KR20090112137A - Organic Light Emitting Material and Organic Light Emitting Diode Having The Same - Google Patents

Abstract

PURPOSE: An organic light-emitting material and organic light emitting diode comprising the same are provided to secure high thermal stability, luminescent brightness, and luminous efficiency. CONSTITUTION: An organic light-emitting material is used for organic light emitting diode. An organic light-emitting material comprises a compound represented by formula 1. In formula 1, R1 and R2 are independently non-substituted or substituted C6-C30 aryl groups with alkyl, alkoxy, aryl, styryl, cyano, nitro, or amino group; and D is non-substituted or substituted C6-C18 aryl group having nucleus carbon atoms.

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 non-carbazole compound derivative used as a light emitting material of an organic electroluminescent device, and more particularly to preparing a non-carbazole compound derivative having a high glass transition temperature and By using it as a light emitting material of an organic electroluminescent device, it is to provide an organic electroluminescent device having excellent thermal stability, increasing the life of the device, and excellent in luminescence brightness and luminescence 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-layer organic electroluminescent device comprising two organic layers (hole transport layer and light emitting layer) interposed 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.

Subsequently, materials used in the hole transport layer and the light emitting layer were continuously developed to develop a device having a lifespan and a luminous efficiency that can be put to practical use. However, in order to make the organic electroluminescent device device more practical, in addition to configuring the device in the above multilayer structure, the device material, particularly the hole transport material, must have thermal and electrical stability. 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]

Since CuPC is a metal complex compound, it is widely used because it has excellent adhesion to ITO substrate and is the most stable. However, since absorption occurs in the visible light region, it is difficult to realize a total color, and m-MTDATA or 2-TNATA have a glass transition temperature of 78 Not only low as ℃ and 108 ℃ but also a lot of problems in the process of mass production, there is also 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.

An object of the present invention is to provide a bicarbazole compound derivative having a high glass transition temperature, an organic electroluminescent composition comprising the same, and an organic electroluminescent device to solve the above problems. 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 bicarbazole derivative represented by the following general formula (I).

[Formula I]

(In formula (I), R1 and R2 each represent an aryl group having 6 to 30 nuclear carbon atoms unsubstituted or substituted with an alkyl group, an alkoxy group, an aryl group, a styryl group, a cyano group, a nitro group or an amino group, and D Represents an substituted or unsubstituted aryl group having 6 to 18 nuclear carbon atoms.)

Here, D of Formula I may have a unit structure of d01, R1 may have a unit structure of b01, and R2 may have a unit structure of b01, b02 or b09.

[d01] [b01] [b02] [b09]

In addition, D of Formula I may have a unit structure of d01 or d02, and R1 and R2 may each have a unit structure of b04.

[d01] [d02] [b04]

Another embodiment of the present invention is an organic electroluminescent device comprising at least one organic layer comprising the organic light emitting 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 bicarbazole 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. As a result, the present invention showed better light emission characteristics in terms of current density, brightness, highest brightness, and luminous efficiency than conventional hole transport material NPB (Formula 2).

Accordingly, when the organic electroluminescent device is manufactured by using the non-carbazole derivative according to the present invention as a hole transporting material, the problem of low luminous brightness and low luminous efficiency, which is the biggest disadvantage of the conventional organic electroluminescent device, is simultaneously solved. In addition to the high glass ion, the thermal stability of the organic electroluminescent device is excellent, making it possible to manufacture high-performance organic electroluminescent devices and commercializing full-color organic electroluminescent devices requiring high efficiency, high brightness and long life. Can contribute significantly.

The present invention is a bicarbazole 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 bicarbazole derivative has a high glass transition temperature and excellent hole injection and transport ability. Since the organic electroluminescent device is manufactured using the same as a 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 each represent an aryl group having 6 to 30 nuclear carbon atoms unsubstituted or substituted with an alkyl group, an alkoxy group, an aryl group, a styryl group, a cyano group, a nitro group or an amino group, and D Represents an substituted or unsubstituted aryl group having 6 to 18 nuclear carbon atoms.)

The present invention may be a non-carbazole derivative that can be used as a light emitting material of the organic electroluminescent device as described above, or may be an organic light emitting composition or an organic light emitting material including the same.

In formula (I), R1 and R2 are each substituted by the above-described functional groups or unsubstituted by any functional group, may be an aryl group having 6 to 30 nuclear carbon atoms, examples of such aryl groups are phenyl group, naph And a methyl group, a phenanthryl group, an anthryl group, a biphenyl group, a terphenyl group and the like.

A process for preparing a bicarbazole derivative that enables high luminous efficiency and long life organic electroluminescent device according to the present invention will be described below.

The process for preparing Formula I consists of the following steps. The inventors have been able to prepare compounds having the general structure of formula (I) from carbazole in the same synthetic route as in Scheme 1 below.

Scheme 1

In Scheme 1, X is a leaving group, preferably a halogen atom, and R1 and R2 are each 6 to 30 nuclei unsubstituted or substituted with an alkyl, alkoxy, aryl, styryl, cyano, nitro or amino group. An aryl group having a carbon atom is represented and D represents an aryl group having 6 to 18 nuclear carbon atoms which is substituted or unsubstituted.

First, referring to Yan Gao et al., Macromolecules, 4744 (2007), 3,3-bicarbazole (a) was prepared from two carbazoles using iron chloride, and 3 containing a leaving group (X). Through the amination reaction with the primary amine compound (b), a material of the organic electroluminescent device represented by the general formula (I), which is finally a bicarbazole derivative according to the present invention, was prepared.

There are two main methods for the amination reaction used in the final step of synthesizing the general formula (I) in the manufacturing process.

The first method is the Ulnamm reaction using a copper catalyst, although not particularly limited, copper powder or copper sulfate (CuSO ₄ ) is suitable for the reaction, and potassium carbonate or sodium carbonate is most suitable. N, N -dimethylsulfoxide, nitrobenzene, or decalin is used, which is not used or has a high boiling point. Sometimes crown ether or poly (ethylene glycol) is used to make the reaction run smoother.

The second method is to use a palladium catalyst, which performs an amination reaction using a palladium catalyst, a phosphine catalyst and a base under a suitable reaction solvent. The palladium catalyst used in the reaction is not particularly limited, but mainly palladium acetate or tris (Dibenzylideneacetone) dipalladium (0) and the phosphine catalyst is not particularly limited, and tri- ( o -tolyl) phosphine, 2,2'-bis (diphenylphosphino) -1,1 ' -Vinaphthyl, tri- (n-butyl) phosphine or tri- (t-butyl) phosphine or the like is used. As the reaction base, metal alkoxides such as sodium t-butoxide or potassium th-butoxide are used. The reaction solvent is not particularly limited and may be non-reactive with the reagents used and have a solubility that allows the reaction to proceed smoothly. Specific examples include benzene, toluene, xylene, N, N -dimethylformamide, N, N -dimethylsulfoxide , and the like. The reagent or reaction solvent used in the reaction is not particularly limited thereto.

In the above formula (I), preferred examples of R1 and R2 may each be a unit structure of the formula shown in Table 1 or include such a unit structure, and each unit structure is named with a delimiter as b01 to b19 to distinguish it. It was.

TABLE 1

In addition, in the formula (I), a preferred example of D may be a unit structure of the formula shown in Table 2 below or include such a unit structure, each unit structure is named with a delimiter from d01 to d06 to distinguish it It was.

TABLE 2

Based on Tables 1 and 2, specific examples of the bicarbazole derivatives having the structure of general formula (I) finally enabling organic light emitting devices having high luminous efficiency and long life are shown in Tables 3 to 6 below. It includes a compound represented. However, the present invention is not limited to these.

TABLE 3

Chemical formula D R2 R3 I-001 d01 b01 b01 I-002 d01 b01 b02 I-003 d01 b01 b03 I-004 d01 b01 b04 I-005 d01 b01 b05 I-006 d01 b01 b07 I-007 d01 b01 b09 I-008 d01 b01 b10 I-009 d01 b01 b11 I-010 d01 b01 b12 I-011 d01 b01 b13 I-012 d01 b01 b14 I-013 d01 b01 b15 I-014 d01 b01 b19 I-015 d01 b02 b02 I-016 d01 b02 b03 I-017 d01 b02 b04 I-018 d01 b02 b05 I-019 d01 b02 b10 I-020 d01 b02 b13 I-021 d01 b02 b15 I-022 d01 b02 b16 I-023 d01 b03 b03 I-024 d01 b03 b04 I-025 d01 b03 b05 I-026 d01 b03 b10 I-027 d01 b03 b12 I-028 d01 b03 b13 I-029 d01 b04 b04

TABLE 4

Chemical formula D R2 R3 I-030 d01 b04 b09 I-031 d01 b04 b10 I-032 d01 b04 b13 I-033 d01 b04 b16 I-034 d01 b05 b05 I-035 d01 b05 b10 I-036 d01 b05 b11 I-037 d01 b07 b13 I-038 d01 b09 b12 I-039 d01 b10 b10 I-040 d01 b12 b12 I-041 d01 b13 b13 I-042 d01 b14 b14 I-043 d01 b16 b16 I-044 d01 b01 b06 I-045 d01 b01 b08 I-046 d01 b02 b09 I-047 d01 b02 b12 I-048 d02 b01 b01 I-049 d02 b01 b02 I-050 d02 b01 b03 I-051 d02 b01 b04 I-052 d02 b01 b09 I-053 d02 b01 b12 I-054 d02 b01 b16 I-055 d02 b02 b02 I-056 d02 b02 b04 I-057 d02 b03 b03 I-058 d02 b03 b04

TABLE 5

Chemical formula D R2 R3 I-059 d02 b03 b09 I-060 d02 b04 b04 I-061 d02 b04 b09 I-062 d02 b04 b10 I-063 d02 b04 b12 I-064 d03 b01 b01 I-065 d03 b01 b02 I-066 d03 b01 b03 I-067 d03 b01 b04 I-068 d03 b01 b09 I-069 d03 b01 b12 I-070 d03 b02 b02 I-071 d03 b02 b04 I-072 d03 b03 b03 I-073 d03 b03 b04 I-074 d03 b04 b04 I-075 d03 b04 b13 I-076 d04 b01 b01 I-077 d04 b01 b02 I-078 d04 b01 b03 I-079 d04 b01 b04 I-080 d04 b01 b09 I-081 d04 b01 b13 I-082 d04 b01 b17 I-083 d04 b01 b18 I-084 d04 b02 b02 I-085 d04 b02 b03 I-086 d04 b02 b04 I-087 d04 b03 b03

TABLE 6

Chemical formula D R2 R3 I-088 d04 b03 b04 I-089 d04 b04 b04 I-090 d04 b04 b09 I-091 d05 b01 b01 I-092 d05 b01 b02 I-093 d05 b01 b03 I-094 d05 b01 b04 I-095 d05 b01 b09 I-096 d05 b02 b02 I-097 d05 b02 b03 I-098 d05 b03 b03 I-099 d05 b04 b04 I-100 d06 b01 b01 I-101 d06 b01 b02 I-102 d06 b01 b03 I-103 d06 b01 b04 I-104 d06 b01 b09 I-105 d06 b01 b13 I-106 d06 b02 b02 I-107 d06 b02 b03 I-108 d06 b03 b03 I-109 d06 b04 b04

According to the present invention, the bicarbazole derivative represented by Chemical Formula I may be prepared by the above method, and the present invention may be a material or composition for an organic electroluminescent device including the same. When such a material or composition is used as a hole transport material of an 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 non-carbazole 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.

The bicarbazole derivatives represented by Formula I of the present invention synthesized as described above were purified using recrystallization and sublimation in view of the characteristics of organic electroluminescent devices 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 I-001

1-1. Preparation of 3,3'-bicarbazole (Formula a)

This synthesis example is to prepare 3,3'-bicarbazole of the formula (a) according to Scheme 1 above.

100 g (0.598 mol) of carbazole and 1000 ml of chloroform were added to a 3000-ml, four-necked round bottom flask and stirred. A solution in which 400 g of iron chloride was suspended in 1000 ml of chloroform was slowly added to the reaction solution at room temperature. The reaction solution is stirred at room temperature for 2 hours and then poured into 6000 ml of methanol being stirred vigorously. The resulting solid was filtered, washed with ammonia water, distilled water and methanol, and the collected solid was dried in vacuo to obtain 96.4 g of the target compound (yield 97%).

¹ H NMR (400 MHz, DMSO-d6): δ 8.43 (s, 2H), 8.22 (d, J = 7.6 Hz, 2H), 7.77 (dd, J = 8.4, 2.0 Hz, 2H), 7.53 (d, J = 8.4 Hz, 2H), 7.47-7.41 (m, 8H), 7.33-7.25 (m, 14H), 7.24-7.20 (m, 8H), 7.08 (t, J = 6.8 Hz, 4H).

1-2. 4- Of bromotriphenylamine  Produce

This synthesis example is to prepare a tertiary amine compound of formula b according to Scheme 1 above.

After 5000-ml and 4-necked round bottom flask was completely dried, 300 g (1.77 mol) of diphenylamine was added under a nitrogen atmosphere and dissolved in 3000 ml of anhydrous toluene. In this solution, 651 g (2.30 mol) of 1-bromo-4-iodobenzene, 10.77 g (35.4 mmol) of tri ( o -tolyl) phosphine, and 16.2 g (17.7 g) of tris (dibenzylideneacetone) dipalladium (0) mmol) and 255.7 g (2.66 mol) of sodium t-butoxide. The mixture was refluxed for 1 day, cooled to 40 ° C., 500 ml of toluene and 1000 ml of distilled water were added, and the target compound was extracted. The separated organic layer was dried, concentrated under reduced pressure to about 500 ml of toluene, and then 3000 ml of methanol was added to form a solid. The resulting solid was filtered, washed with methanol and dried in vacuo to give 441.9 g (yield 77%) of the title compound.

¹ H NMR (600 MHz, CDCl ₃ ): δ 7.33 (d, J = 8.9 Hz, 2H), 7.28-7.25 (m, 4H), 7.08 (d, J = 7.6 Hz, 4H), 7.05 (t, J = 7.4 Hz, 2H), 6.95 (d, J = 8.9 Hz, 2H).

MALDI-TOF mass (M + H ⁺ ): C18H14BrN: 323.9308 (324.0310)

1-3. Preparation of Formula I-001

In a 250-ml, three-necked round bottom flask, 11 g (0.033 mol) of 3,3'-bicarbazole prepared in Example 1-1, 4-bromotriphenylamine 22.5 prepared in Example 1-2 above g, 0.015 g of palladium acetate (II), 0.27 g of tri- (t-butyl) phosphine (10% hexane solution), 7.6 g of sodium t-butoxide and 100 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 24.1 g (yield 89%) of the title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.43 (s, 2H), 8.22 (d, J = 7.6 Hz, 2H), 7.77 (dd, J = 8.4, 2.0 Hz, 2H), 7.53 (d, J = 8.4 Hz, 2H), 7.47-7.41 (m, 8H), 7.33-7.25 (m, 14H), 7.24-7.20 (m, 8H), 7.08 (t, J = 6.8 Hz, 4H).

MALDI-TOF mass (M + H ⁺ ): C60H42N4: 819.0435 (819.0024)

UV (λ _max ): 307 nm PL: 412 nm (see Fig. 1)

Glass transition temperature (measured by Tg, DSC): 156 ° C (see Figure 5)

1-4. Other Preparations of Formula I-001

This Example relates to an example of preparing Chemical Formula I-001 as in Example 1-3, but in this example, the Ulman reaction using a copper catalyst instead of a palladium catalyst was used as the condition for the amination reaction. .

In a 250-ml, three-necked round bottom flask, 11 g (0.033 mol) of 3,3'-bicarbazole prepared in Example 1-1, 4-bromotriphenylamine 22.5 prepared in Example 1-2 above g, 13.7 g of potassium carbonate and 0.31 g of copper powder are added. After heating the reaction vessel for 20 hours at 220 ° C. to 230 ° C., the reaction solution was cooled to 60 ° C. while adding an appropriate amount of N, N -dimethylformamide to prevent the reaction solution from hardening. Tetrahydrofuran was added to the suspension and filtered to remove insoluble matters. The filtrate was concentrated appropriately and excess methanol was added to precipitate the target compound as a solid. The obtained solid was filtered, washed sequentially with distilled water and methanol, and then dried in vacuo to obtain 21.9 g (yield 81%) of the title compound.

Example 2 Preparation of Chemical Formula I-002

2-1. (4- Bromophenyl ) -Naphthalen-1-yl- Phenylamine  Produce

This synthesis example is to prepare a tertiary amine compound of formula b according to Scheme 1 above.

After 2000-ml and 4-necked round bottom flask was completely dried, 150 g (0.68 mol) of naphthalen-1-yl-phenylamine was added under a nitrogen atmosphere and dissolved in 1500 ml of anhydrous toluene. To this solution, 196 g of 1-bromo-4-iodobenzene, 2.1 g of tri ( o -tolyl) phosphine, 3.1 g of tris (dibenzylideneacetone) dipalladium (0) and 85.5 g of sodium t-butoxide Input. The mixture was refluxed for 5 hours, cooled to 40 ° C, 500 ml of toluene and 1000 ml of distilled water were added to extract the target compound. The separated organic layer was dried and concentrated under reduced pressure such that the residual amount of toluene was about 500 ml, and then a solid was formed in 3000 ml of 90% aqueous methanol solution. The resulting solid was filtered, washed with methanol and dried in vacuo to afford the crude product, which was then recrystallized to obtain 133.9 g (yield 52%) of the title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.87 (d, J = 4.4 Hz, 1H), 7.85 (d, J = 3.6 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.45 (t , J = 7.8 Hz, 2H), 7.34 (t, J = 8.2 Hz, 1H), 7.29-7.16 (m, 5H), 7.03-6.92 (m, 3H), 6.84 (d, J = 9.2 Hz, 2H) .

2-2. Preparation of Formula I-002

3,3′-bicarbazole 12.2 g (0.037ol) prepared in Example 1-1 in a 250-ml, three-necked round bottom flask, (4-bromophenyl) prepared in Example 2-1 29 g of naphthalen-1-yl-phenylamine, 0.017 g of palladium acetate (II), 0.3 g of tri- (t-butyl) phosphine (10% hexane solution), 8.5 g of sodium t-butoxide and 120 ml of o-xylene Was added. The reaction solution was refluxed for 20 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 83%) of the title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.41 (s, 2H), 8.20 (d, J = 7.6 Hz, 2H), 8.03 (d, J = 8.4 Hz, 2H), 7.91 (d, J = 8.0 Hz , 2H), 7.82 (d, J = 8.4 Hz, 2H), 7.74 (d, J = 8.4 Hz, 2H), 7.55-7.36 (m, 18H), 7.29-7.26 (m, 4H), 7.22-7.17 ( m, 10H), 7.00 (t, J = 7.2 Hz, 2H).

MALDI-TOF mass (M + H ⁺ ): C68H46N4: 918.5753 (918.3722)

UV (λ _max ): 330 nm PL: 443 nm (see FIG. 2)

Melting point (mp): 303 ° C Glass transition temperature (measured by Tg, DSC): 161 ° C (see Fig. 6)

Example 3 Preparation of Chemical Formula I-007

3-1. Phenanthrene-9-day- Diphenylamine  Produce

This synthesis example is to prepare a precursor for preparing a tertiary amine compound of formula b according to Scheme 1 above.

After 1000-ml and 4-necked round bottom flask was completely dried, 46.6 g (0.28 mol) of diphenylamine was added under a nitrogen atmosphere and dissolved in 470 ml of anhydrous toluene. To this solution was added 70 g of 9-bromophenanthrene, 1 g of tri- (t-butyl) phosphine (10% hexane solution), 0.06 g of palladium acetate (II) and 31.4 g of sodium t-butoxide. The mixture was refluxed for 4 hours, cooled to 40 ° C, 200 ml of toluene and 1000 ml of distilled water were added, and the target compound was extracted. The separated organic layer was dried, concentrated under reduced pressure to a residual amount of toluene of about 100 ml, and then formed a solid with excess methanol. The resulting solid was filtered, washed with methanol and dried in vacuo to yield 75 g (yield 79%) of the title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.71 (d, J = 7.6 Hz, 1H), 8.67 (d, J = 8.0 Hz, 1H), 8.02 (d, J = 7.6 Hz, 1H), 7.73 (d , J = 7.2 Hz, 1H), 7.64-7.53 (m, 4H), 7.45 (t, J = 7.6 Hz, 1H), 7.22-7.06 (m, 8H), 6.92 (t, J = 7.4 Hz, 2H) .

3-2. (4- Bromophenyl ) -Phenanthrene-9-day- Phenylamine  Produce

This synthesis example is to prepare a tertiary amine compound of formula b according to Scheme 1 above.

After 1000-ml and 4-necked round bottom flask was completely dried, 70 g (0.203 mol) of phenanthrene-9-yl-diphenylamine was added under a nitrogen atmosphere and dissolved in 700 ml of chloroform. After cooling this solution to 10 degreeC, 36 g of N-bromosuccinimides are added at the same temperature. After stirring for 3 hours at room temperature, the precipitated solid was removed by vacuum filtration. The collected filtrate was concentrated and the residue was dissolved in 100 ml of tetrahadrofuran. Excess methanol was added to the solution to precipitate the crystals and vacuum filtered. The filtered solid was washed with methanol and dried in vacuo to give 58 g (yield 67%) of the title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.71 (d, J = 8.0 Hz, 1H), 8.67 (d, J = 8.0 Hz, 1H), 7.96 (d, J = 8.4 Hz, 1H), 7.73 (d , J = 8.0 Hz, 1H), 7.63 (t, J = 7.6 Hz, 2H), 7.58-7.44 (m, 3H), 7.28-7.07 (m, 6H), 6.98-6.92 (m, 3H).

3-3. Preparation of Formula I-007

250-ml, 3-necked round bottom flask was prepared in Example 1-1, 3,3'-bicarbazole 10g (0.030mol), (4-bromophenyl)-prepared in Example 3-2 36 g of phenanthrene-9-yl-phenylamine, 0.014 g of palladium acetate (II), 0.24 g of tri- (t-butyl) phosphine (10% hexane solution), 7.3 g of sodium t-butoxide and 100 ml of o-xylene Was added. The reaction solution was refluxed for 22 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 27 g (yield 87%) of the title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.76 (d, J = 8.4 Hz, 2H), 8.71 (d, J = 8.0 Hz, 2H), 8.40 (s, 2H), 8.19 (d, J = 8.0 Hz , 2H), 8.14 (d, J = 8.4 Hz, 2H), 7.83 (d, J = 8.0 Hz, 2H), 7.75-7.54 (m, 11H), 7.50 (d, J = 8.4 Hz, 2H), 7.43 -7.37 (m, 7H), 7.30-7.22 (m, 16H), 7.03-7.00 (m, 2H).

MALDI-TOF mass (M + H ⁺ ): C76H50N4: 1018.2147 (1018.4035)

UV (λ _max ): 307 nm PL: 448 nm (see Fig. 3)

Melting point (mp): 188 ° C Glass transition temperature (measured by Tg, DSC): 406 ° C (see Fig. 7)

Example 4 Preparation of Chemical Formula I-029

In this example, 40 g of bis-biphenyl-4-yl- (4-bromophenyl) amine was used instead of 36 g of (4-bromophenyl) -phenanthrene-9-yl-phenylamine in Example 3-3. Except for the synthesis of the formula I-029 in the same manner as in Example 3-3 to obtain 27g (yield 79%).

Example 5 Preparation of Chemical Formula I-060

In this example, in Example 3-3, bis-biphenyl-4-yl- (4-bromonaphthalen-1-yl) instead of 36 g of (4-bromophenyl) -phenanthren-9-yl-phenylamine. Except for using 45g of amines, the compound of Formula I-060 was synthesized in the same manner as in Example 3-3, and 28g (yield 77%) was obtained.

Example 6 Preparation of Chemical Formula I-076

6-1. 4'- Chlorobiphenyl -4- days- Diphenylamine  Produce

This synthesis example is to prepare a tertiary amine compound of formula b according to Scheme 1 above.

In a 10-L, 5-necked round bottom flask, (4-bromophenyl) -diphenylamine 90g (0.28mol), 82.1g of 4-chlorophenylboronic acid, 153.5g of potassium carbonate, 4.5g of tetrabutylammonium bromide, toluene 3200ml, ethanol 1200ml and distilled water 2000ml was added. In the state of blocking light, 6.4 g of tetrakis (triphenylphosphine) palladium (0) was added while stirring the above mixture. The mixture was refluxed for 20 hours, cooled to room temperature, and the target compound was extracted. The separated organic layer was dried, concentrated under reduced pressure and formed a solid with excess methanol. The resulting solid was filtered, washed with methanol and dried in vacuo to give 98 g (yield 99%) of the title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.47 (d, J = 8.8 Hz, 2H), 7.40 (d, J = 8.8 Hz, 2H), 7.36 (d, J = 8.8 Hz, 2H), 7.27-7.23 (m, 5H), 7.12-7.09 (m, 5H), 7.02 (t, J = 7.4 Hz, 2H).

6-2. Preparation of Formula I-076

In a 250-ml, three-necked round bottom flask, 13 g (0.039 mol) of 3,3'-bicarbazole prepared in Example 1-1, 4'-chlorobiphenyl-4 prepared in Example 6-1 31 g of -yl-diphenylamine, 0.018 g of palladium acetate (II), 0.32 g of tri- (t-butyl) phosphine (10% hexane solution), 9.4 g of sodium t-butoxide and 130 ml of o-xylene were added thereto. . The reaction solution was refluxed for 20 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered and dried in vacuo to give 32 g (yield 85%) of the title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 8.46 (s, 2H), 8.24 (d, J = 7.6 Hz, 2H), 7.81-7.77 (m, 6H), 7.65 (d, J = 8.4 Hz, 4H) , 7.57 (d, J = 8.4 Hz, 4H), 7.50 (d, J = 8.0 Hz, 2H), 7.44 (t, J = 7.2 Hz, 2H), 7.33-7.15 (m, 24H), 7.05 (t, J = 7.2 Hz, 4H).

MALDI-TOF mass (M + H ⁺ ): C72H50N4: 970.1827 (970.4035)

UV (λ _max ): 347 nm PL: 410 nm (see FIG. 4)

Example 7

Formula I- 001  Fabrication of organic electroluminescent device used as single layer material

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 I-001 of the present invention was deposited to have a thickness of 1000 kPa. Finally, aluminum and lithium were simultaneously deposited to form a cathode having a thickness of 1000 mW. The current was measured by applying a voltage of 0 to 12V to the organic electroluminescent device manufactured as described above. At 6 V applied voltage, the current density was 3.46 mA / cm ² .

Example 8

Fabrication of Organic Electroluminescent Device Using Chemical Formula I-002 as Single Layer Material

In the present Example, the organic electroluminescent device was manufactured and evaluated in the same manner as in Example 7, except that Formula I-002 was used instead of Formula I-001 in Example 7. At 6 V applied voltage, the current density was 6.75 mA / cm ² .

Example 9

Formula I- 007  Fabrication of organic electroluminescent device used as single layer material

In the present Example was manufactured and evaluated in the same manner as in Example 7, except for using the formula I-007 instead of the formula I-001 in Example 7. At 6 V applied voltage, the current density was 15.3 mA / cm ² .

Example 10

Fabrication of Organic Electroluminescent Device Using Chemical Formula I-060 as Single Layer Material

In the present Example, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 7, except that Formula I-060 was used instead of Formula I-001 in Example 7. At 6 V applied voltage, the current density was 0.332 mA / cm ² .

Example 11

Fabrication of Organic Electroluminescent Device Using Chemical Formula I-076 as Single Layer Material

In the present Example, the organic electroluminescent device was manufactured and evaluated in the same manner as in Example 7, except that Formula I-076 was used instead of Formula I-001 in Example 7. At 6 V applied voltage, the current density was 13.0 mA / cm ² .

Comparative Example 1

NPB Manufacture of Organic Electroluminescent Device Using Alkali as Single Layer Material

In the present Comparative Example, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 1, except that NPB of the following Chemical Formula 2, which is widely known in the art, was used instead of Chemical Formula I-001. At 6 V applied voltage, the current density was 0.0112 mA / cm ² .

[Formula 1] [Formula 2] [Formula 3]

Example 12

Fabrication of Green Organic Electroluminescent Device Using Chemical Formula I-001 as Hole Transport Layer Material

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 500 kPa, thereby forming a hole injection layer. Subsequently, the chemical formula I-001 of the present invention was deposited to have a thickness of 300 GPa to form a hole transport layer. Subsequently, Alq ₃ of Chemical Formula 3 was deposited to have a thickness of 500 μs to form a light emitting layer. Subsequently, lithium fluoride was deposited to have a thickness of 8 GPa to form an electron injection layer. Finally, aluminum and lithium were simultaneously deposited to form a cathode having a thickness of 1000 mW. A luminescence test was performed by applying a voltage of 0 to 17 V to the organic electroluminescent device (see FIG. 8) manufactured as described above. At 9V applied voltage, the current density was 31.55mA / cm ² , the luminance was 1485cd / m ² , the luminous efficiency was 4.71cd / A, 1.64lm / W and the highest luminance was 25910cd / m ² . The electroluminescence spectrum graph is shown in FIG. 9.

Example 13

Fabrication of Green Organic Electroluminescent Device Using Chemical Formula I-002 as Hole Transport Layer Material

In the present Example, the organic electroluminescent device was manufactured and evaluated in the same manner as in Example 12, except that Formula I-002 was used instead of Formula I-001 in Example 12. At 9V applied voltage, the current density was 7.30mA / cm ² , the luminance was 306cd / m ² , the luminous efficiency was 4.19cd / A, 1.46lm / W, and the highest luminance was 14590cd / m ² . The electroluminescent spectral graph is shown in FIG. 9.

Example 14

Formula I-007 Hole transport layer  Fabrication of Green Organic Electroluminescent Devices Using Materials

In the present Example, the organic electroluminescent device was manufactured and evaluated in the same manner as in Example 12, except that Formula I-007 was used instead of Formula I-001 in Example 12. At 9V applied voltage, the current density was 9.42mA / cm ² , the luminance was 426cd / m ² , the luminous efficiency was 4.52cd / A, 1.58lm / W, and the highest luminance was 9837cd / m ² . The electroluminescent spectral graph is shown in FIG. 9.

Example 15

Formula I-029 Hole transport layer  Fabrication of Green Organic Electroluminescent Devices Using Materials

In the present Example, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 12, except that Formula I-029 was used instead of Formula I-001 in Example 12. At 9V applied voltage, the current density was 8.73mA / cm ² , the luminance was 324cd / m ² , the luminous efficiency was 3.71cd / A, 1.30lm / W, and the highest luminance was 19390cd / m ² .

Example 16

Formula I-060 Hole transport layer  Fabrication of Green Organic Electroluminescent Devices Using Materials

In the present Example, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 12 except that Formula I-060 was used instead of Formula I-001 in Example 12. At 9V applied voltage, the current density was 7.62mA / cm ² , the luminance was 283cd / m ² , the luminous efficiency was 3.71cd / A, 1.30lm / W, and the highest luminance was 16150cd / m ² .

Example 17

Formula I-076 Hole transport layer  Fabrication of Green Organic Electroluminescent Devices Using Materials

In the present Example, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 12, except that Formula I-076 was used instead of Formula I-001 in Example 12. At 9V applied voltage, the current density was 19.80mA / cm ² , the luminance was 734cd / m ² , the luminous efficiency was 3.71cd / A, 1.30lm / W, and the maximum luminance was 22080cd / m ² . The electroluminescent spectral graph is shown in FIG. 9.

Comparative Example 2

NPB To Hole transport layer  Fabrication of Green Organic Electroluminescent Devices Using Materials

In Comparative Example 12, an organic electroluminescent device was manufactured and evaluated in the same manner as in Example 12, except that NPB of Chemical Formula 2, which is well known in the art, was used instead of Chemical Formula I-001. At 9V applied voltage, the current density was 5.07A / cm ² , the luminance was 183cd / m ² , the luminous efficiency was 3.60cd / A, 1.26lm / W, and the highest luminance was 14310d / m ² . The electroluminescence spectrum graph is shown in FIG. 9.

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.

1 is a UV / Vis. For the bicarbazole derivatives of Formula I-001 in accordance with an example of the invention. And fluorescence spectral graphs.

FIG. 2 is a UV / Vis. And fluorescence spectral graphs.

Figure 3 is a UV / Vis for the bicarbazole derivatives of formula I-007 in accordance with an example of the present invention. And fluorescence spectral graphs.

4 is a UV / Vis. For the bicarbazole derivatives of Formula I-076 in accordance with an example of the present invention. And fluorescence spectral graphs.

FIG. 5 is a differential scanning calorimetry (DSC) curve graph of a bicarbazole derivative of Formula (I-001) according to one embodiment of the present invention. FIG.

6 is a differential scanning calorimeter curve graph of a bicarbazole derivative of Formula (I-002) according to an embodiment of the present invention.

7 is a differential scanning calorimeter curve graph of a bicarbazole derivative of Formula (I-007) according to one embodiment of the present invention.

8 is a diagram illustrating a multilayer structure of an organic electroluminescent device manufactured using a bicarbazole derivative according to an example of the present invention.

9 is an electroluminescence (EL) spectrum graph of an organic electroluminescent device manufactured using a bicarbazole derivative according to an example of the present invention.

Claims (4)

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

(In formula (I), R1 and R2 each represent an aryl group having 6 to 30 nuclear carbon atoms unsubstituted or substituted with an alkyl group, an alkoxy group, an aryl group, a styryl group, a cyano group, a nitro group or an amino group, and D Represents an substituted or unsubstituted aryl group having 6 to 18 nuclear carbon atoms.) 2. The organic electroluminescence device of claim 1, wherein D of Formula I has a unit structure of d01, R1 has a unit structure of b01, and R2 has a unit structure of b01, b02, or b09. Composition. [d01] [b01] [b02] [b09]

The organic electroluminescent composition according to claim 1, wherein D in Formula I has a unit structure of d01 or d02, and R1 and R2 each have a unit structure of b04. [d01] [d02] [b04]

An organic electroluminescent device comprising at least one organic layer comprising the organic electroluminescent composition according to any one of claims 1 to 3.

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