KR102503221B1 - Heterocyclic compound and organic light emitting device including the same - Google Patents

Abstract

The present specification relates to a heterocyclic compound represented by Chemical Formula 1 and an organic light emitting device including the same.

Description

Heterocyclic compound and an organic light emitting device including the same

The present specification relates to a heterocyclic compound and an organic light emitting device including the same.

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

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

The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound capable of constituting the light emitting layer by itself may be used, or a compound capable of serving as a host or dopant of the host-dopant type light emitting layer may be used. In addition, as a material for the organic thin film, a compound capable of performing roles such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.

In order to improve the performance, lifespan or efficiency of organic light emitting devices, the development of materials for organic thin films is continuously required.

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

The present specification is to provide a heterocyclic compound and an organic light emitting device including the same.

In one embodiment of the present specification, a heterocyclic compound represented by Formula 1 is provided.

[Formula 1]

In Formula 1,

L ₁ and L ₂ are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,

R ₁ and R ₂ are each independently a halogen group; cyano group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; Or a substituted or unsubstituted phosphine oxide group.

In addition, according to an exemplary embodiment of the present application, the first electrode; a second electrode provided to face the first electrode; and an organic material layer provided between the first electrode and the second electrode, wherein the organic material layer includes at least one heterocyclic compound represented by Chemical Formula 1.

The compounds described in this specification can be used as a material for an organic material layer of an organic light emitting device. The compound may serve as a hole injection material, a hole transport material, a light emitting material, an electron transport material, or an electron injection material in an organic light emitting device. In particular, the compound may be used as a material for a light emitting layer of an organic light emitting device.

Formula 1 is a linker between triphenylene and indolo[2,3-a]carbazole, and has a triazine group, thereby forming indolo[2,3-a]carbazole as a strong donor and a triazine group as a strong acceptor. is bonded, and these compounds have bipolar characteristics. Triphenylene can be bonded to the triazine group to create delocalization of the LUMO orbital and increase the stability of electrons to improve lifetime.

In addition, when the heterocyclic compound of Chemical Formula 1 is used as a material for the light emitting layer of the organic light emitting device, the driving voltage of the device can be lowered, light efficiency can be improved, and lifespan characteristics of the device can be improved.

1 to 3 are views each exemplarily illustrating a stacked structure of an organic light emitting device according to an exemplary embodiment of the present specification.

Hereinafter, this specification will be described in more detail.

In this specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

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

는 치환되는 위치를 의미한다.In this specification,

means the position to be substituted.

In the present specification, "substituted or unsubstituted" is a straight-chain or branched-chain alkyl group having 1 to 60 carbon atoms; A straight or branched alkenyl group having 2 to 60 carbon atoms; a straight or branched alkynyl group having 2 to 60 carbon atoms; a monocyclic or polycyclic cycloalkyl group having 3 to 60 carbon atoms; a monocyclic or polycyclic heterocycloalkyl group having 2 to 60 carbon atoms; a monocyclic or polycyclic aryl group having 6 to 60 carbon atoms; A monocyclic or polycyclic heteroaryl group having 2 to 60 carbon atoms; silyl group; phosphine oxide group; And substituted or unsubstituted with one or more substituents selected from the group consisting of an amine group, or substituted or unsubstituted with a substituent in which two or more substituents selected from the above exemplified substituents are connected.

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

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

In the present specification, the alkenyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The alkenyl group may have 2 to 60 carbon atoms, specifically 2 to 40, and more specifically, 2 to 20. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1 -butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but is not limited thereto.

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

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

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

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

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

,

,

,

,

,

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

,

,

,

,

,

etc., but is not limited thereto.

In the present specification, the heteroaryl group includes O, S, SO ₂ Se, N or Si as a hetero atom, and includes a monocyclic or polycyclic group having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which a heteroaryl group is directly connected or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may also be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, an aryl group, and the like. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40, and more specifically 3 to 25 carbon atoms. Specific examples of the heteroaryl group include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, and a thiazolyl group. group, isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , thiazinyl group, dioxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolilyl group, naphthyridyl group, acridinyl group, phenanthridi Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triazaindene group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , Dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, A phenoxazinyl group, a phenanthridyl group, an imidazopyridinyl group, a thienyl group, an indolo[2,3-a]carbazolyl group, an indolo[2,3-b]carbazolyl group, an indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenantrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthyridinyl group, phenanthrolinyl group, Benzo [c] [1,2,5] thiadiazolyl group, 5,10-dihydrodibenzo [b, e] [1,4] azasilinyl group, pyrazolo [1,5-c] quinazolinyl group , pyrido [1,2-b] indazolyl group, pyrido [1,2-a] imidazo [1,2-e] indolinyl group, benzofuro [2,3-d] pyrimidyl group; Benzothieno [2,3-d] pyrimidyl group; Benzofuro[2,3-a]carbazolyl group, benzothieno[2,3-a]carbazolyl group, 1,3-dihydroindolo[2,3-a]carbazolyl group, benzofuro [3,2-a] carbazolyl group, benzothieno [3,2-a] carbazolyl group, 1,3-dihydroindolo [3,2-a] carbazolyl group, benzofuro [2, 3-b] carbazolyl group, benzothieno [2,3-b] carbazolyl group, 1,3-dihydroindolo [2,3-b] carbazolyl group, benzofuro [3,2-b] ]carbazolyl group, benzothieno[3,2-b]carbazolyl group, 1,3-dihydroindolo[3,2-b]carbazolyl group, benzofuro[2,3-c]carbazolyl group group, benzothieno[2,3-c]carbazolyl group, 1,3-dihydroindolo[2,3-c]carbazolyl group, benzofuro[3,2-c]carbazolyl group, benzo Thieno[3,2-c]carbazolyl group, 1,3-dihydroindolo[3,2-c]carbazolyl group, 1,3-dihydroindeno[2,1-b]carbazolyl group , 5,11-dihydroindeno [1,2-b] carbazolyl group, 5,12-dihydroindeno [1,2-c] carbazolyl group, 5,8- dihydroindeno [2, 1-c] carbazolyl group, 7,12-dihydroindeno [1,2-a] carbazolyl group, 11,12-dihydroindeno [2,1-a] carbazolyl group, etc. , but is not limited thereto.

In the present specification, the phosphine oxide group may be specifically substituted with an aryl group, and the above-described examples may be applied to the aryl group. For example, the phosphine oxide group includes, but is not limited to, a dimethylphosphine oxide group, a diphenylphosphine oxide group, and a dinaphthylphosphine oxide group.

In the present specification, the amine group is a monoalkylamine group; monoarylamine group; Monoheteroarylamine group; -NH ₂ ; Dialkylamine group; Diaryl amine group; Diheteroarylamine group; an alkyl arylamine group; Alkylheteroarylamine group; And it may be selected from the group consisting of an arylheteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a dibiphenylamine group, an anthracenylamine group, a 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluorene Examples include a ylamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group, and the like, but are not limited thereto.

In the present specification, examples of the above-described aryl group may be applied to the arylene group, except that the arylene group is a divalent group.

In the present specification, examples of the above-described heteroaryl group may be applied to the heteroarylene group, except that the heteroarylene group is a divalent group.

In one embodiment of the present specification, a heterocyclic compound represented by Formula 1 is provided.

The heterocyclic compound according to the present specification is characterized in that triphenylin and indolo[2,3-a]carbazole have a triazine as a linker.

Compared to compounds containing pyrimidine or pyridine as a linker instead of triazine, the heterocyclic compound according to the present specification has a low LUMO level and high electron mobility, so that when used in a device, the lifetime of the device is improved.

The heterocyclic compound according to the present specification includes indolo[2,3-a]carbazole, and compared to compounds containing other types of condensed carbazole, the balance of holes and electrons in the light emitting layer is not disturbed and hole stability is improved. As a result, lifespan can be improved.

In one embodiment of the present specification, the L ₁ and L ₂ are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

In one embodiment of the present specification, the L ₁ and L ₂ are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 40 carbon atoms; or a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms.

In one embodiment of the present specification, the L ₁ and L ₂ are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 20 carbon atoms; or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.

In one embodiment of the present specification, the L ₁ and L ₂ are each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted terphenylene group; A substituted or unsubstituted anthracenylene group; Or a substituted or unsubstituted divalent carbazole group.

In one embodiment of the present specification, the L ₁ and L ₂ are each independently a direct bond; phenylene group; Biphenylene group; Terphenylene group; Anthracenylene group; or a divalent carbazole group.

In one embodiment of the present specification, the L _One Is a direct bond; phenylene group; Biphenylene group; Terphenylene group; Anthracenylene group; or a divalent carbazole group.

In one embodiment of the present specification, the L ₂ is a direct bond; or a phenylene group.

In one embodiment of the present specification, the R ₁ and R ₂ are each independently a halogen group; cyano group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; Or a substituted or unsubstituted phosphine oxide group.

In one embodiment of the present specification, R ₁ is a cyano group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms; Or a substituted or unsubstituted phosphine oxide group.

In one embodiment of the present specification, R ₁ is a cyano group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms; Or a substituted or unsubstituted phosphine oxide group.

In one embodiment of the present specification, R ₁ is a cyano group; A substituted or unsubstituted silyl group; A substituted or unsubstituted methyl group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted anthracenyl group; A substituted or unsubstituted phenanthrenyl group; A substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted pyrenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted phosphine oxide group; Or any one selected from the following structural formula.

In one embodiment of the present specification, R ₁ is a cyano group; A silyl group unsubstituted or substituted with an aryl group; A methyl group unsubstituted or substituted with an aryl group; A phenyl group unsubstituted or substituted with a deuterium or cyano group; biphenyl group; terphenyl group; naphthyl group; an anthracenyl group unsubstituted or substituted with an aryl group; phenanthrenyl group; triphenylenyl group; pyrenyl group; A fluorenyl group unsubstituted or substituted with an alkyl group or an aryl group; 9,9'-spirobi[fluorene]; Dibenzofuran group; Dibenzothiophene group; a carbazole group unsubstituted or substituted with an aryl group or a heteroaryl group; A phosphine oxide group unsubstituted or substituted with an aryl group; Or any one selected from the following structural formula.

In one embodiment of the present specification, R ₂ is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

In one embodiment of the present specification, R ₂ is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted carbazole group.

In one embodiment of the present specification, R ₂ is a phenyl group; biphenyl group; terphenyl group; A fluorenyl group unsubstituted or substituted with an alkyl group; Dibenzofuran group; Dibenzothiophene group; or a carbazole group unsubstituted or substituted with an aryl group.

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

[Formula 1-2]

In Formula 1-2, each substituent has the same definition as in Formula 1.

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

In addition, by introducing various substituents into the structure of Chemical Formula 1, compounds having unique characteristics of the introduced substituents can be synthesized. For example, by introducing a substituent mainly used in the hole injection layer material, the hole transport layer material, the light emitting layer material, the electron transport layer material, and the charge generation layer material used in the manufacture of an organic light emitting device into the core structure, the conditions required by each organic layer are met. substances can be synthesized.

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

In one embodiment of the present specification, the first electrode; a second electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes at least one heterocyclic compound represented by Chemical Formula 1.

In one embodiment of the present specification, at least one layer among the organic material layers includes one type of heterocyclic compound represented by Chemical Formula 1.

In one embodiment of the present specification, the organic material layer further includes a compound represented by Formula 2 below.

[Formula 2]

In Formula 2,

R _a , R _b , R ₂₁ and R ₂₂ are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

r and s are each an integer from 1 to 7;

When r and s are each 2 or more, the substituents in parentheses are the same as or different from each other.

In one embodiment of the present specification, Chemical Formula 2 may be represented by any one of Chemical Formulas 2-1 to 2-4.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Chemical Formulas 2-1 to 2-4, the definition of each substituent is the same as that in Chemical Formula 2.

In one embodiment of the present specification, R ₂₁ and R ₂₂ are each independently a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present specification, R ₂₁ and R ₂₂ are each independently a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present specification, R ₂₁ and R ₂₂ are each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted fluorenyl group; 9,9'-spirobi[fluorene]; or a substituted or unsubstituted dibenzothiophene group.

In an exemplary embodiment of the present specification, R ₂₁ and R ₂₂ are each independently a cyano group or a phenyl group substituted with a triphenylsilyl group; biphenyl group; terphenyl group; naphthyl group; triphenylenyl group; A fluorenyl group unsubstituted or substituted with a methyl group or a phenyl group; 9,9'-spirobi[fluorene]; or a dibenzothiophene group unsubstituted or substituted with a phenyl group, biphenyl group, naphthyl group, 9,9-dimethyl-9H-fluorene, dibenzofuran group or dibenzothiophene group.

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

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

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

In one embodiment of the present specification, the organic light emitting device may be a blue organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material for the blue organic light emitting device. For example, the heterocyclic compound represented by Chemical Formula 1 may be included in the light emitting layer of the blue organic light emitting device.

In one embodiment of the present specification, the organic light emitting device may be a green organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material for the green organic light emitting device. For example, the heterocyclic compound represented by Chemical Formula 1 may be included in a light emitting layer of a green organic light emitting device.

In one embodiment of the present specification, the organic light emitting device may be a red organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 may be used as a material for the red organic light emitting device. For example, the heterocyclic compound represented by Chemical Formula 1 may be included in the light emitting layer of the red organic light emitting device.

The organic light emitting device of the present specification may be manufactured by conventional organic light emitting device manufacturing methods and materials, except for forming one or more organic material layers using the above compounds.

The compound may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

The organic material layer of the organic light emitting device of the present specification may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like 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.

In the organic light emitting device of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer may include the heterocyclic compound represented by Chemical Formula 1.

In the organic light emitting device of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a host, and the host may include a heterocyclic compound represented by Chemical Formula 1.

In the organic light emitting device of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a host, and the host may include a heterocyclic compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2.

In one embodiment of the present specification, the heterocyclic compound of Formula 1 and the compound of Formula 2 are 1:10 to 10:1, 1:8 to 8:1, 1:5 to 5:1, 1:2 to It may be included in a weight ratio of 2:1, but is not limited thereto. (The weight ratio is appropriate.)

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

1 to 4 illustrate the stacking order of the electrode and the organic material layer of the organic light emitting device according to an exemplary embodiment of the present specification. However, it is not intended that the scope of the present application be limited by these drawings, and structures of organic light emitting devices known in the art may be applied to the present application as well.

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

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

The organic material layer including the heterocyclic compound represented by Chemical Formula 1 may further include other materials as needed.

In the organic light emitting device according to an exemplary embodiment of the present specification, materials other than the heterocyclic compound represented by Formula 1 are exemplified below, but these are for illustrative purposes only and are not intended to limit the scope of the present application. Materials known in the art may be substituted.

Materials having a relatively high work function may be used as the anode material, and transparent conductive oxides, metals, or conductive polymers 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, but are not limited thereto.

Materials having a relatively low work function may be used as the cathode material, and metals, metal oxides, or conductive polymers may be used. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

As the hole injection material, a known hole injection material may be used. For example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or described in [Advanced Material, 6, p.677 (1994)] starburst amine derivatives, such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine (m- MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), polyaniline/dodecylbenzenesulfonic acid, a soluble conductive polymer, or poly( 3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), polyaniline/camphor sulfonic acid or polyaniline/ Poly(4-styrenesulfonate) (Polyaniline/Poly(4-styrenesulfonate)) or the like can be used.

As the hole transport material, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, and the like may be used, and low molecular weight or high molecular weight materials may also be used.

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

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

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

When the host of the light emitting material is mixed and used, hosts of the same series may be mixed and used, or hosts of different series may be mixed and used. For example, two or more materials selected from among n-type host materials and p-type host materials may be selected and used as host materials for the light emitting layer.

An organic light emitting device according to an exemplary embodiment of the present specification may be a top emission type, a bottom emission type, or a double side emission type depending on materials used.

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

The present specification is a heterocyclic compound represented by Formula 1; And it provides a composition for forming an organic material layer comprising a compound represented by the following formula (2).

[Formula 1]

In Formula 1,

L ₁ and L ₂ are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,

R ₁ and R ₂ are each independently a halogen group; cyano group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; Or a substituted or unsubstituted phosphine oxide group,

[Formula 2]

In Formula 2,

R _a , R _b , R ₂₁ and R ₂₂ are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

r and s are each an integer from 1 to 7;

When r and s are each 2 or more, the substituents in parentheses are the same as or different from each other.

The composition for forming an organic layer according to an exemplary embodiment of the present specification may include the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 in a weight ratio of 1:10 to 10:1, preferably 1:8 to 8:1, 1:5 to 5:1, 1:2 to 2:1.

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

<Production Example>

<Preparation Example 1> Preparation of compound 1-1

1) Preparation of compound 1-1-1

2,4-dichloro-6-phenyl-1,3,5-triazine (2,4-dichloro-6-phenyl-1,3,5-triazine) 10.0 g (44.2 mM), triphenylene-2- Ilboronic acid (triphenylen-2-ylboronic acid) 9.3g (34.0mM), Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium (0)) 2.0g (1.7mM), Na ₂ CO ₃ 5.4g (51.0mM) was dissolved in THF (tetrohydrofuran)/H ₂ O 250mL/50mL and then refluxed for 24 hours. After the reaction was completed, distilled water and DCM (dichloromethane) were added at room temperature for extraction, and the organic layer was dried with MgSO ₄ and the solvent was removed using a rotary evaporator. The reactant was purified by column chromatography (DCM:Hex=1:3) and recrystallized with methanol (MeOH) to obtain 10.6 g (75%) of the target compound 1-1-1.

2) Preparation of Compound 1-1

Compound 1-1-1 10.6g (25.5mM), 11-phenyl-11,12-dihydroindolo[2,3-a]carbazole (11-phenyl-11,12-dihydroindolo[2,3-a ]carbazole) 9.3 g (28.1 mM), Pd ₂ (dba) ₃ (tris (dibenzylideneacetone) dipalladium (0)) 1.2 g (1.3 mM), Xphos (2-dicyclohexylphosphino-2', After dissolving 4',6'-triisopropylbiphenyl) 1.2g (2.6mM) and NaOt-Bu 4.9g (51.0mM) in 200mL of 1,4-dioxane, the mixture was refluxed for 24 hours. After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried with MgSO ₄ and the solvent was removed using a rotary evaporator. The reactant was purified by column chromatography (DCM:Hexane=1:3) and recrystallized with methanol to obtain 15.5 g (85%) of the target compound 1-1.

In Preparation Example 1, the target compound was synthesized by preparing in the same manner as in Preparation Example 1, except that Intermediate A in Table 1 was used instead of 2,4-dichloro-6-phenyl-1,3,5-triazine. did

compound
number Intermediate A target compound 1-3

1-4

1-24

1-25

1-31

1-32

1-33

1-36

1-43

1-44

1-59

It was prepared in the same manner as in Preparation Example 1, except that Intermediate B in Table 2 was used instead of 11-phenyl-11,12-dihydroindolo[2,3-a]carbazole in Preparation Example 1. compound was synthesized.

compound
number Intermediate B target compound 1-92

1-93

1-99

1-103

1-104

1-107

1-110

<Preparation Example 2> Synthesis of compound 2-2

1) Preparation of compound 2-2-2

2-bromodibenzo[b,d]thiophene 4.2 g (15.8 mM), 9-phenyl-9H,9'H-3,3'-bicarbazole 6.5 g (15.8 mM), CuI 3.0 g (15.8 mM) ), 1.9 mL (15.8 mM) of trans-1,2-diaminocyclohexane, and 3.3 g (31.6 mM) of K ₃ PO ₄ were dissolved in 100 mL of 1,4-dioxane and refluxed for 24 hours. After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried with MgSO ₄ and the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) and recrystallized with methanol to obtain 7.9 g (85%) of the target compound 2-2-2.

2) Preparation of compound 2-2-1

To a mixed solution containing 8.4 g (14.3 mmol) of Compound 2-2-1 and 100 mL of THF, 7.4 mL (18.6 mmol) of 2.5M n-BuLi was added dropwise at -78°C and stirred at room temperature for 1 hour. 4.8mL (42.9mmol) of trimethyl borate was added dropwise to the reaction mixture and stirred at room temperature for 2 hours. After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried with MgSO ₄ and the solvent was removed using a rotary evaporator. The reactant was purified by column chromatography (DCM:MeOH=100:3) and recrystallized with DCM to obtain 3.9 g (70%) of the target compound 2-2-1.

3) Preparation of compound 2-2

Compound 2-2-1 6.7 g (10.5 mM), iodobenzene 2.1 g (10.5 mM), Pd (PPh ₃ ) ₄ 606 mg (0.52 mM), K ₂ CO ₃ 2.9 g (21.0 mM) were mixed with toluene/EtOH/ After dissolving in H ₂ O 100/20/20 mL, it was refluxed for 12 hours. After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried with MgSO ₄ and the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) and recrystallized from methanol to obtain the target compound 2-2. 4.9 g (70%) was obtained.

<Preparation Example 3> Synthesis of compound 2-3

Compound 2-3 (83%) was obtained in the same manner as in Preparation Example 2, except that 4-iodo-1,1'-biphenyl was used instead of iodobenzene.

<Preparation Example 4> Synthesis of Compound 3-3

1) Preparation of compound 3-3

3-bromo-1,1'-biphenyl 3.7 g (15.8 mM), 9-phenyl-9H,9'H-3,3'-bicarbazole 6.5 g (15.8 mM), CuI 3.0 g (15.8 mM) ), trans-1,2-diaminocyclohexane 1.9mL (15.8mM) and K ₃ PO ₄ 3.3g (31.6mM) were dissolved in 100mL of 1,4-dioxane and refluxed for 24 hours. After the reaction was completed, distilled water and DCM were added at room temperature for extraction, and the organic layer was dried with MgSO ₄ and the solvent was removed using a rotary evaporator. The reactant was purified by column chromatography (DCM:Hexane=1:3) and recrystallized with methanol to obtain 7.5 g (85%) of the target compound 3-3.

In Preparation Example 4, Intermediate A of Table 3 was used instead of 3-bromo-1,1`-biphenyl, and 9-phenyl-9H,9'H-3,3'-bicarbazole was replaced with Table 3 A target compound was synthesized in the same manner as in Preparation Example 4, except that Intermediate B was used.

compound
number Intermediate A Intermediate B target compound 3-4

3-7

3-31

3-32

3-42

The rest of the compounds other than the compounds described in Preparation Examples 1 to 4 and Tables 1 to 3 were also prepared in the same manner as described in the above-described Preparation Examples. Table 4 and Table 5 show the synthesis confirmation results.

compound
number ¹ H NMR (CDCl ₃ , 200 Mz) 1-1 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.36-8.30 (4H, m), 8.15-8.12 (2H, m), 7.94 (2H, m), 7.70- 7.50 (15H, m), 7.35 (2H, t), 7.16 (2H, t) 1-3 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.38-8.30 (3H, m), 8.15-8.12 (2H, m), 7.94 (3H, m), 7.75- 7.35 (21H, m), 7.16 (2H, t) 1-4 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.33-8.30 (2H, m), 8.15-8.12 (2H, m), 7.96-7.94 (4H, m), 7.75-7.35 (19H, m), 7.25-7.16 (2H, t) 1-24 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.33-8.30 (2H, m), 8.15-8.12 (2H, m), 7.94-7.90 (3H, m), 7.70-7.28 (20H, m), 7.16 (2H, t), 1.69 (6H, s) 1-25 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.33-8.30 (2H, m), 8.15-8.12 (2H, m), 7.98-7.94 (3H, m), 7.82 (1H, d), 7.70-7.50 (15H, m), 7.39-7.31 (4H, m), 7.16 (2H, t) 1-31 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.33-8.30 (2H, m), 8.15-8.09 (3H, m), 7.94-7.89 (4H, m), 7.76-7.50 (14H, m), 7.38-7.28 (4H, m), 1.69 (6H, s) 1-32 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.33-8.30 (2H, m), 8.15-8.12 (2H, m), 8.03-7.94 (4H, m), 7.82 (1H, d), 7.76-7.50 (15H, m), 7.39-7.31 (4H, m), 7.16 (2H, t) 1-33 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.45 (1H, d), 8.33-8.12 (6H, m), 7.94 (2H, m), 7.70-7.49 ( 14H, m), 7.35 (2H, t), 7.16 (2H, t) 1-36 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (3H, d), 8.45 (1H, d), 8.33-8.30 (2H, m), 8.15-8.12 (2H, m), 7.94- 7.92 (4H, m), 7.70-7.50 (15H, m), 7.35 (2H, t), 7.16 (2H, t) 1-43 δ = 9.60 (1H, d), 9.27 (1H, s), 8.56-8.55 (3H, m), 8.33-8.30 (2H, m), 8.15-8.12 (2H, m), 8.02-7.94 (3H, m) ), 7.85 (1H, s), 7.72-7.50 (13H, m), 7.35 (2H, t), 7.16 (2H, t) 1-44 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.33-8.30 (2H, m), 8.15-8.12 (2H, m), 7.94 (2H, m), 7.70- 7.50 (12H, m), 7.35 (2H, t), 7.16 (2H, t) 1-59 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.33-8.30 (2H, m), 8.19-8.12 (3H, m), 7.94 (3H, m), 7.70- 7.50 (14H, m), 7.35 (3H, m), 7.20-7.16 (4H, m) 1-92 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.36-8.30 (4H, m), 8.21-8.12 (3H, m), 7.94 (2H, m), 7.70- 7.35 (20H, m), 7.16 (2H, t) 1-93 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.36-8.30 (4H, m), 8.15-8.12 (2H, m), 7.94-7.91 (6H, m), 7.75-7.35 (17H, m), 7.16 (2H, t) 1-99 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.36-8.30 (4H, m), 8.15-8.12 (2H, m), 7.98-7.94 (3H, m), 7.70-7.50 (13H, m), 7.39-7.16 (7H, m) 1-103 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.36-8.30 (4H, m), 8.15-8.12 (2H, m), 7.98-7.94 (4H, m), 7.70-7.50 (14H, m), 7.39-7.16 (7H, m) 1-104 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.45 (1H, d), 8.36-8.30 (4H, m), 8.19-8.12 (3H, m), 7.98- 7.93 (4H, m), 7.70-7.45 (13H, m), 7.35 (2H, t), 7.16 (2H, t) 1-107 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.36-8.30 (4H, m), 8.15-8.12 (2H, m), 7.98-7.94 (3H, m), 7.74-7.50 (12H, m), 7.39-7.31 (5H, m), 7.16 (2H, t) 1-110 δ = 9.60 (1H, d), 9.27 (1H, s), 8.55 (2H, d), 8.36-8.30 (4H, m), 8.19-8.08 (4H, m), 7.94 (2H, m), 7.74- 7.50 (19H, m), 7.35 (2H, t), 7.16 (2H, t) 2-2 δ = 8.55 (1H, d), 8.45 (1H, d), 8.30 (1H, d), 8.19 (1H, d), 8.13 (1H, d), 8.00 to 7.89 (6H, m), 7.77 (2H, m), 7.62~7.35(15H, m), 7.20~7.16(2H, m) 3-3 δ = 8.55 (1H, d), 8.30 (1H, d), 8.21-8.13 (3H, m), 7.99-7.89 (4H, m), 7.77-7.35 (17H, m), 7.20-7.16 (2H, m) ) 3-4 δ = 8.55 (1H, d), 8.30 (1H, d), 8.19-8.13 (2H, m), 7.99-7.89 (8H, m), 7.77-7.75 (3H, m), 7.62-7.35 (11H, m) ), 7.20-7.16 (2H, m) 3-7 δ = 8.55 (1H, d), 8.31-8.30 (3H, d), 8.19-8.13 (2H, m), 7.99-7.89 (5H, m), 7.77-7.75 (5H, m), 7.62-7.35 (14H , m), 7.20-7.16 (2H, m) 3-31 δ = 8.55 (1H, d), 8.30 (1H, d), 8.21-8.13 (4H, m), 7.99-7.89 (4H, m), 7.77-7.35 (20H, m), 7.20-7.16 (2H, m) ) 3-32 δ = 8.55 (1H, d), 8.30 (1H, d), 8.21-8.13 (3H, m), 7.99-7.89 (8H, m), 7.77-7.35 (17H, m), 7.20-7.16 (2H, m) )

compound FD-MS compound FD-MS 1-1 m/z = 713.26 (C ₅₁ H ₃₅ N ₅ =713.84) 1-3 m/z = 789.29 (C ₅₇ H ₃₅ N ₅ =789.94) 1-4 m/z = 789.29 (C ₅₇ H ₃₅ N ₅ =789.94) 1-24 m/z = 829.32 (C ₆₀ H ₃₉ N ₅ =830.01) 1-25 m/z= 803.27 (C ₅₇ H ₃₃ N ₅ O=803.92) 1-31 m/z = 829.32 (C ₆₀ H ₃₉ N ₅ =830.01) 1-32 m/z= 803.27 (C ₅₇ H ₃₃ N ₅ O=803.92) 1-33 m/z = 819.25 (C ₅₇ H ₃₃ N ₅ S = 819.99) 1-36 m/z = 819.25 (C ₅₇ H ₃₃ N ₅ S = 819.99) 1-43 m/z = 738.25 (C ₅₂ H ₃₀ N ₆ =738.85) 1-44 m/z = 718.29 (C ₅₁ H ₂₆ D ₅ N ₅ =718.87) 1-59 m/z = 802.28 (C ₅₇ H ₃₄ N ₆ =802.94) 1-92 m/z = 789.29 (C ₅₇ H ₃₅ N ₅ =789.94) 1-93 m/z = 789.29 (C ₅₇ H ₃₅ N ₅ =789.94) 1-99 m/z= 803.27 (C ₅₇ H ₃₃ N ₅ O=803.92) 1-103 m/z= 803.27 (C ₅₇ H ₃₃ N ₅ O=803.92) 1-104 m/z = 819.25 (C ₅₇ H ₃₃ N ₅ S = 819.99) 1-107 m/z= 803.27 (C ₅₇ H ₃₃ N ₅ O=803.92) 1-110 m/z = 878.32 (C ₆₃ H ₃₈ N ₆ =879.04) 2-2 m/z = 666.84 (C ₄₈ H ₃₀ N ₂ =666.21) 3-3 m/z = 560.23 (C ₄₂ H ₂₈ N ₂ =560.70) 3-4 m/z = 560.23 (C ₄₂ H ₂₈ N ₂ =560.70) 3-7 m/z = 636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 3-31 m/z = 636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 3-32 m/z = 636.26 (C ₄₈ H ₃₂ N ₂ =636.80)

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

A glass substrate coated with a thin film of indium tin oxide (ITO) to a thickness of 1,500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning was performed with solvents such as acetone, methanol, and isopropyl alcohol, and after drying, UVO (Ultraviolet ozone) treatment was performed for 5 minutes using UV in a UV (Ultraviolet) cleaner. Thereafter, the substrate was transferred to a plasma cleaner (PT), plasma treated to remove the ITO work function and residual film in a vacuum state, and transferred to a thermal evaporation equipment for organic deposition.

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

A light emitting layer was thermally vacuum deposited thereon as follows. The emission layer was deposited with 400 Å of a heterocyclic compound of Formula 1 shown in Table 6 as a host, and a green phosphorescent dopant was deposited by doping Ir(ppy) ₃ at 7% of the deposition thickness of the emission layer. Thereafter, 60 Å of bathocuproine (BCP) was deposited as a hole blocking layer, and 200 Å of Alq3 was deposited thereon as an electron transport layer. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited on the electron injection layer to a thickness of 1,200 Å to form a cathode. An electroluminescent device was manufactured.

Meanwhile, all organic compounds required for OLED device fabrication were purified by vacuum sublimation under 10 ⁻⁸ to 10 ⁻⁶ torr for each material and used for OLED fabrication.

The electroluminescence (EL) characteristics of the organic electroluminescent device manufactured as described above were measured with McSyers' M7000, and the standard luminance was measured at 6,000 At cd/m ² , T ₉₀ was measured.

The results of measuring the driving voltage, luminous efficiency, color (EL color), and lifetime of the organic light emitting device manufactured according to the present invention are shown in Table 6 below.

light emitting layer
compound drive voltage
(V) efficiency
(cd/A) color
EL color life span
(T ₉₀ ) Example 1 1-1 4.97 72 green 299 Example 2 1-3 4.38 71 472 Example 3 1-4 4.14 80 487 Example 4 1-24 4.48 77 438 Example 5 1-25 4.34 79 464 Example 6 1-31 4.67 76 434 Example 7 1-32 4.43 77 452 Example 8 1-33 4.32 79 447 Example 9 1-36 4.68 76 442 Example 10 1-43 4.68 74 429 Example 11 1-44 4.84 73 321 Example 12 1-59 4.61 75 359 Example 13 1-92 4.63 71 353 Example 14 1-93 4.63 70 353 Example 15 1-99 4.49 76 344 Example 16 1-103 4.64 71 333 Example 17 1-104 4.60 72 332 Example 18 1-107 4.71 74 321 Example 19 1-110 4.93 71 328 Comparative Example 1 Ref. One 5.44 49 67 Comparative Example 2 Ref. 2 5.49 48 75 Comparative Example 3 Ref. 3 5.66 45 58 Comparative Example 4 Ref. 4 5.37 56 108 Comparative Example 5 Ref. 5 5.33 51 92 Comparative Example 6 Ref. 6 5.41 57 91 Comparative Example 7 Ref. 7 5.56 60 88 Comparative Example 8 Ref. 8 5.26 47 35 Comparative Example 9 Ref. 9 5.64 43 41 Comparative Example 10 Ref. 10 5.94 39 20

As can be seen from the results of Table 6, organic electroluminescent devices using the organic electroluminescent device light emitting layer material of the present invention had a lower driving voltage and improved luminous efficiency as well as significantly improved lifespan compared to Comparative Examples 1 to 10. .

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

A glass substrate coated with a thin film of indium tin oxide (ITO) to a thickness of 1,500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning was performed with solvents such as acetone, methanol, and isopropyl alcohol, and after drying, UVO (Ultraviolet ozone) treatment was performed for 5 minutes using UV in a UV (Ultraviolet) cleaner. Thereafter, the substrate was transferred to a plasma cleaner (PT), plasma treated to remove the ITO work function and residual film in a vacuum state, and transferred to a thermal evaporation equipment for organic deposition.

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

A light emitting layer was thermally vacuum deposited thereon as follows. As shown in Table 7 below, the light emitting layer was pre-mixed with one heterocyclic compound of Formula 1 and one compound of Formula 2, and deposited at 400 Å in one park after pre-mixing, and a green phosphorescent dopant [Ir(ppy) ₃ ] was doped with 7% of the deposition thickness of the light emitting layer and deposited.

Thereafter, 60 Å of bathocuproine (BCP) was deposited as a hole blocking layer, and 200 Å of Alq3 was deposited thereon as an electron transport layer. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited on the electron injection layer to a thickness of 1,200 Å to form a cathode. An electroluminescent device was manufactured.

Meanwhile, all organic compounds required for OLED device fabrication were purified by vacuum sublimation under 10 ⁻⁸ to 10 ⁻⁶ torr for each material and used for OLED fabrication.

The electroluminescence (EL) characteristics of the organic electroluminescent device manufactured as described above were measured with McSyers' M7000, and the standard luminance was measured at 6,000 At cd/m ² , T ₉₀ was measured.

The results of measuring the driving voltage, luminous efficiency, color (EL color), and lifetime of the organic light emitting device manufactured according to the present invention are shown in Table 7 below.

light emitting layer
compound ratio drive voltage
(V) efficiency
(cd/A) color
EL color life span
(T ₉₀ ) Example 20 1-25:3-3 1:8 4.83 53 green 546 Example 21 1:5 4.81 58 552 Example 22 1:2 4.45 78 667 Example 23 1:1 4.51 74 660 Example 24 2:1 4.77 72 608 Example 25 5:1 4.42 67 541 Example 26 8:1 4.31 68 533 Example 27 1-36:3-4 1:2 4.43 73 630 Example 28 1:1 4.52 73 621 Example 29 2:1 4.76 70 596 Example 30 1-24:3-7 1:2 4.48 77 607 Example 31 1:1 4.55 71 590 Example 32 2:1 4.76 72 568 Example 33 1-33:3-31 1:2 4.43 74 637 Example 34 1:1 4.58 71 611 Example 35 2:1 4.79 68 586 Example 36 1-4:3-32 1:2 4.33 76 747 Example 37 1:1 4.48 69 614 Example 38 2:1 4.69 70 593 Example 39 1-3:3-32 1:2 4.33 74 688 Example 40 1:1 4.48 71 650 Example 41 2:1 4.69 68 611 Example 42 1-32:2-2 1:2 4.31 78 654 Example 43 1:1 4.42 76 626 Example 44 2:1 4.66 70 604

Looking at the results of Table 7, when the heterocyclic compound of Formula 1 and the compound of Formula 2 are included at the same time, better efficiency and lifespan effect are shown. This result can be expected that an exciplex phenomenon occurs when the two compounds are included at the same time.

The exciplex phenomenon is a phenomenon in which energy of the size of the HOMO level of the donor (p-host) and the LUMO level of the acceptor (n-host) is released through electron exchange between two molecules. When the exciplex between two molecules occurs, Reverse Intersystem Crossing (RISC) occurs, and this can increase the internal quantum efficiency of fluorescence to 100%. When a donor (p-host) with good hole transport ability and an acceptor (n-host) with good electron transport capability are used as the host of the light emitting layer, holes are injected into the p-host and electrons are injected into the n-host. can be lowered, thereby helping to improve the lifespan. In the present invention, it was confirmed that excellent device characteristics were exhibited when the donor role was the compound of Formula 2 and the acceptor role was the heterocyclic compound of Formula 1 used as the light emitting layer host.

Tables 8 to 11 show the LUMOs of the compounds used in Examples and Comparative Examples.

In the results of Tables 6 and 8, the LUMO orbital of Compound 1-1 is widely spread with triazine and surrounding substituents. But Ref. In the case of pyrimidine or pyridine instead of triazine as in the compounds 1, 2, and 3, the LUMO level of compound 1-1 is higher and the electron mobility is lowered, so that the balance of holes and electrons in the light emitting layer is broken, resulting in a decrease in lifetime. there was.

In the results of Tables 6 and 9, the HOMO orbital of Compound 1-1 is localized to indolocarbazole. But Ref. When indolocarbazole having a different condensation site is substituted as in the compounds of 4 and 5, it has a higher HOMO level and higher hole mobility than Compound 1-1. These results confirm that the balance of holes and electrons in the light emitting layer is broken and the lifetime is reduced.

Also, Ref. Compounds 6 and 7 are substituted with condensed carbazole instead of indolocarbazole. Carbazole condensed with 1,1-dimethylindene and benzofuran has a lower HOMO level than compound 1-1. These results confirm that the movement of holes from the HOMO of the host to the HOMO of the dopant is not smooth and the lifetime is reduced.

In the results of Tables 6 and 10, Ref. When there is no triazine, such as in the compounds 8, 9, and 10, the LUMO orbital is delocalized to the aryl group, so electrons cannot be stabilized more than triazine, and the LUMO level is higher than that of compound 1-1 (-1.96). These results confirm that the lifespan of the light emitting layer is reduced due to the decrease in stability and mobility of electrons.

Looking at the results of Tables 6 and 11 together, the LUMO orbital of the biphenylene-substituted compound 1-4 is delocalized to triphenylene, triazine, and biphenylene rather than the phenylene-substituted compound 1-1. can know that Therefore, it was confirmed that compound 1-4 effectively stabilized electrons and improved lifespan compared to compound 1-1.

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

Claims (15)

A heterocyclic compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
L ₁ and L ₂ are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,
R ₁ is a cyano group; A substituted or unsubstituted silyl group; A methyl group substituted with an aryl group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted anthracenyl group; A substituted or unsubstituted phenanthrenyl group; A substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted pyrenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted phosphine oxide group; Or any one selected from the following structural formulas,

R ₂ is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted carbazole group,
When L ₁ is a direct bond, R ₁ is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted anthracenyl group; A substituted or unsubstituted phenanthrenyl group; A substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted pyrenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted carbazole group; Or any one selected from the following structural formulas,

When L ₁ and L ₂ are each a direct bond and R ₁ is an unsubstituted phenyl group, R ₂ is A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted carbazole group. The method of claim 1,
Formula 1 is a heterocyclic compound represented by Formula 1-2:
[Formula 1-2]

In Formula 1-2, each substituent has the same definition as in Formula 1. The method of claim 1,
The L ₁ and L ₂ are each independently a direct bond; phenylene group; Biphenylene group; Terphenylene group; Anthracenylene group; Or a heterocyclic compound that is a divalent carbazole group. delete delete The method of claim 1,
Formula 1 is a heterocyclic compound represented by any one of the following compounds:

. a first electrode; a second electrode; and an organic material layer provided between the first electrode and the second electrode,
The organic material layer is an organic light emitting device comprising at least one heterocyclic compound according to any one of claims 1 to 3 and 6. The method of claim 7,
The organic material layer is an organic light emitting device comprising two kinds of the heterocyclic compound. The method of claim 7,
The organic light emitting device further comprises a compound represented by Formula 2 below:
[Formula 2]

In Formula 2,
R _a , R _b , R ₂₁ and R ₂₂ are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
r and s are each an integer from 1 to 7;
When r and s are each 2 or more, the substituents in parentheses are the same as or different from each other. The method of claim 9,
Formula 2 is an organic light emitting device represented by any one of the following compounds:

. The method of claim 7,
The organic material layer includes a light emitting layer,
The light emitting layer is an organic light emitting device that includes one or more kinds of the heterocyclic compound. The method of claim 7,
The organic material layer includes a light emitting layer,
The light emitting layer includes a host material,
The host material is an organic light emitting device comprising the heterocyclic compound. The method of claim 7,
The organic light emitting device further comprises one layer selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer. A heterocyclic compound represented by Formula 1 below; And a composition for forming an organic material layer comprising a compound represented by Formula 2 below:
[Formula 1]

In Formula 1,
L ₁ and L ₂ are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,
R ₁ is a cyano group; A substituted or unsubstituted silyl group; A methyl group substituted with an aryl group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted anthracenyl group; A substituted or unsubstituted phenanthrenyl group; A substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted pyrenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted phosphine oxide group; Or any one selected from the following structural formulas,

R ₂ is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted carbazole group,
When L ₁ is a direct bond, R ₁ is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted anthracenyl group; A substituted or unsubstituted phenanthrenyl group; A substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted pyrenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; A substituted or unsubstituted carbazole group; Or any one selected from the following structural formulas,

When L ₁ and L ₂ are each a direct bond and R ₁ is an unsubstituted phenyl group, R ₂ is A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuran group; A substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted carbazole group,
[Formula 2]

In Formula 2,
R _a , R _b , R ₂₁ and R ₂₂ are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,
r and s are each an integer from 1 to 7;
When r and s are each 2 or more, the substituents in parentheses are the same as or different from each other. The method of claim 14,
The weight ratio of the heterocyclic compound represented by Formula 1 and the compound represented by Formula 2 is 1:10 to 10:1.

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