KR20220139504A - Heterocyclic compound, organic light emitting device comprising the same, manufacturing method of the same and composition for organic layer of organic light emitting device - Google Patents

Abstract

The present invention relates to a heterocyclic compound represented by chemical formula 1, an organic light emitting device including the same, a method for manufacturing the same, and a composition for an organic material layer. The compound described in the present specification can be used as a material for an organic material layer of the organic light emitting device. In particular, the compound can be used as the material for the light emitting layer of the organic light emitting device.

Description

Heterocyclic compound, organic light emitting device including same, manufacturing method thereof, and composition for organic material layer

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

The organic light emitting device is a type of self-emission type display device, and has 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 a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes combine in the organic thin film to form a pair, and then disappear and emit light. The organic thin film may be composed of a single layer or multiple layers, if necessary.

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

In order to improve the performance, lifespan or efficiency of the organic light emitting device, the development of a material for the organic thin film is continuously required.

US Patent No. 4,356,429

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

In order to achieve the above object,

The present invention provides a heterocyclic compound represented by the following formula (1).

[Formula 1]

In Formula 1,

Wherein X1 and X2 are the same as or different from each other, each independently O or S,

wherein R1 to R9 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; a substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; and -NR101R102, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle, wherein R101, R102 and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

The N-Het is a substituted or unsubstituted, C2 to C60 monocyclic or polycyclic heterocyclic group containing one or more N.

In addition, the present invention is a first electrode;

An organic light emitting device comprising a; at least one organic material layer provided between the first electrode and the second electrode,

At least one layer of the organic material layer provides an organic light emitting device comprising the heterocyclic compound represented by Formula 1 above.

In addition, the present invention provides an organic light emitting device wherein the organic material layer further comprises a heterocyclic compound represented by the following formula (6).

[Formula 6]

In Formula 6,

Wherein X21 and X22 are the same as or different from each other, and each independently O or S,

wherein R45 to R59 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; a substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; and -NR101R102, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle, wherein R101, R102 and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

L is a direct bond; a substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group.

In addition, the present invention provides a composition for an organic material layer of an organic light emitting device comprising the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 6 above.

In addition, the present invention comprises the steps of 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,

It provides a method for manufacturing an organic light emitting device, wherein the forming of the organic material layer includes the step of forming one or more organic material layers using the composition for an organic material layer of the organic light emitting device.

The compound described herein can be used as 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, a light emitting layer material, an electron transport layer material, a hole blocking layer material, an electron injection layer material, etc. in the organic light emitting device. In particular, the compound may be used as a material for the light emitting layer of the organic light emitting device.

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

More specifically, the heterocyclic compound represented by Chemical Formula 1 of the present invention has high thermal stability and has a molecular weight and a band gap suitable for use in a light emitting layer of an organic light emitting device. This facilitates the formation of the emission layer of the organic light emitting device, and prevents loss of electrons and holes in the emission layer, thereby helping to form an effective recombination region. In addition, since the hole blocking phenomenon occurring in the dopant can be solved, the driving voltage can be lowered, and the luminous efficiency and lifespan characteristics can be improved.

1 to 3 are views schematically showing a stacked structure of an organic light emitting device according to an embodiment of the present invention, respectively.

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 position at which the hydrogen atom is substituted, that is, the position where the substituent is substitutable, is not limited. , 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 C1 to C60 straight-chain or branched alkyl; C2 to C60 linear or branched alkenyl; C2 to C60 linear 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 that it is substituted or unsubstituted with one or more substituents, or substituted or unsubstituted with a substituent to which two or more substituents selected from the above-exemplified substituents are connected.

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

In the present specification, the alkyl group includes a straight or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms in the alkyl group may be 1 to 60, specifically 1 to 40, 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, and the like, 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 carbon number of the alkenyl group may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20. Specific examples include a vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 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 are not limited thereto.

In the present specification, the alkynyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The carbon number of the alkynyl group may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C20. 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. may be It is not limited.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic refers to 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 be a different type of ring group, for example, a heterocycloalkyl group, an aryl group, a heteroaryl group, or the like. The number of carbon atoms of the cycloalkyl group may be 3 to 60, specifically 3 to 40, 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, and the like, but is 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, polycyclic refers to 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 be a different type of ring group, for example, a cycloalkyl group, an aryl group, a heteroaryl group, or the like. The heterocycloalkyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, 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 by other substituents. Here, polycyclic means a group in which an aryl group is directly connected to another ring group or condensed. Here, the other ring group may be an aryl group, but may be a different type of ring group, for example, a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, or the like. The aryl group includes a spiro group. The carbon number of the aryl group may be 6 to 60, specifically 6 to 40, more specifically 6 to 25. Specific examples of the aryl group include a phenyl group, a biphenyl group, a triphenyl group, a naphthyl group, an anthryl group, a chrysenyl group, a phenanthrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a phenalenyl group, a pyrethyl 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 phosphine oxide group is represented by -P(=O)R101R102, R101 and R102 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specifically, it may be substituted with an aryl group, and the above-described examples may be applied to the aryl group. For example, the phosphine oxide group includes a diphenylphosphine oxide group, a dinaphthylphosphine oxide group, and the like, but is not limited thereto.

In the present specification, the silyl group is a substituent including Si and the Si atom is directly connected as a radical, and is represented by -SiR101R102R103, R101 to R103 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specific examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. It is not limited.

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

,

, When the fluorenyl group is substituted,

,

,

,

,

,

등이 될 수 있으나, 이에 한정되는 것은 아니다.

,

,

,

and the like, 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 ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic refers to 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 be a different type of ring group, for example, a cycloalkyl group, a heterocycloalkyl group, an aryl group, or the like. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, 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, 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, quinazolylyl group, naphthyridyl group, acridinyl group, phenanthridyl group 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, Phenoxazinyl group, phenanthridyl group, imidazopyridinyl group, thienyl group, indolo[2,3-a]carbazolyl group, indolo[2,3-b]carbazolyl group, indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenothiazinyl group, phthalazinyl group, naphthylidinyl group, phenanthrolinyl group, Benzo[c][1,2,5]thiadiazolyl group, 5,10-dihydrodibenzo[b,e][1,4]azasilinyl, 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 ] a 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; diarylamine group; diheteroarylamine group; an alkylarylamine group; an alkyl heteroarylamine group; And it may be selected from the group consisting of an arylheteroarylamine group, 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, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluorene There is a nylamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group, and the like, but is not limited thereto.

In the present specification, the arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied. In addition, the heteroarylene group means that the heteroaryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the heteroaryl group described above may be applied.

As used herein, the "adjacent" group means a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom in which the substituent is substituted. can For example, two substituents substituted at an ortho position 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 a substituent is not indicated in the chemical formula or compound structure" means that a hydrogen atom is bonded to a carbon atom. However, since deuterium ( ² H, Deuterium) is an isotope of hydrogen, some hydrogen atoms may be deuterium.

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

In one embodiment of the present invention, in "when a substituent is not indicated in the chemical formula or compound structure", "the content of deuterium is 0%", "the content of hydrogen is 100%", "the substituents are all hydrogen", etc. If deuterium is not explicitly excluded, hydrogen and deuterium may be used in combination in the compound.

In one embodiment of the present invention, deuterium is an element having a deuteron consisting of one proton and one neutron as one of the isotopes of hydrogen 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 having the same atomic number (Z) but different mass numbers (A) have the same number of protons, but neutrons It can also be interpreted as elements with different numbers of (neutrons).

In one embodiment of the present invention, the meaning of the content of specific substituents T% is T2 when the total number of substituents that the basic compound can have is defined as T1, and the number of specific substituents is defined as T2. It can be defined as /T1Х100 = T%.

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

The 20% content of deuterium in the phenyl group represented by means that the total number of substituents that the phenyl group can 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 a deuterium atom, that is, has 5 hydrogen atoms.

In the present invention, the content of deuterium in the heterocyclic compound represented by Formula 1 may be 0 to 100%, more preferably 30 to 100%.

In the present invention, C6 to C60 aromatic hydrocarbon ring means a compound including an aromatic ring consisting of C6 to C60 carbons and hydrogen, for example, benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene, etc., but are not limited thereto, and aromatic hydrocarbon ring compounds known in the art as satisfying the above carbon number include all

The present invention provides a heterocyclic compound represented by the following formula (1).

[Formula 1]

In Formula 1,

Wherein X1 and X2 are the same as or different from each other, each independently O or S,

wherein R1 to R9 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; a substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; and -NR101R102, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle, wherein R101, R102 and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

The N-Het is a substituted or unsubstituted, C2 to C60 monocyclic or polycyclic heterocyclic group containing one or more N.

In one embodiment of the present invention, R1 to R9 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C2 to C30 alkenyl group; a substituted or unsubstituted C2 to C30 alkynyl group; a substituted or unsubstituted C1 to C30 alkoxy group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C2 to C30 heterocycloalkyl group; a substituted or unsubstituted C6 to C30 aryl group; a substituted or unsubstituted C2 to C30 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; Or it may be a group represented by -NR101R102.

In another embodiment of the present invention, R1 to R9 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; a substituted or unsubstituted C2 to C20 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; Or it may be a group represented by -NR101R102.

In another embodiment of the present invention, R1 to R9 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C6 to C20 aryl group; a substituted or unsubstituted C2 to C20 heteroaryl group; Or it may be a group represented by -NR101R102.

In another embodiment of the present invention, R1 to R9 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted phenyl group, a naphthyl group, a carbazolyl group, a benzocarbazolyl group; triphenylamine group; phenylcarbazolyl group; Alternatively, it may be a group represented by -NR101R102, wherein R101 and R102 are the same as or different from each other, and may be a substituted or unsubstituted C6 to C20 aryl group.

In one embodiment of the present invention, the N-Het may be a substituted or unsubstituted, C2 to C60 monocyclic or polycyclic heterocyclic group containing 1 or more and 3 or less N.

In another embodiment of the present invention, the N-Het may be a substituted or unsubstituted, C2 to C30 monocyclic or polycyclic heterocyclic group containing 1 or more and 3 or less N.

In another embodiment of the present invention, the N-Het may be a substituted or unsubstituted, C2 to C30 monocyclic or polycyclic heterocyclic group containing 2 or more and 3 or less N.

In another embodiment of the present invention, the N-Het may be a substituted or unsubstituted, C2 to C20 monocyclic or polycyclic heterocyclic group containing 2 or more and 3 or less N.

In one embodiment of the present invention, the content of deuterium based on the total number of hydrogen atoms and deuterium atoms in Formula 1 is 0% or more, 10% or more, 20% or more, 30% or more, 40% or more, or 50% or more. and may be 100% or less, 90% or less, 80% or less, 70% or less, 60% or less.

In another embodiment of the present invention, the content of deuterium may be 30% to 100% based on the total number of hydrogen atoms and deuterium atoms in Formula 1 above.

In another embodiment of the present invention, the content of deuterium may be 30% to 80% based on the total number of hydrogen atoms and deuterium atoms in Formula 1 above.

In another embodiment of the present invention, the content of deuterium may be 50% to 60% based on the total number of hydrogen atoms and deuterium atoms in Formula 1 above.

In one embodiment of the present invention, N-Het may be a substituent represented by the following formula (2).

[Formula 2]

In Formula 2,

Wherein X11 to X13 are the same as or different from each other, and each independently is N or CR13,

Wherein X11 to X13 are at least two or more N,

wherein R11 to R13 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; a substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; and -NR101R102, wherein R101, R102, and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

L is a direct bond; a substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group.

In an embodiment of the present invention, R11 to R13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C2 to C30 alkenyl group; a substituted or unsubstituted C2 to C30 alkynyl group; a substituted or unsubstituted C1 to C30 alkoxy group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C2 to C30 heterocycloalkyl group; a substituted or unsubstituted C6 to C30 aryl group; a substituted or unsubstituted C2 to C30 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; Or it may be a group represented by -NR101R102.

In another embodiment of the present invention, R11 to R13 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; a substituted or unsubstituted C2 to C20 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; Or it may be a group represented by -NR101R102.

In another embodiment of the present invention, R11 to R13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C6 to C20 aryl group; a substituted or unsubstituted C2 to C20 heteroaryl group; Or it may be a group represented by -NR101R102.

In one embodiment of the present invention, L is a direct bond; a substituted or unsubstituted C6 to C30 arylene group; Or it may be a substituted or unsubstituted C2 to C30 heteroarylene group.

In another embodiment of the present invention, L is a direct bond; a substituted or unsubstituted C6 to C20 arylene group; Or it may be a substituted or unsubstituted C2 to C20 heteroarylene group.

In another embodiment of the present invention, L is a direct bond; Or it may be a substituted or unsubstituted phenylene group or a naphthylene group.

Specific examples of L are shown below, but are not limited to these examples.

In one embodiment of the present invention, Chemical Formula 2 may be represented by any one of Chemical Formulas 3 to 5 below.

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5,

wherein R21 to R28 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; a substituted or unsubstituted C2 to C60 heteroaryl group; and -P(=0)R101R102; -SiR101R102R103; and -NR101R102, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle, wherein R101, R102 and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

The definition of L is the same as the definition in Formula 2 above.

In one embodiment of the present invention, R21 to R28 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C2 to C30 alkenyl group; a substituted or unsubstituted C2 to C30 alkynyl group; a substituted or unsubstituted C1 to C30 alkoxy group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C2 to C30 heterocycloalkyl group; a substituted or unsubstituted C6 to C30 aryl group; a substituted or unsubstituted C2 to C30 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; and -NR101R102, or two or more groups adjacent to each other may combine with each other to form a substituted or unsubstituted C6 to C30 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C30 heterocycle.

In another embodiment of the present invention, R21 to R28 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; a substituted or unsubstituted C2 to C20 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; and -NR101R102, or two or more groups adjacent to each other may combine with each other to form a substituted or unsubstituted C6 to C20 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C20 hetero ring.

In another embodiment of the present invention, R21 to R28 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C6 to C20 aryl group; Or a substituted or unsubstituted C2 to C20 heteroaryl group selected from the group consisting of, or two or more adjacent groups are bonded to each other to form a substituted or unsubstituted C6 to C20 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C20 Heterocyclic rings may be formed.

In one embodiment of the present invention, R21 and R22 are the same as or different from each other, and each independently 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, R21 and R22 are the same as or different from each other, and each independently 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, R21 and R22 are the same as or different from each other, and each independently 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, R21 and R22 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group; Alternatively, it may be a substituted or unsubstituted carbazolyl group, a dibenzofuranyl group, or a dibenzothiophenyl group.

In an embodiment of the present invention, R26 to R28 are the same as or different from each other, and at least two of R26 to R28 are each independently a substituted or unsubstituted C6 to C60 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another embodiment of the present invention, R26 to R28 are the same as or different from each other, and at least two of R26 to R28 are each independently a substituted or unsubstituted C6 to C30 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C30 heteroaryl group.

In another embodiment of the present invention, R26 to R28 are the same as or different from each other, and at least two of R26 to R28 are each independently a substituted or unsubstituted C6 to C20 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C20 heteroaryl group.

In another embodiment of the present invention, R26 to R28 are the same as or different from each other, and at least two of R26 to R28 are each independently a substituted or unsubstituted phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group ; Or it may be a substituted or unsubstituted dibenzothiophenyl group.

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

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

In Formulas 4-1 to 4-4,

wherein R31 to R48 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; a substituted or unsubstituted C2 to C60 heteroaryl group; and -P(=0)R101R102; -SiR101R102R103; and -NR101R102, wherein R101, R102, and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

The Y1 and Y2 are the same as or different from each other, and each independently O or S,

The definition of L is the same as the definition in Formula 2 above.

In one embodiment of the present invention, R31 to R48 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C2 to C30 alkenyl group; a substituted or unsubstituted C2 to C30 alkynyl group; a substituted or unsubstituted C1 to C30 alkoxy group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C2 to C30 heterocycloalkyl group; a substituted or unsubstituted C6 to C30 aryl group; a substituted or unsubstituted C2 to C30 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; Or it may be a group represented by -NR101R102.

In another embodiment of the present invention, R31 to R48 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; a substituted or unsubstituted C2 to C20 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; Or it may be a group represented by -NR101R102.

In another embodiment of the present invention, R31 to R48 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; 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, R31 to R33 are the same as or different from each other, and at least two of R31 to R33 are each independently a substituted or unsubstituted C6 to C60 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another embodiment of the present invention, R31 to R33 are the same as or different from each other, and at least two of R31 to R33 are each independently a substituted or unsubstituted C6 to C30 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C30 heteroaryl group.

In another embodiment of the present invention, R31 to R33 are the same as or different from each other, and at least two of R31 to R33 are each independently a substituted or unsubstituted C6 to C20 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C20 heteroaryl group.

In another embodiment of the present invention, R31 to R33 are the same as or different from each other, and at least two of R31 to R33 are each independently a substituted or unsubstituted phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group; Or it may be a substituted or unsubstituted carbazolyl group, dibenzofuranyl group.

In one embodiment of the present invention, any one of R34 to R38 is a substituted or unsubstituted C6 to C60 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another embodiment of the present invention, any one of R34 to R38 is a substituted or unsubstituted C6 to C30 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C30 heteroaryl group.

In another embodiment of the present invention, any one of R34 to R38 is a substituted or unsubstituted C6 to C20 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C20 heteroaryl group.

In another embodiment of the present invention, any one of R34 to R38 may be a substituted or unsubstituted phenyl group, a biphenyl group, or a terphenyl group.

In one embodiment of the present invention, any one of R39 to R43 is a substituted or unsubstituted C6 to C60 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another embodiment of the present invention, any one of R39 to R43 is a substituted or unsubstituted C6 to C30 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C30 heteroaryl group.

In another embodiment of the present invention, any one of R39 to R43 is a substituted or unsubstituted C6 to C20 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C20 heteroaryl group.

In another embodiment of the present invention, any one of R39 to R43 may be a substituted or unsubstituted phenyl group, a biphenyl group, or a terphenyl group.

In one embodiment of the present invention, any one of R44 to R48 is a substituted or unsubstituted C6 to C60 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C60 heteroaryl group.

In another embodiment of the present invention, any one of R44 to R48 is a substituted or unsubstituted C6 to C30 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C30 heteroaryl group.

In another embodiment of the present invention, any one of R44 to R48 is a substituted or unsubstituted C6 to C20 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C20 heteroaryl group.

In another embodiment of the present invention, any one of R44 to R48 may be a substituted or unsubstituted phenyl group, a biphenyl group, or a terphenyl group.

In one embodiment of the present invention, Chemical Formula 1 may be a heterocyclic compound represented by any one of the following compounds.

In addition, by introducing various substituents into the structure of Formula 1, compounds having intrinsic properties of the introduced substituents can be synthesized. For example, a substituent mainly used for a hole injection layer material, an electron blocking layer material, a hole transport layer material, a light emitting layer material, an electron transport layer material, a hole blocking layer material, and a charge generating layer material used in manufacturing an organic light emitting device is introduced into the core structure By doing so, a material that satisfies the conditions required by each organic material layer can be synthesized.

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

Also, the present invention

a first electrode;

a second electrode provided to face the first electrode; and

An organic light emitting device comprising a; at least one organic material layer provided between the first electrode and the second electrode,

At least one layer of the organic material layer relates to an organic light emitting device comprising the heterocyclic compound represented by Formula 1 above.

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, 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 Formula 1 may be used as a material of the red organic light emitting device.

In another 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 light emitting layer material of the red organic light emitting device.

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

The organic light emitting device of the present invention may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except for forming one or more organic material layers using the above-described heterocyclic compound.

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

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but 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, an electron blocking layer, a hole transport layer, a light emitting layer, an electron transport layer, a hole blocking layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.

In the organic light emitting device according to an embodiment of the present invention, the organic material layer including the heterocyclic compound represented by Formula 1 further includes a heterocyclic compound represented by the following Formula 6 It provides an organic light emitting device .

[Formula 6]

In Formula 6,

Wherein X21 and X22 are the same as or different from each other, and each independently O or S,

wherein R51 to R59 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; a substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; and -NR101R102, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle, wherein R101, R102 and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

The definition of L is the same as the definition in Formula 2 above.

In one embodiment of the present invention, R51 to R59 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C1 to C60 alkyl group; 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, R51 to R59 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; 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 one embodiment of the present invention, R51 to R59 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C1 to C20 alkyl group; 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, R51 to R59 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group; It may be a substituted or unsubstituted phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, an isochrysenyl group;

When the compound represented by Formula 1 and the compound represented by Formula 6 are included at the same time, better efficiency and lifespan effect are exhibited. From this, when both compounds are included at the same time, it can be expected that an exciplex phenomenon occurs.

The exciplex phenomenon is a phenomenon in which energy having the size of the HOMO energy level of the donor (p-host) and the LUMO energy level of the acceptor (n-host) is emitted through electron exchange between two molecules. When an exciplex phenomenon occurs between two molecules, reverse intersystem crossing (RISC) occurs, thereby increasing the internal quantum efficiency of fluorescence to 100%. When a donor (p-host) with good hole transport ability and an acceptor (n-host) with good electron transport ability are used as hosts of the emission layer, holes are injected into the p-host and electrons are transferred to the n-host Since it is injected into That is, when the compound represented by Formula 1 is used as the acceptor and the compound represented by Formula 6 is used as the donor, excellent device characteristics are exhibited.

In one embodiment of the invention, the heterocyclic compound represented by Formula 6 may be any one selected from the following compounds.

In addition, one embodiment of the present invention provides a composition for an organic material layer of an organic light emitting device comprising the heterocyclic compound represented by Formula 1, and the heterocyclic compound represented by Formula 6 above.

Specific details of the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 6 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 6 in the composition for an organic material layer of the organic light emitting device may be 1:10 to 10:1, and , 1: 8 to 8: 1, may be 1: 5 to 5: 1, may be 1: 2 to 2: 1, but is not limited thereto.

The composition for the organic material layer of the organic light emitting device may be used when forming the organic material of the organic light emitting device, and in particular, it may 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 Formula 1, and a heterocyclic compound represented by Formula 6, 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.

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

The L is an anionic bidentate ligand coordinated to the M by sp ² carbon and a hetero atom, and X may function to trap electrons or holes. Non-limiting examples of L include 2-(1-naphthyl)benzoxazole, (2-phenylbenzoxazole), (2-phenylbenzothiazole), (2-phenylbenzothiazole), (7,8 -benzoquinoline), (thiophenepyrizine), phenylpyridine, benzothiophenepyrizine, 3-methoxy-2-phenylpyridine, thiophenepyrizine, tolylpyridine, and the like. Non-limiting examples of X′ and X″ include acetylacetonate (acac), hexafluoroacetylacetonate, salicylidene, picolinate, 8-hydroxyquinolinate, and the like.

Specific examples of the phosphorescent dopant are shown below, but are not limited thereto.

In one embodiment of the present invention, the organic material layer includes the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 6, and may be used together with an iridium-based dopant.

In one embodiment of the present invention, as the iridium-based dopant, (piq) ₂ (Ir)(acac) may be used as the red phosphorescent 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 the electron transport layer may include the heterocyclic compound.

In the organic light emitting device according to another embodiment, the organic material layer may include an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer may include the heterocyclic compound.

In the organic light emitting device according to another embodiment, 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 the heterocyclic compound.

In the organic light emitting device according to another embodiment, the organic material layer may include a light emitting layer, and the light emitting layer may include the heterocyclic compound.

An organic light emitting device according to an embodiment of the present invention includes a light emitting layer, a hole injection layer, and a hole transport layer. It may further include one or more layers selected from the group consisting of an electron injection layer, an electron transport 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 the structure of an organic light emitting device known in the art may also be applied to the present application.

Referring 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 illustrated. 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 in which the organic material layer is multi-layered. The organic light emitting diode according to FIG. 3 includes a hole injection layer 301 , a hole transport layer 302 , a light emitting 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 if necessary, the remaining layers except for the light emitting layer may be omitted, and other necessary functional layers may be further added.

In one embodiment of the present invention, the method comprising: preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer, wherein the forming of the organic material layer is 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 of manufacturing an organic light emitting device comprising the step of.

In one embodiment of the present invention, the step of forming the organic material layer is a pre-mixed (pre-mixed) heterocyclic compound represented by the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 6, thermal vacuum deposition method It may be formed using.

The pre-mixed means, before depositing the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 6 on the organic layer, first mixing the materials and putting them in one source and mixing.

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

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

The organic material layer including the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 6 at the same time 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 6 are exemplified below, but these are for illustration only. It is not intended to limit the scope, and may be substituted with materials known in the art.

Materials having a relatively large work function may be used as the anode material, and transparent conductive oxides, metals, conductive polymers, or the like may be used. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO2: a combination of metals and oxides such as 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 a metal, metal oxide, conductive polymer, or the like may be used. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multi-layered material such as LiF/Al or LiO2/Al, but is 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 Advanced Material, 6, p.677 (1994). Starburst-type amine derivatives described, such as tris(4-carbazolyl-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), soluble conductive polymer polyaniline/dodecylbenzenesulfonic acid, or Poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), polyaniline/Camphor sulfonic acid or Polyaniline/Poly(4-styrene-sulfonate) (Polyaniline/Poly(4-styrene-sulfonate)) may be used.

As the hole transport layer material, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, etc. may be used, and a low molecular weight or high molecular material may be used.

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

As the 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 the light emitting layer material, and if necessary, two or more light emitting materials may be mixed and used. In this case, two or more light emitting materials may be deposited and used as individual sources, or may be premixed and deposited as a single source for use. In addition, although a fluorescent material can be used as a light emitting layer material, it can also be used as a phosphorescent material. As the light emitting layer material, a material that emits light by combining holes and electrons injected from the anode and the cathode, respectively, may be used alone, but materials in which the host material and the dopant material together participate in light emission may be used.

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

The organic light emitting device according to an embodiment of the present invention may be a top emission type, a back emission type, or a double side emission type depending on a 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 examples are presented to help the understanding of the present invention, but the following examples are only provided for easier understanding of the present invention, and the present invention is not limited thereto.

<Production Example>

Preparation Example 1. Preparation of compound 42

Preparation Example 1-1. Preparation of compound 42-2

Compound 42-1 (A) 30g (0.081mol, 1eq), phenylboronic acid (B) 11.8g (0.096mol, 1.2q), potassium carbonate (K ₂ CO ₃ ) 26.7g (0.194mol, 2.4) eq) and tetrakis(triphenylhosphine)palladium(0)(tetrakis(triphenylhosphine)palladium(0), Pd(PPh ₃ ) ₄ ) 4.6 g (0.004 mol, 0.05 eq) of 1,4-dioxane (1 ,4-Dioxane) was added to 360 mL and distilled water 90 mL and stirred at 90° C. for 8 hours. After the reaction was terminated by adding distilled water, the reaction solution was extracted with dichloromethane and distilled water, and moisture was removed using MgSO ₄ . Then, it was separated by a silica gel column to obtain 25 g of compound 43-2 (yield 84%).

Preparation 1-2. Preparation of compound 42-3

Compound 42-2 25g (0.067mol, 1eq), 4,4,4',4',5,5,5',5'-octamethyl-2,2'- ratio (1,3,2-dioxa Bororane) (4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane)) 25.8g (0.101mol, 1.5eq ), Bis(dibenzylideneacetone)palladium, Pd(dba) ₂ ) 1.9 g (0.003 mol, 0.05 eq) and Tricyclohexylphosphine (P(Cy) ₃ ) 1.9 g (0.007 mol) , 0.1eq) was dissolved in 250 mL of 1,4-dioxane (1,4-Dioxane) and stirred at 90° C. for 8 hours. After the reaction was terminated by adding distilled water, the reaction solution was extracted with dichloromethane and distilled water, and moisture was removed using MgSO ₄ . Then, it was separated by a silica gel column to obtain 20 g of compound 42-3 (yield 64%).

Preparation Example 1-3. Preparation of compound 43

Compound 42-3 10g (0.022ol, 1eq), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (2-( [1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine) (C) 8.2 g (0.024 mol, 1.1 eq), potassium carbonate (K ₂ CO ₃ ) 6.6 g (0.194 mol, 2.2 eq) and tetrakis (triphenylphosphine) palladium (0) (tetrakis (triphenylhosphine) palladium (0), Pd (PPh ₃ ) ₄ ) 1.3 g (0.001 mol, 0.05 eq) 1,4-Dioxane (1,4-Dioxane) was added to 120 mL and distilled water 30 mL, and stirred at 90° C. for 8 hours. After the reaction was terminated by adding distilled water, the reaction solution was extracted with dichloromethane and distilled water, and moisture was removed using MgSO ₄ . Then, it was separated by a silica gel column to obtain 10 g of compound 43 (yield 72%).

Preparation Example 2. Preparation of compound 63

Preparation Example 2-1. Preparation of compound 63-2

Compound 63-1 (A) 30g (0.081mol, 1eq), diphenylamine (B) 15g) (0.089mol, 1.1eq), t-butoxy sodium (NaOt-Bu) 11.6 g (0.121 mol, 1.5eq), tris(dibenzylideneacetone)dipalladium, Pd ₂ (dba) ₃ ) 3.7 g (0.004 mol, 0.05eq) and tri-tert-butylphosphine ( Tri-tert-butylphosphine, P(t-bu) ₃ ) 1.6 g (0.008 mol, 0.1 eq) was dissolved in 450 mL of toluene and stirred at 100° C. for 6 hours. After the reaction was terminated by adding distilled water, the reaction solution was extracted with dichloromethane and distilled water, and moisture was removed using MgSO ₄ . Then, it was separated by a silica gel column to obtain 28 g of compound 63-2 (yield 75%).

Preparation Example 2-2. Preparation of compound 63-3

Compound 63-2 28g (0.061mol, 1eq), 4,4,4',4',5,5,5',5'-octamethyl-2,2'- ratio (1,3,2-dioxa Bororane) (4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane)) 23.2g (0.091mol, 1.5eq ), Bis(dibenzylideneacetone)palladium, Pd(dba) ₂ ) 1.7 g (0.003 mol, 0.05 eq) and Tricyclohexylphosphine (P(Cy) ₃ ) 1.7 g (0.006 mol) , 0.1eq) was dissolved in 1,4-dioxane (1,4-Dioxane) 280mL and stirred at 90°C for 6 hours. After the reaction was terminated by adding distilled water, the reaction solution was extracted with dichloromethane and distilled water, and moisture was removed using MgSO ₄ . Then, it was separated by a silica gel column to obtain 25 g of compound 63-3 (yield 74%).

Preparation 2-3. Preparation of compound 63

Compound 63-3 10g (0.018mol, 1eq), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (2-( [1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine) (C) 6.9 g (0.020 mol, 1.1 eq), potassium carbonate (K ₂ CO ₃ ) 5.5 g (0.040 mol, 2.2 eq) and tetrakis (triphenylphosphine) palladium (0) (tetrakis (triphenylhosphine) palladium (0), Pd (PPh ₃ ) ₄ ) 1 g (0.001 mol, 0.05 eq) of 1 ,4-Dioxane (1,4-Dioxane) was added to 120mL and distilled water 30mL and stirred at 90°C for 6 hours. After the reaction was terminated by adding distilled water, the reaction solution was extracted with dichloromethane and distilled water, and moisture was removed using MgSO ₄ . Then, it was separated by a silica gel column to obtain 9 g of compound 63 (yield 68%).

The following compounds were synthesized in the same manner as in Preparation Examples 1 and 2, except that intermediates A, B and C of Table 1 were used instead of (A), (B) and (C) of Preparation Examples 1 and 2 .

compound Intermediate A Intermediate B Intermediate C target compound 5

-

28

-

91

106

-

132

-

141

163

188

203

-

230

-

242

269

294

310

324

349

363

401

-

The synthesis results of the compounds described in Preparation Examples 1 to 2 and Table 1 are shown in Tables 2 and 3 below. Table 2 below is a measurement value of 1H NMR (CDCl ₃ , 300Mz), and Table 3 below is a measurement value of an FD-mass spectrometer (FD-MS: Field desorption mass spectrometry).

compound ¹ H NMR (CDCl ₃ , 200 Mz) 5 δ = 9.09 (1H, s), 8.49 (1H, d), 8.28 (2H, m), 7.89 (5H, m), 7.66 to 7.32 (12H, m) 28 δ = 9.09(2H, s), 8.49(2H, d), 8.00(10H, m), 7.59(6H, m), 7.45(1H, s), 7.32(6H, m) 42 δ = 8.28 (2H, m), 7.85 (4H, m), 7.75 (1H, d), 7.64 (2H, m), 7.52 to 7.32 (18H, m) 63 δ = 8.24 (3H, m), 7.89 (1H, d), 7.66 (3H, m), 7.57 to 7.41 (14H, m), 7.20 (4H, m), 6.81 (2H, m), 6.63 (4H, m), 6.39 (1H, d) 91 δ = 8.55 (1H, d), 8.28 (4H, m), 8.16 (2H, m), 7.89 (2H, m), 7.80 (1H, s), 7.66 (4H, m), 7.51 to 7.25 (14H, m) 106 δ = 8.30 (2H, m), 8.23 (1H, s), 8.00 (2H, m), 7.89 to 7.38 (21H, m) 132 δ = 8.55(2H, m), 8.30(4H, m), 8.23(1H, s), 8.01(2H, m), 7.85(4H, m), 7.66(2H, m), 7.55~7.32(15H, m) 141 δ = 8.23 (1H, s), 7.79 (7H, m), 7.66 (1H, m), 7.52 to 7.38 (15H, m) 163 δ = 8.23(1H, s), 7.89(1H, d), 7.65(6H, m), 7.51(14H, m), 7.20(4H, m), 6.81(2H, m), 6.63(4H, m) , 6.39(1H, d) 188 δ = 9.09(1H, s), 8.55(2H, m), 8.34(1H, s), 8.23(1H, s), 8.12(1H, d), 7.92(10H, m), 7.63~7.25(15H, m) 203 δ = 8.16 (1H, d), 7.89 to 7.32 (21H, m) 230 δ = 8.30 (2H, m), 7.85 (6H, m), 7.66 (4H, m), 7.52 to 7.32 (14H, m) 242 δ = 8.30 (2H, m), 8.16 (1H, d), 7.75 (7H, m), 7.66 to 7.32 (16H, m) 269 δ= 7.85~7.38 (24H, m) 294 δ = 8.45(1H, d), 8.30(2H, m), 7.98(1H, d), 7.85(3H, m), 7.66(2H, m), 7.52~7.32(11H, m), 7.20(4H, m), 6.81 (2H, m), 6.63 (4H, m), 6.39 (1H, d) 310 δ = 8.30 (2H, m), 7.85 (3H, m), 7.64 (4H, m), 7.52 to 7.32 (18H, m), 7.20 (2H, m), 6.81 (1H, t), 6.63 (4H, m), 6.33 (1H, d) 324 δ = 8.55 (1H, d), 8.12 (2H, m), 7.89 (4H, m), 7.66 to 7.29 (26H, m) 349 δ = 8.55 (1H, d), 8.16 (2H, m), 7.94 (3H, m), 7.79 (2H, m), 7.67 (5H, m), 7.55 to 7.32 (14H, m) 363 δ = 8.28(2H, m), 8.23(1H, s), 7.89(1H, d), 7.72(6H, m), 7.45(11H, m), 7.20(4H, m), 6.81(2H, m) , 6.69 (6H, m) 401 δ = 7.89 (2H, d), 7.66 (2H, d), 7.45 (1H, s), 7.32 (4H, m)

compound FD-MS compound FD-MS 5 m/z=539.16 203 m/z=538.17 28 m/z=665.21 230 m/z=654.19 42 m/z=641.21 242 m/z=614.20 63 m/z=732.25 269 m/z=628.18 91 m/z=704.22 294 m/z=761.21 106 m/z=614.20 310 m/z=821.27 132 m/z=690.23 324 m/z=779.26 141 m/z=564.18 349 m/z=717.21 163 m/z=731.26 363 m/z=731.26 188 m/z=753.24 401 m/z=659.32

<Experimental example>

Experimental Example 1.

Experimental Example 1-1. Fabrication of organic light emitting devices

A glass substrate coated with a thin film of ITO to a thickness of 1,500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic washing was performed with a solvent such as acetone, methanol, isopropyl alcohol, etc., dried, and UVO (Ultraviolet Ozone) treatment was performed for 5 minutes using UV in a UV washer. After transferring the substrate to a plasma cleaner (PT), plasma treatment was performed to remove the ITO work function and residual film in a vacuum state, and the substrate was transferred to a thermal deposition equipment for organic deposition.

Then, after evacuating the chamber until the vacuum degree reached 10 ^-6 torr, an electric current was applied to the cell to 4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine (4, 4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine), 2-TNATA) was evaporated to deposit a 600Å-thick hole injection layer on the ITO substrate. The following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (N,N'-bis(α-naphthyl)-N, N'-diphenyl-4,4'-diamine: NPB) was added, and a current was applied to the cell to evaporate it, and a 300 Å-thick hole transport layer was deposited on the hole injection layer.

A light emitting layer was deposited thereon by thermal vacuum deposition as follows. For the emission layer, the compounds shown in Table 4 were deposited as a red host, and (piq) ₂ (Ir)(acac) was doped to the host at 3 wt% using (piq) ₂ (Ir)(acac) as a red phosphorescent dopant. and deposited to a thickness of 400 Å. Thereafter, Bphen was deposited to a thickness of 30 Å as a hole blocking layer, and Alq ₃ as an electron transport layer was deposited thereon to a thickness of 250 Å. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited to a thickness of 1,200 Å on the electron injection layer to form a cathode. An organic electroluminescent device was prepared.

Meanwhile, all organic compounds required for manufacturing OLED devices were vacuum sublimated and purified under 10 ^-6 to 10 ^-8 torr for each material, respectively, and used for OLED (Organic Light Emitting Device) production.

Experimental Example 1-2. Driving 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 M7000 of McScience, and the reference luminance was 6,000 cd through the life instrumentation measuring device (M6000) manufactured by McScience with the measurement result. At /m ² , T ₉₀ was measured. Table 4 shows the results of measuring the driving voltage, luminous efficiency, color coordinates (CIE) and lifetime of the organic light emitting diode manufactured according to the present invention.

The T ₉₀ denotes a lifetime (unit: time) that is 90% of the initial luminance.

compound drive voltage
(V) luminous efficiency
(cd/A) CIE
(x, y) life span
(T ₉₀ ) Example 1 5 5.19 52.80 (0.680, 0.321) 119 Example 2 28 5.22 56.64 (0.679, 0.319) 123 Example 3 42 5.13 54.36 (0.678, 0.323) 130 Example 4 63 5.24 54.77 (0.681, 0.322) 108 Example 5 91 5.19 57.50 (0.678, 0.319) 132 Example 6 106 5.17 56.65 (0.682, 0.324) 137 Example 7 132 5.20 52.34 (0.677, 0.321) 113 Example 8 141 5.11 53.88 (0.680, 0.320) 128 Example 9 163 5.14 53.76 (0.681, 0.324) 115 Example 10 188 5.29 57.51 (0.683, 0.323) 138 Example 11 203 5.20 57.23 (0.683, 0.322) 128 Example 12 230 5.25 55.32 (0.679, 0.324) 116 Example 13 242 5.17 56.44 (0.680, 0.319) 119 Example 14 269 5.23 52.18 (0.677, 0.320) 123 Example 15 294 5.24 51.63 (0.682, 0.323) 119 Example 16 310 5.20 53.37 (0.681, 0.324) 138 Example 17 324 5.17 55.40 (0.678, 0.321) 113 Example 18 349 5.21 54.56 (0.680, 0.324) 124 Example 19 363 5.28 52.93 (0.681, 0.319) 119 Example 20 401 5.20 54.09 (0.681, 0.322) 137 Comparative Example 1 H1 5.98 46.83 (0.673, 0.330) 93 Comparative Example 2 H2 5.90 46.31 (0.678, 0.327) 81 Comparative Example 3 H3 5.88 45.28 (0.677, 0.325) 99 Comparative Example 4 H4 5.96 45.77 (0.680, 0.321) 82 Comparative Example 5 H5 5.91 46.06 (0.676, 0.324) 80 Comparative Example 6 H6 5.94 46.27 (0.677, 0.322) 87

[Comparative compounds H1-H6]

From the results of Table 4, it can be confirmed that the organic light-emitting devices of Examples 1 to 20 using the heterocyclic compound of the present invention as a host material had lower driving voltages and significantly improved luminous efficiency and lifespan compared to Comparative Examples 1 to 6 there was.

The heterocyclic compound of the present invention has high thermal stability, and a suitable molecular weight (m/z=500 to m/z=850) and a band gap (2.4eV to 3.2eV) for use in the light emitting layer of an organic light emitting device. An appropriate molecular weight facilitates the formation of the light emitting layer of the organic light emitting device, and an appropriate band gap prevents the loss of electrons and holes in the light emitting layer, thereby helping to form an effective recombination region. In addition, the heterocyclic compound having an electron transport property substituted at an appropriate position can solve the hole blocking phenomenon occurring in the dopant than the compound substituted at another position. Therefore, as shown in Table 4, it can be seen that the heterocyclic compound of the present invention is superior to the results of Comparative Examples in all aspects of driving voltage, luminous efficiency and lifespan.

Experimental Example 2.

Experimental Example 2-1. Fabrication of organic light emitting devices

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

4,4',4''-tris[2-naphthyl(phenyl)amino]triphenylamine (4,4',4''-Tris[ 2-naphthyl(phenyl)amino] triphenylamine), 2-TNATA), N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (N,N) as a hole transport layer '-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine: NPB) and cyclohexylidenebis[N,N-bis(4-methylphenyl)benzeneamine] as an electron blocking layer ( cyclohexylidenebis[N,N-bis(4-methylphenyl)benzenamine], TAPC) or Tris(4-carbazoyl-9-ylphenyl)amine (TCTA) as an exciton-blocking layer was formed.

A light emitting layer was deposited thereon by thermal vacuum deposition as follows. For the light emitting layer, two types of compounds described in Table 5 below were deposited as a red host from a single source, and (piq) ₂ (Ir)(acac) was used as a red phosphorescent dopant as a host (piq) ₂ (Ir) (acac). ) was doped with 3 wt% and deposited to a thickness of 400 Å.

At this time, when two hosts are used, the compound used as the p-Host is as follows.

Thereafter, Bphen was deposited to a thickness of 30 Å as a hole blocking layer, and TPBI was deposited to a thickness of 250 Å as an electron transport layer thereon. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited to a thickness of 1,200 Å on the electron injection layer to form a cathode. An organic electroluminescent device was prepared.

Meanwhile, all organic compounds required for manufacturing OLED devices were vacuum sublimated and purified under 10 ^-6 to 10 ^-8 torr for each material, respectively, and used for OLED (Organic Light Emitting Device) production.

Experimental Example 2-2. Driving 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 M7000 of McScience, and the reference luminance was 6,000 cd through the life instrumentation measuring device (M6000) manufactured by McScience with the measurement result. At /m ² , T ₉₀ was measured. Table 5 shows the results of measuring the driving voltage, luminous efficiency, color coordinates (CIE) and lifespan of the organic light emitting device manufactured according to the present invention.

compound ratio
(P/N) drive voltage
(V) luminous efficiency
(cd/A) CIE
(x, y) life span
(T ₉₀ ) Example 21 PH3:5 1:3 4.78 55.10 (0.681, 0.321) 110 Example 22 PH3:5 1:2 4.74 56.64 (0.680, 0.322) 111 Example 23 PH3:5 1:1 4.68 56.80 (0.679, 0.321) 124 Example 24 PH3:5 2:1 4.80 56.36 (0.678, 0.323) 109 Example 25 PH3:5 3:1 4.98 55.77 (0.677, 0.323) 104 Example 26 PH5:28 1:1 4.71 56.51 (0.680, 0.321) 109 Example 27 PH7:42 1:1 4.73 55.63 (0.678, 0.323) 117 Example 28 PH9:63 1:1 4.67 54.32 (0.681, 0.324) 107 Example 29 PH3:91 1:1 4.74 55.47 (0.681, 0.320) 110 Example 30 PH11:106 1:1 4.79 56.16 (0.679, 0.318) 105 Example 31 PH13:132 1:1 4.80 55.51 (0.678, 0.319) 128 Example 32 PH3:141 1:1 4.71 54.73 (0.679, 0.324) 118 Example 33 PH7:163 1:1 4.78 55.66 (0.681, 0.323) 106 Example 34 PH9:188 1:1 4.69 57.40 (0.682, 0.320) 109 Example 35 PH13:203 1:1 4.76 56.33 (0.679, 0.319) 118 Example 36 PH15:230 1:1 4.79 54.63 (0.681, 0.321) 126 Example 37 PH3:242 1:1 4.74 55.37 (0.684, 0.322) 124 Example 38 PH5:269 1:1 4.80 54.41 (0.679, 0.320) 108 Example 39 PH7:294 1:1 4.69 55.56 (0.680, 0.323) 112 Example 40 PH11:310 1:1 4.71 54.13 (0.679, 0.320) 128 Example 41 PH13:324 1:1 4.75 55.35 (0.681, 0.321) 113 Example 42 PH15:349 1:1 4.80 56.83 (0.683, 0.324) 128 Example 43 PH6:363 1:1 4.73 55.92 (0.680, 0.325) 109 Example 44 PH10:401 1:1 4.70 55.22 (0.681, 0.320) 129 Comparative Example 7 PH3:H1 1:1 5.27 47.76 (0.679, 0.323) 89 Comparative Example 8 PH5:H2 1:1 5.20 48.81 (0.678, 0.319) 80 Comparative Example 9 PH7:H3 1:1 5.29 47.63 (0.676, 0.320) 82 Comparative Example 10 PH5:H4 1:1 5.28 48.37 (0.679, 0.321) 81 Comparative Example 11 PH7:H5 1:1 5.19 49.03 (0.680, 0.323) 87 Comparative Example 12 PH9:H6 1:1 5.28 47.88 (0.681, 0.312) 85

[Comparative compounds H1-H6]

From the results of Table 5, when the heterocyclic compound of the present invention was used as an N-type host and mixed with a P-type host for deposition, it was confirmed that the driving voltage, luminous efficiency and lifespan of the organic light-emitting device were improved.

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, due to the exciplex phenomenon of the N+P compound, is injected into the p-host, and electrons are injected into the n-host, so that it is possible to balance the charge in the device. Through this, it was found that when the N-type host compound having excellent electron transport properties and the P-type host compound having excellent hole transport properties were combined in an appropriate ratio, it could help to improve the driving voltage, luminous efficiency, and lifespan.

All simple modifications and variations of the present invention fall within the scope of the present invention, and the specific protection scope of the present invention will become clear from the appended claims.

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

Claims (16)

Heterocyclic compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
Wherein X1 and X2 are the same as or different from each other, each independently O or S,
wherein R1 to R9 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; a substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; and -NR101R102, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle, wherein R101, R102 and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
The N-Het is a substituted or unsubstituted, C2 to C60 monocyclic or polycyclic heterocyclic group containing one or more N.
According to claim 1,
The N-Het is a heterocyclic compound, characterized in that represented by the formula (2):
[Formula 2]

In Formula 2,
Wherein X11 to X13 are the same as or different from each other, and each independently is N or CR13,
Wherein X11 to X13 are at least two or more N,
wherein R11 to R13 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; a substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; and -NR101R102, wherein R101, R102, and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
L is a direct bond; a substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group.
3. The method of claim 2,
Formula 2 is a heterocyclic compound, characterized in that represented by any one of Formulas 3 to 5:
[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5,
wherein R21 to R28 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; a substituted or unsubstituted C2 to C60 heteroaryl group; and -P(=0)R101R102; -SiR101R102R103; and -NR101R102, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle, wherein R101, R102 and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
The definition of L is the same as the definition in Formula 2 above.
4. The method of claim 3,
Formula 4 is a heterocyclic compound, characterized in that represented by any one of the following Formulas 4-1 to 4-4:
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

In Formulas 4-1 to 4-4,
wherein R31 to R48 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; a substituted or unsubstituted C2 to C60 heteroaryl group; and -P(=0)R101R102; -SiR101R102R103; and -NR101R102, wherein R101, R102, and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
The Y1 and Y2 are the same as or different from each other, and each independently O or S,
The definition of L is the same as the definition in Formula 2 above.
4. The method of claim 3,
wherein R21 and R22 are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C60 aryl group; Or, a substituted or unsubstituted C2 to C60 heteroaryl group,
wherein R26 to R28 are the same as or different from each other, and at least two of R26 to R28 are each independently a substituted or unsubstituted C6 to C60 aryl group; Or, a heterocyclic compound characterized in that it is a substituted or unsubstituted C2 to C60 heteroaryl group.
5. The method of claim 4,
wherein R31 to R33 are the same as or different from each other, and at least two of R31 to R33 are a substituted or unsubstituted C6 to C60 aryl group; Or, a substituted or unsubstituted C2 to C60 heteroaryl group,
Any one of R34 to R38 is a substituted or unsubstituted C6 to C60 aryl group; Or, a substituted or unsubstituted C2 to C60 heteroaryl group,
Any one of R39 to R43 is a substituted or unsubstituted C6 to C60 aryl group; Or, a substituted or unsubstituted C2 to C60 heteroaryl group,
Any one of R44 to R48 is a substituted or unsubstituted C6 to C60 aryl group; Or, a heterocyclic compound characterized in that it is a substituted or unsubstituted C2 to C60 heteroaryl group.
According to claim 1,
Heterocyclic compound, characterized in that the content of deuterium is 30% to 100% based on the total number of hydrogen atoms and deuterium atoms in Formula 1 above.
According to claim 1,
The heterocyclic compound represented by Formula 1 is a heterocyclic compound, characterized in that it is represented by any one of the following compounds:

a first electrode;
a second electrode provided to face the first electrode; and
An organic light emitting device comprising a; at least one organic material layer provided between the first electrode and the second electrode,
At least one layer of the organic material layer comprises the heterocyclic compound according to any one of claims 1 to 8, an organic light emitting device.
10. The method of claim 9,
The organic material layer is an organic light emitting device, characterized in that it further comprises a heterocyclic compound represented by the following Chemical Formula 6:
[Formula 6]

In Formula 6,
Wherein X21 and X22 are the same as or different from each other, and each independently O or S,
wherein R51 to R59 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; a substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; and -NR101R102, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle, wherein R101, R102 and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
The definition of L is the same as the definition in Formula 2 above.
11. The method of claim 10,
The heterocyclic compound represented by Formula 6 is an organic light emitting device, characterized in that any one selected from the following compounds:

10. The method of claim 9,
The organic light emitting device includes a light emitting layer, a hole injection layer, and a hole transport layer. An organic light-emitting device comprising one or more layers selected from the group consisting of an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.
A composition for an organic material layer of an organic light emitting device comprising the heterocyclic compound according to any one of claims 1 to 8 and the heterocyclic compound represented by the following Chemical Formula 6:
[Formula 6]

In Formula 6,
Wherein X21 and X22 are the same as or different from each other, and each independently O or S,
wherein R51 to R59 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; a substituted or unsubstituted C2 to C60 heteroaryl group; -P(=O)R101R102; -SiR101R102R103; and -NR101R102, or two or more groups adjacent to each other combine with each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle, wherein R101, R102 and R103 are the same as or different from each other, and each independently a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
The definition of L is the same as the definition in Formula 2 above.
14. The method of claim 13,
The composition for an organic material layer of an organic light emitting device, characterized in that the weight ratio of the heterocyclic compound represented by Formula 1 to the heterocyclic compound represented by Formula 6 is 1:10 to 10:1.
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,
The method of manufacturing an organic light emitting device, wherein the forming of the organic material layer comprises the step of forming one or more organic material layers using the composition for an organic material layer according to claim 13 .
16. The method of claim 15,
In the step of forming the organic material layer, the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 6 are pre-mixed, and the organic light emitting device is formed using a thermal vacuum deposition method. manufacturing method.

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