KR20240113653A - Carbazole derivative compounds and electroluminescent device comprising the same - Google Patents

Abstract

The present invention is an organic compound represented by the following [Chemical Formula I], which has excellent hole injection and transport performance, high triplet exciton confinement performance, excellent electron blocking performance, and excellent stability in a thin film state, When used in an organic layer, preferably an electron blocking layer, in an organic light emitting device, it is possible to implement an organic light emitting device with excellent light emitting properties such as luminous efficiency and quantum efficiency.
[Formula Ⅰ]

Description

Carbazole derivative compounds and organic light-emitting device comprising the same {Carbazole derivative compounds and electroluminescent device comprising the same}

The present invention relates to carbazole derivative compounds, and more specifically, carbazole derivative compounds used in organic layers such as electron blocking layers in organic light-emitting devices, and device characteristics such as low-voltage operation, long life, and luminous efficiency are significantly improved by employing the same. It is about organic light emitting devices.

Organic light emitting devices not only can be formed on transparent substrates, but also can be driven at low voltages of 10 V or less compared to plasma display panels or inorganic electroluminescence (EL) displays, and consume relatively little power. , It has the advantage of excellent color and can display three colors of green, blue, and red, so it has recently been the subject of much attention as a next-generation display device.

In an organic light emitting device, electrons injected from an electron injection electrode (cathode electrode) and holes injected from a hole injection electrode (anode electrode) combine in the light emitting layer to form an exciton, and the exciton produces energy. It is a self-luminous device that emits light while emitting light, and such organic light-emitting devices are attracting attention as next-generation light sources due to the advantages of low driving voltage, high luminance, wide viewing angle, fast response speed, and applicability to full-color flat panel light-emitting displays. .

However, in order for these organic light-emitting devices to exhibit the above characteristics, the structure of the organic layer within the device must be optimized, and the materials that make up each organic layer: hole injection material, hole transport material, hole blocking material, light-emitting material, electron transport material, and electron. Although injection materials, electron blocking materials, etc. must be supported by stable and efficient materials, there is still a need for the development of stable and efficient organic layer structures and materials for organic light-emitting devices.

In particular, in order to achieve higher luminous efficiency, hole mobility is also increased, so there is a need for the development of materials that can be used not only as a hole injection layer or hole transport layer, but also as an electron blocking layer.

Therefore, the present invention aims to provide an organic compound that can be used as an organic layer material such as an electron blocking layer in an organic light-emitting device to significantly improve device characteristics such as low-voltage driving characteristics, long life, and luminous efficiency, and an organic light-emitting device containing the same. do.

In order to solve the above problems, the present invention provides a carbazole derivative organic compound represented by the following [Chemical Formula I] and an organic light-emitting device containing the same.

[Formula Ⅰ]

The specific structure of [Chemical Formula I], the specific compounds implemented thereby, and the definitions of X, R ₁ to R ₁₁ , p, q, and r will be described later.

Additionally, according to one embodiment of the present invention, the compound of [Formula I] according to the present invention is a compound partially substituted with deuterium (D) and may be represented by [Formula II] below.

[Formula Ⅱ]

The specific structure of [Chemical Formula II], the specific compounds implemented thereby, and the definitions of X, R ₁ to R ₁₁ , p, q, and r will be described later.

D is deuterium, n means the number of hydrogens in [Formula II] replaced with deuterium (D), and n is an integer from 0 to 60.

The organic compound according to the present invention has excellent hole injection and transport performance, high triplet exciton confinement performance, excellent electron blocking performance, and excellent stability in a thin film state, and is employed in organic layers such as electron blocking layers. An organic light-emitting device has significantly superior device characteristics such as low-voltage operation, long lifespan, and luminous efficiency compared to conventional devices, and can be usefully used in various lighting devices and display devices.

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

The present invention relates to a novel organic compound capable of realizing an organic light-emitting device with significantly improved device characteristics such as low-voltage operation, long life, and luminous efficiency when applied to various organic layers in an organic light-emitting device, preferably an electron blocking layer. , It is characterized by being represented by the following [Chemical Formula I].

The compound of [Formula I] according to the present invention has excellent hole injection and transport performance, high triplet exciton confinement performance, excellent electron blocking performance, and excellent stability in a thin film state, so it is adopted as an electron blocking layer. This makes it possible to implement an organic light-emitting device with high luminous efficiency, and in addition, the compound according to the present invention can implement an organic light-emitting device with optimized luminous efficiency even when combined with a phosphorescent material that emits blue as well as green light.

The compound represented by the following [Chemical Formula I] according to the present invention is structurally characterized in that (i) phenyl connected to the N-terminal of carbazole is connected to carbazole and dibenzofuran or dibenzothiophene as a linking group, , (ii) It is characterized by a structure in which an aryl (hetero)amine group is introduced into carbazole.

[Formula Ⅰ]

In the above [Chemical Formula I],

X is O or S.

R ₁ to R ₃ are each independently hydrogen or deuterium, p and q are integers from 0 to 4, r is an integer from 0 to 3, and when p, q and r are 2 or more, a plurality of R ₁ to R ₃ are the same or different from each other.

At this time, each one of the plurality of R ₂ and R ₃ is connected to the '*'.

R ₄ to R ₁₁ are the same or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group with 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 30 carbon atoms, and a substituted or unsubstituted carbon number. 3 to 20 cycloalkyl group, substituted or unsubstituted heterocycloalkyl group with 3 to 30 carbon atoms, substituted or unsubstituted aryl group with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group with 2 to 50 carbon atoms, substituted or It is selected from unsubstituted aliphatic aromatic mixed ring groups having 3 to 50 carbon atoms, substituted or unsubstituted silyl groups, substituted or unsubstituted germanium groups, cyano groups, and halogen groups.

However, at least one of R ₄ to R ₁₁ is represented by the following [Structural Formula 1], and is characterized in that an amine group of the following [Structural Formula 1] is introduced into carbazole.

[Structural Formula 1]

In [Structural Formula 1] above,

Ar ₁ and Ar ₂ are the same or different from each other, are each independently the same as or different from each other, and are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms and a substituted or unsubstituted aromatic hetero ring having 2 to 50 carbon atoms selected from among the rings.

At this time, according to an embodiment of the present invention, any one selected from R ₄ , R ₆ and R ₇ ; and any one selected from R ₈ , R ₁₀ , and R ₁₁ ; are each of the [Structural Formula 1]. That is, structures in which an amine group is bonded to the 2nd position of carbazole (R ₅ or R ₉ ) are excluded.

According to one embodiment of the present invention, one selected from R ₄ , R ₆ and R ₇ is characterized in that [Structural Formula 1].

In addition, according to one embodiment of the present invention, when dibenzofuran or dibenzothiophene is connected to phenylene, it is characterized in that it binds at the 1 or 3 position of dibenzofuran (thiophene), and thus The [Chemical Formula I] is characterized by being represented by the following [Chemical Formula I-1] or [Chemical Formula I-2].

[Formula Ⅰ-1] [Formula Ⅰ-2]

In the [Formula Ⅰ- ₁ ] and [Formula _Ⅰ -2], the definitions of Any one of R ₃ is a region connected to the '*'.

As such, the compound represented by [Chemical Formula I] according to the present invention is (i) a carbazole structure and a dibenzofuran (thiophene) structure using phenylene as a linking group, respectively ortho and meta to phenylene. ), para (para), respectively, and (ii) a characteristic combination of amine group positions bonded to carbazole, and (iii) limiting the position bonded to dibenzofuran (thiophene) as a structural feature. As a result, it is possible to implement a compound with a structure that has excellent hole injection and transport performance, high triplet exciton confinement performance, excellent electron blocking performance, and excellent stability in a thin film state.

In addition, according to one embodiment of the present invention, the compound of [Formula I] according to the present invention is characterized in that the hydrogen present in the substituents defined in R ₁ to R ₁₁ is partially further substituted with deuterium (D) As a compound, it can be represented by the following [Chemical Formula II], and accordingly, an organic light-emitting device with superior luminous efficiency and significantly improved lifespan characteristics can be implemented.

[Formula Ⅱ]

In the above [Chemical Formula II],

_{Where ​} And n is an integer from 0 to 60.

According to one embodiment of the present invention, the deuterium (D) substitution rate may be 10 to 90%, according to a preferred embodiment, the deuterium (D) substitution rate may be 20 to 80%, and according to a more preferred embodiment, the deuterium (D) substitution rate may be 10 to 90%. D) The substitution rate may be 30 to 70%.

Meanwhile, in the definitions of R ₁ to R ₁₁ , Ar ₁ and Ar ₂ in [Formula I] and [Formula II], ‘substituted or unsubstituted’ means that R ₁ to R ₁₁ , Ar ₁ and Ar ₂ are each Deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, halogenated alkyl group, alkoxy group, halogenated alkoxy group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, aliphatic aromatic mixed ring group, amine group, It means that it is substituted with one or two or more substituents selected from a silyl group and a germanium group, or is substituted with a substituent in which two or more of the substituents are connected, or does not have any substituent, and the hydrogen in the substituent can be replaced with one or more deuterium. In addition, two or more adjacent substituents may be connected to each other to form an additional alicyclic or aromatic monocyclic or polycyclic ring.

For specific examples, a substituted aryl group refers to a phenyl group, biphenyl group, naphthalene group, fluorenyl group, pyrenyl group, phenanthrenyl group, perylene group, tetracenyl group, anthracenyl group, etc. substituted with another substituent such as deuterium. means, and substituted heteroaryl group refers to pyridyl group, thiophenyl group, triazine group, quinoline group, phenanthroline group, imidazole group, thiazole group, oxazole group, carbazole group and condensed heterocyclic groups thereof, such as This means that benzquinoline group, benzimidazole group, benzoxazole group, benzthiazole group, benzcarbazole group, dibenzothiophenyl group, dibenzofuran group, etc. are also substituted with other substituents such as deuterium.

In addition, in the present invention, additionally forming a ring by linking with each other or adjacent groups means that adjacent substituents among the specified substituents are bonded to each other, or adjacent groups other than the specified substituents are bonded to each other to form a substituted or unsubstituted alicyclic or aromatic ring. means that it can form, and 'adjacent group' refers to a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent group located sterically closest to the substituent, or a substituent substituted on the atom on which the substituent is substituted. may refer to other substituents. For example, two substituents substituted at the ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring can be interpreted as 'adjacent groups'.

In the present invention, the alkyl group may be straight chain or branched, and 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, etc., but is not limited to these.

In the present invention, the alkoxy group may be straight chain or branched chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20, which is within a range that does not cause steric hindrance. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, i-propyloxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group. , neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group , benzyloxy group, p-methylbenzyloxy group, etc., but is not limited thereto.

In the present invention, the alkyl group and the alkoxy group may be a deuterated alkyl group or alkoxy group, a halogenated alkyl group, or an alkoxy group, respectively, and the alkyl group or alkoxy group refers to an alkyl group or alkoxy group substituted with a deuterium or halogen group.

In the present invention, the aromatic hydrocarbon ring or aryl group may be monocyclic or polycyclic, and polycyclic refers to a group directly connected or condensed with another ring group. The other ring group may be an aromatic hydrocarbon ring, but may be a different type of ring. It may be a group, such as an aliphatic heterocycle, an aliphatic hydrocarbon ring, an aromatic heterocycle, etc. Examples of monocyclic aryl groups include phenyl group, biphenyl group, and terphenyl group, and examples of polycyclic aryl groups include naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, tetracenyl group, and chrysenyl group. group, fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthene group, etc., but the scope of the present invention is not limited to these examples.

In the present invention, the fluorenyl group is a structure in which two ring organic compounds are connected through one atom, for example , , etc.

In the present invention, the fluorenyl group includes the structure of an open fluorenyl group, where the open fluorenyl group is a structure in which one ring compound is disconnected in a structure where two ring organic compounds are connected through one atom. , for example , etc.

Additionally, the carbon atom of the ring may be substituted with one or more heteroatoms selected from N, S, and O, for example , , , etc.

Additionally, in the present invention, the fluorenyl group may have a structure in which a monocyclic or polycyclic aromatic ring and a monocyclic or polycyclic alicyclic ring, etc. are further condensed to the above connected structure or open structure.

In the present invention, the aromatic heterocycle or heteroaryl group is an aromatic ring containing one or more heteroatoms, examples of which include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, and oxadia. Sol group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group , pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, indolocarbazole group, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group. , benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, pheno Thiazinyl group, etc., but is not limited to these.

In the present invention, an aliphatic hydrocarbon ring or cycloalkyl group refers to a non-aromatic ring consisting only of carbon and hydrogen atoms, examples of which include monocyclic or polycyclic, and may be further substituted by other substituents. A ring refers to a group directly connected to or condensed with another ring group. The other ring group may be an aliphatic hydrocarbon ring, but may also be another type of ring group, such as an aliphatic heterocycle, an aromatic hydrocarbon ring, or an aromatic heterocycle. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, adamantyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclo Cycloalkyl groups such as hexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, and cyclooctyl group, and cyclohexane and cyclo It includes, but is not limited to, cycloalkanes such as pentane, and cyclocycloalkenes such as cyclohexene and cyclobutene.

In the present invention, an aliphatic heterocycle or heterocycloalkyl group refers to an aliphatic ring containing one or more heteroatoms, and includes heteroatoms such as O, S, Se, N or Si, and is also monocyclic or polycyclic. It may be further substituted by other substituents, and polycyclic refers to a group in which heterocycloalkyl, heterocycloalkane, etc. are directly connected or condensed with another ring group. The other ring group may be an aliphatic heterocycle. It may be other types of ring groups, such as aliphatic hydrocarbon rings, aromatic hydrocarbon rings, aromatic heterocycles, etc.

In the present invention, an aliphatic aromatic mixed ring (group) refers to a ring in which two or more rings are connected and condensed, and the aliphatic ring and the aromatic ring are condensed to have overall non-aromaticity. More specifically, is an aromatic hydrocarbon ring condensed with an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring condensed with an aliphatic heterocycle, an aromatic heterocyclic ring condensed with an aliphatic hydrocarbon ring, an aromatic heterocycle condensed with an aliphatic heterocycle, an aliphatic hydrocarbon ring condensed with an aromatic hydrocarbon ring. , an aliphatic hydrocarbon ring group condensed with an aromatic hetero ring, an aliphatic hetero ring group condensed with an aromatic hydrocarbon ring, an aliphatic hetero ring group condensed with an aromatic hetero ring, etc. In addition, the polycyclic aliphatic aromatic mixed ring may contain heteroatoms such as N, O, S, Si, Ge, and P in addition to carbon.

In the present invention, the silyl group is an unsubstituted silyl group or a silyl group substituted with an alkyl group, an aryl group, etc., and specific examples of such silyl groups include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, and dimethoxysilyl. Examples include phenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl, etc., but are not limited thereto.

In the present invention, the germanium group (or germanium group) may include -GeH ₃ , an alkyl germanium group, an aryl germanium group, a heteroaryl germanium group, an alkylaryl germanium group, an alkylheteroaryl germanium group, an arylheteroaryl germanium group, etc. These definitions follow those described for the silyl group, but can be applied to each substituent as a substituent obtained by substituting a germanium atom (Ge) in place of a silicon atom (Si) in the silyl group.

In addition, specific examples of the germanium group include trimethylgermain, triethylgermain, triphenylgermain, trimethoxygermain, dimethoxyphenylgermain, diphenylmethylgermain, diphenylvinylgermain, methylcyclobutylgermain, dimethylfurylgermain, etc. One or more hydrogen atoms of the germanium group can be replaced with the same substituent as that of the aryl group.

In the present invention, the amine group may be -NH ₂ , an alkylamine group, an arylamine group, an arylheteroarylamine group, etc., an arylamine group refers to an amine substituted with aryl, and an alkylamine group refers to an amine substituted with alkyl. The arylheteroarylamine group refers to an amine substituted with aryl and heteroaryl groups. Examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or There is an unsubstituted triarylamine group, and the aryl group and heteroaryl group in the arylamine group and arylheteroarylamine group may be a monocyclic aryl group, a monocyclic heteroaryl group, or a polycyclic aryl group or a polycyclic heteroaryl group. and the aryl group, the arylamine group containing two or more heteroaryl groups, and the arylheteroarylamine group include a monocyclic aryl group (heteroaryl group), a polycyclic aryl group (heteroaryl group), or a monocyclic aryl group (heteroaryl group). It may contain both an aryl group) and a polycyclic aryl group (heteroaryl group). In addition, the aryl group and heteroaryl group of the arylamine group and arylheteroarylamine group may be selected from examples of the above-mentioned aryl group and heteroaryl group.

Specific examples of the halogen group used in the present invention include fluorine (F), chlorine (Cl), and bromine (Br).

Additionally, various specific examples of substituents according to the present invention can be clearly identified in the specific compounds described below.

As described above, the organic compound according to the present invention represented by [Chemical Formula I] can be used as an organic layer of an organic light-emitting device due to its structural specificity, and more specifically, electron blocking of the organic layer depending on the characteristics of various substituents introduced. It can be used as a material for layers, etc.

Preferred specific examples of the compound represented by [Chemical Formula I] according to the present invention include the following compounds, but are not limited to these.

Through the above-mentioned characteristic skeletal structure and substituents, organic compounds with unique characteristics of the skeletal structure and substituents can be synthesized. For example, when manufacturing an organic light-emitting device, an organic compound material that satisfies the conditions required for each organic layer can be manufactured. In particular, when the compound of [Chemical Formula I] according to the present invention is used in the electron blocking layer, etc., device characteristics such as luminous efficiency of the device can be further improved.

The organic compound according to the present invention can be applied to an organic light-emitting device according to a conventional manufacturing method.

The organic light emitting device according to an embodiment of the present invention may have a structure including a first electrode, a second electrode, and an organic layer disposed between them, except that the organic compound according to the present invention is used in the organic layer of the device. It can be manufactured using conventional device manufacturing methods and materials.

The organic layer of the organic light emitting device according to the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic layers are stacked. For example, it 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, an electron blocking layer, etc. However, it is not limited to this and may include fewer or more organic layers.

As such, the organic light emitting device according to an embodiment of the present invention may include a hole injection layer, a hole transport layer, a light emitting layer, etc. formed on an anode, and may also include a hole blocking layer, an electron injection layer, an electron transport layer, an electron blocking layer, It may include a light emitting auxiliary layer, etc., but is not limited thereto.

Therefore, in the organic light emitting device according to the present invention, the organic layer may include an electron blocking layer, etc., and one or more of the layers may include the organic compound represented by [Chemical Formula I].

In addition, the organic light emitting device according to the present invention deposits a metal, a conductive metal oxide, or an alloy thereof on a substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation. is deposited to form an anode, and an organic layer including a hole injection layer, a hole transport layer, a hole blocking layer, a light-emitting layer, an electron blocking layer, an electron transport layer, an electron blocking layer, etc. is formed thereon, and then an organic layer that can be used as a cathode is formed thereon. It can be manufactured by depositing the material.

In addition to this method, an organic light-emitting device can also be made by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate. The organic layer may have a multilayer structure including a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, an electron transport layer, an electron blocking layer, etc., but is not limited to this and may have a single layer structure. In addition, the organic layer uses a variety of polymer materials to form a smaller number of layers by a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than deposition. It can be manufactured in layers.

The anode is usually preferably a material with a large work function to ensure smooth hole injection into the organic layer. Specific examples of anode materials that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metal oxides, combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT) , conductive polymers such as polypyrrole and polyaniline, but are not limited to these.

The cathode is generally preferably made of a material with a low work function to facilitate electron injection into the organic layer. Specific examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof, multilayers such as LiF/Al or LiO ₂ /Al. Structural materials, etc., but are not limited to these.

The hole injection layer is a material that can easily inject holes from the anode at a low voltage. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene, quinacridone-based organic substances, perylene-based organic substances, Examples include anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited to these.

The hole transport layer is a material that can transport holes from the anode or hole injection layer and transfer them to the light emitting layer, and a material with high mobility for holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions, but are not limited to these.

The electron blocking layer is a layer that blocks the movement of electrons and can be formed on the hole transport layer. An electron blocking layer that can block the movement of electrons without affecting the transport of holes can be used. Additionally, a light-emitting layer may be formed on the electron blocking layer, and a hole blocking layer, an electron transport layer, and an electron injection layer may be formed.

The hole blocking layer can be used to prevent the movement of holes without affecting the transport of electrons. An example of such a hole blocking layer is TPBi (1,3,5-tri(1-phenyl-1H-benzo). [d]imidazol-2-yl)phenyl), BCP (2,9-dimethyl4,7-diphenyl-1,10-phenanthroline), CBP (4,4-bis(N-carbazolyl)-1,1'-biphenyl ), PBD (2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole), PTCBI (bisbenzimidazo[2,1-a:1',2-b']anthra [2,1,9-def:6,5,10-d'e'f']diisoguinoline-10,21-dione) or BPhen (4,7-diphenyl-1,10-phenanthroline), etc. It is not limited.

The light-emitting layer is a material that can emit light in the visible light range by transporting holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining them, and a material with good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole, and Examples include benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, and rubrene, but are not limited to these.

The electron injection layer can be one that has high injection efficiency of electrons transferred from the cathode. Examples of such electron injection layers include, but are not limited to, lithium quinolate (Liq).

The electron transport layer is a material that can easily receive electrons from the cathode and transfer them to the light emitting layer, and a material with high electron mobility is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline, a complex containing Alq ₃ , an organic radical compound, and a hydroxyflavone-metal complex.

The organic light emitting device according to the present invention may be a front emitting type, a back emitting type, or a double-sided emitting type depending on the material used.

In addition, the organic compound according to the present invention can function in organic electronic devices, including organic solar cells, organic photoreceptors, organic transistors, etc., on a principle similar to that applied to organic light-emitting devices.

Hereinafter, synthesis examples of preferred compounds and device examples are presented to aid understanding of the present invention. However, the following examples are for illustrating the present invention and are not intended to limit the scope of the present invention.

Synthesis example 1: Synthesis of Compound 2

(One) Manufacturing example 1: Synthesis of intermediate 2-1

1-Bromodibenzo[b,d]furan (10.0 g, 0.041 mol), 2-Fluorophenylboronic acid (6.8 g, 0.049 mol), K ₂ CO ₃ (16.8 g, 0.121 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.8 mmol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.1 g (yield 58.4%) of <Intermediate 2-1>.

(2) Manufacturing example 2: Synthesis of intermediate 2-2

Add 500 mL of DMF to Intermediate 2-1 (10.0 g, 0.038 mol), 1-Bromo-9H-carbazole (11.3 g, 0.046 mol), and Cs ₂ CO ₃ (7.9 g, 0.057 mol) and stir at 150°C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 11.4 g (yield 61.2%) of <Intermediate 2-2>.

(3) Manufacturing example 3: Synthesis of intermediate 2-3

[1,1':2',1"-terphenyl]-4'-amine (10.0 g, 0.041 mol), 4-Bromobiphenyl (14.3 g, 0.061 mol), NaOtBu (11.8 g, 0.122 mol), Pd(dba ) ₂ (0.9 g, 1.6 mmol) and t-Bu ₃ P (0.7 g, 3.3 mmol) were mixed with 150 mL of By recrystallization, 10.5 g (yield 64.8%) of <Intermediate 2-3> was obtained.

(4) Manufacturing example 4: Synthesis of Compound 2

Intermediate 2-2 (10.0 g, 0.021 mol), Intermediate 2-3 (12.2 g, 0.031 mol), NaOtBu (5.9 g, 0.061 mol), Pd(dba) ₂ (0.4 g, 0.8 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.3 g, 1.5 mmol) and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.4 g of <Compound 2> (yield 69.2%).

LC/MS: m/z=804[(M) ⁺ ]

Synthesis example 2: Synthesis of Compound 17

(One) Manufacturing example 1: Synthesis of intermediate 17-1

3-Bromodibenzo[b,d]furan (10.0 g, 0.041 mol), 4-Fluorophenylboronic acid (6.8 g, 0.049 mol), K ₂ CO ₃ (16.8 g, 0.121 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.8 mmol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.7 g (yield 63.1%) of <Intermediate 17-1>.

(2) Manufacturing example 2: Synthesis of intermediate 17-2

Add 500 mL of DMF to Intermediate 17-1 (10.0 g, 0.038 mol), 1-Bromo-9H-carbazole (11.3 g, 0.046 mol), and Cs ₂ CO ₃ (7.9 g, 0.057 mol) and stir at 150°C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 12.2 g of <Intermediate 17-2> (yield 65.5%).

(3) Manufacturing example 3: Synthesis of Compound 17

Intermediate 17-2 (10.0 g, 0.021 mol), N-(biphenyl-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (11.1 g, 0.031 mol), NaOtBu (5.9 g, 0.061 mol) ), Pd(dba) ₂ (0.5 g, 0.8 mmol), and t-Bu ₃ P (0.3 g, 1.6 mmol) were added to 150 mL of Xylene and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.1 g of <Compound 17> (yield 70.5%).

LC/MS: m/z=768[(M) ⁺ ]

Synthesis example 3: Synthesis of Compound 37

(One) Manufacturing example 1: Synthesis of intermediate 37-1

Add 500 mL of DMF to Intermediate 2-1 (10.0 g, 0.038 mol), 3-Bromo-9H-carbazole (11.3 g, 0.046 mol), and Cs ₂ CO ₃ (7.9 g, 0.057 mol) and stir at 150°C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 12.4 g of <Intermediate 37-1> (yield 64.5%).

(2) Manufacturing example 2: Synthesis of Compound 37

Intermediate 37-1 (10.0 g, 0.021 mol), N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-3-amine (10.3 g, 0.031 mol), NaOtBu (5.9 g, 0.061 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), and t-Bu ₃ P (0.3 g, 1.6 mmol) were mixed with 150 mL of xylene and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.4 g of <Compound 37> (yield 75.0%).

LC/MS: m/z=742[(M) ⁺ ]

Synthesis example 4: Synthesis of Compound 57

(One) Manufacturing example 1: Synthesis of intermediate 57-1

3-Bromodibenzo[b,d]furan (10.0 g, 0.041 mol), 2-Fluorophenylboronic acid (6.8 g, 0.049 mol), K ₂ CO ₃ (16.8 g, 0.121 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.8 mmol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.5 g of <Intermediate 57-1> (yield 61.2%).

(2) Manufacturing example 2: Synthesis of intermediate 57-2

Add 500 mL of DMF to Intermediate 57-1 (10.0 g, 0.038 mol), 3-Bromo-9H-carbazole (11.3 g, 0.046 mol), and Cs ₂ CO ₃ (7.9 g, 0.057 mol) and stir at 150°C for 12 hours. The reaction was carried out by refluxing and stirring. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 10.9 g (yield 58.5%) of <Intermediate 57-2>.

(3) Manufacturing example 3: Synthesis of intermediate 57-3

9,9'-Spirobi[fluoren]-4-amine (10.0 g, 0.030 mol), 2-Bromobiphenyl (10.6 g, 0.045 mol), NaOtBu (8.7 g, 0.091 mol), Pd(dba) ₂ (0.7 g, 1.2 mmol), 150 mL of xylene was added to t-Bu ₃ P (0.5 g, 2.4 mmol) and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 9.2 g of <Intermediate 57-3> (yield 63.1%).

(4) Manufacturing example 4: Synthesis of Compound 57

Intermediate 57-2 (10.0 g, 0.021 mol), Intermediate 57-3 (14.9 g, 0.031 mol), NaOtBu (5.9 g, 0.061 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.3 g, 1.6 mmol) and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.9 g of <Compound 57> (yield 65.2%).

LC/MS: m/z=890[(M) ⁺ ]

Synthesis example 5: Synthesis of Compound 80

(One) Manufacturing example 1: Synthesis of intermediate 80-1

3-Bromodibenzo[b,d]furan (10.0 g, 0.041 mol), 3-Fluorophenylboronic acid (6.8 g, 0.048 mol), K ₂ CO ₃ (16.8 g, 0.121 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.8 mmol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.3 g of <Intermediate 80-1> (yield 59.4%).

(2) Manufacturing example 2: Synthesis of intermediate 80-2

Add 500 mL of DMF to Intermediate 80-1 (10.0 g, 0.038 mol), 3-Bromo-9H-carbazole (11.3 g, 0.046 mol), and Cs ₂ CO ₃ (7.9 g, 0.057 mol) and stir at 150°C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.1 g of <Intermediate 80-2> (yield 59.6%).

(3) Manufacturing example 3: Synthesis of Compound 80

Intermediate 80-2 (10.0 g, 0.021 mol), N-[1,1'-biphenyl]-2-yl-[1,1'-biphenyl]-2-amine (9.9 g, 0.031 mol), NaOtBu (5.9 g, 0.061 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), and t-Bu ₃ P (0.3 g, 1.6 mmol) were mixed with 150 mL of xylene and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 10.4 g of <Compound 80> (yield 69.7%).

LC/MS: m/z=728[(M) ⁺ ]

Synthesis example 6: Synthesis of compound 114

(One) Manufacturing example 1: Synthesis of intermediate 114-1

1-Bromodibenzo[b,d]furan (10.0 g, 0.041 mol), 4-Fluorophenylboronic acid (6.8 g, 0.049 mol), K ₂ CO ₃ (16.8 g, 0.121 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.8 mmol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then columnarized to obtain 6.8 g (yield 64.1%) of <Intermediate 114-1>.

(2) Manufacturing example 2: Synthesis of intermediate 114-2

Add 500 mL of DMF to Intermediate 114-1 (10.0 g, 0.038 mol), 3-Bromo-9H-carbazole (11.3 g, 0.046 mol), and Cs ₂ CO ₃ (7.9 g, 0.057 mol) and stir at 150°C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.8 g of <Intermediate 114-2> (yield 63.4%).

(3) Manufacturing example 3: Synthesis of Compound 114

Intermediate 114-2 (10.0 g, 0.021 mol), N-[1,1'-biphenyl]-4yl-dibenzothiophene-3-amine (10.8 g, 0.031 mol), NaOtBu (5.9 g, 0.061 mol), Pd(dba ) ₂ (0.5 g, 0.8 mmol) and t-Bu ₃ P (0.3 g, 1.6 mmol) were mixed with 150 mL of Xylene and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.0 g of <Compound 114> (yield 70.8%).

LC/MS: m/z=758[(M) ⁺ ]

Synthesis example 7: Synthesis of Compound 126

(One) Manufacturing example 1: Synthesis of intermediate 126-1

Add 500 mL of DMF to Intermediate 2-1 (10.0 g, 0.038 mol), 4-Bromo-9H-carbazole (11.3 g, 0.046 mol), and Cs ₂ CO ₃ (7.9 g, 0.057 mol) and stir at 150°C for 12 hours. The reaction was carried out by refluxing and stirring. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.4 g of <Intermediate 126-1> (yield 61.2%).

(2) Manufacturing example 2: Synthesis of Compound 126

Intermediate 126-1 (10.0 g, 0.021 mol), Bis(4-biphenylyl)amine (9.9 g, 0.031 mol), NaOtBu (5.9 g, 0.061 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), t 150 mL of Xylene was added to -Bu ₃ P (0.3 g, 1.6 mmol) and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.1 g of <Compound 126> (yield 74.4%).

LC/MS: m/z=728[(M) ⁺ ]

Synthesis example 8: Synthesis of Compound 144

(One) Manufacturing example 1: Synthesis of intermediate 144-1

3-Dibenzofuranamine (10.0 g, 0.055 mol), 2-Bromo-9,9'-dimethylfluorene (22.4 g, 0.082 mol), NaOtBu (15.7 g, 0.164 mol), Pd(dba) ₂ (1.3 g, 2.2 mmol) , 150 mL of Xylene was added to t-Bu ₃ P (0.9 g, 4.4 mmol) and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 12.8 g of <Intermediate 144-1> (yield 62.5%).

(2) Manufacturing example 2: Synthesis of Compound 144

Intermediate 126-1 (10.0 g, 0.021 mol), Intermediate 144-1 (11.5 g, 0.031 mol), NaOtBu (5.9 g, 0.061 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.3 g, 1.6 mmol) and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 10.9 g of <Compound 144> (yield 68.0%).

LC/MS: m/z=782[(M) ⁺ ]

Synthesis example 9: Synthesis of Compound 155

(One) Manufacturing example 1: Synthesis of Compound 155

Intermediate 126-1 (10.0 g, 0.021 mol), N-Phenyl-9,9'-spirobi[9H-fluoren]-4-amine (12.5 g, 0.031 mol), NaOtBu (5.9 g, 0.061 mol), Pd( 150 mL of xylene was added to dba) ₂ (0.5 g, 0.8 mmol) and t-Bu ₃ P (0.3 g, 1.6 mmol) and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.6 g of <Compound 155> (yield 69.5%).

LC/MS: m/z=814[(M) ⁺ ]

Synthesis example 10: Synthesis of Compound 184

(One) Manufacturing example 1: Synthesis of intermediate 184-1

Add 500 mL of DMF to Intermediate 57-1 (10.0 g, 0.038 mol), 4-Bromo-9H-carbazole (11.3 g, 0.046 mol), and Cs ₂ CO ₃ (7.9 g, 0.057 mol) and stir at 150°C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.4 g of <Intermediate 184-1> (yield 61.2%).

(2) Manufacturing example 2: Synthesis of Compound 184

Intermediate 184-1 (10.0 g, 0.021 mol), Bis(4-biphenylyl)amine (9.9 g, 0.031 mol), NaOtBu (5.9 g, 0.061 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), t 150 mL of Xylene was added to -Bu ₃ P (0.3 g, 1.6 mmol) and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 10.7 g of <Compound 184> (yield 71.7%).

LC/MS: m/z=728[(M) ⁺ ]

Synthesis example 11: Synthesis of compound 212

(One) Manufacturing example 1: Synthesis of intermediate 212-1

1-Bromodibenzo[b,d]furan (10.0 g, 0.041 mol), 3-Fluorophenylboronic acid (6.8 g, 0.049 mol), K ₂ CO ₃ (16.8 g, 0.121 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.8 mmol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 7.3 g (yield 68.7%) of <Intermediate 212-1>.

(2) Manufacturing example 2: Synthesis of intermediate 212-2

Add 500 mL of DMF to Intermediate 212-1 (10.0 g, 0.038 mol), 4-Bromo-9H-carbazole (11.3 g, 0.046 mol), and Cs ₂ CO ₃ (7.9 g, 0.057 mol) and stir at 150°C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 12.5 g of <Intermediate 212-2> (yield 67.1%).

(3) Manufacturing example 3: Synthesis of Compound 212

Intermediate 212-2 (10.0 g, 0.021 mol), N-([1,1'-biphenyl]-4-yl)-[1,1':3',1"-terphenyl]-5'-amine (12.2 _{Add 150} mL of After the reaction was completed by stirring at ℃, extraction, concentration, and recrystallization were performed on a column to obtain 10.9 g of <Compound 212> (yield 66.1%).

LC/MS: m/z=804[(M) ⁺ ]

Synthesis example 12: Synthesis of compound 285

(One) Manufacturing example 1: Synthesis of intermediate 285-1

1-Bromodibenzo[b,d]thiophene (10.0 g, 0.038 mol), 2-Fluorophenylboronic acid (6.4 g, 0.046 mol), K ₂ CO ₃ (15.8 g, 0.114 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.8 mmol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.2 g (yield 58.6%) of <Intermediate 285-1>.

(2) Manufacturing example 2: Synthesis of intermediate 285-2

Add 500 mL of DMF to Intermediate 285-1 (10.0 g, 0.036 mol), 3-Bromo-9H-carbazole (10.6 g, 0.043 mol), and Cs ₂ CO ₃ (7.5 g, 0.054 mol) and stir at 150°C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 10.6 g of <Intermediate 285-2> (yield 58.5%).

(3) Manufacturing example 3: Synthesis of Compound 285

Intermediate 285-2 (10.0 g, 0.020 mol), N-([1,1'-biphenyl]-4-yl)-9,9-diphenyl-9H-fluoren-2-amine (14.4 g, 0.030 mol), _{Add 150} mL of . After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.9 g of <Compound 285> (yield 66.0%).

LC/MS: m/z=908[(M) ⁺ ]

Synthesis example 13: Synthesis of Compound 324

(One) Manufacturing example 1: Synthesis of intermediate 324-1

Add 500 mL of DMF to Intermediate 285-1 (10.0 g, 0.036 mol), 4-Bromo-9H-carbazole (10.6 g, 0.043 mol), and Cs ₂ CO ₃ (7.5 g, 0.054 mol) and stir at 150°C for 12 hours. The reaction was carried out by refluxing and stirring. After completion of the reaction, it was extracted, concentrated, and then recrystallized with a column to obtain 10.7 g of <Intermediate 324-1> (yield 59.0%).

(2) Manufacturing example 2: Synthesis of Compound 324

Intermediate 324-1 (10.0 g, 0.020 mol), Bis(4-biphenylyl)amine (9.6 g, 0.030 mol), NaOtBu (5.7 g, 0.060 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), t 150 mL of Xylene was added to -Bu ₃ P (0.3 g, 1.6 mmol) and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.7 g of <Compound 324> (yield 72.5%).

LC/MS: m/z=744[(M) ⁺ ]

Synthesis example 14: Synthesis of Compound 360

(One) Manufacturing example 1: Synthesis of intermediate 360-1

3-Bromodibenzo[b,d]thiophene (10.0 g, 0.038 mol), 2-Fluorophenylboronic acid (6.4 g, 0.046 mol), K ₂ CO ₃ (15.8 g, 0.114 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.8 mmol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.4 g (yield 60.5%) of <Intermediate 360-1>.

(2) Manufacturing example 2: Synthesis of intermediate 360-2

Add 500 mL of DMF to Intermediate 360-1 (10.0 g, 0.036 mol), 4-Bromo-9H-carbazole (10.6 g, 0.043 mol), and Cs ₂ CO ₃ (7.5 g, 0.054 mol) and stir at 150°C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.4 g of <Intermediate 360-2> (yield 62.9%).

(3) Manufacturing example 3: Synthesis of Compound 360

Intermediate 360-2 (10.0 g, 0.020 mol), N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-3-amine (10.0 g, 0.030 mol), NaOtBu (5.7 g, 0.060 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), and t-Bu ₃ P (0.3 g, 1.6 mmol) were mixed with 150 mL of xylene and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 10.6 g of <Compound 360> (yield 70.5%).

LC/MS: m/z=758[(M) ⁺ ]

Synthesis example 15: Synthesis of Compound 393

(One) Manufacturing example 1: Synthesis of intermediate 393-1

1-Bromodibenzo[b,d]thiophene (10.0 g, 0.038 mol), 4-Fluorophenylboronic acid (6.4 g, 0.046 mol), K ₂ CO ₃ (15.8 g, 0.114 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.8 mmol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 7.0 g (yield 66.2%) of <Intermediate 393-1>.

(2) Manufacturing example 2: Synthesis of intermediate 393-2

Add 500 mL of DMF to Intermediate 393-1 (10.0 g, 0.036 mol), 4-Bromo-9H-carbazole (10.6 g, 0.043 mol), and Cs ₂ CO ₃ (7.5 g, 0.054 mol) and stir at 150°C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.8 g of <Intermediate 393-2> (yield 65.1%).

(3) Manufacturing example 3: Synthesis of Compound 393

Intermediate 393-2 (10.0 g, 0.020 mol), Bis(9,9-dimethyl-9H-fluoren-2-yl)amine (11.9 g, 0.030 mol), NaOtBu (5.7 g, 0.060 mol), Pd(dba) 150 mL of Xylene was added to ₂ (0.5 g, 0.8 mmol) and t-Bu ₃ P (0.3 g, 1.6 mmol) and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.4 g of <Compound 393> (yield 69.7%).

LC/MS: m/z=824[(M) ⁺ ]

Synthesis example 16: Synthesis of Compound 438

(One) Manufacturing example 1: Synthesis of intermediate 438-1

1-Bromodibenzo[b,d]furan (10.0 g, 0.041 mol), 4-Fluoro(phenyl-d4)-boronic acid (7.0 g, 0.049 mol), K ₂ CO ₃ (16.8 g, 0.121 mol), Pd( To PPh ₃ ) ₄ (0.9 g, 0.8 mmol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.6 g (yield 61.2%) of <Intermediate 438-1>.

(2) Manufacturing example 2: Synthesis of intermediate 438-2

Add 500 mL of DMF to Intermediate 438-1 (10.0 g, 0.038 mol), 4-Bromo-9H-carbazole (11.1 g, 0.045 mol), and Cs ₂ CO ₃ (7.8 g, 0.056 mol) and stir at 150°C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 12.6 g (yield 68.1%) of <Intermediate 438-2>.

(3) Manufacturing example 3: Synthesis of intermediate 438-3

9,9'-Spirobi[fluoren]-4-amine (10.0 g, 0.030 mol), 4-bromo-1,1'-biphenyl-2,2',3,3',4',5,5', 6,6'-d9 (11.0 g, 0.045 mol), NaOtBu (8.7 g, 0.091 mol), Pd(dba) ₂ (0.7 g, 1.2 mmol), t-Bu ₃ P (0.5 g, 2.4 mmol) Add 150 mL and stir at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 9.8 g of <Intermediate 438-3> (yield 65.9%).

(4) Manufacturing example 4: Synthesis of Compound 438

Intermediate 438-2 (10.0 g, 0.020 mol), Intermediate 438-3 (15.0 g, 0.031 mol), NaOtBu (5.9 g, 0.061 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.3 g, 1.6 mmol) and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 12.4 g of <Compound 438> (yield 67.5%).

LC/MS: m/z=903[(M) ⁺ ]

device Example (blue EBL )

In an embodiment according to the present invention, the ITO transparent electrode is patterned so that the light emitting area is 2 mm × 2 mm using an ITO glass substrate to which the ITO transparent electrode is attached on a glass substrate of 25 mm × 25 mm × 0.7 mm. and then washed. After the substrate was mounted in a vacuum chamber and the base pressure was set to 1 × 10 ^-6 torr, organic materials and metals were deposited on the ITO in the following structure.

device Example 1 to 38

The compound implemented according to the present invention was employed in the electron blocking layer to produce a blue organic light-emitting device having the following device structure, and then the light emission and driving characteristics of the compound implemented according to the present invention were measured.

ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (HT1, 100 nm) / electron blocking layer (10nm) / emission layer (20 nm) / electron transport layer (ET1:Liq, 30 nm) / LiF (1 nm) / Al (100 nm)

[HAT-CN] was deposited to a thickness of 5 nm on the top of the ITO transparent electrode to form a hole injection layer, and then [HT1] was deposited to a thickness of 100 nm to form a hole transport layer. Afterwards, the compound according to the present invention shown in [Table 1] below was deposited to a thickness of 10 nm to form an electron blocking layer, and the emitting layer was formed at a thickness of 20 nm using [BH1] as the host compound and [BD1] as the dopant compound. It was formed by vapor deposition. Afterwards, 30 nm of an electron transport layer (50% doped with [ET1] compound Liq below) was deposited, and then LiF was deposited to a thickness of 1 nm to form an electron injection layer. Afterwards, Al was deposited to a thickness of 100 nm to produce a blue organic light emitting device.

device Comparative example One

The organic light-emitting device for Comparative Device Example 1 was manufactured in the same manner as the device structures of Examples 1 to 38, except that [EB1] below was used in the electron blocking layer instead of the compound according to the present invention.

device Comparative example 2

The organic light emitting device for Device Comparative Example 2 was manufactured in the same manner as the device structures of Examples 1 to 38 except that [EB2] below was used instead of the compound according to the present invention in the electron blocking layer.

Experiment example 1: element Example Luminous properties from 1 to 38

The driving voltage, current efficiency, and color coordinates of the organic light emitting devices manufactured according to the above examples and comparative examples were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and were measured at 1,000 nit. The standard result values are shown in [Table 1] below.

Example electronic low layer V cd/A CIEx CIey One Formula 2 4.27 7.58 0.1336 0.1390 2 Formula 17 4.32 7.35 0.1344 0.1369 3 Formula 23 4.28 7.16 0.1337 0.1351 4 Formula 37 4.16 7.23 0.1329 0.1375 5 Formula 45 4.37 7.58 0.1329 0.1390 6 Formula 57 4.26 7.54 0.1348 0.1358 7 Formula 63 4.14 7.55 0.1325 0.1339 8 Formula 69 4.08 7.47 0.1350 0.1357 9 Formula 80 4.40 7.13 0.1342 0.1369 10 Formula 97 4.11 7.35 0.1342 0.1373 11 Formula 114 4.19 7.58 0.1354 0.1381 12 Formula 126 4.22 7.17 0.1337 0.1358 13 Formula 132 4.16 7.50 0.1350 0.1365 14 Formula 138 4.22 7.37 0.1337 0.1358 15 Formula 144 4.39 7.22 0.1351 0.1355 16 Formula 155 4.20 7.11 0.1359 0.1371 17 Formula 164 4.39 7.18 0.1338 0.1358 18 Formula 172 4.08 7.66 0.1358 0.1349 19 Formula 184 4.44 7.30 0.1334 0.1360 20 Formula 199 4.25 7.38 0.1361 0.1339 21 Formula 209 4.15 7.52 0.1355 0.1347 22 Formula 212 4.21 7.36 0.1333 0.1338 23 Formula 225 4.38 7.21 0.1358 0.1356 24 Formula 228 4.19 7.13 0.1348 0.1340 25 Formula 236 4.24 7.52 0.1326 0.1377 26 Formula 255 4.40 7.36 0.1322 0.1371 27 Formula 270 4.12 7.26 0.1345 0.1367 28 Formula 285 4.09 7.29 0.1326 0.1363 29 Formula 298 4.27 7.44 0.1336 0.1375 30 Formula 324 4.35 7.10 0.1333 0.1381 31 Formula 335 4.18 7.67 0.1355 0.1437 32 Formula 354 4.30 7.48 0.1334 0.1348 33 Chemical formula 360 4.26 7.43 0.1344 0.1326 34 Formula 378 4.24 7.41 0.1329 0.1375 35 Formula 393 4.42 7.41 0.1354 0.1370 36 Formula 397 4.27 7.19 0.1341 0.1358 37 Formula 413 4.13 7.32 0.1324 0.1360 38 Formula 438 4.24 7.43 0.1333 0.1371 Comparative Example 1 EB1 4.67 6.65 0.1353 0.1517 Comparative Example 2 EB2 4.54 6.68 0.1342 0.1387

Looking at the results shown in [Table 1], when the compound according to the present invention is employed in the electron blocking layer in an organic light-emitting device, the characteristic structure of the compound according to the present invention as a compound used as a conventional electron blocking layer material is compared with the characteristic structure of the compound according to the present invention. It can be seen that the luminous properties, such as low-voltage driving characteristics, luminous efficiency, and quantum efficiency, are significantly superior to those of devices employing the compound (Comparative Examples 1 and 2).

[HAT-CN] [HT1] [BH1] [BD1] [ET1]

[EB1] [EB2]

device Example (green EBL )

In an embodiment according to the present invention, the ITO transparent electrode is patterned so that the light emitting area is 2 mm × 2 mm using an ITO glass substrate to which the ITO transparent electrode is attached on a glass substrate of 25 mm × 25 mm × 0.7 mm. and then washed. After the substrate was mounted in a vacuum chamber and the base pressure was set to 1 × 10 ^-6 torr, organic materials and metals were deposited on the ITO in the following structure.

device Example 39 to 69

The compound implemented according to the present invention was employed in the electron blocking layer to produce a green organic light-emitting device having the following device structure, and then the light-emitting properties, including current efficiency, were measured.

ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (HT1, 100 nm) / electron blocking layer (EB1, 10 nm) / light emitting layer (1st host: 2nd host: Ir(ppy) ₃ , 30 nm) / electron transport layer (ET1, 30 nm) / LiF (1 nm) / Al (100 nm)

[HAT-CN] was deposited to a thickness of 5 nm on the top of the ITO transparent electrode to form a hole injection layer, and then [HT1] was deposited to a thickness of 100 nm to form a hole transport layer. Afterwards, the compound according to the present invention shown in [Table 2] below was deposited to a thickness of 10 nm to form an electron blocking layer, and the emitting layer consisted of [GH1] as the first host and [GH2] as the second host in a ratio of 6:4. A mixed host was used, and the dopant was doped with Ir(ppy) ₃ and co-deposited to a thickness of 30 nm. Additionally, a 30 nm electron transport layer (50% doped with [ET1] compound Liq below) was deposited. Then, LiF was deposited to a thickness of 1 nm as an electron injection layer, and then Al 100 nm was deposited to produce an organic light emitting device.

device Comparative example 3

The organic light emitting device for Device Comparative Example 3 was manufactured in the same manner as the device structures of Examples 39 to 69, except that [EB1] below was used instead of the compound according to the present invention in the electron blocking layer.

device Comparative example 4

The organic light emitting device for Device Comparative Example 4 was manufactured in the same manner as the device structures of Examples 39 to 69, except that [EB2] below was used in the electron blocking layer instead of the compound according to the present invention.

Experiment example 2: element Example Luminous properties of 39 to 69

The driving voltage, current efficiency, and color coordinates of the organic light emitting devices manufactured according to the above examples and comparative examples were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and were measured at 1,000 nit. The standard result values are shown in [Table 2] below.

Example electronic low layer V cd/A CIEx CIey 39 Formula 2 3.64 49.11 0.327 0.618 40 Formula 17 3.53 53.05 0.319 0.614 41 Formula 30 3.69 49.73 0.330 0.615 42 Formula 37 3.70 52.17 0.324 0.617 43 Formula 49 3.66 49.89 0.328 0.612 44 Formula 57 3.59 52.32 0.321 0.620 45 Formula 66 3.74 50.50 0.316 0.615 46 Formula 80 3.53 52.04 0.320 0.618 47 Formula 103 3.65 50.84 0.324 0.615 48 Formula 114 3.51 53.99 0.327 0.613 49 Formula 126 3.56 51.38 0.333 0.619 50 Formula 130 3.67 49.98 0.320 0.610 51 Formula 144 3.70 53.05 0.315 0.614 52 Formula 155 3.63 54.55 0.327 0.619 53 Formula 159 3.55 53.33 0.315 0.611 54 Formula 168 3.57 51.01 0.316 0.622 55 Formula 184 3.65 50.93 0.317 0.615 56 Formula 212 3.60 51.44 0.324 0.617 57 Formula 221 3.49 51.87 0.322 0.614 58 Formula 240 3.73 50.55 0.314 0.618 59 Formula 261 3.52 52.09 0.328 0.612 60 Formula 285 3.64 50.80 0.327 0.612 61 Formula 316 3.70 52.88 0.322 0.621 62 Formula 324 3.55 51.01 0.320 0.611 63 Chemical formula 350 3.64 51.08 0.326 0.615 64 Chemical formula 360 3.69 49.50 0.323 0.622 65 Formula 372 3.60 50.88 0.325 0.613 66 Formula 393 3.72 50.76 0.328 0.615 67 Formula 412 3.55 52.10 0.326 0.614 68 Formula 438 3.60 50.77 0.324 0.611 69 Formula 445 3.73 52.85 0.320 0.623 Comparative Example 3 EB1 4.11 45.29 0.326 0.602 Comparative Example 4 EB2 3.98 41.32 0.332 0.609

Looking at the results shown in [Table 2], when the compound according to the present invention is employed in the electron blocking layer in an organic light emitting device, the characteristic structure of the compound according to the present invention as a compound used as a conventional electron blocking layer material is compared with the characteristic structure of the compound according to the present invention. It can be seen that the light emitting properties, such as low voltage driving characteristics and current efficiency, are significantly superior to those of devices employing the compound (Comparative Examples 3 to 4).

[HAT-CN] [HT1] [ET1]

[GH1] [GH2] [Ir(ppy) ₃ ]

[EB1] [EB2]

Claims (12)

Carbazole derivative compounds represented by the following [Chemical Formula I]:
[Formula Ⅰ]

In the above [Chemical Formula I],
X is O or S,
R ₁ to R ₃ are each independently hydrogen or deuterium,
p and q are each an integer from 0 to 4, r is an integer from 0 to 3, and when p, q and r are 2 or more, a plurality of R ₁ to R ₃ are the same or different from each other,
Among the plurality of R ₂ and R ₃ , each one is connected to the '*',
R ₄ to R ₁₁ are the same or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group with 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group with 1 to 30 carbon atoms, and a substituted or unsubstituted carbon number. 3 to 20 cycloalkyl group, substituted or unsubstituted heterocycloalkyl group with 3 to 30 carbon atoms, substituted or unsubstituted aryl group with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group with 2 to 50 carbon atoms, substituted or Any one selected from an unsubstituted aliphatic aromatic mixed ring group having 3 to 50 carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted germanium group, a cyano group, and a halogen group,
At least one of R ₄ to R ₁₁ is characterized in that it is represented by the following [structural formula 1],
[Structural Formula 1]

In [Structural Formula 1] above,
Ar ₁ and Ar ₂ are the same or different from each other, are each independently the same as or different from each other, and are each independently a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 50 carbon atoms and a substituted or unsubstituted aromatic hetero ring having 2 to 50 carbon atoms It is one selected from among the rings. According to paragraph 1,
Any one selected from R ₄ , R ₆ and R ₇ ; and any one selected from R ₈ , R ₁₀ and R ₁₁ ; each of the above [Structural Formula 1]. According to paragraph 1,
A carbazole derivative compound, wherein any one selected from R ₄ , R ₆ and R ₇ is the [Structural Formula 1]. According to paragraph 1,
The [Formula I] is a carbazole derivative compound characterized in that it is represented by the following [Formula I-1] or [Formula I-2]:
[Formula Ⅰ-1] [Formula Ⅰ-2]

In the [Formula Ⅰ- ₁ ] and [Formula _Ⅰ -2], the definitions of Any one of R ₃ is a region connected to the '*'. According to paragraph 1,
In the definition of R ₁ to R ₁₁ , Ar ₁ and Ar ₂ in [Formula I], ‘substituted or unsubstituted’ means that R ₁ to R ₁₁ , Ar ₁ and Ar ₂ are respectively deuterium, cyano group, and halogen group. , hydroxy group, nitro group, alkyl group, halogenated alkyl group, alkoxy group, halogenated alkoxy group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, aliphatic aromatic mixed ring group, amine group, silyl group and germanium group. It means that it is substituted with 1 or 2 or more substituents, or is substituted with a substituent in which 2 or more of the substituents are connected, or does not have any substituent, and the hydrogen in the substituent can be replaced by one or more deuterium, and 2 or more adjacent substituents may be connected to each other to further form an alicyclic or aromatic monocyclic or polycyclic ring. According to paragraph 1,
[Formula I] is a carbazole derivative compound characterized in that R ₁ to R ₁₁ are partially substituted with deuterium (D), and the deuterium (D) substitution rate is 10 to 90%. According to clause 6,
A carbazole derivative compound characterized in that the deuterium (D) substitution rate is 20 to 80%. According to clause 6,
A carbazole derivative compound characterized in that the deuterium (D) substitution rate is 30 to 70%. According to paragraph 1,
[Formula I] is an organic compound selected from the following [Formula 1] to [Formula 447]:









































An organic light-emitting device comprising a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode,
An organic light-emitting device comprising a plurality of organic layers, wherein at least one layer among the plurality of organic layers includes at least one organic compound represented by [Chemical Formula I] according to claim 1. According to clause 10,
The organic layer includes one or more of an electron injection layer, an electron transport layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, and a light emitting layer,
An organic light-emitting device, wherein at least one of the layers includes an organic compound represented by the formula (I). According to clause 11,
An organic light-emitting device comprising an organic compound represented by [Chemical Formula I] in the electron blocking layer.