高品質鉛鈣鈦礦膜的製備及其光電性能之研究

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蔡宗佑(Tsung-Yu Tsai) 查詢紙本館藏

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化學學系

論文名稱

高品質鉛鈣鈦礦膜的製備及其光電性能之研究

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至系統瀏覽論文 (2026-8-23以後開放)

摘要(中)

鉛鈣鈦礦太陽能電池(PSCs)，元件中的鈣鈦礦膜與載子傳遞層之間的界面缺陷會使鈣鈦礦膜吸光產生的電子電洞再結合無法順利傳遞到外線路，而鈣鈦礦膜的晶界處易被水降解，導致PSCs元件的光電轉換效率降低及穩定性變差。本研究透過在鉛鈣鈦礦前驅溶液中添加非富勒烯小分子材料(TIIQ-b16或DPPQ-b16)並透過旋轉塗佈法來製備含添加劑之鈣鈦礦膜，含TIIQ-b16和DPPQ-b16之鈣鈦礦膜分別稱T-PSK和D-PSK，而將PDTON加入在反溶劑中所製備的鈣鈦礦膜稱T-PSK@PD和D-PSK@PD，未添加任何添加劑的鈣鈦礦膜稱PSK，將上述五種鈣鈦礦膜稱為(PSK-TD)。FT-IR穿透光譜顯示TIIQ-b16和DPPQ-b16與PbI2混合後其氰基吸收峰分別往低波數位移10 cm-1和8 cm-1，表示這兩個分子中的氰基上未鍵結的電子會與鈣鈦礦膜中配位未飽和的Pb2+配位。從SEM表面形貌圖看到以T-PSK@PD膜最為平整且晶粒最大，PL強度以T-PSK@PD最強，(100)晶面的繞射峰強度也是T-PSK@PD最強，顯示T-PSK@PD膜品質最好。在PSK-TD上沉積Spiro-OMeTAD膜的TRPL圖所測得的激子半生期以Spiro-OMeTAD沉積在T-PSK@PD最短，表示添加TIIQ-b16和PDTON的鈣鈦礦膜較能順利的將電洞傳遞至電洞傳遞層。以PSK、T-PSK、D-PSK、T-PSK@PD和D-PSK@PD作為吸收層所組裝的元件最高光電轉換效率分別為20.89%、21.39%、21.23%、22.01%和21.70%。以T-PSK@PD和D-PSK@PD作為吸光層所組裝的元件在未封裝且放置在手套箱中，經1920小時後，效率仍維持原始效率的95%和94%，在相同測試環境下，以PSK作為吸收層所組裝的元件僅剩原始效率的82%，以T-PSK和D-PSK做為吸收層所組裝的元件經960小時維持原效率的95%和93%。

摘要(英)

The interface defects between perovskite absorber and hole transport layer (HTL) of perovskite solar cells (PSCs) will cause electrons and holes recombination, decreasing the power conversion efficiency and long-term stability of PSCs. In this study, non-fullerene small molecules (TIIQ-b16 and DPPQ-b16) were used as additives for perovskite precursor solutions and the resulting perovskite films were called T-PSK and D-PSK, respectively. Furthermore, when PDTON was used as an additive of antisolvent (CB) to crystallize perovskite films, the resulting films were called T-PSK@PD and D-PSK@PD. The perovskite film prepared without any additive was called PSK. FT-IR transmission spectra indicate that the cyano absorption peaks of TIIQ-b16 and DPPQ-b16 have a shift 10 cm⁻¹ and 8 cm⁻¹ to lower wavenumbers respectively when they were mixed with PbI₂, suggesting a coordination interaction between the lone pair electrons on the cyano groups and the unsaturated Pb²⁺ sites in perovskite film. SEM images show that T-PSK@PD is the smoothest film with the largest grains. PL intensity and XRD data suggested that T-PSK@PD is the best quality film. TRPL curve also show that Spiro-OMeTAD-coated on PSK-TD film has the shortest exciton half-life, these data reveal that perovskite film prepared with TIIQ-b16 (in precursor solution) and PDTON (in anti-solvent) additives has the highest quality. Devices based on PSK, T-PSK, D-PSK, T-PSK@PD, and D-PSK@PD absorbers achieve the maximum PCEs of 20.89%, 21.39%, 21.23%, 22.01%, and 21.70% respectively. Devices using T-PSK@PD and D-PSK@PD as the absorption layers maintained 95% and 94%, respectively of their initial efficiency after 1920 hours of storing in a glove box without encapsulation, while device used PSK as absorber retained only 82% of their initial efficiency under the same conditions, while device used T-PSK and D-PSK as the absorber retained 95% and 93%, respectively of their initial efficiency after 960 hours

關鍵字(中)

★ 鈣鈦礦
★ 添加劑

關鍵字(英)

★ Pervoskite

論文目次

摘要 V
Abstract VI
Graphical Abstract VIII
謝誌 IX
目錄 X
圖目錄 XVI
表目錄 XXI
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. 鈣鈦礦太陽能電池結構 3
1-2-2. 鈣鈦礦太陽能電池(PSCs)的架構 4
1-2-3. 一般式鉛鈣鈦礦太陽能電池的工作原理 4
1-2-4. 第一篇將鈣鈦礦材料應用於太陽能電池之研究 6
1-2-5. 將固態電解質應用於鉛鈣鈦礦太陽能電池 8
1-2-6. 文獻中一般式鉛鈣鈦礦太陽能電池的最高光電轉換效率 9
1-3、製備鈣鈦礦膜的方法 10
1-3-1. 一步驟合成法 (Single-step method) 11
1-3-2. 兩步驟合成法 (Two-step method) 12
1-3-3. 一步驟反溶劑處理法(one-step anti-solvent engineering method) 13
1-4、一般式鉛鈣鈦礦太陽能電池面臨的考驗 14
1-4-1. 一般式鉛鈣鈦礦太陽能電池中鈣鈦礦層的晶界問題 14
1-4-2. 一般式鉛鈣鈦礦太陽能電池的鈣鈦礦膜的缺陷 15
1-5、一般式PSC中鈣鈦礦膜的修飾方法 16
1-5-1. 在鉛鈣鈦礦膜上沉積一層修飾膜 16
1-5-2. 在鉛鈣鈦礦前驅溶液中加入添加劑 22
1-5-3. 在反溶劑中加入添加劑製備高品質的鈣鈦礦膜 31
1-6、 TIIQ-b16有良好的平面性增加?–?堆積，誘導有更好的分子排列 36
1-7、研究動機 37
第二章、實驗部分 41
2-1、實驗藥品及儀器設備 41
2-1-1. 藥品 41
2-1-2. 儀器設備 42
2-2、一般式鈣鈦礦太陽能電池之電池組裝步驟 43
2-2-1. 藥品配製 43
2-2-2. 元件組裝步驟 45
2-3、儀器原理、樣品製備及量測 48
2-3-1. 熱蒸鍍系統(Thermal evaporation system) 48
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 ) 48
2-3-3. 太陽能電池外部量子效率量測系統 (Incident Photon to Current Conversion Efficiency (IPCE), Enlitech PVCS-I) 49
2-3-4. 接觸角量測儀(Contact angle, Grandhand Ctag01) 50
2-3-5. 超高解析場發射掃描式電子顯微鏡 (Ultra-High Resolution FE-SEM，Nova NanoSEM-230) 51
2-3-6. X-ray繞射光譜儀(X-Ray Diffractometer, BRUKER D8 Discover) 52
2-3-7. 化學分析電子能譜儀(Electron Spectroscopy for Chemical Analysis，ESCA) 53
2-3-8. 光激發螢光光譜儀(Photoluminescence Spectrometer, Uni think Uni-RAM) 54
2-3-9. 空間電荷限制電流量測 56
2-3-10. 傅立葉轉換紅外光光譜儀(Fourier transform infrared spectrometer, Jasco 4100) 57
2-3-11. 恆電位儀(Potentiostat, Metrohm Autolab PGSTAT30 ) 58
第三章、結果與討論 59
3-1、將TIIQ-b16或DPPQ-b16分子加入鈣鈦礦前驅溶液中製備鈣鈦礦膜作為吸光層組裝成元件的光伏表現 59
3-1-1. 篩選不同濃度TIIQ-b16(DMF:DMSO)作為鈣鈦礦前驅溶液的添加劑所製備的鈣鈦礦膜所組裝之元件的光伏表現 59
3-1-2. 篩選不同濃度PDTON作為氯苯反溶劑的添加劑所製備的鈣鈦礦膜之光伏表現 61
3-1-3. 添加TIIQ-b16作為鈣鈦礦前驅溶液的添加劑，篩選滴反溶劑的轉速 62
3-1-4. 添加TIIQ-b16作為鈣鈦礦前驅溶液的添加劑，篩選界面修飾層BHT塗佈轉速 64
3-1-5. 以DPPQ-b16添加在鈣鈦礦前驅溶液，篩選反溶劑中的PDTON(CB)溶液濃度 65
3-1-6. PSK-TD作為鈣鈦礦吸收層，篩選未使用BHT做為界面修飾層，組裝成元件的光伏表現 67
3-1-7. PSK-TD作為鈣鈦礦吸收層，組裝成元件的最佳光伏表現 68
3-2、 PSK-TD做為鈣鈦礦吸光層組裝成元件的IPCE表現 70
3-3、 PSK-TD作為吸光層組裝之元件的遲滯因子 72
3-4、 PSK-TD作為吸收層所組裝之元件的最大功率點輸出 73
3-5、 PSK-TD作為吸收層所組裝之元件的暗電流 76
3-6、 PSK-TD作為吸光層所組裝之元件在黑暗條件下的電阻 77
3-7、 PSK-TD作為吸光層所組裝之元件的在大氣下及手套箱中的長時間穩定性 79
3-8、 PSK-TD沉積在SnO2膜上的SEM表面形貌圖及剖面形貌圖 81
3-9、 T-PSK@PD沉積在SnO2膜上的表面EDS元素Mapping圖 84
3-10、 PSK-TD沉積在SnO2上的XRD圖 85
3-11、 PSK-TD作為吸光層的前置軌域能階圖 86
3-12、 PSK-TD沉積在SnO2上的水接觸角圖 90
3-13、 PSK-TD的光致螢光光譜圖及時間解析螢光曲線 92
3-14、 PSK、TPSK@PD及DPSK@PD的導電度 99
3-15、 PSK-TD的電洞遷移率、電子遷移率及缺陷密度 101
3-16、 PbI2、TIIQ-b16、TIIQ-b16+PbI2、DPPQ-b16和DPPQ-b16+PbI2的IR光譜圖 105
3-17、 PSK-TD之XPS能譜圖 107
第四章、結論 109
參考文獻 110
附錄 115
附錄1.以TIIQ-b16或DPPQ-b16作為電洞傳遞層組裝之元件的光伏參數 115

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指導教授

吳春桂(Chun-Guey Wu)

審核日期

2024-8-21

推文