Effect of Oxygen Vacancy on Electrical Property of Acceptor Doped BaTiO3–Na0.5Bi0.5TiO3–Nb2O5 X8R Systems

In this study, we reported a new BaTiO₃–Na_0.5Bi_0.5TiO₃–Nb₂O₅–Mn₂O₃/Fe₂O₃/Co₃O₄/In₂O₃ X8R system with high dielectric constant (>2100) at room temperature. The impacts of oxygen vacancy ( ) on dielectric, electrical conductivity, and ferroelectric properties were systematically studied. The Curie point is largely depended on the concentration, which can be confirmed by the dielectric behavior and A_1g octahedral breathing modes in Raman spectrum. In addition, the activation energy of diffusion is greatly reduced with the increase in concentration. It was found that the remnant polarization and coercive field were both decreased with increasing concentration, due to the facilitated defect dipoles reorientation and domain switching.     

Dielectric nonlinear behavior of (Ba0.95Ca0.05)(Ti0.83Zr0.17)O3‐based multi‐layer ceramic capacitor

The influence of temperature on the variation in dielectric nonlinearity and domain structures was investigated for the (Ba_0.95Ca_0.05)(Ti_0.83Zr_0.17)O₃ (BCTZ)‐based multilayer ceramic capacitor that shows a diffuse phase transition. Whereas the dielectric constant (ε_r) vs temperature shows a broadened maximum peak at low ac driving field, such a peaked behavior disappears at high ac driving field due to an abrupt increase in dielectric constants at low temperatures. Such low temperature effect can be associated with an enhanced spontaneous polarization (P_S) and a significant increase in irreversible domain wall contribution to polarization representing normal ferroelectric behavior based on the Preisach analysis. No ferroelectric domain contrasts were observed at room temperature through transmission electron microscopy. However, they appeared and became more and more distinct with the decrease in temperature, and the crystal structure also changed from cubic to rhombohedral with increased lattice constants. It demonstrates that the dramatic increase in the dielectric nonlinearity with decreasing temperatures originates from the corresponding changes in domain and crystal structure, where the polar‐micro‐regions of BCTZ at room temperature change to normal ferroelectric domains at low temperatures.     

Structure‐property relationships in BiScO3–PbTiO3–PbMg1/3Nb2/3O3 ceramics near the morphotropic phase boundary

The phase structure, dielectric, ferroelectric, and piezoelectric properties of (1?2x)BiScO₃–xPbTiO₃–xPbMg_1/3Nb_2/3O₃ ceramics (x = 0.30‐0.46) were studied. It was found that an increase in x leads to a structural phase transition between the rhombohedral and tetragonal phase via an intermediate monoclinic phase and to a crossover from the nonergodic relaxor state to the ferroelectric one. It was proposed that at x > 0.42 the phase transition changes from second to first order. The assumption about the existence of a tricritical point on the phase diagram at x ≈ 0.42 with the enhanced dielectric response has been made. The observed structure‐property relationships of the studied solid solutions are discussed. It is shown that the solid solutions with x = 0.42 are characterized by the high piezoelectric parameters (d₃₃ = 509 pC/N, d₃₁ = ?178 pC/N, d_h = 153 pC/N), which makes possible their applications in sonar equipment.     

Defect mechanisms in BaTiO3‐BiMO3 ceramics

Often, addition of BiMO₃ to BaTiO₃ (BT) leads to improvement in resistivity with a simultaneous shift to n‐type conduction from p‐type for BT. In considering one specific BiMO₃ composition, that is, Bi(Zn_1/2Ti_1/2)O₃ (BZT), several prospective candidates for the origin of this n‐type behavior in BT‐BZT were studied—loss of volatile cations, oxygen vacancies, bismuth present in multiple valence states and precipitation of secondary phases. Combined x‐ray and neutron diffraction, prompt gamma neutron activation analysis and electron energy loss spectroscopy suggested much higher oxygen vacancy concentration in BT‐BZT ceramics (>4%) as compared to BT alone. X‐ray photoelectron spectroscopy and x‐ray absorption spectroscopy did not suggest the presence of bismuth in multiple valence states. At the same time, using transmission electron microscopy, some minor secondary phases were observed, whose compositions were such that they could result in effective donor doping in BT‐BZT ceramics. Using experimentally determined thermodynamic parameters for BT and slopes of Kröger‐Vink plots, it has been suggested that an ionic compensation mechanism is prevalent in these ceramics instead of electronic compensation. These ionic defects have an effect of shifting the conductivity minimum in the Kröger‐Vink plots to higher oxygen partial pressure values in BT‐BZT ceramics as compared to BT, resulting in a significantly higher resistivity values in air atmosphere and n‐type behavior. This provides an important tool to tailor transport properties and defects in BT‐BiMO₃ ceramics, to make them better suited for dielectric or other applications.     

The properties of Al2O3 coated fine‐grain temperature stable BaTiO3‐based ceramics sintered in reducing atmosphere

Chemical coating, an effective doping modification method, was employed to fabricate fine‐grain BaTiO₃‐based ceramics. Based on the consideration of subsequently using base metal as inner electrodes in multilayer ceramic devices, green bodies are generally sintered in reducing atmosphere, which generates more charged point defects and thus affects the electric properties. According to the elements distribution analysis, Al element is greatly enriched in the grain boundary and shell region. Coating Al₂O₃ achieves not only a smaller grain size and narrower distribution but also a higher breakdown strength, discharge energy density and energy efficiency at ambient temperature. In addition, temperature dependences of dielectric and energy storage properties under a same field were also investigated. Over the whole measuring temperature range, the sample with Al₂O₃ remains higher discharge energy density and energy efficiency.     

Correlative chemical and structural nanocharacterization of a pseudo-binary 0.75Bi(Fe0.97Ti0.03)O3-0.25BaTiO3 ceramic

Fast cooling after sintering or annealing of BiFeO₃-BaTiO₃ mixed-oxide ceramics yields core-shell structures that give excellent functional properties, but their precise phase assemblage and nanostructure remains an open question. By comparing conventional electron energy loss spectroscopy (EELS) with scanning precession electron diffraction (SPED) mapping using a direct electron detector, we correlate chemical composition with the presence or absence of octahedral tilting and with changes in lattice parameters. This reveals that some grains have a three-phase assemblage of a BaTiO₃-rich pseudocubic shell; a BiFeO₃-rich outer core with octahedral tilting consistent with an R3c structure; and an inner core richer in Ba and even poorer in Ti, which seems to show a pseudocubic structure of slightly smaller lattice parameter than the shell region. This last structure has not been previously identified in these materials, but the composition and structure fit with previous studies. These inner cores are likely to be non-polar and play no part in the ferroelectric properties. Nevertheless, the combination of EELS and SPED clearly provides a novel way to examine heterogeneous microstructures with high spatial resolution, thus revealing the presence of phases that may be too subtle to detect with more conventional techniques.     

Electrocaloric Effect in Ba(Zr,Ti)O3–(Ba,Ca)TiO3 Ceramics Measured Directly

In this paper, we report on studies of the electrocaloric (EC) effect in lead‐free (1?x)Ba(Zr_0.2Ti_0.8)O₃–x(Ba_0.7Ca_0.3)TiO₃ ceramics with compositions range between 0.32 ≤ x ≤ 0.45. The EC effect was measured directly using a modified differential scanning calorimeter. The maximum EC temperature change, ΔT_direct = 0.33 K under an electric field of 2 kV/mm, was observed for the composition with x = 0.32 at ~63°C. We found that the EC effect peaks not only around the Curie temperature but also at the transition between the ferroelectric phases with different symmetries. A strong discrepancy observed between the results of the direct measurements and indirect estimations points out that using Maxwell's equations is invalid for the thermodynamic nonequilibrium conditions that accompany only partial (incomplete) poling of ceramics. We also observe a nonlinearity of the EC effect above the Curie temperature and in the temperature range corresponding to the tetragonal ferroelectric phase.     

Phase coexistence and large piezoelectricity in BaTiO3‐CaSnO3 lead‐free ceramics

Ferroelectric phase coexistence was constructed in (1?x)BaTiO₃‐xCaSnO₃ lead‐free ceramics, and its relationship with the piezoelectricity of the materials was investigated to ascertain potential factors for strong piezoelectric response. It is found that the addition of CaSnO₃ caused a series of phase transitions in the (1?x)BaTiO₃‐xCaSnO₃ ceramics, and a ferroelectric coexistence of rhombohedral, orthorhombic, and tetragonal phases is formed at x = 0.08, where the ceramics exhibit the lowest energy barrier and consequently facilitate the polarization rotation and extension, resulting in the optimal piezoelectricity of d₃₃ and k_p values of 550 pC/N and 0.60, respectively. Our study provides an intuitive insight to understand the origin of high piezoelectricity in the ceramics with the coexistence of multiferroelectric phases.     

High strain (0.4%) Bi(Mg2/3Nb1/3)O3‐BaTiO3‐BiFeO3 lead‐free piezoelectric ceramics and multilayers

The relationship between the piezoelectric properties and the structure/microstructure for 0.05Bi(Mg_2/3Nb_1/3)O₃‐(0.95‐x)BaTiO₃‐xBiFeO₃ (BBFT, x = 0.55, 0.60, 0.63, 0.65, 0.70, and 0.75) ceramics has been investigated. Scanning electron microscopy revealed a homogeneous microstructure for x < 0.75 but there was evidence of a core‐shell cation distribution for x = 0.75 which could be suppressed in part through quenching from the sintering temperature. X‐ray diffraction (XRD) suggested a gradual structural transition from pseudocubic to rhombohedral for 0.63 < x < 0.70, characterized by the coexistence of phases. The temperature dependence of relative permittivity, polarization‐electric field hysteresis loops, bipolar strain‐electric field curves revealed that BBFT transformed from relaxor‐like to ferroelectric behavior with an increase in x, consistent with changes in the phase assemblage and domain structure. The largest strain was 0.41% for x = 0.63 at 10 kV/mm. The largest effective piezoelectric coefficient (d₃₃^*) was 544 pm/V for x = 0.63 at 5 kV/mm but the largest Berlincourt d₃₃ (148 pC/N) was obtained for x = 0.70. We propose that d₃₃^* is optimized at the point of crossover from relaxor to ferroelectric which facilitates a macroscopic field induced transition to a ferroelectric state but that d₃₃ is optimized in the ferroelectric, rhombohedral phase. Unipolar strain was measured as a function of temperature for x = 0.63 with strains of 0.30% achieved at 175°C, accompanied by a significant decrease in hysteresis with respect to room temperature measurements. The potential for BBFT compositions to be used as high strain actuators is demonstrated by the fabrication of a prototype multilayer which achieved 3 μm displacement at 150°C.     

BaTiO3–Bi(Mg2/3Nb1/3)O3 Ceramics for High‐Temperature Capacitor Applications

Solid solutions of (1?x)BaTiO₃–xBi(Mg_2/3Nb_1/3)O₃ (0 ≤ x ≤ 0.6) were prepared via a standard mixed‐oxide solid‐state sintering route and investigated for potential use in high‐temperature capacitor applications. Samples with 0.4 ≤ x ≤ 0.6 showed a temperature independent plateau in permittivity (ε_r). Optimum properties were obtained for x = 0.5 which exhibited a broad and stable relative ε_r ~940 ± 15% from ~25°C to 550°C with a loss tangent <0.025 from 74°C to 455°C. The resistivity of samples increased with increasing Bi(Mg_2/3Nb_1/3)O₃ concentration. The activation energies of the bulk were observed to increase from 1.18 to 2.25 eV with an increase in x from 0 to 0.6. These ceramics exhibited excellent temperature stable dielectric properties and are promising candidates for high‐temperature multilayer ceramic capacitors for automotive applications.     

High permittivity (1−x)Bi1/2Na1/2TiO3‐xPbMg1/3Nb2/3O3 ceramics for high‐temperature‐stable capacitors

(1?x)Bi_1/2Na_1/2TiO₃‐xPbMg_1/3Nb_2/3O₃[(1?x)BNT‐xPMN] ceramics have been fabricated via a conventional solid‐state method for compositions x ≤ 0.3. The microstructure, phase structure, ferroelectric, and dielectric properties of ceramics were systematically studied as high‐temperature capacitor materials. XRD pattern certified perovskite phase with no secondary phase in all compositions. As PMN concentration increased, the phase of (1?x)BNT‐xPMN ceramics transformed from ferroelectric to relaxor gradually at room temperature, with prominent enhancement of dielectric temperature stability. For the composition x = 0.2, the temperature coefficient of capacitance (TCC) was <15% in a wide temperature range from 56 to 350°C with high relative permittivity (>3300) and low dielectric loss (<0.02) at 150°C, which indicated promising future for (1?x)BNT‐xPMN system as high‐temperature stable capacitor materials.     

Large strain response with low driving field in Bi1/2Na1/2TiO3–Bi1/2K1/2TiO3–Bi(Mg2/3Nb1/3)O3 ceramics

The (1?x)(0.8Bi_1/2Na_1/2TiO₃–0.2Bi_1/2K_1/2TiO₃)?xBiMg_2/3Nb_1/3O₃ (100xBMN) ternary solid solutions were designed and prepared using a conventional solid‐state reaction. Temperature and compositional dependent ferroelectric, piezoelectric, dielectric features, and structural evolution were systematically studied. At the critical composition of 2BMN, a large bipolar strain of 0.43% was achieved at 55 kV/cm, and the normalized strain reaches to 862 pm/V at a low driving electric field of 40 kV/cm. It was found that the substitution of BiMg_2/3Nb_1/3O₃ induces a transformation from ferroelectric to relaxor phase by disrupting the long range ferroelectric order. Therefore, as the external electric field was applied, a relaxor‐ferroelectric phase transition will be induced. This is contributed to the giant strain. The results above suggest that such a ternary composition is a promising candidate for application to actuator.     

Solid-State Preparation of BaTiO3-Based Dielectrics, Using Ultrafine Raw Materials

BaTiO₃ and Ba(Ti,Zr)O₃ dielectric powders have been prepared from submicrometer BaCO₃, TiO₂, and ZrO₂. By use of submicrometer BaCO₃ the intermediate formation of Ba₂TiO₄ second phase can be widely suppressed. Monophase perovskites of BaTiO₃ were already formed at 900°C and Ba(Ti,Zr)O₃ at 1050°C. Aggregates of very small subgrains could be easily disintegrated to particle sizes <0.5 μm.     

Structure–Property Relationships in Aligned Electrospun Barium Titanate Nanofibers

Barium titanate nanofibers were uniaxially aligned by electrospinning onto a rotating copper wire drum and alignment was maintained during calcination of the fibers. Two methods for maintaining alignment during calcination were tested, by either using carbon tape or a peeling off method to remove the aligned fibers from the mandrel followed by calcination. The carbon tape removal method led to the formation of shorter aligned nanowires while the peeling off method resulted in longer nanofibers. Additionally, the effects of calcination temperature and time on crystal structure were also examined. The degree of tetragonality in the barium titanate nanofibers increased at higher calcination temperatures and times. Piezoelectricity was confirmed in the nanofibers calcined using piezoeresponse force microscopy, yielding a d₃₃ value of 15.5 pm/V. Using the methods presented here, large quantities of aligned piezoelectric barium titanate and other ceramic fibers or wires can be produced to fulfill their demand in novel microelectronics.     

Influence of [Ba + Ca]/[Ti + Zr] Ratio on the Interfacial Property of (Ba,Ca)(Ti,Zr)O3 (BCTZ) Powders in an Aqueous Medium

We report findings on the electrokinetic and solubility behaviors of (Ba,Ca)(Ti,Zr)O₃ (BCTZ) powders having three different [Ba + Ca]/[Ti + Zr] ratios: 0.995, 1.000, and 1.005. Electrokinetic and solubility properties of BCTZ powders in aqueous media are phenomenologically similar to BaTiO₃. Ba and Ca ions, occupying primarily A-sites on the perovskite lattice, dissolve during acid titration, which results in surface depletion of A-site cations in the surface region of BCTZ particles. The electrokinetics of colloidal BCTZ powders reflects changes in the surface chemistry that occur as a result of dissolution and adsorption/reprecipitation of surface ions. An increase in [Ba + Ca]/[Ti + Zr] ratio results in an increase in the dynamic mobility at all pH values, an increase in the titration hysteresis, and an increase in the isoelectric pH. Each of these effects can be attributed to Ba and Ca in the near-surface region of BCTZ.     

Giant electromechanical strain response in lead‐free SrTiO3‐doped (Bi0.5Na0.5TiO3–BaTiO3)–LiNbO3 piezoelectric ceramics

Lead‐free 0.985[(0.94?x)Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–xSrTiO₃]–0.015LiNbO₃ [(BNT–BT–xST)–LN, x=0‐0.05] piezoelectric ceramics were prepared using a conventional solid‐state reaction method. It was found that the long‐range ferroelectric order in the unmodified (BNT–BT)–LN ceramic was disrupted and transformed into the ergodic relaxor phase with the ST substitution, which was well demonstrated by the dramatic decrease in remnant polarization (P_r), coercive field (E_c), negative strain (S_neg) and piezoelectric coefficient (d₃₃). However, the degradation of the ferroelectric and piezoelectric properties was accompanied by a significant increase in the usable strain response. The critical composition (BNT–BT–0.03ST)–LN exhibited a maximum unipolar strain of ~0.44% and corresponding normalized strain, S_max/E_max of ~880 pm/V under a moderate field of 50 kV/cm at room temperature. This giant strain was associated with the coexistence of the ferroelectric and ergodic relaxor phases, which should be mainly attributed to the reversible electric‐field‐induced transition between the ergodic relaxor and ferroelectric phases. Furthermore, the large field‐induced strain showed relatively good temperature stability; the S_max/E_max was as high as ~490 pm/V even at 120°C. These findings indicated that the (BNT–BT–xST)–LN system would be a suitable environmental‐friendly candidate for actuator applications.     

(1-x)BaTiO3-xLiNbO3陶瓷的制备及性能研究

采用复合溶胶凝胶法制粉技术结合传统陶瓷制备工艺，制备了（1-x）BaTiO3-xLiNbO3陶瓷，并对其晶相特征、介电及压电、铁电性能进行了研究。在1250℃下烧结的陶瓷形成了单一相的钙钛矿结构固溶体，该固溶体在20-40℃之间存在二级相变，介电常数及介电损耗出现异常变化。陶瓷的铁电、压电性能随LiNbO3的加入得到显著提高。LiNbO3加入量为0．005mol的陶瓷压电常数d33为121pC／N，剩余极化强度为2．8μC／cm^2。     

Roles of Ba/Ti Ratios in the Dielectric Properties of BaTiO3 Ceramics

The effect of the Ba/Ti ratio on microstructure, dielectric/ferroelectric properties, and domain width was studied using optical microscopy, ɛ( T ) curves, D – E hysteresis, and transmission electron microscopy. Although Ti-excess samples showed abnormal grain growth and a decrease of room-temperature permittivity due to a liquid phase at grain boundaries, its ferroelectric properties were similar to those of stoichiometric BaTiO₃ ceramics. However, in Ba-excess samples, an increase of permittivity and ferroelectric properties different from those of stoichiometry were found. Changes in domain width and ferroelectric transition behavior indicated that the variation of dielectric properties was related to the internal stress. It is proposed that this internal stress originated from differences in the thermal expansion coefficient between the matrix and the second phase.     

Structure and Dielectric Properties of Pb(Sc2/3W1/3)O3–Pb(Zr/Ti)O3 Relaxors

The structure and dielectric properties of (1− x )Pb(Sc_2/3W_1/3)O₃–( x )Pb(Zr/Ti)O₃ ceramics have been investigated over a full substitution range. All compositions with x < 0.5 adopt a cubic perovskite structure; however, for x ≤ 0.25 a doubled cell results from a 1:1 ordered distribution of the B-site cations. The structural order in Pb(Sc_2/3W_1/3)O₃ (PSW) can be described by a random-site model with one cation site occupied by Sc³⁺ and the other by a random distribution of (Sc_1/3³⁺W_2/3⁶⁺). The ordering is destabilized in solid solutions of PSW with PbZrO₃ (PSW–PZ), but stabilized by PbTiO₃ in the (1− x )PSW–( x )PT system. The changes in order are accompanied by alterations in the dielectric response of the two systems. For PSW–PZ the temperature of the permittivity maximum ( T _ɛ,max) increases linearly with x ; however, for PSW–PT T _ɛ,max decreases in the ordered region (up to x = 0.25) and then increases rapidly as the order is lost. Similar effects were produced by modifying the degree of order of (0.75)PSW–(0.25)PT; when the order parameter was reduced from ∼1.0 to ∼0.65, T _ɛ,max increased by more than 60°C.