KR20130120855A - Using thiophen derivative as hole transporting mateial and organic electroluminescent device using the same - Google Patents

Abstract

The present invention provides a tertiary aryl amine containing thiophene and an organic electroluminescent compound containing the same. The compound has superior electrical properties, light emitting properties, and high charge transport ability and is useful as a charge transport material which is suitable for fluorescent and phosphorescent dopants with red, blue, and white colors. Also, the synthetic process of the compound is economical. The compound has superior hole deliver ability and electron transport ability due to an asymmetric structure, has high glass transition temperature, and shows thermal and electrical stability, thereby improving lifetime of a device with little crystallization phenomenon when the device is stored and driven. [Reference numerals] (01) Substrate;(02) Anode;(03) Cathode;(06) Light-emitting layer

Description

   Hole transporting material using thiophene and organic electroluminescent device including same TECHNICAL FIELD

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

The organic electroluminescent device was first discovered in 1965 by an organic light emitting material from anthracene single crystals by Pope et al., And has a laminated structure of functional separation type by dividing organic material into hole receiving layer and emitting layer by Kodak's Tang in 1987. Since the light emitting diodes have been proposed, "low voltage driving organic EL devices by stacked devices" (CWTang, SAVanslyke, Applied Physics Letters, 1987, 51 , 913), materials for light emitting devices including various kinds of organic materials have been developed so far. have.

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. Therefore, organic light-emitting diodes (OLEDs) are attracting attention as next-generation display devices that can compensate for these problems. OLEDs are self-luminous display devices that have wide viewing angles, excellent contrast, and fast response times.

A general organic light emitting device is a self-light emitting device using a principle that electrons and holes injected through a cathode and an anode form an exciton having recombination energy in an organic thin film, and light of a specific wavelength is generated from the formed excitons.

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 EL device includes an anode, a hole injection layer (HIL) that receives holes from an anode, a hole transport layer (HTL) that transports holes, an emission layer (EML) that combines holes and electrons, and emits electrons. It consists of an electron transport layer (ETL) and a cathode which receive from and deliver to a light emitting layer. 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 commercialize and improve the characteristics of the organic electroluminescent device, not only the device is configured in a multilayer structure as described above, but also the device material, in particular, the hole transport material must be thermally and electrically stable. 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 up to now 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, TPD and NPB also have a low glass transition temperature of 60 ℃ and 96 ℃, respectively, There is a fatal disadvantage of shortening the lifespan.

The conventional hole transport materials used in organic electroluminescent devices still need to improve performance, and thus there is a need for excellent materials that can improve device lifetime and luminous efficiency.

The present invention is designed to improve the problems of the prior art as described above, by introducing aromatic and florene heteroaryl groups in the tertiary amine, and excellent thermal stability as a transport material of the organic electroluminescent device of a multi-layer structure and increase the lifespan In addition, the present invention provides an organic EL device having excellent luminescence brightness and efficiency.

In the present invention to achieve the above object,

It provides a tertiary aryl amine compound using thiophene represented by the formula (2), (3).

Formula 1

Ar ₁ and Ar ₂ in Formula 1 Are the same or different and are each selected from an arylene group of C5 to C30 and a heteroarylene group of C5 to C30,

R Is the same or different and is any one selected from H, C5 to C30 aryl groups, C5 to C30 arylene groups, and heteroarylene groups.

   L represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 15 carbon atoms, or a substituted or unsubstituted condensed polycyclic group having 4 to 20 carbon atoms.

Ar ₁ of Chemical Formula ₁ And Ar ₂ Are halogen, amino group, nitrile group, nitro group, amine group, arylamine group or C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₁ ~ C ₄₀ At least one selected from the group consisting of an alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₃ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group and a C ₅ to C ₄₀ heteroaryl group Thiophene compounds characterized by the same or different characteristics:

In Formula 1, Ar ₁ and Ar ₂ are each independently an aryl group selected from a phenyl group, a naphthyl group, a biphenyl group, a fluorene group, and a carbazole group, or a C1-C4 alkyl, C1-C5 alkoxy, sia A thiophene compound characterized by being an aryl group in which one to three of the furnace, amine, phenoxy, phenyl, fluorene group or halogen are substituted.

R ₃ in Formula 1 is each independently a thiophene compound, characterized in that any one selected from the group consisting of a hydrogen atom, phenyl group, naphthyl group, fluorene group, carbazolyl group

   In Formula 1, L is a thiophene compound, characterized in that selected from the following structures:

    In Formula 1, L has a substituted or unsubstituted group

If R ₃ is C ₀ ,

Thiophene compound represented by the following formula:

(2)

A thiophene compound represented by the following Formula in Formula 1, wherein L is a simple linking group:

(3)

The tertiary aryl amine using the thiophene is a flat panel display, a flat light emitter, a light emitter of an illuminated surface emitting OLED, a flexible light emitter, a copier, a printer, an LCD backlight, a meter light source, a display panel, an organic light emitting diode (OLED), an organic solar cell It may be applied to any one selected from an OSC, an electronic paper, an organic photoconductor, and an organic transistor, but is not limited thereto.

The present invention also provides an organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer between these electrodes, wherein at least one layer of the organic layer comprises the tertiary aryl amine.

The at least one organic layer may include a light emitting layer, and may further include at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

Compound according to the present invention is designed to improve the problems of the prior art, by introducing an aromatic and florene hetero aryl group in the aryl amine as a transport material of the organic electroluminescent device of a multi-layer structure, excellent thermal stability and increase the lifespan In addition, it will be possible to provide an organic EL device having excellent luminescence brightness and efficiency. In addition, the arylamine 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 may serve as a 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 EL device having excellent color purity.

Compound according to the present invention is designed to improve the problems of the prior art, by introducing an aromatic and florene hetero aryl group in the aryl amine as a transport material of the organic electroluminescent device of a multi-layer structure, excellent thermal stability and increase the lifespan In addition, it will be possible to provide an organic EL device having excellent luminescence brightness and efficiency. In addition, the arylamine 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 may serve as a 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 EL device having excellent color purity.

The present invention provides a tertiary aryl amine compound using thiophene represented by the following formula (1), (2) and (3).

Formula 1

Ar ₁ and Ar ₂ in Formula 1 Are the same or different and are each selected from an arylene group of C5 to C30 and a heteroarylene group of C5 to C30,

R Is the same or different and is any one selected from H, C5 to C30 aryl groups, C5 to C30 arylene groups, and heteroarylene groups.

   L represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 15 carbon atoms, or a substituted or unsubstituted condensed polycyclic group having 4 to 20 carbon atoms.

Ar ₁ of Chemical Formula ₁ And Ar ₂ is halogen, amino group, nitrile group, nitro group, amine group, arylamine group or C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₁ Any one selected from the group consisting of -C ₄₀ alkoxy group, C ₃ -C ₄₀ cycloalkyl group, C ₃ -C ₄₀ heterocycloalkyl group, C ₆ -C ₄₀ aryl group and C ₅ -C ₄₀ heteroaryl group Thiophene compounds characterized by the same or different from each other above:

In Formula 1, Ar ₁ and Ar ₂ are each independently an aryl group selected from a phenyl group, a naphthyl group, a biphenyl group, a fluorene group, and a carbazole group, or a C1-C4 alkyl, C1-C5 alkoxy, sia A thiophene compound characterized by being an aryl group in which one to three of the furnace, amine, phenoxy, phenyl, fluorene group or halogen are substituted.

R ₃ in Formula 1 is each independently a thiophene compound, characterized in that any one selected from the group consisting of a hydrogen atom, phenyl group, naphthyl group, fluorene group, carbazolyl group

   In Formula 1, L is a thiophene compound, characterized in that selected from the following structures:

    In Formula 1, L has a substituted or unsubstituted group

If R is C ₀ ,

Thiophene compound represented by the following formula:

(2)

A thiophene compound represented by the following Formula in Formula 1, wherein L is a simple linking group:

(3)

.

 3 and 4 show data on UV / (Ulttraviolet) / PL (Photoluminescence) spectrum and thermal stability of Compound A1, which is an example of the tertiary aryl amine represented by Chemical Formula 1.

The UV (Ultraviolet) / PL (Photoluminescene) spectrum of FIG. 3 measures the emission wavelength of each compound to characterize the OLED, and measures the wavelength at which the most emission occurs by irradiating light of the wavelength absorbed through the UV. One graph.

The UV (Ultraviolet) / PL (Photoluminescene) spectrum can be obtained through a method known in the art, in the present invention is about 340nm wavelength in a solid film prepared by coating a solution containing the compound 1 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 1 was weighed on the sample, and the weight change of the sample was measured while increasing the temperature at a constant rate, thereby obtaining data on thermal stability. As a result, as shown in FIG. 4, it was confirmed that the thermal decomposition temperature of the compound 1 had excellent thermal stability at about 300 ° C. or more. Based on this, the tertiary aryl amine represented by Formula 1 according to the present invention was about 300 ° C. It can be seen that the thermal stability is shown even at high temperature.

On the other hand, the present invention also provides an organic electroluminescent material comprising the arylamine compound of Formula 1 as described above.

The organic electroluminescent material may be prepared by a conventional method and material for manufacturing an organic electronic device, except that at least one organic layer is formed using the arylamine compound of Formula 1 described above.

That is, the organic electronic device of the present invention includes a first electrode, a second electrode and one or more organic material layers disposed between these electrodes, and at least one or more of the organic material layers is an arylamine derivative represented by Chemical Formula 1 of the present invention. It includes.

In addition, in the organic electronic 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, and an electron transport layer, and if necessary, one or two hole injection layers, hole transport layers, hole blocking layers, and electron transport layers. It can be used with the 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, 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, for example, it is 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), electron It may have a structure in which an electron transport layer or the like is stacked.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in Figs. 1 to 3, but is not limited thereto.

For example, the organic light emitting device according to the present invention is a metal oxide having a metal or conductivity on a substrate or a metal oxide on a substrate using known physical vapor deposition (PVD) methods such as sputtering or e-beam evaporation It can be prepared by depositing an alloy of the anode to form an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon have.

In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode 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), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-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 LiO2 / Al, but are not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material 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 benzimidazole with blue ADN or MADN and DPVBi, BAlq and green Alq3 and other anthracenes, pyrenes, fluorenes, spiros, etc. Compounds represented by the series, and polymeric 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.

Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used. The compound according to the present invention may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, 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.

Since the aryl amine compound of the present invention exhibits excellent electrical and hole transport properties, it may be usefully used as a hole transport layer material of an organic light emitting device.

Synthetic example  1: Preparation of Compound A

A

A

2-bromo-9,9-dimethyl-9H-fluorene (5 g, 18.30 mmol) 1.0 eq, 4-aminobiphenyl (4.65 g, 27.45 mmol) 1.5 eq, 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) After filling, 50 ml of anhydrous toluene was added and 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 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 (5 g, 18.30 mmol) 1.0 eq, aniline (2.55 g, 27.45 mmol) 1.5 eq, 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 thoroughly with nitrogen 50 ml of toluene was added and 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 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 (2.6 g, 27.45mmol) 1.5eq was added, 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)

Synthetic example  4: Preparation of Compound D

D

    2-thienyl boronic acid (0.5 g, 1.6 mmol) 1.0 eq, 4,4-dibromobiphenyl (204 mg, 1.6 mmol) 1 eq, tetrakis (triphenylphosphine) palladium (0)

(55mg, 0.048mmol) Add 0.02eq, 2M Na ₂ CO ₃ and sufficiently fill with nitrogen, add 20ml of anhydrous toluene and stir at reflux at 110 ° C 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 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)

(55mg, 0.048mmol) Add 0.02eq, 2M Na ₂ CO ₃ and sufficiently fill with nitrogen, add 20ml of anhydrous toluene and stir at reflux at 110 ° C 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 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-Spyrofluorene-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 and 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), 6.80d, 2H), 6.60-6.55 (m, 4H)

Synthetic example  7: Preparation of Compound A1

A1

Compound A (5g, 13.83mmol) 1.0eq, Compound B (8.77g, 27.84mmol) 1.5eq, Tris (dibenzyldineacetone) dipalladium (0) (340mg, 0.372mmol) 0.02eq, Tri in a dried round flask -Tut-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 it stirred under reflux for 3 hours at 85 degreeC. .

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)

Synthetic example  8: Preparation of Compound A31

A31

Compound B (5g, 17.52mmol) 1.0eq, Compound B (5.94g, 26.28mmol) 1.5eq, Tris (dibenzyldineacetone) dipalladium (0) (320mg, 0.35mmol) 0.02eq, Tri -Tut-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 stirred under 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 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 -Tut-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 it stirred under reflux for 3 hours at 85 degreeC. .

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)

Synthetic example  10: Preparation of Compound B7

B7

Compound A (5g, 12.94mmol) 1.0eq, Compound F (9.9g, 20.74mmol) 1.5eq, Tris (dibenzyldineacetone) dipalladium (0) (340mg, 0.372mmol) 0.02eq, Tri -Tut-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 it stirred under reflux for 3 hours at 85 degreeC. .

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: Organic field  Manufacture of light emitting 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. After ITO was fined for 30 minutes, the ultrasonic cleaning was performed twice with distilled water 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 for 5 minutes using an oxygen plasma and then transferred to a vacuum evaporator.

An amine-based ELM200 was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. After vacuum depositing Compound A1 (300 kPa) obtained in Synthesis Example 8 as a hole transporting material, an anthracene-based MADN was vacuum deposited to a thickness of 300 kPa as an emitting layer, and an 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 thickness of 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: Organic field  Manufacture of light emitting device

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Compound B1 obtained in Synthesis Example 12 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: Organic field  Manufacture of light emitting 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 was used as a material for transporting holes In the same manner, an organic EL device was manufactured.

Formula 4

The characteristics of the driving voltage, light emission luminance, color coordinate, and light emission efficiency at the current density of 50 mA / cm ² of the organic light emitting device manufactured above are shown in Table 1 below.

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 tertiary aryl amine having an asymmetric structure represented by the formula (1) according to the present invention as a hole transporting material in the organic light emitting device is compared with the result of using NPB, which is a commercially available material in the organic light emitting device, All of the organic light emitting diodes exhibited excellent IVL characteristics with significantly improved efficiency while low driving voltage. As described above, according to the present invention, excellent mobility of holes and electrons is improved, and thus low-voltage, high-efficiency, high brightness, and long-life organic light emitting devices based on excellent hole transport and electron transport capabilities can be manufactured.

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

Claims (12)

Tertiary aryl amines represented by Formula 1:
Formula 1

Ar ₁ and Ar ₂ in Formula 1 Are the same or different and are each selected from an arylene group of C5 to C30 and a heteroarylene group of C5 to C30,
R is the same or different and is any one selected from H, a C5 to C30 aryl group, a C5 to C30 arylene group, and a heteroarylene group.
L represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 4 to 15 carbon atoms, or a substituted or unsubstituted condensed polycyclic group having 4 to 20 carbon atoms. The method of claim 1,
Ar ₁ of Chemical Formula ₁ And Ar ₂ Are halogen, amino group, nitrile group, nitro group, amine group, arylamine group or C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₁ ~ C ₄₀ At least one selected from the group consisting of an alkoxy group, a C ₃ to C ₄₀ cycloalkyl group, a C ₃ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group and a C ₅ to C ₄₀ heteroaryl group Thiophene compounds characterized by the same or different The C1-C4 alkyl, C1-C5 alkoxy of claim ₁ , wherein Ar ₁ and Ar ₂ are each independently an aryl group selected from a phenyl group, a naphthyl group, a biphenyl group, a fluorene group, and a carbazole group or an aromatic ring thereof. , Thiophene compound, characterized in that cyano, amine, phenoxy, phenyl, fluorene group or halogen is an aryl group substituted with 1 to 3 The thiophene compound according to claim 1, wherein in Formula 1, R ₃ is each independently selected from a group consisting of a hydrogen atom, a phenyl group, a naphthyl group, a fluorene group, and a carbazolyl group: The thiophene compound according to claim 1, wherein L is selected from the following structures:

The method of claim 1,
In the above formula, L has a substituted or unsubstituted group
If R is C ₀ ,
Thiophene compound represented by the following formula:
Formula 2

The method of claim 1,
A thiophene compound represented by the following formula in which L is a simple linking group:
Formula 3

Specific examples of the compound belonging to Formula 2, which is a compound based on a thiophene derivative, according to an embodiment of the present invention include the compounds of Formula 4 below, but the present invention is not limited thereto.
Formula 4

Specific examples of the compound belonging to Formula 3, which is a compound based on a thiophene derivative, according to an embodiment of the present invention include the compounds of Formula 5 below, but the present invention is not limited thereto.
Formula 5

10. The method according to any one of claims 1 to 9,
The thiophene compound may be a flat panel display, a flat light emitter, a light emitter of an illuminated surface emitting OLED, a flexible light emitter, a copier, a printer, an LCD backlight, a meter light source, a display panel, an organic light emitting diode (OLED), an organic solar cell (OSC), Thiophene compound, characterized in that applied to any one selected from e-paper, organic photoconductor (OPC) and organic transistor (OTFT) At least one organic layer between the first electrode, the second electrode and these electrodes, wherein at least one layer of the organic layer comprises the tertiary aryl amine according to any one of claims 1 to 9. An organic electroluminescent device characterized by. 12. The method of claim 11,
The at least one organic material layer includes a light emitting layer, and further comprising at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer and an electron injection layer.

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