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 PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003960 organic solvent Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 8
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 8
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 8
- SGCLBIRCSTXTIU-UHFFFAOYSA-N boric acid;2,3-dimethylbutane-2,3-diol Chemical compound OB(O)O.CC(C)(O)C(C)(C)O.CC(C)(O)C(C)(C)O SGCLBIRCSTXTIU-UHFFFAOYSA-N 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 4
- FNKCOUREFBNNHG-UHFFFAOYSA-N 1,3-dibromo-5-chlorobenzene Chemical compound ClC1=CC(Br)=CC(Br)=C1 FNKCOUREFBNNHG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
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- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 2
- -1 boric acid ester Chemical class 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 6
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
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- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
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- 238000003996 delayed luminescence Methods 0.000 description 1
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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Abstract
Description
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:
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:
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:
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:
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;
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:
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:
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:
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:
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:合成路线如下:
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%)。
(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)。
(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%)。
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
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)
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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