TWI831900B - 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 application for organic light-emitting Composition of the organic material layer of the device

This application claims the priority and rights of Korean Patent Application No. 10-2018-0172475, which was filed with the Korean Intellectual Property Office on December 28, 2018. The entire content of the Korean patent application is incorporated into this case for reference.

This specification relates to an organic light-emitting device, a method for manufacturing an organic light-emitting device, and a composition of an organic material layer for an organic light-emitting device.

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 provided between two electrodes. When a voltage is applied to an organic light-emitting device having such a structure, electrons and holes injected from the two electrodes are coupled in the organic film, and when these electrons When the electric hole annihilates, light will be emitted. The organic thin film may be formed in a single layer or multiple layers as needed.

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

To enhance the performance, lifetime, or efficiency of organic light-emitting devices, there is a continuing need to develop organic thin film materials.

[Prior Technical Document]

[Patent document]

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

The present 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.

One embodiment of the present application provides an organic light-emitting device. The organic light-emitting device includes: a first electrode; a second electrode; and one or more organic material layers disposed between the first electrode and the second electrode. between, The one or more 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.

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; a substituted or unsubstituted aromatic group; or a 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 as or different from each other, and R ₁ to R ₁₉ are the same as or different from each other. , and each is independently selected from the group consisting of: hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkyne base; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted Substituted heteroaryl; substituted or unsubstituted phosphine oxide group; and 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 amine group. Substituted aliphatic or aromatic hydrocarbon ring or 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 are the same as or different from each other, when c is 2 or greater than 2, R ₁₀ are the same as or different from each other, and when d is an integer 2, R ₁₉ are the same as or different from each other, A ₁ and A ₂ are the same as or different from each other Different, and each is independently O; S; NR _a ; or CR _b R _c , and R _a to R _c are the same as each other or different from each other, and each is independently hydrogen; substituted or unsubstituted alkyl; Substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl.

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 heterocyclic compound represented by Chemical Formula 2 compound.

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

The heterocyclic compound according to one embodiment of the present application can be used as a material for an organic material layer of an organic light-emitting device. Heterocyclic compounds can be used as materials for hole injection layers, hole transfer layers, light emitting layers, electron transfer layers, electron injection layers, charge generation layers, etc. in organic light emitting devices. Specifically, the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 can be used simultaneously as materials for the light-emitting layer of the organic light-emitting device. In addition, when the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 are used simultaneously in an organic light-emitting device, the driving voltage of the device can be reduced, the light efficiency can be improved, and the thermal stability of the compound can be to improve the lifespan of the device.

Specifically, in the heterocyclic compound represented by Chemical Formula 1, the carbon position No. 3 of the dibenzofuran structure is substituted by an N-containing ring and the benzene that is not substituted by the N-containing ring in the dibenzofuran structure is carbazole. By structural substitution, an electronically more stable structure is obtained and, therefore, the device lifetime can be increased.

100:Substrate

200:Anode

300: Organic material layer

301: Hole injection layer

302: Hole transfer layer

303: Luminous layer

304: Hole blocking layer

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 one embodiment of the present application.

Figures 4 and 5 are graphs showing the thermal stability of compound 2-8 of the present application.

Figures 6 and 7 are curves showing the thermal stability of compound 2-18 of the present application. Figure.

Figures 8 and 9 are graphs showing the thermal stability of compound 2-79 of the present application.

Figures 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.

Figures 14 and 15 are graphs showing the thermal stability of compound 2-20 of the present application.

Figures 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.

20 and 21 are graphs showing the thermal stability of compound C of the present application.

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

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

In this specification, "substituted or unsubstituted" means a group selected from the group consisting of C1 to C60 linear or branched alkyl; C2 to C60 linear or branched alkenyl; C2 to C60 linear 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 heteroaryl One or more substituents of the group consisting of amines are substituted or unsubstituted, or are substituted or unsubstituted by a substituent bonded 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 one embodiment of the present application, R, R' and R" are the same as each other or different from each other, and can each independently be hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted aryl ; Or substituted or unsubstituted heteroaryl.

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

In this specification, the alkyl group includes a linear or branched chain alkyl group having 1 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkyl group may be from 1 to 60, specifically from 1 to 40 and more specifically from 1 to 20. Specific examples of the alkyl group may include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl- Butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, 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, tertiary octyl, 1 -Methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, Isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but are not limited thereto.

In this specification, alkenyl groups include straight-chain or branched-chain alkenyl groups having 2 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkenyl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 2 to 20. Specific examples of the alkenyl group 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 are not limited thereto.

In this specification, an alkynyl group includes a linear or branched chain alkynyl group having 2 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkynyl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 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 is preferably 1 to 20. Specific examples of the alkoxy group may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy Oxygen, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octyloxy, n- Nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc., but are not limited thereto.

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

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

基、菲基、苝基、第蒽基、三伸苯基、萉基、芘基、稠四苯基、稠五苯基、芴基、茚基、苊基、苯並芴基、螺二芴基、2,3-二氫-1H-茚基、其稠環等，但不限於此。 In this specification, the aryl group includes a monocyclic or polycyclic aryl group having 6 to 60 carbon atoms, and may be further substituted by other substituents. As used herein, polycyclic means a group in which an aryl group is directly bonded 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 includes spiro. The number of carbon atoms of the aryl group may be from 6 to 60, specifically from 6 to 40 and more specifically from 6 to 25. Specific examples of the aryl group may include phenyl, biphenyl, triphenyl, naphthyl, anthracenyl,

Base, phenanthrenyl, perylene, anthracenyl, triphenyl, pyrenyl, pyrenyl, tetraphenyl, pentaphenyl, fluorenyl, indenyl, acenaphthyl, benzofluorenyl, spirobifluorenyl base, 2,3-dihydro-1H-indenyl, its fused ring, etc., but are not limited to these.

In the present 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 may include

,

,

,

,

,

etc., however, the structure is not limited thereto.

嗪基、噻嗪基、二氧雜環己烯基(dioxynyl group)、三嗪基(triazinyl group)、四嗪基(tetrazinyl group)、喹啉基、異喹啉基、喹唑啉基、異喹唑啉基、喹嗪啉基(qninozolinyl group)、氮雜萘基(naphthyridyl group)、吖啶基、啡啶基(phenanthridinyl group)、咪唑並吡啶基、二氮亞萘基(diazanaphthalenyl group)、三氮茚基、吲哚基、吲哚嗪基、苯並噻唑基、苯並噁唑基、苯並咪唑基、苯並噻吩基、苯並呋喃基、二苯並噻吩基、二苯並呋喃基、咔唑基、苯並咔唑基、二苯並咔唑基、吩嗪基、二苯並噻咯基(dibenzosilole group)、螺二(二苯並噻咯)(spirobi(dibenzosilole))、二氫吩嗪基、吩

嗪基、啡啶基(phenanthridyl group)、咪唑並吡啶基、噻吩基、吲哚並[2,3-a]咔唑基、吲哚並[2,3-b]咔唑基、吲哚啉基、10,11-二氫二苯並[b,f]氮呯基、9,10-二氫吖啶基、菲嗪基(phenanthrazinyl group)、啡噻嗪基、呔嗪基、萘啶基、菲咯啉基(phenanthrolinyl group)、苯並[c][1,2,5]噻二唑基、5,10-二氫苯並[b,e][1,4]氮雜矽烷啉基(5,10-dihydrobenzo[b,e][1,4]azasilinyl)、吡唑並[1,5-c]喹唑啉基、吡啶並[1,2-b]吲哚基、吡啶並[1,2-a]咪唑並[1,2-e]吲哚基、5,11-二氫茚並[1,2-b]咔唑基等，但不限於此。 In the present specification, heteroaryl groups include O, S, Se, N or Si as heteroatoms, include monocyclic or polycyclic heteroaryl groups having 2 to 60 carbon atoms, and may be further substituted by other substituents. As used herein, polycyclic means a heteroaryl group directly bonded 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 groups. The number of carbon atoms of the heteroaryl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 3 to 25. Specific examples of the heteroaryl group may include pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, Triazolyl, furfuryl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl,

Azinyl, thiazinyl, dioxynyl group, triazinyl group, tetrazinyl group, quinolinyl, isoquinolyl, quinazolinyl, iso Quinazolinyl group, qninozolinyl group, naphthyridyl group, acridinyl group, phenanthridinyl group, imidazopyridinyl group, diazanaphthalenyl group, Indolinyl, indolyl, indolazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuran base, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, phenazinyl, dibenzosilole group, spirobi(dibenzosilole), Dihydrophenazinyl, phenylene

Azinyl, phenanthridyl group, imidazopyridyl, thienyl, indolo[2,3-a]carbazolyl, indolo[2,3-b]carbazolyl, indoline base, 10,11-dihydrodibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenanthrazinyl group, frizinyl group, naphthyridinyl group , phenanthrolinyl group, benzo[c][1,2,5]thiadiazolyl, 5,10-dihydrobenzo[b,e][1,4]azesasilanyl 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 are not limited thereto.

In this specification, the amine group may be selected from the group consisting of: monoalkylamino group; monoarylamino group; monoheteroarylamino group; -NH ₂ ; dialkylamino group; diarylamine group ; diheteroarylamine group; alkylarylamine 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 amine group may include methylamino group, dimethylamino group, ethylamine group, diethylamine group, phenylamine group, naphthylamino group, diphenylamine group, diphenylamine group base, anthracenylamino group, 9-methyl-anthracenylamino group, diphenylamino group, phenylnaphthylamine group, ditolylamino group, phenyltolylamino group, triphenylamine group, bis- Phenylnaphthylamino, phenylbiphenylamino, biphenylfluorenylamino, phenyltriphenylamino, biphenyltriphenylamino, etc., but are not limited thereto.

In this specification, an aryl group means an aryl group having two bonding sites, that is, a divalent group. The description given above for aryl groups applies to aryl groups, except where each is divalent. In addition, heteroaryl means a heteroaryl group having two bonding sites, that is, a divalent group. The description given above for heteroaryl groups applies to heteroaryl groups, except where each is divalent.

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 group; alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; and heterocyclic group. Specifically, the phosphine oxide group may be specifically substituted by an aryl group, and as the aryl group, the above-mentioned examples may be used. Examples of the phosphine oxide group may include diphenylphosphine oxide group, dinaphthylphosphine 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 each other or different from each other, and may each independently be a substituent formed from at least one of the following: hydrogen; deuterium; halogen group; alkyl group; alkenyl group; alkoxy group; cycloalkyl group; Aryl; and heterocyclyl. Specific examples of the silyl group may include trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group , diphenylsilyl group, phenylsilyl group, etc., but are not limited to these.

In this specification, an "adjacent" group may mean a substituent that replaces an atom directly linked to the atom replaced by the corresponding substituent, a substituent that is spatially closest to the corresponding substituent, or a substituent that is substituted by the corresponding substituent. another substituent for the atom. For example, two substituents substituting ortho positions in a benzene ring and two substituents substituting the same carbon in an aliphatic ring can be interpreted as groups that are "adjacent" to each other.

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

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

In one 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 6]

In Chemical Formula 3 to Chemical Formula 6, the substituents have the same definitions as in Chemical Formula 1.

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

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's.

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 heterocycle substituted by one or more substituents 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 heterocycle substituted with one or more substituents and including one or more N and including three or less N.

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

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

In one embodiment of the present application, N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocycle and includes two or more Ns.

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

In one embodiment of the present application, N-Het can be pyrimidinyl which is unsubstituted or substituted by phenyl; unsubstituted or selected from phenyl, biphenyl, naphthyl, dimethylfluorenyl, Triazinyl substituted by one or more substituents of the group consisting of dibenzofuranyl and dibenzothienyl; benzimidazolyl unsubstituted or substituted by phenyl; unsubstituted or selected from benzene A quinolinyl group substituted by one or more substituents of the group consisting of a base and a biphenyl group; or an unsubstituted or phenanthrolinyl group substituted by a phenyl group.

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

[Chemical Formula 7]

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 The group consisting of: hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted Substituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl ; Substituted or unsubstituted phosphine oxide groups; and substituted or unsubstituted amine groups, 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.

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。 In one embodiment of the present application,

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

is the site linked to L.

[Chemical formula 11]

In Chemical Formula 10, one or more of X1, X3, and X5 is N, and the others have the same definitions as in Chemical Formula 7, and in Chemical Formula 11, one or more of X1, N, and the others have the same definitions as in Chemical Formula 7, in Chemical Formula 12, one or more of X1 to X3 is N, and the others have the same definitions as in Chemical Formula 7, and R22, R24 and R33 to R36 are the same as each other 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 base; 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 An 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 heterocycle.

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

In the structural formula, R21 to R25 are the same as each other 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 Substituted 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 Multiple groups are bonded to each other to form substituted or unsubstituted aliphatic or aromatic hydrocarbon rings or heterocycles.

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

The substituents in Chemical Formula 13 have the same definitions as in Chemical Formula 11.

In one embodiment of the present application, Chemical Formula 12 may be represented by the following Chemical Formula 14.

The substituents in Chemical Formula 14 have the same definitions as in Chemical Formula 12 definition.

In one embodiment of the present application, Chemical Formula 11 may be represented by the following Chemical Formula 15.

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

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

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

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

In another embodiment, R9 and R10 are hydrogen.

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

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

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

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

In another embodiment, two or more adjacent substituents in R1 to R8 are bonded to each other to form an unsubstituted or substituted 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 heterocycle that is unsubstituted or substituted by an aryl group or an 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 heterocycle that is unsubstituted or substituted by 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 phenyl-substituted indole ring; 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。 In another embodiment,

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

is the site of attachment to the dibenzofuran structure.

In Chemical Formula 16, R1 to R4 have the same definitions as in Chemical Formula 1, Y is O, S, NR _d or CR _e R _f , R _d , _Re , R _f , R41 and R42 are the same as each other or different from each other. , and each is independently selected from the group consisting of: hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkyne base; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted Substituted heteroaryl; substituted or unsubstituted phosphine oxide group; and 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 amine group. Substituted aliphatic or aromatic hydrocarbon ring or substituted or unsubstituted heterocyclic ring, f is an integer from 0 to 4, and when f is 2 or greater than 2, R41 is the same as or different from each other, and g is 0 to 4 an integer of 2, and when g is 2 or greater than 2, R42 are the same as each other or different from each other.

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

In the structural formula, the substituents have the same definitions as in Chemical Formula 16.

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

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

In another embodiment, R28 to R31 are hydrogen.

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

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

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

In another embodiment, R27 and R32 are phenyl.

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

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

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

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

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

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

In one embodiment of the present application, R33 to R36 are the same as or different from each other, and each is independently hydrogen; deuterium; aryl; or heteroaryl, or two or more groups adjacent to each other are bonded to each other Combined to form substituted or unsubstituted aliphatic or aromatic hydrocarbon rings or heterocycles.

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

In another embodiment, R33 to R36 are the same as each other or different from each other, and each is independently hydrogen; deuterium; 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 each other or different from each other, and each is 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 each other or different from each other, and each is 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 one embodiment of the present 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 one embodiment of the present application, Y is O or S.

In another embodiment, Y is _NRd , and _Rd is aryl.

In another embodiment, Y is _NRd , and _Rd is phenyl.

In another embodiment, Y is _{CReRf ,} and Re _{and Rf} are alkyl.

In another embodiment, Y is _{CReRf ,} and Re _{and Rf} are methyl.

In one embodiment of the present 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 one embodiment of this application, R42 is hydrogen; or deuterium.

In another embodiment, R42 is hydrogen.

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

In one embodiment of the present application, R _a to R _c are the same as each other or different from each other, and can each independently be 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 each other or different from each other, and can 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 group.

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

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

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

In another embodiment, R ₁₁ to R ₁₉ are the same as each other or different from each other, and can 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 each other or different from each other, and can each independently be 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 each other or different from each other, and can each independently be 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 each other or different from each other, and can each independently be hydrogen; C6 to C40 aryl; or C2 to C40 hetero that is unsubstituted or substituted by C6 to C40 aryl. Aryl.

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

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

In one embodiment of the present application, R ₁₁ and R ₁₄ can be hydrogen.

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

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

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

[Chemical formula 2-1]

[Chemical formula 2-3]

[Chemical formula 2-5]

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 in Chemical Formula 2.

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

[Chemical formula 2-7]

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 as each other or different from each other, and each independently 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 one 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 substituted or unsubstituted C6 to C60 aryl.

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

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

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

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

In one embodiment of the present application, R ₅₂ and R ₅₃ can be hydrogen.

In one embodiment of the present application, _Rg may be substituted or unsubstituted aryl.

In another embodiment, _Rg may be substituted or unsubstituted C6 to C60 aryl.

In another embodiment, _Rg can be substituted or unsubstituted C6 to C40 aryl.

In another embodiment, _Rg can be C6 to C40 aryl.

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 together with the heterocyclic compound shown in Chemical Formula 1 in an organic light-emitting device, especially as a host material, Very fast hole transfer properties are obtained, which lowers the threshold voltage and drive voltage of the device, and therefore the device can be driven even at low voltages.

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

Chemical formula 2-9 is a case where the fused 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 conjugated region as in chemical formula 2-8, so it can be used as Various heteroaryl substitutions are an auxiliary means to control the band gap. Specifically, since dibenzofuran/dibenzothienyl, etc. have the largest structure in structure, the driving voltage is slightly increased compared to the basic skeleton. However, due to the property of maintaining a higher T1 energy level, In addition, it also has the highest structural stability, so it will obtain particularly superior device life properties.

When both the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 are included in the organic material layer of the organic light-emitting device, superior efficiency and lifetime effects will be obtained. Such results may lead to the prediction that an exciplex phenomenon will occur when both compounds are included simultaneously.

The excitation complex phenomenon is due to the electron exchange between two molecules that releases the donor (p-body) HOMO energy level and the acceptor (n-body) lowest unoccupied molecular orbital (LUMO) energy level Phenomena of large and small energy. When excitation complexation 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 desired hole transfer capability and an acceptor (n-host) with a desired electron transfer capability are used as hosts of the light-emitting layer, holes are injected into the p-host, and electrons is injected into the n-body, and therefore, the driving voltage can be reduced, which ultimately contributes to lifetime improvement.

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

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

In addition, by introducing various substituents into the structures represented by Chemical Formula 1 and Chemical Formula 2, compounds having unique properties of the introduced substituents can be synthesized. For example, by introducing 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 manufacturing organic light-emitting devices into the core structure, it can be synthesized Materials that meet the requirements for each organic material layer.

In addition, by introducing various substituents into the structures represented by Chemical Formula 1 and Chemical Formula 2, the energy band gap can be finely controlled, and at the same time, 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 excellent thermal stability. This increase in thermal stability becomes an important factor in providing drive stability to the device.

Heterocyclic compounds according to one embodiment of the present application can be prepared using multi-step chemical reactions. First some intermediate compounds are prepared and can be obtained from the intermediate compounds The compound represented by Chemical Formula 1 or Chemical Formula 2 is prepared. More specifically, the heterocyclic compound according to one embodiment of the present application can be prepared based on the preparation example to be explained 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.

Specific details regarding 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 thereto.

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

The composition has a form of simply mixing two or more of the compounds, and the materials in powder form may be mixed before forming the organic material layer of the organic light-emitting device, or the liquid compounds may be mixed 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 the 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 above-mentioned heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 to form one or more organic material layers, according to the present application The organic light-emitting device according to an embodiment of the invention can be manufactured using 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 can be formed into 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 printing, spray method, roller coating. roll coating), etc., but not limited to this.

The organic material layer of the organic light-emitting device of the present disclosure may be formed into a single-layer structure, or may be formed into a multi-layer structure in which two or more organic material layers are laminated. For example, an organic light-emitting device according to one 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 organic material layers. 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 the One or more organic material layers include a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2.

In one 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 materials for 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 materials 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 a material of the red organic light-emitting device.

The organic light-emitting device of the present disclosure may further include one, two or more 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 one 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 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, 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 compound represented by Chemical Formula 2 compound.

1 to 3 illustrate the laminating sequence of electrodes and organic material layers of an organic light-emitting device according to one embodiment of the present application. However, the scope of the present application is not limited to these figures, and structures of organic light-emitting devices known in the art may also be used in the present 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.

Figure 3 shows a case where the organic material layer is multiple layers. 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, other layers except the light-emitting layer may not be included, and other necessary functional layers may be further included.

One embodiment of the present application provides a method for manufacturing an organic light-emitting device, the method including: 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 forming the organic material layer includes forming one or more organic material layers using a 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 one embodiment of the present application, the forming of the organic material layer is after premixing the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 Deposition using thermal vacuum method to form.

Premixing means that the material composed of the heterocyclic compound represented by Chemical Formula 1 and the material composed of the heterocyclic compound represented by Chemical Formula 2 are premixed in a supply source before being deposited on the organic material layer.

According to one embodiment of the present application, the premixed material may be referred to as a composition for the organic material layer.

In the organic light-emitting device according to one embodiment of the present application, materials other than the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 are shown below, however, these are only for illustration are not intended to limit the scope of the present application and may be substituted by materials known in the art.

As the anode material, a material with a relatively large work function can be used, and a transparent conductive oxide, a metal, a conductive polymer, and the like can be used. Specific examples of anode materials include metals, such as vanadium, chromium, copper, zinc and gold or alloys thereof; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (ITO). oxide, IZO); combinations of metals and oxides, such as ZnO:Al or _SnO2 :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 are not limited thereto.

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

As the hole injection material, known hole injection materials can be used, and for example, phthalocyanine compounds, such as copper phthalocyanine disclosed in US Pat. No. 4,356,429; or starburst amine derivatives, such as tris(4-carbazoyl-9-ylphenyl)amine described in the literature [Advanced Materials, 6, p.677 (1994)], TCTA), 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine, m- MTDATA) or 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene, m -MTDAPB); polyaniline/dodecylbenzenesulfonic acid, poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate), polyaniline/ 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 weight or high molecular weight 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, and tetracyanoanthraquinodimethane can be used Metal complexes such as its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and its derivatives, etc., and polymers can also be used materials and low molecular materials.

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

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

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

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

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

In the following, the present description will be explained in more detail with reference to examples, which, however, are for illustrative purposes only 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 (r.b.f), 1-bromo-2,3-difluorobenzene (50 g, 259 mmol), (4-chloro-2-methoxyphenyl) Boric acid (57.7 g, 310 mmol), tetrakis(triphenylphosphine)palladium(0) (29 g, 25.9 mmol), potassium carbonate (71.5 g, 51.8 mmol) and toluene/ethanol/water ( 800 ml/160 ml/160 ml) mixture was refluxed at 110°C.

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

Preparation of compound 1-2

In a single-neck round bottom flask (RBF), 4'-chloro-2,3-difluoro-2'-methoxy-1,1'-biphenyl (65 g, 255 mmol) was mixed with MC ( The mixture (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 quenched with distilled water, and the resultant was extracted with dichloromethane and dried over _MgSO4 . The resultant was subjected to column purification (MC:Hex=1:2) to obtain compound 1-2 (49 g, 80%).

Preparation of compounds 1-3

In a single-neck round bottom flask (rbf), 4-chloro-2',3'-difluoro-[1,1'-biphenyl]-2-ol (49 g, 203 mmol) was mixed 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 (Hex:MC=5:1) was performed to obtain compound 1-3 (10.1 g, 88%).

Preparation of compounds 1-4

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

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

Preparation of compounds 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 mmol), bis(frequency (13.9 g, 54.9 mmol), XPhos (2.6 g, 5.48 mmol), potassium acetate (8 g, 82 mmol) and Pd(dba) ₂ (1.57 g, 2.74 mmol) A mixture of moles) in 1,4-dioxane (100 ml) was refluxed at 140°C.

The resultant was extracted with dichloromethane, concentrated and then The alkane/MeOH pair was processed to obtain compound 1-5 (13.4 g, out of yield).

Preparation of compound 1

In a single-neck round bottom flask (r.b.f), 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 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (8.74 g, 32.6 mmol), tetrakis(triphenylphosphine)palladium(0) (3.1 g, 2.72 mmol), potassium carbonate (7.5 g, 54.5 mmol) and 1,4-dioxane/water (150 ml/30 ml) was filtered at 60°C and then washed with 1,4-dioxane at 60°C, distilled water and MeOH to obtain compound 1 (11.2 g, 71 in two steps %).

The following compound C was synthesized in the same manner as in 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 8]

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

The target compound 137 (D) ( 7.3 g, 45%).

The following compound D was synthesized in the same manner as in 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.

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

The target compound 189 (E) ( 8.4 g, 47%).

The following compound E was synthesized in the same manner as in 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]

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

The target compound 241 (F) ( 6.4 g, 37%).

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

In addition to the compounds described in Tables 1 to 14, compounds 1 to 316 were also prepared in the same manner as described in the preparation examples provided above.

<Preparation Example 5> Synthesis of Compound 2-6

1) Preparation of compound 2-6

In 5-phenyl-5,7-dihydroindolo[2,3-b]carbazole (6.0 g, 18.05 mmol/L (mM)), 4-bromo-1,1'; 4 ',1"-terphenyl (6.7 g, 21.66 mmol/L), Pd ₂ (dba) ₃ (0.824 g, 0.90 mmol/L), Sphos (0.74 g, 1.80 mmol/L) and After t-BuONa (3.47 g, 36.10 mmol/L) was dissolved in 1,4-dioxane (60 ml), 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), purified by silica gel filtration, and recrystallized with methanol to obtain target compound 2-6 (8.6 g, 85%).

In addition to using intermediate A-1 shown in the following table 15 instead of 4-bromo-1,1'; 4',1"-terphenyl and using intermediate B-1 shown in the following table 15 instead of 5-phenyl- Target compound A was synthesized in the same manner as in Preparation Example 5 except for 5,7-indodo[2,3-b]carbazole.

<Preparation Example 6> Synthesis of Compound 2-79

1) Preparation of compound 2-79-2

2-Chloro-7-phenyl-5,7-dihydroindolo[2,3-b]carbazole (7.0 g, 19.08 mmol/L), iodobenzene (4.28 g, 20.99 mmol/L) ear/L), Pd ₂ (dba) ₃ (0.873 g, 0.95 mmol/L), (t-Bu) ₃ P (0.58 g, 2.86 mmol/L), t-BuONa (3.67 g, 38.16 After dissolving 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 thereto at room temperature, and after drying the organic layer with _MgSO4 , 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 target compound 2-79-2 (6.93 g, 82%).

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

2) Preparation of compound 2-79-1

In the presence of 2-chloro-5,7-diphenyl-5,7-dihydroindo[2,3-b]carbazole (6.93 g, 15.65 mmol/L), bis-pinacolyldi Borane (5.96 g, 23.47 mmol/L), Pd ₂ (dba) ₃ (1.43 g, 1.56 mmol/L), XPhos (1.49 g, 3.13 mmol/L) and KOAc (4.61 g, After dissolving (46.94 mmol/L) in 1,4-dioxane (70 ml), the resultant was refluxed for 5 hours. After the reaction was completed, the resultant was extracted by introducing distilled water and DCM thereto at room temperature, and after drying the organic layer with _MgSO4 , the solvent was removed using a rotary evaporator. The reaction material was subjected to column purification (MC/Hex), and the filtrate was concentrated in vacuo to obtain target compound 2-79-1 (6.8 g, 81%).

Prepare with The target compound C-1 was synthesized in the same manner as the preparation of compound 2-79-1 in Example 6.

3) Preparation of compound 2-79

In the case of 5,7-diphenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)-5,7-dihydroindolo[ 2,3-b]carbazole (6.8 g, 12.72 mmol/L), 3-bromo-9-phenylcarbazole (4.51 g, 14.00 mmol/L), Pd(PPh ₃ ) ₄ (0.74 g, 0.64 mmol/L) and K ₂ CO ₃ (3.52 g, 25.45 mmol/L) were dissolved in toluene (70 ml)/ethanol (15 ml)/water (15 ml), and the resulting Reflowed for 4 hours. After the reaction was completed, the resultant was extracted by introducing distilled water and DCM thereto at room temperature, and after drying the organic layer with _MgSO4 , the solvent was removed using a rotary evaporator. The reaction material was subjected to column purification (MC/HEX), and the filtrate was concentrated in vacuo to obtain target compound 2-79 (6.61 g, 80%).

Except using intermediate C-1 shown in Table 18 below instead of 5,7-diphenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl )-5,7-indolino[2,3-b]carb Target compound C was synthesized in the same manner as the preparation of compound 2-79 in Preparation Example 6, except that intermediate D-1 was used instead of 3-bromo-9-phenylcarbazole.

Except for the preparation examples, the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 were also prepared in the same manner. The synthesis identification data of the compounds prepared above are as described in [Table 19] and [Table 20] below.

<Experimental Example 1> Manufacturing of organic light-emitting device

A glass substrate coated with a thin film of indium tin oxide (ITO) with a thickness of 1,500 angstroms (Å) was cleaned using distilled water ultrasonic waves. Using distilled water After the first line of cleaning is completed, the substrate is ultrasonically cleaned with solvents such as acetone, methanol, and isopropyl alcohol, followed by drying and UV ozone (UV) for 5 minutes in an 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 equipment 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 electron hole transfer layer NPB (N,N'-bis(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine).

As follows, the luminescent layer is thermally vacuum deposited on the hole injection layer 2-TNATA and the hole transfer layer NPB. As the light-emitting layer, one type of compound described in Chemical Formula 1 and one type of compound described in Chemical Formula 2 in Table 22 below were deposited to 400 angstroms in each respective supply source as a host, and by 7% Doping deposits Ir(ppy) ₃ as a green phosphorescent dopant. Thereafter, bathocuproine (BCP) was deposited to 60 angstroms as the hole blocking layer, and Alq ₃ was deposited to 200 angstroms on the hole blocking layer to serve as the 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 on the electron injection layer by depositing an aluminum (Al) cathode to a thickness of 1,200 Angstroms. A cathode is formed, and thus, an organic electroluminescent device is manufactured.

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

<Experimental Example 2> Manufacturing of organic light-emitting device

A glass substrate coated with a thin film of ITO with a thickness of 1,500 angstroms was cleaned using distilled water ultrasonic waves. After cleaning with distilled water was completed, the substrate was ultrasonically cleaned with solvents such as acetone, methanol and isopropyl alcohol, followed by drying and UVO treatment using UV in a UV cleaner for 5 minutes. 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 equipment 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 electron hole transfer layer NPB (N,N'-bis(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine).

As follows, the luminescent layer is thermally vacuum deposited on the hole injection layer 2-TNATA and the hole transfer layer NPB. As the light-emitting layer, one type of compound as described in Chemical Formula 1 and one type of compound as described in Chemical Formula 2 in Table 23 were premixed in a supply source and deposited to 400 angstroms as a host, and by 7% doping Ir(ppy) ₃ is deposited as a green phosphorescent dopant. Thereafter, BCP was deposited to 60 angstroms to serve as the hole blocking layer, and Alq ₃ was deposited to 200 angstroms on the hole blocking layer to serve as the 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 on the electron injection layer by depositing an aluminum (Al) cathode to a thickness of 1,200 Angstroms. A cathode is formed, and thus, an organic electroluminescent device is manufactured.

At the same time, for each material intended to be used in OLED manufacturing, all organic compounds required to make OLEDs 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 was 6,000 candelas/square meter ( cd/m ² ), T ₉₀ was measured using a life measurement system (M6000) manufactured by Mike Scientific Corporation.

The properties of the organic electroluminescent device of the present disclosure are shown in Tables 21 to 23 below. For reference, Table 22 is an example of depositing two host compounds simultaneously in separate supply sources in Experimental Example 1, and Table 23 is an example of depositing two light-emitting layer compounds in one supply source after premixing in Experimental Example 2, Table 21 shows an example using a single main body material in Experimental Example 1.

As seen from Table 21 to Table 23, it was recognized that when both the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 are included in the organic material layer of the organic light-emitting device, compared to when alone Inclusion of each of the compounds results in superior efficiency and longevity properties. Such excellent results may lead to It is predicted that when the two compounds are contained simultaneously, an excited complex phenomenon will occur.

The excitation complex phenomenon is the exchange of electrons between two molecules, and the release of electron donor molecules (donor, p-host) HOMO energy level and electron acceptor molecules (acceptor, n-host) LUMO energy A phenomenon of magnitude of energy. When an electron donor molecule (donor, p-host) with a desired electron hole transfer ability and an electron acceptor molecule (acceptor, n-host) with a desired electron transfer ability 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 excitation complex occurs between two molecules, inverse intersystem crossover (RISC) occurs smoothly, and therefore the internal quantum efficiency of luminescence can reach 100%. In addition, the driving voltage can be reduced, which is significantly beneficial to improving the service life.

In addition, after premixing the compounds, a luminescent body formed of multiple types of compounds was deposited, and the luminescent body was 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 film properties. In addition, while reducing the overall process cost by simplifying the process, devices with improved efficiency, driving voltage and lifetime can be formed.

As can be seen from Table 22 and Table 23, the fused carbazole structure as the heterocyclic compound structure represented by Chemical Formula 2 of the present application is a structure including two carbazole or one carbazole and one heterocycle, and thereby Since there are non-shared electron pairs between nitrogen and heteroatoms in carbazole, it has strong electron donor properties. In other words, as can be seen from Table 22 and Table 23, the heterocycle corresponding to Chemical Formula 1 of the present application is identified compared to When one of the compounds and compounds corresponding to compounds A to E (biscarbazole type; or a structure in which carbazole and a heterocyclic ring are bonded), the total driving voltage/efficiency/lifetime is superior.

In addition, by corresponding to the wide region of π conjugation of the entire basic skeleton, a wider HOMO energy level region is obtained compared to unfused carbazole compounds, resulting in a wider hole distribution. Thus, fast hole transfer properties are identified when the device is driven, and thereby, by lowering the drive voltage, there are expected to be advantages in increased current efficiency and lowered device threshold voltage.

In addition, the fused carbazole as Chemical Formula 2 has a form in which pentagonal or hexagonal rings are fused by π-π bonds. This leads to the formation of a structure with minimal intramolecular distortion (rigid structure), and thus a high thermal stability (T _d95 : 400° C. or above, high T _g ). High thermal stability is an advantage in overcoming the harsh high vacuum and high temperature conditions of organic light emitting device (OLED) deposition processes, and is also beneficial against device degradation when driving the device over long periods of time. Therefore, it was seen that the fused carbazole structure as the structure represented by Chemical Formula 2 is useful as a basic structure of a material having a desirable life based on low voltage, high efficiency, and high thermal stability.

Additionally, when premixing as in Table 23, the unique thermal properties of each of the materials need to be identified during the mixing. In this article, when premixed host materials are deposited from a supply source, the unique thermal properties of the materials can significantly affect deposition conditions, including deposition rate. When the thermal properties between two or more types of premixed materials are dissimilar and very different, repeatability and reproducibility may not be maintained during the deposition process. This means that it is impossible to fabricate a complete product in one deposition process. Uniform OLED.

In view of the above, the thermal properties of the material can also be controlled based on the shape of the molecular structure, while the electrical properties of the material can be tuned using the appropriate combination of the basic structure and substituents of each of the materials. Therefore, in addition to the basic structure, various substituents in Chemical Formula 2 and C-N bonding of the fused carbazole in Chemical Formula 2 can also be used to enhance device performance, and by controlling the thermal properties of each of the materials To ensure the diversity of various premixed deposition processes from body to body. This has the advantage of ensuring the diversity of premixed deposition processes using three, four or more host materials as well as two compounds as hosts.

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

The fused carbazole structure illustrated in Chemical Formula 2 is a fused 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 or above 400°C. It is seen that this is a material that is strong enough to withstand the harsh high vacuum/high temperature regime of the OLED deposition process and is stable enough to prevent device degradation even when the device is driven over long periods of time.

Figures 4 to 21 show chemical formula 2 measured using a Mettler Toledo thermogravimetric analysis (Thermogravimetric Analysis, TGA)/differential scanning calorimetry (Differential Scanning Calorimetry, DSC) device. Thermal analysis data for each material and specific compounds. The measured _Td95 was measured by heating to increase the temperature up to 600°C such that the temperature increased from 30°C at 10 Kelvin (K) per minute. Identify the glass transition temperature and decomposition temperature among thermal properties such as glass transition temperature (Tg), crystallization temperature (Tc), melting temperature (Tm) and decomposition temperature (Td/95%) corresponding to Chemical Formula 2 and specific compounds, To first identify the stability of the device in 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. Figures 6 and 7 are graphs showing the thermal stability of compound 2-18 of the present application. Figure 8 and Figure 9 is a graph showing the thermal stability of compound 2-79 of the present application, and Figures 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, Figures 14 and 15 are graphs showing the thermal stability of compound 2-20 of the present application, and Figures 16 and 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 Figures 4 to 21, Td ₉₅ is the point at which the temperature is measured when 95% of the mass is maintained after applying the temperature, and a high Td ₉₅ means stable at high temperatures.

As identified by comparing Figures 4 to 17 with Figures 18 to 21, in Compound A (Figures 18 and 19) and Compound C (Figures 20 and 21) having a biscarbazole structure, Td ₉₅ Measured as low as or below 400°C, resulting in lower thermal stability compared to fused carbazole compounds.

Therefore, identifying the basic structure including both the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 is useful in manufacturing devices with low voltage/high efficiency goals or OLEDs with high efficiency/long life or low voltage/long life properties. is effective enough.

100:Substrate

200:Anode

300: Organic material layer

400:Cathode

Claims (15)

An organic light-emitting device, including: a first electrode; a second electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein the one or more organic material layers Also included are a heterocyclic compound represented by the following Chemical Formula 1 and a heterocyclic compound represented by any one of the following Chemical Formulas 2-7 to Chemical Formulas 2-9:

[Chemical formula 2-8]

In Chemical Formula 1 and Chemical Formula 2-7 to Chemical Formula 2-9, N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclyl group, and includes one or more N; L is a direct bond; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl, a is an integer from 1 to 3, and when a is 2 or greater than 2, L is the same as or different from each other; R ₁ to R ₁₁ and R ₁₄ are the same as each other 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 base; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted Substituted 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 groups bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted heterocyclic ring, b and c are each an integer from 1 to 3, when b is 2 or greater than 2 , R ₉ are the same as or different from each other, and when c is 2 or greater than 2, R ₁₀ are the same as or different from each other; A ₁ and A ₂ are the same as or different from each other, and each is independently O; S; NR _a ; or CR _b R _c ; A ₃ is O; S; or NR _g ; R _a to R _c are the same or different from each other, and each is independently hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted Substituted aryl; or substituted or unsubstituted heteroaryl; R ₅₀ and R ₅₁ are hydrogen; or substituted or unsubstituted aryl, and at least one of R ₅₀ and R ₅₁ is substituted or unsubstituted aryl; R _g , R ₅₂ and R ₅₃ are the same as each other or different from each other, and each is independently 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 of claim 1, wherein Chemical Formula 1 is represented by one of the following Chemical Formulas 3 to 6: [Chemical Formula 3]

[Chemical formula 6]

In Chemical Formula 3 to Chemical Formula 6, the substituents have the same definitions as in Chemical Formula 1. The organic light-emitting device of claim 1, wherein Chemical Formula 1 is represented by one of the following Chemical Formulas 7 to 9:

[Chemical formula 8]

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, and X4 is CR24 or N, and 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 group; and substituted or unsubstituted An 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 heterocycle. The organic light-emitting device according to claim 3, wherein

Represented by one of the following Chemical Formulas 10 to 12:

[Chemical formula 12]

In Chemical Formula 10, one or more of X1, X3, and X5 is N, and the others have the same definitions as in Chemical Formula 7; in Chemical Formula 11, one or more of X1, X2, and N, and the others have the same definitions as in Chemical Formula 7; in Chemical Formula 12, one or more of X1 to X3 is N, and the others have the same definitions as in Chemical Formula 7; and R22, R24 and R33 to R36 are the same as each other 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 base; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted Substituted 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 The groups are bonded to each other to form substituted or unsubstituted aliphatic or aromatic hydrocarbon rings or heterocycles. The organic light-emitting device of claim 4, wherein the chemical formula 10 is selected from the following structural formulas:

In the structural formula, R21 to R25 are the same as each other 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 adjacent to each other or more groups bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or heterocycle. The organic light-emitting device of claim 1, wherein Chemical Formula 1 is represented by any one of the following compounds:

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

The organic light-emitting device of claim 1, wherein the one or more organic material layers include at least one of a hole blocking layer, an electron injection layer, and an electron transfer layer, and the hole blocking layer, the At least one of the electron injection layer and the electron transfer layer includes the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by any one of Chemical Formulas 2-7 to Chemical Formulas 2-9. The organic light-emitting device of claim 1, wherein the one or more organic material layers include a light-emitting layer, and the light-emitting layer includes the heterocyclic compound represented by Chemical Formula 1 and Chemical Formulas 2-7 to Chemical Formula 2 The heterocyclic compound represented by any one of -9. The organic light-emitting device of claim 1, wherein the one or more organic material layers include 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 represented by any one of Chemical Formula 2-7 to Chemical Formula 2-9. The organic light-emitting device as claimed in claim 1, including selected from the following A group of one, two or more layers 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. A composition for an organic material layer of an organic light-emitting device, the composition comprising a heterocyclic compound represented by the following Chemical Formula 1 and a heterocyclic compound represented by any one of the following Chemical Formulas 2-7 to Chemical Formulas 2-9 :

[Chemical formula 2-8]

In Chemical Formula 1 and Chemical Formula 2-7 to Chemical Formula 2-9, N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclyl group, and includes one or more N; L is a direct bond; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl, a is an integer from 1 to 3, and when a is 2 or greater than 2, L is the same as or different from each other; R ₁ to R ₁₁ and R ₁₄ are the same as each other 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 base; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted Substituted 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 groups bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted heterocyclic ring, b and c are each an integer from 1 to 3, when b is 2 or greater than 2 , R ₉ are the same as or different from each other, and when c is 2 or greater than 2, R ₁₀ are the same as or different from each other; A ₁ and A ₂ are the same as or different from each other, and each is independently O; S; NR _a ; or CR _b R _c ; A ₃ is O; S; or NR _g ; R _a to R _c are the same or different from each other, and each is independently hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted Substituted aryl; or substituted or unsubstituted heteroaryl; R ₅₀ and R ₅₁ are hydrogen; or substituted or unsubstituted aryl, and at least one of R ₅₀ and R ₅₁ is substituted or unsubstituted aryl; R _g , R ₅₂ and R ₅₃ are the same as each other or different from each other, and each is independently 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 composition for an organic material layer of an organic light-emitting device according to claim 12, wherein in the composition, the heterocyclic ring represented by Chemical Formula 1 Compound: The heterocyclic compound represented by any one of Chemical Formula 2-7 to Chemical Formula 2-9 has a weight ratio of 1:10 to 10:1. 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 on the one or A second electrode is formed on a plurality of organic material layers, wherein forming the one or more organic material layers includes forming the one or more organic materials using the composition for an organic material layer as described in claim 12 layer. The method of manufacturing an organic light-emitting device according to claim 14, wherein the forming the one or more organic material layers is premixing the heterocyclic compound represented by Chemical Formula 1 and Chemical Formula 2-7 to Chemical Formula 2- The heterocyclic compound shown in any of 9 is then formed using a thermal vacuum deposition method.