KR20240055927A - 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], which has a lower refractive index value in each of the blue, green, and red wavelength bands compared to conventional hole transport materials, so when it is used in the hole transport layer to construct a device, the organic compound Optimization of the efficiency of the light-emitting device can be expected, and accordingly, when the compound according to the present invention is employed in the hole transport layer within the 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

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 hole transport 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. will be.

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 the optical and luminous properties of materials and the development of organic layer structures within devices.

Therefore, the present invention seeks to provide an organic compound that can be used as an organic layer material such as a hole transport 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. .

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 in an organic layer such as a hole transport layer.

[Formula Ⅰ]

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

The organic light-emitting device employing the organic compound according to the present invention in an organic layer such as a hole transport 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. there is.

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 has significantly improved device characteristics such as low voltage driving, long life, and luminous efficiency when employed in various organic layers in an organic light-emitting device, preferably in a hole transport layer. It is possible to implement a light emitting device.

In addition, the organic compound represented by the following [Chemical Formula I] according to the present invention has a lower refractive index value in each of the blue, green, and red wavelength bands (450, 520, and 630 nm) compared to conventional hole transport materials, and thus When used in the transport layer to form a device, optimization of the efficiency of the organic light emitting device can be expected.

[Formula Ⅰ]

In the above [Chemical Formula I],

R ₁ is hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted halogenated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, It is selected from substituted or unsubstituted cycloalkyl groups having 3 to 20 carbon atoms and substituted or unsubstituted heterocycloalkyl groups having 2 to 20 carbon atoms.

m is an integer from 1 to 5, and when m is 2 or more, a plurality of R _1s are the same or different from each other.

According to one embodiment of the present invention, at least one of R ₁ is a substituted or unsubstituted alkyl group.

R ₂ is selected from a substituted or 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. .

According to one embodiment of the present invention, R ₂ is substituted with one or two or more substituents selected from deuterium, halogen group, alkyl group, halogenated alkyl group, alkylsilyl group and cycloalkyl group, or a substituent where two or more of the substituents are connected. It may be an aryl group having 6 to 30 carbon atoms substituted with .

Ar ₁ and Ar ₂ are the same as 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 ₁ , R ₂ and Ar ₁ to Ar ₂ , substituted or unsubstituted means that R ₁ , R ₂ and Ar ₁ to Ar ₂ are each selected from the group consisting of deuterium, cyano group, halogen group, carbonyl group, alkyl group, and alkoxy group. group, halogenated alkoxy group, halogenated alkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, fluorenyl group, heteroaryl group, silyl group, and amine group. It means that the substituent is substituted with a linked substituent or does not have any substituent.

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 or alkoxy group may be a deuterated alkyl group or alkoxy group, a halogenated alkyl group, or an alkoxy group, which means an alkyl group or alkoxy group in which the alkyl group or alkoxy group is 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. 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 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, depending on the characteristics of the various substituents introduced, it can be used as a hole transport layer of the organic layer. It can be used as a material, 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, organic light emitting devices that meet the conditions required for each organic layer, such as a hole transport layer, when manufacturing an organic light-emitting device. Compound materials can be manufactured, and in particular, when the compound of [Chemical Formula I] according to the present invention is employed in the hole transport layer, etc., device characteristics such as luminous efficiency of the device can be further improved.

The organic light-emitting 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.

Therefore, in the organic light emitting device according to the present invention, the organic layer may include a hole transport layer or an electron blocking layer, 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.

As an anode material, a material with a large work function is generally preferred 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 material is generally preferably a material with a small 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 material 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 material 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. Additionally, the compound represented by [Chemical Formula I] according to the present invention can be used.

The light-emitting material 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 preferred. 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 transport material is a material that can easily inject electrons from the cathode and transfer them to the light-emitting layer, and a material with high mobility for electrons 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 light-emitting compound according to the present invention can function in organic electronic devices, including organic solar cells, organic photoreceptors, and organic transistors, 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

3,6-Dibromocarbazole (10.0 g, 0.031 mol), 1-(1,1-Dimethylethyl)-2-fluorobenzene (5.6 g, 0.037 mol), Cs ₂ CO ₃ (6.4 g, 0.046 mol) in 500 mL of DMF. It was added and stirred under reflux at 150°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.3 g of <Intermediate 1-1> (yield 59.0%).

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

Intermediate 1-1 (10.0 g, 0.022 mol), (3,5-di-tert-butylphenyl)boronic acid (6.2 g, 0.026 mol), K ₂ CO ₃ (9.1 g, 0.066 mol), Pd(PPh ₃ ) To ₄ (0.5 g, 0.4 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 6.4 g of <Intermediate 1-2> (yield 51.6%).

(3) Manufacturing example 3: Synthesis of Compound 1

Intermediate 1-2 (10.0 g, 0.017 mol), diphenylamine (4.5 g, 0.027 mol), NaOtBu (5.1 g, 0.053 mol), Pd(dba) ₂ (0.4 g, 0.7 mmol), t-Bu ₃ P (0.3 g, 1.4 mmol) was 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 7.7 g of <Compound 1> (yield 66.6%).

LC/MS: m/z=654[(M) ⁺ ]

Synthesis example 2: Synthesis of Compound 9

(One) Manufacturing example 1: Synthesis of Compound 9

Intermediate 1-2 (10.0 g, 0.017 mol), 3,5-diphenyl-N-(4-phenylphenyl)aniline (10.5 g, 0.027 mol), NaOtBu (5.1 g, 0.053 mol), Pd(dba) ₂ (0.4 g, 0.7 mmol) and t-Bu ₃ P (0.3 g, 1.4 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 10.8 g of <Compound 9> (yield 69.3%).

LC/MS: m/z=882[(M) ⁺ ]

Synthesis example 3: Synthesis of Compound 20

(One) Manufacturing example 1: Synthesis of intermediate 20-1

2-Aminobiphenyl (10.0 g, 0.059 mol), 3-Bromo-9,9'-spirobi[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 then recrystallized with a column to obtain 17.6 g of <Intermediate 20-1> (yield 61.6%).

(2) Manufacturing example 2: Synthesis of Compound 20

Intermediate 1-2 (10.0 g, 0.017 mol), Intermediate 20-1 (12.8 g, 0.027 mol), NaOtBu (5.1 g, 0.053 mol), Pd(dba) ₂ (0.4 g, 0.7 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.3 g, 1.4 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 12.2 g of <Compound 20> (yield 71.3%).

LC/MS: m/z=969[(M) ⁺ ]

Synthesis example 4: Synthesis of compound 29

(One) Manufacturing example 1: Synthesis of intermediate 29-1

9,9-dimethyl-9H-fluoren-2-amine (10.0 g, 0.048 mol), 3-Bromodibenzofuran (17.7 g, 0.072 mol), NaOtBu (13.8 g, 0.143 mol), Pd(dba) ₂ (1.1 g, 1.9 mmol), 150 mL of xylene was added to t-Bu ₃ P (0.8 g, 3.8 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 <Intermediate 29-1> (yield 65.2%).

(2) Manufacturing example 2: Synthesis of Compound 29

Intermediate 1-2 (10.0 g, 0.018 mol), Intermediate 29-1 (10.0 g, 0.027 mol), NaOtBu (5.1 g, 0.053 mol), Pd(dba) ₂ (0.4 g, 0.7 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.3 g, 1.4 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 11.0 g of <Compound 29> (yield 72.3%).

LC/MS: m/z=860[(M) ⁺ ]

Synthesis example 5: Synthesis of Compound 39

(One) Manufacturing example 1: Synthesis of intermediate 39-1

3,6-dibromocarbazole (10.0 g, 0.031 mol), 1,3-di-tert-butyl-5-fluorobenzene (7.7 g, 0.037 mol), and Cs ₂ CO ₃ (6.4 g, 0.046 mol) were mixed with 500 mL of DMF. It was added and stirred under reflux at 150°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 10.1 g (yield 64.0%) of <Intermediate 39-1>.

(2) Manufacturing example 2: Synthesis of intermediate 39-2

Intermediate 39-1 (10.0 g, 0.020 mol), (3,5-di-tert-butylphenyl)boronic acid (5.5 g, 0.023 mol), K ₂ CO ₃ (8.1 g, 0.058 mol), Pd(PPh ₃ ) To ₄ (0.5 g, 0.4 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 39-2> (yield 54.4%).

(3) Manufacturing example 3: Synthesis of Compound 39

Intermediate 39-2 (10.0 g, 0.016 mol), N-[1,1'-Biphenyl]-4-yl-3-dibenzofuranamine (8.1 g, 0.024 mol), NaOtBu (4.6 g, 0.048 mol), Pd(dba ) ₂ (0.4 g, 0.6 mmol) and t-Bu ₃ P (0.3 g, 1.3 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 recrystallized using a column to obtain 10.0 g of <Compound 39> (yield 71.0%).

LC/MS: m/z=877[(M) ⁺ ]

Synthesis example 6: Synthesis of Compound 43

(One) Manufacturing example 1: Synthesis of intermediate 43-1

3,6-dibromocarbazole (10.0 g, 0.031 mol), 1,4-di-tert-butyl-2-fluorobenzene (7.7 g, 0.037 mol), and Cs ₂ CO ₃ (6.4 g, 0.046 mol) were mixed with 500 mL of DMF. It was added and stirred under reflux at 150°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 9.4 g of <Intermediate 43-1> (yield 59.5%).

(2) Manufacturing example 2: Synthesis of intermediate 43-2

Intermediate 43-1 (10.0 g, 0.020 mol), (2,5-di-tert-butylphenyl)boronic acid (5.5 g, 0.023 mol), K ₂ CO ₃ (8.1 g, 0.058 mol), Pd(PPh ₃ ) To ₄ (0.5 g, 0.4 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 (yield 51.9%) of <Intermediate 43-2>.

(3) Manufacturing example 3: Synthesis of intermediate 43-3

3,4-diphenylaniline (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), t-Bu ₃ 150 mL of Xylene was added to P (0.7 g, 3.3 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 10.6 g of <Intermediate 43-3> (yield 65.4%).

(4) Manufacturing example 4: Synthesis of Compound 43

Intermediate 43-2 (10.0 g, 0.016 mol), Intermediate 43-3 (9.6 g, 0.024 mol), NaOtBu (4.6 g, 0.048 mol), Pd(dba) ₂ (0.4 g, 0.6 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.3 g, 1.3 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 10.2 g of <Compound 43> (yield 67.6%).

LC/MS: m/z=939[(M) ⁺ ]

Experiment example 1: Optical properties of the compound according to the present invention

In order to test the optical properties of the compound according to the present invention, quartz glass having a size of 25 mm × 25 mm is cleaned, mounted in a vacuum chamber, and when the base pressure is greater than 1 × 10-6 torr, the glass substrate is placed on the glass substrate as shown below [Table 1 The example compounds and Comparative Example 1 compounds according to the present invention described in ] were deposited, respectively, and optical properties were measured.

Example 1 to 6

Examples of implementing an organic light emitting device according to the present invention Compounds 1 to 6 were each deposited at 100 nm on a glass substrate, and the refractive index was measured.

Quartz glass / organic matter (100 nm)

Comparative example One

The substrate for Comparative Example 1 was manufactured in the same manner except that the following α-NPB was used instead of Example Compounds 1 to 6 according to the present invention, and optical properties were measured.

Experiment example One : Example Optical properties of compounds 1 to 6

The refractive index of the substrate manufactured according to the above example was measured using Ellipsometry (Elli-SE), and the refractive index was measured in each of the blue (450 nm), green (520 nm), and red (630 nm) wavelength regions. The results are shown in [Table 1] below.

division refractive index Blue (450 nm) Green (520 nm) Red (630 nm) Example 1 (Compound 1) 1.80 1.76 1.69 Example 2 (Compound 9) 1.81 1.72 1.66 Example 3 (Compound 20) 1.77 1.67 1.66 Example 4 (Compound 29) 1.79 1.75 1.68 Example 5 (Compound 39) 1.84 1.82 1.74 Example 6 (Compound 43) 1.76 1.69 1.65 Comparative Example 1 (α-NPB) 1.92 1.84 1.78

Looking at [Table 1], the organic compound according to the present invention has a refractive index value in each of the blue, green, and red wavelength bands (450, 520, and 630 nm), and is the compound of Comparative Example 1 (α-NPB), which is a conventional hole transport material. It can be confirmed that it is significantly lower compared to the other, and accordingly, when the compound according to the present invention with a low refractive index value is employed in the hole transport layer in the device, optimization of the efficiency of the organic light-emitting device can be expected.

[α-NPB]

device Example ( HTL )

In an example according to the present invention, the anode was patterned to have a light emitting area of 2 mm × 2 mm using an ITO glass substrate containing Ag of 25 mm × 25 mm × 0.7 mm and then cleaned. After the patterned ITO substrate was mounted in a vacuum chamber, organic materials and metals were deposited on the substrate in the structure below at a process pressure of 1 × 10 ^-6 torr or more.

device Example 7 to 23

After manufacturing an organic light-emitting device having the following device structure by employing the compound implemented according to the present invention in the hole transport layer, the light emission and driving characteristics of the compound implemented according to the present invention and the device employing the same in the hole transport layer was measured.

Ag/ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (60 nm) / electron blocking layer (TCTA, 10 nm) / emission layer (20 nm) / electron transport layer (201:Liq, 30 nm) / LiF (1 nm) / Mg:Ag (15 nm) / Light efficiency improvement layer (70 nm)

[HAT-CN] was deposited to a thickness of 5 nm on the ITO transparent electrode containing Ag on a glass substrate to form a hole injection layer. Afterwards, the compound according to the present invention shown in [Table 2] below was deposited to a thickness of 60 nm to form a hole transport layer. Afterwards, [TCTA] was deposited to a thickness of 10 nm to form an electron blocking layer. Afterwards, [BH1] as a host compound and [BD1] as a dopant compound were co-deposited to a thickness of 20 nm to form an emitting layer. Afterwards, an electron transport layer (50% doped with [201] compound Liq below) was deposited to a thickness of 30 nm, and then LiF was deposited to a thickness of 1 nm to form an electron injection layer. Afterwards, a cathode was formed by forming a film of Mg:Ag at a ratio of 1:9 to a thickness of 15 nm. In addition, an organic electroluminescent device was manufactured by forming an Alq ₃ compound to a thickness of 70 nm as a capping layer compound.

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 7 to 23, except that α-NPB was used instead of the compound according to the present invention in the hole transport layer.

Experiment example 2: element Example Luminous properties of 7 to 23

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 hole transport layer V cd/A CIEx CIey 7 Formula 1 3.87 8.43 0.1333 0.0585 8 Formula 3 3.90 8.36 0.1347 0.0580 9 Formula 5 3.74 8.48 0.1343 0.0565 10 Formula 9 3.62 8.52 0.1349 0.0559 11 Formula 13 3.65 8.41 0.1325 0.0531 12 Formula 17 3.73 8.34 0.1380 0.0486 13 Formula 20 3.61 8.27 0.1393 0.0467 14 Formula 22 3.82 8.35 0.1378 0.0562 15 Formula 25 3.75 8.58 0.1367 0.0554 16 Formula 29 3.74 8.22 0.1353 0.0481 17 Formula 32 3.78 8.57 0.1372 0.0456 18 Formula 35 3.66 8.30 0.1370 0.0593 19 Formula 37 3.70 8.35 0.1388 0.0534 20 Formula 39 3.75 8.54 0.1323 0.0573 21 Formula 41 3.70 8.45 0.1375 0.0486 22 Formula 43 3.65 8.24 0.1372 0.0497 23 Formula 46 3.62 8.13 0.1371 0.0517 Comparative Example 2 α-NPB 4.33 7.84 0.1471 0.0583

Looking at the results shown in [Table 2] above, in the case of an organic light-emitting device employing a compound according to the present invention in the hole transport layer within the device, the organic light-emitting device employing a compound widely used as a conventional hole transport material (Comparative Example 2) In comparison, it can be seen that the driving voltage decreases and the current efficiency improves.

As confirmed in [Table 1] above, it can be clearly confirmed that the luminous efficiency is improved as the refractive index of the organic compound employing hole transport according to the present invention is significantly lowered compared to the comparative example compound.

[HAT_CN] [α-NPB] [BH1] [BD1] [ET1]

[EB1]

Claims (7)

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

In the above [Chemical Formula I],
R ₁ is hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted halogenated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, Any one selected from a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms and a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms,
m is an integer from 1 to 5, and when m is 2 or more, a plurality of R ₁ are the same or different from each other,
R ₂ is selected from a substituted or 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. Which one,
Ar ₁ and Ar ₂ 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. According to paragraph 1,
In the definition of R ₁ , R ₂ and Ar ₁ to Ar ₂ , substituted or unsubstituted means that R ₁ , R ₂ and Ar ₁ to Ar ₂ are each selected from the group consisting of deuterium, cyano group, halogen group, carbonyl group, alkyl group, alkoxy group, It is substituted with one or two or more substituents selected from a halogenated alkoxy group, a halogenated alkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, fluorenyl group, heteroaryl group, silyl group and amine group, or two or more substituents among the above substituents An organic compound, meaning that it is substituted with a linked substituent or has no substituent. According to paragraph 1,
R ₂ is an aryl having 6 to 30 carbon atoms substituted with 1 or 2 or more substituents selected from deuterium, halogen group, alkyl group, halogenated alkyl group, alkylsilyl group and cycloalkyl group, or substituted with a substituent in which 2 or more of the substituents are connected. An organic compound characterized by being a group. According to paragraph 1,
[Formula I] is an organic compound selected from the following [Formula 1] to [Formula 59]:




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 5,
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 6,
An organic light-emitting device comprising an organic compound represented by [Chemical Formula I] in the hole transport layer.