Ferroelectric and optical properties of Ba5Li2Ti2Nb8O30 ceramics potential for memory applications

Giant grained (42 μm) translucent Ba₅Li₂Ti₂Nb₈O₃₀ ceramic was fabricated by conventional sintering technique using the powders obtained via solid state reaction route. These samples were confirmed to possess tetragonal tungsten bronze structure (P4bm) at room temperature. The scanning electron microscopy established the average grain size to be close to 20 μm. The photoluminescence studies carried out on these ceramics indicated sharp emission bands around 433 and 578 nm at an excitation wavelength of 350 nm which were attributed to band-edge emission as the band gap was 2.76 eV determined by Kubelka–Munk function. The dielectric properties of these ceramics were studied over wide frequency range (100–1 MHz) at room temperature. The decrease in dielectric constant with frequency could be explained on the basis of Koops theory. The dielectric constant and the loss were found to decrease with increasing frequency. The Curie temperature was confirmed to be ~370 °C based on the dielectric anomaly observed when these measurements were carried out over a temperature range of 30–500 °C. This shows a deviation from Curie–Weiss behaviour and hence an indicator of the occurrence of disordering in the system, the γ = 1.23 which confirms the diffuse ferroelectric transition. These ceramics at room temperature exhibited P–E hysteresis loops, though not well saturated akin to that of their single crystalline counterparts. These are the suitable properties for ferroelectric random access memory applications.     

Effect of sintering temperature on the microstructure and electrical properties of zirconium doped barium titanate ceramics

Lead-free Ba(Zr_0.15Ti_0.85)O₃ (BZT15) ceramics were synthesized by adopting the solid-state synthesis method. The effect of increasing sintering temperature (T_s) in the range of 1,350–1,450 °C on the microstructure, dielectric, polarization, and electric field induced strain of the ceramics was studied. Fine grained (~260 nm) BZT15 ceramics displayed single phase perovskite structure with relative densities >94 % of the theoretical density. Both grain size and shape were influenced by the sintering parameters. With increase in T_s, not only the maximum dielectric constant decreased from 11,412 to 8,734 along with an increase in the degree of diffuseness, but also interestingly the Curie temperatures were found to vary within an interval of 61–73 °C. Optimum sintering temperature has been found resulting in high remnant polarisation and strain in these ceramics. The properties observed are attributed to a contribution from all polar vectors present in coexistent phases.     

Enhanced dielectric and electrical properties in CaZrO3-doped X8R BaTiO3-based ceramics sintered at medium temperature

Lead-free X8R BaTiO₃-based ceramics were prepared by conventional solid-state method. The influence of the composition and procedures on the microstructures, lattice parameters and dielectric properties of ceramics materials were systemically studied. XRD results indicate that no secondary phase is formed in the CaZrO₃-doped samples after sintering. The content of Ca²⁺ ions and Zr⁴⁺ ions decrease from grain boundaries to grain interiors referring to EDS results, which indicate that the ions mainly locate in the grain boundaries. The Curie temperatures of all CaZrO₃ doped samples increase due to the increasing tetragonality caused by the addition of CaZrO₃. SEM micrographs reveal that the grain size of CaZrO₃-doped BaTiO₃-based samples are not uniform, ranging from 0.2 to 0.8 µm. Furthermore, samples doped with 1.0 wt % CaZrO₃ exhibit optimal dielectric properties with high temperature stability of capacitance, due to the fine-grain microstructures. Moreover, we obtained a lead-free high performance X8R dielectric ceramic composition sintered at medium temperature (1,135 °C).     

Study on low temperature sintering and electrical properties of CuO-doped Ca0.28Ba0.72Nb2O6 ceramics

Ca_0.28Ba_0.72Nb₂O₆ (CBN28) ceramics with different content of CuO were prepared by the conventional ceramic fabrication technique. The effects of CuO content on the phase structure, microstructure, dielectric and ferroelectric properties of obtained CBN28 ceramics were investigated. XRD results showed that pure tungsten bronze structure was obtained in all ceramics and CuO additive could accelerate the phase formation at lower temperatures. The CuO aid was effective for the uniform grain size in CBN28 ceramics, as it could facilitate the sintering behavior and suppress the anisotropic growth behavior obviously. The dielectric and ferroelectric properties of CBN28 ceramics depended greatly on the CuO content. Curie temperature T _c and dielectric loss tanδ both shifted downward, whereas the maximum dielectric constant ε _m and the dielectric constant around room temperature ε _r all increased initially and then decreased as x increased from 0.1 to 0.4 wt%. Normal ferroelectric hysteresis loops could be observed in all compositions, and the remnant polarization P _r decreased gradually. It was found that the comprehensive electric performance was optimized in CBN28-0.2 wt% CuO ceramics: ε _r = 453, ε _m = 3,371, T _c = 226 °C, tanδ = 0.048, P _r = 4.72 μC/cm² and E _c = 13.81 kV/cm, showed that CuO sintering aid could not only ameliorate the sintering behavior but also improve the electrical properties.     

Raman and electrical studies of multiferroic BiFeO3

Monophasic rhombohedral structure of BiFeO₃ electroceramic is successfully synthesized by conventional solid state reaction route followed by slow step sintering schedule. Effect of sintering temperature is found to greatly influence its structural, dielectric, ferroelectric, capacitance and leakage behavior of bulk ceramic. From XRD analysis it is seen that at lower sintering temperature (750 °C) bulk BiFeO₃ sample showed rhombohedral structure (R3c) along with few impurity phases, which become suppressed at higher sintering temperature and facilitates the compactness of grains and formation of dense microstructure. The leakage current and capacitive characteristic of the sample was improved significantly with increase in sintering temperature of BiFeO₃ (850 °C). At higher sintering temperature, ferroelectric behavior of the sample is found to change its shape from semi elliptical lossy P–E features to a typical ferroelectric loop with improvement of its remnant as well as saturation polarization value. Raman spectra over the frequency range of 100–700 cm^?1 have been systematically investigated. Besides the changes of the peak position and the line width of all modes, the prominent frequency shift, the line broadening and variation of the intensity were observed with increase in sintering temperature.     

Dielectric properties of CaCu3Ti4O12 ceramics: effect of high purity nanometric powders

The dielectric properties of CaCu₃Ti₄O₁₂ ceramics fabricated with nano-size fine powders (~30 nm) are compared with that fabricated with micro-size coarse powders (0.1–0.3 μm). For the same sintering conditions, the ceramic samples with nano-size fine powders have more uniform and denser microstructures and higher room temperature dielectric constant (~10⁵, in the frequency range of 10^?1–10⁵ Hz) than that with micro-size coarse powders. That the use of nano powders facilitates the formation of Cu-rich amorphous phase in the grain boundary led to an increasing dielectric loss in low frequency range. Besides the common intrinsic defect structure of V _O ⁺ and V _O ⁺⁺ , the energy level of ~0.72 eV detected in high temperature range is attributed to the conduction relaxations, and the energy level of 0.30–0.40 eV which is only detected in the sample synthesized by common submicron powders is suggested to originate from the defect level of grain boundary related to Cu ions. This research provides a technical guidance for the application of this material.     

Microstructure,ferroelectric, piezoelectric and ferromagnetic properties of BiFeO3–BaTiO3–Bi(Zn0.5Ti0.5)O3 lead-free multiferroic ceramics

Multiferroic ceramics of (0.70?x)BiFeO₃–0.30BaTiO₃–xBi(Zn_0.5Ti_0.5)O₃ + 1 mol% MnO₂ with perovskite structure were prepared by a conventional ceramic technique and the effects of Bi(Zn_0.5Ti_0.5)O₃ doping and sintering temperature on the microstructure, multiferroic and piezoelectric properties of the ceramics were studied. All the ceramics possess a pure perovskite structure and no second phases can be detected. After the addition of a small amount of Bi(Zn_0.5Ti_0.5)O₃ (x ≤ 0.05), the ferroelectric and piezoelectric properties of the ceramics are improved and the grain growth is promoted. However, excess Bi(Zn_0.5Ti_0.5)O₃ (x ≥ 0.10) retards the grain growth, degrades the ferroelectricity and piezoelectricity, and induces two dielectric anomalies at high temperature. The ceramics can be well sintered at the very wide range of low sintering temperatures (880–980 °C) and exhibit good densification (relative density: 96.2–98.4 %) and strong electric insulation. The increase in the sintering temperature promotes the grain growth and improves the ferroelectricity of the ceramics. The ceramic with x = 0.05 sintered at 880–980 °C possesses improved ferroelectric and piezoelectric properties with remanent polarizations P _r of 21.9–28.1 μm/cm², piezoelectric constants d ₃₃ of 125–139 pC/N and planar electromechanical coupling factors k _p of 30.1–32.4 %, and high Curie temperatures T _C of 523–565 °C. A weak ferromagnetism with remanent magnetizations M _r of 0.0411–0.0422 emu/g and coercive fields H _c of 1.70–1.99 kOe were observed in the ceramics with x = 0–0.025.     

Grain size effects on the dielectric properties of ferroelectric Bi2VO5.5 ceramics

Dielectric properties and microstructural characteristics of ferroelectric bismuth vanadate (Bi₂VO_5.5) ceramics exhibiting grain sizes of 7, 10, 20 and 25 m have been studied. Microstructural studies indicate the presence of ferroelectric 90° domain patterns on the surface as well as in the bulk of the coarse-grained ceramics. The dielectric constant and the loss tangent both at room temperature and in the vicinity of the Curie temperature have been found to increase with increasing grain size. The Curie temperature (725 K) is found to shift slightly (by about 7 K) towards higher temperatures as the grain size increases (7–25 m). The magnitude of the dielectric anomaly around 725 K is found to be higher for coarse-grained ceramics. The dielectric constant and the loss have been found to decrease with increase in frequency (1–100 kHz) for all the ceramics studied. The increase in dielectric constant with increasing grain size is attributed to a decrease in thickness of the relatively more insulating grain boundary layer.     

The electrostrictive effect and dielectric properties of lead-free 0.5Ba(ZrxTi1−x)O3–0.5(Ba0.75Ca0.25)TiO3 ceramics

Lead-free 0.5Ba(Zr_xTi_1?x)O₃–0.5(Ba_0.75Ca_0.25)TiO₃ (x = 0.25, 0.30, 0.35, 0.40) ceramics have been synthesized by a conventional solid state sintering method. The room temperature ferroelectric and electrostrictive properties of these ceramics were studied. Based on the measured properties, these ceramics showed a typical relaxor behavior. The Curie temperature of BZT–BCT ceramics decreases with increasing the Zr content. The largest electrostrictive strain and electrostrictive coefficient are founded in BZT–BCT ceramic with x = 0.25, the value is 0.16 % and 0.079 m⁴ C^?2, respectively. The polarization, electrostrictive strain and electrostrictive coefficient (Q ₁₁) decrease with increase in Zr concentration. For samples with low Curie temperature, which have large room temperature dielectric constant (ε), electrostrictive coefficient increases (Q ₁₁) is smaller. Because doping can disrupt the long range cation order, and electrostrictive (Q ₁₁) coefficient increases with cation order from disordered, through partially-ordered, simple relaxor and then ordered perovskites, ferroelectrics with a disordered structure have a huge permittivity, but a small electrostrictive coefficient (Q ₁₁).     

Structure, dielectric, ferroelectric, and energy density properties of (1 − x)BZT–xBCT ceramic capacitors for energy storage applications

We investigate the dielectric, ferroelectric, and energy density properties of Pb-free (1 ? x)BZT–xBCT ceramic capacitors at higher sintering temperature (1600 °C). A significant increase in the dielectric constant, with relatively low loss was observed for the investigated {Ba(Zr_0.2Ti_0.8)O₃}_(1?x ){(Ba_0.7Ca_0.3)TiO₃} _x (x = 0.10, 0.15, 0.20) ceramics; however, electric breakdown was low (~140, 170, 134 kV/cm), and of which room temperature (300 K) charging curve energy density values are largest ~0.88, 0.94, and 0.87 J/cm³ with maximum high dielectric constant values ~7800, 8400, and 5200, respectively. Bulk ceramic BZT–BCT materials have shown interesting energy densities with good energy storage efficiency (~72 %) at high sintering temperature; they might be one of the strong candidates for high energy density capacitor applications in an environmentally protective atmosphere.     

Effects of glass additions on the dielectric properties and energy storage performance of Pb0.97La0.02(Zr0.56Sn0.35Ti0.09)O3 antiferroelectric ceramics

In this work, CdO–Bi₂O₃–PbO–ZnO–Al₂O₃–B₂O₃–SiO₂ low softening point glass powders were prepared and employed as sintering aid to improve the dielectric breakdown strength and reduce the sintering temperature of Pb_0.97La_0.02(Zr_0.56Sn_0.35Ti_0.09)O₃ antiferroelectric ceramics. The effects of glass content and sintering temperature on the densification, microstructure, dielectric properties and energy storage performance of Pb_0.97La_0.02(Zr_0.56Sn_0.35Ti_0.09)O₃ antiferroelectric ceramics have been investigated. With inclusion of glass, sintered densities comparable to those obtained by conventional sintering are achieved at only 1,050 °C. The breakdown strength of glass-added samples was notably improved due to the reduction of the grain size. The antiferroelectric to ferroelectric switching field and the ferroelectric to antiferroelectric field both increased with increasing glass content. The dielectric constant and dielectric loss decreased gradually with increasing glass content. As a result, the highest recoverable energy density of 3.3 J/cm³ with an energy efficiency of 80 % was achieved in 4 wt% glass-added sample sintered at 1,130 °C.     

Effect of vanadium doping on the electric properties of barium titanate hafnate ceramics

Pure and V-doped barium titanate hafnate (BaHf_0.1Ti_0.9O₃, short for BHT) ceramics were prepared by sol–gel method. The microstructures, dielectric and ferroelectric properties of BaHf_0.1V _x Ti_0.9?x O₃ (x = 0, 0.02, 0.05, 0.08, 0.1) ceramics have been investigated. From the X-ray patterns it implies that V⁵⁺ ions have entered the unit cell maintaining the perovskite structure of solid solution. The a-axis and c-axis lattice constants gradually increase and the tetragonality gradually decreases with the increasing of vanadium content. The content of vanadium has an inconspicuous effect on the grain size and the Curie temperature. The addition of vanadium can decrease the dielectric loss of BHT ceramics. It is found that well-behaved hysteresis loops can be observed in all samples at room temperature. The coercive electric field gradually decreases and then increases with the increasing of vanadium content.     

Size effect on magnetic and dielectric properties in nanocrystalline LaFeO3

Nanocystalline LaFeO₃ powders with different grain sizes (30–150 nm) have been synthesized by a polymerized complex method to investigate their magnetic and dielectric properties. Thermogravimetric–differential thermal analysis curves of the precursory powders reveal the thermal decomposition and crystallization temperature should be at above 650 °C. The precursory powders were sintered at temperatures of 650, 700, 800, and 900 °C for 2 h. X-ray diffraction identify that all the samples are phase-pure. Weak ferromagnetic behaviors and finite exchange bias (EB) effects were observed for all the samples at room temperature, and both M_r and H_EB decreases monotonically with the increase of grain size. For 30 nm sample, the remnant magnetization and the EB field are 0.086 emu/g and 310 Oe, respectively. On the other hand, the dielectric constants decrease with the decreasing of grain size. Among all the samples, 150 nm samples show the largest dielectric constant about 6 × 10³.     

Effect of synthesized BaTiO3 doping on the dielectric properties of ultra temperature-stable ceramics

The high performance X9R ceramics could be sintered at as low as 1,120?°C by doping 3?mol% synthesized BaTiO₃ (SB) additives into the BaTiO₃-based ceramics, with a dielectric constant greater than 2,200 at 25?°C and dielectric loss lower than 1.7?%. The effects of SB additives on the microstructure and dielectric properties of BaTiO₃-based ceramics were investigated. The dielectric constant of BaTiO₃-based ceramics doped with 3?mol% SB was increased due to the promotion of the densification of ceramics. With SB content up to 4.5?mol%, Ti⁴⁺’s polarization was depressed, which resulted in the decrease of augmented dielectric constant at 25?°C. The partial solid solution was formed between Pb(Ti, Sn)O₃ and BaTiO₃, and the substitutions of Pb at A-sites and Sn at B-sites were existed. The strengthen of Ti–O bonds and higher Curie point of Pb(Ti_0.55Sn_0.45)O₃ was helpful to increased the Curie point of the ceramics effectively. Doped with SB additives, the volume of ferroelectric core was increased, and the sharp peak intensity at Curie point was increased accordingly. Capacitance temperature characteristics was improved attributed to the mutual effects of SB and Pb(Ti_0.55Sn_0.45)O₃. The formation of core–shell structure was sensitive to the sintering temperature, so the dielectric properties of ceramics were highly depended on the sintering temperature.     

Low-temperature sintering and piezoelectric properties of Pb(Fe2/3W1/3)O3–added Pb(Zn1/3Nb2/3)O3–Pb(Ni1/3Nb2/3)O3–Pb(Zr,Ti)O3 ceramics

Low-temperature sintering of (a–x)Pb(Zr_0.48Ti_0.52)O₃–bPb(Ni_1/3Nb_2/3) O₃–cPb(Zn_1/3Nb_2/3)O₃–xPb(Fe_2/3W_1/3)O₃ (a + b + c + x = 1, 0.06 ≤ x ≤ 0.10) ceramics were prepared through two-step synthesis process using perovskites-structured ferroelectric materials Pb(Fe_2/3W_1/3)O₃ (PFW) as a sintering aid. The effects of PFW content on the densification, microstructure, phase structure, dielectric and piezoelectric properties of the ceramics were investigated. The sintering temperature was reduced from 1,180 °C (without PFW addition) to 940 °C when the material was PFW-doped. PFW-doping increased the sintered density and the average grain size of PFW–PNN–PZN–lead zirconate titanate ceramics. The ceramics sintered at 940 °C for 4 h with x = 0.08 exhibited favorable properties, which were listed as follows: d₃₃ = 496pC/N, εT 33/ε₀ = 3,119, tanδ = 2.1 % and Curie temperature = 242 °C. These values indicated that the newly developed composition might be suitable for multilayer piezoelectric devices application.     

Effect of piezoelectric grain size on magnetoelectric coefficient of Pb(Zr0.52Ti0.48)O3–Ni0.8Zn0.2Fe2O4 particulate composites

This study investigates the variation of magnetoelectric (ME) coefficient as a function of the piezoelectric grain size in the composite system of 0.8 Pb(Zr_0.52Ti_0.48)O₃–0.2 Ni_0.8Zn_0.2Fe₂O₄. It was found that as the piezoelectric-phase grain size increases the overall resistivity, piezoelectric, dielectric, and ferroelectric property of the composite increases and saturates above 600 nm. Below 200 nm average grain size, piezoelectric and dielectric properties decrease rapidly. The ferroelectric Curie temperature was found to decrease from 377 to 356 °C as the average grain size decreases from 830 to 111 nm. ME coefficient of the composite showed a rapid change below grain size of 200 nm and was found to saturate above 600 nm to a value of 155 mV/cm.Oe.     

Effects of BaNb2O6 addition on microstructure and dielectric properties of BaTiO3 ceramics

(1 ? x)BaTiO₃–xBaNb₂O₆ [(1 ? x)BT–xBN] ceramics with x = 0, 0.005, 0.008, 0.01, 0.02, 0.03 were prepared by a conventional solid-state reaction route. The effect of BN addition on phase composition, microstructure and dielectric properties of BT-based ceramics were investigated by X-ray diffraction, scanning electron microscope and impedance spectroscopy. The results showed that a systematic structure change from the ferroelectric tetragonal phase to pseudo-cubic phase was observed near x = 0.01 at room temperature. It resulted in a considerable change of density, grain size and dielectric properties of the samples when BN was introduced. Meanwhile, it also lowered the sintering temperature of the ceramics. The dielectric constant peak and the variation rate of capacitance at Curie temperature are markedly depressed and broaden with increasing BN content. Especially, the ceramics with x = 0.008 and x = 0.01 showed good dielectric properties over the measured temperature range. Optimal dielectric properties of ε = 3,851, tanδ = 0.7 % at room temperature and Δε/ε₂₅ ≤ ±6.8 % (?55 to 125 °C) were obtained for the BT-based ceramics doped with 0.8 mol% BN, which was obviously superior to BaTiO₃ and BaNb₂O₆ ceramic, and it met the requirements of EIA X7R specifications.     

Preparation of lead magnesium niobate by a coprecipitation method

The ferroelectric complex perovskite lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), was prepared by a coprecipitation method. As the niobium component, niobium oxalate was used. Among the various precipitants, tetramethylammonium hydroxide was effective for the formation of single-phase PMN without pyrochlore phase. The dielectric constant and the dissipation factor of PMN changed either the sintering temperature or the grain size. The maximum dielectric constant at the Curie point was obtained by sintering at 1220 °C in air for 2 h.     

Phase evolutions and electric properties of BaTiO3 ceramics by a low-temperature sintering process

BaTiO₃ (BT) nanoparticles were synthesized by a modified polymeric precursor method in a weak acid solution. The synthesized process of BT precursor with increasing calcination temperature was investigated through thermal analysis (DTA/TG), X-ray diffraction, transmission electron microscope and Fourier-transform infrared spectroscopy. Good dispersive and homogeneous cubic BT nanoparticles were calcined at 800 °C, whereas dense BT ceramics were sintered at ~1,160 °C. The present results showed that the dielectric, piezoelectric and ferroelectric properties of BT ceramics were dependent on the ceramics densification and crystallographic structure. The excellent electric properties (P _r = 10.5 μC/cm², d ₃₃ = 217 pC/N, k _p = 0.32 %) were found at a sintering temperature of 1,160 °C, which was due to the coexistence of tetragonal and orthorhombic phase. The depressed electric properties at higher sintering temperature were associated to oxygen vacancies and impurity phases. In addition, phase evolutions of BT nanoparticles and ceramics were all stated in detail.     

Giant dielectric properties of nanocrystalline Pb1−xSnxF2 solid solutions

Nanocrystalline Pb_1?xSn_xF₂ (x = 0.2, 0.3) solid solutions have been synthesized by mechanochemical milling at room temperature with grain size as small as 26 nm. These fluoride ion conducting materials exhibit giant values of the dielectric constant of ?′ > 10⁵ that is independent of temperature and frequency over wide ranges. The giant values of ?′ are suggested to be due to internal effects in the materials. The dielectric response has been analyzed by appropriate equivalent circuit representing the grain and internal effects in the materials. Interestingly, the dielectric constant of the current samples is found to be larger for the samples with smaller grain size, a behavior that is quite opposite to what usually observed in giant dielectric oxide materials, where ?′ is enhanced with substantial growth of the grain size. The possible origin of the giant dielectric constant is discussed in the present study.