KR101007516B1 - Organic electroluminescent composition and organic electroluminescent device comprising 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, and more particularly, to prepare a dicarbazolylbenzene derivative compound and to use it as a hole transport material of the organic electroluminescent device. It is to provide an organic electroluminescent device which increases the lifespan and has excellent luminous brightness and luminous efficiency.

Description

Organic electroluminescent composition and organic electroluminescent device comprising same {Organic Light Emitting Material and Organic Light Emitting Diode Having The Same}

The present invention relates to an organic electroluminescent device, and more particularly, to a dicarbazolylbenzene derivative used as a light emitting material of an organic electroluminescent device, and more particularly, to prepare a dicarbazolylbenzene compound and to deliver the hole in the organic electroluminescent device. It is used as a material to increase the life of the device, to provide an organic electroluminescent device excellent in light emission luminance and light emission efficiency.

Organic electroluminescent devices with various advantages such as low voltage driving, self-luminous, light weight, wide viewing angle and fast response speed are one of the most researched fields as one of the next generation flat panel displays to replace LCD.

In US Pat. No. 4,356,429, Tang et al. Disclosed a two-layered organic electroluminescent device comprising two organic layers (hole transport layer and light emitting layer) sandwiched between an anode and a cathode. That is, the hole transport layer adjacent to the anode contains a hole transport material and has a function of transferring only holes to the light emitting layer mainly in the organic electroluminescent device. Similarly, the electron transport layer adjacent to the cathode contains an electron transport material, and the organic electroluminescent device device having a two-layer structure selected to mainly transmit only electrons within the organic electroluminescent device device achieves high luminous efficiency and thus substantially organic electroluminescence. The technology of the device was improved. Therefore, in terms of luminous efficiency, a multilayer structure including a hole transport layer such as a hole injection layer and a hole transporting layer, an electron transporting layer, a hole blocking layer, and the like ( Without the multilayer system, it is impossible to expect high efficiency and high luminance.

In order to realize the organic electroluminescent device device, in addition to configuring the device in the above multilayer structure, the role of the device material, in particular, the hole transport material is very important. For long life devices, the hole transport material must be thermally and electrically stable. Because of the heat generated by the device when the voltage is applied, molecules with low thermal stability have low crystal stability, resulting in rearrangement. Finally, if localization occurs and an inhomogeneous part exists, the electric field concentrates on this part. This is because it is accepted to bring about deterioration and destruction of the device. Therefore, the organic layer is usually used in an amorphous state. Furthermore, since the organic electroluminescent device is a current injection type device, if the material used has a low glass transition temperature (Tg), the heat generated during use causes the organic electroluminescent device to deteriorate and shorten the life of the device. Let's go. In this respect, materials having a high glass transition temperature are preferred.

Representative examples of hole-transfer materials used in the past include CuPC [copper phthalocyanine], 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] of 1, TPD [ N, N' -diphenyl- N, N' -di (3-methylphenyl) -4,4'-diaminobiphenyl] and NPB [ N, N' -di (naphthalen-1-yl) -N, N' -diphenylbenzidine] Etc.

[Formula 1] [Formula 2]

However, since CuPC is a metal complex, it is widely used because it has excellent adhesion to ITO substrate and is the most stable, but it is difficult to realize total color due to absorption in the visible region, and m-MTDATA or 2-TNATA have a glass transition temperature. Since not only is low as 78 ℃ and 108 ℃ but also a lot of disadvantages in the process of mass production, this also has a problem in realizing the total color. In addition, TPD or NPB also has a fatal disadvantage of shortening the life of the device for the same reason because the glass transition temperature (Tg) as low as 60 ℃ and 96 ℃, respectively.

As described above, the hole transport material used in the conventional organic electroluminescent device still contains many problems, and there is a demand for improved performance having excellent physical properties. Therefore, there is an urgent need for development of an excellent material having an improved luminous efficiency of an organic electroluminescent device and having high thermal stability and high glass transition temperature.

The present invention for solving the above problems is to provide a dicarbazolylbenzene compound derivative having a high glass transition temperature, an organic electroluminescent composition comprising the same, and an organic electroluminescent device. Another object of the present invention is to provide a hole transport material for an organic electroluminescent device having excellent thermal stability and a method of manufacturing the same, which can improve the luminous efficiency of the organic electroluminescent device and increase the lifetime of the device. Still another object of the present invention is to provide an organic electroluminescent device exhibiting high luminous efficiency. Another object of the present invention is to provide an organic electroluminescent device having an extended lifetime.

First, the present invention is an organic electroluminescent composition, which is used as a light emitting material of an organic electroluminescent device and comprises a dicarbazolylbenzene derivative represented by the following general formula (I).

[Formula I]

(In Formula I, R1 and R2 are each a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R3 to R5 are each hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted Heteroaryl group, or alkyl group, D is a linker, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.)

Another embodiment of the invention is an organic electroluminescent device comprising at least one organic layer comprising the organic electroluminescent composition described above. Here, 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. It is apparent to those skilled in the art that various applications such as diodes can be made.

Other embodiments are described in the detailed description and drawings below.

Since the dicarbazolylbenzene derivative according to the present invention has a high glass transition temperature and a high pyrolysis temperature of 140 ° C. or higher, the thermal stability is excellent, and the light emitting property of the dicarbazolylbenzene derivative using the composition including the same as a hole transporting material of an organic electroluminescent device As a result of the evaluation, the light emission characteristics were superior in current density, brightness, highest brightness, and luminous efficiency than conventional 2-TNATA (Formula 1) or NPB (Formula 2).

Accordingly, when the organic electroluminescent device is manufactured using the dicarbazolylbenzene derivative according to the present invention as a hole transporting material, the problem of low emission luminance and low luminous efficiency, which is the biggest disadvantage of the conventional organic electroluminescent device, is simultaneously solved. In addition to the high glass transition temperature, the thermal stability of the organic electroluminescent device is excellent, making it possible not only to manufacture a high performance organic electroluminescent device but also to commercialize a full-color organic electroluminescent device requiring high efficiency, high brightness and long life. Can contribute significantly.

1 is a UV / Vis for the dicarbazolylbenzene derivative of formula 22 in accordance with an embodiment of the present invention. And fluorescence spectral graphs.
2 is a differential scanning calorimetry (DSC) curve graph of the dicarbazolylbenzene derivative of Chemical Formula 22 according to an embodiment of the present invention.
Figure 3 is a UV / Vis for the dicarbazolylbenzene derivative of formula 26 in accordance with an embodiment of the present invention. And fluorescence spectral graphs.
4 is a differential scanning calorimetry (DSC) curve graph of the dicarbazolylbenzene derivative of Chemical Formula 26 according to an embodiment of the present invention.
5 is a view showing a multilayer structure of an organic electroluminescent device manufactured using a dicarbazolylbenzene derivative according to an embodiment of the present invention.

The present invention is a dicarbazolylbenzene derivative represented by the following general formula (I), which is useful for use as a hole transport material or an organic electroluminescent material in an organic electroluminescent device, and the dicarbazolylbenzene derivative has a high glass transition temperature and excellent hole injection, Since it has a transport capacity, if the organic electroluminescent device is manufactured by using it as a hole transport material or the like, the luminous efficiency can be increased and the life of the device can be increased.

[Formula I]

(In Formula I, R1 and R2 are each a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R3 to R5 are each hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted Heteroaryl group, or alkyl group, D is a linker, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.)

In the above formula (I), the substituted or unsubstituted aryl group means an aryl group which is substituted by a specific functional group or is not substituted by any functional group, and examples of such an aryl group are phenyl group, naphthyl group, phenanthryl group and anthryl Groups, biphenyl groups, terphenyl groups, fluorene groups and the like. In addition, in the present specification, D is a linking group (linker) is a bridging group that simply connects without hydrogen or other functional groups, for example, in the case of formula (I), for example, the phenyl group of the carbazole having R 3 and R 1 and This means that the amine (N) having R 2 is directly connected, that is, that D is not particularly present.

Accordingly, specific examples of the dicarbazolylbenzene derivative having the structure of Formula (I), which enables the organic electroluminescent device having a particularly high luminous efficiency and long life, include the following Chemical Formulas 11 to 48. However, the present invention is not limited to these.

[Formula 11] [Formula 12]

[Formula 13] [Formula 14]

[Formula 15] [Formula 16]

[Formula 17] [Formula 18]

[Formula 19] [Formula 20]

[Formula 21] [Formula 22]

[Formula 23] [Formula 24]

[Formula 25] [Formula 26]

[Formula 27] [Formula 28]

[Formula 29] [Formula 30]

[Formula 31] [Formula 32]

[Formula 33] [Formula 34]

[Formula 35] [Formula 36]

[Formula 37] [Formula 38]

[Formula 39] [Formula 40]

[Formula 41] [Formula 42]

[Formula 43] [Formula 44]

[Formula 45] [Formula 46]

[Formula 47] [Formula 48]

The present invention may be a dicarbazolylbenzene derivative which can be used as a light emitting material of an organic electroluminescent device as described above, or may be an organic light emitting composition or an organic light emitting material including the same. When the derivative, composition or material is used as a hole transport material of the organic electroluminescent device, high luminous efficiency can be obtained, and a device having excellent durability can be manufactured because the glass transition temperature of the dicarbazolylbenzene derivative is high. Here, the hole transport material refers to a material used for the hole injection layer or the hole transport layer, in some cases may be a material used for the light emitting layer.

In addition, the dicarbazolylbenzene derivatives according to the present invention may be purified using recrystallization and sublimation methods due to the characteristics of the organic electroluminescent device requiring high purity.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The invention can be better understood by the following examples and comparative examples, which are intended to illustrate the invention and are not intended to limit the scope of protection defined by the appended claims.

Example 1 Preparation of Chemical Formula 12

In the present invention, the dicarbazolylbenzene derivative represented by Chemical Formula I may be prepared by a synthetic route as in Scheme 1 below.

Scheme 1

1-1. Preparation of Formula 102

3000-ml, 4-necked round bottom flask under nitrogen atmosphere, 167 g (0.707 mol) of 1,4-dibromobenzene, 248 g of carbazole (Formula 101), 0.79 g of palladium acetate (II), tri- (t-butyl) 14 g of phosphine (10% hexane solution), 156 g of sodium t-butoxide and 2000 ml of O-xylene were added thereto. The reaction solution was refluxed for 8 hours, cooled to room temperature and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 269 g (yield 93%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.29 (d, J = 7.6 Hz, 4H), 7.93 (s, 4H), 7.61 (d, J = 8.4 Hz, 4H), 7.51 (t, J = 8 Hz, 4H), 7.35 (t, J = 8 Hz, 4H).

1-2. Preparation of Chemical Formula 103

259 g (0.634 mol) of Chemical Formula 102 compound prepared in Example 1-1 were added to a 20000-ml, four-necked round bottom flask, and diluted with 8000 ml of chloroform. The diluent was cooled to 0 ° C., and 113 g of N -bromosuccinimide (NBS) was slowly added thereto, followed by stirring for 3 hours. 8000 ml of distilled water was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried and concentrated, then recrystallized with acetone and methanol and dried in vacuo to give 229 g (yield 74%) of the title compound.

H NMR (400 MHz, CDCl): δ 8.27 (d, J = 2.2 Hz, 1H), 8.17 (d, J = 7.7 Hz, 2H), 8.11 (d, J = 7.7 Hz, 1H), 7.83-7.76 (m , 4H), 7.57-7.50 (m, 4H), 7.48-7.40 (m, 4H), 7.35-7.31 (m, 3H).

1-3. Preparation of Formula 12

45 g (0.092 mol) of the compound of formula 103 prepared in Example 1-2 in a 1000-ml, four-necked round bottom flask under nitrogen atmosphere, 22.3 g of N -phenyl-1-naphthylamine, 0.12 g of palladium acetate (II), 2 g of tri- (t-butyl) phosphine (10% hexane solution), 12 g of sodium t-butoxide and 450 ml of o-xylene were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to yield 49 g (yield 85%) of the title compound. MS ( m / z , [M] ⁺ ): C46H31N3: 625.46

Example 2 Preparation of Chemical Formula 17

1000-ml, 4 sphere formula prepared in Example 1-2 under a nitrogen atmosphere a round bottom flask was added compound 103 45g (0.092mol), N - ( 1- naphthyl) 9,9-dimethyl -9 H - fluoren 33 g of 2-amine, 0.12 g of palladium acetate (II), 2 g of tri- (t-butyl) phosphine (10% hexane solution), 12 g of sodium t-butoxide and 450 ml of o-xylene were added thereto. The reaction solution was refluxed for 4 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried under vacuum to obtain 49 g (yield 72%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.27 (d, J = 7.6 Hz, 2H), 8.13 (d, J = 7.6 Hz 1H), 8.08 (s, 1H), 8.02 (t, J = 8.8 Hz, 2H), 7.94-7.87 (m, 5H) 7.64-7.57 (m, 7H), 7.53-7.40 (m, 7H), 7.35-7.30 (m, 3H), 7.28-7.17 (m, 3H), 7.00 (s, 1 H), 6.68 (d, J = 8.8 Hz, 1 H), 1.28 (m, 6 H).

UV (λ _max ): 342nm PL: 464nm

Glass transition temperature (measured by Tg, DSC): 173 ℃

Example 3 Preparation of Chemical Formula 22

1000-ml, 4 gu a formula 103 compound prepared in Example 1-2 in a nitrogen atmosphere in a round bottom flask, 56g (0.115mol), N - ( 4- biphenyl), 9,9-dimethyl -9 H - fluoren 40 g of 2-amine, 0.13 g of palladium acetate (II), 2.5 g of tri- (t-butyl) phosphine (10% hexane solution), 13 g of sodium t-butoxide and 450 ml of o-xylene were added thereto. The reaction solution was refluxed for 4 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 78 g (yield 88%) of the title compound.

H NMR (400 MHz, DMSO): δ 8.27 (d, J = 7.7 Hz, 2H), 8.22 (d, J = 8.0 Hz, 1H), 8.16 (d, J = 1.8 Hz, 1H), 7.96-7.90 (m , 4H), 7.70 (t, J = 7.3 Hz, 2H), 7.64-7.57 (m, 8H), 7.49-7.45 (m, 4H), 7.41 (t, J = 7.7 Hz, 2H), 7.34-7.21 ( m, 8H), 7.10 (d, J = 8.8 Hz, 2H), 7.04 (dd, J = 8.4 Hz, 2.2 Hz, 1H), 1.37 (s, 6H).

UV (λ _max ): 340 nm PL: 425 nm (see Fig. 1)

Glass transition temperature (measured by Tg, DSC): 167 ° C (see Figure 2)

Example 4 Preparation of Chemical Formula 23

4-1. Preparation of Formula 104

80 g (0.164 mol) of the compound of formula 103 prepared in Example 1-2 were added to a 3000-ml, four-necked round bottom flask, and diluted with 1600 ml of tetrahydrofuran. 22 g of benzeneboronic acid, 164 ml of 3M-potassium carbonate aqueous solution and 2.1 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluent, and the reaction solution was refluxed for 1 day. After cooling the reaction solution to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried to obtain 72 g (yield 90%) of the title compound.

4-2. Preparation of Formula 105

Into a 10000-ml, four-necked round bottom flask was added 70 g (0.144 mol) of the compound of formula 104 prepared in Example 4-1 and diluted with 2800 ml of chloroform. 26 g of N -bromosuccinimide (NBS) was slowly added to the diluent and stirred for 6 hours. 2800 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 with acetone and methanol and dried in vacuo to give 54 g (yield 67%) of the title compound.

4-3. Preparation of Formula 23

In a 1000-ml, four-necked round-bottom flask, 52 g (0.092 mol) of Formula 105 compound prepared in Example 4-2, 17.1 g of diphenylamine, 0.12 g of palladium acetate (II), tri- (t-butyl) 2 g of phosphine (10% hexane solution), 12 g of sodium t-butoxide and 450 ml of o-xylene were added thereto. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 52 g (yield 87%) of the title compound.

MS ( m / z , [M] ⁺ ): C48H33N3: 651.45

Example 5 Preparation of Chemical Formula 26

5-1. Preparation of Formula 106

80 g (0.164 mol) of the compound of formula 103 prepared in Example 1-2 were added to a 3000-ml, four-necked round bottom flask, and diluted with 1600 ml of tetrahydrofuran. 28 g of 4-chlorobenzeneboronic acid, 164 ml of 3M-potassium carbonate aqueous solution and 2.1 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluent, and the reaction solution was refluxed for 1 day. After cooling the reaction solution to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried to give 73 g (yield 86%) of the title compound.

H NMR (400 MHz, CDCl): δ 8.32 (d, J = 2.2 Hz, 1H), 8.20 (d, J = 8.0 Hz, 1H), 8.17 (d, J = 7.7 Hz, 2H), 7.82-7.80 (m , 2H), 7.66-7.63 (m, 3H), 7.61-7.54 (m, 4H), 7.50-7.43 (m, 6H), 7.37-7.31 (m, 4H).

5-2. Preparation of Formula 26

40 g (0.077 mol) of formula 106 compound prepared in Example 5-1 in a 1000-ml, four-necked round bottom flask under nitrogen atmosphere, 19 g of N -phenyl-1-naphthylamine, 0.09 g of palladium acetate (II), tri 1.6 g of-(t-butyl) phosphine (10% hexane solution), 9 g of sodium t-butoxide and 400 ml of o-xylene were added thereto. The reaction solution was refluxed for 4 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 46 g (yield 85%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.52 (s, 1H), 8.33 (d, J = 7.6 Hz, 1H), 8.27 (d, J = 7.6 Hz, 2H), 8.01 (d, J = 8.4 Hz, 1H), 7.94-7.88 (m, 6H), 7.72-7.58 (m, 8H), 7.56-7.44 (m, 5H), 7.39 (d, J = 7.6 Hz, 1H), 7.32 (t, J = 7.6 Hz, 3H), 7.25 (t, J = 7.2 Hz, 2H), 7.04-6.93 (m, 5H).

UV (λ _max ): 327 nm PL: 447 nm (see FIG. 3)

Glass transition temperature (measured by Tg, DSC): 146 ° C (see Figure 4)

Example 6 Preparation of Chemical Formula 27

40 g (0.077 mol) of formula 106 compound prepared in Example 5-1 in a 1000-ml, four-necked round bottom flask under nitrogen atmosphere, 19 g of N -phenyl-2-naphthylamine, 0.09 g of palladium acetate (II), tri 1.6 g of-(t-butyl) phosphine (10% hexane solution), 9 g of sodium t-butoxide and 400 ml of o-xylene were added thereto. The reaction solution was refluxed for 4 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 44 g (yield 82%) of the title compound.

UV (λ _max ): 330nm PL: 425nm

Glass transition temperature (measured by Tg, DSC): 143 ℃

Example 7 Preparation of Chemical Formula 31

40 g (0.077 mol) of formula 106 compound prepared in Example 5-1, 25 g of N- (4-biphenyl) -1-naphthylamine in a 1000-ml, four-necked round bottom flask under nitrogen atmosphere, palladium acetate (II ) 0.09g, tri- (t-butyl) phosphine (10% hexane solution) 1.6g, sodium t-butoxide 9g and 400ml o-xylene was added. The reaction solution was refluxed for 5 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 43 g (yield 72%) of the title compound. MS ( m / z , [M] ⁺ ): C58H39N3: 777.48

Example 8 Preparation of Chemical Formula 35

1000-ml, 4 gu embodiment a formula 106 compound 40g (0.077mol) prepared in Example 5-1 in a nitrogen atmosphere in a round bottom flask, N - (2- naphthyl) 9,9-dimethyl -9 H - fluoren 28 g of 2-amine, 0.09 g of palladium acetate (II), 1.6 g of tri- (t-butyl) phosphine (10% hexane solution), 9 g of sodium t-butoxide and 400 ml of o-xylene were added. The reaction solution was refluxed for 5 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 43 g (yield 68%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.63 (s, 1H), 8.39 (d, J = 7.6 Hz, 1H), 8.29 (d, J = 7.6 Hz, 2H), 7.98-7.95 (m, 4H), 7.89-7.72 (m, 8H) 7.67-7.60 (m, 4H), 7.53-7.48 (m, 5H), 7.44-7.22 (m, 11H), 7.08 (d, J = 8.4 Hz, 1H), 1.40 (s, 6 H).

Example 9 Preparation of Chemical Formula 37

1000-ml, 4 gu Example 5-1 A formula 106 compound 40g (0.077mol) prepared in a nitrogen atmosphere in a round bottom flask, N - (4- biphenyl), 9,9-dimethyl -9 H - fluoren 28 g of 2-amine, 0.09 g of palladium acetate (II), 1.6 g of tri- (t-butyl) phosphine (10% hexane solution), 9 g of sodium t-butoxide and 400 ml of o-xylene were added. The reaction solution was refluxed for 5 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 50 g (yield 77%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.62 (s, 1H), 8.39 (d, J = 7.6 Hz, 1H), 8.30 (d, J = 8 Hz, 2H), 7.98-7.93 (m, 4H ), 7.82-7.74 (m, 5H), 7.67-7.60 (m, 8H), 7.53-7.42 (m, 6H), 7.37-7.27 (m, 7H), 7.23 (d, J = 8.4 Hz, 2H), 7.18 (d, J = 8.8 Hz, 2H), 7.09 (dd, J = 8,1.8 Hz, 1H), 1.42 (s, 6H).

UV (λ _max ): 351nm PL: 413nm

Glass transition temperature (measured by Tg, DSC): 166 ℃

Example 10 Preparation of Chemical Formula 43

10-1. Preparation of Formula 107

N -phenylcarbazole 50g (0.205mol) was added to a 1000-ml, four-necked round bottom flask and diluted with 300ml of dichloromethane. 38 g of N -bromosuccinimide (NBS) was slowly added to the diluent, and the reaction solution was stirred at room temperature for 4 hours. 300 ml of distilled water was added to the reaction solution, the mixture was stirred for 30 minutes, and the organic layer was separated. The separated organic layer was dried and concentrated, then recrystallized with acetone and methanol and dried in vacuo to give 55 g (yield 83%) of the title compound.

10-2. Preparation of Formula 108

53 g (0.165 mol) of the compound of formula 107 prepared in Example 10-1 were added to a 5000-ml, four-necked round bottom flask, and diluted with 1000 ml of tetrahydrofuran. 28.4 g of 4-chlorophenylboronic acid, 70 ml of 3M-potassium carbonate aqueous solution, and 3.6 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluent, and the reaction solution was refluxed for 1 day. After cooling the reaction solution to room temperature, 1000 ml of ethyl acetate and 1000 ml of distilled water were added and stirred. The organic layer was separated, concentrated to remove moisture. Methanol was added to this concentrate, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried to obtain 42 g (yield 72%) of the title compound.

10-3. Preparation of Formula 109

2000-ml, 4 gu formula prepared in Example 10-2 in a nitrogen atmosphere in a round bottom flask 108 Compound 61g (0.172mol), N - ( 4- biphenyl), 9,9-dimethyl -9 H - fluoren 62.2 g of 2-amine, 0.19 g of palladium acetate (II), 3.4 g of tri- (t-butyl) phosphine (10% hexane solution), 18 g of sodium t-butoxide and 600 ml of o-xylene were added. The reaction solution was refluxed for 8 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 96 g (yield 82%) of the title compound.

10-4. Preparation of Formula 110

Into a 3000-ml, four-necked round bottom flask was added 90 g (0.133 mol) of the compound of formula 109 prepared in Example 10-3 and diluted with 900 ml of dichloromethane. 24 g of N -bromosuccinimide (NBS) was slowly added to the diluent, and the reaction solution was stirred at room temperature for 4 hours. 900 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, concentrated and then recrystallized with acetone and methanol and dried in vacuo to give 96 g (yield 95%) of the title compound.

10-5. Preparation of Formula 111

80 g (0.106 mol) of the Formula 110 compound prepared in Example 10-4 were added to a 3000-ml, four-necked round bottom flask, and diluted with 1600 ml of tetrahydrofuran. 20 g of 2-naphthylboronic acid, 110 ml of 3M-potassium carbonate aqueous solution and 3.7 g of tetrakis (triphenylphosphine) palladium (0) were added to the diluent, and the reaction solution was refluxed for 1 day. After cooling the reaction solution to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compound was vacuum dried to obtain 57 g (yield 67%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.89 (s, 1H), 8.76 (s, 1H), 8.34 (s, 1H), 8.03-7.92 (m, 5H), 7.81-7.63 (m, 13H ), 7.57-7.42 (m, 8H), 7.36-7.25 (m, 4H), 7.23 (d, J = 8.5 Hz, 2H), 7.16 (d, J = 8.4 Hz, 2H), 7.07 (dd, J = 7.7, 1.5 Hz, 1 H), 1.42 (s, 6 H).

10-6. Preparation of Formula 112

Into a 3000-ml, four-necked round bottom flask, 55 g (0.068 mol) of the formula 111 compound prepared in Example 10-5 were added and diluted with 1000 ml of dichloromethane. 13 g of N -bromosuccinimide (NBS) was slowly added to the diluent, and the reaction solution was stirred at room temperature for 7 hours. 1000 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 with acetone and methanol and dried in vacuo to give 54 g (yield 89%) of the title compound.

10-7. Preparation of Formula 43

52 g (0.059 mol) of Formula 112 compound, 11 g of carbazole, 0.06 g of palladium acetate (II), tri- (t-butyl) force, prepared in Example 10-6 in a 2000-ml, four-necked round bottom flask under nitrogen atmosphere 1.2 g of pin (10% hexane solution), 6.2 g of sodium t-butoxide and 500 ml of o-xylene were added. The reaction solution was refluxed for 12 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 42 g (yield 73%) of the title compound.

MS ( m / z , [M] ⁺ ): C73H51N3: 969.57

Example 11

Fabrication of Organic Electroluminescent Device Using Chemical Formula 12

A transparent anode of indium tin oxide (ITO) having a thickness of 750 kPa was formed on a glass substrate having a size of 25 mm x 75 mm x 1.1 mm. The glass substrate was placed in a vacuum deposition apparatus to reduce the pressure to about 10 ⁻⁷ torr. Subsequently, the chemical formula 12 of the present invention was deposited to a thickness of 600 kPa to form a hole injection layer. Subsequently, NPB of Formula 2 was deposited to a thickness of 600 kPa, thereby forming a hole transport layer. Subsequently, the light emitting layer was formed by simultaneously depositing a-ADN of Formula 3, which is a blue host, and perylene of Formula 4, which is a blue dopant, in a weight ratio of 95: 5. Subsequently, Alq ₃ of Formula 5 was deposited to a thickness of 200 μs, thereby forming an electron transport layer. Subsequently, lithium fluoride (LiF) was deposited to a thickness of 10 GPa to form an electron injection layer. Finally, aluminum was deposited to have a thickness of 1000 Å to form a cathode (see FIG. 5). The luminescence test was performed by applying a voltage to the organic electroluminescent device manufactured as described above. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

[Formula 2] [Formula 3]

[Formula 4] [Formula 5]

Example 12

Fabrication of Organic Electroluminescent Device Using Chemical Formula 17

In Example 11, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 11, except that Chemical Formula 17 was used instead of Chemical Formula 12 as the hole injection layer. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

Example 13

Fabrication of Organic Electroluminescent Device Using Chemical Formula 22

In Example 11, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 11, except that Chemical Formula 22 was used instead of Chemical Formula 12 as the hole injection layer. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

Example 14

Fabrication of Organic Electroluminescent Device Using Chemical Formula 23

In Example 11, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 11, except that Chemical Formula 23 was used instead of Chemical Formula 12 as the hole injection layer. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

Example 15

Fabrication of Organic Electroluminescent Device Using Chemical Formula 26

A transparent anode of indium tin oxide (ITO) having a thickness of 750 kPa was formed on a glass substrate having a size of 25 mm x 75 mm x 1.1 mm. The glass substrate was placed in a vacuum deposition apparatus to reduce the pressure to about 10 ⁻⁷ torr. Subsequently, 2-TNATA of Chemical Formula 1 was deposited to have a thickness of 600 μs to form a hole injection layer. Subsequently, the chemical formula 26 of the present invention was deposited to a thickness of 600 kPa to form a hole transport layer. Subsequently, the light emitting layer was formed by simultaneously depositing a-ADN of Formula 3, which is a blue host, and perylene of Formula 4, which is a blue dopant, in a weight ratio of 95: 5. Subsequently, Alq ₃ of Formula 5 was deposited to have a thickness of 200 μs to form an electron transport layer. Subsequently, lithium fluoride (LiF) was deposited to a thickness of 10 GPa to form an electron injection layer. Finally, aluminum was deposited to have a thickness of 1000 mW to form a cathode. The luminescence test was performed by applying a voltage to the organic electroluminescent device manufactured as described above. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

[Formula 1]

Example 16

Fabrication of Organic Electroluminescent Device Using Chemical Formula 27

In Example 15, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 15, except that Chemical Formula 27 was used instead of Chemical Formula 26 as the hole transport layer. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

Example 17

Fabrication of Organic Electroluminescent Device Using Chemical Formula 31

In Example 15, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 15, except that Chemical Formula 31 was used instead of Chemical Formula 26 as the hole transport layer. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

Example 18

Fabrication of Organic Electroluminescent Device Using Chemical Formula 35

In Example 15, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 15, except that Chemical Formula 35 was used instead of Chemical Formula 26 as the hole transport layer. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

Example 19

Fabrication of Organic Electroluminescent Device Using Formula 37

In Example 15, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 15, except that Chemical Formula 37 was used instead of Chemical Formula 26 as the hole transport layer. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

Example 20

Fabrication of Organic Electroluminescent Device Using Chemical Formula 27

In Example 15, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 15, except that Chemical Formula 43 was used instead of Chemical Formula 26 as the hole transport layer. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

Comparative Example 1

Fabrication of organic electroluminescent device using 2-TNATA and NPB

A transparent anode of indium tin oxide (ITO) having a thickness of 750 kPa was formed on a glass substrate having a size of 25 mm x 75 mm x 1.1 mm. The glass substrate was placed in a vacuum deposition apparatus to reduce the pressure to about 10 ⁻⁷ torr. Subsequently, 2-TNATA of Chemical Formula 1 was deposited to have a thickness of 600 μs to form a hole injection layer. Subsequently, NPB of Formula 2 was deposited to a thickness of 600 kPa, thereby forming a hole transport layer. Subsequently, a-ADN of Formula 3, which is a blue host, and perylene of Formula 4, which is a blue dopant, were simultaneously deposited in a weight ratio of 95: 5 to form a light emitting layer to have a thickness of 300 GPa. Subsequently, Alq ₃ of Formula 5 was deposited to have a thickness of 200 μs to form an electron transport layer. Subsequently, lithium fluoride (LiF) was deposited to a thickness of 10 GPa to form an electron injection layer. Finally, aluminum was deposited to have a thickness of 1000 mW to form a cathode. The luminescence test was performed by applying a voltage to the organic electroluminescent device manufactured as described above. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

Comparative Example 2

Fabrication of Organic Electroluminescent Device Using Chemical Formula 6

In Comparative Example 1, an organic electroluminescent device was manufactured and evaluated in the same manner as in Comparative Example 1 except for using the following Chemical Formula 6 instead of NPB of Chemical Formula 2 as the hole transport layer. The measured highest luminance, maximum luminous efficiency and luminous color are shown in Table 1.

[Formula 6]

Luminescence Characteristics of Organic Electroluminescent Devices Example Compound of hole injection layer Compound of hole transport layer Brightness
(cd / m ² ) Efficiency
(cd / A) Luminous color Example 11 Formula 12 NPB 9948 3.65 blue Example 12 Formula 17 NPB 14592 4.21 blue Example 13 Formula 22 NPB 19290 4.42 blue Example 14 Formula 23 NPB 12620 3.82 blue Example 15 2-TNATA Formula 26 18267 4.22 blue Example 16 2-TNATA Formula 27 20456 4.66 blue Example 17 2-TNATA Formula 31 11041 3.79 blue Example 18 2-TNATA Formula 35 17204 4.65 blue Example 19 2-TNATA Formula 37 21152 4.97 blue Example 20 2-TNATA Formula 43 11254 4.73 blue Comparative Example 1 2-TNATA NPB 7546 3.22 blue Comparative Example 2 2-TNATA 6 8561 3.48 blue

As can be seen in Table 1, it can be seen that the organic electroluminescent device according to Examples 11 to 20 of the present invention has a higher luminance and efficiency than Comparative Example 1 and Comparative Example 2.

Simple modifications or changes of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be included in the scope of the present invention.

The organic light emitting composition and the organic electroluminescent device including the same according to the present invention are not only organic light emitting diodes but also organic field-effect transistors, organic thin film transistors, organic laser diodes, organic solar cells, organic light emitting electrochemical cells, and organic integrated circuits. Can also be used in the field.

Claims (3)

An organic electroluminescent composition, which is used as a light emitting material of an organic electroluminescent device, comprises a dicarbazolylbenzene derivative represented by the following general formula (I).
(I)

(In Formula I, R1 and R2 are each a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R3 to R5 are each hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted Heteroaryl group, or alkyl group, D is a linker, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.)
The organic electroluminescent composition according to claim 1, wherein Chemical Formula I is selected from the group consisting of Chemical Formulas 11 to 48.
[Formula 11] [Formula 12]

[Formula 13] [Formula 14]

[Formula 15] [Formula 16]

[Formula 17] [Formula 18]

[Formula 19] [Formula 20]

[Formula 21] [Formula 22]

[Formula 23] [Formula 24]

[Formula 25] [Formula 26]

[Formula 27] [Formula 28]

[Formula 29] [Formula 30]

[Formula 31] [Formula 32]

[Formula 33] [Formula 34]

[Formula 35] [Formula 36]

[Formula 37] [Formula 38]

[Formula 39] [Formula 40]

[Formula 41] [Formula 42]

[Formula 43] [Formula 44]

[Formula 45] [Formula 46]

[Formula 47] [Formula 48]

An organic electroluminescent device comprising at least one organic layer comprising the organic electroluminescent composition according to claim 1.

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