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中国物理学会期刊

激基复合物与电致激基复合物共存体系中Dexter能量传递导致的负磁效率

CSTR: 32037.14.aps.71.20221288

Negative magnetic efficiency induced by Dexter energy transfer in coexistence system of exciplex and electroplex

CSTR: 32037.14.aps.71.20221288
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  • 因具有反向系间窜越过程(reverse intersystem crossing, RISC)在低成本就可实现高效率发光, 激基复合物(exciplex)型有机发光二极管(organic light-emitting diodes, OLEDs)是目前的一个研究热点. 其微观过程通常表现为极化子对的系间窜越(ISC)过程占主导, 引起的磁电致发光(magneto-electroluminescence, MEL)效应和磁电导(magneto-conductance, MC)效应都是正值, 且MEL幅值大于MC幅值; 由于在一般电流(I)范围内存在线形关系EL \propto \eta \cdot I , 对应的磁效率(magneto-efficiency, Mη)也是正值. 本工作却在激基复合物与电致激基复合物(electroplex)共存的器件中发现: 虽然在小电流下MEL值也大于MC值, 但是电流增大后MEL值逐渐小于MC值, 即Mη值由正变成负. 通过对比该型器件与纯激基复合物型器件中不同的物理微观过程发现: 激基复合物与电致激基复合物共存器件中存在从激基复合物到电致激基复合物的Dexter能量转移(Dexter energy transfer, DET)过程, 此过程会增强电致激基复合物的RISC过程, 且DET过程会随电流的增大而增强, 导致器件在大电流下表现为RISC过程主导的负Mη. 本工作有助于认识激基复合物型OLEDs中激发态间的相互作用规律, 也为制作高效率发光器件提供了理论参考.

     

    Exciplex-type organic light-emitting diodes (OLEDs) are research focus at present, because of their high-efficiency luminescence at low cost due to the reverse intersystem crossing (RISC, EX1 ← EX3). Their microscopic processes usually exhibit intersystem crossing (ISC, PP1 → PP3) process dominated by polar pairs, leading the magneto-electroluminescence MEL, MEL = (ΔEL)/EL × 100% effect values and the magneto-conductance MC, MC = (ΔI)/I × 100% effect values to be both positive, the amplitude of MEL to be greater than that of MC at the same current, and the corresponding magnetic efficiency Mη, Mη = (Δη)/η × 100% values to be also positive due to the linear relationship EL \propto \eta\cdot I within general current (I) range. Surprisingly, although the MEL value of the device coexisting with exciplex and electroplex is also greater than the MC value at low current, MEL value is less than MC value at high current. In other words, Mη value of this device undergoes a conversion from positive to negative with current increasing. In this work, to find out the reason why Mη value of exciplex-type OLED formed by TAPC and TPBi shows a negative value under high current and also to study the micro-dynamic evolution mechanism of spin-pair states in this device, three OLEDs are fabricated and their luminescence spectra and organic magnetic field effect curves are measured. The results indicate that the electroplex is produced in the exciplex-type OLED formed by TAPC and TPBi. Since the triplet exciton energy of monomers TAPC and TPBi is higher than those of triplet charge-transfer states of exciplex (CT_3^\rmex ), and the CT_3^\rmex energy is greater than the energy of triplet charge-transfer states of electroplex (CT_3^\rmel ), the CT_3^\rmex energy can only be transferred to CT_3^\rmel through Dexter energy transfer (DET) process without other loss channels. The electroluminescence (EL) spectrum of this device shows that the luminescence intensity of exciplex is greater than that of electroplex, which indicates that the quantity of exciplex is more than that of electroplex. Besides, EL spectra at different currents prove that the formation rate of exciplex is faster than that of electroplex with current increasing. Owing to less quantity of exciplex at low current, the DET process from CT_3^\rmex to CT_3^\rmel is too weak to facilitate the RISC process of charge-transfer states of electroplex (CTel). Therefore, the low field amplitude of Mη curve is positive at low current. The number of spin-pair states of exciplex increases with current increasing, which enhances the DET process. These processes of direct charge carriers trapped and energy transferred critically increase the number of CT_3^\rmel at high current, which greatly strengthens the RISC process of CTel. Therefore, the low field amplitude of Mη curve changes from positive to negative with current increasing. Furthermore, the Mη curves of this device are measured when only exciplex exists and only electroplex exists in the employing filter, respectively. As expected, the results confirm the accuracy of the mechanism of the negative value of the total Mη for this device. Obviously, this work contributes to the comprehension of the internal micro-physical mechanism in OLEDs and the law of interactions between excited states.

     

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