大面积氧化物薄膜材料的微纳结构可控制备与性能调控技术

发布时间：2018-05-30 03:30

本文选题：氧化物薄膜 + 微纳结构　；参考：《浙江大学》2014年博士论文

【摘要】：镀膜玻璃是最主要的新型建筑节能玻璃,既可以保持玻璃的透光性,又可以高效阻隔热量的传递,赋予普通平板玻璃特殊的功能,满足节能、环保、安全和装饰等多种需求,按功能可分为阳光控制镀膜玻璃、低辐射镀膜玻璃、自清洁镀膜玻璃等。利用不同氧化物材料各自的物理和化学性能,采用浮法在线化学气相沉积技术,通过对氧化物薄膜微纳结构与性能的调控,以实现节能镀膜玻璃大面积均匀与高性能的兼顾,在建筑节能领域有着广阔的应用前景。同时,开展纳米尺度氧化物薄膜的可控制备,研究制备工艺-结构-性能之间的相互关系,对于这类材料的发展及应用拓宽具有重要的科学意义。本文首先简要概述了建筑节能镀膜玻璃的研究与应用现状,主要针对低辐射镀膜玻璃与自清洁镀膜玻璃,重点总结和评述了以SnO2:F为代表的透明导电薄膜和Ti02薄膜的制备与性能的研究现状,以及该类薄膜具有节能效果的原理。针对氧化物薄膜制备中存在的大面积均匀稳定镀膜困难、多层膜结构匹配与节能优化技术缺乏等问题,提出开展新型节能玻璃的材料膜系设计、多层匹配和微结构调控技术的研究,本文采用浮法在线化学气相沉积技术,在玻璃表面首次制得微纳结构SnO2：F薄膜、纳米镶嵌结构SiCxOy薄膜以及纳米Ti02薄膜。采用多种分析测试技术对三类薄膜的结构、均匀性、稳定性、光学性能、电学性能和亲水性等性能进行了研究。同时系统研究了低辐射镀膜玻璃在温度场作用下结构与性能变化的过程与机理。本文主要研究内容和结果如下： (1)采用浮法在线MOCVD法,以单丁基氯化锡和三氟乙酸作为先驱体,通过反应温度、薄膜前驱体流量等工艺参数调控、退火处理等手段控制晶体成核-生长过程,首次在玻璃基体表面制得了大面积、均匀、金红石相、柱状生长的微纳结构SnO2:F薄膜,即薄膜是由尺寸为5nm-10nm的SnO2晶粒取向聚集成的100nm-300nm颗粒所形成。微纳结构的SnO2:F薄膜通过对载流子的散射作用,有利于薄膜获得更为优异的低辐射性能。通过结构的调控,获得了雾度值达到～10.3%,方块电阻～11Ω·sq-1,辐射率低于0.16,可见光品质因数～10-3数量级,硬度值达到15.08GPa,杨氏模量达到206.93GPa的SnO2:F透明导电薄膜,该类薄膜在低辐射镀膜玻璃与薄膜太阳能电池领域具有很好的应用前景。 (2)采用浮法在线常压CVD法,以硅烷、乙烯、CO2作为前驱体,通过控制表面梯度氧化、薄膜沉积的反应温度和时间等参数调节纳米Si成核-生长过程,获得了大面积、均匀的纳米镶嵌SiCxOy薄膜,即由5nm大小的Si晶粒均匀镶嵌在Si-C-O无序网络中形成。这类薄膜被选择作为阻挡层的膜层材料。 (3)结合SnO2:F薄膜和SiCxOy薄膜的制备,在浮法生产线上,采用热分解CVD方法在锡槽内镀硅碳氧等多元化合物薄膜,然后采用MOCVD方法在退火窑内镀氧化锡等氧化物薄膜,制备得到了大面积、均匀的SnO2:F/SiCxOy复合镀膜玻璃。采用FIB-TEM手段,观察到了薄膜的三明治结构,其中SnO2:F膜层趋于柱状生长,具有很好的结晶性,SiCxOy阻挡层为多层纳米镶嵌结构,在膜层与膜层之间存在元素组分的过渡层。 (4)系统研究了阻挡层对SnO2:F薄膜结构与性能的影响,选择了SiCxOy和SixSnyO2作为阻挡层膜层材料进行研究和对比。具有阻挡层的SnO2:F薄膜具有更为均匀的表面形貌,颗粒分布在～200nm-300nm,且呈现更为明显的金字塔结构。阻挡层的引入弥补SnO2:F膜层与玻璃基体之间由于晶格不匹配而产生的大量孔洞,保证了膜层之间较好的结合力,改善了薄膜的力学性能。在结构上,阻挡层的引入提高了SnO2:F薄膜的结晶性,增强了其在(200)晶面的取向生长。在性能上,由于结构与形貌的改善,且阻挡了玻璃基体中的Na+、K+离子的扩散,具有阻挡层尤其是SiCxOy阻挡层的SnO2:F薄膜具有更为优异的光电学性能,电阻率下降到4.9×10-4,中远红外反射率提高到～85%,辐射率降低到0.16。因此,SiCxOy薄膜为一种理想的运用于FTO薄膜的阻挡层材料。 (5)对低辐射镀膜玻璃的稳定性进行了研究,发现当较长时间热处理且温度高于～580℃,将导致薄膜中微米尺寸的多面体颗粒分裂成纳米尺寸小颗粒,同时产生大量的颗粒界面,这些界面的产生使SnO2:F薄膜的霍尔迁移率和方块电阻增大,进而导致薄膜低辐射性能的劣化。定义了一个“H”因子来定量标定SnO2:F薄膜表面形貌的一致程度,并且将其与薄膜的性能联系起来,从而通过表面形貌的变化来考察薄膜的性能。发现低的“H”因子对应于低辐射性能较优异,方块电阻较小,对低辐射镀膜玻璃的工业化生产具有指导意义。 (6)模拟了玻璃钢化的过程,研究了原位和非原位钢化过程中SnO2:F低辐射镀膜玻璃结构与性能的变化。当钢化温度达到650℃,钢化时间大于10min,薄膜的方块电阻明显增大、中远红外反射率降低、低辐射性能明显变差。这是由于薄膜在空气中高温处理,氧气的化学吸附和F的向外扩散,导致了薄膜空位的减少,载流子浓度的降低。同时,薄膜内部界面的变化,通过界面散射导致薄膜霍尔迁移率的明显降低。因此,薄膜的载流子浓度和霍尔迁移率发生明显下降,最终导致薄膜光电性能的劣化。为了保证SnO2:F低辐射镀膜玻璃在钢化过程中保持较好的光电性能以及满足国家标准的低辐射率,钢化时间需控制在10min之内。 (7)以四异丙醇钛(TTIP)作为先驱体,采用常压MOCVD方法,通过控制镀膜温度、镀膜气体流量和速度,控制晶体成核-生长过程,在玻璃基体表面快速制备出大面积、均匀的TiO2薄膜,该类薄膜为一种锐钛矿相结构纳米薄膜,由尺寸小于10nm的TiO2纳米晶粒组成,表面均匀、致密,粗糙度小于10nm,从光学参数上分析可以分为致密层与表面粗糙层,具有较好的结晶性,晶态含量大于60%。 (8)通过调控TTIP浓度和前驱体总流量,系统研究了浮法在线制备参数对TiO2薄膜结构与形貌的影响,优化了锐钛矿相TiO2薄膜的结晶性,获得了表面致密、粗糙度小于5nm的纳米TiO2薄膜。同时,该类薄膜兼具优异的可见光透过率和亲水性,满足自清洁镀膜玻璃对采光和自清洁性能的要求,是一种较为理想的阳光易洁镀膜玻璃。
[Abstract]:Coated glass is the most important new type of building energy saving glass. It can not only keep the light transmittance of glass, but also effectively block the transfer of heat. It gives the special function of ordinary flat glass to meet the needs of energy saving, environmental protection, safety and decoration. According to the function, it can be divided into sunlight controlled coating glass, low radiation coated glass and self cleaning coating glass. Using the physical and chemical properties of different oxide materials, using floating on line chemical vapor deposition (CVD), through the control of the microstructure and properties of the oxide film, in order to realize the large area uniformity and high performance of the energy-saving coating glass, it has a broad application prospect in the energy saving area of the building. At the same time, the nano scale is carried out. The controllable preparation of the oxide film and the study of the relationship between the structure and properties of the preparation process are of great scientific significance for the development and application of this kind of materials.
In this paper, the research and application of energy saving coated glass for building is briefly summarized. The research status of the preparation and performance of transparent conductive and Ti02 films, represented by SnO2:F, is mainly summarized and reviewed, mainly for low radiation coated glass and self cleaning coated glass. The film system of large area and uniform stability in the preparation of chemical film is difficult, the structure matching of multilayer film and the lack of energy saving optimization technology are lacking. The material membrane system design of the new type energy saving glass, multi-layer matching and micro structure control technology are put forward. In this paper, the float process on-line gas phase deposition technology is used in this paper to make the micro surface of the glass for the first time. Nanoscale SnO2:F film, nanostructured SiCxOy film and nano Ti02 thin film are used to study the structure, uniformity, stability, optical properties, electrical properties and hydrophilic properties of the three types of thin films, and the structure and properties of low radiation coated glass under the temperature field are studied systematically. The main contents and results of this study are as follows:
(1) using the buoy on-line MOCVD method, using the single butyl tin chloride and three FLUOROACETIC acid as the precursor, through the reaction temperature, the membrane precursor flow and other technological parameters control, annealing treatment and other means to control the crystal nucleation and growth process, for the first time, the large surface, uniform, rutile and columnar growth of the micro nano structure SnO2:F thin on the surface of the glass matrix is made. The film, that is, is formed by the SnO2 grain oriented 100nm-300nm particles with the size of 5nm-10nm. The micro nano structure SnO2:F thin film is beneficial to the film to obtain more excellent low radiation performance through the scattering of the carrier. Through the structure regulation, the fog value is reached to 10.3%, the block resistance to 11 Omega SQ-1, the radiation rate. Under 0.16, the visible light quality factor is 10-3 orders of magnitude, the hardness value reaches 15.08GPa and the young's modulus reaches 206.93GPa SnO2:F transparent conductive film. This kind of film has a good application prospect in the field of low radiation coated glass and thin film solar cells.
(2) using the floating on-line atmospheric pressure CVD method, using silane, ethylene and CO2 as precursors, by controlling the surface gradient oxidation, the reaction temperature and time of the film deposition, the nanoscale Si nucleation and growth process are adjusted. A large area, uniform nanoscale SiCxOy film is obtained, that is, the Si grains of 5nm size are inlaid evenly in the Si-C-O disorder network. These films are selected as barrier coatings.
(3) combined with the preparation of SnO2:F film and SiCxOy film, on the float production line, the thin film of silicon carbon oxygen and other compounds was plated by thermal decomposition CVD method in the tin slot. Then MOCVD method was used to plating tin oxide thin film in the annealing kiln, and a large area and uniform SnO2:F/SiCxOy composite coating glass was prepared. FIB-TEM method was used. The sandwich structure of the film is observed, in which the SnO2:F film tends to columnar growth and has good crystallinity. The SiCxOy barrier layer is a multilayer nanomosaic structure, and there is a transition layer between the element components between the film and the film layer.
(4) the influence of barrier layer on the structure and properties of SnO2:F film is studied systematically. SiCxOy and SixSnyO2 are selected as barrier layer materials to study and compare. The SnO2:F films with barrier layer have more uniform surface morphology, the particles are distributed in 200nm-300nm, and the structure of Pyramid is more obvious. A large number of holes produced by the lattice mismatch between the SnO2:F film and the glass substrate ensure a better bonding force between the layers and improve the mechanical properties of the film. In structure, the introduction of the barrier layer improves the crystallinity of the SnO2:F film and enhances its orientation growth at (200) surface. In performance, due to structure and morphology The improvement has blocked the diffusion of Na+ and K+ ions in the glass matrix. The SnO2:F films with the barrier layer, especially the SiCxOy barrier layer, have better photoelectrical properties, the resistivity drops to 4.9 x 10-4, the mid far infrared reflectance is increased to 85%, the radiation rate is reduced to 0.16., and the SiCxOy film is an ideal resistance to the FTO film. Block material.
(5) the stability of low radiation coated glass is studied. It is found that when the heat treatment is longer and the temperature is higher than 580 C, the polyhedron particles in the thin film are divided into small size particles, and a large number of particle interfaces are produced. The production of these interfaces makes the Holzer mobility and the block resistance of the SnO2:F film increase. This leads to the deterioration of the low radiation performance of the film. A "H" factor is defined to calibrate the consistency of the surface morphology of the SnO2:F thin film, and it is associated with the properties of the film to investigate the performance of the film by the change of the surface morphology. It is found that the low "H" factor corresponds to the low radiation performance, and the block resistance is better. It is of little significance to the industrial production of low radiation coated glass.
(6) the process of glass tempering was simulated. The structure and properties of SnO2:F low radiation coated glass were studied in the process of in-situ and in situ steel. When the tempering temperature reached 650, the toughening time was greater than 10min, the block resistance of the film increased obviously, the albedo of the medium and far infrared decreased and the low radiation performance was obviously worse. This is due to the film in the air. The medium high temperature treatment, the chemical adsorption of oxygen and the outward diffusion of F lead to the decrease of the film vacancy and the decrease of the carrier concentration. At the same time, the change of the inner interface of the film leads to the apparent decrease of the mobility of the film Holzer by the interface scattering. Therefore, the carrier concentration and the mobility of the Holzer film are obviously decreased, and the film light is eventually led to the film light. In order to ensure the good photoelectric performance of the SnO2:F low radiation coated glass during the toughening process and meet the low radiation rate of the national standard, the tempering time should be controlled within the 10min.
(7) using four isopropanol titanium (TTIP) as a precursor, the normal pressure MOCVD method is used to control the nucleation and growth process of the crystal by controlling the temperature of the coating, the flow and velocity of the coating gas, and the large area and uniform TiO2 thin film is quickly prepared on the surface of the glass matrix. This kind of film is a kind of anatase phase structure nanomiltration, which is from the TiO2 nano size less than 10nm. The grain of rice is composed of uniform, compact surface, and the roughness is less than 10nm. From the optical parameters, it can be divided into dense layer and surface rough layer. It has good crystallinity and the crystalline content is greater than 60%..
(8) by controlling the TTIP concentration and the total flow rate of the precursor, the influence of the parameters on the structure and morphology of the TiO2 film was systematically studied. The crystallinity of the anatase TiO2 films was optimized. The nano TiO2 films with dense surface and less than 5nm were obtained. At the same time, the film has excellent visible light transmittance and hydrophilicity. Self cleaning coated glass is an ideal and easy to clean glass for sunlight.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：TB383.2;TQ171.72

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