KR20130135181A - New compounds and organic light emitting device using the same - Google Patents

Abstract

The present invention provides a new compound capable of remarkably improving the lifetime, the efficiency, the electrochemical stability, and the thermal stability of an organic light emitting element and an organic light emitting device in which the new compound is contained in the organic compound. The compound of the present invention can be utilized for the organic light emitting element as an organic layer material, especially as a luminous material, and as an electron carrying material. When the compound is utilized for the organic light emitting element, the compound reduces a driving voltage of the element, improves optical efficiency, and extends the lifetime of the element by the thermal stability of the compound.

Description

New organic light emitting device material and organic light emitting device using the same {NEW COMPOUNDS AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME}

This application claims the benefit of the filing date of Korean Patent Application No. 10-2012-0058937 filed with the Korea Intellectual Property Office on May 31, 2012, the entire contents of which are incorporated herein.

The present invention relates to an organic light emitting device in which a novel compound is contained in the organic compound layer that can greatly improve the lifetime, efficiency, electrochemical stability, and thermal stability of the organic light emitting device.

The organic light emission phenomenon is one example in which current is converted into visible light by an internal process of a specific organic molecule. The principle of organic luminescence phenomenon is as follows. When an organic layer is positioned between an anode and a cathode, when a voltage is applied between the two electrodes, electrons and holes are injected into the organic layer from the cathode and the anode, respectively. Electrons and holes injected into the organic material layer recombine to form an exciton, and the exciton falls back to the ground state to emit light. An organic light emitting device using such a principle may be generally composed of an organic material layer including a cathode, an anode, and an organic material layer disposed therebetween, for example, a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer.

As a material used in an organic light emitting device, a pure organic material or a complex in which an organic material and a metal form a complex is mostly used. Depending on the application, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, . As the hole injecting material and the hole transporting material, an organic material having a p-type property, that is, an organic material that is easily oxidized and electrochemically stable at the time of oxidation is mainly used. On the other hand, as an electron injecting material or an electron transporting material, an organic material having an n-type property, that is, an organic material that is easily reduced and electrochemically stable when being reduced is mainly used. As the light emitting layer material, a material having both a p-type property and an n-type property, that is, a material having both a stable form in oxidation and in a reduced state is preferable, and a material having a high luminous efficiency for converting an exciton into light desirable.

In addition to the above, it is preferable that the material used in the organic light emitting device further has the following properties.

First, the material used in the organic light emitting device is preferably excellent in thermal stability. This is because joule heating occurs due to the movement of charges in the organic light emitting device. Currently, NPB, which is mainly used as a hole transporting material, has a glass transition temperature of 100 ° C. or less, and thus, it is difficult to use in an organic light emitting device requiring a high current.

Secondly, in order to obtain a highly efficient organic light emitting device capable of driving at a low voltage, holes or electrons injected into the organic light emitting element should be smoothly transferred to the light emitting layer, and injected holes and electrons should not escape from the light emitting layer. For this purpose, the material used in the organic light emitting device should have an appropriate band gap and a HOMO or LUMO energy level. Currently, PEDOT: PSS used as a hole transporting material in an organic light emitting device manufactured by a solution coating method has a low LUMO energy level compared to the LUMO energy level of an organic material used as a light emitting layer material. There is a difficulty.

In addition, materials used in organic light emitting devices should have excellent chemical stability, charge mobility, and interface characteristics with electrodes or adjacent layers. That is, the material used in the organic light emitting device should have little deformation of the material due to moisture or oxygen. In addition, by having appropriate hole or electron mobility, it is necessary to maximize the formation of excitons by balancing the density of holes and electrons in the light emitting layer of the organic light emitting device. And, for the stability of the device, the interface with the electrode including the metal or the metal oxide should be good.

Accordingly, there is a need in the art to develop organic materials having the above-mentioned requirements.

Republic of Korea Patent Publication No. 10-2003-0067773

Compounds having a chemical structure capable of satisfying the conditions required for materials usable in the organic light emitting device, such as appropriate energy level, electrochemical stability and thermal stability, and can play various roles required in the organic light emitting device according to substituents. There is a need for a study on an organic light emitting device comprising a.

The present invention provides novel compounds.

In addition, the present invention is an organic light emitting device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, at least one of the organic layer comprises the compound. An organic light emitting device is provided.

The compound of the present invention can be used as an organic layer material, in particular a light emitting material, an electron transporting material in the organic light emitting device, when the compound is used in the organic light emitting device to lower the driving voltage of the device, improve the light efficiency, and thermal stability of the compound As a result, lifespan characteristics of the device can be improved.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig.
2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is.

Hereinafter, the present invention will be described in more detail.

The novel compounds according to the present invention can be represented by the following formula (1).

[Formula 1]

In Formula 1,

At least one of R1 to R4 is F or CN, and the rest are each independently hydrogen, deuterium, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl having 6 to 20 carbon atoms. Group, and a heteroaryl group having 5 to 20 carbon atoms,

R5, R7, R8, R9, R10 and R12 are hydrogen,

R6 and R11 are the same as each other and are selected from the group consisting of an aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms.

In the compound according to the present invention, the substituents of the above formula (1) will be described in more detail as follows.

The alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 12. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl.

The alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 12. Specific examples thereof include, but are not limited to, an alkenyl group having an aryl group such as a stilbenyl group or a styrenyl group.

The alkoxy group preferably has 1 to 12 carbon atoms, more specifically, methoxy, ethoxy, isopropyloxy, and the like, but is not limited thereto.

The aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 40. Examples of the monocyclic aryl group include phenyl group, biphenyl group, terphenyl group, stilbene, and the like. Examples of the polycyclic aryl group include naphthyl group, anthracenyl group, phenanthrene group, pyrenyl group, perrylenyl group, and cryo. Although a cenyl group, a fluorene group, etc. are mentioned, It is not limited to this.

The heteroaryl group is a cyclic group containing hetero atoms such as O, N or S, and the number of carbon atoms is not particularly limited, but is preferably 3 to 30 carbon atoms. Examples of the heteroaryl group include a carbazole group, a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a pyrazine group, a quinolinyl group, an isoquinoline group And, there is an acrydyl group and the like, compounds such as the following structural formula is preferable, but is not limited thereto.

The term "substituted or unsubstituted" in the present specification means a group selected from the group consisting of deuterium, halogen, alkyl, alkenyl, alkoxy, silyl, arylalkenyl, aryl, Substituted or unsubstituted fluorenyl group and a nitrile group, or has no substituent group.

Substituents which may be further substituted with R1 to R12 of Chemical Formula 1 may include a halogen group, an alkyl group, an alkenyl group, an alkoxy group, a silyl group, an aryl alkenyl group, an aryl group, a heteroaryl group, a carbazole group, an arylamine group, and an aryl group. Substituted or unsubstituted fluorenyl group, nitrile group and the like can be mentioned, but is not limited thereto.

At least one of R1 to R4 of Formula 1 may be F or CN, and the rest may be hydrogen.

In addition, at least two of R1 to R4 of Formula 1 may be F or CN, and the rest may be hydrogen.

In the compound according to the present invention, Chemical Formula 1 may be represented by any one of the following Chemical Formulas, but is not limited thereto.

The conjugation length of the compound and the energy band gap are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy bandgap. Since the core of the compound of Formula 1 contains limited conjugation, it has a large energy bandgap.

In the present invention, a compound having various energy bandgap can be synthesized by introducing various substituents into R1 to R12 of the core structure having a large energy bandgap as described above. In general, it is easy to control the energy band gap by introducing a substituent to the core structure having a large energy band gap, but when the core structure has a small energy band gap, it is difficult to control the energy band gap by introducing a substituent. In addition, in the present invention, the HOMO and LUMO energy levels of the compound may be adjusted by introducing various substituents at the R1 to R12 positions of the core structure as described above.

In addition, by introducing various substituents into the structure of the formula (1) it is possible to synthesize a compound having the intrinsic properties of the introduced substituents. For example, by incorporating a substituent mainly used in the hole injection layer material, the hole transport material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic light emitting device into the core structure, it is possible to synthesize a material satisfying the requirements of each organic material layer. Can be.

In addition, by introducing a variety of substituents in the structure of the formula (1) it is possible to finely control the energy bandgap, on the other hand to improve the characteristics at the interface between the organic material and to vary the use of the material.

On the other hand, the compound has a high glass transition temperature (Tg) is excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.

The compound of formula 1 according to the present invention may be prepared by a multistage chemical reaction. Some intermediate compounds may be prepared first, and compounds of formula 1 may be prepared from the intermediate compounds. More specifically, the compound of Formula 1 according to the present invention may be prepared by the same method as in Scheme 1, but is not limited thereto.

[Reaction Scheme 1]

In Scheme 1, X is a halogen group such as bromine.

In addition, the organic light emitting device according to the present invention is an organic light emitting device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, at least one of the organic layer It is characterized by including the compound.

The organic light emitting device of the present invention may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that at least one organic material layer is formed using the above-described compound.

The compound may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers.

Therefore, in the organic light emitting device of the present invention, the organic material layer may include one or more layers of a hole injection layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes, wherein at least one layer of the layers may contain the compound. It may include.

In addition, the organic material layer may include a light emitting layer, and the light emitting layer may include the compound.

In addition, the organic material layer may include one or more layers of an electron transport layer, an electron injection layer, and a layer for simultaneously transporting and transporting electrons, and one or more of the layers may include the compound.

In the organic layer of the multilayer structure, the compound may be included in a light emitting layer, a layer for simultaneously injecting / holes transporting and emitting light, a layer for simultaneously transporting holes and emitting light, or a layer for simultaneously transporting electrons and emitting light.

In the organic light emitting device according to the present invention, the compound represented by Chemical Formula 1 is particularly preferably included in the electron transport layer.

The structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.

1 illustrates the structure of an organic light emitting device in which an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated on a substrate 1. In FIG. In such a structure, the compound may be included in the light emitting layer (3).

2 shows an organic light emitting device in which an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 are sequentially laminated on a substrate 1 Structure is illustrated. In such a structure, the compound may be included in the hole injection layer 5, the hole transport layer 6, the light emitting layer 7, or the electron transport layer 8.

For example, the organic light emitting device according to the present invention may be formed by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form a metal oxide or a metal oxide having conductivity on the substrate, To form an anode, an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, and an electron transporting layer is formed on the anode, and a material which can be used as a cathode is deposited thereon. In addition to such a method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. The organic material layer may be formed using a variety of polymeric materials by a method such as a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, Layer.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode 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), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methyl compounds), poly [3,4- (ethylene-1,2-dioxy) compounds] (PEDT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene , An anthraquinone, and a conductive polymer of polyaniline and a poly-compound, but the present invention is not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injecting layer to the light emitting layer and having high mobility to holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is suitable for electrons, is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

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

The compound according to the present invention may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors and the like.

The present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.

< Example >

< Synthetic example  1> Preparation of the substance represented by Chemical Formula 1-1

1) Preparation of Compound 1

1-dibromo-4-fluorobenzene (50 g, 196.9 mmol) and 3-hydroxyphenyl boronic acid (CAS) in a 1 L round bottom flask No. 87199-18-6, 59.7 g, 432.8 mmol), potassium phosphate (125.4 g, 590.8 mmol), bis (dibenzylideneacetone) palladium (3.4 g, 5.9 mmol), tricyclohexylphosphine (3.3 g, 11.8mmol), tetrahydrofuran 500ml, water 250ml was added and refluxed with stirring for 8 hours. After cooling to room temperature, the organic layer was separated. Distillation under reduced pressure and concentration and column purification yielded Compound 1 (32.3 g, 115.2 mmol) in a yield of 58.5%.

MS: [M + H] ⁺ = 281

2) Preparation of Compound 2

Compound 1 (30 g, 107 mmol) was dissolved in 600 ml of dichloromethane in a 1 L round bottom flask. Ferric chloride (20.8 g, 128.2 mmol) was added slowly and stirred for 3 hours. 200 ml of water was added thereto, stirred for 30 minutes, and the organic layer was separated. Distillation under reduced pressure and concentration and column purification yielded Compound 2 (20.8 g, 74.7 mmol) in a yield of 69.9%.

MS: [M] ⁺ = 278

3) Preparation of Compound 3

Compound 2 (20 g, 71.9 mmol) was dissolved in 300 ml of pyridine and cooled to 0 ° C. in a 500 ml round bottom flask. Trifluoromethanesulfonic anhydride (42.6g, 151mmol) was slowly added for 40 minutes and stirred for 3 hours. After the reaction was completed, 100ml of water was added thereto, stirred for 30 minutes, and the organic layer was separated. Distillation under reduced pressure, concentration and column purification gave compound 3 (27.2 g, 50.1 mmol) in 69.7% yield.

MS: [M + H] ⁺ = 543

4) Preparation of Chemical Formula 1-1

In a 250 ml round bottom flask, Compound 3 (10 g, 18.4 mmol), phenanthrene-9-boronic acid (CAS No. 68572-87-2, 9 g, 40.5 mmol), potassium carbonate (15.3 g) , 110.4mmol), tetrakis (triphenylphosphine) palladium (0.85g, 0.74mmol), tetrahydrofuran 100ml, water 40ml was added to reflux with stirring for 7 hours. After cooling to room temperature, the organic layer was separated. Distillation under reduced pressure, concentration and column purification yielded Chemical Formula 1-1 (7.8 g, 13 mmol) in a yield of 70.7%.

MS: [M + H] ⁺ = 599

< Synthetic example  2> Preparation of substance represented by Chemical Formula 1-6

[Chemical Formula 1-6]

Compound 3 (8 g, 14.7 mmol) and 3,5-diphenylphenyl boronic acid (3,5-diphenylphenyl boronic acid, CAS No. 128388-54-5, 8.8 g, 32.1 of Synthesis Example 1) in a 250 ml round bottom flask mmol), potassium carbonate (12.2 g, 88.2 mmol), tetrakis (triphenylphosphine) palladium (0.68 g, 0.59 mmol), 100 ml of tetrahydrofuran, and 30 ml of water were added and refluxed with stirring for 8 hours. After cooling to room temperature, the organic layer was separated. Distillation under reduced pressure and concentration and column purification yielded Chemical Formula 1-6 (7.5 g, 10.7 mmol) in a yield of 72.8%.

MS: [M + H] ⁺ = 703

< Synthetic example  3> Preparation of the substance represented by Chemical Formula 1-7

1) Preparation of Compound 1

In a 250 ml round bottom flask, Compound 3 (11.4 g, 21 mmol), bis (pinacolato) diboron (10.7 g, 42 mmol), potassium acetate (10.3 g, 105 mmol), and dioxane 150 ml were added to a 250 ml round bottom flask, followed by heating. It was. At reflux, bis (dibenzylideneacetone) palladium (0.48g, 0.84mmol) and tricyclohexylphosphine (0.47g, 1.68mmol) were added and stirred for 6 hours. After cooling to room temperature, 50ml of water was added and stirred for 30 minutes. The organic layer was separated and dried over anhydrous magnesium sulfate. Distillation under reduced pressure and concentration and column purification yielded Compound 1 (6.9 g, 13.8 mmol) in a yield of 65.7%.

MS: [M + H] ⁺ = 499

2) Preparation of Chemical Formula 1-7

In a 250 ml round bottom flask, Compound 1 (6.5 g, 13 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5 -triazine, CAS No. 3842-55-5, 7g, 26.1mmol), potassium carbonate (9g, 65.1mmol), tetrakis (triphenylphosphine) palladium (0.6g, 0.52mmol), tetrahydrofuran 100ml, water 30 ml was added and refluxed with stirring for 8 hours. After cooling to room temperature, the resulting solid was filtered and washed sequentially with 300 ml of water and 500 ml of tetrahydrofuran. The filtered solid was recrystallized with chloroform and ethanol to give the formula 1-7 (6.8g, 9.6mmol) in 73.8% yield.

MS: [M + H] ⁺ = 709

< Synthetic example  4> Preparation of substance represented by Chemical Formula 1-23

1) Preparation of Compound 1

In a 1 L round bottom flask, 1,2-dibromo-4,5-difluorobenzene (1,2-dibromo-4,5-difluorobenzene, 50 g, 183.9 mmol) and 3-hydroxyphenyl boronic acid (3- hydroxyphenyl boronic acid, CAS No. 87199-18-6, 50.7g, 367.8mmol), potassium phosphate (117.1g, 551.7mmol), bis (dibenzylideneacetone) palladium (3.2g, 5.5mmol), tricyclohexylphosphate Fin (3.1g, 11mmol), tetrahydrofuran 500ml, 250ml of water was added to reflux with stirring for 8 hours. After cooling to room temperature, the organic layer was separated. Distillation under reduced pressure, concentration and column purification yielded Compound 1 (34.1 g, 114.3 mmol) in a yield of 62.2%.

MS: [M + H] &lt; ⁺ &gt; = 299

2) Preparation of Compound 2

Compound 1 (33 g, 110.6 mmol) was dissolved in 600 ml of dichloromethane in a 1 L round bottom flask. Ferric chloride (20 g, 123.3 mmol) was slowly added thereto and stirred for 3 hours. 200 ml of water was added thereto, stirred for 30 minutes, and the organic layer was separated. Distillation under reduced pressure and concentration were carried out and the column was purified to obtain compound 2 (23.5 g, 79.3 mmol) in a yield of 71.7%.

MS: [M + H] &lt; ⁺ &gt; = 297

3) Preparation of Compound 3

Compound 2 (21 g, 70.9 mmol) was dissolved in 300 ml of pyridine and cooled to 0 ° C. in a 500 ml round bottom flask. Trifluoromethanesulfonic anhydride (42g, 148.9mmol) was slowly added for 40 minutes and stirred for 4 hours. After the reaction was completed, 100ml of water was added thereto, stirred for 30 minutes, and the organic layer was separated. Distillation under reduced pressure, concentration and column purification afforded Compound 3 (26.2 g, 46.8 mmol) in a yield of 66%.

MS: [M + H] ⁺ = 561

4) Preparation of Chemical Formula 1-23

In a 250 ml round bottom flask, compound 3 (9 g, 16.1 mmol), naphthalene-1-boronic acid (5.8 g, 33.7 mmol), potassium carbonate (13.3 g, 96.2 mmol), and tetrakis (tree) Phenylphosphine) palladium (0.74 g, 0.64 mmol), tetrahydrofuran 100ml, and 40ml of water were added and refluxed with stirring for 8 hours. After cooling to room temperature, the organic layer was separated. Distillation under reduced pressure, concentration and column purification yielded Chemical Formula 1-23 (5.8 g, 11.2 mmol) in 69.9% yield.

MS: [M + H] ⁺ = 517

< Synthetic example  5> Preparation of substance represented by Chemical Formula 1-26

[Chemical Formula 1-26]

Compound 3 (10 g, 17.8 mmol) and 3,5-diphenylphenyl boronic acid (3,5-diphenylphenyl boronic acid, CAS No. 128388-54-5, 10.2 g, 37.2 of Synthesis Example 4) in a 250 ml round bottom flask mmol), potassium carbonate (12.3g, 89mmol), tetrakis (triphenylphosphine) palladium (0.82g, 0.71mmol), tetrahydrofuran 100ml, water 30ml were added and refluxed with stirring for 8 hours. The resulting solid was filtered and washed sequentially with 200 ml of water and 400 ml of tetrahydrofuran. The filtered solid was recrystallized with chloroform and ethanol to give the formula 1-26 (8.5g, 11.8mmol) in 66.2% yield.

MS: [M + H] ⁺ = 721

< Synthetic example  6> Preparation of substance represented by Chemical Formula 1-30

1) Preparation of Compound 1

In a 250 ml round bottom flask, Compound 3 (12 g, 21.4 mmol), bis (pinacolato) diboron (11.9 g, 46.9 mmol), potassium acetate (10.5 g, 107 mmol), and dioxane 150 ml of Synthesis Example 4 were heated and heated. Stirred. At reflux, bis (dibenzylideneacetone) palladium (0.48g, 0.84mmol) and tricyclohexylphosphine (0.47g, 1.68mmol) were added and stirred for 6 hours. After cooling to room temperature, 50ml of water was added and stirred for 30 minutes. The organic layer was separated and dried over anhydrous magnesium sulfate. Distillation under reduced pressure and concentration and column purification yielded Compound 1 (8.2 g, 15.9 mmol) in a yield of 74.2%.

MS: [M + H] ⁺ = 517

2) Preparation of Chemical Formula 1-30

Compound 1 (8 g, 15.5 mmol) and 2- (4-bromophenyl) -1-phenyl-1H-benzoimidazole (2- (4-bromophenyl) -1-phenyl-1H-benzoimidazole in a 250 ml round bottom flask , CAS No. 2620-76-0, 11.9 g, 34.1 mmol), potassium carbonate (12.9 g, 93.3 mmol), tetrakis (triphenylphosphine) palladium (0.72 g, 0.62 mmol), tetrahydrofuran 80 ml, water 30 ml was added and refluxed with stirring for 8 hours. After cooling to room temperature, the resulting solid was filtered and washed sequentially with 200 ml of water and 400 ml of tetrahydrofuran. The filtered solid was recrystallized with chloroform and ethanol to give the formula 1-30 (8.8g, 11mmol) with a yield of 70.9%.

MS: [M + H] ⁺ = 801

< Example  1>

The glass substrate coated with ITO (indium tin oxide) film with a thickness of 1,500 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, Fischer Co. was used as a detergent, and distilled water was filtered secondly as a filter of Millipore Co. as a distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

Hexanitrile hexaazatriphenylene (HAT) of the following chemical formula was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer.

[LINE]

4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (400 kPa) of the following formula, which is a material for transporting holes on the hole injection layer, was vacuum deposited to form a hole transport layer. Formed.

[NPB]

Subsequently, the light emitting layer was formed by vacuum depositing the following GH and GD at a film thickness ratio of 20: 1 on the hole transport layer at a film thickness of 300 kPa.

The compound of Formula 1-1 prepared in Synthesis Example 1 was vacuum deposited to a thickness of 200 kPa on the light emitting layer to form an electron injection and transport layer.

On the electron injection and transport layer, lithium fluoride (LiF) and aluminum were deposited to a thickness of 2,000 kPa in order to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å / sec, the lithium fluoride of the cathode was maintained at a deposition rate of 0.3 Å / sec, aluminum is 2 Å / sec, the vacuum degree during deposition is 2 × 10 ⁻⁷ to 5 × 10 ⁻⁸ torr was maintained.

As a result of applying a forward electric field of 4.7 V to the organic light emitting device manufactured above, green light was observed as 20.8 cd / A at a current density of 5 mA / cm 2.

< Example  2>

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compound of Formula 1-6 was used instead of the compound of Formula 1-1.

As a result of applying a forward electric field of 4.6 V to the organic light emitting device, green light was observed at 21.5 cd / A at a current density of 5 mA / cm 2.

< Example  3>

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compound of Formula 1-7 was used instead of the compound of Formula 1-1.

As a result of applying a forward electric field of 4.8 V to the organic light emitting device, green light was observed at 19.8 cd / A at a current density of 5 mA / cm 2.

< Example  4>

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound of Formula 1-23 instead of the compound of Formula 1-1.

As a result of applying a forward electric field of 4.5 V to the organic light emitting device manufactured above, green light was observed to be 21.7 cd / A at a current density of 5 mA / cm 2.

< Example  5>

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound of Formula 1-26 instead of the compound of Formula 1-1.

As a result of applying a forward electric field of 4.7 V to the organic light emitting device manufactured above, green light was observed to be 21.3 cd / A at a current density of 5 mA / cm 2.

< Example  6>

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compound of Formula 1-30 was used instead of the compound of Formula 1-1.

As a result of applying a forward electric field of 4.3 V to the organic light emitting device, green light was observed as 22.1 cd / A at a current density of 5 mA / cm 2.

< Comparative Example  1>

Hexanitrile hexaazatriphenylene (500 Å), 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (IB) on an ITO electrode prepared in the same manner as in Example 1 400 kV), GH: GD (film thickness ratio 20: 1) (300 kV) and electron transport material (200 kV) represented by the following chemical formula described in Korean Laid-Open Patent 2003-0067773, lithium fluoride (LiF) 12 kPa in sequence By evaporation, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer were formed in this order. 2,000 의 thick aluminum was deposited thereon to form a cathode and to manufacture an organic light emitting device.

[Electron transport material]

As a result of applying a forward electric field of 4.6V to the organic light emitting device, green light was observed at 19.2 cd / A at a current density of 5 mA / cm 2.

As a result, the compound according to the present invention can be used as an organic material layer in the organic light emitting device, when the compound is used in the organic light emitting device lowers the driving voltage of the device, improves the light efficiency, and by the thermal stability of the compound The life characteristics of the device can be improved.

Claims (8)

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

In Formula 1,
At least one of R1 to R4 is F or CN, and the rest are each independently hydrogen, deuterium, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl having 6 to 20 carbon atoms. Group, and a heteroaryl group having 5 to 20 carbon atoms,
R5, R7, R8, R9, R10 and R12 are hydrogen,
R6 and R11 are the same as each other and are selected from the group consisting of an aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms. The compound of claim 1, wherein at least one of R 1 to R 4 of Formula 1 is F or CN, and the other is hydrogen. The compound of claim 1, wherein at least two of R 1 to R 4 of Formula 1 are F or CN, and the remaining ones are hydrogen. The compound of claim 1, wherein Formula 1 is represented by any one of the following Formulas:

An organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is any one of claims 1 to 4. An organic light-emitting device comprising the compound of formula (1) described. The organic light emitting device of claim 5, wherein the organic material layer includes at least one of an electron injection layer and an electron transport layer, and at least one layer of the electron injection layer and the electron transport layer includes the compound of Formula 1. The organic light emitting device of claim 5, wherein the organic material layer comprises a light emitting layer, and the light emitting layer comprises the compound of Formula 1. The method according to claim 5, wherein the organic layer comprises at least one layer of a hole injection layer, a hole transport layer, and a hole injection and hole transport at the same time, wherein one of the layers comprises the compound of Formula 1 An organic light emitting device characterized in that.

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