CN108486685A - 一种共轭聚合物膜层的制备方法及其应用 - Google Patents

一种共轭聚合物膜层的制备方法及其应用 Download PDF

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CN108486685A
CN108486685A CN201810270635.1A CN201810270635A CN108486685A CN 108486685 A CN108486685 A CN 108486685A CN 201810270635 A CN201810270635 A CN 201810270635A CN 108486685 A CN108486685 A CN 108486685A
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夏曾强
白清云
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BOE Technology Group Co Ltd
Chengdu BOE Optoelectronics Technology Co Ltd
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Chengdu BOE Optoelectronics Technology Co Ltd
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Abstract

本发明涉及显示领域，特别涉及一种共轭聚合物膜层的制备方法及其应用。本发明的共轭聚合物膜层的制备方法，包括以下步骤:形成含有纤维状的共轭聚合物的溶液，通过溶液成膜法，得到共轭聚合物膜层。由于纤维状的共轭聚合物具有一定的长度和取向，在其维度方向上具有很高的电子迁移率，能够很好的提高载流子迁移率。将所述方法制备的共轭聚合物膜层用于有机发光二极管或者太阳能电池时，由于共轭聚合物膜层具有较高载流子迁移率，因此提高了器件的性能。

Description

一种共轭聚合物膜层的制备方法及其应用
技术领域
本发明涉及显示领域，特别涉及一种共轭聚合物膜层的制备方法及其应用。
背景技术
有机发光二极管(OLED)，具有亮度高、材料选择范围宽、驱动电压低、全固化主动发光等特性，同时拥有高清晰、广视角，以及响应速度快等优势，符合信息时代移动通信和信息显示的发展趋势，以及绿色照明技术的要求，是目前国内外众多研究者的关注重点。
有机发光二极管一般包括阳极、空穴传输层、空穴注入层、发光层、电子注入层、电子传输层、阴极等膜层。各个膜层通常以蒸镀技术、或者通过溶液成膜法形成。其中，溶液成膜法包括溶液旋涂技术或者喷墨打印技术等，具有操作简便等优点，但是由于溶剂的存在，导致材料积聚状态疏松，容易导致载流子传输速率慢，迁移长度短。
特别是涉及电子迁移率的膜层，例如电子注入层、电子传输层、发光层，多采用共轭聚合物半导体材料。而共轭聚合物半导体材料的分子链间的跃迁传输是制约电子迁移效率的重要瓶颈，若以溶液成膜法形成相应膜层，则直接导致载流子尤其是电子在同一分子链上的传输长度短，容易在分子间跃迁，造成载流子迁移效率低。
发明内容
本发明要解决的技术问题是：提供一种共轭聚合物膜层的制备方法，载流子迁移率高。所述膜层可用于有机发光二极管以及太阳能电池中。
本发明公开了一种共轭聚合物膜层的制备方法，包括以下步骤:
形成含有纤维状的共轭聚合物的溶液，通过溶液成膜法，得到共轭聚合物膜层。
优选地，所述纤维状的共轭聚合物的制备方法包括：
(A)，通过同轴静电纺丝得到以共轭聚合物为内层，高分子聚合物为外层的纤维材料；
(B)，剥离所述纤维材料外层的高分子聚合物，得到所述纤维状的共轭聚合物。
优选地，所述步骤(A)具体为：
以共轭聚合物为溶质形成内层纺丝溶液，以高分子聚合物为溶质形成外层溶液，经过同轴静电纺丝，得到以共轭聚合物为内层，高分子聚合物为外层的纤维材料，所述纤维材料为纳米纤维材料。
优选地，所述共轭聚合物包括聚3-己基噻吩、萘酰亚胺和噻吩的共轭聚合物、聚苯乙烯、聚喹喔啉或者聚芴；所述内层纺丝溶液的质量百分比浓度约为1～15％。
优选地，所述高分子聚合物包括聚对苯二甲酸乙二醇酯或者聚甲基丙烯酸甲酯；所述外层溶液的质量百分比浓度约为1～20％。
优选地，所述同轴静电纺丝时的工作电压为1～500kv。
优选地，所述同轴静电纺丝包括：利用针头将所述内层纺丝溶液和所述外层溶液喷射在平板电极上，所述针头与所述平板电极之间的距离大于5cm。
优选地，所述内层纺丝溶液以及外层溶液的泵送速度约为0.01ul/h～10ml/h。
优选地，所述步骤(B)具体包括：
将所述纤维材料浸泡于处理液中，经过加热、震荡以及超声处理，剥离外层的高分子聚合物，得到所述纤维状的共轭聚合物。
优选地，所述处理液包括甲醇或者乙腈。
本发明公开了一种有机发光二极管，包括由上述技术方案所述方法制备的共轭聚合物膜层。
优选地，所述共轭聚合物膜层包括电子注入层、电子传输层或者发光层。
优选地，所述共轭聚合物膜层包括p型共轭聚合物和n型共轭聚合物。
本发明公开了一种显示器件，包括上述技术方案所述的有机发光二极管。
本发明还公开了一种太阳能电池，包括由上述技术方案所述方法制备的共轭聚合物膜层。
与现有技术相比，本发明的共轭聚合物膜层的制备方法，包括以下步骤:形成含有纤维状的共轭聚合物的溶液，通过溶液成膜法，得到共轭聚合物膜层。本发明以纤维状的共轭聚合物为原料，通过溶液成膜法，形成膜层。由于纤维状的共轭聚合物具有一定的长度和取向，在其维度方向上具有很高的电子迁移率，能够很好的提高载流子迁移率。将所述方法制备的共轭聚合物膜层用于有机发光二极管或者太阳能电池时，由于共轭聚合物膜层具有较高载流子迁移率，因此提高了器件的性能。
附图说明
图1表示本发明一实施例共轭聚合物膜层的制备方法的流程图；
图2表示同轴静电纺丝装置的结构示意图；
图3表示本发明一实施例共轭聚合物膜层的制备方法的流程图；
图4表示本发明实施例1制备的纳米纤维状的共轭聚合物的扫描电镜图；
图5表示本发明实施例2制备的纳米纤维状的共轭聚合物的扫描电镜图。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明的限制。
本发明涉及的“约”指与端点数值存在一定偏差，如相差2％。
本发明实施例公开了一种共轭聚合物膜层的制备方法，包括以下步骤，具体参见图1：
形成含有纤维状的共轭聚合物的溶液，通过溶液成膜法，得到共轭聚合物膜层。
本发明涉及的共轭聚合物膜层可用于有机发光二极管或者太阳能电池等涉及利用半导体的器件中。本发明以纤维状的共轭聚合物为原料，由于纤维状的共轭聚合物具有一定的长度和取向，在其维度方向上具有很高的电子迁移率，能够很好的提高载流子迁移率，进而提高器件性能。
所述溶液成膜法可以包括喷墨打印法、丝网印刷法以及旋涂法任意一种。
在本发明中具体为，将含有纤维状共轭聚合物的溶液通过旋涂、丝网印刷法或者喷墨打印的方式涂覆于支撑物或者其他膜层上，经过干燥，即可得到共轭聚合物膜层、
由于，纤维状的共轭聚合物用于制备的膜层厚度较低，因此所述纤维状的共轭聚合物优选为纳米级纤维状的共轭聚合物，所述纤维状共轭聚合物的直径优选为1～200nm。
所述共轭聚合物的链段具有刚性，属于半导体材料，可以为p型共轭聚合物，也可以是n型共轭聚合物。所述溶液中可以含有p型纤维状共轭聚合物或者n型纤维状共轭聚合物，还可以同时含有p型纤维状共轭聚合物和n型纤维状共轭聚合物。所述溶液中同时含有p型纤维状共轭聚合物和n型纤维状共轭聚合物，可以构建纳米级别的互穿网络结构，p型纤维状共轭聚合物和n型纤维状共轭聚合物通过溶液法成膜法得到的共轭聚合物膜层电子和空穴的分离和传输率均较高。
所述共轭聚合物可以是形成电子注入层、电子传输层或者发光层的材料，优选地包括聚3-己基噻吩(P3HT)、萘酰亚胺和噻吩的共轭聚合物(NDI)、聚苯乙烯、聚喹喔啉或者聚芴。所述萘酰亚胺和噻吩的共轭聚合物可以为聚{2,7-[9,9’-双(N,N-二甲基丙基-3-胺基)芴]-交替-5,5’-[2,6-(双-2-噻吩基)-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺]}(PNDIT-F3N)和聚{2,7-[9,9’-双(N,N-二甲基丙基-3-乙基溴化铵)芴]-交替-5,5’-[2,6-(双-2-噻吩基)-N,N’-二异辛基-1,4,5,8-萘并二酰亚胺]}(PNDIT-F3N-Br)。
在现有技术中，所述共轭聚合物较难制备形成纤维状。
本发明克服了该技术难点，制备得到了纤维状的共轭聚合物。优选地，所述纤维状的共轭聚合物的制备方法包括：
(A)，通过同轴静电纺丝得到以共轭聚合物为内层，高分子聚合物为外层的纤维材料；
(B)，剥离所述纤维材料外层的高分子聚合物，得到所述纤维状的共轭聚合物。
以下具体说明所述纤维状的共轭聚合物的制备方法：
(A)，通过同轴静电纺丝得到以共轭聚合物为内层，高分子聚合物为外层的纤维材料；
所述同轴静电纺丝包括：利用针头将所述内层纺丝溶液和所述外层溶液喷射在平板电极上。
优选地，所述步骤(A)具体包括：
以共轭聚合物为溶质形成内层纺丝溶液，以高分子聚合物为溶质形成外层溶液，经过同轴静电纺丝，得到以共轭聚合物为内层，高分子聚合物为外层的纤维材料，所述纤维材料为纳米纤维材料。由于高分子聚合物通过纺丝形成纤维状，因此以其外层形成纤维状后过程中将共轭聚合物包裹在其中，使得共轭聚合物在内层也形成纤维状。
所述共轭聚合物溶于溶剂中，形成以共轭聚合物为溶质的内层纺丝溶液。所述溶剂为共轭聚合物的良溶剂，优选为氯仿、二氯甲烷、氯苯等溶解性好、沸点低的溶剂。
所述内层纺丝溶液的质量百分比浓度优选约为1～15％。
作为外层的所述高分子聚合物优选为具有柔性链段，即分子链的化学键自由度高的高分子聚合物，更优选地包括聚对苯二甲酸乙二醇酯(PET)或者聚甲基丙烯酸甲酯(PMMA)，更优选为相对分子量为200000的PET，相对分子量为100000的PET，相对分子量为50000的PMMA。
该种具有柔性链段的高分子聚合物更容易通过纺丝形成纤维状。
所述具有柔性链段的高分子聚合物，其主链以C-C单键、C-O单键、O-O键为主，分子量优选大于10000。由于所述高分子聚合物具有长分子链以及链柔性，因此能较好的纺丝。
所述外层溶液的质量百分比浓度优选地约为1～20％。
根据内层纺丝溶液以及外层溶液的浓度，调节同轴静电纺丝过程中的纺丝电压、针头与平板电极之间的距离以及溶液泵送速度，以形成长度及直径最佳的纤维材料。
在静电纺丝的过程中，若内层纺丝溶液中的溶剂挥发性质达不到效果，优选地通过加热内层纺丝溶液，提升内层纺丝溶液的温度，促进溶剂的挥发，从而达到纺丝成形的效果。
同轴静电纺丝的设备示意图如图2所示，图2中，1为外层溶液输入通道，2为内层纺丝溶液输入通道，3为针头，4为平板电极。外层溶液和内层纺丝溶液通过针头3喷出，经过电场作用进行拉丝，从而形成纤维材料。
根据共轭聚合物以及高分子聚合物的种类不同，适当选择同轴静电纺丝的工作电压。
根据对纤维材料的直径要求，针头与平板电极之间的距离可以调节，针头与平板电极之间的距离越远，纤维状材料的直径越小。
所述内层纺丝溶液以及外层溶液的泵送速度，也可以影响纤维状材料的直径，当外层溶液的并送速率越高，纤维材料的直径越小；反之亦然。
所述同轴静电纺丝时的工作电压约为1～500kv；
所述同轴静电纺丝包括，利用针头将所述内层纺丝溶液和所述外层溶液喷射在平板电极上，针头与平板电极之间的距离大于5cm；所述内层纺丝溶液以及外层溶液的泵送速度约为0.01ul/h～10ml/h。
(B)，剥离所述纤维材料外层的高分子聚合物，得到所述纤维状的共轭聚合物。
所述步骤(B)具体为：
将所述纤维材料浸泡于处理液中，经过加热、震荡以及超声处理，剥离外层的高分子聚合物，得到所述纤维状的共轭聚合物。
所述处理液的作用是清除外层的高分子聚合物，因此，所述处理液对于高分子聚合物具有较好的溶解性，但是难以溶解内层的共轭聚合物。所述处理液与共轭聚合物以及高分子聚合物的选择直接相关。当共轭聚合物为聚3-己基噻吩，高分子聚合物为聚对苯二甲酸乙二醇酯时，所述处理液优选为甲醇。当共轭聚合物为聚3-己基噻吩，高分子聚合物为聚甲基丙烯酸甲酯时，所述处理液优选为乙腈。
为了达到彻底剥离外层的高分子聚合物，需要经过加热、震荡以及超声处理，所述加热、震荡以及超声处理共同进行，优选地，反复处理三次以上。最终得到纤维状的共轭聚合物。
图3为本发明实施例优选地共轭聚合物膜层制备方法的流程图，包括以下步骤：
通过同轴静电纺丝得到以共轭聚合物为内层，高分子聚合物为外层的纤维材料；
剥离所述纤维材料外层的高分子聚合物，得到纤维状的共轭聚合物；
形成含有纤维状共轭聚合物的溶液；
经过溶液成膜法，得到共轭聚合物膜层。
本发明制备的共轭聚合物膜层可用于有机发光二极管或者太阳能电池中。
本发明实施例公开了一种有机发光二极管，包括上述技术方案所述方法制备的共轭聚合物膜层。
由于电子迁移在溶液成膜法中更容易受到影响，因此，优选地，所述共轭聚合物膜层主要涉及电子迁移率的膜层，包括电子注入层、电子传输层或者发光层。
优选地，所述共轭聚合物膜层包括p型共轭聚合物和n型共轭聚合物，p型共轭聚合物和n型共轭聚合物可以构建纳米级别的互穿网络结构，从而提高电子和空穴的分离和传输。
本发明的实施例还公开一种显示器件，包括上述技术方案所述的有机发光二极管。
本发明的实施例还公开了一种太阳能电池，包括由上述技术方案所述方法制备的共轭聚合物膜层。
以下对于为了进一步理解本发明，下面结合实施例对本发明提供的共轭聚合物膜层的制备方法及其应用进行详细说明，本发明的保护范围不受以下实施例的限制。
实施例1
以质量百分比浓度为8％的聚3-己基噻吩的氯仿溶液为内层纺丝溶液，质量百分比浓度为3％的聚对苯二甲酸乙二醇酯的乙醇溶液为外层溶液，在纺丝工作电压为30KV，针头与平板电极之间的距离为20CM以及0.1ul/h的泵送速率下，得到纳米纤维材料。其中纳米纤维材料直径均匀稳定在100nm左右，长径比达到2000以上。
将所述材料纤维材料浸泡于甲醇中，经过加热、震荡以及超声处理，并反复三次，完全剥离外层的聚对苯二甲酸乙二醇酯，得到纳米纤维状的聚3-己基噻吩。图4为所述纳米纤维状的共轭聚合物的扫描电镜图。
将所述纳米纤维状的聚3-己基噻吩形成溶液，通过喷墨打印法，得到聚3-己基噻吩膜层。
以所述聚3-己基噻吩膜层的有机发光二极管和传统的溶液法制作的有机发光二极管相比，其测试的电荷迁移率有显著提高。
实施例2
以质量百分比浓度为5％的萘酰亚胺和噻吩的共轭聚合物的氯仿溶液为内层纺丝溶液，质量百分比浓度为3％的聚对苯二甲酸乙二醇酯的乙醇溶液为外层溶液，在纺丝工作电压为45KV，针头与平板电极之间的距离为20CM以及0.1ul/h的泵送速率下，得到纳米纤维材料。其中纳米纤维材料直径均匀稳定在150nm左右，长径比达到2000以上。
将所述纳米纤维材料浸泡于甲醇中，经过加热、震荡以及超声处理，并反复三次，完全剥离外层的聚对苯二甲酸乙二醇酯，得到纳米纤维状的萘酰亚胺和噻吩的共轭聚合物。图5为所述纳米纤维状的共轭聚合物的扫描电镜图。
将所述纳米纤维状的萘酰亚胺和噻吩的共轭聚合物形成溶液，通过喷墨打印法，得到萘酰亚胺和噻吩的共轭聚合物膜层。
以所述萘酰亚胺和噻吩的共轭聚合物膜层的有机发光二极管和传统的溶液法制作的有机发光二极管相比，其测试的电荷迁移率有显著提高。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (15)

1.一种共轭聚合物膜层的制备方法，其特征在于，包括以下步骤:
形成含有纤维状的共轭聚合物的溶液，通过溶液成膜法，得到共轭聚合物膜层。
2.根据权利要求1所述的制备方法，其特征在于，所述纤维状的共轭聚合物的制备方法包括：
(A)，通过同轴静电纺丝得到以共轭聚合物为内层，高分子聚合物为外层的纤维材料；
(B)，剥离所述纤维材料外层的高分子聚合物，得到所述纤维状的共轭聚合物。
3.根据权利要求2所述的制备方法，其特征在于，所述步骤(A)具体包括：
以共轭聚合物为溶质形成内层纺丝溶液，以高分子聚合物为溶质形成外层溶液，经过同轴静电纺丝，得到以共轭聚合物为内层，高分子聚合物为外层的纤维材料，所述纤维材料为纳米纤维材料。
4.根据权利要求3所述的制备方法，其特征在于，所述共轭聚合物包括聚3-己基噻吩、萘酰亚胺和噻吩的共轭聚合物、聚苯乙烯、聚喹喔啉或者聚芴；所述内层纺丝溶液的质量百分比浓度约为1～15％。
5.根据权利要求3所述的制备方法，其特征在于，所述高分子聚合物包括聚对苯二甲酸乙二醇酯或者聚甲基丙烯酸甲酯；所述外层溶液的质量百分比浓度约为1～20％。
6.根据权利要求3所述的制备方法，其特征在于，所述同轴静电纺丝的工作电压约为1～500kv。
7.根据权利要求3所述的制备方法，其特征在于，所述同轴静电纺丝包括：利用针头将所述内层纺丝溶液和所述外层溶液喷射在平板电极上，所述针头与所述平板电极之间的距离大于5cm。
8.根据权利要求3所述的制备方法，其特征在于，所述内层纺丝溶液以及外层溶液的泵送速度约为0.01ul/h～10ml/h。
9.根据权利要求2所述的制备方法，其特征在于，所述步骤(B)具体包括：
将所述纤维材料浸泡于处理液中，经过加热、震荡以及超声处理，剥离外层的高分子聚合物，得到所述纤维状的共轭聚合物。
10.根据权利要求9所述的制备方法，其特征在于，所述处理液包括甲醇或者乙腈。
11.一种有机发光二极管，其特征在于，包括由权利要求1～10中任意一项所述方法制备的共轭聚合物膜层。
12.根据权利要求11所述的有机发光二极管，其特征在于，所述共轭聚合物膜层包括电子注入层、电子传输层或者发光层。
13.根据权利要求11所述的有机发光二极管，其特征在于，所述共轭聚合物膜层包括p型共轭聚合物和n型共轭聚合物。
14.一种显示器件，其特征在于，包括权利要求11～13中任意一项所述的有机发光二极管。
15.一种太阳能电池，其特征在于，包括由权利要求1～10中任意一项所述方法制备的共轭聚合物膜层。
CN201810270635.1A 2018-03-29 2018-03-29 一种共轭聚合物膜层的制备方法及其应用 Pending CN108486685A (zh)

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