CN101058672A - 一种组合物及由其制成的场致发光器件 - Google Patents

一种组合物及由其制成的场致发光器件 Download PDF

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CN101058672A
CN101058672A CNA2007101091169A CN200710109116A CN101058672A CN 101058672 A CN101058672 A CN 101058672A CN A2007101091169 A CNA2007101091169 A CN A2007101091169A CN 200710109116 A CN200710109116 A CN 200710109116A CN 101058672 A CN101058672 A CN 101058672A
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E·P·伍
M·T·比尼厄斯
M·印巴斯卡兰
吴唯实
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Abstract

包含10-90wt%式(I)基团和10-90wt%选自式(II)、(III)和(IV)基团及其混合物的共聚物。其中,R1分别独立地为H,C1-C20烃基或含一个或多个S、N、O、P或Si原子的C1-C20烃基,C4-C16烃基羰基氧基,C4-C16芳基(三烷基硅烷氧基),或者两个R1可与芴环上的9位碳原子形成C5-C20脂肪环结构或含一个或多个S、N或O杂原子的C4-C20脂肪环结构;R2分别独立地为C1-C20烃基、C1-C20烃氧基、C1-C20硫醚、C1-C20烃基羰基氧基或氰基;R3分别独立地为羧基、C1-C20烷基、C1-C20烷氧基或式为-CO2R4的基团,其中R4为C1-C20烷基;a和b分别独立地为0至3的整数。

Description

一种组合物及由其制成的场致发光器件
本申请是国际申请日为1999年4月9日,国际申请号为PCT/US99/07768,名称为“含芴聚合物及由其制成的场致发光器件”的中国专利申请No.99800587.8的分案申请。
已知含有共轭基团的聚合物可作为制备有机基发光二极管的材料使用,但是,这些二极管在低驱动电压下的光辐射和效率不能满足特定应用的需要。因此,需要具有改进效率的器件和可在低驱动电压下提供高亮度的器件。
一方面,本发明是共聚物,该共聚物包含10-90wt%式(I)的基团和10-90wt%选自式(II)、(III)和(IV)的基团及其混合物:
Figure A20071010911600041
其中,R1分别独立地为H,C1-C20烃基或含一个或多个S、N、O、P或Si原子的C1-C20烃基,C4-C16烃基羰基氧基,C4-C16芳基(三烷基硅烷氧基)或两个R1可与芴环上的9位碳原子形成C5-C20脂肪环结构或含一个或多个S、N或O杂原子的C4-C20脂肪环结构;
R2分别独立地为C1-C20烃基、C1-C20烃氧基、C1-C20硫醚、C1-C20烃基羰基氧基或氰基;
R3分别独立地为羧基、C1-C20烷基、C1-C20烷氧基或式为-CO2R4的基团,其中R4为C1-C20烷基;
a和b分别独立地为0至3的整数。
第二方面,本发明是组合物,该组合物包含(a)1-99wt%的本发明第一方面中所述共聚物和(b)99-1wt%的至少一种含式(I)基团和任选地不同于式(II)、(III)和(IV)的共轭基团的聚合物。
第三方面,本发明是场致发光(EL)器件,该场致发光器件包含至少一个有机膜,至少一个有机膜为发光有机膜,有机膜安置在阳极材料和阴极材料之间,以便当加正向偏压于该器件时,在使用电压下空穴由阳极材料注入与阳极材料邻接的有机膜,而电子由阴极材料注入与阴极材料邻接的有机膜,从而导致发光有机膜发光;其中至少一层包含本发明第一方面中所述的共聚物。
当用做场致发光器件中的发光和/或空穴传输层时,在低驱动电压下,本发明共聚物使器件的效率和亮度均高于不含本发明共聚物的相应器件。以流明/瓦特(Lm/W)表示效率。下列叙述将明显体现本发明的这些及其它优势。
在此使用的“共轭基团”一词是指含双键、参键和/或芳香环的物种。这样的基团进入聚合物链后,可改进聚合物的光吸收、电离势和/或电性质。在此使用的“烃基”是指除非另外说明只含氢和碳的任何有机物种,其可包括芳香族、脂肪族、脂肪环和含两个或更多脂肪族、脂肪环和芳香族物种的物种。
在上述式中,R1优选H、C1-C12烷基、C6-C10芳基或烷基取代芳基、C4-C16烃基羰基氧基、(C9-C16芳基)三烷基硅烷氧基、含端羟基的聚(亚烷基氧基)基团、C1-C10烃氧基,或具有式-(CH2)bCO2R6、-(CH2)bSO3R6、-(CH2)bN(R1)2、-(CH2)bN+(R1)3或-(CH2)b-CN的基团,其中R6为C1-C6烃基、H、Li+、Na+或K+,b的定义同前。在两个R1与芴环中的9位碳原子形成环结构的实施方案中,形成的环结构优选C5-C20脂肪环结构或含一个或多个S、N或O杂原子的C4-C10脂肪环结构,甚至更优选C5-C10脂肪环或含一个或多个S或O的C4-C10脂肪环,最优选C5-C10环烷基或含氧原子的C4-C10环烷基。
上述式(I)中的芴基可进一步在3-、4-、5-或6-位被既不负面影响相应单体形成齐聚物或聚合物,也不影响齐聚物或聚合物后续加工的取代基(R2)取代。优选地,R2为C1-C4烷氧基、苯氧基、C1-C4烷基、苯基或氰基。但是,“a”优选为0。
以共聚物的重量计,共聚物中式(I)基团的含量优选至少10%,更优选至少20%,最优选至少50%;但优选不高于99%,更优选不高于85%,最优选不高于75%。以共聚物的重量计,共聚物中式(II)、(III)和(IV)基团的含量优选至少5%,更优选至少10%,最优选至少20%;但优选不高于95%,更优选不高于85%,最优选不高于75%。
本发明的聚合物和共混物在稀溶液或在固态表现出强光致发光性。当这样的材料暴露于波长为300-700纳米(nm)的光线下时,这些材料发射波长在400nm至800nm范围内的光。更优选地,这样的材料吸收波长为350-400nm的光,发射波长在400-650nm范围内的光。本发明的聚合物和共混物易溶于常见的有机溶剂,可通过传统技术将其加工成薄膜或涂层。
本发明的芴齐聚物或聚合物优选具有1000道尔顿(Daltons)或更高的重均分子量,更优选5000Daltons或更高,甚至更优选10000Daltons或更高,甚至更加优选15000Daltons或更高,最优选20000Daltons或更高;优选1000000Daltons或更小,更优选500000Daltons或更小,最优选200000Daltons或更小。以聚苯乙烯为标准,根据凝胶渗透色谱法测定分子量。本发明聚合物的聚合度优选至少3。
优选地,本发明共聚物的多分散度(Mw/Mn)表现为5或更小,更优选4或更小,甚至更优选3或更小,甚至更加优选2.5或更小,最优选2.0或更小。
优选地,本发明第一方面中所述的共聚物具有下列结构之一:
Figure A20071010911600071
Figure A20071010911600081
Figure A20071010911600091
其中,n为大于3的数.
制备聚合物的方法
含式(I)-(IV)基团的聚合物可以任何适宜的方法制备,但优选以下述方法之一制备。通常被称为“Suzuki反应”的芳香硼酸酯和溴化物的缩合反应,在N.Miyaua和A.Suzuki的论文“ChemicalReviews,Vol.95,PP.457-2483(1995)”中有所描述。该反应可用于制备高分子量的聚合物和共聚物。在Pd和三苯基膦的催化作用下,含选自式(I)-(IV)或其混合物的内在基团的二溴化物,与等摩尔量含选自式(I)-(IV)或其混合物的内在基团的二硼酸或二硼酸酯反应制备聚合物。该反应典型地在70-120℃下、在芳烃溶剂如甲苯内进行,也可单独使用其它溶剂如二甲基甲酰胺和四氢呋喃,或与芳烃溶剂混合使用。碱性水溶液,优选碳酸钠或碳酸氢钠的水溶液用做HBr的接收剂。依反应物的反应性不同,聚合反应可能需要2-100小时。其它反应条件参数见T.I.Wallow和B.M.Novak的论文Journal of Organic Chemistry,Vol.59,PP.5034-5037(1994),M.Remmers,M.Schulze和G.Wegner的论文Macromolecular Rapid Communications,Vol.17,PP.239-252(1996),及美国专利5777070。当含一类选自式(I)-(IV)的内在基团的二溴化物与含选自式(I)-(IV)的不同内在基团的含硼单体反应时,则产生交替共聚物。若有必要,可使用单官能团芳基卤化物或芳基硼酸酯作为这样反应的链终止剂,这将导致端芳基的形成。为制备高分子量聚合物,Suzuki聚合反应中可使用不止一种二硼酸/二硼酸酯和不止一种二溴化物,只要二硼酸/二硼酸酯的总摩尔量与二溴化物的总量基本相等。
通过控制Suzuki反应单体进料的次序和组成可控制单体单元在所得共聚物中的顺序。例如,只要在硼酸基团与溴基团之间存在总体平衡,通过以合适比例首先加入反应物制备交替芴-共聚单体齐聚物,然后加入其余的芴单体的方式,可制备主要包含与短嵌段交替芴-共聚单体齐聚物相连的大嵌段芴均聚物的高分子量共聚物。
另一可供选择的聚合方法仅涉及二卤官能团反应物,可使用镍偶联反应完成。一个这样的偶联反应在Colon等人的论文Journalof Polymer Science,Part A,Polymer Chemistry Edition,Vol.28,P.367(1990)和论文Journal of Organic Chemistry,Vol.51,P.2627(1986)中有所描述。反应典型地在催化用量的镍盐、足量三苯基膦和大量过量锌粉的存在下,在极性非质子传递溶剂(例如,二甲基乙酰胺)中进行。该方法的衍生方法在loyda等的论文Bulletin of the Chemical Society of Japan,Vol.63,p.80(1990)中有所描述,其中使用有机可溶性碘化物作为促进剂。另一镍偶联反应在Yamamoto的Progress in Polymer Science,Vol.17,p.1153(1992)中有所报道,其中,在惰性溶剂中以过量的镍(1,5-环辛二烯)配合物处理二卤代芳香化合物的混合物。当应用于两种或多种芳香二卤化物的反应混合物时,所有的镍-偶联反应均主要得到无规共聚物。可向聚合反应混合物内加入少量水终止这样的聚合反应,这将以氢基团替代端基卤素基团。可选择地,可使用单官能团芳基卤化物作为这类反应的链终止剂,这将导致端芳基的形成。
在一个实施方案中,本发明第二方面中所述成分(b)的聚合物含不同于上述芴和胺基的共轭基团。这样的聚合物可使用上述方法,掺入至少一种不同于上述芴和胺基的共轭单体化合物来制备。
共轭共聚单体的例子包括1,2-二苯乙烯、二苯乙炔、C6-C20单核/多核芳烃和C2-C10单核/多核杂环化合物。
单核/多核芳烃的例子包括苯、萘、二氢苊、菲、蒽、荧蒽、芘、红荧烯和(C18H12)。单核/多核杂环的例子包括:五元杂环,如呋喃、噻吩、吡咯、噁唑、异噁唑、噻唑、异噻唑、咪唑、噁二唑、噻二唑和吡唑;六元杂环,如吡啶、哒嗪、嘧啶、吡嗪、三嗪和四氮烯;苯并稠环体系,如苯并噁唑、苯并噻唑、苯并咪唑、喹啉、异喹啉、噌啉、喹唑啉、喹喔啉、2,3-二氮杂萘、苯并噻二唑和苯并三嗪;多核稠环体系,如吩嗪、菲啶、吖啶、咔唑和二苯并呋喃。一般而言,含至多30个碳原子的共轭化合物可用于本目的,它们可任意地被一个或多个对聚合物组合物的光致发光性质无害的取代基取代。取代基的例子包括C1-C20烃基、C1-C20烷氧(硫)基、C1-C20芳氧(硫)基、氰基、氟、氯、C1-C20烷氧基羰基、C1-C20芳氧基羰基、C1-C20羧基和烷基(芳基)硫酰基。不希望出现已知为荧光猝灭剂的取代基,如芳羰基和硝基。
也可使用结构式(1)-(8)所示的更复杂结构的共轭单体单元。
Y=S或O
Figure A20071010911600121
含芴单体
可用于制备本发明聚合物的含芴单体包括下列式的化合物:
Figure A20071010911600122
其中,R1、R2和a的定义同前;
X分别独立地为卤素部分;
Z分别独立地为-B(OH)2、-B(OR4)2
Figure A20071010911600123
其中R4分别独立地为C1-C10烷基,R5分别独立地为C2-C10亚烷基。
X优选为氯或溴,但最优选溴。Z优选为由乙二醇或丙二醇衍生的环形硼酸酯。
可以任何适宜的方法制备含硼芴化合物。用于制备含硼化合物的反应条件的例子在Remmers等的论文Macromolecular RapidCommunications,Vol.17,PP.239-253(1996)中有所描述。通过与两当量丁基锂反应,可将相应二卤官能团化合物的化合物转化为相应的二锂衍生物。二锂衍生物与硼酸三烷基酯反应,然后水解,得到相应的二硼酸(Z=B(OH)2)。二硼酸与亚烷基二醇如乙二醇发生酯化过程,得到双环硼酸酯。
含胺单体
可根据美国专利5728801中公开的过程制备用于合成本发明第一方面中所述共聚物的含胺单体。
聚合物共混物
第二方面,本发明是组合物,该组合物包含(a)1-99wt%的本发明第一方面中所述共聚物和(b)99-1wt%的至少一种含式(I)基团和任选地不同于式(II)、(III)和(IV)的共轭基团的聚合物。
本发明第一方面中含胺共聚物的特征在于,其对空穴由阳极注入的低位垒。因此,包含至少一种这些共聚物的场致发光器件通常表现出低于不含这些共聚物的相应器件的启动电压。通过构造含胺共聚物作为其中的独立层的多层器件,或构造含胺共聚物与发光聚合物的共混物作为一层的单层器件,均可实现这些共聚物向发光器件中的掺入。
以成分(a)和(b)的总重量计,优选成分(a)为至少1wt%、更优选至少10Wt%、最优选至少20Wt%,但优选不高于99wt%、更优选不高于95wt%、最优选不高于90wt%。
本发明共混物的成分(b)可为共轭均聚物或无规、嵌段或交替共聚物,聚合度至少为3。优选地,聚合物或共聚物高度发光并易溶于大多数常见有机溶剂。含共轭基团的适宜聚合物的例子包括包含式(XV)单体单元的聚芴、交替共聚物:
Figure A20071010911600131
其中,R7分别独立地为C1-C12烃基和选自结构(1)-(8)的其它单体单元。
聚合物应用
本发明的另一方面是由本发明共聚物形成的薄膜。这样的薄膜可用于聚合物发光二极管。优选地,这样的薄膜用做发光层或电荷载体传输层。这些聚合物也可用做电子器件的保护涂层和用做发光涂层,涂层或薄膜的厚度取决于最终应用,一般地,这样的厚度为0.01-200微米。在将涂层用做发光涂层的实施方案中,涂层或薄膜的厚度为50-200微米;在将涂层用做电子保护层的实施方案中,涂层的厚度为5-20微米;在将涂层用做聚合物发光二极管的实施方案中,形成的层厚为0.05-2微米。本发明的齐聚物或高聚物形成良好的无细针孔和缺陷的薄膜。这样的薄膜可通过本领域熟知的方法制备,这些方法包括旋涂、喷涂、浸涂和辊涂。这样的涂层以包括将组合物涂敷于基体、将已涂敷的组合物置于可形成薄膜的条件下的方法制备。形成薄膜的条件取决于涂敷方法。优选地,使用溶液加工方法,采用所需聚合物在常见有机溶剂中的0.1-10wt%溶液。对于薄涂层,用于形成薄膜的组合物优选含有0.5-5.0wt%的齐聚物或高聚物。然后以所需方法将这一组合物涂敷于合适的基体上,使溶剂蒸发。以真空和/或加热的方式除去残留溶剂。若溶剂沸点低,则需要低溶液浓度,例如,0.1-2%。若溶剂沸点高,则需要高溶液浓度,例如,3-10%。
本发明的另一方面涉及包含本发明聚合物薄膜的有机场致发光(EL)器件。有机EL器件典型地由如三明治般夹于阳极和阴极之间的有机薄膜组成,以便当向器件施正偏压时,空穴由阳极注入有机薄膜,而电子由阴极注入有机薄膜。空穴和电子的组合可能产生激子,激予可能通过释放光子发生辐射衰变至基态。实践中,由于锡和铟混合氧化物的电导率和透明度,阳极通常是锡和铟的混合氧化物。将混合氧化物(ITO)沉积于透明基体如玻璃或塑料上,以便可观察到有机薄膜的发射光。有机薄膜可以是几个单个层的复合,每一半个层设计为不同的功能。由于空穴由阳极注入,因此与阳极邻接的层需有传输空穴的功能,相似地,与阴极邻接的层需有传输电子的功能。多数情况下,空穴(电子)传输层也充当发射层。在某些情况下,一层即表现出传输空穴和电子及发光的综合功能。有机薄膜的各个层可本质上是聚合物的,或是聚合物膜和通过热蒸发沉积的小分子膜的组合。有机薄膜的总厚度优选小于1000nm,更优选小于500nm,最优选小于300nm。本发明的一个实施方案是其有机薄膜包含至少一种本发明聚合物组合物的EL器件。
以洗涤剂、有机溶剂和UV-臭氧处理进行常规清洁后,作为基体和阳极的ITO-玻璃可用于涂布。也可先以导电物质的薄层对其进行涂布,以便于空穴注射。这样的物质包括酞菁铜、聚苯胺和聚(3,4-亚乙二氧基-噻吩)(PEDT),可通过掺杂强有机酸如聚(苯乙烯磺酸)的方式使后两种物质具备导电性。该层的厚度优选200nm或更小,更优选100nm或更小。
在使用独立空穴传输层的情况下,可使用1996年2月23日申请的美国专利申请No.08/606180、1996年8月13日申请的美国专利申请No.08/696280和美国专利5728801中所述的聚合芳胺。也可使用其它已知的空穴传导聚合物如聚乙烯基咔唑。此传输层抵抗下一步将要涂敷的共聚物薄膜溶液浸蚀的能力对多层器件的成功制作非常关键。因为本发明共聚物是以二甲苯或甲苯溶液施用的,因此,要求该空穴传输层不溶于这些溶剂。该传输层的厚度可为500nm或更小,优选300nm或更小,最优选150nm或更小。可选择地,用于这些器件的空穴传输聚合物可选自半导体聚合物,如掺杂的聚苯胺、掺杂的聚(3,4-亚乙二氧基噻吩)和掺杂的聚吡咯。“掺杂”是指半导体聚合物(如聚苯胺和聚(3,4-亚乙二氧基噻吩)的翠绿亚胺碱)与可使所得聚合物组合物导电性更强的添加剂的共混。优选地,导电聚合物由聚(3,4-亚乙二氧基噻吩)和聚合酸的共混产生,更优选地,聚合酸含磺酸基团,最优选聚合酸是聚苯乙烯磺酸。最优选的聚合物组合物由聚(3,4-亚乙二氧基噻吩)和至少两当量聚苯乙烯磺酸的共混产生。
在使用电子传输层的情况下,其可通过低分子量材料热挥发或通过聚合物溶液涂布的方式涂敷,聚合物溶液所用的溶剂不对底层薄膜造成明显的损坏。
低分子量材料的例子包括8-羟基喹啉的金属配合物(如在Burrows等人的论文Applied Physics Letters,Vol.64,PP.2718-2720(1994)中所描述的)、10-羟基苯并喹啉的金属配合物(如在Hamada等人的论文Chemistry Letters,PP.906-906(1993)中所描述的)、1,3,4-噁二唑(如在Hamada等人的论文Optoelectronics-Devices and Technologies,Vol.7,Pp.83-93(1992)中所描述的)、1,3,4-三唑(如在Kido等人的论文Chemistry Letters,PP.47-48(1996)中所描述的)和芘的二羧酸酰亚胺(如在Yoshida等人的论文Applied Physics Letters,Vol.69,pp.734-736(1996)中所描述的)。
聚合电子传输材料的例子包括含1,3,4-噁二唑的聚合物(如在Li等人的论文Journal of Chemistry Society,PP.2211-2212(1995)及Yang和Pei等人的论文Journal of Applied Physics,Vol.77,pp.4807-4809(1995)中所描述的)、含1,3,4-三唑的聚合物(如在Strukeli等人的论文Science,Vol.267,pp.1969-1972(1995)中所描述的)、含喹喔啉的聚合物(如在Yamamoto等人的论文JapanJournal of Applied Physics,Vol.33,PP.L250-L253(1994)及O’Brien等人的论文Synthetic Metals,Vol.76,pp.105-108(1996)中所描述的)和氰基-PPV(如在Weaver等人的论文Thin SolidFilms,Vol.273,pp.39-47(1996)中所描述的)。此传输层的厚度可为500nm或更小,优选300nm或更小,最优选150nm或更小。
可采用热挥发或喷涂的方式沉积金属阴极。阴极的厚度可为100-10000nm。优选的金属为钙、镁、铟和铝。也可使用这些金属的合金。优选含1-5%锂的铝合金和含至少80%镁的镁合金。
当置于50伏或更小的使用电压下,本发明的EL器件即发光,其发光效率为至少0.1流明/瓦特,但可高达2.5流明/瓦特。
在优选的实施方案中,场致发光器件包括至少一种本发明的共聚物,其置于阳极材料和阴极材料之间,以便当施加正向偏压于该器件时,在使用电压下,空穴可由阳极材料注入空穴传输聚合物薄膜,而电子由阴极材料注入发光聚合物薄膜,使发光层发光。
在此使用的“阳极材料”一词是指半透明或透明的导电薄膜,其功函数在4.5eV至5.5eV之间。其例子包括铟、锡和金的氧化物或它们的混合氧化物。在此使用的“阴极材料”一词是指功函数在2.5eV至4.5eV之间的导电薄膜。其例子包括锂、钙、镁、铟、银、铝、钇,或上述金属的共混物或合金。
示例性实施方案
下列实施例仅为示例性目的,其并不限制权利要求书的范围。
此处实施例中含胺共聚物具有式(V)-(XII)的结构。此处实施例中命名的其它聚合物具有下列结构:
Figure A20071010911600171
将本发明第一方面的含胺共聚物与F8或与F8和BT的混合物共混,制备本发明第二方面中所述共混物。符号“3BTF8”代表F8内含3wt%BT的共混物;相似地,“5BTF8”代表F8内含5wt%BT的共混物。
这些聚合物及其前体单体的合成在PCT公开WO97/05184及1997年10月23日申请的题为“制备共轭聚合物的方法”的美国专利申请No.08/956797中有所描述。
实施例1-单层器件
将合适的聚合物共混物的二甲苯溶液旋涂于ITO-玻璃上,然后沉积钙阴极,制备单层场致发光器件。聚合物共混物的成分为5BTF8和胺共聚物。亮度为1000Cd/m2下的器件操作参数列于表1,表1同时列出了根据公式“πL/(10JV)”得到的效率,即流明/瓦特,公式中的L即是1000Cd/m2。偏压(V)是亮度达到1000Cd/m2的电压;相似地,电流密度(J)是1000Cd/m2下器件每单位面积的电流,单位为mA/cm2
表1.单层器件
器件 膜厚(nm) 胺共聚物 比例* V J(mA/cm2) 流明/瓦特
1a 150 0∶1 16.8 39.1 0.48
1b 100 TFB 1∶3 6.6 21.9 2.17
1c 100 PFB 1∶3 5.6 63.4 0.88
1d 150 PFMO 1∶3 9.3 41.6 0.81
1e 150 BFE 1∶5 10.9 47.7 0.60
1f 150 BFE 1∶3 5.6 21.1 2.66
1g 150 PFE 1∶3 9.3 37.5 0.90
*胺共聚物与5BTF8的重量比
以聚合物薄膜为基质但不含胺共聚物的器件1a达到1000Cd/m2亮度所需要的驱动电压明显高于以聚合物薄膜为基质且含胺共聚物的器件所需要的电压,1a的效率最低。
实施例2-双层器件
双层器件如下所述制备。由聚合物的N,N-二甲基甲酰胺溶液旋涂形成第一层(BFA或PFA)。形成的薄膜在60-90℃下真空干燥。由聚合物或聚合物共混物的二甲苯溶液旋涂形成第二层。在每一个情况下,层2均为发光层。
 表2.双层器件
  器件  层1(nm)  层2(nm)* V J(mA/cm2) 流明/瓦特
  1a   5BTF8(150) 16.8 39.1 0.48
  2a  BFA(25)   5BTF8(100) 9.3 36.5 0.93
  2b  PFA(25)   3BTF8(100) 8.4 31.8 1.17
  2c  BFA(40)   F8(150) 24伏下的最大亮度=120Cd/m2
  2d  BFA(60)   10wt.%TFMO/90WT.%F8(100) 11 174 0.16
*括号内的数字是以nm为单位的膜厚。
对比2a和2b与1a的性能发现,存在于ITO和层2(发光层)之间的本发明胺共聚物层明显地降低了使亮度达到1000Cd/m2所需要的电压,同时伴随效率的提高。器件2d具有含本发明胺共聚物的发光聚合物膜,而2c没有。前者在11伏达到1000Cd/m2,而后者在24伏下仅能达到120Cd/m2。这些结果明显说明,不论是作为独立的空穴传输层,还是作为发光层的共混物成分,本发明的共聚物均存在优势。

Claims (3)

1.一种组合物,它包含(a)如下物质的共聚物:1-99wt%的共聚物,该共聚物包括10-90wt%的如式(I)的基团和10-90wt%的选自式(II)、(III)和(IV)基团及其混合物的基团;和(b)99-1wt%至少一种含式(I)基团和任选地不同于式(II)、(III)或(IV)的共轭基团的聚合物;
Figure A2007101091160002C1
其中,R1分别独立地为H,C1-C20烃基或含一个或多个S、N、O、P或Si原子的C1-C20烃基,C4-C16烃基羰基氧基,C4-C16芳基(三烷基硅烷氧基),或两个R1可与芴环上的9位碳原子形成C5-C20脂肪环结构或含一个或多个S、N或O杂原子的C4-C20脂肪环结构;
R2分别独立地为C1-C20烃基、C1-C20烃氧基、C1-C20硫醚、C1-C20烃基羰基氧基或氰基;
式(II)的R3独立地为C1-C20烷基或C1-C20烷氧基,
式(III)的R3独立地为C1-C20烷基或C1-C20烷氧基,
式(IV)的R3独立地为羧基;
且所述共聚物的重均分子量为1,000-1,000,000道尔顿。
2.场致发光器件,其包含至少一个有机膜,有机膜中的至少一个为场致发光有机膜,其安置在阳极材料和阴极材料之间,以便在使用电压下场致发光有机膜发射透过该器件外部透明部分的可见光,其中至少一个有机膜为权利要求1所述共聚物的薄膜。
3.一种器件,它包含透明基体、膜和金属电极,其中透明基体的一个侧面上有透明或半透明导电层,该透明或半透明的导电铟和锡的混合氧化物层构成阳极,而金属电极为阴极,膜包含权利要求1所述的组合物,膜位于包含铟和锡的混合氧化物的该导电层和该金属电极之间。
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