做為反式鈣鈦礦太陽能電池的電子傳遞材料B-N缺電子共軛高分子

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黃志源(Jhih-Yuan Huang) 查詢紙本館藏

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論文名稱

做為反式鈣鈦礦太陽能電池的電子傳遞材料B-N缺電子共軛高分子

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至系統瀏覽論文 (2026-1-29以後開放)

摘要(中)

反式鉛鈣鈦礦太陽能電池(Perovskite solar cells，簡稱PSCs)中的電子傳遞層(Electron Transport Layer，簡稱ETL)功能是將鈣鈦礦層吸光所激發的電子萃取後並傳遞至外線路，因此合成出低LUMO能階的高分子就很重要。本研究合成D-A type共軛高分子P-BNBP-BT-CN，Donor為四環共平面結構的BNBP (double B ← N bridged bipyridine)具有高平面性、低LUMO能階的優點，Acceptor為ITN-CN (benzo[c]thiophene-5,6-dicarbonitrile)結構及帶有兩個強拉電子的氰基，能降低LUMO能階，同時屬於路易斯鹼的氰基可與鈣鈦礦層中屬於路易士酸的Pb2+作用，修飾鈣鈦礦層表面的缺陷。另外使用與ITN-CN結構少一個芳香環的Th-CN ( Thiophene-3,4-dicarbonitrile )結構作為Acceptor單元，合成出高分子P-BNBP-Th-CN。高分子P-BNBP-BT-CN及高分子P-BNBP-Th-CN具有有良好的熱穩定性(熱裂解溫度分別為271 ℃及276 ℃)及良好的疏水性(水接觸角分別為96度及93度) ；由兩個高分子各別與PbI2混合後之FTIR穿透光譜顯示P-BNBP-BT-CN結構中之CN(氰)基往低波數位移6 cm-1、P-BNBP-Th-CN結構中之CN(氰)基往低波數位移4 cm-1，證實CN能與Pb2+作用修飾鈣鈦礦層中的Pb2+缺陷；P-BNBP-BT-CN的HOMO與LUMO能階則為-5.48 eV及-3.81 eV，P-BNBP-Th-CN的HOMO與LUMO能階則為-5.51 eV及-3.7 eV，以兩個高分子分別做為ETL所組裝之反式PSCs (吸光層組成為(FAPbI3)0.9(MAPbBr3)0.1 )的光電轉換效率(PCE)值分別是0.42%及0.42%。

摘要(英)

Perovskite solar cells (PSCs) employ an electron transport layer (ETL) to extract and transfer electrons from the perovskite layer by exciting with light to the external circuit. Therefore, it is crucial that conjugated polymers ETL should have a low-lying frontier orbital energy level for ETL. In this study, a D-A type conjugated polymer, P-BNBP-BT-CN, was synthesized. The donor component, BNBP (double B ← N bridged bipyridine), is a four-ring planar structure that offers high planarity and a low-lying LUMO energy level. The acceptor component, ITN-CN (benzo[c]thiophene-5,6-dicarbonitrile), contains two strong electron-withdrawing cyano groups. Which can further reduce the LUMO energy level. Additionally, the cyano groups act as Lewis bases, which can interact with the Pb2+ defect in the perovskite layer to passivate the perovskite suface. Another acceptor unit, Th-CN (thiophene-3,4-dicarbonitrile), which lacks one aromatic ring compared to ITN-CN, was incorporated into the polymer to form P-BNBP-Th-CN. Both P-BNBP-BT-CN and P-BNBP-Th-CN exhibit good thermal stability (decomposition temperatures of 271°C and 276°C, respectively) and hydrophobicity (water contact angles are 96 degrees and 93 degrees, respectively). FTIR transmittance spectra of the two polymers mixed with PbI2 show a red-shift of the CN stretching vibration by 6 cm-1 for P-BNBP-BT-CN and 4 cm-1 for P-BNBP-Th-CN, indicating the interaction of CN groups with coordination unsaturated Pb2+. The HOMO and LUMO energy levels of P-BNBP-BT-CN are -5.48 eV and -3.81 eV, respectively, while those of P-BNBP-Th-CN are -5.51 eV and -3.7 eV, respectively. When used P-BNBP-BT-CN and P-BNBP-Th-CN as ETLs in inverted PSCs with a composition of (FAPbI3)0.9(MAPbBr3)0.1 as perovskite absorber, the power conversion efficiency (PCE) values of the corresponding devices based on P-BNBP-BT-CN and P-BNBP-Th-CN are both around 0.42%.

關鍵字(中)

★ 鈣鈦礦太陽能電池
★ 共軛高分子

關鍵字(英)

論文目次

摘要 i
Abstract ii
目錄 v
圖目錄 vii
表目錄 ix
第一章、緒論 1
1-1、前言 1
1-2、太陽能電池種類 1
1-3、鈣鈦礦太陽能電池(PSC)之架構與工作原理 3
1-4、反式鈣鈦礦太陽能電池的電子傳遞層所需性質 7
1-4-1、聚合物電子傳遞層的設計策略 8
1-4-2、目前反式 PSCs常見有機電子傳遞材料 8
1-5、使用BNBP構成的聚合物電子傳遞材料及設計 9
1-6、合成具有低前置軌域能階共聚物的策略 12
1-7、研究動機 17
第二章實驗部分 18
2-1、實驗藥品 18
2-2、中間產物與產物結構簡稱與分子量 23
2-3、實驗步驟 27
2-3-1、Donor: B(PIN)2-BNBP的合成，如圖2-3-1所示 27
2-3-2、Acceptor 1: ITN-CN的合成，如圖2-3-2所示 31
2-3-3、Acceptor 2: Br-CN-Th的合成【47】，如圖2-3-3所示 34
2-3-4、Pd(PPh3)4催化劑合成，如圖2-3-4所示 35
2-3-5、P-BNBP-BT-CN、P-BNBP-Th-CN的合成圖，如圖2-3-5所示 36
2-4、儀器分析與樣品製備 38
2-4-1核磁共振光譜儀(Nuclear Magnetic Resonance Spectrometer) 38
2-4-2熱重分析(Thermogravimetric Analysis) 39
2-4-3電化學測量(Electrochemical Measurement System) 40
2-4-4紫外光/可見光吸收光譜儀 (Ultraviolet Visible Spectrophoto-meter, UV/Vis Spectrophotometer) 42
2-4-5接觸角量測儀(Contact angle meter) 43
2-4-6聚焦微波化學反應系統(CEM) 43
2-4-7傅立葉轉換紅外光光譜儀(Fourier transform infrared spectrometer) 44
第三章結果與討論 46
3-1、結構鑑定 46
3-2、前置軌域理論計算 48
3-3、兩個高分子的紫外光/可見光光譜圖 49
3-4、電化學循環伏安圖及前置軌域能階 51
3-5、高分子膜的親疏水性 52
3-6、兩個高分子的熱重分析 53
3-7、兩個高分子及其與PbI2混合後的FTIR穿透光譜圖 55
3-8、兩個高分子做為電子傳遞材料所組裝之反式鈣鈦礦太陽能電池元件的光伏表現 57
第四章結論 59
參考文獻 60
附錄 65

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指導教授

吳春桂(Chun-Guey Wu)

審核日期

2024-1-30

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