KR102649025B1 - Novel compound and organic electroluminescent divice including the same - Google Patents

Abstract

This application is about a novel arylamine compound, which can increase hole injection and transport characteristics when used as a hole transport layer (HTL), luminescent auxiliary layer (HT), or hole injection layer (HIL), resulting in high efficiency and long lifespan of the device. can be provided.

Description

Novel compounds and organic light-emitting devices containing the same {NOVEL COMPOUND AND ORGANIC ELECTROLUMINESCENT DIVICE INCLUDING THE SAME}

The present application relates to novel arylamine compounds and organic light-emitting devices containing the same.

Materials used as organic layers in organic light-emitting diodes can be broadly classified into light-emitting materials, hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their function. In addition, the light-emitting materials can be classified into high molecules and low molecules according to their molecular weight, and can be classified into fluorescent materials derived from the singlet excited state of electrons and phosphorescent materials derived from the triplet excited state of electrons depending on the luminescence mechanism, Light-emitting materials can be divided into blue, green, and red light-emitting materials according to their emission color, and yellow and orange light-emitting materials necessary to realize better natural colors. Additionally, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system can be used as a luminescent material. The principle is that when a small amount of dopant, which has a smaller energy band gap and higher luminous efficiency than the host that mainly constitutes the light-emitting layer, is mixed into the light-emitting layer, excitons generated in the host are transported to the dopant, producing highly efficient light. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of the desired wavelength can be obtained depending on the type of dopant and host used.

To date, various compounds are known as materials used in such organic light-emitting devices, but in the case of organic light-emitting devices using known materials, the development of new materials is continuously required due to high driving voltage, low efficiency, and short lifespan. Therefore, efforts have been made to develop organic light-emitting devices with low voltage operation, high brightness, and long lifespan using materials with excellent properties.

Japanese published patent 10-2015-530735

The present application seeks to provide a novel arylamine compound and an organic light-emitting device containing the same.

However, the problem to be solved by the present application is not limited to the problems described above, and other problems not described will be clearly understood by those skilled in the art from the description below.

A first aspect of the present application provides a compound represented by the following formula (1):

[Formula 1]

In Formula 1,

R and R` are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an aryl group of C ₆ to C ₃₀ that may be substituted, or a heteroaryl group of C ₅ to C ₃₀ that may be substituted. ego,

Ar ₁ to Ar ₄ are each independently a C ₆ to C ₃₀ aryl group that may be substituted or a C ₅ to C ₃₀ heteroaryl group that may be substituted,

Ar is an aryl group of C ₆ to C ₁₀ that may be substituted,

R ₁ to R ₃ are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an alkenyl group of C ₂ to C ₃₀ that may be substituted, an aryl group of C ₆ to C ₃₀ that may be substituted or a C ₅ to C ₃₀ heteroaryl group that may be substituted,

l is an integer from 0 to 4, m is an integer from 0 to 3, n is an integer from 0 to 5, and o is an integer from 0 to 4, provided that n+o is 1 or more.

A second aspect of the present application provides an organic light-emitting device comprising the compound according to the present application.

In the present invention, the N of arylamine is directly bonded to the 1, 3, or 4th position of fluorene, and the aryl on one side of the arylamine contains three or more aryls, forming a deep HOMO and a high LUMO at the same time, thereby preventing electron blocking. It is easy to use, and the expansion of three or more aryl groups increases pi-conjugation and improves the thin film arrangement of molecules, suppressing the roll-off phenomenon through fast hole mobility and realizing a long-life device, and has a high Tg even with a relatively small molecular weight. Therefore, recrystallization can be prevented during operation. In addition, by fixing the aryl group on the other side of the arylamine to an aryl group with 10 carbon atoms or less (C ₁₀ or less), it is possible to have appropriate HOMO and LUMO and maintain a high T1, thereby efficiently forming excitons in the light-emitting layer, resulting in a highly efficient organic light-emitting device. Implementation is possible.

The compound of the present invention has effects such as high luminous efficiency and high color purity, and can greatly contribute to the OLED industry such as flexible displays and lighting by applying it to organic light-emitting devices, organic light devices for solar power generation, etc.

Figure 1 shows a schematic diagram of an organic light-emitting device according to an embodiment of the present application.

Hereinafter, with reference to the attached drawings, implementation examples and embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention.

However, the present application may be implemented in various different forms and is not limited to the implementation examples and examples described herein. In order to clearly explain the present invention in the drawings, parts that are not related to the description are omitted, and similar parts are given similar reference numerals throughout the specification.

Throughout this specification, when a member is said to be located “on” another member, this includes not only the case where the member is in contact with the other member, but also the case where another member exists between the two members.

Throughout the specification of the present application, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary. As used throughout the specification, the terms “about,” “substantially,” and the like are used to mean at or close to a numerical value when manufacturing and material tolerances inherent in the stated meaning are given, and are used to convey the understanding of the present application. Precise or absolute figures are used to assist in preventing unscrupulous infringers from taking unfair advantage of stated disclosures. As used throughout the specification, the terms “step of” or “step of” do not mean “step for.”

Throughout this specification, the term "combination thereof" included in the Markushi format expression means a mixture or combination of one or more components selected from the group consisting of the components described in the Markushi format expression, It means including one or more selected from the group consisting of.

Throughout this specification, description of “A and/or B” means “A or B, or A and B.”

Throughout this specification, the term “aryl” refers to a C _6-30 aromatic hydrocarbon ring group, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, perylethyl. It means containing an aromatic ring such as nyl, chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzochrysenyl, anthracenyl, stilbenyl, pyrenyl, etc., and “heteroaryl” means at least one ring. A C _5-30 aromatic ring containing a hetero atom, for example, pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, Benzothiophenyl, dibenzothiophenyl, quinolyl group, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, thienyl, and pyridine ring, pyrazine ring, pyrimidine ring , pyridazine ring, triazine ring, indole ring, quinoline ring, acridine ring, pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, piperazine ring, carbazole ring, furan ring, t Ophen ring, oxazole ring, oxadiazole ring, benzooxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, imidazole ring, benzoimidazole ring, pyran ring, dibenzofuran It means including an aromatic heterocyclic group formed from a ring.

Throughout this specification, the term “alkyl” may include linear or branched, saturated or unsaturated C ₁ -C ₆ alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl or any of these. It may include all possible isomers, but may not be limited thereto.

Throughout the specification herein, the term “substituted” or “substituted” refers to deuterium, halogen, amino group, nitrile group, nitro group, silane group, alkyl group or C ₁ to C ₂₀ alkyl group, alkenyl group or C ₂ to C ₂₀ group. Alkenyl group, alkoxy group or C ₁ to C ₂₀ alkoxy group, cycloalkyl group or C ₃ to C ₂₀ cycloalkyl group, heterocycloalkyl group or C ₃ to C ₂₀ heterocycloalkyl group or C ₅ to C ₃₀ aryl group or It means that it may be substituted with one or more groups selected from the group consisting of C ₅ ~ C ₃₀ heteroaryl groups.

Additionally, the same symbols throughout the specification may have the same meaning unless otherwise specified.

A first aspect of the present application provides a compound represented by the following formula (1):

[Formula 1]

In Formula 1,

R and R` are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an aryl group of C ₆ to C ₃₀ that may be substituted, or a heteroaryl group of C ₅ to C ₃₀ that may be substituted. ego,

Ar ₁ to Ar ₄ are each independently a C ₆ to C ₃₀ aryl group that may be substituted or a C ₅ to C ₃₀ heteroaryl group that may be substituted,

Ar is an aryl group of C ₆ to C ₁₀ that may be substituted,

R ₁ to R ₃ are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an alkenyl group of C ₂ to C ₃₀ that may be substituted, an aryl group of C ₆ to C ₃₀ that may be substituted or a C ₅ to C ₃₀ heteroaryl group that may be substituted,

l is an integer from 0 to 4, m is an integer from 0 to 3, n is an integer from 0 to 5, and o is an integer from 0 to 4, provided that n+o is 1 or more.

In one embodiment of the present invention, the compound may include a compound represented by the following formula (2):

[Formula 2]

In Formula 2,

R, R`, Ar ₁ to Ar ₄ , R ₁ to R ₃ , l, m, n and o are as defined in Formula 1 above,

R ₄ is hydrogen, deuterium, a C ₁ to C ₃₀ alkyl group, or a C ₂ to C ₃₀ alkenyl group that may be substituted,

p is an integer from 0 to 5.

In one embodiment of the present invention, the compound may include a compound represented by the following formula (3):

[Formula 3]

In Formula 3 above,

R, R`, Ar ₃ , Ar ₄ , R ₁ to R ₃ , l, m, n and o are as defined in Formula 1 above,

R ₄ is hydrogen, deuterium, a C ₁ to C ₃₀ alkyl group, or a C ₂ to C ₃₀ alkenyl group that may be substituted,

R ₅ and R ₆ are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an alkenyl group of C ₂ to C ₃₀ that may be substituted, an aryl group of C ₆ to C ₃₀ that may be substituted or a C ₅ to C ₃₀ heteroaryl group that may be substituted,

p is an integer from 0 to 5.

In one embodiment of the present invention, the compound may include a compound represented by the following formula (4):

[Formula 4]

In Formula 4 above,

Ar ₃ , Ar ₄ , R ₁ to R ₃ , l, m, n and o are as defined in Formula 1 above,

R ₄ is hydrogen, deuterium, a C ₁ to C ₃₀ alkyl group, or a C ₂ to C ₃₀ alkenyl group that may be substituted,

R ₅ and R ₆ are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an alkenyl group of C ₂ to C ₃₀ that may be substituted, an aryl group of C ₆ to C ₃₀ that may be substituted or a C ₅ to C ₃₀ heteroaryl group that may be substituted,

Ar` and Ar`` are each independently a C ₆ to C ₃₀ aryl group that may be substituted or a C ₅ to C ₃₀ heteroaryl group that may be substituted,

p is an integer from 0 to 5.

In one embodiment of the present invention, the compound may include a compound represented by the following formula (5):

[Formula 5]

In Formula 5 above,

Ar ₃ , Ar ₄ , R ₁ to R ₃ , l, m, n and o are as defined in Formula 1 above,

R ₄ is hydrogen, deuterium, a C ₁ to C ₃₀ alkyl group, or a C ₂ to C ₃₀ alkenyl group that may be substituted,

R ₅ and R ₆ are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an alkenyl group of C ₂ to C ₃₀ that may be substituted, an aryl group of C ₆ to C ₃₀ that may be substituted or a C ₅ to C ₃₀ heteroaryl group that may be substituted,

R” and R’” are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an alkenyl group of C ₂ to C ₃₀ that may be substituted, an aryl group of C ₆ to C ₃₀ that may be substituted group or a heteroaryl group of C ₅ to C ₃₀ that may be substituted,

p is an integer from 0 to 5.

In one embodiment of the present invention, n may be 1 and o may be 0 in the compounds of Formulas 1 to 5.

In one embodiment of the present invention, in the compounds of Formulas 1 to 5, R ₃ may be hydrogen, and in this case, the substituents of fluorene are minimized to suppress molecular distortion and maintain rapid mobility.

In one embodiment of the present invention, Ar ₁ to Ar ₄ may be phenyl or biphenyl, but are not limited thereto.

In one embodiment of the present invention, Ar may be phenyl or naphthyl, but is not limited thereto.

In one embodiment of the present invention, the compound represented by Formula 1 can be synthesized by the process shown in Scheme 1 below:

[Scheme 1]

In one embodiment of the present invention, the compound represented by Formula 1 may include, but may not be limited to, the following compounds:

Among the above specific compounds, compounds numbered 1 to 98, 139 to 236, 277 to 374, 415 to 516, 547 to 648, and 679 to 780 can maintain a higher T1 by minimizing condensation groups, thereby trapping excitons in the light emitting layer. The effect can be maximized.

A second aspect of the present application provides an organic light-emitting device including the compound represented by Formula 1 above. The organic light emitting device may include one or more organic layers containing the compound according to the present invention between the first electrode and the second electrode.

In one embodiment of the present invention, the organic material layer may be one or more layers among a hole injection layer, a hole transport layer, and a light-emitting auxiliary layer, for example, but may not be limited to a light-emitting auxiliary layer. In this case, the organic material layer of the present invention may be The compound may be used alone or in combination with a known organic luminescent compound.

In the present invention, the light-emitting auxiliary layer is a layer formed between the hole transport layer and the light-emitting layer, and may also be referred to as a second hole transport layer or a third hole transport layer, depending on the number of hole transport layers.

In one embodiment of the present invention, the organic light-emitting device may include, but may not be limited to, an organic material layer containing a hole transport material and an organic material layer containing the compound represented by Chemical Formula 1.

The organic light-emitting device has 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), and an electron injection layer (EIL) between an anode and a cathode. It may contain more than one.

For example, the organic light emitting device may be manufactured according to the structure shown in FIG. 1. The organic light emitting device consists of an anode (hole injection electrode (1000))/hole injection layer (200)/hole transport layer (300)/light emitting layer (400)/electron transport layer (500)/electron injection layer (600)/cathode (electron) from below. Injection electrodes (2000) may be stacked in that order.

In FIG. 1, the substrate 100 may be a substrate used in an organic light emitting device. In particular, it may be a transparent glass substrate or a flexible plastic substrate with excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofing. there is.

The hole injection electrode 1000 is used as an anode for hole injection into an organic light emitting device. A material with a low work function is used to enable hole injection, and it can be made of transparent materials such as indium tin oxide (ITO), indium zinc oxide (IZO), and graphene.

The hole injection layer 200 may be formed by depositing a hole injection layer material on the anode electrode using a method such as vacuum deposition, spin coating, casting, or Langmuir-Blodgett (LB) method. When forming a hole injection layer by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material for the hole injection layer, the structure and thermal characteristics of the desired hole injection layer, but generally a deposition temperature of 50-500°C, 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 ㎛ can be appropriately selected.

Next, the hole transport layer 300 can be formed by depositing a hole transport layer material on top of the hole injection layer 200 by a method such as vacuum deposition, spin coating, casting, or LB method. When forming a hole transport layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but it is generally better to select conditions within the same range as those for forming the hole injection layer. The hole transport layer may be one or more, for example, it may be two layers: a first hole transport layer and a second hole transport layer (light-emitting auxiliary layer). At least one of the first hole transport layer and the second hole transport layer may include the compound of Formula 1 according to the present invention.

Thereafter, the light-emitting layer 400 can be formed by depositing a light-emitting layer material on the hole transport layer or the light-emitting auxiliary layer by a method such as vacuum deposition, spin coating, casting, or LB method. When forming a light-emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but it is generally recommended to select conditions within the same range as those for forming the hole injection layer. Additionally, the light emitting layer material may use a known compound as a host or dopant.

In addition, when used with a phosphorescent dopant in the light emitting layer, a hole blocking material (HBL) can be additionally laminated by vacuum deposition or spin coating to prevent diffusion of triplet excitons or holes into the electron transport layer. The hole blocking material that can be used at this time is not particularly limited, but any material can be selected from known hole blocking materials and used. For example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, or hole blocking materials described in Japanese Patent Application Laid-Open No. 11-329734 (A1), etc., representative examples include Balq (bis (8-hyde) Roxy-2-methylquinolinolnato)-aluminum biphenoxide), phenanthrolines-based compounds (e.g., UDC's BCP (bassocuproin)), etc. can be used.

An electron transport layer 500 is formed on the light emitting layer 400 formed as described above. At this time, the electron transport layer can be formed by a method such as vacuum deposition, spin coating, or casting. In addition, the deposition conditions for the electron transport layer vary depending on the compound used, but it is generally better to select conditions within the same range as those for forming the hole injection layer.

Thereafter, an electron injection layer material may be deposited on top of the electron transport layer 500 to form an electron injection layer 600. At this time, the electron injection layer may be formed using a typical electron injection layer material using a vacuum deposition method, a spin coating method, or a vacuum deposition method. It can be formed by a method such as a casting method.

The hole injection layer 200, hole transport layer 300, light emitting layer 400, and electron transport layer 500 of the above device can be made of a compound according to the present invention or the following materials can be used, or a compound according to the present invention and Known substances can be used together.

A cathode 2000 for electron injection is formed on the electron injection layer 600 by a method such as vacuum deposition or sputtering. Various metals can be used as the cathode. Specific examples include materials such as aluminum, gold, and silver.

The organic light-emitting device of the present invention is capable of forming not only an anode, hole injection layer, hole transport layer, light-emitting layer, electron transport layer, electron injection layer, and cathode structure, but also various structures of organic light-emitting device, depending on the need. It is also possible to further form a layer or an intermediate layer of two layers.

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

In addition, the present invention has the advantage that the organic material layer containing 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 on a molecular basis.

All of the content described in the first aspect of the present application may be applied to the organic light-emitting compound according to this aspect, but may not be limited thereto.

Hereinafter, the present application will be described in more detail through examples, but the scope of the present application is not limited by these examples.

[ Example ]

Manufacturing example One. IM's synthesis

The intermediate IM for synthesizing the target compound can be synthesized as follows, but is not limited thereto.

or

The reactant IM1 used to synthesize the target compound was synthesized as follows:

The synthesis method of IM1 is as follows.

In a round bottom flask, 27.6 g of [1,1'-biphenyl]-4-ylboronic acid and 50.0 g of 4-bromo-4'-iodo-1,1'-biphenyl were added to 800 ml of 1,4-dioxane. After dissolving, 210 ml of K ₂ CO ₃ (2M) and 4.8 g of Pd(PPh ₃ ) ₄ were added, followed by refluxing and stirring. The reaction was confirmed by TLC and the reaction was terminated after adding water. The organic layer was extracted with MC, filtered under reduced pressure, and recrystallized to obtain 50.4 g of intermediate IM1 (yield 74%).

The following IM2 to IM9 were synthesized using the same method as IM1, using different starting materials.

Manufacturing example 2. Synthesis of OP

The synthesis method of OP1 is as follows.

In a round bottom flask, 10.0 g of 3-bromo-9,9-diphenyl-9H-fluorene, 3.8 g of aniline, 5.3 g of t-BuONa, 1.4 g of Pd ₂ (dba) ₃ , and (t-Bu) ₃ P1. .6ml was dissolved in 150ml of toluene and stirred under reflux. The reaction was confirmed by TLC and the reaction was terminated after adding water. The organic layer was extracted with MC, filtered under reduced pressure, and recrystallized to obtain 7.3g of OP1 (yield 70%).

The following OP2 to OP5 were synthesized using the same method as OP1, using different starting materials.

Synthesis example One. Compound 1 synthesis

In a round bottom flask, 7.0 g of IM1, 5.2 g of OP1, 2.6 g of t-BuONa, 0.7 g of Pd ₂ (dba) ₃ , and 0.7 ml of (t-Bu) ₃ P were dissolved in 200 ml of toluene and stirred under reflux. The reaction was confirmed by TLC and the reaction was terminated after adding water. The organic layer was extracted with MC, filtered under reduced pressure, then column purified and recrystallized to obtain 7.07 g of Compound 1 (yield 66%).

m/z: 589.28 (100.0%), 590.28 (49.1%), 591.28 (11.8%), 592.29 (1.8%)

Synthesis example 2. Compound 2 synthesis

Compound 2 was synthesized in the same manner as Compound 1 using OP2 instead of OP1 (yield 64%).

m/z: 589.28 (100.0%), 590.28 (49.1%), 591.28 (11.8%), 592.29 (1.8%)

Synthesis example 3. Compound 3 synthesis

Compound 3 was synthesized in the same manner as Compound 1, using IM2 and OP3 instead of IM1 and OP1 (yield 70%).

m/z: 637.28 (100.0%), 638.28 (53.4%), 639.28 (14.0%), 640.29 (2.4%)

Synthesis example 4. Compound 4 synthesis

Compound 4 was synthesized in the same manner as Compound 1, using IM3 and OP3 instead of IM1 and OP1 (yield 64%).

m/z: 637.28 (100.0%), 638.28 (53.4%), 639.28 (14.0%), 640.29 (2.4%)

Synthesis example 5. Compound 5 synthesis

Compound 5 was synthesized in the same manner as Compound 1, using IM4 and OP3 instead of IM1 and OP1 (yield 65%).

m/z: 637.28 (100.0%), 638.28 (53.4%), 639.28 (14.0%), 640.29 (2.4%)

Synthesis example 6. Compound 6 synthesis

Compound 6 was synthesized in the same manner as Compound 1, using IM5 and OP3 instead of IM1 and OP1 (yield 60%).

m/z: 637.28 (100.0%), 638.28 (53.4%), 639.28 (14.0%), 640.29 (2.4%)

Synthesis example 7. Compound 7 synthesis

Compound 7 was synthesized in the same manner as Compound 1, using IM6 and OP3 instead of IM1 and OP1 (yield 60%).

m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%)

Synthesis example 8. Compound 8 synthesis

Compound 8 was synthesized in the same manner as Compound 1, using IM7 and OP3 instead of IM1 and OP1 (yield 60%).

m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%)

Synthesis example 9. Compound 9 synthesis

Compound 9 was synthesized in the same manner as Compound 1, using IM8 and OP3 instead of IM1 and OP1 (yield 67%).

m/z: 713.31 (100.0%), 714.31 (60.3%), 715.31 (17.6%), 716.32 (3.4%)

Synthesis example 10. Compound 10 synthesis

Compound 10 was synthesized in the same manner as Compound 1 using IM2 and OP4 instead of IM1 and OP1 (yield 70%).

m/z: 637.28 (100.0%), 638.28 (53.4%), 639.28 (14.0%), 640.29 (2.4%)

Synthesis example 11. Compound 11 synthesis

Compound 11 was synthesized in the same manner as Compound 1 using IM3 and OP4 instead of IM1 and OP1 (yield 62%).

m/z: 637.28 (100.0%), 638.28 (53.4%), 639.28 (14.0%), 640.29 (2.4%)

Synthesis example 12. Compound 12 synthesis

Compound 12 was synthesized in the same manner as Compound 1, using IM4 and OP4 instead of IM1 and OP1 (yield 65%).

m/z: 637.28 (100.0%), 638.28 (53.4%), 639.28 (14.0%), 640.29 (2.4%)

Synthesis example 13. Compound 13 synthesis

Compound 13 was synthesized in the same manner as Compound 1 using IM2 and OP5 instead of IM1 and OP1 (yield 58%).

m/z: 637.28 (100.0%), 638.28 (53.4%), 639.28 (14.0%), 640.29 (2.4%)

Synthesis example 14. Compound 14 synthesis

Compound 14 was synthesized in the same manner as Compound 1 using IM3 and OP5 instead of IM1 and OP1 (yield 52%).

m/z: 637.28 (100.0%), 638.28 (53.4%), 639.28 (14.0%), 640.29 (2.4%)

Synthesis example 15. Compound 15 synthesis

Compound 15 was synthesized in the same manner as Compound 1, using IM4 and OP5 instead of IM1 and OP1 (yield 55%).

m/z: 637.28 (100.0%), 638.28 (53.4%), 639.28 (14.0%), 640.29 (2.4%)

Example 1: Preparation of organic light emitting device

A glass substrate coated with a 1500 Å thin film of indium tin oxide (ITO) was washed with distilled water ultrasonic waves. After cleaning with distilled water, ultrasonic cleaning with solvents such as isopropyl alcohol, acetone, and methanol, drying, and transferring to a plasma cleaner, the substrate is cleaned for 5 minutes using oxygen plasma, and then a thermal vacuum evaporator (thermal vacuum evaporator) is placed on the top of the ITO substrate. Using an evaporator, a hole injection layer of HI01 600 Å, HATCN 50 Å, a hole transport layer of 250 Å of BPA, and a light-emitting auxiliary layer of 100 Å were formed, and then the light-emitting layer was doped with 3% BH01:BD01 to form a 250 Å film. Next, an organic light-emitting device was manufactured by depositing 300 Å of ET01:Liq (1:1) as an electron transport layer, followed by 10 Å of LiF and 1000 Å of aluminum (Al), and encapsulating the device in a glove box.

Examples 2 to 15: Preparation of organic light-emitting devices

An organic light-emitting device was manufactured using the same method as Example 1, but using Compounds 2 to 15 instead of Compound 1.

Comparative Examples 1 to 10

An organic light-emitting device was manufactured using the same method as Example 1, but using Ref.1 to Ref.10 below instead of Compound 1.

Experimental Example 1: Performance evaluation of organic light emitting device

Apply voltage to the Keithley 2400 source measurement unit to inject electrons and holes, and measure the luminance when light is emitted using a Konica Minolta spectroradiometer (CS-2000). By doing so, the performance of the organic light emitting devices 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.

Op. V mA/cm2 Cd/A QE(%) CIEx CIey LT95 Example 1 3.86 10 7.18 6.14 0.140 0.110 185 Example 2 3.90 10 7.25 6.22 0.140 0.110 190 Example 3 3.92 10 7.37 6.30 0.140 0.109 222 Example 4 3.93 10 7.45 6.48 0.140 0.110 223 Example 5 3.92 10 7.40 6.35 0.141 0.109 222 Example 6 3.94 10 7.37 6.35 0.140 0.110 221 Example 7 3.92 10 7.40 6.33 0.140 0.110 222 Example 8 3.92 10 7.40 6.30 0.140 0.109 220 Example 9 3.93 10 7.38 6.32 0.139 0.110 223 Example 10 3.97 10 7.35 6.28 0.141 0.111 220 Example 11 3.98 10 7.35 6.24 0.140 0.110 220 Example 12 3.97 10 7.48 6.30 0.140 0.111 224 Example 13 3.97 10 7.48 6.32 0.140 0.110 223 Example 14 3.98 10 7.42 6.30 0.140 0.110 220 Example 15 3.97 10 7.47 6.39 0.141 0.111 221 Comparative Example 1 4.03 10 6.40 5.23 0.142 0.112 60 Comparative example 2 4.07 10 6.68 5.60 0.143 0.110 122 Comparative example 3 4.03 10 6.38 5.25 0.141 0.112 65 Comparative example 4 4.10 10 6.60 5.48 0.141 0.110 122 Comparative Example 5 4.23 10 6.72 5.60 0.141 0.110 118 Comparative Example 6 4.30 10 6.91 5.81 0.143 0.110 143 Comparative example 7 4.18 10 6.71 5.58 0.141 0.111 119 Comparative example 8 4.27 10 6.91 5.79 0.141 0.110 150 Comparative Example 9 4.09 10 6.70 5.59 0.141 0.110 105 Comparative Example 10 4.13 10 6.74 5.62 0.141 0.110 110

As can be seen in Table 1, it can be seen that the efficiency and lifespan of Examples 1 to 15 using the compounds of the present invention as the hole transport layer are increased compared to Comparative Examples 1 to 10.

More specifically, comparing Comparative Examples and Examples, compared to Comparative Examples 1, 2, 3, and 4, the compounds of Examples form a deep HOMO suitable for a light-emitting auxiliary layer by bonding fluorene 1, 3, and 4, Compared to Comparative Examples 5 and 6, the compounds of the Examples had increased hole mobility by expanding the pi-conjugation and improving the molecular arrangement of the thin film by connecting three or more aryl groups. Compared to Comparative Examples 7, 8, 9, and 10, The compounds of the examples maintain deep HOMO, high LUMO, and T1 by minimizing the other part of the arylamine to an aryl group of C ₁₀ or less. Therefore, when the compound of the present invention is applied to an organic light emitting device, the driving voltage is low, and the efficiency and lifespan are low. You can see that this has improved significantly.

The description of the present application described above is for illustrative purposes, and those skilled in the art will understand that the present application can be easily modified into other specific forms without changing its technical idea or essential features. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive. For example, each component described as unitary may be implemented in a distributed manner, and similarly, components described as distributed may also be implemented in a combined form.

The scope of the present application is indicated by the claims described below rather than the detailed description above, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present application. .

100: substrate
200: Hole injection layer
300: Hole transport layer
400: light emitting layer
500: electron transport layer
600: Electron injection layer
1000: anode
2000: Cathode

Claims (13)

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

In Formula 1,
R and R` are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an aryl group of C ₆ to C ₃₀ that may be substituted, or a heteroaryl group of C ₅ to C ₃₀ that may be substituted. ego,
Ar ₁ to Ar ₄ are each independently C ₆ to C ₃₀ aryl groups that may be substituted,
Ar is an aryl group of C ₆ to C ₁₀ that may be substituted,
R ₁ to R ₃ are each independently hydrogen, deuterium, a substituted C ₁ to C ₃₀ alkyl group, a substituted C ₂ to C ₃₀ alkenyl group, or a substituted C ₆ to C ₃₀ aryl group. It's awesome,
l is an integer from 0 to 4, m is an integer from 0 to 3, n is an integer from 0 to 5, and o is an integer from 0 to 4, provided that n+o is 1 or more. According to paragraph 1,
The compound includes a compound represented by the following formula (2).
[Formula 2]

In Formula 2,
R, R`, Ar ₁ to Ar ₄ , R ₁ to R ₃ , l, m, n and o are as defined in claim 1,
R ₄ is hydrogen, deuterium, a C ₁ to C ₃₀ alkyl group, or a C ₂ to C ₃₀ alkenyl group that may be substituted,
p is an integer from 0 to 5. According to paragraph 1,
The compound includes a compound represented by the following formula (3).
[Formula 3]

In Formula 3 above,
R, R`, Ar ₃ , Ar ₄ , R ₁ to R ₃ , l, m, n and o are as defined in clause 1,
R ₄ is hydrogen, deuterium, a C ₁ to C ₃₀ alkyl group, or a C ₂ to C ₃₀ alkenyl group that may be substituted,
R ₅ and R ₆ are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an alkenyl group of C ₂ to C ₃₀ that may be substituted, or aryl of C ₆ to C ₃₀ that may be substituted It's awesome,
p is an integer from 0 to 5. According to paragraph 1,
The compound includes a compound represented by the following formula (4).
[Formula 4]

In Formula 4 above,
Ar ₃ , Ar ₄ , R ₁ to R ₃ , l, m, n and o are as defined in claim 1,
R ₄ is hydrogen, deuterium, a C ₁ to C ₃₀ alkyl group, or a C ₂ to C ₃₀ alkenyl group that may be substituted,
R ₅ and R ₆ are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an alkenyl group of C ₂ to C ₃₀ that may be substituted, or aryl of C ₆ to C ₃₀ that may be substituted It's awesome,
Ar` and Ar`` are each independently C ₆ to C ₃₀ aryl groups that may be substituted,
p is an integer from 0 to 5. According to paragraph 1,
The compound includes a compound represented by the following formula (5).
[Formula 5]

In Formula 5 above,
Ar ₃ , Ar ₄ , R ₁ to R ₃ , l, m, n and o are as defined in claim 1,
R ₄ is hydrogen, deuterium, a C ₁ to C ₃₀ alkyl group, or a C ₂ to C ₃₀ alkenyl group that may be substituted,
R ₅ and R ₆ are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an alkenyl group of C ₂ to C ₃₀ that may be substituted, or aryl of C ₆ to C ₃₀ that may be substituted It's awesome,
R” and R’” are each independently hydrogen, deuterium, an alkyl group of C ₁ to C ₃₀ that may be substituted, an alkenyl group of C ₂ to C ₃₀ that may be substituted, or an alkenyl group of C ₆ to C ₃₀ that may be substituted. It is an aryl group,
p is an integer from 0 to 5. According to any one of claims 1 to 5,
In Formulas 1 to 5, n is 1 and o is 0. According to any one of claims 1 to 5,
In Formulas 1 to 5, R ₃ is hydrogen. According to paragraph 1,
Ar ₁ above to Ar ₄ are each independently phenyl or biphenyl. According to paragraph 1,
A compound wherein Ar is phenyl or naphthyl. According to paragraph 1,
The compound represented by Formula 1 includes any one of the following compounds:






























An organic light-emitting device comprising an organic material layer containing the compound of claim 1 between the first electrode and the second electrode. According to clause 11,
An organic light emitting device wherein the organic material layer is at least one of a hole injection layer, a hole transport layer, and a light emitting auxiliary layer. According to clause 12,
An organic light-emitting device in which the organic material layer is a light-emitting auxiliary layer.