延遲退火對大氣下一步驟無反溶劑法製備之鈣鈦礦膜的影響

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研究生：	林其鋒 Chi-Feng Lin
論文名稱：	延遲退火對大氣下一步驟無反溶劑法製備之鈣鈦礦膜的影響
指導教授：	吳春桂 Chun-Guey Wu
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
論文出版年：	2023
畢業學年度：	111
語文別：	中文
論文頁數：	169
中文關鍵詞：	鈣鈦礦太陽能電池
外文關鍵詞：	Perovskite solar cell
相關次數：	點閱：10 下載：0
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一般式鈦礦太陽能電池(Perovskite solar cells，簡稱PSCs)當中的鈣鈦礦膜在製備時常使用非揮發性溶劑(如：DMF和DMSO)溶解鈣鈦礦前驅物，這些非揮發性溶劑需要透過反溶劑以及高溫退火等方式移除，並且製膜需在手套箱中進行，此複雜且高成本的處理方式使得PSC在商品化過程中受到限制。本研究在大氣下，以揮發性液體做為可快速蒸發的溶劑，使鈣鈦礦快速結晶而不需使用反溶劑，並讓鈣鈦礦膜的製備可在大氣下操作，不受到水氣及氧氣的影響製備出高品質的鈣鈦礦膜。為了提高元件的效率，以本實驗室自行合成之分子BT-IDT做為鈣鈦礦與電洞傳遞層之間的界面修飾，期望以BT-IDT上的CN-基團以及噻吩上的S原子之孤對電子，與鈣鈦礦層中未配位飽和的Pb2+作用，以達到鈍化鈣鈦礦的效果，然而隨著實驗的進行發現元件效率的提高並不是因為BT-IDT分子的界面修飾，而是透過延遲退火提供鈣鈦礦膜足夠的時間晶粒生長。SEM圖顯示延遲退火的鈣鈦礦膜平整緻密，以其為吸收層所組裝之元件光電轉化效率可達22.8%，比直接退火的鈣鈦礦膜所組裝之元件的20.7%增加了約10%。從XRD圖可以看到不管是直接退火或是延遲退火製備的鈣鈦礦膜都沒有PbI2的繞射峰，而有延遲退火的鈣鈦礦膜其 (110) 面的繞射峰強度比直接退火的鈣鈦礦膜強，表示鈣鈦礦膜的結晶度更好，延遲退火30分鐘所製備的鈣鈦礦膜的結晶區塊為23.4 nm，比直接退火所製備的鈣鈦礦膜的結晶區塊(為22.0 nm)大，體現在所組裝之元件的FF值 (從原本的73%增加至78%)。延遲退火的鈣鈦礦膜有較強的PL強度以及更長的激子半生期，這些數據都顯示延遲退火所製備的鈣鈦礦膜的品質較好，載子在膜上傳遞時能量損失較少，增加所組裝之元件的Voc值(從1.13 V增加至1.16 V)，因此整體元件效率增加10%。

Perovskite film in perovskite solar cells (PSCs) is generally prepared by spin-coating from its precursor solution using non-volatile solvents (such as Dimethylformamide or Dimethyl sulfoxide) to dissolve the perovskite precursor salts. These non-volatile solvents need to be removed by anti-solvent and high-temperature annealing, which need to be carried out in a glove box. This complex and high-cost processing method could be a problem for industrial development. In this study, quick crystallization of perovskite films was achieved by using volatile solvents without using an anti-solvent under ambient environment without affecting by moisture and oxygen. Therefore, high-quality perovskite films were prepared. In order to improve the efficiency of the device, BT-IDT, a molecule synthesized in our laboratory, was used as the interface (between the perovskite and the hole transport layer (HTL)) modification agent. The CN-group in BT-IDT and the lone pair electrons on S atoms of thiophene could interact with the coordination unsaturated Pb2+ in the perovskite film to achieve the passivation. However, later studies found that the improved efficiency of the device is not due to the interphase modification by BT-IDT but due to the delayed annealing of the wet film to provide sufficient time for grain growth. SEM images show a flatter and denser perovskite film. The PSCs based on perovskite film prepared by using volatile solvent and delay annealing exhibit the highest power conversion efficiency (PCE) of 22.8%, which is higher than 20.7% of cells assembled by using directly annealing perovskite film as an absorber. XRD patterns show that both perovskite films prepared by direct annealing and delayed annealing have no PbI2 diffraction peak but the (110) direction intensity of perovskite films prepared by delayed annealing is stronger than the prepared by direct annealing. The domain size of the perovskite films prepared by 30 minutes delayed annealing is 23.4 nm which is larger than that (22.0 nm) of the perovskite films prepared by direct annealing, which reflected in the FF value of the corresponding device (increased from 73% to 78%). The delayed annealed perovskite film has a stronger photoluminescence intensity and a longer exciton half-life than the film prepared by direct annealing, which indicates that the quality of the former perovskite film is better. Therefore, the Voc value of PSCs increases to 1.16 V due to the carriers travel through perovskite film with less energy loss. Overall the PSCs achieved the highest PCE of 22.8%.

摘要    vii
Abstract    ix
Graphical Abstract    xi
謝誌    xii
目錄    xiii
圖目錄    xx
表目錄    xxviii
第一章、    緒論    1
1-1、    前言    1
1-2、    鈣鈦礦太陽能電池    3
1-2-1.    鈣鈦礦太陽能電池的架構    3
1-2-2.    一般式鈣鈦礦太陽能電池的工作原理    4
1-2-3.    鈣鈦礦太陽能電池的光電轉換效率    5
1-3、    電子傳遞層的製備方法    7
1-3-1.    高溫製備的SnO2膜    7
1-3-2.    高溫及低溫製備SnO2膜    9
1-3-3.    以sol-gel法或奈米懸浮液製備SnO2膜    10
1-4、    鈣鈦礦活性層在大氣下的製備方法    12
1-4-1.    大氣下一步驟反溶劑法製備鈣鈦礦活性層    13
1-4-2.    大氣下兩步驟合成法製備鈣鈦礦活性層    14
1-4-3.    在大氣下一步驟無反溶劑法製備鈣鈦礦活性層    16
1-5、    以揮發性溶劑作為鈣鈦礦起始溶液    18
1-5-1.    使用揮發溶劑在大氣下製備FAPbI3鈣鈦礦膜組裝之元件的最高光電轉換效率    20
1-5-2.    使用ACN/MA系統製備MAPbI3鈣鈦礦膜組裝之元件的最高光電轉換效率    22
1-6、    MA氣體能幫助MAPbI3溶解在ACN中的原因    24
1-7、    以2-ME做為FAPbI3前驅溶液之溶劑一步驟無反溶劑法製備成膜…    27
1-8、    以2-ME做為MAPbI3前驅溶液之溶劑一步驟無反溶劑法製備成膜    29
1-9、    添加MABr至鈣鈦礦組成中增加所組裝之元件的Voc及FF值……    33
1-10、    以噻吩修飾Psk與HTL之間的界面    35
1-11、    透過延遲退火來控制鈣鈦礦膜的成核和相變    37
1-12、    研究動機    40
謝誌    實驗部分    42
2-1、    實驗藥品及儀器設備    42
2-1-1.    藥品    42
2-1-2.    儀器設備    44
2-2、    一般式鈣鈦礦太陽能電池之電池組裝步驟    45
2-2-1.    藥品配製    45
2-2-2.    元件組裝步驟    49
2-3、    儀器原理、樣品製備及量測    53
2-3-1.    熱蒸鍍系統(Thermal evaporation system，高敦科技)    53
2-3-2.    太陽光模擬器及光電轉換效率量測 (Solar Simulator, DENSO KXL-500F及Keithley 2400)    54
2-3-3.    太陽能電池外部量子效率量測系統 (Incident Photon to Current Converion Efficiency (IPCE)，QE-S3011)    55
2-3-4.    X-ray繞射光譜儀(X-Ray Diffractometer, BRUKER D8 Discover)    56
2-3-5.    紫外光/可見光/近紅外光光譜儀(Ultraviolet-visible-NIR spectroscopy, HITACHI U-4100)    57
2-3-6.    光激發螢光光譜及時間解析光譜 (Photoluminescence (PL) Spectra and Time-Resolved Photoluminescence (TRPL)，Uni think Uni-RAM)    58
2-3-7.    紫外光電子能譜儀(Ultraviolet photoelectron spectroscopy, Thermo VG-Scientific Sigma Probe)    59
2-3-8.    超高解析場發射掃描式電子顯微鏡 (Ultra-High Resolution FE-SEM，Nova NanoSEM-230)    60
2-3-9.    接觸角量測儀(Contact angle, Grandhand Ctag01)    61
2-3-10.    空間電荷限制電流量測 (Space Charge Limited Current，簡稱SCLC)    62
第三章、    結果與討論    64
3-1、    大氣下以揮發性溶劑製備鈣鈦礦膜所組裝之一般式元件的條件優化    64
3-1-1.    電子傳遞層篩選    64
3-1-2.    鈣鈦礦起始溶液的濃度篩選    66
3-1-3.    鈣鈦礦起始溶液旋轉塗佈之轉速篩選    67
3-1-4.    鈣鈦礦起始溶液的組成篩選    69
3-2、    以本實驗室自行合成之高分子做為電洞傳遞層    72
3-2-1.    以噻吩衍生物做為鈣鈦礦層與P15之間的界面修飾層來提高元件的光電轉換效率    73
3-2-2.    P15溶液旋轉塗佈篩選    75
3-2-3.    以PBT-IDT及PBT-F-IDT做為HTL    76
3-2-4.    篩選配置PBT-IDT的溶劑    78
3-2-5.    篩選配置PBT-IDT溶液的濃度    80
3-3、    以BT-IDT小分子作為鈣鈦礦層與Spiro-OMeTAD HTL之間的界面修飾層研究    82
3-3-1.    篩選界面修飾材料BT-IDT(CB)溶液的濃度    83
3-3-2.    確認BT-IDT界面修飾層的功能    84
3-4、    篩選大氣下以揮發性溶劑製備鈣鈦礦膜的後處理方式    89
3-4-1.    旋轉塗佈之鈣鈦礦膜的第一次退火溫度篩選    90
3-4-2.    篩選鈣鈦礦膜在大氣下最佳的靜置時間    92
3-4-3.    篩選鈣鈦礦膜最佳的延遲退火溫度    94
3-4-4.    篩選鈣鈦礦膜延遲退火的最佳退火時間    95
3-4-5.    以不同鈣鈦礦起始物配置成鈣鈦礦前驅溶液    97
3-4-6.    鈣鈦礦膜靜置在不同環境下延遲退火的影響    99
3-5、    不同延遲時間退火的鈣鈦礦膜之XRD測試    101
3-6、    直接退火及不同時間延遲退火之鈣鈦礦膜的水接觸角    102
3-7、    有無延遲退火鈣鈦礦膜沉積在SnO2膜上的SEM表面形貌和剖面圖    103
3-8、    以不同鈣鈦礦起始物配置成鈣鈦礦前驅溶液沉積在SnO2膜上的SEM表面形貌    105
3-9、    不同環境下延遲退火30分鐘鈣鈦礦膜沉積在SnO2膜上的SEM表面形貌    106
3-10、    鈣鈦礦膜有無延遲退火對所組裝元件之長時間穩定性的影響……..    107
3-11、    鈣鈦礦膜有無延遲退火對所組裝元件之IPCE    110
3-12、    直接退火及不同時間延遲退火之鈣鈦礦膜的UV-Vis吸收光譜…..    113
3-13、    直接退火及不同時間延遲退火之鈣鈦礦膜的前置軌域能階………..    114
3-14、    有無延遲退火之鈣鈦礦膜的PL及TRPL圖    116
3-15、    有無延遲鈣鈦礦膜的電洞遷移率、電子遷移率及缺陷密度………..    122
3-16、    有無延遲退火之鈣鈦礦膜對所組裝之一般式元件的穩態電流密度及效率輸出的影響    126
3-17、    有無延遲退火之鈣鈦礦膜做為吸收層所組裝之一般式元件的暗電流    127
結論    129
第四章、    參考文獻    131


                                

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