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研究生： 林思羽
Lin, Ssu-Yu
論文名稱： 結合電沉積二氧化鈦緻密層與板鈦礦支架層製備高效率塑膠鈣鈦礦太陽能電池
High Efficiency Plastic Perovskite Solar Cell Using Low Temperature Processable Electrodeposited TiO2 Compact Layer and Brookite Scaffold
指導教授： 衛子健
Wei, Tzu-Chien
口試委員: 竇維平
Dow, Wei-Ping
李建良
Lee, Chien-Liang
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： 2017
畢業學年度： 105
語文別： 中文
論文頁數： 73
中文關鍵詞： 鈣鈦礦 、塑膠基板 、低溫 、電沉積 、板鈦礦
相關次數： 點閱：4  下載：0 
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    • 鈣鈦礦太陽能電池的效率在近十年來快速的成長至22.1 %，使得商業化的可能性大幅提升，但傳統形式的鈣鈦礦太陽能電池結構中，緻密層與多孔支架層二氧化鈦薄膜需高溫燒結製程，不僅不利於大面積連續生產，更消耗大量的能源。因此發展低溫製程的鈣鈦礦太陽能電池便成為實用化與否的一大重要技術挑戰。低溫製程的鈣鈦礦太陽能電池仍然可以硬式玻璃基板與塑膠高分子基板上施作，然一般認為塑膠高分子基板擁有輕量與可彎曲的特性，應用範圍較玻璃基板廣泛，因此此篇研究著重於發展低溫塑膠基板的鈣鈦礦太陽能電池。
    低溫鈣鈦礦太陽能電池的挑戰在於傳統緻密層與多孔支架層的二氧化鈦需高溫燒結，因此，此篇研究在緻密層的部分，為使不耐酸鹼性的塑膠高分子基板不被電沉積溶液腐蝕，添加螯合劑(EDTA)至電沉積溶液中，增加三氯化鈦在溶液中的溶解度，達到增加電沉積溶液pH值的目的，再進行電沉積反應沉積緻密層，並經由循環伏安法的結果發現沉積的薄膜具有良好的覆蓋率。而多孔支架層為不含黏著劑(Binder-free)的特殊多孔漿料，此漿料可在70 oC即形成板鈦礦二氧化鈦結晶，其結晶經由XRD確認，從TEM得知其幾何形狀為扁平狀且直徑相較於原先所使用的銳鈦礦二氧化鈦較小(約25奈米)，大約16-18奈米，除此之外，結合UV與UPS的結果發現，此漿料導帶位置也較銳鈦礦低，表示未經高溫燒結的多孔漿料可藉由顆粒較小且扁平狀增加與鄰近顆粒的接觸面積，以彌補未經燒結所增加的電子傳遞電阻與導帶位置低增加電子的注入能力。結合以上的電沉積緻密層與特殊多孔漿料，可製備出目前塑膠高分子基板的多孔結構最高效率，效率高達15.76 %。

    In recent years, fabricating plastic perovskite solar cells (PSCs) becomes increasingly attractive because of their light-weight and bendability. However, commercial plastic substrate like Indium Tin Oxide-polyethylene naphthalate (ITO-PEN) substrate cannot endure in high temperature and acidic condition, which are safe while making PSC on glass substrate. Previously, our group developed an electrodeposition technology to replace commonly-used spin coating to deposit more compact and thinner hole blocking TiOx layer at ambient temperature. In this research, modified electrodeposition is developed to deposit TiOx blocking layer (ED-BL) on ITO-PEN. As to scaffold layer, commercial brookite slurry are used to substitute conventional anatase slurry, because brookite slurry does not require high temperature post-treatment to remove binder so that entire process to be available below 150 oC. However, ITO-PEN is easily corroded in acidic solution bath with pH value below 3. Here, we adjusted the pH value to 4.8 and applied EDTA to solution bath to prevent particle aggregation and make the solution be suitable for ITO-PEN substrate. For brookite slurry, the XRD pattern evidenced that brookite crystal can be formed after annealing at 70 °C. Sheet-like structure of brookite particles with particle size between 16-18 nm was investigated by TEM, which was believed to provide more contact area with near particles, benefiting electron transfer. After process optimization, the flexible device fabricated in low temperature showed a champion photovoltaic efficiency of 15.76%.

    總目錄 摘要 I Abstract II 致謝 III 第一章 緒論 1 1-1前言 1 1-3太陽能電池的發展 3 第二章 文獻回顧 5 2-1鈣鈦礦太陽能電池 5 2-1-1鈣鈦礦起源與材料介紹 5 2-1-2鈣鈦礦太陽能電池的發展與近況 6 2-2低溫鈣鈦礦太陽能電池發展 8 2-2-1低溫多孔超結構鈣鈦礦太陽能電池發展 8 2-2-2低溫平面異質接面結構鈣鈦礦太陽能電池發展 10 2-3塑膠鈣鈦礦太陽能電池發展 13 2-3-1氧化鋅平面異質接面結構ETL 13 2-3-2氧化錫平面異質接面結構ETL 16 2-3-3 Zn2SnO4(ZSO)平面異質接面結構ETL 17 2-3-4 二氧化鈦平面異質接面結構ETL 19 2-3-5多孔結構鈣鈦礦太陽能電池 23 2-4研究動機與目的 25 第三章 實驗方法與儀器分析 26 3-1設備與儀器 26 3-2儀器原理 27 3-2-1太陽光模擬器 27 3-2-2 X光繞射儀 32 3-2-3二次飛行離子質譜儀(TOF-SIMS) 33 3-2-4紫外光/可見光光譜儀(UV-Vis) 34 3-2-5穿透式電子顯微鏡(TEM) 35 3-2-6 場發射掃描式電子顯微鏡(FE-SEM) 36 3-3藥品與材料 37 3-4實驗藥品製備與配置 38 3-4-1甲基碘化胺(CH3NH3I，MAI)合成方法 38 3-4-2電洞傳輸層製備 38 3-5理論與分析原理 39 3-5-1半導體能隙(Band gap)量測分析 39 3-5-3循環伏安法原理介紹 39 3-6實驗方法 43 3-6-1電沉積二氧化鈦緻密層 43 3-6-2塑膠鈣鈦礦太陽能電池製備流程 45 第四章 結果與討論 47 4-1電沉積二氧化鈦緻密層分析 47 4-1-1掃描式電子顯微鏡分析(SEM) 47 4-1-2 TiOx薄膜材料特性鑑定 49 4-1-3 TiOx薄膜緻密性及阻隔效果檢測 50 4-1-4 TiOx薄膜厚度檢測 52 4-1-5低溫TiOx緻密層鈣鈦礦太陽能元件光伏表現 53 4-2板鈦礦二氧化鈦多孔層特徵分析 55 4-2-1 多孔支架層結晶特徵鑑定 55 4-2-2多孔支架層幾何特徵鑑定 57 4-2-3多孔支架層能階分析 58 4-2-4優化低溫多孔支架層之元件表現 60 4-3 結合最適化電沉積TiOx緻密層與低溫板鈦礦多孔支架層之元件表現 61 4-4元件表現之機械性質測試與長效穩定性 63 第五章 結論 66 第六章 未來方向 67 參考文獻 68

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