Densification and electrical properties of solution coated lead zirconate titanate thick films

Ferroelectric Pb(Zr_0.7Ti_0.3)O₃ (PZT(70/30)) powder was prepared by a sol-gel method and PZT thick films were fabricated by the screen-printing method on the alumina substrates. A concentration of a coating solution was 0.5, 1.0 mol/L and the number of coating was repeated from 0-6. The thickness of the all PZT thick films was about 60 μm. All PZT multilayered thick films showed the XRD patterns of typical peroveskite polycrystalline structure. The relative dielectric constant of the 0.5 M coated PZT-6 (6-number of sol coatings) and 1.0 M coated PZT-6 thick films were 540 and 656.2, respectively. The dielectric loss of the 0.5 M coated PZT-6 and 1.0 M coated PZT-6 thick films were 3.2% and 2.7%, respectively.     

Thickness and erbium doping effects on the electrical properties of lead zirconate titanate thin films

Thin films of erbium doped lead zirconate titanate (PZT) of different thickness were deposited by sol–gel technique on Pt/TiO₂/SiO₂/Si substrates. Capacitance–voltage measurements show that the dielectric constant continuously increases with the thickness. This is interpreted in terms of effects due to a low permittivity interfacial layer in series with the ferroelectric bulk. The linear fit of the reciprocal of capacitance vs. thickness leads to a true dielectric constant of the ferroelectric of 774 and interfacial capacitance of 14.6 nF. The leakage current properties also depend on thickness and temperature. The calculated interfacial potential barrier height amounts to 0.81 and 0.74 eV, respectively for erbium doped and pure PZT thin 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.     

Fabrication and electrical properties of lead zirconate titanate thick films using a new sol-gel processing technique

Lead zirconate titanate (Pb ( , PZT) ferroelectric films 2–60 m in thickness have been successfully fabricated on Pt-coated oxidized Si substrates by a new sol-gel-based process. The films are a 0-3 ceramic–ceramic composite formed by dispersing ceramic powders in a sol-gel solution. The precursor solution for spin coating was prepared from lead acetate, tetrabutyl titanate, and zirconium nitrate. The microstructure and morphology of the prepared PZT thick films were investigated via X-ray diffractometry (XRD) and scanning electron microscopy techniques. XRD analysis shows that the thick films possess single-phase perovskite-type structure, no pyrochlore phase exists in thick films, and SEM micrographs suggest that the PZT thick films were uniform, dense, and crack free. A dielectric constant of 860, loss tangent of 0.03, remanent polarization of , and a coercive field of were measured on 50 m thick films.     

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.     

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.     

Densification, crystallization, and electrical properties of lead zirconate titanate glass-ceramics

Piezoelectric glass-ceramics in the lead zirconate titanato-lead silicate system were developed. SiO(2) was required for glass formability, and excess PbO allowed low temperature processing. The amounts of those constituents were limited by the optimization of the piezoelectric properties. Only a small region of compositions in this system yielded the desired combination of glass formability, crystallization and densification behavior, and resulting piezoelectric properties. Selected compositions were melted and roller quenched to form glass ribbon, then milled into glass powder. Pressed glass powder densified to closed porosity at 850 degrees C with piezoelectric d(33 ) and g(33) coefficients of 26 pC/N and 33x10(-3 ) Vm/N. The low temperature sintering behavior of these ferroelectric glass-ceramics provides the possibility of incorporating a piezoelectric material as a sensor or actuator in thick film circuits or low-fire multilayer packages.     

Improvement electrical properties of sol–gel derived lead zirconate titanate thick films for ultrasonic transducer application

In this work, a fabrication process of piezoelectric PZT [Pb(Zr_0.52Ti_0.48)O₃] thick films up to 60 μm deposited on silicon and aluminum substrates is reported. Crystalline spherical modified PZT powder about 300 nm in diameter was used as filler. PZT polymeric precursor produced by Chemat Inc. was used as the matrix material. Spinning films were annealed at 700 °C for one hour in the furnace in air. The thickness of the thick films was measured using a scanning electron microscope (SEM). Compared with previous piezoelectric PZT composite films, the modified piezoelectric thick films exhibit better dielectric properties. The dielectric constant is over 780 and dielectric loss is 0.04 at 1 KHz. Using a PiezoCAD model, the high frequency transducer was designed and fabricated. It showed a bandwidth of 75% at 40 MHz.     

不锈钢衬底上锆钛酸铅膜的制备

以改性二氧化锆为过渡层,用溶胶－凝胶法在不锈钢衬底上成功制备了锆钛比为52／48的锆钛酸铅膜,扫描电镜分析表明,膜的表面平整,无裂纹,X射线分析结果说明,经650℃退火30min后,膜为纯的钙钛矿相,以衬底为下电极、直径为0.32mm的金上电极,测量了0.8μm膜的电滞回线及其它性能,膜的剩余极化为18μC/cm^2。     

Improved fatigue properties of lead zirconate titanate films made on oxygen-implanted platinum electrodes

Pb(Zr_0.3Ti_0.7)O₃ (PZT) thin film capacitors fabricated on an oxygen-implanted Pt bottom electrode were studied. Oxygen was implanted at a low acceleration voltage (40 kV) and dose (1×10¹⁵ cm⁻²). Structural examination by grazing-incident X-ray diffraction (GIXD) and chemical analysis by X-ray photoelectron spectroscopy (XPS) revealed that the implantation generated a very thin amorphous top surface layer (approx. 20 nm), which contained approximately 7% of oxygen that stayed in the film in the form of PtO bonding. The amorphous layer, however, resumed the crystalline structure accompanied by the dissociation of PtO under the rapid thermal annealing at 600 °C for 5 min. The remnant polarization of sol–gel derived Pb(Zr_0.3Ti_0.7)O₃ (PZT) films fabricated on the oxygen-implanted Pt was slightly reduced from 11.92 μC/cm² for the PZT capacitors fabricated on a Pt electrode without implanted oxygen to 9.07 μC/cm². Nevertheless, the fatigue endurance was significantly increased. The switching polarization of PtO_x/PZT/Pt (O-implanted) capacitors remained within 95% of the starting value after 4×10¹⁰ switching cycles, which is comparable to that of PZT capacitors made with other conducting oxides.     

Improved dielectric properties of lead lanthanum zirconate titanate thin films on copper substrates

Thin films of lead lanthanum zirconate titanate (PLZT) were directly deposited on copper substrates by chemical solution deposition and crystallized at temperatures of ~ 650 °C under low oxygen partial pressure (pO₂) to create film-on-foil capacitor sheets. The dielectric properties of the capacitors formed have much improved dielectric properties compared to those reported previously. The key to the enhanced properties is a reduction in the time that the film is exposed to lower pO₂ by employing a direct insertion strategy to crystallize the films together with the solution chemistry employed. Films exhibited well-saturated hysteresis loops with remanent polarization of ~ 20 μC/cm², dielectric constant of > 1100, and dielectric loss of < 0.07. Energy densities of ~ 32 J/cm³ were obtained at a field of ~ 1.9 MV/cm on a ~ 1 μm thick film with 250 μm Pt electrodes.     

Ultra-thin and isolated dots in polycrystalline lead zirconate titanate films

Size effects with critical thickness or minimum volume for ferroelectricity are of importance in the application of polycrystalline PZT thin films as future memory devices and as storage media. Isolated dots of perovskite phases in the matrix of pyrochlore were synthesized by isothermal annealing through transformation from amorphous to perovskite. Control of the transformation kinetics allows us to produce the isolated ferroelectric dots with a diameter of 50 nm. Domain structure of the isolated dots is also studied by piezoresponse force microscopy. As prepared, all isolated dots contain perpendicularly polarized monodomains. Domain structures and switching behaviors of the isolated dots are similar to those of the single crystalline PZT films. Polycrystalline PZT films with a thickness of 50 nm were also investigated. They show excellent piezoresponse properties and switching behaviors. Ultra-thin polycrystalline PZT films can play a major role in the application of future ferroelectric memories and field-effect transistors as well as for storage media using the local probe technique.     

Effect of calcining temperature on microstructures and electrical properties in modified lead zirconate titanate ceramics

The effect of calcining temperature on microstructures and electrical properties of modified lead zirconate titanate ceramics has been investigated. Specimens of the modified lead zirconate titanate ceramics, formed with different powders calcined over the temperature range from 800 to 950 °C, were prepared by roll forming process. It is observed that the calcining temperature of the powders alters the grain size, which, in turn, modifies the electrical properties of the ceramics. The results also show that dielectric constant, saturated polarization and piezoelectric coefficient tend to increase with increasing calcining temperature up to 900 °C and then to sharply decrease. The best electrical properties were obtained from the samples with the calcining temperature of 900 °C. At the lower calcining temperatures, a small PbO excess seems to result in PbO-rich grain boundaries and anomalous grain growth during sintering process. In addition, when the calcining temperature was increased to 950 °C, a PbO deficiency appears to take place by breaking up the stoichiometry.     

Piezoelectric and mechanical properties of ceria-doped lead zirconate titanate ceramics

Phases, microstructures and properties of lead-zirconate-titanate (PZT) ceramics with the compositions Pb(Zr_0.535– Ce Ti_0.465) O₃ where =0.0, 0.001, 0.01, 0.02 and 0.05 were studied. Rhombohedral and tetragonal phases were present at =0.0. The amount of the rhombohedral phase increased with increasing , and only the tetragonal phase was present for >0.001. Thec/a ratio of the tetragonal phase also increases with increasing . Particles of CeO₂ were found to be present in compositions with >0.01, indicating that the solubility of CeO₂ is less than 1a/o on the metals basis. The piezoelectric and electromechanical constants achieved maximum values for =0.001. The hardness increased monotonically with increasing . The modulus of rupture and the fracture toughness, however, went through a minimum and both stayed lower than their values for =0.     

Structural and electrical studies of CeO2 modified lead zirconate titanate ceramics

The present study is an investigation of the structural and electrical properties of solid solution processed lead zirconate titanate (PZT) ceramics modified by CeO₂. The PZT composition studied is Pb(Zr_0.535Ti_0.465)O₃ modified with 0.0–0.2 mol % CeO₂. Studies of the loss of lead oxide during sintering have been performed. The lead loss increases with increasing Ce in the sample up to 0.1 mol % Ce and becomes nearly constant on further addition of Ce. The lattice parameters and cell volume of the tetragonal phase of PZT also increase with addition of Ce up to 0.1 mol % Ce. The lead loss and X-ray data indicate that Ce is being reduced to Ce³⁺ and is going onto the A-site of the PZT perovskite system. The study concludes that controlled modification of the MPB composition of PZT using 0.1 mol % CeO₂ results in substantial enhancement of piezoelectric strain coefficients, dielectric constant and electromechanical coupling coefficients.     

Peculiarities of crystallization of thin ferroelectric films of lead zirconate titanate

The thermodynamics of processes involved in the growth and annealing of ferroelectric films of lead zirconate titanate Pb(Ti,Zr)O₃ (PZT) has been studied using the method of synchronous thermal analysis (STA). Thin PZT films were grown by the RF magnetron sputtering and then annealed in air or in an inert gas (argon) at atmospheric pressure and various temperatures within 20–600°C. It was found that the annealing in an oxygen-containing medium (air) is accompanied by changes in the enthalpy and mass of the system, which is due to the interaction with oxygen, while the heat treatment in an inert medium did not lead to any changes in the PZT film. It is established that the observed changes are related to the conversion of lead monoxide into orthoplumbate in the PZT film volume. STA experiments demonstrate that this transformation leads to a significant change in the structure of the ferroelectric film. Based on these data, a mechanism is proposed that accounts for the structural changes involved in the annealing of PZT films.     

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.     

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.