CN116507619A - Compound and organic light emitting device comprising the same - Google Patents

Compound and organic light emitting device comprising the same Download PDF

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Publication number
CN116507619A
CN116507619A CN202180076967.6A CN202180076967A CN116507619A CN 116507619 A CN116507619 A CN 116507619A CN 202180076967 A CN202180076967 A CN 202180076967A CN 116507619 A CN116507619 A CN 116507619A
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车龙范
曹宇珍
洪性佶
李炯珍
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LG Chem Ltd
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LG Chem Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H10K50/181—Electron blocking layers

Abstract

The present specification relates to a compound and an organic light emitting device including the same.

Description

Compound and organic light emitting device comprising the same
Technical Field
The present application claims priority from korean patent application No. 10-2021-0004536, filed by the korean patent office on day 2021, month 13, the entire contents of which are incorporated herein.
The present specification relates to a compound and an organic light emitting device including the same.
Background
The organic light emitting device has a structure in which an organic thin film is disposed between 2 electrodes. If a voltage is applied to the organic light emitting device of such a structure, electrons and holes injected from 2 electrodes are combined in an organic thin film to be quenched and emitted light in pairs. The organic thin film may be formed of a single layer or a plurality of layers as required.
As the substance used in the organic light-emitting device, a pure organic substance or a complex compound of an organic substance and a metal constituting a complex is largely classified into a hole-injecting substance, a hole-transporting substance, a light-emitting substance, an electron-transporting substance, an electron-injecting substance, and the like depending on the application. Here, as the hole injecting substance or the hole transporting substance, an organic substance having a p-type property, that is, an organic substance which is easily oxidized and has an electrochemically stable state when oxidized is mainly used. On the other hand, as the electron injecting substance or the electron transporting substance, an organic substance having n-type property, that is, an organic substance which is easily reduced and has an electrochemically stable state at the time of reduction is mainly used. As the light-emitting layer material, a material having both p-type property and n-type property, that is, a material having a stable form in both the oxidized and reduced states, and a material having high light emission efficiency for converting excitons (exiton) generated by recombination of holes and electrons in the light-emitting layer into light when formed, is preferable.
In order to improve the performance, lifetime, or efficiency of an organic light emitting device, development of materials for organic thin films is continuously required.
Disclosure of Invention
Technical problem
The present specification provides compounds and organic light emitting devices comprising the same.
Solution to the problem
An embodiment of the present specification provides a compound of the following chemical formula 1.
[ chemical formula 1]
In the above-mentioned chemical formula 1,
r1 and R2 are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
l1 to L3 are identical to or different from each other and are each independently a direct bond or a substituted or unsubstituted arylene group,
ar1 and Ar2 are the same as or different from each other, each independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
a is an integer of 1 to 4, and when a is 2 or more, 2 or more R1 s are the same or different from each other,
b is an integer of 1 to 4, and when b is 2 or more, 2 or more R2 s are the same or different from each other,
r1 to r3 are each integers of 1 to 3, and when r1 to r3 are each 2 or more, the structures in each bracket are the same or different from each other.
In addition, an embodiment of the present specification provides an organic light emitting device, including: a first electrode, a second electrode, and 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 or more of the organic layers contain the compound.
Effects of the invention
The compound according to an embodiment of the present specification may be used as a material of an organic layer of an organic light emitting device, and by using the compound, an improvement in efficiency, a lower driving voltage, and/or an improvement in lifetime characteristics may be achieved in the organic light emitting device.
In particular, when the compound of the present invention is used for a hole injection layer, a hole transport layer, or an electron blocking layer, the effect of reducing the driving voltage of the device, increasing the efficiency of the device, and prolonging the lifetime can be obtained.
Drawings
Fig. 1 to 3 illustrate an organic light emitting device according to an embodiment of the present specification.
1: substrate board
2: first electrode
3: light-emitting layer
4: second electrode
5: hole injection layer
6: hole transport layer
7: light-emitting layer
8: electron transport layer
9: electron blocking layer
10: hole blocking layer
11: electron injection and transport layers
Detailed Description
The present specification will be described in more detail below.
The present specification provides a compound of the following chemical formula 1.
[ chemical formula 1]
In the above-mentioned chemical formula 1,
r1 and R2 are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
L1 to L3 are identical to or different from each other and are each independently a direct bond or a substituted or unsubstituted arylene group,
ar1 and Ar2 are the same as or different from each other, each independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
a is an integer of 1 to 4, and when a is 2 or more, 2 or more R1 s are the same or different from each other,
b is an integer of 1 to 4, and when b is 2 or more, 2 or more R2 s are the same or different from each other,
r1 to r3 are each integers of 1 to 3, and when r1 to r3 are each 2 or more, the structures in each bracket are the same or different from each other.
The compound of chemical formula 1 is characterized in that when the carbon atom of the naphthyl group is numbered as shown below, the carbon atom No. 1 is substituted with an amine group and the carbon atom No. 2 is substituted with a carbazole group.
In this specification, when it is stated that a certain member is located "on" another member, it includes not only the case where the certain member is connected to the other member but also the case where another member exists between the two members.
In the present specification, when a certain component is referred to as "including" or "comprising" a certain component, unless otherwise specified, it means that other components may be further included, and not excluded.
Hereinafter, the substituents of the present specification will be described in detail, but are not limited thereto.
In the present description of the invention,represents a site of binding to another substituent or binding moiety.
In the present specification, the term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the substituted position is not limited as long as it is a position where a hydrogen atom can be substituted, that is, a position where a substituent can be substituted, and when 2 or more substituents are substituted, 2 or more substituents may be the same or different from each other.
In the present specification, the term "substituted or unsubstituted" means substituted with 1 or 2 or more substituents selected from deuterium, halogen group, cyano (-CN), amino, alkoxy, alkyl, aryl and heterocyclic group, or substituted with a substituent in which 2 or more substituents out of the above exemplified substituents are linked, or does not have any substituent. For example, the "substituent in which 2 or more substituents are linked" may be a biphenyl group. That is, biphenyl may be aryl or may be interpreted as a substituent in which 2 phenyl groups are linked.
In the present specification, as examples of the halogen group, there are fluorine (-F), chlorine (-Cl), bromine (-Br) or iodine (-I).
In the present specification, the alkyl group may be a straight chain or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples thereof include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.
In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, for example, an aryl group having 6 to 30 carbon atoms, and the aryl group may be a single ring or a multiple ring.
When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30. Specifically, the monocyclic aryl group may be phenyl, biphenyl, terphenyl, or the like, but is not limited thereto.
When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 10 to 30. Specifically, the polycyclic aryl group may be naphthyl, anthryl, phenanthryl, triphenylene, pyrenyl, phenalenyl, perylenyl,A group, a fluorenyl group, a fluoranthenyl group, and the like, but is not limited thereto.
In the present specification, the above fluorenyl group may be substituted, and adjacent groups may be bonded to each other to form a ring.
In the case where the fluorenyl group is substituted, it may be thatAnd->Etc. However, the present invention is not limited thereto.
In the present specification, arylene means a group having two bonding positions on an aryl group, i.e., a 2-valent group. These are not limited to the 2-valent groups, and the above description of the aryl groups may be applied.
In this specification, a heterocyclic group contains 1 or more heteroatoms which are non-carbon atoms, and specifically, the heteroatoms may contain 1 or more atoms selected from O, N, S, P and the like. The number of carbon atoms is not particularly limited, but is preferably 1 to 50, more preferably 2 to 30, and the heterocyclic group may be a single ring or a multiple ring. The heterocyclic group may be an aromatic ring, an aliphatic ring, or a ring obtained by fusing them. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, and the like, Azolyl, (-) -and (II) radicals>Diazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzo->Oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, benzofuranyl, phenanthroline (phenanthrinyl), iso>Oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but are not limited thereto.
In the present specification, a heteroaryl group is an aromatic ring group containing 1 or more heteroatoms which are non-carbon atoms, and specifically, the heteroatoms may contain 1 or more atoms selected from O, N, se, S and the like. The number of carbon atoms is not particularly limited, but is preferably 2 to 60. According to one embodiment, the heteroaryl group has 2 to 30 carbon atoms. Examples of heteroaryl groups may be selected from examples of heterocyclic groups described above.
In the present specification, the above-mentioned alkoxy group may be a straight chain, branched or cyclic. The carbon number of the alkoxy group is not particularly limited, but is preferably 1 to 30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decyloxy and the like are possible, but not limited thereto.
In the present specification, the amine group may be selected from the group consisting of-NH 2 The alkyl amine group, the N-alkylaryl amine group, the aryl amine group, the N-arylheteroaryl amine group, the N-alkylheteroaryl amine group and the heteroaryl amine group are not particularly limited, but are preferably 0 to 30 in carbon number. Specific examples of the amine group include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a phenylamine group, a naphthylamino group, a biphenylamino group, an anthracenylamino group, a 9-methyl-anthracenylamino group, a diphenylamino group, an N-phenylnaphthylamino group, a xylylamino group, an N-phenyltolylamino group, a triphenylamino group, an N-phenylbiphenylamino group, an N-phenylnaphthylamino group, an N-biphenylnaphthylamino group, an N-naphthylfluorenylamino group, an N-phenylphenanthrylamino group, an N-biphenylphenanthrenylamino group, an N-phenylfluorenylamino group, an N-biphenylfluorenylamino group, and the like, but are not limited thereto.
In the present specification, the N-alkylaryl amine group means an amine group in which an alkyl group and an aryl group are substituted on N of the amine group.
In the present specification, an N-arylheteroarylamino group means an amino group substituted with an aryl group and a heteroaryl group on N of the amino group.
In the present specification, an N-alkylheteroarylamino group means an amino group in which an alkyl group and a heteroaryl group are substituted on N of the amino group.
In the present specification, alkyl groups and aryl groups in the alkylamino group, the N-arylalkylamino group, and the N-alkylheteroarylamino group are the same as those exemplified for the alkyl groups and the aryl groups described above.
In one embodiment of the present specification, R1 and R2 are the same or different from each other, and each is independently hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
In one embodiment of the present specification, R1 and R2 are the same or different from each other, and each is independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic group having 1 to 50 carbon atoms.
In one embodiment of the present specification, R1 and R2 are the same or different from each other, and each is independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
In one embodiment of the present specification, R1 and R2 are the same or different from each other, and each is independently hydrogen or deuterium.
In one embodiment of the present specification, each of R1 and R2 is hydrogen.
In one embodiment of the present specification, a is an integer of 1 to 4, and when a is 2 or more, 2 or more R1 s are the same or different from each other.
In one embodiment of the present specification, R1 is hydrogen, and a is 4.
In one embodiment of the present specification, b is an integer of 1 to 4, and when b is 2 or more, 2 or more R2 are the same or different from each other.
In one embodiment of the present specification, R2 is hydrogen, and b is 4.
In one embodiment of the present specification, L1 to L3 are the same or different from each other, and each is independently a direct bond, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.
In an embodiment of the present specification, the above-mentioned L1 to L3 are the same or different from each other, and each is independently a direct bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted fluorenylene group.
In one embodiment of the present specification, L1 and L2 are the same or different from each other, and each is independently a direct bond, or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms.
In one embodiment of the present specification, the above-mentioned L1 and L2 are the same or different from each other, and each is independently a direct bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted fluorenylene group.
In one embodiment of the present specification, the above-mentioned L1 and L2 are the same or different from each other, and each is independently a direct bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, or a substituted or unsubstituted naphthylene group.
In one embodiment of the present specification, the above L1 and L2 are the same or different from each other, and each is independently a direct bond, phenylene, biphenylene, terphenylene or naphthylene.
In one embodiment of the present specification, L3 is a direct bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group.
In one embodiment of the present specification, the L3 is a direct bond, phenylene or biphenylene.
In one embodiment of the present specification, the L3 is phenylene or biphenylene.
In one embodiment of the present specification, ar1 and Ar2 are the same or different and each is independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
In one embodiment of the present specification, ar1 and Ar2 are the same or different from each other and are each independently 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 phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothienyl group.
In one embodiment of the present specification, ar1 and Ar2 mentioned above are the same or different from each other, and each is independently a phenyl group substituted or unsubstituted with an alkyl group, an aryl group or a heterocyclic group; biphenyl substituted or unsubstituted with alkyl, aryl, or heterocyclyl; terphenyl substituted or unsubstituted with alkyl, aryl or heterocyclyl; naphthyl substituted or unsubstituted with alkyl, aryl or heterocyclyl; phenanthryl substituted or unsubstituted with alkyl, aryl or heterocyclyl; triphenylene substituted or unsubstituted with alkyl, aryl or heterocyclyl; fluorenyl substituted or unsubstituted with alkyl, aryl, or heterocyclyl; carbazolyl substituted or unsubstituted with alkyl, aryl or heterocyclyl; dibenzofuranyl substituted or unsubstituted with alkyl, aryl, or heterocyclyl; or dibenzothienyl substituted or unsubstituted with alkyl, aryl or heterocyclyl.
In an embodiment of the present specification, ar1 and Ar2 are the same or different from each other, and are each independently phenyl substituted or unsubstituted with an aryl group or a heterocyclic group, biphenyl substituted or unsubstituted with an aryl group or a heterocyclic group, terphenyl substituted or unsubstituted with an aryl group, naphthyl substituted or unsubstituted with an aryl group, phenanthryl substituted or unsubstituted with an aryl group, triphenylene substituted or unsubstituted with an aryl group, fluorenyl substituted or unsubstituted with an alkyl group or an aryl group, carbazolyl, dibenzofuranyl, or dibenzothienyl.
In one embodiment of the present specification, ar1 and Ar2 mentioned above are the same or different from each other, and each is independently a phenyl group substituted or unsubstituted with a naphthyl group, a carbazolyl group or a dibenzofuranyl group; biphenyl substituted or unsubstituted with naphthyl; a terphenyl group; naphthyl substituted or unsubstituted by phenyl, naphthyl or carbazolyl; phenanthryl; triphenylene; fluorenyl substituted or unsubstituted with methyl or phenyl; carbazolyl; dibenzofuranyl; or dibenzothienyl.
In one embodiment of the present specification, each of Ar1 and Ar2 is represented by any one of the following structures.
In the above structures, the dotted line represents the binding site and R101 is a substituted or unsubstituted aryl group.
In one embodiment of the present specification, the above chemical formula 1 is any one of the following chemical formulas 1-1 to 1-4.
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formulas 1-4]
In the above chemical formulas 1-1 to 1-4,
r1, R2, L1, L2, ar1, ar2, R1, R2, a and b are as defined in the above chemical formula 1,
r3 to R5 are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
c is an integer of 1 to 4, and when c is 2 or more, 2 or more R3 s are the same or different from each other,
d is an integer of 1 to 4, and when d is 2 or more, 2 or more R4 s are the same or different from each other,
e is an integer of 1 to 4, and when e is 2 or more, 2 or more R5 s are the same or different from each other,
in one embodiment of the present specification, the above chemical formula 1-1 is any one of the following chemical formulas 1-1-1 to 1-1-3.
[ chemical formulas 1-1-1]
[ chemical formulas 1-1-2]
[ chemical formulas 1-1-3]
In the above chemical formulas 1-1 to 1-1-3, R1, R2, L1, L2, ar1, ar2, R1, R2, a and b are as defined in the above chemical formula 1,
r3 is hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
c is an integer of 1 to 4, and when c is 2 or more, 2 or more R3 are the same or different from each other.
In one embodiment of the present specification, the above chemical formula 1-2 is any one of the following chemical formulas 1-2-1 to 1-2-3.
[ chemical formula 1-2-1]
[ chemical formulas 1-2-2]
[ chemical formulas 1-2-3]
In the above chemical formulas 1-2-1 to 1-2-3, R1, R2, L1, L2, ar1, ar2, R1, R2, a and b are as defined in the above chemical formula 1,
r4 and R5 are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
d is an integer of 1 to 4, and when d is 2 or more, 2 or more R4 s are the same or different from each other,
e is an integer of 1 to 4, and when e is 2 or more, 2 or more R5 s are the same or different from each other.
In one embodiment of the present specification, the above chemical formula 1-3 is any one of the following chemical formulas 1-3-1 to 1-3-3.
[ chemical formulas 1-3-1]
[ chemical formulas 1-3-2]
[ chemical formulas 1-3-3]
In the above chemical formulas 1-3-1 to 1-3-3, R1, R2, L1, L2, ar1, ar2, R1, R2, a and b are as defined in the above chemical formula 1,
r4 and R5 are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
d is an integer of 1 to 4, and when d is 2 or more, 2 or more R4 s are the same or different from each other,
e is an integer of 1 to 4, and when e is 2 or more, 2 or more R5 s are the same or different from each other.
In one embodiment of the present specification, the above chemical formula 1-4 is any one of the following chemical formulas 1-4-1 to 1-4-3.
[ chemical formulas 1-4-1]
[ chemical formulas 1-4-2]
[ chemical formulas 1-4-3]
In the above chemical formulas 1-4-1 to 1-4-3, R1, R2, L1, L2, ar1, ar2, R1, R2, a and b are as defined in the above chemical formula 1,
r4 and R5 are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
d is an integer of 1 to 4, and when d is 2 or more, 2 or more R4 s are the same or different from each other,
e is an integer of 1 to 4, and when e is 2 or more, 2 or more R5 s are the same or different from each other,
in one embodiment of the present specification, R3 to R5 are the same or different from each other and each is independently hydrogen or a substituted or unsubstituted aryl group.
In one embodiment of the present specification, R3 to R5 are the same or different from each other and each is independently hydrogen or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
In one embodiment of the present specification, R3 to R5 are the same or different from each other and each independently is hydrogen or aryl.
In one embodiment of the present specification, R3 to R5 are the same or different from each other and each independently is hydrogen or phenyl.
In one embodiment of the present specification, the compound of formula 1 is any one of the following compounds.
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The compound of chemical formula 1 in the present specification can produce a core structure as shown in the following reaction formula. The substituents may be combined by methods known in the art, and the kinds, positions and number of the substituents may be changed according to techniques known in the art.
< reaction >
In the above reaction formula, R1, R2, L1 to L3, ar1 to Ar3, a, b, R1 to R3 are as defined in chemical formula 1.
In this specification, by introducing various substituents into the core structure as described above, compounds having various energy bandgaps can be synthesized. In addition, in the present invention, by introducing various substituents into the core structure of the structure shown above, HOMO and LUMO energy levels of the compounds can also be adjusted.
In addition, by introducing various substituents into the core structure of the structure shown above, a compound having the inherent characteristics of the introduced substituents can be synthesized. For example, a substance satisfying the conditions required in each organic layer can be synthesized by introducing substituents mainly used in the hole injection layer substance, the hole transport layer substance, the electron blocking layer substance, the light emitting layer substance, and the electron transport layer substance used in manufacturing an organic light emitting device into the above-described core structure.
In addition, the organic light emitting device according to the present specification includes: a first electrode, a second electrode, and 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 or more of the organic layers contains the compound of chemical formula 1.
The organic light-emitting device of the present specification can be manufactured by a general method and material for manufacturing an organic light-emitting device, except that one or more organic layers are formed using the above-described compound.
The compound may be used not only in the vacuum vapor deposition method but also in the solution coating method to form an organic layer in the production of an organic light-emitting device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spray coating, roll coating, and the like, but is not limited thereto.
For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. This can be manufactured as follows: a first electrode is formed by vapor deposition of a metal or a metal oxide having conductivity or an alloy thereof on a substrate by a physical vapor deposition method (PVD: physical vapor deposition (physical Vapor Deposition)) such as sputtering or electron beam evaporation, an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is then formed on the first electrode, and then a substance usable as a second electrode is vapor deposited on the organic layer. In addition to this method, the second electrode material, the organic layer, and the first electrode material may be sequentially deposited on the substrate to manufacture an organic light-emitting device. In addition, in the case of manufacturing an organic light-emitting device, the heterocyclic compound represented by the above chemical formula 1 may be used to form an organic layer not only by a vacuum evaporation method but also by a solution coating method. Here, the solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, roll coating, and the like, but is not limited thereto.
When the organic light emitting device includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.
The organic layer may have a multilayer structure of 2 or more layers including a hole injection layer, a hole transport layer, a layer that performs hole injection and hole transport simultaneously, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a layer that performs electron injection and electron transport simultaneously, or the like, but the organic layer is not limited to this and may have a single layer structure. The organic layer may be formed into a smaller number of layers by a solvent process (solvent process) other than vapor deposition, such as spin coating, dip coating, knife coating, screen printing, ink jet printing, or thermal transfer printing, using various polymer materials.
In one embodiment of the present specification, the organic layer may be formed of a single layer structure or a multilayer structure in which 2 or more organic layers are stacked. For example, the organic light-emitting device of the present specification may have a structure including a hole injection layer, a hole transport layer, a layer that performs hole transport and hole injection simultaneously, an electron blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer, a layer that performs electron transport and electron injection simultaneously, and the like as organic layers. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller or larger number of organic layers.
In an embodiment of the present specification, the organic layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include the compound.
In an embodiment of the present disclosure, the organic layer includes a hole injection layer, a hole transport layer, or an electron blocking layer, and the hole injection layer, the hole transport layer, or the electron blocking layer may include the compound.
In one embodiment of the present specification, the organic layer includes a light-emitting layer, and the light-emitting layer includes the compound.
In one embodiment of the present specification, the organic layer includes a light emitting layer, and the light emitting layer may include the compound as a dopant of the light emitting layer.
In one embodiment of the present specification, the organic layer includes a light-emitting layer including the compound as a dopant of the light-emitting layer, and may further include a host.
In one embodiment of the present disclosure, the organic layer includes a light emitting layer including the compound as a dopant of the light emitting layer, a fluorescent host or a phosphorescent host, and other organic compounds, metals, or metal compounds as dopants.
In one embodiment of the present specification, the organic layer includes a light emitting layer including the compound as a dopant of the light emitting layer, and further includes a fluorescent host or a phosphorescent host, and may be used together with an iridium (Ir) dopant.
In one embodiment of the present specification, the organic layer includes a light-emitting layer, and the light-emitting layer may include the compound as a host of the light-emitting layer.
In one embodiment of the present specification, the organic layer includes a light-emitting layer including the compound as a host of the light-emitting layer, and may further include a dopant.
In one embodiment of the present disclosure, the organic layer includes an electron blocking layer, and the electron blocking layer may include the compound.
In one embodiment of the present disclosure, the first electrode is an anode, and the second electrode is a cathode.
According to another embodiment, the first electrode is a cathode, and the second electrode is an anode.
For example, the structure of the organic light emitting device of the present specification may have the structure shown in fig. 1 to 3, but is not limited thereto.
Fig. 1 illustrates an example of an organic light emitting device constituted by a substrate 1, a first electrode 2, a light emitting layer 3, and a second electrode 4.
Fig. 2 illustrates an example of an organic light-emitting device constituted by a substrate 1, a first electrode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a second electrode 4.
Fig. 3 illustrates an example of an organic light-emitting device constituted by the substrate 1, the first electrode 2, the hole injection layer 5, the hole transport layer 6, the electron blocking layer 9, the light-emitting layer 7, the hole blocking layer 10, the layer 11 in which electron transport and electron injection are performed simultaneously, and the second electrode 4.
Specifically, the organic light emitting device may have a laminated structure such as the following, in addition to the structure explicitly shown in the above-described drawings, but is not limited thereto.
(1) Anode/hole transport layer/light emitting layer/cathode
(2) Anode/hole injection layer/hole transport layer/light emitting layer/cathode
(3) Anode/hole transport layer/light emitting layer/electron transport layer/cathode
(4) Anode/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode
(5) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode
(6) Anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode
(7) Anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode
(8) Anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode
(9) Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode
(10) Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode
(11) Anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode
(12) Anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode
(13) Anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode
(14) Anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode
(15) Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/cathode for simultaneous electron transport and electron injection
In one embodiment of the present description, the above-described "electron transport layer/electron injection layer" may be replaced by an electron injection and transport layer.
In an embodiment of the present specification, the hole transport layer may be formed of a multilayer structure. For example, it may be constituted of a first hole transport layer and a second hole transport layer containing substances different from each other.
The anode is an electrode for injecting holes, and is preferably a substance having a large work function as an anode substance in order to allow holes to be smoothly injected into the organic layer. Examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, and alloys thereof; metal oxides such as zinc Oxide, indium Tin Oxide (ITO), and Indium zinc Oxide (IZO, indium Zinc Oxide); znO of Al or SnO 2 A combination of metals such as Sb and the like and oxides; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]Conductive polymers such as (PEDOT), polypyrrole and polyaniline, but not limited thereto.
The cathode is an electrode for injecting electrons, and is preferably a substance having a small work function as a cathode substance in order to facilitate injection of electrons into the organic layer. Examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof; liF/Al or LiO 2 And/or Al, but is not limited thereto.
The hole injection layer is a layer that functions to smooth injection of holes from the anode to the light-emitting layer. The hole injecting substance is a substance that can well inject holes from the anode at a low voltage, and preferably has a HOMO (highest occupied molecular orbital ) interposed between the work function of the anode substance and the HOMO of the surrounding organic layer. Examples of the hole injection substance include, but are not limited to, metalloporphyrin (porphyrin), oligothiophene, arylamine-based compounds, hexanitrile hexaazabenzophenanthrene-based compounds, quinacridone-based compounds, perylene-based compounds, benzonitrile-based compounds, anthraquinone, polyaniline, and polythiophene-based conductive polymers. Specifically, an arylamine compound and a benzonitrile compound can be used for the hole injection layer. More specifically, a benzonitrile compound substituted with a halogen group and an arylamine compound substituted with a carbazole group may be used, but are not limited thereto. The thickness of the hole injection layer may be 1nm to 150nm. When the thickness of the hole injection layer is 1nm or more, there is an advantage that the degradation of the hole injection characteristic can be prevented, and when the thickness of the hole injection layer is 150nm or less, there is an advantage that the increase of the driving voltage for improving the migration of holes can be prevented.
The hole transport layer can function to smooth the transport of holes. The hole-transporting substance is a substance capable of receiving holes from the anode or the hole-injecting layer and transferring the holes to the light-emitting layer, and a substance having a large mobility to the holes is suitable. For example, the hole-transporting substance includes, but is not limited to, an arylamine compound, a carbazole compound, a conductive polymer, and a block copolymer having both a conjugated portion and a non-conjugated portion. Specifically, the hole transport layer may be formed using a carbazole-based compound substituted with an arylamine group, but is not limited thereto.
A hole buffer layer may be further provided between the hole injection layer and the hole transport layer, and may include a hole injection or transport material known in the art.
An electron blocking layer may be disposed between the hole transport layer and the light emitting layer. The electron blocking layer may be formed using the above-described compound or a material known in the art.
The light-emitting layer may emit red, green, or blue light, and may be made of a phosphorescent material or a fluorescent material. The light-emitting material is capable of being transported from the hole transport layerAnd an electron transport layer which receives holes and electrons, respectively, and combines them to emit light in the visible light region, and is preferably a substance having high quantum efficiency for fluorescence or phosphorescence. For example, the above-mentioned luminescent material may be 8-hydroxy-quinoline aluminum complex (Alq 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Carbazole-based compounds; dimeric styryl (dimerized styryl) compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzo (E) benzo (EAzole, benzothiazole, and benzimidazole compounds; poly (p-phenylene vinylene) (PPV) based polymers; spiro (spiro) compounds; polyfluorene; rubrene, etc., but is not limited thereto.
Examples of the host material of the light-emitting layer include an aromatic condensed ring derivative and a heterocyclic compound. For example, as the aromatic condensed ring derivative, there are anthracene derivative, pyrene derivative, naphthalene derivative, pentacene derivative, phenanthrene compound, fluoranthene compound, and the like, and as the heterocyclic compound, there are carbazole derivative, dibenzofuran derivative, and ladder-type furan compoundPyrimidine derivatives, and the like, but are not limited thereto. Specifically, as the main body of the light-emitting layer, an anthracene derivative can be used, but is not limited thereto.
When the light-emitting layer emits red light, as a light-emitting dopant, a phosphorescent substance such as PIQIr (acac) (bis (1-phenylisoquinoline) acetylacetonate iridium, bis (1-phenylisoquinoline) acetylacetonateiridi um), PQIr (acac) (bis (1-phenylquinoline) acetylacetonate iridium, bis (1-phenylquinoline) ac etylacetonate iridium), PQIr (tris (1-phenylquinoline) iridium), ptOEP (platinum octaethylporphyrin, octaethylporphyrin platinum), or Alq may be used 3 Fluorescent substances such as (tris (8-hydroxyquinoline) aluminum, tris (8-hydroxyquinoline) aluminum), etc., but are not limited thereto. When the light emitting layer emits green light, ir (ppy) can be used as a light emitting dopant 3 Phosphorescent substances such as (planar tris (2-phenylpyridine) iridium) and factris (2-phenylpyridine) iridiumOr Alq 3 Fluorescent substances such as (tris (8-hydroxyquinoline) aluminum), but are not limited thereto. When the light-emitting layer emits blue light, as the light-emitting dopant, (4, 6-F 2 ppy) 2 Examples of the fluorescent substance include, but are not limited to, phosphorescent substances such as Irpic, fluorescent substances such as spiro-DPVBi (spiro-DPVBi), spiro-6P (spiro-6P), distyrylbenzene (DSB), distyrylarylene (DSA), pyrene-based compounds, PFO-based polymers, and PPV-based polymers. Specifically, as the dopant, a pyrene compound may be used, but is not limited thereto.
A hole blocking layer may be disposed between the electron transport layer and the light emitting layer. The hole blocking layer is a layer that prevents holes from reaching the cathode, and can be formed generally under the same conditions as those of the hole injection layer. For example, as a substance suitable for the hole blocking layer, there isThe diazole derivative or triazole derivative, triazine derivative, phenanthroline derivative, BCP, aluminum complex (aluminum complex), and the like, but are not limited thereto. Specifically, a triazine derivative may be used, but is not limited thereto.
The electron transport layer can play a role in enabling electron transport to be smooth. The electron transporting substance is a substance that can well receive electrons from the cathode and transfer them to the light-emitting layer, and is suitable for a substance having high mobility of electrons. For example, the electron-transporting substance may be an Al complex of 8-hydroxyquinoline or an Al complex containing Alq 3 But not limited to, complexes of (c) and (d), organic radical compounds, hydroxyflavone-metal complexes, and the like. The thickness of the electron transport layer may be 1nm to 50nm. When the thickness of the electron transport layer is 1nm or more, there is an advantage that the degradation of the electron transport property can be prevented, and when it is 50nm or less, there is an advantage that the increase of the driving voltage for the purpose of improving the electron transfer can be prevented when the thickness of the electron transport layer is too thick.
The electron injection layer can perform a function of smoothly injecting electrons. As the electron injecting substance, the following compounds are preferable: having the ability to transport electrons, with injection of electrons from the cathodeHas an excellent electron injection effect for a light-emitting layer or a light-emitting material, prevents migration of excitons generated in the light-emitting layer to a hole injection layer, and is excellent in a thin film forming ability. Examples of the electron-injecting substance include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, and the like, Azole,/->The diazoles, triazoles, triazines, imidazoles, perylenetetracarboxylic acids, fluorenylenemethanes, anthrones, and the like, and their derivatives, metal complexes, and nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.
Examples of the metal complex include, but are not limited to, lithium 8-hydroxyquinoline, zinc bis (8-hydroxyquinoline), copper bis (8-hydroxyquinoline), manganese bis (8-hydroxyquinoline), aluminum tris (2-methyl-8-hydroxyquinoline), gallium tris (8-hydroxyquinoline), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (10-hydroxybenzo [ h ] quinoline), gallium chloride bis (2-methyl-8-quinoline) (o-cresol) gallium, aluminum bis (2-methyl-8-quinoline) (1-naphthol), gallium bis (2-methyl-8-quinoline) (2-naphthol).
The electron transport layer and the electron injection layer may be formed of a single layer. For example, the electron injection and transport layer may be formed by vacuum evaporation of the electron injection material and the electron transport material simultaneously. The electron injection and transport layer may further comprise a metal complex. Examples of the metal complex include Al complexes of 8-hydroxyquinoline (Alq 3 ) LiQ, metal complex, etc., but is not limited thereto. For example, the above electron injection and transport layer may use triazine derivatives and lithium quinoline (LiQ), but is not limited thereto.
The organic light emitting device according to the present invention may be of a top emission type, a bottom emission type, or a bi-directional emission type, depending on the materials used.
Modes for carrying out the invention
In the following, experimental examples will be described in detail for the purpose of specifically describing the present specification. However, the embodiments according to the present specification may be modified into various forms, and the scope of the present application is not to be construed as limited to the embodiments described in detail below. The embodiments of the present application are provided to more fully explain the present description to those skilled in the art.
< production example >
Production example 1.
In a 500mL round bottom flask, compound 9- (1- (4-chlorophenyl) naphthalen-2-yl) -9H-carbazole (9- (1- (4-chlorophenyl) naphthalen-2-yl) -9H-carbazole) (8.26 g,20.45 mmol) and compound a1 (10.06 g,22.49 mmol) were completely dissolved in 270mL of Xylene (Xylene) under nitrogen atmosphere, sodium tert-butoxide (NaOtBu) (2.95 g,30.67 mmol) was added, bis (tri-tert-butylphosphine) palladium (0) (Bis (tris-tert-butylphenne) pa lladium (0)) (0.21 g,0.41 mmol) was added, and after this, the mixture was heated and stirred for 4 hours. After the temperature was lowered to ordinary temperature and the base (base) was removed by filtration (filter), xylene was concentrated under reduced pressure and recrystallized from 280mL of ethyl acetate to yield compound 1 (11.24 g, yield: 67%).
MS[M+H] + ＝816
Production example 2.
After complete dissolution of compound 9- (1- (4-chlorophenyl) naphthalen-2-yl) -9H-carbazole (8.05 g,19.93 mmol) and compound a2 (9.22 g,21.92 mmol) in 280mL of xylene under nitrogen in a 500mL round bottom flask, naOtBu (2.87 g,29.89 mmol) was added and bis (tri-t-butylphosphine) palladium (0) (0.20 g,0.40 mmol) was added and heated for 5 hours with stirring. After the temperature was lowered to room temperature and the alkali was removed by filtration, xylene was concentrated under reduced pressure and recrystallized from 270mL of ethyl acetate to yield Compound 2 (8.96 g, yield: 57%).
MS[M+H] + ＝789
Production example 3.
After complete dissolution of compound 9- (1- (4-chlorophenyl) naphthalen-2-yl) -9H-carbazole (7.88 g,19.50 mmol) and compound a3 (9.39 g,21.46 mmol) in 270mL of xylene under nitrogen in a 500mL round bottom flask, naOtBu (2.81 g,29.26 mmol) was added and bis (tri-t-butylphosphine) palladium (0) (0.20 g,0.39 mmol) was added and heated for 4 hours with stirring. After the temperature was lowered to room temperature and the alkali was removed by filtration, xylene was concentrated under reduced pressure and recrystallized from 250mL of ethyl acetate to give compound 3 (11.34 g, yield: 57%).
MS[M+H] + ＝806
Preparation example 4.
After complete dissolution of compound 9- (1- (4-chlorophenyl) naphthalen-2-yl) -9H-carbazole (8.37 g,20.72 mmol) and compound a4 (9.97 g,22.79 mmol) in 260mL of xylene under nitrogen in a 500mL round bottom flask, naOtBu (2.99 g,31.08 mmol) was added and bis (tri-t-butylphosphine) palladium (0) (0.21 g,0.41 mmol) was added and heated for 4 hours with stirring. After the temperature was lowered to room temperature and the alkali was removed by filtration, xylene was concentrated under reduced pressure and recrystallized from 270mL of ethyl acetate to give Compound 4 (9.76 g, yield: 58%).
MS[M+H] + ＝779
Production example 5.
After 9- (1- (4 '-chloro- [1.1' -biphenyl ] -4-yl) naphthalen-2-yl) -9H-carbazole (9- (1- (4 '-biphen-1, 1' -yl) -9H-carbazol) (7.55 g,15.73 mmol) and compound a5 (5.97 g,17.30 mmol) were completely dissolved in 270mL of xylene in a 500mL round bottom flask, naOtBu (2.27 g,23.59 mmol) was added and bis (tri-t-butylphosphine) palladium (0) (0.16 g,0.31 mmol) was added and the mixture was heated and stirred for 5 hours. After the temperature was lowered to room temperature and the alkali was removed by filtration, xylene was concentrated under reduced pressure and recrystallized from 280mL of ethyl acetate to give Compound 5 (7.39 g, yield: 60%).
MS[M+H] + ＝789
Preparation example 6.
After 9- (1- (3 ' -chloro- [1,1' -biphenyl ] -3-yl) naphthalen-2-yl) -9H-carbazole (9- (1- (3 ' -biphen-1-yl) -9H-carbazol) (7.88 g,16.42 mmol) and compound a6 (6.72 g,18.06 mmol) were completely dissolved in 290mL of xylene in a 500mL round bottom flask under nitrogen atmosphere, naOtBu (2.37 g,24.63 mmol) was added and bis (tri-t-butylphosphine) palladium (0) (0.17 g,0.33 mmol) was added and the mixture was heated and stirred for 5 hours. After the temperature was lowered to room temperature and the alkali was removed by filtration, xylene was concentrated under reduced pressure and recrystallized from 250mL of ethyl acetate to give Compound 6 (9.14 g, yield: 68%).
MS[M+H] + ＝816
Preparation example 7.
After 9- (1- (2 '-chloro- [1,1' -biphenyl ] -2-yl) naphthalen-2-yl) -9H-carbazole (9- (1- (2 '-chloro- [1,1' -biphen yl ] -2-yl) -9H-carbazole) (7.28 g,15.17 mmol) and compound a7 (7.04 g,16.68 mmol) were completely dissolved in 240mL of xylene in a 500mL round bottom flask, naOtBu (2.19 g,22.75 mmol) was added and bis (tri-t-butylphosphine) palladium (0) (0.16 g,0.30 mmol) was added, followed by stirring with heating for 5 hours. After the temperature was lowered to room temperature and the alkali was removed by filtration, xylene was concentrated under reduced pressure and recrystallized from 310mL of ethyl acetate to give Compound 7 (8.82 g, yield: 67%).
MS[M+H] + ＝866
Preparation example 8.
After 9- (1- (3 '-chloro- [1,1' -biphenyl ] -4-yl) naphthalen-2-yl) -9H-carbazole (9- (1- (3 '-chloro- [1,1' -biphen-yl ] -4-yl) naphthalen-2-yl) -9H-carbazole) (7.66 g,15.96 mmol) and compound a8 (6.94 g,17.55 mmol) were completely dissolved in 260mL of xylene in a 500mL round bottom flask, naOtBu (2.30 g,23.94 mmol) was added and bis (tri-t-butylphosphine) palladium (0) (0.16 g,0.32 mmol) was added and the mixture was heated and stirred for 5 hours. After the temperature was lowered to room temperature and the alkali was removed by filtration, xylene was concentrated under reduced pressure and recrystallized from 250mL of ethyl acetate to give Compound 8 (7.68 g, yield: 57%).
MS[M+H] + ＝840
Preparation example 9.
After the compound 9- (1- (2 '-chloro- [1,1' -biphenyl ] -4-yl) naphthalen-2-yl) -9H-carbazole (9- (1- (2 '-chloro- [1,1' -biphen-yl ] -4-yl) -9H-carbazole) (7.83 g,16.31 mmol) and the compound a9 (7.20 g,17.94 mmol) were completely dissolved in 270mL of xylene in a 500mL round bottom flask, naOtBu (2.35 g,24.47 mmol) was added and bis (tri-t-butylphosphine) palladium (0) (0.17 g,0.33 mmol) was added, followed by stirring with heating for 5 hours. After the temperature was lowered to room temperature and the alkali was removed by filtration, xylene was concentrated under reduced pressure and recrystallized from 250mL of tetrahydrofuran to give Compound 9 (8.63 g, yield: 63%).
MS[M+H] + ＝846
Example 1.
ITO (indium tin oxide) toThe glass substrate coated to have a thin film thickness is put into distilled water in which a detergent is dissolved, and washed with ultrasonic waves. In this case, a product of fei he er (Fischer co.) was used as the detergent, and distilled water was filtered twice using a Filter (Filter) manufactured by millbore co. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After the distilled water washing is completed, ultrasonic washing is performed by using solvents of isopropanol, acetone and methanol, and the obtained product is dried and then conveyed to a plasma cleaning machine. After the substrate was cleaned with oxygen plasma for 5 minutes, the substrate was transferred to a vacuum vapor deposition machine.
On the ITO transparent electrode as an anode thus prepared, the following compound HI1 and the following compound HI2 were mixed in a ratio of 98:2 (molar ratio)And performing thermal vacuum evaporation to form a hole injection layer. On the hole injection layer, a compound represented by the following formula HT1 is added>Vacuum evaporation is performed to form a hole transport layer. Next, on the hole transport layer, the film thickness is +.>The compound 1 produced in production example 1 was vacuum-evaporated to form an electron blocking layer. Next, on the above electron blocking layer, the film thickness is +.>A compound represented by the following chemical formula BH and a compound represented by the following chemical formula BD were vacuum-evaporated at a weight ratio of 25:1 to form a light-emitting layer. On the above-mentioned light-emitting layer, the film thickness is +.>A hole blocking layer was formed by vacuum evaporation of a compound represented by HB1 described below. Next, on the hole blocking layer, a compound represented by the following chemical formula ET1 and a compound represented by the following chemical formula LiQ were vacuum-evaporated at a weight ratio of 1:1 to form ∈ ->Form an electron injection and transport layer. On the electron injection and transport layer, lithium fluoride (LiF) is sequentially added +. >Is made of aluminum +.>And vapor deposition is performed to form a cathode.
In the above process, the vapor deposition rate of the organic matter is maintainedSecond to->Lithium fluoride maintenance of cathode per secondVapor deposition rate per second, aluminum maintenance->Vapor deposition rate per second, vacuum degree was maintained at 2×10 during vapor deposition -7 To 5x10 -6 The support is thus fabricated into an organic light emitting device.
Examples 2 to 9.
An organic light emitting device was manufactured in the same manner as in example 1, except that the compound described in table 1 below was used instead of the compound 1 in example 1.
Comparative examples 1 to 6.
An organic light emitting device was manufactured in the same manner as in example 1 above, except that the compound described in table 1 below was used instead of the compound 1 in example 1 above. The compounds of EB2, EB3, EB4, EB5, EB6 and EB7 used in table 1 below are shown below.
When a current was applied to the organic light emitting devices manufactured in the above examples and comparative examples, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in table 1 below. T95 refers to the time required for the luminance to decrease from the initial luminance (1600 nit) to 95%.
TABLE 1
As shown in table 1 above, the organic light emitting device using the compound of the present invention as an electron blocking layer shows excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light emitting device.
In contrast, an organic light emitting device using a compound other than the compound of chemical formula 1 as an electron blocking layer exhibits characteristics of an increase in driving voltage, a decrease in efficiency, and a decrease in lifetime.
Specifically, comparative examples 1 to 6 to which a compound (EB 2) in which a ring portion other than N of a carbazolyl group is substituted with naphthalene, a compound (EB 3 and EB 5) in which naphthalene is substituted with a substituent other than an amine group and a carbazolyl group, a compound (EB 6 and EB 7) in which the substitution positions of an amine group in naphthalene are different, and a compound (EB 4) in which the substitution positions of an amine group and a carbazolyl group in naphthalene are both different, exhibited characteristics of an increase in driving voltage, efficiency, and a reduction in lifetime, as compared with examples 1 to 9.
While the preferred embodiment (electron blocking layer) of the present invention has been described above, the present invention is not limited thereto, and various modifications may be made within the scope of the invention as claimed and the detailed description of the invention, and the present invention is also within the scope of the invention.

Claims (7)

1. A compound of the following chemical formula 1:
chemical formula 1
In the chemical formula 1 described above, a compound having the formula,
r1 and R2 are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
L1 to L3 are identical to or different from each other and are each independently a direct bond or a substituted or unsubstituted arylene group,
ar1 and Ar2 are the same as or different from each other, each independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
a is an integer of 1 to 4, and when a is 2 or more, 2 or more R1 s are the same or different from each other,
b is an integer of 1 to 4, and when b is 2 or more, 2 or more R2 are the same or different from each other,
r1 to r3 are each integers of 1 to 3, and when r1 to r3 are each 2 or more, the structures in each bracket are the same or different from each other.
2. The compound of claim 1, wherein L1 and L2 are the same or different from each other and are each independently a direct bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted fluorenylene group.
3. The compound of claim 1, wherein Ar1 and Ar2 are the same or different from each other and are each independently 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 phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothienyl group.
4. The compound according to claim 1, wherein the chemical formula 1 is any one of the following chemical formulas 1-1 to 1-4:
chemical formula 1-1
Chemical formula 1-2
Chemical formulas 1-3
Chemical formulas 1-4
In the chemical formulas 1-1 to 1-4,
r1, R2, L1, L2, ar1, ar2, R1, R2, a and b are as defined in the chemical formula 1,
r3 to R5 are the same or different from each other and are each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
c is an integer of 1 to 4, and when c is 2 or more, 2 or more R3 are the same or different from each other,
d is an integer of 1 to 4, and when d is 2 or more, 2 or more R4 s are the same or different from each other,
e is an integer of 1 to 4, and when e is 2 or more, 2 or more R5 are the same or different from each other.
5. The compound of claim 1, wherein the compound of formula 1 is any one of the following compounds:
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6. an organic light emitting device, comprising: a first electrode, a second electrode, and 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 or more of the organic layers contains the compound according to any one of claims 1 to 5.
7. The organic light-emitting device of claim 6, wherein the organic layer comprises a hole injection layer, a hole transport layer, or an electron blocking layer, the hole injection layer, the hole transport layer, or the electron blocking layer comprising the compound.
CN202180076967.6A 2021-01-13 2021-12-16 Compound and organic light emitting device comprising the same Pending CN116507619A (en)

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