KR102394381B1 - Novel hole injecting· hole-transporting compound and organic electroluminescent device comprising same - Google Patents

Abstract

The hole injection and hole transport compound of the present invention has a HOMO energy level that facilitates hole injection, has a high LUMO energy level that can block electrons, has excellent hole transport characteristics, and is a hole injection layer or a hole transport layer in an organic light emitting device It can have excellent low voltage, high efficiency, high Tg stability and long lifespan when applied to

Description

Novel hole injection and hole transport compound and organic light emitting device including the same {NOVEL HOLE INJECTING HOLE-TRANSPORTING COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING SAME}

The present invention relates to a novel hole injection and hole transport compound and an organic light emitting device comprising the same.

Recently, the organic light emitting device capable of low voltage driving as a self-emitting type has excellent viewing angle and contrast ratio, and does not require a backlight, compared to a liquid crystal display (LCD), which is the mainstream of flat panel display devices. It is also advantageous in terms of power consumption and has a wide color reproduction range, attracting attention as a next-generation display device.

A material used as an organic layer in an organic light emitting device may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to a function.

Until now, many amine derivatives having a carbazole skeleton have been studied for hole injection and hole transport materials used in such organic light emitting devices, but there were many difficulties in commercialization due to higher driving voltage, low efficiency and short lifespan. Accordingly, efforts have been made to develop an organic light emitting diode having low voltage driving, high luminance, and long lifespan using a material having excellent properties.

In order to solve the above problems, the present invention has a HOMO energy level that facilitates hole injection, has a high LUMO energy level that can block electrons, has excellent hole transport characteristics, and provides a hole injection layer or An object of the present invention is to provide a novel compound capable of having excellent low voltage, high efficiency, high Tg stability and long lifespan when applied to a hole transport layer.

The present invention also aims to provide an organic light emitting device having improved hole injection and hole transport properties, including the above compound, having electron blocking properties, excellent low voltage, high efficiency, and stability and long lifespan due to high Tg. .

In order to achieve the above object, the present invention provides a hole injection / hole transport compound represented by the following formula (1):

[Formula 1]

In the above formula,

each X is independently O, S, Se or Te;

Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, A C _6-50 aryl group unsubstituted or substituted with a C _1-30 alkoxy group, a C _6-30 aryloxy group, a C _6-30 aryl group, or a C _2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryl An oxy group, a C _6-30 aryl group, or a C _2-30 heteroaryl group substituted or unsubstituted C _2-50 heteroaryl group, wherein Ar ₂ and Ar ₃ may be connected to each other,

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro; C _2-30 alkenyl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _1-30 alkoxy group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, or nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-50 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group,

n is 1 or 2,

*- is a binding site.

In addition, the present invention provides an organic light emitting device comprising the compound represented by the formula (1).

The hole injection and hole transport compound of the present invention has a HOMO energy level that facilitates hole injection, has a high LUMO energy level that can block electrons, has excellent hole transport characteristics, and is a hole injection layer or hole transport layer of an organic light emitting device. It can have excellent low voltage, high efficiency, high Tg stability and long lifespan when applied to

1 schematically shows a cross-section of an OLED according to an embodiment of the present invention.
drawing sign
10: substrate
11: positive electrode
12: hole injection layer
13: hole transport layer
14: light emitting layer
15: electron transport layer
16: cathode

The compound of the present invention is characterized in that it is represented by the following formula (1).

[Formula 1]

In the above formula,

each X is independently O, S, Se or Te;

Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, A C _6-50 aryl group unsubstituted or substituted with a C _1-30 alkoxy group, a C _6-30 aryloxy group, a C _6-30 aryl group, or a C _2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryl An oxy group, a C _6-30 aryl group, or a C _2-30 heteroaryl group substituted or unsubstituted C _2-50 heteroaryl group, wherein Ar ₂ and Ar ₃ may be connected to each other,

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro; C _2-30 alkenyl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _1-30 alkoxy group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, or nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-50 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group,

n is 1 or 2,

*- is a binding site.

In the present invention, the compound represented by Formula 1 may be one of those represented by Formulas 2 to 4 below.

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4, X, Ar ₁ , Ar ₃ , Ar ₄ , R ₁ and R ₂ are as defined in Formula 1, and R ₃ and R ₄ are each independently defined as R ₁ and R ₂ in Formula 1 same as

In the present invention, preferred examples of the compound represented by Formula 1 are as follows:

The compound of Formula 1 according to the present invention has a HOMO energy level that facilitates hole injection, has a high LUMO energy level that can block electrons, has excellent hole transport properties, and has excellent low voltage when applied to a hole transport layer in an organic light emitting device. , high efficiency, stability and long life due to high Tg.

In addition, the compound of the present invention can be prepared through the reaction scheme represented by the following Scheme 1:

[Scheme 1]

In the above scheme, in Formula 2 or 3, X, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , R ₁ , R ₂ and n are as defined in Formula 1, and R is R ₁ or R ₂ .

In addition, the present invention provides an organic light emitting device comprising the compound represented by Formula 1 in an organic material layer. In this case, the compound of the present invention is preferably used alone as a hole injection material or a hole transport material, or may be used together with a known process injection material or a hole transport compound.

In addition, since the organic light emitting device of the present invention includes one or more organic material layers including the compound represented by Formula 1, a method for manufacturing the organic light emitting device will be described as follows.

The organic light emitting device includes an organic material layer such as a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL) between an anode and a cathode. It may contain more than one.

First, an anode is formed by depositing a material for an anode electrode having a high work function on a substrate. In this case, as the substrate, a substrate used in a conventional organic light emitting device may be used, and in particular, it is preferable to use a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness. In addition, transparent and excellent indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc. may be used as the material for the anode electrode. The material for the anode electrode may be deposited by a conventional anode forming method, and specifically, may be deposited by a deposition method or a sputtering method.

Then, the hole injection layer material on the anode electrode can be formed by a method such as vacuum deposition, spin coating, casting, LB (Langmuir-Blodgett) method, etc., but it is easy to obtain a uniform film quality, and also It is preferable to form by a vacuum evaporation method from the point of being difficult to generate|occur|produce. In the case of forming the hole injection layer by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal characteristics of the desired hole injection layer, etc., but in general, a deposition temperature of 50-500 ℃, It is preferable to appropriately select a vacuum degree of 10 ^-8 to 10 ^-3 torr, a deposition rate of 0.01 to 100 Å/sec, and a layer thickness of 10 Å to 5 μm.

As the hole injection layer material, the compound represented by Formula 1 of the present invention may be used alone or a known hole injection layer material may be used. For example, a phthalocyanine compound such as copper phthalocyanine disclosed in US Patent No. 4,356,429 or starburst Type amine derivatives TCTA (4,4',4"-tri(N-carbazolyl)triphenylamine), m-MTDATA (4,4',4"-tris(3-methylphenylamino)triphenylamine) , m-MTDAPB(4,4',4"-tris(3-methylphenylamino)phenoxybenzene), HI-406(N ¹ ,N ¹ '-(biphenyl-4,4'-diyl)bis(N ^1- (naphthalen-1-yl)-N ⁴ ,N ⁴ -diphenylbenzene-1,4-diamine) may be used as the hole injection layer material.

Next, the hole transport layer material on the hole injection layer can be formed by a method such as vacuum deposition, spin coating, casting, LB method, etc., but it is easy to obtain a uniform film quality, It is preferable to form by vapor deposition. In the case of forming the hole transport layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same range of conditions as those for the hole injection layer formation.

In addition, as the hole transport layer material, the compound represented by Formula 1 of the present invention may be used alone or a mixture of known hole transport layer materials may be used. Specifically, the known hole transport layer material includes carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1, 1-biphenyl]-4,4'-diamine (TPD), N.N'-di(naphthalen-1-yl)-N,N'-diphenyl benzidine (α-NPD) having an aromatic condensed ring Conventional amine derivatives and the like can be used.

After that, the light emitting layer material on the hole transport layer can be formed by methods such as vacuum deposition, spin coating, casting, LB, etc., but it is easy to obtain a uniform film quality and it is difficult to generate pin holes. It is preferable to form by In the case of forming the light emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same range of conditions as those for the formation of the hole injection layer. In addition, the light emitting layer material may be used as a known host or dopant. For example, as a fluorescent dopant, IDE102 or IDE105, or BD142 (N ⁶ ,N ¹² -bis(3,4-dimethylphenyl)-N ⁶ ,N ¹² -dimethylchrysene- 6,12-diamine) can be used, and the phosphorescent dopant is a green phosphorescent dopant Ir(ppy) ₃ (tris(2-phenylpyridine) iridium), and a blue phosphorescent dopant F2Irpic (iridium(III) bis[4,6- Difluorophenyl)-pyridinato-N,C2'] picolinic acid salt), UDC's red phosphorescent dopant RD61, etc. may be co-evacuated (doped). The doping concentration of the dopant is not particularly limited, but it is preferable that the dopant be doped in an amount of 0.01 to 15 parts by weight relative to 100 parts by weight of the host.

In addition, when used with a phosphorescent dopant in the light emitting layer, in order to prevent the phenomenon of triplet excitons or holes from being diffused into the electron transport layer, it is preferable to further laminate a hole blocking material (HBL) by vacuum deposition or spin coating. At this time, the hole-blocking material that can be used is not particularly limited, and any one of the known hole-blocking materials used as the hole-blocking material can be selected and used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or a hole-inhibiting material described in Japanese Patent Application Laid-Open No. Hei 11-329734 (A1), etc. are mentioned. Representatively, Balq (bis(8-hyde) Roxy-2-methylquinolinol nato)-aluminum biphenoxide), phenanthrolines-based compounds (eg, UDC's BCP (vasocuproin)), etc. may be used.

An electron transport layer is formed on the light emitting layer formed as described above. In this case, the electron transport layer is formed by a vacuum deposition method, a spin coating method, a casting method, etc., and is particularly preferably formed by a vacuum deposition method.

The electron transport layer material functions to stably transport electrons injected from the electron injection electrode, and the type thereof is not particularly limited. For example, a quinoline derivative, particularly tris(8-quinolinolato)aluminum (Alq ₃ ) ), or ET4 (6,6'-(3,4-dimethyl-1,1-dimethyl-1H-silol-2,5-diyl)di-2,2'-bipyridine) can be used. In addition, an electron injection layer (EIL), which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer, and as the electron injection layer material, LiF, NaCl, CsF, Li ₂ O, BaO, etc. material can be used.

In addition, although the deposition conditions of the electron transport layer vary depending on the compound used, in general, it is preferable to select the electron transport layer in the same range of conditions as those for the formation of the hole injection layer.

Thereafter, an electron injection layer material may be formed on the electron transport layer, in which case the electron transport layer is formed by a method such as a vacuum deposition method, a spin coating method, a casting method, etc. of a conventional electron injection layer material, especially in a vacuum deposition method It is preferable to form by

Finally, a metal for forming a cathode on the electron injection layer is formed by a method such as vacuum deposition or sputtering and used as a cathode. Here, as the metal for forming the cathode, a metal having a low work function, an alloy, an electrically conductive compound, and a mixture thereof may be used. Specific examples include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), etc. There is this. In addition, in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

The organic light emitting device of the present invention can have an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and an organic light emitting device having a cathode structure, as well as a structure of an organic light emitting device having a variety of structures. It is also possible to further form a layer or an intermediate layer of two layers.

As described above, the thickness of each organic material layer formed according to the present invention can be adjusted according to the required degree, preferably 10 to 1,000 nm, more preferably 20 to 150 nm.

In addition, in the present invention, the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent shape stability because the thickness of the organic material layer can be adjusted in molecular units.

The organic light emitting device of the present invention has improved hole injection and hole transport properties, and at the same time has electron blocking properties, and has excellent device characteristics such as excellent low voltage, high efficiency, stability due to high Tg and long life.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are only illustrative of the present invention and the scope of the present invention is not limited to the following examples.

Synthesis of Intermediate A

[Synthesis of A-1]

In a round-bottom flask, 28.5 g of benzofuran-3-ylboronic acid and 50 g of methyl 5-bromo-2-iodobenzoate were dissolved in 600 ml of toluene, 220 ml of K ₂ CO ₃ (2M) and 5.1 g of Pd(PPh ₃ ) ₄ were added. Then, the mixture was stirred under reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and column purified to obtain 35.8 g of Intermediate A-1 (yield 72%).

[Synthesis of A-2]

After dissolving 35 g of the A-1 in 800 ml of THF, the temperature was lowered to 0 °C. 105 ml of CH ₃ MgBr was slowly added, and the mixture was slowly raised to room temperature, stirred for 1 hour, and stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 25.2 g of Intermediate A-2 (yield 70%).

[Synthesis of A]

After adding 250 ml of acetic acid and 1 ml of hydrochloric acid to 25 g of A-2, the mixture was stirred under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column to obtain 14.2 g of Intermediate A (yield: 60%).

Synthesis of Intermediate B

[Synthesis of B-1]

In a round-bottom flask, 28.5 g of benzofuran-3-ylboronic acid and 50 g of methyl 5-bromo-2-iodobenzoate were dissolved in 600 ml of toluene, 220 ml of K ₂ CO ₃ (2M) and 5.1 g of Pd(PPh ₃ ) ₄ were added. Then, the mixture was stirred under reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and column purified to obtain 35.8 g of Intermediate B-1 (yield 72%).

[Synthesis of B-2]

After dissolving 35 g of the B-1 in 850 ml of THF, the temperature was lowered to 0 °C. 105 ml of PhMgBr was slowly added, and the mixture was slowly raised to room temperature, stirred for 1 hour, and then stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and purified by column to obtain 33.7 g of Intermediate B-2 (yield 70%).

[Synthesis of B]

After adding 330 ml of acetic acid and 1.3 ml of hydrochloric acid to 33 g of B-2, the mixture was stirred under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column to obtain 20.6 g of Intermediate B (yield 65%).

Synthesis of Intermediate C

[Synthesis of C-1]

In a round-bottom flask, 31.3 g of benzo[b]thiophen-3-ylboronic acid and 50 g of methyl 5-bromo-2-iodobenzoate are dissolved in 600 ml of toluene, 220 ml of K ₂ CO ₃ (2M) and Pd(PPh ₃ ) ₄ After adding 5.1 g, the mixture was stirred under reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and column purified to obtain 38.2 g of Intermediate C-1 (yield 75%).

[Synthesis of C-2]

After dissolving 38 g of C-1 in 900 ml of THF, the temperature was lowered to 0 °C. 110 ml of CH ₃ MgBr was slowly added, and the mixture was slowly raised to room temperature, stirred for 1 hour, and then stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 26.6 g of Intermediate C-2 (yield 70%).

[Synthesis of C]

After adding 260 ml of acetic acid and 1 ml of hydrochloric acid to 26 g of C-2, the mixture was stirred under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column to obtain 14.8 g of Intermediate C (yield: 60%).

Synthesis of Intermediate D

[Synthesis of D-1]

In a round-bottom flask, 31.3 g of benzo[b]thiophen-3-ylboronic acid and 50 g of methyl 5-bromo-2-iodobenzoate are dissolved in 600 ml of toluene, and 220 ml of K ₂ CO ₃ (2M) and Pd(PPh ₃ ) ₄ 5.1 g, and then stirred under reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and purified by column to obtain 38.2 g of Intermediate D-1 (yield 75%).

[Synthesis of D-2]

After dissolving 38 g of D-1 in 900 ml of THF, the temperature was lowered to 0 °C. 110ml of PhMgBr was slowly added, and the mixture was slowly raised to room temperature, stirred for 1 hour, and then stirred under reflux. The organic layer was extracted with MC, filtered under reduced pressure, and column purified to obtain 36.6 g (yield 71%) of Intermediate D-2.

[Synthesis of D]

After adding 360 ml of acetic acid and 1.5 ml of hydrochloric acid to 36 g of D-2, the mixture was stirred under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column to obtain 23.2 g of Intermediate D (yield 67%).

Synthesis of 1A-1

Intermediate A 20 g, aniline 7.14 g, t-BuONa 9.21 g, Pd ₂ (dba) ₃ 2.34 g, (t-Bu) ₃ P 3.1 ml were dissolved in 270 ml toluene and stirred under reflux. Upon completion of the reaction, after adding water, the organic layer was extracted with EA, filtered under reduced pressure, and column purified to obtain 12.4 g of Intermediate 1A (yield 60%).

7 g of Intermediate 1A, 8.8 g of 1-bromo-4-iodobenzene, 8.8 g of t-BuONa, 0.8 g of Pd ₂ (dba) ₃ , and 1.1 ml of (t-Bu) ₃ P were dissolved in 140 ml of toluene and heated to 60 ° C. stirred. Upon completion of the reaction, after adding water, the organic layer was extracted with EA, filtered under reduced pressure, and column purified to obtain 4.4 g of Intermediate 1A-1 (yield 41%).

Synthesis of 2A-1

2A and 2A-1 were synthesized in the same manner as in Intermediate 1A-1, except that Aniline was reacted with naphthalen-1-amine. (Yield 44%)

Synthesis of 3A-1

3A and 3A-1 were synthesized in the same manner as in Intermediate 1A-1, except that Aniline was reacted with [1,1'-biphenyl]-4-amine. (Yield 40%)

Synthesis of 4A-1

4A and 4A-1 were synthesized in the same manner as in Intermediate 1A-1, except that Aniline was reacted with 9,9-dimethyl-9H-fluoren-2-amine. (Yield 44%)

Synthesis of 1B-1

1B and 1B-1 were synthesized in the same manner as in Intermediate 1A-1, except that Intermediate B was used instead of Intermediate A. (Yield 45%)

Synthesis of 2B-1

2B and 2B-1 were synthesized in the same manner as in Intermediate 1B-1, except that naphthalen-1-amine was used instead of Aniline. (Yield 38%)

Synthesis of 3B-1

3B and 3B-1 were synthesized in the same manner as in Intermediate 1B-1, except that [1,1'-biphenyl]-4-amine was used instead of Aniline. (Yield 40%)

Synthesis of 4B-1

4B and 4B-1 were synthesized in the same manner as in Intermediate 1B-1, except that 9,9-dimethyl-9H-fluoren-2-amine was used instead of Aniline. (Yield 37%)

Synthesis of 1C-1

1C and 1C-1 were synthesized in the same manner as in Intermediate 1A-1, except that Intermediate C was used instead of Intermediate A. (Yield 40%)

Synthesis of 2C-1

2C and 2C-1 were synthesized in the same manner as in Intermediate 1C-1, except that naphthalen-1-amine was used instead of Aniline. (Yield 39%)

Synthesis of 3C-1

3C and 3C-1 were synthesized in the same manner as in Intermediate 1C-1, except that [1,1'-biphenyl]-4-amine was used instead of Aniline. (Yield 45%)

Synthesis of 4C-1

4C and 4C-1 were synthesized in the same manner as in Intermediate 1C-1, except that 9,9-dimethyl-9H-fluoren-2-amine was used instead of Aniline. (Yield 42%)

Synthesis of 1D-1

1D and 1D-1 were synthesized in the same manner as in Intermediate 1A-1, except that Intermediate D was used instead of Intermediate A. (Yield 40%)

Synthesis of 2D-1

2D and 2D-1 were synthesized in the same manner as in Intermediate 1D-1, except that naphthalen-1-amine was used instead of Aniline. (Yield 35%)

Synthesis of 3D-1

3D and 3D-1 were synthesized in the same manner as in Intermediate 1D-1, except that [1,1'-biphenyl]-4-amine was used instead of Aniline. (Yield 44%)

Synthesis of 4D-1

4D and 4D-1 were synthesized in the same manner as in Intermediate 1D-1, except that 9,9-dimethyl-9H-fluoren-2-amine was used instead of Aniline. (Yield 37%)

Example 1: Synthesis of compound 1

4-bromo-N,N-diphenylaniline 20.0 g bis(pinacolato)diboron 20.36 g, Pd(dppf)Cl ₂ 0.2 g, and KOAc 18.1 g were dissolved in 400 ml toluene and stirred under reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and purified by column to obtain 19.5 g of intermediate OP1 (yield 85%).

In a round bottom flask, 4.0 g of Intermediate 1A-1, 3.7 g of OP1 and 70 ml of toluene were dissolved, and 12 ml of K ₂ CO ₃ (2M) and 0.3 g of Pd(PPh ₃ ) ₄ were added thereto, followed by stirring under reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and column purified to obtain 2.0 g of Compound 1 (yield 72%).

m/z: 644.28 (100.0%), 645.29 (51.3%), 646.29 (13.1%), 647.29 (2.3%)

Example 2: Synthesis of compound 2

Compound 2 was synthesized in the same manner as in Compound 1, except that it was reacted with 2A-1 instead of Intermediate 1A-1. (Yield 64%)

m/z: 694.30 (100.0%), 695.30 (56.4%), 696.31 (15.2%), 697.31 (2.8%)

Example 3: Synthesis of compound 3

OP2 was synthesized in the same manner as OP1, except that it was reacted with N-(4-bromophenyl)-N-phenylnaphthalen-1-amine instead of 4-bromo-N,N-diphenylaniline. (Yield 60%)

Compound 3 was synthesized in the same manner as in Compound 1, except that Intermediate 2A-1 and OP2 were reacted. (Yield 68%)

m/z: 744.31 (100.0%), 745.32 (60.0%), 746.32 (17.9%), 747.32 (3.6%)

Example 4: Synthesis of compound 4

Compound 4 was synthesized in the same manner as in Compound 1, except that 3A-1 was used instead of Intermediate 1A-1. (Yield 60%)

m/z: 720.31 (100.0%), 721.32 (57.8%), 722.32 (16.6%), 723.32 (3.2%)

Example 5: Synthesis of compound 5

Replace 4-bromo-N,N-diphenylaniline with N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-[1,1'-biphenyl]-4-amine Except for the reaction, OP3 was synthesized in the same manner as OP1. (Yield 81%)

Compound 5 was synthesized in the same manner as in Compound 1, except that Intermediate 3A-1 and OP3 were reacted. (Yield 60%)

m/z: 872.38 (100.0%), 873.38 (70.9%), 874.38 (25.1%), 875.39 (5.7%), 876.39 (1.0%)

Example 6: Synthesis of compound 6

N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine in place of 4-bromo-N,N-diphenylaniline OP4 was synthesized in the same manner as OP1 except that it was reacted with

Compound 6 was synthesized in the same manner as in Compound 1, except that Intermediate 3A-1 and OP4 were reacted. (Yield: 67%)

m/z: 912.41 (100.0%), 913.41 (74.2%), 914.41 (27.4%), 915.42 (6.7%), 916.42 (1.3%)

Example 7: Synthesis of compound 7

N-(4-bromophenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-dimethyl-9H-fluoren-2- in place of 4-bromo-N,N-diphenylaniline Except for the reaction with amine, OP5 was synthesized in the same way as OP1. (Yield 75%)

Compound 7 was synthesized in the same manner as in Compound 1, except that Intermediate 3A-1 and OP5 were reacted. (Yield 60%)

m/z: 952.44 (100.0%), 953.44 (77.6%), 954.45 (29.6%), 955.45 (7.6%), 956.45 (1.4%)

Example 8: Synthesis of compound 8

Compound 8 was synthesized in the same manner as in Compound 1, except that Intermediate 1A-1 was reacted with 1B-1. (Yield 60%)

m/z: 768.31 (100.0%), 769.32 (62.1%), 770.32 (19.2%), 771.32 (4.0%)

Example 9: Synthesis of compound 9

Compound 9 was synthesized in the same manner as in Compound 1, except that 3B-1 was used instead of Intermediate 1A-1. (Yield 58%)

m/z: 844.35 (100.0%), 845.35 (68.7%), 846.35 (23.9%), 847.36 (5.1%)

Example 10: Synthesis of compound 10

In a round-bottom flask, 3.0 g of the intermediate 1A-1 and 2.2 g of (9-phenyl-9H-carbazol-3-yl)boronic acid were dissolved in 70 ml of toluene, and 9.5 ml of K ₂ CO ₃ (2M) and Pd(PPh ₃ ) After adding 0.2 g of ₄ , the mixture was stirred under reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and column purified to obtain 2.4 g of Compound 10 (yield 60%).

m/z: 642.27 (100.0%), 643.27 (51.3%), 644.27 (13.2%), 645.28 (2.1%)

Example 11: Synthesis of compound 11

Compound 11 was synthesized in the same manner as in Compound 10, except that it was reacted with 2A-1 instead of Intermediate 1A-1. (Yield 62%)

m/z: 692.28 (100.0%), 693.29 (55.6%), 694.29 (15.4%), 695.29 (2.9%)

Example 12: Synthesis of compound 12

Compound 12 was synthesized in the same manner as in Compound 10, except that 3A-1 was used instead of Intermediate 1A-1. (Yield 65%)

m/z: 718.30 (100.0%), 719.30 (58.5%), 720.31 (16.4%), 721.31 (3.2%)

Example 13: Synthesis of compound 13

Compound 13 was synthesized in the same manner as in Compound 10, except that it was reacted with 4A-1 instead of Intermediate 1A-1. (Yield 64%)

m/z: 758.33 (100.0%), 759.33 (61.3%), 760.34 (18.3%), 761.34 (3.7%)

Example 14: Synthesis of compound 14

Compound 14 was synthesized in the same manner as in Compound 10 except that Intermediate 1A-1 was reacted with 3B-1. (Yield 55%)

m/z: 842.33 (100.0%), 843.33 (68.9%), 844.34 (23.2%), 845.34 (5.3%)

Example 15: Synthesis of compound 15

Compound 15 was synthesized in the same manner as in Compound 10, except that it was reacted with 4B-1 instead of Intermediate 1A-1. (Yield 51%)

m/z: 882.36 (100.0%), 883.36 (72.1%), 884.37 (25.7%), 885.37 (6.1%), 886.37 (1.1%)

Manufacturing of organic light emitting device

An organic light emitting diode was manufactured according to the structure shown in FIG. 1 . The organic light emitting device is from the bottom anode (hole injection electrode 11) / hole injection layer 12 / hole transport layer 13 / light emitting layer 14 / electron transport layer 15 / cathode (electron injection electrode 16) stacked in order.

The following materials were used for the hole injection layer 12, the hole transport layer 13, the light emitting layer 14, and the electron transport layer 15 of Examples and Comparative Examples.

,

,

비교화합물1

,

,

,

,

,

Comparative compound 1

,

,

,

Example 16

A glass substrate coated with indium tin oxide (ITO) having a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After cleaning with distilled water, ultrasonic cleaning is performed with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, and transferred to a plasma cleaner. After cleaning the substrate for 5 minutes using oxygen plasma, a thermal vacuum evaporator (thermal) evaporator) was used to form a hole injection layer HT01 600 Å and Compound 1 250 Å as a hole transport layer. Next, the light emitting layer was doped with 5% BH01:BD01 to form a film of 250 Å. Next, ET01:Liq (1:1) 300 Å was formed as an electron transport layer, LiF 10 Å, and aluminum (Al) 1000 Å were formed into a film, and an organic light emitting device was manufactured by encapsulating the device in a glove box.

Examples 17 to 30

In the same manner as in Example 16, an organic light emitting device in which the hole transport layer was formed into a film using the compounds 2 to 15, respectively, was manufactured.

Comparative Example 1

A device was manufactured in the same manner as in Example 1, except that NPB was used instead of Compound 1 as the hole transport layer.

Comparative Example 2

A device was manufactured in the same manner except that Comparative Compound 1 was used instead of Compound 1 as the hole transport layer of Example 1.

Performance evaluation of organic light emitting devices

Electrons and holes are injected by applying voltage with a Kiethley 2400 source measurement unit, and the luminance when light is emitted is measured using a Konica Minolta spectroradiometer (CS-2000). By doing so, the performances of the organic light emitting devices of Examples and Comparative Examples were evaluated by measuring current density and luminance with respect to applied voltage under atmospheric pressure conditions, and the results are shown in Table 1.

Op. V mA/cm2 Cd/A lm/w CIEx CIEy life span Example 1 4.131 10 6.09 3.80 0.141 0.121 30 Example 2 4.122 10 6.25 3.79 0.141 0.120 31 Example 3 4.130 10 5.98 3.91 0.142 0.120 30 Example 4 4.053 10 5.95 3.89 0.139 0.119 33 Example 5 4.100 10 6.10 3.90 0.138 0.119 31 Example 6 4.112 10 5.94 3.88 0.140 0.117 31 Example 7 4.094 10 6.17 3.91 0.140 0.118 34 Example 8 4.077 10 6.10 3.92 0.140 0.117 41 Example 9 4.012 10 6.13 3.87 0.138 0.118 42 Example 10 4.101 10 5.99 3.89 0.141 0.119 37 Example 11 4.008 10 6.00 3.90 0.142 0.116 39 Example 12 4.001 10 6.27 3.93 0.141 0.115 45 Example 13 4.091 10 6.03 3.88 0.142 0.115 40 Example 14 4.101 10 6.17 3.90 0.141 0.116 40 Example 15 4.112 10 5.98 3.85 0.141 0.114 32 Comparative Example 1 5.032 10 4.67 3.26 0.143 0.128 12 Comparative Example 2 4.737 10 4.78 3.54 0.141 0.122 15

As shown in Table 1, it can be seen that the Examples of the present invention have superior physical properties in all respects compared to Comparative Examples 1 and 2, and particularly have excellent lifespan. It can be seen that the compound of the present invention has easy hole injection and excellent hole transport ability, so that it has low voltage driving, high efficiency and long life.

Claims (6)

A hole injection and hole transport compound represented by the following formula (1):
[Formula 1]

In the above formula,
each X is independently O, S, Se or Te;
Ar ₁ , Ar ₃ and Ar ₄ are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1- A C _6-50 aryl group unsubstituted or substituted with a ₃₀ alkoxy group, a C _6-30 aryloxy group, a C _6-30 aryl group, or a C _2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryl an oxy group, a C _6-30 aryl group, or a C _2-50 heteroaryl group that is unsubstituted or substituted with a C _2-30 heteroaryl group,
Ar ₂ is deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 An aryloxy group of, a C _6-30 aryl group, or a C _6-50 arylene group unsubstituted or substituted with a C _2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryl an oxy group, a C _6-30 aryl group, or a C _2-50 heteroarylene group that is unsubstituted or substituted with a C _2-30 heteroaryl group,
The Ar ₂ and Ar ₃ may be connected to each other,
R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro; C _2-30 alkenyl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _1-30 alkoxy group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group,
n is 1 or 2,
*- is a binding site. According to claim 1,
A compound characterized in that it is represented by any one of the following formulas 2 to 4:
[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4, X, Ar ₁ , Ar ₃ , Ar ₄ , R ₁ and R ₂ are as defined in Formula 1, and R ₃ and R ₄ are each independently defined as R ₁ and R ₂ in Formula 1 same as According to claim 1,
A compound characterized in that it is represented by any one of the following formulas:

The preparation method of Formula 1 represented by the following Reaction Scheme 1:
[Scheme 1]

[Formula 1]

in the above reaction
each X is independently O, S, Se or Te;
Ar ₁ , Ar ₃ and Ar ₄ are each independently deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1- A C _6-50 aryl group unsubstituted or substituted with a ₃₀ alkoxy group, a C _6-30 aryloxy group, a C _6-30 aryl group, or a C _2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryl an oxy group, a C _6-30 aryl group, or a C _2-50 heteroaryl group that is unsubstituted or substituted with a C _2-30 heteroaryl group,
Ar ₂ is deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 An aryloxy group of, a C _6-30 aryl group, or a C _6-50 arylene group unsubstituted or substituted with a C _2-30 heteroaryl group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _1-30 alkoxy group, C _6-30 aryl an oxy group, a C _6-30 aryl group, or a C _2-50 heteroarylene group that is unsubstituted or substituted with a C _2-30 heteroaryl group,
The Ar ₂ and Ar ₃ may be connected to each other,
R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro; C _2-30 alkenyl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _1-30 alkoxy group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, or nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; Or a C _2-50 heteroaryl group that is unsubstituted or substituted with a deuterium, halogen, amino group, nitrile group, or nitro group,
n is 1 or 2,
R is R ₁ or R ₂ . An organic light emitting device comprising an anode, a cathode, and at least one organic material layer containing the compound of claim 1 between the two electrodes. 6. The method of claim 5,
The organic light emitting device, characterized in that the organic layer is a hole injection layer or a hole transport layer.

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