CN110684524A - 一种电致发光化合物、热激活延迟荧光材料及其应用 - Google Patents
一种电致发光化合物、热激活延迟荧光材料及其应用 Download PDFInfo
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- CN110684524A CN110684524A CN201911063213.8A CN201911063213A CN110684524A CN 110684524 A CN110684524 A CN 110684524A CN 201911063213 A CN201911063213 A CN 201911063213A CN 110684524 A CN110684524 A CN 110684524A
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Abstract
本发明提供一种电致发光化合物、热激活延迟荧光材料及其应用,所述电致发光化合物具有如式I所示结构,是一种含硼杂环的小分子化合物。所述电致发光化合物具有TADF特性,可作为热激活延迟荧光材料应用于OLED器件的发光层中,所述OLED器件包括阳极、阴极和位于阳极和阴极之间的至少一层有机薄膜层,所述有机薄膜层中的发光层中包括所述热激活延迟荧光材料。本发明提供的电致发光化合物通过分子结构的特殊设计有效降低了HOMO和LUMO间的重叠,使ΔEST降低到0.25eV以下,满足三线态能量向单线态逆向窜越,有效提高了两种载流子的传输能力、改善载流子平衡,从而显著提升了OLED器件的发光效率。
Description
技术领域
本发明属于有机电致发光材料技术领域,具体涉及一种电致发光化合物、热激活延迟荧光材料及其应用。
背景技术
有机电致发光器件(Organic Light Emitting Display,OLED)是一种新型的平板显示技术,与液晶显示器(Liquid Crystal Display,LCD)相比,OLED具有主动发光、响应速度快、能耗小、驱动电压低、轻薄、视角宽、发光颜色连续可调、成本低、生产工艺简单、发光效率高及可柔性显示等优点,得到了产业界和科学界的极大关注,已广泛应用于柔性显示、平板显示、固态照明和车载显示等行业。目前,OLED已经进入产业化阶段,高性能有机光电材料的开发依然是本领域的焦点课题。
研究表明,用于OLED的发光层材料根据其发光机制可分为以下四种:荧光材料、磷光材料、三线态-三线态湮灭(TTA)材料和热激活延迟荧光(TADF)材料。其中,荧光材料的单线激发态S1通过辐射跃迁回到基态S0,根据自旋统计,激子中单线态和三线态激子的比例为1:3,所以荧光材料最大内量子产率不大于25%;依据朗伯发光模式,光取出效率约为20%,因此基于荧光材料的OLED器件的外量子效率EQE一般不高于5%。磷光材料的三线激发态T1直接辐射衰减到基态S0,由于重原子效应,可以通过自旋偶合作用加强分子内部系间窜越,可以直接利用75%的三线态激子,从而实现在室温下S1和T1共同参与的发射,理论最大内量子产率可达100%;依据朗伯发光模式,光取出效率约为20%,故基于磷光材料的OLED器件的EQE可以达到20%;但是磷光材料多为Ir、Pt、Os、Re、Ru等重金属配合物,生产成本较高,不利于大规模生产;且在高电流密度下,磷光材料存在严重的效率滚降现象,导致磷光发光OLED器件的稳定性欠佳。TTA材料的两个三线态激子相互作用,复合生成一个更高能级的单线激发态分子和一个基态分子;但是两个三线态激子产生一个单线态激子,所以理论最大内量子产率只能达到62.5%;为了防止产生较大的效率滚降现象,在这个过程中三线态激子的浓度需要调控。
TADF材料中,当S1态和T1态的能级差较小、且T1态激子寿命较长时,在一定温度条件下,T1态激子可以逆向系间窜越(RISC),实现T1态转换到S1态的过程,再由S1态辐射衰减至基态S0。因此,TADF材料可同时利用75%的三线态激子和25%的单线态激子,理论最大内量子产率可达100%;更为重要的是,TADF材料主要为有机化合物,不需要稀有金属元素,生产成本低,并且可通过多种方法进行化学修饰,实现性能的进一步优化。
CN109134520A、CN109503508A、CN108530357A等公开了TADF材料及其应用,但目前已发现的TADF材料较少,且性能难以满足人们对高性能OLED器件的要求。
因此,开发更多种类、高性能的新型TADF材料,是本领域亟待解决的问题。
发明内容
为了开发更多种类、更高性能的TADF材料,本发明的目的之一在于提供一种电致发光化合物,所述电致发光化合物具有如式I所示结构:
式I中,R、R1、R2、R3各自独立地选自取代或未取代的C6~C40芳基、取代或未取代的C3~C40杂芳基、取代或未取代的C6~C30芳基氨基中的任意一种,且R、R1、R2、R3为供电子基团。
所述C6~C40可以是C7、C8、C10、C13、C15、C18、C20、C23、C25、C28、C30、C33、C35、C37或C39等。
所述C3~C40可以是C4、C5、C6、C8、C10、C13、C15、C18、C20、C23、C25、C28、C30、C33、C35、C37或C39等。
所述C6~C30可以是C7、C8、C9、C10、C13、C15、C18、C20、C23、C25、C27或C29等。
所述“供电子基团”意指能提高苯环上电子云密度的基团,示例性地包括但不限于咔唑基、芳胺基、吖啶基、吩噻嗪基或吩恶嗪基等。
当上述基团存在取代基时,所述取代基选自C1~C10直链或支链烷基、C1~C10烷氧基或C1~C10硫代烷氧基中的至少一种。
所述C1~C10可以是C1、C2、C3、C4、C5、C6、C7、C8、C9或C10。
式I中,L为C6~C30亚芳基或C3~C30亚杂芳基。
所述C6~C30可以是C7、C8、C9、C10、C13、C15、C18、C20、C23、C25、C27或C29等。
所述C3~C30可以是C4、C5、C6、C8、C10、C13、C15、C18、C20、C23、C25、C27或C29等。
式I中,n1为0~3的整数,例如0、1、2或3。
式I中,n2为0~4的整数,例如0、1、2、3或4。
式I中,n3为0~2的整数,例如0、1或2。
本发明的目的之二在于提供一种热激活延迟荧光材料,所述热激活延迟荧光材料包括上述电致发光化合物中的任意一种或至少两种组合。
本发明的目的之三在于提供一种显示面板,所述显示面板包括OLED器件,所述OLED器件包括阳极、阴极以及位于所述阳极和阴极之间的至少1层有机薄膜层,所述有机薄膜层包括发光层。
所述发光层包括如上所述的热激活延迟荧光材料,且所述热激活延迟荧光材料用作主体材料、客体材料或共同掺杂材料中的任意一种。
本发明的目的之四在于提供一种电子设备,所述电子设备包括如上所述的显示面板。
相对于现有技术,本发明具有以下有益效果:
(1)本发明提供的电致发光化合物是一种含硼杂环的小分子化合物,通过大位阻基团的接入避免了化合物的聚集,避免共轭平面的直接堆积形成π聚集或激基缔合物,从而提高了发光效率。
(2)基于本发明所述电致发光化合物的热激活延迟荧光材料具有TADF特性,分子中大刚性扭曲的结构有效降低了HOMO和LUMO之间的重叠,使三重态和单重态之间的能级差可以降低到0.25eV以下,甚至低至0.10eV以下,满足三线态能量向单线态逆向窜越,提高器件效率,荧光寿命大幅度提高并达到μs级别,具有明显的延迟荧光效应。
(3)本发明提供的电致发光化合物HOMO和LUMO之间的差值比较大,化合物的扭曲程度较大,通过取代基实现可见光内全波谱的发射,可作为红光、蓝光、绿光等的发光层材料应用于多种需求的发光层材料中。
(4)本发明所述电致发光化合物的母体结构(硼代萘并喹啉)为干性,热稳定性好,不易发生分解,玻璃态转化温度比较高、可达到100℃以上,在成膜过程中出现非晶态,使膜层的致密性较好、器件的稳定性较高。此外,所述电致发光化合物的母体结构分子量相对较小,蒸镀温度较低,材料的分解程度低,能够应用于蒸镀工艺中得到高性能的OLED器件。
(5)本发明提供的电致发光化合物本身具有双极性特性,作为OLED器件的发光层可以有效提高两种载流子的传输能力和改善载流子平衡,提高器件的发光效率,降低器件电压,使器件的外量子效率达到16.5~23.5%,电流效率达到19.0~61.3Cd/A,能够充分满足高性能OLED器件的应用需求。
附图说明
图1为本发明提供的OLED器件的结构示意图,其中101为阳极,102为阴极,103为发光层,104为第一有机薄膜层,105为第二有机薄膜层;
图2为本发明实施例1提供的电致发光化合物M1的HOMO轨道排布图;
图3为本发明实施例1提供的电致发光化合物M1的LUMO轨道排布图。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
本发明的目的之一在于提供一种电致发光化合物,所述电致发光化合物具有如式I所示结构:
式I中,R、R1、R2、R3各自独立地选自取代或未取代的C6~C40芳基、取代或未取代的C3~C40杂芳基、取代或未取代的C6~C30芳基氨基中的任意一种,且R、R1、R2、R3为供电子基团。
所述C6~C40可以是C7、C8、C10、C13、C15、C18、C20、C23、C25、C28、C30、C33、C35、C37或C39等。
所述C3~C40可以是C4、C5、C6、C8、C10、C13、C15、C18、C20、C23、C25、C28、C30、C33、C35、C37或C39等。
所述C6~C30可以是C7、C8、C9、C10、C13、C15、C18、C20、C23、C25、C27或C29等。
所述“供电子基团”意指能提高苯环上电子云密度的基团,示例性地包括但不限于咔唑基、芳胺基、吖啶基、吩噻嗪基或吩恶嗪基等。
当上述基团存在取代基时,所述取代基选自C1~C10直链或支链烷基、C1~C10烷氧基或C1~C10硫代烷氧基中的至少一种。
所述C1~C10可以是C1、C2、C3、C4、C5、C6、C7、C8、C9或C10。
式I中,L为C6~C30亚芳基或C3~C30亚杂芳基。
所述C6~C30可以是C7、C8、C9、C10、C13、C15、C18、C20、C23、C25、C27或C29等。
所述C3~C30可以是C4、C5、C6、C8、C10、C13、C15、C18、C20、C23、C25、C27或C29等。
式I中,n1为0~3的整数,例如0、1、2或3。
式I中,n2为0~4的整数,例如0、1、2、3或4。
式I中,n3为0~2的整数,例如0、1或2。
本发明提供的电致发光化合物以硼代萘并喹啉为核心并作为电子受体,连接基团R以及R1、R2、R3作为电子给体,通过大位阻基团的接入避免了化合物的聚集,避免共轭平面的直接堆积形成π聚集或激基缔合物,从而提高了发光效率。基于所述电致发光化合物的热激活延迟荧光材料具有TADF特性,可以利用传统荧光分子跃迁禁阻的三线态激子来发光,从而提高器件效率;其根本原因在于所述电致发光化合物的分子中具有大的刚性扭曲,降低了HOMO和LUMO之间的重叠,使三重态和单重态之间的能级差可以降低到0.25eV以下,满足三线态能量向单线态逆向窜越,提高器件效率;并通过取代基的特殊设计实现可见光内全波谱的发射。所述电致发光化合物本身具有双极性特性,作为OLED器件的发光层可以有效提高两种载流子的传输能力和改善载流子平衡,提高器件的荧光量子效率,降低器件电压。
在一个实施方式中,所述R、R1、R2、R3各自独立地选自如下基团的任意一种,或被取代基取代的如下基团的任意一种:
其中,虚线表示基团的连接位点。
Z1-Z7各自独立地选自O、S或N-RN1中的任意一种;所述N-RN1通过N原子与五元环连接。下文中涉及到相同描述时,具有相同的意义。
U1、U2各自独立地选自O、S、N-RN2或RC1-C-RC2中的任意一种;所述N-RN2通过N原子与六元环连接,所述RC1-C-RC2通过C原子与六元环连接。下文中涉及到相同描述时,具有相同的意义。
RN1、RN2、RC1、RC2选自氢、C1~C10(例如C2、C3、C4、C5、C6、C7、C8或C9)直链或支链烷基、C1~C10(例如C2、C3、C4、C5、C6、C7、C8或C9)烷氧基、C6~C20(例如C7、C9、C10、C12、C14、C15、C17或C19等)芳基、C3~C20(例如C4、C6、C8、C10、C12、C14、C16或C18等)杂芳基中的任意一种。
所述取代基选自C1~C10(例如C2、C3、C4、C5、C6、C7、C8或C9)直链或支链烷基、C1~C10(例如C2、C3、C4、C5、C6、C7、C8或C9)烷氧基或C1~C10(例如C2、C3、C4、C5、C6、C7、C8或C9)硫代烷氧基中的至少一种。
在一个实施方式中,所述电致发光化合物具有如式II所示结构:
式II中,R1、R2、R3各自独立地具有与上述式I中相同的限定范围。
式II中,L为C6~C30(例如C7、C8、C9、C10、C13、C15、C18、C20、C23、C25、C27或C29等)亚芳基或C3~C30(例如C4、C5、C6、C8、C10、C13、C15、C18、C20、C23、C25、C27或C29等)亚杂芳基。
式II中,n1为0~3的整数,例如0、1、2或3。
式II中,n2为0~4的整数,例如0、1、2、3或4。
式II中,n3为0~2的整数,例如0、1或2。
在一个实施方式中,所述电致发光化合物具有如式III所示结构:
式III中,U选自O、S、N-RU1或RU2-C-RU3中的任意一种;其中,RU1、RU2、RU3各自独立地选自氢、C1~C10(例如C2、C3、C4、C5、C6、C7、C8或C9)直链或支链烷基、C1~C10(例如C2、C3、C4、C5、C6、C7、C8或C9)烷氧基、C6~C20(例如C7、C9、C10、C12、C14、C15、C17或C19等)芳基、C3~C20(例如C4、C6、C8、C10、C12、C14、C16或C18等)杂芳基中的任意一种。
式III中,R1、R2、R3各自独立地具有与上述式I中相同的限定范围。
式III中,L为C6~C30(例如C7、C8、C9、C10、C13、C15、C18、C20、C23、C25、C27或C29等)亚芳基或C3~C30(例如C4、C5、C6、C8、C10、C13、C15、C18、C20、C23、C25、C27或C29等)亚杂芳基。
式III中,n1为0~3的整数,例如0、1、2或3。
式III中,n2为0~4的整数,例如0、1、2、3或4。
式III中,n3为0~2的整数,例如0、1或2。
在一个实施方式中,所述U选自O、S、N-RU1或中的任意一种,RU1为C6~C20(例如C7、C9、C10、C12、C14、C15、C17或C19等)芳基或C3~C20(例如C4、C6、C8、C10、C12、C14、C16或C18等)杂芳基。
在一个实施方式中,所述电致发光化合物具有如式IV所示结构:
式IV中,R1、R2、R3各自独立地具有与上述式I中相同的限定范围。
式IV中,L为C6~C30(例如C7、C8、C9、C10、C13、C15、C18、C20、C23、C25、C27或C29等)亚芳基或C3~C30(例如C4、C5、C6、C8、C10、C13、C15、C18、C20、C23、C25、C27或C29等)亚杂芳基。
式IV中,n1为0~3的整数,例如0、1、2或3。
式IV中,n2为0~4的整数,例如0、1、2、3或4。
式IV中,n3为0~2的整数,例如0、1或2。
在一个实施方式中,所述L选自C6~C24(例如C7、C8、C9、C10、C13、C15、C18、C20、C22或C23等)亚芳基、C3~C20(例如C4、C6、C8、C10、C12、C14、C16或C18等)含N亚杂芳基或C3~C20(例如C4、C6、C8、C10、C12、C14、C16或C18等)含O亚杂芳基。
在一个实施方式中,所述L选自如下基团的任意一种:
其中,虚线表示基团的连接位点。
在一个实施方式中,所述R1、R2、R3各自独立地选自如下基团的任意一种,或被取代基取代的如下基团的任意一种:
其中,虚线表示基团的连接位点。
所述取代基选自C1~C10(例如C2、C3、C4、C5、C6、C7、C8或C9)直链或支链烷基、C1~C10(例如C2、C3、C4、C5、C6、C7、C8或C9)烷氧基或C1~C10(例如C2、C3、C4、C5、C6、C7、C8或C9)硫代烷氧基中的至少一种。
在一个实施方式中,所述电致发光化合物选自如下化合物M1~M50中的任意一种:
本发明的目的之二在于提供一种热激活延迟荧光材料,所述热激活延迟荧光材料包括上述电致发光化合物中的任意一种或至少两种组合。
在一个实施方式中,所述热激活延迟荧光材料的最低单重态S1与最低三重态T1态之间的能极差ΔEST=ES1-ET1≤0.30eV,例如能级差ΔEST为0.29eV、0.27eV、0.25eV、0.24eV、0.23eV、0.22eV、0.21eV、0.20eV、0.19eV、0.18eV、0.16eV、0.14eV、0.13eV、0.12eV、0.11eV、0.10eV、0.09eV、0.08eV、0.07eV、0.06eV、0.05eV、0.04eV、0.03eV、0.02eV或0.01eV等。
本发明的目的之三在于提供一种显示面板,所述显示面板包括OLED器件,所述OLED器件包括阳极、阴极以及位于所述阳极和阴极之间的至少1层有机薄膜层,所述有机薄膜层包括发光层。
所述发光层包括如上所述的热激活延迟荧光材料,且所述热激活延迟荧光材料用作主体材料、客体材料或共同掺杂材料中的任意一种。
在一个实施方式中,所述有机薄膜层还包括空穴传输层、空穴注入层、电子阻挡层、空穴阻挡层、电子传输层、电子注入层中的任意一种或至少两种的组合。
本发明所述OLED器件中,阳极材料可以为金属、金属氧化物或导电性聚合物;其中,所述金属包括铜、金、银、铁、铬、镍、锰、钯、铂等及它们的合金,所述金属氧化物包括氧化铟锡(ITO)、氧化铟锌(IZO)、氧化锌、氧化铟镓锌(IGZO)等,所述导电性聚合物包括聚苯胺、聚吡咯、聚(3-甲基噻吩)等。除以上有助于空穴注入材料及其组合,还包括已知的适合做阳极的材料。
所述OLED器件中,阴极材料可以为金属或多层金属材料;其中,所述金属包括铝、镁、银、铟、锡、钛等及它们的合金,所述多层金属材料包括LiF/Al、LiO2/Al、BaF2/Al等。除以上有助于电子注入的材料及其组合,还包括已知的适合做阴极的材料。
所述OLED器件中,有机薄膜层包括至少一层发光层(EML)和设置于发光层两侧的空穴传输层(HTL)、空穴注入层(HIL)、电子阻挡层(EBL)、空穴阻挡层(HBL)、电子传输层(ETL)、电子注入层(EIL)中的任意一种或至少两种的组合,其中空穴/电子注入及传输层可以为咔唑类化合物、芳胺类化合物、苯并咪唑类化合物及金属化合物等。
所述OLED器件的示意图如图1所示,包括阳极101和阴极102,设置于所述阳极101和阴极102之间的发光层103,在发光层103的两侧设置有第一有机薄膜层104和第二有机薄膜层105,所述第一有机薄膜层104和第二有机薄膜层105各自独立地为空穴传输层(HTL)、空穴注入层(HIL)、电子阻挡层(EBL)、空穴阻挡层(HBL)、电子传输层(ETL)、电子注入层(EIL)中的任意1种或至少2种的组合。
所述OLED器件可以通过以下方法制备:在透明或不透明的光滑的基板上形成阳极,在阳极上形成有机薄层,在有机薄层上形成阴极。其中,形成有机薄层可采用如蒸镀、溅射、旋涂、浸渍、离子镀等已知的成膜方法。
本发明的目的之四在于提供一种电子设备,所述电子设备包括如上所述的显示面板。
本发明提供的具有如式I所示结构的化合物示例性的通过如下合成路线制备得到:
其中,R、R1、R2、R3、L、n1、n2、n3各自独立地具有与上述式I中相同的限定范围,TMS为三甲基硅烷基。
实施例1
本实施例提供一种电致发光化合物,结构如下:
制备方法包括以下步骤:
在微波小瓶中依次加入A(0.5mmol)和B(0.5mmol),用乙醇(6mL)溶解,然后加入四丁基乙酸盐(Bu4NOAc,1mmol)和钯催化剂Pd En Cat(63mg,5mol%);反应用微波装置在120℃下照射10分钟。在微波腔中冷却到室温后,将反应混合物在SCXII柱上纯化,使用二氯甲烷(DCM,10mL)作为洗脱液并蒸发至干,得到中间体C。
1H-NMR(400MHz,CDCl3):δ8.91(s,1H),8.12(d,J=4.0Hz,2H),7.84(s,1H),7.66(s,1H),7.53(s,1H),7.44(s,1H),7.32(d,J=20.0Hz,2H)。
13C-NMR(100MHz,CDCl3):δ148.63(s),148.12(s),147.36(s),143.88(s),134.18(s),132.82(s),131.31(s),130.07(s),129.65(s),127.95(s),127.51(s),126.95(s),120.99(s),119.91(s),118.80(s)。
在250mL三口瓶中加入中间体C 7.22g(20mmol),用四氢呋喃(THF,80mL)溶解,氮气置换三次;降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加正丁基锂20mL(n-BuLi,50mmol),滴加完全后搅拌30min;再缓慢滴加三甲基氯硅烷4.35g(TMS-Cl,40mmol),升温至0℃反应4h。结束后加入冰水淬灭;加入DCM萃取,收集有机相旋蒸,得到淡黄色油状物;用甲苯和乙醇的混合溶剂析晶得到淡黄色固体;在200mL闷罐中依次加入淡黄色固体、70mL无水甲苯溶液和三溴化硼0.76mL(8mmol),120℃搅拌12h。反应结束后H2O(100mL)淬灭;用DCM萃取反应液,收集有机相,干燥过滤,旋蒸去除溶剂;使用二氯甲烷和乙醇的混合溶剂析晶得到中间体D。
1H-NMR(400MHz,CDCl3):δ8.87(s,1H),8.56(s,1H),8.17(s,1H),7.94(s,2H),7.77(s,1H),7.59(s,1H),7.50(s,1H),7.42(s,1H)。
13C-NMR(100MHz,CDCl3):δ152.83(s),152.33(s),142.66(s),137.45(s),133.10(s),132.00(s),130.42(s),129.95(s),129.74(s),128.11(s),127.38(s),125.83(s),111.38(s)。
将化合物E 9-(4-溴苯基)咔唑6.16g(19.13mmol)加入反应瓶中,用乙醚(50mL)溶解,氮气置换三次;降温至-78℃,待温度达到后控制温度在-65℃以下缓慢滴加n-BuLi8.04mL(2.5M,20.09mmol),滴加完全后搅拌30min;用甲苯(Tol,60mL)溶解中间体D 4.4g(15mmol),然后缓慢滴加至反应液中,滴加完成后自然升至室温反应6h。反应结束后加入冰水(100mL)淬灭反应,再加入DCM萃取,最后用饱和食盐水萃取一次。收集有机相旋蒸,得到淡黄色油状物。以柱层析方法(流动相为正己烷与二氯甲烷体积比3:1的混合溶剂)纯化产物,得到目标产物M1。
1H-NMR(400MHz,CDCl3):δ8.87(s,1H),8.63(s,1H),8.55(s,1H),8.18(d,J=8.0Hz,2H),7.94(s,2H),7.89(s,2H),7.75(d,J=16.0Hz,3H),7.59(s,1H),7.51(d,J=8.0Hz,2H),7.41(d,J=8.0Hz,2H),7.16(dd,J=22.0,14.0Hz,4H)。
13C-NMR(100MHz,CDCl3):δ154.08(s),151.64(s),149.09(s),145.60(s),139.35(s),135.38(s),135.09(s),134.82(s),131.99(s),130.97(s),129.86–129.49(m),127.77(d,J=9.8Hz),126.91(s),125.67(s),125.32(s),121.91(s),121.15(d,J=2.7Hz),114.95(s),113.74(s)。
实施例2
本实施例提供一种电致发光化合物,结构如下:
1H-NMR(400MHz,CDCl3):δ8.87(s,1H),8.63(s,1H),8.55(s,1H),8.18(d,J=8.0Hz,2H),7.94(s,4H),7.89(s,4H),7.75(d,J=16.0Hz,3H),7.59(s,1H),7.51(d,J=8.0Hz,2H),7.41(d,J=8.0Hz,2H),7.16(dd,J=22.0,14.0Hz,4H)。
13C-NMR(100MHz,CDCl3):δ154.08(s),151.67(d,J=7.0Hz),146.93(s),145.60(s),139.35(s),135.09(s),134.01(s),131.99(s),130.97(s),129.86-129.49(m),129.27(s),127.82(s),127.11(s),126.91(s),125.32(s),124.67(s),122.99(s),113.74(s)。
实施例3
本实施例提供一种电致发光化合物,结构如下:
1H-NMR(400MHz,CDCl3):δ8.87(s,1H),8.62(s,1H),8.17(s,1H),7.94(s,1H),7.74(d,J=24.0Hz,3H),7.55(d,J=36.0Hz,2H),7.42(s,1H),7.18(dd,J=8.0,4.0Hz,8H),6.94(s,2H),1.69(s,6H)。
13C-NMR(100MHz,CDCl3):δ154.08(s),152.78(s),151.64(s),145.60(s),142.44(s),139.35(s),135.09(s),134.24(s),133.37(s),131.99(s),130.97(s),29.86-129.49(m),128.95(s),127.82(s),127.11(s),126.83(d,J=15.7Hz),125.32(s),122.86(s),120.00(s),113.74(s),35.71(s),29.68(s)。
实施例4
本实施例提供一种电致发光化合物,结构如下:
1H-NMR(400MHz,CDCl3):δ8.87(s,1H),8.64(s,1H),8.17(s,1H),7.94(s,1H),7.74(d,J=24.0Hz,3H),7.55(d,J=36.0Hz,2H),7.42(s,1H),7.27-7.00(m,6H),6.98(s,2H),6.93(s,2H)。
13C-NMR(100MHz,CDCl3):δ154.08(s),152.78(s),151.64(s),146.79(s),145.60(s),139.35(s),135.09(s),134.24(s),132.27(s),131.99(s),130.97(s),129.86-129.49(m),127.82(s),127.11(s),126.91(s),125.32(s),123.59(d,J=16.4Hz),119.00(s),116.41(s),113.74(s)。
实施例5
本实施例提供一种电致发光化合物,结构如下:
制备方法与实施例1中制备方法的区别在于,将步骤(3)中的化合物E用等摩尔量的化合物E5替换,其它制备条件不变,得到目标产物M5。
1H-NMR(400MHz,CDCl3):δ8.87(s,1H),8.64(s,1H),8.17(s,1H),7.94(s,1H),7.74(d,J=24.0Hz,3H),7.55(d,J=36.0Hz,2H),7.42(s,1H),7.25-7.06(m,8H),6.97(s,2H).
13C-NMR(100MHz,CDCl3):δ154.08(s),152.78(s),151.64(s),145.60(s),141.45(s),139.35(s),135.09(s),134.24(s),131.99(s),130.97(s),129.86-129.49(m),127.82(s),127.22-127.01(m),126.91(s),126.62(s),125.32(s),124.39(s),122.70(s),115.74(s),113.74(s).
实施例6
本实施例提供一种电致发光化合物,结构如下:
1H-NMR(400MHz,CDCl3):δ9.96(s,1H),8.87(s,1H),8.59(d,J=30.8Hz,2H),8.18(d,J=8.0Hz,2H),7.94(s,1H),7.77(s,3H),7.71-7.29(m,3H),7.41(d,J=8.0Hz,2H),7.41(d,J=8.0Hz,2H),7.16(dd,J=22.0,14.0Hz,2H).
13C-NMR(100MHz,CDCl3):δ154.08(s),151.64(s),146.81(s),145.60(s),139.95(s),137.03(s),135.23(s),134.62(s),134.27(s),132.22(s),131.39(s),129.98(s),129.61(d,J=2.1Hz),127.35(d,J=18.4Hz),126.10(s),125.05(s),122.16(s),120.90(s),116.82(s),113.74(s).
应用例1
本应用例提供一种OLED器件,所述OLED器件依次包括:基板、ITO阳极、空穴注入层、空穴传输层、发光层、第一电子传输层、第二电子传输层、阴极(镁银电极,镁银质量比为9:1)和盖帽层(CPL),其中ITO阳极的厚度是15nm,空穴注入层的厚度是10nm、空穴传输层的厚度是110nm、发光层的厚度是30nm、第一电子传输层的厚度是30nm、第二电子传输层的厚度是5nm、镁银电极的厚度是15nm、盖帽层(CPL)的厚度是100nm。
OLED器件的制备步骤如下:
(1)将玻璃基板切成50mm×50mm×0.7mm的大小,分别在异丙醇和去离子水中超声处理30分钟,然后臭氧中清洗10分钟;将所得的具有ITO阳极的玻璃基板安装到真空沉积设备上;
(2)在真空度为2×10-6Pa下,在ITO阳极层上真空蒸镀上空穴注入层材料HAT-CN,厚度为10nm;
(3)在空穴注入层上真空蒸镀TAPC作为空穴传输层,厚度为110nm;
(4)在空穴传输层上共沉积发光层,其中,用本发明实施例1提供的电致发光化合物M1作为发光层的掺杂材料,3,3'-二(N-咔唑基)-1,1'-联苯(mCBP)作为发光层的主体材料,M1和mCBP的质量比为1:9,厚度为30nm;
(5)在发光层上真空蒸镀TPBi作为第一电子传输层,厚度为30nm;
(6)在第一电子传输层上真空蒸镀Alq3作为第二电子传输层,厚度为5nm;
(7)在第二电子传输层上真空蒸镀镁银电极作为阴极,厚度为15nm;
(8)在阴极上真空蒸镀CBP作为阴极覆盖层(盖帽层),厚度为100nm。
应用例2
本应用例与应用例1的区别在于,将步骤(4)中的M1用等量的M2替换。
应用例3
本应用例与应用例1的区别在于,将步骤(4)中的M1用等量的M3替换。
应用例4
本应用例与应用例1的区别在于,将步骤(4)中的M1用等量的M4替换。
应用例5
本应用例与应用例1的区别在于,将步骤(4)中的M1用等量的M5替换。
应用例6
本应用例与应用例1的区别在于,将步骤(4)中的M1用等量的M11替换。
对比例1
对比例2
对比例3
性能测试:
(1)化合物的模拟计算:
电致发光化合物的单线态和三线态的能级差可以通过Guassian 09软件(Guassian Inc.)完成,能级差ΔEST具体的模拟方法可参照文献J.Chem.Theory Comput.,2013,DOI:10.1021/ct400415r,分子结构优化和激发均可用TD-DFT方法“B3LYP”和基组“6-31g(d)”完成;按照上述方法模拟本发明提供的电致发光化合物M1、M2、M3、M4、M5、M11以及BczVBi,结果如表1所示。
(2)化合物的轨道排布模拟:
按照现有技术中的方法模拟本发明提供的电致发光化合物M1的轨道排布图,例如参考Furche F,Ahlrichs R.Adiabatic time-dependent density functional methodsfor excited state properties[J].Journal of Chemical Physics,2002,117(16):7433。其中M1的HOMO轨道排布图如图2所示,M1的LUMO轨道排布图如图3所示,对比图2和图3可知,M1的HOMO和LUMO分别排布在不同的区域,实现了完全的分离,有助于减小隙间能差△EST,从而提高逆隙间窜越能力。
表1
从表1的数据可知,本发明提供的电致发光化合物通过分子结构的特殊设计,其△EST均降低到0.25eV以下,甚至低于0.10eV,实现了较小的单线态和三线态能级差,利于反向隙间窜越;荧光寿命大幅度提高,可以达到μs级别,甚至达到14.0μs,具有明显的延迟荧光效应。相比于对比例中的BczVBi,更适宜用作OLED器件的发光层材料。
(3)OLED器件的性能评价:
用Keithley 2365A数字纳伏表测试OLED器件在不同电压下的电流,然后用电流除以发光面积得到OLED器件的在不同电压下的电流密度;用Konicaminolta CS-2000分光辐射亮度计测试OLED器件在不同电压下的亮度和辐射能流密度;根据OLED器件在不同电压下的电流密度和亮度,得到在相同电流密度下(10mA/cm2)的电流效率(Cd/A)和外量子效率(%)。按照上述方法测试应用例1~6、对比例1~3中提供的OLED器件的启亮电压(Vturn-on)、电流效率(CE)、外量子效率(EQE)、功率效率(hp)和色度坐标CIE(x,y),结果如表2所示。
表2
从表2的数据可得,与对比例1中使用现有发光层掺杂材料BczVBi的OLED器件相比,基于本发明实施例1~6提供的电致发光化合物为发光层材料制备的OLED器件具有更低的启亮电压,更高的电流效率、功率效率和外量子效率,OLED器件的电流效率达到19.0~61.3Cd/A,功率效率可达到19.4~58.4lm/W,外量子效率高于16.59%、甚至达到23.4%。本发明提供的电致发光化合物通过分子结构的特殊设计获得了较高的三线态能量以及较小的能级差△EST,作为OLED器件的发光层材料,可以效果提高器件的效率,降低启亮电压。
本发明提供的电致发光化合物通过取代基的设计可以实现可见光内全波谱的发射,根据表2中色度坐标CIE(x,y)的数据可知,M1、M5可作为OLED器件的蓝光发光层材料,M2可作为绿光发光层材料,M4可作为红光发光层材料,M3、M11可作为黄光发光层材料。
本发明提供的电致发光化合物以硼代萘并喹啉为核心并作为电子受体,连接R、R1、R2、R3为供电子基团,使其具有TADF特性,可以利用传统荧光分子跃迁禁阻的三线态激子来发光,从而提高器件效率;此外,大位阻基团的接入避免了化合物的聚集,避免共轭平面的直接堆积形成π聚集或激基缔合物,同样有助于提升器件的发光效率。如果不使用本发明所述的硼代萘并喹啉的核心结构(对比化合物1和对比化合物2),则其作为发光层掺杂材料的OLED器件启亮电压升高、发光效率降低,难以满足高性能发光器件的性能需求。
申请人声明,本发明通过上述实施例来说明本发明的电致发光化合物、热激活延迟荧光材料及其应用,但本发明并不局限于上述工艺步骤,即不意味着本发明必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明所选用原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (15)
7.根据权利要求1~6任一项所述的电致发光化合物,其特征在于,所述L选自C6~C24亚芳基、C3~C20含N亚杂芳基或C3~C20含O亚杂芳基。
9.根据权利要求1所述的电致发光化合物,其特征在于,所述R1、R2、R3各自独立地选自如下基团的任意一种,或被取代基取代的如下基团的任意一种:
其中,虚线表示基团的连接位点;
所述取代基选自C1~C10直链或支链烷基、C1~C10烷氧基或C1~C10硫代烷氧基中的至少一种。
11.一种热激活延迟荧光材料,其特征在于,所述热激活延迟荧光材料包括权利要求1~10任一项所述的电致发光化合物中的任意一种或至少两种组合。
12.根据权利要求11所述的热激活延迟荧光材料,其特征在于,所述热激活延迟荧光材料的最低单重态S1与最低三重态T1态之间的能极差ΔEST=ES1-ET1≤0.30eV。
13.一种显示面板,其特征在于,所述显示面板包括OLED器件,所述OLED器件包括阳极、阴极以及位于所述阳极和阴极之间的至少1层有机薄膜层,所述有机薄膜层包括发光层;
所述发光层包括如权利要求11或12所述的热激活延迟荧光材料,且所述热激活延迟荧光材料用作主体材料、客体材料或共同掺杂材料中的任意一种。
14.根据权利要求13所述的显示面板,其特征在于,所述有机薄膜层还包括空穴传输层、空穴注入层、电子阻挡层、空穴阻挡层、电子传输层、电子注入层中的任意一种或至少两种的组合。
15.一种电子设备,其特征在于,所述电子设备包括如权利要求13或14所述的显示面板。
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