CN115417885B - Carbazole derivative and application thereof in organic light-emitting element - Google Patents

Carbazole derivative and application thereof in organic light-emitting element Download PDF

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CN115417885B
CN115417885B CN202211140953.9A CN202211140953A CN115417885B CN 115417885 B CN115417885 B CN 115417885B CN 202211140953 A CN202211140953 A CN 202211140953A CN 115417885 B CN115417885 B CN 115417885B
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carbazole derivative
organic electroluminescent
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CN115417885A (en
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曹建华
冯静
张昊
边坤
刘殿君
郭文龙
李程辉
王振宇
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Shanghai 800 Million Spacetime Advanced Material Co ltd
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Abstract

The invention relates to a carbazole derivative and application thereof in an organic light-emitting element. The carbazole derivative has a structure shown in a formula (I), has a high triplet state energy level, and increases conjugation of a carbazole parent nucleus, so that thermal stability of the material and capability of transporting carriers are improved. The carbazole derivative is applied to an organic electroluminescent element, and can remarkably reduce driving voltage, improve luminous efficiency and prolong service life. The structural formula of the carbazole derivative is shown as a formula (I).

Description

Carbazole derivative and application thereof in organic light-emitting element
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a carbazole derivative and application thereof in an organic light-emitting element.
Background
In general, an organic light emitting phenomenon refers to a phenomenon that emits light when electric energy is applied to an organic substance. That is, when an organic layer is disposed between an anode and a cathode, if a voltage is applied between the two electrodes, holes are injected from the anode to the organic layer, electrons are injected from the cathode to the organic layer, excitons are formed when the injected holes and electrons meet, and light and heat are emitted when the excitons transition to a ground state.
In recent years, organic electroluminescent display technology has tended to mature, and some products have entered the market, but in the industrialization process, many problems still remain to be solved. In particular, various organic materials for manufacturing elements, which have carrier injection and transport properties, material electroluminescent properties, service life, color purity, matching between various materials and between various electrodes, and the like, have not been solved; especially, the luminous efficiency and the service life of the light emitting element do not meet the practical requirements, which greatly limits the development of organic light-emitting Diode (OLED) technology. While the metal complex phosphorescent material using triplet light emission has high light emission efficiency, its green and red light materials have reached the use requirements, but the metal complex phosphorescent material requires a phosphorescent material having a high triplet energy level or a hole material to match it. Therefore, the development of phosphorescent materials or hole materials having high triplet energy levels is an urgent need for the development of current OLEDs.
Under current technological development, improvements are still needed, both for fluorescent materials and for phosphorescent materials, in particular in terms of operating voltage, efficiency and lifetime for use in organic electroluminescent elements and in terms of thermal stability during sublimation.
In view of this, the present invention has been made.
Disclosure of Invention
In order to overcome the above-described problems of the conventional techniques and to further improve the characteristics of the organic electroluminescent element, development of a more stable and effective substance that can be used as a phosphorescent material or a hole material in the organic electroluminescent element has been continuously demanded.
It is emphasized that in the present invention, "substituted or unsubstituted" means: is selected from hydrogen, deuterium, halogen atom, hydroxyl, nitrile, nitro, amino, amidine, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 60 Alkyl, C 2 -C 60 Alkenyl, C 2 -C 60 Alkynyl, C 1 -C 60 Alkoxy, C 3 -C 60 Cycloalkyl, C 3 -C 60 Cycloalkenyl, C 6 -C 60 Aryl, C 6 -C 60 Aryloxy, C 6 -C 60 Aryl sulfide group and C 2 -C 60 More than 1 substituent in the heterocyclic aryl group is substituted or unsubstituted, or a substituent which is linked by more than 2 substituents in the substituents exemplified above is substituted or unsubstituted.
It should be emphasized that, in the present invention,ar is represented by 1 A bond to N.
The invention provides a carbazole derivative, which can improve the thermal stability of materials and the capacity of transporting carriers, and an organic electroluminescent element prepared by the carbazole derivative can obviously reduce driving voltage, improve luminous efficiency and prolong service life.
The structural formula of the carbazole derivative is shown as a formula (I):
wherein,
X 1 selected from O, S or CR 0 ；
R 1 ～R 13 The same or different radicals are selected from hydrogen, deuterium, fluorine, hydroxyl, nitrile, nitro, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 40 Alkyl, C 1 -C 40 Alkoxy, C 2 -c 40 Alkenyl, C 1 -c 40 Alkylthio, C 1 -C 40 Alkoxy, C 3 -C 40 Cycloalkyl, C 1 -C 40 Alkyl sulfoxide group, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylamine group, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 6 -C 60 Aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 Silyl, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups;
R 0 selected from the group consisting of substituted and unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Arylamine group, substituted or unsubstituted C 6 -C 60 Arylthio, substituted or unsubstituted C 6 -C 60 Aryl sulfoxide group, substituted or unsubstituted C 3 -C 40 Silyl, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups;
Ar 1 selected from the group consisting of substituted and unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, or substituted or unsubstituted C 2 -C 60 A heterocyclic aryl group.
Aryl groups in the sense of the present invention contain 6 to 60 carbon atoms, heteroaryl groups contain 2 to 60 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O or s. In this case, two or more rings of the heteroaryl group may be attached to each other simply or in a condensed form, or may further include a condensed form with the aryl group. As non-limiting examples of such heteroaryl groups, six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, and the like can be cited; polycyclic rings such as phenoxazolyl, indolizinyl, indolyl, purinyl, quinolinyl, benzothiazolyl, carbazolyl, and the like; 2-furyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidinyl, and the like.
Preferably, the aryl, heteroaryl or heteroaryl group is preferably selected from the group consisting of phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthryl, pyrenyl,a group, perylene group, fluoranthenyl group, naphthacene group, pentacene group, benzopyrene group, biphenyl group, terphenyl group, tripolyphenyl group, tetrabiphenyl group, fluorenyl group, spirobifluorenyl group, dihydrophenanthrene group, triphenylene group, dihydropyrenyl group, tetrahydropyrenyl group, cis-or trans-indenofluorenyl group, cis-or trans-indenocarbazolyl group, indolocarbazolyl group, benzofuranocarbazolyl group, benzothiophenocarbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, azadibenzo [ g, iD ]Naphtho [2,1,8-cde]Azulene, triindenyl, heterotrimeric indenyl, spirotrimeric indenyl, spiroheterotrimeric indenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyridyl, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, benzo [5,6 ]]Quinolinyl, benzo [6,7]Quinolinyl, benzo [7,8]Quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthaimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthazolyl, anthracrooxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazaanthracenyl2, 7-diazapyrenyl, 2, 3-diazapyrenyl, 1, 6-diazapyrenyl, 1, 8-diazapyrenyl, 4,5,9, 10-tetraazaperylene, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorozinyl, naphthyridinyl, azacarbazolyl, benzocarboline, carboline, phenanthroline, 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, indolizinyl, diazolidinyl, or combinations thereof.
Alkyl radicals in the sense of the present invention contain 1 to 40 carbon atoms and in which the individual hydrogen atoms or-CH 2 -linear alkyl groups or alkyl groups with branches, the groups of which may also be substituted; alkenyl or alkynyl groups contain at least two carbon atoms, and alkyl, alkenyl or alkynyl groups are preferably considered to mean, by way of non-limiting example, the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.
Alkoxy is preferably an alkoxy group having 1 to 40 carbon atoms, which is taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octoxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2, 2-trifluoroethoxy.
Heteroalkyl is preferably an alkyl radical having from 1 to 40 carbon atoms, meaning in which the hydrogen atom or-CH is alone 2 Groups substituted with oxygen, sulfur, halogen atoms, as non-limiting examples, alkoxy, alkylthio, fluoroalkoxy, fluoroalkylthio, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2-trifluoroethoxy, 2-trifluoroethylthio, ethyleneoxy, ethylenethio, propyleneoxy, propylenethio, butylenethio, butyleneoxy, pentenyloxy, pentenylthio, cyclopentenyloxy, cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexene thio, acetylenyloxy, acetylenylthio, propynyloxy, butynylthio, pentynyloxy, pentynylthio, hexyloxy, hexylynylthio.
In general, cycloalkyl, cycloalkenyl groups according to the invention may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, wherein one or more-CH 2 The groups may be replaced by the groups described above; in addition, one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups.
The heterocycloalkyl group used in the present invention means a monovalent functional group obtained by removing one hydrogen atom from a non-aromatic hydrocarbon having a atomic number of 3 to 40. At this time, one or more carbons, preferably 1 to 3 carbons, in the ring are substituted with a heteroatom such as N, O or S. As non-limiting examples thereof, tetrahydrofuran, tetrahydrothiophene, morpholine, piperazine, and the like are given.
The condensed ring aryl group used in the present invention means a monovalent functional group obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms, which is a combination of two or more rings. In this case, two or more rings may be attached to each other singly or in a condensed form. As a non-limiting example thereofSuch as phenanthryl, anthracyl, fluoranthracyl, pyrenyl, triphenylene, perylene, and,A base, etc.
As the arylamine group used in the present invention, an arylamine group refers to an amine substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylamine group, there are a diphenylamino group, an N-phenyl-1-naphthylamine group, an N- (1-naphthyl) -2-naphthylamine group and the like. The heteroarylamino group means an amine substituted with an aryl group having 6 to 60 carbon atoms and a heteroaryl group having 2 to 60 carbon atoms, and as non-limiting examples of the heteroarylamino group, there are N-phenylpyridine-3-amino, N- ([ 1,1 '-biphenyl ] -4-yl) dibenzo [ b, d ] furan-2-amino, N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluorene-2-amino, and the like.
Alkoxy as used herein refers to a monovalent functional group represented by RO-, R is an alkyl group having 1 to 40 carbon atoms, and may include a straight chain, branched chain, or cyclic structure. Non-limiting examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, cyclopentoxy, cyclohexyloxy, and the like.
The aryloxy group used in the present invention means a monovalent functional group represented by R 'O-and R' is an aryl group having 6 to 60 carbon atoms. As non-limiting examples of such aryloxy groups, there are phenoxy, naphthoxy, biphenyloxy, and the like.
The alkylsilyl group used in the present invention means a silyl group substituted with an alkyl group having 1 to 40 carbon atoms, and the number of carbon atoms constituting the alkylsilyl group is at least 3, and as non-limiting examples of the alkylsilyl group, there are trimethylsilyl group, triethylsilyl group and the like. Arylsilyl refers to silyl groups substituted with aryl groups having from 6 to 60 carbon atoms.
The arylphosphorus group used in the present invention means a diarylphosphorus group substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylphosphorus group, there are diphenylphosphorus group, bis (4-trimethylsilylbenzene) phosphorus group and the like. The phosphorus atom of the aryl phosphorus oxide group is the diaryl phosphorus group is oxidized to the highest valence state.
The arylboron group used in the present invention means a diarylboroyl group substituted with an aryl group having 6 to 60 carbon atoms, and as non-limiting examples of the arylboron group, there are diphenyl boron group, bis (2, 4, 6-trimethylbenzene) boron group and the like. The alkylboryl group means a dialkylboryl group substituted with an alkyl group having 1 to 40 carbon atoms, and as non-limiting examples of the alkylboryl group, there are di-t-butylboryl group, diisobutylboryl group and the like.
Preferably, the R 0 Selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylenyl, carbazolyl, dibenzofuranyl, or dibenzothiophenyl.
Preferably, said R 1 ～R 13 Each independently selected from the group consisting of hydrogen, deuterium, fluorine, nitrile, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, carbazolyl, dibenzofuranyl, or dibenzothiophenyl.
Preferably, the Ar 1 Selected from phenyl, naphthyl, anthryl, benzanthraceyl, phenanthryl, pyrenyl, and,A group, perylene group, fluoranthenyl group, naphthacene group, pentacene group, benzopyrene group, biphenyl group, terphenyl group, trimeric phenyl group, tetrabiphenyl group, fluorenyl group, spirobifluorenyl group, dihydrophenanthrene group, triphenylene group, dihydropyrenyl group, tetrahydropyrenyl group, cis-or trans-indenofluorenyl group, cis-or trans-indenocarbazolyl group, cis-or trans-indolocarbazolyl group, trimeric indenyl group, heterotrimeric indenyl group, spiro-iso-tril indenyl group, furyl group, benzofuryl group, isobenzofuryl group, dibenzofuryl group, dibenzothienyl group, isobenzothienyl group, dibenzothienyl group, pyrrolyl group, indolyl group, isoindolyl group, carbazolyl group, pyridyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthridinyl group, benzo [5,6 ]Quinolinyl, benzo [6,7]Quinolinyl, benzo [7,8]Quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthamidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, and benzBenzoxazolyl, naphthooxazolyl, anthracoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazaanthracenyl, 2, 7-diazapyrenyl, 2, 3-diazapyrenyl, 1, 6-diazapyrenyl, 1, 8-diazapyrenyl, 4,5,9, 10-tetraazaperylene, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorozinyl, naphthyridinyl, azacarbazolyl, benzocarboline, carboline, phenanthroline, 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, indolizinyl, or combinations thereof.
According to an embodiment of the invention, the R 0 Selected from the group consisting of phenyl, biphenyl, naphthyl.
According to an embodiment of the invention, the R 1 ～R 13 Each independently selected from the group consisting of hydrogen or deuterium.
According to an embodiment of the present invention, ar1 is selected from the group consisting of pyrrolyl, pyridyl, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, benzo [5,6] quinolinyl, benzo [6,7] quinolinyl, benzo [7,8] quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, napthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, hexaazabenzophenanthryl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazaanthracenyl, 2, 7-diazapyrenyl, 2, 3-diazapyrenyl, 1, 6-diazapyrenyl, 1, 8-diazapyrenyl, 4, 5-dipentadienyl, 10-tetraazaperylene, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorozinyl, naphthyridinyl, azacarbazolyl, benzocarboline, carboline, phenanthroline, 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, pteridinyl, indolizinyl, quinazolinyl, benzothiadiazolyl, or groups derived from combinations of these systems.
Further, the Ar 1 Selected from the group consisting of the groups shown in II-1 to II-17 below:
wherein,
Z 1 、Z 2 each independently selected from the group consisting of hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 40 Alkyl, C 2 -C 40 Alkenyl, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy, C 3 -C 40 Naphthene radical, C 3 -C 40 Cycloalkenyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T 1 represent O, S, CR ' R ' or NAr ';
r ', R' are each independently selected from hydrogen, deuterium, C 1 ～C 40 Alkyl, C of (2) 1 ～C 40 Is optionally substituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 Heteroaryl, R 'and R' may optionally be joined or fused to form one or more additional substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or s in the ring formed; more preferably, R' is methyl, phenyl or fluorenyl;
Ar' is selected from C 1 ～C 40 Alkyl, C of (2) 1 ～C 40 Heteroalkyl of (C) 3 ～C 40 Cycloalkyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 A group consisting of heteroaryl groups; more preferably, ar' is methyl, ethyl, phenyl, biphenyl, or naphthyl.
In the present invention, the term "substituted or unsubstituted" means that the compound is selected from hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group or carboxylate thereof, sulfonic acid group or sulfonate thereof, phosphoric acid group or phosphate thereof, and C 1 -C 40 Alkyl, C 2 -C 40 Alkenyl, C 2 -C 40 Alkynyl, C 1 -C 40 Alkoxy, C 3 -C 40 Cycloalkyl, C 3 -C 40 Cycloalkenyl, C 6 -C 60 Aryl, C 6 -C 60 Aryloxy, C 6 -C 60 Aryl sulfide group and C 2 -C 60 More than 1 substituent in the heterocyclic aryl group may be substituted or unsubstituted, or 2 substituents as exemplified above may be usedThe substituent groups formed by connecting the above substituent groups are substituted or unsubstituted.
In the present invention, the "halogen" or "halogen atom" means F, clBr or l.
Preferably, the carbazole derivative is selected from the group consisting of compounds represented by the following formulas P01 to P333:
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based on the same technical concept, the invention further provides a preparation method of the carbazole derivative, as shown in scheme 1:
Scheme 1:
in scheme 1, the symbols used are as defined in formula (I), and Y 1 、Y 2 、Y 3 Each independently selected from Cl, br, l or OTf;
the raw materials for synthesizing the carbazole derivative shown in the formula (I) can be purchased through commercial paths, the principle of the method, the operation process, the conventional post-treatment, the column purification, the recrystallization purification and other means are well known to the synthesis personnel in the field, the synthesis process can be completely realized, and the target product is obtained through theory and practice.
In particular, the method comprises the steps of,the carbazole derivative of formula (I) is represented by Y 1 Carrying out SUZUKI coupling reaction on the substituted I-0 and substituted o-nitrobenzeneboronic acid or pinacol borate to prepare an intermediate I-1; intermediate I-1 and ortho-Y 2 The substituted halogenated benzene is subjected to Buchwald-Hartwig coupling reaction to prepare an intermediate I-2; the intermediate I-2 undergoes a ring closure reaction to obtain a carbazole derivative intermediate I-3; the intermediate I-3 is subjected to substitution coupling reaction under alkaline condition to prepare the parent nucleus compound I-4; compounds I-4 and Ar 1 -Y 3 And (3) performing a coupling reaction to prepare the compound shown as the formula (1). Intermediate Ar 1 -Y 3 Can be prepared by palladium-catalyzed or base-catalyzed coupling reactions.
The palladium catalyst which can be used for the palladium-catalyzed coupling reaction may be selected from: pd (P- t Bu 3 ) 2 、Pd(PPh 3 ) 4 、Pd 2 (dba) 3 、Pd 2 (dba) 3 CHCl 3 、PdCl 2 (PPh 3 ) 2 、PdCl 2 (cH 3 CN) 2 、Pd(OAc) 2 、Pd(acac) 2 、Pd/c、PdCl 2 、[Pd(allyl)cl] 2 Or the like, or a mixture of two or more kinds thereof.
In addition, the base used for palladium-catalyzed or base-catalyzed coupling reactions may be selected from: sodium tert-butoxide, potassium tert-butoxide, sodium hydride, lithium hydride, sodium tert-amyl alcohol, sodium ethoxide, sodium methoxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium, potassium hydride, triethylamine, cesium fluoride, or the like, or a mixture of two or more thereof is used.
The coupling reaction may be carried out in an organic solvent, wherein the organic solvent may be selected from the group consisting of: ether solvents such as diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, ethylene glycol diethyl ether, ethylene glycol methyl ether, diethylene glycol diethyl ether, and anisole; aromatic hydrocarbon agents such as benzene, toluene, xylene, etc.; chlorobenzene, dichlorobenzene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane and the like, and one or a mixture of two or more kinds may be used.
The invention also provides an organic electroluminescent material, which comprises the carbazole derivative as a raw material; preferably, the raw material includes at least one carbazole derivative having a structure represented by P01 to P333 as described above.
The invention also provides an application of the organic electroluminescent material in preparing the organic electroluminescent element.
The present invention also provides an organic electroluminescent element comprising: a first electrode, a second electrode, a capping layer, and one or more organic layers disposed between the first electrode and the second electrode; the material of at least one of the organic layer or the capping layer includes the carbazole derivative described above.
Preferably, the organic layer or the capping layer includes at least one carbazole derivative having a structure represented by P01 to P333 as described above.
The organic electroluminescent element comprises a cathode, an anode and at least one light emitting layer. In addition to these layers, it may contain other layers, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and/or charge generation layers. An intermediate layer having, for example, an exciton blocking function can likewise be introduced between the two light-emitting layers. It should be noted, however, that not every one of these layers need be present. The organic electroluminescent device described herein may comprise one light emitting layer, or it may comprise a plurality of light emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred is a system with three light-emitting layers, wherein the three layers can display blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises a carbazole derivative according to the present invention.
Preferably, the light-emitting layer includes at least one carbazole derivative having a structure represented by P01 to P333 as described above.
Further, the organic electroluminescent element according to the present invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light emitting layer is directly adjacent to the electron blocking layer or hole transport layer or anode and/or the light emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode.
In the other layers of the organic electroluminescent element according to the invention, in particular in the hole injection and hole transport layers and in the electron injection and electron transport layers, all materials can be used in the manner generally used according to the prior art. A person of ordinary skill in the art will thus be able to use all materials known in relation to organic electroluminescent elements in combination with the light-emitting layer according to the invention without inventive effort.
Furthermore, preference is given to organic electroluminescent elements in which one or more layers are applied by means of a sublimation process, wherein the sublimation process is carried out in a vacuum at a temperature of less than 10 -5 Pa, preferably below 10 -6 The material is applied by vapor deposition at an initial pressure of Pa. However, the initial pressure may also be even lower, for example below 10 -7 Pa。
Preference is likewise given to organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where at 10 -5 The material is applied at a pressure between Pa and 1 Pa. A particular example of this method is an organic vapor jet printing method, wherein the material is applied directly through a nozzle and is thus structured.
Furthermore, organic electroluminescent elements are preferred, from which one or more layers are produced, for example by spin coating, or by means of any desired printing method, for example screen printing, flexography, lithography, photoinitiated thermal imaging, thermal transfer, inkjet printing or nozzle printing. Soluble compounds the soluble compounds are obtained, for example, by suitable substitution of the compounds of formula (I). These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, a hybrid method is possible, in which one or more layers are applied, for example from a solution, and one or more further layers are applied by vapor deposition.
These methods are generally known to those of ordinary skill in the art and they can be applied to the organic electroluminescent element comprising the compound according to the present invention without inventive effort.
The invention therefore also relates to a method for manufacturing an organic electroluminescent element according to the invention, at least one layer being applied by means of a vacuum sublimation method, and/or characterized in that at least one layer is applied by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or in that at least one layer is applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to a carbazole derivative comprising at least one of the above-indicated invention. The same preferable cases as indicated above with respect to the organic electroluminescent element apply to the compound of the present invention. In particular, the compounds may furthermore preferably comprise further compounds. Treatment of the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, requires preparations of the compounds according to the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchyl ketone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylanisole, 3, 5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1-bis (3, 4-dimethylphenyl) ethane, or mixtures of these solvents.
The invention also provides a consumer product comprising the organic electroluminescent element.
In addition, unless otherwise specified, all raw materials used in the present invention are commercially available, and any ranges recited in the present invention include any numerical value between the end values and any sub-range constituted by any numerical value between the end values or any numerical value between the end values.
The beneficial effects of the invention are as follows:
the carbazole derivative provided by the invention has a structure shown in a formula (I), and the parent nucleus of the carbazole derivative has a triarylamine group and a carbazole group, so that the three-dimensional structure of molecules can be effectively regulated and controlled, and the stacking density of the molecules is improved; meanwhile, the triarylamine structure and the carbazole structure act together, so that the compound has excellent hole transmission performance, the HOMO energy level of the compound is regulated and improved, the HOMO energy level of the compound is more matched with the energy level of the doped dye, the hole injection and transmission capacity of the compound is improved, the acquisition of low voltage is facilitated, and the stability of carrier transmission in an electric field environment is obviously improved. In addition, the compound has a special tetrahedral conjugated structure, so that a good amorphous film can be prepared, and therefore, when the carbazole derivative is applied to an organic electroluminescent element, the driving voltage can be remarkably reduced, the luminous efficiency can be improved, and the service life can be prolonged.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 shows a schematic diagram of an organic light emitting device 100. The illustrations are not necessarily drawn to scale. The device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111. The device 100 may be fabricated by sequentially depositing the layers described.
Fig. 2 shows a schematic diagram of an organic light emitting device 200 with two light emitting layers. The device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first emissive layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second emissive layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 may be prepared by sequentially depositing the layers described. Because the most common OLED device has one light emitting layer, and device 200 has a first light emitting layer and a second light emitting layer, the light emitting peaks of the first and second light emitting layers may be overlapping or cross-overlapping or non-overlapping. In the corresponding layers of device 200, materials similar to those described with respect to device 100 may be used. Fig. 2 provides one example of how some layers may be added from the structure of device 100.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more; the orientation or positional relationship indicated by the terms "upper", "lower", etc. are based on the orientation or positional relationship shown in the drawings, are merely for convenience of description and to simplify the description, and are not indicative or implying that the apparatus or elements in question must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The experimental materials and related equipment used in the examples below, unless otherwise specified, are all commercially available, and the percentages, such as the percentages without otherwise specified, are all mass percentages.
The following examples are examples of the test apparatus and method for testing the performance of OLED materials and devices as follows:
OLED element performance detection conditions:
luminance and chromaticity coordinates: photoresearch PR-715 was tested using a spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
Power efficiency: NEWPORT 1931-C test was used.
Example 1
A process for the preparation of compound P07 comprising the steps of:
the first step: preparation of intermediate Int-1
20.0mmol of 1-chloro-10H-phenoxazine are dissolved in 50mL of DMF and under the protection of nitrogen, 30.0mmol of potassium acetate, 22.0mmol of pinacol borate and 2.0mmol of PdCl are added 2 (dppf) and 2.0mmol of cuprous iodide, heating to 100deg.C, reacting for 16 hours, cooling to room temperature, pouring the reaction solution into 150mL of ice water, extracting with ethyl acetate, washing the organic phase with saturated saline, collecting the organic phase, drying, filtering, concentrating the filtrate under reduced pressure, and separating and purifying the residue with silica gel column to obtain compound Int-1 as yellow solid with yield: 82%.
And a second step of: preparation of intermediate Int-2
21.0mmol of Int-1, 20.0mmol of o-nitrobenzol, 45.0mmol of anhydrous sodium carbonate, 0.01mmol of Pd0132, 60mL of toluene, 40mL of ethanol and 40mL of water are mixed under the protection of nitrogen, the mixture is heated to reflux and stirred for reaction for 12 hours, the mixture is cooled to room temperature, 50mL of water is added, the mixture is extracted by EA, the organic phase is dried, filtered and concentrated to dryness under reduced pressure, and the mixture is separated and purified by a silica gel column to obtain yellow solid Int-2 with the yield: 86%.
And a third step of: preparation of intermediate Int-3
Under the protection of nitrogen, 20.0mmol of Int-2 is dissolved in 80mL of dimethylbenzene, 22.0mmol of o-chlorobromobenzene, 30.0mmol of sodium tert-butoxide and 0.1mmol of Pd are added 2 (dba) 3 And 0.2mmol Xantphos, raise the temperature to 110 ℃ for 16 hours, reduce the temperature to room temperature, add 50mL ice water, extract with ethyl acetate, collect the organic phase, dry, filter, the filtrate is concentrated to dryness under reduced pressure, the residue is separated and purified with silica gel column to obtain compound Int-3, yellow solid, yield: 78%.
Fourth step: preparation of intermediate Int-4
Under the protection of nitrogen, 10.0mmol of Int-3 is dissolved in 40mL of dichlorobenzene, 35.0mmol of triphenylphosphine is added, the mixture is heated to reflux and stirred for reaction for 24 hours, the mixture is cooled to room temperature, 100mL of toluene and 70.0mmol of anhydrous magnesium chloride are added, the mixture is heated to reflux for 2 hours, the mixture is cooled to room temperature and filtered, a filter cake is washed by methylene dichloride, the filtrate is concentrated to dryness under reduced pressure, and the yellow solid Int-4 is obtained by separating and purifying by a silica gel column, and the yield: 65%.
Fifth step: preparation of intermediate Int-5
Under the protection of nitrogen, 20.0mmol of Int-4 is dissolved in 60mL of pyridine, 30.0mmol of sodium tert-butoxide and 0.2mmol of Pd are added 2 (dba) 3 And 0.04mL of 10% tri-tert-butyl phosphorus toluene solution, heating to 90 ℃, stirring and reacting for 12 hours, cooling to room temperature, adding 50mL of water, extracting with EA, drying an organic phase, filtering, concentrating and drying under reduced pressure, dispersing and filtering with normal hexane to obtain yellow solid Int-5, and obtaining the yield: 76%.
Sixth step: preparation of Compound P07
10.0mmol of intermediate Int-5 (reactant 1) is dissolved in 40mL of DMF, cooled to 0 ℃, 12.0mmol of sodium hydride solid is added in portions, the mixture is stirred and reacted for 1 hour, and 11.0mmol of 2-chloro-4- (dibenzo [ b, d) is added]Furan-4-yl) -6-phenyl-1, 3, 5-triazine (reactant 2) is warmed to room temperature, stirred and reacted for 12 hours, 120mL of ice water is added dropwise, filtration is carried out, filter cakes are washed with water and ethanol, yellow solid is separated and purified by a silica gel column and recrystallized by toluene/THF, yellow solid P07 is obtained, yield is 87%, MS (MALDI-TOF): m/z=668.2094 [ m+h ]] + ； 1 HNMR(δ、CDCl 3 )：8.75(1H，s)；8.59～8.55(2H，m)；8.13～8.11(1H，m)；8.01～7.94(4H，m)；7.54～7.50(3H，m)；7.46～7.37(5H，m)；7.33～7.27(2H，m)；7.21～7.14(4H，m)；7.00～6.95(3H，m)。
Referring to the above synthetic method, the following compounds shown in table 1 were prepared:
TABLE 1
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Example 2
Preparation of compound P136:
under nitrogen protection, 10.0mmol of intermediate Int-6 (reactant 1) is dissolved in 50mL of dry xylene, 12.0mmol of 2- (2-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (reactant 2), 15.0mmol of sodium tert-butoxide, 0.1mmol of Pd are added 2 (dba) 3 And 0.2mmol XPhos, raise the temperature to 110 ℃ and stir for reaction for 12 hours, cool to room temperature, add 50mL water, filter, wash the filter cake with water, ethanol, separate and purify with silica gel column, re-crystallize with dichloromethane/THF to give yellow solid P136, yield 83%, MS (MALDI-TOF): m/z=670.2071 [ m+h ] ] + ； 1 HNMR(δ、CDCl 3 )：8.78～8.74(4H，m)；8.42～8.40(1H，m)；7.89～7.87(1H，m)；7.73～7.70(2H，m)；7.55～7.47(6H，m)；7.45～7.36(5H，m)；7.28～7.25(2H，m)；7.21～7.19(1H，m)；7.15～7.07(2H，m)；7.04～6.97(2H，m)；6.95～7.93(1H，m)。
Referring to the above synthetic method, the following compounds shown in table 2 were prepared:
TABLE 2
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Example 3
The preparation method of the compound P232 comprises the following steps:
the first step: preparation of intermediate Int-7
20.0mmol of carbazole is dissolved in 50mL of DMF, 20.0mmol of cesium carbonate and 20.0mmol of cuprous iodide are added under the protection of nitrogen, the temperature is raised to reflux for reaction for 5 hours, the temperature is reduced to room temperature, the reaction solution is poured into 150mL of ice water, the ethyl acetate is used for extraction, the organic phase is washed with saturated saline, the organic phase is collected, dried, filtered, the filtrate is concentrated under reduced pressure to dryness, and the residue is separated and purified by a silica gel column to obtain a compound Int-7, yellow solid, yield: 87%.
And a second step of: preparation of intermediate Int-8
Under the protection of nitrogen, 10.0mmol of Int-7 is added into 35.0mmol of triphenylphosphine at 180 ℃ in batches, stirred and reacted for 5 hours, cooled to 120 ℃, added into 200mL of toluene and 70.0mmol of anhydrous magnesium chloride, heated to reflux for 2 hours, cooled to room temperature, filtered, the filter cake is washed with dichloromethane, the filtrate is concentrated to dryness under reduced pressure, and separated and purified by a silica gel column to obtain yellow solid Int-8, the yield: 60%.
And a third step of: preparation of intermediate Int-9
Referring to the synthetic procedure of the first step of example 1, substituting only 1-chloro-10H-phenoxazine in the first step of example 1 with Int-8, the compound Int-9 was prepared as a yellow solid with yield: 79%.
Fourth step: preparation of intermediate Int-10
Referring to the synthetic procedure of example 1, second step, substituting only Int-1 of example 1 with Int-9, compound Int-10 was prepared as a yellow solid, yield: 87%.
Fifth step: preparation of intermediate Int-11
Referring to the synthetic procedure of the third step of example 1, only Int-2 in the third step of example 1 was replaced with Int-10 to prepare Compound Int-11 as a yellow solid, yield: 82%.
Sixth step: preparation of intermediate Int-12
Referring to the synthetic procedure of the fourth step of example 1, substituting only Int-3 in the fourth step of example 1 with Int-11, compound Int-12 was prepared as a yellow solid, yield: 68%.
Seventh step: preparation of intermediate Int-13
Referring to the synthesis of the fifth step of example 1, substituting only Int-4 in the fifth step of example 1 with Int-12, compound Int-13 was prepared as a yellow solid, yield: 74%.
Eighth step: preparation of Compound P232
10.0mmol of intermediate Int-13 (reactant 1) is dissolved in 40mL of DMSO, cooled to 0 ℃, 13.0mmol of potassium hydroxide solid is added in portions, stirred and reacted for 1 hour, 12.0mmol of 2-chloro-4-naphthylquinazoline (reactant 2) is added, the temperature is raised to 45 ℃ and stirred and reacted for 12 hours, the reaction solution is poured into 150mL of ice water and filtered, a filter cake is washed with water and ethanol, the yellow solid is separated and purified by a silica gel column and recrystallized by toluene/THF, and yellow solid P232 is obtained, the yield is obtained: 85%, MS (MALDI-TOF): m/z=674.2358 [ m+h ] ] + ； 1 HNMR(δ、CDCl 3 )：8.74(1H，s)；8.28～8.26(1H，d)；8.18～8.16(1H，m)；7.93～7.84(6H，m)；7.73～7.68(2H，m)；7.61～7.52(3H，m)；7.50～7.44(5H，m)；7.41～7.34(3H，m)；7.25～7.21(1H，m)；7.15～7.11(2H，m)；7.07～7.01(2H，m)。
Referring to the above synthetic method, the following compounds shown in table 3 were prepared:
TABLE 3 Table 3
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Example 4
Preparation of compound P307:
10.0mmol of intermediate Int-14 (reactant 1) was dissolved in 60mL of dry toluene under nitrogen and 12.0mmol of 2- (2-bromophenyl) -4 was added6-diphenyl-1, 3, 5-triazine (reactant 2), 15.0mmol sodium tert-butoxide, 0.1mmol Pd 2 (dba) 3 And 0.2mmol of 10% tri-tert-butyl phosphorus toluene solution, heating to 100 ℃ and stirring for reaction for 12 hours, cooling to room temperature, adding 50mL of water, extracting with dichloromethane, collecting an organic phase, drying, filtering, concentrating the filtrate under reduced pressure to dryness, separating and purifying with a silica gel column, and recrystallizing with dichloromethane/ethanol to obtain yellow solid P307 with a yield of 87%, MS (MALDI-TOF): m/z=727.2624 [ m+h ]] + ； 1 HNMR(δ、CDCl 3 )：8.78～8.74(4H，m)；8.42～8.40(1H，m)；8.23～8.20(1H，m)；7.87～7.82(3H，m)；7.73～7.71(1H，m)；7.55～7.50(6H，m)；7.48～7.34(8H，m)；7.31～7.29(1H，m)；7.23～7.19(1H，m)；7.14～7.07(3H，m)；7.05～7.03(1H，m)。
Referring to the above synthetic method, the following compounds shown in table 4 were prepared:
TABLE 4 Table 4
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Example 5
As shown in fig. 1, the OLED element of the present embodiment is a top-emission light element, and includes a substrate 101, an anode layer 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode layer 102, a hole transport layer 104 disposed on the hole injection layer 103, an electron blocking layer 105 disposed on the hole transport layer 104, an organic light emitting layer 106 disposed on the electron blocking layer 105, an electron transport layer 107 disposed on the organic light emitting layer 106, an electron injection layer 108 disposed on the electron transport layer 107, a cathode layer 109 disposed on the electron injection layer 108, and a capping layer 110 disposed on the cathode layer 109, wherein the method for preparing the OLED element includes the following steps:
1) The glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, rinsed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dried, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the above ITO glass substrate in vacuum chamber, and vacuumizing to less than 1×10 -5 Pa, depositing metallic silver as an anode layer on the ITO film, the thickness of the deposited film beingContinuing to vapor deposit the compounds HI01 and F4TCNQ as hole injection layers respectively, wherein F4TCNQ is 3% of HI01 by mass, and the vapor deposition film thickness is +.>
3) Continuously evaporating a compound HTM112 as a hole transport layer on the hole injection layer to obtain an evaporated film thickness of/>
4) Continuously evaporating compound EBL as electron blocking layer on the hole transport layer to obtain an evaporating film thickness of
5) Continuing to vapor deposit the compound of the invention with the formula (I) as a main material and RD015 as a doping material on the electron blocking layer, wherein RD015 is 3% of the mass of the formula (I) as a memberAn organic light-emitting layer of the product, the film thickness of the organic light-emitting layer obtained by vapor deposition being
6) Continuously evaporating an electron transport layer of LiQ and ET012 as elements on the organic light-emitting layer, wherein the ET012 is 50% of LiQ mass, and the evaporating film thickness is
7) Continuously evaporating a LiF layer on the electron transport layer to form an electron injection layer with an evaporating film thickness of
8) Evaporating metal magnesium and silver on the electron injection layer to serve as a transparent cathode layer of the element, wherein the mass ratio of the magnesium to the silver is 1:10, the thickness of the vapor deposition film is
9) A layer of HTM112 is deposited on the transparent cathode layer as CPL of the element, and the thickness of the deposited film isThe OLED element provided by the invention is obtained.
The structure of the compound used in example 5 above is as follows:
example 6
An organic electroluminescent device 200 having a structure as shown in fig. 2, which comprises a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213, was prepared by vacuum evaporation of the layers according to the preparation method of example 5.
Comparative example 1
By following the same procedure as in example 5, substituting the compound of formula I in step 5) with HS01, comparative element 1 was obtained;
comparative example 2
By following the same procedure as in example 5, substituting the compound of formula I in step 5) with HS02, comparative element 2 was obtained;
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The organic electroluminescent element prepared by the above process was subjected to the following performance test:
the driving voltage and current efficiency and the lifetime of the organic electroluminescent elements prepared in example 5 and comparative examples 1 and 2 were measured using a digital source meter and a luminance meter. Specifically, the luminance of the organic electroluminescent element was measured to reach 1000cd/m by increasing the voltage at a rate of 0.1V per second 2 The voltage at the time is the driving voltage, and the current density at the time is measured; the ratio of brightness to current density is the current efficiency; LT90% life test is as follows: at 1000cd/m using a luminance meter 2 The luminance decay of the organic electroluminescent element was measured to be 900cd/m while maintaining a constant current at luminance 2 Time in hours. The data listed in table 5 are relative data compared to comparative element 1.
TABLE 5
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As is clear from Table 5, the carbazole derivative of the present invention produced devices having lower driving voltages than HS01 and HS02, significantly improved current efficiency up to as much as 1.2 times that of the comparative devices, and significantly improved LT90% lifetime of the devices at the same luminance.
Compared with the compound of the invention, the compound HS01 in the comparative example 1 is different in that the conjugated capability of the biscarbazole plane is weak, and the carbazole derivative of the invention increases the conjugated plane of the carbazole plane and improves the conjugated capability of the parent nucleus by introducing bonded phenoxazine, phenothiazine, phenazine or carbazole and the like on the basis of carbazole, so that the performance of the compound is excellent in molecular film formation and charge transmission, the charge transmission in the element is more balanced, and the element performance is improved.
The compound HS02 in comparative example 2 is different from the compound of the present invention in that HS02 is indolocarbazole, and although the planar conjugation ability is enhanced, the planar conjugation ability is weak and the introduction of oxygen, sulfur and nitrogen hetero atoms forms a large conjugated condensed ring structure as compared with the carbazole derivative of the present invention, so that it is excellent in both molecular film formation and charge transport, and the charge transport in the element is more balanced, and in element performance, particularly, the LT90% lifetime is much higher than that of the comparative element, and therefore the carbazole derivative of the present invention is an organic electroluminescent material excellent in performance.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (5)

1. A carbazole derivative, characterized in that the carbazole derivative is selected from compounds represented by the following formulae P01-P333:
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2. an organic electroluminescent material, characterized in that a raw material of the organic electroluminescent material comprises the carbazole derivative as described in claim 1.
3. Use of the organic electroluminescent material as claimed in claim 2 for the preparation of an organic electroluminescent element.
4. An organic electroluminescent element, characterized in that the organic electroluminescent element comprises: a first electrode, a second electrode, a capping layer, and one or more organic layers disposed between the first electrode and the second electrode; the material of at least one of the organic layer or the capping layer includes the carbazole derivative as claimed in claim 1.
5. The organic electroluminescent element according to claim 4, wherein the organic layer comprises a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2344084A1 (en) * 2001-04-12 2002-10-12 National Research Council Of Canada Conjugated polycarbazole derivatives in organic light emitting diodes
CN108440537A (en) * 2018-04-18 2018-08-24 石家庄诚志永华显示材料有限公司 Carbazole derivates, material and organic electroluminescence device comprising the carbazole derivates
CN112480128A (en) * 2020-11-23 2021-03-12 北京八亿时空液晶科技股份有限公司 Carbazole derivative and application thereof
TW202219257A (en) * 2020-11-02 2022-05-16 大陸商北京八億時空液晶科技股份有限公司 Carbazole derivative and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2344084A1 (en) * 2001-04-12 2002-10-12 National Research Council Of Canada Conjugated polycarbazole derivatives in organic light emitting diodes
CN108440537A (en) * 2018-04-18 2018-08-24 石家庄诚志永华显示材料有限公司 Carbazole derivates, material and organic electroluminescence device comprising the carbazole derivates
TW202219257A (en) * 2020-11-02 2022-05-16 大陸商北京八億時空液晶科技股份有限公司 Carbazole derivative and application thereof
CN112480128A (en) * 2020-11-23 2021-03-12 北京八亿时空液晶科技股份有限公司 Carbazole derivative and application thereof

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