有機無機混和型鈣鈦礦如甲胺碘化鉛和甲脒碘化鉛，因為擁有優異的光電性質，包括了在可見光波段有高消光係數、合適且可調整的能隙大小，以及長的載子傳遞長度，因此吸引了許多研究團隊研究，並且被廣泛應用在太陽能電池上。發展至此，鈣鈦礦太陽能電池的光電轉換效率已達24.2%。然而，在製備鈣鈦礦中，常用碘化鉛的二甲基甲醯胺溶液作為前驅物，但是二甲基甲醯胺卻具有高毒性而限制了其未來商用化的可能性。有鑑於此，本團隊過去成功發展出以硝酸鉛水溶液作為前驅物製備鈣鈦礦太陽能電池的技術，但是同時也發現硝酸鉛轉變成鈣鈦礦是兩步驟轉換，需要較長反應時間才可有高轉化率，然而反應時間過長而容易使鈣鈦礦產生過大晶粒與剝離的現象。為此，本研究創新了一製備鈣鈦礦的技術：三步法，即先利用碘-醇類溶液碘化硝酸鉛，再浸泡於碘甲胺/氯甲胺溶液得到鈣鈦礦。雖然步驟增加，卻可縮短反應時間並減少高毒性溶劑的使用。
在實驗結果上，浸泡碘液後，硝酸鉛從島狀分布轉變成片狀結構，且由X光繞射之分析確認其組成為碘化鉛，再將之浸泡於碘甲胺/氯甲胺溶液中即可轉變成鈣鈦礦。在碘液溶劑的部分，研究發現以異丁醇系統為最佳，效率達2.78%。經由第三步驟總濃度的調控後，碘甲胺和氯甲胺的重量比9：0.9為最佳條件，效率進一步提升至4.23%。在碘-氯比例的部分，以增加氯甲胺和減少碘甲胺的方式調控比例，避免第三步驟的溶液總濃度變化過大，加上三步法製備出的鈣鈦礦表面粗糙度高，所以降低轉速來得到較厚的電洞傳輸層，以減少金電極和鈣鈦礦的接觸機會，使效率再提升至8.49%。最後，優化反應時間，以浸泡1.5和0.5分鐘的條件為最佳，元件效率最高可達8.85%。
與標準系統(兩步法)比較，三步法所得之鈣鈦礦在結晶度、電子與電洞傳遞上均弱於標準系統，故短路電流和電壓上較低。此外，藉由二次離子質譜儀的檢測，可得知鈣鈦礦於多孔層內的填孔率不佳，進而影響載子的傳遞效率。由SEM的結果可觀察到，在鈣鈦礦的表面上因為有突出的晶粒生成，薄膜粗糙度是較高的，所以需要相對較厚的電洞傳輸層來避免金和鈣鈦礦的直接接觸，使元件效率降低。

Organic-inorganic hybrid perovskite, such as MAPbI3 and FAPbI3, has attracted the attention of many research groups due to its promising optoelectronic properties, including high extinction coefficient in the range of visible light, appropriate and tunable band gap, and long carrier transport length. It renders that perovskite has been widely used in solar cells. So far, the efficiency of perovskite solar cells (PSCs) has rapidly progressed to 24.2%. For fabricating perovskite films, PbI2 dissolved in DMF is the commonly used precursor for solution process. However, DMF inhibits the commercialization of PSCs due to its toxicity. As a result, our research group developed the technology to fabricate perovskite films by using the aqueous Pb(NO3)2 precursor, but converting Pb(NO3)2 to perovskite was 2-step process, so it took longer reaction time to convert into perovskite completely. However, it caused perovskite films were delaminated from the mesoporous layer. Also, it formed coarsened grains. Therefore, develop the new technology to form perovskite: 3-step method, i.e., iodizing Pb(NO3)2 first by iodine-alcohol solution, and then dipping into MAI/MACl solution to fabricate perovskite films. Although steps increased, it minimized the toxicity due to solvents and decreased reaction time.
From experiment results, the island-like Pb(NO3)2 morphology was transformed into the flake-like structure after dipping into iodine solution. From XRD results, Pb(NO3)2 can be converted into PbI2 and then further become perovskite by reacting with MAI/MACl solution. In the part of the solvent of the iodine, the best was i-butanol system, and the efficiency was 2.78%. In the part of controlling overall concentration of MAI/MACl solution, the appropriate ratio was 9:0.9 (w:w), and then the efficiency increased to 4.23%. In the part of adjusting the ratio of MAI and MACl, the adequate result was 8.1:2. Besides, the roughness of perovskite films fabricated by 3-step method was high, so it needed thicker hole-transport layer (HTL) to cover perovskite films. It can avoid direct contact between perovskite films and the gold electrode. So, the efficiency was improved to 8.49%. Finally, by adjusting reaction time, the best dipping condition was 1.5 and 0.5 minutes. The highest efficiency was 8.85%.
In comparison with standard process of our research group (2-step method), the crystallinity and carrier transport ability of perovskite films fabricated by 3-step method were lower. Thus, it decreased short-circuit current density and open-circuit voltage. Also, from SIMS resuls, the hole filling ratio of perovskite was not good in the mesoporous layer. It caused lower electron-transport efficiency. From SEM result, the roughness of perovskite films was higher, so it needed thicker HTL to decrease the connection between perovskite films and the gold electrode.

摘要...............................................................I
Abstract.........................................................III
總目錄.............................................................V
圖目錄...........................................................VII
表目錄............................................................XI
第一章 緒論.........................................................1
第二章 文獻回顧.....................................................6
2-1 鈣鈦礦太陽能電池(Perovskite solar cell).........................6
2-1.1 鈣鈦礦發現與特性介紹..........................................6
2-1.2 鈣鈦礦太陽能電池的起源和發展...................................9
2-1.3 鈣鈦礦太陽能電池運作原理......................................20
2-2 鈣鈦礦鉛前驅物介紹.............................................23
2-3 鈣鈦礦層之製備方式.............................................26
2-3.1 濕式製程製備鈣鈦礦薄膜.......................................26
2-3.2 乾式製程製備鈣鈦礦薄膜.......................................31
2-4 研究目的與動機.................................................34
第三章 研究方法與儀器分析...........................................36
3-1 實驗儀器和相關分析設備.........................................36
3-2 實驗藥品和相關材料.............................................37
3-3 實驗步驟與方法.................................................39
3-3.1 HTM, Spiro-OMeTAD溶液製備...................................39
3-3.2 碘甲胺CH3NH3I, MAI之製備.....................................40
3-3.3 基板至多孔層之製備...........................................41
3-3.4 碘液與鈣鈦礦太陽能電池之製備..................................42
3-3.5 標準兩步法鈣鈦礦薄膜製備流程..................................44
3-4 儀器分析、理論與分析原理........................................46
3-4.1 X光繞射儀(X-ray diffractometer, XRD)........................46
3-4.2 紫外光-可見光光譜儀(UV-Vis spectrometer).....................49
3-4.3 傅立葉轉換紅外線光譜儀(Fourier-transform infrared spectroscopy (FTIR))...........................................................53
3-4.4 掃描式電子顯微鏡(Scanning electron microscopy, SEM)..........56
3-4.5 太陽光模擬器(Solar simulator)與電流密度-電壓曲線..............58
3-4.6 光致放光光譜(Photoluminescence spectra, PL)..................64
3-4.7 飛行時間二次離子質譜儀(Time-of-flight secondary ion mass spectrometer, TOF-SIMS)...........................................67
3-4.8 能量色散X-射線光譜(Energy-dispersive X-ray spectroscopy, EDX) ..................................................................72
第四章 實驗結果與討論..............................................74
4-1 水相製備碘化鉛薄膜與有機碘液之分析..............................74
4-2 三步法所得碘化鉛與鈣鈦礦薄膜之性質分析...........................80
4-3 浸泡條件之優化對元件效率之影響..................................92
4-4 三步法系統之問題以及與標準系統之比較...........................101
第五章 結論.......................................................107
第六章 未來工作...................................................109
第七章 引用文獻與資料.............................................110

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