氧化物薄膜电化学沉积的研究进展

综述了氧化物薄膜电化学沉积的工艺条件与参数及其影响，给出了氧化物薄膜沉积的对象，描述了氧化物薄膜的作用和用途。     

Effects of oxygen content on bioactivity of titanium oxide films fabricated on titanium by electron beam evaporation

The titanium oxide films were fabricated on titanium metal by e-beam deposition technique in various oxygen partial pressures in order to investigate the effects of oxygen content in titanium oxide film on the bioactivity of titanium implant. The nano-sized titanium oxide particles were observed on the surface of specimens. Raman spectra showed that titanium oxide films deposited by e-beam evaporator had oxygen deficient TiO2 structure. The oxygen content in oxide films was calculated from the high resolution XPS spectra of Ti 2p. The densities of HA particles formed on the sample surfaces after immersion test in SBF became higher as the contents of oxygen in titanium oxide films increased. We concluded that the degree of hydroxyl group formation in SBF depended on the stoichiometry of TiO2, which enhanced the bioactivity of titanium.     

水解沉积--阳极氧化法形成Al-Ti复合氧化膜

通过含钛无机盐的水解沉积及高温热处理,铝电极箔表面形成高介电常数氧化物———TiO2 膜层,然后在己二酸铵溶液中恒电流阳极氧化,形成 Al Ti复合氧化膜。AFM观测了含钛无机盐水解沉积过程中,铝电极箔表面形貌的变化。在铬酸和磷酸的混合溶液中测试了氧化膜的耐电压随溶解时间的变化。通过SIMS检测了复合氧化膜中 Al3 、Ti4 的强度随溅射时间的变化。膜溶解试验及 SIMS 检测结果表明Al Ti复合氧化膜由 3 层组成,外层和中间层为 Al、Ti、O不同配比的混合物,内层则为纯的 Al2O3。铝电极箔比容随氧化膜耐电压的变化关系曲线表明,60V耐电压下,Al Ti复合氧化膜的比容提高率为51%。     

Optical properties of vapour chopped and nonchopped tin oxide thin films

The optical properties of vapour chopped and nonchopped undoped tin oxide thin films (1000 Å) have been studied. The films were prepared by thermal oxidation (in air) of vacuum evaporated vapour chopped and nonchopped tin thin films. Effect of varied oxidation temperature and duration was also studied. As revealed by X ray diffraction studies, polycrystalline (both tetragonal and orthorhombic) films were obtained. The refractive indices ranged from 1.575 to 1.667 and 1.600 to 1.810 for nonchopped and vapour chopped tin oxide films respectively. Refractive index was found to increase after ageing. The effect was found lower in vapour chopped films. The direct band gap values ranged from 2.18 to 2.51 and 2.95 to 3.08 for nonchopped and vapour chopped tin oxide films respectively. The films showed high optical transmittance in the visible range of the spectrum. It was observed that the heat treatment process strongly affects the properties of the films. The vapour chopped tin oxide thin films showed higher packing density, optical band gap and refractive index with lower ageing effect.     

The effect of hydrogen on the electric conductivity of tin oxide doped with yttrium

Amorphous films of tin oxide doped with yttrium were obtained by ion beam sputter deposition. After crystallization, the films acquired a nanocrystalline structure. The introduction of yttrium leads to an increase in the crystallization temperature of tin oxide. The electric conductivity of films containing yttrium in excess of 1 at. % is highly sensitive to hydrogen. Nanocrystalline films of tin oxide doped with yttrium may serve as hydrogen-sensitive media.     

Polyelectrolyte-mediated assembly of copper-phthalocyanine tetrasulfonate multilayers and the subsequent production of nanoparticulate copper oxide thin films

An approach to producing films of nanometer-sized copper oxide particulates, based on polyelectrolyte-mediated assembly of the precursor, copper(II)phthalocyanine tetrasulfonate (CPTS), is described. Multilayered CPTS and polydiallyldimethylammonium chloride (PDADMAC) were alternately assembled on different planar substrates via the layer-by-layer (LbL) procedure. The growth of CPTS multilayers was monitored by UV-visible spectrometry and quartz crystal microbalance (QCM) measurements. Both the UV-visible spectra and the QCM data showed that a fixed amount of CPTS could be attached to the substrate surface for a given adsorption cycle. Cyclic voltammograms at the CPTS/PDADMAC-covered gold electrode exhibited a decrease in peak currents with the layer number, indicating that the permeability of CPTS multilayers on the electrodes had diminished. When these CPTS multilayered films were calcined at elevated temperatures, uniform thin films composed of nanoparticulate copper oxide could be produced. Ellipsometry showed that the thickness of copper oxide nanoparticulate films could be precisely tailored by varying the thickness of CPTS multilayer films. The morphology and roughness of CPTS multilayer and copper oxide thin films were characterized by atomic force microscopy. X-ray diffraction (XRD) measurements indicated that these thin films contained both CuO and Cu2O nanoparticles. The preparation of such copper oxide thin films with the use of metal complex precursors represents a new route for the synthesis of inorganic oxide films with a controlled thickness.     

Surface characterization of Ag-ITO cermet films prepared by a new sol-gel method

Incorporation of Ag nanocrystal into indium tin oxide films (Ag-ITO) could enhance the conductivity of transparent oxide thus attracts more and more interest. Ag-ITO films were prepared by a modified sol-gel method. The surface structure was investigated by X-ray diffraction, X-ray diffuse scattering, and X-ray photoelectron spectroscope techniques. The results showed that stannous chloride worked well as the reduction agent of silver and ion donor source, resulting in high quality nanocomposite thin films. The embedment of silver nanoparticles decreased the crystallization temperature and inhibited the growth of indium oxide. Ag-ITO films have a hierarchical structure. Furthermore, the nanocomposite films were densified and homogenized through prolonging the thermal duration time. XPS results confirmed that a small amount of silver oxide appeared.     

Study on the effect of annealing on the electrical properties of n-type cuprous oxide

n-Type cuprous oxide was synthesized by controlling the bath pH of the electro-deposition. Thereafter, cuprous oxide films were annealed in nitrogen at different temperatures. The electrical properties of n-type cuprous oxide films before and after annealing were studied by the capacitance-voltage measurements. By analysis of the Mott-Schottky curves, it was found that the carrier concentration of cuprous oxide films varied with the deposition bath pH and the annealing temperature. Also, the flat-band potential shifted with the increasing annealing temperature.     

Surface structure of silver thin films on In2O3:Sn and Al2O 3 †

Surface structure of thin silver films (200 Å) on two technologically important films, indium tin oxide (ITO) and aluminium oxide, has been studied using scanning tunneling microscope. ITO films were prepared by reactive electron beam evaporation. Aluminium oxide films were prepared by oxidizing 2000 Å thick aluminium films evaporated on to H₂ terminated single crystal silicon substrates. The surface structure of silver on ITO and aluminium oxide appeared to be same and was characteristic of Stranski-Krastanov type. The observed asymmetry in the island shape was attributed to the anisotropic nature of the strain fields surrounding the nucleation centres.     

The use of silane silicon dioxide films to contour oxide edges

This paper demonstrates the use of silane silicon dioxide films to obtain controlled contours of oxide steps. In particular, the etch properties of composite oxide films are adjusted by controlling the amount of boron or phosphorous in chemically vapor deposited silane silicon dioxide films. The dependence of etch rate on impurity concentration is presented. Using the etch rate data, specific examples of composite oxide films are fabricated and the profiles after etching are examined by use of the scanning electron miscoscope.     

包铝层和氧化时间对2E12铝合金硫酸阳极氧化及膜层性能的影响

对保留表面包铝和去除包铝的2E12-T3铝合金采用硫酸阳极氧化处理工艺,研究了包铝层和氧化时间对铝合金阳极氧化行为及膜层耐蚀性的影响。采用扫描电子显微镜观察氧化膜的表面以及截面形貌,应用动电位扫描极化曲线和电化学阻抗谱对膜层的电化学性能进行分析。结果表明:两种铝合金表面均能形成具有防护性能的阳极氧化膜,膜层随氧化时间延长而增厚。富铜的第二相颗粒会使得不带包铝的2E12铝合金氧化膜具有更多孔洞缺陷,甚至出现微裂纹。保留包铝的2E12铝合金表面氧化膜更厚,孔洞缺陷少,耐蚀性更好。阳极氧化30min和45min的2E12铝合金阳极氧化膜具有较低的腐蚀电流和较高的多孔层阻抗,耐蚀性好。     

UV absorption studies of undoped and fluorine-doped tin oxide films

Tin oxide films undoped and doped with fluorine are prepared by a chemical vapour deposition technique involving the oxidation of SnCl₂. For fluorine doping a mixture of trifluoroacetic acid and deionized water is used. The optical properties of these films are investigated in the UV region (225–350 nm). It is observed that for an undoped tin oxide the absorption edge lies at 3.71 eV. It is also observed that for fluorine-doped tin oxide films the absorption edge shifts towards higher energies, which is related to the Moss-Burstein shift. In the case of fluorine-doped tin oxide films, depending on the fluorine concentration, the absorption edge lies in the range 3.89–4.07 eV. Undoped and fluorine-doped tin oxide films show a direct transition at 4.03 eV and in the range 4.17–4.29 eV respectively, whereas the indirect transition for undoped and fluorine-doped tin oxide films occurs at 3.35 eV and in the range 3.55–3.67 eV respectively.     

High resolution X-ray photoelectron spectroscopy of beta gallium oxide films deposited by ultra high vacuum radio frequency magnetron sputtering

The gallium oxide thin films with amorphous, crystalline, and nanostructure morphologies were deposited by a radio frequency magnetron sputtering system in ultra high vacuum conditions. High resolution X-ray photoelectron spectroscopy spectra of films were analyzed relating on the preparation conditions. On the amorphous films, the density of states at valence band region is dependent on the sputtering gas compositions. Beta gallium oxide (100) films are epitaxially deposited on magnesium oxide (100) crystalline substrate. The high resolution X-ray photoelectron spectra suggest the presence of the density of states valence band region with oxygen deficiency out of the stoichiometry on the epitaxial crystalline beta gallium oxide films.     

Influence of concentration and annealing temperature on spin-coated metal oxide thin films for optoelectronic devices

Journal of Materials Science: Materials in Electronics - The metal oxide thin films, such as cadmium oxide (CdO) and zinc oxide (ZnO) thin films, were deposited by sol–gel-derived spin...     

12Cr2MoWVTiB钢高温再热器管氧化膜的特征

电厂的12Cr2MoWVTiB钢高温再热器管实际运行中易出现氧化失效,为了对其实施有效的监督,采用扫描电镜、电子探针和X射线衍射对高温高压水蒸气下运行5.0×10~4h形成的氧化膜形貌、结构、成分及物相进行了分析.结果表明:氧化膜蒸汽侧形貌呈丘状或蘑菇云状,氧化膜基体侧呈方解石状,氧化膜横断面呈石状;氧化膜结构明显分为3层,外层、中间层和内层氧化膜均由粗大的柱状晶构成,各柱状晶层间有大量孔洞,而内层氧化膜与基体结合处氧化膜晶粒为细小等轴晶;O元素含量从外层氧化膜到靠近基体处,存在正的浓度梯度分布,而Fe,Cr,Mo元素含量存在负的浓度梯度分布,Cr,Mo元素在紧靠基体的氧化膜侧产生富集,含量均高于钢基体中的含量;氧化膜物相为Fe_3O_4和FeCr_2O_4.     

Fabrication of Flexible Metal‐Nanoparticle Films Using Graphene Oxide Sheets as Substrates

Graphene‐based sheets that possess a unique nanostructure and a variety of fascinating properties are appealing as promising nanoscale building blocks of new composites. Herein, graphene oxide sheets are used as the nanoscale substrates for the formation of silver‐nanoparticle films. These silver‐nanoparticle films assembled on graphene oxide sheets are flexible and can form stable suspensions in aqueous solutions. They can also be easily processed, forming macroscopic films with high reflectivity. Raman signals of graphene oxide in such hybrid films are increased by the attached silver nanoparticles, displaying surface‐enhanced Raman scattering activity. The degree of enhancement can be adjusted by varying the quantity of silver nanoparticles on the graphene oxide sheets.     

Nanostructured copper and copper oxide thin films fabricated by hydrothermal treatment of copper hydroxide nitrate

Metallic copper and copper oxide thin films were fabricated on surface of glass slide substrates. Copper oxide thin films were prepared by a hydrothermal method using an α-phase layered hydroxide, copper hydroxide nitrate as a precursor. Morphology, thickness and crystallite size of the obtained copper oxide thin films changed by changing the time of hydrothermal treatment. Accordingly, the copper oxide thin films showed various water contact angles and optical band gaps. As, the optical band gap of the nanostructured copper oxide thin films increased with an increase in hydrothermal time from 1.85 to 2.95 eV. Moreover, the water contact angles changed from 16.4 to 38.8° by changing the hydrothermal time. By a reductive hydrothermal-treatment route, the copper oxide thin film was reduced to metallic copper thin film without any particle growth.     

XPS and X-ray diffraction studies of aluminum-doped zinc oxide transparent conducting films

Aluminum-doped zinc oxide transparent conducting films are prepared by spray pyrolysis at different dopant concentrations. These films are subsequently characterized by X-ray diffractometric and X-ray photoelectron spectroscopic (XPS) techniques. The results are compared with those obtained from pure zinc oxide films prepared under identical conditions. X-ray diffraction measurements show an increase in lattice parameters (c and a) for aluminum-doped films while their ratio remains the same. This study also indicates that within the XPS detection limit the films are chemically identical to pure zinc oxide. However, a difference in the core-electron line shape of the Zn 2p_3/2 photoelectron peaks is predicted. An asymmetry in Zn 2p_3/2 photoelectron peaks has been observed for aluminium-doped films. The asymmetry parameters evaluated from core-electron line-shape analysis yield a value of the order of 0.04±0.01. The value is found to lie between those obtained for pure zinc oxide and has been attributed to the presence of excess zinc in the films.     

掺杂氧化钨薄膜的电致变色特性

掺杂氧化钼对氧化钨薄膜的电致变色特性有一定的影响,本文介绍了用电子束蒸发制备不同MoO3掺杂比例的氧化钨膜,对其着色态与漂白态的光学特性以及循环伏安特性进行了实验研究,通过对循环伏安曲线的分析,对杂氧化钨薄膜电致变色的机理进行了讨论。     

Characterization of tin oxide films prepared as gas sensors by conversion electron Mössbauer spectrometry

Mn and Ni oxides incorporated tin oxide films, prepared by a spray pyrolysis technique and treated in hydrogen atmospheres, were characterized by conversion electron Mössbauer spectrometry and electron spin resonance to study the gas-sensing mechanism of tin oxides by the addition of metal oxides. Although the chemical state of Sn in undoped tin oxide film did not change after treatment with 5% H₂ at 400°C, the reduced Sn species was detected in the tin oxide films doped with Pd. In Sn-Mn oxide films with the addition of Pd, the chemical state of Sn did not change, but the state of Mn changed on exposure to H₂. In Sn-Ni oxide films with and without Pd, the chemical states of Sn and Ni were strongly affected by H₂. A mechanism of hydrogen spillover effect on the tin oxide films is discussed.