本論文討論以溶膠凝膠法 ( Sol-gel method ) 製備 TiO2 奈米薄膜光電極利用於染料敏化太陽電池 ( Dye-Sensitized Solar Cells, DSSCs )，主要討論光電極的製作為重要研究方向。
TiO2 奈米薄膜光電極製作方面，先以溶膠凝膠法製備TiO2 sol，旋轉塗佈 ( spin coating ) 成膜後，以超臨界乾燥 ( Supercritical Drying ) 及烘箱乾燥去溶劑2種方法來討論 TiO2 奈米薄膜光電極的晶相與表面結構。利用不同乾燥法製作之光電極組裝成染料敏化太陽電池，以超臨界乾燥的方式製作之 TiO2 奈米薄膜光電極具有高度的孔隙性質，而使染料可以充填的更多，得到較佳的效率。

The thesis discusses how to utilize Sol-gel method to prepare nano-sized TiO2 films of photoelectrodes and the their use in Dye-Sensitized Solar Cells. The main goal is the study on the production of TiO2 photoelectrodes.

When making nano-sized TiO2 films of photoelectrodes, we have to first produce TiO2 sol via the Sol-gel method optical thin films are then made by spin coating. After its spin coating, we study the crystalline phase and morphology of nano-sized TiO2 films of photoelectrodes in terms of two ways: Supercritical drying and oven drying. Among the Dye-Sensitized Solar Cells that are made with different drying methods, owing to higher porosity and surface area, the nano-sized TiO2 films of photoelectrodes made by supercritical drying adsorb more dye molecules and are thus more efficient.

摘 要 I
ABSTRACT II
誌 謝 III
目 錄 IV
圖目錄 VII
表目錄 X
第一章 序論 1
1.1、前言 1
1.2、溶膠-凝膠法之發展與現況 3
1.3、溶膠-凝膠反應程序 (Sol-Gel process) 5
1.4、溶膠-凝膠法製備薄膜 7
1.5、薄膜熱處理程序 9
1.6、超臨界流體簡介 12
1.7、染料敏化太陽電池 ( Dye-Sensitized Solar Cells, DSSCs ) 17
1.8、研究背景與目的 19
第二章 實驗藥品與儀器 20
2.1、實驗藥品 20
2.2、實驗儀器 22
第三章 實驗 31
3.1、實驗方法 31
3.1.1、TiO2溶凝膠製備 33
3.1.2、TiO2溶凝膠TGA分析 33
3.1.3、TiO2薄膜製備 33
3.1.4、TiO2薄膜表面觀察 35
3.1.5、TiO2薄膜乾燥處理 36
3.1.6、XRD繞射分析 37
3.1.7、SEM結構分析 37
3.2、染料敏化太陽電池 ( DSSCs ) 組裝與量測 38
3.2.1、染料敏化太陽電池 ( DSSCs ) 組裝 38
3.2.2、染料敏化太陽電池效率量測 42
第四章 結果與討論 44
4.1、TiO2光電極分析 44
4.1.1、TiO2溶凝膠TGA分析 44
4.1.2、TiO2薄膜表面觀察分析 46
4.1.3、XRD分析 48
4.1.4、SEM分析 52
4.2、染料敏化太陽電池效率分析 57
第五章 結論 61
參考文獻 62

[1] B. O’Regan, M. Gratzel, “A low, high-efficiency solar cell based on dye-sensitized colloidal TiO2 film.” Nature, Vol. 353, Oct 24 1991.
[2] O. Harizanovl, A. Harizanova, “Development and Investigation of Sol-Gel Solutions for the Formation of TiO2 Coatings”Solar Energy Materials & Solar Cells 2000, 63, 185-195.
[3] B. L. Bischoff, M. A. Anderson, “Peptization Process in the Sol-Gel Preparation of Porous Anatase(TiO2)”Chemistry Material 1995, 7, 1772-1778.
[4] K. R. Patil, S. D. Sathaue, Y. B. Khollam, S. B. Deshpande, N. R. Pawaskar, A. B. Mandale, “Preparation of TiO2 Thin Films by Modified Spin-Coating Method Using an Aqueous Precursor” Materials Letter 2003, 57, 1775-1780.
[5] R. S. Sonawane, S. G. Hegde, M. K. Dongare, “Preparation of Titanium(IV) Oxide Thin Film Photocatalyst by Sol-Gel Dip Coating” Materials Chemistry and Physics 2002, 77, 744-750.
[6] N. Kaliwoh, J. Y. Zhamg, I. W. Boyd, “Titanium Dioxide Films Prepared by Photo-Induced Sol-gel Processing Using 172 nm Excimer Lamps” Surface Coatings Technology 2000, 125, 424-427.
[7] J. Y. Zhang, I. W. Boyd, L. J. Bie, V. Dusastre, “Thin Tantalum Oxide Films Prepared by 172 nm Excimer Lamp Irradiation Using Sol-gel Method” Thin Solid Film 1998, 318, 252-256.
[8] H. Sakai, H. Kawahara, M. Shimazaki, M. Abe, “Preparation of Ultrafine Titanium Dioxide Particles Using Hydrolysis and Condensation Reaction in the Inner Aqueous Phase of Reversed Micelles：Effect of Alcohol Addition” Langmuir 1998, 14, 2208-2212.
[9] J. Yu, J. C. Yu, W. Ho, Z. Jiang, “Effects of Calcination Temperature on the Photocatalytic Activity and Photo-Induced Super-Hydrophilicity of Mesoporous TiO2 Thin Films” New Journal Chemistry 2002, 26, 607-613.
[10] Y. Tanaka, M. Suganuma, “Effects of Heat Treatment on Photocatalytic Property of Sol-gel Derived Polycrystalline TiO2” Journal of Sol-Gel Science and Technology 2001, 22, 83-89.
[11] J. W. Lee, C. W. Won, B. S. Chun, H. Y. Sohn, “Dip coating of alumina films by the sol-gel method” J. Mater. Res. 1993, 8, 3151-3157.
[12] M. Shane, M. L. Mecartncy, “Sol-gel synthesis of zirconia barrier coatings” Journal of Materials Science. 1990, 25, 1537-1544.
[13] B. G. Odi’lio, M. Assia, L. A. Avaca, “Some properties of protective sol-gel glass coatings on sintered stainless steels” Journal of Non-Crystalline solid. 2000, 273, 159-163.
[14] 尤耿賢, 國立台灣大學化工所博士論文 2000年11月.
[15] M. Perrut, “Supercritical Fluids. ”Tom 1, 1988, France.
[16] A. Hagfeldt, M. Gratzel, “Light-Induced Redox Reactions in Nanocrystalline Systems” Chem. Rev. 1995, 95, 49-68.
[17] M. Gratzel, “Mesoporous oxide junctions and nanostructured solar cells” Current Opinion in Colloid & Interface Science 1999, 4, 314-321.
[18] K. Kalyanasundaram and M. Gratzel, “Applications of functionalized transition metal complexes in photonic and optoelectronic devices” Coord. Chem. Rev. 1998, 77, 347-414.
[19] A. Fujishima et al., “Show interfacial charge recombination in solid-state dye-sensitized solar cell using Al2O3-coated nanoporous TiO2 films” Sol. Energy Mater. Sol. Cells. 2004, 81, 197-203.
[20] Cahen et al., “Nature of Photovoltaic Action in Dye-Sensitized Solar Cells” J. Phys. Chem. B 2000, 104, 2053-2059.
[21] http://www.solaronix.ch/index.htm
[22]汪建民主編, 材料分析, 中國材料科學學會。
[23] K. M. Reddy, S. V. Manorama, A. R. Reddy, ＂Bandgap Studies on Anatase Titanium Dioxide Nanoparticles＂Materials Chemistry and Physics 2002, 78. 239-245.
[24] K. Nagaveni, M. S. Hegde, N. Ravishankar, G. N. Subbanna, G. Madras, ＂Synthesis and Structure of Nanocrystalline TiO2 with Lower Band Gap Showing High Photocatalytic Activity＂Langmuir 2004, 20, 2900-2907.