KR20240036471A - 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 in each of the blue, green, and red wavelength bands compared to conventional hole transport materials, and is used in the hole transport layer to construct a device. Optimization of the efficiency of organic light-emitting devices 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, organic compounds employed in organic layers such as hole transport layers and electron blocking layers in organic light-emitting devices, and organic compounds whose device characteristics, such as low-voltage operation, long life, and luminous efficiency, are significantly improved by employing them. It is about light emitting devices.

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, green, blue, and red, so it has recently been the subject of much attention as a next-generation display device.

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

Therefore, there is a continued need for the development of new materials that can improve 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 R ₁ to 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. When constructing a device by using it in the hole transport layer, 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, and a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms.

m and n are each integers from 0 to 4 (provided that n+m ≥ 1), and when m and n are each 2 or more, a plurality of R ₁ and R ₂ are the same or different from each other, and R ₁ and R Among _{the 2} , at least one is not hydrogen.

Accordingly, the organic compound represented by [Formula I] according to the present invention is characterized by having at least one substituent other than hydrogen on each phenyl skeleton, that is, the biphenyl skeleton, into which R ₁ and R ₂ are introduced.

Ar ₁ and Ar ₂ are the same or different from each other, and each independently represents 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 an unsubstituted cycloalkyl group having 3 to 20 carbon atoms, 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.

Ar ₃ and Ar ₄ 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 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, 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 addition, according to one embodiment of the present invention, each of R ₁ , R ₂ and Ar ₁ to Ar ₄ or their substituent may be a carbonyl-substituted heterocycloalkyl group, and more specifically, the following [Structural Formula 1 ] may be derivatives of aziridinone, azetidinone, pyrrolidinone, piperidinone, etc.

[Structural Formula 1]

R in the [Structural Formula 1] may 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 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 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 8

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

2,5-dibromo-p-xylene (10.0 g, 0.038 mol), 2-Chlorophenylboronic acid (7.1 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 5.4 g of <Intermediate 8-1> (yield 48.2%).

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

Intermediate 8-1 (10.0 g, 0.034 mol), (3,5-di-tert-butylphenyl)boronic acid (9.5 g, 0.041 mol), K ₂ CO ₃ (14.0 g, 0.102 mol), Pd(OAc) ₂ ( _2.0 g, 1.7 mmol), After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 9.5 g (yield 62.5%) of <Intermediate 8-2>.

(3) Manufacturing example 3: Synthesis of intermediate 8-3

Intermediate 8-2 (10.0 g, 0.022 mol), 4-(Trifluoromethyl)aniline (5.4 g, 0.033 mol), NaOtBu (6.4 g, 0.067 mol), Pd(dba) ₂ (0.5 g, 0.9 mmol), t- 150 mL of xylene was added to Bu ₃ P (0.4 g, 1.8 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 5.4 g of <Intermediate 8-3> (yield 45.8%).

(4) Manufacturing example 4: Synthesis of Compound 8

Intermediate 8-3 (10.0 g, 0.019 mol), 1-Bromo-3,5-di-tert-butylbenzene (7.6 g, 0.028 mol), NaOtBu (5.4 g, 0.057 mol), Pd(dba) ₂ (0.4 g , 0.8 mmol) and t-Bu ₃ P (0.3 g, 1.5 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 8.5 g of <Compound 8> (yield 62.7%).

LC/MS: m/z=717[(M) ⁺ ]

Synthesis example 2: Synthesis of Compound 37

(One) Manufacturing example 1: Synthesis of intermediate 37-1

2,5-dibromo-p-xylene (10.0 g, 0.038 mol), N-[1,1'-Biphenyl]-4-yl[1,1'-biphenyl]-4-amine (18.3 g, 0.057 mol) , NaOtBu (10.9 g, 0.114 mol), Pd(dba) ₂ (0.9 g, 1.5 mmol), and t-Bu ₃ P (0.6 g, 3.0 mmol) were mixed with 150 mL of I ordered it. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.2 g (yield 42.9%) of <Intermediate 37-1>.

(2) Manufacturing example 2: Synthesis of intermediate 37-2

Intermediate 37-1 (10.0 g, 0.020 mol), 2-Chloro-4-fluorophenylboronic acid (4.2 g, 0.024 mol), K ₂ CO ₃ (8.2 g, 0.060 mol), Pd(PPh ₃ ) ₄ (0.5 g, 0.4 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, it was extracted, concentrated, and recrystallized with a column to obtain 7.5 g of <Intermediate 37-2> (yield 68.3%).

(3) Manufacturing example 3: Synthesis of Compound 37

Intermediate 37-2 (10.0 g, 0.018 mol), 1-Bromo-3,5-di-tert-butylbenzene (5.1 g, 0.022 mol), K ₂ CO ₃ (7.5 g, 0.054 mol), Pd(OAc) ₂ ( _1.0 g, 0.9 mmol), After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 8.6 g of <Compound 37> (yield 67.3%).

LC/MS: m/z=707[(M) ⁺ ]

Synthesis example 3: Synthesis of Compound 62

(One) Manufacturing example 1: Synthesis of intermediate 62-1

2,5-dibromo-p-xylene (10.0 g, 0.038 mol), B-[2-Chloro-5-(1,1-dimethylethyl)phenyl]boronic acid (9.7 g, 0.046 mol), K ₂ CO ₃ ( Toluene 200 mL, EtOH 50 mL, and H ₂ O 50 mL were added to 15.7 g, 0.114 mol) and Pd(PPh ₃ ) ₄ (0.9 g, 0.8 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 6.7 g (yield 50.3%) of <Intermediate 62-1>.

(2) Manufacturing example 2: Synthesis of intermediate 62-2

Intermediate 62-1 (10.0 g, 0.028 mol), 3,5-Bis(trifluoromethyl)phenylboronic acid (8.8 g, 0.034 mol), K ₂ CO ₃ (11.8 g, 0.085 mol), Pd(OAc) ₂ (1.6 g , 1.4 mmol) _, After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 7.5 g of <Intermediate 62-2> (yield 49.8%).

(3) Manufacturing example 3: Synthesis of intermediate 62-3

4-(Trifluoromethyl)aniline (10.0 g, 0.062 mol), 1-Bromo-3,5-bis(trifluoromethyl)benzene (27.3 g, 0.093 mol), NaOtBu (17.9 g, 0.186 mol), Pd(dba) ₂ ( 1.4 g, 2.5 mmol) and t-Bu ₃ P (1.0 g, 5.0 mmol) were mixed with 150 mL of xylene and stirred at 70°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 9.5 g of <Intermediate 62-3> (yield 41.0%).

(4) Manufacturing example 4: Synthesis of Compound 62

Intermediate 62-2 (10.0 g, 0.019 mol), Intermediate 62-3 (10.6 g, 0.028 mol), NaOtBu (5.5 g, 0.057 mol), Pd(dba) ₂ (0.4 g, 0.8 mmol), t-Bu ₃ 150 mL of Xylene was added to P (0.3 g, 1.5 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 8.6 g of <Compound 62> (yield 55.4%).

LC/MS: m/z=821[(M) ⁺ ]

Synthesis example 4: Synthesis of Compound 122

(One) Manufacturing example 1: Synthesis of intermediate 122-1

1,4-dibromo-2,5-dichlorobenzene (10.0 g, 0.033 mol), 2-Pyrrolidinone (6.7 g, 0.079 mol), K ₃ PO ₄ (29.9 g, 0.092 mol), Pd(dba) ₂ (1.9 g , 3.3 mmol), Xant-Phos (13.7 g, 2.4 mmol), and 50 mL of dioxane were added and stirred under reflux for 16 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.2 g (yield 79.8%) of <Intermediate 122-1>.

(2) Manufacturing example 2: Synthesis of intermediate 122-2

1-Bromo-2-chlorobenzene (10.0 g, 0.052 mol), (3,5-dimethylphenyl)boronic acid (9.4 g, 0.063 mol), K ₂ CO ₃ (21.7 g, 0.157 mol), Pd(PPh ₃ ) ₄ (1.2 g, 1.0 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 7.5 g (yield 66.3%) of <Intermediate 122-2>.

(3) Manufacturing example 3: Synthesis of intermediate 122-3

Intermediate 122-2 (10.0 g, 0.046 mol), Bis(pinacolato)diboron (14.1 g, 0.055 mol), CH ₃ COOK (13.6 g, 0.138 mol), Pd(dppf)Cl ₂ (1.7 g, 2.3 mmol), Dioxane was added to XPhos (2.0 g, 4.2 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 10.3 g of <Intermediate 122-3> (yield 72.4%).

(4) Manufacturing example 4: Synthesis of intermediate 122-4

Intermediate 122-1 (10.0 g, 0.032 mol), Intermediate 122-3 (11.8 g, 0.038 mol), K ₂ CO ₃ (13.2 g, 0.096 mol), Pd(OAc) ₂ (1.8 g, 1.6 mmol), -Phos (1.5 g, 3.2 mmol), 200 mL of THF, and 50 mL of H ₂ O were added and stirred at 70°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 122-4> (yield 46.4%).

(5) Manufacturing example 5: Synthesis of Compound 122

Intermediate 122-4 (10.0 g, 0.022 mol), diphenylamine (5.5 g, 0.033 mol), NaOtBu (6.3 g, 0.065 mol), Pd(dba) ₂ (0.5 g, 0.9 mmol), t-Bu ₃ P (0.4 g, 1.7 mmol) and reacted by adding 150 mL of xylene and stirring at 70°C for 4 hours. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 8.1 g of <Compound 122> (yield 62.8%).

LC/MS: m/z=591[(M) ⁺ ]

Example 5: Synthesis of Compound 138

(One) Manufacturing example 1: Synthesis of intermediate 138-1

1,4-dibromo-2,5-bis(1,1-dimethylethyl)benzene (10.0 g, 0.029 mol), 2-Chloro-5-methylphenylboronic acid (5.9 g, 0.035 mol), K ₂ CO ₃ (11.9 g , 0.086 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.6 mmol) were 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 6.3 g (yield 55.7%) of <Intermediate 138-1>.

(2) Manufacturing example 2: Synthesis of intermediate 138-2

Intermediate 138-1 (10.0 g, 0.025 mol), (3,5-di-tert-butylphenyl)boronic acid (7.1 g, 0.031 mol), K ₂ CO ₃ (10.6 g, 0.076 mol), Pd(OAc) ₂ ( _1.5 g, 1.3 mmol), After completion of the reaction, it was extracted, concentrated, and recrystallized with a column to obtain 7.3 g of <Intermediate 138-2> (yield 52.5%).

(3) Manufacturing example 3: Synthesis of Compound 138

Intermediate 138-2 (10.0 g, 0.018 mol), Bis(4-biphenylyl)amine (8.8 g, 0.027 mol), NaOtBu (5.3 g, 0.055 mol), Pd(dba) ₂ (0.4 g, 0.7 mmol), t 150 mL of Xylene was added to -Bu ₃ P (0.3 g, 1.5 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 9.3 g of <Compound 138> (yield 64.6%).

LC/MS: m/z=787[(M) ⁺ ]

Synthesis example 6: Synthesis of Compound 153

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

1,4-dibromo-2,5-ditert-butylbenzene (10.0 g, 0.029 mol), 2-Chlorophenylboronic acid (5.4 g, 0.035 mol), K ₂ CO ₃ (11.9 g, 0.086 mol), Pd(PPh ₃ ) _{To 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 5.8 g (yield 53.2%) of <Intermediate 153-1>.

(2) Manufacturing example 2: Synthesis of intermediate 153-2

Intermediate 153-1 (10.0 g, 0.026 mol), 3,5-Bis(trifluoromethyl)phenylboronic acid (8.2 g, 0.032 mol), K ₂ CO ₃ (10.9 g, 0.079 mol), Pd(OAc) ₂ (1.5 g) , 1.3 mmol) _, After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 6.9 g of <Intermediate 153-2> (yield 47.0%).

(3) Manufacturing example 3: Synthesis of Compound 153

Intermediate 153-2 (10.0 g, 0.018 mol), Bis(4-biphenylyl)amine (8.7 g, 0.027 mol), NaOtBu (5.2 g, 0.054 mol), Pd(dba) ₂ (0.4 g, 0.7 mmol), t 150 mL of Xylene was added to -Bu ₃ 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 9.5 g of <Compound 153> (yield 66.4%).

LC/MS: m/z=797[(M) ⁺ ]

Synthesis example 7: Synthesis of Compound 170

(One) Manufacturing example 1: Synthesis of intermediate 170-1

Intermediate 153-1 (10.0 g, 0.026 mol), 3,5-Dicyclohexylphenylboronic Acid (9.0 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 then recrystallized with a column to obtain 7.9 g of <Intermediate 170-1> (yield 51.2%).

(2) Manufacturing example 2: Synthesis of Compound 170

Intermediate 170-1 (10.0 g, 0.017 mol), Bis(4-biphenylyl)amine (8.2 g, 0.027 mol), NaOtBu (4.9 g, 0.051 mol), Pd(dba) ₂ (0.4 g, 0.7 mmol), t 150 mL of Xylene was added to -Bu ₃ 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 8.7 g of <Compound 170> (yield 61.7%).

LC/MS: m/z=826[(M) ⁺ ]

Synthesis example 8: Synthesis of Compound 195

(One) Manufacturing example 1: Synthesis of intermediate 195-1

2,5-dibromo-p-xylene (10.0 g, 0.038 mol), N-[1,1'-Biphenyl]-4-yl[1,1'-biphenyl]-2-amine (18.3 g, 0.057 mol) , NaOtBu (10.9 g, 0.114 mol), Pd(dba) ₂ (0.9 g, 1.5 mmol), and t-Bu ₃ P (0.6 g, 3.0 mmol) were mixed with 150 mL of I ordered it. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 11.7 g of <Intermediate 195-1> (yield 57.6%).

(2) Manufacturing example 2: Synthesis of intermediate 195-2

Intermediate 195-1 (10.0 g, 0.020 mol), (2-Chloro-5-fluorophenyl)boronic acid (4.2 g, 0.024 mol), K ₂ CO ₃ (8.2 g, 0.060 mol), Pd(PPh ₃ ) ₄ ( 0.5 g, 0.4 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 and concentrated, followed by column and recrystallization to obtain 5.4 g of <Intermediate 195-2> (yield 49.2%).

(3) Manufacturing example 3: Synthesis of Compound 195

Intermediate 195-2 (10.0 g, 0.018 mol), B-[3,5-Bis(1,1-dimethylethyl)phenyl]boronic acid (5.1 g, 0.022 mol), K ₂ CO ₃ (7.5 g, 0.054 mol) _, Pd(OAc) ₂ (1.0 g, 0.9 mmol), After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 5.8 g of <Compound 195> (yield 45.4%).

LC/MS: m/z=707[(M) ⁺ ]

Synthesis example 9: Synthesis of Compound 215

(One) Manufacturing example 1: Synthesis of intermediate 215-1

1,4-Dibromo-2,5-bis(trifluoromethyl)benzene (10.0 g, 0.027 mol), N-[1,1'-Biphenyl]-2-yl[1,1'-biphenyl]-2-amine ( _Add 150 _mL of The reaction was stirred at 70°C. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.1 g (yield 49.2%) of <Intermediate 215-1>.

(2) Manufacturing example 2: Synthesis of intermediate 215-2

Intermediate 215-1 (10.0 g, 0.016 mol), 2-Chloro-5-methylphenylboronic acid (3.3 g, 0.020 mol), K ₂ CO ₃ (6.8 g, 0.049 mol), Pd(PPh ₃ ) ₄ (0.4 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 2.7 g of <Intermediate 215-2> (yield 25.1%).

(3) Manufacturing example 3: Synthesis of Compound 215

Intermediate 215-2 (10.0 g, 0.015 mol), B-[3,5-Bis(1,1-dimethylethyl)phenyl]boronic acid (4.3 g, 0.018 mol), K ₂ CO ₃ (6.3 g, 0.046 mol) _, Pd(OAc) ₂ (0.9 g, 0.8 mmol), After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 6.4 g of <Compound 215> (yield 51.9%).

LC/MS: m/z=811[(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 9

Example compounds 1 to 9 shown in Table 1 below, which implement the organic light emitting device according to the present invention, 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 9 according to the present invention, and optical properties were measured.

Experiment example One : Example Optical properties of compounds 1 to 9

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

division refractive index Blue (450 nm) Green (520 nm) Red (630 nm) Example 1 (Compound 8) 1.83 1.74 1.67 Example 2 (Compound 37) 1.82 1.73 1.65 Example 3 (Compound 62) 1.78 1.68 1.61 Example 4 (Compound 122) 1.79 1.71 1.63 Example 5 (Compound 138) 1.75 1.72 1.68 Example 6 (Compound 153) 1.77 1.69 1.67 Example 7 (Compound 170) 1.80 1.72 1.66 Example 8 (Compound 195) 1.83 1.70 1.64 Example 9 (Compound 215) 1.79 1.73 1.69 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 an embodiment according to the present invention, the ITO transparent electrode is patterned so that the light emitting area is 2 mm × 2 mm using an ITO glass substrate to which the ITO transparent electrode is attached on a glass substrate of 25 mm × 25 mm × 0.7 mm. and then washed. After the substrate was mounted in a vacuum chamber and the base pressure was set to 1 × 10 ^-6 torr, organic materials and metals were deposited on the ITO in the following structure.

device Example 10 to 30

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 10 to 30, 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 10 to 30

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 10 Formula 1 4.25 7.35 0.1370 0.1373 11 Formula 8 4.30 7.29 0.1356 0.1365 12 Formula 21 4.33 7.25 0.1349 0.1382 13 Formula 37 4.28 7.17 0.1346 0.1360 14 Formula 41 4.29 7.34 0.1370 0.1338 15 Formula 49 4.26 7.31 0.1335 0.1352 16 Formula 53 4.31 7.29 0.1326 0.1347 17 Formula 62 4.33 7.26 0.1344 0.1360 18 Formula 71 4.29 7.42 0.1339 0.1356 19 Formula 89 4.35 7.28 0.1328 0.1335 20 Formula 93 4.24 7.31 0.1335 0.1359 21 Formula 122 4.25 7.28 0.1348 0.1330 22 Formula 133 4.32 7.30 0.1356 0.1355 23 Formula 138 4.26 7.29 0.1332 0.1372 24 Formula 142 4.25 7.43 0.1335 0.1368 25 Formula 153 4.29 7.40 0.1341 0.1351 26 Formula 170 4.34 7.29 0.1342 0.1355 27 Formula 183 4.30 7.33 0.1337 0.1361 28 Formula 195 4.31 7.35 0.1348 0.1356 29 Formula 215 4.36 7.30 0.1340 0.1364 30 Formula 229 4.28 7.27 0.1352 0.1358 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 (6)

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 and a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms,
m and n are each integers from 0 to 4 (provided that n+m ≥ 1), and when m and n are each 2 or more, a plurality of R ₁ and R ₂ are the same or different from each other, and R ₁ and R Among _{the 2} , at least one is not hydrogen,
Ar ₁ and Ar ₂ are the same or different from each other, and each independently represents 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 an unsubstituted cycloalkyl group having 3 to 20 carbon atoms, 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,
Ar ₃ and Ar ₄ 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. 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, 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,
[Formula I] is an organic compound selected from the following [Formula 1] to [Formula 232]:


















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 4,
The organic layer includes one or more of an electron injection layer, an electron transport layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, and a light emitting layer,
An organic light-emitting device, wherein at least one of the layers includes an organic compound represented by the formula (I). According to clause 5,
An organic light-emitting device comprising an organic compound represented by [Chemical Formula I] in the hole transport layer.