WO2016021923A2 - Novel compound and orgarnic light emitting device containing same - Google Patents

Abstract

The present invention relates to a novel compound and, especially, to a novel compound which, when applied to an organic light emitting device, has excellent hole injection and hole transport properties and simultaneously has an excellent electron blocking property, can implement high triplet energy and high Tg, and enables the organic light emitting device to have low driving voltage, low power consumption, high efficiency, and long lifetime.

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, in particular, when applied to the organic light emitting device has excellent hole injection and hole transfer characteristics, at the same time excellent electron blocking characteristics, high triplet energy and high Tg The present invention relates to a novel compound that can be implemented and has a low driving voltage, low power consumption, high efficiency, and long life.

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. The light emitting material may be classified into a polymer and a low molecule according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. According to the emission color can be divided into blue, green, red light emitting material and yellow and orange light emitting material required to implement a better natural color. In addition, in order to increase luminous efficiency through an increase in color purity and energy transfer, a host / dopant system may be used as a light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to produce high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant and the host to be used.

In particular, many amine derivatives having a carbazole skeleton have been studied for the hole injection and hole transport materials used in the organic light emitting device. However, due to the higher driving voltage, lower efficiency, and shorter lifetime, there are many difficulties in practical use. 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 is excellent in the hole injection and hole transfer characteristics when applied to the organic light emitting device, and at the same time excellent in the electron blocking characteristics, high triplet energy and high Tg can be realized, low driving It is an object of the present invention to provide a novel compound capable of having voltage, low power consumption, high efficiency and long life.

The present invention also includes an organic compound capable of achieving excellent triplet energy and high Tg at the same time with excellent hole injection and hole transport characteristics, including low drive voltage, low power consumption, high efficiency and long life. It is an object to provide a light emitting element.

In order to achieve the above object, the present invention provides a compound represented by the following Chemical Formula 1:

[Formula 1]

Where

l, m, n, o are each independently an integer selected from 1 to 4, Ar is each independently deuterium, halogen, amino, nitrile, nitro, C _1-30 alkyl, C _1-30 alkoxy C _6-50 aryl group which is _optionally substituted with a group, a C _2-30 alkenyl group, a silane group; Or C _2-50 heteroaryl unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, silane group Gigi,

R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; Silane group; 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; Deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, C _6-50 aryl group which is unsubstituted or substituted; Or C _2-50 heteroaryl unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, silane group It is.

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

When the compound of the present invention is applied to an organic light emitting device, it has excellent hole injection and hole transport characteristics, and at the same time, excellent electron blocking characteristics, high triplet energy and high Tg, low driving voltage, low power consumption, high efficiency and It can have a long life.

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

l, m, n, o are each independently an integer selected from 1 to 4, Ar is each independently deuterium, halogen, amino, nitrile, nitro, C _1-30 alkyl, C _1-30 alkoxy C _6-50 aryl group which is _optionally substituted with a group, a C _2-30 alkenyl group, a silane group; Or C _2-50 heteroaryl unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, silane group Gigi,

R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; Silane group; 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; Deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, C _6-50 aryl group which is unsubstituted or substituted; Or C _2-50 heteroaryl unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, silane group It is.

Preferably, the compound of Formula 1 may be a compound represented by the following Formula 2 or 3. In this case, lifespan and efficiency can be further improved.

[Formula 2]

[Formula 3]

In Formula 2 or Formula 3, l, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are the same as defined in Formula 1, and Ar ₁ , Ar ₂ , and Ar ₃ are each independently deuterium, halogen, C _6-50 aryl group which is unsubstituted or substituted with an amino group, a nitrile group, a nitro group, a C _1-30 alkyl group, a C _1-30 alkoxy group, a C _2-30 alkenyl group, a silane group; Or C _2-50 heteroaryl unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, silane group Gigi,

X is O, S, CR ₉ R ₁₀ , or SiR ₁₁ R ₁₂ ,

R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; Silane group; 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; Deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, C _6-50 aryl group which is unsubstituted or substituted; Or C _2-50 heteroaryl unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, silane group It is.

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

The compound of formula 1 according to the present invention has excellent hole injection and hole transport characteristics when applied to an organic light emitting device, and at the same time excellent in electron blocking characteristics, high triplet energy and high Tg, low driving voltage, low consumption It can have power, high efficiency and long life. In particular, when Ar included in the repeating unit l in Formula 1 includes a biphenyl group or a fluorene group, life and efficiency may be further improved.

Compounds of the invention can also be prepared via Scheme 1 or Scheme 2:

Scheme 1

Scheme 2

In Schemes 1 and 2, l, m, n, o, Ar, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ 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. Preferably it is included as a hole injection material or a hole transport material, In this case, the compound of the present invention may be used alone or in combination with a known organic light emitting compound. In particular, when Ar included in the repeating unit l in Formula 1 includes a biphenyl group or a fluorene group, the life and efficiency may be further improved, and when the two or more compounds are mixed, the life and efficiency may be further improved. In addition, when the difference in molecular weight of the compound used to be mixed is less than 50 is possible to be deposited at the same time when the deposition, Ar in the repeating unit l in Formula 1 includes a compound containing a biphenyl group and in the repeating unit l in Formula 1 When Ar is mixed with two or more compounds including a fluorene group, it may bring about excellent life and efficiency improvement effects. In particular, when used together with an anthracene-based fluorescent host, life and efficiency may be greatly improved.

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.

The hole injection layer material may be a compound represented by Formula 1 of the present invention, it may be used with a known material. The known material is not particularly limited, and TCTA (4,4 ′, 4 ″ -tri (N-carbazolyl) triphenyl, which is a phthalocyanine compound or starburst amine derivatives such as copper phthalocyanine disclosed in US Pat. No. 4,356,429 Amine), 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 material may be a compound represented by the formula (1) of the present invention, it may be used with a known material. The known material is not particularly limited, and may be arbitrarily selected and used from conventional known materials used in the hole transport layer. Specifically, the hole transport layer material is carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-ratio Ordinary amines having aromatic condensed rings such as phenyl] -4,4'-diamine (TPD), N.N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD) 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 use a known compound as a host or dopant, and preferably include a compound represented by the following formula (4). In this case, low driving voltage, low power consumption, high efficiency, and long life can be improved.

[Formula 4]

In Chemical Formula 4,

Ar ₄ and Ar ₅ are each independently 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 which is unsubstituted or substituted with deuterium, a halogen, an amino group, a nitrile group, a nitro group, preferably Ar ₄ and Ar ₅ are asymmetrical, and in this case, the effect of improving life and efficiency is confirmed. Can and

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , and R ₂₀ are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; 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.

The compound represented by Chemical Formula 4 may be one of compounds represented by the following chemical formula as a specific example.

In addition, as an example, in addition to the compound, as a light emitting layer material, a fluorescent dopant may be IDE102 or IDE105, or BD142 (N ⁶ , N ¹² -bis (3,4-dimethylphenyl) -N ⁶ , N, which may be purchased from Idemitsu. ¹² -dimethycrylicene-6,12-diamine) can be used, green phosphorescent dopant Ir (ppy) ₃ (tris (2-phenylpyridine) iridium), blue phosphorescent dopant F 2 Irpic (iridium ( III) bis [4,6-difluorophenyl) -pyridinato-N, C2 '] picolinate), 7 red phosphorescent dopant RD61 from UDC, and the like can be co-vacuum deposited (doped).

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 includes the compound represented by Chemical Formula 1, and has excellent hole injection and hole transport characteristics, and at the same time, excellent electron blocking characteristics, high triplet energy and high Tg, and low driving voltage. It has low power consumption, high efficiency 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.

OP synthesis

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

Synthesis of OP1 below is as follows.

Toluene was added 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 and} 2.6 ml of (t-Bu) ₃ P in a round bottom flask. After dissolving in 100 ml and stirred at 50 ℃. 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 OP1-1.

6.62 g of the OP1-1 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 OP1 (yield 81%).

In the same manner as in OP1, the following OP2 to OP9 were synthesized.

Synthesis of Compound 1

In a round bottom flask, 3.0 g of 2-bromo-1-phenyl-1H-indole and 5.11 g of OP1 5.11 g were dissolved in 30 ml of 1,4-dioxan, followed by 16 ml of K ₂ CO ₃ (2M) and 0.38 g of Pd (PPh ₃ ) _4. 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 MC, filtered under reduced pressure and recrystallized after column purification to obtain 2.84 g (yield 53%) of compound 1.

m / z: 486.21 (100.0%), 487.21 (39.7%), 488.22 (7.5%)

Synthesis of Compound 2

Compound 2 was synthesized using OP 2 instead of OP 1 in the same manner as compound 1. (Yield 57%)

m / z: 588.26 (100.0%), 589.26 (48.0%), 590.26 (11.4%), 591.27 (1.7%)

Synthesis of Compound 3

Compound 3 was synthesized using OP3 instead of OP1 in the same manner as compound 1. (50% yield)

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

Synthesis of Compound 4

Compound 4 was synthesized using OP4 instead of OP1 in the same manner as compound 1. (Yield 55%)

m / z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)

Synthesis of Compound 5

Compound 5 was synthesized using OP5 instead of OP1 in the same manner as compound 1. (Yield 48%)

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

Synthesis of Compound 6

Compound 6 was synthesized using OP6 instead of OP1 in the same manner as compound 1. (Yield 42%)

m / z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)

Synthesis of Compound 7

Compound 7 was synthesized using OP7 instead of OP1 in the same manner as compound 1. (Yield 45%)

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 using OP4 instead of OP1 with 3-bromo-1-phenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole in the same manner as compound 1. (61% yield)

m / z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)

Synthesis of Compound 9

Compound 9 was synthesized using OP5 instead of OP1 as 3-bromo-1-phenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole in the same manner as compound 1. (Yield 55%)

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

Synthesis of Compound 10

Compound 10 was synthesized using OP6 instead of OP1 as 3-bromo-1-phenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole in the same manner as compound 1. (61% yield)

m / z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)

Synthesis of Compound 11

Compound 11 was synthesized using OP7 instead of OP1 with 3-bromo-1-phenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole in the same manner as compound 1. (Yield 55%)

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 using OP8 instead of OP1 with 3-bromo-1-phenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole in the same manner as compound 1. (Yield 40%)

m / z: 664.29 (100.0%), 665.29 (54.5%), 666.29 (14.7%), 667.30 (2.5%)

Synthesis of Compound 13

Compound 13 was synthesized using OP9 instead of OP1 with 3-bromo-1-phenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole in the same manner as compound 1. (Yield 38%)

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

Synthesis of Compound 14

Compound 14 was synthesized using OP5 instead of OP1 as 3-bromo-1,2-diphenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole in the same manner as compound 1. (Yield 52%)

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

Synthesis of Compound 15

Compound 15 was synthesized in the same manner as in compound 1, using OP7 instead of OP1 as 3-bromo-1,2-diphenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole. (Yield 43%)

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

Synthesis of Compound 16

Compound 16 was synthesized in the same manner as in compound 1, using 3-bromo-1-phenyl-indole-d5 instead of 2-bromo-1-phenyl-1H-indole and OP5 instead of OP1. (Yield 57%)

m / z: 709.35 (100.0%), 710.35 (58.1%), 711.36 (16.4%), 712.36 (3.0%)

Synthesis of Compound 17

Compound 17 was synthesized in the same manner as in compound 1, using 3-bromo-1-phenyl-indole-d5 instead of 2-bromo-1-phenyl-1H-indole and OP7 instead of OP1. (50% yield)

m / z: 709.35 (100.0%), 710.35 (58.1%), 711.36 (16.4%), 712.36 (3.0%)

Synthesis of Compound 18

Compound 18 was synthesized in the same manner as in compound 1, using OP10 instead of OP1 as 3-bromo-1-phenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole. (Yield 59%)

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

Synthesis of Compound 19

Compound 19 was synthesized using OP11 instead of OP1 as 3-bromo-1-phenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole in the same manner as compound 1. (Yield 51%)

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

Synthesis of Compound 20

Compound 20 was synthesized in the same manner as in compound 1, using OP10 instead of OP1 as 3-bromo-1,2-diphenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole. (Yield 49%)

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

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 is laminated in order.

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

Fabrication of Organic Light Emitting Diode

Example 1

A glass substrate coated with an indium tin oxide (ITO) 1500 Å thick thin film was washed by distilled water ultrasonically. After the distilled water is washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. is dried, transferred to a plasma cleaner, and the substrate is cleaned for 5 minutes using an oxygen plasma. Compound 1 250 Å was formed into a hole injection layer HI01 600 Å and a hole transport layer using an evaporator. Next, the light emitting layer was doped with 3% of the dopant BD01 to the host BH01 to form a 250-kV film. 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 2-20

In the same manner as in Example 1, an organic light emitting diode was manufactured in which the hole transport layer was formed by using compounds 2 to 20, respectively.

Example 21

In the same manner as in Example 1, an organic light emitting device was manufactured by using the composition in which the hole transport layer was mixed (weight ratio) with Compound 4 and Compound 50:50:50.

Example 22

In the same manner as in Example 1, an organic light emitting diode was manufactured by using the composition in which the hole transport layer was mixed (weight ratio) with Compound 5 and Compound 9 50:50.

Example 23

In the same manner as in Example 1, an organic light emitting device was manufactured by using the composition in which the hole transport layer was mixed (weight ratio) with Compound 9 and Compound 16 50:50.

Example 24

In the same manner as in Example 1, an organic light emitting diode was manufactured by using the composition in which the hole transport layer was mixed (weight ratio) with Compound 9 and Compound 18 50:50.

Example 25

In the same manner as in Example 1, an organic light emitting diode was manufactured by using the composition in which the hole transport layer was mixed (weight ratio) with Compound 11 and Compound 17 50:50.

Example 26

AND instead of BH01 as the host of the light emitting layer of Example 16 The device was fabricated in the same manner except that it was used.

Example 27

A device was manufactured in the same manner as in Example 16, except that BH02 was used instead of BH01 as the host.

Example 28

A device was manufactured in the same manner as in Example 16, except that BH03 was used instead of BH01 as the host.

Example 29

The device was manufactured in the same manner as in the light emitting layer of Example 23, except that BH03 was used instead of BH01 as the light emitting layer.

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.

Comparative Examples 2 to 5

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

Comparative Example 6

In Example 1, the hole transport layer is Ref. 3, and the light emitting layer is a host. The device was fabricated in the same manner except that it was used.

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

	Drive voltage Open V	Current density mA / cm2	Current Efficiency Cd / A	Power efficiency lm / w	Color coordinates CIEx	Color coordinates	LifespanLT97 (hr)
Example 1	4.40	10	6.32	5.15	0.141	0.112	27
Example 2	4.21	10	6.75	5.27	0.141	0.112	34
Example 3	4.16	10	6.75	5.33	0.142	0.112	37
Example 4	4.05	10	6.97	5.61	0.141	0.111	51
Example 5	4.00	10	6.93	5.65	0.142	0.111	53
Example 6	4.07	10	6.90	5.60	0.141	0.111	50
Example 7	4.02	10	6.95	5.63	0.142	0.110	52
Example 8	3.87	10	7.22	6.23	0.140	0.110	59
Example 9	3.80	10	7.33	6.15	0.139	0.109	62
Example 10	3.90	10	7.29	6.19	0.140	0.110	61
Example 11	3.83	10	7.37	6.21	0.140	0.109	65
Example 12	3.92	10	7.20	6.12	0.140	0.110	60
Example 13	3.85	10	7.35	6.09	0.140	0.110	64
Example 14	3.81	10	7.31	6.24	0.140	0.110	61
Example 15	3.84	10	7.21	6.15	0.140	0.110	61
Example 16	3.80	10	7.41	6.35	0.140	0.109	71
Example 17	3.82	10	7.39	6.31	0.140	0.110	72
Example 18	3.81	10	7.37	6.17	0.140	0.110	65
Example 19	3.79	10	7.21	6.14	0.141	0.111	59
Example 20	3.82	10	7.32	6.19	0.140	0.110	61
Example 21	3.65	10	7.91	6.65	0.140	0.109	80
Example 22	3.63	10	7.99	6.61	0.140	0.110	90
Example 23	3.63	10	7.97	6.67	0.140	0.110	94
Example 24	3.64	10	7.91	6.64	0.141	0.110	99
Example 25	3.60	10	7.92	6.69	0.140	0.109	105
Example 26	3.85	10	7.03	6.00	0.140	0.111	39
Example 27	3.85	10	7.34	6.28	0.140	0.110	73
Example 28	3.85	10	7.40	6.33	0.140	0.110	69
Example 29	3.65	10	7.92	6.70	0.140	0.109	101
Comparative Example 1	4.65	10	5.74	4.67	0.143	0.113	15
Comparative Example 2	5.03	10	4.84	4.10	0.145	0.120	-
Comparative Example 3	4.43	10	6.03	4.85	0.141	0.113	18
Comparative Example 4	4.35	10	6.15	5.01	0.141	0.112	22
Comparative Example 5	4.82	10	5.15	4.14	0.141	0.125	-
Comparative Example 6	4.37	10	6.08	4.90	0.141	0.113	7

"-" In Table 1 is the case where the luminescence disappeared within one hour.

As shown in Table 1, Examples 1 to 29 of the present invention can be confirmed that the physical properties are excellent in all aspects compared to Comparative Examples 1 to 6. Even though they have the same indole moiety as compared to Comparative Examples 2 and 6, it was found that indole 2,3-positioned aryl amine-substituted compounds had a great effect on efficiency and lifespan due to excellent molecular arrangement and excellent hole mobility in the thin film state. Can be.

Particularly, as shown in the results of Examples 4 to 20, when Ar included in the repeating unit l in Formula 1 included a biphenyl group or a fluorene group, it was confirmed that the lifespan and efficiency were further improved. Examples 21 to 25 and 29 using a mixture of two or more compounds showed a further improvement in lifespan and efficiency, and Ar in the repeating unit l in Formula 1 includes a biphenyl group and a fluorene group In the case of mixing above, excellent life and efficiency improvement effects were confirmed, and when Ar ₄ and Ar ₅ in Formula 4 were different, the life and efficiency improvement effects were confirmed.

When the compound of the present invention is applied to an organic light emitting device, it has excellent hole injection and hole transport characteristics, and at the same time, excellent electron blocking characteristics, high triplet energy and high Tg, low driving voltage, low power consumption, high efficiency and It can have a long life.

Claims (11)

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

   [Formula 1]

   

   Where

   l, m, n, o are each independently an integer selected from 1 to 4, Ar is each independently deuterium, halogen, amino, nitrile, nitro, C _1-30 alkyl, C _1-30 alkoxy C _6-50 aryl group which is _optionally substituted with a group, a C _2-30 alkenyl group, a silane group; Or C _2-50 heteroaryl unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, silane group Gigi,

   R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; Silane group; 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; Deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, C _6-50 aryl group which is unsubstituted or substituted; Or C _2-50 heteroaryl unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, silane group It is.
2. The method of claim 1,

   The compound is a compound characterized in that the compound represented by the following formula (2) or (3):

   [Formula 2]

   

   [Formula 3]

   

   In Formula 2 or Formula 3, l, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are the same as defined in Formula 1, and Ar ₁ , Ar ₂ , and Ar ₃ are each independently deuterium, halogen, C _6-50 aryl group which is unsubstituted or substituted with an amino group, a nitrile group, a nitro group, a C _1-30 alkyl group, a C _1-30 alkoxy group, a C _2-30 alkenyl group, a silane group; Or C _2-50 heteroaryl unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, silane group Gigi,

   X is O, S, CR ₉ R ₁₀ , or SiR ₁₁ R ₁₂ ,

   R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; Silane group; 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; Deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, C _6-50 aryl group which is unsubstituted or substituted; Or C _2-50 heteroaryl unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, silane group It is.
3. The method of claim 1,

   -(Ar) ₁ -is a compound represented by the formula (1), characterized in that biphenyl or fluorene.
4. The method according to claim 1 or 2,

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

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
5. An organic light emitting device comprising an anode, a cathode, and at least one organic material layer containing a compound according to any one of claims 1 to 4 between two electrodes.
6. The method of claim 5,

   An organic light emitting device, characterized in that the organic material layer comprises two or more compounds according to claim 4.
7. The method of claim 5,

   The organic light emitting device, characterized in that the organic layer contains the compound of claim 1 as a hole injection material or a hole transport material.
8. The method of claim 5,

   The organic light-emitting device, characterized in that the organic compound is a compound containing Ar in the repeating unit l in the formula 1 includes a biphenyl group and Ar in the repeating unit l in the formula (1) including a fluorene group device.
9. The method of claim 5,

   The organic light emitting device is an organic light emitting device characterized in that it comprises a compound represented by the formula (4) in the light emitting layer:

   [Formula 4]

   

   In Chemical Formula 4,

   Ar ₄ and Ar ₅ are each independently 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 ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , and R ₂₀ are each independently hydrogen; heavy hydrogen; halogen; Amino group; Nitrile group; Nitro group; 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.
10. The method of claim 9,

    Organic light emitting device, characterized in that the Ar ₄ and Ar ₅ of the general formula (4) is asymmetric
11. The method of claim 9,

    The compound represented by Formula 4 is an organic light emitting device, characterized in that any one of the compounds represented by the following formula:

    

    

    

    

    

    

    

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