KR101375542B1 - Hole transporting material comprising thiophen derivative and organic electroluminescent device using the same - Google Patents

Abstract

The present invention provides a tertiary aryl amine including a thiophene and an organic electroluminescent compound comprising the same, which has excellent electrical properties, luminescence properties and high charge transport ability, and has red, blue, white and the like. It is useful as a charge transport material suitable for fluorescent and phosphorescent dopants of the color of. In addition, since the synthesis process is economical and the asymmetric structure proposed in the present invention is excellent, the hole transporting and electron transporting ability is excellent, and the glass transition temperature is high, so that the device is thermally and electrically stable, There is an effect of improving the lifetime of the battery.

Description

Hole transporting material including thiophene derivative and organic light emitting device using same TECHNICAL FIELD [0001] HOLE TRANSPORTING MATERIAL COMPRISING THIOPHEN DERIVATIVE AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME

The present invention relates to an amine-based hole transport material derivative and an organic light emitting device using the same, and more particularly, to an organic light emitting device including a specific structure of tertiary aryl amine and thiophene.

Organic electroluminescent devices have been developed by Pope et al. In 1965, since organic luminescent materials were first discovered from single crystals of anthracene. In 1987, organic electroluminescent devices were developed by Tang, Kodak Co., (CWTang, SAVanslyke, Applied Physics Letters, 1987, 51 , 913)], a material for a light emitting device including various kinds of organic materials has been developed .

The criteria for the basic performance of the display device are driving voltage, power consumption, efficiency, brightness, contrast, response time, lifetime, display color (color coordinate) and color purity. One of the non-luminous display devices, LCD, is the most widely used because of its light weight, low power consumption. However, the characteristics such as response time, contrast, viewing angle, etc. have not reached a satisfactory level, and there is still much room for improvement. Accordingly, organic light-emitting diodes (OLEDs) have been attracting attention as next-generation display devices capable of solving these problems. OLEDs are self-luminous display devices that have wide viewing angles, excellent contrast, and fast response times.

A typical organic electroluminescent device is a self-luminous device using the principle that excitons having recombination energy of electrons and holes injected through a cathode and an anode are formed in an organic thin film and light of a specific wavelength is generated from the excitons formed.

Such a light emitting material is largely divided into fluorescence and phosphorescence. The method of forming a light emitting layer includes a method of doping a fluorescent host with a dopant, a method of increasing a quantum efficiency by doping a fluorescent dopant into a fluorescent host, (DCM, Rubrene, DCJTB, etc.) and moving the emission wavelength to a long wavelength. Through such doping, the emission wavelength, efficiency, driving voltage, and lifespan are improved.

The structure of a general organic electroluminescent device includes an anode, a hole injection layer (HIL) for receiving holes from the anode, a hole transport layer (HTL) for transporting holes, a light emitting layer (EML) An electron transport layer (ETL) for receiving the electrons from the electron transport layer and transferring the electrons to the light emitting layer, and a cathode. Such a thin film structure formed by the vacuum evaporation method can adjust the moving speed of holes and electrons to balance the densities of holes and electrons in the light emitting layer, thereby enhancing the luminous efficiency. In addition, in order to realize practical use and improve the characteristics of the organic electroluminescent device, the device material, particularly, the hole transport material must be thermally and electrically stable as well as constituting the device with the multilayer structure as described above. This is because molecules with low thermal stability due to the heat generated from the device when the voltage is applied are low in crystal stability and are rearranged, resulting in local crystallization and deterioration and destruction of the device.

The hole transport materials that have been used so far include m-MTDATA [4,4 ', 4 "-tris ( N- 3-methylphenyl- N -phenylamino) -triphenylamine, 2-TNATA [4,4', 4" -Tris ( N- (naphthylene-2-yl) -N -phenylamino) -triphenylamine], TPD [ N , N' -diphenyl- N , N' -di (3-methylphenyl) -4,4 '-Diaminobiphenyl], and NPB [ N , N' -di (naphthalen-1-yl) -N , N' -diphenylbenzidine]. M-MTDATA and 2-TNATA have a glass transition temperature ( Tg) is not only low, but also a lot of problems occur in the process of mass production, there is a problem in realizing the total color, and TPD and NPB also have a low glass transition temperature of 60 ℃ and 96 ℃, respectively, There is a fatal disadvantage of shortening the lifespan.

There is still a need for an excellent material that can improve the lifetime and luminous efficiency of a device because the conventional hole transport material used in the organic electroluminescent device still requires improvement in performance.

The present invention is designed to improve the problems of the prior art as described above, by introducing aromatics, florene, heteroaryl groups, etc. in the tertiary amine as a transfer material of the organic EL device having a multi-layer structure excellent thermal stability and lifespan It provides an organic light emitting device that is not only increased but also excellent in light emission brightness and efficiency.

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또한, 유기전계 발광소자의 정공수송층 물질로 사용되며, 하기 구조식으로 표시되는 화합물 그룹 중에서 선택되는 것을 특징으로 하는 비대칭 구조의 3차 아릴 아민 화합물을 제공한다:

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아울러, 제 1전극; 제 2전극; 및 상기 제 1전극 및 상기 제2 전극 사이에 형성된 1층 이상의 유기물층;을 포함하고 있는 유기전계 발광소자에 있어서, 상기 유기물층은 발광층 및 정공수송층을 포함하며, 상기 정공수송층은 상기 비대칭 구조의 3차 아릴 아민 화합물을 포함하는 것을 특징으로 하는 유기전계 발광소자를 제공한다.
In the present invention to achieve the above object,
It provides a tertiary aryl amine compound having an asymmetric structure, which is used as a hole transport layer material of an organic light emitting device, and is selected from the group of compounds represented by the following structural formulas:

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In addition, it provides a tertiary aryl amine compound having an asymmetric structure, which is used as a hole transport layer material of an organic light emitting device, and is selected from the group of compounds represented by the following structural formulas:

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In addition, the first electrode; A second electrode; And at least one organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer and a hole transport layer, and the hole transport layer is a tertiary structure of the asymmetric structure. It provides an organic electroluminescent device comprising an aryl amine compound.

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The present invention is designed to improve the problems of the prior art as described above, by introducing aromatics, florene, heteroaryl groups, etc. in the tertiary amine as a transfer material of the organic EL device having a multi-layer structure excellent thermal stability and lifespan It provides an organic light emitting device that is not only increased but also excellent in light emission brightness and efficiency. In addition, the aryl amine derivative according to the present invention may have various characteristics depending on the type of substituents in addition to the material for hole transport, and can play all roles of hole injection, hole transport, electron injection, and transport depending on the substituent, and high efficiency In addition, it is expected to contribute to the improvement of technology of the display industry by providing an organic light emitting device having excellent color purity.

1 is a schematic view illustrating a single layer structure of an organic electroluminescent device according to an embodiment of the present invention,
2 is a view schematically showing a multiple layer structure of an organic electroluminescent device according to another embodiment of the present invention,
Figure 3 is a UV / PL spectrum of a compound according to one embodiment of the present invention,
Figure 4 is data on the thermal stability of a compound according to one embodiment of the present invention.

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도 3 및 도 4에는 본 발명에 따른 3차 아릴 아민의 일 예인 하기 화합물 A1의 UV(Ultraviolet)/PL(Photoluminescence) 스펙트럼 및 열적 안정성에 대한 데이터를 나타내었다.The present invention relates to a tertiary aryl amine compound having an asymmetric structure, which is used as a hole transport layer material of an organic light emitting device and is selected from the group of compounds represented by the following structural formulas:

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3 and 4 show data on UV (Ultraviolet) / PL (Photoluminescence) spectrum and thermal stability of the following Compound A1, which is an example of a tertiary aryl amine according to the present invention.

The UV (Ultraviolet) / PL (Photoluminescence) spectrum of FIG. 3 measures the emission wavelength of each compound in order to characterize the OLED. It measures the wavelength at which the most luminescent light is emitted by irradiating light of a wavelength absorbed through UV It is a graph.

The UV (Ultraviolet) / PL (Photoluminescene) spectrum can be obtained through a method known in the art, in the present invention, the wavelength of about 340nm to a solid film prepared by coating a solution containing the compound A1 in the quartz (quartz) The spectrum of FIG. 3 was obtained by irradiating the excitation light, and since it has a maximum emission peak at about 430 nm as shown in FIG. 3, the emission efficiency is expected to be excellent. However, the specific value will vary depending on the purity of the compound, the surrounding environment, etc., and thus, the trend of the data is more important than the detailed value.

Figure 4 is to determine the thermal stability of the hole transport material, which can also be evaluated through a method known in the art, in the present invention using a thermogravimetric analysis (TGA) in a fan under a nitrogen atmosphere A sample of Compound A1 of constant weight was weighed and the change in weight of the sample was measured while increasing the temperature at a constant rate to obtain data on thermal stability. As a result, as shown in FIG. 4, it was confirmed that the thermal decomposition temperature of Compound A1 was about 300 ° C. or more, and the tertiary aryl amine according to the present invention exhibited thermal stability even at a high temperature of about 300 ° C. FIG. It can be seen that.

The present invention further provides an organic electroluminescent material comprising an arylamine compound as described above.

The organic electroluminescent material can be produced by a conventional method and materials for manufacturing an organic electroluminescent device, except that the above-mentioned arylamine compound is used to form one or more organic layers.

That is, the organic light emitting device of the present invention includes a first electrode, a second electrode and one or more organic material layers disposed between the electrodes, and at least one of the organic material layers includes the aryl amine derivative of the present invention.
Specifically, the present invention is a first electrode; A second electrode; And at least one organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer and a hole transporting layer, and the hole transporting layer has three asymmetric structures. It provides an organic electroluminescent device comprising a primary aryl amine compound.

In addition, in the organic light emitting device of the present invention, the organic material layer includes a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and if necessary, one hole injection layer, a hole transport layer, a hole blocking layer, or an electron transport layer. It can be used with the two layers omitted.

The organic material layer of the organic light emitting device of the present invention may be a single layer structure consisting of one layer, or may be a multilayer structure of two or more layers including a light emitting layer. When the organic material layer of the organic light emitting device of the present invention has a multi-layer structure, it is, for example, a hole injection layer (Hole Injection Layer), a hole transport layer (Hole Transport Layer), an emission layer (Electroluminescence Layer), a hole blocking layer, (Hole Blocking Layer), It may have a structure in which an electron transport layer or the like is stacked.

For example, the structure of the organic electroluminescent device of the present invention may have a structure as shown in Figs. 1 and 2, but is not limited thereto.

For example, the organic electroluminescent device according to the present invention can be manufactured by using a known physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, An anode is formed by depositing an alloy thereof, an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, a hole blocking layer and an electron transporting layer is formed on the anode, and a substance usable as a cathode is deposited thereon .

In addition to such a method, an organic electroluminescent 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, a hole blocking 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 polymer materials by a method such as a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, .

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), titanium oxide (TiO), 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-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (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 LiAl and LiF / Al or LiO ₂ / Al, but the present invention is not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. In addition, a material having good surface adhesion with the positive electrode and having a planarization ability that can alleviate the surface roughness of the positive electrode is preferable. And a material having HOMO and LUMO values larger than the bandgap of the light emitting layer is preferable. In addition, materials having high thermal stability in chemical structure are preferable.

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 , Anthraquinone, polyaniline and polythiophene-based conductive polymers, 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 injection layer to the light emitting layer and having high mobility to holes is suitable. A material having HOMO and LUMO values larger than the bandgap of the light emitting layer is suitable. Materials with high chemical stability and thermal stability are also 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.

As the light emitting material, a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, is preferably a material having good quantum efficiency.

Specific examples include fluorene, carbazole, benzoxazole, benzthiazole and benzimi with blue ADN or MADN and DPVBi, BAlq and green Alq ₃ and other anthracenes, pyrenes, fluorenes, spiros, etc. Compounds represented by the dazole series and high molecular weight poly (p-phenylenevinylene), polypyro, polyfluorene and the like, but are not limited thereto.

As the hole blocking layer material, a material larger than the HOMO value of luminescence is suitable. Materials with high chemical stability and thermal stability are also suitable.

Specifically, TPBi and BCP are mainly used, and CBP, PBD, PTCBI, BPhen, and the like can be used, but 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 highly mobile, is suitable. Materials with high chemical stability and thermal stability are also suitable.

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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 electroluminescent 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, electronic paper (e-Paper) and the like.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

The arylamine compound of the present invention exhibits excellent electrical properties and hole transporting properties, and thus can be usefully used as a hole transport layer material of an organic electroluminescent device.

Synthetic example  1: Preparation of Compound A

A

A

2-bromo-9,9-dimethyl-9H-fluorene (5g, 18.30mmol) 1.0eq, 4-aminobiphenyl (4.65g, 27.45mmol) 1.5eq, Tris (Dibenzyldine) in a dried round flask Acetone) dipalladium (0) (335mg, 0.366mmol) 0.02eq, tri-tert-butylphosphine (74mg, 0.366mmol) 0.02eq, sodium tert-butoxide (2.6g, 27.45mmol) 1.5eq was added After sufficiently filling, 50 ml of anhydrous toluene was added thereto, followed by stirring at reflux for 3 hours at 85 ° C.

After the reaction mixture was cooled to room temperature, distilled water was added thereto to complete the reaction. The mixture was extracted with diethyl ether and distilled water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, and the mixture was separated by column with ethyl acetate and hexane to obtain a compound A (5.3 g, 80%).

1 H NMR (400 MHz, CDCl 3): δ 9.77 (s, 1H, NH), 7.81 (q, 1H), 7.75 (q, 2H), 7.38 to 7.59 (m, 8H), 7.28 (m, 1H), 6.75 (d, 1H), 6.52-6.58 (m, 3H), 1.67 (s, 6H)

Synthetic example  2: Preparation of compound B

B

B

2-bromo-9,9-dimethyl-9H-fluorene (5g, 18.30mmol) 1.0eq, aniline (2.55g, 27.45mmol) 1.5eq, tris (dibenzyldineacetone) dipalladium in a dried round flask (0) (335mg, 0.366mmol) 0.02eq, tri-tert-butylphosphine (74mg, 0.366mmol) 0.02eq, sodium tert-butoxide (2.6g, 27.45mmol) 1.5eq was added and filled with nitrogen 50 ml of anhydrous toluene was added, and it stirred at reflux at 85 degreeC for 3 hours.

After the reaction mixture was cooled to room temperature, distilled water was added thereto to complete the reaction. The mixture was extracted with diethyl ether and distilled water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, and the obtained mixture was separated by column with ethyl acetate and hexane to obtain a compound B (4.1 g, 80%).

¹ H NMR (400 MHz, CDCl 3): δ 9.75 (s, 1H, NH), 7.80 (q, 1H), 7.74 (q, 2H), 7.39 to 7.58 (m, 8H), 7.27 (m, 1H), 6.72 (d, 1H), 6.52-6.58 (m, 3H), 1.65 (s, 1H)

Synthetic example  3: Preparation of compound C

                                                               C

 2-bromo-9,9-dimethyl-9H-fluorene (5 g, 18.30 mmol) 1.0eq, 4-amino (1,1-biphenyl) -4-carbonitrile) (3.55 g) in a dried round flask , 27.45 mmol) 1.5eq, tris (dibenzyldineacetone) dipalladium (0) (335mg, 0.366mmol) 0.02eq, tri-tert-butylphosphine (74mg, 0.366mmol) 0.02eq, sodium tert-butoxide ( 2.6g, 27.45mmol) 1.5eq was added and nitrogen was sufficiently filled, 50ml of anhydrous toluene was added, and the mixture was stirred under reflux at 85 ° C for 3 hours.

  After the reaction mixture was cooled to room temperature, distilled water was added thereto to complete the reaction. The mixture was extracted with diethyl ether and distilled water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, and the mixture was separated by column with ethyl acetate and hexane to obtain a compound C (5.3 g, 75%).

¹ H NMR (400 MHz, CDCl 3): δ 9.79 (s, 1H, NH), 7.88 (q, 1H), 7.79 (q, 2H), 7.40-7.61 (m, 8H), 7.30 (m, 1H), 6.78 (d, 1H), 6.55 to 6.59 (m, 3H), 1.69 (s, 5H)

Synthesis Example 4 Preparation of Compound D

D

2-thienyl boronic acid (0.5g, 1.6mmol) 1.0eq, 4,4-dibromobiphenyl (204mg, 1.6mmol) 1eq in a dried round flask, tetrakis (triphenylphosphine) palladium (0) (55mg, 0.048mmol) 0.02eq, 2M Na ₂ CO ₃ was added, and the nitrogen was sufficiently filled, 20ml of anhydrous toluene was added and stirred under reflux for 24 hours at 110 ℃.

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After the reaction mixture was cooled to room temperature, distilled water was added thereto to complete the reaction. The mixture was extracted with diethyl ether and distilled water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, and the mixture was separated by column with ethyl acetate and hexane to obtain a compound D (0.35 mg, 70%).

1 H NMR (400 MHz, CDCl 3): δ 7.79 (q, 2H), 7.71 (q, 2H), 7.34 ~ 7.30 (m, 4H), 7.20 (m, 3H)

Synthetic example  5: Preparation of Compound E

E

2-thienyl boronic acid (0.5 g, 1.6 mmol) 1.0 eq, 9,10-dibromoanthracene (537 mg, 1.6 mmol) 1 eq, tetrakis (triphenylphosphine) palladium (0) in a dried round flask 55mg, 0.048mmol) 0.02eq, 2M Na ₂ CO ₃ and the nitrogen was sufficiently filled, 20ml of anhydrous toluene was added and stirred under reflux at 110 ℃ for 24 hours.

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After the reaction mixture was cooled to room temperature, distilled water was added thereto to complete the reaction. The mixture was extracted with diethyl ether and distilled water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, and the mixture was separated by column with ethyl acetate and hexane to obtain a compound E (0.39 g, 72%).

1 H NMR (400 MHz, CDCl 3): δ 7.53-7.48 (q, 4H), 7.34-7.30 (m, 4H), 7.20 (m, 3H)

Synthetic example  6: Preparation of Compound F

F

9,9-Spirofluorene-2-boronic acid (0.5g, 1.388mmol) 1.0eq, 2,5-dibromothiophene (335mg, 1.388mmol) 1eq, tetrakis (triphenyl) in a dried round flask Phosphine) palladium (0) (55mg, 0.048mmol) 0.02eq, 2M Na ₂ CO ₃ was added to the nitrogen and sufficiently filled with 20ml of anhydrous toluene was stirred at reflux at 110 ℃ for 24 hours.

After the reaction mixture was cooled to room temperature, distilled water was added thereto to complete the reaction. The mixture was extracted with diethyl ether and distilled water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, and the mixture was separated by column with ethyl acetate and hexane to obtain a compound F (0.52 g, 79%).

1 H NMR (400 MHz, CDCl 3): δ 7.60 (m, 5H), 7.38-7.35 (m, 5H), 7.29 (m, 1H), 6.80 (d, 2H), 6.60-6.55 (m, 4H)

Synthesis Example 7: Preparation of Compound A1

A1

Compound A (5g, 13.83mmol) 1.0eq, Compound D (8.77g, 27.84mmol) 1.5eq, Tris (dibenzyldineacetone) dipalladium (0) (340mg, 0.372mmol) 0.02eq, Tri -Tarter-butylphosphine (75mg, 0.372mmol) 0.02eq, sodium tert-butoxide (2.67g, 27.84mmol) 1.5eq was added and filled with nitrogen sufficiently, 50ml of anhydrous toluene was added and reflux stirring at 85 ° C for 3 hours. I was.

After the reaction mixture was cooled to room temperature, distilled water was added thereto to complete the reaction. The mixture was extracted with diethyl ether and distilled water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, and the mixture was separated with ethyl acetate and hexane, and the filtrate was separated by a column to obtain Compound A1 (6.3 g, 77%).

¹ H NMR (400 MHz, CDCl3): δ 7.75 ~ 7.70 (m, 6H), 7.38 ~ 7.32 (m, 8H), 7.28 ~ 7.24 (m, 9H), 6.75 (d, 1H), 6.52 ~ 6.58 (m , 3H), 1.67 (s, 6H)

Synthesis Example 8: Preparation of Compound A31

A31

Compound B (5g, 17.52mmol) 1.0eq, Compound E (5.94g, 26.28mmol) 1.5eq, Tris (dibenzyldineacetone) dipalladium (0) (320mg, 0.35mmol) 0.02eq, Tri -Tarter-butylphosphine (70mg, 0.35mmol) 0.02eq, sodium tert-butoxide (2.53g, 26.28mmol) 1.5eq was added and filled with nitrogen sufficiently, 50ml of anhydrous toluene was added and reflux stirring at 85 ° C for 3 hours. I was.

After the reaction mixture was cooled to room temperature, distilled water was added thereto to complete the reaction. The mixture was extracted with diethyl ether and distilled water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, and the mixture was separated by column with ethyl acetate and hexane to obtain a compound A31 (6.8 g, 72%).

1 H NMR (400 MHz, CDCl 3): δ 7.70 to 7.85 (m, 6H), 7.41 to 7.38 (m, 5H), 7.30 to 7.31 (m, 8H), 6.51 to 6.50 (m, 4H), 1.67 (s, 6H)

Synthesis Example 9: Preparation of Compound B1

B1

Compound A (5g, 13.83mmol) 1.0eq, Compound F (9.9g, 20.74mmol) 1.5eq, Tris (dibenzyldineacetone) dipalladium (0) (340mg, 0.372mmol) 0.02eq, Tri -Tarter-butylphosphine (75mg, 0.372mmol) 0.02eq, sodium tert-butoxide (2.67g, 27.84mmol) 1.5eq was added and filled with nitrogen sufficiently, 50ml of anhydrous toluene was added and reflux stirring at 85 ° C for 3 hours. I was.

After the reaction mixture was cooled to room temperature, distilled water was added thereto to complete the reaction. The mixture was extracted with diethyl ether and distilled water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, and the mixture was separated with ethyl acetate and hexane, and the filtrate was separated by a column to obtain Compound B1 (7.6 g, 73%).

¹ H NMR (400 MHz, CDCl3): δ 7.71-7.65 (m, 6H), 7.40-7.36 (m, 11H), 7.24-7.20 (m, 11H), 7.15-7.71 (m, 6H), 6.52-6.58 (m, 5H)

Synthesis Example 10 Preparation of Compound B7

B7

Compound C (5g, 12.94mmol) 1.0eq, Compound F (9.9g, 20.74mmol) 1.5eq, Tris (dibenzyldineacetone) dipalladium (0) (340mg, 0.372mmol) 0.02eq, Tri -Tarter-butylphosphine (75mg, 0.372mmol) 0.02eq, sodium tert-butoxide (2.67g, 27.84mmol) 1.5eq was added and filled with nitrogen sufficiently, 50ml of anhydrous toluene was added and reflux stirring at 85 ° C for 3 hours. I was.

After the reaction mixture was cooled to room temperature, distilled water was added thereto to complete the reaction. The mixture was extracted with diethyl ether and distilled water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, and the mixture was separated with ethyl acetate and hexane, and the filtrate was separated by a column to obtain Compound B7 (6.1 g, 61%).

¹ H NMR (400 MHz, CDCl3): δ 7.73 ~ 7.68 (m, 6H), 7.42 ~ 7.38 (m, 11H), 7.28 ~ 7.23 (m, 11H), 7.18 ~ 7.14 (m, 6H), 6.52 ~ 6.58 (m, 4H)

Example 1: Fabrication of organic electroluminescent device

A glass substrate coated with a film of ITO (indium tin oxide) having a thickness of 1500 Å was placed in secondary distilled water in which Fischer's detergent was dissolved, and ultrasonically cleaned. 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 transferred to a plasma cleaner. The substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transferred to a vacuum evaporator.

The hole injection layer was formed by thermally vacuum depositing an amine-based ELM200 with a thickness of 500 kPa on the prepared ITO transparent electrode. After vacuum depositing Compound A1 (300 kPa) obtained in Synthesis Example 7 as a hole transporting material, the anthracene-based MADN was vacuum deposited to a thickness of 300 kPa as a light emitting layer, and the Alq3 compound was vacuumed to a thickness of 300 kPa as an electron transporting layer. After deposition, lithium fluoride (LiF) 7 Å and 1000 Å thick aluminum were deposited to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at the deposition rate of 3-7 Å / sec.

Table 1 shows the characteristics of the organic electroluminescent device manufactured at the current density of 50 mA / cm ² , such as driving voltage, luminescence brightness, coloring coordinates, and luminous efficiency.

Example 2: Fabrication of organic electroluminescent device

An organic EL device was manufactured in the same manner as in Example 1, except that Compound B1, obtained in Synthesis Example 9, was used instead of Compound A1 as a material for transporting holes.

The characteristics of the organic electroluminescent device at a current density of 50 mA / cm ² , such as driving voltage, luminescence brightness, coloring coordinates, and luminous efficiency, were shown in Table 1.

Comparative Example 1: Fabrication of organic electroluminescent device

Example 1, except that N, N'-di (naphthalen-1-yl) -N, N'-diphenylbenzidine (NPB) represented by the following formula (4) instead of compound A1 as a material for transporting holes In the same manner as in the organic EL device was manufactured.

Formula 4

Table 1 shows the characteristics of the organic electroluminescent device manufactured at the current density of 50 mA / cm ² , such as driving voltage, luminescence brightness, coloring coordinates, and luminous efficiency.

Example 1 Example 2 Comparative Example 1 The driving voltage (V) 6.55 6.65 7.45 Light emission luminance (cd / m2) 5941 4950 4305 Color coordinates (0.14, 0.19) (0.14, 0.18) (0.14, 0.19) The luminous efficiency (cd / A) 10.7 10.2 9.3

When the result of using the asymmetric structure of the tertiary aryl amine according to the present invention as the hole transporting material in the organic light emitting device is compared with the result of using the commercially available material NPB in the organic light emitting device, the organic electroluminescence according to the present invention All of the devices showed excellent IVL characteristics with significantly improved efficiency while lower driving voltage. As described above, according to the present invention, the ability of the holes and the electrons to be improved is improved, thereby making it possible to manufacture organic light emitting diodes having low voltage, high efficiency, high brightness, and long life based on excellent hole transport and electron transport capabilities.

01 substrate
02 Anode
03 cathode
04 Hole injection layer
05 hole transport layer
06 Light emitting layer
08 Electron transport layer
09 Electron injection layer

Claims (12)

delete delete delete delete delete delete delete Used as a hole transport layer material of organic electroluminescent device,
Tertiary aryl amine compound having an asymmetric structure, characterized in that it is selected from the group of compounds represented by the following structural formula:

.
Used as a hole transport layer material of organic electroluminescent device,
Tertiary aryl amine compound having an asymmetric structure, characterized in that it is selected from the group of compounds represented by the following structural formula:

.
delete A first electrode; A second electrode; And at least one organic material layer formed between the first electrode and the second electrode.
Wherein the organic material layer includes a light emitting layer and a hole transporting layer,
The hole transport layer is an organic electroluminescent device comprising a tertiary aryl amine compound having an asymmetric structure according to claim 8 or 9. delete

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