TW201632486A - 有機電子材料 - Google Patents

有機電子材料 Download PDF

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TW201632486A
TW201632486A TW104130135A TW104130135A TW201632486A TW 201632486 A TW201632486 A TW 201632486A TW 104130135 A TW104130135 A TW 104130135A TW 104130135 A TW104130135 A TW 104130135A TW 201632486 A TW201632486 A TW 201632486A
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unsubstituted
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phenyl
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錦鴻 魯
李哲
陳金鑫
蔡麗菲
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廣東阿格蕾雅光電材料有限公司
北京阿格蕾雅科技發展有限公司
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Abstract

本發明涉及一種有機電子材料，屬於有機電致發光器件顯示材料技術領域。本發明所述的有機電子材料具有式(I) 所述的結構式，具有較好熱穩定性，高發光效率，高發光純度。採用該有機發光材料製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。□式（I）

Description

有機電子材料
本發明涉及新型的有機電致發光材料，通過真空蒸渡沉積成薄膜，作為藍光電致發光材料應用在有機電致發光二極體上，屬於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、回應速度快、適用溫度範圍廣、低驅動電壓、可製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沉積一層有機材料而製備的器件，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。對於藍光材料，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（Idemitsu Kosan Co.,Ltd）的二苯乙烯基聯苯(DPVBi）類化合物，以這類化合物製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於天藍光，往往CIE值中的y＞0.15。所以由於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。 （DPVBi)                                      (ADN)                       (四叔丁基苝）
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，由它製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：（I）
其中，R1 -R17 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 -Ar3 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 -R17 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，或結合成C1-C4烷基取代或未取代的芴基；Ar1 -Ar3 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，吡啶基，N- C6-C30的芳基或者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 -R2 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，或結合成C1-C4烷基取代或未取代的芴基；其中，R3 -R17 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 -Ar3 為獨立地表示苯基，甲苯基，二甲苯基，叔丁基苯基，萘基，吡啶基，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，R3 -R17 優選為氫，R1 ，R2 可以獨立優選表示為氫，甲基，乙基，丙基，異丙基，叔丁基，苯基，聯苯基，萘基，或結合成芴基；Ar1 -Ar3 為獨立地表示苯基，吡啶基，甲苯基，二甲苯基，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：R3 -R17 優選為氫；R1 ，R2 為獨立地表示氫，甲基，或結合成芴基；Ar1 ，Ar2 ，Ar3 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，有機薄膜電晶體或有機光感受器領域的應用。
如上面提到的，本發明具體實施例如下，但不限於所列舉的結構： 。
本發明提供的有機電子材料可以製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，電子傳輸層或/和電子注入層，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。
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，但是不限於這些，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，除含有本發明的結構式（I）化合物外，還可以含有如下化合物，但是不限於此，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，但是不限於此，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，主要選自鹼金屬或者鹼金屬的化合物，或選自鹼土金屬或者鹼土金屬的化合物，可以選擇如下化合物，但是不限於此，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。採用該有機發光材料製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。
為了更詳細敘述本發明，特舉以下例子，但是不限於此。(其中下面的化合物1a、1b、1e、1h，3a、89a為市售的常用材料）
實施例1
中間體1c的合成 向反應燒瓶中加入 1a (240.00 g, 0.88 mol), 1b (496.32 g, 1.76 mol), Pd(PPh3 )4 (20.35g, 17.60 mmol)，碳酸鉀 (302.52 g, 2.20 mol)，甲苯 (2400 mL)，純水 (1200 mL)。抽放氮氣三次後開啟加熱，待反應液溫度達到95-105℃，保持此溫度反應8-12h，取樣TLC及HPLC，原料反應完全。停止加熱，降溫至20-30℃，抽濾，濾液分出有機層，水層再用乙酸乙酯萃取，合併有機層，再用水洗，無水硫酸鎂乾燥，抽濾，濾液濃縮得到暗黃色固體粗產品。石油醚重結晶，得到灰白色固體產品，收率90%，純度95%。
中間體1d的合成 向反應燒瓶中加入相應比例的1c (302 g, 0.78 mol), B(OEt)3 (142 g, 0.97 mol), n-BuLi/THF (1.6 M, 600 mL), 無水THF (3000 mL)，抽放氮氣三次後冷卻降溫至反應液溫度至-75 ~ -65o C，緩慢滴加n-BuLi/THF溶液，控制反應液溫度在-75 ~ -65o C，滴加完畢後，繼續保持此溫度反應0.5-1h。後將一定量的B(OEt)3 滴加進去，控制反應液溫度在-75 ~ -65o C，滴加完畢後，繼續保持此溫度反應0.5-1h，後反應液移至室溫自然升溫反應4 - 6 h，然後加入2M稀鹽酸，調節PH值至2 - 3，攪拌約1h，停止反應。加入乙酸乙酯萃取，水層再用EA萃取，合併有機層，無水硫酸鎂乾燥，抽濾，濾液濃縮得到灰白色固體產品，純度95%，收率62.5%。
中間體1f的合成 向反應燒瓶中加入1d (150g, 0.43mol), 1e (500g, 0.86mol), Pd(PPh3 )4 (5.0 g, 0.44 mmol)，碳酸鉀 (130 g, 0.92 mol)，甲苯 (1000 mL)，純水 (500 mL), 抽放氮氣三次開啟加熱，待反應液溫度達到95-105o C，保持此溫度反應8-12h，取樣TLC及HPLC，原料反應完全。停止加熱，降溫至20-30o C，抽濾，濾液分出有機層，水層再用乙酸乙酯萃取，合併有機層，無水硫酸鎂乾燥，抽濾，濾液濃縮得到暗黃色固體粗產品，純度80%，收率78.1%。
中間體1g的合成 向反應燒瓶中加入 1f (210g, 0.42mol), NBS (135 g, 0.71mol), DMF (5L)。抽放氮氣三次開啟加熱，待反應液溫度達到60-65℃，保持此溫度反應6-8h，取樣TLC及HPLC，原料反應完全。停止加熱，降溫至20-30℃，反應液倒入冰水中，析出暗黃色固體，抽濾得到黃色固體，烘乾得到1g粗產品。粗產品加入DCM/MeOH至溶液稍微變混濁，繼續攪拌約30min，析出大量固體，抽濾，得到淺黃色固體產品，收率約54.05%，純度98.5%1 H NMR (300 MHz, CDCl3 ) δ 8.64 (d,J = 8.8 Hz, 2H), 7.99 – 7.90 (m, 4H), 7.87 (t,J = 1.6 Hz, 1H), 7.78 (dd,J = 9.3, 2.3 Hz, 6H), 7.61 (ddd,J = 8.8, 6.5, 1.1 Hz, 2H), 7.56 – 7.48 (m, 6H), 7.46 – 7.38 (m, 4H).13 C NMR (76 MHz, CDCl3 ) δ 142.67 (s), 142.03 (s), 141.26 (s), 140.69 (s), 137.83 (s), 137.52 (s), 131.87 (s), 131.24 (s), 130.44 (s), 129.09 (s), 128.80 (s), 128.38 – 127.40 (m), 127.18 (s), 126.05 – 125.21 (m), 123.08 (s), 77.74 (s), 77.31 (s), 76.89 (s), 30.10 (s).
化合物1的合成 向500ml三口燒瓶中依次加入1g (9.5g, 16.92mmol), 1h (6.41g, 30.51mmol), Pd(PPh3 )4 (1.5g, 1.3mmol)，碳酸鉀 (5.84g, 42.3mmol)，甲苯 (150 mL)，純水 (75 mL)。抽放氮氣三次後105℃下反應。由液相檢測停反應時間，約12h左右。反應開始時反應液為催化劑的土黃色，之後慢慢變成黃色溶液，停反應後上層為清亮淺黃色，下層為水。停止反應後，過濾，用乙酸乙酯洗濾渣直至濾渣中無產物，收集濾液，旋乾，大量的灰白色固體析出，收集濾渣乾燥，得到目標產物，純度98%。真空昇華得到純度為99.5%灰白色固體粉末。1 H-NMR (300 MHz, CDCl3 ) δ 8.10–8.21 (d，2H)，7.96–7.98 (dd，3H)，7.87–7.89 (m，2H)，7.81–7.86 (m，4H)，7.78–7.81 (d，4H), 7.62–7.65 (m，2H)，7.59 (s，1H)，7.51–7.57 (m，5H)，7.45–7.48 (m，2H)，7.36–7.43 (m，7H)，3.88 (s，2H).
實施例2 化合物3的合成向500ml三口燒瓶中依次加入1g (9.5g, 16.92 mmol), 3a (7.25g, 30.46 mmol), Pd(PPh3 )4 (1.5g, 1.3mmol)，碳酸鉀 (5.84g, 42.3mmol)，甲苯 (150 mL)，純水 (75 mL)。抽放氮氣三次後105℃下反應。由液相檢測停反應時間，約12h左右。反應開始時反應液為催化劑的土黃色，之後慢慢變成黃色溶液，停反應後上層為清亮淺黃色，下層為水。停止反應後，過濾，用乙酸乙酯洗濾渣直至濾渣中無產物，收集濾液，旋乾，大量的灰白色固體析出，收集濾渣乾燥，得到目標產物，純度98%。真空昇華得到純度為99.7%灰白色固體粉末。1 H-NMR (300 MHz, CDCl3 ) δ 8.1–8.2 (d，2H)，7.96–7.99 (dd，3H)，7.88–7.89 (m，2H)，7.81–7.86 (m，4H)，7.78–7.81 (d，4H), 7.61–7.65 (m，2H)，7.59 (s，1H)，7.51–7.56 (m，5H)，7.46–7.48 (m，2H)，7.35–7.43 (m，7H)，1.61 (s，6H).
實施例3 化合物89的合成向反應容器中依次加入1g (10.0 g, 17.8 mmol), 89a (7.1 g, 19.6 mmol), Pd(PPh3 )4 (432.2 mg, 0.35 mmol), K2 CO3 (6.14 g, 44.5 mmol), 甲苯 (300 mL) 和水 (150 mL)，對裝置進行除氧、通入氮氣保護，然後加熱到100℃反應過夜。用DCM：PE=1:5的比例點板，產物點在365 nm波長的紫外燈下發強烈的藍光，Rf值在0.2左右。將反應液用矽膠抽濾，然後將濾餅用乙酸乙酯（100 mL）洗滌兩次，分液，用乙酸乙酯（100 mL）萃取水層一次，合併有機層，再用水（200 mL）洗滌一次有機相。旋乾除去溶劑。粗品用120ml DCM/MeOH重結晶，抽濾得到黃色固體粉末13.1g，純度為98.7%，收率92.2%。真空昇華得到純度為99.7%淺黃色固體粉末。m/z = 797.
從圖2和圖3可見化合物89的氫譜，碳譜與結構完全一致。從圖4化合物89的高效液相色譜圖可見根據本發明的合成方法製備的產物具有高純度。從圖5化合物89的熱重分析圖可見這類型化合物的分解溫度高於攝氏400度，表明其非常高熱穩定性。
實施例4 有機電致發光器件1的製備 使用本發明的有機電子材料製備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。 然後，在ITO上蒸渡10 nm 厚的HAT-CN6 作為空穴注入層30。 然後，蒸渡NPB,形成30 nm厚的空穴傳輸層40。 然後，在空穴傳輸層上蒸渡30 nm厚的化合物3作為發光層50。 然後，在發光層上蒸渡15 nm厚的TPBi作為電子傳輸層60。 最後，蒸渡15 nm BPhen:Li為電子注入層70和150 nm Al作為器件陰極80。 所製備的器件在20 mA/cm2 的工作電流密度下的電壓為3.58 V，電流效率達到3.21 cd/A，在1000 cd/m2 亮度下 CIEy 座標為0.0853，發射藍光。   器件中所述結構式
實施例5 有機電致發光器件2的製備 方法同實施例4, 將化合物3，換成化合物89，製作有機電致發光器件。 所製備的器件在20 mA/cm2 的工作電流密度下的電壓為3.84 V,電流效率達到2.83 cd/A，在1000 cd/m2 亮度下 CIEy 座標為0.0888，發射藍光。
比較例1 方法同實施例4，將化合物3替換成下列化合物TAT，製作對比用有機電致發光器件。 TAT結構式所製備的器件在20 mA/cm2 的工作電流密度下的電壓為4.00 V,電流效率達到2.46 cd/A，在1000 cd/m2 亮度下 CIEy 座標為0.0952，發射藍光。
實施例4和5是本發明材料的具體應用，所製備的器件，本發明發射藍光，效率和亮度都高於對比例。如上所述，本發明的材料具有高的穩定性，本發明製備的有機電致發光器件具有高的效率和光純度。
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89的1 H NMR圖。 圖3 為化合物89的13 C NMR圖。 圖4 為化合物89的HPLC圖。 圖5 為化合物89的TGA圖。 圖6 為實施例4, 實施例5及比較例1的電壓–電流密度曲線圖。 圖7 為實施例4, 實施例5及比較例1的亮度–CIEy座標圖。 圖8 為實施例4, 實施例5及比較例1的電致發光光譜。 圖9 為實施例4, 實施例5及比較例1的電流密度–電流效率曲線圖。

Claims (8)

  1. 一種有機電子材料，其具有式(I)所述的結構式：（I） 其中，R1 -R17 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 -Ar3 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。
  2. 如申請專利範圍第1項所述的有機電子材料，其中，R1 -R17 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，或結合成C1-C4烷基取代或未取代的芴基；Ar1 -Ar3 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，吡啶基，N- C6-C30的芳基或者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。
  3. 如申請專利範圍第2項所述的有機電子材料，其中，R1 -R2 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，或結合成C1-C4烷基取代或未取代的芴基；其中，R3 -R17 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，Ar1 -Ar3 為獨立地表示苯基，甲苯基，叔丁基苯基，萘基，吡啶基，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。
  4. 如申請專利範圍第3項所述的有機電子材料，其中，R3 -R17 優選為氫，R1 ，R2 可以獨立優選表示為氫，甲基，乙基，丙基，異丙基，叔丁基，苯基，萘基，或結合成芴基；Ar1 -Ar3 為獨立地表示苯基，吡啶基，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。
  5. 如申請專利範圍第4項所述的有機電子材料，其中，R3 -R17 優選為氫；R1 ，R2 為獨立地表示氫，甲基，或結合成芴基；Ar1 ，Ar2 ，Ar3 為獨立地表示苯基，萘基。
  6. 如申請專利範圍第1項所述的有機電子材料，為下列結構化合物： 。
  7. 如申請專利範圍第6項所述的有機電子材料，為下列結構化合物：，，。
  8. 如申請專利範圍第1至7項中之任一項所述的有機電子材料，其中，係被使用在有機電致發光器件、有機太陽能電池、有機薄膜電晶體或有機光感受器領域的應用。
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US10347843B2 (en) 2019-07-09
DE112015006276T5 (de) 2018-01-25
TWI561498B (en) 2016-12-11
DE112015006276B4 (de) 2022-08-25
US20180047909A1 (en) 2018-02-15
JP6516861B2 (ja) 2019-05-22
CN106032350B (zh) 2019-03-01
KR20170117482A (ko) 2017-10-23
KR101992318B1 (ko) 2019-06-24
CN106032350A (zh) 2016-10-19
JP2018513884A (ja) 2018-05-31

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