热处理对TiO_2薄膜微观结构及催化性能的影响
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摘要
TiO_2薄膜是众多氧化物半导体薄膜中研究最为广泛的一种材料，由于其具有较好的化学稳定性、可靠的物理、光电子特性和高折射率、高介电常数等优良性能，因此被广泛应用于气敏材料、光催化材料、集成电路以及光电太阳能电池等领域；特别是TiO_2光催化剂因具有稳定性好、光催化活性高等优点，在污水处理、空气净化和杀菌消毒等研究领域受到了人们的高度重视。TiO_2光催化剂的晶体结构、晶粒尺寸、结晶度和表面微结构等因素对其光催化活性具有较大的影响。另外，为改善纳米TiO_2的结晶度和微结构，热处理是一种简单而有效的方法。因此研究不同热处理温度对TiO_2的晶相结构和光催化性能影响，具有重要的理论和现实意义。
本论文采用直流反应磁控溅射的方法在高纯石英玻璃上制备了TiO_2薄膜，并进行了不同温度的退火热处理。采用原子力显微镜(AFM)、X射线衍射仪(XRD)、紫外-可见分光光度计(UV-vis)和透射电子显微镜(TEM)等分析方法对薄膜的晶相结构和表面形貌进行了测定和表征，分析并探讨了热处理对薄膜结构形貌及光催化性能的影响。研究结果表明：热处理对样品的微结构以及光催化活性有很大的影响。随着热处理温度的升高，薄膜的晶型从非晶态转变为锐钛矿晶型，且锐钛矿的结晶度逐渐提高，薄膜的光催化活性随之增强，在500°C时，达到最大值。当热处理温度为600°C时，TiO_2薄膜出现金红石相，由于晶型转变和颗粒尺寸增大产生的综合效果，导致薄膜光催化降解能力显著降低。
Titanium dioxide (TiO_2) has been extensively investigated in the past decades dueto its excellent electric, optical and catalytic properties, chemical stability andnon-toxicity. The performance for a given application depends strongly on the structure,morphology, grain size and specific surface area. And heat treatment is a simple andeffective method to improve the crystalline and microstructure of TiO_2films. Asystematic study of the effect of the heat treatment temperature on crystalline structure,morphology, and photocatalytic activity of the TiO_2thin films is important.
The TiO_2thin films were prepared on high purity silica substrates using DCreactive magnetron sputtering method and by heat treatment at different temperatures.X-ray diffraction (XRD), Atomic force microscope (AFM), ultraviolet-visiblespectrophotometry (UV-vis) and transmission electron microscope (TEM) were used tocharacterize the structure and morphology of the TiO_2thin films. And the effect of heattreatment on the structure and photocatalytic activity of the TiO_2thin films is discussed.The results showed that heat treatment have a great influence on the microstructure andphotocatalytic activity of the TiO_2thin films. With increasing heat treatmenttemperature, the films structure changed from amorphous to crystalline anatase and thecrystallization of anatase has improved gradually. At500°C, the TiO_2thin film showedthe highest photocatalytic activity. When the heat treatment temperature increased to600°C, the photocatalytic activity of thin film decreased, which is owing to theformation of rutile phase and growth of TiO_2crystallites resulting in the decrease ofsurface area.
本论文采用直流反应磁控溅射的方法在高纯石英玻璃上制备了TiO_2薄膜，并进行了不同温度的退火热处理。采用原子力显微镜(AFM)、X射线衍射仪(XRD)、紫外-可见分光光度计(UV-vis)和透射电子显微镜(TEM)等分析方法对薄膜的晶相结构和表面形貌进行了测定和表征，分析并探讨了热处理对薄膜结构形貌及光催化性能的影响。研究结果表明：热处理对样品的微结构以及光催化活性有很大的影响。随着热处理温度的升高，薄膜的晶型从非晶态转变为锐钛矿晶型，且锐钛矿的结晶度逐渐提高，薄膜的光催化活性随之增强，在500°C时，达到最大值。当热处理温度为600°C时，TiO_2薄膜出现金红石相，由于晶型转变和颗粒尺寸增大产生的综合效果，导致薄膜光催化降解能力显著降低。
Titanium dioxide (TiO_2) has been extensively investigated in the past decades dueto its excellent electric, optical and catalytic properties, chemical stability andnon-toxicity. The performance for a given application depends strongly on the structure,morphology, grain size and specific surface area. And heat treatment is a simple andeffective method to improve the crystalline and microstructure of TiO_2films. Asystematic study of the effect of the heat treatment temperature on crystalline structure,morphology, and photocatalytic activity of the TiO_2thin films is important.
The TiO_2thin films were prepared on high purity silica substrates using DCreactive magnetron sputtering method and by heat treatment at different temperatures.X-ray diffraction (XRD), Atomic force microscope (AFM), ultraviolet-visiblespectrophotometry (UV-vis) and transmission electron microscope (TEM) were used tocharacterize the structure and morphology of the TiO_2thin films. And the effect of heattreatment on the structure and photocatalytic activity of the TiO_2thin films is discussed.The results showed that heat treatment have a great influence on the microstructure andphotocatalytic activity of the TiO_2thin films. With increasing heat treatmenttemperature, the films structure changed from amorphous to crystalline anatase and thecrystallization of anatase has improved gradually. At500°C, the TiO_2thin film showedthe highest photocatalytic activity. When the heat treatment temperature increased to600°C, the photocatalytic activity of thin film decreased, which is owing to theformation of rutile phase and growth of TiO_2crystallites resulting in the decrease ofsurface area.
引文
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[24]洪孝挺,王正鹏,陆峰,等.可见光响应型非金属掺杂TiO2的研究进展[J]．化工进展,2004,23(10):1077-1080．
[25] Yalcin, Yelda, Murat. The Role of Non-Metal Doping in TiO2Photocatalysis [J], Journal ofAdvanced Oxidation Technologies,2010,(16):281-296.
[26] Yan Wang, Caixia Feng, Min Zhang, Jianjun Yang, and Zhijun Zhang. Enhanced visible lightphotocatalytic activity of N-doped TiO2in relation to single-electron-trapped oxygen vacancyand doped-nitrogen [J],Applied Catalysis B:Environmental,2010,100:84-90.
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[38]刘海津.新型掺杂二氧化钛纳米管光催化材料的制备及其光催化性能的研究[D].河南师范大学,2010.
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[40] Nishijima K., Fukahori T., Murakami N., et al., Development of a titania nanotube (TNT)loaded site-selectively with Pt nanoparticles and their photocatalytic activities.[J].Appl.Catal.,A,2008,337(1):105–109.
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[45] Choi H C, Jung Y M, Kim S B. size effects in the Raman spectra of TiO2nanoparticles. Vib.Spectrosc,2005,37:33.
[46] Wang J., Zhang Q.W., Yin S., et al., Raman spectroscopic analysis of sulphur-doped TiO2bycogrinding with TiS2.[J]. J. Phys. Chem. Solids,2007,68(2):189–192.、
[47]GeffckenW, BegerrE, Dtshc Rei ChsPatnet. Jenaaer Galwsekr Shoal and Gen.Jean.GDR.1939，736:411.
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