Synthesis of TiO2 and TiO2-SiO2, Carbon-TiO2 Composites by Evaporation Induced Self- assembly and Their Applications in Dye-sensitized Solar Cell

利用蒸發誘導式自組裝法製備二氧化鈦、二氧化鈦與二氧化矽複合物、二氧化鈦與碳複合物。第一個部份本研究以簡易自組裝法並以triton X-100當介面活性劑模板，titanium (IV) isopropoxide為鈦的來源且改變Ti/H2O 莫耳比例可合成出可調控直徑的球狀二氧化鈦。其直徑分別為500 nm, 700 nm, and 1100 nm且命名為TiO2-500、TiO2-700 以及TiO2-1100。並且將其運用於染敏化太陽能電池的工作電極，其電極第一層塗佈商業化二氧化鈦吸附層(P25)第二層分別塗佈TiO2-500、TiO2-700 以及TiO2-1100為反射層製成雙層元件。 第二部分以相同簡易自主裝法並以titanium (IV) isopropoxide 與tetraethoxysilane分別為鈦以及矽的來源合成出二氧化鈦與二氧化矽複合物。另一方面以碳的寡聚體取代矽源合成出二氧化鈦與碳的複合物。分別將兩種複合物運用在染敏化太陽能電池工作電極中以及對電極。其中二氧化鈦與二氧化矽複合物光電轉換效率已達7.92﹪。The size tunable TiO2 sphere, SiO2-TiO2 composite and C-TiO2 composite were synthesized via a simple evaporation induced self-assembly (EISA) process. First, We report a simple method for the preparation of the size tunable TiO2 sphere from titanium (IV) isopropoxide and nonionic surfactant colloids (triton X-100) as the template. The synthetic procedure is easy to control by changing the Ti/H2O ratios in the process of evaporation-induced self-assembly. We are able to tune the size of sphere TiO2 particles with diameters of 500 nm, 700 nm, and 1100 nm, named as TiO2-500, TiO2-700 and TiO2-1100. They are suitable for the fabrication of DSSCs with a comparable efficiency to the commercial photocatalyst P25. The three different TiO2 sphere size were applied as a scattering overlayer on a transparent nanocrystalline TiO2 film, bi-layered dye-sensitized solar cells (DSSCs) have been fabricated. In second part, SiO2-TiO2 composite has been reported, which uses nonionic surfactant colloids (triton X-100) as the template as a template, a titanium (IV) isopropoxide and Tetraethoxysilane as a titanium and silica source by evaporation-induced self-assembly. The SiO2-TiO2 composite can be easily shaped. The synthesized SiO2-TiO2 composite were then applied as the as a scattering overlayer on a transparent nanocrystalline TiO2 film, bi-layered dye-sensitized solar cells (DSSCs) have been fabricated. As a result the photovoltaic conversion efficiency (η) of DSSC was improved with our materials. In addition, we synthetize C-TiO2 composite by the same method. It has been investigated as a counter electrode for dye-sensitized solar cells.目錄………………………………………………………………………………......Ⅰ 圖目錄………………………………………………………………………………..Ⅲ 表目錄………………………………………………………………………………..Ⅴ 第一章 緒論………………………………………………………………………...1 1.1 前言………………………………………………………………………1 1.2 太陽能電池簡介…………………………………………………………...2 1.2.1矽太陽能電池……………………………………………………….4 1.2.2 薄膜太陽能電池…………………………………………………... 6 1.3有機太陽能電池…………………………………………………………....7 1.3.1 染料敏化太陽能電池………………………………………………8 1.3.2 染料敏化太陽能電池工作原理…………………………………....8 1.3.3太陽能電池-電壓輸出特性………………………………………..11 1.3.4染敏化太陽能電池元件結構……………………………………...13 第二章 中孔性材料簡介…………………………………………………………....22 2.1 中孔洞材料之發展……………………………………………………….22 2.2 中孔洞氧化矽SBA-15…………………………………………………...23 2.2.1 SBA-15簡介……………………………………………………….23 2.2.2 SBA-15合成機制…………………………………………………23 2.3 實驗原理…………………………………………………………………24 2.3.1溶膠凝膠法(sol-gel method)………………………………………24 2.3.2自組裝法(self-assembly)………………………………………….26 2.3.3揮發誘導自組裝法(evaporation-induced self-assembly, EISA)…29 第三章 實驗儀器……………………………………………………………………32 3.1粉末X-光繞射(Powder XRD)…………………………………………….32 3.2氮氣等溫吸附/脫附(N2 adsorption/desorption…………………………32 3.3穿透式電子顯微鏡(TEM)………………………………………………33 3.4場發射掃描式電子顯微鏡(SEM)………………………..34 3.5熱重分析儀………………………………………………………………..34 第四章 製備可調控TiO2粒子半徑及其敏化太陽能電池運用…………35 4.1 簡介………………………………………………………………………35. 4.2 實驗方法……………………………………………………………….37 4.2.1 顆粒直徑可調式二氧化鈦粉末製備……………………………37 4.2.2 工作電極漿料配…………………………………………………37 4.2.3敏化太陽能電池元件之製備…………………………………….39 4.3 樣品鑑定及染敏化太陽能電池效率測試……………………………41 4.3.1 場發射掃描式電子顯微鏡影像 ( FESEM)……………….41 4.3.2 氮氣等溫吸附與脫附曲線(BET)及X射線繞射光譜(XRD)…….44 4.3.3球狀TiO2形成機構示意圖………………………………………48 II 4.3.4 UV-VIS測試結果………………………………………………….49 4.3.5染料敏化太陽能電池測試結果…………………………………...50 4.4 結論……………………………………………………………………….53 第五章 製備TiO2及SiO2複合物粒子及其敏化太陽能電池運用……………….54 5.1 簡介……………………………………………………………………….54 5.2 實驗方法………………………………………………………………….58 5.2.1 TiO2/SiO2複合物粒子製備……………………………………….58 5.2.2 工作電極漿料配製………………………………………………..60 5.2.3敏化太陽能電池元件之製備……………………………………...60 5.3 結果與討論……………………………………………………………….62 5.3.1 場發射掃描式電子顯微鏡影像 ( FESEM )……………………..62 5.3.2能量分散光譜儀…………………………………………………...64 5.3.3 氮氣等溫吸脫附…………………………………………………..67 5.3.4球狀TiO2-SiO2 composite形成機構示意圖……………………..68 5.3.5染料敏化太陽能電池測試結果…………………………………...69 5.4 結論……………………………………………………………………….71 第六章 製備Carbon-TiO2複合物粒子運用於敏化太陽能電池對電極…………72 6.1 前言……………………………………………………………………….72 6.2 實驗方法………………………………………………………………….72 6.2.1 C-TiO2複合物粒子製備…………………………………………..75 6.2.2 C-TiO2漿料配製……………….………………………………….75 6.3 結果與討論……………………………………………………………….79 6.3.1場發射掃描式電子顯微鏡影像 ( FESEM………………………..79 6.3.2 氮氣等溫吸附與脫附曲線(BET)…………………………………81 6.3.3球狀C-TiO2 composite形成機構示意圖…………………………83 6.3.4染料敏化太陽能電池測試結果…………………………………...84 6.4 結論……………………………………………………………………….8