WO2019185060A1 - 一种以芳胺接双二甲基芴为核心的化合物及其应用 - Google Patents
一种以芳胺接双二甲基芴为核心的化合物及其应用 Download PDFInfo
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- WO2019185060A1 WO2019185060A1 PCT/CN2019/080632 CN2019080632W WO2019185060A1 WO 2019185060 A1 WO2019185060 A1 WO 2019185060A1 CN 2019080632 W CN2019080632 W CN 2019080632W WO 2019185060 A1 WO2019185060 A1 WO 2019185060A1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C211/54—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 two or three six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
Definitions
- the invention relates to a compound with arylamine and didimethyl hydrazine as its core and its application, and belongs to the technical field of semiconductors.
- OLED Organic Light Emission Diodes
- the OLED light-emitting device is like a sandwich structure, including an electrode material film layer and an organic functional material sandwiched between different electrode film layers, and various functional materials are superposed on each other according to the purpose to form an OLED light-emitting device.
- the OLED light-emitting device functions as a current device.
- the positive and negative charges in the organic layer functional material film layer are applied by the electric field, the positive and negative charges are further recombined in the light-emitting layer, that is, the OLED electroluminescence is generated.
- OLED display technology has been applied in the fields of smart phones, tablet computers, etc., and will further expand to large-size applications such as television, but the luminous efficiency and service life of OLED devices are compared with actual product application requirements. Further improvement is needed.
- research on improving the performance of OLED light-emitting devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and improving the service life of the device.
- the OLED optoelectronic functional materials applied to OLED devices can be divided into two categories from the use of charge injection transport materials and luminescent materials. Further, the charge injection transport material may be further classified into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and the luminescent material may be further divided into a host luminescent material and a dopant material.
- organic functional materials are required to have good photoelectric properties.
- a charge transport material it is required to have good carrier mobility, high glass transition temperature, etc., as a main body of the light-emitting layer.
- the material has good bipolarity, appropriate HOMO/LUMO energy levels, and the like.
- the OLED photoelectric functional material film layer constituting the OLED device includes at least two layers or more, and the industrially applied OLED device structure includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron transport.
- Layers, electron injection layers and other film layers, that is to say, the photoelectric functional materials applied to the OLED device include at least hole injection materials, hole transport materials, luminescent materials, electron transport materials, etc., and the material types and combinations are rich. And the characteristics of diversity.
- the optoelectronic functional materials used have strong selectivity, and the performance of the same materials in different structural devices may be completely different.
- the photoelectric characteristics of devices must be selected to be more suitable and higher performance OLED functional materials or material combinations in order to achieve high efficiency and long life of the device. And the comprehensive characteristics of low voltage.
- the development of OLED materials is still far from enough. It is lagging behind the requirements of panel manufacturers, and it is especially important to develop higher performance organic functional materials as material enterprises.
- One of the objects of the present invention is to provide a compound having an aromatic amine and didimethyl hydrazine as a core.
- the compound provided by the invention has arylamine and didimethyl hydrazine as the core, has high glass transition temperature and molecular thermal stability, suitable HOMO and LUMO energy levels, high Eg, and can be effectively improved by device structure optimization.
- Ar is represented by a single bond, a C 6 -C 60 aryl group or a C 5 -C 60 heteroaryl group, and any of the C 6 -C 60 aryl group or the C 5 -C 60 heteroaryl group
- a H atom may be substituted by a C 1 -C 10 alkyl group
- R is represented by the structure represented by the formula (2) or the formula (3);
- Z and Y are the same or different, they are represented by an N atom or CR 1 , and when R 1 is present, the same or different is represented by a hydrogen atom, a cyano group or a C 1 -C. a 20- or branched-chain substituted alkyl group, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms;
- L 1 and L 2 are represented as a single bond, a C 6 -C 60 aryl group or a C 5 -C 60 heteroaryl group, and any H atom of the C 6 -C 60 aryl group or the C 5 -C 60 heteroaryl group Can be substituted by a C 1 -C 10 alkyl group;
- X represents an oxygen atom, a sulfur atom, an alkyl-substituted alkylene group, an aryl-substituted alkylene group, an alkyl-substituted imido group or an aryl-substituted imido group.
- the compound of the invention is an arylamine-bis-dimethyl hydrazine compound, and the arylamine is bonded to the bisdimethyl hydrazine structure, so that it has strong hole transporting ability, high hole mobility, and can be used as a hole transporting material.
- the high hole transport rate can improve the efficiency of the organic electroluminescent device; at the appropriate LUMO level, it acts as an electron blocking, enhances the recombination efficiency of the excitons in the light-emitting layer, and lowers the high current density.
- the efficiency roll-off reduces the device voltage and improves the current efficiency and lifetime of the device.
- the present invention can also be improved as follows.
- Ar is represented by a phenylene group, a biphenylylene group, a triphenylene group, a naphthylene group or a pyridylene group, and the phenylene group, a biphenylylene group, and a triphenylene group.
- Any one of the H, naphthylene or pyridylene groups may be substituted by methyl, ethyl, propyl, isopropyl, butyl, t-butyl;
- Z or Y is represented by the same or different N atom or CR 1
- R 1 is represented by a hydrogen atom, a cyano group, a methyl group, and a B group.
- L 1 and L 2 are represented by a single bond, a phenylene group, a biphenylylene group, a triphenylene group, a naphthylene group or a pyridylene group, and the phenylene group, a biphenylylene group, a triphenylene group, a naphthylene group.
- Any H atom in the group or pyridylene group may be substituted with a methyl group, an ethyl group, a propyl group, and an isomer thereof.
- Another object of the present invention is to provide an organic electroluminescent device.
- the compound of the invention can maintain high film stability by optimizing the structure of the device, can effectively improve the photoelectric performance of the OLED device and the lifetime of the OLED device, and the compound of the invention has good performance in the OLED light-emitting device. Application effects and industrialization prospects.
- An organic electroluminescent device wherein at least one functional layer contains the above-mentioned compound having an aromatic amine and didimethyl fluorene as a core.
- the present invention can also be improved as follows.
- the functional layer is a light-emitting layer and/or an electron blocking layer and/or a hole transport layer.
- a third object of the invention is to provide an illumination or display element.
- the organic electroluminescent device of the invention can be applied to illumination or display originals, so that the current efficiency, power efficiency and external quantum efficiency of the device are greatly improved; at the same time, the device lifetime is improved obviously, and the OLED light-emitting device has good performance.
- the application effect has a good industrialization prospect.
- an illumination or display element comprising the organic electroluminescent device as described above.
- the compound of the present invention is an arylamine-bis-dimethyl hydrazine compound, and the arylamine is bonded to a bisdimethyl hydrazine structure to have a strong hole transporting ability and a high hole mobility as a hole transporting material.
- the high hole transport rate can improve the efficiency of the organic electroluminescent device; at the appropriate LUMO level, it acts as an electron blocking, enhances the recombination efficiency of the excitons in the light-emitting layer, and lowers the high current density.
- the efficiency roll-off reduces the device voltage and improves the current efficiency and lifetime of the device.
- the compound of the present invention is mainly composed of an aromatic amine and didimethyl fluorene, and the three branches connected are radial. After the material is formed into a film, the branches can cross each other to form a dense layer, thereby reducing the material in the film. Leakage current after application of OLED devices, thus increasing device lifetime.
- the compound of the invention can maintain high film stability by optimizing the device structure, can effectively improve the photoelectric performance of the OLED device and the lifetime of the OLED device, and the compound of the invention is in the OLED light-emitting device. Has a good application effect and industrialization prospects.
- the compound of the invention has high glass transition temperature and molecular thermal stability, suitable HOMO and LUMO energy levels, high Eg, and optimized by device structure, can effectively improve the photoelectric performance of the OLED device and the lifetime of the OLED device.
- the organic electroluminescent device of the invention can be applied to illumination or display originals, so that the current efficiency, power efficiency and external quantum efficiency of the device are greatly improved; at the same time, the device lifetime is greatly improved, in the OLED light-emitting device. It has good application effect and has good industrialization prospects.
- Figure 1 is a schematic view showing the structure of a device to which the compound of the present invention is applied, wherein the components represented by the respective numerals are as follows:
- FIG. 2 is a graph showing current efficiency versus temperature for an OLED device of the present invention.
- FIG. 3 is a graph showing a leakage current test of a reverse voltage of a device fabricated in Device Example 1 and Device Comparative Example 1 of the present invention.
- the structure of the materials involved is as follows:
- the transparent substrate layer 1 is a transparent substrate such as a transparent PI film, glass, or the like.
- the ITO anode layer 2 (having a film thickness of 150 nm) was washed, that is, washed with alkali, washed with pure water, dried, and subjected to ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO.
- molybdenum trioxide MoO 3 having a thickness of 10 nm was deposited as a hole injecting layer 3 by a vacuum vapor deposition apparatus.
- NPB having a thickness of 40 nm was vapor-deposited as the hole transport layer a.
- the hole transport layer b a compound 1 having a thickness of 80 nm was evaporated as the hole transport layer b.
- the light emitting layer 6 of the OLED light emitting device is fabricated, and the structure thereof includes CBP used as the host material of the OLED light emitting layer 6, and GD19 is used as a doping material, and the doping ratio of the doping material is 5% by weight.
- the thickness of the light-emitting layer was 40 nm.
- the vacuum evaporation of the electron transport layer material was continued to be TPBI.
- the vacuum evaporation film thickness of this material was 40 nm, and this layer was the electron transport layer 7.
- a lithium fluoride (LiF) layer having a film thickness of 1 nm was formed by a vacuum evaporation apparatus, and this layer was an electron injection layer 8.
- an aluminum (Al) layer having a film thickness of 80 nm was formed by a vacuum deposition apparatus, and this layer was used as the cathode reflective electrode layer 9.
- the life test system is the OLED device life tester jointly researched by the owner of the invention and Shanghai University.
- the compound of the present invention has good application effects as a hole transport layer material in an OLED light-emitting device, and has a good industrialization prospect. Further, the OLED device prepared by the material of the present invention is relatively stable when operating at a low temperature, and the device examples 1, 6, and 10 and the device comparative example 1, the comparative example 2, and the comparative example 3 are in the range of -10 to 80 ° C. Test, the results are shown in Table 3 and Figure 2.
- device examples 1, 6, and 10 are device structures in which the materials of the present invention and known materials are matched, and compared with device comparative example 1, comparative example 2, and comparative example 3, not only low temperature efficiency High, and the efficiency rises steadily during the temperature rise.
- the devices fabricated in Device Example 1 and Device Comparative Example 1 of the present invention were subjected to a reverse voltage leakage current test, and the test data is shown in FIG.
- FIG. 3 compared with the device fabricated in the device example 1 and the device comparative example 1 of the compound of the present invention, the leakage current is small and the current curve is stable. Therefore, the material of the present invention is applied to the device after fabrication. Long service life.
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Abstract
本发明公开了一种以芳胺接双二甲基芴为核心的化合物及其应用，属于半导体技术领域。本发明提供的化合物的结构如通式(1)所示：本发明还公开了上述化合物的应用。本发明的化合物具有分子间不易结晶、不易聚集、成膜性好的特点。本发明的化合物可以作为空穴传输层材料应用于有机电致发光器件上，应用本发明化合物的有机电致发光器件具有良好的光电性能，可以更好的适应和满足面板制造企业的应用要求。
Description
本发明涉及一种以芳胺接双二甲基芴为核心的化合物及其应用，属于半导体技术领域。
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
本发明的目的之一，是提供一种以芳胺接双二甲基芴为核心的化合物。本发明提供的化合物以芳胺接双二甲基芴为核心，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。
本发明解决上述技术问题的技术方案如下：一种以芳胺接双二甲基芴为核心的化合物，该化合物的结构如通式(1)所示：
通式(1)中，Ar表示为单键、C
6-C
60芳基或C
5-C
60杂芳基，所述C
6-C
60芳基或C
5-C
60杂芳基的任一H原子可被C
1-C
10的烷基取代；
R表示为通式(2)或通式(3)所示结构；
通式(2)和通式(3)中，Z、Y出现时相同或不同的表示为N原子或C-R
1，R
1出现时相同或不同的表示为氢原子、氰基或C
1-C
20直链或支链取代的烷基、具有5-30个芳族环原子的芳族或杂芳族环系；
L
1和L
2表示为单键、C
6-C
60芳基或C
5-C
60杂芳基，所述C
6-C
60芳基或C
5-C
60杂芳基的任一H原子可被C
1-C
10的烷基取代；
X表示为氧原子、硫原子、烷基取代的亚烷基、芳基取代的亚烷基、烷基取代的亚胺基或芳基取代的亚胺基。
本发明的化合物为芳胺接双二甲基芴类化合物，芳胺接双二甲基芴类结构使得其有很强的空穴传输能力，空穴迁移率高，可作为空穴传输材料使用，高的空穴传输速率能够提高有机电致发光器件的效率；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，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。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，所述通式(1)中，Ar表示为亚苯基、亚联苯基、亚三苯基、亚萘基或亚吡啶基，所述亚苯基、亚联苯基、亚三苯基、亚萘基或亚吡啶基中任一H原子可被甲基、乙基、丙基、异丙基、丁基、叔丁基取代；
通式(2)和通式(3)中，Z、Y出现时相同或不同的表示为N原子或C-R
1，R
1出现时相同或不同的表示为氢原子、氰基、甲基、乙基、丙基、丁基、异丙基、叔丁基、戊基、己基、苯基、联苯基、三苯基、萘基、二苯并呋喃基、二苯并噻吩基或咔唑基，其中所述甲基、乙基、丙基、丁基、异丙基、叔丁基、戊基、己基、苯基、联苯基、三苯基、萘基、二苯并呋喃基、二苯并噻吩基或咔唑基中任一H原子可被甲基、乙基、丙基、异丙基、叔丁 基、苯基或联苯基取代；
L
1和L
2表示为单键、亚苯基、亚联苯基、亚三苯基、亚萘基或亚吡啶基，所述亚苯基、亚联苯基、亚三苯基、亚萘基或亚吡啶基中任一H原子可被甲基、乙基、丙基及其异构体取代。
更进一步，所述化合物的具体结构式为：
本发明的目的之二，是提供一种有机电致发光器件。本发明的化合物在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。
本发明解决上述技术问题的技术方案如下：一种有机电致发光器件，至少一层功能层含有上述以芳胺接双二甲基芴为核心的化合物。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，所述功能层为发光层和/或电子阻挡层和/或空穴传输层。
本发明的目的之三，是提供一种照明或显示元件。本发明的有机电致发光器件可以应用在照明或显示原件，使器件的电流效率，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，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。
本发明解决上述技术问题的技术方案如下：一种照明或显示元件，包括如上所述的有机电致发光器件。
本发明的有益效果是：
1.本发明的化合物为芳胺接双二甲基芴类化合物，芳胺接双二甲基芴类结构使得其有很强的空穴传输能力，空穴迁移率高，作为空穴传输材料使用，高的空穴传输速率能够提高有机电致发光器件的效率；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，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。
2.本发明的化合物以芳胺接双二甲基芴为中心，连接的3个支链呈放射状，材料成膜后，各支链可相互交叉形成致密性高的膜层，从而降低材料在OLED器件应用后的漏电流，因此提高器件使用寿命。
3.本发明的化合物在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。
4.本发明的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。
5.本发明的有机电致发光器件可以应用在照明或显示原件，使器件的电流效率，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，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。
图1为本发明化合物应用的器件结构示意图，其中，各标号所代表的部件如下：
1、透明基板层，2、ITO阳极层，3、空穴注入层，4、空穴传输层a，5、空穴传输层b，6、发光层，7、电子传输层，8、电子注入层，9、阴极反射电极层。
图2为本发明OLED器件的电流效率随温度的变化曲线。
图3为本发明器件实施例1与器件比较例1所制作的器件进行反向电压的漏电流测试曲线图。
以下结合附图对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
以下的合成例1～10中所合成的中间体的结构如下所述。
合成例1(中间体1的合成)
将0.1mol原料2-氨基-9,9-二甲基芴与0.12mol原料2-溴-9,9-二甲基芴溶解于500mL无水甲苯中，除氧后加入0.005mol Pd
2(dba)
3和0.15mol三叔丁基磷,在惰性气氛下110℃反应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，得到中间体1；元素分析结构(分子式C
30H
27N)：理论值C,89.73；H,6.78；N,3.49；测试值：C,89.74；H,6.78；N,3.48；ESI-MS(m/z)(M+)：理论值为401.55，实测值为401.90。
合成例2(中间体2的合成)
将0.01mol中间体1与0.012mol 1,4-二溴苯溶解于150mL无水甲苯中，除氧后加入0.0005mol Pd
2(dba)
3和0.015mol三叔丁基磷,在惰性气氛下110℃反应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，得到中间体2；元素分析结构(分子式C
36H
30BrN)：理论值C,77.69；H,5.43；Br,14.36；N,2.52；测试值：C,77.68；H,5.43；Br,14.36；N,2.53；ESI-MS(m/z)(M+)：理论值为556.55，实测值为556.84。
合成例3(中间体3的合成)
合成例2中，除了使用1,3-二溴苯来代替1,4-二溴苯之外，同样地进行反应后，得到中间体3；元素分析结构(分子式C
36H
30BrN)：理论值C,77.69；H,5.43；Br,14.36；N,2.52；测试值：C,77.69；H,5.43；Br,14.37；N,2.53；ESI-MS(m/z)(M+)：理论值为556.55，实测值为556.74。
合成例4(中间体4的合成)
将0.01mol原料3,5-二溴联苯和0.012mol原料4-二苯并呋喃硼酸溶解于甲苯和乙醇的150mL(V
甲苯：V
乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh
3)
4和0.02mol K
2CO
3，在惰性气氛下110℃反应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，得到中间体4；元素分析结构(分子式C
24H
15BrO)：理论值C,72.19；H,3.79；Br,20.01；测试值：C,72.19；H,3.79；Br,20.02；ESI-MS(m/z)(M+)：理论值为399.29，实测值为399.63。
合成例5(中间体5的合成)
在惰性气氛下，称取0.01mol中间体4、0.0075mol双(频哪醇合)二硼、0.0005molPd(dppf)Cl
2和0.022mol醋酸钾溶于150ml甲苯中，100-120℃下反应12-24小时，取样点板，反应完全，自然冷却，过滤，滤液旋蒸，得到粗产品，过中性硅胶柱，得到中间体5；元素分析结构(分子式C
24H
17BO
3)：理论值C,79.15；H,4.71；B,2.97；测试值：C,79.15；H,4.71；B,2.98；ESI-MS(m/z)(M+)：理论值为364.21，实测值为364.88。
合成例6(中间体6的合成)
合成例4中，除了使用2,5-二溴联苯来代替1,3,5-三溴苯之外，同样 地进行反应后，得到中间体6；元素分析结构(分子式C
24H
15BrO)：理论值C,72.19；H,3.79；Br,20.0；测试值：C,72.19；H,3.79；Br,20.00；ESI-MS(m/z)(M+)：理论值为399.29，实测值为399.53。
合成例7(中间体7的合成)
合成例5中，除了使用中间体6来代替中间体4之外，同样地进行反应后，得到中间体7；元素分析结构(分子式C
24H
17BO
3)：理论值C,79.15；H,4.71；B,2.97；测试值：C,79.15；H,4.71；B,2.98；ESI-MS(m/z)(M+)：理论值为364.21，实测值为364.56。
合成例8(中间体8的合成)
合成例4中，除了使用2,5-二溴联苯来代替1,3,5-三溴苯，用二苯并呋喃-2-硼酸来代替4-二苯并呋喃硼酸之外，同样地进行反应后，得到中间体8；元素分析结构(分子式C
24H
15BrO)：理论值C,72.19；H,3.79；Br,20.01；测试值：C,72.19；H,3.79；Br,20.02；ESI-MS(m/z)(M+)：理论值为399.29，实测值为399.76。
合成例9(中间体9的合成)
合成例5中，除了使用中间体8来代替中间体4之外，同样地进行反应后，得到中间体9；元素分析结构(分子式C
24H
17BO
3)：理论值C,79.15；H,4.71；B,2.97；测试值：C,79.14；H,4.71；B,2.97；ESI-MS(m/z)(M+)：理论值为364.21，实测值为364.42。
合成例10(中间体10的合成)
合成例4中，除了使用3,5-二溴联苯来代替1,3,5-三溴苯，用9,9-二甲基芴-2-硼酸来代替4-二苯并呋喃硼酸之外，同样地进行反应后，得到中间体10；元素分析结构(分子式C
27H
21Br)：理论值C,76.24；H,4.98；Br,18.78；测试值：C,76.25；H,4.98；Br,18.77；ESI-MS(m/z)(M+)：理论值为425.37，实测值为425.86。
合成例11(中间体11的合成)
合成例5中，除了使用中间体10来代替中间体4之外，同样地进行反应后，得到中间体11；元素分析结构(分子式C
27H
23BO
2)：理论值C,83.09；H,5.94；B,2.77；测试值：C,83.08；H,5.94；B,2.77；ESI-MS(m/z)(M+)：理论值为390.29，实测值为390.97。
合成例12(中间体12的合成)
合成例4中，除了使用2,4-二溴联苯来代替1,3,5-三溴苯，用9,9-二甲基芴-2-硼酸来代替4-二苯并呋喃硼酸之外，同样地进行反应后，得到中间体12；元素分析结构(分子式C
27H
21Br)：理论值C,76.24；H,4.98；Br,18.78；测试值：C,76.25；H,4.98；Br,18.77；ESI-MS(m/z)(M+)：理论值为425.37，实测值为425.74。
合成例13(中间体13的合成)
合成例5中，除了使用中间体12来代替中间体4之外，同样地进行反应后，得到中间体13；元素分析结构(分子式C
27H
23BO
2)：理论值C,83.09；H,5.94；B,2.77；测试值：C,83.09；H,5.94；B,2.78；ESI-MS(m/z)(M+)：理论值为390.29，实测值为390.88。
合成例14(中间体14的合成)
合成例4中，除了使用2,5-二溴联苯来代替1,3,5-三溴苯，用9,9-二甲基芴-4-硼酸来代替4-二苯并呋喃硼酸之外，同样地进行反应后，得到中间体14；元素分析结构(分子式C
27H
21Br)：理论值C,76.24；H,4.98；Br,18.78；测试值：C,76.25；H,4.98；Br,18.77；ESI-MS(m/z)(M+)：理论值为425.37，实测值为425.54。
合成例15(中间体15的合成)
合成例5中，除了使用中间体14来代替中间体4之外，同样地进行反应后，得到中间体15；元素分析结构(分子式C
27H
23BO
2)：理论值C,83.09；H,5.94；B,2.77；测试值：C,83.08；H,5.94；B,2.77；ESI-MS(m/z)(M+)：理论值为390.29，实测值为390.83。
合成例16(中间体16的合成)
合成例4中，除了使用3,5-二溴联苯来代替1,3,5-三溴苯，用N-苯基-3-咔唑硼酸来代替4-二苯并呋喃硼酸之外，同样地进行反应后，得到中间体16；元素分析结构(分子式C
30H
20BrN)：理论值C,75.95；H,4.25；Br,16.84；N,2.95；测试值：C,75.95；H,4.25；Br,16.85；N,2.95；ESI-MS(m/z)(M+)：理论值为474.40，实测值为474.71。
合成例17(中间体17的合成)
合成例4中，除了使用2,5-二溴联苯来代替1,3,5-三溴苯，用N-苯基 -2-咔唑硼酸来代替4-二苯并呋喃硼酸之外，同样地进行反应后，得到中间体17；元素分析结构(分子式C
30H
20BrN)：理论值C,75.95；H,4.25；Br,16.84；N,2.95；测试值：C,75.95；H,4.25；Br,16.84；N,2.96；ESI-MS(m/z)(M+)：理论值为474.40，实测值为474.82。
合成例18(中间体18的合成)
合成例5中，除了使用中间体17来代替中间体4之外，同样地进行反应后，得到中间体18；元素分析结构(分子式C
30H
22BNO
2)：理论值C,82.02；H,5.05；B,2.46；N,3.19；测试值：C,82.02；H,5.05；B,2.46；N,3.18；ESI-MS(m/z)(M+)：理论值为439.32，实测值为439.93。
合成例19(中间体19的合成)
合成例4中，除了使用2,4-二溴联苯来代替1,3,5-三溴苯，用N-苯基-3-咔唑硼酸来代替4-二苯并呋喃硼酸之外，同样地进行反应后，得到中间体19；元素分析结构(分子式C
30H
20BrN)：理论值C,75.95；H,4.25；Br,16.84；N,2.95；测试值：C,75.96；H,4.25；Br,16.84；N,2.95；ESI-MS(m/z)(M+)：理论值为474.40，实测值为474.86。
合成例20(中间体20的合成)
合成例5中，除了使用中间体19来代替中间体4之外，同样地进行反应后，得到中间体20；元素分析结构(分子式C
30H
22BNO
2)：理论值C,82.02；H,5.05；B,2.46；N,3.19；测试值：C,82.02；H,5.05；B,2.46；N,3.18；ESI-MS(m/z)(M+)：理论值为439.32，实测值为439.76。
合成例21(中间体21的合成)
合成例2中，除了使用9H-吡啶[3,4-b]吲哚来代替中间体1，用3,5-二溴联苯来代替1,4-二溴苯之外，同样地进行反应后，得到中间体21；元素分析结构(分子式C
23H
15BrN
2)：理论值C,69.19；H,3.79；Br,20.01；N,7.02；测试值：C,69.19；H,3.79；Br,20.00；N,7.02；ESI-MS(m/z)(M+)：理论值为399.29，实测值为399.86。
合成例22(中间体22的合成)
合成例5中，除了使用中间体21来代替中间体4之外，同样地进行反应后，得到中间体22；元素分析结构(分子式C
23H
17BN
2O
2)：理论值C,75.85；H,4.70；B,2.97；N,7.69；测试值：C,75.84；H,4.70；B,2.97；N,7.69； ESI-MS(m/z)(M+)：理论值为364.21，实测值为364.64。
合成实施例1(化合物1的合成)
将0.01mol中间体2和0.012mol中间体5溶解于甲苯和乙醇的150mL(V
甲苯：V
乙醇＝5：1)混合溶液中，除氧后加入0.0002mol Pd(PPh
3)
4和0.02mol K
2CO
3，在惰性气氛下110℃反应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，得到化合物1；元素分析结构(分子式C
60H
45NO)：理论值C,90.53；H,5.70；N,1.76；测试值：C,90.54；H,5.70；N,1.76；ESI-MS(m/z)(M+)：理论值为796.03，实测值为796.88。
合成实施例2(化合物13的合成)
合成实施例1中，除了使用中间体3来代替中间体2，用中间体7来代替中间体5之外，同样地进行反应后，得到化合物13；元素分析结构(分子式C
60H
45NO)：理论值C,90.53；H,5.70；N,1.76；测试值：C,90.53；H,5.70；N,1.75；ESI-MS(m/z)(M+)：理论值为796.03，实测值为796.68。
合成实施例3(化合物30的合成)
合成实施例1中，除了使用中间体3来代替中间体2，用中间体9来代替中间体5之外，同样地进行反应后，得到化合物30；元素分析结构(分子式C
60H
45NO)：理论值C,90.53；H,5.70；N,1.76；测试值：C,90.52；H,5.70；N,1.76；ESI-MS(m/z)(M+)：理论值为796.03，实测值为796.41。
合成实施例4(化合物41的合成)
合成实施例1中，除了使用中间体11来代替中间体5之外，同样地进行反应后，得到化合物41；元素分析结构(分子式C
63H
51N)：理论值C,92.04；H,6.25；N,1.70；测试值：C,92.04；H,6.25；N,1.71；ESI-MS(m/z)(M+)：理论值为822.11，实测值为822.83。
合成实施例5(化合物59的合成)
合成实施例1中，除了使用中间体13来代替中间体5之外，同样地进行反应后，得到化合物59；元素分析结构(分子式C
63H
51N)：理论值C,92.04；H,6.25；N,1.70；测试值：C,92.03；H,6.25；N,1.72；ESI-MS(m/z)(M+)：理论值为822.11，实测值为822.97。
合成实施例6(化合物73的合成)
合成实施例1中，除了使用中间体15来代替中间体5之外，同样地进行反应后，得到化合物73；元素分析结构(分子式C
63H
51N)：理论值C,92.04；H,6.25；N,1.70；测试值：C,92.04；H,6.26；N,1.70；ESI-MS(m/z)(M+)：理论值为822.11，实测值为822.47。
合成实施例7(化合物87的合成)
合成实施例1中，除了使用中间体3来代替中间体2，用中间体16来代替中间体5之外，同样地进行反应后，得到化合物87；元素分析结构(分子式C
66H
50N
2)：理论值C,91.00；H,5.79；N,3.22；测试值：C,91.00；H,5.78；N,3.22；ESI-MS(m/z)(M+)：理论值为871.14，实测值为871.67。
合成实施例8(化合物98的合成)
合成实施例1中，除了使用中间体18来代替中间体5之外，同样地进行反应后，得到化合物98；元素分析结构(分子式C
66H
50N
2)：理论值C,91.00；H,5.79；N,3.22；测试值：C,91.01；H,5.79；N,3.20；ESI-MS(m/z)(M+)：理论值为871.14，实测值为871.57。
合成实施例9(化合物108的合成)
合成实施例1中，除了使用中间体20来代替中间体5之外，同样地进行反应后，得到化合物108；元素分析结构(分子式C
66H
50N
2)：理论值C,91.00；H,5.79；N,3.22；测试值：C,91.00；H,5.79；N,3.21；ESI-MS(m/z)(M+)：理论值为871.14，实测值为871.54。
合成实施例10(化合物126的合成)
合成实施例1中，除了使用中间体22来代替中间体5之外，同样地进行反应后，得到化合物126；元素分析结构(分子式C
59H
45N
3)：理论值C,89.02；H,5.70；N,5.28；测试值：C,89.03；H,5.70；N,5.27；ESI-MS(m/z)(M+)：理论值为796.03，实测值为796.43。
以下通过实施例1-10和比较例1、2、3详细说明本发明合成的化合物在器件中作为空穴传输层材料的应用效果。各实施例得到的器件的结构组成如表1所示。所得器件的测试结果见表2所示。
器件实施例1
透明基板层/ITO阳极层/空穴注入层(三氧化钼MoO
3，厚度10nm)/空穴传输层a(NPB，厚度40nm)/空穴传输层b(上述实施例制备的化合物1， 厚度80nm)/发光层(CBP和GD19按照100：5的重量比混掺，厚度40nm)/电子传输层(TPBI，厚度40nm)/电子注入层(LiF，厚度1nm)/阴极反射电极层(Al)。涉及到的材料结构式如下：
具体制备过程如下：
如图1所示，透明基板层1为透明基材，如透明PI膜、玻璃等。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的三氧化钼MoO
3作为空穴注入层3使用。接着蒸镀40nm厚度的NPB作为空穴传输层a。紧接着蒸镀80nm厚度的化合物1作为空穴传输层b。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CBP作为主体材料，GD19作为掺杂材料，掺杂材料掺杂比例为5％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TPBI。该材料的真空蒸镀膜厚为40nm，此层为电子传输层7。在电子传输层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80nm的铝(Al)层，此层为阴极反射电极层9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，测量器件的电流效率以及器件的寿命。
表1
表2
说明: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，并且与比较例1、2、3相比，无论是效率还是寿命均获得较大改观，特别是器件的驱动寿命获得较大的提升。
从实施例所提供的测试数据来看，本发明化合物作为空穴传输层材料在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。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1、6、10和器件比较例1、比较例2、比较例3在-10～80℃区间进行效率测试，所得结果如表3和图2所示。
表3 效率测试结果
从表3和图2的数据可知，器件实施例1、6、10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、比较例2、比较例3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。
为进一步测试本发明化合物所产生的有益效果，将本发明器件实施例1和器件比较例1所制作器件进行反向电压的漏电流测试，测试数据如图3所示。从图3中可得知，应用本发明化合物的器件实施例1和器件比较例1所制作器件相比，漏电流很小，且电流曲线稳定，因此，本发明材料应用于器件制作后，具有较长使用寿命。
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 (6)
- 一种以芳胺接双二甲基芴为核心的化合物，其特征在于，该化合物的结构如通式(1)所示：
通式(1)中，Ar表示为单键、C 6-C 60芳基或C 5-C 60杂芳基，所述C 6-C 60芳基或C 5-C 60杂芳基的任一H原子可被C 1-C 10的烷基取代；R表示为通式(2)或通式(3)所示结构；
通式(2)和通式(3)中，Z、Y出现时相同或不同的表示为N原子或C-R 1，R 1出现时相同或不同的表示为氢原子、氰基或C 1-C 20直链或支链取代的烷基、具有5-30个芳族环原子的芳族或杂芳族环系；L 1和L 2表示为单键、C 6-C 60芳基或C 5-C 60杂芳基，所述C 6-C 60芳基或C 5-C 60杂芳基的任一H原子可被C 1-C 10的烷基取代；X表示为氧原子、硫原子、烷基取代的亚烷基、芳基取代的亚烷基、烷基取代的亚胺基或芳基取代的亚胺基。 - 根据权利要求1所述的一种以芳胺接双二甲基芴为核心的化合物，其特征在于，所述通式(1)中，Ar表示为亚苯基、亚联苯基、亚三苯基、亚萘基或亚吡 啶基，所述亚苯基、亚联苯基、亚三苯基、亚萘基或亚吡啶基中任一H原子可被甲基、乙基、丙基、异丙基、丁基、叔丁基取代；通式(2)和通式(3)中，Z、Y出现时相同或不同的表示为N原子或C-R 1，R 1出现时相同或不同的表示为氢原子、氰基、甲基、乙基、丙基、丁基、异丙基、叔丁基、戊基、己基、苯基、联苯基、三苯基、萘基、二苯并呋喃基、二苯并噻吩基或咔唑基，其中所述甲基、乙基、丙基、丁基、异丙基、叔丁基、戊基、己基、苯基、联苯基、三苯基、萘基、二苯并呋喃基、二苯并噻吩基或咔唑基中任一H原子可被甲基、乙基、丙基、异丙基、叔丁基、苯基或联苯基取代；L 1和L 2表示为单键、亚苯基、亚联苯基、亚三苯基、亚萘基或亚吡啶基，所述亚苯基、亚联苯基、亚三苯基、亚萘基或亚吡啶基中任一H原子可被甲基、乙基、丙基及其异构体取代。
- 根据权利要求1所述的一种以芳胺接双二甲基芴为核心的化合物，其特征在于，所述化合物的具体结构式为：
中的任意一种。
- 一种有机电致发光器件，其特征在于，至少一层功能层含有权利要求1-3任一项所述的以芳胺接双二甲基芴为核心的化合物。
- 根据权利要求4所述的一种有机电致发光器件，其特征在于，所述功能层为发光层和/或电子阻挡层和/或空穴传输层。
- 一种照明或显示元件，其特征在于，包括如权利要求4或5所述的有机电致发光器件。
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