Vapor-Gel Deposition Method for Oxide Thin Films

In this paper, we attempt to formally establish the chemistry of a vapor-gel process for the low temperature deposition of thin films. A number of applications of such a process will be discussed mostly on a theoretical basis, with the exception of one or two particular aspects that we have experimentally demonstrated so far. The essential components of the deposition apparatus will be described in detail along with some discussions on their operation conditions. Finally, we conclude this paper by systematically comparing the vapor-gel method to other well-known thin film fabrication techniques including the sol-gel method.     

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.     

Chiral Thin Films of Metal Oxide

In this paper, we describe for the first time the synthesis of new chiral nanosized metal oxide surfaces based on chiral self‐assembled monolayers (SAMs) coated with metal oxide (TiO₂) nanolayers. In this new type of nanosize chiral surface, the metal oxide nanolayers enable the protection of the chiral self‐assembled monolayers while preserving their enantioselective nature. The chiral nature of the SAM/TiO₂ films was characterized by variety of unique techniques, such as second‐harmonic generation circular dichroism (SHG‐CD), quartz crystal microbalance, and chiral adsorption measurements with circular dichroism spectroscopy. The chiral resolution abilities of the SAMs coated with metal oxide (TiO₂) nanolayers were investigated in the crystallization of a racemic mixture of threonine and glutamic acid. Our proposed methodology for the preparation of nanoscale chiral surfaces described in this article could open up opportunities in other fields of chemistry, such as chiral catalysis.     

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.     

溶液法制备氧化锌半导体薄膜及其顶栅极晶体管器件

采用旋涂法用浓度分别为0.05,0.10和0.25 mol·L^-1的氧化锌前躯体溶液制备了氧化锌薄膜,并且制备了基于氧化锌多层膜的顶栅极晶体管器件,其中以利用光刻工艺刻蚀的氧化铟锡为源漏电极。通过原子力显微镜(AFM)和X-射线衍射(XRD)分别表征了薄膜的形貌以及结晶情况,并且讨论了前躯体的浓度顺序对氧化锌多层膜的影响。按照浓度从大到小的顺序依次旋涂前躯体溶液制备的氧化锌薄膜表现出了较高的载流子迁移率(7.1×10^-3 cm²·V^-1·s^-1),而按照浓度从小到大的顺序依次旋涂前躯体溶液制备的氧化锌薄膜的载流子迁移率为5.2×10^-3 cm²·V^-1·s^-1。文中通过对两种多层薄膜的形貌和结晶性能的分析表明影响顶栅极薄膜晶体管性能的主要因素是薄膜的粗糙度。平整的薄膜有利于形成较好的半导体层/绝缘层接触界面,从而有利于提高器件的载流子迁移率。     

Synthesis and Characterization of Nano-Crystalline Fluorine-Doped Tin Oxide Thin Films by Sol-Gel Method

Thin films of fluorine-doped tin-oxide (FTO) were prepared by sol-gel dip-coating technique. Stannous chloride (SnCl₂2H₂O) and hydrogen fluoride (HF) were mixed with isopropyl alcohol to serve as source solution. X-ray diffraction (XRD) spectrum showed all the peaks of the crystalline SnO₂. Analysis of XRD spectrum showed the particle size to be nearly 6 nm, which indicated the nanocrystalline structure of the films. Strain calculation by integral breadth (IB) method from XRD data showed a value of 0.010. UV-Visible spectrophotometric measurement showed high transparency of the films in the visible region and the band gap was calculated to be 3.34 eV. The room temperature resistivity of the films were of the order of 1 cm. Fluorine concentration in the films was determined from energy dispersive X-ray (EDX) study. Current-voltage (I-V) characteristics at high temperatures showed the Poole-Frenkel effect of thermionic emission. SEM study indicated the existence of fine grains in the film. FT-IR spectroscopy showed strong Sn—O and Sn—O—Sn bonding.     

Metal Oxide Thin Films Containing Au Nano-Particles Prepared with Gas Diffusion Method

Au particles dispersed thin metal oxide films were prepared from precursor films containing HAuCl₄ with H₂S gas diffusion method. HAuCl₄ was uniformly dissolved in the films as promoted by hydroxypropyl cellulose (HPC). The mechanism of the Au particle formation was studied. It was found that HAuCl₄ was converted directly to Au metal particles upon contacting with H₂S gas. Au particles generated by this method were characterized with small particle size, sharp size distribution and high volume fraction in the films. The surface plasma resonance absorption of Au particles shifted to longer wavelength when TiO₂ component was introduced in the matrix.     

氧化锌薄膜的电化学沉积和表征

以透明导电玻璃(TCO)为衬底，用硝酸锌水溶液作为电解液，研究了阴极还原沉积ZnO薄膜的反应机理和电化学行为. 通过改变工艺条件来控制ZnO的生长速率， 得到了粒径为10～15 nm的纳米ZnO薄膜. XRD分析显示纳米ZnO薄膜纯度高， 呈纤锌矿结构. 光学测试结果表明，在可见光区其透光度高达90%，禁带宽度为3.37 eV.     

Y2O3薄膜/锡掺杂玻璃光波导气敏元件及其气敏性

采用溶胶-凝胶法将氧化钇(Y2O3)敏感膜固定在锡掺杂玻璃光波导表面,研制出了Y2O3薄膜/锡掺杂玻璃光波导气敏元件,并对挥发性有机气体进行了检测.通过XRD测试对敏感薄膜的结构及晶粒尺寸进行了表征.实验结果表明,在室温下Y2O3薄膜/锡掺杂玻璃光波导气敏元件对二甲苯、氯苯气体有较好的选择性响应,其响应浓度范围为l×10-3 ～1×10-5(V/V).Y2O3薄膜/锡掺杂玻璃光波导气敏元件具有灵敏度高、成本低、响应速度快、制作工艺简单和可逆性好等优点.     

自生长燃烧法合成纳米铁酸钇固溶体光催化剂

以硝酸铁和硝酸钇作为前驱体,甘氨酸为燃料用自生长燃烧法合成了可见光光催化剂YFeO₃及其固溶体。样品通过X射线粉末衍射(XRD)、N₂吸附、紫外-可见漫反射(UV-Vis DRS)、扫描电子显微镜(SEM)和透射电镜(TEM)等表征了其晶相结构、BET比表面积和形貌。结果表明掺杂一定量的金属能有效地提高自生长燃烧法合成的YFeO₃的纯度,所合成的样品晶粒大小约为55 nm。与YFeO₃相比其固溶体吸收边红移。光催化降解亚甲基蓝(MB)和罗丹明B(RhB)结果表明YFeO₃及其固溶体均具有活性,Bi修饰的YFeO₃表现出最高的光催化活性,而且对于不同染料的降解程度不同。     

化学气相沉积法制备ZnO纳米结构薄膜及其SERS活性研究

提供了半导体作为光、电和生物等功能材料的表面和界面信息, 同时也为SERS的研究开拓了新的领域.     

Analysis of Antimony Doping in Tin Oxide Thin Films Obtained by the Sol-Gel Method

The antimony doping in SnO₂ thin films prepared by the sol-gel dip-coating method has been studied using two characterization techniques. In order to determine the actual doping level directly in the deposited layers, X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) have been used. We found that this doping level is systematically lower than expected from the starting solutions composition, and that two oxidation states are present: Sb³⁺ and Sb⁵⁺. As the antimony content increases, there is a competition between Sb⁵⁺ and Sb³⁺ species.The SnO₂: Sb thin films have also been observed by transmission electron microscopy (TEM), showing that the measured mean size of crystallites decreases as the Sb content increases in the oxide. No precipitates of either Sn or Sb oxides (other than SnO₂) could be detected.     

Chemical Liquid Phase Deposition of Thin Aluminum Oxide Films

Introduction Inorganic oxide films have attracted a lot of interest in the last several decades. Among them, silicon dioxide films are widely used in modern microelectronics, optics and mechanics. This material has been grown by various methods including thermal oxidation, chemical vapor phase deposition, plasma-enhanced chemical vapor phase deposition, and so on.1,2 Recently, Nagayama et al.3 have reported that SiO2 thin films could be produced by a new chemical method of liquid phase depos…     

金属β-二酮化合物用于MOCVD法生长铁电氧化物薄膜

对用于MOCVD法生长铁电氧化物薄膜的金属β－二酮化合物的制备、结构及性质进行了评述，对它们在生长铁电薄膜中的应用现状进行了介绍，并对它们的应用前景作了展望。     

Electrochemical and Electrochromic Properties of Ni Oxide Thin Films Prepared by a Sol–Gel Method

Nickel oxide thin films, which are well known anodic coloration materials that are used in electrochromic devices, were prepared by a sol–gel method, and their electrochemical and electrochromic properties were investigated. The sol was prepared from Ni(OH)₂ powder with an average size of 7 nm, in a mixture of ethylene glycol and absolute ethanol. The films were coated on an ITO substrate using the powder, dispersed in the solution. When additive materials, acetyl acetone and glycerol, were added to the sol its hardness and adhesion properties were improved. The optimized thin film formed an amorphous, porous structure, and showed a large current density during continuous potential and pulse potential cycling. The film also was transparent and had a high coloration efficiency (33.5 cm²/C) and a rapid response time (1.0–2.5 s) during the coloring/bleaching process.     

纳米多孔阳极氧化铁膜的形成及其形貌演变

阳极氧化法制备具有纳米多孔结构的阳极氧化铁膜因其潜在的应用价值而倍受关注。然而,在阳极氧化过程中多孔结构的形成机制至今尚不清楚。本文结合电流密度-电位响应（I-V曲线）及法拉第定律的推导,分析了形成纳米多孔阳极氧化铁膜的过程中阳极电流的组成。结果表明,离子电流（导致离子迁移形成氧化物）和电子电流（导致析出氧气）共同组成阳极电流,并且纳米多孔阳极氧化铁膜的形成与两种电流的占比相关。分段式氧化物之间的空腔以及在阳极氧化初期纳米孔道上覆盖的致密膜,表明氧气泡可能是从氧化膜内部析出。此时,阳离子和阴离子绕过作为模具的氧气泡实现传质,最终导致纳米多孔结构的形成。此外,在阳极氧化铁膜形貌演变过程中,氧气泡不断向外溢出会使表面氧化物被冲破,导致表面孔径不断增大。     

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.     

金属β－二酮化合物用于MOCVD法生长铁电氧化物薄膜

对用于MOCVD法生长铁电氧化物薄膜的金属β－二酮化合物的制备、结构及性质进行了评述，对它们在生长铁电薄膜中的应用现状进行了介绍，并对它们的应用前景作了展望。     

氯醇盐溶胶-凝胶法纳米结构氧化钨薄膜的光谱学特性

由非离子型Gemini表面活性剂TMDD(HO(EO)xC14(EO)yOH)为结构导向模板, 改进EISA(挥发诱导自组装)镀膜工艺经300 ℃焙烧制得具有连续、均一和光学透明特点的蠕虫介孔纳米晶孔壁氧化钨薄膜. 采用SEM、TEM和Raman光谱对此种薄膜的介孔纳米结构进行了表征, 通过光谱电化学、XPS和椭偏谱等方法, 研究了该薄膜在电解质溶液中的电致变色行为. 结果表明, 所制备的纳米结构氧化钨薄膜在633 nm波长处的循环可逆透过率调制幅度可达75%以上, 并且其电致变色机理具有显著的双注入吸收调制特性.     

二氧化钛纳米管阵列薄膜的超声辐射阳极氧化制备

通过使用铂片作为对电极在含有氢氟酸的二甲基亚砜溶液中, 将金属钛片进行阳极氧化的方法制备得到二氧化钛纳米管阵列薄膜. 在施加40 V偏压超声辐射作用下阳极氧化24 h条件下得到的二氧化钛纳米管长达到680 nm, 管内直径25 nm, 管壁厚度约3～5 nm. 采用了XRD和TEM等分析手段表征了二氧化钛纳米管阵列薄膜的微观结构和表面形貌, 分别测试了薄膜的光吸收性能、循环伏安特性和光化学转换效率, 并和碱性溶胶-凝胶方法制备的纳米晶二氧化钛薄膜作了对比研究. 实验制备的二氧化钛纳米管阵列薄膜电极的光吸收率比纳米晶二氧化钛薄膜提高了40%, 光电化学转换效率前者是后者的6倍, 实验结果表明二氧化钛纳米管阵列薄膜结构有利于加快电子的传输, 并能减少电荷复合, 采用这种二氧化钛纳米管阵列薄膜结构的染料敏化太阳能电池光电极有望进一步提高太阳能电池的效率. 本文还探讨了在超声波辐射作用下二氧化钛纳米管阵列薄膜的形成机理.