CN106432158A - 一种有机发光化合物材料及其应用 - Google Patents

一种有机发光化合物材料及其应用 Download PDF

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CN106432158A
CN106432158A CN201610833207.6A CN201610833207A CN106432158A CN 106432158 A CN106432158 A CN 106432158A CN 201610833207 A CN201610833207 A CN 201610833207A CN 106432158 A CN106432158 A CN 106432158A
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叶中华
李崇
张兆超
徐凯
张小庆
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Jiangsu Sunera Technology Co Ltd
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Jiangsu Sanyue Optoelectronic Technology Co Ltd
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Abstract

本发明公开了一种有机发光化合物及其应用，该化合物材料的结构式如通式(1)所示。该种材料易形成非晶型薄膜，具有良好的热稳定性以及高单线态能级，因此该类材料可做为有机电致发光器件中的发光层主体材料使用。

Description

一种有机发光化合物材料及其应用
技术领域
本发明涉及半导体技术领域，尤其是涉及一种荧光化合物的合成，以及作为发光层主体材料在有机发光二极管上的应用。
背景技术
有机电致发光(OLED:Organic Light Emission Diodes)器件技术既可以用来制造新型显示产品，也可以用于制作新型照明产品，有望替代现有的液晶显示和荧光灯照明，应用前景十分广泛。
当前，OLED显示技术已经在智能手机，平板电脑等领域获得应用，进一步还将向电视等大尺寸应用领域扩展。但是，和实际的产品应用要求相比，OLED器件的发光效率，使用寿命等性能还需要进一步提升。
OLED发光器件犹如三明治的结构，包括电极材料膜层，以及夹在不同电极膜层之间的有机功能材料，各种不同功能材料根据用途相互叠加在一起共同组成OLED发光器件。作为电流器件，当对OLED发光器件的两端电极施加电压，并通过电场作用有机层功能材料膜层中正负电荷，正负电荷进一步在发光层中复合，即产生OLED电致发光。
对于OLED发光器件提高性能的研究包括：降低器件的驱动电压，提高器件的发光效率，提高器件的使用寿命等。为了实现OLED器件的性能的不断提升，不但需要从OLED器件结构和制作工艺的创新，更需要OLED光电功能材料不断研究和创新，创制出更高性能OLED的功能材料。
应用于OLED器件的OLED光电功能材料从用途上可划分为两大类，即电荷注入传输材料和发光材料，进一步，还可将电荷注入传输材料分为电子注入传输材料和空穴注入传输材料，还可以将发光材料分为主体发光材料和掺杂材料。为了制作高性能的OLED发光器件，要求各种有机功能材料具备良好的光电特性，譬如，作为电荷传输材料，要求具有良好的载流子迁移率，高玻璃化转化温度等，作为发光层的材料要求材料具有良好的荧光量子效率、材料蒸镀稳定性、适当的HOMO/LUMO能级等。
构成OLED器件的OLED光电功能材料膜层至少包括两层以上结构，产业上应用的OLED器件结构，则包括空穴注入层、空穴传输层、发光层、电子注入层等多种膜层，也就是说应用于OLED器件的光电功能材料至少包含空穴注入材料，空穴传输材料，发光材料，电子注入材料等，材料类型和搭配形式具有丰富性和多样性的特点。另外，对于不同结构的OLED器件搭配而言，所使用的光电功能材料具有较强的选择性，相同的材料在不同结构器件中的性能表现，也可能完全迥异。
目前，荧光材料研究方面已经取得了长足的发展，能够满足产业化的需求；但是其效率、寿命方面依然存在不足，不易达到全彩RGB的要求。主要的原因是缺乏高效、稳定的主体材料；特别是对于提升器件寿命而言，主体材料的稳定性尤其重要。良好的主体材料能够防止器件长时间工作时因热量导致有机材料发生结晶，降低器件效率；同时能够提高主客体之间的能量传递效率，提升器件效率。
因而，具有良好热稳定性，高单线态能级的主体材料的研究和开发一直是产业化的热点。
发明内容
针对现有技术存在的上述问题，本申请人提供了一种有机发光化合物及其应用。本发明化合物作为发光层主体材料制作出的OLED器件具有良好的外量子效率、材料稳定性以及色纯度，能够满足面板制造企业的要求。
本发明的技术方案如下：
本申请人提供了一种有机电致发光化合物，所述化合物的结构如通式(1)所示：
通式(1)中，R1表示为取代或者未取代的苯基，并且与C1-C2、C2-C3、或C3-C4键结成环；当R1表示为取代的苯基时，其取代基为氢、碳原子数1-6的烷基、芳基、或杂芳基；
R3、R4分别独立的表示为氢、碳原子数1-6的烷基、苯基；或者R3、R4通过键结形成碳原子数为10-16的芳基环；
R2表示为通式(4)、(5)、(6)中的一种：
a选自中的一种；
a与C5-C6键、C6-C7键、或C7-C8键连接；
X1、X2、X3分别独立的表示为氧原子、硫原子、C1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基或芳基取代的叔胺基中的一种；
X4、X5分别独立的表示为氢、碳原子数1-6的烷基、苯基；或者X4、X5通过键结的形成碳原子数为10-16的芳基环；
R5独立地表示为氢、碳原子数1-6的烷基、芳基、杂芳基。
优选的，所述化合物材料选自通式(1a)-(3a)的任一种：
其中，通式(1a)-(3a)中的Ra分别独立的表示为氢、碳原子数1-6的烷基、芳基、杂芳基。
优选的，所述Ra、R5分别独立的表示取代或未取代的苯基、吡啶基、二联苯基、三联苯基、萘基、蒽基、菲基、三嗪基、嘧啶基、喹啉基、二苯并呋喃基、二苯并噻吩基、9,9-二甲基芴基、9,9-二苯基芴基、咔唑基、苯并咔唑基、噻吩基、呋喃基、或苯并咪唑基中的一种。
优选的，所述Ra、R5分别独立的采用通式(7)表示：
通式(7)中，X6为氧原子、硫原子、C1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基或芳基取代的叔胺基中的一种；
R6表示为氢、碳原子数1-6的烷基、芳基、或杂芳基。
优选的，所述化合物的具体结构为：
中的任一种。
本申请人还提供了一种含有所述有机电致发光化合物的有机电致发光器件，所述化合物作为发光层主体材料应用于有机电致发光二极管。
本发明有益的技术效果在于：
本发明所述化合物可应用于OLED发光器件制作，并且可以获得良好的器件表现，所述化合物作为OLED发光器件的发光层主体材料搭配掺杂材料使用时，器件的发光效率，功率效率和外量子效率均得到很大改善；器件色纯度得到明显改善，器件寿命得到提升。本发明所述化合物在OLED发光器件中具有良好的应用效果，具有良好的产业化前景。
本发明以苯并庚烯骨架为核心，并于稠环基团间接成环，该类结构的分子具有较强的空间立体作用，能够有效降低分子间的聚集效应，抑制材料的结晶程度，同时具有良好的热稳定性和单线态能级。该类材料运用于有机发光二极管中，可以有效提高器件效率和寿命。
附图说明
图1为本发明化合物制成的OLED器件的示意图。
图中：1、透明基板层，2、ITO阳极层，3、空穴注入层，4、空穴传输层，5、发光层，6、电子传输层，7、电子注入层，8、阴极反射电极层。
具体实施方式
为了更加清楚的了解本发明的技术手段和实用目的，通过列举实施例和比较例，同时辅以图片加以说明。
实施例1(化合物05)
现提供该化合物的具体合成路线：
250ml的四口瓶，氮气保护下，加入0.01mol化合物1，0.0105mol邻羟基苯硼酸，甲苯、乙醇、水各50ml，0.05克pd(pph3)4(四三苯基磷合钯)，0.025mol碳酸钠，加热回流12小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后得到白色中间体A。
250ml的四口瓶，氮气保护下，加入0.01mol中间体A，0.025mol碳酸钾，150ml NMP，150度下搅拌反应12小时。反应完全，自然冷却至室温。将反应液加入到分液漏斗中，加400ml水，用醋酸乙酯萃取3次，合并萃取液。萃取液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后得到白色固体，纯度(HPLC)为98.0％，收率60.1％。
元素分析结构(分子式C27H20O)：理论值C,89.97；H,5.59；N,4.44；
测试值：C,90.05；H,5.68；N,4.27。
实施例2(化合物14)
现提供该化合物的具体合成路线：
250ml的四口瓶，氮气保护下，加入0.01mol化合物2，0.012mol(2-氟苯基)苯基胺，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝3:1(体积比)混合溶剂打浆，重结晶后白色中间体B。
250ml的四口瓶，氮气保护下，加入0.01mol中间体B，0.025mol碳酸钾，150ml NMP，150度下搅拌反应15小时。反应完全，自然冷却至室温。将反应液加入到分液漏斗中，加400ml水，用醋酸乙酯萃取3次，合并萃取液。萃取液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后得到白色固体，纯度(HPLC)为97.8％，收率58.4％。
元素分析结构(分子式C43H27N)：理论值C,92.61；H,4.88；N,2.51；
测试值：C,92.54；H,4.93；N,2.53。
实施例3(化合物40)
现提供该化合物的具体合成路线：
250ml的四口瓶，氮气保护下，加入0.01mol中间体C，0.025mol 1-萘硼酸，0.05克pd(pph3)4(四三苯基磷合钯)，0.025mol碳酸钠，甲苯、乙醇、水各60ml，加热回流15小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后得到白色固体，纯度(HPLC)为98.5％，收率62.7％。
元素分析结构(分子式C53H37N)：理论值C,92.54；H,5.42；N,2.04；
测试值：C,92.61；H,5.50；N,1.89。
实施例4(化合物170)
现提供该化合物的具体合成路线：
250ml的四口瓶，氮气保护下，加入0.01mol中间体D，0.025mol 1-萘硼酸，0.05克pd(pph3)4(四三苯基磷合钯)，0.025mol碳酸钠，甲苯、乙醇、水各60ml，加热回流15小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后得到白色固体，纯度(HPLC)为98.1％，收率5.8％。
元素分析结构(分子式C62H42)：理论值C,94.62；H,5.38
测试值：C,94.54；H,5.46。
实施例5(化合物20)
现提供该化合物的具体合成路线：
250ml的四口瓶，氮气保护下，加入0.01mol中间体E，0.025mol苯硼酸，0.025mol1-萘硼酸，0.05克pd(pph3)4(四三苯基磷合钯)，0.025mol碳酸钠，甲苯、乙醇、水各60ml，加热回流15小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后得到白色固体，纯度(HPLC)为97.8％，收率58.8％。
元素分析结构(分子式C55H35N)：理论值C,93.06；H,4.97；N,1.97。
测试值：C,92.95；H,4.89；N,2.16。
实施例6(化合物36)
现提供该化合物的具体合成路线：
250ml的四口瓶，氮气保护下，加入0.01mol中间体F，0.0105mol 2-苯硼二苯并呋喃，0.05克pd(pph3)4(四三苯基磷合钯)，0.025mol碳酸钠，甲苯、乙醇、水各60ml，加热回流15小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后得到白色固体，纯度(HPLC)为98.4％，收率63.8％。
元素分析结构(分子式C42H32O)：理论值C,91.27；H,5.84；O,2.89。
测试值：C,91.18；H,5.89；N,2.93。
实施例7(化合物52)
现提供该化合物的具体合成路线：
250ml的四口瓶，氮气保护下，加入0.01mol中间体G，0.0105mol9-硼酸菲，0.05克pd(pph3)4(四三苯基磷合钯)，0.025mol碳酸钠，甲苯、乙醇、水各60ml，加热回流15小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后得到白色固体，纯度(HPLC)为98.5％，收率61.2％。
元素分析结构(分子式C54H36)：理论值C,94.70；H,5.30。
测试值：C,94.78；H,5.23。
实施例8(化合物81)
现提供该化合物的具体合成路线：
250ml的四口瓶，氮气保护下，加入0.01mol中间体H，0.025mol 6-硼酸喹啉，0.05克pd(pph3)4(四三苯基磷合钯)，0.025mol碳酸钠，甲苯、乙醇、水各60ml，加热回流15小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后得到白色固体，纯度(HPLC)为97.2％，收率63.6％。
元素分析结构(分子式C55H32N2O：理论值C,89.65；H,4.38；N,3.80；O,2.17
测试值：C,89.46；H,4.43；N,3.84；O,2.27
实施例9(化合物149)
现提供该化合物的具体合成路线：
250ml的四口瓶，氮气保护下，加入0.01mol中间体I，0.0105mol 4-(1-萘基)苯硼酸，0.05克pd(pph3)4(四三苯基磷合钯)，0.025mol碳酸钠，甲苯、乙醇、水各60ml，加热回流12小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后得到白色固体，纯度(HPLC)为97.8％，收率62.7％。
元素分析结构分子式C56H38O：理论值C,92.53；H,5.27；O,2.20
测试值：C,92.48；H,5.30；O,2.22
实施例10(化合物146)
现提供该化合物的具体合成路线：
250ml的四口瓶，氮气保护下，加入0.01mol中间体J，0.0105mol 4-(1-萘基)苯硼酸，0.05克pd(pph3)4(四三苯基磷合钯)，0.025mol碳酸钠，甲苯、乙醇、水各60ml，加热回流12小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后得到白色固体，纯度(HPLC)为98.4％，收率65.4％。
元素分析结构分子式C39H26O3：理论值C,86.32；H,4.83；O,8.85
测试值：C,86.41；H,4.76；O,8.83
实施例11(化合物154)
现提供该化合物的具体合成路线：
250ml的四口瓶，氮气保护下，加入0.01mol中间体K，0.011咔唑，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝3:1(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为98.6％，收率67.8％。
元素分析结构(分子式C49H29NO2)：理论值C,88.67；H,4.40；N,2.11；O,4.82
测试值：C,88.58；H,4.46；N,2.14；O,4.82
实施例12(化合物165)
现提供该化合物的具体合成路线：
250ml的四口瓶，氮气保护下，加入0.01mol中间体L，0.011mol吩噁嗪，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝3:1(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为97.9％，收率61.8％。
元素分析结构(分子式C43H29NO3)：理论值C,88.67；H,4.40；N,2.11；O,4.82
测试值：C,84.99；H,4.81；N,2.30；O,7.90
本发明化合物可以作为发光层体材料使用，也可以和其他主体材料搭配成双主体使用。对本发明化合物52、化合物170、现有材料CBP分别进行热性能、发光光谱、循环伏安稳定性的测定，检测结果如表1所示。
表1
化合物 Td(℃) Tg(℃) 单线态能级 循环伏安稳定性
化合物52 415 110 3.0eV 优
化合物170 405 125 2.9eV 优
材料CBP 353 90 2.7eV 差
注：热失重温度Td是在氮气气氛中失重1％的温度，在日本岛津公司的TGA-50H热重分析仪上进行测定，氮气流量为20mL/min；Tg日本岛津公司的DSC-60热差扫描分析仪进行测定，氮气流量为10mL/min。单线态能级是样品溶液荧光发射波长的起始位置计算得到(1240除以起始波长)，利用日本拓普康SR-3分光辐射度计测定；循环伏安稳定性是通过循环伏安法观测材料的氧化还原特性来进行鉴定；测试条件：测试样品溶于体积比为2:1的二氯甲烷和乙腈混合溶剂，浓度1mg/mL，电解液是0.1M的四氟硼酸四丁基铵或六氟磷酸四丁基铵的有机溶液。参比电极是Ag/Ag+电极，对电极为钛板，工作电极为ITO电极，循环次数为20次。
由上表数据可知，本发明化合物具有较好的氧化还原稳定性，较高的热稳定性和单线态能级，适合作为发光层的主体材料使用，能够明显提升OLED器件效率和寿命。
以下通过对比例1和实施例13～23详细说明本发明合成的材料在OLED器件上的应用效果。所述实施例13～23与对比例1相比，所述器件的制作工艺完全相同，并且所采用了相同的基板材料和电极材料，电极材料的膜厚也保持一致，所不同的是对器件中所使用的部分材料进行了一些调整，对比例1使用了本发明所述部分OLED材料。
对比例1
透明玻璃基板1采用透明材料。对ITO阳极层2(膜厚为150nm)进行洗涤，即依次进行碱洗涤、纯水洗涤、干燥后再进行紫外线-臭氧洗涤以清除透明ITO表面的有机残留物。
在进行了上述洗涤之后的ITO阳极层2上，利用真空蒸镀装置，蒸镀HAT-CN，其膜厚为10nm，这层有机材料作为空穴注入层3使用。紧接着蒸镀80nm厚度的TCTA(4,4',4”-三(咔唑-9-基)三苯胺)作为空穴传输层4。
上述空穴传输材料蒸镀结束后，制作OLED发光器件的发光层5，其结构包括OLED发光层5所使用材料CBP【4,4'-二(9-咔唑)联苯】作为主体材料，GD-19作为掺杂材料，掺杂比例为5％重量比，发光层膜厚为30nm。
在上述发光层5之后，继续真空蒸镀电子传输层材料为TPBi。该材料的真空蒸镀膜厚为40nm，此层为电子传输层6。
在电子传输层6上，通过真空蒸镀装置，制作膜厚为1nm的氟化锂(LiF)层，此层为电子注入层7。
在电子注入层7上，通过真空蒸镀装置，制作膜厚为80nm的铝(Al)层，此层为阴极反射电极层8使用。各层材料结构如下所示：
所制作的OLED发光器件器件结构如表2所示，测试结果如表3所示。
如上所述地完成OLED发光器件后，用公知的驱动电路将阳极和阴极连接起来，测量器件的发光效率，发光颜色以及器件寿命(LT95：亮度衰减到初始亮度的95％)。
实施例13
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度80nm)/发光层5(化合物05和GD-19按照100:5的重量比混掺，厚度30nm)/电子传输层6(TPBi，厚度40nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例14
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度80nm)/发光层5(化合物20和GD-19按照100:5的重量比混掺，厚度30nm)/电子传输层6(TPBi，厚度40nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例15
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度80nm)/发光层5(化合物36和GD-19按照100:5的重量比混掺，厚度30nm)/电子传输层6(TPBi，厚度40nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例16
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度80nm)/发光层5(化合物40和GD-19按照100:5的重量比混掺，厚度30nm)/电子传输层6(TPBi，厚度40nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例17
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度80nm)/发光层5(化合物81和GD-19按照100:5的重量比混掺，厚度30nm)/电子传输层6(TPBi，厚度40nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例18
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度80nm)/发光层5(化合物149和GD-19按照100:5的重量比混掺，厚度30nm)/电子传输层6(TPBi，厚度40nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例19
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度80nm)/发光层5(化合物40和GD-19按照100:5的重量比混掺，厚度30nm)/电子传输层6(TPBi，厚度40nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例20
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度80nm)/发光层5(化合物52、GH-204和GD-19按照70:30:5的重量比混掺，厚度30nm)/电子传输层6(TPBi，厚度40nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例21
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度80nm)/发光层5(化合物146、GH-204和GD-19按照70:30:5的重量比混掺，厚度30nm)/电子传输层6(TPBi，厚度40nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例22
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度80nm)/发光层5(化合物154、GH-204和GD-19按照70:30:5的重量比混掺，厚度30nm)/电子传输层6(TPBi，厚度40nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例23
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度80nm)/发光层5(化合物165、GH-204和GD-19按照70:30:5的重量比混掺，厚度30nm)/电子传输层6(TPBi，厚度40nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
表2
表3
器件代号 发光效(cd/A) 颜色 LT95寿命(H)
对比例1 6.50 绿光 3.80
实施例13 7.5 绿光 4.6
实施例14 8.0 绿光 4.4
实施例15 7.1 绿光 5.0
实施例16 7.6 绿光 5.1
实施例17 8.1 绿光 5.2
实施例18 7.7 绿光 5.0
实施例19 8.1 绿光 5.2
实施例20 8.2 绿光 5.4
实施例21 8.2 绿光 5.3
实施例22 7.8 绿光 4.8
实施例23 7.5 绿光 5.0
注：以上数据都是以对比例1作为标准器件，对比例1的电流效率为6.5cd/A(@10mA/cm2)；CIE色坐标为(0.32,0.61)；5000亮度下LT95寿命衰减为3.8Hr。寿命测试系统为本发明所有权人与上海大学共同研究的OLED器件寿命测试仪。
由表3的结果可以看出，本发明所述化合物可应用于OLED发光器件制作，并且可以获得良好的器件表现。器件的发光效率、外量子效率均得到很大改善；同时器件寿命提升非常明显。本发明所述化合物在OLED发光器件中具有良好的应用效果，并具有良好的产业化前景。
虽然已通过实施例和优选实施方式公开了本发明，但应理解，本发明不限于所公开的实施方式。相反，本领域技术人员应明白，其意在涵盖各种变型和类似的安排。因此，所附权利要求的范围应与最宽的解释相一致以涵盖所有这样的变型和类似的安排。

Claims (6)

1.一种有机电致发光化合物，其特征在于所述化合物的结构如通式(1)所示：
通式(1)中，R1表示为取代或者未取代的苯基，并且与C1-C2、C2-C3、或C3-C4键结成环；当R1表示为取代的苯基时，其取代基为氢、碳原子数1-6的烷基、芳基、或杂芳基；
R3、R4分别独立的表示为氢、碳原子数1-6的烷基、苯基；或者R3、R4通过键结形成碳原子数为10-16的芳基环；
R2表示为通式(4)、(5)、(6)中的一种：
a选自中的一种；
a与C5-C6键、C6-C7键、或C7-C8键连接；
X1、X2、X3分别独立的表示为氧原子、硫原子、C1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基或芳基取代的叔胺基中的一种；
X4、X5分别独立的表示为氢、碳原子数1-6的烷基、苯基；或者X4、X5通过键结的形成碳原子数为10-16的芳基环；
R5独立地表示为氢、碳原子数1-6的烷基、芳基、杂芳基。
2.根据权利要求1所述的有机电致发光化合物，其特征在于所述化合物材料选自通式(1a)-(3a)的任一种：
其中，通式(1a)-(3a)中的Ra分别独立的表示为氢、碳原子数1-6的烷基、芳基、杂芳基。
3.根据权利要求1或2所述的有机电致发光化合物材料，其特征在于所述Ra、R5分别独立的表示取代或未取代的苯基、吡啶基、二联苯基、三联苯基、萘基、蒽基、菲基、三嗪基、嘧啶基、喹啉基、二苯并呋喃基、二苯并噻吩基、9,9-二甲基芴基、9,9-二苯基芴基、咔唑基、苯并咔唑基、噻吩基、呋喃基、或苯并咪唑基中的一种。
4.根据权利要求1或2所述的有机电致发光化合物，其特征在于所述Ra、R5分别独立的采用通式(7)表示：
通式(7)中，X6为氧原子、硫原子、C1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基或芳基取代的叔胺基中的一种；
R6表示为氢、碳原子数1-6的烷基、芳基、或杂芳基。
5.根据权利要求1所述的有机电致发光化合物，其特征在于所述化合物的具体结构为：
中的任一种。
6.一种含有所述有机电致发光化合物的有机电致发光器件，其特征在于所述化合物作为发光层主体材料应用于有机电致发光二极管。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107089990A (zh) * 2017-06-07 2017-08-25 江苏三月光电科技有限公司 一种以芴为核心的有机化合物及其在有机电致发光器件上的应用
CN107216279A (zh) * 2017-06-12 2017-09-29 江苏三月光电科技有限公司 一种以二苯并环庚烯为核心的化合物及其在有机电致发光器件上的应用
CN107586261A (zh) * 2017-09-29 2018-01-16 江苏三月光电科技有限公司 一种含有螺二苯并环庚烯芴的有机化合物及其应用
CN109232596A (zh) * 2018-09-05 2019-01-18 大连九信精细化工有限公司 一种二苯并呋喃咔唑的合成方法
CN110655498A (zh) * 2018-06-29 2020-01-07 江苏三月光电科技有限公司 一种以二苯并环庚烯为中心骨架的化合物及其应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120093076A (ko) * 2011-02-14 2012-08-22 에스에프씨 주식회사 플루오렌 유도체 및 이를 포함하는 유기전계발광소자
CN105254561A (zh) * 2015-11-10 2016-01-20 江苏三月光电科技有限公司 一种用于oled的含芴有机化合物及其应用
CN105418357A (zh) * 2015-11-20 2016-03-23 江苏三月光电科技有限公司 一种苯并螺芴化合物及其在oled上的应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120093076A (ko) * 2011-02-14 2012-08-22 에스에프씨 주식회사 플루오렌 유도체 및 이를 포함하는 유기전계발광소자
CN105254561A (zh) * 2015-11-10 2016-01-20 江苏三月光电科技有限公司 一种用于oled的含芴有机化合物及其应用
CN105418357A (zh) * 2015-11-20 2016-03-23 江苏三月光电科技有限公司 一种苯并螺芴化合物及其在oled上的应用

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107089990A (zh) * 2017-06-07 2017-08-25 江苏三月光电科技有限公司 一种以芴为核心的有机化合物及其在有机电致发光器件上的应用
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CN107216279A (zh) * 2017-06-12 2017-09-29 江苏三月光电科技有限公司 一种以二苯并环庚烯为核心的化合物及其在有机电致发光器件上的应用
CN107216279B (zh) * 2017-06-12 2020-07-17 中节能万润股份有限公司 一种以二苯并环庚烯为核心的化合物及其在有机电致发光器件上的应用
CN107586261A (zh) * 2017-09-29 2018-01-16 江苏三月光电科技有限公司 一种含有螺二苯并环庚烯芴的有机化合物及其应用
CN107586261B (zh) * 2017-09-29 2020-12-18 中节能万润股份有限公司 一种含有螺二苯并环庚烯芴的有机化合物及其应用
CN110655498A (zh) * 2018-06-29 2020-01-07 江苏三月光电科技有限公司 一种以二苯并环庚烯为中心骨架的化合物及其应用
CN109232596A (zh) * 2018-09-05 2019-01-18 大连九信精细化工有限公司 一种二苯并呋喃咔唑的合成方法
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