KR20130123484A - Amine derivative and organic electroluminescent device including the same - Google Patents

Abstract

Provided is an amine derivative indicated as Formula 1 below. [Formula 1] [In Formula 1 above, the definition of each substituent is the same as the definition defined in the detailed explanation of the invention.] [Reference numerals] (AA) Comparative example;(BB) Example 3

Description

Amine derivative and organic electroluminescent device including the same

The present invention relates to an amine derivative and an organic electroluminescent device including the same, and more particularly, to an organic electroluminescent device having high luminous efficiency and a novel aromatic amine derivative therefor.

In 1987, Tang and Van Slyke reported high-efficiency characteristics using multilayered thin film structures of organic light emitting diodes (OLEDs) [Tang, C. W., Van Slyke, S. A. Appl. Phys. Lett. 51, 91 (1987)], OLEDs have a high potential for use in LCD backlights and lighting as well as excellent characteristics as next-generation displays, and many studies are being conducted under the spotlight [Kido, J., Kimura, M., and Nagai, K., Science 267, 1332 (1995)]. In particular, various approaches have been taken to improve the luminous efficiency, such as structural change of the device and material development [Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263 503 (2007) / Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364]. In particular, it is very important to study the device structure showing balanced emission of color by controlling the appropriate exciton distribution and energy transfer in the light emitting layer by optimizing the hole transport layer.

Optimization of the hole transport layer is a word that provides a stable supply of holes to the light emitting layer through the hole injection layer. This is because the HOMO level of the hole transport layer is higher than the HOMO level of the light emitting layer to facilitate smooth hole transport. In this case, the hole mobility of the hole transport layer is improved due to the charge balancing effect (the effect that the number of holes and electrons should be injected into the light emitting layer similarly to obtain high efficiency of light efficiency). Acts as an important factor. The materials of the hole transporting layer generally include electron donor components and can be thought of as p-types of semiconductors. They are mainly composed of aromatic amines, and are representative examples of aryl amine type NPB and flu. Orene (fluorene) type TPD and the like, carbazole (carbazole) derivatives are also variously studied as a hole transport layer material.

       NPB spiro-TPD spiro-TAD

The hole transport material not only transports holes easily but also binds electrons to the emission region, thereby increasing the probability of forming excitons, requiring high hole mobility and a glass transition temperature (Tg) of 150 ° C. or higher. It is preferable that the material used in the organic light emitting device has excellent thermal stability because joule heating occurs due to the movement of charges in the organic light emitting device. NPB, which is mainly used as the hole transport layer material, has a glass transition temperature of 100. Since it has a value of ° C or less, there is a problem that is difficult to use in the organic light emitting device that requires a high current. TPD was also initially used as a hole transport material, but the glass transition temperature (Tg) is unstable at about 60 ° C, so that the NPD-based or TPD-based fluorene dimer spiro-TAD is stable even at 95 ° C. HTL).

 In addition, the material used in the organic light emitting device is preferably less deformation of the material by moisture or oxygen. In addition, by having an appropriate hole or electron mobility, it is preferable to maximize the exciton formation by balancing the density of holes and electrons in the light emitting layer of the organic light emitting device. In addition, for the stability of the device, it is necessary to improve the interface with an electrode including a metal or a metal oxide. Therefore, research on such HTL materials is continuously required.

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel amine derivative having better luminous efficiency and durability than conventional materials, and an organic electroluminescent device in which the amine derivative is included in an organic material layer, so that the driving voltage of the device is low and the luminous efficiency is improved. To provide.

According to one aspect of the invention, an amine derivative represented by the following formula (1) is provided.

[Formula 1]

[In Formula 1, R ₁ to R ₄ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C ₁ -C ₆₀ alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl, substituted or unsubstituted 5- to 6-membered substituted or unsubstituted heterocycloalkyl containing at least one selected from C ₃ -C ₆₀ heteroaryl, N, O and S, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl, substituted or Unsubstituted triC ₁ -C ₆₀ alkylsilyl, substituted or unsubstituted diC ₁ -C ₆₀ alkyl C ₆ -C ₆₀ arylsilyl, substituted or unsubstituted triC ₆ -C ₆₀ arylsilyl, substituted or unsubstituted Adamantyl, substituted or unsubstituted C ₇ -C ₆₀ bicycloalkyl, cyano, substituted or unsubstituted C ₁ -C ₆₀ alkyloxy, substituted or unsubstituted C ₁ -C ₆₀ alkylthio, substituted or unsubstituted C ₆ -C ₆₀ aryloxy, substituted or unsubstituted C ₆ -C ₆₀ arylthio, a substituted or unsubstituted C ₁ -C ₆₀ alkoxycarbonyl, substituted again Unsubstituted C ₁ -C ₆₀ alkylcarbonyl, substituted or unsubstituted C ₆ -C ₆₀ arylcarbonyl, a substituted or unsubstituted C ₆ -C ₆₀ aryloxy carbonyl group, a substituted or unsubstituted C ₁ -C ₆₀ alkoxycarbonyloxy, substituted or unsubstituted C ₁ -C ₆₀ alkylcarbonyloxy, substituted or unsubstituted C ₆ -C ₆₀ arylcarbonyloxy, substituted or unsubstituted C ₆ -C ₆₀ aryloxycarbonyl Oxy, carboxyl, nitro or hydroxy;

Provided that R ₃ and R ₄ are linked to each other with substituted or unsubstituted C ₃ -C ₆₀ alkylene or substituted or unsubstituted C ₃ -C ₆₀ alkenylene, with or without fused ring, to form a fused ring Can do it;

L is a substituted or unsubstituted C ₃ -C ₆₀ heteroarylene comprising at least one selected from substituted or unsubstituted C ₆ -C ₆₀ arylene, N, O and S;

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C ₆ -C ₆₀ aryl, substituted or unsubstituted C ₃ -C ₆₀ heteroaryl;

Z ₁ is CR ₅ or N;

R ₅ is as defined in R ₁ to R _4. ]

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising the amine derivative described above.

According to still another aspect of the present invention, there is provided an organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic film disposed between the electrodes, wherein the organic film comprises the amine derivative described above. .

The amine derivative according to an embodiment of the present invention may be included in an organic material layer, preferably a hole injection layer or a hole transport layer, of the organic electroluminescent device to lower the driving voltage of the device and improve luminous efficiency. In particular, the lifetime of the device can be improved by the thermal stability of the compound.

1 is a graph showing the current density versus voltage of the HOD device according to Example 3 and Comparative Examples.

Hereinafter, the present invention will be described in detail.

An amine derivative according to an embodiment of the present invention may be represented by the following formula (1).

[Formula 1]

[In Formula 1, R ₁ to R ₄ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C ₁ -C ₆₀ alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl, substituted or unsubstituted 5- to 6-membered substituted or unsubstituted heterocycloalkyl containing at least one selected from C ₃ -C ₆₀ heteroaryl, N, O and S, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl, substituted or Unsubstituted triC ₁ -C ₆₀ alkylsilyl, substituted or unsubstituted diC ₁ -C ₆₀ alkyl C ₆ -C ₆₀ arylsilyl, substituted or unsubstituted triC ₆ -C ₆₀ arylsilyl, substituted or unsubstituted Adamantyl, substituted or unsubstituted C ₇ -C ₆₀ bicycloalkyl, cyano, substituted or unsubstituted C ₁ -C ₆₀ alkyloxy, substituted or unsubstituted C ₁ -C ₆₀ alkylthio, substituted or unsubstituted C ₆ -C ₆₀ aryloxy, substituted or unsubstituted C ₆ -C ₆₀ arylthio, a substituted or unsubstituted C ₁ -C ₆₀ alkoxycarbonyl, substituted again Unsubstituted C ₁ -C ₆₀ alkylcarbonyl, substituted or unsubstituted C ₆ -C ₆₀ arylcarbonyl, a substituted or unsubstituted C ₆ -C ₆₀ aryloxy carbonyl group, a substituted or unsubstituted C ₁ -C ₆₀ alkoxycarbonyloxy, substituted or unsubstituted C ₁ -C ₆₀ alkylcarbonyloxy, substituted or unsubstituted C ₆ -C ₆₀ arylcarbonyloxy, substituted or unsubstituted C ₆ -C ₆₀ aryloxycarbonyl Oxy, carboxyl, nitro or hydroxy;

Provided that R ₃ and R ₄ are linked to each other with substituted or unsubstituted C ₃ -C ₆₀ alkylene or substituted or unsubstituted C ₃ -C ₆₀ alkenylene, with or without fused ring, to form a fused ring Can do it;

L is a substituted or unsubstituted C ₃ -C ₆₀ heteroarylene comprising at least one selected from substituted or unsubstituted C ₆ -C ₆₀ arylene, N, O and S;

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C ₆ -C ₆₀ aryl, substituted or unsubstituted C ₃ -C ₆₀ heteroaryl;

Z ₁ is CR ₅ or N;

R ₅ is as defined in R ₁ to R _4. ]

In the term of substituents described herein, "alkyl" is a saturated hydrocarbon radical having a straight or branched chain consisting of only carbon atoms and hydrogen atoms. "C ₁ -C ₆₀ alkyl" may have 1 to 60 carbon atoms, may have 1 to 20 carbon atoms, may have 1 to 10 carbon atoms, or may have 1 to 6 carbon atoms. In addition, "alkyloxy" or "alkylthio" is an -O-alkyl group or -S-alkyl group, respectively.

In the term substituents described herein, "aryl" is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal. The aryl includes single or fused ring systems containing from 4 to 7, preferably 5 or 6 ring atoms, as appropriate for each ring. It also includes structures in which one or more aryls are bonded via chemical bonds. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like. Do not. "C ₆ -C ₆₀ aryl" may have 6 to 60 carbon atoms, may have 6 to 20 carbon atoms, and may have 6 to 12 carbon atoms.

“Heteroaryl” as described herein includes from 1 to 4 heteroatoms selected from nitrogen (N), oxygen (O), sulfur (S), phosphorus (P) or silicon (Si) as aromatic ring skeleton atoms. , Aryl group in which the remaining aromatic ring skeleton atom is carbon. The heteroaryl includes 5 to 6 membered monocyclic heteroaryl, and polycyclic heteroaryl fused with one or more benzene rings, and may be partially saturated. Also included are structures in which one or more heteroaryls are bonded via chemical bonds. Such heteroaryl groups include divalent aryl groups in which heteroatoms in the ring are oxidized or quaternized to form, for example, N-oxides or quaternary salts. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetra Monocyclic heteroaryl such as zolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothia Zolyl, Benzoisoxazolyl, Benzooxazolyl, Isoindoleyl, Indolyl, Indazolyl, Benzothiadiazolyl, Quinolyl, Isoquinolyl, Cinolinyl, Quinazolinyl, Quinoxalinyl, Carbazolyl, Phenantridinyl , Polycyclic heteroaryls such as benzodioxolyl and the like, and their corresponding N-oxides (eg, pyridyl N-oxides, quinolyl N-oxides), quaternary salts thereof, and the like. . "C ₃ -C ₆₀ heteroaryl" may have 3 to 60 carbon atoms, may have 4 to 20 carbon atoms, and may have 4 to 12 carbon atoms.

Further, "C ₃ -C ₆₀ cycloalkyl" may have 3 to 60 carbon atoms, may have 3 to 20 carbon atoms, or may have 3 to 7 carbon atoms.

In addition, "C ₂ -C ₆₀ alkenyl or alkynyl" may have 2 to 60 carbon atoms, may have 2 to 20 carbon atoms, or may have 2 to 10 carbon atoms.

The term "substituted" in the expression "substituted or unsubstituted ", as used herein, refers to a case where at least one hydrogen atom in a hydrocarbon is substituted with the following substituents. Such substituents include, but are not limited to, -F; -Cl; -Br; -CN; -NO ₂ ; -OH; A C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted by -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C ₁ -C ₂₀ alkoxy group unsubstituted or substituted with -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C ₆ -C ₃₀ aryl group which is unsubstituted or substituted by a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C ₆ -C ₃₀ heteroaryl group which is unsubstituted or substituted by a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, -F, -Cl, -Br, -CN, -NO ₂ or -OH; C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or substituted by -OH or unsubstituted C ₅ -C ₂₀ cycloalkyl group; C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or substituted by -OH or unsubstituted C ₅ -C ₃₀ heterocycloalkyl group; And a group represented by -N (G1) (G2). Wherein G1 and G2 are each independently selected from the group consisting of hydrogen; A C ₁ -C ₁₀ alkyl group; Or a C ₆ -C ₃₀ aryl group unsubstituted or substituted with a C ₁ -C ₁₀ alkyl group.

In Formula 1, L may be specifically selected from the structures of Formula 2 below.

(2)

[The above R ₁₁ and R ₁₂ are the same as the definition of R ₁ to R ₄ , and Ar ₃ is the same as the definition of Ar ₁ and Ar _2. ]

는 구체적으로 하기 화학식 3에 나열된 구조들 중에서 선택될 수 있다.In Chemical Formula 1, the

Specifically, it may be selected from the structures listed in the formula (3).

(3)

는 구체적으로 하기 화학식 4에 나열된 구조들 중에서 선택될 수 있다.In Chemical Formula 1, the

Specifically, it may be selected from the structures listed in the following formula (4).

[Formula 4]

The compound represented by Formula 1 may be selected from one of the compounds represented by Formula 5, but is not limited thereto.

[Chemical Formula 5]

The amine derivative represented by Chemical Formula 1 can be synthesized using a known organic synthesis method. Synthesis method of the amine derivative can be easily recognized by those skilled in the art with reference to the preparation examples described below.

According to the present invention, there is provided an organic electroluminescent device comprising an amine derivative represented by the formula (1).

The amine derivative of Chemical Formula 1 may be useful as a hole injection material or a hole transport material, and may be used as a host material for blue, green, red fluorescent and phosphorescent devices.

In addition, the organic electroluminescent device according to the present invention includes a first electrode, a second electrode and at least one organic film disposed between these electrodes. The organic layer includes at least one amine derivative represented by Chemical Formula 1.

The organic layer has a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and an electron transport function and an electron injection function It may include one or more layers selected from the group consisting of functional layers having at the same time.

For example, the amine derivative may be included in at least one selected from the group consisting of an emission layer, an organic layer disposed between the anode and the emission layer, and an organic layer disposed between the emission layer and the cathode. Preferably, the amine derivative may be included in at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, and a functional layer having a hole injection function and a hole transport function at the same time. The amine derivative may be included in the organic layer as a single material or a combination of different materials. Alternatively, the amine derivative may be used in combination with a conventionally known compound such as a hole transport layer and a hole injection layer.

The organic electroluminescent device according to the present invention is an anode / light emitting layer / cathode, anode / hole injection layer / light emitting layer / cathode, anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode, or anode / hole injection layer / hole transport layer It may have a structure of / light emitting layer / electron transport layer / electron injection layer / cathode. Alternatively, the organic electroluminescent device may include a functional layer / light emitting layer / electron transport layer / cathode having an anode / hole injection function and a hole transport function at the same time, or a functional layer / light emitting layer / electron transport layer / having an anode / hole injection function and a hole transport function at the same time. It may have a structure of an electron injection layer / cathode, but is not limited thereto.

The organic electroluminescent device may be manufactured using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. For example, an anode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, and an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon. It can then be prepared by depositing a material that can be used as a cathode thereon. In addition to the above method, an organic electroluminescent device may be manufactured by sequentially depositing a cathode material, an organic film, and an anode material on a substrate.

On the other hand, the organic film may be produced by a solution process (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method) using various polymer materials.

The organic electroluminescent device according to the present invention may be a top emission type, a bottom emission type or a double side emission type according to the material used.

Hereinafter, the present invention will be described in more detail with reference to various examples. The following examples are provided to illustrate the present invention, but the scope of the present invention is not limited thereto.

Example 1: Synthesis of Compound 1

The synthetic route of compound 1 is shown below.

1) Synthesis of Intermediate a

Methyl 2-bromobenzoate (150 g, 697.5 mmol) and Naphthalene-1-yl Boronic acid (131.96 g, 767.3 mmol) were added to a two-neck 2 L flask. It was dissolved in toluene (700ml). After complete melting, ethanol (300ml) and 5M potassium carbonate solution (212ml, 1534.5mmol) were added thereto, and N ₂ bubbling was performed for 30 minutes. Then, tetrakis (triphenylphosphine) palladium (Tetrakis (triphenylphosphine) palladium, [Pd (PPh ₃ ) ₄ ] (4.03g, 3.48mmol)) was added thereto, and a mechanical stirrer was used at 78 to 80 ° C. for 5 hours. It stirred. After the reaction was completed, it was dissolved in methylene chloride and filtered through a celite filter. The filtered solution was distilled under reduced pressure, and extracted with methylene chloride and distilled water. The extracted methylene chloride layer was grated with MgSO ₄ , and then the solvent was removed by distillation under reduced pressure to obtain a yellow solid. This solid was separated using a column chromatography method (methylene chloride and hexane eluent) to give a white solid (a). Yield and yield of the obtained intermediate a was 153 g and 84%.

2) Synthesis of Intermediate b

The intermediate a, ie methyl 2- (naphthalen-1-yl) benzoic acid (153 g, 583.3 mmol), was dissolved in ethanol (1000 ml) at 90 ° C. in a two-neck 2 L flask. gave. After melting, sodium hydroxide (46.6g, 1166mmol) was dissolved in distilled water (100ml) and slowly added. It was refluxed for 1 hour at 88 ~ 90 ℃. After completion of the reaction, slowly poured into 2M hydrochloric acid solution to crystallize the white solid. The solid was filtered and washed several times with distilled water, and then the white solid b was separated using column chromatography (eluent: methylene chloride and hexane). The yield and yield of the obtained intermediate b were 144 g and 94%.

3) synthesis of intermediate c

The intermediate b, 2- (naphthalen-1-yl) benzoic acid (2- (naphthalen-1-yl) benzoic acid, 144g, 500.1mmol) and methanesulfonic acid (7329mmol) were added to a 2-neck 2L flask at 30-35. Stirred for 8 hours with a mechanical stirrer. After completion of the reaction, the reaction mixture was poured slowly into ice water to crystallize. The crystallized solid was filtered under reduced pressure and washed several times with saturated sodium bicarbonate solution and distilled water. The filtered solid was extracted with methylene chloride and distilled water. The extracted methylene chloride layer was grated with MgSO ₄ , and then the solvent was removed by distillation under reduced pressure to obtain an orange solid. This solid was separated by column chromatography (eluents: methylene chloride and hexane) to give an orange solid c. Yield and yield of intermediate c was 116 g and 87%.

4) Synthesis of Intermediate d

In a two-neck 2L flask, intermediate c, 7H-benzo [c] fluoren-7-one (42g, 182.4mmol) and hydrazine monohydrate (133.5ml, 2736mmol), and potassium hydroxide (153.5g, 2736mmol) and 1.2L of diethylene glycol were added and stirred for 8 hours with a mechanical stirrer at 137 ~ 139 ℃. After completion of the reaction, the mixture was extracted with methylene chloride and distilled water. The extracted methylene chloride layer was grated with MgSO ₄ , and then the solvent was removed by distillation under reduced pressure to obtain a pink solid. This solid was separated using a column chromatography method (elution solvents: methylene chloride and hexane) to give a white solid d. Yield and yield of intermediate d was 32 g and 87%.

5) Synthesis of Intermediate e

Into a two-necked 1 L flask, intermediate d, 7H-benzo [c] fluorene (32 g, 147.9 mmol) and potassium hydroxide (6.63 g, 1183.2 mmol) was added and dimethyl sulfoxide (400 ml) Distilled water (40ml) was slowly dissolved at 10 ℃. And methyl iodide (36.8ml, 591.6mmol) was put over 10 minutes at 10 ℃, and stirred for 24 hours at room temperature. After completion of the reaction, the mixture was extracted with methylene chloride and distilled water. The extracted methylene chloride layer was grated with MgSO ₄ , and then the solvent was removed by distillation under reduced pressure to obtain a solid. This solid was separated by white column e using column chromatography (eluents: ethyl acetate and hexane). Yield and yield of intermediate e was 25 g and 89%.

6) Synthesis of Intermediate f

In a two-neck 1 L flask, intermediate e, ie, 7,7-dimethyl-7H-benzo [c] fluorene (7,7-dimethyl-7H-benzo [c] fluorene, 30 g, 122.8 mmol) and NBS (41.4 g, 234 mmol) was added thereto, dissolved in tetrahydrofuran (800 ml), and stirred at room temperature for 5 hours (orange yellow). After completion of the reaction, the mixture was extracted with methylene chloride and distilled water. The extracted methylene chloride layer was grated with MgSO ₄ , and then the solvent was removed by distillation under reduced pressure to obtain a solid. This solid was separated by column chromatography (eluent: ethyl acetate and hexane) to give a white solid f. Yield and yield of intermediate f was 32 g and 81%.

7) reaction of intermediate f with g

Intermediate f and g were reacted as follows to obtain Compound 1 as a final product.

Intermediate f (9.97g, 0.031mol), Intermediate g (15g, 0.031mol), Sodium-tert-butoxide (8.89g, 0.093mol) was added to toluene (300ml) and stirred under nitrogen, and the reaction temperature was increased to 80 ° C. It heated up and made it react for 1 hour. To this was added bis (dibenzylideneacetone) palladium (Bis (dibenzylideneacetone) palladium, 0.53g, 0.93mmol), tri-tert-butyl phosphine (0.19g, 0.93mmol) and reacted at 80 ° C for 4-5 hours. I was. The reaction solution was filtered to remove salts. The filtrate was distilled to remove toluene and the concentrate was separated by column and the yield of compound 1 was 18 g (yield: 80%). The NMR analysis result of obtained compound 1 is as follows.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.81 (d, 1H), 8.34 (d, 1H), 8.30 (s, 1H), 8.14 (t, 2H), 7.54 (m, 6H), 7.50 (m, 5H), 7.40 (m, 5H), 7.33 (m, 6H), 7.26 (d, 2H), 7.21 (m, 4H), 7.16 (s, 1H), 1.49 (s, 6H)

¹³ C NMR (300 MHz, CDCl ₃ ): δ 155.1, 153.4, 148.0, 147.1, 143.4, 141.5, 140.9, 140.3, 140.1, 137.9, 135.7, 134.3, 133.2, 132.3, 131.5, 131.3, 130.1, 129.0, 128.2, 128.0 , 127.7, 127.5, 127.2, 126.9, 126.8, 126.7, 126.3, 126.0, 125.8, 125.3, 124.7, 124.1, 123.7, 123.2, 122.8, 122.6, 121.8, 120.6, 120.3, 118.5, 110.3, 110.1, 47.2, 27.0

Example 3 Fabrication of HOD Device Containing Compound 1

After cleaning with 10 mm / sq indium tin oxide (ITO), patterned with an effective area of 9 mm ² , 2 min at 125 W under low vacuum (2X10 ^-2 Torr) in a loading chamber. O ₂ plasma treatment. Thereafter, the ITO substrate was moved to a main chamber, and 500 Å was deposited at a rate of 1 Å / sec using Compound 1 as a hole transport layer (HTL) material, and TCTA (4,4,4-triscarbazol-9- yl-triphenylamine) was deposited at 100 kPa at a rate of 0.3 kPa / sec. Finally, Al (aluminum) was deposited at 1000 kW at a rate of 10 kW / sec. After that, the substrate was moved to the loading chamber again, and then encapsulated with glass to fabricate a HOD device (hole-only device).

Comparative Example: Fabrication of HOD device including NPB ((4-4bis [N- (1-napthyl-N-phenyl-amino) biphenyl])

A HOD device was manufactured in the same manner as in Example 3, except that NPB was used as the HTL material instead of Compound 1 as a comparative example.

(evaluation)

The manufactured HOD device was measured using a Keithley 236 SMU while increasing the DC voltage from 0 V to 8 V at 0.2 V / step while measuring the current flowing through the device. Finally, the effective area of the device was divided by the measured current value to obtain a graph of current density versus voltage. 1 is a graph showing the current density versus voltage of the HOD device according to Example 3 and Comparative Examples. Referring to FIG. 1, it can be seen that Compound 1 has better hole mobility than the reference material NPB at a driving voltage of 3.0 V or higher.

Claims (10)

An amine derivative represented by the following formula (1).
[Chemical Formula 1]

[In Formula 1, R ₁ to R ₄ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C ₁ -C ₆₀ alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl, substituted or unsubstituted 5- to 6-membered substituted or unsubstituted heterocycloalkyl containing at least one selected from C ₃ -C ₆₀ heteroaryl, N, O and S, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl, substituted or Unsubstituted triC ₁ -C ₆₀ alkylsilyl, substituted or unsubstituted diC ₁ -C ₆₀ alkyl C ₆ -C ₆₀ arylsilyl, substituted or unsubstituted triC ₆ -C ₆₀ arylsilyl, substituted or unsubstituted Adamantyl, substituted or unsubstituted C ₇ -C ₆₀ bicycloalkyl, cyano, substituted or unsubstituted C ₁ -C ₆₀ alkyloxy, substituted or unsubstituted C ₁ -C ₆₀ alkylthio, substituted or unsubstituted C ₆ -C ₆₀ aryloxy, substituted or unsubstituted C ₆ -C ₆₀ arylthio, a substituted or unsubstituted C ₁ -C ₆₀ alkoxycarbonyl, substituted again Unsubstituted C ₁ -C ₆₀ alkylcarbonyl, substituted or unsubstituted C ₆ -C ₆₀ arylcarbonyl, a substituted or unsubstituted C ₆ -C ₆₀ aryloxy carbonyl group, a substituted or unsubstituted C ₁ -C ₆₀ alkoxycarbonyloxy, substituted or unsubstituted C ₁ -C ₆₀ alkylcarbonyloxy, substituted or unsubstituted C ₆ -C ₆₀ arylcarbonyloxy, substituted or unsubstituted C ₆ -C ₆₀ aryloxycarbonyl Oxy, carboxyl, nitro or hydroxy;
Provided that R ₃ and R ₄ are linked to each other with substituted or unsubstituted C ₃ -C ₆₀ alkylene or substituted or unsubstituted C ₃ -C ₆₀ alkenylene, with or without fused ring, to form a fused ring Can do it;
L is a substituted or unsubstituted C ₃ -C ₆₀ heteroarylene comprising at least one selected from substituted or unsubstituted C ₆ -C ₆₀ arylene, N, O and S;
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C ₆ -C ₆₀ aryl, substituted or unsubstituted C ₃ -C ₆₀ heteroaryl;
Z ₁ is CR ₅ or N;
R ₅ is the same as defined in R ₁ to R _4. ] The method according to claim 1,
In Chemical Formula 1, the

Specifically, it may be selected from the structures listed in the formula (3).
(3)

The method according to claim 1,
Said Formula 1

Is an amine derivative selected from the structures listed in formula (4).
[Chemical Formula 4]

An organic electroluminescent device comprising the amine derivative according to any one of claims 1 to 3. 5. The method of claim 4,
An organic electroluminescent device in which the amine derivative is used as a hole injection material or a hole transport material. 5. The method of claim 4,
An organic electroluminescent device in which the amine derivative is used as a host material for blue, green, red fluorescent and phosphorescent devices. A first electrode, a second electrode, and at least one organic layer disposed between the electrodes,
The organic film is an organic electroluminescent device comprising the amine derivative of any one of claims 1 to 3. The method of claim 7, wherein
The organic layer has a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and an electron transport function and an electron injection function An organic electroluminescent device comprising at least one layer selected from the group consisting of functional layers having simultaneously. The method of claim 7, wherein
The amine derivative is an organic electroluminescent device included in at least one selected from the group consisting of a light emitting layer, an organic film disposed between the anode and the light emitting layer, and an organic film disposed between the light emitting layer and the cathode. The method of claim 7, wherein
The amine derivative is an organic electroluminescent device included in at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, and a functional layer having a hole injection function and a hole transport function at the same time.

Images