KR20200009971A - 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, wherein 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. The present application provides a novel organic compound and the organic light emitting device comprising the same.

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,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C ₆ ~ C ₅₀ aryl group, or a substituted or unsubstituted C ₅ ~ C ₅₀ heteroaryl group,

R ₁ to R ₃ are each independently hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted Of a substituted C ₁ to C ₃₀ alkoxy group, a substituted or unsubstituted C ₁ to C ₃₀ sulfide group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, or a substituted or unsubstituted C ₅ to C _{30 group} Heteroaryl group,

L is a direct bond, a substituted or unsubstituted C ₆ ~ C ₃₀ arylene group, or a substituted or unsubstituted C ₅ ~ C ₃₀ hetero arylene group, provided that L is a direct bond or C ₆ arylene 1) Ar ₁ is a substituted or unsubstituted C ₁₃ ~ C ₅₀ aryl group, or a substituted or unsubstituted C ₁₂ ~ C ₅₀ heteroaryl group, 2) q is an integer of 1, Ar ₁ and Ar ₂ is all a substituted or unsubstituted C ₁₀ ~ C ₅₀ aryl group,

n, o, and p are each independently an integer of 0, 1 or 2, and q is an integer of 0 or 1.

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.

In the arylamine compound according to an embodiment of the present invention, ninth of phenanthrene is connected to nitrogen at the ortho or para position of phenylene to form a suitable HOMO level for the light emitting auxiliary layer, and at the same time, high LUMO level which is easy to block electrons. The organic light emitting diode may be configured to maintain a high T1 and to provide a low driving voltage. In addition, it is possible to implement an organic light emitting device having high efficiency by maximizing the exciton confinement effect in the light emitting layer.

In addition, since nitrogen is combined with phenanthrene in the ortho or para position of phenylene, distortion of substituents around nitrogen is improved, so that the intermolecular thin film arrangement is excellent, thereby enabling long-life organic light emitting device through suppression of roll-off phenomenon.

In addition, the aryl group bonded to nitrogen increases the intermolecular pi-conjugation to improve the hole mobility (Hole Mobility) to implement a low driving voltage and a long life of the organic light emitting device.

The arylamine according to the embodiment of the present invention may form a high Tg including phenanthrene and an aryl group to prevent thin film recrystallization to secure 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, phenantridinyl, acridinyl, phenanthrolinyl, thienyl, and pyridine ring, pyrazine ring, pyrimidine ring , Pyridazine ring, triazine ring, indole ring, quinol Ring, 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,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C ₆ ~ C ₅₀ aryl group, or a substituted or unsubstituted C ₅ ~ C ₅₀ heteroaryl group,

R ₁ to R ₃ are each independently hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted Of a substituted C ₁ to C ₃₀ alkoxy group, a substituted or unsubstituted C ₁ to C ₃₀ sulfide group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, or a substituted or unsubstituted C ₅ to C _{30 group} Heteroaryl group,

L is a direct bond, a substituted or unsubstituted C ₆ ~ C ₃₀ arylene group, or a substituted or unsubstituted C ₅ ~ C ₃₀ hetero arylene group, provided that L is a direct bond or C ₆ arylene 1) Ar ₁ is a substituted or unsubstituted C ₁₃ ~ C ₅₀ aryl group, or a substituted or unsubstituted C ₁₂ ~ C ₅₀ heteroaryl group, 2) q is an integer of 1, Ar ₁ and Ar ₂ is all a substituted or unsubstituted C ₁₀ ~ C ₅₀ aryl group,

n, o, and p are each independently an integer of 0, 1 or 2, and q is an integer of 0 or 1.

In the arylamine compound according to one embodiment of the present invention, ninth of phenanthrene is connected with nitrogen to an ortho or para position of phenylene to form a suitable HOMO level for the light emitting auxiliary layer, and at the same time, high LUMO level with which electron blocking is easy. The organic light emitting diode may be configured to maintain a high T1 and to provide a low driving voltage. In addition, it is possible to implement an organic light emitting device having high efficiency by maximizing the exciton confinement effect in the light emitting layer.

In addition, since nitrogen is combined with phenanthrene in the ortho or para position of phenylene, distortion of substituents around nitrogen is improved, so that the intermolecular thin film arrangement is excellent, thereby enabling long-life organic light emitting device through suppression of roll-off phenomenon.

In addition, the aryl group bonded to nitrogen increases the intermolecular pi-conjugation to improve the hole mobility (Hole Mobility) to implement a low driving voltage and a long life of the organic light emitting device.

The arylamine according to the embodiment of the present invention may form a high Tg including phenanthrene and an aryl group to prevent thin film recrystallization to secure 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).

[Formula 2]

The compound represented by Chemical Formula 2 is a case where phenanthrene is connected to nitrogen in the para position of phenylene in Chemical Formula 1. In this case, it has a fast hole mobility can be effective in improving the driving voltage.

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

[Formula 3]

In Chemical Formula 3,

Ar ₁ and Ar ₂ `` are each independently a substituted or unsubstituted C ₁₀ to C ₅₀ aryl group,

l is an integer of 0 or 1.

The compound represented by Chemical Formula 3 is a case where phenanthrene is connected to nitrogen at a para position of phenylene in Chemical Formula 1, and n, o, p, and q are 1. In such a case, the PI conjugation may be increased to have faster hole mobility.

In one embodiment of the present invention, the compound may be represented by the following formula (4).

[Formula 4]

In Chemical Formula 4,

R ₅ and R ₆ are each independently hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted Substituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ sulfide group, substituted or unsubstituted C ₆ to C ₂₄ aryl group, or substituted or unsubstituted C ₅ to C ₂₄ Heteroaryl group,

m and m` are each independently an integer of 0, 1 or 2, provided that m + m` is an integer of 1 or more.

The compound represented by Formula 4 is embodied in a form in which L may have a substituent in Formula 1, wherein n, o, p, and q are 1. In this case, L is expanded to the arylene group, so that the thin film arrangement of the molecules is excellent, and thus may be effective in suppressing the roll-off phenomenon.

In one embodiment of the present invention, the compound may be represented by the following formula (5) or formula (6).

[Formula 5]

[Formula 6]

In Chemical Formula 5 or Chemical Formula 6,

X is O or S,

L ₁ and L ₂ are each independently a direct bond, a substituted or unsubstituted C ₆ ~ C ₃₈ arylene group, or a substituted or unsubstituted C ₅ ~ C ₃₈ heteroarylene group,

R ₇ and R ₈ are each independently hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted Substituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ sulfide group, substituted or unsubstituted C ₆ to C ₃₆ aryl group, or substituted or unsubstituted C ₅ to C ₃₆ Heteroaryl group,

The compound represented by Formula 5 is when Ar ₁ is embodied as L ₂ and unsubstituted phenanthrene in Formula 1, and n, o, p, and q are 1. In this case, the unsubstituted phenanthrene may further minimize the bulky characteristics, thereby enabling low voltage driving.

In addition, the compound represented by Chemical Formula 6 is embodied as dibenzofuranyl or dibenzothiophenyl in which Ar ₁ may have a substituent with L ₂ in Chemical Formula 1, and n, o, p, and q are 1 If it is. In this case, mobility can be improved, and even in a relatively low molecule, it has a high Tg, thereby preventing recrystallization of the thin film and having excellent driving stability.

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

[Formula 7]

The compound represented by the above formula (7) may be embodied in phenanthryl Ar ₁ is an unsubstituted Transistor in Formula 1, and L is a direct bond, and when the n, o, p, and q 1. In this case, it is possible to maintain high LUMO and T1 by minimizing the connector, which may be effective for blocking electrons and excitons, and further minimizing the bulky characteristics with unsubstituted phenanthrene, thereby enabling low voltage driving.

According to an embodiment of the present invention, in Formulas 1 to 7, R ₁ to R- ₈ may be each independently hydrogen or a phenyl group.

Further, according to one embodiment of the present invention, in Formulas 1 to 6, L, L ₁ and L ₂ are each independently a group consisting of a direct bond, phenylene, biphenylene, terphenylene and combinations thereof Can be selected from.

According to an embodiment of the present invention, in Formulas 1 to 3 and 5 to 7, Ar ₁ and Ar ₂ are each independently phenyl, naphthyl, biphenyl, terphenyl, phenanthrenyl, dibenzofu May be selected from the group consisting of ranyl, dibenzothiophenyl, and combinations thereof. Also, specifically, in Formulas 1 to 3 and 5 to 7, Ar ₁ and Ar ₂ may be each independently selected from the group consisting of phenyl, biphenyl, terphenyl, 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 according to the present invention described above. 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 light emitting device may include an organic material layer containing a hole transport material and an organic material layer containing a compound according to the present invention, but may not be limited thereto.

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.

As described above, the compound according to the present invention may be represented by any one of Formulas 1 to 7.

In addition, in one embodiment of the present invention, the light emitting auxiliary layer may contain a compound according to the present invention, a hole injection layer containing a compound represented by the following formula (8) between the first electrode and the light emitting auxiliary layer or It may include a hole transport layer.

[Formula 8]

In Chemical Formula 8,

Ar _a and Ar _b are each independently a substituted or unsubstituted C ₆ ~ C ₅₀ aryl group, or a substituted or unsubstituted C ₅ ~ C ₅₀ heteroaryl group,

R ₁ ′ to R ₄ ′ each independently represent hydrogen, a halogen, a nitro group, a nitrile group, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, a substituted or Unsubstituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ sulfide group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, or substituted or unsubstituted C ₅ to C ₃₀ heteroaryl group,

L` is a direct bond, a substituted or unsubstituted C ₆ ~ C ₃₀ arylene group, or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroarylene group,

The dotted line means that the R ₁ 'and R _2' may not be associated with or connected to each other.

The compound represented by Formula 8 may be any one of the following compounds, 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.

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

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.

To a round bottom flask was dissolved phenanthren-9-ylboronic acid 30.0g, 1-bromo-4-iodobenzene 42.0g in _{1,4-dioxan 1000ml K 2 CO 3} (2M) into a 200ml and Pd (PPh _{3) 4} 4.7g After stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure and recrystallized to obtain 31.1 g of intermediate IM1 (yield 69%).

Synthesis of Intermediate IM2

Using the same method as IM1, IM2 was synthesized by changing starting materials as follows.

Synthesis of Intermediate IM3

Using the same method as IM1, IM3 was synthesized by changing starting materials as follows.

Synthesis of Intermediate IM4

Intermediate IM4 was synthesized in the following manner.

In a round bottom flask, 20.0 g of phenanthren-9-ylboronic acid and 32.4 g of bis (4-bromophenyl) amine were dissolved in 800 ml of 1,4-dioxan, and 150 ml of K ₂ CO ₃ (2M) and 3.1 g of Pd (PPh ₃ ) ₄ were added. After stirring under reflux. The reaction was confirmed by TLC and the reaction was terminated after the addition of water. The organic layer was extracted with MC, filtered under reduced pressure and recrystallized to obtain 21.6 g of an intermediate IM4 (yield 72%).

Compound synthesis

The intermediate compounds IM1 to IM4 were used to synthesize the target compounds as follows.

Synthesis of Compound 1

In a round bottom flask, IM1 3.0g, di ([1,1 ': 4', 1 ''-terphenyl] -4-yl) amine 3.9g, t-BuONa 1.3g, Pd ₂ (dba) ₃ 0.3g, ( 0.4 ml of t-Bu) ₃ P was dissolved in 100 ml 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 then purified and recrystallized to obtain 4.6 g (yield 70%) of compound 1. m / z: 725.31 (100.0%), 726.31 (61.4%), 727.31 (18.2%), 728.32 (3.6%)

Synthesis of Compound 2

N-([1,1'-biphenyl] -4-yl)-[1,1 ': 4', 1 ''-terphenyl] -4-amine instead of N-([1,1 ': 4', 1 Compound 2 was synthesized by the same method as Compound 1 using '' -terphenyl] -4-yl)-[1,1 ': 3', 1 ''-terphenyl] -4-amine (yield 65%). m / z: 725.31 (100.0%), 726.31 (61.4%), 727.31 (18.2%), 728.32 (3.6%)

Synthesis of Compound 3

Di ([1,1 ': 3', 1 'instead of N-([1,1'-biphenyl] -4-yl)-[1,1': 4 ', 1' '-terphenyl] -4-amine Compound 3 was synthesized in the same manner as compound 1 using '-terphenyl] -4-yl) amine. (Yield 65%) m / z: 725.31 (100.0%), 726.31 (61.4%), 727.31 (18.2% ), 728.32 (3.6%)

Synthesis of Compound 4

Compound 4 was synthesized in the same manner as Compound 1 using IM2 instead of IM1 (yield 68%) m / z: 801.34 (100.0%), 802.34 (67.4%), 803.35 (22.5%), 804.35 (4.9%)

Synthesis of Compound 5

IM2 and N-([1,1 ': 4', 1 ''-terphenyl] -4-yl instead of IM1 and di ([1,1 ': 4', 1 ''-terphenyl] -4-yl) amine Compound 5 was synthesized by the same method as Compound 1 using)-[1,1 ': 3', 1 ''-terphenyl] -4-amine. (Yield 70%) m / z: 801.34 (100.0%) , 802.34 (67.4%), 803.35 (22.5%), 804.35 (4.9%)

Synthesis of Compound 6

IM3 and di ([1,1'-biphenyl) instead of IM1 and N-([1,1'-biphenyl] -4-yl)-[1,1 ': 4', 1 ''-terphenyl] -4-amine ] -4-yl) amine was used to synthesize compound 6 in the same manner as compound 1 (yield 63%) m / z: 725.31 (100.0%), 726.31 (61.4%), 727.31 (18.2%), 728.32 (3.6%)

Synthesis of Compound 7

IM1 and N-([1,1'-biphenyl] -4-yl)-[1,1 ': 4', 1 ''-terphenyl] -4-amine instead of IM4 and 4-bromo-1,1'- Compound 7 was synthesized by the same method as compound 1 using biphenyl. (Yield 67%) m / z: 673.28 (100.0%), 674.28 (56.6%), 675.28 (15.7%), 676.29 (2.9%)

Synthesis of Compound 8

IM4 and 4-bromo-1,1 'instead of IM1 and N-([1,1'-biphenyl] -4-yl)-[1,1': 4 ', 1' '-terphenyl] -4-amine: Compound 8 was synthesized in the same manner as in Compound 1 using 4 ', 1' '-terphenyl. (Yield 70%) m / z: 749.31 (100.0%), 750.31 (63.5%), 751.31 (19.6%), 752.32 (4.0%)

Synthesis of Compound 9

IM4 and 4-bromo-1,1 'instead of IM1 and N-([1,1'-biphenyl] -4-yl)-[1,1': 4 ', 1' '-terphenyl] -4-amine: Compound 9 was synthesized using 3 ', 1' '-terphenyl in the same manner as in compound 1. (Yield 70%) m / z: 749.31 (100.0%), 750.31 (63.5%), 751.31 (19.6%), 752.32 (4.0%)

Synthesis of Compound 10

IM4 and 4- (4-bromophenyl) dibenzo [instead of IM1 and N-([1,1'-biphenyl] -4-yl)-[1,1 ': 4', 1 ''-terphenyl] -4-amine Compound 10 was synthesized in the same manner as Compound 1 using b, d] furan. (Yield 65%) m / z: 763.29 (100.0%), 764.29 (63.2%), 765.29 (19.8%), 766.30 (4.1 %)

Synthesis of Compound 11

2-bromo-9,9-diphenyl-9H-fluorene 2.0g, 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine 1.6g, t-BuONa 0.7g, Pd ₂ (dba ₃ ) 0.2 g and (t-Bu) ₃ P 0.2 ml were dissolved in 60 ml 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 then purified by column and recrystallized to obtain 2.2 g of Compound 11 (yield 73%). m / z: 601.28 (100.0%), 602.28 (50.2%), 603.28 (12.3%), 604.29 (2.0%)

Organic light emitting device manufacturing

Example 1

An indium tin oxide (ITO) 1500 Å thick thin 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 600 주, HATCN 50 화합물, Compound 11 250 Å with a hole transport layer and Compound 1 100 으로 with a light emitting auxiliary layer were formed using an evaporator, and then doped with 3% BH01: BD01 with a light emitting layer to form a 250 Å film. . Next, ET01: Liq (1: 1) 300 Å was formed into an electron transport layer, followed by LiF 10 Å and aluminum (Al) 1000 막. The organic light emitting device was manufactured by encapsulating the device in a glove box.

Examples 2-10

In the same manner as in Example 1, an organic light emitting diode was manufactured by using the compound 2 to 10 instead of the compound 1 as a light emitting auxiliary layer.

Comparative Examples 1 to 11

In the same manner as in Example 1, an organic light emitting diode was manufactured by using Ref. 1 to Ref. 11 instead of compound 1.

Comparative Example 12

An indium tin oxide (ITO) 1500 Å thick thin 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 Using an evaporator, a hole injection layer HI01 600Å, HATCN 50Å, a hole transport layer Ref.2 250Å and a light emitting auxiliary layer were formed into a film, and the light emitting layer was doped with BH01: BD01 3%. It produced. Next, ET01: Liq (1: 1) 300 Å was formed into an electron transport layer, followed by LiF 10 Å and aluminum (Al) 1000 막. The organic light emitting device was manufactured by encapsulating the device in a glove box.

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 1 below.

Op. V mA / cm2 Cd / A QE (%) CIEx CIEy LT95 Example 1 3.8 10 8.2 7.2 0.140 0.109 155 Example 2 3.9 10 8.3 7.2 0.139 0.110 151 Example 3 3.9 10 8.3 7.3 0.140 0.111 151 Example 4 3.8 10 8.4 7.4 0.140 0.109 164 Example 5 3.8 10 8.4 7.4 0.142 0.110 160 Example 6 3.9 10 8.5 7.4 0.140 0.110 160 Example 7 3.8 10 8.6 7.5 0.141 0.110 175 Example 8 3.8 10 8.8 7.7 0.140 0.109 190 Example 9 3.9 10 8.9 7.8 0.141 0.109 180 Example 10 3.8 10 8.5 7.5 0.140 0.110 170 Comparative Example 1 4.5 10 4.2 3.0 0.140 0.111 15 Comparative Example 2 4.0 10 6.3 5.1 0.141 0.110 123 Comparative Example 3 4.2 10 6.7 5.6 0.140 0.110 85 Comparative Example 4 4.3 10 6.9 5.9 0.141 0.110 80 Comparative Example 5 4.4 10 7.1 6.0 0.140 0.111 95 Comparative Example 6 4.1 10 7.5 6.3 0.141 0.111 90 Comparative Example 7 4.1 10 7.3 6.3 0.140 0.110 100 Comparative Example 8 4.1 10 6.9 5.8 0.140 0.110 95 Comparative Example 9 4.3 10 7.2 6.0 0.140 0.110 66 Comparative Example 10 4.4 10 7.1 6.0 0.140 0.110 60 Comparative Example 11 4.0 10 7.8 6.9 0.140 0.110 105 Comparative Example 12 4.4 10 5.9 4.2 0.140 0.111 77

As shown in Table 1, Examples 1 to 10 using the compound of the present invention as a light emitting auxiliary layer can be seen that the efficiency and life is increased compared to Comparative Examples 1 to 12, showing a low driving voltage .

More specifically, the exemplary embodiments of the present invention have a linking group between phenanthrene and nitrogen, and include terphenyl on the other side of nitrogen, compared to Comparative Examples 1 and 2, so that the aryl group is expanded to increase the conjugation. Thus, it can have a fast hole mobility, and at the same time has a high Tg has the effect that the drive stability is improved.

In addition, in comparison with Comparative Examples 3, 4, and 5, the embodiments of the present invention can maintain high LUMO and HOMO at the same time as the ninth position of the phenanthrene is easily connected to nitrogen, and thus the light emitting layer. The hole transfer can be facilitated, and the electronic blocking is effectively performed to lower the driving voltage and exhibit high efficiency.

In addition, in comparison with Comparative Examples 6, 7, and 8, the embodiments of the present invention are phenyl is directly bonded to nitrogen, so that the condensed ring is not directly bonded to nitrogen, thereby maintaining a high T1 and effecting exciton confinement in the emission layer. It can be maximized, showing high efficiency.

In addition, compared to Comparative Examples 9 and 10, the embodiments of the present invention are connected to the aryl group in the para or ortho position of the phenylene adjacent to nitrogen to minimize the twist angle of the molecule and maintain fast mobility, thereby suppressing the roll-off phenomenon Low drive voltage and long life.

In addition, compared with Comparative Example 11, the embodiments of the present invention has a linear expanded aryl group without having a deuterium as a substituent, easy to purify high purity and excellent in the thin film arrangement of the molecules showed high efficiency and long life.

In addition, compared with Comparative Example 12, the embodiments of the present invention has a high HOMO by using a fluorene-substituted arylamine compound as a hole transport layer, the compound of the present invention as a light emitting auxiliary layer between the hole transport layer and the light emitting layer By minimizing the hole transport barrier between the hole transport layer and the light emitting layer, the hole transport in the light emitting layer is facilitated, resulting in low voltage driving, high efficiency and long life.

In view of the above evaluation results, it is determined that the compound according to the present invention is effective in lowering the driving voltage of the organic light emitting device and improving efficiency and lifespan.

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 (14)

A compound represented by Formula 1;
[Formula 1]

In Chemical Formula 1,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C ₆ ~ C ₅₀ aryl group, or a substituted or unsubstituted C ₅ ~ C ₅₀ heteroaryl group,
R ₁ to R ₃ are each independently hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ ~ C ₃₀ alkyl group, substituted or unsubstituted C ₂ ~ C ₃₀ alkenyl group, substituted or unsubstituted Of a substituted C ₁ to C ₃₀ alkoxy group, a substituted or unsubstituted C ₁ to C ₃₀ sulfide group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, or a substituted or unsubstituted C ₅ to C _{30 group} Heteroaryl group,
L is a direct bond, a substituted or unsubstituted C ₆ ~ C ₃₀ arylene group, or a substituted or unsubstituted C ₅ ~ C ₃₀ hetero arylene group, provided that L is a direct bond or C ₆ arylene 1) Ar ₁ is a substituted or unsubstituted C ₁₃ ~ C ₅₀ aryl group, or a substituted or unsubstituted C ₁₂ ~ C ₅₀ heteroaryl group, 2) q is an integer of 1, Ar ₁ and Ar ₂ is a substituted or unsubstituted C ₁₀ ~ C ₅₀ aryl group
n, o, and p are each independently an integer of 0, 1 or 2, and q is an integer of 0 or 1. The method of claim 1,
The compound is a compound represented by the formula (2);
[Formula 2]

The method of claim 1,
The compound is a compound represented by the formula (3);
[Formula 3]

In Chemical Formula 3,
Ar ₁ and Ar ₂ `` are each independently a substituted or unsubstituted C ₁₀ to C ₅₀ aryl group,
l is an integer of 0 or 1. The method of claim 1,
The compound is a compound represented by the formula (4);
[Formula 4]

In Chemical Formula 4
R ₅ and R ₆ are each independently hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted Substituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ sulfide group, substituted or unsubstituted C ₆ to C ₄₄ aryl group, or substituted or unsubstituted C ₅ to C ₄₄ Heteroaryl group,
m and m` are each independently an integer of 0, 1 or 2, provided that m + m` is an integer of 1 or more. The method of claim 1,
The compound is a compound represented by the following formula (5) or (6);
[Formula 5]

[Formula 6]

In Chemical Formula 5 or Chemical Formula 6,
X is O or S,
L ₁ and L ₂ are each independently a direct bond, a substituted or unsubstituted C ₆ ~ C ₃₈ arylene group, or a substituted or unsubstituted C ₅ ~ C ₃₈ heteroarylene group,
R ₇ and R ₈ are each independently hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted Substituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ sulfide group, substituted or unsubstituted C ₆ to C ₃₆ aryl group, or substituted or unsubstituted C ₅ to C ₃₆ Heteroaryl group. The method of claim 1,
The compound is a compound represented by the formula (7);
[Formula 7]

The method according to any one of claims 1 to 6,
R ₁ to R ₈ are each independently hydrogen or a phenyl group. The method according to any one of claims 1 to 5,
L, L ₁ and L ₂ are each independently selected from the group consisting of a direct bond, phenylene, biphenylene, terphenylene and combinations thereof. The method according to any one of claims 1 to 6,
Ar ₁ and Ar ₂ are each independently selected from the group consisting of phenyl, naphthyl, biphenyl, terphenyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, and combinations thereof. The method according to any one of claims 1 to 6,
Ar ₁ and Ar ₂ are each independently selected from the group consisting of phenyl, biphenyl, terphenyl and combinations thereof. The method of claim 1,
Compound represented by Formula 1 is 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 material 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. The method of claim 13,
The organic material layer is a light emitting auxiliary layer, the organic light emitting device further comprises a hole injection layer or a hole transport layer containing a compound represented by the formula (8) between the light emitting auxiliary layer and the first electrode;
[Formula 8]

In Chemical Formula 8,
Ar _a and Ar _b are each independently a substituted or unsubstituted C ₆ ~ C ₅₀ aryl group, or a substituted or unsubstituted C ₅ ~ C ₅₀ heteroaryl group,
R ₁ ′ to R ₄ ′ each independently represent hydrogen, a halogen, a nitro group, a nitrile group, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, a substituted or Unsubstituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ sulfide group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, or substituted or unsubstituted C ₅ to C ₃₀ heteroaryl group,
L` is a direct bond, a substituted or unsubstituted C ₆ ~ C ₃₀ arylene group, or a substituted or unsubstituted C ₅ ~ C ₃₀ heteroarylene group,
The dotted line means that the R ₁ 'and R _2' may not be associated with or connected to each other.

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