WO2023033351A1

WO2023033351A1 - Heterocyclic compound, organic light-emitting device comprising same, and composition for organic layer of organic light-emitting device

Info

Publication number: WO2023033351A1
Application number: PCT/KR2022/010212
Authority: WO
Inventors: 박건유; 노영석; 김동준
Original assignee: 엘티소재주식회사
Priority date: 2021-08-31
Filing date: 2022-07-13
Publication date: 2023-03-09
Also published as: TW202319510A; KR20230032537A

Abstract

The present specification relates to a heterocyclic compound represented by chemical formula 1, an organic light-emitting device comprising same, and a composition for an organic layer of an organic light-emitting device.

Description

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

This application claims the benefit of priority based on Korean Patent Application No. 10-2021-0115492 dated August 31, 2021, and includes all contents disclosed in the literature of the Korean patent application as part of this specification.

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.

[Prior art literature]

[Patent Literature]

(Patent Document 1) 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, each independently represent NAr1, O, S or CR13R14, at least two or more of X1, X2 and X3 are NAr1, the plurality of Ar1s are different from each other, any of these One is a group represented by Formula 1-1 below,

Ar1 is 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; And it is selected from the group consisting of 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,

R101 to R114 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)R201R202; and -SiR201R202R203; wherein R201, R202, and R203 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.

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 (2H) is an isotope of hydrogen, some hydrogen atoms may be deuterium.

In one embodiment of the present invention, "when no substituent is shown in the chemical formula or compound structure" may mean that all positions at which 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 "when no substituent is shown in the chemical formula or compound structure", "deuterium content is 0%", "hydrogen content is 100%", "substituents are all 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 2H.

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%.

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, phenyl, biphenyl, terphenyl, 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.

[Formula 1]

In Formula 1,

[Formula 1-1]

In Formula 1-1,

In one embodiment of the present invention, X1 and X2 are NAr1, and X3 can be O, S or CR13R14.

In another embodiment of the invention, X1 and X3 are NAr1 and X2 can be O, S or CR13R14.

In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 may be any one of Formula 1-a and Formula 1-b, 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 above,

Ar1' is the same as the definition of Ar1,

Ar1 and Ar1' are different from each other, and one of them is a group represented by Formula 1-1;

[Formula 1-b]

In Formula 1-b,

X2 is O, S or CR13R14;

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

Ar1' is the same as the definition of Ar1,

Ar1 and Ar1' are different from each other, and either one of them is a group represented by Formula 1-1.

In another embodiment of the present invention, in Formula 1-a, Ar1 is a group represented by Formula 1-1, and Ar1' is 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-a, Ar1 is a group represented by Formula 1-1, and Ar1' is 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-a, Ar1' is a group represented by Formula 1-1, and Ar1 is a substituted or unsubstituted C6 to C30 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-a, Ar1' is a group represented by Formula 1-1, and Ar1 is 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-b, Ar1 is a group represented by Formula 1-1, and Ar1' is 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-b, Ar1 is a group represented by Formula 1-1, and Ar1' is 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-b, Ar1' is a group represented by Formula 1-1, and Ar1 is 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-b, Ar1' is a group represented by Formula 1-1, and Ar1 is a substituted or unsubstituted C6 to C20 aryl group; Or it may be a substituted or unsubstituted C2 to C20 heteroaryl group.

In one embodiment of the present invention, in Formula 1-a and Formula 1-b, Ar1 and Ar1' are each independently a group represented by Formula 1-1 and Formula 1-2-a to 1-2- It may be a heterocyclic compound which is any one of the groups represented by g:

[Formula 1-1]

[Formula 1-2-a]

[Formula 1-2-b]

[Formula 1-2-c]

[Formula 1-2-d]

[Formula 1-2-e]

[Formula 1-2-f]

[Formula 1-2-g]

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 a substituted or unsubstituted C2 to C30 heteroaryl group,

L1, L2, a and b are as defined in Formula 1 above,

In Formula 1-2-a to Formula 1-2-g,

R21 to R60 are hydrogen or deuterium;

X4 is O, S or CR61R62;

R61 and R62 are methyl groups,

p, q and r are the same as or different from each other, and are each independently an integer of 3 to 5.

In another embodiment of the present invention, 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.

In another embodiment of the present invention, R21 to R60 in Chemical Formulas 1-2-a to 1-2-g may be deuterium.

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 heterocyclic compound represented by Formula 1 may not contain deuterium as a substituent, or may have a deuterium content of 1% to 100% based on the total number of hydrogen atoms and deuterium atoms.

In another embodiment of the present invention, the heterocyclic compound represented by Formula 1 may not contain deuterium as a substituent, or the content of deuterium may be 10% to 100% based on the total number of hydrogen atoms and deuterium atoms.

In another embodiment of the present invention, the heterocyclic compound represented by Formula 1 may not contain deuterium as a substituent, or the content of deuterium based on the total number of hydrogen atoms and deuterium atoms may be 20% to 90%.

In another embodiment of the present invention, the heterocyclic compound represented by Formula 1 may not contain deuterium as a substituent, or the content of deuterium may be 30% to 80% based on the total number of hydrogen atoms and deuterium atoms.

For example, the heterocyclic compound represented by Formula 1 does not contain deuterium as a substituent, or the content of deuterium is greater than 0%, 5% or more, 10% or more, or 15% based on the total number of hydrogen atoms and deuterium atoms. 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, 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, the heterocyclic compound represented by Formula 1 does not contain deuterium as a substituent, or the content of deuterium in R1 to R12 is greater than 0%, 5% or more, or 10% based on the total number of hydrogen atoms and deuterium atoms. Can be greater than, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, 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 Formula 1-1, Ar2 and Ar3 may be an aryl group or a heteroaryl group substituted with deuterium, and in this case, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms is 1 % to 100%.

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

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

For example, in Formula 1-1, when Ar2 and Ar3 are aryl groups or heteroaryl groups substituted with deuterium, the substituents do not contain deuterium, or the content of deuterium in the substituent is based on the total number of hydrogen atoms and deuterium atoms can be greater than 0%, greater than 1%, greater than 5%, greater than 10%, greater than 15%, greater than 20%, greater than 25%, greater than 30%, greater than 35%, greater than 40%, greater than 45%, or greater than 50% 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 Formulas 1-2-a to 1-2-g, R21 to R60 do not contain deuterium, or the content of deuterium in R21 to R60 is based on the total number of hydrogen atoms and deuterium atoms. It may be 1% to 100%.

In another embodiment of the present invention, in Formulas 1-2-a to 1-2-g, R21 to R60 do not contain deuterium, or the content of deuterium in R21 to R60 is based on the total number of hydrogen atoms and deuterium atoms. It may be 5% to 95%.

In another embodiment of the present invention, in Formulas 1-2-a to 1-2-g, R21 to R60 do not contain deuterium, or the content of deuterium in R21 to R60 is based on the total number of hydrogen atoms and deuterium atoms. It may be 10% to 90%.

For example, in Formulas 1-2-a to 1-2-g, R21 to R60 do not contain deuterium, or the content of deuterium in R21 to R60 exceeds 0% based on the total number of hydrogen atoms and deuterium atoms; 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 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.

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,

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, R101 to R114 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, R101 to R114 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, R101 to R114 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)R201R202; and -SiR201R202R203; wherein R201, R202, and R203 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(=O)R201R202; and -SiR201R202R203; wherein R201, R202, and R203 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 heterocyclic compound represented by Formula 2 may not contain deuterium as a substituent, or may have a deuterium content of 1% to 100% based on the total number of hydrogen atoms and deuterium atoms.

In another embodiment of the present invention, the heterocyclic compound represented by Formula 2 may not contain deuterium as a substituent, or the content of deuterium may be 10% to 100% based on the total number of hydrogen atoms and deuterium atoms.

In another embodiment of the present invention, the heterocyclic compound represented by Formula 2 may not contain deuterium as a substituent, or the content of deuterium may be 20% to 90% based on the total number of hydrogen atoms and deuterium atoms.

In another embodiment of the present invention, the heterocyclic compound represented by Formula 2 may not contain deuterium as a substituent, or the content of deuterium may be 30% to 80% based on the total number of hydrogen atoms and deuterium atoms.

For example, the heterocyclic compound represented by Formula 2 does not contain deuterium as a substituent, or the content of deuterium is greater than 0%, 10% or more, 20% or more, or 30% based on the total number of hydrogen atoms and deuterium atoms. It may be more than, 40% or more, or 50% or more, and may be 100% or less, 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, the heterocyclic compounds contain deuterium as a substituent. Alternatively, at least one of the heterocyclic compounds may have a deuterium content 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, the heterocyclic compounds contain deuterium as a substituent. It may not contain, or at least one of the heterocyclic compounds may have a deuterium content of 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, the heterocyclic compounds contain deuterium as a substituent. It may not contain, or at least one of the heterocyclic compounds may have a deuterium content of 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, the heterocyclic compounds contain deuterium as a substituent. It may not contain, or at least one of the heterocyclic compounds may have a deuterium content of 20% to 80%.

For example, 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, the heterocyclic compounds do not contain deuterium as a substituent, or At least one of the heterocyclic compounds has a deuterium content of more than 0%, 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, 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", L2MX', and L3M 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 sp ² 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, 7,8-benzoquinoline, phenylpyridine, benzo thiophenylpyridine, 3-methoxy-2-phenylpyridine, thiophenylpyridine, tolylpyridine, etc. Non-limiting examples of X' and X" include acetylacetonate (acac), hexafluoroacetylacetonate, salicylate Silidene, 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 SnO2: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/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.

<제조예><Production Example>

제조예 1: 화합물 1-1의 제조Preparation Example 1: Preparation of compound 1-1

1)One) 화합물 1-1-6의 제조Preparation of compound 1-1-6

Dibenzo[b,d]furan-4-amine (9.5g, 51.9mM), 2-bromo-1-chloro-3-fluorobenzene (2- bromo-1-chloro-3-fluorobenzene) (13.0g, 62.3mM), Palladium (II) acetate (Pd(OAc) ₂ ) (0.58g, 2.6mM), XantPhos (3g, 5.2 mM) and sodium tert-butoxide ( t -BuONa) (10.0g, 103.8mM) were dissolved in 1,4-dioxane (200mL) and refluxed for 12 hours. did 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 12.9 g of the target compound 1-1-6 (yield: 80%).

2)2) 화합물 1-1-5의 제조Preparation of compound 1-1-5

Compound 1-1-6 (12.9g, 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 (200mL) 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 10.4 g of the target compound 1-1-5 (yield: 91%).

3)3) 화합물 1-1-4의 제조Preparation of compound 1-1-4

Compound 1-1-5 (4.4g, 15.8mM), bromobenzene (3.0g, 19.0mM), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ ) (0.72g, 0.8 mM), XPhos (0.74g, 1.6mM) and sodium tert-butoxide ( t -BuONa) (3.0g, 31.6mM) were added to xylene (100mL) and dissolved. Refluxed for 24 hours. After the reaction was completed, extraction was performed by adding distilled water and dichloromethane (DCM) at room temperature. 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 4.9 g of the target compound 1-1-4 (yield: 89%).

4)4) 화합물 1-1-3의 제조Preparation of compound 1-1-3

Compound 1-1-4 (4.9g, 14.1mM), 2-chloroaniline (2.2g, 16.9mM) and potassium tert-butoxide ( t -BuOK) (3.2g, 28.2 mM) was added to dimethyl sulfoxide (DMSO) (100 mL), dissolved, and refluxed for 12 hours. After the reaction was completed, extraction was performed by adding distilled water and dichloromethane (DCM) at room temperature. 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 4.6 g of the target compound 1-1-3 (yield: 71%).

5)5) 화합물 1-1-2의 제조Preparation of compound 1-1-2

Compound 1-1-3 (19.0 g, 41.5 mM), Palladium (II) acetate (Pd(OAc) ₂ ) (0.47 g, 2.1 mM), 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 15.3 g of the target compound 1-1-2 (yield: 87%).

6)6) 화합물 1-1-1의 제조Preparation of compound 1-1-1

After dissolving compound 1-1-2 (15.3g, 36.2mM) and triflic acid (80.1mL, 905.0mM) in benzene-d6 (150mL), the mixture 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 12.4 g of the target compound 1-1-1 (yield: 78%).

7)7) 화합물 1-1의 제조Preparation of compound 1-1

Compound 1-1-1 (12.4 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- Butoxide (sodium tert-butoxide, t -BuONa) (5.4g, 56.4mM) was dissolved in xylene (200mL) 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 13.8 g of the target compound 1-1 (yield: 73%).

In Preparation Example 1, Intermediate A of Table 1 was used instead of dibenzo [b,d] furan-4-amine, and instead of bromobenzene, Using Intermediate B of Table 1 below, instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, The target compounds in Table 1 below were synthesized in the same manner as in Preparation Example 1 using Intermediate C of Table 1 below.

[Table 1]

제조예 2: 화합물 1-361의 제조Preparation Example 2: Preparation of compound 1-361

1) 화합물 1-361-4의 제조1) Preparation of compound 1-361-4

After dissolving compound 1-1-5 (10.0g, 36.2mM) and triflic acid (80.1mL, 905.0mM) in benzene-d6 (100mL), the mixture 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 8.8 g of the target compound 1-361-4 (yield: 85%).

2) 화합물 1-361-3의 제조2) Preparation of compound 1-361-3

Compound 1-361-4 (8.0 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- Butoxide (sodium tert-butoxide, t -BuONa) (5.4g, 56.4mM) was dissolved in xylene (200mL) 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 11.2 g of the target compound 1-361-3 (yield: 77%).

3) 화합물 1-361-2의 제조3) Preparation of compound 1-361-2

Compound 1-361-3 (7.3g, 14.1mM), 2-chloroaniline (2.2g, 16.9mM) and potassium tert-butoxide ( t -BuOK) (3.2g, 28.2mM) was dissolved in dimethyl sulfoxide (DMSO) (100mL), 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 6.1 g of the target compound 1-361-2 (yield: 69%).

4) 화합물 1-361-1의 제조4) Preparation of Compound 1-361-1

Compound 1-361-2 (26.0 g, 41.5 mM), Palladium (II) acetate (Pd(OAc) ₂ ) (0.47 g, 2.1 mM), 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 13.5 g of the target compound 1-361-1 (yield: 88%).

4) 화합물 1-361의 제조4) Preparation of compound 1-361

Compound 1-361-1 (9.3g, 15.8mM), 1-bromobenzene-2,3,4,5,6-d5 (1-bromobenzene-2,3,4,5,6-d5) (3.1 g, 19.0 mM), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ ) (0.72 g, 0.8 mM), XPhos (0.74 g, 1.6 mM) and sodium tert-butoxide (sodium tert-butoxide, t -BuONa) (3.0g, 31.6mM) was dissolved in xylene (100mL) and refluxed for 24 hours. After the reaction was completed, extraction was performed by adding distilled water and dichloromethane (DCM) at room temperature. 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 5.3 g of the target compound 1-361 (yield: 85%).

In Preparation Example 2, instead of Compound 1-1-5, Intermediate A of Table 2 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 2 were synthesized in the same manner as in Preparation Example 2, using Intermediate B in Table 2 below.

[Table 2]

제조예 3: 화합물 1-461의 제조Preparation Example 3: Preparation of Compound 1-461

1) 화합물 1-461-4의 제조1) Preparation of compound 1-461-4

12-phenyl-12H-benzofuro[2,3-a]carbazole (13.8g, 41.5mM) was mixed with tetrahydrofuran (THF ) (260mL) and dissolved, nitrogen substitution was performed at -78 ° C, 2.5M n-Butyllithium, n-BuLi (20.0mL, 49.8mM) was slowly added and stirred to room temperature, followed by iodine ( iodine) (15.8 g, 62.3 mM) was added and stirred for 1 hour. After the reaction was completed, distilled water and dichloromethane (DCM) were added 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 13.2 g of the target compound 1-461-4 (yield: 69%).

2) 화합물 1-461-3의 제조2) Preparation of compound 1-461-3

Compound 1-461-4 (23.8g, 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), 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:Hexane=1:3) to obtain 19.3 g of the target compound 1-461-3 (yield: 81%).

3) 화합물 1-461-2의 제조3) Preparation of compound 1-461-2

Compound 1-461-3 (19.0 g, 41.5 mM), Palladium (II) acetate (Pd(OAc) ₂ ) (0.47 g, 2.1 mM), 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 13.9 g of the target compound 1-461-2 (yield: 79%).

4) 화합물 1-461-1의 제조4) Preparation of compound 1-461-1

Compound 1-461-2 (15.3g, 36.2mM) and triflic acid (80.1mL, 905.0mM) were dissolved in benzene-d6 (100mL) 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 13.5 g of the target compound 1-461-1 (yield: 85%).

5) 화합물 1-461의 제조5) Preparation of compound 1-461

Compound 1-461-1 (12.4 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- Butoxide (sodium tert-butoxide, t -BuONa) (5.4g, 56.4mM) was dissolved in xylene (200mL) 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 14.6 g of the target compound 1-461 (yield: 77%).

Intermediate A in Table 3 was used instead of 12-phenyl-12H-benzofuro[2,3-a]carbazole in Preparation Example 3. And, instead of 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine), intermediate B in Table 3 was used Thus, the target compounds in Table 3 below were synthesized in the same manner as in Preparation Example 3.

[Table 3]

제조예 4: 화합물 1-541의 제조Preparation Example 4: Preparation of Compound 1-541

In Preparation Example 1, instead of dibenzo [b, d] furan-4-amine (dibenzo [b, d] furan-4-amine), 2-chloro-6-fluoroaniline (2-chloro-6-fluoroaniline) Using, instead of 2-bromo-1-chloro-3-fluorobenzene (2-bromo-1-chloro-3-fluorobenzene), 1-bromo-9,9-dimethyl-9H-fluorene (1 -bromo-9,9-dimethyl-9H-fluorene) was used to synthesize the target compound in the same manner as in Preparation Example 1.

제조예 5: 화합물 1-545의 제조Preparation Example 5: Preparation of Compound 1-545

Instead of compound 1-1-5 in Preparation Example 2, 10-fluoro-12,12-dimethyl-11,12-dihydroindeno[2,1-a]carbazole (10-fluoro-12,12- A target compound was synthesized in the same manner as in Preparation Example 2 using dimethyl-11,12-dihydroindeno[2,1-a]carbazole).

제조예 6: 화합물 1-549의 제조Preparation Example 6: Preparation of compound 1-549

1) 화합물 1-549-5의 제조1) Preparation of Compound 1-549-5

(9-phenyl-9H-carbazol-2-yl)boronic acid (8.1g, 28.2mM), methyl 2-bromo-6-fluoro Benzoate (methyl 2-bromo-6-fluorobenzoate) (7.9g, 33.9mM), tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) (1.6g, 1.4mM) and potassium carbonate , K ₂ CO ₃ ) (7.8g, 56.2mM) was dissolved in 1,4-dioxane (200mL) and water (H ₂ O) (40mL), 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 9.6 g of the target compound 1-549-5 (yield: 86%).

2) 화합물 1-549-4의 제조2) Preparation of Compound 1-549-4

After dissolving compound 1-549-5 (5.0g, 12.6mM) in tetrahydrofuran (THF) (100mL), nitrogen was substituted at 0 ° C, and 3.0M methylmagnesium bromide (MeMgBr) was slowly added. Stir at room temperature for 3 hours. After dissolving the reactants in methylene chloride (MC) (100mL), boron trifluoride diethyl etherate (BF ₃ OEt ₂ ) (4.7mL, 37.9mM) was added and stirred for 1 hour. After the reaction was completed, distilled water and dichloromethane (DCM) were added 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 2.2 g of the target compound 1-549-4 (yield: 46%).

3) 화합물 1-549-3의 제조3) Preparation of compound 1-549-3

Compound 1-549-4 (5.3g, 14.1mM), 2-chloroaniline (2.2g, 16.9mM) and potassium tert-butoxide ( t -BuOK) (3.2g, 28.2 mM) was added to dimethyl sulfoxide (DMSO) (100 mL), dissolved, and refluxed for 12 hours. After the reaction was completed, extraction was performed by adding distilled water and dichloromethane (DCM) at room temperature. 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 1-549-3 (yield: 73%).

4) 화합물 1-549-2, 1-549-1, 1-549의 제조4) Preparation of compounds 1-549-2, 1-549-1, 1-549

The target compound was synthesized in the same manner as in the preparation of compounds 1-461-2, 1-461-1 and 1-461 in Preparation Example 3.

제조예 7: 화합물 1-553의 제조Preparation Example 7: Preparation of Compound 1-553

In Preparation Example 4, 2-([1 ,1'-biphenyl]-4-yl-d9)-4-chloro-6-(phenyl-d5)-1,3,5-triazine (2-([1,1'-biphenyl]-4- The target compound was synthesized in the same manner as in Preparation Example 4 using yl-d9)-4-chloro-6-(phenyl-d5)-1,3,5-triazine).

제조예 8: 화합물 1-557의 제조Preparation Example 8: Preparation of Compound 1-557

In Preparation Example 5, 2-([1 ,1'-biphenyl]-4-yl-d9)-4-chloro-6-(phenyl-d5)-1,3,5-triazine (2-([1,1'-biphenyl]-4- The target compound was synthesized in the same manner as in Preparation Example 5 using yl-d9)-4-chloro-6-(phenyl-d5)-1,3,5-triazine).

제조예 9: 화합물 1-559의 제조Preparation Example 9: Preparation of compound 1-559

In Preparation Example 6, 2-([1, 1'-biphenyl] -4-yl-d9) -4-chloro-6- (phenyl-d5) -1,3,5-triazine (2-([1,1'-biphenyl] -4-yl -d9) -4-chloro-6- (phenyl-d5) -1,3,5-triazine) was prepared in the same manner as in Preparation Example 6 to synthesize the target compound.

제조예 10: 화합물 2-3의 제조Preparation Example 10: Preparation of Compound 2-3

1) 화합물 2-3의 제조1) 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), it was refluxed for 24 hours. After the reaction was completed, extraction was performed by adding distilled water and dichloromethane (DCM) at room temperature. 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 10, Intermediate A of Table 4 was used instead of 3-bromo-1,1'-biphenyl, and 9-phenyl-9H,9'H -3,3'-bicarbazole (9-phenyl-9H,9'H-3,3'-bicarbazole), using Intermediate B of Table 4 below, in the same manner as in Preparation Example 10, Table 4 of target compounds were synthesized.

[Table 4]

제조예 11: 화합물 2-73의 제조Preparation Example 11: Preparation of compound 2-73

1) 화합물 2-73-2의 제조1) 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 ( 1,4-dioxane) (100mL) was dissolved and refluxed for 24 hours. After the reaction was completed, extraction was performed by adding distilled water and dichloromethane (DCM) at room temperature. 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) 화합물 2-73-1의 제조2) Preparation of Compound 2-73-1

After dissolving compound 2-73-2 (8.4g, 14.3mmol) in tetrahydrofuran (THF) (100mL), nitrogen substitution was performed 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 stirred at room temperature for 2 hours. After the reaction was completed, extraction was performed by adding distilled water and dichloromethane (DCM) at room temperature. 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) 화합물 2-73의 제조3) 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 ) and potassium carbonate (K ₂ CO ₃ ) (2.9 g, 21.0 mM) in toluene (100 mL), ethanol (EtOH) (20 mL) and water (H ₂ O) (20 mL). After melting, it was refluxed for 12 hours. After the reaction was completed, extraction was performed by adding distilled water and dichloromethane (DCM) at room temperature. 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%).

제조예 12: 화합물 3-2의 제조Preparation Example 12: Preparation of Compound 3-2

1) 화합물 3-2-1의 제조1) 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'-D ₉ ) (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. 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 13.9 g of the target compound 3-2-1 (yield: 94%).

2) 화합물 3-2의 제조2) 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 12. That is, when compound A and compound A' are the same, preparation of compound 3-2-1 may be omitted.

In Preparation Example 12, 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 in Table 5 was used, and 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'), using Intermediate A' of Table 5 below, in the same manner as in Preparation Example 12. The target compounds in Table 5 were synthesized.

[Table 5]

제조예 13: 화합물 3-26의 제조Preparation Example 13: Preparation of compound 3-26

1) 화합물 3-26-2의 제조1) Preparation of compound 3-26-2

9H,9'H-3,3'-bicarbazole (12.0g, 36.2mM) and triflic acid (80.1mL, 905.0mM) After dissolving in benzene-d6 (100mL), it was refluxed at 40℃. 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) 화합물 3-26-1의 제조2) 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 -potassium phosphate, K ₃ PO ₄ ) (3.3g, 31.6mM) was dissolved in 1,4-dioxane (100mL), and then refluxed for 24 hours. After the reaction was completed, extraction was performed by adding distilled water and dichloromethane (DCM) at room temperature. 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) 화합물 3-26의 제조2) Preparation of compound 3-26

Compound 3-26-1 (14.0g, 28.0mM), 4-bromo-1,1'-biphenyl (B') (6.8g, 28.0mM), 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), it was refluxed at 125℃ 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 15.8 g 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 13. That is, when Compound B and Compound B' are the same, the preparation of Compound 3-26-1 may be omitted.

In Preparation Example 13, 4-bromo-1,1'-biphenyl (4-bromo-1,1'-biphenyl) instead of (B), using the intermediate B of Table 6, 4-bromo -1,1'-biphenyl (4-bromo-1,1'-biphenyl) (B'), using Intermediate B' in Table 6, in the same manner as in Preparation Example 13, to the purpose of Table 6 compounds were synthesized.

[Table 6]

제조예 14: 화합물 3-50의 제조Preparation Example 14: Preparation of Compound 3-50

1) 화합물 3-50-1의 제조1) 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℃ for 8 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 15.9g of the target compound 3-50-1 (yield: 89%).

2) 화합물 3-50의 제조2) Preparation of compound 3-50

Compound 3-50-1 (23.0g, 36.2mM) and triflic acid (80.1mL, 905.0mM) were dissolved in benzene-d6 (100mL) 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 16.9g of the target compound 3-50 (yield: 70%).

In Preparation Example 14, 9-([1,1'-biphenyl]-4-yl)-9H,9'H-3,3'-bicarbazole (9-([1,1'-biphenyl Instead of] -4-yl) -9H,9'H-3,3'-bicarbazole), intermediate C in Table 7 was used, and 4-bromo-1,1'-biphenyl (4-bromo-1 , 1'-biphenyl), the target compounds in Table 7 were synthesized in the same manner as in Preparation Example 14 using Intermediate C' in Table 7 below.

[Table 7]

The remaining compounds other than the compounds described in Preparation Examples 1 to 14 and Tables 1 to 7 were also prepared in the same manner as described in the above Preparation Examples, and the synthesis results are shown in Table 8 below. Table 8 below is a measurement value of ¹ H NMR (CDCl ₃ , 200 Mz), and Table 9 below is a measurement value of FD-mass spectrometer (FD-MS: Field desorption mass spectrometry).

[Table 8]

[Table 9]

<실험예><Experimental example>

실험예 1Experimental Example 1

(1)(One) 유기 발광 소자의 제조Manufacturing of organic light emitting devices

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)(2) 유기 발광 소자의 구동 전압 및 발광 효율Driving Voltage and Luminous Efficiency of Organic Light-Emitting Devices

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 , the lifetime T ₉₀ , which is the time to reach 90% of the initial luminance, 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 10.

[Table 10]

[Comparative compound Ref. 1 to Ref.13]

From the results of Table 10, 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 13.

The heterocyclic compound according to the present invention is a deuterium-substituted compound, and the compounds of Comparative Examples 1 to 13 are hydrogen-substituted or partially deuterium-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, the deuterium-substituted heterocyclic compound 1-184 according to the present invention is a comparative example compound substituted with hydrogen due to molecular stability and non-crystallinity Ref. It can be seen that the driving voltage and lifetime are improved compared to 1, 2, 3, 4, 6, 8, 9, 10, 11, 12 and 13, and the loss of energy due to the low vibration energy of the deuterium-substituted heterocyclic compound By minimizing and facilitating energy transfer to the dopant, it was possible to improve the luminous efficiency of the organic light emitting device.

In addition, the deuterium-substituted heterocyclic compound 1-549 according to the present invention is a comparative example compound Ref. 5, the compound 1-549 is different in that it is a compound in which R1 to R12 are substituted with deuterium in the compound of Formula 1 (hereinafter, referred to as a compound in which condensed carbazole is substituted with deuterium), and the present invention Heterocyclic compound 1-181 substituted with deuterium according to Comparative Example Compound Ref. 7, compounds 1-181 are compounds in which R1 to R12 are substituted with deuterium in the compound of Formula 1 (hereinafter, referred to as a compound in which condensed carbazole is substituted with deuterium) and Ar1 to R12 in the compound of Formula 1 It differs in that Ar3 is a compound substituted with deuterium (hereinafter, referred to as a compound having an aryl group substituted with deuterium).

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 1-181 and 1-549 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. 5 and 7 confirmed that the deuterium substituted only for the aryl group among the substituents did not contribute to the stabilization of the radical cation of the condensed carbazole. Therefore, it was confirmed that the lifespan of the organic light emitting device using compounds 1-181 and 1-549 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 1-349 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 1-184, in which only condensed carbazole is substituted with deuterium, has an increased intermolecular interaction than compound 1-349, resulting in a smaller intermolecular distance and improved mobility, thereby improving the driving voltage of the organic light emitting device.

<실험예 2><Experimental Example 2>

A glass substrate coated with a thin film of indium tin oxide (ITO) to 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.

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.

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 , the lifetime T ₉₀ , which is the time to reach 90% of the initial luminance, 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 11.

[Table 11]

In the results of Table 11, the compound represented by Formula 1, which is a heterocyclic compound of the present invention, 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 When mixed and deposited, 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

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, each independently represent NAr1, O, S or CR13R14, at least two or more of X1, X2 and X3 are NAr1, the plurality of Ar1s are different from each other, any of these One is a group represented by Formula 1-1 below,

Ar1 is 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; And it is selected from the group consisting of 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 and 1-b, a heterocyclic compound:

[Formula 1-a]

In Formula 1-a,

X3 is O, S or CR13R14;

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

Ar1' is the same as the definition of Ar1,

Ar1 and Ar1' are different from each other, and one of them is a group represented by Formula 1-1;

[Formula 1-b]

In Formula 1-b,

X2 is O, S or CR13R14;

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

Ar1' is the same as the definition of Ar1,

Ar1 and Ar1' are different from each other, and either one of them is a group represented by Formula 1-1.
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 2,

Ar1 and Ar1' are each independently any one of a group represented by Formula 1-1 and a group represented by Formulas 1-2-a to 1-2-g below, a heterocyclic compound:

[Formula 1-1]

[Formula 1-2-a]

[Formula 1-2-b]

[Formula 1-2-c]

[Formula 1-2-d]

[Formula 1-2-e]

[Formula 1-2-f]

[Formula 1-2-g]

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 a substituted or unsubstituted C2 to C30 heteroaryl group,

L1, L2, a and b are as defined in claim 1 above,

In Formula 1-2-a to Formula 1-2-g,

R21 to R60 are hydrogen or deuterium;

X4 is O, S or CR61R62;

R61 and R62 are methyl groups;

p, q and r are the same as or different from each other, and are each independently an integer of 3 to 5.
According to claim 5,

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 5,

In Formulas 1-2-a to 1-2-g, the content of deuterium in R21 to R60 is 1% to 100% based on the total number of hydrogen atoms and deuterium atoms, 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 8,

Of the heterocyclic compound represented by Formula 1, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms is 30% 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 10, an organic light emitting device.
According to claim 11,

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 11,

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 11,

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 11,

The organic material layer further comprises a heterocyclic compound represented by Formula 2 below, an organic light emitting device:

[Formula 2]

In Formula 2,

R101 to R114 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)R201R202; and -SiR201R202R203; wherein R201, R202, and R203 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 15,

The content of deuterium based on the total number of hydrogen atoms and deuterium atoms in the heterocyclic compound represented by Formula 2 is 30% to 100%, or deuterium is not included, the organic light emitting device.
According to claim 15,

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 15,

At least one of the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 has a deuterium content greater than 0% and less than 100%, an organic light emitting device.
A composition for an organic material layer of an organic light emitting device comprising the heterocyclic compound represented by Formula 1 according to any one of claims 1 to 10 and the heterocyclic compound represented by Formula 2 below:

[Formula 2]

In Formula 2,

R101 to R114 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)R201R202; and -SiR201R202R203; wherein R201, R202, and R203 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 19,

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, which is a composition for an organic layer of an organic light emitting device.