CN110800122B - Organic electroluminescent device - Google Patents
Organic electroluminescent device Download PDFInfo
- Publication number
- CN110800122B CN110800122B CN201880042379.9A CN201880042379A CN110800122B CN 110800122 B CN110800122 B CN 110800122B CN 201880042379 A CN201880042379 A CN 201880042379A CN 110800122 B CN110800122 B CN 110800122B
- Authority
- CN
- China
- Prior art keywords
- substituted
- unsubstituted
- group
- chemical formula
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- 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
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
-
- 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
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- 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
Abstract
The present specification relates to an organic electroluminescent device.
Description
Technical Field
The present invention claims priority from korean patent application No. 10-2017-0098073, filed to the korean patent office on the basis of month 8 and day 2 of 2017, the entire contents of which are incorporated herein.
The present specification relates to organic light emitting devices.
Background
In general, the organic light emitting phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic layer therebetween. Here, in order to improve efficiency and stability of the organic light-emitting device, the organic layer is often formed of a multilayer structure composed of different substances, and may be formed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, or the like. With the structure of such an organic light emitting device, if a voltage is applied between both electrodes, holes are injected from the anode to the organic layer, electrons are injected from the cathode to the organic layer, excitons (exiton) are formed when the injected holes and electrons meet, and light is emitted when the excitons re-transition to the ground state.
There is a continuing need to develop new materials for use in organic electroluminescent devices as described above.
Disclosure of Invention
Technical problem
The present specification provides an organic electroluminescent device.
Solution to the problem
Provided is an organic electroluminescent device, including: the light-emitting device includes an anode, a cathode disposed opposite to the anode, and a light-emitting layer disposed between the anode and the cathode, wherein the light-emitting layer includes a first body represented by chemical formula 1 and a second body represented by chemical formula 2.
[ chemical formula 1]
In the above-mentioned chemical formula 1,
r3 is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituent of the following chemical formula 3,
[ chemical formula 2]
[ chemical formula 3]
In the above-mentioned chemical formulas 1 to 3,
r1, R2 and R4 to R7 are the same or different from each other and are each independently hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or are combined with adjacent groups to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring,
x1 to X7 are identical to or different from each other and are each independently CRa or N,
Y1 and Y2 are identical to or different from each other and are each, independently of one another, CRbRc, NRd, O or S,
y3 is CReRf, NRg, O or S, and the total number of the components is,
l is a direct bond, or a substituted or unsubstituted arylene,
ra is hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted aryl, heteroaryl, arylthio
Or aryloxy, or R4, to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring,
rb to Rg are the same or different from each other and are each independently hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted aryl, or heteroaryl,
a is an integer of 0 to 8,
b. e and f are integers of 0 to 7 respectively,
c is an integer of 0 or 1,
d is an integer of 0 to 2,
g is an integer of 0 to 5,
b+c is an integer of 0 to 7,
a. when b, d, e, f and g are plural, each of R1, R2, and R4 to R7 is the same or different from each other independently.
Effects of the invention
The organic electroluminescent device according to an embodiment of the present specification may use the compounds of chemical formulas 1 and 2 as a material of the organic material layer, and by using the compounds of chemical formulas 1 and 2, an improvement in efficiency, a low driving voltage, and/or an improvement in lifetime characteristics may be achieved in the organic electroluminescent device.
Specifically, when the compound represented by chemical formula 1 is used as a single host in a light-emitting layer, the HOMO level difference from the adjacent hole-transporting layer is large, a barrier (barrier) to holes is generated, and hole transfer to the light-emitting layer is not easily achieved, so that a light-emitting region is formed adjacent to the hole-transporting layer. For this reason, holes are unbalanced with electrons and efficiency and lifetime are reduced. Accordingly, by using the second host compound represented by the above chemical formula 2 together, the efficiency and lifetime of the organic light emitting device can be improved.
Drawings
Fig. 1 illustrates an organic electroluminescent device according to an embodiment of the present specification.
FIG. 2 shows the results of liquid chromatography analysis of Compound 1A.
FIG. 3 is the result of mass spectrometry of Compound 1A.
[ description of the symbols ]
1: substrate board
2: anode
3: organic layer
4: cathode electrode
Detailed Description
The present specification will be described in more detail below.
The present specification provides an organic electroluminescent device, comprising: the light-emitting device includes an anode, a cathode provided opposite to the anode, and a light-emitting layer provided between the anode and the cathode, wherein the light-emitting layer includes a first body represented by chemical formula 1 and a second body represented by chemical formula 2.
In the present specification, when a certain component is indicated as being "included" in a certain portion, unless otherwise stated, it means that other components may be further included, and not excluded.
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 in contact with the other member but also the case where another member exists between the two members.
In the present specification, examples of the substituents are described below, but are not limited thereto.
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, nitrile group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted aryl group, and substituted or unsubstituted 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 aryl substituted with aryl, aryl substituted with heteroaryl, heterocyclic group substituted with aryl, aryl substituted with alkyl, or the like.
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, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.
In the present specification, the silyl group specifically includes, but is not limited to, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like.
In the present specification, the aryl group is not particularly limited, but an aryl group having 6 to 30 carbon atoms is preferable, 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, triphenyl, pyrenyl, phenalenyl, perylenyl,
A group, a fluorenyl group, etc., 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 above fluorenyl group is substituted, it may be
Etc. However, the present invention is not limited thereto.
In the present specification, as examples of the arylamine group, there are a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamino group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing 2 or more of the above-described aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or may contain both a monocyclic aryl group and a polycyclic aryl group. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.
In the present specification, the aryl group in the N-arylalkylamine group and the N-arylalkylamine group is the same as the above-described examples of the aryl group.
In the present specification, impuritiesThe aryl group contains one or more heteroatoms which are non-carbon atoms, and specifically, the heteroatoms may contain one 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 30, and the heteroaryl group may be monocyclic or polycyclic. 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, as examples of the heteroarylamino group, there are a substituted or unsubstituted mono-heteroarylamino group, a substituted or unsubstituted di-heteroarylamino group, or a substituted or unsubstituted tri-heteroarylamino group. The heteroarylamine group containing 2 or more of the above heteroaryl groups may contain a monocyclic heteroaryl group, a polycyclic heteroaryl group, or may contain both a monocyclic heteroaryl group and a polycyclic heteroaryl group. For example, the heteroaryl group in the above heteroaryl amine group may be selected from the examples of heteroaryl groups described above.
In the present specification, examples of heteroaryl groups in the N-arylheteroarylamino group and the N-alkylheteroarylamino group are the same as those described above.
In this specification, the arylene group is not a 2-valent group, and the above description of the aryl group can be applied.
In this specification, the heteroarylene group may be used in addition to the 2-valent group, as described above.
According to an embodiment of the present specification, the above chemical formula 1 is any one of the following chemical formulas 4 to 6.
[ chemical formula 4]
[ chemical formula 5]
[ chemical formula 6]
In the above-mentioned chemical formulas 4 to 6,
ar is a substituted or unsubstituted terphenyl group, a substituted or unsubstituted phenanthryl group, or a substituted or unsubstituted triphenylene group,
x4 and X7 are identical to or different from each other and are each independently CRh or N,
y4 is NRi or O, and the total number of the catalyst is equal to or less than zero,
r8 is hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted silyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, or is combined with adjacent groups to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocycle,
rh and Ri are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted aryl group,
h is an integer of 0 to 4,
g is an integer of 0 to 3,
r1 to R4, R7, X1 to X3, a to d, and Ra to Rd are as defined in the above chemical formulas 1 and 3.
According to an embodiment of the present specification, the above R1 and R2 are the same or different from each other, and are each independently hydrogen, deuterium, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
According to an embodiment of the present specification, R1 and R2 are the same or different from each other, and each is independently hydrogen, deuterium, nitrile group, alkyl group, aryl group, or heteroaryl group.
According to an embodiment of the present specification, R1 and R2 are hydrogen.
According to an embodiment of the present specification, R3 is hydrogen, deuterium, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.
According to one embodiment of the present disclosure, R3 is a substituted or unsubstituted aryl group.
According to an embodiment of the present specification, R3 is aryl substituted or unsubstituted with alkyl.
According to an embodiment of the present specification, R3 is phenyl substituted or unsubstituted with an alkyl group, biphenyl substituted or unsubstituted with an alkyl group, terphenyl substituted or unsubstituted with an alkyl group, phenanthryl substituted or unsubstituted with an alkyl group, triphenylene substituted or unsubstituted with an alkyl group, or fluorenyl substituted or unsubstituted with an alkyl group.
According to one embodiment of the present specification, R3 is phenyl, biphenyl, terphenyl, phenanthryl, triphenylene, or dimethylfluorenyl.
According to one embodiment of the present disclosure, R3 is a substituted or unsubstituted heteroaryl.
According to one embodiment of the present disclosure, R3 is a substituted or unsubstituted heteroaryl group containing N, O or S.
According to an embodiment of the present specification, R3 is a substituted or unsubstituted dibenzofuranyl group or a substituted or unsubstituted dibenzothienyl group.
According to one embodiment of the present disclosure, R3 is a substituted or unsubstituted carbazolyl group.
According to an embodiment of the present specification, R3 is a carbazolyl group substituted or unsubstituted with an aryl group substituted or unsubstituted with deuterium, a nitrile group, an alkyl group, an aryl group, or a heteroaryl group.
According to an embodiment of the present specification, R3 is a carbazolyl group substituted or unsubstituted with deuterium, or phenyl substituted or unsubstituted with a nitrile group.
According to an embodiment of the present specification, R3 is a carbazolyl group substituted or unsubstituted with a phenyl group, a tert-butyl group, a dibenzofuranyl group, or a dibenzothiophenyl group.
According to one embodiment of the present specification, R3 is a carbazolyl group substituted or unsubstituted with a naphthyl group.
According to an embodiment of the present specification, R3 is a carbazolyl group substituted or unsubstituted with dibenzofuranyl or dibenzothiophenyl.
According to an embodiment of the present specification, the above R3 may be selected from substituents selected from which may be substituted or unsubstituted with phenyl.
According to an embodiment of the present specification, R4 is hydrogen, deuterium, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or is combined with an adjacent group to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring.
According to an embodiment of the present specification, R4 is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
According to an embodiment of the present specification, R4 is aryl substituted or unsubstituted or heteroaryl substituted or unsubstituted with aryl.
According to an embodiment of the present specification, R4 is an aryl group substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms, or a heteroaryl group substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms.
According to an embodiment of the present specification, R4 is an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 6 to 20 carbon atoms substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms.
According to an embodiment of the present specification, R4 is an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with a phenyl group, or a heteroaryl group having 6 to 20 carbon atoms substituted or unsubstituted with a phenyl group.
According to an embodiment of the present specification, R4 is phenyl substituted or unsubstituted, biphenyl, pyridyl, dibenzofuranyl substituted or unsubstituted with phenyl, or dibenzothienyl substituted or unsubstituted with phenyl.
According to an embodiment of the present specification, R5 and R6 are the same or different from each other, and each is independently hydrogen, deuterium, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or are combined with an adjacent group to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring.
According to an embodiment of the present specification, the above R5 and R6 are the same or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
According to an embodiment of the present specification, the above R5 and R6 are the same or different from each other, and each is independently hydrogen, deuterium, a silyl group substituted or unsubstituted with an aryl group, or a substituted or unsubstituted aryl group.
According to an embodiment of the present specification, the above R5 and R6 are the same or different from each other, and are each independently hydrogen, deuterium, a silyl group substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
According to an embodiment of the present specification, the above R5 and R6 are the same or different from each other, and each is independently hydrogen, deuterium, a silyl group substituted or unsubstituted with a phenyl group, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
According to an embodiment of the present specification, R5 and R6 are the same or different from each other, and each is independently hydrogen, deuterium, triphenylsilyl, phenyl, biphenyl, terphenyl, or naphthyl.
According to an embodiment of the present specification, R7 is hydrogen, or is combined with an adjacent group to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.
According to one embodiment of the present disclosure, R7 is hydrogen or is combined with an adjacent group to form a heterocyclic ring substituted or unsubstituted with an aryl group.
According to an embodiment of the present specification, R7 is hydrogen or is combined with an adjacent group to form a heterocyclic ring substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms.
According to one embodiment of the present specification, R7 is hydrogen or is combined with an adjacent group to form a heterocyclic ring substituted or unsubstituted with phenyl.
According to one embodiment of the present specification, R7 is hydrogen or is combined with an adjacent group to form a heterocyclic ring substituted or unsubstituted with phenyl and containing N.
According to an embodiment of the present specification, the above X1 to X7 are the same or different from each other, and each is independently CRa or N.
According to an embodiment of the present specification, at least any one of X1 to X3 is N.
According to an embodiment of the present disclosure, each of X1 to X3 is CRa.
According to an embodiment of the present specification, ra is hydrogen.
According to an embodiment of the present specification, ra is arylthio or aryloxy.
According to an embodiment of the present specification, ra and R4 adjacent thereto are bonded to each other to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.
According to an embodiment of the present specification, the above Ra and R4 adjacent thereto are each other Is combined to form
The dotted line is a portion bonded to the benzene ring of the nucleus.
According to an embodiment of the present specification, the above Y1 and Y2 are the same or different from each other, and are each independently CRbRc, NRd, or O.
According to an embodiment of the present specification, the above Y1 and Y2 are the same or different from each other, and each is independently NRd.
According to an embodiment of the present disclosure, Y3 is CReRf, NRg, O or S.
According to an embodiment of the present specification, Y4 is NRi or O.
According to an embodiment of the present specification, rb and Rc are hydrogen.
According to an embodiment of the present specification, rd is hydrogen, deuterium, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.
According to an embodiment of the present specification, rd is hydrogen, deuterium, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
According to an embodiment of the present specification, rd is hydrogen; deuterium; aryl groups of 6 to 20 carbon atoms substituted or unsubstituted with a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted silyl group.
According to an embodiment of the present specification, rd is hydrogen; deuterium; aryl substituted or unsubstituted with a halogen group, an alkyl group, a substituted or unsubstituted aryl group, or a silyl group substituted or unsubstituted with an aryl group, the number of carbon atoms of which is 6 to 20.
According to an embodiment of the present specification, rd is hydrogen; deuterium; an aryl group having 6 to 20 carbon atoms which is substituted or unsubstituted with F, cl, br, I, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a silyl group which is substituted or unsubstituted with a phenyl group.
According to an embodiment of the present specification, rd is hydrogen; deuterium; an aryl group having 6 to 20 carbon atoms which is substituted or unsubstituted with F, cl, br, I, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a triphenylsilyl group.
According to an embodiment of the present specification, rd is hydrogen; deuterium; aryl groups of 6 to 20 carbon atoms substituted or unsubstituted with F, cl, br, I, methyl, phenyl, biphenyl, naphthyl, or triphenylsilyl groups.
According to an embodiment of the present specification, rd is hydrogen; deuterium; phenyl substituted or unsubstituted with F, methyl, phenyl, biphenyl, naphthyl, or with triphenylsilyl; biphenyl substituted or unsubstituted with F, methyl, phenyl, biphenyl, naphthyl, or triphenylsilyl; terphenyl substituted or unsubstituted with F, methyl, phenyl, biphenyl, naphthyl, or triphenylsilyl; fluorenyl substituted or unsubstituted with F, methyl, phenyl, biphenyl, naphthyl, or triphenylsilyl.
According to an embodiment of the present specification, rd is hydrogen.
According to an embodiment of the present specification, rd is phenyl substituted or unsubstituted with F, phenyl, biphenyl, naphthyl, or triphenylsilyl.
According to an embodiment of the present disclosure, rd is a terphenyl group.
According to an embodiment of the present specification, rd is phenyl or naphthyl substituted or unsubstituted with triphenylsilyl.
According to an embodiment of the present specification, rd is dimethylfluorenyl.
According to an embodiment of the present specification, the above Re and Rf are the same or different from each other, each independently hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.
According to an embodiment of the present specification, the above Re and Rf are the same or different from each other, each independently hydrogen, deuterium, or alkyl.
According to an embodiment of the present specification, the above Re and Rf are the same or different from each other, and are each independently hydrogen, deuterium, or an alkyl group having 1 to 10 carbon atoms.
According to an embodiment of the present specification, the Re and Rf are the same or different from each other, and are each independently hydrogen, deuterium, or methyl.
According to an embodiment of the present specification, rg is hydrogen or a substituted or unsubstituted aryl group.
According to an embodiment of the present specification, rg is hydrogen or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
According to an embodiment of the present specification, rg is hydrogen or a substituted or unsubstituted phenyl group.
According to an embodiment of the present specification, the above Rg is a phenyl group substituted or unsubstituted with deuterium, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
According to an embodiment of the present specification, rg is an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with deuterium, a nitrile group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with an alkyl group, or a heteroaryl group containing O or S.
According to an embodiment of the present specification, the Rg is phenyl substituted or unsubstituted with deuterium, nitrile, tert-butyl, phenyl, naphthyl, dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl.
According to an embodiment of the present specification, rh and Ri described above are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted aryl group.
According to an embodiment of the present specification, rh is hydrogen.
According to an embodiment of the present specification, ri is an aryl group having 6 to 20 carbon atoms.
According to an embodiment of the present specification, ri is phenyl.
According to one embodiment of the present disclosure, L is a direct bond, or a substituted or unsubstituted arylene group.
According to an embodiment of the present specification, L is a directly bonded or substituted or unsubstituted arylene group having 6 to 20 carbon atoms.
According to an embodiment of the present disclosure, L is a direct bond.
According to an embodiment of the present specification, L is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.
According to an embodiment of the present specification, the above L is a substituted or unsubstituted phenylene group substituted or unsubstituted silyl group, or a substituted or unsubstituted alkyl group; a biphenylene group substituted or unsubstituted by a substituted or unsubstituted silyl group, or a substituted or unsubstituted alkyl group; or a naphthylene group substituted or unsubstituted by a substituted or unsubstituted silyl group, or a substituted or unsubstituted alkyl group.
According to an embodiment of the present specification, the above L is a silyl group substituted or unsubstituted with a phenyl group, or an alkyl group having 1 to 10 carbon atoms, or an unsubstituted phenylene group; a biphenylene group substituted or unsubstituted with a silyl group substituted or unsubstituted with a phenyl group, or an alkyl group having 1 to 10 carbon atoms; or a naphthylene group which is substituted or unsubstituted by a silyl group substituted or unsubstituted by a phenyl group or an alkyl group having 1 to 10 carbon atoms.
According to an embodiment of the present specification, the above L is phenylene substituted or unsubstituted with triphenylsilyl or methyl; biphenylene; or naphthylene.
According to an embodiment of the present specification, the above chemical formula 1 may be selected from the following compounds.
According to an embodiment of the present specification, the above chemical formula 2 may be selected from the following compounds.
According to an embodiment of the present specification, the compounds of the above chemical formulas 1 and 2 may be manufactured according to the following reaction formula, but are not limited thereto. In the following reaction scheme, the type and number of substituents can be determined by appropriately selecting known starting materials by those skilled in the art. The kind of reaction and the reaction conditions may be those known in the art.
The compound represented by the above chemical formula 1 can be synthesized by the following method.
X1 to X3 are as defined in the above chemical formula 1,
rv to Rx are the same or different from each other and are each independently hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
The compound represented by the above chemical formula 2 can be synthesized by the following method.
Ry and Rz are the same or different from each other and are each independently hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
In addition, the organic electroluminescent device according to the present invention is characterized by comprising: the light-emitting device includes an anode, a cathode provided opposite to the anode, and a light-emitting layer provided between the anode and the cathode, wherein the light-emitting layer includes a first body represented by chemical formula 1 and a second body represented by chemical formula 2.
The organic light-emitting device of the present invention can be manufactured by a usual method and material for manufacturing an organic light-emitting device, in addition to forming one or more organic layers using the above-described compound.
The organic layer of the organic light-emitting device of the present invention may be formed of a single-layer structure, or may be formed of a multilayer structure in which two or more organic layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or the like as an organic layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers. The organic layer may include one or more of an electron transport layer, an electron injection layer, and a layer that performs electron transport and electron injection at the same time, and one or more of the layers may include the compound.
The organic layer containing the compound of chemical formula 1 may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and the like, but is not limited thereto, 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, for example, spin coating, dip coating, doctor blading, screen printing, ink jet printing, or thermal transfer printing, using various polymer materials.
For example, the structure of the organic light emitting device of the present invention may have the same structure as that shown in fig. 1, but is not limited thereto.
Fig. 1 illustrates a structure of an organic light emitting device in which an anode 2, a second organic layer 3 including a compound of the above chemical formula 1 and a compound of the above chemical formula 2, and a cathode 4 are sequentially stacked on a substrate 1.
In one embodiment of the present invention, the organic layer including the first body and the second body may include at least one of a light emitting layer, an electron injecting layer, an electron transporting layer, and a layer in which electrons are injected and transported simultaneously, and the light emitting layer in the layer may include the first body and the second body.
In one embodiment of the present invention, the light emitting layer is formed by a method comprising the steps of: 3 to 3:1 comprises a first body and a second body.
In one embodiment of the present invention, the light emitting layer is formed by a method comprising the steps of: 2 to 2:1 comprises a first body and a second body.
In an embodiment of the present invention, the light emitting layer is formed by a process of 95:5 to 70:30 comprises a first body and a second body by volume: a dopant.
In an embodiment of the present invention, the light emitting layer is formed by a process of 90:10 to 80:20 comprises a first body and a second body by volume: a dopant.
For example, the organic light emitting device according to the present invention may be manufactured as follows: an anode is formed by vapor deposition of a metal or a metal oxide having conductivity or an alloy thereof on a substrate by PVD (physical vapor deposition) method such as sputtering (sputtering) or electron beam evaporation (e-beam evaporation), then an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an organic layer including a compound of chemical formula 1 or chemical formula 2 are formed on the anode, and then a substance that can be used as a cathode is vapor deposited on the organic layer. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate.
As the anode material, a material having a large work function is generally preferable in order to allow holes to be smoothly injected into the organic layer. Specific examples of the anode material that can be used in the present invention 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); znO: al or SnO 2 : a combination of a metal such as Sb and an oxide; of poly (3-methyl) compounds, poly [3,4- (ethylene-1, 2-dioxy) compounds]Conductive polymers such as (PEDOT), polypyrrole and polyaniline, but not limited thereto.
As the cathode material, a material having a small work function is generally preferred in order to facilitate injection of electrons into the organic layer. Specific 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 material is a material that can satisfactorily receive injected holes from the anode at a low voltage, and preferably has a HOMO (highest occupied molecular orbital) between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection substance include, but are not limited to, metalloporphyrin (porphyrin), oligothiophenes, arylamine-based organic substances, hexanitrile hexaazabenzophenanthrene-based organic substances, quinacridone-based organic substances, perylene-based organic substances, and conductive polymers of anthraquinone, polyaniline, and a polymer compound.
The hole-transporting substance is preferably a substance that can receive holes from the anode or the hole-injecting layer and transfer the holes to the light-emitting layer, and has a large mobility to the holes. Specific examples include, but are not limited to, arylamine-based organic substances, conductive polymers, and block copolymers having both conjugated and unconjugated portions.
The light-emitting substance is a substance capable of receiving holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and combining them to emit light in the visible light region, and preferably has high quantum efficiency for fluorescence or phosphorescence. Specifically, there are 8-hydroxyquinoline 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 (E
Azole, benzothiazole, and benzimidazole compounds; poly (p-phenylene vinylene) (PPV) based polymers; spiro (spiro) compounds; polyfluorene, rubrene, and the like, but is not limited thereto.
The method of manufacturing the compound of chemical formula 1 above and the manufacture of an organic light emitting device using the same are specifically described in the following examples. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited thereto.
In the present invention, iridium phosphorescent dopants may be used as the dopant.
In the present invention, an iridium complex used as a dopant of the light-emitting layer is as follows.
In one embodiment of the present invention, the dopant is included in a weight ratio of 1 to 20%.
In one embodiment of the invention, the dopant is included in a weight ratio of 5 to 15%.
Modes for carrying out the invention
Synthesis example
Production of Compound P1
4-bromo-2-iodoaniline (100 g,335.6 mmol) and (2-chloro-6-fluorophenyl) boronic acid (58.5 g,335.6 mmol) were dissolved in 800ml of Tetrahydrofuran (THF). To this was added sodium carbonate (Na 2 CO 3 ) 2M solution (500 mL), tetrakis (triphenylphosphine) palladium (0) [ Pd (PPh) 3 ) 4 ](7.7 g,6.7 mmol) was refluxed for 12 hours. After the completion of the reaction, the mixture was cooled to room temperature, and the resultant mixture was extracted with water and toluene 3 times. After separation of the toluene layer, the filtrate dried over magnesium sulfate (magnesium sulfate) and filtered was distilled under reduced pressure. Concentrated compound was purified using 10:1 n-hexane: the ethyl acetate solution was subjected to column chromatography to obtain 120.0g. The peak was confirmed by mass spectrometry of the resulting solid at M/z=283.
Production of Compound P2
5-bromo-2 '-chloro- [1,1' -biphenyl]-2-amine (100 g,353.9 mmol), [1,1' -biphenyl)]4-Ylboronic acid (70.1 g,353.9 mmol) was dissolved in 800ml of Tetrahydrofuran (THF). To this was added sodium carbonate (Na 2 CO 3 ) 2M solution (520 mL), tetrakis (triphenylphosphine) palladium (0) [ Pd (PPh) 3 ) 4 ](7.7 g,6.7 mmol) was refluxed for 12 hours. Cooling to normal temperature after the reaction is finishedThe resulting mixture was extracted 3 times with water and toluene at room temperature. After separation of the toluene layer, the filtrate dried over magnesium sulfate (magnesium sulfate) and filtered was distilled under reduced pressure. Subsequently, the mixture was recrystallized from ethanol to obtain 100.8g of compound P2. The peak was confirmed by mass spectrometry of the resulting solid at M/z=356.
Production of Compound P3
Next, 47.0g (132 mmol) of 2-chloro- [1,1':3', 1': 4 ', 1' -tetrabiphenyl as described above]480mL of glacial acetic acid, 120mL of sulfuric acid, 120mL of distilled water are added to the 6' -amine and heated. Then, when turned into a clear solution, it was cooled to 3-4℃and 120mL of a 1.64M aqueous sodium nitrite solution was added and stirred for 30 minutes. The above solution was slowly dropped at 3 to 4℃to copper bromide (CuBr) dissolved with 32.6g (146 mmol) 2 ) 96mL of hydrochloric acid (HCl). Then, the mixture was heated to 45℃and stirred for 30 minutes, heated to 80℃and stirred for 30 minutes. After cooling to room temperature, the organic layer was extracted 3 times with 75mL of chloroform. The organic layer was washed with aqueous sodium hydrogencarbonate and water, and the obtained organic layer was washed with anhydrous magnesium sulfate (MgSO 4 ) And (5) drying. Then, after separation by filtration, the solvent was distilled off under reduced pressure, and recrystallized from ethanol to obtain 41.0g of compound P3. The peak was confirmed by mass spectrometry of the resulting solid at M/z=420.
Production of Compound P4
After the above 42g (100 mmol) of 6 '-bromo-2-chloro-1, 1':3', 1': 4 ', 1' -tetrabiphenyl was dissolved in 300ml of anhydrous tetrahydrofuran under nitrogen, the ambient temperature of the reactor was maintained at-78 ℃. Subsequently, 40ml of 2.5M-butyllithium was slowly added dropwise. After completion of the dropwise addition, stirring was carried out for 30 minutes, and then, 22.8g of 9H-xanthen-9-one was dissolved in 200ml of purified tetrahydrofuran and then, dropwise addition was slowly carried out. After the reaction solution was stirred at-78℃for about 1 hour, the temperature was raised to room temperature and stirring was continued for 12 hours. After the reaction was completed by adding diluted hydrochloric acid to the reaction solution, liquid-separation extraction was performed with methylene chloride. The obtained organic layer was dried over magnesium sulfate, filtered and distilled under reduced pressure. Then, after adding to 400ml of acetic acid, a catalytic amount of hydrochloric acid was added dropwise, followed by stirring at reflux temperature for 12 hours. After completion of the reaction, the mixture was cooled to obtain a solid, which was filtered and subjected to column chromatography to obtain 38.2g of Compound P4. Peaks were confirmed by mass spectrometry of the resulting solid at M/z=519.
Production of Compound P5
15.9g (30 mmol) of the compound represented by the above P4, 8.38g (33 mmol) of bis (pinacolato) diboron, 8.83g (90 mol) of potassium acetate, 200mL of 1, 4-di
After the alkane, 0.86g (1.5 mmol) of Pd (dba) was added 2 And 0.84g (3.0 mmol) of PCy 3 1, 4-Di ∈1 dissolved in 20mL>
The alkane was added dropwise. After stirring under reflux for 24 hours and cooling to room temperature, 200mL of distilled water was added and extracted 2 times with 200mL of methylene chloride. The resulting organic layer was washed with magnesium sulfate (MgSO 4 ) And (5) drying. Then, after separation by filtration, the solvent was distilled off under reduced pressure, and 10.0g of compound P5 was obtained by column chromatography on silica gel (silica gel). The peak was confirmed by mass spectrometry of the resulting solid at M/z=611.
Production of Compound 1A
After dispersing compound P5 (22.6 g,38 mmol) and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (10.3 g,38 mmol) in tetrahydrofuran (150 ml), 2M aqueous potassium carbonate (aq. K) 2 CO 3 ) (58 ml,115 mmol) tetrakis (triphenylphosphine) palladium [ Pd (PPh) 3 ) 4 ](0.45 g,1 mol%) was followed by stirring and refluxing for 6 hours. The temperature was lowered to room temperature, and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethyl acetate, and after filtration, it was dried to produce 19.2g (70.1%) of compound 1A. The peak was confirmed by mass spectrometry of the resulting solid at M/z=716.
FIG. 2 shows the results of liquid chromatography analysis of Compound 1A.
FIG. 3 is the result of mass spectrometry of Compound 1A.
Production of Compound 1B
18.8g (69.2%) of Compound 1B was obtained by the same method as that for Compound 1A except that 4-chloro-2, 6-diphenylpyrimidine (10.1 g,38 mmol) was used. The peak was confirmed by mass spectrometry of the resulting solid at M/z=715.
Production of Compound P6
110.4g of compound P6 was obtained by the same method as that for compound P2 except that (9-phenyl-9H-carbazol-3-yl) boronic acid (101.6 g,353.9 mmol) was used. The peak was confirmed by mass spectrometry of the resulting solid at M/z=445.
Production of Compound P7
Then, the production was performed in the same manner as for the compound P3 except that 58.7g (132 mmol) of 2 '-chloro-5- (9-phenyl-9H-carbazol-3-yl) - [1,1' -biphenyl ] -2-amine was used, whereby 42.6g of the compound P7 was produced. The peak was confirmed by mass spectrometry of the resulting solid at M/z=509.
Production of Compound P8
Then, the same procedure as for compound P4 was repeated except for using 50.8g (100 mmol) of 3- (6-bromo-2 '-chloro- [1,1' -biphenyl ] -3-yl) -9-phenyl-9H-carbazole, whereby 29.8g of compound P8 was obtained. The peak was confirmed by mass spectrometry of the resulting solid at M/z=608.
Production of Compound P9
Then, the same procedure as for compound P5 was followed except that 18.2g (30 mmol) of the compound represented by P8 was used, whereby 9.6g of compound P9 was obtained. The peak was confirmed by mass spectrometry of the resulting solid at M/z=700.
Production of Compound 1C
Compound P9 (26.6 g,38 mmol) and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (10.3g,38 mmol) in tetrahydrofuran (150 ml), 2M aqueous potassium carbonate (aq. K) 2 CO 3 ) (58 ml,115 mmol) tetrakis (triphenylphosphine) palladium [ Pd (PPh) 3 ) 4 ](0.45 g,1 mol%) was followed by stirring and refluxing for 6 hours. The temperature was lowered to room temperature, and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethyl acetate, and after filtration, it was dried to produce 19.2g (49.7%) of compound 1C. The peak was confirmed by mass spectrometry of the resulting solid at M/z=805.
Production of Compound 1D
14.0g (45.8%) of Compound 1D was obtained by the same method as that for Compound 1C except that 4-chloro-2, 6-diphenylpyrimidine (10.1 g,38 mmol) was used. The peak was confirmed by mass spectrometry of the resulting solid at M/z=804.
Production of Compound P11
Compound P10 (110.6 g,353.9 mmol) was dissolved in 800ml of toluene (tolene). To this was added sodium tert-butoxide (54.4 g,566.2 mmol), bis (tri-tert-butylphosphine) palladium [ Pd (P-tBu) 3 ) 2 ](1.8 g,3.5 mmol) was refluxed for 12 hours. After the completion of the reaction, the mixture was cooled to room temperature, and the resultant mixture was extracted with water and toluene 3 times. After separation of the toluene layer, drying was performed with magnesium sulfate (magnesium sulfate), and the filtered filtrate was distilled under reduced pressure. Then, after dissolving in 1000ml of methanol, palladium/activated carbon was slowly charged at room temperature and stirred, 100ml of hydrazine monohydrate was slowly added dropwise, and stirred under reflux for 24 hours. The temperature was lowered to room temperature, palladium was removed by filtration, and the organic layer was extracted 3 times with 400mL of chloroform. The organic layer was washed with aqueous sodium hydrogencarbonate and water, and the obtained organic layer was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying. Then, after separation by filtration, the solvent was distilled off under reduced pressure, and recrystallized from ethanol to obtain 36.0g of compound P11. The peak was confirmed by mass spectrometry of the resulting solid at M/z=369.
Production of Compound P12
Then, the same procedure as for compound P7 was repeated except for using 48.7g (132 mmol) of 5- (9H-carbazol-9-yl) -2 '-chloro- [1,1' -biphenyl ] -2-amine, whereby 30.6g of compound P12 was obtained. The peak was confirmed by mass spectrometry of the resulting solid at M/z=433.
Production of Compound P13
Then, the same procedure as for compound P8 was followed except for using 43.3g (100 mmol) of 9- (6-bromo-2 '-chloro- [1,1' -biphenyl ] -3-yl) -9H-carbazole, whereby 22.4g of compound P13 was produced. The peak was confirmed by mass spectrometry of the resulting solid at M/z=532.
Production of Compound P14
Next, the same procedure as for compound P9 was followed except that 16.0g (30 mmol) of the compound represented by P13 was used, whereby 8.2g of compound P15 was obtained. The peak was confirmed by mass spectrometry of the resulting solid at M/z=624.
Production of Compound 1E
After dispersing compound P14 (23.7 g,38 mmol) and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (10.3 g,38 mmol) in tetrahydrofuran (150 ml), 2M aqueous potassium carbonate (aq. K) 2 CO 3 ) (58 ml,115 mmol) tetrakis (triphenylphosphine) palladium [ Pd (PPh) 3 ) 4 ](0.45 g,1 mol%) was followed by stirring and refluxing for 6 hours. The temperature was lowered to room temperature, and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethyl acetate, and after filtration, it was dried to produce 16.8g (60.7%) of compound 1E. The peak was confirmed by mass spectrometry of the resulting solid at M/z=729.
Production of Compound 1F
9.0g (31.3%) of Compound 1F was obtained by the same method as that for Compound 1E except that 4-chloro-2, 6-diphenylpyrimidine (10.1 g,38 mmol) was used. The peak was confirmed by mass spectrometry of the resulting solid at M/z=728.
Production of Compound P15
The same procedure as for compound P2 was repeated except for using (9-phenyl-9H-carbazol-3-yl) boronic acid (96.3 g,353.9 mmol) to obtain 98.6g of compound P15. The peak was confirmed by mass spectrometry of the resulting solid at M/z=430.
Production of Compound P16
Then, the production was carried out in the same manner as in the compound P3 except that 56.7g (132 mmol) of 2 '-chloro-5- (triphenylen-2-yl) - [1,1' -biphenyl ] -2-amine was used, whereby 34.2g of the compound P16 was produced. The peak was confirmed by mass spectrometry of the resulting solid at M/z=494.
Production of Compound P17
Then, the same procedure as for compound P4 was followed except that 49.4g (100 mmol) of 2- (6-bromo-2 '-chloro- [1,1' -biphenyl ] -3-yl) triphenylene was used, whereby 23.0g of compound P17 was obtained. The peak was confirmed by mass spectrometry of the resulting solid at M/z=593.
Production of Compound P18
Next, the same procedure as for compound P5 was followed except that 17.8g (30 mmol) of the compound represented by compound P17 was used, whereby 9.0g of compound P18 was obtained. The peak was confirmed by mass spectrometry of the resulting solid at M/z=685.
Production of Compound 1G
After dispersing compound P18 (26.0 g,38 mmol) and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (10.3 g,38 mmol) in tetrahydrofuran (150 ml), 2M aqueous potassium carbonate (aq. K) 2 CO 3 ) (58 ml,115 mmol) tetrakis (triphenylphosphine) palladium [ Pd (PPh) 3 ) 4 ](0.45 g,1 mol%) was followed by stirring and refluxing for 6 hours. The temperature was lowered to room temperature, and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethyl acetate, and after filtration, it was dried to produce 17.8G (59.3%) of compound 1G. The peak was confirmed by mass spectrometry of the resulting solid at M/z=790.
Production of Compound 1H
9.8G (31.3%) of Compound 1H was obtained by the same method as that for Compound 1G except that 4-chloro-2, 6-diphenylpyrimidine (10.1G, 38 mmol) was used. The peak was confirmed by mass spectrometry of the resulting solid at M/z=789.
Production of Compound 2A
Compound 9- ([ 1,1' -biphenyl)]-3-yl) -3-bromo-9H-carbazole (10.8 g,27 mmol) and compound (9- ([ 1,1' -biphenyl)]After dispersing (9.8 g,27 mmol) of-3-yl) -9H-carbazol-3-yl-boronic acid in tetrahydrofuran (80 ml), 2M aqueous potassium carbonate (aq. K) was added 2 CO 3 ) After (40 ml,81 mmol) tetrakis (triphenylphosphine) palladium [ Pd (PPh) 3 ) 4 ](0.3 g,1 mol%) was followed by stirring and refluxing for 6 hours. The temperature was lowered to room temperature, the aqueous layer was removed, concentrated under reduced pressure, ethyl acetate was added, stirred under reflux for 1 hour, cooled to room temperature, and the solid was filtered. Chloroform was added to the obtained solid, and the mixture was dissolved under reflux, followed by addition of ethyl acetate, and recrystallization was performed to obtain 11.2g (65.1%) of Compound 2A. The peak was confirmed by mass spectrometry of the resulting solid at M/z=637.
Production of Compound 2B
10.6g (70.0%) of Compound 2B was obtained by the same method as that for Compound 2A except that (9-phenyl-9H-carbazol-3-yl) boronic acid (7.8 g,27 mmol) was used. The peak was confirmed by mass spectrometry of the resulting solid at M/z=561.
Production of Compound 2C
Compound 9- ([ 1,1' -biphenyl)]After dispersing (10.8 g,27 mmol) of-4-yl) -3-bromo-9H-carbazole and (7.8 g,27 mmol) of the compound (9-phenyl-9H-carbazol-3-yl) boric acid in tetrahydrofuran (80 ml), 2M aqueous potassium carbonate (aq. K) 2 CO 3 ) (40 ml,81 mmol) and tetrakis (triphenylphosphine) palladium [ Pd (PPh) 3 ) 4 ](0.3 g,1 mol%) was followed by stirring and refluxing for 8 hours. The temperature was lowered to room temperature, the aqueous layer was removed, concentrated under reduced pressure, ethyl acetate was added, stirred under reflux for 1 hour, cooled to room temperature, and the solid was filtered. Chloroform was added to the obtained solid, and the mixture was dissolved under reflux, followed by addition of ethyl acetate, and recrystallization was performed to obtain 9.8g (64.7%) of Compound 2C. The peak was confirmed by mass spectrometry of the resulting solid at M/z=561.
Production of Compound 2D
Compound 9- ([ 1,1' -biphenyl)]-4-yl) -3-bromo-9H-carbazole (10.8 g,27 mmol) and compound (9- ([ 1,1' -biphenyl)]After dispersing (9.8 g,27 mmol) of-3-yl) -9H-carbazol-3-yl-boronic acid in tetrahydrofuran (80 ml), 2M aqueous potassium carbonate (aq. K) was added 2 CO 3 ) After (40 ml,81 mmol) tetrakis (triphenylphosphine) palladium [ Pd (PPh) 3 ) 4 ](0.3 g,1 mol%) was followed by stirring and refluxing for 8 hours. Cooling to room temperature, removing water layer, concentrating under reduced pressure, adding ethyl acetate, and concentrating under reduced pressureStirring was carried out for 1 hour under reflux, cooling to room temperature and filtering the solid. Chloroform was added to the obtained solid, and the mixture was dissolved under reflux, followed by addition of ethyl acetate, and recrystallization was performed to obtain 7.2g (41.9%) of Compound 2D. The peak was confirmed by mass spectrometry of the resulting solid at M/z=637.
Examples 1 to 16
To ITO (indium tin oxide)
The 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 thus prepared, HI-1 compound as described below was used as a substrate
Is thermally vacuum evaporated to form a hole injection layer.
On the hole injection layer, HT-1 compound is used as the active material
Forming a hole transport layer by thermal vacuum vapor deposition, and forming an HT-2 compound on the HT-1 vapor deposited film by +.>
Vacuum deposition is performed to form an electron blocking layer.
Then, on the HT-2 vapor deposited film, the compound 1 (host) and compound 2 (dopant) produced as described above are deposited ) At a specific volume ratio (ratio as described in Table 1) by simultaneous evaporation
The thickness of (2) is evaporated, and the phosphorescent dopant GD-1 is co-evaporated at a volume ratio of 6 to 15% to form a light-emitting layer.
On the light-emitting layer, the ET-1 substance is used as
Vacuum evaporation of the thickness of (2) and, furthermore, the ET-2 substance in +.>
The electron transport layer and the electron injection layer were formed by co-evaporation of Li with a thickness of 2 wt%. On the electron injection layer, by +.>
Aluminum was deposited in a thickness to form a cathode.
In the above process, the vapor deposition rate of the organic matter is maintained
Aluminum maintenance->
Is to maintain a vacuum degree of 1X 10 during vapor deposition -7 Up to 5X 10 -8 And (5) a bracket.
Comparative example
An organic light emitting device was fabricated by the same method as the above example, except that the contents of the phosphorescent host material and the dopant were changed as shown in table 1 below at the time of forming the light emitting layer. At this time, the host materials A and B used in the comparative example are as follows. The organic light emitting devices fabricated in the above examples to comparative examples 1 to 5 were subjected to current application, voltage, efficiency, brightness, color coordinates and lifetime were measured,the results are shown in table 1 below. At this time, T95 represents the light density of 20mA/cm 2 The time required for the luminance to decrease to 95% when the initial luminance is set to 100%.
Comparative example 1
Compound 1A was isolated as
An OLED device was fabricated in the same manner as in the above example, except that the phosphorescent dopant GD-1 was co-evaporated at a weight ratio of 10% by thickness evaporation.
Comparative example 2
By reacting compound A
An OLED device was fabricated in the same manner as in the above example, except that the phosphorescent dopant GD-1 was co-evaporated at a weight ratio of 10% by thickness evaporation.
Comparative example 3
Compound B and compound PH-1 were combined at 1:1 by simultaneous evaporation
An OLED device was fabricated in the same manner as in the above example, except that the phosphorescent dopant GD-1 was co-evaporated at a thickness of 15% by weight.
Comparative example 4
Compound 1A and compound 1B were combined in 1:1 by simultaneous evaporation
An OLED device was fabricated in the same manner as in the above example, except that the phosphorescent dopant GD-1 was co-evaporated at a thickness of 12% by weight.
Comparative example 5
Compound 2A and compound 2B were combined in 1:1 by simultaneous evaporation
An OLED device was fabricated in the same manner as in the above example, except that the phosphorescent dopant GD-1 was co-evaporated at a weight ratio of 10% by thickness.
The voltage, EGE, color coordinates, and lifetime were measured for the organic light emitting devices manufactured in example 1 and comparative examples 1 to 5, and the results thereof are shown in table 1 below.
EGE was carried out at a current density of 10mA/cm 2 The spectroradiometer CS-1000 (manufactured by Konica Minolta Co.) was used to measure the spectroradiometer spectrum when a voltage was applied to the device. Based on the obtained spectrum of the above-described spectroradiometric luminance, the external quantum efficiency is calculated assuming lambertian radiation is performed.
TABLE 1
In table 1 above, in example 1, the light-emitting layer was prepared by mixing compound 1A and compound 2A in a ratio of 1:1
Is vapor deposited->
The dopant (GD) is used by doping at a ratio of 12% of the total volume of the host and the dopant. Comparative example 4 uses compound 1A and compound 1B instead of compound 1A and compound 2A as the main bodies, and comparative example 5 uses compound 2A and compound 2B instead of compound 1A and compound 2A as the main bodies. Examples 1 to 16 were found to have a voltage lower by about 40%, an EQE higher by about 64%, and a lifetime higher by about 1170% than comparative examples 4 and 5. />
Claims (6)
1. An organic electroluminescent device, comprising: an anode, a cathode provided opposite to the anode, and a light-emitting layer provided between the anode and the cathode, wherein the light-emitting layer includes a first body represented by the following chemical formula 1 and a second body represented by the following chemical formula 2:
Chemical formula 1
In the above-mentioned chemical formula 1,
r3 is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituent of the following chemical formula 3,
chemical formula 2
Chemical formula 3
In the chemical formulas 1 to 3 described above,
in the chemical formulas 1 to 3 described above,
r1, R2 and R4 to R7 are the same or different from each other and are each independently hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or are combined with adjacent groups to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring,
x1 to X7 are identical to or different from each other and are each independently CRa or N,
y1 and Y2 are identical to or different from each other and are each, independently of one another, CRbRc, NRd, O or S,
y3 is CReRf, NRg, O or S, and the total number of the components is,
l is a direct bond, or a substituted or unsubstituted arylene,
ra is hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted aryl, heteroaryl, arylthio, or aryloxy, or is combined with R4 to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring,
rb to Rg are the same or different from each other and are each independently hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted aryl, or heteroaryl,
a is an integer of 0 to 8,
b. e and f are integers of 0 to 7 respectively,
c is an integer of 0 or 1,
d is an integer of 0 to 2,
g is an integer of 0 to 5,
b+c is an integer of 0 to 7,
a. when b, d, e, f and g are plural, each of R1, R2, and R4 to R7 is the same or different from each other independently.
2. The organic electroluminescent device according to claim 1, wherein the chemical formula 1 is any one of the following chemical formulas 4 to 6:
chemical formula 4
Chemical formula 5
Chemical formula 6
In the chemical formulas 4 to 6 described above,
ar is a substituted or unsubstituted terphenyl group, a substituted or unsubstituted phenanthryl group, or a substituted or unsubstituted triphenylene group,
x4 and X7 are identical to or different from each other and are each independently CRh or N,
y4 is NRi or O, and the total number of the catalyst is equal to or less than zero,
r8 is hydrogen, deuterium, nitrile, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted silyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, or is combined with adjacent groups to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocycle,
rh and Ri are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted aryl group,
h is an integer of 0 to 4,
g is an integer of 0 to 3,
R1 to R4, R7, X1 to X3, a to d, and Ra to Rd are as defined in the chemical formulas 1 and 3.
3. The organic electroluminescent device of claim 1, wherein R4 is aryl substituted or unsubstituted, or heteroaryl substituted or unsubstituted with aryl.
4. The organic electroluminescent device according to claim 1, wherein the first host represented by chemical formula 1 is selected from the following compounds:
5. the organic electroluminescent device according to claim 1, wherein the second host represented by chemical formula 2 is selected from the following compounds:
6. the organic electroluminescent device of claim 1, wherein the light emitting layer is at least one of: 5 to 70:30 comprises a first body and a second body by volume: a dopant.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20170098073 | 2017-08-02 | ||
| KR10-2017-0098073 | 2017-08-02 | ||
| PCT/KR2018/008568 WO2019027189A1 (en) | 2017-08-02 | 2018-07-27 | Organic electroluminescent device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110800122A CN110800122A (en) | 2020-02-14 |
| CN110800122B true CN110800122B (en) | 2023-05-02 |
Family
ID=65232767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880042379.9A Active CN110800122B (en) | 2017-08-02 | 2018-07-27 | Organic electroluminescent device |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR102144164B1 (en) |
| CN (1) | CN110800122B (en) |
| WO (1) | WO2019027189A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102139859B1 (en) * | 2017-08-02 | 2020-07-30 | 주식회사 엘지화학 | Hetero-cyclic compound and organic light emitting device comprising the same |
| KR102172584B1 (en) * | 2018-03-09 | 2020-11-02 | 주식회사 엘지화학 | Compound and organic light emitting device comprising same |
| KR20200129988A (en) * | 2019-05-10 | 2020-11-18 | 주식회사 엘지화학 | Organic light emitting device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015152650A1 (en) * | 2014-04-04 | 2015-10-08 | 주식회사 엘지화학 | Heterocyclic compound and organic light-emitting element comprising same |
| WO2016012075A1 (en) * | 2014-07-21 | 2016-01-28 | Merck Patent Gmbh | Materials for electronic devices |
| CN105722826A (en) * | 2013-11-08 | 2016-06-29 | Mbk有限公司 | Novel organic compound, and organic electroluminescent element and electronic device comprising same |
| CN106660940A (en) * | 2015-06-08 | 2017-05-10 | 出光兴产株式会社 | Compound, material for organic electroluminescent element, and electronic device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10135513B4 (en) | 2001-07-20 | 2005-02-24 | Novaled Gmbh | Light-emitting component with organic layers |
| US20150115241A1 (en) * | 2012-04-02 | 2015-04-30 | Novaled Gmbh | Use of a Semiconducting Compound in an Organic Light Emitting Device |
| KR101849827B1 (en) * | 2015-03-17 | 2018-04-17 | 주식회사 엘지화학 | Organic light emitting device |
| KR101593368B1 (en) * | 2015-04-22 | 2016-02-11 | 주식회사 엘지화학 | Hetero-cyclic compound and organic light emitting diode comprising the same |
| KR101742436B1 (en) * | 2015-12-15 | 2017-05-31 | 주식회사 두산 | Organic compounds and organic electro luminescence device comprising the same |
-
2018
- 2018-07-27 CN CN201880042379.9A patent/CN110800122B/en active Active
- 2018-07-27 KR KR1020180087802A patent/KR102144164B1/en active IP Right Grant
- 2018-07-27 WO PCT/KR2018/008568 patent/WO2019027189A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105722826A (en) * | 2013-11-08 | 2016-06-29 | Mbk有限公司 | Novel organic compound, and organic electroluminescent element and electronic device comprising same |
| WO2015152650A1 (en) * | 2014-04-04 | 2015-10-08 | 주식회사 엘지화학 | Heterocyclic compound and organic light-emitting element comprising same |
| WO2016012075A1 (en) * | 2014-07-21 | 2016-01-28 | Merck Patent Gmbh | Materials for electronic devices |
| CN106536485A (en) * | 2014-07-21 | 2017-03-22 | 默克专利有限公司 | Materials for electronic devices |
| CN106660940A (en) * | 2015-06-08 | 2017-05-10 | 出光兴产株式会社 | Compound, material for organic electroluminescent element, and electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190014472A (en) | 2019-02-12 |
| CN110800122A (en) | 2020-02-14 |
| WO2019027189A1 (en) | 2019-02-07 |
| KR102144164B1 (en) | 2020-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3032606B1 (en) | Organic optoelectric device and display device | |
| EP3016169B1 (en) | Organic optoelectric device and display device | |
| CN111433216A (en) | Heterocyclic compound and organic light-emitting device comprising same | |
| EP3428163A1 (en) | Polycyclic compound and organic light emitting element comprising same | |
| CN112334463B (en) | Compound and organic light emitting device comprising the same | |
| KR20200063053A (en) | Novel compound and organic light emitting device comprising the same | |
| CN111225905B (en) | Heterocyclic compound and organic light-emitting device comprising same | |
| CN110088110B (en) | Novel compound and organic light-emitting element comprising same | |
| CN111527081B (en) | Polycyclic compound and organic light emitting diode including the same | |
| CN111683941B (en) | Heterocyclic compound and organic light-emitting device comprising same | |
| CN110536887B (en) | Novel compound and organic light emitting device comprising the same | |
| CN112041315A (en) | Novel compound and organic light emitting device comprising the same | |
| CN107257787B (en) | Heterocyclic compound and organic light-emitting element comprising same | |
| CN110944991B (en) | Heterocyclic compound and organic light emitting device including the same | |
| JP2020514335A (en) | Novel compound and organic light emitting device using the same | |
| CN110800122B (en) | Organic electroluminescent device | |
| KR101833665B1 (en) | Hetero-cyclic compound and organic light emitting device comprising the same | |
| CN116057040A (en) | Novel compound and organic light emitting device comprising the same | |
| CN113039183B (en) | Novel compound and organic light emitting device comprising the same | |
| CN115461339A (en) | Novel compound and organic light emitting device comprising same | |
| CN112334472B (en) | Novel compound and organic light emitting device comprising the same | |
| CN112533912B (en) | Compound and organic light emitting device comprising the same | |
| CN112912375A (en) | Novel compound and organic light emitting device comprising same | |
| CN110520427B (en) | Novel heterocyclic compound and organic light-emitting element using same | |
| KR20200068568A (en) | Novel compound and organic light emitting device comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |