【作者】 余登斌；

【导师】 钟安永；

【作者基本信息】 四川大学 ， 高分子化学与物理， 2007， 硕士

【摘要】 本论文系统介绍了有机发光材料和静电自组装技术的发展概况。自从1987年Tang和Van Slyke第一次报道用8-羟基喹啉铝(AlQ3)制得有效的有机电致发光器件(organic light-emitting diode, OLED)后,近20年来,人们投入了大量的精力研究应用于下一代显示器件的电致发光材料。有机、聚合物薄膜电致发光器件成为近年来热门的研究领域。高分子化8-羟基喹啉金属螯合物具有良好的发光特性,其可溶性聚合物还具有优良的机械性能和良好的成膜性能,季铵型高分子化8-羟基喹啉金属离子(Al3+、Zn2+和Li+)螯合物与聚阴离子电解质能够静电自组装制得功能超薄膜,可用于制备有机电致发光器件,本文在此基础上提出研究设想。本文从设计合成甲基丙烯酸二甲氨基乙酯(DM)含量分别为9.69%和16.29%的丙烯酸酯类共聚物(CPA1和CPA2)出发,将制得的5-氯甲基-8-羟基喹啉(CHQ)挂接到CPA1和CPA2上,得到季铵型高分子化8-羟基喹啉(CPA1-HQ和CPA2-HQ),然后与金属离子Al3+螯合得到CPA1-HQ-Al和CPA2-HQ-Al,这是首次报道合成季铵型高分子化8-羟基喹啉铝,最后与聚阴离子电解质(全氟磺酸)静电自组装,成功制得了多层超薄膜。化合物结构通过红外、紫外和荧光光谱表征;高分子化8-羟基喹啉及其金属螯合物的热稳定性通过DSC表征;凝胶渗透色谱法(GPC)确定CPA1、CPA2、CPA1-HQ、CPA2-HQ、CPA1-HQ-Al和CPA2-HQ-Al为高分子量化合物;高分子化8-羟基喹啉铝易溶于四氢呋喃(THF)、二氯甲烷、氯仿等常用有机溶剂;自组装膜的紫外和荧光光谱相对溶液红移,与文献报道一致,这可能是由于螯合物所处的环境在膜表面与在溶液中不同所至;紫外吸收和光致发光(photoluminescence, PL)光谱说明聚合物的发光来自于AlQ3基团,膜的紫外吸收强度随组装膜层数增加线性递增,荧光强度随膜层数增加线性递减;通过原子力显微镜测试膜的表面形貌,说明形成了均匀致密的多层超薄膜。实验结果表明制得的季铵型高分子化8-羟基喹啉铝是一种溶解性好,热稳定性强、荧光效率高的新型绿色发光材料,与聚阴离子电解质的静电自组装超薄膜可望应用于OLEDs的制备。作为与高分子化8-羟基喹啉铝结构类似的高分子化8-羟基喹啉锌/锂的自组装研究也取得了很好的成果。更多还原

【Abstract】 The organic luminescence materials and electrostatic self-assembly (ESA) were reviewed briefly in this paper. Since the first efficient organic light-emitting diode (OLED) was reported by Tang and Van Slyke with aluminum quinolate (AlQ3) in 1987, the last 10 years have been devoted to intensive research into coordination compound light-emitting materials for applications in next-generation display technologies. The soluble 8-hydroxyquinolate-containing copolymers metal chelates displayed both the excellent fluorescent properties and the processing properties of polymers. The ESA thin films of 8-hydroxyquinolate-containing quaternary ammonium copolymers metal cations (Al3+、Zn2+ and Li+) complexes and the anion polyelectrolytes can be used in preparing OLEDs. The research design of this paper is put forward be based upon above foundation.The co-polymerization of methacrylic esters (CPA1 and CPA2) containing of the 2-(Dimethylamino) ethyl methacrylate(DM, 9.69 wt % and 16.29 wt %) was the firstly synthesized. 5-chloromethyl-8-hydroxyquinoline (CHQ) was obtained by chloromethylation of 8-hydroxyquinoline and ingrafted to CPA1 and CPA2 to synthesize the opposite hight molecular weight quaternary ammonium polymers containing 8-hydroxyquinoline (CPA1-HQ and CPA2-HQ). Then the new cation type luminescence materials——8-hydroxyquinoline aluminium-containing copolymers (CPA1-HQ-Al and CPA2-HQ-Al) were prepared by CPA1-HQ and CPA2-HQ chelated with metal ion Al3+, which is the first report of the attachment of AlQ3 complexes as side chains to a quaternary ammonium polymers, then multilayer films were prepared by ESA of the cations (CPA1-HQ-Al and CPA2-HQ-A) and anion polyelectrolytes (Nafion 117). The chemical structure of the polymers and the polymeric complexes were characterized by infrared absorption spectroscopy (FT-IR), ultraviolet absorption spectroscopy(UV-Vis)and photoluminescence (PL). The thermal performance of the polymers and the polymeric complexes were studied by differential scanning calorimeter (DSC). The CPA1, CPA2, CPA1-HQ, CPA2-HQ, CPA1-HQ-Al and CPA2-HQ-Al are proved to be opposite hight molecular weight polymers by gel permeation chromatography (GPC). PolymerⅥis quite soluble in common organic solvents such as tetrahydrofuran, DMF and CHCl3 etc. and suitable to form films. The UV-Vis absorption spectra and photoluminescence (PL) excitation and emission spectra of the AlQ3-containing polymers were consistent with the literature date of metaloquinolinolate complexes. And the UV-Vis and fluorescence spectrum of the multilayer films red shift compare those in solutions for the different circumstance. The surface of the multilayer films were quite disciplinarian and compact observed by atom force microscope (AFM). The experimental results indicated that these kinds of materials were thermally stable, highly fluorescence and have excellent electron-transporting mobility, the multilayer films can be used for practical applications in OLEDs with Nafion 117 by ESA. The better results of studies on ESA of thezinc/lithium-8-hydroxyquinolate-containing quaternary ammonium copolymers have also been acquired on in the third and fourth chapter be similar to those in second chapter by using the analogous research methods.更多还原