CN103965591A - 光电器件特别是倒置型opv电池的形成方法 - Google Patents

光电器件特别是倒置型opv电池的形成方法 Download PDF

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CN103965591A
CN103965591A CN201310717113.9A CN201310717113A CN103965591A CN 103965591 A CN103965591 A CN 103965591A CN 201310717113 A CN201310717113 A CN 201310717113A CN 103965591 A CN103965591 A CN 103965591A
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thiophene
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马蒂厄·桑戈尔
索伦·贝尔松
马蒂厄·芒索
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Abstract

本发明的形成光电器件的方法涉及包含以下成分的组合物:聚(3,4-亚乙基二氧噻吩)或PEDOT;聚苯乙烯磺酸酯或PSS;具有下式的化合物(A),其中0<x/y<1;Ar1和Ar2表示可相同或不同的两个芳香环;Ar1和/或Ar2在其环上包含至少一个疏水取代基。

Description

光电器件特别是倒置型OPV电池的形成方法
技术领域
本发明属于有助于光电器件(特别是“倒置”型有机光伏(OPV)电池)形成的技术方案的研究框架。
更具体地,本发明提供了向包含PEDOT(聚(3,4-亚乙基二氧噻吩))和PSS(聚苯乙烯磺酸酯)的制剂或分散体中添加导电添加剂或半导体添加剂,所述包含PEDOT和PSS的制剂或分散体特别地用来形成OPV电池的HTL(“空穴传输层”)。这种添加剂的存在旨在改变制剂对疏水层表面的润湿能力。然后制剂可直接在疏水层上容易地沉积成层的形式,例如由存在于倒置OPV电池中的疏水半导体材料制成的有源层。这样的沉积可进而通过常规技术例如喷墨印刷来进行。
该方案可在OPV电池,以及任意其他光电器件例如光检测器(OPD、“有机光检测器”)、OLED(“有机发光二极管”)或PLED(“聚合物发光二级管”)中获得应用。
背景技术
有机光伏(OPV)电池是能够通过使用有机半导体材料将太阳能转化为电能以产生光伏效应的器件。活性材料,以及这些器件的架构仍然正在发展以满足能够加宽这些技术应用领域的性能和寿命标准。用于制造这些器件的方法也仍然是一直关注的问题。
在常规OPV电池结构中,基底1覆盖有以下连续的层:
-包含用作第一电极的导电氧化物的导电层2;
-半导体空穴传输层3,也称为HTL或也称为P层;
-由有机半导体材料制成的有源层4;
-半导体电子传输层5,也称为ETL或也称为N层;以及
-用作第二电极的导电层6。
在倒置结构(也称为NIP结构)中,例如图1中示意性示出的,堆叠体具有以下顺序:
-基底1;
-包含用作第一电极的导电氧化物的导电层6;
-n(或N)半导体层5;
-有源层4;
-p(或P)半导体层3;
-用作第二电极或上电极的导电层2。
OPV技术的主要优点之一是可经由多种印刷和/或涂覆方法通过湿法完全形成器件,所述印刷和/或涂覆方法为:喷墨、丝网印刷、狭缝模头涂布(slot-die)、凹版印刷、喷涂、旋涂、柔版印刷或刮片涂布……
迄今为止,由于OPV电池所谓的“倒置”结构能够实现最长的寿命,所以其看起来是最有前景的。因此,在这样的构造中,P层(空穴传输层或HTL)被布置在有源层的表面上。
目前,空穴传输层通常得自于包含PEDOT:PSS的制剂或分散体。其包含:
-具有以下化学结构的聚(3,4-亚乙基二氧噻吩)或PEDOT:
n是正整数;
-具有以下化学结构的质子形式(右手边)或非质子形式(左手边)的聚苯乙烯磺酸酯或PSS:
x和y是正整数。
PSS是水溶性聚合物,大多数PEDOT:PSS制剂包含水。
现在,在OPV电池中,预期在其上沉积含PEDOT:PSS制剂的有源层是强疏水的,并因此具有不良的水溶液的可润湿性。
因此,PEDOT:PSS悬浮液铺在有源层上的润湿能力或能力通常是不良的。因此在不进行表面处理的情况下难以进行连续且均匀的沉积。
这种处理的替代方法是使预期的制剂适合于形成空穴传输层以改善其润湿疏水有源层的能力。
因此,作为一个实例,已设想了不同的方案以解决有源层与包含PEDOT:PSS的P层之间的这种相容性问题。
文献Voigt等(Solar Energy Materials and Solar Cells,95,2011,731-734)描述了将溶剂(异丙醇)和/或非离子且非导电的含氟表面活性剂(FS300)添加到PEDOT:PSS制剂中以使其通过凹版印刷布置在有源层上。然而,由此获得的OPV电池具有相对低的性能并且表面的等离子处理仍是有必要的。
文献Weickert等(Solar Energy Materials and Solar Cells,95,2010,2371-2374)公开了将制剂稀释在大量醇(2-丙醇)中并通过喷涂在有源层上进行沉积。然而,稀释后的干物质含量非常低,所以层的最终厚度很小。关于具体的喷涂技术,可通过重复操作来弥补这种小的厚度,但是这对于大多数沉积技术是不可行的。此外,这样的技术似乎与电极的后续印刷不相容,所述文章报道有电极蒸发。
文件Lloyd等(Solar Energy Materials and Solar Cells,95,2011,1382-1388)中提供了另一个选择。其包括在有源层上进行等离子处理以使其更亲水。然而,这样的处理产生了缺陷并使层降解。
因此似乎明显地需要确定新的技术解决方案来改善光电器件疏水有源层上包含PEDOT:PSS的空穴传输层的形成,并且更通常地改善疏水载体上包含PEDOT:PSS的层的形成。
发明内容
因此,并且在本发明的框架中,确定了表面活性型的新化合物,以结合在包含PEDOT:PSS的制剂或分散体中,尤其是用于形成OPV电池的空穴传输层,其同时能够:
-增加其对疏水层(特别是在OPV电池有源层表面上)的润湿能力;
-不降低由此形成的层的导电性;
-在OPV电池的环境中使该层在其表面与电极印刷相容。
根据第一方面,本发明涉及包含以下成分的组合物:
-聚(3,4-亚乙基二氧噻吩)或PEDOT;
-聚苯乙烯磺酸酯或PSS;
-具有下式的化合物(A):
并且,·0<x/y<1;
·Ar1和Ar2表示可相同或不同的芳香环;
·Ar1和/或Ar2在其环上包含至少一个疏水取代基。
应注意,聚苯乙烯磺酸酯或PSS可以是质子形式(SO3H)或非质子形式(SO3 -)或者是两种形式。
因此化合物(A)在这样的组合物中旨在起表面活性剂的作用。其更有利地是导电的或电的半导体。
由于其结构,所以它是具有被磺酸基取代的样式的共轭共聚物。此外,至少一种样式的共聚物被疏水侧链取代。
合适地且有利地,芳香环Ar2不支持导电离子基团,并且特别地不支持磺酸基。
化合物(A)有利地具有选自包括以下的组的芳香环(Ar1和/或Ar2):噻吩、联噻吩、三联噻吩、噻吩并噻吩、吡咯、咔唑、吡咯并吡咯二酮(DPP)、硒酚、环戊并二噻吩(CPDT)、二噻吩并环戊二噻吩、Si-环戊并二噻吩(Si-CPDT)、二噻吩-Si-环戊并二噻吩、芴、二噻吩芴、苯、苯并噻唑、苯并噻二唑、二噻吩苯并噻二唑、喹喔啉、噻唑、磷杂茂(phosphole);有利地是噻吩。
根据一个优选的实施方案,两个芳香环(Ar1和Ar2)相同,并且有利地是噻吩。
此外,并且优选地,疏水取代基是由芳香环的碳原子之一支持的醚链(-O-R)。R可以是直链或支链,包含碳原子(有利地为1至15个)和可能的杂原子,例如O或N(有利地为1至10个)。有利地,R包含至少一个醚键(R’-O-R’’)。更有利地,取代基具有下式:
有利地,这样的疏水取代基至少由芳香环Ar2支持。根据一个具体的实施方案,Ar1和Ar2二者均包含至少一个疏水取代基,Ar1和Ar2可能支持相同的疏水取代基。
根据一个具体的实施方案,化合物(A)具有下式:
化合物(A)对应于聚(3-[2-(2-甲氧基乙氧基)]噻吩-2,5-二基-co-3-[2-(2-甲氧基乙氧基)]-4-磺酸-噻吩-2,5-二基)。其为由于磺酸基(SO3H)而具有亲水特征并且由于醚链而具有疏水特征二者的共聚物。这样的基团位于噻吩基团上,其链接能够提供良好的导电性。
应注意,化合物是所谓的“p型”共轭共聚物,常规地用作OPV电池HTL的唯一组分。其具有良好的润湿OPV电池有源层的能力,但是由于其高溶解度,其与用于形成OPV电池上电极的含银墨不相容。因此,结合有该材料作为HTL和印刷银电极的器件是系统短路的。
根据本发明的组合物可对应于墨。因此并且更通常地,除包含PEDOT:PSS的分散体和化合物A之外,其可包含有利地选自以下的至少一种溶剂:水、丙-2-醇、2-丁氧基乙醇(或乙二醇单丁醚,EGMBE)、乙醇、丁-1-醇、丁-2醇、乙二醇、丙二醇、二甘醇、二丙二醇甲醚(dowanolDPM)、乙二醇甲醚。
根据一个具体的实施方案,根据本发明的组合物包含丙-2-醇和2-丁氧基乙醇和可能的水的混合物。更具体地,其可包含:
-水,有利地按体积计的比例小于5%,更有利地还小于2%,并且最佳地等于0%;
-丙-2-醇,有利地按体积计的比例大于30%,更有利地还在40%与60%之间,并且最佳地在50%与55%之间;
-2-丁氧基乙醇,有利地按体积计的比例在10%与50%之间,并且更有利地还在15%与35%之间。
此外并且在实践中,预期与化合物A并可能与上述溶剂的一种或多种混合的包含PEDOT:PSS的分散体,可还包含选自包括以下的组的添加剂的一种或多种:
-高沸点溶剂,例如N-甲基-2-吡咯烷酮;
-溶剂,例如异丙醇;
-交联剂,例如γ-环氧丙氧基丙基三甲氧基硅烷(MomentivePerformance Materials Inc商业化的Silquest A187TM);
-表面活性剂,例如包含炔二醇的添加剂,例如Air Product商业化的DynlTM604。
有利地,化合物(A)相当于按根据本发明的组合物的重量计0.01%至0.2%,更有利地还为按重量计0.05%至0.2%,并且特别地相当于按重量计0.1%或更多。
根据另一个方面,本发明涉及用于制备根据本发明的组合物的方法,其包括可在以下所定义的溶剂的一种或多种存在下并且通过所提到的有利比例使化合物(A)混合在包含PEDOT:PSS的分散体中。
在本发明的上下文中,这样的组合物在沉积在基底上之后特别地旨在提供层。例如并且如已提到的,根据本发明的组合物可以是这样的墨,其旨在沉积在基底上,有利地沉积在光电器件的有源层上,特别地通过喷墨印刷的技术。在沉积并干燥使得组合物的溶剂蒸发之后,由根据本发明的组合物中存在的聚合物(特别是PEDOT、PSS和化合物(A))制成了所获得的层,有利地制成了光电器件的空穴传输层。
因此并且根据另一个方面,本发明涉及具有包含以下成分的层的光电器件:
-聚(3,4-亚乙基二氧噻吩)或PEDOT;
-聚苯乙烯磺酸酯或PSS;
-如上文所定义的化合物(A)。
如已提到的,这样的光电器件可以是有机光伏(OPV)电池,有利地为倒置构造,也可以是OPD(“有机光检测器”)、OLED(“有机发光二级管”)或PLED(“聚合物发光二级管”)。
有利地,化合物(A)相当于按所述层干重计的1%至30%,有利地为25%至30%。
这样的层有利地布置在光电器件有源层的表面上。因此,这样的层特别有利地作为空穴传输层,沉积在光电器件例如光伏器件的有源层上,有利地沉积在倒置构造(NIP)的有机光伏电池的有源层上。
常规地,光电器件(有利地为光伏器件)的有源层将电子供体和电子受体组合起来。因此并且根据一个具体的实施方案,有源层由以下成分制成:
-作为电子供体的P3HT(聚(3-己基噻吩-2,5-二基)或聚(3-己基噻吩)),其具有式:
n是正整数;
-作为电子受体的PCBM或PC60BM([6,6]-苯基-C61丁酸甲酯),其具有式:
作为一个变化方案,电子供体聚合物可选自包括以下的组:
-聚[[9-(1-辛基壬基)-9H-咔唑-2,7-二基]-2,5-噻吩二基-2,1,3-苯并-噻二唑-4,7-二基-2,5-噻吩二基]或PCDTBT:
-聚[2,1,3-苯并噻二唑-4,7-二基[4,4-双(2-乙基己基)-4H-环戊并[2,1-b:3,4-b']二噻吩-2,6-二基]]或PCPDTBT:
-PBDTTPD:
-PTB7:
类似地,电子受体可以是选自包括以下的组的另一种富勒烯:
-PC70BM([6,6]-苯基-C71丁酸甲酯):
-IC60BA(1’,1’’,4’,4’’-四氢-二[1,4]甲桥萘并[5,6]富勒烯-C60):
-双-PC60BM(双(1-[3-(甲氧羰基)丙基]-1-苯基)-[6.6]C62):
根据本发明的HTL具有在其表面与电极印刷相容的有利特征。因此并且根据另一个方面,根据本发明的光电器件(有利地为光伏器件)在HTL表面上包括印刷电极。常规地,其由银(Ag)制成。其也可由铜、铝、石墨乃至这些材料的混合物制成。
更具体地,关于倒置构造的光伏电池,其还包括:
-基底,有利地为塑料基底,例如由PET(聚对苯二甲酸乙二醇酯)、PEN(聚萘二甲酸乙二醇酯)或聚碳酸酯制成的塑料基底;
-用作电极的导电氧化物层,有利地通过TCO(“透明导电氧化物”),例如ITO(“铟锡氧化物”或“锡掺杂氧化铟”)、GZO(“镓掺杂氧化锌”)、AZO(含铝)、YZO(含钇)、IZO(含铟)或FTO(SnO2:F)形成;
-N层,通常为可能有掺杂的半导体金属氧化物,例如,可能掺杂有铝(Al)、铟(In)或镓(Ga)的氧化锌(ZnO),或者可能掺杂有锰(Mn)的二氧化钛(TiO2)。
应注意,根据本发明,形成光电器件(特别是倒置构造的光伏层)的方法可仅借助在工业用途中容易实施的简单沉积技术通过湿法完全实施。因此并作为实例,N层和有源层可通过旋涂沉积,并且HTL和上电极通过喷墨印刷沉积。
因此,本发明提供了用于形成光电器件(有利地是倒置构造(NIP)的光伏电池)的方法,其包括使例如上文描述的组合物沉积在层上,有利地在有源层上形成HTL。优选地,沉积通过喷墨印刷来进行。
应注意,在旨在提供HTL的制剂中添加化合物(A)能够实现有源层上均匀的沉积,从而其可在没有任何表面处理的情况下完成。
此外,由此获得的HTL与上电极的印刷相容。因此并且根据一个具体方面,所述形成方法包括上电极(例如,由银制成的上电极)在HTL表面上的后续沉积,有利地通过喷墨印刷进行。
更通常地,本发明涉及化合物(A)(例如上文定义的化合物(A))增加包含PEDOT:PSS的组合物润湿疏水层,特别是在由光电器件(例如倒置结构(NIP)的光伏电池)的半导体材料制成的有源层表面上润湿疏水层的能力的用途。
本发明的优点通过以下实施方案将更明显。
附图说明
图1示出了所谓的倒置或NIP结构的有机PV电池的图。
图2举例说明了没有添加剂(A)和具有根据本发明的组合物(B)的PEDOT:PSS制剂在T=30℃的温度下的液滴喷出的质量。
图3举例说明了没有添加剂(A)和具有根据本发明的组合物(B)的PEDOT:PSS制剂的有源层上的接触角。
具体实施方案
结合附图,以下的非限制性实施方案的目的在于举例说明本发明。
1/添加剂选择
用于实施方案的实施例上下文的具体添加剂具有以下化学式:
其中0<x/y<1。
其为由于磺酸基(SO3H)而具有亲水特征并且因为醚链而具有疏水特征二者的共聚物。这样的基团定位在噻吩基团上,其链接能够提供良好的导电性。其为聚(3-[2-(2-甲氧基乙氧基)]噻吩-2,5-二基-co-3-[2-(2-甲氧基乙氧基)]-4-磺酸-噻吩-2,5-二基)。
2/墨制剂
a.商用PEDOT:PSS溶液
用Heraeus商业化的如下两种PEDOT:PSS制剂测试了添加剂的效果:
-CPP105D
-F010。
下表1列出了这些制剂的主要物理化学性质:
干物质含量(%) 700s-1下的粘度(cP) pH 逸出功(eV)
CPP105D ~1 30 2.8 4.8
F010 ~1 30-60 2.8 4.8
b.溶剂
为了优化墨的性质(喷出、铺开、干燥)和最终沉积厚度,将以下溶剂添加到包含PEDOT:PSS的分散体中的添加剂混合物中:
-丙-2-醇(IPA);
-2-丁氧基乙醇(或乙二醇单丁醚,EGMBE)。
c.所用制剂和所得干膜的组成
下表2给出了两种已开发的制剂的组成,其量以按体积计的比例给出。
Plexcore HTL:包含添加剂的商用溶液;
IPA(溶剂)=异丙醇或丙-2-醇;
EGMBE(溶剂)=乙二醇单丁醚。
从PEDOT:PSS的商用分散体(CPP105D或F010),向其中添加包含添加剂的商用Plexcore HTL溶液,以及异丙醇、EGMBE和可能的水,制备了墨。
添加的plexcore HTL的量使得最终墨中添加剂的量在按重量计0.01%至0.2%的范围中。优选地,其为按重量计至少0.1%。
墨1的制备:
为了制备10mL墨1,开始取样1.6mL商用PEDOT:PSS制剂,向其中添加0.1mL包含添加剂的plexcore HTL的商用制剂,然后添加5mL异丙醇,并最终添加3.3mL EGMBE。
制备墨2:
为了制备10mL墨2,开始取样2.5mL商用PEDOT:PSS制剂,向其中添加0.5mL包含添加剂的plexcore HTL的商用制剂,然后添加5.5mL异丙醇,并最终添加1.5mL EGMBE。
然后将由此制备的溶液在环境温度和气氛下搅拌一夜后使用。
墨1和2中添加剂的量分别是按重量计0.02%和0.1%。
下表3中给出了干膜(墨印刷和干燥之后)中并因此例如存在于最终器件中的PEDOT:PSS和添加剂的比例,值对应于质量比例:
PEDOT:PSS(%) 添加剂(%)
干膜墨1 87.5 12.5
干膜墨2 71.5 28.5
3/对液滴喷出能力的影响
借助FujiFilm Dimatix DMP2800型材料打印机测试了墨液滴喷出能力,其中在30℃下进行液滴喷出并同时施加30V电压。
测试了墨1并与包含PEDOT:PSS的悬浮液进行比较。
如图2所举例说明的,添加添加剂能够改善液滴喷出能力,并且特别地增加液滴喷出稳定性。
4/对接触角的影响
测试了上述墨1和2(含有添加剂)以及没有添加剂的相同墨(对应于包含PEDOT:PSS的分散体)。
对具有与OPV器件结构类似的结构的样品进行了测试,所述结构为:
基底/导电氧化物/N层/有源层
在通过旋涂进行沉积之前,通过乙酸锌衍生物的热转化形成N层。其最终厚度为约20nm。有源层由聚(3-己基噻吩)(P3HT)和([6,6]-苯基-C61-丁酸甲酯)(PCBM)的混合物制成。其干燥厚度为200nm并且P3HT:PCBM质量比为1:0.6。在惰性气氛下通过邻二氯苯中溶液的旋涂使其沉积。
借助由软件Drop Shape Analysis II控制的Krüss EasyDrop DSA20装置以静态模式在温度(~25℃)和湿度(~35%)的环境条件下进行接触角测量。
下表4的每个值对应于9次测量的平均值。
由该表和图3所显而易见的,制剂中添加剂的存在能够改善其铺在器件有源层上的能力。对于根据本发明的两种制剂,确实可观察到在添加剂存在下的显著降低。
5/对干膜导电性的影响
为了这些测量,通过旋涂在玻璃基底上制备了厚度为约100nm的沉积物。然后使样品在热板上在120℃下在惰性气氛中退火10分钟。
如下表5所指示的,所测试比例的添加剂的存在不显著改变干膜的导电性:
6/根据本发明的器件的性能
在具有以下结构的NIP型器件上进行了测试:
PET基底(1)/导电氧化物(6)/N层(5)/有源层(4)/P层(3)/银上电极(2)
其中,N层(5)=氧化锌(ZnO);
有源层(4)=聚(3-己基噻吩)/[6,6]-苯基-C61-丁酸甲酯(P3HT:PCBM)
通过旋涂形成了第一两个层(N层和有源层),同时通过喷墨印刷形成了P层(3)和银电极(2)。器件的活性表面面积是1.8cm2,并且在标准光照条件(1,000W/m2,AM1.5G)下在25℃下测量了其性能。
下表6公开了根据所测试制剂的器件的性能:
制剂 效率
墨1 1.20%
墨2 2.10%
墨1和2可通过喷墨施用并且与印刷电极相容。
如由以上内容所显而易见的,本发明主张添加已很好鉴定的导电或半导体添加剂,其具有以下优点:
-在不需要任何表面处理的情况下,能够实现HTL在有源层上的均一且均匀的沉积;
-在OPV电池中具有满意的性能;
-与印刷电极相容。
更通常地,本发明提供了配制改善其润湿疏水表面之能力的包含PEDOT:PSS的组合物的技术方案。因此,本发明可用于其中包含EDOT:PSS的层应沉积在疏水层上,特别是光电器件(如OLED和PLED)由疏水材料制成的有源层上的所有器件。

Claims (18)

1.一种组合物,其包含:
-聚(3,4-亚乙基二氧噻吩)或PEDOT;
-聚苯乙烯磺酸酯或PSS;
-具有下式的化合物(A):
其中
-0<x/y<1;
-Ar1和Ar2表示可相同或不同的芳香环;
-Ar1和/或Ar2在其环上包含至少一个疏水取代基。
2.根据权利要求1所述的组合物,其特征在于所述化合物(A)是导电的或者是电的半导体。
3.根据权利要求1或2所述的组合物,其特征在于所述芳香环(Ar1、Ar2)选自包括以下的组:噻吩、联噻吩、三联噻吩、噻吩并噻吩、吡咯、咔唑、吡咯并吡咯二酮(DPP)、硒酚、环戊并二噻吩(CPDT)、二噻吩环戊并二噻吩、Si-环戊并二噻吩(Si-CPDT)、二噻吩-Si-环戊并二噻吩、芴、二噻吩芴、苯、苯并噻唑、苯并噻二唑、二噻吩苯并噻二唑、喹喔啉、噻唑、磷杂茂(phosphole)。
4.根据权利要求3所述的组合物,其特征在于芳香环Ar1和Ar2是噻吩。
5.根据前述权利要求中任一项所述的组合物,其特征在于所述疏水取代基是醚链(-O-R),其中R可以是直链或支链,包含碳原子,有利地为1至15个,以及可能的杂原子,例如O或N,有利地为1至10个。
6.根据权利要求5所述的组合物,其特征在于Ar1和/或Ar2,有利地Ar1和Ar2包含具有以下结构的疏水取代基:
7.根据前述权利要求中任一项所述的组合物,其特征在于所述化合物(A)具有下式:
8.根据前述权利要求中任一项所述的组合物,其特征在于其还包含选自包括以下的组的至少一种溶剂:水、丙-2-醇、2-丁氧基乙醇(或乙二醇单丁醚,EGMBE)、乙醇、丁-1-醇、丁-2醇、乙二醇、丙二醇、二甘醇、二丙二醇甲醚、乙二醇甲醚。
9.根据权利要求8所述的组合物,其特征在于其包含:
-水,有利地按体积计的比例小于5%,更有利地还小于2%,并且最佳地等于0%;
-丙-2-醇,有利地按体积计的比例大于30%,更有利地还在40%与60%之间,并且最佳地在50%与55%之间;
-2-丁氧基乙醇,有利地按体积计的比例在10%与50%之间,并且更有利地在15%与35%之间。
10.根据前述权利要求中任一项所述的组合物,其特征在于所述化合物(A)相当于按所述组合物重量计的0.05%至0.2%。
11.一种用于制备根据权利要求1至10中任一项所述的组合物的方法,其包括使化合物(A)混合在包含PEDOT:PSS的分散体中。
12.一种形成光电器件的方法,有利地形成倒置构造(NIP)的光伏电池(OPV)的方法,其包括使根据权利要求1至10中任一项所述的组合物在层上沉积,以有利地在有源层上形成HTL。
13.根据权利要求12所述的形成光电器件的方法,其特征在于所述沉积通过喷墨印刷进行。
14.根据权利要求12或13所述的形成光伏器件的方法,其特征在于然后使例如由银制成的上电极沉积在所述HTL的表面上,其有利地通过喷墨印刷进行。
15.一种光电器件,有利地是一种倒置构造(NIP)的光伏电池,其具有包含以下成分的层:
-聚(3,4-亚乙基二氧噻吩)或PEDOT;
-聚苯乙烯磺酸酯或PSS;
-根据权利要求1至7中任一项所限定的化合物(A)。
16.根据权利要求15所述的光电器件,其特征在于所述化合物(A)相当于按所述层干重计的1%至30%,有利地为25%至30%。
17.根据权利要求15或16所述的光电器件,其特征在于所述层布置在所述器件的有源层的表面上。
18.根据权利要求1至7中任一项所述的化合物(A)用于增加包含PEDOT:PSS的组合物润湿层的润湿能力的用途,所述层有利地为光电器件的有源层。
CN201310717113.9A 2013-01-31 2013-12-23 光电器件特别是倒置型opv电池的形成方法 Pending CN103965591A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105038411A (zh) * 2015-07-14 2015-11-11 浙江中科立德新材料有限公司 一种导电油墨及其制备方法和使用方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3023064B1 (fr) * 2014-06-25 2018-02-02 Dracula Technologies Dispositif photovoltaique et son procede de fabrication
FR3059671B1 (fr) * 2016-12-01 2020-10-30 Arkema France Composition polymere electriquement conductrice et transparente a base de poly(3,4-ethylenedioxythiophene) et de polyelectrolyte

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7582707B2 (en) * 2004-01-12 2009-09-01 Air Products And Chemicals, Inc. Aqueous blends and films comprising a first electrically conducting conjugated polymer and a second electrically conducting conjugated polymer
JP4519679B2 (ja) * 2005-02-21 2010-08-04 Necトーキン株式会社 導電性高分子組成物およびそれを用いた固体電解コンデンサ
GB2433646A (en) * 2005-12-14 2007-06-27 Seiko Epson Corp Printing ferroelectric devices
EP2049582B1 (en) * 2006-07-21 2019-02-27 Nissan Chemical Corporation Sulfonation of conducting polymers and oled, photovoltaic, and esd devices
EP2257594B1 (en) * 2008-03-06 2014-11-12 Plextronics, Inc. Modified planarizing agents and devices
JP2010192863A (ja) * 2008-05-23 2010-09-02 Sumitomo Chemical Co Ltd 有機光電変換素子およびその製造方法
JP2010040512A (ja) * 2008-07-10 2010-02-18 Sumitomo Chemical Co Ltd 有機エレクトロルミネッセンス素子およびその製造方法
CN102333825B (zh) * 2008-12-31 2014-02-26 埃西勒国际通用光学公司 增强导电性聚合物基涂料的抗静电性能的添加剂
KR20120006562A (ko) * 2009-05-01 2012-01-18 플렉스트로닉스, 인크 수성을 비수성 용매로 대체하는 방법
CN107104186B (zh) * 2009-09-29 2020-06-30 索尔维美国有限公司 有机电子器件、组合物和方法
JP5682887B2 (ja) * 2010-11-02 2015-03-11 学校法人東京理科大学 導電性高分子ナノ微粒子分散溶液、当該分散溶液を用いた導電薄膜及び導電薄膜の製造方法
KR20120073809A (ko) * 2010-12-27 2012-07-05 삼성전기주식회사 전도성 고분자 조성물 및 이를 이용한 전도성 필름
WO2012132828A1 (ja) * 2011-03-29 2012-10-04 住友化学株式会社 有機光電変換素子の製造方法
JP5676363B2 (ja) * 2011-05-26 2015-02-25 国立大学法人広島大学 光起電力素子およびその製造方法
KR101644770B1 (ko) * 2011-09-06 2016-08-01 데이카 가부시키가이샤 도전성 고분자의 분산액, 도전성 고분자 및 그 용도

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105038411A (zh) * 2015-07-14 2015-11-11 浙江中科立德新材料有限公司 一种导电油墨及其制备方法和使用方法

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