KR102098063B1 - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides a novel compound capable of improving the luminous efficiency, stability and lifespan of a device, an organic electrical device using the same, and an electronic device thereof.

Description

Compounds for organic electrical devices, organic electrical devices using the same, and electronic devices thereof {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}

The present invention relates to a compound for an organic electric element, an organic electric element using the same, and an electronic device thereof.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as the organic material layer in the organic electric device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their function. In addition, the light emitting material may be classified into a high molecular weight type and a low molecular weight type according to the molecular weight, and may be classified into a fluorescent material derived from the singlet excited state of the electron and a phosphorescent material derived from the triplet excited state of the electron according to the light emission mechanism. You can. In addition, the luminescent material may be divided into blue, green, and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color according to the luminous color.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength moves to a long wavelength due to intermolecular interaction, and the color purity is reduced or the efficiency of the device is reduced due to the light emission attenuation effect. In order to increase the luminous efficiency through, a host / dopant system may be used as a luminescent material. The principle is that when a small amount of the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with the light emitting layer, excitons generated in the light emitting layer are transported to the dopant to produce light with high efficiency. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of a desired wavelength can be obtained according to the type of dopant used.

The most important issues in organic electroluminescent devices are life and efficiency. As the display becomes larger, these efficiency and life problems must be solved. Efficiency, life, and driving voltage are related to each other, and when the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic substances due to Joule heating generated during driving decreases, and as a result, It shows a tendency to increase the life.

However, it is not possible to maximize efficiency by simply improving the organic material layer, and the optimal combination of energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) When achieved, long life and high efficiency can be achieved simultaneously. Therefore, there is a need to develop a light-emitting material that has high thermal stability and can efficiently achieve charge balance in the light-emitting layer. That is, in order to sufficiently exhibit the excellent characteristics of the organic electric device, materials constituting an organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, are supported by stable and efficient materials. It should be preceded, but the development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently made, and among them, development of a material for a light emitting layer is urgently required.

An object of the present invention is to provide a compound capable of improving the device's high luminous efficiency, low driving voltage, high heat resistance, color purity, and lifetime, and an organic electric device using the same and its electronic device.

In one aspect, the present invention provides a compound represented by the following formula.

In another aspect, the present invention provides an organic electric device using the compound represented by the formula and an electronic device thereof.

By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and lifetime of the device can be greatly improved.

1 is an exemplary view of an organic electroluminescent device according to the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

It should be noted that in adding reference numerals to the components of each drawing, the same components have the same reference numerals as possible even though they are displayed on different drawings. In addition, in describing the present invention, when it is determined that detailed descriptions of related well-known configurations or functions may obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.

In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only for distinguishing the component from other components, and the nature, order, or order of the component is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to the other component, but another component between each component It should be understood that elements may be "connected", "coupled" or "connected".

As used in this specification and the appended claims, unless otherwise stated, the meaning of the following terms is as follows:

The terms "halo" or "halogen" as used herein are fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), unless otherwise noted.

The term "alkyl" or "alkyl group" used in the present invention has a single bond of 1 to 60 carbon atoms, unless otherwise specified, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cycle. By radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.

The term "haloalkyl group" or "halogenalkyl group" as used in the present invention means an alkyl group substituted with halogen unless otherwise specified.

The term "heteroalkyl group" used in the present invention means that at least one of the carbon atoms constituting the alkyl group is replaced with a heteroatom.

The term "alkenyl group" or "alkynyl group" used in the present invention has a double or triple bond of 2 to 60 carbon atoms, and includes straight or branched chain groups, and is not limited thereto, unless otherwise specified. It is not.

As used herein, the term "cycloalkyl" means an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, but is not limited thereto.

The term "alkoxyl group", "alkoxy group", or "alkyloxy group" used in the present invention means an alkyl group to which an oxygen radical is attached, and has a carbon number of 1 to 60 unless otherwise specified, and is limited thereto. It is not.

As used herein, the terms "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and 2 to 60 unless otherwise specified. It has a carbon number, and is not limited thereto.

The term "aryloxyl group" or "aryloxy group" used in the present invention means an aryl group to which an oxygen radical is attached, and has a carbon number of 6 to 60 unless otherwise specified, and is not limited thereto.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, and are not limited thereto unless otherwise specified. In the present invention, an aryl group or an arylene group means a single ring or multi-ring aromatic, and includes an aromatic ring formed by adjacent substituents participating in a bond or reaction. For example, the aryl group may be a phenyl group, biphenyl group, fluorene group, or spirofluorene group.

The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and a radical substituted with an aryl group has a carbon number described herein.

Also, when the prefix is named in succession, it means that the substituents are listed in the order described first. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxycarbonyl group, it means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonyl alkenyl group, it means an alkenyl group substituted with an arylcarbonyl group. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

As used herein, the term "heteroalkyl" means alkyl containing one or more heteroatoms, unless otherwise specified. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or an arylene group having 2 to 60 carbon atoms each containing at least one heteroatom, unless otherwise specified, and is not limited thereto. No, it includes at least one of a single ring and multiple rings, and may be formed by combining adjacent functional devices.

The term "heterocyclic group" used in the present invention includes at least one heteroatom, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, heteroaliphatic ring and hetero, unless otherwise specified. Aromatic rings. Adjacent functional groups may also be formed by bonding.

The term “heteroatom” as used herein refers to N, O, S, P or Si, unless otherwise stated.

Unless otherwise specified, the term "aliphatic" as used herein refers to an aliphatic hydrocarbon having 1 to 60 carbon atoms, and "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise stated, the term "saturated or unsaturated ring" as used herein refers to a saturated or unsaturated aliphatic ring or an aromatic ring or heterocycle having 6 to 60 carbon atoms.

Other hetero compounds or hetero radicals other than the above-described hetero compounds include one or more hetero atoms, but are not limited thereto.

Unless otherwise specified, the term "carbonyl" used in the present invention is represented by -COR ', where R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, 3 to 30 carbon atoms. Is a cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise specified, the term "ether" used in the present invention is represented by -RO-R ', wherein R or R' are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or 6 to 30 carbon atoms. It is an aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ arylthiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, substituted with deuterium C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron Means a group, a germanium group, and one or more substituents selected from the group consisting of C ₂ to C ₂₀ heterocyclic groups, and is not limited to these substituents.

In addition, unless expressly stated, in the following formula used in the present invention

When a is an integer of 0, the substituent R ¹ is absent, and when a is an integer of 1, one substituent R ¹ is bound to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3, And R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it binds to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bound to the carbon forming the benzene ring is omitted. do.

1 is an exemplary view of an organic electric device according to an embodiment of the present invention.

Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180 and a first electrode 110 and a second electrode 180 formed on the substrate 110. ) Is provided with an organic material layer containing the compound represented by Formula 1. At this time, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170 sequentially on the first electrode 120. At this time, layers other than the emission layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light-emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and the electron transport layer 160 may also serve as a hole blocking layer.

In addition, although not shown, the organic electric device according to the present invention may further include a protective layer formed on one surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode.

The compound according to the present invention applied to the organic layer is the material of the host or dopant or capping layer of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, the light emitting layer 150 Can be used as

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, an anode 120 is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, and a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, and an electron transport layer are formed thereon. 160) and after forming an organic material layer including the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.

In addition, the organic material layer is made by using a variety of polymer materials, and less by a method such as a solution process or a solvent process (e.g. spin coating, dip coating, doctor blading, screen printing, inkjet printing or thermal transfer), not a deposition method. It can be prepared by a number of layers. Since the organic material layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the formation method.

The organic electric device according to the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.

In addition, the organic electric device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoreceptor (OPC), an organic transistor (organic TFT), a monochromatic or white lighting device.

Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electric element of the present invention and a control unit for controlling the display device. At this time, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game machines, various TVs, and various computers.

Hereinafter, a compound according to an aspect of the present invention will be described.

The compound according to one aspect of the present invention is represented by the following formula (1).

    Formula (1)

In the above formula,

또는

이고, A ring and B ring are independent of each other

or

ego,

X is one selected from the group consisting of N (R _a ), O, S and C (R _a ) (R _b ),

Y ¹ and Y ² are each independently selected from the group consisting of N (R _c ), O, S and C (R _c ) (R _d ), provided that only one of Y ¹ and Y ² is present, and the rest One is absent, and the absence is a single bond),

L is a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And C ₃ ~ C _{60 It} is selected from the group consisting of a fused ring group of an aliphatic ring and an aromatic ring of C ₆ ~ C ₆₀ ,

R _a to R _d are independently of each other hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L ¹ -N (Ar ² ) (Ar ³ ); (wherein L ¹ is the same as the definition of L, and Ar ² and Ar ³ are independently of each other C ₆ ~ C ₆₀ aryl group; fluorene group; C ₃ ~ C a fused ring of an aromatic ring of an aliphatic ring and a C ₆ ~ C ₆₀ groups of _60; and O, N, S, Si and C containing at least one hetero atom of the P ₂ ~ C ₆₀ heterocyclic group; selected from the group consisting of), or R _a and R _b , and / or R _c and R _d are bonded to each other to form a ring,

Ar ¹ is hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L ² -N (Ar ⁴ ) (Ar ⁵ ); (where L ² , Ar ⁴ and Ar ⁵ are the same as the definitions of L ¹ , Ar ² and Ar ³ , respectively),

l, m, n and o are each independently an integer from 0 to 4,

R ¹ to R ⁴ are independently of each other, and when l, m, n, and o are 2 or more, they are the same as or different from each other as a plurality, Deuterium independently of each other; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L ³ -N (Ar ⁶ ) (Ar ⁷ ), wherein L ³ , Ar ⁶ and Ar ⁷ are the same as the definitions of L ¹ , Ar ² and Ar ³ , respectively, or

Alternatively, R ¹ to R ⁴ are the same as or different from each other as a plurality when l and m are 2 or more, and multiple R ¹ Between, R ² between, R ³ between, and / or R ⁴ Each of them combines to form a ring,

The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group and fluorenylene group are independently of each other, deuterium, halogen, silane group, silox Acid group, boron group, germanium group, cyano group, nitro group, -L ⁴ -N (Ar ⁸ ) (Ar ⁹ ) (where L ⁴ , Ar ⁸ and Ar ⁹ are definitions of L ¹ , Ar ² and Ar ³ , respectively) Same as), C ₁ ~ C ₂₀ alkylthio, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₆ ~ C ₂₀ aryl group, substituted with deuterium C ₆ ~ C ₂₀ aryl group, fluorenyl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ It may be further substituted with one or more substituents selected from the group consisting of an arylalkyl group, and C ₈ ~ C ₂₀ aryl alkenyl group.

Looking at the specific compounds 1-12,1-29, 2-1 and 2-15, etc. of the present invention where only one of Y ¹ and Y ² is present, and the other one is absent and directly connected, Y ¹ and Y ^Notice that only one of the ^two exists.

Meanwhile, the compound represented by Chemical Formula (1) may be represented by one of the following Chemical Formulas.

     Formula (2) Formula (3)

Formula (4) Formula (5)

In Formulas 2 to 5, X, R ¹ to R ⁴ , L, Ar ¹ , L, l, m, n, and o, which are the same symbols as Formula 1, are the same as defined in Formula 1, and Y is the same as in claim 1 It can be defined in the same way as defined Y ¹ .

Specifically, the compound represented by the formula (1) is any one of the compounds represented by the following compounds, but is not limited thereto.

In another embodiment according to the present invention, the present invention includes a first electrode, a second electrode, and an organic material layer located between the first electrode and the second electrode, the organic material layer according to an embodiment of the present invention It provides an organic electric device characterized in that it contains a compound.

In another embodiment according to the present invention, the present invention provides an organic electric device further comprising a light efficiency improving layer formed on at least one of the lower portion of the first electrode or the upper portion of the second electrode.

In another embodiment according to the present invention, the present invention provides an organic electric device that forms an organic material layer by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process.

In another embodiment according to the present invention, the present invention provides an organic electroluminescent device characterized in that it contains a compound according to an embodiment of the present invention as a material of a light emitting layer.

In another embodiment according to the present invention, the present invention provides an electronic device including a display device including the above-described organic electric element and a control unit driving the display device.

In another embodiment according to the present invention, the present invention is an organic electroluminescent device (OLED), an organic solar cell, an organic photoreceptor (OPC), an organic transistor (organic TFT), and a device for monochromatic or white lighting It provides an electronic device characterized in that at least one.

Hereinafter, examples of the synthesis of the compound represented by the formula (1) according to the present invention and the production example of the organic electric device will be specifically described with reference to examples, but the present invention is not limited to the following examples.

Synthetic example

Synthesis of the compound was carried out in the following manner.

Final product ( final products ) Synthesis Example

Illustratively, the compounds according to the present invention (final products: products 1-1 to 4-20) may be prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1.

<Scheme 1>

One. Sub  1, Compound

Sub 1 of Scheme 1 may be synthesized by the following Reaction Scheme 2, but is not limited thereto.

<Reaction Scheme 2>

(One) Sub  One- Synthesis Example 2

Put tert -butyl lithium (1.1 eq) in Sub 1-1 (1 eq) and stir at -78 ^o C for 1 hour. After raising to room temperature, S ₈ (1.5 eq) was added and stirred for 3 hours. After that, add HCL and stir for 30 minutes. After the reaction was completed, extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain Sub 1-2.

(2) Sub  One- 4 Synthesis example

After dissolving Sub 1-2 (1 eq) and Sub 1-3 (1 eq), potassium tert-butoxide (1.1 eq), (NHC) ₂ Ni (0.04 eq) obtained in the above synthesis in DMF, for 16 hours. Stir at 110 ^o C. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product by column chromatography to obtain the desired Sub 1-4.

(3) Sub 1 Synthesis example

Sub 1-3 (1 eq.), I ₂ (1.25 eq.) And cyclohexane were added to a Hanovia photoreactor with a 1450 W medium pressure Hg lamp and argon was replaced for 20 minutes. Then, propylene oxide (6 equivalents) was added and irradiated for 30 minutes. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product by column chromatography to obtain the desired Sub 1.

Meanwhile, examples of Sub 1 are as follows, but are not limited thereto, and their FD-MS are shown in Table 1 below.

2. Sub  2 compounds

Examples of Sub 2 are as follows, but are not limited thereto, and their FD-MS are shown in Table 2 below.

3. Final product ( final product Synthesis of)

Round bottom flask with Sub 1 compound (1 eq), Sub 2 compound (1.2 eq), Pd ₂ (dba) ₃ (0.05 eq), P (t-Bu) ₃ (0.1 eq), NaO t -Bu (3 eq) ), toluene (10.5 mL / 1 mmol) was added, and the reaction proceeded at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, and the organic layer was dried over MgSO ₄ and concentrated, and then the resulting organic product was obtained by silicagel column and recrystallization.

(One) Product  1-1 of Synthetic example

9-membered heterocyclic compound (10.8g, 20mmol), bromobenzene (3.8g, 24mmol), Pd ₂ (dba) ₃ (0.03 ~ 0.05 mmol), P (t-Bu) ₃ (0.1 eq), NaO in a round bottom flask After adding t- Bu (3 eq.) and toluene (10.5 mL / 1 mmol), the reaction proceeds at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, and the organic layer was dried over MgSO ₄ and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain 10.0 g of product (yield: 81%).

(2) Product  2-5 of Synthetic example

9-atomic heterocyclic compound (10.8g, 20mmol), 2-bromo-4-phenylquinazoline (6.8g, 24mmol), Pd ₂ (dba) ₃ (0.03 ~ 0.05 mmol), P (t-Bu) _{3 in a} round bottom flask (0.1 eq), NaO t -Bu (3 eq), toluene (10.5 mL / 1 mmol) was added and the reaction proceeded at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, and the organic layer was dried over MgSO ₄ and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain 10.1 g of product (yield: 68%).

(3) Product  Synthesis example of 3-6

9-membered heterocyclic compound (10.8g, 20mmol), 4-bromo-N, N-diphenylaniline (7.8g, 24mmol), Pd ₂ (dba) ₃ (0.03 ~ 0.05 mmol), P (t-Bu) in a round bottom flask ) ₃ (0.1 eq), NaO t -Bu (3 eq), toluene (10.5 mL / 1 mmol) was added and the reaction proceeded at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 12.2 g of product (yield: 78%).

(4) Product  4-15 Synthetic example

9-membered heterocyclic compound (10.5g, 20mmol), 5-bromo-2,4-diphenylpyrimidine (7.5g, 24mmol), Pd ₂ (dba) ₃ (0.03 ~ 0.05 mmol), P (t-Bu) ) ₃ (0.1 eq), NaO t -Bu (3 eq), toluene (10.5 mL / 1 mmol) was added and the reaction proceeded at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, and the organic layer was dried over MgSO ₄ and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain 10.5 g of product (yield: 70%).

On the other hand, FD-MS values of the compounds 1-1 to 4-20 of the present invention prepared according to the above synthesis example are shown in Table 3 below.

Manufacturing evaluation of organic electric devices

[ Experimental example  1] to [ Experimental example  80] Red organic electroluminescent device (Phosphorescence Red  Host)

The organic electroluminescent device was manufactured according to a conventional method using the compound obtained through synthesis as a light emitting host material of the light emitting layer.

First, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N ¹ on the ITO layer (anode) formed on the glass substrate After forming a hole injection layer having a thickness of 60 nm by vacuum-deposition of a -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film, 4,4-bis [N- (1-) as a hole transport compound on the hole injection layer -Naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 60 nm to form a hole transport layer. Next, doping the compound of the present invention as a host on the hole transport layer and (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate] as a dopant material in a 95: 5 weight ratio Then, a light emitting layer was deposited to a thickness of 30 nm. Subsequently, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolinoleito) aluminum (hereinafter abbreviated as BAlq) as a hole blocking layer on the light emitting layer is vacuumed to a thickness of 10 nm. It was deposited, and tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited as an electron transport layer to a thickness of 40 nm. Subsequently, an organic electroluminescent device was manufactured by depositing LiF, an alkali metal halide as an electron injection layer, to a thickness of 0.2 nm, and then depositing Al to a thickness of 150 nm to use as a cathode.

[ Comparative example  One]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example except that Comparative Example 1 was used instead of the compound of the present invention as a host material for the light emitting layer.

Comparative Compound (1) CBP

[ Comparative example  2]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example, except that Comparative Example 2, instead of the compound of the present invention, was used as the host material for the light emitting layer, the following Comparative Compound 2 was used.

Comparative Compound (2)

[ Comparative example  3]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example, except that Comparative Example 3, instead of the compound of the present invention, was used as the host material for the light emitting layer, the following Comparative Compound 3 was used.

Comparative Compound (3)

As described above was applied with a forward bias DC voltage to the prepared Experimental Example and Comparative Example An organic electroluminescence element Photo Research (photoresearch) 's were measured and electroluminescence (EL) properties by PR-650, from the measurement result 2500cd / m ² based on the luminance T95 life was measured by a life measurement equipment manufactured by Max Science.

Table 4 below shows the device fabrication and evaluation results for Experimental Examples 1 to 80 and Comparative Examples 1 to 3 to which the compounds according to the invention were applied.

As can be seen from the results of Table 4, when the compound of the present invention is used as a material for an organic electroluminescent device as a red emitting layer material, it is possible to not only lower the driving voltage of the organic electroluminescent device, but also significantly improve the luminous efficiency and lifetime. have.

This can be explained that the compounds in which the nine rings of the present invention are fused have a high thermal stability and a bipolar system is formed, thereby exhibiting an effect of increasing driving, efficiency, and lifetime.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains will be capable of various modifications without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed herein are not intended to limit the present invention, but to explain the present invention, and the spirit and scope of the present invention are not limited by these embodiments.

The scope of protection of the present invention should be interpreted by the following claims, and all technologies within the equivalent range should be interpreted as being included in the scope of the present invention.

100: organic electrical element 110: substrate
120: first electrode 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (9)

delete Compound represented by one of the following formulas 2 to 5:
<Formula 2><Formula3>

<Formula 4><Formula5>

In Chemical Formulas 2 to 5,
X is N (R _a ), O, S or C (R _a ) (R _b ),
Y is N (R _c ), O, S or C (R _c ) (R _d ),
Ar ¹ is a C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; And -L ² -N (Ar ⁴ ) (Ar ⁵ );
L is a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And C ₃ ~ C _{60 It} is selected from the group consisting of a fused ring group of an aliphatic ring and an aromatic ring of C ₆ ~ C ₆₀ ,
R ¹ to R ⁴ are independently of each other deuterium; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L ³ -N (Ar ⁶ ) (Ar ⁷ ) is selected from the group consisting of a plurality of R ¹ , R ² , R ³ , or R ⁴ may be combined with each other to form a ring,
l, m, n and o are each independently an integer of 0 to 4, and when each of these is an integer of 2 or more, each of R ^1, each of R ^2, each of R ^{3, and} each of R ⁴ are the same or different from each other,
R _a to R _d are independently of each other hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryloxy group; And -L ¹ -N (Ar ² ) (Ar ³ );
In C (R _a ) (R _b ), R _a and R _b may combine with each other to form a ring,
In C (R _c ) (R _d ), R _c and R _d may combine with each other to form a ring,
L ¹ to L ³ are each independently a single bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And C ₃ ~ C _{60 It} is selected from the group consisting of a fused ring group of an aliphatic ring and an aromatic ring of C ₆ ~ C ₆₀ ,
Ar ² to Ar ⁷ are independently of each other C ₆ ~ C ₆₀ aryl group; Fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; And O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom; is selected from the group consisting of,
The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group and fluorenylene group, respectively, deuterium, halogen, silane group, siloxane group, boron Group, germanium group, cyano group, nitro group, -L ⁴ -N (Ar ⁸ ) (Ar ⁹ ), where L ⁴ , Ar ⁸ and Ar ⁹ are the same as the definitions of L ¹ , Ar ² and Ar ³ , respectively. ), C ₁ ~ C ₂₀ alkylthio, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₆ ~ C ₂₀ aryl group, substituted with deuterium, C ₆ ~ C ₂₀ aryl group, fluorenyl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ arylalkyl group And, C ₈ ~ C ₂₀ It may be substituted with one or more substituents selected from the group consisting of aryl alkenyl group. Compounds characterized by being one of the following compounds:

In the organic electrical device including a first electrode, a second electrode, and an organic material layer located between the first electrode and the second electrode,
The organic material layer comprises an organic electroluminescent device comprising the compound of claim 2 or 3. The method of claim 4,
And an optical efficiency improving layer formed on at least one surface opposite to the organic material layer among one surface of the first electrode and one surface of the second electrode. The method of claim 4,
The organic layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. The method of claim 4,
The compound is an organic electric device characterized in that it is used as a light emitting layer material. A display device comprising the organic electroluminescent element of claim 4; And
An electronic device comprising; a control unit for driving the display device. The method of claim 8,
The organic electroluminescent device is an electronic device characterized in that it is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoreceptor (OPC), an organic transistor (organic TFT), and a monochromatic or white lighting device.

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