Organic light emitting device, method for manufacturing the same, and composition for organic material layer

Abstract

This specification relates to organic light emitting devices, methods for manufacturing the same, and compositions for organic material layers.

Description

[0001] Cross Reference to Related Applications

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2019-0103920, filed on August 23, 2019, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present specification relates to an organic light emitting device, a method for manufacturing the same, and a composition for an organic material layer. BACKGROUND

[0004] An electroluminescent device is a self-emissive display device, and has advantages of having a wide viewing angle and high response speed and having excellent contrast.

[0005] An organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to an organic light emitting device having such a structure, electrons and holes injected from the two electrodes combine and pair in the organic thin film, and light is emitted when these annihilate. The organic thin film can be formed as a single layer or multiple layers as needed.

[0006] The material of the organic thin film can have a light emitting function as needed. For example, as a material of the organic thin film, a compound capable of forming a light emitting layer by itself can be used alone, or a compound capable of playing a role of a host or a dopant of a light emitting layer based on a host-dopant can also be used. In addition thereto, a compound capable of playing a role of hole injection, hole transport, electron blocking, hole blocking, electron transport, electron injection, etc. can also be used as a material of the organic thin film.

[0007] There is a continuous need to develop an organic thin film material to improve the performance, lifespan, or efficiency of an organic light emitting device.

[0008] Prior art documents

[0009] Patent documents

[0010] (Patent Document 1) U.S. Patent No. 4,356,429 SUMMARY

[0011] TECHNICAL PROBLEM

[0012] The present application relates to an organic light emitting device, a method for manufacturing the same, and a composition for an organic material layer.

[0013] TECHNICAL SOLUTION

[0014] One embodiment of the present application provides an organic light emitting device including: a first electrode, a second electrode, and one or more organic material layers disposed between the first electrode and the second electrode,

[0015] wherein one or more layers of the organic material layers comprise a heterocyclic compound represented by the following Chemical Formula 1 and a heterocyclic compound represented by the following Chemical Formula 24.

[0016] [Chemical Formula 1]

[0017]

[0018] [Chemical Formula 24]

[0019]

[0020] In Chemical Formulas 1 and 24,

[0021] N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclic group including one or more N,

[0022] L and L1 are a direct bond; a substituted or unsubstituted C6 to C60 arylene; or a substituted or unsubstituted C2 to C60 heteroarylene, a is an integer of 1 to 3, and when a is 2 or more, L are the same as or different from each other,

[0023] R1 to R14 are the same as or different from each other, and each is independently selected from the group consisting of hydrogen; deuterium; a halogen; a cyano; a substituted or unsubstituted C1 to C60 alkyl; a substituted or unsubstituted C2 to C60 alkenyl; a substituted or unsubstituted C2 to C60 alkynyl; a substituted or unsubstituted C2 to C60 alkoxy; a substituted or unsubstituted C3 to C60 cycloalkyl; a substituted or unsubstituted C2 to C60 heterocycloalkyl; a substituted or unsubstituted C6 to C60 aryl; a substituted or unsubstituted C2 to C60 heteroaryl; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle,

[0024] b and c are each an integer of 1 to 3, and when b is 2 or more, R9 are the same as or different from each other, and when c is 2 or more, R10 are the same as or different from each other,

[0025] m, p, and q are integers of 0 to 4,

[0026] n is an integer of 0 to 2,

[0027] R11are the same as or different from each other when m is 2 or more, R12are the same as or different from each other when n is an integer of 2, R13are the same as or different from each other when p is 2 or more, and R14are the same as or different from each other when q is 2 or more,

[0028] Ar1is a substituted or unsubstituted C6to C60aryl; or a substituted or unsubstituted C2to C60heteroaryl including at least one of S and O, and

[0029] Ar2is a substituted or unsubstituted C6to C60aryl; or a substituted or unsubstituted C2to C60heteroaryl.

[0030] In addition, another embodiment of the present application provides a composition for an organic material layer of an organic light emitting device, the composition including a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 24.

[0031] Finally, one embodiment of the present application provides a method for manufacturing an organic light emitting device, the method including 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 formation of the organic material layer includes forming one or more organic material layers using a composition for an organic material layer according to the present application.

[0032] Advantageous Effects

[0033] The heterocyclic compound according to one embodiment of the present application can be used as a material for an organic material layer of an organic light emitting device. The heterocyclic compound can be used as a material for a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a charge generation layer, etc. in an organic light emitting device. In particular, the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 24 can be simultaneously used as a material for a light emitting layer of an organic light emitting device. In addition, when the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 are simultaneously used in an organic light emitting device, the driving voltage of the device can be reduced, the light efficiency can be improved, and the lifespan characteristics of the device can be improved by the thermal stability of the compounds.

[0034] In particular, by substituting the benzene ring on one side of the dibenzofuran structure with an N-containing ring and substituting the benzene ring in the dibenzofuran structure which is not substituted with the N-containing ring with a carbazole structure, a more electron-stable structure is obtained in the heterocyclic compound represented by Chemical Formula 1, and as a result, the device lifespan can be improved. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figures 1 to 3FIGS. 1 to 3 are each a schematic view illustrating a laminated structure of an organic light emitting device according to an embodiment of the present application. DETAILED DESCRIPTION

[0036] Hereinafter, the present application will be described in detail.

[0037] The term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent, and the position of substitution is not limited as long as the position is a position where a hydrogen atom is substituted (i.e., a position where a substituent can be substituted), and when two or more substituents are substituted, the two or more substituents can be the same as or different from each other.

[0038] In the present specification, "substituted or unsubstituted" means substituted with one or more substituents selected from the group consisting of C1 to C60 linear 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, or unsubstituted, or substituted with a substituent selected from two or more substituents among the substituents shown above, or unsubstituted. R, R’, and R” are the same as or different from each other, and each independently hydrogen; deuterium; cyano; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl.

[0039] In an embodiment of the present application, R, R’, and R” are the same as or different from each other, and can each independently be hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl.

[0040] In the present specification, halogen can be fluorine, chlorine, bromine, or iodine.

[0041] In the present specification, an alkyl group includes a linear or branched alkyl group having 1 to 60 carbon atoms, and can be further substituted with other substituent groups. The number of carbon atoms of the alkyl group can be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples thereof can include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, t-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, t-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, t-octyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, iso-hexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

[0042] In the present specification, an alkenyl group includes a linear or branched alkenyl group having 2 to 60 carbon atoms, and can be further substituted with other substituent groups. The number of carbon atoms of the alkenyl group can be 2 to 60, specifically 2 to 40, and more specifically 2 to 20. Specific examples thereof can include ethenyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butanedienyl, allyl, 1-phenylethen-1-yl, 2-phenylethen-1-yl, 2,2-diphenylethen-1-yl, 2-phenyl-2-(naphthyl-1-yl)ethen-1-yl, 2,2-bis(diphenyl-1-yl)ethen-1-yl, stilbenyl, styryl, and the like, but are not limited thereto.

[0043] In the present specification, an alkynyl group includes a linear or branched alkynyl group having 2 to 60 carbon atoms, and can be further substituted with other substituent groups. The number of carbon atoms of the alkynyl group can be 2 to 60, specifically 2 to 40, and more specifically 2 to 20.

[0044] In the present specification, an alkoxy group can be linear, branched, or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20. Specific examples thereof can include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, benxyloxy, p-methylbenxyloxy, and the like, but are not limited thereto.

[0045] In the present specification, a cycloalkyl group includes a monocyclic or polycyclic cycloalkyl group having 3 to 60 carbon atoms, and can be further substituted with other substituent groups. Here, polycyclic means a group in which a cycloalkyl group is directly connected to or fused with other cyclic groups. Here, the other cyclic groups can be cycloalkyl groups, but can also be different types of cyclic groups, such as heterocycloalkyl groups, aryl groups, and heteroaryl groups. The number of carbon atoms of the cycloalkyl group can be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specific examples thereof can include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

[0046] In the present specification, a heterocycloalkyl group includes O, S, Se, N, or Si as a heteroatom, includes a monocyclic or polycyclic heterocycloalkyl group having 2 to 60 carbon atoms, and can be further substituted with other substituent groups. Here, polycyclic means a group in which a heterocycloalkyl group is directly connected to or fused with other cyclic groups. Here, the other cyclic groups can be heterocycloalkyl groups, but can also be different types of cyclic groups, such as cycloalkyl groups, aryl groups, and heteroaryl groups. The number of carbon atoms of the heterocycloalkyl group can be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.

[0047] In the present specification, an aryl group includes a monocyclic or polycyclic aryl group having 6 to 60 carbon atoms, and can be further substituted with other substituent groups. Here, polycyclic means a group in which an aryl group is directly connected to or fused with other cyclic groups. Here, the other cyclic groups can be aryl groups, but can also be different types of cyclic groups, such as cycloalkyl groups, heterocycloalkyl groups, and heteroaryl groups. The aryl group includes a spirocyclic group. The number of carbon atoms of the aryl group can be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of the aryl group can include phenyl, biphenyl, terphenyl, naphthyl, anthryl, The aryl group includes a spirocyclic group. The number of carbon atoms of the aryl group can be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of the aryl group can include phenyl, biphenyl, terphenyl, naphthyl, anthryl,

[0048] In the present specification, a fluorenyl group can be substituted, and adjacent substituents can be bonded to each other to form a ring.

[0049] When the fluorenyl group is substituted, it can include and the like, however, the structure is not limited thereto.

[0050] In the present specification, a heteroaryl group includes O, S, Se, N, or Si as a heteroatom, includes a monocyclic or polycyclic heteroaryl group having 2 to 60 carbon atoms, and can be further substituted with other substituent groups. Here, polycyclic means a group in which a heteroaryl group is directly connected to other cyclic groups or fused with other cyclic groups. Here, the other cyclic groups can be heteroaryl groups, but can also be different types of cyclic groups, such as cycloalkyl groups, heterocycloalkyl groups, and aryl groups. The number of carbon atoms of the heteroaryl group can be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of the heteroaryl group can include pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furanyl, thienyl, imidazolyl, oxazolyl, isothiazolyl, oxazolyl, isothiazolyl, oxazolyl, isothiazolyl, oxazolyl, isothiazolyl, oxazolyl, isothiazolyl, oxazolyl, isothiazolyl, oxazolyl, isothiazolyl, oxazolyl, isothiazolyl,

[0051] In the present specification, an amine group can be selected from the group consisting of a monoalkylamine group; a monoarylamine group; a monoheteroarylamine group; -NH2; a dialkylamine group; a diarylamine group; a diheteroarylamine group; an alkylarylamine group; an alkylheteroarylamine group; and an arylheteroarylamine group, and although not particularly limited thereto, the number of carbon atoms is preferably 1 to 30. Specific examples of the amine group can 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 anthrylamine group, a 9-methyl-anthrylamine group, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, a biphenylnaphthylamine group, a phenylbiphenylamine group, a biphenylfluorenylamine group, a phenyltriphenylylamine group, a biphenyltriphenylylamine group, and the like, but is not limited thereto.

[0052] In the present specification, an arylene group means an aryl group having two bonding sites, i.e., a divalent group. The above description provided for the aryl group can be applied to the arylene group, except that each arylene group is divalent. Further, a heteroarylene group means a heteroaryl group having two bonding sites, i.e., a divalent group. The above description provided for the heteroaryl group can be applied to the heteroarylene group, except that each heteroarylene group is divalent.

[0053] In the present specification, a phosphine oxide group is represented by -P(=O)R 101 R 102 , and R 101 and R 102 are the same as or different from each other, and can each independently be a substituent formed from at least one of hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; an aryl group; and a heterocyclic group. Specifically, the phosphine oxide group can be specifically substituted with an aryl group, and as the aryl group, the examples described above can be used. Examples of the phosphine oxide group can include a diphenylphosphine oxide group, a dinaphthylphosphine oxide group, and the like, but are not limited thereto.

[0054] In the present specification, a silyl group is a substituent including Si, having a directly connected Si atom as a group, and is represented by -SiR 104 R 105 R 106 . R 104 to R 106 are the same as or different from each other, and can each independently be a substituent formed from at least one of hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; an aryl group; and a heterocyclic group. Specific examples of the silyl group can include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyl dimethylsilyl group, a propyl dimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like, but are not limited thereto.

[0055] In the present specification, "adjacent" groups can mean a substituent that substitutes an atom directly connected to an atom substituted with a corresponding substituent, a substituent located spatially closest to a corresponding substituent, or another substituent that substitutes an atom substituted with a corresponding substituent. For example, two substituents substituted at the ortho position of a benzene ring and two substituents substituted at the same carbon in an aliphatic ring can be interpreted as groups "adjacent" to each other.

[0056] As an aliphatic or aromatic hydrocarbon ring or heterocyclic ring that can be formed as adjacent groups, the structures shown as the above-mentioned cycloalkyl, cycloheteroalkyl, aryl, and heteroaryl can be used, with the difference that those are not monovalent.

[0057] One embodiment of the present application provides an organic light emitting device including: a first electrode, a second electrode, and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more layers of the organic material layers contain a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 24.

[0058] In one embodiment of the present application, Chemical Formula 1 can be represented by the following Chemical Formula 2 or Chemical Formula 3.

[0059] [Chemical Formula 2]

[0060]

[0061] [Chemical Formula 3]

[0062]

[0063] In Chemical Formulas 2 and 3,

[0064] R1 to R10, L, N-Het, a, b, and c have the same definition as in Chemical Formula 1.

[0065] In one embodiment of the present application, Chemical Formula 2 can be represented by any one of the following Chemical Formulas 4 to 7.

[0066] [Chemical Formula 4]

[0067]

[0068] [Chemical Formula 5]

[0069]

[0070] [Chemical Formula 6]

[0071]

[0072] [Chemical Formula 7]

[0073]

[0074] In Chemical Formula 4 to 7,

[0075] R1to R10, L, N-Het, a, b, and c have the same definition as in Chemical Formula 2.

[0076] In one embodiment of the present application, Chemical Formula 3 can be represented by one of the following Chemical Formulae 8 to 11.

[0077] [Chemical Formula 8]

[0078]

[0079] [Chemical Formula 9]

[0080]

[0081] [Chemical Formula 10]

[0082]

[0083] [Chemical Formula 11]

[0084]

[0085] In Chemical Formula 8 to 11,

[0086] R1to R10, L, N-Het, a, b, and c have the same definition as in Chemical Formula 3.

[0087] In one embodiment of the present application, N-Het is a monocyclic or polycyclic heterocycle which is substituted or unsubstituted and contains one or more N.

[0088] In another embodiment, N-Het is a monocyclic or polycyclic heterocycle which is unsubstituted or substituted with one or more substituents selected from the group consisting of aryl and heteroaryl and contains one or more N.

[0089] In another embodiment, N-Het is a monocyclic or polycyclic heterocycle which is unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, biphenyl, naphthyl, dimethylfluorenyl, dibenzofuranyl, and dibenzothiophenyl and contains one or more N.

[0090] In another embodiment, N-Het is a monocyclic or polycyclic heterocycle which is unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, biphenyl, naphthyl, dimethylfluorenyl, dibenzofuranyl, and dibenzothiophenyl and contains one or more and three or less N.

[0091] In an embodiment of the present application, N-Het is a monocyclic heterocycle that is substituted or unsubstituted and contains one or more N.

[0092] In an embodiment of the present application, N-Het is a divalent or higher valent heterocycle that is substituted or unsubstituted and contains one or more N.

[0093] In an embodiment of the present application, N-Het is a monocyclic or polycyclic heterocycle that is substituted or unsubstituted and contains two or more N.

[0094] In an embodiment of the present application, N-Het is a divalent or higher valent polycyclic heterocycle that contains two or more N.

[0095] In an embodiment of the present application, Chemical Formula 1 is represented by one of the following Chemical Formulas 12 to 14.

[0096] [Chemical Formula 12]

[0097]

[0098] [Chemical Formula 13]

[0099]

[0100] [Chemical Formula 14]

[0101]

[0102] In Chemical Formulas 12 to 14,

[0103] X1is CR21or N, X2is CR22or N, X3is CR23or N, X4is CR24or N, X5is CR25or N, and at least one of X1to X5is N,

[0104] R21to R25and R27to R32are the same as or different from each other, and each is independently selected from the group consisting of hydrogen; deuterium; a halogen; a cyano group; a substituted or unsubstituted C1to C60alkyl group; a substituted or unsubstituted C2to C60alkenyl group; a substituted or unsubstituted C2to C60alkynyl group; a substituted or unsubstituted C2to C60alkoxy group; a substituted or unsubstituted C3to C60cycloalkyl group; a substituted or unsubstituted C2to C60heterocycloalkyl group; a substituted or unsubstituted C6to C60aryl group; a substituted or unsubstituted C2to C60heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6to C60aromatic hydrocarbon ring or a substituted or unsubstituted C2to C60heterocycle.

[0105] In one embodiment of the present application, the chemical formula 12 is may be represented by one of the following chemical formulas 15 to 18. Here, is a site to be linked with L.

[0106] [Chemical Formula 15]

[0107]

[0108] [Chemical Formula 16]

[0109]

[0110] [Chemical Formula 17]

[0111]

[0112] [Chemical Formula 18]

[0113]

[0114] In the chemical formula 15, one or more of X1, X3, and X5 is N, and the rest has the same definition as in the chemical formula 12,

[0115] In the chemical formula 16, one or more of X1, X2, and X5 is N, and the rest has the same definition as in the chemical formula 12,

[0116] In the chemical formula 17, one or more of X1 to X3 is N, and the rest has the same definition as in the chemical formula 12,

[0117] In the chemical formula 18, one or more of X1, X2, and X5 is N, and the rest has the same definition as in the chemical formula 12, and

[0118] R22, R24, and R33 to R36 are the same as or different from each other, and each is independently selected from the group consisting of hydrogen; deuterium; a halogen; a cyano group; a substituted or unsubstituted C1 to C60 alkyl; a substituted or unsubstituted C2 to C60 alkenyl; a substituted or unsubstituted C2 to C60 alkynyl; a substituted or unsubstituted C2 to C60 alkoxy; a substituted or unsubstituted C3 to C60 cycloalkyl; a substituted or unsubstituted C2 to C60 heterocycloalkyl; a substituted or unsubstituted C6 to C60 aryl; a substituted or unsubstituted C2 to C60 heteroaryl; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more of the groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocyclic ring.

[0119] In one embodiment of the present application, Chemical Formula 15 can be selected from the following structural formulas.

[0120]

[0121] In the structure, R21 to R25 have the same definition as in Chemical Formula 15.

[0122] In one embodiment of the present application, Chemical Formula 16 can be represented by the following Chemical Formula 19.

[0123] [Chemical Formula 19]

[0124]

[0125] The substituents of Chemical Formula 19 have the same definition as in Chemical Formula 16.

[0126] In one embodiment of the present application, Chemical Formula 17 can be represented by the following Chemical Formula 20.

[0127] [Chemical Formula 20]

[0128]

[0129] The substituents of Chemical Formula 20 have the same definition as in Chemical Formula 17.

[0130] In one embodiment of the present application, Chemical Formula 16 can be represented by the following Chemical Formula 21.

[0131] [Chemical Formula 21]

[0132]

[0133] In Chemical Formula 21,

[0134] R37 is selected from the group consisting of hydrogen; deuterium; a halogen; a 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 C2 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; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more radicals adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle, e is an integer of 0 to 7, and when e is 2 or more, R37 are the same or different from each other.

[0135] In an embodiment of the application, Chemical Formula 18 can be represented by the following Chemical Formula 22.

[0136] [Chemical Formula 22]

[0137]

[0138] The substituents of Chemical Formula 22 have the same limitations as in Chemical Formula 18.

[0139] In an embodiment of the application, L is a direct bond or a C6 to C60 arylene group.

[0140] In another embodiment, L is a direct bond or a phenylene group.

[0141] In another embodiment, R9 and R10 are hydrogen; or deuterium.

[0142] In another embodiment, R9 and R10 are hydrogen.

[0143] In another embodiment, R1 to R8 are hydrogen; deuterium; C6 to C60 aryl group; C2 to C60 heteroaryl group; or C2 to C60 heteroaryl group substituted with C6 to C60 aryl group.

[0144] In another embodiment, R1 to R8 are hydrogen; deuterium; C6 to C60 aryl group; C2 to C60 heteroaryl group; or C2 to C60 heteroaryl group substituted with C6 to C60 aryl group.

[0145] In another embodiment, R1 to R8 are hydrogen; deuterium; phenyl group; dibenzofuranyl group; dibenzothiophenyl group; carbazolyl group; or carbazolyl group substituted with phenyl group.

[0146] In another embodiment, R1 to R8 are hydrogen; deuterium; phenyl group; dibenzofuranyl group; or carbazolyl group substituted with phenyl group.

[0147] In another embodiment, two or more adjacent substituents among R1 to R8 are bonded to each other to form a substituted or unsubstituted ring.

[0148] In another embodiment, two or more adjacent substituents among R1 to R8 are bonded to each other to form a ring unsubstituted or substituted with C6 to C60 aryl group or C1 to C60 alkyl group.

[0149] In another embodiment, two or more adjacent substituents among R1 to R8 are bonded to each other to form a C6 to C60 aromatic hydrocarbon ring or C2 to C60 heterocyclic ring unsubstituted or substituted with C6 to C60 aryl group or C1 to C60 alkyl group.

[0150] In another embodiment, two or more adjacent substituents among R1to R8are bonded to each other to form a C6to C60aromatic hydrocarbon ring or a C2to C60heterocyclic ring which is unsubstituted or substituted with a phenyl or a methyl group.

[0151] In another embodiment, two or more adjacent substituents among R1to R8may be bonded to each other to form a benzene ring; an indole ring which is unsubstituted or substituted with a phenyl group; a benzothiophene ring; a benzofuran ring; or an indene ring which is unsubstituted or substituted with a methyl group.

[0152] In another embodiment, the chemical formula 1 of may be represented by the following chemical formula 23. Herein, is a site connected to the dibenzofuran structure.

[0153] [Chemical Formula 23]

[0154]

[0155] In the chemical formula 23,

[0156] R1to R4have the same definition as in the chemical formula 1,

[0157] Y is O, S, NR d or CR e R f ,

[0158] R d , R e , R f , R41and R42are the same as or different from each other, and are selected from the group consisting of hydrogen; deuterium; a halogen; a cyano group; a substituted or unsubstituted C1to C60alkyl group; a substituted or unsubstituted C2to C60alkenyl group; a substituted or unsubstituted C2to C60alkynyl group; a substituted or unsubstituted C2to C60alkoxy group; a substituted or unsubstituted C3to C60cycloalkyl group; a substituted or unsubstituted C2to C60heterocycloalkyl group; a substituted or unsubstituted C6to C60aryl group; a substituted or unsubstituted C2to C60heteroaryl group; a substituted or unsubstituted phosphine group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6to C60aromatic hydrocarbon ring or a substituted or unsubstituted C2to C60heterocyclic ring, f is an integer of 0 to 4, and when f is 2 or more, R41are the same as or different from each other, g is an integer of 0 to 2, and when g is 2 or more, R42are the same as or different from each other.

[0159] In another embodiment, the chemical formula 23 can be selected from the following structural formulas.

[0160]

[0161] In the structural formulae,

[0162] Each substituent has the same definition as in Chemical Formula 23.

[0163] In one embodiment of the present application, R28 to R31 are the same as or different from each other, and each is independently hydrogen; deuterium; C6 to C60 aryl; or C2 to C60 heteroaryl.

[0164] In another embodiment, R28 to R31 are the same as or different from each other, and each is independently hydrogen; or deuterium.

[0165] In another embodiment, R28 to R31 are hydrogen.

[0166] In one embodiment of the present application, R27 and R32 are the same as or different from each other, and each is independently hydrogen; deuterium; C6 to C60 aryl; or C2 to C60 heteroaryl.

[0167] In another embodiment, R27 and R32 are the same as or different from each other, and each is independently C6 to C60 aryl; or C2 to C60 heteroaryl.

[0168] In another embodiment, R27 and R32 are the same as or different from each other, and each is independently C6 to C60 aryl.

[0169] In another embodiment, R27 and R32 are phenyl.

[0170] In one embodiment of the present application, R21 to R25 are the same as or different from each other, and each is independently hydrogen; deuterium; C6 to C60 aryl unsubstituted or substituted with C1 to C60 alkyl; or substituted or unsubstituted C2 to C60 heteroaryl.

[0171] In another embodiment, R21 to R25 are the same as or different from each other, and each is independently hydrogen; deuterium; C6 to C60 aryl unsubstituted or substituted with C1 to C60 alkyl; or C2 to C60 heteroaryl.

[0172] In another embodiment, R21 to R25 are the same as or different from each other, and each is independently hydrogen; C6 to C60 aryl unsubstituted or substituted with methyl; or C2 to C60 heteroaryl.

[0173] In another embodiment, R21 to R25 are the same as or different from each other, and each is independently hydrogen; phenyl; biphenyl; naphthyl; dimethylfluorenyl; dibenzofuranyl; or dibenzothiophenyl.

[0174] In another embodiment, R22and R24are the same or different from each other and each is independently C6to C60aryl unsubstituted or substituted with C1to C60alkyl; or C2to C60heteroaryl.

[0175] In another embodiment, R22and R24are the same or different from each other and each is independently phenyl; biphenyl; naphthyl; dimethylfluorenyl; dibenzofuranyl; or dibenzothiophenyl.

[0176] In one embodiment of the application, R33to R36are the same or different from each other and each is independently hydrogen; deuterium; C6to C60aryl; or C2to C60heteroaryl.

[0177] In another embodiment, R33to R36are the same or different from each other and each is independently hydrogen; deuterium; or C6to C60aryl.

[0178] In another embodiment, R33to R36are the same or different from each other and each is independently hydrogen; or C6to C60aryl.

[0179] In another embodiment, R33to R36are the same or different from each other and each is independently hydrogen; phenyl; or biphenyl.

[0180] In one embodiment of the application, R37is hydrogen; deuterium; C6to C60aryl; or C2to C60heteroaryl.

[0181] In another embodiment, R37is hydrogen; deuterium; or C6to C60aryl.

[0182] In another embodiment, R37is hydrogen; or C6to C60aryl.

[0183] In another embodiment, R37is hydrogen; or phenyl.

[0184] In one embodiment of the application, Y is O or S.

[0185] In another embodiment, Y is NR d , and R d is C6to C60aryl.

[0186] In another embodiment, Y is NR d , and R d is phenyl.

[0187] In another embodiment, Y is CR e R f , and R e and R f are C1to C60alkyl.

[0188] In another embodiment, Y is CR e R f , and R e and R f are methyl.

[0189] In one embodiment of the present application, R41is hydrogen; deuterium; C6to C60aryl; or C2to C60heteroaryl.

[0190] In another embodiment, R41is hydrogen; deuterium; or C6to C60aryl.

[0191] In another embodiment, R41is hydrogen; or phenyl.

[0192] In one embodiment of the present application, R42is hydrogen; or deuterium.

[0193] In another embodiment, R42is hydrogen.

[0194] In one embodiment of the present application, Chemical Formula 24 can be represented by any one of the following Chemical Formulas 25 to 28.

[0195] [Chemical Formula 25]

[0196]

[0197] [Chemical Formula 26]

[0198]

[0199] [Chemical Formula 27]

[0200]

[0201] [Chemical Formula 28]

[0202]

[0203] In Chemical Formulas 25 to 28,

[0204] R11to R14, L1, Ar1, Ar2, m, n, p, and q have the same definitions as in Chemical Formula 24.

[0205] In one embodiment of the present application, L1may be a direct bond; or a substituted or unsubstituted C6to C60arylene.

[0206] In another embodiment, L1may be a direct bond; or a substituted or unsubstituted C6to C40arylene.

[0207] In another embodiment, L1may be a direct bond; or a substituted or unsubstituted C6to C20arylene.

[0208] In another embodiment, L1may be a direct bond; or a substituted or unsubstituted C6to C20monocyclic arylene.

[0209] In another embodiment, L1may be a direct bond; or a C6to C20monocyclic arylene.

[0210] In another embodiment, L1may be a direct bond; or a phenylene.

[0211] In one embodiment of the application, Ar1may be a substituted or unsubstituted C6to C60aryl; or a substituted or unsubstituted C2to C60heteroaryl comprising at least one of S and O.

[0212] In another embodiment, Ar1may be a substituted or unsubstituted C6to C40aryl; or a substituted or unsubstituted C2to C40heteroaryl comprising at least one of S and O.

[0213] In another embodiment, Ar1may be a C6to C20aryl unsubstituted or substituted with a C1to C10alkyl; or a substituted or unsubstituted C2to C20heteroaryl comprising at least one of S and O.

[0214] In another embodiment, Ar1may be a C6to C20aryl unsubstituted or substituted with a C1to C10alkyl; or a C2to C20heteroaryl comprising at least one of S and O.

[0215] In another embodiment, Ar1may be a C6to C20monocyclic or polycyclic aryl unsubstituted or substituted with a C1to C10alkyl; or a polycyclic C2to C20heteroaryl comprising at least one of S and O.

[0216] In another embodiment, Ar1may be a phenyl; a biphenyl; a naphthyl; a dimethylfluorenyl; a dibenzothiophenyl; or a dibenzofuranyl.

[0217] In one embodiment of the application, Ar2is a substituted or unsubstituted C6to C60aryl; or a substituted or unsubstituted C2to C60heteroaryl.

[0218] In another embodiment, Ar2may be a substituted or unsubstituted C6to C60aryl.

[0219] In another embodiment, Ar2may be a substituted or unsubstituted C6to C40aryl.

[0220] In another embodiment, Ar2may be a substituted or unsubstituted C6to C20aryl.

[0221] In another embodiment, Ar2may be a C6to C20aryl.

[0222] In another embodiment, Ar2may be a C6to C20monocyclic aryl.

[0223] In another embodiment, Ar2may be a C10to C20monocyclic aryl.

[0224] In another embodiment, Ar2may be a phenyl.

[0225] In an embodiment of the present application, R11to R14are the same as or different from each other, and each is independently selected from the group consisting of hydrogen; deuterium; a halogen; a cyano; a substituted or unsubstituted C1to C60alkyl; a substituted or unsubstituted C2to C60alkenyl; a substituted or unsubstituted C2to C60alkynyl; a substituted or unsubstituted C2to C60alkoxy; a substituted or unsubstituted C3to C60cycloalkyl; a substituted or unsubstituted C2to C60heterocycloalkyl; a substituted or unsubstituted C6to C60aryl; a substituted or unsubstituted C2to C60heteroaryl; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more of the groups adjacent to each other can be bonded to each other to form a substituted or unsubstituted C6to C60aromatic hydrocarbon ring or a substituted or unsubstituted C2to C60hetero ring.

[0226] In another embodiment, R11to R14may be hydrogen.

[0227] In an embodiment of the present application, when a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 24 are contained in an organic material layer of an organic light emitting device, more excellent efficiency and lifespan effects are obtained. Such a result can lead to a prediction that an exciplex phenomenon occurs when the two compounds are contained at the same time.

[0228] The exciplex phenomenon is a phenomenon in which energy having the size of a donor (p-host) HOMO level and an acceptor (n-host) LUMO level is released due to electron exchange between two molecules. When the exciplex phenomenon occurs between two molecules, reverse intersystem crossing (RISC) occurs, as a result, the internal quantum efficiency of fluorescence can increase up to 100%. When a donor (p-host) having a good hole transport ability and an acceptor (n-host) having a good electron transport ability are used as a host of an emission layer, holes are injected to the p-host and electrons are injected to the n-host, thus, it is possible to reduce a driving voltage, thereby contributing to improvement in lifespan.

[0229] The heterocyclic compound represented by Chemical Formula 24 introduces dibenzothiophene group as a heteroaryl group into a biscarbazole form, and by expanding the HOMO to thereby improve the hole transport ability, an excellent characteristic in terms of efficiency is obtained. In other words, when having dibenzothiophene as the heterocyclic compound of Chemical Formula 24 of the present application, stronger aromaticity is obtained compared to dibenzofuran, and thus, due to the structural stability, a longer lifespan characteristic can be obtained.

[0230] In particular, by introducing a substituent to the 4th carbon in dibenzothiophene (a position having relatively good reactivity), the reactivity is also inhibited, which is a factor in producing a long lifespan characteristic.

[0231] According to one embodiment of the present application, Chemical Formula 1 can be represented by any one of the following Group 1 and Group 2 compounds, but is not limited thereto.

[0232] [Group 1]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246] [Group 2]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260] In one embodiment of the present application, Chemical Formula 24 can be represented by any one of the following compounds, but is not limited thereto.

[0261]

[0262]

[0263]

[0264]

[0265]

[0266] Further, by introducing various substituents into the structures of Chemical Formulas 1 and 24, compounds having unique characteristics of the introduced substituents can be synthesized. For example, by introducing substituents commonly used as hole injection layer materials, hole transport layer materials, light emitting layer materials, electron transport layer materials, and charge generation layer materials for manufacturing organic light emitting devices into the core structure, materials satisfying the required conditions of each organic material layer can be synthesized.

[0267] Further, by introducing various substituents into the structures of Chemical Formulas 1 and 24, the band gap can be finely controlled, and at the same time, the characteristics at the interface between organic materials can be enhanced, and material applications can become diversified.

[0268] Meanwhile, the heterocyclic compound has a high glass transition temperature (Tg), and has excellent thermal stability. Such an increase in thermal stability becomes an important factor in providing driving stability to a device.

[0269] The heterocyclic compound according to one embodiment of the present application can be prepared using a multi-step chemical reaction. Some intermediate compounds are first prepared, and a compound of Chemical Formula 1 or 24 can be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to one embodiment of the present application can be prepared based on the preparation examples described later.

[0270] In addition, another embodiment of the present application provides a composition for an organic material layer of an organic light emitting device, the composition including a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 24.

[0271] Specific details of the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24 are the same as the descriptions provided above.

[0272] In the composition, the weight ratio of the heterocyclic compound represented by Chemical Formula 1 : the heterocyclic compound represented by Chemical Formula 24 can be 1:10 to 10:1, 1:8 to 8:1, 1:5 to 5:1, or 1:2 to 2:1, however, the weight ratio is not limited thereto.

[0273] The composition can be used when forming an organic material of an organic light emitting device, and in particular, can be more preferably used when forming a host of an emission layer.

[0274] The composition has a form in which two or more compounds are simply mixed, and a material in a powder form can be mixed before forming an organic material layer of an organic light emitting device, or a compound in a liquid state can be mixed at a temperature higher than an appropriate temperature. The composition is in a solid state lower than the melting point of each material, and can be kept in a liquid state by adjusting the temperature.

[0275] The composition can further include materials known in the art, for example, a solvent and an additive.

[0276] An organic light emitting device according to one embodiment of the present application can be manufactured using common organic light emitting device manufacturing methods and materials, except that one or more organic material layers are formed using the above-described heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24.

[0277] When the organic light emitting device is manufactured, the compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24 can be formed into an organic material layer by a solution coating method as well as a vacuum deposition method. Herein, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

[0278] The organic material layer of the organic light emitting device of the present disclosure can be formed into a single layer structure, or can also be formed into a multi-layer structure in which two or more organic material layers are laminated. For example, the organic light emitting device according to one embodiment of the present disclosure can have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc., as the organic material layer. However, the structure of the organic light emitting device is not limited thereto, and can include a smaller number of organic material layers.

[0279] Specifically, the organic light emitting device according to one embodiment of the present application includes a first electrode, a second electrode, and one or more organic material layers disposed between the first electrode and the second electrode, and one or more layers of the organic material layers contain the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24.

[0280] In one embodiment of the present application, the first electrode can be an anode, and the second electrode can be a cathode.

[0281] In another embodiment, the first electrode can be a cathode, and the second electrode can be an anode.

[0282] In one embodiment of the present application, the organic light emitting device can be a blue organic light emitting device, and the heterocyclic compound according to Chemical Formula 1 and the heterocyclic compound according to Chemical Formula 24 can be used as a material for the blue organic light emitting device.

[0283] In one embodiment of the present application, the organic light emitting device can be a green organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24 can be used as a material for the green organic light emitting device.

[0284] In one embodiment of the present application, the organic light emitting device can be a red organic light emitting device, and the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24 can be used as a material for the red organic light emitting device.

[0285] The organic light emitting device of the present disclosure can further include one, two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

[0286] In an organic light emitting device provided in one embodiment of the present application, the organic material layer includes at least one of a hole blocking layer, an electron injecting layer, and an electron transporting layer, and at least one of the hole blocking layer, the electron injecting layer, and the electron transporting layer contains the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24.

[0287] In an organic light emitting device provided in one embodiment of the present application, the organic material layer includes a light emitting layer, and the light emitting layer contains the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24.

[0288] In an organic light emitting device provided in one embodiment of the present application, the organic material layer includes a light emitting layer, the light emitting layer contains a host material, and the host material contains the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24.

[0289] In an organic light emitting device provided in one embodiment of the present application, the organic material layer includes a light emitting layer, the light emitting layer contains a host material and a dopant material, the host material contains the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24, and the content of the dopant material is greater than or equal to 1 part by mass and less than or equal to 15 parts by mass with respect to 100 parts by mass of the host material.

[0290] In one embodiment of the present application, the content of the dopant material can be greater than or equal to 1 part by mass and less than or equal to 15 parts by mass, preferably greater than or equal to 2 parts by mass and less than or equal to 13 parts by mass, and more preferably greater than or equal to 3 parts by mass and less than or equal to 7 parts by mass with respect to 100 parts by mass of the host material.

[0291] In a general light emitting device, as the dopant concentration is reduced, the driving voltage and efficiency are reduced, and the lifetime is improved, whereas as the dopant concentration is increased, the efficiency improving effect can be expected due to an increase in the possibility of energy transfer from the host to the dopant, however, it is known that this has the following disadvantages: the lifetime of the device itself is inhibited due to charge trapping, and the driving voltage is increased.

[0292] However, in the present disclosure, the efficiency of low dopant doping has a similar or enhanced effect compared to high doping, and this is considered to be due to the fact that the host used in the present disclosure (the mixture of Chemical Formula 1 and Chemical Formula 24 of the present application) has a good charge transport ability, which facilitates energy transfer from the host to the dopant even in the case of low doping, thereby contributing to the improvement of efficiency and lifetime, and thus, there is an advantage of using a small amount of dopant when the dopant is used together with the host used in the present disclosure.

[0293] Figures 1 to 3The lamination order of the electrode and the organic material layer of the organic light emitting device according to one embodiment of the present application is shown. However, the scope of the present application is not limited to these figures, and the structure of the organic light emitting device known in the art can also be used in the present application.

[0294] Figure 1 An organic light emitting device in which an anode (200), an organic material layer (300), and a cathode (400) are sequentially laminated on a substrate (100) is shown. However, the structure is not limited to such a structure, and as Figure 2 indicated in the above, an organic light emitting device in which a cathode, an organic material layer, and an anode are sequentially laminated on a substrate can also be obtained.

[0295] Figure 3 The case where the organic material layer is a multi-layer is shown. The organic light emitting device according to Figure 3 the present application 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 to such a lamination structure, and other layers other than the light emitting layer can not be included as necessary, and other necessary functional layers can also be included.

[0296] One embodiment of the present application provides a method for manufacturing an organic light emitting device, the method including 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 formation of the organic material layer includes forming one or more organic material layers using a composition for an organic material layer according to one embodiment of the present application.

[0297] In the method for manufacturing an organic light emitting device provided in one embodiment of the present application, the formation of the organic material layer is formed using a method of thermal vacuum deposition after pre-mixing the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 24.

[0298] Pre-mixing means that the materials of the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 24 are mixed in one supply source in advance before being deposited on the organic material layer. Since one supply source is used instead of using 2 to 3 supply sources, pre-mixing has the advantage of making the process simpler.

[0299] The pre-mixed material can be referred to as a composition for an organic material layer according to one embodiment of the present application.

[0300] When the pre-mixing is performed as above, it is necessary to determine the unique thermal characteristics of each material at the time of mixing. In this regard, when the pre-mixed host material is deposited from one supply source, the unique thermal characteristics of the material can significantly affect the deposition conditions including the deposition rate. When the thermal characteristics between two or more types of pre-mixed materials are not similar but are very different, it can be impossible to maintain the reproducibility and the repeatability during the deposition, which means that it can be impossible to manufacture an all-uniform OLED in one deposition process.

[0301] In view of the above, it is also possible to control the thermal characteristics of the material by simultaneously adjusting the electrical characteristics of the molecular structure according to the type of the molecular structure by using an appropriate combination of the base structure and the substituents of each material. Accordingly, it is possible to improve the device performance by using various substituents in Chemical Formula 24 as well as the base structure and the C-C bonding of the biscarbazole as in Chemical Formula 24, and by controlling the thermal characteristics of each material, it is possible to secure the diversification of various pre-mixing deposition processes between the hosts. This has the advantage of securing the diversification of the pre-mixing deposition processes using three, four, or more host materials and two compounds as the host.

[0302] In the organic light emitting device according to one embodiment of the present application, materials other than the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 24 are shown below, however, these are for illustrative purposes only, not for limiting the scope of the present application, and can be replaced by materials known in the art.

[0303] As the anode material, a material having a relatively large work function can be used, and a transparent conductive oxide, a metal, a conductive polymer, or the like can be used. Specific examples of the anode material include: a metal such as vanadium, chromium, copper, zinc, and gold, or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); a combination of a metal and an oxide such as ZnO:Al or SnO2:Sb; a conductive polymer such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, or the like, but are not limited thereto.

[0304] As the cathode material, a material having a relatively small work function can be used, and a metal, a metal oxide, a conductive polymer, or the like can be used. Specific examples of the cathode material include: a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or an alloy thereof; a multi-layered structure material such as LiF / Al or LiO2 / Al; and the like, but are not limited thereto.

[0305] As hole injection materials, known hole injection materials can be used, such as phthalocyanine compounds, such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429; or starburst-type amine derivatives, such as tris(4-carbazolyl-9-ylphenyl)amine (TCTA), 4,4',4”-tris[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA), or 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB) as described in the literature [Advanced Material, 6, p. 677 (1994)]; as conductive polymers with solubility, such as polyaniline / dodecylbenzenesulfonic acid, poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonic acid), polyaniline / camphorsulfonic acid, or polyaniline / poly(4-styrene-sulfonic acid), etc.

[0306] As hole transport materials, pyrazoline derivatives, arylamine-based derivatives, arsenic derivatives, triphenyldiamine derivatives, etc., can be used, and low-molecular-weight or high-molecular-weight materials can also be used.

[0307] As an electron transport material, it can be used Metal complexes of diazole derivatives, anthraquinone dimethyl ether and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethyl ether and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, biphenylquinone derivatives, 8-hydroxyquinoline and its derivatives, etc., and can also use polymeric and low molecular weight materials.

[0308] LiF is commonly used in the art as an example of an electron injection material; however, this application is not limited thereto.

[0309] Red, green, or blue luminescent materials can be used, and two or more luminescent materials can be mixed and used as needed. Here, two or more luminescent materials can be used either by deposition as a single supply source or by pre-mixing and deposition as a single supply source. Furthermore, fluorescent materials can also be used as luminescent materials; however, phosphorescent materials can also be used. As luminescent materials, materials that emit light by combining holes and electrons injected separately from the anode and cathode can be used alone; however, materials having a host material and a dopant material that participate in luminescence together can also be used.

[0310] When mixing luminescent material substrates, substrates from the same series or different series can be mixed. For example, any two or more types of materials, either n-type or p-type substrate materials, can be selected and used as the substrate material for the luminescent layer.

[0311] Depending on the materials used, an organic light-emitting device according to one embodiment of this application can be a top-emitting, bottom-emitting, or bilaterally emitting type.

[0312] Heterocyclic compounds according to one embodiment of this application can also be used in organic electronic devices, including organic solar cells, organic photoconductors, organic transistors, etc., based on similar principles used in organic light-emitting devices.

[0313] The present specification will be described in more detail below with reference to embodiments; however, these are for illustrative purposes only, and the scope of the present application is not limited thereto.

[0314] <Preparation Example>

[0315] <Preparation of Compounds with Chemical Formula 24>

[0316] [Preparation Example 1] Preparation of Compound 2

[0317]

[0318] Preparation of compound 2-2 (ref 2)

[0319] 2-Bromodibenzo[b,d]thiophene (4.2 g, 15.8 mM), 9-phenyl-9H,9'H-3,3'-bicarbazole (6.5 g, 15.8 mM), CuI (3.0 g, 15.8 mM), trans-1,2-diaminocyclohexane (1.9 mL, 15.8 mM) and K3PO4 (3.3 g, 31.6 mM) were dissolved in 1,4-di... After being placed in alkyl (100 mL), the product was refluxed for 24 hours. Once the reaction was complete, the product was extracted by introducing distilled water and dichloromethane (DCM), and the solvent was removed by rotary evaporation after drying the organic layer with MgSO4. The reactants were purified by column chromatography (DCM:Hex = 1:3) and recrystallized from methanol to obtain the target compound 2-2 (7.9 g, 85%).

[0320] Preparation of compound 2-1

[0321] To a mixed solution in which compound 2-2 (8.4 g, 14.3 mmol) and tetrahydrofuran (THF) (100 mL) were introduced, 2.5M n-BuLi (7.4 mL, 18.6 mmol) was dropped at -78℃, and the resultant was stirred at room temperature for 1 hour. To the reaction mixture, trimethyl borate (4.8 mL, 42.9 mmol) was dropped, and the resultant was stirred at room temperature for 2 hours. After the completion of the reaction, the resultant was extracted by introducing distilled water and DCM thereto, and after the organic layer was dried with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified using column chromatography (DCM:MeOH=100:3), and recrystallized with DCM to obtain the target compound 2-1 (3.9 g, 70%).

[0322] Preparation of compound 2

[0323] After compound 2-1 (6.7 g, 10.5 mM), iodobenzene (2.1 g, 10.5 mM), Pd(PPh3)4 (606 mg, 0.52 mM), and K2CO3 (2.9 g, 21.0 mM) were dissolved in toluene / EtOH / H2O (100 / 20 / 20 mL), the resultant was refluxed for 12 hours. After the completion of the reaction, the resultant was extracted by introducing distilled water and DCM thereto, and after the organic layer was dried with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified using column chromatography (DCM:Hex=1:3), and recrystallized with methanol to obtain the target compound 2 (4.9 g, 70%).

[0324] The target compound A was synthesized in the same manner as in the preparation of compound 2, except that the intermediate A of Table 1 below was used instead of iodobenzene.

[0325] Table 1

[0326]

[0327]

[0328]

[0329]

[0330] The target compound B was synthesized in the same manner as in the preparation of compound 2, except that the intermediate B and the intermediate C of Table 2 below were used.

[0331] Table 2

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338] Preparation of Comparative Example not corresponding to Chemical Formula 24

[0339] [Preparation Example 2] Preparation of compound ref 3

[0340]

[0341] After dissolving 2-bromodibenzo[b,d]furan (3.9 g, 15.8 mM), 9-phenyl-9H,9'H-3,3'-bicarbazole (6.5 g, 15.8 mM), CuI (3.0 g, 15.8 mM), trans-1,2-diaminocyclohexane (1.9 mL, 15.8 mM), and K3PO4 (3.3 g, 31.6 mM) in 1,4-dioxane (100 mL), the resulting product was refluxed for 24 hours. After the completion of the reaction, the resulting product was extracted by introducing distilled water and DCM thereto, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified using column chromatography (DCM:Hex=1:3), and recrystallized with methanol to obtain the target compound ref 3 (7.7 g, 85%). [Preparation Example 3] Preparation of compound ref 4

[0342]

[0343]

[0344] Preparation of compound ref 4-2

[0345] After introducing 1.8 M LDA (88.0 mL, 157.8 mM) dropwise into a mixed solution of 2-bromodibenzofuran (30.0 g, 121.4 mM) and THF (300 mL) at -78℃, the resulting product was stirred for 1 hour. Iodine (11.0 g, 42.9 mmol) was introduced into the reaction mixture, and the resulting product was stirred at room temperature for 2 hours. After the completion of the reaction, the resulting product was extracted by introducing distilled water and DCM thereto, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified using column chromatography (DCM), and recrystallized with MeOH to obtain the target compound ref 4-2 (23.1 g, 51%). ​

[0346] Preparation of compound ref 4-1

[0347] After dissolving compound ref 4-2 (3.9 g, 10.5 mM), phenylboronic acid (1.3 g, 10.5 mM), Pd(PPh3)4(606 mg, 0.52 mM) and K2CO3(2.9 g, 21.0 mM) in toluene / EtOH / H2O (100 / 20 / 20 mL), the resultant was refluxed for 12 hours. After completion of the reaction, the resultant was extracted by introducing distilled water and DCM thereto, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified using column chromatography (DCM:Hex=1:3), and recrystallized with methanol to obtain the target compound ref 4-1 (2.4 g, 70%).

[0348] Preparation of compound ref 4

[0349] After dissolving compound ref 4-1 (5.1 g, 15.8 mM), 9-phenyl-9H,9’H-3,3’-bicarbazole (6.5 g, 15.8 mM), CuI (3.0 g, 15.8 mM), trans-1,2-diaminocyclohexane (1.9 mL, 15.8 mM) and K3PO4(3.3 g, 31.6 mM) in 1,4-dioxane (100 mL), the resultant was refluxed for 24 hours. After completion of the reaction, the resultant was extracted by introducing distilled water and DCM thereto, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified using column chromatography (DCM:Hex=1:3), and recrystallized with methanol to obtain the target compound ref 4 (8.7 g, 85%).

[0350] [Preparation Example 4] Preparation of compound ref 5

[0351]

[0352] Preparation of compound ref 5-2

[0353] After dissolving 2-bromodibenzo[b,d]thiophene (5.0 g, 19.0 mM), 9H-carbazole (2.6 g, 15.8 mM), CuI (3.0 g, 15.8 mM), trans-1,2-diaminocyclohexane (1.9 mL, 15.8 mM) and K3PO4(3.3 g, 31.6 mM) in 1,4-dioxane (100 mL), the resultant was refluxed for 24 hours. After completion of the reaction, the resultant was extracted by introducing distilled water and DCM thereto, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified using column chromatography (DCM:Hex=1:3), and recrystallized with methanol to obtain the target compound ref 5 (5.0 g, 70%). ​After dissolving ref 5-1 (7.5 g, 19.0 mM), 2-bromodibenzo[b,d]thiophene (5.0 g, 19.0 mM), Pd(PPh3)4 (1.1 g, 0.95 mM) and K2CO3 (5.2 g, 38.0 mM) in toluene / EtOH / H2O (100 / 20 / 20 mL), the resultant was refluxed for 12 hours. After the completion of the reaction, the resultant was extracted by introducing distilled water and DCM thereto, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified using column chromatography (DCM:Hex=1:3), and recrystallized with methanol to obtain the target compound ref 5 (7.1 g, 70%).

[0354] Preparation of compound ref 5-1

[0355] After dissolving ref 5-1 (7.5 g, 19.0 mM), 2-bromodibenzo[b,d]thiophene (5.0 g, 19.0 mM), Pd(PPh3)4 (1.1 g, 0.95 mM) and K2CO3 (5.2 g, 38.0 mM) in toluene / EtOH / H2O (100 / 20 / 20 mL), the resultant was refluxed for 12 hours. After the completion of the reaction, the resultant was extracted by introducing distilled water and DCM thereto, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified using column chromatography (DCM:Hex=1:3), and recrystallized with methanol to obtain the target compound ref 5 (7.1 g, 70%).

[0356] Preparation of compound ref 5

[0357] After dissolving ref 5-1 (7.5 g, 19.0 mM), 2-bromodibenzo[b,d]thiophene (5.0 g, 19.0 mM), Pd(PPh3)4 (1.1 g, 0.95 mM) and K2CO3 (5.2 g, 38.0 mM) in toluene / EtOH / H2O (100 / 20 / 20 mL), the resultant was refluxed for 12 hours. After the completion of the reaction, the resultant was extracted by introducing distilled water and DCM thereto, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified using column chromatography (DCM:Hex=1:3), and recrystallized with methanol to obtain the target compound ref 5 (7.1 g, 70%).

[0358] [Preparation Example 5] Preparation of compound ref 6

[0359]

[0360] After 4,4'-dibromo-2,3-difluoro-2'-methoxy-1,1'-biphenyl (65 g, 200 mmol), 2,3-difluoro-4-methoxyphenyl boronic acid (35.6 g, 200 mmol), Pd(PPh3)4 (1.1 g, 1.0 mmol) and K2CO3 (54.9 g, 400 mmol) were dissolved in toluene / EtOH / H2O (100 / 20 / 20 mL), the resulting was refluxed for 12 hours. After the completion of the reaction, the resulting was extracted by introducing distilled water and DCM thereto, and after drying the organic layer with MgSO4, the solvent was removed using a rotary evaporator. The reaction material was purified using column chromatography (DCM:Hex=1:3), and recrystallized with methanol to obtain the target compound ref 5 (60 g, 90%).

[0361] <Preparation of the 1st group compounds>

[0362] [Preparation Example 6] Preparation of the 1st group compound 1 (C)

[0363]

[0364] Preparation of compound 1-5

[0365] In a single necked round bottom flask (r.b.f), a mixture of 1-bromo-2,3-difluorobenzene (50 g, 259 mmol), (4-chloro-2-methoxyphenyl)boronic acid (57.7 g, 310 mmol), tetrakis(triphenylphosphine)palladium(0) (29 g, 25.9 mmol), potassium carbonate (71.5 g, 51.8 mmol) and toluene / ethanol / water (800 mL / 160 mL / 160 mL) was refluxed at 110°C.

[0366] The resulting was extracted with dichloromethane and dried with MgSO4. The resulting was filtered with silica gel and then concentrated to obtain compound 1-5 (65 g, 99%).

[0367] Preparation of compound 1-4

[0368] In a single necked round bottom flask (r.b.f), a mixture of 4'-chloro-2,3-difluoro-2'-methoxy-1,1'-biphenyl (65 g, 255 mmol) and MC (1000 mL) was cooled to 0°C, BBr3 (48 mL, 500 mmol) was added dropwise thereto, and after the temperature was increased to room temperature, the resulting was stirred for 2 hours.

[0369] The reaction was terminated with distilled water, and the resulting was extracted with dichloromethane and dried with MgSO4. The resulting was column-purified (MC:HX=1:2) to obtain compound 1-4 (49 g, 80%).

[0370] Preparation of compound 1-3

[0371] A mixture of 4-chloro-2',3'-difluoro-[1,1 '-biphenyl]-2-ol (49 g, 203 mmol) and Cs2C03(331 g, 1018 mmol) in dimethylacetamide (500 ml) was stirred at 120 °C in a single necked round bottom flask (r.b.f). The resulting was cooled then filtered and after removing the solvent of the filtrate, column purification (HX:MC = 5:1) was performed to obtain compound 1-3 (10.1 g, 88%).

[0372] Preparation of compound 1-2

[0373] A mixture of 3-chloro-6-fluorodibenzo[b,d]furan (9 g, 40.7 mmol), 9H-carbazole (8.1 g, 48.9 mmol) and Cs2C03(66.3 g, 203.5 mmol) in dimethylacetamide (100 ml) was refluxed at 170 °C for 12 hours in a single necked round bottom flask (r.b.f).

[0374] The resulting was cooled then filtered and after removing the solvent of the filtrate, column purification (HX:MC = 4:1) was performed to obtain compound 1-2 (10.1 g, 67%).

[0375] Preparation of compound 1-1

[0376] A mixture of 9-(7-chlorodibenzo[b,d]furan-4-yl)-9H-carbazole (10.1 g, 27.4 mmol), bis(pinacolato)diboron (13.9 g, 54.9 mmol), XPhos (2.6 g, 5.48 mmol), potassium acetate (8 g, 82 mmol) and Pd(dba)2(1.57 g, 2.74 mmol) in 1,4-dioxane (100 ml) was refluxed at 140 °C in a single necked round bottom flask (r.b.f).

[0377] The resulting was extracted with dichloromethane, concentrated then treated with dichloromethane / MeOH to obtain compound 1-1 (13.4 g, overall yield).

[0378] Preparation of compound 1

[0379] ​In a single necked round bottom flask (r.b.f), 9-(7-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)dibenzo[b,d]furan-4-yl)-9H-carbazole (12.5 g, 27.2 mmol), 2- chloro-4,6-diphenyl-1,3,5-triazine (8.74 g, 32.6 mmol), tetrakis(triphenylphosphine) palladium (0) (3.1 g, 2.72 mmol), potassium carbonate (7.5 g, 54.5 mmol) and 1,4- dioxane (150 mL) were mixed with water (30 mL) and the mixture was refluxed at 120 °C for 3 hours. The resulting product was filtered at 120 °C and washed with 1,4-dioxane, distilled water and MeOH to obtain compound 1(C) (11.2 g, 71% overall yield for two steps) In a single necked round bottom flask (r.b.f), 9-(7-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)dibenzo[b,d]furan-4-yl)-9H-carbazole (12.5 g, 27.2 mmol), 2- chloro-4,6-diphenyl-1,3,5-triazine (8.74 g, 32.6 mmol), tetrakis(triphenylphosphine) palladium (0) (3.1 g, 2.72 mmol), potassium carbonate (7.5 g, 54.5 mmol) and 1,4- dioxane (150 mL) were mixed with water (30 mL) and the mixture was refluxed at 120 °C for 3 hours. The resulting product was filtered at 120 °C and washed with 1,4-dioxane, distilled water and MeOH to obtain compound 1(C) (11.2 g, 71% overall yield for two steps) In a single necked round bottom flask (r.b.f), 9-(7-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)dibenzo[b,d]furan-4-yl)-9H-carbazole (12.5 g, 27.2 mmol), 2- chloro-4,6-diphenyl-1,3,5-triazine (8.74 g, 32.6 mmol), tetrakis(triphenylphosphine) palladium (0) (3.1 g, 2.72 mmol), potassium carbonate (7.5 g, 54.5 mmol) and 1,4- dioxane (150 mL) were mixed with water (30 mL) and the mixture was refluxed at 120 °C for 3 hours. The resulting product was filtered at 120 °C and washed with 1,4-dioxane, distilled water and MeOH to obtain compound 1(C) (11.2 g, 71% overall yield for two steps)

[0380] The following compounds C were synthesized in the same manner as in the preparation of compound 1(C) of Preparation Example 6, except that A and B of the following [Table 3] were used as intermediates.

[0381] Table 3

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390] [Preparation Example 7] Preparation of compound 137(D) of Group 1

[0391]

[0392] The target compound 137(D) (7.3 g, 45%) was obtained in the same manner as in the preparation of compound 1(C) of Preparation Example 6, except that 1-bromo-2,4- difluorobenzene was used instead of 1-bromo-2,3-difluorobenzene.

[0393] The following compounds D were synthesized in the same manner as in the preparation of compound 137 of Preparation Example 7, except that A and B of the following [Table 4] were used as intermediates.

[0394] Table 4

[0395]

[0396]

[0397]

[0398] [Preparation Example 8] Preparation of Compound 189 (E) of Group 1

[0399]

[0400] The target compound 189 (E) (8.4 g, 47%) was obtained in the same manner as in the preparation of Compound 1 (C) of Preparation Example 6, except that 2-bromo-1,4-difluorobenzene was used instead of 1-bromo-2,3-difluorobenzene.

[0401] The following compounds E were synthesized in the same manner as in the preparation of Compound 189 of Preparation Example 8, except that A and B of the following [Table 5] were used as intermediates.

[0402] Table 5

[0403]

[0404]

[0405]

[0406] [Preparation Example 9] Preparation of Compound 241 (F) of Group 1

[0407]

[0408] The target compound 241 (F) (6.4 g, 37%) was obtained in the same manner as in the preparation of Compound 1 (C) of Preparation Example 6, except that 2-bromo-1,3-difluorobenzene was used instead of 1-bromo-2,3-difluorobenzene.

[0409] The following compounds F were synthesized in the same manner as in the preparation of Compound 241 of Preparation Example 9, except that A and B of the following [Table 6] were used as intermediates.

[0410] Table 6

[0411]

[0412]

[0413]

[0414] The 1st group compounds other than the compounds described in Tables 3 to 6 were also prepared in the same manner as in the above Preparation Examples.

[0415] <Preparation of the 2nd group compounds>

[0416] [Preparation Example 10] Preparation of the 2nd group compound 1 (G)

[0417]

[0418] Preparation of Compound 1-5

[0419] In a single necked round bottom flask (r.b.f), a mixture of 1-bromo-2,3-difluorobenzene (40.5 g, 209 mmol), (2-chloro-6-methoxyphenyl)boronic acid (43 g, 230 mmol), tetrakis(triphenylphosphine)palladium(0) (24 g, 20.9 mmol), potassium carbonate (57.9 g, 419 mmol) and toluene / ethanol / water (500 ml / 100 ml / 100 ml) was refluxed at 110°C. The resulting was extracted with dichloromethane and dried over MgSO4. The resulting was filtered over silica gel and then concentrated to obtain compound 1-5 (40.8 g, 76%).

[0420] Preparation of compound 1-4

[0421] In a single necked round bottom flask (r.b.f), a mixture of 2'-chloro-2,3-difluoro-6'-methoxy-1,1'-biphenyl (40.8 g, 160 mmol) and MC (600 mL) was cooled to 0°C to which BBr3(30 mL, 320 mmol) was added dropwise and after the temperature was raised to room temperature, the resulting was stirred for 1 hour. The reaction was quenched with distilled water and the resulting was extracted with dichloromethane and dried over MgSO4. The resulting was column purified (MC:HX = 1:1) to obtain compound 1-4 (21 g, 54%).

[0422] Preparation of compound 1-3

[0423] In a single necked round bottom flask (r.b.f), a mixture of 4-chloro-2',3'-difluoro-[1,1'-biphenyl]-2-ol (21 g, 87.2 mmol) and Cs2CO3(71 g, 218 mmol) in dimethylacetamide (200 ml) was stirred at 120°C. The resulting was cooled, then filtered, and after the solvent of the filtrate was removed, column purification (HX:MC = 4:1) was performed to obtain compound 1-3 (17 g, 88%).

[0424] Preparation of compound 1-2

[0425] In a single-necked round-bottom flask (rbf), a mixture of 1-chloro-6-fluorodibenzo[b,d]furan (6 g, 27.19 mmol), 9H-carbazole (5 g, 29.9 mmol), and Cs₂CO₃ (22 g, 101.7 mmol) in dimethylacetamide (60 mL) was refluxed at 170 °C for 12 h. The result was cooled, filtered, and after removing the solvent from the filtrate, column purification (HX:MC = 3:1) was performed to obtain compounds 1-2 (9 g, 90%).

[0426] Preparation of compound 1-1

[0427] In a single-necked round-bottom flask (RBF), 9-(9-chlorodibenzo[b,d]furan-4-yl)-9H-carbazole (9 g, 24.4 mmol), bis(pinacol)diboron (12.4 g, 48.9 mmol), Pcy3 (1.37 g, 4.89 mmol), potassium acetate (7.1 g, 73 mmol), and Pd2(dba)3 (2.2 g, 2.44 mmol) in a 1,4-dicarboxylic acid solution were added. The alkane (100 ml) mixture was refluxed at 140 °C. The result was cooled, and the filtered filtrate was concentrated and purified by column purification (HX:MC = 3:1) to obtain compound 1-1 (7.2 g, 64%).

[0428] Preparation of compound 1

[0429] In a single-necked round-bottom flask (RBF), 9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)dibenzo[b,d]furan-4-yl)-9H-carbazole (7.2 g, 15.6 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5 g, 18.8 mmol), tetra(triphenylphosphine)palladium(O) (1.8 g, 1.56 mmol), potassium carbonate (4.3 g, 31.2 mmol), and 1,4-diphenylphosphine were added. The mixture of alkyl / water (100 ml / 25 ml) was refluxed at 120 °C for 4 hours. The result was filtered at 120 °C and then subjected to 1,4-dialkyl ... The mixture was washed with alkane, distilled water and MeOH to obtain compound 1(G) (6.6 g, 75%).

[0430] The following compound G was synthesized in the same manner as in the preparation of compound 1 (G) of Preparation Example 10, except that A and B from [Table 7] were used as intermediates.

[0431] Table 7

[0432]

[0433]

[0434]

[0435]

[0436]

[0437]

[0438]

[0439]

[0440]

[0441] [Preparation Example 11] Preparation of compound 129 (H) of Group 2

[0442]

[0443] Preparation of compound 129-5

[0444] In a single necked round bottom flask (r.b.f), a mixture of 1-bromo-2,4-difluorobenzene (40 g, 207 mmol), (2-chloro-6-methoxyphenyl)boronic acid (42.4 g, 227 mmol), tetrakis(triphenylphosphine)palladium(0) (23 g, 20.7 mmol), potassium carbonate (57 g, 414 mmol) and toluene / ethanol / water (600 ml / 150 ml / 150 ml) was refluxed at 110°C.

[0445] The resulting product was extracted with dichloromethane, dried over MgSO4, filtered over silica gel and concentrated to obtain compound 129-5 (50 g, 94%).

[0446] Preparation of compound 129-4

[0447] In a single necked round bottom flask (r.b.f), a mixture of 2'-chloro-2,4-difluoro-6'-methoxy-1,1'-biphenyl (50 g, 196 mmol) and dichloromethane (700 ml) was cooled to 0°C, to which BBr3(28.3 mL, 294 mmol) was added dropwise and after the temperature was raised to room temperature, the resulting product was stirred for 2 hours.

[0448] The reaction was quenched with distilled water and the resulting product was extracted with dichloromethane and dried over MgSO4. The resulting product was filtered over silica gel to obtain compound 129-4 (27.5 g, 58%).

[0449] Preparation of compound 129-3

[0450] In a single-necked round-bottom flask (RBF), a mixture of 4-chloro-2',4'-difluoro-[1,1'-biphenyl]-2-ol (27 g, 114 mmol) and Cs₂CO₃ (83 g, 285 mmol) in dimethylacetamide (300 ml) was stirred at 120 °C. The result was cooled and then filtered, and after removing the solvent from the filtrate, it was filtered through silica gel to obtain compound 129-3 (23 g, 92%).

[0451] Preparation of compound 129-2

[0452] In a single-necked round-bottom flask (rbf), a mixture of 1-chloro-7-fluorodibenzo[b,d]furan (5.5 g, 24.9 mmol), 9H-carbazole (4.58 g, 27.4 mmol), and Cs₂CO₃ (20 g, 62 mmol) in dimethylacetamide (60 mL) was refluxed at 170 °C for 6 h. The result was cooled and filtered, and after removing the solvent from the filtrate, column purification (HX:MC = 3:1) was performed to obtain compound 129-2 (7.6 g, 83%).

[0453] Preparation of compound 129-1

[0454] In a single-necked round-bottom flask (RBF), 9-(9-chlorodibenzo[b,d]furan-3-yl)-9H-carbazole (7.5 g, 20.3 mmol), bis(pinacol)diboron (10.3 g, 40.7 mmol), Pcy3 (1.14 g, 4.07 mmol), potassium acetate (5.97 g, 60.9 mmol), and Pd2(dba)3 (1.85 g, 2.03 mmol) were reacted with 1,4-dicarbazole. The alkane (80 ml) mixture was refluxed at 140 °C. The result was cooled, and the filtered filtrate was concentrated and purified by column purification (HX:MC = 2:1) to obtain compound 129-1 (6.5 g, 70%).

[0455] Preparation of compound 129

[0456] In a single-necked round-bottom flask (RBF), 9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)dibenzo[b,d]furan-3-yl)-9H-carbazole (6.5 g, 14.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (4.54 g, 16.9 mmol), tetrakis(triphenylphosphine)palladium(O) (1.6 g, 1.41 mmol), potassium carbonate (3.9 g, 28.2 mmol), and 1,4-diphenylphosphine were prepared. A mixture of hexane / water (80 ml / 28.2 ml) was refluxed at 120 °C for 4 hours. The resulting product was filtered at 60 °C, and then washed with 60 °C 1,4-dioxane, distilled water and MeOH to obtain compound 129(H) (5.4 g, 68%). Compound 129(H) (5.4 g, 68%) was obtained.

[0457] The following compounds H were synthesized in the same manner as in the preparation of compound 129 of Preparation Example 11, except that D and E of Table 8 below were used as intermediates.

[0458] Table 8

[0459]

[0460]

[0461]

[0462]

[0463]

[0464]

[0465]

[0466]

[0467]

[0468] The second group of compounds, except for the compounds described in Tables 7 and 8, were also prepared in the same manner as in the above preparation examples.

[0469] The synthesis identification data of the above-prepared compounds are as follows. Specifically, the FD-Mass data of the compounds represented by Chemical Formula 24 according to one embodiment of the present application are shown in Table 9 below, the FD-Mass data of the first group of compounds represented by Chemical Formula 1 according to one embodiment of the present application are shown in Table 10 below, and the FD-Mass data of the second group of compounds represented by Chemical Formula 1 according to one embodiment of the present application are shown in Table 11 below.

[0470] [Table 9]

[0471]

[0472]

[0473]

[0474] [Table 10]

[0475]

[0476]

[0477]

[0478]

[0479]

[0480]

[0481] [Table 11]

[0482]

[0483]

[0484]

[0485]

[0486]

[0487] In addition, the synthetic identification data of the above-prepared compounds are as follows. Specifically, the H NMR (CDC13, 200 Mz) data of the compounds represented by Chemical Formula 24 according to one embodiment of the present application are as shown in Table 12 below. 1 H NMR (CDC13, 200 Mz) data of the 1st group of compounds represented by Chemical Formula 1 according to one embodiment of the present application are as shown in Table 12 below. 1 H NMR (CDC13, 200 Mz) data of the 2nd group of compounds represented by Chemical Formula 1 according to one embodiment of the present application are as shown in Table 13 below. 1 H NMR (CDC13, 200 Mz) data are as shown in Table 14 below.

[0488] [Table 12]

[0489]

[0490] [Table 13]

[0491]

[0492]

[0493]

[0494] [Table 14]

[0495]

[0496]

[0497] <Experimental Example 1> Fabrication of an Organic Light-Emitting Device

[0498] A coating of thickness of [missing information] was applied to it using distilled water. Indium tin oxide (ITO) was used as the glass substrate for the thin film, which underwent ultrasonic cleaning. After cleaning with distilled water, the substrate was ultrasonically cleaned with solvents such as acetone, methanol, and isopropanol, then dried, and treated with UVO for 5 minutes in a UV cleaner. The substrate was then transferred to a plasma cleaner (PT) and subjected to plasma treatment under vacuum for ITO work function and residual film removal before being transferred to a thermal deposition apparatus for organic deposition.

[0499] A hole injection layer 2-TNATA (4,4',4”-tris[2-naphthyl(phenyl)amino]triphenylamine) and a hole transport layer NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) are formed on a transparent ITO electrode (anode) as common layers.

[0500] The following describes the thermal vacuum deposition of a luminescent layer on the hole transport layer. As the luminescent layer, a compound of type 1 described in Chemical Formula 1 and a compound of type 24 are deposited as the host material from each separate supply source. Ir(ppy)3 was deposited as a green phosphorescent dopant through 7% doping. Subsequently, BCP was deposited... As a hole-blocking layer, Alq3 was deposited on the hole-blocking layer. As an electron transport layer. Finally, lithium fluoride (LiF) is deposited to... The thickness is used to form an electron injection layer on the electron transport layer, and then an aluminum (Al) cathode is deposited to... The thickness of the electron injection layer is used to form a cathode, thereby creating an organic electroluminescent device.

[0501] Meanwhile, for each material to be used in OLED manufacturing, in 10 -6 Up to 10 -8 All the organic compounds required for OLED manufacturing are purified by vacuum sublimation.

[0502] <Experimental Example 2> Fabrication of an Organic Light-Emitting Device

[0503] It is coated with a thickness of The ITO of the glass substrate used as a thin film was cleaned with distilled water using an ultrasonic cleaner. After the cleaning with distilled water was completed, the substrate was cleaned with solvents such as acetone, methanol, and isopropanol using an ultrasonic cleaner, then dried, and subjected to UVO treatment for 5 minutes using UV in a UV cleaner. Thereafter, the substrate was transferred to a plasma cleaner (PT), and after plasma treatment for ITO work function and residual film removal under vacuum, the substrate was transferred to a thermal deposition apparatus for organic deposition.

[0504] A hole injection layer 2-TNATA (4,4',4"-tris[2-naphthyl(phenyl)amino]triphenylamine) and a hole transport layer NPB (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) were formed as common layers on a transparent ITO electrode (anode).

[0505] The light emitting layer was thermally vacuum deposited on the hole transport layer as follows. As the light emitting layer, one type of compound described in Chemical Formula 1 and one type of compound described in Chemical Formula 24 were previously mixed and deposited as a host in one supply source to and Ir(ppy)3 was deposited as a green phosphorescent dopant by 7% doping. Thereafter, BCP was deposited to as a hole blocking layer, and Alq3 was deposited on the hole blocking layer to as an electron transport layer. Finally, lithium fluoride (LiF) was deposited to a thickness of 10 nm on the electron transport layer, and then an aluminum (Al) cathode was deposited to a thickness of 100 nm on the electron injection layer, thus manufacturing an organic electroluminescent device.

[0506] Meanwhile, for each material to be used in the manufacture of the OLED, the purity was 10 -6 mg / g or more. -8 All of the organic compounds required for the manufacture of the OLED were vacuum sublimation purified at 10

[0507] For the organic electroluminescent device manufactured as above, electroluminescence (EL) characteristics were measured using M7000 manufactured by McScience Inc., and with the measurement results, T 2 was measured at a standard luminance of 6000 cd / m 90 .

[0508] The organic electroluminescent devices according to Experimental Example 1 and Experimental Example 2 had the driving voltage and luminous efficiency as follows.

[0509] Table 15 below shows the driving voltage and luminous efficiency of the organic electroluminescent device when the heterocyclic compound of Chemical Formula 24 of the present application is used alone, Table 16 below shows the driving voltage and luminous efficiency of the organic electroluminescent device when the 1st group of compounds of the heterocyclic compound of Chemical Formula 1 of the present application is used alone, and Table 17 below shows the driving voltage and luminous efficiency of the organic electroluminescent device when the 2nd group of compounds of the heterocyclic compound of Chemical Formula 1 of the present application is used alone.

[0510] [Table 15]

[0511]

[0512]

[0513] [Table 16]

[0514] Light-emitting layer compound Driving voltage (V) Efficiency (cd / A) Color coordinates (x, y) Life (T 90 )]]> Comparative Example 13 139 4.22 71.2 (0.282,0.672) 171 Comparative Example 14 143 4.09 69.1 (0.278,0.669) 143 Comparative Example 15 190 4.32 78.6 (0.273,0.673) 181 Comparative Example 16 191 4.27 77.3 (0.278,0.682) 176 Comparative Example 17 204 4.11 61.3 (0.280,0.664) 137 Comparative Example 18 205 4.19 65.1 (0.294,0.682) 185 Comparative Example 19 219 4.24 64.9 (0.272,0.684) 176

[0515] [Table 17]

[0516] Light-emitting layer compound Driving voltage (V) Efficiency (cd / A) Color coordinates (x, y) Life (T 90 )]]> Comparative Example 20 129 3.92 73.8 (0.269,0.665) 143 Comparative Example 21 136 4.02 67.3 (0.274,0.677) 153 Comparative Example 22 139 3.89 72.1 (0.262,0.688) 148 Comparative Example 23 144 4.10 80.5 (0.290,0.681) 187

[0517] In addition, Table 18 below shows the driving voltage and luminous efficiency of the organic electroluminescent device when the heterocyclic compound of Chemical Formula 24 of the present application and the 1st group of compounds of the heterocyclic compound of Chemical Formula 1 of the present application are mixed and used, and specifically, shows data on constructing a device by changing the ratio of the heterocyclic compound of Chemical Formula 24 to the 1st group of compounds of the heterocyclic compound of Chemical Formula 1. Table 19 below shows the driving voltage and luminous efficiency of the organic electroluminescent device when the heterocyclic compound of Chemical Formula 24 of the present application and the 2nd group of compounds of the heterocyclic compound of Chemical Formula 1 of the present application are mixed and used, and specifically, shows data on constructing a device by changing the ratio of the heterocyclic compound of Chemical Formula 24 to the 2nd group of compounds of the heterocyclic compound of Chemical Formula 1.

[0518] [Table 18]

[0519]

[0520]

[0521] [Table 19]

[0522]

[0523]

[0524]

[0525] Table 20 below shows the driving voltage and luminous efficiency of the organic electroluminescent device when the heterocyclic compound of Chemical Formula 24 of the present application and the 1st group compounds of the heterocyclic compound of Chemical Formula 1 of the present application are mixed and used, and specifically, shows data on constructing a device according to the compound type after fixing the ratio of the heterocyclic compound of Chemical Formula 24 to the 1st group compounds of the heterocyclic compound of Chemical Formula 1. Table 21 below shows the driving voltage and luminous efficiency of the organic electroluminescent device when the heterocyclic compound of Chemical Formula 24 of the present application and the 2nd group compounds of the heterocyclic compound of Chemical Formula 1 of the present application are mixed and used, and specifically, shows data on constructing a device according to the compound type after fixing the ratio of the heterocyclic compound of Chemical Formula 24 to the 2nd group compounds of the heterocyclic compound of Chemical Formula 1.

[0526] [Table 20]

[0527]

[0528] [Table 21]

[0529]

[0530]

[0531] Table 22 below shows the driving voltage and luminous efficiency of the organic electroluminescent device according to the doping concentration when the heterocyclic compound of Chemical Formula 24 of the present application and the 1st group compounds of the heterocyclic compound of Chemical Formula 1 of the present application are mixed and used, and Table 23 below shows the driving voltage and luminous efficiency of the organic electroluminescent device according to the doping concentration when the heterocyclic compound of Chemical Formula 24 of the present application and the 2nd group compounds of the heterocyclic compound of Chemical Formula 1 of the present application are mixed and used.

[0532] [Table 22]

[0533]

[0534]

[0535] [Table 23]

[0536]

[0537] As seen from Tables 15 to 23, it was determined that when both the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24 are contained in the organic material layer of the organic light-emitting device, more excellent efficiency and lifespan effects are obtained compared to when the heterocyclic compound of Chemical Formula 1 alone or the heterocyclic compound of Chemical Formula 24 alone is contained in the organic material layer. Such a result leads to a prediction that an excimer phenomenon occurs when both compounds are contained at the same time.

[0538] Exciplex phenomenon is a phenomenon in which energy having the size of the HOMO level of a donor (p-host) and the size of the LUMO level of an acceptor (n-host) is released due to exchange of electrons between two molecules. When exciplex phenomenon occurs between two molecules, reverse intersystem crossing (RISC) occurs as a result, and the internal quantum efficiency of fluorescence can increase up to 100%. When a donor (p-host) having good hole transport ability and an acceptor (n-host) having good electron transport ability are used as a host of a light-emitting layer, holes are injected to the p-host and electrons are injected to the n-host, and thus, it is possible to reduce driving voltage, thereby contributing to improvement in lifespan.

[0539] In particular, it was determined that the heterocyclic compound represented by Chemical Formula 24 introduces dibenzothiophene group as a heteroaryl group into a bis-carbazole form, and by expanding the HOMO to thereby enhance hole transport ability, excellent characteristics in efficiency were obtained. When Comparative Examples 30 and 31 of Table 18 were compared with the organic light-emitting device of the present application, it was determined that when dibenzothiophene as the heterocyclic compound of Chemical Formula 24 of the present application was present, stronger aromaticity was obtained compared to dibenzofuran, and thus, characteristics of longer lifespan were obtained due to structural stability.

[0540] When Comparative Examples 28 and 29 of Table 18 were compared with the organic light-emitting device of the present application, it was determined that suppression of reactivity by introducing a substituent to the 4th carbon (a position having relatively good reactivity) in dibenzothiophene was also a factor in generating long lifespan characteristics.

[0541] In addition, Tables 22 and 23 were measured by changing the dopant concentration, and in general light-emitting devices, as the dopant concentration decreases, the driving voltage and efficiency decrease and the lifespan increases, and as the dopant concentration increases, the efficiency-improving effect can be expected due to the increased possibility of energy transfer from the host to the dopant, however, it is known that this has the disadvantage that the lifespan of the device itself is suppressed due to occurrence of charge trapping, and the driving voltage is increased.

[0542] However, as determined in Tables 22 and 23, it was determined that the efficiency of low dopant doping in the present disclosure has similar or enhanced effects compared to high doping. This is considered to be due to the fact that the host used in the present disclosure (a mixture of Chemical Formula 1 and Chemical Formula 24 of the present application) has good charge transport ability, which facilitates energy transfer from the host to the dopant even in the case of low doping, thereby contributing to improvement in efficiency and lifespan, and thus, it was determined that there is an advantage in using a small amount of dopant when used together with the host used in the present disclosure.

[0543] [Reference Signs]

[0544] 100: substrate

[0545] 200: anode

[0546] 300: organic material layer

[0547] 301: hole injection layer

[0548] 302: hole transport layer

[0549] 303: light emitting layer

[0550] 304: hole blocking layer

[0551] 305: electron transport layer

[0552] 306: electron injection layer

[0553] 400: cathode

Claims

1. An organic light emitting device comprising: a first electrode; a second electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more layers of the organic material layers comprise a heterocyclic compound represented by the following Chemical Formula 1 and a heterocyclic compound represented by the following Chemical Formula 24: [Chemical Formula 1] [Chemical Formula 24] In Chemical Formulas 1 and 24, N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclic group containing one or more N; L and L1 are a direct bond; a substituted or unsubstituted C6 to C60 arylene; or a substituted or unsubstituted C2 to C60 heteroarylene, a is an integer of 1 to 3, and when a is 2 or more, L are the same as or different from each other; R9 to R12 are the same as or different from each other, and each is independently selected from hydrogen; and deuterium; R1 to R8, R13 and R14 are the same as or different from each other, and each is independently selected from hydrogen; deuterium; halogen; cyano; a substituted or unsubstituted C1 to C60 alkyl; a substituted or unsubstituted C2 to C60 alkenyl; a substituted or unsubstituted C2 to C60 alkynyl; a substituted or unsubstituted C2 to C60 alkoxy; a substituted or unsubstituted C3 to C60 cycloalkyl; a substituted or unsubstituted C2 to C60 heterocycloalkyl; a substituted or unsubstituted C6 to C60 aryl; a substituted or unsubstituted C2 to C60 heteroaryl; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more of the groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring or a substituted or unsubstituted C2 to C60 heterocycle; b and c are each an integer of 1 to 3; when b is 2 or more, R9 are the same as or different from each other, and when c is 2 or more, R10 are the same as or different from each other; m, p and q are integers of 0 to 4; n is an integer of 0 to 2; when m is 2 or more, R11 are the same as or different from each other, when n is the integer 2, R12 are the same as or different from each other, when p is 2 or more, R13 are the same as or different from each other, and when q is 2 or more, R14 are the same as or different from each other; Ar1 is a substituted or unsubstituted C6 to C60 aryl; or a substituted or unsubstituted C2 to C60 heteroaryl containing at least one of S and O; and Ar2 is a substituted or unsubstituted C6 to C60 aryl; or a substituted or unsubstituted C2 to C60 heteroaryl. 2.The organic light emitting device according to claim 1, wherein Chemical Formula 1 is represented by the following Chemical Formula 2 or Chemical Formula 3: [Chemical Formula 2] [Chemical Formula 3] In Chemical Formulas 2 and 3, R1 to R10, L, N-Het, a, b and c have the same definition as in Chemical Formula 1. 3.The organic light emitting device according to claim 1, wherein Chemical Formula 1 is represented by one of the following Chemical Formulas 12 to 14: [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] In Chemical Formulas 12 to 14, X1is CR21or N, X2is CR22or N, X3is CR23or N, X4is CR24or N, X5is CR25or N, and at least one of X1to X5is N; and R21to R25and R27to R32are the same as or different from each other, and each is independently selected from the group consisting of hydrogen; deuterium; a halogen; a cyano; a substituted or unsubstituted C1to C60alkyl; a substituted or unsubstituted C2to C60alkenyl; a substituted or unsubstituted C2to C60alkynyl; a substituted or unsubstituted C2to C60alkoxy; a substituted or unsubstituted C3to C60cycloalkyl; a substituted or unsubstituted C2to C60heterocycloalkyl; a substituted or unsubstituted C6to C60aryl; a substituted or unsubstituted C2to C60heteroaryl; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more radicals adjacent to each other are bonded to each other to form a substituted or unsubstituted C6to C60aromatic hydrocarbon ring or a substituted or unsubstituted C2to C60hetero ring.

4. The organic light emitting device according to claim 3, wherein the chemical formula 12 is is represented by one of the following chemical formulas 15 to 18: [Chemical Formula 15] [Chemical Formula 16] [Chemical Formula 17] [Chemical Formula 18] In Chemical Formula 15, one or more of X1, X3, and X5is N, and the rest have the same definition as in Chemical Formula 12; In Chemical Formula 16, one or more of X1, X2, and X5is N, and the rest have the same definition as in Chemical Formula 12; In Chemical Formula 17, one or more of X1to X3is N, and the rest have the same definition as in Chemical Formula 12; In Chemical Formula 18, one or more of X1, X2, and X5is N, and the rest have the same definition as in Chemical Formula 12; and R22, R24, and R33to R36are the same as or different from each other, and each is independently selected from the group consisting of hydrogen; deuterium; a halogen; a cyano; a substituted or unsubstituted C1to C60alkyl; a substituted or unsubstituted C2to C60alkenyl; a substituted or unsubstituted C2to C60alkynyl; a substituted or unsubstituted C2to C60alkoxy; a substituted or unsubstituted C3to C60cycloalkyl; a substituted or unsubstituted C2to C60heterocycloalkyl; a substituted or unsubstituted C6to C60aryl; a substituted or unsubstituted C2to C60heteroaryl; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more radicals adjacent to each other are bonded to each other to form a substituted or unsubstituted C6to C60aromatic hydrocarbon ring or a substituted or unsubstituted C2to C60hetero ring.

5. The organic light emitting device according to claim 4, wherein Chemical Formula 15 is selected from the following structural formulas: In the structure, R21to R25have the same definition as in Chemical Formula 15.

6. The organic light emitting device according to claim 1, wherein Chemical Formula 24 is represented by any one of the following Chemical Formulas 25 to 28: [Chemical Formula 25] [Chemical Formula 26] [Chemical Formula 27] [Chemical Formula 28] In Chemical Formulas 25 to 28, R11to R14, L1, Ar1, Ar2, m, n, p, and q have the same definitions as in Chemical Formula 24.

7. The organic light emitting device according to claim 1, wherein Ar1of Chemical Formula 24 is C6to C20monocyclic or polycyclic aryl unsubstituted or substituted with C1to C10alkyl; or polycyclic C2to C20heteroaryl including at least one of S and O; and Ar2of Chemical Formula 24 is C6to C20aryl.

8. The organic light emitting device according to claim 1, wherein Chemical Formula 1 is represented by any one of the following Group 1 and Group 2 compounds: [Group 1] [Group 2] 9. The organic light emitting device according to claim 1, wherein Chemical Formula 24 is represented by any one of the following compounds:

10. The organic light emitting device according to claim 1, wherein the organic material layer includes at least one of a hole blocking layer, an electron injecting layer, and an electron transporting layer, and at least one of the hole blocking layer, the electron injecting layer, and the electron transporting layer includes the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24.

11. The organic light emitting device according to claim 1, wherein the organic material layer includes an emitting layer including a host material, and the host material includes the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24.

12. The organic light emitting device according to claim 1, wherein the organic material layer includes an emitting layer including a host material and a dopant material, and the host material includes the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 24; and The content of the dopant material is greater than or equal to 1 part by weight and less than or equal to 15 parts by weight with respect to 100 parts by weight of the host material.

13. The organic light emitting device according to claim 1, comprising one, two or more layers selected from the group consisting of an emitting layer, a hole injecting layer, a hole transporting layer, an electron injecting layer, an electron transporting layer, an electron blocking layer, and a hole blocking layer.

14. A composition for an organic material layer of an organic light emitting device, the composition comprising: a heterocyclic compound represented by the following Chemical Formula 1; and a compound represented by the following Chemical Formula 24: [Chemical Formula 1] [Chemical Formula 24] In Chemical Formulas 1 and 24, N-Het is a monocyclic or polycyclic heterocyclic group substituted or unsubstituted and including one or more N; L and L1are a direct bond; a substituted or unsubstituted C6to C60arylene; or a substituted or unsubstituted C2to C60heteroarylene, a is an integer of 1 to 3, and when a is 2 or more, L are the same as or different from each other; R9to R12are the same as or different from each other, and each is independently selected from the group consisting of hydrogen; and deuterium; R1to R8, R13, and R14are the same as or different from each other, and each is independently selected from the group consisting of hydrogen; deuterium; a halogen; a cyano group; a substituted or unsubstituted C1to C60alkyl; a substituted or unsubstituted C2to C60alkenyl; a substituted or unsubstituted C2to C60alkynyl; a substituted or unsubstituted C2to C60alkoxy; a substituted or unsubstituted C3to C60cycloalkyl; a substituted or unsubstituted C2to C60heterocycloalkyl; a substituted or unsubstituted C6to C60aryl; a substituted or unsubstituted C2to C60heteroaryl; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more of the groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C6to C60aromatic hydrocarbon ring or a substituted or unsubstituted C2to C60heterocyclic ring; b and c are each an integer of 1 to 3; R9are the same as or different from each other when b is 2 or more, and R10are the same as or different from each other when c is 2 or more; m, p, and q are integers of 0 to 4; n is an integer of 0 to 2; R11are the same as or different from each other when m is 2 or more, R12are the same as or different from each other when n is the integer 2, R13are the same as or different from each other when p is 2 or more, and R14are the same as or different from each other when q is 2 or more; Ar1is a substituted or unsubstituted C6to C60aryl; or a substituted or unsubstituted C2to C60heteroaryl including at least one of S and O; and Ar2is a substituted or unsubstituted C6to C60aryl; or a substituted or unsubstituted C2to C60heteroaryl.

15. The composition for an organic material layer of an organic light emitting device according to claim 14, wherein, In the composition, the weight ratio of the heterocyclic compound represented by Chemical Formula 1: the heterocyclic compound represented by Chemical Formula 24 is 1:10 to 10:

1.

16. A method for manufacturing an organic light emitting device, the method comprising: preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layers, wherein the forming of the organic material layers comprises forming one or more organic material layers using the composition for an organic material layer according to claim 14.

17. The method for manufacturing an organic light emitting device according to claim 16, wherein the forming of the organic material layers is formed using a method of thermal vacuum deposition after pre-mixing the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 24.

18. The method for manufacturing an organic light emitting device according to claim 16 or 17, wherein the forming of the first electrode is formed using a method of thermal vacuum deposition after pre-mixing the heterocyclic compound of Chemical Formula 1 and the heterocyclic compound of Chemical Formula 24.

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