KR20200006406A - Novel compound and organic electroluminescent divice including the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic light emitting device comprising the same. The novel compound according to an embodiment of the present invention is applied to the organic light emitting device to secure high efficiency, long lifespan, low driving voltage, and driving stability of the organic light emitting device. A compound according to an embodiment of the present invention can form a high Tg through a fluorene and branched aryl linkage group, thereby being able to ensure driving stability of the organic light emitting device.

Description

Novel compound and organic light emitting device including the same {NOVEL COMPOUND AND ORGANIC ELECTROLUMINESCENT DIVICE INCLUDING THE SAME}

The present application relates to a novel compound and an organic light emitting device comprising the same.

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

To date, various compounds are known as materials used in such organic light emitting devices. However, in the case of organic light emitting devices using materials known to date, 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 having low voltage driving, high brightness and long life using materials having excellent properties.

Korea Patent Publication 10-2015-0086721

The present application provides a novel organic compound, and an organic light emitting device comprising the same.

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

A first aspect of the present application provides a compound represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

X is O or S,

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

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

R, R ', R ₁ to R ₄ 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 Substituted C ₁ to C ₃₀ alkoxy, nitro group, nitrile group, sulfide group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, or substituted or unsubstituted C ₅ to 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 ~ C ₃₀ arylene group, or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroarylene group,

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

The arylamine compound according to one embodiment of the present invention has a fluorene and dibenzofuran or dibenzothiophene substituent, and has a branched aryl linkage between nitrogen and dibenzofuran or dibenzothiophene. By introducing fluorene and branched aryl linkage groups into arylamines, deep HOMO levels can be formed, and high LUMO levels can be easily formed to block electron transfer, thereby achieving low voltage and high efficiency of the organic light emitting device.

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

In addition, the compound according to the embodiment of the present invention may increase the pyconjugation due to the fluorene and branched aryl linking groups, and may have an excellent thin film arrangement of the molecules. Accordingly, hole mobility is improved and a long-life organic light emitting device can be realized by suppressing a rolloff phenomenon.

In addition, the compound according to an embodiment of the present invention can form a high Tg through fluorene and branched aryl linkages to prevent thin film recrystallization to ensure driving stability of the organic light emitting device.

1 shows a schematic view of an organic light emitting device according to an embodiment of the present disclosure.

Hereinafter, with reference to the accompanying drawings will be described in detail the embodiments and embodiments of the present application to be easily carried out by those of ordinary skill in the art.

As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding other components unless specifically stated otherwise. As used throughout this specification, the terms "about", "substantially", and the like, are used at, or in proximity to, the numerical values of the preparations and material tolerances inherent in the meanings indicated, and refer to the understanding herein. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers. As used throughout this specification, the term "step to" or "step of" does not mean "step for."

Throughout this specification, the term "combination of these" included in the expression of the makushi form refers to one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.

Throughout this specification, the 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, for example phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenylenyl, perylene It means containing an aromatic ring such as nil, chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzocrisenyl, anthracenyl, stilbenyl, pyrenyl, etc., "heteroaryl" means at least one As an aromatic ring of C _3-30 containing a hetero element, for example, pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindoleyl, 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 high Li, acridine ring, pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, piperazine ring, carbazole ring, furan ring, thiophene ring, oxazole ring, oxadiazole ring, benzo Heterocyclic groups formed from oxazole ring, thiazole ring, thiadiazole ring, benzothiazole ring, triazole ring, imidazole ring, benzoimidazole ring, pyran ring, dibenzofuran ring, dibenzothiophene ring It may mean to include.

Throughout this specification, the term "substituted or unsubstituted" refers to deuterium, halogen, amino, nitrile, nitro or C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C ₃ ~ C ₂₀ to a cycloalkyl group, C ₃ ~ C ₂₀ heterocycloalkyl group, C ₆ ~ C ₃₀ aryl group and C ₃ ~ substituted with one or more groups selected from a heteroaryl group the group consisting of C ₃₀ or is replaced in the Can mean.

In addition, the same symbol throughout the present specification may have the same meaning unless specifically noted.

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 substituted with hydrogen bonded to carbon 9, or a substituted or unsubstituted C. _And substituted with _3-30 heteroaryl groups.

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

[Formula 1]

In Chemical Formula 1,

X is O or S,

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

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

R, R ', R ₁ to R ₄ 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 Substituted C ₁ to C ₃₀ alkoxy, nitro group, nitrile group, sulfide group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, or substituted or unsubstituted C ₅ to 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 ~ C ₃₀ arylene group, or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroarylene group,

1, 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 a fluorene and dibenzofuran or dibenzothiophene substituent, and has a branched aryl linkage between nitrogen and dibenzofuran or dibenzothiophene. By introducing fluorene and branched aryl linkage groups into arylamines, deep HOMO levels can be formed, and high LUMO levels can be easily formed to block electron transfer, thereby achieving low voltage and high efficiency of the organic light emitting device.

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

In addition, the compound according to the embodiment of the present invention may increase the pyconjugation due to the fluorene and branched aryl linking groups, and may have an excellent thin film arrangement of the molecules. Accordingly, hole mobility is improved and a long-life organic light emitting device can be realized by suppressing a rolloff phenomenon.

In addition, the compound according to an embodiment of the present invention can form a high Tg through fluorene and branched aryl linkages to prevent thin film recrystallization to ensure driving stability of the organic light emitting device.

In one embodiment of the present invention, the compound may be represented by the following formula (2) or (3).

[Formula 2]

[Formula 3]

In the compound represented by Formula 2, when Ar ₁ is phenylene in Formula 1, p is 1, q is 0, and the compound represented by Formula 3 is Ar ₂ in Formula 1, phenylene, 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 the following formula (4) or (5).

[Formula 4]

[Formula 5]

The compound represented by the above formula (4) is Ar ₁ is phenylene in formula (I), wherein p is 1, q is 0, and if L ₂ is a direct bond. In this case, the fast hole mobility may be effective for improving driving voltage.

In the compound represented by Formula 5, Ar ₂ in Formula 1 is phenylene, p is 0, q is 1, and a hetero ring including X is bonded to phenylene at a meta position. In this case, it is possible to effectively improve the efficiency of the organic light emitting device through the meta phenylene bond.

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

In one embodiment of the present invention, the compound may be represented by the following formula (6) or formula (7).

[Formula 6]

[Formula 7]

In Chemical Formula 6 or Chemical 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 is an alkoxy, nitro group, nitrile group, sulfide group, substituted or unsubstituted C ₆ -C ₂₄ aryl group, or substituted or unsubstituted C ₅ -C ₂₄ heteroaryl group, and the dotted lines are connected to each other It may not be connected.

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

Compound represented by Formula 6 is Ar ₁ is phenylene in formula (I), wherein p is 1, q is 0, L ₂ is a direct bond, and when R and R 'is phenyl, in the formula (7) In the compound represented by Formula 1, Ar ₂ is phenylene, p is 0, q is 1, and a 3-ring compound including X is bonded to phenylene at a meta position, and R and R 'are In the case of phenyl. In this case, by minimizing the linker, it can be effective in blocking unnecessary movement of electrons with high LUMO and T1.

In one embodiment of the present invention, the compound may be represented by the following formula (8) or formula (9).

[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 is an alkoxy, nitro group, nitrile group, sulfide group, substituted or unsubstituted C ₆ -C ₂₄ aryl group, or substituted or unsubstituted C ₅ -C ₂₄ heteroaryl group, and the dotted lines are connected to each other It may not be connected.

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

The compound represented by the above formula (8) and Ar ₁ is phenylene in formula (I), wherein p is 1, q is 0, and L ₁ and L ₂ is a bond, the nitrogen is directly bonded to the 2-position of the fluorene Wherein R and R 'are phenyl, and the compound represented by Formula 9 is Ar ₂ in the formula 1, phenylene, p is 0, q is 1, L ₁ is a direct bond, and nitrogen is This is the case when the 3 ring compound including X directly bonds to position 2 of fluorene, and is bonded to phenylene at a meta position, and R and R 'are phenyl. In this case, it is possible to have a faster hole mobility to suppress the roll-off phenomenon, it can be effective in improving the life.

According to an embodiment of the present invention, in Chemical Formulas 1 to 9, l, m, n, and o may all be zero. In addition, when l is an integer of 2 or more, R ₁ may be the same or different from each other. The same applies to R ₂ to R ₄ , Ar ₃ and Ar ₄ even when m, n, o, p and q are integers of 2 or more.

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

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

Further, according to one embodiment of the present invention, in Chemical Formulas 1 to 9, X may be O. In this case, it may be effective to improve the life of the organic light emitting device.

Further, according to one embodiment of the present invention, in Chemical Formulas 1 to 9, X may be S. In this case, it may be effective to improve the efficiency of the organic light emitting device.

According to one embodiment of the present invention, in Formula 1 to Formula 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.

The second aspect of the present application provides an organic light emitting device comprising the compound represented by Formula 1. The organic light emitting device may include one or more organic material layers containing a compound according to the present application 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. In addition, the compounds of the present invention may be used alone or in combination with known compounds when forming the organic layer.

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

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 between a first electrode (anode) and a second electrode (cathode, cathode). One or more organic material layers, such as a layer (EIL), may be included.

For example, the organic light emitting device may be manufactured as shown in FIG. 1. The organic light emitting device is 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 The injection electrodes 2000 may be stacked in this order.

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

The hole injection electrode 1000 is used as an anode for hole injection of the organic light emitting device. A material having a low work function may be used to inject holes, and may be formed of a transparent material such as indium tin oxide (ITO), indium zinc oxide (IZO), and graphene.

A hole injection layer 200 may be formed on the anode by depositing a hole injection layer material by a method such as vacuum deposition, spin coating, casting, or Langmuir-Blodgett (LB). When the hole injection layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer 200, the structure and thermal properties of the desired hole injection layer, and generally, 50-500 deposition. Temperature, a vacuum of 10 ⁻⁸ to 10 ⁻³ torr, a deposition rate of 0.01 to 100 kPa / sec, and a layer thickness of 10 Pa to 5 μm may be appropriately selected.

Next, a hole transport layer 300 may be formed by depositing a hole transport layer material on the hole injection layer 200 by a method such as vacuum deposition, spin coating, cast, or LB. When the hole transport layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, the hole transport layer is preferably selected in the same condition range as the formation of the hole injection layer.

The hole transport layer 300 may use 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. In addition, according to one embodiment of the present invention, the hole transport layer 300 may be one or more layers, and may include a hole transport layer formed only of a known material. In addition, according to the exemplary embodiment of the present invention, an auxiliary light emitting layer may be formed on the hole transport layer 300.

The light emitting layer 400 may 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, cast, LB, or the like. In the case of forming the light emitting layer by the vacuum deposition method, the deposition conditions vary depending on the compound used, but in general, it is preferable to select within the same condition range as the formation of the hole injection layer. In addition, the light emitting layer material may use a known compound as a host or dopant.

In addition, when used with a phosphorescent dopant in the light emitting layer, to prevent the phenomenon of triplet excitons or holes diffused into the electron transport layer, the hole suppression material (HBL) may be further laminated by vacuum deposition or spin coating. The hole-suppressing material which can be used at this time is not particularly limited, but any one of the well-known ones used as the hole-inhibiting material can be selected and used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the hole-inhibiting material described in Japanese Patent Laid-Open No. 11-329734 (A1) can be cited. Oxy-2-methylquinolinolato) -aluminum biphenoxide), a phenanthrolines-based compound (e.g., BDC (vasocuproin) from UDC), etc. may be used.

The electron transport layer 500 is formed on the light emitting layer 400 formed as described above, and the electron transport layer may be formed by a vacuum deposition method, a spin coating method, a casting method, or the like. In addition, although the deposition conditions of the electron transport layer are different depending on the compound used, it is generally preferable to select within the same condition range as the formation of the hole injection layer.

Subsequently, an electron injection layer 600 may be formed by depositing an electron injection layer material on the electron transport layer 500, wherein the electron transport layer is formed by vacuum deposition, spin coating, or casting a conventional electron injection layer material. It can form by a method, such as a method.

The hole injection layer 200, the hole transport layer 300, the light emitting layer 400, the electron transport layer 500 of the organic light emitting device may use the compound according to the present invention or may use the following materials, or according to the present invention Compounds and known materials can be used together.

The cathode 2000 for electron injection is formed on the electron injection layer 600 by a method such as vacuum deposition or sputtering. Various metals may 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 not only an organic light emitting device having an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode structure, but also a structure of an organic light emitting device having various structures. It is also possible to form a layer or two intermediate layers.

As described above, the thickness of each organic material layer formed in accordance with the present invention can be adjusted according to the required degree, specifically 1 to 1,000 nm, more specifically may be 5 to 200 nm.

In addition, the present invention has an advantage that the organic layer including the compound represented by the formula (1) is uniform in surface and excellent in shape stability because it can adjust the thickness of the organic layer in molecular units.

For the organic light emitting compound according to the present aspect may be all applied to the first aspect of the present application, but may not be limited thereto.

Hereinafter, the embodiments of the present application will be described in more detail, and the scope of the present application is not limited by the present embodiment.

EXAMPLE

Synthesis of Compound Represented by Formula 1

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

Synthesis of Intermediate IM

Intermediate IM may be synthesized through the following reaction for synthesis of the desired compound, but is not limited thereto.

Synthesis of Intermediate IM1

Intermediate IM1 was synthesized in the following manner.

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 ( 3.3 g of PPh ₃ ) ₄ was added thereto, followed by stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure and recrystallized to obtain 22.6 g of intermediate IM1-1 (yield 60%). In a round bottom flask, 21-1 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 thereto, followed by stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure and recrystallized to obtain 19.2 g of an 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 thereto, followed by stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure and recrystallized to obtain 13.2 g of intermediate IM1 (yield 65%).

Synthesis of Intermediates IM2 to IM8

By varying the starting material as shown in Table 1, the following IM2 to IM8 was synthesized in the same manner as the IM1.

Compound synthesis

The intermediates IM1 to IM8 were used to synthesize the target compounds as follows.

Synthesis of Compound 1

In a round bottom flask, IM1 2.0g, N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine 1.7g, t-BuONa 0.6g, Pd ₂ ( dba) ₃ 0.2g, (t-Bu) ₃ P 0.2ml was dissolved in 60ml of toluene and stirred under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure, and purified by column 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 by the same method 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, instead of N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine 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

N-([1,1'-biphenyl] -2-yl) -9, instead of N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine 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 using (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 using (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 using (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 using (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 using (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 using (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 using (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

An indium tin oxide (ITO) 1500 µm thick glass substrate was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, transferred to a plasma cleaner, and then cleaned the substrate using oxygen plasma for 5 minutes and then a thermal vacuum evaporator on the top of the ITO substrate (thermal A hole injection layer HI01 600Å, HATCN 50 50, a hole transport layer HT01 250Å and a light emitting auxiliary layer were formed using an evaporator), and then the light emitting layer was doped with 9% GH01: GD01 to form 250 250. Next, ET01: Liq (1: 1) 300 Å was formed into an electron transport layer, followed by LiF 10 Å and aluminum (Al) 1000 Å.

Examples 2-15

In the same manner as in Example 1, an organic light emitting diode was manufactured by using the compound 2 to 15 instead of the compound 1.

Comparative Examples 1 to 8

In the same manner as in Example 1, an organic light-emitting device was manufactured by using Ref. 1 to Ref. 8 instead of compound 1.

Performance Evaluation of Organic Light Emitting Diode

Inject electrons and holes by applying voltage to a Keithley 2400 source measurement unit and measure the luminance when light is emitted using the Konica Minolta Spectroradiometer (CS-2000) As a result, the performance of the organic light emitting diodes of Examples and Comparative Examples was evaluated by measuring current density and luminance with respect to an applied voltage under atmospheric pressure, 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, Examples 1 to 15 using the compound of the present invention as a hole transport layer can be seen that the efficiency and life is increased compared to Comparative Examples 1 to 8, showing a low driving voltage.

More specifically, the embodiments of the present invention, compared with Comparative Example 1, is combined with dibenzofuran or dibenzothiophene to form a deep HOMO level and at the same time have a fast hole mobility, has a low driving voltage, excellent efficiency and long life The effect was shown.

In addition, compared with Comparative Examples 2 to 4, the embodiments of the present invention had a branched aryl linking group to exhibit high efficiency by maximizing the exciton confinement effect in the light emitting layer by forming a high LUMO level and maintaining T1.

In addition, in comparison with Comparative Example 5, the embodiments of the present invention are linked to the dibenzofuran or dibenzothiophene through the nitrogen through three or more branched aryl linkages, thereby increasing the PI conjugation, thereby improving the hole mobility It has low driving voltage, high efficiency and long life.

In addition, in comparison with Comparative Examples 6 and 7, embodiments of the present invention have dibenzofuran or dibenzothiophene on one side of the arylamine, and at the same time have fast hole mobility by including fluorene on the other side of the arylamine. Low drive voltage, high efficiency and long life.

In addition, compared to Comparative Example 8, the embodiments of the present invention may include a branched aryl linkage between fluorene-bonded nitrogen and dibenzofuran or dibenzothiophene to maintain high LUMO level formation and T1 At the same time, the bulky structure can be minimized to induce efficient pi overlap between molecules, resulting in excellent molecular arrangement and reduced roll-off, resulting in low driving voltage, high efficiency and long life.

The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are 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 Formula 1;
[Formula 1]

In Chemical Formula 1,
X is O or S,
Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group,
Ar ₅ is a substituted or unsubstituted C ₆ ~ C ₃₀ aryl group, or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroaryl group,
R, R ', R ₁ to R ₄ 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 Substituted C ₁ to C ₃₀ alkoxy, nitro group, nitrile group, sulfide group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, or substituted or unsubstituted C ₅ to 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 ~ C ₃₀ arylene group, or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroarylene group,
1, 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 method of claim 1,
The compound is a compound represented by the following formula (2) or (3);
[Formula 2]

[Formula 3]

The method of claim 1,
The compound is a compound represented by the following formula (4) or (5);
[Formula 4]

[Formula 5]

The method of claim 1,
The compound is a compound represented by the following formula (6) or formula (7);
[Formula 6]

[Formula 7]

In Chemical Formula 6 or Chemical 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 is an alkoxy, nitro group, nitrile group, sulfide group, substituted or unsubstituted C ₆ -C ₂₄ aryl group, or substituted or unsubstituted C ₅ -C ₂₄ heteroaryl group, and the dotted lines are connected to each other It may not be connected. The method of claim 1,
The compound is a compound represented by the following formula (8) or formula (9);
[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 is an alkoxy, nitro group, nitrile group, sulfide group, substituted or unsubstituted C ₆ -C ₂₄ aryl group, or substituted or unsubstituted C ₅ -C ₂₄ heteroaryl group, and the dotted lines are connected to each other It may not be connected. The method according to any one of claims 1 to 5,
X is O. The method according to any one of claims 1 to 5,
X is S. The method according to any one of claims 3 to 5,
L ₂ is phenylene. The method according to any one of claims 1 to 5,
Ar ₁ to Ar ₄ are each independently selected from the group consisting of phenyl, biphenyl, naphthyl and combinations thereof. The method 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. The method of claim 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 a compound according to any one of claims 1 to 11 between a first electrode and a second electrode. The method of claim 12,
The organic layer is an organic light emitting device of at least one of a hole injection layer, a hole transport layer and a light emitting auxiliary layer.

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