CN110003115B - 一种蓝色有机发光材料、发光器件及制备方法 - Google Patents

一种蓝色有机发光材料、发光器件及制备方法 Download PDF

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CN110003115B
CN110003115B CN201910219245.6A CN201910219245A CN110003115B CN 110003115 B CN110003115 B CN 110003115B CN 201910219245 A CN201910219245 A CN 201910219245A CN 110003115 B CN110003115 B CN 110003115B
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孟鸿
施明
贺耀武
孙越
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Peking University Shenzhen Graduate School
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Abstract

本发明公开了一种蓝色有机发光材料、发光器件及制备方法，其中，蓝色有机发光材料的分子结构式如下：
Figure DDA0002003052770000011
其中，D为1,3‑二苯胺基苯，A为含氮芳杂环，n＝1～4。含氮芳杂环，具有优异的稳定性和强吸电子能力，与1,3‑二苯胺基苯具有接近的载流子传输能力，平衡的载流子传输能力有利于提高发光效率。此外，本发明中，L选择的是苯链，苯的个数取1至4，分子量不超过1000，合成较容易。

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一种蓝色有机发光材料、发光器件及制备方法
技术领域
本发明涉及有机发光材料领域，尤其涉及一种蓝色有机发光材料、发光器件及制备方法。
背景技术
基于有机电致发光材料的OLED显示技术，在智能手机、电视、照明，大屏显示等领域已取得成功的应用，其柔性显示，质量轻薄，响应快速，高纯显色，主动发光且能耗低等优势，受到了学术界和工业界的广泛重视和研究。
根据光的三原色，有机发光材料可以分为蓝色，红色和绿色三种发光材料，目前的白光显示中最大的瓶颈就是蓝光材料，尤其是浅蓝色到深蓝色的高性能蓝光材料。有机磷光蓝光材料由于需要贵金属(Ir,Pt等)，而且器件的稳定性和发光纯度都有很大的困难；有机荧光蓝光材料更有优势。荧光材料按照发光的过程可以分为普通荧光和延迟荧光。普通荧光就是单线态上的25％的单线态激子直接跃迁回基态所发射的荧光，这类荧光材料的理论最大内部量子效率为25％，如果外部光量子耦合效率为0.2，它的最大外部发光效率为5％，这远远不能满足商业的需求；另一类就是延迟荧光材料，目前根据延迟发光机理不同分为三种：热激发延迟荧光(TADF)，三线态-三线态激子湮灭延迟荧光(TTA)和高线态逆转换延迟荧光(HLCT)。目前研究最多也是效果最好的就是TADF蓝光材料，由于热激发下三线态激子可以逆转换单线态，从而内部量子效率可以实现100％，这类延迟荧光材料在发光效率上和传统荧光相比取得了巨大的突破。但是基于TADF材料的发光器件的效率滚降是一个十分严重的问题，这是由于三线态长的激子寿命和过高的激子浓度所致。
因此，现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种蓝色有机发光材料、发光器件及制备方法，旨在解决现有的蓝色有机发光材料发光效率不高的问题。
本发明的技术方案如下：
一种蓝色有机发光材料，分子结构式如下：
Figure BDA0002003052750000021
其中，D为1,3-二苯胺基苯，A为含氮芳杂环，n＝1～4。
所述的蓝色有机发光材料，其中，所述A选自如下有机分子中的一种：
Figure BDA0002003052750000022
Figure BDA0002003052750000031
一种蓝色有机发光材料的制备方法，包括：步骤A、制备硼酸酯：
Figure BDA0002003052750000032
步骤B、保护气氛下，将所述硼酸酯、化合物1-B、四三苯基磷钯和无水碳酸钠分散于第一有机溶剂中，反应得到蓝色有机发光材料：
Figure BDA0002003052750000041
其中所述化合物1-B的分子结构为：
Figure BDA0002003052750000042
所述的蓝色有机发光材料的制备方法，其中，所述步骤A包括：
步骤A1、保护气氛下，将1-氯-3,5-二溴苯、二苯胺、三(二亚苄基丙酮)二钯和三叔丁基磷分散于所述第一有机溶剂中，反应得到第一中间体；
步骤A2、保护气氛下，将所述第一中间体、联频哪醇硼酸酯分散于第二有机溶剂中，反应得到第二中间体；
步骤A3、保护气氛下，将所述第二中间体、联频哪醇硼酸酯、溴代原料分散于所述第二有机溶剂中，反应得到所述硼酸酯；
其中，所述溴代原料为：
Figure BDA0002003052750000043
所述的蓝色有机发光材料的制备方法，其中，所述步骤A1中，所述反应得到第一中间体的反应条件为：(105-115)℃下反应10h以上。
和/或所述步骤A2中，所述反应得到第二中间体的反应条件为：(95-105)℃下反应10h以上。
所述的蓝色有机发光材料的制备方法，其中，所述第一有机溶剂为甲苯。
所述的蓝色有机发光材料的制备方法，其中，所述第二有机溶剂为无水1,4-二氧六环。
一种发光器件，从上至下依次包括阴极、发光层和阳极，所述发光层由如上所述的蓝色有机发光材料制作而成。
所述的发光器件，其中，所述发光层采用蒸镀法或溶液法制作。
有益效果：本发明提供了一种如上所述的蓝色有机发光材料，结构模型为：Donor(D)-Ligand(L)-Acceptor(A)，其中，D选择的是1,3-二苯胺基苯；A选择的是含氮芳杂环，具有优异的稳定性和强吸电子能力，与D具有接近的载流子传输能力，平衡的载流子传输能力有利于提高发光效率。此外，本发明中，L选择的是苯链，苯的个数取1至4，分子量不超过1000，合成较容易。
附图说明
图1为本发明实施例1的紫外吸收光谱图。
图2为本发明实施例1的荧光发光光谱图。
具体实施方式
本发明提供了一种蓝色有机发光材料、发光器件及制备方法，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明提供蓝色有机发光材料，分子结构式如下：
Figure BDA0002003052750000051
其中，D为1,3-二苯胺基苯，L为苯的个数取1-4的苯链，A为含氮芳杂环。通过高斯计算，这一类材料的HOMO和LUMO能级差都在3.0eV以上，蓝光的发光带隙的要求是不低于2.90eV，因此可以判定这一类材料属于蓝光材料。
本发明材料结构模型为：Donor(D)-Ligand(L)-Acceptor(A)，D-L-A。其中，D选择的是1,3-二苯胺基苯；A选择的是含氮芳杂环，具有优异的稳定性和强吸电子能力，与D具有接近的载流子传输能力，平衡的载流子传输能力有利于提高发光效率。同时由于氮原子强的电负性，在形成含氮芳杂环之后，芳环的共轭效应，使整个基团都呈现较强的电负性；并且由于氮原子的SP2杂化，含氮芳杂环具有很好的稳定性和电子传输能力。
具体的，A可选自如下有机分子中的一种：
Figure BDA0002003052750000061
Figure BDA0002003052750000071
D-A之间的配体对分子内电荷转移的影响至关重要，本发明中，L选择的是苯链，苯的个数取1至4。当苯的个数为1或2的时候，D和A之间的距离为8.6埃，小于1nm，分子内的能量转移机制为Dexter能量转移，当增加到3和4的时候，Fostor能量转移也可以发生，苯的个数可以调节D和A之间的距离，距离的变化对分子发光效率有很大的影响。
本发明中，苯的个数取限制在4以内，另一个原因在于：OLED发光的小分子分子量一般不超过1000，若超过1000，会给材料的纯化带来困难。因此，本发明选定的给体基团的分子量为411，受体最小的分子量为232，当中间苯的个数为4的时候，整个分子的分子量是947，接近但不超过1000；同时苯的个数增加到5个以上时，会大大增加的合成的难度。
D-A型分子的二面角对分子的性质影响重大，从给受体之间的二面角来看(通过Spartan软件构型优化后的计算结果)，苯的个数由1至4，已经实现了90°-0°之间的梯度变化，从二面角层面来看分子设计，1至4的苯的个数以满足研究要求，这是一类具有很好的空穴传输能力和强供电子能力的分子结构。
基于上述发明思路及相应的受体基团A，本发明的蓝色有机发光材料可以是如下分子式1-108中的任意一种：
Figure BDA0002003052750000081
Figure BDA0002003052750000091
Figure BDA0002003052750000101
Figure BDA0002003052750000111
Figure BDA0002003052750000121
Figure BDA0002003052750000131
Figure BDA0002003052750000141
Figure BDA0002003052750000151
Figure BDA0002003052750000161
Figure BDA0002003052750000171
Figure BDA0002003052750000181
Figure BDA0002003052750000191
Figure BDA0002003052750000201
本发明的蓝色有机发光材料可通过Suzuki偶联反应制备得到，本发明提供了一种较佳实施例，以结构式为
Figure BDA0002003052750000202
的受体A为例进行说明，制备步骤包括如下：
步骤A、首先制备硼酸酯：
Figure BDA0002003052750000203
具体的，本发明提供了上述硼酸酯的一种制备方法实施例，具体步骤包括：
步骤A1、保护气氛下，将1-氯-3,5-二溴苯、二苯胺、三(二亚苄基丙酮)二钯和三叔丁基磷分散于所述第一有机溶剂中，反应得到第一中间体；具体的，第一有机溶剂可以选择无水甲苯，反应可以于(105-115)℃下反应10h以上，待反应体系冷却至室温后硅胶漏斗过滤，溶液低压浓缩后，采用二氯甲烷和正己烷进行柱层析得到中间产物。
步骤A2、保护气氛下，将所述第一中间体、联频哪醇硼酸酯分散于第二有机溶剂中，反应得到第二中间体；具体的，第二有机溶剂可以选择无水1,4-二氧六环，可以将第一中间体和联频哪醇硼酸酯加入到无水1,4-二氧六环中，于(95-105)℃下反应10h以上。待反应体系冷却至室温后硅胶漏斗过滤，溶液低压浓缩后，采用二氯甲烷和正己烷进行柱层析得到第二中间体。
步骤A1、A2的合成路线如下：
Figure BDA0002003052750000211
步骤A3、保护气氛下，将所述第二中间体、联频哪醇硼酸酯、溴代原料分散于所述第二有机溶剂中，反应得到所述硼酸酯；具体的，可以于(95-105)℃下反应10h以上。待反应体系冷却至室温后硅胶漏斗过滤，溶液低压浓缩后，采用二氯甲烷和正己烷进行柱层析得到硼酸酯。其中，所述溴代原料为：
Figure BDA0002003052750000212
合成路线如下：
Figure BDA0002003052750000221
步骤B、保护气氛下，将所述硼酸酯、化合物1-B、四三苯基磷钯和无水碳酸钠分散于第一有机溶剂中，反应得到蓝色有机发光材料：
Figure BDA0002003052750000222
其中所述化合物1-B的分子结构为：
Figure BDA0002003052750000223
合成路线如下：
Figure BDA0002003052750000224
本发明还提供了上述蓝色有机发光材料的应用，将其应用于电致发光显示装置中。通过计算和测试，本发明的这类材料的带隙都在3.0eV以上，都具备很好的蓝光荧光。当作为发光材料的时候，由于自身的双极性特性，以及对电子和空穴两种载流子相对平衡的传输能力，器件结构可简化为阴极-发光层-阳极的极简结构。
进一步的，由于材料自身具有优越的热稳定性和一定的溶解性，器件制备时，除了传统的蒸镀发，还可以采用溶液法，溶液法加工OLED器件不仅简化了工艺，而且可以大大降低设备投资。
下面通过具体实施例对本发明进行详细说明。
实施例1化合物1的制备
(1)氮气条件下向100ml无水甲苯中加入1-氯-3,5-二溴苯(7.98g，29.5mmol)和二苯胺(10g，59.1mmol)，三(二亚苄基丙酮)二钯(0.67g，0.58mmol)，三叔丁基磷(15％，0.15mmol)，110℃下搅拌12小时。反应冷却至室温后硅胶漏斗过滤，溶液低压浓缩后，采用二氯甲烷和正己烷进行柱层析得到第一中间体(11.21g，25mmol)，产率85％；
(2)氮气条件下将中间产物干燥后，加入无水1,4-二氧六环、联频哪醇硼酸酯(7.62g，30mmol)，100℃下搅拌12小时。反应冷却至室温后硅胶漏斗过滤，溶液低压浓缩后二氯甲烷和正己烷进行柱层析得到第二中间体(10.77g，80％)。
Figure BDA0002003052750000231
(3)氮气条件下将上述第二中间体、溴苯(30mmol)加入无水1,4-二氧六环，然后加入联频哪醇硼酸酯(7.62g，30mmol)，100℃下搅拌12小时。反应冷却至室温后硅胶漏斗过滤，溶液低压浓缩后二氯甲烷和正己烷层柱析得到硼酸酯(1-A)。
Figure BDA0002003052750000241
(4)氮气条件下向100ml无水甲苯中加入1-A(6.15g，10.0mmol)、1-B(3.23g，10.0mmol)、四三苯基磷钯(5％，0.58g)、无水碳酸钠(3.20g，30.0mmol)，110℃下搅拌12小时。反应冷却至室温后硅胶漏斗过滤，所得溶液低压浓缩后，采用二氯甲烷和正己烷进行柱层析得到化合物1(5.12g，产率70％)。
Figure BDA0002003052750000242
化合物2-104的制备方法和化合物1的制备方法相同，本发明不再赘述，其中所有的给体片段均为已公开的化合物，可从正规渠道购买。
性能测试
图1为本发明实施例1合成的材料的UV吸收图，从吸收边可以计算出带隙宽为3.35eV,这样的带隙表明该材料属于深蓝光范畴；图2为本发明实施例1合成的材料的PL图，发射峰的最高点的位移为420nm，且半峰宽只有65nm，表明该材料的蓝光发光纯度非常高。
表1为本发明实施例1合成的材料的光学和电学性能表征结果。除了UV和PL外，还进行了电化学实验，测试材料的HOMO和LUMO能级，分别为-5.49eV和-1.98Ev，从而计算出带隙为3.51Ev,同时也说明该材料具有双极性。同时本发明还测试了材料的三线态，从而计算出了单线态和三线态能极差为0.34Ev。
表1光学和电学性能表征
Figure BDA0002003052750000251
综上所述，本发明提供了一种蓝色有机发光材料、发光器件及制备方法，本发明的蓝色有机发光材料结构模型为：Donor(D)-Ligand(L)-Acceptor(A)，D-L-A。其中，D选择的是1,3-二苯胺基苯；A选择的是含氮芳杂环，具有优异的稳定性和强吸电子能力，与D具有接近的载流子传输能力，平衡的载流子传输能力有利于提高发光效率。此外，本发明中，L选择的是苯链，苯的个数取1至4，分子量不超过1000，合成较容易。本发明的这类材料的带隙都在3.0eV以上，都具备很好的蓝光荧光。由于材料自身具有优越的热稳定性和一定的溶解性，还可以采用溶液法制备器件的发光层，工艺简单。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (9)

1.一种蓝色有机发光材料，其特征在于，分子结构式如下：
Figure FDA0003718530640000011
其中，D为1,3-二苯胺基苯，A为含氮芳杂环，n＝1～4，所述A选自如下有机分子中的一种，其中，
Figure FDA0003718530640000012
为连接位点；
Figure FDA0003718530640000013
Figure FDA0003718530640000021
2.根据权利要求1所述的蓝色有机发光材料，其特征在于，分子结构式为如下分子式1-108任意一种：
Figure FDA0003718530640000031
Figure FDA0003718530640000041
Figure FDA0003718530640000051
Figure FDA0003718530640000061
Figure FDA0003718530640000071
Figure FDA0003718530640000081
Figure FDA0003718530640000091
Figure FDA0003718530640000101
Figure FDA0003718530640000111
Figure FDA0003718530640000121
Figure FDA0003718530640000131
Figure FDA0003718530640000141
Figure FDA0003718530640000151
3.一种蓝色有机发光材料的制备方法，其特征在于，包括：
步骤A、制备硼酸酯：
Figure FDA0003718530640000152
步骤B、保护气氛下，将所述硼酸酯、化合物1-B、四三苯基磷钯和无水碳酸钠分散于第一有机溶剂中，反应得到蓝色有机发光材料：
Figure FDA0003718530640000153
其中所述化合物1-B的分子结构为：
Figure FDA0003718530640000154
4.根据权利要求3所述的蓝色有机发光材料的制备方法，其特征在于，所述步骤A包括：
步骤A1、保护气氛下，将1-氯-3,5-二溴苯、二苯胺、三(二亚苄基丙酮)二钯和三叔丁基磷分散于所述第一有机溶剂中，反应得到第一中间体；
步骤A2、保护气氛下，将所述第一中间体、联频哪醇硼酸酯分散于第二有机溶剂中，反应得到第二中间体；
步骤A3、保护气氛下，将所述第二中间体、联频哪醇硼酸酯、溴代原料分散于所述第二有机溶剂中，反应得到所述硼酸酯；
其中，所述溴代原料为：
Figure FDA0003718530640000161
n＝1～4。
5.根据权利要求4所述的蓝色有机发光材料的制备方法，其特征在于，所述步骤A1中，所述反应得到第一中间体的反应条件为：(105-115)℃下反应10h以上；
和/或所述步骤A2中，所述反应得到第二中间体的反应条件为：(95-105)℃下反应10h以上。
6.根据权利要求3所述的蓝色有机发光材料的制备方法，其特征在于，所述第一有机溶剂为甲苯。
7.根据权利要求4所述的蓝色有机发光材料的制备方法，其特征在于，所述第二有机溶剂为无水1,4-二氧六环。
8.一种发光器件，其特征在于，从上至下依次包括阴极、发光层和阳极，所述发光层由权利要求1-2任一所述的蓝色有机发光材料制作而成。
9.根据权利要求8所述的发光器件，其特征在于，所述发光层采用蒸镀法或溶液法制作。
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