【作者】 赵青南；

【导师】 赵修建；

【作者基本信息】 武汉理工大学 ， 材料学， 2004， 博士

【摘要】 由于能源和资源的日益枯竭、环境污染的日益严重，人们迫切需要新材料，使其具有生态功能，体现在建筑玻璃上就是使窗玻璃的功能除采光、避风、遮雨外，还要有保温、光催化自洁净等功能。二氧化钛是目前氧化物半导体中稳定性最好的光催化降解有机污染物材料，在紫外线的照射下，它几乎可以把有机污染物完全降解为水和二氧化碳等小分子无机物。把二氧化钛膜镀在玻璃上使玻璃具有光催化自洁净功能，被认为是最希望实现的未来产品。因此，它具有广泛的应用前景。在建筑节能方面，窗玻璃是室内节能的薄弱环节，为了防止室内、外热量通过窗玻璃交换，目前采取在玻璃上镀功能膜的方法来反射红外线：阳光控制镀膜玻璃的可见光透射率太低，影响室内采光，低辐射镀膜玻璃的膜面需要安装在中空玻璃的内面并（或）加惰性气体保护密封。本学位论文的目的是探索用磁控溅射法在玻璃上镀二氧化钛膜，使玻璃具有光催化自洁净等功能；在玻璃上镀TiO₂／TiN／TiO₂多层复合膜，使玻璃同时具有光催化和节能双重功能。 首先，用磁控反应溅射法在普通浮法玻璃上沉积了二氧化钛膜，研究了二氧化钛膜的制备工艺，包括溅射气体中氧气／氩气比例、离线热处理温度、在线热处理温度等；用X-射线衍射仪（XRD）表征了薄膜的析晶状况和晶面取向，用X-射线光电子能谱（XPS）表征了薄膜表面的元素组成和离子存在状态，用扫描电镜（SEM）、透射电镜（TEM）和原子力显微镜（AFM）观察了薄膜的形貌和端面，用荧光发射光谱研究了薄膜中的氧缺陷，用紫外和可见光谱仪研究了薄膜的可见光透射率，用紫外灯做照射光源、测试了薄膜的水润湿角、降解水溶液中甲基橙、以及降解乙醛气体的能力。 第二，研究了Ce、N离子掺杂对石英玻璃基二氧化钛光催化膜结构与性能的影响，在溅射工艺上改变氧气／氩气比例，用XRD和TEM表征了薄膜的析晶状态、用XPS表征了薄膜的表面组成和离子状态，并用SEM观察了薄膜的表面形貌，测试了薄膜的水润湿角和降解水溶液中甲基橙的能力。 第三，在不同氮气分压下，用磁控溅射法在普通玻璃基片上沉积了TiN薄膜，对薄膜在不同温度下进行了热处理。用XRD和TEM表征了薄膜析晶状况，用SEM和AFM表征了薄膜的形貌，用XPS分析了薄膜的组成和离子状态，测试武汉理工大学博士学位论文了薄膜的面电阻和薄膜的可见光透射率。 第四，在理论上利用固体物理学和光学薄膜的基本原理，研究了寻找反射红外线功能膜的方法、及其确定膜厚的方法。在玻璃基片上根据诱导透射原理，用计算机模拟了TIOZ/TIN/Ti仇膜系的光学性能。 第五，在玻璃基片上用磁控溅射法沉积了Ti仇/TIN/Tio:复合膜，用紫外-可见一红外光谱仪表征了复合膜在20Onm³300nm波长的透射率和反射率，用XPS表征了复合膜的组成和离子状态，用SEM观察了薄膜的形貌，分析了复合膜的节能特性，研究了热处理对复合膜光谱性能的影响，表征了复合膜的水润湿角和光催化降解水溶液中甲基橙的能力，表征了薄膜的耐久性。 最后，得到以下结论: 1.在0.SOPa的溅射总气压下，用直流反应磁控溅射法制备玻璃基Ti02薄膜时，氧气与氢气的比例02/Ar二0.06、0.12和0.18时，未经热处理的试样都呈非晶态，500℃大气氛环境下处理Ti02薄膜o.sh，试样呈锐钦矿结晶相，并在（101）晶面择优取向。非晶氧化钦薄膜，无论是否用紫外线（UV）照射，亲水性都差。化学计量比高、析晶完善的Ti仇薄膜在LTV照射下，润湿角可以很快降低到5。。 2.为了提高溅射沉积Ti02薄膜的效率、并使薄膜析出二氧化钦锐钦矿结晶相，应采用氧气/氢气流量比仇/Ar二0.12或0.18、基片温度260℃³20℃的溅射工艺，得到膜面在（101）晶面择优取向;为了阻止玻璃基片中Na离子向膜扩散破坏晶体结构，膜的厚度要不小于25Onm。氧气/氢气流量比增加，薄膜结晶取向完善、化学计量比高，镀膜试样的光催化水润湿角很快达到5“、能够降解甲基橙和乙醛气体，结晶完善、表面形成颗粒一微孔结构的膜面有较好的光催化性能。 3.荧光发射光谱研究，二氧化钦膜带隙为3.35eV。溅射气氛中氧气/氢气分压比例从0.06增加到0.18（基片温度都是260℃），氧缺位能级减少。 4.在Ce厂Fi原子比小于0.07时，Ce以ce仍的形式掺杂到二氧化钦膜，它能提高二氧化钦膜的光催化效率:Ce离子掺杂的二氧化钦膜可以较好地阻止紫外线。N离子能够掺杂到二氧化钦膜的量极少，其中Nls结合能为396.25eV的间隙N离子提高二氧化钦膜的光催化性能，掺N二氧化钦膜水润湿角可达5。。 5.氮气分压对TIN膜的结构和性能影响较大。单一（200）晶面取向的TIN膜面电阻最小。溅射时的工作总气压为0.SOPa时，NZ/Ar比值在0.30⁰.35之间，溅射时间控制在5⁷分钟，TIN膜的可见光透射率峰值在45%左右、并对武汉理工大学博士学位论文应520nm波长。TIN膜容易氧化，表面生成Ti一N一O、Ti一0。 6.玻璃基TIOZ汀iN厅102多层薄膜同时具有节能和光催化降解有机污染物 （高亲水性）的功能。各膜层分别控制在40nln⁵0nln（内层二氧化钦）、35nm⁴5lun（TIN厚度）、45nm一60nln（外层二氧化钦），得到的镀膜玻璃试样具有50%⁶0%的可见光透射率，可见光反射率?更多还原

【Abstract】 More and more new materials with ecological function have been needed because of environmental problems, such as energy and natural resource will be used up in a near future, and environment is being polluted. In the field of building the glass should have energy-conserving and self-cleaning properties except for transmittance, shielding rain and wind. Up to now TiO2 is the most stable semi-conductors with photocatalytic properties, which can almost degrade all the organic pollutants into water and small inorganic molecular under the irradiation of ultraviolet. The TiO2 films coated on the glass will make the glass have photocatalytic properties, which have been thought as the most interested product in the near future, and the coated glass will have bright future. In the field of energy conservation of buildings, Window glass is weak. Coatings with the properties of reflecting infrared are coated on the glass in order to prevent the energy exchange between inside and outside of the room. The Solar control glass has low visible transmittance, but it makes room dark, low-e glass can only be used in sealed window spaces, which are filled with inert gas. The aim of the thesis is to explore the TiO2 films deposited on glass using magnetron sputtering, to make the coated glass have photocatalytic self-cleaning properties, and to deposited TiO2/TiN/TiO2 multi-films using magnetron sputtering, to make the multi-films have both self-cleaning and energy conserving properties.First, the processing conditions have been determined in order to get the better properties of the TiO2, including the sputtering gas ratio of O2 to Ar, heat-treatment temperature off line and in line. The crystalline phases and preferred orientation of the TiO2 films were investigated using X-ray diffraction (XRD),the chemical composition and ionic state on the surface of the films were characterized using X-ray photoelectron spectroscopy(XPS), the morphology and surface microstructure of the films were analyzed using scanning electron microscopy (SEM) ,Transmission electron microscopy (TEM) and atomic force microscopy (AFM), the oxygen defect of the films was researched using photoluminescence (PL) spectra, the transmittance of the films in the visible region is analyzed using ultraviolet-visible spectra(UV-Vis), photocatalytic activity of the films was evaluated by examining photocatalyticdecolorization of aqueous methyl orange, degradation of acetaldehyde and hydrophilic properties under irradiation of a high-pressure mercury lamp(125W)(UV).Second, the structure and properties of the Ce-doping and N-doping films coated on quartz glass were characterized using XRD and TEM for crystalline phases, XPS for the chemical composition and ionic state on the surface of the films, SEM for the morphology of the films, the photocatalytic activity of the films was evaluated by examining the water contact angle and photocatalytic decolorization of aqueous methyl orange.Third, under different N2 pressure,TiN films were deposited on soda-lime glass using magnetron sputtering. The TiN films were annealed at different temperature, and the crystalline phases were analyzed using XRD and TEM, the morphology of the TiN films was investigated using SEM and AFM, the chemical composition and ionic state on the surface of the TiN films were analyzed using XPS, the transmittance of the TiN films was analyzed using UV-Vis, the sheet resistance of the films was tested using four-point method.Fourth, the methods to look for materials of reflecting infrared have been researched using the basic theory of solid physics and optical films, the optical properties of the TiO2/TiN/TiO2 multi-films were simulated using computer.Fifth, the multi-films TiO2/TiN/TiO2 were deposited on soda-lime glass using sputtering, the reflectance and transmittance of the films in the region of 200nm-3300nm wavelength were analyzed using Beckman UV 5240 and Cary 500, instrument version 8.01. The composition and ionic state of the films were analyzed using XPS, the performance of the energy con更多还原