KR102284692B1 - Organic light emitting device, manufacturing method of the same and composition for organic layer of organic light emitting device - Google Patents

Abstract

The present specification relates to an organic light emitting device, a method for manufacturing the same, and a composition for an organic material layer.

Description

Organic light emitting device, manufacturing method thereof, and composition for organic material layer

The present specification relates to an organic light emitting device, a method for manufacturing the same, and a composition for an organic material layer.

The electroluminescent device is a type of self-luminous display device, and has a wide viewing angle, excellent contrast, and fast response speed.

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes combine in the organic thin film to form a pair, and then disappear and emit light. The organic thin film may be composed of a single layer or multiple layers, if necessary.

The material of the organic thin film may have a light emitting function if necessary. For example, as the organic thin film material, a compound capable of forming the light emitting layer by itself may be used, or a compound capable of serving as a host or dopant of the host-dopant light emitting layer may be used. In addition, as a material of the organic thin film, a compound capable of performing the functions of hole injection, hole transport, electron blocking, hole blocking, electron transport, electron injection, and the like may be used.

In order to improve the performance, lifespan, or efficiency of the organic light emitting device, the development of a material for the organic thin film is continuously required.

U.S. Patent No. 4,356,429

The present application relates to an organic light emitting device, a method for manufacturing the same, and a composition for an organic material layer.

An exemplary embodiment of the present application is an organic light emitting device including a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode,

At least one layer of the organic material layer provides an organic light-emitting device comprising a heterocyclic compound represented by the following Chemical Formula 1, and a heterocyclic compound represented by the following Chemical Formula 2.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclic group containing one or more N,

L is a direct bond; a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group, a is an integer from 1 to 3, and when a is 2 or more, L is the same as or different from each other,

R1 to R19 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring, b and c are each is an integer of 1 to 3, d is an integer of 0 to 2, when b is 2 or more, R9 is the same as or different from each other, when c is 2 or more, R10 is the same as or different from each other, and when d is an integer of 2, R19 is same or different from each other,

A ₁ and A ₂ are the same as or different from each other and each independently O; S; NR _a ; or CR _b R _c ,

Wherein R _{a To} R _{c Are} the same as or different from each other, and each independently, hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In addition, another exemplary embodiment of the present application provides a composition for an organic material layer of an organic light emitting device comprising the heterocyclic compound represented by Formula 1, and the compound represented by Formula 2 above.

Finally, an exemplary embodiment of the present application comprises the steps of preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer, wherein the forming of the organic material layer comprises the step of forming one or more organic material layers using the composition for an organic material layer according to an exemplary embodiment of the present application. A method of manufacturing an organic light emitting device is provided.

The heterocyclic compound according to an exemplary embodiment of the present application may be used as an organic material layer material of an organic light emitting device. The heterocyclic compound may be used as a material for a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a charge generation layer, etc. in an organic light emitting device. In particular, the heterocyclic compound represented by Formula 1 and the compound represented by Formula 2 may be simultaneously used as a material of the light emitting layer of the organic light emitting device. In addition, when the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 are used in an organic light emitting device at the same time, the driving voltage of the device is lowered, the light efficiency is improved, and the thermal stability of the compound increases the efficiency of the device. Lifespan characteristics can be improved.

In particular, in the heterocyclic compound represented by Formula 1, an N-containing ring is substituted at the 3rd carbon position of the dibenzofuran structure, and a carbazole structure is substituted for benzene in which the N-containing ring is unsubstituted in the structure of the dibenzofuran. As a result, it has a more electronically stable structure, thereby improving the device lifetime.

1 to 3 are views schematically showing a stacked structure of an organic light emitting device according to an exemplary embodiment of the present application, respectively.
4 and 5 are graphs showing the thermal stability of Compound 2-8 of the present application.
6 and 7 are graphs showing the thermal stability of Compound 2-18 of the present application.
8 and 9 are graphs showing the thermal stability of compound 2-79 of the present application.
10 and 11 are graphs showing the thermal stability of Compound 2-123 of the present application.
12 and 13 are graphs showing the thermal stability of Compound 2-19 of the present application.
14 and 15 are graphs showing the thermal stability of Compound 2-20 of the present application.
16 and 17 are graphs showing the thermal stability of Compound 2-22 of the present application.
18 and 19 are graphs showing the thermal stability of Compound A.
20 and 21 are graphs showing the thermal stability of Compound C.

Hereinafter, the present application will be described in detail.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is substituted. , two or more substituents may be the same as or different from each other.

In the present specification, "substituted or unsubstituted" means C1 to C60 linear or branched alkyl; C2 to C60 linear or branched alkenyl; C2 to C60 linear or branched alkynyl; C3 to C60 monocyclic or polycyclic cycloalkyl; C2 to C60 monocyclic or polycyclic heterocycloalkyl; C6 to C60 monocyclic or polycyclic aryl; C2 to C60 monocyclic or polycyclic heteroaryl; -SiRR'R"; -P(=O)RR'; C1 to C20 alkylamine; C6 to C60 monocyclic or polycyclic arylamine; and C2 to C60 monocyclic or polycyclic heteroarylamine selected from the group consisting of It means that it is substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with a substituent to which two or more substituents selected from the above-exemplified substituents are connected.

In an exemplary embodiment of the present application, R, R' and R" are the same as or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted hetero It may be an aryl group.

In the present specification, the halogen may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group includes a straight or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms in the alkyl group may be 1 to 60, specifically 1 to 40, more specifically, 1 to 20. Specific examples include methyl group, ethyl group, 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, and the like, but is not limited thereto.

In the present specification, the alkenyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The carbon number of the alkenyl group may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20. Specific examples include a vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl 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)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but are not limited thereto.

In the present specification, the alkynyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The carbon number of the alkynyl group may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C20. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. may be It is not limited.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic refers to a group in which a cycloalkyl group is directly connected or condensed with another ring group. Here, the other ring group may be a cycloalkyl group, but may be a different type of ring group, for example, a heterocycloalkyl group, an aryl group, a heteroaryl group, or the like. The carbon number of the cycloalkyl group may be 3 to 60, specifically 3 to 40, more specifically 5 to 20. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 ,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, and the like, but is not limited thereto.

In the present specification, the heterocycloalkyl group includes O, S, Se, N or Si as a hetero atom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic refers to a group in which a heterocycloalkyl group is directly connected or condensed with another ring group. Here, the other ring group may be a heterocycloalkyl group, but may be a different type of ring group, for example, a cycloalkyl group, an aryl group, a heteroaryl group, or the like. The heterocycloalkyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 3 to 20 carbon atoms.

In the present specification, the aryl group includes a monocyclic or polycyclic having 6 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which an aryl group is directly connected or condensed with another ring group. Here, the other ring group may be an aryl group, but may be a different type of ring group, for example, a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, or the like. The aryl group includes a spiro group. The carbon number of the aryl group may be 6 to 60, specifically 6 to 40, more specifically 6 to 25. Specific examples of the aryl group include a phenyl group, a biphenyl group, a triphenyl group, a naphthyl group, an anthryl group, a chrysenyl group, a phenanthrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a phenalenyl group, a pyrethyl group Nyl group, tetracenyl group, pentacenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, condensed ring groups thereof and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may combine with each other to form a ring.

,

,

,

,

,

등이 될 수 있으나, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

,

and the like, but is not limited thereto.

In the present specification, the heteroaryl group includes S, O, Se, N or Si as a hetero atom, and includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic refers to a group in which a heteroaryl group is directly connected or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may be a different type of ring group, for example, a cycloalkyl group, a heterocycloalkyl group, an aryl group, or the like. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 3 to 25 carbon atoms. Specific examples of the heteroaryl group include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group group, isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , thiazinyl group, deoxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolilyl group, naphthyridyl group, acridinyl group, phenanthridyl group Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triazaindene group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, Phenoxazinyl group, phenanthridyl group, imidazopyridinyl group, thienyl group, indolo[2,3-a]carbazolyl group, indolo[2,3-b]carbazolyl group, indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenothiazinyl group, phthalazinyl group, naphthylidinyl group, phenanthrolinyl group, Benzo[c][1,2,5]thiadiazolyl group, 5,10-dihydrodibenzo[b,e][1,4]azasilinyl, pyrazolo[1,5-c]quinazolinyl group , pyrido [1,2-b] indazolyl group, pyrido [1,2-a] imidazo [1,2-e] indolinyl group, 5,11-dihydroindeno [1,2-b ] a carbazolyl group, and the like, but is not limited thereto.

In the present specification, the amine group is a monoalkylamine group; monoarylamine group; monoheteroarylamine group; -NH ₂ ; dialkylamine group; diarylamine group; diheteroarylamine group; an alkylarylamine group; an alkyl heteroarylamine group; And it may be selected from the group consisting of an aryl heteroarylamine group, the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a dibiphenylamine group, an anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluorene There is a nylamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group, and the like, but is not limited thereto.

In the present specification, the arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied. In addition, the heteroarylene group means that the heteroaryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the heteroaryl group described above may be applied.

In the present specification, the phosphine oxide group is represented by _{-P(=O)R 101} R _{102 , R 101} and R ₁₀₂ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specifically, it may be substituted with an aryl group, and the above-described examples may be applied to the aryl group. For example, the phosphine oxide group includes a diphenylphosphine oxide group, a dinaphthyl phosphine oxide group, and the like, but is not limited thereto.

In the present specification, the silyl group is a substituent including Si and the Si atom is directly connected as a radical, and is represented by _{-SiR 104} R ₁₀₅ R _{106 , R 104} to R ₁₀₆ are the same or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specific examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. It is not limited.

As used herein, "adjacent" group means a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom in which the substituent is substituted. can 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" to each other.

The structures exemplified by the above-described cycloalkyl group, cycloheteroalkyl group, aryl group and heteroaryl group may be applied, except that the aliphatic or aromatic hydrocarbon ring or heterocycle that adjacent groups may form is not a monovalent group.

An exemplary embodiment of the present application is an organic light emitting device including a first electrode, a second electrode, and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers is the formula (1) It provides an organic light emitting device comprising a heterocyclic compound represented by, and a heterocyclic compound represented by Formula 2 above.

In an exemplary embodiment of the present application, Chemical Formula 1 may be represented by any one of Chemical Formulas 3 to 6 below.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 3 to 6, the substituents are as defined in Formula 1 above.

In an exemplary embodiment of the present application, N-Het is a monocyclic or polycyclic heterocycle including one or more N-substituted or unsubstituted.

In another exemplary embodiment, N-Het is a monocyclic or polycyclic heterocycle including one or more N, which is unsubstituted or substituted with one or more substituents selected from the group consisting of an aryl group and a heteroaryl group.

In another embodiment, N-Het is unsubstituted or substituted with one or more substituents selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, a dimethyl fluorene group, a dibenzofuran group, and a dibenzothiophene group, It is a monocyclic or polycyclic heterocyclic ring containing one or more N.

In another embodiment, N-Het is unsubstituted or substituted with one or more substituents selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, a dimethyl fluorene group, a dibenzofuran group, and a dibenzothiophene group, It is a monocyclic or polycyclic heterocyclic ring containing 1 or more and 3 or less N.

In an exemplary embodiment of the present application, N-Het is a monocyclic heterocycle which is substituted or unsubstituted, and includes one or more N.

In an exemplary embodiment of the present application, N-Het is a substituted or unsubstituted, bicyclic or more heterocyclic ring including one or more N.

In an exemplary embodiment of the present application, N-Het is a monocyclic or polycyclic heterocyclic ring that is substituted or unsubstituted, and includes two or more N.

In an exemplary embodiment of the present application, N-Het is a bicyclic or more polycyclic heterocycle containing two or more N.

In an exemplary embodiment of the present application, N-Het is a pyrimidine group unsubstituted or substituted with a phenyl group; a triazine group unsubstituted or substituted with one or more substituents selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, a dimethyl fluorene group, a dibenzofuran group, and a dibenzothiophene group; a phenyl group-substituted or unsubstituted benzimidazole group; a quinazoline group unsubstituted or substituted with one or more substituents selected from the group consisting of a phenyl group and a biphenyl group; Or it may be a phenanthroline group substituted or unsubstituted with a phenyl group.

In an exemplary embodiment of the present application, Chemical Formula 1 is represented by one of Chemical Formulas 7 to 9 below.

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 7 to 9, the definitions of R1 to R10, L, a, b and c are as defined in Formula 1 above,

X1 is CR21 or N, X2 is CR22 or N, X3 is CR23 or N, X4 is CR24 or N, X5 is CR25 or N,

R21 to R25 and R27 to R32 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group or adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a hetero ring.

는 하기 화학식 10 내지 12 중 하나로 표시될 수 있다. 여기서,

은 L에 연결되는 부위이다. In an exemplary embodiment of the present application,

may be represented by one of the following Chemical Formulas 10 to 12. here,

is a region connected to L.

[Formula 10]

[Formula 11]

[Formula 12]

In Formula 10, at least one of X1, X3 and X5 is N, and the rest are as defined in Formula 7,

In Formula 11, at least one of X1, X2 and X5 is N, and the rest are as defined in Formula 7,

In Formula 12, at least one of X1 to X3 is N, and the rest are as defined in Formula 7,

R22, R24 and R33 to R36 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group or adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a hetero ring.

In the exemplary embodiment of the present application, Chemical Formula 10 may be selected from the following structural formulas.

In the above structural formula, R21 to R25 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group or adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a hetero ring.

In the exemplary embodiment of the present application, Chemical Formula 11 may be represented by Chemical Formula 13 below.

[Formula 13]

The substituents of Formula 13 are as defined in Formula 11.

In an exemplary embodiment of the present application, Chemical Formula 12 may be represented by Chemical Formula 14 below.

[Formula 14]

The substituents of Formula 14 are as defined in Formula 12.

In an exemplary embodiment of the present application, Chemical Formula 11 may be represented by Chemical Formula 15 below.

[Formula 15]

In Formula 15, R37 is the same as or different from each other and is hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or hetero ring, e is an integer from 0 to 7, and e is In the case of 2 or more, R37 is the same as or different from each other.

In an exemplary embodiment of the present application, L is a direct bond or an arylene group.

In another exemplary embodiment, L is a direct bond or a phenylene group.

In an exemplary embodiment of the present application, R9 and R10 are hydrogen; or deuterium.

In another exemplary embodiment, R9 and R10 are hydrogen.

In an exemplary embodiment of the present application, R1 to R8 are hydrogen; heavy hydrogen; an aryl group unsubstituted or substituted with an alkyl group, an aryl group, or a heteroaryl group; or a heteroaryl group unsubstituted or substituted with an aryl group or a heteroaryl group.

In another exemplary embodiment, R1 to R8 are hydrogen; heavy hydrogen; aryl group; heteroaryl group; or a heteroaryl group substituted with an aryl group.

In another exemplary embodiment, R1 to R8 are hydrogen; heavy hydrogen; phenyl group; dibenzofuran group; dibenzothiophene group; a carbazole group; or a carbazole group substituted with a phenyl group.

In another exemplary embodiment, two adjacent substituents among R1 to R8 are bonded to each other to form a substituted or unsubstituted ring.

In another exemplary embodiment, two adjacent substituents of R1 to R8 combine with each other to form a ring unsubstituted or substituted with an aryl group or an alkyl group.

In another exemplary embodiment, two adjacent substituents among R1 to R8 are bonded to each other to form an aromatic hydrocarbon ring or heterocycle unsubstituted or substituted with an aryl group or an alkyl group.

In another exemplary embodiment, two adjacent substituents among R1 to R8 combine with each other to form an aromatic hydrocarbon ring or heterocycle unsubstituted or substituted with a phenyl group or a methyl group.

In another exemplary embodiment, two adjacent substituents of R1 to R8 are bonded to each other to form an indole ring unsubstituted or substituted with a phenyl group; benzothiophene ring; benzofuran ring; Alternatively, an indene ring substituted or unsubstituted with a methyl group may be formed.

는 하기 화학식 16으로 표시될 수 있다. 여기서,

은 디벤조퓨란 구조에 연결되는 부위이다.In another embodiment,

may be represented by the following formula (16). here,

is a site connected to the dibenzofuran structure.

[Formula 16]

In the formula (16),

R1 to R4 are as defined in Formula 1,

Y is O, S, NR _d or CR _e R _f ,

R _d , R _e , R _f , R41 and R42 are the same as or different from each other and are hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring, and f is 0 to 4 is an integer of and when f is 2 or more, R41 is the same as or different from each other, g is an integer of 0 to 2, and when g is 2 or more, R42 is the same as or different from each other.

In another exemplary embodiment, Chemical Formula 16 may be selected from the following structural formulas.

In the above structural formula,

The definition of the substituent is as defined in Formula 16 above.

In an exemplary embodiment of the present application, R28 to R31 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; aryl group; or a heteroaryl group.

In another exemplary embodiment, R28 to R31 are the same as or different from each other, and each independently hydrogen; or deuterium.

In another exemplary embodiment, R28 to R31 are hydrogen.

In an exemplary embodiment of the present application, R27 and R32 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; aryl group; or a heteroaryl group.

In another exemplary embodiment, R27 and R32 are the same as or different from each other, and each independently an aryl group; or a heteroaryl group.

In another exemplary embodiment, R27 and R32 are the same as or different from each other, and each independently represents an aryl group.

In another exemplary embodiment, R27 and R32 are phenyl groups.

In an exemplary embodiment of the present application, R21 to R25 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an aryl group unsubstituted or substituted with an alkyl group; Or a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, R21 to R25 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an aryl group unsubstituted or substituted with an alkyl group; or a heteroaryl group.

In another exemplary embodiment, R21 to R25 are the same as or different from each other, and each independently hydrogen; an aryl group unsubstituted or substituted with a methyl group; or a heteroaryl group.

In another exemplary embodiment, R21 to R25 are the same as or different from each other, and each independently hydrogen; phenyl group; biphenylyl group; naphthyl group; dimethyl fluorenyl group; dibenzofuran group; or a dibenzothiophene group.

In an exemplary embodiment of the present application, R22 and R24 are the same as or different from each other, and each independently an aryl group unsubstituted or substituted with an alkyl group; or a heteroaryl group.

In another exemplary embodiment, R22 and R24 are the same as or different from each other, and each independently a phenyl group, a biphenylyl group, a naphthyl group, a dimethyl fluorenyl group; dibenzofuran group; or a dibenzothiophene group.

In an exemplary embodiment of the present application, R33 to R36 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; aryl group; Or a heteroaryl group, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a hetero ring.

In another exemplary embodiment, R33 to R36 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or an aryl group, or two or more groups adjacent to each other combine with each other to form an aliphatic or aromatic hydrocarbon ring or a hetero ring.

In another exemplary embodiment, R33 to R36 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or an aryl group, or two or more groups adjacent to each other are bonded to each other to form a pyridine ring.

In another exemplary embodiment, R33 to R36 are the same as or different from each other, and each independently hydrogen; Or an aryl group, or two or more groups adjacent to each other are bonded to each other to form a pyridine ring.

In another exemplary embodiment, R33 to R36 are the same as or different from each other, and each independently hydrogen; phenyl group; Or a biphenylyl group, or two or more groups adjacent to each other combine with each other to form a pyridine ring.

In an exemplary embodiment of the present application, R37 is hydrogen; heavy hydrogen; aryl group; or a heteroaryl group.

In another exemplary embodiment, R37 is hydrogen; heavy hydrogen; or an aryl group.

In another exemplary embodiment, R37 is hydrogen; or an aryl group.

In another exemplary embodiment, R37 is hydrogen; or a phenyl group.

In an exemplary embodiment of the present application, Y is O or S.

In another exemplary embodiment, Y is NR _d and R _d is an aryl group.

In another exemplary embodiment, Y is NR _d and R _d is a phenyl group.

In another exemplary embodiment, Y is CR _e R _f , and R _e and R _f are alkyl groups.

In another exemplary embodiment, Y is CR _e R _f , and R _e and R _f are methyl groups.

In an exemplary embodiment of the present application, R41 is hydrogen; heavy hydrogen; aryl group; or a heteroaryl group.

In another exemplary embodiment, R41 is hydrogen; heavy hydrogen; or an aryl group.

In another exemplary embodiment, R41 is hydrogen; or a phenyl group.

In an exemplary embodiment of the present application, R42 is hydrogen; or deuterium.

In another exemplary embodiment, R42 is hydrogen.

In an exemplary embodiment of the present application, A ₁ and A ₂ of Formula 2 are the same as or different from each other and each independently O; S; NR _a ; or CR _b R _c .

In an exemplary embodiment of the present application, R _{a To} R _{c Are} the same as or different from each other, and each independently, hydrogen; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another exemplary embodiment, the R _{a To} R _{c Are} the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C6 to C40 aryl group; Or it may be a substituted or unsubstituted C2 to C40 heteroaryl group.

In another exemplary embodiment, the R _{a To} R _{c Are} the same as or different from each other, and each independently hydrogen; C1 to C40 alkyl group; a C6 to C40 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a C1 to C40 alkyl group, a C6 to C40 aryl group, and a triphenylsilyl group; Or it may be a C2 to C40 heteroaryl group unsubstituted or substituted with a C6 to C40 aryl group.

In another exemplary embodiment, R _{a To} R _{c Are} the same as or different from each other, and each independently a methyl group; a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a phenyl group and a triphenylsilyl group; a biphenyl group unsubstituted or substituted with a phenyl group; naphthyl group; triphenylenyl group; diphenylfluorenyl group; dimethyl fluorenyl group; a carbazole group unsubstituted or substituted with a phenyl group; dibenzofuran group; Or it may be a dibenzothiophene group.

In an exemplary embodiment of the present application, R11 to R19 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or adjacent to each other may combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring.

In another exemplary embodiment, R11 to R19 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, R11 to R19 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted C6 to C60 aryl group; Or it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another exemplary embodiment, R11 to R19 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted C6 to C40 aryl group; Or it may be a substituted or unsubstituted C2 to C40 heteroaryl group.

In another exemplary embodiment, R11 to R19 are the same as or different from each other, and each independently hydrogen; C6 to C40 aryl group; Or it may be a C2 to C40 heteroaryl group unsubstituted or substituted with a C6 to C40 aryl group.

In another exemplary embodiment, R11 to R19 are the same as or different from each other, and each independently hydrogen; phenyl group; triphenylenyl group; a carbazole group unsubstituted or substituted with a phenyl group or a biphenyl group; dibenzofuran group; Or it may be a dibenzothiophene group.

In an exemplary embodiment of the present application, R15 to R19 may be hydrogen.

In the exemplary embodiment of the present application, R11 and R14 may be hydrogen.

In an exemplary embodiment of the present application, R11 and R14 to R19 may be hydrogen.

In an exemplary embodiment of the present application, R12 and R13 are the same as or different from each other, and each independently hydrogen; phenyl group; triphenylenyl group; a carbazole group unsubstituted or substituted with a phenyl group or a biphenyl group; dibenzofuran group; Or it may be a dibenzothiophene group.

In an exemplary embodiment of the present application, Chemical Formula 2 may be represented by any one of Chemical Formulas 2-1 to 2-6 below.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In Formulas 2-1 to 2-6,

Definitions of R11 to R19, A ₁ , A ₂ and d are the same as those in Formula 2 above.

In an exemplary embodiment of the present application, Chemical Formula 2 may be represented by any one of the following Chemical Formulas 2-7 to 2-9.

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

In Formulas 2-7 to 2-9,

The definitions of A ₁ , A ₂ , R11 , and R14 are the same as the definitions in Formula 2 above,

A ₃ is O; S; or NR _g ,

R50 and R51 are hydrogen; Or a substituted or unsubstituted aryl group, at least one is a substituted or unsubstituted aryl group,

R _g , R52 and R53 are the same as or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

r is an integer from 0 to 3,

q is an integer from 0 to 4.

In an exemplary embodiment of the present application, R50 and R51 are hydrogen; Or it may be a substituted or unsubstituted aryl group.

In another exemplary embodiment, R50 and R51 are hydrogen; Or it may be a substituted or unsubstituted C6 to C60 aryl group.

In another exemplary embodiment, R50 and R51 are hydrogen; Or it may be a substituted or unsubstituted C6 to C40 aryl group.

In another exemplary embodiment, R ₅₀ and R ₅₁ are hydrogen; Or it may be a C6 to C40 aryl group.

In another exemplary embodiment, R50 and R51 are hydrogen; phenyl group; Or it may be a triphenylenyl group.

In an exemplary embodiment of the present application, at least one of R50 and R51 may be a substituted or unsubstituted aryl group.

In the exemplary embodiment of the present application, R52 and R53 may be hydrogen.

In an exemplary embodiment of the present application, R _g may be a substituted or unsubstituted aryl group.

In another exemplary embodiment, R _g may be a substituted or unsubstituted C6 to C60 aryl group.

In another exemplary embodiment, R _g may be a substituted or unsubstituted C6 to C40 aryl group.

In another exemplary embodiment, R _g may be a C6 to C40 aryl group.

In another exemplary embodiment, R _g is a phenyl group; or a biphenyl group.

In the case of having a condensed basic ring as shown in Formula 2-7, when applied to an organic light emitting device together with the heterocyclic compound of Formula 1, it has very fast hole transport properties as a host material, in particular, the threshold voltage of the device and The driving voltage is made low, and accordingly, the device has a characteristic that can be driven even at a low voltage.

When it has a substituent (R50) in the condensed ring structure as shown in Chemical Formula 2-8, it has a larger structure than in Chemical Formula 2-7, and due to its characteristics, a substituent (R50) extended from the basic skeleton The conjugation region becomes wider and the region of the HOMO level is more expanded. Therefore, holes are distributed over a wide HOMO level region, and more stable hole transport capability can be maintained. That is, in the case of Formula 2-8, the driving voltage is increased to a certain extent, but overall lifespan characteristics are more excellent.

In the case of Formula 2-9, when a heteroaryl group is substituted in the condensed ring structure, the substitution of several heteroaryl groups is performed along with the property of maintaining a stable HOMO level through a wide conjugation region as shown in Formula 2-8. It can be used as an auxiliary means of bandgap control. In particular, as the dibenzofuran/dibenzothiophene group has the largest structural structure, the driving voltage rises slightly compared to the basic skeleton. The lifespan characteristics are particularly excellent.

When the compound of Formula 1 and the compound of Formula 2 are simultaneously included in the organic material layer of the organic light emitting device, better efficiency and lifespan effect are exhibited. This result can be expected to occur when both compounds are included at the same time exciplex (exciplex) phenomenon.

The exciplex phenomenon is a phenomenon in which energy having a size of a HOMO level of a donor (p-host) and a LUMO level of an acceptor (n-host) is emitted through electron exchange between two molecules. When an exciplex phenomenon occurs between two molecules, Reverse Intersystem Crossing (RISC) occurs, thereby increasing the internal quantum efficiency of fluorescence to 100%. When a donor (p-host) with good hole transport ability and an acceptor (n-host) with good electron transport ability are used as hosts of the emission layer, the driving voltage is because holes are injected into the p-host and electrons are injected into the n-host. can be lowered, thereby helping to improve lifespan.

In an exemplary embodiment of the present application, Chemical Formula 1 may be represented by any one of the following compounds, but is not limited thereto.

In an exemplary embodiment of the present application, Chemical Formula 2 may be represented by any one of the following compounds, but is not limited thereto.

In addition, by introducing various substituents into the structures of Formulas 1 and 2, compounds having the intrinsic properties of the introduced substituents can be synthesized. For example, by introducing a substituent mainly used for a hole injection layer material, a hole transport material, a light emitting layer material, an electron transport layer material, and a charge generation layer material used in manufacturing an organic light emitting device into the core structure, the conditions required for each organic material layer are satisfied. substances can be synthesized.

In addition, by introducing various substituents into the structures of Chemical Formulas 1 and 2, it is possible to finely control the energy band gap, while improving the properties at the interface between organic materials and diversifying the use of the material. .

On the other hand, the heterocyclic compound has a high glass transition temperature (Tg) and excellent thermal stability. This increase in thermal stability is an important factor in providing driving stability to the device.

The heterocyclic compound according to an exemplary embodiment of the present application may be prepared by a multi-step chemical reaction. Some intermediate compounds are prepared first, and compounds of Formula 1 or 2 can be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to an exemplary embodiment of the present application may be prepared based on Preparation Examples to be described later.

In addition, another exemplary embodiment of the present application provides a composition for an organic material layer of an organic light emitting device comprising the heterocyclic compound represented by Formula 1, and the compound represented by Formula 2 above.

Specific details of the heterocyclic compound represented by Formula 1 and the compound represented by Formula 2 are the same as described above.

The weight ratio of the heterocyclic compound represented by Formula 1 in the composition to the compound represented by Formula 2 may be 1: 10 to 10: 1, 1: 8 to 8: 1, and 1: 5 to 5 : may be 1, and may be 1: 2 to 2: 1, but is not limited thereto.

The composition may be used when forming an organic material of an organic light emitting device, and in particular, it may be more preferably used when forming a host of a light emitting layer.

The composition is a form in which two or more compounds are simply mixed, and a material in a powder state may be mixed before forming the organic material layer of the organic light emitting device, or a compound in a liquid state at an appropriate temperature or higher may be mixed. The composition is in a solid state below the melting point of each material, and can be maintained in a liquid state by adjusting the temperature.

The composition may further include materials known in the art, such as solvents and additives.

The organic light emitting device according to an exemplary embodiment of the present application is a conventional organic light emitting device, except for forming one or more organic material layers using the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 above. It may be manufactured by a method and material for manufacturing a light emitting device.

The compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.

Specifically, the organic light emitting device according to an exemplary embodiment of the present application includes a first electrode, a second electrode, and at least one organic material layer provided between the first electrode and the second electrode, and at least one of the organic material layers is and a heterocyclic compound represented by Formula 1, and a heterocyclic compound represented by Formula 2 above.

In the exemplary embodiment of the present application, the first electrode may be an anode, and the second electrode may be a cathode.

In another exemplary embodiment, the first electrode may be a cathode, and the second electrode may be an anode.

In the exemplary embodiment of the present application, the organic light emitting device may be a blue organic light emitting device, and the heterocyclic compound according to Formula 1 and the heterocyclic compound according to Formula 2 may be used as a material of the blue organic light emitting device. .

In an exemplary embodiment of the present application, the organic light emitting device may be a green organic light emitting device, and the compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 may be used as a material of the green organic light emitting device .

In an exemplary embodiment of the present application, the organic light emitting device may be a red organic light emitting device, and the compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 may be used as a material of the red organic light emitting device. .

The organic light emitting device of the present invention includes a light emitting layer, a hole injection layer, and a hole transport layer. It may further include one or more layers selected from the group consisting of an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

In an exemplary embodiment of the present application, the organic material layer includes at least one of a hole blocking layer, an electron injection layer, and an electron transport layer, and at least one of the hole blocking layer, the electron injection layer and the electron transport layer is represented by Formula 1 It provides an organic light emitting device comprising the heterocyclic compound represented by, and the heterocyclic compound represented by Formula 2 above.

In an exemplary embodiment of the present application, the organic material layer includes a light emitting layer, and the light emitting layer provides an organic light emitting device comprising a heterocyclic compound represented by Formula 1, and a heterocyclic compound represented by Formula 2 do.

In an exemplary embodiment of the present application, the organic material layer includes a light emitting layer, the light emitting layer includes a host material, and the host material is a heterocyclic compound represented by Formula 1, and a heterocyclic compound represented by Formula 2 It provides an organic light emitting device comprising a.

1 to 3 illustrate the stacking order of the electrode and the organic material layer of the organic light emitting device according to an exemplary embodiment of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and the structure of an organic light emitting device known in the art may also be applied to the present application.

Referring to FIG. 1 , an organic light emitting device in which an anode 200 , an organic material layer 300 , and a cathode 400 are sequentially stacked on a substrate 100 is illustrated. However, it is not limited to such a structure, and as shown in FIG. 2 , an organic light emitting device in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate may be implemented.

3 illustrates a case in which the organic material layer is multi-layered. The organic light emitting diode according to FIG. 3 includes a hole injection layer 301 , a hole transport layer 302 , a light emitting layer 303 , a hole blocking layer 304 , an electron transport layer 305 , and an electron injection layer 306 . However, the scope of the present application is not limited by such a laminated structure, and if necessary, the remaining layers except for the light emitting layer may be omitted, and other necessary functional layers may be further added.

In an exemplary embodiment of the present application, the method comprising: preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer, wherein the forming of the organic material layer comprises the step of forming one or more organic material layers using the composition for an organic material layer according to an exemplary embodiment of the present application. A method of manufacturing an organic light emitting device is provided.

In an exemplary embodiment of the present application, the step of forming the organic material layer is formed by using a thermal vacuum deposition method by pre-mixing the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 A method of manufacturing an organic light emitting diode is provided.

The pre-mixed refers to mixing the materials in one park before depositing the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 on the organic layer.

The premixed material may be referred to as a composition for an organic material layer according to an exemplary embodiment of the present application.

In the organic light emitting device according to an exemplary embodiment of the present application, materials other than the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 are exemplified below, but these are for illustration only, and the scope of the present application It is not intended to be limiting, and materials known in the art may be substituted.

Materials having a relatively large work function may be used as the anode material, and transparent conductive oxides, metals, conductive polymers, or the like may be used. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO ₂ : Combination of metals and oxides such as Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

Materials having a relatively low work function may be used as the cathode material, and metal, metal oxide, conductive polymer, or the like may be used. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

As the hole injection material, a known hole injection material may be used, for example, a phthalocyanine compound such as copper phthalocyanine disclosed in US Pat. No. 4,356,429 or Advanced Material, 6, p.677 (1994). starburst-type amine derivatives such as tris(4-carbazolyl-9-ylphenyl)amine (TCTA), 4,4′,4″-tri[phenyl(m-tolyl)amino]triphenylamine (m- MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), soluble conductive polymers polyaniline/dodecylbenzenesulfonic acid (Polyaniline/Dodecylbenzenesulfonic acid) or poly( 3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), polyaniline/Camphor sulfonic acid (Polyaniline/Camphor sulfonic acid) or polyaniline/ Poly(4-styrenesulfonate) (Polyaniline/Poly(4-styrene-sulfonate)) and the like may be used.

As the hole transport material, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, etc. may be used, and a low molecular weight or high molecular material may be used.

Examples of the electron transport material include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, and fluorenone. Derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, etc. may be used, and polymer materials as well as low molecular weight materials may be used.

As the electron injection material, for example, LiF is typically used in the art, but the present application is not limited thereto.

A red, green or blue light emitting material may be used as the light emitting material, and if necessary, two or more light emitting materials may be mixed and used. In this case, two or more light emitting materials may be deposited and used as individual sources, or may be pre-mixed and deposited as a single source after pre-mixing. In addition, although a fluorescent material can be used as a light emitting material, it can also be used as a phosphorescent material. As the light emitting material, a material that emits light by combining holes and electrons respectively injected from the anode and the cathode may be used, but materials in which the host material and the dopant material together participate in light emission may be used.

When mixing and using a host of a light emitting material, a host of the same series may be mixed and used, or a host of different series may be mixed and used. For example, any two or more types of n-type host material or p-type host material may be selected and used as the host material of the light emitting layer.

The organic light emitting device according to the exemplary embodiment of the present application may be a top emission type, a back emission type, or a double side emission type depending on a material used.

The heterocyclic compound according to an exemplary embodiment of the present application may act on a principle similar to that applied to an organic light emitting device in an organic electronic device including an organic solar cell, an organic photoreceptor, and an organic transistor.

Hereinafter, the present specification will be described in more detail through examples, but these are only for illustrating the present application and not for limiting the scope of the present application.

[ Preparation Example 1 ] Preparation of compound 1 (C)

Preparation of compound 1-1

1-bromo-2,3-difluorobenzene (50 g, 259 mmol), (4-chloro-2-methoxyphenyl) boronic acid (57.7 g, 310 mmol) in a one-necked round bottom flask (One neck rbf) , tetrakis(triphenylphosphine)palladium(0) (29g, 25.9mmol), potassium carbonate (71.5g, 51.8mmol), and toluene/ethanol/water (800ml/160ml/160ml) mixture was refluxed at 110°C.

It was extracted with dichloromethane and dried over _{MgSO 4 .} After silica gel filter, it was concentrated to obtain compound 1-1. (65g, 99%)

Preparation of compound 1-2

A mixture of 4'-chloro-2,3-difluoro-2'-methoxy-1,1'-biphenyl (65 g, 255 mmol) and MC (1000 ml) in a one-necked round bottom flask (one neck rbf) The temperature was lowered to 0° C., BBr ₃ (48 mL, 500 mmol) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 2 hours.

The reaction was terminated with distilled water, extracted with dichloromethane, and dried _{over MgSO 4 .} Column purification was lowered to MC:HX = 1:2 to obtain compound 1-2. (49g, 80%)

Preparation of compound 1-3

4-Chloro-2',3'-difluoro-[1,1'-biphenyl]-2-ol (49 g, 203 mmol), Cs ₂ CO ₃ ( A mixture of 331 g, 1018 mmol) of dimethylacetamide (500 ml) was stirred at 120°C. After cooling, the filtrate was filtered and the solvent of the filtrate was removed, and column purification was lowered to HX:MC = 5:1 to obtain compound 1-3. (10.1 g, 88%)

Preparation of compound 1-4

3-chloro-6-fluorodibenzo [b, d] furan (9 g, 40.7 mmol), 9H-carbazole (8.1 g, 48.9 mmol), Cs ₂ CO ₃ ( 66.3 g, 203.5 mmol) of a mixture of dimethylacetamide (100 ml) was refluxed at 170° C. for 12 h.

After cooling, the filtrate was filtered and the solvent of the filtrate was removed. Then, column purification was lowered to HX:MC = 4:1 to obtain compound 1-4. (10.1 g, 67%)

Preparation of compounds 1-5

9-(7-chlorodibenzo[b,d]furan-4-yl)-9H-carbazole (10.1, 27.4 mmol), bis(pinacolato)diboron in one neck round bottom flask (One neck rbf) (13.9 g, 54.9 mmol), XPhos (2.6 g, 5.48 mmol), potassium acetate (8 g, 82 mmol), Pd(dba) ₂ (1.57 g, 2.74 mmol) 1,4-dioxane (100 ml) mixture of 140 It was refluxed at ℃.

After concentration by extraction with dichloromethane, dichloromethane /MeOH treatment was performed to obtain compound 1-5 (13.4 g, over yield).

Preparation of compound 1

9-(7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d] in one neck round bottom flask (One neck rbf) ] furan-4-yl) -9H-carbazole (12.5 g, 27.2 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (8.74 g, 32.6 mmol), tetrakis ( Triphenylphosphine) palladium (0) (3.1 g, 2.72 mmol), potassium carbonate (7.5 g, 54.5 mmol), 1,4-dioxane/water (150 ml/30 ml) mixture was filtered at 60 ° C. , 4-dioxane, distilled water, and washed with MeOH to obtain compound 1 (11.2 g, over two step 71%).

In Preparation Example 1, the following compound C was synthesized in the same manner as in the preparation of compound 1, except that A and B of the following [Table 1] to [Table 8] were used as intermediates.

[ manufacturing example 2] Preparation of compound 137(D)

The target compound was prepared in the same manner as in the preparation of Compound 1, except that 1-bromo-2,4-difluorobenzene was used instead of 1-bromo-2,3-difluorobenzene in Preparation Example 1 137(D) was obtained (7.3 g, 45%).

In Preparation Example 2, the following compound D was synthesized in the same manner as in the preparation of compound 137, except that A and B of the following [Table 9] and [Table 10] were used as intermediates.

[ manufacturing example 3] Preparation of compound 189(E)

The target compound was prepared in the same manner as in the preparation of Compound 1, except that 2-bromo-1,4-difluorobenzene was used instead of 1-bromo-2,3-difluorobenzene in Preparation Example 1 189(E) was obtained (8.4 g, 47%).

In Preparation Example 3, the following compound E was synthesized in the same manner as in the preparation of compound 189, except that A and B of the following [Table 11] and [Table 12] were used as intermediates.

[ manufacturing example 4] Preparation of compound 241 (F)

In Preparation Example 1, the target compound 241 ( F) was obtained (6.4 g, 37%).

In Preparation Example 4, the following compound F was synthesized in the same manner as in the preparation of compound 241, except that A and B of the following [Table 13] and [Table 14] were used as intermediates.

Compounds 1 to 316 other than those described in Tables 1 to 14 were prepared in the same manner as described in Preparation Examples.

< manufacturing example 5> Synthesis of compound 2-6

1) Preparation of compound 2-6

5-phenyl-5,7-dihydroindolo[2,3-b]carbazole 6.0g (18.05mM), 4-bromo-1,1`;4',1"-terphenyl 6.7g (21.66) mM), Pd ₂ (dba) ₃ 0.824 g (0.90 mM), Sphos 0.74 g (1.80 mM), t-BuONa 3.47 g (36.10 mM), 1,4-oxane 60 mL, and refluxed for 24 hours. After completion, distilled water and dichloromethane (DCM, Dichloromethane) were added at room temperature for extraction, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction product was dissolved in DCB 100ml, filtered through silica gel, and purified with methanol. Recrystallization gave the target compound 2-6, 8.6 g (85%).

Using the intermediate A-1 of Table 15 below instead of 4-bromo-1,1`;4',1"-terphenyl in Preparation Example 5, 5-phenyl-5,7-dihydroindolo [2 ,3-b] The target compound A was synthesized in the same manner as in Preparation Example 5 using Intermediate B-1 of Table 15 below instead of carbazole.

< manufacturing example 6> compound 2- 79 Synthesis

1) Preparation of compound 2-79-2

2-chloro-7-phenyl-5,7-dihydroindolo [2,3-b] carbazole 7.0 g (19.08 mM), iodobenzene 4.28 g (20.99 mM), Pd ₂ (dba) ₃ 0.873 g (0.95 mM), (t-Bu) 3P 0.58 g (2.86 mM), t-BuONa 3.67 g (38.16 mM), and dissolved in 70 mL toluene, and refluxed for 4 hours. After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction product was purified by MC/HEX column and the solvent was removed using a rotary evaporator to obtain the target compound 2-79-2, 6.93 g (82%).

Intermediate C-3 of Table 16 was used instead of 2-chloro-7-phenyl-5,7-dihydroindolo [2,3-b] carbazole in the preparation of compound 2-79-2 of Preparation Example 6 The target compound C-2 was synthesized in the same manner as in the preparation of compound 2-79-2 of Preparation Example 6 except that.

2) Preparation of compound 2-79-1

2-chloro-5,7-diphenyl-5,7-dihydroindolo [2,3-b] carbazole 6.93 g (15.65 mM), bispinacolatodiborane 5.96 g (23.47 mM), Pd2 ( dba)3 1.43g (1.56mM), XPhos 1.49g (3.13mM), KOAc 4.61g (46.94mM), 1,4-oxane 70mL, and refluxed for 5 hours. After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction product was purified by MC/HEX column, and the filtrate was concentrated under reduced pressure to obtain 6.8 g (81%) of the target compound 2-79-1.

Intermediate C of Table 17 below instead of 2-chloro-5,7-diphenyl-5,7-dihydroindolo [2,3-b] carbazole in the preparation of compound 2-79-1 of Preparation Example 6 The target compound C-1 was synthesized in the same manner as in the preparation of compound 2-79-2 of Preparation Example 6 except that 2 was used.

3) Preparation of compound 2-79

5,7-diphenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborenyl)-5,7-dihydroindolo[2,3-b]carbazole 6.8 g (12.72 mM), 3-bromo-9-phenyl-carbazole 4.51 g (14.00 mM), Pd (PPh ₃ ) ₄ 0.74 g (0.64 mM), K ₂ CO ₃ 3.52 g (25.45 mM), toluene It was dissolved in 70 mL/ethanol 15 mL/water 15 mL and refluxed for 4 hours. After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction product was purified by MC/HEX column, and the filtrate was concentrated under reduced pressure to obtain 6.61 g (80%) of the target compound 2-79.

5,7-diphenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborenyl)-5,7-di in the preparation of compound 2-79 of Preparation Example 6 The compound of Preparation Example 6, except that Intermediate C-1 of Table 18 below was used instead of hydroindolo [2,3-b] carbazole, and Intermediate D-1 was used instead of 3-bromo-9-phenyl-carbazole The target compound C was synthesized in the same manner as in the preparation of 2-79.

A compound of Formula 1 and a compound of Formula 2 were prepared in the same manner as in Preparation Examples. Synthesis confirmation data of the compounds prepared above are as shown in [Table 19] and [Table 20] below.

compound FD-Mass compound FD-Mass One m/z = 564.63 (C39H24N4O=564.20) 2 m/z = 640.73 (C45H28N4O=640.23) 3 m/z = 640.73 (C45H28N4O=640.23) 4 m/z = 716.83 (C51H32N4O=717.26) 5 m/z = 716.83 (C51H32N4O=717.26) 6 m/z=729.82 (C51H31N5O=729.25) 7 m/z=729.82 (C51H31N5O=729.25) 8 m/z = 805.92 (C57H35N5O=805.28) 9 m/z = 730.81 (C51H30N4O2=730.81) 10 m/z = 680.79 (C48H32N4O=680.26) 11 m/z = 680.79 (C48H32N4O=680.26) 12 m/z = 680.79 (C48H32N4O=680.26) 13 m/z = 670.78 (C45H26N4OS=670.18) 14 m/z = 654.71 (C45H26N4O2=654.21) 15 m/z = 654.71 (C45H26N4O2=654.21) 16 m/z = 670.78 (C45H26N4OS=670.18) 17 m/z = 640.73 (C45H2N4O=640.23) 18 m/z = 716.83 (C51H32N4O=716.26) 19 m/z = 716.83 (C51H32N4O=716.26) 20 m/z = 792.92 (C57H36N4O=792.29) 21 m/z = 792.92 (C57H36N4O=792.29) 22 m/z = 640.73 (C45H2N4O=640.23) 23 m/z = 792.92 (C57H36N4O=792.29) 24 m/z = 792.92 (C57H36N4O=792.29) 25 m/z = 792.92 (C57H36N4O=792.29) 26 m/z = 728.84 (C52H32N4O=728.26) 27 m/z = 728.84 (C52H32N4O=728.26) 28 m/z = 804.93 (C58H36N4O=804.29) 29 m/z = 746.21 (C51H30N4OS=746.21) 30 m/z = 756.89 (C54H36N4O=756.29) 31 m/z = 756.89 (C54H36N4O=756.29) 32 m/z = 679.81 (C49H33N3O=679.26) 33 m/z = 746.88 (C51H30N4OS=746.21) 34 m/z = 730.81 (C51H30N4O2=730.24 35 m/z = 730.81 (C51H30N4O2=730.24 36 m/z = 669.79 (C46H27N3OS=669.19) 37 m/z = 640.73 (C45H28N4O=640.23) 38 m/z = 640.73 (C45H28N4O=640.23) 39 m/z = 716.83 (C51H32N4O=717.26) 40 m/z = 716.83 (C51H32N4O=717.26) 41 m/z = 716.83 (C51H43N4O=716.26) 42 m/z = 716.83 (C51H32N4O=717.26) 43 m/z = 715.84 (C52H33N3O=715.26) 44 m/z = 715.84 (C52H33N3O=715.26) 45 m/z = 640.73 (C45H28N4O=640.23 46 m/z = 716.83 (C51H32N4O=716.26) 47 m/z = 716.83 (C51H32N4O=716.26) 48 m/z = 792.92 (C57H36N4O=792.29) 49 m/z = 756.89 (C54H36N4O=756.29) 50 m/z = 716.83 (C51H32N4O=716.26) 51 m/z = 716.83 (C51H32N4O=716.26) 52 m/z = 716.83 (C51H32N4O=716.26) 53 m/z = 792.92 (C57H36N4O=792.29) 54 m/z = 792.92 (C57H36N4O=792.29) 55 m/z = 601.69 (C43H27N3O=601.69) 56 m/z = 601.69 (C43H27N3O=601.69) 57 m/z = 677.79 (C49H31N3O=677.25) 58 m/z = 677.79 (C49H31N3O=677.25) 59 m/z = 677.79 (C49H31N3O=677.25) 60 m/z = 677.79 (C49H31N3O=677.25) 61 m/z = 753.89 (C55H35N3O=753.28) 62 m/z = 753.89 (C55H35N3O=753.28) 63 m/z = 753.89 (C55H35N3O=753.28) 64 m/z = 753.89 (C55H35N3O=753.28) 65 m/z = 717.85 (C52H35N3O=717.28) 66 m/z = 717.85 (C52H35N3O=717.28) 67 m/z = 707.84 (C49H29N3OS=707.20) 68 m/z = 691.77 (C49H29N3O2=691.23) 69 m/z = 613.70 (C44H27N3O=613.22) 70 m/z = 689.80 (C50H31N3O=689.25) 71 m/z = 689.80 (C50H31N3O=689.25) 72 m/z = 689.80 (C50H31N3O=689.25) 73 m/z = 765.90 (C56H35N3O=765.28) 74 m/z = 765.90 (C56H35N3O=765.28) 75 m/z = 729.86 (C53H35N3O=729.28) 76 m/z = 719.20 (C50H29N3OS=719.20) 77 m/z = 537.61 (C38H23N3O=537.18) 78 m/z = 613.70 (C44H27N3O=613.22) 79 m/z = 613.70 (C44H27N3O=613.22) 80 m/z = 613.70 (C44H27N3O=613.22) 81 m/z = 689.80 (C50H31N3O=689.25) 82 m/z = 689.80 (C50H31N3O=689.25) 83 m/z = 702.80 (C50H30N4O=702.24) 84 m/z = 702.80 (C50H30N4O=702.24) 85 m/z = 537.61 (C38H23N3O=537.18) 86 m/z = 613.70 (C44H27N3O=613.22) 87 m/z = 613.70 (C44H27N3O=613.22) 88 m/z = 613.70 (C44H27N3O=613.22) 89 m/z = 689.80 (C50H31N3O=689.25) 90 m/z = 689.80 (C50H31N3O=689.25) 91 m/z = 778.90 (C56H34N4O=78.27) 92 m/z = 703.78 (C50H29N3O2=703.23) 93 m/z = 536.62 (C39H24N2O=536.19) 94 m/z = 612.72 (C45H28N2O=612.22) 95 m/z = 612.72 (C45H28N2O=612.22) 96 m/z = 612.72 (C45H28N2O=612.22) 97 m/z = 688.81 (C51H32N2O=688.25) 98 m/z = 688.81 (C51H32N2O=688.25) 99 m/z = 652.78 (C48H32N2O=652.25) 100 m/z = 652.78 (C48H32N2O=652.25) 101 m/z = 536.62 (C39H24N2O=536.19) 102 m/z = 612.72 (C45H28N2O=612.22) 103 m/z = 612.72 (C45H28N2O=612.22) 104 m/z = 612.72 (C45H28N2O=612.22) 105 m/z = 688.81 (C51H32N2O=688.25) 106 m/z = 688.81 (C51H32N2O=688.25) 107 m/z = 642.77 (C45H26N2OS=642.18) 108 m/z = 626.70 (C45H27N2O2=626.20) 109 m/z = 587.67 (C42H25N3O=587.20) 110 m/z = 663.76 (C48H29N3O=663.23) 111 m/z = 663.76 (C48H29N3O=663.23) 112 m/z = 663.76 (C48H29N3O=663.23) 113 m/z = 739.86 (C54H33N3O=739.26) 114 m/z = 739.86 (C54H33N3O=739.26) 115 m/z = 677.75 (C48H27N3O2=677.21) 116 m/z=693.81 (C48H27NOS=693.19) 117 m/z = 563.65 (C40H25N3O=563.20) 118 m/z = 639.73 (C46H29N3O=639.23) 119 m/z = 639.73 (C46H29N3O=639.23) 120 m/z = 715.84 (C52H33N3O=715.26) 121 m/z = 715.84 (C52H33N3O=715.26) 122 m/z = 715.84 (C52H33N3O=715.26) 123 m/z = 639.74 (C46H29N3O=639.23) 124 m/z = 715.84 (C52H33N3O=715.26) 125 m/z = 664.75 (C47H28N4O=664.23) 126 m/z = 740.85 (C53H32N4O=740.26) 127 m/z = 740.85 (C53H32N4O=740.26) 128 m/z = 740.85 (C53H32N4O=740.26) 129 m/z = 816.94 (C59H36N4O=816.29) 130 m/z = 816.94 (C59H36N4O=816.29) 131 m/z = 829.94 (C59H35N5O=829.28) 132 m/z = 829.94 (C59H35N5O=829.28) 133 m/z=729.82 (C51H31N5O=729.25) 134 m/z = 805.92 (C57H35N5O=805.28) 135 m/z = 702.80 (C50H30N4O=702.24) 136 m/z = 766.27 (C55H34N4O=766.27) 137 m/z = 564.63 (C39H24N4O=564.20) 138 m/z = 640.73 (C45H28N4O=640.23) 139 m/z = 640.73 (C45H28N4O=640.23) 140 m/z = 716.83 (C51H32N4O=717.26) 141 m/z = 716.83 (C51H32N4O=717.26) 142 m/z=729.82 (C51H31N5O=729.25) 143 m/z=729.82 (C51H31N5O=729.25) 144 m/z = 805.92 (C57H35N5O=805.28) 145 m/z = 730.81 (C51H30N4O2=730.81) 146 m/z = 680.79 (C48H32N4O=680.26) 147 m/z = 680.79 (C48H32N4O=680.26) 148 m/z = 680.79 (C48H32N4O=680.26) 149 m/z = 670.78 (C45H26N4OS=670.18) 150 m/z = 654.71 (C45H26N4O2=654.21) 151 m/z = 654.71 (C45H26N4O2=654.21) 152 m/z = 670.78 (C45H26N4OS=670.18) 153 m/z = 640.73 (C45H2N4O=640.23) 154 m/z = 716.83 (C51H32N4O=716.26) 155 m/z = 716.83 (C51H32N4O=716.26) 156 m/z = 792.92 (C57H36N4O=792.29) 157 m/z = 792.92 (C57H36N4O=792.29) 158 m/z = 640.73 (C45H2N4O=640.23) 159 m/z = 792.92 (C57H36N4O=792.29) 160 m/z = 792.92 (C57H36N4O=792.29) 161 m/z = 792.92 (C57H36N4O=792.29) 162 m/z = 728.84 (C52H32N4O=728.26) 163 m/z = 728.84 (C52H32N4O=728.26) 164 m/z = 804.93 (C58H36N4O=804.29) 165 m/z = 746.21 (C51H30N4OS=746.21) 166 m/z = 756.89 (C54H36N4O=756.29) 167 m/z = 756.89 (C54H36N4O=756.29) 168 m/z = 679.81 (C49H33N3O=679.26) 169 m/z = 746.88 (C51H30N4OS=746.21) 170 m/z = 730.81 (C51H30N4O2=730.24 171 m/z = 730.81 (C51H30N4O2=730.24 172 m/z = 669.79 (C46H27N3OS=669.19) 173 m/z = 640.73 (C45H28N4O=640.23) 174 m/z = 640.73 (C45H28N4O=640.23) 175 m/z = 716.83 (C51H32N4O=717.26) 176 m/z = 716.83 (C51H32N4O=717.26) 177 m/z = 716.83 (C51H43N4O=716.26) 178 m/z = 716.83 (C51H32N4O=717.26) 179 m/z = 715.84 (C52H33N3O=715.26) 180 m/z = 715.84 (C52H33N3O=715.26) 181 m/z = 664.75 (C47H28N4O=664.23) 182 m/z = 740.85 (C53H32N4O=740.26) 183 m/z = 740.85 (C53H32N4O=740.26) 184 m/z = 740.85 (C53H32N4O=740.26) 185 m/z = 816.94 (C59H36N4O=816.29) 186 m/z = 816.94 (C59H36N4O=816.29) 187 m/z = 829.94 (C59H35N5O=829.28) 188 m/z = 829.94 (C59H35N5O=829.28) 189 m/z = 564.63 (C39H24N4O=564.20) 190 m/z = 640.73 (C45H28N4O=640.23) 191 m/z = 640.73 (C45H28N4O=640.23) 192 m/z = 716.83 (C51H32N4O=717.26) 193 m/z = 716.83 (C51H32N4O=717.26) 194 m/z=729.82 (C51H31N5O=729.25) 195 m/z=729.82 (C51H31N5O=729.25) 196 m/z = 805.92 (C57H35N5O=805.28) 197 m/z = 730.81 (C51H30N4O2=730.81) 198 m/z = 680.79 (C48H32N4O=680.26) 199 m/z = 680.79 (C48H32N4O=680.26) 200 m/z = 680.79 (C48H32N4O=680.26) 201 m/z = 670.78 (C45H26N4OS=670.18) 202 m/z = 654.71 (C45H26N4O2=654.21) 203 m/z = 654.71 (C45H26N4O2=654.21) 204 m/z = 670.78 (C45H26N4OS=670.18) 205 m/z = 640.73 (C45H2N4O=640.23) 206 m/z = 716.83 (C51H32N4O=716.26) 207 m/z = 716.83 (C51H32N4O=716.26) 208 m/z = 792.92 (C57H36N4O=792.29) 209 m/z = 792.92 (C57H36N4O=792.29) 210 m/z = 640.73 (C45H2N4O=640.23) 211 m/z = 792.92 (C57H36N4O=792.29) 212 m/z = 792.92 (C57H36N4O=792.29) 213 m/z = 792.92 (C57H36N4O=792.29) 214 m/z = 728.84 (C52H32N4O=728.26) 215 m/z = 728.84 (C52H32N4O=728.26) 216 m/z = 804.93 (C58H36N4O=804.29) 217 m/z = 746.21 (C51H30N4OS=746.21) 218 m/z = 756.89 (C54H36N4O=756.29) 219 m/z = 756.89 (C54H36N4O=756.29) 220 m/z = 679.81 (C49H33N3O=679.26) 221 m/z = 746.88 (C51H30N4OS=746.21) 222 m/z = 730.81 (C51H30N4O2=730.24 223 m/z = 730.81 (C51H30N4O2=730.24 224 m/z = 669.79 (C46H27N3OS=669.19) 225 m/z = 640.73 (C45H28N4O=640.23) 226 m/z = 640.73 (C45H28N4O=640.23) 227 m/z = 716.83 (C51H32N4O=717.26) 228 m/z = 716.83 (C51H32N4O=717.26) 229 m/z = 716.83 (C51H43N4O=716.26) 230 m/z = 716.83 (C51H32N4O=717.26) 231 m/z = 715.84 (C52H33N3O=715.26) 232 m/z = 715.84 (C52H33N3O=715.26) 233 m/z = 664.75 (C47H28N4O=664.23) 234 m/z = 740.85 (C53H32N4O=740.26) 235 m/z = 740.85 (C53H32N4O=740.26) 236 m/z = 740.85 (C53H32N4O=740.26) 237 m/z = 816.94 (C59H36N4O=816.29) 238 m/z = 816.94 (C59H36N4O=816.29) 239 m/z = 829.94 (C59H35N5O=829.28) 240 m/z = 829.94 (C59H35N5O=829.28) 241 m/z = 564.63 (C39H24N4O=564.20) 242 m/z = 640.73 (C45H28N4O=640.23) 243 m/z = 640.73 (C45H28N4O=640.23) 244 m/z = 716.83 (C51H32N4O=717.26) 245 m/z = 716.83 (C51H32N4O=717.26) 246 m/z=729.82 (C51H31N5O=729.25) 247 m/z=729.82 (C51H31N5O=729.25) 248 m/z = 805.92 (C57H35N5O=805.28) 249 m/z = 730.81 (C51H30N4O2=730.81) 250 m/z = 680.79 (C48H32N4O=680.26) 251 m/z = 680.79 (C48H32N4O=680.26) 252 m/z = 680.79 (C48H32N4O=680.26) 253 m/z = 670.78 (C45H26N4OS=670.18) 254 m/z = 654.71 (C45H26N4O2=654.21) 255 m/z = 654.71 (C45H26N4O2=654.21) 256 m/z = 670.78 (C45H26N4OS=670.18) 257 m/z = 640.73 (C45H2N4O=640.23) 258 m/z = 716.83 (C51H32N4O=716.26) 259 m/z = 716.83 (C51H32N4O=716.26) 260 m/z = 792.92 (C57H36N4O=792.29) 261 m/z = 792.92 (C57H36N4O=792.29) 262 m/z = 640.73 (C45H2N4O=640.23) 263 m/z = 792.92 (C57H36N4O=792.29) 264 m/z = 792.92 (C57H36N4O=792.29) 265 m/z = 792.92 (C57H36N4O=792.29) 266 m/z = 728.84 (C52H32N4O=728.26) 267 m/z = 728.84 (C52H32N4O=728.26) 268 m/z = 804.93 (C58H36N4O=804.29) 269 m/z = 746.21 (C51H30N4OS=746.21) 270 m/z = 756.89 (C54H36N4O=756.29) 271 m/z = 756.89 (C54H36N4O=756.29) 272 m/z = 679.81 (C49H33N3O=679.26) 273 m/z = 746.88 (C51H30N4OS=746.21) 274 m/z = 730.81 (C51H30N4O2=730.24 275 m/z = 730.81 (C51H30N4O2=730.24 276 m/z = 669.79 (C46H27N3OS=669.19) 277 m/z = 640.73 (C45H28N4O=640.23) 278 m/z = 640.73 (C45H28N4O=640.23) 279 m/z = 716.83 (C51H32N4O=717.26) 280 m/z = 716.83 (C51H32N4O=717.26) 281 m/z = 716.83 (C51H43N4O=716.26) 282 m/z = 716.83 (C51H32N4O=717.26) 283 m/z = 715.84 (C52H33N3O=715.26) 284 m/z = 715.84 (C52H33N3O=715.26) 285 m/z = 664.75 (C47H28N4O=664.23) 286 m/z = 740.85 (C53H32N4O=740.26) 287 m/z = 740.85 (C53H32N4O=740.26) 288 m/z = 740.85 (C53H32N4O=740.26) 289 m/z = 816.94 (C59H36N4O=816.29) 290 m/z = 816.94 (C59H36N4O=816.29) 291 m/z = 829.94 (C59H35N5O=829.28) 292 m/z = 829.94 (C59H35N5O=829.28) 293 m/z = 716.83 (C51H32N4O=716.26) 294 m/z=654.71 (C45H26N4O2=654.21) 295 m/z=730.81 (C51H30N4O2=730.24) 296 m/z=654.71 (C45H26N4O2=654.21) 297 m/z=730.81 (C51H30N4O2=730.24) 298 m/z=730.81 (C51H30N4O2=730.24) 299 m/z = 716.83 (C51H32N4O=716.26) 300 m/z=654.71 (C45H26N4O2=654.21) 301 m/z=730.81 (C51H30N4O2=730.24) 302 m/z=730.81 (C51H30N4O2=730.24) 303 m/z=746.88 (C51H30N4OS=741.21) 304 m/z=756.89 (C54H36N4O=756.29) 305 m/z = 716.83 (C51H32N4O=716.26) 306 m/z=654.71 (C45H26N4O2=654.21) 307 m/z=730.81 (C51H30N4O2=730.24) 308 m/z=746.88 (C51H30N4OS=741.21) 309 m/z=730.81 (C51H30N4O2=730.24) 310 m/z=730.81 (C51H30N4O2=730.24) 311 m/z=756.89 (C54H36N4O=756.29) 312 m/z = 716.83 (C51H32N4O=716.26) 313 m/z=730.81 (C51H30N4O2=730.24) 314 m/z=654.71 (C45H26N4O2=654.21) 315 m/z=730.81 (C51H30N4O2=730.24) 316 m/z=730.81 (C51H30N4O2=730.24) 2-1 m/z = 408.16 (C30H20N2 = 408.50) 2-2 m/z = 484.19 (C36H24N2=484.60) 2-3 m/z = 484.19 (C36H24N2=484.60) 2-4 m/z = 458.18 (C34H22N2 = 458.56) 2-5 m/z = 458.18 (C34H22N2 = 458.56) 2-6 m/z = 560.23 (C42H28N2 = 560.70) 2-7 m/z = 560.23 (C42H28N2 = 560.70) 2-8 m/z= 558.21 (C42H26N2=558.68) 2-9 m/z = 560.23 (C42H28N2 = 560.70) 2-10 m/z= 666.25 (C48H34N2Si=666.90) 2-11 m/z= 524.23 (C39H28N2=524.67) 2-12 m/z= 524.23 (C39H28N2=524.67) 2-13 m/z= 648.26 (C49H32N2=648.26) 2-14 m/z = 498.17 (C36H22N2O=498.58) 2-15 m/z = 498.17 (C36H22N2O=498.58) 2-16 m/z= 514.15 (C36H22N2S=514.65) 2-17 m/z= 514.15 (C36H22N2S=514.65) 2-18 m/z= 573,22 (C4H27N3=573.70) 2-19 m/z = 560.23 (C42H28N2 = 560.70) 2-20 m/z = 560.23 (C42H28N2 = 560.70) 2-21 m/z= 712.29 (C54H36N2=712.90) 2-22 m/z= 712.29 (C54H36N2=712.90) 2-23 m/z= 708.26 (C54H32N2=708.86) 2-24 m/z = 588.18 (C42H24N2O=588.67) 2-25 m/z = 588.18 (C42H24N2O=588.67) 2-26 m/z= 620.14 (C42H24N2S2=620.79) 2-27 m/z= 620.14 (C42H24N2S2=620.79) 2-28 m/z= 738.28 (C54H34N4=738.89) 2-29 m/z = 408.16 (C30H20N2 = 408.50) 2-30 m/z = 560.23 (C42H28N2 = 560.70) 2-31 m/z = 560.23 (C42H28N2 = 560.70) 2-32 m/z= 712.29 (C54H36N2=712.90) 2-33 m/z= 712.29 (C54H36N2=712.90) 2-34 m/z= 708.26 (C54H32N2=708.86) 2-35 m/z= 640.29 (C48H36N2=640.83) 2-36 m/z = 588.18 (C42H24N2O=588.67) 2-37 m/z = 588.18 (C42H24N2O=588.67) 2-38 m/z= 620.14 (C42H24N2S2=620.79) 2-39 m/z= 620.14 (C42H24N2S2=620.79) 2-40 m/z= 738.28 (C54H34N4=738.89) 2-41 m/z = 408.16 (C30H20N2 = 408.50) 2-42 m/z = 560.23 (C42H28N2 = 560.70) 2-43 m/z = 560.23 (C42H28N2 = 560.70) 2-44 m/z= 712.29 (C54H36N2=712.90) 2-45 m/z= 712.29 (C54H36N2=712.90) 2-46 m/z= 708.26 (C54H32N2=708.86) 2-47 m/z= 640.29 (C48H36N2=640.83) 2-48 m/z = 588.18 (C42H24N2O=588.67) 2-49 m/z = 588.18 (C42H24N2O=588.67) 2-50 m/z= 620.14 (C42H24N2S2=620.79) 2-51 m/z= 620.14 (C42H24N2S2=620.79) 2-52 m/z= 738.28 (C54H34N4=738.89) 2-53 m/z = 408.16 (C30H20N2 = 408.50) 2-54 m/z = 560.23 (C42H28N2 = 560.70) 2-55 m/z = 560.23 (C42H28N2 = 560.70) 2-56 m/z= 712.29 (C54H36N2=712.90) 2-57 m/z= 712.29 (C54H36N2=712.90) 2-58 m/z= 708.26 (C54H32N2=708.86) 2-59 m/z= 640.29 (C48H36N2=640.83) 2-60 m/z = 588.18 (C42H24N2O=588.67) 2-61 m/z = 588.18 (C42H24N2O=588.67) 2-62 m/z= 620.14 (C42H24N2S2=620.79) 2-63 m/z= 620.14 (C42H24N2S2=620.79) 2-64 m/z= 738.28 (C54H34N4=738.89) 2-65 m/z = 408.16 (C30H20N2 = 408.50) 2-66 m/z = 560.23 (C42H28N2 = 560.70) 2-67 m/z = 560.23 (C42H28N2 = 560.70) 2-68 m/z= 712.29 (C54H36N2=712.90) 2-69 m/z= 712.29 (C54H36N2=712.90) 2-70 m/z= 708.26 (C54H32N2=708.86) 2-71 m/z= 640.29 (C48H36N2=640.83) 2-72 m/z = 588.18 (C42H24N2O=588.67) 2-73 m/z = 588.18 (C42H24N2O=588.67) 2-74 m/z= 620.14 (C42H24N2S2=620.79) 2-75 m/z= 620.14 (C42H24N2S2=620.79) 2-76 m/z= 738.28 (C54H34N4=738.89) 2-77 m/z = 484.19 (C36H24N2=484.60) 2-78 m/z= 634.24 (C48H30N2=634.78) 2-79 m/z= 649.25 (C48H31N3=649.80) 2-80 m/z= 725.28 (C54H35N3=725.89) 2-81 m/z= 725.28 (C54H35N3=725.89) 2-82 m/z= 649.25 (C48H31N3=649.80) 2-83 m/z= 649.25 (C48H31N3=649.80) 2-84 m/z= 649.25 (C48H31N3=649.80) 2-85 m/z = 574.20 (C42H26N2O=574.68) 2-86 m/z = 574.20 (C42H26N2O=574.68) 2-87 m/z = 590.18 (C42H26N2S=590.74) 2-88 m/z = 590.18 (C42H26N2S=590.74) 2-89 m/z= 649.25 (C48H31N3=649.80) 2-90 m/z= 725.28 (C54H35N3=725.89) 2-91 m/z= 725.28 (C54H35N3=725.89) 2-92 m/z= 649.25 (C48H31N3=649.80) 2-93 m/z = 574.20 (C42H26N2O=574.68) 2-94 m/z = 574.20 (C42H26N2O=574.68) 2-95 m/z = 590.18 (C42H26N2S=590.74) 2-96 m/z = 590.18 (C42H26N2S=590.74) 2-97 m/z= 649.25 (C48H31N3=649.80) 2-98 m/z= 725.28 (C54H35N3=725.89) 2-99 m/z= 725.28 (C54H35N3=725.89) 2-100 m/z= 649.25 (C48H31N3=649.80) 2-101 m/z = 574.20 (C42H26N2O=574.68) 2-102 m/z = 574.20 (C42H26N2O=574.68) 2-103 m/z = 590.18 (C42H26N2S=590.74) 2-104 m/z = 590.18 (C42H26N2S=590.74) 2-105 m/z= 649.25 (C48H31N3=649.80) 2-106 m/z= 725.28 (C54H35N3=725.89) 2-107 m/z= 725.28 (C54H35N3=725.89) 2-108 m/z= 649.25 (C48H31N3=649.80) 2-109 m/z = 574.20 (C42H26N2O=574.68) 2-110 m/z = 574.20 (C42H26N2O=574.68) 2-111 m/z = 590.18 (C42H26N2S=590.74) 2-112 m/z = 590.18 (C42H26N2S=590.74) 2-113 m/z= 649.25 (C48H31N3=649.80) 2-114 m/z= 725.28 (C54H35N3=725.89) 2-115 m/z= 725.28 (C54H35N3=725.89) 2-116 m/z= 649.25 (C48H31N3=649.80) 2-117 m/z = 574.20 (C42H26N2O=574.68) 2-118 m/z = 574.20 (C42H26N2O=574.68) 2-119 m/z = 590.18 (C42H26N2S=590.74) 2-120 m/z = 590.18 (C42H26N2S=590.74) 2-121 m/z= 425.12 (C30H19NS=425.55) 2-122 m/z= 575.17 (C42H25NS=515.73) 2-123 m/z = 590.18 (C42H26N2S=590.74) 2-124 m/z= 515.13 (C36H21NOS=515.63) 2-125 m/z= 531.11 (C36H21NS2=531.69) 2-126 m/z= 666.21 (C48H30N2S=666.84) 2-127 m/z= 666.21 (C48H30N2S=666.84) 2-128 m/z= 666.21 (C48H30N2S=666.84) 2-129 m/z= 742.24 (C54H34N2S=742.94) 2-130 m/z= 740.23 (54H32N2S=740.92) 2-131 m/z = 574.20 (C42H25N2O=574.68) 2-132 m/z= 600.26 (C45H32N2=600.76) 2-133 m/z = 590.18 (C42H26N2S=590.74) 2-134 m/z = 574.20 (C42H25N2O=574.68) 2-135 m/z= 600.26 (C45H32N2=600.76) 2-136 m/z = 590.18 (C42H26N2S=590.74) 2-137 m/z = 574.20 (C42H25N2O=574.68) 2-138 m/z= 600.26 (C45H32N2=600.76) 2-139 m/z = 590.18 (C42H26N2S=590.74) 2-140 m/z = 574.20 (C42H25N2O=574.68) 2-141 m/z= 600.26 (C45H32N2=600.76) 2-142 m/z = 590.18 (C42H26N2S=590.74) 2-143 m/z = 574.20 (C42H25N2O=574.68) 2-144 m/z= 600.26 (C45H32N2=600.76) 2-145 m/z= 425.12 (C30H19NS=425.55) 2-146 m/z= 575.17 (C42H25NS=515.73) 2-147 m/z = 590.18 (C42H26N2S=590.74) 2-148 m/z= 515.13 (C36H21NOS=515.63) 2-149 m/z= 531.11 (C36H21NS2=531.69) 2-150 m/z= 666.21 (C48H30N2S=666.84) 2-151 m/z= 666.21 (C48H30N2S=666.84) 2-152 m/z= 666.21 (C48H30N2S=666.84) 2-153 m/z= 742.24 (C54H34N2S=742.94) 2-154 m/z= 740.23 (54H32N2S=740.92) 2-155 m/z = 574.20 (C42H25N2O=574.68) 2-156 m/z= 600.26 (C45H32N2=600.76) 2-157 m/z = 590.18 (C42H26N2S=590.74) 2-158 m/z = 574.20 (C42H25N2O=574.68) 2-159 m/z= 600.26 (C45H32N2=600.76) 2-160 m/z = 590.18 (C42H26N2S=590.74) 2-161 m/z = 574.20 (C42H25N2O=574.68) 2-162 m/z= 600.26 (C45H32N2=600.76) 2-163 m/z = 590.18 (C42H26N2S=590.74) 2-164 m/z = 574.20 (C42H25N2O=574.68) 2-165 m/z= 600.26 (C45H32N2=600.76) 2-166 m/z = 590.18 (C42H26N2S=590.74) 2-167 m/z = 574.20 (C42H25N2O=574.68) 2-168 m/z= 600.26 (C45H32N2=600.76)

compound ¹ H NMR (CDCl ₃ , 200 Mz) One δ = 8.55 (1H,d), 8.28 (4H, d), 8.12 (1H,d), 7.95 to 7.89 (3H, m)6, 7.75 (1H, d), 7.64 to 7.63 (2H, d), 7.51 ~7.32 (12H, m) 2 δ = 8.55 (1H, d), 8.28 (4H, d), 8.18 (1H, d), 7.95 to 7.89 (3H, m)7.79 to 7.75 (2H, q), 7.64 to 7.62 (2H, d), 7.52 ~7.32 (15H, m) 3 δ = 8.55 (1H, d), 8.28 (4H, d), 7.95 to 7.87 (4H, m), 7.77 to 7.89 (3H, m), 7.75 (1H, d), 7.63 to 7.32 (26H, m) 5 δ = 8.28 (4H, m), 8.18 (1H, d), 8.00 to 7.87 (4H, m), 7.77 to 7.64 (5H, m), 7.52 to 7.32 (18H, m) 7 δ = 8.55 (1H, d), 8.28 (4H, d), 8.12 (1H, d), 7.95 to 7.89 (3H, m), 7.75 (1H, d), 7.63 to 7.32 (26H, m) 20 δ = 8.49 (1H, d), 8.28 to 8.14 (4H, m), 8.10 (1H, d), 7.95 (1H, d), 7.89 (1H, d), 7.79 to 7.70 (3H, m), 7.62 to 7.32 (25H, m) 30 δ = 8.39 (1H, s), 8.28 to 8.24 (3H, m), 8.12 to 8.09 (2H, d), 7.95 (1H, d), 7.89 (1H, d), 7.75 to 7.24 (22H, m), 1.72 (6H, s) 126 δ = 9.09 (2H, s), 8.49 (2H, d), 8.55 (1H, d), 8.18 (1H, d), 8.00 to 7.92 (9H, m), 7.79 to 7.75 (2H, m), 7.59 to 7.32 (15H, m) 137 δ = 8.55 (1H, d), 8.25 (4H, d), 8.12 (2H, d), 7.95 to 7.89 (3H., m), 7.75 to 7.73 (2H, m), 7.64 to 7.63 (2H, m) , 7.51~7.25 (1H, m) 138 δ = 8.57 (1H, d), 8.28 (4H, d), 8.12 (1H, d), 7.95 to 7.89 (3H, m), 7.79 to 7.73 (3H, m), 7.64 to 7.62 (2H, d), 7.51~7.25 (14H, m) 139 δ = 8.55 (1H, d), 8.28 (4H, d), 7.95 to 7.87 (4H, m), 7.77 to 7.73 (5H, m), 7.52 to 7.25 (14H, m) 141 δ = 8.27 (4H, d), 8.17 (1H, d), 8.00 to 7.87 (4H, m), 7.77 to 7.73 (6H, m), 7.52 to 7.41 (17H, m) 173 δ = 8.55 (1H, d), 8.28 (4H, d), 8.12 (1H, d), 7.95 to 7.85 (5H, m), 7.75 to 7.73 (2H, d), 7.64 to 7.63 (2H, d), 7.51~7.25 (13H, m) 174 δ = 8.55 (1H, d), 8.28 (4H, d), 8.12 (1H, d), 7.95 to 7.89 (3H, m), 7.70 to 7.25 (18H, m) 189 δ = 8.56 (1H, d), 8.28 (4H, d), 8.12 (1H, d), 7.95 to 7.94 (2H, m), 7.80 to 7.75 (2H, m), 7.66 to 7.63 (3H, m), 7.51~7.25 (11H, m) 190 δ = 8.55 (1H, d), 8.28 (4H, d), 8.18 (1H, d), 7.95 to 7.94 (2H, m), 7.66 to 7.62 (3H, m), 7.52 to 7.25 (14H, m) 242 δ = 8.55 (1H, d), 8.27 to 8.26 (4H, d), 8.18 (1H, d), 7.95 to 7.94 (2H, m), 7.79 to 7.75 (2H, m), 7.66 to 7.62 (3H, m) ), 7.52~7.25 (15H, m) 245 δ = 8.28(4H, d), 8.17 (1H, d), 8.00 to 7.95 (2H, q), 7.87 (1H, d), 7.87 (1H, d), 7.77 to 7.64 (6H, m), 7.51 to 7.38 (18H, m) 301 δ = 8.28(2H,d), 8.18~8.12 (2H, q), 8.00~7.73 (9H, m), 7.66~7.63 (3H, m), 7.52~7.29 (14H, m) 305 δ = 8.55 (1H, d), 8.24 (2H, d), 8.12 (1H, d), 7.95 to 7.94 (2H, d), 7.80 to 7.25 (26H, m) 314 δ = 8.55(1H, d), 8.28 (2H, d), 8.12(1H, d), 7.94 to 7.81 (6H, m), 7.66 to 7.63 (4H, m), 7.51 to 7.25 (12H, m) 2-6 δ = 8.55 (1H, d), 8.19 (1H, d), 7.94-7.91 (5H, m), 7.75 (2H, d), 7.62-7.35 (13H, m), 7.25-7.16 (6H, m) 2-19 δ = 8.55 (1H, d), 8.19 (1H, d), 7.94 to 7.91 (9H, m), 7.75 (4H, d) 7.58-7.35 (11H, m) 7.20-7.16 (2H, m) 2-22 δ = 8.55 (1H, d), 8.19 (1H, d), 7.94-7.91 (11H, m), 7.75-7.73 (6H, m) 7.61-7.35 (15H, m) 7.20-7.16 (2H, m) 2-25 δ = 8.55 (1H, d), 8.19 (1H, d), 7.98~7.94 (3H, m), 7.74 (2H, d) 7.61-7.50 (7H, m), 7.40-7.31 (8H, m), 7.20 -7.16 (2H, m) 2-30 δ = 8.55 (1H, d), 8.21-8.19 (3H, m), 7.94 (1H, d), 7.75-7.35 (21H, m), 7.20-7.16 (2H, m) 2-40 δ = 8.55 (3H, d), 8.19 (1H, d), 7.94 (3H, d), 7.72-7.47 (18H, m), 7.38-7.35 (5H, m), 7.20-7.16 (4H, m) 2-70 δ = 9.08-9.06 (4H, d), 8.55 (1H, d), 8.33-8.19 (5H, m), 8.00-7.94 (5H, m), 7.70-7.52 (14H, m), 7.35 (1H, t) ), 7.20-7.16 (2H, m) 2-78 δ = 9.27 (1H, s), 8.79 (1H, d), 8.37-8.30 (5H, m), 8.19-8.13 (2H, d), 7.89 (1H, s), 7.70-7.50 (18H, m), 7.40 (1H, s), 7.20 (1H, t) 2-79 δ = 8.30 (2H, d), 8.19-8.13 (4H, m), 7.89 (2H, s), 7.62-7.50 (20H, m), 7.40 (1H, s), 7.20 (2H, t) 2-113 δ = 8.55 (1H, d), 8.39 (2H, d), 8.19-8.12 (4H, m), 7.94 (1H, d), 7.89 (2H, s), 7.62-7.50 (17H, m), 7.35 ( 1H, t), 7.20-7.16 (3H, m) 2-123 δ = 8.45 (1H, d), 8.30 (2H, d), 8.19-8.13 (3H, m), 7,93-7.89 (4H, m), 7.78 (1H, s), 7.62-7.49 (13H, m) ), 7.20 (1H, t) 2-142 δ = 8.45 (1H, d), 8.30 (2H, d), 8.19-8.08 (4H, m), 7.93 (1H, d), 7.89 (2H, s), 7.80 (1H, d), 7.62-7.49 ( 14H, m), 7.20 (1H, t)

< Experimental example 1> Fabrication of organic light emitting device

A glass substrate coated with a thin film of indium tin oxide (ITO) to a thickness of 1,500 Å was washed with distilled water ultrasonically. After washing with distilled water, ultrasonic washing was performed with a solvent such as acetone, methanol, isopropyl alcohol, etc., dried, and then treated with UVO (ultravioletozone) for 5 minutes using UV in a UV (ultraviolet) washer. After transferring the substrate to a plasma cleaner (PT), plasma treatment was performed to remove the ITO work function and residual film in a vacuum state, and the substrate was transferred to a thermal deposition equipment for organic deposition.

The hole injection layer 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine) as a common layer on the ITO transparent electrode (anode) and the hole transport layer NPB (N,N'-Di ( 1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) was formed.

A light emitting layer was deposited thereon by thermal vacuum deposition as follows. As a host, as shown in Table 22 below, 400 Å of one compound described in Formula 1 and one compound described in Formula 2 were deposited as a host as 400 Å, and a green phosphorescent dopant was deposited by _{doping Ir(ppy) 3} with 7%. After that, 60Å of BCP was deposited as a hole blocking layer, and Alq _{3 as an electron transport layer thereon} was deposited at 200 Å. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited to a thickness of 1,200 Å on the electron injection layer to form a cathode. An electroluminescent device was manufactured.

Meanwhile, all organic compounds required for manufacturing OLED devices ^{were vacuum sublimated and purified under 10 -6} to 10 ^-8 torr for each material, respectively, and used for OLED manufacturing.

< Experimental example 2> Fabrication of organic light emitting device

A glass substrate coated with a thin film of ITO to a thickness of 1,500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning was performed with a solvent such as acetone, methanol, isopropyl alcohol, etc., dried, and UVO-treated for 5 minutes using UV in a UV washer. After transferring the substrate to a plasma cleaner (PT), plasma treatment was performed to remove the ITO work function and residual film in a vacuum state, and the substrate was transferred to a thermal deposition equipment for organic deposition.

The hole injection layer 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine) as a common layer on the ITO transparent electrode (anode) and the hole transport layer NPB (N,N'-Di ( 1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) was formed.

A light emitting layer was deposited thereon by thermal vacuum deposition as follows. As a host, as shown in Table 23, one type of compound described in Formula 1 and one compound described in Formula 2 were pre-mixed as a host, and then 400 Å were deposited in one park, and a green phosphorescent dopant was deposited by _{doping Ir(ppy) 3} with 7%. . After that, 60Å of BCP was deposited as a hole blocking layer, and Alq _{3 as an electron transport layer thereon} was deposited at 200 Å. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited to a thickness of 1,200 Å on the electron injection layer to form a cathode. An electroluminescent device was manufactured.

On the other hand, all organic compounds required for manufacturing OLED devices were vacuum sublimated and purified under ^{10 -6} to 10 ^{-8 torr for each material and used for OLED manufacturing.}

For the organic electroluminescent device manufactured as described above, electroluminescence (EL) characteristics were measured with M7000 of McScience, and the reference luminance was 6,000 through the life instrumentation measuring device (M6000) manufactured by McScience with the measurement result. At cd/m ² , T90 was measured.

The characteristics of the organic electroluminescent device of the present invention are shown in Tables 21 to 23 below. For reference, Table 22 is an example of simultaneous deposition of two host compounds of Experimental Example 1 as separate sources, Table 23 is an example of depositing two light emitting layer compounds of Experimental Example 2 as a single source after premixing, Table 21 shows This is an example of applying a single host material in Experimental Example 1.

light emitting layer
compound drive voltage
(V) efficiency
(cd/A) color coordinates
(x, y) life span
(T ₉₀ ) Comparative Example 1 17 3.88 77.2 (0.275,0.672) 158 Comparative Example 2 18 3.74 76.3 (0.279, 0.675) 162 Comparative Example 3 30 3.84 740.4 (0.280, 0.676) 170 Comparative Example 4 133 4.32 70.2 (0.281, 0.678) 137 Comparative Example 5 189 3.86 68.2 (0.278, 0.682) 141 Comparative Example 6 192 3.62 75.3 (0.274, 0.671) 170 Comparative Example 7 199 3.85 72.3 (0.274, 0.679) 169 Comparative Example 8 221 3.90 79.9 (0.277, 0.676) 148 Comparative Example 9 223 3.77 73.4 (0.280, 0.674) 167 Comparative Example 10 243 4.02 72.8 (0.280, 0.679) 121 Comparative Example 11 244 3.88 69.4 (0.277, 0.681) 132 Comparative Example 12 269 3.81 78.4 (0.281, 0.673) 180 Comparative Example 13 271 3.61 76.2 (0.277, 0.672) 171 Comparative Example 14 2-3 2.49 57.9 (0.272, 0.682) 89 Comparative Example 15 2-8 2.63 58.6 (0.275, 0.676) 92 Comparative Example 16 2-21 2.62 58.1 (0.276, 0.680) 96 Comparative Example 17 2-27 2.51 59.8 (0.274, 0.677) 103 Comparative Example 18 2-28 2.69 60.1 (0.279, 0.669) 94 Comparative Example 19 2-31 2.65 59.0 (0.272, 0.680) 111 Comparative Example 20 2-72 2.70 60.3 (0.278, 0.673) 102 Comparative Example 21 2-77 3.03 59.7 (0.278, 0.683) 127 Comparative Example 22 2-79 3.50 61.2 (0.276, 0.664) 154 Comparative Example 23 2-91 3.51 63.1 (0.275, 0.667) 157 Comparative Example 24 2-102 3.47 62.4 (0.277, 0.674) 149 Comparative Example 25 2-122 3.52 61.9 (0.271, 0.683) 151 Comparative Example 26 2-123 3.42 62.1 (0.273, 0.672) 158

compound 1 compound 2 ratio drive voltage
(V) efficiency
(cd/A) color coordinates
(x, y) life span
(T ₉₀ ) Comparative Example 27 17 A 1:1 5.63 76.8 (0.276, 0.672) 242 Comparative Example 28 E 6.91 67.1 (0.281, 0.681) 180 Comparative Example 29 18 C 1:1 5.23 78.9 (0.278, 0.677) 264e3 Comparative Example 30 D 5.68 80.1 (0.277, 0.679) 286 Comparative Example 31 189 A 1:1 5.77 82.3 (0.284, 0.669) 301 Comparative Example 32 C 5.51 86.4 (0.267, 0.673) 273 Comparative Example 33 18 A 1:2 5.72 76.3 (0.271, 0.680) 233 Comparative Example 34 1:1 5.59 78.7 (0.264, 0.685) 247 Comparative Example 35 189 B 1:2 6.55 63.6 (0.269, 0.674) 206 Comparative Example 36 1:1 6.12 67.8 (0.273, 0.681) 219 Example 1 17 2-3 1:8 4.68 101.7 (0.261 0.680) 322 Example 2 1: 5 4.52 108.2 (0.267, 0.675) 368 Example 3 1: 2 4.26 110.4 (0.275, 0.678) 387 Example 4 1:1 3.98 113.9 (0.276, 0.674) 401 Example 5 2:1 4.18 120.3 (0.274, 0.676) 398 Example 6 5:1 4.43 117.0 (0.276, 0.680) 386 Example 7 8:1 4.61 109.8 (0.275, 0.679) 354 Example 8 18 2-8 1: 2 4.54 116.1 (0.267, 0.680) 392 Example 9 1:1 4.01 118.3 (0.270, 0.678) 417 Example 10 30 2-21 1: 2 4.37 116.2 (0.260, 0.674) 397 Example 11 1:1 4.06 119.7 (0.263, 0.683) 409 Example 12 133 2-27 1: 2 4.33 118.3 (0.282, 0.677) 384 Example 13 1:1 4.12 120.1 (0.282, 0.683) 415 Example 14 189 2-28 1: 2 4.27 120.5 (0.267, 0.670) 377 Example 15 1:1 4.09 123.1 (0.278, 0.683) 411 Example 16 192 2-31 1: 2 4.32 110.3 (0.271, 0.680) 354 Example 17 1:1 4.08 119.7 (0.263, 0.671) 408 Example 18 199 2-72 1: 2 4.58 115.3 (0.281, 0.683) 392 Example 19 1:1 4.11 120.8 (0.262, 0.675) 421 Example 20 221 2-77 1: 2 4.67 121.5 (0.276, 0.673) 404 Example 21 1:1 4.21 128.9 (0.266, 0.685) 467 Example 22 223 2-79 1: 2 4.77 124.2 (0.275, 0.669) 432 Example 23 1:1 4.41 132.7 (0.280, 0.679) 488 Example 24 243 2-91 1: 2 4.88 126.2 (0.263, 0.678) 459 Example 25 1:1 4.67 131.5 (0.270, 0.677) 490 Example 26 244 2-102 1: 2 4.86 133.8 (0.284, 0.680) 469 Example 27 1:1 4.58 140.2 (0.277, 0.681) 505 Example 28 269 2-122 1: 2 4.56 124.8 (0.275, 0.673) 429 Example 29 1:1 4.37 131.2 (0.269, 0.680) 467 Example 30 271 2-123 1: 2 4.86 138.7 (0.286, 0.678) 507 Example 31 1:1 4.65 143.2 (0.281, 0.679) 563

compound 1 compound 2 ratio drive voltage
(V) efficiency
(cd/A) color coordinates
(x, y) life span
(T ₉₀ ) Comparative Example 37 17 A 1:1 5.79 83.9 (0.273, 0.675) 258 Comparative Example 38 C 1:1 5.62 90.2 (0.276, 0.684) 297 Comparative Example 39 189 D 1:1 5.42 92.8 (0.284, 0.678) 330 Comparative Example 40 E 1:1 6.09 74.5 (0.269, 0.680) 254 Comparative Example 41 244 A 1:1 5.55 88.6 (0.271, 0.683) 284 Comparative Example 42 B 1:1 6.13 70.6 (0.286, 0.666) 237 Example 32 17 2-8 1:1 3.17 124.8 (0.274, 0.671) 502 Example 33 2-28 1:1 3.21 123.6 (0.268, 0.681) 511 Example 34 18 2-77 1:1 3.48 134.2 (0.282, 0.679) 575 Example 35 2-79 1:1 3.59 140.4 (0.280, 0.676) 601 Example 36 189 2-91 1:1 3.62 141.2 (0.277, 0.682) 609 Example 37 2-102 1:1 3.64 143.6 (0.263, 0.675) 618 Example 38 271 2-122 1:1 3.50 136.7 (0.275, 0.677) 591 Example 41 2-123 1:1 3.60 151.3 (0.276, 0.670) 653

As can be seen in Tables 21 to 23, when the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 are simultaneously included in the organic material layer of the organic light emitting device, better efficiency and lifespan compared to the case where each is included alone characteristics were confirmed. Based on these excellent results, it can be expected that an exciplex phenomenon occurs when both compounds are included at the same time.

The exciplex phenomenon is a phenomenon in which electron exchange occurs between two molecules, which emits energy of the size of the HOMO level of the electron donor molecule (donor, p-host) and the LUMO level of the electron acceptor molecule (acceptor, n-host). It is a phenomenon. When an electron donor molecule (donor, p-host) with good hole transport ability and an electron acceptor molecule (acceptor, n-host) with good electron transport ability are used together as a host of the light emitting layer, the hole becomes an electron donor molecule (donor, p-host) ), and electrons are injected into the electron acceptor molecule (acceptor, n-host). When the exciplex phenomenon occurs, Reverse Intersystem Crossing (RISC) occurs smoothly, so that the internal quantum efficiency of light emission can reach 100%. In addition, the driving voltage can be lowered, which is a great advantage in improving the lifespan.

In addition, in the present invention, the light emitting host composed of a plurality of compounds was pre-mixed with the compounds and then deposited as a single deposition source (Experimental Example 2, Table 23). In this case, since multiple depositions are not performed, the thin film It has the advantage of maintaining the uniformity of the surface and the characteristics of the thin film. In addition, it is possible to form a device with improved efficiency, driving voltage, and lifespan as well as reducing overall process cost through simplification of the process process.

As can be seen in Tables 22 and 23, the condensed carbazole structure as in the heterocyclic compound structure of Formula 2 herein is a structure including two carbazoles or one carbazole and a hetero ring, and nitrogen and hetero Due to the lone pair of electrons present in the atom, it has a strong electron donor property. That is, as can be seen in Tables 22 and 23, one of the compounds corresponding to the heterocyclic compound corresponding to Formula 1 and the compounds A to E (biscarbazole form; or the combined structure of carbazole and heterocycle) It was confirmed that the overall driving voltage/efficiency/lifetime was superior compared to the case of using .

In addition, through π-conjugation of a wide area corresponding to the entire basic skeleton, it has a HOMO level of a wider area than the non-condensed carbazole compound, and thus has a wider hole distribution. Therefore, it was confirmed that the device exhibited fast hole transport characteristics when driving, and through this, it was confirmed that the device's threshold voltage and the driving voltage were lowered at the same time, thereby improving the current efficiency.

In addition, the condensed carbazole as in Chemical Formula 2 is a form in which pentagonal to hexagonal rings are condensed through π-π bonds. This shows high thermal stability because it has a rigid structure with minimal intramolecular distortion. (Td ₉₅ : 400℃ or higher, high T _g ) High thermal stability is a good factor to overcome the harsh high vacuum and high temperature conditions of the organic light emitting device (OLED) deposition process, and it is also advantageous for device deterioration when the device is driven for a long time . Therefore, it can be seen that the condensed carbazole structure as in the structure of Chemical Formula 2 is a basic structure that can become a material with a good lifespan based on low voltage, high efficiency and high thermal stability.

In addition, as shown in Table 23 above, when premixing, the unique thermal properties of each material should be checked and mixed. In this case, when the premixed host material is deposited from a single deposition source, the deposition conditions including the deposition rate may be greatly affected according to the intrinsic thermal properties of the material. If the thermal properties between two or more premixed materials are not similar and very different, repeatability and reproducibility in the deposition process cannot be maintained, which means that uniform OLED devices cannot be manufactured in one deposition process. .

In order to overcome this problem, the electrical properties of materials can be tuned by using an appropriate combination of the basic structure and substituents of each material, and at the same time, the thermal properties can be controlled according to the shape of the molecular structure. Therefore, not only the CN bonding of the condensed carbazole as shown in Chemical Formula 2, but also various substituents in Chemical Formula 2 other than the basic skeleton are used to improve device performance, as well as to control the thermal properties of each material to provide a host-host relationship It is possible to secure the diversity of the pre-mixed deposition process. Through this, it was confirmed that there is an advantage of securing the diversity of the premix deposition process using not only two compounds as hosts, but also three to four or more host materials.

In addition, when driving an OLED device, the inside of the device is exposed to various types of heat for a long time due to heat energy generated by non-raditive emission caused by non-raditive emission and heat energy generated from resistance to current flow. will be exposed Unlike metals, since the thermal resistance of organic materials is very low, it is necessary to secure the thermal stability of the material through accurate thermal stability data. In addition, the deposition process of the OLED device is also carried out at a high temperature in a high vacuum state, and the material with low thermal stability is already deteriorated in the deposition process, so that it cannot be driven at all as an OLED device. Therefore, confirming the thermal stability of the material constituting the device is a very important preliminary work in constructing the OLED device.

The condensed carbazole structure described in Formula 2 has a rigid structure in which several pentagonal/hexagonal rings strongly linked by π-π bonds are condensed, and thus a high Tg of 100°C or more and a very high Td of 400°C or more (95%) temperature. It can be seen that this is a material that can sufficiently withstand the severe high vacuum/high temperature conditions of the OLED device deposition process, and has sufficient stability to prevent device degradation even after long-time operation of the device.

4 to 21 are thermal analysis data of each material of Chemical Formula 2 and a specific compound measured using Mettler Toledo's TGA/DSC equipment. The measured Td ₉₅ was ^{measured by heating at 30 o} C to increase the temperature of 10 K per minute to 600 ° C. Confirmation of glass transition temperature and decomposition temperature among thermal properties such as glass transition temperature (Tg), crystallization temperature (Tc), melting temperature (Tm), and decomposition temperature (Td/95%) corresponding to Chemical Formula 2 and the specific compound Through this, it was possible to first confirm the long-term operation of the device and the stability of the high-vacuum deposition process.

4 and 5 are graphs showing the thermal stability of Compound 2-8 of the present application, FIGS. 6 and 7 are graphs showing the thermal stability of Compound 2-18 of the present application, and FIGS. 8 and 9 are graphs of Compound 2-79 of the present application It is a graph showing the thermal stability, and FIGS. 10 and 11 are graphs showing the thermal stability of the compound 2-123 of the present application. 12 and 13 are graphs showing the thermal stability of Compound 2-19 of the present application, FIGS. 14 and 15 are graphs showing the thermal stability of Compound 2-20 of the present application, and FIGS. 16 and 17 are graphs of Compound 2-22 of the present application It is a graph showing thermal stability.

In addition, FIGS. 18 and 18 are graphs showing the thermal stability of the compound A, and FIGS. 20 and 21 are graphs showing the thermal stability of the compound C. FIG.

In the graphs showing the thermal stability of FIGS. 4 to 21 , Td ₉₅ is a point obtained by measuring the temperature when 95% of the mass is left by applying the temperature, and if the Td ₉₅ is high, it means that it is stable even at a high temperature.

As can be seen when comparing FIGS. 4 to 17 and FIGS. 18 to 21 , in the case of Compound A ( FIGS. 18 and 19 ) and Compound C ( FIGS. 20 and 21 ) having a biscarbazole structure, Td ₉₅ is 400° C. It can be confirmed that the measurement is as follows, which was confirmed to represent a lower thermal stability compared to the condensed carbazole compound.

Therefore, when the compound of Formula 1 and the compound of Formula 2 are included at the same time, it can be confirmed that the basic structure is sufficiently effective to fabricate a low-voltage/high-efficiency device or an OLED device having high-efficiency/long-life, low-voltage/long-life characteristics.

100: substrate
200: positive electrode
300: organic layer
301: hole injection layer
302: hole transport layer
303: light emitting layer
304: hole blocking layer
305: electron transport layer
306: electron injection layer
400: cathode

Claims (17)

An organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer provided between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic light emitting device that simultaneously contains a heterocyclic compound represented by the following Chemical Formula 1, and a heterocyclic compound represented by any one of the following Chemical Formulas 2-7 to 2-9:
[Formula 1]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

In Formulas 1 and 2-7 to 2-9,
N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclic group containing one or more N,
L is a direct bond; a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group, a is an integer from 1 to 3, and when a is 2 or more, L is the same as or different from each other,
R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring, R9, R10, R11 and R14 is hydrogen, b and c are each an integer of 1 to 3, when b is 2 or more, R9 is the same as or different from each other, and when c is 2 or more, R10 is the same as or different from each other,
A ₁ and A ₂ are the same as or different from each other and each independently O; S; NR _a ; or CR _b R _c ,
Wherein R _{a To} R _{c Are} the same as or different from each other, and each independently, hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
A ₃ is O; S; or NR _g ,
R50 and R51 are hydrogen; Or a substituted or unsubstituted aryl group, at least one is a substituted or unsubstituted aryl group,
R _g , R52 and R53 are the same as or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
r is an integer from 0 to 3,
q is an integer from 0 to 4. The organic light emitting diode of claim 1, wherein Chemical Formula 1 is represented by one of Chemical Formulas 3 to 6:
[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 3 to 6, the substituents are as defined in Formula 1 above. The organic light emitting diode of claim 1, wherein Chemical Formula 1 is represented by one of Chemical Formulas 7 to 9:
[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 7 to 9, the definitions of R1 to R10, L, a, b and c are as defined in Formula 1 above,
X1 is CR21 or N, X2 is CR22 or N, X3 is CR23 or N, X4 is CR24 or N, X5 is CR25 or N,
R21 to R25 and R27 to R32 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group or adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a hetero ring. 4. The method according to claim 3,

is an organic light emitting device represented by one of the following Chemical Formulas 10 to 12:
[Formula 10]

[Formula 11]

[Formula 12]

In Formula 10, at least one of X1, X3 and X5 is N, and the rest are as defined in Formula 7,
In Formula 11, at least one of X1, X2 and X5 is N, and the rest are as defined in Formula 7,
In Formula 12, at least one of X1 to X3 is N, and the rest are as defined in Formula 7,
R22, R24 and R33 to R36 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group or adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a hetero ring. The organic light emitting diode of claim 4, wherein Chemical Formula 10 is selected from the following structural formulas:

In the above structural formula, R21 to R25 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group or adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a hetero ring. delete delete The organic light emitting diode of claim 1, wherein Chemical Formula 1 is represented by any one of the following compounds:

. The organic light-emitting device according to claim 1, wherein Chemical Formulas 2-7 to 2-9 are represented by any one of the following compounds:

. The heterocyclic ring of claim 1, wherein the organic material layer comprises at least one of a hole blocking layer, an electron injection layer, and an electron transport layer, and at least one of the hole blocking layer, the electron injection layer, and the electron transport layer is represented by Formula 1 An organic light-emitting device comprising a compound, and a heterocyclic compound represented by any one of Chemical Formulas 2-7 to 2-9. The method according to claim 1, wherein the organic material layer comprises a light emitting layer, the light emitting layer is an organic compound represented by the heterocyclic compound represented by Formula 1, and the heterocyclic compound represented by any one of Formulas 2-7 to 2-9 light emitting element. The method according to claim 1, wherein the organic material layer comprises a light emitting layer, the light emitting layer comprises a host material, the host material is a heterocyclic compound represented by Formula 1, and any one of Formulas 2-7 to 2-9 An organic light emitting device comprising the heterocyclic compound represented. The method according to claim 1, wherein the organic light emitting device is a light emitting layer, a hole injection layer, a hole transport layer. An organic light-emitting device further comprising one or more layers selected from the group consisting of an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer. A composition for an organic material layer of an organic light emitting device comprising a heterocyclic compound represented by the following Chemical Formula 1, and a compound represented by any one of the following Chemical Formulas 2-7 to 2-9:
[Formula 1]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

In Formula 1 and Formula 2-7 to 2-9,
N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclic group containing one or more N,
L is a direct bond; a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group, a is an integer from 1 to 3, and when a is 2 or more, L is the same as or different from each other,
R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring, R9, R10, R11 and R14 is hydrogen, b and c are each an integer of 1 to 3, when b is 2 or more, R9 is the same as or different from each other, and when c is 2 or more, R10 is the same as or different from each other,
A ₁ and A ₂ are the same as or different from each other and each independently O; S; NR _a ; or CR _b R _c ,
Wherein R _{a To} R _{c Are} the same as or different from each other, and each independently, hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
A ₃ is O; S; or NR _g ,
R50 and R51 are hydrogen; Or a substituted or unsubstituted aryl group, at least one is a substituted or unsubstituted aryl group,
R _g , R52 and R53 are the same as or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
r is an integer from 0 to 3,
q is an integer from 0 to 4. The method according to claim 14, wherein the weight ratio of the heterocyclic compound represented by Formula 1 in the composition: the compound represented by any one of Formulas 2-7 to 2-9 is 1: 10 to 10: 1 of the organic light emitting device. A composition for an organic layer. preparing a substrate;
forming a first electrode on the substrate;
forming one or more organic material layers on the first electrode; and
Forming a second electrode on the organic material layer,
The method of manufacturing an organic light emitting device, wherein the forming of the organic material layer comprises forming one or more organic material layers using the composition for an organic material layer according to claim 14 . The method according to claim 16, wherein the forming of the organic material layer is performed by pre-mixing the heterocyclic compound of Formula 1 and any one of Formulas 2-7 to 2-9 using a thermal vacuum deposition method. A method of manufacturing an organic light emitting device to form.

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