TW202031646A - Organic light emitting device, manufacturing method of the same and composition for organic material layer of organic light emitting device - Google Patents

Abstract

The present specification relates to an organic light emitting device, a method for manufacturing the same, and a composition for an organic material layer of the organic light emitting device. The organic light emitting device comprising: a first electrode; a second electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein the one or more organic material layers comprise a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2 at the same time. In Chemical Formula 1 and Chemical Formula 2, the definition of each substituents is the same as in the detailed description.

Description

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

This specification is about an organic light-emitting device, a method for manufacturing an organic light-emitting device, and a composition for an organic material layer.

An electroluminescent (EL) device is a self-luminous display device, and has the advantages of wide viewing angle, high response speed, and excellent contrast.

An organic light emitting device has a structure in which an organic thin film is arranged between two electrodes. When a voltage is applied to the organic light-emitting device having such a structure, the electrons and holes injected from the two electrodes are connected to form a pair in the organic thin film, and when the electrons and holes are annihilated, light will be emitted. The organic film may be formed in a single layer or multiple layers as needed.

The material of the organic thin film may have a light-emitting function if necessary. For example, as the material of the organic thin film, only a compound capable of forming a light-emitting layer may be used, or a compound capable of functioning as a host or dopant of the light-emitting layer based on a host dopant may also be used. In addition, compounds that can play the role of hole injection, hole transfer, electron blocking, hole blocking, electron transfer, electron injection, etc. can also be used as materials for organic thin films.

In order to enhance the effectiveness, lifespan, or efficiency of organic light-emitting devices, there is a constant need to develop organic thin-film materials. [Prior Technical Document] [Patent Document] U.S. Patent No. 4,356,429

[technical problem] This application relates to an organic light-emitting device, a method for manufacturing an organic light-emitting device, and a composition for an organic material layer.

[化學式2]

[Technical Solution] An embodiment of the present application provides an organic light-emitting device, the organic light-emitting device comprising: a first electrode; a second electrode; and one or more organic material layers disposed on the first electrode and Between the second electrodes, one or more of the organic material layers include a heterocyclic compound represented by the following Chemical Formula 1 and a heterocyclic compound represented by the following Chemical Formula 2. [Chemical formula 1]

[Chemical formula 2]

In Chemical Formula 1 and Chemical Formula 2, N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclic group, and includes one or more N, L is a direct bond; substituted or unsubstituted aromatic Group; or substituted or unsubstituted heteroaryl group, a is an integer from 1 to 3, and when a is 2 or more than 2, L is the same or different from each other, and R ₁ to R ₁₉ are the same or different from each other , And each independently selected from the group consisting of: hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkyne Substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted A substituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted A substituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted heterocyclic ring, b and c are each an integer from 1 to 3, d is an integer from 0 to 2, and when b is 2 or greater than 2, R _{9 is the} same or different from each other, when c is 2 or greater than 2, R _{10 is the} same or different from each other, and when d is an integer 2, R _{19 is the} same or different from each other, A ₁ and A ₂ are the same or different from each other different and are each independently O; S; NR _a; or CR _b R _c, and R _a to R _c are the same or different from each other, and each independently hydrogen; substituted or unsubstituted alkyl group; by A substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.

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

Finally, an embodiment of the present application provides a method for manufacturing an organic light-emitting device, the method includes: preparing a substrate; forming a first electrode on the substrate; and forming one or more An organic material layer; and forming a second electrode on the organic material layer, wherein the forming the organic material layer includes forming one or more organic materials using the composition for an organic material layer according to an embodiment of the present application Floor.

[Beneficial effect] The heterocyclic compound according to an embodiment of the present application may be used as a material of an organic material layer of an organic light-emitting device. The heterocyclic compound can be used as a material for a hole injection layer, a hole transfer layer, a light emitting layer, an electron transfer layer, an electron injection layer, a charge generation layer, etc. in an organic light emitting device. Specifically, the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 may be simultaneously used as the material of 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 are used in the organic light emitting device at the same time, the driving voltage of the device can be reduced, the light efficiency can be improved, and the thermal stability of the compound can be improved. To improve the life of the device.

Specifically, in the heterocyclic compound represented by Chemical Formula 1, the carbon position 3 of the dibenzofuran structure is substituted with an N-containing ring and the benzene in the dibenzofuran structure that is not substituted with the N-containing ring is carbazole The structure is replaced, and an electronically more stable structure is obtained, and therefore, the device life can be improved.

In the following, this application will be explained in detail.

The term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is changed to another substituent, and the substitution position is not limited, as long as it is the position where the hydrogen atom is substituted (that is, the substituent can be substituted Position) is sufficient, and when two or more substituents are substituted, the two or more substituents may be the same as or different from each other.

In the present specification, "substituted or unsubstituted" means selected from C1 to C60 linear or branched chain alkyl; C2 to C60 linear or branched alkenyl; C2 to C60 straight Chain or branched alkynyl; C3 to C60 monocyclic or polycyclic cycloalkyl; C2 to C60 monocyclic or polycyclic heterocycloalkyl; C6 to C60 monocyclic or polycyclic aryl; C2 to C60 monocyclic or polycyclic Cyclic heteroaryl; -SiRR'R''; -P(=O)RR'; C1 to C20 alkylamine; C6 to C60 monocyclic or polycyclic arylamine; and C2 to C60 monocyclic or polycyclic hetero One or more substituents of the group consisting of arylamines are substituted or unsubstituted, or substituted or unsubstituted by substituents linked to two or more substituents selected from the substituents shown above. R, R', and R" are the same as or different from each other, and are each independently hydrogen; deuterium; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or Unsubstituted aryl; or substituted or unsubstituted heteroaryl.

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

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

In the present specification, the alkyl group includes a straight or branched chain alkyl group having 1 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples of alkyl groups may include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tertiary butyl, second butyl, 1-methyl- Butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl , Octyl, n-octyl, third octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl Propyl, 1,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but not limited thereto.

In the present specification, the alkenyl group includes linear or branched alkenyl groups having 2 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkenyl group may be 2 to 60, specifically 2 to 40, and more specifically 2 to 20. Specific examples of alkenyl groups may include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3 -Pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl , 2,2-Diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl) ) Vinyl-1-yl, distyryl, styryl, etc., but not limited thereto.

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

In this specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but it is preferably 1-20. Specific examples of alkoxy groups may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tertiary butoxy, second butoxy, n-pentoxy Oxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octyloxy, n-nonyloxy, n-decyloxy , Benzyloxy, p-methylbenzyloxy, etc., but not limited thereto.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic cycloalkyl group having 3 to 60 carbon atoms, and may be further substituted with other substituents. In this context, polycyclic means a group in which a cycloalkyl group is directly linked to or fused with another cyclic group. In this context, other cyclic groups may be cycloalkyl groups, but may also be different types of cyclic groups such as heterocycloalkyl groups, aryl groups, and heteroaryl groups. The number of carbon groups of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specific examples of cycloalkyl groups may include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4 -Methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tertiarybutylcyclohexyl, cycloheptyl, cyclooctyl, etc., but not limited to these .

In the present specification, the heterocycloalkyl group includes O, S, Se, N, or Si as a heteroatom, includes a monocyclic or polycyclic heterocycloalkyl group having 2 to 60 carbon atoms, and may be further substituted by other substituents. replace. In this context, polycyclic means a group in which a heterocycloalkyl group is directly connected to or fused with another cyclic group. In this context, other cyclic groups may be heterocycloalkyl groups, but may also be different types of cyclic groups such as cycloalkyl groups, aryl groups, and heteroaryl groups. The number of carbon atoms of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.

In the present specification, the aryl group includes a monocyclic or polycyclic aryl group having 6 to 60 carbon atoms, and may be further substituted with other substituents. In this context, polycyclic means a group in which an aryl group is directly linked to or fused with other cyclic groups. In this context, other cyclic groups may be aryl groups, but may also be different types of cyclic groups such as cycloalkyl, heterocycloalkyl, and heteroaryl. Aryl groups include spiro groups. 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 aryl groups may include phenyl, biphenyl, triphenyl, naphthyl, anthracenyl, phenanthryl, perylene, anthracenyl, triphenylene, pyrenyl, pyrenyl Phenyl, fused pentaphenyl, fluorenyl, indenyl, acenaphthylene, benzofluorenyl, spirobifluorenyl, 2,3-dihydro-1H-indenyl, its fused ring, etc., but not limited thereto.

In this specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

、

、

、

、

、

等，然而，所述結構不限於此。When the fluorenyl group is substituted, it can include

,

,

,

,

,

Etc. However, the structure is not limited to this.

In the present specification, the heteroaryl group includes O, S, Se, N, or Si as a heteroatom, includes a monocyclic or polycyclic heteroaryl group having 2 to 60 carbon atoms, and may be further substituted with other substituents. In this context, polycyclic means a group in which a heteroaryl group is directly linked to or fused with other cyclic groups. In this context, other cyclic groups may be heteroaryl groups, but may also be different types of cyclic groups such as cycloalkyl, heterocycloalkyl, and aryl. The number of carbon atoms of the heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of heteroaryl groups may include pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, Triazolyl, furyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl, azazinyl, thiazinyl, dioxane Dioxynyl group, triazinyl group, tetrazinyl group, quinolinyl, isoquinolinyl, quinazolinyl, isoquinazolinyl, quinazinyl group (qninozolinyl) group), naphthyridyl group, acridinyl group, phenanthridinyl group, imidazopyridinyl group, diazanaphthalenyl group, triazindanyl group, indolyl group, indole Azinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl, carbazolyl, benzocarbazolyl , Dibenzocarbazolyl, phenazinyl, dibenzosilole group, spirobi (dibenzosilole), dihydrophenazinyl, phenazinyl, Phenanthridyl group, imidazopyridyl, thienyl, indolo[2,3-a]carbazolyl, indolo[2,3-b]carbazolyl, indolinyl, 10 ,11-Dihydrodibenzo[b,f]azinyl, 9,10-dihydroacridinyl, phenanthrazinyl group, phenanthrazinyl, piperazinyl, naphthyridinyl, phenanthroline Phenanthrolinyl group, benzo[c][1,2,5]thiadiazolyl, 5,10-dihydrobenzo[b,e][1,4]azasilinyl group (5, 10-dihydrobenzo[b,e][1,4]azasilinyl), pyrazolo[1,5-c]quinazolinyl, pyrido[1,2-b]indolyl, pyrido[1,2 -a]imidazo[1,2-e]indolyl, 5,11-dihydroindeno[1,2-b]carbazolyl, etc., but not limited thereto.

In this specification, the amine group can be selected from the group consisting of: monoalkylamino group; monoarylamino group; monoheteroarylamino group; -NH ₂ ; dialkylamino group; diarylamino group ; Diheteroarylamine group; Alkylarylamino group; Alkylheteroarylamine group; and arylheteroarylamine group, and although not particularly limited thereto, the number of carbon atoms is preferably 1 to 30. Specific examples of the amino group may include methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, naphthylamino, biphenylamino, diphenylamine Group, anthrylamino group, 9-methyl-anthrylamino group, diphenylamino group, phenylnaphthylamino group, xylylamino group, phenyltolylamino group, triphenylamino group, biphenyl Phenyl naphthyl amino group, phenyl biphenyl amino group, biphenyl fluorenyl amino group, phenyl terphenyl amino group, biphenyl terphenyl amino group, etc., but not limited thereto.

In this specification, an aryl group means an aryl group having two bonding sites, that is, a divalent group. The description of the aryl group provided above can be applied to the aryl group, except for the divalent ones. In addition, the heteroaryl group means a heteroaryl group having two bonding sites, that is, a divalent group. The descriptions of heteroaryl groups provided above can be applied to heteroaryl groups, except for the divalent ones.

In this specification, the phosphine oxide group is represented by -P(=O)R ₁₀₁ R ₁₀₂ , and R ₁₀₁ and R ₁₀₂ are the same as or different from each other, and may each independently be a substituent formed by at least one of the following : Hydrogen; deuterium; halogen; alkyl; alkenyl; alkoxy; cycloalkyl; aryl; and heterocyclic group. Specifically, the phosphine oxide group may be specifically substituted with an aryl group, and as the aryl group, the above-mentioned examples can be used. Examples of the phosphine oxide group may include a diphenyl phosphine oxide group, a dinaphthyl phosphine oxide group, etc., but are not limited thereto.

In this specification, a silyl group is a substituent including Si, has a Si atom directly connected as a radical, and is represented by -SiR ₁₀₄ R ₁₀₅ R ₁₀₆ . R ₁₀₄ to R ₁₀₆ are the same as or different from each other, and may each independently be a substituent formed by at least one of the following: hydrogen; deuterium; halogen; alkyl; alkenyl; alkoxy; cycloalkyl; Aryl; and heterocyclic group. Specific examples of the silyl group may include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl , Diphenylsilyl, phenylsilyl, etc., but not limited to these.

In this specification, the "adjacent" group may mean a substituent that replaces the atom directly connected to the atom substituted by the corresponding substituent, the substituent closest to the corresponding substituent in space, or the substitution is substituted by the corresponding substituent Another substituent of the atom. For example, two substituents substituted for the ortho position in the benzene ring and two substituents substituted for the same carbon in the aliphatic ring can be interpreted as groups "adjacent" to each other.

As the aliphatic or aromatic hydrocarbon ring or heterocyclic ring that can be formed by adjacent groups, the structures described above as cycloalkyl, cycloheteroalkyl, aryl and heteroaryl can be used, except for non-monovalent ones .

An embodiment of the present application provides an organic light-emitting device, the organic light-emitting device comprising: a first electrode; a second electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein One or more organic material layers include the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2.

[化學式4]

[化學式5]

[化學式6]

In an embodiment of the present application, Chemical Formula 1 may be represented by any one of the following Chemical Formula 3 to Chemical Formula 6. [Chemical formula 3]

[Chemical formula 4]

[Chemical formula 5]

[Chemical formula 6]

In Chemical Formula 3 to Chemical Formula 6, The substituent has the same definition as that in Chemical Formula 1.

In one embodiment of this application, N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclic ring, and includes one or more N.

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

In another embodiment, N-Het is unsubstituted or selected from the group consisting of phenyl, biphenyl, naphthyl, dimethylfluorenyl, dibenzofuranyl and dibenzothienyl A monocyclic or polycyclic heterocyclic ring substituted by one or more substituents of and including one or more N.

In another embodiment, N-Het is unsubstituted or selected from the group consisting of phenyl, biphenyl, naphthyl, dimethylfluorenyl, dibenzofuranyl and dibenzothienyl A monocyclic or polycyclic heterocyclic ring substituted by one or more substituents of and includes one or more N and includes three or less N.

In one embodiment of this application, N-Het is a substituted or unsubstituted monocyclic heterocyclic ring, and includes one or more N.

In an embodiment of the present application, N-Het is a substituted or unsubstituted divalent or higher valent heterocyclic ring, and includes one or more N.

In an embodiment of this application, N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclic ring, and includes two or more Ns.

In one embodiment of the present application, N-Het is a divalent or higher polycyclic heterocyclic ring including two or more Ns.

In an embodiment of this application, N-Het can be unsubstituted or substituted with phenyl pyrimidinyl; unsubstituted or selected from phenyl, biphenyl, naphthyl, dimethylfluorenyl, Triazinyl substituted with one or more substituents of the group consisting of dibenzofuranyl and dibenzothienyl; unsubstituted or benzimidazolyl substituted with phenyl; unsubstituted or selected from benzene Quinolinyl substituted with one or more substituents of the group consisting of phenyl and biphenyl; or phenanthroline substituted with phenyl or unsubstituted.

[化學式8]

[化學式9]

In an embodiment of the present application, Chemical Formula 1 is represented by one of the following Chemical Formula 7 to Chemical Formula 9. [Chemical formula 7]

[Chemical formula 8]

[Chemical formula 9]

In Chemical Formula 7 to Chemical Formula 9, R1 to R10, L, a, b, and c have the same definitions as those in Chemical Formula 1, X1 is CR21 or N, X2 is CR22 or N, X3 is CR23 or N, X4 is CR24 or N, and X5 is CR25 or N, and R21 to R25 and R27 to R32 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted Alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted Or unsubstituted aryl; substituted or unsubstituted heteroaryl; substituted or unsubstituted phosphine oxide group; and substituted or unsubstituted amine group, or two or more adjacent to each other The groups are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or heterocyclic ring.

可由以下化學式10至化學式12中的一者表示。在本文中，

為聯結至L的位點。 [化學式10]

[化學式11]

[化學式12]

In an embodiment of this application,

It can be represented by one of the following Chemical Formula 10 to Chemical Formula 12. in the text,

It is the site of attachment to L. [Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12]

In Chemical Formula 10, one or more of X1, X3, and X5 is N, and the rest have the same definition as in Chemical Formula 7, In Chemical Formula 11, one or more of X1, X2, and X5 is N, and the rest have the same definition as in Chemical Formula 7, In Chemical Formula 12, one or more of X1 to X3 is N, and the rest have the same definition as in Chemical Formula 7, and R22, R24, and R33 to R36 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted Alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted Or unsubstituted aryl; substituted or unsubstituted heteroaryl; substituted or unsubstituted phosphine oxide group; and substituted or unsubstituted amine group, or two or more adjacent to each other The groups are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or heterocyclic ring.

In an embodiment of the present application, the chemical formula 10 can be selected from the following structural formulae.

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

In an embodiment of the present application, Chemical Formula 11 may be represented by Chemical Formula 13 below. [Chemical formula 13]

The substituent in Chemical Formula 13 has the same definition as that in Chemical Formula 11.

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

The substituent in Chemical Formula 14 has the same definition as that in Chemical Formula 12.

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

In chemical formula 15, R37 is the same or different from each other and is selected from the group consisting of hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted Substituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; A substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a A substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or heterocyclic ring, e is an integer from 0 to 7, and when e is 2 or more than 2, R37 are the same as or different from each other.

In an embodiment of the application, L is a direct bond or an aryl group.

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

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

In another embodiment, R9 and R10 are hydrogen.

In one embodiment of this application, R1 to R8 are hydrogen; deuterium; unsubstituted or substituted by alkyl, aryl or heteroaryl; or unsubstituted or substituted by aryl or heteroaryl Group substituted heteroaryl.

In another embodiment, R1 to R8 are hydrogen; deuterium; aryl; heteroaryl; or heteroaryl substituted with aryl.

In another embodiment, R1 to R8 are hydrogen; deuterium; phenyl; dibenzofuranyl; dibenzothienyl; carbazolyl; or carbazolyl substituted with phenyl.

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

In another embodiment, two or more adjacent substituents among R1 to R8 are bonded to each other to form an unsubstituted or aryl or alkyl substituted ring.

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

In another embodiment, two or more adjacent substituents in R1 to R8 are bonded to each other to form an aromatic hydrocarbon ring or heterocyclic ring which is unsubstituted or substituted with phenyl or methyl.

In another embodiment, two or more adjacent substituents in R1 to R8 are bonded to each other to form an unsubstituted or substituted indole ring with a phenyl group; a benzothiophene ring; a benzofuran ring; Or unsubstituted or methyl substituted indene ring.

可由以下化學式16表示。在本文中，

為聯結至二苯並呋喃結構的位點。 [化學式16]

In another embodiment,

It can be represented by the following Chemical Formula 16. in the text,

It is the site of attachment to the dibenzofuran structure. [Chemical formula 16]

In Chemical Formula 16, R1 to R4 have the chemical formula 1 defined in the same defined, Y is the same or different O, S, NR _d or _{CR e R f, R d,} R e, R f, R41 and R42 each other , And each independently selected from the group consisting of: hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkyne Substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted A substituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted A substituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted heterocyclic ring, f is an integer from 0 to 4, and when f is 2 or more than 2, R41 is the same or different from each other, and g is 0 to An integer of 2, and when g is 2 or greater, R42 is the same as or different from each other.

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

In the structural formula, The substituent has the same definition as that in Chemical Formula 16.

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

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

In another embodiment, R28 to R31 are hydrogen.

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

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

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

In another embodiment, R27 and R32 are phenyl.

In an embodiment of the present application, R21 to R25 are the same as or different from each other, and are each independently hydrogen; deuterium; unsubstituted or substituted aryl groups; or substituted or unsubstituted hetero Aryl.

In another embodiment, R21 to R25 are the same as or different from each other, and are each independently hydrogen; deuterium; unsubstituted or substituted with alkyl groups; or heteroaryl groups.

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

In another embodiment, R21 to R25 are the same as or different from each other, and are each independently hydrogen; phenyl; biphenyl; naphthyl; dimethylfluorenyl; dibenzofuranyl; or dibenzothiophene base.

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

In another embodiment, R22 and R24 are the same or different from each other, and are each independently phenyl, biphenyl, naphthyl, dimethylfluorenyl; dibenzofuranyl; or dibenzothienyl.

In an embodiment of the present application, R33 to R36 are the same as or different from each other, and are each independently hydrogen; deuterium; aryl; or heteroaryl, or two or more groups adjacent to each other are bonded to each other Together to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or heterocyclic ring.

In another embodiment, R33 to R36 are the same as or different from each other, and are each independently hydrogen; deuterium; or aryl group, or two or more groups adjacent to each other are bonded to each other to form aliphatic or aromatic Group hydrocarbon ring or heterocyclic ring.

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

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

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

In an embodiment of this application, R37 is hydrogen; deuterium; aryl; or heteroaryl.

In another embodiment, R37 is hydrogen; deuterium; or aryl.

In another embodiment, R37 is hydrogen; or aryl.

In another embodiment, R37 is hydrogen; or phenyl.

In an embodiment of this application, Y is O or S.

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

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

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

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

In an embodiment of this application, R41 is hydrogen; deuterium; aryl; or heteroaryl.

In another embodiment, R41 is hydrogen; deuterium; or aryl.

In another embodiment, R41 is hydrogen; or phenyl.

In an embodiment of this application, R42 is hydrogen; or deuterium.

In another embodiment, R42 is hydrogen.

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

In one embodiment of the present application embodiment, R _a to R _c identical or different from each other, and each independently hydrogen; substituted or unsubstituted C1 to C60 alkyl; substituted or unsubstituted C6 To C60 aryl; or substituted or unsubstituted C2 to C60 heteroaryl.

In another embodiment, R _a to R _c are the same as or different from each other, and may each independently be hydrogen; substituted or unsubstituted C1 to C40 alkyl; substituted or unsubstituted C6 to C40 aryl Group; or substituted or unsubstituted C2 to C40 heteroaryl.

In another embodiment, R _a to R _c identical or different from each other, and each independently hydrogen; C1 to C40 alkyl; unsubstituted or is selected from the group consisting of C1 to C40 alkyl, C6 to C40 aryl A C6 to C40 aryl group substituted with one or more substituents of the group consisting of a phenyl group and a triphenylsilyl group; or a C2 to C40 heteroaryl group that is unsubstituted or substituted with a C6 to C40 aryl group.

In another embodiment, R _a to R _c are the same or different from each other, and may each independently be a methyl group; unsubstituted or selected from the group consisting of phenyl and triphenylsilyl group; Phenyl substituted with multiple substituents; biphenyl unsubstituted or substituted by phenyl; naphthyl; terphenylene; diphenylfluorenyl; dimethylfluorenyl; unsubstituted or benzene Group-substituted carbazolyl; dibenzofuranyl; or dibenzothienyl.

In an embodiment of the present application, R ₁₁ to R ₁₉ are the same as or different from each other, and are each independently selected from the group consisting of hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkane Group; substituted or unsubstituted alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted Substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; substituted or unsubstituted phosphine oxide group; and substituted or unsubstituted amine group, or Two or more groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.

In another embodiment, R ₁₁ to R ₁₉ are the same as or different from each other, and may each independently be hydrogen; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl.

In another embodiment, R ₁₁ to R ₁₉ are the same as or different from each other, and may be each independently hydrogen; substituted or unsubstituted C6 to C60 aryl; or substituted or unsubstituted C2 to C60 Heteroaryl.

In another embodiment, R ₁₁ to R ₁₉ are the same as or different from each other, and may be each independently hydrogen; substituted or unsubstituted C6 to C40 aryl; or substituted or unsubstituted C2 to C40 Heteroaryl.

In another embodiment, R ₁₁ to R ₁₉ are the same as or different from each other, and may be each independently hydrogen; C6 to C40 aryl; or C2 to C40 heterocyclic which is unsubstituted or substituted with C6 to C40 aryl. Aryl.

In another embodiment, R ₁₁ to R ₁₉ are the same as or different from each other, and may each independently be hydrogen; phenyl; trimethylene; carbazole that is unsubstituted or substituted with phenyl or biphenyl Group; dibenzofuranyl; or dibenzothienyl.

In an embodiment of the present application, R ₁₅ to R ₁₉ may be hydrogen.

In an embodiment of the present application, R ₁₁ and R ₁₄ may be hydrogen.

In an embodiment of the present application, R ₁₁ and R ₁₄ to R ₁₉ may be hydrogen.

In an embodiment of the present application, R ₁₂ and R ₁₃ are the same as or different from each other, and can be each independently hydrogen; phenyl; trimethylene; unsubstituted or substituted by phenyl or biphenyl的carbazolyl; dibenzofuranyl; or dibenzothienyl.

[化學式2-2]

[化學式2-3]

[化學式2-4]

[化學式2-5]

[化學式2-6]

In an embodiment of the present application, Chemical Formula 2 may be represented by any of the following Chemical Formula 2-1 to Chemical Formula 2-6. [Chemical formula 2-1]

[Chemical formula 2-2]

[Chemical formula 2-3]

[Chemical formula 2-4]

[Chemical formula 2-5]

[Chemical formula 2-6]

In Chemical Formula 2-1 to Chemical Formula 2-6, R ₁₁ to R ₁₉ , A ₁ , A ₂ and d have the same definitions as those in Chemical Formula 2.

[化學式2-8]

[化學式2-9]

In an embodiment of the present application, Chemical Formula 2 can be represented by any of the following Chemical Formulas 2-7 to 2-9. [Chemical formula 2-7]

[Chemical formula 2-8]

[Chemical formula 2-9]

In Chemical Formula 2-7 to Chemical Formula 2-9, A ₁ , A ₂ , R ₁₁ and R ₁₄ have the same definitions as in Chemical Formula 2, and A ₃ is O; S; or NR _g , R ₅₀ and R ₅₁ Is hydrogen; or a substituted or unsubstituted aryl group, and at least one of R ₅₀ and R ₅₁ is a substituted or unsubstituted aryl group, R _g , R ₅₂ and R ₅₃ are the same or different from each other, And each independently is hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl, r is an integer from 0 to 3, and q is An integer from 0 to 4.

In an embodiment of the present application, R ₅₀ and R ₅₁ may be hydrogen; or substituted or unsubstituted aryl.

In another embodiment, R ₅₀ and R ₅₁ may be hydrogen; or a substituted or unsubstituted C6 to C60 aryl group.

In another embodiment, R ₅₀ and R ₅₁ may be hydrogen; or a substituted or unsubstituted C6 to C40 aryl group.

In another embodiment, R ₅₀ and R ₅₁ may be hydrogen; or a C6 to C40 aryl group.

In another embodiment, R ₅₀ and R ₅₁ may be hydrogen; phenyl; or trimethylene.

In an embodiment of the present application, at least one of R ₅₀ and R ₅₁ may be a substituted or unsubstituted aryl group.

In an embodiment of the present application, R ₅₂ and R ₅₃ may be hydrogen.

In an embodiment of this application, R _g can be a substituted or unsubstituted aryl group.

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

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

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

In another embodiment, R _g can be phenyl; or biphenyl.

When having a fused-type base ring as in Chemical Formula 2-7, when used with the heterocyclic compound shown in Chemical Formula 1 in an organic light-emitting device, especially as a host material, A very fast hole transfer property is obtained, which reduces the threshold voltage and driving voltage of the device, and therefore, the device can be driven even at low voltage.

When there is a substituent (R ₅₀ ) in the condensed ring structure as in the chemical formula 2-8, a larger structure is obtained compared to the chemical formula 2-7, and due to the property, the conjugate The region becomes wider toward the substituent (R ₅₀ ) extending from the basic skeleton, and a further broadened form of the highest occupied molecular orbital (HOMO) energy level region is obtained. Therefore, holes are distributed to a wide HOMO energy level region, and a more stable hole transfer ability can be maintained. In other words, in the case of chemical formulas 2-8, for example, the driving voltage will be increased to a certain extent, however, more superior overall life properties will be obtained.

Chemical formula 2-9 is a case where the condensed ring structure is substituted by a heteroaryl group, and at the same time, it has the property of maintaining a stable HOMO energy level through a wide conjugation region as in Chemical formula 2-8, so it can be used as Various heteroaryl substitutions are used as auxiliary means to control the band gap. Specifically, because dibenzofuran/dibenzothienyl and the like have the largest structure in terms of structure, the driving voltage is slightly increased compared to the basic skeleton. However, in addition to maintaining a higher T1 energy level, It also has the highest structural stability, so it will obtain particularly superior device life properties.

When both the heterocyclic compound shown in Chemical Formula 1 and the heterocyclic compound shown in Chemical Formula 2 are included in the organic material layer of the organic light-emitting device, superior efficiency and lifetime effects will be obtained. This result may lead to the prediction that when the two compounds are included at the same time, an exciplex phenomenon will occur.

The phenomenon of excited complexes is due to the exchange of electrons between two molecules to release the HOMO energy level of the donor (p-host) and the lowest unoccupied molecular orbital (LUMO) energy level of the acceptor (n-host) The phenomenon of large and small energy. When an excited complex phenomenon occurs between two molecules, reverse intersystem crossing (RISC) occurs, and therefore the internal quantum efficiency of fluorescence can be increased up to 100%. When a donor (p-host) with a desirable hole transfer capability and an acceptor (n-host) with a desirable electron transfer capability are used as the host of the light-emitting layer, holes are injected into the p-host, and electrons It is injected into the n-body, and therefore, the driving voltage can be reduced, which ultimately contributes to the improvement of life.

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

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

In addition, by introducing various substituents into the structures shown in Chemical Formula 1 and Chemical Formula 2, compounds with unique properties of the introduced substituents can be synthesized. For example, by introducing into the core structure substituents commonly used as hole injection layer materials, hole transfer layer materials, light emitting layer materials, electron transfer layer materials, and charge generation layer materials for the manufacture of organic light-emitting devices, synthesis Materials that meet the requirements of each organic material layer.

In addition, by introducing various substituents into the structures shown in Chemical Formula 1 and Chemical Formula 2, the energy band gap can be finely controlled, and at the same time, the properties at the interface between organic materials are enhanced, and material applications can become diversified.

At the same time, heterocyclic compounds have a high glass transition temperature (Tg), and have excellent thermal stability. This increase in thermal stability becomes an important factor in providing driving stability for the device.

The heterocyclic compound according to an embodiment of the present application can be prepared using a multi-step chemical reaction. First, some intermediate compounds are prepared, and the compounds shown in Chemical Formula 1 or Chemical Formula 2 can be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to an embodiment of the present application can be prepared based on the preparation example to be described later.

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

The specific details about the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 are the same as the description provided above.

In the composition, the heterocyclic compound represented by Chemical Formula 1: The compound represented by Chemical Formula 2 may have 1:10 to 10:1, 1:8 to 8:1, 1:5 to 5:1, or 1: A weight ratio of 2 to 2:1, however, the weight ratio is not limited to this.

The composition may be used when forming an organic material of an organic light-emitting device, and specifically, may be more preferably used when forming a main body of the light-emitting layer.

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

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

In addition to using the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 to form one or more organic material layers, the organic light-emitting device according to an embodiment of the present application may use a common organic light-emitting device Manufacturing methods and materials.

When manufacturing an organic light-emitting device, the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 may be formed as an organic material layer by a solution coating method and a vacuum deposition method. In this article, the solution coating method means spin coating, dip coating, inkjet printing, screen priting, spray method, roll coating ( roll coating), but not limited to this.

The organic material layer of the organic light-emitting device of the present disclosure may be formed as a single-layer structure, or may also be formed as a multi-layer structure in which two or more organic material layers are laminated. For example, the organic light emitting device according to an embodiment of the present disclosure may have a structure including a hole injection layer, a hole transfer layer, a light emitting layer, an electron transfer 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, an organic light-emitting device according to an embodiment of the present application includes: a first electrode; a second electrode; and one or more organic material layers disposed between the first electrode and the second electrode, and one or The multilayer organic material layer includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2.

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

In another 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, and the heterocyclic compound according to Chemical Formula 1 and the heterocyclic compound according to Chemical Formula 2 may be used as the material of the 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, and the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 may be used as the material of the 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, and the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 may be used as the material of the red organic light-emitting device.

The organic light-emitting device of the present disclosure may further include one, two or one selected from the group consisting of a light-emitting layer, a hole injection layer, a hole transfer layer, an electron injection layer, an electron transfer layer, an electron blocking layer, and a hole blocking layer. More layers.

In the organic light-emitting device provided in an embodiment of the present application, the organic material layer includes at least one of a hole blocking layer, an electron injection layer, and an electron transfer layer, and the hole blocking layer, the electron injection layer, and the electron transfer layer At least one of the transfer layers includes the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2.

In the organic light emitting device provided in an embodiment of the present application, the organic material layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2.

In the organic light emitting device provided in one 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 includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic ring represented by Chemical Formula 2. Compound.

1 to 3 illustrate the lamination sequence of electrodes and organic material layers of an organic light-emitting device according to an embodiment of the present application. However, the scope of the application is not limited to these drawings, and the structure of the organic light-emitting device known in the art can also be used in the application.

FIG. 1 shows an organic light emitting device in which an anode (200), an organic material layer (300), and a cathode (400) are sequentially laminated on a substrate (100). However, the structure is not limited to this structure, and as shown in FIG. 2, an organic light-emitting device in which a cathode, an organic material layer, and an anode are sequentially laminated on a substrate can also be obtained.

Fig. 3 shows 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 transfer layer (302), a light emitting layer (303), a hole blocking layer (304), an electron transfer layer (305), and an electron injection layer (306) ). However, the scope of the present application is not limited to such a laminated structure, and if necessary, it may not include other layers other than the light-emitting layer, and may further include other necessary functional layers.

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

In the method for manufacturing an organic light-emitting device provided in an embodiment of the present application, the organic material layer is formed after premixing the heterocyclic compound shown in Chemical Formula 1 and the heterocyclic compound shown in Chemical Formula 2. It is formed using a thermal vacuum deposition method.

Pre-mixing means that the material composed of the heterocyclic compound shown in Chemical Formula 1 and the material composed of the heterocyclic compound shown in Chemical Formula 2 are pre-mixed in one supply source before being deposited on the organic material layer.

According to an embodiment of the present application, the pre-mixed material may be referred to as a composition for the organic material layer.

In the organic light-emitting device according to an embodiment of the present application, materials other than the heterocyclic compound shown in Chemical Formula 1 and the heterocyclic compound shown in Chemical Formula 2 are shown below, however, these are only for illustration. The purpose is not to limit the scope of this application, and it can be replaced by materials known in the art.

As the anode material, a material having a relatively large work function can be used, and transparent conductive oxides, metals, conductive polymers, etc. can be used. Specific examples of anode materials include metals such as vanadium, chromium, copper, zinc and gold or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (indium zinc oxide). 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-di Oxy)thiophene] (poly[3,4-(ethylene-1,2-dioxy)thiophene], PEDOT), polypyrrole and polyaniline; and the like, but not limited thereto.

As the cathode material, materials having a relatively small work function can be used, and metals, metal oxides, conductive polymers, etc. can be used. Specific examples of cathode materials include metals, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gamma, aluminum, silver, tin, and lead, or alloys thereof; multilayer structure materials, such as LiF/Al or LiO ₂ /Al; and the like, but not limited to this.

As the hole injection material, a known hole injection material can be used, and for example, a phthalocyanine compound, such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429; or a starburst amine derivative, such as Tris(4-carbazoyl-9-ylphenyl)amine (tris(4-carbazoyl-9-ylphenyl)amine, described in the literature [Advanced Material, 6, p.677 (1994)] TCTA), 4,4',4''-tris[phenyl(m-tolyl)amino]triphenylamine (4,4',4''-tri[phenyl(m-tolyl)amino]triphenylamine, m-MTDATA) or 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene , M-MTDAPB); polyaniline/dodecylbenzenesulfonic acid, poly(3,4-ethylenedioxythiophene)/poly(4-styrene sulfonate), poly(4-styrenesulfonate) as a conductive polymer with solubility Aniline/camphorsulfonic acid or polyaniline/poly(4-styrene-sulfonate); and the like.

As the hole transfer material, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, etc. can be used, and low molecular or high molecular materials can also be used.

As electron transfer materials, oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane, And its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and its derivatives and other metal complexes, and polymers can also be used Materials and low molecular materials.

As an example of the electron injection material, LiF is generally used in this technology, however, the application is not limited to this.

As the luminescent material, a red, green or blue luminescent material can be used, and if necessary, two or more luminescent materials can be mixed and used. In this context, two or more luminescent materials can be used by deposition as separate supply sources or by premixing and deposition as one supply source. In addition, fluorescent materials can also be used as luminescent materials, however, phosphorescent materials can also be used. As the light-emitting material, a material that emits light by bonding electrons and holes injected from the anode and the cathode, respectively, can be used alone, however, a material having a host material and a dopant material involved in light-emitting together can also be used.

When mixing luminescent material hosts, the same series of hosts can be mixed, or different series of hosts can be mixed. For example, any two or more types of materials from the n-type host material or the p-type host material can be selected, and the materials are used as the host material of the light-emitting layer.

Depending on the materials used, the organic light-emitting device according to an embodiment of the present application may be a top-emission type, a bottom-emission type, or a dual-emission type. ).

Based on principles similar to those used in organic light-emitting devices, the heterocyclic compound according to an embodiment of the present application can also be used in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like.

化合物 1-1 的製備 Hereinafter, the present specification will be explained in more detail with reference to examples, however, these examples are only for illustrative purposes, and the scope of the application is not limited thereto. [ Preparation Example 1] Preparation of Compound 1 ( C )

Preparation of compound 1-1

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

The resultant was extracted with dichloromethane (DCM) and dried with MgSO ₄ . The resultant was subjected to silica gel filtration and then concentrated to obtain compound 1-1 (65 g, 99%). Preparation of compound 1-2

In a single-neck round bottom flask (rbf), combine 4'-chloro-2,3-difluoro-2'-methoxy-1,1'-biphenyl (65 g, 255 millimoles) with MC ( The mixture of 1000 ml) was cooled to 0°C, BBr ₃ (48 ml, 500 mmol) was added dropwise thereto, and after the temperature was raised to room temperature, the resultant was stirred for 2 hours.

The reaction was terminated with distilled water, and the resultant was extracted with dichloromethane and dried with MgSO ₄ . The resultant was subjected to column purification (MC: HX=1:2) to obtain compound 1-2 (49 g, 80%). Preparation of compound 1-3

In a single-necked round-bottom flask (rbf), mix 4-chloro-2',3'-difluoro-[1,1'-biphenyl]-2-ol (49 g, 203 millimoles) with Cs _A mixture of ₂ CO ₃ (331 g, 1018 mmol) in dimethylacetamide (500 ml) was stirred at 120°C. The resultant was cooled and then filtered, and after removing the solvent of the filtrate, column purification (HX:MC=5:1) was performed to obtain compound 1-3 (10.1 g, 88%). Preparation of compound 1-4

In a single-neck round-bottom flask (rbf), mix 3-chloro-6-fluorodibenzo[b,d]furan (9 g, 40.7 millimoles), 9H-carbazole (8.1 g, 48.9 millimoles) ) And Cs ₂ CO ₃ (66.3 g, 203.5 mmol) in dimethylacetamide (100 ml) were refluxed at 170°C for 12 hours.

The resultant was cooled and then filtered, and after removing the solvent of the filtrate, column purification (HX:MC=4:1) was performed to obtain compound 1-4 (10.1 g, 67%). Preparation of compound 1-5

In a single-neck round-bottom flask (rbf), 9-(7-chlorodibenzo[b,d]furan-4-yl)-9H-carbazole (10.1 g, 27.4 millimoles), double (frequency Alcohol group) diboron (13.9 g, 54.9 millimoles), XPhos (2.6 g, 5.48 millimoles), potassium acetate (8 grams, 82 millimoles) and Pd(dba) ₂ (1.57 grams, 2.74 millimoles) A mixture of 1,4-dioxane (100 ml) in mol) was refluxed at 140°C.

The resultant was extracted with dichloromethane, concentrated, and then treated with dichloromethane/MeOH pair to obtain compound 1-5 (13.4 g, exceeding the yield). Preparation of compound 1

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

71% 3

74% 5

67% 7

66% 10

70% 17

66% [表2] 化合物 A B C 良率 （1-3至C） 18

71% 19

74% 22

78% 28

61% 29

67% 30

68% 34

71% [表3] 化合物 A B C 良率 （1-3至C） 38

77% 39

74% 43

62% 45

49% 48

53% 51

51% [表4] 化合物 A B C 良率 （1-3至C） 53

46% 55

59% 59

68% 62

67% 65

63% 67

71% 70

70% [表5] 化合物 A B C 良率 （1-3至C） 71

69% 75

68% 77

70% 80

63% 82

69% 83

65% 86

67% [表6] 化合物 A B C 良率 （1-3至C） 90

66% 92

61% 95

51% 100

54% 101

49% 109

61% 111

55% [表7] 化合物 A B C 良率 （1-3至C） 115

60% 118

59% 121

68% 126

64% 127

66% 129

69% [表8] 化合物 A B C 良率 （1-3至C） 133

72% 135

70% 293

69% 294

73% 297

62% 298

64% [ 製備實例2]化合物137（D）的製備

The following compound C was synthesized in the same manner as the preparation of compound 1 in Preparation Example 1, except that A and B shown in the following [Table 1] to [Table 8] were used as intermediates. [Table 1] Compound A B C Yield rate (1-3 to C) 2

71% 3

74% 5

67% 7

66% 10

70% 17

66% [Table 2] Compound A B C Yield rate (1-3 to C) 18

71% 19

74% twenty two

78% 28

61% 29

67% 30

68% 34

71% [table 3] Compound A B C Yield rate (1-3 to C) 38

77% 39

74% 43

62% 45

49% 48

53% 51

51% [Table 4] Compound A B C Yield rate (1-3 to C) 53

46% 55

59% 59

68% 62

67% 65

63% 67

71% 70

70% [table 5] Compound A B C Yield rate (1-3 to C) 71

69% 75

68% 77

70% 80

63% 82

69% 83

65% 86

67% [Table 6] Compound A B C Yield rate (1-3 to C) 90

66% 92

61% 95

51% 100

54% 101

49% 109

61% 111

55% [Table 7] Compound A B C Yield rate (1-3 to C) 115

60% 118

59% 121

68% 126

64% 127

66% 129

69% [Table 8] Compound A B C Yield rate (1-3 to C) 133

72% 135

70% 293

69% 294

73% 297

62% 298

64% [ Preparation Example 2] Preparation of Compound 137(D)

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

73% 139

72% 140

70% 141

67% 146

69% 152

63% [表10] 化合物 A B D 良率 （137-3至D） 153

68% 154

71% 155

76% 173

67% 176

66% 179

72% 299

71% 301

67% 303

63% [ 製備實例 3] 化合物 189 （ E ）的製備

The following compound D was synthesized in the same manner as the preparation of compound 137 in Preparation Example 2, except that A and B shown in the following [Table 9] and [Table 10] were used as intermediates. [Table 9] Compound A B D Yield rate (137-3 to D) 138

73% 139

72% 140

70% 141

67% 146

69% 152

63% [Table 10] Compound A B D Yield rate (137-3 to D) 153

68% 154

71% 155

76% 173

67% 176

66% 179

72% 299

71% 301

67% 303

63% [ Preparation Example 3] Preparation of Compound 189 ( E )

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

69% 191

73% 192

68% 193

66% 198

72% 204

68% [表12] 化合物 A B E 良率 （137-3至E） 205

67% 206

74% 207

72% 215

70% 255

69% 228

69% 231

76% 305

59% 306

62% 308

64% [ 製備實例 4] 化合物 241 （ F ）的製備

The following compound E was synthesized in the same manner as the preparation of compound 189 in Preparation Example 3, except that A and B shown in the following [Table 11] and [Table 12] were used as intermediates. [Table 11] Compound A B E Yield rate (189-3 to E) 190

69% 191

73% 192

68% 193

66% 198

72% 204

68% [Table 12] Compound A B E Yield rate (137-3 to E) 205

67% 206

74% 207

72% 215

70% 255

69% 228

69% 231

76% 305

59% 306

62% 308

64% [ Preparation Example 4] Preparation of Compound 241 ( F )

The target compound 241(F) was synthesized in the same manner as the preparation of compound 1 in Preparation Example 1, except that 2-bromo-1,3-difluorobenzene was used instead of 1-bromo-2,3-difluorobenzene ( 6.4 grams, 37%).

66% 243

68% 244

63% 245

59% 250

70% 256

65% [表14] 化合物 A B D 良率 （241-3至F） 257

61% 258

62% 259

57% 272

61% 277

64% 280

66% 283

70% 312

63% 314

65% 315

60% The following compound F was synthesized in the same manner as the preparation of compound 241 in Preparation Example 4, except for using A and B shown in the following [Table 13] and [Table 14] as intermediates. [Table 13] Compound A B F Yield rate (241-3 to F) 242

66% 243

68% 244

63% 245

59% 250

70% 256

65% [Table 14] Compound A B D Yield rate (241-3 to F) 257

61% 258

62% 259

57% 272

61% 277

64% 280

66% 283

70% 312

63% 314

65% 315

60%

1 ）化合物 2-6 的製備 In addition to the compounds described in Tables 1 to 14, compounds 1 to 316 were also prepared in the same manner as the method described in the preparation examples provided above. > Preparation Example 5> Synthesis of Compound 2-6

1 ) Preparation of compound 2-6

In the 5-phenyl-5,7-indoline [2,3-b]carbazole (6.0 g, 18.05 millimoles/liter (mM)), 4-bromo-1,1'; 4 ',1''-terphenyl (6.7 g, 21.66 millimoles/liter), Pd ₂ (dba) ₃ (0.824 grams, 0.90 millimoles/liter), Sphos (0.74 grams, 1.80 millimoles/liter) And t-BuONa (3.47 g, 36.10 mmol/L) was dissolved in 1,4-oxane (1,4-oxane) (60 mL), and the resultant was refluxed for 24 hours. After the reaction was completed, the resultant was extracted by introducing distilled water and dichloromethane (DCM) thereto at room temperature, and after drying the organic layer with MgSO ₄ , the solvent was removed using a rotary evaporator. The reaction material was dissolved in dichlorobenzoyl chloride (DCB) (100 ml), filtered with silica gel for purification, and recrystallized with methanol to obtain the target compound 2-6 (8.6 g, 85%) ).

83% 2-19

84% 2-22

80% 2-25

81% 2-30

80% 2-40

74% 2-70

82% > 製備實例 6> 化合物 2-79 的合成

1 ）化合物 2-79-2 的製備 Except that the intermediate A-1 shown in Table 15 below was used instead of 4-bromo-1,1';4',1''-terphenyl and the intermediate B-1 shown in Table 15 below was used instead of 5-phenyl -5,7-Indolo[2,3-b]carbazole, the target compound A was synthesized in the same manner as in Preparation Example 5. [Table 15] Compound number Intermediate A-1 Intermediate B-1 Target compound A Yield 2-6

83% 2-19

84% 2-22

80% 2-25

81% 2-30

80% 2-40

74% 2-70

82% > Preparation Example 6> Synthesis of Compound 2-79

1 ) Preparation of compound 2-79-2

The 2-chloro-7-phenyl-5,7-indoline [2,3-b]carbazole (7.0 g, 19.08 millimoles/liter), iodobenzene (4.28 g, 20.99 millimoles) Ears/liter), Pd ₂ (dba) ₃ (0.873 g, 0.95 millimoles/liter), (t-Bu) ₃ P (0.58 grams, 2.86 millimoles/liter), t-BuONa (3.67 grams, 38.16 After dissolving millimoles/liter in toluene (70 ml), the resultant was refluxed for 4 hours. After the reaction was completed, the resultant was extracted by introducing distilled water and DCM into it at room temperature, and after drying the organic layer with MgSO ₄ , the solvent was removed using a rotary evaporator. The reaction material was subjected to column purification (MC/HEX), and then the solvent was removed using a rotary evaporator to obtain the target compound 2-79-2 (6.93 g, 82%).

82% 2-113-2

85% 2-123-2

81% 2-142-2

80% 2 ）化合物 2-79-1 的製備

Except that the intermediate C-3 shown in Table 16 below was used instead of 2-chloro-7-phenyl-5,7-indoline[2,3-b]carbazole, it was similar to that in Preparation Example 6. The target compound C-2 was synthesized in the same way as the preparation of compound 2-79-2. [Table 16] Compound number Intermediate C-3 Intermediate D-3 Target compound C-2 Yield 2-79-2

82% 2-113-2

85% 2-123-2

81% 2-142-2

80% 2 ) Preparation of compound 2-79-1

After mixing 2-chloro-5,7-diphenyl-5,7-indoline[2,3-b]carbazole (6.93 g, 15.65 millimoles/liter), bipinacol two Borane (5.96 g, 23.47 millimoles/liter), Pd ₂ (dba) ₃ (1.43 grams, 1.56 millimoles/liter), XPhos (1.49 grams, 3.13 millimoles/liter) and KOAc (4.61 grams, After 46.94 mmol/L) was dissolved in 1,4-oxane (70 ml), the resultant was refluxed for 5 hours. After the reaction was completed, the resultant was extracted by introducing distilled water and DCM into it at room temperature, and after drying the organic layer with MgSO ₄ , the solvent was removed using a rotary evaporator. The reaction material was subjected to column purification (MC/HEX), and the filtrate was vacuum concentrated to obtain the target compound 2-79-1 (6.8 g, 81%).

81% 2- 123-1

75% 2- 113-1

80% 2- 142-1

76% 3 ）化合物 2-79 的製備

In addition to using the intermediate C-2 shown in Table 17 below instead of 2-chloro-5,7-diphenyl-5,7-indo[2,3-b]carbazole, it can be used to prepare The target compound C-1 was synthesized in the same way as the preparation of compound 2-79-1 in Example 6. [Table 17] Compound number Intermediate C-2 Target compound C-1 Yield Compound number Intermediate C-2 Target compound C-1 Yield 2- 79-1

81% 2- 123-1

75% 2- 113-1

80% 2- 142-1

76% 3 ) Preparation of compound 2-79

In the 5,7-diphenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)-5,7-indoline [ 2,3-b]carbazole (6.8 g, 12.72 millimoles/liter), 3-bromo-9-phenylcarbazole (4.51 g, 14.00 millimoles/liter), Pd(PPh ₃ ) ₄ (0.74 G, 0.64 millimoles/liter) and K ₂ CO ₃ (3.52 grams, 25.45 millimoles/liter) were dissolved in toluene (70 mL)/ethanol (15 mL)/water (15 mL), and the resultant Refluxed for 4 hours. After the reaction was completed, the resultant was extracted by introducing distilled water and DCM into it at room temperature, and after drying the organic layer with MgSO ₄ , the solvent was removed using a rotary evaporator. The reaction material was subjected to column purification (MC/HEX), and the filtrate was vacuum concentrated to obtain the target compound 2-79 (6.61 g, 80%).

83% 2-78

83% 2-79

80% 2-113

82% 2-123

75% 2-142

79% Except that the intermediate C-1 shown in Table 18 below is used instead of 5,7-diphenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan )-5,7-indoline[2,3-b]carbazole and the use of intermediate D-1 instead of 3-bromo-9-phenylcarbazole to compare with compound 2- in Preparation Example 6. The target compound C was synthesized in the same way as the preparation of 79. [Table 18] Compound number Intermediate C-1 Intermediate D-1 Target compound C Total yield 2-77

83% 2-78

83% 2-79

80% 2-113

82% 2-123

75% 2-142

79%

Except for the preparation examples, the compound shown in Chemical Formula 1 and the compound shown in Chemical Formula 2 were also prepared in the same manner. The synthetic identification data of the compound prepared above is as described in the following [Table 19] and [Table 20]. [Table 19] Compound FD-quality Compound FD-quality 1 m/z=564.63(C39H24N4O=564.20) 2 m/z=640.73(C45H28N4O=640.23) 3 m/z=640.73(C45H28N4O=640.23) 4 m/z=716.83(C51H32N4O=717.26) 5 m/z=716.83(C51H32N4O=717.26) 6 m/z=729.82(C51H31N5O=729.25) 7 m/z=729.82(C51H31N5O=729.25) 8 m/z=805.92(C57H35N5O=805.28) 9 m/z=730.81(C51H30N4O2=730.81) 10 m/z=680.79(C48H32N4O=680.26) 11 m/z=680.79(C48H32N4O=680.26) 12 m/z=680.79(C48H32N4O=680.26) 13 m/z=670.78(C45H26N4OS=670.18) 14 m/z=654.71(C45H26N4O2=654.21) 15 m/z=654.71(C45H26N4O2=654.21) 16 m/z=670.78(C45H26N4OS=670.18) 17 m/z=640.73(C45H2N4O=640.23) 18 m/z=716.83(C51H32N4O=716.26) 19 m/z=716.83(C51H32N4O=716.26) 20 m/z=792.92(C57H36N4O=792.29) twenty one m/z=792.92(C57H36N4O=792.29) twenty two m/z=640.73(C45H2N4O=640.23) twenty three m/z=792.92(C57H36N4O=792.29) twenty four m/z=792.92(C57H36N4O=792.29) 25 m/z=792.92(C57H36N4O=792.29) 26 m/z=728.84(C52H32N4O=728.26) 27 m/z=728.84(C52H32N4O=728.26) 28 m/z=804.93(C58H36N4O=804.29) 29 m/z=746.21(C51H30N4OS=746.21) 30 m/z=756.89(C54H36N4O=756.29) 31 m/z=756.89(C54H36N4O=756.29) 32 m/z=679.81(C49H33N3O=679.26) 33 m/z=746.88(C51H30N4OS=746.21) 34 m/z=730.81(C51H30N4O2=730.24 35 m/z=730.81(C51H30N4O2=730.24 36 m/z=669.79(C46H27N3OS=669.19) 37 m/z=640.73(C45H28N4O=640.23) 38 m/z=640.73(C45H28N4O=640.23) 39 m/z=716.83(C51H32N4O=717.26) 40 m/z=716.83(C51H32N4O=717.26) 41 m/z=716.83(C51H43N4O=716.26) 42 m/z=716.83(C51H32N4O=717.26) 43 m/z=715.84(C52H33N3O=715.26) 44 m/z=715.84(C52H33N3O=715.26) 45 m/z=640.73(C45H28N4O=640.23 46 m/z=716.83(C51H32N4O=716.26) 47 m/z=716.83(C51H32N4O=716.26) 48 m/z=792.92(C57H36N4O=792.29) 49 m/z=756.89(C54H36N4O=756.29) 50 m/z=716.83(C51H32N4O=716.26) 51 m/z=716.83(C51H32N4O=716.26) 52 m/z=716.83(C51H32N4O=716.26) 53 m/z=792.92(C57H36N4O=792.29) 54 m/z=792.92(C57H36N4O=792.29) 55 m/z=601.69(C43H27N3O=601.69) 56 m/z=601.69(C43H27N3O=601.69) 57 m/z=677.79(C49H31N3O=677.25) 58 m/z=677.79(C49H31N3O=677.25) 59 m/z=677.79(C49H31N3O=677.25) 60 m/z=677.79(C49H31N3O=677.25) 61 m/z=753.89(C55H35N3O=753.28) 62 m/z=753.89(C55H35N3O=753.28) 63 m/z=753.89(C55H35N3O=753.28) 64 m/z=753.89(C55H35N3O=753.28) 65 m/z=717.85(C52H35N3O=717.28) 66 m/z=717.85(C52H35N3O=717.28) 67 m/z=707.84(C49H29N3OS=707.20) 68 m/z=691.77(C49H29N3O2=691.23) 69 m/z=613.70(C44H27N3O=613.22) 70 m/z=689.80(C50H31N3O=689.25) 71 m/z=689.80(C50H31N3O=689.25) 72 m/z=689.80(C50H31N3O=689.25) 73 m/z=765.90(C56H35N3O=765.28) 74 m/z=765.90(C56H35N3O=765.28) 75 m/z=729.86(C53H35N3O=729.28) 76 m/z=719.20(C50H29N3OS=719.20) 77 m/z=537.61(C38H23N3O=537.18) 78 m/z=613.70(C44H27N3O=613.22) 79 m/z=613.70(C44H27N3O=613.22) 80 m/z=613.70(C44H27N3O=613.22) 81 m/z=689.80(C50H31N3O=689.25) 82 m/z=689.80(C50H31N3O=689.25) 83 m/z=702.80(C50H30N4O=702.24) 84 m/z=702.80(C50H30N4O=702.24) 85 m/z=537.61(C38H23N3O=537.18) 86 m/z=613.70(C44H27N3O=613.22) 87 m/z=613.70(C44H27N3O=613.22) 88 m/z=613.70(C44H27N3O=613.22) 89 m/z=689.80(C50H31N3O=689.25) 90 m/z=689.80(C50H31N3O=689.25) 91 m/z=778.90(C56H34N4O=78.27) 92 m/z=703.78(C50H29N3O2=703.23) 93 m/z=536.62(C39H24N2O=536.19) 94 m/z=612.72(C45H28N2O=612.22) 95 m/z=612.72(C45H28N2O=612.22) 96 m/z=612.72(C45H28N2O=612.22) 97 m/z=688.81(C51H32N2O=688.25) 98 m/z=688.81(C51H32N2O=688.25) 99 m/z=652.78(C48H32N2O=652.25) 100 m/z=652.78(C48H32N2O=652.25) 101 m/z=536.62(C39H24N2O=536.19) 102 m/z=612.72(C45H28N2O=612.22) 103 m/z=612.72(C45H28N2O=612.22) 104 m/z=612.72(C45H28N2O=612.22) 105 m/z=688.81(C51H32N2O=688.25) 106 m/z=688.81(C51H32N2O=688.25) 107 m/z=642.77(C45H26N2OS=642.18) 108 m/z=626.70(C45H27N2O2=626.20) 109 m/z=587.67(C42H25N3O=587.20) 110 m/z=663.76(C48H29N3O=663.23) 111 m/z=663.76(C48H29N3O=663.23) 112 m/z=663.76(C48H29N3O=663.23) 113 m/z=739.86(C54H33N3O=739.26) 114 m/z=739.86(C54H33N3O=739.26) 115 m/z=677.75(C48H27N3O2=677.21) 116 m/z=693.81(C48H27NOS=693.19) 117 m/z=563.65(C40H25N3O=563.20) 118 m/z=639.73(C46H29N3O=639.23) 119 m/z=639.73(C46H29N3O=639.23) 120 m/z=715.84(C52H33N3O=715.26) 121 m/z=715.84(C52H33N3O=715.26) 122 m/z=715.84(C52H33N3O=715.26) 123 m/z=639.74(C46H29N3O=639.23) 124 m/z=715.84(C52H33N3O=715.26) 125 m/z=664.75(C47H28N4O=664.23) 126 m/z=740.85(C53H32N4O=740.26) 127 m/z=740.85(C53H32N4O=740.26) 128 m/z=740.85(C53H32N4O=740.26) 129 m/z=816.94(C59H36N4O=816.29) 130 m/z=816.94(C59H36N4O=816.29) 131 m/z=829.94(C59H35N5O=829.28) 132 m/z=829.94(C59H35N5O=829.28) 133 m/z=729.82(C51H31N5O=729.25) 134 m/z=805.92(C57H35N5O=805.28) 135 m/z=702.80(C50H30N4O=702.24) 136 m/z=766.27(C55H34N4O=766.27) 137 m/z=564.63(C39H24N4O=564.20) 138 m/z=640.73(C45H28N4O=640.23) 139 m/z=640.73(C45H28N4O=640.23) 140 m/z=716.83(C51H32N4O=717.26) 141 m/z=716.83(C51H32N4O=717.26) 142 m/z=729.82(C51H31N5O=729.25) 143 m/z=729.82(C51H31N5O=729.25) 144 m/z=805.92(C57H35N5O=805.28) 145 m/z=730.81(C51H30N4O2=730.81) 146 m/z=680.79(C48H32N4O=680.26) 147 m/z=680.79(C48H32N4O=680.26) 148 m/z=680.79(C48H32N4O=680.26) 149 m/z=670.78(C45H26N4OS=670.18) 150 m/z=654.71(C45H26N4O2=654.21) 151 m/z=654.71(C45H26N4O2=654.21) 152 m/z=670.78(C45H26N4OS=670.18) 153 m/z=640.73(C45H2N4O=640.23) 154 m/z=716.83(C51H32N4O=716.26) 155 m/z=716.83(C51H32N4O=716.26) 156 m/z=792.92(C57H36N4O=792.29) 157 m/z=792.92(C57H36N4O=792.29) 158 m/z=640.73(C45H2N4O=640.23) 159 m/z=792.92(C57H36N4O=792.29) 160 m/z=792.92(C57H36N4O=792.29) 161 m/z=792.92(C57H36N4O=792.29) 162 m/z=728.84(C52H32N4O=728.26) 163 m/z=728.84(C52H32N4O=728.26) 164 m/z=804.93(C58H36N4O=804.29) 165 m/z=746.21(C51H30N4OS=746.21) 166 m/z=756.89(C54H36N4O=756.29) 167 m/z=756.89(C54H36N4O=756.29) 168 m/z=679.81(C49H33N3O=679.26) 169 m/z=746.88(C51H30N4OS=746.21) 170 m/z=730.81(C51H30N4O2=730.24 171 m/z=730.81(C51H30N4O2=730.24 172 m/z=669.79(C46H27N3OS=669.19) 173 m/z=640.73(C45H28N4O=640.23) 174 m/z=640.73(C45H28N4O=640.23) 175 m/z=716.83(C51H32N4O=717.26) 176 m/z=716.83(C51H32N4O=717.26) 177 m/z=716.83(C51H43N4O=716.26) 178 m/z=716.83(C51H32N4O=717.26) 179 m/z=715.84(C52H33N3O=715.26) 180 m/z=715.84(C52H33N3O=715.26) 181 m/z=664.75(C47H28N4O=664.23) 182 m/z=740.85(C53H32N4O=740.26) 183 m/z=740.85(C53H32N4O=740.26) 184 m/z=740.85(C53H32N4O=740.26) 185 m/z=816.94(C59H36N4O=816.29) 186 m/z=816.94(C59H36N4O=816.29) 187 m/z=829.94(C59H35N5O=829.28) 188 m/z=829.94(C59H35N5O=829.28) 189 m/z=564.63(C39H24N4O=564.20) 190 m/z=640.73(C45H28N4O=640.23) 191 m/z=640.73(C45H28N4O=640.23) 192 m/z=716.83(C51H32N4O=717.26) 193 m/z=716.83(C51H32N4O=717.26) 194 m/z=729.82(C51H31N5O=729.25) 195 m/z=729.82(C51H31N5O=729.25) 196 m/z=805.92(C57H35N5O=805.28) 197 m/z=730.81(C51H30N4O2=730.81) 198 m/z=680.79(C48H32N4O=680.26) 199 m/z=680.79(C48H32N4O=680.26) 200 m/z=680.79(C48H32N4O=680.26) 201 m/z=670.78(C45H26N4OS=670.18) 202 m/z=654.71(C45H26N4O2=654.21) 203 m/z=654.71(C45H26N4O2=654.21) 204 m/z=670.78(C45H26N4OS=670.18) 205 m/z=640.73(C45H2N4O=640.23) 206 m/z=716.83(C51H32N4O=716.26) 207 m/z=716.83(C51H32N4O=716.26) 208 m/z=792.92(C57H36N4O=792.29) 209 m/z=792.92(C57H36N4O=792.29) 210 m/z=640.73(C45H2N4O=640.23) 211 m/z=792.92(C57H36N4O=792.29) 212 m/z=792.92(C57H36N4O=792.29) 213 m/z=792.92(C57H36N4O=792.29) 214 m/z=728.84(C52H32N4O=728.26) 215 m/z=728.84(C52H32N4O=728.26) 216 m/z=804.93(C58H36N4O=804.29) 217 m/z=746.21(C51H30N4OS=746.21) 218 m/z=756.89(C54H36N4O=756.29) 219 m/z=756.89(C54H36N4O=756.29) 220 m/z=679.81(C49H33N3O=679.26) 221 m/z=746.88(C51H30N4OS=746.21) 222 m/z=730.81(C51H30N4O2=730.24 223 m/z=730.81(C51H30N4O2=730.24 224 m/z=669.79(C46H27N3OS=669.19) 225 m/z=640.73(C45H28N4O=640.23) 226 m/z=640.73(C45H28N4O=640.23) 227 m/z=716.83(C51H32N4O=717.26) 228 m/z=716.83(C51H32N4O=717.26) 229 m/z=716.83(C51H43N4O=716.26) 230 m/z=716.83(C51H32N4O=717.26) 231 m/z=715.84(C52H33N3O=715.26) 232 m/z=715.84(C52H33N3O=715.26) 233 m/z=664.75(C47H28N4O=664.23) 234 m/z=740.85(C53H32N4O=740.26) 235 m/z=740.85(C53H32N4O=740.26) 236 m/z=740.85(C53H32N4O=740.26) 237 m/z=816.94(C59H36N4O=816.29) 238 m/z=816.94(C59H36N4O=816.29) 239 m/z=829.94(C59H35N5O=829.28) 240 m/z=829.94(C59H35N5O=829.28) 241 m/z=564.63(C39H24N4O=564.20) 242 m/z=640.73(C45H28N4O=640.23) 243 m/z=640.73(C45H28N4O=640.23) 244 m/z=716.83(C51H32N4O=717.26) 245 m/z=716.83(C51H32N4O=717.26) 246 m/z=729.82(C51H31N5O=729.25) 247 m/z=729.82(C51H31N5O=729.25) 248 m/z=805.92(C57H35N5O=805.28) 249 m/z=730.81(C51H30N4O2=730.81) 250 m/z=680.79(C48H32N4O=680.26) 251 m/z=680.79(C48H32N4O=680.26) 252 m/z=680.79(C48H32N4O=680.26) 253 m/z=670.78(C45H26N4OS=670.18) 254 m/z=654.71(C45H26N4O2=654.21) 255 m/z=654.71(C45H26N4O2=654.21) 256 m/z=670.78(C45H26N4OS=670.18) 257 m/z=640.73(C45H2N4O=640.23) 258 m/z=716.83(C51H32N4O=716.26) 259 m/z=716.83(C51H32N4O=716.26) 260 m/z=792.92(C57H36N4O=792.29) 261 m/z=792.92(C57H36N4O=792.29) 262 m/z=640.73(C45H2N4O=640.23) 263 m/z=792.92(C57H36N4O=792.29) 264 m/z=792.92(C57H36N4O=792.29) 265 m/z=792.92(C57H36N4O=792.29) 266 m/z=728.84(C52H32N4O=728.26) 267 m/z=728.84(C52H32N4O=728.26) 268 m/z=804.93(C58H36N4O=804.29) 269 m/z=746.21(C51H30N4OS=746.21) 270 m/z=756.89(C54H36N4O=756.29) 271 m/z=756.89(C54H36N4O=756.29) 272 m/z=679.81(C49H33N3O=679.26) 273 m/z=746.88(C51H30N4OS=746.21) 274 m/z=730.81(C51H30N4O2=730.24 275 m/z=730.81(C51H30N4O2=730.24 276 m/z=669.79(C46H27N3OS=669.19) 277 m/z=640.73(C45H28N4O=640.23) 278 m/z=640.73(C45H28N4O=640.23) 279 m/z=716.83(C51H32N4O=717.26) 280 m/z=716.83(C51H32N4O=717.26) 281 m/z=716.83(C51H43N4O=716.26) 282 m/z=716.83(C51H32N4O=717.26) 283 m/z=715.84(C52H33N3O=715.26) 284 m/z=715.84(C52H33N3O=715.26) 285 m/z=664.75(C47H28N4O=664.23) 286 m/z=740.85(C53H32N4O=740.26) 287 m/z=740.85(C53H32N4O=740.26) 288 m/z=740.85(C53H32N4O=740.26) 289 m/z=816.94(C59H36N4O=816.29) 290 m/z=816.94(C59H36N4O=816.29) 291 m/z=829.94(C59H35N5O=829.28) 292 m/z=829.94(C59H35N5O=829.28) 293 m/z=716.83(C51H32N4O=716.26) 294 m/z=654.71(C45H26N4O2=654.21) 295 m/z=730.81(C51H30N4O2=730.24) 296 m/z=654.71(C45H26N4O2=654.21) 297 m/z=730.81(C51H30N4O2=730.24) 298 m/z=730.81(C51H30N4O2=730.24) 299 m/z=716.83(C51H32N4O=716.26) 300 m/z=654.71(C45H26N4O2=654.21) 301 m/z=730.81(C51H30N4O2=730.24) 302 m/z=730.81(C51H30N4O2=730.24) 303 m/z=746.88(C51H30N4OS=741.21) 304 m/z=756.89(C54H36N4O=756.29) 305 m/z=716.83(C51H32N4O=716.26) 306 m/z=654.71(C45H26N4O2=654.21) 307 m/z=730.81(C51H30N4O2=730.24) 308 m/z=746.88(C51H30N4OS=741.21) 309 m/z=730.81(C51H30N4O2=730.24) 310 m/z=730.81(C51H30N4O2=730.24) 311 m/z=756.89(C54H36N4O=756.29) 312 m/z=716.83(C51H32N4O=716.26) 313 m/z=730.81(C51H30N4O2=730.24) 314 m/z=654.71(C45H26N4O2=654.21) 315 m/z=730.81(C51H30N4O2=730.24) 316 m/z=730.81(C51H30N4O2=730.24) 2-1 m/z=408.16(C30H20N2=408.50) 2-2 m/z=484.19(C36H24N2=484.60) 2-3 m/z=484.19(C36H24N2=484.60) 2-4 m/z=458.18(C34H22N2=458.56) 2-5 m/z=458.18(C34H22N2=458.56) 2-6 m/z=560.23(C42H28N2=560.70) 2-7 m/z=560.23(C42H28N2=560.70) 2-8 m/z=558.21(C42H26N2=558.68) 2-9 m/z=560.23(C42H28N2=560.70) 2-10 m/z=666.25(C48H34N2Si=666.90) 2-11 m/z=524.23(C39H28N2=524.67) 2-12 m/z=524.23(C39H28N2=524.67) 2-13 m/z=648.26(C49H32N2=648.26) 2-14 m/z=498.17(C36H22N2O=498.58) 2-15 m/z=498.17(C36H22N2O=498.58) 2-16 m/z=514.15(C36H22N2S=514.65) 2-17 m/z=514.15(C36H22N2S=514.65) 2-18 m/z=573,22(C4H27N3=573.70) 2-19 m/z=560.23(C42H28N2=560.70) 2-20 m/z=560.23(C42H28N2=560.70) 2-21 m/z=712.29(C54H36N2=712.90) 2-22 m/z=712.29(C54H36N2=712.90) 2-23 m/z=708.26(C54H32N2=708.86) 2-24 m/z=588.18(C42H24N2O=588.67) 2-25 m/z=588.18(C42H24N2O=588.67) 2-26 m/z=620.14(C42H24N2S2=620.79) 2-27 m/z=620.14(C42H24N2S2=620.79) 2-28 m/z=738.28(C54H34N4=738.89) 2-29 m/z=408.16(C30H20N2=408.50) 2-30 m/z=560.23(C42H28N2=560.70) 2-31 m/z=560.23(C42H28N2=560.70) 2-32 m/z=712.29(C54H36N2=712.90) 2-33 m/z=712.29(C54H36N2=712.90) 2-34 m/z=708.26(C54H32N2=708.86) 2-35 m/z=640.29(C48H36N2=640.83) 2-36 m/z=588.18(C42H24N2O=588.67) 2-37 m/z=588.18(C42H24N2O=588.67) 2-38 m/z=620.14(C42H24N2S2=620.79) 2-39 m/z=620.14(C42H24N2S2=620.79) 2-40 m/z=738.28(C54H34N4=738.89) 2-41 m/z=408.16(C30H20N2=408.50) 2-42 m/z=560.23(C42H28N2=560.70) 2-43 m/z=560.23(C42H28N2=560.70) 2-44 m/z=712.29(C54H36N2=712.90) 2-45 m/z=712.29(C54H36N2=712.90) 2-46 m/z=708.26(C54H32N2=708.86) 2-47 m/z=640.29(C48H36N2=640.83) 2-48 m/z=588.18(C42H24N2O=588.67) 2-49 m/z=588.18(C42H24N2O=588.67) 2-50 m/z=620.14(C42H24N2S2=620.79) 2-51 m/z=620.14(C42H24N2S2=620.79) 2-52 m/z=738.28(C54H34N4=738.89) 2-53 m/z=408.16(C30H20N2=408.50) 2-54 m/z=560.23(C42H28N2=560.70) 2-55 m/z=560.23(C42H28N2=560.70) 2-56 m/z=712.29(C54H36N2=712.90) 2-57 m/z=712.29(C54H36N2=712.90) 2-58 m/z=708.26(C54H32N2=708.86) 2-59 m/z=640.29(C48H36N2=640.83) 2-60 m/z=588.18(C42H24N2O=588.67) 2-61 m/z=588.18(C42H24N2O=588.67) 2-62 m/z=620.14(C42H24N2S2=620.79) 2-63 m/z=620.14(C42H24N2S2=620.79) 2-64 m/z=738.28(C54H34N4=738.89) 2-65 m/z=408.16(C30H20N2=408.50) 2-66 m/z=560.23(C42H28N2=560.70) 2-67 m/z=560.23(C42H28N2=560.70) 2-68 m/z=712.29(C54H36N2=712.90) 2-69 m/z=712.29(C54H36N2=712.90) 2-70 m/z=708.26(C54H32N2=708.86) 2-71 m/z=640.29(C48H36N2=640.83) 2-72 m/z=588.18(C42H24N2O=588.67) 2-73 m/z=588.18(C42H24N2O=588.67) 2-74 m/z=620.14(C42H24N2S2=620.79) 2-75 m/z=620.14(C42H24N2S2=620.79) 2-76 m/z=738.28(C54H34N4=738.89) 2-77 m/z=484.19(C36H24N2=484.60) 2-78 m/z=634.24(C48H30N2=634.78) 2-79 m/z=649.25(C48H31N3=649.80) 2-80 m/z=725.28(C54H35N3=725.89) 2-81 m/z=725.28(C54H35N3=725.89) 2-82 m/z=649.25(C48H31N3=649.80) 2-83 m/z=649.25(C48H31N3=649.80) 2-84 m/z=649.25(C48H31N3=649.80) 2-85 m/z=574.20(C42H26N2O=574.68) 2-86 m/z=574.20(C42H26N2O=574.68) 2-87 m/z=590.18(C42H26N2S=590.74) 2-88 m/z=590.18(C42H26N2S=590.74) 2-89 m/z=649.25(C48H31N3=649.80) 2-90 m/z=725.28(C54H35N3=725.89) 2-91 m/z=725.28(C54H35N3=725.89) 2-92 m/z=649.25(C48H31N3=649.80) 2-93 m/z=574.20(C42H26N2O=574.68) 2-94 m/z=574.20(C42H26N2O=574.68) 2-95 m/z=590.18(C42H26N2S=590.74) 2-96 m/z=590.18(C42H26N2S=590.74) 2-97 m/z=649.25(C48H31N3=649.80) 2-98 m/z=725.28(C54H35N3=725.89) 2-99 m/z=725.28(C54H35N3=725.89) 2-100 m/z=649.25(C48H31N3=649.80) 2-101 m/z=574.20(C42H26N2O=574.68) 2-102 m/z=574.20(C42H26N2O=574.68) 2-103 m/z=590.18(C42H26N2S=590.74) 2-104 m/z=590.18(C42H26N2S=590.74) 2-105 m/z=649.25(C48H31N3=649.80) 2-106 m/z=725.28(C54H35N3=725.89) 2-107 m/z=725.28(C54H35N3=725.89) 2-108 m/z=649.25(C48H31N3=649.80) 2-109 m/z=574.20(C42H26N2O=574.68) 2-110 m/z=574.20(C42H26N2O=574.68) 2-111 m/z=590.18(C42H26N2S=590.74) 2-112 m/z=590.18(C42H26N2S=590.74) 2-113 m/z=649.25(C48H31N3=649.80) 2-114 m/z=725.28(C54H35N3=725.89) 2-115 m/z=725.28(C54H35N3=725.89) 2-116 m/z=649.25(C48H31N3=649.80) 2-117 m/z=574.20(C42H26N2O=574.68) 2-118 m/z=574.20(C42H26N2O=574.68) 2-119 m/z=590.18(C42H26N2S=590.74) 2-120 m/z=590.18(C42H26N2S=590.74) 2-121 m/z=425.12(C30H19NS=425.55) 2-122 m/z=575.17(C42H25NS=515.73) 2-123 m/z=590.18(C42H26N2S=590.74) 2-124 m/z=515.13(C36H21NOS=515.63) 2-125 m/z=531.11(C36H21NS2=531.69) 2-126 m/z=666.21(C48H30N2S=666.84) 2-127 m/z=666.21(C48H30N2S=666.84) 2-128 m/z=666.21(C48H30N2S=666.84) 2-129 m/z=742.24(C54H34N2S=742.94) 2-130 m/z=740.23(C54H32N2S=740.92) 2-131 m/z=574.20(C42H25N2O=574.68) 2-132 m/z=600.26(C45H32N2=600.76) 2-133 m/z=590.18(C42H26N2S=590.74) 2-134 m/z=574.20(C42H25N2O=574.68) 2-135 m/z=600.26(C45H32N2=600.76) 2-136 m/z=590.18(C42H26N2S=590.74) 2-137 m/z=574.20(C42H25N2O=574.68) 2-138 m/z=600.26(C45H32N2=600.76) 2-139 m/z=590.18(C42H26N2S=590.74) 2-140 m/z=574.20(C42H25N2O=574.68) 2-141 m/z=600.26(C45H32N2=600.76) 2-142 m/z=590.18(C42H26N2S=590.74) 2-143 m/z=574.20(C42H25N2O=574.68) 2-144 m/z=600.26(C45H32N2=600.76) 2-145 m/z=425.12(C30H19NS=425.55) 2-146 m/z=575.17(C42H25NS=515.73) 2-147 m/z=590.18(C42H26N2S=590.74) 2-148 m/z=515.13(C36H21NOS=515.63) 2-149 m/z=531.11(C36H21NS2=531.69) 2-150 m/z=666.21(C48H30N2S=666.84) 2-151 m/z=666.21(C48H30N2S=666.84) 2-152 m/z=666.21(C48H30N2S=666.84) 2-153 m/z=742.24(C54H34N2S=742.94) 2-154 m/z=740.23(C54H32N2S=740.92) 2-155 m/z=574.20(C42H25N2O=574.68) 2-156 m/z=600.26(C45H32N2=600.76) 2-157 m/z=590.18(C42H26N2S=590.74) 2-158 m/z=574.20(C42H25N2O=574.68) 2-159 m/z=600.26(C45H32N2=600.76) 2-160 m/z=590.18(C42H26N2S=590.74) 2-161 m/z=574.20(C42H25N2O=574.68) 2-162 m/z=600.26(C45H32N2=600.76) 2-163 m/z=590.18(C42H26N2S=590.74) 2-164 m/z=574.20(C42H25N2O=574.68) 2-165 m/z=600.26(C45H32N2=600.76) 2-166 m/z=590.18(C42H26N2S=590.74) 2-167 m/z=574.20(C42H25N2O=574.68) 2-168 m/z=600.26(C45H32N2=600.76) [Table 20] Compound ¹ H NMR (CDCl ₃ , 200 Mz) 1 δ=8.55 (1H, d), 8.28 (4H, d), 8.12 (1H, d), 7.95~7.89 (3H, m)6, 7.75 (1H, d), 7.64~7.63 (2H, d), 7.51 ~7.32 (12H, m) 2 δ=8.55 (1H, d), 8.28 (4H, d), 8.18 (1H, d), 7.95~7.89 (3H, m), 7.79~7.75 (2H, q), 7.64~7.62 (2H, d), 7.52~7.32 (15H, m) 3 δ=8.55 (1H, d), 8.28 (4H, d), 7.95~7.87 (4H, m), 7.77~7.89(3H, m), 7.75 (1H, d), 7.63~7.32 (26H, m) 5 δ=8.28 (4H, m), 8.18 (1H, d), 8.00~7.87 (4H, m), 7.77~7.64 (5H, m), 7.52~7.32 (18H, m) 7 δ=8.55 (1H, d), 8.28 (4H, d), 8.12 (1H, d), 7.95~7.89 (3H, m), 7.75 (1H, d), 7.63~7.32 (26H, m) 20 δ=8.49 (1H, d), 8.28~8.14 (4H, m), 8.10 (1H, d), 7.95 (1H, d), 7.89 (1H, d), 7.79~7.70 (3H, m), 7.62~ 7.32 (25H, m) 30 δ=8.39 (1H, s), 8.28~8.24 (3H, m), 8.12~8.09 (2H, d), 7.95 (1H, d), 7.89 (1H, d), 7.75~7.24 (22H, m), 1.72(6H, s) 126 δ=9.09 (2H, s), 8.49 (2H, d), 8.55 (1H, d), 8.18 (1H, d), 8.00~7.92 (9H, m), 7.79~7.75 (2H, m), 7.59~ 7.32 (15H, m) 137 δ=8.55 (1H, d), 8.25 (4H, d), 8.12 (2H, d), 7.95~7.89 (3H., m), 7.75~7.73 (2H, m), 7.64~7.63 (2H, m) , 7.51~7.25 (1H, m) 138 δ=8.57 (1H, d), 8.28 (4H, d), 8.12 (1H, d), 7.95~7.89 (3H, m), 7.79~7.73 (3H, m), 7.64~7.62 (2H, d), 7.51~7.25 (14H, m) 139 δ=8.55 (1H, d), 8.28 (4H, d), 7.95~7.87 (4H, m), 7.77~7.73 (5H, m), 7.52~7.25 (14H, m) 141 δ=8.27 (4H, d), 8.17 (1H, d), 8.00~ 7.87 (4H, m), 7.77~7.73 (6H, m), 7.52~7.41 (17H, m) 173 δ=8.55 (1H, d), 8.28 (4H, d), 8.12 (1H, d), 7.95~7.85 (5H, m), 7.75~7.73 (2H, d), 7.64~7.63 (2H, d), 7.51~7.25 (13H, m) 174 δ=8.55 (1H, d), 8.28 (4H, d), 8.12 (1H, d), 7.95~7.89 (3H, m), 7.70~7.25 (18H, m) 189 δ=8.56 (1H, d), 8.28 (4H, d), 8.12 (1H, d), 7.95~7.94 (2H, m), 7.80~7.75 (2H, m), 7.66~7.63 (3H, m), 7.51~7.25 (11H, m) 190 δ=8.55 (1H, d), 8.28 (4H, d), 8.18 (1H, d), 7.95~7.94 (2H, m), 7.66~~7.62 (3H, m), 7.52~7.25 (14H, m) 242 δ=8.55 (1H, d), 8.27~8.26 (4H, d), 8.18 (1H, d), 7.95~7.94 (2H, m), 7.79~7.75 (2H, m), 7.66~7.62 (3H, m) ), 7.52~7.25 (15H, m) 245 δ=8.28(4H, d), 8.17 (1H, d), 8.00~7.95 (2H, q), 7.87 (1H, d), 7.87 (1H, d), 7.77~7.64 (6H, m), 7.51~ 7.38 (18H, m) 301 δ=8.28(2H, d), 8.18~8.12 (2H, q), 8.00~7.73 (9H, m), 7.66~7.63 (3H, m), 7.52~7.29 (14H, m) 305 δ=8.55 (1H, d), 8.24 (2H, d), 8.12 (1H, d), 7.95~7.94(2H, d), 7.80~7.25 (26H, m) 314 δ=8.55(1H, d), 8.28 (2H, d), 8.12(1H, d), 7.94~7.81 (6H, m), 7.66~7.63 (4H, m), 7.51~7.25 (12H, m) 2-6 δ=8.55 (1H, d), 8.19 (1H, d), 7.94-7.91 (5H, m), 7.75 (2H, d), 7.62-7.35 (13H, m), 7.25-7.16 (6H, m) 2-19 δ=8.55 (1H, d), 8.19 (1H, d), 7.94~7.91 (9H, m), 7.75 (4H, d) 7.58-7.35 (11H, m) 7.20-7.16 (2H, m) 2-22 δ=8.55 (1H, d), 8.19 (1H, d), 7.94~7.91 (11H, m), 7.75-7.73 (6H, m) 7.61-7.35 (15H, m) 7.20-7.16 (2H, m) 2-25 δ=8.55 (1H, d), 8.19 (1H, d), 7.98~7.94 (3H, m), 7.74 (2H, d) 7.61-7.50 (7H, m), 7.40-7.31 (8H, m), 7.20 -7.16 (2H, m) 2-30 δ=8.55 (1H, d), 8.21-8.19 (3H, m), 7.94 (1H, d), 7.75-7.35 (21H, m), 7.20-7.16 (2H, m) 2-40 δ=8.55 (3H, d), 8.19 (1H, d), 7.94 (3H, d), 7.72-7.47 (18H, m), 7.38-7.35 (5H, m), 7.20-7.16 (4H, m) 2-70 δ=9.08-9.06 (4H, d), 8.55 (1H, d), 8.33-8.19 (5H, m), 8.00-7.94 (5H, m), 7.70-7.52 (14H, m), 7.35 (1H, t ), 7.20-7.16 (2H, m) 2-78 δ=9.27 (1H, s), 8.79 (1H, d), 8.37-8.30 (5H, m), 8.19-8.13 (2H, d), 7.89 (1H, s), 7.70-7.50 (18H, m), 7.40 (1H, s), 7.20 (1H, t) 2-79 δ=8.30 (2H, d), 8.19-8.13 (4H, m), 7.89 (2H, s), 7.62-7.50 (20H, m), 7.40 (1H, s), 7.20 (2H, t) 2-113 δ=8.55 (1H, d), 8.39 (2H, d), 8.19-8.12 (4H, m), 7.94 (1H, d), 7.89 (2H, s), 7.62-7.50 (17H, m), 7.35 ( 1H, t), 7.20-7.16 (3H, m) 2-123 δ=8.45 (1H, d), 8.30 (2H, d), 8.19-8.13 (3H, m), 7,93-7.89 (4H, m), 7.78 (1H, s), 7.62-7.49 (13H, m) ), 7.20 (1H, t) 2-142 δ=8.45 (1H, d), 8.30 (2H, d), 8.19-8.08 (4H, m), 7.93 (1H, d), 7.89 (2H, s), 7.80 (1H, d), 7.62-7.49 ( 14H, m), 7.20 (1H, t) > Experimental example 1> Manufacturing of organic light-emitting device

The glass substrate coated with indium tin oxide (ITO) with a thickness of 1,500 angstroms (Å) as a thin film was cleaned with distilled water ultrasonic waves. After the cleaning with distilled water was completed, the substrate was ultrasonically cleaned with solvents such as acetone, methanol, and isopropanol, followed by drying, and UV was used for 5 minutes in an ultraviolet (ultraviolet, UV) cleaner. Ultraviolet ozone (UVO) treatment. Thereafter, the substrate is transferred to a plasma cleaner (PT), and after plasma treatment is performed under vacuum to remove the ITO work function and residual film, the substrate is transferred to a thermal deposition device for organic deposition.

On the transparent ITO electrode (anode), a hole injection layer 2-TNATA (4,4',4"-tris[2-naphthyl(phenyl)amino]triphenylamine) is formed as a common layer ) And the hole transfer layer NPB (N,N'-bis(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine).

As follows, a light-emitting layer is thermally vacuum deposited on the hole injection layer 2-TNATA and the hole transfer layer NPB. As the light-emitting layer, a type of compound illustrated in Chemical Formula 1 and a type of compound illustrated in Chemical Formula 2 in the following Table 22 were deposited to 400 angstroms in each respective supply source as the main body, and 7% Doping deposits Ir(ppy) ₃ as a green phosphorescent dopant. Thereafter, bath cuproine (BCP) was deposited to 60 angstroms as a hole blocking layer, and Alq _{3 was} deposited to 200 angstroms on the hole blocking layer as an electron transfer layer. Finally, an electron injection layer was formed on the electron transfer layer by depositing lithium fluoride (LiF) to a thickness of 10 angstroms, and then an aluminum (Al) cathode was deposited to a thickness of 1,200 angstroms on the electron injection layer A cathode is formed, and therefore, an organic electroluminescence device is manufactured.

At the same time, for each material to be used in OLED manufacturing, all the organic compounds required to manufacture OLED were purified by vacuum sublimation at 10 ^-6 Torr to 10 ^-8 Torr. > Experimental example 2> Manufacturing of organic light emitting device

The glass substrate coated with ITO with a thickness of 1,500 angstroms as a thin film was cleaned by ultrasonic with distilled water. After the cleaning with distilled water was completed, the substrate was ultrasonically cleaned with solvents such as acetone, methanol, and isopropanol, followed by drying, and UVO treatment with UV for 5 minutes in a UV cleaner. Thereafter, the substrate is transferred to a plasma cleaner (PT), and after plasma treatment is performed under vacuum to remove the ITO work function and residual film, the substrate is transferred to a thermal deposition device for organic deposition.

On the transparent ITO electrode (anode), a hole injection layer 2-TNATA (4,4',4"-tris[2-naphthyl(phenyl)amino]triphenylamine) is formed as a common layer ) And the hole transfer layer NPB (N,N'-bis(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine).

As follows, a light-emitting layer is thermally vacuum deposited on the hole injection layer 2-TNATA and the hole transfer layer NPB. As the light-emitting layer, a type of compound illustrated in Chemical Formula 1 and a type of compound illustrated in Chemical Formula 2 in Table 23 were pre-mixed in a supply source and deposited to 400 angstroms as the host, and doped by 7% The dopant deposits Ir(ppy) ₃ as a green phosphorescent dopant. Thereafter, BCP was deposited to 60 angstroms as a hole blocking layer, and Alq _{3 was} deposited to 200 angstroms on the hole blocking layer as an electron transfer layer. Finally, an electron injection layer was formed on the electron transfer layer by depositing lithium fluoride (LiF) to a thickness of 10 angstroms, and then an aluminum (Al) cathode was deposited to a thickness of 1,200 angstroms on the electron injection layer A cathode is formed, and therefore, an organic electroluminescence device is manufactured.

At the same time, for each material to be used in OLED manufacturing, all the organic compounds required to manufacture OLED were purified by vacuum sublimation at 10 ^-6 Torr to 10 ^-8 Torr.

For the organic electroluminescence device manufactured as above, the electroluminescence (EL) properties were measured using M7000 manufactured by McScience InC., and using the measurement results, when the standard brightness is 6,000 cd/m² ( cd/m ² ), T ₉₀ was measured using the life measurement system (M6000) manufactured by Mike Scientific.

The properties of the organic electroluminescence device of the present disclosure are shown in Tables 21 to 23 below. For reference, Table 22 is an example of simultaneously depositing two host compounds in the respective supply sources of Experimental Example 1, and Table 23 is an example of depositing two luminescent layer compounds in one supply source after the pre-mixing of Experimental Example 2. And Table 21 is an example of using a single host material in Experimental Example 1. [Table 21] Light-emitting layer compound Drive voltage (V) Efficiency (cd/A) Color coordinates (x, y) Life (T ₉₀ ) Comparative example 1 17 3.88 77.2 (0.275, 0.672) 158 Comparative example 2 18 3.74 76.3 (0.279, 0.675) 162 Comparative example 3 30 3.84 740.4 (0.280, 0.676) 170 Comparative example 4 133 4.32 70.2 (0.281, 0.678) 137 Comparative example 5 189 3.86 68.2 (0.278, 0.682) 141 Comparative example 6 192 3.62 75.3 (0.274, 0.671) 170 Comparative example 7 199 3.85 72.3 (0.274, 0.679) 169 Comparative example 8 221 3.90 79.9 (0.277, 0.676) 148 Comparative example 9 223 3.77 73.4 (0.280, 0.674) 167 Comparative example 10 243 4.02 72.8 (0.280, 0.679) 121 Comparative example 11 244 3.88 69.4 (0.277, 0.681) 132 Comparative example 12 269 3.81 78.4 (0.281, 0.673) 180 Comparative example 13 271 3.61 76.2 (0.277, 0.672) 171 Comparative example 14 2-3 2.49 57.9 (0.272, 0.682) 89 Comparative example 15 2-8 2.63 58.6 (0.275, 0.676) 92 Comparative example 16 2-21 2.62 58.1 (0.276, 0.680) 96 Comparative example 17 2-27 2.51 59.8 (0.274, 0.677) 103 Comparative Example 18 2-28 2.69 60.1 (0.279, 0.669) 94 Comparative Example 19 2-31 2.65 59.0 (0.272, 0.680) 111 Comparative example 20 2-72 2.70 60.3 (0.278, 0.673) 102 Comparative Example 21 2-77 3.03 59.7 (0.278, 0.683) 127 Comparative example 22 2-79 3.50 61.2 (0.276, 0.664) 154 Comparative example 23 2-91 3.51 63.1 (0.275, 0.667) 157 Comparative example 24 2-102 3.47 62.4 (0.277, 0.674) 149 Comparative example 25 2-122 3.52 61.9 (0.271, 0.683) 151 Comparative Example 26 2-123 3.42 62.1 (0.273, 0.672) 158 [Table 22] Compound 1 Compound 2 ratio Drive voltage (V) Efficiency (cd/A) Color coordinates (x, y) Life (T ₉₀ ) Comparative Example 27 17 A 1:1 5.63 76.8 (0.276, 0.672) 242 Comparative Example 28 E 6.91 67.1 (0.281, 0.681) 180 Comparative Example 29 18 C 1:1 5.23 78.9 (0.278, 0.677) 264e3 Comparative example 30 D 5.68 80.1 (0.277, 0.679) 286 Comparative example 31 189 A 1:1 5.77 82.3 (0.284, 0.669) 301 Comparative example 32 C 5.51 86.4 (0.267, 0.673) 273 Comparative Example 33 18 A 1:2 5.72 76.3 (0.271, 0.680) 233 Comparative Example 34 1:1 5.59 78.7 (0.264, 0.685) 247 Comparative Example 35 189 B 1:2 6.55 63.6 (0.269, 0.674) 206 Comparative Example 36 1:1 6.12 67.8 (0.273, 0.681) 219 Example 1 17 2-3 1:8 4.68 101.7 (0.261 0.680) 322 Example 2 1:5 4.52 108.2 (0.267, 0.675) 368 Example 3 1:2 4.26 110.4 (0.275, 0.678) 387 Example 4 1:1 3.98 113.9 (0.276, 0.674) 401 Example 5 2:1 4.18 120.3 (0.274, 0.676) 398 Example 6 5:1 4.43 117.0 (0.276, 0.680) 386 Example 7 8:1 4.61 109.8 (0.275, 0.679) 354 Example 8 18 2-8 1:2 4.54 116.1 (0.267, 0.680) 392 Example 9 1:1 4.01 118.3 (0.270, 0.678) 417 Example 10 30 2-21 1:2 4.37 116.2 (0.260, 0.674) 397 Example 11 1:1 4.06 119.7 (0.263, 0.683) 409 Example 12 133 2-27 1:2 4.33 118.3 (0.282, 0.677) 384 Example 13 1:1 4.12 120.1 (0.282, 0.683) 415 Example 14 189 2-28 1:2 4.27 120.5 (0.267, 0.670) 377 Example 15 1:1 4.09 123.1 (0.278, 0.683) 411 Example 16 192 2-31 1:2 4.32 110.3 (0.271, 0.680) 354 Example 17 1:1 4.08 119.7 (0.263, 0.671) 408 Example 18 199 2-72 1:2 4.58 115.3 (0.281, 0.683) 392 Example 19 1:1 4.11 120.8 (0.262, 0.675) 421 Example 20 221 2-77 1:2 4.67 121.5 (0.276, 0.673) 404 Example 21 1:1 4.21 128.9 (0.266, 0.685) 467 Example 22 223 2-79 1:2 4.77 124.2 (0.275, 0.669) 432 Example 23 1:1 4.41 132.7 (0.280, 0.679) 488 Example 24 243 2-91 1:2 4.88 126.2 (0.263, 0.678) 459 Example 25 1:1 4.67 131.5 (0.270, 0.677) 490 Example 26 244 2-102 1:2 4.86 133.8 (0.284, 0.680) 469 Example 27 1:1 4.58 140.2 (0.277, 0.681) 505 Example 28 269 2-122 1:2 4.56 124.8 (0.275, 0.673) 429 Example 29 1:1 4.37 131.2 (0.269, 0.680) 467 Example 30 271 2-123 1:2 4.86 138.7 (0.286, 0.678) 507 Example 31 1:1 4.65 143.2 (0.281, 0.679) 563 [Table 23] Compound 1 Compound 2 ratio Drive voltage (V) Efficiency (cd/A) Color coordinates (x, y) Life (T ₉₀ ) Comparative Example 37 17 A 1:1 5.79 83.9 (0.273, 0.675) 258 Comparative Example 38 C 1:1 5.62 90.2 (0.276, 0.684) 297 Comparative Example 39 189 D 1:1 5.42 92.8 (0.284, 0.678) 330 Comparative Example 40 E 1:1 6.09 74.5 (0.269, 0.680) 254 Comparative Example 41 244 A 1:1 5.55 88.6 (0.271, 0.683) 284 Comparative Example 42 B 1:1 6.13 70.6 (0.286, 0.666) 237 Example 32 17 2-8 1:1 3.17 124.8 (0.274, 0.671) 502 Example 33 2-28 1:1 3.21 123.6 (0.268, 0.681) 511 Example 34 18 2-77 1:1 3.48 134.2 (0.282, 0.679) 575 Example 35 2-79 1:1 3.59 140.4 (0.280, 0.676) 601 Example 36 189 2-91 1:1 3.62 141.2 (0.277, 0.682) 609 Example 37 2-102 1:1 3.64 143.6 (0.263, 0.675) 618 Example 38 271 2-122 1:1 3.50 136.7 (0.275, 0.677) 591 Example 41 2-123 1:1 3.60 151.3 (0.276, 0.670) 653

As can be seen from Tables 21 to 23, it is recognized that when both the heterocyclic compound shown in Chemical Formula 1 and the heterocyclic compound shown in Chemical Formula 2 are included in the organic material layer of the organic light-emitting device, it is compared When each of the compounds is included, superior efficiency and lifetime properties are obtained. Such excellent results may lead to the prediction that when the two compounds are included at the same time, the phenomenon of excitation complexes will occur.

The phenomenon of excited complex is a phenomenon in which electrons are exchanged between two molecules, and it releases HOMO energy level of electron donor molecules (donor, p-host) and LUMO energy of electron acceptor molecules (acceptor, n-host) The phenomenon of the magnitude of energy. When an electron donor molecule (donor, p-host) with a desirable hole transfer capability and an electron acceptor molecule (acceptor, n-host) with a desirable electron transfer capability are used together as the host of the light-emitting layer, Holes are injected into electron donor molecules (donor, p-host), and electrons are injected into electron acceptor molecules (acceptor, n-host). When an excited complex phenomenon occurs between two molecules, reverse inter-system crossover (RISC) will occur smoothly, and therefore the internal quantum efficiency of light emission can reach 100%. In addition, the driving voltage can be reduced, which significantly contributes to the improvement of life.

In addition, after premixing the compounds, a light-emitting host formed of multiple types of compounds is deposited, and the light-emitting host is formed as a deposition supply source in the present disclosure (Experimental Example 2, Table 23). In this article, avoiding multiple depositions has the advantage of maintaining the uniformity of the film surface and the properties of the film. In addition, while reducing the overall process cost by simplifying the process, it is possible to form a device with improved efficiency, driving voltage, and lifespan.

As seen from Table 22 and Table 23, the condensed carbazole structure of the heterocyclic compound structure shown in Chemical Formula 2 of the present application is a structure including two carbazoles or one carbazole and one heterocyclic ring, and thereby Since the nitrogen in carbazole and heteroatoms have unshared electron pairs, they have strong electron donor properties. In other words, as can be seen from Table 22 and Table 23, it is recognized that the heterocyclic compound corresponding to Chemical Formula 1 and the compound corresponding to compounds A to E (biscarbazole type; or wherein the carbazole And a heterocyclic bonding structure), the total driving voltage/efficiency/lifetime is superior.

In addition, due to the wide region of π-conjugation corresponding to the entire basic skeleton, a wider HOMO energy level region is obtained compared to the unfused carbazole compound, resulting in a wider hole distribution. Therefore, the fast hole transfer property is recognized when the device is driven, and thereby, by reducing the driving voltage, it is recognized that there are expected advantages of improved current efficiency and reduced device threshold voltage.

In addition, the fused carbazole as Chemical Formula 2 has a form in which a pentagonal or hexagonal ring is fused by a π-π bond. This results in the formation of a structure (rigid structure) with minimal intramolecular distortion, and thus high thermal stability (T _d95 : 400° C. or higher, high T _g ) is obtained. High thermal stability is a favorable factor for overcoming the harsh high vacuum and high temperature conditions of the organic light emitting device (OLED) deposition process, and is also favorable for device degradation when the device is driven for a long period of time. Therefore, it is seen that, based on low voltage, high efficiency, and high thermal stability, the condensed carbazole structure as the structure shown in Chemical Formula 2 is a basic structure that can be used as a material having a desirable lifetime.

In addition, when pre-mixing is performed as in Table 23, it is necessary to identify the unique thermal properties of each of the materials during the mixing. In this article, when depositing a pre-mixed host material from a source, the unique thermal properties of the material can significantly affect the deposition conditions including the deposition rate. When the thermal properties of two or more types of pre-mixed materials are dissimilar and very different, the repeatability and reproducibility may not be maintained in the deposition process, which means that it is impossible to make a complete deposition process in one deposition process. Uniform OLED.

In view of the above circumstances, the thermal properties of the material can also be controlled according to the shape of the molecular structure, and the appropriate combination of the basic structure and substituents of each of the materials can be used to adjust the electrical properties of the material. Therefore, in addition to the basic structure, various substituents in Chemical Formula 2 and the CN bonding of the fused carbazole in Chemical Formula 2 can also be used to enhance device performance, and the thermal properties of each of the materials can be controlled To ensure the diversity of various pre-mixed deposition processes between the main body and the main body. This has the advantage of ensuring the diversity of the pre-mixed deposition process using three, four or more host materials and two compounds as the host.

In addition, when the OLED is driven, due to the thermal energy generated by the non-radiative emission and the thermal energy generated by the current resistance caused by the device driving for a long period of time, the inside of the device is exposed to various forms of heat for a long period of time. Unlike metals, organic materials have very low thermal resistance, and therefore, accurate thermal stability information is required to ensure the thermal stability of the materials. In addition, the OLED deposition process is also performed in a high vacuum state at a high temperature, and the material with low thermal stability has deteriorated during the deposition process, making it impossible to drive as an OLED. Therefore, checking the thermal stability of the materials forming the device is a very important preparatory work for building OLEDs.

The condensed carbazole structure described in Chemical Formula 2 is a condensed structure in which many pentagonal/hexagonal rings are strongly connected by π-π bonds, and has a rigid structure, and therefore has a temperature of 100°C or higher High Tg at 100°C and very high Td (95%) at 400°C or higher. It can be seen that this is a material that can withstand the harsh high vacuum/high temperature state of the OLED deposition process and has sufficient stability to prevent device degradation even when the device is driven for a long period of time.

Figures 4 to 21 are shown in chemical formula 2 measured by Mettler Toledo's Thermogravimetric Analysis (TGA)/Differential Scanning Calorimetry (DSC) device Thermal analysis data for each material and specific compound. The measured Td ₉₅ is measured by raising the temperature to 600°C by heating, so that the temperature rises from 30°C at 10 Kelvin (K) per minute. In thermal properties such as the glass transition temperature (Tg), crystallization temperature (Tc), melting temperature (Tm) and decomposition temperature (Td/95%) corresponding to chemical formula 2 and specific compounds, the glass transition temperature and decomposition temperature are identified, To first identify the stability of the device during long-term driving and high-vacuum deposition processes.

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

In addition, FIGS. 18 and 19 are graphs showing the thermal stability of Compound A, and FIGS. 20 and 21 are graphs showing the thermal stability of Compound C.

In the graphs showing the thermal stability of FIGS. 4 to 21, Td ₉₅ is a point at which the temperature is measured when 95% of the mass is maintained after the temperature is applied, and a high Td ₉₅ means stability at high temperatures.

As recognized by comparing Figures 4 to 17 with Figures 18 to 21, in compound A (Figure 18 and Figure 19) and compound C (Figure 20 and Figure 21) with biscarbazole structure, Td ₉₅ It is measured as low as or below 400°C, which results in lower thermal stability compared to fused carbazole compounds.

Therefore, it is recognized that the basic structure including both the compound shown in Chemical Formula 1 and the compound shown in Chemical Formula 2 is used to manufacture devices with low voltage/high efficiency targets or OLEDs with high efficiency/long life or low voltage/long life properties. Medium is effective enough.

100: substrate 200: anode 300: organic material layer 301: hole injection layer 302: Hole Transfer Layer 303: light-emitting layer 304: hole barrier 305: electron transfer layer 306: electron injection layer 400: Cathode

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

100: substrate

200: anode

300: organic material layer

400: Cathode

Claims (17)

An organic light-emitting device, comprising: a first electrode; a second electrode; and one or more organic material layers arranged between the first electrode and the second electrode, wherein one or more of the organic material layers are simultaneously The heterocyclic compound represented by the following Chemical Formula 1 and the heterocyclic compound represented by the following Chemical Formula 2 are included: [Chemical Formula 1]

[Chemical formula 2]

In Chemical Formula 1 and Chemical Formula 2, N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclic group, and includes one or more N; L is a direct bond; substituted or unsubstituted aromatic Group; or substituted or unsubstituted heteroaryl group, a is an integer from 1 to 3, and when a is 2 or greater than 2, L is the same or different from each other; R ₁ to R ₁₉ are the same or different from each other , And each independently selected from the group consisting of: hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkyne Substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted A substituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted A substituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted heterocyclic ring, b and c are each an integer of 1 to 3, d is an integer of 0 to 2, when b is 2 or greater than 2, R ₉ are the same or different from each other, when c is 2 or greater than 2, R ₁₀ are the same or different from each other, and when d is an integer 2, R ₁₉ are the same or different from each other; A ₁ and A ₂ are the same or different from each other and are each independently O; S; NR _a; or CR _b R _c; and R _a to R _c are the same or different from each other, and each independently hydrogen; substituted or unsubstituted alkyl; substituted Or unsubstituted aryl; or substituted or unsubstituted heteroaryl. The organic light-emitting device according to claim 1, wherein Chemical Formula 1 is represented by one of the following Chemical Formula 3 to Chemical Formula 6: [Chemical Formula 3]

[Chemical formula 4]

[Chemical formula 5]

[Chemical formula 6]

In Chemical Formula 3 to Chemical Formula 6, the substituent has the same definition as that in Chemical Formula 1. The organic light-emitting device according to claim 1, wherein Chemical Formula 1 is represented by one of the following Chemical Formulas 7 to 9: [Chemical Formula 7]

[Chemical formula 8]

[Chemical formula 9]

In Chemical Formula 7 to Chemical Formula 9, R1 to R10, L, a, b and c have the same definitions as in Chemical Formula 1; X1 is CR21 or N, X2 is CR22 or N, X3 is CR23 or N, X4 is CR24 or N, and X5 is CR25 or N; and R21 to R25 and R27 to R32 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen; deuterium; halogen; cyano; substituted or unsubstituted Substituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted Or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; substituted or unsubstituted phosphine oxide; and substituted or unsubstituted The amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or heterocyclic ring. The organic light-emitting device according to claim 3, wherein

It is represented by one of the following Chemical Formula 10 to Chemical Formula 12: [Chemical Formula 10]

[Chemical formula 11]

[Chemical formula 12]

In Chemical Formula 10, one or more of X1, X3, and X5 is N, and the rest have the same definition as in Chemical Formula 7; In Chemical Formula 11, one or more of X1, X2, and X5 are N, and the rest have the same definition as in Chemical Formula 7; In Chemical Formula 12, one or more of X1 to X3 is N, and the rest have the same definition as in Chemical Formula 7; and R22, R24 and R33 to R36 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkene Group; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted Substituted aryl groups; substituted or unsubstituted heteroaryl groups; substituted or unsubstituted phosphine oxide groups; and substituted or unsubstituted amine groups, or two or more groups adjacent to each other The groups are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or heterocyclic ring. The organic light-emitting device according to claim 4, wherein the chemical formula 10 is selected from the following structural formulae:

In the structural formula, R21 to R25 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or Unsubstituted alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl ; Substituted or unsubstituted aryl groups; substituted or unsubstituted heteroaryl groups; substituted or unsubstituted phosphine oxide groups; and substituted or unsubstituted amine groups, or two adjacent to each other Or more groups are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or heterocyclic ring. The organic light-emitting device according to claim 1, wherein Chemical Formula 2 is represented by any one of the following Chemical Formulas 2-7 to 2-9: [Chemical Formula 2-7]

[Chemical formula 2-8]

[Chemical formula 2-9]

In Chemical Formula 2-7 to Chemical Formula 2-9, A ₁ , A ₂ , R ₁₁ and R ₁₄ have the same definitions as in Chemical Formula 2; A ₃ is O; S; or NR _g ; R ₅₀ and R ₅₁ Is hydrogen; or a substituted or unsubstituted aryl group, and at least one of R ₅₀ and R ₅₁ is a substituted or unsubstituted aryl group; R _g , R ₅₂ and R ₅₃ are the same or different from each other, And each independently is hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl; r is an integer from 0 to 3; and q is An integer from 0 to 4. The organic light-emitting device according to claim 1, wherein R ₁₁ and R ₁₄ to R ₁₉ of Chemical Formula 2 are hydrogen. The organic light-emitting device according to claim 1, wherein Chemical Formula 1 is represented by any one of the following compounds:

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

. The organic light-emitting device according to claim 1, wherein the organic material layer includes at least one of a hole blocking layer, an electron injection layer, and an electron transfer layer, and the hole blocking layer, the electron injection layer, and At least one of the electron transfer layers includes the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2. The organic light emitting device according to claim 1, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2. The organic light-emitting device according to claim 1, wherein the organic material layer includes a light-emitting layer, the light-emitting layer includes a host material, and the host material includes the heterocyclic compound represented by Chemical Formula 1 and The heterocyclic compound. The organic light emitting device according to claim 1, comprising one, two or more layers selected from the group consisting of: light emitting layer, hole injection layer, hole transfer layer, electron injection layer, electron transfer layer , Electron blocking layer and hole blocking layer. A composition for an organic material layer of an organic light-emitting device, the composition including a heterocyclic compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2: [Chemical Formula 1]

[Chemical formula 2]

In Chemical Formula 1 and Chemical Formula 2, N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclic group, and includes one or more N; L is a direct bond; substituted or unsubstituted aromatic Group; or substituted or unsubstituted heteroaryl group, a is an integer from 1 to 3, and when a is 2 or greater than 2, L is the same or different from each other; R ₁ to R ₁₉ are the same or different from each other , And each independently selected from the group consisting of: hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkyne Substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted A substituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted A substituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted heterocyclic ring, b and c are each an integer of 1 to 3, d is an integer of 0 to 2, when b is 2 or greater than 2, R ₉ are the same or different from each other, when c is 2 or greater than 2, R ₁₀ are the same or different from each other, and when d is an integer 2, R ₁₉ are the same or different from each other; A ₁ and A ₂ are the same or different from each other and are each independently O; S; NR _a; or CR _b R _c; R _a to R _c, and the same or different from each other, and each independently hydrogen; substituted or unsubstituted alkyl; substituted Or unsubstituted aryl; or substituted or unsubstituted heteroaryl. The composition for an organic material layer of an organic light-emitting device according to claim 14, wherein, in the composition, the heterocyclic compound represented by Chemical Formula 1: the heterocyclic compound represented by Chemical Formula 2 With a weight ratio of 1:10 to 10:1. A method for manufacturing an organic light-emitting device, the method comprising: Prepare the substrate; Forming a first electrode on the substrate; Forming one or more organic material layers on the first electrode; and Forming a second electrode on the organic material layer, Wherein said forming an organic material layer includes forming one or more organic material layers using the composition for an organic material layer according to claim 14. The method of manufacturing an organic light-emitting device according to claim 16, wherein the forming of the organic material layer is performed by using a thermal vacuum after premixing the heterocyclic compound shown in Chemical Formula 1 and the heterocyclic compound shown in Chemical Formula 2 Deposition method to form.

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