CN110911562A - 聚合物-多金属氧酸盐复合涂布液及其应用 - Google Patents
聚合物-多金属氧酸盐复合涂布液及其应用 Download PDFInfo
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Abstract
本发明涉及一种聚合物‑多金属氧酸盐复合涂布液，其包含一种溶剂、一种聚合物或二种以上聚合物交缠，以及一种多金属氧酸盐，其中，所述聚合物或二种以上聚合物交缠结构与多金属氧酸盐之间的重量比例范围为1:0.001～1:0.09。上述复合涂布液可用以制造载子传递薄膜，以及具备载子传递薄膜的有机电子装置。
Description
本申请要求2018年9月17日申请的美国临时专利申请案第62/732,165号的优先权，其揭露的全部内容通过引用并入本案。
技术领域
本发明涉及一种复合涂布液，特别是一种聚合物-多金属氧酸盐复合涂布液及其应用。
背景技术
有机电子装置包含有机光伏装置、有机光感测装置、有机发光二极管以及有机薄膜晶体管(OTFT)，近年来在新制作过程开发下发展兴盛，特别是溶液加工法不需要真空环境，低操作温度，具有成本低、可大面积卷对卷生产等优势。
以有机光伏装置的结构为例，通常包括透明基板、透明电极(例如ITO)、载子传递层一、主动层、载子传递层二、金属电极(例如铝或银)，其中用于电洞传递之载子传递材料主要有聚合物和金属氧化物两大类。金属氧化物例如：氧化钼、氧化钒、氧化镍、氧化钨等因具有能阶匹配、材料稳定性高等优点。但传统的金属氧化物薄膜多采用真空蒸镀方法沉积，与基于溶液态的印刷涂布方法不兼容，也不利于大面积卷对卷生产。
另一类常用于电洞传递的材料为聚合物，主要是聚(3,4乙烯二氧噻吩):聚(笨乙烯磺酸)(poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate))，即PEDOT:PSS导电聚合物，它是已商业化广泛使用的一类材料。该材料可良好分散于水性溶剂中，可大面积涂布、易于搭配各种涂布或印刷技术进行使用，且成膜质量高。但是与使用金属氧化物的电洞传递层的有机光伏装置相比，PEDOT:PSS始终由于载子传递特性与能阶匹配性上不及蒸镀型之金属氧化物，显著降低终端产品的光电效能。
综上所述，仍需要学界与业界大力投入开发，以便于开发兼顾适合大面积生产，以及维持高光电效能的电洞传递层材料。
发明内容
本发明的目的在于提供一种含有PMA:PEDOT:PSS的复合涂布液
本发明的另一个目的在于提供一种兼顾适合大面积生产，以及维持高光电效能的电洞传递层材料。
附图说明
图1A至图1C为显示载子传递薄膜的成膜质量的图。
图2A至图2D为显示PMA浓度如何影响有机光伏装置的光电性能的图。
图3A至图3D为显示使用PMA:PEDOT:PSS载子传递薄膜的组件光电性能与单独使用PEDOT:PSS载子传递薄膜的组件光电性能比较的图。
具体实施方式
定义
本文所用的填充因子(FF)，是指实际最大可获得功率(Pm或Vmp×Jmp)与理论(非实际可获得)功率的比值(Jsc×Voc)。因此，填充因子可由下式决定：
FF＝(Vmp×Jmp)/(Voc×Jsc)
其中Jmp及Vmp分别表示在最大功率点(Pm)之电流密度及电压，该点是通过变化电路中的电阻直到J×V为最大值而得；Jsc及Voc分别表示开路电流及开路电压。填充因子是评价太阳电池的关键参数。
本文所用的开路电压(Voc)，系在无连接外部负载下组件的阳极与阴极之间的电位差。
本文所用的太阳电池的功率转换效率(PCE)，系指从入射光转变为电力的功率百分比。太阳电池的功率转换效率(PCE)可通过最大功率点(Pm)除以标准测试条件下(STC)入射光辐射照度(E；W/m2)及太阳电池的表面积(Ac；m2)而算出。STC通常指在温度25℃、辐射照度为1000W/m2的AM大气压量(air mass)1.5G光谱。
本文所用的构件(例如薄膜层)，若其包含一个或一个以上的可吸收光子而产生用以产生光电流的激子的化合物，可被视为“光活性”。
本文所用的“溶液加工”，是指化合物(例如聚合物)、材料或组成物可用于溶液态的制备过程，例如旋转涂布、印刷法(例如喷墨印刷、凹版印刷、凸版印刷等)、喷涂法、狭缝涂布、滴铸法、浸涂法及刮刀涂布法。
如本文所用的“退火”，是指在环境中或在减压或加压下，对半结晶聚合物膜进行一定持续时间的沉积后热处理，“退火温度”，是指该退火过程中该聚合物膜或该聚合物与其他分子的混合薄膜可进行小规模分子运动及重新排列的温度。不受任何特定理论束缚，据说退火可在可能的情况下导致聚合物膜中的结晶度的增加，提升聚合物膜或该聚合物与其他分子的混合薄膜的材料载子迁移率，并形成分子交互排列而达到有效电子与电洞的独立传递路径的效果。
本发明的第一实施例涉及一种聚合物-多金属氧酸盐复合涂布液，其包含一种溶剂、一种聚合物或二种以上聚合物交缠结构，以及一种多金属氧酸盐，其中，聚合物或二种以上聚合物交缠结构与多金属氧酸盐的重量比例范围为1:0.001～1:0.09。优选地，聚合物或二种以上聚合物交缠结构聚合物与多金属氧酸盐的重量比例范围为1:0.005～1:0.03。
在一个实施例中，聚合物交缠结构为聚(3,4乙烯二氧噻吩):聚(笨乙烯磺酸)(poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate))(PEDOT:PSS)。
在另一个实施例中，多金属氧酸盐选自含有钼、钨、钒中的任意一种或者两种以上的组合的多金属氧酸盐。优选地，多金属氧酸盐为磷钼酸(phosphomolybdic acid)(PMA)。
通过聚合物交缠结构与多金属氧酸盐之间均匀混合，可降低多金属氧酸盐的团聚现象，提高成膜均匀性。同时，金属氧酸盐也具有调节聚合物交缠结构的功函数，进而改变有机电子装置应用性能的功能。
在又一个实施例中，前述的多金属氧酸盐于复合涂布液中的浓度范围为0.01～0.8mg/ml。优选地，浓度范围为0.05～0.2mg/ml。。
在本实施例中，溶剂选自下列一种或者两种以上的组合：甲醇、乙醇、正丙醇、异丙醇、正丁醇、叔丁醇、乙二醇以及乙二醇单甲醚。
本发明的第二个实施例涉及一种载子传递薄膜，所述载子传递薄膜是由第一实施例中所述的复合涂布液所形成。
本发明的第三个实施例涉及一种有机电子装置，包含第一电极(透明电极))、第一载子传递层、主动层、第二载子传递层、第二电极，前述第一载子传递层位于第一电极与主动层之间，第二载子传递层位于主动层与第二电极之间，前述第二载子传递层为如第二实施例所述的载子传递薄膜。此外，有机电子装置包含有机光伏装置、有机光感测装置、有机发光二极管以及有机薄膜晶体管(OTFT)。
实施例
实施例1：聚合物交缠结构-多金属氧酸盐复合涂布液制备
a.试剂A—将2mg的多金属氧酸盐(polyoxometalate)系列化合物(如磷钼酸(phosphomolybdic acid)，PMA)溶解于1ml的极性溶剂中(如2-丙醇)
b.将试剂A与试剂B—聚(3,4乙烯二氧噻吩):聚(笨乙烯磺酸)(poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate))(PEDOT:PSS)溶液以体积比1:9进行混合(例：1ml试剂A加入9ml试剂B，其中试剂B的PEDOT:PSS固含量约在水中1％，因此9ml(9g)PEDOT:PSS溶液中约含90mg PEDOT:PSS固体)
c.每10ml的试剂A与试剂B混合溶液中，PEDOT:PSS(固体)对多金属氧酸盐(固体)的重量比为90mg:2mg＝1:0.022
d.每10ml的试剂A与试剂B混合溶液中，含有2mg PMA。PMA在溶液中的浓度为2mg/10ml＝0.20mg/ml。
实施例2：有机光伏装置的制造及测试
使用具有～15Ω/sq的薄层电阻的预图案化的ITO涂覆的玻璃作为基板。依顺序在肥皂去离子水、去离子水、丙酮及异丙醇中超声波震荡处理，在每个步骤中清洗15分钟。用UV-ozone清洁器进一步处理洗涤过的基材30分钟。将ZnO(二乙基锌溶液，在甲苯中15wt％，用四氢呋喃稀释)的顶涂层，以5000rpm的旋转速率30秒旋转涂布在ITO基板上，然后在空气中在150℃下烘烤20分钟。在o-xylene中制备主动层溶液。主动层材料为共轭聚合物与富勒烯衍生物的混合物，主动层材料浓度为35mg ml-1。为将主动层材料完全溶解，主动层溶液需在加热板上以120℃下搅拌至少1小时。随后将主动层材料回复至室温进行旋转涂布。最后将涂布完成的主动层薄膜在120℃下退火5分钟。然后将实施例1所提供的试剂A与试剂B的混合溶液涂布或印刷于主动层上，并干燥以便于形成载子传递薄膜。
关于载子传递薄膜的成膜质量请参考表一所列不同配方，以及图1A、图1B与图1C，图1A是配方A于光伏组件主动层上所制成的薄膜，图1B是配方B于光伏组件主动层上所制成的薄膜，图1C是配方D于光伏组件主动层上所制成的薄膜。影响成膜质量最重要的因素是PMA在PEDOT:PSS溶液中的浓度，表一中控制组是完全没有PMA的PEDOT:PSS溶液，溶液没有胶化(gelled)情形，成膜完整。配方A与配方B由于PMA浓度偏高(0.83与0.67mg/ml)且试剂A(溶剂为醇类)与试剂B(溶剂为水)的混合比例也较相近(1:5与1:2)，因此可发现在醇类溶剂与水及PMA与PEDOT:PSS交替作用下，混合溶液发生胶化现象，无法形成完整薄膜，请参考图1A与图1B。而配方C虽然试剂A与试剂B的混合比例已提高至1:10，但由于试剂A中的PMA含量相对较高(10mg/ml)，整体PMA于试剂B内的含量为0.91mg/ml，同样无法得到理想的膜面，也显见PMA含量对成膜性的重要。配方D的试剂A与试剂B比例调整为1:9，PMA于试剂B内的浓度调低至0.80mg/ml，可以发现混合溶液虽然发生胶化现象，但是速度较慢，可以形成完整薄膜。
表一
随后沉积100nm厚度的银作为上电极。使用环氧树脂在手套箱内封装所有组件。使用class AAA太阳光仿真器，在1000W/m2的AM1.5G光强度下测量组件J-V特性。此处用于校正光强度的校正电池乃采用具有KG5滤波片的标准硅二极管，并于使用前先经过第三方校正。此实验使用Keithley 2400 source meter仪器记录J-V特性。电池面积为4mm2，并由金属屏蔽对准组件进行面积定义。
实施例3：有机光伏装置的效能分析
关于PMA浓度如何影响光电性能请参考表二、图2A、图2B、图2C与图2D，图2A显示当PMA浓度维持在0.1mg/ml以上，装置的开路电压(Voc)也一直维持在0.8V左右。图2B显示当PMA浓度在0.01mg/ml-0.2mg/ml之间，装置的开路电流(Jsc)可以维持在15mA/cm2以上。图2C显示当PMA浓度在0.2mg/ml以上，装置的填充因子(FF)可以维持在72％以上。图2D显示当PMA浓度在0.01mg/ml-0.3mg/ml之间，装置的功率转换效率(PCE)可以维持在8.4％以上。
再请参阅图3A至图3D，方块数据是控制组配方制成有机光伏装置，圆圈数据是配方E制成有机光伏装置，可以发现使用PMA:PEDOT:PSS载子传递薄膜的组件光电性能优于单独使用PEDOT:PSS载子传递薄膜的组件光电性能。此外，使用PMA:PEDOT:PSS载子传递薄膜的组件在长时间工作中的稳定性都能维持良好。
表二
Claims (10)
1.一种聚合物-多金属氧酸盐复合涂布液，该复合涂布液包含:
一种溶剂；
一种聚合物或二种以上聚合物交缠结构；以及
一种多金属氧酸盐，其中，该聚合物或二种以上聚合物交缠结构与该多金属氧酸盐的重量比例范围为1:0.001～1:0.09。
2.根据权利要求1所述的聚合物-多金属氧酸盐复合涂布液，其中该聚合物或二种以上聚合物交缠结构与该多金属氧酸盐的重量比例范围为1:0.005～1:0.03。
3.根据权利要求1所述的聚合物-多金属氧酸盐复合涂布液，其中该多金属氧酸盐于该复合涂布液中的浓度范围为0.01～0.8mg/ml。
4.根据权利要求1所述的聚合物-多金属氧酸盐复合涂布液，其中该多金属氧酸盐在该复合涂布液中的浓度范围为0.05～0.2mg/ml。
5.根据权利要求1所述的聚合物-多金属氧酸盐复合涂布液，其中该二种以上聚合物交缠结构为聚(3,4乙烯二氧噻吩):聚(笨乙烯磺酸)(PEDOT:PSS)。
6.根据权利要求1所述的聚合物-多金属氧酸盐复合涂布液，其中，该多金属氧酸盐选自含有钼、钨、钒中的任意一种或者两种以上的组合的多金属氧酸盐。
7.根据权利要求1所述的聚合物-多金属氧酸盐复合涂布液，其中该多金属氧酸盐为磷钼酸(PMA)。
8.根据权利要求1所述的聚合物-多金属氧酸盐复合涂布液，其中该溶剂选自下列一种或者两种以上的组合：甲醇、乙醇、正丙醇、异丙醇、正丁醇、叔丁醇、乙二醇以及乙二醇单甲醚。
9.一种载子传递薄膜，该载子传递薄膜是由如权利要求1所述的聚合物-多金属氧酸盐复合涂布液所形成。
10.一个有机电子装置，包含：
第一电极，该第一电极是为透明电极；
第一载子传递层；
主动层，其中，该第一载子传递层位于该第一电极与该主动层之间；
第二载子传递层；以及
第二电极，其中，该第二载子传递层位于该主动层与该第二电极之间，该第二载子传递层为如权利要求9所述的载子传递薄膜。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114351482A (zh) * | 2021-12-14 | 2022-04-15 | 华南理工大学 | 一种电致变色艺术服装面料及其制备方法与应用 |
| CN114351482B (zh) * | 2021-12-14 | 2022-10-25 | 华南理工大学 | 一种电致变色艺术服装面料及其制备方法与应用 |
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| US11124662B2 (en) | 2021-09-21 |
| TW202033680A (zh) | 2020-09-16 |
| US20200087524A1 (en) | 2020-03-19 |
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