CN111763133A - 基于芴单元的蓝光发射体 - Google Patents
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title claims abstract description 35
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Abstract
本发明公开了基于芴单元的蓝光发射体。由于芴的刚性平面联苯结构使材料易于发生分子间聚集,从而大大降低了其色纯度,效率和稳定性。因此发明以芴原子为核心,在其9号位上引入不同的基团,生成一系列的芴基衍生物,从而在很宽的范围内微调其溶解性,热稳定性,光物理性质,能级和载流子迁移率。本发明提出了一种独特的分子骨架(如FTRZ),其有助于实现最有组织的薄膜和最高的载流子迁移率,并且已验证类似于FTRZ的连接模型是生产高效且稳定的蓝光发射器的更可行方法。
Description
技术领域
本发明涉及有机电致发光材料技术领域,具体涉及基于芴单元的蓝光发射体。
背景技术
自21世纪以来,有机发光材料因其出色的光电性能,在有机场效应晶体管、生物和化学传感器、用于平板显示器和固态照明的有机发光二极管(OLED)中均得到有效的应用。根据发光机理,有机发光材料可以分为荧光和磷光材料。荧光发射仅使用单重态(S1)激子,其内部量子效率(IQE)最高可达25%。为了通过使用三重态(T1)激子来提高磷光OLED的发光效率,必须使用基于重金属配合物的磷光染料来提高自旋轨道耦合,以促进从最低T1到基态的辐射跃迁。磷光可以同时使用S1和T1发光,IQE可以高达100%。然而,重金属络合物的高成本和潜在毒性限制了磷光OLED的大规模生产。
为了克服上述问题,研究出了对热激活延迟荧光(TADF)发射器,其中T1通过反向系统间交叉热激活而被上转换为S1。这样,基于TADF发射器的OLED的IQE可以达到100%而无需使用稀有的贵金属磷光配合物。
而为了拥有更为高效的OLED,必须平衡电荷注入和传输,捕获所有注入的电荷以形成激子和所有激子的辐射衰减,这突出了固体薄膜的能带隙和载流子迁移率的重要性。芴是一种具有很高的热稳定性、光致发光量子效率和宽禁带宽度的蓝光发射类材料,但其所具有的刚性平面联苯结构使其易于发生分子间聚集,从而大大降低了其色纯度、效率和稳定性。为了能在很宽的范围内微调其溶解度、热稳定性、光物理性质、能级和载流子迁移率,相关领域技术人员尝试将各种取代基引入其2位、7位和9位碳上以获得一系列芴基衍生物,现有成果表明该方法是可行的。
根据TADF机理,研究人员提出了一种有机供体-受体(D-A)共轭分子的合成方法,可以精细地调节所获得的芴基蓝色发射体的发射波长、效率和寿命。例如,有机TADF发射体通常由富含电子的供体和缺乏电子的受体杂环产生,以形成扭曲的DA结构,以确保S1状态和T1状态之间的能级差很小(ΔEST),保证强的分子内电荷转移(ICT)。同时,载流子的注入和运输也得到改善,这导致发光效率和发射波长的变化。
现有技术中,基于芴原子的不同侧基部分的发光体的结构-性能相关性的研究还鲜有报道。为了更为深入地了解其作用机理,我们以芴(F)作为模型发射极,并且在其9位碳上引入了不同侧基,生成一系列的芴基衍生物,通过比较各自的光电性能以获得结构-性能相关性方面的启示。这项工作对于设计和合成高效,稳定的有机芴基蓝色发光材料具有重要的指导意义。
发明内容
本发明的目的在于解决现有技术中存在的不足,提供基于芴单元的蓝光发射体及其制备方法和应用,为开发新的适用于可溶液加工的高效OLED主体材料提供新的设计方法。
本发明公开一类基于芴单元的蓝光发射体,其结构通式如下:
其中,R1、R2为C4-C8的烷基链或烷氧链、或苯环及其衍生物。
进一步地,当其为基于9,9-双苯基-9H-芴的衍生物时,具有如下通式所示化学结构,
其中,R1、R2为氢原子、或C4-C8的烷基链或烷氧链,或者苯环及其衍生物;
具体可以包括如下所示结构:
进一步地,当其为基于1,3,5-三嗪和芴原子的衍生物时,具有如下通式所示化学结构,
其中,R1、R2、R3为氢原子、或C4-C8的烷基链或烷氧链,或者苯环及其衍生物;
具体可以包括如下所示结构:
进一步地,该类蓝光发射体具有良好的热稳定性。
进一步地,该类蓝光发射体具有很好的结晶性。
进一步地,该类发射体具有很好的成膜性。
进一步地,该类发射体在有机溶剂中具有可溶解性;所述有机溶剂包括但不限于甲苯、氯苯或二氯甲烷。
进一步地,该类发射体具有很好的电子迁移率和空穴迁移率。
本发明的有益效果为:
本发明以芴原子为核心,通过在其9位碳上引入不同的基团后生成一系列的芴基衍生物,进而可在很宽的范围内微调其溶解性,热稳定性,光物理性质,能级和载流子迁移率;
在三嗪结构上引入大空间位阻的供电子基团,分子内形成较大的空间扭曲,限制苯环的共轭,提供高的三重态能级,且有利于非晶薄膜的形成,可以提高OLED器件效率;
在芳环上引入烷氧链,改善分子的溶解性,实现可溶液加工过程,降低OLED器件的制作成本;
本发明考察了分子拓扑结构的改变对材料的热稳定性,三重态能级,HOMO与LUMO能级的影响,为开发新的适用于可溶液加工的高效OLED主体材料提供新的设计方法。
附图说明
图1为化合物F、DBF、BOPF和FTRZ的DSC曲线图;
图2中(a)为化合物F、DBF、BOPF和FTRZ的紫外可见吸收光谱和光致发光光谱图;(b)为化合物FTRZ在不同浓度甲苯溶液中的光致发光光谱图;
图3为化合物F、DBF、BOPF和FTRZ在无水无氧二氯甲烷中的氧化曲线;
图4为化合物F、DBF、BOPF、FTRZ和pTFTRZ的优化分子结构的LUMO和HOMO分布图;
图5中(a)为晶体状态的化合物F的堆积结构图,(b)为晶体状态的化合物DBF的堆积结构图,(c)为晶体状态的化合物BOPF的堆积结构图,(d)为晶体状态的化合物FTRZ的堆积结构图;
图6中(a)为厚度为50nm的BOPF、FTRZ和pTFTRZ固体薄膜的电子和空穴迁移率图(H:空穴,E:电子),(b)为发射体BOPF、FTRZ和pTFTRZ固体薄膜的形态图;
图7为化合物DBF的氢谱图;
图8为化合物BOPF的氢谱图;
图9为化合物FTRZ的氢谱图。
具体实施方式
以下实施例进一步说明本发明的内容,但不应理解为对本发明的限制。在不背离本发明实质的情况下,对本发明方法、步骤或条件所作的修改和替换,均属于本发明的范围。
实施例1:化合物DBF,BOPF和FTRZ的合成
具体反应路线如下:
9,9-二丁基-9H-芴(DBF)的制备:将芴(0.83g,5mmol)和四丁基溴化铵(0.65g,2mmol)在NaOH溶液(15ml 50wt%)中于60℃条件下搅拌加热15分钟,然后将正丁基溴(1.2mL,1mmol)加入到悬浮液中,并将混合物在氮气保护下搅拌12h。所得混合物用二氯甲烷和水萃取3次,过滤,减压浓缩。残余物固体通过硅胶柱色谱纯化(洗脱剂:乙酸乙酯/石油醚=1/25体积),得到0.95g白色固体,产率为68%。
1H NMR(400MHz,CDCl3)δ7.76–7.70(m,2H),7.34(m,J=9.2,4.2Hz,6H),2.05–1.92(m,4H),1.08(m,J=14.9,7.5Hz,4H),0.73–0.59(m,10H)。
4,4'-(9H-芴-9,9-二基)双酚的制备:将芴酮(1.26g,7mmol)和苯酚(6.2mL,70mmol)的10mL甲基磺酸溶液在氮气保护下于50℃水浴中搅拌12小时。将所得混合物用二氯甲烷和水萃取3次,过滤,并减压浓缩。残余物固体通过硅胶柱色谱法纯化(洗脱剂:乙酸乙酯/石油醚=1/3体积),得到0.88g白色固体,产率为35%。
1H NMR(400MHz,CDCl3)δ7.77(d,J=7.5Hz,2H),7.35(m,J=19.1,15.5,4.3Hz,5H),7.28–7.23(m,1H),7.12–7.03(m,4H),6.72–6.65(m,4H),4.82(s,2H)。
9,9-双(4-丁氧基苯基)-9H-芴(BOPF)的制备:将4,4'-(9H-芴-9,9-二基)联苯酚(1g,2.9mmol)和K2CO3(2g,14.5mmol)在20mL DMF溶液中于80℃下搅拌半小时,然后将正丁基溴化物(0.7mL,6mmol)添加到该溶液中,并在氮气保护下在60℃搅拌12h。将所得混合物用二氯甲烷和水萃取3次,过滤,减压浓缩。残余物固体通过硅胶柱色谱法纯化(洗脱剂:乙酸乙酯/石油醚=1/3体积)。质量为1.153g,产率为88%。
1H NMR(400MHz,CDCl3)δ7.76(d,J=7.5Hz,2H),7.41–7.34(m,4H),7.29(d,J=1.4Hz,1H),7.27(d,J=7.5Hz,1H),7.12(d,J=8.9Hz,4H),6.75(d,J=8.9Hz,4H),3.91(t,J=6.5Hz,4H),1.78–1.71(m,4H),1.47(m,J=15.0,7.4Hz,4H),0.97(t,J=7.4Hz,6H)。
2-(4-(9-(4-(己氧基氧基)苯基)-9H-芴-9-基)苯基)-4,6-二苯基-1,3,5-三嗪(FTRZ)的制备:2-(4-溴苯基)-4,6-二苯基-1,3,5-三嗪(0.344g,0.89mmol)、三(二亚苄基丙酮)二钯(0)(21.3mg,0.036mmol)溶液、叔丁基二苯膦(17.9mg,0.074mmol)、9-(4-(己氧基)苯基)-9H-芴(0.253mg,0.74mmol)和叔丁醇钾(0.103mg,0.88mmol)溶于3mL甲苯(无水)中,在氮气气氛下于100℃搅拌12小时。所得混合物用二氯甲烷和水萃取3次,过滤,并减压浓缩。残余物固体通过硅胶柱色谱法纯化(洗脱剂:石油醚/二氯甲烷=5/1体积)得到0.322g白色固体,产率为67%。
1H NMR(400MHz,CDCl3)δ8.77–8.70(m,4H),8.63–8.58(m,2H),7.80(d,J=7.6Hz,2H),7.61–7.52(m,6H),7.46–7.36(m,6H),7.29(m,J=7.5,1.1Hz,2H),7.17–7.12(m,2H),6.82–6.76(m,2H),3.91(t,J=6.6Hz,2H),1.83–1.69(m,2H),1.47–1.38(m,2H),1.35–1.30(m,4H),0.91–0.87(m,3H)。
2,4,6-三(4-(9-(4-(己氧基氧基)苯基)-9H-芴-9-基)苯基)-1,3,5-三嗪(pTFTRZ)的制备:将2,4,6-三(4-溴苯基)-1,3,5-三嗪溶液(0.11g,0.2mmol)、三(二亚苄基丙酮)二钯(0)(17.1mg,0.03mmol)、叔丁基二苯基膦(14.5mg,0.06mmol)、叔丁醇钾(84mg,0.6mmol)和9-(4-(己氧基)苯基)-9H-芴(0.274g,0.8mmol)溶于2mL甲苯(无水)中,在氮气气氛下于110℃搅拌24小时。所得混合物用二氯甲烷和水萃取3次,过滤,并减压浓缩。残余物固体通过硅胶柱色谱法纯化(洗脱剂:石油醚/二氯甲烷=5/1体积)得到0.12g pTFTRZ(白色固体),产率为45%
结果表征:
热分析:如图1所示,用DSC表征发射体F(芴)、DBF、BOPF和FTRZ固体粉末的Tm值分别为117℃,57℃,67℃和186℃,从该数据看出,当将柔性正丁基链和对烷氧基苯基链引入芴侧基时,发射体的Tm降低,而刚性的2,4,6-三苯基-1,3,5-三嗪基的引入则增加了发射体的Tm值。
光物理表征:图2a显示了F、DBF、BOPF和FTRZ在10-5mol/L甲苯溶液中的紫外可见吸收光谱和光致发光光谱。从图中结果可知,F在293nm和304nm处有两个吸收峰,DBF在297nm和311nm处有两个吸收峰。甲苯溶液中,F、DBF、BOPF和FTRZ四个发射体的最大紫外可见光吸收峰分别在304nm、311nm、284nm和286nm处,这主要是由芴基的π-π*电子跃迁引起的。由于芴基与2,4,6-三苯基-1,3,5-三嗪基之间存在较大的二面角,阻碍了给电子基团和吸电子基团的相互作用,因此没有明显的电荷转移。
如图2a所示,F、DBF、BOPF和FTRZ的光致发光发射峰分别在315nm、319nm、325nm和400nm处。随着侧基从氢、正丁基、对烷氧基苯基到2,4,6-三苯基-1,3,5-三嗪的转变,发射体的光致发光发射光谱也发生红移。与其他三个发射器相比,FTRZ的最大光致发光发射红移为85nm,主要原因是缺电子的2,4,6-三苯基-1,3,5-三嗪基团导致ICT的明显转变。
如图2b所示,甲苯溶液中FTRZ的最大发射强度随浓度从10-6mol/L变为10-1mol/L而增加,但发射峰位置保持不变,表明溶液中的红移并不是由浓溶液中形成的潜在聚集引起的。
电化学和理论计算:四个发射体的电化学性质用CV表征。图3显示了在无水无氧二氯甲烷中四个发射器的氧化曲线。四个发射体都显示出不可逆的氧化峰,从CV曲线获得的四个发射体的氧化电位分别是:F为1.2V、DBF为1.27V、BOPF为1.36V、FTRZ为1.39V。根据公式EHOMO=-4.75-Eox(eV),所获得的HOMO能级对于F为5.95eV,对于DBF为-6.02eV,对于BOPF为-6.11eV,对于FTRZ为-6.23eV。将来自四个发射器在甲苯溶液中的紫外可见吸收起点的光能隙Eg与它们的电化学HOMO能级结合起来,四个发射器的LUMO能级计算结果是:F为-2.03eV,DBF为-2.19eV,BOPF为-2.25eV,FTRZ为-2.55eV。在芴的9位碳上的正丁基,对烷氧基苯基和2,4,6-三苯基-1,3,5-三嗪的侧基依次降低LUMO和HOMO能级。为了深入了解这些发射体的分子构象和电子结构,在B3LYP/6-31G(d)水平上计算了HOMO和LUMO分子轨道和Eg值。每个发射器的优化结构以及HOMO和LUMO分布如图4所示。F和DBF的LUMO和HOMO均分布在芴基上,芴基是局部激发中心,有助于激子的辐射跃迁。发射体BOPF的HOMO分布在芴和与芴基相连的苯基上,而LUMO主要分布在芴基上。对于发射极FTRZ和pTFTRZ,LUMO主要分布在2,4,6-三苯基-1,3,5-三嗪基团上,而HOMO主要分布在芴和与芴连接的对烷氧基苯基上。FTRZ中的芴与2,4,6-三苯基-1,3,5-三嗪基团之间存在扭曲角,这有助于分子内电荷转移以及不同状态下其光致发光发射的红移。通过量子化学计算,FTRZ和pTFTRZ的LUMO能级相对于其他发射体的明显降低与从CV实验获得的结果相符。
单晶解析:图5是四个处于晶体状态的发射器的堆积结构。通过分析四个发射体的晶体构象,获得了相邻芴环之间的距离和二面角,F分别为68.94°和DBF为75.49°和BOPF为34.92°和FTRZ分别为34.88°和发射极F,DBF和BOPF的分子之间存在明显的二面角,大分子间距以及C-H...π键相互作用。发射极FTRZ的相邻分子之间的1.3.5-三嗪平面彼此平行,并且在平面之间不仅存在强的π-π堆叠,而且芴部分之间存在C-H...π键相互作用。对芴氧基苯基和2,4,6-三苯基-1,3,5-三嗪相对于芴骨架的高度扭曲的空间构型,使其HOMO和LUMO有效分离,ΔEST较小。
迁移率和AFM:ITO/(BOPF,FTRZ或pTFTRZ(50nm))/Al的单电子器件用于测量空穴迁移率。Ca/Ag用于测量电子迁移率。图6a是在0-4V电压范围内的三个发射器的载流子迁移率图。可以看出,它们的电子迁移率和空穴迁移率按FTRZ,BOPF和pTFTRZ的顺序降低。对于FTRZ,在4×104V/cm的电场下观察到的最高电子迁移率为10-4cm2/V·s,是其空穴迁移率的一倍。BOPF和pTFTRZ固体薄膜的空穴迁移率高于其电子迁移率,并且BOPF和pTFTRZ中主要的p型芴基增强了电子给体能力,导致其空穴迁移率高于电子迁移率。FTRZ的固体薄膜在三个发射器中均表现出最高的空穴和电子迁移率,这突出了FTRZ的独特结构,可改善固体薄膜的载流子迁移率。
最后,我们使用原子力显微镜(AFM)来探测BOPF,FTRZ和pTFTRZ的膜形态,图6b显示了通过旋涂1,2,3-三氯苯溶液获得的三种厚度为50nm的薄膜形态。在ITO上浓度为16mg/mL的发光体。对应于三个发射器的高度偏差的均方根平均值的RMS值对于BOPF为4.32nm,对于FTRZ为1.11nm,对于pTFTRZ为11.8nm。阻抗谱表明,相对光滑的表面形态和FTRZ分子的均匀堆叠有利于载流子迁移。相反,以2,4,6-三苯基-1,3,5-三嗪为缺电子核的pTFTRZ的高度扭曲的星形三维结构无助于提高PLQY和载流子迁移率。通过结合膜形态学和载流子迁移率结果,我们发现像FTRZ这样独特的分子骨架有助于获得最光滑的膜以及相应的最高空穴和电子迁移率。
以上显示和描述了本发明的基本原理、主要特征及优点。但是以上所述仅为本发明的具体实施例,本发明的技术特征并不局限于此,任何本领域的技术人员在不脱离本发明的技术方案下得出的其他实施方式均应涵盖在本发明的专利范围之中。
Claims (8)
4.如权利要求1所述的基于芴单元的蓝光发射体,其特征在于,该类蓝光发射体具有良好的热稳定性。
5.如权利要求1所述的基于芴单元的蓝光发射体,其特征在于,该类蓝光发射体具有很好的结晶性。
6.如权利要求1所述的基于芴单元的蓝光发射体,其特征在于,该类发射体具有很好的成膜性。
7.如权利要求1所述的基于芴单元的蓝光发射体,其特征在于,该类发射体在有机溶剂中具有可溶解性;所述有机溶剂包括但不限于甲苯、氯苯或二氯甲烷。
8.如权利要求1所述的基于芴单元的蓝光发射体,其特征在于,该类发射体具有很好的电子迁移率和空穴迁移率。
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