利用发光磁效应研究同分异构体mCBP和CBP作为给体的激基复合物器件的微观过程

本文把同分异构体3,3’-Di(9H-carbazol-9-yl)biphenyl (m CBP)和4,4’-Bis(carbazol-9-yl)biphenyl (CBP)作为给体, PO-T2T作为受体,以质量比1∶1制备了两种激基复合物器件,并在不同温度和偏压下测量了器件的发光磁效应(magneto-electroluminescence, MEL).发现室温下m CBP为给体的器件,其MEL的低磁场部分表现出反向系间窜越(reverse intersystem crossing, RISC)过程,降温时该RISC转变为系间窜越(intersystem crossing, ISC)过程;而CBP为给体的器件则表现出ISC过程,且降温时ISC过程先减弱后增强.室温下两种器件MEL的高磁场部分都体现为三重态激子与电荷的猝灭,但在20 K下CBP为给体的器件还出现了三重态-三重态激子湮灭.两种完全相反的低磁场线型与m CBP和CBP不同的结构导致三重态激子能量的高低有关.低温下微观过程的改变是因为低温不利于RISC过程、ISC过程和能量损失等演化通道.此外,当m CBP:PO-T2T质...     

纯红荧烯器件中极化子对的系间窜越与高能三重态激子的反向系间窜越过程“消失”的原因

有机发光二极管(OLEDs)中电致发光磁效应(MEL)是一种能够揭示多种激发态微观过程的探测工具.最新研究成果(Tang X T, Pan R H, Zhao X, Jia W Y, Wang Y, Ma C H 2020 Adv. Funct. Mater. 5 765)表明:将低浓度的红荧烯(Rubrene)分子掺杂在一定主体作为发光层的OLEDs中,存在一种高能三重态激子(T_2,Rub)的反向系间窜越过程(HL-RISC, S_1,Rub←T_2,Rub).但本文发现:以Rubrene作为纯发光层且其两边的载流子传输层也不存在T_2,Rub激子的能量损失通道的OLEDs中,在室温下只观察到单重态激子(S1)的分裂过程(S₁+S₀→T₁+T₁),却没能观察到该T_2,Rub激子的HL-RISC过程;而且,最基本的因电子和空穴在纯Rubrene发光层中直接注入形成极化子对(polaron-pair...     

激基复合物有机发光二极管中系间窜越和反向系间窜越过程的非单调电流依赖关系

激基复合物有机发光二极管(exciplex-based organic light-emitting diodes,EB-OLEDs)中自旋对态(spin-pair states)的系间窜越(intersystem crossing,ISC)和反向系间窜越(reverse ISC,RISC)是重要的自旋混合过程.它们通常展示正常的电流依赖关系,即随电流的增大而减弱.本文利用磁电致发光(magneto-electroluminescence,MEL)作为指纹式探测工具,在具有不同电荷平衡的EB-OLEDs中观察到多种电流依赖的ISC和RISC过程.它们有趣的表现为:随着器件注入电流增大,非平衡器件中电流依赖的MEL曲线呈现从正常ISC(1—25μA)向反常ISC (25—200μA)过程的转换,而平衡器件中电流依赖的MEL曲线则展示从正常ISC(1—5μA)→反常RISC (10—50μA)→正常RISC (50—150μA)→反常ISC (200—300μA)过程的转换.通过拟合和解析MEL曲线,发现非平衡和平衡器件中的ISC和RISC过程随着电流增大都先增强后减弱.这些丰富而有趣的转...     

类富勒烯团簇发光性能的理论研究

热激活延迟荧光(TADF)作为一种特殊的分子荧光机制,对于提高发光效率有着重要意义.以C₆₀和C₇₀为代表的碳富勒烯具有高对称结构和离域π电子,被广泛证明具有显著的TADF效应;相比之下,其他类富勒烯团簇的光物理性质尚不清楚.本文利用含时密度泛函理论探索了一系列类富勒烯团簇的激发态性质,包括实验合成的具有不同尺寸的氮化硼笼型团簇B₁₂N₁₂, B₂₄N₂₄和B₃₆N₃₆,以及与B₁₂N₁₂结构相同、元素组成不同的B₁₂P₁₂, Al₁₂N₁₂和Ga₁₂N₁₂.计算结果表明,这些类富勒烯化合物团簇具有2.83—6.54 eV的能隙,主要吸收紫外光,荧光发射波长在可见光区间,包括红光、橙光、蓝光和紫光.它们的第一激发单重态和三重态的能量差较小(...     

采用瞬态EL和延迟EL测试方法研究磷光掺杂体系的内部发光过程

有机磷光发光二极管(OLED)因为理论内量子效率能达到100%而成为研究热点,但是至今有机磷光OLED器件发光机理及过程仍然不完全清楚,需进一步研究. 本文中搭建了一套瞬态电致发光和延迟电致发光的测量系统,并首次综合运用瞬态电致发光和延迟电致发光测量来探测有机磷光OLED 器件发光层内部电荷载流子的运动,从而分析研究其内部发光过程及机理. 研究中首先制备了一种高效红色磷光材料(pbt)₂Ir(acac)衍生物(Irf)掺杂荧光材料作为发光层的器件,对其进行了瞬态EL测量,发现当驱动脉冲信号撤销时瞬态发光强度会突然出现一个瞬时过冲现象(transient overshoot),通过实验分析证实这个发光的瞬时过冲是由于发光层内部电子和空穴累积造成的,还证实了在发光层与空穴传输层界面存在空穴的累积. 通过延迟电致发光的研究发现在这种掺杂体系中发光主要来自于客体材料Irf的直接俘获电子空穴复合发光,而不是来自于主客体之间的能量传递,器件中的空穴传输发生在客体材料Irf上,而电子传递则主要在主体材料TAZ上. 同时还发现空穴注入是整个掺杂体系中重要的影响因素. 关键词： 瞬态EL 延迟电致发光 三线态-三线态湮没 overshoot     

Interaction behaviours of solitoffs: fission, fusion, reconnection and annihilation

The interactions between solitoffs are extensively investigated. Besides the known solitoff fission and fusion interactions, two new types of solitoff interactions are discovered, named the solitoff reconnection and the solitoff annihilation. Taking the asymmetric Nizhnik--Novikov--Veselov equation as an illustrative system, five types of solitoff interactions are graphically revealed on the basis of the analytical solution obtained by the modified tanh function expansion method.     

Determination of the rate constants of excited-complex formation and the diffusion rate constants for triplet-triplet annihilation kinetics for tetrapyrrole molecules in liquid solutions

With the flash-photolysis method, the kinetis of triplet-triplet annihilation (TTA) is investigated for a number of tetrapyrrole molecules in liquid solutions. Based on the analysis of the kinetic scheme of TTA through the formation of excited complexes (TT) a procedure for determining the constant of the rate of (TT) formation from two molecules in the triplet state (k₁) is proposed. The k₁ values obtained are equal to the rate constants for the processes controlled by molecular diffusion in the solution (K_d), which are calculated by a modified Vavilov-Debye formula. The values of K_d can be determined experimentally by the proposed procedure for processing the data on TTA. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 4, pp. 521–527, July–August, 1998.     

Heterogeneous triplet-triplet annihilation of erythrosine and anthracene molecules on a fractal anodized aluminum surface

We have studied exchange resonance processes of homogeneous triplet-triplet annihilation and heterogeneous triplet-triplet annihilation for erythrosine and anthracene molecules on an anodized aluminum surface over a broad temperature range. We have shown that the kinetics of the considered processes are determined by the dimensionality of the molecular clusters on the porous anodized aluminum surface. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 205–210, March–April, 2007.     

Similarity measures between excited singlet and triplet electron densities in linear acenes: an application to singlet fission

A theoretical framework for modelling the electronic structure of absorbing molecules that may contribute to explain and even predict phenomena where a singlet exciton is converted to triplet is reported. The pathway is suggested to occur when the excited singlet and triplet electron density maps are similarly shaped at Frank Condon states. Calculations were carried for some linear acene excitons from their multielectronic wave functions and corresponding charge maps after a configuration interaction of singly excited determinants. For cases where the singlet fission effect has been reported, charge maps of certain higher energy singlet excitons show a relevant shape similarity with the corresponding lowest triplet. This method could enlighten the way for predicting transit between singlets and triplets of very big systems and also may help to explain experimental phenomena at femto and even attosecond scales.     

Optically detected magnetic resonance studies of luminescence‐quenching processes in π‐conjugated materials and organic light‐emitting devices

It is widely recognized that nonradiative quenching of excitons by other excitons and polarons become the dominant decay mechanism of these excitons at high excitation densities. These quenching processes cause the roll‐off in the efficiency of organic light‐emitting devices (OLEDs) and prevent lasing at high injection current densities. This review presents the optically‐detected magnetic resonance (ODMR) evidence for these photoluminescence‐ and electroluminescence‐quenching processes. And while it provides such evidence for quenching of singlet excitons by polarons and triplet excitons, it reveals the central role of the strongly spin‐dependent annihilation of triplet excitons by polarons, since under normal excitation conditions the steady‐state polaron and triplet exciton populations are 100–10⁴ times the singlet exciton population. In addition, it also suggests that quenching of singlet excitons by bipolarons, likely stabilized by a counterpolaron or countercharge at specific sites, may also be a significant quenching mechanism that also affects the charge transport properties.     

电场诱导聚合物分子取向对单线态和三线态激子形成截面的影响

通过对聚乙烯咔唑(PVK) 掺杂三(2-苯基吡啶)铱(Ir(ppy)₃)和4-二氰亚甲基-2-叔丁基-6-(1,1,7,7-四甲基久咯呢定基-9-烯基)-4H-吡喃(DCJTB)，PVK 掺杂DCJTB和PVK掺杂Ir(ppy)₃聚合物在成膜时高压电场作用下分子取向变化对单线态和三线态激子形成截面的研究，发现，随着成膜时电场的增强，单线态激子的形成截面在增加，而三线态激子的形成截面却减小. 关键词： 分子取向 激子形成截面 三线态 单线态     

变系数(2+1)维Broer-Kaup系统的特殊孤子结构及孤子的裂变和湮没现象

利用改进的Riccati方程映射法，得到了变系数(2+1)维 Broer-Kaup 系统的孤波解、周期波解和变量分离解.根据得到的孤波解，构造出了系统的几种不同形状的孤子结构，研究了孤子的裂变和湮没现象. 关键词： 变系数(2+1)维 Broer-Kaup 系统 孤子结构 裂变 湮没     

Regularities of triplet-triplet annihilation of aromatic hydrocarbons in aqueous micellar solutions of sodium dodecyl sulfate

Investigation of deactivation processes in triplet states of a series of aromatic hydrocarbon molecules (antracene, 1,2-benzantracene, and 3,4-benzpyrene) made it possible to reveal the presence of triplet-triplet annihilation of the molecules in aqueous micellar solutions of sodium dodecyl sulfate. It is shown that the effect of microheterogeneous solutions on the process of triplet-triplet annihilation manifests itself in an increase in the probability of excimerization upon dissociation of triplet pairs of 1,2-benzantracene and 3,4-benpyrene molecules compared to one-component solutions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 626–628, September–October, 1997.     

纳米Cu固体材料的X射线衍射与正电子湮没研究

 采用自悬浮-冷压法,在不同压力下制得纳米Cu固体材料并对其在不同温度和保温时间下进行退火,利用X射线衍射(XRD)和正电子湮没寿命谱(PAS)分析对材料的结构和微观缺陷进行了表征。XRD分析表明,压制而得的样品晶粒度为20 nm,低于300 ℃退火3 h后并未发现晶粒显著长大;PAS分析表明,压制后的样品缺陷主要为单空位和空位团,大空隙很少,随着退火温度的升高和退火时间的延长,单空位通过扩散结合成空位团,大空隙也在温度较高时分解为空位团,导致空位团的含量增加,而单空位和大空隙的含量降低。