WO2024076117A1 - Organic compound and organic light-emitting element comprising same - Google Patents

Abstract

The present invention is an organic compound used in an organic layer provided in an organic light-emitting element. In particular, when the organic compound is used in an electron blocking layer of an organic light-emitting element, it is possible to achieve an organic light-emitting element that can be driven at a lower voltage than existing elements and has significantly improved element characteristics such as long lifespan characteristics and luminous efficiency, and thus the organic compound can be effectively used commercially in lighting elements as well various display elements such as flat panel, flexible, wearable, and virtual or augmented reality displays.

Description

Organic compounds and organic light-emitting devices containing them

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 should 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 [Chemical Formula I], the specific compounds implemented thereby, and the definitions of R ₁ to R ₅ , X, L, and Ar ₁ to Ar ₄ 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 an organic compound represented by the following [Chemical Formula I], which structurally (i) contains specific positions (positions 4 and 6) of the dibenzofuran (thiophene) or fluorene structure, that is, Ar ₁ and Ar It is characterized by introducing an aryl group at position ₂ , and (ii) by introducing an aryl (heteroaryl)amine group at position 2 by directly bonding it without an additional linking group.

Due to these structural features, it is possible to implement an organic light-emitting device with significantly improved device characteristics such as low-voltage driving, long life, and luminous efficiency when used in various organic layers in the organic light-emitting device, preferably in the electron blocking layer.

[Formula Ⅰ]

In the above [Chemical Formula I],

Ar ₁ and Ar ₂ are the same or different from each other and are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

R ₁ to R ₅ are the same as or different from each other and are each independently hydrogen or deuterium.

X is O, S or CR ₆ R ₇ , the R ₆ and R ₇ are the same or different with each other, respectively, independently of hydrogen, heavy hydrogen, cyano group, halogen group, alkyl groups of 1 to 20 carbon ate or shifted or beached. or an unsubstituted cycloalkyl group having 3 to 20 carbon atoms, 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.

In addition, R ₆ and R ₇ may be connected to each other to further form an alicyclic or aromatic monocyclic or polycyclic ring.

L is a divalent linking group, which is a single bond or one selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, and n is an integer of 0 to 3. And when n is 2 or more, the plurality of Ls are the same or different from each other.

Ar ₃ and Ar ₄ 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.

Meanwhile, in the definition of R ₆ , R ₇ , L and Ar ₁ to Ar ₄ , substituted or unsubstituted means that R ₆ , R ₇ , L and Ar ₁ to Ar ₄ are each a deuterium group, a cyano group, a halogen group, or a hydroxy group. , nitro group, alkyl group, alkoxy group, halogenated alkoxy group, cycloalkyl group, heterocycloalkyl group, aryl group, fluorenyl group, heteroaryl group, silyl group and amine group, or the above substituents It means that two or more substituents are substituted with a linked substituent, or do not have 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 addition, according to one embodiment of the present invention, the compound represented by [Formula I] according to the present invention may contain at least one or more deuterium in [Formula I], and accordingly, any one or more of R ₁ to R ₇ This may be deuterium, and R ₆ , R ₇ , L and Ar ₁ to Ar ₄ defined above may have one or more deuterium as an additional substituent.

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, fluorene in a fluorenyl group or fluorene moiety is a structure in which two ring organic compounds are connected through one atom, for example

,

,

etc.

In addition, it includes an open fluorene structure, where open fluorene is a structure in which one ring compound is disconnected from a structure in which 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 linked 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, benzoxazole 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. It 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 the 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 properties 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 receive holes from the anode at a low voltage, and 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 rear 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 1

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

4-bromo-6-phenyldibenzo[b,d]furan (10.0 g, 0.031 mol), Phenylboronic acid (4.5 g, 0.037 mol), K ₂ CO ₃ (12.8 g, 0.093 mol), Pd(PPh ₃ ) ₄ ( 0.7 g, 0.0006 mol), 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 7.4 g (yield 74.7%) of <Intermediate 1-1>.

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

Intermediate 1-1 (10.0 g, 0.031 mol) was dissolved in 100 mL of CHCl ₃ , and then bromine (in CHCl ₃ , 12.5 g, 0.078 mol) was slowly added dropwise and stirred at room temperature for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 5.2 g of <Intermediate 1-2> (yield 41.7%).

(3) Manufacturing example 3: Synthesis of Compound 1

Intermediate 1-2 (10.0 g, 0.025 mol), Bis(4-biphenylyl)amine (12.1 g, 0.038 mol), NaOtBu (7.2 g, 0.075 mol), Pd(dba) ₂ (0.6 g, 1.0 mmol), t 150 mL of Xylene was added to -Bu ₃ P (0.4 g, 2.0 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 1> (yield 72.4%).

LC/MS: m/z=639[(M) ⁺ ]

Synthesis example 2: Synthesis of Compound 32

(One) Manufacturing example 1: Synthesis of intermediate 32-1

2-Aminobiphenyl (10.0 g, 0.059 mol), 4-Bromo-9,9'-spirobi[9H-fluorene] (35.0 g, 0.089 mol), NaOtBu (17.0 g, 0.177 mol), Pd(dba) ₂ (1.4 g, 2.4 mmol), 150 mL of xylene was added to t-Bu ₃ P (1.0 g, 4.7 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 13.3 g of <Intermediate 32-1> (yield 46.5%).

(2) Manufacturing example 2: Synthesis of Compound 32

Intermediate 1-2 (10.0 g, 0.025 mol), Intermediate 32-1 (18.2 g, 0.038 mol), NaOtBu (7.2 g, 0.075 mol), Pd(dba) ₂ (0.6 g, 1.0 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.4 g, 2.0 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 11.8 g of <Compound 32> (yield 58.8%).

LC/MS: m/z=801[(M) ⁺ ]

Synthesis example 3: Synthesis of Compound 60

(One) Manufacturing example 1: Synthesis of intermediate 60-1

9,9'-Spirobi[9H-fluoren]-4-amine (10.0 g, 0.030 mol), 4'-Bromo-1,1'-biphenyl-2,2',3,3',4,5,5 150 mL of Xylene was added to ',6,6'-d9 (0.7 g, 1.2 mmol) and 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 7.9 g of <Intermediate 60-1> (yield 53.1%).

(2) Manufacturing example 2: Synthesis of Compound 60

Intermediate 1-2 (10.0 g, 0.025 mol), Intermediate 60-1 (18.5 g, 0.038 mol), NaOtBu (7.2 g, 0.075 mol), Pd(dba) ₂ (0.6 g, 1.0 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.4 g, 2.0 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 8.1 g of <Compound 60> (yield 39.9%).

LC/MS: m/z=810[(M) ⁺ ]

Synthesis example 4: Synthesis of Compound 84

(One) Manufacturing example 1: Synthesis of intermediate 84-1

3-Aminodibenzofuran (10.0 g, 0.055 mol), 2-(4-Bromophenyl)-9,9-dimethyl-9H-fluorene (28.6 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 recrystallized using a column to obtain 11.4 g of <Intermediate 84-1> (yield 46.3%).

(2) Manufacturing example 2: Synthesis of Compound 84

Intermediate 1-2 (10.0 g, 0.025 mol), Intermediate 84-1 (17.0 g, 0.038 mol), NaOtBu (7.2 g, 0.075 mol), Pd(dba) ₂ (0.6 g, 1.0 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.4 g, 2.0 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 14.6 g of <Compound 84> (yield 75.7%).

LC/MS: m/z=769[(M) ⁺ ]

Synthesis example 5: Synthesis of Compound 141

(One) Manufacturing example 1: Synthesis of intermediate 141-1

9,9'-Spirobi[fluoren]-4-ylboronic acid (10.0 g, 0.028 mol), 1-Bromo-4-chlorobenzene (6.4 g, 0.033 mol), K ₂ CO ₃ (11.5 g, 0.083 mol), Pd (PPh ₃ ) ₄ (0.6 g, 0.0006 mol) was added with 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.1 g (yield 68.3%) of <Intermediate 141-1>.

(2) Manufacturing example 2: Synthesis of intermediate 141-2

2-Aminobiphenyl (10.0 g, 0.059 mol), intermediate 141-1 (37.8 g, 0.089 mol), NaOtBu (17.0 g, 0.177 mol), Pd(dba) ₂ (1.4 g, 2.4 mmol), t-Bu ₃ P (1.0 g, 4.7 mmol) was added with 150 mL of xylene and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 15.2 g of <Intermediate 141-2> (yield 42.9%).

(3) Manufacturing example 3: Synthesis of Compound 141

Intermediate 1-2 (10.0 g, 0.025 mol), Intermediate 141-2 (21.0 g, 0.038 mol), NaOtBu (7.2 g, 0.075 mol), Pd(dba) ₂ (0.6 g, 1.0 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.4 g, 2.0 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 <Compound 141> (yield 66.8%).

LC/MS: m/z=877[(M) ⁺ ]

Synthesis example 6: Synthesis of Compound 143

(One) Manufacturing example 1: Synthesis of intermediate 143-1

[1,1':3',1"-Terphenyl]-5'-amine (10.0 g, 0.041 mol), intermediate 141-1 (26.1 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 and recrystallized to obtain 14.9 g (57.5% yield) of <Intermediate 143-1>.

(2) Manufacturing example 2: Synthesis of Compound 143

Intermediate 1-2 (10.0 g, 0.025 mol), Intermediate 143-1 (23.9 g, 0.038 mol), NaOtBu (7.2 g, 0.075 mol), Pd(dba) ₂ (0.6 g, 1.0 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.4 g, 2.0 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 15.1 g of <Compound 143> (yield 63.2%).

LC/MS: m/z=954[(M) ⁺ ]

Synthesis example 7: Synthesis of Compound 182

(One) Manufacturing example 1: Synthesis of Compound 182

Intermediate 1-2 (10.0 g, 0.025 mol), N-[4-(4-Dibenzofuranyl)phenyl][1,1'-biphenyl]-4-amine (15.5 g, 0.038 mol), NaOtBu (7.2 g, 0.075 mol), Pd(dba) ₂ (0.6 g, 1.0 mmol), and t-Bu ₃ P (0.4 g, 2.0 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 12.1 g of <Compound 182> (yield 66.2%).

LC/MS: m/z=729[(M) ⁺ ]

Synthesis example 8: Synthesis of Compound 229

(One) Manufacturing example 1: Synthesis of intermediate 229-1

4-bromo-6-phenyldibenzo[b,d]furan (10.0 g, 0.031 mol), 2-Biphenylboronic acid (7.4 g, 0.037 mol), K ₂ CO ₃ (12.8 g, 0.093 mol), Pd(PPh ₃ ) 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to ₄ (0.7 g, 0.0006 mol) and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 9.3 g (yield 75.8%) of <Intermediate 229-1>.

(2) Manufacturing example 2: Synthesis of intermediate 229-2

Intermediate 229-1 (10.0 g, 0.025 mol) was dissolved in 100 mL of CHCl ₃ , and then bromine (in CHCl ₃ , 10.1 g, 0.063 mol) was slowly added dropwise and stirred at room temperature for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 4.6 g (yield 38.4%) of <Intermediate 229-2>.

(3) Manufacturing example 3: Synthesis of Compound 229

Intermediate 229-2 (10.0 g, 0.021 mol), Bis(4-biphenylyl)amine (10.1 g, 0.032 mol), NaOtBu (6.1 g, 0.063 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), t 150 mL of Xylene was added to -Bu ₃ P (0.3 g, 1.7 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 11.2 g of <Compound 229> (yield 74.4%).

LC/MS: m/z=715[(M) ⁺ ]

Synthesis example 9: Synthesis of Compound 265

(One) Manufacturing example 1: Synthesis of intermediate 265-1

4,6-dibromodibenzothiophene (10.0 g, 0.029 mol), Phenylboronic acid (8.6 g, 0.070 mol), K ₂ CO ₃ (24.2 g, 0.175 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.6 mmol) toluene 200 mL, 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 7.8 g (yield 79.3%) of <Intermediate 265-1>.

(2) Manufacturing example 2: Synthesis of intermediate 265-2

Intermediate 265-1 was dissolved in 100 mL of CHCl ₃ , and bromine (in CHCl ₃ , 11.9 g, 0.074 mol) was slowly added dropwise and stirred at room temperature for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 4.9 g of <Intermediate 265-2> (yield 36.7%).

(3) Manufacturing example 3: Synthesis of Compound 265

Intermediate 265-2 (10.0 g, 0.024 mol), N-[1,1'-Biphenyl]-4-yl-9,9-diphenyl-9H-fluoren-3-amine (17.5 g, 0.036 mol), NaOtBu ( 6.9 g, 0.072 mol), Pd(dba) ₂ (0.6 g, 1.0 mmol), and t-Bu ₃ P (0.4 g, 1.9 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 12.8 g of <Compound 265> (yield 64.8%).

LC/MS: m/z=819[(M) ⁺ ]

Synthesis example 10: Synthesis of Compound 276

(One) Manufacturing example 1: Synthesis of intermediate 276-1

dibenzo[b,d]furan-3-amine (10.0 g, 0.055 mol), 4-Bromo-9,9'-spirobi[9H-fluorene] (32.4 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 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 13.1 g of <Intermediate 276-1> (yield 48.2%).

(2) Manufacturing example 2: Synthesis of Compound 276

Intermediate 265-2 (10.0 g, 0.024 mol), Intermediate 276-1 (18.0 g, 0.036 mol), NaOtBu (6.9 g, 0.072 mol), Pd(dba) ₂ (0.6 g, 1.0 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.4 g, 1.9 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 12.2 g of <Compound 276> (yield 61.0%).

LC/MS: m/z=831[(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 48

After manufacturing an organic light emitting device having the following device structure by employing the compound implemented according to the present invention in an electron blocking layer, the light emitted by the compound implemented according to the present invention and the organic light emitting device containing the same in the electron blocking layer and driving characteristics were measured.

ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (HT1, 100 nm) / electron blocking layer (10 nm) / 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, an organic light-emitting device was manufactured by forming an Al film to a thickness of 100 nm.

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 48 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 Device Comparative Example 2 was manufactured in the same manner as the device structures of Examples 1 to 48 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 Comparative Device Example 3 was manufactured in the same manner as the device structures of Examples 1 to 48, except that [EB3] below was used in the electron blocking layer instead of the compound according to the present invention.

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 1 to 48 except that [EB4] below was used instead of the compound according to the present invention in the electron blocking layer.

device Comparative example 5

The organic light-emitting device for Comparative Device Example 5 was manufactured in the same manner as the device structures of Examples 1 to 48, except that [EB5] 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 48

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 1	4.31	7.33	0.1361	0.1329
2	Formula 5	4.22	7.40	0.1343	0.1347
3	Formula 7	4.17	7.47	0.1342	0.1367
4	Formula 15	4.28	7.63	0.1341	0.1332
5	Formula 18	4.18	7.51	0.1397	0.1335
6	Formula 19	4.15	7.61	0.1388	0.1328
7	Formula 20	4.28	7.81	0.1332	0.1364
8	Formula 22	4.31	7.42	0.1316	0.1391
9	Formula 23	4.12	7.75	0.1327	0.1342
10	Formula 24	4.24	7.61	0.1334	0.1351
11	Formula 25	4.22	7.71	0.1344	0.1361
12	Formula 28	4.26	7.65	0.1329	0.1391
13	Formula 32	4.09	7.82	0.1387	0.1329
14	Formula 40	4.31	7.58	0.1354	0.1346
15	Formula 53	4.31	7.33	0.1361	0.1329
16	Formula 56	4.18	7.56	0.1358	0.1364
17	Formula 60	4.07	7.78	0.1365	0.1349
18	Formula 73	4.23	7.64	0.1342	0.1313
19	Formula 84	4.18	7.66	0.1324	0.1398
20	Formula 96	4.21	7.68	0.1378	0.1329
21	Formula 107	4.27	7.72	0.1369	0.1337
22	Formula 120	4.33	7.53	0.1354	0.1352
23	Formula 124	4.29	7.42	0.1362	0.1345
24	Formula 141	4.15	7.61	0.1388	0.1328
25	Formula 143	4.31	7.58	0.1374	0.1348
26	Formula 149	4.15	7.61	0.1388	0.1328
27	Formula 165	4.07	7.79	0.1378	0.1327
28	Formula 171	4.19	7.66	0.1364	0.1351
29	Formula 177	4.23	7.52	0.1345	0.1366
30	Formula 182	4.26	7.44	0.1338	0.1378
31	Formula 192	4.22	7.65	0.1389	0.1335
32	Chemical formula 220	4.34	7.51	0.1344	0.1381
33	Formula 229	4.23	7.68	0.1336	0.1385
34	Formula 231	4.19	7.65	0.1345	0.1367
35	Formula 252	4.25	7.49	0.1372	0.1337
36	Formula 256	4.38	7.54	0.1393	0.1316
37	Formula 265	4.26	7.62	0.1350	0.1342
38	Formula 270	4.11	7.89	0.1353	0.1372
39	Formula 271	4.28	7.81	0.1332	0.1364
40	Formula 285	4.33	7.62	0.1353	0.1357
41	Chemical formula 303	4.25	7.80	0.1358	0.1432
42	Formula 316	4.29	7.62	0.1341	0.1318
43	Formula 325	4.30	7.81	0.1343	0.1362
44	Formula 336	4.24	7.64	0.1336	0.1332
45	Formula 345	4.31	7.46	0.1317	0.1394
46	Formula 363	4.23	7.81	0.1344	0.1353
47	Chemical formula 409	4.14	7.85	0.1380	0.1316
48	Formula 411	4.24	7.63	0.1393	0.1325
Comparative Example 1	EB1	4.67	6.65	0.1353	0.1517
Comparative Example 2	EB2	4.56	6.94	0.1345	0.1458
Comparative Example 3	EB3	4.63	6.79	0.1343	0.1485
Comparative Example 4	EB4	4.60	6.85	0.1338	0.1442
Comparative Example 5	EB5	4.53	6.98	0.1347	0.1445

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 to that 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 5).

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

[EB1] [EB2] [EB3] [EB4]

[EB5]

The present invention is an organic compound employed in an organic layer provided in an organic light-emitting device, and when used in particular in the electron blocking layer of an organic light-emitting device, low-voltage operation is possible compared to conventional devices, and device characteristics such as long lifespan and luminous efficiency are possible. Since this significantly improved organic light emitting device can be implemented, it can be used industrially in various display devices such as lighting devices as well as flat panel, flexible, wearable, and virtual or augmented reality displays.

Claims (6)

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

   [Formula Ⅰ]

   

   In the above [Chemical Formula I],

   Ar ₁ and Ar ₂ are the same or different from each other and are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

   R ₁ to R ₅ are the same or different from each other and are each independently hydrogen or deuterium,

   X is O, S or CR ₆ R ₇ ,

   R ₆ and R ₇ are the same or different from each other and are each independently hydrogen, deuterium, cyano group, halogen group, substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group with 3 to 20 carbon atoms, Any one 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,

   R ₆ and R ₇ may be connected to each other to further form an alicyclic or aromatic monocyclic or polycyclic ring,

   L is a divalent linking group, which is a single bond or one selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms,

   n is an integer from 0 to 3, and when n is 2 or more, the plurality of Ls are the same or different from each other,

   Ar ₃ and Ar ₄ 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.
2. According to paragraph 1,

   In the definition of R ₆ , R ₇ , L and Ar ₁ to Ar ₄ , substituted or unsubstituted means that R ₆ , R ₇ , L and Ar ₁ to Ar ₄ are each selected from the group consisting of deuterium, cyano group, halogen group, hydroxy group and nitro group. group, alkyl group, alkoxy group, halogenated alkoxy group, cycloalkyl group, heterocycloalkyl group, aryl group, fluorenyl group, heteroaryl group, silyl group and amine group, or 2 of the above substituents An organic compound meaning that the above substituents are substituted with a linked substituent or do not have any substituents.
3. According to paragraph 1,

   [Formula I] is an organic compound selected from the following [Formula 1] to [Formula 423]:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
4. 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.
5. According to paragraph 4,

   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).
6. According to clause 5,

   An organic light-emitting device comprising an organic compound represented by [Chemical Formula I] in the electron blocking layer.