KR20210143532A - Organic light emitting device - Google Patents

Abstract

The present specification relates to an organic light emitting element which comprises: a first electrode; a second electrode; and two or more organic material layers installed between the first electrode and the second electrode. The organic material layers include a light emitting layer. The organic material layers further comprise at least one layer of a hole injection layer, a hole transport layer, an electron blocking layer, and a hole transport auxiliary layer. At least one layer of the hole injection layer, the hole transport layer, the electron blocking layer and the hole transport auxiliary layer contains a heterocyclic compound represented by chemical formula 1. The light emitting layer comprises a heterocyclic compound represented by chemical formula 2 or chemical formula 3.

Description

Organic light emitting device {ORGANIC LIGHT EMITTING DEVICE}

The present specification relates to an organic light emitting device.

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

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

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

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

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

An object of the present application is to provide an organic light emitting device having excellent performance.

An exemplary embodiment of the present application is an organic light emitting device including a first electrode, a second electrode, and two or more organic material layers provided between the first electrode and the second electrode,

The organic material layer includes a light emitting layer,

The organic light emitting device is provided between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, and further comprises at least one layer of an organic material layer comprising a heterocyclic compound represented by the following Chemical Formula 1,

The light emitting layer provides an organic light emitting device comprising a heterocyclic compound represented by the following Chemical Formula 2 or Chemical Formula 3.

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,

Ar _{1 To} Ar _{4 Are} the same as or different from each other, and are each independently a substituted or unsubstituted C 6 to C 60 aryl group,

R _m is hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C 1 to C 60 alkyl group; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, m is an integer from 0 to 4, and when m is 2 or more, R _m are the same as or different from each other,

n is an integer of 1 to 3, and when n is 2 or more, the substituents in parentheses are the same as or different from each other,

N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclic group containing one or more N,

L is a direct bond; a substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms, a is an integer of 1 to 3, and when a is 2 or more, L is the same as or different from each other,

R _a and R _b are the same as or different from each other, and each independently a substituted or unsubstituted C 6 to C 60 aryl group; Or a substituted or unsubstituted C 2 to C 60 heteroaryl group,

R1 to R10, R _c and R _d are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C 1 to C 60 alkyl group; a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; a substituted or unsubstituted C 3 to C 60 cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; a substituted or unsubstituted C 6 to C 60 aryl group; a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; a substituted or unsubstituted silyl 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 aliphatic or aromatic hydrocarbon ring or a hetero ring,

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

r and s are integers from 0 to 7, R _c is the same as or different from each other _{when r is 2 or more, and R d} is the same as or different from each other when s is 2 or more.

Heterocyclic compounds according to an exemplary embodiment of the present application may be used as an organic material layer material of an organic light emitting device. Each of the heterocyclic compounds may be used as a material for a hole injection layer, a hole transport layer, an electron blocking layer, a hole transport auxiliary layer (prime layer), a light emitting layer, and the like in an organic light emitting device.

Specifically, the heterocyclic compound represented by Formula 1 is used in at least one layer of a hole injection layer, a hole transport layer, an electron blocking layer, and a hole transport auxiliary layer of an organic light emitting device, and is represented by Formula 2 or Formula 3 When the heterocyclic compound is used in the light emitting layer of the organic light emitting device, it is possible to lower the driving voltage of the device, improve the light efficiency, and improve the lifespan characteristics of the device by thermal stability of the compound.

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

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

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

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

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

More specifically, In the present specification, "substituted or unsubstituted" means a monocyclic or polycyclic aryl group having 6 to 60 carbon atoms; or a monocyclic or polycyclic heteroaryl group having 2 to 60 carbon atoms; It may mean unsubstituted or substituted with one or more substituents selected from the group.

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

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

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

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

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C20. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. may be It is not limited.

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

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

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

In the present specification, the phosphine oxide group is represented by -P(=O)R101R102, R101 and R102 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. The phosphine oxide group specifically includes, but is not limited to, a diphenylphosphine oxide group, a dinaphthylphosphine oxide, and the like.

In the present specification, the silyl group is a substituent including Si and the Si atom is directly connected as a radical, and is represented by -SiR104R105R106, R104 to R106 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specific examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. It is not limited.

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

In the present specification, the spiro group is a group including a spiro structure, and may have 15 to 60 carbon atoms. For example, the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro bonded to a fluorenyl group. Specifically, the following spiro group may include any one of the groups of the following structural formula.

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

In the present specification, the amine group is a monoalkylamine group; monoarylamine group; monoheteroarylamine group; -NH ₂ ; dialkylamine group; diarylamine group; diheteroarylamine group; an alkylarylamine group; an alkyl heteroarylamine group; And it may be selected from the group consisting of an aryl heteroarylamine group, the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a dibiphenylamine group, an anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluorene There is a nylamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group, and the like, but is not limited thereto.

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

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

The structures exemplified by the above-described cycloalkyl group, cycloheteroalkyl group, aryl group and heteroaryl group may be applied, except that the aliphatic or aromatic hydrocarbon ring or heterocycle that adjacent groups may form is not a monovalent group.

In an exemplary embodiment of the present application, an organic light emitting device including a first electrode, a second electrode, and two or more organic material layers provided between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, The organic light emitting device further includes at least one organic material layer provided between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, the organic material layer including a heterocyclic compound represented by the following Chemical Formula 1, wherein the light emitting layer includes the It provides an organic light emitting device comprising a heterocyclic compound represented by Formula 2 or Formula 3.

In an exemplary embodiment of the present application, the organic material layer including the heterocyclic compound represented by Formula 1 is one or two layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, and a hole transport auxiliary layer. may be more than

As used herein, the term "hole transport auxiliary layer" is a layer disposed between the hole transport layer and the light emitting layer of the organic light emitting device, and prevents electrons from passing from the light emitting layer to the anode layer, thereby preventing the luminance, efficiency, and lifespan characteristics of the organic light emitting device. It means a functional layer used for the purpose of enhancement, also called "prime layer" or "electron defense layer".

The material constituting the hole transport auxiliary layer may be determined according to the light emitting material of the light emitting layer. For example, a hole transport auxiliary layer used together with a light emitting layer using a red host as a light emitting material is referred to as a red prime layer. Highest Occupied Molecular Orbital (HOMO) level and Lowest Unoccupied Molecular Orbital (LUMO) level and high T1 for use in layers such as a hole transport layer, an electron blocking layer, and a hole transport auxiliary (HT-prime) layer It has a value and can realize a long-life device by securing excellent hole transport ability and thermal stability. Here, the T1 value means the energy level value of the triplet state.

At least one of the hole injection layer, the hole transport layer, the electron blocking layer and the hole transport auxiliary layer of the organic light emitting device contains the compound represented by Formula 1, and at the same time, the compound represented by Formula 2 or Formula 3 is used in the organic light emitting device. When the light emitting layer of the organic light emitting device is included, it shows better efficiency and lifespan effect.

From this result, it can be expected that an exciplex phenomenon occurs when the two compounds are simultaneously included in each layer.

The exciplex phenomenon is a phenomenon in which energy having a size of a HOMO level of a donor (p-host) and a LUMO level of an acceptor (n-host) is emitted through electron exchange between two molecules. When an exciplex phenomenon occurs between two molecules, Reverse Intersystem Crossing (RISC) occurs, thereby increasing the internal quantum efficiency of fluorescence to 100%.

In an exemplary embodiment of the present application, an organic light emitting device comprising an anode, a cathode, and two or more organic material layers provided between the anode and the cathode, wherein the organic material layer includes a light emitting layer, and the organic light emitting device includes the light emitting layer and the It is provided between the anode or between the light emitting layer and the cathode, and further comprises at least one layer of an organic material layer comprising a heterocyclic compound represented by Formula 1, wherein the light emitting layer comprises a heterocyclic compound represented by Formula 2 and Formula 3 It is possible to provide an organic light emitting device that is included at the same time.

In an exemplary embodiment of the present application, Ar ₁ to Ar ₄ of Formula 1 may be the same as or different from each other, and each independently a substituted or unsubstituted C 6 to C 60 aryl group.

In another exemplary embodiment of the present application, Ar _{1 To} Ar ₄ may be the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

In another exemplary embodiment of the present application, Ar _{1 To} Ar ₄ may be the same as or different from each other, and may each independently be a substituted or unsubstituted C 6 to C 20 aryl group.

More specifically, Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted anthracenyl group; a substituted or unsubstituted phenanthrenyl group; or a substituted or unsubstituted pyrene group.

Wherein Ar _{1 To} Ar _{4 Are} each independently a phenyl group; biphenyl group; terphenyl group; naphthyl group; anthracenyl group; phenanthrenyl group; or pyrene.

In an exemplary embodiment of the present application, R _m of Formula 1 is hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C 1 to C 60 alkyl group; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, m is an integer of 0 to 4, and when m is 2 or more, R _m are the same as or different from each other.

In another exemplary embodiment of the present application, R _m is hydrogen.

In an exemplary embodiment of the present application, n is an integer of 1 to 3, and when n is 2 or more, the substituents in parentheses may be the same as or different from each other.

In an exemplary embodiment of the present application, n is 1.

In an exemplary embodiment of the present application, n is 2.

In an exemplary embodiment of the present application, n is 3.

In an exemplary embodiment of the present application, when n is 2, the substituents in parentheses may be the same as or different from each other.

In an exemplary embodiment of the present application, when n is 3, the substituents in parentheses may be the same as or different from each other.

In the exemplary embodiment of the present application, Chemical Formula 1 may be represented by any one of the following Chemical Formulas A-1 to A-3.

[Formula A-1]

[Formula A-2]

[Formula A-3]

In the formulas A-1 to A-3,

Ar ₁ to Ar ₄ are the same as in Formula 1,

Ar ₅ is a substituted or unsubstituted C 6 to C 60 aryl group,

R _m1 to R _m6 are each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C 1 to C 60 alkyl group; Or a substituted or unsubstituted C 6 to C 60 aryl group,

m1 to m5 are each independently an integer of 0 to 4, and when m1 to m5 are each 2 or more, the substituents in each parenthesis are the same as or different from each other,

m6 is an integer of 0 to 3, and when m6 is 2 or more, the substituents in parentheses are the same as or different from each other.

In the exemplary embodiment of the present application, R _m1 to R _m6 in Formulas A-1 to A-3 are hydrogen.

In the exemplary embodiment of the present application, Ar ₅ of Formula A-3 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment of the present application, Ar ₅ is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

In another exemplary embodiment of the present application, Ar ₅ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

More specifically, Ar ₅ is a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted anthracenyl group; a substituted or unsubstituted phenanthrenyl group; or a substituted or unsubstituted pyrene group.

The Ar ₅ is a phenyl group; biphenyl group; terphenyl group; naphthyl group; anthracenyl group; phenanthrenyl group; or pyrene.

At least one of the hole injection layer, the hole transport layer, the electron blocking layer, and the hole transport auxiliary layer of the organic light emitting device contains the compound represented by Formulas A-1 to A-3, and is represented by Formula 2 or Formula 3 When the light emitting layer of the organic light emitting device includes the compound to be used, the organic light emitting device exhibits better efficiency and lifespan effect.

In particular, when the compound represented by Formula A-2 is used as a prime layer, it is easier to implement a long-life device, and when the compound represented by Formula A-2 is used as a red prime layer, organic light emitting diode is used. It is possible to further increase the efficiency in the device.

In an exemplary embodiment of the present application, Chemical Formula 2 may be represented by Chemical Formula 4 or 5 below.

[Formula 4]

[Formula 5]

In Formula 4 or 5, the definitions of N-Het, L, R1 to R10, and a to c are the same as those in Formula 2 above.

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

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

In Formulas 4-1 to 4-4, the substituents are as defined in Formula 4 above.

In an exemplary embodiment of the present application, Chemical Formula 5 may be represented by any one of Chemical Formulas 5-1 to 5-4 below.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

In Formulas 5-1 to 5-4, the substituents are as defined in Formula 5 above.

In particular, when the N-containing ring is substituted at the 1st and 3rd carbon positions of the dibenzofuran structure of the heterocyclic compound represented by Formula 2, the tendency to draw electrons toward the electron withdrawing unit Therefore, it is possible to more stabilize the bond of the carbazole group substituted on the opposite side of dibenzofuran. This helps to secure the stability of the molecular structure.

In particular, in the heterocyclic compound represented by Formula 2, when the N-containing ring is substituted at the 3rd carbon position of the dibenzofuran structure, the linearity of the entire material increases, resulting in a stronger electron attraction effect. and has the effect of increasing the stability of the overall structure. In particular, when triazine is substituted, dibenzofuran at the center of the structure maintains an electron-deficient state, which requires more electrical energy (electrons) to break the bond. In this case, the higher the linearity of the material, the stronger the electrons are attracted, and as electrons in the molecule are concentrated around the triazine structure, the effect of further increasing the electron depletion effect of the entire structure can be obtained. Therefore, there is an effect of preventing the decomposition of the host material by the flow of current when driving the device, and when it is used in an organic light emitting device, the device lifespan can be improved. However, the molecular structure is elongated longer than at No. 1 and other positions, resulting in a more bulky form.

In an exemplary embodiment of the present application, the N-Het is a monocyclic or polycyclic heterocycle including one or more N-substituted or unsubstituted.

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

In another embodiment, the N-Het is substituted or unsubstituted with one or more substituents selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, a dimethyl fluorene group, a dibenzofuran group, and a dibenzothiophene group, and , is a monocyclic or polycyclic heterocycle containing one or more N.

In another embodiment, the N-Het is substituted or unsubstituted with one or more substituents selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, a dimethyl fluorene group, a dibenzofuran group, and a dibenzothiophene group, and , It is a monocyclic or polycyclic heterocyclic ring containing 1 or more and 3 or less N.

In the exemplary embodiment of the present application, the N-Het is a monocyclic heterocycle that is substituted or unsubstituted, and includes one or more N.

In an exemplary embodiment of the present application, the N-Het is a substituted or unsubstituted, two or more heterocyclic rings including one or more N.

In the exemplary embodiment of the present application, the N-Het is a monocyclic or polycyclic heterocycle including two or more N-substituted or unsubstituted.

In an exemplary embodiment of the present application, the N-Het is a bicyclic or more polycyclic heterocycle including two or more N.

In an exemplary embodiment of the present application, the N-Het is a pyrimidine group unsubstituted or substituted with a phenyl group; a triazine group unsubstituted or substituted with one or more substituents selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, a dimethyl fluorene group, a dibenzofuran group, and a dibenzothiophene group; a phenyl group-substituted or unsubstituted benzimidazole group; a quinazoline group unsubstituted or substituted with one or more substituents selected from the group consisting of a phenyl group and a biphenyl group; Or it may be a phenanthroline group substituted or unsubstituted with a phenyl group.

In an exemplary embodiment of the present application, the N-Het is a pyrimidine group unsubstituted or substituted with a phenyl group; a triazine group unsubstituted or substituted with one or more substituents selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, a dimethyl fluorene group, a dibenzofuran group, and a dibenzothiophene group; a phenyl group-substituted or unsubstituted benzimidazole group; a quinazoline group unsubstituted or substituted with one or more substituents selected from the group consisting of a phenyl group and a biphenyl group; Or it may be a phenanthroline group substituted or unsubstituted with a phenyl group.

In an exemplary embodiment of the present application, Chemical Formula 2 may be represented by any one of Chemical Formulas 6 to 11 below.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

In Formulas 6 to 11,

R1 to R10, L, a, b and c have the same definitions as in Formula 2,

X1 is CR11 or N, X2 is CR12 or N, X3 is CR13 or N, X4 is CR14 or N, X5 is CR15 or N;

R11 to R15 and R17 to R22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C 1 to C 60 alkyl group; a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; a substituted or unsubstituted C 3 to C 60 cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; a substituted or unsubstituted C 6 to C 60 aryl group; a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a hetero ring.

는 하기 화학식 12 내지 15 중 하나로 표시될 수 있다.In an exemplary embodiment of the present application, the formulas 6 and 9

may be represented by one of the following Chemical Formulas 12 to 15.

은 상기 화학식 6 및 9의 L에 연결되는 부위이다. here,

is a site connected to L in Formulas 6 and 9 above.

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

In Formula 12, at least one of X1, X3 and X5 is N, and the rest are as defined in Formulas 6 and 9,

In Formula 13, at least one of X1, X2 and X5 is N, and the rest are as defined in Formulas 6 and 9,

In Formula 14, at least one of X1 to X3 is N, and the rest are as defined in Formulas 6 and 9,

In Formula 15, at least one of X1, X2 and X5 is N, and the rest are as defined in Formulas 6 and 9,

R12, R14 and R23 to R26 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C 1 to C 60 alkyl group; a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; a substituted or unsubstituted C 3 to C 60 cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; a substituted or unsubstituted C 6 to C 60 aryl group; a substituted or unsubstituted heteroaryl group having 6 to 60 carbon atoms; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group or adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a hetero ring.

In an exemplary embodiment of the present application, Chemical Formula 12 may be selected from any one of the following structural formulas of Group A.

[Group A]

Substituent definitions of the structural formulas of Group A are the same as in Chemical Formula 12.

In the exemplary embodiment of the present application, Chemical Formula 13 may be represented by the following Chemical Formula 16.

[Formula 16]

The substituents of Formula 16 are as defined in Formula 13.

In the exemplary embodiment of the present application, Chemical Formula 14 may be represented by Chemical Formula 17 below.

[Formula 17]

The substituents of Formula 17 are as defined in Formula 14.

In the exemplary embodiment of the present application, Chemical Formula 13 may be represented by the following Chemical Formula 18.

[Formula 18]

In Formula 18, R27 is the same as or different from each other and is hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C 1 to C 60 alkyl group; a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; a substituted or unsubstituted C 3 to C 60 cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; a substituted or unsubstituted C 6 to C 60 aryl group; a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; a substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a hetero ring, e is an integer from 0 to 7, and e is In the case of 2 or more, R27 is the same as or different from each other.

In an exemplary embodiment of the present application, Chemical Formula 15 may be represented by Chemical Formula 19 below.

[Formula 19]

The substituents of Formula 19 are as defined in Formula 15.

In an exemplary embodiment of the present application, L is a direct bond; a substituted or unsubstituted arylene group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

In another embodiment, the L is a direct bond; a substituted or unsubstituted arylene group having 6 to 40 carbon atoms; or a substituted or unsubstituted C 2 to C 40 heteroarylene group.

In another embodiment, the L is a direct bond; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; or a substituted or unsubstituted C 2 to C 20 heteroarylene group.

In another exemplary embodiment, L is a direct bond; or a phenylene group.

In another exemplary embodiment, L is a direct bond.

In another exemplary embodiment, L is a phenylene group.

In another exemplary embodiment, R9 and R10 are hydrogen; or deuterium.

In another exemplary embodiment, R9 and R10 are hydrogen.

In another exemplary embodiment, R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C 1 to C 30 alkyl group; a substituted or unsubstituted C 6 to C 60 aryl group; a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a hetero ring.

In another exemplary embodiment, R1 to R8 are hydrogen; heavy hydrogen; an aryl group unsubstituted or substituted with an alkyl group, an aryl group, or a heteroaryl group; or a heteroaryl group unsubstituted or substituted with an aryl group or a heteroaryl group.

In another exemplary embodiment, R1 to R8 are hydrogen; heavy hydrogen; aryl group; heteroaryl group; or a heteroaryl group substituted with an aryl group.

In another exemplary embodiment, R1 to R8 are hydrogen; heavy hydrogen; phenyl group; dibenzofuran group; dibenzothiophene group; a carbazole group; or a carbazole group substituted with a phenyl group.

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

In another exemplary embodiment, two adjacent substituents of R1 to R8 combine with each other to form a ring unsubstituted or substituted with an aryl group or an alkyl group.

In another exemplary embodiment, two adjacent substituents among R1 to R8 are bonded to each other to form an aromatic hydrocarbon ring or heterocycle unsubstituted or substituted with an aryl group or an alkyl group.

In another exemplary embodiment, two adjacent substituents among R1 to R8 combine with each other to form an aromatic hydrocarbon ring or heterocycle unsubstituted or substituted with a phenyl group or a methyl group.

In another exemplary embodiment, two adjacent substituents of R1 to R8 are bonded to each other to form an indole ring unsubstituted or substituted with a phenyl group; benzothiophene ring; benzofuran ring; Alternatively, an indene ring substituted or unsubstituted with a methyl group may be formed.

는 하기 화학식 20으로 표시될 수 있다. 여기서,

은 상기 화학식 2의 디벤조퓨란 구조에 연결되는 부위이다.In another embodiment, the formula (2)

may be represented by the following formula (20). here,

is a site connected to the dibenzofuran structure of Formula 2 above.

[Formula 20]

In Formula 20,

R1 to R4 are as defined in Formula 2,

Y is O, S, NR or CR'R";

R, R', R", R31 and R32 are the same as or different from each other and are hydrogen; deuterium; halogen; cyano group; substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms ; A substituted or unsubstituted C2 to C60 alkynyl group; A substituted or unsubstituted C1 to C20 alkoxy group; A substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C2 to C60 a heterocycloalkyl group; a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group Two or more groups selected from the group or adjacent to each other combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a hetero ring, f is an integer from 0 to 4, and when f is 2 or more, R31 is the same as or different from each other and g is an integer of 0 to 2, and when g is 2 or more, R32 is the same as or different from each other.

In another exemplary embodiment, Chemical Formula 20 may be selected from any one of the structural formulas of Group B below.

[Group B]

Substituent definitions of the structural formulas of Group B are the same as in Chemical Formula 20.

In another exemplary embodiment, R18 to R21 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an aryl group having 6 to 60 carbon atoms; or a heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R18 to R21 are the same as or different from each other, and each independently hydrogen; or deuterium.

In another exemplary embodiment, R18 to R21 are hydrogen.

In another exemplary embodiment, R17 and R22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an aryl group having 6 to 60 carbon atoms; or a heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R17 and R22 are the same as or different from each other, and each independently an aryl group having 6 to 60 carbon atoms; or a heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R17 and R22 are the same as or different from each other, and each independently represents an aryl group.

In another exemplary embodiment, R17 and R22 are a phenyl group.

In another exemplary embodiment, R11 to R15 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an aryl group having 6 to 60 carbon atoms that is unsubstituted or substituted with an alkyl group; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R11 to R15 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an aryl group having 6 to 60 carbon atoms that is unsubstituted or substituted with an alkyl group; or a heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R11 to R15 are the same as or different from each other, and each independently hydrogen; an aryl group having 6 to 60 carbon atoms that is unsubstituted or substituted with a methyl group; or a heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R11 to R15 are the same as or different from each other, and each independently hydrogen; phenyl group; biphenylyl group; naphthyl group; dimethyl fluorenyl group; dibenzofuran group; or a dibenzothiophene group.

In another exemplary embodiment, R12 and R14 are the same as or different from each other, and each independently an aryl group having 6 to 60 carbon atoms unsubstituted or substituted with an alkyl group; or a heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R12 and R14 are the same as or different from each other, and each independently a phenyl group, a biphenylyl group, a naphthyl group, a dimethyl fluorenyl group; dibenzofuran group; or a dibenzothiophene group.

In another exemplary embodiment, R23 to R26 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an aryl group having 6 to 60 carbon atoms; or a heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R23 to R26 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or an aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, R23 to R26 are the same as or different from each other, and each independently hydrogen; or an aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, R23 to R26 are the same as or different from each other, and each independently hydrogen; phenyl group; or a biphenylyl group.

In another exemplary embodiment, R27 is hydrogen; heavy hydrogen; an aryl group having 6 to 60 carbon atoms; or a heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R27 is hydrogen; heavy hydrogen; or an aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, R27 is hydrogen; or an aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, R27 is hydrogen; or a phenyl group.

In another exemplary embodiment, Y is O or S.

In another exemplary embodiment, Y is NR, and R is an aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, Y is NR, and R is a phenyl group.

In another exemplary embodiment, Y is CR′R″, and R′ and R″ are an alkyl group having 1 to 60 carbon atoms.

In another exemplary embodiment, Y is CR'R", and R' and R" are methyl groups.

In another exemplary embodiment, R31 is hydrogen; heavy hydrogen; an aryl group having 6 to 60 carbon atoms; or a heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R31 is hydrogen; heavy hydrogen; or an aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, R31 is hydrogen; or a phenyl group.

In another exemplary embodiment, R32 is hydrogen; or deuterium.

In another exemplary embodiment, R32 is hydrogen.

In an exemplary embodiment of the present application, R _c and R _d of Formula 3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or it may be a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In an exemplary embodiment of the present application, R _c and R _d of Formula 3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or it may be a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

In an exemplary embodiment of the present application, R _c and R _d of Formula 3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or it may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In an exemplary embodiment of the present application, R _c and R _d of Formula 3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted phenyl group; Or it may be a substituted or unsubstituted biphenyl group.

In an exemplary embodiment of the present application, R _c and R _d of Formula 3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; phenyl group; or a biphenyl group.

In another exemplary embodiment, r is an integer of 0 to 7, when r is 2 or more, R _c are the same as or different from each other, and two or more R _c adjacent to each other are bonded to each other to form a substituted or unsubstituted aliphatic or It may form an aromatic hydrocarbon ring or a hetero ring.

In the exemplary embodiment of the present application, R _c and R _d in Formula 3 may be hydrogen.

In another exemplary embodiment, R _a and R _b of Formula 3 may be the same as or different from each other, and each independently a substituted or unsubstituted C 6 to C 60 aryl group.

In another exemplary embodiment, R _a and R _b in Formula 3 may be the same as or different from each other, and each independently a substituted or unsubstituted C 6 to C 40 aryl group.

In another exemplary embodiment, R _a and R _b in Formula 3 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; a substituted or unsubstituted triphenylene group; Or it may be a substituted or unsubstituted naphthyl group.

In another exemplary embodiment, R _a and R _b of Formula 3 are the same as or different from each other, and each independently a phenyl group; biphenyl group; terphenyl group; triphenylene group; or a naphthyl group.

According to an exemplary embodiment of the present application, Chemical Formula 1 may be represented by any one of the following compounds, but is not limited thereto.

According to an exemplary embodiment of the present application, Chemical Formula 2 may be represented by any one of the following compounds, but is not limited thereto.

In an exemplary embodiment of the present application, Chemical Formula 3 may be represented by any one of the following compounds, but is not limited thereto.

In addition, by introducing various substituents into the structures of Chemical Formulas 1 to 3, compounds having intrinsic properties of the introduced substituents can be synthesized. For example, by introducing a substituent mainly used for a hole injection layer material, a hole transport material, a light emitting layer material, an electron transport layer material, and a charge generation layer material used in manufacturing an organic light emitting device into the core structure, the conditions required for each organic material layer are satisfied. substances can be synthesized.

In addition, by introducing various substituents into the structures of Chemical Formulas 1 to 3, it is possible to finely control the energy band gap, while improving the properties at the interface between organic materials and diversifying the use of the material. .

On the other hand, the heterocyclic compound has a high glass transition temperature (Tg) and excellent thermal stability. This increase in thermal stability is an important factor in providing driving stability to the device.

The heterocyclic compound according to an exemplary embodiment of the present application may be prepared by a multi-step chemical reaction. Some intermediate compounds are prepared first, and compounds of Formulas 1 to 3 can be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to an exemplary embodiment of the present application may be prepared based on Preparation Examples to be described later.

The composition may be used when forming an organic material of an organic light emitting device, and in particular, it may be more preferably used when forming a host of a light emitting layer.

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

The organic light emitting device according to an exemplary embodiment of the present application forms at least one layer of a hole injection layer, a hole transport layer, an electron blocking layer, and a hole transport auxiliary layer with the heterocyclic compound represented by Formula 1 above, and Formula 2 or 3 Except for forming a light emitting layer using a heterocyclic compound represented by , it may be manufactured by a conventional method and material for manufacturing an organic light emitting device.

The compounds represented by Chemical Formulas 1 to 3 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

The organic material layer of the organic light emitting device of the present invention may have a multilayer structure in which two or more organic material layers further including at least one of a light emitting layer, a hole injection layer, a hole transport layer, an electron blocking layer, and a hole transport auxiliary layer are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.

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

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

In the exemplary embodiment of the present application, the organic light emitting device may be a blue organic light emitting device, and the heterocyclic compound according to Chemical Formulas 1 to 3 may be used as a material of the blue organic light emitting device.

In the exemplary embodiment of the present application, the organic light emitting device may be a green organic light emitting device, and the heterocyclic compound according to Chemical Formulas 1 to 3 may be used as a material of the green organic light emitting device.

In the exemplary embodiment of the present application, the organic light emitting device may be a red organic light emitting device, and the heterocyclic compound according to Chemical Formulas 1 to 3 may be used as a material of the red organic light emitting device.

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

In an exemplary embodiment of the present application, the organic material layer includes a light emitting layer, and the light emitting layer provides an organic light emitting device that simultaneously contains the heterocyclic compound represented by Formula 2 and the heterocyclic compound represented by Formula 3 do.

In an exemplary embodiment of the present application, the organic material layer includes a light emitting layer, the light emitting layer includes a host material, and the host material is a heterocyclic compound represented by Formula 2 and a heterocyclic compound represented by Formula 3 It provides an organic light emitting device that is included at the same time.

In the organic light emitting device of the present application, the light emitting layer may be used by pre-mixing the heterocyclic compound represented by Formula 2 and the heterocyclic compound represented by Formula 3, and at least one of the two or more host materials. One may include the heterocyclic compound as a host material of the light emitting material.

The pre-mixed (pre-mixed) means that the light emitting layer is mixed with two or more host materials before depositing the organic material layer in a single park. As such, there is an advantage of making the process simpler because one deposition source is used instead of two or three deposition sources during preliminary mixing.

In the organic light emitting device of the present application, the heterocyclic compound represented by Formula 2 may be used as an N-type host for the phosphorescence emission layer.

In the organic light emitting device of the present application, the heterocyclic compound represented by Chemical Formula 3 may be used as a phosphorescent light emitting layer P-type host.

In addition, another exemplary embodiment of the present application provides a composition for an organic material layer of an organic light emitting device that includes the heterocyclic compound represented by Formula 2 and the compound represented by Formula 3 at the same time.

Specific details of the heterocyclic compound represented by Formula 2 and the compound represented by Formula 3 are the same as described above.

The weight ratio of the heterocyclic compound represented by Formula 2 in the composition to the compound represented by Formula 3 may be 1: 10 to 10: 1, 1: 8 to 8: 1, and 1: 5 to 5 : may be 1, and may be 1: 2 to 2: 1, but is not limited thereto.

The composition may be used when forming an organic material of an organic light emitting device, and in particular, it may be more preferably used when forming a host of a light emitting layer.

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

1 to 3 illustrate the stacking order of the electrode and the organic material layer of the organic light emitting device according to an exemplary embodiment of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and the structure of an organic light emitting device known in the art may also be applied to the present application.

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

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

In the organic light emitting device according to an exemplary embodiment of the present application, materials other than the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 are exemplified below, but these are for illustration only, and the scope of the present application It is not intended to be limiting, and materials known in the art may be substituted.

Materials having a relatively large work function may be used as the anode material, and transparent conductive oxides, metals, conductive polymers, or the like may be used. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO ₂ : Combination of metals and oxides such as Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

Materials having a relatively low work function may be used as the cathode material, and metal, metal oxide, conductive polymer, or the like may be used. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

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

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

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

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

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

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

The organic light emitting device according to the exemplary embodiment of the present application may be a top emission type, a back emission type, or a double side emission type depending on a material used.

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

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

[Preparation Example 1] Preparation of compound 1 (C)

Preparation of compound 1

N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (N4,N4'-diphenyl-[1,1'-biphenyl) in a one-necked round bottom flask (one neck rbf) ]-4,4'-diamine) (20g, 59 mmol), 5'-bromo-1,1':3',1''-terphenyl (5'-bromo-1,1':3', 1''-terphenyl) (40.3 g, 0.13 mol), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ) (5.4 g, 5.9 mmol), tri-tert-butylphosphine solution (Tri- tert -butylphosphine solution) (23.6ml , 11.8mmol), sodium tert- butoxide (sodium tert -butoxide) (28.3g, 0.295mol), and toluene (toluene) 4 sigan refluxed 800ml mixture at 120 ^o C did. The refluxed mixture was passed through silica and then concentrated. The concentrated mixture was boiled with ethyl acetate and filtered to obtain compound 1 (C). (46g, 98%)

In the preparation of compound 1 (C), N4, N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (N4,N4'-diphenyl-[1,1'-biphenyl]- 4,4'-diamine) using Compound A of Table 1 below, 5'-bromo-1,1':3',1''-terphenyl (5'-bromo-1,1':3 ',1''-terphenyl) was prepared in the same manner, except that compound B of Table 1 was used instead of compound C of Table 1 below.

[Preparation Example 2] Preparation of compound 15

Preparation of compound 15(D)

1,4-dibromobenzene (1,4-dibromobenzene) (10g, 42 mmol), N-phenyl-[1,1'-biphenyl]-4-amine in a one-necked round bottom flask (One neck rbf) (N-phenyl-[1,1'-biphenyl]-4-amine) (22.6g, 92.4mol), tris(dibenzylideneacetone)dipalladium(0) (Pd ₂ (dba) ₃ ) (1.9 g, 2.1mmol), tree -tert- butylphosphine solution (Tri- tert -butylphosphine solution) (8.2ml , 4.2mmol), sodium tert- butoxide (sodium tert -butoxide) (12g, 0.126mol), and toluene (toluene ) 200 ml of the mixture was ^{refluxed at 120 o} C for 4 hours. The refluxed mixture was passed through silica and then concentrated. The concentrated mixture was boiled with ethyl acetate and filtered to obtain compound 15(D). (15g, 64%)

In the preparation of the compound 15 (D), N-phenyl- [1,1'-biphenyl] -4-amine (N-phenyl- [1,1'-biphenyl] -4-amine) instead of the compound of Table 2 Except for using C, it was prepared in the same manner to prepare compound D in Table 2 below.

[Preparation Example 3] Preparation of compound 23

Preparation of compound 23 (G)

4,4''-dibromo-5'-phenyl-1,1':3',1''-terphenyl (4,4''-dibromo-5) in a one-necked round bottom flask (one neck rbf) '-phenyl-1,1':3',1''-terphenyl) (10g, 21mmol), diphenylamine (7.9g, 47mol), tris(dibenzylideneacetone)dipalladium(0) _{(Pd 2 (dba) 3)} (0.9g, 1mmol), tree -tert- butylphosphine solution (Tri- tert -butylphosphine solution) (4.2ml , 2.1mmol), sodium tert- butoxide (sodium tert -butoxide) (10 g, 0.1 mol), and toluene (Toluene) 200ml mixture was ^{refluxed at 120 o} C for 4 hours. The refluxed mixture was passed through silica and then concentrated. The concentrated mixture was boiled with ethyl acetate and filtered to obtain compound 23 (G). (10g, 74%)

In the preparation of compound 23 (G), 4,4''-dibromo-5'-phenyl-1,1':3',1''-terphenyl (4,4''-dibromo-5'- phenyl-1,1':3',1''-terphenyl) in the same manner, except for using the compound E of Table 3 below, and using the compound F of Table 3 instead of diphenylamine prepared to prepare compound G of Table 3 below.

[Preparation Example 4] Preparation of compound 1-1 (J)

Preparation of compound P5

1-bromo-2,3-difluorobenzene (4-bromo-2,3-difluorobenzene) (40.5 g, 209 mmol), (2-chloro-6-) in a one-necked round bottom flask (One neck rbf) Methoxyphenyl) boronic acid ((2-chloro-6-methoxyphenyl) boronic acid) (43 g, 230 mmol), tetrakis (triphenylphosphine) palladium (0) (Pd(PPh ₃ ) ₄ ) (24 g, 20.9 mmol) ), potassium carbonate (K ₂ CO ₃ ) (57.9 g, 419 mmol), and toluene/ethanol/water (500ml/100ml/100ml) mixture was refluxed at ^{110 o C.} After extraction with dichloromethane (dichloromethane), it was dried over _{MgSO 4 .} After silica gel filter, it was concentrated to obtain compound P5. (40.8 g, 76%)

Preparation of compound P4

2'-chloro-2,3-difluoro-6'-methoxy-1,1'-biphenyl (2'-chloro-2,3-difluoro-6) in a one-necked round bottom flask (one neck rbf) A mixture of '-methoxy-1,1'-biphenyl) (40.8 g, 160 mmol), and methyl chloride (MC) (600 ml) ^{was lowered to 0 o} C, and BBr ₃ (30 mL, 320 mmol) was added dropwise. Then, the temperature was raised to room temperature and stirred for 1 hour. The reaction was terminated with distilled water, extracted with dichloromethane, and dried over _{MgSO 4 .} After this, the mixture was subjected to column purification MC:HX = 1:1 to obtain compound P4. (21 g, 54%) (Hexane, HX)

Preparation of compound P3

4-chloro-2',3'-difluoro-[1,1'-biphenyl]-2-ol (4-chloro-2',3'-difluoro) in a one-necked round bottom flask (One neck rbf) -[1,1'-biphenyl]-2-ol) (21g, 87.2 mmol), Cs ₂ CO ₃ (71g, 218mmol) and a (200ml) mixture of dimethylacetamide (dimethylacetamide) was stirred at ^{120 o C.} After cooling the mixture, the mixture was filtered, and the solvent of the filtrate was removed. Then, column purification was lowered to HX:MC = 4:1 to obtain compound P3. (17 g, 88%)

Preparation of compound P2

1-chloro-6-fluorodibenzo[b,d]furan (6g, 27.19 mmol), 9H- in a one-necked round bottom flask (One neck rbf) A mixture of carbazole (5 g, 29.9 mmol), Cs ₂ CO ₃ (22 g, 101.7 mmol), and dimethylacetamide (60 ml) was ^{refluxed at 170 °} C for 12 hours (h). After cooling the mixture, the mixture was filtered, and the solvent of the filtrate was removed. Then, column purification was lowered to HX:MC = 3:1 to obtain compound P2. (9g, 90%)

Preparation of compound P1

9-(9-chlorodibenzo[b,d]furan-4-yl)-9H-carbazole (9-(9-chlorodibenzo[b,d]furan-4) in one neck round bottom flask (One neck rbf) -yl)-9H-carbazole) (9g, 24.4 mmol), bis(pinacolato)diboron) (12.4g, 48.9mmol), Pcy ₃ (1.37g, 4.89mmol), potassium acetate (KOAc) (7.1 g, 73 mmol), Pd ₂ (dba) ₃ (2.2 g, 2.44 mmol) and (100 ml) mixture of 1,4-dioxane (1,4-dioxane) was refluxed at ^{140 o C.} After that, the mixture was cooled and the filtered filtrate was concentrated, and column purification was lowered to HX:MC = 3:1 to obtain compound P1 (7.2 g , 64%).

Preparation of compound 1-1 (J)

9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d] in one neck round bottom flask (One neck rbf) furan-4-yl)-9H-carbazole (9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-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 (2-chloro-4,6-diphenyl-1,3,5) -triazine) (5g,18.8mmol), tetrakis(triphenylphosphine)palladium(0)(Pd(PPh ₃ ) ₄ )(1.8g, 1.56mmol), potassium carbonate (K ₂ CO ₃ ) (4.3 g, 31.2 mmol), and a 1,4-dioxane/water (100ml/25ml) mixture was ^{refluxed at 120 o} C for 4 hours. After this mixture was then filter at 120 ^o C 120 ^o C 1,4- dioxane, given washed with distilled water and methanol (MeOH) to give the compound 1-1 (J). (6.6g, 75%)

In Preparation Example 4 of the compound 1-1 (J), 9H-carbazole (9H-carbazole) (H) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro- 4,6-diphenyl-1,3,5-triazine) (I), except that H and I of Tables 4 to 10 were used as intermediates, and the same method as for the preparation of Compound 1-1 (J) Thus, compounds J of Tables 4 to 10 were synthesized.

[Preparation Example 5] Preparation of compound 1-129 (M)

Preparation of compound Q5

In a one neck round bottom flask (One neck rbf), 1-bromo-2,4-difluorobenzene (1-bromo-2,4-difluorobenzene) (40 g, 207 mmol), (2-chloro-6-methyl Toxyphenyl) boronic acid ((2-chloro-6-methoxyphenyl) boronic acid) (42.4 g, 227 mmol), tetrakis (triphenylphosphine) palladium (0) (Pd(PPh ₃ ) ₄ ) (23 g, 20.7 mmol) ), potassium carbonate (K ₂ CO ₃ ) (57 g, 414 mmol), and toluene/ethanol/water (600ml/150ml/150ml) mixture was refluxed at ^110°C. Thereafter, the mixture was extracted with dichloromethane and dried over _{MgSO 4 .} After silica gel filter, it was concentrated to obtain compound Q5. (50g, 94%)

Preparation of compound Q4

2'-chloro-2,4-difluoro-6'-methoxy-1,1'-biphenyl (2'-chloro-2,4-difluoro-6) in a one-necked round bottom flask (one neck rbf) '-methoxy-1,1'-biphenyl) (50g, 196 mmol), and a mixture of dichloromethane (700ml) ^{was lowered to 0 o} C, BBr ₃ (28.3mL, 294 mmol) was added dropwise and room temperature The temperature was raised to , and the mixture was stirred for 2 hours.

After that, the reaction was terminated with distilled water, extracted with dichloromethane, and dried over _{MgSO 4 .} Compound Q4 was obtained by silica gel filter. (27.5g, 58%)

Preparation of compound Q3

4-chloro-2',4'-difluoro-[1,1'-biphenyl]-2-ol (4-chloro-2',4'-difluoro) in a one-necked round bottom flask (One neck rbf) A mixture of -[1,1'-biphenyl]-2-ol) (27g, 114 mmol), Cs ₂ CO ₃ (83 g, 285 mmol) and dimethylacetamide (300 ml) was stirred at ^{120 o C.} Thereafter, the mixture was cooled, filtered, and the solvent of the filtrate was removed, followed by silica gel filter to obtain compound Q3. (23g, 92%)

Preparation of compound Q2

1-chloro-7-fluorodibenzo[b,d]furan (5.5g, 24.9 mmol), 9H in a one-necked round bottom flask (One neck rbf) - A mixture of carbazole (9H-carbazole) (4.58 _{g, 27.4 mmol), Cs 2} CO ₃ (20 g, 62 mmol) dimethylacetamide (60 ml) was ^{refluxed at 170 °} C for 6 hours (h). After cooling the mixture, the mixture was filtered and the solvent of the filtrate was removed, and column purification was lowered to HX:MC = 3:1 to obtain compound Q2. (7.6 g, 83%)

Preparation of compound Q1

9-(9-chlorodibenzo[b,d]furan-3-yl)-9H-carbazole (9-(9-chlorodibenzo[b,d]furan-3) in one neck round bottom flask (One neck rbf) -yl)-9H-carbazole) (7.5g, 20.3mmol), Bis(pinacolato)diboron) (10.3g, 40.7mmol), Pcy ₃ (1.14g, 4.07mmol), Potassium A mixture of acetate (KOAc) ((5.97 _{g, 60.9 mmol), Pd 2} (dba) ₃ (1.85 g, 2.03 mmol) and 1,4-dioxane (80 ml) at 140 ^o C After cooling the mixture, the filtered filtrate was concentrated, and column purification was lowered to HX:MC = 2:1 to obtain compound Q1 (6.5 g , 70%).

Preparation of compound 1-129 (M)

9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d] in one neck round bottom flask (One neck rbf) furan-3-yl)-9H-carbazole (9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-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 (2-chloro-4,6-diphenyl-1,3,5) -triazine) (4.54g,16.9mmol), tetrakis(triphenylphosphine)palladium(0)(Pd(PPh ₃ ) ₄ ) (1.6g, 1.41mmol), potassium carbonate (K ₂ CO ₃ ) (3.9 g , 28.2mmol), 1,4-dioxane/water (80ml/28.2ml) mixture was ^{refluxed at 120 o} C for 4 hours. Thereafter, after the filter of the mixture at 120 ^o C, washed given to 1,4-dioxane, distilled water and methanol (MeOH) at 120 ^o C to give the compound 1-129 (M) (5.4g, 68 %).

In Preparation Example 5 of 1-129 (M), 9H-carbazole (9H-carbazole) (K) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4 ,6-diphenyl-1,3,5-triazine) (L), except that K and L of Tables 11 to 17 were used as intermediates, and the same method as for the preparation of Compound 1-129 (M) As a result, compounds M of Tables 11 to 17 were synthesized below.

<Preparation Example 6> Synthesis of compound 2-3 (C)

1) Preparation of compound 2-3

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

Intermediate A of Table 18 was used instead of 3-bromo-1,1`-biphenyl (A) in Preparation Example 6, and 9-phenyl-9H,9 'H-3,3'-bicarbazole (9-phenyl-9H,9'H-3,3'-bicarbazole) (B) in place of the preparation of Preparation Example 6, except that the intermediate B of Table 18 was used By preparing in the same manner, the target compound C shown in Table 18 was synthesized.

Compounds were prepared in the same manner as in Preparation Examples, and the synthesis confirmation results are shown in Tables 19 to 21 below. Tables 19 and 20 below are the measurement values of FD-mass spectrometry (FD-MS: Field desorption mass spectrometry), and Table 21 below is the measurement values of ¹ H NMR (CDCl _{3 , 200Mz).}

compound FD-Mass compound FD-Mass One m/z=792.35 (C60H44N2=793.03) 2 m/z=792.35 (C60H44N2=793.03) 3 m/z=792.35 (C60H44N2=793.03) 4 m/z= 1096.48 (C84H60N2=1097.42) 5 m/z= 1096.48 (C84H60N2=1097.42) 6 m/z= 892.38 (C68H48N2=893.15) 7 m/z= 892.38 (C68H48N2=893.15) 8 m/z=792.35 (C60H44N2=793.03) 9 m/z= 740.32 (C56H40N2=740.95) 10 m/z= 740.32 (C56H40N2=740.95) 11 m/z= 740.32 (C56H40N2=740.95) 12 m/z = 892.38 (C68H48N2 = 893.15) 13 m/z = 892.38 (C68H48N2 = 893.15) 14 m/z = 892.38 (C68H48N2 = 893.15) 15 m/z= 564.26 (C42H32N2= 564.73) 16 m/z= 512.23 (C38H28N2= 512.66) 17 m/z = 664.29 (C50H36N2 = 664.85) 18 m/z= 612.26 (C46H32N2= 612.78) 19 m/z= 660.26 (C50H32N2= 660.82) 20 m/z= 612.26 (C46H32N2= 612.78) 21 m/z= 716.32 (C54H40N2= 716.93) 22 m/z = 1020.44 (C78H56N2 = 1021.32) 23 m/z = 640.29 (C48H36N2 = 640.83) 24 m/z= 740.32 (C56H40N2= 740.95) 25 m/z = 792.35 (C60H44N2 = 793.03) 26 m/z = 944.41 (C72H52N2 = 945.22) 27 m/z = 690.30 (C52H38N2 = 690.89) 28 m/z= 716.32 (C54H40N2= 716.93) 29 m/z= 740.32 (C56H40N2= 740.95)

compound FD-Mass compound FD-Mass 1-1 m/z = 564.63 (C39H24N4O=564.20) 1-2 m/z = 640.73 (C45H28N4O=640.23) 1-3 m/z = 640.73 (C45H28N4O=640.23) 1-4 m/z = 716.83 (C51H32N4O=717.26) 1-5 m/z = 716.83 (C51H32N4O=717.26) 1-6 m/z=729.82 (C51H31N5O=729.25) 1-7 m/z=729.82 (C51H31N5O=729.25) 1-8 m/z = 805.92 (C57H35N5O=805.28) 1-9 m/z = 730.81 (C51H30N4O2=730.81) 1-10 m/z = 680.79 (C48H32N4O=680.26) 1-11 m/z = 680.79 (C48H32N4O=680.26) 1-12 m/z = 680.79 (C48H32N4O=680.26) 1-13 m/z = 670.78 (C45H26N4OS=670.18) 1-14 m/z = 654.71 (C45H26N4O2=654.21) 1-15 m/z = 654.71 (C45H26N4O2=654.21) 1-16 m/z = 670.78 (C45H26N4OS=670.18) 1-17 m/z = 640.73 (C45H2N4O=640.23) 1-18 m/z = 716.83 (C51H32N4O=716.26) 1-19 m/z = 716.83 (C51H32N4O=716.26) 1-20 m/z = 792.92 (C57H36N4O=792.29) 1-21 m/z = 792.92 (C57H36N4O=792.29) 1-22 m/z = 640.73 (C45H2N4O=640.23) 1-23 m/z = 792.92 (C57H36N4O=792.29) 1-24 m/z = 792.92 (C57H36N4O=792.29) 1-25 m/z = 792.92 (C57H36N4O=792.29) 1-26 m/z = 728.84 (C52H32N4O=728.26) 1-27 m/z = 728.84 (C52H32N4O=728.26) 1-28 m/z = 804.93 (C58H36N4O=804.29) 1-29 m/z = 746.21 (C51H30N4OS=746.21) 1-30 m/z = 756.89 (C54H36N4O=756.29) 1-31 m/z = 756.89 (C54H36N4O=756.29) 1-32 m/z = 679.81 (C49H33N3O=679.26) 1-33 m/z = 746.88 (C51H30N4OS=746.21) 1-34 m/z = 730.81 (C51H30N4O2=730.24 1-35 m/z = 730.81 (C51H30N4O2=730.24 1-36 m/z = 669.79 (C46H27N3OS=669.19) 1-37 m/z = 640.73 (C45H28N4O=640.23) 1-38 m/z = 640.73 (C45H28N4O=640.23) 1-39 m/z = 716.83 (C51H32N4O=717.26) 1-40 m/z = 716.83 (C51H32N4O=717.26) 1-41 m/z = 716.83 (C51H43N4O=716.26) 1-42 m/z = 716.83 (C51H32N4O=717.26) 1-43 m/z = 715.84 (C52H33N3O=715.26) 1-44 m/z = 715.84 (C52H33N3O=715.26) 1-45 m/z = 640.73 (C45H28N4O=640.23 1-46 m/z = 716.83 (C51H32N4O=716.26) 1-47 m/z = 716.83 (C51H32N4O=716.26) 1-48 m/z = 792.92 (C57H36N4O=792.29) 1-49 m/z = 756.89 (C54H36N4O=756.29) 1-50 m/z = 716.83 (C51H32N4O=716.26) 1-51 m/z = 716.83 (C51H32N4O=716.26) 1-52 m/z = 716.83 (C51H32N4O=716.26) 1-53 m/z = 792.92 (C57H36N4O=792.29) 1-54 m/z = 792.92 (C57H36N4O=792.29) 1-55 m/z = 601.69 (C43H27N3O=601.69) 1-56 m/z = 601.69 (C43H27N3O=601.69) 1-57 m/z = 677.79 (C49H31N3O=677.25) 1-58 m/z = 677.79 (C49H31N3O=677.25) 1-59 m/z = 677.79 (C49H31N3O=677.25) 1-60 m/z = 677.79 (C49H31N3O=677.25) 1-61 m/z = 753.89 (C55H35N3O=753.28) 1-62 m/z = 753.89 (C55H35N3O=753.28) 1-63 m/z = 753.89 (C55H35N3O=753.28) 1-64 m/z = 753.89 (C55H35N3O=753.28) 1-65 m/z = 717.85 (C52H35N3O=717.28) 1-66 m/z = 717.85 (C52H35N3O=717.28) 1-67 m/z = 707.84 (C49H29N3OS=707.20) 1-68 m/z = 691.77 (C49H29N3O2=691.23) 1-69 m/z = 613.70 (C44H27N3O=613.22) 1-70 m/z = 689.80 (C50H31N3O=689.25) 1-71 m/z = 689.80 (C50H31N3O=689.25) 1-72 m/z = 689.80 (C50H31N3O=689.25) 1-73 m/z = 765.90 (C56H35N3O=765.28) 1-74 m/z = 765.90 (C56H35N3O=765.28) 1-75 m/z = 729.86 (C53H35N3O=729.28) 1-76 m/z = 719.20 (C50H29N3OS=719.20) 1-77 m/z = 537.61 (C38H23N3O=537.18) 1-78 m/z = 613.70 (C44H27N3O=613.22) 1-79 m/z = 613.70 (C44H27N3O=613.22) 1-80 m/z = 613.70 (C44H27N3O=613.22) 1-81 m/z = 689.80 (C50H31N3O=689.25) 1-82 m/z = 689.80 (C50H31N3O=689.25) 1-83 m/z = 702.80 (C50H30N4O=702.24) 1-84 m/z = 702.80 (C50H30N4O=702.24) 1-85 m/z = 537.61 (C38H23N3O=537.18) 1-86 m/z = 613.70 (C44H27N3O=613.22) 1-87 m/z = 613.70 (C44H27N3O=613.22) 1-88 m/z = 613.70 (C44H27N3O=613.22) 1-89 m/z = 689.80 (C50H31N3O=689.25) 1-90 m/z = 689.80 (C50H31N3O=689.25) 1-91 m/z = 778.90 (C56H34N4O=78.27) 1-92 m/z = 703.78 (C50H29N3O2=703.23) 1-93 m/z = 536.62 (C39H24N2O=536.19) 1-94 m/z = 612.72 (C45H28N2O=612.22) 1-95 m/z = 612.72 (C45H28N2O=612.22) 1-96 m/z = 612.72 (C45H28N2O=612.22) 1-97 m/z = 688.81 (C51H32N2O=688.25) 1-98 m/z = 688.81 (C51H32N2O=688.25) 1-99 m/z = 652.78 (C48H32N2O=652.25) 1-100 m/z = 652.78 (C48H32N2O=652.25) 1-101 m/z = 536.62 (C39H24N2O=536.19) 1-102 m/z = 612.72 (C45H28N2O=612.22) 1-103 m/z = 612.72 (C45H28N2O=612.22) 1-104 m/z = 612.72 (C45H28N2O=612.22) 1-105 m/z = 688.81 (C51H32N2O=688.25) 1-106 m/z = 688.81 (C51H32N2O=688.25) 1-107 m/z = 642.77 (C45H26N2OS=642.18) 1-108 m/z = 626.70 (C45H27N2O2=626.20) 1-109 m/z = 563.65 (C40H25N3O=563.20) 1-110 m/z = 639.73 (C46H29N3O=639.23) 1-111 m/z = 639.73 (C46H29N3O=639.23) 1-112 m/z = 715.84 (C52H33N3O=715.26) 1-113 m/z = 715.84 (C52H33N3O=715.26) 1-114 m/z = 715.84 (C52H33N3O=715.26) 1-115 m/z = 639.74 (C46H29N3O=639.23) 1-116 m/z = 715.84 (C52H33N3O=715.26) 1-117 m/z = 664.75 (C47H28N4O=664.23) 1-118 m/z = 740.85 (C53H32N4O=740.26) 1-119 m/z = 740.85 (C53H32N4O=740.26) 1-120 m/z = 740.85 (C53H32N4O=740.26) 1-121 m/z = 816.94 (C59H36N4O=816.29) 1-122 m/z = 816.94 (C59H36N4O=816.29) 1-123 m/z = 829.94 (C59H35N5O=829.28) 1-124 m/z = 829.94 (C59H35N5O=829.28) 1-125 m/z=729.82 (C51H31N5O=729.25) 1-126 m/z = 805.92 (C57H35N5O=805.28) 1-127 m/z = 702.80 (C50H30N4O=702.24) 1-128 m/z = 766.27 (C55H34N4O=766.27) 1-129 m/z = 564.63 (C39H24N4O=564.20) 1-130 m/z = 640.73 (C45H28N4O=640.23) 1-131 m/z = 640.73 (C45H28N4O=640.23) 1-132 m/z = 716.83 (C51H32N4O=717.26) 1-133 m/z = 716.83 (C51H32N4O=717.26) 1-134 m/z=729.82 (C51H31N5O=729.25) 1-135 m/z=729.82 (C51H31N5O=729.25) 1-136 m/z = 805.92 (C57H35N5O=805.28) 1-137 m/z = 730.81 (C51H30N4O2=730.81) 1-138 m/z = 680.79 (C48H32N4O=680.26) 1-139 m/z = 680.79 (C48H32N4O=680.26) 1-140 m/z = 680.79 (C48H32N4O=680.26) 1-141 m/z = 670.78 (C45H26N4OS=670.18) 1-142 m/z = 654.71 (C45H26N4O2=654.21) 1-143 m/z = 654.71 (C45H26N4O2=654.21) 1-144 m/z = 670.78 (C45H26N4OS=670.18) 1-145 m/z = 640.73 (C45H2N4O=640.23) 1-146 m/z = 716.83 (C51H32N4O=716.26) 1-147 m/z = 716.83 (C51H32N4O=716.26) 1-148 m/z = 792.92 (C57H36N4O=792.29) 1-149 m/z = 792.92 (C57H36N4O=792.29) 1-150 m/z = 640.73 (C45H2N4O=640.23) 1-151 m/z = 792.92 (C57H36N4O=792.29) 1-152 m/z = 792.92 (C57H36N4O=792.29) 1-153 m/z = 792.92 (C57H36N4O=792.29) 1-154 m/z = 728.84 (C52H32N4O=728.26) 1-155 m/z = 728.84 (C52H32N4O=728.26) 1-156 m/z = 804.93 (C58H36N4O=804.29) 1-157 m/z = 746.21 (C51H30N4OS=746.21) 1-158 m/z = 756.89 (C54H36N4O=756.29) 1-159 m/z = 756.89 (C54H36N4O=756.29) 1-160 m/z = 679.81 (C49H33N3O=679.26) 1-161 m/z = 746.88 (C51H30N4OS=746.21) 1-162 m/z = 730.81 (C51H30N4O2=730.24 1-163 m/z = 730.81 (C51H30N4O2=730.24 1-164 m/z = 669.79 (C46H27N3OS=669.19) 1-165 m/z = 640.73 (C45H28N4O=640.23) 1-166 m/z = 640.73 (C45H28N4O=640.23) 1-167 m/z = 716.83 (C51H32N4O=717.26) 1-168 m/z = 716.83 (C51H32N4O=717.26) 1-169 m/z = 716.83 (C51H43N4O=716.26) 1-170 m/z = 716.83 (C51H32N4O=717.26) 1-171 m/z = 715.84 (C52H33N3O=715.26) 1-172 m/z = 715.84 (C52H33N3O=715.26) 1-173 m/z = 640.73 (C45H28N4O=640.23 1-174 m/z = 716.83 (C51H32N4O=716.26) 1-175 m/z = 716.83 (C51H32N4O=716.26) 1-176 m/z = 792.92 (C57H36N4O=792.29) 1-177 m/z = 756.89 (C54H36N4O=756.29) 1-178 m/z = 716.83 (C51H32N4O=716.26) 1-179 m/z = 716.83 (C51H32N4O=716.26) 1-180 m/z = 716.83 (C51H32N4O=716.26) 1-181 m/z = 792.92 (C57H36N4O=792.29) 1-182 m/z = 792.92 (C57H36N4O=792.29) 1-183 m/z = 601.69 (C43H27N3O=601.69) 1-184 m/z = 601.69 (C43H27N3O=601.69) 1-185 m/z = 677.79 (C49H31N3O=677.25) 1-186 m/z = 677.79 (C49H31N3O=677.25) 1-187 m/z = 677.79 (C49H31N3O=677.25) 1-188 m/z = 677.79 (C49H31N3O=677.25) 1-189 m/z = 753.89 (C55H35N3O=753.28) 1-190 m/z = 753.89 (C55H35N3O=753.28) 1-191 m/z = 753.89 (C55H35N3O=753.28) 1-192 m/z = 753.89 (C55H35N3O=753.28) 1-193 m/z = 717.85 (C52H35N3O=717.28) 1-194 m/z = 717.85 (C52H35N3O=717.28) 1-195 m/z = 707.84 (C49H29N3OS=707.20) 1-196 m/z = 691.77 (C49H29N3O2=691.23) 1-197 m/z = 613.70 (C44H27N3O=613.22) 1-198 m/z = 689.80 (C50H31N3O=689.25) 1-199 m/z = 689.80 (C50H31N3O=689.25) 1-200 m/z = 689.80 (C50H31N3O=689.25) 1-201 m/z = 765.90 (C56H35N3O=765.28) 1-202 m/z = 765.90 (C56H35N3O=765.28) 1-203 m/z = 729.86 (C53H35N3O=729.28) 1-204 m/z = 719.20 (C50H29N3OS=719.20) 1-205 m/z = 537.61 (C38H23N3O=537.18) 1-206 m/z = 613.70 (C44H27N3O=613.22) 1-207 m/z = 613.70 (C44H27N3O=613.22) 1-208 m/z = 613.70 (C44H27N3O=613.22) 1-209 m/z = 689.80 (C50H31N3O=689.25) 1-210 m/z = 689.80 (C50H31N3O=689.25) 1-211 m/z = 702.80 (C50H30N4O=702.24) 1-212 m/z = 702.80 (C50H30N4O=702.24) 1-213 m/z = 537.61 (C38H23N3O=537.18) 1-214 m/z = 613.70 (C44H27N3O=613.22) 1-215 m/z = 613.70 (C44H27N3O=613.22) 1-216 m/z = 613.70 (C44H27N3O=613.22) 1-217 m/z = 689.80 (C50H31N3O=689.25) 1-218 m/z = 689.80 (C50H31N3O=689.25) 1-219 m/z = 778.90 (C56H34N4O=78.27) 1-220 m/z = 703.78 (C50H29N3O2=703.23) 1-221 m/z = 536.62 (C39H24N2O=536.19) 1-222 m/z = 612.72 (C45H28N2O=612.22) 1-223 m/z = 612.72 (C45H28N2O=612.22) 1-224 m/z = 612.72 (C45H28N2O=612.22) 1-225 m/z = 688.81 (C51H32N2O=688.25) 1-226 m/z = 688.81 (C51H32N2O=688.25) 1-227 m/z = 652.78 (C48H32N2O=652.25) 1-228 m/z = 652.78 (C48H32N2O=652.25) 1-229 m/z = 536.62 (C39H24N2O=536.19) 1-230 m/z = 612.72 (C45H28N2O=612.22) 1-231 m/z = 612.72 (C45H28N2O=612.22) 1-232 m/z = 612.72 (C45H28N2O=612.22) 1-233 m/z = 688.81 (C51H32N2O=688.25) 1-234 m/z = 688.81 (C51H32N2O=688.25) 1-235 m/z = 642.77 (C45H26N2OS=642.18) 1-236 m/z = 626.70 (C45H27N2O2=626.20) 1-237 m/z = 563.65 (C40H25N3O=563.20) 1-238 m/z = 639.73 (C46H29N3O=639.23) 1-239 m/z = 639.73 (C46H29N3O=639.23) 1-240 m/z = 715.84 (C52H33N3O=715.26) 1-241 m/z = 715.84 (C52H33N3O=715.26) 1-242 m/z = 715.84 (C52H33N3O=715.26) 1-243 m/z = 639.74 (C46H29N3O=639.23) 1-244 m/z = 715.84 (C52H33N3O=715.26) 1-245 m/z = 664.75 (C47H28N4O=664.23) 1-246 m/z = 740.85 (C53H32N4O=740.26) 1-247 m/z = 740.85 (C53H32N4O=740.26) 1-248 m/z = 740.85 (C53H32N4O=740.26) 1-249 m/z = 816.94 (C59H36N4O=816.29) 1-250 m/z = 816.94 (C59H36N4O=816.29) 1-251 m/z = 829.94 (C59H35N5O=829.28) 1-252 m/z = 829.94 (C59H35N5O=829.28) 1-253 m/z=729.82 (C51H31N5O=729.25) 1-254 m/z = 805.92 (C57H35N5O=805.28) 1-255 m/z = 702.80 (C50H30N4O=702.24) 1-256 m/z = 766.27 (C55H34N4O=766.27) 1-257 m/z = 716.83 (C51H32N4O=716.26) 1-258 m/z=654.71 (C45H26N4O2=654.21) 1-259 m/z=730.81 (C51H30N4O2=730.24) 1-260 m/z=654.71 (C45H26N4O2=654.21) 1-261 m/z=730.81 (C51H30N4O2=730.24) 1-262 m/z=730.81 (C51H30N4O2=730.24) 1-263 m/z = 716.83 (C51H32N4O=716.26) 1-264 m/z=654.71 (C45H26N4O2=654.21) 1-265 m/z=730.81 (C51H30N4O2=730.24) 1-266 m/z=730.81 (C51H30N4O2=730.24) 1-267 m/z=746.88 (C51H30N4OS=741.21) 1-268 m/z=756.89 (C54H36N4O=756.29) 1-269 m/z=614.71 (C43H26N4O=614.21) 1-270 m/z=664.77 (C47H28N4O=664.23) 1-271 m/z=729.84 (C51H31N5O=729.25) 1-272 m/z=729.84 (C51H31N5O=729.25) 1-273 m/z=654.73 (C45H26N4O2=654.21) 1-274 m/z=670.79 (C45H26N4OS=670.18) 1-275 m/z=779.90 (C55H33N5O=779.27) 1-276 m/z=829.96 (C59H35N5O=829.28) 1-277 m/z=704.79 (C49H28N4O2=704.22) 1-278 m/z=720.85 (C49H28N4OS=720.20) 1-279 m/z=754.85 (C53H30N4O2=754.24) 1-280 m/z=770.91 (C53H30N4OS=770.21) 1-281 m/z=693.82 (C48H27N3OS=693.19) 1-282 m/z=758.90 (C52H30N4OS=758.21) 1-283 m/z=799.97 (C54H29N3OS2=799.18) 1-284 m/z=783.90 (C54H29N3O2S=783.20) 1-285 m/z = 716.83 (C51H32N4O=717.26) 1-286 m/z = 716.83 (C51H32N4O=717.26) 2-1 m/z = 484.19 (C ₃₆ H ₂₄ N ₂ =484.60) 2-2 m/z= 560.23 (C ₄₂ H ₂₈ N ₂ =560.70) 2-3 m/z= 560.23 (C ₄₂ H ₂₈ N ₂ =560.70) 2-4 m/z= 560.23 (C ₄₂ H ₂₈ N ₂ =560.70) 2-5 m/z= 636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 2-6 m/z= 636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 2-7 m/z= 636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 2-8 m/z= 534.21 (C ₄₀ H ₂₆ N ₂ =534.66) 2-9 m/z= 534.21 (C ₄₀ H ₂₆ N ₂ =534.66) 2-10 m/z= 600.26 (C ₄₅ H ₃₂ N ₂ =600.76) 2-11 m/z= 600.26 (C ₄₅ H ₃₂ N ₂ =600.76) 2-12 m/z= 724.29 (C ₅₅ H ₃₆ N ₂ =724.91) 2-13 m/z= 724.29 (C ₅₅ H ₃₆ N ₂ =724.91) 2-14 m/z= 722.27 (C ₅₅ H ₃₄ N ₂ =722.89) 2-15 m/z= 722.27 (C ₅₅ H ₃₄ N ₂ =722.89) 2-16 m/z= 634.24 (C ₄₈ H ₃₀ N ₂ =634.78) 2-17 m/z = 509.19 (C ₃₇ H ₂₃ N ₃ =509.61) 2-18 m/z= 742.28 (C ₅₄ H ₃₈ N ₂ Si=743.00) 2-19 m/z= 636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 2-20 m/z= 636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 2-21 m/z= 636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 2-22 m/z= 712.29 (C ₅₄ H ₃₆ N ₂ =712.90) 2-23 m/z= 712.29 (C ₅₄ H ₃₆ N ₂ =712.90) 2-24 m/z= 712.29 (C ₅₄ H ₃₆ N ₂ =712.90) 2-25 m/z= 610.24 (C ₄₆ H ₃₀ N ₂ =610.76) 2-26 m/z= 610.24 (C ₄₆ H ₃₀ N ₂ =610.76) 2-27 m/z= 676.29 (C ₅₁ H ₃₆ N ₂ =676.86) 2-28 m/z= 710.27 (C ₅₄ H ₃₄ N ₂ =710.88) 2-29 m/z = 585.22 (C ₄₃ H ₂₇ N ₃ =585.71) 2-30 m/z= 818.31 (C ₆₀ H ₄₂ N ₂ Si=819.10) 2-31 m/z= 636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 2-32 m/z= 636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 2-33 m/z= 712.29 (C ₅₄ H ₃₆ N ₂ =712.90) 2-34 m/z= 712.29 (C ₅₄ H ₃₆ N ₂ =712.90) 2-35 m/z= 712.29 (C ₅₄ H ₃₆ N ₂ =712.90) 2-36 m/z= 610.24 (C ₄₆ H ₃₀ N ₂ =610.76) 2-37 m/z= 610.24 (C ₄₆ H ₃₀ N ₂ =610.76) 2-38 m/z= 676.29 (C ₅₁ H ₃₆ N ₂ =676.86) 2-39 m/z= 710.27 (C ₅₄ H ₃₄ N ₂ =710.88) 2-40 m/z = 585.22 (C ₄₃ H ₂₇ N ₃ =585.71) 2-41 m/z= 818.31 (C ₆₀ H ₄₂ N ₂ Si=819.10) 2-42 m/z= 636.26 (C ₄₈ H ₃₂ N ₂ =636.80) 2-43 m/z= 712.29 (C ₅₄ H ₃₆ N ₂ =712.90) 2-44 m/z= 712.29 (C ₅₄ H ₃₆ N ₂ =712.90) 2-45 m/z= 712.29 (C ₅₄ H ₃₆ N ₂ =712.90) 2-46 m/z= 610.24 (C ₄₆ H ₃₀ N ₂ =610.76) 2-47 m/z= 610.24 (C ₄₆ H ₃₀ N ₂ =610.76) 2-48 m/z= 676.29 (C ₅₁ H ₃₆ N ₂ =676.86) 2-49 m/z= 710.27 (C ₅₄ H ₃₄ N ₂ =710.88) 2-50 m/z = 585.22 (C ₄₃ H ₂₇ N ₃ =585.71) 2-51 m/z= 818.31 (C ₆₀ H ₄₂ N ₂ Si=819.10) 2-52 m/z= 788.32 (C ₆₀ H ₄₀ N ₂ =788.99) 2-53 m/z= 788.32 (C ₆₀ H ₄₀ N ₂ =788.99) 2-54 m/z= 788.32 (C ₆₀ H ₄₀ N ₂ =788.99) 2-55 m/z= 686.27 (C ₅₂ H ₃₄ N ₂ =686.86) 2-56 m/z= 686.27 (C ₅₂ H ₃₄ N ₂ =686.86) 2-57 m/z= 752.32 (C ₅₇ H ₄₀ N ₂ =752.96) 2-58 m/z= 786.30 (C ₆₀ H ₃₈ N ₂ =786.98) 2-59 m/z= 661.25 (C ₄₉ H ₃₁ N ₃ =661.81) 2-60 m/z= 894.34 (C ₆₆ H ₄₆ N ₂ Si=895.19) 2-61 m/z= 788.32 (C ₆₀ H ₄₀ N ₂ =788.99) 2-62 m/z= 788.32 (C ₆₀ H ₄₀ N ₂ =788.99) 2-63 m/z= 686.27 (C ₅₂ H ₃₄ N ₂ =686.86) 2-64 m/z= 686.27 (C ₅₂ H ₃₄ N ₂ =686.86) 2-65 m/z= 752.32 (C ₅₇ H ₄₀ N ₂ =752.96) 2-66 m/z= 786.30 (C ₆₀ H ₃₈ N ₂ =786.98) 2-67 m/z= 661.25 (C ₄₉ H ₃₁ N ₃ =661.81) 2-68 m/z= 894.34 (C ₆₆ H ₄₆ N ₂ Si=895.19) 2-69 m/z= 788.32 (C ₆₀ H ₄₀ N ₂ =788.99) 2-70 m/z= 686.27 (C ₅₂ H ₃₄ N ₂ =686.86) 2-71 m/z= 686.27 (C ₅₂ H ₃₄ N ₂ =686.86) 2-72 m/z= 752.32 (C ₅₇ H ₄₀ N ₂ =752.96) 2-73 m/z= 786.30 (C ₆₀ H ₃₈ N ₂ =786.98) 2-74 m/z= 661.25 (C ₄₉ H ₃₁ N ₃ =661.81) 2-75 m/z= 894.34 (C ₆₆ H ₄₆ N ₂ Si=895.19) 2-76 m/z= 584.23 (C ₄₄ H ₂₈ N ₂ =584.72) 2-77 m/z= 584.23 (C ₄₄ H ₂₈ N ₂ =584.72) 2-78 m/z= 650.27 (C ₄₉ H ₃₄ N ₂ =650.83) 2-79 m/z= 684.26 (C ₅₂ H ₃₂ N ₂ =684.84) 2-80 m/z= 559.20 (C ₄₁ H ₂₅ N ₃ =559.67) 2-81 m/z= 792.30 (C ₅₈ H ₄₀ N ₂ Si=793.06) 2-82 m/z= 584.23 (C ₄₄ H ₂₈ N ₂ =584.72) 2-83 m/z= 650.27 (C ₄₉ H ₃₄ N ₂ =650.83) 2-84 m/z= 684.26 (C ₅₂ H ₃₂ N ₂ =684.84) 2-85 m/z= 559.20 (C ₄₁ H ₂₅ N ₃ =559.67) 2-86 m/z= 792.30 (C ₅₈ H ₄₀ N ₂ Si=793.06)

compound ¹ H NMR (CDCl ₃ , 200 Mz) 1-18 δ = 8.52 (1H, d), 8.28~8.24 (3H, m), 8.12 (1H, d), 7.94~7.89 (2H, d), 7.75~7.70 (2H, m), 7.62~7.25 (19H, m) ) 1-19 δ = 8.53 (1H, d), 8.28~8.18 (4H, m), 7.94~7.89 (2H, q), 7.79~7.70 (3H, m), 7.62~7.25 (22H, m) 1-131 δ = 8.55 (1H, d), 8.28 (4H, d), 7.94 to 7.87 (3H, m), 7.77 to 7.73 (5H, m), 7.52 to 7.25 (15H, m) 1-133 δ = 8.28 (4H, d), 8.18 (1H, d), 8.0 (1H, d), 7.89 to 7.87 (2H, t), 7.77 to 7.73 (5H, m), 7.62 (1H, m), 7.52 to 7.41 (18H, m) 1-135 δ = 8.55 (1H, d), 8.28 (4H, m), 8.12 (1H, d), 7.94 to 7.89 (2H, m), 7.75 to 7.73 (2H, d), 7.63 to 7.25 (21H, m) 1-138 δ = 8.39 (1H, d), 8.28 (4H, d), 8.12 to 8.09 (2H, t), 7.89 (1H, d), 7.75 to 7.61 (6H, m), 7.51 to 7.41 (10H, m) 1-147 δ = 8.55 (1H, d), 8.28~8.24 (3H, m), 7.94~7.87 (3H, m), 7.73~7.25 (25H, m) 1-150 δ = 8.55 (1H, d), 8.28 (2H, d), 8.12 (1H, d), 7.94 to 7.85 (4H, m), 7.75 to 7.73 (2H, d), 7.63 to 7.62 (2H, d), 7.52~7.25 (16H, m) 1-264 δ = 8.55 (1H, d), 8.28 (2H, d), 8.12 (1H, d), 7.94~7.25 (22H, m) 1-265 δ = 8.28 (2H, m), 8.18~8.12 (2H, m), 8.00 (1H, d), 7.89~7.73 (7H, m), 7.66~7.62 (3H, m), 7.51~7.29 (15H, m) ) 1-271 δ = 8.55 (2H,d), 8.36(4H,t), 7.98~7.94(3H,m), 7.82(1H,d), 7.69~7.50(15H,m), 7.35(2H,t), 7.26~ 7.25(2H,d), 7.16(2H,t) 1-285 δ = 8.55 (1H, d), 8.28 (2H, d), 8.18 (1H, d), 7.94 to 7.73 (7H, m), 7.62 (2H,d), 7.52 to 7.25 (19H, m) 1-286 δ = 8.55 (1H, d), 8.28 (2H, d), 7.94 to 7.85 (5H, m), 7.77 to 7.69 (3H, m), 7.62 (1H, d), 7.51 to 7.25 (20H, m) 2-4 δ = 8.55(1H, d), 8.30(1H, d), 8.19~8.13(2H, m), 7.99~7.89(8H, m), 7.77~7.75(3H, m), 7.62~7.35(11H, m) ), 7.20~7.16 (2H, m) 2-7 δ = 8.55 (1H, d), 8.31 to 8.30 (3H, d), 8.19 to 8.13 (2H, m), 7.99 to 7.89 (5H, m), 7.77 to 7.75 (5H, m), 7.62 to 7.35 (14H) , m), 7.20~7.16 (2H, m) 2-16 δ = 8.93~8.90 (3H, d), 8.55 (1H, d), 8.18~8.10 (5H, m), 8.00~7.77 (10H, m), 7.58~7.45 (8H, m), 7.33~7.29 (2H) , m) 2-31 δ = 8.55 (1H, d), 8.30 (1H, d), 8.21 to 8.13 (4H, m), 7.99 to 7.89 (4H, m), 7.77 to 7.35 (20H, m), 7.20 to 7.16 (2H, m) ) 2-42 δ = 8.55 (1H, d), 8.18 to 8.12 (2H, m), 8.00 to 7.87 (3H, m), 7.79 to 7,77 (6H, m), 7.69 to 7.63 (6H, m), 7.52 to 7.25 (14H, m) 2-97 δ = 8.55 (1H, d), 8.18~8.09 (3H, m), 8.00~7.94 (2H, m), 7.87(1H, d), 7.79~7.77 (4H, m), 7.57~7.29 (25H, m) )

<Experimental Example> Fabrication of an organic light emitting device

1) Fabrication of an organic light emitting device

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

Then, after evacuating the chamber ^{until the vacuum level reached 10 -6} torr, an electric current was applied to the cell to form 2-TNATA (4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine) By evaporation, a hole injection layer having a thickness of 600 Å was deposited on the ITO substrate. The following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (N,N'-bis(α-naphthyl)-N, N'-diphenyl-4,4'-diamine: NPB) was added, and the cell was evaporated by applying a current to deposit a hole transport layer having a thickness of 300 Å on the hole injection layer.

The compound shown in Table 22 was deposited on the hole transport layer to form a hole transport auxiliary layer having a thickness of 350 Å.

Subsequently, the compound of Table 22 below was used as a host on the hole transport auxiliary layer at the same weight ratio as shown in Table 22, and the green phosphorescent dopant was _{deposited by doping 7 wt% of Ir(ppy) 3} to form a light emitting layer having a thickness of 400 Å. did. Then, BCP (Bathocuproine) was deposited at 60 Å as a hole blocking layer, and Alq ₃ was deposited at 200 Å as an electron transport layer thereon. Finally, lithium fluoride (LiF) is deposited to a thickness of 10 Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) cathode is deposited to a thickness of 1,200 Å on the electron injection layer to form a cathode. An electroluminescent device was manufactured.

Comparative compounds A and B used in Comparative Examples 3 to 6 of Table 22 are as follows.

hole transport auxiliary layer light emitting layer
compound ratio drive voltage
(V) efficiency
(cd/A) life span
(T ₉₀ ) Comparative Example 1 NPB 1-17 - 4.88 110.62 256 Comparative Example 2 NPB 2-4 4.97 108 260 Comparative Example 3 One Comparative compound A - 4.92 106.20 290 Comparative Example 4 15 Comparative compound B - 4.76 104 275 Comparative Example 5 One Comparative compound A: Comparative compound B 1:1 4.02 103 300 Comparative Example 6 15 Comparative compound A: Comparative compound B 1:1 4.05 105 304 Example 1 One 1-17 - 4.43 101.1 354 Example 2 One 2-42 - 4.31 111.1 310 Example 3 One 1-17: 2-42 1:1 3.36 104.3 510 Example 4 6 1-17: 2-42 1:1 3.42 111.4 467 Example 5 6 1-19: 2-4 2:1 3.59 113.2 401 Example 6 15 1-17: 2-42 5:1 4.42 100.8 362 Example 7 15 1-19: 2-4 8:1 4.87 102.7 365 Example 8 One 1-131: 2-7 1: 2 3.53 103.1 520 Example 9 One 1-131: 2-7 1:1 3.47 110.3 454 Example 10 6 1-19: 2-4 1: 2 3.43 103.5 481 Example 11 6 1-131: 2-7 1:1 3.66 112.6 543 Example 12 15 1-131: 2-7 1: 2 3.38 105.3 560 Example 13 15 1-131: 2-7 1:1 3.39 115.3 500 Example 14 23 1-18: 2-16 1: 2 3.56 102.8 532 Example 15 23 1-18: 2-16 1:1 3.58 116.6 499 Example 16 24 1-133: 2-16 1: 2 3.42 108.4 581 Example 17 24 1-133: 2-16 1:1 3.38 119.5 532 Example 18 28 1-138: 2-7 1: 2 3.72 103.4 592 Example 19 28 1-138: 2-7 1:1 3.89 115.6 552 Example 20 One 1-138: 2-7 1: 2 3.63 100.7 521 Example 21 One 1-147: 2-16 1:1 3.68 109.6 487 Example 22 9 1-147: 2-16 1: 2 3.53 106.7 520 Example 23 9 1-150: 2-7 1:1 3.50 112.8 489 Example 24 21 1-150: 2-7 1: 2 3.46 110.5 544 Example 25 21 1-264 : 2-31 1:1 3.43 118.7 501 Example 26 23 1-264 : 2-31 1: 2 3.22 113.8 603 Example 27 23 1-265 : 2-97 1:1 3.24 120.3 559 Example 28 24 1-265 : 2-97 1: 2 3.45 105.3 541 Example 29 24 1-271 : 2-31 1:1 3.44 115.4 477 Example 30 28 1-271 : 2-31 1: 2 3.03 114.4 680 Example 31 28 1-285: 2-16 1:1 3.08 123.3 552 Example 32 9 1-285: 2-16 1: 2 3.12 114.8 660 Example 33 9 1-285: 2-16 1:1 3.16 120.6 541

As can be seen in Table 22, when the heterocyclic compound represented by Formula 1 of the present application is used for the hole transport auxiliary layer, and the heterocyclic compound represented by Formula 2 or 3 of the present application is used for the light emitting layer, exciplex By the (exciplex) phenomenon, the driving voltage of the device of the organic light emitting device can be lowered and the light efficiency can be partially improved. I was able to confirm that it could be built.

Specifically, as in the heterocyclic compound represented by Formula 1 of the present application, a structure having two or more amine structures substituted with an aryl group, that is, in a diamine structure, both sides have the same structure and a linker is phenyl When a compound fixed with a structure of (phenyl) or higher is used for the hole transport auxiliary layer (prime layer), the aryl group of the amine group delocalizes the energy level of the HOMO (Highest Occupied Molecular Orbital) to homo By stabilizing energy, it effectively prevents electrons from passing from the opposite side of the electron transport layer, so that the luminous efficiency and lifespan are superior to those of the organic light emitting devices of Comparative Examples 1 and 2 that do not use the compound according to the present application when forming the prime layer. could check

In addition, an embodiment in which the heterocyclic compound represented by Formula 1 is used for the hole transport auxiliary layer and the heterocyclic compound represented by Formula 2 or 3 of the present application is used for an organic light emitting device is represented by Formula 1 of the present application In the case of the organic light emitting device of Comparative Examples 3 and 4 in which the heterocyclic compound to be used was used for the hole transport auxiliary layer (prime layer), but the heterocyclic compound represented by Chemical Formula 2 or 3 of the present application was not used in the light emitting layer, multi-device It was confirmed that the efficiency and lifespan of the

In addition, the heterocyclic compound represented by Formula 1 is used in the hole transport auxiliary layer, and the heterocyclic compound represented by Formula 2 or 3 of the present application is used in the light emitting layer, respectively, than when the heterocyclic compound represented by Formula 1 is used. When the compound was used for the hole transport auxiliary layer and the heterocyclic compound represented by Chemical Formulas 2 and 3 of the present application was used simultaneously, it was confirmed that the device had better performance.

The compound represented by Formula 1, which corresponds to a symmetric structure having 1 to 3 phenyls in the diarylamine structure and the linker part, increases the bond dissociation energy of the molecular structure, thereby increasing the rigidity of the structure itself. have thermal stability. Accordingly, thermal stability, which is a major factor of the hole transport auxiliary layer, can be secured, and a long lifespan device can be realized.

In addition, it was confirmed that the hole and electron velocities of the device can be controlled by specifically controlling the deposition ratio of the compounds represented by Chemical Formulas 2 and 3, and the results of the ratios vary depending on the device structure, but in the case of the experimental example It was confirmed that the device exhibited the best performance at a ratio of 1:1.

The compound represented by Formula 2 in which an N-containing cyclic group corresponding to an electron withdrawing group is substituted in the substituent of dibenzofuran is capable of increasing the electron speed in the organic light emitting device due to the N-containing cyclic group. can At this time, it is judged that there is an effect of suppressing the compound represented by Formula 3, which is a structure in which two carbazoles are arranged symmetrically as much as possible, such as biscarbazole, so as not to excessively speed the electron speed. do.

In the case of a mixture, since the amount of the mixing ratio affects the characteristics, it is very important to derive a mixing ratio that can maximize the charge balance of the mixture used in the light emitting layer.

From the experimental example results, it was confirmed that the closer the mixing ratio was to 1:1, the better the electron speed control effect occurred, and this electron speed control is helpful when adjusting the driving voltage.

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

Claims (11)

An organic light emitting device comprising a first electrode, a second electrode, and two or more organic material layers provided between the first electrode and the second electrode,
The organic material layer includes a light emitting layer,
The organic light emitting device is provided between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, and further comprises at least one layer of an organic material layer comprising a heterocyclic compound represented by the following Chemical Formula 1,
The light emitting layer is an organic light emitting device comprising a heterocyclic compound represented by Formula 2 or Formula 3:
[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3,
Ar _{1 To} Ar _{4 Are} the same as or different from each other, and are each independently a substituted or unsubstituted C 6 to C 60 aryl group,
R _m is hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C 1 to C 60 alkyl group; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, m is an integer from 0 to 4, and when m is 2 or more, R _m are the same as or different from each other,
n is an integer of 1 to 3, and when n is 2 or more, the substituents in parentheses are the same as or different from each other,
N-Het is a substituted or unsubstituted monocyclic or polycyclic heterocyclic group containing one or more N,
L is a direct bond; a substituted or unsubstituted arylene group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms, a is an integer of 1 to 3, and when a is 2 or more, L is the same as or different from each other,
R _a and R _b are the same as or different from each other, and each independently a substituted or unsubstituted C 6 to C 60 aryl group; Or a substituted or unsubstituted C 2 to C 60 heteroaryl group,
R1 to R10, R _c and R _d are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C 1 to C 60 alkyl group; a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; a substituted or unsubstituted C 3 to C 60 cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; a substituted or unsubstituted C 6 to C 60 aryl group; a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; a substituted or unsubstituted silyl 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 aliphatic or aromatic hydrocarbon ring or a hetero ring,
b and c are each an integer of 1 to 3, when b is 2 or more, R9 is the same as or different from each other, and when c is 2 or more, R10 is the same as or different from each other,
r and s are integers from 0 to 7, R _c is the same as or different from each other _{when r is 2 or more, and R d} is the same as or different from each other when s is 2 or more. The method according to claim 1,
The organic material layer including the heterocyclic compound represented by Formula 1 is an organic light emitting device that is one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, and a hole transport auxiliary layer. The method according to claim 1,
Formula 1 is an organic light emitting device represented by any one of the following Formulas A-1 to A-3:
[Formula A-1]

[Formula A-2]

[Formula A-3]

In the formulas A-1 to A-3,
Ar ₁ to Ar ₄ are the same as in Formula 1,
Ar ₅ is a substituted or unsubstituted C 6 to C 60 aryl group,
R _m1 to R _m6 are each independently hydrogen; heavy hydrogen; halogen; cyano group; a substituted or unsubstituted C 1 to C 60 alkyl group; Or a substituted or unsubstituted C 6 to C 60 aryl group,
m1 to m5 are each independently an integer of 0 to 4, and when m1 to m5 are each 2 or more, the substituents in each parenthesis are the same as or different from each other,
m6 is an integer of 0 to 3, and when m6 is 2 or more, the substituents in parentheses are the same as or different from each other. The organic light emitting diode of claim 1, wherein Chemical Formula 2 is represented by Chemical Formula 4 or 5:
[Formula 4]

[Formula 5]

In Formulas 4 and 5, the definitions of N-Het, L, R1 to R10, and a to c are the same as those in Formula 2 above. The organic light emitting diode of claim 1, wherein R _c and R _{d of Formula 3 are hydrogen.} The organic light emitting diode of claim 1, wherein R _a and R _b of Formula 3 are the same as or different from each other, and each independently represent a substituted or unsubstituted C 6 to C 40 aryl group. The organic light emitting diode of claim 1, wherein Chemical Formula 1 is represented by any one of the following compounds:

The organic light emitting diode of claim 1, wherein Chemical Formula 2 is represented by any one of the following compounds:

The organic light emitting diode of claim 1, wherein Chemical Formula 3 is represented by any one of the following compounds:

The organic light emitting device according to claim 1, wherein the light emitting layer includes the heterocyclic compound represented by Formula 2 and the heterocyclic compound represented by Formula 3 simultaneously. The organic light emitting device of claim 1, wherein the light emitting layer includes a host material, and the host material simultaneously includes the heterocyclic compound represented by Formula 2 and the heterocyclic compound represented by Formula 3 above.

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