在本篇論文中，我們設計並合成一系列含有吡啶-3,5-二氰基結構
作為拉電子基的高效率熱活化延遲螢光發光體，名稱為CzdmPPC、
tCzdmPPC、DBAZdmPPC、SPACdmPPC、DPAdmPPC。氰基的熱
穩定性好，且可以抑制分子在激發態的結構緩解現象，與高能隙的吡
啶搭配作為強度適中的拉電子基，藉由改變推電子基的種類，增加推
電子基、橋基之間的二面角度以及分子內電荷轉移性質，在甲苯溶液
中不同分子的光色為天藍光至黃綠光。經由量測摻雜在主體材料中的
室溫螢光光譜與低溫磷光光譜，最低單重激發態和最低三重激發態的
能量差ΔEST 分別為0.273、0.126、0.023、0.046、0.018 eV，分子
CzdmPPC、tCzdmPPC 較大的ΔEST 不利於由最低三重激發態回到最
低單重激發態的逆系統間跨越，其他分子的ΔEST 接近於室溫的環境
能，顯示橋基的甲基可以縮短電子共振長度，並減低最高佔有分子軌
域和最低未佔有分子軌域的重疊。我們製作多層有機發光二極體元件，
分子CzdmPPC、tCzdmPPC、SPACdmPPC、DPAdmPPC 摻雜在
mCPCN 的最大外部量子效率都高於15 %，對應到這些材料的高螢光
量子效率和有效的逆系統間跨越。隨著不同分子ΔEST 的縮小，延遲
螢光生命期縮短，外部量子效率大幅提升，同時減緩高亮度時的效率
滾降。分子DPAdmPPC 具有極小的ΔEST 和100 %的螢光量子效率，延遲螢光生命期只有3.4 μs，摻雜在主體材料中的水平偶極矩為0.88，
且元件擁有良好的載子平衡，最大外部量子效率高達41.2%，最大發
光效率和功率效率為135.8 Cd/A 和142.2 lm/W，電激發光最大值為
532 nm，CIE 色度座標為(0.33, 0.57)。因為分子DPAdmPPC 作為客
發光體的優異元件表現，我們也將其應用於非摻雜發光體，剛性的結
構避免濃度淬熄，最大外部量子效率、發光效率、功率效率分別可達
21.3 %、65.9 Cd/A、82.8 lm/W，電激發光最大值紅位移至556 nm。
這一系列分子的外部量子效率不僅遠超過螢光分子的理論值，與文獻
中的熱活化延遲螢光發光體相比也相當突出，我們預期此種分子設計
策略能應用於高效率熱活化延遲螢光材料。

In this thesis, we designed and synthesized a series of highly efficient
thermally activated delayed fluorescence (TADF) emitters which contain
pyridine-3,5-dicarbonitrile as electron acceptor, named CzdmPPC,
tCzdmPPC, DBAZdmPPC, SPACdmPPC, DPAdmPPC. In addition to
high bond dissociation energies, carbonitrile moieties suppress geometry
relaxation of molucule’s excited states. Dicarbonitrile group combines
with pyridine, which contins high energy gap (Eg), gives moderate
acceptor strength. By changing the moieties of electron donors, dihedral
angles between donor and phenyl linker increases, and intramolecular
charge transfer (ICT) characteristics could be enhanced. The maximum
photoluminance (PL) wavelength of different molecules in toluene varies
from 482 nm to 544 nm. By measuring fluorescence at room temperature
and phosphorescence at low temperature, the energy splitting between S1
and T1, namely ΔEST, is 0.273, 0.126, 0.023, 0.046, 0.018 eV. Compound
CzdmPPC, tCzdmPPC have larger ΔESTs, which is disadvantageous to
reverse intersystem crossing (RISC) process from T1 to S1. Other
molecules have ΔESTs close to thermal energy at room temperature,
which indicates the xylene bridge could shorten the electron conjugation and efficient RISC of these materials, the
fabricated devices with CzdmPPC, tCzdmPPC, SPACdmPPC,
DPAdmPPC doped in mCPCN show maximum external quantum
efficiencies (EQEs) higher than 15 %. EQE significantly increases as Δ
EST and delayed fluorescence (DF) lifetime decrease, which also results in
reduction in efficiency roll-off at high luminance. DPAdmPPC has small
ΔEST , 100 % PLQY and delayed fluorescence lifetime of 3.4 μs. The
horizontal dipole ratio is 0.88 doped in mCPCN, and the device shows the
maximum EQE, curent efficiency (C.E.), power efficiency (P.E.) of 41.2
%, 135.8 Cd/A, 142.2 lm/W. Due to the extraodinary device performance
of DPAdmPPC, we also apply it as non-doped emitter. The rigid structure
avoids concentration quenching in neat film, and it shows maximum EQE,
C.E., P.E. of 21.3 %, 65.9 Cd/A, 82.8 lm/W. The series of molecules’
efficiencies not only surprass the theorical value of fluorescent materials,
but also show one of the best performance among reported TADF emitter.
We expect that the molecular design strategies would be applied to highly
efficient TADF materials.

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