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研究生： 黃哲緯
Huang, Che-Wei
論文名稱： 有機染料分子修飾溶膠凝膠之氧化鋅應用於反式高分子太陽能電池
Sol-gel ZnO modified by organic dye molecules for efficient inverted polymer solar cells
指導教授： 溫添進
Wen, Ten-Chin
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2019
畢業學年度： 107
語文別： 中文
論文頁數： 84
中文關鍵詞： 高分子太陽能電池 、氧化鋅 、界面修飾 、有機染料分子
外文關鍵詞： polymer solar cell, ZnO, interfacial modification, organic dye molecules
相關次數： 點閱：64  下載：0 
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    • 本論文以三苯基甲烷類染料分子做為氧化鋅之添加劑，藉由將染料分子直接加入溶膠凝膠法製程的氧化鋅前驅液裡，去修飾氧化鋅上的缺陷，並將改質後的氧化鋅應用在高分子太陽能電池裡，藉由摻雜的方式，可以在製備氧化鋅薄膜的同時一併完成界面修飾，以此提升整體元件的效率。
    此研究主要使用結晶紫(Crystal violet, CV)和乙基紫(Ethyl violet, EV)作為氧化鋅電子萃取層的添加劑，經證實摻雜之染料分子會分布在整個氧化鋅層並鈍化其缺陷，其濃度會由表面往下逐漸遞減，存在表面之染料分子會藉由氯離子填補氧化鋅表面的氧空缺，存在氧化鋅層裡晶粒邊界的染料分子則會傾向未完全反應的羥基，降低其干擾電子傳輸的可能性。此外添加之染料分子可以形成界面偶極，使氧化鋅之功函數降低，進一步降低界面傳輸電子的能障，且摻雜染料分子後能使氧化鋅表面更趨疏水，促進其與主動層的界面相容性，也使得元件穩定性上升。因此經由結晶紫和乙基紫修飾後之元件效率可以從7.59%分別提升到8.80%和9.06%，約為16%和19%的增幅。

    In this study, doped ZnO layer is prepared by blending organic dye molecules, Crystal violet (CV) and Ethyl violet (EV) to a typical sol-gel process and used as the electron transport layer in inverted polymer solar cells (PSCs). The CV or EV distributed in the whole ZnO layer and decreased progressively from surface to bottom are confirmed by depth profile of chloride. X-ray photoelectron spectroscopy (XPS) results further showed the presence of CV or EV in ZnO surface and indicated that the surface oxygen defect occupied by Cl by the formation of Zn-Cl bond. The dye molecules remained inside ZnO layer would lean to unreacted hydroxyl groups by the lone pair of nitrogen, hence reduce the possibility of interfering the electron transport. Besides, the formation of interface dipole by quaternary ammonium chloride would slightly reduce the work function of ZnO surface, further cut down the energy barrier between the ZnO layer and the active layer. The doped ZnO layer presented a smoother and more hydrophobic because of the dimethylaniline group and therefore enhance the contact with active layer. As a result, inverted PSCs based on CV doped ZnO and EV doped ZnO possess better morphology, better electron extraction ability and exhibit the power conversion efficiency (PCE) up to 8.80% and 9.06% respectively, in comparison to the pristine ZnO (7.59%) is about 16% and 19% enhancement. Here, we demonstrate a facile way to improve morphological and electrical properties of ZnO by simply doping organic dye molecules, and apply it to inverted PSCs to enhance the PCE.

    摘要 I Extended Abstract II 誌謝 XII 目錄 XIII 圖目錄 XVII 表目錄 XXI 符號與縮寫 XXII 符號 XXII 縮寫 XXIV 第一章 緒論 1 1-1. 前言 1 1-2. 有機太陽能電池簡介 4 1-2-1. 有機太陽能電池之光電轉換原理 4 1-2-2. 有機太陽能電池材料之發展 9 1-3. 陰極修飾層之簡介 14 1-3-1. 金屬氧化物做為電子萃取層 14 1-3-2. 氧化鋅之溶液製程簡介 15 1-4. 氧化鋅之界面修飾 18 1-4-1. 共軛聚電解質 (Conjugated polyelectrolyte, CPE) 18 1-4-2. 雙離子共軛高分子(Water/alcohol soluble conjugated polymers with zwitterionic groups) 20 1-4-3. 絕緣體高分子 (Insulating polymer) 21 1-4-4. 有機小分子材料 24 1-4-5. 雙離子型小分子材料 26 1-4-6. 自組裝單分子層 28 1-4-7. 摻雜 (Doping) 29 1-5. 研究動機 33 第二章 摻雜三苯基甲烷類染料於氧化鋅做為陰極修飾層應用於反式高分子太陽能電池 34 2-1. 前言 34 2-2. 實驗部分 36 2-2-1. 藥品與材料來源 36 2-2-2. 元件製備流程 37 2-2-3. 元件特性量測 41 2-2-4. 掃描式電子顯微鏡量測 41 2-2-5. 原子力顯微鏡量測 41 2-2-6. 影像式接觸角量測 42 2-2-7. 熱重分析量測 42 2-2-8. X光與紫外光光電子能譜儀分析 42 2-2-9. 化學分析電子光譜儀之縱深分析 43 2-2-10. X光薄膜繞射儀之分析 43 2-2-11. 外部量子效率量測 43 2-2-12. 載子萃取能力量測 44 2-3. 結果與討論 45 2-3-1. 表面形貌與影響 45 2-3-2. 三苯基甲烷類染料之熱穩定性分析 50 2-3-3. X光光電子能譜對氧化鋅薄膜之分析 51 2-3-4. 化學分析電子光譜儀(ESCA)對氧化鋅之縱深分析 57 2-3-5. X光薄膜繞射分析 59 2-3-6. 光電性質之分析 61 2-3-7. 電子萃取能力之分析 64 2-3-8. 摻雜三苯基甲烷類染料對太陽能元件表現之影響 68 2-3-9. 三苯基甲烷類染料對元件穩定性的影響 71 第三章 摻雜染料分子於氧化鋅之機制 73 3-1. 前言 73 3-2. 溶膠凝膠法氧化鋅之製程 73 3-3. 染料分子對於氧化鋅之影響與機制 75 第四章 總結與建議 78 參考文獻 79

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