KR20100079458A - Bis-carbazole chemiclal and organic electroric element using the same, terminal thererof - Google Patents

Abstract

PURPOSE: An asymmetry bis-carbazole compound and organic electric device using the same are provided to lower device driving voltage in applying to the organic electric device and terminal and to improve optical efficiency. CONSTITUTION: An asymmetry bis-carbazole compound is denoted by chemical formula. An organic electric device comprises one or more layers of an organic layer containing the asymmetry bis-carbazole compound. The organic electric device is an organic electroluminescence device. The organic layer comprises a hole injection/transport layer, light emitting layer, and electron injection layer. The hole injection/transport layer contains the asymmetry bis-carbazole. A terminal comprises a display device and control unit.

Description

Bis-carbazole 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 an asymmetric bis-carbazole 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 shifts to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be 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 inventors have found asymmetric bis-carbazole derivatives having a novel structure, and have also found that when the compound is applied to an organic electronic device, the luminous efficiency, stability and lifespan of the device can be greatly improved.

Accordingly, an object of the present invention is to provide a novel bis-carbazole 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 bis-carbazole compound according to an embodiment of the present invention has a non-symmetric structure around Y. On the other hand, when Y is a single bond, it has an asymmetrical structure around this single bond.

Meanwhile, at least one of R ¹ to R ⁶ may include a structure of -N (R ⁷ ) ₂ or -N (R ⁷ ) (R ⁸ ).

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 and improve the light efficiency.

Hereinafter, some embodiments of the present invention will be described in detail through 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 only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

The present invention provides a compound of Formula 1 below.

In Formula 1, (1) Y independently means a single bond, a substituted or unsubstituted alkyl group of C1-C50, a substituted or unsubstituted alkenyl group of C1-C50, a substituted or unsubstituted C5-C60 Arylene group, C5-C60 substituted or unsubstituted aryl group, C, C50 substituted or unsubstituted alkyl group containing at least one hetero atom, S, N, O, P and Si, S, N, O , C-C50 substituted or unsubstituted alkenyl group containing at least one hetero atom, P and Si, C5-C60 containing at least one hetero atom, S, N, O, P and Si of C5-C60 It may be one selected from the group consisting of a substituted or unsubstituted arylene group of, C5-C60 S, N, O, P and Si of C5-C60 substituted or unsubstituted aryl group containing at least one hetero atom. .

(2) R ¹ to R ⁶ are each independently 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 A substituted or unsubstituted C5-C60 aryl group comprising one, S, N, O, P and Si selected from the group consisting of a substituted or unsubstituted C5-C60 aryloxy group containing at least one hetero atom Can be.

At this time, it has an asymmetric structure necessarily around Y. On the other hand, when Y is a single bond, it necessarily has an asymmetric structure around this single bond.

(3) at least one of R ¹ to R ⁶ may include a structure of —N (R ⁷ ) ₂ or —N (R ⁷ ) (R ⁸ ). In this case, R ⁷ , R ⁸ are the same as R ¹ to R ⁶ defined above, and must have an asymmetric structure around Y. When Y means a single bond, it must have an asymmetric structure around this single bond. do.

로 구성된 군으로부터 선택된 하나이며, 이때 Y의 기본골격구조는 S, N, O, P 및 Si를 포함하는 적어도 하나 이상의 헤테로 원자를 포함할 수도 있다. Preferred examples of Y are a single bond,

It is one selected from the group consisting of, wherein the basic skeleton structure of Y may include at least one or more hetero atoms including S, N, O, P and Si.

At this time, R ⁹ to R ²⁰ may be the same as R ¹ to R ⁶ defined above, more preferably hydrogen atom, F, Cl, Br, I, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, sec-butyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, t-butoxy group, sec-butoxy group, cyano group, thiol group, alkylamine group, arylamine group, 1 -Naphthyl group, 2-naphthyl group, biphenyl group, anthryl group, pyridyl group, perylene group, pyrene group, quinoline group, isoquinoline group, carbazole group, fluorene group. In this case, R ⁹ to R ²⁰ may be substituted or unsubstituted.

The present invention provides a compound of Formulas 2 to 7 below. In this case, the formula (2) is the same structure as in formula (1), but is distinguished from the formulas 3 to 7 are represented by a separate formula to be divided into subgroups not substituted with an amine group. At this time, in Formulas 2 to 7 R ⁷ , R ⁸ may be the same as R ¹ to R ⁶ defined above.

As a specific example of the asymmetric bis-carbazole according to an embodiment of the present invention, specific examples of the asymmetric bis-carbazole belonging to Formula 2 include the compounds of Formula 7 (Number 1 to 32), but the present invention It is not limited only to.

As a specific example of the asymmetric bis-carbazole according to one embodiment of the present invention, specific examples of the asymmetric bis-carbazole belonging to Formula 3 include the compounds of the following formula (9) (Number 33 to 69), the present invention It is not limited only to.

As a specific example of the asymmetric bis-carbazole according to an embodiment of the present invention, specific examples of the asymmetric bis-carbazole belonging to formula (4) are the compounds of formula (10) below (number 70 to 88), the present invention It is not limited only to.

As a specific example of the asymmetric bis-carbazole according to an embodiment of the present invention, specific examples of the asymmetric bis-carbazole belonging to Formula 5 include the compounds of Formula 11 (Nos. 92 to 105). It is not limited only to.

As a specific example of the asymmetric bis-carbazole according to an embodiment of the present invention, specific compounds of the asymmetric bis-carbazole belonging to formulas (6) and (7) (12-118), but the present invention Is not limited to these.

Various organic electronic devices exist in which the asymmetric bis-carbazole compounds described with reference to Chemical Formulas 1 to 12 are used as the organic material layer. Organic electronic devices in which the asymmetric bis-carbazole compounds described with reference to Chemical Formulas 1 to 12 may be used include, for example, an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor (organic). Organic semiconductor materials such as TFT, photodiode, organic laser, laser diode, etc. may be used.

As an example of the organic electroluminescent device to which the asymmetric bis-carbazole compounds described with reference to Chemical Formulas 1 to 12 may be applied, the present invention is not limited thereto, and the present invention is not limited thereto. Asymmetric bis-carbazole compounds can 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 of the organic material layer of the organic electric field comprising the compounds of Formula 1 to 12 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 12, 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 asymmetric bis-carbazole compound described with reference to Chemical Formulas 1 to 12 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 asymmetric bis-carbazole compound described with reference to Formulas 1 to 12 may be used instead 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. . It is not only used in one layer of the organic material layer, but may be formed in two or more layers, for example, the hole injection layer and the hole transport layer, respectively, or replace the existing materials with the existing materials.

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 by using a variety of polymer materials, and by using a process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than a deposition method. It can be prepared in layers.

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, and the like, but are not limited thereto. .

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. The materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium Oxide compounds, silicon 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.

Alq3 for green, Balq (8-hydroxyquinoline beryllium salt), DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl) for green Series, Spiro substance, 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 complexes, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 '[( 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. .

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 control, a navigation device, a game machine, various TVs, and various computers.

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.

Production Example

Hereinafter, preparation or synthesis examples of the asymmetric bis-carbazole compounds belonging to the formulas (2) to (7) will be described. However, only one of the asymmetric bis-carbazole compounds belonging to the general formulas 2 to 7 is exemplarily described since the number of the asymmetric bis-carbazole compounds belonging to the general formulas 2 to 7 is exemplarily described. Those skilled in the art, that is, those skilled in the art can prepare asymmetric bis-carbazole compounds belonging to the present invention which are not illustrated through the preparation examples described below.

의 제조) Preparation Example 1 (Compound No. 2 belonging to the group of Formula 2

Manufacture)

1. Synthesis of Intermediate 2a

Carbazole, iodobenzene, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ , and t -BuONa are dissolved in toluene and then stirred at 60 ^° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with CH ₂ Cl ₂ , followed by removal of moisture contained in the organic solvent using MgSO ₄ . The product of the oil condition generated by concentrating the organic solvent is n - by using hexane (n -hexane) and acetone (acetone) solvent to produce a precipitate gradually settled obtained. The precipitate thus obtained was dissolved again using a toluene solvent and filtered. The filtered solution is concentrated and then slowly reprecipitated at low temperature to give the desired 2a as a white solid. (Yield: 78%)

2. Synthesis of Intermediate 2a-1

_

Acetic acid was added to intermediate 2a, followed by addition of iodine and iodine acid in solid state, followed by stirring at 80 ^o C for 2 hours. After completion of the reaction, the mixture was extracted three times with diethyl ether, and the combined organic layers were dried over MgSO ₄ and the solvent was evaporated to obtain a solid. The obtained solid is separated and purified by silica gel column chromatography to obtain intermediate 2a-1 as a white solid. (Yield 83%).

3. Synthesis of Intermediate 2a-2

Intermediate 2a-1, Bis (pinacolato) diboron, PdCl ₂ (dppf) and potassium acetate were dissolved in DMF (10 L) and stirred at 130 ° C. for 2 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, diethyl ether and distilled water are further added, and the mixture is stirred again at room temperature. After the stirring was stopped, the organic layer and the water layer were separated, the organic layer was repeated twice in the same manner, and the obtained organic layer was concentrated to obtain a solid. The solid thus obtained was recrystallized using acetonitrile to obtain intermediate 2a-2 as a white solid. (Yield 71%)

4. Synthesis of Intermediate 2b

Carbazole (Carbazole) and 3 hours 9,9-dimethyl-2-bromofluorene, Pd 2 (dba) 3, P (t -Bu) 3, and 60 ^o C was dissolved in toluene t -BuONa (toluene) the solvent Stir. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with CH ₂ Cl ₂ , followed by removal of moisture contained in the organic solvent using MgSO ₄ . The product of the oil condition generated by concentrating the organic solvent is n - by using hexane (n -hexane) and acetone (solvent acetone0 produce was gradually precipitated and the precipitate obtained.

The precipitate thus obtained was dissolved again using a toluene solvent and filtered. The filtered solution is concentrated and then slowly reprecipitated at low temperature to give the desired 2b as a white solid. (Yield: 78%)

5. Synthesis of Intermediate 2b-1

2b and bromine are dissolved in a CH ₂ Cl ₂ solvent and stirred at room temperature for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with CH ₂ Cl ₂ , followed by removal of moisture contained in the organic solvent using MgSO ₄ . The reaction product obtained by concentrating the organic solvent was separated and purified by silica gel column chromatography to obtain intermediate 2b-1 as a white solid. (Yield: 78%)

6. Synthesis of Compound 2

2a-2, 2b-1, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ were added to a reaction flask filled with nitrogen, dissolved in THF and water as a solvent, followed by stirring at 80 ° C. for 12 hours. After the reaction is completed, the temperature of the reaction solution is cooled to room temperature, extracted with CH ₂ Cl ₂ , and the moisture contained in the organic solvent is removed using MgSO ₄ . The reaction product obtained by concentrating the organic solvent was separated and purified by silica gel column chromatography to obtain Compound 2 as a yellow solid (yield: 72%).

의 제조) Preparation Example 2 (Compound No. 49 belonging to Group 3)

Manufacture)

1. Synthesis of Intermediate 49a

It can be synthesized in the same manner as the synthesis method of the intermediate 2a described above. (Yield 67%)

2. Synthesis of Intermediate 49a-1

Synthesis can be carried out in the same manner as in the synthesis of Intermediate 2b-1 described above. (Yield: 70%)

3. Synthesis of Intermediate 49a-2

Synthesis can be carried out in the same manner as in the synthesis of Intermediate 2a-2 described above. (Yield 66%)

4. Synthesis of Compound 49

Synthesis can be carried out in the same manner as in the synthesis of Compound 2 described above. (Yield 69%)

의 제조) Preparation Example 3 (Compound No. 70 belonging to Group 4

Manufacture)

1. Synthesis of Intermediate 70a

It can be synthesized in the same manner as the synthesis method of the intermediate 2a described above. (Yield 74%)

2. Synthesis of Intermediate 70a-1

Synthesis can be carried out in the same manner as in the synthesis of Intermediate 2b-1 described above. (Yield 76%)

3. Synthesis of Compound 70

Synthesis can be carried out in the same manner as in the synthesis of Compound 2 described above. (Yield 62%)

의 제조) Preparation Example 4 (Compound No. 92 belonging to Group 5)

Manufacture)

1. Synthesis of Intermediate 92a

 In addition to doubling the number of bromine (Bromine) in the above-described synthesis method of compound 2b-1, the rest of the process can be synthesized in the same manner as before. (Yield 69%)

2. Synthesis of Intermediate 92a-1

 It can be synthesized in the same manner as the synthesis method of the intermediate 2a described above. (Yield 52%)

3. Synthesis of Compound 92

 Synthesis can be carried out in the same manner as in the synthesis of Compound 2 described above. (Yield 66%)

의 제조) Preparation Example 5 Compound No. 106 belonging to Group 6

Manufacture)

1. Synthesis of Intermediate 106a

 Synthesis can be carried out in the same manner as in the synthesis of Intermediate 2a-2 described above. (Yield 53%)

2. Synthesis of Intermediate 106b

 It can be synthesized in the same manner as the synthesis method of the intermediate 2a described above. (Yield 74%)

3. Synthesis of Compound 106

 Synthesis can be carried out in the same manner as in the synthesis of Compound 2 described above. (Yield 62%)

의 제조) Preparation Example 6 (Compound No. 111 belonging to Group 7)

Manufacture)

1.Synthesis of Compound 111

 Synthesis can be carried out in the same manner as in the synthesis of Compound 2 described above. (Yield: 73%)

Experimental Example

For comparison with the compounds 70, 92, and 106 of the present invention, the physical properties of the organic light emitting diodes using 2-TNATA as the hole injection layer were measured and compared.

An organic light emitting diode was manufactured according to a conventional method using 2-TNATA (4,4 ', 4''Tris [2-naphthyl (phenyl) amino] -triphenylamine) as a hole injection layer material.

First, a 600 Å hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole transport layer (hole transport layer material: NPB), and a 450 Å BD- layer on the ITO layer (anode) formed on the glass substrate. Luminescent layer doped with 052X (Idemitsu) 7% (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 전자 thick electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), 10 Å thick electron injection layer (electron injection layer material: LiF), and 1500 Å thick aluminum cathode Evaporation was carried out to produce an organic light emitting display device.

The driving voltage, current density, efficiency, and color coordinates of the organic light emitting diodes manufactured as described above were measured to be 6.95 V, 14.31 mA / cm ² , 5.21 cd / A, and (0.145, 0.143), respectively.

Experimental Example 1 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 70 of the Present Invention as Hole Injection Layer)

Using the compound 70 as the hole injection layer material, an organic light emitting display device was manufactured according to a conventional method.

First, a 600 Å hole injection layer (hole injection layer material: compound 70), a 300 Å hole transport layer (hole transport layer material: NPB), and 450 Å thickness BD-052X on the ITO layer (anode) formed on the glass substrate. (Idemitsu Co., Ltd.) 7% doped light emitting layer (where BD-052X is a blue fluorescent dopant, and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 Hz Deposition of a thick electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), a 10-thick electron injection layer (electron injection layer material: LiF), and an aluminum cathode of 1500 Å in order To produce an organic light emitting device.

The driving voltage, current density, luminous efficiency, and color coordinates of the organic light emitting display device manufactured by Experimental Example 1 were measured as 5.87 V, 13.44 mA / cm ² , 6.64 cd / A, and (0.145, 0.146), respectively.

Experimental Example 2 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 92 of the Present Invention as Hole Injection Layer)

Using the compound 92 as the hole injection layer material, an organic light emitting display device was manufactured according to a conventional method. First, a 600 Å hole injection layer (hole injection layer material: Compound 92), a 300 Å hole transport layer (hole transport layer material: NPB), 450 Å thickness BD-052X on the ITO layer (anode) formed on the glass substrate (Idemitsu Co., Ltd.) 7% doped light emitting layer (where BD-052X is a blue fluorescent dopant, and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 Hz Deposition of a thick electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), a 10-thick electron injection layer (electron injection layer material: LiF), and an aluminum cathode of 1500 Å in order To produce an organic light emitting device.

The driving voltage, current density, luminous efficiency, and color coordinates of the organic light emitting device manufactured by Experimental Example 2 were measured to be 6.26V, 13.07mA / cm ² , 6.46cd / A, (0.145, 0.149), respectively.

Experimental Example 3 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 106 of the Present Invention as Hole Injection Layer)

An organic light emitting display device was manufactured according to a conventional method using compound 106 as a hole injection layer material.

First, a 600 Å hole injection layer (hole injection layer material: Compound 92), a 300 Å hole transport layer (hole transport layer material: NPB), 450 Å thickness BD-052X (on the ITO layer (anode) formed on the glass substrate Idemitsu) 7% doped light emitting layer (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 mW Electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), 10 electron thickness injection layer (electron injection layer material: LiF) and 1500 Å thick aluminum cathode An organic electroluminescent device was manufactured.

The driving voltage, current density, luminous efficiency, and color coordinates of the organic light emitting display device manufactured by Experimental Example 2 were measured to be 5.92V, 13.43mA / cm ² , 6.87cd / A, and (0.145, 0.145), respectively.

Table 1 summarizes the physical properties of the organic light emitting device using 2TNATA as the hole injection layer material and the organic light emitting device of Experimental Examples 1 to 3.

TABLE 1

Hole injection layer material Voltage
(V) Currentdensity
(mA / cm ² ) Efficiency
(㏅ / A) CIE
(x, y) Control 1 2TNATA 6.95 14.31 5.21 (0.145, 0.143) Experimental Example 1 Compound 70 5.87 13.44 6.64 (0.145, 0.146) Experimental Example 2 Compound 92 6.26 13.07 6.46 (0.145, 0.149) Experimental Example 3 Compound 106 5.92 13.43 6.87 (0.145, 0.145)

As can be seen from Table 1, the organic light emitting display devices of Experimental Examples 1 to 3 exhibit substantially the same color coordinates as the organic electroluminescent device using 2TNATA as the hole injection layer material, and have the driving voltage, current density, and luminous efficiency. It can be seen that this critical improvement has been achieved.

In addition, the physical properties of the organic electroluminescent device using NPB as the hole transport layer was measured for comparison with the compounds 2, 49, 111 of the present invention.

An organic light emitting diode was manufactured according to a conventional method using NPB (N, N'-Di-1-naphthyl-N, N'-diphenylbenzidine) as a hole transport material.

First, a 600 Å hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole transport layer (hole transport layer material: NPB), and 450 Å thickness BD- on the ITO layer (anode) formed on the glass substrate. Light-emitting layer doped with 052X (Idemitsu Co., Ltd.) 7% (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 전자 thick electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), 10 Å thick electron injection layer (electron injection layer material: LiF) and 1500 Å thick aluminum cathode Evaporation was carried out to produce an organic light emitting display device.

The driving voltage, current density, efficiency, and color coordinates of the organic light emitting diodes thus manufactured were measured as 6.73 V, 15.23 mA / cm ² , 5.32 cd / A, and (0.145, 0.147), respectively.

Experimental Example 4 ( Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 2 of the Present Invention)

Using organic compound 2 as a hole transport material, an organic light emitting display device was manufactured according to a conventional method.

First, a 600 Å hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole transport layer (hole transport layer material: compound 2), and a 450 Å BD on the ITO layer (anode) formed on the glass substrate. A light emitting layer doped with -052X (Idemitsu Co., Ltd.) 7% (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), An electron transport layer of 250 Å thickness (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), an electron injection layer of 10 Å thickness (electron injection layer material: LiF), and an aluminum cathode of 1500 Å thickness By sequentially depositing, an organic light emitting display device was manufactured.

The driving voltage, current density, efficiency, and color coordinates of the organic light emitting diode thus manufactured were measured as 5.77 V, 14.02 mA / cm ² , 6.83 cd / A, and (0.145, 0.151), respectively.

Experimental Example 5 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 49 of the Present Invention as Hole Transport Layer)

 Using an compound 49 as a hole transport material, an organic light emitting display device was manufactured according to a conventional method.

First, a 600 Å hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole transport layer (hole transport layer material: Compound 49), and a 450 Å BD on the ITO layer (anode) formed on the glass substrate. A light emitting layer doped with -052X (Idemitsu Co., Ltd.) 7% (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), An electron transport layer of 250 Å thickness (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), an electron injection layer of 10 Å thickness (electron injection layer material: LiF), and an aluminum cathode of 1500 Å thickness By sequentially depositing, an organic light emitting display device was manufactured.

The driving voltage, current density, efficiency, and color coordinates of the organic light emitting diode thus manufactured were measured as 5.63 V, 13.92 mA / cm ² , 6.685.21 cd / A, and (0.145, 0.146), respectively.

Experimental Example 6 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 111 of the Present Invention)

An organic light emitting display device was manufactured according to a conventional method using compound 111 as a hole transport layer material.

First, a 600 Å hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole transport layer (hole transport layer material: Compound 111), and a 450 BD BD on the ITO layer (anode) formed on the glass substrate. A light emitting layer doped with -052X (Idemitsu Co., Ltd.) 7% (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), An electron transport layer of 250 Å thickness (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), an electron injection layer of 10 Å thickness (electron injection layer material: LiF), and an aluminum cathode of 1500 Å thickness By sequentially depositing, an organic light emitting display device was manufactured.

The driving voltage, current density, efficiency, and color coordinates of the organic light emitting diode thus manufactured were measured as 6.14 V, 13.78 mA / cm ² , 6.53 cd / A, and (0.145, 0.147), respectively.

Table 2 shows the physical properties of the organic light emitting display device using NPB as the hole transport layer material and the organic light emitting display device of Experimental Examples 4 to 6.

TABLE 2

Hole transport material Voltage
(V) Currentdensity
(mA / cm ² ) Efficiency
(㏅ / A) CIE
(x, y) Control 2 NPB 6.73 15.23 5.32 (0.145, 0.147) Experimental Example 4 Compound 2 5.77 14.02 6.83 (0.145, 0.151) Experimental Example 5 Compound 49 5.63 13.92 6.68 (0.145, 0.146) Experimental Example 6 Compound 111 6.14 13.78 6.53 (0.145, 0.147)

As can be seen from Table 2, the organic light emitting diodes of Experimental Examples 4 to 6 exhibit substantially the same color coordinates as compared to the organic light emitting diodes using NPB as the hole transport layer material, and have high driving voltage, current density, and luminous efficiency. It can be seen that it improved with critical significance.

Through the above results, the compounds of the present invention can be seen that the physical properties such as driving voltage, current density, luminous efficiency is improved when used in the organic light emitting device as a hole injection layer or a hole transport layer material. On the other hand, even if the compounds of the present invention are used in other organic material layer of the organic light emitting device it is obvious that the same effect can be obtained.

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. Therefore, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, 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 (10)

A compound represented by the following formula;

In the above formula, (1) Y independently means a single bond, a substituted or unsubstituted alkyl group of C1-C50, a substituted or unsubstituted alkenyl group of C1-C50, a substituted or unsubstituted aryl of C5-C60 A benzene group, a substituted or unsubstituted aryl group of C5-C60, a C1-C50 substituted or unsubstituted alkyl group containing at least one hetero atom, S, N, O, P, and Si, S, N, O, P And a substituted or unsubstituted alkenyl group of C 1 -C 50 containing at least one hetero atom, Si, a substituted of C 5 -C 60 containing at least one hetero atom of S, N, O, P and Si of C 5 -C 60. Or an unsubstituted arylene group, C 5 -C 60 S, N, O, P and Si selected from the group consisting of C 5 -C 60 substituted or unsubstituted aryl groups containing at least one hetero atom; (2) R ¹ to R ⁶ are each independently 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 one selected from the group consisting of substituted or unsubstituted C5-C60 aryloxy group containing at least one hetero atom . The method of claim 1, Wherein at least one of R ¹ to R ⁶ is a structure of —N (R ⁷ ) ₂ or —N (R ⁷ ) (R ⁸ ). The method of claim 2, R ⁷ and R ⁸ are the same as those of R ¹ to R ⁶ . A compound represented by one of the following formulae;

,

,

,

,

,

(1) Y independently means a single bond, a substituted or unsubstituted alkyl group of C1-C50, a substituted or unsubstituted alkenyl group of C1-C50, a substituted or unsubstituted arylene group of C5-C60, C5- A substituted or unsubstituted aryl group of C 60, S, N, O, P, and Si a substituted or unsubstituted alkyl group of C 1 -C 50 containing at least one hetero atom, S, N, O, P and Si at least A substituted or unsubstituted alkenyl group of C1-C50 containing one or more hetero atoms, S, N, O, P and Si of C5-C60 substituted or unsubstituted C5-C60 containing at least one hetero atom Arylene group, C 5 -C 60 S, N, O, P and Si are one selected from the group consisting of C 5 -C 60 substituted or unsubstituted aryl groups containing at least one hetero atom; (2) R ¹ to R ⁸ are each independently 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 one selected from the group consisting of substituted or unsubstituted C5-C60 aryloxy group containing at least one hetero atom . The method according to claim 1 or 4, Y is a single bond or

One is selected from the group consisting of, when the Y is not a single bond, the basic skeleton includes at least one hetero atom including S, N, O, P and Si, wherein R ⁹ to R ²⁰ is the R ¹ to R ^{6 the} same compound. The method of claim 5, R ⁹ to R ²⁰ are hydrogen atom, F, Cl, Br, I, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, sec-butyl group, methoxy group, ethoxy group, propoxy group, Isopropoxy group, t-butoxy group, sec-butoxy group, cyano group, thiol group, alkylamine group, arylamine group, 1-naphthyl group, 2-naphthyl group, biphenyl group, anthryl group, pyridyl group, peryl A compound selected from the group consisting of a ethylene group, a pyrene group, a quinoline group, an isoquinoline group, a carbazole group and a fluorene group, and is a substituted or unsubstituted compound. An organic electronic device comprising at least one organic material layer comprising a compound of claim 1 or claim 4. The method of claim 7, wherein 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 organic electronic device of claim 8, wherein the organic material layer includes a hole injection / transport layer, a light emitting layer, and an electron injection layer, and the compound of claim 1 is included in the sperm injection / transport layer. A display device comprising the organic electric element of claim 7; And a control unit for driving the display device.

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