Photoinduced superhydrophilic properties of Ti-B binary oxide thin films and their photocatalytic reactivity for the decomposition of NO

Characterizations of Ti-B binary oxide thin films by means of various spectroscopic measurements have shown that Ti-B binary oxide thin films are formed by ultra fine TiO2 nanoparticles. A dramatic decrease in the contact angle of water droplets to 0 degree under ultraviolet (UV) light irradiation and a return to only half of its initial value under dark conditions were observed for the Ti-B binary oxide thin films. Moreover, ultraviolet irradiation of these thin film photocatalysts in the presence of NO led to photocatalytic decomposition of NO into N2 and O2. Especially when the Ti content was low, the size of the primary nanoparticles of the thin films was smaller and the photocatalytic reaction proceeded efficiently with a high selectivity for the formation of N2 and O2 from NO.     

Titanium monoxide ultra-thin coatings evaporated onto polycrystalline copper films

We evaporated polycrystalline copper thin films of thickness between 10 and 100 nm on silicon substrates with their native oxide under ultra-high-vacuum conditions. Some of them were exposed to air for a period ranging from 1 day to 2 weeks. X-ray photoelectron spectroscopy (XPS) revealed a clean copper surface with a trace of oxygen. These films that were exposed to air presented oxides in the state Cu(II), the amount of CuO depended on the time that the film was exposed to air. Subsequently, we deposited TiO ultra-thin films on polycrystalline copper substrates. Both these thin films were formed by electron beam evaporation. XPS spectra showed that the surface of the titanium monoxide (TiO) films was contamination-free. An evaporation of 0.3 nm of TiO reduced the native oxide of the copper substrates from Cu(II) to Cu(I) or Cu(0) and transformed the TiO into TiO₂ at the interface. Low-energy ion spectroscopy showed that the complete coverage of the substrates depends on the thickness of the copper films. For 10 nm copper thin films the complete coverage occurred at 1.5 nm of TiO, and for 100 nm it occurred at 2.0 nm of TiO. In samples exposed to air, the complete coverage occurred at a film thickness slightly higher than those treated under ultra-high-vacuum conditions.     

柱状晶形貌TiO2膜厚对FTO/TiO2镀膜玻璃光催化活性影响

采用溶胶凝胶法,在FTO(SnO2:F)低辐射镀膜玻璃衬底上制备了柱状晶体结构的TiO2薄膜,获得双层结构FTO/TiO2镀膜玻璃样品.研究了TiO2薄膜厚度对FTO/TiO2镀膜玻璃样品的光催化活性、低辐射性能以及透光性能的影响.结果表明,FTO/TiO2镀膜玻璃样品光催化活性随着TiO2薄膜厚度的增加先升高后下降,在TiO2薄膜厚度为300 nm时光催化活性最佳;低辐射性能随着TiO2薄膜厚度的增加而下降,但TiO2薄膜厚度为300 nm时仍然具备一定的低辐射性能;透光性能与TiO2薄膜膜厚的关系不大,可见光透射比保持在72%左右;表面平均粗糙度约为1 nm,表面光滑,不易沾染油污灰尘.该镀膜玻璃在保证低辐射建筑节能和透光的前提下,兼具光催化自清洁功能,具有很好的应用前景.     

溶胶-凝胶法制备TiO2纳米薄膜的晶粒长大机理研究

通过sol-gel法在普通钠钙玻璃表面制备了均匀透明的锐钛矿型TiO2纳米薄膜.用透射电镜(TEM)、X射线衍射(XRD)和紫外可见吸收光谱(UV-VIS)等对薄膜的晶粒大小和透光率进行了表征.结果表明:随着镀膜次数和热处理时间的增加,薄膜中的平均晶粒大小接近线性增加.仅增加TiO2薄膜的热处理时间,薄膜中晶粒长大不明显,其吸收阀值未发生明显的红移.因此, 薄膜中晶粒长大的机理可能是: 上一次镀的TiO2晶粒成了下一次镀TiO2溶胶的晶核, 并在此基础上逐渐长大.     

Photocatalytic reduction of NO with NH3 using Si-doped TiO2 prepared by hydrothermal method

A series of Si-doped TiO2 (Si/TiO2) photocatalysts supported on woven glass fabric were prepared by hydrothermal method for photocatalytic reduction of NO with NH3. The photocatalytic activity tests were carried out in a continuous Pyrex reactor with the flow rate of 2000mL/min under UV irradiation (luminous flux: 1.1x10(4)lm, irradiated catalyst area: 160cm2). The photocatalysts were characterized by X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) spectrophotometer, transmission electron microscopy (TEM), photoluminescence (PL) and temperature-programmed desorption (TPD). The experiment results showed that NO conversion on Si/TiO2 at 323K could exceed 60%, which was about 50% higher than that on Degussa P25 and pure TiO2. With the doping of Si, photocatalysts with smaller crystal size, larger surface area and larger pore volume were obtained. It was also found that Ti-O-Si bands were formed on the surface of Si/TiO2 and that the surface hydroxyl concentration was greatly increased. As a result, total acidity and NH3 chemisorption amount were enhanced for Si/TiO2 leading to its photocatalytic activity improvement.     

阴极共电沉积法制备 Fe 3+掺杂 TiO 2纳米薄膜及其可见光活性

研究了阴极共电沉积制备Fe^3＋掺杂TiO2纳米薄膜（Fe-TiO2）的新方法.应用该方法、溶胶-凝胶法和浸渍法分别制备了具有可见光响应的Fe-TiO2光催化剂.并用XRD、SEM、EDS和UV-vis吸收光谱对Fe-TiO2进行了表征.结果表明,与溶胶-凝胶法和浸渍法相比共电沉积法不仅能有效地实现Fe^3＋在TiO2中的均匀分布,而且,得到的光催化剂具有最大的比表面积和最好的光降解活性.Rhodamine B（RhB）降解实验表明,在RhB光降解中存在光敏化和光催化降解的协同效应.     

离子注入改善纳米二氧化钛薄膜光催化性能

利用直流磁控反应溅射技术在玻璃衬底上制备了透明的纳米TiO2光催化薄膜。利用离子注入技术将Sn离子注入到TiO2表面以提高其光催化活性。用X射线衍射（XRD）、X射线光电子谱（XPS）以及UV－VIS分光光度计对薄膜进行结构与性能表征。Sn离子注入后的薄膜具有更高的光催化活性，这是因为在TiO2和SnO2半导体的复合体系中，电子－空穴对的分离变得更加有效，从而提高了其催化性能。     

Photocatalytic degradation of methyl orange: influence of H2O2 in the TiO2-based system

The purpose of this study was to investigate the photocatalytic oxidation of a reactive azo dye. The photocatalytic activity of the TiO2 was studied using a reactor equipped with UV-A sources, with maximum emission at 365 nm. The photocatalytic activity of the TiO2 powder (99.9% anatase) and thin films has been measured through the decomposition of methyl orange solutions. The thin film was prepared by doctor blade and spray pyrolysis deposition (SPD). The TiO2 suspensions were prepared at 1 g/L concentration, and the initial methyl orange concentration was fixed at 7.8125 mg/L. The influence of the TiO2 (powder or thin films) and/or O2 and H2O2 on the photobleaching rate, was tested under different experiments, at pH = 5. Thin films (doctor blade) of TiO2 formed of mezo-sized aggregates formed of nanosized anatase crystallites show better photobleaching efficiency than thin film (SPD) due to their large internal surface. The rate is even higher in H2O2 compared to oxygen environment.     

Controlling the crystallinity and roughness of atomic layer deposited titanium dioxide films

The surface roughness of thin films is an important parameter related to the sticking behaviour of surfaces in the manufacturing of microelectomechanical systems (MEMS). In this work, TiO2 films made by atomic layer deposition (ALD) with the TiCl4-H2O process were characterized for their growth, roughness and crystallinity as function of deposition temperature (110-300 degrees C), film thickness (up to approximately 100 nm) and substrate (thermal SiO2, RCA-cleaned Si, Al2O3). TiO2 films got rougher with increasing film thickness and to some extent with increasing deposition temperature. The substrate drastically influenced the crystallization behaviour of the film: for films of about 20 nm thickness, on thermal SiO2 and RCA-cleaned Si, anatase TiO2 crystal diameter was about 40 nm, while on Al2O3 surface the diameter was about a micrometer. The roughness could be controlled from 0.2 nm up to several nanometers, which makes the TiO2 films candidates for adhesion engineering in MEMS.     

磁控溅射制备纳米TiO2薄膜导电性的研究

研究了在纳米厚度范围内，TiO2薄膜的导电性与薄膜厚度和基底材料的关系。利用射频磁控溅射方法，使用高纯Ti(99．99％)靶，通入Ar和O2的混合气体，制备了TiO2薄膜，薄膜膜厚15—225nm,在室温下测量了不同厚度TiO2薄膜的电阻率，发现TiO2薄膜的导电性，先后在导体、半导体和绝缘体范围变化。这归因于基底材料与TiO2的功函数不同，导致了界面电子的转移，功函数差决定了电子转移的深度。     

Interference effects in photoacoustic and reflectance spectroscopies on TiO2/Si structures and TiO2 band gap

Experimental results of photoacoustic (PAS) and reflectance (RS) spectroscopies of titanium dioxide thin films (TiO2), deposited on Si substrates, are compared in a wide optical range including transparent and absorbent regions of TiO2. Due to the fact that the light modulation frequency f used in the photoacoustic experiments was so low that the thermal diffusion length of the TiO2 (mu = 100 microm) is always larger than the thickness of the studied films, the PAS turns out to be complementary to RS over the entire range. The presence of multiple reflection interference effects makes difficult a direct evaluation of the TiO2 band gap from the PAS signal. However, by employing k(lambda) values, obtained from transmission experiments on equivalent TiO2 films deposited on transparent fused quartz substrates, the PAS spectra for the films deposited on silicon are reconstructed by using those theoretical models that consider multiple reflections. The reasonable agreement of the simulated and experimental PAS spectra allows one to obtain reliable Eg values for the TiO2 films deposited on opaque silicon substrates.     

FeS2/TiO2复合薄膜光电性能

采用溶液浸渍法在ITO导电玻璃表面的多孔TiO2薄膜上沉积了FeS2薄膜.使用Fe2O3粉末保护裸露在外的ITO导电膜在硫气氛中热处理后,制得了FeS2/TiO2复合薄膜.应用B531/H数显测厚指示表、数字式四探针测试仪、XJCM-8太阳电池测试仪等研究了FeS2/TiO2复合薄膜的厚度、ITO导电玻璃的电阻率以及FeS2/TiO2复合薄膜的光电性能.结果表明：此方法制得的FeS2/TiO2复合薄膜具有良好的光电性能;且ITO导电膜的电阻率变化较小.因而适宜制备色素增感太阳能电池（DSSC）.     

Chemical gas sensor application of open-pore mesoporous thin films based on integrated optical polarimetric interferometry

Chemical gas sensors that employ integrated optical polarimetric interferometry were fabricated by the sol-gel synthesis of transparent mesoporous thin films of TiO2-P2O5 nanocomposite on tapered layers of TiO2 sputtered on tin-diffused glass waveguides. Atomic force microscopy images of the mesoporous thin film clearly show the open pore mouths on the film surface that favor rapid diffusion and adsorption of gas-phase analytes within the entire film. Adsorption of gas and vapor induces changes (Deltan) in the refractive index of the mesoporous thin film that lead to shifts in the phase difference between the fundamental transverse electric and magnetic modes simultaneously excited in the glass waveguide via single-beam incidence. Upon exposure to NH3 gas at concentrations as low as 100 ppb in dry air at room temperature, the sensor exhibits a reversible change in the phase difference with the response and recovery times of less than 60 and 90 s, respectively. It is unexpected that the sensor is unresponsive to either NO2 or C6H6 vapor, leading to a somewhat selective sensitivity to NH3. Determination of Deltan was carried out with a combination of the experimental results and the theoretical calculations. The sensor design represents a novel, effective, and easily accessible approach to mesoporous thin-film-based integrated optical chemical sensors.     

Photocatalytic Property of TiO2 Films Deposited by Pulsed DC Magnetron Sputtering

TiO2 thin films were prepared by DC magnetron sputtering with the oxygen flow rate higher than the threshold. The film deposited for 5 h was of anatase phase with a preferred orientation along the <220> direction, but the films deposited for 2 and 3 h were amorphous. The transmittance and photocatalytic activity of the TiO2 films increased constantly with increasing film thickness. When the annealing temperature was lower than 700℃, only anatase grew in the TiO2 film. TiO2 phase changed from anatase to rutile when the annealing temperature was above 800℃. The photocatalytic activity decreased with increasing annealing temperature.     

复合电沉积制备SnO2/TiO2薄膜及其光电催化性能

为了寻求廉价、高效和稳定的光催化剂,用复合电沉积技术在紫铜片上制备了Sn/TiO2薄膜,经300℃热氧化使之形成SnO2/TiO2复合电极.利用SEM,XRD对薄膜进行了表征,以甲基橙为模型化合物,对复合电极的光催化和光电催化性能进行了测定.研究表明:该薄膜由0.3~1μm的颗粒构成,每个颗粒又由纳米晶粒形成;电极具有多孔结构,膜中的SnO2以两种不同的晶体结构存在;在薄膜质量相等的情况下,SnO2/TiO2薄膜的光催化活性是纯TiO2粒子膜的2.87倍;外加一定偏压下,其催化性能大幅度提高.     

超亲水TiO_2/SiO_2复合薄膜的制备与表征

通过 ｓｏｌ－ｇｅｌ工艺在普通钠钙玻璃表面制备了均匀透明的 ＴｉＯ２／ＳｉＯ２复合薄膜．实验结果表明：在 ＴｉＯ２薄膜中添加 ＳｉＯ２,可以抑制薄膜中 ＴｉＯ２晶粒的长大,同时薄膜表面的羟基含量增加,水在复合薄膜表面的润湿角下降,亲水能力增强．当 ＳｉＯ２含量为 １０～２０ ｍｏｌ％时获得了润湿角为０°的超亲水性薄膜．     

Effect of surface fluorination of TiO2 particles on photocatalitytic activity of a hybrid multilayer coating obtained by sol-gel method

A multilayer photoactive coating containing surface fluorinated TiO(2) nanoparticles and hybrid matrices by sol gel approach based on renewable chitosan was applied on poly(lactic acid) (PLA) film by a step wise spin-coating method. The upper photoactive layer contains nano-sized functionalized TiO(2) particles dispersed in a siloxane based matrix. For the purpose of improving TiO(2) dispersion at the air interface coating surface, TiO(2) nanoparticles were modified by silane coupling agent 1H,1H,2H,2H-perfluorooctyltriethoxysilane (FTS) with fluoro-organic side chains. An additional hybrid material consisting of chitosan (CS) cross-linked with 3-glycidyloxypropyl trimethoxy silane (GOTMS) was applied as interlayer between the PLA substrate and the upper photoactive coating to increase the adhesion and reciprocal affinity. The multilayer TiO(2)/CS-GOTMS coatings on PLA films showed a thickness of ~4-6 μm and resulted highly transparent. Their structure was exhaustively characterized by SEM, optical microscope, UV-vis spectroscopy and contact angle measurements. The photocatalytic activity of the multilayer coatings were investigated using methyl orange (MeO) as a target pollutant; the results showed that PLA films coated with surface fluorinated particles exhibit higher activity than films with neat particles, because of a better dispersion of TiO(2) particles. The mechanical properties of PLA and films coated with fluorinated particles, irradiated by UV light were also investigated; the results showed that the degradation of PLA substrate was markedly suppressed because of the UV adsorptive action of the multilayer coating.     

Diagnostic in TCOs CVD processes by IR pyrometry

Infra red pyrometry is a sensitive, simple and low-cost technique commonly used for the measurement of the deposition temperature in CVD processes. We demonstrate in this work that this optical technique can be used as diagnostic tool to provide fruitful informations during the growth under atmospheric pressure of TiO₂ films on various substrates chosen as an example of transparent oxide. Significant variations of the pyrometric signal were observed during the deposition of TiO₂ thin films due to interferences in the growing film resulting from multi-reflections at the interfaces and scattering induced by the surface roughness. Modeling of the time dependence of the IR pyrometric signal allows simultaneously the determination of the layer thickness, the growth rate, surface roughness and refractive index of the thin films under the growth conditions. This diagnostic technique can be used for various transparent thin films grown on opaque substrates and is well adapted to control CVD processes operating either under atmospheric or low pressure and more generally any thermal treatment processes.     

TiO2功能薄膜的制备及影响其光催化活性的因素

近些年来，TiO2功能薄膜以其卓越的性能，尤其是优异的光催化性能引起研究人员的广泛关注，本文根据国内外近期TiO2功能薄膜的研究现状，对化学气相沉积法，水解一沉淀法，液相沉积法，溶胶－凝胶法，原子层沉积法，溅射法，激光辅助分子束沉积法等化学和物理制备方法进行评述，并比较详细地探讨了表面羟基含量，膜的厚度和孔径，结晶形态，基片种类，掺杂和光强度等因素对TiO2薄膜光催化性能的影响。     

Effect of filler types and calcination temperature on the microstructure and the nitric oxide photocatalytic activity of composite titanium dioxide films

The composite titanium dioxide (TiO(2)) films coating on the woven glass fabric were prepared by a modified sol-gel process, using pre-calcinated TiO(2) nanoparticle or silica gel as filler. The characterized physicochemical properties of the prepared catalyst films showed that the specific surface area, the microstructure and the crystal structure of the catalysts were greatly affected by the fillers and the calcination temperature. The physicochemical properties of composite films and the photocatalytic activity of nitric oxide (NO) show that the pre-calcinated TiO(2) nanoparticle is more favorable than silica gel as filler. The pre-calcinated TiO(2) nanoparticle filler can increase the photocatalytic activities of the catalysts by increasing the specific surface area, introducing a bimodal mesoporous structure, and creating a polymorphous crystal structure. And the TiO(2)-TiO(2) film calcinated at 400 degrees C exhibits the highest photocatalytic activity for NO oxidation and is more active than Degussa P25.