Effect of bismuth deficiency on structure and electrical properties of (Na0.5Bi0.5)0.93Ba0.07TiO3 ceramics

(Na_0.5Bi_x)_0.93Ba_0.07TiO₃ (x=0.500-0.492) ceramics were prepared by a citrate method, and the structure and electrical properties of the ceramics were investigated with respect to the amount of Bi deficiency. It was detected that the Bi deficiency had a considerable impact on the crystal structure and microstructure. The inspection of both the temperature dependence of the dielectric properties (free permittivity ε₃₃^T/ε₀ and dielectric loss tan δ) and the evolution of the polarization-electrical field (P-E) hysteresis loops with measuring temperature suggests that the Bi deficiency served to increase the depolarization temperature (T_d). The Bi deficiency led to an increase in the coercive field (E_c) and mechanical quality factor (Q_m) together with a decrease in the remanent polarization (P_r) and piezoelectric constants (d₃₃). The variation of the structure and electrical properties with Bi deficiency amount was qualitatively interpreted in terms of the formation of Bi and oxygen vacancies in the Bi-deficient specimens. This research indicates the importance of adequately controlling Bi stoichiometry of (Na_0.5Bi_0.5)_0.93Ba_0.07TiO₃ ceramics in obtaining the desired ferroelectric and piezoelectric properties.     

Bismuth zinc niobate (Bi1.5ZnNb1.5O7) ceramics derived from metallo-organic decomposition precursor solution

The preparation, microstructure development and dielectric properties of Bi_1.5ZnNb_1.5O₇ pyrochlore ceramics by metallo-organic decomposition (MOD) route are reported. Homogeneous precalcined ceramic powders of 13-36 nm crystallite size were obtained at temperatures ranging from 500 to 700 °C. The thermal decomposition/oxidation of the gelled precursor solution was chemically analyzed, TG/DTA, XRD, and SEM, led to the formation of a pure cubic pyrochlore phase with a stoichiometry close to Bi_1.5ZnNb_1.5O₇ which begins to form at 500 °C. The metallo-organic precursor synthesis method, where Bi, Zn and Nb ions are chelated to form metal complexes, allows the control of Bi/Zn/Nb stoichiometric ratio on a molecular scale leading to the rapid formation of bismuth zinc niobate (Bi_1.5ZnNb_1.5O₇) ceramic fine powders with pure pyrochlore structure. The powders were pressed into pellets and can be sintered at temperatures as low as 800-1000 °C. Fine crystalline ceramics with the grain size in the range of 200-500 nm have been obtained at the sintering temperature of 800 °C. The dielectric properties in high frequency to microwave range were measured and discussed.     

Ferroelectric properties of Pr6O11-doped Bi4Ti3O12

Praseodymium doped Bi₄Ti₃O₁₂ (BIT) ceramics with composition Bi_2.9Pr_0.9Ti₃O₁₂ (BPT) were prepared by solid state reaction. These samples have polycrystalline Bi-layered perovskite structure without preferred orientation, and consist of well-developed plate-like grains with random orientation. Pr doping into BIT causes a large shift of the Curie temperature (T_C) of the BIT from 675 to 398 °C. At an electric field of 87 kV/cm, the remanent polarization and the coercive field of the BPT ceramics are 30 μC/cm² and 52 kV/cm, respectively. Furthermore, the dielectric permittivity and the dissipation factor of the BPT ceramics are 300 and 0.003 at 1 MHz, 1 V, and room temperature. Ferroelectric properties of the BPT ceramics are superior to V-doped Bi₄Ti₃O₁₂ (∼20 μC/cm² and 80 kV/cm) and (Sr, Ta)-doped Bi₄Ti₃O₁₂ (∼12 μC/cm² and 71 kV/cm) ceramics. In addition, the dense ceramics of praseodymium-doped B₄Ti₃O₁₂ were obtained by sintering at 1100 °C, about 100-200 °C lower than those of the SrBi₂Ta₂O₉ system.     

Effects of composition on phase structure and electrical properties of (K0.5Na0.5)0.90Li0.06Sr0.02Nb(1−x)SbxO3 ceramics

Lead-free (K_0.5Na_0.5)_0.90Li_0.06Sr_0.02Nb_(1−x)Sb_xO₃ (KNLSN-Sb_x) ceramics were synthesized by ordinary sintering technique. The compositional dependence of phase structure and electrical properties of the ceramics was systematically investigated. All samples possessed pure perovskite structure, showing room temperature symmetries of orthorhombic at x<0.01, coexistence of orthorhombic and tetragonal phases at x=0.01, and tetragonal at 0.02≤x≤0.05. The temperature of the polymorphic phase transition (PPT) was shifted to lower temperature and dielectric relaxor behavior was induced by increasing Sb content. The samples near the coexistence region (x=0.01) exhibited enhanced electrical properties: d₃₃∼145 pC/N, k_p∼38% and P_r∼20.4 μC/cm².     

Dependence of excess bismuth content in precursor sols on ferroelectric and dielectric properties of Bi3.25La0.75Ti3O12 thin films fabricated by chemical solution deposition

Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films were fabricated on Pt/Ti/SiO₂/Si(1 0 0) substrates by chemical solution deposition (CSD), and the dependence of ferroelectric and dielectric properties of the as-deposited BLT thin films on excess Bi content in precursor sols was studied. It is found that the prepared BLT thin film shows the best polarization-electric field, capacitance-voltage and dielectric constant (?_r)-frequency characteristics, when the value of excess Bi content in precursor sols is 10%. In detail, its remnant polarization (2P_r) value is 40 μC/cm², the capacitance tunability is 21% measured at room temperature under conditions of an applied voltage of 8 V and measurement frequency of 10 kHz, and the ?_r is 696 at 100 kHz frequency.     

Phase transformation behavior and dielectric characteristics of BaTi1−x(Al1/2Nb1/2)xO3 (0.01≤x≤0.40) ceramics

Microstructure, phase transformation behavior and dielectric properties of BaTi_1−x(Al_1/2Nb_1/2)_xO₃ (0.01≤x≤0.40) ceramics were investigated. A high level of (Al_1/2Nb_1/2)⁴⁺ substitution for Ti⁴⁺ ions was not conducive to the stability of the perovskite structure and resulted in the formation of BaAl₂O₄. As x was increased, lattice constants and unit cell volume decreased, reached a minimum at x=0.10 and then increased. The BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics at room temperature experienced a transformation from ferroelectric to paraelectric phase with increasing (Al_1/2Nb_1/2)⁴⁺ concentration. Meanwhile, permittivity of the BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics was markedly reduced, while Q value was slightly increased. Frequency dispersion of dielectric peak was obviously increased as x was increased from 0.01 to 0.10. It is of great interest that a dielectric abnormity represented by a broad dielectric peak at 200-400 K was observed for the composition with x=0.40.     

Enhanced ferroelectric properties of (Pb0.90La0.10)Ti0.975O3 multilayered thin films prepared by RF magnetron sputtering

The (Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PLT/PT), PbTiO₃/(Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PT/PLT/PT) multilayered thin films with a PbO_x buffer layer were in situ deposited by RF magnetron sputtering at the substrate temperature of 600 °C. With this method, highly (1 0 0)-oriented PLT/PT and PT/PLT/PT multilayered thin films were obtained. The PbO_x buffer layer leads to the (1 0 0) orientation of the films. The dielectric, ferroelectric and pyroelectric properties of the PLT multilayered thin films were investigated. It is found that highly (1 0 0)-oriented PT/PLT/PT multilayered thin films possess higher remnant polarization 2P_r (44.1 μC/cm²) and better pyroelectric coefficient at room temperature p (p = 2.425 × 10⁻⁸ C/cm² K) than these of PLT and PLT/PT thin films. These results indicate that the design of the PT/PLT/PT multilayered thin films with a PbO_x buffer layer should be an effective way to enhance the dielectric, ferroelectric and pyroelectric properties. The mechanism of the enhanced ferroelectric properties was also discussed.     

Structural and electrical properties of (Na0.85K0.15)0.5Bi0.5TiO3 thin films deposited on LaNiO3 and Pt bottom electrodes

(Na_0.85K_0.15)_0.5Bi_0.5TiO₃ thin films were deposited on LaNiO₃(LNO)/SiO₂/Si(1 0 0) and Pt/Ti/SiO₂/Si(1 0 0) substrates by metal-organic decomposition, and the effects of bottom electrodes LNO and Pt on the ferroelectric, dielectric and piezoelectric properties were investigated by ferroelectric tester, impedance analyzer and scanning probe microscopy, respectively. For the thin films deposited on LNO and Pt electrodes, the remnant polarization 2P_r are about 22.6 and 8.8 μC/cm² under 375 kV/cm, the dielectric constants 238 and 579 at 10 kHz, the dielectric losses 0.06 and 0.30 at 10 kHz, the statistic d_33eff values 95 and 81 pm/V. The improved piezoelectric properties could make (Na_1−xK_x)_0.5Bi_0.5TiO₃ thin film as a promising candidate for piezoelectric thin film devices.     

Dielectric and piezoelectric properties of lead-free (Na0.5K0.5)NbO3-SrTiO3 ceramics

In this article, we report successful preparation of dense [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ (x=0.005-0.100) ceramics by ordinary sintering in air. The dependence of phase structure on doping content of SrO and TiO₂ has been determined by the X-ray diffraction technique. It was found that the crystal structure changed from orthorhombic to tetragonal at x≈0.040. Dielectric study revealed that the dielectric relaxor behavior was induced by doping of SrO and TiO₂ into (Na_0.5K_0.5)NbO₃. The samples in the composition range from x=0.005 to 0.020 exhibited excellent electrical properties, piezoelectric constant of electromechanical planar and thickness coupling coefficients of k_p=26.6-32.5% and k_t=39.8-43.8%. The results show that the [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ ceramics are one of the promising lead-free materials for electromechanical transducer applications.     

Dielectric properties of SrBi2−xPrxNb2O9 ceramics (x=0, 0.04 and 0.2)

SrBi_2−xPr_xNb₂O₉ (x=0, 0.04 and 0.2) ceramics were prepared by a solid state reaction method. X-ray diffraction analysis indicated that single-phase layered perovskite structure ferroelectrics were obtained. A relaxor behavior of frequency dispersion was observed among Pr-doped SrBi₂Nb₂O₉. The degree of frequency dispersion ΔT increased from 0 for x=0-7 °C for x=0.2, and the extent of relaxor behavior γ increased from 0.94 for x=0-1.45 for x=0.2. The substitution of Pr ions for Bi³⁺ ions in the Bi₂O₂ layers resulted in a shift of the Curie point to lower temperatures and a decrease in remanent polarization. In addition, the coercive field 2E_c reduced from 110 kV/cm for an undoped specimen to 90 kV/cm for x=0.2.     

Dielectric and impedance measurements on (1−x)Ba(Fe1/2Ta1/2)O3-xBa(Zn1/3Ta2/3)O3 ceramics

In this work, ((1−x)Ba(Fe_1/2Ta_1/2)O₃-xBa(Zn_1/3Ta_2/3)O₃), ((1−x)BFT-xBZT) ceramics with x = 0.00–0.12 were synthesized by the solid–state reaction method. X-ray diffraction data revealed that both the powders and ceramics were of a pure-phase cubic perovskite structure. All ceramics showed large dielectric constants. For the x = 0.12 sample, a very high dielectric constant (>20,600) was observed. A lowering in the dielectric loss compared to pure BFT ceramics was observed with the BZT addition. The impedance measurements indicated that BZT has a strong effect on the bulk grain and grain boundary resistance of BFT ceramics. These results are in agreement with the measured dielectric properties. Based on dielectric and impedance results, (1−x)BFT-xBZT ceramics could be of great interest for high performance dielectric materials applications due their giant dielectric constant behavior.     

Phase transition, structural and electrical properties of Pb(Zn1/3Nb2/3)O3-doped Pb(Ni1/3Nb2/3)O3-PbTiO3 ceramics prepared by solid-state reaction method

Phase pure perovskite (1−x−y)Pb(Ni_1/3Nb_2/3)O₃-xPb(Zn_1/3Nb_2/3)O₃-yPbTiO₃ (PNN-PZN-PT) ferroelectric ceramics were prepared by conventional solid-state reaction method via a B-site oxide mixing route. The PNN-PZN-PT ceramics sintered at the optimized condition of 1185 °C for 2 h exhibit high relative density and rather homogenous microstructure. With the increase of PbTiO₃ (PT) content, crystal structure and electrical properties of the synthesized PNN-PZN-PT ceramics exhibit successive phase transformation. A morphotropic phase boundary (MPB) is supposed to form in (0.9−x)PNN-0.1PZN-xPT at a region of x=32-36 mol% confirmed by X-ray diffraction (XRD) measurement and dielectric measurement. The MPB composition can be pictured as providing a “bridge” connecting rhombohedral ferroelectric (FE) phase and tetragonal one since crystal structure of the MPB composition is similar to both the rhombohedral and tetragonal lattices. Dielectric response of the sintered PNN-PZN-PT ceramics also exhibits successive phase-transition character. 0.64PNN-0.1PZN-0.26PT exhibits broad, diffused and frequency dependent dielectric peaks indicating a character of diffused FE-paraelectric (PE) phase transition of relaxor ferroelectrics and 0.40PNN-0.1PZN-0.50PT exhibits narrow, sharp and frequency independent dielectric peaks indicating a character of first-order FE-PE phase transition of normal ferroelectrics. The FE-PE phase transition of 0.56PNN-0.1PZN-0.34PT is nearly first-order with some diffused character, which also exhibits the largest value of piezoelectric constant d₃₃ of 462pC/N.     

Influence of mobile space charges on electrical properties of ferroelectric Bi3.5La0.5Ti3O12 thin films

Lanthanum-substituted bismuth titanate, Bi_3.5La_0.5Ti₃O₁₂ (i.e., x=0.5 in Bi_4−xLa_xTi₃O₁₂), thin films have been grown on Pt/Ti/SiO₂/Si substrates using pulsed laser deposition. The frequency dependence of the real part ε′(ω) and the imaginary part ε″(ω) of the dielectric constant has been studied. The ε′(ω) does not show any sudden change within the frequency range of 10²-10⁶ Hz. In contrast, the ε″(ω) shows a large dispersion as frequency decreases. The observed relaxation behavior in ε″(ω) can be explained in terms of a migration of oxygen vacancies in (Bi₂O₂)²⁺ layers, not in Bi₂Ti₃O₁₀ perovskite layers.     

Thermoelectric properties of the Bi2−xYxRu2O7 (x=0-2) pyrochlores

Electrical conductivity and Seebeck coefficient for the Bi_2−xY_xRu₂O₇ pyrochlores with x=0.0,0.5,1.0,1.5,2.0 were measured in the temperature range of 473-1073 K in air. With increasing Bi content, the temperature dependence of the electrical conductivity changed from semiconducting to metallic. The signs of the Seebeck coefficient were positive in the measured temperature range for all the samples, indicating that the major carriers were holes. The temperature dependence of the Seebeck coefficient for the Y₂Ru₂O₇ indicated the thermal activation-type behavior of the holes, while that for the Bi_2−xY_xRu₂O₇ with x=0.0-1.5 indicated the itinerant behavior of the holes. The change in the conduction behavior from semiconductor to metal with increasing Bi content is consistent with the increase in the overlap between the Ru4d t_2g and O2p orbitals, but the mixing of Bi6s, 6p states at E_F may not be ruled out. The thermoelectric power factors for the Bi_2−xY_xRu₂O₇ with x=1.5 and 2.0 were lower than 10⁻⁵ W m⁻¹ K⁻² and those with x=0.0,0.5,1.0 were around 1-3×10⁻⁵ W m⁻¹ K⁻².     

Ferroelectric-relaxor behavior of (Na0.5K0.5)NbO3-based ceramics

We report that ferroelectric-relaxor behavior is induced by doping of SrO and TiO₂, or BaO and TiO₂ into classic ferroelectric (Na_0.5K_0.5)NbO₃. It is found that [(Na_0.5K_0.5)_0.9Sr_0.1](Nb_0.9Ti_0.1)O₃ ceramics exhibit a pronounced ferroelectric-relaxor behavior, comparable to that of [(Na_0.5K_0.5)_0.9Ba_0.1](Nb_0.9Ti_0.1)O₃ ceramics. Our results indicate that the relaxor behavior is closely related to the appearance of micropolar regions in these systems. The relaxor behavior should arise from the dynamic response of micropolar clusters. Raman spectra of [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ ceramics measured in the wavenumber range from 100 to 1200 cm⁻¹ confirm that the first order scattering is dominant in phonon bands should result from both short-range ordered region (micropolar regions) and disordered matrix. The frequency dependence of dielectric permittivity measurements show that the relaxor behavior of SrO and TiO₂, or BaO and TiO₂ doped (Na_0.5K_0.5)NbO₃ ceramics is not a Debye type in the radio frequency range.     

TiO2-nonstoichiometry dependence on piezoelectric properties and depolarization temperature of (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06Ti_xO_1+2x lead-free piezoceramics with x varying from 0.97 to 1.03 were fabricated and characterized in order to investigate the effects of TiO₂-nonstoichiometry on the piezoelectric properties and depolarization temperature of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ composition. X-ray diffraction (XRD) analysis showed that all samples have a single phase of perovskite structure with rhombohedral symmetry. Piezoelectric and dielectric measurements revealed that deficiency of TiO₂ leads to an increase in the piezoelectric coefficient (d₃₃), free relative permittivity (), and loss tangent (tan δ) besides an increase in the electromechanical coupling coefficient (k_p) within a certain amount, while excess of TiO₂ results in a decrease in k_p, d₃₃, and , but an increase in tan δ. Depolarization temperature (T_d) measurement indicated a decrease and an increase in T_d as a result of increasing TiO₂ deficiency and TiO₂ excess, respectively. This TiO₂-nonstoichiometry also induced changes in the remanent polarization (P_r) and coercive field (E_c) of the ceramics.     

Microstructure and piezoelectric properties of Bi0.5(Na0.82K0.18)0.5TiO3−NaSbO3 ceramics

Lead-free piezoelectric ceramics (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ have been prepared by a conventional ceramics technique, and their microstructure and electrical properties have been investigated. The addition of NaSbO₃ has no remarkable effect on the crystal structure within the studied doping content; however, an obvious change in microstructure took place. With increase in NaSbO₃ content, the temperature from a ferroelectric to antiferroelectric phase transition increases, and the temperature for a transition from antiferroelectric phases to paraelectric phases changes insignificantly. Simultaneously, the temperature range between the rhombohedral phase transition point and the Curie temperature point becomes smaller. The piezoelectric properties significantly increase with increase in NaSbO₃ content and the piezoelectric constant and electromechanical coupling factor attain maximum values of d₃₃=160 pC/N and k_p=0.333 at x=0.01. The results indicate that (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ ceramic is a promising lead-free piezoelectric candidate material.     

Synthesis and ion conductivity of (Bi2O3)0.75(Dy2O3)0.25 ceramics with grain sizes from the nano to the micro scale

Using (Bi₂O₃)_0.75(Dy₂O₃)_0.25 nano-powder synthesized by reverse titration co-precipitation method as raw material, dense ceramics were sintered by both Spark Plasma Sintering (SPS) and pressureless sintering. According to the predominance area diagram of Bi-O binary system, the sintering conditions under SPS were optimized. (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with relative density higher than 95% and an average grain size of 20 nm were sintered in only 10 min up to 500 °C. During the pressureless sintering process, the grain growth behavior of (Bi₂O₃)_0.75(Dy₂O₃)_0.25 followed a parabolic trend, expressed as D² − D₀² = Kt, and the apparent activation energy of grain growth was found to be 284 kJ mol^− 1. Dense (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with different grain sizes were obtained, and the effect of grain size on ion conductivity was investigated by impedance spectroscopy. It was shown that the total ion conductivity was not affected by the grain size down to 100 nm, however lower conductivity was measured for the sample with the smallest grain size (20 nm). But, although only the δ phase was evidenced by X-ray diffraction for this sample, a closer inspection by Raman spectroscopy revealed traces of α-Bi₂O₃.     

Effect of Bi substitution on the magnetic and dielectric properties of epitaxially grown BaFe0.3Zr0.7O3−δ thin films on SrTiO3 substrates

The structural, dielectric and magnetic properties of single crystalline Ba_1−xBi_xFe_0.3Zr_0.7O_3−δ (x=0.0-0.29) thin films have been studied. The pseudotetragonal epitaxial thin films were obtained by pulsed laser-beam deposition (PLD) on (0 0 1) SrTiO₃ (STO) single-crystal substrates. The Bi substitution for the Ba ions up to an extent of x=0.18 caused a slight improvement in the leakage current properties, as well as an enhancement of the apparent dielectric constant. The saturation magnetization of the films was significantly decreased following Bi substitution. These changes were thought to be related to the increase in oxygen deficiencies in the films. The effect of the Bi substitution on the dielectric and magnetic properties was analyzed in conjunction with the change in valence value of the Fe ions.     

Study of (Bi2O3)(BaxMo1−xO3) polycrystalline ceramic as relaxor ferroelectric

Solid solutions of bismuth layered (Bi₂O₃)(Ba_xMo_1−xO₃) (0.2≤x≤0.8, x is in step of 0.2) ceramics were prepared by conventional solid-state reaction of the constitutive oxides at optimized temperatures with a view to study its electrical properties. Powder X-ray diffraction has been employed for physical characterization and an average grain size of ∼16 to 22 nm was obtained. XRD study reveals the single phase structure of the samples. Dielectric properties such as dielectric constant (ε′), dielectric loss (tanδ) and ac electrical conductivity (σ_ac) of the prepared ceramics sintered at various temperatures in the frequency range 10¹–10⁷ Hz have been studied. A strong dispersion observed in the dielectric properties shows the relaxor type behavior of the ceramic. The presence of maxima in the dielectric permittivity spectra indicates the ferroelectric behavior of the samples. Impedance plots (Cole–Cole plots) at different frequencies and temperatures were used to analyze the electric behavior. The value of grain resistance increases with the increase in Ba ion concentration. The conductivity mechanism shows a frequency dependence, which can be ascribed to the space charge mainly due to the oxygen vacancies. The relaxation observed for the M″ (ω) or Z″ (ω) curves is correlated to both localized and long range conduction. A single ‘master curve’ for the normalized plots of all the modulus isotherms observed for a given composition indicates that the conductivity relaxation is temperature independent.