Dielectric and Electrical Conductivity Properties of PMS–PZT Ceramics

The dielectric and electrical conductivity properties of x Pb(Mn_1/3Sb_2/3)O₃–(1− x )Pb(Zr_0.52Ti_0.48)O₃ (PMS–PZT) ceramics were studied. X-ray diffraction indicated that all samples exhibit a single-phase perovskite structure. Dielectric study revealed that the dielectric relaxor behavior was induced by co-doping Mn²⁺ and Sb⁵⁺ into Pb(Zr_0.52Ti_0.48)O₃ ceramics. Electrical conductivity measurements showed that the concentration of carriers are increased with the increase in PMS contents. After annealing in an oxygen atmosphere for 30 h, the direct current conductivity of PMSZ15 was much lower than that of the as-sintered sample. The reason why this phenomenon occurs may be the reduction of oxygen-vacancy concentration.     

Fabrication of High Aspect Ratio Ferroelectric Microtubes by Vacuum Infiltration using Macroporous Silicon Templates

Ordered arrays of high aspect ratio (>10:1) ferroelectric Pb(Zr_0.52Ti_0.48)O₃ (PZT) tube structures were fabricated by vacuum infiltration of macroporous silicon (Si) templates. Improved phase purity was achieved when PZT microtubes were pyrolyzed at 300°C and partially released from the Si template to prevent a chemical reaction between the Pb and the Si during subsequent high-temperature crystallization. The free-standing microtubes were crystallized by rapid thermal annealing at 750°C for 1–3 min. Perovskite phase formation was confirmed by X-ray diffraction and transmission electron microscopy methods. Coaxial structures comprised of metallic LaNiO₃, PZT, and Pd layers were also processed to enable future electrical characterization of the ferroelectric microtubes.     

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.     

Modifying Structures and Ferroelectric Properties of Pb(Zr0.6Ti0.4)O3 Thin Films by Constraint-Annealing of Precrystallized Film

A tensile or compressive mechanical constraint was applied, during annealing, on the Pb(Zr_0.6Ti_0.4)O₃ (PZT) ferroelectric films to investigate the effects of stress on its crystal structure and electric properties. The external stress was applied by bending the substrate into a circular section. By using both precrystallized film structure and high constraint strain (0.08%), the stress states of PZT during the crystallization process became controllable. Structural change of polycrystalline PZT was observed when crystallized under a compression constraint. Moreover, these films with compression constraint annealing exhibited enhanced remnant polarization by ∼70% and increased dielectric constant by ∼68%. The variations in ferroelectric behaviors were correlated to domain configuration, texture, amount of pyrochlore phase, grain size and residual stress, which are dependent on the stress state during annealing process.     

Intrinsic Nonstoichiometry in Single-Phase Pb(Zr0.5Ti0.5)O3

Two-phase crucibles made of Pb(Zr,Ti)O₃ with small additions of either PbO or (Zr _x Ti _1-x )O₂, which provide atmospheres of constant PbO activity, permit study of intrinsic nonstoichiometry by thermogravimetry. The width of the single-phase region can be determined by alternate equilibration of a sample with crucible atmospheres of high and low PbO activity. The width of this region for Pb(Zr_0.5Ti_0.5)O₃ is 2.48 mol% PbO at 1100°C.     

Temperature–Time Texture Transition of Pb(Zr1−xTix)O3 Thin Films: I, Role of Pb-rich Intermediate Phases

Lead-rich intermediate phases, in particular Pt_5–7Pb and PbO, are found to form on Pt(111) atop Ti–buffered Si substrates prior to formation of Pb(Zr_{1− x} Ti _x )O₃ (PZT) thin films. Pt_5–7Pb is a [111] textured transient intermetallic phase that nucleates PZT[111] texture. PbO is a [001] textured layer compound that nucleates PZT[100] texture. The formation conditions and lattice matching of these intermediate phases have been examined. The presence of other possible intermediate phases, such as pyrochlore and Zr and Ti-rich phases, has also been investigated but found unrelated to the texture selection of perovskite PZT.     

Substrate Effect on the Magnetoelectric Behavior of Pb(Zr0.52Ti0.48)O3 Film-On-CoFe2O4 Bulk Ceramic Composites Prepared by Direct Solution Spin Coating

Magnetoelectric (ME) composite structures of Pb(Zr_0.52Ti_0.48)O₃ (PZT) and CoFe₂O₄ (CFO) were prepared by directly growing PZT films on highly dense CFO ceramics via a simple solution spin coating, rather than by conventional high-temperature cofiring. An obvious ME response, which had the same bias-dependent trend as the piezomagnetic coefficient of CFO ceramics, was observed in such film-on-bulk ceramic composites. It was found that the PZT films showed a good ferroelectric feature, and the ME response of the composites strongly depended on the resistivity of the CFO ceramics as both a substrate and a bottom electrode. The results suggest plenty of room for further enhancing the ME response of such films-on-ceramic substrate composites.     

Control of Leakage Resistance in Pb(Zr,Ti)O3 Thin Films by Donor Doping

Donor doping, with La and Nb, has been used successfully to improve the leakage resistance of Pb(Zr,Ti)O₃ (PZT) films. Donor doping of Pb(Zr_0.5Ti_0.5)O₃ films has led to an improvement in the leakage resistance of over 2 1/2 orders of magnitude at elevated temperatures (T 100°C). The effect on leakage resistance is the same for the A-site (La) and B-site (Nb) dopants. However, the improvement is only about 1 order of magnitude near room temperature. This temperature effect is due to an increase in the transition temperature from a low activation energy mechanism to a higher activation energy mechanism. Similar improvements in leakage resistance have also been obtained by increasing the Pb concentration in the starting solution, which implies that Pb vacancies are the dominant acceptor species in the undoped films. In addition, donor doping has been effective in improving the electrical breakdown strength at elevated temperatures. Consequently, donor-doped PZT films have been shown to be superior to undoped films for applications requiring high leakage resistance, such as decoupling capacitors.     

Preparation of Lead Zirconate Titanate (Pb(Zr0.52Ti0.48)O3) by Homogeneous Precipitation and Calcination

Preparation of phase-pure PZT (Pb(Zr_0.52Ti_0.48)O₃) powders was achieved, in the presence of urea (CH₄N₂O), by homogeneous precipitation. Aqueous solutions of PbCl₂, ZrOCl₂·8H₂O, and TiCl₄ were used as the starting materials in the synthesis of phase-pure PZT powders. Phase evolution behavior of precursor powders was studied by powder X-ray diffraction (XRD) in air, over the temperature range of 90° to 750°C. The morphology of the formed powders was studied by scanning electron microscopy (SEM). Semiquantitative chemical analyses of the samples were performed by energy-dispersive X-ray spectroscopy (EDXS).     

Formation of Lead Zirconate-Lead Titanate Solid Solutions

Formation of the Pb(Zr,Ti)O₃ solid solution in the system PbO-TiO₂-ZrO₂ was studied by chemical analysis and X-ray powder diffrac-tometry. Only PbTiO₃ and Pb(Zr,Ti)O₃ were found as reaction products. The following three elementary reactions seemed to be reasonable for the formation of the Pb(Zr,Ti)O₃ phase: PbO + TiO₂→ PbTiO₃, PbTiO₃+ PbO + ZrO₂→Pb(Zr_1-λTi_λ)O₃, and Pb(Zr_l-λTi_λ)O₃+ PbTiO₃→ Pb(Zr_1-λ'Ti_λ')O₃ (λ<λ').     

Transmission Electron Microscopy of Pb(Zr0.52Ti0.48)O3

Transmission electron microscopy of Pb(Zr_0.52Ti_0.48)O₃ sintered with 3 wt% excess PbO indicates that there is an amorphous grain-boundary phase 10 nm thick. The grain-boundary phase has a higher Pb content than the bulk material. Influence of such a phase on sintering is discussed.     

Factors Determining Grain Orientation in Bismuth Sodium Potassium Titanate–Lead Zirconate Titanate Solid Solutions Made by the Reactive Templated Grain Growth Method

Grain-oriented Bi_0.5(Na_0.85K_0.15)_0.5TiO₃-Pb(Zr_{1− x} Ti _x )O₃ (BNKT-PZT) ceramics were prepared via the reactive templated grain growth method, using platelike Bi₄Ti₃O₁₂ particles. Factors that determine the degree of orientation were examined. Prereacted PZT gave a larger degree of orientation than PZT raw materials (PbO, ZrO₂, and TiO₂) in the 75BNKT-25PZT ( x = 0.5) system. Increases in the titanium concentration in the PZT of the 75BNKT-25PZT system and in the BNKT concentration in the y BNKT-(100 − y )PZT ( x = 0.5) system increased the degree of orientation. The direction of material transport between BNKT and PZT was important to obtain ceramics with a large degree of orientation.     

Effects of Residual Stress on the Electrical Properties of PZT Films

The effects of the residual stress (either compressive or tensile) induced during the heat-treatment process on the electrical properties of Pb(Zr_0.52Ti_0.48)O₃ (PZT) films were investigated. The PZT films were deposited on platinized silicon substrates by the rf-magnetron sputtering method using a single oxide target. After their deposition, the films were bent elastically by means of a specially designed fixture during the annealing process. Residual stress was induced in the film by removing the substrate from the fixture after annealing. The ferroelectric and piezoelectric properties of the films were markedly changed by the residual stresses; the remnant polarization ( P _r) and saturation polarization ( P _sat) increased when a compressive stress was induced. On the other hand, the piezoelectric properties increased when a tensile stress was induced in the film.     

Properties of Modified Lead Zirconate Titanate Ceramics Prepared at Low Temperature (800°C) by Hot Isostatic Pressing

High-density lead zirconate titanate (PZT) ceramics were fabricated for the first time at a temperature as low as 800°C via the hot isostatic pressing (HIP) of a PZT powder with a modified composition of 0.92Pb(Zr_0.53Ti_0.47)O₃—0.05BiFeO₃—0.03Ba(Cu_0.5W_0.5)O₃ that contained 0.5 mass% MnO₂. The resultant PZT ceramics exhibited a microstructure that was denser and finer than that of PZT sintered at 935°C, which is the lowest temperature for the densification of the same composition via normal sintering. The relevant dielectric and piezoelectric properties of the HIPed PZT ceramics were as follows: coefficient of electromechanical coupling ( K ₃₁), 31.8%; mechanical quality factor ( Q _m), 1364; piezoelectric constant ( d ₃₁), −73.7 × 10⁻¹² C/N; relative dielectric constant (ɛ₃₃^T/ɛ₀), 633; dielectric loss factor (tan δ), 0.5%; Curie temperature ( T _c), 285°C; and density (ρ), 8.06 g/cm³. In addition to these reasonably good piezoelectric properties, the HIPed PZT exhibited better mechanical properties—particularly, higher fracture strength—than the normally sintered PZT.     

Ink-Jet Printing and Sintering of PZT

Suspensions of Pb(Zr_0.53Ti_0.47)O₃ (PZT)-5H powders, with solid contents up to 40 vol% in a paraffin oil/wax medium using a mixed polyester and amine dispersant system, have been prepared for ink-jet printing. Sufficient suspension stability for printing requires a sub-micron particle distribution, and this could only be achieved by attrition milling the as-received powder. The influence of printing parameters on drop velocity is shown to be consistent with simple physical models of the behavior of the suspensions. Trial objects have been fabricated with 35% PZT suspensions. These have been sintered to full density, with porosity less than 1% and without significant distortion, despite a mean linear shrinkage measured at 25%.     

Preparation of Lead Zirconate Titanate Thin Films Derived by Hybrid Processing: Sol-Gel Method and Laser Ablation

Thin films of Pb(Zr_0.52Ti_0.48)O₃ (PZT) were prepared by hybrid processing (sol-gel and excimer laser ablation) on Pt/Ti/SiO₂/Si substrates. Crystalline phases and microstructures of the PZT films were investigated by X-ray diffraction analysis and scanning electron microscopy, respectively. Electrical properties of the films were evaluated by measuring their P - E hysteresis loops and dielectric constants. The temperature of postdeposition annealing in hybrid processing was lower than that in the case of direct film deposition by laser ablation on a Pt/Ti/SiO₂/Si substrate. The preferred orientation of the films derived by hybrid processing could be controlled using the seeding layer deposited by the sol-gel process. The films fabricated by hybrid processing consisted of the perovskite phase with a (111) preferred orientation and had good ferroelectric properties.     

Piezoelectricity in the Field-Induced Ferroelectric Phase of Lead Zirconate-Based Antiferroelectrics

The piezoelectric characteristics were investigated in the field-induced ferroelectric phase of the antiferroelectric Pb_0.99 Nb_0.02[(Zr_0.6Sn_0.4) _{1 − y} Ti _y ]_0.98O₃ family. The electromechanical coupling factors k _p and k _t were measured, and the piezoelectric anisotropy was calculated. The piezoelectricity was controlled easily by the applied electric field pulse. The large piezoelectric anisotropy of these materials in comparison to that of conventional PZT piezoelectric materials makes them very applicable for ultrasonic probes and surface acoustic wave filters.     

Sol-Gel Preparation of Pb(Zr0.50Ti0.50)O3 Ferroelectric Thin Films Using Zirconium Oxynitrate as the Zirconium Source

Lead zirconium titanate (Pb(Zr_0.5Ti_0.5)O₃, PZT) ferroelectric thin films were successfully deposited on platinum-coated silicon substrates and platinum-coated silicon substrates with a PbTiO₃ interlayer by using a modified sol–gel spin-coating process, using zirconium oxynitrate dihydrate as the zirconium source. The precursor solution for spin coating was prepared from lead acetate trihydrate, zirconium oxynitrate dihydrate, and tetrabutyl titanate. The use of zirconium oxynitrate instead of the widely used zirconium alkoxide provided more stability to the PZT precursor solution and a well-crystallized structure of PZT film at a relatively low processing temperature. PZT films that were annealed at a temperature of 700°C for 2 min via a rapid thermal annealing process formed a well-crystallized perovskite phase of PZT films and also had nanoscale uniformity. The microstructure and morphology of the prepared PZT thin films were investigated via X-ray diffractometry, transmission electron microscopy, and atomic force microscopy techniques. The values for the remnant polarization ( P ) and coercive electric field ( E ) of the PZT films that were obtained from the P–E loop measurements were 3.67 μC/cm² and 54.5 kV/cm, respectively.     

Modeling the Dielectric Response and Relaxation Spectra of Relaxor Ferroelectrics

A multi-Debye relaxation model that is based upon the Boltzmann superposition principle has been used to determine the frequency-dispersion behavior of Pb(Mg_1/3-Nb_2/3)O₃ (PMN) and Pb_0.88La_0.08(Zr_0.65Ti_0.35)O₃ (PLZT 8/65/35) relaxor ferroelectrics. For PMN, relaxation times on the order of seconds contribute to the dispersive character of the dielectric properties. A defect-relaxation mechanism that involves Mg cation hopping in a structure that is composed of interpenetrating 〈111〉 chains of ordered Pb(Mg_1/2Nb_1/2)O₃ is proposed for PMN. Motion of the Mg cations results in destruction and reconstruction of these ordered chains, which contributes to the dispersive character of PMN.     

Low-Temperature Densification of Lead Zirconate-Titanate with Vanadium Pentoxide Additive

Additions of 0.1 to 6.0 wt% V₂O, to lead zirconate titanate (PZT) ceramics promoted rapid densification below 975°C, thereby eliminating the need for PbO atmosphere control The base PZT, Pb(Zr_0.53Ti_0.47)O₃, was prepared by coprecipitation from mixed oxides and butoxides. The V₂O₅ was incorporated as a batch addition during the PZT coprecipitation process, as mill additions to the calcined precipitated powder, and to a commercial PZT powder. Densification rates were enhanced by the addition of V₂O₅ (>98% of theoretical density was obtained in ∼15 min at 960°C by the addition of 0.1 to 1.0 wt% V₂O₅, compared to 4 h at 1280°C for the base PZT). Dielectric properties and piezoelectric coefficients varied slightly within the optimum range of 0.25 to 1.0 wt% V₂O₅ addition but were at least comparable to the base PZT. Indications are that V₂O₅ becomes incorporated into the surface layers of the oxide powders during mixing (or in the coprecipitation process) and that the accelerated densification is due to enhanced surface activation and liquid-phase sintering.