KR20240002995A - Organic compound and electroluminescent device comprising the same - Google Patents

Abstract

The present invention is an organic compound represented by the following [Chemical Formula I], and when it is used in an organic layer, preferably an electron blocking layer, in an organic light-emitting device, an organic light-emitting device with excellent luminous properties such as luminous efficiency and quantum efficiency can be realized. possible.
[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 electron blocking layers in organic light-emitting devices, and to organic light-emitting devices whose device characteristics, such as low-voltage operation, long life, and luminous efficiency, are significantly improved by employing the same. It's about.

Organic light emitting devices not only can be formed on transparent substrates, but also can be driven at low voltages of 10 V or less compared to plasma display panels or inorganic electroluminescence (EL) displays, and consume relatively little power. , It has the advantage of excellent color and can display three colors of green, blue, and red, so it has recently been the subject of much attention as a next-generation display device.

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

Therefore, there is a continued need for the development of new materials that can improve luminescence characteristics and the development of organic layer structures within devices.

Therefore, the present invention aims to provide an organic compound that can be used as an organic layer material such as an electron blocking layer in an organic light-emitting device to significantly improve device characteristics such as low-voltage driving characteristics, long life, and luminous efficiency, and an organic light-emitting device containing the same. do.

In order to solve the above problems, the present invention provides an organic compound represented by the following [Chemical Formula I] and an organic light-emitting device containing the same.

[Formula Ⅰ]

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

The organic light-emitting device employing the organic compound according to the present invention in an organic layer such as an electron blocking layer is significantly superior to conventional devices in device characteristics such as low-voltage operation, long lifespan, and luminous efficiency, and can be usefully used in various lighting devices and display devices. You can.

Hereinafter, the present invention will be described in more detail.

The present invention relates to an organic compound represented by the following [Chemical Formula I], which structurally has a skeleton of [Formula I] and a characteristic moiety represented by [Structural Formula 1] to [Structural Formula 3] at the A ₁ and A ₂ positions. It is characterized by the introduction of an organic light-emitting device that has significantly improved device characteristics such as low-voltage driving, long life, and luminous efficiency when applied to various organic layers in the organic light-emitting device, preferably the electron blocking layer, due to these structural features. This is possible.

[Formula Ⅰ]

In the above [Chemical Formula I],

X ₁ and X ₂ are the same as or different from each other, and are each independently O, S, NR ₁ or CR ₂ R ₃ .

R ₁ to R ₃ are the same or different from each other, and each independently represents hydrogen, deuterium, cyano group, halogen group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms. , a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

Additionally, R ₂ and R ₃ may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring.

A ₁ and A ₂ are the same as or different from each other, and are each independently selected from [Structural Formula 1] to [Structural Formula 3] below.

[Structural Formula 1]

[Structural Formula 2]

[Structural Formula 3]

In [Structural Formula 1] to [Structural Formula 3],

L ₁ to L ₃ are the same or different from each other, and are each independently a direct bond or selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, and n is an integer from 0 to 3, and when n is 2 or more, a plurality of L ₁ to L ₃ are the same or different from each other.

L ₄ to L ₇ are the same or different from each other, and are each independently a direct bond or selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, m is an integer from 0 to 3, and when m is 2 or more, a plurality of L ₄ to L ₇ are the same or different from each other.

Ar ₁ to Ar ₆ are the same or different from each other, and are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, and p and q are each It is an integer from 0 to 3, and when p and q are each 2 or more, a plurality of Ar ₁ to Ar ₆ are the same or different from each other.

In [Structural Formula 3], m+p ≥ 1 and m+q ≥ 1.

Meanwhile, in the definitions of R ₁ to R ₃ , L ₁ to L ₇ and Ar ₁ to Ar ₆ , ‘substituted or unsubstituted’ refers to R ₁ to R ₅ , L ₁ to L ₇ and Ar ₁ to Ar ₆ each has one or two or more substituents selected from the group consisting of deuterium, halogen group, cyano group, nitro group, hydroxy group, alkyl group, cycloalkyl group, heterocycloalkyl group, alkoxy group, aryl group, heteroaryl group, amine group, and silyl group. It means that it is substituted with a substituent, or is substituted with a substituent in which two or more of the above substituents are linked, or does not have any substituent.

For specific examples, a substituted aryl group refers to a phenyl group, biphenyl group, naphthalene group, fluorenyl group, pyrenyl group, phenanthrenyl group, perylene group, tetracenyl group, anthracenyl group, etc. substituted with another substituent such as deuterium. means, and substituted heteroaryl group refers to pyridyl group, thiophenyl group, triazine group, quinoline group, phenanthroline group, imidazole group, thiazole group, oxazole group, carbazole group and condensed heterocyclic groups thereof, such as This means that benzquinoline group, benzimidazole group, benzoxazole group, benzthiazole group, benzcarbazole group, dibenzothiophenyl group, dibenzofuran group, etc. are also substituted with other substituents such as deuterium.

In the present invention, examples of the above substituents will be described in detail below, but are not limited thereto.

In the present invention, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but is not limited to these.

In the present invention, the alkoxy group may be straight chain or branched chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20, which is within a range that does not cause steric hindrance. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, i-propyloxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group. , neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group , benzyloxy group, p-methylbenzyloxy group, etc., but is not limited thereto.

In the present invention, 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, electron blocking of the organic layer depending on the characteristics of various substituents introduced. It can be used as a material for layers, etc.

Preferred specific examples of the compound represented by [Chemical Formula I] according to the present invention include the following compounds, but are not limited to these.

Through the above-mentioned characteristic skeletal structure and substituents, organic compounds with unique properties of the skeletal structure and substituents can be synthesized. For example, when manufacturing an organic light-emitting device, an organic compound material that satisfies the conditions required for each organic layer can be manufactured. In particular, when the compound of [Chemical Formula I] according to the present invention is used in the electron blocking layer, etc., device characteristics such as luminous efficiency of the device can be further improved.

The organic compound according to the present invention can be applied to an organic light-emitting device according to a conventional manufacturing method.

The organic light emitting device according to an embodiment of the present invention may have a structure including a first electrode, a second electrode, and an organic layer disposed between them, except that the organic compound according to the present invention is used in the organic layer of the device. It can be manufactured using conventional device manufacturing methods and materials.

The organic layer of the organic light emitting device according to the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, etc. However, it is not limited to this and may include fewer or more organic layers.

As such, the organic light emitting device according to an embodiment of the present invention may include a hole injection layer, a hole transport layer, a light emitting layer, etc. formed on an anode, and may also include a hole blocking layer, an electron injection layer, an electron transport layer, an electron blocking layer, It may include a light emitting auxiliary layer, etc., but is not limited thereto.

Therefore, in the organic light emitting device according to the present invention, the organic layer may include an electron blocking layer, etc., and one or more of the layers may include the organic compound represented by [Chemical Formula I].

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

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

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

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

The hole injection layer is a material that can easily receive holes from the anode at a low voltage, and it is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene, quinacridone-based organic substances, perylene-based organic substances, Examples include anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited to these.

The hole transport layer is a material that can transport holes from the anode or hole injection layer and transfer them to the light emitting layer, and a material with high mobility for holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions, but are not limited to these.

The electron blocking layer is a layer that blocks the movement of electrons and can be formed on the hole transport layer. An electron blocking layer that can block the movement of electrons without affecting the transport of holes can be used. Additionally, a light-emitting layer may be formed on the electron blocking layer, and a hole blocking layer, an electron transport layer, and an electron injection layer may be formed.

The hole blocking layer can be used to prevent the movement of holes without affecting the transport of electrons. An example of such a hole blocking layer is TPBi(1,3,5-tri(1-phenyl-1H-benzo). [d]imidazol-2-yl)phenyl), BCP(2,9-dimethyl4,7-diphenyl-1,10-phenanthroline), CBP(4,4-bis(N-carbazolyl)-1,1'-biphenyl) ), PBD(2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole), PTCBI(bisbenzimidazo[2,1-a:1',2-b']anthra [2,1,9-def:6,5,10-d'e'f']diisoguinoline-10,21-dione) or BPhen (4,7-diphenyl-1,10-phenanthroline), etc. It is not limited.

The light-emitting layer is a material that can emit light in the visible light range by transporting holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining them, and a material with good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole, and Examples include benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, and rubrene, but are not limited to these.

The electron injection layer can be one that has high injection efficiency of electrons transferred from the cathode. Examples of such electron injection layers include, but are not limited to, lithium quinolate (Liq).

The electron transport layer is a material that can easily receive electrons from the cathode and transfer them to the light emitting layer, and a material with high electron mobility is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline, a complex containing Alq ₃ , an organic radical compound, and a hydroxyflavone-metal complex.

The organic light emitting device according to the present invention may be a front emitting type, a 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

4-Bromo-6-chlorodibenzofuran (10.0 g, 0.036 mol), Bis(pinacolato)diboron (10.8 g, 0.043 mol), KOAc (10.5 g, 0.107 mol), Pd(dppf)Cl ₂ (1.3 g, 0.002 mol) Add 200 mL of dioxane and stir at 100°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 7.8 g (yield 66.8%) of <Intermediate 1-1>.

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

Toluene to Intermediate 1-1 (10.0 g, 0.030 mol), 2-Bromoanisole (6.8 g, 0.037 mol), K ₂ CO ₃ (12.6 g, 0.091 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.6 mmol) 200 mL, 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 6.2 g (yield 66.0%) of <Intermediate 1-2>.

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

Intermediate 1-2 (10.0 g, 0.032 mol) is dissolved in 60 mL of Anhydrous DCM. Afterwards, BBr ₃ (in DCM, 20.3 g, 0.081 mol) was added dropwise while maintaining the temperature at 0°C and stirred at 25°C for 16 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.1 g of <Intermediate 1-3> (yield 84.9%).

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

Intermediate 1-3 (10.0 g, 0.034 mol), Pd(OAc) ₂ (0.8 g, 0.003 mol), and 3-nitropyridine (0.4 g, 0.003 mol) were dissolved in C ₆ F ₆ (150 mL) and DMI, tert-butyl peroxybenzoate (13.2 g, 0.068 mol) was added and stirred at 90°C for reaction. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.9 g (yield 69.5%) of <Intermediate 1-4>.

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

Intermediate 1-4 (10.0 g, 0.034 mol) was dissolved in 100 mL of CHCl ₃ , and then bromine (in CHCl ₃ , 13.6 g, 0.085 mol) was slowly added dropwise and stirred at room temperature for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 7.1 g (yield 55.9%) of <Intermediate 1-5>.

(6) Manufacturing example 6: Synthesis of intermediates 1-6

Toluene in Intermediate 1-5 (10.0 g, 0.027 mol), Phenyl Boronic Acid (3.9 g, 0.032 mol), K ₂ CO ₃ (11.2 g, 0.081 mol), Pd(PPh ₃ ) ₄ (0.6 g, 0.5 mmol) 200 mL, 50 mL of EtOH, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 6.1 g of <Intermediate 1-6> (yield 61.5%).

(7) Manufacturing example 7: Synthesis of Compound 1

Intermediate 1-6 (10.0 g, 0.026 mol), (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid (13.7 g, 0.031 mol), K ₂ CO ₃ ( 10.7 g, 0.078 mol), Pd ₍ OAc) ₂ (1.5 g, 0.001 mol), reacted. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 13.5 g of <Compound 1> (yield 71.6%).

LC/MS: m/z=729[(M) ⁺ ]

Synthesis example 2: Synthesis of Compound 6

(One) Manufacturing example 1: Synthesis of intermediate 6-1

Intermediate 1-6 (10.0 g, 0.027 mol), Bis(pinacolato)diboron (18.7 g, 0.033 mol), CH ₃ COOK (5.3 g, 0.054 mol), Pd(dppf)Cl ₂ (0.6 g, 0.0008 mol), Dioxane was added to XPhos (0.5 g, 0.001 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 72.9%) of <Intermediate 6-1>.

(2) Manufacturing example 2: Synthesis of intermediate 6-2

Intermediate 6-1 (10.0 g, 0.022 mol), 1-Bromo-4-iodobenzene (7.4 g, 0.026 mol), K ₂ CO ₃ (9.0 g, 0.065 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, concentrated, and then recrystallized with a column to obtain 6.2 g of <Intermediate 6-2> (yield 58.3%).

(3) Manufacturing example 3: Synthesis of Compound 6

Intermediate 6-2 (10.0 g, 0.020 mol), N-[1,1'-Biphenyl]-4-yl-3-dibenzofuranamine (10.3 g, 0.031 mol), NaOtBu (5.9 g, 0.061 mol), Pd(dba ) ₂ (0.5 g, 0.8 mmol) and t-Bu ₃ P (0.3 g, 1.6 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 9.8 g of <Compound 6> (yield 64.5%).

LC/MS: m/z=743[(M) ⁺ ]

Synthesis example 3: Synthesis of Compound 22

(One) Manufacturing example 1: Synthesis of Compound 22

Intermediate 6-1 (10.0 g, 0.022 mol), 2,2'-(5-Bromo-1,3-phenylene)bis[9,9-dimethyl-9H-fluorene (14.1 g, 0.026 mol), K ₂ CO _{Toluene 3} (9.0 g, 0.065 mol) and Pd(PPh ₃ ) ₄ (0.5 g, 0.4 mmol) were added 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 12.2 g of <Compound 22> (yield 70.6%).

LC/MS: m/z=794[(M) ⁺ ]

Synthesis example 4: Synthesis of Compound 40

(One) Manufacturing example 1: Synthesis of Compound 40

Intermediate 6-2 (10.0 g, 0.020 mol), N-([1,1'-biphenyl]-2-yl)-[1,1':3',1"-terphenyl]-5'-amine (12.2 _Add 150 _mL of The reaction was stirred at ° C. After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 9.2 g of <Compound 40> (yield 55.9%).

LC/MS: m/z=805[(M) ⁺ ]

Synthesis example 5: Synthesis of Compound 67

(One) Manufacturing example 1: Synthesis of intermediate 67-1

(6-phenyldibenzo[b,d]furan-4-yl)boronic acid (10.0 g, 0.035 mol), Methyl 2-bromobenzoate (8.8 g, 0.042 mol), K ₂ CO ₃ (14.4 g, 0.104 mol), Pd Toluene (PPh ₃ ) ₄ (0.8 g, 0.7 mmol) was added with 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O, and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.1 g of <Intermediate 67-1> (yield 61.7%).

(2) Manufacturing example 2: Synthesis of intermediate 67-2

Intermediate 67-1 (10.0 g, 0.026 mol) was dissolved in THF and then lowered to 0°C. Afterwards, 26.4 mL of MeMgBr (3 M, in diethyl ether) was added dropwise and stirred at room temperature for 16 hours. When the reaction was completed, NH ₄ Cl solution was added dropwise, concentrated, and then proceeded with the next reaction.

(3) Manufacturing example 3: Synthesis of intermediate 67-3

Intermediate 67-2 (10.0 g, 0.026 mol) was added to 150 mL of AcOH and stirred at 0 °C for 30 minutes. Afterwards, 15 mL of HCl was slowly added dropwise and stirred at 120°C for 2 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 7.5 g of <Intermediate 67-3> (yield 78.8%).

(4) Manufacturing example 4: Synthesis of intermediate 67-4

After dissolving Intermediate 67-3 in 100 mL of CHCl ₃ , bromine (in CHCl ₃ , 11.1 g, 0.069 mol) was slowly added dropwise and stirred at room temperature for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 6.4 g of <Intermediate 67-4> (yield 52.5%).

(5) Manufacturing example 5: Synthesis of Compound 67

Intermediate 67-4 (10.0 g, 0.023 mol), Bis(4-biphenylyl)amine (11.0 g, 0.034 mol), NaOtBu (6.6 g, 0.068 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 recrystallized using a column to obtain 11.2 g of <Compound 67> (yield 72.4%).

LC/MS: m/z=679[(M) ⁺ ]

device Example ( EBL )

In an embodiment according to the present invention, the ITO transparent electrode is patterned so that the light emitting area is 2 mm × 2 mm using an ITO glass substrate to which the ITO transparent electrode is attached on a glass substrate of 25 mm × 25 mm × 0.7 mm. and then washed. After the substrate was mounted in a vacuum chamber and the base pressure was set to 1 × 10 ^-6 torr, organic materials and metals were deposited on the ITO in the following structure.

device Example 1 to 21

After manufacturing an organic light emitting device having the following device structure by employing the compound implemented according to the present invention as an electron blocking layer in the device, the compound implemented according to the present invention and the organic light emitting device using the same as the electron blocking layer are manufactured. The light emission and driving characteristics of were measured.

ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (α-NPB, 100 nm) / electron blocking layer (10 nm) / emitting layer (20 nm) / electron transport layer (ET1:Liq, 30 nm) / LiF (1 nm) / Al (100 nm)

[HAT-CN] was deposited to a thickness of 5 nm on the top of the ITO transparent electrode to form a hole injection layer, and then α-NPB was deposited to a thickness of 100 nm to form a hole transport layer. Afterwards, the compound according to the present invention shown in [Table 1] below was deposited to a thickness of 10 nm to form an electron blocking layer, and the light emitting layer was formed at a thickness of 20 nm using [BH1] as the host compound and [BD1] as the dopant compound. It was formed by vapor deposition. Afterwards, 30 nm of an electron transport layer (50% doped with [ET1] compound Liq below) was deposited, and then LiF was deposited to a thickness of 1 nm to form an electron injection layer. Afterwards, an organic light emitting device was manufactured by forming Al into a film with a thickness of 100 nm.

device Comparative example One

The organic light emitting device for Device Comparative Example 1 was manufactured in the same manner as the device structures of Examples 1 to 21 except that [EB1] was used instead of the compound according to the present invention in the electron blocking layer.

device Comparative example 2

The organic light emitting device for Device Comparative Example 2 was manufactured in the same manner as the device structures of Examples 1 to 21, except that [EB2] was used instead of the compound according to the present invention in the electron blocking layer.

device Comparative example 3

The organic light emitting device for Comparative Device Example 3 was manufactured in the same manner as the device structures of Examples 1 to 21 except that [EB3] was used instead of the compound according to the present invention in the electron blocking layer.

device Comparative example 4

The organic light emitting device for Device Comparative Example 4 was manufactured in the same manner as the device structures of Examples 1 to 21 except that [EB4] was used instead of the compound according to the present invention in the electron blocking layer.

Experiment example 1: element Example Luminous properties from 1 to 21

The driving voltage, current efficiency, and color coordinates of the organic light emitting devices manufactured according to the above examples and comparative examples were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and were measured at 1,000 nit. The standard result values are shown in [Table 1] below.

Example electronic low layer V cd/A CIEx CIey One Formula 1 4.01 7.62 0.1359 0.1343 2 Formula 2 4.19 7.52 0.1364 0.1336 3 Formula 3 3.94 7.67 0.1339 0.1362 4 Formula 4 4.08 7.61 0.1338 0.1361 5 Formula 6 3.93 7.72 0.1349 0.1353 6 Formula 9 4.11 7.39 0.1325 0.1379 7 Formula 15 3.93 7.96 0.1349 0.1354 8 Formula 16 4.28 7.54 0.1327 0.1376 9 Formula 20 4.15 7.36 0.1326 0.1377 10 Formula 22 4.13 7.70 0.1315 0.1389 11 Formula 24 3.74 7.62 0.1343 0.1358 12 Formula 30 3.86 7.65 0.1312 0.1395 13 Formula 34 4.32 7.58 0.1314 0.1388 14 Formula 36 4.15 7.44 0.1315 0.1392 15 Formula 40 4.24 7.85 0.1324 0.1381 16 Formula 48 3.78 7.76 0.1327 0.1375 17 Formula 57 4.07 7.41 0.1358 0.1347 18 Formula 59 3.88 7.90 0.1327 0.1385 19 Formula 65 4.03 7.79 0.1305 0.1393 20 Formula 67 3.91 7.86 0.1304 0.1399 21 Formula 69 4.10 7.50 0.1351 0.1366 Comparative Example 1 EB1 4.67 6.65 0.1353 0.1517 Comparative Example 2 EB2 4.57 6.62 0.1310 0.1390 Comparative Example 3 EB3 4.42 6.57 0.1314 0.1383 Comparative Example 4 EB4 4.45 6.51 0.1322 0.1374

Looking at the results shown in [Table 1], when the compound according to the present invention is employed in the electron blocking layer in an organic light-emitting device, the characteristic structure of the compound according to the present invention as a compound used as a conventional electron blocking layer material is compared. It can be seen that the low-voltage driving characteristics and light-emitting characteristics are significantly superior to those of devices employing the compound (Comparative Examples 1 to 4).

[HAT-CN] [α-NPB] [BH1] [BD1] [ET1]

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

Claims (6)

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

In the above [Chemical Formula I],
X ₁ and X ₂ are the same as or different from each other, and are each independently O, S, NR ₁ or CR ₂ R ₃ ,
R ₁ to R ₃ are the same or different from each other, and each independently represents hydrogen, deuterium, cyano group, halogen group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms. , a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms,
R ₂ and R ₃ may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring,
A ₁ and A ₂ are the same or different from each other, and are each independently selected from [Structural Formula 1] to [Structural Formula 3],
[Structural Formula 1]

[Structural Formula 2]

[Structural Formula 3]

In [Structural Formula 1] to [Structural Formula 3],
L ₁ to L ₃ are the same or different from each other, and are each independently a direct bond or selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, and n is an integer from 0 to 3, and when n is 2 or more, a plurality of L ₁ to L ₃ are the same or different from each other,
L ₄ to L ₇ are the same or different from each other, and are each independently a direct bond or selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, m is an integer from 0 to 3, and when m is 2 or more, a plurality of L ₄ to L ₇ are the same or different from each other,
Ar ₁ to Ar ₆ are the same or different from each other, and are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, and p and q are each is an integer from 0 to 3, and when p and q are each 2 or more, a plurality of Ar ₁ to Ar ₆ are the same or different from each other,
In [Structural Formula 3], m+p ≥ 1 and m+q ≥ 1. According to paragraph 1,
In the definition of R ₁ to R ₃ , L ₁ to L ₇ and Ar ₁ to Ar ₆ , ‘substituted or unsubstituted’ refers to R ₁ to R ₅ , L ₁ to L ₇ and Ar ₁ to Ar ₆ is each substituted with one or two or more substituents selected from the group consisting of deuterium, halogen group, cyano group, nitro group, hydroxy group, alkyl group, cycloalkyl group, heterocycloalkyl group, alkoxy group, aryl group, heteroaryl group, amine group and silyl group. Or, an organic compound meaning that two or more of the above substituents are substituted with a linked substituent, or that it does not have any substituents. According to paragraph 1,
[Formula I] is an organic compound selected from the following [Formula 1] to [Formula 69]:





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