雖然高效能的紅光和綠光磷光有機發光二極體 (phosphorescent organic light-emitting diode, PhOLED) 已成功商業化，藍光PhOLED因穩定性問題而壽命較短，其中主體材料的穩定性在延長藍光元件壽命方面扮演著重要角色。螺二芴(spirobifluorene, SBF) 衍生物因其高三重態能量和良好的熱穩定性，被認為是有潛力的藍光PhOLED主體材料。先前的研究對SBF衍生物的結構與電化學和光物理性質之間的關係進行了系統性的探討。然而，對於影響PhOLED元件穩定性的關鍵性質──電荷傳輸──的研究仍然缺乏。因此，本篇研究的目標是透過探討一系列SBF衍生物的結構-堆積-載子遷移率之間的關係 (structure–packing–mobility relationship, SPMR)，提供設計平衡且快速電荷傳輸的主體材料所需的分子設計。
在本篇論文中，我們將探討兩系列SBF衍生物的SPMR，第一部分為探討藉由不同取代位置所形成SBF二聚體之結構異構物，第二部分為探討不同取代基與取代位置對於SBF單體之影響。我們採用了多尺度方法來模擬這些分子的載子遷移率，透過分析分子結構、分子堆積以及電荷傳輸參數:重組能、轉移積分和能量紊亂之間的關係，希望透過分子設計實現快速且平衡的電荷傳輸特性。
在第一部分的研究中，我們發現這10個結構異構物的能量紊亂都很低，約在0.1 eV 左右，這是因為這些分子都有非常小的分子偶極矩。此外，連接2號與4號位置的SBF二聚體電子的重組能都較電洞來得高，而轉移積分的分析顯示，大多異構物的電子與電洞轉移積分分布差異不大，因此，這系列的分子電荷傳輸行為主要由重組能主導，轉移積分為次要因素。為方便引用不同連接位置的SBF二聚體，我們以連接位置進行命名，比如SBF二聚體若透過n與m號位置相接，則命名為n,m”-(SBF)2，或簡稱為n,m。我們發現1,1、1,3及1,4分子具有平衡的電荷傳輸性質，而連接2號與4號位置的異構物則具有很不平衡的電荷傳輸性質(電子傳輸遠慢於電洞傳輸)。
在第二部分的研究中，我們觀察到隨著取代基從苯、聯苯到三聯苯的變化，對重組能和能量紊亂的影響較小，而電子與電洞的轉移積分比值隨取代基的變化有所增加。此外，連接2號位置的SBF衍生物具有較為平衡的轉移積分分布。重組能方面，取代基位在2號與4號位置的SBF衍生物表現出較高的電子重組能，這與第一部分中觀察到的趨勢相同。在這個系列的分子中，由於重組能與轉移積分之間的相互補償效應，大部分分子顯示出平衡的電荷傳輸性質。然而2號位置的SBF衍生物是個例外，其電子遷移率遠低於其電洞遷移率。這是由於其轉移積分分布較為平衡，因此較高的電子重組能導致較低的電子載子遷移率。

Although high-performance phosphorescent organic light-emitting diodes (PhOLEDs) for red and green light have been successfully commercialized, blue PhOLEDs suffer from shorter lifetimes due to stability issues. The stability of host materials is crucial for extending the lifetime of blue light devices. Spirobifluorene (SBF) derivatives are considered promising host materials for blue PhOLEDs due to their high triplet energy and good thermal stability. Previous studies have systematically explored the relationship between the structure of SBF derivatives and their electrochemical and photophysical properties. However, the influence of charge transport properties remains unknown. Therefore, this study aims to understanding the complex structure-packing-mobility relationships (SPMR) of a series of SBF derivatives to provide molecular design guidelines for host materials with balanced and efficient charge transport.
In this work, we investigate the SPMR of two series of SBF derivatives. The first part investigates the structural isomers of SBF dimers with varying substitution positions, while the second part investigates the effects of different substituents and substitution positions on SBF monomers. We employ a multiscale approach to simulate the charge transport properties of these molecules and analyze the relationships between molecular structure, molecular packing, and charge transport parameters, including reorganization energy (λ), transfer integral (V), and energetic disorder (σ). Our goal is to achieve rapid and balanced charge transport characteristics through systematic molecular design.
In the first part of the study, we found that the energetic disorder of the ten structural isomers was low, around 0.1 eV, due to their very small molecular dipole moments. Additionally, the electron reorganization energy of the SBF dimers linked at positions 2 and 4 were higher than those of the hole. The analysis of transfer integral showed that the differences in electron and hole transfer integral were generally small among most of the isomers. Therefore, the charge transport behavior of this series of molecules is primarily governed by reorganization energy, with transfer integral being a secondary factor. Finally, we observed that the 1,1, 1,3, and 1,4 substituted molecules exhibited balanced charge transport properties, while the isomers linked at positions 2 and 4 exhibited highly unbalanced charge transport properties (with electron transport being much slower than hole transport).
In the second part of the study, we observed that the effect of substituents changing from benzene, biphenyl, to terphenyl had a minimal impact on reorganization energy and energetic disorder. However, the ratio of electron to hole transfer integral increased with the change in substituents. Additionally, SBF derivatives connected at position 2 exhibit a more balanced distribution of transfer integral. Regarding reorganization energy, SBF derivatives with substituents at positions 2 and 4 show higher electron reorganization energy, consistent with the trends observed in the first part. In this series of molecules, due to the compensatory effect between reorganization energy and transfer integral, most molecules exhibit balanced charge transport properties. However, SBF derivatives at position 2 are an exception, with electronic mobility significantly lower than hole mobility. This is attributed to their more balanced distribution of transfer integral, where the higher electron reorganization energy leads to reduced electronic carrier mobility.

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