全溶液法制备OLED显示屏及相关研究
发布时间：2019-06-03 20:27
【摘要】：有机发光二极管显示器(OLED)具有自发光、强对比、大色域、广视角、快响应、高效率、低电压等优点,而且适用环境广、面板厚度薄、制程简单、可制作大尺寸与柔性面板,被誉为下一代的“梦幻显示器”。“全溶液制备”技术被认为是OLED进一步降低成本和实现大面积的有效途径,但目前国际上溶液制备的主要工作和成果集中在有机功能层上,尚未有采用印刷金属电极制备OLED显示屏的相关技术,因此还不能称之为OLED的“全溶液制备”技术。采用完全省去真空蒸镀环节的“全溶液制备”技术开发显示屏,是一项崭新的科学领域,更是一个世界级的技术难题。 遴选出高发光效率的材料是全溶液法制备OLED显示屏的前提。固体有机薄膜的光致发光外量子效率(PLQE)是有机荧光材料最重要的性能参数之一。我们成功地设计了一套可靠的实验方法,通过直接推算样品吸收的光子数和发射的光子数,来测量有机发光材料的PLQE。由于取消了测定样品吸收率的步骤并革新了算法思想,我们的方法不仅减少了操作步骤和数据处理,更避免了复杂模型和额外假设所可能带来的系统误差。我们的方法可以广泛应用于大部分有机发光材料,包括一些其他方法无法测量或者需要复杂数据处理的样品,例如高散射薄膜样品。结果显示我们的方法能利用更简单的设备,更容易的操作,更少的数据处理来得到更准确的实验结果和更小的偶然误差区间。此外,有机材料的PLQE在不同衬底上的测量结果,也显示了位于金属/有机界面的导体对于PLQE具有强烈的q 灭效应。 立足于高效率的聚合物发光材料,通过结合多功能缓冲层的制备和精细阴极的加工,我们首次成功实现了全溶液法制备高分辨率无源聚合物OLED显示屏。与其它的印刷方法和印刷材料不同,喷墨打印制备的导电纳米颗粒阴极能保证高分辨率的阴极图案,以及精细的阴极线的良好导通,且加工过程中不会对有机层产生机械压力。缓冲层位于印刷阴极和发光层之间,由水/醇溶性共轭聚合物——聚[9,9-二辛基芴-9,9-双(N,N-二甲基胺丙基)芴](PFNR_2)与一种可固化的环氧树脂粘合剂共混而成。它能阻止溶剂侵蚀,保证电子注入,并能与阴极墨水保持适当的亲和能力。交联结构的缓冲层不仅提升了器件的性能,尤其是极大地降低了漏电流,还导致了一种“线性η-J衰减”的有趣现象,由之能推导出实用的结果。制得的红、绿、蓝单色OLED显示屏和全彩色OLED显示屏像素结构为96×3×64,无坏点坏线。经过最优化的烧结工序后,纳米银墨水形成连续性好、无缺陷、低电阻的阴极行,且无任何形变。在红、绿、蓝显示中,电流效率分别为0.62、4.38、0.93 cd/A,色坐标分别为(0.63, 0.37)、(0.39, 0.57)、(0.18, 0.16)。全溶液加工消除了对高真空热蒸镀阴极金属的依赖,为实现工业化的“卷对卷”方式生产平板显示器铺平了道路。 在喷墨打印OLED发光材料和电极材料的研究中我们发现,固液界面的润湿性问题是全溶液技术面临的一项重要科学问题。我们以超疏水表面上的水滴这种自然界最常见、最典型的不浸润现象为研究对象,对润湿性问题的本质进行了系统地观测和分析。虽然人们普遍认为水和超疏水表面之间囚陷着空气,但一直未能有直接的实验证据表明这一微观层次的空气的存在。早在1944年Wenzel态和Cassie态就已被提出并用于分析超疏水表面,但也由于对包埋着的界面缺乏直接、定量的观测,对于不同情况下究竟哪种态占主导一直陷于热议。我们利用激光共聚焦扫描显微镜,首次实现了一种原位的、无损的方法来对水滴与超疏水表面间的包埋界面进行直接的三维成像。其界面间囚陷着的一层十微米级的空气垫层被定量观测,并被证明与超低流动阻力有关。一直以来都无法观测和辨别的Wenzel态和Cassie态,可以通过这种技术来清楚地观测。我们的这种新观测方法,可用于对发生在气液固界面间的复杂现象和微妙过程进行探索和调节,为相应的基础研究和工业应用开辟了一条新的道路。 全溶液法制备OLED的研究中最关键的技术在于导电阴极的溶液加工,由于目前最适合高分辨率阴极加工的是喷墨打印工艺,因此开发和优化出适用的纳米银导电墨水也就成为首要任务之一。我们成功发展了一种环境友好的“绿色”溶液工艺,来实现多晶结构的纳米银多面体的大规模、高产率合成。通过使用单宁酸和聚乙烯基吡咯烷酮(PVP),高质量的纳米银多面体可在水相一锅煮反应中生成,而不需任何模板或辅助剂。将生成的纳米银颗粒在不同的溶剂中分散,可得到能满足不同需要的各种导电墨水。使用导电墨水在刚性和柔性衬底上退火,可以得到高导电的纳米银膜。在玻璃衬底上的银膜样品能实现的最高导电率为8.5×104 S·cm~(-1)。而在PET衬底上,即使退火温度仅为160°C,银膜的导电率也能达到3.6×104 S·cm~(-1)。弯折测试表明,我们的纳米银膜在经过50,000次的反复弯折后,仍保持导电率基本不变。由于能制成高机械强度、高导电率、低退火温度、长寿命的纳米银膜,我们研制的导电墨水在印刷电子学和柔性电子器件中具有广阔应用。至此,我们实现了全溶液法制备OLED中从上游原材料到下游整机的整个生产链都在本实验室内完成,并将印刷阴极的成本降为使用进口导电墨水时的1/10。
[Abstract]:The organic light-emitting diode display (OLED) has the advantages of self-luminescence, strong contrast, large color gamut, wide viewing angle, fast response, high efficiency, low voltage and the like, and is wide in application environment, thin in panel thickness and simple in process, and can be used for manufacturing large-size and flexible panels, and is regarded as the next-generation "Dream display". The "full solution preparation" technology is considered to be an effective way for the OLED to further reduce the cost and realize large area, but the main work and the result of the solution preparation at present are concentrated on the organic functional layer, and the related technology for preparing the OLED display screen by using the printed metal electrode is not provided, Therefore, it is also not possible to refer to the "full solution preparation" technology of the OLED. It is a brand-new field of science and a world-class technical problem by using the "full solution preparation" technology development display screen which completely omits the vacuum evaporation process. The method for selecting high light-emitting efficiency by the method of the invention is that the OLED display screen is prepared by a full-solution method, The photoluminescence external quantum efficiency (PLQE) of the solid organic thin film is the most important performance parameter of the organic fluorescent material. We have successfully designed a set of reliable experimental methods to measure the PL of the organic light-emitting material by directly calculating the number of photons absorbed by the sample and the number of photons emitted. QE. Our approach not only reduces operational steps and data processing, but also avoids the system that is likely to be brought about by complex models and additional assumptions, as a result of the elimination of the steps to determine the absorbance of the sample and to innovate the algorithm's mind The error. Our approach can be widely used in most of the organic light-emitting materials, including some other methods that are not measurable or require complex data processing, such as high-scattering films The results show that our method can take advantage of simpler equipment, easier operation and less data processing to get more accurate experimental results and less even error in addition, the measurement of the PLQE of the organic material on different substrates also shows that the conductor located at the metal/ machine interface has a strong q-out for the PLQE Based on the high-efficiency polymer light-emitting material, by combining the preparation of the multi-function buffer layer and the processing of the fine cathode, we successfully realized the high-resolution passive polymer OL by the full solution method. the conductive nano-particle cathode prepared by the ink-jet printing can ensure the high-resolution cathode pattern and the fine cathode line in good conduction, and the organic layer can not be produced during the processing process, The buffer layer is located between the printing cathode and the light-emitting layer, and is bonded to a curable epoxy resin by a water/ alcohol-soluble co-polymer _ poly[9,9-dioctylphenyl-9,9-bis (N, N-dimethylamine propyl) benzene] (PFNR _ 2) It can prevent the solvent from being eroded, ensure the electron injection and keep the cathode ink suitable. The buffer layer of the cross-linking structure not only improves the performance of the device, but also greatly reduces the leakage current, and also leads to an interesting phenomenon of the "linear J-J attenuation", which can be deduced The prepared red, green, blue single-color OLED display screen and the full-color OLED display screen pixel structure are 96-3-64, the nano-silver ink forms a cathode row with good continuity, no defect and low resistance after the optimized sintering process, and The current efficiency is 0.62, 4.38, 0.93 cd/ A, respectively (0.63, 0.37), (0.39, 0.57), (0.18, 0.16). The full solution processing eliminates the dependence on the cathode metal for high vacuum thermal evaporation, and the flat panel display is produced for realizing the industrial "volume-to-volume" mode. The road is paved. In the study of ink-jet printing of OLED light-emitting materials and electrode materials, we have found that the wetting problem of the solid-liquid interface is the whole solution technology. The most common and typical non-wetting phenomenon of water droplets on the super-hydrophobic surface is the study object, and the essence of the wettability problem is Systematic observation and analysis. Although it is widely believed that air is trapped between water and superhydrophobic surfaces, there has been no direct experimental evidence that this micro- The existence of the air in the hierarchy has been proposed and used for the analysis of the super-hydrophobic surface in the Wenzel state and the Cassie state in 1944, but also because of the lack of direct and quantitative observation of the embedded interface, which state accounts for different situations The lead has been in hot debate. We use the laser confocal scanning microscope for the first time to realize an in-situ and non-destructive method to feed the embedded interface between the water droplets and the super-hydrophobic surface. a direct three-dimensional imaging. An air cushion layer of a ten-micron level that is trapped between its interfaces is quantitatively observed and is demonstrated to Ultra-low flow resistance. It has been impossible to observe and distinguish the Wenzel state and the Cassie state all the time, and this can be done by this This new method of observation can be used to explore and adjust the complex phenomena and delicate processes occurring in the gas-liquid solid interface, and to open the corresponding basic research and industrial application. A new road is developed. The most critical technique in the preparation of OLED by the solution process is that the solution of the conductive cathode is processed, and since the most suitable for high-resolution cathode processing is the ink-jet printing process, the applicable nano-silver conductive ink is developed and optimized. Water has also become one of the top priorities. We have successfully developed an environment-friendly "green" solution process to realize the nano-silver multi-face of the polycrystalline structure The high-quality nano-silver polyhedra can be generated in a one-pot boiling reaction of the water phase by using tannic acid and polyethylene-based polydioxanone (PVP), and the generated nano-silver particles are dispersed in different solvents, so that the nano-silver particles can be obtained, various conductive inks are required to be annealed on a rigid and flexible substrate using conductive ink, The high conductivity of the silver film sample on the glass substrate is 8.5%. 04S 路 cm ~ (-1). On the PET substrate, even if the annealing temperature is only 160 掳 C, the conductivity of the silver film can reach 3.6%. 04S 路 cm ~ (-1). The bending test shows that our nano-silver film has been bent over 50,000 times. because the nano-silver film with high mechanical strength, high conductivity, low annealing temperature and long service life can be made, the conductive ink developed by the method has the advantages of high mechanical strength, high conductivity, low annealing temperature and long service life, In that electronic device, the whole production chain from the upstream raw material to the downstream complete machine is complete in the laboratory, and the cost of the printing cathode is reduced to the use of the whole production chain of the whole solution method for preparing the OLED from the upstream raw material to the downstream complete machine.
【学位授予单位】：华南理工大学
【学位级别】：博士
【学位授予年份】：2011
【分类号】：TN383.1
本文编号：2492204
[Abstract]:The organic light-emitting diode display (OLED) has the advantages of self-luminescence, strong contrast, large color gamut, wide viewing angle, fast response, high efficiency, low voltage and the like, and is wide in application environment, thin in panel thickness and simple in process, and can be used for manufacturing large-size and flexible panels, and is regarded as the next-generation "Dream display". The "full solution preparation" technology is considered to be an effective way for the OLED to further reduce the cost and realize large area, but the main work and the result of the solution preparation at present are concentrated on the organic functional layer, and the related technology for preparing the OLED display screen by using the printed metal electrode is not provided, Therefore, it is also not possible to refer to the "full solution preparation" technology of the OLED. It is a brand-new field of science and a world-class technical problem by using the "full solution preparation" technology development display screen which completely omits the vacuum evaporation process. The method for selecting high light-emitting efficiency by the method of the invention is that the OLED display screen is prepared by a full-solution method, The photoluminescence external quantum efficiency (PLQE) of the solid organic thin film is the most important performance parameter of the organic fluorescent material. We have successfully designed a set of reliable experimental methods to measure the PL of the organic light-emitting material by directly calculating the number of photons absorbed by the sample and the number of photons emitted. QE. Our approach not only reduces operational steps and data processing, but also avoids the system that is likely to be brought about by complex models and additional assumptions, as a result of the elimination of the steps to determine the absorbance of the sample and to innovate the algorithm's mind The error. Our approach can be widely used in most of the organic light-emitting materials, including some other methods that are not measurable or require complex data processing, such as high-scattering films The results show that our method can take advantage of simpler equipment, easier operation and less data processing to get more accurate experimental results and less even error in addition, the measurement of the PLQE of the organic material on different substrates also shows that the conductor located at the metal/ machine interface has a strong q-out for the PLQE Based on the high-efficiency polymer light-emitting material, by combining the preparation of the multi-function buffer layer and the processing of the fine cathode, we successfully realized the high-resolution passive polymer OL by the full solution method. the conductive nano-particle cathode prepared by the ink-jet printing can ensure the high-resolution cathode pattern and the fine cathode line in good conduction, and the organic layer can not be produced during the processing process, The buffer layer is located between the printing cathode and the light-emitting layer, and is bonded to a curable epoxy resin by a water/ alcohol-soluble co-polymer _ poly[9,9-dioctylphenyl-9,9-bis (N, N-dimethylamine propyl) benzene] (PFNR _ 2) It can prevent the solvent from being eroded, ensure the electron injection and keep the cathode ink suitable. The buffer layer of the cross-linking structure not only improves the performance of the device, but also greatly reduces the leakage current, and also leads to an interesting phenomenon of the "linear J-J attenuation", which can be deduced The prepared red, green, blue single-color OLED display screen and the full-color OLED display screen pixel structure are 96-3-64, the nano-silver ink forms a cathode row with good continuity, no defect and low resistance after the optimized sintering process, and The current efficiency is 0.62, 4.38, 0.93 cd/ A, respectively (0.63, 0.37), (0.39, 0.57), (0.18, 0.16). The full solution processing eliminates the dependence on the cathode metal for high vacuum thermal evaporation, and the flat panel display is produced for realizing the industrial "volume-to-volume" mode. The road is paved. In the study of ink-jet printing of OLED light-emitting materials and electrode materials, we have found that the wetting problem of the solid-liquid interface is the whole solution technology. The most common and typical non-wetting phenomenon of water droplets on the super-hydrophobic surface is the study object, and the essence of the wettability problem is Systematic observation and analysis. Although it is widely believed that air is trapped between water and superhydrophobic surfaces, there has been no direct experimental evidence that this micro- The existence of the air in the hierarchy has been proposed and used for the analysis of the super-hydrophobic surface in the Wenzel state and the Cassie state in 1944, but also because of the lack of direct and quantitative observation of the embedded interface, which state accounts for different situations The lead has been in hot debate. We use the laser confocal scanning microscope for the first time to realize an in-situ and non-destructive method to feed the embedded interface between the water droplets and the super-hydrophobic surface. a direct three-dimensional imaging. An air cushion layer of a ten-micron level that is trapped between its interfaces is quantitatively observed and is demonstrated to Ultra-low flow resistance. It has been impossible to observe and distinguish the Wenzel state and the Cassie state all the time, and this can be done by this This new method of observation can be used to explore and adjust the complex phenomena and delicate processes occurring in the gas-liquid solid interface, and to open the corresponding basic research and industrial application. A new road is developed. The most critical technique in the preparation of OLED by the solution process is that the solution of the conductive cathode is processed, and since the most suitable for high-resolution cathode processing is the ink-jet printing process, the applicable nano-silver conductive ink is developed and optimized. Water has also become one of the top priorities. We have successfully developed an environment-friendly "green" solution process to realize the nano-silver multi-face of the polycrystalline structure The high-quality nano-silver polyhedra can be generated in a one-pot boiling reaction of the water phase by using tannic acid and polyethylene-based polydioxanone (PVP), and the generated nano-silver particles are dispersed in different solvents, so that the nano-silver particles can be obtained, various conductive inks are required to be annealed on a rigid and flexible substrate using conductive ink, The high conductivity of the silver film sample on the glass substrate is 8.5%. 04S 路 cm ~ (-1). On the PET substrate, even if the annealing temperature is only 160 掳 C, the conductivity of the silver film can reach 3.6%. 04S 路 cm ~ (-1). The bending test shows that our nano-silver film has been bent over 50,000 times. because the nano-silver film with high mechanical strength, high conductivity, low annealing temperature and long service life can be made, the conductive ink developed by the method has the advantages of high mechanical strength, high conductivity, low annealing temperature and long service life, In that electronic device, the whole production chain from the upstream raw material to the downstream complete machine is complete in the laboratory, and the cost of the printing cathode is reduced to the use of the whole production chain of the whole solution method for preparing the OLED from the upstream raw material to the downstream complete machine.
【学位授予单位】：华南理工大学
【学位级别】：博士
【学位授予年份】：2011
【分类号】：TN383.1
【引证文献】
相关博士学位论文 前2条
1 薛善锋;有机荧光分子的溶液加工薄膜及器件[D];吉林大学;2012年
2 冯姝;湿法制备的有机电致发光小分子薄膜性质研究[D];清华大学;2012年
相关硕士学位论文 前3条
1 吴绪虎;几种微纳米环境功能材料的水热法制备、表征及应用[D];安徽大学;2012年
2 柏松虎;基于金属氧化物TFT的AMOLED显示屏驱动技术的研究[D];华南理工大学;2012年
3 王春阜;基于氧化物TFT技术的AMOLED显示屏驱动与测试研究[D];华南理工大学;2013年
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