KR20090107209A - Asymmetric naphthalenylcarbazole derivatives, the organic thin layer material and the organic electroluminescent element employing the same - Google Patents

Abstract

PURPOSE: An asymmetry naphthalenyl carbazol derivative is provided to ensure excellent light emitting efficiency in the blue wavelength range when producing an organic electric light emitting device. CONSTITUTION: An asymmetry naphthalenyl carbazol derivative is denoted by the chemical formula 1. In chemical formula 1, Ar1 is two or three aryl group of 6-20 carbon atoms which are differently or uniformly linked each other. Ar2 is hydrogen, substituted or non-substituted phenyl group, pyridine group, naphthyl group or quinolinyl group. An organic electric light emitting device comprises an anode, cathode, and plural organic thin film between the anode and cathode.

Description

Asymmetric naphthalenylcarbazole derivatives, the organic thin layer material and the organic electroluminescent element employing the same} Asymmetric naphthalenylcarbazole derivatives, organic thin film materials and organic electroluminescent devices using the same

The present invention relates to an asymmetric naphthalenyl carbazole derivative, an organic thin film material for an organic electroluminescent device comprising the same, and an organic electroluminescent device.

An organic electroluminescent device is a self-luminous device that uses a principle that a fluorescent material emits light by recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field. Since the report of CWTang et al. Of low-voltage driving organic electroluminescent devices (CWTang, SAVanslyke, Applied Physics Letters, Vol. 51, p. 913, 1987, etc.) by stacked devices, organic materials Research on organic electroluminescent elements made of materials has been actively conducted.

In the organic light emitting device, the biggest influence on the life of the organic light emitting device is a blue light emitting material, there have been many attempts to improve the life by improving the blue light emitting material. Among them, the conventionally developed organic organic light emitting device is designed by using a distyryl compound as a organic light emitting material and further adding styrylamine or the like (International Patent Publication No. 94-6175). Phenylanthracene derivatives as a light emitting material (Japanese Patent Publication No. 1996-012600), a material having a naphthyl group at positions 9 and 10 of anthracene (Japanese Patent Publication No. 1999-3782), or anthracene 9 Those using an element material having a fluoranthene group at the 10 position (Japanese Patent Laid-Open No. 2001-257074) have been disclosed. However, in the case of using such anthracene derivative, there is a problem of device life and the formation of uniform thin film is not easy, the film forming processability is not excellent, the heat resistance is not excellent, and due to the plate-like structure (aggregation) between molecules during deposition This occurs, in particular, there is a problem in realizing long life with high efficiency and high quality blue light emission.

An object of the present invention is to solve the above problems, the present invention is to provide a novel asymmetric naphthalenyl carbazole derivative that can provide a high efficiency and long life of the organic electroluminescent device.

Still another object of the present invention is to provide an organic thin film material for organic electroluminescent device and organic electroluminescent device having high efficiency and long life, using asymmetric naphthalenyl carbazole derivative according to the present invention.

The present invention for achieving the above object,

It provides an asymmetric naphthalenylcarbazole derivative of formula (I):

[Formula 1]

Where

Ar1 is the same or different aryl group having 6 to 20 carbon atoms are connected to each other or three,

Ar2 is hydrogen; Or a substituted or unsubstituted phenyl group, pyridine group, naphthyl group, or quinoline group.

The aryl group of Ar1 may be selected from the following Chemical Formulas 2 to 4:

Ar2 is independently from each other at one or more hydrogen positions, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, It may be substituted with a substituent selected from the group consisting of a cyano group and a trifluoromethyl group.

For another object of the present invention,

The present invention provides an organic thin film material for an organic electroluminescent device comprising the asymmetric naphthalenylcarbazole derivative of Chemical Formula 1.

For another object of the present invention,

The present invention provides an organic electroluminescent device having an anode, a cathode and a plurality of organic thin film layers positioned between the anode and the cathode,

Some or all of the plurality of organic thin film layers provide an organic electroluminescent device comprising an asymmetric naphthalenylcarbazole derivative.

According to the present invention, the naphthalenylcarbazole compound of formula (1) incorporating naphthalene having excellent electron transporting properties and carbazole groups having excellent hole transporting properties can be used for forming an organic film of an organic electroluminescent device, and in particular, Alternatively, when used as a host material or in combination with a fluorescent dopant, when the organic electroluminescent device is manufactured, excellent light emission efficiency and excellent lifetime characteristics are exhibited in the blue wavelength region.

Hereinafter, the present invention will be described in more detail. The following detailed description illustrates the present invention by way of example, and the present invention is not limited thereto.

The present invention provides an asymmetric naphthalenylcarbazole derivative of formula (I):

[Formula 1]

Where

The Ar1 is the same or different aryl group having 6 to 20 carbon atoms are connected to each other two or three, Ar2 is hydrogen; Or a substituted or unsubstituted phenyl group, pyridine group, naphthyl group or quinoline group.

In the general formula (1), the solid line representing the bonding position is drawn through all the rings of naphthalene, but this means that the bonding position of Ar 1 and carbazole may be any position of carbon of naphthalene.

The aryl group of Ar 1 may be selected from compounds of Formulas 2 to 4 below:

In addition, Ar1 may be preferably selected from the following Chemical Formulas 5 to 16:

Ar 2 in Formula 1 may be preferably selected from Formula 17 to Formula 21 below:

Ar2 may have a substituent at one or more hydrogen positions, and as a substituent, independently of each other, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, and a carbon number It may be selected from the group consisting of 1 to 20 alkoxy group, cyano group, trifluoromethyl group.

According to one embodiment of the present invention, the asymmetric naphthalenyl carbazole derivative of Formula 1 may be any one of the following Compounds 1 to 9, but is not limited thereto:

Methods of synthesizing important intermediates of the asymmetric naphthalenylcarbazole derivatives of Formula 1 according to the present invention are shown in Schemes 1 and 2.

Scheme 3 below shows the synthesis of Compound 1 and Scheme 4 wherein Compound 1 has a structural isomer relationship with Compound 1. And the method for synthesizing compound 5 is shown in Scheme 6 and the scheme for synthesizing compound 8, respectively. Other compounds can be synthesized through the same synthetic route, and those skilled in the art can synthesize asymmetric naphthalenylcarbazole derivatives having structural characteristics in which the naphthalene and carbazole of the present invention are bonded according to the present invention or a known method. It is possible to do The present invention is not limited to the above compounds 1 to 9.

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Hereinafter, an organic electroluminescent device material and an organic electroluminescent device according to the present invention will be described.

The present invention provides an organic thin film material for an organic electroluminescent device comprising the asymmetric naphthalenylcarbazole derivative of Chemical Formula 1. Any organic thin film material for an organic electroluminescent device containing the asymmetric naphthalenylcarbazole derivative of Chemical Formula 1 is included in the present invention.

According to an embodiment of the present invention, the organic thin film material including the asymmetric naphthalenylcarbazole derivative of Formula 1 is preferably a light emitting material or a host material.

Except for the asymmetric naphthalenylcarbazole derivative of Formula 1 according to the present invention, an organic thin film material for an organic electroluminescent device is well known in the art, and thus a detailed description thereof will be omitted, except for the organic electroluminescent device of the present invention. An example is given in the explanation.

The organic electroluminescent device according to the present invention is an organic electroluminescent device having an anode, a cathode, and a plurality of organic thin film layers positioned between the anode and the cathode, wherein all or part of the plurality of organic thin film layers of Formula 1 Asymmetric naphthalenylcarbazole derivatives having. The organic thin film layer may include at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and an electron transport layer.

According to an embodiment of the present invention, the organic thin film layer including the asymmetric naphthalenylcarbazole derivative of Formula 1 is preferably a light emitting layer.

A more specific example is described as follows.

1 is a cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention. As illustrated, the substrate 1, the anode 2, the hole transport layer 4, the light emitting layer 5, the electron transport layer 6, and the cathode 7 may be provided. It may further include an electron injection layer (not shown) between the electron transport layer and the cathode, and a hole injection layer 3 between the anode and the hole transport layer.

The organic thin film layer refers to a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc., all or part of these include naphthalenylcarbazole derivatives of the formula (1).

Examples of the material for the anode 2 include metal oxides or metal nitrides such as ITO, IZO, tin oxide, zinc oxide, zinc aluminum oxide, and titanium nitride; Metals such as gold, platinum, silver, copper, aluminum, nickel, cobalt, lead, molybdenum, tungsten, tantalum and niobium; Alloys of these metals or alloys of copper iodides; Conductive polymers such as polyaniline, polythiopine, polypyrrole, polyphenylenevinylene, poly (3-methylthiopine), and polyphenylenesulfagard. The anode 2 may be formed of only one type of the aforementioned materials or may be formed of a mixture of a plurality of materials. In addition, a multilayer structure composed of a plurality of layers of the same composition or different compositions can be formed.

The hole injection layer 3 of the present invention may be a material known in the art, in addition to the naphthalenylcarbazole derivative of Formula 1 according to the present invention, but is not limited to PEDOT / PSS or copper phthalocyanine (CuPc), 4 A material such as, 4 ', 4' '-tris (3-methylphenylphenylamino) triphenylamine (m-MTDATA) is formed to a thickness of 5 nm to 40 nm.

The hole transport layer 4, in addition to the naphthalenylcarbazole derivative of formula 1 according to the present invention, 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] -biphenyl (NPD) Or a substance such as N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine (TPD).

The light emitting layer 5 may be a material known in the art, in addition to the naphthalenylcarbazole derivative of Chemical Formula 1 according to the present invention, but is not limited to 4,4'-N, N-dicarbazole biphenyl ( CBP) and 1,3-N, N-dicarbazolebenzene (mCP) and its derivatives are well known. Also, recently, BAlq or similar Al complex materials having electron transport properties are known to be useful as phosphorescent hosts. Specifically, (4,4'-bis (2,2-diphenyl-ethen-1-yl) di Phenyl (DPVBi), bis (styryl) amine (DSA) system, bis (2-methyl-8-quinolinolato) (triphenylsiloxy) aluminum (III) (SAlq), bis (2-methyl-8 -Quinolinolato) (para-phenolato) aluminum (III) (BAlq), bis (salen) zin (II), 1,3-bis [4- (N, N-dimethylamino) phenyl-1,3 , 4-oxadiazolyl] benzene (OXD8), 3- (biphenyl-4-yl) -5- (4-dimethylamino) 4- (4-ethylphenyl) -1,2,4-triazole (p -EtTAZ), 3- (4-biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole (TAZ), 2,2 ', 7,7' Tetrakis (non-phenyl-4-yl) -9,9'-spirofluorene (Spiro-DPVBI), tris (para-ter-phenyl-4-yl) amine (p-TTA), 5,5- Bis (dimethythylboryl) -2,2-bithiophene (BMB-2T) and perylene.

Tris (8-quinolinato) aluminum (III) (Alq3), DCM1 (4-dicyanomethylene-2-methyl-6- (para-dimethylaminostyryl) -4H-pyran), DCM2 (4- Dicyanomethylene-2-methyl-6- (zulolidin-4-yl-vinyl) -4H-pyran), DCJT (4- (dicyanomethylene) -2-methyl-6- (1,1,7, 7-tetramethylzulolidil-9-enyl) -4H-pyran), DCJTB (4- (dicyanomethylene) -2-tertbutylbutyl-6- (1,1,7,7-tetramethylzololidyl -9-enyl) -4H-pyran), DCJTI (4-dicyanomethylene) -2-isopropyl-6- (1,1,7,7-tetramethylzulolidil-9-enyl) -4H-pyran ) And nile red, rubrene, etc. can be used as a host or dopant.

In the organic electroluminescent device of the present invention, an iridium metal complex may be used as a dopant to form an organic layer, in particular, a light emitting layer, and iridium (III) bis (7,8-benzoquinoline) acetylacetonate (Bzq), Iridium metal complexes such as iridium (III) bis (1-phenylisoquinoline) acetylacetonate (Piq) and iridium (III) bis [1- (4-thibutylphenyl) isoquinoline] acetylacetonate are light emitting layer forming materials. It is very useful as a phosphor dopant material and shows excellent luminescence properties.

Dopants may be omitted or optionally added, but are not limited to those listed as host materials above.

The electron transport layer (6) is a aryl substituted oxadiazole, aryl-substituted triazole, aryl-substituted phenanthroline, benzoxazole, or benzsi, in addition to the naphthalenylcarbazole derivative of Formula 1 according to the present invention Azole compounds, for example, 1,3-bis (N, Nt-butyl-phenyl) -1,3,4-oxadiazole (OXD-7); 3-phenyl-4- (1'-naphthyl) -5-phenyl-1,2,4-triazole (TAZ); 2,9-dimethyl-4,7-diphenyl-phenanthroline (vasocuproin or BCP); Bis (2- (2-hydroxyphenyl) -benzoxazolate) zinc; Or bis (2- (2-hydroxyphenyl) -benziazolate) zinc; As the electron transporting material, (4-biphenyl) (4-t-butylphenyl) oxydiazole (PDB) and tris (8-quinolinato) aluminum (III) (Alq3) can be used, preferably Tris ( Preference is given to 8-quinolinato) aluminum (III) (Alq3).

The electron injection layer and the cathode 7 may use a material known in the art, but is not limited to LiF as an electron injection layer and a metal having a low work function such as Al, Ca, Mg, Ag or the like may be used as the cathode. And Al is preferred.

Hereinafter, the present invention will be described in more detail through synthesis examples and examples.

Suzuki coupling reactions applied for synthesizing the object of the present invention have been made up to date (Manufacturing 'Chem. Rev., Vo1.95, No.7, 2457 (1995)', etc.) It can carry out under reaction conditions. The reaction is usually carried out under an inert atmosphere such as nitrogen, argon, helium and the like under normal pressure, but may be carried out under pressurized conditions as necessary. Although reaction temperature is the range of 15-300 degreeC, Especially preferably, it is 30-200 degreeC.

As halogen used for halogenation, an iodine atom, a bromine atom, a chlorine atom, etc. are mentioned, For example, Iodine atom and a bromine atom are preferable. Although the halogenating agent in a halogenation reaction is not specifically limited, For example, N-halogenation succinimide is used suitably. The reaction is usually carried out in an inert solvent under an inert atmosphere such as nitrogen, argon or helium. As an inert solvent used, for example, N, N-dimethylformamide, N, N-dimethylacetoamide, N-methylpyrrolidone, dimethyl sulfoxide, carbon tetrachloride, chlorobenzene, dichlorobenzene, nitro Benzene, toluene, xylene methyl cellosolve, ethyl cellosolve, water, etc. are mentioned, Preferably, they are N, N- dimethylformamide and N-methylpyrrolidone.

The boration reaction may be carried out by a known method (Japanese Chemical Society, 4th Edition, vol. 61, 90, J. Org. Chem., Vol. 60, 7508 (1995), etc.). It is possible.

The synthesis method of the naphthalenylcarbazole compound 10, the compound 11, and the compound 12 which are intermediates used in various synthesis examples from the starting materials are as follows.

Scheme 1

Scheme 2

< Synthesis Example  1> Synthesis of Compound 10.

1,4-bromonaphthalene 14.6g (51mmol) and 9 H - carbazol 1.45g (8.7mmol) was dissolved in 1,4-dioxane and copper iodide 0.31g (1.6mmol), trans-1,2-dia Minocyclohexane 1.9 g (16.9 mmol) and 22.8 g (107 mmol) of potassium triphosphate are added, followed by stirring at a boiling point of 1,4-dioxane for 24 hours. After cooling to room temperature, the reaction product was extracted with ethyl acetate, the solvent was removed under reduced pressure, and then separated and purified by chromatography using silica gel using a solution of ethyl acetate and hexane in a 15: 1 volume ratio as a developing solvent. After the desired product was separated, the desired product 9- (4-bromo-naphthalen-1-yl) -9 H -carbazole (Compound 10, 2.00 g) was obtained in 62% yield by drying under reduced pressure.

MS (EI) (calcd for C ₂₂ H ₁₄ BrN, 372.26; Found: 371).

< Synthesis Example  2> Synthesis of Compound 11.

Dissolve 1.00 g (2.7 mmol) of 9- (4-bromo-naphthalen-1-yl) -9 H -carbazole (Compound 10) in tetrahydrofuran, lower the temperature to add n-BuLi (11 mmol), and Stir for 1 hour. Bis (pinacolato) diboron (13 mmol) was added thereto, followed by stirring at room temperature for one hour. After the reaction was completed, 2M aqueous hydrochloric acid solution was added to the reaction mixture, followed by stirring for one hour, and the reaction was terminated. The reaction solution was extracted with ethyl acetate, the solvent was removed under reduced pressure, and then added dropwise into hexane to precipitate as a solid 9- [4- (4,4,5,5-tetramethyl- [1,3,2] Dioxaborolan-2-yl) -naphthalen-1-yl] -9 H -carbazole (Compound 11) was isolated through filtration under reduced pressure and dried to give 0.81 g in 72% yield.

MS (EI) (calcd for C ₂₈ H ₂₆ BNO ₂ , 419.32; Found: 418).

< Synthesis Example  3> Synthesis of Compound 12.

Synthesis was carried out in the same manner as in Synthesis Example 1, except that 2, 6-dibromonaphthalene was used instead of 1,4-dibromonaphthalene.

MS (EI) (calcd for C ₂₂ H ₁₄ BrN, 372.26; Found: 371).

In Scheme 5, a method for synthesizing Compound 5 corresponding to one of the final targets of the present patent using Compound 12 as an intermediate will be described.

Scheme 5

< Synthesis Example  4> Synthesis of Compound 13.

9-bromoanthracene (3.2 g) was added 2-naphthalene boronic acid (4.3 g) in 1,2-dimethoxymethane solvent (49 mL), followed by Pd catalyst [tetrakis (triphenylphosphine) -palladium (0 )] (0.9 g) and 2M aqueous sodium carbonate solution (25 mL) were added and 9-naphthalen-2-yl-anthracene (2.6 g) was obtained by Suzuki coupling at a temperature corresponding to the boiling point of the solvent for 14 hours.

9-naphthalen-2-yl-anthracene (2.6 g) was added to 4.6 g of N-bromosuccinimide in dimethylformamide solvent (26 mL) and brominated by stirring at room temperature for 4 hours to give 9-bromo- 10-naphthalen-2-yl-anthracene (3.0 g) was obtained.

9-bromo-10-naphthalen-2-yl-anthracene (3.0 g) was added dropwise to 5.3 mL of 1.6M n-butyllithium under THF solvent (30 mL) at -78 ° C, followed by lithium halide exchange reaction by stirring for 1 hour. Proceed. After stirring for one hour, after adding trimethylborane (0.97g), the temperature was raised to room temperature, and then stirred for one hour at room temperature, 30 mL of 2M aqueous hydrochloric acid solution was added and stirred for an additional hour to terminate the reaction, followed by 10-naphthelan 2-yl-anthracene-9-yl-bombroronic acid (2.2 g) was obtained.

MS (EI) (calcd for C ₂₄ H ₁₇ BO ₂ , 348.20; Found: 347).

< Synthesis Example  5> Synthesis of Compound 5.

In a 100 mL three-necked flask, a mixture of 1,2 g of intermediate compound 12, prepared in Synthesis Example 3, and 10-naphthalen-2-yl-anthracene-9-yl-boronic acid (1.1 g) prepared in Synthesis Example 3 under a nitrogen atmosphere was used as a 1,2-dimethoxyethane solvent ( 25 mL) was added at 0.066 g of a Pd catalyst [tetrakis- (triphenylphosphine) palladium (0)] to add 2M aqueous sodium carbonate solution (12 mL) to reflux for 20 hours at 95 degrees Celsius. After the completion of the reaction, the reaction temperature was lowered to room temperature, the organic layer was extracted with distilled water and ethyl acetate, dried over magnesium sulfate, the solvent was removed under reduced pressure, and then filtered with tetrahydrofuran and methanol. 9- [6- (10-naphthalen-2-yl-anthracene-9-yl) -naphthalen-2-yl] -9H-carbazole was obtained after vacuum drying.

MS (EI) (calcd for C ₄₆ H ₂₉ N, 595.73; Found: 595).

In Scheme 6, a method for synthesizing Compound 8, which corresponds to one of the final targets of the present patent, using Compound 11, which is an intermediate, will be described.

Scheme 6

< Synthesis Example  6> Synthesis of Compound 8.

In a 100 mL three-necked flask, a compound 10-naphthalen-2-yl-anthracene-9-yl-boronic acid (1.1 g) and 0.96 g of 2-bromo-6-iodonaphthalene prepared in Synthesis Example 4 were added under a nitrogen atmosphere. The temperature corresponding to the boiling point of the solvent for 14 hours was added by adding 2M aqueous sodium carbonate solution (12 mL) using 0.066 g of a Pd catalyst [tetrakis- (triphenylphosphine) palladium (0)] in 2 dimethoxyethane solvent (25 mL). 1.2 g of 9- (6-bromo-naphthalen-2-yl) -10-naphthalen-2-yl-anthracene in 82% yield was obtained by Suzuki coupling reaction.

In a 100 mL three-necked flask, 1.2 g of 9- (6-bromo-naphthalen-2-yl) -10- or phthalen-2-yl-anthracene under nitrogen atmosphere and the intermediate 9- [4- ( 1.1 g of 4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) -naphthalen-1-yl] -9 H -carbazole (Compound 11), and a catalytic amount of 0.056 g of tetrakis- (triphenylphosphine) palladium was added and 30 mL of 1,2-dimethoxyethane and 15 mL of 2M-sodium carbonate aqueous solution were added, and the mixture was refluxed at 95 degrees Celsius for 20 hours. After the completion of the reaction, the reaction temperature was lowered to room temperature, the organic layer was extracted with distilled water and ethyl acetate, dried over magnesium sulfate, the solvent was removed under reduced pressure, and then filtered with tetrahydrofuran and methanol. 9- [6 '-(10-naphthalen-2-yl-anthracene-9-yl)-[1,2'] binaphthalenyl-4-yl as a target in a yield of 0.98 g (68%) after vacuum drying ] -9H-carbazole (Compound 8) was obtained by 1.6g in 68% yield.

MS (EI) (calcd for C ₅₆ H ₃₅ N, 721.88; Found: 721).

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited only to the following examples. Fabrication of the organic electroluminescent device of the present invention does not require a special device or method, and can be manufactured according to the method of manufacturing an organic electroluminescent device using a conventional light emitting material as described with reference to FIG.

The equipment used in the following Examples and Comparative Examples used EL deposition machine of VTS. The characteristics, ie driving voltage, color coordinates, and efficiency measuring method of the organic electroluminescent device manufactured as described above are as follows.

1) Driving voltage

The change of current density according to the voltage change was measured for the manufactured organic electroluminescent device. The measurement was performed by measuring the current density flowing from the unit device using a current-voltmeter (Kethely 237) while applying a current density of 2.5 mA from 2.5 mA / cm ² to 100 mA / cm ² .

2) color coordinates

The current density of the prepared organic electroluminescent device was measured using a luminance meter (PR650) while increasing the current density by 2.5 mA from 2.5 mA / cm ² to 100 mA / cm ² .

3) luminance

Power was supplied from a current-voltmeter (Kethley SMU 236) and measured using a luminance meter (PR650).

4) efficiency

Luminous efficiency was calculated using the brightness and current density measured above.

As shown in FIG. 1, an ITO electrode was formed on a glass substrate, and then subjected to UV-ozone cleaning or oxygen plasma cleaning, and then m-TDATA was deposited to a thickness of 500 으로 with a hole injection layer thereon. NPD (N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) benzidine) was deposited to a thickness of 400 kPa as a hole transport layer, and the present invention was used as a host material for blue light emission. Compounds were co-deposited alone or fluorescent dopants of the formula (24) at an appropriate ratio to form the desired light emitting layer to a thickness of 400Å. Alq3 (tris- (8-hydroxyquinoline) aluminium (III)) was vacuum deposited to a thickness of 200 으로 with an electron transport layer. Thereafter, an Al: Li layer was vacuum-deposited on the upper portion to form an 1000 μm thick aluminum / lithium electrode, thereby manufacturing an organic electroluminescent device.

Example  1: Fabrication and Evaluation of Organic Electroluminescent Device 1

A glass substrate with an ITO transparent electrode coated with an insulating film so as to be fabricated as a 22 mm × 2 mm unit device was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, followed by UV ozone cleaning for 30 minutes. The glass substrate with a transparent electrode line after cleaning is mounted on the substrate holder of the vacuum deposition apparatus, and first, the transparent electrode is covered on the side of the side where the transparent electrode line is formed, and m-TDATA, which is a hole injection material, is used for resistive heating deposition. It formed into a film. NPD as a hole transport material was formed on it by the same vapor deposition method. The compound 5 prepared in Synthesis Example 5 was deposited to a thickness of 40 nm using a light emitting layer thereon, and then Alq 3 was formed into an electron transport material. An Li film was formed thereon at a film thickness of 10 nm at a film formation rate of 1.5 msec / sec: 1 m / min, and Al was deposited on the Li film to form a metal cathode having a thickness of 100 nm to fabricate an organic electroluminescent device. The evaluation results are shown in Table 1.

Example  2: Fabrication and Evaluation of Organic Electroluminescent Device 2

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound 8 prepared in Synthesis Example 6 was used instead of Compound 5. The evaluation results are shown in Table 1.

Example  3: Fabrication and Evaluation of Organic Electroluminescent Device 3

A glass substrate with an ITO transparent electrode coated with an insulating film so as to be produced as a 2 mm × 2 mm unit device was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, followed by UV ozone cleaning for 30 minutes. The glass substrate with a transparent electrode line after cleaning is mounted on the substrate holder of the vacuum deposition apparatus, and first, the transparent electrode is covered on the side of the side where the transparent electrode line is formed, and m-TDATA, which is a hole injection material, is used for resistive heating deposition. It formed into a film. NPD as a hole transport material was formed on it by the same vapor deposition method. Then, the compound 5 and the fluorescent dopant (3% by weight) of Chemical Formula 24 were co-deposited to a thickness of 40 nm on the light emitting layer, and then Alq 3 was formed by using an electron transport material. An Li film was formed thereon at a film thickness of 10 nm at a film formation rate of 1.5 msec / sec: 1 m / min, and Al was deposited on the Li film to form a metal cathode having a thickness of 100 nm, thereby producing an organic electroluminescent device. The evaluation results are shown in Table 1.

Comparative example  1: Fabrication and Evaluation of Organic Electroluminescent Device 5

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of Formula 22 was used instead of Compound 5. The evaluation results are shown in Table 1.

Comparative example  2: Fabrication and Evaluation of Organic Electroluminescent Device 6

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of Formula 23 was used instead of Compound 5. The evaluation results are shown in Table 1.

Comparative example  3: Fabrication and Evaluation of Organic Electroluminescent Device 7

An organic electroluminescent device was manufactured in the same manner as in Example 3, except that the compound of Formula 22 was used instead of Compound 5. The evaluation results are shown in Table 1.

 [Formula 22] [Formula 23]

[Formula 24]

TABLE 1

Current density (mA / cm ² ) Color coordinates CIE1931 (x, y) Efficiency (cd / A) Life (@ 1000nit) Example 1 20 (0.156, 0.126) 4.04 120 Example 2 20 (0.178, 0.193) 6.09 85 Example 3 20 (0.155,0.152) 5.54 420 Comparative Example 1 20 (0.159, 0.095) 2.78 90 Comparative Example 2 20 (0.170, 0.125) 2.77 70 Comparative Example 3 20 (0.154,0.135) 5.53 400

The naphthalenylcarbazole compound represented by Chemical Formula 1 from the results of Table 1 can be used to form an organic thin film layer of an organic electroluminescent device. It can be seen that the light emission efficiency and lifetime characteristics are superior to those of known materials.

1 is a view showing the structure of a conventional organic electroluminescent device.

* Explanation of the major symbols in the drawings *

1: Substrate # 2: Anode

3: hole injection layer 4: hole transport layer

5: light emitting layer 6: electron transport layer

7: cathode

Claims (10)

Asymmetric naphthalenylcarbazole derivatives of formula [Formula 1]

Where Ar1 is the same or different aryl group having 6 to 20 carbon atoms are connected to each other or three, Ar2 is hydrogen; Or a substituted or unsubstituted phenyl group, pyridine group, naphthyl group or quinoline group. The method of claim 1, Asymmetric naphthalenylcarbazole derivatives, characterized in that Ar1 is a substituent selected from the following Chemical Formulas 2 to 4.

The method of claim 1, The asymmetric naphthalenylcarbazole derivatives, wherein Ar 1 is selected from substituents of the following Chemical Formulas 5 to 16.

The method of claim 1, Ar 2 independently of one another at one or more hydrogen positions is a halogen atom, a nitro group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group and a trifluoromethyl group Naphthalenylcarbazole derivatives, characterized in that substituted with a substituent selected from the group. The method of claim 1, Naphthalenyl carbazole derivative of the formula (1) is characterized in that selected from the group consisting of the following compounds.

An organic thin film material for an organic electroluminescent device, comprising the asymmetric naphthalenylcarbazole derivative of any one of claims 1 to 5. The method of claim 6, The organic thin film material for an organic electroluminescent device, wherein the organic thin film material is a light emitting material or a host material. In an organic electroluminescent device having an anode, a cathode and a plurality of organic thin film layers positioned between the anode and the cathode, An organic electroluminescent device, characterized in that some or all of the plurality of organic thin film layers comprises the asymmetric naphthalenylcarbazole derivative of any one of claims 1 to 5. The method of claim 8, And the organic thin film layer comprises at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and an electron transport layer. The method of claim 8, The organic light emitting device, characterized in that the organic thin film layer is a light emitting layer.

Images