超声喷雾法制备太阳电池减反射膜的研究
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摘要
提高太阳电池的光电转化效率是光伏研究中最重要的问题，然而，有10%以上的光能在太阳能电池的封装玻璃表面由于反射而损失掉。在玻璃表面制备减反射膜可以起到增透作用，针对不同种类太阳电池的不同响应波段制备减反射膜可以使电池的转换效率得到有效的提高。
本文探索性地采用成本低、设备简单、生产周期短的超声喷雾热解法和优化的超声雾化模式制备出适用于不同太阳电池的SiO_2/TiO_2减反射薄膜。
研究了喷射距离、载气流量、前驱液的选择和流量、衬底温度、热处理时间等工艺条件对薄膜结构和光学性能的影响，找到最优化的工艺条件并确定薄膜材料的光学参数。发现500℃时制备出的TiO_2薄膜呈锐钛矿，SiO_2薄膜呈非晶结构，保温热处理10min后的折射率分别为2.23和1.42。
根据所得单层薄膜的光学参数结果，结合光学薄膜理论，利用软件优化设计出适用于非晶硅太阳电池的双层减反射膜系和适用于微晶、非/微叠层及晶硅太阳电池的六层减反射膜系，理论平均剩余反射率为1.193%和0.879%。
根据膜系的优化结果，采用载玻片为衬底，制备出两种应用于太阳能电池的减反射膜，使玻璃的透过率分别提高了10.8%和10.4%。通过附着性测试和机械性能测试表明减反射膜具有较强的物理性能。
The most important issue of photovoltaic research is to improve the photoelectricconversion efficiency of solar cells. However, more than 10% of solar energy in the glasspackage is lost due to reflection. Preparation of anti-reflective film on the glass surface canplay an antireflective role. For the different responses band of different types of solar cells,preparation of the antireflection film can increase the conversion efficiency effectively.
In this thesis, the SiO_2/TiO_2 antireflection films for different kinds of solar cells wereprepared by the ultrasonic spray pyrolysis, which has low cost, simple equipment, shortproduction cycle, and the ultrasonic spray model optimized in the practice.
In the ultrasonic spray pyrolysis, many process conditions have an influence on thefilms’structure and optical properties, such as the spray distance, the flow rate of carriergas, the choice and flow rate of precursor solution, the temperature of substrate and theheat treatment time, which were studied in this thesis. The most optimal conditions arefound and the optical parameters of thin film materials are determined. We found that thecrystalline nature of the TiO_2 film was anatase, the SiO_2 film was amorphous prepared at500℃, and the corresponding refractive indexs were 2.23 and 1.42 after 10min heattreatment.
On the basis of the results of single-layer thin film optical parameters, and through thecombination of the theory of optical thin films and software, double layers anti-reflectivecoating applied for amorphous silicon solar cells and six layers anti-reflective coatingapplied forμc-Si solar cell, a-Si/μc-Si tandem solar cell and crystalline silicon solar cellwere designed and optimized. The average residual reflectance theoretical rates were1.193% and 0.879%.
According to the optimization results of the coating, using glass slides as substrates,we prepared two kinds of antireflection films for solar cells, the transmittance of the glassincreased by 10.8% and 10.4%. Through the adhesion test and mechanical test, we foundthat the antireflection films have strong physical properties.
本文探索性地采用成本低、设备简单、生产周期短的超声喷雾热解法和优化的超声雾化模式制备出适用于不同太阳电池的SiO_2/TiO_2减反射薄膜。
研究了喷射距离、载气流量、前驱液的选择和流量、衬底温度、热处理时间等工艺条件对薄膜结构和光学性能的影响，找到最优化的工艺条件并确定薄膜材料的光学参数。发现500℃时制备出的TiO_2薄膜呈锐钛矿，SiO_2薄膜呈非晶结构，保温热处理10min后的折射率分别为2.23和1.42。
根据所得单层薄膜的光学参数结果，结合光学薄膜理论，利用软件优化设计出适用于非晶硅太阳电池的双层减反射膜系和适用于微晶、非/微叠层及晶硅太阳电池的六层减反射膜系，理论平均剩余反射率为1.193%和0.879%。
根据膜系的优化结果，采用载玻片为衬底，制备出两种应用于太阳能电池的减反射膜，使玻璃的透过率分别提高了10.8%和10.4%。通过附着性测试和机械性能测试表明减反射膜具有较强的物理性能。
The most important issue of photovoltaic research is to improve the photoelectricconversion efficiency of solar cells. However, more than 10% of solar energy in the glasspackage is lost due to reflection. Preparation of anti-reflective film on the glass surface canplay an antireflective role. For the different responses band of different types of solar cells,preparation of the antireflection film can increase the conversion efficiency effectively.
In this thesis, the SiO_2/TiO_2 antireflection films for different kinds of solar cells wereprepared by the ultrasonic spray pyrolysis, which has low cost, simple equipment, shortproduction cycle, and the ultrasonic spray model optimized in the practice.
In the ultrasonic spray pyrolysis, many process conditions have an influence on thefilms’structure and optical properties, such as the spray distance, the flow rate of carriergas, the choice and flow rate of precursor solution, the temperature of substrate and theheat treatment time, which were studied in this thesis. The most optimal conditions arefound and the optical parameters of thin film materials are determined. We found that thecrystalline nature of the TiO_2 film was anatase, the SiO_2 film was amorphous prepared at500℃, and the corresponding refractive indexs were 2.23 and 1.42 after 10min heattreatment.
On the basis of the results of single-layer thin film optical parameters, and through thecombination of the theory of optical thin films and software, double layers anti-reflectivecoating applied for amorphous silicon solar cells and six layers anti-reflective coatingapplied forμc-Si solar cell, a-Si/μc-Si tandem solar cell and crystalline silicon solar cellwere designed and optimized. The average residual reflectance theoretical rates were1.193% and 0.879%.
According to the optimization results of the coating, using glass slides as substrates,we prepared two kinds of antireflection films for solar cells, the transmittance of the glassincreased by 10.8% and 10.4%. Through the adhesion test and mechanical test, we foundthat the antireflection films have strong physical properties.
引文
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[2]苗向阳，太阳能玻璃的加工及应用技术研究，博士学位论文，中国建筑材料科学研究总院，2009
[3]苗向阳，太阳能玻璃及标准，建筑玻璃与工业玻璃，2008，5（32）：32~35
[4]谢光明，丹麦减反射玻璃简介，太阳能，2007（6）：33
[5]周九林，光学薄膜技术（尹树百），北京：国防工业出版社，1974：26~29
[6]宋利民，软X射线多层膜反射镜的设计与制作，硕士学位论文，大连理工大学，2002
[7] Crew H, Thomas Young's place in the history of the wave theory of light, Journal of theOptical Society of America, 1930, 20(1):3~10
[8] Thomas E G, Maxwell's equations and their application, Bristol: Adam Hilger Ltd,1985: 56~59
[9]尹树百，薄膜光学——理论与实践，北京：科学出版社，1987：1~2
[10] Martin S, Rivory J, Schoenauer M, Synthesis of optical multiplayer systems usinggenetic algorithm, Applied Optics, 1995, 34(13):2247~2254
[11] Greiner H, Robust optical coating design with evolutionary strategies, Applied Optics,1996, 35(28):5477~5483
[12] Chang C P, Lee H Y, Optimization of a thin-film multiplayer design by use of thegeneralized simulated-annealing method, Optics Letters, 2003, 15(11): 595~597
[13]李景镇，陈沅，王诺等，光学手册，西安：陕西科学技术出版社，1986：1330~1338
[14]许生，侯晓波，范垂祯等，硅靶中频反应磁控溅射二氧化硅薄膜的特性研究，真空，2001，（5）：1~6
[15]王永珍，龚国权，崔敬忠，二氧化硅薄膜的制备及应用，真空与低温，2003，9（4）：228~232
[16]严晖，高反射的高精度镀制研究，博士学位论文，合肥工业大学，2004
[17] Koelscb M., Cassaignon S, Guillemoles J F, Comparison of optical andelectrochemical properties of anatase and brookite TiO2 synthesized by the sol-gelmethod, Thin Solid Films, 2002, 403:312~319
[18] Frank S N, Bard A. J., Heterogeneous photocatalytic oxidation of cyanide and sulfitein aqueous solutions at semiconductor powders, The Journal of Chemical Physics,1977, 81:1484~1488
[19] Nakajima A, Koizumi S, Watanabe T, et al. highly hydrophilic surfaces of cathodicallypolarized amorphous TiO2 electrodes, The Electrochemical Society, 2001,148(10):395~398
[20] Richards B S, Single-material TiO2 double-layer antireflection coatings, Solar EnergyMaterials and Solar Cells, 2003, 79:369~390
[21] Abdullah M, Effects of common inorganic anions on rates of photocatalytic oxidationof organic carbon over illuminated titanlum dioxide, The Journal of Chemical Physics,1990, 94: 62~80
[22] Escobar-Alarcon L, Haro-Poniatowski E, Camacho-Lopez M A, et al. Structuralcharacteri- zation of TiO2 thin films obtained by pulsed laser deposition, AppliedSurface Science, 1999, (137):38~44
[23] Liu Xiaohua, Yin J, Liu Z G, et al. Structural characterization of TiO2 thin filmsprepared by pulsed laser deposition on GaAs(100) Substrates, Applied SurfaceScience, 2001, (174):35~39
[24] Leprince W Y, Yu Z K, Nguyen V, et al. Correlation between microstructure and theoptical properties of TiO2 thin films prepared on different substrates, Thin Solid Films,1997, 307(2):38~42
[25] Mergel D, Buschendorf D, Eggert S, et al. Density and refractive index of TiO2 filmsprepared by reactive evaporation, Thin Solid Films, 2000, 371(1-2):218~224
[26]王永杰，付勇，李智超等，离子辅助沉积法制备纳米TiO2光催化薄膜，材料导报，2008（1）：60~62
[27] Rand Dannenberg, Phil Greene, Reactive sputter deposition of titanium dioxide, ThinSolid Films, 2000, (360):122~127
[28] Banakh O, Schmid P E, Sanjines R, et al. Electrical and optical properties of TiOx thinfilms deposited by reactive magnetron sputtering, Surface and Coatings Technology,2002, (151-152):272~275
[29] Jiaguo Yu, Xiujian Zhao, Qingnan Zhao, Photocatalytic activity of nanometer TiO2thin films prepared by the sol-gel method, Materials Chemistry and Physics,2001,69:25~29
[30] Martinet C, Paillord V, Gagnaire A, et al. Deposition of SiO2 and TiO2 thin films byplasma enhanced chemical vapor deposition for antireflection coating, Journal ofNon-Crystalline Solids, 1997, 216:77~82
[31]张嘉琪，郑嗣华，黄积涛，基于超声波雾化技术的TiO2纳米膜制备及表征，无机材料学报，2006，21（3）：719~724
[32] Ble?ic M. Dj, ?aponji? Z V, Nedeljkovi? J M, et al. TiO2 films prepared by ultrasonicspray pyrolysis of nanosize precursor, Materials Letters, 2002, 54:298~302
[33]何胜，羊亿，刘敏等超声喷雾热解法制备TiO2薄膜，电子器件，2008，31（1）：236~238
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