WO2023136595A1 - Organic compound and organic light emitting device comprising same - Google Patents

Abstract

The present invention is directed to an organic compound employed in an organic layer, such as a hole transport layer, in an organic light emitting device, wherein the organic compound has a lower refractive index than conventional hole transport materials in each of blue, green, and red wavelength bands, so that when a device is configured by employing the organic compound in a hole transport layer, the optimization of efficiency of the organic light emitting device can be expected, and therefore, the employment of the compound according to the present invention in a hole transport layer or the like in a device can implement an organic light emitting device with superb light emission characteristics, such as light-emitting efficiency and quantum efficiency.

Description

Organic compound and organic light emitting device including the same

The present invention relates to a compound used in an organic light emitting device, and more particularly, an organic compound characterized in that it is employed as an organic layer material in an organic light emitting device, and luminous properties such as low voltage driving and excellent luminous efficiency of the device by employing the same It relates to a remarkably improved organic light emitting device.

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

However, in order for the organic light emitting device to exhibit the above characteristics, the materials constituting the organic layer in the device, such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, and electron injection materials, are supported by stable and efficient materials. However, the development of stable and efficient organic layer materials for organic light emitting devices has not yet been sufficiently accomplished.

Therefore, in order to implement a more stable organic light emitting device, and to achieve high efficiency, long lifespan, and large size of the device, further improvement in terms of efficiency and lifespan characteristics is required. In particular, optical properties and The development of new materials capable of further improving light emitting properties is required, and the development of organic layer structures in devices is also continuously required.

In addition, recently, studies for improving the mobility of existing organic materials have been actively conducted for the hole transport layer material in the structure of the organic light emitting device.

Accordingly, an object of the present invention is to provide an organic compound capable of realizing excellent light emitting characteristics such as low voltage driving and improved light emitting efficiency by being employed in an organic layer such as a hole transport layer in an organic light emitting device, and an organic light emitting device including the same.

In order to solve the above problems, the present invention is represented by the following [Formula I], and at least one of A and B is represented by [Structural Formula 1], characterized in that an organic compound and an organic layer such as a hole transport layer in a device Provides an organic light emitting device comprising a.

[Formula I]

[Structural Formula 1]

The characteristic structures of [Formula I] and [Structural Formula 1] and the specific compounds according to the present invention realized thereby and the definitions of A, B, R, L ₁ to L ₃ , Ar ₁ and Ar ₂ will be described later. do.

When the organic compound according to the present invention is employed as a material for an organic layer such as a hole transport layer in an organic light emitting device, it can realize light emitting characteristics such as low voltage driving of the device and excellent light emitting efficiency, and thus can be usefully used in various display devices.

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

The present invention relates to a compound employed in an organic layer in an organic light emitting device capable of achieving light emitting characteristics such as low voltage driving of the device and excellent luminous efficiency, and is structurally composed of dibenzofuran or dibenzo as represented by [Chemical Formula I] It is characterized in that at least one or more of A and B is represented by the following [Structural Formula 1] while introducing an amine group with thiophene as a skeleton and introducing substituents of A and B at the following characteristic positions.

In addition, the organic compound represented by the following [Chemical Formula I] according to the present invention has a lower refractive index than the conventional hole transport material in each of the blue, green, and red wavelength bands (450, 520, and 630 nm), so that it can be used as a hole transport material. When a device is configured by employing it in the transport layer, efficiency optimization of the organic light emitting device can be expected.

[Formula I]

In the above [Formula I],

X is O or S.

A and B 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, provided that at least one of A and B At least one is characterized by being represented by [Structural Formula 1] below.

[Structural Formula 1]

In [Structural Formula 1],

R is hydrogen, heavy hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms , a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 1 to 20 carbon atoms It is selected from an alkylsilyl group of and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms.

s is an integer from 0 to 4, and when s is 2 or more, a plurality of R's are the same as or different from each other.

L ₁ to L ₃ 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 o, p and q is each independently an integer of 0 to 4, and when o, p, and q are 2 or more, respectively, a plurality of L ₁ to L ₃ are the same as or different from each other.

Ar ₁ and Ar ₂ are each independently any one 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 n and m are each 0 to 4 is an integer of , and when n and m are 2 or more, respectively, a plurality of A and B are the same as or different from each other.

In addition, in the compound represented by [Chemical Formula I] according to the present invention, at least one of A and B is characterized in that it is represented by [Structural Formula 1], wherein n + m ≥ 1.

Meanwhile, in the definition of A, B, R, L ₁ to L ₃ , Ar ₁ and Ar ₂ , “substituted or unsubstituted” means A, B, R, L ₁ to L ₃ , Ar ₁ and Ar ₂ is deuterium, a halogen group, a cyano group, an alkyl group, a halogenated alkyl group, a deuterated alkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkoxy group, a halogenated alkoxy group, a deuterated alkoxy group, an amine group, an aryl group, It means that it is substituted with one or two or more substituents selected from the group consisting of a heteroaryl group, an alkylsilyl group, and an arylsilyl group, or is substituted with a substituent in which two or more substituents among the substituents are connected, or does not have any substituent.

For example, a substituted aryl group means that a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, and the like are substituted with other substituents. do.

In addition, the substituted heteroaryl group refers to a pyridyl group, a thiophenyl group, a triazine group, a quinoline group, a phenanthroline group, an imidazole group, a thiazole group, an oxazole group, a carbazole group, and condensed heterocyclic groups thereof, such as a benzquinoline group. , It means that a benzimidazole group, a benzoxazole group, a benzthiazole group, a benzcarbazole group, a dibenzothiophenyl group, a dibenzofuran group, and the like are substituted with other substituents.

In addition, the substituted heteroaryl group refers to a pyridyl group, a thiophenyl group, a triazine group, a quinoline group, a phenanthroline group, an imidazole group, a thiazole group, an oxazole group, a carbazole group, and condensed heterocyclic groups thereof, such as a benzquinoline group. , It means that a benzimidazole group, a benzoxazole group, a benzthiazole group, a benzcarbazole group, a dibenzothiophenyl group, a dibenzofuran group, and the like are substituted with other substituents.

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

In the present invention, the alkyl group may be straight 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 and the like, but is not limited thereto.

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 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.

Further, in the present invention, the alkyl group or alkoxy group may be a deuterium or alkoxy group substituted with deuterium or/and a halogen group, or a halogenated alkyl or alkoxy 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, and also includes a polycyclic aryl group structure in which cycloalkyl or the like is fused, and a monocyclic aryl group Examples of include a phenyl group, a biphenyl group, a terphenyl group, a stilbene group, and the like, and examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a tetracenyl group, and a chrysenyl group. , fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthrene group, etc., but the scope of the present invention is not limited only to these examples.

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 preferably has 2 to 30 carbon atoms, and is a polycyclic group in which cycloalkyl or heterocycloalkyl is fused. It includes a heteroaryl group structure, and specific examples thereof in the present invention include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, and a bipyridyl group. , pyrimidyl group, triazine group, triazole group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl 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., and specific examples of such a silyl group include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxy phenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl, and the like, but are not limited thereto.

Specific examples of the substituent halogen group used in the present invention include fluorine (F), chlorine (Cl), and bromine (Br).

In the present invention, the cycloalkyl group refers to and includes monocyclic, polycyclic and spiroalkyl radicals, preferably containing ring carbon atoms of 3 to 20 carbon atoms, cyclopropyl, cyclopentyl, cyclohexyl, bicyclo heptyl, spirodecyl, spirundecyl, adamantyl, and the like, 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, one or more heteroatoms being O, S, N, P, B, Si and Se, It is preferably selected from O, N, or S, and specifically, when N is included, it may be aziridine, pyrrolidine, piperidine, azepane, azocan, and the like.

In the present invention, the amine group may be -NH ₂ , an alkylamine group, an arylamine group, an arylheteroarylamine group, etc., the arylamine group refers to an amine substituted with an aryl, and the alkylamine group refers to an amine substituted with an alkyl. The arylheteroarylamine group refers to an amine substituted with aryl and heteroaryl groups, and examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted diarylamine group. There is an unsubstituted triarylamine group, and the aryl group and heteroaryl group in the arylamine group and the arylheteroarylamine group may be a monocyclic aryl group or a monocyclic heteroaryl group, or may be a polycyclic aryl group or a polycyclic heteroaryl group. And, the aryl group and heteroaryl group including two or more arylamine groups and arylheteroarylamine groups are monocyclic aryl groups (heteroaryl groups), polycyclic aryl groups (heteroaryl groups), or monocyclic aryl groups (heteroaryl groups). aryl group) and polycyclic aryl group (heteroaryl group) may be included at the same time. In addition, the aryl group and heteroaryl group of the arylamine group and the arylheteroarylamine group may be selected from examples of the aryl group and heteroaryl group described above.

The organic compound according to the present invention represented by [Formula I] can be used in various organic layers in an organic light emitting device due to its structural specificity, and can be preferably used in a hole transport layer.

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 thereto.

As described above, the organic compound according to the present invention can synthesize organic compounds having various properties by using a characteristic backbone that exhibits unique properties and a moiety having unique properties introduced thereto, and as a result The organic compound according to the present invention can be applied to various organic layer materials such as a light emitting layer, a hole transport layer, an electron transport layer, an electron blocking layer, and a hole blocking layer. can make it

In addition, the compound of the present invention can be applied to a device according to a general organic light emitting device manufacturing method, and an organic light emitting device according to an embodiment of the present invention includes a first electrode and a second electrode and an organic layer disposed therebetween. It can be made of a structure, and can be manufactured using conventional device manufacturing methods and materials, except that the organic compound according to the present invention is used in the organic layer of the device.

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 include 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 the like, and a structure including a light efficiency improvement layer (capping layer) provided in an organic light emitting device. However, it is not limited thereto and may include fewer or more organic layers.

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

In addition, the organic light emitting device according to the present invention uses a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form a metal or conductive metal oxide or an alloy thereof on a substrate. It can be manufactured by depositing 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 may be manufactured 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 light emitting layer and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic layer can be formed by using various polymer materials and using a solvent process rather than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. Can be made in layers.

As the anode material, a material having a high work function is generally preferred so that holes can be smoothly injected into the organic layer. Specific examples of the anode material 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) , but conductive polymers such as polypyrrole and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function so as to easily inject electrons into the organic layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof, and multilayers such as LiF/Al or LiO ₂ /Al. structural materials, etc., but are not limited thereto.

The hole injection material is a material capable of receiving holes well from the anode at a low voltage, and the hole injection material preferably has a highest occupied molecular orbital (HOMO) between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high hole mobility is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts. can be further improved.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having 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, benzoxazoles, benzthiazoles, and Examples include benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, and rubrene, but are not limited thereto.

As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Specific examples include Al complexes of 8-hydroxyquinoline, complexes containing Alq ₃ organic radical compounds, hydroxyflavone-metal complexes, etc., but are not limited thereto.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are intended to explain 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 spirit of the present invention. It will be self-evident to those who have knowledge.

synthesis example 1: Synthesis of Compound 25

(One) manufacturing example 1: synthesis of intermediate 25-1

1-Bromo-3-iodo-2-methoxybenzene (10.0 g, 0.032 mol), 3-bromo-4-chloro-2-fluorophenylboronic acid (9.7 g, 0.038 mol), K ₂ CO ₃ (13.3 g, 0.096 mol) 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O were added to Pd(PPh ₃ ) ₄ (0.7 g, 0.0006 mol), followed by stirring at 100 °C for 6 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 8.5 g of <Intermediate 25-1> (yield: 67.4%).

(2) manufacturing example 2: synthesis of intermediate 25-2

Intermediate 25-1 (10.0 g, 0.025 mol) was dissolved in anhydrous DCM, and BBr ₃ (in DCM) (15.9 g, 0.063 mol) was added dropwise at 0 °C. The mixture was stirred and reacted at room temperature for 16 hours. After completion of the reaction, after extraction and concentration, 7.1 g (yield 73.6%) of <Intermediate 25-2> was obtained by column.

(3) manufacturing example 3: synthesis of intermediate 25-3

500 mL of NMP was added to Intermediate 25-2 (10.0 g, 0.026 mol) and K ₂ CO ₃ (9.1 g, 0.066 mol), followed by stirring at 180 °C for 24 hours. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 4.8 g of <Intermediate 25-3> (yield: 50.7%).

(4) manufacturing example 4: synthesis of intermediate 25-4

Intermediate 25-3 (10.0 g, 0.028 mol), 3-Pyridylboronic acid (8.2 g, 0.067 mol), K ₂ CO ₃ (23.0 g, 0.167 mol), Pd(PPh ₃ ) ₄ (0.6 g, 0.0006 mol) 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O were added and reacted by stirring at 100 °C for 6 hours. After completion of the reaction, 6.2 g (yield: 62.6%) of <Intermediate 25-4> was obtained by extraction and concentration, followed by column and recrystallization.

(5) manufacturing example 5: synthesis of compound 25

Intermediate 25-4 (10.0 g, 0.028 mol), N-[1,1'-Biphenyl]-4-yl-9,9-dimethyl-9H-fluoren-2-amine (15.2 g, 0.042 mol), NaOtBu ( Toluene 150 mL was added to 8.1 g, 0.084 mol), Pd(dba) ₂ (0.6 g, 0.001 mol), and t-Bu ₃ P (0.5 g, 0.002 mol), followed by stirring at 70 °C for 4 hours. After completion of the reaction, 11.3 g (yield: 59.1%) of <Compound 25> was obtained by extraction, concentration, column and recrystallization.

LC/MS: m/z=681 [(M) ⁺ ]

synthesis example 2: synthesis of compound 27

(One) manufacturing example 1: Synthesis of Compound 27

Intermediate 25-4 (10.0 g, 0.028 mol), N-(9,9-Dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluoren-2-amine (16.9 g, 0.042 mol) , NaOtBu (8.1 g, 0.084 mol), Pd (dba) ₂ (0.6 g, 0.001 mol), and t-Bu ₃ P (0.5 g, 0.002 mol) were added with 150 mL of Toluene and stirred at 70 °C for 4 hours to react. made it After completion of the reaction, 10.8 g (yield: 53.4%) of <Compound 27> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=721 [(M) ⁺ ]

synthesis example 3: Synthesis of Compound 42

(One) manufacturing example 1: synthesis of intermediate 42-1

Intermediate 25-3 (10.0 g, 0.028 mol), B-[4-(3-Pyridinyl)phenyl]boronic acid (13.3 g, 0.067 mol), K ₂ CO ₃ (23.0 g, 0.067 mol), Pd (PPh ₃ ) ₄ (0.6 g, 0.0006 mol) was added with 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours. After completion of the reaction, 7.5 g (yield: 53.1%) of <Intermediate 42-1> was obtained by extraction, concentration, column and recrystallization.

(2) manufacturing example 2: Synthesis of Compound 42

Intermediate 42-1 (10.0 g, 0.020 mol), N-[1,1'-Biphenyl]-4-yl-9,9-dimethyl-9H-fluoren-2-amine (10.7 g, 0.030 mol), NaOtBu ( Toluene (150 mL) was added to 5.7 g, 0.059 mol), Pd(dba) ₂ (0.5 g, 0.0008 mol), and t-Bu ₃ P (0.3 g, 0.002 mol), followed by stirring at 70 °C for 4 hours. After completion of the reaction, 8.1 g (yield 49.4%) of <Compound 42> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=834 [(M) ⁺ ]

synthesis example 4: Synthesis of Compound 118

(One) manufacturing example 1: synthesis of intermediate 118-1

1-Bromo-3-iodo-2-methoxybenzene (10.0 g, 0.032 mol), (3-bromo-5-chloro-2-fluorophenyl)boronic acid (9.7 g, 0.038 mol), K ₂ CO ₃ (13.3 g, 0.096 mol) and Pd(PPh ₃ ) ₄ (0.7 g, 0.0006 mol) were added with 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours. After completion of the reaction, the mixture was extracted, concentrated, and columnized to obtain 7.2 g of <Intermediate 118-1> (yield: 57.1%).

(2) manufacturing example 2: synthesis of intermediate 118-2

Intermediate 118-1 (10.0 g, 0.025 mol) was dissolved in anhydrous DCM, and BBr ₃ (in DCM) (15.9 g, 0.063 mol) was added dropwise at 0 °C. The mixture was stirred and reacted at room temperature for 16 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 8.1 g of <Intermediate 118-2> (yield: 84.0%).

(3) manufacturing example 3: synthesis of intermediate 118-3

500 mL of NMP was added to Intermediate 118-2 (10.0 g, 0.026 mol) and K ₂ CO ₃ (9.1 g, 0.066 mol), followed by stirring at 180 °C for 24 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columnized to obtain 5.4 g of <Intermediate 118-3> (yield: 57.0%).

(4) manufacturing example 4: synthesis of intermediate 118-4

Intermediate 118-3 (10.0 g, 0.028 mol), (6-(2-(trifluoromethyl)phenyl)pyridin-3-yl)boronic acid (17.8 g, 0.067 mol), K ₂ CO ₃ (23.0 g, 0.167 mol) 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O were added to Pd(PPh ₃ ) ₄ (0.6 g, 0.0006 mol), followed by stirring at 100 °C for 6 hours. After completion of the reaction, 11.8 g (yield 65.9%) of <Intermediate 118-4> was obtained by extraction and concentration, followed by column and recrystallization.

(5) manufacturing example 5: Synthesis of Compound 118

Intermediate 118-4 (10.0 g, 0.016 mol), Bis(4-biphenylyl)amine (7.5 g, 0.023 mol), NaOtBu (4.5 g, 0.047 mol), Pd(dba) ₂ (0.4 g, 0.0006 mol), t Toluene 150 mL was added to -Bu ₃ P (0.3 g, 0.001 mol) and reacted by stirring at 70 °C for 4 hours. After completion of the reaction, the mixture was extracted, concentrated, and recrystallized with a column to obtain 7.7 g of <Compound 118> (yield: 53.4%).

LC/MS: m/z=929 [(M) ⁺ ]

synthesis example 5: Synthesis of Compound 152

(One) manufacturing example 1: synthesis of intermediate 152-1

Intermediate 118-2 (10.0 g, 0.028 mol), B-(3,5-Di-3-pyridinylphenyl)boronic acid (18.4 g, 0.067 mol), K ₂ CO ₃ (23.0 g, 0.167 mol), Pd (PPh) ₃ ) 200 mL of Toluene, 50 mL of EtOH, and 50 mL of H ₂ O were added to ₄ (0.6 g, 0.0006 mol), followed by stirring at 100 °C for 6 hours. After completion of the reaction, 10.2 g (yield: 55.4%) of <Intermediate 152-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) manufacturing example 2: Synthesis of compound 152

Intermediate 152-1 (10.0 g, 0.015 mol), Bis(4-biphenylyl)amine (7.3 g, 0.045 mol), NaOtBu (4.4 g, 0.045 mol), Pd(dba) ₂ (0.4 g, 0.0006 mol), t Toluene 150 mL was added to -Bu ₃ P (0.2 g, 0.001 mol) and reacted by stirring at 70 °C for 4 hours. After completion of the reaction, 6.8 g (yield: 47.6%) of <Compound 152> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=948 [(M) ⁺ ]

Experimental example 1: optical properties of the compound according to the present invention

For Experimental Example 1 according to the present invention, quartz glass having a size of 25 mm × 25 mm was cleaned. Thereafter, when the base pressure was 1 × 10 ^-6 torr or more after mounting in a vacuum chamber, the compound according to the present invention and the comparative compound were deposited on a glass substrate, respectively, and optical properties were measured.

device Example 1 to 5

100 nm of Example Compounds 1 to 5 embodying the organic light emitting device according to the present invention was deposited on a glass substrate, respectively, and the refractive index was measured.

Quartz glass / Organic (100 nm)

comparative example One

The substrate for Comparative Example 1 was manufactured in the same manner except for using [α-NPB] instead of Example Compounds 1 to 5, and optical properties were measured.

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

Refractive indices were measured using Ellipsometry (Elli-SE) for the substrates prepared using the compounds of Examples and Comparative Examples. The refractive index was measured in each wavelength region of blue (450 nm), green (520 nm), and red (630 nm), and the results are shown in [Table 1].

division	refractive index
	Blue (450 nm)	green (520 nm)	red (630 nm)
Example 1 (Compound 25)	1.84	1.79	1.69
Example 2 (Compound 27)	1.83	1.76	1.67
Example 3 (Compound 42)	1.79	1.72	1.66
Example 4 (Compound 118)	1.81	1.74	1.68
Example 5 (Compound 152)	1.85	1.81	1.76
Comparative Example 1 (α-NPB)	1.92	1.84	1.78

As such, the Example compound according to the present invention has a refractive index value significantly lower than that of Comparative Example 1 compound (α-NPB) in each wavelength range (450, 520, 630 nm), and the compound according to the present invention having a low refractive index value When employed in the hole transport layer, optimization of device efficiency can be expected.

[α-NPB]

device Example ( HTL )

In an example according to the present invention, the anode was patterned to have a light emitting area of 2 mm × 2 mm using an ITO glass substrate containing Ag of 25 mm × 25 mm × 0.7 mm, and then washed. After mounting the patterned ITO substrate in a vacuum chamber, an organic material and a metal were deposited on the substrate at a process pressure of 1 × 10 ^-6 torr or more in the following structure.

device Example 6 to 33

After employing the compound implemented according to the present invention as a hole transport layer and fabricating an organic light emitting device having the following device structure, emission and driving characteristics of the compound implemented according to the present invention were measured.

Ag/ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (60 nm) / electron blocking layer (EB1, 10 nm) / light emitting layer (20 nm) / electron transport layer (ET1:Liq, 30 nm) / LiF (1 nm) / Mg:Ag (15nm) / light efficiency improvement layer (70 nm)

After forming a hole injection layer by depositing [HAT-CN] to a thickness of 5 nm on the top of an ITO transparent electrode containing Ag on a glass substrate, the compound according to the present invention described in [Table 2] is deposited to a thickness of 60 nm. Thus, a hole transport layer was formed, and [EB1] was formed to a thickness of 10 nm to form an electron blocking layer. The light emitting layer was formed by co-evaporation to a thickness of 20 nm using [BH1] as a host compound and [BD1] as a dopant compound. Thereafter, an electron transport layer (the [ET1] compound Liq 50% doped) was deposited to a thickness of 30 nm, and then LiF was deposited to a thickness of 1 nm to form an electron injection layer. Thereafter, a film of 15 nm in thickness was formed with Mg:Ag at a ratio of 1:9 to form a cathode. And Alq ₃ as a capping layer compound An organic light emitting device was fabricated by forming a film of the compound to a thickness of 70 nm.

device comparative example 2

The organic light emitting device for Device Comparative Example 2 was manufactured in the same manner as in the device structures of Examples 6 to 33, except that the following [α-NPB] was used instead of the compound according to the present invention in the hole transport layer.

Experimental example 2: device Example Luminescence characteristics of 6 to 33

Driving voltage, current efficiency and color coordinates were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research) for the organic light emitting device manufactured according to the above Examples and Comparative Examples, 1,000 nit The standard result values are shown in [Table 2] below.

Example	hole transport layer	V	cd/A	CIEx	CIEy
6	Formula 3	3.84	8.14	0.1353	0.0538
7	Formula 18	3.73	8.10	0.1341	0.0569
8	Formula 21	3.82	8.28	0.1354	0.0512
9	Formula 25	3.66	8.16	0.1339	0.0526
10	Formula 27	3.80	8.21	0.1348	0.0531
11	Formula 33	3.64	8.27	0.1366	0.0503
12	Formula 42	3.71	8.23	0.1371	0.0481
13	Formula 55	3.63	8.19	0.1369	0.0489
14	Formula 71	3.82	8.28	0.1372	0.0550
15	Formula 89	3.76	8.11	0.1356	0.0561
16	Formula 97	3.91	8.25	0.1367	0.0533
17	Formula 101	3.86	8.19	0.1368	0.0513
18	Formula 118	3.87	8.02	0.1347	0.0533
19	Formula 129	3.95	8.17	0.1351	0.0541
20	Formula 131	3.84	8.20	0.1343	0.0563
21	Formula 137	3.70	8.23	0.1379	0.0531
22	Formula 143	3.82	8.29	0.1373	0.0526
23	Formula 152	3.65	7.98	0.1376	0.0528
24	Formula 197	3.68	8.13	0.1380	0.0554
25	Formula 203	3.74	8.21	0.1371	0.0561
26	Formula 218	3.86	8.17	0.1363	0.0540
27	Formula 230	3.91	8.24	0.1372	0.0525
28	Formula 241	3.74	7.95	0.1362	0.0496
29	Formula 267	3.82	8.03	0.1354	0.0554
30	Formula 274	3.79	8.18	0.1359	0.0578
31	Formula 301	3.80	8.21	0.1343	0.0569
32	Formula 322	3.91	8.13	0.1343	0.0592
33	Formula 348	3.88	8.29	0.1348	0.0586
Comparative Example 2	α-NPB	4.33	7.84	0.1471	0.0583

Looking at the results shown in [Table 2], in the case of the organic light emitting device employing the compound according to the present invention in the hole transport layer in the device, the organic light emitting device employing the compound widely used as a conventional hole transport material (Comparative Example 2) In comparison, it can be seen that the driving voltage is reduced and the current efficiency is improved.

As confirmed in [Table 1], it can be clearly seen that the luminous efficiency is optimized and improved as the refractive index of the organic compound according to the present invention is significantly lower than that of the comparative compound used as the conventional hole transport material.

[HAT-CN] [α-NPB] [BH1] [BD1] [ET1]

[EB1]

The present invention is an organic compound characterized in that it is employed as an organic layer material in an organic light emitting device, and the compound according to the present invention has a lower refractive index than a conventional hole transport material in each of the blue, green, and red wavelength bands. In the case of constructing a device by employing it in the hole transport layer, improved low-voltage driving characteristics as well as optimization of luminous efficiency can be expected, so that it can be industrially useful for various lighting devices and display devices.

Claims (6)

1. A compound represented by the following [Formula I]:

   [Formula I]

   

   In the above [Formula I],

   X is O or S;

   A and B are the same as or different from each other, and are each independently any one 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,

   At least one of A and B is characterized in that it is represented by [Structural Formula 1]

   [Structural Formula 1]

   

   In [Structural Formula 1],

   R is hydrogen, heavy hydrogen, a cyano group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms , a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 1 to 20 carbon atoms Any one selected from an alkylsilyl group and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms,

   s is an integer from 0 to 4, and when s is 2 or more, a plurality of R's are the same as or different from each other,

   L ₁ to L ₃ 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;

   o, p, and q are each independently an integer of 0 to 4, and when o, p, and q are each 2 or more, a plurality of L ₁ to L ₃ are the same as or different from each other,

   Ar ₁ and Ar ₂ are each independently any one 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;

   n and m are each an integer from 0 to 4 (n+m ≥ 1), and when n and m are each 2 or more, a plurality of A and B are the same as or different from each other.
2. According to claim 1,

   In the definition of A, B, R, L ₁ to L ₃ , Ar ₁ and Ar ₂ , 'substituted or unsubstituted' refers to A, B, R, L ₁ to L ₃ , Ar ₁ and Ar ₂ are each deuterium, halogen group, cyano group, alkyl group, halogenated alkyl group, deuterated alkyl group, cycloalkyl group, heterocycloalkyl group, alkoxy group, halogenated alkoxy group, deuterated alkoxy group, amine group, aryl group, heteroaryl group A compound characterized in that it is substituted with one or two or more substituents selected from the group consisting of a group, an alkylsilyl group, and an arylsilyl group, or is substituted with a substituent in which two or more substituents among the substituents are connected, or does not have any substituents.
3. According to claim 1,

   [Formula I] is a compound characterized in that any one selected from the following [Compound 1] to [Compound 356]:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
4. 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,

   At least one layer of the organic layer is an organic light emitting device that includes a compound represented by [Chemical Formula I] according to claim 1.
5. According to claim 4,

   The organic layer is selected from a hole injection layer, a hole transport layer, a layer that simultaneously performs hole injection and hole transport functions, an electron transport layer, an electron injection layer, a layer that simultaneously performs electron transport and electron injection functions, an electron blocking layer, a hole blocking layer, and a light emitting layer. Including one or more floors,

   An organic light emitting device, wherein at least one of the layers includes the compound represented by [Chemical Formula I].
6. According to claim 5,

   An organic light emitting device comprising the compound represented by [Chemical Formula I] in any one of the hole transport layer, the hole injection layer, and the hole transport and hole injection layers.