基于溶液处理的有机半导体器件及其应用
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摘要
有机发光二极管（organic light-emitting diodes, OLEDs），具有自发光、响应快、全固态、制备工艺简单、宽视角、超薄、耐高低温、柔性等优点，被誉为最理想和最有潜力的下一代显示技术。有机电致发光显示（OLED）可分为小分子发光显示（SMOLED）和聚合物发光显示（PLED）两种形式。SMOLED起步较早，但需要比较昂贵的真空和掩模设备，生产成本相对较高，而PLED一般采用溶液加工方式制备薄膜，具有低成本的优势。
高质量聚合物薄膜的制备是PLED器件制作的关键。旋涂法无疑是最简便快捷的，而且成膜质量好。单色显示屏可以用旋涂法制备，但是全彩显示屏要用到微图案化技术，分别沉积三种不同颜色的电致发光聚合物。目前最有前途的方法就是喷墨打印。
喷墨打印彩色图案化技术可以通过调整溶剂的挥发性来得到厚度均匀的膜层。这种非接触式打印方式避免了对功能溶液的接触性污染，而且能极大地节省昂贵的发光材料，因此在PLED制造领域已被确认为向产业化发展的主流技术。在喷墨打印制备全彩PLED显示屏过程中，如何配置可打印的墨水，如何选择溶剂调节参数控制液滴干燥成膜的过程形成均匀的薄膜是制备高性能显示屏的关键。我们将可溶性小分子溶液与聚合物溶液共混调节打印溶液的特性，同时利用高低沸点溶剂共混的方法有效地抑制了咖啡环现象。通过将共轭结构的树枝状蓝色荧光化合物与蓝光材料ADS329BE按照一定比例共混来调节蓝光能量转移层的表面能，改善了液滴在像素坑内的成膜，得到了均匀铺展的膜层，提高了像素的发光面积和显示屏性能。
近年来，半导体纳米材料因为它们在纳米/微米集成光电器件应用方面展现出的巨大潜力吸引了无数的吸引力。自组装有机一维纳米晶体结构也因为它们可以通过分子设计调节电学和光学性质、器件制备成本低、操作简单逐渐成为高效有机场效应晶体管，高灵敏光探测器件的重要构成要素。但是目前大多数的工作都集中在FET方面，关于有机一维纳米结构光导器件的工作较少有见报道，而已报道的研究重点也更多偏向新分子的设计与合成。
在这里，我们对化合物1的自组装条件进行优化，得到性能优越的有机一维纳米线单晶；接着通过对有机半导体材料和衬底之间的界面进行修饰，即在二者间旋涂PMMA和PS介电层，最终得到了目前已报道的最高性能的基于有机纳米/微米结构的光探测器件。光导增益相比之前提高到1.3×10~4，电场2×10~6V下得到的响应度为4,372A W~(-10，最高开关比高达10~4。讨论得出结论，这种相当高的光导增益主要得益于引入介电层之后，材料的载流子迁移率和寿命都得到了提高。
Owing to the advantages of self light-emission, fast response, solid thin film device, easyfabrication, wide view-angle, thin form factor, wide operation temperature, flexibility, etc.,organic light-emitting diodes (OLEDs) are considered as the next generation displaytechnology.
There are two variations of the OLED display technology. One is so called “smallmolecule”(SMOLED) technology. The other is “conjugated polymer”(PLED) basedtechnology. Though SMOLED technology has become the most popular technology in theflat panel display, its fabrication requires vacuum deposition with shadow mask, leading to ahigh production cost. PLED are usually fabricated by solution process, such as spin-coating,dip-coating, screen printing, slot-die coating, and inkjet printing. The solution process can becarried out at low or room temperature without any shadow mask, which are more promisingfor large size, high definition, and high resolution displays.
High quality film formation is critical in PLED device. The simplest process to achievehigh quality film is spin-coating. Spincoating is fit for fabricating monochrome PLED display.However, since we need to deposive three kind of polymer of different color to specific pixelsrepectively to achieve micro-patterning of full color display, the most promising option isinkjet printing.
Inkjet printing is of great potential to patter colors for full color PLED display with theadvantages of material savings, low cost, and being environmentally friendly. Since inkjetprinting is a non-contact printing method, it avoids contamination to the functional layer. Toachieve uniform, pin-hole free, optical-quality solid films by inkjet printing, the most criticalprocess is to achieve high quality jetted solution drops. The quality of the drops depend on themolecular weight of the polymer, and the viscosity and the surface tension of the solution. Weblended the conjugated polymer with solution-procesable small molecule to obtain inkjetprintable inks with high performance. Moreover, the coffee ring was successfully suppressedby using the mixture of high and low boiling point solvents, leading to a more uniform filmand a larger fill factor for PLED displays.
In recent years, semiconducting nanostructures have attracted enormous attention fortheir potential applications in the integrated nano-or micro-optoelectronics. Self-assembled,crystalline, organic, one-dimensional (1D) nanostructures become promising building blocksfor high-performance organic field-effect transistors (FETs), and highly sensitivephotodetectors, due to their tunable electronic and optical properties via molecular design, low-cost device fabrication, and process simplicity. While most efforts have beenconcentrated on FETs, only a few photoconductive organic1D nanostructures have beenreported, most of which focus on the design and synthesis of new molecules. By combining abetter crystalline structure with proper surface engineering, i.e. coating a dielectric layer ofPMMA between the substrate and the organic semiconductor, we achieved the world-recordperformance of organic nano/micro-structure based photodetectors with two-terminal devicestructure. The photoconductivity gain is enhanced to1.3×10~4, and the responsivity isimproved to4,372A W-1at the field of about2×106V m~(-1). The highest on/off ratio reaches104. The extremely high gain is attributed to the high mobility and the long photo carrier’slifetime induced by the dielectric layer.
高质量聚合物薄膜的制备是PLED器件制作的关键。旋涂法无疑是最简便快捷的，而且成膜质量好。单色显示屏可以用旋涂法制备，但是全彩显示屏要用到微图案化技术，分别沉积三种不同颜色的电致发光聚合物。目前最有前途的方法就是喷墨打印。
喷墨打印彩色图案化技术可以通过调整溶剂的挥发性来得到厚度均匀的膜层。这种非接触式打印方式避免了对功能溶液的接触性污染，而且能极大地节省昂贵的发光材料，因此在PLED制造领域已被确认为向产业化发展的主流技术。在喷墨打印制备全彩PLED显示屏过程中，如何配置可打印的墨水，如何选择溶剂调节参数控制液滴干燥成膜的过程形成均匀的薄膜是制备高性能显示屏的关键。我们将可溶性小分子溶液与聚合物溶液共混调节打印溶液的特性，同时利用高低沸点溶剂共混的方法有效地抑制了咖啡环现象。通过将共轭结构的树枝状蓝色荧光化合物与蓝光材料ADS329BE按照一定比例共混来调节蓝光能量转移层的表面能，改善了液滴在像素坑内的成膜，得到了均匀铺展的膜层，提高了像素的发光面积和显示屏性能。
近年来，半导体纳米材料因为它们在纳米/微米集成光电器件应用方面展现出的巨大潜力吸引了无数的吸引力。自组装有机一维纳米晶体结构也因为它们可以通过分子设计调节电学和光学性质、器件制备成本低、操作简单逐渐成为高效有机场效应晶体管，高灵敏光探测器件的重要构成要素。但是目前大多数的工作都集中在FET方面，关于有机一维纳米结构光导器件的工作较少有见报道，而已报道的研究重点也更多偏向新分子的设计与合成。
在这里，我们对化合物1的自组装条件进行优化，得到性能优越的有机一维纳米线单晶；接着通过对有机半导体材料和衬底之间的界面进行修饰，即在二者间旋涂PMMA和PS介电层，最终得到了目前已报道的最高性能的基于有机纳米/微米结构的光探测器件。光导增益相比之前提高到1.3×10~4，电场2×10~6V下得到的响应度为4,372A W~(-10，最高开关比高达10~4。讨论得出结论，这种相当高的光导增益主要得益于引入介电层之后，材料的载流子迁移率和寿命都得到了提高。
Owing to the advantages of self light-emission, fast response, solid thin film device, easyfabrication, wide view-angle, thin form factor, wide operation temperature, flexibility, etc.,organic light-emitting diodes (OLEDs) are considered as the next generation displaytechnology.
There are two variations of the OLED display technology. One is so called “smallmolecule”(SMOLED) technology. The other is “conjugated polymer”(PLED) basedtechnology. Though SMOLED technology has become the most popular technology in theflat panel display, its fabrication requires vacuum deposition with shadow mask, leading to ahigh production cost. PLED are usually fabricated by solution process, such as spin-coating,dip-coating, screen printing, slot-die coating, and inkjet printing. The solution process can becarried out at low or room temperature without any shadow mask, which are more promisingfor large size, high definition, and high resolution displays.
High quality film formation is critical in PLED device. The simplest process to achievehigh quality film is spin-coating. Spincoating is fit for fabricating monochrome PLED display.However, since we need to deposive three kind of polymer of different color to specific pixelsrepectively to achieve micro-patterning of full color display, the most promising option isinkjet printing.
Inkjet printing is of great potential to patter colors for full color PLED display with theadvantages of material savings, low cost, and being environmentally friendly. Since inkjetprinting is a non-contact printing method, it avoids contamination to the functional layer. Toachieve uniform, pin-hole free, optical-quality solid films by inkjet printing, the most criticalprocess is to achieve high quality jetted solution drops. The quality of the drops depend on themolecular weight of the polymer, and the viscosity and the surface tension of the solution. Weblended the conjugated polymer with solution-procesable small molecule to obtain inkjetprintable inks with high performance. Moreover, the coffee ring was successfully suppressedby using the mixture of high and low boiling point solvents, leading to a more uniform filmand a larger fill factor for PLED displays.
In recent years, semiconducting nanostructures have attracted enormous attention fortheir potential applications in the integrated nano-or micro-optoelectronics. Self-assembled,crystalline, organic, one-dimensional (1D) nanostructures become promising building blocksfor high-performance organic field-effect transistors (FETs), and highly sensitivephotodetectors, due to their tunable electronic and optical properties via molecular design, low-cost device fabrication, and process simplicity. While most efforts have beenconcentrated on FETs, only a few photoconductive organic1D nanostructures have beenreported, most of which focus on the design and synthesis of new molecules. By combining abetter crystalline structure with proper surface engineering, i.e. coating a dielectric layer ofPMMA between the substrate and the organic semiconductor, we achieved the world-recordperformance of organic nano/micro-structure based photodetectors with two-terminal devicestructure. The photoconductivity gain is enhanced to1.3×10~4, and the responsivity isimproved to4,372A W-1at the field of about2×106V m~(-1). The highest on/off ratio reaches104. The extremely high gain is attributed to the high mobility and the long photo carrier’slifetime induced by the dielectric layer.
引文
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