KR20110105664A - Organic light emitting material and organic light emitting diode having 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, and more particularly, to prepare a carbazole derivative compound, and to use this as a hole transport material of the organic electroluminescent device To increase, to provide an organic electroluminescent device excellent in luminescence 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 carbazole derivative used as a light emitting material of an organic electroluminescent device, and more particularly to preparing a carbazole compound and using it as a hole transport material of the organic electroluminescent device. It is to provide an organic electroluminescent device which increases the life of the device and is 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 carbazole 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 carbazole derivative represented by the following general formula (I).

[Formula I]

(In Formula I, R1 and R2 are each hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group, and R3 to R5 are each a substituted or unsubstituted aryl group, or substituted Unsubstituted heteroaryl 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.

The carbazole derivatives according to the present invention have excellent thermal stability because they have a high glass transition temperature and a high pyrolysis temperature of 140 ° C. or higher, and the light emitting properties of the carbazole derivatives are evaluated using a composition including the same as a hole transport material of an organic electroluminescent device. As a result, the present invention showed superior luminescence properties in terms of current density, brightness, highest brightness, and luminous efficiency than conventional hole transport materials, 2-TNATA (Formula 1) or NPB (Formula 2).

Accordingly, when the organic electroluminescent device is manufactured using the carbazole derivative according to the present invention as a hole transporting material, the problems of low luminance and low luminous efficiency, which are the biggest disadvantages of the conventional organic electroluminescent device, can be solved at the same time. In addition, since the glass transition temperature is high, the thermal stability of the organic electroluminescent device is excellent. Therefore, it is possible to manufacture a high-performance organic electroluminescent device and to commercialize a full-color organic electroluminescent device requiring high efficiency, high brightness and long life. Can contribute.

1 is a UV / Vis. For the carbazole derivative of Formula 35 according to an embodiment of the present invention. And fluorescence spectral graphs.
Figure 2 is a differential scanning calorimetry (DSC) curve graph for the carbazole derivative of Formula 35 according to an embodiment of the present invention.
Figure 3 is a UV / Vis for the carbazole derivative of formula 133 according to an embodiment of the present invention. And fluorescence spectral graphs.
4 is a differential scanning calorimetry (DSC) curve graph of a carbazole derivative of Formula 133 according to an embodiment of the present invention.
5 is a view showing a multilayer structure of an organic electroluminescent device manufactured using a carbazole derivative according to an embodiment of the present invention.

The present invention is a carbazole 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 carbazole derivative has a high glass transition temperature and excellent hole injection and transport ability. Therefore, when the organic electroluminescent device is manufactured using the hole transport material, the light emitting efficiency can be increased and the life of the device can be increased.

[Formula I]

(In Formula I, R1 and R2 are each hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group, and R3 to R5 are each a substituted or unsubstituted aryl group, or substituted Unsubstituted heteroaryl 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, that D is a linking group is a bridging group that simply connects without hydrogen or other functional groups, for example, in the case of the formula (I), a phenyl group of carbazole having R 2 and R 4 and This means that the amine (N) having R 5 is directly connected, that is, that D is not particularly present.

In addition, in the general formula (I), preferred examples of R1 to R5 are the same as the unit structure of the chemical formula shown in Table 1 below. Each unit structure is named by b01 to b15 to distinguish them.

division Unit structure division Unit structure division Unit structure b01

b02

b03

b04

b05

b06

b07

b08

b09

b10

b11

b12

b13

Methyl
b14

tert -Butyl b15

H

In addition, in the general formula (I), a preferable example of D is the same as the unit structure of the chemical formula shown in Table 2. In each unit structure, the division symbols are named d01 to d06 to distinguish them.

division Unit structure division Unit structure division Unit structure d01 coupler d02

d03

d04

d05

d06

Based on Tables 1 and 2, specific examples of carbazole derivatives having a structure of general formula (I) that finally enable organic electroluminescent devices of high luminous efficiency and long life are shown in Tables 3 to 10 below. It includes a compound of Formula 11 to Formula 212 which is a compound. However, the present invention is not limited to these.

Chemical formula D R1 R2 R3 R4 R5 11 d01 b15 b15 b01 b01 b01 12 d01 b15 b15 b01 b01 b02 13 d01 b15 b15 b01 b01 b03 14 d01 b15 b15 b01 b01 b04 15 d01 b15 b15 b01 b01 b05 16 d01 b15 b15 b01 b01 b06 17 d01 b15 b15 b01 b01 b08 18 d01 b15 b15 b01 b01 b09 19 d01 b15 b15 b01 b01 b10 20 d01 b15 b15 b01 b01 b11 21 d01 b15 b15 b01 b01 b12 22 d01 b15 b15 b01 b02 b03 23 d01 b15 b15 b01 b02 b04 24 d01 b15 b15 b01 b02 b08 25 d01 b15 b15 b01 b02 b09 26 d01 b15 b15 b01 b02 b11 27 d01 b15 b15 b01 b02 b12 28 d01 b15 b15 b01 b03 b03 29 d01 b15 b15 b01 b03 b04 30 d01 b15 b15 b01 b03 b08 31 d01 b15 b15 b01 b03 b09 32 d01 b15 b15 b01 b03 b12 33 d01 b15 b15 b01 b04 b04 34 d01 b15 b15 b01 b04 b08 35 d01 b15 b15 b01 b04 b12 36 d01 b15 b15 b01 b08 b09

Chemical formula D R1 R2 R3 R4 R5 37 d01 b15 b15 b02 b01 b01 38 d01 b15 b15 b02 b01 b02 39 d01 b15 b15 b02 b01 b03 40 d01 b15 b15 b02 b01 b04 41 d01 b15 b15 b02 b01 b08 42 d01 b15 b15 b02 b01 b12 43 d01 b15 b15 b02 b02 b04 44 d01 b15 b15 b02 b02 b12 45 d01 b15 b15 b02 b03 b03 46 d01 b15 b15 b02 b03 b04 47 d01 b15 b15 b02 b03 b12 48 d01 b15 b15 b03 b01 b01 49 d01 b15 b15 b03 b01 b02 50 d01 b15 b15 b03 b01 b03 51 d01 b15 b15 b03 b01 b04 52 d01 b15 b15 b03 b01 b08 53 d01 b15 b15 b03 b01 b12 54 d01 b15 b15 b03 b02 b04 55 d01 b15 b15 b03 b02 b12 56 d01 b15 b15 b03 b03 b03 57 d01 b15 b15 b03 b03 b04 58 d01 b15 b15 b03 b03 b12 59 d01 b15 b15 b04 b01 b01 60 d01 b15 b15 b04 b01 b02 61 d01 b15 b15 b04 b01 b03 62 d01 b15 b15 b04 b01 b04

Chemical formula D R1 R2 R3 R4 R5 63 d01 b15 b15 b04 b01 b12 64 d01 b15 b15 b04 b02 b04 65 d01 b15 b15 b04 b02 b12 66 d01 b15 b15 b04 b03 b03 67 d01 b15 b15 b04 b03 b12 68 d01 b15 b15 b04 b04 b04 69 d01 b15 b15 b04 b04 b12 70 d01 b15 b01 b01 b01 b02 71 d01 b15 b01 b01 b01 b03 72 d01 b15 b01 b01 b01 b12 73 d01 b15 b01 b01 b02 b04 74 d01 b15 b01 b01 b02 b12 75 d01 b15 b01 b01 b03 b04 76 d01 b15 b01 b01 b03 b12 77 d01 b15 b01 b01 b04 b04 78 d01 b15 b01 b01 b04 b12 79 d01 b15 b01 b04 b03 b04 80 d01 b15 b01 b04 b03 b12 81 d01 b15 b01 b04 b04 b04 82 d01 b15 b01 b04 b04 b12 83 d01 b15 b02 b01 b01 b02 84 d01 b15 b02 b01 b01 b12 85 d01 b15 b02 b01 b03 b04 86 d01 b15 b02 b01 b03 b12 87 d01 b15 b02 b01 b04 b04 88 d01 b15 b02 b01 b04 b12

Chemical formula D R1 R2 R3 R4 R5 89 d01 b15 b03 b01 b01 b02 90 d01 b15 b03 b01 b01 b12 91 d01 b15 b03 b01 b03 b04 92 d01 b15 b03 b01 b03 b12 93 d01 b15 b03 b01 b04 b04 94 d01 b15 b03 b01 b04 b12 95 d01 b15 b04 b01 b01 b02 96 d01 b15 b04 b01 b04 b12 97 d01 b01 b15 b01 b01 b02 98 d01 b01 b15 b01 b01 b03 99 d01 b01 b15 b01 b01 b12 100 d01 b01 b15 b01 b02 b04 101 d01 b01 b15 b01 b02 b12 102 d01 b01 b15 b01 b03 b04 103 d01 b01 b15 b01 b03 b12 104 d01 b01 b15 b01 b04 b04 105 d01 b01 b15 b01 b04 b12 106 d01 b01 b15 b04 b03 b04 107 d01 b01 b15 b04 b03 b12 108 d01 b01 b15 b04 b04 b04 109 d01 b01 b15 b04 b04 b12 110 d01 b03 b15 b01 b01 b02 111 d01 b03 b15 b01 b01 b12 112 d01 b03 b15 b01 b03 b04 113 d01 b03 b15 b01 b03 b12 114 d01 b03 b15 b01 b04 b04

Chemical formula D R1 R2 R3 R4 R5 115 d01 b03 b15 b01 b04 b12 116 d01 b01 b01 b01 b04 b12 117 d01 b13 b01 b01 b04 b12 118 d01 b14 b01 b01 b04 b12 119 d02 b15 b15 b01 b01 b01 120 d02 b15 b15 b01 b01 b02 121 d02 b15 b15 b01 b01 b03 122 d02 b15 b15 b01 b01 b04 123 d02 b15 b15 b01 b01 b07 124 d02 b15 b15 b01 b01 b08 125 d02 b15 b15 b01 b01 b12 126 d02 b15 b15 b01 b02 b03 127 d02 b15 b15 b01 b02 b04 128 d02 b15 b15 b01 b02 b08 129 d02 b15 b15 b01 b02 b12 130 d02 b15 b15 b01 b03 b03 131 d02 b15 b15 b01 b03 b04 132 d02 b15 b15 b01 b03 b08 133 d02 b15 b15 b01 b03 b12 134 d02 b15 b15 b01 b04 b04 135 d02 b15 b15 b01 b04 b12 136 d02 b15 b15 b02 b01 b01 137 d02 b15 b15 b02 b01 b02 138 d02 b15 b15 b02 b01 b03 139 d02 b15 b15 b02 b01 b04 140 d02 b15 b15 b02 b01 b12

Chemical formula D R1 R2 R3 R4 R5 141 d02 b15 b15 b02 b02 b04 142 d02 b15 b15 b02 b02 b12 143 d02 b15 b15 b02 b03 b04 144 d02 b15 b15 b02 b03 b12 145 d02 b15 b15 b03 b01 b02 146 d02 b15 b15 b03 b01 b03 147 d02 b15 b15 b03 b01 b04 148 d02 b15 b15 b03 b01 b12 149 d02 b15 b15 b03 b02 b04 150 d02 b15 b15 b03 b02 b12 151 d02 b15 b15 b03 b03 b03 152 d02 b15 b15 b03 b03 b04 153 d02 b15 b15 b03 b03 b12 154 d02 b15 b15 b04 b01 b02 155 d02 b15 b15 b04 b01 b03 156 d02 b15 b15 b04 b01 b04 157 d02 b15 b15 b04 b01 b12 158 d02 b15 b15 b04 b02 b04 159 d02 b15 b15 b04 b02 b12 160 d02 b15 b15 b04 b03 b03 161 d02 b15 b15 b04 b03 b12 162 d02 b15 b15 b04 b04 b04 163 d02 b15 b15 b04 b04 b12 164 d02 b15 b01 b01 b01 b02 165 d02 b15 b01 b01 b01 b03 166 d02 b15 b01 b01 b01 b12

Chemical formula D R1 R2 R3 R4 R5 167 d02 b15 b01 b01 b02 b04 168 d02 b15 b01 b01 b02 b12 169 d02 b15 b01 b01 b03 b04 170 d02 b15 b01 b01 b03 b12 171 d02 b15 b01 b01 b04 b04 172 d02 b15 b01 b01 b04 b12 173 d02 b15 b01 b04 b03 b04 174 d02 b15 b01 b04 b03 b12 175 d02 b15 b01 b04 b04 b04 176 d02 b15 b01 b04 b04 b12 177 d02 b15 b02 b01 b01 b02 178 d02 b15 b02 b01 b01 b12 179 d02 b15 b02 b01 b03 b04 180 d02 b15 b02 b01 b03 b12 181 d02 b15 b02 b01 b04 b04 182 d02 b15 b02 b01 b04 b12 183 d02 b15 b03 b01 b01 b02 184 d02 b15 b03 b01 b01 b12 185 d02 b15 b03 b01 b03 b04 186 d02 b15 b03 b01 b03 b12 187 d02 b15 b03 b01 b04 b04 188 d02 b15 b03 b01 b04 b12 189 d02 b15 b04 b01 b01 b02 190 d02 b15 b04 b01 b04 b12 191 d02 b01 b15 b01 b01 b02 192 d02 b01 b15 b01 b01 b03

Chemical formula D R1 R2 R3 R4 R5 193 d02 b01 b15 b01 b01 b12 194 d02 b01 b15 b01 b02 b12 195 d02 b01 b15 b01 b03 b12 196 d02 b01 b15 b01 b04 b12 197 d02 b01 b15 b04 b03 b04 198 d02 b01 b15 b04 b03 b12 199 d02 b01 b15 b04 b04 b04 200 d02 b01 b15 b04 b04 b12 201 d02 b03 b15 b01 b01 b02 202 d02 b03 b15 b01 b01 b12 203 d02 b03 b15 b01 b03 b04 204 d02 b03 b15 b01 b03 b12 205 d02 b03 b15 b01 b04 b04 206 d02 b03 b15 b01 b04 b12 207 d02 b01 b01 b01 b04 b12 208 d03 b15 b15 b01 b01 b02 209 d03 b15 b15 b01 b04 b12 210 d04 b15 b15 b01 b04 b12 211 d05 b15 b15 b01 b04 b12 212 d06 b15 b15 b01 b04 b12

Accordingly, specific examples of the carbazole derivative having the structure of Chemical Formula (I), which enable an organic electroluminescent device having a particularly high luminous efficiency and a long lifetime, are represented by the following Chemical Formulas 12, 29, 32, 33, 35, 69, 116, 120, 121, 125, 129, 131, 133, 134, 135, 207 or 208. However, the present invention is not limited to these.

[Formula 12] [Formula 29]

[Formula 32] [Formula 33]

[Formula 35] [Formula 69]

[Formula 116] [Formula 120]

[Formula 121] [Formula 125]

[Formula 129] [Formula 131]

[Formula 133] [Formula 134]

[Formula 135] [Formula 207]

[Formula 208]

The present invention may be an organic light emitting composition or an organic light emitting material comprising or a carbazole derivative that can be used as a light emitting material of the organic electroluminescent device as described above. Using such a derivative, composition or material as a hole transporting material of the organic electroluminescent device can obtain a high luminous efficiency, it is possible to manufacture a device having excellent durability because of the high glass transition temperature of the carbazole derivatives. 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 carbazole 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 carbazole derivative represented by Formula I may be prepared by a synthetic route as in Scheme 1 below.

Scheme 1

1-1. Preparation of Formula A02

Into a 2000-ml, four-necked round bottom flask, 100 g (0.410 mol) of N -phenylcarbazole (Formula A01) was added and diluted with 600 ml of dichloromethane. 76 g of N -bromosuccinimide (NBS) was slowly added to the diluent, and the reaction solution was stirred at room temperature for 4 hours. After distilled water 600ml 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 110 g (yield 83%) of the title compound.

1-2. Preparation of Formula A03

100 g (0.310 mol) of formula A02 compound prepared in Example 1-1, 57 g of carbazole, 0.34 g of palladium acetate (II), tri- (t-butyl) force, in a 2000-ml, four-necked round bottom flask under nitrogen atmosphere 6.1 g of pin (10% hexane solution), 36 g of sodium t-butoxide and 1000 ml of O-xylene were added thereto. 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 76%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.53 (s, 1H), 8.33 (d, J = 8.1 Hz, 1H), 8.26 (d, J = 7.7 Hz, 2H), 7.73-7.70 (m, 4H), 7.61-7.57 (m, 3H), 7.51-7.41 (m, 4H), 7.36-7.26 (m, 5H).

1-3. Preparation of Formula A04

40 g (0.098 mol) of the compound of Formula A03 prepared in Example 1-2 were added to a 2000-ml, four-necked round bottom flask and diluted with 400 ml of dichloromethane. After cooling the dilution solution to 0 ° C., 17.4 g of N -bromosuccinimide (NBS) was slowly added thereto, followed by stirring for 3 hours. 400 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 45 g (yield 94%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.54 (d, J = 5.2 Hz, 2H), 8.32 (d, J = 7.7 Hz, 2H), 7.72 (d, J = 4.4 Hz, 4H), 7.60 -7.42 (m, 6 H), 7.37-7.29 (m, 5 H).

1-4. Preparation of Formula 12

45 g (0.092 mol) of Formula A04 compound prepared in Example 1-3, 22.3 g of N -phenyl-1-naphthylamine, 0.12 g of palladium acetate (II), in a 1000-ml, 4-necked round bottom flask under nitrogen atmosphere 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 give 51 g (yield 88%) of the title compound. MS ( m / z , [M] ⁺ ): C46H31N3: 625.46

Example 2 Preparation of Chemical Formula 35

1000-ml, 4 sphere formula prepared in Example 1-3 in a nitrogen atmosphere in a round bottom flask, compound A04 45g (0.092mol), N - ( 4- biphenyl), 9,9-dimethyl -9 H - fluoren 34 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 5 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 67 g (yield 94%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.58 (s, 1 H), 8.35 (d, J = 7.7 Hz, 1 H), 8.23 (d, J = 7.3 Hz, 1 H), 8.16 (s, 1 H) , 7.73-7.69 (m, 6H), 7.66-7.57 (m, 7H), 7.51-7.39 (m, 7H), 7.35-7.21 (m, 8H), 7.08 (d, J = 8.8 Hz, 2H), 7.02 (d, J = 8.1 Hz, 1H), 1.39 (s, 6H).

UV (λ _max ): 332 nm PL: 427 nm (see FIG. 1)

Glass transition temperature (measured by Tg, DSC): 168 ° C (see Figure 2)

Example 3 Preparation of Chemical Formula 129

3-1. Preparation of Formula A05

80 g (0.164 mol) of the compound of Formula A04 prepared in Example 1-3 were added to a 3000-ml, four-necked round bottom flask and diluted with 1600 ml of tetrahydrofuran. 28.2 g of 4-chlorobenzene boronic 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 75 g (yield 88%) of the title compound.

3-2. Preparation of Formula 129

1000-ml, 4 sphere formula A05 compound 40g (0.077mol) prepared in Example 3-1 in a nitrogen atmosphere in a round bottom flask, N - (1- naphthyl) 9,9-dimethyl -9 H - fluoren 27 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 6 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 26 g (yield 85%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.54 (d, J = 7.0 Hz, 2H), 8.33 (t, J = 6.2 Hz, 2H), 8.02 (d, J = 8.5 Hz, 1H), 7.92 (d, J = 8.4 Hz, 2H), 7.73-7.57 (m, 13H), 7.54-7.35 (m, 9H), 7.33-7.21 (m, 5H), 7.04 (d, J = 8.6 Hz, 2H), 6.89 (dd, J = 8.1, 1.8 Hz, 1H), 1.35 (s, 6H).

Example 4 Preparation of Chemical Formula 133

4-1. Preparation of Formula A06

40 g (0.077 mol) of formula A05 compound prepared in Example 3-1, 13 g of 2-naphthylamine, 0.07 g of palladium acetate (II), and tri- (t- 1.2 g of butyl) phosphine (10% hexane solution), 9 g of sodium t-butoxide and 450 ml of toluene were added thereto. The reaction solution was refluxed for 2 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried under vacuum to obtain 40 g (yield 83%) of the title compound.

4-2. Preparation of Formula 133

27 g (0.077 mol) of formula A06 compound prepared in Example 4-1 in a 1000-ml, four-necked round bottom flask under nitrogen atmosphere, 14 g of 2-bromo-9,9-dimethyl-9 H -fluorene, palladium acetate (II) 0.05 g, 0.8 g of tri- (t-butyl) phosphine (10% hexane solution), 4.6 g of sodium t-butoxide and 300 ml of o-xylene were added. 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 28 g (yield 79%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.60 (d, J = 11.2 Hz, 2H), 8.36 (dd, J = 7.7, 4.8 Hz, 2H), 7.88-7.83 (m, 3H), 7.79- 7.63 (m, 9H), 7.60 (s, 2H), 7.58-7.48 (m, 4H), 7.46-7.36 (m, 6H), 7.34-7.26 (m, 6H), 7.22 (d, J = 8.4 Hz, 2H), 7.08 (dd, J = 8.0, 1.6 Hz, 1H), 1.39 (s, 6H).

UV (λ _max ): 346 nm PL: 438 nm (see FIG. 3)

Glass transition temperature (measured by Tg, DSC): 169 ° C (see Figure 4)

Example 5 Preparation of Chemical Formula 135

1000-ml, 4 sphere formula prepared in Example 3-1 in a nitrogen atmosphere in a round bottom flask, compound A05 19g (0.037mol), N - ( 4- biphenyl), 9,9-dimethyl -9 H - fluoren 14 g of 2-amine, 0.05 g of palladium acetate (II), 0.7 g of tri- (t-butyl) phosphine (10% hexane solution), 4 g of sodium t-butoxide and 200 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 26 g (yield 85%) of the title compound.

¹ H NMR (400 MHz, DMSO-d ₆ ): δ 8.58 (d, J = 11.7 Hz, 2H), 8.35 (t, J = 7.0 Hz, 2H), 7.79-7.73 (m, 9H), 7.66-7.57 ( m, 7H), 7.50 (t, J = 7.3 Hz, 2H), 7.45-7.24 (m, 12H), 7.20 (d, J = 8.8 Hz, 2H), 7.15 (d, J = 8.8 Hz, 2H), 7.06 (dd, J = 8.1, 1.8 Hz, 1 H), 1.41 (s, 6 H).

UV (λ _max ): 355nm PL: 415nm

Glass transition temperature (measured by Tg, DSC): 170 ℃

Example 6

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 α-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 and luminous efficiency are shown in Table 10.

[Formula 2] [Formula 3]

[Formula 4] [Formula 5]

Example 7

Fabrication of Organic Electroluminescent Device Using Chemical Formula 29

In Example 6, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 6, except that Chemical Formula 29 was used instead of Chemical Formula 12 as the hole injection layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 8

Fabrication of Organic Electroluminescent Device Using Chemical Formula 32

In Example 6, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 6, except that Chemical Formula 32 was used instead of Chemical Formula 12 as the hole injection layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 9

Fabrication of Organic Electroluminescent Device Using Chemical Formula 33

In Example 6, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 6, except that Chemical Formula 33 was used instead of Chemical Formula 12 as the hole injection layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 10

Fabrication of Organic Electroluminescent Device Using Chemical Formula 35

In Example 6, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 6, except that Chemical Formula 35 was used instead of Chemical Formula 12 as the hole injection layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 11

Fabrication of Organic Electroluminescent Device Using Chemical Formula 69

In Example 6, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 6, except that Chemical Formula 69 was used instead of Chemical Formula 12 as the hole injection layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 12

Fabrication of Organic Electroluminescent Device Using Chemical Formula 116

In Example 6, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 6, except that Chemical Formula 116 was used instead of Chemical Formula 12 as the hole injection layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 13

Fabrication of Organic Electroluminescent Device Using Chemical Formula 120

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. Then, the chemical formula 120 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 α-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 and luminous efficiency are shown in Table 10.

[Formula 1]

Example 14

Fabrication of Organic Electroluminescent Device Using Chemical Formula 121

In Example 13, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 13, except that Chemical Formula 121 was used instead of Chemical Formula 120 as the hole transport layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 15

Fabrication of Organic Electroluminescent Device Using Chemical Formula 125

In Example 13, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 13, except that Chemical Formula 125 was used instead of Chemical Formula 120 as the hole transport layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 16

Fabrication of Organic Electroluminescent Device Using Chemical Formula 129

In Example 13, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 13, except that Chemical Formula 129 was used instead of Chemical Formula 120 as the hole transport layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 17

Fabrication of Organic Electroluminescent Device Using Chemical Formula 131

In Example 13, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 13, except that Chemical Formula 131 was used instead of Chemical Formula 120 as the hole transport layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 18

Fabrication of Organic Electroluminescent Device Using Chemical Formula 133

In Example 13, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 13, except that Formula 133 was used instead of Formula 120 as the hole transport layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 19

Fabrication of Organic Electroluminescent Device Using Chemical Formula 134

In Example 13, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 13, except that Formula 134 was used instead of Formula 120 as the hole transport layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 20

Fabrication of Organic Electroluminescent Device Using Chemical Formula 135

In Example 13, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 13, except that Chemical Formula 135 was used instead of Chemical Formula 120 as the hole transport layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Example 21

Fabrication of Organic Electroluminescent Device Using Formula 207

In Example 13, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 13, except that Chemical Formula 207 was used instead of Chemical Formula 120 as the hole transport layer. The measured highest luminance and luminous efficiency are shown in Table 10.

[Example 22]

Fabrication of Organic Electroluminescent Device Using Chemical Formula 208

In Example 13, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 13, except that Formula 208 was used instead of Formula 120 as the hole transport layer. The measured highest luminance and luminous efficiency are shown in Table 10.

Comparative Example 1

Fabrication of organic electroluminescent device using 2-TNATA and NPB

A transparent anode of indium tin oxide (ITO) having a film 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, the light emitting layer was formed by simultaneously depositing α-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 and luminous efficiency are shown in Table 11.

Luminescence Characteristics of Organic Electroluminescent Devices Example Compound of hole injection layer Compound of hole transport layer Brightness
(cd / m ² ) Efficiency
(cd / A) Example 6 Formula 12 NPB 9119 4.63 Example 7 Formula 29 NPB 18620 3.71 Example 8 Formula 32 NPB 11610 3.50 Example 9 Formula 33 NPB 9970 4.29 Example 10 Formula 35 NPB 20440 3.57 Example 11 Formula 69 NPB 12210 3.66 Example 12 Formula 116 NPB 12080 3.59 Example 13 2-TNATA Formula 120 13309 3.79 Example 14 2-TNATA Formula 121 10590 3.95 Example 15 2-TNATA Formula 125 15240 5.86 Example 16 2-TNATA Formula 129 10980 4.66 Example 17 2-TNATA Formula 131 14170 3.82 Example 18 2-TNATA Formula 133 20490 4.75 Example 19 2-TNATA Formula 134 20440 3.72 Example 20 2-TNATA Formula 135 14170 4.02 Example 21 2-TNATA Formula 207 9491 4.03 Example 22 2-TNATA Formula 208 8498 3.82 Comparative Example 1 2-TNATA NPB 7546 3.22

As can be seen in Table 11, it can be seen that the organic electroluminescent device according to Examples 6 to 22 of the present invention has a higher luminance and efficiency than Comparative Example 1.

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 carbazole derivative represented by the following general formula (I).
(I)

(In Formula I, R1 and R2 are each hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group, and R3 to R5 are each a substituted or unsubstituted aryl group, or substituted Unsubstituted heteroaryl group, D is a linker, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.)
According to claim 1, wherein the formula I is any one of the following formula 12, 29, 32, 33, 35, 69, 116, 120, 121, 125, 129, 131, 133, 134, 135, 207 or 208 An organic electroluminescent composition characterized by.
[Formula 12] [Formula 29]

[Formula 32] [Formula 33]

[Formula 35] [Formula 69]

[Formula 116] [Formula 120]

[Formula 121] [Formula 125]

[Formula 129] [Formula 131]

[Formula 133] [Formula 134]

[Formula 135] [Formula 207]

Formula 208

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

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