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研究生： 牛崇愷
Niou, Chong-Kai
論文名稱： 利用高通量篩選具備空間限制電荷轉移特性的熱活化延遲螢光分子
Discovery of TADF Emitters with Space-confined Charge-transfer Characteristics via High-throughput Screening
指導教授： 林昆翰
Lin, Kun-Han
口試委員: 吳典霖
Wu, Tien-Lin
林玠廷
Lin, Chieh-Ting
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2024
畢業學年度： 112
語文別： 中文
論文頁數： 165
中文關鍵詞： 有機發光二極體 、熱活化延遲螢光 、SCCT 、計算性高通量篩選
外文關鍵詞： OLED, TADF, SCCT, Computational high-throughput screening
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    • 熱活化延遲螢光 (thermally activated delayed fluorescence, TADF) 是第三代有機發光二極體 (organic light-emitting diodes, OLED) 材料所具有的發光機制。其原理是利用發光分子相近的單重態與三重態能量差 (ΔEST)，使三重激發態可以透過反向系間轉換 (reverse intersystem crossing, rISC) 躍遷至單重激發態，進而衰退回基態並釋放螢光。由於高能量的三重態，藍光OLED在壽命與效率方面仍相對落後。本研究的動機是藉由尋找高效率的藍光TADF分子，期望能夠改善藍光OLED裝置的壽命與效率，。
    為了提高效率以解決藍光OLED壽命問題，本研究採用空間限制電荷轉移 (space-confined charge-transfer, SCCT) 的分子設計策略，以加快分子的rISC速率。SCCT不同於傳統的TBCT (through-bond charge transfer) 和MR-TADF (multi-resonance thermally activated delayed fluorescence)，其利用連接體限制供體與受體相對構型，增加兩者之間的相互作用，進一步促進單重態與三重態的電荷轉移 (charge transfer, CT) 和局域激發 (local excitation, LE) 的混成。這能在保持較小的ΔEST的同時，增加分子的自旋軌域耦合 (spin-orbit coupling, SOC)，
    本研究利用計算性高通量篩選的方法尋找高效率的發光分子，通過自動化建立SCCT分子資料庫並進行篩選。我們利用已合成的SCCT分子資料庫確立了可靠的計算方法，並設計了半自動化的高通量篩選工作流程，包括結構最佳化、激發態計算和rISC速率常數的估算等。
    接著，在確立本次研究所要使用的供體、受體和連接體分子組件後，我們首先建立了約有一萬個分子的結構資料庫。目前為止，我們從分子資料庫中已計算完畢的3418個分子中，篩選出了41個符合篩選需求的分子，其中有五個分子可能成為高效率的藍色SCCT發光分子。除了對資料庫內各項性質進行了統計與趨勢分析，我們從多個角度對分子資料庫進行了討論，包括相關係數矩陣、分子組件能階對性質的影響等。我們對表現最佳的供體、受體組合進行了詳細討論，並從分子設計的角度提出了推薦的供體與受體組合。此外，我們進行了計算與實驗反向隙間速率常數的相關性分析，以驗證本研究的計算方法論。最後，我們進一步探討了在相同供體-受體組合下，不同連接體對分子性質的影響。

    Thermally activated delayed fluorescence (TADF) is a luminescence mechanism characteristic of third-generation organic light-emitting diode (OLED) materials. This mechanism leverages the small energy gap between the singlet and triplet states (ΔEST) of the emitting molecules, allowing the triplet excitons to transition to the singlet excited state through reverse intersystem crossing (rISC) and subsequently decay to the ground state while emitting fluorescence. Despite significant advancements, blue OLEDs still lag in terms of lifetime and efficiency due to the high energy of triplet states. The motivation behind this study is to identify highly efficient blue TADF molecules to enhance the lifetime and efficiency of blue OLED devices.

    To address blue OLEDs' efficiency and lifetime issues, this study employs a space-confined charge-transfer (SCCT) molecular design strategy to accelerate the rISC rate. Unlike traditional through-bond charge transfer (TBCT) and multi-resonance TADF (MR-TADF), SCCT utilizes linkers to constrain the relative configuration of donors and acceptors, thereby increasing their interaction. This design promotes the hybridization of charge transfer (CT) and local excitation (LE) states, maintaining a small ΔEST while enhancing spin-orbit coupling (SOC).

    This study employs a computational high-throughput screening approach to identify efficient luminescent molecules by automatically constructing and screening an SCCT molecular database. We established a reliable computational methodology based on synthesized SCCT molecules and designed a semi-automated high-throughput screening workflow, including structure optimization, excited-state calculations, and rISC rate constant estimation.

    After determining the donor, acceptor, and linker components to be used in this study, we constructed a structural database comprising approximately 10,000 molecules. To date, we have completed calculations for 3,418 molecules from the database, identifying 41 molecules that meet the screening criteria, among which five have the potential to be highly efficient blue SCCT emitters. In addition to statistical and trend analyses of various properties within the database, we conducted an in-depth analysis from multiple perspectives, including correlation matrices and the impact of molecular component energy levels on properties. We discussed the best-performing donor-acceptor combinations in detail and proposed recommended donor-acceptor pairs from a molecular design perspective. Furthermore, we performed a correlation analysis between calculated and experimental rISC rate constants to validate our computational methodology. Finally, we explored the influence of different linkers on molecular properties within the same donor-acceptor combinations.

    摘要 i Abstract iii 目錄 v 圖目錄 viii 表目錄 xvi 第 一 章 緒論 1 1.1 有機發光二極體 1 1.1.1 前言 1 1.1.2 工作原理 2 1.1.3 發展歷程 5 1.2 熱活化延遲螢光 10 1.2.1 反向系間轉換 10 1.2.2 分子設計策略 11 1.2.3 Space-confined charge transfer分子設計 16 1.3 有機發光二極體之物理參數的量測 21 1.3.1 最低單重激發態與最低三重激發態的能量差 21 1.3.2 反向系間轉換速率常數 24 1.4 研究動機與目標 26 1.5 計算性高通量篩選 27 第 二 章 計算方法與工作流程 30 2.1 自動化生成結構 31 2.2 密度泛函理論 32 2.2.1 密度泛函理論簡介 32 2.2.2 範圍分離泛函 34 2.2.3 ω值最佳化調控 36 2.3 建立可靠的計算方法論 37 2.3.1 不同DFT泛函的影響 37 2.3.2 建立已合成SCCT分子資料庫 40 2.3.3 方法基準測試與實驗校準 42 2.3.4 計算方法確認結果 46 2.4 工作流程 49 2.4.1 結構最佳化 49 2.4.2 激發態能量 50 2.4.3 電荷轉移特性 52 2.4.4 自旋軌域耦合常數 53 2.4.5 反向系間轉換速率常數 55 第 三 章 結果與討論 57 3.1 分子資料庫的建立 57 3.1.1 分子組件的選擇 57 3.1.2 分子性質的數據統計 62 3.2 分子資料庫的篩選 65 3.3 分子資料庫的分析 82 3.3.1 相關係數矩陣 82 3.3.2 分子組件的HOMO/LUMO對分子性質的影響 85 3.3.3 供體與受體的組合分析 87 3.3.4 計算與實驗反向系間速率值的相關性分析 89 3.4 連接體對分子性質的影響 91 3.4.1 連接體加入tert-butyl的影響 92 3.4.2 benzene與triptycene連接體的比較 102 3.4.3 不同供體、受體位置的fluorene連接體比較 110 3.4.4 不同供體、受體位置的carbazole連接體比較 116 3.4.5 不同供體、受體位置的triptycene連接體比較 123 3.4.6 D-spiro資料庫分析 129 3.4.7 A-spiro資料庫分析 141 第 四 章 結論 150 參考文獻 152

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