CN111018880B - 热活化延迟荧光材料及使用其所制备的有机发光二极管 - Google Patents
热活化延迟荧光材料及使用其所制备的有机发光二极管 Download PDFInfo
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Abstract
Description
技术领域
本发明是有关于一种有机发光材料技术领域,特别是有关于一种热活化延迟荧光材料以及使用所述热活化延迟荧光材料所制备的有机发光二极管。
背景技术
有机发光二极管(organic light-emitting diodes,OLEDs)在固态照明及平板显示等领域具有广阔的应用前景,而发光客体材料是影响有机发光二极管的发光效率的主要因素。在早期,有机发光二极管使用的发光客体材料为荧光材料,其在有机发光二极管中的单重态和三重态的激子比例为1:3,因此在理论上有机发光二极管的内量子效率(internalquantum efficiency,IQE)只能达到25%,使荧光电致发光器件的应用受到限制。再者,重金属配合物磷光发光材料由于重原子的自旋轨道耦合作用,而能够同时利用单重态和三重态激子,进而达到100%的内量子效率。然而,通常重金属配合物磷光发光材料所使用的重金属都是铱(Ir)或铂(Pt)等贵重金属,并且重金属配合物磷光发光材料在蓝光材料方面尚有待改良。纯有机热活化延迟荧光材料(thermally activated delayed fluorescence,TADF)具有低单三重态的能级差(single-triplet energy gap,ΔEST),使得三重态激子可以通过反向系间窜越(reverse intersystem crossing,RISC)回到单重态,再通过辐射跃迁至基态而发光,从而能够同时利用单重态激子及三重态激子,在理论上亦可以实现100%的内量子效率。
对于热活化延迟荧光材料,低单三线态能级差、高反向系间窜越常数(kRISC)及高光致发光量子产率(photoluminescence quantum yield,PLQY)是制备高效率有机发光二极管的必要条件。然而,目前具备上述条件的热活化延迟荧光材料相对于重金属配合物而言还是比较缺乏的。因此,有必要提供一种新颖的热活化延迟荧光材料,以解决现有技术所存在的问题。
发明内容
有鉴于此,本发明提供一种热活化延迟荧光材料,其具有如式(I)所示的结构:
本发明另一实施例提供一种有机发光二极管,其包括:一阳极;一阴极;以及位于所述阳极与所述阴极之间的一发光层,所述发光层包括前述的热活化延迟荧光材料。
在本发明的一实施例中,所述热活化延迟荧光材料为下列化合物1:
在本发明的一实施例中,所述化合物1是通过下述合成路线合成出:
在本发明的一实施例中,所述热活化延迟荧光材料为下列化合物2:
在本发明的一实施例中,所述化合物2是通过下述合成路线合成出:
在本发明的一实施例中,所述热活化延迟荧光材料为下列化合物3:
在本发明的一实施例中,所述化合物3是通过下述合成路线合成出:
相较于先前技术,本发明实施例的高热活化延迟荧光材料具有较低的单三线态能级差、高反向系间窜越常数及高光致发光量子产率,进而有利于实现具有高发光效率的有机发光二极管。
附图说明
图1是本发明实施例的热活化延迟荧光材料在室温下于甲苯溶液中的光致发光光谱。
图2是本发明实施例的有机发光二极管的示意图。
具体实施方式
一般热活化延迟荧光材料具有电子给体和电子受体相结合的分子结构,本发明通过调控给体单元的结构来改变其给电子能力,有效的增加热活化延迟荧光材料的发光效率,进而有利于实现具有高性能的有机发光二极管。本发明提供的热活化延迟荧光材料,其主要具有如式(I)所示的结构:
以下结合实施例和附图来对本发明作进一步的详细说明,其目的在于帮助更好的理解本发明的内容,但本发明的保护围不仅限于这些实施例。
实施例1:制备结构式如下的热活化延迟荧光材料
合成步骤如下所示:
首先,向250mL二口瓶中加入原料1(3.0g,5mmol)、咔唑(2.0g,12mmol)、醋酸钯(90mg,0.4mmol)和三叔丁基膦四氟硼酸盐(0.34g,1.2mmol)。然后,将二口瓶放到手套箱中,并在二口瓶中加入NaOt-Bu(1.16g,12mmol)。接着,在氩气氛围下,于二口瓶中打入100mL事先除水除氧的甲苯,在120℃反应48小时后获得反应液。冷却至室温后,将二口瓶中的反应液倒入300mL冰水中。随后,用二氯甲烷对反应液进行萃取,萃取三次后,合并每次萃取取得的有机相,并用柱层析法(二氯甲烷:正己烷,v:v,1:2)进行分离纯化,最终获得目标化合物1(淡蓝色粉末)2.1g,产率55%。MS(EI)m/z:770.01。
实施例2:制备结构式如下的热活化延迟荧光材料
合成步骤如下所示:
首先,向250mL二口瓶中加入原料1(3.0g,5mmol)、9,9-二甲基吖啶(2.5g,12mmol)、醋酸钯(90mg,0.4mmol)和三叔丁基膦四氟硼酸盐(0.34g,1.2mmol)。然后,将二口瓶放到手套箱中,并在二口瓶中加入NaOt-Bu(1.16g,12mmol)。接着,在氩气氛围下,于二口瓶中打入100mL事先除水除氧的甲苯,在120℃反应48小时后获得反应液。冷却至室温后,将二口瓶中的反应液倒入300mL冰水中。随后,用二氯甲烷对反应液进行萃取,萃取三次后,合并每次萃取取得的有机相,并用柱层析法(二氯甲烷:正己烷,v:v,2:3)进行分离纯化,最终获得目标化合物2(绿色粉末)2.0g,产率47%。MS(EI)m/z:854.10。
实施例3:制备结构式如下的热活化延迟荧光材料
合成步骤如下所示:
首先,向250mL二口瓶中加入原料1(3.0g,5mmol)、吩恶嗪(2.2g,12mmol)、醋酸钯(90mg,0.4mmol)和三叔丁基膦四氟硼酸盐(0.34g,1.2mmol)。然后,,将二口瓶放到手套箱中,并在二口瓶中加入NaOt-Bu(1.16g,12mmol)。接着,在氩气氛围下,于二口瓶中打入100mL事先除水除氧的甲苯,在120℃反应48小时后获得反应液。冷却至室温后,将二口瓶中的反应液倒入300mL冰水中。随后,用二氯甲烷对反应液进行萃取,萃取三次,合并每次萃取取得的有机相,并用柱层析法(二氯甲烷:正己烷,v:v,1:1)进行分离纯化,最终获得目标化合物3(红色粉末)1.8g,产率45%。MS(EI)m/z:801.98。
目标化合物1-3的物理特性:
目标化合物1-3的光致发光光谱峰值(photoluminescence peak,PL peak)最低单重态能级(S1)、最低三重态能级(T1)、单三重态能级差(ΔEST)、最高占据分子轨域(highest occupied molecular orbital,HOMO)的能级和最低未占分子轨域(lowestunoccupied molecular orbital,LUMO)的能级,如下表1所示:
表1
参考图1,图1是本发明实施例的热活化延迟荧光材料(化合物1-3)在甲苯溶液中的光致发光光谱,其中化合物1-3的光致发光光谱峰值(PL peak)如表1所述分别为460nm、530nm及612nm,亦即化合物1-3分别为本发明蓝光热活化延迟荧光材料、绿光热活化延迟荧光材料及红光热活化延迟荧光材料的代表实例。
有机发光二极管的制备:
参考图2,本发明有机发光二极管包括一导电玻璃阳极层1、一空穴注入层2、一空穴传输层3、一发光层4,一电子传输层5及一阴极层6。具体而言,导电玻璃阳极层1是藉由将玻璃基板镀上一层可导电的氧化铟锡(indium tin oxide,ITO)来形成的。空穴注入层2是由三氧化钼(MoO3)所组成。空穴传输层3是由4,4',4”-三(咔唑-9-基)三苯胺(4,4',4”-tris(carbazol-9-yl)triphenylamine,TCTA)所组成。发光层4是由二[2-((氧代)二苯基膦基)苯基]醚(bis[2-[(oxo)diphenylphosphino]phenyl]ether,DPEPO)及本发明热活化延迟荧光材料所组成。电子传输层5是由1,3,5-三[3-(3-吡啶基)苯基]苯(1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene,Tm3PyPB)。阴极层60由氟化锂及铝所组成。有机发光二极管可按本发明技术领域已知的方法完成,例如参考文献「Adv.Mater.2003,15,277」所公开的方法。具体方法为:在高真空条件下,在ITO导电玻璃上,依次蒸镀形成MoO3、TCTA、DPEPO+本发明热活化延迟荧光材料(化合物1-3)、Tm3PyPB、LiF及Al。
在此,使用本发明目标化合物1-3来制备有机发光二极管I-III。有机发光二极管I-III的结构从导电玻璃阳极层1至阴极层6的结构依次如下所示:
有机发光二极管I:ITO/MoO3(2nm)/TCTA(35nm)/DPEPO:化合物1(10%,20nm)/Tm3PyPB(40nm)/LiF(1nm)+Al(100nm)
有机发光二极管II:ITO/MoO3(2nm)/TCTA(35nm)/DPEPO:化合物2(10%20nm)/Tm3PyPB(40nm)/LiF(1nm)+Al(100nm)
有机发光二极管III:ITO/MoO3(2nm)/TCTA(35nm)/DPEPO:化合物3(10%20nm)/Tm3PyPB(40nm)/LiF(1nm)+Al(100nm)
有机发光二极管I-III的性能数据如下表2所示。有机发光二极管的电流、亮度及电压是由带有校正过的硅光电二极管的Keithley源测量系统(Keithley2400Sourcemeter、Keithley 2000Currentmeter)所测量的,有机发光二极管的电致发光光谱是由法国JY公司SPEX CCD3000光谱仪所测量的,所有测量均在室温大气中完成。
表2
本发明实施例的热活化延迟荧光材料,包括蓝光、绿光及红光热活化延迟荧光材料,皆具有低单三重态能级差,进而具有高反向系间窜越常数及高光致发光量子产率。再者,本发明实施例所提供的热活化延迟荧光材料制备方法具有高合成效率。最后,使用本发明实施例的热活化延迟荧光材料作为发光层的有机发光二极管具有高发光效率,进而具有长寿命,可应用于各种显示设备和电子装置中。
虽然本发明结合其具体实施例而被描述,应该理解的是,许多替代、修改及变化对于那些本领域的技术人员将是显而易见的。因此,其意在包含落入所附权利要求书的范围内的所有替代、修改及变化。
Claims (8)
8.一种有机发光二极管,其特征在于:所述有机发光二极管包括:一阳极;
一阴极;以及位于所述阳极与所述阴极之间的一发光层,其中所述发光层包括如权利要求1所述的热活化延迟荧光材料。
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