本研究系統性探討三重態–三重態融合機制在高分子與有機發光二極體螢光發光行為中所扮演的角色，並以磁電致發光測作為解析三重態相關物理機制的關鍵探針。在典型 poly(9,9-dialkylfluorene) 衍生物（PF Green B）為發光層之高分子發光二極體中，於不同偏壓條件與操作溫度下所量測之磁電致發光響應清楚顯示，螢光發光行為部分源自三重態激子經由三重態–三重態融合過程轉化為單重態激子的貢獻。研究結果進一步指出，三重態–三重態融合機制的貢獻程度與三重態激子的濃度、壽命以及極化子猝滅行為密切相關，且可透過陰極工程進行有效調控，包括引入激子阻擋層與不同陰極緩衝層材料，以改變載子動力學並調節三重態–三重態融合對螢光發光的影響。
在此基礎上，本研究進一步發展藍光超級三重態–三重態融合有機發光二極體結構，於三重態–三重態融合發光層相鄰位置引入三重態復合層（triplet tank layer, TTL），以主動強化三重態–三重態融合機制。三重態復合層可有效侷限載子復合區域、抑制三重態–極化子猝滅，並產生大量三重態激子，這些激子主要透過 Dexter 能量轉移機制注入至三重態–三重態融合發光層中，進而轉化為可輻射的單重態激子。此一以三重態–三重態融合機制為主導的發光行為，可於暫態電致發光量測中觀察到延遲螢光特徵，並於磁電致發光響應中呈現具代表性的指紋型曲線。隨著三重態–三重態融合機制效率的提升，超級三重態–三重態融合有機發光二極體的外部量子效率有明顯的提升。整體而言，本研究揭示了傳統螢光發光中長期被忽略的三重態激子貢獻，並證實透過精準調控三重態–三重態融合機制，能作為實現高效能高分子與有機螢光發光二極體之可行且具實用價值的策略。

This study investigates the hidden contribution of triplet–triplet fusion (TTF) to fluorescence emission in polymer light-emitting diodes (PLEDs) based on poly(9,9-dialkylfluorene) derivatives. Traditionally, fluorescence emission is attributed solely to singlet excitons; however, this work demonstrates that triplet excitons can also contribute through the TTF process. Magneto-electroluminescence (MEL) measurements are employed to identify spin-dependent processes, including hyperfine interaction (HFI) and TTF, via their characteristic fingerprint curves. By varying injection current and operating temperature, the triplet exciton density and lifetime are systematically modulated. The results reveal that the TTF contribution increases with higher current density and lower temperature due to enhanced triplet population and reduced phonon interactions. Furthermore, device configuration via cathode modifications, including exciton-blocking and buffer layers, effectively suppresses triplet quenching and enhances TTF intensity. These findings provide direct evidence that fluorescence emission in conventional PLEDs is significantly contributed to by triplet excitons via TTF, offering a new perspective for improving device efficiency.

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