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CN111747932B - Compound, application thereof and organic electroluminescent device - Google Patents

Compound, application thereof and organic electroluminescent device Download PDF

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CN111747932B
CN111747932B CN201910238292.5A CN201910238292A CN111747932B CN 111747932 B CN111747932 B CN 111747932B CN 201910238292 A CN201910238292 A CN 201910238292A CN 111747932 B CN111747932 B CN 111747932B
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CN111747932A (en
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孙恩涛
陈继荣
刘叔尧
吴俊宇
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Beijing Eternal Material Technology Co Ltd
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • 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
    • 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
    • H—ELECTRICITY
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    • 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
    • H10K50/16—Electron transporting layers
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    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
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    • 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
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    • 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

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  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to a compound and application thereof, and an organic electroluminescent device, wherein the compound has a structure shown in a formula (1); the compound is used as an electron transport material in an organic electroluminescent device; the organic electroluminescent device comprises a substrate, a first electrode, a second electrode and at least one organic layer interposed between the first electrode and the second electrode, wherein the organic layer contains any one or at least two of the compounds. The compound provided by the invention has higher electron injection capability and electron migration capability, and can ensure that the device has higher luminous efficiency, lower starting voltage, longer service life and high stability when being used for an organic electroluminescent device.

Description

Compound, application thereof and organic electroluminescent device
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a compound and application thereof, and an organic electroluminescent device.
Background
An organic electroluminescent (OLED: organic Light Emission Diodes) device is a device with a sandwich-like structure, comprising positive and negative electrode layers and an organic functional material layer sandwiched between the electrode layers. And applying voltage to the electrode of the OLED device, injecting positive charges from the positive electrode, injecting negative charges from the negative electrode, and transferring and meeting the positive charges and the negative charges in the organic layer to emit light compositely under the action of an electric field. Because the OLED device has the advantages of high brightness, quick response, wide viewing angle, simple process, flexibility and the like, the OLED device has a great deal of attention in the novel display technical field and the novel illumination technical field. At present, the technology is widely applied to display panels of products such as novel illumination lamps, smart phones and tablet computers, and further expands the application field of large-size display products such as televisions, and is a novel display technology with rapid development and high technical requirements.
In order to prepare the OLED light-emitting device with lower driving voltage, better light-emitting efficiency and longer service life of the device, the performance of the OLED device is continuously improved, the structure and the manufacturing process of the OLED device are required to be innovated, and the photoelectric functional material in the OLED device is required to be continuously researched and innovated so as to prepare the functional material with higher performance. Based on this, the OLED material community has been striving to develop new organic electroluminescent materials to achieve low starting voltage, high luminous efficiency and better service life of the device, but currently used electron transport materials have yet to be optimized, especially the electron mobility and electron injection capability thereof are not high, which on one hand can lead to a decrease in the probability of recombination of holes and electrons due to unbalanced injection and transport of carriers, thereby decreasing the luminous efficiency of the device, and on the other hand, electron transport materials with lower electron mobility can lead to an increase in the starting voltage of the device, thereby affecting the power efficiency and unfavorably saving energy.
CN108822114a discloses an OLED electron transport material and application thereof, the material uses electron-deficient 2, 7-diphenyl-1, 3,6, 8-tetraazapyrene as a core, and a proper substituent is introduced into the electron-deficient center to form a small molecule OLED functional layer material with excellent electron transport performance, the molecular mass is 510-820, and the material has a closed loop structure and excellent thermal stability, thus being applicable to the vapor deposition process for manufacturing small molecule organic electroluminescent devices.
CN105051019B discloses a compound, an electron transport material, and an organic electroluminescent element using the electron transport material, wherein two or more aromatic hydrocarbons or aromatic heterocycles substituted with monovalent groups represented by thiazolylphenyl, oxazolylphenyl, thiazolylpyridyl, or oxazolylpyridyl are used for the electron transport layer of the organic electroluminescent element, thereby contributing to a reduction in driving voltage, an increase in luminous efficiency, an increase in device lifetime, and the like.
CN107353285a discloses an electron transport material, a synthesis method and an organic electroluminescent device thereof, and by connecting different ligands on a main structure, the pi conjugation degree and the electrophilicity of the material are regulated, so that the charge migration directionality of the material is improved, the electron mobility is improved, and the electron transport capability of the material is further improved. The synthesis method is simple and easy to operate. The material is applied to preparing the organic electroluminescent device, can be particularly used as an electron transport layer of the organic electroluminescent device, balances carrier injection and transport, and has the advantages of high luminous efficiency and long service life.
In the above prior art, in order to improve the performance of the electron transport material and the performance of the OLED device, electron transport materials with specific structures are disclosed, but with the gradual improvement of the performance requirements of the OLED device in the market, the types of devices are also various, so that the performances of various OLED devices are required to be met, the types and performances of the existing electron transport materials cannot fully meet the requirements of the devices, and more types of high-performance electron transport materials are yet to be developed.
Accordingly, there is a need in the art to develop a novel electron transport material having higher electron injection capability and electron mobility and an OLED device having higher luminous efficiency and lower starting voltage.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a compound having the structure of formula (1);
in the formula (1), L is a substituted or unsubstituted arylene group formed by connecting 2-10 benzene rings in sequence by single bonds.
In the formula (1), the R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Each independently selected from one of a hydrogen atom, a deuterium atom, a halogen, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group.
Ar is selected from one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl.
When substituents are present on the above groups, each of the substituents is independently selected from one of cyano, halogen, C1-C10 alkanyl or cycloalkyl, C2-C10 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C30 monocyclic or fused-ring aromatic hydrocarbon group, C3-C30 monocyclic or fused-ring heteroaromatic hydrocarbon group.
According to the invention, when a compound is designed, two electron-deficient groups of triazine and derivative groups thereof and quinazoline and derivative groups thereof are simultaneously introduced, and the two groups are connected by using substituted or unsubstituted arylene which is formed by sequentially connecting 2-10 benzene rings by single bonds, and the special connection mode is matched with the respective electron-deficient characteristics of the triazine and the quinazoline, so that the compound has stronger electron-deficient property, is more beneficial to electron injection and migration, has high electron injection capability and high electron migration capability, and can effectively improve the electron injection and migration efficiency in an organic electroluminescent device when being used as an electron transport layer material, thereby ensuring that the device obtains excellent effects of high luminous efficiency and low starting voltage, the starting voltage is less than or equal to 4.49V, the current efficiency is more than or equal to 7.92cd/A, and the device has long service life and high stability.
In addition, the invention provides compounds in which the substituents (R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 ) All are connected with the mother nucleus through single bonds, and substituent groups cannot be mutually condensed and cannot be condensed with the mother nucleus.
The compound has higher electron affinity and thus stronger electron accepting capability, is suitable for being used as an electron transport material in an organic electroluminescent device, and can be applied to the technical fields of optical sensors, solar cells, lighting elements, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information labels, electronic artificial skin sheets, large-area sensors such as sheet scanners, electronic papers and the like.
Preferably, ar is selected from one of substituted or unsubstituted C6-C10 alkyl, substituted or unsubstituted C6-C16 aryl, and substituted or unsubstituted C6-C12 heteroaryl.
Preferably, the molecular weight of the compound is 550 to 750, preferably 600 to 700.
The invention preferably selects the molecular weight range, thereby ensuring that the molecules have higher glass transition temperature and being beneficial to the thermal stability of the molecules, and further prolonging the service life and the stability of the device; meanwhile, the risk of thermal decomposition caused by overlarge molecular weight and overlarge vapor deposition temperature of molecules during vapor deposition is avoided, and unnecessary troubles in the manufacturing process of the device are avoided.
Preferably, the compound has the structure of formula (1-1);
the R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Each independently selected from one of a hydrogen atom, a deuterium atom, a halogen, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group;
ar is selected from one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
the R is a 、R b Each independently selected from one of a hydrogen atom, a deuterium atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group;
Each of n and m is independently selected from integers of 1 to 4;
a is an integer from 1 to n, b is an integer from 1 to m;
when substituents are present on the above groups, each of the substituents is independently selected from one of halogen, C1-C10 alkanyl or cycloalkyl, C2-C10 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C30 monocyclic or fused ring aromatic hydrocarbon group, C3-C30 monocyclic or fused ring heteroaromatic hydrocarbon group.
In the invention, in a preferred scheme, arylene formed by sequentially connecting 2 benzene rings is selected as a connecting group of triazine and quinazoline groups, and the specific connection mode of the 2 benzene rings endows the compound with optimal electron migration and injection capability.
Preferably, the compound has the structure of formula (3-1):
the R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Each independently selected from one of a hydrogen atom, a deuterium atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group.
Ar is selected from one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl.
When substituents are present on the above groups, each of the substituents is independently selected from one of cyano, halogen, C1-C10 alkanyl or cycloalkyl, C2-C10 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C30 monocyclic or fused-ring aromatic hydrocarbon group, C3-C30 monocyclic or fused-ring heteroaromatic hydrocarbon group.
Preferably, the compound has any one of the following structures.
The R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl groupIs a kind of the above-mentioned materials.
Ar is selected from one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl.
When substituents are present on the above groups, each of the substituents is independently selected from one of cyano, halogen, C1-C10 alkanyl or cycloalkyl, C2-C10 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C30 monocyclic or fused-ring aromatic hydrocarbon group, C3-C30 monocyclic or fused-ring heteroaromatic hydrocarbon group.
Preferably, the compound has the structure of formula (4-1);
the R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Each independently selected from one of a hydrogen atom, a deuterium atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group.
Ar is selected from one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl.
When substituents are present on the above groups, each of the substituents is independently selected from one of cyano, halogen, C1-C10 alkanyl or cycloalkyl, C2-C10 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C30 monocyclic or fused-ring aromatic hydrocarbon group, C3-C30 monocyclic or fused-ring heteroaromatic hydrocarbon group.
According to the invention, the structure of (4-1) is optimized, and the triazine and quinazoline groups are connected into benzene rings through meta positions, so that a substituent group and a connecting group form a specific angle, and thus, a specific connecting mode is matched with electron-deficient characteristics of the triazine and quinazoline groups, so that electron injection and migration are facilitated, the device has excellent luminous efficiency and starting voltage, and meanwhile, the service life is long and the stability is high. In addition, the molecules can have better film forming property.
Preferably, the compound has the structure of formula (4-3);
the R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Each independently selected from one of a hydrogen atom, a deuterium atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group.
Ar is selected from one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl.
When substituents are present on the above groups, each of the substituents is independently selected from one of cyano, halogen, C1-C10 alkanyl or cycloalkyl, C2-C10 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C30 monocyclic or fused-ring aromatic hydrocarbon group, C3-C30 monocyclic or fused-ring heteroaromatic hydrocarbon group.
The structure of (4-3) is optimized, the specific connection mode is matched with the electron-deficient characteristic of the triazine and quinazoline groups, and the electron injection and migration are facilitated, so that the luminous efficiency of the device is improved, the starting voltage is reduced, the service life is long, and the stability is high.
Preferably, said R 1 、R 2 、R 3 And R is 4 Are all hydrogen atoms.
Preferably, said R 5 、R 6 And Ar is each independently selected from one of a substituted or unsubstituted C6-C16 aryl, a substituted or unsubstituted C6-C12 heteroaryl.
Preferably, one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluoranthenyl group;
when the substituent is present in the above groups, the substituent is selected from one of alkyl, cycloalkyl, cyano, phenyl, and naphthyl.
Preferably, said R 1 、R 2 、R 3 And R is 4 Are all hydrogen atoms, R is 5 、R 6 And Ar is each independently selected from one of phenyl, cyano-substituted phenyl, biphenyl, cyano-substituted biphenyl, naphthyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, phenanthryl, or fluoranthenyl.
Preferably, said R 1 、R 2 、R 3 And R is 4 Are all hydrogen atoms, R is 5 And R is 6 Each independently selected from phenyl. Preferably, the compound is selected from one of the following compounds C1-C129:
it is a second object of the present invention to provide the use of a compound according to one of the objects as an electron transport material in an organic electroluminescent device.
It is still another object of the present invention to provide an organic electroluminescent device comprising a substrate, a first electrode, a second electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the organic layer contains any one or a combination of at least two of the compounds according to one of the objects.
Preferably, the organic electroluminescent device comprises a substrate, and an anode layer, a plurality of light emitting functional layers and a cathode layer sequentially formed on the substrate; the light-emitting functional layer comprises a hole injection layer, a hole transmission layer, a light-emitting layer and an electron transmission layer, wherein the hole injection layer is formed on the anode layer, the hole transmission layer is formed on the hole injection layer, the cathode layer is formed on the electron transmission layer, and the light-emitting layer is arranged between the hole transmission layer and the electron transmission layer; wherein the electron transport layer contains any one or at least two of the compounds of one of the purposes.
In particular embodiments, a substrate may be used below the first electrode or above the second electrode. The substrates are all glass or polymer materials with excellent mechanical strength, thermal stability, water resistance and transparency. A Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material serving as the first electrode on the substrate. When the first electrode is used as the anode, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) 2 ) An oxide transparent conductive material such as zinc oxide (ZnO), and any combination thereof. When the first electrode is used as the cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag) and any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compounds used as the organic material layer may be small organic molecules, large organic molecules and polymers, and combinations thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer hole transport layer containing only one compound and a single layer hole transport layer containing a plurality of compounds. The hole transport region may have a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or conductive dopant containing polymers such as polystyrene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives such as the compounds shown below HT-1 to HT-34, or any combination thereof.
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more of the compounds HT-1 through HT-34 described above, or one or more of the compounds HI1 through HI3 described below; one or more of the compounds HT-1 to HT-34 may also be used to dope one or more of the compounds HI1 to HI3 described below.
The luminescent layer comprises luminescent dyes (i.e. dopants) that can emit different wavelength spectra, and may also comprise Host materials (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The plurality of monochromatic light emitting layers with different colors can be arranged in a plane according to the pixel pattern, or can be stacked together to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light emitting layer may be a single color light emitting layer capable of simultaneously emitting different colors such as red, green, and blue.
According to different technologies, the luminescent layer material can be made of different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescence luminescent material and the like. In an OLED device, a single light emitting technology may be used, or a combination of different light emitting technologies may be used. The different luminescent materials classified by the technology can emit light of the same color, and can also emit light of different colors.
When the luminescent layer adopts the fluorescence electroluminescence technology, the luminescent layer fluorescent host material can be selected from, but not limited to, one or more combinations of BFH-1 to BFH-16 listed below.
When the luminescent layer employs fluorescence electroluminescence, the luminescent layer fluorescent dopant may be selected from, but is not limited to, one or more combinations of BFD-1 through BFD-12 listed below.
When the luminescent layer adopts phosphorescence electroluminescence technology, the main material of the luminescent layer is selected from, but not limited to, one or a combination of a plurality of GPH-1 to GPH-80.
When the light emitting layer employs phosphorescent light emitting technology, the light emitting layer phosphorescent dopant may be selected from, but is not limited to, one or more combinations of GPD-1 to GPD-47 listed below.
When the luminescent layer adopts phosphorescence electroluminescence technology, the main material of the luminescent layer is selected from, but not limited to, one or a combination of a plurality of RH-1 to RH-31.
When the light emitting layer employs phosphorescent light emitting technology, the light emitting layer phosphorescent dopant may be selected from, but is not limited to, one or more combinations of RPD-1 through RPD-28 listed below.
When the light-emitting layer employs the technique of phosphorescence, the phosphorescent dopant of the light-emitting layer may be selected from, but not limited to, one or more of YPD-1 to YPD-11 listed below.
When the light-emitting layer employs a technique of thermally activating delayed fluorescence emission, the light-emitting layer fluorescent dopant thereof may be selected from, but is not limited to, one or more combinations of TDE-1 to TDE-39 listed below.
When the light-emitting layer adopts a technology of thermally activating and delaying fluorescence luminescence, the main material of the light-emitting layer is selected from one or a combination of a plurality of TDH1 to TDH24, but not limited to.
The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single layer structure including a single layer electron transport layer containing only one compound and a single layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
The electron transport region may also be formed by applying the compound of the present invention to a multi-layer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL), although the material of the electron transport region may also be combined with one or more of ET-1 to ET-57 listed below.
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, a combination of one or more of the following.
Liq、LiF、NaCl、CsF、Li 2 O、Cs 2 CO 3 、BaO、Na、Li、Ca。
Methods for forming the above layers are well known, and for example, vapor deposition, sputtering, solution coating, and the like can be used.
In one embodiment, the preparation method of the organic electroluminescent device provided by the invention comprises the following steps:
(1) Ultrasonic treating the glass plate coated with the anode transparent conductive layer in a commercial cleaning agent, flushing in deionized water, ultrasonic degreasing in a mixed solvent of acetone and ethanol, baking in a clean environment until water is completely removed, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam;
(2) Placing the glass substrate with the anode in a vacuum cavity, vacuumizing, and evaporating a hole transport material on the anode layer film by utilizing a multi-source co-evaporation method;
(3) Vacuum evaporating a first hole transport layer on the hole injection layer;
(4) Vacuum evaporating a second hole transport layer on the first hole transport layer;
(5) Vacuum evaporating a light-emitting layer of the device on the second hole transport layer, wherein the light-emitting layer comprises a main material and a dye material, and a multi-source co-evaporation method is utilized;
(6) Vacuum evaporating a hole blocking layer on the light-emitting layer;
(7) Evaporating a first electron transport material (any one or at least two of the compounds provided by the invention) and a second electron transport material on the hole blocking layer by utilizing a multi-source co-evaporation method;
(8) And vacuum evaporating an electron injection layer on the electron transport layer, and finally evaporating a cathode.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, triazine and derivative groups thereof and quinazoline and derivative groups thereof are simultaneously introduced into the compound, and the two groups are connected by using substituted or unsubstituted arylene which is formed by sequentially connecting 2-10 benzene rings by single bonds, and the special connection mode is matched with the specific electron deficiency characteristic of the triazine and the quinazoline, so that the compound has stronger electron deficiency property, is more beneficial to electron injection and migration, and has high electron injection capability and high electron migration capability, when being used as an electron transport layer material in an organic electroluminescent device, the electron injection and migration efficiency in the device can be effectively improved, thereby ensuring that the device obtains excellent effects of high luminous efficiency and low starting voltage, the starting voltage is less than or equal to 4.49V, the current efficiency is more than or equal to 7.92cd/A, and the device has long service life and high stability.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The synthetic route of the compound of formula (1) of the present invention is as follows:
compound M1 and compound M2 are subjected to a Suzuki coupling reaction to produce a compound of formula (1) of the present invention.
Wherein L is a substituted or unsubstituted arylene group formed by sequentially connecting 2-10 benzene rings by single bonds;
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently selected from one of a hydrogen atom, a cyano group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group;
ar is selected from one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
when substituents are present on the above groups, each of the substituents is independently selected from one of cyano, halogen, C1-C10 alkanyl or cycloalkyl, C2-C10 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C30 monocyclic or fused-ring aromatic hydrocarbon group, C3-C30 monocyclic or fused-ring heteroaromatic hydrocarbon group.
The specific preparation method of the above novel compound of the present invention will be described in detail below by taking a plurality of preparation examples as examples, but the preparation method of the present invention is not limited to these preparation examples.
Preparation example 1
Synthesis of compound C1:
(1) Preparation of Compounds 1-2
1-1 (38.7 g,100 mmol), 3-chlorobenzoic acid (15.6 g,100 mmol), potassium carbonate (41.4 g,300 mmol), tetraphenylpalladium phosphate (1.15 g,1 mmol), 300mL of toluene, 100mL of ethanol, 60mL of water were added and the reaction was refluxed overnight under nitrogen at 110 ℃. Solid is separated out in the reaction process. Thin Layer Chromatography (TLC) detects the completion of the reaction of the starting materials, stops the reaction, cools to room temperature, filters the precipitated solid, and rinses with water and ethanol, respectively, and dries. The target compound 1-2 (38.5 g, yield 92%) was obtained.
(2) Preparation of Compounds 1-3
Compounds 1-2 (33.5 g,0.08 mol), pinacol borate (30.5 g,0.12 mol) and potassium acetate (24 g,0.24 mol) were added to a flask containing 1, 4-dioxane (300 mL), and Pd was added after nitrogen was replaced with stirring at room temperature 2 (dba) 3 (733 mg,0.8 mmol) and spos (1 g,1.6 mmol). After the addition was completed, the reaction was stirred at reflux for 24 hours and TLC monitored for the end of the reaction. The precipitated solid was filtered. Washing with water and drying gave compound 1-3 (30.6 g, yield 75%).
(3) Preparation of Compound C1
Compounds 1-3 (10.2 g,20 mmol) and 2-chloro-4-phenylquinazoline (4.8 g,20 mmol) were added to a three-necked flask, then potassium carbonate (8.3 g,60 mmol) was dissolved in 30mL of water and added to the three-necked flask, 150mL of tetrahydrofuran was added, and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (146 mg,0.2 mmol) was further added to replace nitrogen 3 times, and the oil bath was heated to 80℃for 4-5 hours, and TLC monitored the end of the reaction. Cooling the reaction solution to room temperature, extracting with ethyl acetate, mixing organic phases, drying, and concentrating; DCM was dissolved, column chromatographed, the product was collected and concentrated, recrystallized from toluene, dried to give compound C1 (8.4 g, yield 71%) as a white solid. Calculated molecular weight: 589.23, ZAB-HS Mass Spectrometry (manufactured by Micromass Co., UK) found C/Z:589.2.
Preparation example 2
Synthesis of Compound C17:
(1) Preparation of Compound 2-1
To a single flask was added 4-bromobenzene cyanide (18.1 g,100 mmol), 4-chlorobenzoic acid (15.6 g,100 mmol), potassium carbonate (41.4 g,300 mmol), tetrakis triphenylphosphine palladium (1.15 g,1 mmol), 300mL of toluene, 100mL of ethanol and 60mL of water, and the mixture was reacted under nitrogen at 110℃for 4 hours under reflux. TLC detects that the raw materials are reacted completely, stops the reaction and cools to room temperature, separates liquid, washes the organic phase with water, dries, removes the solvent under reduced pressure, purifies by column chromatography, and dries. The objective compound 2-1 (19.2 g, yield 90%) was obtained.
(2) Preparation of Compound 2-2
Into a flask containing 1, 4-dioxane (300 mL) was charged compound 2-1 (17 g,0.08 mol), pinacol borate (30.5 g,0.12 mol) and potassium acetate (24 g,0.24 mol), and Pd was added after nitrogen was replaced with stirring at room temperature 2 (dba) 3 (733 mg,0.8 mmol) and spos (1 g,1.6 mmol). After the addition was completed, the reaction was stirred at reflux for 24 hours and TLC monitored for the end of the reaction. The precipitated solid was filtered. Washing with water and drying gave compound 2-2 (18.8 g, yield 77%).
(3) Preparation of Compounds 2-3
Compound 2-2 (15.2 g,50 mmol), 2, 4-dichloroquinazoline (12 g,50 mmol), potassium carbonate (20.7 g,150 mmol), and tetraphenylpalladium phosphate (577 mg,0.5 mmol) were put into a three-necked flask containing 150mL of toluene, 50mL of ethanol, and 50mL of water, and reacted at 110℃under nitrogen atmosphere for 3 hours under reflux. TLC detects that the raw materials are reacted completely, the reaction is stopped and cooled to room temperature, the obtained solid is filtered, washed with water and ethanol respectively, and dried. Purifying by column chromatography, and drying. The objective compound 2-3 (15.5 g, yield 91%) was obtained.
(4) Preparation of Compound C17
Compounds 1-3 (10.2 g,20 mmol) and 2-3 (6.8 g,20 mmol) were added to a three-necked flask, then potassium carbonate (8.3 g,60 mmol) was dissolved in 30mL of water and added to the flask, 150mL of tetrahydrofuran was added, and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (146 mg,0.2 mmol) was further added to displace nitrogen 3 times, and the reaction was allowed to proceed to 80℃for 4-5 hours with heating in an oil bath, and TLC monitored for the end of the reaction. The reaction solution was cooled to room temperature, and the resulting solid was filtered, rinsed with water and ethanol, dried, column chromatographed, the product was collected and concentrated, recrystallized from toluene, and dried to give compound C17 (9 g, yield 65%) as a white solid. Calculated molecular weight: 690.25, ZAB-HS Mass Spectrometry observed C/Z:690.3.
Preparation example 3
Synthesis of compound C25:
the specific synthesis procedure differs from that of preparation 1 in that starting material 1-1 was replaced by starting material 3-1 in an equivalent amount to give compound C25 as a white solid, calculated molecular weight: 665.25, found C/Z665.3.
Preparation example 4
Synthesis of Compound C41
The specific synthesis steps are different from those of preparation example 1 in that 3-chlorobenzeneboronic acid is replaced with equal amount of 4-chlorobenzeneboronic acid in step (1), 2-chloro-4-phenylquinazoline is replaced with equal amount of compound 4-3 in step (3), and white solid compound C41 is obtained, and the molecular weight calculated value is: 679.23, ZAB-HS Mass Spectrometry found C/Z679.2.
The preparation method of the compound 4-3 comprises the following steps:
the compound dibenzofuran-3-boronic acid (10.6 g,50 mmol), 2, 4-dichloroquinazoline (12 g,50 mmol), potassium carbonate (20.7 g,150 mmol), and tetraphenylpalladium phosphate (577 mg,0.5 mmol) were added to a three-necked flask containing 150mL of toluene, 50mL of ethanol, and 50mL of water, and reacted at 110℃under nitrogen protection for 3 hours under reflux. TLC detects that the raw materials are reacted completely, the reaction is stopped and cooled to room temperature, the obtained solid is filtered, washed with water and ethanol respectively, and dried. Purifying by column chromatography, and drying. The objective compound 4-3 (16.5 g, yield 93%) was obtained.
Preparation example 5
Synthesis of Compound C60
(1) Synthesis of Compound 5-1
Compound 2-2 (30.5 g,0.1 mol), 2, 4-dichloro-6-phenyl-1, 3, 5-triazine (24.8 g,0.11 mol) and potassium carbonate (41.4 g,0.3 mol) were dissolved in a flask containing tetrahydrofuran/water (300 mL/100 mL), and after nitrogen was replaced with stirring at room temperature, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (732 mg,1 mmol) was added. After the addition was completed, the reaction was stirred at reflux for 4 hours and TLC monitored for the end of the reaction. After cooling to room temperature, the solution was separated, the organic phase was washed with water, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by spin-drying under reduced pressure. The crude product was purified by column chromatography to give compound 5-1 (20.2 g, yield 55%).
(2) Preparation of Compound 5-2
Intermediate 5-1 (18.4 g,50 mmol), 3-chlorobenzeneboronic acid (7.8 g,50 mmol), potassium carbonate (20.7 g,150 mmol), tetraphenylpalladium phosphate (0.58 g,0.5 mmol) were added to 150mL of toluene, 50mL of ethanol, 50mL of water, and the mixture was refluxed overnight at 110℃under nitrogen. Solid is separated out in the reaction process. TLC detects that the starting material was reacted, stops the reaction and cools to room temperature, filters the precipitated solid, and rinsed with water and ethanol, respectively, and dries. The target compound 5-2 (20.2 g, yield 91%) was obtained.
(3) Preparation of Compound 5-3
The compound 5-2 (17.8 g,40 mol), pinacol borate (15.3 g,60 mol) and potassium acetate (12 g,120 mol) were added to a 1, 4-dioxane (150 mL) containing burnIn a bottle, pd was added after nitrogen was replaced with stirring at room temperature 2 (dba) 3 (366 mg,0.4 mmol) and spos (0.5 g,0.8 mmol). After the addition was completed, the reaction was stirred at reflux for 24 hours and TLC monitored for the end of the reaction. The precipitated solid was filtered. Washing with water and drying gave compound 5-3 (15.4 g, yield 72%).
(4) Preparation of Compounds 5-4
Intermediate 5-3 (16 g,30 mmol), 4-chloro-bromobenzene (5.7 g,30 mmol), potassium carbonate (12.4 g,90 mmol), tetraphenylpalladium phosphate (348 mg,0.3 mmol) were added to toluene 150mL, ethanol 50mL, water 50mL, and reacted under nitrogen at 110℃overnight at reflux. Solid is separated out in the reaction process. TLC detects that the starting material was reacted, stops the reaction and cools to room temperature, filters the precipitated solid, and rinsed with water and ethanol, respectively, and dries. The target compound 5-4 (14.7 g, yield 94%) was obtained.
(5) Preparation of Compounds 5-5
Into a flask containing 1, 4-dioxane (150 mL) was charged compound 5-4 (13 g,25 mol), pinacol borate (9.7 g,38 mol) and potassium acetate (7.4 g,75 mol), pd was added after displacing nitrogen with stirring at room temperature 2 (dba) 3 (230 mg,0.25 mmol) and spos (210 mg,0.5 mmol). After the addition was completed, the reaction was stirred at reflux for 24 hours and TLC monitored for the end of the reaction. The precipitated solid was filtered. Washing with water and drying gave compound 5-5 (12.2 g, yield 80%).
(6) Preparation of Compound C60
Compounds 5-5 (12.2 g,20 mmol) and 2-chloro-4-phenylquinazoline (4.8 g,20 mmol) were added to a three-necked flask, then potassium carbonate (8.3 g,60 mmol) was dissolved in 30mL of water and added to the three-necked flask, 150mL of tetrahydrofuran was added, and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (146 mg,0.2 mmol) was further added to replace nitrogen 3 times, and the oil bath was heated to 80℃for 4-5 hours, and TLC monitored the end of the reaction. The resulting solid was filtered, dried, dissolved in DCM, column chromatographed, collecting the product and concentrating, recrystallised from toluene, oven dried to give compound C60 as a white solid (8.4 g, 70% yield). Calculated molecular weight: 690.25, ZAB-HS Mass Spectrometry observed C/Z:690.3.
Preparation example 6
Synthesis of Compound C72
(1) Synthesis of intermediate 6-1
The compound 9, 9-dimethylfluorene-2-boronic acid (11.9 g,50 mmol), 2, 4-dichloroquinazoline (12 g,50 mmol), potassium carbonate (20.7 g,150 mmol), and tetraphenylpalladium phosphate (577 mg,0.5 mmol) were added to a three-necked flask containing 150mL of toluene, 50mL of ethanol, and 50mL of water, and the mixture was refluxed under nitrogen for 3 hours at 110 ℃. TLC detects that the raw materials are reacted completely, the reaction is stopped and cooled to room temperature, the obtained solid is filtered, washed with water and ethanol respectively, and dried. Purifying by column chromatography, and drying. The target compound 6-1 (16.2 g, yield 91%) was obtained.
(2) Synthesis of intermediate 6-3
Raw material 6-2 (38.7 g,100 mmol), 3-chlorobenzeneboronic acid (15.6 g,100 mmol), potassium carbonate (41.4 g,300 mmol), tetra-triphenylpalladium phosphate (1.15 g,1 mmol) were added to a three-port sintered piece containing 300mL of toluene, 100mL of ethanol, and 100mL of water, and reacted under nitrogen at 110℃under reflux overnight. Solid is separated out in the reaction process. TLC detects that the starting material was reacted, stops the reaction and cools to room temperature, filters the precipitated solid, and rinsed with water and ethanol, respectively, and dries. The target compound 6-3 (38 g, yield 91%) was obtained.
(3) Preparation of Compounds 6-4
Compound 6-3 (33.5 g,0.08 mol), pinacol borate (30.5 g,0.12 mol) and potassium acetate (24 g,0.24 mol) were charged into a flask containing 1, 4-dioxane (300 mL), and Pd was added after nitrogen was replaced with stirring at room temperature 2 (dba) 3 (733 mg,0.8 mmol) and spos (1 g,1.6 mmol). After the addition was completed, the reaction was stirred at reflux for 24 hours and TLC monitored for the end of the reaction. The precipitated solid was filtered. Washing with water and drying gave compound 6-4 (31.4 g, yield 77%).
(4) Preparation of Compound C72
Compound 6-4 (10.2 g,20 mmol) and compound 6-1 (7.1 g,20 mmol) were added to a three-necked flask, then potassium carbonate (8.3 g,60 mmol) was dissolved in 30mL of water and added to the flask, 150mL of tetrahydrofuran was added, and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (146 mg,0.2 mmol) was further added to replace nitrogen 3 times, and the reaction was allowed to proceed to 80℃for 4-5 hours with heating in an oil bath, and TLC was monitored to end the reaction. Cooling the reaction solution to room temperature, extracting with ethyl acetate, mixing organic phases, drying, and concentrating; DCM was dissolved, column chromatographed, the product was collected and concentrated, recrystallized from toluene, dried to give compound C72 (8.4 g, yield 70%) as a white solid. Calculated molecular weight: 705.28, ZAB-HS Mass Spectrometry found C/Z705.3.
Preparation example 7
Synthesis of Compound C91
The difference between the specific implementation steps and the preparation example 1 is that in the step (1), the raw material 1-1 is replaced by the raw material 7-1 with equal mass, and the 3-chlorobenzoic acid is replaced by the 4-chlorobenzoic acid with equal mass, so that a white solid compound C91 is obtained, and the molecular weight calculated value is: 705.28, ZAB-HS Mass Spectrometry found C/Z705.3.
Preparation example 8
Synthesis of Compound C121
(1) Synthesis of intermediate 8-1
Intermediate 1-3 (15.3 g,30 mmol), 3-chloro-bromobenzene (5.7 g,30 mmol), potassium carbonate (12.4 g,90 mmol), tetraphenylpalladium phosphate (348 mg,0.3 mmol) were added to toluene 150mL, ethanol 50mL, water 50mL, and the reaction was refluxed overnight at 110℃under nitrogen. Solid is separated out in the reaction process. TLC detects that the starting material was reacted, stops the reaction and cools to room temperature, filters the precipitated solid, and rinsed with water and ethanol, respectively, and dries. The target compound 8-1 (13.7 g, yield 92%) was obtained.
(2) Preparation of Compound 8-2
Compound 8-1 (12.4 g,25 mol), pinacol borate(9.7 g,38 mol) and potassium acetate (7.4 g,75 mol) were charged into a flask containing 1, 4-dioxane (150 mL), and Pd was added after replacing nitrogen with stirring at room temperature 2 (dba) 3 (230 mg,0.25 mmol) and spos (210 mg,0.5 mmol). After the addition was completed, the reaction was stirred at reflux for 24 hours and TLC monitored for the end of the reaction. The precipitated solid was filtered. Washing with water and drying gave compound 8-2 (11.9 g, yield 81%).
(3) Preparation of Compound C121
Compound 8-2 (11.7 g,20 mmol) and 2-chloro-4-phenylquinazoline (4.8 g,20 mmol) were added to a three-necked flask, then potassium carbonate (8.3 g,60 mmol) was dissolved in 30mL of water and added to the three-necked flask, 150mL of tetrahydrofuran was added, and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (146 mg,0.2 mmol) was further added to replace nitrogen 3 times, and the oil bath was heated to 80℃for 4-5 hours, and TLC monitored the end of the reaction. The resulting solid was filtered, dried, dissolved in DCM, column chromatographed, collecting the product and concentrating, recrystallised from toluene, oven dried to give compound C121 (8.6 g, 65% yield) as a white solid. Calculated molecular weight: 665.25, measured C/Z of ZAB-HS mass spectrometer 665.3.
Example 1
The embodiment provides an organic electroluminescent device, which is prepared by the following steps:
(1) Ultrasonic treating the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, flushing in deionized water, ultrasonic degreasing in a mixed solvent of acetone and ethanol, baking in a clean environment until water is completely removed, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam;
(2) Placing the glass substrate with anode in vacuum chamber, vacuumizing to pressure less than 10 -5 Pa, regulating the evaporation rate of the hole transport material HT-28 to 0.1nm/s by utilizing a multi-source co-evaporation method on the anode layer film, setting the evaporation rate of the hole injection material HI-2 to 7% and setting the total film thickness of the evaporation to 10nm;
(3) Vacuum evaporating HT-28 on the hole injection layer as a first hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 40nm;
(4) Vacuum evaporating HT-32 on the first hole transport layer to serve as a second hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 10nm;
(5) Vacuum evaporating a luminescent layer of the device on the second hole transport layer, wherein the luminescent layer comprises a main material and a dye material, the evaporation rate of the main material BFH-4 is regulated to be 0.1nm/s by utilizing a multi-source co-evaporation method, the evaporation rate of the dye BFD-4 is set to be 5% in proportion, and the total film thickness of evaporation is 20nm;
(6) Vacuum evaporating ET-17 on the luminescent layer as a hole blocking layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 5nm;
(7) Evaporating an electron transport material on the hole blocking layer by utilizing a multi-source co-evaporation method, regulating the evaporation rate of the compound C1 of the invention to 0.1nm/s, setting the ratio of the evaporation rate to the evaporation rate of ET-57 to 100%, and setting the total film thickness of the evaporation to 23nm;
(8) LiF with the thickness of 1nm is evaporated in vacuum on the electron transport layer to serve as an electron injection layer, and finally an Al layer with the thickness of 80nm is evaporated to serve as a cathode of the device.
Example 2
The difference from example 1 is that compound C1 is replaced by compound C17.
Example 3
The difference from example 1 is that compound C1 is replaced by compound C25.
Example 4
The difference from example 1 is that compound C1 is replaced with compound C41.
Example 5
The difference from example 1 is that compound C1 is replaced by compound C60.
Example 6
The difference from example 1 is that compound C1 is replaced by compound C72.
Example 7
The difference from example 1 is that compound C1 is replaced with compound C91.
Example 8
The difference from example 1 is that compound C1 is replaced with compound C109.
Example 9
The difference from example 1 is that compound C1 is replaced by compound C56.
Example 10
The difference from example 1 is that compound C1 is replaced with compound C123.
Example 11
The difference from example 1 is that compound C1 is substituted for compound C124.
Example 12
The difference from example 1 is that compound C1 is substituted for compound C125.
Example 13
The difference from example 1 is that compound C1 is substituted for compound C121.
Comparative example 1
The difference from example 1 is that compound C1 is replaced by compound ET-9.
Comparative example 2
The difference from example 1 is that compound C1 is replaced by compound ET-46.
Comparative example 3
The difference from example 1 is that compound C1 is replaced by compound D1.
Comparative example 4
The difference from example 1 is that compound C1 is replaced by compound D2.
Performance testing
(1) The driving voltage and current efficiency of the organic electroluminescent devices prepared in examples and comparative examples were measured using a Photo Research company PR 750 type optical radiometer ST-86LA type luminance meter (university of Beijing photoelectric instrumentation Co.) and Keithley4200 test system at the same luminance. Specifically, the luminance of the organic electroluminescent device was measured to reach 1000cd/m by increasing the voltage at a rate of 0.1V per second 2 The voltage at the time is the driving voltage, and the measurement is carried out simultaneouslyThe current density at this time is outputted; the ratio of brightness to current density is the current efficiency.
(2) The lifetime test of LT95 is as follows: at 1500cd/m using a luminance meter 2 Under the condition of brightness, constant current is kept, and the brightness of the organic electroluminescent device is measured to be reduced to 1425cd/m 2 Time in hours.
The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the OLED devices in the examples have a starting voltage of less than or equal to 4.49V, a current efficiency of more than or equal to 7.92cd/A, and the devices have higher luminous efficiency and lower starting voltage, and have longer service life, the service life is 49 hours or more, namely the device stability is high; compared with the example, the electron transport material of the device of the comparative example 1 is replaced by ET-9 only containing triazine groups, and the starting voltage, the current efficiency and the service life are obviously deteriorated; the electron transport material of the device of comparative example 2 was replaced with ET-46 containing only quinazoline groups, and the starting voltage, current efficiency, and lifetime were significantly degraded; the electron transport material of the device of comparative example 3 was replaced with D1, which contained a triazine group, and also contained a phenanthropyrimidine group, and the starting voltage, current efficiency, and lifetime were significantly deteriorated; the electron transport material of the device of comparative example 4 was changed to D2, which also contained both triazine and quinazoline groups, but the two electron-deficient groups were connected by only one benzene ring, the starting voltage and luminous efficiency of the device were less different from those of most of the examples, but the performance of the device with the best effect was more different from that of the examples, and the lifetime of the device was significantly lower than that of the examples, with poor stability.
The results prove that when the compound provided by the invention is used as an electron transport material of an OLED device, the luminous efficiency of the device can be improved, the starting voltage is reduced, and the service life is prolonged, because triazine and derivative groups thereof and quinazoline and derivative groups thereof are simultaneously introduced, and the two groups are connected by using a substituted or unsubstituted arylene which is formed by sequentially connecting 2-10 benzene rings by single bonds, the special connection mode is matched with the two electron-deficient groups, so that the compound has stronger electron deficiency, is more beneficial to electron injection and migration, and can effectively improve the electron injection and migration efficiency in the device when the compound is used as an electron transport layer material in an organic electroluminescent device, thereby ensuring the excellent effects of high luminous efficiency and low starting voltage of the device, and simultaneously improving the service life and stability of the device.
As can be seen from comparative examples 1, 12 and 13, when the structure of the compound is the structure of formula (4-1) or (4-3) (examples 1 and 12), the device has better luminous efficiency and starting voltage, and also has optimized stability and lifetime, because the two specific substituent connection modes are matched with the electron-deficient characteristics of triazine and quinazoline groups, the injection and migration of electrons are facilitated, so that the device has excellent luminous efficiency and starting voltage, long lifetime and high stability.
The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (12)

1. A compound, characterized in that the compound has the structure of formula (3-1);
in the formula (1-1), the R 1 、R 2 、R 3 And R is 4 Each independently selected from hydrogenOne of an atom, a deuterium atom, a halogen, a cyano group, a C1-C12 alkyl group, a C6-C30 aryl group, a C3-C30 heteroaryl group;
the R is 5 And R is 6 Each independently selected from one of cyano, C1-C12 alkyl, substituted or unsubstituted C6-C16 aryl, substituted or unsubstituted C6-C12 heteroaryl;
ar is selected from one of substituted or unsubstituted C6-C16 aryl and substituted or unsubstituted C6-C12 heteroaryl;
when the substituent groups exist in the groups, the substituent groups are independently selected from cyano groups, halogen, C1-C10 chain alkyl groups or one of cycloalkyl groups, phenyl groups and naphthyl groups.
2. The compound of claim 1, wherein the compound has any one of the following structures:
the R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 And Ar each independently has the same definition as claim 1.
3. The compound of claim 1, wherein the compound has the structure of formula (4-1);
the R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 And Ar each independently has the same definition as claim 1.
4. The compound of claim 1, wherein the compound has the structure of formula (4-3);
the R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 And Ar each independently has the same definition as claim 1.
5. The compound of any one of claims 1-4, wherein R 1 、R 2 、R 3 And R is 4 Are all hydrogen atoms.
6. The compound of any one of claims 1-4, wherein R 5 、R 6 And Ar is each independently selected from one of a substituted or unsubstituted C6-C16 aryl, a substituted or unsubstituted C6-C12 heteroaryl.
7. The compound of any one of claims 1-4, wherein R 5 、R 6 And Ar is each independently selected from one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted phenanthryl group, and a substituted or unsubstituted fluoranthenyl group;
When the substituent groups exist in the groups, the substituent groups are selected from one of C1-C10 alkyl groups or cycloalkyl groups, cyano groups, phenyl groups and naphthyl groups.
8. The compound of any one of claims 1-4, wherein R 1 、R 2 、R 3 And R is 4 Are all hydrogen atoms, R is 5 、R 6 And Ar is each independently selected from phenyl, cyano-substituted phenyl, biphenyl, cyano-substituted biphenyl, naphthyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, phenanthryl, or fluoranthenylOne of the two.
9. The compound of any one of claims 1-4, wherein R 1 、R 2 、R 3 And R is 4 Are all hydrogen atoms, R is 5 And R is 6 Each independently selected from phenyl.
10. The compound according to claim 1, wherein the compound is selected from one of the following compounds C1-C125:
11. use of a compound according to any one of claims 1-10 as an electron transport material in an organic electroluminescent device.
12. An organic electroluminescent device, characterized in that the organic electroluminescent device comprises a substrate, a first electrode, a second electrode and at least one organic layer interposed between the first electrode and the second electrode, wherein the organic layer contains any one or at least two of the compounds according to any one of claims 1 to 10.
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