CN114213314A - Organic electroluminescent material based on carbazole-9-yl-diphenylamine derivatives and electronic device thereof - Google Patents

Organic electroluminescent material based on carbazole-9-yl-diphenylamine derivatives and electronic device thereof Download PDF

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CN114213314A
CN114213314A CN202111678081.7A CN202111678081A CN114213314A CN 114213314 A CN114213314 A CN 114213314A CN 202111678081 A CN202111678081 A CN 202111678081A CN 114213314 A CN114213314 A CN 114213314A
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carbazole
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diphenylamine
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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 material based on carbazole-9-yl-diphenylAn organic electroluminescent material of amine derivatives and an electronic device thereof. The carbazole-9-yl-diphenylamine derivatives have a structure shown in a general formula (1): wherein L is1～L4Each independently represents 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; by introducing an electron donor group into a carbazole-9-yl-diphenylamine rigid structure, the obtained carbazole-9-yl-diphenylamine derivative has excellent film forming property and thermal stability. The carbazole-9-yl-diphenylamine derivative can be used as a constituent material of a light-emitting layer, and can reduce driving voltage, improve efficiency, brightness, service life and the like. In addition, the preparation method of the carbazole-9-yl-diphenylamine derivative is simple, raw materials are easy to obtain, and the industrial development requirement can be met.

Description

Organic electroluminescent material based on carbazole-9-yl-diphenylamine derivatives and electronic device thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an organic electroluminescent material based on carbazole-9-yl-diphenylamine derivatives and an electronic device thereof.
Background
The organic electroluminescent device has a series of advantages of self-luminescence, low-voltage driving, full curing, 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.
Organic electroluminescent devices generally comprise 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, a host-guest structure is often used for the light-emitting layer. That is, the light emitting material is doped in the host material at a certain concentration to avoid concentration quenching and triplet-triplet annihilation, improving the light emitting efficiency. Therefore, the host material is generally required to have a higher triplet energy level and, at the same time, a higher stability.
At present, research on organic electroluminescent materials has been widely conducted in academia and industry, and a large number of organic electroluminescent materials with excellent performance have been developed. In view of the above, the future direction of organic electroluminescent devices is to develop high efficiency, long lifetime, low cost white light devices and full color display devices, but the industrialization of the technology still faces many key problems. Therefore, designing and searching a stable and efficient compound as a novel material of an organic electroluminescent device to overcome the defects of the organic electroluminescent device in the practical application process is a key point in the research work of the organic electroluminescent device material and the future research and development trend.
At present, in an organic light emitting device, a device structure using an organic electroluminescent host material in a light emitting layer shows advantages of high light emitting efficiency and low driving voltage, but the lifetime of the device is not particularly good, and the material composition of the light emitting layer is yet to be optimized. Patent CN 112341375a discloses an application of carbazole diphenylamine N-N coupling derivatives in luminescence, wherein a luminescent layer contains the carbazole diphenylamine N-N coupling derivatives and a guest material, the guest material is FIrpic, the mass fraction of carbazole diphenylamine N-N coupling derivatives in the luminescent layer is 4-10%, and the rest is the guest material FIrpic. Since FIrpic is expensive due to the adoption of a phosphorescent light-emitting material of a rare noble metal, the use of an excessive proportion of FIrpic in the device increases the cost of the device and affects the commercial development of the device.
Therefore, there is a need for an economical, efficient, stable and durable carbazole-9-yl-diphenylamine derivatives, and a preparation method and application thereof in luminescence.
Disclosure of Invention
The invention provides an organic electroluminescent material based on carbazole-9-yl-diphenylamine derivatives and an electronic device thereof, and aims to solve the problems that the device structure using an organic electroluminescent main material in a luminescent layer in the existing organic luminescent device has low luminescent efficiency, high driving voltage, short service life and poor material composition of the luminescent layer.
In order to achieve the above objects, embodiments of the present invention provide a carbazole-9-yl-diphenylamine derivative having a structure represented by general formula (1):
Figure BDA0003452926610000021
wherein L is1～L4Each independently represents 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;
R1represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO2、N(R2)2、OR2、SR2、C(＝O)R2、P(＝O)R2、Si(R2)3Substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl of (a), substituted or unsubstituted C2-C20Alkynyl, substituted or unsubstituted C6-C40Or substituted or unsubstituted C5-C40The aromatic heterocyclic group of (1);
R2represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C30Or substituted or unsubstituted C5-C30The aromatic heterocyclic group of (1).
[ radical definitions ]
<L1～L4>
L1～L4Each independently represents 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 selected from N, O and/or S. In the present invention, the number of hetero atoms may be 1 to 5. An aromatic hydrocarbon group or 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, systems of 9, 9' -spirobifluorenes, 9, 9-diarylfluorenes, triarylamines, diaryl ethers, etc., 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, 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 bonded directly to one another, such as biphenyl, terphenyl or quaterphenyl, are likewise intended to be regarded as aromatic hydrocarbon groups or aromatic heterocyclic groups.
From L1～L4The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be exemplified by: phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, hydropyranyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, perylenyl, anthryl, benzopyrenyl, terphenylenyl, terphenylindenyl, etc, Phenanthridinyl, benzo-5, 6-quinolinyl, benzo-6, 7-quinolinyl, benzo-7, 8-quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinylimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazenanthrayl, 2, 7-diazapyranyl, 2, 3-diazapyranyl, 1, 6-diazapyranyl, 1, 8-diazapyranyl, benzo,4, 5-diazapyranyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluoresceinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 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, pteridinyl, indolizinyl, benzothiadiazolyl, and the like.
In the present invention, preferably, L1～L4Each independently represents 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, L1～L4Each independently represents a single bond, a carbonyl group, a phenyl group, a triazinyl group or a biphenyl group.
From L1～L4The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be unsubstituted, but may also have a substituent. The substituents may be exemplified by the following: a deuterium atom; a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, or a n-hexyl group; alkoxy having 1 to 6 carbon atoms such as methoxy, ethoxy or propoxy; alkenyl, such as vinyl or allyl; aryloxy groups such as phenoxy or tolyloxy; arylalkoxy, such as benzyloxy or phenethyloxy; aromatic hydrocarbon radicals or condensed polycyclic aromatic radicals, e.g. phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthryl, benzo [9,10 ] benzo]Phenanthryl or spirobifluorenyl; aromatic heterocyclic radicals, e.g. pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazoleA group selected from the group consisting of phenyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, azafluorenyl, diazafluorenyl, carbolinyl, azaspirobifluorenyl and diazafluorafluorafluorenyl; arylethenyl, such as styryl or naphthylethenyl; and acyl groups such as acetyl or benzoyl and the like.
The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be linear or branched. Any of the above substituents may be further substituted with the above exemplary substituents. The above substituents may be present independently of each other, but may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.
Donor1～Donor4Each independently represents Ar1～Ar4、
Figure BDA0003452926610000041
Ar1～Ar8Each independently represents optionally substituted one or more R1A substituted aromatic electron donor group having 6 to 30 carbon atoms or an aromatic heterocyclic electron donor group having 5 to 30 carbon atoms optionally substituted with one or more R1;
m to p are respectively independent integers of 0 to 4, and m to p are not 0 at the same time;
further, the carbazole-9-yl-diphenylamine derivatives have a structure shown in a general formula (I) or (II):
Figure BDA0003452926610000051
wherein L is1～L4And Ar1～Ar8Has the meaning as defined for the general formula (1).
Further, said Ar1～Ar8Each independently selected from one of the following groups:
Figure BDA0003452926610000052
Figure BDA0003452926610000061
wherein the dotted line represents and L1～L4Or a N-bonded bond, R1Has the meaning as defined for the general formula (1).
Further, from Ar1～Ar8The aromatic electron donor group having 6 to 30 carbon atoms or the aromatic heterocyclic electron donor group having 5 to 30 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from Ar1～Ar8An aromatic electron donor group having 6 to 30 carbon atoms or an aromatic heterocyclic electron donor group having 5 to 30 carbon atoms represented by one or more R1Substituted aromatic electron donor groups having 5 to 30 carbon atoms or substituted by one or more R1A substituted, aromatic heterocyclic electron donor group having from 5 to 30 carbon atoms.
R1Represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO2、N(R2)、OR2、SR2、C(＝O)R2、P(＝O)R2、Si(R2)3A 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.
From R1The alkyl group having 1 to 20 carbon atoms represented may be exemplified by: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl, hexadecyl, octadecyl, eicosyl, cyclopropyl, cyclobutyl, hexadecyl, octadecyl, eicosyl, and tert-butylCyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic.
From R1The alkyl group having 1 to 20 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from R1Alkyl having 1 to 20 carbon atoms represented by one or more of the following R2And (4) substitution. In addition, one or more non-adjacent CH in the alkyl group2The group can be represented by R2C＝CR2、C≡C、Si(R2)3、C＝O、C＝NR2、P(＝O)R2、SO、SO2、NR2O, S or CONR2And wherein one or more hydrogen atoms may be replaced with deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group.
From R1The alkenyl group having 2 to 20 carbon atoms represented may be exemplified by: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexenyl, allyl, cyclohexenyl and the like. The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic.
From R1The alkenyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R1The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.
From R1The alkynyl group having 2 to 20 carbon atoms represented may be exemplified by: ethynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl and the like.
From R1The alkynyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R1The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.
From R1The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by the above formula may be exemplified by the group consisting of Ar1～Ar8The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by the above formula represent the same groups.
From R1The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R1The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents. In addition, two adjacent R1Substituents or two adjacent R2The substituents optionally may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more R2Substitution; where two or more substituents R1May be connected to each other and may form a ring.
Preferably represented by R1The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by (a) may be exemplified by: phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazolyl, benzofurocarbazolyl, benzofluorenocarbazolyl, benzanthracenyl, benzophenanthryl, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron, triphenyl phosphoxy, diphenyl phosphoxy, triphenyl silicon, and mixtures thereof,Tetraphenylsilyl 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 R2And (4) substitution.
R2Represents 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.
From R2The alkyl group having 1 to 20 carbon atoms represented by R can be enumerated by1The alkyl groups represented by the formulae having 1 to 20 carbon atoms represent the same groups.
From R2The 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 the formula R1The same groups as those shown for the aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.
From R2The 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 may be unsubstituted, or may also have a substituent. The substituents may be exemplified by: a deuterium atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; cyano, and the like.
Further, the carbazole-9-yl-diphenylamine derivatives are selected from one of the following compounds:
Figure BDA0003452926610000081
Figure BDA0003452926610000091
in another aspect of the present invention, there is provided a method for preparing carbazol-9-yl-diphenylamine derivatives, comprising the steps of:
Figure BDA0003452926610000092
Figure BDA0003452926610000101
the obtained compound can be purified by, for example, purification by 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 compounds can be carried out by mass spectrometry, elemental analysis.
In another aspect of the present invention, there is provided an organic light emitting layer comprising a carbazole-9-yl-diphenylamine derivative as described in any one of the above.
Further, the organic light emitting layer comprises a dual-body material and a doping material, the dual-body material comprises a cavity-type body and an electron-type body, the cavity-type body is a carbazole-9-yl-diphenylamine 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.
Further, the doping material includes any one of an aromatic amine derivative, a styryl amine compound, a boron complex, a fluoranthene compound, and a metal complex.
Further, the content of the carbazole-9-yl-diphenylamine derivative is 40 wt% -53 wt%, and the content of the doped material is 0.1 wt% -20 wt%.
In a further aspect of the object of the present invention, there is provided an organic electroluminescent device comprising the organic light emitting layer described in any one of the above.
Further, the organic electroluminescent device of the present invention comprises: the organic electroluminescence device includes a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer includes the carbazole-9-yl-diphenylamine derivative of the present invention.
The scheme of the invention has the following beneficial effects:
1) the organic electroluminescent device provided by the scheme of the invention has the advantages of high luminous efficiency, long service life and low driving voltage by using the carbazole-9-yl-diphenylamine derivative as the luminous layer, and is obviously superior to the existing organic electroluminescent device.
2) The invention uses a double-main body device structure in the light-emitting layer of the organic electroluminescent device, wherein the double main body is respectively selected from a hole type main body and an electron type main body. The hole type main body is selected from the carbazole-9-yl-diphenylamine compound, an electron donor group is introduced into the hole type main body, and the hole type main body has high thermal stability, chemical stability and hole transmission performance, and more importantly has proper singlet state, triplet state and molecular orbital energy level. Therefore, the organic electroluminescent material is taken as a main material to be introduced into a luminescent layer of an organic electroluminescent device, and is matched with an electronic main body, so that the luminous efficiency of the device is improved, the driving voltage of the device is reduced, and particularly, the service life of the device is greatly prolonged.
3) The invention can regulate and control the balance of holes and electrons by regulating and controlling the doping ratio of the hole type main body and the electron type main body, has stronger flexibility than a bipolar material, can give consideration to the transmission characteristic and the energy level, and can be applied to a blue light device and a green light device with high energy level.
4) The preparation method of the carbazole-9-yl-diphenylamine derivative is simple, raw materials are easy to obtain, a large amount of expensive luminescent materials are not needed in an organic electroluminescent device, the cost is low, and the industrialized development requirement can be met.
Drawings
FIG. 1 is a fluorescence spectrum (PL) of example 3 (compound 18) of the present invention in a dichloromethane solution;
FIG. 2 is an electroluminescence spectrum of example 4 (organic electroluminescence device 1) of the present invention;
FIG. 3 is a structural view of the organic electroluminescent devices of examples 4 to 6 of the present invention and the organic electroluminescent devices of comparative examples 1 to 2.
[ description of reference ]
1 a substrate; 2 an anode; 3 a hole injection layer; 4 a 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; 10 cathode.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Aiming at the existing problems, the invention provides an organic electroluminescent material based on carbazole-9-yl-diphenylamine derivatives and an electronic device thereof.
The production of the compound represented by the above general formula (1) and the organic electroluminescent device comprising the same is specifically described in the following examples, and the organic electroluminescent device of the present invention comprises: the organic electroluminescence device includes a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer includes the carbazole-9-yl-diphenylamine derivative of the present invention.
Fig. 3 is a structural view showing an organic electroluminescent device of the present invention. As shown in fig. 3, in the organic electroluminescent device of the present invention, 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, some organic layers may be omitted in the multi-layer structure. For example, it may be a configuration in which 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 are omitted, and the anode 2, the hole transport layer 4, the light emitting layer 6, the electron transport layer 8, and the cathode 10 are sequentially provided 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 organic layer contains the compound represented by the above 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 laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, the following can be made: an anode is formed by depositing metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method, 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 a substance which can be used as a cathode is deposited on the organic layer. However, the production method is not limited thereto.
In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is 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 an alloy thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and the like; such as ZnO, Al or SNO2A combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]Conductive polymers such as (PEDOT), polypyrrole, and polyaniline, and ITO is preferable.
As the hole injection layer of the organic electroluminescent device of the present invention, a known material having a hole injection property can be used. Examples thereof include: porphyrin compounds represented by copper phthalocyanine, naphthalenediamine derivatives, star-shaped triphenylamine derivatives, triphenylamine trimers such as arylamine compounds having a structure in which 3 or more triphenylamine structures are connected by a single bond or a divalent group containing no heteroatom in the molecule, tetramers, receptor-type heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
As the hole transport layer of the organic electroluminescent device of the present invention, a known material having a hole transporting property can be preferably used. Examples thereof include: a compound containing a m-carbazolylphenyl group; 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 ' -tetrakisbiphenylylbenzidine, and the like; 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC); various triphenylamine trimers and tetramers; 9,9 ', 9 "-triphenyl-9H, 9' H, 9" H-3,3 ': 6', 3 "-tricarbazole (Tris-PCz), and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
In addition, in the hole injection layer or the hole transport layer, a material obtained by further P-doping tribromoaniline antimony hexachloride, an axial olefin derivative, or the like to a material generally used in the layer, a polymer compound having a structure of a benzidine derivative such as TPD in a partial structure thereof, or the like may be used.
The electron blocking layer of the organic electroluminescent element 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), and 2, 2-bis (4-carbazol-9-ylphenyl) 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; and compounds having an electron-blocking effect, such as monoamine compounds having a high electron-blocking property and various triphenylamine dimers. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
As the light-emitting layer of the organic electroluminescent device of the present invention, a light-emitting layer containing the carbazole-9-yl-diphenylamine derivative of the present invention is preferably used. In addition, various metal complexes such as metal complexes of hydroxyquinoline derivatives including Alq3, compounds having a pyrimidine ring structure, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like can be used.
The light emitting layer may be composed of a host material and a dopant material. As the host material, a carbazole-9-yl-diphenylamine derivative containing the present invention is preferably used. In addition to these, mCBP, mCP, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, heterocyclic compounds having a partial structure in which an indole ring is a condensed ring, and the like can be used.
As the doping material, an aromatic amine derivative, a styryl amine compound, a boron complex, a fluoranthene compound, a metal complex, or the like can be used. Examples thereof include pyrene derivatives, anthracene derivatives, quinacridones, coumarins, rubrenes, perylenes and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, spirobifluorene derivatives, and the like. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
The hole-blocking layer of the organic electroluminescent device of the present invention is preferably formed using a known compound having a hole-blocking property. For example, a phenanthroline derivative 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), a metal complex of a quinolyl derivative such as aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenate (BAlq), and a compound having a hole-blocking effect such as various rare earth complexes, oxazole derivatives, triazole derivatives, and triazine derivatives can be used. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
The above-described material having a hole-blocking property can also be used for formation of an electron transport layer described below. That is, by using the known material having a hole-blocking property, a layer which serves as both a hole-blocking layer and an electron-transporting layer can be formed.
The electron-transporting layer of the organic electroluminescent element of the present invention is preferably formed using a known compound having an electron-transporting property. For example, metal complexes of hydroxyquinoline derivatives such as Alq3 and BAlq; various metal complexes; a triazole derivative; a triazine derivative; an oxadiazole derivative; a pyridine derivative; bis (10-hydroxybenzo [ H ] quinoline) beryllium (be (bq) 2); benzimidazole derivatives such as 2- [4- (9, 10-dinaphthalen-2-anthracen-2-yl) phenyl ] -1-phenyl-1H-benzimidazole (ZADN); a thiadiazole derivative; an anthracene derivative; a carbodiimide derivative; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives; silole derivatives and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.
As the electron injection layer of the organic electroluminescent device of the present invention, a material known per se can be used. For example, alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; metal complexes of quinolinol derivatives such as lithium quinolinol; and metal oxides such as alumina.
In the electron injection layer or the electron transport layer, a material obtained by further N-doping a metal such as cesium, a triarylphosphine oxide derivative, or the like can be used as a material generally used for the layer.
As the cathode of the organic electroluminescent device of the present invention, 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 is preferably used 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, can be used. In the present invention, a glass substrate is selected.
Example 1: synthesis of Compound 3
(Synthesis of intermediate 1-1)
The synthetic route of intermediate 1-1 is shown below:
Figure BDA0003452926610000161
under the protection of nitrogen, potassium iodide (KI, 332mg, 2mmol) and potassium periodate (KIO) were sequentially added to a dry and clean 100mL reaction tube46.9g, 30mmol), 4,4' -dibromodiphenylamine (3.3g, 10mmol), carbazole (1.7g, 10mmol) and 50mL anhydrous acetonitrile (MeCN) and reacted at room temperature overnight. After the reaction was completed, the solvent was distilled off under reduced pressure, and the crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 4: 1 (V/V)). The solvent was evaporated to give 3.4g of a white solid with a yield of 70%. Ms (ei): m/z: 491.87[ M ]+]。Anal.calcd for C24H16Br2N2(％)：C 58.56，H 3.28，N 5.69；found：C 58.54，H 3.30，N 5.66。
(Synthesis of Compound 3)
The synthetic route for compound 3 is shown below:
Figure BDA0003452926610000162
under nitrogen protection, intermediate 1-1(2.5g, 5mmol), phenoxazine (2.0g, 11mmol), palladium acetate (22.4mg, 0.1mmol), tri-tert-butylphosphine tetrafluoroborate (73mg, 0.25mmol), sodium tert-butoxide (1.9g, 20mmol) and 120mL of toluene were added in sequence to a 250mL Schlenk flask, and the reaction was stirred under reflux for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of methylene chloride and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of methylene chloride, and the organic layers were combined. After the solvent was distilled off, the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). After evaporation of the solvent and drying, 2.6g of a white solid was obtained in 76% yield. Ms (ei): m/z: 696.38[ M ]+]。Anal.calcd for C48H32N4O2(％)：C 82.74，H 4.63，N 8.04；found：C 82.72，H 4.65，N 8.02。
Example 2: synthesis of Compound 14
(Synthesis of intermediate 1-2)
The synthetic route of intermediate 1-2 is shown below:
Figure BDA0003452926610000171
under the protection of nitrogen, potassium iodide (KI, 332mg, 2mmol) and potassium periodate (KIO) were sequentially added to a dry and clean 100mL reaction tube46.9g, 30mmol), diphenylamine (1.7g, 10mmol), 3, 6-dibromocarbazole (3.3g, 10mmol) and 50mL anhydrous acetonitrile (MeCN) and reacted at room temperature overnight. After the reaction was completed, the solvent was distilled off under reduced pressure, and the crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 4: 1 (V/V)). The solvent was evaporated to give 3.6g of a white solid with a yield of 74%. Ms (ei): m/z: 491.76[ M ]+]。Anal.calcd for C24H16Br2N2(％)：C 58.56，H 3.28，N 5.69；found：C 58.53，H 3.32，N 5.67。
(Synthesis of Compound 14)
The synthetic route for compound 14 is shown below:
Figure BDA0003452926610000172
under nitrogen protection, intermediates 1-2(2.5g, 5mmol), phenoxazine (2.0g, 11mmol), palladium acetate (22.4mg, 0.1mmol), tri-tert-butylphosphine tetrafluoroborate (73mg, 0.25mmol), sodium tert-butoxide (1.9g, 20mmol) and 120mL of toluene were added in sequence to a 250mL Schlenk flask, and the reaction was stirred at reflux for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of methylene chloride and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of methylene chloride, and the organic layers were combined. After the solvent was distilled off, the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). The solvent was distilled off, and after drying, 3.0g of a white solid was obtained in 86% yield. Ms (ei): m/z: 696.69[ M ]+]。Anal.calcd for C48H32N4O2(％)：C 82.74，H 4.63，N 8.04；found：C 82.71，H 4.66，N 8.03。
Example 3: synthesis of Compound 18
(Synthesis of intermediates 1 to 3)
The synthetic route of intermediates 1-3 is shown below:
Figure BDA0003452926610000181
under the protection of nitrogen, potassium iodide (KI, 332mg, 2mmol) and potassium periodate (KIO) were sequentially added to a dry and clean 100mL reaction tube46.9g, 30mmol), 4-bromodiphenylamine (2.5g, 10mmol), 3-bromocarbazole (2.5g, 10mmol) and 50mL anhydrous acetonitrile (MeCN) and reacted at room temperature overnight. After the reaction was completed, the solvent was distilled off under reduced pressure, and the crude product was further purified by column chromatography (petroleum ether: dichloromethane ═ 4: 1 (V/V)). The solvent was distilled off to leave 3.9g of a white solid in a yield of 79%. Ms (ei): m/z: 492.08[ M ]+]。Anal.calcd for C24H16Br2N2(％)：C 58.56，H 3.28，N 5.69；found：C 58.55，H 3.29，N 5.66。
(Synthesis of Compound 18)
The synthetic route for compound 18 is shown below:
Figure BDA0003452926610000191
under the protection of nitrogen, 1-3(2.5g, 5mmol) of intermediate and 7, 7-dimethyl-5, 7-dihydroindeno [2,1-b ] are sequentially added into a 250mL Schlenk bottle]Carbazole (3.1g, 11mmol), palladium acetate (11mg, 0.05mmol), tri-tert-butylphosphine tetrafluoroborate (29mg, 0.1mmol), sodium tert-butoxide (1.9g, 20mmol) and 120mL of toluene were reacted under reflux for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of methylene chloride and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of methylene chloride, and the organic layers were combined. After the solvent was distilled off, the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). After evaporation of the solvent and drying, 2.9g of a white solid was obtained in 65% yield. Ms (ei): m/z: 897.02[ M ]+]。Anal.calcd for C66H48N4(％)：C 88.36，H 5.39，N 6.25；found：C 88.34，H 5.42，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, washed three times in acetone and ethanol, respectively, baked in a clean environment to completely remove moisture, washed with ultraviolet light and ozone, and bombarded on the surface with a low-energy cation beam. The glass substrate with the ITO electrode is placed in a vacuum chamber,vacuum-pumping to 4X 10-4-2×10-5Pa. Then, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN) was deposited on the ITO electrode-equipped glass substrate at a deposition rate of 0.2 nm/sec 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 deposited on the hole transport layer at a deposition rate of 0.2nm/s to form a layer having a thickness of 10nm as an Electron Blocking Layer (EBL). On the electron-blocking layer, double-source co-evaporation was performed at a deposition rate of 0.2nm/s for the compound of example 1 (compound 3) as a host material and 0.016nm/s for GD1 as a dopant material to form a layer with a thickness of 20nm as a light-emitting layer, and the proportion by weight of the dopant of GD1 was 8 wt%. On the light-emitting layer, aluminum (III) bis (2-methyl-8-quinolinolato) -4-phenylphenolate (BALq) was vapor-deposited at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 10nm as a Hole Blocking Layer (HBL). On the hole-blocking layer, BALq was deposited at a deposition rate of 0.2nm/s to form a layer having a thickness of 40nm as an electron-transporting layer (ETL). On the electron transport layer, 8-hydroxyquinoline-lithium (Liq) was vapor-deposited 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 vapor-deposited at a vapor deposition rate of 0.5nm/s or more to form a cathode having a film thickness of 100 nm.
Examples 5 to 6: preparation of organic EL devices 2-3
An organic EL device 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.
Comparative examples 1 to 2: preparation of organic EL device comparative examples 1 to 2
Comparative examples of organic EL devices were prepared 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.
The examples and comparative examples relate to the following structures of compounds:
Figure BDA0003452926610000211
table 1 shows compounds used for the production of organic EL devices 1 to 3 in examples of the present invention and comparative examples 1 to 2 of organic EL devices.
TABLE 1
Figure BDA0003452926610000212
The light emission characteristics of the organic EL devices 1 to 3 produced in examples 4 to 6 and the organic EL devices 1 to 2 produced in comparative examples 1 to 2 were measured at normal temperature under the application of a direct current voltage in the atmosphere.
The current-luminance-voltage characteristics of the device were obtained from a Keithley source measuring system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with calibrated silicon photodiodes, the electroluminescence spectra were measured by a Photo research PR655 spectrometer, and the external quantum efficiencies of the devices were calculated by the method of the documents adv.mater, 2003,15, 1043-.
The lifetime of the device was measured as: the light emission luminance at the start of light emission (initial luminance) was set to 10000cd/m2, and constant current driving was performed until the light emission luminance decayed to 9000cd/m2 (corresponding to 90%, where the initial luminance was taken as 100%: 90% decay). The lifetime of the device with GD1 as dopant refers to the time to decay to 9000cd/m2 (corresponding to 90%, where the initial luminance is taken as 100%: 90% decay) with 10000cd/m2 as initial luminance. All devices were encapsulated in a nitrogen atmosphere. The measurement results are shown in table 2.
TABLE 2
Figure BDA0003452926610000221
As can be seen from the data of the organic EL devices 1-3 in the table 2, the carbazole-9-yl-diphenylamine derivatives have excellent performance data, the dosage of doping materials is small, and the cost is low.
Organic EL devices comparative examples 1 and 2 and organic EL device 2 used GD1 as a dopant, and the host material constituting materials of organic EL device 2 were compound ET1 and compound 14 of the present invention. As can be seen from the comparison of the device performance data, the organic EL device 2 has a lower operating voltage, the external quantum efficiency is relatively improved by nearly 20% and 35%, respectively, and the device lifetime (90%) is significantly longer.
By comparing the examples with the comparative examples, we can find that the bipolar dual-host material adopted by the organic EL devices 1 to 3 of the present invention has a significant improvement in the performance of the material device compared with the unipolar host and the unipolar dual-host material of the devices 1 and 2 of the comparative examples.
Therefore, the light-emitting layer in the organic electroluminescent device uses the carbazole-9-yl-diphenylamine derivative as one of the double main bodies, so that the working voltage can be effectively reduced, the external quantum efficiency can be improved and the service life of the device can be prolonged compared with the common material in the prior art.
Industrial applicability
The carbazole-9-yl-diphenylamine derivative has excellent luminous efficiency, life characteristics 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: 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 various changes, modifications, equivalents, and improvements may be made without departing from the spirit and scope of the invention as defined in the following claims
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (9)

1. A carbazole-9-yl-diphenylamine derivative, characterized in that the carbazole-9-yl-diphenylamine derivative has a structure represented by the general formula (1):
Figure FDA0003452926600000011
wherein L is1～L4Each independently represents 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;
Donor1～Donor4each independently represents Ar1～Ar4、
Figure FDA0003452926600000012
Ar1～Ar8Each independently represents optionally substituted one or more R1A substituted aromatic electron donor group having 6 to 30 carbon atoms or an aromatic heterocyclic electron donor group having 5 to 30 carbon atoms optionally substituted with one or more R1;
m to p are respectively independent integers of 0 to 4, and m to p are not 0 at the same time;
R1represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO2、N(R2)2、OR2、SR2、C(＝O)R2、P(＝O)R2、Si(R2)3Substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C2-C20Alkenyl of (a), substituted or unsubstituted C2-C20Alkynyl, substituted or unsubstituted C6-C40Or substituted or unsubstituted C5-C40The aromatic heterocyclic group of (1);
R2represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C30Or substituted or unsubstituted C5-C30The aromatic heterocyclic group of (1).
2. The carbazole-9-yl-diphenylamine derivatives according to claim 1, wherein the carbazole-9-yl-diphenylamine derivative has a structure represented by general formula (I) or (II):
Figure FDA0003452926600000021
wherein L is1～L4And Ar1～Ar8Has the meaning as defined for the general formula (1).
3. The carbazol-9-yl-diphenylamine derivatives according to claim 1, wherein said Ar is selected from the group consisting of1～Ar8Each independently selected from one of the following groups:
Figure FDA0003452926600000022
Figure FDA0003452926600000031
wherein the dotted line represents and L1～L4Or a N-bonded bond, R1Has the meaning as defined for the general formula (1).
4. The carbazol-9-yl-diphenylamine derivatives according to claim 1, wherein R is1And R2 each independently represents phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolylN-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenylboranyl, triphenylphosphinyl, diphenylphosphinyloxy, triphenylsilyl or tetraphenylsilyl.
5. Carbazole-9-yl-diphenylamine derivatives according to claim 1, characterized in that said carbazole-9-yl-diphenylamine derivatives are selected from one of the following compounds:
Figure FDA0003452926600000032
Figure FDA0003452926600000041
6. a process for the preparation of carbazol-9-yl-diphenylamine derivatives as claimed in any one of claims 1 to 5, which comprises the steps of:
dissolving potassium iodide, potassium periodate, bromodiphenylamine and bromocarbazole in acetonitrile, stirring, and reacting to obtain a first intermediate with a structural formula of
Figure FDA0003452926600000042
B1. Adding the first intermediate, anhydrous sodium carbonate, boric acid compound and tetrakis (triphenylphosphine palladium) into a mixed solvent of 1, 4-dioxane and water for coupling reaction to obtain a general formula (I), wherein the structural formula is shown in the specification
Figure FDA0003452926600000043
B2. Adding the first intermediate, the amine compound, palladium acetate and tri-tert-butylphosphine tetrafluoroborate in the step A into toluene, and performing coupling reaction to obtain a general formula (II) with a structural formula
Figure FDA0003452926600000051
Dissolving potassium iodide, potassium periodate, bromodiphenylamine and carbazole in acetonitrile, stirring, and reacting to obtain a second intermediate, wherein the structural formula of the second intermediate is as follows:
Figure FDA0003452926600000052
D1. and D, adding the second intermediate, anhydrous sodium carbonate, a boric acid compound and tetrakis (triphenylphosphine palladium) in the step C into a mixed solvent of 1, 4-dioxane and water to perform a coupling reaction to obtain a general formula (I), wherein the structural formula is shown in the specification
Figure FDA0003452926600000053
D2. Adding the second intermediate, the amine compound, palladium acetate and tri-tert-butylphosphine tetrafluoroborate in the step C into toluene to perform coupling reaction to obtain a general formula (II) with a structural formula
Figure FDA0003452926600000054
E, dissolving potassium iodide, potassium periodate, diphenylamine and bromocarbazole in acetonitrile, stirring, and reacting to obtain a third intermediate with a structural formula
Figure FDA0003452926600000061
F1. And E, adding the third intermediate, anhydrous sodium carbonate, a boric acid compound and tetrakis (triphenylphosphine palladium) in the step E into a mixed solvent of 1, 4-dioxane and water for coupling reaction to obtain a general formula (I), wherein the structural formula is shown in the specification
Figure FDA0003452926600000062
F2. And E, adding the third intermediate, the amine compound, palladium acetate and tri-tert-butylphosphine tetrafluoroborate in the step E into toluene to perform coupling reaction to obtain a general formula (II) with a structural formula
Figure FDA0003452926600000063
G, dissolving potassium iodide, potassium periodate, bromodiphenylamine and bromocarbazole in acetonitrile, stirring, and reacting to obtain a fourth intermediate with a structural formula
Figure FDA0003452926600000064
H1. And G, adding the fourth intermediate, anhydrous sodium carbonate, a boric acid compound and tetrakis (triphenylphosphine palladium) into a mixed solvent of 1, 4-dioxane and water to perform coupling reaction to obtain a general formula (I), wherein the structural formula is shown in the specification
Figure FDA0003452926600000071
H2. And G, adding the fourth intermediate, the amine compound, palladium acetate and tri-tert-butylphosphine tetrafluoroborate into toluene to perform coupling reaction to obtain a general formula (II) with a structural formula
Figure FDA0003452926600000072
7. An organic light emitting layer comprises a double-host material and a doping material, the double-host material comprises a cavity-type host and an electron-type host, the electron-type host comprises one or more of a cyano derivative, a triazine derivative, a phenanthroline derivative, a quinazoline derivative and a pyrazine derivative, and the organic light emitting layer is characterized in that the cavity-type host is the carbazole-9-yl-diphenylamine derivative according to any one of claims 1 to 5.
8. The organic light-emitting layer according to claim 8, wherein the carbazole-9-yl-diphenylamine derivative is contained in an amount of 40 wt% to 53 wt%, and the dopant material is contained in an amount of 0.1 wt% to 20 wt%.
9. An organic electroluminescent device comprising the organic light-emitting layer according to claim 7 or 8.
CN202111678081.7A 2021-12-31 Organic electroluminescent material based on carbazole-9-yl-diphenylamine derivatives and electronic device thereof Active CN114213314B (en)

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