CN108586319A - 一种双极性主体有机电致发光材料及应用 - Google Patents

一种双极性主体有机电致发光材料及应用 Download PDF

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CN108586319A
CN108586319A CN201810332502.2A CN201810332502A CN108586319A CN 108586319 A CN108586319 A CN 108586319A CN 201810332502 A CN201810332502 A CN 201810332502A CN 108586319 A CN108586319 A CN 108586319A
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electroluminescent organic
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李庆
李子澍
石宇
孟凡民
周银波
胡葆华
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Valiant Co Ltd
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Abstract

本发明属于有机电致发光领域，尤其涉及一种双极性主体有机电致发光材料及应用。本发明的双极性主体有机电致发光材料具有较高的载流子注入和传输能力，具有良好的传输空穴和电子的双极特性，因此，使用这种材料制备的有机电致发光器件具有启亮电压低、发光效率高等优点；本发明的双极性主体有机电致发光材料具有较大的分子量，具有较高玻璃化转变温度和热分解温度，化合物的稳定性高，有利于显著提高器件的寿命；本发明的双极性主体有机电致发光材料具有较高的单线态和三线态能级，可优选作为绿光主体材料使用。应用本发明的双极性主体有机电致发光材料作为主体材料，制备的器件能够有效提升外量子效率、功率效率和电流效率。

Description

一种双极性主体有机电致发光材料及应用
技术领域
本发明属于有机电致发光领域，尤其涉及一种双极性主体有机电致发光材料及应用。
背景技术
磷光材料可以充分利用电致发光器件中电子空穴复合产生的占75％比例的三线态激子，单线态激子发生系间窜越，向更低能级的三线态转移，能使磷光器件的激子利用率达到100％。磷光材料通常作为客体材料掺杂在主体材料中，有效的主体材料应具有理想的带隙以便使能量有效转移到客体，良好的载流子传输性质以便在发射层中实现载流子的平衡重组，与邻近层的能级匹配以实现有效的电荷注入，足够的热和形态学稳定性以延长器件寿命，因此主体材料的开发对于高效率的电致磷光发光极其重要。
传统的主体材料通常只具有单一载流子传输性质，这种不平衡的载流子传输性质已经显示出对OLED的开启电压和寿命的不利性。开发新的主体材料要求必须具有好的双极载流子(空穴和电子)注入和传输性质，以避免载流子在发光层和电荷传输层之间累计，引起界面处激基复合物发光，导致器件的外量子效率、功率效率、电流效率等主要参数偏低、启亮电压偏高、光谱不稳定等现象。因此，近年来可平衡载流子传输的双极主体材料引起了相当大的关注。
发明内容
本发明所要解决的技术问题是，提供一种双极性主体有机电致发光材料及应用。
本发明解决上述技术问题的技术方案如下：一种双极性主体有机电致发光材料，其特征在于，其结构式如下：
其中，Ar为C1-C10的取代或未取代的脂肪族直链或支链烷基、C6-C30 的取代或未取代的芳基或C3-C30的取代或未取代的含杂原子芳基；
R1、R2、R3、R4、R5、R6、R7、R8各自独立地为氢原子、氘原子、C1-C10 的脂肪族直链或支链烷基、C1-C10的脂肪族直链或支链烷氧基。
进一步，所述的含杂原子芳基中所述的杂原子为氮、氧或硫原子中的一种或两种以上；
R1、R2、R3、R4、R5、R6、R7、R8中，任意两个相邻基团相互键合形成饱和或不饱和的环结构。
更进一步，R1、R2、R3、R4、R5、R6、R7、R8中，任意两个相邻基团相互键合形成蒽或苯并菲结构。
进一步，Ar为如下基团中的任意一种：
下式所列化合物C1-C40，是符合本发明精神和原则的代表结构，应当理解，列出以下化合物结构，只是为了更好地解释本发明，并非是对本发明的限制。
本发明的第二个目的在于提供上述双极性主体有机电致发光材料的制备方法：
在氮气环境下，将M类/N类中间体、卤代物ArX、叔丁醇钾按照摩尔比为1∶(1.0-1.5)∶(1.5-3.0)混合，添加到含有催化剂Pd(OAc)2、配体三叔丁基膦四氟硼酸盐的邻二甲苯溶液中；回流保温反应12-20h，降温，抽滤，过柱除机械杂质，脱溶剂，经柱层析分离提纯得到目标物；反应式如下：
当R1、R2、R3、R4、R5、R6、R7、R8均为氢原子时，M类中间体或N类中间体可以直接作为中间体M或中间体N。下面列出中间体M和中间体N的制备方法。
1、中间体A的制备
(1)制备中间体A-1
在氮气环境下，将邻溴苯乙酮、联硼酸频哪醇酯、醋酸钾按照摩尔比为1.0∶(1.0-1.5)∶3.0混合，添加到含有催化剂Pd(PPh3)4的甲苯溶液中；回流保温反应10-12h，降温，经柱层析分离提纯得到中间体A-1；
(2)制备中间体A-2
在氮气环境下，将中间体A-1、1-溴-2-碘-4-硝基苯、碳酸钾按照摩尔比为1∶(1.0-1.2)∶3.0混合，添加到含有催化剂醋酸钯、4，5-双二苯基膦-9，9-二甲基氧杂蒽的甲苯/水的混合溶液中，氮气保护下回流反应24h，降温冷却，反应液静置分液，干燥，经柱层析分离提纯得到中间体A-2；
(3)制备中间体A-3
氮气保护环境下，内温0℃条件下，将1.5-2.0eq甲基溴化镁的2-甲基四氢呋喃溶液滴加入含有1.0eq中间体A-2的四氢呋喃溶液中，滴加毕，室温25℃搅拌3-5h，加入1M稀盐酸溶液淬灭反应体系；加入乙酸乙酯萃取有机相，静置分液，水洗有机相至中性，无水硫酸钠干燥有机相，减压脱溶剂，经柱层析分离提纯得到中间体A-3；
(4)制备中间体A
将中间体A-3加入到100-1000mL圆底烧瓶中，以10-20mL/1g中间体A-3 的比例加入醋酸和催化量浓盐酸，加热回流12-18h；加入去离子水淬灭反应，乙酸乙酯萃取有机相，去离子水洗有机相至中性，无水硫酸钠干燥有机相，减压脱溶剂，经柱层析分离提纯得到中间体A。
2、中间体M的制备
(1)制备中间体A-BE
在氮气环境下，将中间体A、联硼酸频哪醇酯、醋酸钾按照摩尔比为 1.0∶(1.0-1.5)∶3.0混合，添加到含有催化剂Pd(PPh3)4的甲苯溶液中；回流保温反应10-12h，降温，经柱层析分离提纯得到中间体A-BE；
(2)制备中间体M-1
在氮气环境下，将中间体A-BE、1-溴-8-氯萘、碳酸钾按照摩尔比为1∶ (1.0-1.2)∶3.0混合，添加到含有催化剂醋酸钯、三叔丁基膦四氟硼酸盐的甲苯/水的混合溶液中，氮气保护下回流反应12-16h，降温冷却，反应液静置分液，干燥，经柱层析分离提纯得到中间体M-1；
(3)制备中间体M-2
在氮气环境下，将中间体M-1、DBU、Pd(PPh3)按照摩尔比为1.0∶ (1.0-3.0)∶(0.1-0.2)混合，添加到DMF溶液中；回流保温反应10-12h，降温，将反应液倒入水中，析出大量浅黄绿色固体，抽滤，经柱层析分离提纯得到中间体M-2；
(4)制备中间体M-3
将中间体M-2加入到100-1000mL高压釜内，以0.1-0.2g/1g中间体M-2 的比例加入Pd/C(5％)，以50-100mL/1g中间体M-2的比例加入四氢呋喃；氮气置换三次、进一步氢气置换三次，保持体系氢气环境；保持温度50-60℃，压力1.0-1.5MPa，反应10-15h，降温，抽滤，除掉Pd/C，过柱除机械杂质，进一步脱溶剂，经柱层析分离提纯得到中间体M-3；
(5)制备中间体M-4
在氮气环境下，将中间体M-3、邻氯溴苯、叔丁醇钾按照摩尔比为1∶ (1.0-1.2)∶(2.0-3.0)的，添加到含有催化剂醋酸钯，三叔丁基膦四氟硼酸盐的邻二甲苯溶液中，氮气保护下回流反应12-16小时，降温冷却，抽滤，水洗有机相至中性，干燥，脱溶剂，经柱层析分离提纯得到中间体M-4；
(6)制备中间体M
在氮气环境下，将中间体M-4、碳酸钾、Pd(OAc)2按照摩尔比为1.0∶ (2.0-3.0)∶(0.1-0.2)混合，添加到DMF溶液中；回流保温反应20-24h，降温，将反应液倒入水中，析出大量黄绿色固体，抽滤，经柱层析分离提纯得到中间体M。
3、中间体N的制备
(1)制备中间体N-1
在氮气环境下，将中间体A-BE、2-溴-2′-氯联苯、碳酸钾按照摩尔比为1∶(1.0-1.2)∶3.0混合，添加到含有催化剂醋酸钯、三叔丁基膦四氟硼酸盐的甲苯/水的混合溶液中，氮气保护下回流反应12-16h，降温冷却，反应液静置分液，干燥，经柱层析分离提纯得到中间体N-1；
(2)制备中间体N-2
在氮气环境下，将中间体N-1、DBU、Pd(PPh3)2Cl2按照摩尔比为1.0∶ (1.0-3.0)∶(0.1-0.2)混合，添加到DMF溶液中；回流保温反应10-12h，降温，将反应液倒入水中，析出大量黄绿色固体，抽滤，经柱层析分离提纯得到中间体N-2；
(3)制备中间体N-3
将中间体N-2加入到100-1000mL高压釜内，以0.1-0.2g/1g中间体N-2 的比例加入Pd/C(5％)，以50-100mL/1g中间体N-2的比例加入四氢呋喃；氮气置换三次、进一步氢气置换三次，保持体系氢气环境；保持温度50-60℃，压力1.0-1.5MPa，反应10-15h，降温，抽滤，除掉Pd/C，过柱除机械杂质，进一步脱溶剂，经柱层析分离提纯得到中间体N-3；
(4)制备中间体N-4
在氮气环境下，将中间体N-3、邻氯溴苯、叔丁醇钾按照摩尔比为1∶(1.0-1.2)∶(2.0-3.0)混合，添加到含有催化剂醋酸钯、三叔丁基膦四氟硼酸盐的邻二甲苯溶液中，氮气保护下回流反应12-16h，降温冷却，抽滤，水洗有机相至中性，干燥，脱溶剂，经柱层析分离提纯得到中间体N-4；
(5)制备中间体N
在氮气环境下，将中间体N-4、碳酸钾、Pd(OAc)2按照摩尔比为1.0∶ (2.0-3.0)∶(0.1-0.2)的，添加到DMF溶液中；回流保温反应20-24h，降温，将反应液倒入水中，析出大量黄绿色固体，抽滤，经柱层析分离提纯得到中间体N。
本发明的第三个目的在于提供上述双极性主体有机电致发光材料作为发光层材料，在制作有机电致发光器件领域的应用。
应用时，所制备的有机电致发光器件一般包括依次迭加的ITO导电玻璃衬底(阳极)、空穴注入层(HATCN)、空穴传输层(NPB)、发光层(本发明中所述材料+其他)、电子传输层(TPBI)、电子注入层(LiF)和阴极层(AI)。所有功能层均采用真空蒸镀工艺制成。该类器件中所用到的有机化合物的分子结构式如下所示。
本发明的有益效果是：
本发明的双极性主体有机电致发光材料具有较高的载流子注入和传输能力，具有良好的传输空穴和电子的双极特性，因此，使用这种材料制备的有机电致发光器件具有启亮电压低、发光效率高等优点；本发明的双极性主体有机电致发光材料具有较大的分子量，具有较高玻璃化转变温度和热分解温度，化合物的稳定性高，有利于显著提高器件的寿命；本发明的双极性主体有机电致发光材料具有较高的单线态和三线态能级，可优选作为绿光主体材料使用。应用本发明的双极性主体有机电致发光材料作为主体材料，制备的器件能够有效提升外量子效率、功率效率和电流效率。
附图说明
图1为本发明有机电致发光器件的结构示意图；
图中，1、ITO导电玻璃衬底；2、空穴注入层；3、空穴传输层；4、发光层；5、电子传输层；6、电子注入层；7、阴极层。
具体实施方式
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1化合物C15的制备
向250ml三口瓶中依次加入中间体M(4.07g，0.01mol)、2-(4-溴苯基)-4，6-二苯基-1，3，5-三嗪(4.66g，0.012mol)、邻二甲苯(100mL)、催化剂Pd(OAc)2(45mg，0.0002mol)、三叔丁基膦四氟硼酸盐(116mg，0.0004 mol)和叔丁醇钾(2.24g，0.02mol)，25℃搅拌10min，浴温设置为145-150℃，氮气保护下回流搅拌反应16.0hrs，TLC监测原料反应完全后降温至25℃；抽滤除去大部分机械杂质及盐分，滤液水洗至中性，无水硫酸钠干燥有机相，有机相脱溶剂，得棕黄色固物；使用1L四氢呋喃将滤饼热溶后降至室温，直接柱层析除去全部机械杂质，过柱液脱溶剂得棕黄色粉末状固体；柱层析提纯分离得到2.66g黄色粉末状固体，收率37.3％；进一步可使用四氢呋喃/ 无水乙醇重结晶。
实施例2化合物C16的制备
向250ml三口瓶中依次加入中间体N(4.33g，0.01mol)、2-(4-溴苯基)-4，6-二苯基-1，3，5-三嗪(4.66g，0.012mol)、邻二甲苯(100mL)、催化剂Pd(OAc)2(45mg，0.0002mol)、三叔丁基膦四氟硼酸盐(116mg，0.0004 mol)和叔丁醇钾(2.24g，0.02mol)，25℃搅拌10min，浴温设置为145-150℃，氮气保护下回流搅拌反应16.0hrs，TLC监测原料反应完全后降温至25℃；抽滤除去大部分机械杂质及盐分，滤液水洗至中性，无水硫酸钠干燥有机相，有机相脱溶剂，得棕黄色固物；使用1L四氢呋喃将滤饼热溶后降至室温，直接柱层析除去全部机械杂质，过柱液脱溶剂得棕黄色粉末状固体；柱层析提纯分离得到3.24g黄色粉末状固体，收率43.8％；进一步可使用四氢呋喃/ 无水乙醇重结晶。
本发明选取化合物C15、C16作为发光层，制作有机电致发光器件。
应当理解，器件实施过程与结果，只是为了更好地解释本发明，并非对本发明的限制。
应用例1
化合物C15在有机电致发光器件中的应用：
a)清洗ITO(氧化铟锡)玻璃：分别用去离子水、丙酮、乙醇超声清洗ITO玻璃各30分钟，然后在等离子体清洗器中处理5分钟；
b)在阳极ITO玻璃上真空蒸镀空穴注入层HATCN，厚度为10nm；
c)在空穴注入层HATCN之上，真空蒸镀空穴传输层NPB，厚度为30nm；
d)在空穴传输层NPB之上，真空蒸镀发光层实施例1制备的化合物C15 和lr(ppy)3，厚度为30nm；
e)在发光层之上，真空混合蒸镀作为电子传输层的TPBI，厚度为30nm；
f)在电子传输层之上，真空蒸镀电子注入层LiF，厚度为1nm；
g)在电子注入层之上，真空蒸镀阴极Al，厚度为100nm。
器件一的结构为ITO/HATCN(10nm)/NPB(30nm)/化合物C15：lr(ppy) 3＝93：7，(w/w，30nm)/TPBI(30nm)/LiF(1nm)/Al(100nm)，以化合物C15作为器件一的主体材料，所得器件测试结果见表1所示。
应用例2
根据与应用例1相同的方法制作有机电致发光器件二，区别在于使用C16作为发光层的主体材料，所得器件的测试结果见表1所示。
对比例
根据与应用例1相同的方法制作有机电致发光器件，区别在于使用 4，4′-二(9H-咔唑)-1，1′-联苯(CBP)作为发光层的主体材料，所得器件的测试结果见表1所示。
表1
如表1所示，基于CBP的器件，具有4.8V的高启亮电压，最大功率效率12.8lm/W，最大电流效率17.1cd/A；基于本发明主体材料制备的有机电致发光器件，展示了较好的性能，化合物C15器件启亮电压4.0V，最大电流效率28.2cd/A，最大功率效率22.0lm/W；化合物C16器件启亮电压4.1V，最大电流效率26.9cd/A，最大功率效率20.3lm/W。与常规主体材料CBP比较，本发明的器件在效率、驱动电压和稳定性方面表现出出色的特性，特别地在效率方面显示出较高发光特性，且具有显著的双极特性。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (6)

1.一种双极性主体有机电致发光材料，其特征在于，其结构式如下：
其中，Ar为C1-C10的取代或未取代的脂肪族直链或支链烷基、C6-C30的取代或未取代的芳基或C3-C30的取代或未取代的含杂原子芳基；
R1、R2、R3、R4、R5、R6、R7、R8各自独立地为氢原子、氘原子、C1-C10的脂肪族直链或支链烷基、C1-C10的脂肪族直链或支链烷氧基。
2.根据权利要求1所述的有机电致发光材料，其特征在于，所述的含杂原子芳基中所述的杂原子为氮、氧或硫原子中的一种或两种以上；
R1、R2、R3、R4、R5、R6、R7、R8中，任意两个相邻基团相互键合形成饱和或不饱和的环结构。
3.根据权利要求1所述的有机电致发光材料，其特征在于，R1、R2、R3、R4、R5、R6、R7、R8中，任意两个相邻基团相互键合形成蒽或苯并菲结构。
4.根据权利要求1所述的有机电致发光材料，其特征在于，Ar为如下基团中的任意一种：
5.根据权利要求1-4任一项所述的有机电致发光材料，其特征在于，其结构式为如下结构式中的任意一种：
6.一种权利要求1所述双极性主体有机电致发光材料作为发光层材料，在制作有机电致发光器件领域的应用。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111039928A (zh) * 2020-03-16 2020-04-21 北京夏禾科技有限公司 一种含螺烯结构的有机电致发光材料及器件
CN112442044A (zh) * 2019-08-29 2021-03-05 南京高光半导体材料有限公司 一种双极性绿色磷光主体材料及有机电致发光器件

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CN112442044A (zh) * 2019-08-29 2021-03-05 南京高光半导体材料有限公司 一种双极性绿色磷光主体材料及有机电致发光器件
CN111039928A (zh) * 2020-03-16 2020-04-21 北京夏禾科技有限公司 一种含螺烯结构的有机电致发光材料及器件
CN111039928B (zh) * 2020-03-16 2020-12-11 北京夏禾科技有限公司 一种含螺烯结构的有机电致发光材料及器件
CN113402501A (zh) * 2020-03-16 2021-09-17 北京夏禾科技有限公司 一种含螺烯结构的有机电致发光材料及器件
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