WO2013178041A1 - 有机电子材料 - Google Patents

有机电子材料 Download PDF

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WO2013178041A1
WO2013178041A1 PCT/CN2013/076236 CN2013076236W WO2013178041A1 WO 2013178041 A1 WO2013178041 A1 WO 2013178041A1 CN 2013076236 W CN2013076236 W CN 2013076236W WO 2013178041 A1 WO2013178041 A1 WO 2013178041A1
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substituted
phenyl
unsubstituted
group
naphthyl
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PCT/CN2013/076236
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English (en)
French (fr)
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戴雷
黄锦海
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 KR1020147031149A priority Critical patent/KR101775519B1/ko
Priority to US14/404,604 priority patent/US9905774B2/en
Publication of WO2013178041A1 publication Critical patent/WO2013178041A1/zh

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Definitions

  • the invention relates to a novel organic electroluminescent material, which is deposited into a thin film by vacuum evaporation, and is applied as a blue electroluminescent material on an organic electroluminescent diode, and belongs to the technical field of organic electroluminescent device display.
  • 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 make organic electroluminescent device technology suitable for use in 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 classical three-layer organic electroluminescent device comprises a hole transporting layer, a light emitting layer and an electron transporting 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, efficient and color-only 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 and are also in line with the market demand for panels.
  • blue light materials there are also a series of commercial materials, among which the early use of stilbene biphenyl (DPVB compounds), which is produced by such compounds, has higher efficiency, but Often the stability of these materials is relatively poor, and moreover, the luminescent color of such compounds belongs to sky blue, and y>0.15 in CIE values. Therefore, due to its poor temperature and impure color, it is very large. The use of such compounds in full color display devices is limited.
  • Another type of blue light material is Kodak's ADN and tetra-tert-butyl fluorene.
  • the invention overcomes the defects of the above compounds, and provides a series of organic electroluminescent materials having good thermal stability, high luminous efficiency and high luminous purity, and the organic electroluminescent device prepared therefrom has good electroluminescence efficiency and color. Excellent in purity and long life.
  • the organic electronic material of the present invention has the structural formula described in (I):
  • RR 8 is independently represented by hydrogen, deuterium, halogen, cyano, nitro, C1-C8 alkyl, C1-C8 alkoxy, C6-C30 substituted or unsubstituted aryl, C3-C30 a substituted or unsubstituted heteroaryl group containing one or more, a C2-C8 substituted or unsubstituted olefinic group, a C2-C8 substituted or unsubstituted alkynyl group, wherein ⁇ - ⁇ 4 independently represents C6- C60 substituted or unsubstituted aryl, C3-C60 substituted or unsubstituted heteroaryl with one or more heteroatoms, triaromatic (C6-C30) amine.
  • - is independently represented by hydrogen, halogen, cyano, nitro, C1-C8 alkyl, C1-C8 alkoxy, C2-C8 substituted or unsubstituted olefinic alkyl, C2-C8 substituted or not Substituted alkynyl, C1-C4 alkyl substituted or unsubstituted phenyl, C1-C4 alkyl substituted or unsubstituted naphthyl; ⁇ - ⁇ 4 independently represents C1-C4 alkyl or C6-C30 aryl substituted Phenyl, C1-C4 alkyl or C6-C30 aryl substituted naphthyl, phenyl, naphthyl, N-aryl (C6-C30) or C1-C4 alkyl-substituted carbazolyl, diphenyl And thienyl, dibenzofuranyl, fluorenyl, phenanth
  • - may independently be preferably represented by hydrogen, halogen, C1-C4 alkyl, C1-C4 alkyl substituted or unsubstituted phenyl, C1-C4 alkyl substituted or unsubstituted naphthyl;
  • - ⁇ 4 is independently represented by phenyl, tolyl, tert-butylphenyl, naphthyl, methylnaphthalene, biphenyl, diphenylphenyl, naphthylphenyl, diphenylbiphenyl, diarylamine Phenylphenyl, N-phenylcarbazolyl, (9,9-dialkyl)fluorenyl, (9,9-dialkyl substituted or unsubstituted phenyl) anthracenyl, 9,9-spirobenyl.
  • R 2 , R 3 , R 6 and R 7 are independently and preferably represented by hydrogen, fluorine, methyl, ethyl, propyl, isopropyl, t-butyl, phenyl, naphthyl.
  • ⁇ - ⁇ 4 is independently represented by phenyl, tolyl, naphthyl, methylnaphthalene, biphenyl, diphenylphenyl, naphthylphenyl, diphenylbiphenyl, (9,9-dioxane) Base, fluorenyl, (9,9-dimethyl substituted or unsubstituted phenyl) anthracenyl, 9,9-spiropurinyl.
  • Ar 2 , Ar 3 , Ar 4 are independently phenyl, naphthyl, biphenyl, oxime phenyl, naphthyl, biphenyl, diphenylphenyl, naphthylphenyl, diphenyl Biphenyl, (9,9-dialkyl)fluorenyl, (9-tolyl, 9'-phenyl) anthracenyl, 9,9-spiropurinyl.
  • R 2 , R 3 , and R 7 are hydrogen, and Ar 2 , Ar 3 and Ar 4 independently represent a phenyl group and a naphthyl group.
  • organic electronic materials are used in the field of organic electroluminescent devices, organic solar cells, organic thin film transistors or organic photoreceptors.
  • the organic electronic material provided by the present invention can be fabricated into an organic electroluminescent device comprising an anode, a cathode and one or more organic layers, at least one of which contains an organic electronic material as described in Structural Formula I.
  • the plurality of organic layers are a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, and an electron transport layer, respectively. It is to be noted that the organic layer may not necessarily be present in each layer as needed.
  • the hole transport layer, the electron transport layer and the light-emitting layer contain the organic material as described in Structural Formula 1.
  • the compound of formula I acts as an undoped single luminescent layer or a doped luminescent layer.
  • the doped luminescent layer comprises a host material and a guest material.
  • the concentration thereof 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.
  • the concentration thereof is from 0.01 to 80%, preferably from 1 to 20%, more preferably from 1 to 10% by weight based on the weight of the light-emitting 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 hole transporting layer and the hole injecting layer in the present invention have a material having 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 fluorene vinyl compound of the present invention, the following compounds, but is not limited thereto, naphthalene compounds, terpenoids, terpenoids, phenanthrene compounds, quinone compounds , fluoranthene compounds, terpenoids, pentacene compounds, terpenoids, diarylene compounds, triphenylamine vinyl compounds, amine compounds, benzimidazoles, furan compounds, organometallic chelation Things.
  • 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 as needed, which can effectively inject electrons from the cathode into the organic layer, mainly selected from alkali metal or alkali metal compounds, or selected from alkaline earth metals. Or an alkaline earth metal compound, which can be selected
  • the following compounds are selected, but are not limited thereto, lithium, lithium fluoride, lithium oxide, lithium nitride, lithium 8-hydroxyquinolate, hydrazine, cesium carbonate, 8-hydroxyquinolinium, calcium, calcium fluoride, calcium oxide, Magnesium, magnesium fluoride, magnesium carbonate, magnesium oxide.
  • the device experiments show that the organic electronic material of the present invention as described in the formula (I) has good thermal stability, high luminous efficiency, and high luminous purity.
  • An organic electroluminescent device made of the organic luminescent material has excellent 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 2 is an iH NMR chart of Compound 110.
  • the transparent conductive ITO glass substrate 10 (with the anode 20 on the surface) is sequentially washed with detergent solution and deionized water, ethanol, acetone, deionized water, and then treated with oxygen plasma for 30 seconds, followed by plasma treatment.
  • CF X processing is sequentially washed with detergent solution and deionized water, ethanol, acetone, deionized water, and then treated with oxygen plasma for 30 seconds, followed by plasma treatment.
  • P1 is vaporized to form a 50 nm thick hole transport layer 40.
  • a compound 110 having a thickness of 20 nm was vapor-deposited on the hole transporting layer as the light-emitting layer 50.
  • the device was fabricated to have a luminance of 980 cd/m 2 at a working voltage of 7 V, a current efficiency of 4.3 cd/A, a power efficiency of 2.1 lm/W, and emit blue light.
  • Example 4 (method is the same as embodiment 3)
  • the compound 110 was replaced with the compound 122 to prepare an organic electroluminescent device.
  • the fabricated device has a luminance of 470 cd/m 2 at a working voltage of 7 V, a current efficiency of 4.6 cd/A, a power efficiency of 1.95 lm/W, and emits blue light.
  • the fabricated device has a luminance of 289 cd/m 2 at a working voltage of 7 V, a current efficiency of 2.4 cd/A, and a power efficiency of 1.1 lm/W.
  • Shoot blue light
  • Examples 3 and 4 are specific applications of the materials of the present invention.
  • the devices produced, the present invention emit blue light, and the efficiency and brightness are higher than the comparative examples.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

公开了具有式（I）结构的有机电子材料，各取代基的定义如说明书中所述。该有机电致发光材料，通过真空蒸镀沉积成薄膜，作为蓝光电致发光材料应用在有机电致发光二极管上，具有高的稳定性、高的发光效率和光纯度。

Description

有机电子材料 技术领域
本发明涉及新型的有机电致发光材料， 通过真空蒸渡沉积成薄膜， 作为蓝光电致发光材料应用在有机 电致发光二极管上， 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， 也符合面板的市场需求。 对于蓝光材料，也有一系列的商品化的材料，其中早期用得比较多的为出光兴产的二苯乙烯基联苯 (DPVB 类化合物， 以这类化合物制备的器件具有较高的效率， 但是往往这些材料的稳定性比较差， 更有甚地， 这 类化合物的发光的颜色属于天蓝光， 往往 CIE值中的 y>0.15。所以由于其不好的温度性和不纯的颜色很大 程度地限制了这类化合物在全彩显示器件中的应用。另外一类蓝光材料为柯达公司的 ADN和四叔丁基茈， 。
Figure imgf000003_0001
(DPVBi) (ADN) (四叔丁基茈）
发明内容
本发明就是克服上面化合物的缺陷， 提供一系列具有较好热稳定性， 高发光效率， 高发光纯度的有机 电致蓝光材料， 由它制备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。 本发明所述的有机电子材料具有 (I)所述的结构式：
Figure imgf000004_0001
其中， R R8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， ΑΠ-ΑΓ4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， - 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； ΑΠ-ΑΓ4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， N-芳基 （C6-C30)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， 茈基， 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， - 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 ΑΠ-ΑΓ4为独立地表示苯基， 甲苯基， 叔丁基苯基， 萘基， 甲 基萘， 联苯基， 二苯基苯基， 萘基苯基， 二苯基联苯基， 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， 优选为氢， R2， R3， R6， R7可以独立优选表示为氢， 氟， 甲基， 乙基， 丙基， 异丙基， 叔丁基， 苯基， 萘基； ΑΠ-ΑΓ4为独立地表示苯基， 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。
优选 Ar2， Ar3， Ar4为独立地表示苯基， 萘基， 联苯基， Αι^为苯基， 萘基， 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-甲苯基， 9' -苯基） 芴基， 9,9-螺芴基。
优选： R2， R3， ， R7为氢， Ar2， Ar3， Ar4为独立地表示苯基， 萘基。
优选：
Figure imgf000004_0002
Figure imgf000005_0001
上述有机电子材料在有机电致发光器件， 有机太阳能电池， 有机薄膜晶体管或有机光感受器领域的应 用。
如上面提到的， 本发明的具体实施例如下， 但不限于所列举的结构:
Figure imgf000005_0002
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000008_0001
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
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Figure imgf000016_0001
Figure imgf000017_0001
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本发明提供的有机电子材料可以制成有机电致发光器件，该器件包含阳极，阴极和一层或多层有机层， 所述有机层中至少有一层含有如结构式 I所述的有机电子材料。
所述多层有机层分别为空穴注入层， 空穴传输层， 发光层， 空穴阻挡层和电子传输层， 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， 电子传输层和发光层中含有如结构式 1所述的有机材料。
结构式 I化合物作为无掺杂单一发光层或掺杂发光层。
所述掺杂发光层包括主体材料和客体材料， 结构式（I)化合物作为主体材料时， 其浓度为整个发光层 重量的 20-99.9%， 优选 80-99%， 更优选为 90-99%。 结构式（I)化合物作为客体材料时， 其浓度为这个发 光层重量的 0.01-80%， 优选 1-20%， 更优选为 1-10%。
包括同时使用结构式 I的两个化合物分别作主体材料和客体材料。
本发明的电子器件有机层的总厚度为 1-1000 nm， 优选 1-500 nm， 更优选 50-300 nm。
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， 除含有本发明的蒽乙烯基化合物外， 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， 茈类化合物， 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， 本发明如式 （I ) 所述的有机电子材料， 具有较好热稳定性， 高发光效率， 高发光纯 度。 采用该有机发光材料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 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 110的 iH NMR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。
实施例 1
化合物 110的合成
Figure imgf000019_0001
化合物 " 0 中间体 1-1的合成
在 1 L的单口烧瓶中， 加入 25.5 gl-萘硼酸和 25 g对溴苯甲醛， 400 ml二氧六环， 80 ml 2 M碳酸钾水 溶液， 在氮气保护下， 加入 1.0 g四三苯基磷钯， 加热回流 12小时， 冷却， 用乙酸乙酯萃取三遍， 有机相 用无水硫酸钠干燥， 浓缩， 粗品用乙醇重结晶， 得到固体 29 g， 产率为 92 %。
中间体 1-3的合成
在 500 ml的单口烧瓶中， 25 g对溴苄溴跟 49.8 ml亚磷酸三乙酯（1-2 )加热回流 2个小时， 除去多余 的亚磷酸三乙酯， 加入 23.4 g中间体 1-1和 250 ml DMF， 在冰浴下， 加入 16.8 g叔丁醇钾， 升至室温， 搅 拌过夜， 把反应液倒入蒸熘水里面， 过滤， 滤饼用乙醇重结晶， 得到 31.8 g， 产率 83 %。
中间体 1-4的合成
在 1 L 的单口烧瓶中，加入 45 g3,5-二苯基苯硼酸和 42.5 g对溴碘苯， 450 ml二氧六环， 150 ml 2M碳 酸钾水溶液， 在氮气保护下， 加入 1.7 g四三苯基磷钯， 加热回流 12小时， 冷却， 用乙酸乙酯萃取三遍， 有机相用无水硫酸钠干燥， 浓缩， 粗品用乙醇重结晶， 得到固体 54.6 g， 产率为 95 %。
中间体 1-5的合成
在氮气保护下，把 20 g中间体 1-4和 300 ml THF加入到 1 L的三口烧瓶中，冷却到 -78度，滴加 21 ml 2.5M的正丁基锂， 在此温度下， 保持 2小时， 加入 16.6 g硼酸三异丙酯， 在此温度下保持 1个小时， 升至 室温， 反应 12小时， 往反应液加入 2N的稀盐酸， 调节到中性， 用乙酸乙酯萃取三次， 有机相用无水硫 酸钠干燥， 浓缩， 粗品用乙酸乙酯和正己烷重结晶， 得到固体 14 g， 产率为 78 %。
中间体 1-6的合成
在 500 ml的单口烧瓶中， 加入 20 g中间体 1-3和 14 g 9-蒽硼酸， 350 ml二氧六环， 70 ml碳酸钾水溶 液， 在氮气保护下， 加入 0.6 g四三苯基磷钯， 加热回流 12小时， 冷却， 用乙酸乙酯萃取三遍， 有机相用 无水硫酸钠干燥， 浓缩， 粗品用 THF加热回流， 冷却过滤， 得到固体 20 g， 产率为 80%。
中间体 1-7的合成
在 500 ml 的单口烧瓶中， 加入 20 g中间体 1-6， 10.4 g NBS和 400 ml氯仿， 25度下搅拌 12小时， 除 去二氯甲烷， 用 THF和乙醇重结晶得到 17 g， 产率 73.3%。
化合物 110的合成
在 250 ml的单口烧瓶中， 加入 5.5 g中间体 1-5和 7.3 g中间体 1-7， 75 ml二氧六环， 20 ml 2M碳酸 钾水溶液， 在氮气保护下， 加入 0.15 g四三苯基磷钯， 加热回流 12小时， 冷却， 用乙酸乙酯萃取三遍， 有机相用无水硫酸钠干燥，浓缩，粗品用 THF加热回流，冷却过滤，得到固体 7.7 g，产率为 75.5%。 NMR (400 MHz, CD2C12, δ): 7.99-8.02 (m, 5 Η), 7.88-7.95 (m, 3 Η), 7.76-7.86 (m, 12 Η), 7.38-7.63 (m, 22 Η). MALDI-TOF-MS m/s 计算值（ 62 2 : 786.3， 实测值 [M+]: 786.5。 化合物 110的1 H NMR如图 2。
实施例 2
Figure imgf000021_0001
中间体 2-2的合成
在氮气保护下， 把 36.3g中间体 （2-1 ) 和 400 ml THF加入到 1L的三口烧瓶中， 冷却到 -78度， 滴加 50 ml 2.5M的正丁基锂， 在此温度下， 保持 2小时， 加入 30 g硼酸三异丙酯， 在此温度下保持 1个小时， 升至室温， 反应 12小时， 往反应液加入 2N的稀盐酸， 用乙酸乙酯萃取三次， 有机相用无水硫酸钠干燥， 浓缩， 粗品用乙酸乙酯和正己烷重结晶， 得到固体 27 g， 产率为 90%。
中间体 2-3的合成
在 500 ml的单口烧瓶中， 加入 25 g中间体 2-2和 14.5 g对溴碘苯， 300 ml二氧六环， 60 ml 2M碳酸 钾水溶液， 在氮气保护下， 加入 0.6 g四三苯基磷钯， 加热回流 12小时， 冷却， 用乙酸乙酯萃取三遍， 有 机相用无水硫酸钠干燥， 浓缩， 粗品用 THF加热回流， 冷却过滤， 得到固体 22 g， 产率为 70%。
中间体 2-4的合成
在氮气保护下， 把 15.5 g中间体 2-3和 300 ml THF加入到 250 ml的三口烧瓶中， 冷却到 -78度， 滴加 17 ml 2.5M的正丁基锂， 在此温度下， 保持 2小时， 加入 10.2 g硼酸三异丙酯， 在此温度下保持 1个小时， 升至室温， 反应 12小时， 往反应液加入 2N的稀盐酸， 用乙酸乙酯萃取三次， 有机相用无水硫酸钠干燥， 浓缩， 粗品用乙酸乙酯和正己烷重结晶， 得到固体 14 g， 产率为 90 %。
化合物 122的合成
在 250 ml的单口烧瓶中， 加入 7 g中间体 2-5和 8 g中间体 1-7， 120 ml二氧六环， 24 ml 2M碳酸钾 水溶液， 在氮气保护下， 加入 0.16g四三苯基磷钯， 加热回流 12小时， 冷却， 用乙酸乙酯萃取三遍， 有机 相用无水硫酸钠干燥，浓缩，粗品用 THF加热回流，冷却过滤，得到固体 10g，产率为 79%。 ^ NMR (400 MHz, CD2C12, δ): 7.98-8.00 (d, J= 8.4 Hz, 2 H), 7.94-7.96(d, J= 7.6 Hz, 2 H), 7.89-7.91 (d, J= 8.0 Hz, 2 H), 7.76-7.86 (m, 12 H), 7.65-7.67(d, J= 8.4 Hz, 2 H),7.48-7.58 (m, 11 H), 7.32-7.43 (m, 11 H), 7.09-7.17 (m, 6 H) 2.32 (s, 3 H) . MALDI-TOF-MS m/s 计算值 （ 70 8 : 888.4， 实测值 [M+]: 888.7。 实施例 3 蓝色有机电致发光器件的制备
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， 接着用等离子处理的 CFX处理。
然后， 在 ITO上蒸渡 5 nm厚的 Mo03作为空穴注入层 30。
然后， 蒸渡 P1,形成 50 nm厚的空穴传输层 40。
然后， 在空穴传输层上蒸渡 20 nm厚的化合物 110作为发光层 50。
然后， 在发光层上蒸渡 40 nm厚的 P2作为电子传输层 60。
最后， 蒸渡 1.2 nm LiF为电子注入层 70和 150 nmAl作为器件阴极 80 。
所制备的器件在 7V的工作电压下的亮度为 980cd/m2， 电流效率达到 4.3 cd/A， 功率效率为 2.1 lm/W， 发 射蓝光。
器件中所述结构式
Figure imgf000022_0001
Figure imgf000022_0002
实施例 4 (方法同实施例 3 )
将化合物 110， 换成化合物 122， 制作有机电致发光器件。
所制备的器件在 7V的工作电压下的亮度为 470 cd/m2， 电流效率达到 4.6 cd/A， 功率效率为 1.95 lm/W， 发 射蓝光。
比较例 1
方法同实施例 3， 将化合物 110替换成下列化合物 P3， 制作对比用有机电致发光器件。
所制备的器件在 7V的工作电压下的亮度为 289 cd/m2, 电流效率达到 2.4 cd/A, 功率效率为 1.1 lm/W, 发 射蓝光。
实施例 3和 4是本发明材料的具体应用， 所制备的器件， 本发明发射蓝光， 效率和亮度都高于对比例。 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。
Figure imgf000023_0001

Claims

权利要求书
1、 有机电子材料具有式 (I)所述 :
Figure imgf000024_0001
其中， RrR8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， An-Ar4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所述的有机电子材料， 其中， RrR8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； ΑΠ-ΑΓ4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， N-芳基（C6-C30)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， 茈基， 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所述的有机电子材料， 其中， ！^-！^可以独立地表示为氢， 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； Ari-Ar4为独立地表示苯基， 甲苯基， 叔丁基苯基， 萘基， 甲基萘， 联苯基， 二苯基苯基， 萘基苯基， 二苯基联苯基， 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所述的有机电子材料， 其中， 1^, , , 1 8， 为氢， ， ， R6， R7可以独立表示 为氢， 氟， 甲基， 乙基， 丙基， 异丙基， 叔丁基， 苯基， 萘基； A^-A 为独立地表示苯基， 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所述的有机电子材料， 其中 Ar2， Ar3， Ar4为独立地表示苯基， 萘基， 联苯基， An 为苯基， 萘基， 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-甲苯基 ,9 ' -苯 基） 芴基， 9,9-螺芴基。
6、 根据权利要求 5所述的有机电子材料， 其中： R2， R3， R6， R7为氢， Ar2， Ar3， Ar4为独立地表 示苯基， 萘基。 、 根据权利要求 2所述的有机电子材料， 为下列结构化合物：
Figure imgf000025_0001
Figure imgf000026_0001
CZ9Z.0/fT0ZN3/X3d WOSJ/ OZ ΟΛ\
Figure imgf000027_0001
SI
¾ OsiAV一z3/:iz>d 9s9/-oz
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000029_0002
OΟίAV /ί卜一Π ι3d誦 /1/π09
Figure imgf000030_0001
29
Figure imgf000031_0001
Figure imgf000032_0001
一、 lf08/.T/£T0i OAV 31
Figure imgf000033_0001
Figure imgf000034_0001
33
Figure imgf000035_0001
ίιιί囊/ioAV s
Figure imgf000036_0001
Figure imgf000037_0001
、 根据权利要求 7所述的有机电子材料， 为下列结构化合物，
Figure imgf000038_0001
9、权利要求 1-8任一所述有机电子材料在有机电致发光器件， 有机太阳能电池， 有机薄膜晶体管或有 机光感受器领域的应用。
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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102050484B1 (ko) 2013-03-04 2019-12-02 삼성디스플레이 주식회사 안트라센 유도체 및 이를 포함하는 유기전계발광소자
KR102107106B1 (ko) 2013-05-09 2020-05-07 삼성디스플레이 주식회사 스티릴계 화합물 및 이를 포함한 유기 발광 소자
KR102269131B1 (ko) 2013-07-01 2021-06-25 삼성디스플레이 주식회사 화합물 및 이를 포함한 유기 발광 소자
US10062850B2 (en) 2013-12-12 2018-08-28 Samsung Display Co., Ltd. Amine-based compounds and organic light-emitting devices comprising the same
KR20150132795A (ko) 2014-05-16 2015-11-26 삼성디스플레이 주식회사 유기 발광 소자
KR102327086B1 (ko) * 2014-06-11 2021-11-17 삼성디스플레이 주식회사 유기 발광 소자
KR102329051B1 (ko) * 2014-11-04 2021-11-19 삼성디스플레이 주식회사 유기 화합물 및 이를 포함하는 유기 발광 장치
KR102343145B1 (ko) 2015-01-12 2021-12-27 삼성디스플레이 주식회사 축합환 화합물 및 이를 포함한 유기 발광 소자
CN106033801B (zh) 2015-03-09 2018-04-06 广东阿格蕾雅光电材料有限公司 有机电致发光器件
CN106033798B (zh) 2015-03-09 2017-11-14 广东阿格蕾雅光电材料有限公司 有机电致发光器件
US11108002B2 (en) * 2016-09-26 2021-08-31 Pioneer Corporation Light emitting device
CN106632446B (zh) * 2016-12-30 2018-08-28 上海升翕光电科技有限公司 一种苯并噻咯类衍生物及其制备方法和有机发光器件

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1094101A2 (en) * 1999-10-20 2001-04-25 Eastman Kodak Company Electroluminescent devices having naphthylanthracene-based polymers
JP2002093582A (ja) * 2000-06-13 2002-03-29 Eastman Kodak Co 電界発光デバイス
CN1407053A (zh) * 2001-08-13 2003-04-02 三星Sdi株式会社 发蓝光的化合物和用其作为彩色显影物质的电致发光装置
JP2007227717A (ja) * 2006-02-24 2007-09-06 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子
CN101143830A (zh) * 2007-01-31 2008-03-19 清华大学 一种有机电致发光材料及其应用
CN101698795A (zh) * 2008-11-24 2010-04-28 上海拓引数码技术有限公司 9-(6-取代-2萘基-)-10-取代蒽类衍生物的蓝光有机电致发光材料及其制备方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000053677A (ja) * 1998-08-10 2000-02-22 Idemitsu Kosan Co Ltd 芳香族炭化水素化合物およびそれを用いた有機エレクトロルミネッセンス素子
KR100274871B1 (ko) * 1998-11-12 2000-12-15 김순택 발광 화합물 및 이를 발색 재료로서 채용하고 있는 표시소자2
EP1009042A3 (en) * 1998-12-09 2002-07-03 Eastman Kodak Company Electroliuminescent device with arylethylene derivatives in hole transport layer
EP1167488B1 (en) * 1999-09-21 2007-04-25 Idemitsu Kosan Company Limited Organic electroluminescent device and organic luminous medium
JP4255610B2 (ja) * 1999-12-28 2009-04-15 出光興産株式会社 白色系有機エレクトロルミネッセンス素子
EP1404160A4 (en) * 2001-06-06 2008-09-24 Idemitsu Kosan Co ORGANIC ELECTROLUMINESCENCE DEVICE
JP2004231563A (ja) * 2003-01-30 2004-08-19 Idemitsu Kosan Co Ltd ビアントリル誘導体、それを含む発光性塗膜形成用材料及び有機エレクトロルミネッセンス素子
US7651787B2 (en) * 2003-02-19 2010-01-26 Lg Display Co., Ltd. Organic electroluminescent device
US7147938B2 (en) * 2004-06-30 2006-12-12 Eastman Kodak Company Organic element for electroluminescent devices
JP4796081B2 (ja) * 2005-11-18 2011-10-19 エルジー・ケム・リミテッド 発光物質およびそれを用いた有機発光素子
KR20100048203A (ko) * 2008-10-30 2010-05-11 다우어드밴스드디스플레이머티리얼 유한회사 신규한 유기 발광 화합물 및 이를 발광재료로서 채용하고 있는 유기 발광 소자
CN101857548B (zh) * 2009-04-28 2012-12-05 广东阿格蕾雅光电材料有限公司 二芳香胺基封端的双蒽类化合物、制备方法及其应用
KR20110098293A (ko) * 2010-02-26 2011-09-01 다우어드밴스드디스플레이머티리얼 유한회사 신규한 유기 발광 화합물 및 이를 포함하는 유기 발광 소자
CN101928559B (zh) * 2010-07-07 2014-02-19 中山大学 同时含三苯乙烯和四苯乙烯结构的聚集诱导发光材料及其合成方法和应用
KR101954980B1 (ko) * 2011-11-03 2019-05-31 삼성디스플레이 주식회사 헤테로고리 화합물 및 이를 포함하는 유기 전계 발광 소자
KR101695351B1 (ko) * 2012-07-25 2017-01-13 삼성디스플레이 주식회사 축합환 화합물 및 이를 포함하는 유기 전계 발광 소자

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1094101A2 (en) * 1999-10-20 2001-04-25 Eastman Kodak Company Electroluminescent devices having naphthylanthracene-based polymers
JP2002093582A (ja) * 2000-06-13 2002-03-29 Eastman Kodak Co 電界発光デバイス
CN1407053A (zh) * 2001-08-13 2003-04-02 三星Sdi株式会社 发蓝光的化合物和用其作为彩色显影物质的电致发光装置
JP2007227717A (ja) * 2006-02-24 2007-09-06 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子
CN101143830A (zh) * 2007-01-31 2008-03-19 清华大学 一种有机电致发光材料及其应用
CN101698795A (zh) * 2008-11-24 2010-04-28 上海拓引数码技术有限公司 9-(6-取代-2萘基-)-10-取代蒽类衍生物的蓝光有机电致发光材料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HUANG, HONG ET AL.: "Solution-processable 1,3,5-tri(9-anthracene)-benzene cored propeller-shaped materials with high Tg for blue organic light-emitting diodes", ORGANIC ELECTRONICS, vol. 12, no. 10, 18 July 2011 (2011-07-18), pages 1716 - 1723 *

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