WO2014173324A1 - 有机电子材料 - Google Patents

有机电子材料 Download PDF

Info

Publication number
WO2014173324A1
WO2014173324A1 PCT/CN2014/076285 CN2014076285W WO2014173324A1 WO 2014173324 A1 WO2014173324 A1 WO 2014173324A1 CN 2014076285 W CN2014076285 W CN 2014076285W WO 2014173324 A1 WO2014173324 A1 WO 2014173324A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
unsubstituted
substituents
substituted
phenyl
Prior art date
Application number
PCT/CN2014/076285
Other languages
English (en)
French (fr)
Inventor
黄锦海
蔡丽菲
戴雷
鲁锦鸿
Original Assignee
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 JP2016509286A priority Critical patent/JP6133495B2/ja
Priority to KR1020157030961A priority patent/KR101781114B1/ko
Priority to US14/787,266 priority patent/US9647215B2/en
Publication of WO2014173324A1 publication Critical patent/WO2014173324A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C07D219/08—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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
    • 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]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a novel organic electronic material, which can be deposited by vacuum evaporation or spin-coated into a film, and is applied to an organic electroluminescent diode, and belongs to the field of organic electroluminescent materials. Background technique
  • 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 depositing an organic material between two metal electrodes by spin coating or vacuum evaporation.
  • 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 with 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. It is also possible to cause the device to emit white light by material matching in the luminescent layer.
  • the hole injection material copper phthalocyanine (CuPc) has been used, which has low degradation rate and high energy consumption, which is not conducive to environmental protection.
  • the common hole transport material is TPD of NPB and, despite having a good hole mobility, respectively 1.0 * 10_ 3 and S. lO ⁇ cm 2 ⁇ 1, but the glass transition temperature of the two materials were 65 ° ⁇ and 981, its stability is still far from meeting the needs of oled applications. Therefore, it is necessary to develop efficient and stable Qualitative organic electroluminescent materials. Summary of the invention
  • the present invention is to overcome the defects of the above compounds, and provides a series of hole transporting and injecting materials having good thermal stability, high hole mobility and good solubility, and the organic electroluminescent device prepared therefrom has good electroluminescence efficiency. Excellent color purity and long life.
  • R r R 3 is represented as hydrogen, helium atom, . , cyano group, nitro group, amine group, C1-C8 fluorenyl group, C1-C8 decyloxy group, and C6-C30 contains one or more substituents R Or an unsubstituted aryl group, C3-C30 containing one or more substituents R or unsubstituted one or more hetero atom aryl groups, C2-C8 containing one or more substituents R or unsubstituted An olefin group, a C2-C8 group having one or more substituents R substituted or unsubstituted alkynyl group, a C8-C30 group having one or more substituents R substituted or unsubstituted diarylene, C8-C30 a substituted or unsubstituted diarylethynyl group having one or more substituents R, a trimethylsilyl group, a C6-C30 group
  • a ri -Ar 2 is independently represented by C6-C30 as an aryl group having one or more substituents R, and contains one or more substituents R or an unsubstituted aromatic fused ring group, and C6-C30 contains one or more Substituent R or An unsubstituted carbazolyl group, C6-C30 containing one or more substituents R or an unsubstituted triarylamine group, wherein R independently represents a fluorenyl group, a five- or six-membered ring aryl group, a decyloxy group , oxime, halogen, cyano, nitro, amine.
  • RrR 3 is independently selected from the group consisting of hydrogen, halogen, C1-C8 fluorenyl, and C6-C30 contains one or more substituents R or unsubstituted phenyl group, containing one or more substituents R or unsubstituted a diarylamine group, C6-C30 containing one or more substituents R or an unsubstituted aromatic fused ring group, C6-C30 containing one or more substituents R or an unsubstituted carbazolyl group, or two Spiro structure;
  • Ar r A r2 is independently represented as an aryl group containing one or more substituents R, and C6-C30 contains one or more substituents R or an unsubstituted aromatic fused ring group, and the C6-C30 content One or more substituents R or an unsubstituted carbazolyl group, C6-C30 containing one or more substituents R or an unsubstituted carbazo
  • RrR 3 is independently selected from the group consisting of hydrogen, C1-C8 fluorenyl, one or more C1-C3 fluorenyl, C1-C3 decyloxy, aryl-substituted or unsubstituted phenyl, one or more C1-C3 fluorenyl, C1-C3 decyloxy, aryl-substituted or unsubstituted naphthyl, one or more C1-C3 fluorenyl, C1-C3 decyloxy, aryl-substituted or unsubstituted An aromatic amine group containing one or more C1-C3 fluorenyl groups, a C1-C3 decyloxy group an aryl-substituted or unsubstituted carbazolyl group, or a spiro structure formed between two R 2 groups.
  • R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclohexyl , n-octyl, isooctyl, C1-C3 fluorenyl substituted or unsubstituted phenyl, C1-C3 decyl substituted or unsubstituted phenyl, naphthyl, or a spiro structure formed between two groups, One or more methyl, phenyl substituted or unsubstituted diarylamine groups, one or more methyl, phenyl substituted or unsubstituted oxazolyl groups, R 3 independently selected from hydrogen, C1-C8 fluorene Base, C1-C3 substituted or unsubstituted
  • Ri, R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclohexyl , n-octyl, isooctyl, phenyl, tolyl, wherein are independently selected from the group consisting of hydrogen, C1-C3 fluorenyl, C1-C3 fluorenyl substituted or unsubstituted phenyl.
  • R 3 is preferably hydrogen, methyl, phenyl
  • Ri is independently selected from hydrogen, methyl, tert-butyl, phenyl or a spiro structure between two groups
  • a -Ar 2 independent representation Is any group in the list below.
  • An organic electroluminescent device prepared from the material of the present invention, the device comprising an anode, a cathode and one or more organic layers, at least one of the organic layers comprising an organic material as described in Structural Formula I.
  • the organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer. It is to be noted that the above organic layers may be present in each of the organic layers as needed.
  • the organic electroluminescent device of the present invention comprises at least one layer of the organic material containing the structural formula I between the anode and the light-emitting layer, which may be present as a single layer or as one of the mixed components.
  • the organic electroluminescent device of the present invention comprises at least one layer of an organic material as described in Structural Formula I as a hole transporting layer or a hole injecting layer. It can be used as a single layer or in combination with other chemical components.
  • the organic electroluminescent device of the present invention may comprise a light-emitting layer, the light-emitting layer comprising at least one A compound of formula I.
  • the light-emitting region of the light-emitting layer is in the range of 380-740 nm and covers the entire white light region.
  • the invention ranges from 380 to 550 nm, more preferably emits blue light, and ranges from 440 to 490 nm.
  • the compound of the formula I when used as the light-emitting layer, it can be used as an undoped single light-emitting layer or a doped light-emitting layer.
  • the doped luminescent layer comprises a host material and a guest material, and the compound of formula I may be a host material or a guest material as needed. This includes the simultaneous use of two compounds of structural formula I as the host material and the guest material, respectively.
  • the compound of the formula I When the compound of the formula I is used as a host material, its concentration 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. When the compound of the formula I is used as a guest material, 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 hole transporting layer and the hole injecting 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.
  • the above may also include small molecules and high molecular organic materials, which may include, but are not limited to, triarylamine compounds, biphenyldiamine compounds, thiazole compounds, oxazole compounds, imidazoles.
  • the organic electroluminescent layer of the present invention may contain, in addition to the 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 chelates.
  • 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.
  • an alkaline earth metal compound the following compounds may be 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 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, each of the organic electroluminescent devices of the present invention, which may be vaporized or spin coated. , or inkjet printing, etc.
  • the invention is prepared by steaming by means of vacuum evaporation with a vacuum of less than W 5 bar, preferably less than 1 (J 6 bar.
  • the device experiments show that the organic light-emitting material of the invention according to the formula (I) has good thermal stability, high hole mobility, high luminous efficiency and high luminous purity.
  • An organic electroluminescent device fabricated using the organic luminescent material has the advantages of good electroluminescence efficiency, excellent color purity, and long life.
  • 1 is a structural view of a device of the present invention
  • 10 is a glass substrate
  • 20 is an anode
  • 30 is a hole injection layer
  • 40 is a hole transport layer
  • 50 is a light-emitting layer
  • 60 is an electron transport layer.
  • 70 represents an electron injection layer
  • 80 represents a cathode.
  • FIG. 2 is a current density and voltage diagram of a device of Example 3, Example 5, and Comparative Example 1
  • FIG. 3 is a diagram showing luminous efficiency and current density of a device of Example 3, Example 5, and Comparative Example 1 of the present invention.
  • 4 is an electrospray ionization mass spectrum of Compound 2 of Example 1 of the present invention. detailed description
  • the transparent conductive ITO glass substrate 10 (with the anode 20 thereon) was sequentially washed with a detergent solution and deionized water, ethanol, acetone, deionized water, and then treated with oxygen plasma for 30 seconds.
  • the compound NPB was distilled to form a hole transport layer 40 having a thickness of 60 nm.
  • the transparent conductive ITO glass substrate 10 (with the anode 20 thereon) was sequentially washed with a detergent solution and deionized water, ethanol, acetone, deionized water, and then treated with oxygen plasma for 30 seconds.
  • the compound NPB was distilled to form a hole transport layer 40 having a thickness of 60 nm.
  • the transparent conductive ITO glass substrate 10 (with the anode 20 thereon) was sequentially washed with a detergent solution and deionized water, ethanol, acetone, deionized water, and then treated with oxygen plasma for 30 seconds.
  • Compound 2 having a thickness of 30 nm was vapor-deposited on the ITO as the hole injecting layer 30.
  • the compound NPB was distilled to form a hole transport layer 40 having a thickness of 60 nm.
  • the transparent conductive ITO glass substrate 10 (with the anode 20 thereon) was sequentially washed with a detergent solution and deionized water, ethanol, acetone, deionized water, and then treated with oxygen plasma for 30 seconds.
  • compound 40 having a thickness of 40 nm was vapor-deposited on the ITO as the hole injecting layer 30.
  • the compound NPB was distilled to form a hole transport layer 40 having a thickness of 60 nm.
  • 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. Then, the compound NPB was vaporized on the ITO to form a 60 nm thick hole transport layer 40.
  • the device illuminating data is shown in Figure 2 and 3.
  • Table 1 is a CIE coordinate of an embodiment 2 - 5 device of the present invention
  • Comparative Example 1 the organic light-emitting material of the formula (I) of the present invention was used as a hole injecting material, and the luminous efficiency was only 2.7 cd/A, but the effect was remarkably improved after being added as a hole injecting material.
  • Example 5 the organic light-emitting material of the present invention as in the formula (I) was used as a 40 nm thick hole injecting material, and the luminous efficiency was increased by more than 37% to 3.7 cd/A as compared with Comparative Example 1.
  • the device experiments show that the organic light-emitting material of the invention of the formula (I) has good thermal stability, high hole mobility, high luminous efficiency and high luminous purity.
  • the organic electroluminescent device produced by using the organic light-emitting material has the advantages of good electroluminescence efficiency, excellent color purity, and long life.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)

Abstract

本发明涉及一种有机电子材料，具有式（I）所示结构，其为具有较好热稳定性，高空穴迁移率和良好溶解性的空穴传输、注入材料，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。

Description

说明书
有机电子材料 技术领域
本发明涉及新型的有机电子材料， 可以通过真空蒸渡沉积或者旋涂成薄膜， 应 用在有机电致发光二极管上， 属于有机电致发光材料领域。 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。
有机电致发光器件为在两个金属电极之间通过旋涂或者真空蒸渡沉积一层有机 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。 也可以通过在发光层进行材料搭配， 使器件发射白光。
可是， 现在的 OLED器件由于效率低， 使用寿命短等因素制约其应用， 因此要 改善这些条件的限制。 其中， 降低空穴注入 /传输材料与发光材料之间的能垒和提到 空穴传输材料的热稳定性有助于改善 OLED器件的效率和提高使用寿命。 另外， 由 于小分子的空穴注入 /传输材料的溶解性比较差， 只能通过蒸渡来制备器件， 不利于 商品化使用， 因此发展良好溶解性的高空穴迁移率的材料实现旋涂或者喷墨打印有 利于大面积应用。
已有使用的空穴注入材料 copper phthalocyanine (CuPc),其降解慢，制备耗能高， 不利于环境保护。而常见的空穴传输材料为 TPD和 NPB，尽管具有很好的空穴迁移 率， 分别是 1.0*10_3和 S. lO^ cm2^^1, 但是这两个材料的玻璃化温度分别为 65 °〇和981， 其稳定性还是远远不能满足 oled的应用需求。 因而， 需要发展高效和稳 定性的有机电致发光材料。 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， 高空穴迁移 率和良好溶解性的空穴传输、 注入材料， 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。
一种有机电子材料， 具有如下化学式 I所述结构式： 结构式 I
Figure imgf000004_0001
其中， RrR3 立地表示为氢， 氘原子， ., 氰基， 硝基， 胺基， C1-C8焼基、 C1-C8垸氧基， C6-C30的含一个或者多个取代基 R或者未取代的芳基， C3-C30的 含一个或者多个取代基 R或者未取代的含有一个或者多个的杂原子芳基， C2-C8的 含一个或者多个取代基 R或者未取代的烯垸基， C2-C8的含一个或者多个取代基 R 取代或者未取代的炔垸基， C8-C30的含一个或者多个取代基 R取代或者未取代的二 芳乙烯基， C8-C30的含一个或者多个取代基 R取代或者未取代的二芳乙炔基，三垸 基硅， C6-C30的含一个或者多个取代基 R或者未取代的三芳香硅基， C6-C30的含 一个或者多个取代基 R或者未取代的二芳香氧磷基、 C6-C30的含一个或者多个取代 基 R或者未取代的芳香羰基、 C6-C30的含一个或者多个取代基 R或者未取代的芳 硫基， C6-C30的含一个或者多个取代基 R或者未取代的芳香稠环基， C6-C30的含 杂原子的取代或者未取代的芳香稠环基， C6-C30含一个或者多个取代基 R或者未取 代的咔唑基， C6-C30的含一个或者多个取代基 R或者未取代的二芳香胺基，或者两 个 基团之间形成螺结构， 所述杂原子为 B, 0, S, N, Se;
Ari-Ar2独立地表示为 C6-C30的含有一个或者多个取代基 R的芳基， 含一个或 者多个取代基 R或者未取代的芳香稠环基， C6-C30的含一个或者多个取代基 R或 者未取代的咔唑基， C6-C30的含一个或者多个取代基 R或者未取代的三芳香胺基， 其中 R独立地表示垸基， 五元或六元环的芳基， 垸氧基， 氘， 卤素， 氰基， 硝 基， 胺基。
优选： 其中 RrR3独立地选自氢， 卤素、 C1-C8焼基， C6-C30的含有一个或者多 个取代基 R或者未取代的苯基，含有一个或者多个取代基 R或者未取代的二芳香胺 基， C6-C30的含有一个或者多个取代基 R或者未取代的芳香稠环基， C6-C30的含 一个或者多个取代基 R或者未取代的咔唑基， 或者两个 形成螺芴结构； ArrAr2 独立地表示为含有一个或者多个取代基 R的芳基， C6-C30的含一个或者多个取代基 R或者未取代的芳香稠环基， C6-C30的含一个或者多个取代基 R或者未取代的咔唑 基， C6-C30的含一个或者多个取代基 R或者未取代的三芳香胺基， 其中 R独立地 表示垸基， 五元或六元环的芳基， 垸氧基， 卤素。
再优选：其中 RrR3独立地选自氢， C1-C8垸基，一个或者多个 C1-C3垸基、 C1-C3 垸氧基、 芳香基取代的或者未取代的苯基， 一个或者多个 C1-C3垸基、 C1-C3垸氧 基、 芳香基取代的或者未取代的萘基， 一个或者多个 C1-C3垸基、 C1-C3垸氧基、 芳香基取代的或者未取代的二芳香胺基， 含有一个或者多个 C1-C3垸基、 C1-C3垸 氧基、 芳香基取代或者未取代的咔唑基， 或者两个 R2基团之间形成螺结构。
进一步优选： 其中 Ri， R2独立地选自氢， 甲基， 乙基， 丙基， 异丙基， 丁基， 叔丁基， 正戊基， 异戊基， 正己基， 异己基， 环己基， 正辛基， 异辛基， C1-C3 垸 基取代或未取代的苯基， C1-C3垸氧基取代或未取代的苯基， 萘基， 或者两个 基 团之间形成螺结构， 一个或者多个甲基、 苯基取代或者未取代的二芳香胺基， 一个 或者多个甲基、 苯基取代或者未取代的咔唑基， R3独立地选自氢， C1-C8的焼基， C1-C3取代或者未取代的苯基。
更优选： 其中 Ri， R2独立地选自氢， 甲基， 乙基， 丙基， 异丙基， 丁基， 叔丁基， 正戊基， 异戊基， 正己基， 异己基， 环己基， 正辛基， 异辛基， 苯基， 甲苯基， 其 中 独立地选自氢， C1-C3焼基， C1-C3垸基取代或未取代的苯基。
更优选： 其中 R3优选为氢， 甲基， 苯基， Ri 独立地选自氢， 甲基， 叔丁基， 苯基或者两个 基团之间形成螺结构， A -Ar2独立的表示为下列表中任一基团。
Figure imgf000005_0001
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000008_0001
S8Z9.0/M0ZN3/X3d
Figure imgf000009_0001
S Z9L0/n0ZSLJ/∑Jd tZ££Ll/nOZ OAV
Figure imgf000010_0001
S8Z9.0/M0ZN3/X3d
Figure imgf000011_0001
本发明材料制备的有机电致发光器件， 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所述的有机材料。 所述有机层可以 包括空穴注入层， 空穴传输层， 发光层， 空穴阻挡层， 电子传输层和电子注入层。 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。
本发明的有机电致发光器件在阳极和发光层之间至少包含有一层含有结构式 I 所述的有机材料， 可以单独作为一层存在， 也可以作为混合组分中的一种。
本发明的有机电致发光器件至少包含一层如结构式 I所述有机材料作为空穴传 输层或者空穴注入层。可以单独以一层形式存在， 也可以跟其他化学组分混合使用。
本发明的有机电致发光器件可以包含有一层发光层， 该发光层至少包含一个具 有结构式 I的化合物。 该发光层的发光区域在 380-740 nm范围内， 覆盖整个白光区 域。 优选本发明范围在 380-550 nm， 更优选发射蓝光， 范围在 440-490 nm。
结构式 I化合物作为发光层时， 可以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化合物根据需要可以主体 材料或者客体材料。 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。
当结构式 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%。
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。 除了上述具有结构式 1所述材料外， 还 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。
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 本发明的有机电致发光器件中的每一层， 可以通过蒸渡或者旋涂的方式， 或者 喷墨打印等方式制备。 本发明使用蒸渡方式制备是， 是通过真空蒸渡， 真空度为小 于 W5 bar， 优选小于 l(J6bar。
器件实验表明， 本发明如式 （I) 所述的有机发光材料， 具有较好热稳定性， 高空穴迁移率， 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点。 附图说明
图 1为本发明的器件结构图， 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为本发明的实施例 3, 实施例 5, 比较例 1器件的电流密度与电压图， 图 3为本发明的实施例 3, 实施例 5, 比较例 1器件的发光效率与电流密度图， 图 4为本发明的实施例 1的化合物 2的电喷雾离子化质谱图。 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 2的合成
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000014_0003
P(t-Bu)3 中间体 1-1的合成
在 1L的三口烧瓶中加入化合物邻氨基苯甲酸甲酯和对溴碘苯，碘化亚铜，和碳酸钾， 邻二氯苯， 氮气保护下， 加热到 180度 24小时， 冷却至 100度， 过滤， 滤液减压除 去溶剂， 然后用柱层析过柱子分离得到化合物 1-1。 收率 92%， HPLC纯度 96% 中间体 1-2的合成
在 1L的三口烧瓶中， 加入化合物 1-1， 和四氢呋喃， 氮气保护下， 冷却至 0度， 然 后滴加甲基溴化镁试剂， 滴完， 缓慢升温至室温， 过夜反应， 然后加入 1N的盐酸 水溶液中， 用乙酸乙酯萃取， 干燥， 浓缩， 而后用柱层析过柱分离得到化合物 1-2。 收率 83%， HPLC纯度 93%。
中间体 1-3的合成
在 1L的三口烧瓶中， 加入化合物 1-2， 磷酸， 搅拌， 反应完全， 加入水中， 过滤， 滤饼用甲醇洗涤 2遍， 得到中间体 1-3。 收率 80% HPLC含量 90% 中间体 1-4的合成
在 1L的三口烧瓶中加入化合物 1-3和碘苯， 叔丁醇钾， 三叔丁基磷， 二甲苯， 氮气 保护下， 加热到 120度 24小时， 冷却至室温， 过滤， 滤液减压除去溶剂， 然后用柱 层析过柱子分离得到化合物 1-4。
化合物 2的合成
在 1L的三口烧瓶中加入化合物 1-4和联苯二胺， 叔丁醇钾， 三叔丁基磷， 二甲苯， 氮气保护下， 加热到 120度 24小时， 冷却至 100度， 过滤， 滤液减压除去溶剂， 然 后用柱层析过柱子分离得到化合物 2。 ESI-MS m/z 902.4. 实施例 2
有机电致发光器件的制备
使用本发明的有机电致发光材料制备 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 10 nm厚的化合物 2作为空穴注入层 30。
然后， 蒸渡化合物 NPB,形成 60 nm厚的空穴传输层 40。
然后， 在空穴传输层上蒸渡 50 nm厚的化合物 Alq3作为发光层 50。
然后， 在发光层上蒸渡 lO nm厚的八1 作为电子传输层 60。
最后， 蒸渡 1 nm Liq为电子注入层 70和 100 nm Al作为器件阴极 80 。 实施例 3
有机电致发光器件的制备
使用本发明的有机电致发光材料制备 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 20 nm厚的化合物 2作为空穴注入层 30。
然后， 蒸渡化合物 NPB,形成 60 nm厚的空穴传输层 40。
然后， 在空穴传输层上蒸渡 50 nm厚的化合物 Alq3作为发光层 50。
然后， 在发光层上蒸渡 lO nm厚的八1 作为电子传输层 60。 最后， 蒸渡 1 nm Liq为电子注入层 70和 100 nm Al作为器件阴极 80 。 实施例 4
有机电致发光器件的制备
使用本发明的有机电致发光材料制备 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 30 nm厚的化合物 2作为空穴注入层 30。
然后， 蒸渡化合物 NPB,形成 60 nm厚的空穴传输层 40。
然后， 在空穴传输层上蒸渡 50 nm厚的化合物 Alq3作为发光层 50。
然后， 在发光层上蒸渡 lO nm厚的八1 作为电子传输层 60。
最后， 蒸渡 1 nm Liq为电子注入层 70和 100 nm Al作为器件阴极 80 。 实施例 5
有机电致发光器件的制备
使用本发明的有机电致发光材料制备 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 40 nm厚的化合物 2作为空穴注入层 30。
然后， 蒸渡化合物 NPB,形成 60 nm厚的空穴传输层 40。
然后， 在空穴传输层上蒸渡 50 nm厚的化合物 Alq3作为发光层 50。
然后， 在发光层上蒸渡 lO nm厚的八1 作为电子传输层 60。
最后， 蒸渡 1 nm Liq为电子注入层 70和 100 nm Al作为器件阴极 80 。 比较例 1
有机电致发光器件的制备
使用本发明的有机电致发光材料制备 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上蒸渡化合物 NPB,形成 60 nm厚的 穴传输层 40。
然后， 在空穴传输层上蒸渡 50 nm厚的化合物 Alq3作为发光层 50。
然后， 在发光层上蒸渡 lO nm厚的八1 作为电子传输层 60。
最后， 蒸渡 1 nm Liq为电子注入层 70和 100 nm Al作为器件阴极 80 。 器件中所述结构式
Figure imgf000017_0001
器件发光数据如图 2、 3所示。
表 1为本发明的实施例 2 - 5器件的 CIE坐标
Figure imgf000017_0002
比较例 1在没有本发明如式 （I)所述的有机发光材料作为空穴注入材料， 发光 效率只有 2.7 cd/A, 但加入作为空穴注入材料后， 效果明显提升。 在实施例 5采用 本发明如式（I)所述的有机发光材料作为 40 nm厚空穴注入材料， 发光效率与比较 例 1相比增加超过 37%达到 3.7 cd/A。
器件实验表明， 本发明如式 （I)所述的有机发光材料， 具有较好热稳定性， 高空穴 迁移率， 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点。

Claims

权利要求书
Figure imgf000018_0001
其中， RrR3独立地表示为氢， 氘原子， 卤素， 氰基， 硝基， 胺基， C1-C8垸基、 C1-C8垸氧基， C6-C30的含一个或者多个取代基 R或者未取代的芳基， C3-C30的 含一个或者多个取代基 R或者未取代的含有一个或者多个的杂原子芳基， C2-C8的 含一个或者多个取代基 R或者未取代的烯垸基， C2-C8的含一个或者多个取代基 R 取代或者未取代的炔垸基， C8-C30的含一个或者多个取代基 R取代或者未取代的二 芳乙烯基， C8-C30的含一个或者多个取代基 R取代或者未取代的二芳乙炔基，三垸 基硅， C6-C30的含一个或者多个取代基 R或者未取代的三芳香硅基， C6-C30的含 一个或者多个取代基 R或者未取代的二芳香氧磷基、 C6-C30的含一个或者多个取代 基 R或者未取代的芳香羰基、 C6-C30的含一个或者多个取代基 R或者未取代的芳 硫基， C6-C30的含一个或者多个取代基 R或者未取代的芳香稠环基， C6-C30的含 杂原子的取代或者未取代的芳香稠环基， C6-C30含一个或者多个取代基 R或者未取 代的咔唑基， C6-C30的含一个或者多个取代基 R或者未取代的二芳香胺基，或者两 个 R2基团之间形成螺结构， 所述杂原子为 B, 0, S, N, Se;
ArrAr2独立地表示为 C6-C30的含有一个或者多个取代基 R的芳基， 含一个或 者多个取代基 R或者未取代的芳香稠环基， C6-C30的含一个或者多个取代基 R或 者未取代的咔唑基， C6-C30的含一个或者多个取代基 R或者未取代的三芳香胺基， 其中 R独立地表示垸基， 五元或六元环的芳基， 垸氧基， 氘， 卤素， 氰基， 硝 基， 胺基。
2、根据权利要求 1所述的有机电子材料，其中 RrR3独立地选自氢，卤素、 C1-C8 垸基， C6-C30的含有一个或者多个取代基 R或者未取代的苯基，含有一个或者多个 取代基 R或者未取代的二芳香胺基， C6-C30的含有一个或者多个取代基 R或者未 取代的芳香稠环基， C6-C30的含一个或者多个取代基 R或者未取代的咔唑基，或者 两个 R2形成螺芴结构； An-Ar2独立地表示为含有一个或者多个取代基 R的芳基， C6-C30的含一个或者多个取代基 R或者未取代的芳香稠环基， C6-C30的含一个或 者多个取代基 R或者未取代的咔唑基， C6-C30的含一个或者多个取代基 R或者未 取代的三芳香胺基， 其中 R独立地表示垸基， 五元或六元环的芳基， 垸氧基， 卤素。
3、根据权利要求 2所述的有机电子材料，其中 RrR3独立地选自氢， C1-C8垸基， 一个或者多个 C1-C3垸基、 C1-C3垸氧基、 芳香基取代的或者未取代的苯基， 一个 或者多个 C1-C3垸基、 C1-C3垸氧基、 芳香基取代的或者未取代的萘基， 一个或者 多个 C1-C3垸基、 C1-C3垸氧基、 芳香基取代的或者未取代的二芳香胺基， 含有一 个或者多个 C1-C3垸基、 C1-C3垸氧基、 芳香基取代或者未取代的咔唑基， 或者两 个 基团之间形成螺结构。
4、 根据权利要求 3所述的有机电子材料， 其中 ， R2独立地选自氢， 甲基， 乙基， 丙基， 异丙基， 丁基， 叔丁基， 正戊基， 异戊基， 正己基， 异己基， 环己基， 正辛基， 异辛基， C1-C3垸基取代或未取代的苯基， C1-C3垸氧基取代或未取代的 苯基， 萘基， 或者两个 基团之间形成螺结构， 一个或者多个甲基、 苯基取代或者 未取代的二芳香胺基， 一个或者多个甲基、 苯基取代或者未取代的咔唑基， R3独立 地选自氢， C1-C8的垸基， C1-C3取代或者未取代的苯基。
5、 根据权利要求 4所述的有机电子材料， 其中 ， 独立地选自氢， 甲基， 乙 基， 丙基， 异丙基， 丁基， 叔丁基， 正戊基， 异戊基， 正己基， 异己基， 环己基， 正辛基， 异辛基， 苯基， 甲苯基， 其中 R3独立地选自氢， C1-C3垸基， C1-C3垸基 取代或未取代的苯基。
6、 根据权利要求 5所述的有机电子材料， 其中 R3优选为氢， 甲基， 苯基， Ri R2独立地选自氢， 甲基， 叔丁基， 苯基或者两个 R2基团之间形成螺结构， ArrAr2 独立的表示为下列表中任一基团。
1
Figure imgf000020_0001
S8Z9.0/M0ZN3/X3d
Figure imgf000021_0001
Figure imgf000022_0001
S8Z9.0/M0ZN3/X3d
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
8、根据权利要求 7所述的有机电子材料， 其中 独立地选自氢， 甲基， 苯基， ArrAr2独立的表示苯基、 萘基或联苯基。
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。
PCT/CN2014/076285 2013-04-27 2014-04-25 有机电子材料 WO2014173324A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2016509286A JP6133495B2 (ja) 2013-04-27 2014-04-25 有機電子材料
KR1020157030961A KR101781114B1 (ko) 2013-04-27 2014-04-25 유기전자재료
US14/787,266 US9647215B2 (en) 2013-04-27 2014-04-25 Organic electronic material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310154057.2 2013-04-27
CN201310154057 2013-04-27

Publications (1)

Publication Number Publication Date
WO2014173324A1 true WO2014173324A1 (zh) 2014-10-30

Family

ID=51765505

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/076285 WO2014173324A1 (zh) 2013-04-27 2014-04-25 有机电子材料

Country Status (7)

Country Link
US (1) US9647215B2 (zh)
JP (1) JP6133495B2 (zh)
KR (1) KR101781114B1 (zh)
CN (1) CN104119861B (zh)
HK (1) HK1200865A1 (zh)
TW (1) TWI541239B (zh)
WO (1) WO2014173324A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11424417B2 (en) 2018-11-16 2022-08-23 Samsung Display Co., Ltd. Organic electroluminescence device and compound for organic electroluminescence device
US11985893B2 (en) 2019-11-08 2024-05-14 Samsung Display Co., Ltd. Organic electroluminescence device and aromatic compound for organic electroluminescence device

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106866499B (zh) * 2016-12-26 2020-01-10 广东阿格蕾雅光电材料有限公司 有机空穴传输材料
CN108832013B (zh) * 2018-06-19 2020-06-12 长春海谱润斯科技有限公司 一种有机电致发光器件
CN108863918B (zh) * 2018-06-19 2022-02-11 长春海谱润斯科技股份有限公司 一种芳胺衍生物及其有机电致发光器件
CN111848619A (zh) * 2019-04-24 2020-10-30 上海和辉光电有限公司 一种有机光电材料及其制备方法和应用
CN111039924A (zh) * 2019-11-26 2020-04-21 武汉华星光电半导体显示技术有限公司 以乙烯双吖啶为核的空穴传输材料及有机发光二极管

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1906267A (zh) * 2003-11-07 2007-01-31 索尼株式会社 有机发光材料和制备有机材料的方法
CN101405255A (zh) * 2006-03-23 2009-04-08 Lg化学株式会社 新的二胺衍生物、其制备方法以及使用该二胺衍生物的有机电子器件
KR20100006072A (ko) * 2008-07-08 2010-01-18 주식회사 하나화인켐 유기 발광 화합물 및 이를 구비한 유기 발광 소자
CN101679150A (zh) * 2007-05-17 2010-03-24 Lg化学株式会社 新型蒽衍生物和使用该蒽衍生物的有机电子器件

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110132721A (ko) * 2010-06-03 2011-12-09 다우어드밴스드디스플레이머티리얼 유한회사 신규한 유기 발광 화합물 및 이를 채용하고 있는 유기 전계 발광 소자
KR101529157B1 (ko) * 2012-08-23 2015-06-17 주식회사 엠비케이 유기 발광 화합물 및 이를 이용한 유기 발광 소자
WO2014101178A1 (en) * 2012-12-31 2014-07-03 Dow Global Technologies LLC (Formerly known as Dow Global Technologies Inc.) Tetraphenylene ethylene based compound and oled device containing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1906267A (zh) * 2003-11-07 2007-01-31 索尼株式会社 有机发光材料和制备有机材料的方法
CN101405255A (zh) * 2006-03-23 2009-04-08 Lg化学株式会社 新的二胺衍生物、其制备方法以及使用该二胺衍生物的有机电子器件
CN101679150A (zh) * 2007-05-17 2010-03-24 Lg化学株式会社 新型蒽衍生物和使用该蒽衍生物的有机电子器件
KR20100006072A (ko) * 2008-07-08 2010-01-18 주식회사 하나화인켐 유기 발광 화합물 및 이를 구비한 유기 발광 소자

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11424417B2 (en) 2018-11-16 2022-08-23 Samsung Display Co., Ltd. Organic electroluminescence device and compound for organic electroluminescence device
US11985893B2 (en) 2019-11-08 2024-05-14 Samsung Display Co., Ltd. Organic electroluminescence device and aromatic compound for organic electroluminescence device

Also Published As

Publication number Publication date
KR101781114B1 (ko) 2017-09-22
HK1200865A1 (zh) 2015-08-14
JP6133495B2 (ja) 2017-05-24
JP2016523990A (ja) 2016-08-12
TW201441217A (zh) 2014-11-01
US9647215B2 (en) 2017-05-09
KR20160028406A (ko) 2016-03-11
CN104119861A (zh) 2014-10-29
US20160087222A1 (en) 2016-03-24
TWI541239B (zh) 2016-07-11
CN104119861B (zh) 2016-03-09

Similar Documents

Publication Publication Date Title
TWI541323B (zh) 有機電致發光器件
JP4308663B2 (ja) 新しい電子輸送用物質及びこれを利用した有機発光素子
TWI541239B (zh) 有機電子材料
JP6154802B2 (ja) 有機電界発光素子
WO2016158191A1 (ja) 有機電界発光素子
TWI290582B (en) Anthracene compound and organic electroluminescent device including the anthracene compound
KR20160049083A (ko) 퀴녹살린 유도체 화합물 및 이를 이용한 유기전계 발광소자
KR20210042873A (ko) 유기발광소자
WO2013178041A1 (zh) 有机电子材料
JP5783749B2 (ja) エキシマー特性を有する１，８−アリール置換ナフタレン誘導体及びこれを用いた有機ｅｌ素子
CN106892903B (zh) 基于酚嗪和咔唑的有机电致发光化合物及其发光器件
WO2016141694A1 (zh) 有机电致发光器件
Grigalevicius et al. 9, 9′-bis (2, 2-diphenylvinyl)[3, 3′] bicarbazole as low cost efficient hole transporting material for application in red PhOLEDs
WO2018137296A1 (zh) 含有喹喔啉和联苯基团的化合物及其有机电致发光器件
JP2011037743A (ja) ピレン誘導体及びこれを用いた有機発光素子
WO2022131123A1 (ja) 有機電界発光素子及びその製造方法
WO2011040631A1 (en) Diindenopicene compound and organic light emitting device using the same
JP2016150920A (ja) 有機電界発光素子用化合物およびこれを用いた有機電界発光素子
JP5495606B2 (ja) 新規縮合多環化合物およびそれを有する有機発光素子
JP6383623B2 (ja) 有機電界発光素子
JP2012017272A (ja) 新規有機化合物およびそれを有する有機発光素子
JP2008308449A (ja) 縮合環芳香族化合物及びそれを用いた有機発光素子
KR101641351B1 (ko) 아이소퀴놀린 유도체 화합물 및 이를 이용한 유기전계 발광소자
KR102118875B1 (ko) 유기전자소자용 화합물, 이를 포함하는 유기전자소자 및 유기전자소자를 포함하는 표시장치
JP2015218112A (ja) 有機発光デバイスに用いられる化合物およびその化合物を有する有機発光デバイス

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14788326

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016509286

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 14787266

Country of ref document: US

ENP Entry into the national phase

Ref document number: 20157030961

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14788326

Country of ref document: EP

Kind code of ref document: A1