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研究生： 徐彥明
Yan-ming Hsu
論文名稱： 利用超分子團鏈共聚高分子模板合成二氧化鈦奈米孔洞陣列薄膜應用於染敏太陽能電池
Well ordered mesoporous TiO2 nanostructures synthesized from Dendron-jacketed block copolymer templates for Dye-Sensitized Solar Cell
指導教授： 孫亞賢
Ya-sen Sun
口試委員:
學位類別： 博士
Doctor
系所名稱： 工學院 - 化學工程與材料工程學系
Department of Chemical & Materials Engineering
論文出版年： 2014
畢業學年度： 102
語文別： 中文
論文頁數： 66
中文關鍵詞： 超分子團鏈共聚物 、熱回火 、模板合成 、染敏化電池
外文關鍵詞： supramolecular, thermal annealed, nanotemplate, Dye-Sensitized Solar Cell
相關次數： 點閱：18  下載：0 
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    • 本論文研究刮膜製程下，超分子團鏈共聚物薄膜之自組織行為。經由穿透式顯微鏡和掠角小角度Ｘ光散射量測下，我們發現超分子團鏈共聚物薄膜在熱回火過程，內部結構由橢球狀結構，經由rhombohedral之過渡態再轉變成垂直六方排列柱狀結構。利用超分子團鏈共聚物所形成之水平和垂直奈米柱狀陣列模板，透過模板合成方式製備出二氧化鈦孔洞陣列薄膜。最後將製備完成之二氧化鈦薄膜應用於染料敏化太陽能電池工作電極，比較二氧化鈦奈米結構為粒子、水平孔洞陣列、垂直孔洞陣列時的電池效率值。此外，我們也製備出雙層結構工作電極，觀察是否在不同結構的搭配下，效率值之變化。

    In this study, we have demonstrated that supramolecular dendron-jacketed block copolymers can be used as nano-sized templates to synthesize high densities of arrays of TiO2 nanostructures Upon tailoring the grafted fractions of small molecules to change the volume fraction of PS segments within self-assembled PS-P4VP(3C12)0.7 films, the nanostructures of the films can be systematically controlled. Preferential incorporation of 3C12 into the P4VP domains changed the volume fraction (f) of the PS domain. When the volume fraction of PS reached f = 0.29 %, the internal nanostructures of the films changed from spherical nanodomains (S) to perpendicularly-oriented nanocylinders (C┴) after being thermally-annealed at 150 oC for 24 h. By analyzing the cross-section images of TEM and scattering patterns of GISAXS, we discovered that the morphological transition of S→C┴ underwent a rhombohedral state. Next we immersed the self-assembled PS-P4VP(3C12)0.7 films in ethanol containing TiF4, by which TiF4 dissolved to form titanium ions in ethanol. Since 3C12 small molecules were soluble in ethanol and have stronger affinity to the P4VP domain than 3C12, the titanium ions could replace 3C12 to preferentially bond the P4VP domains. We also used GISAXS to characterize the structural evolution of the films in an immersion process. Finally the nanodomains were further used as templates to direct the synthesis of nanoporous TiO2 thin films after immersion in solutions containing TiF4 followed by high-intense light exposure. The synthesized TiO2 nanostructures can be further facilely used for electrodes of dye-sensitized solar cells (DSSC). Various nanostructured DSSCs devices were fabricated, and their performances were also tested and discussed in this thesis.

    摘要 I Abstract II 誌謝 IV 目錄 VI 圖目錄 X 表目錄 XIV 第一章 簡介 1 1-1 前言 1 1-2 染敏化太陽能電池的結構 1 1-1.1 奈米管(nanotube) 2 1-1.2 奈米棒(nanorod) 3 1-1.3 奈米線(nanowire) 4 1-3 一維(1D)TiO2奈米結構之合成 5 1-3.1 溶膠-凝膠方法(sol–gel methods) 5 1-3.2 模板輔助法(template-assisted methods) 6 1-3.3 水/溶熱法(hydro/solvothermal) 8 1-3.4 電化學法(Electrochemical means) 9 1-4 超分子聚合物形態 12 1-5 熱回火對超分子聚合物薄膜之行為 13 1-6 團鏈共聚物模板的應用 14 1-7 實驗動機 16 第二章 實驗 17 2-1 高分子材料 17 2-2 溶劑藥品與基材 18 2-3 實驗儀器 19 2-4 試片製備與實驗步驟 20 2-4.1 塊材超分子團鏈共聚物(PS24k-P4VP9.5k (3CY)X)的製備 20 2-4.2 清洗基材 20 2-4.3 雙團鏈共聚物及超分子團鏈共聚物溶液之製備 20 2-4.4 超分子團鏈共聚物薄膜之製備 21 2-5 超分子團鏈共聚物刮膜之製備 22 2-6 染料敏化太陽能電池製程 23 2-6.1 TiF 4酒精水溶液製備 23 2-6.2 TiO2工作電極(光電極)製備 23 2-7 儀器分析 25 2-7.1 光學顯微鏡 25 2-7.2 原子力顯微鏡 26 2-7.3 場發射掃描式電子顯微鏡 28 2-7.4 低掠角X光散射儀 30 2-7.5 高近似型太陽光模擬器 31 2-7.6 光譜響應量測系統 32 第三章 結果與討論 33 3-1 垂直有序奈米柱狀陣列膜板的製備 34 3-1.1 利用超分子聚合物製備奈米膜板 34 3-1.2 熱回火誘導垂直柱狀結構之成長機理 38 3-1.3 控制奈米柱狀陣列方向之策略 39 3-2 二氧化鈦奈米孔洞陣列薄膜製備 45 3-3 染料敏化太陽能電池(Dye-sensitized solar cell) 57 第四章 結論 61 參考文獻 64

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