Phase Diagram for the 0.4Pb(Ni1/3,Nb1/3)O3–0.6Pb(Zr,Ti)O3 Solid Solution in the Vicinity of a Morphotropic Phase Boundary

A phase diagram based on dielectric-permittivity-versus-temperature measurements and high-temperature X-ray diffractometry was proposed for 0.4Pb(Ni_1/3,Nb_1/3)O₃- x PbZrO₃-(0.6- x )PbTiO₃ (0.2 lessthan equal to x lessthan equal to 0.32) relaxor-ferroelectric solid solution, and a morphotropic phase boundary that sharply bends toward zirconium-rich compositions was found. A spontaneous normal-to-relaxor ferroelectric transition was also observed when heating was performed for all the compositions tested near the morphotropic phase boundary. Additional considerations about previously published phase diagrams for Pb(Zn_1/3,Nb_2/3)O₃-PbTiO₃ and Pb(Mg_1/3,Nb_1/3)O₃-PbTiO₃ might lead to an extension of the presented diagram to these compositions.     

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.     

Low-Field Depoling Characteristics of Pb(Zr, Ti)O3 Ceramics

Low-electric-field depoling measurements were made on Pb(Zr, Ti)O₃ ceramics. The apparent activation energy for the depoling process was calculated to be 33 kcal/mol. The data indicate that the materials tested should be very stable when subjected to depoling fields on the order of one-fourth of the coercive field.     

Electron Paramagnetic Resonance Investigation of Acceptor Centers in Pb(Zr,Ti)O3 Ceramics

The nature of extrinsic point defects in lead zirconate titanate (PZT) ceramics of various compositions prepared by solution chemistry has been explored. Using electron paramagnetic resonance (EPR), several impurity sites have been identified in the as-received materials, which include Fe³⁺oxygen vacancy (V_O^‥) complex and isolated Cu²⁺ ions; both of these ions are incorporated into the lattice by replacing the Ti(Zr) ion. A Fe₃₊V_O^‥ complex serves as a sensitive probe of the local crystalline field environment of the ceramic; the symmetry of this defect is roughly correlated with its phase diagram as the composition is varied from PbTiO₃ to PbZrO₃. The Fe³⁺V_O^‥ complex experiences tetragonal, rhombic, or orthorhombic symmetry as the composition is varied from PbTiO₃ to PbZrO₃. As the composition of the Cu²⁺ ion is varied, it appears as though the addition of Zr, and not necessarily a change in phase, is largely responsible in determining the local environment of this acceptor impurity. Also, the Cu²⁺ resonance parameters weakly reflect the relative Ti–O(Zr–O) bond covalency in the perovskite lattice.     

The Ba(Ti,Zr)O3–(Zr,Ti)O2 Field in the Phase System BaO–TiO2–ZrO2

The two-phase field involves a ZrO₂-TiO₂ solid solution containing no more than 4 mol% TiO₂, and a BaTiO₃-BaZrO₃ solid solution containing a maximum of 75 mol% BaTiO₃. The field narrows above 1300°C, probably because of the intrusion of a liquid-phase field into the ternary, beginning near the BaO-TiO₂ edge.     

Effect of Additives on the Electromechanical Properties of Pb(Zr,Ti)O3–Pb(Y2/3W1/3)O3 Ceramics

Dielectric and piezoelectric properties of 0.02Pb(Y_2/3W_1/3)O₃ 0.98Pb(Zr0.52Ti0.48)O3 ceramics doped with additives (Nb₂O₅, La₂O₃, MnO₂, and Fe₂O₃) were investigated. The grain sizes of these ceramics decreased with increasing amounts of additives. For additions of MnO₂ and Fe₂O₃, dielectric losses decreased, while for Nb₂O₅ and La₂O₃, these values increased. The maximum values of the mechanical quality factor Q_m were found to be 956 and 975 for additions of 0.9 wt% Fe₂O₃ and 0.7 wt% MnO₂, respectively, but donor dopants (Nb₂O₅ and La₂O₃) did not change the values of Q_m . On the other hand, the piezoelectric constant d₃₃ and the electromechanical coupling factor k_p decreased with additions of MnO₂ and Fe₂O₃, but improved with additions of Nb₂O₅ and La₂O₃.     

Piezoelectric Properties of Pb(Mg1/3Nb2/3)O3—PbTiO3—PbZrO3 Solid Solution Ceramics

Ceramic and electrical properties and crystal structures of the system Pb(Mg_l/3Nb_2/3- PbTiO₃-PbZrO₃ are described. The system is composed of three crystal phases at room temperature: pseudocubic, tetragonal, and rhombohedral. A high dielectric constant and radial coupling coefficient and low resonant resistance were obtained for the compositions near the morphotropic transformation. The composition Pb(Mg_l/3Nb_2/3)_0.4375Ti_0.4375Zr_0.125O₃ had the lowest temperature coefficient of resonant frequency.     

Highly Oriented, Chemically Prepared Pb(Zr, Ti)O3 Thin Films

We have fabricated highly oriented, chemically prepared thin films of Pb(Zr_0.04Tio._0.60)O₃ (PZT 40/60) on both insulating and conducting substrates. While (100) MgO single crystals were used as the insulating substrates, the conducting substrates. were fabricated by RF magnetron sputter deposition of 100-nm-thick (100) Pt films onto (100) MgO substrates. For comparison, we also fabricated PZT 40/60 films that had no significant preferential orientation on platinized MgO substrates. Sputter deposition of an underlying amorphous Pt film was used to fabricate randomly oriented PZT 40/60 films. Highly (001) oriented PZT 40/60 films had higher remanent polarization (61 μC/cm² compared to 41 μC/cm²) and lower relative dielectric constant (368 compared to 466) than PZT 40/60 films that were randomly oriented.     

Preparation of Full-Dense Pb(Zr,Ti)O3 Ceramics by Aerosol Deposition

Full-dense fine-grained bulk Pb(Zr,Ti)O₃ (PZT) ceramics with a thicknesses of 300 μm were successfully obtained by aerosol deposition (AD) employing the starting powder subjected to an adequate pretreatment. It was found that formation of internal pores during the postdeposition firing treatment takes place in two different mechanisms on different scales. Residual carbons contained in the as-deposited PZT ceramics are responsible for the formation of extra-large pores, inducing severe distortion to the shape of the sample. On the other hand, trapped agglomerates in the as-deposited PZT ceramics are responsible for the formation of intermediate pores. The revealed mechanisms are discussed with a focus on the positive/negative correlation between the pretreatment procedure of starting powders and the formation of internal pores.     

Shape Evolution of Pb (Zr,Ti)O3 Nanocrystals Under Hydrothermal Conditions

Pb (Zr,Ti)O₃ nanocrystals with different morphologies have been prepared hydrothermally with poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) as surfactants. The morphology of Pb (Zr,Ti)O₃ nanocrystals develops from a particle to a rod and then a wire by adjusting the ratio of PVA/PAA and reaction time in a hydrothermal system. The mixed surfactant system has been shown to promote anisotropic growth effectively and thus the formation of nanorods and single crystalline nanowires of Pb (Zr,Ti)O₃. A possible mechanism for such a shape evolution of nanocrystals is simply discussed.     

Improved Hot-Pressed Electrooptic Ceramics in the (Pb,La)(Zr,Ti)O3 System

Physical, electrical, and optical properties of selected compositions within the lead lanthanum zirconate-titanate (PLZT) system are presented, including chemically and thermally etched microstructures, examples of residual porosity defects, temperature dependence of remanent polarization and coercive field, lateral switching strains, and thermal expansion and optical transmission data. Optical-quality ceramics were produced by stringent raw material selection and improved ceramic processing and hot-pressing. Optimum results were obtained from starting oxides with higher purity (99.9%) and smaller particle size (<2 μm) than those used in previous investigations. These oxides were processed by methods developed to minimize segregation and promote chemical homogeneity and hot-pressed at temperatures (1050° to 1250°C) higher than those used previously to remove residual porosity.     

Excimer Laser Crystallized (Pb,La)(Zr,Ti)O3 Thin Films

A KrF pulsed excimer laser (248 nm) was utilized to crystallize sputtered La-modified Pb(Zr,Ti)O₃ (3:30:70) (PLZT) films on LaNiO₃-coated silicon substrates. The film surface was irradiated with defocused laser pulses in an oxygen ambient at various substrate temperatures. Polycrystalline, phase pure perovskite PLZT thin films were produced for substrate temperatures of 250°C and higher. The dielectric constant and loss tangent values of laser-assisted crystallized (10 min exposure at 10 Hz using a substrate temperature of 400°C) PLZT thin films at 10 kHz were 406 and 0.027; in comparison, rapid thermal annealed films (annealed at 700°C for 1 min) showed values of 400 and 0.021, respectively. Laser crystallized films exhibited a remanent polarization value of 14 μC/cm² with a coercive field |( E _+c+ E _−c)|/2 of 95 kV/cm.     

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 ).     

Bipolar Fatigue Caused by Field Screening in Pb(Zr,Ti)O3 Ceramics

Bipolar cycling of lead zirconate titanate ceramics can lead to massive material damage in regions close to the electrode. The damaged region can be identified by color changes, and the microstructure in this region shows signs of interface melting. This damaged region can screen the sample volume from the applied voltages and reduced fields are applied to the undamaged part of the sample. This has two effects. The first one is that the bulk is effectively subjected to smaller fields, but the measured parameters are assigned to the applied field, yielding apparent fatigue curves. The second effect is that with further cycling, field screening protects the bulk of the sample from fatigue due to the reduced effective fields. If the damaged region is mechanically removed and the ferroelectric hystereses are measured again, nearly unfatigued parameters are obtained.     

Metalorganic Chemical Vapor Deposition of Ferroelectric Pb(Zr,Ti)O3 Thin Films

Ferroelectric Pb(Zr_xT_1–x)O₃, films were successfully and reproducibly deposited by both hot–wall metalorganic chemical vapor deposition (MOCVD) and cold-wall MOCVD. One of the important problems associated with the MOCVD techniques is the selection of ideal precursors. After an intensive investigation for the most suitable precursors for MOCVD PZT films, the safe and stable precursors, namely lead tetramethylheptadione [Pb(thd)₂], zirconium tetramethylheptadione [Zr(thd)₄], and titanium ethoxide [Ti(OEt)₄], were chosen. The films were deposited at temperatures as low as 550°C and were single-phase perovskite in the as-deposited state. Also, the films were smooth, specular, crack-free, and uniform, and adhered well to the substrates. The stoichiometry of the films can be easily controlled by varying the individual precursor temperature and/or the flow rate of the carrier gas. Auger electron spectroscopic (AES) depth profile showed good compositional uniformity through the thickness of the films. The AES spectra also showed no carbon contamination in the bulk of the films. As-deposited films were dense and showed uniform and fine grains (≅0.1 μm).The optical properties of the films on the sapphire disks showed high refractive index ( n = 2.413) and low extinction coeflicient ( k = 0.0008) at a wavelength of 632.8 nm. The PZT (82/18) film annealed at 600°C showed a spontaneous polarization of 23.3 μC/cm² and a coercive field of 64.5 kV/cm.     

Effect of Simultaneous Addition of BiFeO3 and Ba(Cu0.5W0.5)O3 on Lowering of Sintering Temperature of Pb(Zr,Ti)O3 Ceramics

Sintering of 0.5-wt%-MnO₂-added Pb(Zr_0.53Ti_0.47)O₃ ceramics progresses at 935°C for 50 min by the addition of complex oxides of perovskite-type crystal structure, BiFeO₃ and Ba(Cu_0.5W_0.5)O₃. In order to elucidate the low-temperature sintering mechanism of Pb(Zr,Ti)O₃ ceramics, the shrinkage and the evolution of the microstructure of a compacted body during heating were studied. It has been shown that the densification process was separated into the following three stages: the rearrangement of grains, the grain boundary diffusion of atoms, and then grain growth. Also, microstructural and elemental analyses of the ceramics revealed the existence of an amorphous phase at the grain boundaries predominantly composed of lead and copper oxides. Consequently, this process can be facilitated by the occurrence of a transient liquid phase corresponding to the above amorphous phase.     

Hot-Pressed (Pb,La)(Zr,Ti)O3 Ferroelectric Ceramics for Electrooptic Applications

Transparent ferroelectric ceramic materials suitable for a variety of electrooptic applications were found in the quaternary (Pb,La)(Zr,Ti)O₃ system. These PLZT materials are prepared from mixed oxides and hot-pressed typically at 1100°C for 16 h at 2000 psi. Modifying the lead zirconate-titanate system with lanthana linearly reduces the Curie point with increasing lanthana. Transmission measurements in the visible and infrared show that these materials exhibit a nearly constant response from the absorption edge of 0.37 μ to ∼6 μm. The highest transmission values, essentially 100% (neglecting reflection losses of ∼18%) for thin polished plates, were noted for compositions containing 8 at.% La or more. Specific compositions within the system display electrooptic memory or conventional linear or quadratic electrooptic effects; on the basis of the magnitude of the electrooptic effects, they compare quite favorably with single crystals.