喷雾热解法制备二氧化钛薄膜及其亲水性能的研究
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摘要
介绍了TiO_2功能薄膜的发展概况。TiO_2在光能的作用下能够产生良好的光催化特性和超亲水性。利用TiO_2超亲水特性，在普通玻璃上镀一层TiO_2薄膜，沾染在其上的污渍能够容易的被水冲走，使玻璃具有易清洁的特性。这种易清洁玻璃易于维护，在生产和生活中有良好的应用前景。
TiO_2薄膜的亲水性能受到结构形貌及其禁带宽度的影响，锐钛矿相的TiO_2具有最好的亲水特性；平整均匀的表面不仅有利于水的铺展，而且透光率高，适于玻璃镀膜；薄膜禁带宽度降低有利于提高光能的利用率。
根据超亲水TiO_2薄膜的要求展开了工作，通过对制备方法和原理的研究改进TiO_2薄膜的形貌，通过过渡金属离子的掺杂来降低薄膜的禁带宽度。
目前常用的TiO_2镀膜方法主要有溶胶凝胶和反应磁控溅射等方法，溶胶凝胶法薄膜厚度难以控制，磁控溅射需要复杂的真空设备，成本较高，限制了TiO_2镀膜在工业上的大规模生产。喷雾热解法具有沉积温度、速率容易控制，对基板选择性低，所得薄膜形貌均匀致密等特点。而且设备简单，成本低廉，在大规模工业生产方面有很大潜力。
根据防雾易清洁玻璃的性能要求，利用喷雾热解法，以透明载玻片为基板进行薄膜的制备。通过改变工艺参数获得了一系列TiO_2薄膜。并且制备了一系列组成的Fe~(3+)或Zn~(2+)掺杂TiO_2薄膜。通过XRD，SEM，AFM以及UV-VIS光谱分析等一系列手段对薄膜的结构和性能进行了全面的研究，并且测量了不同薄膜在接收光照后接触角的变化。
沉积温度和热处理时间对薄膜材料的结晶度有较大影响。薄膜的表面形貌随着喷雾参数的改变发生了较大的改变，喷雾参数的改变使是雾化液滴大小和液流密度随之发生了一定改变。过大的液滴使薄膜表面不均匀，液滴过小又会使薄膜表面形成孔洞，只有液滴直径在一定范围内制备的薄膜才能满足要求。结果表明，在液滴直径为13μm，液流密度在0.10mL／(min·cm~2)时制备的薄膜表面平整致密，有利于水滴的铺展。
对掺杂样品的研究结果表明，先驱体成分的改变对成膜过程没有影响，结构和形貌与未掺杂试样基本没有区别。Fe~(3+)掺杂离子的引入能够有效降低薄膜的光学能隙，提高薄膜的光响应范围，从而使薄膜的亲水性能提高；而Zn~(2+)掺杂对薄
浙往大’于倾卜、浏亿论文
膜的亲水性能没有改善。
本工作表明使用喷雾热解法可以有效的实现Tio:镀膜玻璃的制备，以及薄
膜的金属离子掺杂改性。讨论了喷雾参数和液滴大小的关系以及对所得薄膜质量
的影响，从而为本方法的工业化应用和推广到其它高质量薄膜的制备提供理论指
〔己
;J，。
A comprehensive introduction of photocatalitic and super hydrophilic material, TiC>2, was presented in this paper. It had many great merits such as excellent optical properties, low-cost and easiness to handle which offered promising prospects in the filed of self-cleaning, anti-fog and so on.
The hydrophilicity of TiO2 was influenced by many factors such as crystal structure, surface morphology, band gap, etc. Preparing method and doping element would take effect on the properties of the film.
The spray pyrolysis method has large application potency to be a method to prepare the economical thin films for its unsophisticated equipment, low-cost and high deposition rate which are great advantages if the technique is to be scaled up for industrial applications.
TiO2 thin films with super hydrophilicity were deposited onto soda-lime glass using the spray pyrolysis method, and the films doped with different content of Fe3+ or Zn2+ were also prepared. The crystal structure and surface morphology were characterized by XRD, SEM and AFM. The optical properties were characterized by uv-vis transmission spectrum. The hydrophilicity of the films was measured by a contact angle meter. And the mechanism of the film formation during the spray pyrolysis procedure was also discussed.
The results turned out that the crystal structure was changed by the variation of the deposition temperature and annealing time. The surface morphology was greatly influenced by the Spray parameters which atomized the precursor droplet in different diameters and different intensities.
When the droplets were in large diameter, the surface morphology would be more rough and heterogeneous. The surface morphology would be porous when the droplets were too small. It was found that the surface would be more smooth and homogenous when the droplets were in the middle scale. The hydrophilicity measurement shows that the smooth and homogenous surface of the TiO2 film showed to favor water spreading.
The influence of the transitional metal ion, Fe3+ and Zn2+, was discussed. Fe dopent can be easily put into the matrix of TiO2 and hardly inflects the crystal structure or surface morphology. It can decrease the band gap of the thin film effectively so that it will improve the hydrophilicity of the thin film. Zn dopent may change the crystal structure while the surface morphology becomes rough. And the band gap remains high. So the hydrophilicity of the thin film decreased.
It shows that the spray pyrolysis method can effectively produce TiO2 thin films with superhydrophilicity and offers an extremely easy way to dope films with other element. The analysis results in this work would be significant for reasonable utilization of spray pyrolysis deposition.
TiO_2薄膜的亲水性能受到结构形貌及其禁带宽度的影响，锐钛矿相的TiO_2具有最好的亲水特性；平整均匀的表面不仅有利于水的铺展，而且透光率高，适于玻璃镀膜；薄膜禁带宽度降低有利于提高光能的利用率。
根据超亲水TiO_2薄膜的要求展开了工作，通过对制备方法和原理的研究改进TiO_2薄膜的形貌，通过过渡金属离子的掺杂来降低薄膜的禁带宽度。
目前常用的TiO_2镀膜方法主要有溶胶凝胶和反应磁控溅射等方法，溶胶凝胶法薄膜厚度难以控制，磁控溅射需要复杂的真空设备，成本较高，限制了TiO_2镀膜在工业上的大规模生产。喷雾热解法具有沉积温度、速率容易控制，对基板选择性低，所得薄膜形貌均匀致密等特点。而且设备简单，成本低廉，在大规模工业生产方面有很大潜力。
根据防雾易清洁玻璃的性能要求，利用喷雾热解法，以透明载玻片为基板进行薄膜的制备。通过改变工艺参数获得了一系列TiO_2薄膜。并且制备了一系列组成的Fe~(3+)或Zn~(2+)掺杂TiO_2薄膜。通过XRD，SEM，AFM以及UV-VIS光谱分析等一系列手段对薄膜的结构和性能进行了全面的研究，并且测量了不同薄膜在接收光照后接触角的变化。
沉积温度和热处理时间对薄膜材料的结晶度有较大影响。薄膜的表面形貌随着喷雾参数的改变发生了较大的改变，喷雾参数的改变使是雾化液滴大小和液流密度随之发生了一定改变。过大的液滴使薄膜表面不均匀，液滴过小又会使薄膜表面形成孔洞，只有液滴直径在一定范围内制备的薄膜才能满足要求。结果表明，在液滴直径为13μm，液流密度在0.10mL／(min·cm~2)时制备的薄膜表面平整致密，有利于水滴的铺展。
对掺杂样品的研究结果表明，先驱体成分的改变对成膜过程没有影响，结构和形貌与未掺杂试样基本没有区别。Fe~(3+)掺杂离子的引入能够有效降低薄膜的光学能隙，提高薄膜的光响应范围，从而使薄膜的亲水性能提高；而Zn~(2+)掺杂对薄
浙往大’于倾卜、浏亿论文
膜的亲水性能没有改善。
本工作表明使用喷雾热解法可以有效的实现Tio:镀膜玻璃的制备，以及薄
膜的金属离子掺杂改性。讨论了喷雾参数和液滴大小的关系以及对所得薄膜质量
的影响，从而为本方法的工业化应用和推广到其它高质量薄膜的制备提供理论指
〔己
;J，。
A comprehensive introduction of photocatalitic and super hydrophilic material, TiC>2, was presented in this paper. It had many great merits such as excellent optical properties, low-cost and easiness to handle which offered promising prospects in the filed of self-cleaning, anti-fog and so on.
The hydrophilicity of TiO2 was influenced by many factors such as crystal structure, surface morphology, band gap, etc. Preparing method and doping element would take effect on the properties of the film.
The spray pyrolysis method has large application potency to be a method to prepare the economical thin films for its unsophisticated equipment, low-cost and high deposition rate which are great advantages if the technique is to be scaled up for industrial applications.
TiO2 thin films with super hydrophilicity were deposited onto soda-lime glass using the spray pyrolysis method, and the films doped with different content of Fe3+ or Zn2+ were also prepared. The crystal structure and surface morphology were characterized by XRD, SEM and AFM. The optical properties were characterized by uv-vis transmission spectrum. The hydrophilicity of the films was measured by a contact angle meter. And the mechanism of the film formation during the spray pyrolysis procedure was also discussed.
The results turned out that the crystal structure was changed by the variation of the deposition temperature and annealing time. The surface morphology was greatly influenced by the Spray parameters which atomized the precursor droplet in different diameters and different intensities.
When the droplets were in large diameter, the surface morphology would be more rough and heterogeneous. The surface morphology would be porous when the droplets were too small. It was found that the surface would be more smooth and homogenous when the droplets were in the middle scale. The hydrophilicity measurement shows that the smooth and homogenous surface of the TiO2 film showed to favor water spreading.
The influence of the transitional metal ion, Fe3+ and Zn2+, was discussed. Fe dopent can be easily put into the matrix of TiO2 and hardly inflects the crystal structure or surface morphology. It can decrease the band gap of the thin film effectively so that it will improve the hydrophilicity of the thin film. Zn dopent may change the crystal structure while the surface morphology becomes rough. And the band gap remains high. So the hydrophilicity of the thin film decreased.
It shows that the spray pyrolysis method can effectively produce TiO2 thin films with superhydrophilicity and offers an extremely easy way to dope films with other element. The analysis results in this work would be significant for reasonable utilization of spray pyrolysis deposition.
引文
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