WO2016141693A1 - 有机电致发光器件 - Google Patents

有机电致发光器件 Download PDF

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WO2016141693A1
WO2016141693A1 PCT/CN2015/088711 CN2015088711W WO2016141693A1 WO 2016141693 A1 WO2016141693 A1 WO 2016141693A1 CN 2015088711 W CN2015088711 W CN 2015088711W WO 2016141693 A1 WO2016141693 A1 WO 2016141693A1
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substituted
unsubstituted
group
organic electroluminescent
layer
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PCT/CN2015/088711
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English (en)
French (fr)
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鲁锦鸿
李哲
陈金鑫
蔡丽菲
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广东阿格蕾雅光电材料有限公司
北京阿格蕾雅科技发展有限公司
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Application filed by 广东阿格蕾雅光电材料有限公司, 北京阿格蕾雅科技发展有限公司 filed Critical 广东阿格蕾雅光电材料有限公司
Priority to US15/557,098 priority Critical patent/US10505118B2/en
Priority to KR1020177025542A priority patent/KR102060582B1/ko
Priority to JP2017547517A priority patent/JP6529196B2/ja
Priority to DE112015006275.0T priority patent/DE112015006275B4/de
Publication of WO2016141693A1 publication Critical patent/WO2016141693A1/zh

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Definitions

  • the invention relates to an organic electroluminescent blue light device prepared by a novel organic host material, and belongs to the technical field of organic electroluminescent device display.
  • organic electroluminescent devices As a new display technology, organic electroluminescent devices have self-luminous, wide viewing angle, low power consumption, high efficiency, thin, rich color, fast response, wide temperature range, low driving voltage, flexible and bendable Transparent display panels and environmentally friendly features, therefore, organic electroluminescent device technology can be applied to flat panel displays and next-generation lighting, as well as backlights for LCDs.
  • An organic electroluminescent device is a device prepared by spin coating or depositing an organic material between two metal electrodes.
  • a classic three-layer organic electroluminescent device comprises a hole transport layer, a light emitting layer and an electron transport layer. The holes generated by the anode pass through the hole transport layer and the electrons generated by the cathode are combined by the electron transport layer to form excitons in the light-emitting layer, and then emit light.
  • the organic electroluminescent device can emit red light, green light, and blue light by changing the material of the light emitting layer. Therefore, stable, high-efficiency and color-purity organic electroluminescent materials play an important role in the application and promotion of organic electroluminescent devices, and are also an urgent need for the application of OLEDs for large-area panel displays.
  • red and green materials have recently achieved great development, although the performance of red and green organic electroluminescent devices has been significantly improved, and also in line with the panel market. Demand, but its efficiency and stability still need to be further improved. Therefore, solving the above problems from material design and device structure is a focus of research in this field.
  • the energy transfer efficiency of the host material to the doped illuminant has a large effect on the performance and stability of the device.
  • Commonly used host materials include mCP and 26DCzPPy and their derivatives, all containing a nitrogen atom. Hydrocarbon-only materials have relatively high relative stability and are suitable for industrial applications and commercialization.
  • DPA 9,10-diphenylfluorene
  • ADN 9,10-di(naphthalene-2-).
  • MADN 2-methyl-9,10-di(naphthalen-2-yl)anthracene
  • the present invention is to overcome the drawbacks of the above devices, and to provide an organic electroluminescent dye-doped blue light-emitting device which has good electroluminescence efficiency, excellent color purity and long life.
  • An organic electroluminescent device comprising an anode, a cathode, and an organic layer, the organic layer being a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and at least a light-emitting layer in the light-emitting layer
  • the luminescent layer is a host-guest doping system composed of a host material and a guest material, the luminescent region of the luminescent layer is blue 440-490 nm, and the host material or guest material has the formula (I) a compound of the structure,
  • R 1 - R 17 are independently represented by hydrogen, deuterium, halogen, cyano, nitro, C1-C8 alkyl, C1-C8 alkoxy, C6-C30 substituted or unsubstituted aryl, C3 a substituted or unsubstituted heteroaryl aryl group of C30, a C2-C8 substituted or unsubstituted olefinic group, a C2-C8 substituted or unsubstituted alkynyl group, wherein Ar 1 -Ar 3 A C6-C60 substituted or unsubstituted aryl group, a C3-C60 substituted or unsubstituted heteroaryl group having one or more hetero atoms, a triaromatic (C6-C30) amine group.
  • R 1 - R 17 are independently represented by hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C1-C8 alkoxy, C2-C8 substituted or unsubstituted olefinic alkyl, C2- a C8 substituted or unsubstituted alkynyl group, a C1-C4 alkyl substituted or unsubstituted phenyl group, a C1-C4 alkyl substituted or unsubstituted naphthyl group, or a C1-C4 alkyl group substituted or unsubstituted fluorene
  • Ar 1 -Ar 3 independently represents a C1-C4 alkyl group or a C6-C30 aryl-substituted phenyl group, a C1-C4 alkyl group or a C6-C30 aryl-substituted naphthyl group, a phenyl group, a
  • R 1 -R 2 may independently be preferably represented by hydrogen, halogen, C1-C4 alkyl, C1-C4 alkyl substituted or unsubstituted phenyl, C1-C4 alkyl substituted or unsubstituted naphthalene Or a C1-C4 alkyl-substituted or unsubstituted fluorenyl group; wherein R 3 - R 17 may independently be preferably represented by hydrogen, halogen, C1-C4 alkyl, C1-C4 alkyl substituted or not Substituted phenyl, C1-C4 alkyl substituted or unsubstituted naphthyl, preferably Ar 1 -Ar 3 independently represents phenyl, tolyl, xylyl, tert-butylphenyl, naphthyl, pyridyl, Methylnaphthalene, biphenyl, diphenylphen
  • R 3 - R 17 are preferably hydrogen
  • R 1 , R 2 may independently and preferably represent hydrogen, methyl, ethyl, propyl, isopropyl, t-butyl, phenyl, biphenyl, naphthalene.
  • Ar 1 -Ar 3 independently represents phenyl, pyridyl, tolyl, xylyl, naphthyl, methylnaphthalene, biphenyl, diphenylphenyl, naphthylbenzene Base, diphenylbiphenyl, (9,9-dialkyl)fluorenyl, (9,9-dimethyl substituted or unsubstituted phenyl) anthracenyl, 9,9-spiropurinyl.
  • R 3 - R 17 are preferably hydrogen; R 1 , R 2 independently represent hydrogen, methyl, or a fluorenyl group; and Ar 1 , Ar 2 , and Ar 3 independently represent a phenyl group, a naphthyl group.
  • the compound of formula (I) is the following structural compound
  • the organic layer is one or more of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer. It is particularly noted that the above organic layers may be present in each of the layers as needed.
  • the hole transport layer, the electron transport layer and/or the light-emitting layer contain the compound of the formula (I).
  • the compound of formula (I) is located in the luminescent layer.
  • the organic electroluminescent device of the present invention comprises at least one light-emitting layer having a light-emitting region of 440-490 nm in blue light.
  • the luminescent layer is a host-guest doping system composed of a host material and a guest material.
  • the compound of formula (I) is a host material and/or a guest material.
  • the concentration of the host material is from 20 to 99.9%, preferably from 80 to 99%, more preferably from 90 to 99% by weight based on the total of the luminescent layer. Accordingly, the concentration of the guest material is from 0.01 to 80%, preferably from 1 to 20%, more preferably from 1 to 10% by weight based on the total of the luminescent layer.
  • the organic layer of the electronic device of the present invention has a total thickness of from 1 to 1000 nm, preferably from 1 to 500 nm, more preferably from 50 to 300 nm.
  • the organic layer may be formed into a film by steaming or spin coating.
  • the hole transport layer and the hole injection layer in the present invention have a good hole transporting property and are capable of efficiently transporting holes from the anode to the organic light-emitting layer. It may include small molecules and high molecular organic materials, and may include, but is not limited to, triarylamine compounds, biphenyldiamine compounds, thiazole compounds, oxazole compounds, imidazole compounds, terpenoids, phthalocyanine compounds, Hexanitrile hexaazatriphenylene, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (F4-TCNQ), polyvinyl Carbazole, polythiophene, polyethylene, polybenzenesulfonic acid.
  • the organic electroluminescent layer of the present invention may contain, in addition to the compound of the structural formula (I) of the present invention, the following compounds, but is not limited thereto, naphthalene compounds, terpenoids, terpenoids, phenanthrene compounds, and quinones. Compounds, fluoranthene compounds, terpenoids, pentacene compounds, terpenoids, diarylene compounds, triphenylamine vinyl compounds, amine compounds, benzimidazoles, furan compounds, organic metal chelate Compound.
  • the organic electron transporting material used in the organic electronic device of the present invention is required to have good electron transporting property, and can efficiently transport electrons from the cathode to the light emitting layer, and the following compounds can be selected, but are not limited thereto, oxazole, thiazole Compounds, triazoles, triazazines, triazabenzenes, porphyrins, diazonium compounds, silicon-containing heterocyclic compounds, quinoline compounds, phenanthroline compounds , metal chelate, fluorine-substituted benzene compound.
  • the organic electronic device of the present invention may be provided with an electron injecting layer which can efficiently inject electrons from the cathode into the organic layer, mainly selected from alkali metal or alkali metal compounds, or selected from alkaline earth metals.
  • an electron injecting layer which can efficiently inject electrons from the cathode into the organic layer, mainly selected from alkali metal or alkali metal compounds, or selected from alkaline earth metals.
  • the alkaline earth metal compound the following compounds may be selected, but are not limited thereto, lithium, lithium fluoride, lithium oxide, lithium nitride, lithium quinolate, hydrazine, cesium carbonate, 8-hydroxyquinolinium, calcium, fluorine Calcium, calcium oxide, magnesium, magnesium fluoride, magnesium carbonate, magnesium oxide.
  • the device experiments show that the organic electroluminescent device of the present invention has the advantages of good electroluminescence efficiency, excellent color purity, and long life.
  • Figure 1 is a structural view of a device of the present invention
  • 10 represents a glass substrate
  • 20 represents an anode
  • 30 represents a hole injection layer
  • 40 represents a hole transport layer
  • 50 represents a light-emitting layer
  • 60 represents an electron transport layer
  • 70 represents an electron injection layer
  • 80 represents an electron injection layer. It is a cathode.
  • Figure 3 is a 13 C NMR chart of Compound 89.
  • Figure 5 is a TGA diagram of Compound 89.
  • Figure 6 is a graph showing voltage-current density curves of Examples 4, 5 and Comparative Example 1.
  • Figure 8 is a graph showing voltage-current density of Examples 8, 9 and Comparative Example 3.
  • Figure 10 is a graph showing current density-current efficiency of Examples 6, 7 and Comparative Example 2.
  • Figure 11 is a graph showing current density-current efficiency of Examples 8, 9 and Comparative Example 3.
  • Figure 12 is an electroluminescence spectrum of Examples 4, 5 and Comparative Example 1.
  • Figure 13 is an electroluminescence spectrum of Examples 6, 7 and Comparative Example 2.
  • Figure 14 is an electroluminescence spectrum of Examples 8, 9 and Comparative Example 3.
  • Figure 15 is a graph of brightness-CIEy of Examples 4, 5 and Comparative Example 1.
  • Figure 16 is a graph of brightness-CIEy of Examples 6, 7 and Comparative Example 2.
  • Figure 17 is a graph of brightness-CIEy of Examples 8, 9 and Comparative Example 3.
  • the transparent conductive ITO glass substrate 10 (with the anode 20 on the surface) was sequentially washed with a detergent solution and deionized water, ethanol, acetone, deionized water, and then treated with oxygen plasma for 30 seconds.
  • NPB was evaporated to form a hole transport layer 40 having a thickness of 30 nm.
  • a compound B1 (2%) and a compound 3 (98%) having a thickness of 30 nm were vapor-deposited on the hole transport layer as the light-emitting layer 50.
  • 15 nm BPhen Li was vaporized into an electron injection layer 70 and 150 nm Al as a device cathode 80.
  • the prepared device had a voltage of 3.87 V at an operating current density of 20 mA/cm 2 , a current efficiency of 4.57 cd/A, a blue light emission peak of 460 nm, and a CIEy of 0.135 at a luminance of 1000 cd/m 2 .
  • the prepared device had a voltage of 4.91 V at an operating current density of 20 mA/cm 2 , a current efficiency of 4.31 cd/A, a blue light emission peak of 456 nm, and a CIEy of 0.143 at a luminance of 1000 cd/m 2 .
  • the prepared device had a voltage of 4.09 V at an operating current density of 20 mA/cm 2 , a current efficiency of 5.27 cd/A, a blue light emission peak of 460 nm, and a CIEy of 0.155 at a luminance of 1000 cd/m 2 .
  • Example 6 The same procedure as in Example 6 was carried out, except that Compound 3 was replaced with Compound 89 to prepare an organic electroluminescent device.
  • the prepared device had a voltage of 4.94 V at an operating current density of 20 mA/cm 2 , a current efficiency of 5.05 cd/A, a blue light emission peak of 460 nm, and a CIEy of 0.160 at a luminance of 1000 cd/m 2 .
  • the prepared device had a voltage of 4.54 V at an operating current density of 20 mA/cm 2 , a current efficiency of 3.07 cd/A, a blue light emission peak of 452 nm, and a CIEy of 0.105 at a luminance of 1000 cd/m 2 .
  • Example 8 The same procedure as in Example 8 was carried out, except that Compound 3 was replaced with Compound 89 to prepare an organic electroluminescent device.
  • the prepared device had a voltage of 5.54 V at an operating current density of 20 mA/cm 2 , a current efficiency of 1.44 cd/A, a blue light emission peak of 452 nm, and a CIEy of 0.101 at a luminance of 1000 cd/m 2 .
  • the prepared device had a voltage of 5.24 V at an operating current density of 20 mA/cm 2 , a current efficiency of 2.60 cd/A, a blue light emission peak of 460 nm, and a CIEy of 0.164 at a luminance of 1000 cd/m 2 .
  • the prepared device had a voltage of 5.18 V at an operating current density of 20 mA/cm 2 , a current efficiency of 4.79 cd/A, a blue light emission peak of 460 nm, and a CIEy of 0.161 at a luminance of 1000 cd/m 2 .
  • the prepared device had a voltage of 4.89 V at an operating current density of 20 mA/cm 2 , a current efficiency of 2.10 cd/A, a blue light emission peak of 456 nm, and a CIEy of 0.132 at a luminance of 1000 cd/m 2 .
  • Examples 4, 5, 6, 7, 8 and 9 are specific applications of the material of the present invention, and the prepared device emits blue light, which has better luminous efficiency and brightness than the comparative example, and has a lower CIEy value, which proves to be suitable for organic electrolysis.
  • the fluorescent dye is doped with a blue light emitting device.
  • the material of the present invention has high stability, and the organic electroluminescent device prepared by the present invention has high efficiency and light purity.

Abstract

一种有机电致发光器件，包含阳极（20）、阴极（80）和有机层，有机层为空穴注入层（30）、空穴传输层（40）、电子注入层（70）、电子传输层（60）、发光层（50）中至少包括发光层（50）在内的一层或多层；发光层（50）为由主体材料和客体材料组成的主客体掺杂体系，发光层（50）的发光区域为蓝色440-490nm，主体材料或客体材料具有式(I)所示结构的化合物，该有机电致发光器件具有电致发光效率良好和色纯度优异以及寿命长的优点。

Description

有机电致发光器件 技术领域
本发明涉及新型的有机主体材料制备的有机电致发光蓝光器件，属于有机电致发光器件显示技术领域。
背景技术
有机电致发光器件作为一种新型的显示技术，具有自发光、宽视角、低能耗、效率高、薄、色彩丰富、响应速度快、适用温度范围广、低驱动电压、可制作柔性可弯曲与透明的显示面板以及环境友好等独特优点，因此，有机电致发光器件技术可以应用在平板显示器和新一代照明上，也可以作为LCD的背光源。
有机电子发光器件为在两个金属电极之间通过旋涂或者沉积一层有机材料而制备的器件，一个经典的三层有机电致发光器件包含空穴传输层，发光层和电子传输层。由阳极产生的空穴经空穴传输层跟由阴极产生的电子经电子传输层结合在发光层形成激子，而后发光。有机电致发光器件可以通过改变发光层的材料来发射红光，绿光和蓝光。因而，稳定的，高效的和色彩纯的有机电致发光材料对有机电致发光器件的应用和推广具有重要作用，同时也是OLEDs大面积面板显示的应用推广的迫切需求。
在三原色(红，蓝，绿)当中，红光和绿光材料最近已经取得了很大的发展，虽然红光、绿光有机电致发光器件的效能已经得到了明显提高，也符合面板的市场需求，但其效率和稳定性仍有待进一步提高。因此从材料设计和器件结构来解决上述问题是此领域研究的一个重点。在染料掺杂有机电致发光器件中，主体材料向掺杂发光体的能量转移效率对器件的效能与稳定性有很大的影响。经常使用的主体材料包括mCP和26DCzPPy及其衍生物，均含有氮原子。只含碳氢化合物的材料相对稳定性比较高，适合工业上应用以及商品化。对于蓝色荧光染料掺杂器件的主体材料，也有一系列的商品化的材料，其中早期使用较多的为9,10-二苯基蒽(DPA)，9,10-二(萘-2-基)蒽(ADN)和2-甲基-9,10-二(萘-2-基)蒽(MADN)，以这类化合物制备的器件具有较一般的效率，也因为分子的对称性所产生的易于结晶特点,在器件的薄膜形态容易发生变化，降低器件的稳定性，从而无法在OLED产业大量使用。
Figure PCTCN2015088711-appb-000001
发明内容
本发明就是克服上述器件的缺陷，提供一种电致发光效率良好和色纯度优异以及寿命长的有机电致荧光染料掺杂蓝光发光器件。
一种有机电致发光器件，包含阳极，阴极，和有机层，所述有机层为空穴注入层、空穴传输层、电子注入层、电子传输层、发光层中至少包括发光层在内的一层或多层；所述发光层为由主体材料和客体材料组成的主客体掺杂体系，发光层的发光区域为蓝色440-490nm，所述主体材料或客体材料具有式(I)所述结构的化合物，
Figure PCTCN2015088711-appb-000002
其中，R1-R17独立地表示为氢，氘原子，卤素，氰基，硝基，C1-C8烷基、C1-C8烷氧基，C6-C30的取代或者未取代的芳基，C3-C30的取代或者未取代的含有一个或者多个的杂原子芳基，C2-C8取代或者未取代的烯烷基，C2-C8取代或者未取代的炔烷基，其中，Ar1-Ar3独立地表示C6-C60取代或者未取代的芳基，C3-C60的取代或者未取代的带有一个或者多个杂原子的杂芳基，三芳香(C6-C30)胺基。
优选：其中，R1-R17独立地表示为氢，卤素，氰基，硝基，C1-C8烷基、C1-C8烷氧基，C2-C8取代或者未取代的烯烷基，C2-C8取代或者未取代的炔烷基，C1-C4烷基取代或未取代的苯基，C1-C4烷基取代或未取代的萘基，或结合成C1-C4烷基取代或未取代的芴基；Ar1-Ar3独立地表示C1-C4烷基或者C6-C30芳基取代的苯基，C1-C4烷基或者C6-C30芳基取代的萘基，苯基，萘基，吡啶基，N-C6-C30的芳基或者C1-C4的烷基取代的咔唑基，二苯并噻吩基，二苯并呋喃基，蒽基，菲基，芘基，苝基，荧蒽基，(9,9-二烷基)芴基，(9,9-二烷基取代或未取代芳基)芴基，9,9-螺芴基。
优选：其中，R1-R2可以独立地优选表示为氢，卤素，C1-C4的烷基，C1-C4烷基取代或未取代的苯基，C1-C4烷基取代或未取代的萘基，或结合成C1-C4烷基取代或未取代的芴基；其中，R3-R17可以独立地优选表示为氢，卤素，C1-C4的烷基，C1-C4烷基取代或未取代的苯基，C1-C4烷基取代或未取代的萘基，优选Ar1-Ar3为独立地表示苯基，甲苯基，二甲苯基，叔丁基苯基，萘基，吡啶基，甲基萘，联苯基，二苯基苯基，萘基苯基，二苯基联苯基，二芳香胺基苯基，N-苯基咔唑基，(9,9-二烷基)芴基，(9,9-二烷基取代或未取代苯基)芴基，9,9-螺芴基。
优选：其中，R3-R17优选为氢，R1，R2可以独立优选表示为氢，甲基，乙基，丙基，异丙基，叔丁基，苯基，联苯基，萘基，或结合成芴基；Ar1-Ar3为独立地表示苯基，吡啶基，甲苯基，二甲苯基，萘基，甲基萘，联苯基，二苯基苯基，萘基苯基，二苯基联苯基，(9,9-二烷基)芴基，(9,9-二甲基取代或未取代苯基)芴基，9,9-螺芴基。
优选：R3-R17优选为氢；R1，R2为独立地表示氢，甲基，或结合成芴基；Ar1，Ar2，Ar3为独立地表示苯基，萘基。
优选：式(I)所的化合物为下列结构化合物
Figure PCTCN2015088711-appb-000003
Figure PCTCN2015088711-appb-000004
所述有机层为空穴注入层，空穴传输层，发光层，空穴阻挡层、电子传输层中的一层或多层。需要特别指出，上述有机层可以根据需要，这些有机层不必每层都存在。
所述空穴传输层，电子传输层和/或发光层中含有式(I)所述的化合物。
所述式(I)所述的化合物位于发光层。
本发明的有机电致发光器件至少包括有一层发光层，该发光层的发光区域在蓝光440-490nm。
所述发光层为由主体材料和客体材料组成的主客体掺杂体系。
所述式(I)所述的化合物为主体材料和/或客体材料。
在掺杂体系中，其中主体材料的浓度为整个发光层重量的20-99.9％，优选80-99％，更优选为90-99％。而相应地客体材料的浓度为整个发光层重量的0.01-80％，优选1-20％，更优选为1-10％。
本发明的电子器件有机层的总厚度为1-1000nm，优选1-500nm，更优选50-300nm。
所述有机层可以通过蒸渡或旋涂形成薄膜。
如上面提到的，本发明的式(I)所述的化合物如下，但不限于所列举的结构：
Figure PCTCN2015088711-appb-000005
Figure PCTCN2015088711-appb-000006
Figure PCTCN2015088711-appb-000007
Figure PCTCN2015088711-appb-000008
Figure PCTCN2015088711-appb-000009
Figure PCTCN2015088711-appb-000010
Figure PCTCN2015088711-appb-000011
Figure PCTCN2015088711-appb-000012
Figure PCTCN2015088711-appb-000013
Figure PCTCN2015088711-appb-000014
Figure PCTCN2015088711-appb-000015
Figure PCTCN2015088711-appb-000016
Figure PCTCN2015088711-appb-000017
Figure PCTCN2015088711-appb-000018
Figure PCTCN2015088711-appb-000019
Figure PCTCN2015088711-appb-000020
Figure PCTCN2015088711-appb-000021
Figure PCTCN2015088711-appb-000022
Figure PCTCN2015088711-appb-000023
Figure PCTCN2015088711-appb-000024
Figure PCTCN2015088711-appb-000025
Figure PCTCN2015088711-appb-000026
Figure PCTCN2015088711-appb-000027
Figure PCTCN2015088711-appb-000028
Figure PCTCN2015088711-appb-000029
Figure PCTCN2015088711-appb-000030
Figure PCTCN2015088711-appb-000031
本发明中的空穴传输层和空穴注入层，所需材料具有很好的空穴传输性能，能够有效地把空穴从阳极传输到有机发光层上。可以包括小分子和高分子有机材料，可以包含如下，但是不限于这些，三芳香胺化合物，联苯二胺化合物，噻唑化合物，恶唑化合物，咪唑类化合物，芴类化合物，酞菁类化合物，六氰基六杂三苯(hexanitrile hexaazatriphenylene)，2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌(F4-TCNQ)，聚乙烯基咔唑，聚噻吩，聚乙烯，聚苯磺酸。
本发明的有机电致发光层，除含有本发明的结构式(I)化合物外，还可以含有如下化合物，但是不限于此，萘类化合物，芘类化合物，芴类化合物，菲类化合物，屈类化合物，荧蒽类化合物，蒽类化合物，并五苯类化合物，苝类化合物，二芳乙烯类化合物，三苯胺乙烯类化合物，胺类化合物，苯并咪唑类化合物，呋喃类化合物，有机金属螯合物。
本发明的有机电子器件使用的有机电子传输材料要求具有很好的电子传输性能，能够有效地把电子从阴极传输到发光层中，可以选择如下化合物，但是不限于此，氧杂恶唑，噻唑类化合物，三氮唑类化合物，三氮嗪类化合物，三氮杂苯类化合物，喔啉类化合物，二氮蒽类化合物，含硅杂环类化合物，喹啉类化合物，菲啰啉类化合物，金属螯合物，氟取代苯类化合物。
本发明的有机电子器件根据需要，可以加入一层电子注入层，该电子注入层可以有效的把电子从阴极注入到有机层中，主要选自碱金属或者碱金属的化合物，或选自碱土金属或者 碱土金属的化合物，可以选择如下化合物，但是不限于此，锂，氟化锂，氧化锂，氮化锂，8-羟基喹啉锂，铯，碳酸铯，8-羟基喹啉铯，钙，氟化钙，氧化钙，镁，氟化镁，碳酸镁，氧化镁。
器件实验表明，本发明的有机电致发光器件具有电致发光效率良好和色纯度优异以及寿命长的优点。
附图说明
图1为本发明的器件结构图，
其中10代表为玻璃基板，20代表为阳极，30代表为空穴注入层，40代表为空穴传输层，50代表为发光层，60代表为电子传输层，70代表为电子注入层，80代表为阴极。
图2为化合物89的1H NMR图。
图3为化合物89的13C NMR图。
图4为化合物89的HPLC图。
图5为化合物89的TGA图。
图6为实施例4,5及比较例1的电压–电流密度曲线图
图7为实施例6,7及比较例2的电压–电流密度曲线图
图8为实施例8,9及比较例3的电压–电流密度曲线图
图9为实施例4,5及比较例1的电流密度–电流效率曲线图
图10为实施例6,7及比较例2的电流密度–电流效率曲线图
图11为实施例8,9及比较例3的电流密度–电流效率曲线图
图12为实施例4,5及比较例1的电致发光光谱
图13为实施例6,7及比较例2的电致发光光谱
图14为实施例8,9及比较例3的电致发光光谱
图15为实施例4,5及比较例1的亮度–CIEy坐标图
图16为实施例6,7及比较例2的亮度–CIEy坐标图
图17为实施例8,9及比较例3的亮度–CIEy坐标图
具体实施方式
为了更详细叙述本发明，特举以下例子，但是不限于此。
(其中下面的化合物1a、1b、1e、1h，3a、89a为市售的常用材料)
实施例1
Figure PCTCN2015088711-appb-000032
中间体1c的合成
向反应烧瓶中加入1a(240.00g,0.88mol),1b(496.32g,1.76mol),Pd(PPh3)4(20.35g,17.60mmol)，碳酸钾(302.52g,2.20mol)，甲苯(2400mL)，纯水(1200mL)。抽放氮气三次后开启加热，待反应液温度达到95-105℃，保持此温度反应8-12h，取样TLC及HPLC，原料反应完全。停止加热，降温至20-30℃，抽滤，滤液分出有机层，水层再用乙酸乙酯萃取，合并有机层，再用水洗，无水硫酸镁干燥，抽滤，滤液浓缩得到暗黄色固体粗产品。石油醚重结晶，得到灰白色固体产品，收率90％，纯度95％。
中间体1d的合成
向反应烧瓶中加入相应比例的1c(302g,0.78mol),B(OEt)3(142g,0.97mol),n-BuLi/THF(1.6M,600mL),无水THF(3000mL)，抽放氮气三次后冷却降温至反应液温度至-75～-65℃，缓慢滴加n-BuLi/THF溶液，控制反应液温度在-75～-65℃，滴加完毕后，继续保持此温度反应0.5-1h。后将一定量的B(OEt)3滴加进去，控制反应液温度在-75～-65℃，滴加完 毕后，继续保持此温度反应0.5-1h，后反应液移至室温自然升温反应4-6h，然后加入2M稀盐酸，调节PH值至2-3，搅拌约1h，停止反应。加入乙酸乙酯萃取，水层再用EA萃取，合并有机层，无水硫酸镁干燥，抽滤，滤液浓缩得到得到灰白色固体产品，纯度95％，收率62.5％。
中间体1f的合成
向反应烧瓶中加入1d(150g,0.43mol),1e(500g,0.86mol),Pd(PPh3)4(5.0g,0.44mmol)，碳酸钾(130g,0.92mol)，甲苯(1000mL)，纯水(500mL),抽放氮气三次开启加热，待反应液温度达到95-105℃，保持此温度反应8-12h，取样TLC及HPLC，原料反应完全。停止加热，降温至20-30℃，抽滤，滤液分出有机层，水层再用乙酸乙酯萃取，合并有机层，无水硫酸镁干燥，抽滤，滤液浓缩得到暗黄色固体粗产品，纯度80％，收率78.1％。
中间体1g的合成
向反应烧瓶中加入1f(210g,0.42mol),NBS(135g,0.71mol),DMF(5L)。抽放氮气三次开启加热，待反应液温度达到60-65℃，保持此温度反应6-8h，取样TLC及HPLC，原料反应完全。停止加热，降温至20-30℃，反应液倒入冰水中，析出暗黄色固体，抽滤得到黄色固体，烘干得到1g粗产品。粗产品加入DCM/MeOH至溶液稍微变混浊，继续搅拌约30min，析出大量固体，抽滤，得到浅黄色固体产品，收率约54.05％，纯度98.5％
1H NMR(300MHz,CDCl3)δ8.64(d,J＝8.8Hz,2H),7.99–7.90(m,4H),7.87(t,J＝1.6Hz,1H),7.78(dd,J＝9.3,2.3Hz,6H),7.61(ddd,J＝8.8,6.5,1.1Hz,2H),7.56–7.48(m,6H),7.46–7.38(m,4H).
13C NMR(76MHz,CDCl3)δ142.67(s),142.03(s),141.26(s),140.69(s),137.83(s),137.52(s),131.87(s),131.24(s),130.44(s),129.09(s),128.80(s),128.38–127.40(m),127.18(s),126.05–125.21(m),123.08(s),77.74(s),77.31(s),76.89(s),30.10(s).
化合物1的合成
向500ml三口烧瓶中依次加入1g(9.5g,16.92mmol),1h(6.41g,30.51mmol),Pd(PPh3)4(1.5g,1.3mmol)，碳酸钾(5.84g,42.3mmol)，甲苯(150mL)，纯水(75mL)。抽放氮气三次后105℃下反应。由液相检测停反应时间，约12h左右。反应开始时反应液为催化剂的土黄色，之后慢慢变成黄色溶液，停反应后上层为清亮浅黄色，下层为水。停止反应后，过 滤，用乙酸乙酯洗滤渣直至滤渣中无产物，收集滤液，旋干，大量的灰白色固体析出，收集滤渣干燥，得到目标产物，纯度98％。真空升华得到纯度为99.5％灰白色固体粉末。
1H-NMR(300MHz,CDCl3)δ8.10–8.21(d，2H)，7.96–7.98(dd，3H)，7.87–7.89(m，2H)，7.81–7.86(m，4H)，7.78–7.81(d，4H),7.62–7.65(m，2H)，7.59(s，1H)，7.51–7.57(m，5H)，7.45–7.48(m，2H)，7.36–7.43(m，7H)，3.88(s，2H).
实施例2
化合物3的合成
Figure PCTCN2015088711-appb-000033
向500ml三口烧瓶中依次加入1g(9.5g,16.92mmol),3a(7.25g,30.46mmol),Pd(PPh3)4(1.5g,1.3mmol)，碳酸钾(5.84g,42.3mmol)，甲苯(150mL)，纯水(75mL)。抽放氮气三次后105℃下反应。由液相检测停反应时间，约12h左右。反应开始时反应液为催化剂的土黄色，之后慢慢变成黄色溶液，停反应后上层为清亮浅黄色，下层为水。停止反应后，过滤，用乙酸乙酯洗滤渣直至滤渣中无产物，收集滤液，旋干，大量的灰白色固体析出，收集滤渣干燥，得到目标产物，纯度98％。真空升华得到纯度为99.7％灰白色固体粉末。
1H-NMR(300MHz,CDCl3)δ8.1–8.2(d，2H)，7.96–7.99(dd，3H)，7.88–7.89(m，2H)，7.81–7.86(m，4H)，7.78–7.81(d，4H),7.61–7.65(m，2H)，7.59(s，1H)，7.51–7.56(m，5H)，7.46–7.48(m，2H)，7.35–7.43(m，7H)，1.61(s，6H).
实施例3
化合物89的合成
Figure PCTCN2015088711-appb-000034
向反应容器中依次加入1g(10.0g,17.8mmol),89a(7.1g,19.6mmol),Pd(PPh3)4(432.2mg,0.35mmol),K2CO3(6.14g,44.5mmol),甲苯(300mL)和水(150mL)，对装置进行除氧、通入氮气保护，然后加热到100℃反应过夜。用DCM：PE＝1:5的比例点板，产物点在365nm波长的紫外灯下发强烈的蓝光，Rf值在0.2左右。将反应液用硅胶抽滤，然后将滤饼用乙酸乙酯(100mL)洗涤两次，分液，用乙酸乙酯(100mL)萃取水层一次，合并有机层，再用水(200mL)洗涤一次有机相。旋干除去溶剂。粗品用120ml DCM/MeOH重结晶，抽滤得到黄色固体粉末13.1g，纯度为98.7％，收率92.2％。真空升华得到纯度为99.7％浅黄色固体粉末。m/z＝797.
从图2和图3可见化合物89的氢谱，碳谱与结构完全一致。从图4化合物89的高效液相色谱图可见根据本发明的合成方法制备的产物具有高纯度。从图5化合物89的热重分析图可见这类型化合物的分解温度高于摄氏400度，表明其非常高热稳定性。
实施例4
有机电致发光器件1的制备
使用本发明的有机电子材料制备OLED
首先，将透明导电ITO玻璃基板10(上面带有阳极20)依次经：洗涤剂溶液和去离子水，乙醇，丙酮，去离子水洗净，再用氧等离子处理30秒。
然后，在ITO上蒸渡10nm厚的HAT-CN6作为空穴注入层30。
然后，蒸渡NPB,形成30nm厚的空穴传输层40。
然后，在空穴传输层上蒸渡30nm厚的化合物B1(2％)与化合物3(98％)作为发光层50。
然后，在发光层上蒸渡15nm厚的TPBi作为电子传输层60。
最后，蒸渡15nm BPhen:Li为电子注入层70和150nm Al作为器件阴极80。所制备的器件在20mA/cm2的工作电流密度下的电压为3.87V，电流效率达到4.57cd/A，发射蓝光峰值460nm，在1000cd/m2亮度下CIEy为0.135。
器件中所述结构式
Figure PCTCN2015088711-appb-000035
Figure PCTCN2015088711-appb-000036
实施例5
有机电致发光器件2的制备
方法同实施例4,将化合物3，换成化合物89，制作有机电致发光器件。
所制备的器件在20mA/cm2的工作电流密度下的电压为4.91V，电流效率达到4.31cd/A，发射蓝光峰值456nm，在1000cd/m2亮度下CIEy为0.143。
实施例6
有机电致发光器件3的制备
方法同实施例4,将化合物B1，换成化合物B2，制作有机电致发光器件。
所制备的器件在20mA/cm2的工作电流密度下的电压为4.09V，电流效率达到5.27cd/A，发射蓝光峰值460nm，在1000cd/m2亮度下CIEy为0.155。
实施例7
有机电致发光器件4的制备
方法同实施例6,将化合物3，换成化合物89，制作有机电致发光器件。
所制备的器件在20mA/cm2的工作电流密度下的电压为4.94V，电流效率达到5.05cd/A，发射蓝光峰值460nm，在1000cd/m2亮度下CIEy为0.160。
实施例8
有机电致发光器件5的制备
方法同实施例4,将化合物B1，换成化合物B3，制作有机电致发光器件。
所制备的器件在20mA/cm2的工作电流密度下的电压为4.54V，电流效率达到3.07cd/A，发射蓝光峰值452nm，在1000cd/m2亮度下CIEy为0.105。
实施例9
有机电致发光器件6的制备
方法同实施例8,将化合物3，换成化合物89，制作有机电致发光器件。
所制备的器件在20mA/cm2的工作电流密度下的电压为5.54V，电流效率达到1.44cd/A，发射蓝光峰值452nm，在1000cd/m2亮度下CIEy为0.101。
比较例1
有机电致发光器件7的制备
方法同实施例4，将化合物3，换成化合物MADN，制作有机电致发光器件。
所制备的器件在20mA/cm2的工作电流密度下的电压为5.24V，电流效率达到2.60cd/A，发射蓝光峰值460nm，在1000cd/m2亮度下CIEy为0.164。
比较例2
有机电致发光器件8的制备
方法同实施例6，将化合物3，换成化合物MADN，制作有机电致发光器件。
所制备的器件在20mA/cm2的工作电流密度下的电压为5.18V，电流效率达到4.79cd/A，发射蓝光峰值460nm，在1000cd/m2亮度下CIEy为0.161。
比较例3
有机电致发光器件9的制备
方法同实施例8，将化合物3，换成化合物MADN，制作有机电致发光器件。
所制备的器件在20mA/cm2的工作电流密度下的电压为4.89V，电流效率达到2.10cd/A，发射蓝光峰值456nm，在1000cd/m2亮度下CIEy为0.132。
实施例4,5,6,7,8和9是本发明材料的具体应用，所制备的器件发射蓝光，较比较例发光效率和亮度更良好，CIEy值较低，证明适合用于有机电致荧光染料掺杂蓝光发光器件。如上所述，本发明的材料具有高的稳定性，本发明制备的有机电致发光器件具有高的效率和光纯度。

Claims (12)

  1. 一种有机电致发光器件，包含阳极，阴极，和有机层，所述有机层为空穴注入层、空穴传输层、电子注入层、电子传输层、发光层中至少包括发光层在内的一层或多层；所述发光层为由主体材料和客体材料组成的主客体掺杂体系，发光层的发光区域为蓝色440-490nm，所述主体材料或客体材料具有式(I)所述结构的化合物，
    Figure PCTCN2015088711-appb-100001
    其中，R1-R17独立地表示为氢，氘原子，卤素，氰基，硝基，C1-C8烷基、C1-C8烷氧基，C6-C30的取代或者未取代的芳基，C3-C30的取代或者未取代的含有一个或者多个的杂原子芳基，C2-C8取代或者未取代的烯烷基，C2-C8取代或者未取代的炔烷基，其中，Ar1-Ar3独立地表示C6-C60取代或者未取代的芳基，C3-C60的取代或者未取代的带有一个或者多个杂原子的杂芳基，三芳香(C6-C30)胺基。
  2. 根据权利要求1所述的有机电致发光器件，其中，R1-R17独立地表示为氢，卤素，氰基，硝基，C1-C8烷基、C1-C8烷氧基，C2-C8取代或者未取代的烯烷基，C2-C8取代或者未取代的炔烷基，C1-C4烷基取代或未取代的苯基，C1-C4烷基取代或未取代的萘基，或结合成C1-C4烷基取代或未取代的芴基；Ar1-Ar3独立地表示C1-C4烷基或者C6-C30芳基取代的苯基，C1-C4烷基或者C6-C30芳基取代的萘基，苯基，萘基，吡啶基，N-C6-C30的芳基或者C1-C4的烷基取代的咔唑基，二苯并噻吩基，二苯并呋喃基，蒽基，菲基，芘基，苝基，荧蒽基，(9,9-二烷基)芴基，(9,9-二烷基取代或未取代芳基)芴基，9,9-螺芴基。
  3. 根根据权利要求2所述的有机电致发光器件，其中，R1-R2可以独立地优选表示为氢，卤素，C1-C4的烷基，C1-C4烷基取代或未取代的苯基，C1-C4烷基取代或未取代的萘基，或结合成C1-C4烷基取代或未取代的芴基；其中，R3-R17可以独立地优选表示为氢，卤素，C1-C4的烷基，C1-C4烷基取代或未取代的苯基，C1-C4烷基取代或未取代的萘基，Ar1-Ar3 为独立地表示苯基，甲苯基，叔丁基苯基，萘基，吡啶基，甲基萘，联苯基，二苯基苯基，萘基苯基，二苯基联苯基，二芳香胺基苯基，N-苯基咔唑基，(9,9-二烷基)芴基，(9,9-二烷基取代或未取代苯基)芴基，9,9-螺芴基。
  4. 根据权利要求3所述的有机电致发光器件，其中，R3-R17优选为氢，R1，R2可以独立优选表示为氢，甲基，乙基，丙基，异丙基，叔丁基，苯基，萘基，或结合成芴基；Ar1-Ar3为独立地表示苯基，吡啶基，甲苯基，萘基，甲基萘，联苯基，二苯基苯基，萘基苯基，二苯基联苯基，(9,9-二烷基)芴基，(9,9-二甲基取代或未取代苯基)芴基，9,9-螺芴基。
  5. 根据权利要求4所述的有机电致发光器件，R3-R17优选为氢；R1，R2为独立地表示氢，甲基，或结合成芴基；Ar1，Ar2，Ar3为独立地表示苯基，萘基。
  6. 根据权利要求1所述的有机电致发光器件，其式(I)所述的化合物为：
    Figure PCTCN2015088711-appb-100002
    Figure PCTCN2015088711-appb-100003
    Figure PCTCN2015088711-appb-100004
    Figure PCTCN2015088711-appb-100005
    Figure PCTCN2015088711-appb-100006
    Figure PCTCN2015088711-appb-100007
    Figure PCTCN2015088711-appb-100008
    Figure PCTCN2015088711-appb-100009
    Figure PCTCN2015088711-appb-100010
    Figure PCTCN2015088711-appb-100011
    Figure PCTCN2015088711-appb-100012
    Figure PCTCN2015088711-appb-100013
    Figure PCTCN2015088711-appb-100014
    Figure PCTCN2015088711-appb-100015
    Figure PCTCN2015088711-appb-100016
    Figure PCTCN2015088711-appb-100017
    Figure PCTCN2015088711-appb-100018
    Figure PCTCN2015088711-appb-100019
    Figure PCTCN2015088711-appb-100020
    Figure PCTCN2015088711-appb-100021
    Figure PCTCN2015088711-appb-100022
    Figure PCTCN2015088711-appb-100023
    Figure PCTCN2015088711-appb-100024
    Figure PCTCN2015088711-appb-100025
    Figure PCTCN2015088711-appb-100026
    Figure PCTCN2015088711-appb-100027
  7. 根据权利要求6所述的有机电致发光器件，为下列结构化合物
    Figure PCTCN2015088711-appb-100028
  8. 根据权利要求1-7任一所述的有机电致发光器件，其中主体材料的浓度为整个发光层重量的20-99.9％，客体材料的浓度为整个发光层重量的0.01-80％。
  9. 根据权利要求8所述的有机电致发光器件，其中主体材料的浓度为整个发光层重量的80-99％，客体材料的浓度为整个发光层重量的1-20％。
  10. 根据权利要求9所述的有机电致发光器件，主体材料为式(I)所示结构的化合物，其浓度为整个发光层重量的90-99％；客体材料的浓度为整个发光层重量的1-10％，所述客体材料为萘类化合物，芘类化合物，芴类化合物，菲类化合物，屈类化合物，荧蒽类化合物，蒽类化合物，并五苯类化合物，苝类化合物，二芳乙烯类化合物，三苯胺乙烯类化合物，胺类化合物，苯并咪唑类化合物，呋喃类化合物，有机金属螯合物。
  11. 根据权利要求9所述的有机电致发光器件，所述客体材料为如下结构中的一种或多种，
    Figure PCTCN2015088711-appb-100029
    Figure PCTCN2015088711-appb-100030
  12. 根据权利要求9所述的有机电致发光器件，所述式(I)所述的化合物还位于空穴注入层、空穴传输层、电子传输层和/或电子注入层。
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KR20170124555A (ko) 2017-11-10
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US10505118B2 (en) 2019-12-10
KR102060582B1 (ko) 2019-12-30
TW201632488A (zh) 2016-09-16
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JP6529196B2 (ja) 2019-06-12
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