玻璃基SnO_2透明导电薄膜及低辐射性能研究
摘要
氟或锑掺杂的氧化锡低辐射涂层玻璃被认为是最经济实用的建筑节能玻璃材料。自1985年英国皮尔金顿公司制造出第一块节能玻璃以来,各国均在低辐射玻璃领域进行了大量的研究,已经成功完善了磁控溅射法制备低辐射玻璃涂层的工艺,然而采用经济实用的喷雾热分解工艺制备低辐射玻璃能够极大地降低生产成本,在今后低辐射玻璃中低端产品领域将占据巨大的市场,因此,本课题着重于采用喷雾热分解法制备大面积低辐射玻璃涂层的研究,以期制备出综合光电性能优良的低辐射玻璃产品。
本课题在前期研究工作的基础上,进行了深入的理论探索,及产业化小试阶段初步尝试,具体工作如下：
1、探索氧化锡喷涂液的配制方法,成功配制出了性能优良的氟锑均掺杂的氧化锡喷涂液,利用FT-IR红外分光光度计、PHS-2F数字pH计等仪器对在配制过程中主要阶段的氧化锡喷涂液进行了红外光谱测试分析及pH值测定,研究其化学反应机理。
2、在生产线上对氟锑掺杂的氧化锡低辐射涂层玻璃制备过程中的各项工艺参数进行了探索,得出在生产线上的最佳制备工艺为：沉积温度700℃、玻璃相对移动速率6.93cm／s、预先喷涂Si02衬底和采用两次喷涂成型的方法。已能成功制备出薄膜的部分部位综合光电性能优良的低辐射玻璃,该部位方阻为23Ω／(?),半球辐射率为0.23,平均可见光透过率达到69%。
3、为节省成本、提高生产效率,对喷涂液进行改进,在实验室条件下成功制备出综合光电性能优良的氟掺杂的氧化锡薄膜,平均可见光透过率高达80%,半球辐射率低达0.11,说明改进后的喷涂液性能更优于改进前的喷涂液。利用XRD、SEM等仪器对氧化锡低辐射玻璃样品进行了微观结构和性能的测试分析,结果表明：制备的氟掺杂氧化锡薄膜为金红石结构的多晶体,具有单一的氧化锡四方相结构,品粒大小均匀、组织致密,缺陷较少。
The F or Sb doped tin dioxide for low-emissivity glass is one of the most economic and practical building materials. Since the British company Pilkington produced the first low-emissivity glass in 1985, many states have studied the low-emissivity glasses and have successfully improved the magnetron sputtering process. However, the use of economic and practical preparation of spray pyrolysis process can greatly reduce the cost of preparation, and its products will account for a huge market in the field of low-end products for the future. Then this paper focuses on the preparation of large-scale Low-E glass by spray pyrolysis, with a view to the integrated optical and conductive performance of Low-E glass products.
In preliminary studies of this topic, the basis of a thorough theoretical exploration have been researched and the small trial phase in the industrialization of the initial attempt has been conducted. Concrete work is as follows.
1. The preparation methods of tin oxide spraying liquid have been explored and the F-Sb doped tin oxide spraying liquid with excellent performance has been prepared successfully. FT-IR and pH value of tin oxide spraying liquid in the preparation of the main stage have been tested by the IR spectra and digital pH value meter, respectively. The chemical reaction mechanism has been explored.
2. The process parameters in the preparation of F-Sb doped tin dioxide for low-emissivity glasses has been studied on the production line and as the result the optimized preparation process has been obtained:700℃deposition temperature,6.93cm/s relative movement of the rate of glass, SiO2 underlay and two-times spray forming method. The excellent integrated optical and electrical performance of low-emissivity glasses have been obtained by this method, which sheet resistance, hemisphere emissivity and the average transmittance in visible region of the sample had reached 23Ω/□,0.23 and 69%respectively.
3. In order to save costs and improve productivity, the spraying liquid has been improved. Then the F doped tin dioxide film with excellent property has been prepared, which hemisphere emissivity and the average transmittance in visible region of the sample had reached 0.25 and 80% respectively. All of these have indicated that the improved spray liquid was better than the spraying liquid. The micro-properties of the F doped tin dioxide samples were investigated by XRD, SEM, and so on. The results showed that the film which had uniform crystal grains and compact structure with fewer defects was polycrystal with the tetragonal rutile structure.
本课题在前期研究工作的基础上,进行了深入的理论探索,及产业化小试阶段初步尝试,具体工作如下：
1、探索氧化锡喷涂液的配制方法,成功配制出了性能优良的氟锑均掺杂的氧化锡喷涂液,利用FT-IR红外分光光度计、PHS-2F数字pH计等仪器对在配制过程中主要阶段的氧化锡喷涂液进行了红外光谱测试分析及pH值测定,研究其化学反应机理。
2、在生产线上对氟锑掺杂的氧化锡低辐射涂层玻璃制备过程中的各项工艺参数进行了探索,得出在生产线上的最佳制备工艺为：沉积温度700℃、玻璃相对移动速率6.93cm／s、预先喷涂Si02衬底和采用两次喷涂成型的方法。已能成功制备出薄膜的部分部位综合光电性能优良的低辐射玻璃,该部位方阻为23Ω／(?),半球辐射率为0.23,平均可见光透过率达到69%。
3、为节省成本、提高生产效率,对喷涂液进行改进,在实验室条件下成功制备出综合光电性能优良的氟掺杂的氧化锡薄膜,平均可见光透过率高达80%,半球辐射率低达0.11,说明改进后的喷涂液性能更优于改进前的喷涂液。利用XRD、SEM等仪器对氧化锡低辐射玻璃样品进行了微观结构和性能的测试分析,结果表明：制备的氟掺杂氧化锡薄膜为金红石结构的多晶体,具有单一的氧化锡四方相结构,品粒大小均匀、组织致密,缺陷较少。
The F or Sb doped tin dioxide for low-emissivity glass is one of the most economic and practical building materials. Since the British company Pilkington produced the first low-emissivity glass in 1985, many states have studied the low-emissivity glasses and have successfully improved the magnetron sputtering process. However, the use of economic and practical preparation of spray pyrolysis process can greatly reduce the cost of preparation, and its products will account for a huge market in the field of low-end products for the future. Then this paper focuses on the preparation of large-scale Low-E glass by spray pyrolysis, with a view to the integrated optical and conductive performance of Low-E glass products.
In preliminary studies of this topic, the basis of a thorough theoretical exploration have been researched and the small trial phase in the industrialization of the initial attempt has been conducted. Concrete work is as follows.
1. The preparation methods of tin oxide spraying liquid have been explored and the F-Sb doped tin oxide spraying liquid with excellent performance has been prepared successfully. FT-IR and pH value of tin oxide spraying liquid in the preparation of the main stage have been tested by the IR spectra and digital pH value meter, respectively. The chemical reaction mechanism has been explored.
2. The process parameters in the preparation of F-Sb doped tin dioxide for low-emissivity glasses has been studied on the production line and as the result the optimized preparation process has been obtained:700℃deposition temperature,6.93cm/s relative movement of the rate of glass, SiO2 underlay and two-times spray forming method. The excellent integrated optical and electrical performance of low-emissivity glasses have been obtained by this method, which sheet resistance, hemisphere emissivity and the average transmittance in visible region of the sample had reached 23Ω/□,0.23 and 69%respectively.
3. In order to save costs and improve productivity, the spraying liquid has been improved. Then the F doped tin dioxide film with excellent property has been prepared, which hemisphere emissivity and the average transmittance in visible region of the sample had reached 0.25 and 80% respectively. All of these have indicated that the improved spray liquid was better than the spraying liquid. The micro-properties of the F doped tin dioxide samples were investigated by XRD, SEM, and so on. The results showed that the film which had uniform crystal grains and compact structure with fewer defects was polycrystal with the tetragonal rutile structure.
引文
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[6]孙永泰.低辐射玻璃[J].能源技术,2003,24(2)：61-62.
[7]负英伟,吴香国,范丰丽.我国建筑节能现状分析及对策[J].重庆科学学院学报(自然科学版),2006,8(1)：62-65.
[8]李蕾等.居住建筑节能评价体系的探讨[J].中国住宅设施,2006,7：50-52.
[9]李明.深圳胜强公司低辐射玻璃项目的投融资策划与经济评价[D].西安：西安交通大学,2006：11-14.
[10]邓力,徐美君.低辐射玻璃生产应用及市场[J].玻璃与搪瓷,2003,31(1)：56-59.
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