WO2011155742A2 - Compound comprising carbazole and aromatic amine derivatives, organic electronic element using same, and terminal comprising the organic electronic element - Google Patents

Abstract

The present invention relates to compound comprising carbazole and aromatic amine derivatives, an organic electronic element using the same, and to a terminal comprising the organic electronic element.

Description

Compound containing carbazole and aromatic amine derivative and organic electric device using 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 emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, 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 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 the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. In order to increase the light emitting efficiency through the light emitting material, a host / dopant system may be used. The principle is that when a small amount of a 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 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.

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, light emitting material and passivation (kepping) material in organic electronic devices, in particular light emitting material and host 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 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 addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

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 as follows.

[Formula 1]

(1) Ar ₁ to Ar ₄ 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 nuclear atoms. Ar ₁ to Ar ₄ may be bonded to adjacent groups, respectively, to form a substituted or unsubstituted saturated or unsaturated aliphatic ring, or a hetero ring having N, O, S, P, and Si as heteroatoms. For example, Ar ₁ and Ar ₂ , Ar ₃ and Ar ₄ may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated aliphatic ring or a hetero ring having N, O, S, P, and Si as heteroatoms. have.

(2) Cz represents the following Chemical Formula 2, wherein R ₁ is a substituted or unsubstituted aryl group having 6 to 60 nuclear carbon atoms, R ₂ is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 60 nuclear carbon atoms, Substituted or unsubstituted C1-C50 alkyl group, substituted or unsubstituted C1-C50 alkoxy group, substituted or unsubstituted C6-C50 alkyl group, substituted or unsubstituted C1-C50 arylcycle Amino, substituted or unsubstituted alkoxycarbonyl groups having 2 to 50 carbon atoms, substituted or unsubstituted aryl groups having 6 to 50 carbon atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups or carboxyl groups Can be. here

Indicates the position of connection with other groups . It is the same below.

[Formula 2]

(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.

More specifically, L

Can be.

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.

[Formula 3]

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

[Formula 4]

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.

[Formula 5]

[Formula 6]

Compounds represented by Formula 1, Formula 3 to Formula 4 may be one of the compounds represented by Formula 5 and Formula 6, but is not limited thereto. In this case, Ar ₁ to Ar ₄ , Cz, and R ₁ to R _{4, which} are substituents of the compounds represented by Formula 1, Formula 3 to Formula 4, are difficult to exemplify all the compounds in a broad relationship. However, the compounds represented by Formula 1, Formula 3, and Formula 4, which are not represented by Formulas 5 to 6, may also form part of the present specification.

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), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO ₂ : 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.

The hole injection material is a material capable of well injecting holes from the anode at low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material 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.

Production 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 carbazole and aromatic amine derivatives belonging to the general formula (1) is large, it will be exemplarily described by selecting among compounds including carbazole and aromatic amine derivatives belonging to the general 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

 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%.

However, in the case of containing 9-phenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole, 3-bromo in the synthesis method of intermediate 1 Intermediate is the same as the above synthesis method, except that 2-bromo-9-phenyl-9H-carbazole is used instead of -9-phenyl-9H-carbazole. 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 (PPh ₃ ) ₄ and potassium carbonate (K ₂ CO ₃ ) 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 obtained by column chromatography was subjected to desired intermediates. 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 (Na ₂ SO ₄ ), copper (Cu), Nitrobenzene was added and refluxed at 190 ° 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 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 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 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 resultant 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 desired compound A-3 was obtained by column chromatography 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%.

Manufacturing evaluation of organic electroluminescent element

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.

[Formula 7]

Meanwhile, Ar ₁ to Ar ₄ , Cz, and R ₁ to R _{4, which} are substituents of the compounds represented by Chemical Formulas 1 and 3 to ₄ , are representative examples of the synthesis of compounds in a wide range. Compounds represented by Formula 1, Formula 3, and Formula 4, which are not described by way of example, may also form part of the present specification.

Comparative Experiment

When the compounds of the present invention were measured by the 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.

Table 1

	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 has high efficiency and color purity as well as long-lasting blue light emission is obtained as a hole transporting material of the organic electroluminescent 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 meanings as commonly understood by one of ordinary skill in the art unless otherwise defined. Terms commonly used, such as terms defined in a dictionary, should be interpreted to coincide with the contextual meaning of the related art, and shall not be construed in an ideal or excessively formal sense unless explicitly defined in the present invention.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, 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.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application claims priority under No. 119 (a) (35 USC § 119 (a)) of the Patent Application No. 10-2010-0054059, filed to South Korea on June 08, 2010. All content is incorporated by reference in this patent application. In addition, if this patent application claims priority for the same reason as above for a country other than the United States, all the contents thereof are incorporated into this patent application by reference.

Claims (12)

1. Compound represented by the following formula:

   

   here

   Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted aromatic hydrocarbon group having 5 to 40 carbon atoms, or a substituted or unsubstituted hetero atom having 3 to 60 nuclear atoms,

   Cz is

   

   Wherein R ₁ is a substituted or unsubstituted aryl group having 6 to 60 nuclear carbon atoms, R ₂ is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, substituted or unsubstituted C 1 to 60 carbon atoms 50 alkyl groups, substituted or unsubstituted alkoxy groups having 1 to 50 carbon atoms, substituted or unsubstituted alkyl groups having 6 to 50 carbon atoms, substituted or unsubstituted arylthio groups having 1 to 50 carbon atoms, substituted or unsubstituted carbon atoms An amino group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, or a carboxyl group substituted with a 2 to 50 alkoxycarbonyl group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms,

   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.
2. The method of claim 1,

   L is specifically,

   

   Compound selected from the group consisting of.
3. The method of claim 2,

   L is specifically

   

   Compound characterized by the above.
4. 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.
5. The compound of claim 2, wherein the compound is

   

   

   

   

   Compounds, characterized in that one selected from the group consisting of.
6. An organic electric device comprising at least one organic material layer comprising the compound of claim 1.
7. The method of claim 6,

   The organic electroluminescent device according to claim 1, wherein the organic layer is formed by a solution process.
8. The method of claim 6,

   The organic electroluminescent 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.
9. 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.
10. The method of claim 8,

    The organic material layer includes a hole transport layer,

    And the compound is used as a hole transport material in the hole transport layer.
11. A display device comprising the organic electric element of claim 8;

    And a control unit for driving the display device.
12. The method of claim 11,

    The organic electroluminescent device is one of an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic transistor (organic TFT).

Images