CN114573499B - 9, 9-Dicarbazole derivative, preparation method thereof and application thereof in luminescence - Google Patents

9, 9-Dicarbazole derivative, preparation method thereof and application thereof in luminescence Download PDF

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CN114573499B
CN114573499B CN202111566915.5A CN202111566915A CN114573499B CN 114573499 B CN114573499 B CN 114573499B CN 202111566915 A CN202111566915 A CN 202111566915A CN 114573499 B CN114573499 B CN 114573499B
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carbon atoms
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dicarbazole
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CN114573499A (en
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朱向东
刘向阳
袁晓冬
陈华
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Weisipu New Material Suzhou Co ltd
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Abstract

The invention relates to the technical field of organic photoelectric materials, and provides a 9, 9-dicarbazole derivative, a preparation method thereof and application thereof in luminescence. According to the invention, the electron donor group is introduced into the 9, 9-dicarbazole rigid structure, so that the obtained 9, 9-dicarbazole derivative has excellent film forming property and thermal stability. The 9, 9-dicarbazole derivative can be used as a constituent material of a light-emitting layer, and can reduce driving voltage, improve efficiency, brightness, prolong service life and the like. In addition, the preparation method of the 9, 9-dicarbazole derivative is simple, raw materials are easy to obtain, and the industrial development requirement can be met.

Description

9, 9-Dicarbazole derivative, preparation method thereof and application thereof in luminescence
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a 9, 9-dicarbazole derivative, a preparation method thereof and application thereof in luminescence.
Background
The organic electroluminescent device has a series of advantages of self-luminescence, low voltage driving, full solidification, wide viewing angle, simple composition and process, and the like, and compared with a liquid crystal display, the organic electroluminescent device does not need a backlight source. Therefore, the organic electroluminescent device has wide application prospect.
The organic electroluminescent device generally includes an anode, a metal cathode, and an organic layer sandwiched therebetween. The organic layer mainly comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. In addition, the light-emitting layer mostly adopts a host-guest structure. That is, the light emitting material is doped in the host material at a concentration to avoid concentration quenching and triplet-triplet annihilation, thereby improving light emitting efficiency. Thus, a host material is generally required to have a higher triplet energy level and at the same time higher stability.
At present, research on organic electroluminescent materials has been widely conducted in academia and industry, and a great number of organic electroluminescent materials with excellent properties have been developed. In general, the direction of the future organic electroluminescent devices is to develop white light devices and full-color display devices with high efficiency, long lifetime and low cost, but the industrialization process of the technology still faces a number of key problems. Therefore, the compound is designed and searched to be a stable and efficient compound which is used as a novel material of the organic electroluminescent device to overcome the defects of the organic electroluminescent device in the practical application process, and is an important point in the research work of the material of the organic electroluminescent device and a research trend in the future.
In the current organic light emitting device, the device structure using one organic electroluminescent host material in the light emitting layer exhibits the advantages of high light emitting efficiency and low driving voltage, but its lifetime is not particularly good, and the material composition of the light emitting layer is also to be optimized. Patent CN 112341375A discloses an application of carbazole diphenylamine N-N coupled derivatives in luminescence, wherein a luminescent layer contains the carbazole diphenylamine N-N coupled derivatives and a guest material, the guest material is FIrpic, the mass fraction of the carbazole diphenylamine N-N coupled derivatives in the luminescent layer is 4-10%, and the rest is the guest material FIrpic. Since FIrpic is a rare noble metal phosphorescent material, the cost is high, and the use of excessive proportions of FIrpic in the device increases the cost of the device, affecting its commercial development. Patent CN 110156663a discloses a compound and an organic light-emitting display device, which can obtain an organic compound with bipolar characteristics by combining a carbazole group with a high triplet energy level with an electron acceptor unit, and has the characteristics of hole transport and electric transport, but the device performance, the light-emitting efficiency and the device life are still to be improved, especially the device life is shorter, and the use is affected; in energy level control, the energy level is often sacrificed by taking the transmission characteristics into consideration, and the method is not suitable for a blue light device with high energy level.
Disclosure of Invention
The present invention aims to overcome at least one of the above disadvantages and drawbacks of the prior art, and provides a 9, 9-dicarbazole derivative, a preparation method thereof and an application thereof in luminescence. The invention is realized based on the following technical scheme:
in one aspect of the present invention, there is provided a 9, 9-dicarbazole derivative having a structure represented by the general formula (1):
Wherein L 1 and L 2 each independently represent a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms;
Donor 1 and Donor 2 each independently represent Ar 1、Ar2,
Ar 1～Ar4 each independently represents an aromatic electron donor group having 6 to 30 carbon atoms optionally substituted with one or more R 1 or an aromatic heterocyclic electron donor group having 5 to 30 carbon atoms optionally substituted with one or more R 1;
m and n are each independently integers from 0 to 4, and m and n are not both 0 at the same time;
R 1 represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group of C 1-C20 substituted or unsubstituted by cyano 、NO2、N(R2)2、OR2、SR2、C(＝O)R2、P(＝O)R2、Si(R2)3、, an alkenyl group of C 2-C20 substituted or unsubstituted, an alkynyl group of C 2-C20 substituted or unsubstituted, an aromatic hydrocarbon group of C 6-C40 substituted or unsubstituted, or an aromatic heterocyclic group of C 5-C40 substituted or unsubstituted;
R 2 represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group of C 1-C20, a substituted or unsubstituted aromatic hydrocarbon group of C 6-C30, or a substituted or unsubstituted aromatic heterocyclic group of C 5-C30.
[ Definition of groups ]
< L 1 and L 2 >
L 1 and L 2 each independently represent a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms.
In the present invention, the hetero atom in the aromatic heterocyclic group having 5 to 18 carbon atoms is preferably N, O and/or S. In the present invention, the number of heteroatoms may be 1 to 5. An aromatic hydrocarbon group or an aromatic heterocyclic group in the sense of the present invention means a system which does not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of non-hydrogen atoms), which may be, for example, carbon atoms, nitrogen atoms, oxygen atoms or carbonyl groups. For example, as well as systems in which two or more aryl groups are interrupted, for example by linear or cyclic alkyl groups or by silyl groups, systems of 9,9' -spirobifluorene, 9-diaryl fluorene, triarylamine, diaryl ether, etc., are also intended to be considered aromatic hydrocarbon groups in the sense of the present invention. Furthermore, systems in which two or more aryl or heteroaryl groups are directly bonded to one another, such as biphenyl, terphenyl or tetrabiphenyl, are likewise intended to be regarded as aromatic hydrocarbon radicals or aromatic heterocyclic radicals.
An aromatic hydrocarbon group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 5 to 18 carbon atoms represented by L 1 and L 2 may be exemplified by: phenyl, naphthyl, anthryl, benzanthraceyl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthryl, naphthaceneyl, pentacenyl, benzopyrenyl, biphenyl, terphenyl, tetrabiphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzoindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, heterotrimeric indenyl, spirotrimeric indenyl, spiroheterotrimeric indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, benzocarbazolyl, benzothienyl pyridyl, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolinyl, benzo-6, 7-quinolinyl, benzo-7, 8-quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthyridinimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthazolyl, anthracooxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazaanthracenyl, 2, 7-diazapyrenyl, 2, 3-diazapyrenyl, 1, 6-diazapyrenyl, 1, 8-diazapyrenyl, 4,5,9, 10-tetraphenylene Pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluoroyl, naphthyridinyl, azacarbazolyl, benzocarboline, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazole, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, naphthyridinyl, benzothiazyl, and the like.
In the present invention, preferably, L 1 and L 2 each independently represent a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 5 to 12 carbon atoms. More preferably, L 1 and L 2 each independently represent a single bond, carbonyl, phenyl, triazinyl or biphenyl.
The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented by L 1 and L 2 may be unsubstituted, but may also have a substituent. Substituents may be exemplified as follows: deuterium atoms; cyano group; a nitro group; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms or iodine atoms; alkyl having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl or n-hexyl; alkoxy having 1 to 6 carbon atoms, such as methoxy, ethoxy or propoxy; alkenyl groups such as vinyl or allyl; aryloxy groups such as phenoxy or tolyloxy; arylalkoxy groups, such as benzyloxy or phenethyl; aromatic hydrocarbon radicals or fused polycyclic aromatic radicals, such as phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthracenyl, benzo [9,10] phenanthrenyl or spirobifluorenyl; aromatic heterocyclic groups such as pyridyl, thienyl, furyl, pyrrolyl, quinolinyl, isoquinolinyl, benzofuryl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, azafluorenyl, diazafluorenyl, carbolinyl, azaspirobifluorenyl, or diazaspirobifluorenyl; aryl vinyl groups such as styryl or naphthylvinyl; and acyl groups such as acetyl or benzoyl, and the like.
Alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms may be straight-chain or branched. Any of the above substituents may be further substituted with the above exemplary substituents. The above substituents may exist independently of each other, but may also bond to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.
Preferably, donor 1 and Donor 2 each independently represent Ar 1、Ar2,
Preferably, the 9, 9-dicarbazole derivative provided by the invention has a structure shown in a general formula (I) or (II):
Wherein L 1、L2 and Ar 1～Ar4 have the meanings defined in claim 1.
Preferably, ar 1、Ar2、Ar3 and Ar 4 are each independently selected from one of the following groups:
wherein the dotted line represents a bond to L 1、L2 or N, and R 1 has the meaning as defined in formula (1).
The aromatic electron donor group having 6 to 30 carbon atoms or the aromatic heterocyclic electron donor group having 5 to 30 carbon atoms represented by Ar 1～Ar4 may be unsubstituted, but may also have a substituent. Preferably, the aromatic electron donor group having 6 to 30 carbon atoms or the aromatic heterocyclic electron donor group having 5 to 30 carbon atoms represented by Ar 1～Ar4 is an aromatic electron donor group having 5 to 30 carbon atoms substituted with one or more R 1 or an aromatic heterocyclic electron donor group having 5 to 30 carbon atoms substituted with one or more R 1.
R 1 represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano 、NO2、N(R2)、OR2、SR2、C(＝O)R2、P(＝O)R2、Si(R2)3、 substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms.
The alkyl group having 1 to 20 carbon atoms represented by R 1 may be exemplified by: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl, hexadecyl, octadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl and the like. The alkyl groups having 1 to 20 carbon atoms may be straight chain, branched or cyclic.
The alkyl group having 1 to 20 carbon atoms represented by R 1 may be unsubstituted, but may also have a substituent. Preferably, the alkyl group having 1 to 20 carbon atoms represented by R 1 is substituted with one or more of R 2 described below. In addition, one or more non-adjacent CH 2 groups in the alkyl group may be replaced by R2C＝CR2、C≡C、Si(R2)3、C＝O、C＝NR2、P(＝O)R2、SO、SO2、NR2、O、S or CONR 2, and one or more hydrogen atoms may be replaced by groups having deuterium, fluorine, chlorine, bromine, iodine, cyano, nitro.
Alkenyl groups having 2 to 20 carbon atoms represented by R 1 may be exemplified by: ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexyl, allyl, cyclohexenyl, or the like. Alkenyl groups having 2 to 20 carbon atoms may be straight chain, branched or cyclic.
The alkenyl group having 2 to 20 carbon atoms represented by R 1 may be unsubstituted or may have a substituent. The substituent may be exemplified by the same substituents as those shown by the substituents optionally possessed by the alkyl group having 1 to 20 carbon atoms represented by R 1. Substituents may take the same pattern as the exemplary substituents.
Alkynyl groups having 2 to 20 carbon atoms represented by R 1 may be exemplified by: ethynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, and the like.
The alkynyl group having 2 to 20 carbon atoms represented by R 1 may be unsubstituted or may have a substituent. The substituent may be exemplified by the same substituents as those shown by the substituents optionally possessed by the alkyl group having 1 to 20 carbon atoms represented by R 1. Substituents may take the same pattern as the exemplary substituents.
The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by R 1 may be the same groups as those shown for the aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by Ar 1～Ar4 described above.
The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by R 1 may be unsubstituted or may have a substituent. The substituent may be exemplified by the same substituents as those shown by the substituents optionally possessed by the alkyl group having 1 to 20 carbon atoms represented by R 1. Substituents may take the same pattern as the exemplary substituents. Furthermore, two adjacent R 1 substituents or two adjacent R 2 substituents optionally may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R 2; where two or more substituents R 1 may be attached to each other and may form a ring.
As a preferable aromatic hydrocarbon group having 6 to 40 carbon atoms or an aromatic heterocyclic group having 5 to 40 carbon atoms represented by R 1, there may be mentioned: phenyl, biphenyl, terphenyl, tetrabiphenyl, pentabiphenyl, benzothiophenocarbazolyl, benzofuranocarbazolyl, benzofluorenocarbazolyl, benzanthracenyl, benzophenanthryl, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boronyl, triphenyl phosphoxy, diphenyl phosphoxy, triphenyl silicon group, tetraphenyl silicon group, and the like. The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms may be substituted with one or more R 2.
R 2 represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.
The alkyl group having 1 to 20 carbon atoms represented by R 2 may be exemplified by the same groups as those shown for the alkyl group having 1 to 20 carbon atoms represented by R 1 described above.
The aromatic hydrocarbon group having 6 to 30 carbon atoms represented by R 2 or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms may be exemplified by the same groups as those exemplified for the aromatic hydrocarbon group having 6 to 30 carbon atoms represented by R 1 or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms described above.
The alkyl group having 1 to 20 carbon atoms, the aromatic hydrocarbon group having 6 to 30 carbon atoms, or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented by R 2 may be unsubstituted or may have a substituent. Substituents may be exemplified by: deuterium atoms; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms or iodine atoms; cyano, and the like.
Preferably, specific examples of a 9, 9-dicarbazole derivative, a preferred compound of the present invention are shown below, but the present invention is by no means limited to one of these compounds:
In another aspect of the object of the present invention, there is provided a method for preparing a 9, 9-dicarbazole derivative, comprising the steps of:
Purification of the obtained compound can be performed, for example, by purification using column chromatography, adsorption purification using silica gel, activated carbon, activated clay, or the like, recrystallization or crystallization using a solvent, sublimation purification, or the like. Identification of the compounds can be performed by mass spectrometry or elemental analysis.
In yet another aspect, the present invention provides an organic light-emitting layer, which includes a 9, 9-dicarbazole derivative as described in any of the above.
Preferably, the organic light-emitting layer comprises a double-body material and a doping material, the double-body material comprises a hole-type body and an electron-type body, the hole-type body is a 9, 9-dicarbazole derivative, and the electron-type body comprises any one of a cyano derivative, a triazine derivative, a phenanthroline derivative, a quinazoline derivative and a pyrazine derivative.
Preferably, the doping material includes any one of an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, and a metal complex.
Preferably, the content of the 9, 9-dicarbazole derivative is 40-53 wt%, and the content of the doping material is 0.1-20 wt%.
In a further aspect of the object of the present invention, an organic electroluminescent device is provided, comprising an organic light-emitting layer as described in any one of the above.
Preferably, the organic electroluminescent device of the present invention includes: the organic light-emitting device comprises a first electrode, a second electrode arranged opposite to the first electrode, and at least one organic layer sandwiched between the first electrode and the second electrode, wherein the at least one organic layer comprises the 9, 9-dicarbazole derivative of the present invention.
The invention can at least obtain one of the following beneficial effects:
The organic electroluminescent device provided by the invention has the advantages of high luminous efficiency, long service life and low driving voltage by using the 9, 9-dicarbazole derivative as a luminous layer, and is obviously superior to the existing organic electroluminescent device.
The present invention is directed to a device structure using a dual host in a light emitting layer of an organic electroluminescent device, wherein the dual host is selected from a hole type host and an electron type host, respectively. The hole type main body is the 9, 9-dicarbazole compound provided by the invention, and an electron donor group is introduced into the hole type main body, so that the hole type main body has higher thermal stability, chemical stability and hole transmission property, and more importantly, the hole type main body has proper singlet state, triplet state and molecular orbital energy level. Therefore, the organic light-emitting diode is introduced into a light-emitting layer of the organic light-emitting diode as a main body material, and is matched with an electronic main body, so that the light-emitting efficiency of the device is improved, the driving voltage of the device is reduced, and the service life of the device is greatly prolonged.
The invention can regulate and control the balance of holes and electrons by regulating and controlling the doping proportion of the hole type main body and the electron type main body, has stronger flexibility than bipolar materials, can consider transmission characteristics and energy levels, and can be applied to blue light devices with high energy levels.
The preparation method of the 9, 9-dicarbazole derivative is simple, raw materials are easy to obtain, a large amount of expensive luminescent materials are not needed in the organic electroluminescent device, the cost is low, and the industrial development requirement can be met.
Drawings
FIG. 1 is a fluorescence spectrum (PL) of example 1 (Compound 3) of the present invention in methylene chloride solution;
FIG. 2 is an electroluminescence spectrum of example 6 (organic electroluminescent device 3) and example 7 (organic electroluminescent device 4) of the present invention;
Fig. 3 is a structural view of the organic electroluminescent devices of examples 4 to 15 and the organic electroluminescent devices of comparative examples 1 to 6;
Reference numerals illustrate: 1, a substrate; 2, anode; 3 a hole injection layer; 4a hole transport layer; 5 an electron blocking layer; 6 a light emitting layer; 7, a hole blocking layer; 8 an electron transport layer; 9 an electron injection layer; and 10 cathode.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The production of the compound represented by the above general formula (1) and the organic electroluminescent device comprising the same will be specifically described in the following examples. The following examples are merely illustrative of the present invention, however, and the scope of the present invention is not limited thereto.
The organic electroluminescent device of the present invention includes: the organic light-emitting device comprises a first electrode, a second electrode arranged opposite to the first electrode, and at least one organic layer sandwiched between the first electrode and the second electrode, wherein the at least one organic layer comprises the 9, 9-dicarbazole derivative of the present invention.
Fig. 3 is a diagram showing the construction of the organic electroluminescent device of the present invention. As shown in fig. 3, in the organic electroluminescent device of the present invention, for example, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 are sequentially disposed on a substrate 1.
The organic electroluminescent device of the present invention is not limited to such a structure, and for example, in the multilayer structure, some organic layers may be omitted. For example, the hole injection layer 3 between the anode 2 and the hole transport layer 4, the hole blocking layer 7 between the light emitting layer 6 and the electron transport layer 8, and the electron injection layer 9 between the electron transport layer 8 and the cathode 10 may be omitted, and the configuration of the anode 2, the hole transport layer 4, the light emitting layer 6, the electron transport layer 8, and the cathode 10 may be sequentially disposed on the substrate 1.
The organic electroluminescent device according to the present invention may be manufactured by materials and methods well known in the art, except that the above-mentioned organic layer contains the compound represented by the above-mentioned general formula (1). In addition, in the case where the organic electroluminescent device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.
For example, the organic electroluminescent device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. At this time, it can be manufactured as follows: an anode is formed by vapor deposition of a metal or a metal oxide having conductivity or an alloy thereof on a substrate by PVD (physical vapor deposition) method such as sputtering or electron beam evaporation, then an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and then a substance that can function as a cathode is vapor deposited on the organic layer. However, the manufacturing method is not limited thereto.
As an example, the first electrode may be an anode, the second electrode may be a cathode, or the first electrode may be a cathode, and the second electrode may be an anode.
The anode of the organic electroluminescent device of the present invention may be made of a known electrode material. For example, an electrode material having a large work function, such as a metal of vanadium, chromium, copper, zinc, gold, or the like, or an alloy thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), and the like; a combination of a metal such as ZnO: al or SNO 2: sb with an oxide; conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene ] (PEDOT), polypyrrole and polyaniline, and the like. Among these, ITO is preferable.
As the hole injection layer of the organic electroluminescent device of the present invention, a known material having hole injection properties can be used. Examples include: porphyrin compounds typified by copper phthalocyanine, naphthalene diamine derivatives, star-shaped triphenylamine derivatives, triphenylamine trimers such as arylamine compounds having a structure in which 3 or more triphenylamine structures are linked by a single bond or a divalent group containing no hetero atom in the molecule, and receptor-type heterocyclic compounds such as tetramers, hexacyanoazabenzophenanthrene, and coated polymer materials. These materials may be formed into thin films by a known method such as vapor deposition, spin coating, or ink jet.
As the hole transport layer of the organic electroluminescent device of the present invention, a known material having hole transport properties can be preferably used. Examples include: a compound containing m-carbazolylphenyl; benzidine derivatives such as N, N ' -diphenyl-N, N ' -di (m-tolyl) benzidine (TPD), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -tetrabiphenyl benzidine, and the like; 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC); various triphenylamine trimers and tetramers; 9,9' -triphenyl-9H, 9' H-3,3':6', 3' -tricarbazole (Tris-PCz), etc. These may be used alone or in a single layer form by mixing with other materials, or may be formed into a laminated structure of layers formed alone, a laminated structure of layers formed by mixing, or a laminated structure of layers formed alone and layers formed by mixing. These materials may be formed into thin films by a known method such as vapor deposition, spin coating, or ink jet.
In the hole injection layer or the hole transport layer, a material obtained by further P-doping a material commonly used for the layer with tribromoaniline antimony hexachloride, an axial derivative, or the like, a polymer compound having a structure of a benzidine derivative such as TPD in a part of the structure, or the like may be used.
The electron blocking layer of the organic electroluminescent device of the present invention is preferably formed using a known compound having an electron blocking effect. For example, there may be mentioned: carbazole derivatives such as 4,4',4 "-tris (N-carbazolyl) triphenylamine (TCTA), 9-bis [4- (carbazol-9-yl) phenyl ] fluorene, 1, 3-bis (carbazol-9-yl) benzene (mCP), 2-bis (4-carbazol-9-yl) adamantane (Ad-Cz); a compound having a triphenylsilyl and triarylamine structure represented by 9- [4- (carbazol-9-yl) phenyl ] -9- [4- (triphenylsilyl) phenyl ] -9H-fluorene; monoamine compounds having high electron blocking properties, and compounds having an electron blocking effect such as various triphenylamine dimers. These may be used alone or in a single layer form by mixing with other materials, or may be formed into a laminated structure of layers formed alone, a laminated structure of layers formed by mixing, or a laminated structure of layers formed alone and layers formed by mixing. These materials may be formed into thin films by a known method such as vapor deposition, spin coating, or ink jet.
As the light-emitting layer of the organic electroluminescent device of the present invention, a 9, 9-dicarbazole derivative containing the present invention is preferably used. In addition, various metal complexes such as metal complexes of hydroxyquinoline derivatives including Alq 3, compounds having a pyrimidine ring structure, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, poly-p-phenylene vinylene derivatives, and the like can be used.
The light emitting layer may be composed of a host material and a doping material. The host material preferably contains the 9, 9-dicarbazole derivative of the present invention. In addition, mCBP, mCP, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, heterocyclic compounds having an indole ring as a partial structure of the condensed ring, and the like can be used.
As the doping material, an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, a metal complex, or the like can be used. For example, pyrene derivatives, anthracene derivatives, quinacridones, coumarin, rubrene, perylene and derivatives thereof, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, spirobifluorene derivatives and the like can be cited. These may be used alone or in a single layer form by mixing with other materials, or may be formed into a laminated structure of layers formed alone, a laminated structure of layers formed by mixing, or a laminated structure of layers formed alone and layers formed by mixing. These materials may be formed into thin films by a known method such as vapor deposition, spin coating, or ink jet.
The hole blocking layer of the organic electroluminescent device of the present invention is preferably formed using a known compound having hole blocking properties. For example, phenanthroline derivatives such as 2,4, 6-tris (3-phenyl) -1,3, 5-triazine (T2T), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), bathocuproine (BCP), metal complexes of quinolinol derivatives such as aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenol salt (BAlq), and various compounds having a hole blocking effect such as rare earth complexes, oxazole derivatives, triazole derivatives, and triazine derivatives can be used. These may be used alone or in a single layer form by mixing with other materials, or may be formed into a laminated structure of layers formed alone, a laminated structure of layers formed by mixing, or a laminated structure of layers formed alone and layers formed by mixing. These materials may be formed into thin films by a known method such as vapor deposition, spin coating, or ink jet.
The above-described material having hole blocking property can also be used for formation of an electron transport layer described below. That is, by using the above known material having hole blocking property, a layer which serves as both a hole blocking layer and an electron transport layer can be formed.
The electron transport layer of the organic electroluminescent device of the present invention is preferably formed using a known compound having electron transport properties. For example, metal complexes of hydroxyquinoline derivatives such as Alq 3 and BAlq; various metal complexes; triazole derivatives; triazine derivatives; oxadiazole derivatives; pyridine derivatives; bis (10-hydroxybenzo [ H ] quinoline) beryllium (Be (bq) 2); benzimidazole derivatives such as 2- [4- (9, 10-dinaphthyl-2-anthracen-2-yl) phenyl ] -1-phenyl-1H-benzimidazole (ZADN); thiadiazole derivatives; an anthracene derivative; a carbodiimide derivative; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives; silole derivatives, and the like. These may be used alone or in a single layer form by mixing with other materials, or may be formed into a laminated structure of layers formed alone, a laminated structure of layers formed by mixing, or a laminated structure of layers formed alone and layers formed by mixing. These materials may be formed into thin films by a known method such as vapor deposition, spin coating, or ink jet.
The electron injection layer of the organic electroluminescent device of the present invention may be formed using a material known per se. For example, alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; metal complexes of hydroxyquinoline derivatives such as lithium hydroxyquinoline; metal oxides such as alumina, and the like.
As a material commonly used for the electron injection layer or the electron transport layer, a material obtained by further doping N with a metal such as cesium, a triarylphosphine oxide derivative, or the like can be used.
As the cathode of the organic electroluminescent device of the present invention, it is preferable to use an electrode material having a low work function such as aluminum, magnesium, or an alloy having a low work function such as magnesium silver alloy, magnesium indium alloy, aluminum magnesium alloy as the electrode material.
As the substrate of the present invention, a substrate in a conventional organic light emitting device, such as glass or plastic, may be used. In the present invention, a glass substrate is selected.
The following are specific examples.
Example 1: synthesis of Compound 3
(Synthesis of intermediate 1-1)
The synthetic route for intermediate 1-1 is shown below:
2-bromocarbazole (2.5 g,10 mmol) was dissolved in 100mL of acetone at room temperature, potassium permanganate powder (4.0 g,25 mmol) was added with stirring, and after the addition was completed, the system was gradually warmed to reflux and reacted under reflux for 6h. After completion of the reaction, the solvent was distilled off, and the residue was washed with chloroform. The residue was neutralized with a sodium thiosulfate solution and extracted with chloroform. The organic phases were combined, dried and the solvent was distilled off, and the crude product was recrystallized from chloroform and n-hexane to give 1.5g of a white solid in yield 61％.MS(EI)：m/z：487.92[M+].Anal.calcd for C24H14Br2N2(％)：C 58.81,H 2.88,N 5.71;found：C 58.78,H 2.90,N 5.69.
(Synthesis of Compound 3)
The synthetic route for compound 3 is shown below:
In a 250mL Schlenk flask, under nitrogen protection, intermediate 1-1 (2.5 g,5 mmol), phenoxazine (2.0 g,11 mmol), palladium acetate (22.4 mg,0.1 mmol), tri-tert-butylphosphine tetrafluoroborate (73 mg,0.25 mmol), sodium tert-butoxide (1.9 g,20 mmol) and 120mL toluene were added sequentially, and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the solvent was distilled off, the residue was dissolved with 200mL of methylene chloride and 50mL of water, the mixture was washed with water, an organic layer was separated, an aqueous layer was extracted twice with 15mL of methylene chloride, and the organic layers were combined. After evaporation of the solvent, the residue was separated by column chromatography (petroleum ether: dichloromethane=2:1 (V/V)). The solvent was distilled off, and after drying, 2.6g of a white solid was obtained in yield 76％.MS(EI)：m/z：694.30[M+].Anal.calcd for C48H30N4O2(％)：C 82.98,H 4.35,N 8.06;found：C 82.96,H 4.38,N 8.04.
Example 2: synthesis of Compound 11
(Synthesis of Compound 11)
The synthetic route for compound 11 is shown below:
To a clean 250mL three-necked flask under nitrogen was added sequentially intermediate 1-1 (5.8 g,10 mmol), anhydrous sodium carbonate (4.2 g,40 mmol), dibenzofuran-2-boronic acid (5.9 g,24 mmol), tetrakis (triphenylphosphine palladium) (460 mg,0.4 mmol) and 150mL of a mixed solvent (1, 4-dioxane: water=5:1, (V/V)), and the system was warmed to reflux and reacted overnight under reflux. After the reaction is completed, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with methylene chloride. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (petroleum ether: ethyl acetate=3:1, (V/V)) to give 3.4g of a white solid, yield 50％.MS(EI)：m/z：664.28[M+].Anal.calcd for C48H28N2O2(％)：C 86.73,H 4.25,N 4.21;found：C 86.68,H 4.17,N 4.16.
Example 3: synthesis of Compound 29
(Synthesis of intermediate 1-2)
The synthetic route for intermediate 1-2 is shown below:
3-bromocarbazole (2.5 g,10 mmol) was dissolved in 100mL of acetone at room temperature, potassium permanganate powder (4.0 g,25 mmol) was added with stirring, and after the addition was completed, the system was gradually warmed to reflux and reacted under reflux for 6h. After completion of the reaction, the solvent was distilled off, and the residue was washed with chloroform. The residue was neutralized with a sodium thiosulfate solution and extracted with chloroform. The organic phases were combined, dried and the solvent was distilled off, and the crude product was recrystallized from chloroform and n-hexane to give 1.8g of a white solid in yield 75％.MS(EI)：m/z：487.88[M+].Anal.calcd for C24H14Br2N2(％)：C 58.81,H 2.88,N 5.71;found：C 58.77,H 2.92,N 5.68.
(Synthesis of Compound 29)
The synthetic route for compound 29 is shown below:
In a 250mL Schlenk flask, under nitrogen protection, intermediate 1-2 (2.5 g,5 mmol), 7-dimethyl-5, 7-indano [2,1-b ] carbazole (3.1 g,11 mmol), palladium acetate (11 mg,0.05 mmol), tri-tert-butylphosphine tetrafluoroborate (29 mg,0.1 mmol), sodium tert-butoxide (1.9 g,20 mmol) and 120mL toluene were sequentially added, and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the solvent was distilled off, the residue was dissolved with 200mL of methylene chloride and 50mL of water, the mixture was washed with water, an organic layer was separated, an aqueous layer was extracted twice with 15mL of methylene chloride, and the organic layers were combined. After evaporation of the solvent, the residue was separated by column chromatography (petroleum ether: dichloromethane=2:1 (V/V)). The solvent was distilled off, and after drying, 3.2g of a white solid was obtained in yield 72％.MS(EI)：m/z：894.42[M+].Anal.calcd for C66H46N4(％)：C 88.56,H 5.18,N 6.26;found：C 88.54,H 5.20,N 6.23.
Example 4: preparation of organic electroluminescent device 1 (organic EL device 1)
A hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 were sequentially formed on a transparent anode 2 previously formed on a glass substrate 1 to prepare an organic electroluminescent device as shown in fig. 3.
Specifically, a glass substrate on which an ITO film having a film thickness of 100nm was formed was subjected to ultrasonic treatment in a Decon 90 alkaline cleaning solution, rinsed in deionized water, rinsed three times each in acetone and ethanol, baked in a clean environment until the moisture was completely removed, rinsed with ultraviolet light and ozone, and bombarded with a low-energy cation beam. The glass substrate with the ITO electrode is placed in a vacuum cavity, and vacuum is pumped to 4 multiplied by 10 -4-2×10-5 Pa. Then, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene (HAT-CN) was vapor deposited on the glass substrate with ITO electrode at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 10nm as a hole injection layer. N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was vapor deposited on the hole injection layer at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 40nm as a hole transport layer. 3,3 '-bis (N-carbazolyl) -1,1' -biphenyl (mCBP) was vapor-deposited on the hole transport layer at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 10nm as an Electron Blocking Layer (EBL). On the electron blocking layer, the compound of example 1 (compound 3) and the compound ET1 as host materials were mixed at 1;1, the vapor deposition rate was 0.2nm/s, and the vapor deposition rate of GD1 as a dopant was 0.16nm/s, and the mixture was co-evaporated by double evaporation to form a layer having a film thickness of 20nm as a light-emitting layer, with a doped weight ratio of GD1 of 8wt%. Aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenol salt (BAlq) was deposited on the light-emitting layer at a deposition rate of 0.2nm/s to form a layer having a film thickness of 10nm as a Hole Blocking Layer (HBL). BAlq was vapor-deposited on the hole blocking layer at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 40nm as an Electron Transport Layer (ETL). 8-hydroxyquinoline-lithium (Liq) was vapor-deposited on the electron transport layer at a vapor deposition rate of 0.1nm/s to form a layer having a film thickness of 2nm as an electron injection layer. Finally, aluminum is deposited at a deposition rate of 0.5nm/s or more to form a cathode having a film thickness of 100 nm.
Examples 5 to 17: preparation of organic EL devices 2 to 14
An organic EL device was fabricated under the same conditions as the organic EL device 1, except that the compounds in table 1 below were used instead of the compounds in each layer of example 4, respectively.
Comparative examples 1 to 8: preparation of organic EL devices comparative examples 1 to 8
An organic EL device comparative example was produced under the same conditions as the organic EL device 1, except that the compounds in table 1 below were used instead of the compounds in each layer of example 4, respectively.
The structures of the compounds related to the examples and comparative examples are as follows:
Table 1 shows the compounds used for the preparation of the organic EL devices 2 to 14 and the organic EL device comparative examples 1 to 8 in the examples of the present invention.
TABLE 1
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When a direct current voltage was applied to the organic EL devices 1 to 14 produced in examples 4 to 17 and the organic EL devices produced in comparative examples 1 to 8 were measured for light emission characteristics of comparative examples 1 to 8 in the atmosphere at normal temperature.
The current-luminance-voltage characteristics of the device were completed by the Keithley source measurement system with corrected silicon photodiodes (Keithley 2400Sourcemeter, keithley 2000 Currentmeter), the electroluminescence spectra were measured by the Photo research company PR655 spectrometer, and the external quantum efficiency of the device was calculated by the method of literature adv.
The device lifetime was measured as: the light-emitting luminance (initial luminance) at the start of light emission was set to 10000cd/m 2, and constant current driving was performed until the light-emitting luminance decayed to 9000cd/m 2 (corresponding to 90% where the initial luminance was taken as 100% to 90% decay). The device lifetime with GD1 as dopant refers to the time to decay to 9000cd/m 2 (corresponding to 90% where initial brightness is taken as 100% to 90% decay) with 10000cd/m 2 as initial brightness. The device lifetime of 4CzIPN as dopant refers to the time to decay to 9000cd/m 2 (corresponding to 90% where initial brightness is taken as 100% to 90% decay) with 10000cd/m 2 as initial brightness. All devices were packaged in a nitrogen atmosphere.
The measurement results are shown in table 2.
TABLE 2
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As can be seen from the data of the organic EL devices 1-14 in Table 2, the 9, 9-dicarbazole derivatives of the present invention obtain excellent performance data, and the dosage of the doping materials is less, and the cost is lower; as can be seen from comparison of the organic EL device 1 and the organic EL devices 13 to 14, the amounts of the host material and the doping material are changed within a certain range, and good performance data can be obtained, and the organic EL device can be adjusted according to practical application conditions, so that the flexibility is high.
Organic EL devices comparative example 2, comparative example 4, and organic EL device 4 GD1 was used as a dopant, and the host materials of the organic EL device 4 were the compounds ET1 and 11 of the present invention. As can be seen by comparison of the device performance data, the organic EL device 4 has a lower operating voltage, the external quantum efficiency is relatively improved by nearly 19%, and the device lifetime (90%) is significantly longer.
In addition, the organic EL devices of comparative example 1, comparative example 3 and organic EL device 3 each use 4CzIPN as a dopant, and the host materials of the organic EL device 3 are the compound ET1 and the compound 11 of the present invention, and it is seen from comparison of device performance data that the organic EL device 3 has a longer device lifetime.
By comparing examples with comparative examples, it was found that the bipolar bi-host materials used in the organic EL devices 1 to 12 of the present invention significantly improved the performance of the material device, compared to the unipolar host and unipolar bi-host materials of the comparative example devices 3 to 6. And the compound of the present invention is also more excellent in performance in bipolar host materials than in bipolar dual host materials of comparative example devices 1, 2, 7 and 8.
From the above, the light-emitting layer of the organic electroluminescent device uses the 9, 9-dicarbazole derivative as one of the double main bodies, which can effectively reduce the working voltage, improve the external quantum efficiency and prolong the service life of the device compared with the materials commonly used in the prior art.
Industrial applicability:
The 9, 9-dicarbazole derivative has excellent luminous efficiency, service life characteristic and low driving voltage. Therefore, an organic electroluminescent device having an excellent lifetime can be prepared from the compound.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.

Claims (5)

1. A 9, 9-dicarbazole derivative selected from the group consisting of:
。
2. an organic light-emitting layer comprising a 9, 9-dicarbazole derivative according to claim 1.
3. An organic light-emitting layer according to claim 2, wherein the organic light-emitting layer comprises a double-host material and a doping material, the double-host material comprises a hole-type host and an electron-type host, the hole-type host is 9, 9-dicarbazole derivative, and the electron-type host comprises cyano derivative, triazine derivative, phenanthroline derivative, quinazoline derivative
Any one of biology and pyrazine derivatives.
4. An organic light-emitting layer according to claim 3, wherein the content of the 9, 9-dicarbazole derivative is 40wt% to 53wt%, and the content of the doping material is 0.1 wt% to 20wt%.
5. An organic electroluminescent device comprising the organic luminescent layer according to any one of claims 2 to 4.
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Publication number Priority date Publication date Assignee Title
CN103313980A (en) * 2011-02-07 2013-09-18 出光兴产株式会社 Biscarbazole derivative and organic electroluminescent element using same
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