KR20240032639A - 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.

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

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

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 including the same in a hole transport layer within the device.

[Formula Ⅰ]

The specific structure of [Chemical Formula I], the specific compounds implemented thereby, and the definitions of R ₁ , R ₂ , 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 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 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, or a substituted or unsubstituted carbon number. It is selected from cycloalkyl groups having 3 to 20 carbon atoms and substituted or unsubstituted heterocycloalkyl groups having 2 to 30 carbon atoms.

Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted fluorenyl group, and It is selected from substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms.

Ar ₃ and Ar ₄ are the same or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 20 carbon atoms, substituted or unsubstituted. It is selected from a halogenated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted fluorenyl group.

n and m are each integers of 1 or more, n+m ≥ 2, and when n and m are each 2 or more, a plurality of Ar ₃ and Ar ₄ are the same or different from each other.

According to one embodiment of the present invention, n and m are each 1, and accordingly, the [Formula I] compound according to the present invention is any one selected from the following [Formula I-1] to [Formula I-6]. It may be an organic compound as indicated.

[Formula Ⅰ-1] [Formula Ⅰ-2] [Chemical Formula Ⅰ-3]

[Chemical Formula Ⅰ-4] [Chemical Formula Ⅰ-5] [Formula Ⅰ-6]

In [Formula I-1] to [Formula I-6], the definitions of R ₁ , R ₂ and Ar ₁ to Ar ₄ are the same as those in [Formula I].

Meanwhile, in the definition of R ₁ , R ₂ and Ar ₁ to Ar ₄ , substituted or unsubstituted means that R ₁ , R ₂ and Ar ₁ to Ar ₄ are each selected from the group consisting of deuterium, cyano group, halogen group, hydroxy group, nitro group, Substituted with one or two or more substituents selected from alkyl group, halogenated alkyl group, deuterated alkyl group, alkoxy group, halogenated alkoxy group, deuterated alkoxy group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group and silyl group. Alternatively, it means that two or more of the above substituents are substituted with a linked substituent, or that it does 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., and other groups defined above such as deuterium. It means substituted with a substituent, 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 their condensed heterocycles. It means that groups such as benzquinoline group, benzimidazole group, benzoxazole group, benzthiazole group, benzcarbazole group, dibenzothiophenyl group, dibenzofuran group, etc. are also substituted with other substituents defined above 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, a deuterated alkyl group or alkoxy group, and a halogenated alkyl group or alkoxy group mean 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, 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, etc., and one or more of the layers may include the organic compound represented by [Chemical Formula I].

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

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

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

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

The hole injection layer is a material that can easily 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 back emitting type, or a double-sided emitting type depending on the material used.

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

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

Synthesis example 1: Synthesis of Compound 1

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

1,3-dibromo-5-chlorobenzene (10.0 g, 0.037 mol), B-[3,5-Bis(1,1-dimethylethyl)phenyl]boronic acid (20.8 g, 0.089 mol), K ₂ CO ₃ (30.7 g, 0.222 mol), Pd(PPh ₃ ) ₄ (0.9 g, 0.7 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 columnarized to obtain 11.2 g of <Intermediate 1-1> (yield 61.9%).

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

Intermediate 1-1 (10.0 g, 0.020 mol), Bis(pinacolato)diboron (6.2 g, 0.025 mol), CH ₃ COOK (6.0 g, 0.061 mol), Pd(dppf)Cl ₂ (0.8 g, 0.001 mol), Dioxane was added to XPhos (0.9 g, 0.002 mol) and stirred at 100°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.5 g of <Intermediate 1-2> (yield 71.6%).

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

1,4-dibromo-2,5-dimethylbenzene (10.0 g, 0.038 mol), intermediate 1-2 (26.4 g, 0.046 mol), K ₂ CO ₃ (15.7 g, 0.114 mol), Pd(PPh ₃ ) ₄ ( 0.9 g, 0.8 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 columnarized to obtain 15.2 g of <Intermediate 1-3> (yield 62.9%).

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

4-tert-Butylaniline (10.0 g, 0.067 mol), 1-Bromo-3,5-bis(1,1-dimethylethyl)benzene (27.1 g, 0.101 mol), NaOtBu (19.3 g, 0.201 mol), Pd(dba ) ₂ (1.5 g, 2.7 mmol) and t-Bu ₃ P (1.1 g, 5.4 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 14.3 g of <Intermediate 1-4> (yield 63.2%).

(5) Manufacturing example 5: Synthesis of Compound 1

Intermediate 1-4 (10.0 g, 0.030 mol), Intermediate 1-3 (28.3 g, 0.044 mol), NaOtBu (8.5 g, 0.089 mol), Pd(dba) ₂ (0.7 g, 1.2 mmol), t-Bu ₃ 150 mL of Xylene was added to 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 then recrystallized with a column to obtain 15.2 g of <Compound 1> (yield 57.4%).

LC/MS: m/z=894[(M) ⁺ ]

Synthesis example 2: Synthesis of Compound 29

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

1,4-dibromo-2-chlorobenzene (10.0 g, 0.037 mol), (3,5-Dimethylphenyl)boronic acid (13.3 g, 0.089 mol), K ₂ CO ₃ (30.7 g, 0.222 mol), Pd(PPh ₃ ) Toluene 200 mL, EtOH 50 mL, and H ₂ O 50 mL were added to ₄ (0.9 g, 0.7 mmol) and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.9 g (yield 75.0%) of <Intermediate 29-1>.

(2) Manufacturing example 2: Synthesis of intermediate 29-2

Intermediate 29-1 (10.0 g, 0.031 mol), Bis(pinacolato)diboron (9.5 g, 0.037 mol), CH ₃ COOK (9.2 g, 0.094 mol), Pd(dppf)Cl ₂ (1.1 g, 1.6 mmol), Dioxane was added to XPhos (1.3 g, 2.8 mol) and stirred at 100°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 9.1 g (yield 70.8%) of <Intermediate 29-2>.

(3) Manufacturing example 3: Synthesis of intermediate 29-3

1,4-dibromo-2,5-bis(trifluoromethyl)benzene (10.0 g, 0.027 mol), intermediate 29-2 (13.3 g, 0.032 mol), K ₂ CO ₃ (11.2 g, 0.081 mol), Pd(PPh ₃ ) To ₄ (0.6 g, 0.5 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 9.1 g of <Intermediate 29-3> (yield 58.6%).

(4) Manufacturing example 4: Synthesis of compound 29

Intermediate 1-4 (10.0 g, 0.030 mol), Intermediate 29-3 (25.7 g, 0.044 mol), NaOtBu (8.5 g, 0.065 mol), Pd(dba) ₂ (0.7 g, 1.2 mmol), t-Bu ₃ 150 mL of Xylene was added to 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 then recrystallized with a column to obtain 14.8 g of <Compound 29> (yield 59.9%).

LC/MS: m/z=833[(M) ⁺ ]

Synthesis example 3: Synthesis of Compound 52

(One) Manufacturing example 1: Synthesis of intermediate 52-1

1,3-dibromo-5-chlorobenzene (10.0 g, 0.037 mol), B-(3,5-dicyclohexylphenyl)boronic acid (25.4 g, 0.089 mol), K ₂ CO ₃ (30.7 g, 0.222 mol), Pd( Toluene 200 mL, EtOH 50 mL, and H ₂ O 50 mL were added to PPh ₃ ) ₄ (0.9 g, 0.7 mmol) and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 13.3 g (yield 60.6%) of <Intermediate 52-1>.

(2) Manufacturing example 2: Synthesis of intermediate 52-2

Intermediate 52-1 (10.0 g, 0.017 mol), Bis(pinacolato)diboron (5.1 g, 0.020 mol), CH ₃ COOK (5.0 g, 0.051 mol), Pd(dppf)Cl ₂ (0.6 g, 0.8 mmol), Dioxane was added to XPhos (0.7 g, 1.5 mmol) and stirred at 100°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.2 g (yield 71.0%) of <Intermediate 52-2>.

(3) Manufacturing example 3: Synthesis of intermediate 52-3

1,4-dibromo-2,5-difluorobenzene (10.0 g, 0.037 mol), intermediate 52-2 (30.2 g, 0.044 mol), K ₂ CO ₃ (15.3 g, 0.110 mol), Pd(PPh ₃ ) ₄ ( 0.9 g, 0.7 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 recrystallized using a column to obtain 12.7 g of <Intermediate 52-3> (yield 46.1%).

(4) Manufacturing example 4: Synthesis of Compound 52

Intermediate 52-3 (10.0 g, 0.013 mol), Intermediate 1-4 (6.8 g, 0.020 mol), NaOtBu (3.8 g, 0.040 mol), Pd(dba) ₂ (0.3 g, 0.5 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.2 g, 1.1 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 52> (yield 60.4%).

LC/MS: m/z=1005[(M) ⁺ ]

Synthesis example 4: Synthesis of Compound 99

(One) Manufacturing example 1: Synthesis of Compound 99

Intermediate 1-3 (10.0 g, 0.016 mol), N-([1,1'-Biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (8.5 g, 0.024 mol), Add _{150 mL} of . After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 8.6 g of <Compound 99> (yield 59.7%).

LC/MS: m/z=917[(M) ⁺ ]

Synthesis example 5: Synthesis of Compound 111

(One) Manufacturing example 1: Synthesis of intermediate 111-1

1,4-dibromo-2,5-dimethylbenzene (10.0 g, 0.038 mol), (3,5-di-tert-butylphenyl)boronic acid (10.6 g, 0.046 mol), K ₂ CO ₃ (15.7 g, 0.114 mol) ), Pd(PPh ₃ ) ₄ (0.9 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 then recrystallized with a column to obtain 6.8 g of <Intermediate 111-1> (yield 48.1%).

(2) Manufacturing example 2: Synthesis of Compound 111

Intermediate 111-1 (10.0 g, 0.027 mol), N-([1,1'-Biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (14.5 g, 0.040 mol), Add _{150 mL} of . After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 10.7 g of <Compound 111> (yield 61.1%).

LC/MS: m/z=653[(M) ⁺ ]

Synthesis example 6: Synthesis of Compound 150

(One) Manufacturing example 1: Synthesis of intermediate 150-1

1,4-dibromo-2,5-dichlorobenzene (10.0 g, 0.033 mol), Cyclohexylboronic acid (10.1 g, 0.079 mol), K ₂ CO ₃ (27.2 g, 0.020 mol), Pd(PPh ₃ ) ₄ (0.8 g , 0.7 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 columnarized to obtain 5.8 g (yield 56.8%) of <Intermediate 150-1>.

(2) Manufacturing example 2: Synthesis of intermediate 150-2

Intermediate 150-1 (10.0 g, 0.032 mol), (3,5-di-tert-butylphenyl)boronic acid (9.0 g, 0.039 mol), K ₂ CO ₃ (13.3 g, 0.096 mol), Pd(OAc) ₂ (1.9 _g , 0.002 mol), After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 8.5 g of <Intermediate 150-2> (yield 56.9%).

(3) Manufacturing example 3: Synthesis of Compound 150

Intermediate 150-2 (10.0 g, 0.022 mol), N-[1,1'-Biphenyl]-4-yl[1,1'-biphenyl]-4-amine (10.4 g, 0.033 mol), NaOtBu (6.2 g , 0.065 mol), Pd(dba) ₂ (0.5 g, 0.9 mmol), and t-Bu ₃ P (0.4 g, 1.7 mmol) were mixed with 150 mL of xylene and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 8.7 g of <Compound 150> (yield 54.0%).

LC/MS: m/z=749[(M) ⁺ ]

Synthesis example 7: Synthesis of Compound 178

(One) Manufacturing example 1: Synthesis of intermediate 178-1

1-Bromo-2-(1,1-dimethylethyl)benzene (10.0 g, 0.047 mol), 9,9-Dimethyl-9H-fluoren-2-amine (14.7 g, 0.070 mol), NaOtBu (13.5 g, 0.141 mol) ), Pd(dba) ₂ (1.1 g, 1.9 mmol), and t-Bu ₃ P (0.8 g, 3.8 mmol) were mixed with 150 mL of Xylene and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 10.8 g of <Intermediate 178-1> (yield 67.4%).

(2) Manufacturing example 2: Synthesis of Compound 178

Intermediate 1-3 (10.0 g, 0.016 mol), Intermediate 178-1 (8.0 g, 0.025 mol), NaOtBu (4.5 g, 0.047 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 then recrystallized with a column to obtain 8.8 g of <Compound 178> (yield 62.5%).

LC/MS: m/z=898[(M) ⁺ ]

Synthesis example 8: Synthesis of Compound 191

(One) Manufacturing example 1: Synthesis of intermediate 191-1

1-Bromo-3-chloro-5-iodobenzene (10.0 g, 0.032 mol), B-[3,5-Bis(1,1-dimethylethyl)phenyl] boronic acid (8.9 g, 0.038 mol), K ₂ CO ₃ (13.1 g, 0.095 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.6 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 columnarized to obtain 4.8 g (yield 40.1%) of <Intermediate 191-1>.

(2) Manufacturing example 2: Synthesis of intermediate 191-2

Intermediate 191-1 (10.0 g, 0.026 mol), 2-Trifluoromethylphenylboronic acid (6.0 g, 0.032 mol), K ₂ CO ₃ (10.9 g, 0.079 mol), Pd(PPh ₃ ) ₄ (0.6 g, 0.5 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 columnarized to obtain 6.1 g (yield 52.1%) of <Intermediate 191-2>.

(3) Manufacturing example 3: Synthesis of intermediate 191-3

Intermediate 191-2 (10.0 g, 0.023 mol), Bis(pinacolato)diboron (6.9 g, 0.027 mol), CH ₃ COOK (6.6 g, 0.067 mol), Pd(dppf)Cl ₂ (0.8 g, 1.1 mmol), Dioxane was added to XPhos (1.0 g, 2.0 mol) and stirred at 100°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.6 g (yield 71.3%) of <Intermediate 191-3>.

(4) Manufacturing example 4: Synthesis of intermediate 191-4

2,5-Dibromo-p-xylene (10.0 g, 0.038 mol), intermediate 191-3 (24.4 g, 0.046 mol), K ₂ CO ₃ (15.7 g, 0.114 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.8 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 9.1 g of <Intermediate 191-4> (yield 40.5%).

(5) Manufacturing example 5: Synthesis of Compound 191

Intermediate 191-4 (10.0 g, 0.017 mol), N-([1,1'-Biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (9.1 g, 0.025 mol), _{150 mL} of . After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 10.0 g of <Compound 191> (yield 67.9%).

LC/MS: m/z=874[(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 x 25 mm was cleaned, mounted in a vacuum chamber, and when the base pressure was 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 8

Examples of implementing an organic light emitting device according to the present invention Compounds 1 to 8 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 [HT1] below 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 8

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) 1.82 1.73 1.66 Example 2 (Compound 29) 1.80 1.72 1.64 Example 3 (Compound 52) 1.76 1.67 1.60 Example 4 (Compound 99) 1.78 1.70 1.64 Example 5 (Compound 111) 1.74 1.76 1.69 Example 6 (Compound 150) 1.79 1.69 1.68 Example 7 (Compound 178) 1.77 1.72 1.62 Example 8 (Compound 191) 1.83 1.73 1.67 Comparative Example 1 (HT1) 1.92 1.84 1.78

Looking at [Table 1], the refractive index value of the organic compound according to the present invention in each of the blue, green, and red wavelength bands (450, 520, and 630 nm) is significantly higher than that of Comparative Example 1 compound [HT1], which is a conventional hole transport material. It can be confirmed that it is low, 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.

[HT1]

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 9 to 28

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 Device Comparative Example 2 was manufactured in the same manner as the device structures of Examples 9 to 28, except that [HT1] was used instead of the compound according to the present invention in the hole transport layer.

Experiment example 2: element Example Luminous properties of 9 to 28

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 9 Formula 1 4.24 7.36 0.1371 0.1372 10 Formula 5 4.29 7.28 0.1358 0.1366 11 Formula 12 4.32 7.25 0.1348 0.1383 12 Formula 29 4.35 7.19 0.1345 0.1361 13 Formula 38 4.19 7.41 0.1371 0.1339 14 Formula 49 4.26 7.33 0.1333 0.1353 15 Formula 52 4.31 7.28 0.1316 0.1348 16 Formula 64 4.32 7.25 0.1343 0.1361 17 Formula 83 4.28 7.41 0.1349 0.1357 18 Formula 99 4.26 7.49 0.1316 0.1341 19 Formula 103 4.36 7.29 0.1392 0.1334 20 Formula 111 4.22 7.32 0.1336 0.1358 21 Formula 119 4.27 7.24 0.1358 0.1331 22 Formula 141 4.33 7.31 0.1366 0.1358 23 Formula 150 4.22 7.28 0.1342 0.1371 24 Formula 178 4.24 7.39 0.1364 0.1353 25 Formula 179 4.27 7.42 0.1352 0.1369 26 Chemical formula 180 4.19 7.51 0.1371 0.1349 27 Formula 191 4.29 7.26 0.1363 0.1347 28 Formula 199 4.33 7.28 0.1346 0.1354 Comparative Example 2 HT1 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] [HT1] [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 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, or a substituted or unsubstituted carbon number. Any one selected from 3 to 20 cycloalkyl groups and substituted or unsubstituted heterocycloalkyl groups with 2 to 30 carbon atoms,
Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted fluorenyl group, and Any one selected from substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms,
Ar ₃ and Ar ₄ are the same or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group with 3 to 20 carbon atoms, substituted or unsubstituted. Any selected from a halogenated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted fluorenyl group. It is one,
n and m are each integers of 1 or more, n+m ≥ 2, and when n and m are each 2 or more, a plurality of Ar ₃ and Ar ₄ are the same or different from each other. According to paragraph 1,
The [Formula I] is an organic compound represented by any one selected from the following [Formula I-1] to [Formula I-6]:
[Formula Ⅰ-1] [Formula Ⅰ-2] [Formula Ⅰ-3]

[Formula Ⅰ-4] [Formula Ⅰ-5] [Formula Ⅰ-6]

In [Formula I-1] to [Formula I-6], the definitions of R ₁ , R ₂ and Ar ₁ to Ar ₄ are the same as those in [Formula I]. According to paragraph 1,
In the definition of R ₁ , R ₂ and Ar ₁ to Ar ₄ , substituted or unsubstituted means that R ₁ , R ₂ and Ar ₁ to Ar ₄ are each selected from the group consisting of deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, Substituted with one or two or more substituents selected from a halogenated alkyl group, a deuterated alkyl group, an alkoxy group, a halogenated alkoxy group, a deuterated alkoxy group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, and a silyl group, An organic compound meaning that two or more of the above substituents are substituted with a linked substituent, or do not have any substituents. According to paragraph 1,
The [Formula I] is an organic compound selected from the following [Formula 1] to [Formula 201]:
















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