Effect of B-site isovalent doping on electrical and ferroelectric properties of lead free bismuth titanate ceramics

In the present work, zirconium modified bismuth titanate ceramics have been studied as potential lead-free ferroelectric materials over a broad temperature range (RT – 800 °C). Polycrystalline samples of Bi₄Ti_3−xZr_xO₁₂ (x=0.2, 0.4, 0.6) (BZrT) with high electrical resistivity were prepared using the solution combustion technique. The effect of Zr doping on the crystalline structure, ferroelectric properties and electrical conduction characteristics of BZrT ceramics were explored. Addition of zirconium to bismuth titanate enhances its dielectric constant and reduces the loss factor as it introduces orthorhombic distortion in bismuth titanate lattice which is exhibited by the growth along (0010) lattice plane. Activation energy due to relaxation is found to be greater than that due to conduction thus confirming that electrical conduction in these ceramics is not due to relaxation of dipoles. Remanent polarization of the doped samples increases as the Zirconium content increases.     

Effect of sintering temperature on the structural, dielectric and ferroelectric properties of tungsten substituted SBT ceramics

Structural, dielectric and ferroelectric properties of tungsten (W) substituted SrBi₂(Ta_1−xW_x)₂O₉ (SBTW) [x=0.0, 0.025, 0.05, 0.075, 0.1 and 0.2] have been studied as a function of sintering temperature (1100-1250 °C). X-ray diffraction patterns confirm the single-phase layered perovskite structure formation up to x=0.05 at all sintering temperatures. The present study reveals an optimum sintering temperature of 1200 °C for the best properties of SBTW samples. Maximum T_c of ∼390 °C is observed for x=0.20 sample sintered at 1200 °C. Peak-dielectric constant (ε_r) increases from ∼270 to ∼700 on increasing x from 0.0 to 0.20 at 1200 °C sintering temperature. DC conductivity of the SBTW samples is nearly two to three orders lower than that of the pristine sample. Remnant polarization (P_r) increases with the W content up to x≤0.075. A maximum 2P_r (∼25 μC/cm²) is obtained with x=0.075 sample sintered at 1200 °C. The observed behavior is explained in terms of improved microstructural features, contribution from the oxygen and cationic vacancies in SBTW. Such tungsten substituted samples sintered at 1200 °C exhibiting enhanced dielectric and ferroelectric properties should be useful for memory applications.     

Effects of sintering condition on phase formation,microstructure and dielectric properties of lead titanate ceramics

Lead titanate ceramics have been prepared by two different processing methods: conventional (or single-stage) and two-stage sintering. Effects of designed sintering conditions on phase formation, densification, microstructure and dielectric properties of the ceramics were characterized via X-ray diffraction, Archimedes density measurement, scanning electron microscopy and dielectric measurement, respectively. The potentiality of a two-stage sintering technique as a simple ceramic fabrication method to obtain highly dense and pure lead titanate ceramics was demonstrated. It has been found that, under suitable two-stage sintering conditions, dense perovskite lead titanate ceramics can be successfully achieved with better dielectric properties than those of ceramics from a single-stage sintering technique. PACS 77.22.-d; 77.84.-s; 77.84.Dy     

Effect of Zr:Sn ratio in the lead lanthanum zirconate stannate titanate ceramics on microstructure and electric properties

The effect of variations of the Zr:Sn ratio on the microstructure and electric properties of lead lanthanum zirconate stannate titanate (PLZST) antiferroelectric ceramics were investigated. The precursor powders were synthesized by the modified coprecipitation method and all the samples were pure perovskite phase in the XRD patterns. The ceramics sintered at 1100 °C exhibited the highest relative density. With the increasing of Sn⁴⁺ content, the grain size of the ceramics was decreased in the SEM and the maximum dielectric constant and the corresponding temperature were decreased. The P-E hysteresis loops indicated that it is helpful to steady the antiferroelectric phase by increasing Sn⁴⁺ content.     

A strong correlation of crystal structure and Curie point of barium titanate ceramics with Ba/Ti ratio of precursor composition

A series of barium titanate powders were synthesized from precursors BaCO₃ and TiO₂ with Ba/Ti ratio ranged from 0.96 to 1.04. For the ceramics sintered at 1300 °C for 2 h, with increasing Ba/Ti ratio from 0.96 to 1.04, the tetragonal distortion of perovskite barium titanate phase was decreased continuously and the Curie point was decreased monotonously from 122.9 to 98.0 °C. At the same time, the content of secondary phases was very low. This correlation of crystal structure and Curie point of barium titanate ceramics was explained by composition variation of the perovskite phase itself rather than by the influence from secondary phases. Due to very controversial results reported by different groups, it was proposed that BaTiO₃ has some different states with different solubilities for BaO and TiO₂. Further investigations should be conducted on the preparation and the properties of BaTiO₃ with much BaO or TiO₂ dissolved.     

Synthesis of bismuth titanate with urea as fuel by solution combustion route and its dielectric and ferroelectric properties

Preparation of ferroelectric bismuth titanate (Bi₄Ti₃O₁₂) is carried out by solution combustion route with urea as fuel at much lower calcinations temperatures. The single phase bismuth titanate was obtained after calcinations at 800 °C. SEM micrographs of the calcined powders show agglomerated, flaky and foamy morphology, which is typical of combustion synthesis and that of sintered ceramics shows the grain formation. Behavior of dielectric constant and dielectric loss as a function of temperature of as-prepared sample are reported in this communication. Ferroelectric to paraelectric phase transition occurs at the temperature T_c ∼ 660 °C. Its remnant polarization (2P_r) is very less of the order of 0.012 μC/cm².     

Preparation and optical properties of barium titanate thin films

Barium titanate (BTO) films were prepared by sol-gel spin-coating technique. The crystal structure and optical properties of BTO films have been investigated. The results indicate that the BTO films are single perovskite phase having tetragonal symmetry. The band gap of the BTO films increases with the increasing of layer number and decreasing of solution concentration. The transmittance and band gap of the BTO films annealed at 900 °C is more than that of the BTO films annealed at 700 °C when wavelength is 200-1000 nm. When wavelength is 400-1000 nm, the absorption coefficient α obtained by experiment is higher than that obtained by calculation (close to zero).     

Influence of zirconium doping on structure,microstructure, dielectric and impedance properties of strontium bismuth niobate ceramics

Efforts have been made in this work to enhance the dielectric properties of SrBi₂Nb₂O₉ (SBN) by partial substitution of Zr⁴⁺ for Nb⁵⁺. Systematic investigations on structure, microstructure, dielectric and impedance properties of the SrBi₂(Nb_2−(4/5)xZr_x)O₉ [where, x = 0, 0.1 and 0.2] ceramic samples were carried out to understand the effect of substitution of Zr⁴⁺ for Nb⁵⁺ in SrBi₂Nb₂O₉. The X-ray diffraction (XRD) investigations indicated that the lattice volume of SrBi₂(Nb_{2− (4/5)x}Zr_x)O₉ with x = 0.1 and 0.2 decreases compared to SBN. The SEM investigations revealed an increase in the size of grains and the change on shape of grains to elongated plate shaped structure with the increase of x (x = 0.1 and 0.2) in SrBi₂(Nb_2−(4/5)xZr_x)O₉. Higher Curie temperature and enhanced peak dielectric constant at the Curie temperature were observed for both the SrBi₂(Nb_2−(4/5)xZr_x)O₉ with x = 0.1 and 0.2 ceramic samples compared to SBN. Among the investigated compositions the higher Curie temperature and enhanced peak dielectric constant at the Curie temperature was observed for SrBi₂(Nb_2−(4/5)xZr_x)O₉ with x = 0.1.     

Dielectric properties of barium titanate ceramics modified by SiO2 and by BaO-SiO2

The influence of SiO₂ on the dielectric properties of barium titanate ceramics was investigated. SiO₂ had been doped solely and together with BaO into barium titanate before calcination. X-ray diffraction showed that all the ceramics were of a pure perovskite phase after sintering at 1275 °C for 2 h. For SiO₂-doping, there was about 2.5 °C increase in Curie temperature per molar percentage of doping and the leakage current was obviously increased, especially at low voltages for relatively high doping levels. While for the co-doping of SiO₂ and BaO, there was little change in Curie temperature. The point defects formed through the dopings were proposed responsible for the effects. It was suggested that SiO₂ is important to barium titanate ceramics not only for sintering but also for modifying their properties.     

Uniaxial stress dependence of the dielectric properties of barium titanate single crystals

BaTiO₃ single crystals were grown by the melt-grown method. The effect of uniaxial pressure (0–1700 bar) on the dielectric properties of these crystals has been systematically studied. The external stress showed obvious effects on these properties. An increase in the difference between the Curie T_c and Curie–Weiss T₀ temperatures induced by the applied pressure is observed. This could be ascribed to the inducing of non-ferroelectric cubic islands in the tetragonal phase by the applied compressive stress. On the other hand, the pressure behavior of thermal hysteresis and the ??/?T vs. T plot strongly suggests that the phase transition changes to second-order type with increasing pressure. The Curie–Weiss constant obtained from a modified Curie–Weiss law strongly decreases with increasing pressure, suggesting that the mechanism of phase transition is going to order–disorder type. An increase in the difference between the Curie T_c and Burn's T_B temperatures with increasing pressure is observed. This could be ascribed to the narrowing of the temperature range on which the Curie–Weiss law is valid. In general, the obtained results are in good agreement with hydrostatic pressure data. Some kind of relaxation near T_c, which is strongly coupled with strain caused by applied compressive stress, is postulated.     

Effect of Nb-doping on phase transitions and selected properties of (Ba0.90Pb0.10)TiO3 ceramics

Dielectric, pyroelectric characteristics as well as the changes of electric conductivity were investigated for Nb₂O₅-doped (Ba_0.90Pb_0.10)TiO₃ ceramics. The influence of this dopant on the ceramic microstructure and the lattice parameters were also studied. The analysis of the results of electric conductivity and Seebeck coefficient has led to the conclusion that Nb⁵⁺ ions reducing the conductivity by about two orders play the role of donors. The correlation between investigated electric characteristics and the dopant concentration was confirmed. Due to these findings some progress in understanding the influence of Nb-dopant was achieved.     

Enhanced dielectric properties of lead barium zirconate thin films by manganese doping

(Pb_0.5Ba_0.5)ZrO₃ (PBZ) and 1 mol% Mn-doped (Pb_0.5Ba_0.5)ZrO₃ (Mn-PBZ) sol were successfully fabricated, and corresponding thin films were deposited on Pt(1 1 1)/TiO₂/SiO₂/Si(1 0 0) substrates by spin-coating method. Effects of Mn doping on the microstructure and electrical properties of PBZ thin films were investigated systemically. X-ray diffraction patterns showed that both films had a polycrystalline perovskite structure, and that the degree of (1 1 1) orientation were increased by Mn doping. Dielectric measurements illustrated that Mn-doped PBZ thin films not only had a larger dielectric constant, but also possessed a smaller dielectric loss. Accordingly, the tunability and the figure of merit of PBZ films were improved by Mn doping.     

Optimized growth and dielectric properties of barium titanate thin films on polycrystalline Ni foils

Barium titanate(BTO) thin films were deposited on polycrystalline Ni foils by using the polymer assisted deposition(PAD) technique.The growth conditions including ambient and annealing temperatures were carefully optimized based on thermal dynamic analysis to control the oxidation processing and interdiffusion.Crystal structures,surface morphologies,and dielectric performance were examined and compared for BTO thin films annealed under different temperatures.Correlations between the fabrication conditions,microstructures,and dielectric properties were discussed.BTO thin films fabricated under the optimized conditions show good crystalline structure and promising dielectric properties with εr～ 400 and tan δ < 0.025 at 100 kHz.The data demonstrate that BTO films grown on polycrystalline Ni substrates by PAD are promising in device applications.     

Low-temperature sintering and microwave dielectric properties of Ca2Zn4Ti15O36 ceramics

The sintering behavior, microstructures, and microwave dielectric properties of Ca₂Zn₄Ti₁₅O₃₆ ceramics with B₂O₃ addition were investigated. The crystalline phases and microstructures of Ca₂Zn₄Ti₁₅O₃₆ ceramics with 0-10 wt% B₂O₃ addition were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS). The sintering temperature of Ca₂Zn₄Ti₁₅O₃₆ ceramic was lowered from 1170 to 930 °C by 10 wt% B₂O₃ addition. Ca₂Zn₄Ti₁₅O₃₆ ceramics with 8 wt% B₂O₃ addition sintered at 990 °C for 2 h exhibited good microwave dielectric properties, i.e., a quality factor (Qf) 11,400 GHz, a relative dielectric constant (ε_r) 41.5, and a temperature coefficient of resonant frequency (τ_f) 94.4 ppm/°C.     

High-temperature dielectric properties of Gd2CuO4 ceramics

A sample of Gd₂CuO₄ (GCO) has been prepared through the solid state reaction technique. Dielectric properties of this material have been measured in detail as functions of temperature (between 285 and 450 K) and frequency (20 Hz-10 MHz). A step-like increase below 330 K and a broad peak around 360 K were observed in the real part of the permittivity (ε′) which were found to be originated from the oxygen vacancy hopping motions that cause a dipolar relaxation, followed by a Maxwell-Wagner relaxation as the hopping carriers are blocked by the interfaces and surfaces of the sample.     

Effect of sintering temperature on structure and nonlinear dielectric properties of Ba0.6Sr0.4TiO3 ceramics prepared by the citrate method

Ba_0.6Sr_0.4TiO₃ ceramics were prepared by a citrate precursor method. The structure and nonlinear dielectric properties of the resulting ceramics were investigated within the sintering temperature range 1200-1300 °C. Adopting fine Ba_0.6Sr_0.4TiO₃ powder derived from the citrate method was confirmed to be effective in reducing the sintering temperatures required for densification. The ceramic specimens sintered at 1230-1280 °C presented relative densities of around 95%. A significant influence of sintering temperature on the microstructure and nonlinear dielectric properties was detected. The discrepancy in nonlinear dielectric behavior among the specimens sintered at different temperatures was qualitatively interpreted in terms of the dielectric response of polar micro-regions under bias electric field. The specimens sintered at 1230 and 1250 °C attained superior nonlinear dielectric properties, showing relatively low dielectric losses (tan δ) of 0.24% and 0.22% at 10 kHz together with comparatively large figure of merits (FOM) of 121 and 142 at 10 kHz and 20 kV/cm, respectively.