KR101627211B1 - Organic Light Emitting Material Having Aromatic Amine Compound and Organic Light Emitting Diode Using The Same - Google Patents

Abstract

The present invention relates to a compound derivative used in an organic electroluminescent device and an organic electroluminescent device using the same. More particularly, the present invention relates to an aromatic compound having an indolocarbazolyl group and a carbazolyl group, And an organic electroluminescent device having a high luminous efficiency can be provided.

Description

TECHNICAL FIELD The present invention relates to an organic electroluminescent composition comprising an aromatic compound and an organic electroluminescent device using the same. BACKGROUND ART [0002] Organic electroluminescent (EL)

The present invention relates to an organic electroluminescent device, and more particularly to an organic electroluminescent device having an aromatic compound containing an indolocarbazolyl group and a carbazolyl group and having a lower driving voltage and a higher luminous efficiency than conventional ones .

Organic electroluminescent devices having various advantages such as low-voltage driving, self-luminescence, lightweight thin type, wide viewing angle, and fast response speed are one of the next generation flat panel displays to replace LCDs.

In U.S. Patent No. 4,356,429, Tang et al. Disclosed an organic electroluminescent device having a two-layer structure including two organic layers (a hole transporting layer and a light emitting layer) placed between an anode and a cathode. That is, the hole transporting layer adjacent to the anode contains a hole-transporting material and has a function of only transmitting holes mainly to the light-emitting layer in the organic EL device. Similarly, the electron transport layer adjacent to the cathode contains an electron transporting material, and the organic electroluminescent device of a two-layer structure selected to mainly transmit only electrons mainly in the organic electroluminescent device achieves a high luminous efficiency, The technology of the device was improved. Therefore, a multilayer structure including a hole transport layer, an electron transporting layer, and a hole blocking layer, such as a hole injection layer and a hole transporting layer, multilayer system), it is impossible to expect high-efficiency and high-luminance light emission characteristics.

In order to put the organic electroluminescence device device into practical use, the role of the device material, in particular, the hole-transporting material, in addition to the device having the multilayer structure described above is very important. For long-life devices, the hole-transporting material must have thermal and electrical stability. This is because molecules having low thermal stability due to heat generated from the device when voltage is applied are low in crystal stability and re-arranged. As a result, local crystallization occurs, and if there is a heterogeneous part, This is accepted as bringing about deterioration and destruction of the device. Therefore, the organic layer is usually used in an amorphous state. Further, since the organic electroluminescent device is a current injection type device, if the material used has a low glass transition temperature (Tg), heat generated during use causes deterioration of the organic electroluminescent device, shortening the lifetime of the device . In this respect, a material having a high glass transition temperature is preferable.

Representative examples of the hole transport material used in the conventional CuPC [copper phthalocyanine], m-MTDATA [4,4 ' , 4 "- tris (N -3- phenyl-N-phenylamino) triphenylamine] to the formula 2 2-TNATA [4,4 of the 4, 4 ', 4 "-tris (N - (naphthylene-2-yl) - N-phenylamino) triphenylamine], TPD [N, N' - diphenyl - N, N '- di (3-methylphenyl) -4,4'-diamino-biphenyl] and to the formula 7 NPB [N, N' - di (naphthalene-1-yl) - N, N '- diphenyl-benzidine; .

[Formula 2] < EMI ID =

However, since CuPC is a metal complex compound, it has excellent adhesion with ITO substrate and is widely used because it is most stable. However, since it absorbs in visible light region, it is difficult to realize total color, m-MTDATA or 2-TNATA has a glass transition temperature Is not only low at 78 캜 and at 108 캜, but also has disadvantages in mass production. TPD or NPB has a glass transition temperature (Tg) of 60 占 폚 and 96 占 폚, respectively, which is a critical disadvantage of shortening the lifetime of the device.

Further, the most important factor for determining the luminous efficiency in the organic EL device is the light emitting material. The luminescent material can be divided into a host material and a dopant material in terms of function. Generally, it is known that an EL material has the best EL structure to form a light emitting layer by doping a host with a dopant. In recent years, development of high-efficiency, long-life organic EL devices has become an urgent task. In particular, considering the level of EL characteristics required for middle- or large-sized OLED panels, it is urgent to develop materials superior to conventional light-emitting materials.

The light emitting material may be classified into a fluorescent material using a singlet exciton in a singlet state and a phosphorescent material using a triplet exciton in accordance with a light emitting mechanism thereof. As a light emitting material, a fluorescent material has been widely used so far, but when a phosphor is used as a light emitting layer forming material, it can have a much higher luminous efficiency than a fluorescent material.

Until now, the iridium (III) complex series has been widely known as a dopant compound of a phosphorescent emitter. For each RGB, bis (2- (2'-benzothienyl) -pyridinate-N, C-3 ' acetonate) [(acac) Ir (btp ) 2], tris (2-phenylpyridine) iridium [Ir (ppy) _3] and bis (4,6-difluorophenyl pyridinyl Nei Sat -N, C2), P And collinaito iridium [Firpic] are known. 4,4'-N, N'-dicarbazole-biphenyl (CBP) is the most widely known host compound for phosphorescent emitters and has been widely used as a host compound for bathocuproine (BCP) and aluminum (III) bis -Methyl-8-quinolinate) (4-phenylphenolate) (BAlq) is known as a high-efficiency OLED. However, when a conventional light emitting layer containing a dopant compound and a host compound is applied to an organic electroluminescent device, power efficiency is poor and operation life is unsatisfactory.

Korean Patent Publication No. KR2007050438A refers to a dopant compound contained in the luminescent layer of an organic electroluminescent device, in which an alkyl or aryl group is introduced into a Ir (ppy) ₃ structure which is a conventional dopant compound, but a combination with a specific host compound And still can not solve the problem of luminous efficiency and the like.

As described above, the materials used in the conventional organic electroluminescent devices still have many problems, and improvement of performance with excellent physical properties is required. Accordingly, there is an urgent need to develop an excellent material having an improved luminous efficiency of an organic electroluminescent device, a high thermal stability and a high glass transition temperature.

In order to solve the above problems, the present invention provides an organic compound containing an aromatic compound containing an indolocarbazolyl group and a carbazolyl group, and an organic electroluminescent device and an organic electroluminescent device. It is another object of the present invention to provide a material for an organic electroluminescent device which can improve the luminous efficiency of the organic electroluminescent device and increase the lifetime of the device, and a method for manufacturing the same. It is still another object of the present invention to provide an organic electroluminescent device exhibiting high luminous efficiency. It is still another object of the present invention to provide an organic electroluminescent device having an extended lifetime.

It is another object of the present invention to provide an organic electroluminescent device capable of providing an organic electroluminescent device having a driving voltage and a high luminous efficiency lower than those of the prior art and being variously utilized in a hole transporting layer, to be.

The present invention relates to an organic electroluminescent composition which is used as a light emitting material of an organic electroluminescent device and comprises an aromatic compound represented by the following general formula (1).

[Chemical Formula 1]

(Wherein IC is a substituted or unsubstituted indolocarbazolyl group, CZ is a substituted or unsubstituted carbazolyl group, and m and n each represent an integer of 1 to 3.)

Another embodiment of the present invention is an organic electroluminescent device comprising at least one organic layer comprising the organic electroluminescent composition described above. The organic electroluminescent device includes an organic light emitting diode, an organic field effect transistor, an organic thin film transistor, an organic laser diode, an organic solar cell, an organic light emitting electrochemical cell or an organic integrated circuit. Diodes, and the like are obvious to those of ordinary skill in the art.

The details of other embodiments are included in the detailed description and drawings.

According to the present invention, when an organic electroluminescent device is manufactured using an aromatic compound containing an indolocarbazolyl group and a carbazolyl group, problems of low emission brightness and low luminous efficiency, which are the biggest disadvantages of existing organic electroluminescent devices, It is possible to manufacture a high-performance organic electroluminescent device.

1 is a view showing a multi-layer structure of an organic electroluminescence device manufactured using an aromatic compound according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and will be described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

The present invention relates to an organic electroluminescent composition which is used as a light emitting material of an organic electroluminescent device and comprises an aromatic compound represented by the following general formula (1).

[Chemical Formula 1]

(Wherein IC is a substituted or unsubstituted indolocarbazolyl group, CZ is a substituted or unsubstituted carbazolyl group, and m and n each represent an integer of 1 to 3.)

Such a composition is characterized by containing an aromatic compound having an indolocarbazolyl group and a carbazolyl group, and is useful for use as a hole transport material, a luminescent material or an electron transport material in an organic electroluminescent device. Such an aromatic compound is used It has a high glass transition temperature, excellent electron / hole injection, transportation ability and high light emitting ability depending on the application. Thus, when the organic electroluminescent device is manufactured using the same, the luminous efficiency can be increased and the lifetime of the device can be increased.

In the above formula (1), the term "substituted or unsubstituted" means substituted or unsubstituted by any functional group known in the art, and the term "functional group" means a group of organic Means a common atomic group that is responsible for its properties in a compound or its binding mode. For example, the functional group may be a hydrogen atom, an aryl group, a heteroaryl group, an alkyl group, an alkenyl group, an aryloxy group, an alkoxy group, an alkoxycarbonyl group, an amino group, a halogen atom, a cyano group, a nitro group, The aryl group may be a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a biphenyl group, a terphenyl group, a fluorene group, or the like. .

As an example, specific examples of an organic compound having the structure of Formula 1 and having a high luminescence efficiency and a long lifetime, and having a low driving voltage and a high luminous efficiency, It is preferable to include at least one selected from the group, but the present invention is not limited thereto.

[Formula 101] < EMI ID =

,

,

,

,

,

,

(105)

,

,

,

,

[Chemical Formula 106]

,

,

,

,

(109)

,

,

,

,

(111)

,

,

,

,

[Formula 112]

,

,

,

,

,

,

(115)

,

,

,

,

[Chemical Formula 118]

,

,

,

,

,

,

(120)

,

,

,

,

(122)

(In the above Chemical Formulas 101 to 122, IC is a substituted or unsubstituted indolocarbazolyl group and CZ is a substituted or unsubstituted carbazolyl group.)

Specific examples of the aromatic compound represented by Formula 1 include at least one selected from the group consisting of the following Formulas 11 to 56, but the present invention is not limited thereto.

As described above, the present invention may be an aromatic compound or an organic light emitting composition or an organic light emitting material including the same which can be used as a light emitting material of an organic electroluminescence device. When such a compound, a derivative, a composition, or a material is used as a material of an organic electroluminescent device, high luminous efficiency can be obtained, and since the aromatic compound has a high glass transition temperature, a device having excellent durability can be manufactured. Here, the aromatic compound may be a material used for a hole injection layer, a hole transporting layer, a light emitting layer, or a dopant. It is also possible to use a material used for an electron injecting layer or an electron transporting layer.

The organic electroluminescent device and the organic electroluminescent device including the organic electroluminescent device according to the present invention can be used not only as organic light emitting diodes but also as organic electroluminescent devices such as organic field effect transistors, organic thin film transistors, organic laser diodes, organic solar cells, Also available in the field.

The aromatic compound according to the present invention can be purified by recrystallization and sublimation because of the characteristics of an organic electroluminescent device requiring high purity.

The following examples are provided for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims .

[ Example  1] Preparation of Compound 14

1-1. Preparation of Compound 14-1

65 g (0.270 mol) of indolo [3,2,1-jk] carbazole was added to a 5,000-mL, 5-necked round bottom flask and diluted with 1600 mL of chloroform. The diluted solution was cooled to 0, 48 g of N -bromosuccinimide (NBS) was slowly added thereto, and the mixture was stirred at room temperature for 12 hours. 1600 mL of distilled water was added to the reaction solution, stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried and concentrated, followed by recrystallization from acetonitrile and ethyl acetate, followed by vacuum drying to obtain 54 g (yield: 63%) of Compound 14-1 .

1-2. Preparation of Compound 14-2

A 500-mL, four-necked round bottom flask was equipped with a stirrer and thoroughly dried. 31 g (0.098 mol) of the compound 14-1 prepared in Example 1-1 was placed in a nitrogen atmosphere and 180 mL of dried tetrahydrofuran . The above solution was cooled to -50 ° C and 98 mL of butyl lithium (2.5 N -hexane solution) was slowly added thereto at the same temperature, followed by stirring for 30 minutes. A solution prepared by diluting 80 mL of triisopropyl borate with 320 mL of tetrahydrofuran was slowly added to the above reaction solution while maintaining the temperature at -50 ° C or less. The temperature of the reaction solution was slowly raised to room temperature, 600 mL of a 10 N aqueous hydrochloric acid solution was added, and the mixture was stirred for 1 hour. Water and dichloromethane were added to the reaction solution to extract the target compound, remove moisture, and concentrate. The obtained solid was suspended and stirred in hexane, filtered and vacuum dried to obtain 18.7 g (yield 67%) of Compound 14-2 .

1-3. Preparation of Compound 14-3

20 g (0.081 mol) of 3-bromocarbazole, 22.8 g of 2-chloro-4,6-diphenyl-1,3,5-triazine and 16.9 g of potassium carbonate were charged into a 500-mL three- And diluted with 200 mL of N, N -dimethylformamide. The diluted solution was heated to 110 DEG C and stirred for 6 hours. The reaction solution was poured into distilled water to precipitate a solid, which was then filtered and washed with distilled water and methanol. The obtained solid was vacuum-dried to obtain 33.8 g (yield: 87%) of Compound 14-3 .

1-4. Preparation of Compound 14

16.3 g (0.034 mol) of the compound 14-3 prepared in Example 1-3 was added to a 1000-mL, four-neck round bottom flask, and diluted with 400 mL of tetrahydrofuran. 10.7 g of the compound 14-2 prepared in Example 1-2, 34.2 mL of 3M-potassium carbonate aqueous solution and 0.51 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluted solution, and the reaction solution was refluxed for 12 hours . After the reaction solution was cooled to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried and then separated into a column to obtain 15.5 g (yield: 71%) of Compound 14 .

[ Example  2] Preparation of compound 15

2-1. Preparation of Compound 15-1

9.3 g of carbazole, 0.07 g of palladium acetate (II), 0.07 g of tri- (t-butyl) pentaacetate were added to 18 g (0.056 mol) of Compound 14-1 prepared in Example 1-1 in a 1000-mL, 0.12 g of pin, 7.0 g of sodium t-butoxide and 300 mL of o -xylene. The reaction solution was refluxed for 9 hours, cooled, and poured into an excess amount of methanol to precipitate a solid. The obtained solid was filtered, dried in vacuo and then separated into a column to obtain 16.8 g (yield 74%) of Compound 15-1 .

2-2. Preparation of compound 15-2

15 g (0.037 mol) of the compound 15-1 prepared in Example 2-1 was introduced into a 1000-mL, four-neck round bottom flask, and diluted with 380 mL of chloroform. 6.9 g of N -bromosuccinimide (NBS) was slowly added to the diluted solution, and the mixture was stirred at room temperature for 12 hours. 380 mL of distilled water was added to the reaction solution, stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried and concentrated, then recrystallized from acetonitrile and ethyl acetate and vacuum dried to obtain 15.1 g (yield: 84%) of compound 15-2 .

2-3. Preparation of compound 15

5.1 g of 4- (phenylamino) benzonitrile, 0.03 g of palladium acetate (II), 0.03 g of tri-tert-butylbenzoyl chloride were added to 11.6 g (0.024 mol) of the compound 15-2 prepared in Example 2-2 in a 500-mL, (t-butyl) phosphine, 3.0 g of sodium t-butoxide and 120 mL of o -xylene. The reaction solution was refluxed for 12 hours, cooled, and poured into an excess amount of methanol to precipitate a solid. The obtained solid was filtered, dried in vacuo and then separated into a column to obtain 9.3 g (yield 65%) of Compound 15. [

[ Example  3] Preparation of Compound 19

3-1. Preparation of Compound 19-1

20 g (0.041 mol) of the compound 15-2 prepared in Example 2-2 was added to a round bottom flask and diluted with 500 mL of tetrahydrofuran. 6.1 g of 4-chlorophenylboronic acid, 41 ml of 3M-potassium carbonate aqueous solution and 0.65 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluted solution, and the reaction solution was refluxed for 12 hours. After the reaction solution was cooled to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried and then separated into a column to obtain 18.3 g (yield: 86%) of Compound 19-1 .

3-2. Preparation of Compound 19

7.7 g of di ([1,1-biphenyl] -4-yl) amine, 0.03 g of palladium acetate (II), and 10.0 g of triethylamine were added to 12.4 g (0.024 mol) of the compound 19-1 prepared in Example 3-1, 0.05 g of tri- (t-butyl) phosphine, 3.0 g of sodium t-butoxide and 120 mL of o -xylene. The reaction solution was refluxed for 8 hours, cooled, poured into an excess amount of methanol, and a solid was precipitated. The resulting solid was filtered, dried in vacuo and then separated into a column to obtain 16.5 g (yield 86%) of Compound 19 .

[ Example  4] Preparation of Compound 23

4-1. Preparation of Compound 23-1

After thoroughly drying the round bottom flask, 5.4 g (0.017 mol) of the compound 14-1 prepared in Example 1-1, 4.8 g of bis (panacolato) diboron, 5.1 g of potassium acetate, Bis (diphenylphosphino) ferrocene] dichloropalladium (II) was diluted with 100 mL of dioxane. The diluted solution was stirred at 80 for 9 hours and then cooled to room temperature. Dichloromethane and water were added to the mixed solution to extract the objective compound, remove moisture, and concentrate. The resulting solid was suspended and stirred in ether, followed by filtration and vacuum drying to obtain 5.2 g (yield: 83%) of Compound 23-1 .

4-2. Preparation of Compound 23-2

In a round bottom flask, 4.8 g (0.013 mol) of the compound 23-1 prepared in Example 4-1 was added and diluted with 120 mL of tetrahydrofuran. 3.2 g of 2-chloro-4,6-diphenyl-1,3,5, -triazine, 12 mL of 3M-potassium carbonate aqueous solution, 0.5 g of tetrakis (triphenylphosphine) palladium (0) And 20 mL of water. The reaction solution was refluxed for 1 day. After the reaction solution was cooled to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried and then recrystallized from ethyl acetate and toluene to obtain 3.7 g (yield: 61%) of Compound 23-2 .

4-3. Preparation of Compound 23-3

3.5 g (7.41 mmol) of the compound 23-2 prepared in Example 4-2 was added to a round bottom flask and diluted with 100 mL of chloroform. After the dilution was cooled to 0, 1.3 g of N -bromosuccinimide (NBS) was slowly added thereto, and the mixture was stirred at room temperature for 10 hours. 100 mL of distilled water was added to the reaction solution, stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried and concentrated, then recrystallized from acetonitrile and ethyl acetate and dried under vacuum to obtain 3.8 g (yield: 92%) of Compound 23-3 .

4-4. Preparation of Compound 23

In the compound 23-3 3.5 g (6.35 mmol) prepared in Example 4-3 in a round bottom flask carbazole 1.1 g, palladium acetate (II) 8.9 mg, tree - (t- butyl) phosphine 13.2 mg, sodium t - butoxide and 70 mL of o -xylene. The reaction solution was refluxed for 10 hours, cooled, and poured into an excess amount of methanol to precipitate a solid. The obtained solid was filtered, dried in vacuo and then separated into a column to obtain 2.9 g (yield: 71%) of Compound 23 .

[ Example  5] Preparation of Compound 24

5-1. Preparation of Compound 24-1

15 g (0.037 mol) of the compound 15-1 prepared in Example 15-1 was introduced into a 1000-mL, four-neck round bottom flask, and diluted with 380 mL of chloroform. 13.9 g of N -bromosuccinimide (NBS) was slowly added to the diluted solution, and the mixture was stirred at room temperature for 12 hours. 380 mL of distilled water was added to the reaction solution, stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried and concentrated, then recrystallized from acetonitrile and ethyl acetate and vacuum dried to obtain 18.4 g (yield: 88%) of Compound 24-1 .

5-2. Preparation of Compound 24

10.2 g of 4- (phenylamino) benzonitrile, 0.06 g of palladium acetate (II), 0.06 g of tri-tert-butylbenzoyl chloride were added to 13.5 g (0.024 mol) of the compound 24-1 prepared in Example 5-1, (t-butyl) phosphine, 6.0 g of sodium t-butoxide and 140 mL of o -xylene. The reaction solution was refluxed for 12 hours, cooled, and poured into an excess amount of methanol to precipitate a solid. The obtained solid was filtered, dried in vacuo and then separated into a column to obtain 10.4 g (yield: 55%) of Compound 24 .

[ Example  6] Preparation of Compound 30

6-1. Preparation of Compound 30-1

13 g (0.041 mol) of the compound 14-1 prepared in Example 1-1 was added to a round bottom flask and diluted with 350 mL of tetrahydrofuran. 6.1 g of 4-chlorophenylboronic acid, 41 ml of 3M-potassium carbonate aqueous solution and 0.65 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluted solution, and the reaction solution was refluxed for 12 hours. After the reaction solution was cooled to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried and then separated into a column to obtain 11.8 g (yield: 82%) of Compound 30-1 .

6-2. Preparation of Compound 30-2

5.0 g of di-4-tolylamine, 0.03 g of palladium acetate (II) and 0.03 g of tri- (t-butyl) phosphine were added to 8.4 g (0.024 mol) of the compound 30-1 prepared in Example 6-1, g, sodium tert-butoxide (3.0 g) and o -xylene (120 mL). The reaction solution was refluxed for 8 hours, cooled, poured into an excess amount of methanol, and a solid was precipitated. The obtained solid was filtered, dried in vacuo and then separated into a column to obtain 11.1 g (yield: 90%) of Compound 30-2 .

6-3. Preparation of Compound 30-3

11 g (0.021 mol) of the compound 30-2 prepared in Example 6-2 was added to a round bottom flask and diluted with 150 mL of chloroform. The diluted solution was cooled to 0, 7.7 g of N -bromosuccinimide (NBS) was slowly added thereto, and the mixture was stirred at room temperature for 10 hours. To the reaction mixture was added 150 mL of distilled water, stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried and concentrated, then recrystallized from acetonitrile and acetone and vacuum dried to obtain 13.1 g (yield: 91%) of Compound 30-3 .

6-4. Preparation of Compound 30

5.2 g of carbazole, 0.02 g of palladium acetate (II), 0.03 mg of tri- (t-butyl) phosphine, 0.50 g of sodium t (t-butyl) phosphine were added to 10.0 g (0.015 mol) of the compound 30-3 prepared in Example 6-3, - butoxide and 100 mL of o -xylene were fed into the flask. The reaction solution was refluxed for 9 hours, cooled, and poured into an excess amount of methanol to precipitate a solid. The resulting solid was filtered, dried in vacuo and then separated into a column to obtain 7.8 g (Yield: 62%) of Compound 30 .

[ Example  7] Preparation of Compound 38

7-1. Preparation of Compound 38-1

30 g (0.037 mol) of the compound 19 prepared in Example 3-2 was added to a round bottom flask and diluted with 750 mL of chloroform. 6.9 g of N -bromosuccinimide (NBS) was slowly added to the diluted solution, and the mixture was stirred at room temperature for 12 hours. To the reaction mixture was added 750 mL of distilled water, stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried and concentrated, then recrystallized from acetonitrile and ethyl acetate and dried under vacuum to obtain 27 g (yield: 82%) of Compound 38-1 .

7-2. Preparation of Compound 38

36 g (0.041 mol) of the compound 38-1 prepared in Example 7-1 was added to a round bottom flask and diluted with 900 mL of tetrahydrofuran. 11.7 g of the compound 14-2 prepared in Example 1-2, 41 mL of 3M-potassium carbonate aqueous solution and 0.65 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluted solution, and the reaction solution was refluxed for 12 hours . After the reaction solution was cooled to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried and then separated into a column to obtain 30.7 g (yield 72%) of Compound 38 .

[ Example  8] Preparation of compound 47

8-1. Preparation of Compound 47-1

23.6 g (0.037 mol) of the compound 14 prepared in Example 1-4 was added to a round bottom flask and diluted with 600 mL of chloroform. 6.9 g of N -bromosuccinimide (NBS) was slowly added to the diluted solution, and the mixture was stirred at room temperature for 12 hours. 600 mL of distilled water was added to the reaction solution, stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried and concentrated, then recrystallized from acetonitrile and acetone and vacuum dried to obtain 23 g (yield: 87%) of the compound 47-1 .

8-2. Preparation of compound 47-2

After completely drying the round bottom flask, 23 g (0.032 mol) of the compound 47-1 prepared in Example 8-1 was added under a nitrogen atmosphere and dissolved in 130 mL of dried tetrahydrofuran. The above solution was cooled to -50 and 32 mL of butyllithium (2.5 N -hexane solution) was added slowly at the same temperature, followed by stirring for 30 minutes. A solution of 26 mL of triisopropyl borate diluted in 230 mL of tetrahydrofuran was slowly added to the above reaction solution while keeping the temperature below -50. The temperature of the reaction solution was slowly raised to room temperature, and 210 mL of a 10 N aqueous hydrochloric acid solution was added thereto, followed by stirring for 1 hour. Water and dichloromethane were added to the reaction solution to extract the target compound, remove moisture, and concentrate. The resulting solid was suspended and stirred in hexane, filtered and dried in vacuo to obtain 13.3 g (yield: 61%) of Compound 47-2 .

8-3. Preparation of compound 47

13 g (0.019 mol) of the compound 47-2 prepared in Example 8-2 was added to a round bottom flask and diluted with 330 mL of tetrahydrofuran. 13.6 g of the compound 47-1 prepared in Example 8-1, 20 mL of 3M-potassium carbonate aqueous solution and 0.3 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluted solution, and the reaction solution was refluxed for 15 hours . After the reaction solution was cooled to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried and then separated into a column to obtain 12.6 g (yield: 52%) of Compound 47 .

[ Example  9] Preparation of Compound 56

9-1. Preparation of Compound 56-1

To a round bottom flask was added 10 g (0.060 mol) of carbazole and 0.02 g of N - ((1,1'-biphenyl-4-yl) -N- (4- bromophenyl) - (1,1'- (T-butyl) phosphine, 6.9 g of sodium t-butoxide and 250 mL of o -xylene were put into the flask, and the reaction solution was stirred for 8 hours The resulting solid was filtered, dried in vacuo and then separated into a column to obtain 24.2 g (yield: 72%) of Compound 56-1 .

9-2. Preparation of Compound 56-2

20 g (0.036 mol) of the compound 56-1 prepared in Example 9-1 was added to a round bottom flask and diluted with 500 mL of chloroform. 6.9 g of N -bromosuccinimide (NBS) was slowly added to the diluted solution, and the mixture was stirred at room temperature for 12 hours. 500 mL of distilled water was added to the reaction solution, stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried and concentrated, followed by recrystallization from acetonitrile and ethyl acetate, followed by vacuum drying to obtain 18.0 g (yield: 79%) of Compound 56-2 .

9-3. Preparation of Compound 56

16.3 g (0.017 mol) of the compound 56-1 10.9 prepared in Example 9-2 was added to a round bottom flask and diluted with 280 mL of tetrahydrofuran. 5.4 g of the compound 14-2 prepared in Example 1-2, 17.1 mL of 3M-potassium carbonate aqueous solution and 0.26 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluted solution, and the reaction solution was refluxed for 12 hours . After the reaction solution was cooled to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried and then separated into a column to obtain 10.1 g (yield 74%) of Compound 56 .

[Example 10]

Organic electroluminescence device fabrication using compound 19

A transparent anode of indium tin oxide (ITO) having a film thickness of 750 was formed on a glass substrate of a size of 25 mm x 75 mm x 1.1 mm. The glass substrate was placed in a vacuum deposition apparatus and reduced in pressure to about 10 ^-7 torr. Next, 2-TNATA of the following Chemical Formula 2 was vapor-deposited to a thickness of 600 ANGSTROM to form a hole injection layer. Then, the compound 19 of the present invention was vapor-deposited to a thickness of 350 ANGSTROM to form a hole transport layer. Next, CBP of Formula 3 and Ir (ppy) ₃ of Formula 4 were simultaneously vapor-deposited at a weight ratio of 90:10 to form a light emitting layer having a thickness of 300 ANGSTROM. Subsequently, BAlq of the following Chemical Formula 5 was vapor-deposited to a thickness of 80 Å to form a hole blocking layer. Subsequently, Alq ₃ of the following Chemical Formula 6 was vapor-deposited to a thickness of 250 ANGSTROM to form an electron transport layer. Lithium quinolate (Liq) was then deposited to a thickness of 15 ANGSTROM to form an electron injecting layer. Finally, aluminum was deposited to a thickness of 1000 ANGSTROM to form a cathode. A voltage was applied to the thus fabricated organic electroluminescent device to perform a luminescence test. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Chemical Formula 2] < EMI ID =

 [Chemical Formula 4] < EMI ID =

[Example 11] Production of organic electroluminescence device using Compound 30

An organic electroluminescent device was fabricated and evaluated in the same manner as in Example 10 except that Compound 30 was used instead of Compound 19 as the hole transport layer in Example 10. [ The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Example 12] Production of organic electroluminescence device using Compound 38

An organic electroluminescence device was fabricated and evaluated in the same manner as in Example 10, except that the compound 38 was used instead of the compound 19 as the hole transport layer. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Example 13] Production of organic electroluminescence device using Compound 56

An organic electroluminescence device was fabricated and evaluated in the same manner as in Example 10, except that the compound 56 was used instead of the compound 19 as the hole transport layer. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Example 14] Production of organic electroluminescence device using compound 15

An organic electroluminescent device was fabricated and evaluated in the same manner as in Example 10, except that Compound 15 was used instead of 2-TNATA as the hole injecting layer in Example 10. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Example 15] Production of organic electroluminescence device using compound 24

In Example 10, an organic electroluminescent device was fabricated and evaluated in the same manner as in Example 10, except that Compound 24 was used instead of 2-TNATA as the hole injecting layer. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Comparative Example 1] Fabrication of organic electroluminescence device using NPB

An organic electroluminescent device was fabricated and evaluated in the same manner as in Example 10 except that NPB of the following formula (7) was used instead of the compound 19 as the hole transport layer in the above Example 10. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

(7)

[Comparative Example 2] Production of organic electroluminescence device using Compound A

An organic electroluminescence device was fabricated and evaluated in the same manner as in Example 10, except that the following compound A was used in place of the compound 19 as the hole transport layer in Example 10. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Compound A]

[Comparative Example 3] Production of organic electroluminescence device using Compound B

An organic electroluminescence device was fabricated and evaluated in the same manner as in Example 10, except that the following compound B was used in place of the compound 19 as the hole transport layer in Example 10. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Compound B]

[Comparative Example 4] Production of organic electroluminescence device using Compound C

An organic electroluminescence device was fabricated and evaluated in the same manner as in Example 10, except that the compound C was used instead of the compound 19 as the hole transport layer. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Compound C]

[Example 16]

Organic Electroluminescent Device Fabrication Using Compound 14

A transparent anode of indium tin oxide (ITO) having a film thickness of 750 ANGSTROM was formed on a glass substrate of 25 mm x 75 mm x 1.1 mm size. The glass substrate was placed in a vacuum deposition apparatus and reduced in pressure to about 10 ^-7 torr. Then, 2-TNATA of Formula 2 was deposited to a thickness of 600 Å to form a hole injection layer. Next, NPB of Formula 7 was vapor-deposited to a thickness of 350 ANGSTROM to form a hole transport layer. Compound 14 of the present invention and Ir (ppy) ₃ of Formula 4 were simultaneously vapor-deposited at a weight ratio of 90:10 to form a light emitting layer having a thickness of 300 ANGSTROM. Then, BAlq of Formula 5 was deposited to a thickness of 80 Å to form a hole blocking layer. Subsequently, Alq ₃ of Formula 6 was vapor-deposited to a thickness of 250 Å to form an electron transport layer. Lithium quinolate (Liq) was then deposited to a thickness of 15 ANGSTROM to form an electron injecting layer. Finally, aluminum was deposited to a thickness of 1000 ANGSTROM to form a cathode. A voltage was applied to the thus fabricated organic electroluminescent device to perform a luminescence test. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Example 17] Production of organic electroluminescence device using Compound 23

An organic electroluminescence device was fabricated and evaluated in the same manner as in Example 16, except that the compound 23 was used instead of the compound 14 as the emitting layer in Example 16. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Example 18] Production of organic electroluminescence device using compound 47

An organic electroluminescent device was prepared and evaluated in the same manner as in Example 16 except that the compound 47 was used instead of the compound 14 as the luminescent layer. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Comparative Example 5] Production of organic electroluminescence device using Compound D

An organic electroluminescent device was fabricated and evaluated in the same manner as in Example 16, except that the compound D was used instead of the compound 14 as the luminescent layer. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Compound D]

[Comparative Example 6] Production of organic electroluminescence device using Compound E

An organic electroluminescent device was fabricated and evaluated in the same manner as in Example 16, except that Compound E was used instead of Compound 14 as the emitting layer in Example 16. The measured driving voltage, maximum luminous efficiency and luminous color are shown in Table 1.

[Compound E]

Example Hole injection layer Hole transport layer Host Driving voltage
(V) Luminous efficiency
(cd / A) Luminous color Example 10 2-TNATA Compound 19 CBP 5.1 33.1 green Example 11 2-TNATA Compound 30 CBP 4.8 32.9 green Example 12 2-TNATA Compound 38 CBP 5.0 37.2 green Example 13 2-TNATA Compound 56 CBP 4.5 34.6 green Example 14 Compound 15 NPB CBP 6.0 28.7 green Example 15 Compound 24 NPB CBP 5.9 27.5 green Example 16 2-TNATA NPB Compound 14 4.7 32.5 green Example 17 2-TNATA NPB Compound 23 5.2 31.3 green Example 18 2-TNATA NPB Compound 47 4.6 35.1 green Comparative Example 1 2-TNATA NPB CBP 6.5 20.8 green Comparative Example 2 2-TNATA Compound A CPB 6.1 27.2 green Comparative Example 3 2-TNATA Compound B CBP 6.3 25.5 green Comparative Example 4 2-TNATA Compound C CBP 6.0 28.7 green Comparative Example 5 2-TNATA NPB Compound D 6.3 22.3 green Comparative Example 6 2-TNATA NPB Compound E 6.0 26.2 green

* 2-TNATA: Formula 2

CBP: Formula 3

* Ir (ppy) ₃ : Formula 4

* BAlq: Formula 5

* Alq ₃ : Formula 6

NPB: Formula 7

As can be seen from Table 1, the organic electroluminescent devices according to Examples 10 to 18 of the present invention have lower driving voltage and higher luminous efficiency than those of Comparative Examples 1 to 4.

That is, the compounds according to the present invention were compared with Examples 11 to 18 and Comparative Example 1 according to the present invention. The compounds according to the present invention were used in the hole transport layer (Examples 10, 11, 12 and 13), the hole injection layer (Examples 14 and 15) And has a lower driving voltage and a higher luminous efficiency when used as a host (Examples 16, 17, 18).

Specifically, when Examples 10 to 13 and Comparative Examples 2, 3 and 4 according to the present invention are compared, when the compound according to the present invention is used as the hole transport layer (Examples 10, 11, 12, and 13) And high luminous efficiency.

Comparing Examples 16 to 18 and Comparative Examples 5 and 6 according to the present invention, when the compound according to the present invention is used as a host (Examples 16, 17, and 18), it has lower driving voltage and higher luminescence efficiency .

Although the present invention has been shown and described with respect to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the following claims It will be apparent to those skilled in the art.

Claims (4)

delete delete An organic electroluminescent composition comprising an aromatic compound selected from the group consisting of the following Formulas 14, 15, 19, 23, 24, 30, 38, 47,

An organic electroluminescent device comprising at least one organic layer comprising the organic electroluminescent composition according to claim 3.

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