WO2019000494A1 - 一种芴类有机电致发光化合物及其有机电致发光器件 - Google Patents

一种芴类有机电致发光化合物及其有机电致发光器件 Download PDF

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WO2019000494A1
WO2019000494A1 PCT/CN2017/092792 CN2017092792W WO2019000494A1 WO 2019000494 A1 WO2019000494 A1 WO 2019000494A1 CN 2017092792 W CN2017092792 W CN 2017092792W WO 2019000494 A1 WO2019000494 A1 WO 2019000494A1
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organic electroluminescent
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compound
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substituted
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黄锦海
苏建华
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上海道亦化工科技有限公司
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Definitions

  • the invention relates to the field of organic electroluminescent materials, in particular to a terpenoid organic electroluminescent material and an organic electroluminescent device thereof, and belongs to the technical field of organic electroluminescent device display.
  • OLEDs are devices prepared by spin coating or vacuum evaporation of an organic material between two metal electrodes.
  • a classic three-layer organic electroluminescent device comprises a hole transport layer. Light emitting layer and 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 adjust the emission of various desired light by changing the material of the light-emitting layer as needed.
  • 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
  • the unique advantages of a transparent display panel and environmental friendliness can be applied to flat panel displays and next-generation lighting, or as a backlight for LCDs.
  • organic electroluminescent devices have been used in the industry, such as screens such as cameras and mobile phones, but current OLED devices are constrained by wider applications due to low efficiency and short service life. Especially for large screen displays, it is necessary to increase the efficiency of the device. An important factor limiting this is the performance of organic electroluminescent materials in organic electroluminescent devices.
  • the OLED device since the OLED device generates Joule heat when the voltage is applied, the organic material is easily crystallized, which affects the life and efficiency of the device. Therefore, it is also required to develop a stable and efficient organic electroluminescent material.
  • the organic electrophosphorescence phenomenon has broken the theoretical limit of the quantum efficiency of organic electroluminescence below 25%, and has been increased to 100%, and its application has greatly improved the efficiency of organic electroluminescent devices.
  • electrophosphorescence requires the use of host-guest doping technology.
  • CBP 4,4'-bis(9-carbazolyl)-biphenyl
  • CBP 4,4'-bis(9-carbazolyl)-biphenyl
  • the triplet energy can be efficiently transferred from the luminescent host material to the guest phosphorescent material.
  • the holes of CBP are easily transported and the electrons are difficult to flow, the charge of the light-emitting layer is unbalanced, and as a result, the efficiency of the device is lowered.
  • the present invention first provides a quinone-based organic electroluminescent compound which is a compound having the following structural formula I:
  • R 1 -R 10 are each independently selected from hydrogen, C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted 5 Or a 6-membered heterocycloalkyl group, a substituted or unsubstituted C12-C30 diarylamine group, a substituted or unsubstituted C18-C30 triarylamine group, or a carbazolyl group.
  • R 1 is selected from a C1-C12 alkyl group, an aryl group of a C6-C30 group substituted or unsubstituted by a C1-C12 alkyl group, a C3-C30 heteroaryl group substituted by a C1-C12 alkyl group or unsubstituted.
  • R 2 and R 3 are each independently selected from the group consisting of hydrogen, methyl, and benzene.
  • R 4 to R 8 are each independently selected from the group consisting of hydrogen, benzene, naphthalene, triphenyl, C6-C30 N-aryl, C1-C4 alkyl-substituted oxazolyl, fluorenyl, fluorene Azathiol, carbazolyl, fluorenyl, phenanthryl, fluorenyl, fluorenyl, fluorantyl, (9,9-dialkyl) fluorenyl, (9,9-disubstituted or unsubstituted aryl Mercapto, 9,9-spiroblyl, C18-C60 triarylamine, C12-C30 dibenzofuranyl, pyridyl, pyrimidinyl, anthracene substituted or unsubstituted by C1-C12 alkyl Azinyl, triazinyl, imidazolyl, oxazolyl, thiazolyl
  • R 9 is selected from the group consisting of hydrogen, C1-C12 alkyl.
  • the oxime-based organic electroluminescent compound of the present invention is a compound of the following structural formula 1-154:
  • the present invention also provides an organic electroluminescent device comprising an anode, a cathode and an organic layer, the organic layer comprising a light-emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, and an electron transport At least one of the layers, wherein at least one of the organic layers comprises an organic electroluminescent material as described in Structural Formula I:
  • the organic layer is a light-emitting layer
  • the organic layer is a light emitting layer and an electron transport layer
  • the organic layer is a light emitting layer, an electron transport layer, and an electron injection layer;
  • the organic layer is a hole transport layer and a light emitting layer
  • the organic layer is a hole injection layer, a hole transport layer, and a light-emitting layer
  • the organic layer is a hole transport layer, a light emitting layer, and an electron transport layer;
  • the organic layer is a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer;
  • the organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer;
  • the organic layer is a hole injection layer, a hole transport layer, a barrier layer, a light-emitting layer, an electron transport layer, and an electron injection layer;
  • the organic layer is a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer;
  • the organic layer is a hole transport layer, a light emitting layer, an electron injecting layer, and a hole blocking layer.
  • the layer of the quinone-based organic electroluminescent compound as described in Structural Formula I is any one or two of the light-emitting layer and the electron transport layer.
  • the oxime-based organic electroluminescent compound of formula I is a compound of structural formula 1-154.
  • the quinone compound of the formula I When used for the preparation of the light-emitting device, it may be used alone or in combination with other compounds; the quinone compound of the formula I may be used alone or in combination. Two or more compounds of structural formula I.
  • the organic electroluminescent device comprises an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a cathode, wherein the light emitting layer
  • the luminescent layer contains one or more compounds of formula 1-154.
  • the light-emitting layer of the organic electroluminescent device of the present invention comprises a phosphorescent guest material and a compound of the formula I as a host material, wherein the compound of the formula I is used as a host material at a concentration of from 20 to 99.9%, preferably 80-by weight of the entire light-emitting layer. 99%.
  • the organic electroluminescent device of the present invention has a total thickness of the organic layer of from 1 to 1000 nm, preferably from 50 to 500 nm.
  • the organic electroluminescent device of the present invention can be used in combination with other materials such as a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a barrier layer when using the compound of the formula I of the present invention.
  • a hole injecting layer a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a barrier layer when using the compound of the formula I of the present invention.
  • a barrier layer when using the compound of the formula I of the present invention.
  • the hole transport layer and the hole injection layer of the organic electroluminescent device of the present invention have a good hole transporting property and can efficiently transport holes from the anode to the light emitting layer.
  • other small molecules and high molecular organic compounds may be included, including but not limited to carbazole compounds, triarylamine compounds, biphenyldiamine compounds, terpenoids, phthalocyanine compounds, Hexanitrilehexaazatriphenylene, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (F4-TCNQ), polyvinyl fluorene Oxazole, polythiophene, polyethylene or polybenzenesulfonic acid.
  • the light-emitting layer of the organic electroluminescent device of the present invention has excellent light-emitting characteristics, and the range of visible light can be adjusted as needed.
  • the compound of the present invention may be used as a host luminescent material, and may also contain the following compounds, including but not limited to naphthalene compounds, terpenoids, terpenoids, phenanthrene compounds, Compounds, fluoranthene compounds, terpenoids, pentacene compounds, terpenoids, diarylene compounds, triphenylamine vinyl compounds, amine compounds, benzimidazoles, furans, organometallics Chelates, which may be used singly or in combination of plural kinds.
  • the organic electron transporting material of the organic electroluminescent 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 has a large electron mobility.
  • the following compounds may be selected, but are not limited thereto: oxazolylazole, thiazole compound, triazole compound, triazine compound, triazabenzene compound, Porphyrin compounds, diazonium compounds, silicon-containing heterocyclic compounds, quinoline compounds, phenanthroline compounds, metal chelates (such as Alq 3 ), fluorine-substituted benzenes, benzimidazoles .
  • the electron injecting layer of the organic electroluminescent device of the invention can effectively inject electrons from the cathode into the organic layer, mainly selected from alkali metal or alkali metal compounds, or compounds selected from alkaline earth or alkaline earth metals or alkali metal networks.
  • the compound may be selected from, but not limited to, an alkali metal, an alkaline earth metal, a rare earth metal, an oxide or halide of an alkali metal, an oxide or a halide of an alkaline earth metal, an oxide or a halide of a rare earth metal, or a base.
  • An organic complex of a metal or an alkaline earth metal preferably lithium, lithium fluoride, lithium oxide, lithium nitride, lithium quinolate, hydrazine, cesium carbonate, 8-hydroxyquinolinium, calcium, calcium fluoride, Calcium oxide, magnesium, magnesium fluoride, magnesium carbonate, magnesium oxide, these compounds may be used singly or in combination with other organic electroluminescent materials.
  • Each layer of the organic layer in the organic electroluminescent device of the present invention may be subjected to vacuum evaporation, molecular beam evaporation, solvent dip coating, spin coating, bar coating or inkjet printing.
  • the metal motor can be prepared by an evaporation method or a sputtering method.
  • the device experiments show that the ruthenium-based organic electroluminescent compound of the invention of the formula I has good thermal stability, high luminous efficiency and high luminescence purity.
  • the organic electroluminescent device produced by using the organic electroluminescent compound has the advantages of good electroluminescence efficiency, excellent color purity, and long life.
  • FIG. 1 is a schematic structural view of an organic electroluminescent device of the present invention
  • FIG. 2 is a schematic view showing the structure of another organic electroluminescent device of the present invention.
  • 110 represents a glass substrate
  • 120 represents an anode
  • 130 represents a hole injection layer
  • 140 represents a hole transport layer
  • 150 represents a barrier layer
  • 160 represents a light-emitting layer
  • 170 represents an electron transport layer
  • 180 represents an electron injection layer
  • 190 represents a cathode.
  • reaction mixture was cooled to room temperature, and the tetrahydrofuran was removed by rotary evaporation, then washed with water, and extracted three times with dichloromethane (10 mL each time). The organic phase was combined and dried over anhydrous sodium sulfate.
  • reaction mixture was cooled to room temperature, and the tetrahydrofuran was removed by rotary evaporation, then washed with water, and extracted three times with dichloromethane (10 mL each time). The combined organic layers were dried over anhydrous sodium sulfate and then evaporated
  • the synthesis method was the same as that of the intermediate 11-1, and the material used was Intermediate 37-1, yield 77%.
  • the synthesis method was the same as that of the intermediate 8-1, and the starting material was 2-amino-6-bromothiophenol, and the yield was 69%.
  • the synthesis method was the same as that of the intermediate 8-1, and the yield was 64%.
  • the synthesis method was the same as the intermediate 37-1, and the yield was 57%.
  • the transparent conductive ITO glass substrate 110 (with the anode 120 on the surface) (China CSG Group Co., Ltd.) was successively washed with deionized water, ethanol, acetone and deionized water, and then treated with oxygen plasma for 30 seconds.
  • NPB was evaporated to form a hole transport layer 130 having a thickness of 60 nm.
  • the compound 8 of the present invention was evaporated on the hole transport layer to form a light-emitting layer 140 having a thickness of 30 nm.
  • LiF LiF was deposited as an electron injection layer 160 and 100 nm of Al as the device cathode 170.
  • the prepared device (see Fig. 1 for the structure) was subjected to a blue light at a current efficiency of 2.1 cd/A at 20 mA/cm 2 as measured by a Photo Research PR650 spectrometer.
  • Example 13 The same procedure as in Example 13 was carried out except that the luminescent layer was replaced with MADN in place of the compound of the present invention.
  • the measured current efficiency was 1.4 cd/A, and blue light was emitted.
  • the current efficiency of the organic electroluminescent device prepared by using the organic electroluminescent compound of the present invention was higher than that of the comparative example.
  • the compound of the present invention has high stability, and the organic electroluminescent device prepared by the present invention has low driving voltage, high efficiency and light purity.
  • the transparent conductive ITO glass substrate 110 (with the anode 120 on the surface) (China CSG Group Co., Ltd.) was successively washed with deionized water, ethanol, acetone and deionized water, and then treated with oxygen plasma for 30 seconds.
  • NPB was evaporated to form a hole transport layer 130 having a thickness of 60 nm.
  • a compound of the present invention having a thickness of 37.5 nm and Liq as an electron transport layer 150 were deposited on the light-emitting layer, and the ratio of the compound of the present invention to Liq was 1:1.
  • LiF LiF was deposited as an electron injection layer 160 and 100 nm of Al as the device cathode 170.
  • the prepared device (see Fig. 1 for a schematic structure) was measured by a Photo Research PR650 spectrometer at a current density of 20 mA/cm 2 as shown in Table 1.
  • the prepared device (see Fig. 2 for a schematic structure) was measured by a Photo Research PR650 spectrometer at a current density of 20 mA/cm 2 as shown in Table 1.
  • the transparent conductive ITO glass substrate 110 (with the anode 120 on the surface) (China CSG Group Co., Ltd.) was successively washed with deionized water, ethanol, acetone and deionized water, and then treated with oxygen plasma for 30 seconds.
  • MnO 3 mobdenum oxide
  • TAPC vapor-deposited on the hole injection layer to form a hole transporting material 140.
  • TCTA was evaporated to form a 5 nm thick electron blocking layer 150.
  • a 20 nm thick light-emitting layer 160 was deposited on the electron blocking layer, wherein the compound of the present invention was a host light-emitting material, and 3% by weight of Ir(ppy) 3 was used as the phosphorescent dopant guest material.
  • LiF LiF was deposited as an electron injection layer 180 and 80 nm of Al as the device cathode 190.
  • the external quantum efficiency at a luminance of 5000 cd/m 2 as measured by a Photo Research PR650 spectrometer was as shown in Table 2 for the prepared device (see FIG. 2).
  • Example 38 The preparation method of Example 38 was the same as that of Examples 28 to 37 except that the light-emitting layer was co-evaporated with CBP and Compound 11 as a host material, and the mass ratio thereof was 7:3.
  • Example 39 The preparation method of Example 39 was the same as that of Example 38 except that the light-emitting layer was co-evaporated with CBP and Compound 25 as a host material, and the mass ratio was 7:3.
  • the device prepared in the comparative example was the same as the preparation method of Examples 28-37 except that CBP was used instead of the compound of the present invention as a host material.
  • the prepared device (see Fig. 2 for a schematic structure) was measured by a Photo Research PR650 spectrometer at a current density of 20 mA/cm 2 as shown in Table 2.
  • the organic electroluminescent device prepared by the organic electroluminescent compound of the present invention can reduce the operating voltage and improve the device efficiency, and is a phosphorescent host material having excellent properties.
  • the compound of the present invention has high stability, and the prepared organic electroluminescent device has high efficiency and light purity.

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Abstract

提供一种芴类有机电致发光化合物，其具有如下结构：该化合物具有较好的热稳定性，高发光效率，高发光纯度，可以用于制作有机电致发光器件，应用于有机太阳能电池、有机薄膜晶体管或有机光感受器领域。还提供一种有机电致发光器件，该器件包括阳极、阴极和有机层，有机层包含发光层、空穴注入层、空穴传输层、电子注入层、电子传输层中的至少一层，有机层中至少一层包含如结构式Ⅰ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

一种芴类有机电致发光化合物及其有机电致发光器件 技术领域
本发明涉及有机电致发光材料领域，具体涉及一种芴类有机电致发光材料及其有机电致发光器件，属于有机电致发光器件显示技术领域。
技术背景
有机电致发光器件(OLEDs)为在两个金属电极之间通过旋涂或者真空蒸镀沉积一层有机材料制备而成的器件，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根据需要通过改变发光层的材料来调节发射各种需要的光。
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，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。
自从20世纪80年代底发明以来，有机电致发光器件已经在产业上有所应用，比如作为相机和手机等屏幕，但是目前的OLED器件由于效率低，使用寿命短等因素制约其更广泛的应用，特别是大屏幕显示器，因此需要提高器件的效率。而制约其中的一个重要因素就是有机电致发光器件中的有机电致发光材料的性能。另外由于OLED器件在施加电压运行的时候，会产生焦耳热，使得有机材料容易发生结晶，影响了器件的寿命和效率，因此，也需要开发稳定高效的有机电致发光材料。
有机电致磷光现象，突破了有机电致发光量子效率低于25％的理论限制，提升到100％，其应用也大大地提高了有机电致发光器件的效率。一般地，电致磷光需要采用主客体掺杂技术，常用的作为磷光主体材料的CBP(4,4'-bis(9-carbazolyl)-biphenyl)具有高效和高三线态能级，当其作为主体材料时，三线态能量能够有效地从发光主体材料转移到客体磷光发光材料。但是由于CBP的空穴易传输而电子难流动的特性，使得发光层的电荷不平衡，结果降低了器件的效率。
发明内容
本发明首先提供一种芴类有机电致发光化合物，其为具有如下结构式I的化合物：
Figure PCTCN2017092792-appb-000001
其中，X选自-N＝、-NR10、-O-、-S-，Y选自-N＝、-NR10、-O-、-S-，且X、Y不同时为-N＝；
R1-R10分别独立地选自氢、C1-C12的烷基、取代或者未取代的C6-C30的芳基、取代或者未取代的C3-C30的杂芳基、取代或者未取代的5或6元杂环烷基、取代或者未取代的C12-C30的二芳香胺基、取代或者未取代的C18-C30的三芳香胺基、咔唑基。
优选地，X为-N＝时，Y选自-O-、-S-；Y为-N＝时，X选自-O-、-S-。
优选地，R1选自C1-C12烷基、被C1-C12烷基取代或者未取代的C6-C30的芳基、被C1-C12烷基取代或者未取代的C3-C30的杂芳基。
优选地，R2和R3分别独立地选自氢、甲基、苯。
优选地，R4-R8分别独立的选自氢、苯、萘、三并苯基、C6-C30的N-芳基、C1-C4的烷基取代的咔唑基、吲哚基、咔唑吲哚基、芴咔唑基、蒽基、菲基、芘基、苝基、荧蒽基、(9,9-二烷基)芴基、(9,9-二取代或者未取代的芳基)芴基、9,9-螺芴基、C18-C60的三芳香胺基、被C1-C12烷基取代或者未取代的C12-C30的二苯并呋喃基、吡啶基、嘧啶基、哒嗪基、三嗪基、咪唑基、噁唑基、噻唑基、噻二唑基、喹啉基、异喹啉基、喹唑啉基、喹喔啉基、氮杂二苯并呋喃基、咪唑基，或以上芳基或杂芳基进一步被C1-C12的烷基取代。
优选地，R9选自氢、C1-C12的烷基。
进一步优选地，本发明的芴类有机电致发光化合物为下列结构式1-154的化合物：
Figure PCTCN2017092792-appb-000002
Figure PCTCN2017092792-appb-000003
Figure PCTCN2017092792-appb-000004
Figure PCTCN2017092792-appb-000005
Figure PCTCN2017092792-appb-000006
Figure PCTCN2017092792-appb-000007
Figure PCTCN2017092792-appb-000008
Figure PCTCN2017092792-appb-000009
Figure PCTCN2017092792-appb-000010
Figure PCTCN2017092792-appb-000011
Figure PCTCN2017092792-appb-000012
Figure PCTCN2017092792-appb-000013
Figure PCTCN2017092792-appb-000014
Figure PCTCN2017092792-appb-000015
Figure PCTCN2017092792-appb-000016
Figure PCTCN2017092792-appb-000017
Figure PCTCN2017092792-appb-000018
Figure PCTCN2017092792-appb-000019
Figure PCTCN2017092792-appb-000020
本发明还提供了一种有机电致发光器件，该器件包含阳极、阴极和有机层，有机层包含发光层、空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层中的至少一层，其中所述有机层中至少有一层含有如结构式I所述的有机电致发光材料：
Figure PCTCN2017092792-appb-000021
其中，X、Y和R1-R9的定义如前所述。
其中有机层为发光层；
或者有机层为发光层和电子传输层；
或者有机层为发光层、电子传输层和电子注入层；
或者有机层为空穴传输层和发光层；
或者有机层为空穴注入层、空穴传输层和发光层；
或者有机层为空穴传输层、发光层和电子传输层；
或者有机层为空穴注入层、空穴传输层、发光层和电子传输层；
或者有机层为空穴注入层、空穴传输层、发光层、电子传输层和电子注入层；
或者有机层为空穴注入层、空穴传输层、阻挡层、发光层、电子传输层和电子注入层；
或者有机层为空穴传输层、发光层、电子传输层、电子注入层和空穴阻挡层；
或者有机层为空穴传输层、发光层、电子注入层和空穴阻挡层。
优选地，如结构式I所述的芴类有机电致发光化合物所在层为发光层和电子传输层中的任意一层或两层。
优选地，如结构式I所述的芴类有机电致发光化合物为结构式1-154的化合物。
如结构式I所述的芴类化合物用于发光器件制备时，可以单独使用，也可以和其他化合物混合使用；如结构式I所述的芴类化合物可以单独使用其中的一种化合物，也可以同时使用结构式I中的两种或两种以上的化合物。
本发明的有机电致发光器件，进一步优选的方式为，该有机电致发光器件包含阳极、空穴注入层、空穴传输层、发光层、电子传输层、电子注入层和阴极，其中发光层中含有一种或一种以上的结构式I的化合物；进一步优选地，发光层中含有一种或一种以上的结构式1-154的化合物。
本发明的有机电致发光器件的发光层含有磷光发光客体材料和具有结构式I的化合物作为主体材料，其中结构式I化合物作为主体材料，其浓度为整个发光层重量的20-99.9％，优选80-99％。
本发明的有机电致发光器件有机层的总厚度为1-1000nm，优选50-500nm。
本发明的有机电致发光器件在使用本发明具有结构式I的化合物时，可以搭配使用其他材料，如在空穴注入层、空穴传输层、发光层、电子传输层、电子注入层和阻挡层中等，而获得蓝光、绿光、黄光、红光或者白光。
本发明有机电致发光器件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发光层上。除了上述具有结构式I所述化合物外，可以包括其他小分子和高分子有机化合物，包括但不限于咔唑类化合物、三芳香胺化合物、联苯二胺化合物、芴类化合物、酞菁类化合物、六氰基六杂三苯(hexanitrilehexaazatriphenylene)、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、聚乙烯或聚苯磺酸。
本发明的有机电致发光器件的发光层，具有很好的发光特性，可以根据需要调节可见光的范围。本发明的化合物可以作为主体发光材料，还可以含有如下化合物，包括但是不限于萘类化合物，芘类化合物，芴类化合物，菲类化合物，
Figure PCTCN2017092792-appb-000022
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，它们可以单独使用，也可以多种混合物使用。
本发明有机电致发光器件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，具有很大的电子迁移率。除了可以使用具有本发明I的化合物外，还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(如Alq3)、氟取代苯类化合物、苯并咪唑类化合物。
本发明有机电致发光器件的电子注入层，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或者碱金属络合物，可以选择如下化合物，但是不限于此：碱金属、碱土金属、稀土金属、碱金属的氧化物或者卤化物、碱土金属的氧化物或者卤化物、稀土金属的氧化物或者卤化物、碱金属或者碱土金属的有机络合物；优选为锂、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，这些化合物可以单独使用也可以混合使用，也可以跟其他有机电致发光材料配合使用。
本发明的有机电致发光器件中有机层的每一层，可以通过真空蒸镀法、分子束蒸镀法、溶于溶剂的浸涂法、旋涂法、棒涂法或者喷墨打印等方式制备。对于金属电机可以使用蒸镀法或者溅射法进行制备。
器件实验表明，本发明如结构式I所述的芴类有机电致发光化合物，具有较好热稳定性，高发光效率，高发光纯度。采用该有机电致发光化合物制作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是本发明的一种有机电致发光器件结构示意图；
图2是本发明的另一种有机电致发光器件结构示意图。
其中，110代表玻璃基板，120代表阳极，130代表空穴注入层，140代表空穴传输层，150代表阻挡层，160代表发光层，170代表电子传输层，180代表电子注入层，190代表阴极。
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。
实施例1
化合物8的合成
Figure PCTCN2017092792-appb-000023
中间体8-1的合成
在250mL单口烧瓶中，加入2-氨基-6-溴苯酚(25g,0.13mol)，苯甲酸(16.25g,0.13mol)和50mL多聚磷酸，160℃下反应6小时。反应结束后，待反应混合物冷却至室温，水洗，过滤得到粗产物，粗产品经柱层析提纯，得到白色固体25.75g，产率为70.7％。
中间体8-2的合成
将中间体8-1(25.75g,0.09mol)，硼酸三异丙酯(21.20g,0.11mol)和干燥处理过的四氢呋喃(150mL)混合加入三口烧瓶中，在-78℃下氩气保护中，搅拌15分钟，然后再通过一次性注射器向混合物中注入2.5M正丁基锂(37.6mL,0.09mol)的正己烷溶液，并继续搅拌2小时。随后，在室温下反应3小时。反应结束后，向混合反应液中加入稀盐酸，调节pH至弱酸性，然后用二氯甲烷多次萃取，合并得到有机相，旋转蒸发除去有机溶剂。粗产物用石油醚重结晶，得到白色固体16.85g，产率为75.3％。
中间体8-3的合成
将中间体8-2(2.0g,8.4mmol)和邻溴碘苯(2.61g,9.2mmol)溶于40mL四氢呋喃中，再和K2CO3(2.29g,16.8mmol)，20mL水混合一起加入到单口烧瓶中。氩气保护下，再向混合物中加入四(三苯基膦)钯(0.14g,0.12mmol)，加热回流4小时。反应结束后，待反应混合物冷却至室温，旋蒸除去四氢呋喃，然后水洗，二氯甲烷萃取三次(每次10mL)。合并有机相，无水硫酸钠干燥，粗产物用经柱层析提纯，得到产品1.32g，产率为45.5％。
中间体8-4的合成
将中间体8-3(1.32g,3.8mmol)和干燥处理过的四氢呋喃(15mL)混合加入三口烧瓶中，在-78℃下氩气保护中，搅拌15分钟，然后再通过一次性注射器向混合物中注入2.5M正丁基锂(1.5mL,3.8mmol)的正己烷溶液，并继续搅拌1小时。加入溶于10mL四氢呋喃的4-溴二苯甲酮(0.98g,3.8mmol)，低温反应1小时后，移至室温下反应3小时。反应结束后，用二氯甲烷多次萃取，合并得到有机相，旋转蒸发除去有机溶剂。粗产物用进行柱层析提纯后，加入15mL冰醋酸和1mL浓盐酸，加热回流1小时。反应结束后，旋转蒸发除去有机溶剂，粗产物用乙醇重结晶，得到白色固体1.15g，产率为62.2％。
化合物8的合成
合成方法跟中间体8-3一样，所用原料为中间8-4和10-(2-萘硼酸)-9-蒽硼酸，产率为85％。
实施例2
化合物11的合成
Figure PCTCN2017092792-appb-000024
中间体11-1的合成
将中间体8-4(10g,20mmol)和联硼酸频哪醇酯(6.7g,26mmol)溶于150mL二氧六环中，再和乙酸钾(5g,51mmol)混合一起加入到单口烧瓶中。氩气保护下，再向混合物中加入催化剂量的[1,1'-双(二苯基膦基)二茂铁]二氯化钯，加热回流5小时。反应结束后，待反应混合物冷却至室温，过硅胶，旋蒸除去有机溶剂，经柱层析纯化得到9.5g，产率为87％。
化合物11的合成
将中间体11-1(1.8g,3.6mmol)和2-氯-4,6-二苯基-1,3,5-三嗪(0.95g,3.6mmol)溶于20mL四氢呋喃中再和K2CO3(1g,7.2mmol)，10mL水混合一起加入到单口烧瓶中。氩气 保护下，再向混合物中加入催化剂量的醋酸钯和配体X-Phos，加热回流4小时。反应结束后，待反应混合物冷却至室温，旋蒸除去溶剂，水洗，二氯甲烷萃取三次(每次10mL)。合并有机相，粗产品经柱层析纯化得到1.7g，产率为73％。
实施例3
化合物15的合成
Figure PCTCN2017092792-appb-000025
将中间体8-4(2g,3.9mmol)和咔唑(0.72g,4.2mmol)溶于30mL甲苯中，再和叔丁醇钠(0.87g,7.8mmol)混合一起加入到单口烧瓶中。氩气保护下，再向混合物中加入催化剂量的醋酸钯和配体X-Phos，加热回流4小时。反应结束后，待反应混合物冷却至室温，过硅胶，旋蒸除去有机溶剂，粗产物经柱层析纯化得到1.9g，产率为81％。
实施例4
化合物25的合成
Figure PCTCN2017092792-appb-000026
合成方法跟化合物11一样，所用原料为中间体11-1和4,6-二苯基-2-(3-溴苯基)-1,3,5-三嗪，产率为69％。
实施例5
化合物26的合成
Figure PCTCN2017092792-appb-000027
合成方法跟化合物11的一样，所用原料为中间体8-4和B-[4-(1-苯基-1H-苯并咪唑-2-基)苯基]-硼酸，产率为87％。
实施例6
化合物31的合成
Figure PCTCN2017092792-appb-000028
中间体31-1的合成
合成方法跟中间体8-4一样，除了用4,4-二苯甲酮代替4-溴二苯甲酮外，产率为53％。
化合物31的合成
合成方法跟化合物11的一样，所用原料为中间体31-1和3-吡啶硼酸，产率为48％。
实施例7
化合物37的合成
Figure PCTCN2017092792-appb-000029
中间体37-1的合成
将中间体8-2(4.0g,16.8mmol)和5-溴-2-碘苯甲酸甲酯(6.3g,18.5mmol)溶于50mL四氢呋喃中再和K2CO3(4.56g,33.6mmol)，25mL水混合一起加入到单口烧瓶中。氩气保护下，再向混合物中加入四(三苯基膦)钯(0.28g,0.24mmol)，加热回流4小时。反应结束后，待反应混合物冷却至室温，旋蒸除去四氢呋喃，然后水洗，二氯甲烷萃取三次(每次10mL)。合并有机相，无水硫酸钠干燥，粗产物用行柱层析提纯，得到5.67g，产率为82.7％。
中间体37-2的合成
合成方法跟中间体11-1一样，所用原料为中间体37-1，产率为77％。
化合物37的合成
合成方法跟化合物11的一样，所用原料为中间体37-3，产率为80％。
实施例8
化合物48的合成
Figure PCTCN2017092792-appb-000030
中间体48-1的合成
合成方法跟中间体8-1一样，原料为2-氨基-6-溴苯硫酚，产率为69％。
中间体48-2的合成
合成方法跟中间体8-2一样，所用原料为中间体48-1，产率为71％。
中间体48-3的合成
合成方法跟中间体8-3一样，所用原料为中间体48-2，产率为51％。
中间体48-4的合成
合成方法跟中间体8-4一样，所用原料为中间体48-3，产率为46％。
中间体48-5的合成
合成方法跟中间体8-5一样，所用原料为中间体48-4，产率为83％。
化合物48的合成
合成方法跟化合物11的合成一样，所用原料为中间体48-5，产率为86％。
实施例9
化合物51的合成
Figure PCTCN2017092792-appb-000031
合成方法跟化合物15的合成一样，除了用中间体48-4代替中间体8-4外，产率为78％。
实施例10
化合物109的合成
Figure PCTCN2017092792-appb-000032
中间体109-1的合成
合成方法跟中间体8-1一样，产率为64％。
中间体109-2的合成
合成方法跟中间体8-2一样，产率为69％。
中间体109-3的合成
合成方法跟中间体37-1一样，产率为57％。
中间体109-4的合成
合成方法跟中间体37-2一样，所用原料为中间体109-3，产率为49％。
中间体109-5的合成
合成方法跟中间体37-3一样，所用原料为中间体109-4，产率为77％。
化合物109的合成
合成方法跟化合物11的合成一样，所用原料为中间体109-5，产率为75％。
实施例11
化合物147的合成
Figure PCTCN2017092792-appb-000033
合成方法跟化合物8一样，所用原料为中间体37-2和9-苯基咔唑-2-硼酸，产率为83％。
实施例12
化合物153的合成
Figure PCTCN2017092792-appb-000034
合成方法跟化合物15的一样，除了用中间体37-2代替中间体8-4外，产率为66％。
实施例13
有机电致发光器件的制备
使用本发明化合物和比较例的化合物制备OLED
首先，将透明导电ITO玻璃基板110(上面带有阳极120)(中国南玻集团股份有限公司)依次经：去离子水，乙醇，丙酮和去离子水洗净，再用氧等离子处理30秒。
然后，蒸镀NPB，形成60nm厚的空穴传输层130。
然后，在空穴传输层上蒸镀本发明化合物8，形成30nm厚的发光层140。
然后，在发光层上蒸镀30nm厚的Alq3作为电子传输层150。
最后，蒸镀1nm LiF为电子注入层160和100nm Al作为器件阴极170。
所制备的器件(结构示意图见图1)用Photo Research PR650光谱仪测得的在 20mA/cm2的电流效率2.1cd/A，发射蓝光。
比较例1
除了发光层用MADN代替本发明化合物外，其他的跟实施例13一样。测得的电流效率为1.4cd/A，发射蓝光。
在相同的条件下，应用本发明的有机电致发光化合物制备的有机电致发光器件的电流效率高于比较例。如上所述，本发明的化合物具有高的稳定性，本发明制备的有机电致发光器件具有低驱动电压，高的效率和光纯度。
器件中所述化合物的结构式如下：
Figure PCTCN2017092792-appb-000035
实施例14-27
有机电致发光器件的制备
使用本发明的化合物和比较例的化合物制备OLED
首先，将透明导电ITO玻璃基板110(上面带有阳极120)(中国南玻集团股份有限公司)依次经：去离子水，乙醇，丙酮和去离子水洗净，再用氧等离子处理30秒。
然后，蒸镀NPB，形成60nm厚的空穴传输层130。
然后，在空穴传输层上蒸镀37.5nm厚的Alq3掺杂1％C545T作为发光层140。
然后，在发光层上蒸镀37.5nm厚的本发明化合物和Liq作为电子传输层150，本发明化合物和Liq的比例为1:1。
最后，蒸镀1nm LiF为电子注入层160和100nm Al作为器件阴极170。
所制备的器件(结构示意图见图1)用Photo Research PR650光谱仪测得的在20mA/cm2的电流密度下的效率如表1。
比较例2
除了电子传输层用Alq3代替本发明化合物外，其他的跟实施例14-20一样。
所制备的器件(结构示意图见图2)用Photo Research PR650光谱仪测得的在20mA/cm2的电流密度下的效率如表1。
表1
实施例 化合物 功率效率(lm/W) 颜色
14 11 6.3 绿光
15 25 6.4 绿光
16 26 6.0 绿光
17 29 6.2 绿光
18 31 6.3 绿光
19 37 6.1 绿光
20 48 6.2 绿光
21 60 5.9 绿光
22 72 6.0 绿光
23 84 5.8 绿光
24 109 6.1 绿光
25 111 5.9 绿光
26 119 5.8 绿光
27 138 6.2 绿光
比较例2 Alq3 5.0 绿光
实施例28-37
有机电致发光器件的制备
使用实施例的化合物制备OLED
首先，将透明导电ITO玻璃基板110(上面带有阳极120)(中国南玻集团股份有限公司)依次经：去离子水，乙醇，丙酮和去离子水洗净，再用氧等离子处理30秒。
然后，在ITO上蒸镀3nm厚的MnO3(氧化钼)为空穴注入层130。
然后，在空穴注入层上蒸镀50nm厚的TAPC为空穴传输材料140。
然后，蒸镀TCTA，形成5nm厚的电子阻挡层150。
然后，在电子阻挡层上蒸镀20nm厚的发光层160，其中，本发明化合物为主体发光材料，而以3％重量比的Ir(ppy)3作为磷光掺杂客体材料。
然后，在发光层上蒸镀40nm厚的BmPYPB作为电子传输层170。
最后，蒸镀1nm LiF为电子注入层180和80nm Al作为器件阴极190。
所制备的器件(结构示意图见图2)用Photo Research PR650光谱仪测得的在5000cd/m2的亮度下的外量子效率为如表2。
实施例38
实施例38的制备方法跟实施例28-37的一样，除了发光层用CBP和化合物11共蒸作为主体材料外，其质量比为7:3。
实施例39
实施例39的制备方法跟实施例38一样，除了发光层用CBP和化合物25共蒸作为主体材料外，质量比为7:3。
比较例3
比较例制备的器件跟实施例28-37件制备方法一样，除了用CBP代替本发明化合物作为主体材料外。
所制备的器件(结构示意图见图2)用Photo Research PR650光谱仪测得的在20mA/cm2的电流密度下的效率如表2。
表2
实施例 化合物 电流效率(cd/A) 发光颜色
28 15 61 绿光
29 16 57 绿光
30 18 61 绿光
31 20 59 绿光
32 51 60 绿光
33 64 61 绿光
34 90 58 绿光
35 122 60 绿光
36 147 58 绿光
37 153 59 绿光
38 CBP:11 65 绿光
39 CBP:25 63 绿光
比较例3 CBP 45 绿光
从表中可以看出，本发明的有机电致发光化合物制备的有机电致发光器件，可以降低工作电压，提高器件效率，是具有优良性能的磷光主体材料。如上所述，本发明的化合物具有高的稳定性，制备的有机电致发光器件具有高的效率和光纯度。
器件中所述化合物的结构式如下：
Figure PCTCN2017092792-appb-000036
Figure PCTCN2017092792-appb-000037
以上详细描述了本发明的较佳具体实施例。应当理解，本领域的普通技术人员无需创造性劳动就可以根据本发明的构思作出诸多修改和变化。因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。

Claims (13)

  1. 一种芴类有机电致发光化合物，其特征在于，为具有如下结构式I的化合物：
    Figure PCTCN2017092792-appb-100001
    其中，X选自-N＝、-NR10、-O-、-S-，Y选自-N＝、-NR10、-O-、-S-，且X、Y不同时为-N＝；
    R1-R10分别独立地选自氢、C1-C12的烷基、取代或者未取代的C6-C30的芳基、取代或者未取代的C3-C30的杂芳基、取代或者未取代的5或6元杂环烷基、取代或者未取代的C12-C30的二芳香胺基、取代或者未取代的C18-C30的三芳香胺基、咔唑基。
  2. 根据权利要求1所述的芴类有机电致发光化合物，其特征在于，X为-N＝时，Y选自-O-、-S-；Y为-N＝时，X选自-O-、-S-。
  3. 根据权利要求1所述的芴类有机电致发光化合物，其特征在于，R1选自C1-C12烷基、被C1-C12烷基取代或者未取代的C6-C30的芳基、被C1-C12烷基取代或者未取代的C3-C30的杂芳基。
  4. 根据权利要求1所述的芴类有机电致发光化合物，其特征在于，R2和R3分别独立地选自氢、甲基、苯。
  5. 根据权利要求1所述的芴类有机电致发光化合物，其特征在于，R4-R8分别独立地选自氢、苯、萘、三并苯基、C6-C30的N-芳基、C1-C4的烷基取代的咔唑基、吲哚基、咔唑吲哚基、芴咔唑基、蒽基、菲基、芘基、苝基、荧蒽基、(9,9-二烷基)芴基、(9,9-二取代或者未取代的芳基)芴基、9,9-螺芴基、C18-C60的三芳香胺基、被C1-C12烷基取代或者未取代的C12-C30的二苯并呋喃基、吡啶基、嘧啶基、哒嗪基、三嗪基、咪唑基、噁唑基、噻唑基、噻二唑基、喹啉基、异喹啉基、喹唑啉基、喹喔啉基、氮杂二苯并呋喃基、咪唑基，或以上芳基或杂芳基进一步被C1-C12的烷基取代。
  6. 根据权利要求1所述的芴类有机电致发光化合物，其特征在于，R9选自氢、C1-C12的烷基。
  7. 根据权利要求1所述的一种芴类有机电致发光化合物，其特征在于，其为下列结构式1-154的化合物：
    Figure PCTCN2017092792-appb-100002
    Figure PCTCN2017092792-appb-100003
    Figure PCTCN2017092792-appb-100004
    Figure PCTCN2017092792-appb-100005
    Figure PCTCN2017092792-appb-100006
    Figure PCTCN2017092792-appb-100007
    Figure PCTCN2017092792-appb-100008
    Figure PCTCN2017092792-appb-100009
    Figure PCTCN2017092792-appb-100010
    Figure PCTCN2017092792-appb-100011
    Figure PCTCN2017092792-appb-100012
    Figure PCTCN2017092792-appb-100013
    Figure PCTCN2017092792-appb-100014
    Figure PCTCN2017092792-appb-100015
    Figure PCTCN2017092792-appb-100016
    Figure PCTCN2017092792-appb-100017
    Figure PCTCN2017092792-appb-100018
    Figure PCTCN2017092792-appb-100019
  8. 一种有机电致发光器件，该器件包含阳极、阴极和有机层，有机层包含发光层、空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层中的至少一层，其特征在于，其中所述有机层中至少有一层含有如权利要求1所述的芴类有机电致发光材料。
  9. 根据权利要求8所述的有机电致发光器件，其特征在于，如结构式I所述的芴类有机 电致发光化合物所在层为发光层和电子传输层中的任意一层或两层。
  10. 根据权利要求8所述的有机电致发光器件，其特征在于，如结构式I所述的芴类有机电致发光化合物为结构式1-154的化合物。
  11. 根据权利要求8所述的有机电致发光器件，其特征在于，如结构式I所述的芴类有机电致发光化合物单独使用其中的一种化合物，或同时使用结构式I中的两种以上的化合物。
  12. 根据权利要求8所述的有机电致发光器件，其特征在于，如结构式I所述的芴类有机电致发光化合物作为发光层的主体材料，其浓度为整个发光层重量的20-99.9％。
  13. 根据权利要求8所述的有机电致发光器件，其特征在于，所述有机电致发光器件有机层的总厚度为1-1000nm。
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