CN111943829A - 一种激基复合物及其应用及采用该激基复合物的有机电致发光器件 - Google Patents

一种激基复合物及其应用及采用该激基复合物的有机电致发光器件 Download PDF

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CN111943829A
CN111943829A CN202010732387.5A CN202010732387A CN111943829A CN 111943829 A CN111943829 A CN 111943829A CN 202010732387 A CN202010732387 A CN 202010732387A CN 111943829 A CN111943829 A CN 111943829A
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CN111943829B (zh
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段炼
张东东
宋晓增
张晨
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Tsinghua University
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Abstract

本发明涉及有机电致发光技术领域,特别涉及一种激基复合物及其应用、以及包含该激基复合物的有机电致发光器件,所述激基复合物包括电子给体型材料和电子受体型材料,电子给体型材料的中心基团与电子受体型材料的中心基团的外围均分别连接有双极性传输基团,分别具有式(1)和式(2)所示的结构。本发明的激基复合物在中心基团的外围引入双极性传输基团能够抑制激基复合物激子淬灭,使其发光蓝移,提高其反向系间窜越速率。

Description

一种激基复合物及其应用及采用该激基复合物的有机电致发 光器件
技术领域
本发明涉及有机电致发光技术领域,特别涉及一种激基复合物及其应用、以及包含该激基复合物的有机电致发光器件。
背景技术
有机电致发光器件(Organic Light Emission Diodes,OLED)是一类具有类三明治结构的器件,包括正负电极膜层及夹在电极膜层之间的有机功能材料层。对OLED器件的电极施加电压,正电荷从正极注入,负电荷从负极注入,在电场作用下正负电荷在有机层中迁移相遇复合发光。由于OLED器件具有高亮度、快响应、宽视角、工艺简单、可柔性化等优点,该技术已被广泛应用于照明灯具、智能手机及平板电脑等产品的显示面板,是一种发展快、技术要求高的新显示技术。
效率好、寿命长的OLED器件通常需要器件结构以及各种有机材料的优化搭配。常见的功能化有机材料有:空穴注入材料、空穴传输材料、空穴阻挡材料、电子注入材料、电子传输材料,电子阻挡材料以及发光主体材料和发光客体(染料)等。为了制备驱动电压更低、发光效率更好、器件使用寿命更长的OLED,材料界一直致力于开发新的有机电致发光材料以实现器件低启动电压、高发光效率和更优的使用寿命。
激基复合物(exciplex)材料单线态-三线态能隙(ΔEST)非常小(<0.2eV),三线态激子可以通过反向系间窜越(RISC)转变成单线态激子发光,器件的内量子效率可以达到100%。除此之外,激基复合物还可以降低器件的驱动电压,引起了科研界和产业界的广泛关注。但是,蓝光激基复合物难于实现且激基复合物发光特性难于调控。现有技术中有通过在电子给体型材料或电子受体型材料上引入惰性位阻基团如叔丁基、环烷基等来增大二者之间的距离,对激基复合物光色及RISC进行调控,但是这会造成激基复合物传输能力降低而使器件驱动电压升高,大大限制了激基复合物材料在低电压、高效率和长寿命有机电致发光器件中的进一步应用。
发明内容
为解决上述技术问题,本发提供了一种激基复合物,可应用于有机电致发光领域。
本发明的这种激基复合物,包括电子给体型材料和电子受体型材料,所述电子给体型材料的中心基团与电子受体型材料的中心基团的外围均分别连接有双极性传输基团。双极性传输基团的引入能够抑制激基复合物激子淬灭,使其发光蓝移,提高其反向系间窜越,并克服因增大电子给体与电子受体型材料之间距离而导致激基复合物传输能力降低的缺陷。
具体而言,本发明提供一种激基复合物,由电子给体型材料和电子受体型材料组成,电子给体型材料具有式(1)所示的结构,电子受体型材料具有式(2)所示的结构:
Figure BDA0002603787120000021
式(1)中,A是具有空穴传输性质的基团,A为取代或未取代的下述基团:二苯氨基、吲哚并咔唑基、呋喃基、苯并呋喃基、异苯并呋喃基、二苯并呋喃基、噻吩基、苯并噻吩基、异苯并噻吩基、二苯并噻吩基、异吲哚基、咔唑基、茚并咔唑基、吡唑基、吲唑基、咪唑基、苯并咪唑基、萘并咪唑基、菲并咪唑基、吡嗪基、吩嗪基、吩噻嗪基、萘啶基、氮杂咔唑基或者9,9-二甲基吖啶基。
式(2)中,B是具有电子传输性质的基团,B为取代或未取代的下述基团:羰基、三唑并三嗪基、呫吨酮基、氮杂咔唑基、三氟甲基、氮杂菲基、吡啶基、嘧啶基、三嗪基、咪唑基、邻菲啰啉基、砜基、庚嗪基、噁二唑基、氰基或者二苯基膦酰基。
式(1)和(2)中,π1、π2、π3、π4分别独立地选自氢、氘或者含有芳环或杂芳环的具有空间位阻且空穴和电子传输性质的基团。具体说,π1、π2、π3、π4分别独立地选自氢、氘、取代或未取代的C6~C60的单环芳基或稠环芳基、取代或未取代的C4~C60的单环杂芳基或稠环杂芳基中的一种。
当A、B、π1、π2、π3、π4具有取代基时,该取代基选自卤素、C1~C30的链状烷基、C3~C30的环烷基、C2~C30的烯基、C1~C30的烷氧基或硫代烷氧基、氰基、硝基、羰基、羧基、氨基、C6~C30芳基、C3~C30杂芳基中的一种或多种的组合。
进一步的,π1、π2、π3、π4分别独立地选自氢、氘、苯基、萘基、蒽基、苯并蒽基、菲基、苯并菲基、四苯基硅基、四苯基碳基、金刚烷基、硅杂芴基、三亚苯基、芘基、窟基、茈基、荧蒽基、并四苯基、并五苯基、苯并芘基、联苯基、偶苯基、三联苯基、三聚苯基、四联苯基、芴基、螺二芴基、二氢菲基、二氢芘基、四氢芘基、顺式或反式茚并芴基、三聚茚基、异三聚茚基、螺三聚茚基、螺异三聚茚基、呋喃基、苯并呋喃基、异苯并呋喃基、二苯并呋喃基、噻吩基、苯并噻吩基、异苯并噻吩基、二苯并噻吩基、吡咯基、异吲哚基、咔唑基、茚并咔唑基、吡啶基、喹啉基、异喹啉基、吖啶基、菲啶基、苯并-5,6-喹啉基、苯并-6,7-喹啉基、苯并-7,8-喹啉基、吡唑基、吲唑基、咪唑基、苯并咪唑基、萘并咪唑基、菲并咪唑基、吡啶并咪唑基、吡嗪并咪唑基、喹喔啉并咪唑基、嗯唑基、苯并嗯唑基、萘并嗯唑基、蒽并嗯唑基、菲并嗯唑基、1,2-噻唑基、1,3-噻唑基、苯并噻唑基、哒嗪基、苯并哒嗪基、嘧啶基、苯并嘧啶基、喹喔啉基、1,5-二氮杂蒽基、2,7-二氮杂芘基、2,3-二氮杂芘基、1,6-二氮杂芘基、1,8-二氮杂芘基、4,5-二氮杂芘基、4,5,9,10-四氮杂茈基、吡嗪基、吩嗪基、吩噻嗪基、萘啶基、氮杂咔唑基、苯并咔啉基、菲咯啉基、1,2,3-三唑基、1,2,4-三唑基、苯并三唑基、1,2,3-噁二唑基、1,2,4-嗯二唑基、1,2,5_嗯二唑基、1,2,3-噻二唑基、1,2,4-噻二唑基、1,2,5-噻二唑基、1,3,4-噻二唑基、1,3,5-三嗪基、1,2,4-三嗪基、1,2,3-三嗪基、四唑基、1,2,4,5-四嗪基、1,2,3,4-四嗪基、1,2,3,5-四嗪基、嘌呤基、蝶啶基、吲嗪基、苯并噻二唑基、9,9-二甲基吖啶基、三芳胺基、氟代苯基、甲基苯基、三甲基苯基、氰基苯基中的一种或多种的组合。
再进一步的,上述通式(1)的化合物优选如下述通式(1-1)至(1-33)所示:
Figure BDA0002603787120000031
Figure BDA0002603787120000041
Figure BDA0002603787120000051
再进一步的,上述通式(2)的化合物优选如下述通式(2-1)至(2-60)所示:
Figure BDA0002603787120000052
Figure BDA0002603787120000061
Figure BDA0002603787120000071
再进一步的,上述通式(1)、式(2)、式(1-1)至式(1-33)和式(2-1)至式(2-60)中,所述π1、π2、π3、π4分别独立地选自下述取代基团中的一种或多种的组合:
Figure BDA0002603787120000081
Figure BDA0002603787120000091
其中,····*代表与式(1)或式(2)中的A或B的连接位点。
更进一步的,本发明的通式(1)所述的化合物可以优选出下述具体结构化合物:这些化合物仅为代表性的,并不限定本发明的范围:
Figure BDA0002603787120000101
Figure BDA0002603787120000111
Figure BDA0002603787120000121
Figure BDA0002603787120000131
Figure BDA0002603787120000141
Figure BDA0002603787120000151
Figure BDA0002603787120000161
更进一步的,本发明的通式(2)所述的化合物可以优选出下述具体结构化合物:这些化合物仅为代表性的,并不限定本发明的范围:
Figure BDA0002603787120000171
Figure BDA0002603787120000181
Figure BDA0002603787120000191
Figure BDA0002603787120000201
Figure BDA0002603787120000211
Figure BDA0002603787120000221
Figure BDA0002603787120000231
Figure BDA0002603787120000241
Figure BDA0002603787120000251
Figure BDA0002603787120000261
Figure BDA0002603787120000271
Figure BDA0002603787120000281
本发明的上述激基复合物作为有机电子器件中的功能材料的应用,所述有机电子器件包括:有机电致发光器件、光学传感器、太阳能电池、照明元件、有机薄膜晶体管、有机场效应晶体管、有机薄膜太阳能电池、信息标签、电子人工皮肤片材、片材型扫描器或电子纸,优选为有机电致发光器件。
本发明还提供一种有机电致发光器件,包括基板,包括第一电极、第二电极和插入在所述第一电极和第二电极之间的一层或多层有机层,其中,所述有机层包含上述本发明提供的激基复合物,由通式(1)与式(2)组成,或者由式(1-1)至式(1-33)中的任一所示的化合物与式(2-1)至式(2-60)中任一所示的化合物组成,或者由具体化合物A1至A93中的任一个与具体化合物B1至B241中的任一个组成。
具体而言,本发明的实施方案提供了一种有机电致发光器件,包括基板,以及依次形成在所述基板上的阳极层、多个发光功能层和阴极层;所述的发光功能层包括空穴注入层、空穴传输层、发光层、电子传输层,所述的空穴注入层形成在所述的阳极层上,所述的空穴传输层形成在所述的空穴注入层上,所述的阴极层形成在所述的电子传输层上,所述的空穴传输层与所述的电子传输层之间为发光层;其中,优选的,所述的发光层中含有上述本发明提供的激基复合物,由通式(1)与式(2)组成,或者由式(1-1)至式(1-33)中的任一所示的化合物与式(2-1)至式(2-60)中任一所示的化合物组成,或者由具体化合物A1至A93中的任一个与具体化合物B1至B66中的任一个组成。
进一步优选,本发明所述的有机电致发光器件,所述的发光功能层中还包括位于空穴传输层与发光层之间的电子阻挡层,所述电子阻挡层中含有上述本发明中通式(1)或者式(1-1)至式(1-33)或者具体化合物A1至A93中任一所示的化合物。
进一步优选,本发明所述的有机电致发光器件,所述的发光功能层中还包括位于发给层与电子传输层之间的空穴阻挡层,所述空穴阻挡层中含有上述本发明中通式(2)或者式(2-1)至式(2-60)或者具体化合物B1至B241中任一所示的化合物。
再一步优选,本发明所述有机电致发光器件中,空穴阻挡层厚度为1nm-200nm,优选厚度为10nm-30nm;发光层厚度为1nm-100nm,优选厚度为20nm-80nm;电子阻挡层厚度为1nm-200nm,优选厚度为10nm-30nm。
更进一步优选,本发明所述的有机电致发光器件中,发光层中含有上述本发明提供的激基复合物,选自通式(1)或者式(1-1)至式(1-33)中的任一所示的化合物与选自通式(2)或者式(2-1)至式(2-60)中任一所示的化合物,两种化合物按质量比为1:10~10:1组成,优选按质量比为3:7~7:3组成,更优选按质量比为4:6~6:4组成,最优选两种化合物按质量比为1:1组成。发光层中含有上述本发明提供的激基复合物,选自具体化合物A1至A93中的任一个与选自具体化合物B1至B241中的任一个,两种化合物按质量比为1:10~10:1组成,优选按质量比为3:7~7:3组成,更优选按质量比为4:6~6:4组成,最优选两种化合物按质量比为1:1组成。
本发明的化合物可以用作有机电致发光器件中的发光层材料,也可以用作有机电致发光器件中的敏化材料。
采用本发明激基复合物制备的有机电致发光器件具有低启动电压、高发光效率和更优的使用寿命。
上述本发明激基复合物被用作有机电致发光器件中时性能优异的具体原因尚不明确,以下是发明人的推测,但这些推测并不限定本发明的保护范围。
本发明的激基复合物包括电子给体型材料和电子受体型材料,电子给体型材料的中心基团与电子受体型材料的中心基团的外围分别设计连接有具备位阻效应的优选特定结构的双极性传输基团,这些双极性传输外围基团的引入能够抑制激基复合物激子淬灭,使其发光蓝移,并且提高激基复合物反向系间窜越速率,从而克服了因增大电子给体与受体型材料之间距离而使激基复合物传输能力降低的缺陷。
具体实施方式
下面将以多个合成和应用实施例为例来详述本发明的上述激基复合物的具体制备方法和用途,但本发明的制备方法和用途并不限于这些合成实施例。
合成实施例
合成实施例1:电子给体型化合物A59的合成
Figure BDA0002603787120000301
在氮气保护下,在250ml圆底烧瓶中加入A59-1(0.82g,2mmol),3-溴-9,9'-螺二芴(0.79g,2mmol),用邻二甲苯(80mL)做溶剂,加入S-phos(49.3mg,0.12mmol),叔丁醇钠(0.58g,6mmol)和Pd(dba)3(55mg,0.06mmol)作为催化剂,加热回流12个小时,冷却后减压蒸馏除去溶剂,通过柱层析纯化(洗脱液为5:1石油醚:二氯甲烷)得到目标产物A59(1.0g,产率69%,HPLC分析纯度99.66%)。MALDI-TOF-MS结果:分子离子峰:722.27元素分析结果:理论值:C:91.38%;H:4.74%;N:3.88%;实验值:C:91.32%;H:4.76%;N:3.92%。
合成实施例2:合成给体A23
Figure BDA0002603787120000302
本实施例与合成实施例1基本相同,其不同之处在于:本例中需将A59-1换为1/2物质的量(mol)的A23-1。终产物A23(0.8g,产率83%,HPLC分析纯度99.46%)。MALDI-TOF-MS结果:分子离子峰:960.35元素分析结果:理论值:C:92.47%;H:4.61%;N:2.91%;实验值:C:92.46%;H:4.60%;N:2.93%。
合成实施例3:合成给体A19
Figure BDA0002603787120000303
本实施例与合成实施例1基本相同,其不同之处在于:本例中需将A59-1换为1/2物质的量(mol)的A19-1,并将3-溴-9,9'-螺二芴替换为等物质的量的4-溴四苯基硅烷。终产物A19(0.9g,产率90%,HPLC分析纯度99.53%)。MALDI-TOF-MS结果:分子离子峰:1000.37元素分析结果:理论值:C:86.36%;H:5.23%;N:2.80%;Si:5.61%;实验值:C:86.32%;H:5.25%;N:2.82%;Si:5.70%。
合成实施例4:合成给体A24
Figure BDA0002603787120000311
在氮气保护下,在250ml圆底烧瓶中加入A24-1(0.82g,2mmol),3-溴-9,9-二苯基芴(0.79g,2mmol),用邻二甲苯(80mL)做溶剂,加入S-phos(49.3mg,0.12mmol),叔丁醇钠(0.58g,6mmol)和Pd(dba)3(55mg,0.06mmol)作为催化剂,加热回流12个小时,冷却后加入乙醇析出白色固体,过滤得到A24-2,直接用于下步反应。
Figure BDA0002603787120000312
在氮气保护下,在250ml圆底烧瓶中加入A24-2(0.82g,2mmol),3-溴螺环[芴-9,9-氧杂蒽](0.82g,2mmol),用邻二甲苯(80mL)做溶剂,加入S-phos(49.3mg,0.12mmol),叔丁醇钠(0.58g,6mmol)和Pd(dba)3(55mg,0.06mmol)作为催化剂,加热回流12个小时,冷却后减压蒸馏除去溶剂,通过柱层析纯化(洗脱液为5:1石油醚:二氯甲烷)得到目标产物A24(1.3g,产率66%,HPLC分析纯度99.45%)。MALDI-TOF-MS结果:分子离子峰:978.36元素分析结果:理论值:C:90.77%;H:4.74%;N:2.86%;O:1.63%;实验值:C:90.70%;H:4.71%;N:2.83%;O:1.76%。
合成实施例5:合成给体A30
Figure BDA0002603787120000321
在氮气保护下,在250mL圆底烧瓶中加入A30-1(1mmol),3-(4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷-2-基)-9,9'-螺二[芴](2mmol),用1:3的乙醇/甲苯(100ml)做溶剂,加入9%碳酸钾水溶液(9ml),和四三苯基膦钯(46mg,0.04mmol)作为催化剂,加热回流12个小时,冷却后过滤用乙醇冲洗滤饼得到终产物化学式A30(0.95g,产率77%,HPLC分析纯度99.53%)。MALDI-TOF-MS结果:分子离子峰:1227.56元素分析结果:理论值:C:91.97%;H:5.75%;N:2.28%;实验值:C:91.94%;H:5.72%;N:2.34%。
合成实例6:合成给体A27
Figure BDA0002603787120000322
在氮气保护下,在250mL圆底烧瓶中加入A27-1(2mmol),4-(4,4,5,5-四甲基-1,3,2-二氧杂环戊硼烷-2-基)-四苯基硅烷(2mmol),用1:3的乙醇/甲苯(100ml)做溶剂,加入9%碳酸钾水溶液(9ml),和四三苯基膦钯(46mg,0.04mmol)作为催化剂,加热回流12个小时,冷却后过滤用乙醇冲洗滤饼得到中间产物化学式A27-2,直接用于下步反应。
Figure BDA0002603787120000331
将A27-2在氮气保护下加入250mL圆底烧瓶,加入4-四苯基甲烷硼酸酯(2mmol),用1:3的乙醇/甲苯(100ml)做溶剂,加入9%碳酸钾水溶液(9ml),和四三苯基膦钯(46mg,0.04mmol)作为催化剂,加热回流12个小时,冷却后过滤用乙醇冲洗滤饼得到终产物化学式A27(1.8g,产率72%,HPLC分析纯度99.69%)。MALDI-TOF-MS结果:分子离子峰:1251.60元素分析结果:理论值:C:89.24%;H:6.28%;N:2.24%;Si:2.24%;实验值:C:89.21%;H:6.24%;N:2.22%;Si:2.33%。
合成实施例7:合成给体B45
Figure BDA0002603787120000332
在氮气保护下,在250mL圆底烧瓶中加入B45-1(2mmol),3-溴-9,9'-螺二芴(2mmol),用1:3的乙醇/甲苯(100ml)做溶剂,加入9%碳酸钾水溶液(9ml),和四三苯基膦钯(46mg,0.04mmol)作为催化剂,加热回流12个小时,冷却后过滤用乙醇冲洗滤饼得到终产物化学式B45(1.0g,产率72%,HPLC分析纯度99.45%)。MALDI-TOF-MS结果:分子离子峰:699.27元素分析结果:理论值:C:89.24%;H:4.75%;N:6.00%;实验值:C:89.28%;H:4.70%;N:6.02%。
合成实施例8:合成给体B55
Figure BDA0002603787120000333
本实施例与合成实施例7基本相同,其不同之处在于:本例中需将B45-1换为1/2物质的量(mol)的B55-1。终产物B55(0.72g,产率63%,HPLC分析纯度99.76%)。MALDI-TOF-MS结果:分子离子峰:1089.41元素分析结果:理论值:C:91.43%;H:4.71%;N:3.85%;实验值:C:91.46%;H:4.70%;N:3.84%。
合成实例9:合成给体B53
Figure BDA0002603787120000341
本实施例与合成实施例7基本相同,其不同之处在于:本例中需将B45-1换为1/2物质的量(mol)的B53-1,并将3-溴-9,9'-螺二芴换为等物质的量(mol)的4-溴四苯基硅烷。终产物B53(0.76g,产率69%,HPLC分析纯度99.72%)。MALDI-TOF-MS结果:分子离子峰:1129.42元素分析结果:理论值:C:86.05%;H:5.26%;N:3.72%;Si:4.97%;实验值:C:86.01%;H:5.23%;N:3.77%;Si:4.99%。
合成实例10:合成给体B67
Figure BDA0002603787120000342
在氮气保护下,在250mL圆底烧瓶中加入B67-1(2mmol),3-氯-9,9-二苯基芴(2mmol),用1:3的乙醇/甲苯(100ml)做溶剂,加入9%碳酸钾水溶液(9ml),和四三苯基膦钯(46mg,0.04mmol)作为催化剂,加热回流12个小时,冷却后过滤用乙醇冲洗滤饼得到中间产物B67-2,直接用于下步反应。
Figure BDA0002603787120000351
在氮气保护下,在250mL圆底烧瓶中加入B67-2(2mmol),3-氯螺环[芴-9,9-氧杂蒽](2mmol),用1:3的乙醇/甲苯(100ml)做溶剂,加入9%碳酸钾水溶液(9ml),和四三苯基膦钯(46mg,0.04mmol)作为催化剂,加热回流12个小时,冷却后过滤用乙醇冲洗滤饼得到终产物化学式B67(0.6g,产率63%,HPLC分析纯度99.58%)。MALDI-TOF-MS结果:分子离子峰:955.36元素分析结果:理论值:C:89.19%;H:4.74%;N:4.39%;O:1.67%;实验值:C:89.15%;H:4.71%;N:4.38%;O:1.76%。
合成实例11:合成客体B68
Figure BDA0002603787120000352
本实施例与合成实施例7基本相同,其不同之处在于:本例中需将B45-1换为1/2物质的量(mol)的B68-1。终产物B68(0.78g,产率67%,HPLC分析纯度99.46%)。MALDI-TOF-MS结果:分子离子峰:1165.44元素分析结果:理论值:C:91.64%;H:4.75%;N:3.60%;实验值:C:91.59%;H:4.71%;N:3.70%。
合成实例12:合成客体B69
Figure BDA0002603787120000353
在氮气保护下,在250mL圆底烧瓶中加入B69-1(2mmol),4-氯四苯基硅烷(2mmol),用1:3的乙醇/甲苯(100ml)做溶剂,加入9%碳酸钾水溶液(9ml),和四三苯基膦钯(46mg,0.04mmol)作为催化剂,加热回流12个小时,冷却后过滤用乙醇冲洗滤饼得到中间产物B69-2,直接用于下步反应。
Figure BDA0002603787120000361
在氮气保护下,在250mL圆底烧瓶中加入B69-2(2mmol),4-氯四苯基甲烷(2mmol),用1:3的乙醇/甲苯(100ml)做溶剂,加入9%碳酸钾水溶液(9ml),和四三苯基膦钯(46mg,0.04mmol)作为催化剂,加热回流12个小时,冷却后过滤用乙醇冲洗滤饼得到终产物化学式B69(1.4g,产率59%,HPLC分析纯度99.26%)。MALDI-TOF-MS结果:分子离子峰:1189.48元素分析结果:理论值:C:88.78%;H:5.33%;N3.53%;Si:2.36%;实验值:C:88.72%;H:5.30%;N3.55%;Si:2.43%。
本发明的实施例中有机电致发光器件制备过程如下:
将涂布了ITO透明导电层的玻璃板在商用清洗剂中超声处理,在去离子水中冲洗,在丙酮:乙醇混合溶剂中超声除油,在洁净环境下烘烤至完全除去水份,用紫外光和臭氧清洗,并用低能阳离子束轰击表面;
把上述带有阳极的玻璃基片置于真空腔内,抽真空至1×10-5~5×10-4Pa,在上述阳极层膜上真空蒸镀HATCN空穴注入层,蒸镀速率为0.1nm/s,蒸镀膜厚为5nm;
在空穴注入层之上真空蒸镀NPB作为器件的空穴传输层,蒸镀速率为0.1nm/s,蒸镀总膜厚为30nm;
在空穴传输层上真空蒸镀发光层主体材料中激基复合物的给体材料作为电子阻挡层,蒸镀速率为0.1nm/s,蒸镀总膜厚为1nm-200nm,优选厚度为10nm-30nm;
在电子阻挡层之上真空蒸镀器件的发光层,本发明的发光层中包括主体材料和染料材料,主体材料选自本发明的给体和受体材料组成的激基复合物,将5TCzBN作为染料材料。调节上述主体材料的蒸镀速率均为0.1nm/s,调节发光层中的染料蒸镀速率为主体蒸镀速率的10%-30%比例设定,发光层蒸镀总膜厚为1nm-100nm,优选厚度为20-80nm;
在发光层之上真空蒸镀器件的空穴阻挡层,为发光层主体材料中激基复合物的受体材料,其蒸镀速率为0.1nm/s,蒸镀总膜厚为1nm-200nm,优选厚度为10nm-30nm;
在空穴阻挡层之上真空蒸镀DPyPA作为器件的电子传输材料,其蒸镀速率为0.1nm/s,蒸镀总膜厚为30nm;
在电子传输层(ETL)上真空蒸镀厚度为0.5nm的LiF作为电子注入层,厚度为150nm的Al层作为器件的阴极。
Figure BDA0002603787120000371
实施例1
将涂布了ITO透明导电层的玻璃板在商用清洗剂中超声处理,在去离子水中冲洗,在丙酮:乙醇混合溶剂中超声除油,在洁净环境下烘烤至完全除去水份,用紫外光和臭氧清洗,并用低能阳离子束轰击表面;
在空穴注入层之上真空蒸镀NPB作为器件的空穴传输层,蒸镀速率为0.1nm/s,蒸镀总膜厚为30nm;
在空穴传输层上真空蒸镀A59作为电子阻挡层,蒸镀速率为0.1nm/s,蒸镀总膜厚为10nm;
在电子阻挡层之上真空蒸镀器件的发光层,本发明的发光层中包括主体材料和染料材料,主体材料为A59和B45等比例混合组成的激基复合物,将5TCzBN作为染料材料。调节上述主体材料的蒸镀速率均为0.1nm/s,调节发光层中的染料蒸镀速率为主体蒸镀速率的10%-30%比例设定,发光层蒸镀总膜厚为20-80nm;
在发光层之上真空蒸镀B45作为器件的空穴阻挡层,其蒸镀速率为0.1nm/s,蒸镀总膜厚为10nm;
在空穴阻挡层之上真空蒸镀DPyPA作为器件的电子传输材料,其蒸镀速率为0.1nm/s,蒸镀总膜厚为30nm;
在电子传输层(ETL)上真空蒸镀厚度为0.5nm的LiF作为电子注入层,厚度为150nm的Al层作为器件的阴极。
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45):20wt%5TCzBN(30nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例2
与实施例1的制备方法相同,区别在于,将电子阻挡层、空穴阻挡层由A59、B45分别相应替换为A23、B55,将主体材料由A59和B45等比例混合的激基复合物替换为由A23和B55等比例混合的激基复合物,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A23(10nm)/exciplex(A23:B55):20wt%5TCzBN(30nm)/B55(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例3
与实施例1的制备方法相同,区别在于,将电子阻挡层、空穴阻挡层由A59,B45分别相应替换为A19,B53,将主体材料由A59,B1等比例混合的激基复合物替换为A19,B53等比例混合的激基复合物,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A19(10nm)/exciplex(A19:B53):20wt%5TCzBN(30nm)/B53(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例4
与实施例1的制备方法相同,区别在于,将电子阻挡层、空穴阻挡层由A59,B45分别相应替换为A24,B67,将主体材料由A59,B45等比例混合的激基复合物替换为A24,B67等比例混合的激基复合物,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A24(10nm)/exciplex(A24:B67):20wt%5TCzBN(30nm)/B67(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例5
与实施例1的制备方法相同,区别在于,将电子阻挡层、空穴阻挡层由A59,B45分别相应替换为A30,B68,将主体材料由A59,B45等比例混合的激基复合物替换为A30,B68等比例混合的激基复合物,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A30(10nm)/exciplex(A30:B68):20wt%5TCzBN(30nm)/B68(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例6
与实施例1的制备方法相同,区别在于,将电子阻挡层、空穴阻挡层由A59,B45分别相应替换为A27,B69,将主体材料由A59,B45等比例混合的激基复合物替换为A27,B69等比例混合的激基复合物,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A27(10nm)/exciplex(A27:B69):20wt%5TCzBN(30nm)/B69(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例7
与实施例1的制备方法相同,区别在于,将电子阻挡层、空穴阻挡层由A59、B45分别相应替换为DA、DB,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/DA(10nm)/exciplex(A59:B45):20wt%5TCzBN(30nm)/DB(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例8
与实施例1的制备方法相同,区别在于,将电子阻挡层、空穴阻挡层由A59、B45分别相应替换为DA、DB,将主体材料由A59和B45等比例混合的激基复合物替换为由A23和B55等比例混合的激基复合物,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/DA(10nm)/exciplex(A23:B55):20wt%5TCzBN(30nm)/DB(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例9
与实施例1的制备方法相同,区别在于,将电子阻挡层、空穴阻挡层由A59,B45分别相应替换为DA,DB,将主体材料由A59,B1等比例混合的激基复合物替换为A19,B53等比例混合的激基复合物,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/DA(10nm)/exciplex(A19:B53):20wt%5TCzBN(30nm)/DB(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例10
与实施例1的制备方法相同,区别在于,将电子阻挡层厚度由10nm增加至30nm,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(30nm)/exciplex(A59:B45):20wt%5TCzBN(30nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例11
与实施例1的制备方法相同,区别在于,将空穴阻挡层厚度由10nm增加至30nm,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45):20wt%5TCzBN(30nm)/B45(30nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例12
与实施例1的制备方法相同,区别在于,将发光层厚度由30nm增加至40nm,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45):20wt%5TCzBN(40nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例13
与实施例1的制备方法相同,区别在于,将发光层厚度由30nm降低至20nm,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45):20wt%5TCzBN(20nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例14
与实施例1的制备方法相同,区别在于,将主体材料A59与B45由等比例混合改为1:10比例混合,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45=1:10):20wt%5TCzBN(30nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例15
与实施例1的制备方法相同,区别在于,将主体材料A59与B45由等比例混合改为1:8比例混合,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45=1:8):20wt%5TCzBN(30nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例16
与实施例1的制备方法相同,区别在于,将主体材料A59与B45由等比例混合改为1:6比例混合,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45=1:6):20wt%5TCzBN(30nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例17
与实施例1的制备方法相同,区别在于,将主体材料A59与B45由等比例混合改为1:4比例混合,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45=1:4):20wt%5TCzBN(30nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例18
与实施例1的制备方法相同,区别在于,将主体材料A59与B45由等比例混合改为1:2比例混合,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45=1:2):20wt%5TCzBN(30nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例19
与实施例1的制备方法相同,区别在于,将主体材料A59与B45由等比例混合改为2:1比例混合,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45=2:1):20wt%5TCzBN(30nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例20
与实施例1的制备方法相同,区别在于,将主体材料A59与B45由等比例混合改为4:1比例混合,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45=4:1):20wt%5TCzBN(30nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例21
与实施例1的制备方法相同,区别在于,将主体材料A59与B45由等比例混合改为6:1比例混合,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45=6:1):20wt%5TCzBN(30nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例22
与实施例1的制备方法相同,区别在于,将主体材料A59与B45由等比例混合改为8:1比例混合,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45=1:8):20wt%5TCzBN(30nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例23
与实施例1的制备方法相同,区别在于,将主体材料A59与B45由等比例混合改为10:1比例混合,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A59(10nm)/exciplex(A59:B45=10:1):20wt%5TCzBN(30nm)/B45(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例24
与实施例2的制备方法相同,区别在于,将主体材料A23与B55由等比例混合改为1:2比例混合,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A23(10nm)/exciplex(A23:B55=1:2):20wt%5TCzBN(30nm)/B55(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
实施例25
与实施例2的制备方法相同,区别在于,将主体材料A23与B55由等比例混合改为2:1比例混合,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/A23(10nm)/exciplex(A23:B55=2:1):20wt%5TCzBN(30nm)/B55(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
对比实施例1
与实施例1的制备方法相同,区别在于,将电子阻挡层、空穴阻挡层由A59、B45分别相应替换为DA1、DB1,将主体材料由A59、B45等比例混合的激基复合物替换为DA1,DB1等比例混合的激基复合物,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/DA1(10nm)/exciplex(DA1:DB1):20wt%5TCzBN(30nm)/DB1(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
Figure BDA0002603787120000431
对比实施例2:
与实施例1的制备方法相同,区别在于,将电子阻挡层、空穴阻挡层由A59、B45分别相应替换为DA2、DB2,将主体材料由A59、B45等比例混合的激基复合物替换为DA2,DB2等比例混合的激基复合物,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/DA2(10nm)/exciplex(DA2:DB2):20wt%5TCzBN(30nm)/DB2(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
Figure BDA0002603787120000432
Figure BDA0002603787120000441
对比实施例3:
与实施例1的制备方法相同,区别在于,将电子阻挡层、空穴阻挡层由A59、B45分别相应替换为DA3、DB3,将主体材料由A59、B45等比例混合的激基复合物替换为DA3,DB3等比例混合的激基复合物,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/DA3(10nm)/exciplex(DA3:DB3):20wt%5TCzBN(30nm)/DB3(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
Figure BDA0002603787120000442
对比实施例4:
与实施例1的制备方法相同,区别在于,将电子阻挡层、空穴阻挡层由A59、B45分别相应替换为DA4、DB4,将主体材料由A59、B45等比例混合的激基复合物替换为DA4,DB4等比例混合的激基复合物,器件结构如下:
ITO/HATCN(5nm)/NPB(30nm)/DA4(10nm)/exciplex(DA4:DB4):20wt%5TCzBN(30nm)/DB4(10nm)/DPyPA(30nm)/LiF(0.5nm)/Al(150nm)。
Figure BDA0002603787120000451
上述各个器件实施例和对比器件实施例所制备的有机电致发光器件性能见下表1。
表1:
Figure BDA0002603787120000452
Figure BDA0002603787120000461
就实施例1-6与比较例1而言,在有机电致发光器件结构中其他材料相同的情况下,本发明涉及的化合物相比于比较例1中的材料电压有所降低,效率有较大幅度提升并且寿命有相应的提高。
就实施例1-6与比较例2-4而言,在有机电致发光器件结构中其他材料相同的情况下,本发明涉及的化合物相比于比较例2-4中的材料电压有所降低,效率有较大幅度提升并且寿命有相应的提高。
以上实验数据表明,本发明的有机材料是性能良好的有机发光功能材料,有望推广商业化应用。
尽管结合实施例对本发明进行了说明,但本发明并不局限于上述实施例,应当理解,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合,为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。

Claims (12)

1.一种激基复合物,由电子给体型材料和电子受体型材料组成,所述电子给体型材料具有式(1)所示的结构,所述电子受体型材料具有式(2)所示的结构:
Figure FDA0002603787110000011
式(1)中,A选自取代或未取代的下述基团:二苯氨基、吲哚并咔唑基、呋喃基、苯并呋喃基、异苯并呋喃基、二苯并呋喃基、噻吩基、苯并噻吩基、异苯并噻吩基、二苯并噻吩基、异吲哚基、咔唑基、茚并咔唑基、吡唑基、吲唑基、咪唑基、苯并咪唑基、萘并咪唑基、菲并咪唑基、吡嗪基、吩嗪基、吩噻嗪基、萘啶基、氮杂咔唑基或者9,9-二甲基吖啶基;
式(2)中,B选自取代或未取代的下述基团:羰基、三唑并三嗪基、呫吨酮基、氮杂咔唑基、三氟甲基、氮杂菲基、吡啶基、嘧啶基、三嗪基、咪唑基、邻菲啰啉基、砜基、庚嗪基、噁二唑基、氰基或者二苯基膦酰基;
式(1)和(2)中,π1、π2、π3、π4分别独立地选自氢、氘、取代或未取代的C6~C60的单环芳基或稠环芳基、取代或未取代的C4~C60的单环杂芳基或稠环杂芳基中的一种;
当A、B、π1、π2、π3、π4具有取代基时,该取代基选自卤素、C1~C30的链状烷基、C3~C30的环烷基、C2~C30的烯基、C1~C30的烷氧基或硫代烷氧基、氰基、硝基、羰基、羧基、氨基、C6~C30芳基、C3~C30杂芳基中的一种或多种的组合。
2.根据权利要求1所述的激基复合物,所述式(1)的化合物为下述通式(1-1)至(1-33)表示的化合物:
Figure FDA0002603787110000012
Figure FDA0002603787110000021
Figure FDA0002603787110000031
π1、π2、π3、π4与在式(1)中限定的意思相同。
3.根据权利要求1所述的激基复合物,所述式(2)的化合物为下述通式(2-1)至(2-60)所示的化合物:
Figure FDA0002603787110000032
Figure FDA0002603787110000041
Figure FDA0002603787110000051
π1、π2、π3、π4与在式(2)中限定的意思相同。
4.根据权利要求1-3中任一所述的激基复合物,式(1)、式(2)、式(1-1)至式(1-33)和式(2-1)至式(2-60)中,所述π1、π2、π3、π4分别独立地选自下述取代基团中的一种:
Figure FDA0002603787110000061
Figure FDA0002603787110000071
其中,····*代表与式(1)或式(2)中的A或B的连接位点。
5.根据权利要求1-3中任一所述的激基复合物,所述π1、π2、π3、π4分别独立地选自氢、氘、苯基、萘基、蒽基、苯并蒽基、菲基、苯并菲基、四苯基硅基、四苯基碳基、金刚烷基、硅杂芴基、三亚苯基、芘基、窟基、茈基、荧蒽基、并四苯基、并五苯基、苯并芘基、联苯基、偶苯基、三联苯基、三聚苯基、四联苯基、芴基、螺二芴基、二氢菲基、二氢芘基、四氢芘基、顺式或反式茚并芴基、三聚茚基、异三聚茚基、螺三聚茚基、螺异三聚茚基、呋喃基、苯并呋喃基、异苯并呋喃基、二苯并呋喃基、噻吩基、苯并噻吩基、异苯并噻吩基、二苯并噻吩基、吡咯基、异吲哚基、咔唑基、茚并咔唑基、吡啶基、喹啉基、异喹啉基、吖啶基、菲啶基、苯并-5,6-喹啉基、苯并-6,7-喹啉基、苯并-7,8-喹啉基、吡唑基、吲唑基、咪唑基、苯并咪唑基、萘并咪唑基、菲并咪唑基、吡啶并咪唑基、吡嗪并咪唑基、喹喔啉并咪唑基、嗯唑基、苯并嗯唑基、萘并嗯唑基、蒽并嗯唑基、菲并嗯唑基、1,2-噻唑基、1,3-噻唑基、苯并噻唑基、哒嗪基、苯并哒嗪基、嘧啶基、苯并嘧啶基、喹喔啉基、1,5-二氮杂蒽基、2,7-二氮杂芘基、2,3-二氮杂芘基、1,6-二氮杂芘基、1,8-二氮杂芘基、4,5-二氮杂芘基、4,5,9,10-四氮杂茈基、吡嗪基、吩嗪基、吩噻嗪基、萘啶基、氮杂咔唑基、苯并咔啉基、菲咯啉基、1,2,3-三唑基、1,2,4-三唑基、苯并三唑基、1,2,3-噁二唑基、1,2,4-嗯二唑基、1,2,5_嗯二唑基、1,2,3-噻二唑基、1,2,4-噻二唑基、1,2,5-噻二唑基、1,3,4-噻二唑基、1,3,5-三嗪基、1,2,4-三嗪基、1,2,3-三嗪基、四唑基、1,2,4,5-四嗪基、1,2,3,4-四嗪基、1,2,3,5-四嗪基、嘌呤基、蝶啶基、吲嗪基、苯并噻二唑基、9,9-二甲基吖啶基、三芳胺基、氟代苯基、甲基苯基、三甲基苯基、氰基苯基中的一种或多种的组合。
6.根据权利要求1所述的激基复合物,式(1)所述的化合物为下述具体结构化合物:
Figure FDA0002603787110000091
Figure FDA0002603787110000101
Figure FDA0002603787110000111
Figure FDA0002603787110000121
Figure FDA0002603787110000131
Figure FDA0002603787110000141
Figure FDA0002603787110000151
7.根据权利要求1所述的激基复合物,式(2)所述的化合物为下述具体结构化合物:
Figure FDA0002603787110000161
Figure FDA0002603787110000171
Figure FDA0002603787110000181
Figure FDA0002603787110000191
Figure FDA0002603787110000201
Figure FDA0002603787110000211
Figure FDA0002603787110000221
Figure FDA0002603787110000231
Figure FDA0002603787110000241
Figure FDA0002603787110000251
Figure FDA0002603787110000261
Figure FDA0002603787110000271
8.根据权利要求1-7中任一所述的激基复合物作为有机电子器件中的功能材料的应用,所述有机电子器件包括:有机电致发光器件、光学传感器、太阳能电池、照明元件、有机薄膜晶体管、有机场效应晶体管、有机薄膜太阳能电池、信息标签、电子人工皮肤片材、片材型扫描器或电子纸。
9.一种有机电致发光器件,包括基板,包括第一电极、第二电极和插入在所述第一电极和第二电极之间的一层或多层有机层,其中,所述有机层包含上述本发明提供的激基复合物,由权利要求1中通式(1)与式(2)组成,或者由权利要求2和3中的式(1-1)至式(1-33)中的任一所示的化合物与式(2-1)至式(2-60)中任一所示的化合物组成,或者由权利要求6和7中的具体化合物A1至A93中的任一个与具体化合物B1至B241中的任一个组成。
10.根据权利要求9所述的有机电致发光器件,其特征在于,所述的发光功能层包括空穴注入层、空穴传输层、发光层、电子传输层,所述的空穴注入层形成在所述的阳极层上,所述的空穴传输层形成在所述的空穴注入层上,所述的阴极层形成在所述的电子传输层上,所述的空穴传输层与所述的电子传输层之间为发光层;其中,所述的发光层中含有上述本发明提供的激基复合物,由通式(1)与式(2)组成,或者由式(1-1)至式(1-33)中的任一所示的化合物与式(2-1)至式(2-60)中任一所示的化合物组成,或者由具体化合物A1至A93中的任一个与具体化合物B1至B241中的任一个组成;
进一步的,所述的发光功能层中还包括位于空穴传输层与发光层之间的电子阻挡层,所述电子阻挡层中含有上述本发明中通式(1)或者式(1-1)至式(1-33)或者具体化合物A1至A93中任一所示的化合物;
进一步的,所述的发光功能层中还包括位于发给层与电子传输层之间的空穴阻挡层,所述空穴阻挡层中含有上述本发明中通式(2)或者式(2-1)至式(2-60)或者具体化合物B1至B241中任一所示的化合物。
11.根据权利要求10所述的有机电致发光器件,其特征在于,所述发光层中含有的激基复合物选自权利要求1和2中的通式(1)或者式(1-1)至式(1-33)中的任一所示的化合物与选自权利要求1和3中的通式(2)或者式(2-1)至式(2-60)中任一所示的化合物,两种化合物按质量比为1:10~10:1组成,优选按质量比为3:7~7:3组成,更优选按质量比为4:6~6:4组成,最优选两种化合物按质量比为1:1组成;
或者,发光层中含有的激基复合物选自权利要求6和7中的具体化合物A1至A93中的任一个与选自具体化合物B1至B241中的任一个,两种化合物按质量比为1:10~10:1组成,优选按质量比为3:7~7:3组成,更优选按质量比为4:6~6:4组成,最优选两种化合物按质量比为1:1组成。
12.根据权利要求10或11所述的有机电致发光器件,其特征在于,所述空穴阻挡层厚度为1nm-200nm,优选厚度为10nm-30nm;
所述发光层厚度为1nm-100nm,优选厚度为20nm-80nm;
所述电子阻挡层厚度为1nm-200nm,优选厚度为10nm-30nm。
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