CN111662191A - 一种三芳胺类有机化合物及其应用 - Google Patents
一种三芳胺类有机化合物及其应用 Download PDFInfo
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- CN111662191A CN111662191A CN201910178092.5A CN201910178092A CN111662191A CN 111662191 A CN111662191 A CN 111662191A CN 201910178092 A CN201910178092 A CN 201910178092A CN 111662191 A CN111662191 A CN 111662191A
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- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
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- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
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- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
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- C07D221/20—Spiro-condensed ring systems
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
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- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
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- 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
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- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
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Abstract
本发明涉及一种三芳胺类有机化合物及其应用，属于半导体技术领域，本发明提供化合物的结构如通式(I)所示：
本发明还公开了上述化合物的应用。本发明提供的化合物具有较强的空穴传输能力，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，搭配本发明范围内的支链可有效提高激子利用率和辐射效率。
Description
技术领域
本发明涉及半导体技术领域，尤其涉及一种三芳胺类有机化合物及其应用。
背景技术
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的正负电荷，正负电荷进一步在发光层中复合，即产生OLED电致发光。
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。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、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，作为发光层的主体材料要求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含空穴注入材料，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，具有高性能的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，本发明申请人提供了一种三芳胺类有机化合物及其应用。本发明化合物具有较高的玻璃化转变温度和分子热稳定性，合适的HOMO能级，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：一种三芳胺类有机化合物，该化合物的结构如通式(I)所示：
所述L1、L2分别独立地表示为单键、亚苯基、亚联苯基、亚萘基、亚吡啶基或亚萘啶基；
所述Ar表示为取代或未取代的C6-30芳基、取代或未取代的含有一个或多个杂原子的5至30元杂芳基；
所述X表示为氧原子、硫原子、-C(R1)(R2)-或-N(R3)-；其中，R1～R3各自独立的表示为C1-10烷基、取代或未取代的C6-30芳基、取代或未取代的含有一个或多个杂原子的5-30元杂芳基中的一种；R1与R2还可以相互键结成环；
所述Z每次出现相同或不同的表示为氮原子或C-R；其中，与基团L1或L2键合的Z表示为碳原子；
所述R表示为氢原子、氘原子、氚原子、氰基、卤素、C1-10的烷基、C2-10的烯烃基、取代或未取代的C6-30芳基、取代或未取代的含有一个或多个杂原子的5至30元杂芳基；
所述可取代基团的取代基任选自氰基、卤素原子、C1-10的烷基、C6-30芳基、含有一个或多个杂原子5至30元杂芳基中的一种或多种；
所述杂原子任选自氧原子、硫原子或氮原子中的一种或多种。
作为本发明的进一步改进，所述通式(I)可表示为通式(I-1)至通式(I-5)所示结构：
作为本发明的进一步改进，所述R1～R3各自独立的表示为甲基、乙基、丙基、异丙基、丁基、叔丁基、戊基、己基、环己基、取代或未取代的苯基、取代或未取代的联苯基、取代或未取代的萘基、取代或未取代的吡啶基中的一种；
所述R表示为氢原子、氘原子、氚原子、氰基、氟原子、甲基、乙基、异丙基、叔丁基、环己基、取代或未取代的苯基、取代或未取代的联苯基、取代或未取代的萘基、取代或未取代的吡啶基、取代或未取代的萘啶基；
所述可取代基团的取代基任选自氰基、氟原子、甲基、异丙基、叔丁基、苯基、联苯基、萘基、芴基、二苯并呋喃基、咔唑基、二苯并噻吩基、吡啶基、萘啶基或咔唑啉基中的一种或多种。
作为本发明的进一步改进，所述化合物具体结构为：
一种有机电致发光器件，所述有机电致发光器件至少一层功能层含有所述的三芳胺类有机化合物。
作为本发明的进一步改进，所述有机电致发光器件包括空穴传输层或电子阻挡层，所述空穴传输层或电子阻挡层含有所述的三芳胺类有机化合物。
一种照明或显示元件，包括所述的有机电致发光器件。
与现有技术相比，本发明有益的技术效果在于：
(1)本发明的化合物具有较高的空穴迁移率，作为OLED发光器件的空穴传输层的材料，可提高激子在发光层中的复合效率，提高能量利用率，从而提高器件发光效率。
(2)本发明的化合物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；可有效提高激子利用率，降低器件电压，提高器件的电流效率和寿命。本发明的化合物在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。
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，5为电子阻挡层，6为发光层，7为电子传输或空穴阻挡层，8为电子注入层，9为阴极反射电极层，10为光取出层。
图2为本发明器件实施例与比较例1的OLED器件在-10～80℃区间的电流效率。
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。
下述实施例中所有原料均采购于烟台万润精细化工股份有限公司。
下面所用L1、L2、Ar、X和Z等符号的含义与说明书发明内容部分的相同。
当L1不表示为单键时，中间体N的合成：
(1)氮气氛围下，称取0.01mol原料A溶解于150ml四氢呋喃(THF)中，再将0.03mol双(频哪醇根基)二硼、1×10-4mol(1,1’-双(二苯基膦)二茂铁)二氯钯(II)以及0.03mol乙酸钾加入，搅拌混合物，将上述反应物的混合溶液于反应温度80℃下加热回流10小时；反应结束后，加水冷却且将混合物过滤并将滤饼放在真空干燥箱中干燥，将所获得的残余物过硅胶柱分离纯化，得到中间体M；
(2)在250ml的三口瓶中，通氮气保护下，加入0.01mol中间体M，0.015mol原料B、1×10-4molPd(PPh3)4、100mL甲苯和50mL乙醇搅拌混合，将0.03mol碳酸钠溶解于50mL水中，然后将碳酸钠水溶液加入到反应体系中，加热至110℃，回流反应24小时，取样点板，显示无中间体M剩余，反应完全；自然冷却至室温，过滤，滤液分层，取有机相，进行减压旋蒸(-0.09MPa，85℃)，过中性硅胶柱纯化，得到中间体N；
以上述合成方法制备中间体N，具体结构如表1所示。
表1
实施例1：化合物4的合成
在250ml的三口瓶中，通氮气保护下，加入0.01mol原料A-1，0.012mol原料C-1，150ml甲苯搅拌混合，然后加入5×10-5mol Pd2(dba)3，5×10-5mol三叔丁基磷，0.03mol叔丁醇钠，加热至105℃，回流反应24小时，取样点板，显示无溴代物剩余，反应完全；自然冷却至室温，过滤，滤液旋蒸至无馏分，过中性硅胶柱，得到目标产物，纯度99.8％，收率86.3％。
元素分析结构(分子式C44H35N)：理论值C,91.47；H,6.11；N,2.42；测试值：C,91.43；H,6.12；N,2.45。ESI-MS(m/z)(M+)：理论值为577.77，实测值为578.46。
实施例2：化合物15的合成
化合物15的合成步骤与化合物4的合成步骤相似，只是将原料C-1用原料C-2代替；
元素分析结构(分子式C50H39N)：理论值C,91.85；H,6.01；N,2.14；测试值：C,91.80；H,6.02；N,2.18。ESI-MS(m/z)(M+)：理论值为653.87，实测值为653.28。
实施例3：化合物37的合成
化合物37的合成步骤与化合物4的合成步骤相似，只是将原料C-1用原料C-3代替；
元素分析结构(分子式C53H36N2)：理论值C,90.83；H,5.18；N,4.00；测试值：C,90.78；H,5.20；N,4.03。ESI-MS(m/z)(M+)：理论值为700.88，实测值为700.04。
实施例4：化合物48的合成
化合物48的合成步骤与化合物4的合成步骤相似，只是将原料C-1用原料C-4代替；
元素分析结构(分子式C47H33NO)：理论值C,89.92；H,5.30；N,2.23；O,2.55；测试值：C,89.87；H,5.31；N,2.25；O,2.57。ESI-MS(m/z)(M+)：理论值为627.79，实测值为628.21。
实施例5：化合物77的合成
化合物77的合成步骤与化合物4的合成步骤相似，只是将原料C-1用原料C-5代替；
元素分析结构(分子式C53H38N2)：理论值C,90.57；H,5.45；N,3.99；测试值：C,90.51；H,5.47；N,4.03。ESI-MS(m/z)(M+)：理论值为702.90，实测值为702.15。
实施例6：化合物87的合成
化合物87的合成步骤与化合物4的合成步骤相似，只是将原料A-1用中间体N-1代替；
元素分析结构(分子式C50H39N)：理论值C,91.85；H,6.01；N,2.14；测试值：C,91.81；H,6.02；N,2.17。ESI-MS(m/z)(M+)：理论值为653.87，实测值为653.06。
实施例7：化合物126的合成
化合物126的合成步骤与化合物4的合成步骤相似，只是将原料A-1用原料A-2代替，原料C-1用原料C-6代替；
元素分析结构(分子式C50H39N)：理论值C,91.85；H,6.01；N,2.14；测试值：C,91.82；H,6.01；N,2.17。ESI-MS(m/z)(M+)：理论值为653.87，实测值为653.11。
实施例8：化合物128的合成
化合物128的合成步骤与化合物126的合成步骤相似，只是将原料C-6用原料C-7代替；
元素分析结构(分子式C54H39N)：理论值C,92.40；H,5.60；N,2.00；测试值：C,92.36；H,5.61；N,2.03。ESI-MS(m/z)(M+)：理论值为701.91，实测值为701.19。
实施例9：化合物150的合成
化合物150的合成步骤与化合物126的合成步骤相似，只是将原料C-6用原料C-8代替；
元素分析结构(分子式C47H33NS)：理论值C,87.68；H,5.17；N,2.18；S,4.98；测试值：C,87.64；H,5.18；N,2.20；S,4.99。ESI-MS(m/z)(M+)：理论值为643.85，实测值为643.42。
实施例10：化合物160的合成
化合物160的合成步骤与化合物126的合成步骤相似，只是将原料C-6用原料C-9代替；
元素分析结构(分子式C53H38N2)：理论值C,90.57；H,5.45；N,3.99；测试值：C,90.52；H,5.47；N,4.02。ESI-MS(m/z)(M+)：理论值为702.90，实测值为701.98。
实施例11：化合物180的合成
化合物180的合成步骤与化合物4的合成步骤相似，只是将原料A-1用中间体N-2代替；
元素分析结构(分子式C56H43N)：理论值C,92.14；H,5.94；N,1.92；测试值：C,92.09；H,5.95；N,1.96。ESI-MS(m/z)(M+)：理论值为729.97，实测值为729.07。
实施例12：化合物190的合成
化合物190的合成步骤与化合物4的合成步骤相似，只是将原料A-1用原料A-3代替，原料C-1用原料C-11代替；
元素分析结构(分子式C50H39N)：理论值C,91.85；H,6.01；N,2.14；测试值：C,91.81；H,6.02；N,2.17。ESI-MS(m/z)(M+)：理论值为653.87，实测值为653.01。
实施例13：化合物206的合成
化合物206的合成步骤与化合物190的合成步骤相似，只是将原料C-11用原料C-12代替；
元素分析结构(分子式C54H37N)：理论值C,92.67；H,5.33；N,2.00；测试值：C,92.60；H,5.35；N,2.05。ESI-MS(m/z)(M+)：理论值为699.90，实测值为699.16。
实施例14：化合物214的合成
化合物214的合成步骤与化合物190的合成步骤相似，只是将原料C-11用原料C-13代替；
元素分析结构(分子式C53H37NO)：理论值C,90.44；H,5.30；N,1.99；O,2.27；测试值：C,90.39；H,5.31；N,2.01；O,2.29。ESI-MS(m/z)(M+)：理论值为703.88，实测值为699.16。
实施例15：化合物285的合成
化合物285的合成步骤与化合物4的合成步骤相似，只是将原料A-1用原料A-4代替，原料C-1用原料C-14代替；
元素分析结构(分子式C52H45N)：理论值C,91.32；H,6.63；N,2.05；测试值：C,91.28；H,6.64；N,2.08。ESI-MS(m/z)(M+)：理论值为683.94，实测值为683.17。
实施例16：化合物309的合成
化合物309的合成步骤与化合物4的合成步骤相似，只是将原料A-1用原料A-5代替；
元素分析结构(分子式C50H39N)：理论值C,91.85；H,6.01；N,2.14；测试值：C,91.81；H,6.02；N,2.17。ESI-MS(m/z)(M+)：理论值为653.87，实测值为653.09。
实施例17：化合物318的合成
化合物318的合成步骤与化合物4的合成步骤相似，只是将原料A-1用原料A-6代替，原料C-1用原料C-15代替；
元素分析结构(分子式C52H36N2O)：理论值C,88.61；H,5.15；N,3.97；N,2.27；测试值：C,88.55；H,5.16；N,3.99；N,2.30。ESI-MS(m/z)(M+)：理论值为704.87，实测值为702.99。
实施例18：化合物338的合成
化合物338的合成步骤与化合物4的合成步骤相似，只是将原料A-1用原料A-7代替，原料C-1用原料C-16代替；
元素分析结构(分子式C50H40N2O)：理论值C,87.69；H,5.89；N,4.09；N,2.34；测试值：C,87.62；H,5.90；N,4.11；N,2.38。ESI-MS(m/z)(M+)：理论值为684.88，实测值为684.06。
实施例19：化合物340的合成
化合物340的合成步骤与化合物4的合成步骤相似，只是将原料A-1用中间体N-3代替；
元素分析结构(分子式C49H38N2)：理论值C,89.87；H,5.85；N,4.28；测试值：C,89.84；H,5.86；N,4.30。ESI-MS(m/z)(M+)：理论值为654.86，实测值为653.14。
实施例20：化合物343的合成
化合物343的合成步骤与化合物4的合成步骤相似，只是将原料A-1用中间体N-4代替；
元素分析结构(分子式C53H40N2)：理论值C,90.31；H,5.72；N,3.97；测试值：C,90.26；H,5.74；N,4.00。ESI-MS(m/z)(M+)：理论值为704.92，实测值为704.17。
本发明化合物在发光器件中使用，可以作为空穴传输层材料，也可以作为电子阻挡层材料使用。对本发明上述实施例制备的化合物分别进行热性能、T1能级、HOMO能级和空穴迁移率的测试，检测结果如表2所示：
表2
注：三线态能级T1是由日立的F4600荧光光谱仪测试，材料的测试条件为2*10- 5mol/mL的甲苯溶液；玻璃化转变温度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；最高占据分子轨道HOMO能级是由电离能量测试系统(IPS-3)测试，测试为大气环境；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；空穴迁移率测试，将本发明材料制成单电荷器件，用SCLC方法测定。
由上表数据可知，本发明的有机化合物具有较为合适的HOMO能级，可应用于空穴传输层或电子阻挡层，本发明的有机化合物具有较高的空穴迁移率及较高的热稳定性，使得所制作的含有本发明有机化合物的OLED器件效率和寿命均得到提升。
以下通过器件实施例1-20和器件比较例1详细说明本发明合成的OLED材料在器件中的应用效果。本发明器件实施例2-20以及器件比较例1与器件实施例1相比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的空穴传输层材料或电子阻挡层材料做了更换。
器件实施例1
如图1所示，透明基板层1为透明PI膜，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，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HAT-CN作为空穴注入层3使用。接着蒸镀60nm厚度的化合物4作为空穴传输层4。随后蒸镀20nm厚度的化合物EB-1作为电子阻挡层5。上述空穴传输材料蒸镀结束后，制作OLED发光器件的发光层6，其结构包括OLED发光层6所使用GH-1、GH-2作为主体材料，GD-1作为掺杂材料，掺杂材料掺杂比例为10％重量比，发光层膜厚为40nm。在上述发光层6之后，继续真空蒸镀电子传输层材料为ET-1和Liq。该材料的真空蒸镀膜厚为40nm，此层为空穴阻挡/电子传输层7。在空穴阻挡/电子传输层7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8。在电子注入层8上，通过真空蒸镀装置，制作膜厚为15nm的Mg：Ag电极层，此层为阴极层9。在阴极层9上，真空蒸镀70nm的CP-1，作为CPL层10。相关材料的分子结构式如下所示：
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，测量器件的电流效率，发光光谱以及器件的寿命。用同样的方法制备的器件实施例和比较例如表3所示；所得器件的电流效率、颜色和10mA/cm2电流下的LT97寿命的测试结果如表4所示。所得器件的效率衰减系数
的测试结果如表5所示。所得器件在-10～80℃区间的电流效率测试结果如表6所示。
表3
表4
注：LT97指的是在电流密度为10mA/cm2情况下，器件亮度衰减到97％所用时间；
寿命测试系统为韩国脉冲科学M600型OLED器件寿命测试仪。
由表4的器件数据结果可以看出，与器件比较例1相比，本发明的有机发光器件无论是在效率还是寿命均相对于已知材料的OLED器件获得较大的提升。
为了比较不同器件在高电流密度下效率衰减的情况，定义效率衰减系数
进行表示，它表示驱动电流为100mA/cm2时器件的最大效率μ100与器件的最大效率μm之差与最大效率之间的比值，
值越大，说明器件的效率滚降越严重，反之，说明器件在高电流密度下快速衰降的问题得到了控制。对器件实施例1-20和器件比较例1分别进行效率衰减系数
的测定，检测结果如表5所示：
表5
从表5的数据来看，通过实施例和比较例的效率衰减系数对比我们可以看出，本发明的有机发光器件能够有效地降低效率滚降。
进一步的本发明材料制备的OLED器件在低温下工作时效率也比较稳定，将器件实施例6、13、18和器件比较例1在-10～80℃区间进行效率测试，所得结果如表6和图2所示。
表6
从表6和图2的数据可知，器件实施例6、13、18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，不仅低温效率高，而且在温度升高过程中，效率平稳升高。
综上，以上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 (7)
1.一种三芳胺类有机化合物，其特征在于，该化合物的结构如通式(I)所示：
所述L1、L2分别独立地表示为单键、亚苯基、亚联苯基、亚萘基、亚吡啶基或亚萘啶基；
所述Ar表示为取代或未取代的C6-30芳基、取代或未取代的含有一个或多个杂原子的5至30元杂芳基；
所述X表示为氧原子、硫原子、-C(R1)(R2)-或-N(R3)-；其中，R1～R3各自独立的表示为C1-10烷基、取代或未取代的C6-30芳基、取代或未取代的含有一个或多个杂原子的5-30元杂芳基中的一种；R1与R2还可以相互键结成环；
所述Z每次出现相同或不同的表示为氮原子或C-R；其中，与基团L1或L2键合的Z表示为碳原子；
所述R表示为氢原子、氘原子、氚原子、氰基、卤素、C1-10的烷基、C2-10的烯烃基、取代或未取代的C6-30芳基、取代或未取代的含有一个或多个杂原子的5至30元杂芳基；
所述可取代基团的取代基任选自氰基、卤素原子、C1-10的烷基、C6-30芳基、含有一个或多个杂原子5至30元杂芳基中的一种或多种；
所述杂原子任选自氧原子、硫原子或氮原子中的一种或多种。
2.根据权利要求1所述的有机化合物，其特征在于，所述通式(I)可表示为通式(I-1)至通式(I-5)所示结构：
3.根据权利要求1所述的有机化合物，其特征在于，所述R1～R3各自独立的表示为甲基、乙基、丙基、异丙基、丁基、叔丁基、戊基、己基、环己基、取代或未取代的苯基、取代或未取代的联苯基、取代或未取代的萘基、取代或未取代的吡啶基中的一种；
所述R表示为氢原子、氘原子、氚原子、氰基、氟原子、甲基、乙基、异丙基、叔丁基、环己基、取代或未取代的苯基、取代或未取代的联苯基、取代或未取代的萘基、取代或未取代的吡啶基、取代或未取代的萘啶基；
所述可取代基团的取代基任选自氰基、氟原子、甲基、异丙基、叔丁基、苯基、联苯基、萘基、芴基、二苯并呋喃基、咔唑基、二苯并噻吩基、吡啶基、萘啶基或咔唑啉基中的一种或多种。
4.根据权利要求1-3任一项所述的有机化合物，其特征在于，所述化合物具体结构为：
5.一种有机电致发光器件，其特征在于，所述有机电致发光器件至少一层功能层含有权利1-4任一项所述的三芳胺类有机化合物。
6.根据权利要求5所述的有机电致发光器件，包括空穴传输层或电子阻挡层，其特征在于，所述空穴传输层或电子阻挡层含有权利要求1-4任一项所述的三芳胺类有机化合物。
7.一种照明或显示元件，其特征在于，包括权利要求5或6任一项所述的有机电致发光器件。
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| KR20130102669A (ko) * | 2012-03-07 | 2013-09-23 | 덕산하이메탈(주) | 사이클로 펜타 페난트렌을 포함하는 유기전기소자용 화합물, 이를 포함하는 유기전기소자 및 그 전자 장치 |
| CN103373928A (zh) * | 2012-04-17 | 2013-10-30 | 三星显示有限公司 | 有机发光二极管用化合物、有机发光二极管和平板显示装置 |
| US20140209872A1 (en) * | 2013-01-28 | 2014-07-31 | Samsung Display Co.,Ltd. | Compound, organic light emitting device including the compound, and flat display device including the organic light emitting device |
| CN108623481A (zh) * | 2018-06-04 | 2018-10-09 | 长春海谱润斯科技有限公司 | 一种芳胺化合物及其有机发光器件 |
| CN108774515A (zh) * | 2018-06-04 | 2018-11-09 | 长春海谱润斯科技有限公司 | 一种有机发光组合材料及其有机发光器件 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552291A (zh) * | 2020-12-14 | 2021-03-26 | 河北瑞芯电子新材料有限公司 | 一种有机电致发光材料及其有机电致发光器件 |
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