KR101170666B1 - Bis-carbazole chemiclal and organic electroric element using the same, terminal thererof - Google Patents

Abstract

The present invention provides a biscarbazole compound, an organic electric device using the same, and a terminal thereof.

Organic electric device, biscarbazole

Description

Biscarbazole compound and organic electric device using same, terminal thereof {BIS-CARBAZOLE CHEMICLAL AND ORGANIC ELECTRORIC ELEMENT USING THE SAME, TERMINAL THEREROF}

The present invention relates to a biscarbazole compound, an organic electric device using the same, and a terminal thereof.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their functions. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be. In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. The principle is that when a small amount of dopant having an energy band gap smaller than that of a host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high-efficiency light. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.

The present inventors have found a biscarbazole derivative having a novel structure, and also found that when the compound is applied to an organic electric device, the luminous efficiency, stability and lifetime of the device can be greatly improved.

Accordingly, an object of the present invention is to provide a novel biscarbazole compound, an organic electric device using the same, and a terminal thereof.

In one aspect, the present invention provides a compound of the formula

At this time, the biscarbazole compound according to one embodiment has an asymmetric biscarbazole structure having two or more carbazole rings at the second position of each carbazole.

The biscarbazole compound applied to the organic electric device may be used as a hole injection material, a hole transport material and / or a luminescent material suitable for fluorescence and phosphorescent devices of all colors, such as red, green, blue, and white, depending on the synthesized compound. Biscarbazole compounds applied to organic electrical devices can be used as phosphorescent dopant host materials of various colors.

The compound of the present invention may play various roles in the organic electric device and the terminal, and when applied to the organic electric device and the terminal, it is possible to lower the driving voltage of the device, improve light efficiency and lifespan, and stability of the device.

Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings. In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

The present invention provides a compound of Formula 1 below.

In the formula 1,

(1) Y independently represents a single bond, or -O-,-S-,-CO-,-SO _2- , -NR ^7- , -PR ^8- , -SiR ⁹ R ^10- , or C1- C50 substituted or unsubstituted alkyl group, C1-C50 substituted or unsubstituted alkenyl group, C5-C60 substituted or unsubstituted arylene group, C5-C60 substituted or unsubstituted aryl group, S, N, O Substituted or unsubstituted C1-C50 alkyl group containing at least one hetero atom, P and Si substituted, unsubstituted C1-C50 containing at least one hetero atom, S, N, O, P and Si Alkenyl group, C5-C60 S, N, O, P, and Si substituted or unsubstituted arylene group of C5-C60 containing at least one hetero atom, S5-N, S, N, O, P and Si is a C5-C60 substituted or unsubstituted aryl group containing at least one hetero atom, and two or more carbazoles about Y must be linked to the second position of carbazole All.

(2) R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkoxy group , Substituted or unsubstituted C5-C60 aryl group, substituted or unsubstituted C5-C60 aryloxy group, S, N, O, P and Si substituted or unsubstituted C1 containing at least one hetero atom -A substituted or unsubstituted C1-C50 alkoxy group containing at least one hetero atom, an alkyl group of C50, S, N, O, P and Si, and at least one hetero atom of S, N, O, P and Si Substituted or unsubstituted C5-C60 aryl group containing, S, N, O, P and Si is a substituted or unsubstituted C5-C60 aryloxy group containing at least one hetero atom.

(3) R ¹ to R ⁴ also each include a structure of —N (R ¹¹ ) (R ¹² ), wherein R ¹¹ and R ¹² are the same as R ¹ to R ^{4 as} defined above.

(4) R ⁵ to R ¹⁰ is a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkoxy group, a substituted or unsubstituted C5-C60 aryl group, a substituted or unsubstituted C5 A substituted or unsubstituted C1-C50 alkyl group comprising at least one hetero atom, S, N, O, P and Si, at least one hetero Substituted or unsubstituted C1-C50 alkoxy group containing an atom, S, N, O, P and Si to a substituted or unsubstituted C5-C60 aryl group containing at least one hetero atom, S, N, O, P and Si are substituted or unsubstituted C5-C60 aryloxy groups containing at least one hetero atom.

(5) R ¹³ to R ¹⁴ are the same as R ¹ to R ⁴ defined in the above (2);

In addition, the compound having the above structural formula can be used in a soluble process. Since the solution process can be carried out at low temperature, the thin film can be easily formed on the plastic substrate, and the process cost can be reduced by minimizing the use of vacuum equipment, and the large area process is possible.

As a result, the biscarbazole compound according to the example has an asymmetric biscarbazole structure having two or more carbazole rings in the second position of each carbazole.

The present invention provides a compound of Formulas 2 to 5 below.

At this time, the formula (2) is the same structure as in formula (1), but to be distinguished from the formulas 3 to 5 are represented by a separate formula to separate into subgroups. At this time, R ¹ to R ¹⁴ in Formulas 2 to 5 may be the same as R ¹ to R ¹⁴ defined in Formula 1.

As a specific example of biscarbazole according to one embodiment of the present invention, specific examples of the biscarbazole belonging to Formula 2 include the compounds of Formula 6 below, but the present invention is not limited thereto.

 As a specific example of biscarbazole according to one embodiment of the present invention, specific examples of biscarbazole belonging to Chemical Formula 3 include the compounds of Chemical Formula 7 below, but the present invention is not limited thereto.

As a specific example of biscarbazole according to one embodiment of the present invention, specific examples of biscarbazole belonging to Chemical Formula 4 include the compounds of Chemical Formula 8 below, but the present invention is not limited thereto.

As a specific example of biscarbazole according to one embodiment of the present invention, specific examples of the biscarbazole belonging to Formula 5 include the compounds of Formula 9 below, but the present invention is not limited thereto.

Various organic electronic devices exist in which biscarbazole compounds described with reference to Chemical Formulas 1 to 9 are used as the organic material layer. The organic electronic device in which the biscarbazole compounds described with reference to Chemical Formulas 1 to 9 may be used may be, for example, an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, or an organic transistor (organic TFT). Organic semiconductor materials such as photodiodes, organic lasers, and laser diodes may be used.

As an example of the organic electroluminescent device to which the biscarbazole compounds described with reference to Chemical Formulas 1 to 9 can be applied, the present invention is not limited thereto, but the present invention is not limited thereto. Sol compounds may be applied.

Another embodiment of the present invention is an organic electric device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one layer of the organic material layer comprises an organic electric field comprising the compounds of Formulas 1 to 9 Provided is a light emitting device.

An organic light emitting display device according to another embodiment of the present invention, except that at least one layer of the organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer to form the compound of Formula 1 to 5 It can be prepared in a structure known in the art using conventional manufacturing methods and materials in the art. The structure of the organic light emitting display device according to the present invention is illustrated in FIGS. 1 to 5, but is not limited thereto. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer, 104 a hole transport layer, 105 a light emitting layer, 106 an electron injection layer, and 107 a cathode.

In this case, the biscarbazole compound described with reference to Chemical Formulas 1 to 9 may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer. Specifically, the biscarbazole compound described with reference to Chemical Formulas 1 to 9 may be used in place of one or more of the hole injection layer, hole transport layer, light emitting layer, and electron transport layer described below, or may be used by forming a layer with them. Of course, the organic layer may be used not only in one layer but also in two or more layers.

In particular, the biscarbazole compound described with reference to Chemical Formulas 1 to 9 replaces the existing material or corresponds to one or more of the light emitting layer, for example, blue, green, or red light emitting layer (fluorescent material), respectively. It may also form a layer.

For example, the organic light emitting device according to another embodiment of the present invention is a metal having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation It can be prepared by depositing an oxide or an alloy thereof to form an anode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. .

In addition to the above method, an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.

The organic electroluminescent device according to another embodiment of the present invention may form an organic material layer, for example, a light emitting layer, by the soluble process of the bisbenzoimidazole compound described above.

The substrate is a support of the organic light emitting device, and a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet, or the like can be used.

An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

The hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, when applied for vehicle body display, heat resistance to the device is required, and a material having a glass transition temperature (Tg) of 70 ° C. or higher is preferable. Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compounds, silicone arylamine compounds and the like.

The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.

Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenol lithium salt), bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 ') to increase blue light emission efficiency. [(1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H A small amount of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) is used. When forming a light emitting layer using a process such as inkjet printing, roll coating, or spin coating, a polymer of polyphenylene vinylene (PPV) -based polymer or poly fluorene may be used for the organic light emitting layer. .

As described above, the biscarbazole compound described with reference to Chemical Formulas 1 to 9 replaces the existing material with one or more of the light emitting layer, for example, the blue, green, and red light emitting layers, or forms the layer together with the existing materials. It may be formed.

As described above, the biscarbazole compound described with reference to Chemical Formulas 1 to 9 may be a hole injection material, a hole transport material, and / or suitable for fluorescent and phosphorescent devices of all colors, such as red, green, blue, and white, depending on the synthesized compound. It can be used as a light emitting material.

For example, the biscarbazole compounds described with reference to Formulas 1-9 may be used as phosphorescent dopant host materials of various colors.

The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons. Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The cathode is positioned on the electron transport layer. This cathode serves to inject electrons into the electron transport layer. As the material used as the cathode, it is possible to use the material used for the anode, and a metal having a low work function is more preferable for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.

Meanwhile, the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, various computers, and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Experimental Examples. However, the following Preparation Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example

Hereinafter, preparation examples or synthesis examples of biscarbazole compounds belonging to Chemical Formulas 6 to 9 will be described. However, since the number of biscarbazole compounds belonging to Chemical Formulas 6 to 9 is large, only one or two of biscarbazole compounds belonging to Chemical Formulas 6 to 9 will be exemplarily described. Those skilled in the art, that is, those skilled in the art can prepare the biscarbazole compounds belonging to the present invention not illustrated through the preparation examples described below.

Synthesis of Intermediate 1 (2,7-Dibromocarbazole)

1.Synthesis of 4,4'-Dibromo-2,2'-dinitrobiphenyl

2,5-Dibromonitrobenzene and activated copper powder are dissolved in dimethylformamide (DMF) solvent and stirred at 120 ° C. for 3 hours. Cool the reaction temperature to room temperature, dissolve in Toluene solvent and stir for 30 minutes at room temperature. After filtration under reduced pressure, the organic layer was washed with water and brine, and then a small amount of water was removed with anhydrous MgSO ₄ . Obtained the desired material (yield: 85%).

2. Synthesis of 4,4'-Dibromo-2,2'-diaminobiphenyl

The compound obtained in step 1 and hydrochloric acid (HCl) are dissolved in ethanol, and a small amount of tin (Sn) powder is added and refluxed for 3 hours. Terminate the reaction and pour the reaction into cold water. While stirring, 2 M NaOH aqueous solution was slowly added dropwise to bring the pH of the reactant to 8. The reaction mixture is extracted several times with ether and a small amount of water is removed with anhydrous MgSO ₄ . After filtration under reduced pressure, the organic solvent was concentrated to give the resulting product using column chromatography to give a colorless desired material (yield: 72%).

3. Synthesis of 2,7-Dibromocarbazole

The compound obtained in step 2 is dissolved in phosphoric acid (H ₃ PO ₄ ), and then refluxed at 190 ° C. for 24 hours. The precipitate was filtered off under reduced pressure, washed with water and the precipitate diluted in toluene. After filtration using silica gel, the organic solvent was concentrated, and the resulting product was recrystallized using toluene and hexane solvent to give a white desired substance (yield: 60%).

Synthesis of Intermediate 1 (2-Bromocarbazole)

4. Synthesis of 4-Bromo-2'-nitrobiphenyl

Dissolve 2-Nitrobiphenyl and FeCl ₃ in water and slowly add bromine (Br ₂ ) dropwise. At this time, the temperature of the reaction solution is maintained between 30 ~ 50 ℃. After the dropwise addition is completed, the reaction solution is stirred at 100 ° C for 7 hours. Terminate the reaction and dilute the reaction with ether, and then wipe with 10% Na ₂ CO ₃ , 10% Na ₂ S ₂ O ₃ and brine.

A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was recrystallized using ethanol solvent to give a yellow desired substance (yield: 63%).

5. Synthesis of 2-Bromocarbazole

Into the compound obtained in step 4 and triethylphosphite in the presence of nitrogen and stirred at 160 ℃ for 24 hours.

After completion of the reaction and the temperature of the reactant is cooled to room temperature, the reaction is poured into a methanol solvent to which a small amount of water is added. The resulting precipitate was filtered under reduced pressure and recrystallized with ethanol solvent to give a pale brown desired material (yield: 57%).

의 제조) Preparation Example 1 Compound 2 belonging to the group of Formula 2

Manufacture)

6. Synthesis of Intermediate 2-1

2-bromocarbazole, 2-bromo-9,9-dimethyl-9 H- fluorene, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu synthesized in step 5 were dissolved in toluene, and then 110 Stir for 3 hours at ℃. After completion of the reaction, the temperature of the reactant is cooled to room temperature, extracted with CH ₂ Cl ₂ and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product using column chromatography to give a white desired material (yield: 52%).

7. Synthesis of Intermediate 2-2

Intermediate 21, bis (pinacolato) diboron, PdCl ₂ (dppf) and KOAc synthesized in step 6 were dissolved in DMF and stirred at 130 ° C. for 3 hours. After the reaction is completed, the temperature of the reactant is cooled to room temperature, ether and distilled water are added, and the mixture is stirred again at room temperature. After separating the organic layer and the water layer and repeating the organic layer twice in the same manner, the obtained organic layer is concentrated to obtain a solid. The obtained solid is recrystallized using acetonitrile solvent to give a white desired substance (71%).

8. Synthesis of Intermediate 2-3

After dissolving 2,7-dibromocarbazole, bromobenzene, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu synthesized in step 3 in a toluene solvent, the mixture is stirred at 110 ° C. for 3 hours. After completion of the reaction, the temperature of the reactant is cooled to room temperature, extracted with CH ₂ Cl ₂ and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product by column chromatography to give the desired white material (yield: 74%).

9. Synthesis of Intermediate 2-4

Intermediate 2-3 and 4 (imidazo [1,2 a ] pyridine2yl) phenylboronic acid, Pd (PPh ₃ ) ₄ , K ₂ CO ₃ synthesized in step 8 were dissolved in THF and a small amount of water and then 12 hours at 80 ° C. Stir while. After the reaction is completed, the reaction mixture is cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product using column chromatography to give a white desired material (yield: 44%).

Synthesis of Compound 2

The intermediates 22 and 24, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ synthesized in steps 7 and 9 were dissolved in THF and a small amount of water, and then stirred at 80 ° C. for 24 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product using column chromatography to give a white desired material (yield: 70%).

의 제조) Preparation Example 2 Compound 3 belonging to the group of Formula 3

Manufacture)

10. Synthesis of Intermediate 3-1

2bromocarbazole, iodobenzene, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu synthesized in step 5 were dissolved in a toluene solvent and then stirred at 110 ° C. for 3 hours. After completion of the reaction, the temperature of the reactant is cooled to room temperature, extracted with CH ₂ Cl ₂ and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product using column chromatography to give a white desired material (yield: 65%).

11.Synthesis of Intermediate 3-2

Intermediate 3-1, bis (pinacolato) diboron, PdCl ₂ (dppf), and KOAc synthesized in step 10 were dissolved in DMF and stirred at 130 ° C. for 3 hours. After the reaction is completed, the temperature of the reactant is cooled to room temperature, ether and distilled water are added, and the mixture is stirred again at room temperature. After separating the organic layer and the water layer and repeat the organic layer twice in the same way

The obtained organic layer is concentrated to give a solid. The obtained solid is recrystallized using acetonitrile solvent to give a white desired substance (81%).

12. Synthesis of Intermediate 3-3

2,7dibromocarbazole, 2bromo9,9dimethyl9 H fluorene, Pd ₂ (dba) ₃ , P ( ^t Bu) ₃ and NaO ^t Bu synthesized in step 3 were dissolved in toluene solvent and then stirred at 110 ° C. for 3 hours. After completion of the reaction, the temperature of the reactant is cooled to room temperature, extracted with CH ₂ Cl ₂ and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product using column chromatography to give a white desired material (yield: 70%).

13. Synthesis of Intermediate 3-4

Intermediate 23 and 4 (imidazo [1,2 a ] pyridine2yl) phenylboronic acid, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ synthesized in step 12 were dissolved in THF and a small amount of water and then stirred at 80 ° C. for 12 hours. do. After the reaction is completed, the reaction mixture is cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product using column chromatography to give a white desired material (yield: 40%).

compound 3 Synthesis of

After dissolving intermediates 32 and 34, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ synthesized in steps 11 and 13 in THF and a small amount of water,

Stir at 80 ° C for 24 h. After the reaction is completed, the reaction mixture is cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product using column chromatography to give a white desired material (yield: 68%).

의 제조) Preparation Example 3 Compound 4 belonging to the group of Formula 4

Manufacture)

The intermediates 2-2 and 3-4, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ synthesized in Steps 7 and 13 were dissolved in THF and a small amount of water, followed by stirring at 80 ° C. for 24 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product using column chromatography to give a white desired material (yield: 65%).

Preparation Example 4 (Preparation of Compound 5 belonging to the group of Formula 5)

The intermediates 2-2 and 3-4, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ synthesized in Steps 7 and 13 were dissolved in THF and a small amount of water, followed by stirring at 80 ° C. for 24 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product using column chromatography to give a white desired material (yield: 65%).

The present inventors are to synthesize the biscarbazole compounds according to the embodiments described above by Preparation Examples 1 to 4 using the intermediates described above.

Experimental Example

1. Fabrication of organic electroluminescent device

Compounds 2, 3, and 4 obtained through synthesis were used as light emitting host materials of the light emitting layer, thereby manufacturing an organic light emitting diode according to a conventional method. First, a copper phthalocyanine (hereinafter abbreviated as CuPc) film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a thickness of 10 nm.

Subsequently, 4,4 bis [ N (1 naphthyl) N phenylamino] biphenyl (abbreviated as NPD) was vacuum deposited to a thickness of 30 nm on the membrane to form a hole transport layer. After the hole transport layer was formed, Compound 2, 3 or 4 was deposited on the hole transport layer as a phosphorescent host material to form a light emitting layer.

At the same time, tris (2phenylpyridine) iridium (abbreviated as I r (ppy) ₃ hereinafter) was added as a phosphorescent Ir metal complex dopant. At this time, the concentration of I r (ppy) _{3 in} the light emitting layer was 5% by weight. (1,1'bisphenyl) 4 oleito) bis (2methyl8quinolinoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer, and then tris 8quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic light emitting device.

2. Comparative experiment

For comparison, an organic electroluminescent device having the same structure as the test example was manufactured by using a compound represented by the following formula (hereinafter abbreviated as CBP) as a light emitting host material instead of the compound of the present invention.

Emitting layer
Host material Voltage
(V) Current density
(mA / cm ² ) Luminance
(cd / m ² ) Luminous efficiency
(cd / A) Chromaticity coordinates
(x, y) Example 1 Compound 2 6 0.31 105 48.9 (0.31, 0.61) Example 2 Compound 3 6 0.30 105 48.2 (0.31, 0.61) Example 3 Compound 4 6 0.30 101 42.7 (0.32, 0.61) Comparative Example 1 CBP 6 0.31 101 32.6 (0.33, 0.61)

As can be seen from the results of Table 1, the organic electroluminescent device using the organic electroluminescent device material of the present invention has high efficiency and color purity as well as long-lasting green light emission. Can be used to significantly improve luminous efficiency and lifetime.

On the other hand, it is apparent that the same effect can be obtained even when the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, electron / hole injection and transport layer.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention are not limited by these embodiments.

The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

1 to 5 show examples of the organic electric device to which the compound of the present invention can be applied.

Claims (12)

The compound for organic electric elements represented by following General formula (1).                       Formula (1)

In the above formula (1), (1) Y means single bond, (2) R ¹ to R ⁴ are each independently a hydrogen atom; A halogen atom; Cyano group; Thiol group; An alkyl group of C1-C50; An alkoxy group of C1-C50; C5-C60 aryl group; C5-C60 aryloxy group; C 1 -C 50 heteroalkyl groups containing at least one hetero atom of S, N, O, P and Si; C 1 -C 50 heteroalkoxy groups containing at least one hetero atom of S, N, O, P and Si; C 5 -C 60 heteroaryl groups containing at least one hetero atom of S, N, O, P and Si; C 5 -C 60 heteroaryloxy groups containing at least one hetero atom of S, N, O, P and Si; And amine group; One selected from the group consisting of, (2) R ¹³ and R ¹⁴ are each independently of the other hydrogen atoms; A halogen atom; Cyano group; Thiol group; An alkyl group of C1-C50; An alkoxy group of C1-C50; C5-C60 aryl group; C5-C60 aryloxy group; C 1 -C 50 heteroalkyl groups containing at least one hetero atom of S, N, O, P and Si; C 1 -C 50 heteroalkoxy groups containing at least one hetero atom of S, N, O, P and Si; C 5 -C 60 heteroaryl groups containing at least one hetero atom of S, N, O, P and Si; And S, N, O, P, and Si; C5-C60 heteroaryloxy group containing at least one hetero atom. The method of claim 1, The compound of formula (1) is represented by the following formula (2) or formula (3).            Formula (2) Formula (3)

,

In the above formula (2) or formula (3), Y, R ¹ to R ⁴ , R ¹³ and R ¹⁴ are the same as in the general formula (1). The method according to claim 1 or 2, When R ¹ to R ⁴ are each independently an amine group of -N (R ¹¹ ) (R ¹² ), R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, a cyano group, a thiol group, C 1 -C 50 C 1 -C 50 alkyl group, C 1 -C 50 alkoxy group, C 5 -C 60 aryl group, C 5 -C 60 aryloxy group, S, N, O, P and Si containing at least one hetero atom, C 1 -C 50 alkyl group, S , C1-C50 alkoxy group containing at least one hetero atom, N, O, P and Si, C5-C60 aryl group containing at least one hetero atom, S, N, O, P and Si, S , N, O, P and Si is a C5-C60 aryloxy group containing at least one hetero atom. The method according to claim 1 or 2, The compound is an organic electroluminescent device, characterized in that used in a solution process (soluble process). The method according to claim 1 or 2, The compound is

Compound for an organic electric device, characterized in that one selected from the group consisting of. An organic electronic device comprising at least one organic material layer comprising the compound of claim 1. The method of claim 6, The organic electronic device is an organic electroluminescent device comprising a first electrode, the at least one organic material layer and the second electrode in a stacked form sequentially. The method of claim 6, The organic material layer includes a hole injection / transport layer, a light emitting layer, an electron injection layer, the compound is an organic electronic device, characterized in that included in the light emitting layer. 9. The method of claim 8, The compound is an organic electronic device, characterized in that to form the light emitting layer by a solution process (soluble process). 9. The method of claim 8, The compound is an organic electronic device, characterized in that used as the green phosphorescent host material in the light emitting layer. A display device comprising the organic electric element of claim 6; And a control unit for driving the display device. Compound for an organic electric device represented by one of the following compounds.

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