噻吩吡嗪 (TP) 含氟衍生物之電洞傳輸層與界面修飾層材料開發

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题名:	噻吩吡嗪 (TP) 含氟衍生物之電洞傳輸層與界面修飾層材料開發
作者:	莊凱全;Zhuang, Kai-Quan
贡献者:	化學學系
关键词:	鈣鈦礦;太陽能;電洞傳輸層;界面修飾層;噻吩吡嗪
日期:	2025-06-30
上传时间:	2025-10-17 11:15:12 (UTC+8)
出版者:	國立中央大學
摘要:	本研究主要以噻吩吡嗪 (thienopyrazine, TP) 作為核心，進行其含氟衍生物之合成，，並致力於將其應用在鈣鈦礦太陽能電池，作為電洞傳輸層或界面修飾層，後者包含電子界面修飾材料 (electron transporting interfacial material, ETIM) 及電洞界面修飾材料 (hole transporting interfacial material, HTIM)。第一系列材料將五氟苯基 (pentafluorophenyl, FP) 接在 TP 四端，，並與具苯基 (phenyl, Ph) 之材料相互比較，。共開發出四種分子，： DFP-TPF (1; 四端皆接上 FP)， DP-TPF (2; 核心兩端接 Ph, 下方接 FP) DFP-TP (3; 核心兩端接 FP, 下方接 Ph) 以及 DP-TP (4; 四端皆接上 Ph)。本系列材料 (1~3) 皆已獲得單晶結構之解析。本系列材料均作為界面修飾層應用於鉛鈣鈦礦太陽能電池中，，其中 DFP TPF (1) 作為 ETIM 可獲得 21.19% 之光電轉換效率 (PCE)。而 DP-TPF (2) 及 DFP-TP (3) 作為 HTIM 分別可得到 21.87% 及 21.61% 之 PCE，元件效能仍在優化中。第二系列則是於 TP 一端接上氟代三苯胺 (fluorinated triphenamine, TPAF)，，氟原子具高電負度，除可調整分子能階增進電荷傳輸能力，亦可與鈣鈦礦層中未配位金屬離子形成鍵結進而鈍化缺陷。再於另一端接上錨定基團：丙二腈 (malononitrile, MN)，乙酸烯基 (cyanoacetic acid, CA) 乙磷酸二酯烯基 (diethyl cyanomethylphosphonate, PE) 以及乙磷酸烯基 ((cyanomethyl)phosphonic acid, PA)，合成出 TPAF-TP-MN (5) TPAF-TP-CA (6) TPAF-TP-PE (7) 及 TPAF-TP-PA (8) 四種自組裝材料，。本系列材料均作為電洞傳輸層材料應用於錫鉛鈣鈦礦太陽能電池中，其中 TPAF-TP-PE (7) 效能最高可達 20.7%，， TPAF-TP-MN (5) 及 TPAF-TP-CA (6) 效能亦可高達 20.4%，元件效能仍在優化中。上述兩種系列之全新材料，皆已利用 NMR 與質譜完成其結構鑑定，，接著透過 UV-vis 與 DPV 鑑定光學及電化學性質，再利用其結果計算出 HOMO LUMO 以及 Eg 等數據；最後以 TGA 及 DSC 檢驗材料熱穩定性。;New fluorinated thienopyrazine (TP) derivatives were developed and applied as hole transporting materials (HTMs) or interfacial materials (IMs) in perovskite solar cells (PSCs). The latter includes hole transporting interfacial materials (HTIMs) and electron transporting interfacial materials (ETIMs). In the first series, TP core was end-capped with pentafluorophenyl groups (FP) or phenyl groups (Ph) to give four IMs: DFP-TPF (1), with FP groups at four ends; DP-TPF (2), with Ph at the top ends and FP at the bottom ends; DFP-TP (3), with FP at the top ends and Ph at the bottom ends; DP-TP (4), with Ph groups at four ends. Single-crystal structures were obtained and analyzed for compounds 1, 2, and 3. These compounds were employed as IMs in Pb-PSCs. Preliminary device tests of DFP-TPF (1), used as an ETIM, achieved a power conversion efficiency (PCE) of 21.19%. DP-TPF (2) and DFP-TP (3), used as HTIM, achieved PCEs of 21.87% and 21.61%, respectively. Currently, DP-TP (4) is undergoing device testing. Fluorine atoms are capable of lowering the HOMO energy level to better match the perovskite (PSK) layer, due to their high electronegativity. In addition, fluorine may passivate defects by coordinating with the under-coordinated metal ions in the perovskite layer. Therefore, in the second series, a fluorinated triphenylamine (TPAF) group was first introduced on one end of the TP core. Then the other end of TP was end-capped with four different anchoring groups, including malononitrile (MN), cyanoacetic acid (CA), diethyl cyanomethylphosphonate (PE), and (cyanomethyl)phosphonic acid (PA) to give four self-assembled monolayer compounds (SAMs): TPAF-TP-MN (5), TPAF-TP-CA (6), TPAF-TP-PE (7), and TPAF-TP PA (8). These four SAMs were applied as HTMs in Sn-Pb-PSCs. Notably, TPAF-TP-PE (7) achieved the highest efficiency of 20.7%, while TPAF-TP-MN (5) and TPAF-TP-CA (6) reached 20.4% PCE. Currently, TPAF-TP-PA (8) is undergoing device testing. All newly developed materials from both series were structurally confirmed by NMR and mass spectrometry. Their optical and electrochemical properties were characterized using ultraviolet visible (UV-Vis) absorption and differential pulse voltammetry (DPV), from which the HOMO, LUMO, and optical bandgap (Eg) values were calculated. Thermal stability was evaluated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).
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