KR102628804B1 - Novel compound and organic electroluminescent divice including the same - Google Patents

Abstract

The present application relates to a novel compound and an organic light-emitting device containing the same. The novel compound according to an embodiment of the present invention is applied to an organic light-emitting device to improve the organic light-emitting device's high efficiency, long life, low driving voltage, and driving stability. It can be secured.

Description

New compounds and organic light-emitting devices containing them {NOVEL COMPOUND AND ORGANIC ELECTROLUMINESCENT DIVICE INCLUDING THE SAME}

The present application relates to novel 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. Accordingly, efforts have been made to develop organic light-emitting devices with low-voltage operation, high brightness, and long lifespan using materials with excellent properties.

Korean Patent Publication 10-2015-0086721

The present application provides novel organic compounds and organic light-emitting devices containing the same.

However, the problems to be solved by the present application are 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,

X is O or S,

Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted aryl group of C ₆ to C ₃₀ ,

Ar ₅ is a substituted or unsubstituted C ₆ to C ₃₀ aryl group, or a substituted or unsubstituted C ₅ to C ₃₀ heteroaryl group,

R, R', R ₁ to R ₄ are each independently hydrogen, deuterium, halogen, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted It is a substituted C ₁ ~ C ₃₀ alkoxy, nitro group, nitrile group, sulfide group, a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group, or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroaryl group, Adjacent R and R`, or a plurality of R ₁ , R ₂ , R ₂ , or R ₄ may or may not form a ring with each other,

L ₁ and L ₂ are each independently a direct bond, a substituted or unsubstituted C ₆ to C ₃₀ arylene group, or a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group,

l, o, p, and q are each independently 0 or an integer of 1 to 4, m and n are each independently 0 or an integer of 1 to 3, and p+q is an integer of 1 or more.

A second aspect of the present application provides an organic light emitting device including an organic material layer containing a compound according to the present application between a first electrode and a second electrode.

The arylamine compound according to one embodiment of the present invention has fluorene and dibenzofuran or dibenzothiophene substituents, and has a branched aryl linkage between nitrogen and dibenzofuran or dibenzothiophene. By introducing fluorene and branched aryl linking groups into arylamine, a deep HOMO level can be formed and at the same time a high LUMO level that can easily block electron movement can be formed, thereby achieving low voltage and high efficiency of organic light-emitting devices.

In addition, the compound according to one embodiment of the present invention can maintain a high T1 by having a branched aryl linkage group between nitrogen and the dibenzofuran or dibenzothiophene substituent, thereby maximizing the exciton confinement effect in the emitting layer, resulting in high efficiency. An organic light emitting device can be implemented.

In addition, the compound according to one embodiment of the present invention may have increased pi-conjugation due to the fluorene and branched aryl linkage groups, and may have excellent molecular thin film arrangement. Accordingly, hole mobility is improved, and a long-life organic light emitting device can be implemented by suppressing the roll-off phenomenon.

In addition, the compound according to one embodiment of the present invention forms a high Tg through fluorene and branched aryl linkages, thereby preventing thin film recrystallization and ensuring driving stability of the organic light-emitting device.

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 _5-30 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 _3-30 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 Ophene ring, oxazole ring, oxadiazole ring, benzooxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, imidazole ring, benzoimidazole ring, pyran ring, dibenzofuran It may mean including a heterocyclic group formed from a ring or a dibenzothiophene ring.

Throughout the specification herein, the term “substituted or unsubstituted” refers to deuterium, halogen, amino group, nitrile group, nitro group or C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkoxy group, substituted or unsubstituted with one or more groups selected from the group consisting of C ₃ ~ C ₂₀ cycloalkyl group, C ₃ ~ C ₂₀ heterocycloalkyl group, C ₆ ~ C ₃₀ aryl group, and C ₃ ~ C ₃₀ heteroaryl group It can mean.

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

Throughout this specification, the term "fluorene" refers to a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C _5-30 aryl group, or a substituted or unsubstituted C 1-20 alkyl group, or a substituted or unsubstituted C _5-30 aryl group. It may include cases where it is substituted with a heteroaryl group of _3-30 .

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

[Formula 1]

In Formula 1,

X is O or S,

Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted aryl group of C ₆ to C ₃₀ ,

Ar ₅ is a substituted or unsubstituted C ₆ to C ₃₀ aryl group, or a substituted or unsubstituted C ₅ to C ₃₀ heteroaryl group,

R, R', R ₁ to R ₄ are each independently hydrogen, deuterium, halogen, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted It is a substituted C ₁ ~ C ₃₀ alkoxy, nitro group, nitrile group, sulfide group, a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group, or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroaryl group, Adjacent R and R`, or a plurality of R ₁ , R ₂ , R ₂ , or R ₄ may or may not form a ring with each other,

L ₁ and L ₂ are each independently a direct bond, a substituted or unsubstituted C ₆ to C ₃₀ arylene group, or a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group,

l, o, p, and q are each independently 0 or an integer of 1 to 4, m and n are each independently 0 or an integer of 1 to 3, and p+q is an integer of 1 or more.

The arylamine compound according to one embodiment of the present invention has fluorene and dibenzofuran or dibenzothiophene substituents, and has a branched aryl linkage between nitrogen and dibenzofuran or dibenzothiophene. By introducing fluorene and branched aryl linking groups into arylamine, a deep HOMO level can be formed and at the same time a high LUMO level that can easily block electron movement can be formed, thereby achieving low voltage and high efficiency of organic light-emitting devices.

In addition, the compound according to one embodiment of the present invention can maintain a high T1 by having a branched aryl linkage group between nitrogen and the dibenzofuran or dibenzothiophene substituent, thereby maximizing the exciton confinement effect in the emitting layer, resulting in high efficiency. An organic light emitting device can be implemented.

In addition, the compound according to one embodiment of the present invention may have increased pi-conjugation due to the fluorene and branched aryl linkage groups, and may have excellent molecular thin film arrangement. Accordingly, hole mobility is improved, and a long-life organic light emitting device can be implemented by suppressing the roll-off phenomenon.

In addition, the compound according to one embodiment of the present invention forms a high Tg through fluorene and branched aryl linkages, thereby preventing thin film recrystallization and ensuring driving stability of the organic light-emitting device.

In one embodiment of the present invention, the compound may be represented by Formula 2 or Formula 3 below.

[Formula 2]

[Formula 3]

In the compound represented by Formula 2, in Formula 1, Ar ₁ is phenylene, p is 1, and q is 0, and in the compound represented by Formula 3, in Formula 1, Ar ₂ is phenylene, This is the case where p is 0 and q is 1. In this case, a high T1 can be formed, which can be effective in blocking unnecessary movement of excitons.

In one embodiment of the present invention, the compound may be represented by Formula 4 or Formula 5 below.

[Formula 4]

[Formula 5]

In the compound represented by Formula 4, Ar ₁ is phenylene, p is 1, q is 0, and L ₂ is a direct bond. In this case, fast hole mobility can be effective in improving driving voltage.

The compound represented by Formula 5 is a case where Ar ₂ in Formula 1 is phenylene, p is 0, q is 1, and the heteroring including X is bonded to phenylene in the meta position. In this case, the efficiency of the organic light-emitting device can be effectively improved through the meta-phenylene bond.

According to one embodiment of the present invention, in Formula 5, L ₂ may be phenylene.

In one embodiment of the present invention, the compound may be represented by Formula 6 or Formula 7 below.

[Formula 6]

[Formula 7]

In Formula 6 or Formula 7,

R ₅ and R ₆ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C ₁ ~ C ₃₀ alkyl group, substituted or unsubstituted C ₂ ~ C ₃₀ alkenyl group, substituted or unsubstituted C ₁ ~ C ₃₀ alkoxy, nitro group, nitrile group, sulfide group, substituted or unsubstituted C ₆ to C ₂₄ aryl group, or substituted or unsubstituted C ₅ to C ₂₄ heteroaryl group, and the dotted lines are connected to each other. It may not be connected.

According to one embodiment of the present invention, in Formula 7, L ₂ may be phenylene.

The compound represented by Formula 6 is when Ar ₁ is phenylene, p is 1, q is 0, L ₂ is a direct bond, and R and R' are phenyl, and in Formula 7 In the compound shown in Formula 1, Ar ₂ is phenylene, p is 0, q is 1, a three-ring compound including This is the case in the case of phenyl. In this case, minimizing the linking group can be effective in preventing unnecessary movement of electrons by having high LUMO and T1.

In one embodiment of the present invention, the compound may be represented by Formula 8 or Formula 9 below.

[Formula 8]

[Formula 9]

In Formula 8 or Formula 9,

R ₅ and R ₆ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C ₁ ~ C ₃₀ alkyl group, substituted or unsubstituted C ₂ ~ C ₃₀ alkenyl group, substituted or unsubstituted C ₁ ~ C ₃₀ alkoxy, nitro group, nitrile group, sulfide group, substituted or unsubstituted C ₆ to C ₂₄ aryl group, or substituted or unsubstituted C ₅ to C ₂₄ heteroaryl group, and the dotted lines are connected to each other. It may not be connected.

According to one embodiment of the present invention, in Formula 9, L ₂ may be phenylene.

In the compound represented by Formula 8, in Formula 1, Ar ₁ is phenylene, p is 1, q is 0, L ₁ and L ₂ are direct bonds, and nitrogen is directly bonded to the 2nd position of fluorene. In the case where R and R' are phenyl, the compound represented by Formula 9 is Formula 1 where Ar ₂ is phenylene, p is 0, q is 1, L ₁ is a direct bond, and nitrogen is It is directly bonded to the 2nd position of fluorene, and a three-ring compound containing X is bonded to phenylene in the meta position, and R and R' are phenyl. In this case, the roll-off phenomenon can be suppressed by having faster hole mobility, which can be effective in improving lifespan.

According to one embodiment of the present invention, in Formulas 1 to 9, l, m, n, and o may all be 0. Additionally, when l is an integer of 2 or more, R ₁ may be the same or different. Additionally, even when m, n, o, p and q are integers of 2 or more, the same applies to R ₂ to R ₄ , Ar ₃ and Ar ₄ .

Or according to one embodiment of the present invention, in Formulas 1 to 9, R ₁ to R ₄ are each independently hydrogen, deuterium, substituted or unsubstituted C ₁ to C ₁₀ alkyl, or substituted or unsubstituted It may be an aryl group of C ₆ to C ₃₀ .

According to one embodiment of the present invention, in Formulas 1 to 9, Ar ₁ to Ar ₄ may each be independently selected from the group consisting of phenyl, biphenyl, naphthyl, and combinations thereof, and specifically, all are phenyl It can be.

Additionally, according to one embodiment of the present invention, in Formulas 1 to 9, X may be O. In this case, it can be effective in improving the lifespan of the organic light emitting device.

Additionally, according to one embodiment of the present invention, in Formulas 1 to 9, X may be S. In this case, it can be effective in improving the efficiency of organic light-emitting devices.

According to one embodiment of the present invention, in Formulas 1 to 9, Ar ₅ may be selected from the group consisting of phenyl, biphenyl, naphthyl, dibenzofuran, dibenzothiophene, and combinations thereof.

According to one embodiment of the present invention, the compound represented by Formula 1 may be any one of the following compounds, but may not be limited thereto.

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 disclosure between the first electrode and the second electrode.

In one embodiment of the present invention, the organic material layer may be a hole injection layer, a hole transport layer, and a light emitting auxiliary layer, but may not be limited thereto. Additionally, the compounds of the present invention can be used alone or together with known compounds when forming an organic layer.

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 includes a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), and an electron injection layer between the first electrode (anode) and the second electrode (cathode). It may include one or more organic layers, such as an EIL layer.

For example, the organic light emitting device may be manufactured as 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 200, the structure and thermal characteristics of the desired hole injection layer, but generally 50-500 deposition. Temperature, vacuum degree of 10 ^-8 to 10 ^-3 torr, deposition rate of 0.01 to 100 Å/sec, and 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 300 may be formed using a compound according to the present invention. As described above, the compound according to the present invention may be used alone or a known compound may be used together. Additionally, according to one embodiment of the present invention, the hole transport layer 300 may have one or more layers and may also include a hole transport layer formed only of known materials. Additionally, according to one embodiment of the present invention, a light emitting auxiliary layer can be formed on the hole transport layer 300.

The light emitting layer 400 can be formed by depositing a light emitting layer material on the hole transport layer 300 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 better 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. In this case, 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, the electron injection layer material can be deposited on top of the electron transport layer 500 to form the electron injection layer 600. At this time, the electron transport layer is formed by using a typical electron injection layer material using vacuum deposition, spin coating, or cast. It can be formed through methods such as laws.

The hole injection layer 200, the hole transport layer 300, the light emitting layer 400, and the electron transport layer 500 of the organic light emitting device may be formed using a compound according to the present invention, or the following materials may be used, or a material according to the present invention may be used. Compounds 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 having various structures as well as an organic light-emitting device having an anode, hole injection layer, hole transport layer, light-emitting layer, electron transport layer, electron injection layer, and cathode structure. Depending on the need, 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 layer formed according to the present invention can be adjusted according to the required degree, and may be specifically 1 to 1,000 nm, and more specifically 5 to 200 nm.

In addition, the present invention has the advantage that the organic layer containing the compound represented by Formula 1 has a uniform surface and excellent morphological stability because the thickness of the organic layer can be adjusted on a molecular basis.

All contents described with respect to 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]

Synthesis of the compound represented by Formula 1

The compound represented by Formula 1 can be synthesized through the following reaction, but is not limited thereto.

Synthesis of intermediate IM

To synthesize the target compound, the intermediate IM can be synthesized through the following reaction, but is not limited thereto.

Synthesis of intermediate IM1

Intermediate IM1 was synthesized as follows.

In a round bottom flask, 20.0 g of dibenzo[b,d]furan-4-ylboronic acid and 32.3 g of 3,5-dibromo-1,1'-biphenyl were dissolved in 800 ml of 1,4-dioxan, and 140 ml of K2CO3 (2M) and Pd ( After adding 3.3 g of PPh ₃ ) ₄ , it was refluxed and stirred. 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 22.6 g of intermediate IM1-1 (yield 60%). In a round bottom flask, 22.0 g of IM1-1 and 18.2 g of bis(pinacolato)diboron were dissolved in 450 ml of 1,4-dioxan, 16.2 g of KOAc and 0.2 g of Pd(dppf)Cl ₂ were added, and then refluxed and stirred. 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 19.2 g of intermediate IM1-2 (yield 78%). In a round bottom flask, 19.0 g of IM1-2 and 13.3 g of 1-bromo-4-iodobenzene were dissolved in 500 ml of 1,4-dioxan, 64 ml of K2CO3 (2M) and 1.5 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 13.2 g of intermediate IM1 (yield 65%).

Synthesis of intermediates IM2 to IM8

The following IM2 to IM8 were synthesized in the same manner as IM1, using different starting materials as shown in Table 1 below.

compound synthesis

The target compounds were synthesized using the intermediates IM1 to IM8 as follows.

Synthesis of Compound 1

In a round bottom flask, 2.0g of IM1, 1.7g of N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine, 0.6g of t-BuONa, Pd ₂ ( 0.2 g of dba) ₃ and 0.2 ml of (t-Bu) ₃ P were dissolved in 60 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 2.2 g of Compound 1 (yield 70%).

m/z: 755.32 (100.0%), 756.32 (62.1%), 757.33 (19.0%), 758.33 (3.9%)

Synthesis of Compound 2

Compound 2 was synthesized in the same manner as Compound 1 using IM2 instead of IM1 (yield 65%).

m/z: 755.32 (100.0%), 756.32 (62.1%), 757.33 (19.0%), 758.33 (3.9%)

Synthesis of Compound 3

Compound 3 was synthesized in the same manner as Compound 1 using IM3 instead of IM1 (yield 63%).

m/z: 755.32 (100.0%), 756.32 (62.1%), 757.33 (19.0%), 758.33 (3.9%)

Synthesis of Compound 4

Compound 4 was synthesized in the same manner as Compound 1 using IM4 instead of IM1 (yield 67%).

m/z: 755.32 (100.0%), 756.32 (62.1%), 757.33 (19.0%), 758.33 (3.9%)

Synthesis of Compound 5

Compound using N,9,9-triphenyl-9H-fluoren-2-amine instead of N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine Compound 5 was synthesized in the same manner as 1 (yield 70%).

m/z: 803.32 (100.0%), 804.32 (66.4%), 805.33 (21.7%), 806.33 (4.8%)

Synthesis of Compound 6

N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine instead of N-([1,1'-biphenyl]-4-yl)-9, Compound 6 was synthesized in the same manner as Compound 1 using 9-diphenyl-9H-fluoren-2-amine (yield 68%).

m/z: 879.35 (100.0%), 880.35 (72.9%), 881.36 (26.3%), 882.36 (6.4%), 883.36 (1.1%)

Synthesis of Compound 7

Instead of N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine, N-([1,1'-biphenyl]-2-yl)-9, Compound 7 was synthesized in the same manner as Compound 1 using 9-diphenyl-9H-fluoren-2-amine (yield 66%).

m/z: 879.35 (100.0%), 880.35 (72.9%), 881.36 (26.3%), 882.36 (6.4%), 883.36 (1.1%)

Synthesis of compound 8

IM2 and N,9,9-triphenyl-9H-fluoren-2-amine instead of IM1 and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine Compound 8 was synthesized in the same manner as Compound 1 (yield 71%).

m/z: 803.32 (100.0%), 804.32 (66.4%), 805.33 (21.7%), 806.33 (4.8%)

Synthesis of compound 9

IM3 and N,9,9-triphenyl-9H-fluoren-2-amine instead of IM1 and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine Compound 9 was synthesized in the same manner as Compound 1 (yield 65%).

m/z: 803.32 (100.0%), 804.32 (66.4%), 805.33 (21.7%), 806.33 (4.8%)

Synthesis of compound 10

IM3 and N-([1,1'-biphenyl]-4-yl) instead of IM1 and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine )-9,9-diphenyl-9H-fluoren-2-amine was used to synthesize compound 10 in the same manner as compound 1 (yield 65%).

m/z: 879.35 (100.0%), 880.35 (72.9%), 881.36 (26.3%), 882.36 (6.4%), 883.36 (1.1%)

Synthesis of compound 11

IM5 and N,9,9-triphenyl-9H-fluoren-2-amine instead of IM1 and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine Compound 11 was synthesized in the same manner as Compound 1 (yield 70%).

m/z: 767.32 (100.0%), 768.32 (63.1%), 769.33 (19.7%), 770.33 (4.1%)

Synthesis of compound 12

IM4 and N,9,9-triphenyl-9H-fluoren-2-amine instead of IM1 and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine Compound 12 was synthesized in the same manner as Compound 1 (yield 68%).

m/z: 767.32 (100.0%), 768.32 (63.1%), 769.33 (19.7%), 770.33 (4.1%)

Synthesis of compound 13

IM6 and N,9,9-triphenyl-9H-fluoren-2-amine instead of IM1 and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine Compound 13 was synthesized in the same manner as Compound 1 (yield 65%).

m/z: 819.30 (100.0%), 820.30 (67.2%), 821.30 (22.2%), 822.31 (4.7%), 821.29 (4.5%), 822.30 (3.3%)

Synthesis of compound 14

IM7 and N,9,9-triphenyl-9H-fluoren-2-amine instead of IM1 and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine Compound 14 was synthesized in the same manner as Compound 1 (yield 60%).

m/z: 819.30 (100.0%), 820.30 (67.2%), 821.30 (22.2%), 822.31 (4.7%), 821.29 (4.5%), 822.30 (3.3%)

Synthesis of compound 15

IM8 and N,9,9-triphenyl-9H-fluoren-2-amine instead of IM1 and N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine Compound 15 was synthesized in the same manner as Compound 1 (yield 71%).

m/z: 819.30 (100.0%), 820.30 (67.2%), 821.30 (22.2%), 822.31 (4.7%), 821.29 (4.5%), 822.30 (3.3%)

Organic light emitting device manufacturing

Example 1

A glass substrate coated with a 1500 Å thin film of indium tin oxide (ITO) was washed with distilled water ultrasonic waves. After washing with distilled water, the substrate is ultrasonic cleaned with solvents such as isopropyl alcohol, acetone, and methanol, dried, and then transferred 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, HI01 600 Å, HATCN 50 Å, HT01 250 Å as a hole transport layer, and Compound 1 300 Å as a light-emitting auxiliary layer were formed, and then the light-emitting layer was doped with GH01:GD01 9% 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

An organic light-emitting device was produced in the same manner as in Example 1 using Compounds 2 to 15 instead of Compound 1.

Comparative Examples 1 to 8

An organic light-emitting device was manufactured in the same manner as in Example 1 using Ref.1 to Ref.8 instead of Compound 1.

Performance evaluation of organic light emitting devices

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 2 below.

Op. V mA/cm2 Cd/A CIEx CIey LT95 Example 1 4.1 10 67.1 0.334 0.611 240 Example 2 4.1 10 67.3 0.335 0.611 242 Example 3 3.9 10 65.4 0.334 0.612 245 Example 4 3.9 10 65.5 0.334 0.610 245 Example 5 4.1 10 72.0 0.335 0.610 282 Example 6 4.1 10 72.2 0.335 0.611 280 Example 7 4.1 10 72.0 0.335 0.611 282 Example 8 4.2 10 72.5 0.334 0.611 280 Example 9 3.9 10 70.2 0.335 0.610 270 Example 10 3.9 10 70.1 0.334 0.610 275 Example 11 3.9 10 70.0 0.335 0.611 273 Example 12 3.9 10 70.7 0.334 0.611 275 Example 13 4.2 10 71.7 0.335 0.610 255 Example 14 4.2 10 72.0 0.335 0.610 257 Example 15 4.1 10 71.9 0.334 0.611 260 Comparative Example 1 4.7 10 55.0 0.334 0.610 74 Comparative example 2 4.3 10 56.7 0.335 0.610 125 Comparative Example 3 4.3 10 60.5 0.335 0.612 155 Comparative Example 4 4.4 10 61.1 0.337 0.610 138 Comparative Example 5 4.3 10 56.4 0.334 0.612 115 Comparative Example 6 4.4 10 56.8 0.335 0.611 126 Comparative example 7 4.4 10 57.5 0.335 0.611 120 Comparative example 8 4.5 10 60.0 0.335 0.610 100

As shown in Table 2, it can be seen that Examples 1 to 15 using the compound of the present invention as the hole transport layer have increased efficiency and lifespan and low driving voltage compared to Comparative Examples 1 to 8.

More specifically, compared to Comparative Example 1, the embodiments of the present invention have a low driving voltage by combining dibenzofuran or dibenzothiophene to form a deep HOMO level and at the same time have fast hole mobility, and have superior efficiency and increased lifespan. It showed effect.

In addition, compared to Comparative Examples 2 to 4, the examples of the present invention showed high efficiency by maximizing the exciton confinement effect in the light emitting layer by forming a high LUMO level and maintaining T1 by having a branched aryl linkage.

In addition, compared to Comparative Example 5, in the Examples of the present invention, dibenzofuran or dibenzothiophene is connected to nitrogen through three or more branched aryl linkages, thereby increasing pi conjugation, thereby improving hole mobility. It has a low driving voltage and exhibits high efficiency and long lifespan characteristics.

In addition, compared to Comparative Examples 6 and 7, the examples of the present invention have dibenzofuran or dibenzothiophene on one side of the arylamine and fluorene on the other side of the arylamine, resulting in fast hole mobility. It exhibited low driving voltage, high efficiency, and long lifespan characteristics.

In addition, compared to Comparative Example 8, the examples of the present invention can form a high LUMO level and maintain T1 by including a branched aryl linkage between the fluorene-bonded nitrogen and dibenzofuran or dibenzothiophene. At the same time, by minimizing the bulky structure, efficient pi overlap between molecules can be induced, resulting in excellent molecular arrangement and suppressing the roll-off phenomenon, resulting in low driving voltage and high efficiency and long lifespan characteristics.

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)

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

In Formula 1,
X is O or S,
Ar ₁ to Ar ₄ are each independently an unsubstituted aryl group of C ₆ to C ₁₂ ,
Ar ₅ is an unsubstituted C ₆ to C ₃₀ aryl group, dimethylfluorene, dibenzofuran, or dibenzothiophene,
R and R' are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, or a substituted or unsubstituted C ₆ to C ₃₀ aryl group, and adjacent R and R' form a ring with each other. may or may not form,
R ₁ to R ₄ are each independently hydrogen or deuterium,
L ₁ and L ₂ are each independently a direct bond, or a substituted or unsubstituted arylene group of C ₆ to C ₃₀ ,
l, o, p, and q are each independently 0 or an integer of 1 to 4, m and n are each independently 0 or an integer of 1 to 3, and p+q is an integer of 1 or more. According to paragraph 1,
The compound is a compound represented by Formula 2 or Formula 3 below;
[Formula 2]

[Formula 3]
According to paragraph 1,
The compound is a compound represented by the following formula (4) or formula (5);
[Formula 4]

[Formula 5]
According to paragraph 1,
The compound is a compound represented by the following formula (6) or formula (7);
[Formula 6]

[Formula 7]

In Formula 6 or Formula 7,
R ₅ and R ₆ are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, or a substituted or unsubstituted C ₆ to C ₂₄ aryl group, and the dotted lines may or may not be connected to each other. You can. According to paragraph 1,
The compound is a compound represented by Formula 8 or Formula 9 below;
[Formula 8]

[Formula 9]

In Formula 8 or Formula 9,
R ₅ and R ₆ are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, or a substituted or unsubstituted C ₆ to C ₂₄ aryl group, and the dotted lines may or may not be connected to each other. You can. According to paragraph 1,
A compound wherein X is O. According to any one of claims 1 to 5,
A compound wherein X is S. According to paragraph 3,
The compound wherein L ₂ is phenylene. According to paragraph 1,
Ar ₁ to Ar ₄ are each independently selected from the group consisting of phenyl, biphenyl, naphthyl, and combinations thereof. According to any one of claims 1 to 5,
Ar ₅ is a compound selected from the group consisting of phenyl, biphenyl, naphthyl, dibenzofuran, dibenzothiophene, and combinations thereof. According to paragraph 1,
The compound is a compound represented by any one of the following compounds;



An organic light-emitting device comprising an organic material layer containing the compound according to claim 1 between the first electrode and the second electrode. According to clause 12,
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.