WO2022045817A1 - Phenanthrene derivatives and organic light emitting diodes comprising derivatives - Google Patents

Abstract

The present invention relates to phenanthrene derivatives which can be employed in an organic layer in organic light emitting diodes, and highly efficient and long-life organic light emitting diodes comprising same. Since highly efficient and long-life organic light emitting diodes can be produced by employing the phenanthrene derivatives of the present invention as a hole transport material in diodes, the phenanthrene derivative can be industrially utilized in a flat panel display device, a flexible display device, a monochromatic or white flat panel lighting device, a monochromatic or white flexible lighting device and the like.

Description

Phenanthrene derivative compound and organic light emitting device comprising same

The present invention relates to a phenanthrene derivative compound and a high-efficiency and long-life organic light emitting device comprising the same.

In an organic light emitting device, an electron injected from an electron injection electrode (cathode electrode) and a hole injected from a hole injection electrode (anode electrode) are combined in an emission layer to form an exciton, and the exciton generates energy It is a self-luminous device that emits light while emitting light, and such an organic light-emitting device has a low driving voltage, high luminance, wide viewing angle, and fast response speed, and is in the spotlight as a next-generation light source because of the advantages that it can be applied to a full-color flat panel light emitting display. .

In order for such an organic light emitting device to exhibit the above characteristics, the structure of the organic layer in the device is optimized, and the material constituting each organic layer is a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, an electron blocking material. It should be preceded by a stable and efficient material, but it is still necessary to continuously develop a stable and efficient organic layer structure and each material for an organic light emitting device.

As such, the structure of the device capable of improving the light emitting characteristics of the organic light emitting device and the development of a new material supporting the structure are continuously required.

Accordingly, an object of the present invention is to provide an organic light emitting compound capable of implementing a highly efficient organic light emitting device by being employed in the organic layer of the device and an organic light emitting device including the same.

In order to solve the above problems, the present invention provides a compound having a framework structure represented by the following [Formula A] or [Formula B] and an amine group introduced therein.

[Formula A]

[Formula B]

Specific structures of the [Formula A] to [Formula B] and compounds implemented accordingly, and definitions of L ₁ to L ₆ , Ar ₁ to Ar ₂ and R ₁ to R ₄ will be described later.

In addition, the present invention includes a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer is [Formula A] or [Formula B] It provides an organic light emitting device comprising at least one compound implemented as

According to an embodiment of the present invention, the organic layer including at least one compound embodied by the [Formula A] or [Formula B] may be a hole transport layer.

The phenanthrene derivative compound according to the present invention may be employed as an organic layer in the device, particularly as a hole transport material, thereby realizing a high-efficiency and long-life organic light emitting device.

Hereinafter, the present invention will be described in more detail.

The phenanthrene derivative compound according to the present invention is represented by the following [Formula A] or [Formula B], an amine group is introduced into phenanthrene, and structurally, a characteristic structure is introduced at positions 3 and 10 of phenanthrene. In particular, a highly efficient organic light emitting device is produced by introducing an amine structure (arylamine group, heteroarylamine group, arylheteroarylamine group, etc.) at any one of positions 3 and 10 of phenanthrene. can be implemented

[Formula A]

[Formula A] is characterized in that an aryl group, a heteroaryl group, etc. are introduced at the 10-position of phenanthrene, and an amine structure is introduced through a linking group, etc. at the 3-position.

In the [Formula A],

Ar ₁ is any one selected from a substituted or unsubstituted C 10 to C 50 aryl group and a substituted or unsubstituted C 1 to C 50 heteroaryl group, and according to an embodiment of the present invention, Ar ₁ is aryl In the case of a group, it is structurally characterized in that it does not include phenyl as having 10 or more carbon atoms.

L ₁ To L ₃ Are the same as or different from each other and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroarylene group having 1 to 50 carbon atoms In any one selected from, n, o, and p are each independently an integer of 0 to 3, and when L ₁ to L ₃ are a plurality, they are the same or different from each other.

According to an embodiment of the present invention, each of L ₂ and L ₃ may be a single bond or a substituted or unsubstituted arylene group having 6 to 24 carbon atoms, and o+p is an integer of 1 or more.

According to an embodiment of the present invention, each of L ₂ and L ₃ may be a single bond, or any one selected from the following [Structural Formula 1] to [Structural Formula 5].

[Structural formula 1] [Structural formula 2] [Structural formula 3]

[Structural formula 4] [Structural formula 5]

R ₁ and R ₂ are the same as or different from each other and are each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 30 hetero A cycloalkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, a substituted or unsubstituted C 1 to C 50 heteroaryl group, a substituted or unsubstituted C 6 to C 30 arylamine group, Any one selected from a substituted or unsubstituted heteroarylamine group having 2 to 30 carbon atoms and a substituted or unsubstituted arylheteroarylamine group having 6 to 30 carbon atoms.

According to an embodiment of the present invention, R ₁ and R ₂ are each a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted amine group, a substituted Or it may be any one selected from an unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, and a substituted or unsubstituted fluorenyl group, preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted It may be any one selected from a cyclic naphthyl group, a substituted or unsubstituted phenanthrenyl group, and a substituted or unsubstituted amine group.

[Formula B]

[Formula B] is characterized in that an alkyl group, an aryl group, a heteroaryl group, etc. are introduced at the 3 th position of phenanthrene, and an amine structure is introduced through a linking group at the 10 th position.

In the [Formula B],

Ar ₂ is any one selected from a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, and a substituted or unsubstituted C 1 to C 50 heteroaryl group.

According to an embodiment of the present invention, Ar ₂ may be any one selected from a substituted or unsubstituted phenyl group and a substituted or unsubstituted naphthyl group.

L ₄ To L ₆ Are the same as or different from each other and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroarylene group having 1 to 50 carbon atoms In any one selected from, m, q, and r are each independently an integer of 0 to 3, and L ₄ to L ₆ are the same as or different from each other when a plurality of L 4 to L 6 are each.

According to an embodiment of the present invention, each of L ₅ and L ₆ may be a single bond or a substituted or unsubstituted C6-C24 arylene group, and q+r is an integer of 1 or more.

According to an embodiment of the present invention, each of L ₅ and L ₆ may be a single bond or any one selected from the following [Structural Formula 1] to [Structural Formula 5].

[Structural formula 1] [Structural formula 2] [Structural formula 3]

[Structural formula 4] [Structural formula 5]

R ₃ and R ₄ are the same as or different from each other and each independently represent a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, or a substituted or unsubstituted C 1 to C 30 hetero A cycloalkyl group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 50 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon number Any one selected from a heteroarylamine group having 2 to 30 and a substituted or unsubstituted arylheteroarylamine group having 6 to 30 carbon atoms.

According to an embodiment of the present invention, R ₃ and R ₄ are each a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted amine group, a substituted Or it may be any one selected from an unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, and a substituted or unsubstituted fluorenyl group, preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted It may be any one selected from a cyclic naphthyl group, a substituted or unsubstituted phenanthrenyl group, and a substituted or unsubstituted amine group.

Meanwhile, in the present invention, 'substituted or unsubstituted' means that L ₁ to L ₆ , Ar ₁ to Ar ₂ and R ₁ to R ₄ are deuterium, cyano group, halogen group, hydroxyl group, nitro group, amino group, alkyl group, halogenated at least one substituent selected from the group consisting of an alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, an arylamine group, a heteroarylamine group, an arylheteroarylamine group, an alkylsilyl group and an arylsilyl group It means that it is substituted with, or substituted with a substituent to which two or more of the substituents are connected, or does not have any substituents.

In addition, the carbon number range of the alkyl group or aryl group in the 'substituted or unsubstituted alkyl group having 1 to 30 carbon atoms', 'substituted or unsubstituted aryl group having 6 to 50 carbon atoms', etc., considers the portion in which the substituent is substituted. It refers to the total number of carbon atoms constituting the alkyl part or the aryl part when viewed as unsubstituted. For example, a phenyl group substituted with a butyl group at the para-position corresponds to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

In addition, in the present invention, the meaning that adjacent groups are bonded to each other to form a ring means that adjacent groups can be bonded to each other to form a substituted or unsubstituted alicyclic or aromatic ring, and 'adjacent substituents' The substituent may refer to a substituent substituted on an atom directly connected to the substituted atom, a substituent located three-dimensionally closest to the substituent, or another substituent substituted with the atom in which the substituent is substituted. For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as 'adjacent substituents'.

In the present invention, the alkyl group may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1- Methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group , cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1 -Ethyl-propyl group, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but are not limited thereto.

In the present invention, the alkenyl group includes a straight or branched chain, and may be further substituted by other substituents, specifically, a vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-bute Nyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1-butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group , 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl -1-yl) a vinyl-1-yl group, a stilbenyl group, a styrenyl group, and the like, but are not limited thereto.

In the present invention, the alkynyl group also includes a straight or branched chain, and may be further substituted by other substituents, and may include ethynyl, 2-propynyl, and the like, but limited thereto. it doesn't happen

In the present invention, the aromatic hydrocarbon ring or the aryl group may be monocyclic or polycyclic, and examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, a stilbene group, and the polycyclic aryl group includes a naphthyl group. , anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, tetracenyl group, chrysenyl group, fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthene group, etc., but the scope of the present invention is not It is not limited only to these examples.

In the present invention, the aromatic heterocyclic or heteroaryl group is an aromatic ring containing at least one heteroatom, for example, a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, and an oxadia group. Zol group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group , pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group , dibenzothiophene group, benzofuranyl group, dibenzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, etc. However, the present invention is not limited thereto.

In the present invention, the aliphatic hydrocarbon ring is a non-aromatic ring, which means a ring consisting only of carbon and hydrogen atoms, and includes, for example, a monocyclic or polycyclic ring, and may be further substituted by other substituents, and the polycyclic is another As meaning a group directly connected or condensed with a ring group, the other ring group may be an aliphatic hydrocarbon ring, but may be a different type of ring group, for example, an aliphatic heterocycle, an aryl group, a heteroaryl group, or the like. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, adamantyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclo Cycloalkyl such as hexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclohexane, cyclo cycloalkanes such as pentane, and cyclocycloalkenes such as cyclohexene and cyclobutene, but are not limited thereto.

In the present invention, the aliphatic heterocycle refers to an aliphatic ring including at least one of heteroatoms, and includes heteroatoms such as O, S, Se, N or Si, and also includes monocyclic or polycyclic rings, and other substituents may be further substituted by, and polycyclic refers to a group in which a heterocycloalkyl, heterocycloalkane, heterocycloalgen group, etc. is directly connected or condensed with another ring group, and the other ring group may be an aliphatic heterocycle, It may be another type of cyclic group, such as an aliphatic hydrocarbon ring, an aryl group, a heteroaryl group, and the like.

In the present invention, the aliphatic aromatic mixed ring means a ring in which two or more rings are connected to each other and condensed, and an aliphatic ring and an aromatic ring are condensed to have non-aromaticity as a whole, and also polycyclic aliphatic aromatic It may include a hetero atom selected from N, O, P and S in addition to C in the mixed ring.

In the present invention, the alkoxy group may be specifically methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like, but is not limited thereto.

In the present invention, the silyl group may be -SiH ₃ , an alkylsilyl group, an arylsilyl group, an alkylarylsilyl group, an arylheteroarylsilyl group, and the like, and specific examples of the silyl group include trimethylsilyl, triethylsilyl, triphenylsilyl, and trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, and dimethylfurylsilyl.

In the present invention, the amine group may be -NH ₂ , an alkylamine group, an arylamine group, an arylheteroarylamine group, etc., the arylamine group means an amine substituted with aryl, and the alkylamine group means an amine substituted with an alkyl The aryl heteroarylamine group means an amine substituted with aryl and heteroaryl groups, and examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or There is an unsubstituted triarylamine group, and the aryl group and heteroaryl group in the arylamine group and the arylheteroarylamine group may be a monocyclic aryl group or a monocyclic heteroaryl group, and may be a polycyclic aryl group or a polycyclic heteroaryl group. And, the aryl group, the arylamine group comprising two or more heteroaryl groups, the arylheteroarylamine group is a monocyclic aryl group (heteroaryl group), a polycyclic aryl group (heteroaryl group), or a monocyclic aryl group (hetero) aryl group) and a polycyclic aryl group (heteroaryl group) may be included at the same time. In addition, the aryl group and the heteroaryl group in the arylamine group and the arylheteroarylamine group may be selected from the examples of the above-described aryl group and heteroaryl group.

In the present invention, the aryl group in the aryloxy group and the arylthioxy group is the same as the above-described aryl group, and specifically, the aryloxy group includes 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-phenane and a toryloxy group, a 9-phenanthryloxy group, and the like, and the arylthioxy group includes, but is not limited to, a phenylthioxy group, a 2-methylphenylthioxy group, a 4-tert-butylphenylthioxy group, and the like.

In the present invention, examples of the halogen group include fluorine, chlorine, bromine or iodine.

More specifically, the phenanthrene derivative compound represented by [Formula A] according to the present invention may be any one selected from the following [Compound 1] to [Compound 54], through which a specific substituent can be clearly identified, , The scope of [Formula A] according to the present invention is not limited thereby.

More specifically, the phenanthrene derivative compound represented by [Formula B] according to the present invention may be any one selected from the following [Compound 101] to [Compound 169], and specific substituents can be clearly identified through this, but , The scope of [Formula B] according to the present invention is not limited thereby.

As can be seen from the above specific compound, the compound represented by [Formula A] or [Formula B] according to the present invention is a compound in which a characteristic structure is introduced at positions 3 and 10 of phenanthrene, respectively, of a skeleton and a substituent It is possible to synthesize an organic light emitting material having unique properties, and through this, a high efficiency and long lifespan organic light emitting device can be realized.

In addition, another aspect of the present invention relates to an organic light emitting device comprising a first electrode, a second electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the organic layer has the [Formula A] Or it may include at least one organic light emitting compound according to the present invention represented by [Formula B].

The organic layer includes at least one of an electron injection layer, an electron transport layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, and a light emitting layer, wherein at least one of the layers is the [Formula A] or [Formula A] B] characterized in that it contains an organic light emitting compound represented by.

According to an embodiment of the present invention, the hole transport layer is characterized in that it comprises an organic light emitting compound represented by the [Formula A] or [Formula B].

In addition, according to an embodiment of the present invention, the hole transport layer may be formed of a plurality of hole transport layers, and the hole transport layer of any one of the plurality of hole transport layers is an organic compound represented by [Formula A] or [Formula B]. It is characterized in that it contains a light-emitting compound.

That is, the organic light emitting diode according to an embodiment of the present invention may have a structure including a first electrode and a second electrode and an organic layer disposed therebetween, and according to the present invention [Formula A] or [Formula B] Except that the organic light emitting compound of the device is used in the organic layer of the device, it can be manufactured using a conventional device manufacturing method and material.

The organic layer of the organic light emitting device according to the present invention may have a single-layer structure, but may have a multi-layered structure in which two or more organic layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, an electron transport layer, an electron injection layer, and the like, and each layer may consist of a plurality of layers. However, the present invention is not limited thereto and may include a smaller number or a larger number of organic layers.

In addition, the organic light emitting device according to the present invention includes a light emitting layer interposed between the first electrode and the second electrode, and the light emitting layer consists of a host and a dopant, and in this case, the content of the dopant in the light emitting layer is usually It may be selected from about 0.01 to about 20 parts by weight based on 100 parts by weight of the host, but is not limited thereto.

According to an embodiment of the present invention, the host may be an anthracene derivative represented by the following [Formula C].

[Formula C]

In the [Formula C],

R ₁₁ to R ₁₈ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, a substituted or unsubstituted C A cycloalkyl group of 3 to 30, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, cya selected from a no group, a nitro group and a halogen group.

Ar ₅ and Ar ₆ are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms.

L ₁₁ and L ₁₂ are the same as or different from each other, and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.

n ₁₁ and n ₁₂ are integers of 1 to 2, and when n ₁₁ and n ₁₂ are 2, each of the linking groups L ₁₁ and L ₁₂ is the same as or different from each other.

On the other hand, 'substitution' in the 'substituted or unsubstituted' in [Formula C] is deuterium, cyano group, halogen group, hydroxyl group, nitro group, C1-C24 alkyl group, C1-C24 halogenated Alkyl group, C2-C24 alkenyl group, C2-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C7-C24 arylalkyl group, C2-C24 heteroaryl group , C2-C24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylamino group, C6-C24 arylamino group, C1-C24 heteroarylamino group, C1-C24 alkylsilyl It means being substituted with one or more substituents selected from the group consisting of a group, an arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms.

In addition, according to an embodiment of the present invention, the dopant may be made of any one or more selected from the following [Formula D1] to [Formula D10].

[Formula D1]

[Formula D2]

In the [Formula D1] and [Formula D2],

A ₃₁ , A ₃₂ , E ₁ and F ₁ are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms or a substituted or unsubstituted aromatic heterocycle having 2 to 40 carbon atoms.

Two carbon atoms adjacent to each other in the aromatic ring of A ₃₁ and two carbon atoms adjacent to each other in the aromatic ring of A ₃₂ form a 5-membered ring with the carbon atoms connected to the substituents R ₅₁ and R ₅₂ , respectively. to form

L ₂₁ to L ₃₂ are the same as or different from each other, and each independently represents a single bond, a substituted or unsubstituted C 1 to C 60 alkylene group, a substituted or unsubstituted C 2 to C 60 alkenylene group, substituted or unsubstituted A substituted or unsubstituted C2 to C60 alkynylene group, a substituted or unsubstituted C3 to C60 cycloalkylene group, a substituted or unsubstituted C2 to C60 heterocycloalkylene group, a substituted or unsubstituted C6 to C60 aryl Any one selected from a ene group and a substituted or unsubstituted C 2 to C 60 heteroarylene group.

W and W' are each selected from NR ₅₃ , CR ₅₄ R ₅₅ , SiR ₅₆ R ₅₇ , GeR ₅₈ R ₅₉ , O, S and Se.

R ₅₁ to R ₅₉ , Ar ₂₁ to Ar ₂₈ are the same as or different from each other, and each independently represent hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, A substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 20 alkynyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 5 to C 30 cyclo Alkenyl group, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number A 6 to 30 aryloxy group, a substituted or unsubstituted C 1 to C 30 alkylthioxy group, a substituted or unsubstituted C 6 to C 30 arylthioxy group, a substituted or unsubstituted C 1 to C 30 alkylamine group, A substituted or unsubstituted C6-C30 arylamine group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylsilyl group, a substituted or unsubstituted C1-C30 alkylsilyl group Any one selected from a 30 alkyl germanium group, a substituted or unsubstituted C 6 to C 30 aryl germanium group, a cyano group, a nitro group, and a halogen group.

R ₅₁ and R ₅₂ may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic or aromatic monocyclic or polycyclic ring are N, O, P, Si, S , Ge, Se, and Te may be substituted with any one or more heteroatoms selected from.

p11 to p14, r11 to r14, and s11 to s14 are each an integer of 1 to 3, and when each of these is 2 or more, each of the linking groups L ₂₁ to L ₃₂ is the same or different from each other.

x1 is 1, and y1, z1, and z2 are each an integer from 0 to 1.

Ar ₂₁ and Ar ₂₂ , Ar ₂₃ and Ar ₂₄ , Ar ₂₅ and Ar ₂₆ , and Ar ₂₇ and Ar ₂₈ may be connected to each other to form a ring.

In the [Formula D1], two carbon atoms adjacent to each other in the A ₃₂ ring combine with * of the structural formula Q ₁₁ to form a condensed ring.

In the [Formula D2], two adjacent carbon atoms in the A ₃₁ ring combine with * of the structural formula Q ₁₂ to form a condensed ring, and the two adjacent carbon atoms in the A ₃₂ ring are of the structural formula Q ₁₁ It can combine with * to form a condensed ring.

[Formula D3]

In the [Formula D3],

X ₁ is any one selected from B, P, and P=O.

T1 to T3 are the same as or different from each other, and each independently represent a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, or a substituted or unsubstituted aromatic heterocycle having 2 to 40 carbon atoms.

Y ₁ is any one selected from NR ₆₁ , CR ₆₂ R ₆₃ , O, S and SiR ₆₄ R ₆₅ , and Y ₂ is any one selected from NR ₆₆ , CR ₆₇ R ₆₈ , O, S and SiR ₆₉ R ₇₀ .

wherein R ₆₁ to R ₇₀ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, a substituted or unsubstituted A cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted Or an unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 arylthioxy group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C6-C30 of an arylamine group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylsilyl group, a cyano group, and a halogen group.

Each of R ₆₁ to R ₇₀ may be combined with one or more rings selected from T1 to T3 to further form an alicyclic or aromatic monocyclic or polycyclic ring.

[Formula D4] [Formula D5]

In the [Formula D4] and [Formula D5],

X ₂ is any one selected from B, P, and P=O, and T4 to T6 are the same as those of T1 to T3 in [Formula D3].

Y ₄ is any one selected from NR ₆₁ , CR ₆₂ R ₆₃ , O, S and SiR ₆₄ R ₆₅ , and Y ₅ is any one selected from NR ₆₆ , CR ₆₇ R ₆₈ , O, S and SiR ₆₉ R ₇₀ and Y ₆ is any one selected from NR ₇₁ , CR ₇₂ R ₇₃ , O, S and SiR ₇₄ R ₇₅ .

Each of R ₆₁ to R ₇₅ is the same as the definition of R ₆₁ to R ₇₀ in [Formula D3].

[Formula D6] [Formula D7]

X ₃ is any one selected from B, P and P = O, T7 to T9 are each the same as the definition of T1 to T3 in [Formula D3],

Y ₆ is any one selected from NR ₆₁ , CR ₆₂ R ₆₃ , O, S and SiR ₆₄ R ₆₅ ,

The R ₆₁ to R ₆₅ , R ₇₁ to R ₇₂ are each the same as the definition of R ₆₁ to R ₇₀ in [Formula D3],

R ₇₁ and R ₇₂ are each connected to each other to additionally form an alicyclic or aromatic monocyclic or polycyclic ring, or combine with any one of the T7 to T9 rings to further form an alicyclic or aromatic monocyclic or polycyclic ring can do.

[Formula D8] [Formula D9]

[Formula D10]

In the [Formula D8] to [Formula D10],

X is any one selected from B, P, and P=O, and Q ₁ to Q ₃ are each the same as the definitions of T1 to T3 in [Formula D3].

Y is any one selected from NR ₃ , CR ₄ R ₅ , O, S, and Se, and R ₃ to R ₅ are the same as defined for R ₆₁ to R ₇₀ in [Formula D3], respectively.

Each of R ₃ to R ₅ may be combined with the Q ₂ ring or the Q ₃ ring to further form an alicyclic or aromatic monocyclic or polycyclic ring.

The R ₄ and R ₅ may be connected to each other to further form an alicyclic or aromatic monocyclic or polycyclic ring.

The ring formed by Cy1 has a nitrogen (N) atom, an aromatic carbon atom in the Q1 ring to which the nitrogen (N) atom is bonded, and an aromatic carbon atom in the Q1 ring to be bonded to Cy1, substituted or unsubstituted carbon number 1 to 10 alkylene groups.

In [Formula D9], 'Cy2' may be added to Cy1 to form a saturated hydrocarbon ring, and the ring formed by Cy2 may have 1 to 10 substituted or unsubstituted carbon atoms, except for carbon atoms included in Cy1. is an alkylene group of

In the [Formula D10], the ring formed by Cy3 is an aromatic carbon atom in the Q3 ring to be bonded to Cy3, an aromatic carbon atom in Q3 to be bonded to a nitrogen (N) atom, a nitrogen (N) atom, the nitrogen (N) ) is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, except for carbon atoms in Cy1 to which the atoms are bonded

On the other hand, 'substitution' in the 'substituted or unsubstituted' in the [Formula D1] to [Formula D10] is deuterium, a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group having 1 to 24 carbon atoms, 1 to 24 carbon atoms of a halogenated alkyl group, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aryl group having 7 to 24 carbon atoms. Arylalkyl group, C7-C24 alkylaryl group, C2-C24 heteroaryl group, C2-C24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylamino group, C12-C24 of a diarylamino group, a diheteroarylamino group having 2 to 24 carbon atoms, an aryl (heteroaryl)amino group having 7 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms It means being substituted with one or more substituents selected from the group consisting of an aryloxy group and an arylthionyl group having 6 to 24 carbon atoms.

Hereinafter, a detailed structure of an organic light emitting diode according to an embodiment of the present invention, a manufacturing method thereof, and each organic layer material will be described as follows.

First, an anode is formed by coating a material for an anode electrode on a substrate. Here, as the substrate, a substrate used in a conventional organic light emitting device is used, and an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, handling and water resistance is preferable. In addition, as a material for the anode electrode, transparent and excellent indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc. are used.

A hole injection layer is formed by vacuum thermal evaporation or spin coating of a hole injection layer material on the anode electrode, and then vacuum thermal evaporation or spin coating of a hole transport layer material on the hole injection layer to form a hole transport layer .

The hole injection layer material may be used without particular limitation as long as it is commonly used in the art, and as a specific example, 2-TNATA [4,4',4"-tris(2-naphthylphenyl-phenylamino)-triphenylamine] , NPD [N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine)], TPD [N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'- biphenyl-4,4'-diamine], DNTPD [N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine ] HAT-CN [1,4,5,8,9,11-Hexaazatriphenylenehexacarbonitrile] and the like can be used.

In addition, in the case of the hole transport layer material, the compound according to the present invention may be employed, and in particular, in the case of configuring a plurality of hole transport layers in the organic light emitting device in the present invention, for example, as a first hole transport layer and a second hole transport layer In the case of construction, one layer employs the compound according to the present invention, and the other layer is not particularly limited as long as it is commonly used in the art.

For example, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD) or N,N'-di( Naphthalen-1-yl)-N,N'-diphenylbenzidine (α-NPD) or the like may be used, and a hole transport material conventionally used at the time of deriving the present invention may be used.

In addition, a hole auxiliary layer and a light emitting layer may be sequentially stacked on the hole transport layer, and a thin film may be formed by selectively forming a hole blocking layer on the light emitting layer by a vacuum deposition method or a spin coating method. The hole blocking layer serves to prevent this problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because the lifetime and efficiency of the device are reduced when holes are introduced into the cathode through the organic light emitting layer. . In this case, the hole blocking material used is not particularly limited, but it should have an ionization potential higher than that of a light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, etc. may be used.

As the material used for the hole blocking layer, BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq, etc. may be used, but is not limited thereto.

After depositing an electron transport layer on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer is formed, and a cathode forming metal is vacuum thermally deposited on the electron injection layer to form a cathode electrode. An organic light emitting diode according to an embodiment is completed.

Here, as the metal for forming the cathode, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag) may be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

The electron transport layer material serves to stably transport electrons injected from the cathode, and a known electron transport material may be used. Examples of known electron transport materials include quinoline derivatives, in particular tris(8-quinolinolate)aluminum (Alq3), TAZ, BAlq, beryllium bis(benzoquinolin-10- Materials such as olate: Bebq2) and oxadiazole derivatives PBD, BMD, and BND may be used.

In addition, each of the organic layers may be formed by a single molecule deposition method or a solution process, wherein the deposition method evaporates a material used as a material for forming each layer through heating in a vacuum or low pressure state. It refers to a method of forming a thin film, and the solution process mixes a material used as a material for forming each layer with a solvent, and uses it inkjet printing, roll to roll coating, screen printing, spray coating, dip coating, spin coating It refers to a method of forming a thin film through a method such as this.

In addition, the organic light emitting diode according to the present invention can be used in a device selected from a flat panel display device, a flexible display device, a device for flat panel lighting of a single color or white color, and a device for a flexible lighting device of a single color or white color.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for illustrating the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited thereby.

Synthesis Example 1. Synthesis of compound 1

(1) Synthesis of Intermediate 1-1

Na ₂ CO ₃ (72.66 g, 0.772 mol), Et ₂ NH (91.94 mL, 1.260 mol) and methyl tert-butyl ether (1.6 L, 8 vol.) were added and stirred. H ₂ O (600 mL) was added, and the starting material (200 g, 1.143 mol) was added dropwise while maintaining 15 °C, followed by stirring for 2 hours. The reaction product was extracted with EA/H ₂ O, the organic layers were collected, concentrated, and dried to synthesize a transparent solid intermediate 1-1 (241 g, yield 97%).

(2) Synthesis of Intermediate 1-2

Intermediate 1-1 (200 g, 0.945 mol) and DME (1.2 L, 6 vol.) were put in a reactor, stirred while blowing N ₂ gas, and tripropyl borate (371.9 g, 1.512 mol) was added, followed by LDA at -35 ° C. put When the reaction was completed, it was quenched with water, the reactant was extracted with EA/H ₂ O, and the organic layer was concentrated to synthesize Intermediate 1-2.

(3) Synthesis of Intermediate 1-3

Intermediate 1-2 (241 g, 0.943 mol) and 1-bromotoluene (174.1 g, 1.018 mol), Pd(PPh ₃ ) ₄ (10.4 g, 0.009 mol), Pd(OAc) ₂ (1.05 g, 0.005 mol), K ₂ CO ₃ (325.9 g, 2.358 mol) was put into a reactor, DME (860 mL) was added, and the mixture was stirred under reflux overnight. After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to synthesize Intermediate 1-3 (180 g, yield 63%).

(4) Synthesis of Intermediate 1-4

Intermediate 1-3 (180 g, 0.596 mol) and DME were put into a reactor, N ₂ gas was blown, and LDA was added dropwise at -45° C., followed by stirring for 2 hours. After quenching with 6 M HCl, EA/H ₂ O extraction was performed, the organic layer was concentrated, boiled in Tol, dissolved, cooled, and purified by recrystallization by adding heptane at low temperature to synthesize Intermediate 1-4 (110 g, yield 84%).

(5) Synthesis of compound 1-5

Add compound 1-4 (40 g, 0.175 mol) and MC (280 mL, 7vol.), and add TEA (44.27 g, 0.438 mol). At 0 °C, Tf ₂ O (59.24 g, 0.210 mol) is added dropwise and stirred while checking the reaction by TLC until it reaches room temperature. When the reaction is complete, the reaction product is extracted with EA/H ₂ O, and the organic layers are collected and concentrated. Intermediate 1-5 (47 g, yield 74%) was synthesized by column purification (MC/Hep).

(6) Synthesis of compound 1-6

Compound 1-5 (10 g, 0.028 mol) and 1-naphthylbronic acid (5.4 g, 0.031 mol), Pd(PPh ₃ ) ₄ (0.96 g, 0.84 mmol), K ₂ CO ₃ (11.6 g, 0.084 mol) was added to a reactor, Tol (70 mL), EtOH (30 mL), and H ₂ O (20 mL) were added, followed by reflux overnight at 75 °C. EA/H ₂ O is extracted and the organic layer is concentrated. Intermediate 1-6 (6.86 g, yield 73%) was synthesized by column purification (MC/Hep).

(7) Synthesis of compound 1

Intermediate 1-6 (6.86 g, 0.02 mol) and di([1,1'-biphenyl]-4-yl)amine (7.2 g, 0.022 mol), Pd(Pt-Bu ₃ ) ₂ (0.21 g, 0.0004 mol) ), STB (3.9 g, 0.04 mol), and toluene (70 mL) were put into a reactor and stirred under reflux for 3 hours. Compound 1 (6 g, yield 48%) was synthesized through toluene hot filter, concentration and column purification.

MS(MALDI-TOF) : m/z 623.26 [M]+

Synthesis Example 2. Synthesis of compound 2

Intermediate 1-6 (6.86 g, 0.02 mol) and di([1,1'-biphenyl]-4-yl)amine (6.6 g, 0.022 mol), Pd(Pt-Bu ₃ ) ₂ (0.21 g, 0.0004 mol) ), STB (3.9 g, 0.04 mol), and toluene (70 mL) were put into a reactor and stirred under reflux for 3 hours. Compound 2 (5.32 g, yield 43%) was synthesized through toluene hot filter, concentration and column purification.

MS(MALDI-TOF) : m/z 597.25 [M]+

Synthesis Example 3. Synthesis of compound 30

(1) Synthesis of Intermediate 3-1

Intermediate 1-5 (10 g, 0.028 mol) and 2-(dibenzo[b,d]furan-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.56 g, 0.031) mol), Pd(PPh ₃ ) ₄ (0.96 g, 0.84 mmol), K ₂ CO ₃ (11.6 g, 0.084 mol) was put into a reactor, toluene (70 mL), EtOH (30 mL), H ₂ O (20 mL) were added, and the mixture was stirred at 75 °C. EA/H ₂ O was extracted, and the organic layer was concentrated and then column purified (MC/Hep) to synthesize Intermediate 3-1 (8.61 g, yield 82%).

(2) Synthesis of compound 30

Intermediate 3-1 (8.61 g, 0.023 mol) and di([1,1'-biphenyl]-4-yl)amine (9.2 g, 0.025 mol), Pd(Pt-Bu ₃ ) ₂ (0.23 g, 0.0004 mol) ), STB (4.4 g, 0.04 mol), and toluene (86 mL) were added to the reactor and stirred under reflux for 3 hours. Compound 30 (7.3 g, yield 45%) was synthesized through toluene hot filter, concentration and column purification.

MS(MALDI-TOF) : m/z 713.27 [M]+

Synthesis Example 4. Synthesis of compound 104

(1) Synthesis of Intermediate 4-1

Intermediate 1-5 (50 g, 0.139 mol) and B ₂ Pin ₂ (42.2 g, 0.166 mol), Pd(dppf) ₂ (3.4 g, 4.0 mmol) and KOAc (40.8 g, 0.416 mol) were put in a reactor, 1,4-Dioxane (550 mL) was added, and the mixture was stirred at 100 °C overnight. After concentration, column purification (MC/Hep) 4-1 (35.0 g, yield 74.6%) was synthesized.

(2) Synthesis of Intermediate 4-2

Intermediate 4-1 (9.22 g, 0.027 mol) and N-(4-bromophenyl)-N-(4-(naphthalen-1-yl)phenyl)-[1,1':4',1"-terphenyl]- 4-amine (15.0 g, 0.025 mol), Pd(PPh ₃ ) ₄ (0.58 g, 0.42 mmol), K ₂ CO ₃ (8.60 g, 0.062 mol) was put into a reactor, toluene (105 mL), EtOH (45 mL), H ₂ O (30 mL) were added, and the mixture was stirred at 75 °C overnight. After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to synthesize Intermediate 4-2 (16 g, yield 86.9%).

(3) Synthesis of compound 104

Intermediate 4-2 (9 g, 0.012 mol) and phenylboronic acid (1.8 g, 0.015 mol), Pd ₂ (dba) ₃ (0.56 g, 1 mmol), P(cy) ₃ (0.69 g, 2 mmol) K ₃ PO ₄ (5.2 g, 0.025 mol) was put into a reactor, toluene (50 mL), Dioxane (50 mL), H ₂ O (20 mL) was added, and the mixture was stirred at 100 °C overnight. Compound 104 (4.3 g, yield 45.3%) was synthesized by column purification after concentration with toluene hot filter.

MS(MALDI-TOF) : m/z 775.32 [M]+

Synthesis Example 5. Synthesis of compound 103

(1) Synthesis of Intermediate 5-1

Intermediate 1-5 (23.5 g, 0.065 mol) and 4-bromophenylboronic acid (13.1 g, 0.065 mol), Pd(PPh ₃ ) ₄ (1.51 g, 1 mmol), K ₂ CO ₃ (20.71 g, 0.150 mol) was put into a reactor, toluene (170 mL), EtOH (70 mL), H ₂ O (50 mL) were added, and the mixture was stirred at 75 °C overnight. After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to recrystallize from MeOH to synthesize Intermediate 5-1 (18 g, yield 75%).

(2) Synthesis of Intermediate 5-2

Intermediate 5-1 (9 g, 0.024 mol) and N-(4-(naphthalen-1-yl)phenyl)-[1,1'-biphenyl]-4-amine (10.4 g, 0.028 mol), Pd ₂ ( dba) ₃ (0.44 g, 0.4 mmol), P(t-Bu) ₃ (0.20 g, 0.9 mmol), STB (1.29 g, 0.013 mol), and toluene (100 mL) were placed in a reactor and stirred at 100° C. overnight. After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to synthesize Intermediate 5-2 (8.45 g, yield 76.8%).

(3) Synthesis of compound 103

Intermediate 5-2 (8.5 g, 0.013 mol) and phenylboronic acid (1.9 g, 0.015 mol), Pd ₂ (dba) ₃ (0.56 g, 1 mmol), P(cy) ₃ (0.69 g, 2 mmol) K ₃ PO ₄ (5.2 g, 0.025 mol), toluene (50 mL), Dioxane (50 mL), and H ₂ O (20 mL) were added to a reactor and stirred at 100° C. overnight. Compound 103 (2.33 g, yield 25.9%) was synthesized through toluene hot filter, concentration and column purification.

MS(MALDI-TOF): m/z 699.29 [M]+

Synthesis Example 6. Synthesis of compound 112

(1) Synthesis of Intermediate 6-1

Intermediate 4-1 (10 g, 0.029 mol) and N1-(4-bromophenyl)-N1,N3,N3-triphenylbenzene-1,3-diamine (14.5 g, 0.029 mol), Pd(PPh ₃ ) ₄ (0.68 g, 0.59 mmol), K ₂ CO ₃ (10.2 g, 0.073 mol) is added to a reactor, Tol (70 mL), EtOH (30 mL), H ₂ O (20 mL) are added, and reflux is carried out at 75 °C overnight. Extract with EA/H2O and concentrate the organic layer. Intermediate 5-1 (14.14 g, yield 76.8%) was synthesized by column purification (MC/Hep).

(2) Synthesis of compound 112

Intermediate 6-1 (14.14 g, 0.023 mol) and phenylboronic acid (3.3 g, 0.027 mol), Pd ₂ (dba) ₃ (1.03 g, 1.1 mmol), P(cy) ₃ (0.64 g, 2.2 mmol) K ₃ PO ₄ (9.6 g, 0.045 mol) is added to a reactor, Tol (75 mL), Dioxane (75 mL), and H ₂ O (30 mL) are added, and reflux is carried out at 100 °C overnight. Tol hot filter and concentrate. After silica adsorption and column purification, compound 112 (6.3 g, yield 42.1%) was synthesized.

MS(MALDI-TOF) : m/z 664.29 [M]+

Synthesis Example 7. Synthesis of compound 158

(1) Synthesis of Intermediate 7-1

N-(4-bromophenyl)-[1,1'-biphenyl]-4-amine (25 g, 77 mmol) and phenanthren-9-ylboronic acid (20.55 g, 65 mmol), Pd(PPh ₃ ) ₄ (1.78 g, 2 mmol), K ₂ CO ₃ (24.51 g, 177 mmol) was put into a reactor, toluene (170 mL), EtOH (70 mL), H ₂ O (50 mL) were added, and the mixture was stirred at 75 ° C overnight. . After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to recrystallize from MeOH to synthesize Intermediate 7-1 (31 g, yield 95%).

(2) Synthesis of Intermediate 7-2

Intermediate 7-1 (31 g, 0.074 mol) and 1-Bromo-4-iodobenzene (22.9 g, 0.081 mol), Pd(OAc) ₂ (0.17 g, 0.1 mmol), Xantphos (0.43 g, 0.1 mmol), STB (7.77 g, 0.081 mol) and toluene (300 mL) were put into a reactor and stirred at 100 °C overnight. After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to synthesize 7-2 (35 g, yield 82.5%).

(3) Synthesis of Intermediate 7-3

Intermediate 7-2 (15 g, 0.026 mol) and Intermediate 4-1 (9.63 g, 0.029 mol), Pd(PPh ₃ ) ₄ (0.60 g, 0.42 mmol), K ₂ CO ₃ (8.99 g, 0.062 mol) was put into a reactor, toluene (105 mL), EtOH (45 mL), H ₂ O (30 mL) were added, and the mixture was stirred at 75 °C overnight. After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to synthesize Intermediate 7-3 (14 g, yield 76.1%).

(4) Synthesis of compound 158

Intermediate 7-3 (14 g, 0.020 mol) and phenylboronic acid (2.9 g, 0.024 mol), Pd ₂ (dba) ₃ (0.90 g, 1 mmol), P(cy) ₃ (1.11 g, 4 mmol) K ₃ PO ₄ (8.4 g, 0.040 mol) was added to a reactor, toluene (75 mL), Dioxane (75 mL), and H ₂ O (30 mL) were added thereto, followed by stirring at 100° C. overnight. Compound 158 (3.2 g, yield 21.4%) was synthesized through toluene hot filter, concentration and column purification.

MS(MALDI-TOF): m/z 749.31 [M]+

Synthesis Example 8. Synthesis of compound 138

(1) Synthesis of Intermediate 8-1

di([1,1'-biphenyl]-4-yl)amine (12.5 g, 0.042 mol) and 1-Bromo-4-iodobenzene (13.2 g, 0.047 mol), Pd(OAc) ₂ (0.10 g, 0.1 mmol), Xantphos (0.24 g, 0.1 mmol), STB (4.47 g, 0.047 mol), and toluene (150 mL) were placed in a reactor and stirred at 100 °C overnight. After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to synthesize Intermediate 8-1 (16.3 g, yield 85.3%).

(2) Synthesis of Intermediate 8-2

Intermediate 8-1 (24.3 g, 0.054 mol) and Intermediate 4-1 (19.9 g, 0.059 mol), Pd(PPh ₃ ) ₄ (1.25 g, 0.18 mmol), K ₂ CO ₃ (18.6 g, 0.135 mol) was put into a reactor, toluene (140 mL), EtOH (60 mL), H ₂ O (40 mL) were added, and the mixture was stirred at 75 °C overnight. After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to synthesize Intermediate 8-2 (23 g, yield 73.2%).

(3) Synthesis of compound 138

Intermediate 8-2 (27.2 g, 0.047 mol) and phenylboronic acid (6.84 g, 0.056 mol), Pd ₂ (dba) ₃ (2.14 g, 2 mmol), P(cy) ₃ (2.62 g, 9 mmol) K ₃ PO ₄ (19.9 g, 0.093 mol) was put into a reactor, toluene (150 mL), Dioxane (150 mL), H ₂ O (60 mL) were added, and the mixture was stirred at 100 °C overnight. Compound 138 (14.1 g, yield 48.5%) was synthesized through toluene hot filter, concentration and column purification.

MS(MALDI-TOF) : m/z 623.26 [M]+

Synthesis Example 9. Synthesis of compound 107

(1) Synthesis of Intermediate 9-1

N-(4-(naphthalen-2-yl)phenyl)-[1,1'-biphenyl]-4-amine (27.1 g, 0.073 mol) and 1-Bromo-4-iodobenzene (22.7 g, 0.080 mol), Pd(OAc) ₂ (0.16 g, 0.1 mmol), Xantphos (0.42 g, 0.1 mmol), STB (7.71 g, 0.080 mol), and toluene (300 mL) were placed in a reactor and stirred at 100 °C overnight. After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to synthesize Intermediate 9-1 (35 g, yield 91.1%).

(2) Synthesis of Intermediate 9-2

Intermediate 9-1 (28.0 g, 0.053 mol) and Intermediate 4-1 (19.9 g, 0.059 mol), Pd(PPh ₃ ) ₄ (1.25 g, 0.18 mmol), K ₂ CO ₃ (18.6 g, 0.135 mol) was put into a reactor, toluene (210 mL), EtOH (90 mL), H ₂ O (60 mL) were added, and the mixture was stirred at 75 °C overnight. After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to synthesize Intermediate 9-2 (29 g, yield 82.8%).

(3) Synthesis of compound 107

Intermediate 9-2 (10 g, 0.015 mol) and phenylboronic acid (2.22 g, 0.018 mol), Pd ₂ (dba) ₃ (0.70 g, 1 mmol), P(cy) ₃ (0.85 g, 3 mmol) K ₃ PO ₄ (6.45 g, 0.030 mol) was added to a reactor, toluene (50 mL), Dioxane (50 mL), and H ₂ O (20 mL) were added, followed by stirring at 100 °C overnight. Compound 107 (3.3 g, yield 31.0%) was synthesized through toluene hot filter, concentration and column purification.

MS(MALDI-TOF): m/z 699.29 [M]+

Synthesis Example 10. Synthesis of compound 106

(1) Synthesis of Intermediate 10-1

N-(4-(naphthalen-2-yl)phenyl)-[1,1':4',1"-terphenyl]-4-amine (22.0 g, 0.049 mol) and 1-Bromo-4-iodobenzene (15.3 g, 0.054 mol), Pd(OAc) ₂ (0.11 g, 0.1 mmol), Xantphos (0.28 g, 0.1 mmol), STB (5.20 g, 0.054 mol), and toluene (220 mL) were placed in a reactor and stirred at 100 °C overnight. After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to synthesize Intermediate 10-1 (21 g, yield 70.9%).

(2) Synthesis of Intermediate 10-2

Intermediate 10-1 (15.0 g, 0.025 mol) and Intermediate 4-1 (9.22 g, 0.027 mol), Pd(PPh ₃ ) ₄ (0.58 g, 0.08 mmol), K ₂ CO ₃ (8.6 g, 0.062 mol) was put into a reactor, toluene (105 mL), EtOH (45 mL), H ₂ O (30 mL) were added, and the mixture was stirred at 75 °C overnight. After EA/H ₂ O extraction and concentration of the organic layer, column purification (MC/Hep) was performed to synthesize Intermediate 10-2 (18 g, yield 86.9%).

(3) Synthesis of compound 106

Intermediate 10-2 (9 g, 0.012 mol) and phenylboronic acid (1.79 g, 0.015 mol), Pd ₂ (dba) ₃ (0.56 g, 1 mmol), P(cy) ₃ (0.69 g, 2 mmol) K ₃ PO ₄ (5.20 g, 0.025 mol) was added to a reactor, toluene (50 mL), Dioxane (50 mL), and H ₂ O (20 mL) were added, followed by stirring at 100 °C overnight. Compound 106 (3.1 g, yield 32.6%) was synthesized through toluene hot filter, concentration and column purification.

MS(MALDI-TOF) : m/z 775.32 [M]+

Examples 1 to 14. Preparation of organic light emitting device

After patterning so that the light emitting area of the ITO glass becomes 2 mm × 2 mm in size, it was washed. After mounting the ITO glass in a vacuum chamber, the base pressure was made to 1 × 10 ^-7 torr, and on the ITO, DNTPD (450 Å), [Compound G] (200 Å), as a second hole transport layer material in the present invention The compounds (50 Å) described in the following [Table 1] were respectively formed into a film. After that, [Compound 313]:[D280] was mixed in the light emitting layer in a weight ratio (97:3) to form a film (200 Å), and then [Compound E-2] (300 Å) as an electron transport layer and [Compound E-2] (300 Å) as an electron injection layer E-1] (10 Å) and Al (1000 Å) were formed in the order to prepare an organic light emitting diode. The emission characteristics of the organic light emitting device were measured at 0.4 mA.

[DNTPD] [Compound G] [Compound E-1]

[Compound E-2] [Compound 313] [D 280]

comparative example 1 to 4

In the structure of the organic light emitting device of the embodiment according to the present invention, an organic light emitting device was prepared in the same manner except that the following [Compound B] to [Compound E] were used instead of the compound according to the present invention for the second hole transport layer compound, and the organic light emitting device was prepared. The light emitting characteristics of the light emitting device were measured at 0.4 mA.

[Compound B] [Compound C]

[Compound D] [Compound E]

For the organic light emitting diodes manufactured according to Examples 1 to 14 and Comparative Examples 1 to 4, driving voltage, efficiency, and lifespan were measured, and the results are shown in Table 1 below.

division	compound	Voltage (V)	Efficiency (Cd/A)	External Quantum Efficiency (EQE)	Lifetime (T97, h)
Example 1	compound 1	3.43	8.5	10	100
Example 2	compound 2	3.43	8.5	10	98
Example 3	compound 8	3.47	8.8	10.3	120
Example 4	compound 9	3.43	8.6	10.1	115
Example 5	compound 14	3.44	8.7	10.2	110
Example 6	compound 30	3.39	8.5	10	103
Example 7	compound 103	3.47	9.2	11.1	123
Example 8	compound 104	3.45	9.4	11.2	131
Example 9	compound 106	3.44	8.9	10.7	142
Example 10	compound 107	3.41	9.0	10.9	156
Example 11	compound 112	3.42	9.6	11.5	102
Example 12	compound 137	3.48	8.9	10.5	127
Example 13	compound 138	3.41	9.1	11	173
Example 14	compound 158	3.48	9.9	11.9	143
Comparative Example 1	compound B	3.48	8.1	9.5	74
Comparative Example 2	compound C	3.50	8.4	9.9	65
Comparative Example 3	compound D	3.48	8.3	9.7	69
Comparative Example 4	compound E	3.53	8.5	10	53

Looking at [Table 1] and the device examples, when the compound according to the present invention is employed in the device as the second hole transport layer compound, the [Formula A] compound (Examples 1 to 6) according to the present invention is a comparative compound [Formula B] compounds (Examples 7 to 14) according to the present invention have significantly improved long life characteristics compared to conventional devices (Comparative Examples 1 to 4) employing ), it can be seen that it has better efficiency characteristics and significantly improved long life characteristics.

The phenanthrene derivative compound according to the present invention is employed as an organic layer in the device, particularly as a hole transport material, and thus can realize a high-efficiency and long-life organic light emitting device, so that a flat panel display device, a flexible display device, a device for flat panel lighting of a single color or a white color and a single color or white color It can be usefully used industrially, for example, in a device for flexible lighting.

Claims (17)

1. An organic compound represented by the following [Formula A] or [Formula B]:

   [Formula A]

   

   In the [Formula A],

   Ar ₁ is any one selected from a substituted or unsubstituted C10 to C50 aryl group and a substituted or unsubstituted C1 to C50 heteroaryl group,

   L ₁ To L ₃ Are the same as or different from each other and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroarylene group having 1 to 50 carbon atoms Any one selected from

   n, o, and p are each independently an integer of 0 to 3, and when L ₁ to L ₃ are plural, they are the same as or different from each other,

   R ₁ and R ₂ are the same as or different from each other and are each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, or a substituted or unsubstituted C 1 to C 30 hetero A cycloalkyl group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 50 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon number any one selected from a heteroarylamine group having 2 to 30 and a substituted or unsubstituted arylheteroarylamine group having 6 to 30 carbon atoms;

   [Formula B]

   

   In the [Formula B],

   Ar ₂ is any one selected from a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group and a substituted or unsubstituted C 1 to C 50 heteroaryl group,

   L ₄ To L ₆ Are the same as or different from each other and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroarylene group having 1 to 50 carbon atoms Any one selected from

   m, q, r are each independently an integer of 0 to 3, and when L ₄ to L ₆ are plural, they are the same as or different from each other,

   R ₃ and R ₄ are the same as or different from each other and are each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, or a substituted or unsubstituted C 1 to C 30 hetero A cycloalkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, a substituted or unsubstituted C 1 to C 50 heteroaryl group, a substituted or unsubstituted C 6 to C 30 arylamine group, Any one selected from a substituted or unsubstituted heteroarylamine group having 2 to 30 carbon atoms and a substituted or unsubstituted arylheteroarylamine group having 6 to 30 carbon atoms.
2. According to claim 1,

   'Substitution' in 'substituted or unsubstituted' means that L ₁ to L ₆ , Ar ₁ to Ar ₂ and R ₁ to R ₄ are deuterium, cyano group, halogen group, hydroxyl group, nitro group, alkyl group, halogenated At least one substituent selected from the group consisting of an alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, an arylamine group, a heteroarylamine group, an arylheteroarylamine group, an alkylsilyl group and an arylsilyl group An organic compound that is substituted or is substituted with a substituent in which two or more of the substituents are connected.
3. According to claim 1,

   The L ₂ , L ₃ , L ₅ and L ₆ are each a single bond, or an organic compound selected from the following [Structural Formula 1] to [Structural Formula 5]:

   [Structural formula 1] [Structural formula 2] [Structural formula 3]

   

   [Structural formula 4] [Structural formula 5]

   
4. According to claim 1,

   The L ₂ and L ₃ are each a substituted or unsubstituted arylene group having 6 to 24 carbon atoms, and o+p is an integer of 1 or more,

   wherein L ₅ and L ₆ are each a substituted or unsubstituted C6-C24 arylene group, and q+r is an integer of 1 or more.
5. According to claim 1,

   Wherein R ₁ and R ₂ are each a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted dibenzofuranyl group, Any one selected from a substituted or unsubstituted dibenzothiophenyl group and a substituted or unsubstituted fluorenyl group,

   R ₃ and R ₄ are each a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted dibenzofuranyl group, An organic compound selected from a substituted or unsubstituted dibenzothiophenyl group and a substituted or unsubstituted fluorenyl group.
6. 6. The method of claim 5,

   Each of R ₁ to R ₂ is any one selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, and a substituted or unsubstituted amine group,

   wherein R ₃ and R ₄ are each selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, and a substituted or unsubstituted amine group.
7. According to claim 1,

   wherein Ar ₂ is any one selected from a substituted or unsubstituted phenyl group and a substituted or unsubstituted naphthyl group.
8. According to claim 1,

   The [Formula A] is an organic compound selected from the following [Compound 1] to [Compound 54]:

   

   

   

   

   
9. The method of claim 1,

   The [Formula B] is an organic compound selected from the following [Compound 101] to [Compound 169]:

   

   

   

   

   

   
10. A first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode,

    An organic light emitting device comprising at least one compound represented by the [Formula A] or [Formula B] according to claim 1 in which the organic layer.
11. 11. The method of claim 10,

    The organic layer includes at least one of an electron injection layer, an electron transport layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, and a light emitting layer,

    At least one of the layers is an organic light emitting device comprising an organic light emitting compound represented by the [Formula A] or [Formula B].
12. 12. The method of claim 11,

    An organic light emitting device comprising an organic light emitting compound represented by the [Formula A] or [Formula B] in the hole transport layer.
13. 13. The method of claim 12,

    The hole transport layer is characterized in that it consists of a plurality of hole transport layers, an organic light emitting device comprising an organic light emitting compound represented by the [Formula A] or [Formula B] in any one hole transport layer of the plurality of hole transport layers.
14. 11. The method of claim 10,

    The organic layer interposed between the first electrode and the second electrode includes a light emitting layer, wherein the light emitting layer consists of a host and a dopant,

    The host is an organic light emitting device which is an anthracene derivative represented by the following [Formula C]:

    [Formula C]

    

    In the [Formula C],

    R ₁₁ to R ₁₈ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, a substituted or unsubstituted C A cycloalkyl group of 3 to 30, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, cya Any one selected from a no group, a nitro group, and a halogen group,

    Ar ₅ and Ar ₆ are the same as or different from each other, and each independently represents a substituted or unsubstituted C 6 to C 50 aryl group, or a substituted or unsubstituted C 2 to C 50 heteroaryl group,

    L ₁₁ and L ₁₂ are the same as or different from each other, and are each independently selected from a single bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms; ,

    n ₁₁ and n ₁₂ are integers of 1 to 2, and when n ₁₁ and n ₁₂ are 2, each linking group L ₁₁ and L ₁₂ is the same as or different from each other,

    'Substitution' in the 'substituted or unsubstituted' in the [Formula C] is deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, C2-C24 alkenyl group, C2-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C7-C24 arylalkyl group, C2-C24 heteroaryl group, carbon number A heteroarylalkyl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, It means being substituted with one or more substituents selected from the group consisting of an arylsilyl group having 6 to 24 carbon atoms and an aryloxy group having 6 to 24 carbon atoms.
15. 15. The method of claim 14,

    The dopant is an organic light emitting device consisting of at least one selected from the following [Formula D1] to [Formula D10]:

    [Formula D1]

    

    [Formula D2]

    

    In the [Formula D1] and [Formula D2],

    A ₃₁ , A ₃₂ , E ₁ and F ₁ are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, or a substituted or unsubstituted aromatic heterocycle having 2 to 40 carbon atoms,

    Two carbon atoms adjacent to each other in the aromatic ring of A ₃₁ and two carbon atoms adjacent to each other in the aromatic ring of A ₃₂ form a 5-membered ring with the carbon atoms connected to the substituents R ₅₁ and R ₅₂ , respectively. to form,

    L ₂₁ to L ₃₂ are the same as or different from each other, and each independently represents a single bond, a substituted or unsubstituted C 1 to C 60 alkylene group, a substituted or unsubstituted C 2 to C 60 alkenylene group, substituted or unsubstituted A substituted or unsubstituted C2 to C60 alkynylene group, a substituted or unsubstituted C3 to C60 cycloalkylene group, a substituted or unsubstituted C2 to C60 heterocycloalkylene group, a substituted or unsubstituted C6 to C60 aryl any one selected from a lene group and a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

    W and W' are each one selected from NR ₅₃ , CR ₅₄ R ₅₅ , SiR ₅₆ R ₅₇ , GeR ₅₈ R ₅₉ , O, S and Se;

    R ₅₁ to R ₅₉ , Ar ₂₁ to Ar ₂₈ are the same as or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, A substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 20 alkynyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 5 to C 30 cyclo Alkenyl group, a substituted or unsubstituted C2 to C50 heteroaryl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 A 6 to 30 aryloxy group, a substituted or unsubstituted C 1 to C 30 alkylthioxy group, a substituted or unsubstituted C 6 to C 30 arylthioxy group, a substituted or unsubstituted C 1 to C 30 alkylamine group, A substituted or unsubstituted C6-C30 arylamine group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylsilyl group, a substituted or unsubstituted C1-C30 alkylsilyl group Any one selected from an alkyl germanium group of 30, a substituted or unsubstituted aryl germanium group having 6 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group,

    R ₅₁ and R ₅₂ may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atoms of the formed alicyclic or aromatic monocyclic or polycyclic ring are N, O, P, Si, S , Ge, Se and Te may be substituted with any one or more heteroatoms selected from,

    p11 to p14, r11 to r14, and s11 to s14 are each an integer of 1 to 3, and when each of these is 2 or more, each of the connecting groups L ₂₁ to L ₃₂ is the same as or different from each other,

    x1 is 1, y1, z1 and z2 are each an integer from 0 to 1,

    wherein Ar ₂₁ and Ar ₂₂ , Ar ₂₃ and Ar ₂₄ , Ar ₂₅ and Ar ₂₆ , and Ar ₂₇ and Ar ₂₈ may be connected to each other to form a ring,

    In the [Formula D1], two carbon atoms adjacent to each other in the A ₃₂ ring combine with * of the structural formula Q ₁₁ to form a condensed ring,

    In the [Formula D2], two adjacent carbon atoms in the A ₃₁ ring combine with * of the structural formula Q ₁₂ to form a condensed ring, and the two adjacent carbon atoms in the A ₃₂ ring are of the structural formula Q ₁₁ It can be combined with * to form a condensed ring.

    [Formula D3]

    

    In the [Formula D3],

    X ₁ is any one selected from B, P and P = O,

    T1 to T3 are the same or different from each other, and are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic ring having 2 to 40 carbon atoms,

    Y ₁ is any one selected from NR ₆₁ , CR ₆₂ R ₆₃ , O, S and SiR ₆₄ R ₆₅ ,

    Y ₂ is any one selected from NR ₆₆ , CR ₆₇ R ₆₈ , O, S and SiR ₆₉ R ₇₀ ,

    wherein R ₆₁ to R ₇₀ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, a substituted or unsubstituted A cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted Or an unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C30 arylthioxy group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C6-C30 of an arylamine group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylsilyl group, a cyano group, and a halogen group,

    Each of R ₆₁ to R ₇₀ may be combined with one or more rings selected from T1 to T3 to further form an alicyclic or aromatic monocyclic or polycyclic ring.

    [Formula D4] [Formula D5]

    

    In the [Formula D4] and [Formula D5],

    X ₂ is any one selected from B, P and P = O, T4 to T6 are the same as the definition of T1 to T3 in [Formula D3],

    Y ₄ is any one selected from NR ₆₁ , CR ₆₂ R ₆₃ , O, S and SiR ₆₄ R ₆₅ , and Y ₅ is any one selected from NR ₆₆ , CR ₆₇ R ₆₈ , O, S and SiR ₆₉ R ₇₀ and Y ₆ is any one selected from NR ₇₁ , CR ₇₂ R ₇₃ , O, S and SiR ₇₄ R ₇₅ ,

    Each of R ₆₁ to R ₇₅ is the same as the definition of R ₆₁ to R ₇₀ in [Formula D3].

    [Formula D6] [Formula D7]

    

    X ₃ is any one selected from B, P and P = O, T7 to T9 are each the same as the definition of T1 to T3 in [Formula D3],

    Y ₆ is any one selected from NR ₆₁ , CR ₆₂ R ₆₃ , O, S and SiR ₆₄ R ₆₅ ,

    The R ₆₁ to R ₆₅ , R ₇₁ to R ₇₂ are each the same as the definition of R ₆₁ to R ₇₀ in [Formula D3],

    R ₇₁ and R ₇₂ are each connected to each other to additionally form an alicyclic or aromatic monocyclic or polycyclic ring, or combine with any one of the T7 to T9 rings to further form an alicyclic or aromatic monocyclic or polycyclic ring can do.

    [Formula D8] [Formula D9]

    

    

    [Formula D10]

    

    In the [Formula D8] to [Formula D10],

    X is any one selected from B, P and P = O, Q ₁ to Q ₃ are each the same as the definition of T1 to T3 in [Formula D3],

    Y is any one selected from NR ₃ , CR ₄ R ₅ , O, S and Se, wherein R ₃ to R ₅ are the same as the definitions of R ₆₁ to R ₇₀ in [Formula D3],

    The R ₃ to R ₅ may be combined with each of the Q ₂ ring or the Q ₃ ring to further form an alicyclic or aromatic monocyclic or polycyclic ring,

    The R ₄ and R ₅ may be connected to each other to further form an alicyclic or aromatic monocyclic or polycyclic ring,

    The ring formed by Cy1 has a nitrogen (N) atom, an aromatic carbon atom in the Q1 ring to which the nitrogen (N) atom is bonded, and an aromatic carbon atom in the Q1 ring to be bonded to Cy1, substituted or unsubstituted carbon number 1 to 10 alkylene groups,

    In the [Formula D9], 'Cy2' may be added to Cy1 to form a saturated hydrocarbon ring, and the ring formed by Cy2 has 1 to 10 substituted or unsubstituted carbon atoms, except for carbon atoms included in Cy1. is an alkylene group of

    In the [Formula D10], the ring formed by Cy3 is an aromatic carbon atom in the Q3 ring to be bonded to Cy3, an aromatic carbon atom in Q3 to be bonded to a nitrogen (N) atom, a nitrogen (N) atom, the nitrogen (N) ) is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, except for carbon atoms in Cy1 to which the atoms are bonded;

    'Substitution' in 'substituted or unsubstituted' in [Formula D1] to [Formula D10] is deuterium, cyano group, halogen group, hydroxyl group, nitro group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C2-C24 alkenyl group, C2-C24 alkynyl group, C3-C24 cycloalkyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C7-C24 arylalkyl group , C7-C24 alkylaryl group, C2-C24 heteroaryl group, C2-C24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylamino group, C12-C24 dia Rylamino group, diheteroarylamino group having 2 to 24 carbon atoms, aryl (heteroaryl)amino group having 7 to 24 carbon atoms, alkylsilyl group having 1 to 24 carbon atoms, arylsilyl group having 6 to 24 carbon atoms, arylox having 6 to 24 carbon atoms It means to be substituted with one or more substituents selected from the group consisting of a group and an arylthionyl group having 6 to 24 carbon atoms.
16. 12. The method of claim 11,

    At least one layer selected from the respective layers is an organic light emitting device, characterized in that formed by a deposition process or a solution process.
17. 11. The method of claim 10,

    The organic light emitting device may include a flat panel display device; flexible display devices; devices for flat-panel lighting, either monochromatic or white; and monochromatic or white flexible lighting devices; An organic light emitting device, characterized in that it is used in any one selected from.