CN113336771A - Condensed ring carbazole derivative and organic electroluminescent device thereof - Google Patents

Condensed ring carbazole derivative and organic electroluminescent device thereof Download PDF

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CN113336771A
CN113336771A CN202110709602.4A CN202110709602A CN113336771A CN 113336771 A CN113336771 A CN 113336771A CN 202110709602 A CN202110709602 A CN 202110709602A CN 113336771 A CN113336771 A CN 113336771A
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CN113336771B (en
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王英雪
刘辉
鲁秋
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Changchun Hyperions Technology Co Ltd
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Abstract

The invention provides a condensed ring carbazole derivative and an organic electroluminescent device thereof, and relates to the technical field of organic photoelectric materials. The condensed ring carbazole derivative provided by the invention has a high triplet state energy level, the condensed ring carbazole derivative can be used for effectively reducing concentration quenching generated by a guest material in a light-emitting layer of an organic electroluminescent device, the efficiency roll-off of the organic electroluminescent device is inhibited, and the service life of the device is prolonged.

Description

Condensed ring carbazole derivative and organic electroluminescent device thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a fused ring carbazole derivative and an organic electroluminescent device thereof.
Background
An Organic Light-Emitting Diode (OLED) refers to a device in which an Organic photoelectric material emits Light under the action of current or an electric field, and can directly convert electric energy into Light energy. Since the OLED has the advantages of color development in a full spectrum range, high brightness, high efficiency, flexible display, fast response speed, and the like, it is increasingly applied to the fields of display and illumination.
OLEDs typically comprise an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer of the OLED may include a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and the like. Under the action of an external electric field, holes injected from the anode and electrons (collectively called carriers) injected from the cathode migrate and recombine in the organic layer, and energy is transferred to the luminescent material, so that the luminescent material is excited to form excitons, the radiation is attenuated when the excitons return to the ground state from the excited state, and the attenuated energy is emitted in the form of light, thereby achieving the purpose of luminescence.
In the case of the light emitting layer, when only one material is used as the light emitting layer, concentration quenching occurs due to an interaction between molecules, resulting in a decrease in the light emitting efficiency of the organic electroluminescent device, and thus in order to increase the light emitting efficiency of the organic electroluminescent device, a guest material is generally doped into a host material to form the light emitting layer. The triplet energy level of the host material should be higher than that of the guest material to ensure that triplet excitons of the guest are confined in the light emitting layer. Host materials can be classified into a hole-type host material, an electron-type host material, and a bipolar host material according to the difference in carrier transport properties. Generally, when a hole-type host material is used, the exciton recombination zone is near the interface of the ETL and the EML, and similarly, when an electron-type host material is used, the exciton recombination zone is near the interface of the HTL and the EML. However, a narrow recombination region accelerates triplet-triplet annihilation, which results in a relatively large roll-off of device efficiency and also affects device lifetime. In order to solve this problem, two methods may be adopted, one of which is to use a dual host material, i.e., one material is selected from a hole-type host material, and the other material is selected from an electron-type host material, and the other is to use a bipolar host material, i.e., to introduce a group having both hole transport ability and electron transport ability into the same host. Compared with a simple hole type main body material and an electron type main body material, the double main body or bipolar main body material can obviously enlarge the carrier recombination region, thereby reducing the annihilation of a triplet state and a triplet state, inhibiting the efficient rapid roll-off of the device under high brightness, and simultaneously, the preparation process of the device is simpler and has obvious advantages.
Currently, research on organic electroluminescent materials has been focused on the academic world and the industrial world, and in the future, OLEDs are being developed to have high efficiency, high brightness, long lifetime, and low cost, but the light emitting characteristics of the light emitting layer still need to be improved, so that there is still a need to design new host materials with better performance to improve the performance of the organic electroluminescent device.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a condensed ring carbazole derivative having excellent properties, which is useful as a host material for an organic electroluminescent device; another object of the present invention is to provide an organic electroluminescent device comprising the fused ring carbazole derivative, which has a low driving voltage, high luminous efficiency, and a good lifetime.
The invention is realized by the following technical scheme:
a fused ring carbazole derivative represented by formula I:
Figure BDA0003132968310000021
wherein Ar is1Selected from the group represented by formula A;
Z1selected from O, S, CR1R2、NR3Any one of the above-mentioned (a) and (b),
Z2selected from O, S, CR1R2Any one of the above-mentioned (a) and (b),
R1、R2the aryl radicals are the same or different from each other and are independently selected from any one of hydrogen, deuterium, alkyl radicals of C1-C6 and aryl radicals of C6-C12,
or R1、R2Together with the carbon atom to which they are attached to form
Figure BDA0003132968310000022
R3Any one selected from substituted or unsubstituted aryl of C6-C30 and substituted or unsubstituted heteroaryl of C3-C30;
X1～X3identical or different from each other, independently selected from CH or N atoms, X1～X3At least two of which are selected from N atoms;
Ar2、Ar3the aryl groups are the same or different from each other and are independently selected from any one of substituted or unsubstituted aryl groups of C6-C30 and substituted or unsubstituted heteroaryl groups of C3-C30;
L1any one selected from single bond, substituted or unsubstituted arylene of C6-C30;
L2any one selected from single bond, substituted or unsubstituted arylene of C6-C30 and substituted or unsubstituted heteroarylene of C3-C30;
R0selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstitutedAny one of substituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
Raany one selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
m0an integer selected from 0 to 4, when m1Greater than 1, two or more R0Are the same or different from each other;
m1an integer selected from 0 to 4, when m1Greater than 1, two or more RaTwo R's, equal to or different from each other, or adjacentaThe connection between the two forms an aromatic ring or an aromatic heterocyclic ring.
The invention also provides an organic electroluminescent device which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises a light-emitting layer, and the light-emitting layer comprises the condensed ring carbazole derivative represented by the chemical formula I.
Advantageous effects
The fused ring carbazole derivative provided by the invention has a high triplet state energy level, inhibits triplet state energy backflow from a host to an object, and improves the luminous efficiency of an organic electroluminescent device. When the fused ring carbazole derivative provided by the invention is used as a host material, the concentration quenching generated by a guest material in an organic electroluminescent device can be effectively reduced, the efficiency roll-off of the organic electroluminescent device is inhibited, the service life of the device is prolonged, and meanwhile, the fused ring carbazole derivative provided by the invention has proper HOMO and LUMO energy levels, can be matched with the energy levels of adjacent functional layers, and reduces the injection barrier of holes and electrons, so that the driving voltage of the organic electroluminescent device is reduced; on the other hand, the whole structure of the fused ring carbazole derivative provided by the invention shows bipolarity, has good capability of balancing charge transmission, can effectively improve the luminous efficiency of a device, and reduces the driving voltage; meanwhile, the fused ring carbazole derivative provided by the invention has a larger conjugated unit, good thermal stability and film forming property, and the compound has a nonlinear structure on the whole structure, so that pi conjugation is broken, and further the triplet state energy level is improved, and the service life of the device is further improved.
In conclusion, the fused ring carbazole derivative provided by the invention has good application effect and industrialization prospect.
Drawings
FIG. 1 is a drawing showing the preparation of compounds 1 to 6 of the present invention1H NMR chart; FIG. 2 is a drawing showing the preparation of compounds 1 to 14 of the present invention1H NMR chart;
FIG. 3 is a drawing showing the preparation of compounds 1 to 59 of the present invention1H NMR chart; FIG. 4 is a drawing of compounds 1-64 of the present invention1H NMR chart;
FIG. 5 is a drawing of compounds 1-181 of the present invention1H NMR chart; FIG. 6 is a drawing showing the preparation of compounds 1 to 216 of the present invention1H NMR chart;
detailed description of the preferred embodiments
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. Various equivalent modifications of the invention which fall within the scope of the invention will occur to those skilled in the art after reading the disclosure herein.
Defining:
in the present specification, "+" means a moiety linked to another substituent. Without particular limitation, ""' may be attached to any optional position of the attached group/fragment. For example,
Figure BDA0003132968310000031
to represent
Figure BDA0003132968310000032
Similarly, any group attached to an aromatic ring can be attached to any optional position on the aromatic ring without indicating the position of attachment.
The alkyl group in the present invention refers to a hydrocarbon group obtained by removing one hydrogen atom from an alkane molecule, and may be a straight-chain alkyl group or a branched-chain alkyl group, preferably having 1 to 12 carbon atoms, more preferably having 1 to 10 carbon atoms, and particularly preferably having 1 to 6 carbon atoms, and examples thereof may include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, and the like.
The cycloalkyl group in the present invention means a hydrocarbon group obtained by removing one hydrogen atom from a cycloalkane molecule, preferably 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms, and examples thereof may include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, and the like.
The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from an aromatic nucleus carbon of an aromatic hydrocarbon molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms, and examples may include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, triphenylene group, fluorenyl group, spirofluorenyl group, perylenyl group, and the like, but is not limited thereto.
The heteroaryl group according to the present invention refers to an aromatic heterocyclic ring composed of carbon and hetero atoms, wherein one or more hydrogen atoms are removed from the core carbon, and the remaining monovalent group is N, O, S, and the heterocyclic ring may be monocyclic heteroaryl, polycyclic heteroaryl or fused heteroaryl, preferably having 3 to 30 carbon atoms, more preferably 3 to 16 carbon atoms, particularly preferably 3 to 12 carbon atoms, and most preferably 3 to 8 carbon atoms, and examples may include pyrrolyl, pyridyl, thienyl, furyl, indolyl, quinolyl, isoquinolyl, benzothienyl, benzofuryl, dibenzofuryl, dibenzothienyl, carbazolyl, phenazinyl, quinoxalyl, quinazolinyl, purinyl, imidazolyl, pyrimidyl, triazinyl, and the like, but is not limited thereto.
The arylene group in the present invention refers to a general term of divalent groups remaining after two hydrogen atoms are removed from the aromatic core carbon of the aromatic hydrocarbon molecule, and may be monocyclic arylene group, polycyclic arylene group or condensed ring arylene group, preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms, and examples may include phenylene, biphenylene, terphenylene, naphthylene, anthracenylene, phenanthrenylene, pyrenylene, triphenylene, fluorenylene, spirofluorenylene, peryleneene, and the like, but are not limited thereto.
The heteroarylene group according to the present invention refers to a general term in which two hydrogen atoms are removed from a core carbon of an aromatic heterocyclic ring composed of carbon and a hetero atom, leaving a divalent group, and the hetero atom may be one or more of N, O, S, and may be a monocyclic heteroarylene group, a polycyclic heteroarylene group or a condensed ring heteroarylene group, preferably having 3 to 30 carbon atoms, more preferably 3 to 16 carbon atoms, particularly preferably 3 to 12 carbon atoms, and most preferably 3 to 8 carbon atoms, and examples may include a pyrrolylene group, a pyridylene group, a thienylene group, a furylene group, an indolyl group, a quinolylene group, an isoquinolylene group, a benzothienylene group, a benzofuranylene group, a dibenzofuranylene group, a dibenzothiophenylene group, a carbazolyl group, a phenazinylene group, a quinoxalylene group, a quinazolinylene group, a purinylene group, an imidazolyl group, a pyrimidylene group, a triazinylene group and the like, but is not limited thereto.
The "substitution" as referred to herein means that a hydrogen atom in a compound group is replaced with another atom or group, and the position of substitution is not limited.
The "substituted or unsubstituted" as referred to herein means not substituted or substituted with one or more substituents selected from the group consisting of: deuterium, a halogen atom, an amino group, a cyano group, a nitro group, an alkyl group of C1-C30, a cycloalkyl group of C3-C20, an aryl group of C6-C60, an aryloxy group of C6-C60, an arylamine group of C6-C60, a heteroaryl group of C2-C60, preferably deuterium, a halogen atom, a cyano group, a nitro group, an alkyl group of C1-C12, a cycloalkyl group of C3-C12, an aryl group of C6-C30, a heteroaryl group of C2-C30, and specific examples may include deuterium, fluorine, chlorine, bromine, iodine, amino, cyano group, nitro group, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclohexyl, adamantyl, phenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, pyrenyl, chrysene yl, perylenyl, anthracenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylfluorenyl, 9-carbazolyl, 9-phenylfluorenyl, carbazolyl, and carbazolyl, Carbazolinyl, pyrrolyl, furanyl, thienyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, oxazolyl, thiazolyl, benzoxazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, phenothiazinyl, phenoxazinyl, acridinyl, and the like, but are not limited thereto.
The term "integer selected from 0 to M" as used herein means any one of the integers having a value selected from 0 to M, including 0, 1,2 … M-2, M-1, M. For example, "m" according to the present invention0The integer selected from 0 to 4 "means m0Selected from 0, 1,2, 3 or 4; "m" according to the invention1The integer selected from 0 to 4 "means m1Selected from 0, 1,2, 3 or 4; and so on.
The invention provides a fused ring carbazole derivative represented by chemical formula I:
Figure BDA0003132968310000051
wherein Ar is1Selected from the group represented by formula A;
Z1selected from O, S, CR1R2、NR3Any one of the above-mentioned (a) and (b),
Z2selected from O, S, CR1R2Any one of the above-mentioned (a) and (b),
R1、R2the aryl radicals are the same or different from each other and are independently selected from any one of hydrogen, deuterium, alkyl radicals of C1-C6 and aryl radicals of C6-C12,
or R1、R2Together with the carbon atom to which they are attached to form
Figure BDA0003132968310000052
R3Any one selected from substituted or unsubstituted aryl of C6-C30 and substituted or unsubstituted heteroaryl of C3-C30;
X1～X3identical or different from each other, independently selected from CH or N atoms, X1～X3At least two of which are selected from N atoms;
Ar2、Ar3the aryl groups are the same or different from each other and are independently selected from any one of substituted or unsubstituted aryl groups of C6-C30 and substituted or unsubstituted heteroaryl groups of C3-C30;
L1any one selected from single bond, substituted or unsubstituted arylene of C6-C30;
L2any one selected from single bond, substituted or unsubstituted arylene of C6-C30 and substituted or unsubstituted heteroarylene of C3-C30;
R0any one selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
Raany one selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
m0an integer selected from 0 to 4, when m1Greater than 1, two or more R0Are the same or different from each other;
m1an integer selected from 0 to 4, when m1Greater than 1, two or more RaTwo R's, equal to or different from each other, or adjacentaThe connection between the two forms an aromatic ring or an aromatic heterocyclic ring.
Preferably, the
Figure BDA0003132968310000053
Any one of the following structures:
Figure BDA0003132968310000054
preferably, the compound represented by the chemical formula I is selected from any one of the following chemical formulas I-a to I-f:
Figure BDA0003132968310000061
preferably, Ar is1Any one selected from the following groups:
Figure BDA0003132968310000062
more preferably, Ar is1Any one selected from the following groups:
Figure BDA0003132968310000063
Figure BDA0003132968310000071
preferably, Ar is2、Ar3The aryl group may be any one selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, and a substituted or unsubstituted quinazolinyl group, which may be the same or different from each other.
More preferably, Ar is2、Ar3The same or different from each other, and is independently selected from any one of the following groups:
Figure BDA0003132968310000072
Figure BDA0003132968310000081
preferably, Z is2Selected from O, S, CR1’R2' to any one of the above;
wherein R is1’、R2' same as each other, selected from any one of methyl and phenyl, or R1’、R2' together with the carbon atom to which it is attached to form
Figure BDA0003132968310000082
Preferably, Z is1Selected from O, S, CR1”R2”、NR3' to any one of the above;
wherein, R is1”、R2"the same or different from each other, independently selected from any one of methyl and phenyl, or R1”、R2"together with the carbon atom to which it is attached to form
Figure BDA0003132968310000083
The R is3' is any one selected from phenyl, biphenyl, terphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl and fluorenyl.
Preferably, said L1、L2Independently selected from any one of single bond, phenylene, biphenylene, terphenylene and naphthylene.
The "phenyl, biphenyl, terphenyl, naphthyl" according to the invention may be substituted by one or more of the group consisting of: deuterium, methyl, ethyl, isopropyl, tert-butyl, adamantyl, phenyl, biphenyl, naphthyl. In the case of being substituted with a plurality of substituents, the plurality of substituents may be the same as or different from each other.
Still more preferably, said L1、L2Independently selected from single bond or any one of the following groups:
Figure BDA0003132968310000084
most preferably, the compound of formula I is selected from any one of the following structures:
Figure BDA0003132968310000085
Figure BDA0003132968310000091
Figure BDA0003132968310000101
Figure BDA0003132968310000111
Figure BDA0003132968310000121
Figure BDA0003132968310000131
Figure BDA0003132968310000141
Figure BDA0003132968310000151
Figure BDA0003132968310000161
some specific structural forms of the compound of formula I according to the present invention are listed above, but the present invention is not limited to these listed chemical structures, and all the substituents based on the structure of formula I as defined above are all included.
The invention also provides a preparation method of the compound shown in the chemical formula I, but the preparation method is not limited to the preparation method. The core structure of the compounds of formula I can be prepared by the reaction schemes shown below, the substituents can be bonded by methods known in the art, and the type and position of the substituents or the number of substituents can be varied according to techniques known in the art.
[ preparation of intermediate A ]
Figure BDA0003132968310000162
[ preparation of intermediate B ]
Figure BDA0003132968310000163
[ preparation of the Compound of formula I ]
Figure BDA0003132968310000171
Z2、L1、L2、Ar1～Ar3、X1～X3、R0、Ra、m0、m1The definitions are the same as the above definitions; xa to Xc represent halogen atoms and are independently selected from any one of Br, Cl and I.
The main types of reactions involved in the present invention include the Suzuki-Miyaura reaction and the Buchwald-Hartwig reaction.
The invention also provides an organic electroluminescent device which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises a light-emitting layer, and the light-emitting layer comprises the condensed ring carbazole derivative represented by the chemical formula I.
Preferably, the light-emitting layer includes a first host and a second host, the second host includes a fused ring carbazole derivative represented by formula I, and the first host includes a compound represented by formula ii:
Figure BDA0003132968310000172
wherein Ar is4、Ar5The aryl groups are the same or different from each other and are independently selected from any one of substituted or unsubstituted aryl groups of C6-C30 and substituted or unsubstituted heteroaryl groups of C3-C30;
R4、R5the aryl group is any one of hydrogen, deuterium, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
wherein the "substituted" group is any one or more selected from deuterium, cyano, adamantyl, phenyl, biphenyl, and naphthyl, and when substituted with a plurality of substituents, the plurality of substituents may be the same or different from each other.
Preferably, Ar is4、Ar5The same or different from each other, and is independently selected from any one of the following groups:
Figure BDA0003132968310000173
most preferably, the compound of formula ii is selected from any one of the following structures:
Figure BDA0003132968310000174
Figure BDA0003132968310000181
Figure BDA0003132968310000191
while specific structural forms of the compounds of formula II of the present invention have been illustrated above, the present invention is not limited to these specific structural forms, and any substituent group defined above based on the structure of formula II should be included.
The organic layer of the organic electroluminescent device according to the present invention may include a light emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc., and each of the organic layers may further include one or more layers, for example, the hole transport layer may include a first hole transport layer and a second hole transport layer. However, the structure of the organic electroluminescent device is not limited thereto, and more or less organic layers may be included.
In the organic electroluminescent device of the present invention, the organic layer material may be any material used for the layer in the prior art. Preferably, the light-emitting layer comprises a compound described herein.
As the anode material of the present invention, a high work function material capable of promoting hole injection into the organic layer is preferably used. Specific examples of the anode material usable in the present invention may include: metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO); combinations of metals and oxides, such as ZnO: al or SnO2: sb; conducting polymers, e.g. poly (3-methylthiophene), polypyrrole, polyaniline, poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDT), etc., but not limited thereto.
As the cathode material of the present invention, a low work function material capable of promoting electron injection into the organic layer is preferably used. Specific examples of the cathode material that can be used in the present invention may include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, aluminum, silver, tin, lead, or alloys thereof; and multilayer materials, e.g. LiF/Al or LiO2and/Al, but not limited thereto.
As the hole injecting material of the present invention, a material having a good hole accepting ability is preferable, and the Highest Occupied Molecular Orbital (HOMO) of the hole injecting material is preferably a value between the work function of the anode material and the HOMO of the adjacent organic material layer. Specific examples of the hole injection material that can be used in the present invention may include: phthalocyanine compounds, benzidine compounds, phenazine compounds and the like, such as copper phthalocyanine, titanyl phthalocyanine, N, N '-diphenyl-N, N' -bis- [4- (N, N-diphenylamine) phenyl ] benzidine (NPNPNPB), N, N, N ', N' -tetrakis- (4-methoxyphenyl) benzidine (MeO-TPD), diquinoxalino [2,3-a:2',3' -c ] phenazine (HATNA) and the like, but not limited thereto.
As the hole transport material of the present invention, a material having excellent hole transport properties and a HOMO level matched to a corresponding anode material is preferable. Since the anode material generally has a high energy level, a material having a high HOMO energy level is selected as the hole transport material. Specific examples of the hole transport material usable in the present invention may include aromatic amine-based compounds, fluorene-based compounds, carbazole-based compounds, and the like, such as N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), 4- [1- [4- [ bis (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline (TAPC), N ' -tetrakis (3-methylphenyl) -3,3' -dimethylbiphenyldiamine (HMTPD), N ' -bis (naphthyl) -N, N ' -bis (phenyl) -2, 7-diamino-9, 9-diphenyl-fluorene (DPFL-NPB), and the like, but is not limited thereto.
The light-emitting layer material of the present invention may contain a phosphorescent material, and when a phosphorescent material is used, in order to avoid a concentration quenching phenomenon of the phosphorescent material, the light-emitting layer is usually prepared by co-depositing the phosphorescent material as a dopant material with another matrix material (host material), and the amount of the phosphorescent material is preferably 0.1 to 70 mass%, more preferably 0.1 to 40 mass%, further preferably 1 to 20 mass%, and particularly preferably 1 to 10 mass%.
Specific examples of the phosphorescent material that may be used in the present invention may include: heavy metal complexes (such as iridium complexes, platinum complexes, osmium complexes, etc.), phosphorescent rare earth metal complexes (such as terbium complexes, europium complexes), and the like, but are not limited thereto.
Specific examples of the host material usable in the present invention may include: the host material includes a fused aromatic ring derivative, a heterocyclic compound, a silicon-containing compound, and the like.
Preferably, the light-emitting layer includes the fused ring carbazole derivative represented by formula I described in the present invention.
Still preferably, the light-emitting layer includes a first host and a second host, the second host includes the fused ring carbazole derivative represented by formula I described above, and the first host includes the compound represented by formula ii described above.
The hole blocking material has better hole blocking capability and can block holes in the light emitting layer. Specific examples of the hole blocking material include, but are not limited to, the following: examples of the conjugated aromatic compound having an electron-withdrawing property include imidazole derivatives and phenanthroline derivatives, such as 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), bis (2-methyl-8-hydroxyquinoline-N1, O8) - (1,1' -biphenyl-4-hydroxy) aluminum (BAlq).
As the electron transporting material of the present invention, a material having a strong electron-withdrawing ability and a low HOMO and LUMO levels is preferable, and specific examples of the electron transporting material usable in the present invention may include imidazoles, triazoles, phenanthroline derivatives, quinolines, and the like, such as materials of 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris [ (3-pyridyl) -phenyl ] benzene (TmPyPB), 4' -bis (4, 6-diphenyl-1, 3, 5-triazinyl) biphenyl (BTB), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), 2- (naphthalen-2-yl) -4,7- (diphenyl) -1, 10-phenanthroline (HNBphen), 8-hydroxyquinoline-lithium, etc. (LiQ), but are not limited thereto.
The electron injecting material of the present invention is preferably a material having a small difference in potential barrier with respect to an adjacent organic transport material, host material, or the likeWith the effect of injecting electrons from the cathode. Examples of the electron injecting material that can be used in the present invention include: alkali metal salts (such as LiF, CsF), alkaline earth metal salts (such as MgF)2) Metal oxides (e.g. Al)2O3、MoO3) But is not limited thereto.
The organic electroluminescent device according to the present invention can be manufactured by sequentially laminating the above-described structures. The production method may employ a known method such as a dry film formation method or a wet film formation method. Specific examples of the dry film formation method include a vacuum deposition method, a sputtering method, a plasma method, an ion plating method, and the like. Specific examples of the wet film formation method include various coating methods such as a spin coating method, a dipping method, a casting method, and an ink jet method, but are not limited thereto.
The fabrication of the above-described organic electroluminescent device is specifically described in the following examples. However, the following examples are merely illustrative of the present specification, and the scope of the present specification is not limited to the examples.
Preparation and characterization of the Compounds
Description of raw materials, reagents and characterization equipment:
the raw materials used in the following examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art.
The mass spectrum uses British Watts G2-Si quadrupole rod series time-of-flight high resolution mass spectrometer, chloroform is used as solvent;
the element analysis uses a Vario EL cube type organic element analyzer of Germany Elementar company, and the mass of a sample is 5-10 mg;
nuclear magnetic resonance (1H NMR Spectroscopy) A nuclear magnetic resonance spectrometer model Bruker-510 (Bruker, Germany), 600MHz, CDCl was used3As solvent, TMS as internal standard.
EXAMPLE 1 Synthesis of Compounds 1-6
Figure BDA0003132968310000221
Synthesis of intermediate A-1:
under argon atmosphere, a reaction flask was charged with the starting material a-1(14.50g, 40mmol), the starting material b-1(11.43g, 45mmol), potassium acetate (7.85g, 80mmol) in that order, and then 250mL of toluene solvent and then PdCl were added2(dppf) (3.66g and 0.5mmol), stirring and heating to reflux for reaction for 8h, after the reaction is finished, cooling the mixture to room temperature, filtering through kieselguhr to remove the catalyst, concentrating the filtrate, carrying out suction filtration, and then recrystallizing with a mixed solution of dichloromethane and hexane to obtain an intermediate A-1(12.94g and 79%), wherein the solid purity is not less than 99.6% by HPLC (high performance liquid chromatography). Mass spectrum m/z: 409.2261 (theoretical value: 409.2213).
Synthesis of intermediate B-1:
a mixture of the starting material c-1(6.69g,25mmol), the intermediate A-1(10.64g,26mmol), potassium carbonate (6.91g,50 mmol) and tetrakis (triphenylphosphine) palladium (1.15g,1.0mmol) was added to a reaction flask under argon, followed by addition of a mixture of 20mL ethanol, 20mL water and 100mL toluene, and the mixture was stirred at room temperature under reflux for 16 hours. Pouring the mixture into 200mL of water under stirring, standing for liquid separation, extracting an aqueous phase with 50mL of toluene, combining organic phases, drying the organic phases by using 10g of anhydrous sodium sulfate, filtering, concentrating the filtrate under reduced pressure until no solvent is evaporated, and recrystallizing the filtrate by using toluene to obtain an intermediate B-1(11.19g, 87%), wherein the purity of the solid is not less than 99.7% by HPLC (high performance liquid chromatography). Mass spectrum m/z: 514.2182 (theoretical value: 514.2157).
Synthesis of Compounds 1-6:
raw material d-1(4.02g,12.5mmol), intermediate B-1(6.43g,12.5mmol) and sodium tert-butoxide (2.40g,25mmol) were dissolved in 100mL of dehydrated toluene under argon, and palladium acetate (0.14g,0.63mmol) and triphenylphosphine (0.16g,0.63mmol) were added with stirring to react at 100 ℃ for 8 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered by using kieselguhr, the filtrate is concentrated and filtered, the collected solid substances are recrystallized by using methanol to obtain the compounds 1-6(8.40g and 89%), and the purity of the solid is not less than 99.5% by HPLC (high performance liquid chromatography).
Mass spectrum m/z: 755.3088 (theoretical value: 755.3049). Theoretical element content (%) C54H37N5: c, 85.80; h, 4.93; and N, 9.26. Measured elemental content (%): c,85.83: H, 4.90;N,9.29。1H NMR(600MHz,CDCl3) (δ, ppm) 9.50(s,1H),8.60(s,1H),8.51 (s,1H),8.48(d,1H), 8.41-8.39 (m,2H), 8.37-8.35 (m,2H), 8.29-8.27 (m,1H),8.22(d,1H),8.15(s,1H), 8.12(d,2H),7.97(dd,2H),7.94(d,1H), 7.88-7.87 (m,1H),7.76(dd,1H), 7.70-7.68 (m,1H),7.60(t,2H), 7.54-7.51 (m,1H), 7.51-7.49 (m,6H),7.45(m,1H), 7.36-7.34 (m,1H), 7.29.55 (m,1H), 1H, 7.34(m, 1H). The above results confirmed that the obtained product was the objective product.
EXAMPLE 2 Synthesis of Compounds 1 to 10
Figure BDA0003132968310000231
Compound 1-10(7.14g) was prepared according to the synthetic method of example 1 by replacing d-1 in example 1 with an equimolar amount of d-2, and the solid purity was 99.6% or more by HPLC.
Mass spectrum m/z: 680.2529 (theoretical value: 680.2576). Theoretical element content (%) C48H32N4O: c, 84.68; h, 4.74; and N, 8.23. Measured elemental content (%): c, 84.65; h, 4.76; n, 8.21. The above results confirmed that the obtained product was the objective product.
EXAMPLE 3 Synthesis of Compounds 1 to 14
Figure BDA0003132968310000232
Compounds 1-14(7.51g) were prepared according to the synthetic procedure of example 1 by replacing d-1 in example 1 with an equimolar amount of d-3 and had a solid purity of 99.3% or more as determined by HPLC.
Mass spectrum m/z: 706.3041 (theoretical value: 706.3096). Theoretical element content (%) C51H38N4: c, 86.66; h, 5.42; and N, 7.93. Measured elemental content (%): c, 86.68; h, 5.39; and N, 7.96.1H NMR(600MHz,CDCl3)(δ,ppm):9.48(s,1H),8.49(s,1H), 8.40(m,2H),8.37(d,2H),8.27(d,1H),8.21(s,1H),8.17(d,1H),8.12(d,1H),8.04(s,1H),8.03(d,1H),7.96 (d,1H),7.87(d,1H),7.75(d,1H),7.70–7.67(m,1H),7.65(d,1H),7.56(m,1H), 7.52-7.49 (m,7H), 7.47-7.45 (m,1H),1.79(s,6H), 1.78(s, 6H). The above results confirmed that the obtained product was the objective product.
EXAMPLE 4 Synthesis of Compounds 1 to 23
Figure BDA0003132968310000233
Compounds 1-23(8.36g) were prepared according to the synthetic procedure of example 1 by replacing d-1 in example 1 with an equimolar amount of d-4 and had a solid purity of 99.4% or more as determined by HPLC.
Mass spectrum m/z: 805.3289 (theoretical value: 805.3205). Theoretical element content (%) C57H39N5：C,86.43；H,4.88；N,8.69。
Measured elemental content (%): c, 86.39; h, 4.91; n, 8.67. The above results confirmed that the obtained product was the objective product.
EXAMPLE 5 Synthesis of Compounds 1 to 56
Figure BDA0003132968310000241
Compounds 1-56(7.49g) were prepared according to the synthetic procedure of example 1 by replacing d-1 in example 1 with an equimolar amount of d-5 and had a solid purity of 99.6% or more as determined by HPLC.
Mass spectrum m/z: 696.2374 (theoretical value: 696.2348). Theoretical element content (%) C48H32N4S: c, 82.73; h, 4.63; and N, 8.04. Measured elemental content (%): c, 82.75; h, 4.60; and N, 8.06. The above results confirmed that the obtained product was the objective product.
EXAMPLE 6 Synthesis of Compounds 1 to 59
Figure BDA0003132968310000242
Compound 1-59 (8.03g, 85%) was prepared according to the synthetic method of example 1 by replacing the starting material a-1 in example 1 with an equimolar amount of the starting material a-2, and had a solid purity of 99.8% or more by HPLC.
Mass spectrum m/z: 755.3081 theoretical value: 755.3049). Theoretical element content (%) C54H37N5: c, 85.80; h, 4.93; and N, 9.26. Measured elemental content (%): c, 85.77; h, 4.92; and N, 9.28.1H NMR (600MHz, CDCl3) (Δ, ppm) 9.25(s,1H), 8.44-8.38 (m,4H), 8.20-8.19 (m,1H), 8.12-8.08 (m,1H),8.02(d,1H),7.96(s,1H),7.93(s,1H),7.87(s,1H), 7.66-7.63 (m,2H), 7.55-7.47 (m,10H),7.46(dd,1H), 7.42-7.36 (m,5H), 7.33-7.29 (m,2H),1.55(s, 6H). The above results confirmed that the obtained product was the objective product.
EXAMPLE 7 Synthesis of Compounds 1 to 64
Figure BDA0003132968310000251
d-6 Synthesis:
3-bromocarbazole (12.30g,50mmol), 2-iododibenzofuran (17.64g,60mmol) and sodium tert-butoxide (9.62g,100mmol) were dissolved in 250mL of dehydrated toluene under argon, and palladium acetate (0.56g,2.5mmol) and triphenylphosphine (0.65g,2.5mmol) were added with stirring and reacted at 100 ℃ for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered through celite, the filtrate was concentrated, suction-filtered and recrystallized from methanol to obtain compound d-6(16.07g, 78%) with a solid purity of 99.4% or more by HPLC. Mass spectrum m/z: 411.0274 (theoretical value: 411.0259).
Synthesis of Compounds 1-64:
compounds 1-64(8.88g) were prepared according to the synthetic procedure of example 1 by replacing d-1 in example 1 with an equimolar amount of d-6 and had a solid purity of 99.3% or more as determined by HPLC.
Mass spectrum m/z: 845.3178 (theoretical value: 845.3155). Theoretical element content (%) C60H39N5O: c, 85.18; h, 4.65; and N, 8.28. Measured elemental content (%): c, 85.20; h, 4.67; and N, 8.25.1H NMR(600MHz,CDCl3)(δ,ppm):9.51(s,1H),8.63(s,1H), 8.51(s,1H),8.50(d,1H),8.42–8.40(m,2H),8.40(s,1H),8.39–8.37(m,2H),8.32–8.30(m,1H),8.27(d,1H), 8.19-8.18 (m,1H),8.17(s,1H),8.17(d,1H),8.14(d,1H),8.03(d,1H), 7.99-7.97 (m,1H),7.90(d,1H),7.80 (d,1H), 7.77-7.75 (m,1H), 7.71-7.68 (m,1H),7.54(d,1H), 7.53-7.49 (m,7H), 7.48-7.43 (m,2H), 7.39-7.34 (m,2H),1.55(s, 6H). The above results confirmed that the obtained product was the objective product.
EXAMPLE 8 Synthesis of Compounds 1 to 96
Figure BDA0003132968310000252
Compounds 1-96 (7.84g) were prepared according to the synthetic procedure of example 1 by replacing the starting material a-1 in example 1 with an equimolar amount of starting material a-3 and had a solid purity of 99.8% or more as determined by HPLC.
Mass spectrum m/z: 729.2574 (theoretical value: 729.2529). Theoretical element content (%) C51H31N5O: c, 83.93; h, 4.28; and N, 9.60. Measured elemental content (%): c, 83.90; h, 4.30; and N, 9.63. The above results confirmed that the obtained product was the objective product.
EXAMPLE 9 Synthesis of Compounds 1 to 113
Figure BDA0003132968310000261
Compounds 1-113(6.95g) were prepared according to the synthetic procedure of example 1 by replacing the starting material a-1 with an equimolar amount of starting material a-3 and the starting material d-1 with an equimolar amount of starting material d-7 as in example 1, and had a solid purity of 99.4% or more as determined by HPLC.
Mass spectrum m/z: 670.1849 (theoretical value: 670.1827). Theoretical element content (%) C45H26N4And OS: c, 80.58; h, 3.91; and N, 8.35. Measured elemental content (%): c, 80.55; h, 3.93; n, 8.32. The above results confirmed that the obtained product was the objective product.
EXAMPLE 10 Synthesis of Compounds 1 to 164
Figure BDA0003132968310000262
Compounds 1-164(7.12g) were prepared according to the synthetic method of example 1 by replacing the starting material a-1 in example 1 with an equimolar amount of starting material a-4 and the starting material d-1 with an equimolar amount of starting material d-2, and the solid purity was 99.5% or more by HPLC.
Mass spectrum m/z: 670.1819 theoretical value: (670.1827). Theoretical element content (%) C45H26N4And OS: c, 80.58; h, 3.91; and N, 8.35. Measured elemental content (%): c, 80.60; h, 3.92; n, 8.37. The above results confirmed that the obtained product was the objective product.
EXAMPLE 11 Synthesis of Compounds 1 to 177
Figure BDA0003132968310000263
Compound 1-177 (8.26g) was prepared according to the synthetic method of example 1 by replacing the starting material c-1 of example 1 with an equimolar amount of the starting material c-2, and the solid purity was 99.8% or more by HPLC.
Mass spectrum m/z: 805.3254 (theoretical value: 805.3205). Theoretical element content (%) C58H39N5：C,86.43；H,4.88；N,8.69。
Measured elemental content (%): c, 86.45; h, 4.85; n, 8.67. The above results confirmed that the obtained product was the objective product.
EXAMPLE 12 Synthesis of Compounds 1 to 181
Figure BDA0003132968310000271
Compounds 1-181(8.36g, solid purity ≥ 99.6% by HPLC) were prepared according to the synthetic procedure for example 1, substituting the starting material a-1 for an equimolar amount of starting material a-3 and substituting the starting material c-1 for an equimolar amount of starting material c-3 in example 1.
Mass spectrum m/z: 805.2878 (theoretical value: 805.2842). Theoretical element content (%) C57H35N5O: c, 84.95; h, 4.38; and N, 8.69. Measured elemental content (%): c,84.96；H,4.40；N,8.67。1H NMR(600MHz,CDCl3) (δ, ppm) 9.53(s,1H),8.68(s,1H), 8.53(d,1H),8.52(s,1H), 8.43-8.41 (m,2H),8.30(d,1H),8.26(d,1H),8.20(s,1H), 8.18-8.16 (m,1H),8.13 (m,3H), 7.99-7.97 (m,2H),7.95(d,1H), 7.90-7.88 (m,1H),7.78(d,2H), 7.61-7.58 (m,4H), 7.55-7.53 (m,1H), 7.51-7.49 (m,3H), 7.46-7.43 (m,4H), 7.36-7.29 (m, 4H). The above results confirmed that the obtained product was the objective product.
EXAMPLE 13 Synthesis of Compounds 1-192
Figure BDA0003132968310000272
Compounds 1-192 (8.02g) were prepared according to the synthetic procedure of example 1 by replacing the starting material c-1 of example 1 with an equimolar amount of starting material c-4 and had a solid purity of 99.7% or more as determined by HPLC.
Mass spectrum m/z: 754.3048 (theoretical value: 754.3096). Theoretical element content (%) C55H38N4：C,87.50；H,5.07；N,7.42。
Measured elemental content (%): c, 87.52; h, 5.06; and N, 7.42. The above results confirmed that the obtained product was the objective product.
EXAMPLE 14 Synthesis of Compounds 1-196
Figure BDA0003132968310000273
Compounds 1-196 (8.52g) were prepared according to the synthetic procedure of example 1, substituting the starting material c-1 of example 1 with an equimolar amount of starting material c-5, and had a solid purity of 99.5% or more as determined by HPLC.
Mass spectrum m/z: 831.3325 (theoretical value: 831.3362). Theoretical element content (%) C60H41N5：C,86.62；H,4.97；N,8.42。
Measured elemental content (%): c, 86.63; h, 4.96; and N, 8.45. The above results confirmed that the obtained product was the objective product.
EXAMPLE 15 Synthesis of Compounds 1-216
Figure BDA0003132968310000281
Compounds 1-216 (7.66g) were prepared according to the synthetic procedure of example 1 by replacing the starting material a-1 in example 1 with an equimolar amount of starting material a-5, and had a solid purity of 99.8% or more as determined by HPLC.
Mass spectrum m/z: 729.2548 (theoretical value: 729.2529). Theoretical element content (%) C51H31N5O: c, 83.93; h, 4.28; and N, 9.60. Measured elemental content (%): c, 83.94; h, 4.29; and N, 9.58.1H NMR(600MHz,CDCl3) (delta, ppm) 9.94(s,1H),8.72(d,1H), 8.63(s,1H), 8.51-8.49 (m,1H),8.46(dd,2H), 8.39-8.37 (m,2H), 8.33-8.30 (m,2H), 8.13-8.11 (m,1H), 7.99-7.97 (m,2H),7.95(d,2H), 7.88-7.86 (m,1H),7.79(d,2H), 7.67-7.64 (m,1H),7.60(t,2H), 7.51-7.49 (m,6H), 7.46-7.43 (m,2H), 7.36-7.34 (m,1H), 7.30-7.28 (m, 1H). The above results confirmed that the obtained product was the objective product.
In the invention, all organic materials used in the evaporation process of the device are sublimated, and the purity is over 99.99 percent. The ITO glass substrate used in the experiment is purchased from Shenzhen south glass display device science and technology Limited. The ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning solution, and then ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C.
The device is prepared by adopting a vacuum evaporation system and continuously evaporating under a vacuum uninterrupted condition. The materials are respectively arranged in different evaporation source quartz crucibles, and the temperatures of the evaporation sources can be independently controlled. The thermal evaporation rate of the organic material involved in the evaporation process is generally fixed at 0.1 nm/s, and the evaporation rate of the doping material is adjusted according to the doping ratio; the evaporation rate of the electrode metal is 0.4-0.6 nm/s. Placing the processed glass substrate into an OLED vacuum coating machine, wherein the vacuum degree of the system should be maintained at 5 x 10 in the film manufacturing process-5Respectively evaporating an organic layer and gold below Pa by replacing a mask plateThe evaporation rate of the electrode is detected by an SQM160 quartz crystal film thickness detector of Inficon, and the film thickness is detected by a quartz crystal oscillator.
Device example 1
And (3) performing vacuum evaporation on the cleaned ITO substrate to form a hole injection layer by using 2-TNATA, wherein the evaporation thickness is 60 nm. NPB was vacuum-deposited on the hole injection layer to form a hole transport layer, and the thickness of the deposition was 25 nm. Vacuum evaporation of inventive compounds 1 to 6 on the hole transport layer: ir (dpm) (piq)2(weight ratio: 90:10) to form a light-emitting layer, and the thickness was 30nm by vapor deposition. Vacuum evaporation of Alq on the luminescent layer3An electron transport layer was formed, and the thickness was 40nm by evaporation. And evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, evaporating aluminum with the thickness of 1nm to form a cathode, and then evaporating aluminum with the thickness of 100nm to prepare the organic electroluminescent device 1.
The organic electroluminescent materials used in the device examples of the present invention are as follows:
Figure BDA0003132968310000291
device examples 2 to 15
Organic electroluminescent devices 2 to 15 were produced in the same production method as in device example 1, except that compounds 1 to 10, compounds 1 to 14, compounds 1 to 23, compounds 1 to 56, compounds 1 to 59, compounds 1 to 64, compounds 1 to 96, compounds 1 to 113, compounds 1 to 164, compounds 1 to 177, compounds 1 to 181, compounds 1 to 192, compounds 1 to 196 and compounds 1 to 216 of the present invention were used as host materials instead of compounds 1 to 6 in device example 1.
Comparative examples 1 to 5
Comparative devices 1 to 5 were prepared in the same manner as in device example 1 except that the compounds HOST-1, HOST-2, HOST-3, HOST-4 and HOST-5 were used as HOST materials instead of the compounds 1 to 6 in device example 1.
Device example 16
Vacuum evaporating HI-1 on the cleaned glass substrateA first hole injection layer was formed, and the thickness was 80nm by evaporation. And vacuum evaporating HI-2 on the first hole injection layer to form a second hole injection layer, wherein the evaporation thickness is 5 nm. NPB was vacuum-evaporated as a hole transport layer on the second hole injection layer to a thickness of 20 nm. Vacuum evaporation of inventive Compounds 2-7 as the first host, inventive Compounds 1-10 as the second host, and Ir (dpm) or piq on the hole transport layer at a weight ratio of 45:45:102The light-emitting layer was formed as a dopant and deposited to a thickness of 40 nm. BAlq was vacuum-deposited on the light-emitting layer to form a hole-blocking layer, and the deposition thickness was 5 nm. Vacuum evaporation of Alq on hole blocking layer3An electron transport layer was formed, and evaporation was performed to a thickness of 20nm, LiF was vacuum-evaporated on the electron transport layer to form an electron injection layer, and evaporation was performed to a thickness of 1nm, and then aluminum was evaporated to a thickness of 100nm to form a cathode, thereby preparing the organic electroluminescent device 16.
Device examples 17 to 20
Organic electroluminescent devices 17 to 20 were produced in the same manner as in device example 16, except that compounds 1 to 14, compounds 1 to 56, compounds 1 to 113, and compounds 1 to 164 of the present invention were used as the second host in place of compounds 1 to 10.
Device example 21
An organic electroluminescent device 21 was produced in the same production method as in device example 16, except that the compounds 2 to 9 of the present invention were used as the first host instead of the compounds 2 to 7.
Device example 22
An organic electroluminescent device 22 was produced in the same production method as in device example 16, except that the compounds 2 to 9 according to the present invention were used instead of the compounds 2 to 7 as the first host and the compounds 1 to 14 according to the present invention were used instead of the compounds 1 to 10 as the second host.
Device example 23
An organic electroluminescent device 23 was produced in the same production method as in device example 16, except that the compounds 2 to 9 according to the present invention were used instead of the compounds 2 to 7 as the first host and the compounds 1 to 56 according to the present invention were used instead of the compounds 1 to 10 as the second host.
Device example 24
An organic electroluminescent device 24 was produced in the same production method as in device example 16, except that the compounds 2 to 9 according to the present invention were used instead of the compounds 2 to 7 as the first host and the compounds 1 to 113 according to the present invention were used instead of the compounds 1 to 10 as the second host.
Device example 25
An organic electroluminescent device 25 was produced in the same production method as in device example 16, except that the compounds 2 to 9 according to the present invention were used instead of the compounds 2 to 7 as the first host and the compounds 1 to 164 according to the present invention were used instead of the compounds 1 to 10 as the second host.
Device example 26
An organic electroluminescent device 26 was produced in the same production method as in device example 16, except that the compounds 2 to 22 of the present invention were used as the first host instead of the compounds 2 to 7.
Device example 27
An organic electroluminescent device 27 was produced in the same production method as in device example 16, except that the compounds 2 to 22 according to the present invention were used instead of the compounds 2 to 7 as the first host and the compounds 1 to 14 according to the present invention were used instead of the compounds 1 to 10 as the second host.
Device example 28
An organic electroluminescent device 28 was produced in the same production method as in device example 16, except that the compounds 2 to 22 according to the present invention were used instead of the compounds 2 to 7 as the first host and the compounds 1 to 56 according to the present invention were used instead of the compounds 1 to 10 as the second host.
Device example 29
An organic electroluminescent device 29 was produced in the same production method as in device example 16, except that the compounds 2 to 22 according to the present invention were used instead of the compounds 2 to 7 as the first host and the compounds 1 to 113 according to the present invention were used instead of the compounds 1 to 10 as the second host.
Device example 30
An organic electroluminescent device 30 was produced in the same production method as in device example 16, except that the compounds 2 to 22 according to the present invention were used instead of the compounds 2 to 7 as the first host and the compounds 1 to 164 according to the present invention were used instead of the compounds 1 to 10 as the second host.
[ comparative example 6]
Comparative device 6 was prepared in the same manufacturing method as device example 16, except that the comparative compound HOST-3 was used instead of the compounds 1 to 10 of the present invention as the second HOST.
[ comparative example 7]
Comparative device 7 was prepared in the same manufacturing method as device example 16, except that the comparative compound HOST-4 was used instead of the compounds 1 to 10 of the present invention as the second HOST.
[ comparative example 8]
Comparative device 8 was prepared in the same manufacturing method as device example 16, except that inventive compounds 2-22 were used as the first HOST instead of compounds 2-7, and comparative compound HOST-4 was used as the second HOST instead of inventive compounds 1-10.
[ comparative example 9]
Comparative device 9 was prepared in the same manufacturing method as device example 16 except that inventive compounds 2-22 were used as the first HOST instead of compounds 2-7 and comparative compound HOST-4 was used as the second HOST instead of inventive compounds 1-10.
A joint IVL test system is formed by test software, a computer, a K2400 digital source meter manufactured by Keithley of the United states and a PR788 spectral scanning luminance meter manufactured by Photo Research of the United states to test the driving voltage and the luminous efficiency of the organic light-emitting device. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature. The results of the test of the light emitting characteristics of the organic electroluminescent devices obtained in the device examples 1 to 15 of the present invention and the comparative examples 1 to 4 are shown in table 1. The results of the light-emitting characteristics of the organic electroluminescent devices obtained in device examples 16 to 35 and comparative examples 5 to 8 are shown in Table 2. T95 means the time required for the luminance to drop to 95% of its initial luminance (5000 nits).
Table 1 test of light emitting characteristics of organic electroluminescent device
Figure BDA0003132968310000311
Figure BDA0003132968310000321
The results in table 1 show that when the fused ring carbazole derivative provided by the invention is used as a main material and applied to an organic electroluminescent device, the driving voltage can be reduced to a certain extent, the luminous efficiency of the device is effectively improved, and the service life of the device is effectively prolonged; the overall structure of the compound of the present invention used in device example 1, device example 4, device example 6, device example 7, device example 8, and device examples 11 to 15 shows more excellent bipolar, and has higher triplet energy levels, HOMO and LUMO energy levels are matched with adjacent functional layers, and the compound shows more excellent device performance when used alone as a host material of an organic electroluminescent device.
Table 2 test of light emitting characteristics of organic electroluminescent device
Figure BDA0003132968310000322
Figure BDA0003132968310000331
The results in table 2 show that when the fused ring carbazole derivative provided by the present invention and the compound of formula ii of the present invention are used as host materials in an organic electroluminescent device, the effective combination of the hole-type host material and the electron-type host material can further reduce the driving voltage of the device, improve the luminous efficiency of the device, and prolong the lifetime of the device.
It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.

Claims (10)

1. A fused carbazole derivative represented by the following formula I:
Figure FDA0003132968300000011
wherein Ar is1Selected from the group represented by formula A;
Z1selected from O, S, CR1R2、NR3Any one of the above-mentioned (a) and (b),
Z2selected from O, S, CR1R2Any one of the above-mentioned (a) and (b),
R1、R2the same or different from each other, and is independently selected from any one of hydrogen, deuterium, alkyl of C1-C6, aryl of C6-C12, or R1、R2Together with the carbon atom to which they are attached to form
Figure FDA0003132968300000012
R3Any one selected from substituted or unsubstituted aryl of C6-C30 and substituted or unsubstituted heteroaryl of C3-C30;
X1～X3identical or different from each other, independently selected from CH or N atoms, X1～X3At least two of which are selected from N atoms;
Ar2、Ar3the aryl groups are the same or different from each other and are independently selected from any one of substituted or unsubstituted aryl groups of C6-C30 and substituted or unsubstituted heteroaryl groups of C3-C30;
L1any one selected from single bond, substituted or unsubstituted arylene of C6-C30;
L2any one selected from single bond, substituted or unsubstituted arylene of C6-C30 and substituted or unsubstituted heteroarylene of C3-C30;
R0selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C12 alkyl,Any one of substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
Raany one selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
m0an integer selected from 0 to 4, when m1Greater than 1, two or more R0Are the same or different from each other;
m1an integer selected from 0 to 4, when m1Greater than 1, two or more RaTwo R's, equal to or different from each other, or adjacentaThe connection between the two forms an aromatic ring or an aromatic heterocyclic ring.
2. A fused ring carbazole derivative according to claim 1, wherein the compound represented by formula i is selected from any one of the following formulae i-a to i-f:
Figure FDA0003132968300000013
Figure FDA0003132968300000021
3. a fused ring carbazole derivative according to claim 1, wherein Ar is present1Any one selected from the following groups:
Figure FDA0003132968300000022
4. a fused ring carbazole derivative according to claim 1, whereinAr is described2、Ar3The same or different from each other, and is independently selected from any one of the following groups:
Figure FDA0003132968300000023
Figure FDA0003132968300000031
5. a fused ring carbazole derivative according to claim 1, wherein Z is2Selected from O, S, CR1’R2' to any one of the above;
wherein R is1’、R2' same as each other, selected from any one of methyl and phenyl, or R1’、R2' together with the carbon atom to which it is attached to form
Figure FDA0003132968300000032
6. A fused ring carbazole derivative according to claim 1, wherein the compound represented by formula i is selected from any one of the following structures:
Figure FDA0003132968300000033
Figure FDA0003132968300000041
Figure FDA0003132968300000051
Figure FDA0003132968300000061
Figure FDA0003132968300000071
Figure FDA0003132968300000081
Figure FDA0003132968300000091
Figure FDA0003132968300000101
Figure FDA0003132968300000111
7. an organic electroluminescent device comprising an anode, an organic layer, and a cathode, wherein the organic layer comprises a light-emitting layer, and wherein the light-emitting layer comprises any one of the fused ring carbazole derivatives of claims 1 to 6.
8. The organic electroluminescent device according to claim 7, wherein the light-emitting layer comprises a first host and a second host, the second host comprises any one of the fused ring carbazole derivatives of claims 1 to 6, and the first host comprises a compound represented by formula II:
Figure FDA0003132968300000112
wherein Ar is4、Ar5The aryl groups are the same or different from each other and are independently selected from any one of substituted or unsubstituted aryl groups of C6-C30 and substituted or unsubstituted heteroaryl groups of C3-C30;
R4、R5the aryl group is any one of hydrogen, deuterium, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
wherein the "substituted" group is any one or more selected from deuterium, cyano, adamantyl, phenyl, biphenyl, and naphthyl, and when substituted with a plurality of substituents, the plurality of substituents may be the same or different from each other.
9. The organic electroluminescent device of claim 8, wherein Ar is selected from the group consisting of4、Ar5The same or different from each other, and is independently selected from any one of the following groups:
Figure FDA0003132968300000113
10. the organic electroluminescent device as claimed in claim 8, wherein the compound represented by formula ii is selected from any one of the following structures:
Figure FDA0003132968300000121
Figure FDA0003132968300000131
Figure FDA0003132968300000141
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