KR20230160979A - Organic compound and electroluminescent device comprising the same - Google Patents

Abstract

The present invention provides a novel organic compound represented by the following [Chemical Formula I], which can be used as an organic layer material such as a light-emitting layer and an electron blocking layer in an organic light-emitting device to realize excellent light-emitting properties such as luminous efficiency and quantum efficiency, and an organic compound containing the same. We would like to provide a light emitting device.
[Formula Ⅰ]

Description

Organic compound and electroluminescent device comprising the same}

The present invention relates to organic compounds, and more specifically, organic compounds that are used as organic layer materials such as light-emitting layers, electron blocking layers, or electron transport layers in organic light-emitting devices according to the structural characteristics of the compounds, and luminous efficiency and quantum efficiency by employing them. It relates to an organic light-emitting device with significantly improved luminescence characteristics, such as:

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 such an organic light emitting device to exhibit the above characteristics, the materials that make up the organic layers in the device, such as a hole injection layer, hole transport layer, hole blocking layer, light emitting layer host and dopant, electron blocking layer, electron transport layer, electron injection layer, etc. This should be supported by stable and efficient materials, but the development of stable and efficient organic layer materials for organic light-emitting devices has not yet been sufficiently developed.

Therefore, in order to implement more stable organic light-emitting devices and achieve higher efficiency, longer lifespan, and enlargement of devices, additional improvements in terms of efficiency and lifespan characteristics are required. In particular, development of materials forming each organic layer of organic light-emitting devices is required. It is desperately needed.

Therefore, the present invention provides a novel organic compound that can be used as an organic layer material such as a light-emitting layer, an electron blocking layer, or an electron transport layer in an organic light-emitting device to realize excellent light-emitting properties such as luminous efficiency and quantum efficiency, and an organic light-emitting device containing the same. We would like to provide

In order to solve the above problems, the present invention provides an organic compound selected from compounds represented by the following [Chemical Formula I].

[Formula Ⅰ]

The characteristic structure of [Chemical Formula I] and the specific compounds realized thereby and the definitions of X ₁ , X ₂ , R ₁ , R ₂ , A ₁ to A ₃ will be described later.

The organic compound according to the present invention can be used as an electron blocking layer or electron transport layer material or a light emitting layer host material in an organic light emitting device to realize excellent light emitting properties such as luminous efficiency and quantum efficiency of the device, and can be utilized in various 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, due to its structural characteristics, is employed as an electron blocking layer or electron transport layer material in an organic light-emitting device, or as a light-emitting layer host, and exhibits excellent device characteristics such as luminous efficiency and quantum efficiency. It is possible to implement an organic light emitting device having

[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 ₃ or CR ₄ R ₅ .

R ₁ to R ₅ are each independently selected from deuterium, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

R ₁ and R ₂ and R ₄ and R ₅ may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring.

Any one of A ₁ to A ₃ is characterized in that it is selected from the following [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 n 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.

According to one embodiment of the present invention, the compound represented by [Chemical Formula I] may be represented by the following [Chemical Formula I-1] in which either X ₁ or X ₂ is NR ₃ .

[Formula Ⅰ-1]

_In the [Formula _I - _{1 ] ,} 1], R ₃ may be a substituted or unsubstituted aryl group.

In addition, according to one embodiment of the present invention, L ₁ to L ₃ may each be a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and thus structures according to [Structural Formula 1] to [Structural Formula 3] When introduced into the skeleton structure in A ₁ to A ₃ , a characteristic moiety is bonded through a substituted or unsubstituted arylene linking group such as phenylene, biphenylene, or naphthylene.

Meanwhile, in the definition of R ₁ to R ₅ , 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, substituted aryl group means that phenyl group, biphenyl group, naphthalene group, fluorenyl group, pyrenyl group, phenanthrenyl group, perylene group, tetracenyl group, anthracenyl group, etc. are substituted with other substituents. do.

In the present invention, examples of the above substituents will be described in detail as follows, 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 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, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, Dibenzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, phenoxazine group, phenothiazine group, etc., but only these It is not limited.

In the present invention, the silyl group is an unsubstituted silyl group or a silyl group substituted with an alkyl group, an aryl group, etc. Specific examples of such silyl groups include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, and dimethoxysilyl. Examples include phenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl, etc., but are not limited thereto.

In the present invention, the amine group may be -NH ₂ , an alkylamine group, an arylamine group, etc., an arylamine group refers to an amine substituted with aryl, an alkylamine group refers to an amine substituted with alkyl, and an arylamine group refers to an amine substituted with alkyl. Examples of include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group, and the aryl group in the arylamine group is the same as the definition of the aryl group. , the alkyl group of the alkylamine group is also the same as the definition of the alkyl group.

Specific examples of the halogen group, which is a substituent 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. , preferably selected from O, N or S, and specifically, when it contains N, it may be aziridine, pyrrolidine, piperidine, azepane, azocan, etc.

The organic compound according to the present invention represented by [Formula I] can be used as an organic layer of an organic light-emitting device due to its structural specificity, and more specifically, it can be used as a material such as an electron blocking layer, an electron transport layer, and a light-emitting layer host in the organic layer. You can.

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

In this way, the organic compound according to the present invention can synthesize organic compounds with various properties through a characteristic skeletal structure with unique properties and a moiety with unique properties introduced thereto, and as a result, the present invention When the organic compound according to the invention is applied to various organic layer materials such as an electron transport layer, an electron blocking layer, and a light emitting layer, the luminous properties such as the luminous efficiency of the device can be further improved.

Additionally, the compounds of the present invention can be applied to devices according to general organic light-emitting device manufacturing methods.

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. Then, 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, a hole blocking layer, and, if necessary, a light efficiency improvement layer (capping layer). However, it is not limited to this and may include fewer or more organic layers.

The organic layer structure of the preferred organic light emitting device according to the present invention will be described in more detail in the examples described later.

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. It can be manufactured by depositing to form an anode, forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.

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

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

The hole injection material is a material that can easily inject holes from the anode at a low voltage. It is preferable that the highest occupied molecular orbital (HOMO) 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 materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Examples include anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited to these.

The hole transport material is a material that can transport holes from the anode or hole injection layer and transfer them to the light emitting layer, and a material with high mobility for holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions.

The light-emitting material is a material that can emit light in the visible range by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining them, and a material with good quantum efficiency for fluorescence or phosphorescence is preferred. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole, and These include benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, and rubrene.

The electron transport material is a material that can easily inject electrons from the cathode and transfer them to the light-emitting layer, and a material with high mobility for electrons is suitable. Specific examples include Al complex of 8-hydroxyquinoline, complex containing Alq ₃ , organic radical compound, hydroxyflavone-metal complex, etc.

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, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for illustrating the present invention in more detail, and the scope of the present invention is not limited thereto, and various changes and modifications are possible within the scope and technical idea of the present invention as is known in the art. It will be self-evident to those with knowledge.

Synthesis example 1: Synthesis of Compound 1

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

dibenzo[b,d]furan-1-ylboronic acid (10.0 g, 0.047 mol), Methyl 2-bromo-3-nitrobenzoate (14.7 g, 0.057 mol), K ₂ CO ₃ (19.6 g, 0.142 mol), Pd ( Toluene 200 mL, EtOH 50 mL, and H ₂ O 50 mL were added to PPh ₃ ) ₄ (1.1 g, 0.9 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 10.5 g of <Intermediate 1-1> (yield 64.1%).

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

Intermediate 1-1 (10.0 g, 0.029 mol), PPh ₃ (18.9 g, 0.072 mol), and dichlorobenzene were added and stirred under reflux for 5 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.8 g of <Intermediate 1-2> (yield 74.9%).

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

DMF was added to Intermediate 1-2 (10.0 g, 0.032 mol), Fluorobenzene (3.7 g, 0.038 mol), and Cs ₂ CO ₃ (6.6 g, 0.048 mol), and the mixture was refluxed and stirred for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.1 g (yield 65.3%) of <Intermediate 1-3>.

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

Intermediate 1-3 (10.0 g, 0.026 mol) was dissolved in THF and then lowered to 0°C. Afterwards, 25.5 mL of MeMgBr (3 M, in diethyl ether) was added dropwise and stirred at room temperature for 16 hours. When the reaction was completed, the NH ₄ Cl solution was added dropwise, concentrated, and the next reaction was performed with the obtained <Intermediate 1-4>.

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

Intermediate 1-4 (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 H ₂ SO ₄ was slowly added dropwise and stirred again at room temperature for 1 hour to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 7.5 g (yield 78.6%) of <Intermediate 1-5>.

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

Intermediate 1-5 (10.0 g, 0.027 mol) and N-Bromosuccinimide (5.7 g, 0.032 mol) were added to DMF and stirred for 5 hours at room temperature for reaction. After the reaction was completed, extracted, concentrated, and columnized, <Intermediate 1- 6> was obtained in 7.6 g (yield 62.8%).

(7) Manufacturing example 7: Synthesis of intermediates 1-7

Intermediate 1-6 (10.0 g, 0.022 mol), Bis(pinacolato)diboron (6.7 g, 0.027 mol), KOAc (6.5 g, 0.066 mol), Pd(dppf)Cl ₂ (0.8 g, 0.001 mol) in dioxane 200 mL was added and stirred at 100°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 8.1 g of <Intermediate 1-7> (yield 73.4%).

(8) Manufacturing example 8: Synthesis of Compound 1

Intermediate 1-7 (10.0 g, 0.020 mol), N-[1,1'-biphenyl]-4-yl-N-(4-bromophenyl)[1,1'-biphenyl]-4-amine (11.5 g, Add 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O to 0.024 mol), K ₂ CO ₃ (8.3 g, 0.060 mol), and Pd(PPh ₃ ) ₄ (0.5 g, 0.4 mmol) and incubate at 80°C for 6 hours. The reaction was stirred. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 10.8 g of <Compound 1> (yield 70.1%).

LC/MS: m/z=768[(M) ⁺ ]

Synthesis example 2: Synthesis of Compound 7

(One) Manufacturing example 1: Synthesis of intermediate 7-1

Intermediate 1-7 (10.0 g, 0.020 mol), 1-Bromo-4-iodobenzene (6.8 g, 0.024 mol), K ₂ CO ₃ (8.3 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, concentrated, and then recrystallized with a column to obtain 7.1 g of <Intermediate 7-1> (yield 67.1%).

(2) Manufacturing example 2: Synthesis of Compound 7

Intermediate 7-1 (10.0 g, 0.019 mol), 3-Dibenzofuranamine, N-1[1,1-biphenyl]-4-yl (9.5 g, 0.028 mol), NaOtBu (5.5 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 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 10.2 g of <Compound 7> (yield 68.9%).

LC/MS: m/z=782[(M) ⁺ ]

Synthesis example 3: Synthesis of Compound 22

(One) Manufacturing example 1: Synthesis of Compound 22

Intermediate 7-1 (10.0 g, 0.019 mol), 3,5-diphenylphenylboronic Acid (6.2 g, 0.023 mol), K ₂ CO ₃ (7.9 g, 0.057 mol), Pd(PPh ₃ ) ₄ (0.4 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 9.5 g of <Compound 22> (yield 74.1%).

LC/MS: m/z=677[(M) ⁺ ]

Synthesis example 4: Synthesis of compound 27

(One) Manufacturing example 1: Synthesis of intermediate 27-1

Intermediate 1-7 (10.0 g, 0.020 mol), 1-Bromo-3-iodobenzene (6.8 g, 0.024 mol), K ₂ CO ₃ (8.3 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, concentrated, and then recrystallized with a column to obtain 7.1 g of <Intermediate 27-1> (yield 67.1%).

(2) Manufacturing example 2: Synthesis of Compound 27

Intermediate 27-1 (10.0 g, 0.019 mol), Bis(4-biphenylyl)amine (9.1 g, 0.028 mol), NaOtBu (5.5 g, 0.057 mol), Pd(dba) ₂ (0.4 g, 0.8 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 9.6 g of <Compound 27> (yield 66.0%).

LC/MS: m/z=768[(M) ⁺ ]

Synthesis example 5: Synthesis of Compound 41

(One) Manufacturing example 1: Synthesis of intermediate 41-1

(9-phenyl-9H-carbazol-4-yl)boronic acid (10.0 g, 0.035 mol), Methyl 2-bromo-3-nitrobenzoate (10.9 g, 0.042 mol), K ₂ CO ₃ (14.4 g, 0.105 mol) , 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O were added to Pd(PPh ₃ ) ₄ (0.8 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 9.5 g of <Intermediate 41-1> (yield 64.6%).

(2) Manufacturing example 2: Synthesis of intermediate 41-2

Intermediate 41-1 (10.0 g, 0.024 mol), PPh ₃ (15.5 g, 0.059 mol), and 350 mL of dichlorobenzene were added and stirred under reflux for 5 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.2 g (yield 67.1%) of <Intermediate 41-2>.

(3) Manufacturing example 3: Synthesis of intermediate 41-3

DMF was added to Intermediate 41-2 (10.0 g, 0.026 mol), Fluorobenzene (3.0 g, 0.031 mol), and Cs ₂ CO ₃ (5.3 g, 0.038 mol), and the mixture was refluxed and stirred for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 7.8 g (yield 65.3%) of <Intermediate 41-3>.

(4) Manufacturing example 4: Synthesis of intermediate 41-4

Intermediate 41-3 (10.0 g, 0.021 mol) was dissolved in THF and then lowered to 0°C. Afterwards, 21.4 mL of MeMgBr (3 M, in diethyl ether) was added dropwise and stirred at room temperature for 16 hours. When the reaction was completed, the NH ₄ Cl solution was added dropwise, concentrated, and the next reaction was performed with the obtained <Intermediate 41-4>.

(5) Manufacturing example 5: Synthesis of intermediate 41-5

Intermediate 41-4 (10.0 g, 0.021 mol) was added to 150 mL of AcOH and stirred at 0 °C for 30 minutes. Afterwards, 15 mL of H ₂ SO ₄ was slowly added dropwise, and the reaction was stirred at room temperature again for 1 hour. After the reaction was completed, the reaction was extracted, concentrated, and columnarized to obtain 7.5 g (yield 78.0%) of <Intermediate 41-5>. .

(6) Manufacturing example 6: Synthesis of intermediate 41-6

Intermediate 41-5 (10.0 g, 0.022 mol) and N-Bromosuccinimide (4.8 g, 0.027 mol) were added to 200 mL of DMF and stirred at room temperature for 5 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 5.6 g of <Intermediate 41-6> (yield 47.6%).

(7) Manufacturing example 7: Synthesis of Compound 41

Intermediate 41-6 (10.0 g, 0.019 mol), (4-(di([1,1'-biphenyl]-4-yl)amino)phenyl)boronic acid (10.0 g, 0.023 mol), K ₂ CO ₃ ( Toluene 200 mL, EtOH 50 mL, and H ₂ O 50 mL were added to 7.9 g, 0.057 mol) and Pd(PPh ₃ ) ₄ (0.4 g, 0.4 mmol) 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 41> (yield 76.2%).

LC/MS: m/z=843[(M) ⁺ ]

Synthesis example 6: Synthesis of Compound 51

(One) Manufacturing example 1: Synthesis of Compound 51

Intermediate 1-7 (10.0 g, 0.020 mol), 2-Chloro-4,6-diphenyl-1,3,5-triazine (6.4 g, 0.024 mol), K ₂ CO ₃ (8.3 g, 0.060 mol), Pd (PPh ₃ ) ₄ (0.5 g, 0.4 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 9.6 g of <Compound 51> (yield 79.3%).

LC/MS: m/z=604[(M) ⁺ ]

Synthesis example 7: Synthesis of Compound 62

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

Toluene 200 in cyanuric chloride (10.0 g, 0.054 mol), 4-Cyanophenylboronic acid (19.1 g, 0.130 mol), K ₂ CO ₃ (45.0 g, 0.325 mol), Pd(PPh ₃ ) ₄ (1.3 g, 1.1 mmol) 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 10.2 g (yield 59.2%) of <Intermediate 62-1>.

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

Intermediate 27-1 (10.0 g, 0.019 mol), Bis(pinacolato)diboron (5.8 g, 0.023 mol), KOAc (5.6 g, 0.057 mol), Pd(dppf)Cl ₂ (0.7 g, 0.0009 mol) dioxane 200 mL was added and stirred at 100°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 8.2 g of <Intermediate 62-2> (yield 75.3%).

(3) Manufacturing example 3: Synthesis of Compound 62

Intermediate 62-2 (10.0 g, 0.017 mol), Intermediate 62-1 (6.6 g, 0.021 mol), K ₂ CO ₃ (7.2 g, 0.052 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 9.8 g of <Compound 62> (yield 77.2%).

LC/MS: m/z=730[(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 39

The compound implemented according to the present invention was employed in the electron blocking layer to manufacture an organic light-emitting device having the following device structure, and then the light emission and driving characteristics of the compound implemented according to the present invention 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)

After forming a hole injection layer by depositing [HAT-CN] to a thickness of 5 nm on the top of the ITO transparent electrode, α-NPB was deposited to a thickness of 100 nm to form a hole transport layer, and then the present invention described in [Table 1] below The compound according to 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, and then an electron transport layer (see below [ ET1] After depositing 30 nm of compound Liq (50% doped), 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 39, except that [EB1] 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 39

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

Example electronic low layer V cd/A CIEx CIey One Compound 1 4.01 7.62 0.1359 0.1343 2 compound 2 4.19 7.52 0.1364 0.1336 3 Compound 3 3.94 7.67 0.1339 0.1362 4 Compound 4 4.08 7.61 0.1338 0.1361 5 Compound 5 3.93 7.72 0.1349 0.1353 6 Compound 6 4.11 7.39 0.1325 0.1379 7 Compound 7 3.93 7.96 0.1349 0.1354 8 Compound 8 4.28 7.54 0.1327 0.1376 9 Compound 9 4.15 7.36 0.1326 0.1377 10 Compound 10 4.13 7.70 0.1315 0.1389 11 Compound 11 3.74 7.62 0.1343 0.1358 12 Compound 12 3.86 7.65 0.1312 0.1395 13 Compound 13 4.32 7.58 0.1314 0.1388 14 Compound 14 4.15 7.44 0.1315 0.1392 15 Compound 15 4.24 7.85 0.1324 0.1381 16 Compound 16 3.78 7.76 0.1327 0.1375 17 Compound 17 4.07 7.41 0.1358 0.1347 18 Compound 18 3.88 7.90 0.1327 0.1385 19 Compound 19 4.03 7.79 0.1305 0.1393 20 Compound 20 3.91 7.86 0.1304 0.1399 21 Compound 21 4.10 7.50 0.1351 0.1366 22 Compound 22 3.89 7.77 0.1304 0.1394 23 Compound 24 4.02 7.43 0.1318 0.1385 24 Compound 25 4.21 7.62 0.1305 0.1398 25 Compound 27 4.09 7.83 0.1308 0.1396 26 Compound 28 3.97 7.97 0.1311 0.1396 27 Compound 30 3.84 7.68 0.1321 0.1385 28 Compound 35 3.78 7.85 0.1337 0.1366 29 Compound 36 3.96 7.78 0.1339 0.1365 30 Compound 37 4.25 7.43 0.1340 0.1366 31 Compound 38 3.90 7.84 0.1324 0.1379 32 Compound 39 4.04 7.63 0.1314 0.1388 33 Compound 40 3.89 7.50 0.1329 0.1375 34 Compound 41 3.97 7.86 0.1323 0.1387 35 Compound 42 4.05 7.63 0.1343 0.1359 36 Compound 43 3.79 7.61 0.1312 0.1394 37 Compound 45 3.92 7.74 0.1326 0.1378 38 Compound 46 4.18 7.93 0.1324 0.1371 39 Compound 47 3.86 7.41 0.1347 0.1357 Comparative Example 1 EB1 4.67 6.65 0.1353 0.1517

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 confirmed that the low-voltage driving characteristics and luminous efficiency characteristics are significantly superior to those of the device employing the compound (Comparative Example 1).

[HAT-CN] [α-NPB] [BH1] [BD1] [ET1]

[EB1]

Claims (10)

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 ₃ or CR ₄ R ₅ ,
R ₁ to R ₅ are each independently selected from deuterium, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,
R ₁ and R ₂ and R ₄ and R ₅ may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring,
Any one of A ₁ to A ₃ is selected from [Structural Formula 1] to [Structural Formula 3] below, and the remainder is hydrogen,
[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 any one 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 any one 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
m is an integer from 0 to 3, and when n 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,
p and q are each integers 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. According to paragraph 1,
Wherein X ₁ is NR ₃ and R ₃ is a substituted or unsubstituted aryl group. According to paragraph 1,
The organic compound wherein L ₁ to L ₃ are each a substituted or unsubstituted arylene group having 6 to 30 carbon atoms. According to paragraph 1,
In the definitions of R ₁ to R ₅ , 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 [Compound 1] to [Compound 75]:







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 an organic compound of [Chemical Formula I] according to claim 1. According to clause 6,
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). In clause 7,
An organic light-emitting device comprising an organic compound represented by [Chemical Formula I] in the electron transport layer. In clause 7,
An organic light-emitting device comprising an organic compound represented by [Chemical Formula I] in the electron blocking layer. In clause 7,
An organic light-emitting device comprising an organic compound represented by [Chemical Formula I] in the light-emitting layer.