纳米ZnO-SiO2自清洁增透薄膜的制备及其性能

以乙酸锌醇热法ZnO纳米粒子为基料, 通过溶胶-凝胶浸渍提拉法制备纳米ZnO-SiO₂自清洁增透薄膜. 采用透射电镜, 光谱椭偏仪, 扫描电镜, X-射线衍射, 差热分析仪和UV-vis等技术对样品进行表征, 以亚甲基蓝的光催化降解为目标反应, 评价其光催化活性. 结果表明, ZnO纳米粒子为球粒状结构, 直径约12-20 nm, 特征紫外吸收波长位于375 nm 处; 与未涂覆纳米ZnO-SiO₂自清洁增透薄膜的石英玻璃基底相比, 涂覆后石英玻璃在400-800 nm波长范围内平均透光率提升达4.17%, 具有良好的宽光谱增透行为; 且在紫外光激发下对亚甲基蓝染料具有光催化降解特性, 进而具备良好的自清洁性能.

Preparation and characterization of self-cleaning and anti-reflection ZnO-SiO2 nanometric films

Unlike the general anti-reflection and self-cleaning film such as SiO₂ and TiO₂-SiO₂, the ZnO-SiO₂ nanometric film used as a substrate of excellent transparency in visible region and effective photo-catalytic self-cleaning under UV illumination is seldom studied in the application as a substrate; however, it has a lot of advantages including high transmittance and low refractivity. In this paper, a self-cleaning and anti-reflection ZnO-SiO₂ nanometric film is successfully fabricated by using a sol-gel dip-coating method. The morphology, crystal structure, surface microstructure and light transmittance of the obtained products are characterized by techniques such as TEM, SAD, XRD, SEM, DTA and UV-vis. Photo-catalytic degradation of the methylene blue (MB) in aqueous solution is used as probe reaction to evaluate the photo-catalytic activity of ZnO-SiO₂ nanometric film. The TEM images reveal that the as-prepared ZnO nanoparticles are spherical grains with diameters of 12-20 nm, the average grain diameter is about 14.51 nm. ZnO nanoparticles obtained are of hexagonal wurtzite structure revealed by XRD pattern and there exist no other diffraction peaks, Furthermore, the SAD results show that ZnO microstructurs have good crystallinity. In addition, the ZnO grain size is about 14.41 nm by using the Scherrer formula calculation, which is consistent with the TEM results by the Gauss simulation. The UV-vis spectra reveal that the ultraviolet characteristic absorption peak of ZnO-SiO₂ composite films is located at 368 nm and 375 nm after annealing at different temperatures such as 300℃ and 450℃, corresponding to the band gaps of 3.37 eV and 3.31 eV, respectively. It is highly consistent with that obtained from pure ZnO nanoparticles. Increasing the annealing temperature results in a lower refractive index and the increases of the porosity in of the ZnO-SiO₂ composite films. It has a uniformly refractive index value about 1.23-1.25 and a high porosity value about 50.3-54.7% when the annealing temperature is 450 ℃. Experimental results show that the ZnO-SiO₂ composite film can enhance the light transmittance of the quartz substrate, due to its lower reflective index and higher porosity. Compared with the quartz substrate, the average optical transmission rate of the quartz glass coated with ZnO-SiO₂composite films is increased by about 4.17% at 400-800 nm, which favors greatly anti-reflection characteristics in a wide spectrum range. Meanwhile, the ZnO-SiO₂ composite films are found to be efficient for photo-catalytically degradation of methylene blue dye under UV illumination, which favors greatly the self-cleaning function.