling factor K_p and the dielectric constant ?_r reached 144 pC/N, 0.29 and 893, respectively. The dissipation factor tan δ was 0.037.     

Ferroelectric properties of lithia-doped (Bi0.95Na0.75K0.20)0.5Ba0.05TiO3 ceramics

Lead-free piezoelectric (Bi_0.95Na_0.75K_0.20−xLi_x)_0.5Ba_0.05TiO₃ ceramics have been prepared by conventional process for different lithium substitutions. The SEM images show that the ceramics are well sintered at 1428 K. Dielectric and ferroelectric measurements have been performed. With the increasing of lithium substitution, the Curie temperature of the (Bi_0.95Na_0.75K_0.20−xLi_x)_0.5Ba_0.05TiO₃ ceramics shifts from 570 K to 620 K, but the maximum value of the dielectric constant decreases from 6700 to 4700 correspondingly. A relatively larger remanent polarization of 36.8 μC/cm² has been found in the x = 0.05 sample. The coercive field decreases as the lithium substitution amount increases. An optimized d₃₃ = 194 × 10^− 12 C/N and a relative dielectric constant ε_r = 1510 have been obtained in (Bi_0.95Na_0.75K_0.15Li_0.05)_0.5Ba_0.05TiO₃.     

Influences of poling condition and sintering temperature on piezoelectric properties of (Na0.5Bi0.5)1 − xBaxTiO3 ceramics

The structure, ferroelectric characteristics and piezoelectric properties of (Na_0.5Bi_0.5)_1 − xBa_xTiO₃ (x = 0.04, 0.06, 0.10) ceramics prepared by conventional solid state method were investigated. The influences of poling condition and sintering temperature on the piezoelectric properties of the ceramics were examined. The piezoelectric properties of the ceramics highly depend on poling field and temperature, while no remarkable effect of poling time on the piezoelectric properties was found in the range of 5-25 min. Compared with (Na_0.5Bi_0.5)_0.96Ba_0.04TiO₃ and (Na_0.5Bi_0.5)_0.90Ba_0.10TiO₃, the piezoelectric properties of (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ are more sensitive to poling temperature due to the relatively low depolarization temperature. Moderate increase of sintering temperature improved the poling process and piezoelectric properties due to the development of microstructural densification and crystal structure. With respect to sintering behavior and piezoelectric properties, a sintering temperature range of 1130-1160 °C was ascertained for (Na_0.5Bi_0.5)_0.90Ba_0.10TiO₃.     

Electrical and luminescence properties of Er-doped Bi0.5Na0.5TiO3 ceramics

The influences of Er content on the dielectric and photoluminescence performances of Bi_0.5Na_0.5TiO₃-xEr (x = 0, 0.005, 0.01, 0.015, 0.02, 0.03) ceramics have been investigated. The results show that Bi_0.5Na_0.5TiO₃-xEr ceramics with x = 0.01 Er have maximum values of photoluminescence and piezoelectric properties. A bright green emission at 550 nm and enhanced piezoelectric response are achieved in the ceramic Bi_0.5Na_0.5TiO₃-0.01Er at room temperature. Furthermore, the photoluminescence performance of the ceramics is significantly enhanced by electric poling.     

Dielectric properties of (1 − x)(Mg0.95Zn0.05)TiO3-x(Na0.5Nd0.5)TiO3 ceramic system at microwave frequencies

Ceramics in the system (1 − x)(Mg_0.95Zn_0.05)TiO₃-x(Na_0.5Nd_0.5)TiO₃ were prepared by the conventional mixed oxide route. It shows a two-phase system of an ilmenite structured (Mg_0.95Zn_0.05)TiO₃ and a perovskite structured (Na_0.5Nd_0.5)TiO₃, which were confirmed by XRD and EDX. In addition, (Mg_0.95Zn_0.05)Ti₂O₅ was identified as a second phase. It was also responsible for a rapid drop in the Q × f value. The temperature coefficient of resonant frequency was a function of compositional ratio. Specimen with x = 0.16 possessed an excellent combination of microwave dielectric properties: ε_r ~ 24.27, Q × f ~ 82,000 GHz (at 9 GHz) and τ_f ~ 0 ppm/°C.     

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.     

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.     

Ferroelectric and pyroelectric properties of (Na0.5Bi0.5)TiO3-BaTiO3 based trilayered thin films

Trilayered Bi_3.25La_0.75Ti₃O₁₂ (25 nm)/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ (300 nm)/Bi_3.25La_0.75Ti₃O₁₂ (25 nm) and Pb(Zr_0.4Ti_0.6)O₃ (25 nm)/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ (300 nm)/Pb(Zr_0.4Ti_0.6)O₃ (25 nm) thin films without undesirable phases have been deposited on Pt/Ti/SiO₂/Si substrates. It was found that the Bi_3.25La_0.75Ti₃O₁₂ and Pb(Zr_0.4Ti_0.6)O₃ layers are very effective to inhibit the charge transport in the trilayered films. Much better insulating properties than those of (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ films have been achieved in the trilayered films. The trilayered films show good dielectric, ferroelectric and pyroelectric properties. Remnant polarizations 2P_r of 16 µC/cm² and 34 µC/cm², pyroelectric coefficients of 4.8 × 10^− 4 C m^− 2 K^− 1 and 7.0 × 10^− 4 C m^− 2 K^− 1 have been obtained for the Bi_3.25La_0.75Ti₃O₁₂/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃/Bi_3.25La_0.75Ti₃O₁₂ and Pb(Zr_0.4Ti_0.6)O₃/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃/Pb(Zr_0.4Ti_0.6)O₃ thin films, respectively. The trilayered films are promising candidates for sensor and actuator applications.     

Giant strain in Nb-doped Bi0.5(Na0.82K0.18)0.5TiO3 lead-free electromechanical ceramics

The effect of Nb substitution on the crystal structure, ferroelectric, and electric field induced strain properties of Bi_0.5(Na₈₂K_0.18)_0.5TiO₃ (BNKT) ceramics has been investigated. The coexistence of rhombohedral and tetragonal phases was found in undoped BNKT ceramics, however, Nb doping induced a phase transition to a pseudocubic phase with high electrostriction coefficients. When 3 mol% Nb was substituted on Ti ions, the electric field induced strain was markedly enhanced up to S_max/E_max = 641 pm/V, which is higher than those previously reported on non-textured lead-free electromechanical ceramics.     

KxNa1 − xNbO3 powder synthesized by molten-salt process

K_xNa_1 − xNbO₃ ceramic powders have been successfully synthesized in different salts (NaCl, KCl, NaCl-KCl). Our results reveal that K_xNa_1 − xNbO₃ powders with single-phase perovskite structure can be formed at a low temperature such as 750 °C. The type of salts has significant effects on the morphology and chemical composition of the powders. As Na⁺ has a higher diffusing rate and occupies the A-site in the perovskite structure more easily as compared to K⁺, the powder contains only a small amount of K⁺ (x ∼ 0.10) when it is synthesized according to formula K_0.5Na_0.5NbO₃ and in a flux containing the same molar content of Na⁺ and K⁺. By using a NaCl or KCl salt, the K⁺ concentration x can be adjusted to almost 0 and 0.77, respectively.     

Mixed cation effect in xR2O-(40 − x)Na2O-50B2O3-10Bi2O3 (R = Li, K) glasses

Mass density, glass transition temperature and ionic conductivity are measured in xLi₂O-(40 − x)Na₂O-50B₂O₃-10Bi₂O₃ and xK₂O-(40 − x)Na₂O-50B₂O₃-10Bi₂O₃ glass systems with 0 ≤ x ≤ 40 mol%. The strength of the mixed alkali effect in T_g, dc electrical conductivity and activation energy has been determined in each glass system. The magnitudes of the mixed alkali effect in T_g for the mixed Li/Na glass system are much smaller than those in the mixed K/Na glasses. The impact of mixed alkali effect on dc electrical conductivity in mixed Li/Na glass system is more pronounced than in the K/Na glass system. The results are explained based on dynamic structure model.     

Fabrication of lead-free (Na0.82K0.18)0.5Bi0.5TiO3 piezoelectric nanofiber by electrospinning

(Na_0.82K_0.18)_0.5Bi_0.5TiO₃ nanofibers were synthesized by sol-gel process and electrospinning. Scanning electron microscopy was used to verify that the diameters and lengths are in the range of 150-600 nm and several hundreds of micrometer. Perovskite structure and grain size (20-70 nm) were verified by X-ray diffraction and transmission electron microscopy. The high effective piezoelectric coefficient d₃₃ (96 pm/V) was measured by scanning force microscopy. It may be attributed to easily tilting the polar vector of domain for an electric field and the increase in the number of possible spontaneous polarization direction near the rhombohedral-tetragonal morphotropic phase boundary. The research shows that there are potentional applications for (Na_0.82K_0.18)_0.5Bi_0.5TiO₃ nanofiber in nanoscale lead-free piezoelectric devices.     

Microwave dielectric properties of La1−xBix(Mg0.5Sn0.5)O3 ceramics

The La_1−xBi_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.97Bi_0.03(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. An apparent density of 6.50 g cm⁻³, a dielectric constant (?_r) of 20.2, a quality factor (Q × f) of 58,100 GHz and a temperature coefficient of resonant frequency (τ_f) of −84.2 ppm °C⁻¹ were obtained for La_0.97Bi_0.03(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1550 °C for 4 h.     

Dielectric and piezoelectric properties of Y2O3 doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free piezoelectric ceramics

Y₂O₃ doped lead-free piezoelectric ceramics (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (0-0.7 wt%) were synthesized by the conventional solid state reaction method, and the effect of Y₂O₃ addition on the structure and electrical properties was investigated. X-ray diffraction shows that Y₂O₃ diffuses into the lattice of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ to form a solid solution with a pure perovskite structure. The temperature dependence of dielectric constant of Y₂O₃ doped samples under various frequencies indicates obvious relaxor characteristics different from typical relaxor ferroelectric and the mechanism of the relaxor behavior was discussed. The optimum piezoelectric properties of piezoelectric constant d₃₃ = 137 pC/N and the electromechanical coupling factor k_p = 0.30 are obtained at 0.5% and 0.1% Y₂O₃ addition, respectively.     

Morphotropic phase boundary in high temperature ferroelectric xBi(Zn1/2Ti1/2)O3 − yPbZrO3 − zPbTiO3 perovskite ternary solid solution

A bismuth and lead oxide based perovskite ternary solid solution xBi(Zn_1/2Ti_1/2)O₃ − yPbZrO₃ − zPbTiO₃ (xBZT − yPZ − zPT) was investigated as an attempt to develop a high T_C ferroelectric material for piezoelectric sensor and actuator applications. A morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases was determined through an XRD study on a pseudobinary line 0.1BZT − 0.9[xPT − (1 − x)PZ] for composition 0.1Bi(Zn_1/2Ti_1/2)O₃ − 0.5PbZrO₃ − 0.4PbTiO₃. Enhanced piezoelectric and ferroelectric activities were observed for MPB composition with dielectric constant ε_r′ ~ 23,000 at Curie temperature (T_C) ≈ 320 °C, remanent polarization (P_r) = 35 μC/cm², piezoelectric coefficient (d₃₃) = 300 pC/N, unipolar strain = 0.15%, and electromechanical coupling coefficient (k_P) = 0.45.     

Dielectric properties of Ba(Ti1 − xZrx)O3 solid solutions

This paper reports the structural and dielectric properties of Ba(Ti_1 − xZr_x)O₃ (x = 0-0.3) ceramics. Single-phase solid solutions of the samples were determined by X-ray diffraction. Microscopic observation by scanning electron microscope revealed dense, single-phase microstructure with large grains (20-60 μm). The evolution of dielectric behavior from a sharp ferroelectric peak (for x ≤ 0.08) to a round dielectric peak (for 0.15 ≤ x ≤ 0.25) with pinched phase transitions and successively to a ferroelectric relaxor (for x = 0.3) was observed with increasing Zr concentration. Compared with pure BaTiO₃, broaden dielectric peaks with high dielectric constant of 25,000-40,000 and reasonably low loss (tanδ: 0.01-0.06) in the Ba(Ti_1 − xZr_x)O₃ ceramics have been observed, indicating great application potential as a dielectric material.     

Synthesis and electromagnetic properties of microwave absorbing material: Cox(Cu0.5Zn0.5)1−xFe2O4 (0 < x < 1) nanoparticles

Spinel ferrite Co_x(Cu_0.5Zn_0.5)_1−xFe₂O₄ over a compositional range 0 < x < 1 was prepared using a simple hydrothermal method. Particle sizes could be varied from 14 to 25 nm by changing the x value. X-ray diffraction results confirmed that all the as-prepared nanoparticles revealed typical spinel structure and transmission electron microscopy images showed that the particle size of the samples increased with increasing x value. The magnetic properties of the as-prepared Co_x(Cu_0.5Zn_0.5)_1−xFe₂O₄ nanoparticles have been systematically examined. The maximum saturation magnetization existed at the highest Co content (x = 1). The electromagnetic properties of all the samples have been measured by an Agilent network analyzer and the results showed that Co_0.1(Cu_0.5Zn_0.5)_0.9Fe₂O₄ possessed the best microwave absorbing properties.     

Influence of sintering temperature on piezoelectric properties of (K0.5Na0.5)NbO3-LiNbO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ have been synthesized by traditional ceramics process without cold-isostatic pressing. The effect of the content of LiNbO₃ and the sintering temperature on the phase structure, the microstructure and piezoelectric properties of (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ ceramics were investigated. The result shows that the phase structure transforms from the orthorhombic phase to tetragonal phase with the increase of the content of LiNbO₃, and the orthorhombic and tetragonal phase co-exist in (K_0.5Na_0.5)NbO₃-LiNbO₃ ceramics when the content of LiNbO₃ is about 0.06 mol. The sintering temperature of (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ decreases with the increase of the content of LiNbO₃. The optimum composition for (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ ceramics is 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃. The optimum sintering temperature of 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃ ceramics is 1080 °C. Piezoelectric properties of 0.94 (K_0.5Na_0.5)NbO₃-0.06LiNbO₃ ceramics under the optimum sintering temperature are piezoelectric constant d₃₃ of 215 pC/N, planar electromechanical coupling factor k_p of 0.41, thickness electromechanical coupling factor k_t of 0.48, the mechanical quality factor Q_m of 80, the dielectric constant of 530 and the Curie temperature T_c = 450 °C, respectively. The results indicate that 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃ piezoelectric ceramics is a promising candidate for lead-free piezoelectric ceramics.     

Large area Ba1 − xSrxTiO3 thin films for microwave applications deposited by pulsed laser ablation

Large area Ba_1 − xSr_xTiO₃ (BST) thin films with x = 0.4 or x = 0.5 were deposited on 75 mm diameter Si wafers in a pulsed laser deposition (PLD) chamber enabling full-wafer device fabrication using standard lithography. The deposition conditions were re-optimized for large PLD chambers to obtain uniform film thickness, grain size, crystal structure, orientation, and dielectric properties of BST films. X-ray diffraction and microstructural analyses on the BST films grown on Pt/Au/Ti electrodes deposited on SiO₂/Si wafers revealed films with (110) preferred orientation with a grain size < 100 nm. An area map of the thickness and crystal orientation of a BST film deposited on SiO₂/Si wafer also showed (110) preferred orientation with a film thickness variation < 6%. Large area BST films were found to have a high dielectric tunability of 76% at an electric field of 400 kV/cm and dielectric loss tangent below 0.03 at microwave frequencies up to 20 GHz and a commutation quality factor of ~ 4200.