KR20240029597A - 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 used in a hole transport layer, etc., it is possible to implement an organic light-emitting device with excellent luminescence properties such as luminescence 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, must be used. 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 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.

[Formula Ⅰ]

The specific structure of [Chemical Formula I], the specific compounds implemented thereby, and the definitions of X, A, R ₁ to R ₂ , n, and m 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 and R ₂ are the same or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted halogenated alkyl group having 1 to 20 carbon atoms. , a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 3 to 30 carbon atoms. is selected from heteroaryl groups.

n and m are each independently integers of 1 to 5, and when n and m are each 2 or more, a plurality of R ₁ and R ₂ are the same or different from each other.

X is O, NR ₃ or CR ₄ R ₅ .

R ₃ to R ₅ are the same or different from each other, and are each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and further, the R ₄ and R ₅ can be connected to each other to form a ring.

A is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted amine group.

According to one embodiment of the present invention, A may be an aryl group structure represented by [Structural Formula 1] to [Structural Formula 5] below, and may also be an amine structure represented by [Structural Formula 6] below.

[Structural Formula 1] [Structural Formula 2] [Rescue 3]

[Structural Formula 4] [Structural Formula 5]

In [Structural Formula 1] to [Structural Formula 5],

R is each independently hydrogen, deuterium, a halogen group, a cyano 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, or a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms. is selected from a cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and the plurality of R in each structural formula is the same or different from each other.

n is an integer from 0 to 5, m is an integer from 0 to 7, o is an integer from 0 to 4, and p is an integer from 0 to 3.

[Structural Formula 6]

In [Structural Formula 6] above,

L is a single bond or is 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.

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

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 2 to 30 carbon atoms.

Meanwhile, in the definition of A, R, R ₁ to R ₅ , L and Ar ₁ to Ar ₂ , substituted or unsubstituted means that A, R, R ₁ to R ₅ , L and Ar ₁ to Ar ₂ are each a deuterium , cyano group, halogen group, carbonyl group, alkyl group, alkoxy group, halogenated alkoxy group, halogenated alkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, fluorenyl group, heteroaryl group, silyl group and amine group, or It means being substituted with two or more substituents, being substituted with a substituent where two or more of the substituents are linked, or 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 addition, according to one embodiment of the present invention, each of A, R, R ₁ to R ₅ , L and Ar ₁ to Ar ₂ may have an additional substituent of a heterocycloalkyl group substituted with a carbonyl group, and more specifically, the following It may have derivatives such as aziridinone, azetidinone, pyrrolidinone, and piperidinone represented by [Structural Formula 7] as a substituent.

[Structural Formula 7]

R in the [Structural Formula 7] may each independently be hydrogen, deuterium, cyano group, halogen group, alkyl group, halogenated alkyl group, etc. within each structure.

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 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, 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 such as

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, the conditions required for each organic layer such as a hole transport layer and an electron blocking layer can be met. It is possible to manufacture an organic light-emitting compound material that satisfies the requirements, 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 receiving 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

(9,9-dimethyl-9H-fluoren-4-yl)boronic acid (10.0 g, 0.042 mol), 2-Bromo-4-chloro-1-nitrobenzene (11.9 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), Pd(PPh ₃ ) ₄ (1.0 g, 0.8 mmol) was added with 200 mL of Toluene, 50 mL of EtOH, 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 9.6 g (yield 65.3%) of <Intermediate 1-1>.

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

Intermediate 1-1 (10.0 g, 0.029 mol), PPh ₃ (18.8 g, 0.072 mol), and 350 mL of dichlorobenzene were added and reacted by refluxing and stirring at 180°C for 3 hours. After completion of the reaction, extraction was performed, concentration was performed, and then column was used to obtain 6.7 g of <Intermediate 1-2> (yield 73.7%).

(3) Manufacturing example 3: Synthesis of intermediate 1-3

Add 500 mL of DMF to Intermediate 1-2 (10.0 g, 0.032 mol), 1-fluoro-2-(trifluoromethyl)benzene (6.2 g, 0.038 mol), and Cs ₂ CO ₃ (6.5 g, 0.047 mol) and stir at 150°C. The reaction was stirred under reflux for 12 hours. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 9.8 g of <Intermediate 1-3> (yield 67.4%).

(4) Manufacturing example 4: Synthesis of intermediates 1-4

Intermediate 1-3 (10.0 g, 0.022 mol), (3,5-di-tert-butylphenyl)boronic acid (6.1 g, 0.026 mol), K ₂ CO ₃ (9.0 g, 0.065 mol), Pd(OAc) ₂ (1.3 _g , 0.001 mol), After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 9.7 g (yield 72.8%) of <Intermediate 1-4>.

(5) Manufacturing example 5: Synthesis of intermediates 1-5

Intermediate 1-4 (10.0 g, 0.016 mol) and N-Bromosuccinimide (6.9 g, 0.039 mol) were added to 200 mL of DMF and stirred at room temperature for 5 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 6.5 g of <Intermediate 1-5> (yield 57.6%).

(6) Manufacturing example 6: Synthesis of Compound 1

Intermediate 1-5 (10.0 g, 0.014 mol), (3,5-di-tert-butylphenyl)boronic acid (4.0 g, 0.017 mol), K ₂ CO ₃ (6.0 g, 0.043 mol), Pd(PPh ₃ ) _{To 4} (0.3 g, 0.3 mmol), 200 mL of Toluene, 50 mL of EtOH, 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 6.8 g of <Compound 1> (yield 58.8%).

LC/MS: m/z=803[(M) ⁺ ]

Synthesis example 2: Synthesis of Compound 8

(One) Manufacturing example 1: Synthesis of intermediate 8-1

Intermediate 1-3 (10.0 g, 0.022 mol), 3,5-Bis(trifluoromethyl)benzeneboronic acid (6.7 g, 0.026 mol), K ₂ CO ₃ (9.0 g, 0.065 mol), Pd(OAc) ₂ (1.3 g , 0.001 _mol ), After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 10.5 g of <Intermediate 8-1> (yield 75.8%).

(2) Manufacturing example 2: Synthesis of intermediate 8-2

Intermediate 8-1 (10.0 g, 0.016 mol) and N-Bromosuccinimide (6.7 g, 0.038 mol) were added to 200 mL of DMF and stirred at room temperature for 5 hours to react. After completion of the reaction, the extract was extracted and concentrated, followed by column and recrystallization to obtain 6.1 g of <Intermediate 8-2> (yield 54.3%).

(3) Manufacturing example 3 : Synthesis of Compound 8

Intermediate 8-2 (10.0 g, 0.014 mol), (3,5-di-tert-butylphenyl)boronic acid (3.9 g, 0.017 mol), K ₂ CO ₃ (5.8 g, 0.042 mol), Pd(PPh ₃ ) _{To 4} (0.3 g, 0.3 mmol), 200 mL of Toluene, 50 mL of EtOH, 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 5.7 g of <Compound 8> (yield 49.5%).

LC/MS: m/z=827[(M) ⁺ ]

Synthesis example 3: Synthesis of Compound 45

(One) Manufacturing example 1: Synthesis of Compound 45

Intermediate 8-2 (10.0 g, 0.014 mol), 3,5-Bis(trifluoromethyl)benzeneboronic acid (4.3 g, 0.017 mol), K ₂ CO ₃ (5.8 g, 0.042 mol), Pd(PPh ₃ ) ₄ (0.3 g, 0.3 mmol), 200 mL of Toluene, 50 mL of EtOH, 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 5.1 g of <Compound 45> (yield 43.0%).

LC/MS: m/z=851[(M) ⁺ ]

Synthesis example 4: Synthesis of Compound 99

(One) Manufacturing example 1: Synthesis of intermediate 99-1

Intermediate 1-3 (10.0 g, 0.022 mol), Bis(4-biphenylyl)amine (10.4 g, 0.033 mol), NaOtBu (6.2 g, 0.065 mol), Pd(dba) ₂ (0.5 g, 0.9 mmol), t 150 mL of Xylene was added to -Bu ₃ P (0.4 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 columnarized to obtain 9.9 g (yield 61.2%) of <Intermediate 99-1>.

(2) Manufacturing example 2: Synthesis of intermediate 99-2

Intermediate 99-1 (10.0 g, 0.013 mol) and N-Bromosuccinimide (5.7 g, 0.032 mol) were added to 200 mL of DMF and stirred at room temperature for 5 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 5.7 g of <Intermediate 99-2> (yield 51.6%).

(3) Manufacturing example 3: Synthesis of Compound 99

Intermediate 99-2 (10.0 g, 0.012 mol), (3,5-di-tert-butylphenyl)boronic acid (3.4 g, 0.015 mol), K ₂ CO ₃ (5.0 g, 0.036 mol), Pd(PPh ₃ ) _{To 4} (0.3 g, 0.2 mmol), 200 mL of Toluene, 50 mL of EtOH, 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 5.3 g of <Compound 99> (yield 46.8%).

LC/MS: m/z=934[(M) ⁺ ]

Synthesis example 5: Synthesis of Compound 107

(One) Manufacturing example 1: Synthesis of intermediate 107-1

1,3-dibromo-5-chlorobenzene (10.0 g, 0.037 mol), 2-Pyrrolidone (7.6 g, 0.089 mol), K ₃ PO ₄ (33.7 g, 0.104 mol), Pd(dba) ₂ (2.1 g, 0.004 mol), dioxane was added to Xant-Phos (15.4 g, 0.027 mol) and reacted by refluxing and stirring for 16 hours. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.6 g (yield 83.4%) of <Intermediate 107-1>.

(2) Manufacturing example 2: Synthesis of intermediate 107-2

Intermediate 107-1 (10.0 g, 0.036 mol), Bis(pinacolato)diboron (10.9 g, 0.043 mol), CH ₃ COOK (10.6 g, 0.108 mol), Pd(dppf)Cl ₂ (1.3 g, 1.8 mmol), Dioxane was added to XPhos (1.5 g, 3.2 mmol) and stirred at 100°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 9.5 g of <Intermediate 107-2> (yield 71.5%).

(3) Manufacturing example 3: Synthesis of Compound 107

Intermediate 99-2 (10.0 g, 0.012 mol), Intermediate 107-2 (5.4 g, 0.015 mol), K ₂ CO ₃ (5.0 g, 0.036 mol), Pd(PPh ₃ ) ₄ (0.3 g, 0.2 mmol) 200 mL of toluene, 50 mL of EtOH, 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 4.7 g of <Compound 107> (yield 39.2%).

LC/MS: m/z=988[(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 5

Examples of implementing an organic light emitting device according to the present invention Compounds 1 to 5 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 5 according to the present invention, and optical properties were measured.

Experiment example One : Example Optical properties of compounds 1 to 5

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 wavelength range of blue (450 nm), green (520 nm), and red (630 nm). The results are shown in [Table 1] below.

division refractive index Blue (450 nm) Green (520 nm) Red (630 nm) Example 1 (Compound 1) 1.72 1.69 1.67 Example 2 (Compound 8) 1.70 1.68 1.65 Example 3 (Compound 45) 1.66 1.62 1.61 Example 4 (Compound 99) 1.68 1.65 1.63 Example 5 (Compound 107) 1.84 1.81 1.79 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 others, 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 the device embodiment according to the present invention, the ITO transparent electrode is formed on a glass substrate of 25 mm × 25 mm × 0.7 mm, using an ITO glass substrate to which the ITO transparent electrode is attached, so that the light emitting area is 2 mm × 2 mm. After patterning, it was cleaned. 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 6 to 22

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.

ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (100 nm) / electron blocking layer (EB1, 10 nm) / emission 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 a hole transport layer was formed by depositing a 100 nm thick film of the compound according to the present invention shown in [Table 2] below. Afterwards, [EB1] 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 2

The organic light emitting device for Comparative Device Example 2 was manufactured in the same manner as the device structures of Examples 6 to 22, 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 6 to 22

The driving voltage, current efficiency, and color coordinates of the organic light emitting device manufactured according to the above example were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and the results were based on 1,000 nit. is as shown in [Table 2] below.

Example hole transport layer V cd/A CIEx CIey 6 Formula 1 4.25 7.37 0.1381 0.1352 7 Formula 8 4.28 7.29 0.1368 0.1376 8 Formula 12 4.31 7.32 0.1349 0.1382 9 Formula 26 4.36 7.17 0.1345 0.1361 10 Formula 27 4.18 7.54 0.1371 0.1339 11 Formula 45 4.27 7.32 0.1334 0.1353 12 Formula 51 4.33 7.35 0.1317 0.1358 13 Formula 63 4.41 7.45 0.1363 0.1347 14 Formula 69 4.30 7.22 0.1343 0.1365 15 Formula 79 4.19 7.44 0.1349 0.1358 16 Formula 84 4.35 7.28 0.1392 0.1335 17 Formula 89 4.21 7.34 0.1336 0.1359 18 Formula 99 4.29 7.25 0.1358 0.1332 19 Formula 103 4.32 7.32 0.1366 0.1361 20 Formula 107 4.34 7.27 0.1342 0.1373 21 Formula 119 4.28 7.49 0.1352 0.1368 22 Formula 132 4.37 7.35 0.1316 0.1351 Comparative Example 2 α-NPB 4.67 6.65 0.1353 0.1517

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 and R ₂ are the same or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted halogenated alkyl group having 1 to 20 carbon atoms. , a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 3 to 30 carbon atoms. Any one selected from heteroaryl groups,
n and m are each independently integers of 1 to 5, and when n and m are each 2 or more, a plurality of R ₁ and R ₂ are the same or different from each other,
X is O, NR ₃ or CR ₄ R ₅ ,
R ₃ to R ₅ are the same or different from each other, and are each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,
R ₄ and R ₅ may be connected to each other to form a ring,
A is selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted amine group. According to paragraph 1,
The A is an organic compound selected from the following [Structural Formula 1] to [Structural Formula 6]:
[Structural Formula 1] [Structural Formula 2] [Structural Formula 3]

[Structural Formula 4] [Structural Formula 5] [Structural Formula 6]

Among the [Structural Formula 1] to [Structural Formula 6],
R is each independently hydrogen, deuterium, a halogen group, a cyano 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, or a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms. is any one selected from a cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and the plurality of R in each structural formula are the same or different from each other, and ,
n is an integer from 0 to 5, m is an integer from 0 to 7, o is an integer from 0 to 4, p is an integer from 0 to 3,
L is a single bond or is 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,
q is an integer from 0 to 2, and when q is 2, the plurality of Ls are the same or different from each other,
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 2 to 30 carbon atoms. According to claim 1 or 2,
In the definition of A, R, R ₁ to R ₅ , L and Ar ₁ to Ar ₂ , substituted or unsubstituted means that A, R, R ₁ to R ₅ , L and Ar ₁ to Ar ₂ are respectively deuterium and cyanohydride. One or two or more selected from the group consisting of a cycloalkyl group, a halogen group, a carbonyl group, an alkyl group, an alkoxy group, a halogenated alkoxy group, a halogenated alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a fluorenyl group, a heteroaryl group, a silyl group, and an amine group. An organic compound meaning that it is substituted with a substituent, is substituted with a substituent in which two or more of the substituents are linked, or does not have any substituent. According to paragraph 1,
[Formula I] is an organic compound selected from the following [Formula 1] to [Formula 139]:














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.