Sol-Gel Processing of PbZrO3 Thin Films

PbZrO₃ (PZ) thin films have been prepared by 2-methoxyethanol route from lead oxide or lead acetate and zirconium n-butoxide. The use of lead oxide as lead source and the seeding layer of TiO₂ on Pt/TiO₂/SiO₂/Si substrate facilitate the formation of the perovskite phase.     

New Sol-Gel Route for Processing of PMN Thin Films

Pyrochlore free Pb(Mg_1/3Nb_2/3)O₃ (PMN) thin films were prepared from mixed-metal precursors solutions using the sol-gel process. Lead acetate [Pb(CH₃COO)₂], magnesium acetate [Mg(CH₃COO)₂] and niobium ethoxide [Nb(C₂H₅O)₅] were used as starting materials, while 2-isopropoxy-ethanol was chosen as solvent. The reactivity of the precursors was investigated in order to understand and control the process and thus to prevent the contamination of the PMN with the pyrochlore phase. The solution was spin-coated on TiO₂/Pt/TiO₂/SiO₂/Si substrate. The thin films were characterized by SEM and XRD while dielectric measurements were performed on the bulk ceramic.     

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.     

Crystallization Behavior of SiO2-TiO2 Sol-Gel Thin Films

The aim of this work was to investigate the crystallization behavior of thin films of SiO₂−TiO₂ made by the sol-gel process as function of the TiO₂ content and the temperature and time of heat treatment. Precursor solutions were prepared by hydrolysis of TEOS (tetraethoxysilane) and TPOT (titaniums tetraisopropoxide). Multilayer films were spun on single crystal silicon wafers. The compositions studied were (on a molar percentage basis) 20TiO₂−80SiO₂, 30TiO₂−70SiO₂, 40TiO₂−60SiO₂ and pure TiO₂. The films were heat treated at different temperatures between 300°C and 1200°C, for different periods of time (30 s-90 h). The crystallization kinetics were followed by micro-Raman spectrometry. Grazing incidence X-ray diffraction showed that the films crystallized into one or both of two crystalline phase of TiO₂: anatase and rutile (for pure TiO₂ only). The volume fractions of the crystalline phase varied from very low values (<1%), up to 100%, for a TiO₂ sample heat treated at 800°C for 8 hours. The results show that the volume fraction of crystalline phase is strongly influenced by the heat treatment temperature and also, to a smaller extent, by the heat treatment time. The most important parameter, however, is the composition of the films: the higher their TiO₂ concentration, the lower is the crystallization temperature and the larger is the crystallized fraction.     

Preparation and Characterization of MgO Thin Films by a Novel Sol-Gel Method

MgO thin films have been prepared on Si substrates by a novel and simple sol-gel method using magnesium nitrate and collodion as starting material. Solutions consisting of magnesium nitrate in a mixture of collodion and ethanol were spin-coated onto silicon substrates. It was found that collodion was a necessary component to form stable sols and the crystallization and structures were clearly dependent on the amount of the collodion and the annealing temperature. The MgO thin films with good crystallization were obtained after annealing at 800°C. Meanwhile, the microstructure of the MgO films was examined by transmission electron microscopy and atomic force microscopy.     

Photocatalytic Activity and Characterization of the Sol-Gel Derived Pb-Doped TiO2 Thin Films

Photocatalytically active Pb-doped TiO₂ thin films were prepared on a soda-lime glass substrate by sol-gel dip-coating technique using TiO₂ sols containing lead(II) nitrate. The thin films were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), UV-VIS spectroscopy and X-ray diffraction (XRD). A shift of the UV-VIS absorption towards longer wavelengths was observed, which indicated a decrease in the band-gap of TiO₂ upon Pb doping. XRD results showed both pure and Pb-doped TiO₂ thin films were polycrystalline, anatase type, and oriented predominantly to the (101) plane. A slight shift in the d-spacing for the Pb-doped film indicated the incorporation of Pb into the TiO₂ lattice to form Pb _x Ti_1–x O₂ solid solution. AFM results showed Pb-doped TiO₂ thin films were composed of larger TiO₂ particles and had rougher surface, compared with un-doped TiO₂ thin films. XPS results showed that except for the enrichment of Pb near the surface, Pb exists in the forms of Pb _x Ti_1–x O₂ and PbO. Dimethyl-2,2-dichlorovinyl phosphate (DDVP) was efficiently degraded in the presence of the Pb-doped TiO₂ thin films by exposing the insecticide solution to sunlight. The mechanism of photocatalytic activity enhancement of the Pb-doped TiO₂ thin films was discussed.     

二氧化钛/聚乙烯吡咯烷酮纳米复合薄膜的制备与表征

采用溶胶-凝胶法(so1 gel)制备了TiO2/聚乙烯吡咯烷酮(PVP)有机 无机纳米复合薄膜.采用扫描电子显微镜、接触角测定仪、红外光谱仪、紫外 可见吸收光谱仪和静 动摩擦系数测定仪对所制备的TiO2/PVP纳米复合薄膜进行了结构表征和性能研究.结果表明:所制备的TiO2/PVP纳米复合薄膜表面平整光滑、无裂纹、具有一定的疏水性、良好的透明性、防紫外线性能和减摩抗磨性能.     

Sol-Gel Preparation and Characterization of Ag-TiO2 Nanocomposite Thin Films

Ag-TiO₂ thin films were prepared with a sol-gel route, using titanium isopropoxide and silver nitrate as precursors, at 0.03 and 0.06 Ag/Ti nominal atomic ratios. After drying at 80°C, the films were fired at 300°C and 500°C for 30 min. The films were analysed by X-ray diffraction (XRD) with glancing angle, and X-ray photoelectron spectroscopy (XPS), with depth profiling of the concentration. XPS analysis showed the presence of C and N as impurities in the nanocomposite films. Their concentration decreased with increasing the firing temperature. Chemical state analysis showed that Ag was present in metallic state, except for the very outer layer where it was present as Ag⁺. For the films prepared with a Ag/Ti concentration of 0.06, depth profiling measurements of the film fired at 300°C showed a strong Ag enrichment at the outer surface, while composition remained almost constant within the rest of the film, at 0.019. For the films heated to 500°C, two layers were found, where the Ag/Ti ratios were 0.015 near the surface and 0.026 near the substrate.     

Crystallization and Microstructure of (Sm, Pb)TiO3 Thin Films Prepared from Sol-Gel Synthesized Solutions

A sol-gel route is developed for the synthesis of samarium modified lead titanate precursor solutions. The solutions are used for the deposition of thin films. After thermal treatment of the films, two crystalline phases are observed by X-ray diffraction analysis: an undesirable pyrochlore phase and a ferroelectric perovskite. These two phases are clearly distinguished in the film microstructure, showing a fined grained fraction of pyrochlore anda-axis oriented rosette grains of perovskite. The development of these phases as well as the evolution of the perovskite/pyrochlore ratio in the films is related to the chemistry of the synthesized solutions and the thermal treatment used for crystallization.     

Effect of Niobium Modifications to PZT (53/47) Thin Films Made by a Sol-Gel Route

Niobium-modified lead zirconate titanate thin films (PNZT) with nominal compositions, Pb_(1–0.5x) (Zr_0.53 Ti_0.47)_1–x Nb _x O₃:x = 0.02–0.07, have been prepared using a diol based sol-gel route. Single-layer (0.5 m) films were fabricated on platinised silicon substrates by spin-coating. The effect of niobium additions with regard to phase development, microstructure, and ferroelectric and dielectric properties were investigated for different annealing temperatures. For comparison, unmodified PZT films were also prepared. Niobium substitution increased the crystallisation temperatures for perovskite PNZT phase formation. The values of remanent polarisation P _r and dielectric constant _r were found to decrease with the introduction of Nb. For example, in films heated at 700°C for 15 min, the P _r value of an unmodified PZT film was 31 C cm^–2, compared to 17 C cm^–2 for an x = 0.05 PNZT film, whilst respective relative permittivity values fell from 1190 to 600. The highest Nb concentration film, x = 0.07, did not display any switchable polarisation characteristics, which is consistent with high levels of intermediate pyrochlore phase.     

溶胶凝胶法制备铜铁矿结构p型透明导电氧化物薄膜

铜铁矿结构p型透明导电氧化物(transparent conducting oxide, TCO)薄膜是一类在电子学领域具有广泛应用前景的新材料,因其可与n-TCO薄膜形成真正意义上的“透明器件”而备受关注。本文介绍了铜铁矿结构p-TCO的结构特性以及溶胶凝胶法的基本原理和特点;系统地介绍了溶胶凝胶法制备铜铁矿结构p-TCO薄膜的工艺;分析比较了有机醇盐、无机盐溶胶体系的优缺点;最后讨论了进一步的发展方向,指出溶胶凝胶法是一种高效可行的制备p-TCO薄膜的方法。     

Photoconductivity in Mesostructured Thin Films

Mesostructured silica films are widely studied due to their different structures, properties and variety of possible applications. Sodium dodecyl sulfate (SDS)-templated sol-gel silica films possess highly ordered lamellar phase structure. It is expected that molecules and polymer chains line up with these layered structures when incorporated into the films. Mesostructured thin films were doped with Dispersed Red 1 (DR1) and carbazole ((C₆H₄)₂NH)). The films were poled by corona discharge at 120 C. Absorption spectra were recorded as function of the polarization time. Dependence of the absorption coefficient with polarization time was fitted with a Langevin-Debye equation. It shows a saturation level after 60 minutes of polarization. We compare the efficiency of mesostructured thin films with that of amorphous films. The photoconductivity technique was used to determine the charge transport mechanism of these films. From current density versus electrostatic applied field, the parameters for the photovoltaic effect and photoconductivity were determined. Results of the mesostructured thin films are also compared to those of KNbO₃ crystals.     

Preparation and Characterization of (Ba,Ca)(Ti,Zr)O3 Thin Films Through Sol-Gel Processing

(Ba_0.92,Ca_0.08)(Ti_0.92,Zr_0.08)O₃ thin films were prepared from Ba-Ti and Ca-Zr precursors by sol-gel processing. Polymerizable solutions containing Ba-Ti and Ca-Zr, respectively, were newly synthesized. Decomposition of the starting compounds and crystallization behavior of the film were examined by using TG/DTA and XRD. Microstructure of thin films was observed by using SEM. Polycrystalline (Ba_0.92,Ca_0.08)(Ti_0.92, Zr_0.08)O₃ films obtained by firing at 800°C were dense with fine grains. The thin films showed a dielectric constant of 1200 and dielectric loss of 0.5%.     

Selective Formation of Spinel Iron Oxide in Thin Films by Complexing Agent-Assisted Sol-Gel Processing

The structure of iron oxide was controlled by regulating the hydrolytic polymerization of aquo iron complexes with organic polydentate ligands such as diols. Iron oxides were prepared by calcining the precursor polymers obtained from iron nitrate nonahydrate and diols. When the diols were 1,2-pentanediol, 1,2-hexanediol and 1,2-octanediol, α-Fe₂O₃ with corundum structure appeared exclusively or as the main crystalline phase, in spite of the amount of diol used and the calcination temperature. In the case of 1,2-decanediol and 1,2-dodecanediol, when five moles of the diols were used to one mole of iron nitrate and the calcination temperatures were below 400°C, ψ-Fe₂O₃ with spinel structure appeared as the main phase and, when less than five moles of the diols were used, α-Fe₂O₃ appeared exclusively or as the main phase, irrespective of the calcination temperature. This tendency was also observed in thin films. Thus, a transparent magnetic film composed of γ-Fe₂O₃ could be prepared by applying a benzene solution of the iron polymer, obtained with 5 equivalents of 1,2-decanediol, on quartz and calcining the gel film at 350°C.     

Sol-Gel Derived Barium-Strontium Titanate Films

Sol-gel techniques for the preparation of barium-strontium titanate (BST) films are discussed. The evolution of film microstructure during heat treatment, and the dielectric properties of BST films prepared from alkoxide solutions and from alkoxide solutions modified by 2-ethylhexanoic acid were studied. It is shown that the extent of the modification of the precursors by 2-ethylhexanoic acid changes the precursor molecular complexity governing the microstructure of the films and their electrical properties.     

Preparation and Characterization of TiO2 Thin Films by Sol-Gel Method

Titanium dioxide (TiO₂) thin films have been deposited on silicon and glass substrates by the sol-gel process using titanium iso-propoxide [Ti(O-i-C₃H₇)₄]. The bond configuration of the TiO₂ thin films was analyzed by using FTIR in the wavenumber range from 400 to 4000 cm^–1. The spectral transmittance of as-deposited TiO₂ films deposited on fused silica glass was measured in the wavelength range from 200 to 900 nm. X-ray diffraction measurements were performed to determine the crystallinity of the TiO₂ films. As-deposited films were amorphous. As the film was annealed at higher temperature, the structure was transformed from amorphous to the anatase crystalline state. The chemical composition of the deposited film was investigated using X-ray photoelectron spectroscopy (XPS). The films are essentially stoichiometric with carbon as the dominant impurity on the surface. Raman spectra show the characteristic of TiO₂ anatase phase. The electrical properties of the TiO₂ films were measured using capacitance-voltage (C-V) and current-voltage techniques. From C-V measurements, the dielectric constants were calculated to be approximately 26 for the as-deposited films and 75–82 for films annealed at 700°C in different atmosphere. For the as-deposited samples, the breakdown voltage was 2.7 MV/cm, and for an electric field of 1 MV/cm, the leakage current was 5 × 10^–5 A/cm² and the resistivity was 2.2 × 10¹⁰ -cm.     

Sol-Gel Preparation of α-Fe2O3 Thin Films: Structural Characterization by XAFS and Raman

Films of Fe2O3 have been prepared by two different sol-gel syntheses, starting from inorganic salts as precursors, Fe(NO3)3 · 9H2O or FeCl3 · 6H2O. Differences in the local order between the two preparations are investigated by XAFS (X-Ray Absorption Fine Structure) and Raman measurements.     

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.     

纳米Au-TiO2复合薄膜的溶胶-凝胶法制备、表征和性能

用溶胶-凝胶法制备了纳米Au-TiO₂复合薄膜.X射线衍射、X射线光电子能谱、原子力显微镜、紫外-可见光谱及摩擦磨损实验研究表明,复合薄膜均匀致密,Au以纳米晶粒形式均匀、不连续分散镶嵌于TiO₂基体中,纳米Au粒径为14～25nm;复合薄膜在可见光区有较强的吸收,吸收峰位置和强度与烧结温度和金的添加量有关;复合薄膜具有良好的抗磨减摩性能,在1N负荷下,摩尔分数为5%的Au-TiO₂薄膜的摩擦系数仅为0.09～0.10,耐磨寿命多于2000滑动周次.