Bi(Mg0.5Ti0.5)O3 addition induced high recoverable energy-storage density and excellent electrical properties in lead-free Na0.5Bi0.5TiO3-based thick films

(1-x)Na_0.5Bi_0.5TiO₃-xBi(Mg_0.5Ti_0.5)O₃ (NBT-BMT) thick films were designed for achieving large recoverable energy-storage density (W_rec). A large W_rec of 40.4 J/cm³ was detected in the thick film for x = 0.4, which was more than 4 times larger than that of the pure NBT film. The addition of BMT induced slim polarization hysteresis (P-E) loops at room temperature. The slim P-E loops improved the difference between the maximum polarization (P_max) and the remnant polarization (P_r). Besides, a breakdown strength field (BDS) of 2440 kV/cm was also detected in the thick film for x = 0.4. The high BDS was caused by the reduced leakage current density. Furthermore, the thick film for x = 0.4 possessed superior energy-storage stability under different temperature, frequency and electric-field cycling. In addition, 90% of the pulsed discharge energy density could be released in less than 1100 ns by using a pulsed discharge measurement.     

Structural and electrical properties of La3+-doped Na0.5Bi4.5Ti4O15-Bi4Ti3O12 inter-growth high temperature piezoceramics

New lead-free inter-growth piezoelectric ceramics, Na_0.5Bi_8.5-xLa_xTi₇O₂₇ (NBT-BIT-xLa, 0.00≤x≤1.00), were prepared by the conventional solid-state method. Structural and electrical properties of NBT-BIT-xLa were studied. All the NBT-BIT-xLa samples exhibited a single inter-growth structured phase. XRD and Raman spectroscopy revealed a reduced orthorhombicity, which strongly supports the variation of dielectric and ferroelectric properties. Plate-like grains were found to decrease with the increasing x contents. Impedance spectra analysis indicated that oxygen vacancy defects dominated the contributions to the electrical conductivity. The increased activation energies for dc conductivity evidenced the reduction of oxygen vacancy concentration after La substitution, inducing the enhancement in piezoelectric constant (d₃₃) and remanent polarization (2P_r). The studies of thermal depoling indicated that the optimal d₃₃ of NBT-BIT-0.50La ceramics still remained 22 pC/N at 500 °C, implying that this ceramics could be potentially applied into high temperature devices.     

Low-temperature sintering,structure transition and dielectrical properties of Ba0.85Ca0.15Ti0.9Zr0.1O3 with Na0.5Bi0.5TiO3 addition

Na_0.5Bi_0.5TiO₃-modified Ba_0.85Ca_0.15Ti_0.9Zr_0.1O₃ ceramics were prepared by solid state route and their structural and dielectric properties were investigated. The sintering temperature of BCTZ ceramics has been significantly decreased from 1460 °C to 1280 °C with NBT addition. All samples showed a pure perovskite structure and a stable solid solution has been formed between BCTZ and NBT. Some tetragonal phase gradually transformed to rhombohedral or cubic phase with the addition of NBT. Dielectric peak gradually becomes broader, revealing that the diffuser behavior was enhanced. The prominent superimposed loss peaks related to thermally activated relaxation process. The values of activation energy of the relaxation process are 1.034, 1.285, 1.308 and 1.353 eV, which could be associated with the migration of oxygen vacancies.     

Microstructure and electrical properties of 3-0 type composite of Na0.5Bi2.5Nb2O9-based bismuth-layered piezoceramics

The microstructure and electrical properties of 3-0 type composite of Na_0.5Bi_2.5Nb₂O₉-based bismuth layered piezoceramics modified by Al₂O₃ addition are investigated. The darker and plate-like grains, locating at the grain boundaries, are confirmed to be pure α-Al₂O₃ by high resolution transmission electron microscope, not a Bi₂AlNbO₇ pyrochlore phase. This 3-0 type Na_0.5Bi_2.5Nb₂O₉-Al₂O₃ composite piezoceramics have a large piezoelectric constant d₃₃ of 15.2pC/N with good temperature stability up to 600 °C, and good ferroelectric properties with a relatively large remnant polarization of ~11.6 μC/cm². These demonstrate that designing a 3-0 type composite structure would be an effective approach to tailor the microstructure and improve the electrical properties of bismuth layered piezoceremics for their potential applications at temperature up to 600 °C.     

Luminescence and electrical properties of Eu-modified Bi0.5Na0.5TiO3 multifunctional ceramics

The Eu³⁺-modified Bi_0.5Na_0.5TiO₃ (BNT) ceramics have been fabricated by the solid-state reaction method. The impact of Eu³⁺ doping on the structure, photoluminescence, and electrical properties has been studied by XRD, SEM, PL spectra, and LCR meter. X-ray diffraction analysis reveals that the crystal structure of the samples is well matched with the trigonal perovskite, and the optimal temperature of presintering is 880°C. The Eu³⁺-doped BNT ceramics show excellent red fluorescence at 614 nm corresponding to the ⁵D₀→⁷F₂ transition of Eu³⁺ under 466 nm excitation and relatively long fluorescence lifetime. The BNT-0.02Eu ceramic density is up to 5.68 g/cm³ and the relative density is up to 94.6% with sintering temperature 1075°C. The piezoelectric constant (d₃₃) of samples has been significantly improved up to 110 pC/N by Eu³⁺ doping. The BNT-0.03Eu ceramic presintered at 880°C and sintered at 1050°C has good dielectric properties and excellent luminescence properties. Eu³⁺-doped BNT ceramics make it potential applications for novel integrated electro-optical and multifunctional devices.     

Structural and impedance analysis of Bi0.5Na0.5Ti0.80Mn0.20O3 ceramics

The Bi_0.5Na_0.5Ti_0.80Mn_0.20O₃ ceramic was synthesized by a conventional solid-state reaction technique. Rietveld refinement of X-ray diffraction data confirms the rhombohedral crystal structure of the compound with R3c space group. The optical band gap energy of the compound is found to be 1.93 eV. The substitution of 20% Mn ions at the Ti sites results in the improved dielectric characteristics and a shift in the ferroelectric to paraelectric electric phase transition peak from 330 °C to 370 °C in the material. The frequency dispersion of dielectric constant and its footprint in the Nyquist and Cole-Cole plots have been analyzed. The analysis of complex impedance and modulus spectroscopy confirms the non-Debye type of relaxation mechanisms in the material with contributions from both the grain and grain boundary to the electrical properties. The frequency dependence of AC conductivity data exhibits overlapping large polaron tunneling conduction mechanism in the compound.     

Structural evolution and electrical properties of Na0.5Bi0.5TiO3-CoFe2O4 ceramics with embedded structures

Lead-free 0.9Na_0.5Bi_0.5TiO₃ − 0.1CoFe₂O₄ (0.9NBT-0.1CFO) composite ceramics with novel embedded microstructures were synthesized by an in-situ sol-gel method. The structural evolution, ferroelectricities and dielectricities were studied. The embedded structures were formed around 1000 °C − 1100 °C with contributions of the strong grain boundary mobility and small size of CFO grains, and then were destroyed at 1150 °C. The 0.9NBT-0.1CFO ceramic sintered at 1100 °C showed the optimal ferroelectric hysteresis loop with a remanent polarization of ~ 52 μC/cm². Anomaly peaks in the temperature dependent permittivity curves were observed in all ceramics with embedded structures. These Debye-like type peaks generated by the interface effects of NBT and CFO appeared around ~620 °C, and could reach relatively large values of ~15000 at 100 kHz. The change rate of permittivity between zero magnetic field and 500 Oe reached 2.4%, indicating a noteworthy magnetoelectric effect.     

Thermally-stable large strain in Bi(Mn0.5Ti0.5)O3 modified 0.8Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3 ceramics

(1-x)[0.8Bi_0.5Na_0.5TiO₃-0.2Bi_0.5K_0.5TiO₃]-xBi(Mn_0.5Ti_0.5)O₃ (x = 0–0.06, BNKMT100x) lead-free ferroelectric ceramics were prepared via solid state reaction method. Bi(Mn_0.5Ti_0.5)O₃ induces a structure transition from rhombohedral-tetragonal morphotropic phases to pseudo-cubic phase. Moreover, the wide range of compositions within x = 0.03–0.055 exhibit large strain of 0.31%–0.41% and electrostrictive coefficient of 0.027–0.041 m⁴/C². Especially, at x = 0.04, the large strain and electrostrictive coefficient are nearly temperature-independent in the range of 25–100 °C. The impedance analysis shows the large strain and electrostrictive coefficient originate from polar nanoregions response due to the addition of Bi(Mn_0.5Ti_0.5)O₃.     

High-temperature dielectric and energy storage properties of Bi0.5Na0.5TiO3-based ceramics modified by Sr0.8Na0.4Nb2O6

Sr_0.8Na_0.4Nb₂O₆ with a tungsten bronze structure is introduced into perovskite-structured 0.94(Bi_0.5Na_0.5)TiO₃-0.06BaTiO₃ composition (abbreviated as BNT-BT-xSNN, x = 0-0.04). The temperature stability of dielectric properties and energy storage performance is found to be effectively enhanced by Sr_0.8Na_0.4Nb₂O₆ dopant. When x is 0.03, the temperature ranges covering |ε'-ε'_150°C|/ε'_150°C ≤15% and tanδ ≤ 0.02 are 43°C-404°C and 90°C-422°C, respectively. More importantly, ε′ can be retained as high as 3304 at 150°C. Besides, the variances of energy storage density and its efficiency are 6.4% and 5.3%, respectively, in the temperature range from room temperature (RT) to 180°C. Therefore, this work provides a new method of compositional modification in BNT-based materials to improve their temperature stability of dielectric and energy storage properties.     

Mechanism of Bi0.5Na0.5TiO3 and Bi4.5Na0.5Ti4O15 template synthesis during topochemical microcrystal conversion and texturing of Bi0.5(Na0.8K0.2)0.5TiO3 piezoelectric ceramics

The mechanism by which Bi_0.5Na_0.5TiO₃ and Bi_4.5Na_0.5Ti₄O₁₅ templates are synthesized via a topochemical microcrystal conversion method using Bi₄Ti₃O₁₂ precursor and TiO₂ particles was investigated based on their crystal structures. The Bi_0.5Na_0.5TiO₃ template consisted of a mixture of plate-like and equiaxed particles, whereas the Bi_4.5Na_0.5Ti₄O₁₅ template consisted only of plate-like particles. The size of the plate-like and equiaxed particles was dependent on the size of the Bi₄Ti₃O₁₂ precursor and TiO₂ particles, respectively. The Lotgering factor and piezoelectric constant of textured Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ ceramics prepared using the Bi_0.5Na_0.5TiO₃ template were lower than those of the textured Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ ceramics prepared from the Bi_4.5Na_0.5Ti₄O₁₅ template. This can be attributed to the small amount of plate-like particles in the Bi_0.5Na_0.5TiO₃ template caused by the inevitable co-existence of equiaxed particles.     

Ca2+ doping effects on the structural and electrical properties of Na0.5Bi4.5Ti4O15 piezoceramics

Bismuth layer structured Na_0.5Bi_4.5Ti₄O₁₅ (NBT) ferroelectric is one of the most promising materials for potential applications at high temperature. However, it is challenged to achieve a balance between high Curie temperature piezoelectric coefficient and excellent thermal stability for NBT piezoceramics. Here, through chemical modification at the A site of NBT with Ca²⁺, novel (Na_0.5Bi_0.5)_1-xCa_xBi₄Ti₄O₁₅ piezoceramics with excellent properties fabricated by solid state reaction were studied. After doping of Ca²⁺, the Curie temperature T_C increased from 648 °C to 662 °C while the piezoelectric coefficient d₃₃ increased from 14 pC/N to 22 pC/N which can be attributed to the intrinsic contribution of TiO₆ octahedral lattice distortion (tilting and rotation) and the extrinsic contribution of the increased density of domain walls. The composition of (Na_0.5Bi_0.5)_0.95Ca_0.05Bi₄Ti₄O₁₅ ceramics with x = 0.05 has the optimal performance with high T_C of 655 °C, large d₃₃ of 22 pC/N, high electrical resistivity ρ close to 10⁷ Ω cm at 500 °C and especially excellent thermal stability of d₃₃ only about 5% reduction after being annealed at 625 °C. The work effectively reveals the great potential of CNBT-5 ceramics for high-temperature piezoelectric applications.     

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.     

Mn doping effects on electric properties of 0.93(Bi0.5Na0.5)TiO3‐0.07Ba(Ti0.945Zr0.055)O3 ceramics

The validity of Mn element on 0.93(Bi_0.5Na_0.5)TiO₃‐0.07Ba(Ti_0.945Zr_0.055)O₃ ceramics (BNT‐BZT‐xMn) is certified by doping. On account of multiple effects introduced by Mn, the appropriate Mn content facilitates property improvement effectively. Compared with pure BNT‐BZT, d₃₃ of the component x = 0.25 increases about 8% up to 187 pC/N and Q_m of the component x = 1 increases about 84% up to 197. Thermally stimulated depolarization currents (TSDC) measurement reveals Mn additive is helpful to pyroelectric properties as well. The Mn‐doped component x = 0.125 exhibits better pyroelectric performance at room temperature. Corresponding pyroelectric coefficient and the figures of merit reach up to 0.061 μC/(cm² °C), F_i=217 pm/V, F_ν = 0.023 m²/C, and F_d = 12.6 μPa^?1/2, respectively, even superior to lead‐based ceramics. Similar pyroelectric advantage is also observed in the component x = 0.5 near depolarization temperature T_d. Mn doping has slight harmful influence on the ferroelectric‐to‐relaxor transition temperature T_F?R, as well as T_d, but hardly shows restriction on application. These results confirm Mn doping is an available strategy to improve BNT‐based ceramics. Therefore, Mn‐doped BNT‐BZT ceramics will be excellent candidates in area of high‐power piezoelectric application and pyroelectric detectors.     

Phase transition and electrical properties of Bi0.5(Na0.8K0.2)0.5ZrO3 modified (K0.52Na0.48)(Nb0.95Sb0.05)O3 lead-free piezoelectric ceramics

In this work, (1−x)(K_0.52Na_0.48)Nb_0.95Sb_0.05O₃−xBi_0.5(Na_0.8K_0.2)_0.5ZrO₃ [abbreviated as (1−x)KNNS−xBNKZ, x=0–0.06] lead-free ceramics were fabricated using solid-state reaction method. The effects of BNKZ contents on the phase structure, piezoelectric and ferroelectric properties were investigated. The phase boundaries including orthorhombic-tetragonal (O-T) and rhombohedral-tetragonal (R-T) multiphase coexistence were identified by XRD patterns and temperature-dependent dielectric constant by adding different content of BNKZ. A giant field induced strain (~0.25%) along with converse piezoelectric coefficient d₃₃^* (~629.4 pm/V) and enhanced ferroelectricity P_r (~38 μC/cm²) were obtained when x=0.02, while the specimen with x=0.03 presented the optimal piezoelectric coefficient d₃₃ of 215 pC/N, due to the O-T or R-T phase coexistence near room temperature respectively. These results show that the introduction of Bi_0.5(Na_0.8K_0.2)_0.5ZrO₃ is a very effective way to improve the electrical properties of (K_0.52Na_0.48)(Nb_0.95Sb_0.05)O₃ lead-free piezoelectric ceramics.     

Structural,dielectric and electrical properties of BaSnO3 and BaSeO3 modified Bi0.5Na0.5TiO3 ceramics

In this communication, preliminary structural and detailed electrical (dielectric, polarization, impedence, and conductivity) characteristics of BaSnO₃ and BaSeO₃ modified complex Bi_0.5Na_0.5TiO₃ ceramics with a general chemical formula and composition, (1–2x)[(Bi_0.5Na_0.5) TiO₃]+x(BaSnO₃)+x(BaSeO₃) (with x = 0, 0.05, 0.1, 0.15) (BNT–BSn–BSe) ceramics, synthesized by a high-temperature mixed-oxide technique (calcinations temperature = 925 °C and sintering temperature = 950 °C, for time = 4 h each) have been reported. Analysis of room temperature X-ray diffraction data has confirmed the formation of single phase perovskite of BNT–BSn–BSe in rhombohedral phase and provided crystal data. Studies of impedance spectroscopy and electrical conductivity of the materials in a frequency range of (1 kHz-1MHz) at different temperatures (25–500 °C) have shown the composition (x) effect on electrical characteristics of BSn and BSe modified BNT.The electric field dependent polarization study at room temperature exhibits the existence of ferroelectricity in the materials. Study of the impedance spectroscopy through Nyquist plots shows the contributions of the grains and grain boundary in the resistive and capacitive properties of the materials. This study also determines the existence of NTCR (negative temperature coefficient of resistance) behavior the prepared materials. The J–E characteristics demonstrate the Ohomic behavior with slope closer to 1.     

Preparation and Electric Properties of Bi0.5Na0.5TiO3–Bi(Mg0.5Ti0.5)O3 Lead‐Free Piezoceramics

Lead‐free BNT‐based piezoceramics, (1?x)Bi_0.5Na_0.5TiO₃–xBi(Mg_0.5Ti_0.5)O₃ [(1?x)BNT–xBMT] (0.00 ≤ x ≤ 0.06) binary system, were synthesized using a conventional ceramic fabrication method. Effect of Bi(Mg_0.5Ti_0.5)O₃ (BMT) substitution on room temperature (RT) crystal structure, and temperature dependence of electric properties were investigated. The XRD indicates that a pure perovskite phase is formed. The introduction of BMT decreases E_C of BNT from 7.3 to 4.0 kV/mm, and increases d₃₃ from 58 pC/N to 110 pC/N for the x = 0.05. The system shows a typical ferroelectric (FE) polarization loop P(E) and butterfly bipolar strain‐electric S(E) curve at RT. For the composition of 0.95BNT–0.05BMT antiferroelectric (AFE) phase appears near 80°C, characterized by a constricted P(E) loop and altered bipolar S(E) butterfly, and gradually prevails with increasing temperature. Temperature dependence of dielectric constant shows that T_C increases from 310°C for pure BNT to 352°C for the x = 0.05. The results indicate that the piezoelectric properties of BNT have been improved by means of Bi(Mg_0.5Ti_0.5)O₃ substitution.     

Structural and electrical properties of Na0.5Bi4.0RE0.5Ti4O15 (RE=Tm,Yb and Lu) thin films

In the current study, a series of lanthanide ions, Tm, Yb and Lu, were used for doping at the Bi-site of the Aurivillius phase Na_0.5Bi_4.5Ti₄O₁₅ (NaBTi) to investigate the structural, electrical and ferroelectric properties of the thin films. In this regard, Na_0.5Bi_4.5Ti₄O₁₅ and the rare earth metal ion-doped Na_0.5Bi_4.0RE_0.5i₄O₁₅ (RE=Tm, Yb and Lu, denoted by NaBTmTi, NaBYbTi, and NaBLuTi, respectively) thin films were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. Formations of the Aurivillius phase orthorhombic structures for all the thin films were confirmed by X-ray diffraction and Raman spectroscopic studies. Based on the experimental results, the rare earth metal ion-doped Na_0.5Bi_4.0RE_0.5Ti₄O₁₅ thin films exhibited a low leakage current and the improved ferroelectric properties. Among the thin films, the NaBLuTi thin film exhibited a low leakage current density of 6.96×10⁻⁷ A/cm² at an applied electric field of 100 kV/cm and a large remnant polarization (2P_r) of 26.7 μC/cm² at an applied electric field of 475 kV/cm.     

A correlation of piezoelectricity and photoluminescence of europium doped (Na0.41K0.09Bi0.5)TiO3 with ferroelectric and structural ordering

A correlation between piezoelectricity and photoluminescence is investigated for europium doped (Na_0.41K_0.09Bi_0.5)TiO₃ ceramic. An optimum piezoelectric and dielectric response is observed for 1.0 at.% Eu doped (Na_0.41K_0.09Bi_0.5)TiO₃. For doping concentration higher than 1.0 at.% a gradual fall in the piezoelectric response is observed which is associated to the amphoteric nature of Eu³⁺ ion. On the contrary, the photoluminescence intensity increases monotonically with the increase in Eu concentration. On application of an electric field, although there is no noticeable shift in the position and shape of the photoluminescence line, a quenching of hypersensitive ⁵D₀ → ⁷F₂ transition is observed. The quenching effect is more evident for lower doping concentration (less than 2.0 at.%) of europium. The emergence of irreversible tetragonal phase, after application of the electric field, is attributed to the quenching of ⁵D₀ → ⁷F₂ transition. Based on these investigations it is concluded that the piezoelectric and photo-luminescence lack one-to-one correlation. The PL response is associated to the local site symmetry around Eu³⁺ and it is independent of the development of long-range ordering.     

Dielectric properties of some low-lead or lead-free perovskite-derived materials: Na0.5Bi0.5TiO3–PbZrO3, Na0.5Bi0.5TiO3–BiScO3 and Na0.5Bi0.5TiO3–BiFeO3 ceramics

Na_0.5Bi_0.5TiO₃ (NBT) and its modifications are known to be new lead-free ferroelectric materials and are promising for environment friendly devices. The systems under investigation were (i) NBT (trigonal/ferroelectric)–PbZrO₃ (orthorhombic/antiferroelectric); (ii) NBT (trigonal/ferroelectric)–BiScO₃ (trigonal/paraelectric); and (iii) NBT (trigonal/ferroelectric)–BiFeO₃ (trigonal/antiferromagnetic).The lattice parameters change as expected from the respective ionic radii values. For NBT–PZ, the dielectric permittivity shows a large frequency and temperature dispersion suggesting a relaxor-like behaviour dependent on the thermal annealing of the samples. For NBT–BS, the Curie temperature increases with BS content as well as the diffuseness of the phase transition, connected with the introduced disorder. For NBT–BF, the overall behaviour of the permittivity of NBT is maintained up to 50% BF but anomalies of the permittivity appeared close to 600 °C, which might be connected with the onset of magnetic influence for high BF content.