TWI841655B - 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, method for manufacturing the same, and composition of organic material layer for organic light-emitting device

This application claims the priority and rights of Korean Patent Application No. 10-2018-0172503 filed with the Korean Intellectual Property Office on December 28, 2018. The entire contents of the Korean Patent Application are incorporated into this application 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.

Electroluminescent (EL) devices are self-luminous display devices with the advantages of wide viewing angles, high response speeds, and excellent contrast.

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

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

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

[Previous Technical Documents] [Patent Documents]

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

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

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

In Formula 1 and 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 aryl group; or a substituted or unsubstituted heteroaryl group, a is an integer from 1 to 3, and when a is 2 or greater, L is the same as or different from each other, R ₁ to R ₁₉ are the same as or different from each other and are each independently selected from the group consisting of: hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; substituted or unsubstituted phosphine oxide; and substituted or unsubstituted amine, or two or more adjacent groups are 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, d is an integer from 0 to 2, and when b is 2 or greater, R wherein _{R 9} are the same as or different from each other, when c is 2 or greater, R ₁₀ are the same as or different from each other, and when d is an integer of 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 and are each independently O; S; NR _a ; or CR _b R _c , and R _a to R _c are the same as or different from each other and are each 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, wherein the composition comprises the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2.

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

According to an embodiment of the present application, the heterocyclic compound can be used as a material for an organic material layer of an organic light-emitting device. The heterocyclic compound can be used as a material for a hole injection layer, a hole transfer layer, a light-emitting layer, an electron transfer layer, an electron injection layer, a charge generation layer, etc. in an organic light-emitting device. Specifically, the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 can be used simultaneously as materials for the light-emitting layer of an 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 life properties of the device can be improved by the thermal stability of the compound.

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

100: Substrate

200: Yang pole

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

Figures 1 to 3 are diagrams each schematically showing a laminated structure of an organic light-emitting device according to an embodiment of the present application.

Figures 4 and 5 are graphs showing the thermal stability of compound 2-19 of the present application.

Figures 6 and 7 are graphs showing the thermal stability of compound 2-20 of the present application.

Figures 8 and 9 are graphs showing the thermal stability of compound 2-22 of the present application.

Figures 10 and 11 are graphs showing the thermal stability of compound 2-8 of the present application.

Figures 12 and 13 are graphs showing the thermal stability of compound 2-18 of the present application.

Figures 14 and 15 are graphs showing the thermal stability of compound 2-79 of the present application.

Figures 16 and 17 are graphs showing the thermal stability of compound 2-123 of the present application.

Figures 18 and 19 are graphs showing the thermal stability of compound A.

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

This application will be described in detail below.

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

In the present specification, "substituted or unsubstituted" means a group selected from C1 to C60 straight or branched alkyl; C2 to C60 straight or branched alkenyl; C2 to C60 straight or branched alkynyl; C3 to C60 monocyclic or polycyclic cycloalkyl; C2 to C60 monocyclic or polycyclic heterocyclic alkyl; C6 to C60 monocyclic or polycyclic aryl; C2 to C60 monocyclic or polycyclic heteroaryl; -SiRR'R"; -P(=O)RR'; C1 to C20 alkylamine; C6 to C60 monocyclic or polycyclic heterocyclic alkyl; Cycloarylamine; and C2 to C60 monocyclic or polycyclic heteroarylamines, which are substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with substituents linked to two or more substituents selected from the substituents shown above. R, R' and R" are the same 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 or different from each other, and can be independently hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl.

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

In the present specification, the alkyl group includes a straight or branched alkyl group having 1 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples of the alkyl group may include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, tert-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-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, tert-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 the present specification, alkenyl includes straight or branched alkenyl having 2 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkenyl may be 2 to 60, specifically 2 to 40 and more specifically 2 to 20. Specific examples of alkenyl 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 the present specification, the alkynyl group includes a straight chain 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 2 to 60, specifically 2 to 40, and more specifically 2 to 20.

In the present 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, neopentoxy, isopentoxy, n-hexoxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc., but are not limited thereto.

In this specification, cycloalkyl includes monocyclic or polycyclic cycloalkyl with 3 to 60 carbon atoms, and can be further substituted by other substituents. In this article, polycyclic means that cycloalkyl is directly connected to other cyclic groups or groups fused with other cyclic groups. In this article, other cyclic groups can be cycloalkyl, but can also be different types of cyclic groups such as heterocycloalkyl, aryl and heteroaryl. The number of carbon atoms of cycloalkyl can be 3 to 60, specifically 3 to 40 and more specifically 5 to 20. Specific examples of cycloalkyl groups may include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are not limited thereto.

In the present specification, heterocycloalkyl includes O, S, Se, N or Si as a hetero atom, including monocyclic or polycyclic heterocycloalkyl having 2 to 60 carbon atoms, and may be further substituted by other substituents. In this article, polycyclic means a heterocycloalkyl directly linked to other cyclic groups or fused with other cyclic groups. In this article, other cyclic groups may be heterocycloalkyl, but may also be different types of cyclic groups such as cycloalkyl, aryl and heteroaryl. The number of carbon atoms of the heterocycloalkyl may be 2 to 60, specifically 2 to 40 and more specifically 3 to 20.

基、菲基、苝基、茀蒽基、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 the present specification, aryl includes monocyclic or polycyclic aryl having 6 to 60 carbon atoms, and may be further substituted by other substituents. In this article, polycyclic means that aryl is directly linked to other cyclic groups or groups condensed with other cyclic groups. In this article, other cyclic groups may be aryl, but may also be different types of cyclic groups such as cycloalkyl, heterocycloalkyl and heteroaryl. Aryl includes spiro. The number of carbon atoms of aryl may be 6 to 60, specifically 6 to 40 and more specifically 6 to 25. Specific examples of aryl may include phenyl, biphenyl, triphenyl, naphthyl, anthracenyl,

1H-indenyl, 2,3-dihydro-1H-indenyl, and fused rings thereof.

In this specification, the fluorenyl group may be substituted, and adjacent substituents may bond 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]氮呼基、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 this specification, heteroaryl includes O, S, Se, N or Si as heteroatoms, including monocyclic or polycyclic heteroaryl with 2 to 60 carbon atoms, and can be further substituted by other substituents. In this article, polycyclic means that heteroaryl is directly connected to other cyclic groups or groups fused with other cyclic groups. In this article, other cyclic groups can be heteroaryl, but can also be different types of cyclic groups such as cycloalkyl, heterocycloalkyl and aryl. The number of carbon atoms of heteroaryl can be 2 to 60, specifically 2 to 40 and more specifically 3 to 25. Specific examples of heteroaryl groups may include pyridyl, pyrrolyl, pyrimidinyl, oxazinyl, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, furazanyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl,

azinyl group, a thiazinyl group, a dioxynyl group, a triazinyl group, a tetrazinyl group, a quinolyl group, an isoquinolyl group, a quinazolyl group, an isoquinazolyl group, a quinozolinyl group, a naphthyridyl group, an acridinyl group, a phenanthridinyl group, an imidazopyridyl group, a diazanaphthalenyl group, a triazinyl group, an indolyl group, an indolizinyl group, a benzothiazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiophenyl group, a benzofuranyl group, a dibenzothiophenyl group, a dibenzofuranyl group, a carbazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a phenazinyl group, a dibenzosilole ... group), spirobi(dibenzosilole), dihydrophenazine, phen

azine group, phenanthridyl group, imidazopyridyl group, thienyl group, indolo[2,3-a]carbazole group, indolo[2,3-b]carbazole group, indolinyl group, 10,11-dihydrodibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenathrazinyl group, phenathiazinyl group, phenazine group, naphthyridinyl group, phenanthrolinyl group group), benzo[c][1,2,5]thiadiazolyl, 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 the present specification, the amine group may be selected from the group consisting of monoalkylamine, monoarylamine, monoheteroarylamine, _-NH2 , dialkylamine, diarylamine, diheteroarylamine, alkylarylamine, alkylheteroarylamine, and arylheteroarylamine groups, and although not particularly limited thereto, the number of carbon atoms is preferably 1 to 30. Specific examples of the amino group may include methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, naphthylamino, biphenylamino, diphenylamino, anthracenylamino, 9-methyl-anthrylamino, diphenylamino, phenylnaphthylamino, ditolylamino, phenyltolylamino, triphenylamino, biphenylnaphthylamino, phenylbiphenylamino, biphenylfluorenylamino, phenyltriphenylamino, biphenyltriphenylamino, and the like, but are not limited thereto.

In this specification, an aryl group refers to an aryl group having two bonding sites, i.e., a divalent group. The description of the aryl group provided above can be applied to aryl groups, except that each of them is divalent. In addition, a heteroaryl group refers to a heteroaryl group having two bonding sites, i.e., a divalent group. The description of the heteroaryl group provided above can be applied to heteroaryl groups, except that each of them is divalent.

In the present 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 can 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 can be specifically substituted by an aryl group, and as the aryl group, the above examples can be used. Examples of the phosphine oxide group can include a diphenylphosphine oxide group, a dinaphthylphosphine oxide group, etc., but are not limited thereto.

In the present specification, a silyl group is _a substituent including Si, has a Si atom directly bonded as _{a free radical, and is represented by -SiR104R105R106. R104 to R106 are} the same as or different from each other, and may each independently be a substituent formed of at least one of the following: hydrogen; deuterium; halogen group; alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; and heterocyclic group. 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, and the like, but are not limited thereto.

In this specification, "adjacent" groups may refer to substituents that replace atoms directly connected to the atoms substituted by the corresponding substituents, substituents that are spatially closest to the corresponding substituents, or another substituent that replaces the atoms substituted by the corresponding substituents. For example, two substituents that replace adjacent positions in a benzene ring and two substituents that replace 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 heterocyclic rings that can be formed by adjacent groups, the structures shown above as cycloalkyl, cycloheteroalkyl, aryl and heteroaryl can be used, except for non-monovalent ones.

An embodiment of the present application provides an organic light-emitting device, the organic light-emitting device comprising: a first electrode; a second electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein the one or more organic material layers contain 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 can be represented by one of the following Chemical Formulas 3 to 6.

[Chemical formula 3]

[Chemical formula 5]

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

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

In another embodiment, N-Het is a monocyclic or polycyclic heterocyclic ring which is unsubstituted or substituted by one or more substituents selected from the group consisting of aryl and heteroaryl, and includes one or more N.

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

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

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

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

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

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

[Chemical formula 7]

[Chemical formula 9]

In Chemical Formulae 7 to 9, X1 is CR21 or N, X2 is CR22 or N, X3 is CR23 or N, X4 is CR24 or N, and X5 is CR25 or N, and R21 to R25 and R27 to R32 are the same as or different from each other, and are each independently selected from the group consisting of: hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or Unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; substituted or unsubstituted phosphine oxide; and substituted or unsubstituted amine, or two or more adjacent groups bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or heterocycle.

可由以下化學式10至化學式13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 13. Herein,

is the site for attachment to L.

[Chemical formula 13]

In Chemical Formula 10, one or more of X1, X3 and X5 is N, and the rest have the same definition as in Chemical Formula 7. In Chemical Formula 11, one or more of X1, X2 and X5 is N, and the rest have the same definition as in Chemical Formula 7. In Chemical Formula 12, one or more of X1 to X3 is N, and the rest have the same definition as in Chemical Formula 7. In Chemical Formula 13, one or more of X1, X2 and X5 is N, and the rest have the same definition as in Chemical Formula 7. R22, R24 and R33 to R36 are the same as each other or different from each other. This is different from 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 alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; substituted or unsubstituted phosphine oxide; and substituted or unsubstituted amine, or two or more adjacent groups 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, each substituent has the same definition as in Chemical Formula 10.

In one embodiment of the present application, Chemical Formula 11 can be represented by the following Chemical Formula 14.

The substituents in Chemical Formula 14 have the same definitions as those in Chemical Formula 11.

In one embodiment of the present application, Chemical Formula 12 can be represented by the following Chemical Formula 15.

[Chemical formula 15]

The substituents in Chemical Formula 15 have the same definitions as those in Chemical Formula 12.

In one embodiment of the present application, Chemical Formula 11 can be represented by the following Chemical Formula 16.

In Chemical Formula 16, R37 are the same as or different from each other and are 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; and substituted or unsubstituted amine, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon or heterocyclic ring, e is an integer from 0 to 7, and when e is 2 or greater than 2, R37 are the same as or different from each other.

In one embodiment of the present application, Chemical Formula 13 can be represented by the following Chemical Formula 17.

The substituents in Chemical Formula 17 have the same definitions as those in Chemical Formula 13.

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

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

In another embodiment, R9 and R10 are hydrogen; or deuterium.

In another embodiment, R9 and R10 are hydrogen.

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

In another embodiment, R1 to R8 are hydrogen; deuterium; phenyl; dibenzofuranyl; or carbazolyl substituted with 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 a ring that is unsubstituted or substituted with an aryl or alkyl group.

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

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

可由以下化學式18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 18. In this article,

is the site of attachment to the dibenzofuran structure.

In Chemical Formula 18, R1 to R4 have the same definitions as those 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 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; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more adjacent groups are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted heterocyclic ring, f is an integer from 0 to 4, and when f is 2 or greater than 2, R41 are the same as or different from each other, g is an integer from 0 to 2, and when g is 2 or greater than 2, R42 are the same as or different from each other.

In another embodiment, chemical formula 18 can be selected from the following structural formulas.

In the structural formula, the substituents have the same definitions as in Chemical Formula 18.

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

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

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

In another embodiment, R27 and R32 are phenyl groups.

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

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

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

In another embodiment, R22 and R24 are the same or different from each other, and are each independently an unsubstituted or alkyl-substituted aryl group; or a heteroaryl group.

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

In 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.

In another embodiment, R33 to R36 are the same as or different from each other, and each is independently hydrogen; deuterium; or aryl.

In another embodiment, R33 to R36 are the same as or different from each other, and each is independently hydrogen; or aryl.

In another embodiment, R33 to R36 are the same as or different from each other, and each is independently hydrogen; phenyl; or biphenyl.

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 NR _d , and R _d is aryl.

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

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

In another embodiment, Y is CR _e R _f , and _Re and R _f 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 the present application, R42 is hydrogen; or deuterium.

In another embodiment, R42 is hydrogen.

In one embodiment of the present application, _A1 and _A2 in Chemical Formula 2 are the same as or different from each other, and can be independently O; S; NR _a ; or CR _b R _c .

In one embodiment of the present application, _Ra to _Rc are the same as or different from each other, and may be independently hydrogen; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.

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

In another embodiment, _Ra to _Rc are the same as or different from each other and may each independently be hydrogen; a C1 to C40 alkyl group; a C6 to C40 aryl group which is unsubstituted or substituted with one or more substituents selected from the group consisting of a C1 to C40 alkyl group, a C6 to C40 aryl group and a triphenylsilyl group; or a C2 to C40 heteroaryl group which is unsubstituted or substituted with a C6 to C40 aryl group.

In another embodiment, _Ra to _Rc are the same as or different from each other, and may be each independently methyl; phenyl which is unsubstituted or substituted by one or more substituents selected from the group consisting of phenyl and triphenylsilyl; biphenyl which is unsubstituted or substituted by phenyl; naphthyl; triphenylene; diphenylfluorenyl; dimethylfluorenyl; carbazolyl which is unsubstituted or substituted by phenyl; dibenzofuranyl; or dibenzothienyl.

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

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

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

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

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

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

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

[Chemical formula 2-2]

In Chemical Formulae 2-1 to 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 can be represented by any one of the following Chemical Formulas 2-7 to 2-9.

[Chemical formula 2-7]

In Chemical Formulae 2-7 to 2-9, _A1 , _A2 , _R11 and _R14 have the same definitions as in Chemical Formula 2, _A3 is O; S; or _NRg , _R50 and _R51 are hydrogen; or a substituted or unsubstituted aryl group, and at least one of _R50 and _R51 is a substituted or unsubstituted aryl group, _Rg , _R52 and _R53 are the same as or different from each other and are each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, r is an integer from 0 to 3, 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 a substituted or unsubstituted aryl group.

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

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

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

In another embodiment, R ₅₀ and R ₅₁ can be hydrogen; phenyl; or terphenylene.

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 may be hydrogen.

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

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

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

In another embodiment, _Rg may be a C6 to C40 aryl group.

In another embodiment, _Rg 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, a very fast hole transfer property is obtained, which reduces the critical voltage and driving voltage of the device, and thus, the device can be driven even at a low voltage.

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, the conjugated region becomes wider toward the substituent (R ₅₀ ) extending from the basic skeleton, and a further widened highest occupied molecular orbital (HOMO) energy level region is obtained. Therefore, holes are distributed to the wide HOMO energy level region, and more stable hole transfer ability can be maintained. In other words, in the case of Chemical Formula 2-8, for example, the driving voltage is increased to a certain extent, however, a more superior overall life property is obtained.

Chemical formula 2-9 is a case where the fused ring structure is substituted by a heteroaryl group, and because it has the property of maintaining a stable HOMO energy level through a wide conjugated region as in chemical formula 2-8, it can be used as an auxiliary means to control the band gap through various heteroaryl substitutions. Specifically, since dibenzofuran/dibenzothiophene groups have the largest structure in structure, the driving voltage is slightly increased compared to the basic skeleton. However, in addition to maintaining the property of a higher T1 energy level, it also has the highest structural stability, so it will obtain particularly superior device life properties.

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

The excited complex phenomenon is a phenomenon in which energy having the magnitude of the donor (p-host) HOMO energy level and the acceptor (n-host) lowest unoccupied molecular orbital (LUMO) energy level is released due to electron exchange between two molecules. When the excited complex phenomenon occurs between two molecules, reverse intersystem crossing (RISC) occurs, and thus the internal quantum efficiency of fluorescence can be increased up to 100%. When a donor (p-host) having a desirable hole transfer ability and an acceptor (n-host) having a desirable electron transfer ability are used as hosts of the light-emitting layer, holes are injected into the p-host and electrons are injected into the n-host, and thus the driving voltage can be reduced, which ultimately contributes to an increase in lifetime.

According to an embodiment of the present application, Chemical Formula 1 can be represented by any one of the following compounds, but is not limited thereto.

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

In addition, by introducing various substituents into the structures shown in Chemical Formula 1 and Chemical Formula 2, compounds 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, materials that meet the required conditions for each organic material layer can be synthesized.

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

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

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

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

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

In the composition, the heterocyclic compound represented by Chemical Formula 1: the compound represented by Chemical Formula 2 may have a weight ratio of 1:10 to 10:1, 1:8 to 8:1, 1:5 to 5:1, or 1:2 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 more specifically, can be used more preferably when forming the 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 can be mixed before forming the organic material layer of the organic light-emitting device, or the liquid compounds can be mixed at a temperature higher than an appropriate temperature. The composition is solid below the melting point of each of the materials and can be maintained in a liquid state by adjusting the temperature.

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

In addition to using the 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, the organic light-emitting device according to an embodiment of the present application 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, roll coating, etc., but is not limited thereto.

The organic material layer of the organic light-emitting device disclosed herein 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 an embodiment of the present disclosure may have a structure including a hole injection layer, a hole transfer layer, a light-emitting layer, an electron transfer layer, an electron injection layer, etc. as 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 for 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 materials for the red organic light-emitting device.

The organic light-emitting device disclosed herein may further include one, two or more layers 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.

In an 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 at least one of the hole blocking layer, the electron injection layer, and the electron transfer layer includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2.

In an 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 an 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 main material, and the main material includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2.

Figures 1 to 3 show the lamination sequence of the electrode and the organic material layer of an organic light-emitting device according to an embodiment of the present application. However, the scope of the present application is not limited to these figures, and the structure of the organic light-emitting device known in the art can 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 successively layered 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 successively layered on a substrate can also be obtained.

FIG3 shows a case where the organic material layer is multi-layered. The organic light-emitting device according to FIG3 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 may not include other layers except the light-emitting layer as needed, and may further include other necessary functional layers.

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

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

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 one supply source before being deposited on the organic material layer. Premixing has the advantage of making the process simpler because one supply source is used instead of 2 to 3 supply sources.

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

When premixing as described above, the unique thermal properties of each material in the mix need to be identified. In this context, when premixed host materials are deposited from one 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 in the deposition process, which means that it is impossible to produce a completely uniform organic light emitting diode (OLED) in one deposition process.

In view of the above, the thermal properties of the material can also be controlled according to the shape of the molecular structure, while the electrical properties of the material can be adjusted 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 the C-N bond of the fused carbazole in Chemical Formula 2 can also be used to enhance device performance, and the diversity of various pre-mixed deposition processes between hosts can be ensured by controlling the thermal properties of each of the materials. This has the advantage of ensuring the diversity of pre-mixed deposition processes using three, four or more host materials and two compounds as hosts.

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

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

As the cathode material, a material having a relatively small work function may be used, and metals, metal oxides, conductive polymers, etc. may be used. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structure materials such as LiF/Al or _LiO2 /Al; and the like, but are not limited thereto.

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

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

As electron transfer materials, metal complexes such as oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and its derivatives can be used, and polymer materials and low molecular weight materials can also be used.

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

As the luminescent material, a red, green or blue luminescent material can be used, and two or more luminescent materials can be mixed and used as needed. In this article, two or more luminescent materials can be used by deposition as individual supply sources or by pre-mixing and deposition as one supply source. In addition, a fluorescent material can also be used as a luminescent material, however, a phosphorescent material 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, can be used alone, however, a material having a host material and a dopant material that together involve light emission can also be used.

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

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

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

Hereinafter, this specification will be described in more detail with reference to examples, however, these examples are for illustrative purposes only and the scope of this application is not limited thereto.

<Preparation Example>

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

Preparation of compound 1-1

In a round bottom flask (RBF), a mixture of 1-bromo-2,3-difluorobenzene (40.5 g, 209 mmol), (2-chloro-6-methoxyphenyl)boric acid (43 g, 230 mmol), tetrakis(triphenylphosphine)palladium(0) (24 g, 20.9 mmol), potassium carbonate (57.9 g, 419 mmol) and toluene/ethanol/water (500 ml/100 ml/100 ml) was refluxed at 110°C. The resultant was extracted with dichloromethane (DCM) and dried over MgSO _4. The resultant was filtered through silica gel and then concentrated to obtain compound 1-1 (40.8 g, 76%).

Preparation of compound 1-2

In a single-necked round-bottom flask (rbf), a mixture of 2'-chloro-2,3-difluoro-6'-methoxy-1,1'-biphenyl (40.8 g, 160 mmol) and methylene chloride (MC) (600 ml) was cooled to 0°C, BBr ₃ (30 ml, 320 mmol) was added dropwise thereto, and after the temperature was raised to room temperature, the resultant was stirred for 1 hour. The reaction was terminated with distilled water, and the resultant was extracted with methylene chloride and dried with MgSO _4. The resultant was column purified (MC: Hex = 1: 1) to obtain compound 1-2 (21 g, 54%).

Preparation of Compound 1-3

In a single-necked round-bottom flask (rbf), a mixture of 4-chloro-2',3'-difluoro-[1,1'-biphenyl]-2-ol (21 g, 87.2 mmol) and Cs ₂ CO ₃ (71 g, 218 mmol) in dimethylacetamide (200 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=4:1) was performed to obtain compound 1-3 (17 g, 88%).

Preparation of Compounds 1-4

In a single-necked round-bottom flask (rbf), a mixture of 1-chloro-6-fluorodibenzo[b,d]furan (6 g, 27.19 mmol), 9H-carbazole (5 g, 29.9 mmol) and Cs ₂ CO ₃ (22 g, 101.7 mmol) in dimethylacetamide (60 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=3:1) was performed to obtain compound 1-4 (9 g, 90%).

Preparation of Compounds 1-5

In a single-necked round-bottom flask (rbf), a mixture of 9-(9-chlorodibenzo[b,d]furan-4-yl)-9H-carbazole (9 g, 24.4 mmol), bis(pinacolato)diboron (12.4 g, 48.9 mmol), Pcy ₃ (1.37 g, 4.89 mmol), potassium acetate (7.1 g, 73 mmol) and Pd ₂ (dba) ₃ (2.2 g, 2.44 mmol) in 1,4-dioxane (100 ml) was refluxed at 140° C. The resultant was cooled, and the filtrate was concentrated and column purified (Hex:MC=3:1) to obtain compound 1-5 (7.2 g, 64%).

Preparation of compound 1

In a single neck round bottom flask (r.b.f), a mixture of 9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-4-yl)-9H-carbazole (7.2 g, 15.6 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5 g, 18.8 mmol), tetrakis(triphenylphosphine)palladium(0) (1.8 g, 1.56 mmol), potassium carbonate (4.3 g, 31.2 mmol) and 1,4-dioxane/water (100 ml/25 ml) was refluxed at 120°C for 4 hours. The resultant was filtered at 120°C and then washed with 1,4-dioxane, distilled water and MeOH to obtain Compound 1(C) (6.6 g, 75%).

The following compound C was synthesized in the same manner as compound 1 in Preparation Example 1, except that A and B shown in the following [Table 1] to [Table 7] were used as intermediates.

[Preparation Example 2] Preparation of Compound 129(F)

Preparation of compound 129-1

In a single-necked round-bottom flask (r.b.f), a mixture of 1-bromo-2,4-difluorobenzene (40 g, 207 mmol), (2-chloro-6-methoxyphenyl)boric acid (42.4 g, 227 mmol), tetrakis(triphenylphosphine)palladium(0) (23 g, 20.7 mmol), potassium carbonate (57 g, 414 mmol) and toluene/ethanol/water (600 ml/150 ml/150 ml) was refluxed at 110°C.

The resultant was extracted with dichloromethane, dried over MgSO ₄ , filtered through silica gel and then concentrated to obtain compound 129-1 (50 g, 94%).

Preparation of compound 129-2

In a single-necked round-bottom flask (rbf), a mixture of 2'-chloro-2,4-difluoro-6'-methoxy-1,1'-biphenyl (50 g, 196 mmol) and dichloromethane (700 mL) was cooled to 0°C, BBr ₃ (28.3 mL, 294 mmol) was added dropwise thereto, and after the temperature was raised to room temperature, the resultant was stirred for 2 hours.

The reaction was terminated with distilled water, and the resultant was extracted with dichloromethane and dried over MgSO _4. The resultant was filtered through silica gel to obtain compound 129-2 (27.5 g, 58%).

Preparation of compound 129-3

In a single-necked round-bottom flask (rbf), a mixture of 4-chloro-2',4'-difluoro-[1,1'-biphenyl]-2-ol (27 g, 114 mmol) and Cs ₂ CO ₃ (83 g, 285 mmol) in dimethylacetamide (300 ml) was stirred at 120° C. The resultant was cooled and then filtered, and after removing the solvent of the filtrate, silica gel filtration was performed to obtain compound 129-3 (23 g, 92%).

Preparation of compound 129-4

In a single-necked round-bottom flask (rbf), a mixture of 1-chloro-7-fluorodibenzo[b,d]furan (5.5 g, 24.9 mmol), 9H-carbazole (4.58 g, 27.4 mmol) and Cs ₂ CO ₃ (20 g, 62 mmol) in dimethylacetamide (60 ml) was refluxed at 170° C. for 6 hours. The resultant was cooled and then filtered, and after removing the solvent of the filtrate, column purification (HX:MC=3:1) was performed to obtain compound 129-4 (7.6 g, 83%).

Preparation of compound 129-5

In a single-necked round-bottom flask (rbf), a mixture of 9-(9-chlorodibenzo[b,d]furan-3-yl)-9H-carbazole (7.5 g, 20.3 mmol), bis(pinacolato)diboron (10.3 g, 40.7 mmol), Pcy ₃ (1.14 g, 4.07 mmol), potassium acetate (5.97 g, 60.9 mmol) and Pd ₂ (dba) ₃ (1.85 g, 2.03 mmol) in 1,4-dioxane (80 ml) was refluxed at 140° C. The resultant was cooled, and the filtrate was concentrated and column purified (HX:MC=2:1) to obtain compound 129-5 (6.5 g, 70%).

Preparation of compound 129

In a single neck round bottom flask (r.b.f), a mixture of 9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-3-yl)-9H-carbazole (6.5 g, 14.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (4.54 g, 16.9 mmol), tetrakis(triphenylphosphine)palladium(0) (1.6 g, 1.41 mmol), potassium carbonate (3.9 g, 28.2 mmol) and 1,4-dioxane/water (80 ml/28.2 ml) was refluxed at 120°C for 4 hours. The resultant was filtered at 60°C, and then washed with 60°C 1,4-dioxane, distilled water and MeOH to obtain Compound 129(F) (5.4 g, 68%).

The following compound F was synthesized in the same manner as the preparation of compound 129 in Preparation Example 2, except that D and E shown in the following [Table 8] to [Table 14] were used as intermediates.

[Table 10]

In addition to the compounds described in Tables 1 to 14, compounds 1 to 286 were also prepared in the same manner as described in the preparation examples provided above.

<Preparation Example 3> Synthesis of Compound 2-6

1) Preparation of Compound 2-6

After dissolving 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), _Pd2 (dba) ₃ (0.824 g, 0.90 mmol/L), Sphos (0.74 g, 1.80 mmol/L) and t-BuONa (3.47 g, 36.10 mmol/L) in 1,4-dioxane (60 mL), the resultant was refluxed for 24 hours. After completion of the reaction, the resultant was extracted by introducing distilled water and dichloromethane (DCM) thereto at room temperature, and then the mixture was washed with MgSO4. ₄ After the organic layer was dried, the solvent was removed using a rotary evaporator. The reaction material was dissolved in dichlorobenzoyl chloride (DCB) (100 mL), purified by filtration using silica gel, and recrystallized from methanol to obtain the target compound 2-6 (8.6 g, 85%).

The target compound A was synthesized in the same manner as in Preparation Example 3, except that the intermediate A-1 shown in Table 15 below was used instead of 4-bromo-1,1';4',1"-terphenyl and the intermediate B-1 shown in Table 15 below was used instead of 5-phenyl-5,7-dihydroindole[2,3-b]carbazole.

<Preparation Example 4> Synthesis of Compound 2-79

1) Preparation of compound 2-79-2

After dissolving 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), 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 mmol/L) 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 the organic layer was dried over MgSO ₄ , the solvent was removed using a rotary evaporator. The reaction material was column purified (MC/Hex), and then the solvent was removed using a rotary evaporator to obtain the target compound 2-79-2 (6.93 g, 82%).

The target compound C-2 was synthesized in the same manner as the preparation of compound 2-79-2 in Preparation Example 4, except that the intermediate C-3 shown in Table 16 below was used instead of 2-chloro-7-phenyl-5,7-dihydroindolo[2,3-b]carbazole.

2) Preparation of compound 2-79-1

After dissolving 2-chloro-5,7-diphenyl-5,7-dihydroindolo[2,3-b]carbazole (6.93 g, 15.65 mmol/L), bispinacolatodiborane (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, 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 the organic layer was dried over MgSO ₄ , the solvent was removed using a rotary evaporator. The reaction material was column purified (MC/HEX), and the filtrate was concentrated under vacuum to obtain the target compound 2-79-1 (6.8 g, 81%).

The target compound C-1 was synthesized in the same manner as the preparation of compound 2-79-1 in Preparation Example 4, except that the intermediate C-2 shown in Table 17 below was used instead of 2-chloro-5,7-diphenyl-5,7-dihydroindolo[2,3-b]carbazole.

3) Preparation of Compound 2-79

After dissolving 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) in toluene (70 mL)/ethanol (15 mL)/water (15 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 the organic layer was dried over MgSO ₄ , the solvent was removed using a rotary evaporator. The reaction material was column purified (MC/HEX), and the filtrate was vacuum concentrated to obtain the target compound 2-79 (6.61 g, 80%).

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

In addition to 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 synthetic identification data of the compounds prepared above are described in the following [Table 19] and [Table 20].

<Experimental Example 1> Fabrication of an organic light-emitting device

A glass substrate on which indium tin oxide (ITO) was coated as a thin film with a thickness of 1,500 angstroms (Å) was cleaned by ultrasonication with distilled water. After the cleaning with distilled water was completed, the substrate was ultrasonically cleaned with solvents such as acetone, methanol, and isopropyl alcohol, followed by drying and ultraviolet ozone (UVO) treatment for 5 minutes using UV in an ultraviolet (UV) cleaner. Thereafter, the substrate was transferred to a plasma cleaner (PT), and after plasma treatment under vacuum to remove the ITO work function and residual film, the substrate was transferred to a thermal deposition equipment for organic deposition.

On the transparent ITO electrode (anode), the hole injection layer 2-TNATA (4,4',4"-tri[2-naphthyl(phenyl)amino]triphenylamine) and the hole transfer layer NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) are formed as common layers.

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

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

<Experimental Example 2> Fabrication of an organic light-emitting device

A glass substrate on which ITO was coated with a thickness of 1,500 angstroms as a thin film was cleaned with distilled water ultrasonics. After the 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 for 5 minutes using UV in a UV cleaner. Thereafter, the substrate was transferred to a plasma cleaner (PT), and after plasma treatment under vacuum to remove the ITO work function and residual film, the substrate was transferred to a thermal deposition equipment for organic deposition.

On the transparent ITO electrode (anode), the hole injection layer 2-TNATA (4,4',4"-tri[2-naphthyl(phenyl)amino]triphenylamine) and the hole transfer layer NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) are formed as common layers.

As follows, a light-emitting layer was thermally vacuum deposited on the hole injection layer 2-TNATA and the hole transfer layer NPB. As the light-emitting layer, a compound of a type as described in Chemical Formula 1 and a compound of a type as described in Chemical Formula 2 in Table 23 below were pre-mixed in one supply source and deposited to 400 angstroms as a main body, and Ir(ppy) ₃ was deposited as a green phosphorescent dopant by 7% doping. Thereafter, BCP was deposited to 60 angstroms as a hole blocking layer, and Alq ₃ was deposited to 200 angstroms on the hole blocking layer as an electron transfer layer. Finally, an electron injection layer was formed on the electron transfer layer by depositing lithium fluoride (LiF) to a thickness of 10 angstroms, and then a cathode was formed on the electron injection layer by depositing an aluminum (Al) cathode to a thickness of 1,200 angstroms, and thus, an organic electroluminescent device was manufactured.

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

For the organic electroluminescent device manufactured as above, electroluminescence (EL) properties were measured using M7000 manufactured by McScience InC., and using the measurement results, _T90 was measured using a life measurement system (M6000) manufactured by McScience InC. when the standard brightness was 6,000 cd/ ^m2 .

The properties of the organic electroluminescent device disclosed in the present invention 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, Table 23 is an example of depositing two luminescent layer compounds in one supply source after premixing in Experimental Example 2, and Table 21 is an example of using a single host material in Experimental Example 1.

As can be seen from Tables 21 to 23, when the organic material layer of the organic light-emitting device includes both the heterocyclic compound shown in Chemical Formula 1 and the heterocyclic compound shown in Chemical Formula 2, superior efficiency and life effects are obtained. This result may lead to the prediction that when the two compounds are included at the same time, an excited complex phenomenon will occur.

The excited complex phenomenon is a phenomenon in which energy having the magnitude of the donor (p-host) HOMO energy level and the acceptor (n-host) LUMO energy level is released due to the exchange of electrons between two molecules. When the excited complex phenomenon occurs between two molecules, reverse intersystem crossing (RISC) occurs, and thus the internal quantum efficiency of fluorescence can be increased up to 100%. When a donor (p-host) having a desirable hole transfer ability and an acceptor (n-host) having a desirable electron transfer ability are used as hosts of the light-emitting layer, holes are injected into the p-host and electrons are injected into the n-host, and thus the driving voltage can be reduced, which ultimately contributes to an increase in lifetime.

In addition, after the premixed compounds, a luminescent body formed of various types of compounds is deposited, and the luminescent body is formed as a deposition supply source in the present disclosure (Experimental Example 2, Table 23). In this article, avoiding multiple depositions has the advantage of maintaining the uniformity of the film surface and the film properties as they are. In addition, while reducing the overall process cost by simplifying the process, a device with improved efficiency, driving voltage and life can be formed.

As can be seen from Tables 22 and 23, the fused carbazole structure of the heterocyclic compound structure shown in Chemical Formula 2 of the present application is a structure including two carbazoles or one carbazole and one heterocycle, and thereby has a strong electron donor property due to the presence of non-shared electron pairs between nitrogen and heteroatoms in carbazole. In other words, as can be seen from Tables 22 and 23, it is recognized that the total driving voltage/efficiency/lifetime is superior compared to when one of the heterocyclic compound corresponding to Chemical Formula 1 and the compounds corresponding to Compounds A to E (biscarbazole type; or a structure in which carbazole and heterocycle are bonded) of the present application is used.

In addition, due to the wide region of π-conjugation corresponding to the entire basic skeleton, a wider HOMO energy level region is obtained compared to the unfused carbazole compound, resulting in a wider hole distribution. Therefore, when the device is driven, fast hole transfer properties are recognized, and thereby, by reducing the driving voltage, it is recognized that there is an expected advantage of improved current efficiency and reduced device critical 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 results in the formation of a structure with minimal intramolecular distortion (rigid structure), and thus high thermal stability (T _d95 : 400° C. or higher, high T _g ) is obtained. High thermal stability is an advantageous factor for overcoming the harsh high vacuum and high temperature conditions of the organic light-emitting device (OLED) deposition process, and is also advantageous for device degradation when the device is driven for a long period of time. Therefore, it can be seen that the fused carbazole structure as the structure shown in Chemical Formula 2 is a base structure that can be used as a material with a satisfactory life based on low voltage, high efficiency, and high thermal stability.

In addition, when premixing is performed as in Table 23, the unique thermal properties of each of the materials in the mix need to be identified. In this context, when premixed host materials are deposited from one 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 in the deposition process, which means that it is impossible to produce completely uniform OLEDs in one deposition process.

In view of the above, the thermal properties of the material can also be controlled according to the shape of the molecular structure, while the electrical properties of the material can be adjusted 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 the C-N bond of the fused carbazole in Chemical Formula 2 can also be used to enhance device performance, and the diversity of various pre-mixed deposition processes between hosts can be ensured by controlling the thermal properties of each of the materials. This has the advantage of ensuring the diversity of pre-mixed deposition processes using three, four or more host materials and two compounds as hosts.

In addition, when driving an OLED, the inside 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 device driving 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 the material. In addition, the OLED deposition process is also performed at high temperature in a high vacuum state, and materials with low thermal stability have deteriorated in the deposition process, making it impossible to drive as an OLED. Therefore, checking the thermal stability of the material forming the device is a very important preparation for building an OLED.

-

鍵而強連接的諸多五邊形/六邊形環進行稠合結構，且具有剛性結構，且因此具有100℃或高於100℃的高Tg及400℃或高於400℃的非常高的Td(95%)。看出，此為一種足以承受OLED沈積製程的苛刻的高真空/高溫狀態且即使當在長時間週期內驅動裝置時亦具有足夠的穩定性以防止裝置劣化的材料。 The fused carbazole structure described in Formula 2 is one in which

-

Many pentagonal/hexagonal rings that are strongly bonded form a fused structure and have a rigid structure, and therefore have a high Tg of 100° C. or higher and a very high Td (95%) of 400° C. or higher. It is seen that this is a material that is strong enough to withstand the harsh high vacuum/high temperature conditions of the OLED deposition process and has sufficient stability to prevent device degradation even when the device is driven for a long period of time.

FIG. 4 to FIG. 21 are thermal analysis data of each material shown in Chemical Formula 2 measured using a Mettler Toledo Thermogravimetric Analysis (TGA)/Differential Scanning Calorimetry (DSC) device. The measured Td ₉₅ is measured by heating the temperature up to 600°C so that the temperature increases from 30°C at 10 K per minute. Among the thermal properties such as the glass transition temperature (Tg), crystallization temperature (Tc), melting temperature (Tm) and decomposition temperature (Td/95%) corresponding to Chemical Formula 2, the glass transition temperature and the decomposition temperature are identified to first identify the stability of the device in a long-term drive and high vacuum deposition process.

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

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

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

As can be recognized by comparing FIGS. 4 to 17 with FIGS. 18 to 21 , in compound A ( FIGS. 18 and 19 ) and compound C ( FIGS. 20 and 21 ) having a biscarbazole structure, Td ₉₅ was measured to be as low as 400° C. or lower, resulting in lower thermal stability compared to the condensed carbazole compound.

Therefore, it is recognized that the basic structure including both the compound shown in Chemical Formula 1 and the compound shown in Chemical Formula 2 is sufficiently effective in manufacturing a device with a low voltage/high efficiency target or an OLED with high efficiency/long life or low voltage/long life properties.

100: Substrate

200: Yang pole

300: Organic material layer

400: cathode

Claims (15)

An 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, wherein the one or more organic material layers simultaneously contain a heterocyclic compound represented by the following chemical formula 1 and a heterocyclic compound represented by any one of the following chemical formulas 2-7 to 2-9:

[Chemical formula 2-7]

In Formula 1 and Formulas 2-7 to 2-9, 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 aryl group; or a substituted or unsubstituted heteroaryl group, a is an integer from 1 to 3, and when a is 2 or more, L is the same as or different from each other; R9, R10, _R11 and R _R1 to R8 are the same as or different from each other and are each independently selected from the group consisting of: hydrogen; and deuterium; R1 to R8 are the same as or different from each other and are each independently selected from the group consisting of: hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more adjacent groups are 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 of 1 to 3, when b is 2 or greater, R _{R 9} are the same or different from each other, and when c is 2 or greater, R ₁₀ are the same or different from each other; A ₁ and A ₂ are the same or different from each other and are each independently O; S; NR _a ; or CR _b R _c ; and R _a to R _c are the same or different from each other and are each independently hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl; A ₃ is O; S; or NR _g ; 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 or different from each other and are 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. 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 5]

In Chemical Formulae 3 to 6, R1 to R10, L, N-Het, a, b and c have the same definitions as in Chemical Formula 1 of claim 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 7]

[Chemical formula 9]

In Chemical Formulae 7 to 9, R1 to R10, L, a, b and c have the same definitions as those in Chemical Formula 1 of claim 1; X1 is CR21 or N, X2 is CR22 or N, X3 is CR23 or N, X4 is CR24 or N, and X5 is CR25 or N; and R21 to R25 and R27 to R32 are the same as or different from each other and are each independently selected from the group consisting of: hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; substituted or unsubstituted phosphine oxide; and substituted or unsubstituted amino, 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. An organic light-emitting device as claimed in claim 3, wherein

It is represented by one of the following chemical formulas 10 to 13:

[Chemical formula 13]

In Chemical Formula 10, one or more of X1, X3 and X5 is N, and R22 and R24 have the same definition as in Chemical Formula 7 of claim 3; in Chemical Formula 11, one or more of X1, X2 and X5 is N; in Chemical Formula 12, one or more of X1 to X3 is N; in Chemical Formula 13, one or more of X1, X2 and X5 is N; and R33 to R36 are the same as or different from each other, and are each independently selected from the group consisting of: hydrogen; deuterium; halogen; cyano ; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; substituted or unsubstituted phosphine oxide; and substituted or unsubstituted amino, 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 as claimed in 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 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; and substituted or unsubstituted amine, or two or more adjacent groups are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or heterocycle. The organic light-emitting device as claimed in 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 Formulae 2-7 to 2-9 is represented by any one of the following compounds:

An organic light-emitting device as described in 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 at least one of the hole blocking layer, 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 2-9. An organic light-emitting device as described in 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 the heterocyclic compound represented by any one of Chemical Formulas 2-7 to 2-9. An organic light-emitting device as described in 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 Formulas 2-7 to 2-9. The organic light-emitting device as described in claim 1 comprises one, two or more layers 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. 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 2-9:

[Chemical formula 2-8]

In Formula 1 and Formulas 2-7 to 2-9, 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 aryl group; or a substituted or unsubstituted heteroaryl group, a is an integer from 1 to 3, and when a is 2 or more, L is the same as or different from each other; R9, R10, _R11 and R _R1 to R8 are the same as or different from each other and are each independently selected from the group consisting of: hydrogen; and deuterium; R1 to R8 are the same as or different from each other and are each independently selected from the group consisting of: hydrogen; deuterium; halogen; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more adjacent groups are 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 of 1 to 3, when b is 2 or greater, R _{R 9} are the same as or different from each other, and when c is 2 or greater, 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 are each independently O; S; NR _a ; or CR _b R _c ; and R _a to R _c are the same as or different from each other and are each independently hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl; A ₃ is O; S; or NR _g ; 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 or different from each other and are 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. A composition for an organic material layer of an organic light-emitting device as described in claim 12, wherein in the composition, the heterocyclic compound represented by Chemical Formula 1: the heterocyclic compound represented by any one of Chemical Formulas 2-7 to 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 forming a second electrode on the one or more organic material layers, wherein the forming of the one or more organic material layers comprises forming the one or more organic material layers using the composition of the organic material layer for an organic light-emitting device as described in claim 12. A method for manufacturing an organic light-emitting device as described in claim 14, wherein the formation of the one or more organic material layers is performed by using a thermal vacuum deposition method after premixing the heterocyclic compound shown in Chemical Formula 1 with the heterocyclic compound shown in any one of Chemical Formulas 2-7 to 2-9.