WO2015084047A1 - Novel compound and organic light-emitting element comprising same - Google Patents

Abstract

A compound according to the present invention has a HOMO energy level facilitating hole injection, a high LUMO energy level capable of blocking electrons, a superb hole transport characteristic, and when applied to a hole injection layer or hole transport layer of an organic light-emitting element, can impart stability and extended lifespan thereto due to superbly low voltage, high efficiency and high Tg.

Description

Novel compound and organic light emitting device comprising the same

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

Recently, an organic light emitting device capable of low voltage driving with a self-luminous type has a superior viewing angle, contrast ratio, and the like, and is lighter and thinner than a liquid crystal display (LCD), which is the mainstream of flat panel display devices. In terms of power consumption and wide color reproduction range, it is attracting attention as a next-generation display device.

The material used as the organic material layer in the organic light emitting device can be largely classified into light emitting materials, hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on the function.

Until now, a lot of amine derivatives having carbazole bones have been studied in the hole transport material used in the organic light emitting device, but there are many difficulties in practical use due to the higher driving voltage, lower efficiency and shorter lifespan. Therefore, efforts have been made to develop organic light emitting devices having low voltage driving, high brightness and long life using materials having excellent properties.

In order to solve the above problems, the present invention has a HOMO energy level easy hole injection, has a high LUMO energy level that can block electrons, excellent hole transport characteristics, hole injection layer of the organic light emitting device or It is an object of the present invention to provide a novel compound that can have excellent low voltage, high efficiency, high Tg stability and long life when applied to a hole transport layer.

It is another object of the present invention to provide an organic light emitting device including the compound, which has improved hole injection and hole transport characteristics, and at the same time has electron blocking characteristics, and has 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 Chemical Formula 1:

[Formula 1]

Where

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 an aryl group of an alkynyl group, an alkoxy group of C _1-30, are C _6-30 aryloxy groups, be substituted by a heteroaryl group of the C _6-30 aryl group, or a C _2-30 substituted or the C _6-50; 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 Or a C _2-50 heteroaryl group which is unsubstituted or substituted with an oxy group, a C _6-30 aryl group, or a C _2-30 heteroaryl group, and Ar ₂ and Ar ₃ may be connected to each other,

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

m is 1 or 2,

n is an integer from 0 to 2,

*-Is a coupling site.

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 is easy to inject holes, has a high LUMO energy level that can block electrons, excellent hole transport characteristics, excellent low voltage when applied to the hole injection layer or hole transport layer of the organic light emitting device It has high stability, long life due to high efficiency and high Tg.

1 schematically illustrates a cross section of an OLED according to an embodiment of the invention.

Sign of drawing

10: substrate

11: anode

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 by represented by the following formula (1).

[Formula 1]

Where

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 an aryl group of an alkynyl group, an alkoxy group of C _1-30, are C _6-30 aryloxy groups, be substituted by a heteroaryl group of the C _6-30 aryl group, or a C _2-30 substituted or the C _6-50; 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 Or a C _2-50 heteroaryl group which is unsubstituted or substituted with an oxy group, a C _6-30 aryl group, or a C _2-30 heteroaryl group, and Ar ₂ and Ar ₃ may be connected to each other,

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

m is 1 or 2,

n is an integer from 0 to 2,

*-Is a coupling site.

In the present invention, the compound represented by Chemical Formula 1 may be one of those represented by the following Chemical Formula 2 or 3.

[Formula 2]

[Formula 3]

In Formula 2 or 3, X, Ar ₁ , Ar ₂ , Ar ₄ , R ₁ and R ₂ are the same as defined in Formula 1, and R ₃ is the same as the definition of R ₁ .

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

Compound of Formula 1 according to the present invention has a HOMO energy level easy hole injection, has a high LUMO energy level that can block electrons, excellent hole transport characteristics, in the hole injection layer or hole transport layer of the organic light emitting device When applied, it can have excellent low voltage, high efficiency, high Tg stability and long life.

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

Scheme 1

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

The present invention also provides an organic light emitting device comprising the compound represented by Chemical Formula 1 in an organic material layer. At this time, the compound of the present invention is preferably used alone or in combination with a known compound as a hole injection material or a hole transport 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 the method of manufacturing the organic light emitting device is as follows.

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

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

Subsequently, the hole injection layer material may be formed on the anode by vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB), etc., but it is easy to obtain a uniform film quality and also pinholes. It is preferable to form by the vacuum evaporation method in that it is hard to generate | occur | produce. When the hole injection layer is formed 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 properties of the desired hole injection layer, and generally, a deposition temperature of 50-500 ° C., It is preferable to select appropriately from a vacuum degree of 10 ^-8 to 10 ^-3 torr, a deposition rate of 0.01 to 100 kPa / sec, and a layer thickness of 10 kPa to 5 mu m.

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 or starburst such as copper phthalocyanine disclosed in US Pat. No. 4,356,429. TCTA (4,4 ', 4 "-tri (N-carbazolyl) triphenylamine) and 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) and the like can be used as the hole injection layer material.

Next, the hole transport layer material may be formed on the hole injection layer by a method such as vacuum deposition, spin coating, cast, LB, etc., but it is easy to obtain a uniform film quality and is difficult to generate pin holes. It is preferable to form by a vapor deposition method. 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, the hole transport layer is preferably selected in the same condition range as the formation of the hole injection layer.

In addition, the hole transport layer material may be a compound represented by the formula (1) of the present invention may be used alone or a mixture of known hole transport layer materials. 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, Having an aromatic condensed ring such as 1-biphenyl] -4,4'-diamine (TPD) and N.N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD) Conventional amine derivatives and the like can be used.

Thereafter, the light emitting layer material may be formed on the hole transport layer by a method such as vacuum deposition, spin coating, casting, LB, etc., but the vacuum deposition method is easy to obtain a uniform film quality and hard 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 condition range as 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, a fluorescent dopant may be IDE102 or IDE105 available from Idemitsu, or BD142 (N ⁶ , N ¹² -bis (3,4-dimethylphenyl) -N ⁶ , N ¹² -dimethycrylicene- 6,12-diamine) can be used as green phosphorescent dopant Ir (ppy) ₃ (tris (2-phenylpyridine) iridium), blue phosphorescent dopant F2Irpic (iridium (III) bis [4,6- Difluorophenyl) -pyridinato-N, C2 '] picolinate), a red phosphorescent dopant RD61 from UDC, and the like can be co-vacuum deposited (doped). The doping concentration of the dopant is not particularly limited, but the dopant is preferably doped at 0.01 to 15 parts by weight based on 100 parts by weight of the host.

In addition, when using the phosphorescent dopant in the light emitting layer, it is preferable to further laminate the hole suppression material (HBL) by vacuum deposition or spin coating to prevent the triplet excitons or holes from diffusing into the electron transport layer. The hole-suppressing material that can be used at this time is not particularly limited, but any one of the well-known ones used as the hole-inhibiting material can be selected and used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the hole-inhibiting material described in Japanese Patent Laid-Open No. 11-329734 (A1) can be cited. Oxy-2-methylquinolinolato) -aluminum biphenoxide), a phenanthrolines-based compound (e.g., BCP (vasocuproin) from UDC) can be used.

An electron transport layer is formed on the light emitting layer formed as above, wherein the electron transport layer is formed by a vacuum deposition method, a spin coating method, a casting method, or the like, and is 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, and examples thereof include quinoline derivatives, especially 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). 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 the electron injection layer material may be LiF, NaCl, CsF, Li ₂ O, BaO, or the like. The substance of can be used.

In addition, although the deposition conditions of the electron transport layer are different depending on the compound used, it is generally preferable to select within the same condition range as the formation of the hole injection layer.

Subsequently, an electron injection layer material may be formed on the electron transport layer, wherein the electron transport layer is formed of a conventional electron injection layer material by a vacuum deposition method, a spin coating method, a casting method, and the like. It is preferable to form by.

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

The organic light emitting device of the present invention is not only 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 of the cathode structure, but also the structure of an organic light emitting device of various structures, 1 It is also possible to form a layer or two intermediate 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, the present invention has an advantage that 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 characteristics, and at the same time has electron blocking characteristics, and excellent device characteristics such as excellent low voltage, high efficiency, stability due to high Tg, and long life.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate 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-2-ylboronic acid and 50 g of methyl 5-bromo-2-iodobenzoate were dissolved in 600 ml of toluene, and 220 ml of K ₂ CO ₃ (2M) and 5.1 g of Pd (PPh ₃ ) ₄ were added. After stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with EA, filtered under reduced pressure and purified by column to obtain 35.8 g (72%) of intermediate A-1.

[Synthesis of A-2]

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

[Synthesis of A]

250 g of acetic acid and 1 ml of hydrochloric acid were added to 25 g of A-2, and the mixture was stirred under reflux for 24 hours, and then cooled to room temperature. The precipitated solid was filtered and then column purified to give 14.2 g (60% yield) of intermediate A.

Synthesis of Intermediate B

[Synthesis of B-1]

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

Synthesis of B-2

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

[Synthesis of B]

330 ml of acetic acid and 1.3 ml of hydrochloric acid were added to 33 g of B-2, and the mixture was stirred under reflux for 24 hours, and then cooled to room temperature. The precipitated solid was filtered and then column purified to obtain 20 g of intermediate B (65% yield).

Synthesis of Intermediate C

[Synthesis of C-1]

In a round bottom flask, 31.3 g of benzo [b] thiophen-2-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 5.1 g was added and stirred under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with EA, filtered under reduced pressure and purified by column to obtain 38.2 g (yield 75%) of intermediate C-1.

[Synthesis of C-2]

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

[Synthesis of C]

260 ml of acetic acid and 1 ml of hydrochloric acid were added to 26 g of C-2, and the mixture was stirred under reflux for 24 hours, and then cooled to room temperature. The precipitated solid was filtered and then column purified to give 14.8 g (60% yield) of intermediate C.

Synthesis of Intermediate D

Synthesis of D-1

In a round bottom flask, 31.3 g of benzo [b] thiophen-2-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 5.1 g was added and stirred under reflux. The reaction was confirmed by TLC and the reaction was terminated after the 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

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

Synthesis of D

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

OP synthesis

Preparation of OP for the synthesis of the desired compound was carried out through the following steps.

Synthesis of OP1

15 g of diphenylamine in a round bottom flask, 47.7 g of 4-bromo-4'-iodo-1,1'-biphenyl, 12.8 g of t-BuONa, 3.3 g of Pd ₂ (dba) ₃ , 5.4 ml of (t-Bu) ₃ P Was dissolved in 600 ml of toluene and stirred at 50 ° C. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with EA, filtered under reduced pressure and purified by column to obtain 15.26 g (yield 43%) of intermediate OP1-1.

15 g of the intermediate OP1-1, 7.0 g of [1,1'-biphenyl] -4-amine, 5.4 g of t-BuONa, 1.4 g of Pd ₂ (dba) ₃ , 1.7 ml of (t-Bu) ₃ P and toluene 200 It was dissolved in ml and stirred under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with EA, filtered under reduced pressure and purified by column to obtain 9.15 g (50% yield) of intermediate OP1.

The following intermediate was synthesized in the same manner as in OP1.

Example 1 Synthesis of Compound 1

In a round bottom flask, Intermediate A 2.5 g, di ([1,1'-biphenyl] -4-yl) amine 3.08 g, t-BuONa 1.15 g, Pd ₂ (dba) ₃ 0.3 g, (t-Bu) ₃ P 0.4 ml was dissolved in 60 ml of toluene and stirred at reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with EA, filtered under reduced pressure and purified by column to obtain 2.56 g (yield 58%) of compound 1.

m / z: 553.24 (100.0%), 554.24 (44.8%), 555.25 (9.8%), 556.25 (1.5%)

Example 2: Synthesis of Compound 2

N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2 instead of di ([1,1'-biphenyl] -4-yl) amine in Example 1 Compound 2 was synthesized in the same manner as Compound 1 using -amine.

m / z: 593.27 (100.0%), 594.28 (48.0%), 595.28 (11.5%), 596.28 (1.9%)

Example 3: Synthesis of Compound 3

In Example 1, N-([1,1'-biphenyl] -4-yl)-[1,1 ': 4', 1 'instead of di ([1,1'-biphenyl] -4-yl) amine Compound 3 was synthesized in the same manner as Compound 1 using '-terphenyl] -4-amine.

m / z: 629.27 (100.0%), 630.28 (51.3%), 631.28 (13.1%), 632.28 (2.3%)

Example 4: Synthesis of Compound 4

Compound 4 was synthesized in the same manner as in compound 1, using Intermediate OP1 instead of di ([1,1′-biphenyl] -4-yl) amine in Example 1.

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

Example 5: Synthesis of Compound 5

Compound 5 was synthesized in the same manner as in compound 1, using Intermediate OP2 instead of di ([1,1′-biphenyl] -4-yl) amine in Example 1.

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

Example 6: Synthesis of Compound 6

Compound 6 was synthesized in the same manner as in compound 1, using Intermediate OP3 instead of di ([1,1′-biphenyl] -4-yl) amine in Example 1.

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

Example 7: Synthesis of Compound 7

Compound 9 was synthesized in the same manner as in compound 1, using Intermediate OP4 instead of di ([1,1′-biphenyl] -4-yl) amine in Example 1.

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

Example 8: Synthesis of Compound 8

Compound 8 was synthesized in the same manner as in compound 1, using Intermediate OP5 instead of di ([1,1′-biphenyl] -4-yl) amine in Example 1.

m / z: 760.35 (100.0%), 761.35 (61.1%), 762.35 (19.0%), 763.36 (3.6%)

Example 9: Synthesis of Compound 9

Compound 9 was synthesized in the same manner as Compound 1 using Intermediate B instead of Intermediate A.

m / z: 677.27 (100.0%), 678.28 (55.6%), 679.28 (15.4%), 680.28 (2.9%)

Example 10 Synthesis of Compound 10

Compound 10 was synthesized in the same manner as Compound 2 using Intermediate B instead of Intermediate A.

m / z: 717.30 (100.0%), 718.31 (58.9%), 719.31 (17.2%), 720.31 (3.3%)

Example 11: Synthesis of Compound 11

Compound 11 was synthesized in the same manner as Compound 4 using Intermediate B instead of Intermediate A.

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

Example 12: Synthesis of Compound 12

Compound 14 was synthesized in the same manner as Compound 7 using Intermediate B instead of Intermediate A.

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

Example 13: Synthesis of Compound 13

Compound 13 was synthesized in the same manner as Compound 8 using Intermediate B instead of Intermediate A.

m / z: 884.38 (100.0%), 885.38 (72.0%), 886.38 (25.9%), 887.39 (5.9%), 888.39 (1.1%)

Example 14 Synthesis of Compound 14

Compound 14 was synthesized in the same manner as compound 1 using intermediate C instead of intermediate A.

m / z: 569.22 (100.0%), 570.22 (45.5%), 571.22 (10.1%), 571.21 (4.5%), 572.22 (2.1%), 572.23 (1.4%)

Example 15 Synthesis of Compound 15

Compound 15 was synthesized in the same manner as compound 2 using intermediate C instead of intermediate A.

m / z: 609.25 (100.0%), 610.25 (48.8%), 611.26 (11.3%), 611.24 (4.5%), 612.25 (2.2%), 612.26 (1.8%)

Example 16: Synthesis of Compound 16

Compound 16 was synthesized in the same manner as compound 3 using intermediate C instead of intermediate A.

m / z: 645.25 (100.0%), 646.25 (52.0%), 647.26 (12.9%), 647.24 (4.5%), 648.25 (2.4%), 648.26 (2.2%)

Example 17 Synthesis of Compound 17

Compound 17 was synthesized in the same manner as compound 4 using intermediate C instead of intermediate A.

m / z: 736.29 (100.0%), 737.29 (58.9%), 738.30 (16.4%), 738.29 (5.4%), 739.30 (3.2%), 739.29 (2.7%)

Example 18: Synthesis of Compound 18

Compound 18 was synthesized in the same manner as Compound 5 using Intermediate C instead of Intermediate A.

m / z: 710.28 (100.0%), 711.28 (55.6%), 712.28 (15.8%), 712.27 (4.5%), 713.29 (2.7%), 713.27 (2.5%), 711.27 (1.5%)

Example 19: Synthesis of Compound 19

Compound 19 was synthesized in the same manner as Compound 6 using Intermediate C instead of Intermediate A.

m / z: 658.24 (100.0%), 659.25 (51.2%), 660.25 (13.3%), 660.24 (4.9%), 661.24 (2.3%), 661.25 (2.3%), 659.24 (1.5%)

Example 20 Synthesis of Compound 20

Compound 20 was synthesized in the same manner as compound 7 using intermediate C instead of intermediate A.

m / z: 734.28 (100.0%), 735.28 (57.8%), 736.28 (17.0%), 736.27 (4.5%), 737.29 (3.0%), 737.27 (2.6%), 735.27 (1.5%)

Example 21: Synthesis of Compound 21

Compound 21 was synthesized in the same manner as compound 8 using intermediate C instead of intermediate A.

m / z: 776.32 (100.0%), 777.33 (61.1%), 778.33 (18.8%), 778.32 (5.0%), 779.33 (3.8%), 779.32 (2.8%), 777.32 (1.5%)

Example 22: Synthesis of Compound 22

Compound 22 was synthesized in the same manner as Compound 1 using Intermediate D instead of Intermediate A.

m / z: 693.25 (100.0%), 694.25 (56.3%), 695.26 (15.1%), 695.24 (4.5%), 696.26 (2.8%), 696.25 (2.6%)

Example 23: Synthesis of Compound 23

Compound 23 was synthesized in the same manner as Compound 2 using Intermediate D instead of Intermediate A.

m / z: 733.28 (100.0%), 734.28 (59.6%), 735.29 (17.0%), 735.28 (5.2%), 736.29 (3.4%), 736.28 (2.7%)

Example 24: Synthesis of Compound 24

Compound 24 was synthesized in the same manner as Compound 4 using Intermediate D instead of Intermediate A.

m / z: 860.32 (100.0%), 861.33 (68.6%), 862.33 (23.7%), 863.33 (5.4%), 862.32 (5.0%), 863.32 (3.1%), 861.32 (1.5%), 864.33 (1.1% )

Example 25 Synthesis of Compound 25

Compound 25 was synthesized in the same manner as Compound 7 using Intermediate D instead of Intermediate A.

m / z: 858.31 (100.0%), 859.31 (69.4%), 860.31 (23.9%), 861.32 (5.1%), 860.30 (4.5%), 861.31 (3.5%), 862.31 (1.1%)

Example 26: Synthesis of Compound 26

Compound 26 was synthesized in the same manner as Compound 8 using Intermediate D instead of Intermediate A.

m / z: 900.35 (100.0%), 901.36 (71.9%), 902.36 (26.1%), 903.36 (6.2%), 902.35 (5.1%), 903.35 (3.3%), 901.35 (1.5%), 904.36 (1.2% ), 904.37 (1.0%)

Fabrication of Organic Light Emitting Diode

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

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 used the following materials.

Example 27

A glass substrate coated with an indium tin oxide (ITO) 1500 Å thick thin film was washed by distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a plasma cleaner, and then cleaned the substrate using oxygen plasma for 5 minutes and then a thermal vacuum evaporator (thermal Compound 1 250 Hz was formed into a hole injection layer HT01 600 Hz and a hole transport layer using the evaporator. Next, the light emitting layer was doped with BH01: BD01 5% to form 250 Å. Next, ET01: Liq (1: 1) 300 Å was formed into an electron transport layer, followed by LiF 10 Å and aluminum (Al) 1000 막.

Examples 28-52

In the same manner as in Example 27, an organic light emitting diode was manufactured in which the hole injection layer and the hole transport layer were formed using the compounds 2 to 26, respectively.

Comparative Example 1

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

Comparative Example 2

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

Performance Evaluation of Organic Light Emitting Diode

Inject electrons and holes by applying voltage to a Keithley 2400 source measurement unit and measure the luminance when light is emitted using the Konica Minolta Spectroradiometer (CS-2000) Thus, the performance of the organic light emitting diodes of Examples and Comparative Examples was evaluated by measuring the current density and luminance with respect to the applied voltage under atmospheric pressure conditions, and the results are shown in Table 1.

Table 1

	Op. V	mA / cm2	Cd / A	lm / w	CIEx	CIEy	life span
Example 27	4.031	10	6.09	3.80	0.141	0.121	27
Example 28	4.052	10	6.25	3.79	0.141	0.120	30
Example 29	4.013	10	5.98	3.91	0.142	0.120	29
Example 30	4.031	10	5.95	3.89	0.139	0.119	33
Example 31	4.054	10	6.17	3.91	0.140	0.118	34
Example 32	4.056	10	6.10	3.92	0.140	0.117	41
Example 33	4.035	10	6.13	3.87	0.138	0.118	42
Example 34	4.041	10	5.99	3.89	0.141	0.119	37
Example 35	4.028	10	6.00	3.90	0.142	0.116	39
Example 36	4.021	10	6.27	3.93	0.141	0.115	45
Example 37	4.031	10	6.03	3.88	0.142	0.115	40
Example 38	4.061	10	6.17	3.90	0.141	0.116	40
Example 39	4.052	10	5.98	3.85	0.141	0.114	32
Example 40	4.061	10	5.80	3.80	0.142	0.114	29
Example 41	4.067	10	5.79	3.80	0.142	0.116	29
Example 42	4.067	10	5.78	3.81	0.142	0.116	31
Example 43	4.051	10	5.82	3.79	0.141	0.117	30
Example 44	4.068	10	5.87	3.77	0.141	0.114	30
Example 45	4.059	10	5.80	3.77	0.141	0.114	27
Example 46	4.057	10	5.82	3.80	0.141	0.114	29
Example 47	4.060	10	5.87	3.85	0.140	0.115	35
Example 48	4.060	10	5.89	3.79	0.141	0.115	33
Example 49	4.059	10	5.90	3.78	0.142	0.115	33
Example 50	4.058	10	5.87	3.84	0.142	0.114	30
Example 51	4.055	10	5.90	3.87	0.141	0.113	29
Example 52	4.060	10	5.85	3.87	0.141	0.113	27
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, the embodiments of the present invention can be confirmed that the physical properties are excellent in all aspects compared to Comparative Example 1 and Comparative Example 2. It can be seen that the present compound has low voltage driving, high efficiency and long life due to easy hole injection and excellent hole transport.

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

Claims (6)

1. Compound represented by the following formula (1):

   [Formula 1]

   

   Where

   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 an aryl group of an alkynyl group, an alkoxy group of C _1-30, are C _6-30 aryloxy groups, be substituted by a heteroaryl group of the C _6-30 aryl group, or a C _2-30 substituted or the C _6-50; 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 Or a C _2-50 heteroaryl group which is unsubstituted or substituted with an oxy group, a C _6-30 aryl group, or a C _2-30 heteroaryl group, and Ar ₂ and Ar ₃ may be connected to each other,

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

   m is 1 or 2,

   n is an integer from 0 to 2,

   *-Is a coupling site.
2. The method of claim 1,

   Compounds characterized in that represented by one of the following formulas 2 to 3:

   [Formula 2]

   

   [Formula 3]

   

   In Formula 2 or 3, X, Ar ₁ , Ar ₂ , Ar ₄ , R ₁ and R ₂ are the same as defined in Formula 1, and R ₃ is the same as the definition of R ₁ .
3. The method of claim 1,

   Compounds characterized in that represented by any one of the following formula:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
4. The preparation method of Chemical Formula 1 represented by Scheme 1 below:

   Scheme 1

   

   In Formula 2 or 3, X, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , R ₁ , R ₂ , m and n are the same as defined in Formula 1, wherein R is R ₁ or R ₂ .
5. An organic light emitting device comprising an anode, a cathode and at least one organic layer containing the compound of claim 1 between two electrodes.
6. The method of claim 5,

   The organic light emitting device, characterized in that the organic material layer is a hole injection layer or a hole transport layer.

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