A modified two-stage mixed oxide synthetic route to lead zirconate titanate powders

An approach to synthesis lead zirconate titanate [Pb(Zr_1−xTi_x)O₃; PZT] powders with a modified two-stage mixed oxide synthetic route has been developed. To ensure a single-phase perovskite formation, an intermediate phase of zirconium titanate (ZrTiO₄) was employed as starting precursor. The formation of perovskite phase in the calcined PZT powder has been investigated as a function of calcination temperature, soaking time and heating/cooling rates by differential thermal analysis (DTA) and X-ray diffraction (XRD) techniques. The morphology evolution was determined by scanning electron microscopy (SEM) technique. It has been found that the unreacted PbO and ZrTiO₄ phases tend to form together with PZT, with the latter appearing in both tetragonal and rhombohedral phases, depending on calcination conditions. It is seen that optimisation of calcination conditions can lead to a 100% yield of PZT in a tetragonal phase.     

Pb(Zr0.5, Ti0.5)O3 nanofibres by electrospinning

Lead zirconate titanate Pb(Zr_0.5, Ti_0.5)O₃ nanofibres with diameters ranging from 200–300 nm have been synthesized by calcination of the electrospun lead zirconate titanate/polyvinyl acetate composite fibres. The morphology and crystalline phase features of these lead zirconate titanate (PZT) nanofibres have been studied by various physico-chemical methods such as SEM, AFM, XRD and FT–IR. The formation of perovskite PZT phase was observed at temperatures as low as 550 °C.     

Direct precipitation of lead zirconate titanate by the hydrothermal method

Direct precipitation of fine powders of lead zirconate titanate (PZT) in the complete range of solid solution, is investigated under hydrothermal conditions, starting from lead oxide and titania/zirconia mixed gels. The perovskite phase is formed in the temperature range of 165 – 340°C. Sequence of the hydrothermal reactions is studied by identifying the intermediate phases. The initial formation of PbO: TiO₂ solid solution is followed by the reaction of the same with the remaining mixed gels giving rise to X-ray amorphous PZT phase. Further, through crystallite growth, the X-ray crystalline PZT is formed. This method can be extended for the preparation of PLZT powder as well. The resulting powders are sinterable to high density ceramics.     

Effect of microwave annealing temperatures on lead zirconate titanate thin films

Lead zirconate titanate (Pb(1.1)(Zr(0.52)Ti(0.48))O(3)) thin films of thickness 260?nm on Pt/Ti/SiO(2)/Si substrates were densified by 2.45?GHz microwave annealing. The PZT thin films were annealed at various annealing temperatures from 400 to 700?°C for 30?min. X-ray diffraction showed that the pyrochlore phase was transformed to the perovskite phase at 450?°C and the film was fully crystallized. The secondary (again pyrochlore) phase was observed in the PZT thin films, which were annealed above 550?°C. The surface morphologies were changed above 550?°C of the PZT thin films due to the secondary phase. Higher dielectric constant (ε(r)) and lower dielectric loss coercive field (E(c)) were achieved for the 450?°C film than for the other annealed films.     

Dip-coating conditions and modifications of lead titanate and lead zirconate titanate films

The modifications of dip-coated lead titanate (PT) and lead zirconate titanate (PZT) films strongly depend on the film thickness and the substrate in addition to the heat-treatment temperature. At 500 to 600 ° C, metastable paraelectric pyrochlore grew on glass plates (amorphous plates) when the thickness of the coated films produced by one coating cycle was below 100 nm, while ferroelectric perovskite formed on crystalline substrates or when thick films were coated on amorphous plates. This tendency is discussed in terms of an inhomogeneous reaction and the epitaxial effect. The perovskite PT films coated on single-crystal SrTiO₃ plate at 700 ° C were strongly oriented to thec-axis.     

Seeding effects on crystallization and microstructure of sol-gel derived PZT fibers

Dense and fine micro-structured lead zirconate titanate (PZT) fibers were successfully fabricated by sol-gel process from lead acetate dehydrate, zirconium normal butoxide, and titanium isopropoxide. An addition of perovskite seed particles (2 wt%) can lower the formation temperature of the perovskite phase and a single-phase perovskite PZT fiber can be obtained by heat-treating the precursor fiber at 500°C. Crystallization of perovskite phase was improved with the seed content. The diffraction peaks of (200) and (002) in the PZT fiber with 6 wt% seed was better split than in the PZT fiber without seed, which indicates that the tetragonality of PZT fiber was increased by adding seed particles. Seed particles also affected microstructure development of the PZT fibers.     

Dielectric properties of lead zirconate titanate thin films seeded with barium strontium titanate nanoparticles

A low temperature synthetic method recently proposed by the authors was applied to the fabrication of lead zirconate titanate (PZT) thin films containing crystalline seeds of barium strontium titanate (BST) nanoparticles. PZT precursor and the BST particles were prepared with complex alkoxide methods. Precursor solution suspending the BST particles was spin-coated on Pt/Ti/SiO₂/Si substrate to film thickness of 500–800 nm at particle concentrations of 0–25.1 mol%, and annealed at various temperatures. Seeding of BST particles prevented the formation of pyrochlore phases, which appeared at temperatures above 400 °C in unseeded PZT films, and induced crystallization of PZT into perovskite structures at 420 °C, which was more than 100 °C below the crystallization temperature of the unseeded PZT films. Measurement of dielectric properties at 1 kHz showed that the 25.1 mol% BST-seeded PZT films annealed at 450 °C had a dielectric constant as high as 300 with a dissipation factor of 0.05. Leakage current density of the film was less than 1×10⁻⁶ A/cm² at applied electric field from 0 to 64 kV/cm.     

Micropore formation in lead zirconate titanate films

This paper presents an experimental study of the pyrochlore-to-perovskite phase transition in ferroelectric lead zirconate titanate (PZT) films grown on silicon substrates by rf magnetron sputtering and annealed in air or in an inert (argon) atmosphere at temperatures of up to 600°C and atmospheric pressure. Simultaneous thermal analysis results demonstrate that annealing in air leads to release of the latent heat of the phase transition, which is due to the conversion of lead oxide to lead orthoplumbate in the bulk of the PZT film. This transition is accompanied by changes in the densities of the perovskite phase and parent (pyrochlore) phase. In this case, the possibility of phase transformation should be ensured by changes in the volume of the system. The change in the volume of the film leads to the formation of micropores in the bulk of thin PZT films. The micropore size has been determined by scanning electron microscopy, and the phase composition of the films has been assessed by X-ray diffraction. We present experimental evidence that micropore nucleation and growth at the interface between the new and old phases in thin PZT films is due to the difference in density between these phases.     

Electrohydrodynamic deposition of nanostructured lead zirconate titanate

The deposition of a propanol-based lead zirconate titanate (PZT) sol using electrohydrodynamic atomization (EHDA) in the stable cone-jet mode was investigated. The droplets generated were deposited onto a copper substrate as a film, which was investigated using X-ray diffraction and scanning electron microscopy. The PZT film was shown to contain uniform nano-particles of PZT, which maintained their shape on sintering (650 degrees C, 1 hour) while forming the perovskite phase of PZT.     

Fabrication of Lead Zirconate Titanate Powder Using Ultrasonic Ball Milling Technique

In this research, the ultrasonic ball milling technique has been used to fabricate lead zirconate titanate （PZT） ceramics. PZT with the composition nearly the morphotropic phase boundary （MPB） ： Pb（Zr0.52 Ti0.48 ）03 was studied. The effect of milling time on phase formation of sample powder was examined by X-ray diffraction technique （XRD）. Moreover, the physical, dielectric, piezoelectric properties and microstructure of PZT ceramics were investigated. The present results reveal that the ultrasonic ball milling technique results the homogeneous and small size of PZT powder. Furthermore, there is a significantly change occurs in the size of the particles with the short time of milling process.     

Synthesis of nanophase PLZT (12/40/60) powder by PVA-solution technique

The preparation of high purity ultrafine lanthanum modified lead zirconate titanate powder has been explored with polyvinyl alcohol. The precursor and calcined powders were examined by thermal analyzer, powder X-ray diffractometer and infrared spectrophotometer. The morphology and homogeneity of the calcined powders were investigated by transmission electron microscope and energy dispersive X-ray spectroscopic studies. The precursor powder transformed into single phase PLZT after calcination for 1 h at 600 °C having the crystallite size of 10 nm.     

Pb(Zr0.95Ti0.05)O3 powders prepared by aqueous Pechini method using one-step pyrolysis process: characterization and porous ceramics

Zr-riched lead zirconate titanate, Pb(Zr_0.95Ti_0.05)O₃ (PZT 95/5) powders were prepared using lead acetate, zirconium oxynitrate, and titanium sulfate by aqueous Pechini method. The chelation behaviors of metallic ions and citric acid were investigated and the development of the phase formation of perovskite structure was detected. PZT 95/5 powders were obtained directly from the as-synthesized gels by one-step pyrolysis process at 450 °C for 10 h. Perovskite phase was formed at about 450 °C and no distinct intermediates were obtained. There were some carbonates as impurities but they did not affect the formation of the complete perovskite phase of PZT 95/5 ceramics after sintering at 1,100–1,150 °C for 2 h. The decomposition of few organic residues among the one-step pyrolyzed powders could form uniform porous structure and the formation mechanism of porous ceramics was also presented.     

The effect of acetic acid on morphology of PZT nanofibers fabricated by electrospinning

Lead zirconate titanate (PZT)/poly vinyl acetate (PVAc) green nanofibers were spun by electrospinning PZT/PVAc mixture. The acidification (acetic acid) effect of PZT/PVAc solution on the morphology of PZT ceramic fibers calcined at various temperatures was investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) and X-ray diffraction (XRD). The PZT ceramic fibers processed with acetic acid (CH₃COOH) turned out to be thinner and more compact, compared to the fiber without it. It was also evident that there was an optimal concentration of acetic acid for the dense PZT nanofiber. In addition, FTIR and XRD revealed that the complete perovskite formation was achieved by the calcination between 650 °C and 700 °C.     

Synthesis of high surface area ZnO powder by continuous precipitation

Synthesis of high surface area ZnO powder was achieved by continuous precipitation using zinc ions and urea at low temperature of 90 °C. The powder precipitated resulted in high-purity single-phase ZnO powder when calcined at 280 °C for 3 h in air. The solution pH and the precipitation duration strongly affected the surface area of the calcined ZnO powder. Detailed structural characterizations demonstrated that the synthesized ZnO powder were single crystalline with wurtzite hexagonal phase. The powdered samples precipitated by homogeneous precipitation crystallized directly to hydrozincite without any intermediate phase formation.The phase structures, morphologies and properties of the final ZnO powders were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), dynamic light scattering particle size analysis (DLS), and nitrogen physisorption in order to determine the specific surface area (BET) and the pore size distribution (BJH).     

Preparation of lead zirconate titanate thin films with a combination of self-assembly and spin-coating techniques

A low-temperature synthetic method for preparing lead zirconate titanate (PZT) perovskite film on a Pt substrate is proposed. The method consists of the self-assembly of PZT particles on a substrate and successive spin coating with a precursor of PZT. The PZT particles that had sub-micron sizes and perovskite structures were prepared by annealing amorphous PZT particles formed from a complex alkoxide precursor. The PZT particles were deposited on a Pt substrate that was surface-modified with (3-mercaptopropyl) trimethoxysilane to chemically fix the particles on the substrate. Another PZT precursor solution was used for the spin-coating on the PZT-deposited substrate, and then the spin-coated film was annealed at 350 °C to remove organic residues left in the film. The spin-coated PZT film prepared at 350 °C had a dielectric constant of 118 at a frequency of 1000 Hz.     

以Al2O3为过渡层脉冲激光法制备PZT铁电薄膜

为实现PZT铁电薄膜与半导体衬底的直接集成引入Al2O3为过渡层，首先用真空电子束蒸发法在Si(100)，多昌金刚石（111）衬底上生长约20nm厚的Al2O3过渡层，接着在上述衬底上采用脉冲激光淀积（PLD）法淀积PZT薄膜，衬底温度为350-550℃。X光电子能谱（XPS）测试表明，在高真空下，电子束蒸发Al2O3固态源能获得化学配比接近蒸发源的Al2O3薄膜。X射线衍射（XRD）测试说明，不论衬底是硅还是多晶金刚石，当衬底温度为550℃时，PZT在Al2O3过渡层上呈现（222）取向的焦绿石相结构，当衬底是金刚石时，通过如下工艺：（1）较低温度（350℃）淀积；（2）空气氛围650℃快速退火5min，可以在Al2O3过渡层上获得高度（101）取向的钙钛矿结构的铁电相PZT薄膜，最后AFM测试显示，在硅衬底上，PZT薄膜的表面均方根粗糙度为9.78nm；而在多晶金刚石衬底上，PZT薄膜的表面均方根粗糙度为17.2nm。     

Synthesis and characterization of PLZT (10/65/35)

Lead zirconate titanate (PZT) powder of composition Pb(Zr_0.65Ti_0.35)O₃ was modified by incorporation of 10% lanthanum as a supervalent cation by the process of evaporative decomposition of aqueous solutions of lead nitrate, lanthanum nitrate, zirconyl nitrate and tetra-isopropyl titanate. X-ray diffraction patterns and infrared spectra of the compound calcined at different temperatures indicate that formation of rhombohedral PLZT is possible at 550°C for 1 H. The room-temperature dielectric constant measured at 1 kHz was found to be 991. From the study of dielectric constant as a function of temperature,T _c was found to be at 85°C. SEM study of the compound has shown grain-size homogeneity and quality of the compound. All these results suggest that this PLZT powder may be suitable for device applications.     

PZT thin film preparation by pulsed DC magnetron sputtering

Pulsed DC magnetron sputtering was used in this study to prepare lead zirconate titanate (Pb(Zr_xTi_1−x)O₃, PZT) thin films. A single metallic target was used for the deposition onto a Pt/Ti/SiO₂/Si substrate and parameters such as: pulse frequency, duty cycle, O₂/Ar flow ratio controlled so as to analyze the effect of the parameters on thin film deposition rate, crystalline structure and morphology. After the deposition, the thin film was annealed in a rapid thermal annealing (RTA) furnace. The experimental results showed that, when the pulse frequency was in the range of 10 kHz-100 kHz, along with the lowering of frequency and the oxygen argon flow rate ratio, the deposition rate gradually increased and the formation of PZT thin film perovskite phase was enhanced; however, if the oxygen argon flow rate ratio was too high, it caused the PZT thin film to generate a pyrochlore phase. However, when the duty cycle was in the range of 95%-75%, the highest deposition rate and better perovskite phase could be obtained in the range of 75%-80%.     

Synthetic process of the sol–gel derived Pb(Zr0.53Ti0.47)O3 films using poly vinyl butyral binder

Synthetic process of sol–gel grown lead-zirconate-titanate (PZT) films using poly vinyl butyral (PVB) binder has been studied. By the present method, thick PZT films with about 7 μm in thickness were successfully grown, whereas thick films were not achieved without the use of the binder. In the synthetic process, amorphous PZT particles with 0.6–1.0 μm in diameter were formed at a relatively low temperature of 50°C and Pb projections were observed at 300°C. Furthermore, PbO was observed at the surface of amorphous PZT particles at 400°C. At 500°C, PZT perovskite phase started to be observed together with residual PbO phase. Finally, single PZT perovskite phase, which shows the dielectric constant and dissipation factor of 145.5 and 0.032, respectively, at a frequency of 1 kHz, was obtained at 800°C. We suggest that the use of PVB binder plays an important role in the fabrication of thick PZT film.     

Electrodeposition of lead zirconate titanate nanotubes

Lead zirconate titanate (PZT) nanotubes have been grown using porous anodic alumina templates. Sol–gel electrophoretic deposition method was utilized to form the nanotubes on pore walls. The templates were prepared using various anodizing voltages to achieve different pore diameters. Phosphoric acid solution was employed as the electrolyte. Stabilized PZT sols were prepared using lead acetate trihydrate and modified precursors of zirconium and titanium with acetic acid. The filled templates were then sintered at 700 °C. Scanning electron microscopy (SEM) shows that tubular PZT arrays have been efficiently grown in the alumina templates. Transmission electron microscopy (TEM) further confirms the tubular form and polycrystalline nature of the tubes. Energy dispersive X-ray (EDX) analyses also confirm the composition of the tubes. X-ray diffraction (XRD) spectra indicate the presence of the perovskite PZT as the main phase.