Enhanced electrical properties in W/Cu co-doped CaBi2Nb2O9 high-temperature piezoelectric ceramics

CaBi₂Nb₂O₉ (CBN)-based high-temperature piezoelectric ceramics with the formula of CaBi₂Nb_2−x(W_3/4Cu_1/4)_xO₉ were prepared via the traditional solid-state reaction method. Both the bulk microstructure and the electrical performance of the W/Cu co-doped CBN-based ceramics were systematically investigated. The results indicated that the W/Cu incorporation into the Nb-site altered the crystal structure, which enhanced the piezoelectricity and resistivity. The ceramic with the composition CaBi₂Nb_1.96(W_3/4Cu_1/4)_0.04O₉ exhibited good performance with a high d₃₃ (~14 pC/N) and T_C (~939℃). Moreover, the ceramic exhibited a good electrical resistivity (ρ) of 4.91 × 10⁵ Ω·cm and a low dielectric loss (tanδ) of 0.1 at 600℃. Furthermore, the ceramic that was annealed at 900℃ for 2 h presented a d₃₃ value of 13 pC/N, thus indicating good thermal stability of the piezoelectric properties. All these results confirm that the CaBi₂Nb_1.96(W_3/4Cu_1/4)_0.04O₉ ceramic may act as a potential promising candidate for piezoelectric device applications in high-temperature environments.     

A simple Bi3+ self-doping strategy constructing pseudo-tetragonal phase boundary to enhance electrical properties in CaBi2Nb2O9 high-temperature piezoceramics

Calcium bismuth niobate (CaBi₂Nb₂O₉, CBN)-based ceramics are promising candidates for high temperature application, the electrical properties of which are commonly enhanced by complex ion substitution or texture processes. Here, we report that high piezoelectricity and high resistivity were achieved in Ca_1-xBi_2+xNb₂O₉ by constructing pseudo-tetragonal boundary through a simple strategy of Bi³⁺ self-doping. At the pseudo-tetragonal boundary, Ca_0.96Bi_2.04Nb₂O₉ ceramics maintain high Curie temperature T_c = 942 °C, and show high piezoelectric coefficient d₃₃ = 15.1 pC/N and high resistivity ρ_dc = 2 × 10⁶ Ω cm (@600 °C). It is proved that the good piezoelectric property mainly originates from the increase of domain density. In addition, Ca_0.96Bi_2.04Nb₂O₉ ceramics reveal good thermal depoling performance, remaining 90% of piezoelectricity after thermal depoling at 900 ℃, which is due to small thermal expansion and structural distortion. Our work provides a promising candidate for high temperature applications and an easy way to improve the performance of Aurivillius-type piezoelectric ceramics.     

Enhanced electrical properties related to structural distortion of CaBi2Nb2O9-based piezoelectric ceramics

CaBi₂Nb₂O₉ (CBN)-based high Curie temperature piezoelectric ceramics with formula Ca_0.8-xSr_x(Li_0.5Ce_0.15Bi_0.35)_0.2Bi₂Nb_1.94Ta_0.04W_0.02O₉ were prepared by conventional solid-state reaction method. The effects of strontium substitution for calcium in CBN pseudo-perovskite structure A-site were systematically studied. Results showed that the addition of Sr²⁺ ions lead to an improvement of the tetragonality of lattice structure, which resulted in an enhancement of piezoelectric and ferroelectric properties together with high Curie temperature T_C and good resistance to thermal depolarization. The analysis of dielectric spectrums revealed that the space charge polarization induced an additional dielectric anomaly occurred below T_C. The composition with x = 0.025 showed good integrated performance, the piezoelectric coefficient d₃₃ and T_C were ~17.5 pC/N and ~917°C, respectively. Even though the as-studied ceramics underwent high depolarizing temperature reached up to 875°C, d₃₃ decreased by 8% merely. The remanent polarization 2P_r and the resistivity ρ at 650°C were on the order of ~10 μC/cm² and 3 × 10⁵ Ω cm, respectively.     

Significantly enhanced dc electrical resistivity and piezoelectric properties of Tb-modified CaBi2Nb2O9 ceramics for high-temperature piezoelectric applications

Bismuth layer–structured ferroelectric calcium bismuth niobate (CaBi₂Nb₂O₉, CBN) is considered to be one of the most potential high-temperature piezoelectric materials due to its high Curie temperature T_c of ∼940°C, but the drawbacks of low electrical resistivity at elevated temperature and low piezoelectric performance limit its applications as key electronic components at high temperature (HT). Herein, we report significantly enhanced dc electrical resistivity and piezoelectric properties of CBN ceramics through rare-earth element Tb ions compositional adjustment. The nominal compositions of Ca_1−xTb_xBi₂Nb₂O₉ (abbreviated as CBN-100xTb) have been fabricated by conventional solid-state reaction method. The composition of CBN-3Tb exhibits a significantly enhanced dc electrical resistivity of 1.97 × 10⁶ Ω cm at 600°C, which is larger by two orders of magnitude compared with unmodified CBN. The donor substitutions of Tb³⁺ ions for Ca²⁺ ions reduce the oxygen vacancy concentrations and increase the band-gap energy, which is responsible for the enhancement of dc electric resistivity. The temperature-dependent dc conduction properties reveal that the conduction is dominated by the thermally activated oxygen vacancies in the low-temperature region (200–350°C) and by the intrinsic conduction in the HT region (350–650°C). The CBN-3Tb also exhibits enhanced piezoelectric properties with a high piezoelectric coefficient d₃₃ of ∼13.2 pC/N and a high T_c of ∼966°C. Moreover, the CBN-3Tb exhibits good thermal stabilities of piezoelectric properties, remaining 97% of its room temperature value after annealing at 900°C. These properties demonstrate the great potentials of Tb-modified CBN for high-temperature piezoelectric applications.     

Enhanced piezoelectric response and high-temperature sensitivity by site-selected doping of BiFeO3-BaTiO3 ceramics

Effect of Zn site-selected doping on electrical properties, high-temperature stability and sensitivity of piezoelectric response for BiFeO₃-BaTiO₃ ceramics was investigated. The results revealed that the addition of Zn leaded to an evident modification of the microstructure. The B-site selected doping was a more effective approach in improving piezoelectric properties as well as their thermal stability than those of A-site selected doping. Moreover, the enhanced piezoelectric properties accompanying by excellent high-temperature stability and sensitivity in B-site selected doping ceramics were obtained. The microstructure, domain switching behavior and temperature-dependent piezoelectric response in Zn site-selected doping ceramics were investigated, and their relationships with improving piezoelectric properties and high-temperature stability were explored. These results showed that the B-site selected doping ceramics had excellent piezoelectric properties (d₃₃ = 192pC/N) along with a high-temperature stability (T_d = 450 °C).     

Textured CaBi4Ti4O15 ceramics with large piezoelectricity,excellent thermal stability and high resistivity

The bismuth layer-structured ferroelectrics (BLSF) are promising high-temperature piezoelectric materials, in which large piezoelectricity, good thermal stability and high electrical resistivity are desired. Here highly textured CaBi₄Ti₄O₁₅ BLSF ceramics with orientation factor of 82% have been fabricated by spark plasma sintering technique. The piezoelectric coefficient d₃₃ is significantly enhanced by 250%, from 7.2 pC/N for the texture-less sample to 25.3 pC/N for the textured one, accompanied by a high Curie temperature T_C= 788 °C. The variation of d₃₃ is below 5% in the temperature range of 25–500 °C, showing excellent thermal stability. The textured sample exhibits high electrical resistivity ρ = 2.1 × 10¹¹ Ω·cm, an order of magnitude larger than that of the texture-less sample. At the temperature as high as 500 °C, the textured sample still maintains excellent electrical properties of d₃₃ = 24.2 pC/N, tanδ = 9.9% and ρ = 2.7 × 10⁶ Ω·cm, suggesting that the textured CaBi₄Ti₄O₁₅ ceramics could be a potential candidate for high-temperature piezoelectric sensor or detector applications.     

Enhanced piezoelectric properties and electrical resistivity in W/Cr co-doped CaBi2Nb2O9 high-temperature piezoelectric ceramics

W/Cr co-doped Aurivillius-type CaBi₂Nb_2-x(W_2/3Cr_1/3)_xO₉ (CBN) (x?=?0.025, 0.050, 0.075, 0.100, and 0.150) piezoelectric ceramics were prepared by the conventional solid-state reaction method. The crystal structure, microstructure, dielectric properties, piezoelectric properties, and electrical conductivity of these ceramics were systematically investigated. After optimum W/Cr modification, the CBN ceramics showed both high d₃₃ and T_C. The ceramic with x?=?0.1 showed a remarkably high d₃₃ value of ~15 pC/N along with a high T_C of ~931?°C. Moreover, the ceramic also showed excellent thermal stability evident from the increase in its planar electromechanical coupling factor k_p from 8.14% at room temperature to 11.04% at 600?°C. After annealing at 900?°C for 2?h, the ceramic showed a d₃₃ value of 14?pC/N. Furthermore, at 600?°C, the ceramic also showed a relatively high resistivity of 4.9?×?10⁵ Ω?cm and a low tanδ of 9%. The results demonstrated the potential of the W/Cr co-doped CBN ceramics for high-temperature applications. We also elucidated the mechanism for the enhanced electrical properties of the ceramics.     

Simultaneous enhancement of electrical and mechanical properties in CaBi2Nb2O9-based ceramics

CaBi₂Nb₂O₉ (CBN) with Aurivillius phase has an enormous potential in high-temperature piezoelectric devices due to their high Curie temperature and excellent free-fatigue characteristics. Nevertheless, simultaneous enhancement of electrical and mechanical properties in CBN-based ceramics are still a great challenge because of the trade-off between the electrical and mechanical properties. Herein, a strategy, the synergy effect of lattice distortion and oxygen vacancy, is designed to realize the enhanced electrical and mechanical properties of CBN-based ceramics via the domain structure and grain size engineering. The materials can simultaneously deliver a high piezoelectric property of 17.3 pC/N, large hardness of 4.68 GPa, and intensive bending strength of 113.07 MPa, which are enhanced by 346%, 197%, and 141% over those of unmodified CBN ceramics. We believe that the founding of this research opened up a novel and efficient guideline for exploring new bismuth-layered structure ceramics with excellent electrical and mechanical properties.     

The structure and electrical properties of Ca0.6(Li0.5Bi0.5-xPrx)0.4Bi2Nb2O9 high-temperature piezoelectric ceramics

Ca_0.6(Li_0.5Bi_0.5-xPr_x)_0.4Bi₂Nb₂O₉ ceramics were prepared via a solid-state reaction method. The effect of the Pr content on the structural and electrical properties was systematically investigated. X-ray diffraction (XRD) combined with Rietveld refinement and X-ray photoelectron spectroscopy (XPS) demonstrated that a moderate amount of Pr³⁺ can be incorporated into the NbO₆ octahedra, while excess Pr³⁺ ions probably enter into the (Bi₂O₂)²⁺ layers, thus resulting in an increase in the tetragonality of the crystal structure. The introduction of Pr suppressed the generation of oxygen vacancies and improved the preferential grain growth along the c-axis, which might be responsible for enhancing the resistivity (ρ ~ 10⁶ Ω cm at 600°C). The replacement of Pr³⁺ for A-site Bi³⁺ enhanced the piezoelectric property, and the piezoelectric constant d₃₃ increased from 13.8 pC/N to 16.3 pC/N. The high depolarization temperature (up to 900°C) implied that CBN-LBP100x ceramics are promising candidates for ultrahigh-temperature application.     

A new method to improve the electrical properties of KNN-based ceramics: Tailoring phase fraction

Although both the phase type and fraction of multi-phase coexistence can affect the electrical properties of (K,Na)NbO₃ (KNN)-based ceramics, effects of phase fraction on their electrical properties were few concerned. In this work, through changing the calcination temperature of CaZrO₃ powders, we successfully developed the 0.96 K_0.5Na_0.5Nb_0.96Sb_0.04O₃-0.01CaZrO₃-0.03Bi_0.5Na_0.5HfO₃ ceramics containing a wide rhombohedral-tetragonal (R-T) phase coexistence with the variations of T (or R) phase fractions. It was found that higher T phase fraction can warrant a larger piezoelectric constant (d₃₃) and d₃₃ also showed a linear variation with respect to tetragonality ratio (c/a). More importantly, a number of domain patterns were observed due to high T phase fraction and large c/a ratio, greatly benefiting the piezoelectricity. In addition, the improved ferroelectric fatigue behavior and thermal stability were also shown in the ceramics containing high T phase fraction. Therefore, this work can bring a new viewpoint into the physical mechanism of KNN-based ceramics behind R-T phase coexistence.     

Natural-superlattice structured CaBi2Nb2O9-Bi4Ti3O12 ferroelectric thin films

Natural-superlattice-structured/intergrowth CaBi₂Nb₂O₉-Bi₄Ti₃O₁₂ (CBNO-BIT) ferroelectric thin films were successfully prepared via a magnetron sputtering process. XRD and TEM analysis revealed the [Bi₂O₂-(CaNb₂O₇)-Bi₂O₂-(Bi₂Ti₃O₁₀)]_n intergrowth structure of the film, as well as a (200)/(020) texture. XPS and EDS results confirmed that the film composition is close to the chemical stoichiometry. With its microstructure being successfully tailored at the nanoscale, the CBNO-BIT film exhibits good electrical properties, including a large dielectric constant (ε_r ∼390), a high piezoelectric coefficient (d₃₃ ∼90 pm/V) as well as a high energy storage density (W_E ∼76 J/cm³). Finally, the intergrowth nature of the film was verified by the measured temperature-dependent dielectric response (C-T).     

Effects of (Li0.5Sm0.5)/W co-substitution and sintering temperature on the structure and electrical properties of ultrahigh Curie temperature piezoceramics,Ca0.92(Li0.5Sm0.5)0.08Bi2Nb2-xWxO9

With co-substitution of (Li_0.5Sm_0.5) at A site and W at B site, the electrical properties of modified Ca_0.92(Li_0.5Sm_0.5)_0.08Bi₂Nb_2-xW_xO₉ [(CLS)BN-xW, x = 0, 0.015 and 0.03] piezoceramics with ultrahigh Curie temperature (T_C) of > 930 °C were enhanced dramatically. The increased resistivity induced by the co-substitution ensure them to be polarized under an enough high field. Combined with the increase of spontaneous ferroelectric polarization (P_S), the significant enhancements in the piezoelectric, dielectric and ferroelectric properties can be obtained in the composition x = 0.015. Furthermore, the piezoelectric activity (d₃₃) and bulk resistivity (ρ_b) of (CLS)BN-0.015 W can be further enhanced at an appropriate sintering temperature. This optimum composition sintered at 1170 °C shows ultrahigh T_C of ～948 °C, d₃₃ of ～17.3 pC/N and ρ_b of ～6.9 MΩ cm at 600 °C, which are comparable to those of the reported high-temperature Aurivillius piezoceramics with T_C > 850 °C.     

Influence of Co/W co-doping on structural and electrical properties of Na0.5Bi2.5Nb2O9 piezoelectric ceramics

Co/W co-doped Na_0.5Bi_2.5Nb_2-x(Co_1/3W_2/3)_xO₉ (NBNCW-x) ceramic samples were prepared by the conventional solid state reaction method. The electrical properties and crystal structure of the NBNCW-x ceramic samples were analyzed in detail. The XRD and Rietveld refinement results showed that the samples lattice distortion decreased with the increment of Co/W doping. The XPS results showed that the number of oxygen vacancies in the Na_0.5Bi_2.5Nb₂O₉ ceramics could be reduced by the substitution of a small amount of Co/W. The weakened lattice distortion and reduced number of oxygen vacancies of the Na_0.5Bi_2.5Nb₂O₉ ceramics synergistically contributed to its improved electrical properties. In particular, the Na_0.5Bi_2.5Nb_1.97(Co_1/3W_2/3)_0.03O₉ ceramic exhibited the best performance, and its T_c, d₃₃ and P_r were 780 °C, 24.9 pC/N and 12.6 μC/cm², respectively. The dielectric loss was only 3.3% at 550 °C. In addition, this ceramic exhibited excellent thermal stability, with the d₃₃ value of the ceramic being 95.2% of its original value when annealed at 750 °C. These properties indicate that the Co/W co-doped Na_0.5Bi_2.5Nb₂O₉-based ceramics have potential application in the high-temperature field.     

Ge-doped Li3+xMg2Nb1-xGexO6 ceramics with enhanced low loss and high temperature stability properties

New high-performance materials have attracted much attention due to ever-increasing demands for advanced communication technologies. In present work, Ge-doped Li_3+xMg₂Nb_1-xGe_xO₆ (0 ≤ x ≤ 0.08) ceramics are prepared via solid-state reaction route. Microstructural analysis and crystal structure refinement reveal that moderate substitution can promote grain growth and modify crystal structure, thus enhancing microwave dielectric properties of composites. In that sense, special attention is paid to the behavior of dielectric constant ε_r, quality factor Q×f, and frequency temperature coefficient τ_f of final products. In these systems, ε_r parameter depends on the density, miscellaneous phases, and polarizability; Q×f value is shown to be influenced by Nb-O bond energy, grain size, and bulk density; finally, τ_f characteristic refers to Nb-O bond valence and NbO₆ octahedral distortion. Among above ceramics, Li_3.02Mg₂Nb_0.98Ge_0.02O₆ composite sintered at 1250 °C exhibits outstanding microwave absorption performance with ε_r = 15.32, Q×f = 969 88 GHz, and τ_f = ?8.25 ppm/°C.     

Enhanced piezoelectric properties and low electrical conductivity of Ce-doped Bi7Ti4.5W0.5O21 intergrowth piezoelectric ceramics

New types of Ce-doped Ce_xBi_7-xTi_4.5W_0.5O₂₁ (BTW-BIT-xCe) Aurivillius intergrowth ceramics with high Curie temperatures were synthesized to improve the piezoelectric performances as well as the conduction behaviour, and these ceramics exhibit great potential for high-temperature lead-free piezoelectric applications. The crystal structure, electrical properties and conduction behaviour of BTW-BIT-xCe samples were analysed thoroughly. The XRD patterns combined with Rietveld refinements of the patterns showed that the crystal structure transformed from orthorhombic structure towards pseudo-tetragonal structure with increasing CeO₂ dopant, indicating that a higher symmetry was obtained. The dielectric properties of Ce-doped samples were improved, accompanied by a significant drop in the dielectric loss and a slight decreased Curie temperature (705 °C–683 °C). An enhanced piezoelectric constant d₃₃ of 25.3 pC/N was obtained in BTW-BIT-0.12Ce, which may be attributed to a common decrease in the electrical conductivity and coercive field. Besides, a low electrical conductivity of 2 × 10^-6 S/cm at 540 °C was achieved in the same component owing to a decreased concentration of the oxygen vacancies, which was verified by analyses on XPS spectra. The above results indicate that Ce-doped BTW-BIT samples have great development potential for high temperature piezoelectric applications.     

Structure and electrical properties of Ce-modified Ca1-xCexBi2Nb1.75(Cu0.25W0.75)0.25O9 high Curie point piezoelectric ceramics

Ca_1-xCe_xBi₂Nb_1.975(Cu_0.25W_0.75)_0.025O₉ (CBNCW-xCe: x = 0.00, 0.02, 0.04, 0.06, and 0.09) lead-free piezoelectric ceramics with improved piezoelectric properties were prepared by the traditional solid-state reaction method. The effects of CeO₂ doping on the microstructure and electrical properties were investigated in detail. XRD patterns and Rietveld refinement show that the crystal structures of the samples transform from the orthorhombic phase into the pseudotetragonal phase and that the lattice distortion is weakened. Raman and XPS spectra indicate that Ce ions exist with +3 and + 4 valences in the air sintered ceramics, in which Ce⁴⁺ replaces Nb⁵⁺, causing the weakened NbO₆ octahedral vibration of torsional and tensile and an increase in oxygen vacancies in the doped ceramics. When x = 0.04, it shows excellent comprehensive properties with a high d₃₃ value of 18.1 pC/N, a T_c value of 900 °C, and a ρ_dc value of 2.8 × 10⁵ Ω cm at 500 °C. Our results suggest that the CBNCW-0.04Ce ceramic is a promising candidate in high-temperature piezoelectric applications.     

Effect of (Zn1/3Nb2/3)4+ co-substitution on the microwave dielectric properties of Ce2Zr3(MoO4)9 ceramics

Ce₂[Zr_1-x(Zn_1/3Nb_2/3)_x]₃(MoO₄)₉ (CZ_1-x(ZN)_xM) (x = 0.02–0.08) compounds were successfully prepared to scientifically examine the effect of (Zn_1/3Nb_2/3)⁴⁺ doping on phase composition, microstructures, and properties. The XRD results showed that all compounds formed a pure phase with the space group of R-3c. SEM results indicated that all compounds were compact at 675 °C, and the lattice parameters and average grain size decreased with doping. Performance analysis illustrated that ε_r was closely related to the polarizability, and Q?f was affected by the lattice energy of the Mo–O bond. The τ_f was maintained at an excellent level. Far-infrared analysis indicated that the major dielectric contribution to CZ_1-x(ZN)_xM ceramics was related to the absorption of phonon oscillation. The optimum properties (ε_r = 10.72, Q?f = 59,381 GHz, τ_f = ?11.48 ppm/°C) were obtained when x = 0.04.     

Thermally stimulated depolarization current properties of Co4Nb2O9 ceramics

Thermally stimulated depolarization current in magnetoelectric antiferromagnet Co₄Nb₂O₉ were investigated above Néel temperature, and five current peaks (denoted as P0 ~ P4 in the order of ascending temperature) were observed. These peaks are related to holes which can be trapped by cobalt vacancies, their surrounding medium (self-trapped), internal, and surface barrier layers. In low-temperature range, the holes are bound to cobalt vacancies. The polarization caused by bound holes yields P0 peak at 46 K. In middle-temperature range, the holes are localized by the surrounding medium forming polarons. The hopping motions of the self-trapped holes create P2 peak at ~120 K. The microdisplacements around their locating positions for the self-trapped holes lead to P1 peak, whose peak temperature strongly depends on the poling temperature but lower than that of P2 peak. In high-temperature range, the holes are trapped by internal and surface barrier layers giving rise to P3 peak at ~150 K and P4 peak at ~230 K, respectively.     

Temperature-dependent piezoelectric strain and resonance performance of Fe2O3-modified BiScO3-PbTiO3-Pb(Nb1/3Mn2/3)O3 ceramics

The piezoelectric strain and resonance performance of 0.37BiScO₃-0.6PbTiO₃-0.03Pb(Mn_1/3Nb_2/3)O₃ (BS-PT-PMN-xFe) ceramics with different amounts of Fe content addition were investigated from room temperature to 200 °C. Both the piezoelectric strain and resonance performance are improved by Fe addition in wide temperature range. Piezoelectric strain of BS-PT-PMN-xFe with 1 mol% Fe is 0.23%, which is comparable to that of BiScO₃-PbTiO₃ (BS-PT) ceramics, while the strain hysteresis is only one-third. At 200 °C, the high-field strain coefficient of BS-PT-PMN-Fe with 1 mol% Fe is as large as 700 pm/V. Variation of piezoelectric strain and hysteresis is clearly reducing by Fe addition. The maximum vibration velocity is enhanced up to approximately 1 m/s in 2 mol% Fe-modified BS-PT-PMnN-xFe ceramics, and the vibration velocity is stable from room temperature to 200 °C when the electric voltage magnitude was below 60 V_pp. These results indicate that BS-PT-PMN-xFe ceramics are potential candidates for high-temperature piezoelectric actuator application.