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研究生: 洪柏育
Po-Yu Hung
論文名稱: 發光性二氧化鈦之特性分析與太陽能電池之應用
Investigation of Luminescent Titanium Dioxide and Application on Sensitized Solar Cells
指導教授: 胡淑芬
Hu, Shu-Fen
學位類別: 碩士
Master
系所名稱: 物理學系
Department of Physics
論文出版年: 2009
畢業學年度: 97
語文別: 中文
論文頁數: 146
中文關鍵詞: 二氧化鈦染料敏化太陽能電池
英文關鍵詞: Titanium dioxide, solar cell
論文種類: 學術論文
相關次數: 點閱:207下載:8
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  • 染料敏化太陽能電池 (Dye-Sensitized Solar Cell, DSSC) 目前於世界各國研究仍屬開發階段,其光電轉換效能與商用矽晶太陽能電池相較仍有差距,但因其具備製作簡單、成本低、可撓性 (flexible) 及易製成大面積之產品等商業化優勢,故將成為下階段太陽能新能源急切發展之技術。針對DSSC之研究,主要針對四項組成元件:工作電極、染料、電解質及反電極,探討不同材料對於效率之影響。其中工作電極多屬半導體奈米薄膜如:二氧化鈦 (TiO2) 或氧化鋅 (ZnO)等,已存在多數研究其形貌結構與塗佈方式對於電池效率之影響。而近年來TiO2 摻雜稀土金屬元素之研究,多數僅只探討其發光及觸媒特性,卻未有應用於敏化太陽能電池工作電極之研究。
    本研究將以不同二氧化鈦前趨物及凝膠溶膠法、水熱法合成 TiO2 摻雜 Eu 粉體。主要內容探討 Eu 摻雜對於晶體成長及晶相生成之影響,並討論 Eu3+ 為發光中心引起之特殊發光特性及機制,且 Eu3+之摻雜對於 TiO2 吸收光譜及電子組態之影響也將於文中驗證。由於染料 Black dye 於紅光之特殊吸光特性,本研究將 TiO2: Eu3+ 應用於工作電池以增加染料對於太陽光之利用,且利用TiO2: Eu3+之特殊能階性質,設計雙層工作電極結構電池以增加光電流及電壓,進而提高電池效率,並以硒化鎘 (CdSe) 量子點取代染料 Black dye作為敏化物,觀察其光電特性。於本研究中針對 TiO2: Eu3+ 將進行材料結構鑑定及光譜特性分析,並針對敏化太陽能電池測量其光電特性及理論參數精算。

    第一章 緒論 1 1.1前言 1 1.2 太陽能電池簡介 2 1.3 染料敏化太陽能電池 6 1.3.1 工作原理 6 1.3.2 染料敏化太陽能電池各部分介紹 8 1.3.2.1 奈米結晶多孔膜電極 (nanocrystalline porous electrode) 8 1.3.2.2 染料(dye) 11 1.3.2.3 電解液(electrolyte) 14 1.3.2.4 相對電極(counter electrode) 16 1.3.3 染料敏化太陽能電池之文獻回顧與發展現況 16 1.4 二氧化鈦摻雜元素材料之研究 18 1.4.1 TiO2:Eu粉體發光特性說明 20 1.4.1.1主體晶格(Host) 20 1.4.1.2 活化劑(Activator) 22 1.5 研究動機與目的 23 第二章 實驗步驟與儀器分析方法 25 2.1 化學藥品 25 2.2合成方法 26 2.2.1溶膠凝膠法 (Micelle and sol - gel) 26 2.2.2 水熱法 (Hydrothermal) 27 2.3實驗流程 28 2.3.1 TPT[鈦酸四丁酯;Ti(OC4H9)4 ;Tetrabutyl titanate]系列 28 2.3.2 P25(Degussa P25 TiO2)系列 29 2.4 樣品鑑定分析 30 2.4.1 粉末X-光繞射儀(X-ray diffraction; XRD) 31 2.4.1.1 X-光繞射工作原理 31 2.4.1.2 XRD實驗儀器 34 2.4.1.3 結構精算 35 2.4.2 掃描式電子顯微鏡(Scanning Electron Microscope, SEM) 38 2.4.3 穿透式電子顯微鏡(Transmission Electron Microscopy,TEM) 39 2.4.4 比表面積分析儀(Accelerated surface area and porosimetry ,ASAP) 40 2.4.5 光激發光譜儀(Photoluminescence; PL) 42 2.4.6 拉曼散射光譜儀 (Micro Raman Scattering Spectrometer) 45 2.4.7 紫外可見光擴散式反射光譜(UV-Vis diffuse reflectance spectra; UV-Vis DRS) 46 2.4.7.1 固態粉體之吸收光譜 46 2.4.8 X射線光電子能譜儀( X-ray Photoelectron Spectroscopy,XPS ) 48 2.4.9 X光吸收光譜 (X-ray Absorption Spectroscopy ; XAS) 49 2.4.9.1 X光吸收近吸收邊緣結構 (X-ray Absorption Near-Edge Structure;XANES) 50 2.5 染料敏化太陽能電池之組裝與特性分析 51 2.5.1工作電極漿料配製 51 2.5.2導電玻璃清洗 51 2.5.3電池組裝與特性測試 51 2.5.4染料敏化太陽能電池性能測試 54 2.5.4.1電流電壓效率曲線(I-V curve)量測 54 2.5.4.2 入射單色光之光電轉換效率量測(incident photon to current convers-ion efficiency;IPCE) 56 2.5.4.3電化學阻抗分析(Electrochemical impedance spectroscopy, EIS) 57 2.6量子點敏化太陽能電池之組裝 62 2.6.1硒化鎘 (CdSe) 量子點之製備 62 2.6.2硒化鎘 (CdSe) 量子點之改質 (Ligand exchange) 64 2.6.3量子點敏化電池之組裝 66 第三章 結果與討論 67 3.1 TiO2:Eu3+ 材料結構鑑定分析 68 3.1.1 晶體結構分析 68 3.1.1.1 TiO2:Eu3+ (TBT系列) XRD分析 70 3.1.1.2 TiO2:Eu3+ (P25系列) 74 3.1.2 晶體表面形貌分析 79 3.1.2.1 SEM 與TEM粉體形貌分析 79 3.1.2.2氮氣等溫吸附與脫附分析(Brunauer -Emmett-Teller;BET) 83 3.1.2.2.1 TBT系列粉體BET分析 83 3.1.2.2.2 P25系列粉體BET分析 86 3.2 TiO2:Eu3+ 粉體光譜特性分析 88 3.2.1.1光激發光譜分析(PL) 88 3.2.1.2臨界距離與能量轉移機制 94 3.2.2拉曼散射光譜分析 (Raman scattering spectrum) 95 3.2.2.1 TBT系列粉體拉曼散射光譜分析 96 3.2.2.2 P25系列樣品拉曼散射光譜分析 98 3.2.3紫外-可見光擴散式反射光譜分析(UV-Vis DRS) 100 3.2.3.1 TBT系列粉體紫外-可見光擴散式反射光譜分析 100 3.2.3.2 P25系列粉體紫外-可見光擴散式反射光譜分析 104 3.2.4 X射線光電子能譜儀(XPS) 106 3.2.5 X-光吸收光譜(XAS) 113 3.3 Ti1-xO2:Eux3+粉體於染料敏化太陽能電池之應用研究 117 3.3.1 單層工作電極電池效率量測 117 3.3.2 雙層工作電極結構 121 3.3.2.1雙層工作電極結構電池製作說明 122 3.3.2.2電池效率量測 123 3.3.2.2雙層工作電極結構電池入射單色光子-電子轉化效率(IPCE)量測 128 圖3.52 Eu0.03-TBT/0-TBT電池吸附與未吸附染料工作電極之激發與放射光譜 130 3.3.2.3雙層工作電極結構電池電化學阻抗(EIS)量測 130 3.3.3 CdSe敏化雙層工作電極結構電池光電特性分析 134 第四章 結論 136 參考文獻 138

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