锌配合物光电特性和铱配合物磷光敏化及光电特性研究
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摘要
有机电致发光作为一个新兴的研究领域不断吸引着越来越多的人们,目前已成为平板显示领域的一个研究热点。而有机发光材料是有机电致发光的基础和核心。面对人们对显示设备提出越来越高要求的同时,促使科学界和企业界不断地寻找更新型、更高效的发光材料,深入研究其发光机理,从而制备出性能更高、成本更低廉的显示器件来满足人们不断提出的要求。这个方向本身是一个涉及化学、材料学、物理和电子等多学科的研究领域,这需要人们从材料的设计和合成、发光过程和机理的分析等多方面去研究。本论文旨在采用金属配合物(锌、铱)材料,利用锌金属配合物的光电特性和铱金属配合物的磷光敏化作用设计了不同结构的器件结构,分别对其性能进行系统的研究,探索和分析了实验参数对金属配合物光电特性的影响,得出一些有意义的结论。
首先,研究了新型锌金属配合物发光材料FHQZn、BFHQZn、CzHQZn和MCzHQZn光电性能,验证了这四种锌金属配合物材料具有一定的空穴传输特性和发黄光特性。在此基础上,采用这四种发光材料分别制备了不同结构的器件。其中以CzHQZn材料制备了性能最好的WOLED,该器件结构为ITO/2T-NATA(22 nm)/ CzHQZn(18 nm)/NPBX(5 nm)/ADN(27 nm)/BCP(8 nm)/Alq3(20 nm)/LiF(0.5 nm)/Al。器件的最大亮度为6416 cd/m2(13V),最大发光效率为1.46 cd/A(10V),器件的色坐标由10V时的(0.30,0.31)到13V时的(0.28,0.30)几乎没变。另外,采用简单的水热法合成了一种新型配合物Zn(C19H12N4)2(C7H4O6S)H2O。研究发现,在晶体中晶胞之间通过氢键形成了三维超分子结构,芳环之间的π-π相互作用加固了晶体的结构。
其次,研究了铱金属配合物Ir(ppy)3的磷光敏化作用,详细地讨论了其磷光敏化作用对有机发光器件光电特性的改善。利用Ir(ppy)3分别敏化rubrene、ADN、CzHQZn而制作了白光或黄光器件。研究发现,敏化剂Ir(ppy)3能有效地提高材料的发光效率和亮度,磷光敏化作用的机理是通过磷光敏化剂从母体获得的能量通过共振转移的Forster机制传递给了荧光受主,使其被激发并辐射失活发射出荧光。
第三,研究了铱金属配合物Ir(piq)3的光电性能,采用Ir(piq)3为客体材料,使母客体能级匹配,载流子同时通过母体和客体进行传输,从而制备了具有混合母体结构的红色磷光器件。这种结构的器件使其启亮电压得到显著降低,发光效率得到有效提高。另外,采用物理共混方法来制备器件,研究发现随着rubrene共混比例的增加,器件的色度发生相应的改变,由蓝光经过白光变化到黄光,器件的亮度和电流效率也随电压呈现规律性的变化。该方法有利于简化有机电致发光器件的制备工艺,为实现产业化奠定了一定的基础。
有机电致发光存在生产工艺复杂、寿命不长、成品率较低等问题,通过研究可知,利用这种锌配合物材料制备的发光器件其发光特性较好,本身它也是集空穴传输和发光特性于一体的发光材料,这种多功能于一身的发光材料的开发和研制吸引更多的科技工作者。我们自己也尝试着通过水热法合成了一种锌配合物。另外,为了进一步提高器件的整体性能,利用铱配合物的磷光敏化作用及混合母体、物理共混等方法来提高器件的各项参数,这也是论文研究意义所在。
Organic electroluminescence, as new research field, has been a hot subject in flat panel displays and attracted more and more people. The organic luminous materials are the basis and core of the organic electroluminescence. Now, the new and high efficient organic luminous materials and their mechanisms are required as a result of the higher and higher technology for information display. Organic electroluminescence is by itself a subject relate to chemistry, material, physics, electronics etc., and need people to investigate it from material design and synthesis, luminescence process and mechanism, etc. The main points for this thesis are to research the photoelectric performance and phosphorescent sensitization of metal complexes (Zn and Ir), and analyse the effect of experiment parameter on the photoelectric performance. Finally, the significant results are given in the dissertation.
Firstly, we researched the luminescence performances of metal complexes FHQZn, BFHQZn, CzHQZn and MCzHQZn. The results showed that these metal complexes were yellow luminescence material with a certain hole-transporting characteristics. Base on above research, we finally fabricated the OLEDs with the four metal complexes materials. Among of them, the OLED with the structure of ITO/2T-NATA (22 nm)/CzHQZn (18 nm)/NPBX (5 nm)/ADN (27 nm)/BCP (8 nm)/Alq3(20 nm)/LiF (0.5 nm)/Al had the best luminescence performance with the CzHQZn material. The results showed the WOLED with a maximum luminous efficiency of 1.46 cd/A (at 10 V) and a maximum luminance of 6416 cd/m2 (at 13 V) was achieved. The CIE coordinates of device were from (0.30,0.31) for 10 V to (0.28,0.30) for 13 V, and they were stable on the voltages. In addition, we synthesized a new metal compoud of Zn(C19H12N4)2(C7H4O6S)H2O. The results showed the 3 d supramolecular structure was formed by hydrogen bonding by the unit cells, and theπ-πinteraction was strengthened the crystal structure.
Secondly, we researched the phosphorescent sensitization of the metal complexes Ir(ppy)3. And we mainly discussed the effect of phosphorescent sensitization on the luminescence performance of the OLEDs. At the first, the phosphorescent sensitizer of Ir(ppy)3 sensitized rubrene, ADN and CzHQZn materials were researched. The results showed the phosphorescent sensitizer of Ir(ppy)3 could improved the luminous efficiency and luminance of the luminescence materials. The energy of Ir(ppy)3, which from the host, had been transferred to acceptor by the Forster mechanism. Then it would be excitated and radiation deactivation in order to emit the fluorescence.
Thirdly, we researched the photoelectric performance of the metal complex Ir(piq)3. In the system, the carriers transport via Ir(piq)3 dopant molecules in the emitting layer with single host, while, via both dopant and host molecules when their energy levels were well aligned. Conditions for reduction of driving voltage and enhanced efficiency of red PHOLED were obtained with mixed host structure. In the end, we fabricated the OLEDs by the physical blending method. The device had a corresponding color change from blue through white change to yellow with the increase in the proportion of rubrene blend, and the brightness and current efficiency of the devices also showed regular changes with the voltage. The method can be simplified the preparation technology of the OLEDs.
OLEDs have some disadvantages, such as complex production process, shorter life, lower rate, etc. We find that OLEDs based on the Zn metal complexes have good photoelectric performance by the experiments. And Zn metal complexes we used are not only the hole-transporting materials but also the luminescence materials. These multi-functional organic electroluminescent materials have been attracted more and more people. We also attempt to synthesis the Zn metal complex in the dissertation. In addition, we use the phosphorescent sensitization of the Ir metal complex and different methods, such as the mixed host method and physical blending method to further improve the photoelectric performance of the OLEDs. They are the significance of the dissertation.
首先,研究了新型锌金属配合物发光材料FHQZn、BFHQZn、CzHQZn和MCzHQZn光电性能,验证了这四种锌金属配合物材料具有一定的空穴传输特性和发黄光特性。在此基础上,采用这四种发光材料分别制备了不同结构的器件。其中以CzHQZn材料制备了性能最好的WOLED,该器件结构为ITO/2T-NATA(22 nm)/ CzHQZn(18 nm)/NPBX(5 nm)/ADN(27 nm)/BCP(8 nm)/Alq3(20 nm)/LiF(0.5 nm)/Al。器件的最大亮度为6416 cd/m2(13V),最大发光效率为1.46 cd/A(10V),器件的色坐标由10V时的(0.30,0.31)到13V时的(0.28,0.30)几乎没变。另外,采用简单的水热法合成了一种新型配合物Zn(C19H12N4)2(C7H4O6S)H2O。研究发现,在晶体中晶胞之间通过氢键形成了三维超分子结构,芳环之间的π-π相互作用加固了晶体的结构。
其次,研究了铱金属配合物Ir(ppy)3的磷光敏化作用,详细地讨论了其磷光敏化作用对有机发光器件光电特性的改善。利用Ir(ppy)3分别敏化rubrene、ADN、CzHQZn而制作了白光或黄光器件。研究发现,敏化剂Ir(ppy)3能有效地提高材料的发光效率和亮度,磷光敏化作用的机理是通过磷光敏化剂从母体获得的能量通过共振转移的Forster机制传递给了荧光受主,使其被激发并辐射失活发射出荧光。
第三,研究了铱金属配合物Ir(piq)3的光电性能,采用Ir(piq)3为客体材料,使母客体能级匹配,载流子同时通过母体和客体进行传输,从而制备了具有混合母体结构的红色磷光器件。这种结构的器件使其启亮电压得到显著降低,发光效率得到有效提高。另外,采用物理共混方法来制备器件,研究发现随着rubrene共混比例的增加,器件的色度发生相应的改变,由蓝光经过白光变化到黄光,器件的亮度和电流效率也随电压呈现规律性的变化。该方法有利于简化有机电致发光器件的制备工艺,为实现产业化奠定了一定的基础。
有机电致发光存在生产工艺复杂、寿命不长、成品率较低等问题,通过研究可知,利用这种锌配合物材料制备的发光器件其发光特性较好,本身它也是集空穴传输和发光特性于一体的发光材料,这种多功能于一身的发光材料的开发和研制吸引更多的科技工作者。我们自己也尝试着通过水热法合成了一种锌配合物。另外,为了进一步提高器件的整体性能,利用铱配合物的磷光敏化作用及混合母体、物理共混等方法来提高器件的各项参数,这也是论文研究意义所在。
Organic electroluminescence, as new research field, has been a hot subject in flat panel displays and attracted more and more people. The organic luminous materials are the basis and core of the organic electroluminescence. Now, the new and high efficient organic luminous materials and their mechanisms are required as a result of the higher and higher technology for information display. Organic electroluminescence is by itself a subject relate to chemistry, material, physics, electronics etc., and need people to investigate it from material design and synthesis, luminescence process and mechanism, etc. The main points for this thesis are to research the photoelectric performance and phosphorescent sensitization of metal complexes (Zn and Ir), and analyse the effect of experiment parameter on the photoelectric performance. Finally, the significant results are given in the dissertation.
Firstly, we researched the luminescence performances of metal complexes FHQZn, BFHQZn, CzHQZn and MCzHQZn. The results showed that these metal complexes were yellow luminescence material with a certain hole-transporting characteristics. Base on above research, we finally fabricated the OLEDs with the four metal complexes materials. Among of them, the OLED with the structure of ITO/2T-NATA (22 nm)/CzHQZn (18 nm)/NPBX (5 nm)/ADN (27 nm)/BCP (8 nm)/Alq3(20 nm)/LiF (0.5 nm)/Al had the best luminescence performance with the CzHQZn material. The results showed the WOLED with a maximum luminous efficiency of 1.46 cd/A (at 10 V) and a maximum luminance of 6416 cd/m2 (at 13 V) was achieved. The CIE coordinates of device were from (0.30,0.31) for 10 V to (0.28,0.30) for 13 V, and they were stable on the voltages. In addition, we synthesized a new metal compoud of Zn(C19H12N4)2(C7H4O6S)H2O. The results showed the 3 d supramolecular structure was formed by hydrogen bonding by the unit cells, and theπ-πinteraction was strengthened the crystal structure.
Secondly, we researched the phosphorescent sensitization of the metal complexes Ir(ppy)3. And we mainly discussed the effect of phosphorescent sensitization on the luminescence performance of the OLEDs. At the first, the phosphorescent sensitizer of Ir(ppy)3 sensitized rubrene, ADN and CzHQZn materials were researched. The results showed the phosphorescent sensitizer of Ir(ppy)3 could improved the luminous efficiency and luminance of the luminescence materials. The energy of Ir(ppy)3, which from the host, had been transferred to acceptor by the Forster mechanism. Then it would be excitated and radiation deactivation in order to emit the fluorescence.
Thirdly, we researched the photoelectric performance of the metal complex Ir(piq)3. In the system, the carriers transport via Ir(piq)3 dopant molecules in the emitting layer with single host, while, via both dopant and host molecules when their energy levels were well aligned. Conditions for reduction of driving voltage and enhanced efficiency of red PHOLED were obtained with mixed host structure. In the end, we fabricated the OLEDs by the physical blending method. The device had a corresponding color change from blue through white change to yellow with the increase in the proportion of rubrene blend, and the brightness and current efficiency of the devices also showed regular changes with the voltage. The method can be simplified the preparation technology of the OLEDs.
OLEDs have some disadvantages, such as complex production process, shorter life, lower rate, etc. We find that OLEDs based on the Zn metal complexes have good photoelectric performance by the experiments. And Zn metal complexes we used are not only the hole-transporting materials but also the luminescence materials. These multi-functional organic electroluminescent materials have been attracted more and more people. We also attempt to synthesis the Zn metal complex in the dissertation. In addition, we use the phosphorescent sensitization of the Ir metal complex and different methods, such as the mixed host method and physical blending method to further improve the photoelectric performance of the OLEDs. They are the significance of the dissertation.
引文
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