CN116063267A - 一种螺环类化合物及应用 - Google Patents
一种螺环类化合物及应用 Download PDFInfo
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- CN116063267A CN116063267A CN202211194345.6A CN202211194345A CN116063267A CN 116063267 A CN116063267 A CN 116063267A CN 202211194345 A CN202211194345 A CN 202211194345A CN 116063267 A CN116063267 A CN 116063267A
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004001 molecular interaction Effects 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
本发明涉及有机电致发光材料领域,特别是涉及一种螺环类化合物及应用。所述螺环类化合物的化学结构为
Description
技术领域
本发明涉及有机电致发光材料领域,特别是涉及一种螺环类化合物及应用。
背景技术
有机发光二极管(Organic Light-Emitting Diodes,OLEDs)是一类自发光的电子元器件,最早由美籍华裔科学家邓青云(C.W.Tang)报道(Appl.Phys.Lett.51,913(1987))。OLED显示器具有可视角宽,高对比度,响应速度快,驱动电压低等优点,被广泛应用于各类电子产品中。由于OLED器件是在正向偏压下,依靠载流子在各有机层之间的传导与复合而发光,因此开发性能优良的有机材料是OLED领域的研究重点。
目前,一种被广泛应用的OLED器件结构如下所述:阳极/空穴注入层(HIL)/空穴传输层(HTL)/发光层(EML,发光主体材料:发光客体材料)/电子传输层(ETL)/电子注入层(EIL)/阴极。在发光层中,引入发光主体材料,有利于降低浓度淬灭效应,提升OLED器件的发光效率。其他功能层(例如HIL,HTL,ETL,EIL等)的引入,能够降低载流子的注入势垒,提高载流子迁移速率,有利于OLED器件启亮电压以及功耗的降低。
近年来,随着OLED显示器在消费电子领域的使用占比逐年增加,产业界对于OLED显示器提出了更高的要求,即,以低功率驱动的同时,发光效率和寿命不低于其他常规显示器。在OLED有机材料方面,应当具有良好的载流子(空穴或电子)传输速率和合适的前线轨道能级,保证载流子在各层之间有效的注入和传输。此外,有研究表明,有机薄膜的相态变化是影响OLED器件寿命的重要因素。例如,对于部分OLED器件,其工作过程中产生的焦耳热,会引起薄膜出现结晶或针孔等缺陷,导致器件的加速老化。因此,成膜性和热稳定性也是有机材料开发中需要重点关注的。目前,现有的材料性能仍然有很大的进步空间。故本发明提供一系列基于螺环的化合物,并应用于OLED器件中,表现出优异的器件性能。
发明内容
鉴于以上所述现有技术的缺点,本发明的目的在于提供一种螺环类化合物及其在有机电致发光器件中的应用,用于解决现有技术中的问题。
为实现上述目的及其他相关目的,本发明一方面提供一种螺环类化合物,所述螺环类化合物的化学结构如式(1)所示:
式(1)中,A选自O、S或NR0;其中,R0选自取代或未取代的C1~C12的烷基、取代或未取代的C3~C12的环烷基、取代或未取代的C6~C30的芳基、或取代或未取代的C2~30的杂芳基;
所述环G1、G2,相同或不同地,各自独立地选自取代或未取代的C6~C18的芳香族环,或取代或未取代的C3~C18的杂芳香族环;
所述环G3、G4,相同或不同地,各自独立地选自式(2)~式(4)所示的基团,或苯环,且不同时为苯环;
在式(2)~式(4)中,Z彼此相同或不同,各自独立地选自CRARB、NRC、O或S;其中,任意相邻的两个*碳表示与式(1)上五元环的共用连接位点;
所述RA、RB相同或不同地,各自独立地选自氢、氘、氘代或未氘代的甲基;所述RC选自取代或未取代的C1~C8的烷基、取代或未取代的C1~C8的杂烷基、取代或未取代的C3~C12的环烷基、取代或未取代的C3~C12的杂环烷基、取代或未取代的C6~C12的芳基,取代或未取代的C2~C12的杂芳基;
所述式(1)满足条件:所述G3和G4至少有一个选自式(2)~式(4)中的一个;
所述G3和G4均满足条件:当杂原子NRC、S或O的个数多于1个时,任意两个杂原子NRc、S或O之间均间隔至少一个CRARB;
所述R1、R2、R3、R4分别独立的选自氘、氟、氯、溴、氰基、异腈基、三氟甲基、硝基、取代或未取代的C1~C30的烷基、取代或未取代C3~C30的环烷基、取代或未取代的C1~C30的烷氧基、取代或未取代的C1~C30的烷硫基、取代或未取代的C6~C40的芳基、取代或未取代的C2~C40的杂芳基、取代或未取代的C1~C40的酮基、取代或未取代的C2~C40的烷氧基羰基、取代或未取代的C6~C40的芳氧基羰基、或式(5)所示的基团;
m、n、p、q彼此相同或不同,各自独立地选自0至10之间的整数;当m、n、p、q任意一个大于1时,各个R1、R2、R3、R4彼此相同或不同;
式(5)中,L1和L3各自独立地选自单键、取代或未取代的C6~C40的亚芳基、取代或未取代的C2~C40的亚杂芳基;L2选自氮原子、取代或未取代的C6~C40的亚芳基、取代或未取代的C2~C40的亚杂芳基;Ar选自取代或未取代的C6~C40的芳基、取代或未取代的C2~C40的杂芳基;r选自1~5,且为整数;且当r≥2时,各个L3、Ar基团之间彼此相同或不同;*为连接位点。
本发明另一方面提供一种有机层,包括前述的螺环类化合物。
本发明另一方面提供如本发明前述的螺环类化合物、和/或前述的有机层在有机电致发光器件中的应用。
本发明另一方面提供一种有机电致发光器件,包括第一电极、第二电极和有机层,其中所述有机层为空穴注入层、空穴传输层、发光层、电子注入层或电子传输层中至少一层,且所述有机层包括前述的螺环类化合物。
本发明另一方面提供一种显示或照明装置,包括如本发明前述的有机电致发光器件。
与现有技术相比,本发明的有益效果为:
在螺环化合物的适当位置并入环烷基或杂环烷基,一方面能够对这些位点起到官能团保护的功效,有利于提高分子的稳定性;另一方面,能够减少分子间的相互作用,有利于形成稳定的无定形的薄膜,从而提高OLED器件的寿命。此外,在这类分子片段的不同位置连接不同的取代基团,可大幅度调节分子的前线轨道能级,从而适用于红,绿,蓝等多种色光的OLED器件的各功能层中。
附图说明
图1是实施例中有机电致发光器件的一种结构示意图。
图2是实施例中有机电致发光器件的另一种结构示意图。
图中:
101 基底
102 第一电极
103 空穴注入层
104 第一层空穴传输层
105 第二层空穴传输层
106 发光层
107 空穴阻挡层
108 电子传输层
109 第二电极
110 覆盖层
具体实施方式
以下,详细说明具体公开的螺环类化合物及其在有机电致发光器件中的应用的实施方式。本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用,本说明书中的各项细节也可以基于不同观点与应用,在没有背离本发明的精神下进行各种修饰或改变。
在进一步描述本发明具体实施方式之前,应理解,本发明的保护范围不局限于下述特定的具体实施方案;还应当理解,本发明实施例中使用的术语是为了描述特定的具体实施方案,而不是为了限制本发明的保护范围;在本发明说明书和权利要求书中,除非文中另外明确指出,单数形式“一个”、“一”和“这个”包括复数形式。
当实施例给出数值范围时,应理解,除非本发明另有说明,每个数值范围的两个端点以及两个端点之间任何一个数值均可选用。除非另外定义,本发明中使用的所有技术和科学术语与本技术领域技术人员通常理解的意义相同。除实施例中使用的具体方法、设备、材料外,根据本技术领域的技术人员对现有技术的掌握及本发明的记载,还可以使用与本发明实施例中所述的方法、设备、材料相似或等同的现有技术的任何方法、设备和材料来实现本发明。
本发明发明人经过大量探索研究,目的在于提供一类基于螺环的有机化合物。基于芴的螺环结构,本身能够提供良好的分子热稳定性和载流子传输性质。在分子的适当位置并入环烷基或杂环烷基,不仅能够起到官能团保护的效果,有利于提高分子的稳定性;还能够更进一步地减小分子间相互作用,更容易获得高玻璃化转变温度,无定形的有机分子,从而有利于OLED器件寿命的提升。
此外,本发明提供的螺环片段,其自身具有适中的前线轨道能级,通过引入不同的取代基团,可实现能级的较大范围的调控,从而获得性能优良的各类功能层材料。例如,当连接给电子性的三芳胺基团,所得分子可作为空穴传输材料;而连接缺电子性的取代的均三嗪基团或喹喔啉基团,根据缺电子基团上的取代基的不同,所得分子可作为发光主体材料或电子传输材料。在此基础上,完成了本申请。
本发明第一方面提供一种螺环类化合物,所述螺环类化合物的化学结构如式(1)所示:
为了后面描述方便,将式(1)结构中的五元环和六元环分别标号如下:
在一些实施例中,所述螺环类化合物的化学结构如式(6)~(8)所示:
本申请的式(1)、式(6)~式(8)中,A选自O、S或NR0;其中,R0选自取代或未取代的C1~C12的烷基、取代或未取代的C3~C12的环烷基、或取代或未取代的C6~C30的芳基、取代或未取代的C2~30的杂芳基;
在一些实施例中,所述R0选自如下基团:
所述任意基团中,任意一个且仅有一个芳香环上的碳是键合位点,或任意一个氢原子均可以被氘、氟、氯、溴、氰基、硝基、三氟甲基、甲氧基、乙氧基、甲硫基、乙硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、萘基、吡啶基、吡嗪基、嘧啶基、三嗪基、喹啉基、异喹啉基、喹喔啉基中的一个所取代。
本申请的式(1)、式(6)~式(8)中,所述环G1、G2,相同或不同地,各自独立地选自取代或未取代的C6~C18的芳香族环,取代或未取代的C3~C18的杂芳香族环。
其中,Q独立地选自N、CH、CR5或C*a,并且满足,有且仅有两个相邻的Q为C*a;C*a表示与式(1)上六元环的共用连接位点。这里共用连接位点具体是指,G1环中,相邻的两个C*a对应的就是式(1)中六元环上3位碳、4位碳。G2环中,相邻的两个C*a对应的就是式(1)中六元环上1位碳、2位碳。
R5独立地选自氘、氟、氯、溴、氰基、硝基、三氟甲基、C1~C12的烷基、C3~C12的环烷基、C1~C12的烷氧基、C1~C12的烷硫基、C6~C30的芳基、或C2~C30的杂芳基等。
本申请的一些具体实施例中,所述环G1或G2自独立地选自如下基团:
所述任意基团中,任意两个且仅有两个相邻的碳原子是与式(1)上六元环的共用连接位点;这里共用连接位点具体是指,G1环中,相邻的两个碳原子对应的就是式(1)中六元环上3位碳、4位碳。G2环中,相邻的两个碳原子对应的就是式(1)中六元环上1位碳、2位碳。或任意一个氢原子均可以被氘、氟、氯、溴、氰基、硝基、三氟甲基、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、萘基、吡啶基、吡嗪基、嘧啶基、三嗪基、喹啉基、异喹啉基、喹喔啉基中的一个所取代。
本申请的式(1)中,所述环G3、G4,相同或不同地,各自独立地选自式(2)~式(4)所示的基团,或苯环,且不同时为苯环;
在式(2)~式(4)中,Z彼此相同或不同,各自独立地选自CRARB、NRC、O或S;其中,任意相邻的两个*碳表示与式(1)上苯环的共用连接位点;这里共用连接位点具体是指G3环中,相邻的两个*碳对应的就是式(1)中五元环上5位碳、6位碳。G4环中,相邻的两个碳原子对应的就是式(1)中五元环上7位碳、8位碳。
具体的,所述RA、RB相同或不同地,各自独立地选自氢、氘、氘代或未氘代的甲基;所述RC选自取代或未取代的C1~C8的烷基、取代或未取代的C1~C8的杂烷基、取代或未取代的C3~C12的环烷基、取代或未取代的C3~C12的杂环烷基、取代或未取代的C6~C12的芳基,取代或未取代的C2~C12的杂芳基。所述式(1)满足条件:所述G3和G4至少有一个选自式(2)~式(4)中的一个。所述G3和G4均满足条件:当杂原子NRC、S或O的个数多于1个时,任意两个杂原子NRC、S或O之间均间隔至少一个CRARB。
本申请的式(1)中,所述G5、G6相同或不同地,各自独立地选自式(9)~式(11)所示的基团:
其中,Z的选择同式(2)~式(4);式(9),(10)或式(11)中的*表示连接位点,分别连接式(6)(7)或式(8)中任意一个的苯环上任意两个相邻的未被取代的碳原子。
本申请的一些实施例中,所述环G5或G6自独立地选自如下基团:
其中,R0的选择同式式(1)。*表示连接位点,分别连接式(6)(7)或式(8)中苯环上任意两个相邻的未被取代的碳原子。
具体的,所述R0选自如下基团:
所述任意基团中,任意一个且仅有一个芳香环上的碳是键合位点,或任意一个氢原子均可以被氘、氟、氯、溴、氰基、硝基、三氟甲基、甲氧基、乙氧基、甲硫基、乙硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、萘基、吡啶基、吡嗪基、嘧啶基、三嗪基、喹啉基、异喹啉基、喹喔啉基中的一个所取代。
本申请的式(1)、式(6)~式(8)中,R1、R2、R3、R4分别独立的选自氘、氟、氯、溴、氰基、异腈基、三氟甲基、硝基、取代或未取代的C1~C30的烷基、取代或未取代C3~C30的环烷基、取代或未取代的C1~C30的烷氧基、取代或未取代的C1~C30的烷硫基、取代或未取代的C6~C40的芳基、取代或未取代的C2~C40的杂芳基、取代或未取代的C1~C40的酮基、取代或未取代的C2~C40的烷氧基羰基、取代或未取代的C6~C40的芳氧基羰基、或式(5)所示的基团。
式(5)中,L1和L3各自独立地选自单键,取代或未取代的C6~C40的亚芳基、取代或未取代的C2~C40的亚杂芳基;L2选自氮原子、取代或未取代的C6~C40的亚芳基、取代或未取代的C2~C40的亚杂芳基;Ar选自取代或未取代的C6~C40的芳基、取代或未取代的C2~C40的杂芳基;r选自1~5,且为整数;且当r≥2时,各个L3、Ar基团之间彼此相同或不同;*为连接位点。
在本申请的一些实施例中,r可以为1、2、3、4、5等。
在本申请的一些实施例中,式(5)所示的基团选自如下结构中的一种或多种:
式(12)中,L2不为单键、L3、Ar、*的定义同式(5),r选自1~5,且为整数;
式(13)中,L1,L2均不选自单键,L3、Ar、*的定义同式(5),r选自1~5,且为整数;
式(14)中,L1,L3,Ar,*的定义同式(5),r选自1~5,且为整数。
在本申请的一些实施例中,所述L1、L3各自独立地选自单键或如下基团;L2选自氮原子或如下基团;并且,L1、L2、L3彼此相同或不同:
其中,U独立地选自N、CH、CR6或C*b,并且满足,有且仅有两个U为C*b;R6独立地选自氘、氟、氯、溴、氰基、硝基、三氟甲基、C1~C12的烷基、C3~C12的环烷基、C1~C12的烷氧基、C1~C12的烷硫基、C6~C30的芳基、C2~C30的杂芳基;*b为Ar的键合位点,或*b对应于式(5)中的*;
V选自O、S、NR7、CR8R9、SiR10R11;R7~R11各自独立地选自C1~C12的烷基、C3~C12的环烷基、C6~C30的芳基、C2~C30的杂芳基;或者,R8、R9键合形成C5~C12的脂肪族环、或者键合形成C12~C30的芳香稠环。
在本申请的一些具体实施例中,所述L1、L3各自独立地选自单键或如下基团;L2选自氮原子或如下基团。并且,L1、L2、L3彼此相同或不同:
所述任意基团中,任意两个且仅有两个芳香环上的碳是键合位点;或任意一个氢原子均可以被氘、氟、氯、溴、氰基、硝基、三氟甲基、甲氧基、甲硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、萘基、吡啶基、吡嗪基、嘧啶基、三嗪基、喹啉基、异喹啉基、喹喔啉基中的一个所取代。
本申请的一些实施例中,Ar选自如下基团,且当Ar的个数多于1时,不同Ar之间彼此相同或不同:
其中,X独立地选自N、CH、CR12或C*c;且有一个X选自C*c;R12独立地选自氘、氟、氯、溴、氰基、硝基、C1~C12的烷基、C3~C12的环烷基、C1~C12的烷氧基、C1~C12的烷硫基、C6~C30的芳基、C2~C30的杂芳基;*c为L3的键合位点;
Y选自O、S、NR13、CR14R15、SiR16R17;R13~R17各自独立地选自C1~C12的烷基、C3~C12的环烷基、C6~C30的芳基、C2~C30的杂芳基;或者,R14、R15键合形成C5~C12的脂肪族环、或者键合形成C12~C30的芳香稠环。
本申请的一些具体实施例中,Ar选自如下基团,且当Ar的个数多于1时,不同Ar之间彼此相同或不同:
所述任意基团中,任意一个且仅有一个芳香环上的碳是键合位点,或任意一个氢原子均可以被氘、氟、氯、溴、氰基、硝基、三氟甲基、甲氧基、乙氧基、甲硫基、乙硫基、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、环丙基、环丁基、环戊基、环己基、苯基、甲苯基、特丁基苯基、萘基、吡啶基、吡嗪基、嘧啶基、三嗪基、喹啉基、异喹啉基、喹喔啉基中的一个所取代。
本申请的式(1)、式(6)~式(8)中,m、n、p、q彼此相同或不同,各自独立地选自0至10之间的整数;当m、n、p、q任意一个数字大于1时,每一个取代基团R1、R2、R3、R4彼此相同或不同。以R1举例,即如果m大于1时,多个R1彼此相同或不同。
其中,m为基团R1的数量。在一些实施例中,m可以选自0、1、2、3、4、5、6、7、8、9、10等。
n为基团R2的数量。在一些实施例中,n可以选自0、1、2、3、4、5、6、7、8、9、10等。
p为基团R3的数量。在一些实施例中,p可以选自0、1、2、3、4、5、6、7、8、9、10等。
q为基团R3的数量。在一些实施例中,q可以选自0、1、2、3、4、5、6、7、8、9、10等。
本申请中,碳的个数描述中,例如C1~C12表示的是具有1至12个碳原子。再例如C2~C30表示的是具有2至30个碳原子。其他的同前,不再赘述。
本申请所提供的螺环类化合物中,所述式(1)、式(5)~式(8)中,所述取代或未取代中,取代的取代基选自氘、卤素基团(氟、氯、溴等)、氰基、硝基、三氟甲基、C1~C12的烷基、C3~C12的环烷基、C1~C12的烷氧基、C1~C12的烷硫基、C6~C30的芳基、C2~C30的杂芳基中的一个或多个;并且,R0、R1、R2、R3、R4、L1、L2、L3、Ar中的取代基彼此相同或不相同。
本发明所提供的螺环类化合物中,所述螺环类化合物选自以下化学结构中的任一个:
具体的,上述结构可为未取代或者选自以下的一个或多个取代基取代。例如可以是氘、卤素基团、腈基、硝基、羟基、羰基、酯基、酰亚胺基、胺基、氧化膦基团、烷氧基、芳氧基、烷基硫基、芳基硫基、烷基磺酰基、芳基磺酰基、甲硅烷基、硼基、烷基、环烷基、烯基、芳基、芳烷基、芳烯基、烷基芳基、烷基胺基、芳烷基胺基、杂芳基胺基、芳基胺基、芳基杂芳基胺基、芳基膦基和杂芳基等。
本发明第二方面提供一种有机层,包括本发明第一方面所述的螺环类化合物。
本发明第三方面提供如本发明第一方面所述的螺环类化合物、和/或本发明第二方面所述的有机层在有机电致发光器件中的应用。
本发明第四方面提供一种有机电致发光器件,包括第一电极、第二电极、以及设置在第一电极和第二电极之间的一个或多个有机层,为底部或顶部发光器件结构,其有机层可为单层结构,也可为层合有两个或多个有机层的多层串联结构,所述有机层如具有包括空穴注入层、空穴传输层、发光层、电子注入层或电子传输层中至少一层。可使用制备有机电致发光器件的常见方法和材料来制备。所述有机层包括如本发明第一方面所述的螺环类化合物。
本发明所提供的有机电致发光器件中,第一电极作为阳极层,阳极材料例如可以是具有大功函数的材料,使得空穴顺利地注入有机层。更例如可以是金属、金属氧化物、金属和氧化物的组合、导电聚合物等。金属氧化物例如可以是氧化铟锡(ITO)、氧化锌、氧化铟、和氧化铟锌(IZO)等。
本发明所提供的有机电致发光器件中,第二电极作为阴极层,阴极材料例如可以是具有小功函数的材料,使得电子顺利地注入有机层。阴极材料例如可以是金属或多层结构材料。金属例如可以是镁、银、钙、钠、钾、钛、铟、钇、锂、钆、铝、锡和铅、或其合金。阴极材料优选选自镁和银。
本发明所提供的有机电致发光器件中,空穴注入层的材料,优选最高占据分子轨道(HOMO)介于阳极材料的功函数与周围有机层的HOMO之间的材料作为在低电压下有利地从阳极接收空穴的材料。
本发明所提供的有机电致发光器件中,空穴传输层的材料是对空穴具有高迁移率的材料适合作为接收来自阳极或空穴注入层的空穴并将空穴传输至发光层的材料。空穴传输层的材料包括但不限于芳基胺的有机材料、导电聚合物、同时具有共轭部分和非共轭部分的嵌段共聚物等。
本发明所提供的有机电致发光器件中,发光层的材料通常可以选自对荧光或磷光具有良好量子效率的材料作为能够通过接收分别来自空穴传输层和来自电子传输层的空穴和电子并使空穴与电子结合而在可见光区域内发光的材料。
本发明所提供的有机电致发光器件中,电子传输层的材料是对电子具有高迁移率的材料适合作为有利地接收来自阴极的电子并将电子传输至发光层的材料。
本发明所提供的有机电致发光器件中,覆盖层的材料通常具有高折射率,因此可有助于有机发光器件的光效率提高,尤其是有助于外部发光效率提高。
本发明所提供的有机电致发光器件中,所述有机电致发光器件为有机光伏器件、有机发光器件、有机太阳电池、电子纸、有机感光体、有机薄膜晶体管等。
本发明另一方面提供一种显示或照明装置,包括本发明所述的有机电致发光器件。
下面将以多个合成实施例为例来详述本发明的上述新化合物的具体制备方法,但本发明的制备方法并不限于这多个合成实施例,本领域技术人员可以在其基础上在不悖离本发明原则的前提下进行任何修改、等同替换、改进等,而将该方法扩展到本发明的权利要求书要求保护的技术方案的范围之内。
本发明以结构式(6)为例,给出本发明化合物的代表性合成路径。其余结构的情况同样可参照本合成路径制备:
当A为O时,化合物i中的A1为OH;
当A为S时,化合物i中的A1为SH;
当A为NR0时,化合物i中的A1为NR0H;
合成本发明化合物涉及的主要反应为:第一步,原料化合物i和ii中一者具有卤素官能团碘,另一者具有含活泼氢的官能团(羟基,巯基或胺基),它们在适当的催化体系下反应形成中间体化合物iii;第二步,中间体化合物iii在正丁基锂作用下形成芳基碳负离子,进一步与9-芴酮或其衍生物(化合物iv)反应生成目标化合物。
进一步地,9-芴酮衍生物iv的合成方法可参照非专利文献Org.Lett.2021,23,8688-8693,
具体步骤如下:
中间体化合物vii的合成:
在氮气氛围下,向干燥的三口烧瓶中加入间氯过氧苯甲酸(9.5g,55.0mmol,1.1eq)并溶解于无水二氯甲烷(250mL)中,随后在室温下依次加入碘代化合物v(50.0mmol,1eq)和三氟化硼乙醚(17.7g,125.0mmol,2.5eq),观察到反应体系颜色变为黄色。在室温下将反应体系搅拌1小时,随后降温至0℃,并加入硼酸基化合物vi(55mmol,1.1eq)。投料完毕后将反应体系缓慢恢复至室温,继续搅拌30分钟。随后将反应体系降温至0℃,逐滴加入三氟甲磺酸(8.3g,55.0mmol,1.1eq),并在0℃下继续搅拌15分钟。反应结束后,通过旋转蒸发去除大部分溶剂,加入无水乙醚沉淀出固体,收集所得固体并真空干燥,得到化合物vii。所得固体不经后处理,直接用于下一步反应。
9-芴酮衍生物iv的合成:
在氮气氛围下,向干燥的三口烧瓶中依次加入羧酸基化合物viii(20.0mmol,1eq),二芳基碘化物vii(50.0mmol,2.5eq),醋酸钯(449mg,2.0mmol,10%eq)叔丁醇钠(1.9g,20.0mmol,1eq)和无水二甲苯(Xylene,120mL)。搅拌均匀后,在氮气氛围110℃下反应24小时。通过薄层色谱法分析基本无原料剩余,减压蒸馏去除大部分溶剂。随后向反应瓶中依次加入乙酸乙酯(80mL)和去离子水(100mL),静置分层,收集有机相,水相用乙酸乙酯(3×30mL)萃取,合并所得有机相,并用无水硫酸镁干燥,过滤,减压蒸馏去除溶剂。将所得粗产品经经快速硅胶柱层析分离(流动相为正己烷/乙酸乙酯混合溶剂),得到9-芴酮衍生物iv。
特别地,对于A为NR0的部分实施例,化合物i可通过一步乌尔曼偶联反应合成,合成路线如下:
合成反应的具体步骤为:在氮气氛围下,向干燥的三口烧瓶中依次加入溴代芳基化合物x(1eq),胺基化合物R0-NH2(化合物xi,1eq)和无水甲苯,搅拌均匀后,再依次加入叔丁醇钠(1.5eq),三(二亚苄基丙酮)二钯(0.5%eq),和三叔丁基膦(1.5%eq)。将上述体系混合均匀,并在氮气氛围下升温至回流,反应过夜。通过薄层色谱法分析基本无原料剩余,停止加热。当反应液降温至45℃以下时,向反应体系加入5mL浓盐酸(37%的水溶液)和100mL去离子水的混合溶液,搅拌后静置,用分液漏斗分液,保留有机相,水相用甲苯萃取,与前述保留有机相合并,使用无水硫酸镁干燥,过滤,减压蒸馏去除溶剂,粗产品经快速硅胶柱色谱提纯,得到化合物i。
特别地,对于部分实施例,例如,当R1基团为芳基,杂芳基,或式(3)所述基团时,亦可采用以下的合成路线。使用氯取代的原料化合物i将R1的取代位点以氯原子保留,通过前述“两步法”合成得到中间体化合物v,随后再经历铃木偶联反应或乌尔曼偶联反应连接R1基团,从而得到目标产物。
类似地,对于另一些实施例,例如,当R3或R4基团为芳基,杂芳基,或式(3)所述基团时,亦可以卤代芴酮为起始原料,通过铃木偶联反应或乌尔曼偶联反应连接R3或R4基团,得到中间体化合物iv。
更具体地,以下给出本发明的代表性化合物的合成方法。除特别说明外,本发明中未提及合成方法的化合物均为市售商品;本发明中质谱采用ZABHS型质谱仪测定(英国Micromass公司制造),核磁采用Bruker 400MHz型核磁共振仪(德国Bruker公司制造);
化合物H14的合成:
1、化合物iii-H14的合成
在氮气氛围下,向干燥的烧瓶中依次加入二苯胺(化合物i-H14,6.0g,35.3mmol,1eq)和无水四氢呋喃(350mL),搅拌均匀,随后在室温下将氢化钠(1.7g,70.8mmol,2eq)分批次缓慢地加入前述三口烧瓶中,避免气泡剧烈地产生。氢化钠添加完毕,反应体系呈黄色。在室温下,向反应体系中缓慢滴加1-溴-2-碘苯(化合物ii-H14,10.0g,35.3mmol,1eq),室温下继续反应12小时。将所得反应体系过滤,收集滤液,滤渣用无水四氢呋喃洗涤,洗液与前述滤液合并。合并有机相,通过旋转蒸发去除溶剂。将所得粗产品经快速硅胶柱色谱提纯(流动相为正己烷/乙酸乙酯混合溶剂),得到化合物iii-H14(7.2g,收率62.9%)。质谱(m/z)=324.03[M+H]+
2、化合物iv-H14的合成
首先,参照前述9-芴酮衍生物iv的制备方法合成化合物ix-H14(4.9g,收率78.2%)。质谱(m/z)=313.01[M+H]+。
在氮气氛围下,向干燥的三口烧瓶中依次加入二联苯-4-基胺(化合物xii-H14,4.8g,15.0mmol,1eq)、化合物ix-H14(4.7g,15.0mmol,1eq)和无水甲苯(80mL),搅拌均匀后,再依次加入叔丁醇钠(2.2g,22.5mmol,1.5eq),双二亚苄基丙酮钯(85.0mg,0.15mmol,1%eq),和三叔丁基膦(10%正己烷溶液,0.5mL,0.23mmol,1.5%eq)。将上述体系混合均匀,并在氮气氛围下升温至回流,反应7小时后停止加热。当反应液降温至室温时,向反应体系加入5mL浓盐酸(37%的水溶液)和100mL去离子水的混合溶液,搅拌后静置,用分液漏斗分液,保留有机相,水相用甲苯(3×30mL)萃取,与前述保留有机相合并,使用无水硫酸镁干燥,过滤,减压蒸馏去除溶剂,粗产品经快速硅胶柱色谱提纯(流动相为正己烷/乙酸乙酯混合溶剂),得到化合物iv-H14(6.8g,收率81.8%)。质谱(m/z)=554.24[M+H]+
3、化合物H14的合成
在氮气氛围下,将化合物iii-H14(3.9g,12.0mmol,1eq)溶解于无水四氢呋喃(120mL)中。将溶液置于-78℃浴中,充分冷却后,在此温度氮气氛围下,缓慢滴加正丁基锂的正己烷溶液(浓度2.5M,4.8mL,12.0mmol,1eq),保持-78℃继续搅拌1小时。随后在-78℃的氮气氛围下,向反应体系中逐滴加入化合物iv-H14(6.6g,12.0mmol,1eq)的无水四氢呋喃(30mL)溶液,滴加完毕后使反应体系缓慢恢复至室温,反应8小时。向反应体系中依次缓慢加入去离子水(80mL)淬灭反应,再加入乙酸乙酯(150mL),搅拌后静置分层,用分液漏斗收集有机相,水相用乙酸乙酯(3×50mL)萃取,合并有机相,通过旋转蒸发去除溶剂。随后将所得粗产品溶解于冰乙酸(60mL)中,升温至80℃,逐滴加入0.2mL浓硫酸,在80℃下继续搅拌4小时。随后将反应体系降温至室温,加入蒸馏水(150mL),析出白色固体。过滤,收集滤饼,并用去离子水洗涤,干燥。所得粗产品经快速硅胶柱色谱提纯(流动相为正己烷/甲苯混合溶剂),得到化合物H14(6.7g,收率71.5%)。质谱(m/z)=781.35[M+H]+。从化合物i-H14开始,经化合物iii-H14得到化合物H14,二步反应总收率45.0%。
参照化合物H14的制备方法合成以下化合物(x):H37,H56,H142,H168,H175,H196,H205,H213,不同之处在于,分别使用原料化合物i-x,ii-x,v-x,viii-x和ix-x等当量地代替化合物i-H4,ii-H4,v-14,viii-H4和ix-H4。其中,使用的主要原料、合成的中间体、收率以及质谱表征数据如表1所示。核磁表征数据如表2所示。
表1
表2
化合物H13的合成:
化合物iv-H13的合成方法如下:
首先,参照前述9-芴酮衍生物iv的制备方法合成化合物ix-H13(4.8g,收率79.7%)。质谱(m/z)=300.98[M+H]+。
在氮气氛围下,向三口烧瓶中依次加入化合物ix-H13(4.5g,15.0mmol,1eq),化合物xii-H13(6.6g,15.0mmol,1eq)和脱气甲苯(120mL),混合均匀后,再依次加入碳酸钾(5.2g,37.5mmol,2.5eq),四(三苯基膦)钯(173.3mg,0.15mmol,1%eq),脱气乙醇(40mL)和去离子水(40mL)。开启搅拌,将上述体系充分混合,并在氮气氛围下升温至回流,反应10小时,通过薄层色谱法分析基本无原料剩余,停止加热。待反应体系冷却至室温后倒入80mL甲苯中,静置分层,用甲苯(3×30mL)萃取,合并所得有机相并用无水硫酸镁干燥,过滤并减压蒸馏除去溶剂。将所得粗产品经快速硅胶柱层析分离(流动相为正己烷/二氯甲烷混合溶剂),得到化合物iv-H13(7.2g,收率77.7%)。质谱(m/z)=618.24[M+H]+。
参照化合物H14的制备方法,合成化合物H13,不同之处在于,分别使用化合物i-H13,ii-H13和xii-H13等当量地代替化合物i-H14,ii-H14和xii-H14,经二步反应得到目标化合物H13。二步反应总收率46.9%。化合物H13的质谱(m/z)=898.40[M+H]+。
参照化合物H13的制备方法,合成以下化合物(x):H46,H118,H155,H188,E2,E7,E11,E28,E38,E56,E61,E70,E84,E90,E105,不同之处在于,分别使用原料化合物i-x,ii-x,v-x,viii-x和ix-x等当量地代替化合物i-H13,ii-H13,v-13,viii-H13和ix-H13。其中,使用的主要原料、合成的中间体、收率以及质谱表征数据如表3所示。核磁表征数据如表4所示。
表3
表4
化合物H74的合成:
首先,参照化合物H14的制备方法,合成化合物v-H74,不同之处在于,分别使用化合物i-H74,ii-74和iv-H74等当量地代替化合物i-H14,ii-H14和iv-H14,经两步反应得到中间体化合物v-H74。其中,参照iv-H14的制备方法合成中间体化合物iv-H74。化合物iv-14随后,再参照化合物iv-H14的制备方法合成目标化合物H74,不同之处在于,分别使用化合物v-H74和xii-H74等当量地代替化合物ix-H14和xii-H14,三步反应总收率35.0%。质谱(m/z)=788.38[M+H]+。
另外,化合物H83,H88也可参照化合物H74的制备方法合成。
化合物H83的合成路线如下。其中,参照iv-H14的制备方法合成中间体化合物iv-H83。
三步反应总收率35.6%。质谱(m/z)=895.36[M+H]+。
化合物H88的合成路线如下。其中,参照iv-H14的制备方法合成中间体化合物iv-H88。
三步反应总收率36.5%。质谱(m/z)=969.42[M+H]+。
参照化合物H74的制备方法,合成以下化合物(x):H90,H114,H138,H199,不同之处在于,分别使用原料化合物i-x,ii-x,v-x,viii-x和ix-x等当量地代替化合物i-H74,ii-H74,v-74,viii-H74和ix-H74。其中,使用的主要原料、合成的中间体、收率以及质谱表征数据如表5所示。核磁表征数据如表6所示。
表5
表6
化合物H136的合成
首先,参照化合物H14的制备方法,合成化合物v-H136,不同之处在于,分别使用化合物i-H136,ii-H136和iv-H136等当量地代替化合物i-H14,ii-H14和iv-H14,经两步反应得到中间体化合物v-H136。特别地,参照化合物iv-H14的制备方法合成化合物iv-136。随后,再参照化合物iv-H13的制备方法合成目标化合物H136,采用相同的溶剂和催化体系,通过薄层色谱法判断反应的停止时间点,不同之处在于,分别使用化合物v-H136和xii-H136等当量地代替化合物ix-H13和xii-H13,三步反应总收率35.5%。质谱(m/z)=884.38[M+H]+。
参照化合物H136的制备方法,合成以下化合物(x):E123,E136,E138,E147,E156,E177,不同之处在于,分别使用原料化合物i-x,ii-x,v-x,vii-x和xii-x等当量地代替化合物i-H136,ii-H136,v-H136,vii-136和xii-H116。其中,使用的主要原料、合成的中间体、收率以及质谱表征数据如表7所示。核磁表征数据如表8所示。
表7
表8
化合物E112的合成
三步反应总收率37.5%。质谱(m/z)=849.33[M+H]+。核磁数据1H NMR(400MHz,DMSO-d6)δ9.20(d,J=1.4Hz,2H),8.68–8.59(m,8H),8.47(dt,J=7.5,1.5Hz,2H),8.34–8.28(m,4H),7.91–7.85(m,3H),7.57–7.41(m,6H),7.27(td,J=7.5,1.6Hz,1H),7.22(d,J=7.5Hz,1H),7.18(dd,J=7.5,1.6Hz,1H),7.14–7.08(m,2H),7.05(td,J=7.5,1.5Hz,1H),6.99(dd,J=7.5,1.5Hz,1H),3.00–2.93(m,2H),2.78–2.70(m,2H),1.81–1.68(m,4H)。
器件实施例:
器件所用的本发明的化合物均经过升华提纯,纯度均大于99.98%。
本发明所涉及的化合物,其中部分实施例可作为蓝,绿,红光OLED器件的空穴传输材料使用;另一部分实施例可作为蓝光OLED器件的电子传输材料使用;另一部分实施例可作为红光磷光OLED器件的主体发光材料使用。
蓝色器件实施例:蓝色有机电致发光器件的制备(作为空穴传输材料)
按照如图1所示的结构制作蓝色顶部发光有机电致发光器件,制备工艺为:在玻璃材质的基底101上,通过磁控溅射工艺形成透明阳极ITO膜层(厚度150nm),得到第一电极102作为阳极。在阳极表面,蒸镀化合物1与化合物1-1的混合材料作为空穴注入层103,混合比例为3:97(质量比),厚度为10nm;随后在空穴注入层表面依次蒸镀本发明化合物H13(厚度100nm)和化合物1-2(厚度20nm),分别得到第一层空穴传输层104和第二层空穴传输层105。接下来,在第二空穴传输层105的表面共同蒸镀化合物1-3与化合物1-4(厚度30nm,质量比95:5),形成蓝光发光层106。随后,依次蒸镀化合物5(厚度10nm)形成空穴阻挡层107,以及混合比例为4:6(质量比)的化合物6和LiQ形成电子传输层108(厚度30nm)。之后依次将厚度为3nm厚度镱(Yb),厚度为10nm的镁(Mg)和银(Ag)以1∶9的蒸镀速率真空蒸镀在电子注入层层上,作为第二电极109。最后,蒸镀70nm的化合物7作为覆盖层材料,完成有机发光器件的制造。
表9
蓝色器件实施例2-7
除了在形成空穴注入层和空穴传输层时,分别以下表10中化合物替代化合物H13外,采用与蓝光器件实施例1相同的方法制作有机电致发光器件。
对比例1
除了在形成空穴注入层和空穴传输层时,以化合物1-1替代化合物H13外,采用与蓝光器件实施例1相同的方法制作有机电致发光器件。
所述化合物1,1-1,1-2,1-3,1-4,5,6,7和LiQ的化学结构如表9所示。
对如上制得的有机电致发光器件,其工作电压和效率通过计算机控制的Keithley2400测试系统计算得到。黑暗条件下的器件寿命使用配备电源和光电二极管作为检测单元的Polaronix(McScience Co.)寿命测量系统得到。每一组蓝色器件实施例的器件均与对比例1的器件在同一批次中产出并测试,将对比例1的器件的工作电压、效率和寿命均分别记为1,并分别计算蓝色器件实施例1~7与对比例1的器件相应指标的比值,如表10所示。
表10
空穴传输层 | 相对工作电压 | 相对效率 | 相对寿命 | |
对比例1 | 1-1 | 1 | 1 | 1 |
蓝光器件实施例1 | H13 | 0.960 | 1.067 | 1.580 |
蓝光器件实施例2 | H14 | 0.958 | 1.059 | 1.684 |
蓝光器件实施例3 | H88 | 0.946 | 1.095 | 1.365 |
蓝光器件实施例4 | H114 | 0.932 | 1.076 | 1.431 |
蓝光器件实施例5 | H142 | 0.977 | 1.063 | 1.712 |
蓝光器件实施例6 | H168 | 0.942 | 1.081 | 1.830 |
蓝光器件实施例7 | H205 | 0.951 | 1.054 | 1.778 |
红色器件实施例1:红色有机电致发光器件的制备(作为空穴传输材料)
按照如图2所示的结构制作红色底部发光有机电致发光器件,制备工艺为:在玻璃材质的基底101上,通过磁控溅射工艺形成透明的ITO膜层(厚度150nm),得到第一电极102作为阳极。在阳极表面蒸镀化合物1与化合物1-1的混合材料作为空穴注入层103,混合比例为3:97(质量比),厚度为10nm;随后在空穴注入层表面依次蒸镀化合物1-1(厚度100nm)和本发明化合物H56(厚度10nm),分别得到第一层空穴传输层104和第二层空穴传输层105。接下来,在第二空穴传输层105的表面,将化合物2-3和化合物2-4以95:5的质量比进行共蒸镀,形成有机发光层106(厚度40nm)。随后,在有机发光层表面依次蒸镀化合物5形成空穴阻挡层107(厚度10nm),以及混合比例为4:6(质量比)的化合物6和LiQ形成电子传输层108(厚度30nm)。最后,将镁(Mg)和银(Ag)以1∶9的蒸镀速率混合沉积在电子传输层108的表面,形成厚度为10nm的第二电极109作为阴极,完成有机发光器件的制造。
红色器件实施例2-7
除了在形成第二空穴传输层时,分别以下表12中化合物替代化合物H4外,采用与红光器件实施例1相同的方法制作有机电致发光器件。
对比例2
除了在形成第二空穴传输层时,以化合物HTB替代化合物H4外,采用与红光器件实施例1相同的方法制作有机电致发光器件。
所述化合物1,5,6,7和LiQ的化学结构前所述,化合物2-3,2-4和HTB的化学结构如表11所示。
表11
对如上制得的有机电致发光器件,其工作电压和效率通过计算机控制的Keithley2400测试系统计算得到。黑暗条件下的器件寿命使用配备电源和光电二极管作为检测单元的Polaronix(McScience Co.)寿命测量系统得到。每一组红色器件实施例的器件均与对比例2的器件在同一批次中产出并测试,将对比例2的器件的工作电压、效率和寿命均分别记为1,并分别计算红色实施例器件1~7与对比例2的器件相应指标的比值,如表12所示。
表12
第二空穴传输层 | 相对工作电压 | 相对效率 | 相对寿命 | |
对比例2 | HTB | 1 | 1 | 1 |
红光器件实施例1 | H56 | 0.929 | 1.088 | 1.654 |
红光器件实施例2 | H118 | 0.961 | 1.075 | 1.700 |
红光器件实施例3 | H155 | 0.905 | 1.062 | 1.735 |
红光器件实施例4 | H175 | 0.940 | 1.105 | 1.447 |
红光器件实施例5 | H188 | 0.952 | 1.047 | 1.801 |
红光器件实施例6 | H196 | 0.901 | 1.096 | 1.665 |
红光器件实施例7 | H213 | 0.934 | 1.059 | 1.960 |
绿色器件实施例1:绿色有机电致发光器件的制备(作为空穴传输材料)
按照如图2所示的结构制作绿色底部发光有机电致发光器件,制备工艺为:在玻璃材质的基底101上,通过磁控溅射工艺形成透明的ITO膜层(厚度150nm),得到第一电极102作为阳极。在阳极表面蒸镀化合物1与化合物1-1的混合材料作为空穴注入层103,混合比例为3:97(质量比),厚度为10nm;随后在空穴注入层表面依次蒸镀化合物1-1(厚度100nm)和本发明化合物H37(厚度40nm),分别得到第一层空穴传输层104和第二层空穴传输层105。接下来,在第二空穴传输层105的表面,将化合物3-3和化合物3-4以90:10的质量比进行共蒸镀,形成有机发光层106(厚度40nm)。随后,在有机发光层表面依次蒸镀化合物5形成空穴阻挡层107(厚度10nm),以及混合比例为4:6(质量比)的化合物6和LiQ形成电子传输层108(厚度30nm)。最后,将镁(Mg)和银(Ag)以1∶9的蒸镀速率混合沉积在电子传输层108的表面,形成厚度为10nm的第二电极109作为阴极,完成有机发光器件的制造。
绿色器件实施例2-7
除了在形成第二空穴传输层时,分别以下表14中化合物替代化合物H37外,采用与绿光器件实施例1相同的方法制作有机电致发光器件。
对比例3
除了在形成第二空穴传输层时,以化合物HTC替代化合物H37外,采用与绿光器件实施例1相同的方法制作有机电致发光器件。
以上绿色器件实施例和对比例3使用的主要材料的结构如下表13所示:
表13
对如上制得的有机电致发光器件,其工作电压和效率通过计算机控制的Keithley2400测试系统计算得到。黑暗条件下的器件寿命使用配备电源和光电二极管作为检测单元的Polaronix(McScience Co.)寿命测量系统得到。每一组绿色器件实施例的器件均与对比例3的器件在同一批次中产出并测试,将对比例3的器件的工作电压、效率和寿命均分别记为1,并分别计算绿色器件实施例器件1~7与对比例3的器件相应指标的比值,如表14所示。
表14
第二空穴传输层 | 相对工作电压 | 相对效率 | 相对寿命 | |
对比例3 | HTC | 1 | 1 | 1 |
绿光器件实施例1 | H37 | 0.954 | 1.061 | 1.187 |
绿光器件实施例2 | H46 | 0.948 | 1.079 | 1.175 |
绿光器件实施例3 | H74 | 0.929 | 1.180 | 1.202 |
绿光器件实施例4 | H83 | 0.933 | 1.088 | 1.251 |
绿光器件实施例5 | H90 | 0.917 | 1.085 | 1.315 |
绿光器件实施例6 | H138 | 0.936 | 1.073 | 1.289 |
绿光器件实施例7 | H199 | 0.943 | 1.066 | 1.277 |
蓝色器件实施例8:蓝色有机电致发光器件的制备(作为电子传输材料)
参照蓝光器件实施例1中的有机电致发光器件的制备方法,制备本实施例中的器件,不同之处在于,采用本发明化合物E11和LiQ(混合比例为质量比4:6)共同蒸镀来形成电子传输层108(厚度30nm)。
蓝色器件实施例9~16
除了在形成电子传输层时,分别以下表15中化合物替代化合物E11外,采用与蓝光器件实施例1相同的方法制作有机电致发光器件。
对比例4
除了在形成电子传输层时,以ETA替代化合物E11外,采用与蓝光器件实施例1相同的方法制作有机电致发光器件。化合物ETA的结构如下:
表15
红色器件实施例8:红色有机电致发光器件的制备(作为发光层主体材料)
参照器件对比例2中的红色有机电致发光器件的制备方法,制备本实施例中的器件,不同之处在于,采用本发明化合物E2和化合物2-4以95:5的质量比进行共蒸镀,形成厚度为40nm的有机发光层106。
红色器件实施例9~17
除了在形成电子传输层时,分别以下表16中化合物替代化合物E2外,采用与红光器件实施例1相同的方法制作有机电致发光器件。
对比例5
除了在形成电子传输层时,以HOSTA替代化合物E2外,采用与红光器件实施例1相同的方法制作有机电致发光器件。化合物HOSTA的结构如下:
表16
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (18)
1.一种螺环类化合物,所述螺环类化合物的化学结构如式(1)所示:
式(1)中,A选自O、S或NR0;其中,R0选自取代或未取代的C1~C12的烷基、取代或未取代的C3~C12的环烷基、取代或未取代的C6~C30的芳基、或取代或未取代的C2~30的杂芳基;
所述环G1、G2,相同或不同地,各自独立地选自取代或未取代的C6~C18的芳香族环,或取代或未取代的C3~C18的杂芳香族环;
所述环G3、G4,相同或不同地,各自独立地选自式(2)~式(4)所示的基团,或苯环,且不同时为苯环;
在式(2)~式(4)中,Z彼此相同或不同,各自独立地选自CRARB、NRC、O或S;其中,任意相邻的两个*碳表示与式(1)上五元环的共用连接位点;
所述RA、RB相同或不同地,各自独立地选自氢、氘、氘代或未氘代的甲基;所述RC选自取代或未取代的C1~C8的烷基、取代或未取代的C1~C8的杂烷基、取代或未取代的C3~C12的环烷基、取代或未取代的C3~C12的杂环烷基、取代或未取代的C6~C12的芳基,取代或未取代的C2~C12的杂芳基;
所述式(1)满足条件:所述G3和G4至少有一个选自式(2)~式(4)中的一个;
所述G3和G4均满足条件:当杂原子NRC、S或O的个数多于1个时,任意两个杂原子NRc、S或O之间均间隔至少一个CRARB;
所述R1、R2、R3、R4分别独立的选自氘、氟、氯、溴、氰基、异腈基、三氟甲基、硝基、取代或未取代的C1~C30的烷基、取代或未取代C3~C30的环烷基、取代或未取代的C1~C30的烷氧基、取代或未取代的C1~C30的烷硫基、取代或未取代的C6~C40的芳基、取代或未取代的C2~C40的杂芳基、取代或未取代的C1~C40的酮基、取代或未取代的C2~C40的烷氧基羰基、取代或未取代的C6~C40的芳氧基羰基、或式(5)所示的基团;
m、n、p、q彼此相同或不同,各自独立地选自0至10之间的整数;当m、n、p、q任意一个大于1时,各个R1、R2、R3、R4彼此相同或不同;
*-L1-L2-(L3-Ar)r
(5)
式(5)中,L1和L3各自独立地选自单键、取代或未取代的C6~C40的亚芳基、取代或未取代的C2~C40的亚杂芳基;L2选自氮原子、取代或未取代的C6~C40的亚芳基、取代或未取代的C2~C40的亚杂芳基;Ar选自取代或未取代的C6~C40的芳基、取代或未取代的C2~C40的杂芳基;r选自1~5,且为整数;且当r≥2时,各个L3、Ar基团之间彼此相同或不同;*为连接位点。
3.如权利要求1或2所述的螺环类化合物,其特征在于,所述式(1)、式(5)~式(8)中,所述取代或未取代中,取代的取代基选自氘、卤素基团、氰基、硝基、三氟甲基、C1~C12的烷基、C3~C12的环烷基、C1~C12的烷氧基、C1~C12的烷硫基、C6~C30的芳基、C2~C30的杂芳基中的一个或多个;并且,R0、R1、R2、R3、R4、L1、L2、L3、Ar中的取代基彼此相同或不相同。
8.如权利要求1或7所述的螺环类化合物,其特征在于,所述L1、L3各自独立地选自单键或如下基团;L2选自氮原子或如下基团;并且,L1、L2、L3彼此相同或不同:
其中,U独立地选自N、CH、CR6或C*b,并且满足,有且仅有两个U为C*b;R6独立地选自氘、氟、氯、溴、氰基、硝基、三氟甲基、C1~C12的烷基、C3~C12的环烷基、C1~C12的烷氧基、C1~C12的烷硫基、C6~C30的芳基、C2~C30的杂芳基;*b为Ar的键合位点,或对应于式(5)中的*;
V选自O、S、NR7、CR8R9、SiR10R11;R7~R11各自独立地选自C1~C12的烷基、C3~C12的环烷基、C6~C30的芳基、C2~C30的杂芳基;或者,R8、R9键合形成C5~C12的脂肪族环、或者键合形成C12~C30的芳香稠环。
10.如权利要求1或7所述的螺环类化合物,其特征在于,Ar选自如下基团,且当Ar的个数多于1时,不同Ar之间彼此相同或不同:
其中,X独立地选自N、CH、CR12或C*c;;且有一个X选自C*c;R12独立地选自氘、氟、氯、溴、氰基、硝基、C1~C12的烷基、C3~C12的环烷基、C1~C12的烷氧基、C1~C12的烷硫基、C6~C30的芳基、C2~C30的杂芳基;*c为L3的键合位点;
Y选自O、S、NR13、CR14R15、SiR16R17;R13~R17各自独立地选自C1~C12的烷基、C3~C12的环烷基、C6~C30的芳基、C2~C30的杂芳基;或者,R14、R15键合形成C5~C12的脂肪族环、或者键合形成C12~C30的芳香稠环。
14.一种有机层,包括如权利要求1~13所述的螺环类化合物。
15.如权利要求1~13任一项所述螺环类化合物、和/或如权利要求14所述的有机层在有机电致发光器件中的应用。
16.一种有机电致发光器件,包括第一电极、第二电极和有机层,其中所述有机层为空穴注入层、空穴传输层、发光层、电子注入层或电子传输层中至少一层,且所述有机层包括如权利要求1~13中任一项所述的螺环类化合物。
17.如权利要求16所述的有机电致发光器件,其特征在于,所述有机电致发光器件包括有机光伏器件、有机发光器件、有机太阳电池、电子纸、有机感光体或有机薄膜晶体管。
18.一种显示或照明装置,其特征在于,其包括如权利要求16~17任一项所述的有机电致发光器件。
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