摘要 本研究致力於設計、合成並系統性表徵一系列新型有機光電材料，應用於有機薄膜電晶體 (OTFTs) 及鈣鈦礦太陽能電池 (Perovskite Solar Cells， PSCs)。材料的光學與電化學性質分別透過紫外–可見吸收光譜 (UV–Vis）及差分脈衝伏安法（DPV）進行分析；其熱穩定性則藉由差示掃描量熱法 (DSC) 與熱重分析 (TGA) 評估。薄膜形貌與表面特性則利用 X 光繞射 (XRD)、掠入射 X 光繞射 (GIXRD) 及原子力顯微鏡 (AFM) 進行探討，而分子結構與分子堆疊方式則進一步透過單晶 X 光繞射分析加以確認。 第二章中，設計並合成了一系列以聯噻吩酰亞胺 (BTI) 為核心、並以五氟苯基作為端基修飾的 n 型小分子半導體材料，用於 OTFT 應用。成功獲得 DFP-BTI-b8 (1)與 DFP-BTI-b16 (2) 的單晶結構，顯示其主鏈具有高度平面性。此一顯著的平面結構有利於增強分子間作用力，進而實現最高可達 0.10 cm² V⁻¹ s⁻¹ 的電子遷移率，且元件的開關比高於 10⁶。 第三章中，開發了以咔 (carbazole) 與三苯胺 (triphenylamine) 為基礎的自組裝單分子層 (SHMs)，並應用於鉛基鈣鈦礦太陽能電池。成功取得 CarS-CA (1)、TPAS-CA (3)與 TPA-CA (4) 的單晶結構。其中，CarS-CA 在有機太陽能電池（OPVs）中展現 16.58% 的光電轉換效率（PCE），在一倍太陽光照條件下的鉛基 PSC 中達到 25.66%，並在室內寬能隙（WBG）照明條件下實現高達 44.03% 的效率。 第四章中，進一步開發了 DTPBT 為核心的 SAMs 應用於鉛基 PSCs，其中 DTPBT*F-PA (3) 在一倍太陽光照條件下可達 24.02% 的 PCE，於室內照明條件下則可提升至 40%。第五章中，設計並合成了以聯苯與芘 (pyrene) 為基礎的電子傳輸界面材料(ETIMs)，應用於鉛基 PSCs。成功取得 TFP-Bp (1) 與 TFP-Pyr (2) 的單晶結構，結果顯示其分子呈現明顯扭曲構型，可以有效抑制過度分子聚集。其中，TFP-Pyr (2) 在一倍太陽光照條件下展現 21.50% 的 PCE，並在室內照明條件下達到 43.34%。 第六章中，開發了一種以芘為基礎的電洞傳輸材料 (HTMs) 應用於鉛基 PSCs，目前相關元件性能的最佳化仍在進行中。;Abstract In this research， a series of new organic optoelectronic materials were designed， synthesized， and characterized for organic thin-film transistors (OTFTs) and Perovskite Solar Cells (PSCs). Optical and electrochemical properties were investigated using UV-Visible absorption spectroscopy and differential pulse voltammetry (DPV)， while thermal stability was evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Thin-film morphology and surface characteristics were examined using X-ray diffraction (XRD)， grazing incidence X-ray diffraction (GIXRD)， and atomic force microscopy (AFM). The molecular structures and packing arrangements were confirmed by single-crystal X-ray diffraction analysis. In Chapter 2， bithiophene imide (BTI)-based small-molecule semiconductors functionalized with pentafluorophenyl end groups were designed for n-type OTFT applications. Single-crystal structures of DFP-BTI-b8 (1) and DFP-BTI-b16 (2) were successfully obtained， revealing their highly planar backbones. This pronounced planarity enables strong intermolecular interactions， resulting in excellent electron mobilities of up to 0.10 cm2 V-1 s-1 with on/off ratios above 106. In chapter 3， carbazole and triphenylamine-based SAMs were developed for Pb-based perovskite solar cells， and single crystals were obtained for CarS-CA (1)， TPAS-CA (3) and TPA-CA (4). Notably， CarS-CA achieved excellent 16.58% PCE in organic photovoltaics (OPVs)， 25.66% efficiency in Pb-PSCs under one-sun illumination， and 44.03% indoor wide-bandgap (WBG) photovoltaic conditions. In chapter 4， DTPBT-based SAMs were developed for Pb-PSCs， and DTPBT*F-PA (3) achieves PCE of 24.02% under one-sun condition， and 40% under indoor illumination. In chapter 5， biphenyl and pyrene-based electron-transport interfacial materials (ETIMs)， were designed for Pb-PSCs. A single-crystal structure was obtained for TFP-Bp (1) and TFP-Pyr (2)， reveals markedly twisted conformations， which effectively suppress excessive aggregation. Among these materials， TFP-Pyr (2) achieved good PCE of 21.50% under one-sun conditions， and 43.34% under indoor lighting conditions. In chapter 6， pyrene-based hole transport materials (HTMs) were developed for Pb-PSCs and device performance optimization is currently in progress.
