KR102019831B1 - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents

Abstract

The present invention provides a novel compound that can improve the luminous efficiency, stability and life of the device, an organic electric device using the same, and an electronic device thereof.

Description

COMPONENT FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND A ELECTRONIC DEVICE THEREOF

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

Mr. Eastman Kodak Corporation in the 1980s. W. CW Tang et al. Developed a laminated structure element in which various roles were distributed to each material, thereby making organic electroluminescent elements using organic materials practical. They stack a phosphor that can transport electrons and an organic that can transport holes, and injects charges into both layers of the phosphor to emit light, so that a high brightness of 1000 cd / m ² or more can be obtained at a voltage of 10 V or less. It was.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of 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 element may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their functions. The light emitting material may be classified into a polymer type and a low molecular type 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. Can be. In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

In particular, various studies have been conducted on organic materials inserted into the hole transport layer or the buffer layer for excellent life characteristics of the organic electric device, and for this purpose, a thin film after deposition is provided while providing high hole transport characteristics from the anode to the organic layer. There is a need for a hole injection layer material having high uniformity and low crystallinity in forming.

Delays penetration of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of the shortening of the life of the organic electric device, and stable properties for Joule heating generated when driving the device, that is, high glass transition temperature. There is a need for development of a hole injection layer material having In addition, the low glass transition temperature of the hole transport layer material has been reported to have a significant effect on the device life, depending on the characteristics of the uniformity of the surface of the thin film when driving the device. In addition, the deposition method is the mainstream in the formation of the OLED device, a situation that requires a material that can withstand a long time, that is, a material having a strong heat resistance characteristics.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. In order to increase the light emitting efficiency through the light emitting material, a host / dopant system may be used. The principle is that when a small amount of dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing 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 to be used.

In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material constituting the 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, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.

An object of the present invention is to provide a novel compound that can improve the high luminous efficiency, low driving voltage, color purity, and lifetime of the device, an organic electric device using the same, and an electronic device thereof.

Specifically, the present invention solves the problems of the prior art described above, in order to achieve the object of the present invention to improve the luminous efficiency, low driving voltage, color purity, stability and life of the device is represented by the formula (1) to provide.

In Chemical Formula 1,

(1) R ₁ and R ₂ are hydrogen ; Deuterium ; Tritium ; Halogen group ; Nitro group; Nitrile group; Amide group; Silane group; A condensed ring group of an aromatic ring of C ₆ ~ C ₆₀ and an aliphatic ring of C ₄ ~ C ₆₀ ;

Hydrogen, deuterium, halogen group, C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkylamine group, C ₁ ~ C ₆₀ arylamine group, C ₁ ~ C ₆₀ alkylthiophene group, C ₆ ~ C ₆₀ aryl thiophene group, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ of the aryl A group, a C ₆ to C ₆₀ aryl group substituted with deuterium, a C ₈ to C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and C ₆ ~ C ₆₀ aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a substituted or unsubstituted C ₂ ~ C ₆₀ heterocyclic group ;

C ₁ ~ alkenyl group of the C ₂₀ alkyl group, C ₂ ~ C ₂₀ of, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ aryl group of C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with deuterium, C ₇ C ₁ -C ₅₀ unsubstituted or substituted with one or more substituents selected from the group consisting of -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group and acetylene group Alkyl group ;

Hydrogen, deuterium, halogen, CN, NO ₂ , C ₁ -C ₆₀ alkyl group, C ₁ -C ₆₀ alkoxy group, C ₁ -C ₆₀ alkylamine group, C ₆ -C ₆₀ arylamine group, C ₁ C ₆₀ alkylthiophene group, C ₂ -C ₆₀ alkenyl group, C ₂ -C ₆₀ alkynyl group, C ₃ -C ₆₀ cycloalkyl group, C ₆ -C ₆₀ aryl group, deuterium substituted C _In the group consisting of ₆ to C ₆₀ aryl groups, substituted or unsubstituted silane groups, substituted or unsubstituted boron groups, substituted or unsubstituted germanium groups, and substituted or unsubstituted C ₂ to C ₆₀ heterocyclic groups C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with one or more selected groups and includes at least one heteroatom of O, N, or S ; And

An amine group unsubstituted or substituted with one or more groups selected from the group consisting of C ₁ to C ₆₀ alkyl groups, C ₂ to C ₆₀ alkenyl groups, C ₆ to C ₆₀ aryl groups, and C ₈ to C ₆₀ aryl alkenyl groups It is selected from the group consisting of;

(2) Ar ₁ to Ar ₈ are the same or different, respectively

Hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ aryl thiophene group, a C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C of ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, a heavy hydrogen of the Substituted with one or more substituents selected from the group consisting of C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron group, germanium group, C ₂ ~ C ₂₀ heterocyclic group Or an unsubstituted C ₆ -C ₆₀ aryl group ;

Hydrogen, deuterium, halogen, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ arylamine group, C ₆ -C ₆₀ aryl A C ₆ to C ₂₀ aryl group, a C ₇ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, a C ₂ to C ₂₀ heterocyclic group, a nitrile group and an acetylene group A C ₂ to C ₆₀ heterocyclic group which is unsubstituted or substituted with one or more substituents in the group and includes at least one heteroatom of O, N, or S;

Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₃₀ cycloalkyl group, C ₁ ~ C ₃₀ of unsubstituted or substituted with one or more substituents selected from the group consisting of C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₂ ~ C ₆₀ heterocyclic group Alkoxy group ;

Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₃₀ cycloalkyl group, a C ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₆₀ with one or more substituents selected from the group consisting of a heterocyclic-substituted or unsubstituted C ₆ ~ C ₃₀ substituted by deuterium Aryloxy group ;

Halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ cycloalkyl group, C ₆ ~ C of a ₆₀ aryl group, C ₂ ~ C ₆₀ with one or more substituents selected from the group consisting of a heterocyclic-substituted or unsubstituted C ₆ ~ C ₆₀ arylamine group; And

C ₁ ~ alkenyl group of the C ₂₀ alkyl group, C ₂ ~ C ₂₀ of, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ aryl group of C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with deuterium, C ₇ C ₁ -C ₅₀ alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group ; It is selected from the group consisting of.

(3) R ₁ , R ₂ , Ar ₁ to Ar ₈ may be bonded or reacted with a neighboring group to form a saturated or unsaturated ring. Here, the unsaturated ring includes not only alicyclic and aromatic rings, but also heterocycles. In addition, each of Ar ₁ to Ar _{8 may} be bonded or reacted with a neighboring group to form a saturated or unsaturated aliphatic ring, an aromatic ring, a hetero ring, a spiro compound, or the like.

In this case, the term 'neighborhood group' includes not only a substituent attached to the mother nucleus but also the mother nucleus itself. Accordingly, each of R ₁ , R ₂ , Ar ₁ to Ar ₈ may form a saturated or unsaturated ring by combining or reacting with a neighboring substituent or functional group or a functional group or a carbon included in the mother nucleus. have. In this case, the ring formed may be an aromatic, alicyclic, heterocyclic, spiro compound and the like.

(4) a and b are integers of 1-4, and when a and b are two or more, some R <_1> , R <_2> may be same or different.

As used herein, an "aryl group" refers to a monocyclic or heterocyclic aromatic, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction.

In addition, a "heterocyclic group" means an aromatic or alicyclic monocyclic or heterocyclic ring containing a heteroatom (heteroatom) instead of a carbon forming a ring, a hetero formed by neighboring substituents participating in the bond or reaction Aromatic or cycloaliphatic rings.

In addition, the present invention solves the problems of the prior art described above, in order to achieve the object of the present invention to improve the luminous efficiency, low driving voltage, color purity, stability and life of the device represented by the formula (2) to (4) To provide.

In the formula (2) to (4), Ar ₁ to Ar ₈ are the same as Ar ₁ ~ Ar ₈ of formula (1), R ₁ to R ₆ are the same as R ₁ and R _2, a to f will It is an integer of 1-4.

More specifically, Formula 1 to Formula 4 may be one of the following compounds.

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

The compounds represented by Chemical Formulas 1 to 4 may be one of the compounds represented by Chemical Formulas 1-1 to 4-17, but are not limited thereto. In this case, since each substituent of the compounds represented by Formulas 1 to 4 is practically difficult to exemplify all the compounds in a broad relationship, exemplary compounds have been exemplarily described, but Formulas 1 to 4, which are not shown in Formulas 1-1 to 4-17, are illustrated. The compounds represented by 4 may also form part of the present specification.

By using the novel compound according to the present invention, it is possible to greatly improve the device's high luminous efficiency, low driving voltage, color purity, and lifetime.

1 to 6 show examples of the organic electroluminescent device to which the compound of the present invention can be applied.

Compounds according to the invention having the above formula can be used in a soluble process. In other words, the compounding may form an organic material layer of an organic electric device to be described later by a solution process. In other words, when the compound is used as an organic material layer, the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings.

In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

Example

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Experimental Examples. However, the following Production Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Production Example

Hereinafter, preparation or synthesis examples of the compounds belonging to Chemical Formula 1 will be described. However, some of the compounds belonging to Formula 1 will be exemplarily described since the number of compounds belonging to Formula 1 is large. Those skilled in the art to which the present invention pertains, that is, those skilled in the art can prepare the compounds belonging to the present invention which are not illustrated through the preparation examples described below.

General Synthetic Methods for Compounds of Formula 1 and Formula 2

General Synthetic Methods for Compounds of Formula 3, Formula 4

General Synthesis of Sub Materials

Hereinafter, a method for synthesizing intermediates A to D used in the synthesis of Chemical Formulas 1 to 4 will be described.

Synthesis Example of Intermediate A

Synthesis of 3,5-dibromo-N, N-diphenylaniline

1,3,5-tribromobenzene (18.6 g, 59.1 mmol), diphenylamine (10 g, 59.1 mmol), Pd ₂ (dba) ₃ (1.6 g, 1.77 mmol), P (t-Bu) _{3 in a} 250 mL round bottom flask (3.6 g, 17.73 mmol), NaOtBu (14.2 g, 147.8 mmol) and Toluene (150 mL) were added sequentially, followed by reaction at room temperature for 30 minutes. After completion of the reaction, the mixture was extracted using methylene chloride, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 13.1 g (54.9%) of the product.

Sum of N- (3,5-dibromophenyl) -N- (naphthalen-1-yl) naphthalen-1-amine castle

1,3,5-tribromobenzene (37.2 g, 118.2 mmol), dinaphthalen-1-ylamine (20 g, 118.2 mmol), Pd ₂ (dba) ₃ (7.2 g, 3.54 mmol), P (t) in a 250 mL round bottom flask -Bu) ₃ (7.2 g, 35.46 mmol), NaOtBu (28.4 g, 295.6 mmol) and Toluene (300 mL) were added in this order, followed by reaction for 30 minutes at room temperature. After completion of the reaction, the mixture was extracted using methylene chloride, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was subjected to silicagel column to give 26.2 g (54.9%) of the product.

Synthesis of 3,5-dibromo-N, N-di-p-tolylaniline

Di- p- tolylamine (15 g, 76.03 mmol), 1,3,5-tribromobenzene (23.9 g, 76.03 mmol), Pd ₂ (dba) ₃ (2.09 g, 2.28 mmol), P (t) in a 250 mL round bottom flask -Bu) ₃ (4.6 g, 22.8 mmol), NaOtBu (18.3 g, 190.1 mmol) and Toluene (200 mL) were added in this order, followed by reaction for 30 minutes at room temperature. After completion of the reaction, the mixture was extracted using methylene chloride, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 13.5 g (41.1%) of the product.

Synthesis of Intermediate B

Synthesis of 5,5'-dibromo-N3, N3, N3 ', N3'-tetraphenylbiphenyl-3,3'-diamine (B-1)

Add ether (150 mL) and 3,5-dibromo-N, N-diphenylaniline (13.1 g, 32.5 mmol) to a 250 mL round bottom flask, cool to -78 ° C, and then n-BuLi 2.5M in hexane (14.3 mL, 35.75 mmol) is slowly added dropwise. Stir for about 1 hour at -78 ℃, CuCl ₂ (4.8 g, 35.75 mmol) was added and stirred for 5 hours, and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was extracted using ethyl acetate water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 14 g (66.6%) of the product.

5,5'-dibromo-N3, N3, N3'-tri (naphthalen-1-yl) -N3 '-(naphthalen-2-yl)-[1,1'-biphenyl] -3,3'-diamine ( Synthesis of B-2)

Into a 500 mL round bottom flask, ether (350 mL), N, N- (3,5-dibromophenyl) -N- (naphthalen-2-yl) naphthalen-2-amine (26.2 g, 52.1 mmol) was added, and -78 ° C. After cooling with n-BuLi 2.5M in hexane (22.9 mL, 57.31 mmol) was added slowly dropwise. Stir for about 1 hour at -78 ℃, CuCl ₂ (7.7 g, 57.31 mmol) was added, stirred for 5 hours, and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was extracted using ethyl acetate water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was subjected to silicagel column to give 26.8 g (60.7%) of the product.

Synthesis of 5,5'-dibromo-N3, N3, N3 ', N3'-tetra (naphthalen-2-yl) biphenyl-3,3'-diamine (B-3)

Into a 500 mL round bottom flask, ether (300 mL), N, N- (3,5-dibromophenyl) -N- (naphthalen-2-yl) naphthalen-2-amine (26.2 g, 52.1 mmol) was added, and -78 ° C. After cooling with n-BuLi 2.5M in hexane (22.9 mL, 57.31 mmol) was added slowly dropwise. Stir for about 1 hour at -78 ℃, CuCl ₂ (7.7 g, 57.31 mmol) was added, stirred for 5 hours, and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was extracted using ethyl acetate water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 25.8 g (58.5%) of the product.

Synthesis of 5,5'-dibromo-N3, N3, N3 ', N3'-tetrap-tolylbiphenyl-3,3'-diamine (B-4)

Add ether (150 mL), 3,5-dibromo-N, N-di-p-tolylaniline (13.5 g, 31.3 mmol) to a 250 mL round bottom flask, cool to -78 ° C, and n-BuLi 2.5M in hexane (13.8 mL, 34.4 mmol) is added slowly dropwise. Stir for about 1 hour at -78 ° C, CuCl ₂ (4.6 g, 34.4 mmol) was added, stirred for 5 hours, and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was extracted using ethyl acetate water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 12.8 g (58.2%) of the product.

Synthesis of Intermediate C

Synthesis of 2,4-dibromo-9-phenyl-9H-carbazole

2,4-dibromo-9H-carbazole (5.0 g, 15.38 mmol), iodobenzene (3.14 g, 15.38 mmol), Pd ₂ (dba) ₃ (0.42 g, 0.46 mmol), P (t-Bu) in a 1100 mL round bottom flask ) ₃ (0.94 g, 4.62 mmol), NaOtBu (3.7 g, 38.45 mmol) and Toluene (50 mL) were added in this order, followed by reaction at 80 ° C for 2 hours. After completion of the reaction, the mixture was extracted using methylene chloride, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 5.2 g (84.3%) of the product.

Synthesis of 2,4-dibromo-9- (naphthalen-1-yl) -9H-carbazole

2,4-dibromo-9H-carbazole (5.0 g, 15.38 mmol), 1-iodonaphthalene (3.91 g, 15.38 mmol), Pd ₂ (dba) ₃ (0.42 g, 0.46 mmol), P (t) in a 100 mL round bottom flask -Bu) ₃ (0.94 g, 4.62 mmol), NaOtBu (3.7 g, 38.45 mmol) and Toluene (50 mL) were added in this order, followed by reaction at 80 ° C for 2 hours. After completion of the reaction, the mixture was extracted using methylene chloride, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 5.4 g (77.7%) of the product.

Synthesis of 2,4-dibromo-9- (naphthalen-2-yl) -9H-carbazole

2,4-dibromo-9H-carbazole (5.0 g, 15.38 mmol), 2-iodonaphthalene (3.91 g, 15.38 mmol), Pd ₂ (dba) ₃ (0.42 g, 0.46 mmol), P (t) in a 100 mL round bottom flask -Bu) ₃ (0.94 g, 4.62 mmol), NaOtBu (3.7 g, 38.45 mmol) and Toluene (50 mL) were added in this order, followed by reaction at 80 ° C for 2 hours. After completion of the reaction, the mixture was extracted using methylene chloride, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 5.2 g (77.3%) of the product.

Synthesis of 2,4-dibromo-9- (p-tolyl) -9H-carbazole

2,4-dibromo-9H-carbazole (5.0 g, 15.38 mmol), 1-iodo-4-methylbenzene (3.35 g, 15.38 mmol), Pd ₂ (dba) ₃ (0.42 g, 0.46 mmol) in a 100 mL round bottom flask , P (t-Bu) ₃ (0.94 g, 4.62 mmol), NaOtBu (3.7 g, 38.45 mmol) and Toluene (50 mL) were added in this order, followed by reaction at 80 ° C for 2 hours. After completion of the reaction, the mixture was extracted using methylene chloride, water and brine, and the organic layer was dried over MgSO ₄ . 4.9 g (76.7%) of the product was obtained by silicagel column of the obtained organic layer.

Synthesis of 9-([1,1'-biphenyl] -4-yl) -2,4-dibromo-9H-carbazole

2,4-dibromo-9H-carbazole (5.0 g, 15.38 mmol), 4-iodobiphenyl (4.31 g, 15.38 mmol), Pd ₂ (dba) ₃ (0.42 g, 0.46 mmol), P (t) in a 100 mL round bottom flask -Bu) ₃ (0.94 g, 4.62 mmol), NaOtBu (3.7 g, 38.45 mmol) and Toluene (50 mL) were added in this order, followed by reaction at 80 ° C for 2 hours. After completion of the reaction, the mixture was extracted using methylene chloride, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 5.1 g (69.5%) of the product.

Synthesis of 2,4-dibromo-9- (4-phenylnaphthalen-1-yl) -9H-carbazole

2,4-dibromo-9H-carbazole (5.0 g, 15.38 mmol), 1-iodo-4-phenylnaphthalene (5.1 g, 15.38 mmol), Pd ₂ (dba) ₃ (0.42 g, 0.46 mmol) in a 100 mL round bottom flask , P (t-Bu) ₃ (0.94 g, 4.62 mmol), NaOtBu (3.7 g, 38.45 mmol) and Toluene (50 mL) were added in this order, followed by reaction at 80 ° C for 2 hours. After completion of the reaction, the mixture was extracted using methylene chloride, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 5.4 g (67.6%) of the product.

Synthesis of 2,4-dibromo-9-5D-phenyl-9H-carbazole

2,4-dibromo-9H-carbazole (5.0 g, 15.38 mmol), iodobenzene-D5 (3.22 g, 15.38 mmol), Pd ₂ (dba) ₃ (0.42 g, 0.46 mmol), P (t) in a 100 mL round bottom flask -Bu) ₃ (0.94 g, 4.62 mmol), NaOtBu (3.7 g, 38.45 mmol) and Toluene (50 mL) were added in this order, followed by reaction at 80 ° C for 2 hours. After completion of the reaction, the mixture was extracted using methylene chloride, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was subjected to silicagel column to obtain 4.2 g (67.2%) of the product.

Synthesis of 9-([1,1'-5D-biphenyl] -4-yl) -2,4-dibromo-9H-carbazole

2,4-dibromo-9H-carbazole (5.0 g, 15.38 mmol), 4'-iodo-2,3,4,5,6-d5-biphenyl (4.39 g, 15.38 mmol), Pd _{2 in a} 100 mL round bottom flask (dba) ₃ (0.42 g, 0.46 mmol), P (t-Bu) ₃ (0.94 g, 4.62 mmol), NaOtBu (3.7 g, 38.45 mmol), Toluene (50 mL) in sequence and then at 80 ° C The reaction proceeds for 2 hours. After completion of the reaction, the mixture was extracted using methylene chloride, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 3.7 g (70.5%) of the product.

Synthesis of 2,4-dibromo-9- (5D-4-phenylnaphthalen-1-yl) -9H-carbazole

2,4-dibromo-9H-carbazole (5.0 g, 15.38 mmol), 1-iodo-4-phenyl-d5-naphthalene (5.16 g, 15.38 mmol), Pd ₂ (dba) ₃ (0.42 g) in a 100 mL round bottom flask , 0.46 mmol), P (t-Bu) ₃ (0.94 g, 4.62 mmol), NaOtBu (3.7 g, 38.45 mmol) and Toluene (50 mL) were added in this order, followed by reaction at 80 ° C for 2 hours. . After completion of the reaction, the mixture was extracted using methylene chloride, water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 5.3 g (64.7%) of the product.

Synthesis of Intermediate D

Synthesis of 2,2'-dibromo-9,9'-diphenyl-9H, 9'H-4,4'-bicarbazole (D-1)

Add ether (150 mL), 2,4-dibromo-9-phenyl-9H-carbazole (12 g, 29.9 mmol) to a 250 mL round bottom flask, cool to -78 ° C, and n-BuLi 2.5M in hexane (13.16 mL, 32.9 mmol) was added slowly dropwise. Stir for about 1 hour at -78 ℃, CuCl ₂ (4.4 g, 32.9 mmol) was added, and then stirred for 5 hours, and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was extracted using ethyl acetate water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was subjected to silicagel column to obtain 13.2 g (68.7%) of the product.

Synthesis of 2,2'-dibromo-9,9'-di (naphthalen-1-yl) -9H, 9'H-4,4'-bicarbazole (D-2)

250 mL round bottom flask was charged with ether (150 mL), 2,4-dibromo-9- (naphthalen-1-yl) -9H-carbazole (18 g, 39.9 mmol), cooled to -78 ° C and n-BuLi 2.5 M in hexane (17.6 mL, 43.9 mmol) was slowly added dropwise, stirred at −78 ° C. for about 1 hour, CuCl ₂ (5.9 g, 43.9 mmol) was added thereto, stirred for 5 hours, and stirred at room temperature for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate water and brine, and the organic layer was dried over MgSO _{4. The} obtained organic layer was purified by silicagel column to obtain 18.9 g (63.8%) of the product.

Synthesis of 2,2'-dibromo-9,9'-di (naphthalen-2-yl) -9H, 9'H-4,4'-bicarbazole (D-3)

250 mL round bottom flask was charged with ether (150 mL), 2,4-dibromo-9- (naphthalen-2-yl) -9H-carbazole (18 g, 39.9 mmol), cooled to -78 ° C and n-BuLi 2.5 M in hexane (17.6 mL, 43.9 mmol) was slowly added dropwise, stirred at −78 ° C. for about 1 hour, CuCl ₂ (5.9 g, 43.9 mmol) was added thereto, stirred for 5 hours, and stirred at room temperature for 12 hours. After completion of the reaction, the mixture was extracted using ethyl acetate water and brine, and the organic layer was dried over MgSO _{4. The} obtained organic layer was silicagel column, obtaining 18.4 g (62.1%) of the product.

Synthesis of 2,2'-dibromo-9,9'-di-p-tolyl-9H, 9'H-4,4'-bicarbazole (D-4)

250 mL round bottom flask was charged with ether (150 mL), 2,4-dibromo-9- (p-tolyl) -9H-carbazole (12 g, 29.9 mmol), cooled to -78 ° C and n-BuLi 2.5M in hexane (13.16 mL, 32.9 mmol) is slowly added dropwise. Stir for about 1 hour at -78 ℃, CuCl ₂ (4.4 g, 32.9 mmol) was added, and then stirred for 5 hours, and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was extracted using ethyl acetate water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 12.9 g (64.3%) of the product.

Synthesis of 9,9'-di (biphenyl-4-yl) -2,2'-dibromo-9H, 9'H-4,4'-bicarbazole (D-5)

250 mL round bottom flask with ether (150 mL), 9,9'-di (biphenyl-4-yl) -2,2'-dibromo-9H, 9'H-4,4'-bicarbazole (15 g, 31.43 mmol ), Cooled to -78 ° C and slowly added dropwise n-BuLi 2.5M in hexane (13.8 mL, 34.58 mmol). Stir at -78 ° C for about 1 hour, add CuCl ₂ (4.65 g, 34.58 mmol), then stir for 5 hours, and stir at room temperature for 12 hours. After the reaction was completed, the mixture was extracted using ethyl acetate water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 15.7 g (62.9%) of the product.

Synthesis of 2,2'-dibromo-9,9'-bis (4-phenylnaphthalen-1-yl) -9H, 9'H-4,4'-bicarbazole (D-6)

Into a 250 mL round bottom flask, ether (150 mL), 2,4-dibromo-9- (4-phenylnaphthalen-1-yl) -9H-carbazole (15 g, 28.5 mmol) was added thereto, cooled to -78 ° C and then n -BuLi 2.5M in hexane (12.5 mL, 31.3 mmol) is slowly added dropwise. Stir for about 1 hour at -78 ℃, CuCl ₂ (4.2 g, 31.3 mmol) was added, stirred for 5 hours, and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was extracted using ethyl acetate water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 15.2 g (59.6%) of the product.

Synthesis of 2,2'-dibromo-9,9'-D5-diphenyl-9H, 9'H-4,4'-bicarbazole (D-7)

In a 250 mL round bottom flask, ether (150 mL), 2,4-dibromo-9-D5-phenyl-9H-carbazole (15 g, 36.93 mmol) were added, cooled to -78 ° C and n-BuLi 2.5M in hexane (16.24 mL, 40.6 mmol) is added slowly dropwise. Stir for about 1 hour at -78 ℃, CuCl ₂ (5.5 g, 40.6 mmol) was added, stirred for 5 hours, and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was extracted using ethyl acetate water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 14.9 g (61.7%) of the product.

Synthesis of 9,9'-di (D5-biphenyl-4-yl) -2,2'-dibromo-9H, 9'H-4,4'-bicarbazole (D-8)

Into a 250 mL round bottom flask, ether (150 mL), 2,4-dibromo-9- (4-D5-phenylnaphthalen-1-yl) -9H-carbazole (15 g, 28.2 mmol) were added and cooled to -78 ° C. Then n-BuLi 2.5M in hexane (12.4 mL, 31 mmol) is slowly added dropwise. Stir for about 1 hour at -78 ℃, CuCl ₂ (4.2 g, 31 mmol) was added, stirred for 5 hours, and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was extracted using ethyl acetate water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 15.4 g (60.4%) of the product.

Synthesis of 2,2'-dibromo-9,9'-bis (4-D5-phenylnaphthalen-1-yl) -9H, 9'H-4,4'-bicarbazole (D-9)

In a 250 mL round bottom flask, ether (150 mL), 2,4-dibromo-9-D5-phenyl-9H-carbazole (15 g, 31.1 mmol) were added, cooled to -78 ° C and n-BuLi 2.5M in hexane (13.7 mL, 34.2 mmol) is added slowly dropwise. Stir for about 1 hour at -78 ℃, add CuCl ₂ (4.6 g, 34.2 mmol), and then stirred for 5 hours, and stirred at room temperature for 12 hours. After the reaction was completed, the mixture was extracted using ethyl acetate water and brine, and the organic layer was dried over MgSO ₄ . The obtained organic layer was silicagel column to obtain 14.7 g (58.7%) of the product.

Mass analysis results for B-1 to B-4 of the intermediates obtained through the synthesis are shown in Table 1 below, and D-1 to D-9 are shown in Table 2 below.

Example of final compound synthesis:

In a round bottom flask, intermediate (1 equivalent), sub material (2.5 equivalents), Pd (PPh ₃ ) ₄ (0.06 equivalents), NaOH (6 equivalents), THF (4 mL / 1 mmol), and water (2 / mmol) After the addition, the mixture was heated to reflux at 80 ° C. After completion of the reaction, dilute with distilled water at room temperature, extract with ethyl acetate water and brine, and dry the organic layer with MgSO ₄ . The obtained organic layer was concentrated and the resulting chemical was silicagel column and recrystallized to obtain a product, and the product was confirmed by FD-MS as shown in the table below.

Mass spectrometry of the final compounds obtained through the synthesis is shown in Table 3 below.

On the other hand, each of the substituents of the compounds represented by Formulas 1 to 4 have a broad relationship, exemplarily described the synthesis examples of the representative compounds, but also compounds represented by Formulas 1 to 4 that are not illustratively described as a synthesis example It can form part of the specification.

Moreover, the compound which has the intrinsic property of the introduced substituent can be synthesize | combined by introducing various substituents into the core structure of the above structure. For example, by introducing substituents used in the hole injection layer material, the hole transport layer material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic electric device, including the organic light emitting device to satisfy the conditions required for each organic material layer Materials can be prepared.

The compound according to the present invention can be used for various purposes in the organic electroluminescent device according to the type and nature of the substituent.

The compounds of the present invention can act as various layers other than the host of the phosphorescent or fluorescent light emitting layer because they are freely controlled by the core and the substituents.

The organic electric device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electric device except for forming one or more organic material layers using the above-described compounds.

When the compounds of the present invention are used in other organic material layers of the organic electroluminescent device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.

Meanwhile, the compound of the present invention can be used in a soluble process. In other words, the compound may form an organic material layer of the organic electronic device, which will be described later, by a solution process. In other words, when the compound is used as an organic material layer, the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.

Organic electroluminescent devices in which the compounds of the present invention may be used include, for example, organic electroluminescent devices (OLEDs), organic solar cells, organic photoconductor (OPC) drums, organic transistors (organic TFTs), and the like.

As an example of the organic electroluminescent device to which the compounds of the present invention can be applied, an organic electroluminescent device (OLED) will be described. However, the present invention is not limited thereto, and the above-described compounds may be applied to various organic electroluminescent devices.

Another embodiment of the present invention is an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer comprises an organic electroluminescent device comprising the compounds of the present invention to provide.

1 to 6 show examples of the organic electroluminescent device to which the compound of the present invention can be applied.

The organic electroluminescent device according to another embodiment of the present invention, except that at least one layer of the organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer to include the compound of the present invention. Can be prepared with a structure known in the art using conventional manufacturing methods and materials in the art.

The structure of the organic electroluminescent device according to another embodiment of the present invention is illustrated in Figures 1 to 6, but is not limited to these structures. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode.

Although not shown, the organic electroluminescent device further includes a hole blocking layer (HBL) that prevents the movement of holes, an electron blocking layer (EBL) that prevents the movement of electrons, a light emitting auxiliary layer that helps or assists light emission, and a protective layer. It may be located. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.

In this case, the compound of the present invention may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer.

Specifically, the compound of the present invention is used in place of or in combination with one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer and a protective layer It may be used to form. Of course, the organic layer may be used not only in one layer but also in two or more layers.

In particular, it can be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a luminescent material and a passivation (kepping) material according to the compound of the present invention, in particular a host or in a luminescent material and host / dopant alone Can be used as a dopant, can be used as a hole injection, a hole transport layer.

For example, the organic electroluminescent device according to another embodiment of the present invention is a metal having metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. Can be prepared.

In addition to the above method, an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure.

In addition, the organic layer may be formed using a variety of polymer materials, but not by a deposition process or a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made with a small number of layers.

The organic electroluminescent device according to another embodiment of the present invention may be used in a solution process such as spin coating or ink jet process.

The substrate is a support of the organic electroluminescent device, and a silicon wafer, a quartz or glass plate, a metal plate, a plastic film or sheet, or the like can be used.

An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. The positive electrode material may be a material having a large work function to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SnO 2: Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

The hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.

The hole injection material is a material that can be injected well from the anode at a low voltage, the highest occupied molecular orbital (HOMO) of the hole injection material may be between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, applications for vehicle body display require heat resistance to the device, and may be a material having a glass transition temperature (Tg) of 70 ° C. or higher.

Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compound, a silicon-based arylamine compound, and the like.

The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and may be a material having good quantum efficiency for fluorescence or phosphorescence.

Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenollithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 '[ (1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H Small amounts of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) can be used.

When forming a light emitting layer using a process such as inkjet printing, roll coating, or spin coating, a polymer of polyphenylene vinylene (PPV) -based polymer or poly fluorene may be used for the organic light emitting layer. .

The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons.

Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.

The electron injection layer is stacked on the electron transport layer. The electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular weight material containing boron compounds and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ~ 300Å.

The cathode is positioned on the electron injection layer. This cathode serves to inject electrons. The material used as the cathode may use the material used for the anode, and may be a metal having a low work function for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.

As described above, according to the compound of the present invention, it can be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material suitable for fluorescence and phosphorescent devices of all colors such as red, green, blue, and white, It can be used as a host or dopant material of various colors.

The organic electroluminescent device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.

Meanwhile, the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.

Manufacturing Evaluation of Organic Electrical Device

Several compounds obtained through the synthesis were used as hole transport layers, respectively, to fabricate an organic light emitting device according to a conventional method. First, a 2-TNATA film was vacuum-deposited on the ITO layer (anode) formed on the organic substrate as a hole injection layer to form a thickness of 10 nm. Subsequently, the inventive compound and the comparative example were vacuum deposited to a thickness of 20 nm with a hole transport layer. Vacuum deposition was carried out for comparative experiments. Subsequently, BD-052X (Idemitsu Co., Ltd.) was used as a light emitting dopant and the host material was 9, 10-di- (naphthalene-2-anthracene) = AND], and the doping concentration was fixed at 4% to conduct a comparative experiment. It was. Subsequently, tris (8-quinolinol) aluminum was formed into a film with a thickness of 40 nm with an electron injection layer. Subsequently, LiF as an alkyl halide metal was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to use the Al / LiF as a cathode to prepare an organic light emitting device. The electroluminescent (EL) characteristics were measured by the PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared as described above and the comparative examples. The T90 life was measured using a life measurement instrument manufactured by McScience.

For comparison, an organic electroluminescent device having the same structure as that of the test example was prepared by using the well-known compounds of α-NPD (Comparative Example-1), Comparative Example-2 and Comparative Example-3 as the hole transporting layer instead of the compound of the present invention. Produced.

Comparing the above-described compounds and the performance (driving voltage, current density, brightness, efficiency, life, etc.) of the organic light emitting device manufactured from the hole transport layer material Comparative Examples-1 to Comparative Example-3 is shown in Table 4 below. .

As can be seen through Table 4, in the case of the present invention, compared to the comparative example, most of the driving voltage showed the characteristic of falling up to 1.5V or more, and not only the drop of the driving voltage but also the characteristic of the long life up to 100% or more. Indicated.

That is, the organic light emitting device using the organic light emitting device material of the present invention can be used as a light emitting host, a hole transporting material can significantly improve the low driving voltage, color purity, high luminous efficiency and lifetime.

When the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.

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

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

Claims (9)

A first electrode;
At least one organic material layer containing a compound represented by the formula (1); And
An organic electric device comprising a second electrode; is stacked sequentially.

In Chemical Formula 1,
(1) R ₁ and R ₂ are hydrogen ; Deuterium ; Tritium ; Halogen group ; Nitro group; Nitrile group; Amide group; Silane group; A condensed ring group of an aromatic ring of C ₆ ~ C ₆₀ and an aliphatic ring of C ₄ ~ C ₆₀ ;
Hydrogen, deuterium, halogen group, C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkylamine group, C ₁ ~ C ₆₀ arylamine group, C ₁ ~ C ₆₀ alkylthiophene group, C ₆ ~ C ₆₀ aryl thiophene group, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ of the aryl A group, a C ₆ to C ₆₀ aryl group substituted with deuterium, a C ₈ to C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and C ₆ ~ C ₆₀ aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a substituted or unsubstituted C ₂ ~ C ₆₀ heterocyclic group ;
C ₁ ~ alkenyl group of the C ₂₀ alkyl group, C ₂ ~ C ₂₀ of, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ aryl group of C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with deuterium, C ₇ C ₁ -C ₅₀ unsubstituted or substituted with one or more substituents selected from the group consisting of -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group and acetylene group Alkyl group ;
Hydrogen, deuterium, halogen, CN, NO ₂ , C ₁ -C ₆₀ alkyl group, C ₁ -C ₆₀ alkoxy group, C ₁ -C ₆₀ alkylamine group, C ₁ -C ₆₀ arylamine group, C ₁ C ₆₀ alkylthiophene group, C ₂ -C ₆₀ alkenyl group, C ₂ -C ₆₀ alkynyl group, C ₃ -C ₆₀ cycloalkyl group, C ₆ -C ₆₀ aryl group, deuterium substituted C _In the group consisting of ₆ to C ₆₀ aryl groups, substituted or unsubstituted silane groups, substituted or unsubstituted boron groups, substituted or unsubstituted germanium groups, and substituted or unsubstituted C ₂ to C ₆₀ heterocyclic groups C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with one or more selected groups and includes heteroatoms of at least one of O, N, and S as hetero atoms ; And
An amine group unsubstituted or substituted with one or more groups selected from the group consisting of C ₁ to C ₆₀ alkyl groups, C ₂ to C ₆₀ alkenyl groups, C ₆ to C ₆₀ aryl groups, and C ₈ to C ₆₀ aryl alkenyl groups Selected from the group consisting of;
(2) Ar ₁ to Ar ₈ are the same or different, respectively
Hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ aryl thiophene group, a C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C of ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, a heavy hydrogen of the Substituted with one or more substituents selected from the group consisting of C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron group, germanium group, C ₂ ~ C ₂₀ heterocyclic group Or an unsubstituted C ₆ -C ₆₀ aryl group ;
Hydrogen, deuterium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₈ ~ C ₂₀ arylamine group, C ₆ ~ C ₆₀ aryl A C ₆ to C ₂₀ aryl group, a C ₇ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, a C ₂ to C ₂₀ heterocyclic group, a nitrile group and an acetylene group A C ₂ to C ₆₀ heterocyclic group which is unsubstituted or substituted with one or more substituents in the group and includes at least one heteroatom of O, N, or S;
Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₃₀ cycloalkyl group, C ₁ ~ C ₃₀ of unsubstituted or substituted with one or more substituents selected from the group consisting of C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₂ ~ C ₆₀ heterocyclic group Alkoxy group ;
Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₃₀ cycloalkyl group, a C ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₆₀ substituted or unsubstituted with one or more substituents selected from the group yirwojin group heterocyclic C ₆ ~ C ₃₀ substituted by deuterium Aryloxy group ;
Halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ cycloalkyl group, C ₆ ~ C of a ₆₀ aryl group, C ₂ ~ C ₆₀ with one or more substituents selected from the group consisting of a heterocyclic-substituted or unsubstituted C ₆ ~ C ₆₀ arylamine group; And
C ₁ ~ alkenyl group of the C ₂₀ alkyl group, C ₂ ~ C ₂₀ of, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ aryl group of C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with deuterium, C ₇ C ₁ -C ₅₀ alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group ; Is selected from the group consisting of
(3) a and b are integers of 1-4, and when a and b are two or more, some R <_1> , R <_2> may be same or different. The method of claim 1,
Formula (1) is an organic electric device, characterized in that one of the following compounds.

The method of claim 1,
An organic electric device, characterized in that to form the compound into the organic material layer by a solution process (soluble process) The method of claim 1,
The organic material layer is at least one of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an organic electric device. The method of claim 4, wherein
And the compound is used as a host material of the light emitting layer. The method of claim 3,
The organic electroluminescent element is an organic electroluminescent element (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT) characterized in that one of the organic electroluminescent element. An electronic device comprising the organic electronic device of claim 6. A compound represented by the following formula (1).

In Chemical Formula 1,
(1) R ₁ and R ₂ are hydrogen ; Deuterium ; Tritium ; Halogen group ; Nitro group; Nitrile group; Amide group; Silane group; A condensed ring group of an aromatic ring of C ₆ ~ C ₆₀ and an aliphatic ring of C ₄ ~ C ₆₀ ;
Hydrogen, deuterium, halogen group, C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkylamine group, C ₁ ~ C ₆₀ arylamine group, C ₁ ~ C ₆₀ alkylthiophene group, C ₆ ~ C ₆₀ aryl thiophene group, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ of the aryl A group, a C ₆ to C ₆₀ aryl group substituted with deuterium, a C ₈ to C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and C ₆ ~ C ₆₀ aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a substituted or unsubstituted C ₂ ~ C ₆₀ heterocyclic group ;
C ₁ ~ alkenyl group of the C ₂₀ alkyl group, C ₂ ~ C ₂₀ of, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ aryl group of C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with deuterium, C ₇ C ₁ -C ₅₀ unsubstituted or substituted with one or more substituents selected from the group consisting of -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group and acetylene group Alkyl group ;
Hydrogen, deuterium, halogen, CN, NO ₂ , C ₁ -C ₆₀ alkyl group, C ₁ -C ₆₀ alkoxy group, C ₁ -C ₆₀ alkylamine group, C ₁ -C ₆₀ arylamine group, C ₁ C ₆₀ alkylthiophene group, C ₂ -C ₆₀ alkenyl group, C ₂ -C ₆₀ alkynyl group, C ₃ -C ₆₀ cycloalkyl group, C ₆ -C ₆₀ aryl group, deuterium substituted C _In the group consisting of ₆ to C ₆₀ aryl groups, substituted or unsubstituted silane groups, substituted or unsubstituted boron groups, substituted or unsubstituted germanium groups, and substituted or unsubstituted C ₂ to C ₆₀ heterocyclic groups C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with one or more selected groups and includes heteroatoms of at least one of O, N, and S as hetero atoms ; And
An amine group unsubstituted or substituted with one or more groups selected from the group consisting of C ₁ to C ₆₀ alkyl groups, C ₂ to C ₆₀ alkenyl groups, C ₆ to C ₆₀ aryl groups, and C ₈ to C ₆₀ aryl alkenyl groups Selected from the group consisting of;
(2) Ar ₁ to Ar ₈ are the same or different, respectively
Hydrogen, deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ aryl thiophene group, a C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C of ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, a heavy hydrogen of the Substituted with one or more substituents selected from the group consisting of C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron group, germanium group, C ₂ ~ C ₂₀ heterocyclic group Or an unsubstituted C ₆ -C ₆₀ aryl group ;
Hydrogen, deuterium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₈ ~ C ₂₀ arylamine group, C ₆ ~ C ₆₀ aryl A C ₆ to C ₂₀ aryl group, a C ₇ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, a C ₂ to C ₂₀ heterocyclic group, a nitrile group and an acetylene group A C ₂ to C ₆₀ heterocyclic group which is unsubstituted or substituted with one or more substituents in the group and includes at least one heteroatom of O, N, or S;
Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₃₀ cycloalkyl group, C ₁ ~ C ₃₀ of unsubstituted or substituted with one or more substituents selected from the group consisting of C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₂ ~ C ₆₀ heterocyclic group Alkoxy group ;
Hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₃₀ cycloalkyl group, a C ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₆₀ substituted or unsubstituted with one or more substituents selected from the group yirwojin group heterocyclic C ₆ ~ C ₃₀ substituted by deuterium Aryloxy group ;
Halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ cycloalkyl group, C ₆ ~ C of a ₆₀ aryl group, C ₂ ~ C ₆₀ with one or more substituents selected from the group consisting of a heterocyclic-substituted or unsubstituted C ₆ ~ C ₆₀ arylamine group; And
C ₁ ~ alkenyl group of the C ₂₀ alkyl group, C ₂ ~ C ₂₀ of, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ aryl group of C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with deuterium, C ₇ C ₁ -C ₅₀ alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group ; Is selected from the group consisting of
(3) a and b are integers of 1-4, and when a and b are two or more, some R <_1> , R <_2> may be same or different. The method of claim 8,
Formula (1) is a compound, characterized in that one of the following compounds.

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