KR20040055236A - Blue Light Emitting Polymers Containing Electron-donating and Electron-accepting Moiety, and Electroluminescent Device Using the Same - Google Patents

Abstract

PURPOSE: Provided are a blue organic luminescent polymer containing electron donor and electron acceptor substituents, which has high heat and oxidation stabilities, minimizes the interaction between molecules, transits energy easily, and has an excellent luminescent efficiency, and an electroluminescent device using the luminescent polymer. CONSTITUTION: The blue organic luminescent polymer comprises £E1|-£Ar1|-£Ar2|, £E1|-£E2|-£Ar1|, or £E1|-£E2|-£Ar1|-£Ar2|, wherein £E1| and £E2| are differently represented by the formula 1, the formula 2, or the formula 3 and £Ar1| and £Ar2| are differently represented by the formula 4, the formula 5, or the formula 6. And the electroluminescent device uses the blue organic luminescent polymer as a material of a luminescent layer or a hole transfer layer. In the formula, R1-R6 are identically or differently carbazole or amine or oxadiazole having C1-C30 alkyl, alkoxy, aryl, or alkylaryl, R7-R12 are identically or differently C1-C30 alkyl, alkoxy, aryl, or alkylaryl, and n, m, and l are identically or differently integers of 1-100,000.

Description

Blue Light Emitting Polymers Containing Electron-donating and Electron-accepting Moiety, and Electroluminescent Device Using the Same}

The present invention relates to a blue organic light emitting molecule including an electron donor and an electron acceptor substituent, and an electroluminescence device (EL device) using the same. More particularly, the present invention relates to a carbazole which exhibits excellent injection and transfer properties of electrons or holes. Functional substituents, such as amines, oxadiazoles, etc. are introduced into the main chain or side branches, and the introduction of large substituents minimizes intermolecular interactions, and introduces substituents capable of intramolecular or intermolecular energy transfer and exhibits high-efficiency luminescence properties. It relates to a blue organic light emitting molecule and an electroluminescent device using the same.

Recently, due to the rapid growth of the optical communication and multimedia fields, the development into a highly information society has been accelerated. Accordingly, optoelectronic devices using the conversion of photons to electrons or the conversion of electrons to photons have become the core of the modern information electronics industry. Such semiconductor optoelectronic devices can be broadly classified into electroluminescent devices, light receiving devices, and devices in which they are combined.

Until now, most displays are light-receiving, while self-emissive electroluminescence displays are fast responding and self-luminous, so they do not require backlighting and have excellent brightness. It is attracting attention as a display element.

Electroluminescent devices are classified into inorganic and organic light emitting devices according to the material for forming the light emitting layer. Organic electroluminescence (EL) is a phenomenon in which when an electric field is applied to an organic material, electrons and holes are transferred from the cathode and the anode, respectively, to be combined within the material, and the energy generated is emitted as light. The electroluminescence of these organic materials was reported by Pope et al. In 1963. In 1987, by East et al. By Tang et al, π- was known as alumina-quinone. Many studies have been conducted since a light emitting device having a multilayer structure having a quantum efficiency of 1% and a luminance of 1000 cd / m 2 at 10 V or less as a device made of a dye having a conjugated structure has been reported.

Such an electroluminescent device has an advantage in that the synthesis path is simple and the synthesis of various types of materials is easy and color tuning is possible. However, when the processability and thermal stability are low and the voltage is applied, Joule heat is generated in the light emitting layer, and as the molecules are rearranged, the device is destroyed and causes problems in the luminous efficiency or life of the device. Substitution with organic electroluminescent devices having

1 is a cross-sectional view showing a structure of a general organic electroluminescent device manufactured from a substrate / anode / hole transport layer / light emitting layer / electron transport layer / cathode. Referring to FIG. 1, an anode 12 is formed on the substrate 11. The hole transport layer 13, the light emitting layer 14, the electron transport layer 15, and the cathode 16 are sequentially formed on the anode 12. Here, the hole transport layer 13, the light emitting layer 14 and the electron transport layer 15 are organic thin films made of an organic compound. The driving principle of the organic electroluminescent device of the above structure is as follows.

When a voltage is applied between the anode 12 and the cathode 16, holes injected from the anode 12 are moved to the light emitting layer 14 via the hole transport layer 13. On the other hand, electrons are injected into the light emitting layer 14 from the cathode 16 via the electron transport layer 15, and carriers are recombined in the light emitting layer 14 to generate excitons. This exciton is changed from the excited state to the ground state, whereby the fluorescent molecules of the light emitting layer emit light to form an image.

The organic electroluminescent device driven on the principle described above is classified into a polymer organic electroluminescent device and a low molecular organic electroluminescent device according to the molecular weight of the material for forming an organic film.

In general, in the case of using a low molecule when forming an organic film, the low molecule is easy to purify and can almost remove impurities, it is excellent in the light emission characteristics. However, there is a problem in that spin coating is not possible and heat resistance is poor, thereby deteriorating or recrystallizing by driving heat generated when driving the device. On the other hand, when the polymer is used to form the organic film, the energy level is separated into the conduction band and the electrical appliance diagram by the superposition of the π-electron wave function in the polymer backbone, and the band gap energy corresponding to the energy difference is used. The semiconducting properties of the polymer are determined and full color is possible. Such polymers are called π-conjugated polymers.

An electroluminescent device using poly (p-phenylenevinylene) (PPV), a polymer having conjugated double bonds, was first introduced in 1990 by a team of professors from RH Friend at the University of Cambridge, UK. After being announced, researches using organic polymers have been actively conducted. Compared with the low molecular weight polymer, the polymer has excellent heat resistance and can be spin coated to easily increase the size of the display device. By introducing various suitable substituents, polyphenylenevinylene (PPV) derivatives, polythiophene (Pth) derivatives, and the like, which can improve processability and express various colors, have been reported.

However, materials such as polyphenylenevinylene derivatives and polythiophene derivatives can obtain high-efficiency red and green advertised molecular materials among the three primary colors of light, such as red, green, and blue. Hard to get

In addition, polyphenylene derivatives, polyfluorene derivatives, and the like have been reported as blue baling advertisement molecular materials. Polyphenylene has high oxidation stability and thermal stability, but has a disadvantage of low luminous efficiency and poor solubility. In the case of polyfluorene derivatives, most research has been carried out with blue adsorbed molecules, but there is still a problem of minimizing the interaction between excitons generated in one molecule and excitons of other adjacent molecules.

Accordingly, in the present invention, as a result of repeating various studies to solve the problems described above, the electron donor and electron acceptor substituents, which have excellent thermal stability and high luminous efficiency, have excellent solubility and minimize intermolecular interactions. A new blue light emitting organic electroluminescent molecule comprising the same and an electroluminescent device using the same have been developed, and the present invention has been completed based on this.

Accordingly, an object of the present invention is to provide a blue organic light emitting molecule having high thermal and oxidative stability while minimizing intermolecular interactions and exhibiting excellent luminous efficiency with easy energy transfer.

Another object of the present invention is to provide an electroluminescent device using the blue organic light emitting molecules.

In order to achieve the above object, the blue organic light emitting molecule according to the present invention is [E ₁ ]-[Ar ₁ ]-[Ar ₂ ], [E ₁ ]-[E ₂ ]-[Ar ₁ ], or [E ₁ ] -[E ₂ ]-[Ar ₁ ]-[Ar ₂ ], wherein [E ₁ ] and [E ₂ ] are compounds represented by Formula 1, Formula 2, or Formula 3 differently from each other, [Ar ₁ ] and [Ar ₂ ] is characterized in that the compound represented by the following formula (4), (5) or (6):

Wherein R ₁ to R ₆ may be the same as or different from each other, such as carbazole, or amine having an alkyl group, an alkoxy group, an aryl group, or an alkylaryl group having 1 to 30 carbon atoms; Or oxadiazole having an alkyl group, an alkoxy group, an aryl group or an alkylaryl group having 1 to 30 carbon atoms, wherein R ₇ to R ₁₂ are the same as or different from each other, an alkyl group having 1 to 30 carbon atoms, an alkoxy group, an aryl group or Alkylaryl group, n, m and 1 are the same as or different from each other and are an integer of 1 to 100,000.

Electroluminescent device according to the present invention for achieving the above another object is characterized in that using the blue organic light emitting molecules as a light emitting layer or a hole transport layer material.

1 is a cross-sectional view showing a structure of a general organic electroluminescent device manufactured from a substrate / anode / hole transport layer / light emitting layer / electron transport layer / cathode.

2 is a cross-sectional view showing the structure of an organic electroluminescent device according to an embodiment of the present invention.

3 is a cross-sectional view showing the structure of an organic electroluminescent device according to another embodiment of the present invention.

※ Explanation of code about main part of drawing ※

11 substrate 12 anode

13 hole transport layer 14 light emitting layer

15: electron transport layer 16: cathode (cathode)

17: Poly (3,4-ethylenedioxy-thiophene) (PEDT) layer (500 Hz) coated with poly (styrenesulphonic acid) (PSS)

18: the electro-molecular advertising compound compound layer of the present invention (700Å)

19: lithium fluoride (LiF) (20 °)

20: Aluminum (Al) (700Å)

21: the electro-molecular advertising compound compound layer of the present invention (650Å)

22: calcium (500a)

23: aluminum (Al) (1,500Å)

Looking at the present invention in more detail as follows.

As described above, the present invention has an advantage as a blue light emitting material exhibiting high thermal stability and luminous efficiency, and facilitates injection and transfer of intramolecular or intermolecular energy transition, holes or electrons by the introduction of various substituents. There is provided a blue organic light emitting molecule, and an electroluminescent device using the same.

The blue organic bale molecule according to the present invention is [E ₁ ]-[Ar ₁ ]-[Ar ₂ ], [E ₁ ]-[E ₂ ]-[Ar ₁ ], or [E ₁ ]-[E ₂ ]- [Ar ₁ ]-[Ar ₂ ]

Wherein [E ₁ ] and [E ₂ ] are compounds having fluorene, benzene or stilbene derivatives represented by the following general formula (1), (2) or (3) as components:

Formula 1

Formula 2

Formula 3

Wherein R ₁ to R ₆ may be the same as or different from each other, such as carbazole, or amine having an alkyl group, an alkoxy group, an aryl group, or an alkylaryl group having 1 to 30 carbon atoms; Or oxadiazole having an alkyl group, an alkoxy group, an aryl group or an alkylaryl group having 1 to 30 carbon atoms, and n, m and 1 are the same as or different from each other and are integers of 1 to 100,000.

Preferably as said R <_1> -R <_6> , , , , , , , , , , , , , , , , , , , , , , , , , , And Etc. are included.

In addition, [Ar ₁ ] and [Ar ₂ ] is a compound having a fluorene, benzene or stilbene derivative represented by the following general formula (4), (5), or (6):

Formula 4

Formula 5

Formula 6

In the above formula, R ₇ to R ₁₂ are the same as or different from each other, an alkyl group having 1 to 30 carbon atoms, an alkoxy group, an aryl group or an alkylaryl group, and n, m and 1 are the same as or different from each other.

[Ar ₁ ] and [Ar ₂ ] is preferably , , , , , , , , , , , And Etc. are included.

The above-mentioned blue organic adsorbed molecule of the present invention is preferably a compound represented by the following Chemical Formula 7, Chemical Formula 8, Chemical Formula 9, Chemical Formula 10, Chemical Formula 11, or Chemical Formula 12:

Since the electro-molecule of the present invention has a substituent which can impart steric hindrance to the alpha position of the vinyl group, p-stacking between the polymer chains is suppressed and the band gap is increased to increase the band gap. A blue-footed advertising molecule of color purity can be obtained. By introducing a bulky substituent in the molecule as described above, two-dimensional and three-dimensional interactions between the polymer chains can be prevented and excitons can be suppressed from being quenched by the intermolecular interactions. In addition, electrons and holes flowing into the light emitting layer from the pair of electrodes can be easily taken in the light emitting layer to maximize the generation efficiency of excitons.

Therefore, the organic electroluminescent molecule of the present invention can be used as a material for forming a light emitting layer or a hole transport layer positioned between a pair of electrodes in the electroluminescent device by using such a property, and the light emitting polymer of the present invention is a light emitting material. The blue light emitting organic electroluminescent device used as can realize high luminous efficiency.

One of the methods for manufacturing the organic electro-molecule advertising molecule is as follows.

After preparing monomers through alkylation reaction, Grignard reaction, Wittig reaction, and Suzuki coupling reaction, finally blue light emission through CC coupling reaction such as Yamamoto coupling reaction Polymers can be prepared. The number average molecular weight of the polymer is 1,000 to 10,000,000, and may have a molecular weight distribution of 1 to 100.

In addition, the organic electroluminescent molecules according to the present invention may be used as a material for forming the light emitting layer or the hole and electron transport layer of the organic electroluminescent device. 2 to 3 are cross-sectional views of an organic electroluminescent device according to a preferred embodiment of the present invention.

Referring to Figure 2, the configuration of the electroluminescent device of the present invention is a substrate (11), an anode (12), a poly (3,4- ethylene deoxy doped with poly (styrene sulfonic acid) (PSS) as a hole transport layer A thiophene (PEDT) layer 17, a light emitting layer 18 to which the electro-adhesive molecules of the present invention are applied, a lithium fluoride (LiF) layer as an electron transport layer, and a layer of aluminum 20 which is a cathode.

In addition, referring to Figure 3, the configuration of the electroluminescent device of the present invention is a substrate (11), an anode (12), poly (styrene sulfonic acid) (PSS) doped poly (3,4-ethylene as a hole transport layer A deoxy-thiophene (PEDT) layer 17, a light emitting layer 21 to which the electro-adhesive molecules of the present invention are applied, a calcium (Ca) layer as an electron transporting layer, and a cathode aluminum 20 layer.

On the other hand, the manufacturing method of the organic electroluminescent device applying the electroluminescent molecules of the present invention is as follows.

First, a material for the anode 12 electrode is coated on the substrate. Here, the substrate 11 is a substrate used in a conventional organic electroluminescent device, preferably a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproof. In addition, as the material for the anode 12 electrode, indium tin oxide (ITO), tin oxide (SnO ₂ ), zinc oxide (ZnO), or the like, which is transparent and has excellent conductivity, is used. As the metal for forming the cathode 20, lithium (Li), magnesium (Mg), aluminum (Al), Al: Li, or the like having a small work function is used.

The organic electroluminescent device of the present invention may further include a hole transport layer and / or an electron transport layer as well as the most common device configuration of the anode / light emitting layer / cathode.

In this case, the light emitting layer may be formed by spin coating, the thickness is preferably in the range of 10 ~ 10,000Å. The hole transport layer may be formed by vacuum deposition or sputtering on the anode electrode, and the electron transport layer is formed on the light emitting layer before forming the cathode. The electron transport layer may use a conventional material for forming an electron transport layer, or may be formed by vacuum deposition or spin coating of the electro-adhesive molecule of the present invention. At this time, the hole transport layer and the electron transport layer preferably has a thickness of 10 to 10,000 kPa.

The hole transport layer and the electron transport layer material is not particularly limited, but preferably, the hole transport layer material is N, N'-bis (3-methylphenyl) -N, N-diphenyl- [1,1'-biphenyl] -4,4'-diamine (TPD) is used, and as the electron transport layer material, aluminum trihydroxyquinoline (Alq ₃ ), 1,3,4-oxadiazole derivative PBD (2- (4-biphenylyl) ) -5-phenyl-1,3,4-oxadiazole), TPQ (1,3,4-tris [(3-penyl-6-trifluoromethyl) quinoxaline-2-yl] benzene), a quinoxaline derivative, and triazole Derivatives and the like are used. The electron transport layer and the hole transport layer increases the probability of luminescence bonding in the light emitting polymer by efficiently transporting carriers to the light emitting polymer.

The organic electroluminescent device of the present invention may be manufactured in the order described above, that is, in the order of anode / hole transport layer / light emitting layer / electron transport layer / cathode, or vice versa, that is, cathode / electron transport layer / light emitting layer / hole transport layer / anode You may manufacture in order.

The invention can be more clearly understood by the following examples, the following examples are merely for the purpose of illustrating the invention and are not intended to limit the scope of the invention.

Preparation Example 1

Synthesis of Compound (1,2-bis (4-bromophenyl) -α- (4- (5- (4-t-butylphenyl) -1,2,4-oxazolyl) phenyl) ethane) (1)

The reaction was carried out as shown in Scheme 1 below.

25 g of methyl 4-t-butylbenzoate is added to 250 ml of methanol, dissolved in 7.3 g of hydrazine, and heated to reflux for about 10 hours. After the reaction is completed, the mixture is extracted with water and ethyl acetate (EA), and the solvent is blown on a rotary evaporator. Separation by column chromatography gave 17 g (68%) of compound 4-t-butylbenzoic hydrazide (1-1).

After dissolving 5.5 g of Compound (1-1) in 100 ml of chloroform, the temperature was lowered to 0 ° C., and a solution of 6.3 g (1 equivalent) of 4-bromobenzoyl chloride in 50 ml of chloroform was slowly added dropwise. Here, 3.4 ml (1.5 equivalents) of pyridine was added and reacted at room temperature for 5 hours. The resulting mixture is poured into cold water, filtered through a glass filter and washed several times with water. The product was dried to give 8.5 g (92%) of compound (1-2).

Then, 8.5 g of the compound (1-2) was dissolved in 100 ml of phosphorus oxychloride, and heated to reflux at 90 ° C. for 24 hours. The solvent is removed by vacuum distillation and the remaining mixture is extracted with water and dichloromethane. Recrystallization using a hexane / acetone mixed solution gave 7.2 g of compound (1-3).

After dissolving 7.2 g of the compound (1-3) in THF, the temperature was lowered to -78 ° C., and 6.9 ml (1.2 equivalents) of n-BuLi (1.6M) was added thereto, followed by stirring at low temperature for 30 minutes. Slowly inject 1.9 g (1.1 equiv) of 4-bromobenzaldehyde, raise the temperature gradually to room temperature, extract the product with water and dichloromethane, and separate the residue using column chromatography to obtain 2.3 g of compound (1-4). Was obtained (yield 53%).

Next, 2.0 g of the compound (1-4) was dissolved in 10 ml of DMF, followed by injection of 1.27 g of potassium dichromate dissolved in 10 ml of DMF. The temperature was raised to 100 ° C., stirred for 2 hours, cooled to room temperature, extracted with water and ether, separated by column chromatography, and 1.6 g of Compound (1-5) was obtained (yield: 80%).

1.4 g of the compound (1-5) and 1.12 g (1.2 equivalents) of 4-bromobenzyl diethylphosphonate are dissolved in 300 ml of THF, followed by stirring at room temperature. Potassium t-butoxide (1.4 equiv) was slowly injected and then heated to reflux for 4 hours. After neutralization with concentrated hydrochloric acid, extracted with ether, separated by column chromatography, and recrystallized from ethanol to give a compound (1,2-bis (4-bromophenyl) -α- (4- (5- (4-t- Butylphenyl) -1,2,4-oxadiazolyl) phenyl) ethane) (1) 1.5 g is obtained (yield: 80%).

Preparation Example 2

Synthesis of Compound (1,4-Dibromo-5-methoxy-2- (8-N-carbazolyloctyloxy) benzene) (2)

The reaction was carried out as shown in Scheme 2 below.

After dissolving 5 g of 4-methoxyphenol in 50 ml of ethanol, 4.38 g (2 equivalents) of potassium hydroxide was added and stirred at room temperature for 1 hour. 0.6 g (0.1 equivalents) of sodium iodide and 21.7 g (2 equivalents) of dibromooctane are added and heated to reflux for 40 hours. After neutralization with dilute hydrochloric acid solution and extraction with hexane, the separated product was recrystallized from hexane to give compound (2-1) (4-methoxy-1- (8-bromooctyloxy) benzene) as a white solid ( 2.3 g, 25%).

2.1 g of Compound (2-1) is dissolved in 50 ml of carbon tetrachloride, and 0.01 g of iodine is added thereto and stirred. 2.2 g (2.1 equivalents) of bromine (Br ₂ ) is dissolved in 30 ml of carbon tetrachloride and slowly added dropwise to the reaction solvent. After completion of the reaction, the product was extracted with aqueous sodium hydroxide solution and chloroform and separated by column chromatography to obtain compound (2-2) (2,5-dibromo-4-methoxy-1- (8-bromooctyloxy) Benzene) (2.5 g, 80%).

Then, 2.2 g of carbazole was dissolved in 5 ml of DMF, and then 1.6 g of potassium t-butoxide was added and stirred for 1 hour. The solution is stirred at room temperature while slowly dropping 5.2 g of the compound (2-2) into a solution of 10 ml of DMF. After completion of the reaction, the mixture was extracted with water and dichloromethane and separated by column chromatography to give a colorless liquid Compound (2) (1,4-dibromo-5-methoxy-2- (8-N-carbazolyloctyloxy) Benzene) 5.5 g (yield 75%).

Preparation Example 3

Synthesis of Compound (2,7-Dibromo-9,9- (8-carbazolyloctyl) fluorene) (3)

The reaction was carried out as shown in Scheme 3 below.

10 g of carbazole and 6.7 g of potassium t-butoxide are dissolved in 50 ml of DMF and stirred for 1 hour. This solution is slowly added dropwise to 50 ml of DMF solution, which has dissolved 25.6 g (1.5 equivalents) of dibromooctane and dropped the temperature to 78 ° C. After completion of the reaction, the mixture was extracted with water and dichloromethane and separated by column chromatography to obtain 15.0 g of Compound (3-1) (8-N-carbazolyl-1-bromooctane) (yield 76%).

Then, 4.1 g of 2,7-dibromofluorene and 10.8 g (2.4 equivalents) of the compound (3-1) were dissolved in 500 ml of dimethyl sulfoxide, and then the temperature was lowered to 0 ° C., and 3.8 g of potassium t-butoxide was dissolved. (2.8 equiv.) 250 ml of DMSO solution is slowly added dropwise. After stirring for 12 hours at room temperature, and extracted with water and hexane after completion of the reaction and separated by column chromatography 8.5 g of compound (3) (2,7-dibromo-9,9- (8-carbazolyl jade) (Till) fluorene) is obtained (yield: 76%).

Preparation Example 4

Synthesis of Compound (1,2-bis (4-bromophenyl) -α- (3- (N- (2-ethylhexyl) -6-trimethylsilylcarbazolyl)) ethene) (4)

The reaction was carried out as shown in Scheme 4 below.

30.0 g of carbazole are dissolved in 350 ml of DMF, the temperature is lowered to 0 ° C., and 64.7 g (2.1 equivalents) of N-bromosuccinimide (NBS) is slowly added. After stirring at room temperature, the mixture was extracted with water and ether and reprecipitated with an excess of ether to give 50.5 g (90%) of compound (4-1) (3,6-dibromocarbazole).

25.0 g of the compound (4-1) was dissolved in 80 ml of DMF, and then 31.9 g (3 equivalents) of potassium carbonate was added thereto, followed by stirring at room temperature for 1 hour. 17.6 g (1.05 eq) of 2-ethylhexyl bromide was added thereto, stirred at 50 ° C. for 24 hours, extracted with water and ether, and recrystallized from ether to give 28.0 g of Compound (4-2) (N- (2-ethylhexyl) -3,6-dibromocarbazole) was obtained (yield: 83%).

Then, 12.0 g of the compound (4-2) was dissolved in 240 ml of THF, cooled to 78 ° C, and then 1.76 g (1 equivalent) of n-butyllithium was injected and stirred at a low temperature for 1 hour. While maintaining the low temperature, 3.3 g (1.1 equiv) of chlorotrimethylsilane is slowly added dropwise. After completion of the reaction, the mixture was extracted with water and dichloromethane and separated by column chromatography to obtain 6.5 g of (4-3) ((N- (2-ethylhexyl) -3-bromo-6-trimethylsilylcarbazole). (Yield 55%).

6.5 g of the compound (4-3) was dissolved in 240 ml of THF, cooled to 78 ° C., and then 1.0 g (1 equivalent) of n-butyllithium was injected and stirred at a low temperature for 1 hour. Add 3.05 g (1.1 equiv) of 4-bromobenzaldehyde while maintaining the low temperature. After completion of the reaction, the mixture was extracted with water and dichloromethane and separated by column chromatography. Compound (4-4) (4-bromophenyl)-(N- (2-ethylhexyl) -3-trimethylsilylcarbazolyl) methanol) 6.0 g was obtained (yield: 75%).

Next, 6.0 g of the compound (4-4) is dissolved in 10 ml of DMF, followed by addition of 3.28 g (1 equivalent) of potassium dichromate and 90 ml of DMF. The temperature is raised to 100 ° C. and stirred for about 2 hours. The mixture was cooled to room temperature, extracted with water and ether, the remaining DMF was removed by vacuum distillation, and then separated by column chromatography. Compound (4-5) (4-bromophenyl)-(N- (2-ethylhexyl) 3-triethylsilylcarbazolyl) ketone) was obtained (yield: 82%).

4.8 g of the compound (4-5) and 3.2 g (1.2 equivalents) of 4-bromobenzyl diethylphosphonate are dissolved in 150 ml of THF, followed by stirring at room temperature. Potassium t-butoxide (1.3 equiv) was slowly injected and then heated to reflux for 4 hours. After neutralization with concentrated hydrochloric acid solution, extraction with ether and separation by column chromatography yielded Compound (4) (1,2-bis (4-bromophenyl) -α- (N- (2-ethylhexyl) -3- 5.5 g of trimethylsilylcarbazolyl) ethene) is obtained (yield: 89%).

Example 1

Polymerization of Organic Foot Adsor molecules Represented by Formula 13

The polymerization was carried out as shown in Scheme 5 below.

After dissolving 0.015 g of nickel (II) dichloride, 0.021 g of 2,2-dipyridyl, 0.66 g of triphenylphosphate, and 0.29 g of zinc metal in 4 ml of DMF, the temperature was raised to 60 ° C. and stirred for about 15 minutes. Changes color Here, 0.45 g of 9,9-dihexyl-2,7-dibromofluorene and 1,2-bis (4-bromophenyl) -α- (2- (9,9-dihexyl) fluore 0.12 g of nil) ethene, 0.25 g of compound (4) and 0.23 g of compound (1) are dissolved in 4 ml of toluene, and then added to a black solution, and the temperature is raised to 90 ° C. After reacting for 48 hours, 0.2 ml of bromobenzene was added as an end-capping agent and reacted for 24 hours. The reaction solution was dissolved in THF, precipitated in methanol, and filtered to obtain 0.9 g of a compound represented by Formula 13.

Example 2

Polymerization of Organic Foot-Advertising Molecules of Formula 14

The polymerization was carried out as shown in Scheme 6 below.

After dissolving 0.025 g of nickel (II) dichloride, 0.034 g of 2,2-dipyridyl, 0.88 g of triphenylphosphate, and 0.69 g of zinc metal in 4 ml of DMF, the temperature was raised to 60 ° C. and stirred for about 15 minutes. Changes color Here, 0.44 g of 9,9-dihexyl-2,7-dibromofluorene, 1,2-bis (4-bromophenyl) -α- (2- (9,9-dihexyl) fluore Niel) ethene 0.38g, 0.25g of compound (2) and 0.20g of compound (1) are dissolved in 4ml of toluene, and then added to a black solution, and the temperature is raised to 90 ° C. After reacting for 48 hours, 0.2 ml of bromobenzene was added as an end capping agent and reacted for 24 hours. The reaction solution was dissolved in THF, precipitated in methanol, and filtered to obtain 0.8 g of the compound represented by Formula 14.

Example 3

Polymerization of Organic Foot Ads Molecules of Formula 15

The polymerization was carried out as shown in Scheme 7 below.

Dissolve 0.036 g of nickel (II) dichloride, 0.047 g of 2,2-dipyridyl, 1.48 g of triphenylphosphate, and 0.65 g of zinc metal in 5 ml of DMF, and then raise the temperature to 60 ° C and stir for about 15 minutes. Changes color Herein, 0.14 g of 9,9-dihexyl-2,7-dibromofluorene, 1,2-bis (4-bromophenyl) -α- (2- (9,9-dihexyl) fluore 0.48 g of nil) ethene and 0.38 g of compound (3) are dissolved in 5 ml of toluene, and then added to a black solution, and the temperature is raised to 90 ° C. After reacting for 48 hours, 0.2 ml of bromobenzene was added as an end capping agent and reacted for 24 hours. The reaction solution was dissolved in THF, precipitated in methanol, and filtered to obtain 0.4 g of a compound represented by Formula 15.

Example 4

Polymerization of Organic Foot Adsor molecules Represented by Formula 16

The polymerization was carried out as shown in Scheme 8 below.

After dissolving 0.011 g of nickel (II) dichloride, 0.015 g of 2,2-dipyridyl, 0.46 g of triphenylphosphate, and 0.24 g of zinc metal in 4 ml of DMF, the temperature was raised to 60 ° C. and stirred for about 15 minutes to give a black solution. Changes color Here, 0.30 g of 9,9-dihexyl-2,7-dibromofluorene, 1,2-bis (4-bromophenyl) -α- (2- (9,9-dihexyl) fluore Niel) ethene 0.32 g and 0.073 g of compound (1) are dissolved in 5 ml of toluene, added to a black solution, and the temperature is raised to 90 ° C. After reacting for 48 hours, 0.1 ml of bromobenzene was added as an end capping agent and reacted for 24 hours. The reaction solution was dissolved in THF, precipitated in methanol, and filtered to obtain 0.5 g of a compound represented by Chemical Formula 16.

Example 5

Polymerization of Organic Foot Ads Molecules of Formula 17

The polymerization was carried out as shown in Scheme 9 below.

After dissolving 0.011 g of nickel (II) dichloride, 0.015 g of 2,2-dipyridyl, 0.47 g of triphenylphosphate, and 0.24 g of zinc metal in 5 ml of DMF, the temperature was raised to 60 ° C. and stirred for about 15 minutes to give a black solution. Changes color Here, 0.30 g of 9,9-dihexyl-2,7-dibromofluorene, 1,2-bis (4-bromophenyl) -α- (2- (9,9-dihexyl) fluore 0.24 g of nil) ethene and 0.17 g of compound (3) are dissolved in 5 ml of toluene, and then added to a black solution, and the temperature is raised to 90 ° C. After reacting for 48 hours, 0.2 ml of bromobenzene was added as an end capping agent and reacted for 24 hours. The reaction solution was dissolved in THF, precipitated in methanol, and filtered to obtain 0.4 g of a compound represented by Formula 17.

Example 6

Polymerization of Organic Foot Ads Molecules of Formula 18

The polymerization was carried out as shown in Scheme 10 below.

After dissolving 0.033 g of nickel (II) dichloride, 0.046 g of 2,2-dipyridyl, 1.43 g of triphenylphosphate, and 0.74 g of zinc metal in 8 ml of DMF, the temperature was raised to 60 ° C. and stirred for about 15 minutes. Changes color 1,2-bis (4-bromophenyl) -α- (2- (9,9-dihexyl) fluorenyl) ethene 2.0 g, 1,4-dibromo-2,5-di here 0.36 g of octyloxybenzene and 0.45 g of compound (1) are dissolved in 8 ml of toluene, and then added to a black solution, and the temperature is raised to 90 ° C. After reacting for 48 hours, 0.2 ml of bromobenzene was added as an end capping agent and reacted for 24 hours. The reaction solution was dissolved in THF, precipitated in methanol, and filtered to obtain 0.4 g of the compound represented by Chemical Formula 18.

Examples 7-12

-Fabrication of an electroluminescent device using the organic electroluminescent molecule of the present invention

An electroluminescent device was manufactured using the light emitting polymers obtained in Examples 1 to 6 as light emitting layer materials, respectively.

On a patterned ITO substrate, Baytron 4083 (Bayer's conductive polymer) was spin-coated to a thickness of about 500 mm 3, and then dried on a hot plate at 120 ° C. for 5 minutes. After dissolving with toluene, spin-coating the light emitting layer to a thickness of about 800 kW, vacuum depositing lithium fluoride to about 10 kW thereon, and vacuum-evaporating aluminum to about 700 kW to form an electroluminescent device. Prepared.

The results of measuring the electroluminescent properties of the electroluminescent device thus manufactured are shown in Table 1 below.

Light emitting polymer Molecular Weight (Mw) Molecular Weight Distribution (PDI) Luminous Efficiency (Cd / A) Power efficiency (lm / W) Color purity Example 7 Formula 13 15,122 1.640 1.075 0.671 (0.220, 0.390) Example 8 Formula 14 12,711 1.704 0.186 0.077 (0.193, 0.336) Example 9 Formula 15 3,437 1.471 0.476 0.237 (0.199, 0.323) Example 10 Formula 16 20,568 1.742 0.536 0.279 (0.186, 0.298) Example 11 Formula 17 20,520 1.814 0.425 0.234 (0.234, 0.370) Example 12 Formula 18 13,367 1.650 0.825 0.562 (0.197, 0.347)

As can be seen in Table 1, the electroluminescent device using the organic electroluminescent molecules of the present invention was excellent in electroluminescent properties such as luminous efficiency, power efficiency and color purity.

As described above, the blue light emitting organic electroluminescent molecules of the present invention have excellent thermal stability and high luminous efficiency, using fluorene, benzene and stilbene derivatives including electron donors and electron acceptor substituents as components. It has good solubility and can minimize intermolecular interactions. In addition, it is possible to improve the luminous efficiency of the light emitting device to which it is applied by facilitating the injection and transfer of energy or intramolecular or intermolecular energy transition, holes or electrons by introducing various substituents.

Claims (4)

[E ₁ ]-[Ar ₁ ]-[Ar ₂ ], [E ₁ ]-[E ₂ ]-[Ar ₁ ], or [E ₁ ]-[E ₂ ]-[Ar ₁ ]-[Ar ₂ ] Consists of, Here, [E ₁ ] and [E ₂ ] is a compound represented by the following Formula 1, Formula 2, or Formula 3 different from each other, [Ar ₁ ] and [Ar ₂ ] are different from each other represented by Formula 4, Formula 5 , Or a blue organic bale ad molecule characterized in that the compound represented by the formula (6): Formula 1 Formula 2 Formula 3 Formula 4 Formula 5 Formula 6 Wherein R ₁ to R ₆ may be the same as or different from each other, such as carbazole, or amine having an alkyl group, an alkoxy group, an aryl group, or an alkylaryl group having 1 to 30 carbon atoms; Or oxadiazole having an alkyl group, an alkoxy group, an aryl group or an alkylaryl group having 1 to 30 carbon atoms, wherein R ₇ to R ₁₂ are the same as or different from each other, an alkyl group having 1 to 30 carbon atoms, an alkoxy group, an aryl group or Alkylaryl group, n, m and 1 are the same as or different from each other and are an integer of 1 to 100,000. The method of claim 1, wherein the blue organic speech ad molecule is a blue organic molecule ad molecule, characterized in that the compound represented by the following formula 7, formula 8, formula 9, formula 10, formula 11, or formula 12: Formula 7 Formula 8 Formula 9 Formula 10 Formula 11 Formula 12 An electroluminescent device comprising the blue organic light emitting molecule according to claim 1 or 2 as a light emitting layer or a hole transporting layer material. 4. The electroluminescent device according to claim 3, wherein the electroluminescent device has an anode / light emitting layer / cathode, an anode / hole transporting layer / light emitting layer / cathode, or an anode / hole transporting layer / light emitting layer / electron transporting layer / cathode.