溶液加工有机半导体光电器件的研究
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摘要
有机发光二极管（organic light-emitting diode，OLED）与CRT为代表的第一代显示器和以LCD为代表的第二代显示器相比，具有自主发光、重量轻、厚度薄、无视角、能耗低、响应速度快、耐高低温、柔性可弯曲等优点，近年来受到人们的广泛青睐，被认为是最理想和最有潜力的下一代平板显示技术。
根据发光材料分子量的不同，OLED显示屏可以分为小分子材料显示屏（SMOLED）和聚合物材料显示屏（PLED）。SMOLED起步早，但由于需要昂贵的真空蒸镀设备和高精度的掩膜设备和对位系统，市场成本相对较高。PLED结构简单，在常压下通过各种湿法制备技术即可成膜，不需要昂贵的真空设备，可实现低价格，适用于大型玻璃基板，生产效率高，具有良好的发展前景。
目前，实现OLED全彩化的技术有真空蒸镀掩膜法、喷墨打印技术、激光转移技术、色转换法和彩膜法等。喷墨打印具有图案与文字制作能力、可制作大面积器件、大量节省材料，适用于柔性和玻璃基板、对基板缺陷不敏感、光色均匀等优点，是未来实现PLED全彩化的主流方法。在喷墨打印PLED全彩显示屏的过程中，可打印墨水的调制、液滴的调控、薄膜均匀性及器件结构优化等是制备高性能显示屏的关键。我们采用hybridinkjet printing（HIJP）技术，先在PEDOT层上旋涂一薄层蓝光材料，接着分别喷墨打印红光和绿光材料，得到致密、均匀、针孔少的发光层薄膜，通过有效的能量转移，最后实现了RBG三基色的有效发射。其次，通过往红光材料PFO-DHTBT中掺入少量的P-PPV，有效提高了红光的亮度和效率；另外，通过选用分子量相对较小的P-PPV批次材料，调节出稳定的液滴。通过对相关问题的解决，我们成功制备了1.5英寸无缺陷的聚合物全彩显示屏。
太阳能具有清洁环保、无污染、利用价值高、干净、无公害等特点，是一种取之不尽、用之不竭的理想新能源。太阳电池就是通过光电转换技术把太阳光中的能量转化为电能的。因为有机太阳电池的原料来源广泛且价格便宜、加工性能好、可进行物理改性、电池制作多样化、轻薄和可弯曲等显著优点，致使有机太阳电池尤其是聚合物太阳电池有望成为硅基无机半导体的替代品，并成为国内外研究的热点。
Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)（PEDOT:PSS）作为空穴传输层在有机光伏器件中得到广泛应用，从而获得高的能量转换效率。但是通常使用的PEDOT（AI4083）具有一定的酸性，会腐蚀ITO，从而降低器件的能量转换效率及稳定性。我们采用pH值中性的PEDOT取代酸性PEDOT制备聚合物太阳电池。通过对中性PEDOT薄膜进行简单的表面处理，使得处理后的中性PEDOT器件的效率比未处理的中性PEDOT器件效率提高了一倍多，且稍高于酸性PEDOT器件的效率。同时通过X射线光电子能谱测试分析发现，不论是在空气中存放一段时间的酸性PEDOT样品，还是同样条件下存放的以酸性PEDOT薄膜为基底的活性层样品，它们的样品表面均可探测到In元素。而在相应的中性PEDOT样品和活性层样品中，均未检测到In的存在，这说明中性PEDOT有效抑制了In对空穴传输层和活性层的扩散。最后，与酸性PEDOT器件相比，中性PEDOT器件的寿命提高了一倍多。
Organic light-emitting diode (OLED for short), compared to the first generation displayrepresented with the CRT and the second generation display represented by LCD, with selflight-emission, light weight, thin form factor, wide view-angle, low energy consumption, fastresponse, wide operation temperature, flexibility, etc, has been widely favored in recent years,is considered to be the most ideal and the most promising next generation flat panel displaytechnology.
According to different luminescent material molecular weight, OLED display can bedivided into small molecule materials display (SMOLED) and polymer materials display(PLED). SMOLED started early, but due to the need for expensive vacuum evaporationequipment and high precision mask and registration system, the cost is relatively high. PLEDhas simple structure, forming film under the normal pressure by a variety of wet preparationtechnologys, do not need for expensive vacuum equipment. Moreover, it is suitable for largeglass substrate, realizing low price and having high production efficiency, has gooddevelopment prospect.
At present, the realization of full color OLED technologys are vacuum evaporation maskmethod, ink-jet printing technology, laser transfer technology, color conversion method andcolor film method, etc. Ink-jet printing has many advantages, such as the design and textproduction capacity and large devices production, saving a large number of materials, suitablefor the flexible and glass substrates, not sensitive to substrate defects, light color uniform, etc.,it is the mainstream method to realizing the full-colored PLED. In the process of ink-jetprinting PLED full-color displays, printing ink modulation, regulation of the droplet, filmuniformity and optimization of device structure are the key to the preparation of highperformance display. We use hybrid inkjet printing (HIJP) technology to prapare the ink-jetprinting PLED full-color display. A thin blue emitting layer is spun on the PEDOT layerfirstly, red emitting and green emitting materials are ink-jetted into the related pixelsrespectively, and compact, uniform and pinhole less emitting layer films can be obtained.Then through effective energy transfer, the effective emitting of RBG are finally realized.Secondly, by blending the red emitting material–PFO-DHTBT with a small amount of P-PPV, the brightness and efficiency of the red emitting are improved effectively. In addition,by choosing a relatively small molecular weight of P-PPV material, the stable droplet can beobtained. By solving the related issues, we successfully made a1.5-inch PLED full-colordisplays without defects.
Solar energy is environmental, no pollution, high use value, clean, pollution-free. It is aninexhaustible, inexhaustible ideal new energy. Solar cell uses the photoelectric conversiontechnology to convert the solar energy into electricity. Because of its abroad material sourcesand cheap price, good processability, physical modification, diversification of the battery’sprocessing, thin and flexible etc, organic solar cell, especially polymer solar cell, is analternative to silicon-based inorganic semiconductor, and become the focus of research athome and abroad.
Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)（PEDOT:PSS） is widely usedin organic photovoltaic device as the hole transport layer, so as to obtain high energyconversion efficiency. But the noamal PEDOT (AI4083) is acidic, and it will etch ITO, thenreduce energy conversion efficiency and stability of device. We adopt pH neutral PEDOTreplace acid PEDOT to make polymer solar cell devices. By applied some simple processingson the surface of a neutral PEDOT film, the efficiency of the neutral PEDOT device afterprocessings is more than doubled compared to the untreated neutral PEDOT device, and isslightly higher than the efficiency of the acid PEDOT device. By X-ray photoelectronspectroscopy analysis, whether the acidic PEDOT samples which are stored in the air forsome days, or the active layer samples which use the acidic PEDOT as substrate and werestored in the same conditions, In element could be detected in the surfaces of two typesamples. And in corresponding neutral PEDOT samples and active layer samples, In elementwere not detected, it is illustrated that the neutal PEDOT can restrain the diffusion of Inelement into the hole transport layer and the active layer effectively, the lifetime of the neutralPEDOT device is more than doubled compared with the acidic PEDOT device.
根据发光材料分子量的不同，OLED显示屏可以分为小分子材料显示屏（SMOLED）和聚合物材料显示屏（PLED）。SMOLED起步早，但由于需要昂贵的真空蒸镀设备和高精度的掩膜设备和对位系统，市场成本相对较高。PLED结构简单，在常压下通过各种湿法制备技术即可成膜，不需要昂贵的真空设备，可实现低价格，适用于大型玻璃基板，生产效率高，具有良好的发展前景。
目前，实现OLED全彩化的技术有真空蒸镀掩膜法、喷墨打印技术、激光转移技术、色转换法和彩膜法等。喷墨打印具有图案与文字制作能力、可制作大面积器件、大量节省材料，适用于柔性和玻璃基板、对基板缺陷不敏感、光色均匀等优点，是未来实现PLED全彩化的主流方法。在喷墨打印PLED全彩显示屏的过程中，可打印墨水的调制、液滴的调控、薄膜均匀性及器件结构优化等是制备高性能显示屏的关键。我们采用hybridinkjet printing（HIJP）技术，先在PEDOT层上旋涂一薄层蓝光材料，接着分别喷墨打印红光和绿光材料，得到致密、均匀、针孔少的发光层薄膜，通过有效的能量转移，最后实现了RBG三基色的有效发射。其次，通过往红光材料PFO-DHTBT中掺入少量的P-PPV，有效提高了红光的亮度和效率；另外，通过选用分子量相对较小的P-PPV批次材料，调节出稳定的液滴。通过对相关问题的解决，我们成功制备了1.5英寸无缺陷的聚合物全彩显示屏。
太阳能具有清洁环保、无污染、利用价值高、干净、无公害等特点，是一种取之不尽、用之不竭的理想新能源。太阳电池就是通过光电转换技术把太阳光中的能量转化为电能的。因为有机太阳电池的原料来源广泛且价格便宜、加工性能好、可进行物理改性、电池制作多样化、轻薄和可弯曲等显著优点，致使有机太阳电池尤其是聚合物太阳电池有望成为硅基无机半导体的替代品，并成为国内外研究的热点。
Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)（PEDOT:PSS）作为空穴传输层在有机光伏器件中得到广泛应用，从而获得高的能量转换效率。但是通常使用的PEDOT（AI4083）具有一定的酸性，会腐蚀ITO，从而降低器件的能量转换效率及稳定性。我们采用pH值中性的PEDOT取代酸性PEDOT制备聚合物太阳电池。通过对中性PEDOT薄膜进行简单的表面处理，使得处理后的中性PEDOT器件的效率比未处理的中性PEDOT器件效率提高了一倍多，且稍高于酸性PEDOT器件的效率。同时通过X射线光电子能谱测试分析发现，不论是在空气中存放一段时间的酸性PEDOT样品，还是同样条件下存放的以酸性PEDOT薄膜为基底的活性层样品，它们的样品表面均可探测到In元素。而在相应的中性PEDOT样品和活性层样品中，均未检测到In的存在，这说明中性PEDOT有效抑制了In对空穴传输层和活性层的扩散。最后，与酸性PEDOT器件相比，中性PEDOT器件的寿命提高了一倍多。
Organic light-emitting diode (OLED for short), compared to the first generation displayrepresented with the CRT and the second generation display represented by LCD, with selflight-emission, light weight, thin form factor, wide view-angle, low energy consumption, fastresponse, wide operation temperature, flexibility, etc, has been widely favored in recent years,is considered to be the most ideal and the most promising next generation flat panel displaytechnology.
According to different luminescent material molecular weight, OLED display can bedivided into small molecule materials display (SMOLED) and polymer materials display(PLED). SMOLED started early, but due to the need for expensive vacuum evaporationequipment and high precision mask and registration system, the cost is relatively high. PLEDhas simple structure, forming film under the normal pressure by a variety of wet preparationtechnologys, do not need for expensive vacuum equipment. Moreover, it is suitable for largeglass substrate, realizing low price and having high production efficiency, has gooddevelopment prospect.
At present, the realization of full color OLED technologys are vacuum evaporation maskmethod, ink-jet printing technology, laser transfer technology, color conversion method andcolor film method, etc. Ink-jet printing has many advantages, such as the design and textproduction capacity and large devices production, saving a large number of materials, suitablefor the flexible and glass substrates, not sensitive to substrate defects, light color uniform, etc.,it is the mainstream method to realizing the full-colored PLED. In the process of ink-jetprinting PLED full-color displays, printing ink modulation, regulation of the droplet, filmuniformity and optimization of device structure are the key to the preparation of highperformance display. We use hybrid inkjet printing (HIJP) technology to prapare the ink-jetprinting PLED full-color display. A thin blue emitting layer is spun on the PEDOT layerfirstly, red emitting and green emitting materials are ink-jetted into the related pixelsrespectively, and compact, uniform and pinhole less emitting layer films can be obtained.Then through effective energy transfer, the effective emitting of RBG are finally realized.Secondly, by blending the red emitting material–PFO-DHTBT with a small amount of P-PPV, the brightness and efficiency of the red emitting are improved effectively. In addition,by choosing a relatively small molecular weight of P-PPV material, the stable droplet can beobtained. By solving the related issues, we successfully made a1.5-inch PLED full-colordisplays without defects.
Solar energy is environmental, no pollution, high use value, clean, pollution-free. It is aninexhaustible, inexhaustible ideal new energy. Solar cell uses the photoelectric conversiontechnology to convert the solar energy into electricity. Because of its abroad material sourcesand cheap price, good processability, physical modification, diversification of the battery’sprocessing, thin and flexible etc, organic solar cell, especially polymer solar cell, is analternative to silicon-based inorganic semiconductor, and become the focus of research athome and abroad.
Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)（PEDOT:PSS） is widely usedin organic photovoltaic device as the hole transport layer, so as to obtain high energyconversion efficiency. But the noamal PEDOT (AI4083) is acidic, and it will etch ITO, thenreduce energy conversion efficiency and stability of device. We adopt pH neutral PEDOTreplace acid PEDOT to make polymer solar cell devices. By applied some simple processingson the surface of a neutral PEDOT film, the efficiency of the neutral PEDOT device afterprocessings is more than doubled compared to the untreated neutral PEDOT device, and isslightly higher than the efficiency of the acid PEDOT device. By X-ray photoelectronspectroscopy analysis, whether the acidic PEDOT samples which are stored in the air forsome days, or the active layer samples which use the acidic PEDOT as substrate and werestored in the same conditions, In element could be detected in the surfaces of two typesamples. And in corresponding neutral PEDOT samples and active layer samples, In elementwere not detected, it is illustrated that the neutal PEDOT can restrain the diffusion of Inelement into the hole transport layer and the active layer effectively, the lifetime of the neutralPEDOT device is more than doubled compared with the acidic PEDOT device.
引文
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