KR102448875B1 - Novel compound and organic electroluminescent device comprising same - Google Patents

Abstract

The present invention relates to a novel compound, particularly when applied to an organic light emitting device, has excellent hole injection and hole transport properties, and at the same time has excellent electron blocking properties, high triplet energy and high Tg, and low driving voltage , to a novel compound that can have low power consumption, high efficiency and long lifespan.

Description

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

The present invention relates to a novel compound and an organic light emitting device containing the same, and particularly, when applied to an organic light emitting device, it has excellent hole injection and hole transport properties, and at the same time has excellent electron blocking properties, high triplet energy and high Tg It relates to a novel compound that can be implemented, and can have a low driving voltage, low power consumption, high efficiency and long life.

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

Materials used as organic layers in organic light emitting devices may be classified into light emitting materials, hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, according to their functions. The light emitting material can be classified into high molecular weight and low molecular weight according to the molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to a light emitting mechanism. can be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing better natural colors according to the emission color. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a small amount of a dopant having a smaller energy band gap and excellent luminous efficiency than the host constituting the light emitting layer is mixed in the light emitting layer in a small amount, excitons generated from the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of the dopant and the host used.

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

In order to solve the above problems, the present invention has excellent hole injection and hole transport characteristics when applied to an organic light emitting device, and at the same time excellent electron blocking characteristics, high triplet energy and high Tg, and low driving An object of the present invention is to provide a novel compound capable of having a voltage, low power consumption, high efficiency and long life.

The present invention also includes the novel compound, which has excellent hole injection and hole transport properties, can realize high triplet energy and high Tg, and has low driving voltage, low power consumption, high efficiency and long life. An object of the present invention is to provide a light emitting device.

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

[Formula 1]

In the above formula,

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

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; a C _1-30 alkyl group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro; C _2-30 alkenyl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _1-30 alkoxy group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, or nitro group; 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 unsubstituted or substituted with a silane group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, C _2-50 heteroaryl unsubstituted or substituted with a silane group it's gi

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 properties, and at the same time has excellent electron blocking properties, can realize high triplet energy and high Tg, low driving voltage, low power consumption, high efficiency and can have a long lifespan.

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

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

[Formula 1]

In the above formula,

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

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; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, or nitro group; 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 unsubstituted or substituted with a silane group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, C _2-50 heteroaryl unsubstituted or substituted with a silane group it's gi

Preferably, the compound of Formula 1 is a compound represented by Formula 2 or 3 below. In this case, life 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 as defined in Formula 1, and Ar ₁ , Ar ₂ , and Ar ₃ are each independently deuterium, halogen, 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 C _6-50 aryl group unsubstituted or substituted with a silane group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, C _2-50 heteroaryl unsubstituted or substituted with a silane group gi,

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; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, or nitro group; 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 unsubstituted or substituted with a silane group; Or deuterium, halogen, amino group, nitrile group, nitro group, C _1-30 alkyl group, C _1-30 alkoxy group, C _2-30 alkenyl group, C _2-50 heteroaryl unsubstituted or substituted with a silane group it's gi

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 properties when applied to an organic light emitting device, and at the same time has excellent electron blocking properties, can implement 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, lifespan and efficiency may be further improved.

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

In addition, the present invention provides an organic light emitting device comprising the compound represented by 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 contains a biphenyl group or a fluorene group, lifespan and efficiency may be further improved, and when two or more compounds are mixed and used, the lifespan and efficiency will be further improved. In addition, when the molecular weight difference of the compounds used in mixture is 50 or less, simultaneous deposition is possible during deposition, and Ar included in the repeating unit l in Formula 1 contains a biphenyl group and When two or more compounds including Ar including a fluorene group are mixed, excellent life and efficiency improvement effects can be brought, and in particular, when used with an anthracene-based fluorescent host, lifespan and efficiency can be greatly improved.

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

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

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

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

As the material for the hole injection layer, the compound represented by Formula 1 of the present invention may be used, or it may be used together 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 such as copper phthalocyanine disclosed in US Patent No. 4,356,429 or starburst-type amine derivatives. 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 may be used as the hole injection layer material.

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

In addition, as the hole transport layer material, the compound represented by Formula 1 of the present invention may be used, and may be used together with a known material. The known material is not particularly limited, and may be arbitrarily selected from commonly known materials used in the hole transport layer. Specifically, the hole transport layer material is a carbazole derivative such as N-phenylcarbazole and polyvinylcarbazole, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-bi Ordinary amines having an aromatic condensed ring, such as phenyl]-4,4'-diamine (TPD), N.N'-di(naphthalen-1-yl)-N,N'-diphenyl benzidine (α-NPD), etc. derivatives and the like can be used.

Thereafter, the light emitting layer material on the hole transport layer can be formed by methods such as vacuum deposition, spin coating, casting, LB, etc., but it is easy to obtain a uniform film quality and it is difficult to generate pin holes. It is preferable to form by In the case of forming the light emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select it within the same range of conditions as those for the formation of the hole injection layer. In addition, the light emitting layer material may use a known compound as a host or dopant, and preferably includes a compound represented by the following formula (4). In this case, low driving voltage, low power consumption, high efficiency, and long life can be made more excellent.

[Formula 4]

In Formula 4,

Ar ₄ and Ar ₅ are each independently a C _6-50 aryl group substituted with or unsubstituted with deuterium, halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group, and preferably Ar ₄ and Ar ₅ are asymmetric, in this case, the life and efficiency improvement effect can be further confirmed can,

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; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; or a C _2-50 heteroaryl group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro.

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

In addition, as an example, in addition to the above compound, as a fluorescent dopant as a light emitting layer material, IDE102 or IDE105, or BD142 (N ⁶ ,N ¹² -bis(3,4-dimethylphenyl)-N ⁶ ,N available from Idemitsu) ¹² -dimethylchrysene-6,12-diamine) can be used, and the phosphorescent dopant is a green phosphorescent dopant Ir(ppy) ₃ (tris(2-phenylpyridine) iridium), and a blue phosphorescent dopant F2Irpic (iridium ( III) bis[4,6-difluorophenyl)-pyridinato-N,C2']picolinic acid salt), UDC's 7 red phosphorescent dopant RD61, etc. can be co-evacuated (doped).

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

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

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

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

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

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

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

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

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

The organic light emitting device of the present invention has excellent hole injection and hole transport properties, including the compound represented by Formula 1, and at the same time has excellent electron blocking properties, and realizes high triplet energy and high Tg, so that a low driving voltage, It has low power consumption, high efficiency and long life.

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

Synthesis of OP

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

The synthesis method of the following OP1 is as follows.

In a round-bottom flask, 10 g of N-phenylnaphthalen-1-amine, 18.0 g of 1-bromo-4-iodobenzene, 6.5 g of t-BuONa, 1.7 g of Pd ₂ (dba) ₃ , and 2.6 ml of (t-Bu) ₃ P were mixed with toluene. It was dissolved in 100 ml and stirred at 50 °C. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and column purified to obtain 7.6 g of intermediate OP1-1 (yield 45%).

The OP1-1 7.5 g bis(pinacolato)diboron 6.62 g, Pd(dppf)Cl ₂ 0.07 g, and KOAc 5.9 g were dissolved in 80 ml of toluene and stirred under reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with EA, filtered under reduced pressure, and column purified to obtain 6.8 g (yield 81%) of the intermediate OP1.

The following OP2 to OP9 were synthesized in the same manner as for OP1.

Synthesis of compound 1

In a round bottom flask, 3.0 g of 2-bromo-1-phenyl-1H-indole, 5.11 g of OP1 were dissolved in 30 ml of 1,4-dioxan, and 16 ml of K ₂ CO ₃ (2M) and 0.38 g of Pd(PPh ₃ ) ₄ were added. Then, the mixture was stirred under reflux. The reaction was confirmed by TLC, and the reaction was terminated after addition of water. The organic layer was extracted with MC, filtered under reduced pressure, and recrystallized after column purification to obtain 2.84 g of Compound 1 (yield 53%).

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

Synthesis of compound 2

In the same manner as in Compound 1, Compound 2 was synthesized using OP2 instead of OP1. (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 in Compound 1. (Yield 50%)

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 in 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

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

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

Synthesis of compound 6

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

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

Synthesis of compound 7

In the same manner as in Compound 1, Compound 7 was synthesized using OP7 instead of OP1. (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 3-bromo-1-phenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole and OP4 instead of OP1 in the same manner as in Compound 1. (Yield 61%)

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

Synthesis of compound 9

In the same manner as in Compound 1, 3-bromo-1-phenyl-1H-indole was used instead of 2-bromo-1-phenyl-1H-indole, and Compound 9 was synthesized using OP5 instead of OP1. (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 3-bromo-1-phenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole and OP6 instead of OP1 in the same manner as in Compound 1. (Yield 61%)

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

Synthesis of compound 11

In the same manner as in Compound 1, 3-bromo-1-phenyl-1H-indole was used instead of 2-bromo-1-phenyl-1H-indole, and Compound 11 was synthesized using OP7 instead of OP1. (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 in the same manner as in Compound 1 using 3-bromo-1-phenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole and OP8 instead of OP1. (Yield 40%)

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

Synthesis of compound 13

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

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

Synthesis of compound 14

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

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

Synthesis of compound 15

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

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

Synthesis of compound 16

In the same manner as in Compound 1, 3-bromo-1-phenyl-indole-d5 instead of 2-bromo-1-phenyl-1H-indole and Compound 16 was synthesized using 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 using 3-bromo-1-phenyl-indole-d5 instead of 2-bromo-1-phenyl-1H-indole and OP7 instead of OP1 in the same manner as in Compound 1. (Yield 50%)

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 using 3-bromo-1-phenyl-1H-indole instead of 2-bromo-1-phenyl-1H-indole and OP10 instead of OP1 in the same manner as in Compound 1. (yield 59%)

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

Synthesis of compound 19

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

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

Synthesis of compound 20

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

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

Manufacture of organic light emitting device

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

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

Manufacture of organic light emitting device

Example 1

A glass substrate coated with indium tin oxide (ITO) having a thickness of 1500 Å was washed with distilled water and ultrasonic waves. After cleaning with distilled water, ultrasonic cleaning is performed with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a plasma cleaner. After cleaning the substrate using oxygen plasma for 5 minutes, a thermal vacuum evaporator (thermal) An evaporator) was used to form a hole injection layer HI01 600 Å and Compound 1 250 Å as a hole transport layer. Next, as the light emitting layer, the host BH01 was doped with a dopant BD01 3% to form a film of 250 Å. Next, ET01:Liq(1:1) 300 Å was formed as an electron transport layer, LiF 10 Å, and aluminum (Al) 1000 Å were formed into a film, and the organic light emitting device was manufactured by encapsulating the device in a glove box.

Examples 2 to 20

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

Example 21

In the same manner as in Example 1, an organic light emitting device formed into a film using a composition in which the hole transport layer was mixed (weight ratio) of Compound 4 and Compound 5 50:50 was manufactured.

Example 22

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

Example 23

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

Example 24

In the same manner as in Example 1, an organic light emitting device formed into a film using a composition in which a hole transport layer was mixed (weight ratio) of Compound 9 and Compound 18 50:50 was manufactured.

Example 25

In the same manner as in Example 1, an organic light emitting device formed into a film was manufactured using a composition in which the hole transport layer was mixed (weight ratio) of Compound 11 and Compound 17 at 50:50.

Example 26

Using the light emitting layer of Example 16 as a host, AND instead of BH01 A 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 for the emission layer of Example 16.

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 for the emission layer of Example 16.

Example 29

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

Comparative Example 1

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

Comparative Examples 2 to 5

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

Comparative Example 6

The hole transport layer of Example 1 is Ref. 3, the light emitting layer is the host, AND instead of BH01 A device was fabricated in the same manner except that it was used.

Performance evaluation of organic light emitting devices

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

drive voltage
Open V current density
mA/cm2 current efficiency
Cd/A power efficiency
lm/w color coordinates
CIEx color coordinates
CIEy life span
LT97 (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, "-" indicates that the light emission disappears within one hour.

As shown in Table 1, it can be confirmed that Examples 1 to 29 of the present invention have superior physical properties in all aspects compared to Comparative Examples 1 to 6. Compared with Comparative Examples 2 and 6, even though they have the same indole moiety, it can be seen that the indole 2 and 3-position arylamine-substituted compounds have excellent molecular arrangement and excellent hole mobility in the thin film state, which greatly affected the efficiency and lifespan improvement. can

In particular, as shown in the results of Examples 4 to 20, when Ar included in the repeating unit l in Formula 1 includes 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 composition in which more than two kinds of compounds were mixed showed further improvement in lifespan and efficiency, and Ar included in the repeating unit l in Formula 1 was two types including a biphenyl group and a fluorene group. When the above mixture was mixed, 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 further confirmed.

Claims (11)

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

In the above formula,
l, m, n, o are each independently an integer selected from 1 to 4,
Ar and R ₅ are each independently deuterium, 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 unsubstituted C _{6 -50} is an aryl group,
R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen; heavy hydrogen; nitrile group; nitro group; silane group; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; It is a C _6-30 aryloxy group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, or nitro group. According to claim 1,
The compound is a compound, characterized in that the compound represented by Formula 2 or Formula 3:
[Formula 2]

[Formula 3]

In Formula 2 or Formula 3, l, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are as defined in Formula 1, and Ar ₁ , Ar ₂ , and Ar ₃ are each independently deuterium, halogen, 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 C _6-50 aryl group unsubstituted or substituted with a silane group,
X is CR ₉ R ₁₀ ,
R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ are each independently hydrogen; heavy hydrogen; amino group; nitrile group; nitro group; silane group; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; or a C _6-50 aryl group substituted or unsubstituted with deuterium, 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, or a silane group. According to claim 1,
The -(Ar) _l - is a compound represented by Formula 1, characterized in that biphenyl or fluorene. According to claim 1,
A compound characterized by being represented by any one of the following formulas:

An organic light emitting device comprising an anode, a cathode, and at least one organic material layer containing the compound of any one of claims 1 to 4 between the two electrodes. 6. The method of claim 5,
The organic light emitting device, characterized in that the organic material layer comprises two or more kinds of the compound according to claim 4. 6. 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. 6. The method of claim 5,
Organic light emitting, characterized in that the organic material layer is a compound in which Ar included in the repeating unit l in Formula 1 includes a biphenyl group, and in Formula 1, Ar included in the repeating unit 1 includes a fluorene group, in which two or more compounds are mixed. device. 6. The method of claim 5,
The organic light emitting device is an organic light emitting device comprising a compound represented by the following formula (4) in the light emitting layer:
[Formula 4]

In Formula 4,
Ar ₄ and Ar ₅ are each independently a C _6-50 aryl group substituted with or unsubstituted with deuterium, halogen, an amino group, a nitrile group, or a nitro group; Or a C _2-50 heteroaryl group substituted or unsubstituted with deuterium, halogen, amino group, nitrile group, nitro group,
R 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; a C _1-30 alkyl group substituted with or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _2-30 alkenyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; C _2-30 alkynyl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; a C _1-30 alkoxy group substituted or unsubstituted with deuterium, a halogen, an amino group, a nitrile group, or a nitro group; C _6-30 aryloxy group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, or nitro group; C _6-50 aryl group unsubstituted or substituted with deuterium, halogen, amino group, nitrile group, nitro group; or a C _2-50 heteroaryl group that is unsubstituted or substituted with deuterium, halogen, amino, nitrile, or nitro. 10. The method of claim 9,
An organic light emitting device, characterized in that Ar ₄ and Ar ₅ of Formula 4 are asymmetric: 10. The method of claim 9,
The compound represented by the 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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