On the structural and electrical properties of modified PbTiO3 ceramics

Ceramics (Pb_0·75Ca_0·25)[(Ni_1/2W_1/2) _y Ti_1−y ]O₃ fory = 0 ·05, 0·10, 0·15 and 0·30 have been prepared using high temperature solid state reaction method. X-ray analyses show that these materials are of single-phase perovskite type tetragonal structure. To solve inaccuracy in finding para-ferroelectric phase transition temperatureT _c(ε _max), we have carried out the analyses of the data using a computer program. The role of Ni and W as modifiers on structural and electrical (dielectric and pyroelectric) properties is discussed in terms of the usefulness of these materials. Results indicate that ceramic Pb_0·75Ca_0·25Ni_0·25W_0·025Ti_0·95O₃ is a good candidate for pyroelectric applications. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995     

Transitions of barium strontium titanate ferroelectric ceramics for different strontium content

Ceramic based barium strontium titanate (BST) solid solutions with the formula Ba_1 − xSr_xTiO₃ are very important candidates for a wide range of device applications. Several doped (Mn and Mg) and undoped samples were prepared by standard solid-state reaction. Special emphasis was put on compositions with x = 0.35 and 0.60, with high potential for applications. The samples were sintered at temperatures in the 1200 ÷ 1260 °C range. Structural X-ray diffraction analysis preformed confirms the perovskite structure. The dielectric parameters were investigated in a wide temperature range between − 150 and 150 °C. The temperature was cyclically changed in both directions, up and down, at a rate of less than 2 °C/min. Both permittivity and dielectric loss were measured at low frequencies, 1 kHz. The peak values of the permittivity are increasing from 2000 to 4000 with the sintering temperature increase. Moreover the dielectric parameters were measured at room temperature in microwave domain (1 ÷ 2 GHz). The Curie temperature of BST samples with x = 0.35 and x = 0.6 is in agreement with the Curie point dependence on Sr content, as we have previously reported.     

Preparation and optical characterization of lanthanum modified lead zirconate titanate thin films on indium-doped tin oxide-coated glass substrate

Lanthanum modified lead zirconate titanate (PLZT) thin films were fabricated on indium-doped tin oxide (ITO)-coated glass substrate by sol-gel method. The structure of the films was characterized with X-ray diffraction and scanning electron microscopy. The optical properties were investigated in the wavelength range of 220-2400 nm. The sample was modelled as a three layer structure on finite substrate, and optical constants of this system were calculated from the transmission and reflection spectra. The calculated dielectric function was fitted with the Drude model in the case of ITO and a sum of Lorentzian oscillators in the case of PLZT films. For PLZT film the anomalous behaviour of imaginary part of dielectric function was observed below the absorption edge. The possible reasons of that behaviour were discussed.     

Synthesis and dielectric characterization of Ba0.6Sr0.4TiO3 ferroelectric ceramics

Ferroelectric ceramics Ba_0.6Sr_0.4TiO₃ (BST 40) were prepared, by solid-state reaction in the temperature range 1210-1450 °C. Maximum values of the ceramic densities were around 94% of their theoretical value. X-ray diffraction techniques (XRD) and scanning electron spectroscopy (SEM) were used to analyze the structure and the surface morphology of ceramics. Rounded, well defined or abnormal granular growth was observed in the SEM images, vs. sintering conditions and purity of the raw materials. In all samples, BST 40 ceramic is the major phase, but there are also present small amounts of secondary phases, as revealed in XRD diffraction patterns. Permittivity and dielectric loss measurements were performed in the temperature range − 150 to + 150 °C, and 150 Hz-5 MHz frequency values. Permittivity values rising from 1200 to 12,500, with increasing sintering temperatures, were recorded. Narrow and well defined transition peaks were noticed at higher sintering temperatures. Curie temperature was around 2 °C, for samples with the mentioned composition. Permittivity and losses vs. frequency show different behavior whether BST ceramics are in polar or non-polar state and with the distance toward phase transition. Microwave measurements performed at room temperature have shown lower values of permittivity, compared with similar data at low frequency, and dielectric losses lower than 1% at 0.7 GHz. The sintering conditions (temperatures, sintering time, etc.) and purity of the raw materials lead to important changes of transition temperatures in the polymorphic diagram, which we have built—for the other Ba1−xSrxTiO3 compositions (x = 0.25-0.90) sintered at 1260 °C for 2 h.     

On the fracture toughness anisotropy of mechanically poled ferroelectric ceramics

In this paper an incremental constitutive theory for the deformation due to switching in ferroelectrics is applied to predict the fracture toughness anisotropy in these materials after mechanical poling. Mechanical poling of an initially unpoled specimen differs from electrical poling in that only mechanical stresses are applied to the material. Therefore, no electrical polarization can develop. After mechanical poling, for example by a uniaxial applied stress, the fracture toughness of a ferroelectric ceramic for cracks running parallel or orthogonal to the poling direction will differ. Finite element computations of the steady crack growth process have been carried out to quantify these differences. Results are generated for a range of constitutive properties for three crack growth directions with respect to the initial mechanical poling direction. The results are discussed in relation to available experimental data and to the toughness anisotropy due to electrical poling.     

Magnetic, ferroelectric and magnetoelectric coupling properties of Fe-implanted BaTiO3 films

BaTiO₃ (BTO) nano-films were implanted with iron by means of ion-implantation. According to the results of X-ray diffraction (XRD) and Raman analysis, all the films are single-phase with tetragonal structure. Upon the increase of Fe dosage, on one hand, there is a decrease in c/a ratio of the unit cells. As the grain size and surface roughness of the Fe-implanted films decrease, the well crystallized film was obtained. Consequently, both decreasing of coercivity and boosting of magnetization were observed simultaneously. With the decline of the grain size and surface roughness during thermal treatment of the Fe-implanted films, there is an improvement of Fe distribution across the BTO matrix. Consequently, there is a decrease of coercivity and rise of magnetization. Upon the decrease of Fe dosage, on the other, there is a decline in magnetization, and a ferroelectric hysteresis loop is observed at a Fe dosage of 3.0 × 10¹⁴ cm^− 2. Additionally, the dependence of capacitance on the applied magnetic field and its frequency were also monitored.     

Enhancement of ferroelectric and piezoelectric characteristics in europium substituted SrBi2Ta2O9 ferroelectric ceramics

Europium substituted samples of compositions Sr_1 − xEu_xBi₂Ta₂O₉ were synthesized by solid-state reaction method. The prepared samples were characterized for their structural and electrical properties. X-ray analysis confirms the formation of the single-phase layered perovskite structure. The microstructural studies reveal that the average grain size increases with increase in Eu content. An increase in remanent polarization and d₃₃ values with increasing concentration of europium has been observed. The maximum 2P_r ~ 14 μC/cm² is observed in the sample with x = 0.20. The observed results have been discussed in terms of contribution from the cation vacancies introduced into the lattice structure due to donor doping.     

Temperature-dependent ferroelectric hysteresis properties of modified lead zirconate titanate ceramics

Temperature-dependent ferroelectric hysteresis properties of modified lead zirconate titanate ceramics have been investigated in a wide temperature range from 300 to 433 K. It is observed that remnant polarization, saturation polarization, and coercive field are increasing with an increase of the temperature in a low-field region and decreasing in a high-field region. Such behavior is explained by the competition between switching and backswitching mechanisms. A three-stage dependence of the logarithm of the hysteresis loop area on the logarithm of the electric field is identified. The temperature dependence of backswitching properties has been studied. The obtained results indicate that the temperature dependence of the polarization backswitching can be well described by the Arrhenius law. The activation energy for the domain switching determined from the fitting results exhibits decreasing tendency with the increase of the electric field.     

Ferroelectric, dielectric and piezoelectric properties of potassium lanthanum bismuth titanate K0.5La0.5Bi4Ti4O15 ceramics

The Aurivillius type bismuth layer-structured compound potassium lanthanum bismuth titanate (K_0.5La_0.5Bi₄Ti₄O₁₅) is synthesized using conventional solid-state processing. The phase analysis is performed by X-ray diffraction (XRD) and the microstructural morphology is conducted by scanning electron microscopy (SEM). The ferroelectric, dielectric and piezoelectric properties of K_0.5La_0.5Bi₄Ti₄O₁₅ (KLBT) ceramics are investigated in detail. The remnant polarization (P_r) and coercive field (E_c) are found to be 8.6 μC cm⁻² and 60 kV cm⁻¹, respectively. The Curie temperature T_c and piezoelectric coefficient d₃₃ are 413 °C and 18 pC N⁻¹, respectively.     

Developments in ferroelectric ceramics for capacitor applications

A brief overview of the materials and processes for making ceramic capacitors based on BaTiO₃ and relaxor ferroelectric compositions is presented with special emphasis on more recent developments.     

Abnormal C–V curve and clockwise hysteresis loop in ferroelectric barium stannate titanate ceramics

Reversible hysteresis loop, defined as integral of small signal dielectric constant with electrical field, represents the contribution of the reversible part of polarization. In barium stannate titanate ceramics, field dependence of small signal dielectric constant was abnormal. The subsequent mathematical integral showed an abnormal clockwise hysteresis loop in the temperature range of 10–40 °C. The ferroelectric hysteresis loop measured by Sawyer–Tower circuit showed slim-waist or pinched shape. This phenomenon may reveal abnormal domain switching mechanism and is believed to be related with the strong interaction between point defects and domain walls.     

Flexible and lithography-compatible copper foil substrates for ferroelectric thin films

A process has been developed for preparing a low surface roughness copper foil by evaporation and subsequent peel-off of copper metal layers on glass slides. These 15 micron thick substrates exhibited roughness values between 1 and 2 nm root-mean-square (RMS) and 9 nm RMS over 25 μm² and 100 μm² analysis areas, respectively. The deposition and crystallization of barium strontium titanate layers were demonstrated on these smoother variant foils. The fully processed dielectric layers exhibited field tunability greater than 5:1, and could withstand fields in excess of 750 kV/cm. High field loss tangents below 0.007 were observed, making these materials excellent candidates for microwave devices. Finally, a process of lamination and contact lithography was used to demonstrate patterning of micron-scale features suitable for microwave circuit element designs.     

Fracture toughness of alumina/lanthanum titanate laminate composites with a weak interface

Layers of lanthanum titanate (La₂Ti₂O₇) and α-alumina (α-Al₂O₃) were employed to form a layered composite in order to improve the fracture toughness of monolithic alumina. The composites were produced by two different processing methods. In the first, individually presintered pellets of α-Al₂O₃ and La₂Ti₂O₇ were stacked together and hot-forged. In the second, tape cast molten salt La₂Ti₂O₇ and dense α-Al₂O₃ were stacked together and hot-forged. The forged composite samples were investigated by optical microscopy, scanning electron microscopy (SEM), Vickers indentation and three-point bending. During the hot-forging process, an interphase, aluminum titanate (Al₂TiO₅) was found to form as a result of the reaction between α-Al₂O₃ and La₂Ti₂O₇. The flexural strength and the fracture toughness of the resulting laminate composites were found to be 320 MPa and 7.1 MPa m^1 / 2, respectively. Indentation experiments showed that the newly formed Al₂TiO₅ at the interface is sufficiently weak to promote crack deflection and hence increase the fracture energy and mechanical properties of the composite.     

Structural,dielectric and electrical properties of a new tungsten bronze ferroelectric ceramics

The polycrystalline sample of Li₂Pb₂Nd₂W₂Ti₄Ta₄O₃₀ was prepared by a solid-state reaction technique. Room temperature X-ray structural analysis confirms the formation of a single phase compound. The morphology of the sintered sample recorded by scanning electron microscope exhibits a uniform grain distribution. Detailed studies of the nature of variation of dielectric constant, tangent loss and polarization with temperature and frequency confirmed the existence of ferroelectricity in the material. The temperature and frequency dependence of impedance parameters (impedance, modulus, etc.) of the material exhibits a strong correlation of its micro-structure (i.e., bulk, grain boundary, etc.). The nature of variation of pyroelectric-coefficient and current with temperature suggests that material has good pyroelectric properties useful for pyroelectric detector.     

Preparation of polycrystalline BaTi2O5 ferroelectric ceramics

Polycrystalline BaTi₂O₅ (BT₂) was prepared by solid state sintering in air using BaCO₃ and TiO₂ as starting materials. A rod-like BT₂ sintered bodies in a single phase were obtained above 1025 °C by adding 5 wt.% B₂O₃. The densification of BT₂ sintered bodies decreased with increasing sintering temperature. The maximum permittivity of BT₂ sintered body was 640 at the Curie temperature (T_c) of 461 °C and the frequency of 100 kHz. The addition of B₂O₃ was effective to obtain BT₂ in a single phase at low temperatures with elongated microstructure and to improve the permittivity, indicating the formation of preferred orientation at low temperature was related with liquid-phase sintering mechanism.     

Structural and dielectric properties of La-doped lead titanate ceramics

(Pb_1−xLa_x)TiO₃ (PLT) ceramics of perovskite type were prepared by sol-gel process, and their structural and dielectric properties investigated. The obtained compounds crystallize, under heat treatment, at relatively low temperatures and no secondary phases have been observed on the corresponding XRD spectra. Annealing temperature (T_a) and its duration (t_a) appear to influence notably their structural and dielectric characteristics.     

Structural and ferroelectric properties of europium doped lead zirconate titanate thin films by a sol-gel method

Using a sol-gel method, rare earth element europium doped lead zirconate titanate thin films with a pure perovskite structure were obtained. The effects of excess lead and pyrolyzing temperature on the crystalline structure of the thin films were investigated using X-ray diffraction. Their ferroelectric and dielectric properties were determined by P-E loop and impedance measurements. The remnant polarization is 23.5 μC/cm² and the coercive electric field strength is 5.5 kV/mm. The dielectric constant and the dissipation factor is approximately 950 and 0.07, respectively.     

掺杂Y2O3对钛酸锶钡铁电陶瓷材料显微结构和介电性能的影响

钛酸锶钡(BSTO)铁电陶瓷材料的介电常数随外加直流电场的变化呈现非线性特性.纯BSTO材料由于较高的介电常数和较大的介电损耗不能满足移相器介质材料的要求.通过在BSTO中添加Y2O3来改善BSTO铁电陶瓷材料的介电性能.研究结果是:(1)在BSTO体系中微量掺杂Y2O3,Y3 以取代Ba2 的方式存在于钙钛矿的晶格中,形成均匀的固溶体Ba0.5-xYxSr0.5TiO3;(2)随Y3 添加量的增加,居里峰逐渐变宽,峰高逐渐降低,相变弥散效应增强;(3)Y3 的掺杂能促进BSTO陶瓷的致密化烧结,并显著降低BSTO陶瓷的介电常数.     

Electronic ceramics

Electronic ceramics represent an important segment of advanced ceramics and will probably constitute a major share of the advanced ceramic markets at least till 2000 AD. Yet, other than ferrites, this area has not been sufficiently examined in this country. Therefore, this review covers briefly the science and technology status, the markets and the possible future projections of these ceramics the world overvis a vis the Indian situation and indicates the scope for indigenous effort in this vital area of electronic components.     

Electrical and optical properties of chemical solution deposited barium hafnate titanate thin films

We have investigated the electrical and optical properties of Ba(Hf_xTi_1 − x)O₃ (x = 0, 0.1, 0.2, 0.3, 0.4) (BHT) thin films deposited on platinized silicon and fused quartz substrates. Analyses of the X-ray diffraction patterns reveal that with the increase in Hf contents there is a systematic increase of the lattice constants of BHT films. Irrespective of the measurement frequencies the dielectric constants was found to be systematically decreased, whereas their frequency dispersion was found to be reduced with increasing Hf contents. The leakage current data measured using a metal-insulator–metal configuration reveal that the Schottky emission is the dominant leakage current mechanism in these films. BHT films, deposited on transparent fused quartz substrates, were also characterized in terms of their optical properties. For this purpose the transmittance of the undoped as well as Hf doped barium titanate thin films was measured as a function of wavelength in the range of 290 nm to 800 nm. The transmission spectra were analysed to estimate the wavelength dependence of the refractive indices/extinction coefficients as well as the variation of optical band gap of these films. With the increase of Hf contents, a systematic increase of the band gap [from 3.65 eV (undoped film) to 4.15 eV (40 at.% Hf doped barium titanate film)] was observed. The reduction of the leakage current with increasing hafnium substitution is discussed on the basis of an increasing Schottky barrier height and due to a simultaneous increase in the band gap of the material.