Perovskite Phase Formation in the Relaxor System [Pb(Fe1/2Nb1/2)O3]1-x–[Pb(Zn1/3Nb2/3)O3]x

Phase formation and dielectric properties of the compositions in the system [Pb(Fe_1/2Nb_1/2)O₃]₁_ _x –[Pb(Zn_1/3Nb_2/3)O₃] _x were investigated as possible materials for multilayer ceramic capacitors. The formation of the phase with perovskite structure and dielectric properties of ceramics at room temperature in the entire composition range are presented. The undesirable pyrochlore phase can be suppressed up to x = 0.6 by adopting calcination of B-site oxides, followed by reaction with PbO. Compositions in the single-phase range can be sintered at less than 1000°C.     

Physical and Dielectric Properties of (1–x)PbZrO3·xBaTiO3 Thin Films Prepared by Chemical Solution Deposition

Physical and dielectric properties of (1– x )PbZrO₃· x BaTiO₃ thin films prepared by a chemical coating process have been investigated as a function of BaTiO₃ ( x ) content (0≤ x ≤0.2). Changing the molar ratio between propylene glycol and water prior to the deposition optimized the chemical precursors. (1– x )PbZrO₃- x BaTiO₃ thin films that contained a majority of perovskite phase, but also contained large amounts of other phases, were fabricated. These films could withstand fields of 250 kV/cm at 1 kHz. The microstructure of the thin films was found to depend on the BaTiO₃ content. The phase transition from antiferroelectric to ferroelectric was gradually induced as the BaTiO₃ content increased. A maximum dielectric constant of ∼809 was obtained at the composition of x = 0.1. A maximum dielectric constant of ∼809 was obtained at the composition of x = 0.1. A thin film at the low-field antiferroelectric-ferroelectric phase boundary with x = 0.05 exhibited the highest P _sat and P _r values. The maximum values of these were 45 and 31 μC/cm², respectively.     

Phase Structure and Dielectric Properties of Bi2O3-ZnO-Nb2O5-Based Dielectric Ceramics

Phase structures and dielectric properties of the compounds with formulas BixZn_2/3Nb_4/3O_4+3x/2 (group M), Bi_xZn_8/3-x Nb_4/3O_6+x/2 (group V), and Bi_xZn_2-2x/3Nb_2-x/3O₇ (group W) have been investigated. Initial results indicate that a cubic pyrochlore structure is the predominant phase of these compound. Most of the measured ceramic specimens exhibit dielectric properties suitable as temperatures-stable and temperature-compensating dielectrics in the capacitor industry. The values of the dielectric constant K are 80-160, while those of the temperature coefficient are–500 to + 160 ppm/°C. The composition limits of the single pyrochlore phase are determined mainly by Bi₂O₃ additives.     

Compositional Studies of Lanthanum-Modified Morphotropic Phase Boundary Pb(Mg1/3Nb2/3)O3—PbTiO3 Ceramics

Investigations have been performed on the La-modified (1 - x )Pb(Mg_1/3Nb_2/3)O₃—( x )PbTiO₃ crystalline solution for compositions close to the morphotropic phase boundary (MPB) using energy-dispersive X-ray spectrometry (EDS). Studies were performed on specimens with La contents between 0 and 10 at.% for x = 0.35 which were fabricated by keeping the average Mg/Nb/Ti ratio in the bulk ceramic unchanged. In this series of samples, La3 was compensated for by introducing B-site vacancies. Quantitative analysis by EDS revealed a change in the B-site cation concentrations with La substitution. It was observed that the Nb concentration decreases and the Ti concentration increases with increasing La content, indicating that local charge compensation in the perovskite phase is taking place by an adjustment in B-site cation concentrations. Phase analysis demonstrated the presence of a second phase for La contents above 2 at.%. Scanning electron microscopy then revealed the presence of a secondary pyrochlore phase with an octahedral-like morphology. The composition of the pyrochlore phase was found to be rich in Nb and poor in Ti. The effects of changes in composition on dielectric properties, polarization, and electrically induced strain were then investigated.     

Preparation and Characterization of Relaxor Ferroelectric 0.65Pb(Mg1/3Nb2/3)O3–0.35PbTiO3 by a Polymerizable Complex Method

A modified polymerizable complex (PC) method for the preparation of the relaxor ferroelectric 0.65Pb(Mg_1/3Nb_2/3)O₃–0.35PbTiO₃ (PMN–PT) ceramics has been developed using a novel water-soluble Nb precursor. The effects of Pb content and sintering temperature on the structure, morphology, composition, and electrical properties of PMN–PT powders and ceramics were investigated systematically. It was found that the modified PC method could effectively reduce the initial crystallization temperature of the perovskite phase to 500°C. For PMN–PT samples with 15% excess Pb content sintered at 600°C for 2 h, the 87% perovskite phase can be achieved, which is much higher than that in conventional solid-state reactions and other solution-based methods at the same temperature. On further increasing the sintering temperature to 1100°C, the perovskite phase content basically remains constant. This is attributed to the Pb-deficient pyrochlore phase formation. On increasing the sintering temperature to 1250°C, the dielectric constant and remnant polarization of PMN–PT ceramics significantly improved due to the larger grain sizes, enhanced density, and the decreasing pyrochlore phase. PMN–PT ceramics with a 98.5% content of the perovskite phase have been fabricated at 1250°C. It displays typical ferroelectric relaxor characteristics with a remnant polarization of 18 μC/cm², a coercive field of 9.6 kV/cm, a piezoelectric coefficient of d ₃₃=360 pC/N, and room-temperature and maximum dielectric constants of 3600 and 10 500 at 1 kHz, respectively.     

Dielectric-State Analysis in Solid-Solution Pb(Yb1/2Ta1/2)O3–Pb(Lu1/2Nb1/2)O3

The structure and temperature dependence of complex lead perovskite dielectrics were investigated for the system (1 − x )Pb(Yb_1/2Ta_1/2)O₃– x Pb(Lu_1/2Nb_1/2)O₃. Superlattice reflections for the compositions 0.8 < x < 1.0 were observed by X-ray diffractometry, and the temperature-composition dielectric-state diagram was determined. In the present study, the disordered middle composition, with 0.2 < x < 0.8, showed a diffuse paraelectric–ferroelectric phase transition, whereas the ordered end compositions, with 0 ≤ x < 0.2 and 0.8 < x ≤ 1.0, revealed successive sharp paraelectric–antiferroelectric and weak antiferroelectric–ferroelectric phase transitions. The dielectric state was confirmed by examining the variation of polarization ( P ) with electric field ( E ).     

Control of Microstructure and Orientation in Solution-Deposited BaTiO3 and SrTiO3 Thin Films

Columnar and highly oriented (100) BaTiO₃ and SrTiO₃ thin films were prepared by a chelate-type chemical solution deposition (CSD) process by manipulation of film deposition conditions and seeded growth techniques. Randomly oriented columnar films were prepared on platinum-coated Si substrates by a multilayering process in which nucleation of the perovskite phase was restricted to the substrate or underlying layers by control of layer thickness. The columnar films displayed improvements in dielectric constant and dielectric loss compared to the fine-grain equiaxed films that typically result from CSD methods. Highly oriented BaTiO₃ and SrTiO₃ thin films were fabricated on LaAlO₃ by a seeded growth process that appeared to follow a standard "two-step" growth mechanism that has been previously reported. The film transformation process involved the bulk nucleation of BaTiO₃ throughout the film, followed by the consumption of this matrix by an epitaxial overgrowth process originating at the seed layer. Both BaTiO₃ and PbTiO₃ seed layers were effective in promoting the growth of highly oriented (100) BaTiO₃ films. Based on the various processing factors that can influence thin film microstructure, the decomposition pathway involving the formation of BaCO₃ and TiO₂ appeared to dictate thin film microstructural evolution.     

Dielectric and Ferroelectric Properties of Ceramics in the Pb(Zn 1/3Nb2/3)O3-BaTiO3-PbTiO3 System

The use of Pb(Zn_1/3Nb_2/3)O₃ ceramics is restricted by the formation of a pyrochlore phase detrimental to both dielectric and piezoelectric properties. Recently it has been shown that a 6 mol% addition of BaTiO₃ to PZN suppresses the formation of pyrochlore phase. Phase relations and dielectric properties of ceramics in the PZN-BT-PT system are reported here. Compositions with the perovskite structure, having high dielectric constant and low temperature coefficient of capacitance, have been identified.     

Ferroelectric and Structural Properties of the Pb(Sc1/2Nb1/2)1-x,Tix,O3 System

Extensive solid solution was observed in the system Pb(Sc_1/2/,Nb_1/2,)_1-x,Ti_x,O₃. In the range 0 ≤ x ≤ 0.425 a rhombohedral ferroelectric phase was stable at 25° C. In the range 0.45 ≤ x ≤ 1.00 a tetragonal ferroelectric phase was stable at this temperature. The phase diagram of the system below 500° C strongly resembles that of PbZrO₃−PbTiO₃. The compound Pb(Sc_1/2Nb_1/2)O₃ exhibited rhombohedral perovskite cell symmetry below the ferroelectric ↔ paraelectric transition temperature, and the angle a was acute. The radial coupling coefficient was 0.46 for the composition Sc_1/2Nb_1/2)_0.575Ti_0.4250O₃. At 25°C this composition consisted primarily of the rhombohedral phase with a small amount of the tetragonal phase present. The ferroelectric ↔ paraelectric transition occurred over a temperature range in the rhombohedral phase field. The spontaneous polarization was finite at temperatures considerably above the temperature of the permittivity maximum for a given rhombohedral solid solution.     

Mechanism of Formation of Perovskite Phase and Dielectric Properties of Pb(Zn,Mg)1/3Nb2/3O3 Ceramics Prepared by Columbite Precursor Routes

The mechanism of formation of the perovskite phase and the dielectric properties of Pb(Zn,Mg)_1/3Nb_2/3O₃ (PZMN) ceramics were examined using two different types of columbite precursors, (Mg,Zn)Nb₂O₆ (MZN) and MgNb₂O₆+ ZnNb₂O₆ (MN + ZN). The formation of perovskite phase in the PbO + MN + ZN system is characterized by an initial rapid formation of Mg-rich perovskite phase, followed by a sluggish formation of Zn-rich perovskite phase. On the other hand, due to the formation of pyrochlore phase of mixed divalent cations Pb_{2– x} (Zn,Mg)_yNb_2−yO_{7− x −3y/2}, the pyrochlore/perovskite transformation in the PbO + MZN system proceeded uniformly with a spatial homogeneity. Further analysis suggested that the formation of perovskite phase is a diffusion-controlled process. The degree of diffuseness of the rhombohedral/cubic phase transition (DPT) is higher in the PbO + MN + ZN system than in the PbO + MZN specimen for T > T _max (temperature of the dielectric permittivity maximum), indicating a broadened compositional distribution of the B-site cations in the PbO + MN + ZN system.     

Structure-Property Phase Diagram of BaZrxTi1−xO3 System

In the course of searching environmental friendly lead-free relaxor ferroelectrics a complete phase diagram of barium zirconate titanate, Ba(Zr _x Ti_{1− x} )O₃ system with compositions 0.00≤ x ≤1.00 has been developed based on their dielectric behavior. It has been shown that BaZr _x Ti_{1− x} O₃ system depending on the composition, successively depicts the properties extending from simple dielectric (pure BaZrO₃) to polar cluster dielectric, relaxor ferroelectric, second order like diffuse phase transition, ferroelectric with pinched phase transitions and then to a proper ferroelectric (pure BaTiO₃). A comprehensive structure–property correlation of BaZr _x Ti_{1− x} O₃ ceramics has been studied to understand the various ferroelectric phenomena in the whole phase diagram.     

Synthesis and Dielectric Properties of Solution Sol-Gel-Derived 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 Ceramics

A solution sol-gel method has been developed to prepare 0.9Pb(Mg_1/3Nb_2/3)O₃-0.1PbTiO₃ (0.9PMN-0.1PT) ceramics. During the processing the gel first converted to cubic pyrochlore phase at a calcination temperature of 600°C followed by the formation of pure perovskite phase at 775°C. The ceramics sintered at 1250°C for 4 h showed ≈98% of the theoretical density. The room-temperature dielectric constant of the pellets sintered at 1250°C showed a maximum value of 25035 at 1 kHz. Sintering studies at different temperatures revealed that the dielectric constant increased with increasing grain size in these ceramics.     

Rapid Thermal Processing of Pb(Mg0.7Zn0.3)1/3Nb2/3O3 Multilayer Ceramic Capacitors

Fast firing, with total sintering times of between 3 and 15 min, was utilized to process multilayer ceramic capacitors of dielectric composition Pb(Mg_0.7Zn_0.3)_1/3Nb_2/3O₃. This dielectric composition has been studied extensively because of its diffuse phase transition, which is intrinsic to relaxors, and also its high dielectric constant. The fast-firing procedure, which did not utilize any prevention for PbO volatilization, has been shown to be a feasible method for the processing of these components. Sintering times in the range of 12 to 15 min at 1100°C resulted in components with weak field dielectric constants in excess of 12 000 and grain sizes in the range of 1 μm or less. The development of a pyrochlore phase at the component surfaces was less influential on the dielectric performance of the components because of the internal nature of the electrodes.     

Formation of the Perovskite Phase in the PbMg1/3Nb2/3O3─PbTiO3 System

The reaction sequences during calcination of oxide mixtures were studied for the PbMg_1/3Nb_2/3O₃─PbTiO₃ (PMN-PT) system. The effect of reactivity and composition of the starting mixtures was investigated. In the present study, a B-site-deficient, cubic pyrochlore phase in the PbO-Nb₂O₅ system was formed at 500°C. The perovskite phase of PMN was formed at 7007deg;C through the diffusion of MgO into the pyrochlore phase. The lattice parameter of the pyrochlore phase decreased as this transformation to perovskite progressed.     

Thermodynamic Stability and Mechanisms of Formation and Decomposition of Perovskite Pb(Zn1/3Nb2/3)O3 Prepared by the PbO Flux Method

The mechanisms of formation and decomposition of the ferroelectric perovskite PZN [Pb(Zn_1/3Nb_2/3)O₃] were examined. The formation of perovskite PZN from the excess molten PbO environment is characterized by an inititial rapid formation of pyrochlore phase, followed by a subsequent reaction between the intermediate pyrochlore phase, ZnO, and liquid PbO to produce perovskite phase. The pure perovskite PZN crystal prepared by the PbO flux method is thermodynamically unstable over a wide range of temperature (600° to 1400°C), yielding pyrochlore phase and PbO as the decomposition products. The decomposition reaction of perovskite PZN proceeded uniformly with a spatial homogeneity throughout the specimen. The estimated activation energy of the decomposition reaction is approximatley 18 kcal/mol.     

Ferroelectric and Dielectric Properties of Pb(Mg1/3Ta2/3)0.7Ti0.3O3 Thin Films Derived from RF Magnetron Sputtering

Pb(Mg_1/3Ta_2/3)_0.7Ti_0.3O₃ thin films of single perovskite phase were successfully synthesized by using the RF sputtering deposition technique, followed by post-thermal annealing. While the perovskite structure of Pb(Mg_1/3Ta_2/3)_0.7Ti_0.3O₃ is rather unstable, phase evolution in the thin films was manipulated by controlling both working pressure during the sputtering process and post-thermal annealing temperature. The desirable perovskite phase was promoted by increasing the working pressure in the range of 10–25 mTorr, followed by thermal annealing at 600°C. The ferroelectric, dielectric, and polarization behaviors of Pb(Mg_1/3Ta_2/3)_0.7Ti_0.3O₃ films were characterized over a wide range of frequencies. They are strongly affected by the film thickness, where the relative permittivity and remanent polarization increase, while the coercive field decreases with increasing film thickness in the range of 115–360 nm.     

Low-Temperature Firing and Microwave Dielectric Properties of Ca[(Li1/3Nb2/3)0.84Ti0.16]O3−δ Ceramics for LTCC Applications

The effects of LiF and ZnO–B₂O₃–SiO₂ (ZBS) glass combined additives on phase composition, microstructures, and microwave dielectric properties of Ca[(Li_1/3Nb_2/3)_0.84Ti_0.16]O_3−δ (CLNT) ceramics were investigated. The LiF and ZBS glass combined additives lowered the sintering temperature of CLNT ceramics effectively from 1150° to 880°C. The main diffraction peaks of all the specimens split due to the coexistence of the non-stoichiometric phase (A) and stoichiometric phase (B), which all possess CaTiO₃-type perovskite structures. The transformation from A into B became accelerated with the increase of LiF or ZBS content. ZBS glass restrained the volatilization of lithium salt, which greatly affected the microstructures and microwave dielectric properties. CLNT ceramics with 2 wt% LiF and 3 wt% ZBS sintered at 900°C for 2 h show excellent dielectric properties: ɛ_r=34.3, Q × f =17 400 GHz, and τ_f=−4.6 ppm/°C. It is compatible with Ag electrodes, which makes it a promising ceramic for low-temperature cofired ceramics technology application.     

Sol—Gel Fabrication of Pb(Zr0.52 Ti0.48)O3 Thin Films Using Lead Acetylacetonate as the Lead Source

Lead zirconium titanate (PZT) thin films of the morphotropic phase boundary composition [Pb(Zr_0.52Ti_0.43)O₃] were deposited on platinum-coated silicon by a modified sol-gel process using lead acetylacetonate as the lead source. The precursor solution for spin coating was prepared from lead acetylacetonate, zirconium n -butoxide, and titanium isopropoxide. The use of lead acetylacetonate instead of the widely used lead acetate trihydrate provided more stability to the PZT precursor solution. Films annealed at 700°C for 12 min formed well-crystallized perovskite phase of Pb(Zr_0.52Ti_0.48)O₃. Microstructures of these films indicated the presence of submicrometer grains (0.1 to 0.2 μm). The dielectric constant and loss values of these films measured at 10 kHz were approximately 1200 and 0.04, respectively, while the remanent polarization and coercive field were ∼ 13 μC/cm² and ∼ 35 kV/cm. Aging of the solution had almost no effect on the dielectric and ferroelectric properties of these films.     

Weakly Coupled Relaxor Behavior of BaTiO3–BiScO3 Ceramics

The structural and dielectric properties of (1− x )BaTiO₃– x BiScO₃ ( x =0–0.5) ceramics were investigated to acquire a better understanding of the binary system, including determination of the symmetry of the phases, the associated dielectric properties, and the differences in the roles of Bi₂O₃ and BiScO₃ substitutions in a BaTiO₃ solid solution. The solubility limit for BiScO₃ into the BaTiO₃ perovskite structure was determined to be about x =0.4. A systematic structural change from the ferroelectric tetragonal phase to a pseudo-cubic one was observed at about x =0.05–0.075 at room temperature. Dielectric measurements revealed a gradual change from proper ferroelectric behavior in pure BaTiO₃ to highly diffusive and dispersive relaxor-like characteristics from 10 to 40 mol% BiScO₃. Several of the compositions showed high relative permittivities with low-temperature coefficients of capacitance over a wide range of temperature. Quantification of the relaxation behavior was obtained through the Vogel–Fulcher model, which yielded an activation energy of 0.2–0.3 eV. The attempt characteristic frequency was 10¹³ Hz and the freezing temperature, T _f, ranged from −177° to −93°C as a function of composition. The high coercive fields, low remanent polarization, and high activation energies suggest that in the BiScO₃–BaTiO₃ solid solutions, the polarization in nanopolar regions is weakly coupled from region to region, limiting the ability to obtain long-range dipole ordering in these relaxors under field-cooled conditions.     

A Polyethylene Glycol-Modified Solid-State Reaction Route to Synthesize Relaxor Ferroelectric Pb(Mg1/3Nb2/3)O3–PbTiO3 (PMN–PT)

By introducing polyethylene glycol (PEG) to the conventional simultaneously mixed oxide reaction route, the 0.65Pb(Mg_1/3Nb_2/3)–0.35PbTiO₃ (0.65PMN–0.35PT) powders and ceramics with pure perovskite phase have been successfully synthesized. It is found that PEG interacts with PbO oxide in a way favoring the formation of the desired perovskite phase. As a result, pyrochlore-free 0.65PMN–0.35PT powders are synthesized at a low temperature of 850°C. The ceramics sintered at 1000°C show uniform grains with the size ranging from 1 to 3 μm. The room temperature dielectric constant is 3440. The maximum dielectric constant is 16 220 at 1 kHz. This method can be applied to the synthesis of other Pb-containing and Bi-containing ferroelectric materials, especially the relaxor-type ferroelectrics in which the pyrochlore phase is difficult to eliminate.