鈣鈦礦太陽能電池由於轉換效率進展極為快速，成為新興太陽能電池界的超級新星。以有機鉛之鹵化物為基礎的鈣鈦礦結構材料具備了優異的光電性能與製膜簡易等的優勢，使其應用在薄膜型太陽電池的表現非常突出。然而在製備此類鈣鈦礦薄膜的過程中，不論是常見的一步法或是兩步法，大多會使用具毒性且致癌性碘化鉛及二甲基甲醯胺等溶劑，造成了鈣鈦礦太陽電池發展與大量使用的隱憂。
在此論文中，我們延續並改良的了本團隊先前開發以低毒性硝酸鉛水溶液系統之三步法製備鈣鈦礦薄膜的研究，期望獲得更高的光轉效率。具體而言採取了三個改善方法。此三種方法包括製程中引入太陽光照協助鈣鈦礦成核、甲胺(MA)蒸氣對鈣鈦礦表面進行處理及添加甲脒陽離子(FA+)以調整鈣鈦礦之化學組成。其中第一種方法會同時照射太陽光模擬器提供之太陽光以進行成核的控制，以達縮小鈣鈦礦的晶粒大小與減少晶界以達到更好的表面形貌。第二部分則是在鈣鈦礦薄膜進行MA蒸氣處理，讓薄膜得以蒸氣下溶解再結晶以有效攤平(levelling)原先粗糙的表面。最後一部分，會利用FA+陽離子旋塗方式以完成雙重陽離子的FAMAPbI3的最終鈣鈦礦組成，得以提高元件之光電效率及穩定性。
此一製程可以製作最高效率達14.42%的鈣鈦礦太陽電池，可望為硝酸鉛水溶液系統的應用理出一條嶄新的道路。

Perovskite solar cells (PSCs) has become a new trend in the solar cell industry because of its fast development on efficiency. The lead and halogen based perovskite structure has excellent photoelectronic properties and are easy to fabricate. However, the prevalent use of lead iodide or toxic DMF in either one-step or two-step procedures has become a huge drawback.
In this study, we optimize the non-toxic three step aqueous Pb(NO3)2 system previously reported by our team, expecting to achieve a higher efficiency. We report three kinds of approach to improve the film quality of three-step aqueous Pb(NO3)2 system. These three approach involves a novel method named sun illumination, introduction of methylamine(MA) gas treatment and addition of formaldinium cations(FA+). The sun illumination method is used to control the nucleation and perovskite growth in order to reduce defects. The MA gas treatment approach involves instant liquification and recrystallization which can level the rough morphology. The FA+ incorporation can effectively fabricate a mixed-cation perovskite FAMAPbI3 which improves both stability and efficiency.
The final conversion efficiency( PCE) improved to 14.42%, leading to a new way for three-step lead nitrate procedure.

目錄.......................................................................................................................................................... 4
圖目錄...................................................................................................................................................... 2
表目錄....................................................................................................................................................10
摘要.......................................................................................................................................................... 2
ABSTRACT ............................................................................................................................................ 3
1 第一章 緒論........................................................................................................................................ 11
1-1 前言............................................................................................................................................. 11
1-2 太陽能電池的基本原理 ............................................................................................................13
1-3 太陽能的歷史與發展 ................................................................................................................13
2 第二章 文獻回顧..............................................................................................................................16
2-1 鈣鈦礦太陽能電池.....................................................................................................................16
2-1.1 鈣鈦礦的起源、特性與結構 .............................................................................................16
2-1.2 鈣鈦礦太陽能電池的歷史與發展 .....................................................................................18
2-1.3 鈣鈦礦太陽能電池的結構 ................................................................................................. 19
2-1.4 鈣鈦礦太陽能電池的工作原理 .........................................................................................20
2-2 鈣鈦礦薄膜的製備方式.............................................................................................................21
2-2.1 以碘化鉛為前驅物之旋轉塗佈一步法 .............................................................................22
2-2.2 以碘化鉛前驅物之旋轉塗佈兩步法 .................................................................................23
2-2.3 硝酸鉛水溶液前驅物 .........................................................................................................24
2-3 鈣鈦礦層表面形貌優化的方法................................................................................................. 42
2-3.1 太陽光照射法 ....................................................................................................................42
2-3.2 MA 蒸氣處理法.................................................................................................................44
2-3.3 添加劑方法.........................................................................................................................47
2-3.4 成核溫度控制法 .................................................................................................................49
2-4 兩步法中添加 FA+陽離子進行組成調控工程..........................................................................51
2-5 研究動機....................................................................................................................................56
3 第三章 實驗方法與儀器分析 ..........................................................................................................57
3-1 實驗藥品與材料.........................................................................................................................57
3-2 實驗儀器與分析設備.................................................................................................................58
3-3 儀器介紹....................................................................................................................................59
3-3.1 X 光繞射分析儀 (X-Ray Diffractometer, XRD) .............................................................59
3-3.2 紫外光-可見光光譜儀(Ultraviolet-visible spectrometer, UV-vis)...................................60
3-3.3 場發射掃描式顯微鏡(Field emission scanning electron microscope, FE-SEM)......60
5
3-3.4 聚焦離子束電子束掃瞄式顯微鏡系統 (Dual-beam Focused Ion Beam system， FIB)
......................................................................................................................................................61
3-3.5 太陽光模擬器(Solar Simulator)........................................................................................62
3-3.5.1 短路電流及短路電流密度(Isc＆Jsc)......................................................................................... 64
3-3.5.2 開路電壓(Open circuit voltage,Voc) ......................................................................................... 65
3-3.6 紫外光臭氧清洗機(UV-ozone) ..........................................................................................66
3-4 實驗方法.............................................................................................................................68
3-4.1 鈣鈦礦太陽能元件製備 .....................................................................................................68
FTO 導電玻璃基板前處理..................................................................................................................... 68
二氧化鈦緻密層製備流程...................................................................................................................... 68
二氧化鈦多孔支架層製備流程.............................................................................................................. 68
鈣鈦礦吸光層製備.................................................................................................................................. 68
硝酸鉛水溶液配備 ............................................................................................................................ 69
PbI2/IBA 製備.................................................................................................................................... 69
鈣鈦礦薄膜層製備流程 .................................................................................................................... 69
鈣鈦礦 MA 蒸氣處理方式................................................................................................................ 70
鈣鈦礦添加 FA+離子......................................................................................................................... 70
電洞傳輸層製備流程.............................................................................................................................. 71
金屬背電極蒸鍍...................................................................................................................................... 71
4 第四章 實驗結果與討論..................................................................................................................72
4-1 太陽光照對碘化鉛薄膜之影響................................................................................................. 72
4-1.1 碘化鉛薄膜於 MAI/IPA 溶液浸泡分析............................................................................72
4-1.1.1 光照對 MAPbI3形貌之影響....................................................................................................... 72
4-1.1.2 光照對轉化率之影響.................................................................................................................. 75
4-1.1.3 光照對鈣鈦礦吸收度之影響...................................................................................................... 76
4-1.2 碘化鉛薄膜於 MAX/IPA 溶液浸泡分析 ..........................................................................78
4-1.2.1 光照對形貌之影響...................................................................................................................... 78
4-1.2.2 光照對轉化率之影響.................................................................................................................. 79
4-2 水性硝酸鉛三步法鈣鈦礦太陽能電池之表現 .........................................................................82
4-2.1 MA 蒸氣處理法後之元件性質及表現..............................................................................82
4-2.1.1MA 蒸氣處理後之元件性質....................................................................................................... 82
4-2.1.2MA 蒸氣處理後之元件表現....................................................................................................... 89
4-2.2 FAI 之添加以製備多重陽離子 FAMAPbI3鈣鈦礦元件 .................................................91
5 第五章 結論........................................................................................................................................99
6 第六章 未來工作..............................................................................................................................103
7 第七章 參考文獻..............................................................................................................................104

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