金属配位的有机半导体

《有机半导体材料合成与改性》第五章 金属配位的有机半导体陈军武 材料学院 高分子光电材料与器件研究所纲 要一、基本的金属配位化学反应 二、重要的金属配合物半导体的应用 三、 三线态发光（磷光）一、基本的金属配位化学反应1、金属配合物的特征 从试剂商网站了解金属配合物的特征先认识一些钯（palladium）的配合物Bis(triphenylphosphine)palladium(II) dichlorideSuzuki偶联催化剂(Ph3P)2PdCl2Tetrakis(triphenylphosphine)palladium(0)Suzuki偶联催化剂Bis(benzonitrile)palladium(II) chloride注意体会钯的价态（0价，2价）Bis(dibenzylideneacetone)palladium(0)Bis(3,5,3’,5’-dimethoxydibenzylideneacetone)palladium(0)Bromo(tri-tert-butylphosphine)palladium(I) dimerBis(acetonitrile)dichloropalladium(II)注意体会钯的价态（0价，1价，2价）钯的配合物有很多，上述钯的配合物是其中的部分代表， 它们通常用作化学反应催化剂， 而非有机半导体。

金属配合物有很多种类，以及各式各样的用途，比如：酞菁金属配合物卟啉（4N-大环配体）金属配合物酞菁（8N-大环配体）金属配合物N N N NH N N HN NIntroduction.Phthalocyanine metal complexes (MPc’s) are structurally related to porphyrin complexes, which are widely used by nature in the active sites of enzymes responsible for catalytic aerobic (有 氧的) oxidations, reduction and transport of dioxygen (分子氧), and destruction of peroxides. Although phthalocyanines are purely synthetic ligands (配体) they can, therefore, be regarded as related to bioinspired chemistry usually associated with porphyrin complexes. Among a large variety of porphyrinoid macrocyclic complexes such as porphyrins, porphyrazines, corroles, and corrolazines, MPc’s are probably the most accessible from a preparation point of view.N NH N HNporphyrinporphyrazine四氮杂卟啉corrolecorrolazineporphyrazine四氮杂卟啉Porphyrazines, or tetraazaporphyrins, are tetrapyrrole macrocycles similar to porphyrins and phthalocyanines. Pioneered by R. P. Linstead as an extension of his work on phthalocyanines, porphyrazines differ from porphyrins in that they contain -meso nitrogen atoms, rather than carbon atoms, and differ from phthalocyanines in that their β-pyrrole positions are open for substitution. These differences confer physical properties that are distinct from both porphyrins and phthalocyanines.A corrole is an aromatic organicchemical, the structure of which is similar to the corrin ring, which is also present incobalamin (vitamin B12). The ring consists of nineteen carbonatoms , with four nitrogen atoms in the core of the molecule. In this sense, corrole isvery similar toporphyrin , which is also an organic macrocycle but has twenty carbon atoms and is found in hemoglobin (血红蛋白) and chlorophyll (叶绿素).corroleChlorophyll a(叶绿素)Cobalamin may refer to severalchemical forms of vitamin B12, depending on the upper axial ligandof the cobalt ion.2、代表性的金属配合物有机半导体举例：铂配合物（卟啉铂）铜配合物（酞菁铜, CuPc）锌配合物钌配合物铼配合物锇配合物铜配合物铕配合物3、金属配合物的反应过程举例双金属配合物中间体并被继续转化均配异配铱(iridium)配合物乙酰丙酮（acac ）是重要的异配体环金属配体二齿辅助配体均配异配2006异配Chen CH,异配Chen CH,有众多的配体被用于制备双环金属配合物更多的结构变化4个蓝光配合物两种芴基吡啶配合物acac的变化形式：不同的R取代基铂(platinum)配合物含金属配合物的半导体聚合物金属位于侧链金属连接主链TAPC有机发光二极管的第一篇报导Alq3 发绿光，效率居中，性质稳定C.W. Tang (邓青云)发光光谱包括绿光、黄光、橙光获得了极高的电致发光效率这些配合物被分散在CBP 中成膜为发光层典型的发红、绿、蓝光（RGB三色）的铱配合物的结构：红光绿光蓝光选择了三种金属配合物参混在半导体聚合物中实现了白光蓝光绿光红光获得了很高的电致白光效率金属配合物作为三色白光聚合物的红光单元其中一个聚合物的电致发光光谱：属于白光区2、有机薄膜晶体管酞菁铜大环金属配合物酞菁氧钒Organic field-effect transistors with VOPc/ p-6P films as active layers realized high mobility of above 1 cm2/V s.3、有机太阳能电池的给体以酞菁铜为代表受体给体CuPc酞菁铜受体给体ECE = 1.8% CuPcCuPc效率可达5％三、三线态发光（磷光）1、电致磷光的简要原理用于OLED 中的发光材料可分为两类. 一类是荧光材料, 一类是磷光材料. 根据自旋量子统计理论, 电子和空穴复合后, 单重态激子和三重态激子的形成概率比例是1∶3, 即单重态激子仅占“电子-空穴对”的25%,75%的“电子-空穴对”由于形成了自旋禁阻的三重态激子对“电致发光”没有贡献. 因此, 单纯依靠单重态激子辐射衰减发光的荧光发光材料, 其电致发光的最大内量子效率为25%. 磷光材料能够通过系间窜越, 实现混合了单重态和三重态发光的磷光发射.金属配合物（看作染料）分散在半导体聚合物（看作主体）中时，相互间所能发生的能量转移理论上, 利用磷光材料制作的OLED 内量子效率可达100%, 它的发光效率比荧光材料提高三倍. 20 世纪90 年代末, 美国普林斯顿大学的Forrest 教授和南加州大学的Thompson 教授两个研究小组合作, 成功地利用铂-卟啉配合物, 环金属化的铱-苯基吡啶配合物作为磷光染料与电荷传输主体材料通过共蒸镀的方法制作有机电致发光器件中的发光层, 器件的外量子效率分别达到4%和8%, 相对于电致荧光器件得到了极大的提高. 近几年, 基于重金属配合物, 特别是铱配合物电致磷光材料和器件的研究已成为目前有机电致发光领域研究的热点. 其中, 利用铱配合物作为磷光材料而制作的多层OLED 器件, 其最大外量子效率已达到了19.2%, 能量转换效率为72 lm/W (65 cd/m2)。

卟啉铂PtOEP 第一次获得了电致磷光，效率约4％2、金属配合物小分子的电致磷光p151-154M. A. Baldo et al., Nature, 1998, 395, 151-154.The efficiency of electroluminescent organic light-emitting devices can be improved by the introduction of a fluorescent dye. Energy transfer from the host to the dye occurs via excitons, but only the singlet spin states induce fluorescent emission; these represent a small fraction (about 25%) of the total excited-state population (the remainder are triplet states). Phosphorescent dyes, however, offer a means of achieving improved light-emission efficiencies, as emission may result from both singlet and triplet states.Here we report high-efficiency (90%) energy transfer from both singlet and triplet states, in a host material doped with the phosphorescent dye 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine platinum(II) (PtOEP). Our doped electroluminescent devices generate saturated red emission with peak external and internal quantum efficiencies of 4% and 23%, respectively. The luminescent efficiencies attainable with phosphorescent dyes may lead to new applications for organic materials. Moreover, our work establishes the utility of PtOEP as a probe of triplet behaviour and energy transfer in organic solid-state systems.发光光谱包括绿光、黄光、橙光电致发光效率大幅提高到16％高效率蓝光（白光照明）。