KR102437956B1 - Novel compound and organic electroluminescent device comprising same - Google Patents

Abstract

The novel 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 properties, and is a hole injection layer, a hole transport layer or a hole transport layer of an organic light emitting device. When applied to the auxiliary layer, it can have excellent low voltage, high efficiency, and stability and long lifespan due to high Tg.

Description

Novel compound and organic light emitting device comprising the same {NOVEL COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING SAME}

The present invention relates to a novel compound and an organic light emitting device including the same, and more particularly, to a compound useful as a hole injection material, a hole transport material, or a hole transport auxiliary material.

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

Materials used as organic layers in organic light emitting devices may be classified into light emitting materials, hole injection materials, hole transport materials, hole transport auxiliary materials, electron transport materials, electron injection materials, and the like, according to their functions.

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

In order to solve the above problems, the present invention has a HOMO energy level for easy hole injection, a high LUMO energy level for blocking electrons, excellent hole transport characteristics, and a hole injection layer of an organic light emitting device, 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 or a hole transport auxiliary layer.

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

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

[Formula 1]

In Formula 1,

,

, 수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기 또는 C_1-30의 알킬기이며, L is each independently

,

, hydrogen, deuterium, halogen, an amino group, a nitrile group, a nitro group, or a C _1-30 alkyl group,

Ar is each independently a C _6-50 aryl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group,

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted 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; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a 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 deuterium, halogen, amino group, nitrile group, nitro group substituted or unsubstituted C _2-50 heteroaryl group, R ₁ and R ₂ may form a ring with each other,

l, m, and n are each independently an integer of 0 to 3, and at least one of l, m, and n is not 0, preferably, at least one of m, n is not 0,

o, p, and q are each independently an integer of 0 to 4.

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

The 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, a hole transport layer or a hole transport auxiliary 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 Formula 1,

,

, 수소, 중수소, 할로겐, 아미노기, 니트릴기, 니트로기 또는 C_1-30의 알킬기이며, L is each independently

,

, hydrogen, deuterium, halogen, an amino group, a nitrile group, a nitro group, or a C _1-30 alkyl group,

Ar is each independently a C _6-50 aryl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group,

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted 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; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a 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 deuterium, halogen, amino group, nitrile group, nitro group substituted or unsubstituted C _2-50 heteroaryl group, R ₁ and R ₂ may form a ring with each other,

l, m, and n are each independently an integer of 0 to 3, and at least one of l, m, and n is not 0, preferably, at least one of m, n is not 0,

o, p, and q are each independently an integer of 0 to 4.

Preferably, the compound represented by Formula 1 is one of the compounds represented by Formulas 1-1 to 1-3 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In the above formulas, Ar, R ₁ , R ₂ , o, p and q are as defined in Formula 1. Preferably, in Formula 1-3, o is an integer of 1 to 3.

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 characteristics, and has a hole injection layer, a hole transport layer, Alternatively, when applied to the hole transport auxiliary layer, it can have excellent low voltage, high efficiency, and stability and long life due to high Tg.

In addition, the compound of the present invention can be prepared through the following process.

[Scheme 1]

In Scheme 1, the target compound is a compound represented by Formula 1, and Ar, L, 1, R ₁ , R ₂ , o, p, q are as defined in Formula 1.

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, a hole transport material, or a hole transport auxiliary material, or it may be used together with a known hole injection, hole transport material, or hole transport auxiliary material.

In addition, the organic light emitting device of the present invention includes one or more organic material layers including the compound represented by Chemical Formula 1, and a method of manufacturing the organic light emitting device will be described as an example 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. In addition, a hole transport auxiliary layer may be further included between the hole transport layer and the light emitting layer.

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 water resistance. In addition, as the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, may be used. 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 the 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 formation of the hole injection layer.

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.

Thereafter, 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 it 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 together with a phosphorescent dopant in the light emitting layer, in order to prevent a phenomenon in which triplet excitons or holes are 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 known hole-blocking materials used as a 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 the 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 within 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 vacuum deposition, spin coating, casting, etc., of a conventional electron injection layer material, particularly 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 a vacuum deposition method or a sputtering method 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.

In addition, the organic light emitting device of the present invention may further include a hole transport auxiliary layer between the hole transport layer and the light emitting layer. The hole transport auxiliary layer may be formed through a known method as described in Republic of Korea Void Publication No. 10-2010-0015029, and preferably, the hole transport auxiliary layer using Compound 1 of the present invention as a hole transport auxiliary material. can form.

The organic light emitting device of the present invention may have an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an organic light emitting device having a cathode structure, as well as a structure of an organic light emitting device of various structures is possible, if necessary, 1 It is also possible to further form a layer or an intermediate layer of two layers. Preferably, the organic light emitting device of the present invention further comprises a hole transport auxiliary layer.

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 the present invention, the organic material layer including the compound represented by Formula 1 has a uniform surface and excellent morphological 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 1

[Synthesis of 1-1`]

Dissolve 83.70 g of (1-phenyl-1H-indol-3-yl)boronic acid and 100 g of methyl 4-bromo-2-iodobenzoate in 1200 ml of 1,4-Dioxane in a round-bottom flask, and dissolve K ₂ CO ₃ (2M) 450 ml and 10.2 g of Pd(PPh ₃ ) ₄ were added 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 column purified to obtain 93.2 g of Intermediate 1-1` (yield 78%).

[Synthesis of 1-2`]

After dissolving 50 g of 1-1` in 1300 ml of THF, 48.4 g of CH <sub>3</sub> MgBr was slowly added dropwise at 0° C., the temperature was slowly increased, and the mixture was stirred under reflux for 5 hours. The organic layer was extracted with MC and filtered under reduced pressure to obtain 35.8 g of Intermediate 1-2` (yield 65%).

[Synthesis of Intermediate 1]

35 g of 1-2` was dissolved in 350 ml of acetic acid, 1.5 ml of hydrochloric acid was added, and the mixture was stirred under reflux for 3 hours. After the reaction was completed, the organic layer was extracted with water and MC. Moisture was removed with MgSO ₄ , filtered under reduced pressure, and column purification was performed to obtain 27.8 g of Intermediate 1 (yield 83%).

Synthesis of Intermediate 2

In the same manner as in the synthesis of Intermediate 1, 2-2` 39.2 g (yield 79%) and Intermediate 2 31.7 g (yield 80%) were synthesized using PhMgBr instead of CH ₃ MgBr.

Synthesis of Intermediate 3

Using methyl 5-bromo-2-iodobenzoate instead of methyl 4-bromo-2-iodobenzoate in the same manner as in the synthesis of Intermediate 1, 3-1` 90.9 g (yield 76%), 3-2` 33.0 g (yield 66) %), 24.9 g of Intermediate 3 (yield 79%) was synthesized.

Synthesis of Intermediate 4

In the same manner as in the synthesis of Intermediate 3, 39.2 g of 4-2` (yield 75%) and 30.9 g of Intermediate 4 (yield 82%) were synthesized using PhMgBr instead of CH ₃ MgBr.

Synthesis of Intermediate 5

[Synthesis of 5-1`]

In a round-bottom flask, 90 g of 5-chloro-1-phenyl-1H-indole was dissolved in 1300 ml of DMF, the temperature was lowered to 0 °C, and a solution of 77.3 g of NBS was slowly added dropwise to 600 ml. After slowly raising the temperature to room temperature, the mixture was stirred for 3 hours. The reaction was confirmed by TLC, DMF was filtered under reduced pressure, and the organic layer was extracted with MC and water. Column purification was performed to obtain 88.4 g of Intermediate 5-1` (yield 73%).

[Synthesis of 5-2`]

88 g of 5-1`, 51.7 g of (2-(methoxycarbonyl)phenyl)boronic acid were dissolved in 1000 ml of 1,4-Dioxane, and 430 ml of K <sub>2</sub> CO <sub>3</sub> (2M) and 9.96 g of Pd(PPh <sub>3</sub> ) <sub>4</sub> 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 71.7 g of Intermediate 5-2` (yield 69%).

[Synthesis of 5-3`]

After dissolving 43 g of 5-2` in 950 ml of THF, 39.5 g of CH <sub>3</sub> MgBr was slowly added dropwise at 0° C., the temperature was gradually increased, and the mixture was stirred under reflux for 5 hours. The organic layer was extracted with MC and filtered under reduced pressure to obtain 26.4 g of Intermediate 5-3` (yield 66%).

[Synthesis of Intermediate 5]

After dissolving 26 g of 5-3` in 260 ml of acetic acid, 1.1 ml of hydrochloric acid was added thereto, followed by stirring under reflux for 3 hours. After the reaction was completed, the organic layer was extracted with water and MC. Water was removed with MgSO ₄ , filtered under reduced pressure, and column purification was performed to obtain 19.0 g of Intermediate 5 (yield 77%).

Synthesis of Intermediate 6

In the same manner as in the synthesis of Intermediate 5, 6-3` 32.9 g (yield 79%) and Intermediate 6 24.7 g (yield 80%) were synthesized using PhMgBr instead of CH ₃ MgBr.

Synthesis of Intermediate 7

In the same manner as in the synthesis of Intermediate 1, (1H-indol-3-yl)boronic acid was used instead of (1-phenyl-1H-indol-3-yl)boronic acid, and methyl 2 instead of methyl 4-bromo-2-iodobenzoate Using -bromobenzoate, 7-1` 70.1 g (yield 75%), 3-2` 22.0 g (yield 70%), and 17.5 g of Intermediate 7 (yield 75%) were synthesized.

Synthesis of OP

Preparation of OP for synthesizing the target compound was synthesized through the above steps.

The synthesis method of the following OP1 is as follows.

In a round-bottom flask, 10 g of N-phenylnaphthalen-1-amine, 18.0 g of 1-bromo-4-iodobenzene, 6.5 g of t-BuONa, 1.7 g of Pd ₂ (dba) ₃ , 2.6 ml of (t-Bu) ₃ P were mixed with toluene 100 After dissolving in ml, the mixture was stirred at 50 °C. 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 7.6 g (yield 45%) of the intermediate OP1.

The OP1 7.5 g bis(pinacolato)diboron 6.62 g, Pd(dppf)Cl ₂ 0.07 g, and KOAc 5.9 g were dissolved in 80 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 6.8 g of intermediate OP2 (yield 81%).

The following OP2 to OP10 were synthesized in the same manner as OP1.

Synthesis of compound 1

In a round-bottom flask, 3.0 g of Intermediate 1, 2.73 g of di([1,1'-biphenyl]-4-yl)amine, 1.11 g of t-BuONa, Pd ₂ (dba) ₃ 0.28 g, (t-Bu) ₃ P 0.34 ml was dissolved in 50 ml of 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 3.06 g of Compound 1 (yield 63%).

m/z: 628.29 (100.0%), 629.29 (51.2%), 630.29 (13.0%), 631.30 (2.1%)

Synthesis of compound 2

di([1,1'-biphenyl]-4-yl)amine was reacted with N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine Compound 2 was synthesized in the same manner as in Compound 1, except that. (Yield 66%)

m/z: 668.32 (100.0%), 669.32 (54.8%), 670.33 (14.6%), 671.33 (2.5%)

Synthesis of compound 3

In a round bottom flask, 3.0 g of Intermediate 1 and 4.85 g of OP2 were dissolved in 60 ml of 1,4-dioxan, 12 ml of K ₂ CO ₃ (2M) and 0.27 g of Pd(PPh ₃ ) ₄ were added, 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 MC, filtered under reduced pressure, and purified by column to obtain 3.87 g of compound 3 (yield 71%).

m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)

Synthesis of compound 4

Compound 4 was synthesized in the same manner as in Compound 3, except that OP2 was reacted with OP3. (Yield 67%)

m/z: 744.35 (100.0%), 745.35 (61.3%), 746.36 (18.3%), 747.36 (3.6%)

Synthesis of compound 5

Compound 5 was synthesized in the same manner as in Compound 3, except that OP2 was reacted with OP1. (yield 70%)

m/z: 602.27 (100.0%), 603.28 (49.1%), 604.28 (11.8%), 605.28 (1.9%)

Synthesis of compound 6

Compound 6 was synthesized in the same manner as in Compound 3, except that OP2 was reacted with OP4. (Yield 73%)

m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)

Synthesis of compound 7

Compound 7 was synthesized in the same manner as in Compound 3, except that OP2 was reacted with OP5. (Yield 63%)

m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)

Synthesis of compound 8

Compound 8 was synthesized in the same manner as in Compound 3, except that OP2 was reacted with OP6. (Yield 67%)

m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)

Synthesis of compound 9

Compound 9 was synthesized in the same manner as in Compound 3, except that Intermediate 1 was reacted with Intermediate 2. (yield 75%)

m/z: 828.35 (100.0%), 829.35 (68.9%), 830.36 (23.2%), 831.36 (5.1%)

Synthesis of compound 10

Compound 10 was synthesized in the same manner as in Compound 9, except that OP2 was reacted with OP3. (yield 69%)

m/z: 868.38 (100.0%), 869.39 (71.9%), 870.39 (25.5%), 871.39 (6.1%), 872.40 (1.0%)

Synthesis of compound 11

Compound 11 was synthesized in the same manner as in Compound 3, except that Intermediate 1 was reacted with Intermediate 3 and OP2 was reacted with OP6. (Yield 61%)

m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)

Synthesis of compound 12

Compound 12 was synthesized in the same manner as in Compound 11, except that OP6 was reacted with OP7. (Yield 64%)

m/z: 744.35 (100.0%), 745.35 (61.3%), 746.36 (18.3%), 747.36 (3.6%)

Synthesis of compound 13

Compound 13 was synthesized in the same manner as in Compound 11, except that OP6 was reacted with OP10. (yield 69%)

m/z: 668.32 (100.0%), 669.32 (54.8%), 670.33 (14.6%), 671.33 (2.5%)

Synthesis of compound 14

Compound 14 was synthesized in the same manner as in Compound 1, except that Intermediate 1 was reacted with Intermediate 5. (yield 70%)

m/z: 628.29 (100.0%), 629.29 (51.2%), 630.29 (13.0%), 631.30 (2.1%)

Synthesis of compound 15

di([1,1'-biphenyl]-4-yl)amine was reacted with N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine Compound 15 was synthesized in the same manner as Compound 14, except that. (Yield 63%)

m/z: 668.32 (100.0%), 669.32 (54.8%), 670.33 (14.6%), 671.33 (2.5%)

Synthesis of compound 16

Compound 16 was synthesized in the same manner as in Compound 3, except that Intermediate 1 was reacted with Intermediate 5. (Yield 66%)

m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)

Synthesis of compound 17

Compound 17 was synthesized in the same manner as in Compound 16, except that OP2 was reacted with OP3. (yield 60%)

m/z: 744.35 (100.0%), 745.35 (61.3%), 746.36 (18.3%), 747.36 (3.6%)

Synthesis of compound 18

Compound 18 was synthesized in the same manner as in Compound 3, except that Intermediate 1 was reacted with Intermediate 6. (Yield 65%)

m/z: 828.35 (100.0%), 829.35 (68.9%), 830.36 (23.2%), 831.36 (5.1%)

Synthesis of compound 19

Compound 19 was synthesized in the same manner as in Compound 18, except that OP2 was reacted with OP3. (yield 69%)

m/z: 868.38 (100.0%), 869.39 (71.9%), 870.39 (25.5%), 871.39 (6.1%), 872.40 (1.0%)

Synthesis of compound 20

Compound 20 was synthesized in the same manner as in Compound 3, except that Intermediate 1 was reacted with Intermediate 3. (yield 59%)

m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)

Synthesis of compound 21

Compound 21 was synthesized in the same manner as in Compound 4, except that Intermediate 1 was reacted with Intermediate 3. (Yield 63%)

m/z: 744.35 (100.0%), 745.35 (61.3%), 746.36 (18.3%), 747.36 (3.6%)

Synthesis of compound 22

Compound 22 was synthesized in the same manner as in Compound 3, except that OP2 was reacted with OP11. (yield 60%)

m/z: 780.35 (100.0%), 781.35 (64.6%), 782.36 (20.3%), 783.36 (4.2%)

Synthesis of compound 23

Compound 23 was synthesized in the same manner as in Compound 3, except that OP2 was reacted with OP12. (Yield 65%)

m/z: 820.38 (100.0%), 821.39 (67.6%), 822.39 (22.5%), 823.39 (5.1%)

Synthesis of compound 24

Compound 24 was synthesized in the same manner as in Compound 3, except that OP2 was reacted with OP13. (yield 58%)

m/z: 820.38 (100.0%), 821.39 (67.6%), 822.39 (22.5%), 823.39 (5.1%)

Synthesis of compound 25

Intermediate 1 to Intermediate 7 N,N-di([1,1'-biphenyl]-4-yl)-4'-bromo-[1 instead of di([1,1'-biphenyl]-4-yl)amine Compound 25 was synthesized in the same manner as in Compound 1, except that it was reacted with ,1'-biphenyl]-4-amine. (Yield 55%)

m/z: 704.32 (100.0%), 705.32 (58.1%), 706.33 (16.4%), 707.33 (3.0%)

Synthesis of compound 26

N-([1,1'-biphenyl]-4-yl)-N-(4'-bromo-[1,1'-biphenyl] instead of di([1,1'-biphenyl]-4-yl)amine Compound 26 was synthesized in the same manner as in Compound 25, except that it was reacted with -4-yl)-9,9-dimethyl-9H-fluoren-2-amine. (Yield 52%)

m/z: 744.35 (100.0%), 745.35 (61.3%), 746.36 (18.3%), 747.36 (3.6%)

Synthesis of compound 27

N,N-di([1,1'-biphenyl]-4-yl)-7-bromo-9,9-dimethyl-9H-fluoren instead of di([1,1'-biphenyl]-4-yl)amine Compound 27 was synthesized in the same manner as in Compound 25, except that it was reacted with -2-amine. (Yield 50%)

m/z: 744.35 (100.0%), 745.35 (61.3%), 746.36 (18.3%), 747.36 (3.6%)

Manufacture 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 stacked in the order of the hole injection electrode 11 / hole injection layer 12 / hole transport layer 13 / light emitting layer 14 / electron transport layer 15 / electron injection electrode 16 from the bottom.

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.

Manufacture of organic light emitting device

Example 1

A glass substrate coated with indium tin oxide (ITO) having a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning is performed with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, transferred to a plasma cleaner, and then the substrate is cleaned using oxygen plasma for 5 minutes. An 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 300 Å. Next, Alq3:Liq(1:1) 300 Å was formed as an electron transport layer, Liq 10 Å, and aluminum (Al) 1000 Å were formed into a film, and the organic light emitting device was manufactured by encapsulating the device in a glove box.

Examples 2 to 27

In the same manner as in Example 1, an organic light emitting device in which a hole injection layer and a hole transport layer were formed using Compounds 2 to 27, respectively, was manufactured.

Example 28

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, transferred to a plasma cleaner, and then the substrate is cleaned using oxygen plasma for 5 minutes. Using an evaporator), 600 Å of the hole injection layer HT01, 240 Å of Compound 1 as the first hole transport layer, and 10 Å of Compound 25 as the second hole transport layer were formed. Next, the light emitting layer was doped with 5% BH01:BD01 to form a film of 300 Å. Next, Alq3:Liq (1:1) 300 Å was formed as an electron transport layer, Liq 10 Å, and aluminum (Al) 1000 Å were formed into a film, and the device was encapsulated in a glove box to manufacture an organic light emitting device.

Example 29

In the same manner as in Example 28, an organic light emitting device formed of compound 26 as a second hole transport layer was manufactured.

Example 30

In the same manner as in Example 28, an organic light emitting device formed of compound 27 as a second hole transport layer was manufactured.

Comparative Example 1

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

Comparative Example 2

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

Comparative Example 3

A device was manufactured in the same manner except that the hole transport layer of Example 1 was used as Ref.2.

Comparative Example 4

A device was manufactured in the same manner except that the hole transport layer of Example 1 was used as Ref.3.

Comparative Example 5

A device was manufactured in the same manner except that the hole transport layer of Example 1 was used as Ref.4.

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 LT95
(hr) Example 1 4.05 10 6.49 5.02 0.141 0.112 44 Example 2 4.03 10 6.45 5.00 0.141 0.112 45 Example 3 3.91 10 6.65 5.25 0.142 0.111 55 Example 4 3.90 10 6.82 5.30 0.139 0.111 60 Example 5 3.92 10 6.63 5.95 0.138 0.110 48 Example 6 3.92 10 6.60 5.40 0.140 0.111 50 Example 7 3.90 10 6.70 5.90 0.140 0.110 52 Example 8 3.90 10 6.70 5.27 0.140 0.110 47 Example 9 3.93 10 6.73 5.40 0.138 0.112 45 Example 10 3.87 10 6.89 5.29 0.141 0.111 53 Example 11 3.93 10 6.75 5.35 0.142 0.111 46 Example 12 3.90 10 6.90 5.35 0.141 0.111 58 Example 13 3.92 10 6.80 5.90 0.140 0.111 50 Example 14 4.05 10 6.51 5.42 0.140 0.110 43 Example 15 4.02 10 6.49 5.85 0.140 0.110 45 Example 16 3.92 10 6.69 5.29 0.141 0.111 50 Example 17 3.89 10 6.87 5.35 0.142 0.111 55 Example 18 3.90 10 6.80 5.35 0.141 0.111 49 Example 19 3.92 10 6.88 5.90 0.140 0.111 52 Example 20 3.92 10 6.71 5.42 0.140 0.110 55 Example 21 3.90 10 6.91 5.85 0.140 0.110 61 Example 22 3.94 10 6.69 5.29 0.141 0.111 50 Example 23 3.95 10 6.85 5.35 0.142 0.111 57 Example 24 3.93 10 6.83 5.35 0.141 0.111 55 Example 25 4.05 10 6.80 5.90 0.140 0.111 53 Example 26 4.02 10 6.72 5.42 0.140 0.110 49 Example 27 4.02 10 6.70 5.85 0.140 0.110 52 Example 28 3.83 10 7.11 6.12 0.140 0.109 65 Example 29 3.84 10 7.00 6.04 0.140 0.110 62 Example 30 3.85 10 7.05 6.10 0.140 0.110 62 Comparative Example 1 5.03 10 5.35 4.24 0.143 0.120 13 Comparative Example 2 5.12 10 5.18 4.11 0.145 0.121 8 Comparative Example 3 5.21 10 5.28 4.35 0.141 0.113 10 Comparative Example 4 5.50 10 5.04 4.02 0.141 0.115 19 Comparative Example 5 5.01 10 5.47 4.44 0.141 0.113 23

As shown in Table 1, it can be confirmed that Examples 1 to 30 of the present invention have superior physical properties in all aspects compared to Comparative Examples 1 to 5. This has a high LUMO so that the compound represented by Formula 1 of the present invention can effectively block electrons in the light emitting layer, and forms a HOMO with smooth hole injection by substitution of an arylamine group. In addition, it can be seen that the tetracyclic structure of the compound represented by Formula 1 of the present invention can form a HOMO with smooth hole injection, and excellent hole mobility, resulting in significantly low driving voltage and high efficiency. have.

Claims (7)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1,
L is

,

is,
Ar is each independently a C _6-50 aryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, or nitro group, wherein at least one of Ar is substituted or unsubstituted fluorene or substituted or unsubstituted C ₁₀ . _-50 is an aryl group,
R ₁ and R ₂ are each independently a C _1-30 alkyl group substituted with or unsubstituted with deuterium, halogen, an amino group, a nitrile group, or a nitro group; Deuterium, a halogen, an amino group, a nitrile group, a nitro group or an unsubstituted C _6-50 aryl group, R ₁ and R ₂ may form a ring with each other,
l, m, and n are each independently an integer of 0 to 3, and at least one of l, m, and n is not 0;
o, p, q are each independently an integer of 0 to 4,
However, when n is an integer of 1 to 3, L in -(L)n is

to be. According to claim 1,
a compound in which at least one of m and n is non-zero: According to claim 1,
Formula 1 is a compound represented by any one of Formulas 1-1 to 1-3:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In the above formulas, Ar, R ₁ , R ₂ , o, p and q are as defined in Formula 1 above,
In Formula 1-2, o is 0. According to claim 1,
Formula 1 is a compound represented by any one of the following formulas:

delete An organic light emitting device comprising an anode, a cathode, and at least one organic material layer containing the compound of any one of claims 1 to 4 between the two electrodes. 7. The method of claim 6,
An organic light emitting device in which the organic material layer is a hole injection layer, a hole transport layer, or a hole transport auxiliary layer.

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