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.     

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     

SrBi2Nb2O9 Ferroelectric Powders and Thin Films Prepared by Sol-Gel

Pure SrBi2Nb2O9 powders and thin films were obtained using sol-gel synthesis from mixtures of niobium ethoxide, bismuth and strontium 2-ethylhexanoates. Powders crystallized for 2 hours at 700°C had grain sizes of about 100–150 nm. SrBi2Nb2O9 thin films were prepared by spin-coating a stable precursor solution onto Si/SiO2/TiO2/Pt substrates. Crystallization of pure SrBi2Nb2O9 phase occurred at about 500–550°C. Randomly oriented 0.3 m-thick crack-free films were obtained after 10 successive depositions and heating at 700°C for 2 hours. P-E hysteresis loops have confirmed the ferroelectric behavior of the films: they show a remanent polarization of 2.5 C/cm2 (5 V, 8 ms). No fatigue was observed up to 109 full switchings.     

Aqueous Solution-Gel Synthesis of Strontium Bismuth Niobate (SrBi2Nb2O9)

The synthesis of multimetal oxides containing pentavalent elements like Nb and Ta out of an aqueous solution is very complicated due to the extremely high sensitivity of these metals towards hydrolysis. Moreover the only water-soluble starting compound is the oxalate which is not very suited for gel formation. Nevertheless, from Nb-oxalate it is possible to prepare a water-soluble Nb(V)-precursor by chemical modification. The synthesized precursor remains stable in the pH-range needed for gel formation. This Nb(V)-precursor is used for the synthesis of the ferroelectric material SrBi₂Nb₂O₉ (SBN). An aqueous acetate-citrate solution-gel precursor for SBN was prepared. The chemical homogeneity of this precursor was investigated by means of TEM-experiments. All metal ions were found to be homogeneously dispersed in the precursor gel at least down to 10 nm. The SBN phase formation is followed by means of X-ray Diffraction. It has been shown that the perovskite phase already forms at 550°C.     

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.     

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.     

Stress Measurements and Processing Optimization for Solution Derived SrBi2Ta2O9 Thin Films

The development of stress in the SrBi₂Ta₂O₉ (SBT) films generated from a chemical solution deposition method was monitored during processing using wafer curvature measurements. Stress measurements of the entire Si/SiO₂/Pt/SBT stack revealed an overall tensile stress of 536 MPa. The greatest increase in tensile stress was recorded for the anneal of the Pt bottom electrode and was due to the thermal expansion mismatch. Deposition of an amorphous SBT layer on the Pt, followed by a low temperature anneal (300°C), had little overall effect on the stress of the stack; however, upon crystallization, significantly more tensile stress was introduced into the stack. To further investigate the effect that stress has on the various electrical properties SBT films, wafers with different stress states were produced and SBT films deposited on them. Initial investigations indicate that SBT films on wafers with a higher tensile stress displayed improved ferroelectric hysteresis and switchable polarization.     

Properties and Photoelectrocatalytic Behaviour of Sol-Gel Derived TiO2 Thin Films

Titanium dioxide (TiO₂) thin films have been prepared on indium doped tin oxide (ITO) glass by sol-gel dip-coating method. Properties of the films were determined as a function of heat-treatment by X-ray diffraction, scanning electron microscopy and photoelectrochemical tests. The films heat-treated at higher temperatures show better crystallinity and photoresponse. The microscopic structure on the film after heat-treatment is attributed to the incorporation of organic polymer into the precursor solution. The performance of the electrodes treated at different temperature on photoelectrocatalytic degradation of methyl orange was investigated. The effect of applied potential and the ability of the electrode to be repeatedly used in photoelectrocatalytic degradation were also evaluated.     

Au/Al2O3纳米复合薄膜的制备和表征

用溶胶-凝胶法制备了Au/Al₂O₃纳米复合薄膜。利用X-射线衍射、X-射线光电子能谱、原子力显微镜以及紫外-可见光谱对薄膜的微观结构、表面形貌及光学性能进行了表征,研究表明:Au/Al₂O₃纳米复合薄膜是由纳米微晶组成的颗粒膜, 复合薄膜均匀、致密、无裂纹,Au以纳米晶核形式镶嵌于Al₂O₃基体中,纳米Au晶核的粒径为23～26nm;复合薄膜在可见光区有较强的吸收,吸收峰位置与烧结温度有关,吸收强度随烧结温度和金添加量增大而增大。     

无机盐溶液源溶胶-凝胶法制备锶铋钽铁电陶瓷薄膜过程研究

采用可溶性无机盐Sr(NO₃)₂,Bi(NO₃)₃及HTaF6为原料,以柠檬酸、乙二醇及乙二胺四乙酸(EDTA)为络合剂,利用溶胶-凝胶旋转涂覆工艺,分别在Al₂O₃和Pt/Ti/SiO₂/Si的衬底上制备了SrBi₂Ta₂O₉(SBT)铁电陶瓷薄膜.采用SEM,XRD及FTIR等微观分析手段,对制备的SBT溶胶与薄膜过程机理进行了实验研究.结果表明,由无机盐溶液原料络合合成SBT溶胶是此方法制膜的关键,其中络合剂的种类、用量和pH值的控制等是重要的影响因素.制备了相组成均一、薄膜表面致密、均匀、无开裂、晶粒尺寸为150nm的多晶膜,获得了剩余极化(2P_r)与矫顽电场强度(2E_c)分别为9.6μC/cm²与76kV/cm铁电性能较好的薄膜材料.     

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.     

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.     

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.     

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).     

Fabrication of Single-Phase BaTi4O9 Nanocrystalline Powder by Sol-Gel Process

BaTi₄O₉ nanocrystalline powder was prepared by sol-gel method using Ti(OC₄H₉)₄ and Ba(CH₃COO)₂ as raw materials. The optimum process was obtained by analyzing the synthesis condition of the single-phase BaTi₄O₉ nanocrystalline powder as follows: the content of acetyl-Titanium = 1 mol/L. pH = 4.2, molar ratio of water/alkoxide = 15, and the powder is kept at 1200°C for 2 h. The XRD and TEM analysis showed that the single-phase BaTi₄O₉ nanocrystalline powder of 30 nm in size was well prepared.     

The Effect of SiO2 Addition on the Grain Size and Photocatalytic Activity of TiO2 Thin Films

The uniform transparent TiO₂/SiO₂ nanometer composite thin films were prepared via sol-gel method on the soda lime glass substrates, and were characterized by X-ray photoelectron spectroscopy (XPS), FTIR spectroscopy, UV-VIS spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and BET surface areas. It was found that the addition of SiO₂ to TiO₂ thin films could suppress the grain growth of TiO₂ crystal and increase the hydroxyl content of the surface of TiO₂ films. The photocatalytic activity of the as-prepared TiO₂/SiO₂ composite thin films increases for SiO₂ content of less than 5 mol%.     

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.     

后处理对TiO2纳米薄膜的表面结构和光催化活性的影响

半导体TiO2光催化材料对环境中各种污染物的明显去除效果已引起人们的广泛关注[1～6].在普通钠钙玻璃表面涂制高光催化活性的TiO2纳米薄膜,制成环保建筑材料,不仅可以自洁玻璃表面,而且可以用于净化空气、处理废水等.     

Orientation and Surface Properties of Sol-Gel Derived Y2O3 Films

The orientation, surface and optical properties of sol-gel derived Y₂O₃ films have been investigated. Transparent Y₂O₃ films were prepared on quartz glass substrates by sol-gel processes using YCl₃·6H₂O as a starting material. The water droplet contact angles of the films reached constant values between 79° and 90° after the films were left for 8 to 10 days in air at ambient temperature, indicating that the film surface exhibited hydrophobicity. When 2-(2-methoxyethoxy)ethanol (MEE) was added to the sol, yttria in the films crystallized to a strongly oriented cubic phase at firing temperatures between 400°C and 500°C. The intensity of the XRD peaks increased as the firing temperature was increased to 900°C. However, yttria crystallized to a non-oriented cubic phase when MEE was not used. The refractive index and packing density of the Y₂O₃ films increased from 1.55 to 1.68 and from 0.67 to 0.79, respectively, as the firing temperature was raised from 400°C to 900°C, indicating that sol-gel derived Y₂O₃ films are lower in density than evaporated ones.     

Preparation and Characterization of Bismuth Doped TiO2 Thin Films

A series of Bismuth-doped titanium oxide (Bi-doped TiO₂) thin films on glass substrates have been prepared by sol-gel dip coating process. The prepared catalysts were characterized by XRD and XPS. The photocatlytic activity of the thin film catalysts was evaluated through the photodegradation of aqueous methyl orange under UV illumination. The experiments demonstrated that the Bi-doped TiO₂ prepared was anatase phase. The doped bismuth was in the 3⁺ oxidation state. The presence of Bi significantly enhanced the photocatalytic activity of TiO₂ films. At calcination temperature of 500°C, with doping concentration of 2 wt %, Bi-doped TiO₂ thin film showed the highest photocatalyic activity.