| 摘要: | 鈣鈦礦太陽能電池為當前最具潛力的第三代太陽能電池之一，其光電轉換效率自2009年首次報導的3.9%增加至目前的27.0%。在效率與穩定性持續突破的過程中，電洞傳輸材料扮演關鍵的角色。本研究設計並合成一系列具錨定基團之三苯胺衍生物作為電洞傳輸材料，包括keto-phenol（TKE-o、TKE-m與TKE-p）、α-hydroxyketone（TKET）與1,2-diketone（TKKT）等官能基，探討其分子結構與光電性質。TKE系列化合物皆可溶於氯苯（>10 mg/mL），展現良好的製程相容性。其分子結構經由核磁共振光譜、質譜與X光單晶繞射加以確認，並透過紫外–可見光吸收光譜、循環伏安法及密度泛函理論分析其前緣分子軌域能階。研究結果顯示，TKE系列化合物具備與鈣鈦礦匹配的最高佔據分子軌域及最低未佔分子軌域能階，有助於提取電洞和抑制電子回填。此外，分子設計採用donor–acceptor–donor骨架，搭配酚、醇或酮類錨定基團，預期可與鈣鈦礦中未配位的鉛離子作用，強化界面接觸並降低缺陷密度。TKE系列優異的熱穩定性與光電應用潛力，為開發穩定、無摻雜型電洞傳輸材料提供一項可行的分子設計策略。;Perovskite solar cells (PSCs) are among the most promising third-generation photovoltaic technologies. Since their initial report in 2009 with a power conversion efficiency (PCE) of 3.9%, PSCs have achieved remarkable progress, reaching a certified PCE of 27.0%. In this advancement, hole-transporting materials (HTMs) play a crucial role in improving both device efficiency and operational stability. In this study, a series of triphenylamine-based HTMs bearing anchoring groups were designed and synthesized, featuring keto-phenol (TKE-o, TKE-m, and TKE-p), α-hydroxyketone (TKET), and 1,2-diketone (TKKT) functional groups. The relationship between molecular structure and optoelectronic properties was systematically investigated. All TKE compounds exhibited good solubility in chlorobenzene (>10 mg/mL), indicating excellent process compatibility. Their molecular structures were confirmed by nuclear magnetic resonance spectroscopy, mass spectrometry, and single-crystal X-ray diffraction. The frontier orbital energy levels were further evaluated using ultraviolet–visible absorption spectroscopy, cyclic voltammetry, and density functional theory calculations. The results show that the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of TKE compounds are well aligned with those of typical perovskite absorbers, facilitating efficient hole extraction while suppressing electron back-injection. The donor–acceptor–donor structural framework, combined with hydroxyl, carbonyl, or phenolic anchoring groups, is expected to interact with undercoordinated Pb2+ ions in the perovskite layer, thus enhancing interfacial contact and reducing defect density. Overall, the TKE series exhibits excellent thermal stability and optoelectronic potential, offering a viable molecular design strategy for the development of stable, dopant-free HTMs. |
