KR101694492B1 - Amine compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to an amine compound and an organic electroluminescent device using the same. More particularly, the present invention provides an asymmetric tertiary arylamine compound having a specific structure including a heterocyclic group, The present invention relates to a tertiary arylamine compound which can realize a low driving voltage in addition to excellent luminescent characteristics, luminous efficiency, lifetime characteristics and thermal stability when used as a material, a method for producing the same, and an organic electroluminescent device using the same.

Description

[0001] The present invention relates to an amine compound and an organic electroluminescent device using the same.

The present invention relates to an amine compound and an organic electroluminescent device using the same. More particularly, the present invention provides an asymmetric tertiary arylamine compound having a specific structure including a heterocyclic group, The present invention relates to a tertiary arylamine compound which can realize a low driving voltage in addition to excellent luminescent characteristics, luminous efficiency, lifetime characteristics and thermal stability when used as a material, a method for producing the same, and an organic electroluminescent device using the same.

As the movement toward the information society accelerates, interest in electronic devices using organic semiconductors is rapidly increasing in the information electronics industry. Therefore, over the last 10 years, development of organic materials having semiconductive properties overcoming the durability problems of organic materials has been actively carried out and various applications have been actively studied. The field of applied research using organic semiconductors such as electromagnetic wave shielding films, organic EL displays, organic thin film transistors, and solar cells continues to expand. Organic semiconductors are expected to be indispensable for future industries as they have the advantages of simple fabrication processes, low cost, breakable by impact, and the ability to implement devices on thin and flexible substrates such as paper. In particular, the development of organic displays capable of meeting these needs is an important research area.

Organic light emitting (EL) devices are attracting attention as color display devices that complement the disadvantages of currently used display devices. Due to their high efficiency, self-luminescence, low temperature processability, ) Display. Particularly, the driving life of the organic light emitting diode (OLED) has been largely solved, and the materials to be used have been diversified.

Organic electroluminescent devices use organic electroluminescence characteristics when a voltage is applied, and organic thin films are stacked between an anode and a cathode. When a voltage is applied to the electrode, holes injected from the transparent anode and electrons injected from the cathode recombine in the light emitting layer, and light corresponding to the energy gap generated at this time is generated. However, in a simple structure, efficiency becomes low due to a large energy difference between the layers to the light emitting region of holes and electrons. (HIL), a hole transport layer (HTL), an electron injection layer (EIL), and an electron transport layer (Electron Injection Layer) to obtain high efficiency and low driving voltage by generating a large number of excitons. Transfer Layer (ETL). In this case, holes and electrons that do not form excitons will have a leakage current, so a balanced injection is needed. In order to inject holes and electrons from the electrode, it is necessary to go beyond the energy barrier. Therefore, the anode uses ITO having a small work function and the cathode has a low work function metal (Ca / Al, Li: Al, Mg: Ag , LiF / Al, LiF: Al / Al, etc.) is used.

The light emitting material of the organic electroluminescent device OLED is divided into fluorescence and phosphorescence. The method of forming a light emitting layer includes a method of doping a fluorescent host with a dopant, and a method of doping a fluorescent host with a dopant, (DPVBi, Rubrene, DCJTB, etc.) to the light emitting body, and a method of moving the emission wavelength to a long wavelength. Such doping is intended to improve the emission wavelength, efficiency, driving voltage, lifetime, and the like.

Such a thin film structure formed by a vacuum evaporation method in a general organic electroluminescent device can adjust the moving speed of holes and electrons to balance the density 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, not only the device must be constituted by the multilayer structure, but also the device material (for example, hole transport material, light emitting layer material, etc.) must be thermally and electrically stable. When a voltage is applied, a molecule having a low thermal stability due to heat generated in a device has a low crystal stability and is rearranged. As a result, local crystallization occurs, which causes deterioration and destruction of the device.

The hole transporting materials that have been used so far include m-MTDATA [4,4 ', 4 "-tris (N-3-methylphenyl-N-phenylamino) -triphenylamine], 2-TNATA [4,4' -Tris (N- (naphthylen-2-yl) -N-phenylamino) -triphenylamine], TPD [N, N'- 4'-diaminobiphenyl] and NPB [N, N'-di (naphthalen-1-yl) -N, N'-diphenylbenzidine]. However, since m-MTDATA, 2-TNATA, TPD and NPB have low glass transition temperatures (T _g ) of about 60 ° C and about 96 ° C, they have a fatal disadvantage of shortening the lifetime of the device.

To solve these problems, spiro-based materials such as OMeTAD, spiro-TAD, spiro-m-TTB, spiro-OMeTAD and spiro carb have been developed. However, And the like.

Accordingly, it is required to develop a new organic material which can realize various performance such as light emission characteristics, lifetime characteristics, thermal stability, and low driving voltage when used as an organic material layer material of an organic electroluminescent device, in particular, a hole transporting material.

Korean Patent Publication No. 10-2004-25986 "Spiro compounds and organic light emitting devices containing them" (March 27, 2004)

DISCLOSURE Technical Problem The present invention has been made to solve the problems of the prior art as described above, and it is an object of the present invention to provide an organic compound layer as an organic material layer of an organic electroluminescent device which has a high luminous efficiency and a low driving voltage, A hetero ring compound having a novel structure, a method capable of efficiently and economically synthesizing such a heterocyclic compound, and an organic electroluminescent device using the same.

In order to accomplish the above object, the present invention provides a tertiary arylamine compound having a specific structure including spirobifluorene, fluorene, and heterocyclic group.

The present invention also provides a process for producing the tertiary arylamine compound efficiently and economically.

Also, there is provided an organic electroluminescent device comprising the tertiary arylamine compound as an organic material layer material of an organic electroluminescent device, for example, a hole transporting layer material.

The present invention relates to a novel tertiary arylamine compound containing a spirobifluorene, a fluorene, and various heterocyclic (aryl) groups, in an organic electroluminescent device (for example, a hole transport layer of a multilayer organic electroluminescent device Thereby realizing excellent luminescence characteristics and thermal and electrical stability of the device and greatly improving the driving voltage, luminous efficiency, light emission luminance, color purity and lifetime characteristics.

In addition, the tertiary arylamine compound according to the present invention may have various properties depending on the kind of the substituent, besides the material for hole transport, and it may be a hole injection, a luminescence, a hole transport, an electron injection, And it is expected to contribute greatly to the improvement of the display industry by providing an organic electroluminescent device having high efficiency and 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.
FIG. 2 is a schematic view illustrating a multiple layer structure of an organic electroluminescent device according to another embodiment of the present invention. Referring to FIG.
3 and 4 are UV (Ultraviolet) / PL (Photoluminescence) spectra of the compounds 4A and 4I, respectively, prepared according to the present invention.
Figures 5 and 6 are data on the thermal stability of the compounds 4A and 4I prepared in accordance with the present invention, respectively.

Hereinafter, the present invention will be described in detail.

Tertiary arylamine compound

The tertiary arylamine compound according to the present invention is a heterocyclic compound represented by the following general formula (4). When the compound is used as an organic material layer of an organic electroluminescent device, it can realize excellent luminescence characteristics, thermal stability and electrical stability of the device, And the luminous efficiency, color purity and lifetime characteristics can be remarkably improved.

[Chemical Formula 4]

(In the formula 4,

Ar 1, Ar 2 and Ar 3 are each independently selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, fluorenyl and carbazole, unsubstituted or substituted with a phenyl group or a naphthyl group,

Ar 4 is a heterocyclic group containing at least one element selected from the group consisting of N, S and O,

n is 0 or 1.)

Specifically, the tertiary arylamine compound of the present invention is selected from the group of compounds represented by the following structural formulas, and they can be suitably used as an organic material layer material of an organic electroluminescent device.

FIG. 3 and FIG. 4 respectively show UV (Ultraviolet) / PL (Photoluminescence) spectra of the compounds 4A and 4I according to the present invention, respectively. The UV / PL spectrum is a graph measuring the emission wavelength of each compound in order to characterize the OLED, and measuring the wavelength at which light is most emitted by irradiating light of a wavelength absorbed through UV. UV / PL spectra can be obtained through a method known in the art. In the present invention, a solid film prepared by coating a solution containing the compounds 4A and 4I in quartz is irradiated with excitation light having a wavelength of about 343 nm to 356 nm To obtain a spectrum. As a result, as shown in FIG. 3 and FIG. 4, since the tertiary arylamine compound according to the present invention has the maximum emission peak at about 425 nm to 500 nm, the emission efficiency is expected to be very excellent. However, the specific values will depend on the purity of the compound, the surrounding environment, and so on.

5 and 6 respectively show data on the thermal stability of the compounds 4A and 4I prepared according to the present invention. In order to evaluate the thermal stability of the hole transport material, this can be evaluated by a known method in the art. In the present invention, a thermogravimetric analysis (TGA) Data on thermal stability were obtained by measuring the change in weight of the sample while increasing the temperature at a constant rate with the sample. As a result, as shown in FIG. 5 and FIG. 6, it can be confirmed that the compounds 4A and 4I have a thermal decomposition temperature of about 400 ° C or higher, and the tertiary arylamine compound according to the present invention has excellent thermal stability.

The tertiary arylamine compound according to the present invention can be applied to a flat panel display, a planar light emitter, a light emitting body of a surface emitting OLED for illumination, a flexible light emitter, a copying machine, a printer, an LCD backlight, a meter light source, And organic electronic devices such as organic solar cells (OSC), electronic paper (e-paper), organic photoconductor (OPC) and organic transistor (OTFT) can act on a principle similar to that applied to organic light emitting devices.

Preferably, the tertiary arylamine compound of the present invention is used as an organic material layer material of an organic electroluminescent device. Here, the organic material layer may include at least one of an electroluminescence layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer, Injection Layer), and the tertiary arylamine compound according to the present invention exhibits excellent electrical properties and hole transporting properties, and can be suitably used as a hole transporting material of an organic electroluminescent device .

In addition, the tertiary arylamine compound according to the present invention may have various properties depending on the type of the substituent, besides the hole transporting layer material, and perform all the functions such as hole injection, hole transport, electron injection and electron transport according to the substituent It has diversity that can be done.

Method for producing tertiary arylamine compound

The process for preparing the tertiary arylamine compound according to the present invention comprises the steps of: i) reacting a compound of the formula (1) with bis (tri-olso-tolylphosphine) palladium (II) dichloride to obtain a compound of the formula ) Reacting the resulting compound of formula (2) with a compound of formula (3) to produce a compound of formula (4).

The step i) comprises reacting a spirobifluorene compound of formula 1 with a bis (tri-olso-tolylphosphine) palladium (II) dichloride [(o-Tolyl) ₃ P-ClPdCl-P -Tolyl) ₃ ] to obtain an intermediate represented by the following formula (2).

[Chemical Formula 1]

(2)

(In the above formulas (1) and (2)

Ar1 and Ar2 are each independently selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, fluorenyl, and carbazole, unsubstituted or substituted with a phenyl group or a naphthyl group,

n is 0 or 1.)

In the present invention, it is possible to synthesize the desired tertiary arylamine compound in addition to the bis (tri-ortho-tolylphosphine) palladium (II) dichloride without addition of a ligand, thereby greatly reducing the synthesis cost.

In step ii), the intermediate of formula (2) obtained in step i) is reacted with an aminobutyltin compound of formula (3), which is a reactant for imparting a central element N of the target, to obtain an asymmetric 3- Lt; RTI ID = 0.0 > arylamine < / RTI > compound.

(3)

[Chemical Formula 4]

(In the above formulas 3 and 4,

Ar 1, Ar 2 and Ar 3 are each independently selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, fluorenyl and carbazole, unsubstituted or substituted with a phenyl group or a naphthyl group,

Ar 4 is a heterocyclic group containing at least one element selected from the group consisting of N, S and O,

n is 0 or 1.)

The reaction according to the present invention is carried out at a low and mild temperature, so that it is possible to eliminate side effects or byproducts generated during the reaction at a severe reaction temperature. In one embodiment, the reaction of the compound of Formula 2 with the compound of Formula 3 may be carried out at an experimental temperature of 85-110 ° C. (eg, about 100 ° C.). If the temperature is less than 85 캜, the reaction itself may not proceed or a large amount of unreacted material may remain. If the temperature exceeds 110 캜, undesired side reactions may occur or unnecessary large amounts of energy may be required for the synthesis.

Further, in the production method according to the present invention, even when only a small amount of base is used in the reaction of the compound of Formula 2 and the compound of Formula 3, the target tertiary arylamine compound can be obtained smoothly, Can be saved. In one embodiment, 0.5 to 1.0 equivalent (eq) of base may be used. When the amount of the base used is less than 0.5 equivalent, the reaction proceeds insignificantly and the yield may be lowered. If the amount of the base used is more than 1.0 equivalent, an unnecessary amount of base may be added unnecessarily than the amount required to obtain the target product, .

In addition, the synthesis of the tertiary arylamine compound according to the present invention is advantageous in that the reaction time is short and the desired product can be easily obtained through the column at a high yield.

Organic electroluminescent device

According to another aspect of the present invention, there is provided an organic electroluminescent device including an asymmetric tertiary arylamine compound as described above.

The organic layer of the organic electroluminescent device of the present invention may have a single layer structure of one layer or a multilayer structure of two or more layers including a light emitting layer. When the organic compound layer of the organic electroluminescent device of the present invention has a multilayer structure, it may have a structure in which a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer are stacked. That is, the organic electroluminescent device of the present invention may have the structure shown in FIG. 1 (single layer structure) and FIG. 2 (multiple layer structure), but it is not limited thereto.

Specifically, the present invention comprises a first electrode (02), a second electrode (03) formed on a substrate (01), and at least one organic layer disposed between the electrodes and at least one layer of the organic layer An organic electroluminescent device comprising a tertiary arylamine compound according to the present invention is provided.

In the organic electroluminescent device of the present invention, the organic material layer includes a hole injecting layer 04, a hole transporting layer 05, a light emitting layer 06, a hole blocking layer (not shown), an electron transporting layer 08, And one or two layers of the hole injection layer 04, the hole transport layer 05, the hole blocking layer (not shown), the electron transport layer 08 and the electron injection layer 09 are omitted as necessary Lt; / RTI >

The organic electroluminescent device can be manufactured by a conventional method and materials for manufacturing an organic electroluminescent device, except that one or more organic compound layers are formed using the above-mentioned tertiary arylamine compound.

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, Or an alloy thereof to form an anode and an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, a hole blocking layer, an electron transporting layer, and an electron injecting layer is formed thereon, ≪ / RTI > In addition, an organic electroluminescent device may be manufactured by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate. Here, the organic material layer may be formed by using a variety of polymeric materials and not a deposition method but a fewer number of layers (for example, a single layer) by a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, Can also be produced.

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. Specifically, 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), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; A conductive polymer such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline may be used, no.

As the negative electrode material, a material having a small work function is preferably used to facilitate electron injection into the organic material layer. Specifically, 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 may be used, but the present invention is not limited thereto.

As the hole injection layer material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection layer material be between the work function of the anode material and the HOMO of the peripheral organic layer . It is also preferable to use a material having a surface adhesion with the anode and a planarizing ability capable of alleviating the surface roughness of the anode. Materials having a HOMO value and a lowest unoccupied molecular orbital (LUMO) value larger than the band gap of the light emitting layer and a material having a high chemical stability and thermal stability are preferable. Specifically, examples of the hole injection layer material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene perylene-based organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers may be used, but the present invention is not limited thereto.

As the hole transport layer material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is preferable. Materials having HOMO and LUMO values larger than the band gap of the light emitting layer and materials having high chemical stability and thermal stability are preferable. Specifically, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together may be used, but a tertiary arylamine compound according to the present invention is preferably used.

As the light emitting layer material, a material capable of emitting light in a 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. Specifically, a blue series of ADN or MADN, DPVBi, BAlq and the like and green series Alq ₃ and other anthracene, pyrene, fluorene, spirobifluorene, carbazole, benzoxazole, benzthiazole and benzimidazole series And poly (p-phenylenevinylene), polypyrene, polyfluorene, and the like can be used, but the present invention is not limited thereto.

As the hole blocking layer material, a material larger than the HOMO value of the light emitting layer is preferable. Materials having high chemical stability and thermal stability are also desirable. Specifically, TPBi and BCP are mainly used, and CBP, PBD, PTCBI, and BPhen may be used, but the present invention is not limited thereto.

As the electron transport layer and the electron injection layer material, a material capable of injecting electrons from the cathode well and transferring the electrons to the light emitting layer is preferable. Materials with high chemical stability and thermal stability are also suitable. Specifically, Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complex, and the like may be used, but the present invention is 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.

Hereinafter, the present invention will be described more specifically by way of Synthesis Examples and Examples. However, these synthesis examples and examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

Synthesis Example 1: Preparation of Compound 2A

To a dried round flask was added 1.5 eq of 2-bromo-9,9'-spirobifluorene (8.2 g, 20.74 mmol), bis (tri-olso-tolylphosphine) palladium (II) dichloride (227 mg, 0.29 mmol) and 30 ml of anhydrous toluene were placed, and the mixture was refluxed and stirred at 80 ° C for about 1 hour. After cooling to room temperature, it was concentrated to obtain Compound 2A.

Synthesis Example 2: Preparation of Compound 4A

To a dried round flask was added 1.0 eq of N- (9,9-dimethyl-9H-fluoren-2-yl) thiophene-2-amine (5.1 g, 17.52 mmol) (5.3 g, 14.89 mmol) were charged and sufficiently purged with nitrogen. 40 ml of anhydrous toluene was added and the reaction was carried out at 85 ° C. for 1 hour. Then, Compound 2A was dissolved in 30 ml of anhydrous toluene, And the mixture was refluxed and stirred.

Then, the reaction mixture was cooled to room temperature, and the reaction was terminated. The reaction mixture was extracted with diethyl ether and 4N HCl solution, and the solvent of the organic layer was removed using a vacuum concentrator. The obtained compound was extracted again with diethyl ether and 10% KF aqueous solution, and then 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 subjected to column separation using ethyl acetate and hexane to obtain Compound 4A (5.1 g, 81%).

FD-MS: m / z = 606.22 (C ₄₄ H ₃₁ NS = 605.79)

Synthesis Example 3: Preparation of compound 4B

(9,9-dimethyl-9H-fluoren-2-yl) thiophene-2-amine in Synthesis Example 2 instead of N- (9,9- Compound 4B was prepared in the same manner except using 5- (naphthalen-1-yl) thieno [3,2-b] thiophen-2-amine.

FD-MS: m / z = 788.24 (C ₅₆ H ₃₇ S ₂ = 788.03)

Synthesis Example 4: Preparation of Compound 4C

(9,9-dimethyl-9H-fluoren-2-yl) thiophene-2-amine in Synthesis Example 2 instead of N- (9,9- Benzo [b] thiophen-2-amine, the compound 4C was prepared.

FD-MS: m / z = 656.24 (C ₄₈ H ₃₃ N ₆ S = 655.85)

Synthesis Example 5: Preparation of compound 4D

(9,9-dimethyl-9H-fluoren-2-yl) thiophene-2-amine in Synthesis Example 2 instead of N- (9,9- Benzo [b] thiophen-6-amine, the compound 4D was prepared.

FD-MS: m / z = 656.24 (C ₄₈ H ₃₃ NS = 655.85)

Synthesis Example 6: Preparation of Compound 4E

(9,9-dimethyl-9H-fluoren-2-yl) thiophene-2-amine in Synthesis Example 2 instead of N- (9,9- Compound 4E was prepared in the same manner except that thiazol-2-amine was used.

FD-MS: m / z = 607.22 (C 34 H 30 N 2 S = 606.78)

Synthesis Example 7: Preparation of compound 4F

(9,9-dimethyl-9H-fluoren-2-yl) thiophene-2-amine in Synthesis Example 2 instead of N- (9,9- Benzo [d] thiazol-2-amine, the compound 4F was prepared.

FD-MS: m / z = 657.23 (C ₄₇ H ₃₂ N ₂ S = 656.84)

Synthesis Example 8: Preparation of Compound 4G

(9,9-dimethyl-9H-fluoren-2-yl) thiophene-2-amine in Synthesis Example 2 instead of N- (9,9- Compound 4G was prepared in the same manner except that benzofuran-2-amine was used.

FD-MS: m / z = 640.26 (C ₄₈ H ₃₃ NO = 639.78)

Synthesis Example 9: Preparation of compound 4H

(4- (10H-phenoxazin-10-yl) phenyl) -9 (9,9-dimethyl-9H-fluoren-2-yl) thiophen- , 9-dimethyl-9H-fluoren-2-amine, the compound 4H was prepared in the same manner.

FD-MS: m / z = 781.32 (C ₅₈ H ₄₀ N ₂ O = 780.95)

Synthesis Example 10: Preparation of Compound 4I

(9,9-dimethylacridine-10 (9H-fluoren-2-yl) thiophene-2-amine in Synthesis Example 2 instead of N- ) -Yl) phenyl) -9,9-dimethyl-9H-fluoren-2-amine.

FD-MS: m / z = 807.37 (C ₆₁ H ₄₆ N ₂ = 807.03)

Synthesis Example 11: Preparation of Compound 4J

(10-phenylphenazin-5 (10H) -yl) thiophene-2-amine in Synthesis Example 2 instead of N- (9,9-dimethyl-9H- Phenyl) -9,9-dimethyl-9H-fluoren-2-amine was used in the same manner.

FD-MS: m / z = 856.36 (C ₆₄ H ₇₅ N ₃ = 856.06)

Synthesis Example 12: Preparation of Compound 4K

(4- (3,5-diphenyl-4H-1, 2-dihydro-2H-pyrazol-4-yl) 4-yl) phenyl) -9,9-dimethyl-9H-fluorene-2-amine.

FD-MS: m / z = 819.34 (C ₆₀ H ₄₂ N ₄ = 819.00)

Example 1: Fabrication of organic electroluminescent device

Before the deposition for the device fabrication, a glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1500 Å was cleaned (impurities and particulates on the surface were changed by organic substances, deterioration of interfacial properties between ITO and organic materials, A phenomenon in which light is not partially or totally caused due to burning of impurities at the time of contact, defective contact with ITO, and shortening of the lifetime of the device). In order to remove impurities such as organic substances, ionic substances, and metal substances present on the substrate before the organic material deposition, the substrate was removed by ultrasonic cleaning for 5 minutes at room temperature using acetone, followed by IPA (isopropyl alcohol) Ultrasonic cleaning was performed for a minute and then dried using N ₂ gas.

On the prepared ITO transparent electrode, an amine-based WDH-300 was thermally vacuum deposited to a thickness of 150 Å to form a hole injection layer. Compound 4A obtained in Synthesis Example 2, which is a hole transporting material, was vacuum deposited to a thickness of 250 ANGSTROM. Then, an Ir compound was doped into CBP as a light emitting layer and vacuum evaporated to a thickness of 250 ANGSTROM. , Lithium fluoride (LiF) having a thickness of 5 Å and aluminum having a thickness of 1500 Å were sequentially deposited to form a cathode. Here, the organic material deposition rate was 1 Å / sec, the lithium fluoride deposition rate was 0.2 Å / sec, and the aluminum deposition rate was 2 to 3 Å / sec.

The characteristics of the organic electroluminescent device manufactured at the current density of 10 mA / cm ² , such as driving voltage, luminescence brightness, and luminous efficiency, are shown in Table 1 below.

Example 2: Fabrication of organic electroluminescent device

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the compound 4E obtained in Synthesis Example 6 was used instead of the compound 4A as the hole transport material.

The characteristics of the organic electroluminescent device at a current density of 10 mA / cm ² , such as driving voltage, luminescence brightness, and luminous efficiency, are shown in Table 1 below.

Example 3: Fabrication of organic electroluminescent device

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the compound 4I obtained in Synthesis Example 10 was used instead of the compound 4A as the hole transport material.

The characteristics of the organic electroluminescent device at a current density of 10 mA / cm ² , such as driving voltage, luminescence brightness, and luminous efficiency, are shown in Table 1 below.

Example 4: Fabrication of organic electroluminescent device

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the compound 4J obtained in Synthesis Example 11 was used instead of the compound 4A as the hole transport material.

The characteristics of the organic electroluminescent device at a current density of 10 mA / cm ² , such as driving voltage, luminescence brightness, and luminous efficiency, are shown in Table 1 below.

Example 5: Fabrication of organic electroluminescent device

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the compound 4K obtained in Synthesis Example 12 was used instead of the compound 4A as the hole transport material.

The characteristics of the organic electroluminescent device at a current density of 10 mA / cm ² , such as driving voltage, luminescence brightness, and luminous efficiency, are shown in Table 1 below.

Comparative Example 1: Fabrication of organic electroluminescent device

(Naphthalene-1-yl) -N, N'-diphenylbenzidine (NPB) represented by the following formula 5 was used in place of the compound 4A as the hole transport material, An organic electroluminescent device was fabricated.

[Chemical Formula 5]

The characteristics of the organic electroluminescent device manufactured at the current density of 10 mA / cm ² , such as driving voltage, luminescence brightness, and luminous efficiency, are shown in Table 1 below.

 [Table 1]

As shown in Table 1, when an amine compound according to the present invention is used as a hole transporting layer material, an organic electroluminescent device, such as a low voltage, a high efficiency, a high brightness and a thermal stability, It is possible to realize all the required characteristics harmoniously.

01: substrate
02: anode (or first electrode)
03: cathode (or second electrode)
04: Hole injection layer
05: Hole transport layer
06: light emitting layer
07: Electron transport layer
08: Electron injection layer

Claims (9)

A tertiary arylamine compound selected from the group of compounds represented by the following structural formula:

.
The method according to claim 1,
The tertiary arylamine compound can be used in various fields such as a flat panel display, a planar illuminant, an illuminant of a surface emitting OLED for illumination, a flexible illuminant, a copier, a printer, an LCD backlight, a meter light source, a display plate, an organic electroluminescent device, Characterized in that it is applied to paper (e-paper), organophotoreceptor (OPC) or organic transistor (OTFT).
3. The method of claim 2,
Wherein the tertiary arylamine compound is used as an organic material layer material of an organic electroluminescent device.
The method of claim 3,
Wherein the tertiary arylamine compound is used as a hole transport layer material of an organic electroluminescent device.
Reacting a compound of formula 1 with bis (tri-olso-tolylphosphine) palladium (II) dichloride to give a compound of formula 2,
Reacting the resulting compound of formula (2) with a compound of formula (3) to produce a compound of formula (4)
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

(In the above Chemical Formulas 1 to 4,
Ar 1, Ar 2 and Ar 3 are each independently selected from the group consisting of phenyl, biphenyl, naphthyl, anthracenyl, fluorenyl and carbazole, unsubstituted or substituted with a phenyl group or a naphthyl group,
Ar 4 is a heterocyclic group containing at least one element selected from the group consisting of N, S and O,
n is 0 or 1.)
Wherein the compound of Formula 4 is selected from the group of compounds represented by the following structural formulas:
Method for preparing tertiary arylamine compound:

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1. An organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the electrodes,
Wherein the one or more organic layers include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer,
Wherein the hole transport layer comprises the tertiary aryl amine compound according to claim 1. delete delete delete

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