臺灣博碩士論文加值系統

本研究以「飽和氣相反溶劑法」為基礎，即將蒸氣狀態的反溶劑與含有全無機鈣鈦礦前驅物的前體液進行溶合，混合後的溶劑對前驅物的溶解度下降，經過加熱乾燥後將達到過飽和狀態，誘導前驅物成核並生長成晶體。此方法可以成長高品質全無機鈣鈦礦晶體，然無法控制全無機鈣鈦礦晶體的形狀、尺寸、排列。本實驗室先前已結合微通道的毛細現象，並使用具奈米尺度溝槽狀的PDMS基板，當溶劑蒸發時沿著固定的路徑收縮，在基板溝槽內結晶方向一致且規則排列的線狀鈣鈦礦，形成大面積、有序的奈米線陣列。但在此製程條件所生長的奈米線密度不高、分布不均，且帶有許多顆粒狀副產物而影響奈米線的完整度。為了提高奈米線的結晶密度並抑制副產物的生成，我們嘗試各種方法將原有的基板進行表面修飾，提高奈米線密度。在此條件下，更進一步透過調控溶劑的反應空間，增加其停留在基板的時間，使奈米線的結晶效率最大化，成功合成出大面積、有序、高密度、均勻分布且不含顆粒的奈米線陣列。最終我們將奈米線轉移至其他目標基板，進行各種觀察與量測，以及分析奈米線的形貌、光學特性，並探討其結晶機制與應用範圍。

This thesis aims for development of large-area and high-density all-inorganic perovskite nanowire arrays based on a method called “saturated vapor-assisted crystallization,” which can synthesis various types of low-dimensional perovskite crystals, such as nanowires, nano-plates, etc. For this method, the anti-solvent vapors are introduced into the perovskite precursor to decrease perovskite solubility and then the precursor becomes supersaturation. Then the perovskite nucleates in this supersaturation solution crystalize into various types of low-dimensional perovskite crystal during the precursor drying. However, the shape, size and arrangement of crystals were uncontrollable. To overcome this problem, our team has demonstrated the well-aligned perovskite nanowire array by introducing a nanoscale-groove PDMS substrate into saturated vapor-assisted crystallization method. The well-aligned perovskite nanowires grow along the nanoscale grooves as the perovskite precursor evaporates and its area shrinks. Finally, the large-area, well-aligned perovskite nanowire array accompanying with some perovskite particles are obtained. However, the distribution of perovskite nanowire arrays are not dense and uniform. To further improve this issue about distribution density and uniformity as well as to suppress the perovskite particles, we modified the affinity of substrate surface by different surface treatments. With appropriate surface treatment, the density and uniformity of perovskite nanowire arrays are improved and the perovskite nanoparticles are almost eliminated. After the surface treatment, we further maximize the density and uniformity of perovskite nanowire arrays by manipulating the reaction space to slow down the evaporation rate of precursor. Consequently, we successfully synthesized large-area, periodic and well-aligned, high-density and uniform distribution, and particle-free perovskite nanowire arrays. For showing the potential applications of perovskite nanowire arrays, we also demonstrated that the perovskite nanowire arrays can be transferred on the other target substrates. Finally, we not only analyzed morphology and optical properties of perovskite nanowire arrays, but also investigated the both mechanisms of surface treatment and control of reaction space.

摘要................................................................................………………………................. i
Abstract…………………………………………………………………………….…...... ii
目錄................................................................................………………....………........... iv
圖目錄...............................................................................………………………............ vi
表目錄…................................................................................…………………............... ix
第一章 緒論…................................................................................…………………....... 1
1-1 鈣鈦礦的合成與應用…..............................................................................…....... 1
1-2 研究動機與目的…..............................................................................……........... 3
第二章 基本原理與文獻回顧…....................................................................................... 4
2-1 鈣鈦礦結晶機制…................................................................................………..... 4
2-1-1 鈣鈦礦前體液…................................................................................……...... 4
2-1-2 接觸角…................................................................................………….......... 5
2-1-3 馬倫哥尼效應…..........................................................................………….... 6
2-1-4 古典成核理論…................................................................................……...... 7
2-1-5 飽和氣相反溶劑法原理…............................................................................ 10
2-2 鈣鈦礦微奈米線陣列…....................................................................................... 11
第三章 實驗內容…................................................................................………............. 14
3-1 實驗規劃…................................................................................………............... 14
3-2 實驗器材介紹.................................................................................................….. 15
3-3 鈣鈦礦奈米線實驗製程….....................................................................……….. 19
3-3-1 PDMS基板製作…....................................................................................... 19
3-3-2 鈣鈦礦前體液合成….................................................................................... 20
3-3-3 飽和氣相反溶劑法….................................................................................... 21
3-3-4 基板表面修飾…................................................................................…….... 23
3-3-5 調控反應空間…............................................................................……….... 24
3-4 鈣鈦礦元件實驗製程........................................................................................... 27
3-4-1 奈米線轉印技術............................................................................................ 27
3-4-2 奈米線之光性量測架構................................................................................ 28
第四章 結果與討論....................................................................................................... 29
4-1 基板表面修飾對結晶的影響............................................................................... 29
4-1-1 控溫熏製法.................................................................................................... 29
4-1-2 旋塗修飾法.................................................................................................... 33
4-1-3 基板之接觸角、拉曼光譜量測.................................................................... 39
4-1-4 調控反應空間................................................................................................ 41
4-1-5 不同顏色的奈米線之形貌............................................................................ 51
4-2 奈米線之晶格結構與光性探討........................................................................... 61
4-2-1 奈米線之XRD量測..................................................................................... 61
4-2-2 奈米線之PL、反射與穿透.......................................................................... 63
第五章 結論與未來展望................................................................................................. 73
參考文獻........................................................................................................................... 74
附錄................................................................................................................................... 78

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