Lead Zirconate Titanate Stable Stock Solution: Characterization and Applications

Lead zirconate titanate (PZT) thin films were prepared by the sol-gel process using acetic acid and 1,2-propanediol as solvents. Acetone was used as final solvent and in this way a stable stock sol (for more than 12 months) was obtained. The PZT sols prepared were reproducible and suitable for the preparation of PZT thin films. To study the sol structure evolution gas chromatography mass spectrum (GC-MS) and Fourier-transform-infrared (FT-IR) spectra were recorded and analyzed on each step of the synthesis. The rheological behavior and the stability of the stock sol were checked using a rheometer. It is observed that the addition of acetone leads to a very stable stock sol. The preliminary investigation of the electric properties of the obtained PZT thin films showed that the crystallized films deposited from a fresh prepared sol and a 12 months aged sol exhibit similar ferroelectric properties and comparable to those reported in the literature.     

XPS Analysis of Lead Zirconate Titanate Thin Films Prepared Via a Sol-Gel Process

The crystalline phase and composition of sol-gel-derived lead zirconate titanate (PbZr _x Ti_{1 – x} O₃, PZT) thin films were determined by an X-ray photoelectron spectroscopic (XPS) data processing technique. As a result, it was proved that existence of the surface layer with several tens nm in thickness, of which the crystalline phase and composition were different from those of the inside of the thin films, was found. The newly developed XPS analytical technique is much applicable for the characterization of PZT thin film surface.     

Study of the Lead Environment in Liquid and As-Dried Precursors of PZ, PT and PZT Thin Films

The environment of lead and zirconium atoms in liquid and as-dried precursors for PbZrO3 (PZ), PbTiO3 (PT) and Pb1.1Zr0.53Ti0.47O3 (PZT) thin film deposition were analyzed by EXAFS. The sols were prepared by 2-methoxyethanol route with lead acetate and lead oxide as lead sources. Pb—O—M (M = Zr and/or Ti, depending on the sol composition) linkages were determined in all sols. The choice of lead source weakly influences the lead environment, and strongly influences that of zirconium in both PZ and PZT sols. By drying lead oxide based sols the Pb–M correlation is moderately reduced in PZ, PT and is strongly reduced in PZT.     

Studies of Lead Zirconate Titanate Sol Ageing Part I: Factors Affecting Particle Growth

The formation and growth of polymeric particles during the hydrolysis and condensation of PbZr_0.3Ti_0.7O₃ (PZT 30/70) precursor solutions have been studied as functions of time by using photon correlation spectroscopy (PCS). Particle shape was deduced by measuring the rheological properties of the sols and was found to remain chain-like during sol ageing. Various factors that affect the ageing of PZT sols have been investigated. Ethylene glycol (EG) was found to greatly accelerate the hydrolysis and condensation of the acid-modified Pb-free Zr/Ti solutions but had little effect on the particle growth for the Pb-containing PZT sols. Temperature and H₂O concentration were found to have major effects on the ageing behaviors. The higher the temperature and H₂O concentration, the higher the particle growth rates and the faster the sol gels.     

Studies of Lead Zirconate Titanate Sol Aging Part II: Particle Growth Mechanisms and Kinetics

The kinetics of particle growth in lead zirconate titanate sol gel precursor solutions has been investigated. It was found that chemical reaction limited aggregation was responsible for most of the sol aging, followed by diffusion limited aggregation in the later stage. At the beginning, particles grow by reaction between initial polymers and particles. As the particle number-density increases, a particle-particle aggregation characterised by an exponential growth law becomes the predominant mechanism. When particles grow larger, towards gel formation, the aggregation changes to diffusion limited. Mathematical models derived according to the above mechanisms agreed well with experimentally measured particle growth profiles.     

Development of nanoscale inhomogeneities during drying of sol-gel derived amorphous lead zirconate titanate precursor thin films

The structural evolution of sol-gel derived lead zirconate titanate (PZT) precursor films during and after physical drying was investigated by transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), selected area electron diffraction (SAED), and time-resolved X-ray diffraction (XRD). Films were deposited from initial 0.3 mol/dm(3) precursor sols with varying hydrolysis ratios. Zr-rich grains of 1-10 nm size, embedded in a Pb-, Zr-, and Ti-containing amorphous matrix were found in as-dried films. The Zr-rich regions were crystalline at hydrolysis ratios [H(2)O]/[PZT] < 27.6, and amorphous at ratios > 100. X-ray diffraction analysis of PZT and zirconia sols revealed that the crystalline nanoparticles in both sols are identical and are probably composed of nanosized zirconium oxoacetate-like clusters. This study demonstrates that time-resolved X-ray diffraction combined with electron energy loss spectroscopy mapping is a powerful tool to monitor the nanoscale structural evolution of sol-gel derived thin films.     

Time-resolved small angle X-ray scattering study of sol-gel precursor solutions of lead zirconate titanate and zirconia

The evolution of nanostructure in sol-gel derived lead zirconate titanate (PZT) and zirconia precursor sols at different hydrolysis ratios was investigated by small angle X-ray scattering (SAXS). The shape of the clusters in the zirconia sol could be described by the length-polydisperse cylindrical form factor. The zirconia-based clusters were characterized by a cross-sectional radius, r(0), of 0.28 nm and a practically monodisperse length of ca. 1.85 nm. These clusters were probably constructed of zirconia-related tetrameric building blocks. Similar cylindrical structural motifs were observed in PZT precursor sols with [H(2)O]/[Zr+Ti]=9.26 and 27.6, but the polydispersity in length was much higher. Clear scattering contributions from Ti and Pb centers were not detected, which was interpreted in terms of a homogeneous distribution of unbound lead ions in solution and the relatively low scattering intensity from any Ti-based clusters or oligomers that may have been present in the sols.     

Pt／Ti／Si3N4／SiO2／Si基底的多层薄膜制备及拉曼研究

选用三水醋酸铅、乙酰基丙酮酸锆、四异丙氧基钛、乙酰丙酮作初始材料,用同样的方法分别制备了锆钛酸铅（PZT）和钛酸铅（PT）两种固体前驱物．采用改良型的溶胶-凝胶工艺技术,分别在不同的Pt-Ti-Si3N4-SiO2-Si基底上,按照不同的组合方式,制备了三种多层薄膜：PZT、PT／PZT—PZT／PT、PT／PZT／-／PZT／PT．较详细地讨论了薄膜制备的工艺技术,发现当凝胶通过烧结和干燥后变成固态物质时,薄膜内部存在着较大的残余应力,当薄膜在600℃下退火时其内部残余应力可以被减小．通过拉曼衍射和XRD分析,发现PT／PZT—PZT／PT结构的薄膜具有较好的结晶性和较小的残余应力．XRD分析表明,多层混合薄膜的衍射峰是PZT和PT两种薄膜衍射峰的叠加．     

Effect of sol-gel preparation method on particle morphology in pure and nanocomposite PZT thin films

Double-scale composite lead zirconate titanate Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films of 360 nm thickness were prepared by a modified composite sol-gel method. PZT films were deposited from both the pure sol and the composite suspension on Pt/Al₂O₃ substrates by the spin-coating method and were sintered at 650°C. The composite suspension formed after ultrasonic mixing of the PZT nanopowder and PZT sol at the powder/sol mass concentration 0.5 g mL⁻¹. PZT nanopowder (≈ 40–70 nm) was prepared using the conventional sol-gel method and calcination at 500°C. Pure PZT sol was prepared by a modified sol-gel method using a propan-1-ol/propane-1,2-diol mixture as a stabilizing solution. X-ray diffraction (XRD) analysis indicated that the thin films possess a single perovskite phase after their sintering at 650°C. The results of scanning electron microscope (SEM), energy-dispersive X-ray (EDX), atomic force microscopy (AFM), and transmission electron microscopy (TEM) analyses confirmed that the roughness of double-scale composite PZT films (≈ 17 nm) was significantly lower than that of PZT films prepared from pure sol (≈ 40 nm). The composite film consisted of nanosized PZT powder uniformly dispersed in the PZT matrix. In the surface micrograph of the film derived from sol, large round perovskite particles (≈ 100 nm) composed of small spherical individual nanoparticles (≈ 60 nm) were observed. The composite PZT film had a higher crystallinity degree and smoother surface morphology with necklace clusters of nanopowder particles in the sol-gel matrix compared to the pure PZT film. Microstructure of the composite PZT film can be characterized by a bimodal particle size distribution containing spherical perovskite particles from added PZT nanopowder and round perovskite particles from the sol-matrix, (≈ 30–50 nm and ≈ 100–120 nm), respectively. Effect of the PZT film preparation method on the morphology of pure and composite PZT thin films deposited on Pt/Al₂O₃ substrates was evaluated.     

聚氨酯与铁电陶瓷粉复合物的电致感应性能研究

利用双辊制备了一系列热塑性弹性体聚氨酯（PU）和铁电钛酸锆酸铅盐（PZT）的电感应PZT／PU复合物。X－衍射和SE镜结果显示,复合物中,在铁电相中PZT陶瓷粉呈现结晶态并且均匀分布在PU基体中,复合物的弹性模量和相对电容率随着复合物中PZT体积分数增加而升高,在高压电场下,低PZT含量的复合物呈现负的电致伸缩应力,当PZT体积分数增加到6％以上时,在某个临界电场下,复合物呈现出电致伸缩应力反转的特性,即电致伸缩应力从负转变为正,并且发生应力反转的临界电场随着复合物中PZT体积分数的增加而降低,PU的电致伸缩特性与PZT在高电场下极化反转效应结合,导致了PZT／PU复合物这种有趣的性能,因此PZT／PU复合物将在高电压场方面作为传感器开关材料得到广泛应用。     

Combinatorial synthesis of thin mixed oxide films and automated study of their piezoelectric properties

The development of an automated production of thin films and the characterization of their piezoelectric properties in high-throughput are described. A library of 50 undoped as well as doped lead zirconate titanate Pb(Zr,Ti)O₃ (PZT) coatings was produced by sol deposition. Afterwards, the piezoelectric properties of the library films were analyzed by automated atomic force microscopy employing the ultrasonic piezo-mode.     

Seeding Effects in the Sol-Gel Preparation of Lead Zirconate Titanate (PZT) Powders

Lead zirconate titanate, Pb(Zr, Ti)O₃ (PZT), crystallizes in a perovskite form from an intermediate pyrochlore phase and the effects of the presence of perovskite seeds have been considered. PZT powders have been obtained from lead acetate and Zr and Ti alkoxides using a sol-gel process involving a chemical modification by acetylacetone. Perovskite seeds have been introduced during the process by means of colloidal suspensions in acetylacetone. The seeding effects have been evidenced from DTA and XRD measurements, the formation temperature of pure perovskite phase being lowered by 50°C with 5 wt% seeds. More dense powder microstructure is observed in presence of seeds. Work performed within the Concerted European Action on Sol-Gel Processing for Advanced Industrial Material Technologies, Contract No. BRE2, CT92.0137.     

Ultra light tunable capacitor based on PZT thin film deposited onto aluminium foil

Lead zirconate titanate (PZT) thin films with a Zr/Ti ratio of 57/43, elaborated by a derived sol–gel process, have been deposited onto bare and RuO₂ coated aluminium substrate 16 μm thick. Commercial aluminium foil presents many advantages as ultra light weight (43 g m^?2), conformability, conduction, can be easily cut, and is one of the cheapest substrates used for PZT thin films deposition (<0.1$ m^-2). XRD measurements have shown a well crystallized PZT in the perovskite structure and ferroelectric behaviour has also been observed. By the use of a RuO₂ film 100 nm thick at the PZT/aluminium interface, the coercive field and tunability values have been strongly improved despite an increase of the dielectric losses. The lead excess introduced in the precursor solution has been increased up to 65 % in order to lower the crystallization temperature of the PZT around 560 °C and tunability has been studied as a function of annealing time and temperature.     

Novel single-source precursors for the fabrication of PbTiO3, PbZrO3 and Pb(Zr(1-x)Ti(x))O3 thin-films by chemical vapor deposition

Lead titanate, lead zirconate, and lead zirconate titanate (PZT) films in the sub-μm-range were produced at temperatures around 400 °C using novel single-source precursors in a classical thermal CVD process. The design of two bimetallic alkoxide compounds, a lead titanate and a lead zirconate source with almost identical physical properties and complement miscibility, resulted in a new quasi-single-source PZT precursor, an azeotropic mixture that evaporates at 30 °C and at a pressure of 4 × 10(-1) mbar. After thermal treatment at 650 °C, transparent (100)-oriented PZT films with remnant polarization of 20 μC cm(-2) and a coercive field strength of 20 V μm(-1) were achieved. An additional lead source is not required.     

An acetic acid/water based sol-gel PZT process II: Formation of a water based solution

The chemical reactions underlying the formation of a water based alkoxide sol gel process for lead zirconate titanate thin films using solutions of Ti and Zr alkoxides are outlined. Titanium isopropoxide and zirconium propoxide are chemically modified by acetic acid in order to use water as a solvent. The nature of the hydrolysis reactions in the presence of acetic acid is reviewed. It is shown that the formation of ions and charged polymeric species reduces their rates of condensation and aggregation.     

Investigation of the Crystallisation Behaviour of Lead Titanate (PT), Lead Zirconate (PZ) and Lead Zirconate Titanate (PZT) by EXAFS-Spectroscopy and X-Ray Diffraction

Two solid solutions of lead zirconium titanates PbZr _x Ti_{1 – x} O₃ (x = 0.1 and 0.35) as well as the reference compounds lead titanate and lead zirconate were prepared from zirconium and titanium n-propoxide, dissolved in 2-methoxyethanol, by sol-gel process. The amorphous products after pyrolysis of the dried gels and the crystalline phases were studied by EXAFS spectroscopy to monitor the structural changes from the amorphous oxide mixture to the crystalline ceramics after calcination. Additionally, the crystalline phases were identified by X-ray diffraction (XRD).It follows from the analysis of the EXAFS data that the local order of the amorphous phases seems to be completely different from that of the crystalline phase. There is no indication of a preformation of the local order of the perovskite structure. The analysis of our EXAFS spectra can be interpreted very consistently with the assumption that in the amorphous samples a segregation exists on molecular level and the low crystallisation temperatures are a consequence of very short diffusion paths.     

Effects of metal salts on the thermal decomposition of edta-gel precursors for ferroelectric ceramic powders

Raw chemicals such as metal nitrates and chlorides were found to affect the thermal decomposition behaviour of EDTA-gel precursors used for the production of ceramic powders. Fine, homogeneous ceramic powders were produced from nitrate solutions while chlorides gave segregated phases. In studies on the production of lead zirconate titanate (PZT) using chlorides, the segregation and loss of lead was observed and shown to be caused by the formation and evaporation of PbCl₂. Thermal analysis (DTA/TG) quantitatively proved the suggested reaction mechanism for this phase segregation. Crystallization of the desired perovskite phase of lead zirconate titanate (PZT) and barium titanate (BT) initiated at temperatures as low as 250°C in the nitrate-EDTA precursors. Water of crystallization and formation of BaCO₃ in the barium titanate precursor were suggested to account for differences in the observed decompositional behaviours of the BT and PZT precursors.     

Influence of the Structure of Precursors on the Crystallization of PbTiO3 Thin Films

PbTiO₃ (PT) thin films and their respective sols derived from three lead sources have been studied in order to elucidate the role of the starting materials in the crystallization of the products. EXAFS analysis of sols revealed similar oligomeric Ti-units in PT precursors derived from lead oxide or lead 2-methoxyethoxide acetate and a significantly different local Ti neighborhood in those derived from lead acetate. Structural details of the perovskite phase in the thin films follow the same pattern of similarity.     

SiO2 溶胶及其静电自组装薄膜的制备

Silica sols were prepared by hydrolysis of Si（OC2H5）4（TEOS）using HCl,NH3·H2O,HCl/NH3·H2O as catalyzers,and the different granularities of SiO2 sols which catalyzed by HCl first and then NH3·H2O have the same terminal pH value were prepared. The silica colloidal particles were investigated with Transmission Electron Microscope（TEM）. The results showed sol catalyzed by HCl possesses very little particle,catalyzed by NH3·H2O has particle configuration,catalyzed by HCl/NH3·H2O possesses consecutive configuration. Poly（diallyldimethylammonium chloride）（PDDA）and SiO2 nanoparticulate complex thin films were prepared by electrostatic self-assembly multiplayer（ESAM）method. After assembling films,thin films surface conformation was observed with Electron Microscope and their transmittance was tested with 721 Spectrophotometer. The results showed that the silica sol catalyzed with HCl is not good for the fabrication of ESAM films and the silica sol catalyzed with HCl first and then NH3·H2O or by NH3·H2O only are very suitable for ESAM film fabrication. TEM data indicate that the microstructure of PDDA/ SiO2 prepared from silica sol catalyzed with HCl first and then NH3·H2O is consecutive and that the microstructure of PDDA/ SiO2 prepared from silica sol catalyzed by NH3·H2O only is particulate-parking like. The dependence of the transmittance of assembled films on the bilayer number of the films and the anti-scratching properties of the films were investigated. The results show that PDDA/ SiO2 films prepared from silica sol catalyzed by NH3·H2O only possess higher transmittance but lower anti-scratching properties. The effect of granularity of sols on optical performances of the thin films was studied,results showed the less the granularity of sol,the better the optical performances. For the sake of improving the light transmittance of films,we can reduce the granularity of sol,but it may play down its mechanical damage resist intensity.     

Morphology of RuO2-TiO2 coatings and TEM characterization of oxide sols used for their preparation

Characterization of RuO(2) and TiO(2) sols of different aging times, obtained by forced hydrolysis of appropriate chloride salts, was performed by transmission electron microscopy (TEM). The aging time of TiO(2) sols was observed to affect the size of particles as well as the crystallinity of the solid phase of the sols. The surface morphology of RuO(2)-TiO(2) coatings on titanium, obtained by the sol-gel procedure using TiO(2) sols of different aging times and RuO(2) sol of fixed aging time, was investigated by scanning tunneling microscopy (STM) at three different scan sizes. The STM data indicated uniform microdistribution of the coating material (small microroughness) and an increase in nanoroughness with the aging time of the TiO(2) sol. The observed increase in real coating surface area with increasing TiO(2) particle size confirms the earlier cyclic voltammetry results.