CN106543071B - 一种以二苯并庚烯酮为核心的化合物及其在oled上的应用 - Google Patents

一种以二苯并庚烯酮为核心的化合物及其在oled上的应用 Download PDF

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CN106543071B
CN106543071B CN201610980016.2A CN201610980016A CN106543071B CN 106543071 B CN106543071 B CN 106543071B CN 201610980016 A CN201610980016 A CN 201610980016A CN 106543071 B CN106543071 B CN 106543071B
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叶中华
李崇
徐凯
张小庆
张兆超
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Jiangsu Sunera Technology Co Ltd
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Abstract

本发明公开了一种以二苯并庚烯酮骨架为核心的化合物及其在有机电致发光器件上的应用。该类化合物以二苯并庚烯酮为核心，材料不易结晶，具有良好成膜性和热稳定等特点；同时，该类材料具有较小的三线态和单线态能差，能够充分利用三线态能量。本发明化合物作为OLED发光器件的发光层掺杂材料使用时，器件的电流效率，功率效率和外量子效率均得到很大改善；同时，对于器件寿命提升非常明显。

Description

一种以二苯并庚烯酮为核心的化合物及其在OLED上的应用
技术领域
本发明涉及半导体技术领域，尤其是涉及一种二苯并庚烯酮化合物，以及其作为发光层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能阶等。
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；传统有机荧光材料只能利用电激发形成的25％单线态激子发光，器件的内量子效率较低(最高为25％)、导致外量子效率普遍低于5％；特别是在蓝光寿命方面，依然存在着巨大的挑战。因而，高效率、长寿命的荧光材料的研究和开发一直是产业化的热点。
热激活延迟荧光(TADF)材料是继有机荧光材料和有机磷光材料之后发展的第三代有机发光材料。该类材料一般具有小的单线态-三线态能级差(△EST)，三线态激子可以通过反系间窜越转变成单线态激子发光。这可以充分利用电激发下形成的单线态激子和三线态激子，器件的内量子效率可以达到100％。同时，材料结构可控，性质稳定，价格便宜无需贵重金属，在OLEDs领域的应用前景广阔。
因此，针对当前OLED显示照明产业的实际需求而言，荧光材料的发展还远远不够，落后于面板制造企业的要求，作为材料企业开发更高性能的有机功能荧光材料显得尤为重要。
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含有苯并咪唑的化合物及其在有机电致发光器件上的应用。本发明化合物以苯并咪唑并环为核心，作为发光层主体材料应用于有机发光二极管，本发明制作的器件具有良好的光电性能，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以二苯并庚烯酮骨架为核心的化合物，所述化合物结构如通式(1)所示：
Figure BDA0001148011930000031
通式(1)中，R1、R2分别独立的表示为氢原子、
Figure BDA0001148011930000032
或者
Figure BDA0001148011930000033
并且R1、R2不同时表示为氢原子；
其中，Ar表示苯基、C1-10直链或支链烷基取代的苯基、二联苯基、三联苯基、萘基、吡啶基、嘧啶基、哒嗪基、或吡嗪基；
R表示为取代的咔唑基或者取代的咔唑并环基团。
优选的，所述通式(1)结构中，R采用通式(2)或通式(3)所示：
Figure BDA0001148011930000034
其中，
R3、R4分别独立的表示为氢、碳原子为1-10的烷基、苯基、C1-10直链或支链烷基取代的苯基、二联苯基、三联苯基、萘基、咔唑基、通式(5)或通式(6)所示结构，且R3、R4至少有一个选取通式(4)或通式(5)所示结构；
Figure BDA0001148011930000035
通式(4)中，Ar1、Ar2分别独立的表示为取代或者未取代的芳香基或者杂芳基；通式(5)中，X表示为氧原子、硫原子、硒原子、羰基、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；
R5采用通式(4)表示；
R6采用通式(6)表示：
Figure BDA0001148011930000041
通式(6)中，a为
Figure BDA0001148011930000042
a与通式(3)中的CL1-CL2键、CL2-CL3键、或CL3-CL4键键连接。
优选的，Ar1表示为
Figure BDA0001148011930000043
或者
Figure BDA0001148011930000044
Ar2表示为
Figure BDA0001148011930000045
或者
Figure BDA0001148011930000046
其中，R7选取C1-10直链或支链烷基取代的苯基、二联苯基、三联苯基、萘基、烷基或芳基取代的芴基、烷基或芳基取代的螺芴基、烷基或芳基取代的二苯并呋喃基、烷基或芳基取代的二苯并噻吩基、烷基或芳基取代的咔唑基、烷基或芳基取代的吩嗪基、烷基或芳基取代的吩恶嗪基、烷基或芳基取代的吩噻嗪基、烷基或芳基取代的吖啶基中的一种；
R8选取烷基或芳基取代的二苯并呋喃基、烷基或芳基取代的二苯并噻吩基、烷基或芳基取代的苯并砜基、烷基或芳基取代的芴基、烷基或芳基取代的螺芴基、烷基或芳基取代的咔唑基、烷基或芳基取代的吩嗪基、烷基或芳基取代的吩恶嗪基、烷基或芳基取代的吩噻嗪基、烷基或芳基取代的吖啶基中的一种；
Ar3、Ar4分别独立的表示苯基、C1-10直链或支链烷基取代的苯基、二联苯基、三联苯基、或萘基。
更优选的，所述化合物的具体结构式为：
Figure BDA0001148011930000047
Figure BDA0001148011930000051
Figure BDA0001148011930000061
Figure BDA0001148011930000071
Figure BDA0001148011930000081
Figure BDA0001148011930000091
Figure BDA0001148011930000101
Figure BDA0001148011930000111
Figure BDA0001148011930000121
Figure BDA0001148011930000131
Figure BDA0001148011930000141
中的任一种。
本申请人还提供了一种包含所述化合物的发光器件，所述化合物作为发光层的掺杂材料，应用于OLED器件。
本发明有益的技术效果在于：
本发明化合物以二苯并庚烯酮为母核，再连接芳香杂环基团，破坏了分子对称性，从而破坏分子的结晶性，避免了分子间的聚集作用，所述化合物结构分子内包含电子给体(donor,D)与电子受体(acceptor,A)的组合，该类材料一般具有小的单线态-三线态能级差(△EST)，三线态激子可以通过反系间窜越转变成单线态激子发光。这可以充分利用电激发下形成的单线态激子和三线态激子，器件的内量子效率可以达到100％，提高发光效率，本发明化合物适合作为发光层掺杂材料使用。
本发明所述化合物为TADF材料，二苯基并庚烯酮为A结构，支链为D结构，属于D-A或者D-A-D构型的TADF材料。其D-A分离，具有较小的S1-T1能级差，且具有良好的空间分子取向排列，能大幅提高器件效率。可作为发光层掺杂材料应用于OLED发光器件制作，可以获得良好的器件表现，器件的电流效率，功率效率和外量子效率均得到很大改善；同时，对于器件寿命提升非常明显。
本发明所述化合物材料在OLED发光器件中具有良好的应用效果，与TADF现有母核(A)方向和分子定向排列相比，有非常高的应用潜力和产业化前景。
附图说明
图1为使用本发明化合物的器件结构示意图；
其中，1为透明基板层，2为ITO阳极层，3为空穴注入层，4为空穴传输层，5为发光层，6为电子传输层，7为电子注入层，8为阴极反射电极层。
图2～5分别为化合物46、化合物83、化合物91、化合物GD-19的可视化效果图。
具体实施方式
下面结合附图和实施例，对本发明进行具体描述。
实施例1 化合物02的合成
Figure BDA0001148011930000151
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 3-溴二苯并庚烯酮，0.011mol中间体a，0.03mol碳酸钠，1×10-4mol四(三苯基磷)钯，50ml甲苯，50ml乙醇，50ml水，加热回流20小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度98.40％，收率60.6％。元素分析结构(分子式C45H30N2O)：理论值C,87.92；H,4.92；N,4.56；O,2.60；
测试值：C,87.86；H,4.89；N,4.60；O,2.65
HPLC-MS：材料分子量为614.73，实测分子量614.81。
实施例2 化合物46的合成
Figure BDA0001148011930000161
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 2-溴二苯并庚烯酮，0.011mol中间体b，0.03mol碳酸钠，1×10-4mol四(三苯基磷)钯，50ml甲苯，50ml乙醇，50ml水，加热回流20小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度98.60％，收率61.5％。
元素分析结构(分子式C57H39N3O)：理论值C,87.55；H,5.03；N,5.37；O,2.05；
测试值：C,87.56；H,4.95；N,5.38；O,2.11
HPLC-MS：材料分子量为781.94，实测分子量781.87。
实施例3 化合物48的合成
Figure BDA0001148011930000162
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 2-溴二苯并庚烯酮，0.011mol中间体c，0.03mol碳酸钠，1×10-4mol四(三苯基磷)钯，50ml甲苯，50ml乙醇，50ml水，加热回流20小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度99.20％，收率63.0％。
元素分析结构(分子式C67H41N3O)：理论值C,87.42；H,5.65；N,5.01；O,1.91；
测试值：C,87.50；H,5.61；N,5.05；O,1.84
HPLC-MS：材料分子量为835.05，实测分子量835.10。
实施例4 化合物49的合成
Figure BDA0001148011930000171
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 2-溴二苯并庚烯酮，，0.012mol中间体d，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24小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度98.7％，收率58.7％。
元素分析结构(分子式C51H35N3O)：理论值C,86.78；H,5.00；N,5.95；O,2.27；
测试值：C,86.76；H,4.96；N,6.01；O,2.27
HPLC-MS：材料分子量为705.84，实测分子量705.90。
实施例5 化合物50的合成
Figure BDA0001148011930000172
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 3-溴二苯并庚烯酮，0.011mol中间体b，0.03mol碳酸钠，1×10-4mol四(三苯基磷)钯，50ml甲苯，50ml乙醇，50ml水，加热回流20小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度99.40％，收率64.5％。
元素分析结构(分子式C57H39N3O)：理论值C,87.55；H,5.03；N,5.37；O,2.05；
测试值：C,87.54；H,4.95；N,5.35；O,2.16
HPLC-MS：材料分子量为781.94，实测分子量781.87。
实施例6 化合物51的合成
Figure BDA0001148011930000181
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 3-溴二苯并庚烯酮，，0.012mol中间体d，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24小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度98.4％，收率56.6％。
元素分析结构(分子式C51H35N3O)：理论值C,86.78；H,5.00；N,5.95；O,2.27；
测试值：C,86.80；H,4.99；N,5.99；O,2.22
HPLC-MS：材料分子量为705.84，实测分子量705.88。
实施例7 化合物57的合成
Figure BDA0001148011930000182
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 3-溴二苯并庚烯酮，0.011mol中间体f，0.03mol碳酸钠，1×10-4mol四(三苯基磷)钯，50ml甲苯，50ml乙醇，50ml水，加热回流20小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度99.10％，收率62.5％。
元素分析结构(分子式C64H50N2O)：理论值C,89.06；H,5.84；N,3.25；O,1.85；
测试值：C,89.04；H,5.90；N,3.28；O,1.78
HPLC-MS：材料分子量为863.00，实测分子量863.05。
实施例8 化合物64的合成
Figure BDA0001148011930000183
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 3-溴二苯并庚烯酮，0.012mol中间体g，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24小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度98.30％，收率57.90％。
元素分析结构(分子式C67H63N3O)：理论值C,86.88；H,6.86；N,4.54；O,1.73；
测试值：C,86.84；H,6.90；N,4.49；O,1.77
HPLC-MS：材料分子量为926.24，实测分子量926.30。
实施例9 化合物68的合成
Figure BDA0001148011930000191
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 3-溴二苯并庚烯酮，0.012mol中间体h，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24小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度98.50％，收率59.50％。
元素分析结构(分子式C57H43N3O)：理论值C,87.10；H,5.51N,5.35；O,2.04
测试值：C,87.14；H,5.46；N,5.40；O 2.00
HPLC-MS：材料分子量为785.97，实测分子量785.99。
实施例10 化合物83的合成
Figure BDA0001148011930000192
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 3-溴二苯并庚烯酮，0.012mol中间体i，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24小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度98.65％，收率58.20％。
元素分析结构(分子式C45H28N2O2)：理论值C,85.97；H,4.49；N,4.46；O,5.09
测试值：C,85.94；H,4.46；N,4.49；O,5.11
HPLC-MS：材料分子量为628.72，实测分子量628.68。
实施例11 化合物89的合成
Figure BDA0001148011930000201
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 3-溴二苯并庚烯酮，0.012mol中间体j，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24小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度99.10％，收率59.8％。
元素分析结构(分子式C48H34N2O)：理论值C,88.04；H,5.23；N,4.28；O,2.44
测试值：C,88.10；H,5.26；N,4.31；O,2.33
HPLC-MS：材料分子量为654.80，实测分子量654.74。
实施例12 化合物91的合成
Figure BDA0001148011930000202
250ml的四口瓶，在通入氮气的气氛下，加入0.01mol 3-溴二苯并庚烯酮，0.011mol中间体k，0.03mol碳酸钠，1×10-4mol四(三苯基磷)钯，50ml甲苯，50ml乙醇，50ml水，加热回流20小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，过硅胶柱，得到目标产物，纯度99.30％，收率66.3％。
元素分析结构(分子式C54H38N2O)：理论值C,88.74；H,5.24；N,3.83；O,2.19；
测试值：C,88.80；H,5.20；N,3.86；O,2.14
HPLC-MS：材料分子量为730.89，实测分子量730.95。
本发明化合物可以作为发光层掺杂材料使用，对本发明化合物46、化合物91和现有材料GD-19分别进行热性能、荧光量子效率、三线态-三线态能级差以的测定，检测结果如表1所示。
表1
化合物 Td(℃) PLQY △Est(eV) HOMO(eV) 循环伏安稳定性
化合物46 395 96 0.105 -5.55 优
化合物91 405 92 0.090 -5.60 优
GD-19 375 88 0.750 -5.65 一般
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；λPL是样品溶液荧光发射波长，利用日本拓普康SR-3分光辐射度计测定；Φf是固体粉末荧光量子效率(利用美国海洋光学的Maya2000Pro光纤光谱仪，美国蓝菲公司的C-701积分球和海洋光学LLS-LED光源组成的测试固体荧光量子效率测试系统，参照文献Adv.Mater.1997，9，230-232的方法进行测定)；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高的热稳定性，较小的单线态-三线态能级差，较高的Φf，使得应用本发明化合物作为掺杂材料的OLED器件效率和寿命得到提升。
CBP作为主体材料，本发明化合物作为掺杂发光材料(掺杂质量浓度为8％)，共蒸制作成有机膜。用365nm的紫外光进行激发，测定有机膜荧光强度随测试角度分布情况，通过光学拟合软件测定其各向异性因子α。
α越小，表明有机膜掺杂材料的水平发光子成分越多，掺杂材料辐射发光的利用率越高。测试结果如表2所示:
表2
有机膜(15nm) α(度)
CBP:化合物46(8wt％) 8.4
CBP:化合物83(8wt％) 10.2
CBP:化合物91(8wt％) 12.0.
CBP:GD-19(8wt％) 35
注：有机膜通过ANS蒸镀设备进行双源共蒸，蒸镀基底为高透石英玻璃，客体的掺杂质量浓度为8％。蒸镀完毕后，在手套箱中进行封装(水和氧气的浓度小于1ppm)。样品通过折射率匹配液放置于熔融硅半圆柱棱镜中，通过旋转台改变发光角度,光谱测试采用Sphere Optics SMS-500型光谱仪。
从表2可以看到相对于传统掺杂材料GD-19,本发明化合物的发光子各向异性因子小，因此可以提高有机层的出光效率,提升OLED器件效率。
通过量子化学从头计算软件ORCA对本发明化合物的HOMO、LUMO能级进行计算并进行可视化，计算方法采用B3LYP杂化泛函，基组6-31g(d)。化合物46的可视化效果如图2所示；化合物83的可视化效果如图3所示；化合物91的可视化效果如图4所示；化合物GD-19的可视化效果如图5所示。
从HOMO、LUMO在分子中的空间分布可以看大，本发明化合物的HOMO和LUMO能级处于空间分离状态，HOMO、LUMO重叠度小，从而导致单线态-三线态能级差小，有利于三线态激子通过热激发转化为单线态激子，理论上可使器件内量子效率达到100％。
以下通过实施例13-24和比较例1-2详细说明本发明合成的化合物在器件中作为发光层掺杂材料的应用效果。实施例14-24与实施例13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，所不同的是器件中发光层材料发生了改变。实施例13-24与比较例1-2相比，比较例1所述器件的发光层材料采用的是现有常用原料，而实施例13-24的器件发光层掺杂材料采用的是本发明化合物。各实施例所得器件的结构组成如表3所示。各器件的性能测试结果如表4所示。
实施例13
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP和化合物02按照100：8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)。各相关材料的分子结构式如下所示：
Figure BDA0001148011930000221
Figure BDA0001148011930000231
具体制备过程如下：
透明基板层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，蒸镀膜厚为10nm的三氧化钼MoO3作为空穴注入层3使用。紧接着蒸镀80nm厚度的TAPC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作为主体材料，化合物02作为掺杂材料，掺杂材料掺杂比例为58％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。
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，发光光谱以及器件的电流-电压特性。
实施例14
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP和化合物46按照100:8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)。
实施例15
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP和化合物48按照100:8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)。
实施例16
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP和化合物49按照100:8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)。
实施例17
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP和化合物50按照100:8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)。
实施例18
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP和化合物51按照100:8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)。
实施例19
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP和化合物57按照100:8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)。
实施例20
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP和化合物64按照100:8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)。
实施例21
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP和化合物68按照100:8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)。
实施例22
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP和化合物83按照100:8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)。
实施例23
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP、GH-204和化合物89按照70:30:8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)。
实施例24
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP、GH-204和化合物91按照70:30:8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)。
比较例1
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP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)。
比较例2
ITO阳极层2/空穴注入层3(三氧化钼MoO3，厚度10nm)/空穴传输层4(TAPC，厚度80nm)/发光层5(CBP、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)/阴极电极层8(Al)。
所制作的OLED发光器件的测试结果见表4。
表3
Figure BDA0001148011930000261
表4
Figure BDA0001148011930000262
Figure BDA0001148011930000271
说明:器件测试性能以比较例1作为参照，比较例1器件各项性能指标设为1.0。比较例1的电流效率为15.0cd/A(@10mA/cm2)；CIE色坐标为(0.32,0.61)；5000亮度下LT95寿命衰减为6.5Hr。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。
表4的结果可以看出本发明所述化合物作为发光层掺杂材料可应用与OLED发光器件制作，并且与比较例1、2相比，无论是效率还是寿命均比已知OLED材料获得较大改观，特别是器件的驱动寿命获得较大的提升。
从以上数据应用来看，本发明化合物作为发光层掺杂材料在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。
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 (2)

1.一种以二苯并庚烯酮骨架为核心的化合物，其特征在于所述化合物的具体结构式为：
Figure FDA0002414222930000011
Figure FDA0002414222930000021
中的任一种。
2.一种包含权利要求1所述化合物的发光器件，其特征在于所述化合物作为发光层的掺杂材料，应用于OLED器件。
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