KR20070097138A - Red phosphorescene compounds and organic electroluminescence devices using the same - Google Patents

Abstract

A red phosphorescence compound and an organic electroluminescence device using the same are provided to show higher color purity, higher brightness and prolonged life span. A red phosphorescence compound is represented by the formula 1, wherein the formula (a) is the formula (b), R1 and R2 are selected from a C1-C4 alkyl and alkoxy group, each of R3,R4, R5 and R6 is selected from hydrogen, a C1-C4 alkyl and alkoxy group, the formula (c) is selected from 2,4-pentanedione, 2,2,6,6-tetramethyl heptane-3,5-dione, 1,3-propanedione, 1,3-butanedione, 3,5-heptanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione and 2,2-dimethyl-3,5-hexanedione. An organic electroluminescence device includes a positive electrode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a negative electrode, which are laminated in order, wherein the red phosphorescence compound is employed in an amount of 0.5-20 wt% as a dopant of the light emitting layer.

Description

 Red phosphorescene compounds and organic electroluminescence devices using the same

1 is a graph showing that the visibility is lowered as the color purity of the organic EL element is increased (as the CIE color coordinate X value is larger).

2 shows structural formulas of NPB, copper (II) phthalocyanine (CuPc), (btp) ₂ Ir (acac), Alq ₃ , BAlq and CBP, which are compounds used in Examples of the present invention.

The present invention relates to a red phosphorescent compound and an organic light emitting device using the same. More specifically, the present invention includes a dopant of a light emitting layer of an organic light emitting device comprising a laminate of an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode in this order. It relates to an organic electroluminescent device used in the).

Recently, as the size of the display device increases, the demand for a flat display device having less space is increasing. As one of the flat display devices, an organic light emitting diode (OLED), also called an organic light emitting diode (OLED), has a high speed. It has been developed and several prototypes have already been announced.

The organic electroluminescent device is a device that emits light by dissipating electrons and holes after pairing when electrons are injected into the organic film formed between the electron injection electrode (cathode) and the hole injection electrode (anode). Not only can the device be formed on a flexible transparent substrate such as plastic, but it can also be driven at a lower voltage (10V or less) than a plasma display panel or an inorganic electroluminescent (EL) display. In addition, the power consumption is relatively low, there is an advantage that the color is excellent. In addition, the organic electroluminescent (EL) device can display three colors of green, blue, and red, and thus, has become a subject of much interest as a next-generation rich color display device. Here is a brief look at the process of manufacturing an organic EL device,

(1) First, an anode material is coated on a transparent substrate. Indium tin oxide (ITO) is commonly used as the anode material.

(2) Apply a hole injecting layer (HIL) on it. As the hole injection layer, copper phthalocyanine (CuPc) is mainly coated with a thickness of 10 nm to 30 nm.

(3) Then, introduce a hole transport layer (HTL). As the hole transport layer, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (4,4'-bis [N- (1-naphthyl) -N-phenylamino] -biphenyl (NPB) is deposited by depositing about 30 nm to 60 nm.

(4) Form an organic emitting layer thereon. At this time, a dopant is added as necessary. Green (green) when the light emission is often the organic light emitting layer of tris (8-hydroxy-quinol-rate) aluminum _{(Alq 3) (tris (8} -hydroxy-quinolatealuminum) thick deposited about 30 ~ 60nm and the roneun impurity (dopant), MQD (N Methyl quinacridone) (N-Meth ylquinacridone) is used a lot.

(5) An electron transport layer (ETL) and an electron injecting layer (EI L) are successively coated thereon, or an electron injection transport layer is formed thereon. In the case of green light emission, since Alq ₃ in the above (4) has a good electron transport ability, the electron injection layer / transport layer is often not used.

(6) The next cathode is applied and finally the protective film is overlaid.

In the above structure, blue, green, and red light emitting devices may be implemented depending on how the light emitting layer is formed.

In the case of the light emitting material, excitons are formed by recombination of electrons and holes injected from both electrodes, and singlet excitons are involved in phosphorescence and triplet excitons. Fluorescent materials using triplet excitons with a 75% generation probability involved in phosphorescent materials show superior luminous efficiency than fluorescent materials using singlet excitons with a 25% generation probability. Among these phosphorescent materials, red phosphorescent materials can have very high luminous efficiency compared to fluorescent materials, and thus, many researches have been made as important methods for increasing the efficiency of organic light emitting diodes.

In order to use phosphorescent materials, high luminous efficiency, high color purity and long luminous lifetime are required, and in the case of red color, as shown in FIG. 1, the higher the color purity (as the CIE color coordinate X value becomes larger), the lower the visibility and the higher the luminous efficiency. There is a difficult problem.

Accordingly, development of a red phosphorescent light emitting compound having excellent color coordinate characteristics (CIE color purity X = 0.65 or more), high luminous efficiency, and long luminous lifetime is required.

SUMMARY OF THE INVENTION An object of the present invention is to synthesize a compound of Formula 1 used as a dopant in a light emitting layer of an organic light emitting device to provide an organic light emitting device having high color purity, high brightness and long life.

In order to achieve the above object, the present invention includes a laminate of a red phosphorescent compound represented by the following formula (1) and the anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode in this order An organic electroluminescent device used as a dopant of a light emitting layer of an organic electroluminescent device is provided.

은

이며, R1, R2는 C₁-C₄의 알킬기, 알콕시기로부터 선택되고, R3, R4, R5 및 R6는 각각 수소, C₁-C₄의 알킬기 및 알콕시기로부터 선택되며,

는 2,4-펜테인다이온(

), 2,2,6,6,-테트라메틸헵테인-3,5-다이온(

), 1,3-프로페인다이온(

), 1,3-부테인다이온(

), 3,5-헵테인다이온(

), 1,1,1-트라이플루오로-2,4-펜테인다이온(

), 1,1,1,5,5,5-헥사플루오로-2,4-펜테인다이온(

) 및 2,2-다이메틸 -3,5-헥세인다이온(

)으로부터 선택되는 것을 특징으로 한다.(In Chemical Formula 1)

silver

R 1, R 2 are selected from C ₁ -C ₄ alkyl groups and alkoxy groups, R 3, R 4, R 5 and R 6 are each selected from hydrogen, C ₁ -C ₄ alkyl groups and alkoxy groups,

Is 2,4-pentane ion (

), 2,2,6,6, -tetramethylheptane-3,5-dione (

), 1,3-propane ion (

), 1,3-butanedione (

), 3,5-heptanedionate (

), 1,1,1-trifluoro-2,4-pentaneionate (

), 1,1,1,5,5,5-hexafluoro-2,4-pentaneionate (

) And 2,2-dimethyl-3,5-hexanedione (

It is characterized in that it is selected from.

은 하기 화합물 중 어느 하나인 것을 특징으로 한다.In Chemical Formula 1

Is characterized in that any one of the following compounds.

Preferred examples of the formula (1) is characterized in that any one of the following compounds.

 In the organic electroluminescent device according to the present invention, any one of Al, Zn metal complex and carbazole derivatives may be used as a host of the light emitting layer, and the amount of the dopant is preferably 0.5 wt% to 20 wt%. The organic electroluminescent device exhibits an effect according to the invention when the amount of dopant is used within this range. The ligand of the Al, Zn metal complex is composed of a quinol group, a biphenyl group, an isoquinol group, a phenyl group, a methylquinol group, a dimethylquinol group and a dimethylisoquinol group, and the carbazole derivative is preferably composed of CBP.

Among the red phosphorescent compounds used in the organic electroluminescent device according to the present invention, compounds represented by A-2 (iridium (lll) (2- (3-methylphenyl) -3,6-dimethylquinolinato-N, C ^A method for synthesizing the red phosphorescent compound of the present invention will be described using ^{2 '} ) (2,4-pentanedionate-O, O) as an example.

Synthesis Example

1.Synthesis of 2-chloro-3,6-dimethylquinoline

In a two-necked round bottom flask, N- (4-methylphenyl) -propionamide (5 mmol) was added to 50 ml of a solution of POCl ₃ (1.5 M DMF in 7 M POCl ₃ ), followed by stirring for 4 hours in a bath at 75 ° C. After the reaction is completed, the DMF is removed and extracted with dichloromethane and water. The extracted material was purified by silica gel column, distilled off the solvent under reduced pressure, recrystallized using D-dichloromethane and petroleum ether, and filtered to obtain solid of 2-chloro-3,6-dimethylquinoline. Got it.

2. Synthesis of 2- (3-methylphenyl) -3,6-dimethylquinoline

In a two-necked round bottom flask, 3-methylphenylboric acid (1.3 mmol), 2-chloro-3,6-dimethylquinoline (1 mmol), tetrakis (triphenylphosphine) palladium (0) (0.05 mmol) and potassium carbonate ( 3 mmol) was dissolved in THF (30 mL), H ₂ O (10 mL), stirred for 24 hours in a bath at 100 ° C, and when the reaction was completed, the THF and toluene were removed, and then dichloromethane and water were used. After extraction, the mixture was distilled under reduced pressure, the silica gel column was distilled under reduced pressure, and the solvent was distilled under reduced pressure, and then recrystallized with dichloromethane and petroleum ether. Got.

3. Synthesis of chloro-crosslinked dimer complex

In a dried two-necked round bottom flask, iridium (III) chloride hydrate (1 mmol) and 2- (3-methylphenyl) -3,6-dimethylquinoline (2.5 mmol) were added with 2-ethoxyethanol: distilled water 3: 1. Place in mixed solution (30 mL) and reflux for 24 hours. The solid formed by adding water was filtered and washed with methanol and petroleum ether to obtain a chloro crosslinked dimer complex.

4. Synthesis of Iridium (lll) (2- (3-methylphenyl) -3,6-dimethylquinolinato-N, C ^{2 '} ) (2,4-pentanedionate-O, O)

Chloro-crosslinked dimer complex (1 mmol), 2,4-pentanedione ( ₃ mmol) and Na ₂ CO ₃ (6 mmol) were added to 2-ethoxyethanol (30 ml) and refluxed for 24 hours. After cooling to room temperature, distilled water was added to give a solid after filtration. The solid formed was dissolved in dichloromethane and filtered using silica gel. The dichloromethane was removed under reduced pressure and washed with methanol and petroleum ether to obtain a compound.

Hereinafter, the present invention will be described through the following examples. However, it is not limited to the following embodiments of the present invention.

Example

Example 1

The light emitting area of the ITO glass was patterned to have a size of 3 mm x 3 mm and then washed. After mounting the substrate in the vacuum chamber, the basic pressure is 1 x 10 ^-6 torr, and the organics are placed on ITO CuPC (200Å), NPD (400Å), BAlq + A-2 (7%) (200Å), Alq ₃ It formed into a film in order of (300 microseconds), LiF (5 microseconds), and Al (1000 microseconds).

1328 cd / m ² (5.8 V) at 0.9 mA, where CIE x = 0.465 and y = 0.339. The lifetime (half the initial luminance) was 3900 hours at 2000 cd / m ² .

Example 2

The light emitting area of the ITO glass was patterned to have a size of 3 mm x 3 mm and then washed. After mounting the substrate in the vacuum chamber, the basic pressure is 1 x 10 ^-6 torr, and the organics are placed on ITO CuPC (200Å), NPD (400Å), BAlq + A-3 (7%) (200Å), Alq ₃ It formed into a film in order of (300 microseconds), LiF (5 microseconds), and Al (1000 microseconds).

At 0.9 mA, it showed 1430 cd / m ² (5.9 V) with CIE x = 0.648 and y = 0.342. The lifetime (half the initial luminance) was 4000 hours at 2000 cd / m ² .

Example 3

The light emitting area of the ITO glass was patterned to have a size of 3 mm x 3 mm and then washed. After mounting the substrate in the vacuum chamber, the base pressure was 1 x 10 ^-6 torr, and the organics were placed on ITO CuPC (200Å), NPD (400Å), BAlq + A-6 (7%) (200Å), Alq ₃ It formed into a film in order of (300 microseconds), LiF (5 microseconds), and Al (1000 microseconds).

140.9 cd / m ² (6.2 V) at 0.9 mA, with CIE x = 0.657 and y = 0.337. The lifetime (half the initial luminance) was 4200 hours at 2000 cd / m ² .

Example 4

The light emitting area of the ITO glass was patterned to have a size of 3 mm x 3 mm and then washed. After mounting the substrate in the vacuum chamber, the basic pressure was 1 x 10 ^-6 torr, and the organics were placed on the ITO CuPC (200Å), NPD (400Å), BAlq + A-7 (7%) (200Å), Alq ₃ It formed into a film in order of (300 microseconds), LiF (5 microseconds), and Al (1000 microseconds).

1320 cd / m ² (6.1 V) at 0.9 mA, where CIE x = 0.665 and y = 0.327. The lifetime (half the initial luminance) was 4000 hours at 2000 cd / m ² .

Example 5

The light emitting area of the ITO glass was patterned to have a size of 3 mm x 3 mm and then washed. After mounting the substrate in the vacuum chamber, the basic pressure was 1 x 10 ^-6 torr, and the organics were placed on ITO CuPC (200Å), NPD (400Å), BAlq + A-16 (7%) (200Å), Alq ₃ It formed into a film in order of (300 microseconds), LiF (5 microseconds), and Al (1000 microseconds).

1361 cd / m ² (6.3 V) at 0.9 mA, with CIE x = 0.641 and y = 0.341. The lifetime (half the initial luminance) was 3700 hours at 2000 cd / m ² .

Example 6

The light emitting area of the ITO glass was patterned to have a size of 3 mm x 3 mm and then washed. After mounting the substrate in the vacuum chamber, the basic pressure is 1 x 10 ^-6 torr, and the organics are placed on ITO CuPC (200Å), NPD (400Å), BAlq + A-17 (7%) (200Å), Alq ₃ It formed into a film in order of (300 microseconds), LiF (5 microseconds), and Al (1000 microseconds).

1431 cd / m ² (6.6 V) at 0.9 mA, where CIE x = 0.652 and y = 0.342. The lifetime (half the initial luminance) was 3500 hours at 2000 cd / m ² .

Comparative example

The light emitting area of the ITO glass was patterned to have a size of 3 mm x 3 mm and then washed. The substrate was placed in a vacuum chamber and the base pressure was 1 x 10 ^-6 torr. Organics were then placed on ITO CuPC (200 kPa), NPD (400 kPa), BAlq + (btp) ₂ Ir (acac) (7%) ( 200 mV), Alq ₃ (300 mV), LiF (5 mV), and Al (1000 mV) in order.

780 cd / m ² (7.5 V) at 0.9 mA, with CIE x = 0.659 and y = 0.329. The lifetime (half the initial luminance) was 2500 hours at 2000 cd / m ² .

Table 1 summarizes the efficiency characteristics, color coordinates, luminance characteristics, and lifetime characteristics of organic electroluminescent devices manufactured according to Examples and Comparative Examples.

device Voltage (V) Current (mA) Luminance (cd / m ² ) Current efficiency (cd / A) Power Efficiency (lm / W) CIE (X) CIE (Y) Life (h) Initial Brightness 1/2 Example 1 5.8 0.9 1328 13.28 7.19 0.654 0.3390.342 3900 Example 2 5.9 0.9 1430 14.30 7.61 0.648 0.342 4000 Example 3 6.2 0.9 1411 14.11 7.15 0.657 0.337 4200 Example 4 6.1 0.9 1320 13.20 6.79 0.659 0.327 4000 Example 5 6.3 0.9 1361 13.61 6.78 0.641 0.341 3700 Example 6 6.6 0.9 1431 14.31 6.81 0.644 0.337 3500 Comparative example 7.5 0.9 780 7.8 3.3 0.659 0.329 2500

According to the present invention, an organic electroluminescent device having higher color purity, higher luminance, and longer life than a conventional organic electroluminescent device can be obtained by using the compound of Formula 1 as the light emitting layer of the organic electroluminescent device.

Claims (4)

Red phosphorescent compound represented by the following formula (1): [Formula 1]

(In Chemical Formula 1)

silver

R 1, R 2 are selected from C ₁ -C ₄ alkyl groups and alkoxy groups, R 3, R 4, R 5 and R 6 are each selected from hydrogen, C ₁ -C ₄ alkyl groups and alkoxy groups,

2,4-pentaneione, 2,2,6,6, -tetramethylheptane-3,5-dione, 1,3-propaneinone, 1,3-butaneinone, 3 , 5-heptanedionone, 1,1,1-trifluoro-2,4-pentaneione, 1,1,1,5,5,5-hexafluoro-2,4-pentane Ions and 2,2-dimethyl-3,5-hexane ions). An organic electroluminescent device comprising a laminate of an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode in order, wherein the compound of claim 1 is used as a dopant of the light emitting layer in an amount of 0.5% by weight to 20% by weight. An organic light emitting device, characterized in that the use of%. The method of claim 2, An organic light emitting display device using any one of Al, Zn metal complex and carbazole derivatives as a host of a light emitting layer. The method of claim 3, wherein The ligand of the Al and Zn metal complexes consists of a quinol group, a biphenyl group, an isoquinol group, a phenyl group, a methylquinol group, a dimethylquinol group and a dimethylisoquinol group, and the carbazole derivative is composed of CBP. Electroluminescent element.

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