WO2015174791A1

WO2015174791A1 - Novel compound and organic light-emitting element comprising same

Info

Publication number: WO2015174791A1
Application number: PCT/KR2015/004916
Authority: WO
Inventors: 함호완; 김봉기; 안현철; 김성훈; 김동준; 배유진; 조지은; 이형진; 임동환; 안자은
Original assignee: 주식회사 동진쎄미켐
Priority date: 2014-05-16
Filing date: 2015-05-15
Publication date: 2015-11-19

Abstract

The novel compound according to the present invention has an HOMO energy level that facilitates hole injection, has a high LUMO energy level that enables the blocking of electrons, has excellent hole transportation properties, and, when applied to the hole injection layer, hole transportation layer or hole transportation auxiliary layer of an organic light-emitting element, can impart stability and extended lifespan due to having excellent 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 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, 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 may be largely 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 functions.

Until now, a lot of amine derivatives having a carbazole skeleton have been studied for the hole injection 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 lifetime. Therefore, efforts have been made to develop organic light emitting diodes having low voltage driving, high brightness and long life using materials having excellent characteristics.

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, It is an object of the present invention to provide a novel compound capable of having excellent low voltage, high efficiency, high Tg stability and long life when applied to a hole transport layer or a hole transport auxiliary 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]

In Chemical Formula 1,

L each independently

,

, Hydrogen, deuterium, halogen, amino group, nitrile group, nitro group or C _1-30 alkyl group,

Ar each independently represents a 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,

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, R ₁ and R ₂ may form a ring with each other,

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

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

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

In Chemical Formula 1,

L each independently

,

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

Preferably, the compound represented by Chemical Formula 1 may be one of the compounds represented by the following Chemical Formulas 1-1 to 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

Ar, R ₁ , R ₂ , o, p and q in the above formula are as defined in formula (1). Preferably in the 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:

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

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

Scheme 1

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

The present invention also provides an organic light emitting device comprising the compound represented by Chemical 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 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 as an example, a method of manufacturing the organic light emitting device will be described below.

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. In addition, it may further include a hole transport auxiliary layer 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 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, Usually having an aromatic condensed ring such as 1-biphenyl] -4,4'-diamine (TPD), N.N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (-NPD) 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.

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 Korean Unexamined Patent Publication No. 10-2010-0015029, and preferably, using the compound 1 of the present invention as a hole transport auxiliary material, a hole transport auxiliary layer Can be formed.

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. Preferably, the organic light emitting device of the present invention further includes a hole transport auxiliary layer.

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

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.

중간체 1의 합성 Synthesis of Intermediate 1

[1-1` synthesis]

In a round bottom flask, 83.70 g of (1-phenyl-1H-indol-3-yl) boronic acid and 100 g of methyl 4-bromo-2-iodobenzoate are dissolved in 1200 ml of 1,4-Dioxane and K ₂ CO ₃ (2M) 450 10.2 g of ml and Pd (PPh ₃ ) ₄ were added thereto, followed by 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 93.2 g (yield 78%) of intermediate 1-1`.

[1-2` Synthesis]

After dissolving 50 g of 1-1 ′ in 1300 ml of THF, 48.4 g of CH ₃ MgBr was slowly added dropwise at 0 ° C., and gradually heated to reflux for 5 hours. The organic layer was extracted with MC and filtered under reduced pressure to obtain 35.8 g (yield 65%) of intermediate 1-2 ′.

[Synthesis of Intermediate 1]

After dissolving 35 g of 1-2 ′ in 350 ml of acetic acid, 1.5 ml of hydrochloric acid was added thereto, and the mixture was stirred 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 the mixture was purified by column to obtain 27.8 g of intermediate 1 (yield 83%).

중간체 2의 합성 Synthesis of Intermediate 2

PhMgBr was used instead of CH ₃ MgBr in the same manner as the synthesis of Intermediate 1 to synthesize 39.2 g (yield 79%) and 31.7 g (80% yield) of intermediate 2.

중간체 3의 합성Synthesis of Intermediate 3

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

중간체 4의 합성Synthesis of Intermediate 4

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

중간체 5의 합성 Synthesis of Intermediate 5

[Synthesis of 5-1`]

90 g of 5-chloro-1-phenyl-1H-indole was dissolved in 1300 ml of DMF in a round bottom flask, and the temperature was lowered to 0 ° C. and a solution of 77.3 g of NBS in 600 ml was slowly added dropwise. 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. Purified by column to give an intermediate 5-1` 88.4 g (73% yield).

[5-2` Synthesis]

5-1` 88 g and 51.7 g of (2- (methoxycarbonyl) phenyl) boronic acid were dissolved in 1000 ml of 1,4-Dioxane, and 430 ml of K ₂ CO ₃ (2M) and 9.96 g of Pd (PPh ₃ ) ₄ were added thereto. 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 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 ₃ MgBr was slowly added dropwise at 0 ° C., and gradually heated to 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]

The 5-3` 26 g was dissolved in 260 ml of acetic acid, 1.1 ml of hydrochloric acid was added thereto, and the mixture was stirred 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 purified to obtain 19.0 g (77% yield) of intermediate 5.

중간체 6의 합성 Synthesis of Intermediate 6

In the same manner as the synthesis of Intermediate 5, 62.9` 32.9 g (yield 79%) and Intermediate 6 24.7 g (yield 80%) were synthesized using PhMgBr instead of CH ₃ MgBr.

중간체 7의 합성Synthesis of Intermediate 7

(1H-indol-3-yl) boronic acid instead of (1-phenyl-1H-indol-3-yl) boronic acid and methyl 2 instead of methyl 4-bromo-2-iodobenzoate 7-1` 70.1 g (yield 75%), 3-2` 22.0 g (yield 70%) and intermediate 7 17.5 g (yield 75%) were synthesized using -bromobenzoate.

OP의 합성OP synthesis

Preparation of OP for synthesis of the desired compound was carried out via the above steps.

Synthesis of OP1 below 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 toluene 100 It was dissolved in ml 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 7.6 g (yield 45%) of intermediate OP1.

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

The following OP2 to OP10 were synthesized by the same method as the OP1.

화합물 1의 합성 Synthesis of Compound 1

In a round bottom flask, Intermediate 1 3.0 g, di ([1,1'-biphenyl] -4-yl) amine 2.73 g, t-BuONa 1.11 g, 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 the addition of water. The organic layer was extracted with EA, filtered under reduced pressure and purified by column to obtain 3.06 g (yield 63%) of compound 1.

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

화합물 2의 합성Synthesis of Compound 2

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

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

화합물 3의 합성Synthesis of Compound 3

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

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

화합물 4의 합성Synthesis of Compound 4

Compound 4 was synthesized in the same manner as 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%)

화합물 5의 합성Synthesis of Compound 5

Compound 5 was synthesized in the same manner as 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%)

화합물 6의 합성Synthesis of Compound 6

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

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

화합물 7의 합성Synthesis of Compound 7

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

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

화합물 8의 합성Synthesis 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%)

화합물 9의 합성Synthesis of Compound 9

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

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

화합물 10의 합성Synthesis of Compound 10

Compound 10 was synthesized in the same manner as 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%)

화합물 11의 합성Synthesis 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%)

화합물 12의 합성Synthesis of Compound 12

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

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

화합물 13의 합성Synthesis of Compound 13

Compound 13 was synthesized in the same manner as 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%)

화합물 14의 합성Synthesis 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%)

화합물 15의 합성Synthesis of Compound 15

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

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

화합물 16의 합성Synthesis of Compound 16

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

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

화합물 17의 합성Synthesis of Compound 17

Compound 17 was synthesized in the same manner as 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%)

화합물 18의 합성Synthesis of Compound 18

Compound 18 was synthesized in the same manner as 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%)

화합물 19의 합성Synthesis of Compound 19

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

화합물 20의 합성Synthesis 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%)

화합물 21의 합성Synthesis of Compound 21

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

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

화합물 22의 합성Synthesis of Compound 22

Compound 22 was synthesized in the same manner as 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%)

화합물 23의 합성Synthesis of Compound 23

Compound 23 was synthesized in the same manner as 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%)

화합물 24의 합성Synthesis 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%)

화합물 25의 합성Synthesis of Compound 25

Intermediate 1 as 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 for reacting 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%)

화합물 26의 합성Synthesis 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 Compound 25 except for reacting 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%)

화합물 27의 합성Synthesis 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 Except for reacting with 2-amine, Compound 27 was synthesized in the same manner as Compound 25. (50% yield)

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

유기발광소자의 제조Fabrication 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 stacked in the order of the hole injection electrode 11 / hole injection layer 12 / hole transport layer 13 / light emitting layer 14 / electron transfer layer 15 / electron injection electrode 16 from below.

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.

유기발광소자의 제조Fabrication of Organic Light Emitting Diode

실시예 1Example 1

An indium tin oxide (ITO) 1500 Å thick thin glass substrate was washed with distilled water ultrasonic waves. 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 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 5% of BH01: BD01 to form 300 Å. Next, Alq3: Liq (1: 1) 300 Å was formed into an electron transport layer, followed by Liq 10 Å and aluminum (Al) 1000 막.

실시예 2 내지 실시예 27Examples 2 to 27

In the same manner as in Example 1, 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 27, respectively.

실시예 28 Example 28

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 A hole injection layer HT01 600 Å, Compound 1 240 Å for the first hole transport layer and Compound 25 10 으로 for the second hole transport layer were formed using an evaporator. Next, the light emitting layer was doped with 5% of BH01: BD01 to form 300 Å. Next, Alq3: Liq (1: 1) 300 Å was formed into an electron transport layer, followed by Liq 10 Å and aluminum (Al) 1000 막. The organic light emitting device was fabricated by encapsulating the device in a glove box.

실시예 29 Example 29

In the same manner as in Example 28, an organic light emitting diode obtained by forming a compound 26 into a second hole transport layer was fabricated.

실시예 30Example 30

In the same manner as in Example 28, an organic light emitting diode obtained by forming a compound 27 into a second hole transport layer was manufactured.

비교예 1 Comparative Example 1

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

비교예 2Comparative Example 2

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

비교예 3 Comparative Example 3

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

비교예 4Comparative Example 4

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

비교예 5Comparative Example 5

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

유기발광소자의 성능평가Performance 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	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, Examples 1 to 30 of the present invention can be confirmed that the physical properties are excellent in all aspects compared to Comparative Examples 1 to 5. The compound represented by Chemical Formula 1 of the present invention has a high LUMO to effectively block electrons in the light emitting layer, and the hole injection is smoothly formed by arylamine group substitution, and the hole mobility is greatly improved due to excellent hole mobility. In addition, the tetracyclic structure of the compound represented by the formula (1) of the present invention can be seen that the hole injection can be formed smoothly HOMO, hole mobility is also excellent, it is seen that the driving voltage is significantly low and high efficiency have.

Claims

Compound represented by the following formula (1):

[Formula 1]

In Chemical Formula 1,

L is
,
,

Hydrogen, deuterium, halogen, amino, nitrile, nitro or C 1-30 alkyl;

Ar each independently represents a 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,

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, R 1 and R 2 may form a ring with each other,

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

o, p, q are each independently an integer of 0-4.
The method of claim 1,

at least one of m and n is non-zero:
The method of claim 1,

Compounds characterized in that represented by any one of the formula 1-1 to 1-3:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

Ar, R 1 , R 2 , o, p and q in the above formula are as defined in formula (1).
The method of claim 1,

Compounds characterized in that represented by any one of the following formula:
The preparation method of Chemical Formula 1 represented by Scheme 1 below:

Scheme 1

The target compound in Scheme 1 is a compound represented by Formula 1, Ar, L, l, R 1 , R 2 , o, p, q are as defined in Formula 1.
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.
The method of claim 6,

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