KR20230039445A - Heterocyclic compound, organic light emitting device comprising the same and composition for organic layer of organic light emitting device - Google Patents

Abstract

The present specification relates to a heterocyclic compound represented by chemical formula 1, an organic light emitting device comprising the same, and a composition for an organic material layer of the organic light emitting device. The heterocyclic compound can be used as a light emitting material alone or in combination with a P-type host, and thus can be used as a host material or a dopant material of a light emitting layer.

Description

Heterocyclic compound, an organic light emitting device including the same, and a composition for an organic layer of an organic light emitting device

The present invention relates to a heterocyclic compound, an organic light emitting device including the same, and a composition for an organic material layer of an organic light emitting device.

An organic light emitting 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 functions 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.

US Patent No. 4,356,429

The present invention is to provide a heterocyclic compound, an organic light emitting device including the same, and a composition for an organic material layer of the organic light emitting device.

The present invention provides a heterocyclic compound represented by Formula 1 below:

[Formula 1]

In Formula 1,

R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; selected from the group consisting of, wherein at least one of R1 to R12 is deuterium,

X1, X2, and X3 are the same as or different from each other, and are each independently NAr1, O, S, or CR13R14, and at least one of X1, X2, and X3 is NAr1,

Ar1 is a group represented by Formula 1-1 below,

[Formula 1-1]

In Formula 1-1,

L1 and L2 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,

Ar2 and Ar3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; selected from the group consisting of

a and b are the same as or different from each other, and each independently represents an integer from 0 to 3;

R13 and R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; is selected from the group consisting of.

In addition, the present invention is a first electrode; a second electrode provided to face the first 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 the heterocyclic compound represented by Chemical Formula 1. do.

In addition, the present invention provides an organic light emitting device wherein the organic material layer further includes a heterocyclic compound represented by Chemical Formula 2:

[Formula 2]

In Formula 2,

R21 to R34 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; selected from the group consisting of

L3 and L4 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,

Ar11 and Ar12 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; and -SiR101R102R103; wherein R101, R102, and R103 are the same as or different from each other, and each independently 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,

m and n are the same as or different from each other, and are each independently an integer of 0 to 3.

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

The heterocyclic compound according to an embodiment may be used as a material for an organic material layer of an organic light emitting device. The compound may serve as a hole injection layer material, an electron blocking layer material, a hole transport layer material, an emission layer material, an electron transport layer material, a hole blocking layer material, and an electron injection layer 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.

Specifically, the heterocyclic compound may be used as a light emitting material alone or in combination with a P-type host, and may be used as a host material or a dopant material of a light emitting layer. When the compound represented by Chemical Formula 1 is used in the organic material layer, the driving voltage of the organic light emitting device can be lowered, the light emitting efficiency can be improved, and the lifetime characteristics can be improved.

More specifically, when the heterocyclic compound according to one embodiment is used as a light emitting layer, hole transport and electron transport characteristics are enhanced, and the band gap and triplet energy level (T1 level) value, improve hole transfer ability, increase molecular stability, lower driving voltage of organic light emitting device, improve light efficiency, and improve lifetime characteristics of organic light emitting device by improved thermal stability of compound can make it

1 to 3 are diagrams schematically illustrating a stacked structure of an organic light emitting device according to an exemplary embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

In the present specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is changed to 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 , When two or more substituents are substituted, two or more substituents may be the same as or different from each other.

In the present specification, “substituted or unsubstituted” means deuterium; halogen; cyano; C1 to C60 straight or branched chain 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 heterocycloalkyl; C6 to C60 monocyclic or polycyclic aryl; C2 to C60 monocyclic or polycyclic heteroaryl; -SiRR'R"; -P(=O)RR'; C1 to C20 alkylamine; C6 to C60 monocyclic or polycyclic arylamine; and C2 to C60 monocyclic or polycyclic heteroarylamine selected from the group consisting of It means substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with a substituent in which two or more substituents selected from the substituents exemplified above 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-dimethyl heptyl 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 alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It is not limited.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic group having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, 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, 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 S, O, 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, 5,11-dihydroindeno [1,2-b ] carbazolyl group and the like, but is not limited thereto.

In the present specification, the amine group is a monoalkylamine group; monoarylamine group; Monoheteroarylamine group; -NH ₂ ; Dialkylamine 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, the arylene group means that the aryl group has two bonding sites, that is, a divalent group. The description of the aryl group described above can be applied except that each is a divalent group. In addition, the heteroarylene group means a heteroaryl group having two bonding sites, that is, a divalent group. The above description of the heteroaryl group may be applied except that each is a divalent group.

As used herein, "adjacent" refers to a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located sterically closest to the substituent, or another substituent substituted on the atom on which the substituent is substituted. can For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as “adjacent” to each other.

In the present invention, "when no substituent is shown in the chemical formula or compound structure" means that a hydrogen atom is bonded to a carbon atom. However, since deuterium ( ² H, Deuterium) is an isotope of hydrogen, some hydrogen atoms may be deuterium.

In one embodiment of the present invention, "when a substituent is not indicated in the chemical formula or compound structure" may mean that all positions where the substituent can occur are hydrogen or deuterium. That is, deuterium is an isotope of hydrogen, and some hydrogen atoms may be an isotope of deuterium, and in this case, the content of deuterium may be 0% to 100%.

In one embodiment of the present invention, in the case of “when no substituent is indicated in the chemical formula or compound structure”, “the content of deuterium is 0%”, “the content of hydrogen is 100%”, “all substituents are hydrogen”, etc. When deuterium is not explicitly excluded, hydrogen and deuterium may be mixed and used in a compound.

In one embodiment of the present invention, deuterium is one of the isotopes of hydrogen and is an element having a deuteron composed of one proton and one neutron as an atomic nucleus, hydrogen- It can be expressed as 2, and the element symbol can also be written as D or ² H.

In one embodiment of the present invention, isotopes, which mean atoms having the same atomic number (Z) but different mass numbers (A), have the same number of protons, but have neutrons. It can also be interpreted as an element with a different number of neutrons.

In one embodiment of the present invention, the meaning of the content T% of a specific substituent is when the total number of substituents that a base compound can have is defined as T1, and the number of specific substituents among them is defined as T2. T2 It can be defined as /T1×100 = T%.

로 표시되는 페닐기에 있어서 중수소의 함량 20%라는 것은 페닐기가 가질 수 있는 치환기의 총 개수는 5(식 중 T1)개이고, 그 중 중수소의 개수가 1(식 중 T2)인 경우를 의미할 수 있다. 즉, 페닐기에 있어서 중수소의 함량 20%라는 것인 하기 구조식으로 표시될 수 있다.That is, in one example,

In the phenyl group represented by 20% of the deuterium content may mean that the total number of substituents that the phenyl group may have is 5 (T1 in the formula), and the number of deuterium is 1 (T2 in the formula) . That is, it can be represented by the following structural formula that the content of deuterium in the phenyl group is 20%.

In addition, in one embodiment of the present invention, in the case of “a phenyl group having a deuterium content of 0%”, it may mean a phenyl group that does not contain deuterium atoms, that is, has 5 hydrogen atoms.

In the present invention, the C6 to C60 aromatic hydrocarbon ring means a compound containing an aromatic ring composed of C6 to C60 carbons and hydrogen, for example, benzene, biphenyl, triphenyl, triphenylene, naphthalene, Anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene, etc. may be mentioned, but is not limited thereto, and an aromatic hydrocarbon ring compound known in the art as having the above number of carbon atoms may be used. All inclusive.

The present invention provides a heterocyclic compound represented by Formula 1 below:

[Formula 1]

In Formula 1,

R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; selected from the group consisting of, wherein at least one of R1 to R12 is deuterium,

X1, X2, and X3 are the same as or different from each other, and are each independently NAr1, O, S, or CR13R14, and at least one of X1, X2, and X3 is NAr1,

Ar1 is a group represented by Formula 1-1 below,

[Formula 1-1]

In Formula 1-1,

L1 and L2 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,

Ar2 and Ar3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; selected from the group consisting of

a and b are the same as or different from each other, and each independently represents an integer from 0 to 3;

R13 and R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; is selected from the group consisting of.

In one embodiment of the present invention, X1 is NAr1, X2 and X3 are the same as or different from each other, and each independently may be O, S or CR13R14.

In another embodiment of the present invention, X2 is NAr1, X1 and X3 are the same as or different from each other, and each independently may be O, S or CR13R14.

In another embodiment of the present invention, X3 is NAr1, X1 and X2 are the same as or different from each other, and each independently may be O, S or CR13R14.

In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 may be any one of the following Formulas 1-a to 1-f, but is not limited to these examples:

[Formula 1-a]

In Formula 1-a,

X3 is O, S or CR13R14;

R1 to R14 and Ar1 are as defined in Formula 1 and Formula 1-1 above,

[Formula 1-b]

In Formula 1-b,

X3 is O, S or CR13R14;

R1 to R14 and Ar1 are as defined in Formula 1 and Formula 1-1 above,

[Formula 1-c]

In Formula 1-c,

X3 is O, S or CR13R14;

R1 to R14 and Ar1 are as defined in Formula 1 and Formula 1-1 above,

[Formula 1-d]

In Formula 1-d,

X3 is O, S or CR13R14;

R1 to R14 and Ar1 are as defined in Formula 1 and Formula 1-1 above,

[Formula 1-e]

In Formula 1-e,

X3 is O, S or CR13R14;

R1 to R14 and Ar1 are as defined in Formula 1 and Formula 1-1 above,

[Formula 1-f]

In Formula 1-f,

X3 is O, S or CR13R14;

R1 to R14 and Ar1 are as defined in Formula 1 and Formula 1-1 above.

In one embodiment of the present invention, R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C30 alkyl group; A substituted or unsubstituted C2 to C30 alkenyl group; A substituted or unsubstituted C2 to C30 alkynyl group; A substituted or unsubstituted C1 to C30 alkoxy group; A substituted or unsubstituted C3 to C30 cycloalkyl group; A substituted or unsubstituted C2 to C30 heterocycloalkyl group; A substituted or unsubstituted C6 to C30 aryl group; and a substituted or unsubstituted C2 to C30 heteroaryl group; wherein at least one of R1 to R12 may be deuterium.

In another embodiment of the present invention, R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C20 alkyl group; A substituted or unsubstituted C2 to C20 alkenyl group; A substituted or unsubstituted C2 to C20 alkynyl group; A substituted or unsubstituted C1 to C20 alkoxy group; A substituted or unsubstituted C3 to C20 cycloalkyl group; A substituted or unsubstituted C2 to C20 heterocycloalkyl group; A substituted or unsubstituted C6 to C20 aryl group; and a substituted or unsubstituted C2 to C20 heteroaryl group; wherein at least one of R1 to R12 may be deuterium.

In another embodiment of the present invention, R1 to R12 are hydrogen or deuterium, and at least one of R1 to R12 may be deuterium.

In another embodiment of the present invention, R1 to R12 may be deuterium.

In one embodiment of the present invention, in Formula 1-1, L1 and L2 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted C6 to C30 arylene group; Or it may be a substituted or unsubstituted C2 to C30 heteroarylene group, a and b may be the same as or different from each other, and each independently may be an integer of 0 to 3.

In another embodiment of the present invention, in Formula 1-1, L1 and L2 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted C6 to C20 arylene group; Or it may be a substituted or unsubstituted C2 to C20 heteroarylene group, a and b may be the same as or different from each other, and each independently may be an integer of 0 to 3.

In another embodiment of the present invention, in Formula 1-1, L1 and L2 may be the same as or different from each other, and may each independently have the following structures, but are not limited to these examples:

,

,

.

,

,

.

In one embodiment of the present invention, in Formula 1-1, Ar2 and Ar3 are the same as or different from each other, and each independently represents a substituted or unsubstituted C6 to C60 aryl group; Or it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another embodiment of the present invention, in Formula 1-1, Ar2 and Ar3 are the same as or different from each other, and each independently represents a substituted or unsubstituted C6 to C30 aryl group; Or it may be a substituted or unsubstituted C2 to C30 heteroaryl group.

In another embodiment of the present invention, in Formula 1-1, Ar2 and Ar3 are the same as or different from each other, and each independently represents a substituted or unsubstituted C6 to C20 aryl group; Or it may be a substituted or unsubstituted C2 to C20 heteroaryl group.

In another embodiment of the present invention, in Formula 1-1, Ar2 and Ar3 are the same as or different from each other, and each independently may have the following structure, but is not limited to these examples:

,

,

,

,

,

,

,

.

,

,

,

,

,

,

,

.

In one embodiment of the present invention, R13 and R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C20 alkyl group; A substituted or unsubstituted C2 to C20 alkenyl group; A substituted or unsubstituted C2 to C20 alkynyl group; A substituted or unsubstituted C1 to C20 alkoxy group; A substituted or unsubstituted C3 to C20 cycloalkyl group; A substituted or unsubstituted C2 to C20 heterocycloalkyl group; A substituted or unsubstituted C6 to C20 aryl group; It may be selected from the group consisting of; and a substituted or unsubstituted C2 to C20 heteroaryl group.

In another embodiment of the present invention, R13 and R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C10 alkyl group; A substituted or unsubstituted C2 to C10 alkenyl group; A substituted or unsubstituted C2 to C10 alkynyl group; and a substituted or unsubstituted C1 to C10 alkoxy group.

In another embodiment of the present invention, R13 and R14 are the same as or different from each other, and each independently may be a methyl group, an ethyl group, a propyl group, and the like.

In one embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 1 may be 1% to 100%.

In another embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 1 may be 5% to 100%.

In another embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 1 may be 10% to 100%.

In another embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 1 may be 20% to 100%.

For example, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 1 is 0% or more, 1% or more, 5% or more, 10% or more, 15% or more, 20% or more Can be greater than, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, or 50% or more, and can be 100% or less, 95% or less, 90% or less, 85% or less, 80% or less, 75 % or less, 70% or less, 65% or less or 60% or less.

In one embodiment of the present invention, in the heterocyclic compound represented by Formula 1, the content of deuterium in R1 to R12 may be 1% to 100% based on the total number of hydrogen atoms and deuterium atoms.

In another embodiment of the present invention, in the heterocyclic compound represented by Formula 1, the content of deuterium in R1 to R12 may be 5% to 95% based on the total number of hydrogen atoms and deuterium atoms.

In another embodiment of the present invention, in the heterocyclic compound represented by Formula 1, the content of deuterium in R1 to R12 may be 10% to 90% based on the total number of hydrogen atoms and deuterium atoms.

For example, in the heterocyclic compound represented by Formula 1, the content of deuterium in R1 to R12 is 0% or more, 1% or more, 5% or more, 10% or more, 15% or more based on the total number of hydrogen atoms and deuterium atoms. % or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, or 50% or more, 100% or less, 95% or less, 90% or less, 85% or less, It may be 80% or less, 75% or less, 70% or less, 65% or less or 60% or less.

In one embodiment of the present invention, in Formula 1-1, Ar2 and Ar3 may be a deuterium-substituted C6 to C30 aryl group or a deuterium-substituted C2 to C30 heteroaryl group, in which case, a hydrogen atom and a deuterium content of 1% to 100% based on the total number of deuterium atoms.

In another embodiment of the present invention, in Formula 1-1, Ar2 and Ar3 may be a deuterium-substituted C6 to C30 aryl group or a deuterium-substituted C2 to C30 heteroaryl group, in which case, a hydrogen atom and a deuterium content of 5% to 95% based on the total number of deuterium atoms.

In another embodiment of the present invention, in Formula 1-1, Ar2 and Ar3 may be a deuterium-substituted C6 to C30 aryl group or a deuterium-substituted C2 to C30 heteroaryl group, in which case, a hydrogen atom and a deuterium content of 10% to 90% based on the total number of deuterium atoms.

For example, in Formula 1-1, when Ar2 and Ar3 are C6 to C30 aryl groups substituted with deuterium or C2 to C30 heteroaryl groups substituted with deuterium, the content of deuterium in the substituent is hydrogen atoms and deuterium 0% or more, 1% or more, 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, based on the total number of atoms; Or it may be 50% or more, 100% or less, 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, or 60% or less.

In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 may be any one selected from the group consisting of the following compounds:

.

.

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, a substituent mainly used in hole injection layer materials, hole transport layer materials, electron blocking layer materials, light emitting layer materials, electron transport layer materials, hole blocking layer materials, and electron injection layer materials used in the manufacture of organic light emitting devices is introduced into the core structure. By doing so, it is possible to synthesize a material that satisfies the conditions required by each organic layer.

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 addition, the present invention is a first electrode; a second electrode provided to face the first 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 a heterocyclic compound represented by Chemical Formula 1.

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

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

In one embodiment of the present invention, 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.

In another embodiment of the present invention, 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.

In another embodiment of the present invention, 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.

Details of the heterocyclic compound represented by Formula 1 are the same as described above.

In one embodiment of the present invention, 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 an emission layer of the red organic light emitting device.

In another embodiment of the present invention, 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 a light emitting layer of the green organic light emitting device.

In another embodiment of the present invention, 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 a light emitting layer of the blue organic light emitting device.

Details of the heterocyclic compound represented by Formula 1 are the same as described above.

The organic light emitting diode of the present invention may be manufactured by conventional organic light emitting diode manufacturing methods and materials, except for forming one or more organic material layers using the aforementioned heterocyclic compound.

The heterocyclic compound may form 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 invention 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 injection layer, an electron transport layer, a battery blocking layer, a hole blocking layer, and the like as organic material layers. However, the structure of the organic light emitting diode is not limited thereto and may include a smaller number of organic material layers.

In one embodiment of the present invention, the organic light emitting device includes one layer 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, a battery blocking layer, and a hole blocking layer. It may further include, and the one or more layers may include the heterocyclic compound.

In one embodiment of the present invention, the organic light emitting device may include one or more organic material layers, the organic material layer may include a light emitting layer, and the light emitting layer may include a heterocyclic compound represented by Chemical Formula 1. there is.

In another embodiment of the present invention, the organic material layer may include a light emitting layer, the light emitting layer may include a host material, and the host material may include the heterocyclic compound.

In one embodiment of the present invention, the organic light emitting device may include a heterocyclic compound represented by Formula 1, and may further include a heterocyclic compound represented by Formula 2 below:

[Formula 2]

In Formula 2,

R21 to R34 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; selected from the group consisting of

L3 and L4 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,

Ar11 and Ar12 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; and -SiR101R102R103; wherein R101, R102, and R103 are the same as or different from each other, and each independently 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,

m and n are the same as or different from each other, and are each independently an integer of 0 to 3.

In another embodiment of the present invention, in Formula 2, R21 to R34 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C30 alkyl group; A substituted or unsubstituted C2 to C30 alkenyl group; A substituted or unsubstituted C2 to C30 alkynyl group; It may be selected from the group consisting of; and a substituted or unsubstituted C1 to C30 alkoxy group.

In another embodiment of the present invention, in Formula 2, R21 to R34 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C10 alkyl group; A substituted or unsubstituted C2 to C10 alkenyl group; A substituted or unsubstituted C2 to C10 alkynyl group; It may be selected from the group consisting of; and a substituted or unsubstituted C1 to C30 alkoxy group.

In another embodiment of the present invention, in Formula 2, R21 to R34 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; It may be selected from the group consisting of a halogen and a cyano group.

In another embodiment of the present invention, in Formula 2, R21 to R34 are the same as or different from each other, and each independently may be hydrogen or deuterium.

In another embodiment of the present invention, in Formula 2, L3 and L4 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted C6 to C30 arylene group; Or it may be a substituted or unsubstituted C2 to C30 heteroarylene group, m and n are the same as or different from each other, and each independently may be an integer of 0 to 3.

In another embodiment of the present invention, in Formula 2, L3 and L4 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted C6 to C20 arylene group; Or it may be a substituted or unsubstituted C2 to C20 heteroarylene group, m and n are the same as or different from each other, and each independently may be an integer of 0 to 3.

In another embodiment of the present invention, in Formula 2, Ar11 and Ar12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C30 alkyl group; A substituted or unsubstituted C2 to C30 alkenyl group; A substituted or unsubstituted C2 to C30 alkynyl group; A substituted or unsubstituted C1 to C30 alkoxy group; A substituted or unsubstituted C3 to C30 cycloalkyl group; A substituted or unsubstituted C2 to C30 heterocycloalkyl group; A substituted or unsubstituted C6 to C30 aryl group; A substituted or unsubstituted C2 to C30 heteroaryl group; -P(=O)R101R102; and -SiR101R102R103; wherein R101, R102, and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C30 alkyl group; A substituted or unsubstituted C6 to C30 aryl group; Or it may be a substituted or unsubstituted C2 to C30 heteroaryl group.

In another embodiment of the present invention, in Formula 2, Ar11 and Ar12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C6 to C20 aryl group; A substituted or unsubstituted C2 to C20 heteroaryl group; -P(=0)R101R102; and -SiR101R102R103; wherein R101, R102, and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C10 aryl group; Or it may be a substituted or unsubstituted C2 to C10 heteroaryl group.

In one embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 2 may be 0% to 100%.

In another embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 2 may be 10% to 100%.

In another embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 2 may be 20% to 90%.

In another embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 2 may be 30% to 80%.

For example, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 2 is 0% or more, 10% or more, 20% or more, 30% or more, 40% or more, or 50% It may be more than 100%, 90% or less, 80% or less, 70% or less, or 60% or less.

In one embodiment of the present invention, the heterocyclic compound represented by Formula 2 may be any one selected from the group consisting of the following compounds:

.

.

In manufacturing the organic light emitting device of the present invention, the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 may be included.

In manufacturing the organic light emitting device of the present invention, when the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 are mixed and included, excellent driving voltage, luminous efficiency and lifetime of the organic light emitting device are obtained. can be improved This can be expected to occur when the two heterocyclic compounds are mixed and included at the same time.

The exciplex phenomenon is a phenomenon in which an energy difference between a HOMO energy level of a donor (p-host) and a LUMO energy level of an acceptor (n-host) is released by electron exchange between two molecules. When an exciplex between two molecules occurs, reverse intersystem crossing (RISC) occurs, and as a result, the internal quantum efficiency of fluorescence can be increased to 100%. When a donor (p-host) with good hole transport ability and an acceptor (n-host) with good electron transport ability 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. Since it is injected, the driving voltage can be lowered, thereby helping to improve the lifespan. That is, when the compound represented by Chemical Formula 1 is used as the acceptor and the compound represented by Chemical Formula 2 is used as the donor, excellent characteristics of the organic light emitting device are exhibited.

In one embodiment of the present invention, when the organic light emitting device includes a mixture of the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2, at least one of the heterocyclic compounds is deuterium The content of may be greater than 0% and less than or equal to 100%.

In another embodiment of the present invention, when the organic light emitting device includes a mixture of the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2, at least one of the heterocyclic compounds is deuterium The content of may be 10% to 100%.

In another embodiment of the present invention, when the organic light emitting device includes a mixture of the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2, at least one of the heterocyclic compounds is deuterium The content of may be 15% to 95%.

In another embodiment of the present invention, when the organic light emitting device includes a mixture of the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2, at least one of the heterocyclic compounds is deuterium The content of may be 20% to 90%.

For example, when the organic light-emitting device includes a mixture of the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2, at least one of the heterocyclic compounds has a deuterium content of 0%. 1% or more, 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, or 50% or more, and 100 % or less, 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, or 60% or less.

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

Details of the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 below are the same as described above.

In one embodiment of the present invention, the weight ratio of the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 in the composition for the organic layer of the organic light emitting device is 1:10 to 10:1, 1:8 to 8:1, 1:6 to 6:1, 1:4 to 4:1, 1:3 to 3:1, or 1:2 to 2:1, but not limited thereto it is not going to be

The composition for the organic material layer of the organic light emitting device can be used when forming the organic material layer of the organic light emitting device, and can be more preferably used when forming the host of the light emitting layer.

In one embodiment of the present invention, the organic material layer includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2, and may be used together with a phosphorescent dopant.

As the phosphorescent dopant material, those known in the art may be used. For example, phosphorescent dopant materials represented by LL'MX', LL'L"M, LMX'X", L ₂ MX' and L ₃ M may be used, but the scope of the present invention is not limited by these examples. .

The M may be iridium, platinum, osmium, or the like.

L is an anionic bidentate ligand coordinated to M by sp2 carbon and a hetero atom, and X may function to trap electrons or holes. Non-limiting examples of L, L' and L" include 2-(1-naphthyl)benzoxazole, (2-phenylbenzoxazole), (2-phenylbenzothiazole), (2-phenylbenzothiazole). ), (7,8-benzoquinoline), (thiophenepyrizine), phenylpyridine, benzothiophenepyridine, 3-methoxy-2-phenylpyridine, thiophenepyrizine, tolylpyridine, etc. X' and X″ include, but are not limited to, acetylacetonate (acac), hexafluoroacetylacetonate, salicylidene, picolinate, 8-hydroxyquinolinate, and the like.

Specific examples of the phosphorescent dopant are shown below, but are not limited to these examples:

In one embodiment of the present invention, the organic material layer includes the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2, and may be used together with an iridium-based dopant.

In one embodiment of the present invention, Ir(ppy) ₃ may be used as a green phosphorescent dopant as the iridium-based dopant.

In one embodiment of the present invention, the content of the dopant may have a content of 1% to 15%, preferably 2% to 10%, more preferably 3% to 7% based on the total weight of the light emitting layer. .

In the organic light emitting device according to an embodiment of the present invention, the organic material layer may include an electron injection layer or an electron transport layer, and the electron injection layer or electron transport layer may include a heterocyclic compound represented by Chemical Formula 1.

In the organic light emitting device according to another embodiment of the present invention, the organic material layer may include an electron blocking layer or a hole blocking layer, and the electron blocking layer or hole blocking layer may include a heterocyclic compound represented by Chemical Formula 1. .

In the organic light emitting device according to another embodiment of the present invention, the organic material layer may include an electron transport layer, a light emitting layer, or a hole blocking layer, and the electron transport layer, the light emitting layer, or the hole blocking layer may include a heterocyclic compound represented by Chemical Formula 1. can

In the organic light emitting device according to another embodiment of the present invention, the organic material layer may include a light emitting layer, and the light emitting layer may include a heterocyclic compound represented by Chemical Formula 1.

In the organic light emitting device according to another embodiment of the present invention, the organic material layer includes a light emitting layer, the light emitting layer includes a host material, and the host material may include a heterocyclic compound represented by Chemical Formula 1 above.

The organic light emitting device according to an embodiment of the present invention may further include one layer 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 blocking layer, and a hole blocking layer. .

1 to 3 illustrate the stacking order of the electrode and the organic material layer of the organic light emitting device according to an embodiment of the present invention. 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.

In one embodiment of the present invention, 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 an organic material layer according to an embodiment of the present invention. It provides a method for manufacturing an organic light emitting device comprising the step of doing.

In one embodiment of the present invention, the forming of the organic material layer is performed by pre-mixing the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2, and performing a thermal vacuum deposition method. It may be formed using.

The pre-mixing means that the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 are first mixed and mixed in one source before depositing the heterocyclic compound represented by Chemical Formula 2 on the organic layer.

The premixed material may be referred to as a composition for an organic layer according to an exemplary embodiment of the present application.

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

The organic material layer including both the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 may further include other materials as needed.

In the organic light emitting device according to an embodiment of the present invention, materials other than the heterocyclic compound represented by Formula 1 or the heterocyclic compound represented by Formula 2 are exemplified below, but these are for illustrative purposes only. It is not intended to limit the scope of, and may be replaced with materials known in the art.

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 layer material, a known hole injection layer material may be used. For example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429, or a phthalocyanine compound disclosed in Advanced Material, 6, p.677 (1994). Starburst amine derivatives described, 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) or the like can be used.

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

Materials for the electron transport layer 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 layer 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 a material for the light emitting layer, 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 may be used as a material for the light emitting layer, but it may also be used as a phosphorescent material. As the material for the light emitting layer, a single material that emits light by combining holes and electrons injected from the anode and the cathode may be used, but materials in which a host material and a dopant material are involved in light emission may also be used.

In the case of mixing and using hosts of the light emitting layer material, 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 embodiment of the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

The heterocyclic compound according to an embodiment of the present invention 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.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but the following examples are provided to more easily understand the present invention, but the present invention is not limited thereto.

<Production Example>

Preparation Example 1: Preparation of compound 1-1

1) Preparation of compound 1-1-6

2,3-difluoro-1,4-diiodobenzene (2,3-difluoro-1,4-diiodobenzene) (22.8g, 62.3mM), (2-fluorophenyl)boric acid ((2-fluorophenyl) boronic acid) (7.3g, 51.9mM), tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) (3.0g, 2.6mM) and potassium carbonate (K ₂ CO ₃ ) (14.3g , 103.8mM) was dissolved in 1,4-dioxane (1,4-dioxane) (250mL) and water (H ₂ O) (50mL), and then refluxed for 12 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 13.9g of the target compound 1-1-6 (yield: 80%).

2) Preparation of compound 1-1-5

Compound 1-1-6 (17.3g, 51.9mM), (3-bromo-2-fluorophenyl)boronic acid (13.6g, 62.3mM), tetrakis (triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) (3.0 g, 2.6 mM) and potassium carbonate (K ₂ CO ₃ ) (14.3 g, 103.8 mM) were mixed with 1,4-dioxane (1 ,4-dioxane) (250mL) and water (H ₂ O) (50mL) were added and dissolved, and then refluxed for 12 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 16.8 g of the target compound 1-1-5 (yield: 85%).

3) Preparation of compound 1-1-4

Compound 1-1-5 (16.8g, 44.1mM) and potassium tert-butoxide ( t -BuOK) (29.7g, 264.6mM) were mixed with hexamethylphosphoramide (HMPA) (160mL) After melting it in, it was stirred at 120℃ in a microwave reactor. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 13.8 g of the target compound 1-1-4 (yield: 93%).

4) Preparation of compound 1-1-3

Compound 1-1-4 (17.5g, 51.9mM), 2-chloroaniline (7.9g, 62.3mM), Palladium (II) acetate, Pd(OAc) ₂ (0.58g, 2.6 mM), XantPhos (3 g, 5.2 mM) and sodium tert-butoxide (t-BuONa) (10.0 g, 103.8 mM) were mixed with 1,4-dioxane (1,4- dioxane) (200mL) and dissolved, and then refluxed for 12 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 15.9 g of the target compound 1-1-3 (yield: 80%).

5) Preparation of compound 1-1-2

Compound 1-1-3 (15.9g, 41.5mM), Palladium (II) acetate (Pd(OAc) ₂ ) (0.47g, 2.1mM), 50% tri-tert-butylphosphine (tri-tert -butylphosphine, P( t -Bu) ₃ ) (2mL, 4.2mM) and 1,8-diazabicyclo[5,4,0]undec-7-ene 7-ene, DBU) (9.3mL, 62.3mM) was dissolved in xylene (400mL) and refluxed for 4 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 12.5 g of the target compound 1-1-2 (yield: 87%).

6) Preparation of compound 1-1-1

Compound 1-1-2 (12.5g, 36.2mM) and triflic acid (CF ₃ CO _3H ) (80.1mL, 905.0mM) were dissolved in benzene-d6 (150mL), It was refluxed at 40 °C. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 10.1 g of the target compound 1-1-1 (yield: 78%).

7) Preparation of compound 1-1

Compound 1-1-1 (10.1 g, 28.2 mM), 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5- triazine) (9.1g, 33.9mM), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ ) (1.3g, 1.4mM), XPhos (1.3g, 2.8mM) and sodium tert- After dissolving butoxide (sodium tert-butoxide, t -BuONa) (5.4g, 56.4mM) in xylene (200mL), it was refluxed for 12 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 12.2 g of the target compound 1-1 (yield: 73%).

In Preparation Example 1, instead of 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine), Table 1 Using Intermediate A, the target compounds in Table 1 were synthesized in the same manner as in Preparation Example 1.

number Intermediate A target compound number Intermediate A target compound 1-3

1-4

1-26

1-32

1-56

Preparation Example 2: Preparation of compound 1-61

1) Preparation of compound 1-61-5

4,6-dibromodibenzo[b,d]furan (4,6-dibromodibenzo[b,d]furan) (5.2g, 15.8mM), 2-aminobenzenethiol (2.0g, 15.8mM), Copper(I) iodide (CuI) (3.0g, 15.8mM), trans-1,2-diaminocyclohexane (1.9mL, 15.8mM) and After dissolving tri-potassium phosphate (K ₃ PO ₄ ) (3.3g, 31.6mM) in 1,4-dioxane (100mL), the mixture was refluxed for 24 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 5.0 g of the target compound 1-61-5 (yield: 85%).

2) Preparation of compound 1-61-4

After dissolving compound 1-61-5 (5.2g, 15.8mM) and tert-Butyl nitrite ( t -BuONO) (2.4g, 23.7mM) in acetonitrile (MeCN) (100mL), , After stirring at 0 ° C. for 1 hour, copper (Cu) (2.0 g, 31.6 mM) was added at 0 ° C., and then stirred at 80 ° C. for 3 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then 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 2.9 g of the target compound 1-61-4 (yield: 52%).

3) Preparation of compound 1-61

Compounds 1-1-3, 1-1-2, 1-1-1 and 1-1 were prepared in the same manner as in Preparation Example 1. 1 and 1-61 were prepared, and in Preparation Example 2, instead of 4,6-dibromodibenzo[b,d]furan, Intermediate A of Table 2 below Using, 2-chloro-4,6-diphenyl-1,3,5-triazine instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, Intermediate B of Table 2 below Using, the target compounds of Table 2 were synthesized in the same manner as in Preparation Example 2.

number Intermediate A Intermediate B target compound 1-64

1-114

1-241

1-243

1-244

1-264

1-265

1-272

1-294

1-295

1-296

Preparation Example 3: Preparation of compound 1-121

1) Preparation of compound 1-121-4

12,12-dimethyl-12H-fluoreno[1,2-b]benzofuran (12,12-dimethyl-12H-fluoreno[1,2-b]benzofuran) (11.8g, 41.5mM) was mixed with tetrahydrofuran ( After dissolving in tetrahydrofuran (THF) (260mL), purging with nitrogen at -78 ° C, 2.5M n-Butyllithium, n-BuLi (20.0mL, 49.8mM) was slowly added and stirred to room temperature. After that, iodine (15.8g, 62.3mM) was added and stirred for 1 hour. After the reaction was completed, distilled water and dichloromethane (DCM) were added and extracted. Thereafter, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 11.7 g of the target compound 1-121-4 (yield: 69%).

2) Preparation of compound 1-121

Compounds 1-121-3, 1-121-2, 1-121- 1 and 1-121 were prepared, and in Preparation Example 3, 12,12-dimethyl-12H-fluoreno[1,2-b]benzofuran (12,12-dimethyl-12H-fluoreno[1,2-b] benzofuran), Intermediate A in Table 3 below was used, and 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5- triazine), the target compounds in Table 3 were synthesized in the same manner as in Preparation Example 3 using Intermediate B in Table 3 below.

number Intermediate A Intermediate B target compound 1-123

1-156

1-175

1-301

1-304

1-356

Preparation Example 4: Preparation of compound 1-181

1) Preparation of Compound 1-181-3

Compound 1-181-4 (8.2g, 28.2mM), 2-chloroaniline (4.3g, 33.9mM) and potassium tert-butoxide ( t -BuOK) (6.3g, 56.4mM) was dissolved in dimethyl sulfoxide (DMSO) (200mL) and then refluxed. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 8.2 g of the target compound 1-181-3 (yield: 73%).

2) Preparation of compound 1-181

Compound 1-181-5, 1-181- 4, 1-181-2, 1-181-1 and 1-181 were prepared, and in Preparation Example 4, 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro- 4,6-diphenyl-1,3,5-triazine), the target compound in Table 4 was synthesized in the same manner as in Preparation Example 4 using Intermediate A in Table 4 below.

number Intermediate A target compound number Intermediate A target compound 1-183

1-184

1-238

Preparation Example 5: Preparation of compound 1-361

1) Preparation of compound 1-361-3

4-bromo-3-chlorodibenzo[b,d]furan (14.6g, 51.9mM), dibenzo[b,d]furan-4-amine (dibenzo[b,d]furan-4-amine) (11.4g, 62.3mM), Palladium (II) acetate, Pd(OAc) ₂ (0.58g, 2.6mM), XantPhos ( 3g, 5.2mM) and sodium tert-butoxide ( t -BuONa) (10.0g, 103.8mM) were dissolved in 1,4-dioxane (200mL), Refluxed for 12 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 16.5 g of the target compound 1-361-3 (yield: 83%).

2) Preparation of compound 1-361

It was prepared in the same manner as in the preparation of compounds 1-1-2, 1-1-1 and 1-1 in Preparation Example 21, and 4-bromo-3chlorodibenzo[b,d]furan in Preparation Example 5. Instead of (4-bromo-3-chlorodibenzo[b,d]furan), intermediate A of Table 5 was used, and dibenzo[b,d]furan-4-amine (dibenzo[b,d]furan-4- amine), intermediate B in Table 5 is used, and 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5- triazine), the target compounds in Table 5 were synthesized in the same manner as in Preparation Example 5 using Intermediate C in Table 5 below.

number Intermediate A Intermediate B Intermediate C target compound 1-372

1-379

1-381

1-383

1-398

1-401

1-408

1-416

1-421

1-423

1-436

1-441

1-442

1-455

1-461

1-477

Preparation Example 6: Preparation of compound 2-3

1) Preparation of compound 2-3

3-bromo-1,1'-biphenyl (3-bromo-1,1'-biphenyl) (3.7g, 15.8mM), 9-phenyl-9H,9'H-3,3'-bicarbazole (9-phenyl-9H,9'H-3,3'-bicarbazole) (6.5g, 15.8mM), Copper(I) iodide (CuI) (3.0g, 15.8mM), trans-1,2 -Diaminocyclohexane (trans-1,2-diaminocyclohexane) (1.9mL, 15.8mM) and tri-potassium phosphate (K ₃ PO ₄ ) (3.3g, 31.6mM) were mixed with 1,4-dioxane After dissolving in (1,4-dioxane) (100mL), the mixture was refluxed for 24 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then 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 7.5 g of the target compound 2-3 (yield: 85%).

In Preparation Example 6, Intermediate A of Table 6 was used instead of 3-bromo-1,1'-biphenyl, and 9-phenyl-9H,9' Instead of H-3,3'-bicarbazole (9-phenyl-9H,9'H-3,3'-bicarbazole), using Intermediate B of Table 6 below, in the same manner as in Preparation Example 6, The target compounds in Table 6 were synthesized.

compound
number Intermediate A Intermediate B target compound 2-4

2-7

2-9

2-31

2-32

2-42

Preparation Example 7: Preparation of compound 2-73

1) Preparation of compound 2-73-2

2-Bromodibenzo[b,d]thiophene (4.2g, 15.8mM), 9-phenyl-9H,9'H-3,3'-bicarbazole ( 9-phenyl-9H,9'H-3,3'-bicarbazole) (6.5g, 15.8mM), Copper(I) iodide (CuI) (3.0g, 15.8mM), trans-1,2- Diaminocyclohexane (trans-1,2-diaminocyclohexane) (1.9mL, 15.8mM) and tri-potassium phosphate (K ₃ PO ₄ ) (3.3g, 31.6mM) were mixed with 1,4-dioxane ( After dissolving in 1,4-dioxane) (100mL), it was refluxed for 24 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then 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 7.9g of the target compound 2-73-2 (yield: 85%).

2) Preparation of Compound 2-73-1

Compound 2-73-2 (8.4g, 14.3mmol) was dissolved in tetrahydrofuran (THF) (100mL), nitrogen-substituted at -78°C, and 2.5M n-butyllithium (n-Butyllithium, n -BuLi) (7.4mL, 18.6mmol) was added slowly and stirred at room temperature for 1 hour. Trimethyl borate (B(OMe) ₃ ) (4.8mL, 42.9mmol) was slowly added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:MeOH=100:3) and recrystallized with DCM to obtain 3.9 g of the target compound 2-73-1 (yield: 70%).

3) Preparation of compound 2-73

Compound 2-73-1 (6.7g, 10.5mM), iodobenzene (2.1g, 10.5mM), tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) (606mg, 0.52mM ), potassium carbonate (K ₂ CO ₃ ) (2.9g, 21.0mM) were dissolved in toluene (100mL), ethanol (EtOH) (20mL) and water (H ₂ O) (20mL) and then dissolved. , and refluxed for 12 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexand=1:3) and recrystallized with methanol to obtain 4.9 g of the target compound 2-73 (yield: 70%).

Preparation Example 8: Preparation of compound 3-2

1) Preparation of compound 3-2-1

9H,9'H-3,3'-bicarbazole (10g, 30.0mM), 4-bromo-1,1'-biphenyl-2, 2',3,3',4',5,5',6,6'-D ₉ (4-bromo-1,1'-biphenyl-2,2',3,3',4',5, 5',6,6'- _D9 ) [A] (7.26g, 30mM), Copper(I) iodide (Cul) (0.57g, 3.0mM), trans-1,2-diaminocyclohexane (trans-1,2-diaminocyclohexane) (0.34 g, 3.0 mM) and tri-potassium phosphate (K ₃ PO ₄ ) (12.7 g, 60.0 mM) were mixed with 1,4-dioxane (1,4- dioxane) (100 mL) and dissolved, and then refluxed at 125°C for 8 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Thereafter, water was removed from the organic layer with magnesium sulfate (MgSO ₄ ), and then 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 13.9 g of the target compound 3-2-1 (yield: 94%).

2) Preparation of compound 3-2

Compound 3-2-1 (13.9 g, 28.0 mM), 4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'- D ₉ (4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D ₉ ) [A'] (6.8 g, 28.0 mM ), Copper(I) iodide (Cul) (0.53g, 2.8mM), trans-1,2-diaminocyclohexane (0.32g, 2.8mM) and triphosphate Potassium (tri-potassium phosphate, K ₃ PO ₄ ) (11.9g, 56.0mM) was dissolved in 1,4-dioxane (140mL), and then refluxed at 125°C for 8 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Thereafter, water was removed from the organic layer with magnesium sulfate (MgSO ₄ ), and then 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 16.1 g of the target compound 3-2 (yield: 88%).

When Compound A and Compound A' are the same, the target compound can be directly synthesized by adding 2 equivalents of Compound A in Preparation Example 8. That is, when compound A and compound A' are the same, preparation of compound 3-2-1 may be omitted.

In Preparation Example 8, 4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D ₉ (4-bromo-1 ,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D ₉ ) Instead of [A], intermediate A of Table 7 was used, and 4-broth Mo-1,1'-biphenyl-2,2',3,3',4',5,5',6,6'-D ₉ (4-bromo-1,1'-biphenyl-2,2 ',3,3',4',5,5',6,6'- _D9 ) Instead of [A'], using Intermediate A' in Table 7 below, in the same manner as in Preparation Example 8. The target compounds in Table 7 were synthesized.

compound number Intermediate A Intermediate A' target compound 3-3

3-5

3-6

3-8

3-19

3-22

Preparation Example 9: Preparation of compound 3-26

1) Preparation of compound 3-26-2

9H,9'H-3,3'-bicarbazole (12.0g, 36.2mM) and triflic acid (CF ₃ CO ₃ H) (80.1 mL, 905.0 mM) was dissolved in benzene-d6 (100 mL) and then refluxed at 40°C. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 8.9g of the target compound 3-26-2 (yield: 71%).

2) Preparation of compound 3-26-1

Compound 3-26-2 (5.5 g, 15.8 mM), 4-bromo-1,1'-biphenyl [B] (3.7 g, 15.8 mM), iodide Copper (I) iodide, CuI (3.0 g, 15.8 mM), trans-1,2-diaminocyclohexane (1.9 mL, 15.8 mM) and potassium triphosphate (tri After dissolving -potassium phosphate, K ₃ PO ₄ ) (3.3g, 31.6mM) in 1,4-dioxane (100mL), the mixture was refluxed for 24 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then 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 6.5 g of the target compound 3-26-1 (yield: 83%).

2) Preparation of compound 3-26

Compound 3-26-1 (14.0 g, 28.0 mM), 4-bromo-1,1'-biphenyl [B'] (6.8 g, 28.0 mM), Copper(I) iodide (CuI) (0.53g, 2.8mM), trans-1,2-diaminocyclohexane (0.32g, 2.8mM) and potassium triphosphate ( After dissolving tri-potassium phosphate, K ₃ PO ₄ ) (11.9g, 56.0mM) in 1,4-dioxane (140mL), the mixture was refluxed at 125°C for 8 hours. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Thereafter, water was removed from the organic layer with magnesium sulfate (MgSO ₄ ), and then 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 15.8g of the target compound 3-26 (yield: 87%).

When Compound B and Compound B' are the same, the target compound can be directly synthesized by adding 2 equivalents of Compound B in Preparation Example 9. That is, when Compound B and Compound B' are the same, the preparation of Compound 3-26-1 may be omitted.

In Preparation Example 9, instead of 4-bromo-1,1'-biphenyl (4-bromo-1,1'-biphenyl) [B], intermediate B in Table 8 was used, and 4-bromo- 1,1'-biphenyl (4-bromo-1,1'-biphenyl) [B'], using Intermediate B' in Table 8 below, in the same manner as in Preparation Example 9 for the purpose of Table 8 compounds were synthesized.

compound number Intermediate B Intermediate B' target compound 3-26

3-27

3-29

3-32

3-33

3-36

3-39

3-44

Preparation Example 10: Preparation of Compound 3-50

1) Preparation of compound 3-50-1

9-([1,1'-biphenyl]-4-yl)-9H,9'H-3,3'-bicarbazole (9-([1,1'-biphenyl]-4-yl)- 9H,9'H-3,3'-bicarbazole (13.6g, 28.0mM), 4-bromo-1,1'-biphenyl (6.8g, 28.0 mM), copper (I) iodide (CuI) (0.53g, 2.8mM), trans-1,2-diaminocyclohexane (0.32g, 2.8mM) and After dissolving tri-potassium phosphate (K ₃ PO ₄ ) (11.9g, 56.0mM) in 1,4-dioxane (140mL), it was refluxed at 125°C for 8 hours. . After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Thereafter, water was removed from the organic layer with magnesium sulfate (MgSO ₄ ), and then 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 15.9 g of the target compound 3-50-1 (yield: 89%).

2) Preparation of compound 3-50

Compound 3-50-1 (23.0g, 36.2mM) and triflic acid (CF ₃ CO ₃ H) (80.1mL, 905.0mM) were dissolved in benzene-d6 (100mL), It was refluxed at 40°C. After the reaction was completed, distilled water and dichloromethane (DCM) were added at room temperature and extracted. Then, the organic layer was dried with magnesium sulfate (MgSO ₄ ), and then the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hexane=1:3) to obtain 16.9g of the target compound 3-50 (yield: 70%).

In Preparation Example 10, 9-([1,1'-biphenyl]-4-yl)-9H,9'H-3,3'-bicarbazole (9-([1,1'-biphenyl] -4-yl) -9H,9'H-3,3'-bicarbazole), using Intermediate C in Table 9 below, and 4-bromo-1,1'-biphenyl (4-bromo-1, 1'-biphenyl), the target compound in Table 9 was synthesized in the same manner as in Preparation Example 10 using Intermediate C' in Table 9 below.

compound number Intermediate C Intermediate C' target compound 3-50

3-51

3-53

3-56

3-57

3-58

3-60

3-62

3-63

3-67

The remaining compounds other than the compounds described in Preparation Examples 1 to 10 and Tables 1 to 9 were also prepared in the same manner as described in the above Preparation Examples, and the synthesis results are shown in Tables 10 and 11 below. Table 10 below is a measurement value of ¹ H NMR (CDCl ₃ , 200 Mz), and Table 11 below is a measurement value of FD-mass spectrometer (FD-MS: Field desorption mass spectrometry).

compound
number ^One H NMR (CDCl ₃ , 200 Mz) 1-1 δ = 8.36 (4H, d), 7.50 (6H, m) 1-3 δ= 8.38~8.36 (3H, m), 7.94 (1H, s), 7.75~7.73 (3H, m), 7.61 (1H, d), 7.50~7.41 (6H, m) 1-4 δ = 8.36 (2H, d), 7.96 (2H, d), 7.75 (2H, m), 7.50 to 7.41 (6H, m), 7.25 (2H, d) 1-26 δ = 7.96 (4H, d), 7.75 (4H, m), 7.49~7.41 (6H, m), 7.25 (4H, d) 1-32 δ= 8.36 (2H, d), 8.03 to 7.98 (2H, m), 7.82 to 7.76 (2H, m), 7.54 to 7.50 (4H, m), 7.39 to 7.31 (2H, m) 1-56 δ = deuterium content 100%, no peak 1-61 δ = 8.36 (4H, d), 7.50 (6H, m) 1-64 δ = 8.36 (2H, d), 7.96 (2H, d), 7.75 (2H, m), 7.50~7.41 (6H, m), 7.25 (2H, d) 1-114 δ = deuterium content 100%, no peak 1-121 δ = 8.36 (4H, d), 7.50 (6H, m), 1.69 (6H, s) 1-123 δ= 8.38~8.36 (3H, m), 7.94 (1H, s), 7.75~7.73 (3H, m), 7.61 (1H, d), 7.50~7.41(6H, m), 1.69 (6H, s) 1-156 δ= 8.45 (1H, d), 8.38 (2H, d), 8.24~8.20 (2H, m), 7.94 (1H, d), 7.56~7.49 (5H, m), 1.69 (6H, s) 1-175 δ = deuterium content 100%, no peak 1-181 δ = 8.36 (4H, d), 7.50 (6H, m) 1-183 δ= 8.38~8.36 (3H, m), 7.94 (1H, s), 7.75~7.73 (3H, m), 7.61 (1H, d), 7.50~7.41 (6H, m) 1-184 δ = 8.36 (2H, d), 7.96 (2H, d), 7.75 (2H, m), 7.50~7.41 (6H, m), 7.25 (2H, d) 1-238 δ = deuterium content 100%, no peak 1-241 δ = 8.36 (4H, d), 7.50 (6H, m) 1-243 δ= 8.38~8.36 (3H, m), 7.94 (1H, s), 7.75~7.73 (3H, m), 7.61 (1H, d), 7.50~7.41 (6H, m) 1-244 δ = 8.36 (2H, d), 7.96 (2H, d), 7.75 (2H, m), 7.50~7.41 (6H, m), 7.25 (2H, d) 1-264 δ = 8.38 (2H, d), 7.94 (2H, s), 7.75 to 7.73 (6H, m), 7.61 (2H, d), 7.49 to 7.41 (6H, m) 1-265 δ = 8.38 (1H, d), 7.96 to 7.94 (3H, m), 7.75 to 7.73 (5H, m), 7.61 (1H, d), 7.49 to 7.41 (6H, m), 7.25 (2H, d) 1-272 δ= 8.36 (2H, d), 8.03 to 7.98 (2H, m), 7.82 to 7.76 (2H, m), 7.54 to 7.50 (4H, m), 7.39 to 7.31 (2H, m) 1-294 δ = deuterium content 100%, no peak 1-295 δ = deuterium content 100%, no peak 1-296 δ = deuterium content 100%, no peak 1-301 δ = 8.36 (4H, d), 7.50 (6H, m), 1.69 (6H, s) 1-304 δ = 8.36 (2H, d), 7.96 (2H, d), 7.75 (2H, m), 7.50 to 7.41 (6H, m), 7.25 (2H, d) 1-356 δ = deuterium content 100%, no peak 1-361 δ = 8.36 (4H, d), 7.50 (6H, m) 1-372 δ= 8.36 (2H, d), 8.03 to 7.98 (2H, m), 7.82 to 7.76 (2H, m), 7.54 to 7.50 (4H, m), 7.39 to 7.31 (2H, m) 1-379 δ = deuterium content 100%, no peak 1-381 δ = 8.36 (4H, d), 7.50 (6H, m) 1-383 δ = 8.36 (2H, d), 7.96 (2H, d), 7.75 (2H, m), 7.50 to 7.41 (6H, m), 7.25 (2H, d) 1-398 δ = deuterium content 100%, no peak 1-401 δ = 8.36 (4H, d), 7.50 (6H, m), 1.69 (6H, s) 1-408 δ = 9.27 (1H, s), 8.79 (1H, d), 8.36 to 8.30 (5H, m), 8.15 (1H, d), 7.70 to 7.64 (4H, m), 7.52 to 7.50 (4H, m), 1.69 (6H, s) 1-416 δ = deuterium content 100%, no peak 1-421 δ = 8.36 (4H, d), 7.50 (6H, m) 1-423 δ = 8.36 (2H, d), 7.96 (2H, d), 7.75 (2H, m), 7.50~7.41 (6H, m), 7.25 (2H, d) 1-436 δ = deuterium content 100%, no peak 1-441 δ = 8.36 (4H, d), 7.50 (6H, m), 1.69 (6H, s) 1-442 δ= 8.38~8.36 (3H, m), 7.94 (1H, s), 7.75~7.73 (3H, m), 7.61 (1H, d), 7.50~7.41(6H, m), 1.69 (6H, s) 1-455 δ = deuterium content 100%, no peak 1-461 δ = 8.36 (4H, d), 7.50 (6H, m), 1.69 (12H, s) 1-477 δ= 8.38~8.36 (3H, m), 7.94 (1H, s), 7.75~7.73 (3H, m), 7.61 (1H, d), 7.50~7.41(6H, m), 1.69 (12H, s) 2-42 δ= 8.55 (1H, d), 8.30 (1H, d), 8.19~8.13 (2H, m), 7.99~7.89 (12H, m), 7.77~7.75 (5H, m), 7.50~7.35 (8H, m) ), 7.20~7.16 (2H, m) 3-2 δ= 8.55 (1H, d), 8.30 (1H, d), 8.19~8.13 (2H, m), 7.99~7.89 (4H, m), 7.77 (1H, d), 7.58~7.50 (2H, m), 7.35 (1H, m), 7.20~7.16 (2H, m) 3-26 δ= 7.92 (4H, d), 7.91 (4H, d), 7.75 (2H, d), 7.49~7.41 (6H, m) 3-50 δ = deuterium content 100%, no peak

compound FD-MS compound FD-MS 1-1 Chemical Formula: C ₃₉ H ₁₀ D ₁₂ N ₄ O ₂
Exact Mass: 590.250
Molecular Weight: 590.704 1-3 Chemical Formula: C ₄₅ H ₁₄ D ₁₂ N ₄ O ₂
Exact Mass: 666.281
Molecular Weight: 666.802 1-4 Chemical Formula: C ₄₅ H ₁₄ D ₁₂ N ₄ O ₂
Exact Mass: 666.281
Molecular Weight: 666.802 1-26 Chemical Formula: C ₅₁ H ₁₈ D ₁₂ N ₄ O ₂
Exact Mass: 742.312
Molecular Weight: 742.900 1-32 Chemical Formula: C ₄₅ H ₁₂ D ₁₂ N ₄ O ₃
Exact Mass: 680.260
Molecular Weight: 680.785 1-56 Chemical Formula: C ₅₁ D ₃₀ N ₄ O ₂
Exact Mass: 760.425
Molecular Weight: 761.010 1-61 Chemical Formula: C ₃₉ H ₁₀ D ₁₂ N ₄ OS
Exact Mass: 606.227
Molecular Weight: 606.765 1-64 Chemical Formula: C ₄₅ H ₁₄ D ₁₂ N ₄ OS
Exact Mass: 682.258
Molecular Weight: 682.863 1-114 Chemical Formula: C ₄₅ D ₂₆ N ₄ OS
Exact Mass: 696.346
Molecular Weight: 696.949 1-121 Chemical Formula: C ₄₂ H ₁₆ D ₁₂ N ₄ O
Exact Mass: 616.302
Molecular Weight: 616.786 1-123 Chemical Formula: C ₄₈ H ₂₀ D ₁₂ N ₄ O
Exact Mass: 692.333
Molecular Weight: 692.884 1-156 Chemical Formula: C ₄₈ H ₁₈ D ₁₂ N ₄ OS
Exact Mass: 722.289
Molecular Weight: 722.928 1-175 Chemical Formula: C ₅₄ H ₆ D ₃₀ N ₄ O
Exact Mass: 786.477
Molecular Weight: 787.092 1-181 Chemical Formula: C ₃₉ H ₁₀ D ₁₂ N ₄ OS
Exact Mass: 606.227
Molecular Weight: 606.765 1-183 Chemical Formula: C ₄₅ H ₁₄ D ₁₂ N ₄ OS
Exact Mass: 682.258
Molecular Weight: 682.863 1-184 Chemical Formula: C ₄₅ H ₁₄ D ₁₂ N ₄ OS
Exact Mass: 682.258
Molecular Weight: 682.863 1-238 Chemical Formula: C ₄₅ D ₂₄ N ₄ O ₂ S
Exact Mass: 708.313
Molecular Weight: 708.919 1-241 Chemical Formula: C ₃₉ H ₁₀ D ₁₂ N ₄ S ₂
Exact Mass: 622.204
Molecular Weight: 622.826 1-243 Chemical Formula: C ₄₅ H ₁₄ D ₁₂ N ₄ S ₂
Exact Mass: 698.235
Molecular Weight: 698.924 1-244 Chemical Formula: C ₄₅ H ₁₄ D ₁₂ N ₄ S ₂
Exact Mass: 698.235
Molecular Weight: 698.924 1-264 Chemical Formula: C ₅₁ H ₁₈ D ₁₂ N ₄ S ₂
Exact Mass: 774.267
Molecular Weight: 775.022 1-265 Chemical Formula: C ₅₁ H ₁₈ D ₁₂ N ₄ S ₂
Exact Mass: 774.267
Molecular Weight: 775.022 1-272 Chemical Formula: C ₄₅ H ₁₂ D ₁₂ N ₄ OS ₂
Exact Mass: 712.214
Molecular Weight: 712.907 1-294 Chemical Formula: C ₄₅ D ₂₆ N ₄ S ₂
Exact Mass: 712.323
Molecular Weight: 713.010 1-295 Chemical Formula: C ₅₁ D ₃₀ N ₄ S ₂
Exact Mass: 792.379
Molecular Weight: 793.132 1-296 Chemical Formula: C ₅₁ D ₃₀ N ₄ S ₂
Exact Mass: 792.379
Molecular Weight: 793.132 1-301 Chemical Formula: C ₄₂ H ₁₆ D ₁₂ N ₄ S
Exact Mass: 632.279
Molecular Weight: 632.847 1-304 Chemical Formula: C ₄₈ H ₂₀ D ₁₂ N ₄ S
Exact Mass: 708.310
Molecular Weight: 708.945 1-356 Chemical Formula: C ₅₄ H ₆ D ₃₀ N ₄ S
Exact Mass: 802.454
Molecular Weight: 803.153 1-361 Chemical Formula: C ₃₉ H ₁₀ D ₁₂ N ₄ O ₂
Exact Mass: 590.250
Molecular Weight: 590.704 1-372 Chemical Formula: C ₄₅ H ₁₂ D ₁₂ N ₄ O ₃
Exact Mass: 680.260
Molecular Weight: 680.785 1-379 Chemical Formula: C ₄₅ D ₂₄ N ₄ O ₃
Exact Mass: 692.335
Molecular Weight: 692.858 1-381 Chemical Formula: C ₃₉ H ₁₀ D ₁₂ N ₄ OS
Exact Mass: 606.227
Molecular Weight: 606.765 1-383 Chemical Formula: C ₄₅ H ₁₄ D ₁₂ N ₄ OS
Exact Mass: 682.258
Molecular Weight: 682.863 1-398 Chemical Formula: C ₅₁ D ₂₈ N ₄ OS
Exact Mass: 772.374
Molecular Weight: 773.043 1-401 Chemical Formula: C ₄₂ H ₁₆ D ₁₂ N _4O
Exact Mass: 616.302
Molecular Weight: 616.786 1-408 Chemical Formula: C ₅₄ H ₂₂ D ₁₂ N ₄ O
Exact Mass: 766.349
Molecular Weight: 766.966 1-416 Chemical Formula: C ₄₈ H ₆ D ₂₆ N ₄ O
Exact Mass: 706.421
Molecular Weight: 706.970 1-421 Chemical Formula: C ₃₉ H ₁₀ D ₁₂ N ₄ S ₂
Exact Mass: 622.204
Molecular Weight: 622.826 1-423 Chemical Formula: C ₄₅ H ₁₄ D ₁₂ N ₄ S ₂
Exact Mass: 698.235
Molecular Weight: 698.924 1-436 Chemical Formula: C ₄₅ D ₂₆ N ₄ S ₂
Exact Mass: 712.323
Molecular Weight: 713.010 1-441 Chemical Formula: C ₄₂ H ₁₆ D ₁₂ N ₄ S
Exact Mass: 632.279
Molecular Weight: 632.847 1-442 Chemical Formula: C ₄₈ H ₂₀ D ₁₂ N ₄ S
Exact Mass: 708.310
Molecular Weight: 708.945 1-455 Chemical Formula: C ₄₈ H ₆ D ₂₆ N ₄ S
Exact Mass: 722.398
Molecular Weight: 723.031 1-461 Chemical Formula: C ₄₅ H ₂₂ D ₁₂ N ₄
Exact Mass: 642.354
Molecular Weight: 642.868 1-477 Chemical Formula: C ₅₇ H ₁₂ D ₃₀ N ₄
Exact Mass: 812.529
Molecular Weight: 813.174 2-42 Chemical Formula: C ₄₈ H ₃₂ N ₂
Exact Mass: 636.257
Molecular Weight: 636.798 3-2 Chemical Formula: C ₄₈ H ₁₄ D ₁₈ N ₂
Exact Mass: 654.370
Molecular Weight: 654.908 3-26 Chemical Formula: C ₄₈ H ₁₈ D ₁₄ N ₂
Exact Mass: 650.344
Molecular Weight: 650.883 3-50 Chemical Formula: C ₄₈ D ₃₂ N ₂
Exact Mass: 668.457
Molecular Weight: 668.993

<Experimental example>

Experimental Example 1

(1) Manufacture of organic light emitting device

A glass substrate coated with a thin film of indium tin oxide (ITO) having a thickness of 1,500 Å was washed with ultrasonic waves in distilled water. 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 increase the work function of ITO and remove residual films in a vacuum state, and then transferred to a thermal evaporation equipment for organic deposition.

4,4',4"-tris[2-naphthyl(phenyl)amino]triphenylamine (4,4',4"-Tris[2- naphthyl(phenyl)amino]triphenylamine: 2-TNATA) was deposited, and N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (N,N'-diphenyl-4,4'-diamine) was deposited as a hole transport layer. '-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine: NPB) was deposited.

After forming the hole injection layer and the hole transport layer in this way, a light emitting layer was thermally vacuum deposited thereon as follows. The light emitting layer was deposited with a thickness of 400 Å of the compounds listed in Table 10 as a host, and using Ir(ppy) ₃ as a green phosphorescent dopant, Ir(ppy) ₃ was added to the host in an amount of 7 wt% of the deposition thickness of the light emitting layer. Deposited by doping.

Subsequently, bathocuproine (BCP) was deposited to a thickness of 60 Å as a hole blocking layer, and tris(8-hydroxyquinolinato)aluminium, Alq ₃ as an electron transport layer thereon. ) was deposited to a thickness of 200 Å.

Finally, after depositing lithium fluoride (LiF) to a thickness of 10 Å on the electron transport layer to form an electron injection layer, an aluminum (Al) cathode was deposited on the electron injection layer to a thickness of 1,200 Å to form a cathode. An organic light emitting device was manufactured by forming.

On the other hand, all organic compounds required for the manufacture of an organic light emitting device were purified by vacuum sublimation under 10 ⁻⁸ to 10 ⁻⁶ torr for each material, and used in the manufacture of an organic light emitting device.

(2) Driving voltage and luminous efficiency of organic light emitting device

The electroluminescence (EL) characteristics of the organic light emitting device manufactured as described above were measured with McSyers' M7000, and the standard luminance was 6,000 cd through the lifetime equipment measuring equipment (M6000) manufactured by McScience with the measurement result. /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 12.

light emitting layer
compound driving voltage
(V) luminous efficiency
(cd/A) color
EL color life span
(T ₉₀ ) Example 1 1-1 4.54 73.7 green 331 Example 2 1-3 4.53 74.9 green 338 Example 3 1-4 4.53 73.5 green 347 Example 4 1-26 4.56 73.2 green 352 Example 5 1-32 4.50 75.5 green 340 Example 6 1-56 4.86 82.1 green 440 Example 7 1-61 4.63 73.5 green 368 Example 8 1-64 4.65 73.6 green 370 Example 9 1-114 4.81 82.1 green 471 Example 10 1-121 4.62 73.1 green 363 Example 11 1-123 4.57 77.3 green 368 Example 12 1-156 4.69 74.4 green 366 Example 13 1-175 4.97 86.2 green 455 Example 14 1-181 4.35 75.8 green 390 Example 15 1-183 4.59 76.7 green 394 Example 16 1-184 4.70 76.3 green 402 Example 17 1-238 4.90 85.1 green 509 Example 18 1-241 4.38 75.7 green 431 Example 19 1-243 4.25 76.6 green 424 Example 20 1-244 4.63 73.3 green 441 Example 21 1-264 4.33 75.7 green 427 Example 22 1-265 4.41 74.5 green 435 Example 23 1-272 4.53 74.1 green 439 Example 24 1-294 4.94 82.1 green 550 Example 25 1-295 4.77 84.6 green 532 Example 26 1-296 4.99 80.1 green 588 Example 27 1-301 4.40 75.9 green 405 Example 28 1-304 4.53 74.6 green 415 Example 29 1-356 4.79 83.3 green 519 Example 30 1-361 4.33 74.0 green 260 Example 31 1-372 4.20 73.5 green 266 Example 32 1-379 4.51 82.3 green 353 Example 33 1-381 4.45 74.7 green 291 Example 34 1-383 4.35 75.1 green 297 Example 35 1-398 4.62 83.0 green 888 Example 36 1-401 4.55 72.8 green 272 Example 37 1-408 4.53 74.9 green 277 Example 38 1-416 4.84 83.1 green 353 Example 39 1-421 4.50 74.9 green 320 Example 40 1-423 4.51 73.9 green 326 Example 41 1-436 4.81 82.0 green 416 Example 42 1-441 4.45 74.7 green 303 Example 43 1-442 4.47 74.4 green 311 Example 44 1-455 4.69 83.8 green 423 Example 45 1-461 4.56 73.2 green 282 Example 46 1-477 4.77 83.5 green 395 Example 47 1-481 4.65 73.9 green 382 Example 48 1-484 4.32 82.7 green 486 Example 49 1-485 4.55 78.2 green 374 Example 50 1-488 4.91 87.1 green 481 Example 51 1-489 4.58 77.6 green 382 Example 52 1-492 4.91 86.8 green 489 Comparative Example 1 Ref. One 5.57 64.8 green 160 Comparative Example 2 Ref. 2 5.83 61.2 green 170 Comparative Example 3 Ref. 3 5.65 63.7 green 164 Comparative Example 4 Ref. 4 5.66 61.0 green 188 Comparative Example 5 Ref. 5 5.81 64.3 green 198 Comparative Example 6 Ref. 6 5.62 62.5 green 193 Comparative Example 7 Ref. 7 5.62 64.3 green 130 Comparative Example 8 Ref. 8 5.41 65.5 green 149 Comparative Example 9 Ref. 9 5.62 64.6 green 138 Comparative Example 10 Ref. 10 5.62 65.1 green 157 Comparative Example 11 Ref. 11 5.33 64.2 green 153 Comparative Example 12 Ref. 12 5.52 64.4 green 142 Comparative Example 13 Ref. 13 5.63 62.5 green 183 Comparative Example 14 Ref. 14 5.82 61.2 green 181 Comparative Example 15 Ref. 15 5.55 63.5 green 176 Comparative Example 16 Ref. 16 5.63 62.1 green 185

In Table 12, the compounds of Comparative Examples 1 to 16 are the following compounds Ref. 1 to Ref.16.

From the results of Table 12, it was confirmed that the organic light emitting device using the heterocyclic compound of the present invention as a material for the light emitting layer had a lower driving voltage and significantly improved light emitting efficiency and lifetime compared to the organic light emitting devices of Comparative Examples 1 to 16.

The heterocyclic compound according to the present invention is a deuterium-substituted compound, and the compounds of Comparative Examples 1 to 16 are hydrogen-substituted compounds. Compounds substituted with deuterium, whose atomic mass is twice as large as hydrogen, have lower zero-point energy and lower vibrational energy than compounds substituted with hydrogen, resulting in lower energy in the ground state and reduced collisions due to intermolecular vibrations, turning the thin film into an amorphous state. Therefore, the lifetime of the organic light emitting device can be improved.

The compound substituted with deuterium has low ground state energy, thereby improving the stability of the compound, and high dissociation energy of the C-D bond, improving molecular stability, thereby improving the lifetime of the organic light emitting device.

Specifically, deuterium-substituted heterocyclic compounds 1-1 to 1-492 according to the present invention are comparative example compounds substituted with hydrogen due to molecular stability and non-crystallinity Ref. It can be seen that the driving voltage and lifespan are improved compared to 1 to 16, and the low vibration energy of the deuterium-substituted heterocyclic compound minimizes energy loss and facilitates energy transfer to the dopant, thereby improving the luminous efficiency of the organic light emitting device. could improve

In general, when a radical cation is generated in carbazole, the 3-position of carbazole is activated to form a dimer, thereby impairing the efficiency and lifetime of the device.

On the other hand, when a radical cation is generated in the deuterium-substituted condensed carbazole, the deuterium stabilizes the radical cation to improve the lifespan of the organic light emitting device.

Specifically, the deuterium-substituted heterocyclic compounds 1-1 to 1-492 according to the present invention effectively stabilized the radical cation due to the deuterium substituted in the condensed carbazole, thereby effectively improving the lifespan of the organic light emitting device. , Comparative example compound Ref. It was confirmed that 1 to 16 were substituted with hydrogen and did not contribute to stabilizing the radical cation. Accordingly, it was confirmed that the lifespan of the organic light emitting device using compounds 1-1 to 1-492 in which condensed carbazole was substituted with deuterium was used as a material for the light emitting layer was improved.

In addition, the heterocyclic compound 1-294 substituted with deuterium according to the present invention was able to improve the luminous efficiency of the organic light emitting device by reducing energy loss due to the low vibrational energy of the compound, and lowered the ground state energy of the organic light emitting device. lifespan could be improved.

In addition, compound 1-241 in which only condensed carbazole was substituted with deuterium was able to improve the driving voltage of the organic light emitting device because the intermolecular interaction was increased compared to compound 1-294, resulting in a smaller intermolecular distance and improved mobility.

Experimental Example 2

(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 increase the work function of ITO and remove residual films in a vacuum state, and then transferred to a thermal evaporation equipment for organic deposition.

4,4',4"-tris[2-naphthyl(phenyl)amino]triphenylamine (4,4',4"-Tris[2- naphthyl(phenyl)amino]triphenylamine: 2-TNATA) was deposited, and N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (N,N'-diphenyl-4,4'-diamine) was deposited as a hole transport layer. '-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine: NPB) was deposited.

After forming the hole injection layer and the hole transport layer in this way, a light emitting layer was thermally vacuum deposited thereon as follows. The light emitting layer was pre-mixed with one (N-type) compound listed in Table 11 below and one (P-type) compound represented by Formula 2 as a host, and then 400 Å from one source. The host was doped with Ir(ppy) ₃ in an amount of 7 wt% of the deposition thickness of the light emitting layer using Ir(ppy) ₃ as a green phosphorescent dopant.

Subsequently, bathocuproine (BCP) was deposited to a thickness of 60 Å as a hole blocking layer, and tris(8-hydroxyquinolinato)aluminium, Alq ₃ as an electron transport layer thereon. ) was deposited to a thickness of 200 Å.

Finally, after depositing lithium fluoride (LiF) to a thickness of 10 Å on the electron transport layer to form an electron injection layer, an aluminum (Al) cathode was deposited on the electron injection layer to a thickness of 1,200 Å to form a cathode. An organic light emitting device was manufactured by forming.

On the other hand, all organic compounds required for the manufacture of an organic light emitting device were purified by vacuum sublimation under 10 ⁻⁸ to 10 ⁻⁶ torr for each material, and used in the manufacture of an organic light emitting device.

(2) Driving voltage and luminous efficiency of organic light emitting device

The electroluminescence (EL) characteristics of the organic light emitting device manufactured as described above were measured with McSyers' M7000, and the standard luminance was 6,000 cd through the lifetime equipment measuring equipment (M6000) manufactured by McScience with the measurement result. /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 13.

light emitting layer
compound ratio driving voltage
(V) luminous efficiency
(cd/A) color
EL color life span
(T ₉₀ ) Example 53 1-1:2-42 1:8 4.53 53.7 green 415 Example 54 1-1:2-42 1:5 4.49 56.1 green 524 Example 55 1-1:2-42 1:2 4.32 82.3 green 666 Example 56 1-1:2-42 1:1 4.38 70.1 green 612 Example 57 1-1:2-42 2:1 4.29 69.4 green 589 Example 58 1-1:2-42 5:1 4.22 68.1 green 520 Example 59 1-1:2-42 8:1 4.21 67.4 green 437 Example 60 1-181:3-2 1:2 4.25 82.7 green 651 Example 61 1-181:3-2 1:1 4.43 80.1 green 612 Example 62 1-181:3-2 2:1 4.48 78.5 green 588 Example 63 1-241:3-26 1:2 4.29 81.4 green 715 Example 64 1-241:3-26 1:1 4.46 79.8 green 662 Example 65 1-241:3-26 2:1 4.49 78.4 green 629 Example 66 1-294:3-50 1:2 4.70 94.5 green 742 Example 67 1-294:3-50 1:1 4.83 92.8 green 722 Example 68 1-294:3-50 2:1 4.95 90.1 green 699 Comparative Example 17 Ref.5: 3-2 1:2 5.60 71.5 green 302 Comparative Example 18 Ref.5: 3-2 1:1 5.73 69.8 green 292 Comparative Example 19 Ref.5: 3-2 2:1 5.95 67.4 green 247

From the results of Table 13, the heterocyclic compound of the present invention, the compound represented by Formula 1, was used as an N-type host, and the compound represented by Formula 2 of the present invention was used as a P-type host to obtain the two compounds In the case of mixing and depositing, it was confirmed that the luminous efficiency and lifetime of the organic light emitting device were improved. From this, when the two compounds are mixed and deposited, it can be expected that an exciplex phenomenon occurs.

The exciplex phenomenon is a phenomenon in which energy of the size of the HOMO energy level of a donor (p-host) and the LUMO energy level of an acceptor (n-host) is released by electron exchange between two molecules. When an exciplex between two molecules occurs, reverse intersystem crossing (RISC) occurs, and as a result, the internal quantum efficiency of fluorescence can be increased to 100%. When a donor (p-host) with good hole transport ability and an acceptor (n-host) with good electron transport ability 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. Since it is injected into the organic light emitting diode, the driving voltage of the organic light emitting diode can be lowered, thereby helping to improve the lifetime of the organic light emitting diode.

In the case of the compound represented by Formula 2, it is a compound substituted with hydrogen or partially substituted with deuterium or total deuterium. Compounds substituted with deuterium, whose atomic mass is twice as large as hydrogen, have lower zero-point energy and lower vibrational energy than compounds substituted with hydrogen, resulting in lower energy in the ground state and reduced collisions due to intermolecular vibrations, resulting in thin films in an amorphous state. It can be made to improve the lifespan of the organic light emitting device.

The deuterium-substituted compound has low ground state energy, thereby improving the stability of the compound, and high dissociation energy of the C-D bond, improving molecular stability, thereby improving the lifetime of the organic light emitting device.

In the present invention, when the compound represented by Chemical Formula 2 serves as a donor and the compound represented by Chemical Formula 1 serves as an acceptor, when the compounds are used as a host of the light emitting layer, excellent organic light emission can be obtained. It was confirmed that the characteristics of the device were represented.

Claims (18)

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

In Formula 1,
R1 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; selected from the group consisting of, wherein at least one of R1 to R12 is deuterium,
X1, X2, and X3 are the same as or different from each other, and are each independently NAr1, O, S, or CR13R14, and at least one of X1, X2, and X3 is NAr1,
Ar1 is a group represented by Formula 1-1 below,
[Formula 1-1]

In Formula 1-1,
L1 and L2 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,
Ar2 and Ar3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; selected from the group consisting of
a and b are the same as or different from each other, and each independently represents an integer from 0 to 3;
R13 and R14 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; is selected from the group consisting of. According to claim 1,
The heterocyclic compound represented by Formula 1 is any one of the following Formulas 1-a to 1-f, a heterocyclic compound:
[Formula 1-a]

[Formula 1-b]

[Formula 1-c]

[Formula 1-d]

[Formula 1-e]

[Formula 1-f]

In Formulas 1-a to 1-f,
X3 is O, S or CR13R14;
R1 to R14 and Ar1 are as defined in Formula 1 and Formula 1-1 above. According to claim 1,
A heterocyclic compound in which R1 to R12 are deuterium. According to claim 1,
Among the heterocyclic compounds represented by Formula 1, the content of deuterium in R1 to R12 is 1% to 100% based on the total number of hydrogen atoms and deuterium atoms, the heterocyclic compound. According to claim 1,
In Formula 1-1, Ar2 and Ar3 may be a C6 to C30 aryl group substituted with deuterium or a C2 to C30 heteroaryl group substituted with deuterium, and in this case, based on the total number of hydrogen atoms and deuterium atoms, deuterium A content of 1% to 100% of that, the heterocyclic compound. According to claim 1,
Of the heterocyclic compound represented by Formula 1, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms is 1% to 100%, the heterocyclic compound. According to claim 6,
Of the heterocyclic compound represented by Formula 1, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms is 20% to 100%, the heterocyclic compound. According to claim 1,
The heterocyclic compound represented by Formula 1 is any one selected from the group consisting of the following compounds, the heterocyclic compound:

. a first electrode;
a second electrode provided to face the first electrode; and
An organic light emitting device comprising one or more organic material layers provided between the first electrode and the second electrode,
The organic material layer comprises the heterocyclic compound according to any one of claims 1 to 8, an organic light emitting device. According to claim 9,
The organic light emitting device includes at least 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, a battery blocking layer, and a hole blocking layer,
The organic light-emitting device of claim 1 or more comprising the heterocyclic compound. According to claim 9,
Wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound, the organic light emitting device. According to claim 9,
The organic material layer includes a light emitting layer, the light emitting layer includes a host material, and the host material includes the heterocyclic compound, the organic light emitting device. According to claim 9,
The organic material layer further comprises a heterocyclic compound represented by Formula 2 below, an organic light emitting device:
[Formula 2]

In Formula 2,
R21 to R34 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; selected from the group consisting of
L3 and L4 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,
Ar11 and Ar12 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; -P(=0)R101R102; and -SiR101R102R103; wherein R101, R102, and R103 are the same as or different from each other, and each independently 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,
m and n are the same as or different from each other, and are each independently an integer of 0 to 3. According to claim 13,
The heterocyclic compound represented by Formula 2 does not contain deuterium as a substituent, or the content of deuterium is 1% to 100% based on the total number of hydrogen atoms and deuterium atoms, an organic light emitting device. According to claim 13,
The heterocyclic compound represented by Formula 2 is any one selected from the group consisting of the following compounds, an organic light emitting device:

. According to claim 13,
At least one of the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 does not contain deuterium as a substituent, or has a deuterium content of 1% to 100 based on the total number of hydrogen atoms and deuterium atoms. %, organic light emitting device. A composition for an organic layer of an organic light emitting device comprising the heterocyclic compound represented by Formula 1 according to any one of claims 1 to 8 and the heterocyclic compound represented by Formula 2 below:
[Formula 2]

In Formula 2,
R21 to R34 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; And a substituted or unsubstituted C2 to C60 heteroaryl group; selected from the group consisting of
L1 and L2 are the same as or different from each other, and each independently a single bond; A substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,
Ar11 and Ar12 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C2 to C60 alkenyl group; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C60 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; A substituted or unsubstituted C2 to C60 heteroaryl group; -P(=0)R101R102; and -SiR101R102R103; wherein R101, R102, and R103 are the same as or different from each other, and each independently 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,
m and n are the same as or different from each other, and are each independently an integer of 0 to 3. According to claim 17,
The weight ratio of the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 is 1:10 to 10:1, the composition for an organic layer.

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