CN107226811A - 一种以二联二苯并五元杂环为骨架的有机化合物及其在oled上的应用 - Google Patents
一种以二联二苯并五元杂环为骨架的有机化合物及其在oled上的应用 Download PDFInfo
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- CN107226811A CN107226811A CN201710422476.8A CN201710422476A CN107226811A CN 107226811 A CN107226811 A CN 107226811A CN 201710422476 A CN201710422476 A CN 201710422476A CN 107226811 A CN107226811 A CN 107226811A
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- WNNKEBCYWWGOBS-UHFFFAOYSA-N acridine toluene Chemical compound C1=CC=CC2=NC3=CC=CC=C3C=C12.CC=1C=CC=CC1 WNNKEBCYWWGOBS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
- C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/38—[b, e]-condensed with two six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- H10K50/00—Organic light-emitting devices
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- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Abstract
本发明涉及一种以二联二苯并五元杂环为骨架有机化合物及其在OLED器件上的应用，该化合物二联二苯并五元杂环为骨架，支链是苯基、二联苯或萘基引出的芳香结构。本发明化合物具有较高的玻璃化温度和分子热稳定性，合适的HOMO和LUMO能级，较高的Eg；通过器件结构优化，可有效提升OLED器件的光电性能以及OLED器件的寿命。
Description
技术领域
本发明涉及半导体技术领域，尤其是涉及一种有机化合物及其在有机电致发光器件上的应用。
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。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。OLED发光器件作为电流器件，当对其两端电极施加电压，并通过电场作用有机层功能材料膜层中的正负电荷时，正负电荷进一步在发光层中复合，即产生OLED电致发光。
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器件的发光效率和使用寿命等性能还需要进一步提升。目前对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，创制出更高性能的OLED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，分别为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、电子阻挡材料、空穴注入传输材料和空穴阻挡材料，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性能，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，作为发光层的主体材料具有良好双极性，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、电子阻挡层、发光层、空穴阻挡层、电子传输层、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括空穴注入材料、空穴传输材料、发光材料、电子传输材料等，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。
因此，针对当前OLED器件的产业应用要求以及OLED器件的不同功能膜层，器件的光电特性需求，必须选择更适合、性能更高的OLED功能材料或材料组合，才能实现器件的高效率、长寿命和低电压的综合特性。就当前的OLED显示照明产业的实际需求而言，目前OLED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有机化合物及其在有机电致发光器件上的应用。本发明化合物具有较高的玻璃化温度和分子热稳定性，合适的HOMO和LUMO能级，较高Eg，通过器件结构优化，可有效提升OLED器件的光电性能以及OLED器件的寿命。
本发明的技术方案如下：
本申请人提供了一种以二联二苯并五元杂环为骨架的有机化合物，所述有机化合物的结构如通式(1)所示：
通式(1)中，X1和X2分别独立地表示为氧原子、硫原子、或N-R3，其中R3表示为烷基取代或者未取代的苯基、烷基取代或者未取代的二联苯基、或烷基取代或者未取代的萘基；
R1和R2分别独立地表示为苯基、二联苯或萘基，R1和R2还可以分别独立地表示为单键；
Ar1和Ar2分别独立地表示为通式(2)、通式(3)或通式(4)的结构：
优选的，所述以二联二苯并五元杂环为骨架的有机化合物的结构如通式(5)所示：
优选的，所述以二联二苯并五元杂环为骨架的有机化合物的具体结构式为：
中的任一项。
所述以二联二苯并五元杂环为骨架的有机化合物的制备过程中发生的反应方程式为：
反应A：
具体制备方法为：
称取中间体1、中间体2和中间体3用甲苯溶解，再加入Pd2(dba)3和叔丁醇钠；在惰性气氛下，将上述反应物的混合溶液于反应温度90～110℃下反应10～24小时，冷却、过滤反应溶液，滤液旋蒸，过硅胶柱，得到目标产物；
所述中间体1与中间体2的摩尔比为1:1.0～1.5；中间体1与中间体3的摩尔比为1:1.0～1.5；Pd2(dba)3与中间体1的摩尔比为0.006～0.02:1，叔丁醇钠与中间体1的摩尔比为2.0～3.0:1；
或者反应B：
将中间体4、中间体5和中间体6溶解于甲苯和乙醇的混合溶液中，除氧后加入Pd(PPh3)4和K2CO3，在惰性气氛下95～110℃反应10～24小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到目标化合物；
所述中间体5与中间体4的摩尔比为1.0～2.5:1，中间体6与中间体4的摩尔比为1.0～2.5:1，Pd(PPh3)4与中间体4的摩尔比为0.01～0.03:1，K2CO3与中间体4的摩尔比为2.5～4:1。
本申请人还提供了一种所述的以二联二苯并五元杂环为骨架的有机化合物用于制备有机电致发光器件的应用方法。
本申请人还提供了一种有机电致发光器件，所述有机电致发光器件包括至少一层功能层含有所述的以二联二苯并五元杂环为骨架的有机化合物。
本申请人还提供了一种有机电致发光器件，包括电子阻挡层，所述电子阻挡层材料为所述的以二联二苯并五元杂环为骨架的有机化合物。
本申请人还提供了一种有机电致发光器件，包括发光层，所述发光层含有所述的以二联二苯并五元杂环为骨架的有机化合物。
本发明有益的技术效果在于：
本发明的有机化合物的结构使得电子和空穴在发光层的分布更加平衡，在恰当的HOMO能级下，提升了空穴注入和传输性能；在合适的LUMO能级下，又起到了电子阻挡的作用，提升激子在发光层中的复合效率；作为OLED发光器件的发光功能层材料使用时，本发明分子可有效提高激子利用率和高荧光辐射效率，降低高电流密度下的效率滚降，降低器件电压，提高器件的电流效率和寿命。
本发明化合物均以二联二苯并五元杂环为骨架，碳碳键连接既提高了材料稳定性又避免了支链基团活泼位置裸露；此类化合物是一个大π键共轭的刚性结构，空间位阻大，不易转动，使得本发明化合物材料的立体结构更加稳定；同时，大π键共轭能够分散分子上电子云，电子云密度降低，使得分子的电化学稳定性提高，器件寿命得到提高。本发明化合物作为OLED的电子阻挡层材料使用时，高T1能级能够有效地阻挡能量从发光层向空穴传输层传递，减少了能量损失，使发光层主体材料能量充分传递至掺杂材料，从而提升材料应用于器件后的发光效率。
本发明的有机化合物在OLED器件应用时，通过器件结构优化，可保持高的膜层稳定性，可有效提升OLED器件的光电性能以及OLED器件的寿命。本发明所述化合物在OLED发光器件中具有良好的应用效果和产业化前景。
附图说明
图1为本发明所列举的材料应用于OLED器件的结构示意图；其中，1、透明基板层，2、ITO阳极层，3、空穴注入层，4、空穴传输层5、电子阻挡层，6、发光层，7、空穴阻挡/电子传输层，8、电子注入层，9、阴极反射电极层。
具体实施方式
实施例1：化合物3的合成
250mL的三口瓶，在通入氮气的气氛下，加入0.02mol的原料I，0.015mol Cu粉，再加入150mL无水DMF，100℃加热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，得到中间体I；
在250mL的三口瓶中，通氮气保护下，加入0.008mol中间体I、0.02mol吖啶甲苯，搅拌混合，再加入0.03mol叔丁醇钠、0.002molPd2(dba)3、0.002mol三叔丁基膦，搅拌加热至115℃，回流反应24小时，取样点板，显示无中间体I剩余，反应完全；自然冷却至室温，过滤，滤液减压旋蒸至无馏分，过中性硅胶柱，得到化合物3，HPLC纯度99.1％，收率65.9％；
元素分析结构(分子式C54H40N2O2)：理论值C,86.60；H,5.38；N,3.74；测试值：C,86.68；H,5.35；N,3.76。ESI-MS(m/z)(M+)：理论值为748.91，实测值为748.36。
实施例2：化合物7的合成
250mL的三口瓶，在通入氮气的气氛下，加入0.02mol的原料I，0.015mol Cu粉，再加入150mL无水DMF，100℃加热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，得到中间体II；
在250mL的三口瓶中，通氮气保护下，加入0.008mol中间体II、0.02mol吩恶嗪，搅拌混合，再加入0.03mol叔丁醇钠、0.002molPd2(dba)3、0.002mol三叔丁基膦，搅拌加热至115℃，回流反应24小时，取样点板，显示无中间体II剩余，反应完全；自然冷却至室温，过滤，滤液减压旋蒸至无馏分，过中性硅胶柱，得到化合物7，HPLC纯度99.1％，收率65.9％；
元素分析结构(分子式C54H40N2O2)：理论值C,86.60；H,5.38；N,3.74；测试值：C,86.68；H,5.35；N,3.76。ESI-MS(m/z)(M+)：理论值为748.31，实测值为748.76。
实施例3：化合物9的合成
化合物9的合成步骤与化合物7相似，只是把吩恶嗪换成了吖啶；
元素分析结构(分子式C60H52N2)：理论值C,89.96；H,6.54；N,3.50；测试值：C,89.91；H,6.56；N,3.56。ESI-MS(m/z)(M+)：理论值为801.07，实测值为801.14。
实施例4：化合物14的合成
在250mL的三口瓶中，通氮气保护下，加入0.008mol中间体II、0.01mol吩恶嗪和0.01mol吖啶，搅拌混合，再加入0.03mol叔丁醇钠、0.002molPd2(dba)3、0.002mol三叔丁基膦，搅拌加热至115℃，回流反应24小时，取样点板，显示无中间体II剩余，反应完全；自然冷却至室温，过滤，滤液减压旋蒸至无馏分，过中性硅胶柱，得到化合物14，HPLC纯度99.3％，收率64.2％；
元素分析结构(分子式C57H46N2O)：理论值C,88.34；H,5.98；N,3.61；测试值：C,88.28；H,6.01；N,3.66。ESI-MS(m/z)(M+)：理论值为774.99，实测值为774.54。
实施例5：化合物21的合成
在250mL的三口瓶中，通氮气保护下，加入0.03mol吩恶嗪、0.036mol 1,4-二溴苯、150mL甲苯，搅拌混合，再加入0.09mol叔丁醇钠、0.002molPd2(dba)3，搅拌加热至115℃，回流反应24小时；自然冷却至室温，过滤，滤液减压旋蒸至无馏分，过中性硅胶柱，得到中间体III；
在250mL的三口瓶中，通氮气保护下，依次加入0.02mol中间体III、0.025mol联硼酸频那醇酯、0.04mol碳酸钾、0.002mol Pd(pph3)4、100/30mL甲苯/乙醇混合液，搅拌混合，加热至80℃，反应24小时，取样点板，显示无中间体III剩余，反应完全；自然冷却至室温，加水后有固体析出，过滤，取滤饼用真空干燥箱烘干，然后过中性硅胶柱，得到中间体IV；
在250mL的三口瓶中，通氮气保护下，加入0.01mol中间体II，0.022mol中间体IV，150mL甲苯/50mL乙醇搅拌混合，然后加入20mL碳酸钾水溶液(2M)，1×10-4molPd(PPh3)4，加热至105℃，回流反应24小时，取样点板，显示无原料剩余，反应完全；自然冷却至室温，过滤，滤液进行减压旋蒸(-0.09MPa，85℃)，过中性硅胶柱，得到化合物21，HPLC纯度99.3％，收率65.8％；
元素分析结构(分子式C66H48N2O2)：理论值C,87.97；H,5.37；N,3.11；测试值：C,87.95；H,6.39；N,3.13。ESI-MS(m/z)(M+)：理论值为901.10，实测值为901.17。
实施例6：化合物23的合成
化合物23的合成步骤与化合物21相似，只是把吩恶嗪换成了吖啶；
元素分析结构(分子式C72H60N2)：理论值C,90.72；H,6.34；N,2.94；测试值：C,90.78；H,6.31；N,2.95。ESI-MS(m/z)(M+)：理论值为953.26，实测值为953.31。
实施例7：化合物26的合成
化合物26的合成步骤与化合物23相似，只是把对二溴苯换成了间二溴苯；
元素分析结构(分子式C72H60N2)：理论值C,90.72；H,6.34；N,2.94；测试值：C,90.78；H,6.31；N,2.95。ESI-MS(m/z)(M+)：理论值为953.26，实测值为953.31。
实施例8：化合物35的合成
化合物35的合成步骤与化合物23相似，只是把对二溴苯换成了邻二溴苯；
元素分析结构(分子式C72H60N2)：理论值C,90.72；H,6.34；N,2.94；测试值：C,90.75；H,6.33；N,2.96。ESI-MS(m/z)(M+)：理论值为953.26，实测值为953.56。
实施例9：化合物45的合成
化合物35的合成步骤与化合物23相似，只是把对二溴苯换成了邻二溴苯；
元素分析结构(分子式C84H68N2)：理论值C,91.27；H,6.20；N,2.53；测试值：C,91.22；H,6.30；N,2.46。ESI-MS(m/z)(M+)：理论值为1105.45，实测值为1105.36。
本发明的有机化合物在发光器件中使用，可以作为电子阻挡层材料，也可以作为发光层主客体材料使用。对本发明化合物3、7、9、14、21、23、26、35和45分别进行热性能、HOMO能级的测试，检测结果如表1所示。
表1
注：玻璃化温度Tg由示差扫描量热法(DSC，德国耐驰公司DSC204F1示差扫描量热仪)测定，升温速率10℃/min；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；最高占据分子轨道HOMO能级是由电离能量测试系统(IPS3)测试，测试为大气环境。
由上表数据可知，本发明的有机化合物具有不同的HOMO能级，可应用于不同的功能层，本发明化合物具有较高的热稳定性，使得所制作的含有本发明有机化合物的OLED器件寿命提升。
以下通过器件实施例1～9和比较例1详细说明本发明合成的OLED材料在器件中的应用效果。
器件实施例1：如图1所示，一种电致发光器件，其制备步骤包括：
a)清洗透明基板层1上的ITO阳极层2，分别用去离子水、丙酮、乙醇超声清洗各15分钟，然后在等离子体清洗器中处理2分钟；
b)在ITO阳极层2上，通过真空蒸镀方式蒸镀空穴注入层材料HAT-CN，厚度为10nm，这层作为空穴注入层3；
c)在空穴注入层3上，通过真空蒸镀方式蒸镀空穴传输材料NPB，厚度为60nm，该层为空穴传输层4；
d)在空穴传输层4上，通过真空蒸镀方式蒸镀电子阻挡层材料NPB，厚度为20nm，该层为电子阻挡层5；
e)在电子阻挡层5之上蒸镀发光层6，使用本发明化合物3作为主体材料，Ir(ppy)3作为掺杂材料，Ir(ppy)3和化合物3的质量比为10:90，厚度为30nm；
f)在发光层6之上，通过真空蒸镀方式蒸镀电子传输材料TPBI，厚度为40nm，这层有机材料作为空穴阻挡/电子传输层7使用；
g)在空穴阻挡/电子传输层7之上，真空蒸镀电子注入层LiF，厚度为1nm，该层为电子注入层8；
h)在电子注入层8之上，真空蒸镀阴极Al(100nm)，该层为阴极反射电极层9；
按照上述步骤完成电致发光器件的制作后，测量器件的电流效率和寿命，其结果见表2所示。相关材料的分子结构式如下所示：
器件实施例2
本实施例与器件实施例1的不同之处在于：电致发光器件的电子阻挡层材料为本发明化合物7，电致发光器件的发光层主体材料为CBP，掺杂材料为Ir(ppy)3，Ir(ppy)3和CBP的质量比为10:90，所得电致发光器件的检测数据见表2所示。
器件实施例3
本实施例与器件实施例1的不同之处在于：电致发光器件的发光层主体材料变为本发明化合物9，掺杂材料为Ir(ppy)3，Ir(ppy)3和化合物9的质量比为10:90，所得电致发光器件的检测数据见表2所示。
器件实施例4
本实施例与器件实施例1的不同之处在于：电致发光器件的电子阻挡层材料为本发明化合物14，电致发光器件的发光层主体材料为CBP，掺杂材料为Ir(ppy)3，Ir(ppy)3和CBP的质量比为10:90，所得电致发光器件的检测数据见表2所示。
器件实施例5
本实施例与器件实施例1的不同之处在于：电致发光器件的电子阻挡层材料为本发明化合物21，电致发光器件的发光层主体材料为CBP，掺杂材料为Ir(ppy)3，Ir(ppy)3和CBP的质量比为10:90，所得电致发光器件的检测数据见表2所示。
器件实施例6
本实施例与器件实施例1的不同之处在于：电致发光器件的发光层主体材料变为本发明化合物23，掺杂材料为Ir(ppy)3，Ir(ppy)3和化合物23的质量比为10:90，所得电致发光器件的检测数据见表2所示。
器件实施例7
本实施例与器件实施例1的不同之处在于：电致发光器件的发光层主体材料变为本发明化合物26，掺杂材料为Ir(ppy)3，Ir(ppy)3和化合物26的质量比为10:90，所得电致发光器件的检测数据见表2所示。
器件实施例8
本实施例与器件实施例1的不同之处在于：电致发光器件的发光层主体材料变为本发明化合物35，掺杂材料为Ir(ppy)3，Ir(ppy)3和化合物35的质量比为10:90，所得电致发光器件的检测数据见表2所示。
器件实施例9
本实施例与器件实施例1的不同之处在于：电致发光器件的发光层主体材料变为本发明化合物45，掺杂材料为Ir(ppy)3，Ir(ppy)3和化合物45的质量比为10:90，所得电致发光器件的检测数据见表2所示。
器件比较例1
本实施例与器件实施例1的不同之处在于：电致发光器件的电子阻挡层材料为NPB，电致发光器件的发光层主体材料变为公知化合物CBP，掺杂材料为Ir(ppy)3，Ir(ppy)3和CBP的质量比为10:90，所得电致发光器件的检测数据见表2所示。
表2
| 编号 | 电流效率(cd/A) | 色彩 | LT95寿命(Hr)@5000nits |
| 器件实施例1 | 39.3 | 绿光 | 13.2 |
| 器件实施例2 | 36.4 | 绿光 | 12.3 |
| 器件实施例3 | 42.2 | 绿光 | 12.6 |
| 器件实施例4 | 36.5 | 绿光 | 11.5 |
| 器件实施例5 | 44.7 | 绿光 | 13.8 |
| 器件实施例6 | 42.4 | 绿光 | 13.1 |
| 器件实施例7 | 45.3 | 绿光 | 14.2 |
| 器件实施例8 | 39.7 | 绿光 | 13.5 |
| 器件实施例9 | 40.5 | 绿光 | 14.1 |
| 器件比较例1 | 28 | 绿光 | 2.5 |
注：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2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，并且与器件比较例1相比，无论是效率还是寿命均比已知OLED材料获得较大改观，特别是器件的寿命衰减获得较大的提升。
进一步的本发明材料制备的的OLED器件在高温下能够保持长寿命，将器件实施例1～9和器件比较例1在85℃进行高温驱动寿命测试，所得结果如表3所示。
表3
从表3的数据可知，器件实施例1～9为本发明材料和已知材料搭配的器件结构，和器件比较例1相比，高温下，本发明提供的OLED器件具有很好的驱动寿命。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (8)
1.一种以二联二苯并五元杂环为骨架的有机化合物，其特征在于，所述有机化合物的结构如通式(1)所示：
通式(1)中，X1和X2分别独立地表示为氧原子、硫原子、或N-R3，其中R3表示为烷基取代或者未取代的苯基、烷基取代或者未取代的二联苯基、或烷基取代或者未取代的萘基；
R1和R2分别独立地表示为苯基、二联苯或萘基，R1和R2还可以分别独立地表示为单键；
Ar1和Ar2分别独立地表示为通式(2)、通式(3)或通式(4)的结构：
2.根据权利要求1所述的有机化合物，其特征在于，所述有机化合物的结构如通式(5)所示：
3.根据权利要求1所述的有机化合物，其特征在于，所述有机化合物的具体结构式为：
中的任一项。
4.一种权利要求1～3任一项所述有机化合物的制备方法，其特征在于，制备过程中发生的反应方程式为：
反应A：
具体制备方法为：
称取中间体1、中间体2和中间体3用甲苯溶解，再加入Pd2(dba)3和叔丁醇钠；在惰性气氛下，将上述反应物的混合溶液于反应温度90～110℃下反应10～24小时，冷却、过滤反应溶液，滤液旋蒸，过硅胶柱，得到目标产物；
所述中间体1与中间体2的摩尔比为1:1.0～1.5；中间体1与中间体3的摩尔比为1:1.0～1.5；Pd2(dba)3与中间体1的摩尔比为0.006～0.02:1，叔丁醇钠与中间体1的摩尔比为2.0～3.0:1；
或者反应B：
将中间体4、中间体5和中间体6溶解于甲苯和乙醇的混合溶液中，除氧后加入Pd(PPh3)4和K2CO3，在惰性气氛下95～110℃反应10～24小时，反应过程中不断用TLC监测反应进程，待原料反应完全后，冷却、过滤，将滤液旋蒸除去溶剂，粗产品过硅胶柱，得到目标化合物；
所述中间体5与中间体4的摩尔比为1.0～2.5:1，中间体6与中间体4的摩尔比为1.0～2.5:1，Pd(PPh3)4与中间体4的摩尔比为0.01～0.03:1，K2CO3与中间体4的摩尔比为2.5～4:1。
5.一种如权利要求1～3任一项所述的以二联二苯并五元杂环为骨架的有机化合物用于制备有机电致发光器件。
6.一种有机电致发光器件，其特征在于，所述有机电致发光器件包括至少一层功能层含有权利要求1～3任一项所述的以二联二苯并五元杂环为骨架的有机化合物。
7.一种有机电致发光器件，包括电子阻挡层，其特征在于，所述电子阻挡层材料为权利要求1～3任一项所述的以二联二苯并五元杂环为骨架的有机化合物。
8.一种有机电致发光器件，包括发光层，其特征在于，所述发光层含有权利要求1～3任一项所述的以二联二苯并五元杂环为骨架的有机化合物。
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