KR20200072227A - Organic light emitting device, manufacturing method of the same and composition for organic layer of organic light emitting device - Google Patents

Abstract

The present invention relates to an organic light emitting element, a manufacturing method thereof, and a composition for an organic material layer. The organic light emitting element comprises: a first electrode; a second electrode; and one or more organic material layers provided between the first electrode and the second electrode. Therefore, life characteristics of the element can be improved.

Description

ORGANIC LIGHT EMITTING DEVICE, MANUFACTURING METHOD OF THE SAME AND COMPOSITION FOR ORGANIC LAYER OF ORGANIC LIGHT EMITTING DEVICE

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-emissive display device, and has a wide viewing angle, excellent contrast, and high 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 two electrodes are combined and paired in an organic thin film, and then disappear and shine. 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 as needed. For example, as the organic thin film material, a compound that can itself constitute a light emitting layer may be used, or a compound capable of serving as a host or a dopant of a host-dopant-based light emitting layer may be used. In addition, as a material of the organic thin film, a compound capable of performing a role of hole injection, hole transport, electron blocking, hole blocking, electron transport, electron injection, etc. may be used.

In order to improve the performance, life or efficiency of the organic light emitting device, the development of an organic thin film material 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 and second electrodes,

At least one layer of the organic material layer is a heterocyclic compound represented by Formula 1 below; And a heterocyclic compound represented by the following Chemical Formula 2 or Chemical Formula 3.

[Formula 1]

[Formula 2]

[Formula 3]

In Chemical Formulas 1 to 3,

L1 to L3 are direct bonds; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group, a1, m and p are integers from 1 to 3, and when a1, m and p are 2 or more, the substituents in parentheses are the same or different from each other,

R ₁ to R ₆ , R ₁₀ to R ₁₉ and R ₂₁ to R ₂₉ 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 a substituted or unsubstituted amine 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 substituted or unsubstituted hetero ring, wherein a3 and r are 0. Is an integer from 2 to 2, a4 is an integer from 0 to 3, and when r, a3 and a4 are 2 or more, the substituents in parentheses are the 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 ,

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,

Ar1 is a substituted or unsubstituted heteroaryl group containing at least one N,

Ar3 and Ar4 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, n, q and a2 are integers of 1 or more and 5 or less, and when n, q and a2 are 2 or more, the substituents in parentheses are the same or different from each other,

Ar2 is represented by the following formula 1-1 or 1-2,

[Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2,

Y1 to Y4 are the same as or different from each other, and each independently an substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted aromatic heterocycle,

R ₇ 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 substituted or unsubstituted amine groups.

In addition, another exemplary embodiment of the present application, a heterocyclic compound represented by Formula 1; And a heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3.

Finally, an exemplary embodiment of the present application includes 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, and forming the organic material layer includes forming one or more organic material layers using the composition for an organic material layer according to an exemplary embodiment of the present application. Provided is a method of manufacturing an organic light emitting device.

The organic light emitting device according to the exemplary embodiment of the present application includes a heterocyclic compound represented by Chemical Formula 1; And the heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3 may be used simultaneously as a material for the light emitting layer of the organic light emitting device. In addition, when the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3 are simultaneously used in an organic light emitting device, the driving voltage of the device is lowered, light efficiency is improved, and thermal stability of the compound By doing so, the life characteristics of the device can be improved.

In particular, the heterocyclic compound represented by Formula 1; And when the heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3 is simultaneously included in the organic material layer of the organic light emitting device, hole mobility is particularly excellent, and thus the balance between holes and electrons is excellent, and accordingly, the device life is excellent. It has a characteristic.

In addition, in the heterocyclic compound represented by Formula 1, the N-containing ring is substituted in the carbon position 4 of the dibenzothiophene structure, and the N-containing ring in the dibenzothiophene structure is substituted in the 2nd position of the benzene ring. By having a specific substituent substituted, it has a more electronic stability structure, thereby improving device life.

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.

Hereinafter, the present application will be described in detail.

The term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more are substituted , 2 or more substituents may be the same or different from each other.

In the present specification, "substituted or unsubstituted" means C1 to C60 straight or branched chain alkyl; C2 to C60 straight or branched chain alkenyl; C2 to C60 straight or branched chain 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 It means that it is substituted or unsubstituted with one or more substituents, or substituted with two or more substituents selected from the substituents exemplified above.

In one embodiment of the present application, R, R', and R" 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 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 chain or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. Carbon number of the alkyl group may be 1 to 60, specifically 1 to 40, more specifically, 1 to 20. Specific examples are 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 are 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 alkenyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 2 to 20 carbon atoms. Specific examples include 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, and the like, but are not limited to these.

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. 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. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. 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. It is not limited.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic group having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which a cycloalkyl group is directly connected to or condensed with another ring group. Here, the other cyclic group may be a cycloalkyl group, but may be another kind of cyclic group, such as a heterocycloalkyl group, an aryl group, a heteroaryl group, and the like. The cycloalkyl group may have 3 to 60 carbon atoms, specifically 3 to 40 carbon atoms, and more specifically 5 to 20 carbon atoms. 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, monocyclic or polycyclic having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which a heterocycloalkyl group is directly connected to or condensed with another ring group. Here, the other cyclic group may be a heterocycloalkyl group, but may be another kind of cyclic group, for example, a cycloalkyl group, an aryl group, a heteroaryl group. 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 6 to 60 carbon atoms or a monocyclic ring, 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 another kind of ring group, such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, and the like. The aryl group includes a spiro group. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of the aryl group include a phenyl group, biphenyl group, triphenyl group, naphthyl group, anthryl group, chrysenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenenyl group, pyre Neil group, tetrasenyl group, pentasenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, and condensed ring groups thereof And the like, but are 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, monocyclic or polycyclic having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic group 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 another 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 pyridyl group, pyrrolyl group, pyrimidyl group, pyridazinyl group, furanyl group, thiophene group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl 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, quinozolinyl group, naphthyridyl group, acridinyl group, phenanthridy Niyl group, imidazopyridinyl group, diazanaphthalenyl group, triazinden 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, phenothiathiazinyl group, phthalazinyl group, naphthilidinyl 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 ]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 groups; Diarylamine group; Diheteroarylamine group; Alkylarylamine groups; Alkyl heteroarylamine groups; And may be selected from the group consisting of an aryl heteroarylamine group, the number of carbon is not particularly limited, it is preferably 1 to 30. Specific examples of the amine group are methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, dibiphenylamine group, anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluore A nilamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group, and the like, but is not limited thereto.

In the present specification, an arylene group means one having two bonding positions on the aryl group, that is, a divalent group. These may be applied to the description of the aryl group described above, except that each is a divalent group. In addition, the heteroarylene group means a heteroaryl group having two bonding positions, that is, a divalent group. These may be applied to the description of the heteroaryl group described above, except that each is a divalent group.

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; Alkyl groups; Alkenyl group; Alkoxy groups; Cycloalkyl group; Aryl group; And a heterocyclic group. Specifically, an aryl group may be substituted, and the aryl group may be applied to the above-described examples. For example, the phosphine oxide group includes a diphenylphosphine oxide group, dinaphthyl phosphine oxide, but is not limited thereto.

In the present specification, the silyl group includes Si and the Si atom is a substituent directly connected as a radical, -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; Alkyl groups; Alkenyl group; Alkoxy groups; Cycloalkyl group; Aryl group; And a heterocyclic group. Specific examples of the silyl group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. It is not limited.

In the present specification, the “adjacent” group refers to a substituent substituted on an atom directly connected to an atom in which the substituent is substituted, a substituent positioned closest to the substituent and the other substituent substituted on the atom in which the substituent is substituted. Can be. For example, two substituents substituted at the ortho position on the benzene ring and two substituents substituted on the same carbon in the aliphatic ring may be interpreted as “adjacent” to each other.

The structures exemplified by the aforementioned cycloalkyl group, cycloheteroalkyl group, aryl group and heteroaryl group may be applied, except that the aliphatic or aromatic hydrocarbon ring or heterocycle which 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 one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer is represented by Formula 1 A heterocyclic compound represented by; And a heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3.

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, wherein at least one layer of the organic material layer is represented by Formula 1 A heterocyclic compound represented by; And it provides an organic light emitting device comprising a heterocyclic compound represented by the formula (2).

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, wherein at least one layer of the organic material layer is represented by Formula 1 A heterocyclic compound represented by; And it provides an organic light emitting device comprising a heterocyclic compound represented by the formula (3).

In one embodiment of the present application, R ₁ to R ₆ 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 a substituted or unsubstituted amine group, or two or more groups 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, R ₁ to R ₆ 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 it may be a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, R ₁ to R ₆ 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, R ₁ to R ₆ 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, R ₁ to R ₆ are the same as or different from each other, and each independently hydrogen; C1 to C40 alkyl group; C6 to C40 aryl group; Or it may be a C2 to C40 heteroaryl group.

In another exemplary embodiment, R ₁ to R ₆ may be hydrogen.

In one embodiment of the present application, L1 and L2 are a direct bond; A substituted or unsubstituted arylene group; Or it may be a substituted or unsubstituted heteroarylene group.

In another exemplary embodiment, L1 and L2 are a direct bond; A substituted or unsubstituted C6 to C60 arylene group; Or it may be a substituted or unsubstituted C2 to C60 heteroarylene group.

In another exemplary embodiment, L1 and L2 are a direct bond; A substituted or unsubstituted C6 to C40 arylene group; Or it may be a substituted or unsubstituted C2 to C40 heteroarylene group.

In another exemplary embodiment, L1 and L2 are a direct bond; C6 to C40 arylene group; Or it may be a C2 to C40 heteroarylene group.

In another exemplary embodiment, L1 and L2 are a direct bond; Or it may be a C6 to C40 monocyclic arylene group.

In another exemplary embodiment, L1 and L2 are a direct bond; Or it may be a phenylene group.

In one embodiment of the present application, Ar1 is substituted or unsubstituted, and may be a heteroaryl group including at least one N.

In another exemplary embodiment, Ar1 is substituted or unsubstituted, and may be a C2 to C60 heteroaryl group including at least one N.

In another exemplary embodiment, Ar1 is substituted or unsubstituted, and may be a C2 to C40 heteroaryl group including at least one N.

In another exemplary embodiment, Ar1 is substituted or unsubstituted with one or more substituents selected from the group consisting of C6 to C40 aryl groups, and C2 to C40 heteroaryl groups, and C2 to C40 containing at least one N It may be a heteroaryl group.

In another exemplary embodiment, Ar1 is a C6-C40 aryl group, and a C2-C40 heteroaryl group is substituted or unsubstituted with one or more substituents, a pyridine group; Pyrimidine group; Triazine group; Quinoline group; Quinazoline groups; Phenanthroline groups; Or it may be an imidazole group.

In another exemplary embodiment, Ar1 is a pyridine group unsubstituted or substituted with a phenyl group; A pyrimidine group unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl group, biphenyl group, dibenzothiophene group and dimethylfluorene group; A triazine group unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl group, biphenyl group, dibenzothiophene group and dimethylfluorene group; A quinoline group unsubstituted or substituted with a phenyl group; A quinazoline group unsubstituted or substituted with a phenyl group or a biphenyl group; Phenanthroline groups; Or it may be an imidazole group unsubstituted or substituted with a phenyl group.

In one embodiment of the present application, Ar1 is -CN; Or -NO ₂ .

In an exemplary embodiment of the present application, Ar2 may be represented by Chemical Formula 1-1.

In one embodiment of the present application, Ar2 may be represented by Chemical Formula 1-2.

In one embodiment of the present application, Chemical Formula 1-1 may be represented by any one of the following structural formulas.

In the structural formula, X1 to X6 are the same as or different from each other, and each independently NR ₃₈ , S, O or CR ₃₉ R ₄₀ ,

R ₃₁ to R ₃₇ 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 a substituted or unsubstituted amine 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 substituted or unsubstituted hetero ring,

a is an integer from 0 to 8, b, c, d, e, f and g are each independently an integer from 0 to 6, and when a, b, c, d, e, f and g are integers of 2 or more, parentheses My substituents are the same or different from each other,

R ₃₈ to R ₄₀ are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In an exemplary embodiment of the present application, Chemical Formula 1-2 may be represented by any one of the following structural formulas.

In the structural formula, X7 to X12 are the same as or different from each other, and each independently NR ₄₉ , S, O, or CR ₅₀ R ₅₁ ,

R ₄₁ to R ₄₈ 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 a substituted or unsubstituted amine 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 substituted or unsubstituted hetero ring,

h is an integer from 0 to 7, and when h is an integer of 2 or more, the substituents in parentheses are the same or different from each other,

R ₄₉ to R ₅₁ are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In one embodiment of the present application, R ₃₁ to R ₃₇ 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 it may be a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, R ₃₁ to R ₃₇ 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, R ₃₁ to R ₃₇ 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, R ₃₁ to R ₃₇ 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, R ₃₁ to R ₃₇ are the same as or different from each other, and each independently hydrogen; Phenyl group; Biphenyl group; Naphthyl group; A carbazole group unsubstituted or substituted with a phenyl group; It may be a dibenzothiophene group or a dibenzofuran group.

In one embodiment of the present application, R ₃₈ to R ₄₀ are the same as or different from each other, and each independently, a substituted or unsubstituted C1 to C60 alkyl group; Or it may be a substituted or unsubstituted C6 to C60 aryl group.

In another exemplary embodiment, R ₃₈ to R ₄₀ are the same as or different from each other, and each independently, a substituted or unsubstituted C1 to C40 alkyl group; Or it may be a substituted or unsubstituted C6 to C40 aryl group.

In another exemplary embodiment, R ₃₈ to R ₄₀ are the same as or different from each other, and each independently, a C1 to C40 alkyl group; Or it may be a C6 to C40 aryl group.

In another exemplary embodiment, R ₃₈ to R ₄₀ are the same as or different from each other, and each independently, a methyl group; Or it may be a phenyl group.

In one embodiment of the present application, R ₄₁ to R ₄₈ are the same as or different from each other, and each independently hydrogen; Or it may be a substituted or unsubstituted aryl group.

In another exemplary embodiment, R ₄₁ to R ₄₈ are the same as or different from each other, and each independently hydrogen; Or it may be a substituted or unsubstituted C6 to C60 aryl group.

In another exemplary embodiment, R ₄₁ to R ₄₈ are the same as or different from each other, and each independently hydrogen; Or it may be a substituted or unsubstituted C6 to C40 aryl group.

In another exemplary embodiment, R ₄₁ to R ₄₈ are the same as or different from each other, and each independently hydrogen; Or it may be a C6 to C40 aryl group.

In another exemplary embodiment, R ₄₁ to R ₄₈ are the same as or different from each other, and each independently hydrogen; Or it may be a phenyl group.

In one embodiment of the present application, the R ₄₉ to R ₅₁ are the same or different from each other, and each independently, a substituted or unsubstituted C1 to C60 alkyl group; Or it may be a substituted or unsubstituted C6 to C60 aryl group.

In another exemplary embodiment, R ₄₉ to R ₅₁ are the same or different from each other, and each independently, a substituted or unsubstituted C1 to C40 alkyl group; Or it may be a substituted or unsubstituted C6 to C40 aryl group.

In another exemplary embodiment, R ₄₉ to R ₅₁ are the same as or different from each other, and each independently, a C1 to C40 alkyl group; Or it may be a C6 to C40 aryl group.

In another exemplary embodiment, R ₄₉ to R ₅₁ are the same as or different from each other, and each independently a methyl group; Or it may be a phenyl group.

는 상기 화학식 1의 L2와 연결되는 위치를 의미한다.In an exemplary embodiment of the present application, in Chemical Formula 1-1 and Chemical Formula 1-2

Means a position connected to L2 of Chemical Formula 1 above.

In one embodiment of the present application, Chemical Formula 1 may be represented by the following Chemical Formula 4 or 5.

[Formula 4]

[Formula 5]

In Chemical Formulas 4 and 5,

The definitions of R ₁ to R ₆ , L1, L2, Ar1, p, m and n are the same as those in Formula 1,

R ₅₂ to R ₅₄ 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 a substituted or unsubstituted amine 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 substituted or unsubstituted hetero ring,

i is an integer from 0 to 8,

j is an integer from 0 to 7.

In one embodiment of the present application, R ₅₄ may be a substituted or unsubstituted aryl group.

In another exemplary embodiment, R ₅₄ may be a substituted or unsubstituted C6 to C60 aryl group.

In another exemplary embodiment, R ₅₄ may be a C6 to C60 aryl group.

In another exemplary embodiment, R ₅₄ may be a C6 to C40 aryl group.

In another exemplary embodiment, R ₅₄ may be a C6 to C40 monocyclic aryl group.

In another exemplary embodiment, R ₅₄ may be a phenyl group.

In one embodiment of the present application, R ₅₂ and R ₅₃ 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, 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 substituted or unsubstituted hetero ring.

In another exemplary embodiment, R ₅₂ and R ₅₃ 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 a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle. do.

In another exemplary embodiment, R ₅₂ and R ₅₃ 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 a substituted or unsubstituted C2 to C40 heteroaryl group, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C40 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C40 heterocycle. do.

In another exemplary embodiment, R ₅₂ and R ₅₃ are the same as or different from each other, and each independently hydrogen; C1 to C40 alkyl group; C6 to C40 aryl group; Or a C2 to C40 heteroaryl group substituted or unsubstituted with a C6 to C40 aryl group, or two or more groups adjacent to each other are bonded to each other, or a C6 to C40 aromatic hydrocarbon ring or C6 substituted or unsubstituted with a C1 to C40 alkyl group. To C40 to C40 substituted or unsubstituted C2 to C40 heterocycle.

In another exemplary embodiment, R ₅₂ and R ₅₃ are the same as or different from each other, and each independently hydrogen; Phenyl group; Biphenyl group; Naphthyl group; A carbazole group unsubstituted or substituted with a phenyl group; Dibenzothiophene group; Or a dibenzofuran group, or two or more groups adjacent to each other are bonded to each other and substituted or unsubstituted with a methyl group; An indole ring unsubstituted or substituted with a phenyl group; Benzothiophene ring; Or benzofuran ring.

In an exemplary embodiment of the present application, Chemical Formula 2 may be represented by Chemical Formula 2-1.

[Formula 2-1]

In Chemical Formula 2-1,

The definitions of R ₁₀ to R ₁₉ , L3, Ar3, Ar4, and a1 to a4 are the same as those in Formula 2.

In an exemplary embodiment of the present application, Chemical Formula 2 may be represented by any one of the following Chemical Formulas 2-2 to 2-5.

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

In Chemical Formulas 2-2 to 2-5,

The definitions of R ₁₀ to R ₁₉ , L3, Ar3, Ar4, and a1 to a4 are the same as those in the formula (2).

In one embodiment of the present application, R ₁₀ to R ₁₉ 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 a substituted or unsubstituted amine group, or two or more groups 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, R ₁₀ to R ₁₉ 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 it may be a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, R ₁₀ to R ₁₉ 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, R ₁₀ to R ₁₉ are the same as or different from each other, and each independently hydrogen; C1 to C60 alkyl group; C6 to C60 aryl group; Or it may be a C2 to C60 heteroaryl group.

In another exemplary embodiment, R ₁₀ to R ₁₉ may be hydrogen.

In one embodiment of the present application, L3 is a direct bond; A substituted or unsubstituted arylene group; Or it may be a substituted or unsubstituted heteroarylene group.

In another exemplary embodiment, L3 may be a direct bond.

In one embodiment of the present application, Ar3 is hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, Ar3 is 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, Ar3 is 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, Ar3 is hydrogen; 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 and a C6 to C40 aryl group; Or it may be a C2 to C40 heteroaryl group unsubstituted or substituted with a C1 to C40 alkyl group.

In another exemplary embodiment, Ar3 is a phenyl group; Biphenyl group; A naphthyl group unsubstituted or substituted with a phenyl group; Dimethylfluorene group; Spirobifluorene group; Or it may be a diphenylfluorene group.

In one embodiment of the present application, Ar3 is a substituted or unsubstituted aryl group, or may be represented by the following formula 2-1-1 or 2-1-2.

[Formula 2-1-1]

[Formula 2-1-2]

In the above formula 2-1-1 and 2-1-2,

R ₆₁ to R ₆₈ 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 a substituted or unsubstituted amine 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 substituted or unsubstituted hetero ring,

A ₄ is O; S; Or NR ₆₉ ,

R ₆₉ is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, R ₆₁ to R ₆₈ are the same as or different from each other, and each independently, hydrogen, or two or more groups adjacent to each other are bonded to each other to be substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or substituted or It may form an unsubstituted C2 to C60 heterocycle.

In another exemplary embodiment, R ₆₁ to R ₆₈ are the same or different from each other, and each independently, hydrogen, or two or more groups adjacent to each other are bonded to each other to be substituted or unsubstituted C6 to C40 aromatic hydrocarbon ring or substituted or It may form an unsubstituted C2 to C40 heterocycle.

In another exemplary embodiment, R ₆₁ to R ₆₈ are the same as or different from each other, and each independently, hydrogen, or two or more groups adjacent to each other are bonded to each other and substituted or unsubstituted by an alkyl group of C1 to C40 to C6 to C40 It can form an aromatic hydrocarbon ring or a C2 to C40 heterocycle.

In another exemplary embodiment, R ₆₁ to R ₆₈ are the same as or different from each other, and each independently, hydrogen, or two or more groups adjacent to each other are bonded to each other and substituted or unsubstituted by a methyl group; It may form a benzofuran ring or a benzothiophene ring.

In one embodiment of the present application, R ₆₉ is a substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, R ₆₉ is 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, R ₆₉ may be a substituted or unsubstituted C6 to C40 aryl group.

In another exemplary embodiment, R ₆₉ may be a C6 to C40 aryl group.

In another exemplary embodiment, R ₆₉ may be a phenyl group.

In one embodiment of the present application, Ar4 is hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heteroaryl group.

In another exemplary embodiment, Ar4 may be a substituted or unsubstituted C6 to C60 aryl group.

In another exemplary embodiment, Ar4 may be a substituted or unsubstituted C6 to C40 aryl group.

In another exemplary embodiment, Ar4 may be a C6 to C40 aryl group unsubstituted or substituted with a C6 to C40 aryl group.

In another exemplary embodiment, Ar4 is a phenyl group unsubstituted or substituted with a phenyl group; A biphenyl group unsubstituted or substituted with a phenyl group; Naphthyl group; Or it may be a triphenylenyl group.

In one embodiment of the present application, A ₁ and A ₂ in Chemical Formula 3 are the same as or different from each other, and each independently O; S; NR _a ; Or CR _b R _c .

In one 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, 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, 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 phenyl groups and triphenylsilyl groups; A biphenyl group unsubstituted or substituted with a phenyl group; Naphthyl group; Triphenylenyl group; Diphenyl fluorenyl group; Dimethylfluorenyl group; A carbazole group unsubstituted or substituted with a phenyl group; Dibenzofuran group; Or it may be a dibenzothiophene group.

In one embodiment of the present application, R ₂₁ to R ₂₉ 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 a substituted or unsubstituted amine group, or two or more groups 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, R ₂₁ to R ₂₉ 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, R ₂₁ to R ₂₉ 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, R ₂₁ to R ₁₉ 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, R ₂₁ to R ₂₉ 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, R ₂₁ to R ₂₉ 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 one embodiment of the present application, R ₂₅ to R ₂₉ may be hydrogen.

In one embodiment of the present application, R ₂₁ and R ₂₄ may be hydrogen.

In one embodiment of the present application, R ₂₂ and R ₂₃ 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 3 may be represented by any one of the following Chemical Formulas 3-1 to 3-6.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

In Chemical Formulas 3-1 to 3-6,

The definitions of R ₂₁ to R ₂₉ , A ₁ , A ₂ and r are the same as those in Formula 3.

In an exemplary embodiment of the present application, Chemical Formula 3 may be represented by any one of the following Chemical Formulas 3-7 to 3-9.

[Formula 3-7]

[Formula 3-8]

[Formula 3-9]

In Chemical Formulas 3-7 to 3-9,

The definitions of A ₁ , A ₂ , R ₂₁ , and R ₂₄ are the same as those in Formula 3,

A ₃ is O; S; Or NR _g ,

R ₇₀ and R ₇₁ are hydrogen; Or a substituted or unsubstituted aryl group, at least one is a substituted or unsubstituted aryl group,

R _g , R ₇₂ and R ₇₃ 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,

o is an integer from 0 to 3,

l is an integer from 0 to 4.

In one embodiment of the present application, R ₇₀ and R ₇₁ are hydrogen; Or it may be a substituted or unsubstituted aryl group.

In another exemplary embodiment, R ₇₀ and R ₇₁ are hydrogen; Or it may be a substituted or unsubstituted C6 to C60 aryl group.

In another exemplary embodiment, R ₇₀ and R ₇₁ are hydrogen; Or it may be a substituted or unsubstituted C6 to C40 aryl group.

In another exemplary embodiment, R ₇₀ and R ₇₁ are hydrogen; Or it may be a C6 to C40 aryl group.

In another exemplary embodiment, R ₇₀ and R ₇₁ are hydrogen; Phenyl group; Or it may be a triphenylenyl group.

In one embodiment of the present application, at least one of R ₇₀ and R ₇₁ may be a substituted or unsubstituted aryl group.

In one embodiment of the present application, R ₇₂ and R ₇₃ may be hydrogen.

In one 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 it may be a biphenyl group.

When the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 2 or Chemical Formula 3 are simultaneously included in the organic material layer of the organic light emitting device, superior efficiency and lifetime effect are exhibited. This result can be expected to occur exciplex (exciplex) phenomenon when two compounds are included at the same time.

The exciplex phenomenon is a phenomenon in which electron exchange between two molecules releases energy of a HOMO level of donor (p-host) and an LUMO level of acceptor (n-host). When an exciplex between two molecules occurs, reverse intersystem crossing (RISC) occurs, which can increase 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 capacity are used as hosts for the light emitting layer, holes are injected into p-host and electrons are injected into n-host, so the driving voltage And lower the lifespan.

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

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

In one embodiment of the present application, Formula 3 may be represented by any one of the following compounds, but is not limited thereto.

In addition, compounds having intrinsic properties of the introduced substituents can be synthesized by introducing various substituents to the structures of Formulas 1 to 3 above. 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 generating layer material used in manufacturing an organic light emitting device, the conditions required for each organic material layer are satisfied. You can synthesize a substance to let.

In addition, by introducing various substituents to the structures of Chemical Formulas 1 to 3, it is possible to finely adjust the energy band gap, on the other hand, to improve the properties at the interface between organic materials, and to use various materials. .

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 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 may be prepared from those intermediate compounds. More specifically, the heterocyclic compound according to an exemplary embodiment of the present application may be prepared based on the preparation examples described below.

In addition, an exemplary embodiment of the present application, the heterocyclic compound represented by Formula 1; And a heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3.

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

In addition, another exemplary embodiment of the present application provides a composition for an organic material layer of an organic light emitting device comprising a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 3.

The heterocyclic compound represented by Chemical Formula 1 The details of the heterocyclic compound represented by Chemical Formula 2 and the heterocyclic compound represented by Chemical Formula 3 are the same as described above.

The heterocyclic compound represented by Formula 1 in the composition: The weight ratio of the heterocyclic compound represented by Formula 2 or Formula 3 may be 1: 10 to 10: 1, 1: 8 to 8: 1 , 1: 5 to 5: 1, may be 1: 2 to 2: 1, but is not limited thereto.

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

The heterocyclic compound represented by the formula (1) in the composition: The weight ratio of the heterocyclic compound represented by the formula (3) may be 1: 10 to 10: 1, 1: 8 to 8: 1, may be 1: 5 It may be 5 to 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 particularly preferably 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 powdery material may be mixed before the organic material layer is formed in 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 kept 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 material, except that one or more organic material layers are formed using the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 above. It can be manufactured by a method and a material for manufacturing a light emitting device.

The heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3 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 application method means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.

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 one or more organic material layers provided between the first electrode and the second electrode, and one or more of the organic material layers A heterocyclic compound represented by Formula 1; And a heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3.

In one 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 one embodiment of the present application, the organic light emitting device may be a blue organic light emitting device, the heterocyclic compound according to Formula 1; And the heterocyclic compound according to Chemical Formula 2 or Chemical Formula 3 may be used as a material for a blue organic light emitting device.

In one embodiment of the present application, the organic light emitting device may be a green organic light emitting device, a heterocyclic compound according to Formula 1; And the heterocyclic compound according to Chemical Formula 2 or Chemical Formula 3 may be used as a material for a green organic light emitting device.

In one embodiment of the present application, the organic light emitting device may be a red organic light emitting device, a heterocyclic compound according to Formula 1; And the heterocyclic compound according to Chemical Formula 2 or Chemical Formula 3 may be used as a material for a red organic light emitting device.

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

In an exemplary embodiment of the present application, the organic material layer includes at least one layer of a hole blocking layer, an electron injection layer, and an electron transport layer, and at least one layer of the hole blocking layer, an electron injection layer, and an electron transport layer is represented by Formula 1 Heterocyclic compounds to be displayed; And a heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3.

In one embodiment of the present application, the organic material layer includes a light emitting layer, and the light emitting layer is a heterocyclic compound represented by Formula 1; And a heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3.

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 Chemical Formula 1; And a heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3.

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, the scope of the present application is not intended to be limited by these drawings, and the structure of the organic light emitting device known in the art may 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, the structure is not limited to this, and as illustrated 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 where the organic material layer is a multilayer. The organic light emitting device 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 stacked structure, and if necessary, the remaining layers other than the light emitting layer may be omitted, and other necessary functional layers may be further added.

In an exemplary embodiment of the present application, 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, and forming the organic material layer includes forming one or more organic material layers using the composition for an organic material layer according to an exemplary embodiment of the present application. Provided is a method of manufacturing an organic light emitting device.

In one embodiment of the present application, the step of forming the organic material layer is a heterocyclic compound represented by Formula 1; And a pre-mixed heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3, and formed using a thermal vacuum deposition method.

The pre-mixed (pre-mixed) is a heterocyclic compound represented by Formula 1; And before depositing the heterocyclic compound represented by the formula (2) or the formula (3) on the organic material layer, it means that the material is first mixed and mixed in a single park.

The pre-mixed 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, the heterocyclic compound of Formula 2, and the heterocyclic compound of Formula 3 are illustrated below, but these are for illustrative purposes. It is not intended to limit the scope of the present application, and may be replaced with materials known in the art.

As the anode material, materials having a relatively large work function may be used, and a transparent conductive oxide, metal, or conductive polymer may be used. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide such as ZnO: Al or SnO ₂ : 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.

As the cathode material, materials having a relatively low work function may be used, and a metal, metal oxide, or conductive polymer may be used. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There is 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 U.S. Patent No. 4,356,429, or described in Advanced Material, 6, p.677 (1994). Starburst amine derivatives, such as tris(4-carbazoyl-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 polymer polyaniline/dodecylbenzenesulfonic acid (Polyaniline/Dodecylbenzenesulfonic acid) or poly( 3,4-ethylenedioxythiophene)/poly(4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), polyaniline/Camphor sulfonic acid or polyaniline/ Polyaniline/Poly(4-styrene-sulfonate) can be used.

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

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

Red, green, or blue light-emitting materials may be used as the light-emitting material, and if necessary, two or more light-emitting materials may be mixed and used. At this time, two or more light-emitting materials may be used by depositing them as separate sources, or pre-mixed and pre-mixed and then used as one source. Further, a fluorescent material may be used as the light emitting material, but it may also be used as a phosphorescent material. As the light-emitting material, a material that emits light by combining holes and electrons injected from the anode and the cathode, respectively, may be used, but materials in which the host material and the dopant material are involved in light emission may also be used.

When a host of light-emitting materials is mixed and used, a host of the same series may be mixed or used, or a host of other series may be mixed and used. For example, two or more types of materials 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 an exemplary embodiment of the present application may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.

The heterocyclic compound according to an exemplary embodiment of the present application may function on a principle similar to that applied to an organic light emitting device in organic electronic devices including organic solar cells, organic photoreceptors, and organic transistors.

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

< Manufacturing example 1> Preparation of compound 1-39

1) Preparation of compound 1-39-2

2-bromodibenzo[b,d]thiophene 5.0g (19.0mM), 2-phenyl-9H-carbazole 3.8g (15.8mM), CuI 3.0g (15.8mM), trans-1,2-diamino Cyclohexane 1.9 mL (15.8 mM), K ₃ PO ₄ 3.3 g (31.6 mM) was dissolved in 100 mL of 1,4-oxane and refluxed for 24 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted, and the organic layer was dried with MgSO ₄ and the solvent was removed with a rotary evaporator. The reaction was purified by column chromatography (DCM:Hex=1:3) and recrystallized with methanol to obtain 5.7 g (85%) of the target compound 1-39-2.

2) Preparation of compound 1-39-1

Compound 1-39-2 6.1g (14.3mM) and tetrahydrofuran (THF, tetrahydrofuran) 100 mL of a mixed solution was added dropwise at 2.5% n-BuLi 7.4mL (18.6mM) at -78 ℃ and stirred for 1 hour at room temperature Did. 4.8 mL (42.9 mM) of trimethylborate (B(OMe) ₃ ) was added dropwise to the reaction mixture and stirred at room temperature for 2 hours. After the reaction was completed, distilled water and DCM were added at room temperature and extracted, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM:MeOH=100:3) and recrystallized with DCM to obtain 4.7g (70%) of the target compound 1-39-1.

3) Preparation of Compound 1-39

1-39-1 8.9 g (19.0 mM), 2-chloro-4,6-diphenyl-1,3,5-triazine 5.1 g (19.0 mM), Pd (PPh ₃ ) ₄ 1.1 g (0.95 mM) , K ₂ CO ₃ 5.2g (38.0mM) was dissolved in toluene/EtOH/H ₂ O 100/20/20 mL and refluxed for 12 hours. After the reaction was completed, distilled water and DCM were added at room temperature and extracted, and the organic layer was dried over MgSO ₄ and the solvent was removed by a rotary evaporator. The reaction was purified by column chromatography (DCM:Hex=1:3) and recrystallized with methanol to obtain 8.7g (70%) of the target compound.

In Preparation Example 1, instead of 2-phenyl-9H-carbazole, Intermediate A of Table 1 was used, and instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, Intermediate B of Table 1 was used. The target compound A was synthesized in the same manner as in Preparation Example 1, except that it was used.

< Manufacturing example 2> Preparation of compound A-1

1) Preparation of compound 1

2-bromodibenzofuran (2-bromodibenzofuran) (70g, 1.0eq/283.30mmol) was dissolved in 1100ml tetrahydrofuran (THF, Tetrahydrofuran) in a mixture of 2L two neck flask (two neck flask) to -78 ℃ Cooled. At this time, prior to the reaction, nitrogen (N ₂ ) was filled in the flask first. After 30 minutes, lithium diisopropyl amide (2M in THF, 36.42g, 1.2eq/339.96mmol) was slowly added dropwise to the mixture while maintaining -78°C. After 1 hour, iodine (I ₂ ) (79.09g, 1.1eq/311.63mmol) was dissolved in THF, and then slowly added dropwise while the inside was raised to room temperature (RT). After washing with sodium thiosulfate pentahydrate aqueous solution, it was extracted with MC. The residual moisture of the mixed solution was removed with MgSO 4, and then silica filter was performed. After adsorption, packing was performed with hexane (Hexane) to purify the column, and finally dried to obtain 68.88 g of a white solid compound 1. (68.88g, 70%)

2) Preparation of Compound A-1

2-bromo-4-iododibenzofuran (1.0eq/20g, 53.62 mmol), B-1 (6.86g, 1.05) in a round neck bottom flask (One neck rbf) eq/121.7mmol), Pd(PPh ₃ ) ₄ (3.1g, 0.05eq/2.68mmol), Na ₂ CO ₃ (17g, 3.0eq/60.86mmol) Toluene/EtOH/H ₂ O(5:1:1 ) The mixture was put in 140 ml and refluxed for 3.5 hours. After the reaction was completed, the reactant was filtered, the base was washed with H ₂ O, and then the organic layer was separated by adding MC and concentrated to adsorb.

After packing with hexane (Hexane), after column purification and concentration, the solid stirred in MeOH was filer to obtain white crystal compound A-1. (10.4g, 60%)

A compound represented by A-1 in Table 2 was prepared in the same manner as in Preparation 2, except that in Example 2, the compound represented by B-1 in Table 2 was used instead of B-1. Synthesized.

< Manufacturing example 3> Preparation of compound A-2

1) Preparation of compound 1

2-Bromodibenzofuran (2-bromodibenzofuran) (70g, 1.0eq/283.30mmol) was dissolved in 1100ml THF, the mixture was placed in a 2L two neck flask (two neck flask) and cooled to -78°C. At this time, prior to the reaction, nitrogen (N ₂ ) was filled in the flask first. After 30 minutes, lithium diisopropyl amide (2M in THF, 36.42g, 1.2eq/339.96mmol) was slowly added dropwise to the mixture while maintaining -78°C. After 1 hour, iodine (I ₂ ) (79.09g, 1.1eq/311.63mmol) was dissolved in THF, and then slowly added dropwise while the inside was raised to room temperature (RT). After washing with sodium thiosulfate pentahydrate aqueous solution, it was extracted with MC. The residual moisture of the mixed solution was removed with MgSO 4, and then silica filter was performed. After adsorption, packing was performed with hexane (Hexane) to purify the column, and finally dried to obtain 68.88 g of a white solid compound 1. (68.88g, 70%)

2) Preparation of Compound A-2

2-bromo-4-iodo-dibenzofurnan (8g, 1.2eq/21.45mmol), 4-boronic acid- in a round neck bottom flask (One neck rbf) Dibenzofuran (4-bronic acid-dibenzofuran) (3.5g, 1.0eq/16.50mmol), Pd(PPh ₃ ) ₄ (0.95g, 0.05eq/0.82mmol), K ₂ CO ₃ (6.84g, 3.0eq/ 49.50mmol) was added to 75 ml of a Toluene/EtOH/H2O (5:1:1) mixed solution and refluxed for 12 hours. After the reaction was completed, the reactant was filtered, the base was washed with H ₂ O, and then the organic layer was separated by adding MC and concentrated to adsorb. After packing with MC:HEX=1:7 to concentrate after column purification, the solid stirred in MeOH was filer to obtain white crystal Compound A-2. (3.5g, 55%)

A compound represented by A-2 in Table 3, prepared in the same manner as in Preparation 3, except that in Example 3, the compound represented by B-2 in Table 3 was used instead of B-2. Was synthesized.

< Manufacturing example 4> Preparation of compound A-3

1) Preparation of compound 1

2-Bromodibenzofuran (2-bromodibenzofuran) (70g, 1.0eq/283.30mmol) was dissolved in 1100ml THF, the mixture was placed in a 2L two neck flask (two neck flask) and cooled to -78°C. At this time, prior to the reaction, nitrogen (N ₂ ) was filled in the flask first. After 30 minutes, lithium diisopropyl amide (2M in THF, 36.42g, 1.2eq/339.96mmol) was slowly added dropwise to the mixture while maintaining -78°C. After 1 hour, iodine (I ₂ ) (79.09g, 1.1eq/311.63mmol) was dissolved in THF, and then slowly added dropwise while the inside was raised to room temperature (RT). After washing with sodium thiosulfate pentahydrate aqueous solution, it was extracted with MC. The residual moisture of the mixed solution was removed with MgSO 4, and then silica filter was performed. After adsorption, packing was performed with hexane (Hexane) to purify the column, and finally dried to obtain 68.88 g of a white solid compound 1. (68.88g, 70%)

2) Preparation of Compound A-3

2-bromo-4-iodo-dibenzofuran (10g, 1.2eq/26.81mmol), 7,7-dimethyl in a round neck bottom flask (One neck rbf) -5,7-dihydroindeno[2,1-b]carbazole (7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole) (3.74g, 1.0eq/22.34mmol), CuI (6.33g, 1.0eq/22.34mmol), trans 1,2-cyclohexane diamine (2.55g, 1.0eq/23.34mmol), NaOH (2.23g, 2.5eq/55.85mmmol ) Was added to 75 ml of 1,4-dioxane (1,4-dioxane) and refluxed for 12 hours. After the reaction was completed, the reactant was filtered, the base was washed with H ₂ O, and then MC was added to separate the organic layer, followed by concentration to adsorb. After packing with MC:HEX=1:6 and concentrating after column purification, the solid stirred in MeOH was filer to obtain white crystal Compound A-3. (7.67 g, 65%)

A compound represented by A-3 in Table 4, prepared in the same manner as in Preparation 4, except that the compound represented by B-3 in Table 4 below was used instead of B-3 in Preparation Example 4 Was synthesized.

< Manufacturing example 5> Preparation of compound D

2-bromo-4,4'-bidibenzofuran[A] (3g, 1.0eq/7.26mmol) in a round neck bottom flask (One neck rbf), (9-phenyl-9H-carbazol-3-yl)boronic acid (2.29g, 1.1eq/7.99mmol), Pd(PPh ₃ ) ₄ (0.42g, 0.05eq/0.36mmol), K ₂ CO ₃ (6.84g,3.0eq/49.50mmol) was added to a 40 ml 1,4-dioxane/H2O (4:1) mixed solution and refluxed for 4 hours. After the reaction was completed, the reactant was filtered to filter solids, and then dissolved in CHCl ₃ to filter silica. After concentration, it was supersaturated by heating in toluene and cooled slowly. Then, the resulting crystals were filtered to obtain target compound D as a white solid. (2.72g, 65%)

In Preparation Example 5, the compounds represented by A-1, A-2, and A-3 in Tables 2 to 4 were used instead of A, and instead of C in Preparation Example 5, they were represented by C-1 in Table 5 below. Except for using the compound to be prepared in the same manner as in Preparation of Preparation Example 5, the target compound represented by D in Table 5 was synthesized.

< Manufacturing example 6> Synthesis of Compound 3-6

1) Preparation of compound 3-6

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 dissolved in 60 mL and refluxed for 24 hours. After completion, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried over MgSO ₄ and the solvent was removed by rotary evaporation. 6 8.6 g (85%) was obtained.

In Preparation Example 6, instead of 4-bromo-1,1';4',1"-terphenyl, intermediate A-1 of Table 6 was used, and 5-phenyl-5,7-dihydroindolo[2, 3-b] Using intermediate B-1 of Table 6 instead of carbazole, the target compound A was synthesized by the same method as in Preparation Example 6.

< Manufacturing example 7> Compound 3- 79 Synthesis

1) Preparation of compound 3-79-2

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

In the preparation of compound 3-79-2 of Preparation Example 7, intermediate C-3 of Table 7 below was substituted for 2-chloro-7-phenyl-5,7-dihydroindolo[2,3-b]carbazole. The target compound C-2 was synthesized by the same method as the production of the preparation of compound 3-79-2 of Preparation Example 7 except for the use.

2) Preparation of compound 3-79-1

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

Intermediate C- in Table 8 below instead of 2-chloro-5,7-diphenyl-5,7-dihydroindolo[2,3-b]carbazole in the preparation of compound 3-79-1 of Preparation Example 7 The target compound C-1 was synthesized by the same method as the preparation of compound 3-79-1 of Preparation Example 7, except that 2 was used.

3) Preparation of compound 3-79

5,7-diphenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborenyl)-5,7-dihydroindolo[2,3-b]carbazole 6.8g (12.72mM), 3-bromo-9-phenyl-carbazole 4.51g (14.00mM), Pd(PPh3)4 0.74g (0.64mM), K2CO3 3.52g (25.45mM), toluene 70mL/ethanol 15mL / Dissolve in 15 mL of water and reflux for 4 hours. After the reaction was completed, distilled water and DCM were added and extracted at room temperature, and the organic layer was dried with MgSO ₄ and the solvent was removed by a rotary evaporator. The reactant was purified by MC/HEX column, and the filtrate was concentrated under reduced pressure to obtain 6.61 g (80%) of the target compound 3-79.

In the preparation of compound 3-79 of Preparation Example 7, 5,7-diphenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborenyl)-5,7- Intermediate C-1 in Table 9 below instead of dihydroindolo[2,3-b]carbazole, and Intermediate D-1 in place of 3-bromo-9-phenyl-carbazole, in Preparation Example 7 The target compound C was synthesized by the same method as the preparation of compound 3-79.

The heterocyclic compound of Formula 1, the heterocyclic compound of Formula 2, and the heterocyclic compound of Formula 3 other than the above Preparation Example were also prepared. Synthesis confirmation data of the compounds prepared above are as described in [Table 10] to [Table 13].

< Experimental Example 1> Fabrication of organic light emitting device

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

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

The emissive layer was thermally vacuum-deposited as follows. As a host, a light emitting layer was pre-mixed with one species of the compound of Formula 1 and one of the compounds of Formula 2 or Formula 3 as a host, and then deposited 400 에서 in one park, and the green phosphorescent dopant had Ir(ppy) ₃ of 7%. Deposited by doping. Subsequently, 60 B of BCP was deposited as a hole blocking layer, and Alq ₃ was deposited thereon as an electron transport layer. Was deposited at 200 Pa. 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) negative electrode is deposited on the electron injection layer to a thickness of 1,200 유기 to form a cathode. An electroluminescent device was prepared.

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

The organic light emitting device of the present invention includes a host and a light emitting layer using a phosphorescent dopant, and the host is composed of a host compound (pn type) in which two or more compounds are mixed, and thus includes a host compound composed of a conventional single compound It has the effect of having a longer life characteristics than the organic light emitting device.

Particularly, in the case of the pn type host of the present invention, there is an advantage that the light emission characteristics can be increased by controlling the ratio of the host, which can be achieved by an appropriate combination of a P host having good hole mobility and an n host having good electron mobility. to be.

In addition, in the present invention, the light-emitting host composed of a plurality of compounds was deposited by pre-mixing the compounds and then forming them as one deposition source. At this time, since multiple depositions are not performed, the uniformity and thin film properties of the thin film can be improved, the process can be simplified, the cost can be reduced, and the device with improved efficiency and lifetime can be formed.

Particularly, Comparative Examples 8 to 22 of Table 14 are used when the compounds corresponding to Formulas 1 to 3 of the present application are used alone in the organic light emitting device, and correspond to Formula 1 and Formula 2 or Formula 1 and Formula 3 herein. It was confirmed that the compound to be used was not at the same time as the organic light-emitting device, and the efficiency was not particularly good.

In the case of Comparative Examples 1 to 7 of Table 14, two types of heterocycles were used as the light emitting layer of the organic light emitting device, but the compounds not corresponding to the heterocyclic compounds of Formula 1 and the heterocyclic compounds of Formula 2 or 3 herein were used. Comparative examples are shown in the case of using (Comparative Examples 1 to 3) and the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 or 3 herein (Comparative Examples 4 to 7).

Specifically, when there is no substituent of N-het of Formula 1 of the present application, such as the compound used as the light emitting layer of Comparative Examples 1 and 2 in Table 14, electron mobility is lowered, and the balance of holes and electrons in the light emitting layer is broken, and the life is reduced. Could confirm.

When the carbazole structure and the N-het structure are respectively bonded to each of the benzene rings of the dibenzothiophene of Chemical Formula 1, as the compound used as the light emitting layer of Comparative Example 3 in Table 14, the distance between HTU and ETU As it was increased, charge transfer was reduced, and band gap (bang gap) was increased to confirm that inappropriate HOMO and LUMO levels were formed.

When the heterocyclic compound of Formula 1 and biscarbazole are used together in the organic light emitting device, such as the compound used as the light emitting layer of Comparative Examples 4 to 7 in Table 14, when the compound of Formula 2 or 3 is used Compared to this, it was confirmed that the hole mobility was lowered, and the balance between holes and electrons was broken, and the life was reduced.

Compounds 2-1 and 2-12 of Formula 2 herein can be confirmed that benzene and dibenzothiophene are respectively bonded to the 4th position of dibenzofuran. In the 2-12 compound, dibenzofuran and dibenzothiophene are delocalized with LUMO orbital, and it can be seen that this effectively stabilizes electrons than the 2-1 compound.

In the 3-1, 3-77, and 3-79 compounds of Chemical Formula 3 herein, hydrogen, benzene, and carbazole are respectively bonded to the 2nd position of indolocarbazole. It was confirmed that the 3-79 compound effectively stabilizes holes by delocalizing the HOMO orbital by combining carbazole at position 2 of indolocarbazole. On the other hand, the benzene of the 3-77 compound has less orbital delocalization than the carbazole, and the 3-1 compound is localized only to indolocarbazole. In addition, it was confirmed that the molecular weight increased and the thermal stability increased in the order of 3-1, 3-77, 3-79.

100: substrate
200: anode
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 (20)

An organic light emitting device including a first electrode, a second electrode, and one or more organic material layers provided between the first and second electrodes,
At least one layer of the organic material layer is a heterocyclic compound represented by Formula 1 below; And a heterocyclic compound represented by the following Chemical Formula 2 or Chemical Formula 3:
[Formula 1]

[Formula 2]

[Formula 3]

In Chemical Formulas 1 to 3,
L1 to L3 are direct bonds; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group, a1, m and p are integers from 1 to 3, and when a1, m and p are 2 or more, the substituents in parentheses are the same or different from each other,
R ₁ to R ₆ , R ₁₀ to R ₁₉ and R ₂₁ to R ₂₉ 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 a substituted or unsubstituted amine 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 substituted or unsubstituted hetero ring, wherein a3 and r are 0. Is an integer from 2 to 2, a4 is an integer from 0 to 3, and when r, a3 and a4 are 2 or more, the substituents in parentheses are the 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 ,
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,
Ar1 is a substituted or unsubstituted heteroaryl group containing at least one N,
Ar3 and Ar4 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, n, q and a2 are integers of 1 or more and 5 or less, and when n, q and a2 are 2 or more, the substituents in parentheses are the same or different from each other,
Ar2 is represented by the following formula 1-1 or 1-2,
[Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2,
Y1 to Y4 are the same as or different from each other, and each independently an optionally substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted aromatic heterocycle,
R ₇ 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 substituted or unsubstituted amine groups. The method according to claim 1, wherein the formula 1 is an organic light emitting device represented by the following formula 4 or 5:
[Formula 4]

[Formula 5]

In Chemical Formulas 4 and 5,
The definitions of R ₁ to R ₆ , L1, L2, Ar1, p, m and n are the same as those in Formula 1,
R ₅₂ to R ₅₄ 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 a substituted or unsubstituted amine 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 substituted or unsubstituted hetero ring,
i is an integer from 0 to 8,
j is an integer from 0 to 7. The method according to claim 1, wherein the formula 1-1 is an organic light emitting device represented by any one of the following structural formula:

In the structural formula, X1 to X6 are the same as or different from each other, and each independently NR ₃₈ , S, O or CR ₃₉ R ₄₀ ,
R ₃₁ to R ₃₇ 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 a substituted or unsubstituted amine 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 substituted or unsubstituted hetero ring,
a is an integer from 0 to 8, b, c, d, e, f and g are each independently an integer from 0 to 6, and when a, b, c, d, e, f and g are integers of 2 or more, parentheses My substituents are the same or different from each other,
R ₃₈ to R ₄₀ are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group. The method according to claim 1, wherein the formula 1-2 is an organic light emitting device represented by any one of the following structural formula:

In the structural formula, X7 to X12 are the same as or different from each other, and each independently NR ₄₉ , S, O, or CR ₅₀ R ₅₁ ,
R ₄₁ to R ₄₈ 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 a substituted or unsubstituted amine 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 substituted or unsubstituted hetero ring,
h is an integer from 0 to 7, and when h is an integer of 2 or more, the substituents in parentheses are the same or different from each other,
R ₄₉ to R ₅₁ are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group. The method according to claim 1, wherein Ar1 is a substituted or unsubstituted, C2 to C40 heteroaryl group containing at least one N is an organic light-emitting device. The method according to claim 1, wherein the formula 2 is an organic light emitting device represented by the following formula 2-1:
[Formula 2-1]

In Chemical Formula 2-1,
The definitions of R ₁₀ to R ₁₉ , L3, Ar3, Ar4 and a1 to a4 are the same as those in the formula (2). The method according to claim 1, wherein Ar3 is a substituted or unsubstituted aryl group, or an organic light emitting device represented by the following formula 2-1-1 or 2-1-2:
[Formula 2-1-1]

[Formula 2-1-2]

In the above formula 2-1-1 and 2-1-2,
R ₆₁ to R ₆₈ 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 a substituted or unsubstituted amine 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 substituted or unsubstituted hetero ring,
A ₄ is O; S; Or NR ₆₉ ,
R ₆₉ is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group. The method according to claim 1, wherein the formula 3 is an organic light-emitting device represented by any one of the following formula 3-7 to 3-9:
[Formula 3-7]

[Formula 3-8]

[Formula 3-9]

In Chemical Formulas 3-7 to 3-9,
The definitions of A ₁ , A ₂ , R ₂₁ , and R ₂₄ are the same as those in Formula 3,
A ₃ is O; S; Or NR _g ,
R ₇₀ and R ₇₁ are hydrogen; Or a substituted or unsubstituted aryl group, at least one is a substituted or unsubstituted aryl group,
R _g , R ₇₂ and R ₇₃ 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,
o is an integer from 0 to 3,
l is an integer from 0 to 4. The method according to claim 1, R ₂₁ and R ₂₄ to R ₂₉ of the formula (3) is an organic light emitting device that is hydrogen. The method according to claim 1, wherein the formula 1 is an organic light emitting device represented by any one of the following compounds:

The method according to claim 1, wherein the formula 2 is an organic light-emitting device represented by any one of the following compounds:

The method according to claim 1, wherein the formula 3 is an organic light emitting device represented by any one of the following compounds:

The method according to claim 1, The organic layer includes at least one layer of the hole blocking layer, the electron injection layer and the electron transport layer, the at least one layer of the hole blocking layer, the electron injection layer and the electron transport layer is a heterocyclic ring represented by the formula (1) compound; And a heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3. The method according to claim 1, The organic layer includes a light emitting layer, The light emitting layer is a heterocyclic compound represented by the formula (1); And a heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3. The method according to claim 1, wherein the organic layer includes a light emitting layer, the light emitting layer includes a host material, the host material is a heterocyclic compound represented by the formula (1); And a heterocyclic compound represented by Chemical Formula 2 or Chemical Formula 3. The method according to claim 1, 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 two 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 heterocyclic compound represented by Formula 1 below; And a heterocyclic compound represented by the following Chemical Formula 2 or Chemical Formula 3:
[Formula 1]

[Formula 2]

[Formula 3]

In Chemical Formulas 1 to 3,
L1 to L3 are direct bonds; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group, a1, m and p are integers from 1 to 3, and when a1, m and p are 2 or more, the substituents in parentheses are the same or different from each other,
R ₁ to R ₆ , R ₁₀ to R ₁₉ and R ₂₁ to R ₂₉ 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 a substituted or unsubstituted amine 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 substituted or unsubstituted hetero ring, wherein a3 and r are 0. Is an integer from 2 to 2, a4 is an integer from 0 to 3, and when r, a3 and a4 are 2 or more, the substituents in parentheses are the 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 ,
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,
Ar1 is a substituted or unsubstituted heteroaryl group containing at least one N,
Ar3 and Ar4 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, n, q and a2 are integers of 1 or more and 5 or less, and when n, q and a2 are 2 or more, the substituents in parentheses are the same or different from each other,
Ar2 is represented by the following formula 1-1 or 1-2,
[Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2,
Y1 to Y4 are the same as or different from each other, and each independently an optionally substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted aromatic heterocycle,
R ₇ 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 substituted or unsubstituted amine groups. The method according to claim 17, wherein the heterocyclic compound represented by the formula (1) in the composition: the weight ratio of the heterocyclic compound represented by the formula (2) or (3) is 1: 10 to 10: 1 for the organic material layer of the organic light emitting device Composition. Preparing a substrate;
Forming a first electrode on the substrate;
Forming one or more organic material layers on the first electrode; And
And forming a second electrode on the organic material layer,
The step of forming the organic material layer comprises forming one or more organic material layers using the composition for an organic material layer according to claim 17. The method according to claim 19, The step of forming the organic layer is a heterocyclic compound of Formula 1; And pre-mixing the heterocyclic compound represented by Chemical Formula 2 or the heterocyclic compound represented by Chemical Formula 3 by using a thermal vacuum deposition method.

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