改进溶胶-凝胶法制备PZT50/50铁电薄膜

采用改进的溶胶凝胶法在Ｐｔ／Ｔｉ／ＳｉＯ２／Ｓｉ衬底上制备了ＰＺＴ５０／５０铁电薄膜，用Ｘ射线衍射表征了薄膜的物相，用原子力显微镜（ＡＦＭ）表征薄膜的微观形貌，用ＲＴ６６Ａ测量了薄膜的铁电特性，获得了具有优良的铁电性能的晶粒尺寸为１００ｎｍ的ＰＺＴ５０／５０铁电薄膜，在２０Ｖ电压下，Ｐｒ＝３１．８３μＣ／ｃｍ２。     

Preparation and characterization of sol-gel derived copper-strontium-oxide thin films

P-type transparent conductive oxides have potential applications in photovoltaics, transparent electronics, and organic optoelectronics. In this paper, results are presented on the synthesis of Cu₂SrO₂ thin films, a p-type transparent conducting oxide by a sol-gel route. Cu(II)methoxide and Sr-metal dissolved in anhydrous isopropanol were used as precursor for the sol preparation. For potassium (K) doping, K-acetate dissolved in anhydrous isopropanol was used as the precursor. Films were spin-coated onto substrates and partially pyrolysed in air at 225°C. After partial pyrolization, a two stage annealing sequence was used to achieve the final film microstructure and composition. Although combinations of oxygen pressure, annealing time, and annealing temperature were used to obtain phase pure Cu₂SrO₂ thin films, X-ray diffraction consistently showed the presence of Cu₂O as a second phase with Cu₂SrO₂−the desired phase. Microstructural studies showed similar phase separation in the films and confirmed the microcrystalline nature. The best conductivities obtained for the undoped and 1% K-doped films were 2 × 10^− 3 and 1.2 × 10^− 2 S/cm, respectively. Both films showed a broad optical absorption edge in the visible range.     

Surface characterization of sol-gel derived indium tin oxide films on glass

Indium tin oxide (ITO) films containing different In : Sn atomic ratios, viz. 90 :10, 70 :30, 50 : 50, 30 :70, were deposited on two types of glass substrates by sol-gel spinning technique. XPS analysis of the films was done under as-received and after-sputtering conditions. The narrow spectra obtained for the Na1s, In3d, Sn3d and O1s have been discussed. Oxygen was found to exist in three chemical environments in as-received samples due to the existence of (i) environmental hydroxyl (-OH) group, (ii) crystalline ITO and (iii) amorphous ITO; but it was in two chemical environments, (ii) and (iii), after surface cleaning by sputtering. The presence of both tin metal and tin oxides was confirmed by the peak analysis of Sn3d. The In : Sn atomic ratio taken in the precursor sols did not change considerably in the case of developed films of low Sn content, but considerable change was observed in the films having high Sn content.     

Sol-Gel法制备PZT铁电薄膜新进展

从底电极的选择、过渡层的引入、外延膜的生长、取代阳离子的改性四个方面介绍了Sol-Gel法制备PZT铁电薄膜的研究进展,简述了PZT的Sol-Gel机理研究现状和引起PZT铁电薄膜极化疲劳的原因,分析了Sol-Gel法制备PZT铁电薄膜研究中存在的问题,并提出展望。     

Characteristics of sol-gel derived PZT thin films with lead oxide cover layers and lead titanate interlayers

The sol-gel derived PbZr_0.53Ti_0.47O₃ (PZT) films were fabricated on the bare Pt/Ti/SiO₂/Si substrates or the same substrates coated by the PbTiO₃ (PT) interlayers. The post-deposition annealing temperature and time were optimized when the PbO cover layers and PbO vapour-containing atmosphere were compared with each other and adopted as the method to diminish the lead-loss problem during the high-temperature post-deposition annealing. The X-ray diffraction patterns, microstructures, and electrical properties such as relative permittivity, _r, remanent polarization, P _r, and coercive electrical field, E _c, were investigated in relation to the annealing conditions. The PZT films deposited on the bare Pt/Ti/SiO₂/Si substrates under the PbO vapour-containing atmosphere showed better electrical properties. This indicates that the PbO vapour-containing atmosphere may be the better method of lead-loss-prevention to process the lead-containing films rather than the PbO cover layer method. The electrical characteristics of the PZT films, _r=1150, a dissipation factor of 0.039, P _r=26 C cm^–2, and E _c=40.5 kV cm^–1 were measured at 1 kHz. When PZT films were deposited on substrates coated by the PT layers, PZT-PT films with single perovskite phase were derived by post-deposition annealing at 500 °C for 1 h. However, the relative electrical properties are very poor, i.e. E _r=160, P _r=2.0 C cm^–2 and E _c=75 kVcm^–1. The optimum combination for preparing PZT-PT films is a 40 nm PbTiO₃ interlayer and annealing conditions of 6 h at 550 °C in a PbO vapour-containing atmosphere; the derived films exhibit electrical properties of E _r=885, P _r=21.5 C cm^–2 and E _c=64 kV cm^–1. The combination of inserting a PT interlayer and annealing in a PbO vapour-containing atmosphere can prevent the formation of electrical short paths. In this case, nearly pin-hole-free PZT films can be grown on the PT (interlayer) /Pt/Ti/SiO₂/Si substrates. It is believed that it is possible to prepare the PZT films with nano-scale uniformity, reproducible quality, which may be worth considering for commercial applications.     

Microstructure of sol-gel derived corundum containing coatings

Up to ∼ 3 μm thick alumina coatings on corundum ceramic, soda-lime-silica glass and Inconel718™ were produced from mixtures of boehmite sols and corundum suspensions.Transmission electron micrographs in combination with electron diffraction and energy dispersive X-ray spectroscopy served to identify crystallographic phases and to characterize the microstructure of the coatings. Using corundum ceramic as substrate the initially deposited boehmite transforms via transition aluminas to corundum while heating to 1200 °C. In the cases of glass and Inconel718™ thermal treatments up to 520 °C and 1100 °C, respectively, cause diffusion of ions from the substrates into the coatings. Thus additional oxide phases were formed.All coatings are free of cracks or delaminations and do not show any directed crystal growth.     

Fabrication and characterization of micromachined high-frequency tonpilz transducers derived by PZT thick films

Miniaturized tonpilz transducers are potentially useful for ultrasonic imaging in the 10 to 100 MHz frequency range due to their higher efficiency and output capabilities. In this work, 4 to 10-microm thick piezoelectric thin films were used as the active element in the construction of miniaturized tonpilz structures. The tonpilz stack consisted of silver/lead zirconate titanate (PZT)/lanthanum nickelate (LaNiO3)/silicon on insulator (SOI) substrates. First, conductive LaNiO3 thin films, approximately 300 nm in thickness, were grown on SOI substrates by a metalorganic decomposition (MOD) method. The room temperature resistivity of the LaNiO3 was 6.5 x 10(-6) omega x m. Randomly oriented PZT (52/48) films up to 7-microm thick were then deposited using a sol-gel process on the LaNiO3-coated SOI substrates. The PZT films with LaNiO3 bottom electrodes showed good dielectric and ferroelectric properties. The relative dielectric permittivity (at 1 kHz) was about 1030. The remanent polarization of PZT films was larger than 26 microC/cm2. The effective transverse piezoelectric e31,f coefficient of PZT thick films was about -6.5 C/m2 when poled at -75 kV/cm for 15 minutes at room temperature. Enhanced piezoelectric properties were obtained on poling the PZT films at higher temperatures. A silver layer about 40-microm thick was prepared by silver powder dispersed in epoxy and deposited onto the PZT film to form the tail mass of the tonpilz structure. The top layers of this wafer were subsequently diced with a saw, and the structure was bonded to a second wafer. The original silicon carrier wafer was polished and etched using a Xenon difluoride (XeF2) etching system. The resulting structures showed good piezoelectric activity. This process flow should enable integration of the piezoelectric elements with drive/receive electronics.     

Drying temperature effects on microstructure, electrical properties and electro-optic coefficients of sol-gel derived PZT thin films

Transparent lead zirconium titanate (PZT) thin film is suitable for a variety of electro-optic application, and the increasing of the electro-optic coefficient of PZT film is one of the important factors for this application. In this study, the main processing variable for improving an electro-optic coefficient was the drying temperature: 300, 350, 450 and 500°C in sol-gel derived PZT thin films. The highest linear electro-optic coefficient (1.65×10⁻¹⁰ (m/V)) was observed in PZT film dried at 450°C. The PZT film showed the highest perovskite content, polarization (P_max=49.58 μC/cm², P_r=24.8 μC/cm²) and dielectric constant (532). A new two-beam polarization (TBP) interferometer with a reflection configuration was used for electro-optic testing of PZT thin films which allows measurement of the linear electro-optic coefficient of thin film with strong Fabry–Perot (FP) effect usually present in PZT thin film.     

Optical and microstructural characterization of sol/gel derived cerium-doped PZT thin films

Optical properties of cerium-doped PZT thin films on sapphire prepared by a sol-gel technique are investigated using both transmission and reflection spectra in the wavelength range 200 to 900 nm. The refractive index, extinction coefficient and thickness of the film are determined from the measured transmission spectra. The packing density of the film is calculated from its refractive index using the effective medium approximation (EMA), and average oscillator strength and wavelength are estimated using a Sellmeir-type dispersion equation. Absorption coefficient (α) and the band gap energy (E_g) of each film composition are also calculated. Possible correlations of microstructure and phase formation behaviour with changes in band gap energy and other optical properties are discussed. This revised version was published online in November 2006 with corrections to the Cover Date.     

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.     

SO1-Gel法硅基PZT铁电薄膜研究

介绍了以硝酸锆、醋本以铅和钛酸四丁酯为原料用溶胶－凝胶（sol-gel）方法在硅衬底上制备Pb（Zr0.53Ti0.47)O3(PZT)铁电膜的工艺流程。对铁电薄膜的表面形貌、晶化程度、界面状态等性质进行了分析,结果表明硅基PZT薄膜形成了良好的钙伏矿结构,并在此基础上实现了制备PZT铁电薄膜的低温改进工艺。     

The effects of the PbO content and seeding layers upon the microstructure and orientation of sol-gel derived PZT films

This paper systematically studied the factors including Pb content of precursor, PT seeding layer and TiO₂ and ZrO₂ seeding layers, which influence greatly the crystal orientation of lead zirconate titanate (PZT, Zr/Ti = 52/48) thin films fabricated by a sol-gel process. We find that the PZT films deposited by precursor with 20% mole excess Pb displayed strong (111) preferred orientation, with 5% mole excess Pb showed a little (100) orientation and pyrochlore phase. PT seeding layer was found prompting the PZT films phase transformation with (110) preferred orientation. In addition, the results show that the TiO₂ and ZrO₂ seeding layers had totally different effects on the preferred orientation of PZT films. The films with TiO₂ seeding layer were highly (111) oriented and exhibited better ferroeletric properties (remnant polarization Pr = 14.2 μC⋅ cm⁻², coercive field Ec = 59.1 Kvcm⁻¹) than those of the films with ZrO₂ seeding layer shown (100) orientation (Pr = 7.4 μC⋅cm⁻², Ec = 42.9 Kvcm⁻¹).     

Microstructure of sol-gel derived TiO2 thin films characterized by atmospheric ellipsometric porosimetry

Adsorption of water vapor during ellipsometric measurements was performed in-situ for the characterization of sol-gel derived TiO₂ thin films. The data obtained were compared with complementary results derived from scanning electron microscopy and photocatalytic degradation measurements. Results indicate that a less permeable surface layer encapsulates the porous interior of the films which may become more accessible by defects such as cracks. Atmospheric ellipsometric porosimetry provides a valuable tool for the microstructural characterization of sol-gel films.     

Microstructural evolution of sol-gel derived ZnO thin films

Zinc oxide thin films, with thicknesses between ∼ 20 and 450 nm, were prepared by spin-coating a sol-gel precursor solution (zinc acetate dihydrate and monoethanolamine in an isopropanol solvent) onto glass substrates, followed by heat treatment at temperatures through 773 K. At 298 and 373 K, the films exhibited the structure of a lamellar ZnO precursor, Layered Basic Zinc Acetate (LBZA). At higher temperatures, LBZA released intercalated water and acetate groups and dehydroxylated to form zinc oxide nanograins with wurtzite structure, which were preferentially oriented in the c-axis direction. Both the degree of the films' c-axis orientation and the topography of their surfaces varied with heat treatment and precursor concentration. For films calcined at 773 K, a minimum of micron-scale surface wrinkles coincided with a maximum in c-axis preference at intermediate concentrations, suggesting that release of mechanical stress during densification of thicker films may have disrupted the ordering process that occurs during heat treatment.     

Crystallization kinetics of sol-gel derived hydroxyapatite thin films

The crystallization kinetics of sol-gel derived hydroxyapatite (HA) and tricalcium phosphate (TCP) thin films were studied to determine whether viscous sintering could be used for densification. The films were approximately 900 nm thick, and were synthesized and processed on silicon substrates. The films were fired in air in a rapid thermal annealer (RTA) for various times and the degree of crystallinity was determined by measuring the intensity of characteristic X-ray diffraction lines. The growth kinetics of HA and TCP were measured between 420 and 550 °C, and between 840 and 920 °C, respectively. Films that were subjected to an accelerated aging step before firing, exhibited a significantly lower crystallization growth rate when compared to unaged films. The aged films also became harder, as measured by nanoindentation. At temperatures above 840 °C, HA transformed into both -and -TCP, with the form being dominant at lower temperatures. The activation energies for both transformations (amorphous film to HA, and HA to TCP) were determined, as were the constants for the Avrami equation. Based on the rapid crystallization kinetics observed for the amorphous film to HA transformation, densification through viscous sintering is essentially precluded in this system. © 2001 Kluwer Academic Publishers     

Low-temperature processing and characterization of single-phase PZT powders by sol-gel method

A new sol-gel system using acetoin was developed and employed for the fabrication of PZT powders and films with compositions near the morphotropic phase boundary Pb(Zr_0.52Ti_0.48)O₃. Acetoin was used as chelating agent to replace the highly toxic methoxyethanol used in previous formulations. This route simplified the chemical processing of PZT-based solutions. Powders were completely crystallized by about 450 °C and contained the ferroelectric perovskite single phase. The firing temperature and time were to be the most important variables. Metallic lead formed only when excess Pb was incorporated. The precursor and the heat-treated powders have been characterized by using thermal analysis and X-ray diffractometry (XRD) studies. The average particle size, as measured from X-ray line broadening, was ∼35 nm.     

Microstructure and gas-sensing properties of sol-gel ZnO thin films

The paper presents the properties of zinc oxide thin films deposited on glass substrate via dip-coating technique. Zinc acetate dehydrate, ethanol and monoethanol amine were used as starting materials and N₂ gas was used as thermal annealing atmosphere for film crystallization. The effect of withdrawal speed on the crystalline structure, morphology, zinc and nitrogen chemical states, optical, electrical and gas-sensing properties of the thin films has been investigated using X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, optical transmittance and photoreduction-ozone reoxidation data.     

Preparation and characterization of ultra-thin sol-gel films

The formation and characterization of nanometer thick sol-gel films are reported. The films were prepared by spin-coating of a diluted solution of a silane precursor on a number of different substrates. The effect of dilution, rotation speed and nature of substrate on the thickness and homogeneity of the films was examined. Characterization of the films was carried out by profilometry, reflectance spectroscopy, atomic force microscopy, adhesion test and electrochemistry. We find that the dilution factor has a pronounced effect on the film thickness. Moreover, the time of dilution, namely, whether dilution was carried out before or after a period of hydrolysis, has a noticeable effect on the thickness as well as on the permeability of embedded species.