| Due to the energy-saving demands in the world, oxide thin films coated glass has been considered as a promising novel energy-saving building material. Different oxide thin films are selected due to function of the coated glass, including excellent transparency in the visible spectrum range and high electrical conductivity or other properties. Energy-saving coated glass can be classified as low-emission coated glass, solar control coated glass, self-cleaning coated glass, etc. Investigation on the controllable preparation of oxide thin films on the glass substrate via APCVD method on the float production line and further building the relationship between the microstructures and properties, are highly desired to develop and expand application for these materials.In this dissertation, the status of energy-saving coated glass, emphatically summarized SnO2:F low-emissivity coated glass and TiO2self-cleaning coated glass, have been reviewed firstly. The structure, preparation and the principle of energy saving effect of such oxide thin films have been summarized. However, the preparation of large area uniform oxide thin films, the matching of multilayer films, the optimization of the functional properties of such energy-saving glass remain a challenge. Thus, new type of energy-saving multilayer films system has been designed, multi-layer matching and microstructure control technology have been investigated. Via float on-line APCVD technology, micro-nano structural SnO2:F thin film, nano-particle reinforced structural SiCxOy thin film and nano TiO2thin film were prepared for the first time in the glass substrate. Moreover, various measurement methods were employed to study the structure, stability, optical properties, electrical properties and hydrophilic performance of such thin films. In particular, the variation of the structure and functional properties of SnO2:F low-emission coated glass under high temperature has been systematically explored. The main contents and results are summarized as follows:(1) The homogeneous SnO2:F thin film with stable microstructural and functional properties was successfully deposited on glass substrate at a large-scale of3-m in width via APCVD method on an industrial production line. It was observed for the first time that the as-deposited SnO2:F thin film presented a micro-nano structure type, of which micro-sized grains (100-300nm) assembled by nano-sized crystallites (<10nm). With the control of the structure and morphlogy, such SnO2:F series film exhibited haze value of-10.3%, sheet resistance of～11Ω·sq-1, emissivity lower than0.16, hardness reached15.08GPa, Yong’s modulus reached206.93GPa, allowing its potential applications as the low-emission coated glass and the front TCO for amorphous and microcrystalline silicon based solar cells.(2) The homogeneous SiCxOy thin film with nano-particle reinforced structure, of which nano-sized Si particles (<5nm) embedded in the amorphous Si-C-0network, was successfully deposited on glass substrate at a large-scale of3-m in width via APCVD method on an industrial production line. This kind of thin film presented a potential application as barrier layer material during the production of low-emission coated glass.(3) SnO2:F/SiCxOy multilayer low-emission coated glass was designed and prepared. Thermal decomposition CVD method is used to deposit SiCxOy layer in the tin bath, and MOCVD technique is chosen to deposit SnO2:F layer in the annealing kiln. Vie FIB-TEM method, the sandwich structure of the low-emission glass was observed for the first time. The SnO2:F thin film showed a uniform nanocrystalline nature of cassiterite structure and the SiCxOy showed amorphous multilayer structure.(4) The effect of barrier layer, SiCxOy and SixSnyO2on the modification of the structure, surface morphology and functional properties of SnO2:F thin film was investigated and compared. An improvement in preferential orientation, the (200) crystallographic orientation in particular, has been confirmed via inserting barrier layers. Furthermore, a homogeneous surface morphology and enhanced columnar growth structure are confirmed for SnO2:F films with barrierlayer.(200) orientation preferred SnO2:F/SiCxOy/Glass films with larger grain size and a columnar growth structure were found to exhibit lower resistivity(～4.9×10-4), higher reflectance in the mid-far-infrared region (～80%) and lower emissivity (～0.16). The SiCxOy barrier layer has presented more positive influence in improving the preferentially orientation, surface morphology and functional property of SnO2:F thin film compared with the SixSnyO2layer, suggesting that the SiCxOy film maybe a more ideal potential barrier layer material during SnO2:F thin film production.(5) The stability of SnO2:F thin film was investigated. It was found that post-heating at～580℃or above for20min induced a splitting phenomenon of the micro-sized polyhedron-like grains into smaller ones. Meanwhile, more grain boundaries emerged led to the decreased Hall mobility and increased sheet resistance. In addition, the low-emission property of the SnO2:F thin film was found to drop dramatically with such heating conditions. A harmonic factor,’H’factor, was defined to quantify the structural influence on the low-emission functional property. The study has thus demonstrated the highest temperature for SnO2:F low-emission glass to maintain the good functional properties, and provided a critical guidance for the further modern energy-saving glass industrial production.(6) The glass tempering process in industry was simulated by in-situ and ex-situ technology to SnO2:F/SiCxOy low-emission coated glass. After tempering process at-650℃with varied periods, the sheet resistance of the SnO2:F thin film remained stable for less than10min, but increased dramatically when the tempering period exceeded10min, which was mainly due to the oxygen chemisorptions and fluorine ion diffusion. The calculated emissivity of the SnO2:F glass tempered for less than10min has reached as low as0.16. The study has therefore suggested the appropriate tempering conditions for the SnO2:F low-emission glass in industrial.(7) A series of TiO2thin films were prepared via atmospheric pressure chemical vapor deposition (APCVD) method on an industrial production line. By adjusting the deposition temperature, total flow rate, concentration of precursor, etc, the process of crystal nucleation and growth was controlled. The as-deposited large-are TiO2thin film presented good crystallinity of anatase structure, crystalline content greater than60%, uniform surface morphology with roughness less than10nm.(8) Via controlling the concentration of TOP and the total flow rate of precursor, the relationship between the microstructure and properties of TiO2thin film was investigated. The increased concentration and total flow rate modified the crystallinity, decreased the surface roughness and improved the hydrophilic property of TiO2thin film, which allowed it being a potential applications as the self-cleaning coated glass. |
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