溶胶-凝胶法制备SrBi2Ta2O9铁电陶瓷薄膜

溶胶-凝胶法制备SrBi2Ta2O9铁电陶瓷薄膜     

Ferroelectric Properties of (001)- and (106)-Oriented SrBi2Ta2O9 Epitaxial Thin Films

Epitaxially grown SrBi₂Ta₂O₉ (SBT) thin films with (001) and (106) orientations were prepared on La-doped SrTiO₃ (001) and (110) substrates, respectively, by coating-pyrolysis process. When the films were annealed in air, their epitaxy was poor and no significant difference was observed in the P-E characteristics for the films that have different orientations. By contrast, the crystallinity and epitaxy of the films increased with decreasing oxygen partial pressure, p(O₂), of annealing atmosphere. Using these high quality epitaxial films, we observed a distinct difference in P-E hysteresis curves, which reflects the orientation of the films. After postannealing of these films in O₂ to compensate for possible oxygen deficiency, which might have been introduced into the SBT films owing to low p(O₂) annealing, the anisotropy of the ferroelectric response was maintained and almost the same P-E loops were obtained.     

Bi4Ti3O12 Thin Films from Mixed Bismuth-Titanium Alkoxides

Bi₄Ti₃O₁₂ thin films were obtained by the sol-gel method. The precursor solution was prepared by allowing the two metallic alkoxides, Bi(OC₂H₄OCH₃)₃ and Ti(OC₂H₄OCH₃)₄, to react in 2-methoxy-ethanol to form the mixed alkoxide. This stable sol was deposited by spin-coating onto platinized silicon substrates. X-Ray diffraction patterns indicate that the perovskite initial crystallization temperature is 460°C for powder samples and it ranges between 400 and 500°C, for thin films, as a function of the number of coating layers. Dense, smooth and crack free thin films with grain sizes ranging from 20 nm to 500 nm are obtained, depending on the number of coating layers and on the post-deposition temperature annealing.     

Ferroelectric PZT Thin Films by Sol-Gel Deposition

Sol-gel spin coating has a low thermal budget, is cheap compared to vacuum-based techniques and is now routinely used to produce dense, pore-free ferroelectric films. PbZrx Ti(1 – x)O3 (PZT) is utilized in most applications because it has a large remanent polarization, high piezo- and pyroelectric coefficients and optimized electromechanical coupling factors, depending on precise composition. This paper will review some of the principles and applications of PZT films and highlight using transmission electron microscopy some of the basic problems and solutions involved in producing device-quality material on Si-substrates.     

The Sol-Gel Chemistry of Ferroelectric SrBi2Ta2O9 Thin Layers

A characterization of sol-gel precursors of SrBi₂Ta₂O₉ (SBT) has been carried out. Each molecular precursor, [SrBi_2+x Ta₂(OCH₂CH₂OCH₃)₁₈] _n (1) (x = 0.0, 0.2, and 0.4) and [SrTa₂(OEt)(O ⁱ Pr)₁₁( ⁱ PrOH)₂] (2) was prepared from the mixtures of Bi(OR)₃, Sr(OR)₂, and Ta(OR)₅ (R = Et, ⁱ Pr, and CH₂CH₂OCH₃), respectively. ¹H and ¹³C NMR spectroscopy and powder X-ray diffractometry have been used to characterize precursor molecules and their oxides, respectively. Especially, X-ray single crystal studies of complex 2 show that the molecule is made up of three octahedra; the central [SrO₆] octahedron is sharing two neighboring edges with the peripheral [TaO₆] ones. The SBT film derived from the precursor 1 presents outstanding ferroelectric properties (P _r = 9 C/cm²; E _c = 0.8 V).     

Optical and Electrical Properties of Ferroelectric SBN Thin Films Prepared by Sol-Gel Process

Strontium barium niobate thin films were prepared by sol-gel method on various substrates using an improved process, two-step heating process. The two-step heating process applies an additive heat-treatment before crystallization for enhancement of the densification and the nucleation of films. Also, highly c-axis oriented SBN thin films with various compositions were obtained on MgO(100) and Pt(100)/MgO(100) substrates. Their optical and electrical properties such as optical propagation loss, refractive index, P-E hysteresis, and dielectric constant, were characterized as a function of the film composition.     

Preparation and Characterization of Sol-Gel Derived Y2O3 Thin Films

Sol-gel derived Y2O3 thin films have been prepared on platinum coated silicon wafers and fired to temperatures ranging from 400°C to 750°C. Multiple coats were used to obtain films up to 0.5 m thick with an intermediate firing of 400°C between coatings. Top Pt electrodes were sputtered to form monolithic capacitors. These films exhibited a dielectric constant of 18 and a leakage current of 10–11–10–7 A/cm2, making them attractive candidates for high dielectric constant dielectric films in high density DRAMs.     

Preparation and Properties of Highly Oriented Sr0.3Ba0.7Nb2O6 Thin Films by a Sol-Gel Process

We succeeded in the preparation of epitaxial or highly oriented strontium-barium niobate (Sr_0.3Ba_0.7Nb₂O₆) thin film by a sol-gel process. A homogeneous coating solution was prepared with Sr and Ba acetates and Nb(OEt)₅ as raw materials, and acetic acid and diethylene glycol monomethyl ether as solvents. Sr_0.3Ba_0.7Nb₂O₆ film sintered at 900°C on MgO(1 0 0) was oriented with c-axis perpendicular to the substrate surface. Sr_0.3Ba_0.7Nb₂O₆ film sintered at 700°C on SrTiO₃(1 0 0) was an epitaxial and oriented with c-axis in parallel to the substrate surface. Transmittance of Sr_0.3Ba_0.7Nb₂O₆ film (film thickness: 144 nm) was more than 60% at the range from 400 to 800 nm. Refractive index was 2.33 at 633 nm. Dielectric constant and dielectric loss of the Sr_0.3Ba_0.7Nb₂O₆ thin films prepared on polycrystal Pt substrates were 600 and 0.06 at room temperature and 1 kHz, respectively. The curie temperature (T_c) of polycrystalline Sr_0.3Ba_0.7Nb₂O₆ thin films was about 200°C. At room temperature and 50 kHz, remanent polarization (P_r) and coercive field (E_c) of the polycrystalline thin films were 1.79 C/cm² and 2.69 kV/cm, respectively.     

Ferroelectric Films

The preparation and properties of ferroelectric films are reviewed. Specific attention is directed to ferroelectric films prepared by wet chemical methods. Emphasis is placed on the microstructure and properties of SBT films for memory applications, and their dependence on chemistry and processing, as well as on the effects of chemistry and processing on the properties of piezoelectric and pyroelectric films. Emphasis is placed on recent results obtained in our laboratories, including modeling of the ferroelectric behavior of films and experimental results in each of these areas. Also considered is the use of ferroelectric films in memory, piezoelectric and pyroelectric devices of various types, with specific note made of the recently-announced use of pyroelectric sensors in automobiles.     

Ferroelectric Thin Films of Bismuth Strontium Tantalate Prepared by Alkoxide Route

Study of the interactions in Bi(OR)3-Ta(OR)5-ROH (R = Me, Et, iPr) at 20°C show that metal ethoxides are the best of the investigated precursors for the production of bismuth tantalates via alkoxides. Polycrystalline SrBi2Ta2O9 (SBTO) and BiTaO4 films on Si-SiO2-Ti-Pt substrates with thicknesses of 0.4–0.5 m and 0.4 m, respectively, have been formed by sol-gel processing. The most stable solutions for film application were obtained by using mixed-metal Bi-Ta ethoxides and solutions of Sr carboxylate (2-ethylhexanoic acid derivative) in 2-ethylhexanoic acid. Films annealed at 700–750°C for 30 min were single-phased. SBTO films demonstrated good ferroelectric properties: remanent polarization ranged from 3.5 to 4.0 C/cm2 and coercive voltage 1.5–2.0 V, whereas BiTaO4 films showed dielectric behavior.     

Alkoxide Derived SrBi2Ta2O9 Phase Pure Powder and Thin Films

Phase pure powder and thin films of the novel ferroelectric materials SrBi₂Ta₂O₉ (SBT) have been prepared using the organic precursors. The xero-gel formed was dried and characterized using TGA and DTA to determine the organic burn out and crystallization temperature of SBT. Powder X-ray diffraction was used systematically to check the crystallinity of SBT. Phase pure SBT powder was formed as low as 650°C and thin films at 600°C in comparison to other earlier reported work. SEM micrographs show a grain size of ≈0.1 μm and show crack free films with a film thickness of 2 μm.     

Synthesis of Bi2O3 and Bi4(SiO4)3 Thin Films by the Sol-Gel Method

Bi2O3 thin films were prepared by dipping silica slides in ethanolic solutions of tris(2,2-6,6-tetramethylheptane-3, 5-dionato)bismuth(III) [Bi(dpm)3] [1] and heating in air at temperatures 500°C. Bi4(SiO4)3 homogeneous thin films were obtained from the reaction of the bismuth oxide coating with the silica glass substrate at temperatures higher than 700°C. For heat treatments at temperatures between 600°C and 700°C, Bi2SiO5 coatings were obtained. The composition and microstructure evolution of the films were determined by Secondary Ion-Mass Spectrometry (SIMS), X-Ray Photoelectron Spectroscopy (XPS) and Glancing Angle X-Ray Diffraction (GA-XRD). The synthesis procedure was reproducible and allowed the control of the Bi2O3 phase composition. Moreover, the thin film annealing parameters were correlated with the formation of bismuth silicates, among which Bi4(SiO4)3 (BSO) is very appealing for the production of fast light-output scintillators [2].     

Structure and Optical Properties of 0.1BiFeO3-0.9SrBi2Nb2O9 Thin Films Using a Modified Sol-Gel Technique

Fe-doped SrBi₂Nb₂O₉ precursor solution was synthesized using bismuth nitrate Bi(NO₃)₃·5H₂O, strontium nitrate Sr(NO₃)₂, iron nitrate Fe(NO₃)₃·9H₂O, and niobium ethoxide Nb(OC₂H₅)₅ as starting materials, ethylene glycol monomethyl ether (C₃H₈O₂) as the solvent. 0.1BiFeO₃-0.9SrBi₂Nb₂O₉ thin films were prepared on fused quartz substrates using sol-gel processing. The surface morphology and crystal structure and optical properties of the thin films were investigated. The thin film annealing at 400°C were found to be amorphous, and the thin films crystallize to a perovskite structure after a post-deposition annealing at 600°C for 1 h in air. The grain of thin film was evenly distributed. The thin films exhibit the designed optical transmission, while the optical transition is indirect in nature. Their optical band gap is about 2.5 eV.     

Chemistry-Crystallization-Microstructure Relations of Sol-Gel Derived Lanthanum Modified Lead Titanate Thin Films

Lanthanum modified lead titanate thin films have been obtained by the deposition of sol-gel solutions onto platinized (100) silicon substrates. Crystallization of perovskite films was achieved by thermal treatments at 650°C with slow or rapid heatings. Lead oxide excesses were used in the precursor solutions to counterbalance the lead losses produced during the thermal treatment. Rapid heatings and large excesses of lead produce a preferred orientation of the films. These films have more homogeneous and denser microstructures than slow heated films without lead excess.     

Absorption-Reflection Infrared Spectroscopy Studies of Sol-Gel Prepared Ferroelectric Pb(Zr,Ti)O3 Thin Films on Pt Electrodes

Although the sol-gel method is ideally suited for the preparation of ferroelectric PZT thin films, poor reproducibility and the need to lower crystallization temperatures remain an issue. To address these problems, we have studied the mechanism of thin film formation using absorption-reflection infrared spectroscopy for a novel and less harmful precursor solution system based on butoxyethanol. By recording in situ infrared spectra we were able to monitor hydrolysis, condensation, decomposition and crystallization phenomena versus temperature. We speculate that the lower reactivity of butoxyethanol is responsible for the higher quality of Ti rich PZT based ferroelectric capacitors prepared by a butoxyethanol precursor solution compared with the more widely used methoxyethanol one. Finally, we observed that film's decomposition kinetics is faster as compared to bulk samples and depends on film thickness and electrode layer.     

Preparation and Characterization of Molybdenum Oxide Thin Films by Sol-Gel Process

This paper presents a new sol-gel process to prepare molybdenum oxide thin films. A molybdenum acetylacetonate sol was prepared by employing the system CH₃COCH₂COCH₃/MoO₃/C₆H₅CH₃/HOCH₂CH₂OCH₃. A molybdenum acetylacetonate gel was prepared by addition of aqueous NH₃. Thermal gravimetry (TG) and differential thermal analyses (DTA) of the gel suggested that crystallization of MoO₃ occurs in a 140 K temperature range around 508°C. MoO₃ films were prepared on fused silica, Si (111) and Al₂O₃ (012) substrates by annealing spin coating films of the sol in oxygen environment at 508°C. X-ray diffraction (XRD) showed that all films crystallize in -MoO₃ structure, and crystallites on fused silica substrate are arbitrarily oriented while those on Si (111) and Al₂O₃(012) substrates oriented in the (010) direction. SEM investigations showed that MoO₃ grains of all films are randomly distributed, with a longitudinal dimension of about 1–5 m and the film thickness is about 1 m.     

Elaboration of ZnO Thin Films with Preferential Orientation by a Soft Chemistry Route

Microcrystalline ZnO films presenting well-defined and tunable orientation were obtained by spin coating of alcoholic sols by two different approaches, based on controlled hydrolysis-condensation of Zn-ethanolamine complexes. As-deposited films are formed by amorphous zinc oxide-acetate submicronic particles, which are transformed into oriented ZnO after thermal treatment. The orientation of ZnO depends on the synthesis method, and the solvent. While in ethanol and [Zn] = 0.05 mol·L^–1, films consist of rectangular platelets oriented with the (100) planes parallel to the substrate (a//n), the orientation of the particles changes to (c//n) for systems in 2-methoxyethanol (2-ME) and [Zn] = 0.75 mol·L^–1. A study of chemical factors that influence the orientation (precursor, solvent, MEA/Zn ratio, concentration, coating parameters, heat treatment) is presented.     

Textured PLCT Thin Films Prepared on Pt/Ti/SiO2/Si Substrate by Metal-Organic Decomposition

Textured calcium modified (Pb,La)TiO₃ (PLCT) films were deposited on Pt/Ti/SiO₂/Si substrates by using a metal-organic decomposition (MOD) process. The PLCT films exhibit good ferroelectric properties, a very low leakage current and a sharp PLCT/Pt interface. The (100) texture of the PLCT film is growth-controlled; the (100) oriented grains grow preferentially so as to minimize the surface energy. Particularly, the (100) preferred orientation is easy to form in the PLCT film with a layered structure for which the substrate almost does not affect the nucleation and growth of the film.     

MOCVD生长铁电氧化物薄膜MO源研究进展

高性能铁电氧化物薄膜是当今功能材料的研究热点之一.随着新型MO源的不断研究与开发,利用MOCVD技术制备高质量铁电薄膜材料得到了快速的发展.本文在分析金属醇盐和金属β-二酮化合物等MO源的结构与其物性依赖关系基础上,分类综述了近年来在用于MOCVD方法生长铁电氧化物薄膜的新型MO源研究和开发方面的发展动态与趋势,为MOCVD方法制备铁电薄膜材料MO源的选择提供有用的参考与借鉴.     

Inorganic Thin Films Prepared from Soluble Powders and Their Applications

Sol-gel processing has proved to be a useful method for the preparation of a wide range of inorganic thin films. However, gelation or precipitation of coating solutions and thus limited shelf-life have been drawbacks for the industrial application of this technology.Soluble powders of various compositions can be prepared from modified metal alkoxides commonly employed in sol-gel processing. Even though these powders contain a considerable amount of organic moieties they can be stored indefinitely under ambient conditions, thus diminishing shelf life problems. Redissolution in polar organic solvents, solvent mixtures or even water yields ready-to-use coating solutions. Coating solutions for the preparation of titania (TiO₂), zirconia (ZrO₂) and lead zirconate titanate (PbTi _x Zr_1–x O₃, PZT) films have been synthesized by this method. Thickness, microstructure and properties of the resulting films can be varied by modification of the solvent, the coating procedure and thermal treatment. Inorganic thin films for various applications have been prepared.