CN101679850B - 新型高导电性有机载流子输送材料 - Google Patents
新型高导电性有机载流子输送材料 Download PDFInfo
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Abstract
Description
本发明涉及一种有机材料,尤其是可在有机电子器件中作为半导体材料或导电材料使用的材料。
有机半导体材料分成空穴-和电子-输送材料。需要它们来制备有机电子元件,例如,有机发光二极管(OLED),有机场效应晶体管(OFET)和/或有机太阳能电池。
空穴输送材料方面,在过去15年间,已开发了非常有效且稳定的结构,视应用不同,其提供不同的空穴注入性质,而且在空穴输送的氧化状态下形成稳定的自由基阳离子。
电子输送材料方面,到现在为止,仅有很少的代表物满足用于有机电子器件的电子输送材料的高要求。目前,菲咯啉的衍生物(BCP和BPhen)以及噁二唑的衍生物被认为是优良的电子导体。在这些结构单元运行期间形成的自由基阴离子物质引起杂环结构中的几何改变,从而使电子输送性质由于形成共轭中断而减弱。
已知的材料在电子注入频带宽度以及在其电子输送还原状态时的稳定性方面都表现出缺陷,这样,特别是会长时间不可逆地形成自由基阴离子。
通常,材料的半导电特性通过掺杂来获得,因为基础材料很难单独就具有足够的导电性。
因此,本发明的目的是提供一种有机电子输送材料,其相对于已知材料,具有改善的电子注入频带宽度和电子输送还原状态下的稳定性。具体地说,本发明的目的是提供一种能长时间可逆地形成自由基阴离子的材料。
为了解决此问题,开发了一种更有效的电子导体,其特点是更大的注入频带宽度,和尤其是具有形成高稳定性的可逆自由基阴离子的能力。
本发明的主题是一种有机载流子输送材料,借助该材料可以同样好地输送电子和空穴,其中在150nm厚的未掺杂材料层中,在0.25V时就已获得大于/等于0.5A/cm2的可测电流密度。
本发明的主题是一种有机半导体材料,其包括来自下述结构的杂环母体化合物的低聚亚苯基(Oligophenylene):
包含上述低聚亚苯基结构的BPyPyP-材料,其在最初含义上是有机的,即仅包括碳、氮和氢,当电子和空穴同样地输送时,会显示出对纯有机材料(即仅含C、H和N的结构)来说的非常规特性,具有比至今好数个数量级的导电性。
特别是,150nm厚的层在0.25V时,在正极和负极方向上就已达到0.6A/cm2的电流密度。
根据特别有利的实施方案,所述层是透明的,尤其优选在整个可见光谱区内是透明的。
在此,在未掺杂材料情况下所达到的电流密度相当于目前仅用所谓的掺杂***才达到的电流密度。
除了繁琐的掺杂处理步骤之外,掺杂材料的缺点还在于,通过掺杂通常形成电荷-转移-配合物而且在可见光谱的长波区吸收,因此不是透明的。根据本发明,这两个缺点可以通过在材料中使用这种单一组分BPyPyP来得以克服。
因此,这种BPyPyP材料能够直接代替n-型掺杂的电子输送基质,从而改善在有机电子元件中使用的阴极电子注入。
根据本发明有利的实施方案,所述BPyPyP材料通过与n-掺杂材料或N-掺杂剂共蒸发而沉积为更高导电性的层。
由于BPyPyP材料是一种极佳的电子输送载体(Electronentransporter),因此它可以在所有有机电子元件和设备中引入该功能。
另外,该材料同样还可以在OLED-设备中作为单独的双极基质使用,和以任意的混合物(共混物)用于任意的发射体材料。
另一方面,也可以从该材料和含该材料的混合物制得在任意衬底上的透明电极,其具有阳极和/或阴极功能。
极佳的电流输送似乎可以采用蒸发法,通过分子自动有机化有序沉积作用来得以实现。
下面,本发明将借助三幅附图进行更详细的说明:
图1显示电流-电压-特性曲线,示出所述材料在正电场和负电场中的导电性。
图2显示在UV/VIS-光谱中的材料透明度,和
最后,图3显示所述化合物的光致发光光谱。
有机电子元件的典型结构包括衬底,下电极,半导体有机层和上阳极。用相应的结构获得图中所列的测量数据。在所示实施例中,衬底由玻璃构成、下电极由氧化铟锡(ITO)构成、半导体有机层是150nm厚的BPyPyP层,该层上面是由100nm厚的铝层构成的第二电极。
实施例
双-2-(4-吡啶基)-嘧啶基-5-基-1,4-亚苯基的制备
1)4-吡啶-甲脒盐酸盐1
在500ml烧瓶中,将4-氰基吡啶(50.0g,470mmol,1当量)与甲醇钠(3.0g,53mmol,0.11当量)一起在约230ml干燥甲醇中在RT搅拌1.5小时。向白色悬浮液中加入氯化铵(27.7g,52mmol,1.1当量),并继续搅拌至少24小时。吸滤出细碎的白色沉淀,母液在旋转蒸发器中浓缩至干燥。将滤饼和母液残余物合并,并用水重结晶。吸滤并用***洗涤后,产物在真空内在RT进行干燥。
产量:70.5g(理论值的95%),白色晶体,M=157.6g·mol-1;熔点:250℃。
2)双(1,4-亚苯基)-2-(3-二甲基氨基-2-丙烯-二甲基-亚铵(iminium))-二-高氯酸盐2
在备有温度计、滴液漏斗和回流冷凝器的1000ml三颈烧瓶中,用安装的干燥管预先加入DMF(200ml,2.5mol,30当量),并通过冰/盐冷却混合物冷却至约0℃。在搅拌下缓慢滴加三氯氧化磷(46ml,0.5mol,6当量),其中温度不得升高至超过0℃。继续搅拌10分钟后,向反应混合物中加入1,4-苯二乙酸(16.3g,0.08mol,1当量)。然后,将溶液加热至90℃达6小时,冷却,倒在1kg冰上。为了沉淀产物,将溶于一些水中的高氯酸钠(30.8g,0.25mol,3当量)在搅拌下加入水溶液中。吸滤出沉淀,用甲醇/***和纯***洗涤,然后真空干燥。
产量:31.5g(理论值的71%),白色晶体,M=527.4g·mol-1;熔点:292-296℃。
3)双-2-(4-吡啶基)-嘧啶基-5-基-1,4-亚苯基
在250ml烧杯中,将4-吡啶甲咪盐酸盐1(5.5g,35mmol,2.2当量)与亚苯基双vinamidinium盐2(8.3g,18mmol,1当量)一起在吡啶中在RF加热8小时。吸滤出所形成的褐黄色沉淀,用甲醇、甲醇/***和纯***洗涤,并且在真空中在RT进行干燥。还可以在DMSO中重结晶。
然后,产物于320℃升华。
产量:4.5g(理论值的74%),浅黄色针状晶体,M=388.4g·mol-1;熔点:>310℃:
DC:硅胶/THF,RF=0.81
分析:1H-NMR,
本发明涉及一种有机半导体材料,尤其是可在有机电子器件中用作半导体材料或导电材料的材料。其中,该材料组分包括来自下述结构的杂环母体化合物的低聚亚苯基:
Claims (6)
1.有机载流子输送材料,包括来自下述结构的杂环母体化合物的低聚亚苯基:
借助该材料可以同样好地输送电子和空穴,其中在150nm厚的未掺杂材料层中,在0.25V条件下就已获得大于/等于0.5A/cm2的可测电流密度。
2.权利要求1的载流子输送材料,其中所述材料以薄膜形式是透明的。
3.前述权利要求之一的载流子输送材料,其作为混合物存在。
4.权利要求1或2的载流子输送材料,其经n-型掺杂或p-型掺杂地存在。
5.前述权利要求之一的载流子输送材料在有机电子元件中的用途。
6.具有基于权利要求1-4之一的载流子输送材料的半导电层和/或导电层的有机电子元件。
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DE102006053644A DE102006053644A1 (de) | 2006-11-14 | 2006-11-14 | Neuartiges hochleitfähiges organisches Ladungsträgertransportmaterial |
PCT/EP2007/062210 WO2008058929A1 (de) | 2006-11-14 | 2007-11-12 | Neuartiges hochleitfähiges organisches ladungsträgertransportmaterial |
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DE102009047880A1 (de) | 2009-09-30 | 2011-03-31 | Osram Opto Semiconductors Gmbh | Organische elektronische Vorrichtung und Verfahren zu dessen Herstellung |
EP2395571B1 (en) | 2010-06-10 | 2013-12-04 | Novaled AG | Organic electronic device comprising an organic semiconducting material |
DE102012205945A1 (de) | 2012-04-12 | 2013-10-17 | Siemens Aktiengesellschaft | Organische Superdonoren mit mindestens zwei gekoppelten Carben-Gruppen und deren Verwendung als n-Dotierstoffe |
DE102012217574A1 (de) | 2012-09-27 | 2014-03-27 | Siemens Aktiengesellschaft | Phosphoroxo-Salze als n-Dotierstoffe für die organische Elektronik |
DE102012217587A1 (de) | 2012-09-27 | 2014-03-27 | Siemens Aktiengesellschaft | Salze des Cyclopentadiens als n-Dotierstoffe für die organische Elektronik |
DE102015210388A1 (de) | 2015-06-05 | 2016-12-08 | Siemens Aktiengesellschaft | Organische Heterozyklische Alkalimetallsalze als n-Dotierstoffe in der Organischen Elektronik |
DE102016208298A1 (de) | 2016-05-13 | 2017-11-16 | Siemens Aktiengesellschaft | Organische elektronenleitende Schicht mit n-Dotierstoff |
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EP0690052A2 (de) * | 1994-07-01 | 1996-01-03 | Hoechst Aktiengesellschaft | Verwendung von Pyrimidingruppen enthaltenden konjugierten Verbindungen als Elektrolumineszenzmaterialien |
CN1182114A (zh) * | 1997-11-12 | 1998-05-20 | 南开大学戈德防伪技术公司 | 螺环类光致变色化合物及其制备方法 |
CN1708539A (zh) * | 2002-10-30 | 2005-12-14 | 西巴特殊化学品控股有限公司 | 用于光学器件的新颖聚合物 |
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JPS6025973A (ja) * | 1983-07-20 | 1985-02-08 | Chisso Corp | ピリミジン類 |
US6147802A (en) | 1994-12-28 | 2000-11-14 | Seiko Epson Corporation | Polarization luminaire and projection display |
KR100573137B1 (ko) * | 2004-04-02 | 2006-04-24 | 삼성에스디아이 주식회사 | 플루오렌계 화합물 및 이를 이용한 유기 전계 발광 소자 |
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EP0690052A2 (de) * | 1994-07-01 | 1996-01-03 | Hoechst Aktiengesellschaft | Verwendung von Pyrimidingruppen enthaltenden konjugierten Verbindungen als Elektrolumineszenzmaterialien |
CN1182114A (zh) * | 1997-11-12 | 1998-05-20 | 南开大学戈德防伪技术公司 | 螺环类光致变色化合物及其制备方法 |
CN1708539A (zh) * | 2002-10-30 | 2005-12-14 | 西巴特殊化学品控股有限公司 | 用于光学器件的新颖聚合物 |
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US8309284B2 (en) | 2012-11-13 |
DE502007005097D1 (de) | 2010-10-28 |
CN101679850A (zh) | 2010-03-24 |
WO2008058929A1 (de) | 2008-05-22 |
JP2010509781A (ja) | 2010-03-25 |
KR20090106472A (ko) | 2009-10-09 |
KR101482512B1 (ko) | 2015-01-13 |
DE102006053644A1 (de) | 2008-06-12 |
EP2092041B1 (de) | 2010-09-15 |
JP5193218B2 (ja) | 2013-05-08 |
EP2092041A1 (de) | 2009-08-26 |
ATE481463T1 (de) | 2010-10-15 |
EP2092041B9 (de) | 2011-11-09 |
US20100112471A1 (en) | 2010-05-06 |
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