WO2019160315A1 - Composé hétérocyclique et dispositif électroluminescent organique le comprenant - Google Patents

Composé hétérocyclique et dispositif électroluminescent organique le comprenant Download PDF

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WO2019160315A1
WO2019160315A1 PCT/KR2019/001739 KR2019001739W WO2019160315A1 WO 2019160315 A1 WO2019160315 A1 WO 2019160315A1 KR 2019001739 W KR2019001739 W KR 2019001739W WO 2019160315 A1 WO2019160315 A1 WO 2019160315A1
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group
substituted
unsubstituted
light emitting
layer
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Korean (ko)
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윤홍식
이준엽
박희준
홍완표
강유진
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주식회사 엘지화학
성균관대학교산학협력단
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Priority to CN201980005108.0A priority Critical patent/CN111225905B/zh
Publication of WO2019160315A1 publication Critical patent/WO2019160315A1/fr

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    • H—ELECTRICITY
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
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    • 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
    • C07D405/14—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 three or more hetero rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • 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
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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
    • H10K85/649—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
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    • 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
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • 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

Definitions

  • the present specification relates to a heterocyclic compound and an organic light emitting device formed using the heterocyclic compound.
  • organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
  • An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween.
  • the organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.
  • the present specification provides a heterocyclic compound and an organic light emitting device including the same.
  • X is O or S
  • A1 and A2 are the same as or different from each other, and each independently substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted trialkylsilyl group, substituted or unsubstituted triarylsilyl group, substituted Or an unsubstituted dialkylarylsilyl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents are bonded to each other to form a substituted or unsubstituted aliphatic group.
  • a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted heterocycle To form a ring, a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted heterocycle,
  • L1 and L2 are the same as or different from each other, and each independently a direct bond or an arylene group,
  • R1 and R2 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group,
  • a is an integer of 0 to 3
  • b 0 or 1
  • n is an integer from 0 to 2
  • n is an integer from 0 to 4,
  • R1 is the same as or different from each other
  • the present specification is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the heterocyclic compound.
  • the heterocyclic compound according to the exemplary embodiment of the present specification may be used as a material of the organic material layer of the organic light emitting device, and by using the same, it is possible to improve efficiency, low driving voltage, and / or lifespan characteristics in the organic light emitting device.
  • the compound according to the exemplary embodiment of the present invention has a high electron accepting structure, has a delayed fluorescent property, and can maintain an appropriate deposition temperature when fabricating an organic light emitting device.
  • FIG. 1 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.
  • FIG. 2 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.
  • the present specification provides a heterocyclic compound represented by Chemical Formula 1.
  • substituted means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.
  • substituted or unsubstituted is deuterium; Nitrile group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; And it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, or two or more of the substituents exemplified above are substituted with a substituent, or means that do not have any substituents.
  • a substituent to which two or more substituents are linked may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, or the like.
  • the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 30.
  • Specific examples 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, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-o
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. It is not.
  • the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like.
  • the present invention is not limited thereto.
  • the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.
  • the aryl group is a monocyclic aryl group
  • carbon number is not particularly limited, but is preferably 6 to 30 carbon atoms.
  • the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.
  • Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-30.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, penalenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto. no.
  • the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.
  • examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group.
  • the aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group.
  • the arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.
  • the aryl group in the arylamine group may be selected from the examples of the aryl group described above.
  • the aryl group in the aryloxy group, the N-arylalkylamine group, and the N-arylheteroarylamine group is the same as the aryl group described above.
  • the aryloxy group may be a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3- Biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, and the like.
  • the heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number is not particularly limited, it is preferably 2 to 30 carbon atoms, the heteroaryl group may be monocyclic or polycyclic.
  • heterocyclic group examples include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene
  • examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group.
  • the heteroarylamine group including two or more heteroaryl groups may simultaneously include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group.
  • the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.
  • heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the heteroaryl group described above.
  • arylene is the same as the example of the aryl group mentioned above except that it is bivalent.
  • Formula 1 is represented by any one of the following formula (2) and formula (3).
  • A11 to A14 are the same as the definitions of A1,
  • L11 to L14 are the same as the definition of L1,
  • A21 and A22 are the same as defined in A2,
  • L21 and L22 are the same as the definitions of L2.
  • Chemical Formula 1 may be represented by any one of the compounds of Formulas 4 to 11.
  • A11 to A14 are the same as the definitions of A1,
  • L11 to L14 are the same as the definition of L1,
  • A21 and A22 are the same as defined in A2,
  • L21 and L22 are the same as the definitions of L2.
  • m + n 1.
  • the A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted Arylamine group.
  • the A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, each independently substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number It is a heteroaryl group of 3-30, or a substituted or unsubstituted arylamine group.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently deuterium, nitrile group, halogen group, aryl group, heteroaryl group, silyl group, boron And an aryl group unsubstituted or substituted with a substituent selected from a group, an alkenyl group, a carbonyl group, a phosphine oxide group, and an amine group.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently an aryl group unsubstituted or substituted with an alkyl group.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently represent an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group or an aryl group.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms It is a C6-C30 aryl group.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently a methyl group, ethyl group, propyl group, isopropyl group, butyl group, terbutyl group, pen Substituted or unsubstituted with a methyl group, hexyl group, cyclohexyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, quarterphenyl group, phenanthrene group, anthracene group, pyrene group, triphenylene group, fluorene group, or spirobifluorene group Aryl group having 6 to 30 ring carbon atoms.
  • the A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, each independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms
  • the substituted or unsubstituted An aryl group having 6 to 30 carbon atoms is a phenyl group; Naphthyl group; Biphenyl group; Terphenyl group; Quarter-phenyl group; Phenanthrene group; Anthracene groups; Pyrene group; Triphenylene group; Fluorene group; And spirobifluorene groups, but is not limited thereto.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently a nitrile group, a halogen group, an alkyl group, an aryl group, a heteroaryl group, a silyl group, and boron And a heteroaryl group unsubstituted or substituted with a substituent selected from a group, an alkenyl group, a carbonyl group, a phosphine oxide group, and an amine group.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently a nitrile group, a halogen group, an alkyl group, an aryl group, a heteroaryl group, a silyl group, and boron And a heteroaryl group having 3 to 30 carbon atoms containing at least one of N, O, and S unsubstituted or substituted with a substituent selected from a group, an alkenyl group, a carbonyl group, a phosphine oxide group, and an amine group.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms Monocyclic or polycyclic heteroaryl group containing one or more of N, O, and S,
  • the monocyclic or polycyclic heteroaryl group may be a pyrrole group, a pyridine group, a pyrimidine group, a triadine group, a carbazole group, an imidazole group, a pyrrole group, a quinazol group, a quinoline group, a furan group, a benzofuran group, a dibenzofuran group, a benzo It may be selected from naphthofuran group, thiophene group, benzothiophene group, dibenzothiophene group, and benzonaphthothiophene group, but is not limited thereto.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently a carbazole group, a dibenzofuran group, or a dibenzothiophene group,
  • the carbazole group, dibenzofuran group, or dibenzothiophene group may be substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently deuterium, nitrile group, halogen group, aryl group, heteroaryl group, silyl group, boron And an arylamine group unsubstituted or substituted with a substituent selected from a group, an alkenyl group, a carbonyl group, a phosphine oxide group, and an amine group.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently substituted or unsubstituted with a deuterium, nitrile group, halogen group, aryl group, or heteroaryl group Arylamine group.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently substituted with an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms or It is an unsubstituted arylamine group.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently a monocyclic aryl group having 6 to 30 carbon atoms, and a polycyclic aryl group having 6 to 30 carbon atoms.
  • An arylamine group unsubstituted or substituted with a monocyclic heteroaryl group having 6 to 30 carbon atoms or a polycyclic heteroaryl group having 3 to 20 carbon atoms.
  • A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a methyl group, terbutyl group, or carbazole group; Naphthyl group; Carbazole groups unsubstituted or substituted with a phenyl group or a terbutyl group; Dibenzofuran group; Dibenzothiophene group; Diphenyl fluorene group; Dimethyl fluorene group; Spirobifluorene; Or a diphenylamine group.
  • L1, L2, L11 to L14, L21 and L22 are the same as or different from each other, and each independently a direct bond, or an arylene group having 6 to 30 carbon atoms.
  • L1, L2, L11 to L14, L21 and L22 are the same as or different from each other, and each independently a divalent phenyl group, a divalent biphenylene group, a divalent terphenylene group, a divalent pephenyl It is a nanthrene group, a bivalent anthracene group, or a bivalent triphenylene group.
  • L1, L2, L11 to L14, L21 and L22 are the same as or different from each other, and each independently a direct bond or a phenylene group.
  • n is 0.
  • n is 0.
  • n is 0.
  • n is 1, m is 0.
  • n is 2, m is 0.
  • heterocyclic compound of Formula 1 may be represented by any one selected from the following structural formula.
  • the organic light emitting device comprises a first electrode; A second electrode provided to face the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the heterocyclic compound.
  • the organic light emitting device of the present invention may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that at least one organic material layer is formed using the above-described compound.
  • the organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked.
  • 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 and the like as an organic material layer.
  • the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.
  • the organic material layer may include one or more layers of an electron transport layer, an electron injection layer, and a layer for simultaneously transporting and transporting electrons, and one or more of the layers may include the compound.
  • the organic material layer including the heterocyclic compound of Formula 1 may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure.
  • the organic layer may be prepared by using a variety of polymer materials, and by using a method such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than a deposition method. It can be prepared in layers.
  • the structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.
  • FIG. 1 illustrates a structure of an organic light emitting device in which a first electrode 2, an organic material layer 3, a light emitting layer 4, and a second electrode 5 are sequentially stacked on a substrate 1.
  • the first electrode 2 the hole injection layer 6, the hole transport layer 7, the electron blocking layer 8, the light emitting layer 4, the hole blocking layer 9, the electron injection and transport layer 10, and
  • the structure of the organic light emitting element in which the second electrode 5 is sequentially stacked is illustrated.
  • the heterocyclic compound of Formula 1 is included in the emission layer.
  • 1 and 2 illustrate an organic light emitting diode and are not limited thereto.
  • the organic light emitting device includes a structure in which a first electrode / light emitting layer / second electrode is sequentially stacked.
  • the organic light emitting device includes a structure in which a first electrode / hole transport layer / electron suppression layer / light emitting layer / second electrode is sequentially stacked.
  • the organic light emitting device includes a structure in which a first electrode / hole injection layer / hole transport layer / light emitting layer / second electrode is sequentially stacked.
  • the organic light emitting device includes a structure in which the first electrode / hole injection layer / hole transport layer / light emitting layer / electron injection and transport layer / second electrode are sequentially stacked.
  • the organic light emitting device includes a structure in which the first electrode / hole injection layer / hole transport layer / electron suppression layer / light emitting layer / electron injection and transport layer / second electrode are sequentially stacked.
  • the organic light emitting device includes a structure in which the first electrode / hole injection layer / hole transport layer / electron suppression layer / light emitting layer / hole suppression layer / electron injection and transport layer / second electrode are sequentially stacked.
  • the organic light emitting device may include a light emitting layer, and the light emitting layer may include a heterocyclic compound of Chemical Formula 1.
  • the organic light emitting device comprises a heterocyclic compound of Formula 1 in the light emitting layer as a dopant of the light emitting layer.
  • the organic light emitting device includes an organic compound in the light emitting layer as a host of the light emitting layer.
  • the organic light emitting device includes a heterocyclic compound in the light emitting layer as a host of the light emitting layer.
  • the organic light emitting device includes an N-containing heterocyclic compound as a host of the light emitting layer.
  • the organic light emitting device includes a carbazole compound in the light emitting layer as a host of the light emitting layer.
  • the organic light emitting device includes a carbazole compound in the light emitting layer as a host of the light emitting layer.
  • the organic light emitting device includes a host and a dopant in a weight ratio of 90:10 to 10:90 in the light emitting layer.
  • the organic light emitting diode includes a host and a dopant in a light emitting layer in a weight ratio of 80:20 to 50:50.
  • the organic light emitting device includes a host and a dopant in a weight ratio of 80:20 to 60:40 in the light emitting layer.
  • the organic light emitting device includes an electron injection layer, an electron transport layer, or a hole blocking layer, and the heterocyclic compound of Formula 1 is added to the electron injection layer, the electron transport layer, or the hole blocking layer. It may include.
  • the organic light emitting device comprises a hole injection layer, a hole transport layer, or an electron blocking layer, the hole injection layer, a hole transport layer, or an electron blocking layer in the heterocyclic compound of Formula 1 It may include.
  • the organic light emitting device uses a metal vapor deposition (PVD) method such as sputtering or e-beam evaporation, and has a metal oxide or a metal oxide or an alloy thereof on a substrate.
  • PVD metal vapor deposition
  • an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an organic material layer containing a heterocyclic compound of the formula (1), and then used as a cathode thereon It can be prepared by depositing.
  • an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
  • the anode material a material having a large work function is usually preferred to facilitate hole injection into the organic material layer.
  • the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SnO 2 : Combination of metals and oxides such as Sb; Conductive polymers such as poly (3-methyl compound), poly [3,4- (ethylene-1,2-dioxy) compound] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the cathode material is a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.
  • the hole injection material is a material capable of well injecting holes from the anode at a low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer.
  • the hole injection material include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene-based organics, quinacridone-based organics, and perylene-based Organic compounds, anthraquinones and polyaniline and poly-compounds of conductive polymers, and the like, but are not limited thereto.
  • the hole transporting material a material capable of transporting holes from the anode or the hole injection layer to be transferred to the light emitting layer is suitable.
  • a material capable of transporting holes from the anode or the hole injection layer to be transferred to the light emitting layer is suitable.
  • Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.
  • the light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.
  • Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq 3 ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.
  • the light emitting layer may include a host material and a dopant material.
  • the host material is a condensed aromatic ring derivative or a heterocyclic containing compound.
  • the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds
  • the heterocyclic compounds include heterocyclic compounds, dibenzofuran derivatives, and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • the organic material layers may be formed of the same material or different materials.
  • the organic light emitting device of the present specification may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate.
  • an anode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation.
  • PVD physical vapor deposition
  • an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, and an electron transporting layer thereon, and then depositing a material that can be used as a cathode thereon.
  • an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
  • the electron transporting layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer.
  • an electron transporting material a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer is suitable. Do. Specific examples thereof include Al complexes of 8-hydroxyquinoline; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
  • the electron transport layer can be used with any desired cathode material as used in accordance with the prior art.
  • suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.
  • the electron injection layer is a layer that injects electrons from an electrode, has an ability to transport electrons, has an electron injection effect from a cathode, an electron injection effect with respect to a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer
  • the compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable.
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.
  • Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, It is not limited to this.
  • the hole blocking layer is a layer for preventing the cathode from reaching the hole, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like, but are not limited thereto.
  • the organic light emitting device may be a top emission type, a bottom emission type, or a double side emission type according to a material used.
  • the heterocyclic compound may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
  • the compound of Formula 1 may be prepared according to the following reaction scheme, but is not limited thereto.
  • the type and number of substituents can synthesize various kinds of intermediates as those skilled in the art appropriately select known starting materials.
  • Reaction type and reaction conditions may be used those known in the art.
  • the compound represented by Chemical Formula 1 may be prepared from a process of forming a ring by introducing various types of benzene into benzene substituted with a halide as follows. After introducing cyanide, compounds were synthesized by finally introducing carbazole, heteroaryl, and aryl.
  • the compound represented by Formula 1 according to the exemplary embodiment of the present specification is included in a light emitting layer with a host material (m-CBP) having a triplet value of 2.5 eV or more, to manufacture an organic light emitting device, and characteristics Evaluated.
  • m-CBP host material
  • a glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 ⁇ was placed in distilled water in which detergent was dissolved and ultrasonically cleaned.
  • ITO indium tin oxide
  • Fischer Co. product was used as a detergent
  • distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water.
  • ultrasonic washing was performed twice with distilled water for 10 minutes.
  • ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol dried and transported to a plasma cleaner.
  • the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.
  • Each thin film was deposited on the ITO transparent electrode thus prepared at a vacuum degree of 5.0 ⁇ 10 -4 Pa by vacuum deposition.
  • hexanitrile hexaazatriphenylene (HAT) was thermally vacuum deposited to a thickness of 500 kPa on ITO to form a hole injection layer.
  • the compound N-([1,1'-bisphenyl] -4-yl) -N- (4- (11-([1,1'-biphenyl] -4-yl) having a film thickness of 100 kPa on the hole transport layer ) -11H-benzo [a] carbazole-5-yl) phenyl)-[1,1'-biphenyl] -4-amine (EB1) (100 Pa) was vacuum deposited to form an electron blocking layer.
  • the following m-CBP and the compound 4CzIPN were vacuum-deposited at a weight ratio of 70:30 on the electron blocking layer with a film thickness of 300 Pa to form a light emitting layer.
  • Compound HB1 was vacuum deposited on the light emitting layer at a film thickness of 100 Pa to form a hole blocking layer.
  • Compound ET1 and compound LiQ were vacuum deposited on the hole blocking layer in a weight ratio of 1: 1 to form an electron injection and transport layer at a thickness of 300 ⁇ .
  • lithium fluoride (LiF) and aluminum were deposited sequentially to have a thickness of 12 kW to form a cathode.
  • the deposition rate of the organic material was maintained at 0.4 ⁇ 0.7 ⁇ / sec
  • the lithium fluoride of the cathode was maintained at a deposition rate of 0.3 ⁇ / sec
  • aluminum 2 ⁇ / sec the vacuum degree during deposition is 2 X 10 -7
  • the organic light emitting device was manufactured by maintaining ⁇ 5 ⁇ 10 ⁇ 6 torr.
  • An organic light emitting diode was manufactured according to the same method as Comparative Example 1 except for using the compound of Table 1 instead of the compound 4CzIPN in Comparative Example 1.
  • An organic light emitting diode was manufactured according to the same method as Comparative Example 1 except for using the compound of T1 to T2 instead of the compound 4CzIPN in Comparative Example 1.
  • the compound according to the present invention was confirmed that the excellent light emitting ability and high color purity can be applied to the delayed fluorescent organic light emitting device.

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Abstract

La présente invention concerne un composé hétérocyclique de formule 1 et un dispositif électroluminescent organique le comprenant.
PCT/KR2019/001739 2018-02-13 2019-02-13 Composé hétérocyclique et dispositif électroluminescent organique le comprenant WO2019160315A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3712145A1 (fr) * 2019-03-19 2020-09-23 Samsung Electronics Co., Ltd. Composé cyclique condensé et dispositif électroluminescent organique le comprenant
WO2021127381A1 (fr) * 2019-12-19 2021-06-24 Kyulux, Inc. Composition de substances destinée à être utilisée dans des diodes électroluminescentes organiques
WO2023078812A1 (fr) 2021-11-02 2023-05-11 Merck Patent Gmbh Dérivés de benzofuro[3,2-d]pyrimidino-2,4-dicarbonitrile et composés similaires pour dispositifs électroluminescents organiques

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102233421B1 (ko) * 2018-07-06 2021-03-29 주식회사 엘지화학 신규한 화합물 및 이를 이용한 유기 발광 소자
JP2023500759A (ja) * 2019-11-21 2023-01-11 エルティー・マテリアルズ・カンパニー・リミテッド ヘテロ環化合物、これを含む有機発光素子、有機発光素子の有機物層用組成物および有機発光素子の製造方法
CN114591290A (zh) * 2022-03-31 2022-06-07 陕西维世诺新材料有限公司 一种取代苯并[b]萘苯[2，3-d]噻吩衍生物的制备方法及衍生物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011082238A (ja) * 2009-10-05 2011-04-21 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子、照明装置及び表示装置
WO2016157113A1 (fr) * 2015-03-31 2016-10-06 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazole portant des groupes aryl- ou hétéroarylnitrile pour diodes électroluminescentes organiques
CN107400086A (zh) * 2017-07-27 2017-11-28 长春海谱润斯科技有限公司 一种有机化合物及使用该化合物制备的有机电致发光器件
US20170369439A1 (en) * 2016-06-27 2017-12-28 Samsung Electronics Co., Ltd. Condensed cyclic compound, composition including the same, and organic light-emitting device including the condensed cyclic compound

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10135513B4 (de) 2001-07-20 2005-02-24 Novaled Gmbh Lichtemittierendes Bauelement mit organischen Schichten
KR20110112098A (ko) * 2010-04-06 2011-10-12 다우어드밴스드디스플레이머티리얼 유한회사 신규한 유기 발광 화합물 및 이를 채용하고 있는 유기 전계 발광 소자
JP6007467B2 (ja) * 2010-07-27 2016-10-12 コニカミノルタ株式会社 有機エレクトロルミネッセンス素子材料、有機エレクトロルミネッセンス素子、
KR20120109744A (ko) * 2011-03-25 2012-10-09 롬엔드하스전자재료코리아유한회사 신규한 유기 전자재료용 화합물 및 이를 포함하는 유기 전계 발광 소자
WO2014157371A1 (fr) * 2013-03-28 2014-10-02 日本合成化学工業株式会社 Nouveau composé imidazole, matière pour des dispositifs électroniques, élément émettant de la lumière, dispositif électronique et procédé de fabrication de dispositif électronique
WO2016195406A2 (fr) * 2015-06-03 2016-12-08 주식회사 엘지화학 Composé hétérocyclique et dispositif électroluminescent organique contenant ce composé
KR102577274B1 (ko) * 2015-11-16 2023-09-12 삼성전자주식회사 유기 발광 소자
CN106887444B (zh) * 2015-12-15 2020-01-10 昆山工研院新型平板显示技术中心有限公司 有机发光显示器件及显示装置
KR102504131B1 (ko) * 2017-04-27 2023-02-28 삼성디스플레이 주식회사 헤테로시클릭 화합물 및 이를 포함한 유기 발광 소자

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011082238A (ja) * 2009-10-05 2011-04-21 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子、照明装置及び表示装置
WO2016157113A1 (fr) * 2015-03-31 2016-10-06 Idemitsu Kosan Co., Ltd. Benzimidazolo[1,2-a]benzimidazole portant des groupes aryl- ou hétéroarylnitrile pour diodes électroluminescentes organiques
US20170369439A1 (en) * 2016-06-27 2017-12-28 Samsung Electronics Co., Ltd. Condensed cyclic compound, composition including the same, and organic light-emitting device including the condensed cyclic compound
CN107400086A (zh) * 2017-07-27 2017-11-28 长春海谱润斯科技有限公司 一种有机化合物及使用该化合物制备的有机电致发光器件

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DENG, L.: "Simple bipolar host materials incorporating CN group for highly efficient blue electrophosphorescence with slow efficiency roll-off", JOURNAL OF , MATERIALS CHEMISTRY C, 2013, pages 8140 - 8145, XP055631408 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3712145A1 (fr) * 2019-03-19 2020-09-23 Samsung Electronics Co., Ltd. Composé cyclique condensé et dispositif électroluminescent organique le comprenant
WO2021127381A1 (fr) * 2019-12-19 2021-06-24 Kyulux, Inc. Composition de substances destinée à être utilisée dans des diodes électroluminescentes organiques
WO2023078812A1 (fr) 2021-11-02 2023-05-11 Merck Patent Gmbh Dérivés de benzofuro[3,2-d]pyrimidino-2,4-dicarbonitrile et composés similaires pour dispositifs électroluminescents organiques

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