KR100662430B1 - Red phosphorescene compounds and organic electroluminescence devices using the same - Google Patents

Abstract

Provided is a red phosphorescence compound, which is useful as a dopant for a light emitting layer in an organic electroluminescence device, and has high light emitting efficiency and long light emitting life while showing excellent coordinate characteristics (high color purity). The red phosphorescence compound is a compound represented by the following formula 1. In the formula 1, ring C-N represents the formula (a), wherein each of R1 and R2 represents a C1-C4 alkyl or alkoxy, and each of R3, R4, R5 and R6 represents H, a C1-C4 alkyl or alkoxy; and ring O-O represents 2,4-pentanedione, 2,2,6,6-tetramethylheptane-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 or 2,2-dimethyl-3,5-hexanedione.

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).

Figure 2 shows the structural formula of the compound used in the embodiment of the present invention NPD, copper (II) phthalocyanine (CuPc), (btp) ₂ Ir (acac), Alq ₃ , BAlq and CBP.

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, there is a demand for the 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.

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, 치환기 R1, R2는 탄소수가 1개~4개인 알킬기 및 알콕시기로 이루어지며, R3, R4, R5 및 R6은 수소, 탄소수가 1개 ~ 4개인 알킬기 및 알콕시기로 이루어지며, 화학식 1에서

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(

)인 것을 특징으로 한다.(In the above formula 1

silver

Substituents R1 and R2 each comprise an alkyl group having 1 to 4 carbon atoms and an alkoxy group, and R3, R4, R5 and R6 each comprise hydrogen, an alkyl group having 1 to 4 carbon atoms and an alkoxy group,

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-pentaneion (

) And 2,2-dimethyl-3,5-hexane ions (

It is characterized by the).

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 light emitting device according to the present invention, any one of Al, Zn metal complex and carbazole derivative may be used as a host of the light emitting layer, and the amount of the dopant is preferably 0.5% to 20% by weight based on the host. 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) -4,7-dimethylisoquinolinato-N, A method for synthesizing the red phosphorescent compound of the present invention will be described taking C ^{2 ′} ) (2,4-pentanedionate-O, O) as an example.

Synthesis Example

1.Synthesis of 2- (3-methylphenyl) -4,7-dimethylquinoline

In a two-necked round bottom flask, 3-methylphenyl boric acid (1.3 mmol), 2-chloro-4,6-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 extracted with dichloromethane and water. After distilling under reduced pressure and distilling off the silica gel column, the solvent was distilled under reduced pressure, and then recrystallized using dichloromethane and petroleum ether to obtain a solid of 2- (3-methylphenyl) -4,7-dimethylquinoline as a product. .

2. Synthesis of Chloro-crosslinked Dimer Complex

In a dried two-necked round bottom flask, iridium (III) chloride hydrate (1 mmol) and 2- (3-methylphenyl) -4,7-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.

3. Synthesis of Iridium (lll) (2- (3-methylphenyl) -4,7-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 was 1 x 10 ^-6 torr, and the organics were placed on ITO CuPC (200Å), NPD (400Å), BAlq + A-1 (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, 1020 cd / m ² (6.3 V) was shown, with CIE x = 0.650 and y = 0.361. The lifetime (half the initial luminance) was 6000 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-2 (7%) (200Å), Alq ₃ It formed into a film in order of (300 microseconds), LiF (5 microseconds), and Al (1000 microseconds).

989 cd / m ² (6.2 V) at 0.9 mA, with CIE x = 0.651 and y = 0.362. The lifetime (half the initial luminance) was 6000 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 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).

866 cd / m ² (6.1 V) at 0.9 mA, with CIE x = 0.652 and y = 0.361. The lifetime (half the initial luminance) was 5000 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 base pressure is 1 x 10 ^-6 torr, and the organics are placed on ITO CuPC (200Å), NPD (400Å), BAlq + A-20 (7%) (200Å), Alq ₃ It formed into a film in order of (300 Hz), LiF (5 Hz), and Al (1000 Hz).

At 0.9 mA, it showed 843 cd / m ² (6.2 V), with CIE x = 0.653 and y = 0.363. 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 (200kPa), NPD (400kPa), BAlq + B-2 (7%) (200kPa), Alq ₃ It formed into a film in order of (300 microseconds), LiF (5 microseconds), and Al (1000 microseconds).

883 cd / m ² (6.1 V) at 0.9 mA, with CIE x = 0.652 and y = 0.361. The lifetime (half the initial luminance) was 4000 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 base pressure was 1 x 10 ^-6 torr, and the organics were placed on ITO CuPC (200Å), NPD (400Å), BAlq + B-7 (7%) (200Å), Alq ₃ It formed into a film in order of (300 microseconds), LiF (5 microseconds), and Al (1000 microseconds).

896 cd / m ² (6.0 V) at 0.9 mA, with CIE x = 0.652 and y = 0.362. The lifetime (half the initial luminance) was 5000 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 6.3 0.9 1020 10.20 5.08 0.650 0.3610.362 6000 Example 2 6.2 0.9 989 9.89 5.01 0.651 0.362 6000 Example 3 6.0 0.9 866 8.66 4.53 0.652 0.361 5000 Example 4 6.2 0.9 843 8.43 4.31 0.653 0.363 4000 Example 5 6.1 0.9 883 8.83 4.52 0.652 0.361 4000 Example 6 6.0 0.9 896 8.96 4.69 0.652 0.362 4000 Comparative example 7.5 0.9 780 7.80 3.27 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 the above formula 1

silver

Substituents R1 and R2 each comprise an alkyl group having 1 to 4 carbon atoms and an alkoxy group, and R3, R4, R5 and R6 each comprise hydrogen, an alkyl group having 1 to 4 carbon atoms and an alkoxy group,

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). In 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, the compound of claim 1 is used as a dopant of the light emitting layer, and the amount of use is Organic light emitting device, characterized in that 0.5% to 20% by weight. The method of claim 2, The host is any one of Al, Zn metal complex and carbazole derivatives. 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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