KR101188280B1 - Compound Containing Carbazole and Aromatic Amine Derivative compound, And Organic Electronic Element Using The Same, Terminal Thereof - Google Patents

Abstract

The present invention provides a compound comprising a carbazole and an aromatic amine derivative, an organic electric device using the same, and a terminal thereof.

Description

Compound Containing Carbazole and Aromatic Amine Derivative compound, And Organic Electronic Element Using The Same, Terminal Thereof}

The present invention relates to a compound comprising a carbazole and an aromatic amine derivative, 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 and 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 depending on the molecular weight, and may be classified into a phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . 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.

Embodiments of the present invention to solve the problems of the above-described background, a compound containing a carbazole and an aromatic amine derivative having a novel structure has been found, and also when applying the compound to an organic electronic device organic electronic device It has been found that the effect of increasing the efficiency, lowering the driving voltage, increasing the lifetime and increasing the stability.

Accordingly, an object of the present invention is to provide a compound comprising a novel carbazole and an aromatic amine derivative, an organic electric device using the same, and a terminal thereof.

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

The present invention is a compound containing a carbazole and an aromatic amine derivative can be used as a hole injection, hole transport, electron injection, electron transport, a light emitting material and a passivation (kepping) material in an organic electronic device, in particular a light emitting material and a host alone It can be used as a host or dopant in dopants, and can be used as a hole injection and hole transport layer. The present invention also provides a compound including a carbazole and an aromatic amine derivative, an organic electronic device using the same, and a terminal including the organic electronic device.

The present invention is used as an organic light emitting device as a compound containing a carbazole and an aromatic amine derivative to provide the effect of increasing the efficiency of the organic electronic device, lowering the driving voltage, increase in life and stability when applied to the organic electroluminescent device.

1 to 6 show examples of organic electroluminescent devices to which the compounds of the present invention can be applied.

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 describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may 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 as follows.

(1) Ar1 to Ar4 may each independently be a substituted or unsubstituted aromatic hydrocarbon group having 5 to 40 carbon atoms, or a substituted or unsubstituted hetero atom having 3 to 60 atoms.

(2) Cz represents formula (2) wherein R 1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, R 2 is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted carbon number 1 To 50 alkyl groups, substituted or unsubstituted alkoxy groups having 1 to 50 carbon atoms, substituted or unsubstituted arylthio groups having 1 to 50 carbon atoms, substituted or unsubstituted alkoxycarbonyl groups having 2 to 50 carbon atoms, substituted or unsubstituted It may be an amino group, a halogen atom, a cyano group, a nitro group, a hydroxyl group or a carboxyl group substituted with an aryl group having 6 to 50 carbon atoms.

(3) L independently represents a linking group selected from a substituted or unsubstituted arylene group, a substituted or unsubstituted hetero arylene group, a tetravalent or higher substituted or unsubstituted aliphatic hydrocarbon, and specifically,

It may be selected from the group consisting of.

일 수 있다.
More specifically, L

Lt; / RTI >

Specific examples of the compounds belonging to Formulas 1 and 2, which are compounds including carbazole and aromatic amine derivatives according to an embodiment of the present invention, may be the compounds of Formulas 3 and 4, but the present invention is not limited thereto. .

In another aspect, the present invention provides a compound of formula 3 when comprising 3 carbazole.

In another aspect, the present invention provides a compound of formula 4 when comprising 2 carbazole.

In Formulas 3 and 4, Ar ₁ to Ar ₄ may be the same as Ar ₁ to Ar ₄ in Formula 1, and R ₁ to R ₄ may be the same as R ₁ and R ₂ of Formula 2.

In addition, the compounds of Formulas 3 and 4 may be implemented in the form of Formulas 5 and 6, but the present invention is not limited thereto.

Various organic electric devices exist in which compounds including carbazole and aromatic amine derivatives described with reference to Chemical Formulas 1 to 6 are used as the organic material layer. Examples of organic electroluminescent devices in which compounds including carbazole and aromatic amine derivatives described with reference to Chemical Formulas 1 to 6 may be used include organic electroluminescent devices (OLEDs), organic solar cells, organophotoreceptor (OPC) drums, and organic Transistors (organic TFTs).

As an example of an organic electroluminescent device to which compounds including carbazole and aromatic amine derivatives described with reference to Chemical Formulas 1 to 6 can be applied, an organic light emitting diode (OLED) is described, but the present invention is not limited thereto. Compounds comprising the carbazole and aromatic amine derivatives described above can be applied to the device.

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 6 Provided is a light emitting device.

1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.

In an organic light emitting display device according to another embodiment of the present invention, at least one layer of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer is formed to include the compounds of Formulas 1 to 6 above. Except for the above, it may be manufactured 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 another embodiment of the present invention is illustrated in FIGS. 1 to 6, but is not limited thereto. 1, reference numeral 101 is a substrate, 102 is an anode, 103 is a hole injection layer (HIL), 104 is a hole transport layer (HTL), 105 is a light emitting layer (EML), 106 is an electron injection layer (EIL) ), 107 represents an electron transport layer (ETL), and 108 represents a cathode. Although not shown, the organic light emitting diode may further include a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for preventing the movement of electrons, and a protective layer. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.

In this case, the compound including the carbazole and the aromatic amine derivative described with reference to Chemical Formulas 1 to 6 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 compound including the carbazole and the aromatic amine derivative described with reference to Chemical Formulas 1 to 6 is one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, a protective layer It may be used instead of the above 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 compound including the carbazole and the aromatic amine derivative described with reference to Chemical Formulas 1 to 6 may be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a light emitting material and a passivation (kepping) material, In particular, it can be used alone as a light emitting material and a host or dopant. More specifically, the compound may be used as the hole transport material in the hole transport layer can significantly improve the low driving voltage, high luminous efficiency and life.

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 An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. Can be prepared.

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, an electron transport layer and an electron injection 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 organic electroluminescent device according to another embodiment of the present invention may be used in a solution process such as spin coating or ink jet process of the compound including the carbazole and the aromatic amine derivative described above. have.

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 Compound, a silicon-based arylamine compound, 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 Small amounts of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) can be used. When the light emitting layer is formed using a process such as inkjet printing, roll coating, or spin coating, an organic light emitting layer is formed of a polymer of polyphenylene vinylene (PPV) or a polymer such as poly fluorene. Can be used for

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 electron injection layer is stacked on the electron transport layer. The electron injection layer is an aromatic (aromatic) having an imidazole ring, a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, etc. It can be produced by using low molecular materials containing compounds, boron compounds, etc. In this case, the electron injection layer may be formed in a thickness range of 100 kPa to 300 kPa.

The cathode is positioned on the electron injection layer. This cathode serves to inject electrons. 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, 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, the preparation or synthesis examples of the compounds comprising carbazole and aromatic amine derivatives belonging to formulas (5) and (6) will be described. However, since the number of compounds including the carbazole and the aromatic amine derivative belonging to the general formula (1) is large, it will be exemplarily described by selecting among the compounds including the carbazole and the aromatic amine derivative belonging to the formula (1). Those skilled in the art, that is, those skilled in the art can prepare a compound including carbazole and aromatic amine derivatives belonging to the present invention not illustrated through the preparation examples described below.

Synthetic

1. Synthesis of Intermediate 1

 [Reaction Scheme 1]

To prepare Intermediate 1 with reference to Scheme 1, 3-bromo-9-phenyl-9H-carbazole, bis (pinacolato) diboron, Pd (dppf) Cl 2, and KOAc were dissolved in DMF and stirred at 130 ° C. for 3 hours. The reaction mixture was cooled to room temperature and extracted three times with distilled water and dichloromethane. After removing the dichloromethane of the organic layer, the mixture was recrystallized with dichloromethane and hexane. The solid was filtered and dried in vacuo to afford intermediate 1 in a yield of 65%.

9-phenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H

When -carbazole is included, the intermediate is the same as the above synthesis method except that 2-bromo-9-phenyl-9H-carbazole is used instead of 3-bromo-9 -phenyl-9H -carbazole in the synthesis method of intermediate 1. . Yield 64%.

2. Synthesis of Intermediate 2

 Scheme 2

To prepare Intermediate 2 with reference to Scheme 2, 9-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole, tribromobenzene , Pd (PPh3) 4 and potassium carbonate (K2CO3) were added to tetrahydrofuran (THF) and distilled water and refluxed at 85 ° C for 12 hours. After completion of the reaction, the mixture was extracted three times with distilled water and methyl chloride (MC), and the precipitates in the organic layer were filtered, dried over magnesium sulfate, and the solvent was concentrated. The residue thus obtained was purified by column chromatography. 2 can be obtained in 63% yield.

If intermediate 2 is 2- (3,5-dibromophenyl) -9-phenyl-9H-carbazole, 9-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- except that 9-phenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole is used instead of yl) -9H-carbazole. same. Yield 60%.

3 . Synthesis of Intermediate 3

 Scheme 3

To prepare Intermediate 3 with reference to Scheme 3, 3- (3,5-dibromophenyl) -9-phenyl-9H-carbazole, diphenylamine, potassium carbonate, sodium sulfate (Na2SO4), copper (Cu), nitrobenzene The mixture was refluxed at 190 ° C. for 12 hours. After the completion of the reaction, the mixture was extracted three times with distilled water and methyl chloride, and the precipitate obtained in the organic layer was filtered, dried over magnesium sulfate, and the solvent was concentrated to obtain the desired intermediate 3 in 73% yield using column chromatography. Could.

When Ar of intermediate 3 is naphthyl, it is the same as the synthesis method except that N-phenylnaphthalen-1-amine is used instead of diphenylamine. Yield 70%.

When Ar of Intermediate 3 is fluorene, 2- (3,5-dibromophenyl) -9-phenyl-9H-carbazole and 9 instead of 3- (3,5-dibromophenyl) -9-phenyl-9H-carbazole and diphenylamine It is the same as the above synthesis method except using 9-dimethyl-N-phenyl-9H-fluoren-2-amine. Yield 68%.

If Ar in intermediate 3 is biphenyl, 2- (3,5-dibromophenyl) -9-phenyl-9H-carbazole and N are substituted for 3- (3,5-dibromophenyl) -9-phenyl-9H-carbazole and diphenylamine. It is the same as the above synthesis method except that -phenylbiphenyl-4-amine is used. Yield 65%.

4 . Synthesis of Intermediate 4

 Scheme 4

To prepare Intermediate 4 with reference to Scheme 4, 3-bromo-N, N-diphenyl-5- (9-phenyl-9H-carbazol-3-yl) aniline, bis (pinacolato) diboron, Pd (dppf) Cl ₂ , KOAc is dissolved in dimethylformamide and stirred at 130 ° C. for 3 hours. The reaction mixture was cooled to room temperature and extracted three times with distilled water and dichloromethane. After removing dichloromethane from the organic layer, the mixture was recrystallized with dichloromethane and hexane. The solid was filtered and dried in vacuo to afford intermediate 4 in 61% yield.

If Ar of intermediate 4 is naphthyl, N- (3-bromo-5- (9-phenyl-9H) instead of 3-bromo-N, N-diphenyl-5- (9-phenyl-9H-carbazol-3-yl) aniline Same as the above synthesis method except that -carbazol-3-yl) phenyl) -N-phenylnaphthalen-1-amine is used. Yield 67%.

If Ar of intermediate 4 is fluorene, N- (3-bromo-5- (9-phenyl-) instead of 3-bromo-N, N-diphenyl-5- (9-phenyl-9H-carbazol-3-yl) aniline It is the same as the synthesis method except that 9H-carbazol-2-yl) phenyl) -9,9-dimethyl-N-phenyl-9H-fluoren-2-amine is used. Yield 55%.

If Ar of intermediate 4 is biphenyl, N- (3-bromo-5- (9-phenyl-) instead of 3-bromo-N, N-diphenyl-5- (9-phenyl-9H-carbazol-3-yl) aniline 9H-carbazol-2-yl) phenyl) -N-phenylbiphenyl-4-amine is the same as the synthesis method except that. Yield 60%.

Synthesis of Compound A-3

 Scheme 5

To synthesize Compound A-3 with reference to Scheme 5, 3-bromo-N, N-diphenyl-5- (9-phenyl-9H-carbazol-3-yl) aniline, N, N-diphenyl-3- ( 9-phenyl-9H-carbazol-3-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline, Pd (PPh3) 4, sodium hydroxide It is added to hydrofuran and distilled water and refluxed at 90 ° C for 12 hours. After completion of the reaction, the mixture was extracted three times with distilled water and methyl chloride, and the precipitate obtained in the organic layer was filtered, dried over magnesium sulfate, and the solvent was concentrated. The residue obtained by column chromatography was used to give the desired compound A-3 in 53% yield. Could get by.

Synthesis of Compound A-7

When Ar of compound A-3 is naphthyl, 3-bromo-N, N-diphenyl-5- (9-phenyl-9H-carbazol-3-yl) aniline, N, N-diphenyl-3- (9-phenyl -9H-carbazol-2-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline instead of N- (3-bromo-5- (9-phenyl -9H-carbazol-3-yl) phenyl) -N-phenylnaphthalen-1-amine, N-phenyl-N- (3- (9-phenyl-9H-carbazol-3-yl) -5- (4,4, Same as the above synthesis method except that 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) naphthalen-1-amine is used. Yield 60%

Synthesis Method of Compound B-9

When Ar of compound A-3 is fluorene, 3-bromo-N, N-diphenyl-5- (9-phenyl-9H-carbazol-3-yl) aniline, N, N-diphenyl-3- (9- phenyl-9H-carbazol-2-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline instead of N- (3-bromo-5- (9- phenyl-9H-carbazol-2-yl) phenyl) -9,9-dimethyl-N-phenyl-9H-fluoren-2-amine, 9,9-dimethyl-N-phenyl-N- (3- (9-phenyl -9H-carbazol-2-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -9H-fluoren-2-amine except Is the same as the synthesis method. Yield 55%

Synthesis Method of Compound B-11

When Ar of compound A-3 is biphenyl, 3-bromo-N, N-diphenyl-5- (9-phenyl-9H-carbazol-3-yl) aniline, N, N-diphenyl-3- (9- phenyl-9H-carbazol-2-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) aniline instead of N- (3-bromo-5- (9- phenyl-9H-carbazol-2-yl) phenyl) -N-phenylbiphenyl-4-amine, N-phenyl-N- (3- (9-phenyl-9H-carbazol-2-yl) -5- (4,4 It is the same as the above synthesis method except that 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) biphenyl-4-amine is used. Yield 51%.

abandonment EL  Manufacturing evaluation of the device

Various compounds obtained through synthesis were used as light emitting host materials or hole transporting layers of the light emitting layer, respectively, to fabricate an organic light emitting device according to a conventional method. First, the developed material was first vacuum deposited on the ITO layer (anode) formed on the glass substrate to form a thickness of 10 nm.

Subsequently, NPD (or NPB) was vacuum deposited to a thickness of 30 nm as a major transport compound to form a hole transport layer. After forming the hole transport layer, when the developed material was measured by the hole injection layer, a light emitting layer doped with 7% of BD-052X having a thickness of 45 nm on the hole transport layer (where BD-052X is a blue fluorescent dopant and a light emitting host material) 9,10-di (naphthalene-2-anthracene (AND)) was used as the hole blocking layer (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineole). Ito) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm, and then tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm with an electron injection layer. . 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.

Comparative Experimental Example

When the compounds of the present invention were measured by a hole injection layer, 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine instead of the compound of the present invention for comparison (Hereinafter abbreviated as 2T-NATA) was used as a hole injection material to fabricate an organic light emitting display device having the same structure as the experimental example.

Hole transport
material Voltage
(V) Current density
(mA / cm ² ) Luminous efficiency
(cd / A) Chromaticity coordinates
(x, y) Example 1
Compound A-3 5.74 13.84 8.06 (0.150, 0.147) Example 2
Compound A-7 5.69 13.89 8.12 (0.151, 0.147) Example 3
Compound b-9 6.00 13.72 7.88 (0.151, 0.145) Example 4
Compound B-11 5.99 13.31 7.78 (0.150, 0.146) Comparative Example 1
2-TNATA 6.95 14.31 6.34 (0.150, 0.151)

As can be seen from the results of Table 1, the organic electroluminescent device using the organic electroluminescent device material of the present invention is not only improves the color purity and high efficiency, but also obtains blue light having a long life, so as a hole transporting material of the organic light emitting device. Can be used to significantly improve the low driving voltage, high luminous efficiency and lifetime.

Even if the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a hole transport layer as well as a light emitting layer, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained. .

The terms "comprise", "comprise" or "having" described above mean that a corresponding component may be included, unless otherwise stated, and thus, excludes other components. It should be construed that it may further include other components. All terms, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined. Commonly used terms, such as predefined terms, should be interpreted to be consistent with the contextual meanings of the related art, and are not to be construed as ideal or overly formal, unless expressly defined to the contrary.

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.

delete

Claims (12)

A compound represented by the following formula.

Where Cz is

Indicates.
In the above formulas,
(1) Ar1 to Ar4 each independently represent a substituted or unsubstituted aromatic hydrocarbon group having 5 to 40 carbon atoms; Or substituted or unsubstituted hetero ventilus having 3 to 60 atoms,
(2) R 1 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms,
(3) R 2 is a hydrogen atom; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted alkyl group having 1 to 50 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms; Substituted or unsubstituted arylthio group having 1 to 50 carbon atoms; A substituted or unsubstituted alkoxycarbonyl group having 2 to 50 carbon atoms; Amino groups substituted with a substituted or unsubstituted aryl group having 6 to 50 carbon atoms; A halogen atom; Cyano groups; Nitro group; Hydroxyl group; Or a carboxyl group;
(4) L is independently a substituted or unsubstituted arylene group; Substituted or unsubstituted hetero arylene group; Tetravalent or more substituted or unsubstituted aliphatic hydrocarbons; represents a linking group selected from the group consisting of. The method of claim 1,
The L is a compound represented by any one of the following formula.

The method of claim 2,
L is

Compound characterized by the above. The method of claim 1,
The compound is a compound represented by the formula:

Wherein R ₃ and R ₄ are the same as R ₁ and R ₂ as defined in claim ₁ , respectively. The method of claim 2,
The compound is one of the following compounds.

An organic electric device comprising at least one organic material layer comprising the compound of claim 1. The method according to claim 6,
The organic electroluminescent device according to claim 1, wherein the organic layer is formed by a solution process. The method according to claim 6,
An organic electric device comprising a first electrode, the organic material layer and a second electrode sequentially stacked. The method of claim 8,
The organic material layer is an organic electric element, characterized in that any one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. The method of claim 8,
The organic material layer includes a hole transport layer,
In the hole transport layer, the compound is an organic electric device, characterized in that used as a hole transport material. A display device comprising the organic electric element of claim 8;
And a control unit for driving the display device. The method of claim 11,
The organic electroluminescent device is an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC) drum, characterized in that one of the organic transistor (organic TFT).

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