OLED发光材料的理论计算与分子设计

数次有机发光二极管（OLED）器件效率的突破均源于有机电致发光新机制的发现和有机发光材料的创新。理论探究有机分子激发态的形成和衰变过程可以加深理解发光的微观机理,促进发光材料分子的研发。本文简要介绍了热振动关联函数（TVCF）的速率理论,及其在荧光、磷光和热激活延迟小分子材料中的应用。针对这三类小分子材料,我们揭示了其发光机理,建立了分子结构与性质之间的关系,提出了表征效率的描述符,并理论设计了优良的OLED发光分子。     

基于溶液加工小分子材料发光层的有机-无机复合发光器件

报道了基于溶液加工有机小分子材料发光层、聚乙烯亚胺电子注入层的有机-无机复合发光器件. 优化了空穴传输层和磷光染料的掺杂浓度, 得到最佳发光效率的器件. 蓝光、黄光和红光器件的最大外量子效率为17.3%, 10.7% 和7.3%. 在发光亮度为1000 cd/m² 时, 蓝光、黄光和红光器件的外量子效率分别为17.0%, 10.6% 和5.8%, 器件效率下降较小. 原因在于同时采用空穴传输型和电子传输型的小分子材料作为共同主体材料, 器件具有较宽的载流子复合区域, 降低了三线激发态-三线激发态湮灭和三线激发态-极化子相互作用对器件发光效率的影响. 白光器件在亮度为1000 cd/m²时, 发光效率和功率效率为31 cd/A和 14.8 lm/W. 器件的色度为(0.32, 0.42), 色度比较稳定, 随电流的变化微小. 器件的效率较以往报道的有机-无机复合发光器件有显著的提高, 主要归因于在聚乙烯亚胺上能够制备特性良好的小分子材料薄膜, 以及小分子主体材料拥有较高的三线态能量和平衡的载流子传输特性, 能够获得高效的磷光发射.     

有机发光材料中的三重激发态（英文）

有机发光材料有望广泛应用于新一代柔性光电子器件。由于自旋多重性,有机分子发光材料中单重激发态和三重激发态转换较慢,限制有机发光器件特别是电注入荧光器件的效率。我们介绍下近年来通过分子设计操控激发不同时间尺度三重态的动力学来突破这一限制的策略,通过控制激发单重态和激发三线态之间的电子耦合,利用热激子系间窜越、反向系间窜越、激发三重态稳定化等过程能够有效提高有机发光材料的发光效率。在此基础上实现的热活化延迟荧光、有机长余辉发光等在有机发光二极管、传感器、生物成像等领域有重要潜在应用价值。     

乙醇-水团簇分子形成激基缔合物及荧光发射机理研究

紫外光照射具有特殊结构的长链式乙醇-水团簇分子时,处于激发态和基态的分子形成了分子间激基缔合物,并发射荧光.根据实验结果分析和能量转移理论可知,激发态单分子和激基缔合物间形成了电子迁移洛合物并发生了能量转移.根据Mulliken理论对电子迁移洛合物进行量子力学处理,得出了团簇分子在基态和激发态能量E^b_N和E^b_E以及由于电子迁移而引起的静电相互作用能E^s;根 关键词： 荧光光谱 激基缔合物 电子迁移 乙醇-水团簇     

白光有机发光器件的研究进展

白光有机发光器件(OLED)能够产生高效饱和的白光,且具有驱动电压低、材料柔性好、可实现大面积显示等特点,在信息显示与固态照明等领域有巨大的应用潜力.目前白光OLED主要分为单发光层、多发光层、下转换、叠层等结构,不同的结构具有各自的优势,都受到了很大关注.首先介绍了白光OLED的性能指标.接着,结合所开展的研究工作综述了白光OLED在结构和性能方面的研究进展,总结了实现高效白光OLED的各种方法,重点探讨了提高白光OLED性能的途径及所面临的挑战. 最后,展望了白光OLED的发展趋势. 关键词： 白光有机发光器件 固态照明 电致磷光 光取出     

有机发光材料中的三重激发态

有机发光材料有望广泛应用于新一代柔性光电子器件。由于自旋多重性，有机分子发光材料 中单重激发态和三重激发态转换较慢，限制有机发光器件特别是电注入荧光器件的效率。我们介绍 下近年来通过分子设计操控激发不同时间尺度三重态的动力学来突破这一限制的策略，通过控制激 发单重态和激发三线态之间的电子耦合，利用热激子系间窜越、反向系间窜越、激发三重态稳定化 等过程能够有效提高有机发光材料的发光效率。在此基础上实现的热活化延迟荧光、有机长余辉发 光等在有机发光二极管、传感器、生物成像等领域有重要潜在应用价值。     

4-四氢喹啉酮的合成及发光性能

对喹吖啶酮结构改造合成了新型结构荧光体4-四氢喹啉酮,对其吸收光谱及荧光光谱进行了研究,发现该化合物的吸收峰及荧光发射峰随溶剂极性的增加而不断红移,表明荧光来源于分子内激发态电荷转移发光.该化合物在固态即显示荧光,表明经结构改造后,消除了喹吖啶酮类的固态荧光猝灭效应.4-四氢喹啉酮结构简单,易于合成和结构修饰.这对于寻找新的主体荧光发射材料具有重大意义.     

单分子荧光过程的Monte-Carlo模拟

从单分子发光过程中电子在激发态上的停留时间t服从P(t)=γe^-γt分布出发,对单分子荧光过程进行M-C(Monte-Carlo)随机试验,得到了单分子的激发态相邻两次发光的时间间隔的统计结果以及单分子荧光强度的自相关函数,并对其进行了详细地讨论,这些结果与目前文献报道的实验结果相一致.     

半花菁分子激发态的动力学特性研究

本文利用不同波段的时间分辨荧光和三维荧光谱对半花菁分子激发态的动力学特性进行了研究。在半花菁／花生酸交替的Y型多层膜中,半花菁分子形成的H－聚集体引起其三维荧光谱蓝移,并且荧光峰随时间的变化逐渐向红光方向移动。由于聚集体内所有分子间的相互作用（耦合）相干叠加,使得LB膜中的半花菁分子的激发态寿命比溶液寿命要短,由激发态较高振动能级向低能级过渡较快,因而不同波段的起始发光时间相差也较小。     

单分子-光子制冷泵的热力学行为(Ⅰ)

建立了一般意义上的单分子－光子泵模型,并用计算机模拟了在不同能量的光子激发下单个分子作为制冷泵时的量子跃迁过程,研究了单分子－光子泵处于基态和激发态时的热激发过程以及在发生荧光辐射时的声子参与情况,得出了基态具有较强的制冷能力的结论。基态和激发态在光吸收和发射过程中热力学效应是不同的,因此在选择反斯托克斯芝光制冷材料时,发光中心的基态能级劈裂更具重要性。     

有机电致发光白光器件的研究进展

在十多年的时间里,有机电致发光二极管(Organic Lightemitting Diodes,OLEDs)的研究和应用取得了长足的进展。有机电致发光器件具有许多优点,例如:自发光、视角宽、响应快、发光效率高、温度适应性好、生产工艺简单、驱动电压低、能耗低、成本低等,因此有机电致发光器件极有可能成为下一代的平板显示终端。有机电致发光白光器件因为可以用于全彩色显示和照明,已成为OLED研究中的热点。介绍了有机电致发光白光器件的研究进展,按发光的性质将白光器件分为荧光器件和磷光器件两类,按发光层数将白光器件分为单层和多层器件,对相关材料、器件结构、发光机理等方面进行了讨论。     

General factors governing the efficiency of luminescent devices

Factors which determine the luminescence efficiency of activated wide band gap materials are discussed in general terms. These materials find usage in a large variety of luminescent devices. The factors affecting the efficiency can be classified into two broad categories. The first has been thoroughly studied and entails interactions which lead to nonradiative dissipation of optical energy at the specific active site. The second set concerns interactions leading to the delocalization and the transport of optical energy away from the originally excited state. Recent spectroscopic results from these studies have allowed the absolute placement of the ground state of the active centers with respect to the intrinsic bands of the host crystal and have allowed us to elucidate the systematics of such placement. These results are relevant to materials which evince the property of persistent phosphorescence and which are of our current interest. Developments in these materials, as well as a number of new applications, will be touched upon.     

氧空位对Eu2+, Dy3+掺杂的Ca5MgSi3O12发光及余辉性能的影响

利用高温固相法合成了稀土离子Eu²⁺, Dy³⁺掺杂的Ca₅MgSi₃O₁₂长余辉发光材料. 利用光谱学证明了在材料内部存在与氧空位有关的缺陷发光. 通过对比不同条件下合成样品的发光及余辉性能, 发现氧空位对材料的发光及余辉均起到促进作用. 同时发现氧空位发光可以向发光中心传递能量. 利用热释光曲线系统的分析了氧空位对余辉性能的影响. Ca₅MgSi₃O₁₂:Eu²⁺,Dy³⁺是一种潜在的长余辉发光材料. 关键词： 长余辉 氧空位 能量传递 热释光     

Long-lived luminescence of complex molecules

Results of investigations of all types of long-lived luminescence of organic molecules in the gas phase and condensed media are presented. Methods for identification and separation of contributions of phosphorescence and thermally activated fluorescence in long-lived luminescence of organic-molecule vapors are proposed. Energy transfer and migration processes in the case of the inductive-resonant mechanism of intermolecular interaction leading to the appearance of sensitized phosphorescence and annihilation-induced delayed fluorescence are considered. Experimental results on energy migration obtained for solid solutions of organic compounds are analyzed within the framework of the concepts of percolation theory with account for the microscopic inhomogeneity of the systems under investigation and the fractal properties of the clusters of activator molecules. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, F. Skorina Ave., 70, Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 5, pp. 662–674, September–October, 1998.     

Non-covalent interaction controlled 2D organic semiconductor films: Molecular self-assembly,electronic and optical properties,and electronic devices

The establishment of electronic and opto-electronic products relying on organic semiconductors (OSCs) has been intensely explored over the past few decades due to their great competitiveness in large area, low cost, flexible, wearable and implantable devices. Many of these products already entered our daily lives, such as organic light-emitting diodes-based displays, portable organic solar cells and organic field-effect transistors. The device performance of OSC devices are determined by the supramolecular organization (orientation, morphology) as well as the supramolecular organization dependent energy level alignment at various interfaces (organic/electrode, organic/dielectric, organic/organic). This review focuses on the impact of non-covalent interaction on the molecular self-assembly of organic thin films, their electronic and optical properties, as well as the device performance. Beginning with the growth of multiple OSCs on substrates with different interfacial interaction strengths (metals, insulators, semiconductors), the critical roles of molecule-substrate and intermolecular interactions in determining the thin film organization have been demonstrated. Several non-covalent interactions that contribute to the energy levels of organic materials in solid phase are summarized, mainly including the induction contributions, electrostatic interactions, band dispersions and interface dipoles. The excitonic coupling in specific aggregations of organic molecules and the corresponded effect on their optical properties are also discussed. Finally, the influences of weak intermolecular interactions on the device performance are presented.     

Determination of the stimulated raman scattering threshold for a pump pulse of arbitrary width

The spectral luminescent, photophysical, photochemical, lasing, nonlinear optical, and sensor characteristics of a series of new synthesized complexes of zinc and difluoroborate with dipyrrines of different structure have been studied. It is found that many of these compounds exhibit stimulated emission in different solvents when excited by the second (532 nm) and third (355 nm) harmonics of a Nd:YAG laser in the range of 548–692 nm. It is shown that not only efficient fluorophores belonging to dipyrrine difluoroborates (with a quantum fluorescence yield close to 1), but also compounds with a fluorescence yield equal to 0.3, generate laser radiation with a high resource; phosphorescence is also observed along with fluorescence. Transmission of UV radiation (355 nm) is shown to decrease with an increase in the pulsed excitation power density; this is a manifestation of nonlinear optical properties. The change of phosphorescence signal in dependence of the composition of the gas mixture around a solid-state sample colored by dipyrrinate complexes indicates that a number of the compounds under consideration exhibit sensor abilities.     

有机电致发光器件的磷光发光研究

研制了一种以铕钇络合物（Eu0.1Cd0.9)(TTA)3(TPPO)2为发光材料的新型有机电致发光器件,观察到了三重态的磷光发光现象,分析表明此电致磷发光是Gd^3 对络合物配体电子自旋轨道强烈扰动引起的三重态发光。同时用积分球方法测定了该器件在不同温度下的光致发光和电致发光效率,结果表明此磷发光效地提高了器件的电致发光效率。     

Electronic,structural and chemical effects of charge-transfer at organic/inorganic interfaces

During the last decade, interest on the growth and self-assembly of organic molecular species on solid surfaces spread over the scientific community, largely motivated by the promise of cheap, flexible and tunable organic electronic and optoelectronic devices. These efforts lead to important advances in our understanding of the nature and strength of the non-bonding intermolecular interactions that control the assembly of the organic building blocks on solid surfaces, which have been recently reviewed in a number of excellent papers. To a large extent, such studies were possible because of a smart choice of model substrate-adsorbate systems where the molecule-substrate interactions were purposefully kept low, so that most of the observed supramolecular structures could be understood simply by considering intermolecular interactions, keeping the role of the surface always relatively small (although not completely negligible). On the other hand, the systems which are more relevant for the development of organic electronic devices include molecular species which are electron donors, acceptors or blends of donors and acceptors. Adsorption of such organic species on solid surfaces is bound to be accompanied by charge-transfer processes between the substrate and the adsorbates, and the physical and chemical properties of the molecules cannot be expected any longer to be the same as in solution phase. In recent years, a number of groups around the world have started tackling the problem of the adsorption, self- assembly and electronic and chemical properties of organic species which interact rather strongly with the surface, and for which charge-transfer must be considered. The picture that is emerging shows that charge transfer can lead to a plethora of new phenomena, from the development of delocalized band-like electron states at molecular overlayers, to the existence of new substrate-mediated intermolecular interactions or the strong modification of the chemical reactivity of the adsorbates. The aim of this review is to start drawing general conclusions and developing new concepts which will help the scientific community to proceed more efficiently towards the understanding of organic/inorganic interfaces in the strong interaction limit, where charge-transfer effects must be taken into consideration.     

Electronic energy transfer in benzophenone adlayer

The extent to which energy transfer occurs in electronically excited organic adlayer films on dielectric surfaces is investigated. Migration and subsequent trapping of the energy in the film are observed by pumping the singlet state of an organic adlayer of benzophenone and by monitoring the phosphorescence and fluorescence lifetimes. To observe the effects of adsorption, benzophenone was chosen as the adlayer because the energies of its well characterizedn, carbonyl states are remarkably sensitive to solvent interactions. Upon excitation with a nitrogen laser, the perturbation on the electronic states of benzophenone by the substrate caused the emergence of the normally absent fluorescence from the adlayer traps at the interface between the surface of the dielectric substrate and the adlayer. Energy transfer to this interface was observed as a function of film thickness. On the surface of a single crystal of an organic crystal, naphthalene, energy transfer from the adlayer to the substrate was observed, whereas such transfer was not energetically possible with the other dielectric surfaces.     

印度尼西亚化石树脂的光致发光特征研究

紫外灯下,化石树脂常见荧光现象,但其磷光现象仍有待表征与研究。将印度尼西亚产出的类似多米尼加蓝珀的化石树脂分为白色包体（Part Ⅰ）、暗色包体（Part Ⅱ）和基底（Part Ⅲ）三个部分,使用红外光谱确定其植物来源,借助三维荧光光谱仪表征化石树脂的光致发光现象（包括荧光和磷光）,并探讨印尼化石树脂发光现象随地质过程变化的规律。红外光谱中1 384,1 377和1 367 cm-1的振动峰表征所研究的化石树脂来源于龙脑香科植物。印尼化石树脂的Part Ⅰ~Ⅲ中均存在3种特征荧光峰：紫外区330～380 nm、近紫外区388 nm和蓝绿光区446,474和508 nm,分别可被235,330和440 nm光有效激发;进一步推测可见光区荧光来源于两种不同的发光物质,两者在白色包体、暗色包体和基底中相对含量不同。同时,暗色包体和基底的磷光最强峰在537 nm附近和磷光寿命长达100 ms,比白色包体的430 nm磷光峰更强且衰减时间更长,贡献了印尼化石树脂的黄绿色磷光。结合前人火山活动刺激树脂的产生和还原环境促进芳构化作用的观点,推测印尼化石树脂中白色包体、暗色包体和基底的三维荧光光谱和磷光光谱可有效说明基底部分芳构化程度高于暗色包体,白色包体芳构化最低。