TWI570984B - Organic electronic materials - Google Patents

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TWI570984B
TWI570984B TW102118959A TW102118959A TWI570984B TW I570984 B TWI570984 B TW I570984B TW 102118959 A TW102118959 A TW 102118959A TW 102118959 A TW102118959 A TW 102118959A TW I570984 B TWI570984 B TW I570984B
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compounds
organic
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TW201407853A (zh
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Lei Dai
Jinhai Huang
Jinxin Chen
Lifei Cai
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Guangdong Aglaia Optoectronic Materials Co Ltd
Beijing Aglaia Technology Development Co Ltd
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Description

有機電子材料
本發明涉及新型的有機電致發光材料通過真空蒸渡沈積成薄膜，作為藍光電致發光材料應用在有機電致發光二極管上，屬于有機電致發光器件顯示技術領域。
有機電致發光器件作為一種新型的顯示技術，具有自發光、寬視角、低能耗、效率高、薄、色彩豐富、響應速度快、適用溫度範圍廣、低驅動電壓、可制作柔性可彎曲與透明的顯示面板以及環境友好等獨特優點，因此，有機電致發光器件技術可以應用在平板顯示器和新一代照明上，也可以作為LCD的背光源。
有機電子發光器件為在兩個金屬電極之間通過旋塗或者沈積一層有機材料而制備的器件，一個經典的三層有機電致發光器件包含空穴傳輸層，發光層和電子傳輸層。由陽極產生的空穴經空穴傳輸層跟由陰極產生的電子經電子傳輸層結合在發光層形成激子，而後發光。有機電致發光器件可以通過改變發光層的材料來發射紅光，綠光和藍光。因而，穩定的，高效的和色彩純的有機電致發光材料對有機電致發光器件的應用和推廣具有重要作用，同時也是OLEDs大面積面板顯示的應用推廣的迫切需求。
在三原色(紅，藍，綠)當中，紅光和綠光材料最近已經取得了很大的發展，也符合面板的市場需求。對于藍光材料，也有一系列的商品化的材料，其中早期用得比較多的為出光興產的二苯乙烯基聯苯(DPVBi)類化合物，以這類化合物制備的器件具有較高的效率，但是往往這些材料的穩定性比較差，更有甚地，這類化合物的發光的顏色屬于天藍光，往往CIE值中的y>0.15。所以由于其不好的溫度性和不純的顏色很大 程度地限制了這類化合物在全彩顯示器件中的應用。另外一類藍光材料為柯達公司的ADN和四叔丁基苝，但是這些化合物的發光效率比較差，而且穩定性也不好，從而無法大量使用。
本發明就是克服上面化合物的缺陷提供一系列具有較好熱穩定性，高發光效率，高發光純度的有機電致藍光材料，由它制備的有機電致發光器件具有電致發光效率良好和色純度優異以及壽命長的優點。
本發明所述的有機電子材料具有式(I)所述的結構式：
其中，R1-R8獨立地表示為氫，氘原子，鹵素，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個或者多個的雜原子芳基，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獨立地表示C6-C60取代或者未取代的芳基，C3-C60的取代或者未取代的帶有一個或者多個雜原子的雜芳基，三芳香(C6-C30)胺基。
優選：其中，R1-R8獨立地表示為氫，鹵素，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獨立地表示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的烷基取代的哢唑基，二苯並噻吩基，二苯並呋喃基，蒽基，菲基，芘基，苝基，熒蒽基，(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。
優選：其中，R1-R8可以獨立地優選表示為氫，鹵素，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；優選Ar1-Ar4為獨立地表示苯基，甲苯基，叔丁基苯基，萘基，甲基萘，聯苯基，二苯基苯基，萘基苯基，二苯基聯苯基，二芳香胺基苯基，N-苯基哢唑基，(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。
優選：其中，R1,R4,R5,R8，優選為氫，R2，R3，R6，R7可以獨立優選表示為氫，氟，甲基，乙基，丙基，異丙基，叔丁基，苯基，萘基；Ar1-Ar4為獨立地表示苯基，甲苯基，萘基，甲基萘，聯苯基，二苯基苯基，萘基苯基，二苯基聯苯基，(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。
優選Ar2，Ar3，Ar4為獨立地表示苯基，萘基，聯苯基，Ar1為苯基，萘基，聯苯基，二苯基苯基，萘基苯基，二苯基聯苯基，(9,9-二烷基)芴基，(9-甲苯基，9’-苯基)芴基，9,9-螺芴基。
優選：R2，R3，R6，R7為氫，Ar2，Ar3，Ar4為獨立地表示苯基，萘基。
優選：
上述有機電子材料在有機電致發光器件，有機太陽能電池，有機薄膜晶體管或有機光感受器領域的應用。
如上面提到的，本發明的具體實施例如下，但不限于所列舉的結構：
本發明提供的有機電子材料可以制成有機電致發光器件，該器件包含陽極，陰極和一層或多層有機層，所述有機層中至少有一層含有如結構式I所述的有機電子材料。
所述多層有機層分別為空穴注入層，空穴傳輸層，發光層，空穴阻擋層和電子傳輸層，需要特別指出，上述有機層可以根據需要，這些有機層不必每層都存在。
所述空穴傳輸層，電子傳輸層和發光層中含有如結構式1所述的有機材料。
結構式I化合物作為無摻雜單一發光層或摻雜發光層。
所述摻雜發光層包括主體材料和客體材料，結構式(I)化合物作為主體材料時，其濃度為整個發光層重量的20-99.9%，優選80-99%，更優選為90-99%。結構式(I)化合物作為客體材料時，其濃度為這個發光層重量的0.01-80%，優選1-20%，更優選為1-10%。
包括同時使用結構式I的兩個化合物分別作主體材料和客體材料。
本發明的電子器件有機層的總厚度為1-1000 nm，優選1-500 nm，更優選50-300 nm。
本發明中的空穴傳輸層和空穴注入層，所需材料具有很好的空穴傳輸性能，能夠有效地把空穴從陽極傳輸到有機發光層上。可以包括小分子和高分子有機材料，可以包含如下，但是不限于這些，三芳香胺化合物，聯苯二胺化合物，噻唑化合物，惡唑化合物，咪唑類化合物，芴類化合物，酞菁類化合物，六氰基六雜三苯(hexanitrile hexaazatriphenylene)，2,3,5,6-四氟-7,7',8,8'-四氰二甲基對苯醌(F4-TCNQ)，聚乙烯基哢唑，聚噻吩，聚乙烯，聚苯磺酸。
本發明的有機電致發光層，除含有本發明的蒽乙烯基化合物外，還可以含有如下化合物，但是不限于此，萘類化合物，芘類化合物，芴類化合物，菲類化合物，屈類化合物，熒蒽類化合物，蒽類化合物，並五苯類化合物，苝類化合物，二芳乙烯類化合物，三苯胺乙烯類化合物，胺類化合物，苯並咪唑類化合物，呋喃類化合物，有機金屬螯合物。
本發明的有機電子器件使用的有機電子傳輸材料要求具有很好的電子傳輸性能，能夠有效地把電子從陰極傳輸到發光層中，可以選擇如下化合物，但是不限于此，氧雜惡唑，噻唑類化合物，三氮唑類化合物，三氮嗪類化合物，三氮雜苯類化合物，喔啉類化合物，二氮蒽類化合物，含矽雜環類化合物，喹啉類化合物，菲囉啉類化合物，金屬螯合物，氟取代苯類 化合物。
本發明的有機電子器件根據需要，可以加入一層電子注入層，該電子注入層可以有效的把電子從陰極注入到有機層中，主要選自堿金屬或者堿金屬的化合物，或選自堿土金屬或者堿土金屬的化合物，可以選擇如下化合物，但是不限于此，鋰，氟化鋰，氧化鋰，氮化鋰，8-羥基喹啉鋰，銫，碳酸銫，8-羥基喹啉銫，鈣，氟化鈣，氧化鈣，鎂，氟化鎂，碳酸鎂，氧化鎂。
器件實驗表明，本發明如式(I)所述的有機電子材料，具有較好熱穩定性，高發光效率，高發光純度。采用該有機發光材料制作的有機電致發光器件具有電致發光效率良好和色純度優異以及壽命長的優點。
10‧‧‧玻璃基板
20‧‧‧陽極
30‧‧‧空穴注入層
40‧‧‧空穴傳輸層
50‧‧‧發光層
60‧‧‧電子傳輸層
70‧‧‧電子注入層
80‧‧‧陰極
圖1為本發明的器件結構圖。
圖2為化合物110的1H NMR圖。
為了更詳細敘述本發明，特舉以下例子，但是不限于此。
實施例1 化合物110的合成
中間體1-1的合成
在1 L的單口燒瓶中，加入25.5 g1-萘硼酸和25 g對溴苯甲醛，400 ml二氧六環，80 ml 2 M碳酸鉀水溶液，在氮氣保護下，加入1.0 g四三苯基磷鈀，加熱回流12小時，冷卻，用乙酸乙酯萃取三遍，有機相用無水硫酸鈉幹燥，濃縮，粗品用乙醇重結晶，得到固體29 g，產率為92%。
中間體1-3的合成
在500 ml的單口燒瓶中，25 g對溴苄溴跟49.8 ml亞磷酸三乙酯(1-2)加熱回流2個小時，除去多余的亞磷酸三乙酯，加入23.4 g中間體1-1和250 ml DMF，在冰浴下，加入16.8 g叔丁醇鉀，升至室溫，攪拌過夜，把反應液倒入蒸餾水裏面，過濾，濾餅用乙醇重結晶，得到31.8 g，產率83%。
中間體1-4的合成
在1 L的單口燒瓶中，加入45 g3,5-二苯基苯硼酸和42.5 g對溴碘苯，450 ml二氧六環，150 ml 2M碳酸鉀水溶液，在氮氣保護下，加入1.7 g四三苯基磷鈀，加熱回流12小時，冷卻，用乙酸乙酯萃取三遍，有機相用無水硫酸鈉幹燥，濃縮，粗品用乙醇重結晶，得到固體54.6 g，產率為95%。
中間體1-5的合成
在氮氣保護下，把20 g中間體1-4和300 ml THF加入到1 L的三口燒瓶中，冷卻到-78度，滴加21 ml 2.5M的正丁基鋰，在此溫度下，保持2小時，加入16.6 g硼酸三異丙酯，在此溫度下保持1個小時，升至室溫，反應12小時，往反應液加入2N的稀鹽酸，調節到中性，用乙酸乙酯萃取三次，有機相用無水硫酸鈉幹燥，濃縮，粗品用乙酸乙酯和正己烷重結晶，得到固體14 g，產率為78%。
中間體1-6的合成
在500 ml的單口燒瓶中，加入20 g中間體1-3和14 g 9-蒽硼酸，350 ml二氧六環，70 ml碳酸鉀水溶液，在氮氣保護下，加入0.6 g四三苯基磷鈀，加熱回流12小時，冷卻，用乙酸乙酯萃取三遍，有機相用無水硫酸鈉幹燥，濃縮，粗品用THF加熱回流，冷卻過濾，得到固體20 g，產率為80%。
中間體1-7的合成
在500 ml的單口燒瓶中，加入20 g中間體1-6，10.4 g NBS和400 ml氯仿， 25度下攪拌12小時，除去二氯甲烷，用THF和乙醇重結晶得到17 g，產率73.3%。
化合物110的合成
在250 ml的單口燒瓶中，加入5.5 g中間體1-5和7.3 g中間體1-7，75 ml二氧六環，20 ml 2M碳酸鉀水溶液，在氮氣保護下，加入0.15 g四三苯基磷鈀，加熱回流12小時，冷卻，用乙酸乙酯萃取三遍，有機相用無水硫酸鈉幹燥，濃縮，粗品用THF加熱回流，冷卻過濾，得到固體7.7 g，產率為75.5%。1H NMR(400 MHz,CD2Cl2,δ)：7.99-8.02(m,5 H),7.88-7.95(m,3 H),7.76-7.86(m,12 H),7.38-7.63(m,22 H).MALDI-TOF-MS m/s計算值C62H42：786.3，實測值[M+]：786.5。化合物110的1H NMR如圖2。
實施例2 化合物122的合成
中間體2-2的合成
在氮氣保護下，把36.3g中間體(2-1)和400 ml THF加入到1L的三口燒瓶中，冷卻到-78度，滴加50 ml 2.5M的正丁基鋰，在此溫度下，保持2 小時，加入30 g硼酸三異丙酯，在此溫度下保持1個小時，升至室溫，反應12小時，往反應液加入2N的稀鹽酸，用乙酸乙酯萃取三次，有機相用無水硫酸鈉幹燥，濃縮，粗品用乙酸乙酯和正己烷重結晶，得到固體27 g，產率為90%。
中間體2-3的合成
在500 ml的單口燒瓶中，加入25 g中間體2-2和14.5 g對溴碘苯，300 ml二氧六環，60 ml 2M碳酸鉀水溶液，在氮氣保護下，加入0.6 g四三苯基磷鈀，加熱回流12小時，冷卻，用乙酸乙酯萃取三遍，有機相用無水硫酸鈉幹燥，濃縮，粗品用THF加熱回流，冷卻過濾，得到固體22 g，產率為70%。
中間體2-4的合成
在氮氣保護下，把15.5 g中間體2-3和300 ml THF加入到250 ml的三口燒瓶中，冷卻到-78度，滴加17 ml 2.5M的正丁基鋰，在此溫度下，保持2小時，加入10.2 g硼酸三異丙酯，在此溫度下保持1個小時，升至室溫，反應12小時，往反應液加入2N的稀鹽酸，用乙酸乙酯萃取三次，有機相用無水硫酸鈉幹燥，濃縮，粗品用乙酸乙酯和正己烷重結晶，得到固體14 g，產率為90%。
化合物122的合成
在250 ml的單口燒瓶中，加入7 g中間體2-5和8 g中間體1-7，120 ml二氧六環，24 ml 2M碳酸鉀水溶液，在氮氣保護下，加入0.16g四三苯基磷鈀，加熱回流12小時，冷卻，用乙酸乙酯萃取三遍，有機相用無水硫酸鈉幹燥，濃縮，粗品用THF加熱回流，冷卻過濾，得到固體10g，產率為79%。1H NMR(400 MHz,CD2Cl2,δ)：7.98-8.00(d,J=8.4 Hz,2 H),7.94-7.96(d,J=7.6 Hz,2 H),7.89-7.91(d,J=8.0 Hz,2 H),7.76-7.86(m,12 H),7.65-7.67(d, J=8.4 Hz,2 H),7.48-7.58(m,11 H),7.32-7.43(m,11 H),7.09-7.17(m,6 H)2.32(s,3 H).MALDI-TOF-MS m/s計算值C70H48：888.4，實測值[M+]：888.7。
實施例3 藍色有機電致發光器件的制備 使用本發明的有機電子材料制備OLED
首先，將透明導電ITO玻璃基板10(上面帶有陽極20)依次經：洗滌劑溶液和去離子水，乙醇，丙酮，去離子水洗淨，再用氧等離子處理30秒，接著用等離子處理的CFx處理。
然後，在ITO上蒸渡5 nm厚的MoO3作為空穴注入層30。
然後，蒸渡P1，形成50 nm厚的空穴傳輸層40。
然後，在空穴傳輸層上蒸渡20 nm厚的化合物110作為發光層50。
然後，在發光層上蒸渡40 nm厚的P2作為電子傳輸層60。
最後，蒸渡1.2 nm LiF為電子注入層70和150 nm Al作為器件陰極80。
所制備的器件在7V的工作電壓下的亮度為980cd/m2，電流效率達到4.3 cd/A，功率效率為2.1 lm/W，發射藍光。
器件中所述結構式
實施例4(方法同實施例3)
將化合物110，換成化合物122，制作有機電致發光器件。
所制備的器件在7V的工作電壓下的亮度為470 cd/m2，電流效率達到4.6 cd/A，功率效率為1.95 lm/W，發射藍光。
比較例1
方法同實施例3，將化合物110替換成下列化合物P3，制作對比用有機電致發光器件。
所制備的器件在7V的工作電壓下的亮度為289 cd/m2，電流效率達到2.4 cd/A，功率效率為1.1 lm/W，發射藍光。
實施例3和4是本發明材料的具體應用，所制備的器件，本發明發射藍光，效率和亮度都高于對比例。如上所述，本發明的材料具有高的穩定性，本發明制備的有機電致發光器件具有高的效率和光純度。

Claims (2)

  1. 一種有機電子材料，為下列結構化合物：
  2. 如請求項1所述的有機電子材料，為下列結構化合物：
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TW201407853A (zh) 2014-02-16
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KR20150022758A (ko) 2015-03-04
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