KR20240058220A - Organic compound and electroluminescent device comprising the same - Google Patents

Abstract

The present invention is an organic compound represented by the following [Chemical Formula I], and when it is employed in an organic layer, preferably an electron blocking layer, in an organic light-emitting device, an organic light-emitting device with excellent luminous properties such as luminous efficiency and quantum efficiency can be realized. possible.
[Formula Ⅰ]

Description

Organic compound and electroluminescent device comprising the same}

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

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.

However, in order for this organic light-emitting device to exhibit the above characteristics, the materials that make up the organic layer within the device, such as hole injection material, hole transport material, hole blocking material, light emitting material, electron transport material, electron injection material, and electron blocking material, are required. Support by stable and efficient materials must be a priority, but the development of stable and efficient organic layer materials for organic light-emitting devices has not yet been sufficiently developed.

Therefore, there is a continued need for the development of new materials that can improve luminescence characteristics and the development of organic layer structures within devices.

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 an organic compound represented by the following [Chemical Formula I] and an organic light-emitting device containing the same.

[Formula Ⅰ]

The specific structure of [Formula I], the specific compounds implemented thereby, and the definitions of R ₁ to R ₂ , X ₁ to X ₄ , and Ar ₁ to Ar ₃ will be described later.

The organic light-emitting device employing the organic compound according to the present invention in an organic layer such as an electron blocking layer is significantly superior to conventional devices in device characteristics such as low-voltage operation, long lifespan, and luminous efficiency, and can be usefully used in various lighting devices and display devices. You can.

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

The present invention relates to a novel organic compound capable of implementing 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].

[Formula Ⅰ]

In the above [Chemical Formula I],

Ar ₁ to Ar ₃ are the same or different from each other and are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

X ₁ to X ₄ are the same or different from each other and are each independently CR or N, and R is hydrogen or deuterium.

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

The compound represented by [Formula I] according to the present invention is structurally characterized in that it contains a nitrogen (N)-containing heteroaryl group in the [Formula I] structure.

Accordingly _, at least one _of X _{1 to} , the remainder may be CR (R is hydrogen or deuterium).

In addition _{, according to} this _, when all of X _{1 to} It is characterized by containing an aryl group.

According to one embodiment of the present invention, when all of X ₁ to X ₄ are CR (R is hydrogen or deuterium), at least one of Ar ₁ to Ar ₃ is pyridine in the structure of Ar ₁ to Ar ₃ It is characterized by including a diary.

Meanwhile, in the definition of Ar ₁ to Ar ₃ , substituted or unsubstituted means that Ar ₁ to Ar ₃ are each selected from the group consisting of deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, halogenated alkyl group, and halogenated alkoxy group. is substituted with one or two or more substituents selected from a group, cycloalkyl group, heterocycloalkyl group, aryl group, fluorenyl group, heteroaryl group, silyl group and amine group, or is substituted with a substituent in which two or more substituents of the above substituents are connected, or It means not having any substituents.

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 the present invention, examples of the above substituents will be described in detail below, but are not limited thereto.

In the present invention, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 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, 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 aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 30. It also includes a polycyclic aryl group structure fused with cycloalkyl, etc., and the monocyclic aryl group Examples of phenyl group, biphenyl group, terphenyl group, stilbene group, etc. Examples of polycyclic aryl groups include naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, tetracenyl group, and chrysenyl group. , fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthrene 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 heteroaryl group is a heterocyclic group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, and is a polycyclic group fused with cycloalkyl or heterocycloalkyl, etc. It contains a heteroaryl group structure, and specific examples thereof in the present invention include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, and 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, 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, phenothiazinyl group, phenoxazine group, phenothiazine group, etc., but only these It is not limited.

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. 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.

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

In the present invention, cycloalkyl groups refer to and include monocyclic, polycyclic and spiro alkyl radicals, and preferably contain ring carbon atoms having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, and bicyclo. Includes heptyl, spirodecyl, spiroundecyl, adamantyl, etc., and the cycloalkyl group may be optionally substituted.

In the present invention, heterocycloalkyl groups refer to and include aromatic and non-aromatic cyclic radicals containing one or more heteroatoms, wherein one or more heteroatoms are O, S, N, P, B, Si and Se, It is preferably selected from O, N or S, and specifically, when it contains N, it may be aziridine, pyrrolidine, piperidine, azepane, azocan, etc.

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.

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 and is formed using a solvent process rather than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, to form a smaller number of layers. 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 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 15

(One) Manufacturing example 1: Synthesis of intermediate 15-1

(9-Phenyl-9H-carbazol-4-yl)boronic acid (10.0 g, 0.035 mol), 2,5-dichloropyridine (6.2 g, 0.042 mol), K ₂ CO ₃ (14.4 g, 0.105 mol), Pd ( To PPh ₃ ) ₄ (0.8 g, 0.7 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, it was extracted, concentrated, and recrystallized with a column to obtain 7.6 g of <Intermediate 15-1> (yield 61.5%).

(2) Manufacturing example 2: Synthesis of Compound 15

Intermediate 15-1 (10.0 g, 0.028 mol), Bis(9,9-dimethyl-9H-fluoren-7-yl)amine (17.0 g, 0.042 mol), NaOtBu (8.1 g, 0.085 mol), Pd(dba) ₂ (0.7 g, 1.1 mmol) and t-Bu ₃ P (0.5 g, 2.3 mmol) were mixed with 150 mL of xylene and stirred at 120°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 13.8 g of <Compound 15> (yield 68.0%).

LC/MS: m/z=719[(M) ⁺ ]

Synthesis example 2: Synthesis of Compound 34

(One) Manufacturing example 1: Synthesis of intermediate 34-1

3-Aminodibenzofuran (10.0 g, 0.055 mol), 2-Bromo-9,9'-spirobi[fluorene] (32.4 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 17.5 g of <Intermediate 34-1> (yield 64.4%).

(2) Manufacturing example 2: Synthesis of Compound 34

Intermediate 15-1 (10.0 g, 0.028 mol), Intermediate 34-1 (21.1 g, 0.042 mol), NaOtBu (8.1 g, 0.085 mol), Pd(dba) ₂ (0.7 g, 1.1 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.5 g, 2.3 mmol) and stirred at 120°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 16.2 g of <Compound 34> (yield 70.3%).

LC/MS: m/z=815[(M) ⁺ ]

Synthesis example 3: Synthesis of Compound 56

(One) Manufacturing example 1: Synthesis of intermediate 56-1

Bis-biphenyl-4-yl-amine (10.0 g, 0.031 mol), 2,5-dichloropyridine (6.9 g, 0.047 mol), NaOtBu (9.0 g, 0.093 mol), Pd(dba) ₂ (0.7 g, 1.2 mmol) ), 150 mL of Xylene was added to t-Bu ₃ P (0.5 g, 2.5 mmol) and stirred at 70°C for 4 hours to react. After completion of the reaction, it was extracted, concentrated, and recrystallized with a column to obtain 8.2 g of <Intermediate 56-1> (yield 60.9%).

(2) Manufacturing example 2: Synthesis of Compound 56

(9-Phenyl-9H-carbazol-4-yl)boronic acid (10.0 g, 0.035 mol), intermediate 56-1 (18.1 g, 0.042 mol), K ₂ CO ₃ (14.4 g, 0.105 mol), Pd(OAc _{) 2} (2.0 g, 1.7 mmol), After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 13.0 g of <Compound 56> (yield 58.3%).

LC/MS: m/z=639[(M) ⁺ ]

Synthesis example 4: Synthesis of Compound 95

(One) Manufacturing example 1: Synthesis of intermediate 95-1

3-Aminodibenzofuran (10.0 g, 0.055 mol), 5'-Bromo-1,1':3',1"-terphenyl (25.3 g, 0.082 mol), NaOtBu (15.7 g, 0.164 mol), Pd(dba) ₂ (1.3 g, 2.2 mmol) and t-Bu ₃ P (0.9 g, 4.4 mmol) were mixed with 150 mL of 14.1 g (yield 62.8%) of 95-1> was obtained.

(2) Manufacturing example 2: Synthesis of intermediate 95-2

Intermediate 95-1 (10.0 g, 0.024 mol), 2,5-dichloropyridine (5.4 g, 0.037 mol), NaOtBu (7.0 g, 0.073 mol), Pd(dba) ₂ (0.6 g, 1.0 mmol), t-Bu ₃ Add 150 mL of Xylene to P (0.4 g, 1.9 mmol) and stir at 120°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 8.6 g of <Intermediate 95-2> (yield 67.7%).

(3) Manufacturing example 3: Synthesis of Compound 95

(9-Phenyl-9H-carbazol-4-yl)boronic acid (10.0 g, 0.035 mol), intermediate 95-2 (21.9 g, 0.042 mol), K ₂ CO ₃ (14.4 g, 0.105 mol), Pd(OAc _{) 2} (2.0 g, 1.7 mmol), After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 14.9 g of <Compound 95> (yield 58.6%).

LC/MS: m/z=729[(M) ⁺ ]

Synthesis example 5: Synthesis of Compound 115

(One) Manufacturing example 1: Synthesis of intermediate 115-1

4-Aminobiphenyl (10.0 g, 0.059 mol), 2-Chloro-5-phenylpyridine (16.8 g, 0.089 mol), NaOtBu (17.0 g, 0.177 mol), Pd(dba) ₂ (1.4 g, 2.4 mmol), t- 150 mL of Xylene was added to Bu ₃ P (1.0 g, 4.7 mmol) and stirred at 120°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 14.4 g of <Intermediate 115-1> (yield 75.6%).

(2) Manufacturing example 2: Synthesis of Compound 115

4-(4-Chlorophenyl)-9-phenyl-9H-carbazole (10.0 g, 0.028 mol), intermediate 115-1 (13.7 g, 0.042 mol), NaOtBu (8.2 g, 0.085 mol), Pd(dba) ₂ ( 0.7 g, 1.1 mmol) and t-Bu ₃ P (0.5 g, 2.3 mmol) were added with 150 mL of Xylene and stirred at 120°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 12.4 g of <Compound 115> (yield 68.6%).

LC/MS: m/z=639[(M) ⁺ ]

Synthesis example 6: Synthesis of Compound 153

(One) Manufacturing example 1: Synthesis of intermediate 153-1

3-Aminodibenzofuran (10.0 g, 0.055 mol), 4-Bromo-2,6-diphenylpyridine (25.4 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 then recrystallized with a column to obtain 14.7 g of <Intermediate 153-1> (yield 65.3%).

(2) Manufacturing example 2: Synthesis of Compound 153

4-(4-Chlorophenyl)-9-phenyl-9H-carbazole (10.0 g, 0.028 mol), intermediate 153-1 (17.5 g, 0.042 mol), NaOtBu (8.2 g, 0.085 mol), Pd(dba) ₂ ( 0.7 g, 1.1 mmol) and t-Bu ₃ P (0.5 g, 2.3 mmol) were added with 150 mL of Xylene and stirred at 120°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 13.8 g of <Compound 153> (yield 66.9%).

LC/MS: m/z=729[(M) ⁺ ]

Synthesis example 7: Synthesis of Compound 156

(One) Manufacturing example 1: Synthesis of intermediate 156-1

3-Aminodibenzofuran (10.0 g, 0.055 mol), 2,2'-(5-Bromo-1,3-phenylene)dipyridine (25.5 g, 0.082 mol), NaOtBu (15.7 g, 0.164 mol), Pd(dba) ₂ (1.3 g, 2.2 mmol) and t-Bu ₃ P (0.9 g, 4.4 mmol) were added 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 14.1 g of <Intermediate 156-1> (yield 62.5%).

(2) Manufacturing example 2: Synthesis of Compound 156

4-(4-Chlorophenyl)-9-phenyl-9H-carbazole (10.0 g, 0.028 mol), intermediate 156-1 (17.5 g, 0.042 mol), NaOtBu (8.2 g, 0.085 mol), Pd(dba) ₂ ( 0.7 g, 1.1 mmol) and t-Bu ₃ P (0.5 g, 2.3 mmol) were added with 150 mL of Xylene and stirred at 120°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 13.6 g of <Compound 156> (yield 65.8%).

LC/MS: m/z=730[(M) ⁺ ]

Synthesis example 8: Synthesis of compound 227

(One) Manufacturing example 1: Synthesis of intermediate 227-1

Add 500 mL of DMF to 4-Bromo-9H-carbazole (10.0 g, 0.041 mol), 3-Fluoropyridine (4.7 g, 0.049 mol), and Cs ₂ CO ₃ (8.4 g, 0.061 mol) and reflux at 150°C for 12 hours. The reaction was stirred. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.3 g (yield 63.2%) of <Intermediate 227-1>.

(2) Manufacturing example 2: Synthesis of intermediate 227-2

Intermediate 227-1 (10.0 g, 0.031 mol), (4-Chlorophenyl)boronic acid (5.8 g, 0.037 mol), K ₂ CO ₃ (12.8 g, 0.093 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.6 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 recrystallized with a column to obtain 6.6 g of <Intermediate 227-2> (yield 60.1%).

(3) Manufacturing example 3: Synthesis of Compound 227

Intermediate 227-2 (10.0 g, 0.028 mol), 9,9-dimethyl-N-(4-phenylphenyl)fluoren-2-amine (15.3 g, 0.042 mol), NaOtBu (8.1 g, 0.085 mol), Pd(dba ) ₂ (0.7 g, 1.1 mmol) and t-Bu ₃ P (0.5 g, 2.3 mmol) were mixed with 150 mL of Xylene and stirred at 120°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 13.5 g of <Compound 227> (yield 70.3%).

LC/MS: m/z=679[(M) ⁺ ]

device Example ( 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 43

The compound implemented according to the present invention was employed in the electron blocking layer to manufacture an 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 (α-NPB, 100 nm) / electron blocking layer (10 nm) / emitting layer (20 nm) / electron transport layer (ET1:Liq, 30 nm) / LiF (1 nm) / Al (100 nm)

[HAT-CN] was deposited on the top of the ITO transparent electrode to a thickness of 5 nm to form a hole injection layer, and then α-NPB was deposited to a thickness of 100 nm to form a hole transport layer. According to the present invention described in [Table 1] below, The following compound was deposited to a thickness of 10 nm to form an electron blocking layer, and the light emitting layer was formed by co-depositing to a thickness of 20 nm using [BH1] as a host compound and [BD1] as a dopant compound. 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, an organic light emitting device was manufactured by forming Al into a 100 nm thick film.

device Comparative example One

The organic light emitting device for Device Comparative Example 1 was manufactured in the same manner as the device structures of Examples 1 to 43, except that [EB1] below was used instead of the compound according to the present invention in the electron blocking layer.

device Comparative example 2

The organic light emitting device for Comparative Device Example 2 was manufactured in the same manner as the device structures of Examples 1 to 43, except that [EB2] below was used instead of the compound according to the present invention in the electron blocking layer.

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 1 to 43, except that [EB3] below was used in the electron blocking layer instead of the compound according to the present invention.

Experiment example 1: element Example Luminous properties from 1 to 43

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 4 4.35 7.60 0.1331 0.1384 2 Formula 8 4.08 7.41 0.1344 0.1362 3 Formula 11 4.00 7.36 0.1350 0.1396 4 Formula 15 4.33 7.28 0.1342 0.1353 5 Formula 18 4.33 7.28 0.1342 0.1353 6 Formula 25 4.20 7.57 0.1327 0.1393 7 Formula 31 4.17 7.35 0.1344 0.1349 8 Formula 34 4.38 7.54 0.1347 0.1342 9 Formula 38 4.24 7.48 0.1325 0.1354 10 Formula 53 4.15 7.55 0.1319 0.1366 11 Formula 56 4.19 7.37 0.1324 0.1378 12 Formula 58 4.03 7.34 0.1333 0.1362 13 Formula 71 4.40 7.43 0.1325 0.1384 14 Formula 77 3.99 7.50 0.1348 0.1368 15 Formula 84 4.33 7.61 0.1350 0.1387 16 Formula 95 4.21 7.64 0.1334 0.1368 17 Formula 102 3.95 7.36 0.1341 0.1355 18 Formula 115 4.28 7.44 0.1348 0.1354 19 Formula 118 4.28 7.44 0.1348 0.1354 20 Formula 123 4.08 7.29 0.1344 0.1363 21 Formula 128 4.14 7.34 0.1326 0.1370 22 Formula 139 3.97 7.28 0.1342 0.1356 23 Formula 153 4.18 7.51 0.1326 0.1377 24 Formula 156 4.44 7.22 0.1327 0.1370 25 Formula 165 4.41 7.37 0.1344 0.1348 26 Formula 181 4.27 7.56 0.1351 0.1376 27 Formula 194 4.21 7.40 0.1353 0.1354 28 Formula 198 4.33 7.37 0.1312 0.1391 29 Formula 199 4.26 7.50 0.1313 0.1395 30 Formula 218 4.04 7.34 0.1322 0.1384 31 Formula 227 4.15 7.60 0.1320 0.1386 32 Formula 231 4.38 7.49 0.1336 0.1367 33 Formula 234 4.12 7.28 0.1338 0.1366 34 Formula 247 4.33 7.44 0.1342 0.1359 35 Formula 252 4.25 7.57 0.1328 0.1396 36 Formula 257 4.18 7.30 0.1338 0.1389 37 Formula 260 4.30 7.51 0.1324 0.1399 38 Formula 262 4.19 7.60 0.1349 0.1391 39 Formula 266 3.91 7.77 0.1336 0.1364 40 Formula 269 3.99 7.41 0.1337 0.1364 41 Formula 272 4.17 7.61 0.1333 0.1389 42 Formula 281 4.08 7.45 0.1343 0.1362 43 Formula 290 4.22 7.32 0.1311 0.1390 Comparative Example 1 EB1 4.67 6.65 0.1353 0.1517 Comparative Example 2 EB2 4.79 6.83 0.1349 0.1392 Comparative Example 3 EB3 4.53 6.94 0.1344 0.1378

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 to 3).

[HAT-CN] [α-NPB] [BH1] [BD1] [ET1]

[EB1] [EB2] [EB3]

Claims (8)

Organic compounds represented by the following [Chemical Formula I]:
[Formula Ⅰ]

In the above [Chemical Formula I],
Ar ₁ to Ar ₃ are the same or different from each other and are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms,
X ₁ to X ₄ are the same or different from each other and are each independently CR (R is hydrogen or deuterium) or N,
R ₁ and R ₂ are each independently hydrogen or deuterium, m is an integer from 0 to 4, n is an integer from 0 to 3, and when m and n are each 2 or more, a plurality of R ₁ and R ₂ are each are the same or different from each other,
_{However ,} when all _{of X 1 to} do. According to paragraph 1,
An organic compound wherein at least one of X ₁ to X ₄ is N, and the remainder is CR (R is hydrogen or deuterium). According to paragraph 1,
_{When all of X 1 to} compound. According to paragraph 1,
In the definition of Ar ₁ to Ar ₃ , substituted or unsubstituted means that Ar ₁ to Ar ₃ are respectively deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, halogenated alkyl group, halogenated alkoxy group, It is substituted with one or two or more substituents selected from a cycloalkyl group, heterocycloalkyl group, aryl group, fluorenyl group, heteroaryl group, silyl group and amine group, or is substituted with a substituent in which two or more of the substituents are connected, or any substituent. An organic compound meaning that it does not have any. According to paragraph 1,
[Formula I] is an organic compound selected from the following [Formula 1] to [Formula 293]:
































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, wherein at least one of the organic layers includes at least one organic compound represented by [Chemical Formula I] according to claim 1. According to clause 6,
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). In clause 7,
An organic light-emitting device comprising an organic compound represented by [Chemical Formula I] in the electron blocking layer.