CN103450883B - 有机电子材料 - Google Patents

有机电子材料 Download PDF

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CN103450883B
CN103450883B CN201310185347.3A CN201310185347A CN103450883B CN 103450883 B CN103450883 B CN 103450883B CN 201310185347 A CN201310185347 A CN 201310185347A CN 103450883 B CN103450883 B CN 103450883B
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CN103450883A (zh
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戴雷
黄锦海
陈金鑫
蔡丽菲
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BOE Technology Group Co Ltd
Beijing Aglaia Technology Development Co Ltd
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Beijing Aglaia Technology Development Co Ltd
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Priority to CN201310185347.3A priority Critical patent/CN103450883B/zh
Priority to US14/404,604 priority patent/US9905774B2/en
Priority to PCT/CN2013/076236 priority patent/WO2013178041A1/zh
Priority to KR1020147031149A priority patent/KR101775519B1/ko
Priority to TW102118959A priority patent/TWI570984B/zh
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Abstract

本发明涉及“有机电子材料”，属于有机电致发光器件显示材料技术领域。本发明所述的有机电子材料具有式(I)所述的结构式，具有较好热稳定性，高发光效率，高发光纯度。采用该有机发光材料制作的有机电致发光器件具有电致发光效率良好和色纯度优异以及寿命长的优点。

Description

有机电子材料
技术领域
本发明涉及新型的有机电致发光材料，通过真空蒸渡沉积成薄膜，作为蓝光电致发光材料应用在有机电致发光二极管上，属于有机电致发光器件显示技术领域。
背景技术
有机电致发光器件作为一种新型的显示技术，具有自发光、宽视角、低能耗、效率高、薄、色彩丰富、响应速度快、适用温度范围广、低驱动电压、可制作柔性可弯曲与透明的显示面板以及环境友好等独特优点，因此，有机电致发光器件技术可以应用在平板显示器和新一代照明上，也可以作为LCD的背光源。
有机电子发光器件为在两个金属电极之间通过旋涂或者沉积一层有机材料而制备的器件，一个经典的三层有机电致发光器件包含空穴传输层，发光层和电子传输层。由阳极产生的空穴经空穴传输层跟由阴极产生的电子经电子传输层结合在发光层形成激子，而后发光。有机电致发光器件可以通过改变发光层的材料来发射红光，绿光和蓝光。因而，稳定的，高效的和色彩纯的有机电致发光材料对有机电致发光器件的应用和推广具有重要作用，同时也是OLEDs大面积面板显示的应用推广的迫切需求。
在三原色（红，蓝，绿）当中，红光和绿光材料最近已经取得了很大的发展，也符合面板的市场需求。对于蓝光材料，也有一系列的商品化的材料，其中早期用得比较多的为出光兴产的二苯乙烯基联苯(DPVBi）类化合物，以这类化合物制备的器件具有较高的效率，但是往往这些材料的稳定性比较差，更有甚地，这类化合物的发光的颜色属于天蓝光，往往CIE值中的y>0.15。所以由于其不好的温度性和不纯的颜色很大程度地限制了这类化合物在全彩显示器件中的应用。另外一类蓝光材料为柯达公司的ADN和四叔丁基苝，但是这些化合物的发光效率比较差，而且稳定性也不好，从而无法大量使用。
发明内容
本发明就是克服上面化合物的缺陷，提供一系列具有较好热稳定性，高发光效率，高发光纯度的有机电致蓝光材料，由它制备的有机电致发光器件具有电致发光效率良好和色纯度优异以及寿命长的优点。
本发明所述的有机电子材料具有式(I)所述的结构式：
其中，R1-R8独立地表示为氢，氘原子，卤素，氰基，硝基，C1-C8烷基、C1-C8烷氧基，C6-C30的取代或者未取代的芳基，C3-C30的取代或者未取代的含有一个或者多个的杂原子芳基，C2-C8取代或者未取代的烯烷基，C2-C8取代或者未取代的炔烷基，其中，Ar1-Ar4独立地表示C6-C60取代或者未取代的芳基，C3-C60的取代或者未取代的带有一个或者多个杂原子的杂芳基，三芳香（C6-C30)胺基。
优选：其中，R1-R8独立地表示为氢，卤素，氰基，硝基，C1-C8烷基、C1-C8烷氧基，C2-C8取代或者未取代的烯烷基，C2-C8取代或者未取代的炔烷基，C1-C4烷基取代或未取代的苯基，C1-C4烷基取代或未取代的萘基；Ar1-Ar4独立地表示C1-C4烷基或者C6-C30芳基取代的苯基，C1-C4烷基或者C6-C30芳基取代的萘基，苯基，萘基，N-芳基（C6-C30)或者C1-C4的烷基取代的咔唑基，二苯并噻吩基，二苯并呋喃基，蒽基，菲基，芘基，苝基，荧蒽基，（9,9-二烷基）芴基，（9,9-二烷基取代或未取代芳基）芴基，9,9-螺芴基。
优选：其中，R1-R8可以独立地优选表示为氢，卤素，C1-C4的烷基，C1-C4烷基取代或未取代的苯基，C1-C4烷基取代或未取代的萘基；优选Ar1-Ar4为独立地表示苯基，甲苯基，叔丁基苯基，萘基，甲基萘，联苯基，二苯基苯基，萘基苯基，二苯基联苯基，二芳香胺基苯基，N-苯基咔唑基，（9,9-二烷基）芴基，（9,9-二烷基取代或未取代苯基）芴基，9,9-螺芴基。
优选：其中，R1,R4,R5,R8，优选为氢，R2，R3，R6，R7可以独立优选表示为氢，氟，甲基，乙基，丙基，异丙基，叔丁基，苯基，萘基；Ar1-Ar4为独立地表示苯基，甲苯基，萘基，甲基萘，联苯基，二苯基苯基，萘基苯基，二苯基联苯基，（9,9-二烷基）芴基，（9,9-二甲基取代或未取代苯基）芴基，9,9-螺芴基。
优选Ar2，Ar3，Ar4为独立地表示苯基，萘基，联苯基，Ar1为苯基，萘基，联苯基，二苯基苯基，萘基苯基，二苯基联苯基，（9,9-二烷基）芴基，（9-甲苯基，9’-苯基）芴基，9,9-螺芴基。
优选：R2，R3，R6，R7为氢，Ar2，Ar3，Ar4为独立地表示苯基，萘基。
优选：
上述有机电子材料在有机电致发光器件，有机太阳能电池，有机薄膜晶体管或有机光感受器领域的应用。
如上面提到的，本发明的具体实施例如下，但不限于所列举的结构：
本发明提供的有机电子材料可以制成有机电致发光器件，该器件包含阳极，阴极和一层或多层有机层，所述有机层中至少有一层含有如结构式I所述的有机电子材料。
所述多层有机层分别为空穴注入层，空穴传输层，发光层，空穴阻挡层和电子传输层，需要特别指出，上述有机层可以根据需要，这些有机层不必每层都存在。
所述空穴传输层，电子传输层和发光层中含有如结构式1所述的有机材料。
结构式I化合物作为无掺杂单一发光层或掺杂发光层。
所述掺杂发光层包括主体材料和客体材料，结构式（I）化合物作为主体材料时，其浓度为整个发光层重量的20-99.9%，优选80-99%，更优选为90-99%。结构式（I）化合物作为客体材料时，其浓度为这个发光层重量的0.01-80%，优选1-20%，更优选为1-10%。
包括同时使用结构式I的两个化合物分别作主体材料和客体材料。
本发明的电子器件有机层的总厚度为1-1000nm，优选1-500nm，更优选50-300nm。
本发明中的空穴传输层和空穴注入层，所需材料具有很好的空穴传输性能，能够有效地把空穴从阳极传输到有机发光层上。可以包括小分子和高分子有机材料，可以包含如下，但是不限于这些，三芳香胺化合物，联苯二胺化合物，噻唑化合物，恶唑化合物，咪唑类化合物，芴类化合物，酞菁类化合物，六氰基六杂三苯（hexanitrilehexaazatriphenylene)，2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌（F4-TCNQ），聚乙烯基咔唑，聚噻吩，聚乙烯，聚苯磺酸。
本发明的有机电致发光层，除含有本发明的蒽乙烯基化合物外，还可以含有如下化合物，但是不限于此，萘类化合物，芘类化合物，芴类化合物，菲类化合物，屈类化合物，荧蒽类化合物，蒽类化合物，并五苯类化合物，苝类化合物，二芳乙烯类化合物，三苯胺乙烯类化合物，胺类化合物，苯并咪唑类化合物，呋喃类化合物，有机金属螯合物。
本发明的有机电子器件使用的有机电子传输材料要求具有很好的电子传输性能，能够有效地把电子从阴极传输到发光层中，可以选择如下化合物，但是不限于此，氧杂恶唑，噻唑类化合物，三氮唑类化合物，三氮嗪类化合物，三氮杂苯类化合物，喔啉类化合物，二氮蒽类化合物，含硅杂环类化合物，喹啉类化合物，菲啰啉类化合物，金属螯合物，氟取代苯类化合物。
本发明的有机电子器件根据需要，可以加入一层电子注入层，该电子注入层可以有效的把电子从阴极注入到有机层中，主要选自碱金属或者碱金属的化合物，或选自碱土金属或者碱土金属的化合物，可以选择如下化合物，但是不限于此，锂，氟化锂，氧化锂，氮化锂，8-羟基喹啉锂，铯，碳酸铯，8-羟基喹啉铯，钙，氟化钙，氧化钙，镁，氟化镁，碳酸镁，氧化镁。
器件实验表明，本发明如式（I）所述的有机电子材料，具有较好热稳定性，高发光效率，高发光纯度。采用该有机发光材料制作的有机电致发光器件具有电致发光效率良好和色纯度优异以及寿命长的优点。
附图说明
图1为本发明的器件结构图，
其中10代表为玻璃基板，20代表为阳极，30代表为空穴注入层，40代表为空穴传输层，50代表为发光层，60代表为电子传输层，70代表为电子注入层，80代表为阴极。
图2为化合物110的1HNMR图。
具体实施方式
为了更详细叙述本发明，特举以下例子，但是不限于此。
实施例1
化合物110的合成
中间体1-1的合成
在1L的单口烧瓶中，加入25.5g1-萘硼酸和25g对溴苯甲醛，400ml二氧六环，80ml2M碳酸钾水溶液，在氮气保护下，加入1.0g四三苯基磷钯，加热回流12小时，冷却，用乙酸乙酯萃取三遍，有机相用无水硫酸钠干燥，浓缩，粗品用乙醇重结晶，得到固体29g，产率为92%。
中间体1-3的合成
在500ml的单口烧瓶中，25g对溴苄溴跟49.8ml亚磷酸三乙酯（1-2）加热回流2个小时，除去多余的亚磷酸三乙酯，加入23.4g中间体1-1和250mlDMF，在冰浴下，加入16.8g叔丁醇钾，升至室温，搅拌过夜，把反应液倒入蒸馏水里面，过滤，滤饼用乙醇重结晶，得到31.8g，产率83%。
中间体1-4的合成
在1L的单口烧瓶中，加入45g3,5-二苯基苯硼酸和42.5g对溴碘苯，450ml二氧六环，150ml2M碳酸钾水溶液，在氮气保护下，加入1.7g四三苯基磷钯，加热回流12小时，冷却，用乙酸乙酯萃取三遍，有机相用无水硫酸钠干燥，浓缩，粗品用乙醇重结晶，得到固体54.6g，产率为95%。
中间体1-5的合成
在氮气保护下，把20g中间体1-4和300mlTHF加入到1L的三口烧瓶中，冷却到-78度，滴加21ml2.5M的正丁基锂，在此温度下，保持2小时，加入16.6g硼酸三异丙酯，在此温度下保持1个小时，升至室温，反应12小时，往反应液加入2N的稀盐酸，调节到中性，用乙酸乙酯萃取三次，有机相用无水硫酸钠干燥，浓缩，粗品用乙酸乙酯和正己烷重结晶，得到固体14g，产率为78%。
中间体1-6的合成
在500ml的单口烧瓶中，加入20g中间体1-3和14g9-蒽硼酸，350ml二氧六环，70ml碳酸钾水溶液，在氮气保护下，加入0.6g四三苯基磷钯，加热回流12小时，冷却，用乙酸乙酯萃取三遍，有机相用无水硫酸钠干燥，浓缩，粗品用THF加热回流，冷却过滤，得到固体20g，产率为80%。
中间体1-7的合成
在500ml的单口烧瓶中，加入20g中间体1-6，10.4gNBS和400ml氯仿，25度下搅拌12小时，除去二氯甲烷，用THF和乙醇重结晶得到17g，产率73.3%。
化合物110的合成
在250ml的单口烧瓶中，加入5.5g中间体1-5和7.3g中间体1-7，75ml二氧六环，20ml2M碳酸钾水溶液，在氮气保护下，加入0.15g四三苯基磷钯，加热回流12小时，冷却，用乙酸乙酯萃取三遍，有机相用无水硫酸钠干燥，浓缩，粗品用THF加热回流，冷却过滤，得到固体7.7g，产率为75.5%。1HNMR(400MHz,CD2Cl2,δ)：7.99-8.02（m,5H),7.88-7.95(m,3H),7.76-7.86(m,12H),7.38-7.63(m,22H).MALDI-TOF-MSm/s计算值C62H42：786.3，实测值[M+]:786.5。化合物110的1HNMR如图2。
实施例2
化合物122的合成
中间体2-2的合成
在氮气保护下，把36.3g中间体（2-1）和400mlTHF加入到1L的三口烧瓶中，冷却到-78度，滴加50ml2.5M的正丁基锂，在此温度下，保持2小时，加入30g硼酸三异丙酯，在此温度下保持1个小时，升至室温，反应12小时，往反应液加入2N的稀盐酸，用乙酸乙酯萃取三次，有机相用无水硫酸钠干燥，浓缩，粗品用乙酸乙酯和正己烷重结晶，得到固体27g，产率为90%。
中间体2-3的合成
在500ml的单口烧瓶中，加入25g中间体2-2和14.5g对溴碘苯，300ml二氧六环，60ml2M碳酸钾水溶液，在氮气保护下，加入0.6g四三苯基磷钯，加热回流12小时，冷却，用乙酸乙酯萃取三遍，有机相用无水硫酸钠干燥，浓缩，粗品用THF加热回流，冷却过滤，得到固体22g，产率为70%。
中间体2-4的合成
在氮气保护下，把15.5g中间体2-3和300mlTHF加入到250ml的三口烧瓶中，冷却到-78度，滴加17ml2.5M的正丁基锂，在此温度下，保持2小时，加入10.2g硼酸三异丙酯，在此温度下保持1个小时，升至室温，反应12小时，往反应液加入2N的稀盐酸，用乙酸乙酯萃取三次，有机相用无水硫酸钠干燥，浓缩，粗品用乙酸乙酯和正己烷重结晶，得到固体14g，产率为90%。
化合物122的合成
在250ml的单口烧瓶中，加入7g中间体2-5和8g中间体1-7，120ml二氧六环，24ml2M碳酸钾水溶液，在氮气保护下，加入0.16g四三苯基磷钯，加热回流12小时，冷却，用乙酸乙酯萃取三遍，有机相用无水硫酸钠干燥，浓缩，粗品用THF加热回流，冷却过滤，得到固体10g，产率为79%。1HNMR(400MHz,CD2Cl2,δ)：7.98-8.00(d,J=8.4Hz,2H),7.94-7.96(d,J=7.6Hz,2H),7.89-7.91(d,J=8.0Hz,2H),7.76-7.86(m,12H),7.65-7.67(d,J=8.4Hz,2H),7.48-7.58(m,11H),7.32-7.43(m,11H),7.09-7.17(m,6H)2.32(s,3H).MALDI-TOF-MSm/s计算值C70H48：888.4，实测值[M+]:888.7。
实施例3
蓝色有机电致发光器件的制备
使用本发明的有机电子材料制备OLED
首先，将透明导电ITO玻璃基板10（上面带有阳极20）依次经：洗涤剂溶液和去离子水，乙醇，丙酮，去离子水洗净，再用氧等离子处理30秒，接着用等离子处理的CFx处理。
然后，在ITO上蒸渡5nm厚的MoO3作为空穴注入层30。
然后，蒸渡P1,形成50nm厚的空穴传输层40。
然后，在空穴传输层上蒸渡20nm厚的化合物110作为发光层50。
然后，在发光层上蒸渡40nm厚的P2作为电子传输层60。
最后，蒸渡1.2nmLiF为电子注入层70和150nmAl作为器件阴极80。
所制备的器件在7V的工作电压下的亮度为980cd/m2，电流效率达到4.3cd/A，功率效率为2.1lm/W，发射蓝光。
器件中所述结构式
实施例4（方法同实施例3）
将化合物110，换成化合物122，制作有机电致发光器件。
所制备的器件在7V的工作电压下的亮度为470cd/m2，电流效率达到4.6cd/A，功率效率为1.95lm/W，发射蓝光。
比较例1
方法同实施例3，将化合物110替换成下列化合物P3，制作对比用有机电致发光器件。
所制备的器件在7V的工作电压下的亮度为289cd/m2，电流效率达到2.4cd/A，功率效率为1.1lm/W，发射蓝光。
实施例3和4是本发明材料的具体应用，所制备的器件，本发明发射蓝光，效率和亮度都高于对比例。如上所述，本发明的材料具有高的稳定性，本发明制备的有机电致发光器件具有高的效率和光纯度。

Claims (2)

1.有机电子材料，为下列结构化合物，
2.权利要求1所述有机电子材料在有机电致发光器件，有机太阳能电池，有机薄膜晶体管或有机光感受器领域的应用。
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