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研究生:游翊弘
研究生(外文):Yi-Hong You
論文名稱:以熱注入法合成溴化銫鉛量子點並應用於發光二極體之研究
論文名稱(外文):Synthesis of Cesium Lead Bromide Quantum Dots by Hot Injection Method and Application to Light Emitting Diodes
指導教授:陳良益陳良益引用關係
指導教授(外文):Liang-Yih Chen
口試委員:邱昱誠張志宇
口試委員(外文):Yu-Cheng ChiuChih-Yu Chang
口試日期:2022-07-15
學位類別:碩士
校院名稱:國立臺灣科技大學
系所名稱:化學工程系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2022
畢業學年度:110
語文別:中文
論文頁數:214
中文關鍵詞:熱注入合成法溴化銫鉛鈣鈦礦量子點發光二極體配體移除界面鈍化
外文關鍵詞:hot-injection methodcesium lead bromide quantum dotslight-emitting diodesligand removinginterfacial passivation
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全無機溴化銫鉛量子點由於優秀的光電性質和發光特性被譽為下一世代鈣鈦礦量子點發光二極體的首選材料,然而全無機銫鉛鹵素鈣鈦礦量子點發光二極體之效能受限於:(1)合成量子點時添加的長碳鏈配體(2)各層結構界面工程。本研究主要探討以熱注入合成法進行溴化銫鉛鈣鈦礦綠光量子點製備與光電性質分析,並以短配體置換工程以及表面配體最適化策略製備量子點發光二極體進行光電性質分析。本研究以熱注入合成法製備溴化銫鉛鈣鈦礦綠光量子點用來製備發光二極體,由於量子點表面的長碳鏈配體形成一絕緣層,導致載子注入與傳輸不易。需經過不同次數清洗純化程序後才可應用;清洗程序伴隨螢光量子效率、溶液保存性和成膜性不佳。透過短碳鏈配體置換後可承受多次清洗程序且維持優良的溶液分散性、均勻成膜性和螢光量子效率,透過溴化苯乙胺分子層與聚甲基丙烯酸甲酯的鈍化修飾量子點薄膜底部與頂部之間的界面缺陷,可使發光二極體之啟動電壓降低至2.7 V,最高輝度達354.0 cd/m2,最大電流效率與外部量子效率分別為35.7 cd/A與11.1 %。
All inorganic CsPbBr3 perovskite quantum dots (PeQDs) have praised as prior candidates for next-generation perovskite quantum dots light-emitting diodes (PeQLEDs) applications due to their excellent optoelectronic and light-emitting properties. However, the performance of CsPbBr3 based PeQLEDs is impdede by (i) the long insulating ligands linked on the surface of QDs (ii) the complex issue of device structure. This study synthesized CsPbBr3 quantum dots via hot-injection method and focused on the ligang exchange method and optimizing the density of QD’s surface. Firstly, the photoluminescence quantum yield (PLQY) of cesium lead bromide (CsPbBr3) PQDs may decrease during the wash process. Low ink stability and film morphology also are damaged by the this process. After shor chain ligang exchange, the cesium lead bromide (CsPbBr3) PQDs can endure the damage of anti-solvent. The PQDs were treated by short ligands exchange and different times of wash cycle,The turn-on voltage (Von), maximum luminance (Lummax), current efficiency (CE) and external quantum efficiency (EQE) of purification process cesium lead bromide (CsPbBr3) QD-LED were 4.1 V, 365.0 cd/m2, 23.5 cd/A and 7.34 %. Finally, the passivation strategy maily focus on the interface between hole transport layer and CsPbBr3 thin film and the interface between CsPbBr3 thin film and electron transport layer. 2-phenylethanamine bromide (PEA-Br) and poly(methyl methacrylate) act as passivation layer to modify the interface. The turn-on voltage (Von), maximum luminance (Lummax), current efficiency (CE) and external quantum efficiency (EQE) of purification process cesium lead bromide (CsPbBr3) QD-LED were 2.7 V, 354.0 cd/m2, 35.7 cd/A and 11.1 %
中文摘要 I
Abstract II
致謝 IV
目錄 V
圖目錄 XII
表目錄 XXV
第一章、緒論 1
1-1 前言 1
1-2 研究動機與目的 2
第二章、 理論基礎與回顧 4
2-1 半導體與奈米材料 4
2-1-1 半導體概念與能帶圖 4
2-1-2 奈米材料 9
2-2 鈣鈦礦材料 13
2-2-1 鈣鈦礦結構 13
2-2-2 鈣鈦礦材料發展 14
2-3 鈣鈦礦量子點介紹 15
2-3-1 鈣鈦礦量子點合成 16
2-3-2 鈣鈦礦量子點穩定性 26
2-3-3 鈣鈦礦表面配體種類 36
2-3-4 鈣鈦礦量子點表面工程 38
2-4 鈣鈦礦量子點發光二極體 42
2-4-1 發光二極體各層結構介紹 43
2-4-2 量子點配體對元件性能影響 47
2-4-3 界面鈍化層對元件性能影響 55
第三章、 實驗設計 65
3-1 實驗流程圖 65
3-2 實驗藥品 66
3-3 實驗分析儀器與原理 70
3-3-1 超音波震盪器 (ultrasonic cleaner) 70
3-3-2 攪拌式加熱板 (hot plate) 70
3-3-3 管式高溫爐 (tube furnace) 70
3-3-4 微量天平 (electronic balance) 71
3-3-5 外光燈 (UV lamp) 71
3-3-6 旋轉塗佈機 (spin coater) 72
3-3-7 手套箱 (glove box) 73
3-3-8 金屬蒸發源系統 (metal evaporation source system) 74
3-3-9 紫外光-可見光光譜儀(UV/visible spectrophotometer) 75
3-3-10 螢光光譜儀(fluorescence spectrophotometer) 77
3-3-11 絕對量子效率 78
3-3-12 X光繞射分析儀(X-ray diffraction,XRD) 79
3-3-13 場發穿透式電子顯微鏡 (transmission electron microscope,TEM) 81
3-3-14 時間解析光致發光測量系統(time-resolved photoluminescence,TRPL) 83
3-3-15 紫外光電子能譜儀(ultraviolet photoelectron spectroscopy,UPS) 85
3-3-16 高解析度場發射型掃描式電子顯微鏡 (high resolution field-emission scanning electron microscope,FE-SEM) 87
3-3-17 傅立葉轉換紅外線光譜儀(Fourier transform infrared spectroscopy,FTIR) 89
3-3-18 電致發光量測系統(electroluminescence,EL) 90
3-4 實驗步驟 92
3-4-1 以熱注入法合成長碳鏈配體的CsPbBr3量子點 92
3-4-2 以短碳鏈配體置換法修飾熱注入合成CsPbBr3量子點 94
3-4-3 量測CsPbBr3量子點螢光量子效率 95
3-4-4 CsPbBr3發光二極體製備 98
3-4-5 CsPbBr3發光二極體優化製程 101
3-4-6 電子主導元件(electron only devie,EOD)製作 103
3-4-7 電洞主導元件(hole only devie,HOD)製作 105
3-4-8 發光二極體效能指標介紹 108
3-4-9 電子主導元件與電洞主導元件之分析與計算 115
第四章、 結果與討論 117
4-1 以熱注入法合成長碳鏈CsPbBr3量子點製程優化與性質分析 117
4-1-1 以長碳鏈配體進行CsPbBr3量子點合成與性質分析 117
4-1-2 純化步驟調控CsPbBr3量子點表面長碳鏈配體密度與性質分析 122
4-2 短碳鏈配體置換法探討CsPbBr3量子點製程優化之可行性評估 138
4-2-1 以短碳鏈配體置換法探討CsPbBr3量子點之性質分析 138
4-2-2 純化步驟調控CsPbBr3量子點表面短碳鏈配體密度與性質分析 146
4-2-3 以純化過具短碳鏈配體CsPbBr3量子點進行發光二極體之性能研究 156
4-3 界面修飾對CsPbBr3量子點發光二極體特性研究 168
4-3-1 探討以鈍化層修飾電洞傳輸層與CsPbBr3量子點薄膜界面對發光二極體之性能 169
4-3-2 探討以溶劑修飾CsPbBr3量子點薄膜與電子傳輸層界面對發光二極體之性能之影響 183
第五章、 結論 191
第六章、 參考文獻 193
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